TWI629321B - Eco-friendly single-component aqueous hybridized coating and two-component aqueous hybridized coating - Google Patents

Abstract

The present invention discloses an environmentally-friendly single-liquid aqueous mixed coating comprising: (A) aqueous resin dispersion comprising at least one aqueous resin neutralized by a tertiary amine such as triethyl amine (TEA). Wherein the at least one aqueous resin is selected from the group consisting of an aqueous epoxy resin, an aqueous polyurethane resin, and an aqueous acrylic resin, and the at least one aqueous resin contains a carboxyl group (COO ⁻ ) and other reactive functional groups; And the selected bridging agent (B agent); when the A agent and the B agent are mixed into a single liquid type water-based mixed coating, after being spray-dried, the bridging agent is bridged with the at least one aqueous resin to form a cross-network Interpenetrating Polymeric Networks (IPN). Therefore, the single-liquid type aqueous mixed paint of the present invention can be applied to various materials to form a non-permanent material protective film, and after the material is processed, the protective film can be easily immersed in water (about 30 minutes). The surface is stripped, recycled, and concentrated from the surface of the material, and no organic solvent is used throughout the process. In addition, the present invention also discloses a two-liquid type aqueous mixed paint.

Description

Environmentally friendly single-liquid type water-based mixed coating and two-liquid type water-based mixed coating

The invention relates to an environment-friendly single-liquid type water-based mixed paint, and more particularly to a single-liquid type water-based mixed paint comprising a mixed resin and a bridging agent. The invention also relates to a two-liquid aqueous mixed coating.

Whether in the processing or reprocessing of organic or inorganic materials, it is often exposed to dusty environments with a hardness of 7.0 Mohs scale; generally inorganic materials (metal and non-metal) have higher hardness than organic materials. However, the hardness of inorganic materials is still less than 7.0; inorganic materials include metals and non-metals, such as: 1. Metal: iron, steel, aluminum, copper, metal alloys, plated (nickel, chromium) film metal, etc.; : Wafer, glass (optical, solar panel, ITO, lens, mirror), stone.

The above materials are very susceptible to scratching or abrasion during polishing, material transport and processing, and surface protection film protection is absolutely required.

For organic materials with lower hardness, such as: plastic, engineering plastics, composite materials, painted surfaces, etc., the hardness of the materials is lower (all less than 2.0 Mohs scale), in the process of material processing and transport, more need It has a strong protective film protection; such as: 1. Plastic: Polycarbonate (safety glass for sun visors, spectacle lenses, steam locomotives, etc.), polymethyl methacrylate (PMMA, sunglasses, headlights) Etc.), ABS (3C supplies); 2. Composite materials (such as carbon fiber, glass fiber) and other products; 3. Paint (such as cars, home appliances) and other surfaces.

At present, there are a variety of products for the surface protection of traditional temporary materials on the surface of materials. Only the brief technical data, application and construction methods of the products are introduced. However, in recent years, the contents disclosed in the patent literature can be used to understand the composition and characteristics. Briefly described as follows: 1. U.S. Patent 6,964,989 B1 (2005), using a PVB (polyvinyl butyral resin) film, a solvent-based PU adhesive, and a PVA (polyvinyl alcohol) as a release agent. 2. U.S. Patent No. 6,991,851 B2 (2006), using a sulfonate-containing aqueous PU to form a coating with an acrylic monomer, and using a hydrophilic polyol (polyols), a stearic acid metal soap, a castor oil, etc. as a release agent. . 3. U.S. Patent Application 2012/178862, using a solvent-based acrylic resin and a polyhydric alcohol, a glycerol fatty acid ester as a release agent. 4. U.S. Patent No. 9481806 (2016), using a polyvinyl acetate/acrylic copolymer emulsion as a coating, and polyethylene glycol (PEG, polyethylene glycols) as a thickener and a release agent. 5. U.S. Patent No. 9290677 (2016), using a solvent-based coating comprising a polymer such as cellulose acetate butyrate ester, sucrose acetate isobutyrate, acrylic copolymer After the film is formed, it is necessary to use an organic solvent such as THF, a diol or a diester compound as a release agent. 6. U.S. Patent 8263231 (2012) uses an aqueous polyurethane butyrate emulsion that requires organic solvents for film cleaning. 7. U.S. Patent No. 8048258 (2011) using N,N-diethylacrylate, N-vinyl pyroridone monomer and acrylic copolymer, free radical initiation The agent and the like constitute a coating, and the release agent requires an organic solvent. 8. US Patent 7531221 (2009), 7524536 (2009), both of which use acrylic emulsions and water-based waxes as coatings, and the coatings are not resistant to mechanical properties (such as abrasion resistance, scratch resistance, hardness). 9. U.S. Patent Nos. 6,682,773 (2006), 6849328 (20016), 7252853 (2007), 7165307 (2007), etc., all use water-soluble polymer materials as temporary coatings, and cannot provide materials in various processing processes. Protect the function of the film.

At present, the application of protective material technology (including commercialization or patent) is known, and its application and application properties on the surface of materials have advantages and disadvantages. Their construction process, except for the way of film coating, is required. Organic solvents such as chlorine-containing solvents (for dilute coatings or release coatings), plasticizers (for increasing the flexibility of coatings), and volatile organic compounds (VOC) such as film-forming auxiliaries, therefore, during construction Both front and rear cause doubts about safety, hygiene, fire, and environmental pollution.

Briefly explain the advantages and disadvantages of the prior art as follows: 1. Transparent resin film Advantages: When applied to the surface of small-area materials, it is easy to handle, and the construction is quick and manual film removal is easy. Disadvantages: When applied to large-area and curved or 3D surfaces, the film can not achieve full protection; the film is only relying on static electricity or pressure sensitive adhesive and the surface of the material is not well sealed; the hardness of the film is not good; there may be residual glue ( Pressure sensitive adhesive); poor resistance to processing chemicals. 2. Solvent-based coatings Advantages: Spray coating is easy, and the adhesion and softness can be adjusted. Disadvantages: During the manufacturing, transport and coating process drying process, a large amount of organic solvent (usually >75% solvent) volatilizes, which is not only flammable but also causes air pollution; the final film peeling is not easy, and it depends on a large amount of organic solvent, so it is removed. The subsequent coating film contains a large amount of solvent and is difficult to handle. 3. UV-curable coating film Advantages: It can be quickly hardened by UV light after coating. Disadvantages: During the coating process, there are volatile organic substances (including plasticizers), which cause doubts about work safety and hygiene; and it is not easy to remove the film after processing, and it needs to be destructively treated with strong alkali. 4. Emulsifier Emulsion Resin Advantages: Water-based solvent-based coatings (with emulsifier) can reduce the risk of solvent-borne coatings in transportation and construction. Disadvantages: there is a problem with VOC caused by organic solvent; the added emulsifier is displaced to the surface of the protective material, causing surface contamination; emulsions and additives, additives, often cause the paint to be unstable (the emulsion is subjected to critical microcell concentration (CMC, The limitation of critical micelle concentration, temperature and mechanical agitation will cause the emulsion to be unstable.) The final protective film is not easily peeled off and needs to be cleaned with more organic solvents.

Looking at the above, the way of surface protection of traditional materials not only causes environmental protection, health and safety problems and hidden concerns, but also has limitations in the way of processing materials and the problem of the final protective film stripping treatment needs to be overcome; in the future, it faces environmental pollution regulations and pollution prevention regulations. Increasingly strict, it is indispensable to seek products that meet environmental protection requirements, especially in response to the social responsibility of the industry to protect the planet.

It is an object of the present invention to provide a novel environmentally friendly aqueous hybrid coating to improve the shortcomings of conventional protective material technologies.

In order to achieve the above and other objects, the present invention provides an environmentally-friendly single-liquid aqueous mixed coating comprising a mixed A agent and a B agent to form a single-agent aqueous mixed paint storage reserve: A agent, aqueous resin dispersion, which contains at least An aqueous resin neutralized by a tertiary amine such as triethyl amine (TEA), wherein the at least one aqueous resin is selected from the group consisting of an aqueous epoxy resin, an aqueous polyurethane resin, and an aqueous acrylic resin. And the at least one aqueous resin contains a carboxyl group (COO ⁻ ) and other reactive functional groups; and a B agent, a bridging agent; and when the one-liquid aqueous mixed coating is dried, the bridging agent and the at least one aqueous resin The bridging reaction is carried out to form Interpenetrating Polymeric Networks (IPN).

In one embodiment of the present invention, the one-liquid type aqueous mixed paint system comprises: 100 parts by weight of a resin; and 0.1 to 30.0 parts by weight of a bridging agent.

In one embodiment of the present invention, the one-liquid type aqueous mixed paint further comprises: (C) an organic additive selected from the group consisting of a thickener and an antioxidant; and (D) an inorganic filler. It is selected from the group consisting of calcium carbonate, stone powder, barium sulfate, cerium oxide, aluminum oxide and titanium dioxide.

In one embodiment of the invention, the bridging agent is selected from the group consisting of polyaziridines (such as PICASSIAN XL-706), polycarbodiimides (such as PICASSIAN XL-701), and polyisocyanates (polyisocyanates). Groups such as CORONATE AQ130).

To achieve the above and other objects, the present invention also provides a two-liquid aqueous mixed coating comprising two agents of A and B: A agent comprising: an aqueous resin dispersion comprising at least one tertiary amine An aqueous resin neutralized by a triethyl amine (TEA), wherein the at least one aqueous resin is selected from the group consisting of an aqueous epoxy resin, an aqueous polyurethane resin, and an aqueous acrylic resin, and the at least An aqueous resin containing a carboxyl group (COO ⁻ ) and other reactive functional groups; and a B agent comprising: a bridging agent; wherein, before application, the agent A and the agent B are mixed to form an aqueous mixed coating, and the After the aqueous hybrid coating is dried, the bridging agent is bridged with the at least one aqueous resin to form Interpenetrating Polymeric Networks (IPN).

In one embodiment of the present invention, after the agent A and the agent B are mixed to form an aqueous mixed coating, the aqueous mixed coating comprises: 100 parts by weight of a resin; and 0.1 to 30.0 parts by weight of a bridging agent.

In an embodiment of the present invention, the agent A further comprises: an organic additive selected from the group consisting of a thickener and an antioxidant; and the agent B further comprises: an inorganic filler selected from the group consisting of carbonic acid A group consisting of calcium, stone powder, barium sulfate, barium oxide, aluminum oxide and titanium dioxide. .

In one embodiment of the present invention, the bridging agent in the B agent is selected from the group consisting of polyaziridines (PICASSIAN XL-706), polycarbodiimides (PICASSIAN XL-701), and polyisocyanates ( Group of polyisocyanates, CORONATE AQ130).

In an embodiment of the invention, the aqueous resin dispersion has a pH greater than 8.

Thereby, the one-liquid type aqueous mixed paint and the two-liquid type aqueous mixed paint of the present invention provide non-permanent (temporary) protection for the material. Those having ordinary knowledge in the technical field of the present invention may select a mixed resin formulation such as a non-toxic water-based epoxy resin, an aqueous polyurethane resin, an aqueous acrylic resin dispersion (emulsion) according to the nature and structure of the surface of the material, and combine Various aqueous bridging agents (such as polyaziridines, PICASSIAN XL-706, polycarbodiimides (PICASSIAN XL-701), and polyisocyanates (CORONATE AQ130), etc., form a single-liquid aqueous mixed coating And two-liquid type water-based mixed coating, coated on the surface of materials, such as: metal, non-metal, plastic, stone, or baking materials, etc., through normal temperature or heating to form a material protective coating film (5-150 mm) Thickness); During the drying process, only water evaporation and bridging reactions occur without any toxic volatile organic matter (VOC) emissions.

The invention aims to manufacture an aqueous mixed coating for non-permanent protection purposes: 1. The protective film formed by the coating of the invention is closely adhered to the surface of the material, and the processing of the material is prevented from being processed, stored, transported, cut, punched, recoated, etc. In the final product process, it is subjected to any scratches or stains to achieve the purpose of safety protection materials. 2. After the final processing is completed, the protected material is immersed in an aqueous solution (normal temperature ~80 ° C) without using any organic solvent. The protective film can be easily peeled off and recycled for centralized treatment without causing water pollution, and no material remains on the surface of all the material after the release.

According to the property requirements of the material protective film of the present invention, it can be adjusted by the formulation selection of the aqueous epoxy resin, the polyurethane resin, the aqueous acrylic resin dispersion (emulsion), and the formulation dosage of the bridging agent and other additives and fillers; The release condition of the protective film in the aqueous solution can adjust the bridging density by the dose of the bridging agent to achieve the demand for the protective film of the customized material. As for the application properties of water-based hybrid coatings, such as viscosity, consistency, shake, coating thickness and hardness, it can penetrate fillers such as cerium oxide, aluminum oxide, calcium carbonate (stone powder), barium sulfate, titanium dioxide, etc. The inorganic formula is adjusted. The material protection coating can provide perfect protection properties and functions, environmental protection cleaning process after processing, and the characteristics of the formulation and multi-component application of the customized water-based coating product, which are the characteristics of the water-based mixed coating of the present invention.

In order to fully understand the objects, features and advantages of the present invention, the present invention will be described in detail by the following specific embodiments and the accompanying drawings.

The unit "phr" used in the present invention means the amount of addition per part of the resin, that is, the weight of each additive per 100 parts by weight of the resin. number.

The "pencil hardness" described in the present invention is measured in accordance with the test standard set forth in "ASTM D3363".

The "adhesion" (100-gauge test) described in the present invention is measured in accordance with the test standard set forth in "ASTM D3359".

The "single liquid type" water-based mixed paint and the "two-liquid type" water-based mixed paint of the present invention are required according to chemical, physical materials and protective film properties of materials (whether organic or inorganic materials) (such as pencil hardness, adhesion, and water resistance). Properties, processing chemicals, etc.), using different proportions of epoxy resin, polyurethane (PU) and acrylic resin and other aqueous resin dispersion (emulsion) and bridging agent. When the "single liquid type" water-based mixed paint of the present invention and the "two-liquid type" water-based mixed paint are dried and formed into a film, the common carboxyl group contained in the aqueous resin emulsion micelle is reduced to a carboxylic acid (COOH), and the bridge is started and bridged. Agent (such as polyethylenimine, polyaziridines, PICASSIAN XL-706) ring-opening, or polycarbodiimides (PICASSIAN XL-701) and other bridging reactions; PU resin containing amine groups and bridging agents (polyisocyanate, Polyisocyanates, CORONATE AQ130), an addition reaction, an epoxy group contained in another PU resin, an epoxy group contained in an acryl resin or an epoxy resin, and a bridging reaction in which a chemical bond is generated by a ring-opening reaction. The application properties of water-based hybrid coatings, such as viscosity, consistency, shake, coating thickness and pencil hardness, are adjusted by inorganic formulations such as cerium oxide, aluminum oxide, calcium carbonate (stone powder), barium sulfate, and titanium dioxide. When the coating film is dried, the carboxyl group (COO-) in the aqueous resin is gradually reduced to a carboxylic acid (COOH), so that the aqueous mixed resin is automatically bridged with a bridging agent, and a bridging reaction such as ring-opening is carried out to produce a reaction type of the mixed coating. The coating film of Interpenetrating Polymeric Networks (IPN) forms a custom-made protective film; at the same time, the coating formulation regulates the equivalent number of carboxylic acids and the bridging density of the unbridged reaction contained in the resin, and the coating film can also be adjusted. The hydrophilicity controls the peelability of the finished film of the finished product.

The reactive functional groups contained in the three types of aqueous resins and bridging agents used in the one-liquid aqueous mixed coating and the two-liquid aqueous mixed coating of the present invention are as follows:

First, the three types of water-based resins of the above schematic diagrams are respectively prepared: an epoxy resin, a polyurethane resin (PU), an acrylic resin, and the like, which also contain a carboxylic acid (COOH) resin, and respectively added triethylamine to contain the carboxylic acid (COOH). After neutralization, a hydrophilic anionic group (carboxyl group, COO ^- ) is formed, and then separately stirred with water to form three kinds of stable self-emulsified aqueous emulsions (self-emulsified aqueous emulsion); The hydrophilic nature provides a stable aqueous resin dispersion (emulsion) without the need for an external emulsifier. The three types of resin dispersions (emulsions) are prepared into solid content (5-60%) in pure water to facilitate the blending of subsequent aqueous mixed resin coatings. The average particle size of the three types of aqueous resin dispersions (emulsions) Between about 30-250 nm (nm, 1x10 ^-9 meters), although they are of different chemical structure and properties, they form their own micelles, which are stably dispersed in the water phase, and the periphery of the cells are The hydrophilic anionic group (carboxyl group), the zeta potential formed therebetween, causes the microtubules to repel each other to produce Brownian motion, forming a uniform and stable mixed emulsion; the three types of dispersions are mutually polar Good compatibility, can be blended with resin emulsion in any proportion to form an aqueous mixed resin dispersion, and there is no critical microcell concentration limit due to the ionic-based aqueous resin dispersion (emulsion) (Critical Micelle Concentration) Since each of the stable micelles is present in the aqueous phase, no phase separation occurs, so that the resin dispersion (emulsion) state can be uniformly and stably mixed, and can be stored at room temperature for more than 6 months.

For coating applications, suitable epoxy resin, polyurethane (PU) and acrylic can be selected according to the material surface material and protective film properties (such as pencil hardness, adhesion, water resistance, and processing chemicals). An aqueous resin dispersion (emulsion) such as a resin is blended into a "single liquid type" or "two-liquid type" aqueous mixed resin coating at different ratios and a bridging agent. When dried and formed into a film after coating, the aqueous resin emulsion microcapsules are contained. Reduction of a common carboxyl group to a carboxylic acid (COOH) while simultaneously initiating a bridging reaction with a bridging agent (eg, polyethylenimine, polyaziridines, PICASSIAN XL-706), ring opening, or polycarbodiimide (PICASSIAN XL-701) : for example, an amine group contained in a PU resin and a bridging agent (polyisocyanates, CORONATE AQ130), an addition reaction, an amine group contained in another PU resin, and an epoxy resin contained in an acrylic resin or an epoxy resin. At the same time, a bridging reaction such as a ring-opening reaction to generate a chemical bond is performed. The above reaction is as follows:

The three types of self-emulsifying aqueous resin dispersions (emulsions) used in the present invention can be blended in any ratio with a bridging agent (hydrophobic) to form a "single liquid type" or "two liquid type" aqueous mixed resin coating. At the same time of drying, the reaction such as addition and ring opening can be automatically performed to produce a reactive (3D stereo) cross-linked network structure (IPN, Interpenetrating Polymeric Networks) coating film of the mixed resin to achieve a customized protective film property. At the same time, the equivalent number of carboxylic acids and the bridging density of the unbridged reaction contained in the resin can be adjusted to adjust the hydrophilicity of the coating film so as to control the peelability of the final finished coating film. As shown in FIG. 1, the protective film 10 formed by drying the aqueous mixed resin coating of the present invention may comprise: a bridging agent 11, an epoxy resin 12, a polyurethane resin 13, and an acrylic resin 14, wherein the resin systems are They are cross-linked to each other by the bridging agent 11.

Aqueous resin dispersion ( Emulsion ) The representative processes are briefly described as follows:

Adding water-dilutable epoxy resin type aqueous emulsion (water-reducible aqueous epoxy resin emulsion ):

Epoxy resin (NPS-902 or NPES-904, purchased from Nanya Plastics Co., Ltd.) was placed in a three-necked flask, dissolved in a small amount of tetrahydrofuran (THF, tetrahydrofuran), and the reaction flask was heated to 75 °C, using a mechanical stirrer, slowly add succinic anhydride (succinic anhydride) powder and stir evenly, the reaction temperature is maintained at 75 ° C, after about 8 hours, cooled to room temperature, epoxy resin and succinic anhydride, complete the semi-esterification reaction (such as In addition, triethyl amine was added to pure water (500 ml) to prepare an aqueous solution having a pH of about 8.0 to 10.0. The above epoxy resin and succinic anhydride semi-esterified product liquid, slowly added to the aqueous solution containing triethylamine and rapidly stirred (1000 rpm) using a mechanical stirrer until the half-esterified product is added, and the stirring is maintained at about 4 In the hour, 30~60% solid content aqueous epoxy resin dispersion (emulsion) is completed. EP-1: NPES-902, Epoxy Equivalent (EEW) 600-650 EP-2: NPES-904, Epoxy Equivalent (EEW) 740-850

Self-emulsified water PU Dispersions ( Emulsion (self-emulsified aqueous polyurethane dispersion) :

Polyols (such as polyether polyols (such as PU-1, PU-3), polycarbonate diols (such as PU-2) or polycaprolactone diols (polycaprolactone diols) are selected. For example, PU-4)) and polyisocyanates (such as isophorone diisocyanate or methane diphenyl diisocyanate) are used as PU raw materials, and dimethylol groups are selected. Propionic acid (DMPA, dimethylol propanic acid) is used as the anion-based raw material of the PU main chain to prepare PU prepolymers containing carboxylic acid; firstly, polyols and DMPA are placed in a 4-neck bottle to heat The bag was heated to 120 ° C, vacuumed and dehydrated for about 4 hours, then cooled to room temperature, and then slowly dropped into IPDI. The reaction flask was stirred with a mechanical stirrer, and the reaction temperature was maintained at 75 ° C for about 4 hours until the NCO% was lower than the theoretical value. That is, the reaction of the PU prepolymer is completed. Another preparation of triethylamine (TEA, triethyl amine) was added to pure water (500 ml) to prepare an aqueous solution having a pH of about 10.0, and ethylene diamine (EDA, ethylene diamine) was added as a chain extender. The above aqueous solution containing TEA and EDA was prepared, slowly added to the PU prepolymer, and stirred and dispersed by a rapid stirrer to complete a 30% solid content aqueous PU dispersion (emulsion). PU-1: PTMEG-1000 (polyol), IPDI (polyisocyanate) PU-2: PC-2000 (polyol), IPDI (polyisocyanate) PU-3: PPG-1000 (polyol), IPDI (polyisocyanate) PU-4: PCL-1000 (polyol), MDI (polyisocyanate)

Self-emulsified aqueous polyacrylate emulsion: R= -CH ₃ , - C ₄ H ₉ or - C ₆ H ₁₃

According to the traditional emulsion polymerization method, a self-emulsified aqueous acrylic resin emulsion is prepared; an initiator, an ammonium persulfate, an emulsifier, and a lauryl benzyl sulfonate are dissolved in a distilled aqueous solution. Forming an emulsion; then, reacting the monomer raw materials, acrylic acid, alkyl acrylates, methacrylic acid or glycidyl methacrylate The body mixture (pH adjusted to 8.0 by TEA) is slowly added to the above emulsion containing emulsifier, initiator, etc., and after heating to 40 ° C, the exothermic reaction of the emulsion polymerization is started, and the emulsion is heated by the water bath. The speed is up to 80 ° C, and the emulsion polymerization is completed at 80 ° C for about 4 hours, and contains 30-60% solid content of aqueous acrylic resin emulsion. AC-1: R = hexyl AC-2: R = methyl

The above-mentioned water-reducible water-based epoxy resin, self-emulsifiable aqueous polyurethane resin dispersion (emulsion), and self-emulsified aqueous acrylic resin emulsion, etc., which are representative types of aqueous resin dispersions (emulsions), each of which is The emulsion formed by the independent microcell structure, all of which contain the same anionic carboxyl group, has excellent compatibility, and can be mixed in any ratio to produce a stable mixed resin dispersion (emulsion) without phase separation. The phenomenon that the resin contains an ionic group (carboxyl group), and there is no limitation of "CCM (critical cell concentration)"; when it is formed into a film, the extracellular hydrophilic carboxylic acid and the amine in the microcell Base, which will be associated with a common bridging agent, such as polyaziridines such as PICASSIAN XL-706, purchased from STAHL HOLDINGS BV, or polycarbodiimides such as PICASSIAN XL-701 from STAHL HOLDINGS BV, Isocyanate (polyisocyanates, such as CORONATE AQ130, purchased from Japan Polyurethane Industry Co., Ltd.), etc., undergoes ring-opening or addition bridging reactions, and individually produces amine groups. (aminoester) and urea-based (ureas) chemical bonding, forming a network structure coating film, after drying will automatically form a uniform hybrid resin protective film; the composition of these three types of resin, along with the properties of the protective film The demand for selecting a resin raw material component, a mixing ratio of a resin dispersion (emulsion), and a bridging agent composition to produce a customized resin protective film is an advantage of the application of the mixed resin coating of the present invention.

The three types of water-based resin raw materials are all known industrial sources, and the manufacturing process of the self-emulsified aqueous resin dispersion liquid is also a conventional technique. As for the diversified application properties of the aqueous hybrid resin, the present invention is The characteristics of the custom resin used in the embodiment of the present invention are selected from the characteristic combination of individual aqueous resins, and the characteristics thereof are briefly described as follows: 1. Water-dilutable water-based epoxy resin: excellent rigidity, The toughness and hardness determine the epoxy equivalent weight (EEW) composed of the main component of epoxy resin, bis-phenol A (BPA). The higher the EEW, such as EP-2>EP- 1, EP-2 waterborne epoxy resin has higher properties such as rigidity, toughness and hardness. 2. Self-emulsifying aqueous PU dispersion ( emulsion ) : It has excellent properties such as softness, abrasion resistance, ductility and adhesion, and is determined by the main component of the PU resin, the molecular weight of the polyol and the PU composed of the polyisocyanate. Prepolymer; the higher the molecular weight of the polyol, such as PU-2 > PU-1, the better the PU properties, the softness, the abrasion resistance, the ductility, the adhesion, etc.; if the polyisocyanate is aromatic The better the rigidity, hardness, wear resistance, etc. (PU-4>PU-3) of the PU is formed. 3. Self-emulsifying water-based acrylic resin emulsion: excellent softness, ductility, adhesion, etc.; if using a variety of long-chain alkyl acrylates (such as n-hexyl acrylate), AC-1 ) Acrylic resin prepared from a monomeric material of methyl acrylate having a lower Tg temperature, providing flexibility, ductility, adhesion, etc. of acrylic resin (AC-1) >AC-2) properties, as for the monomeric raw material glycidyl acrylate (GA, glycidyl acrylate) in the acrylic resin, providing an amine-based ring-opening bridging epoxy group to increase the bridging density and adhesion of the mixed coating degree.

The pH values (pH values) of the three types of aqueous resin dispersions (emulsions) were maintained at pH > 8.0 to 11.0, respectively. The common carboxyl group (anionic group) forms a stable aqueous resin dispersion (emulsion), because the same anionic group is contained therein, and two or three aqueous resin dispersions (emulsions) are uniformly mixed in different ratios to become an aqueous mixed resin. The dispersion (emulsion) is still stably present in the aqueous phase in individual cell dispersions (emulsions). The dispersion (emulsion) is not limited by the "critical cell concentration" (CMC) and can be diluted with pure water to any extent. The coating concentration can be applied and the viscosity is adjusted to form a stable aqueous mixed resin coating. The proportion of the three types of aqueous resin dispersions (emulsions) is arbitrarily mixed. With the requirement of the properties of the customized protective film, an appropriate proportion of the aqueous resin dispersion (emulsion) is selected in a short length and the mixture is uniformly stirred to be a stable aqueous mixed resin. The dispersion (emulsion), combined with the bridging agent, forms a non-permanent material protective film, and the final protective film can be easily peeled off. This is the uniqueness of the aqueous mixed-coating formulation of the present invention.

The water-based mixed coating of the invention can not only adjust the application properties of the protective film, but also can be prepared into a "single-liquid type" or "two-liquid type" water-based mixed coating material according to the requirements of various application conditions such as construction conditions, environment, materials, and customers. , as explained below:

A , "single liquid type" water-based mixed coating (single-component aqueous hybridized coating) :

In the process of blending an aqueous resin dispersion (emulsion), a bridging agent (polyaziridines such as PICASSIAN XL-706, (polycarbodiimides such as PICASSIAN XL-701), or/and polyisocyanates (such as CORONATE) is added. AQ130), etc., which can carry out bridging reactions for carboxyl groups and amine groups, organic additives such as thickeners, antioxidants, inorganic fillers, such as calcium carbonate, stone powder, barium sulfate, cerium oxide, aluminum oxide, titanium dioxide, etc. Stir-mixed with a mechanical stirrer to form a "single-component aqueous hybridized coating". When applied to the surface protection of the material, it can be directly coated (select spray, laminating, roller, brush or impregnation). After the method, it is placed in a normal temperature (ventilated environment) to dry or enter the oven to heat and dry, and the mixed resin coating is self-branched to allow the moisture to completely evaporate and dry to form a continuous protective film; the user can complete all the components that have been blended. The "single-liquid" water-based hybrid coatings are self-adjusting the construction viscosity or direct coating application as needed.

B. "Two -component aqueous hybridized coating" :

The formulation of the aqueous hybrid coating of the present invention can also be designed as a "two-liquid" aqueous mixed coating in consideration of the storage conditions and time of the aqueous mixed coating. Aqueous mixed dispersions and organic additives such as thickeners, antioxidants, etc. as "A agent", another bridging agent, polyethylenimine (polyaziridines such as PICASSIAN XL-706), polycarbodiimides (such as polycarbodiimides) PICASSIAN XL-701), or / and polyisocyanates (such as CORONATE AQ130), and other inorganic fillers, such as cerium oxide, aluminum oxide, calcium carbonate (stone powder), barium sulfate or titanium dioxide, etc., when "B "", before the construction, the A/B two doses are mixed according to the ratio, mixed with a mechanical stirrer, and then coated (select spray, laminating, roller, brush or impregnation), dry and self-bridge The reaction process is similar to the "single-liquid" water-based mixed coating; the application of A/B agent before application is a "two-liquid" water-based mixed coating to ensure the stable storage period of the water-based mixed coating.

Whether it is a "single-liquid type" or "two-liquid type" water-based mixed coating, after the coating and drying, the mixed resin coating contains a carboxyl group-containing triethylamine (TEA, triethyl amine), and then the carboxylic acid (COOH). Reductive and initiated bridging reaction with a common bridging agent (polyaziridine, PICASSIAN XL-706) or / and polycarbodiimide, PICASSIAN XL-701); as for polyisocyanate (CORONATE AQ130) bridging agent, after drying, microcells The isocyanate and the amine group have the opportunity to react to form a hybridized protective film; the mixed resin protective film has no phase separation from the electron microscope and thermal analysis. The aqueous mixed resin coating is shown, and the dried protective film has become a new hybrid material.

This is the first water-based resin of the same resin ion group, which is firstly blended in different proportions, and then copolymerized with the carboxyl group of the resin (reduced to carboxyl group) and the amine or polycarbodiimide, PICASSIAN XL- The bridging reaction mode of 701) can be customized to formulate the proportion of the aqueous resin dispersion (emulsion), which is the multi-protection use of the aqueous mixed coating of the present invention in response to the requirements of the final protective film on the surface of different materials.

For the surface of materials with different materials (chemical composition), it is necessary to select different proportions of water-based mixed coatings and bridging agents in order to achieve the expected pencil hardness, adhesion, cutting oil and other protective films that can completely protect the surface, and materials. After the final processing, the protective film on the surface can be easily detached from the surface and peeled off after being immersed in water for several minutes. The properties of the dry protective film (pencil hardness, scratch resistance, adhesion, cutting oil, acid resistant solution, etc.) depend on the composition of the mixed resin coating and are directly related to the chemical and physical properties of the surface of the material; For example, the adhesion between the coating film and the surface of the material, the resistance to cutting oil, the acid-resistant solution, etc., determine the compatibility of the polarity and surface of the aqueous mixed resin. Aqueous mixture resin coating formulation The composition ratio of the bridging agent in the composition ratio of the water-based resin, affecting the bridging density of the microscopic material structure of the coating film, and the coating properties of the giant coating such as pencil hardness, adhesion, scratch resistance, and water resistance. , resistant to processing chemicals (cutting oil, acidic solution). The coating properties related to water-based hybrid coatings, such as viscosity, consistency, shake, film thickness and hardness, can be penetrated by fillers such as cerium oxide, aluminum oxide, calcium carbonate (stone powder), barium sulfate, titanium dioxide, etc. Inorganic formulations are used to make adjustments.

The aqueous hybrid coating of the present invention is mainly used for applying a non-permanent material protective film. In the examples of the present invention, the aqueous resin mixing ratio and the bridging agent composition applicable to the surface of different materials are described; however, the formulation of the aqueous mixed coating of the present invention is described. And the application is not limited to the formulation of the water-based resin, bridging agent and the like used in the following examples, the coating construction method and the material use.

Embodiment 1: Water-based mixed coating for protecting plastic materials

A mixture of aqueous PU resin dispersion (emulsion) (PU-1) and aqueous acrylic resin (AC-2), PU-1/AC-2=4/1, bridging agent, polyaziridines , PICASSIAN XL-706), which is 2.0% (2.0 phr) of the solid content of the resin coating, is prepared as a "single-liquid" water-based hybrid coating; sprayed on the surface of a clean polymethyl methacrylate (PMMA) transparent sheet. Then, it is placed in a 50 ° C oven to be dried by hot air to form a transparent protective film having a thickness of about 35 mm, a hardness of 1H pencil hardness, and a density of 4-5 B. The transparent sheet is immersed in an aqueous solution at 60 ° C for 15 minutes, and then coated. The film peels off automatically and no paint remains on the PMMA surface.

Example 2: Water-based mixed coating for protecting aluminum :

A mixture of waterborne epoxy resin emulsion (EP-1), aqueous PU resin dispersion (emulsion) (PU-1) and aqueous acrylic resin (AC-1), EP-1/PU-1/AC- 2=2/3/1, bridging agent, polyaziridines (PICASSIAN XL-706) and polycarbodiimides (PICASSIAN XL-701) are 2.0% (2.0 phr) of resin coating solids, respectively. It is prepared into a "single-liquid" water-based mixed coating; before construction, 20 phr of a filler such as barium sulfate is added to increase the consistency of the aqueous coating, and increase the thickness of the coating film and the abrasion resistance of the dry film. Before coating and coating, the coating formulation is evenly stirred by a mechanical stirrer, sprayed on the surface of the cleaned aluminum, and then placed in a 90 ° C oven to be dried by hot air to form a protective film with a thickness of about 50 mm and a hardness of 2H pencil. Hardness, adhesion is 5B, cutting oil (10 minutes unchanged white); after immersing the aluminum in 60 ° C aqueous solution for 15 minutes, the coating film will automatically fall off automatically, and no coating remains on the aluminum surface.

Example 3: Water-based coating for protecting stainless steel:

A mixture of waterborne epoxy resin emulsion (EP-2), aqueous PU resin dispersion (emulsion) (PU-3) and aqueous acrylic resin (AC-1) (EP-2/PU-3/AC-) 1=2/3/1), when A agent; mixed bridging agent, polyaziridines (PICASSIAN XL-706) and polyisocyanates (CORONATE AQ130) are 2.0% (2.0 phr) of resin coating solids. When the agent B is prepared into a "two-liquid type" aqueous mixed coating; the two-liquid dosage form (A/B agent) is uniformly mixed before spraying, and 30 phr of barium sulfate and aluminum oxide are added before the application. The consistency of the coating), and increase the thickness of the coating, as well as the wear resistance of the dry film. Before spraying, the coating formulation is uniformly mixed with three rollers, sprayed on the surface of the stainless steel, and then placed in an oven at 80 ° C to be dried by hot air to form a protective film having a thickness of about 55 mm and a hardness of 2-3H pencil hardness and density. The degree of inspection (100-gauge test) is 5B, and meets the specifications of scratch resistance, water resistance, and processing chemicals (cutting oil, acidic solution); the stainless steel is immersed in an aqueous solution at 60 ° C for 15 minutes, and the coating film falls off automatically. , stainless steel surface does not leave paint.

Example 4: Water-based mixed coating for protecting composite materials:

A mixture of aqueous PU resin dispersion (emulsion) (PU-4) and aqueous acrylic resin (AC-2), PU-4/AC-2=2/1; bridging agent, multi-carbodiimide ( Polycarbodiimides, PICASSIAN XL-701), which accounts for 2.0% (2.0 phr) of the solid content of the resin coating, is prepared by mixing the coating formulation with a mechanical stirrer to prepare a "single-liquid" aqueous mixed coating; spraying on a cleaned acrylic The surface of the paint is painted, and then naturally dried after being exposed to a normal temperature and ventilated place to form a protective film having a thickness of about 35 mm, a hardness of 1H pencil hardness, and a density of 3-4 B; after cleaning the acrylic paint surface with a water gun, The coating film peels off smoothly and the coating on the surface of the acrylic paint does not remain.

Example 5: Water-based mixed coating for protecting solar panel glass:

A mixture of waterborne epoxy resin emulsion (EP-1), aqueous PU resin dispersion (emulsion) (PU-2) and aqueous acrylic resin (AC-1) (EP-1/PU-2/AC-) 1=2/4/1), when A; mixed bridging agent polyaziridines (PICASSIAN XL-706) and polyisocyanates (CORONATE AQ130) each accounted for 2.0% (2.0 phr) of resin coating solids When the B agent is prepared, it is prepared into a "two-liquid type" water-based mixed paint; the two-liquid type (A/B agent) is sprayed and mixed with a mechanical stirrer before the spraying, and the paint is cleaned (pickled) The solar panel glass sheet washed with water and immersed in the diluted aqueous mixed coating, and then the coated glass sheet is placed in a 90 ° C oven to be dried by hot air to form a protective film having a thickness of about 50 mm and a hardness of >3H pencil. Hardness, adhesion (100-test) is 5B, cutting oil (10 minutes unchanged white); after immersing the glass sheet in 60 ° C aqueous solution for 20 minutes, the coating film will automatically fall off automatically, and the surface of the glass sheet will not leave any coating. .

Embodiment 6: Protection optics PC Water-based hybrid coating for lenses:

A mixed resin of waterborne epoxy resin emulsion (EP-1), aqueous PU resin dispersion (emulsion) (PU-2) and aqueous acrylic resin (AC-1) (PU-2/AC-1=4/) 1), when A agent; mixed bridging agent polyaziridines (PICASSIAN XL-706) and polyisocyanates (CORONATE AQ130), etc., about 2.0% (2.0 phr) of the solid content of the resin coating when the agent B Prepared into a "two-liquid type" water-based mixed coating; this two-liquid dosage form (A/B agent) is washed and mixed with a mechanical stirrer before the spraying, and the mixture is cleaned (pickled and washed with water) The optical PC lens material is impregnated with the diluted aqueous mixed paint, and then the coated PC lens material is placed in a 60 ° C oven to be dried by hot air to form a protective film having a thickness of about 30 mm, a hardness of 2H, and a hardness of 2H. 5B, cutting oil (10 minutes unchanged white); after the PC lens material was immersed in an aqueous solution of 60 ° C for 20 minutes, the coating film peeled off automatically and the surface of the optical PC lens material did not remain.

Example 7: Water-based mixed coating for protecting stone:

Generally, the stone used for building materials (flooring) (including marble, granite and other stone and parquet) has a porous surface, which is often contaminated by oil (oil, beverage, coffee, betel nut, juice, etc.) and non-wearing. The surface is vulnerable to damage, especially in the process of storage, transportation and decoration, the probability of damage is greater; the choice of waterborne epoxy resin emulsion (EP-1), aqueous PU resin dispersion (emulsion) (PU-1) and water Acrylic resin (AC-1) mixed resin, EP-1/PU-1/AC-2=3/3/1, adding filler (stone powder, barium sulfate) 10 phr each, bridging agent polyethyleneimine (polyaziridines, PICASSIAN XL-706) is 1.5% (1.5 phr) of the solid content of the resin coating, prepared into a "single liquid" aqueous mixed coating; before the construction, adding 20 phr of cerium oxide and 40 phr of calcium carbonate to adjust the water-based coating Consistency, and increase the thickness of the film, as well as the wear resistance of the dry film. The coating formulation is evenly mixed with a three-roller, sprayed on the surface of the cleaned stone, and then dried in a ventilated environment at room temperature for about 24 hours to form a protective film having a thickness of about 100 mm. The hardness is >2H and the adhesion is 3- 5B; After the decoration construction, a non-woven fabric containing an aqueous solution is placed on the surface of the stone, and the overnight coating film is smoothly and automatically peeled off with the non-woven fabric, and no paint remains on the surface of the stone.

Example 8: Aqueous mixed coating for protecting the surface of the paint:

The body is painted with gold, and other parts of the body often need to be properly protected to prevent new paint from contaminating other original body paints. A mixture of an aqueous epoxy resin dispersion (emulsion) (EP-1) and an aqueous acrylic resin (AC-2), EP-1/AC-2=1/1, bridging agent, multiple ethyleneimine (option) Polyaziridines, PICASSIAN XL-706) is a "single-liquid" water-based hybrid coating with a solid content of 1.0% (1.0 phr). It is prepared by adding 50 phr of stone powder to adjust the consistency of the waterborne coating. And increase the thickness of the coating film, as well as the wear resistance of the dry film, stir and mix the coating formulation with a mechanical stirrer, spray it on the surface of the cleaned body paint, and then dry it in a well-ventilated environment, often after overnight temperature. Forming a transparent protective film with a thickness of about 150 mm, a hardness of 1H pencil hardness, and a tightness of 2-4B; the transparent protective film protects the original paint of the vehicle body from paint contamination during the operation of the body sheet metal painting; After completion, it can be cleaned with an aqueous solution spray to remove the transparent protective coating film, restore the original body paint, and no paint remains on the surface.

Example 9: Protection ITO Aqueous mixed coatings for glass:

A mixture of waterborne epoxy resin emulsion (EP-1), aqueous PU resin dispersion (emulsion) (PU-2) and aqueous acrylic resin (AC-1) (EP-1/PU-2/AC-) 1=2/4/1), when A agent; mixed bridging agent polyaziridines (PICASSIAN XL-706) and polycarbodiimides (PICASSIAN XL-701) each accounted for 2.0% of the solid content of the resin coating % (2.0 phr) when the B agent is prepared as a "two-liquid type" water-based mixed coating; the two-liquid dosage form (A/B agent) is a mechanical agitator, and the coating formulation is stirred and uniformly mixed before spraying. The ITO glass sheet cleaned (acid washed and cleaned with water) is impregnated with the diluted aqueous mixed paint, and then the coated glass sheet is placed in an oven at 80 ° C to be dried by hot air to form a protective film having a thickness of about 50 mm. Hardness >3H pencil hardness, adhesion is 5B, cutting oil (10 minutes unchanged white); after immersing the ITO glass sheet in 60 ° C aqueous solution for 20 minutes, the coating film will automatically fall off automatically, and the surface of the glass sheet will not leave any coating. .

As described above, the single-liquid type aqueous mixed paint and the two-liquid type water-based mixed paint of the present invention can be applied to non-permanent material protection; the purpose is to prevent the material from being transported, stored, processed to the finished product, and avoided. The surface is scratched or stained, and after the material is processed, the protective film can be easily peeled off, recovered, and concentrated from the surface of the material without using any organic solvent.

The water-based mixed coating of the invention can be customized according to the individual requirements of the surface material and the protective film performance of the material, and the protection object can cover various hard and soft materials such as metal, non-metal, plastic, stone or baking paint. The aqueous mixed coating is prepared by using an aqueous resin dispersion (emulsion) such as an epoxy resin, a polyurethane (PU) and an acrylic resin containing a reactive functional group and being non-toxic, and is formulated with a single or two or more kinds of resins. The bridging agent is blended to achieve a single-liquid or two-liquid type finished product, and the drying process of the protective film is only a chemically bonded bridging reaction, and does not produce any toxic or volatile organic substances. The water-based mixed paint of the present invention is a cleaning process, and the product is protected by a friendly global environment.

The invention has been described above in terms of the preferred embodiments, and it should be understood by those skilled in the art that the present invention is not intended to limit the scope of the invention. It should be noted that variations and permutations equivalent to those of the embodiments are intended to be included within the scope of the present invention. Therefore, the scope of protection of the present invention is defined by the scope of the patent application.

10‧‧‧Protective film

11‧‧‧Bridge Agent

12‧‧‧Epoxy resin

13‧‧‧Polyurethane resin

14‧‧‧Acrylic resin

Fig. 1 is a schematic view showing a protective film formed by drying the aqueous mixed paint of the present invention.

Claims (6)

A one-liquid type aqueous mixed paint comprising: (A) an aqueous resin dispersion comprising at least one aqueous resin neutralized by a tertiary amine, wherein the at least one aqueous resin is selected from the group consisting of an aqueous epoxy resin and an aqueous polyurethane resin And a group of aqueous acrylic resins, wherein the at least one aqueous resin contains a carboxyl group (COO ⁻ ) and other reactive functional groups; and (B) a bridging agent, when the one-liquid aqueous mixed coating is dried, The bridging agent is bridged with the at least one aqueous resin to form Interpenetrating Polymeric Networks (IPN), wherein the one-liquid aqueous mixed coating comprises: 100 parts by weight of resin; and 0.1~ 30.0 parts by weight of the bridging agent, and the bridging agent is selected from the group consisting of polyaziridines and polyisocyanates. The one-liquid type aqueous mixed paint according to claim 1, further comprising: (C) an organic additive selected from the group consisting of a thickener and an antioxidant; and (D) an inorganic filler, which is A group consisting of calcium carbonate, stone powder, barium sulfate, cerium oxide, aluminum oxide and titanium dioxide is selected. The one-liquid type aqueous mixed paint according to claim 1, wherein the aqueous resin dispersion has a pH of more than 8. A two-liquid aqueous mixed coating comprising: A agent, comprising: an aqueous resin dispersion comprising at least one aqueous resin neutralized by a tertiary amine, wherein the at least one aqueous resin is selected from the group consisting of aqueous epoxy resins a group consisting of an aqueous polyurethane resin and an aqueous acrylic resin, the at least one aqueous resin containing a carboxyl group (COO ⁻ ) and other reactive functional groups; and a B agent comprising: a bridging agent; The agent A and the agent B are mixed to form an aqueous mixed coating, and after the aqueous mixed coating is dried, the bridging agent is bridged with the at least one aqueous resin to form an interpenetrating polymeric network (IPN). Wherein, when the agent A and the agent B are mixed to form an aqueous mixed coating, the aqueous mixed coating comprises: 100 parts by weight of the resin; and 0.1 to 30.0 parts by weight of the bridging agent, and the bridging agent selected from the agent B. A group consisting of polyaziridines and polyisocyanates. The two-liquid type aqueous mixed paint according to claim 4, wherein the agent A further comprises: an organic additive selected from the group consisting of a thickener and an antioxidant; and the agent B further comprises: an inorganic filler It is selected from the group consisting of calcium carbonate, stone powder, barium sulfate, barium oxide, aluminum oxide and titanium dioxide. The two-liquid type aqueous mixed paint according to claim 4, wherein the aqueous resin dispersion has a pH of more than 8.