CN109468049A - The aqueous blending paint of environment-friendly type one-pack-type and the aqueous blending paint of dual liquid type - Google Patents

The aqueous blending paint of environment-friendly type one-pack-type and the aqueous blending paint of dual liquid type Download PDF

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Publication number
CN109468049A
CN109468049A CN201710798866.5A CN201710798866A CN109468049A CN 109468049 A CN109468049 A CN 109468049A CN 201710798866 A CN201710798866 A CN 201710798866A CN 109468049 A CN109468049 A CN 109468049A
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aqueous
agent
resin
type
water
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张娟娟
张建龙
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Sunny General International Co Ltd
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Sunny General International Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/08Polyurethanes from polyethers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/06Polyurethanes from polyesters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/20Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2227Oxides; Hydroxides of metals of aluminium
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/30Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045Sulfates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention discloses a kind of aqueous blending paints of environment-friendly type one-pack-type, include: (A agent) aqueous resin dispersion, it includes at least one by tertiary amine (water-base resin that such as triethylamine neutralizes), at least one water-base resin is selected from the group as composed by aqueous epoxy resins, aqueous polyurethane resin and aqueous acryl resin, and at least one water-base resin contains carboxyl and other reactive functional groups;And the bridging agent of selection is when (B agent);When A agent and B agent are mixed into the aqueous blending paint of one-pack-type, after spraying is dry, bridging agent and at least one water-base resin carry out bridging reaction, to form the reticular structure that intersects.The aqueous blending paint of one-pack-type of the invention can be coated on the material protective film that impermanency is formed in a variety of materials; material after processing is completed; as long as being immersed in the water, protective film can be easily from material surface removing, recycling, centralized processing, and whole process is without using any organic solvent.The present invention also discloses a kind of aqueous blending paint of dual liquid type.

Description

The aqueous blending paint of environment-friendly type one-pack-type and the aqueous blending paint of dual liquid type
Technical field
The present invention relates to a kind of aqueous blending paints of environment-friendly type one-pack-type, more particularly about one kind comprising blending together resin And the aqueous blending paint of one-pack-type of bridging agent.The invention further relates to a kind of aqueous blending paints of dual liquid type.
Background technique
Either during the processing or reprocessing of organic or inorganic material, it is commonly exposed to hardness containing fine sand and rubs up to 7.0 In the dust environment of family name's hardness (Mohs scale);General inorganic material (metal and nonmetallic) is high compared with the hardness of organic material, But the hardness of inorganic material is still less than 7.0;Inorganic material include metal with it is nonmetallic, such as:
1, metal: iron, steel, aluminium, copper, metal alloy, plating (nickel, chromium) film metal material etc.;
2, nonmetallic: wafer, glass (optics, solar panels, ITO, eyeglass, mirror surface), stone material.
Above-mentioned material is in polished surface, material transfer and process, and surface is highly susceptible to scratch or wear, absolutely To needing surface protection film to protect.
As for the lower organic material of hardness, such as: the hardness of plastics, engineering plastics, composite material, baking vanish surface material Lower (respectively less than 2.0 mohs hardnesses (Mohs scale)), in the processing and transport process of material, with greater need for there is firm protection Film protection;Such as:
1, plastics: polycarbonate (polycarbonates, the peace applied to sunshading board, eyeglass, locomotive aircraft etc. Full glass), polymethyl methacrylate (PMMA, sunglasses, car light etc.), ABS (3C articles);
2, composite material (such as carbon fiber, glass) product;
3, baking vanish (such as automobile, household electrical appliances) surface.
The mode of the temporary material surface protection of the tradition of material surface at present, has multiple product listing, only commodity Brief technical data, application and form of construction work introduction, but the content disclosed successively from patent document in recent years, it may be appreciated that wherein Group ingredient and feature, sketch data as follows:
1, (2005) United States Patent (USP) 6964989B1 use PVB (polyvinyl butyral resin) film, solvent type PU glue solid, PVA (polyvinyl alcohol) work as separation agent.
2, (2006) United States Patent (USP) 6991851B2, using aqueous PU and acrylic monomer formation coating containing sulfonate, separately Work as separation agent using hydrophilic polyol (polyols), metallic soap of stearic acid, castor oil etc..
3, U.S. Patent application 2012/178862 uses solvent type acryl resin and polynary poly- propyl alcohol, glycerine fatty acid Ester works as separation agent.
4, United States Patent (USP) 9481806 (2016) is copolymerized using polyvinyl acetate (polyvinyl acetate)/acrylic Object lotion is separately used as thickener and separation agent using polyethylene glycol (PEG, polyethylene glycols) as coating.
5, United States Patent (USP) 9290677 (2016), using including cellulose acetate butyrate ester (cellulose acetate Butyrate ester), sucrose acetate isobutyrate (sucrose acetate isobutyrate), acrylic copolymer) etc. The solvent based coating of polymer, after forming film, it is necessary to use organic solvent (such as THF, double alcohol or diester compound) as de- Film.
6, United States Patent (USP) 8263231 (2012) uses Water-borne modification polyvinylbutyrate (polyvinyl butyrate) cream Liquid, film cleaning need organic solvent.
7, United States Patent (USP) 8048258 (2011) uses N, N- dimethylacrylate (N, N-diethylacrylate), N- Vinyl pyrrolidone (N-vinyl pyroridone) monomer and acrylic copolymer, free radical starting agent etc. form coating, Remover needs organic solvent.
8, United States Patent (USP) 7531221 (2009), both 7524536 (2009) are respectively with acrylic lotion and water-borne wax when painting Material, film can not mechanical resistant (such as: wear-resisting, scratch resistance, hardness) property.
9, United States Patent (USP) 6682773 (2006), 6849328 (20016), 7252853 (2007), 7165307 (2007) etc. Four patents work as temporary coating using water-soluble high-molecular material respectively, can not provide material material in various process The function of material protection film.
It is currently known the application of protection materials technology (containing commercialization or patent), on the surface of the material protection construction and application Property respectively has excellent, disadvantage, their work progress, other protection films in addition to the mode of pad pasting are required to organic solvent Such as: solvent (for diluting coating or release coated film), plasticiser (for increasing the flexibility of film), coalescing agent containing chlorine Equal volatile organic matters (VOC) therefore causes the doubts such as safety, health, fire, environmental pollution before and after construction.
The advantage and disadvantage for briefly explaining the prior art are as follows:
1, transparent resin pad pasting
Advantage: when being applied to small area material surface, being easily processed, and quick, the manual demoulding of construction is easy.
Disadvantage: when applied to large area and having the surface of curved surface or 3D, pad pasting is unable to reach comprehensive protection;Pad pasting only leans on quiet The density of electricity or pressure-sensing glue and material surface is bad;The hardness of pad pasting is bad;There may be residue glue (pressure-sensing glue);Resist processing chemistry Product are bad.
2, solvent type film
Advantage: spraying coating is easy, and density and flexibility are adjustable.
Disadvantage: manufacture, transport with coating waste water drying process, have a large amount of organic solvents (usually > 75% content solvent) Volatilization, it is not only inflammable and cause air pollution;The final film stripping that applies is not easy, and needs to rely on a large amount of organic solvents, therefore after removing Film contains a large amount of solvents, and processing is difficult.
3, ultraviolet light photopolymerization type film
Advantage: can be rapid curing by ultraviolet light after coating.
Disadvantage: in coating process, exist with volatile organic substance (containing plasticiser), cause work peace and health Doubt;And it is not easy demoulding after processing, it needs to do destructive processing with highly basic.
4, emulsifier resin
Advantage: Water-borne modification solvent based coating (additional emulsifier) can reduce wind of the solvent based coating in transporting and constructing Danger.
Disadvantage: there is the puzzlement that VOC is caused containing organic solvent;Additional emulsifier is moved to protection materials surface, causes It stains on surface;Lotion and additive dose object, often result in coating unstability (lotion by critical micro-cell concentration (CMC, Critical micelle concentration) limitation, temperature and mechanical stirring etc. will cause lotion unstability);Most Whole protective film is not easily stripped, and needs to clean using more organic solvents.
Above-mentioned, the mode of traditional material surface protection is taken a broad view of, the puzzlement and secret worry of environmental protection, health, safety are not only caused, and And there are the limitation of its material processing method and the problem needs of final protective film lift-off processing to overcome;Future faces environmental regulation dirt The more stringent of anti-system specification is contaminated, therefore seeks the product for meeting environmental requirement, especially industrial circle responds the society to preserve our planet Meeting responsibility, is duty-bound.
Summary of the invention
A purpose of the present invention is that a kind of novel environment-friendly type aqueous blending paint is provided, to improve traditional protected material The shortcomings that material technology.
For the above-mentioned purpose and other purposes, the present invention propose a kind of aqueous blending paint of environment-friendly type one-pack-type, comprising mixed A agent and B agent are closed, the aqueous blending paint of single formulation is formed and stores for future use:
A agent, aqueous resin dispersion, it includes at least one by tertiary amine (such as triethylamine (triethyl amine, TEA the)) water-base resin neutralized, wherein at least one water-base resin are selected from by aqueous epoxy resins, aqueous polyurethane resin and water Property acryl resin composed by group, and at least one water-base resin contains carboxyl (COO-) and other reactive functional groups; And B agent, bridging agent;After the aqueous blending paint of the one-pack-type is dry, the bridging agent and at least one water-base resin into Row bridging reaction intersects reticular structure (Interpenetrating Polymeric Networks, IPN) to be formed.
In one embodiment of the invention, the aqueous blending paint of one-pack-type includes: the resin of 100 parts by weight;And 0.1~ The bridging agent of 30.0 parts by weight.
In one embodiment of the invention, the aqueous blending paint of one-pack-type is further included:
(C) organic additive is selected from the group as composed by thickener and antioxidant;And
(D) inorganic filler, selected from by calcium carbonate, mountain flour, barium sulfate, silica, aluminium oxide and titanium dioxide institute group At group.
In one embodiment of the invention, bridging agent select free multicomponent aziridine (polyaziridines, such as PICASSIAN XL-706), polynary carbodiimides (polycarbodiimides, such as PICASSIAN XL-701) and polynary Group composed by isocyanates (polyisocyanates, such as CORONATE AQ130).
For the above-mentioned purpose and other purposes, the present invention also propose a kind of aqueous blending paint of dual liquid type, include A agent and B Agent two-form:
A agent, it includes: aqueous resin dispersion, it includes at least one by tertiary amine (such as triethylamine (triethyl Amine, TEA)) neutralize water-base resin, wherein at least one water-base resin be selected from by aqueous epoxy resins, aqueous polyurethane tree Group composed by rouge and aqueous acryl resin, and at least one water-base resin contains carboxyl (COO-) and other reactive officials It can base;And
B agent, it includes: bridging agent;
Wherein, before construction application, the A agent and B agent are mixed to form aqueous blending paint, and the aqueous blending paint After drying, the bridging agent and at least one water-base resin carry out bridging reaction, to form the reticular structure that intersects (Interpenetrating Polymeric Networks,IPN)。
In one embodiment of the invention, after A agent is mixed to form aqueous blending paint with B agent, aqueous blending paint packet Contain: the resin of 100 parts by weight;And 0.1~30.0 parts by weight bridging agent.
In one embodiment of the invention, A agent is further included: organic additive, selected from by thickener and anti-oxidant Group composed by agent;And
B agent further includes: inorganic filler, selected from by calcium carbonate, mountain flour, barium sulfate, silica, aluminium oxide and two Group composed by titanium oxide.
In one embodiment of the invention, the bridging agent in B agent select free multicomponent aziridine (polyaziridines, PICASSIAN XL-706), polynary carbodiimides (polycarbodiimides, PICASSIAN XL-701) and polynary different Group composed by cyanate (polyisocyanates, CORONATE AQ130).
In one embodiment of the invention, the pH value of aqueous resin dispersion is greater than 8.
Whereby, the aqueous blending paint of one-pack-type of the invention and the aqueous blending paint of dual liquid type, for material provide it is non-forever The protection of long property (temporary).Those skilled in the art of the technical field of the invention, can be according to the property and knot of material surface Structure, to select nontoxic aqueous epoxy resins, aqueous polyurethane resin, aqueous acryl resin dispersion liquid (lotion) etc. to blend together tree Rouge formula, and combine various aqueous bridging agents (such as polynary aziridine is (polyaziridines, PICASSIAN XL-706, more First carbodiimides (polycarbodiimides, PICASSIAN XL-701) and multicomponent isocyanate (polyisocyanates, CORONATE AQ130) etc. forms the aqueous blending paint of one-pack-type and dual liquid type is aqueous blendes together painting Material, coating on the surface of the material, such as: metal, nonmetallic, plastics, the various material surfaces such as stone material or baking vanish, via room temperature or Heating, drying, forming material protect film (5-150 mm of thickness);In the drying process, only moisture evaporation and bridging reaction Occur, no any toxic volatile organic matter (VOC) discharge.
The present invention is to manufacture the aqueous blending paint of impermanency protection purposes as target:
1, using coating of the present invention formed protective film be tightly attached to material surface, avoid material through production, storage and transportation, cutting, Punching machine is applied etc. again during processing programs become end product, by any scratch or to stain etc., to reach safeguard protection The purpose of material;
2, finally after processing is completed, protected material is immersed in aqueous solution (room temperature~80 DEG C), without using any Organic solvent, this protective film can easily peel off and recycle centralized processing, not will cause water pollution, and after all demouldings Material surface does not remain any coating yet.
The Property requirements of material protective film according to the present invention, can be by aqueous epoxy resins, polyurethane resin, aqueous acrylic The formula dosage of the formulation selection and bridging agent of resin dispersion liquid (lotion) and other additives and filler etc. adjusts; The demoulding condition of protective film in aqueous solution, then can adjust bridge formation density by the dosage of bridging agent, to reach customized material Expect the demand of protective film.Construction as aqueous blending paint is coated with relevant nature, such as viscosity, consistency, thixotropy, coating thickness , then can be by filler with hardness etc., such as silica, aluminium oxide, calcium carbonate (mountain flour), barium sulfate, titanium dioxide is inorganic Composition formula adjusts.This material protection coating can provide the environmentally friendly scale removal process after perfect protective nature and function, processing, and The characteristics such as the allotment of customized water paint product and diversity application, are the characteristics of the aqueous blending paint of the present invention.
Detailed description of the invention
Fig. 1 is the schematic diagram that aqueous blending paint of the invention is formed by protective film after drying.
Symbol description:
10 protective films
11 bridging agents
12 epoxy resin
13 polyurethane resins
14 acryl resins
Specific embodiment
To fully understand the purpose of the present invention, feature and effect, hereby by following specific embodiments, and cooperate attached drawing, It elaborates, illustrates as after to the present invention:
The unit " phr " of additive amount used in the present invention means resin (parts per hundred per hundred parts Parts resin) additive amount, that is, relative to the resin of every 100 parts by weight, parts by weight contained by each additive.
" pencil hardness " described in the present invention is measured according to " ASTM D3363 " fixed testing standard.
" density " described in the present invention (test of hundred lattice) be according to " ASTM D3359 " fixed testing standard come It is measured.
" one-pack-type " aqueous blending paint and " dual liquid type " aqueous blending paint of the invention according to material (no matter it is organic or Inorganic material) chemistry on surface, physics material and protective film performance requirement (such as pencil hardness, density, water resistance, resist processing Chemicals etc.), select the aqueous resin dispersions (lotion) such as epoxy resin, Polyurethane (PU) and the acryl resin of different proportion It is formed with bridging agent.Through being dried to after " one-pack-type " aqueous blending paint of the invention and " dual liquid type " aqueous blending paint coating When film, common carboxyl reduction contained by resin aqueous emulsion micella is at carboxylic acid (COOH), and (such as polynary ethylene is sub- with bridging agent for starting Amine, polyaziridines, PICASSIAN XL-706) open loop or polynary carbodiimides (polycarbodiimides, PICASSIAN XL-701) etc. bridging reactions;Institute's amino-contained and bridging agent in PU resin (multicomponent isocyanate, Polyisocyanates, CORONATE AQ130), carry out addition reaction, in another PU resin institute's amino-contained and acryl resin or Epoxy group contained in epoxy resin, while carrying out ring-opening reaction etc. and generate the bridging reaction of chemical bonded refractory.Aqueous blending paint Construction property, such as viscosity, consistency, thixotropy, coating thickness and pencil hardness, then by filler, such as silica, oxidation The inorganic composition formula of aluminium, calcium carbonate (mountain flour), barium sulfate, titanium dioxide etc. adjusts;Carboxylic in dried coating film, in water-base resin Base (COO-) is gradually reduced into carboxylic acid (COOH), therefore the aqueous resin that blendes together carries out the bridge formation such as addition, open loop with bridging agent automatically Reaction, the response type for generating blending paint intersect reticular structure (Interpenetrating Polymeric Networks, IPN) film, form customized protection film character;Contained non-bridging reaction in the resin of formulation for coating material regulation simultaneously Carboxylic acid equivalents and bridge formation density, also can adjust the hydrophily of film, control it is final after finished-product material film it is easily peelable Property (peelability).
Three classes water-base resin used in the aqueous blending paint of one-pack-type of the invention and the aqueous blending paint of dual liquid type And reactive functional group contained by bridging agent is as follows:
Manufacture the three classes water-base resin of above-mentioned schematic diagram: epoxy resin, polyurethane resin (PU) and acrylic respectively first Resin etc. equally contains the resin of carboxylic acid (COOH), is separately added into triethylamine, after the carboxylic acid included (COOH) is neutralized, forms parent Aqueous anion base (carboxyl, COO-), then the self-emulsified water-base resin point to form each self-stabilization of three classes is added water and stirred respectively Dispersion liquid (lotion) (self-emulsified aqueous emulsion);Carboxylic hydrophilic nmature, provides stabilization in resin Aqueous resin dispersion (lotion), without additional emulsifier.This three classes resin dispersion liquid (lotion) is modulated into respectively with pure water solid Content (5~60%), with benefit it is subsequent it is aqueous blend together mixing for cold coating and match, this three classes aqueous resin dispersion (lotion) is averaged Partial size is about between 30-250 nanometer (nm, 1x10-9 meters), although belonging to different chemical structures and property, is formed respective micro- Born of the same parents (micelles), are dispersed stably in water phase, and micella periphery is hydrophilic anions base (carboxyl), are formed by therebetween Boundary's tower current potential (zeta potential), promotes micella mutually exclusive and generates Brownian movement (Browanian motion), shape At uniform and stable mixed emulsion;This three classes dispersion liquid has splendid compatibility each other, can be according to the resin emulsion of any ratio Blending formed it is aqueous blend together resin dispersion liquid, and the aqueous resin dispersion because including ion radical (lotion), have no critical micella The limitation (Critical Micelle Concentration) of concentration, is respectively present in water phase, so absolutely with stablizing micella The phenomenon that without mutually separating, therefore resin dispersion liquid (lotion) state can be uniformly and stably blended together, and can be super in normal temperature storage Spend 6 months or more.
Coating in application, can according to material surface material and protection film properties (such as pencil hardness, density, water resistance, it is resistance to plus Work chemicals etc.) demand, select the aqueous resin dispersions such as suitable epoxy resin, Polyurethane (PU) and acryl resin (lotion), is deployed into that " one-pack-type " or " dual liquid type " is aqueous to blend together cold coating with bridging agent in varing proportions, dry after coated When dry film forming, common carboxyl reduction contained by resin aqueous emulsion micella starts (such as more with bridging agent at carboxylic acid (COOH) First aziridine, polyaziridines, PICASSIAN XL-706) open loop or polynary carbodiimides The bridging reaction of (polycarbodiimide, PICASSIAN XL-701): institute's amino-contained and bridging agent are (more in such as PU resin First isocyanates, polyisocyanates, CORONATE AQ130), carry out addition reaction, in another PU resin institute's amino-contained with Epoxy group contained in acryl resin or epoxy resin, while carrying out ring-opening reaction etc. and generate the bridging reaction of chemical bonded refractory Deng.Above-mentioned reaction is as follows:
The self-emulsified type aqueous resin dispersion (lotion) of three classes used in the present invention, can in any proportion and bridging agent (aqueous) blending is formed by " one-pack-type " or " dual liquid type " is aqueous blendes together cold coating, while dry, can automatically into The reaction such as row addition, open loop, generate blend together resin response type (3D three-dimensional) reticular structure that intersects (IPN, Interpenetrating Polymeric Networks) film, to reach customized protection film character;At the same time The equivalents and bridge formation density of the carboxylic acid of contained non-bridging reaction in controllable resin, to adjust the hydrophily of film, so that with Control the easy peelability (peelability) of final finished film.As shown in Figure 1, the aqueous cold coating that blendes together of the invention passes through Protective film 10 is formed by after drying may include: bridging agent 11, epoxy resin 12, polyurethane resin 13 and acryl resin 14, Wherein, resins are waited to be cross-linked to each other by bridging agent 11.
The representative manufacturing process of aqueous resin dispersion (lotion), is summarized as follows respectively:
Add water-reducible aqueous epoxy resin emulsion (water-reducible aqueous epoxy resin Emulsion):
By epoxy resin, (Epoxy resin, NPES-902 or NPES-904 are purchased from the limited public affairs of South Asia plastics industry share Department) merging three-necked bottle, make to be dissolved in a small amount of tetrahydrofuran (THF, tetrahydrofuran), and reaction flask is warming up to 75 DEG C, with mechanical agitator, it is slowly added into succinic anhydride (succinic anhydride) powder uniform stirring, reaction temperature maintains It is cooled to room temperature after 75 DEG C, about 8 hours, epoxy resin and succinic anhydride, completes half-esterification reaction (such as above formula);It is another to prepare triethylamine (triethyl amine) be added pure water (500ml), preparation pH value about 8.0~10.0 aqueous solution.By above-mentioned epoxy resin With the half-esterified products liquid of succinic anhydride, it is slowly added into the aqueous solution containing triethylamine and is quickly stirred using mechanical agitator (1000rpm) until half-esterified products add, and maintains stir about 4 hours, i.e. 30~60% solid content aqueous rings of completion Oxygen resin dispersion liquid (lotion).
EP-1:NPES-902, epoxide equivalent (EEW) 600-650
EP-2:NPES-904, epoxide equivalent (EEW) 740-850
Self-emulsified aqueous PU dispersion liquid (lotion) (the self-emulsified aqueous polyurethane of type Dispersion):
Choose polyalcohol (polyols, such as polyether polyol (polyether polyols, such as PU-1, PU-3), poly- carbonic acid Esterdiol (polycarbonate diols, such as PU-2) or polycaprolactone glycol (polycaprolactone diols, such as PU- ) and multicomponent isocyanate (polyisocyanates, such as isophorone diisocyanate (IPDI, isophorone 4) Diisocyanate) or methyl diphenylene diisocyanate (MDI, methane diphenyl diisocyanate)) as PU Raw material selects dihydromethyl propionic acid (DMPA, dimethylol propanic acid) as the anion base raw material of PU main chain, system Make PU prepolymer carboxylic-containing acid (PU prepolymers);Polyalcohol (polyols) and DMPA are placed in 4 neck bottles first, with Heating packet is heated to 120 DEG C, is cooled to room temperature after vacuumizing dehydration about 4 hours, then slowly instill IPDI, reaction flask is stirred with machinery Device stirring is mixed, reaction temperature maintains 75 DEG C about 4 hours, and until NCO% is lower than theoretical value, i.e., completion PU prepolymer is anti- It answers.Pure water (500ml) is added in another prepare triethylamine (TEA, triethyl amine), preparation pH value about 10.0 aqueous solution, Ethylenediamine (EDA, ethylene diamine) is mixed when chain elongation agent.Aqueous solution by above-mentioned preparation containing TEA and EDA, slowly PU prepolymer is added, and is dispersed with stirring with flash mixer, completes the aqueous PU dispersion liquid (lotion) of 30% solid content.
PU-1:PTMEG-1000 (polyalcohol), IPDI (multicomponent isocyanate)
PU-2:PC-2000 (polyalcohol), IPDI (multicomponent isocyanate)
PU-3:PPG-1000 (polyalcohol), IPDI (multicomponent isocyanate)
PU-4:PCL-1000 (polyalcohol), MDI (multicomponent isocyanate)
The self-emulsified aqueous acryl resin lotion of type (self-emulsified aqueous polyacrylate Emulsion):
R=-CH3 ,-C4H9 or-C6H13
Traditionally emulsion polymerization method prepares the aqueous acryl resin lotion of self-emulsified type;Select initiator, persulfuric acid Ammonium (ammonium persulfate), emulsifier, lauryl phenylbenzimidazole sulfonic acid ester (lauryl benzyl sulfonate) are dissolved in Lotion is made in distilled water solution;Then, by reaction monomers raw material, acrylic acid (acrylic acid), alkyl acrylate (alkyl acrylates), methacrylic acid (methacrylic acid) or the methacrylate containing epoxy group Monomer mixed solutions such as (glycidyl methacrylate) (with TEA adjust pH value > 8.0), be slowly added into it is above-mentioned containing emulsifier, In the lotion of initiator etc., after being heated up to 40 DEG C, start the exothermic reaction for carrying out emulsion polymerization, is voluntarily risen with water-bath control lotion The speed of temperature maintains 80 DEG C of about 4 hours emulsion polymerizations reactions and completes to 80 DEG C, and aqueous sub- gram containing 30~60% solid contents Power resin emulsion.
AC-1:R=hexyl (hexyl)
AC-2:R=methyl (methyl)
More than used herein plus water-reducible aqueous epoxy resins, self-emulsified type aqueous polyurethane resin point Dispersion liquid (lotion) and the aqueous acryl resin lotion of self-emulsified type etc. represent the aqueous resin dispersion (lotion) of type, respectively With the lotion that independent micro-cell structure is formed, three includes identical anionic carboxyl, has splendid compatibility, any ratio The phenomenon that example can mix that manufacture is stable to blend together resin dispersion liquid (lotion), absolutely not mutually separate (phase separation), Resin includes ion radical (carboxyl), also without " critical micro-cell concentration " (CMC, critical micelle concentration) Limitation;Amido in the hydrophilic carboxylic acid and micella outside drying and forming-film, micella will distinguish same bridging agent together, such as polynary Aziridine (polyaziridines such as PICASSIAN XL-706 is purchased from STAHL HOLDINGS B.V.) or polynary carbonization Diimine (polycarbodiimides such as PICASSIAN XL-701 is purchased from STAHL HOLDINGS B.V.), polynary isocyanic acid Ester (polyisocyanates is purchased from Nippon Polyurethane Industry Co., Ltd. such as CORONATE AQ130) etc., carry out open loop or The bridging reaction of addition, individual chemical bonded refractories for generating amido ester (aminoester) and urea groups (ureas), forms reticular structure Film, will be automatically formed after dry and uniformly blend together resin (hybridized resins) protective film;These three types of resins are matched Fang Zucheng selects the mixed proportion and bridge formation of resin raw material ingredient, resin dispersion liquid (lotion) with the demand of protection film character Agent composition, generates the resin protection film that blendes together of customized property, is the advantage that the present invention blendes together cold coating application.
This three classes water-base resin raw material, is known industrial source, and the manufacture of self-emulsified type aqueous resin dispersion Technique is also existing technology, is this as the aqueous diversification application feature for blending together resin (hybridized resins) The characteristics of invention;The present invention uses the customized property for blending together resin in embodiment, selects the feature group of individual water-base resins It closes, feature is briefly described as follows respectively:
1, add water-reducible aqueous epoxy resins: there is excellent rigidity, toughness and hardness etc., determine in epoxy resin Principal component bisphenol-A (bis-phenol A, BPA) composed by high epoxide equivalent (epoxy equivalent weight, EEW), EEW is higher, and such as EP-2 > EP-1, the Nature comparisons such as rigidity, toughness and the hardness of EP-2 aqueous epoxy resins are high.
2, the aqueous PU dispersion liquid (lotion) of self-emulsified type: there is excellent flexibility, wearability, ductility, adherence Etc. properties, determine the principal component in PU resin, PU prepolymer composed by polyol molecular weight and multicomponent isocyanate;It is polynary Alcohol molecular weight is higher, such as PU-2 > PU-1, is formed by then PU property, the properties such as flexibility, wearability, ductility, adherence are got over It is good;If multicomponent isocyanate uses aromatic series, forms (PU-4 > PU-3) properties such as rigidity, hardness, the wearability of PU and get over It is good.
3, the aqueous acryl resin lotion of self-emulsified type: there is excellent flexibility, ductility, adherence etc.;If making Compare methacrylate with a variety of chain alkyl acrylate (such as Hexyl 2-propenoate (n-hexyl acrylate), AC-1) Acryl resin obtained by the raw material monomer of (methyl acrylate) has lower Tg temperature, provides acryl resin (AC-1 > AC-2) property such as flexibility, ductility, adherence, as raw material monomer glycidyl acrylate (GA, Glycidyl acrylate) in acryl resin, the epoxy group of amido open loop bridging reaction is provided, to increase blending paint Bridge formation density and density.
The pH-value (pH value) of this three classes aqueous resin dispersion (lotion), is respectively maintained at pH > 8.0~11.0.Its Common carboxyl (anion base) forms stable aqueous resin dispersion (lotion), because including identical anion base respectively, when Two or three of aqueous resin dispersion (lotion), blending uniformly, becomes aqueous and blendes together resin dispersion liquid (cream in varing proportions Liquid), still steadily it is present in water phase with a other micella dispersion liquid (lotion), dispersion liquid (lotion) does not have that " critical micella is dense The limitation of degree " (CMC), can arbitrarily plus pure water is diluted to the coating concentration that can be coated with and adjustment viscosity, is formed stable aqueous Blend together cold coating.The ratio that three classes aqueous resin dispersion (lotion) arbitrarily mixes, with it is customized protection film character demand, Select proper proportion aqueous resin dispersion (lotion) with drawing on the strong points to offset the weaknesses is uniformly mixed and aqueous blendes together resin to be stable Dispersion liquid (lotion), collocation bridging agent combination, forms non-permanent material protective film, and final protective film can be shelled easily again From this is the uniqueness of the aqueous blending paint formula of the present invention.
Aqueous blending paint of the invention, the not only application feature of adjustable protective film, in response to execution conditions, environment, The requirement of the diversification such as material, client application, it is also adjustable that " one-pack-type " or " dual liquid type " aqueous blending paint is made, it says as follows It is bright:
A, " one-pack-type " aqueous blending paint (single-component aqueous hybridized coating):
In aqueous resin dispersion (lotion) blending procedure, bridging agent (polynary aziridine is added (polyaziridines) as PICASSIAN XL-706, (polycarbodiimides, such as PICASSIAN XL-701) or/ With multicomponent isocyanate (polyisocyanates, such as CORONATE AQ130), can be carried out respectively for carboxyl and amido Bridging reaction, organic additive, such as thickener, antioxidant, inorganic filler, such as calcium carbonate, mountain flour, barium sulfate, oxidation Silicon, aluminium oxide, titanium dioxide etc. are stirred evenly with mechanical agitator and are mixed to form " one-pack-type " aqueous blending paint (single- Component aqueous hybridized coating), protection is in application, can directly coating waste water (choosing on the surface of the material Select the modes such as spraying, lamination, idler wheel, brushing or impregnation) after, it is placed in room temperature (well-ventilated's environment) drying or enters baking oven and heat It is dry, it blendes together cold coating and voluntarily carries out bridging reaction, allow after the complete volatile dry of moisture, form continuous protective film;It uses Person can will deploy " one-pack-type " the aqueous blending paint for completing all compositions, voluntarily adjust working viscosity according to need or directly apply Cloth application.
B, " dual liquid type " aqueous blending paint (two-component aqueous hybridized coating):
If considering condition of storage and the time of aqueous blending paint, the formula of aqueous blending paint of the invention can also be set It is calculated as " dual liquid type " aqueous blending paint.By the aqueous dispersion liquid and organic additive, such as thickener, antioxidant of blending together as " A Agent ", separately by bridging agent, polynary aziridine (polyaziridines such as PICASSIAN XL-706), polynary carbodiimides (polycarbodiimides, such as PICASSIAN XL-701) or/and multicomponent isocyanate (polyisocyanates, such as CORONATE AQ130) etc. and inorganic filler, such as silica, aluminium oxide, calcium carbonate (mountain flour), barium sulfate or titanium dioxide Other formulas of titanium etc. before construction to scale by two doses of A/B, stir evenly mixing when " B agent " with mechanical agitator, then into Row coating (modes such as selection spraying, lamination, idler wheel, brushing or impregnation), drying and the process for voluntarily carrying out bridging reaction, with " one-pack-type " aqueous blending paint is similar;The coating application of allotment A/B agent, becomes " dual liquid type " aqueous blending paint before construction, To ensure the stable shelf life of aqueous blending paint.
Either " one-pack-type " or " dual liquid type " aqueous blending paint blendes together cold coating and divides via coating drying After not volatilizing containing the triethylamine (TEA, triethyl amine) for neutralizing carboxyl, carboxylic acid (COOH) is reduced and starts unit-frame together Bridge agent (polyaziridine, PICASSIAN XL-706) or/and polynary carbon polycarbodiimide, PICASSIAN XL- 701) bridging reaction;As for multicomponent isocyanate (polyisocyanate, CORONATE AQ130) bridging agent, in drying Afterwards, the isocyanates in micella (isocyanate) and amido, just have an opportunity to react, and form reticular structure and blend together protective film (hybridized protection films);It is such to blend together resin protection film, it is seen from electron microscope and heat analysis map Examine, without mutually separating the phenomenon that, show it is aqueous blendes together cold coating, it is dry after protective film have become brand-new hybrid material.
This is the different water-base resins that the present invention uses same resin ion radical first, is blended in varing proportions, then through altogether With bridging agent respectively with the carboxyl of resin (being reduced into carboxyl) and amido or polynary carbodiimides, PICASSIAN XL- 701) bridging reaction mode, can it is customized allotment aqueous resin dispersion (lotion) formula rate, in response to final protective film Property requirements on different materials surface, this is the polynary protection purposes of the aqueous blending paint of the present invention.
For the material surface of unlike material (structure of chemical composition), need to select the aqueous of different composition ratio to blend together painting Material and bridging agent, can be only achieved expected pencil hardness, density, resistance to cutting oil etc. can protect the protective film on surface completely, And the protective film of material surface is soaked in water several minutes after last processing, can easily from surface demoulding, remove back It receives.The property (pencil hardness, scratch resistance, density, resistance to cutting oil, acid resistance solution etc.) of this dry-run protection film depends on mixed There is direct association at the composition of cold coating, and with the chemical and physical features of material surface;Such as film and material surface The properties such as density, resistance to cutting oil, acid resistance solution determine the compatibility in the aqueous polarity for blending together resin and surface.It is aqueous The selection of bridging agent and dosage in the composition ratio of cold coating formula water-base resin are blended together, the microcosmic material structure of film is influenced Bridge formation density and macroscopic coating property, as pencil hardness, density, scratch resistance, water-fast, resist processing chemicals (cutting Oil, acid solution) etc..The coating relevant nature of aqueous blending paint, such as viscosity, consistency, thixotropy, coating thickness and hardness Deng then permeable filler, such as the inorganic composition formula of silica, aluminium oxide, calcium carbonate (mountain flour), barium sulfate, titanium dioxide To adjust.
It is main application, implementation of the invention that aqueous blending paint of the invention, which is applied to non-permanent material protective film, Example sincerely illustrates that the water-base resin that different materials surface is applicable in blendes together ratio and bridging agent composition;But it is of the invention aqueous to blend together The formula of coating and application are not limited in the formula compositions such as water-base resin, bridging agent used in the following example, apply charity Work mode and material applications.
Embodiment one: the aqueous blending paint of plastic material is protected
Select aqueous PU resin dispersion liquid (lotion) (PU-1) and aqueous acryl resin (AC-2's) to blend together resin, PU- 1/AC-2=4/1, bridging agent, it is solid that polynary aziridine (polyaziridines, PICASSIAN XL-706) accounts for cold coating 2.0% (2.0phr) of content, is prepared into " one-pack-type " aqueous blending paint;It is sprayed on the polymethacrylates cleaned up The clear sheet surface (polymethyl methacrylate, PMMA) after being then placed in 50 DEG C of baking oven heated-air dryings, is formed saturating Bright protective film, about 35 millimeters of thickness, hardness are 1H pencil hardness, density 4-5B;60 DEG C of clear sheet immersion is water-soluble After liquid 15 minutes, the smooth Automatic-falling of film, PMMA surface not residual paint.
Embodiment two: the aqueous blending paint of aluminium is protected:
Select aqueous epoxy resin emulsion (EP-1), aqueous PU resin dispersion liquid (lotion) (PU-1) and aqueous acrylic tree Rouge (AC-1) blendes together resin, EP-1/PU-1/AC-2=2/3/1, bridging agent, polynary aziridine (polyaziridines, PICASSIAN XL-706) and polynary carbodiimides (polycarbodiimides, PICASSIAN XL-701) respectively be tree 2.0% (2.0phr) of grease coating material solid content, is prepared into " one-pack-type " aqueous blending paint;Before construction, barium sulfate etc. is added and fills out Object 20phr is filled, the consistency of water paint is increased, and increases the thickness of film and the wearability of dry film.Before coating construction, with Mechanical agitator after mixing evenly by formulation for coating material is sprayed on the aluminium material surface cleaned up, is then placed in 90 DEG C of baking oven hot winds After drying, protective film is formed, about 50 millimeters of thickness, hardness are 2H pencil hardness, density 5B, resistance to cutting oil (10 minutes Do not bleach);Aluminium is immersed 60 DEG C after aqueous solution 15 minutes, the smooth Automatic-falling of film, aluminium material surface not residual paint.
Embodiment three: the water paint of stainless steel is protected:
Select aqueous epoxy resin emulsion (EP-2), aqueous PU resin dispersion liquid (lotion) (PU-3) and aqueous acrylic tree Rouge (AC-1) blendes together resin (EP-2/PU-3/AC-1=2/3/1), when A agent;Mix bridging agent, polynary aziridine (polyaziridines, PICASSIAN XL-706) and multicomponent isocyanate (polyisocyanates, CORONATE AQ130) be cold coating solid content 2.0% (2.0phr) when B agent, be prepared into " dual liquid type " aqueous blending paint;This biliquid Coating of the dosage form (A/B agent) before spraying after mixing before construction, adds barium sulfate and aluminium oxide 30phr (is increased aqueous The consistency of coating), and increase the thickness of film and the wearability of dry film.Before spraying, by formulation for coating material, with the mixing of three rollers After uniformly, it is sprayed on stainless steel surface, after being then placed in 80 DEG C of baking oven heated-air dryings, forms protective film, about 55 milli of thickness Rice, hardness are 2-3H pencil hardness, density (test of hundred lattice) is 5B and meets scratch resistance, water-fast, resist processing chemicals (is cut Cut oil, acid solution) etc. specification;Stainless steel is immersed 60 DEG C after aqueous solution 15 minutes, the smooth Automatic-falling of film, stainless steel Material surface not residual paint.
Example IV: the aqueous blending paint of composite material is protected:
Select aqueous PU resin dispersion liquid (lotion) (PU-4) and aqueous acryl resin (AC-2's) to blend together resin, PU- 4/AC-2=2/1;Bridging agent, polynary carbodiimides (polycarbodiimides, PICASSIAN XL-701) account for resin painting It is aqueous to be prepared into " one-pack-type " so that with mechanical agitator, formulation for coating material to be stirred evenly by 2.0% (2.0phr) of material solid content Blending paint;It is sprayed on the acrylic baking vanish surface cleaned up, after being subsequently placed in the natural drying of room temperature ventilation, forms protection Film, about 35 millimeters of thickness, hardness is 1H pencil hardness, density 3-4B;After cleaning acrylic baking vanish surface with hydraulic giant, apply The smooth Automatic-falling of film, acrylic baking vanish surface not residual paint.
Embodiment five: the aqueous blending paint of protection solar panels glass:
Select aqueous epoxy resin emulsion (EP-1), aqueous PU resin dispersion liquid (lotion) (PU-2) and aqueous acrylic tree Rouge (AC-1) blendes together resin (EP-1/PU-2/AC-1=2/4/1), when A agent;Mix the polynary aziridine of bridging agent (polyaziridines, PICASSIAN XL-706) and multicomponent isocyanate (polyisocyanates, CORONATE AQ130 2.0% (2.0phr) of cold coating solid content) is respectively accounted for when B agent, is prepared into " dual liquid type " aqueous blending paint;This is double Liquor type (A/B agent) is before spraying, and with mechanical agitator, coating after formulation for coating material is uniformly mixed will be cleaned up The solar panels glass sheet of (pickling and clear water wash drying), containing the diluted aqueous blending paint of immersion, the glass being then coated with After glass sheet material is placed in 90 DEG C of baking oven heated-air dryings, protective film, about 50 millimeters of thickness, hardness > 3H pencil hardness, density are formed (test of hundred lattice) is 5B, resistance to cutting is oily (not bleaching within 10 minutes);Glass sheet is immersed into 60 DEG C of aqueous solutions after twenty minutes, film is suitable Sharp Automatic-falling, glass sheet surface not residual paint.
Embodiment six: the aqueous blending paint of protection optics PC eyeglass:
Select aqueous epoxy resin emulsion (EP-1), aqueous PU resin dispersion liquid (lotion) (PU-2) and aqueous acrylic tree Rouge (AC-1) blendes together resin (PU-2/AC-1=4/1), when A agent;Mix the polynary aziridine of bridging agent (polyaziridines, PICASSIAN XL-706) and multicomponent isocyanate (polyisocyanates, CORONATE ) etc. AQ130 2.0% (2.0phr) that dosage accounts for about cold coating solid content is prepared into that " dual liquid type " is aqueous to blend together painting when B agent Material;This biliquid dosage form (A/B agent), with mechanical agitator, will be formulated the coating after being uniformly mixed, clean up before spraying The optics PC eyeglass material of (pickling and clear water wash drying), containing the diluted aqueous blending paint of immersion, the PC eyeglass being then coated with After material is placed in 60 DEG C of baking oven heated-air dryings, protective film is formed, about 30 millimeters of thickness, hardness are 2H pencil hardness, density is 5B, resistance to cutting are oily (not bleaching within 10 minutes);PC eyeglass material immerses 60 DEG C of aqueous solutions after twenty minutes, the smooth Automatic-falling of film, light Learn PC mirror sheet surface not residual paint.
Embodiment seven: the aqueous blending paint of stone material is protected:
The stone material (including the stone materials such as marble, granite and parquets) of usual building materials (floor) has porous table Face suffers from the pollution (greasy dirt, beverage, coffee, betel nut juice, fruit juice etc.) of not easy-clear and intolerant to friction, surface is easily damaged The disadvantages of hurting, especially in storage and transportation, decoration process, impaired probability is bigger;Select aqueous epoxy resin emulsion (EP-1), aqueous PU Resin dispersion liquid (lotion) (PU-1) and aqueous acryl resin (AC-1) blend together resin, EP-1/PU-1/AC-2=3/3/1, Filler (mountain flour, barium sulfate) each 10phr, bridging agent polynary aziridine (polyaziridines, PICASSIAN is added XL-706) be cold coating solid content 1.5% (1.5phr), be prepared into " one-pack-type " aqueous blending paint;Before construction, it is added Silica 20phr and calcium carbonate 40phr increase the consistency of water paint, and increase the thickness of film and the wearability of dry film. Formulation for coating material is uniformly mixed with three rollers, is sprayed on the stone surface cleaned up, is then dried about in ventilated environment room temperature After drying in 24 hours, about 100 millimeters of thickness of protective film, hardness > 2H, density 3-5B are formed;After decoration construction, in The nonwoven fabric of stone surface layer overlay aqueous solution, film overnight smoothly fall off with nonwoven fabric removing automatically, and stone surface is not Residual paint.
Embodiment eight: the aqueous blending paint on protection baking vanish surface:
The spray painting of car body metal plate, vehicle body other parts have often needed suitable protecting, have avoided new baking vanish from polluting other original Car body baking vanish.Selection selection aqueous epoxy resins dispersion liquid (lotion) (EP-1) and aqueous acryl resin (AC-2) blendes together tree Rouge, EP-1/AC-2=1/1, the polynary aziridine of bridging agent (polyaziridines, PICASSIAN XL-706) are that resin applies 1.0% (1.0phr) for expecting solid content, is prepared into " one-pack-type " aqueous blending paint of solid content 30%;Before construction, stone is added Powder 50phr, increases the consistency of water paint, and increases the thickness of film and the wearability of dry film, will with mechanical agitator Formulation for coating material is uniformly mixed, then is sprayed on the vehicle body baking vanish surface cleaned up, then in draughty environment, often After temperature drying overnight, transparent protective film is formed, about 150 millimeters of thickness, hardness is 1H pencil hardness, density 2-4B;? When car body metal plate paint spraying, transparent protective film can protect the baking vanish of vehicle body script not polluted by spray painting;After the completion of metal plate, with water The spray cleaning of solution rifle, can remove transparency protected film, replys the baking vanish of original vehicle body, surface not residual paint.
Embodiment nine: the aqueous blending paint of ito glass is protected:
Select aqueous epoxy resin emulsion (EP-1), aqueous PU resin dispersion liquid (lotion) (PU-2) and aqueous acrylic tree Rouge (AC-1) blendes together resin (EP-1/PU-2/AC-1=2/4/1), when A agent;Mix the polynary aziridine of bridging agent (polyaziridines, PICASSIAN XL-706) and polynary carbodiimides (polycarbodiimides, PICASSIAN XL-701 2.0% (2.0phr) of cold coating solid content) is respectively accounted for when B agent, is prepared into " dual liquid type " aqueous blending paint;This is double Liquor type (A/B agent) is before spraying, and with mechanical agitator, coating after formulation for coating material is uniformly mixed will be cleaned up The ito glass sheet material of (pickling and clear water wash drying), containing the diluted aqueous blending paint of immersion, the glass sheet being then coated with After being placed in 80 DEG C of baking oven heated-air dryings, formed protective film, about 50 millimeters of thickness, hardness > 3H pencil hardness, density 5B, Resistance to cutting is oily (not bleaching within 10 minutes);Ito glass sheet material is immersed into 60 DEG C of aqueous solutions after twenty minutes, the smooth Automatic-falling of film, Glass sheet surface not residual paint.
As described above, the aqueous blending paint of one-pack-type of the invention and the aqueous blending paint of dual liquid type, can be applied to it is non-forever The material protection of long property;Purpose is to make material in the process for transporting, storing in a warehouse, being worked into finished product, avoid its surface by Scratch or stain, and material after processing is completed, this protective film can be easily from material surface removing, recycling, at concentration Reason, whole process is without using any organic solvent.
Aqueous blending paint of the invention can provide visitor in response to individual demand according to material surface material and protection film properties Inhibition and generation design allotment, the object of protection can be covered: metal, nonmetallic, plastics, the various hard such as stone material or baking vanish and soft material The surface of material;This aqueous blending paint is selecting containing reactive functional group and avirulent epoxy resin, Polyurethane (PU) and Asia The aqueous resin dispersions such as gram force resin (lotion) are deployed with single or two or more resins, and blend bridging agent, and single liquid is reached Type or dual liquid type finished product, and the drying process of this protective film, only the bridging reaction of chemical bonded refractory, does not generate any tool poison Property, volatile organic substance.Aqueous blending paint allotment of the invention, belongs to cleaning processing procedure and this product for material Protection process, be the application of friendly global environment.
The present invention has hereinbefore been disclosed with preferred embodiment, so it will be understood by those skilled in the art that embodiment only For describing the present invention, and it is not construed as limiting the scope of the invention.It should be noted that the variation equivalent with embodiment such as With displacement, should all be set as being encompassed within the scope of the present invention.Therefore, protection scope of the present invention is worked as and is defined with claims Range subject to.

Claims (10)

1. a kind of aqueous blending paint of one-pack-type, characterized by comprising:
(A) aqueous resin dispersion, it includes at least one water-base resin neutralized by tertiary amine, the aqueous trees of wherein at least one Rouge is selected from the group as composed by aqueous epoxy resins, aqueous polyurethane resin and aqueous acryl resin, and at least one water Property resin contains carboxyl (COO-) and other reactive functional groups;And
(B) bridging agent, after the aqueous blending paint of the one-pack-type is dry, the bridging agent and at least one water-base resin are carried out Bridging reaction intersects reticular structure (Interpenetrating Polymeric Networks, IPN) to be formed.
2. the aqueous blending paint of one-pack-type as described in claim 1, which is characterized in that it includes: the resin of 100 parts by weight; And 0.1~30.0 parts by weight bridging agent.
3. the aqueous blending paint of one-pack-type as described in claim 1, which is characterized in that further include:
(C) organic additive is selected from the group as composed by thickener and antioxidant;And
(D) inorganic filler, selected from as composed by calcium carbonate, mountain flour, barium sulfate, silica, aluminium oxide and titanium dioxide Group.
4. the aqueous blending paint of one-pack-type as described in claim 1, which is characterized in that the bridging agent selects free multicomponent ethylene Imines (polyaziridines), polynary carbodiimides (polycarbodiimides) and multicomponent isocyanate (polyisocyanates) group composed by.
5. the aqueous blending paint of one-pack-type as described in claim 1, which is characterized in that the pH value of the aqueous resin dispersion Greater than 8.
6. a kind of aqueous blending paint of dual liquid type, characterized by comprising:
A agent, it includes aqueous resin dispersion, it includes at least one water-base resin neutralized by tertiary amine, wherein at least one Kind water-base resin is selected from the group as composed by aqueous epoxy resins, aqueous polyurethane resin and aqueous acryl resin, and extremely A kind of few water-base resin contains carboxyl (COO-) and other reactive functional groups;And
B agent, it includes: bridging agent;
Wherein, after the A agent and B agent are mixed to form aqueous blending paint, and the aqueous blending paint is dry, the bridge formation Agent and at least one water-base resin carry out bridging reaction, to form the reticular structure (Interpenetrating that intersects Polymeric Networks,IPN)。
7. the aqueous blending paint of dual liquid type as claimed in claim 6, which is characterized in that when the A agent and B agent are mixed to form water After property blending paint, the aqueous blending paint includes: the resin of 100 parts by weight;And 0.1~30.0 parts by weight bridge formation Agent.
8. the aqueous blending paint of dual liquid type as claimed in claim 6, which is characterized in that
The A agent further includes: organic additive, is selected from the group as composed by thickener and antioxidant;And
The B agent further includes: inorganic filler, selected from by calcium carbonate, mountain flour, barium sulfate, silica, aluminium oxide and two Group composed by titanium oxide.
9. the aqueous blending paint of dual liquid type as claimed in claim 6, which is characterized in that bridging agent in the B agent be selected from by Polynary aziridine (polyaziridines), polynary carbodiimides (polycarbodiimides) and multicomponent isocyanate (polyisocyanates) group composed by.
10. the aqueous blending paint of dual liquid type as claimed in claim 6, wherein the pH value of the aqueous resin dispersion is greater than 8.
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Application publication date: 20190315