CN113980558A - Coating and coating suitable for PVC (polyvinyl chloride) product and preparation method thereof - Google Patents
Coating and coating suitable for PVC (polyvinyl chloride) product and preparation method thereof Download PDFInfo
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- C08J2327/00—Characterised by the use of 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 a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of 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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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Abstract
The invention relates to a paint suitable for PVC products, which comprises a UV paint, a thermochromic paint and gloss oil; wherein: the UV coating comprises the following components in percentage by weight: 50-80% of UV resin oligomer, 10-30% of reactive diluent, 5-40% of solvent, 2-8% of photoinitiator and 0.2-2% of auxiliary agent; the thermochromic paint comprises the following components in percentage by weight: 50-70% of water-based resin, 15-40% of liquid crystal microcapsule, 0.05-0.5% of wetting agent, 0.05-0.5% of flatting agent, 0.05-1% of defoaming agent, 0.5-2% of thickening agent and the balance of deionized water. When the coating prepared by the coating is applied to PVC products, the coating has the advantages of excellent coating adhesion and environmental protection, can realize reversible color change along with the change of environmental temperature, and has strong market attraction.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a coating and a coating suitable for PVC products and a preparation method thereof.
Background
The PVC toy is mainly prepared from PVC (polyvinyl chloride) raw materials, more plasticizers are generally added into the PVC toy, the plasticizers in the PVC are easy to migrate to the surface, the service life of the PVC is shortened, meanwhile, a decorative coating is dropped, children can contact with harmful substances in the using process and damage children health, therefore, a layer of coating is generally coated on a PVC base material to play a role in protection and decoration, hard PVC is mainly prepared from coatings containing polyvinyl chloride-based copolymer resin, acrylate resin, polyurethane, nitrocotton and the like, soft PVC is prepared from vinyl chloride-vinyl acetate copolymer resin and polyurethane coating, and a large amount of solvents are volatilized in the curing process to damage the environment.
And with the improvement of living standard and the upgrade of consumption, the market attraction of the traditional toy with single color is reduced. The reversible temperature-sensitive liquid crystal coating has the advantages of wide color development temperature range, adjustable temperature range, high coating reflectivity and metallic luster, and the coating can change from colorless to red-orange-yellow-green-blue-purple and then colorless along with the change of temperature. Therefore, the development of a safe reversible thermochromic coating for PVC has wide market prospect.
Disclosure of Invention
The application mainly solves the problem that the market attraction of the traditional toy with a single color is reduced, and provides a coating applied to a PVC product and a preparation method of the coating.
In order to achieve the above object, the present application provides a paint suitable for PVC products, comprising a UV paint, a thermochromic paint and a gloss oil; the UV coating comprises the following components in percentage by weight: 50% -80% of UV resin oligomer; 10 to 30 percent of active diluent; 5 to 40 percent of solvent; 2 to 8 percent of photoinitiator; 0.2 to 2 percent of auxiliary agent; the thermochromic paint comprises the following components in percentage by weight: 50% -70% of water-based resin; 15% -40% of liquid crystal microcapsules; 0.05 to 0.5 percent of wetting agent; 0.05 to 0.5 percent of flatting agent; 0.05 to 1 percent of defoaming agent; 0.5 to 2 percent of thickening agent; the balance being deionized water.
As a further improvement of the application, the UV resin oligomer is formed by compounding an oligomer I and an oligomer II, wherein the oligomer I is epoxy acrylic resin, and the oligomer II is polyurethane acrylic resin.
As a further improvement of the present application, the epoxy acrylic resin is at least one of amine-modified epoxy acrylate and fatty acid-modified epoxy acrylate; the polyurethane acrylic resin is aliphatic polyurethane acrylate.
As a further improvement of the application, the weight percentage of the oligomer I in the UV coating is 40-60%, and the weight percentage of the oligomer II in the UV coating is 10-30%.
As a further improvement of the present application, the reactive diluent comprises at least one of lauryl acrylate, ethoxyethoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl methacrylate, tripropylene glycol diacrylate, 1, 6-ethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate.
As a further improvement of the application, the solvent is a compound solvent of an alcohol solvent and an ester solvent.
As a further improvement of the UV coating, the weight percentage of the alcohol solvent in the UV coating is 1% -30%, and the weight percentage of the ester solvent in the UV coating is 1% -30%.
As a further improvement of the application, the alcohol solvent is at least one of ethanol and isopropanol, and the ester solvent is at least one of ethyl acetate, n-butyl acetate, n-propyl acetate and isopropyl acetate.
As a further improvement of the application, the aqueous resin is at least one of water-soluble acrylic resin, acrylic emulsion and aqueous polyurethane resin.
As a further improvement of the application, the wetting agent is at least one of an anionic surfactant, a nonionic surfactant and a polyether modified polysiloxane compound, the leveling agent is at least one of a silicone type and an acrylic type, and the defoaming agent is at least one of a silicone defoaming agent and a non-silicone defoaming agent.
As a further improvement of the application, the liquid crystal microcapsule is prepared by the following method: s1, preparing a PVA aqueous solution; s2, dissolving PMMA and cholesteric liquid crystal in ethyl acetate to obtain a liquid crystal mixture; s3, stirring the PVA aqueous solution in the step S1, adding the liquid crystal mixture in the step S2 into the PVA aqueous solution, emulsifying and volatilizing ethyl acetate, and centrifuging after the ethyl acetate is volatilized to obtain the liquid crystal microcapsule.
In order to realize the above-mentioned purpose, this application still provides a coating suitable for PVC goods, including UV dope layer, temperature sensing discoloration layer and the gloss oil layer of range upon range of in proper order on the PVC substrate, the UV dope layer by the aforesaid UV coating preparation form, temperature sensing discoloration layer by the aforesaid temperature sensing discoloration coating preparation form, gloss oil be the aforesaid gloss oil.
In order to achieve the above object, the present application also provides a method for preparing a coating suitable for PVC articles, comprising the steps of: s1, preparing a UV coating: mixing, dispersing and standing a UV resin oligomer, a reactive diluent, a photoinitiator, an auxiliary agent and a solvent, wherein the UV coating is the UV coating; s2, preparing the thermochromic paint: sequentially adding water-based resin, liquid crystal microcapsules, deionized water, a wetting agent, a flatting agent, a thickening agent and a defoaming agent, stirring after the addition is finished, and standing at room temperature for later use, wherein the thermochromic paint is the thermochromic paint; s3, spraying the UV coating in the step S1 on a PVC base material, wherein the thickness of a wet film of a UV layer is 10-30 μm, and curing to obtain a UV coating; s4, spraying the temperature-sensitive color-changing coating in the step S2 on the UV coating in the step S3, wherein the thickness of a wet film of the temperature-sensitive color-changing layer is 50-150 mu m, and the surface of the temperature-sensitive color-changing layer is dried and then baked to obtain the temperature-sensitive color-changing coating; s5, spraying gloss oil on the thermochromic coating in the step S4, wherein the thickness of the gloss oil wet film is 20-30 microns, and curing to obtain a gloss oil layer.
The PVC product paint has the beneficial effects that the paint suitable for PVC products comprises UV paint, thermochromic paint and gloss oil; wherein: the UV coating comprises the following components in percentage by weight: 50-80% of UV resin oligomer, 10-30% of reactive diluent, 5-40% of solvent, 2-8% of photoinitiator and 0.2-2% of auxiliary agent; the thermochromic paint comprises the following components in percentage by weight: 50-70% of water-based resin, 15-40% of liquid crystal microcapsule, 0.05-0.5% of wetting agent, 0.05-0.5% of flatting agent, 0.05-1% of defoaming agent, 0.5-2% of thickening agent and the balance of deionized water. When the coating prepared by the coating is applied to PVC products, the coating has the advantages of excellent coating adhesion and environmental protection, can realize reversible color change along with the change of environmental temperature, and has strong market attraction.
Drawings
FIG. 1 is a schematic structural view of a coating for a PVC article of the present application;
in the figure: 1. a UV coating layer; 2. a temperature-sensitive color-changing layer; 3. polishing the oil layer; 4. a PVC substrate.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more clear, the following description of the present application will be made in detail and completely with reference to the specific embodiments and the accompanying drawings. It should be understood that the described embodiments are only a few embodiments of the present application, not all embodiments, and are not intended to limit the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The application provides a coating suitable for PVC goods, including UV coating, temperature sensing coating and gloss oil, can prepare the coating that is applicable to PVC goods by above-mentioned coating, as shown in figure 1, this coating structure is including stacking gradually UV dope layer 1, temperature sensing discoloration layer 2 and gloss oil layer 3 on PVC substrate 4. The coating suitable for the PVC product can block migration of a plasticizer in PVC, has excellent adhesion, good stain resistance and excellent solvent resistance, and can realize reversible color change along with the change of environmental temperature.
The application provides a UV coating, which comprises the following components in percentage by weight: 50-80% of UV resin oligomer; 10-30% of reactive diluent; 5 to 40 percent of solvent; 2 to 8 percent of photoinitiator; 0.2 to 2 percent of auxiliary agent. The UV coating has the characteristics of low toxicity, low pollution and low VOC, and the UV coating layer prepared from the UV coating can obstruct the migration of a plasticizer in PVC and prolong the service life of PVC plastics.
In some embodiments, the UV resin oligomer in the UV coating is formulated from oligomer i and oligomer ii, the oligomer i being an epoxy acrylic resin and the oligomer ii being a urethane acrylic resin. Preferably, the weight percentage of the oligomer I in the UV coating is 40-60%, and the weight percentage of the oligomer II in the UV coating is 10-30%. Furthermore, the epoxy acrylic resin is at least one of amine modified epoxy acrylate and fatty acid modified epoxy acrylate, the amine modified epoxy acrylate can improve the curing rate and the adhesion with the substrate, and the fatty acid modified epoxy acrylate has better flexibility and chemical resistance, such as: the oligomer I can be selected from but not limited to at least one of CN 2100 and CN 2101 of Sartomema, Cyanote EB 600, Kening 3105, Pasteur EA 81, EA 8765, cis-Gong-Da EP107, and Bluecurol L-6111 and L-6112; the polyurethane acrylic resin is aliphatic polyurethane acrylate, and the cured film of the aliphatic polyurethane acrylate has good flexibility, such as: the oligomer II can be selected from but not limited to at least one of Saedoma CN 981, CN 968, Cycotex EB 245, Corning 6010, Blucoleya L-6200, and Lcoya 6201. In view of the components in the selected UV resin oligomer, the coating prepared by compounding the oligomer I epoxy acrylate and the oligomer II urethane acrylate has the advantages of flexibility, excellent scratch resistance, excellent adhesion with a PVC substrate, good chemical resistance, capability of blocking the migration of a plasticizer in PVC, excellent adhesion with a liquid crystal coating layer and normal color development of the liquid crystal coating.
In some embodiments, the reactive diluent in the UV coating includes at least one of lauryl acrylate, ethoxyethoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl methacrylate, tripropylene glycol diacrylate, 1, 6-ethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate. Wherein: lauryl Acrylate (LA), ethoxyethoxyethoxyethyl acrylate (EOEOEA), tetrahydrofurfuryl acrylate (THFA) and isobornyl methacrylate (IBOA) are monofunctional, LA and EOEOEA have good plasticizing effect, and THFA and IBOA are beneficial to improving adhesive force; tripropylene glycol diacrylate (TPGDA) and 1, 6-ethylene glycol diacrylate (HDDA) are bifunctional groups, TPGDA has strong diluting capability and high curing speed, and HDDA can improve the adhesion to plastics and the flexibility of a cured film; trimethylolpropane triacrylate (TMPTA) and ditrimethylolpropane tetraacrylate (DTMPTA) are multifunctional groups, and TMPTA and DTMPTA can improve the crosslinking density. Therefore, the compounding of EOEOEOEA, THFA and HDDA can improve the flexibility of the coating and the adhesion with the substrate, and meanwhile, the addition of TMPTA and DTMPTA with the weight percentage of 3-5% can improve the crosslinking density and improve the migration of the plasticizer of the PVC substrate.
In some embodiments, the solvent in the UV coating is a built solvent of an alcohol solvent and an ester solvent. Preferably, the alcohol solvent is at least one of ethanol and isopropanol, and the ester solvent is at least one of ethyl acetate, n-butyl acetate, n-propyl acetate and isopropyl acetate. The alcohol and ester compound solvent selected in the application can adjust the viscosity of the coating, and further, the weight percentage of the alcohol solvent in the UV coating is 1% -30%, and the weight percentage of the ester solvent in the UV coating is 1% -30%. In addition, the photoinitiator in the UV coating is not particularly limited, and may be, but not limited to, at least 1 of basf 184, 819, TPO, 100, 1173, 160; the auxiliary agent in the UV coating comprises a wetting agent, a leveling agent and the like, wherein: the wetting agent can be but not limited to at least one of Lencolo3103, Lencolo3106, Lencolo 3109 and BYK-358N, BYK-333, and the leveling agent can be but not limited to at least one of Lencolo3103, Lencolo3106, Lencolo 3109 and BYK-358N, BYK-333, and the wetting agent and the leveling agent with the function of increasing the slip can influence the repairability and are not optional.
In the application, the reversible temperature-sensitive liquid crystal coating has wide color development temperature range and adjustable temperature range, and the coating can change from colorless to red-orange-yellow-green-blue-purple and then colorless along with the change of temperature, so that the coating has high reflectivity and metallic luster. Consequently, set up one deck temperature sensing discoloration layer in the outside of UV dope layer in this application, but the liquid crystal is because the sensitivity of itself and the crystallization of mixed liquid crystal, easily receive influence such as ambient temperature, solvent, and the liquid crystal coating is direct to be applied to the PVC surface, and the color development effect of liquid crystal can disappear, consequently, prepares into the microcapsule with the liquid crystal earlier and prepares into coating again, and this application provides a practical temperature sensing discoloration layer coating. The thermochromic paint comprises the following components in percentage by weight: 50-70% of water-based resin, 15-40% of liquid crystal microcapsule, 0.05-0.5% of wetting agent, 0.05-0.5% of flatting agent, 0.05-1% of defoaming agent, 0.5-2% of thickening agent and the balance of deionized water.
In some embodiments, the liquid crystal microcapsule in the thermochromic layer coating material is prepared by: s1, preparing a PVA aqueous solution; s2, dissolving PMMA and cholesteric liquid crystal in ethyl acetate to obtain a liquid crystal mixture; s3, stirring the PVA aqueous solution in the step S1, adding the liquid crystal mixture in the step S2 into the PVA aqueous solution, emulsifying and volatilizing ethyl acetate, and centrifuging after the ethyl acetate is volatilized to obtain the liquid crystal microcapsule.
In some embodiments, the aqueous resin in the thermochromic layer coating material is at least one of a water-soluble acrylic resin, an acrylic emulsion, and an aqueous urethane resin. Preferably, the aqueous resin can be at least one of Acure-2750, Acure-509, Bayhydrol U XP 2757, Guangzhou Guangxi New materials 7012, 2301-XP and Andrographis 1720A and 1802A, but not limited to.
In some embodiments, the wetting agent in the thermochromic coating is at least one of an anionic surfactant, a nonionic surfactant and a polyether modified polysiloxane compound, specifically, the wetting agent comprises at least one of BYK-346, BYK-348, BYK-349, TEGO-250, TEGO-260 and TEGO-270, and the wetting agent can also be other commercially available wetting agents. The leveling agent in the temperature-sensitive color-changing layer coating is at least one of an organic silicon type and an acrylic type, specifically, the leveling agent is at least one of AMS 2020, TEGO Glide100, TEGO Glide400 and the like, and the leveling agent can also be other leveling agents sold in the market. The defoaming agent in the temperature-sensitive color-changing layer coating is at least one of a silicone defoaming agent and a non-silicone defoaming agent, specifically, the silicone defoaming agent comprises at least one of BYK-024, BYK-110, TEGO Foamex 925, TEGO Foamex810 and the like, and the defoaming agent can also be other commercially available silicone or non-silicone defoaming agents. The thickener in the thermochromic layer coating material includes at least one of Viscolam PS 166, BYK 420, modified hydroxyethyl cellulose, sodium alginate, and the like, and the thickener of the present application may also be other thickeners that are commercially available.
The gloss oil used for preparing the coating layer of the PVC product is not particularly limited, and the gloss oil can be a UV gloss oil for plastic substrates commonly used in the market, and a Delai coating DL-65-7UV gloss oil is selected in the following examples.
The application also provides a preparation method of the coating for the PVC product, which comprises the following steps: s1, preparing a UV coating: mixing, dispersing and standing the UV resin oligomer, the reactive diluent, the photoinitiator, the auxiliary agent and the solvent, wherein the UV coating is the UV coating given above; preferably, the mixture is dispersed for 30 to 60 minutes at the rotating speed of 400 to 1000r/min, and stands for 30 minutes for standby; s2, preparing the thermochromic paint: sequentially adding water-based resin, liquid crystal microcapsules, deionized water, a wetting agent, a flatting agent, a thickening agent and a defoaming agent, stirring after the addition is finished, and standing at room temperature for later use, wherein the temperature-sensitive color-changing coating is the temperature-sensitive color-changing coating; preferably, the materials are sequentially added at the rotating speed of 400 r/min-1000 r/min, the applied equipment can be a dispersion machine, the stirring time is 30 min-60 min, the standing time at room temperature is 30 min-60 min, and the materials are defoamed for later use; s3, spraying the UV coating in the step S1 on a PVC base material, wherein the thickness of a wet film of a UV layer is 10-30 μm, and curing to obtain a UV coating; preferably, the curing mode can be full-wave band UV mercury lamp curing, and the curing time is 3-10 s; s4, spraying the temperature-sensitive color-changing coating in the step S2 on the UV coating in the step S3, wherein the thickness of a wet film of the temperature-sensitive color-changing layer is 50-150 mu m, and the surface of the temperature-sensitive color-changing layer is dried and then baked to obtain the temperature-sensitive color-changing coating; preferably, the mixture is baked at 40-60 ℃ for 20-40 min; s5, spraying gloss oil on the thermochromic coating in the step S4, wherein the thickness of the gloss oil wet film is 20-30 microns, and curing to obtain a gloss oil layer; preferably, the curing mode can be full-wave band UV mercury lamp curing, and the curing time is 3 s-10 s.
The application further provides a set of embodiments for verifying the technical scheme of the application, and the embodiments of the application have excellent technical effects, and the embodiment of the application provides the temperature-sensitive color-changing layer paint of one embodiment, and corresponds to the UV paints of 5 embodiments, as follows:
preparing microcapsules: 1) preparing PVA water solution with certain concentration; 2) selecting PMMA as a wall material and dissolving cholesteric liquid crystal in ethyl acetate according to a certain proportion; 3) putting a certain amount of PVA aqueous solution into a three-neck flask, stirring, pouring the solution prepared in the step 2 into the three-neck flask, emulsifying and volatilizing ethyl acetate; 4) and after the ethyl acetate is completely volatilized, performing centrifugal separation to obtain the liquid crystal microcapsule for later use.
Preparing the temperature-sensitive color-changing layer coating: the temperature-sensitive color-changing layer coating comprises the following raw materials in percentage by weight: 60% of Guangzhou Zhi 7012 resin, 25% of the liquid crystal microcapsule prepared in the embodiment, 0.4% of a wetting agent BYK-348, 0.2% of a leveling agent BYK-381, 0.2% of a thickening agent BYK-420, 0.20% of a defoaming agent BYK-110, and the balance of deionized water; and sequentially adding the water-based resin, the liquid crystal microcapsule, deionized water, the wetting agent, the flatting agent, the thickening agent and the defoaming agent when the rotating speed of a dispersion machine is 800r/min, stirring for 60min, taking down the mixture, standing for 360min at room temperature, and defoaming to obtain the temperature-sensitive discoloring layer coating.
Preparing the UV coating: sequentially adding the UV resin oligomer, the reactive diluent, the photoinitiator, the auxiliary agent and the solvent according to the proportion in the table, dispersing for 50min by using a dispersion machine with the rotating speed of 600r/min, and standing for 30min for use.
Examples of UV coatings for PVC are shown in table 1:
preparation of a coating for PVC articles: 1) preparing a UV coating layer, namely spraying the UV coating in the embodiment on a PVC substrate, wherein the wet film thickness is 10-20 μm, and curing by using a full-waveband UV mercury lamp for 8s to obtain the UV coating layer; 2) preparing a temperature-sensitive color-changing coating, namely spraying the prepared temperature-sensitive color-changing coating on the coated UV coating layer, controlling the thickness of a wet film to be 100 mu m, and baking the dried surface of the coating in a 50 ℃ oven for 20min to obtain the temperature-sensitive color-changing coating; 3) and (3) spraying UV gloss oil on the temperature-sensitive color-changing coating in a spraying mode, wherein the thickness of a wet film is 20-30 mu m, and curing by using a full-wave band UV mercury lamp for 5s to obtain a gloss oil layer.
Comparative example
And directly spraying the temperature-sensitive color-changing coating on the PVC base material according to the second step in the preparation steps of the coating for the PVC product, and spraying the gloss oil layer according to the same construction mode of the third step after drying.
Performance testing
1) Adhesion force: and carrying out a cross-hatch method adhesion test according to the national standard GB/T9286-1998, wherein the test grades comprise 0-5 grades, the 0 grade is a perfect and undamaged state, and the higher the number is, the more serious the damage condition is.
2) Coating reflectivity: measuring with 3nh spectrophotometer under SCI and D65 mode with measuring aperture of 8mm, and reading reflectance value at 450nm to obtain reflectance not less than 25%.
The results of the performance tests are shown in table 2:
TABLE 2
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example | |
| Adhesion force | Level 0 | Level 0 | Level 0 | Level 0 | Level 0 | Fail to be qualified |
| Reflectivity of coating | 30.5％ | 31.8％ | 31.2％ | 32.1％ | 30.9％ | ＜10％ |
From the experimental results of table 2, it can be seen that:
1) the PVC base material is not sprayed with UV paint, and is directly coated with a temperature-sensitive color-changing layer and a gloss oil layer, the adhesive force of the coating is unqualified, and the reflectivity of the coating is less than 10 percent.
2) After the PVC base material is sprayed with the UV coating in the table 1, the temperature-sensitive color-changing layer and the gloss oil layer are coated, and the adhesive force and the reflectivity of the coating meet the requirements.
In summary, the present application provides a coating suitable for PVC products, comprising a UV coating, a thermochromic coating and a gloss oil; wherein: the UV coating comprises the following components in percentage by weight: 50-80% of UV resin oligomer, 10-30% of reactive diluent, 5-40% of solvent, 2-8% of photoinitiator and 0.2-2% of auxiliary agent; the thermochromic paint comprises the following components in percentage by weight: 50-70% of water-based resin, 15-40% of liquid crystal microcapsule, 0.05-0.5% of wetting agent, 0.05-0.5% of flatting agent, 0.05-1% of defoaming agent, 0.5-2% of thickening agent and the balance of deionized water. The UV coating prepared from the UV coating can block migration of a plasticizer in PVC, the UV coating is excellent in adhesion on a PVC substrate, the thermochromic coating is excellent in adhesion on the UV coating, the stain resistance is good, the solvent resistance is excellent, the form of the liquid crystal microcapsule cannot be interfered by the external environment, reversible color change can be realized along with the change of the environmental temperature, and the market attraction is strong.
Although the description is given in terms of embodiments, not every embodiment includes only a single embodiment, and such description is for clarity only, and those skilled in the art will recognize that the embodiments described herein may be combined as a whole to form other embodiments as would be understood by those skilled in the art.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.
Claims (13)
1. The paint suitable for PVC products is characterized by comprising a UV paint, a thermochromic paint and gloss oil;
the UV coating comprises the following components in percentage by weight:
the thermochromic paint comprises the following components in percentage by weight:
2. the coating suitable for PVC articles according to claim 1, wherein the UV resin oligomer is prepared by compounding an oligomer I and an oligomer II, wherein the oligomer I is epoxy acrylic resin, and the oligomer II is urethane acrylic resin.
3. The coating suitable for PVC products according to claim 2, wherein the epoxy acrylic resin is at least one of amine modified epoxy acrylate and fatty acid modified epoxy acrylate; the polyurethane acrylic resin is aliphatic polyurethane acrylate.
4. The PVC coating according to claim 2, wherein the oligomer I in the UV coating is 40-60 wt%, and the oligomer II in the UV coating is 10-30 wt%.
5. The coating suitable for PVC articles of claim 1 wherein the reactive diluent comprises at least one of lauryl acrylate, ethoxyethoxyethyl acrylate, tetrahydrofurfuryl acrylate, isobornyl methacrylate, tripropylene glycol diacrylate, 1, 6-ethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate.
6. The coating suitable for PVC products as claimed in claim 1, wherein the solvent is a compound solvent of alcohol solvent and ester solvent.
7. The coating suitable for PVC products according to claim 6, wherein the weight percentage of the alcohol solvent in the UV coating is 1-30%, and the weight percentage of the ester solvent in the UV coating is 1-30%.
8. The coating suitable for PVC products according to claim 6 or 7, wherein the alcohol solvent is at least one of ethanol and isopropanol, and the ester solvent is at least one of ethyl acetate, n-butyl acetate, n-propyl acetate and isopropyl acetate.
9. The coating suitable for PVC products as claimed in claim 1, wherein the aqueous resin is at least one of water-soluble acrylic resin, acrylic emulsion, aqueous polyurethane resin.
10. The coating suitable for PVC products according to claim 1, wherein the wetting agent is at least one of anionic surfactant, nonionic surfactant, polyether modified polysiloxane compound, the leveling agent is at least one of silicone type and acrylic type, and the defoaming agent is at least one of silicone type defoaming agent and non-silicone defoaming agent.
11. The coating suitable for PVC articles according to claim 1, wherein the liquid crystal microcapsule is prepared by the following method:
s1, preparing a PVA aqueous solution;
s2, dissolving PMMA and cholesteric liquid crystal in ethyl acetate to obtain a liquid crystal mixture;
s3, stirring the PVA aqueous solution in the step S1, adding the liquid crystal mixture in the step S2 into the PVA aqueous solution, emulsifying and volatilizing ethyl acetate, and centrifuging after the ethyl acetate is volatilized to obtain the liquid crystal microcapsule.
12. A coating suitable for PVC products, which is characterized by comprising a UV coating layer, a temperature-sensitive color-changing layer and a gloss oil layer which are sequentially laminated on a PVC substrate, wherein the UV coating layer is prepared from the UV coating of any one of claims 1 to 11, the temperature-sensitive color-changing layer is prepared from the temperature-sensitive color-changing coating of any one of claims 1 to 11, and the gloss oil is the gloss oil of claim 1.
13. A preparation method of a coating suitable for PVC products is characterized by comprising the following steps:
s1, preparing a UV coating: mixing, dispersing and standing a UV resin oligomer, a reactive diluent, a photoinitiator, an auxiliary agent and a solvent, wherein the UV coating is the UV coating as claimed in any one of claims 1 to 11;
s2, preparing the thermochromic paint: sequentially adding water-based resin, a liquid crystal microcapsule, deionized water, a wetting agent, a flatting agent, a thickening agent and a defoaming agent, stirring after adding, standing at room temperature for later use, wherein the thermochromic paint is the thermochromic paint according to any one of claims 1 to 11;
s3, spraying the UV coating in the step S1 on a PVC base material, wherein the thickness of a wet film of a UV layer is 10-30 μm, and curing to obtain a UV coating;
s4, spraying the temperature-sensitive color-changing coating in the step S2 on the UV coating in the step S3, wherein the thickness of a wet film of the temperature-sensitive color-changing layer is 50-150 mu m, and the surface of the temperature-sensitive color-changing layer is dried and then baked to obtain the temperature-sensitive color-changing coating;
s5, spraying gloss oil on the thermochromic coating in the step S4, wherein the thickness of the gloss oil wet film is 20-30 microns, and curing to obtain a gloss oil layer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115851057A (en) * | 2022-12-22 | 2023-03-28 | 广东希贵光固化材料有限公司 | UV coating for mahjong and preparation method thereof |
| CN116218295A (en) * | 2023-03-01 | 2023-06-06 | 博尔泰(上海)化工科技发展有限公司 | Low-density high-damping PVC (polyvinyl chloride) coating and preparation method thereof |
| CN116500815A (en) * | 2023-06-27 | 2023-07-28 | 佛山(华南)新材料研究院 | Decorative film and preparation method thereof |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103869387A (en) * | 2014-03-27 | 2014-06-18 | 宁波惠之星新材料科技有限公司 | Ultraviolet light curing optic hardened film, preparing device thereof and preparing method thereof |
| CN104031549A (en) * | 2014-07-02 | 2014-09-10 | 江苏海田技术有限公司 | Special UV scraping preventing adhesive force primer for PVC and preparing method of special UV scraping preventing adhesive force primer |
| CN104231725A (en) * | 2014-09-30 | 2014-12-24 | 永发印务(东莞)有限公司 | Optical extraordinary splendor ink composition consisting of multi-shell liquid crystal, and preparation method of optical extraordinary splendor ink |
| CN104817879A (en) * | 2015-04-09 | 2015-08-05 | 深圳万佳原精化科技股份有限公司 | Ultraviolet curing full-shielding protection printing ink |
| CN106479328A (en) * | 2016-11-07 | 2017-03-08 | 徐伟明 | A kind of quick-dry type ultraviolet-cured paint |
| CN106752737A (en) * | 2016-11-14 | 2017-05-31 | 上海普力通新材料科技有限公司 | A kind of PVC floor ultraviolet-curing paint and preparation method thereof |
| CN107236367A (en) * | 2017-06-30 | 2017-10-10 | 厦门理工学院 | PVC temperature-sensitive reversible color UV ink and preparation method, application method |
| JP2019185024A (en) * | 2018-04-09 | 2019-10-24 | Jnc株式会社 | Coating liquid containing liquid crystal capsules, and functional film produced therewith |
| CN110437731A (en) * | 2019-08-27 | 2019-11-12 | 浙江佑泰新材料科技有限公司 | A kind of UV-LED photocuring vacuum coating bottom coating and preparation method thereof |
| CN111025682A (en) * | 2019-12-24 | 2020-04-17 | 江苏汇恒眼镜有限公司 | Multi-color sunglasses and manufacturing method thereof |
| WO2020109363A2 (en) * | 2018-11-27 | 2020-06-04 | TheUnseen Limited | Coating compositions |
| CN111909560A (en) * | 2020-07-14 | 2020-11-10 | 华南师范大学 | Color-changeable reflective coating and preparation method and application thereof |
| CN112358767A (en) * | 2020-11-11 | 2021-02-12 | 深圳市崯涛油墨科技有限公司 | Reversible thermochromic LED curing ink and preparation method thereof |
| CN112721517A (en) * | 2019-10-28 | 2021-04-30 | 江苏集萃智能液晶科技有限公司 | Heat transfer film and preparation and application methods thereof |
| CN112980248A (en) * | 2021-02-23 | 2021-06-18 | 江苏集萃智能液晶科技有限公司 | Thermochromic liquid crystal microcapsule ink and thermochromic coating |
-
2021
- 2021-12-06 CN CN202111480254.4A patent/CN113980558B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103869387A (en) * | 2014-03-27 | 2014-06-18 | 宁波惠之星新材料科技有限公司 | Ultraviolet light curing optic hardened film, preparing device thereof and preparing method thereof |
| CN104031549A (en) * | 2014-07-02 | 2014-09-10 | 江苏海田技术有限公司 | Special UV scraping preventing adhesive force primer for PVC and preparing method of special UV scraping preventing adhesive force primer |
| CN104231725A (en) * | 2014-09-30 | 2014-12-24 | 永发印务(东莞)有限公司 | Optical extraordinary splendor ink composition consisting of multi-shell liquid crystal, and preparation method of optical extraordinary splendor ink |
| CN104817879A (en) * | 2015-04-09 | 2015-08-05 | 深圳万佳原精化科技股份有限公司 | Ultraviolet curing full-shielding protection printing ink |
| CN106479328A (en) * | 2016-11-07 | 2017-03-08 | 徐伟明 | A kind of quick-dry type ultraviolet-cured paint |
| CN106752737A (en) * | 2016-11-14 | 2017-05-31 | 上海普力通新材料科技有限公司 | A kind of PVC floor ultraviolet-curing paint and preparation method thereof |
| CN107236367A (en) * | 2017-06-30 | 2017-10-10 | 厦门理工学院 | PVC temperature-sensitive reversible color UV ink and preparation method, application method |
| JP2019185024A (en) * | 2018-04-09 | 2019-10-24 | Jnc株式会社 | Coating liquid containing liquid crystal capsules, and functional film produced therewith |
| WO2020109363A2 (en) * | 2018-11-27 | 2020-06-04 | TheUnseen Limited | Coating compositions |
| CN110437731A (en) * | 2019-08-27 | 2019-11-12 | 浙江佑泰新材料科技有限公司 | A kind of UV-LED photocuring vacuum coating bottom coating and preparation method thereof |
| CN112721517A (en) * | 2019-10-28 | 2021-04-30 | 江苏集萃智能液晶科技有限公司 | Heat transfer film and preparation and application methods thereof |
| CN111025682A (en) * | 2019-12-24 | 2020-04-17 | 江苏汇恒眼镜有限公司 | Multi-color sunglasses and manufacturing method thereof |
| CN111909560A (en) * | 2020-07-14 | 2020-11-10 | 华南师范大学 | Color-changeable reflective coating and preparation method and application thereof |
| CN112358767A (en) * | 2020-11-11 | 2021-02-12 | 深圳市崯涛油墨科技有限公司 | Reversible thermochromic LED curing ink and preparation method thereof |
| CN112980248A (en) * | 2021-02-23 | 2021-06-18 | 江苏集萃智能液晶科技有限公司 | Thermochromic liquid crystal microcapsule ink and thermochromic coating |
Non-Patent Citations (1)
| Title |
|---|
| 吕奎: "液晶微胶囊的制备与显示应用性能研究", 《中国优秀硕士学位论文全文数据库 信息科技辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115851057A (en) * | 2022-12-22 | 2023-03-28 | 广东希贵光固化材料有限公司 | UV coating for mahjong and preparation method thereof |
| CN116218295A (en) * | 2023-03-01 | 2023-06-06 | 博尔泰(上海)化工科技发展有限公司 | Low-density high-damping PVC (polyvinyl chloride) coating and preparation method thereof |
| CN116218295B (en) * | 2023-03-01 | 2024-05-07 | 博尔泰(上海)化工科技发展有限公司 | Low-density high-damping PVC (polyvinyl chloride) coating and preparation method thereof |
| CN116500815A (en) * | 2023-06-27 | 2023-07-28 | 佛山(华南)新材料研究院 | Decorative film and preparation method thereof |
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