CN112724747B - Temperature-change liquid crystal microcapsule ink and preparation method thereof - Google Patents
Temperature-change liquid crystal microcapsule ink and preparation method thereof Download PDFInfo
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- CN112724747B CN112724747B CN202011604480.4A CN202011604480A CN112724747B CN 112724747 B CN112724747 B CN 112724747B CN 202011604480 A CN202011604480 A CN 202011604480A CN 112724747 B CN112724747 B CN 112724747B
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- C—CHEMISTRY; METALLURGY
- 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
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
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- C—CHEMISTRY; METALLURGY
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- C—CHEMISTRY; METALLURGY
- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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Abstract
The invention relates to a temperature-change liquid crystal microcapsule ink which comprises the following components: the liquid crystal microcapsule ink comprises a liquid crystal microcapsule, water-based resin, a dark auxiliary material and a dispersing agent, and also provides a preparation method of the temperature-change liquid crystal microcapsule ink. The ink disclosed by the application not only solves the problem of the color change singleness of the traditional color-changing ink, but also solves the problem of the limitation of the use of the base materials of the common temperature-changing liquid crystal microcapsule ink, solves the color development problem of the temperature-changing liquid crystal microcapsule ink on different base color base materials, greatly improves the application range of the temperature-changing liquid crystal microcapsule ink, and can keep excellent color development performance in the use of various base materials.
Description
Technical Field
The invention relates to the technical field of ink preparation, in particular to temperature-change liquid crystal microcapsule ink and a preparation method thereof.
Background
The ink plays an indispensable role in human life and covers aspects such as clothes, eating and housing. In the development process of the ink, the life of human beings is continuously enriched from various single-color inks to various color-changing inks which are produced at the same time. However, the currently studied and used color-changing inks are mainly limited to inks based on color-changing dyes, which are converted between colored and colorless by applying different conditions externally, but are limited to only one color to colorless or colorless to colored. With the development of technology and the demand for life, people have begun to research color-changing inks for various color transitions.
Cholesteric liquid crystals can be considered as a special nematic liquid crystal whose molecules are arranged in layers in the direction of the short axis, the molecules in the layers are disordered but arranged parallel to each other, the long axis orientation of the molecules in different layers is also different, and they are periodically arranged in a helical structure rotating in the direction of the normal to the layer. The twisted rotation of the liquid crystal molecules causes a change in the refractive index, creating a photon forbidden band. When the photon forbidden band falls in the visible light range, the light with the same wavelength as the photon forbidden band can be selectively reflected by the cholesteric liquid crystal, thereby achieving the effect of colorful color development. The wavelength of the photon forbidden band is easily changed by the influence of external factors such as magnetic field, electric field, light, temperature and the like, so that the cholesteric liquid crystal has wide application prospect in the field of optical color development. However, the fluidity of cholesteric liquid crystals makes them poor in processability and stability, and cholesteric liquid crystals are generally microencapsulated to maintain their controllable optical properties.
At present, a large amount of temperature change dye type ink exists in the market, but the temperature change dye type ink can only realize single color change and cannot achieve the effect of multiple color change, in order to enrich the application functions of the ink, a small amount of liquid crystal microcapsules are used for replacing color change dye in the ink in the market, although the problem of colorful color change is solved due to the appearance of the temperature change liquid crystal microcapsule ink, the liquid crystal microcapsules can only have an excellent color developing function on a dark color substrate, and the application range of the liquid crystal microcapsules as the temperature change liquid crystal microcapsule ink is greatly limited.
Disclosure of Invention
The invention aims to solve the problems that the use of the temperature-change liquid crystal microcapsule ink is limited on a black substrate at present, the color development effect of the temperature-change liquid crystal microcapsule ink is poor by adopting substrates with other colors, and the application space of the temperature-change liquid crystal microcapsule ink is greatly limited.
In order to achieve the above object, the present application provides a temperature-sensitive liquid crystal microcapsule ink comprising the following components: liquid crystal microcapsule, water-based resin, dark auxiliary material and dispersing agent.
As a further improvement of the application, the temperature-change liquid crystal microcapsule ink comprises the following components in percentage by mass: the liquid crystal microcapsule accounts for 15-65%, the water-based resin accounts for 30-75%, the deep color auxiliary material accounts for 1-5%, and the dispersing agent accounts for 0.1-2%.
As a further improvement of the application, the liquid crystal microcapsule is one or more of different liquid crystal microcapsules with the temperature change range within 0-100 ℃.
As a further improvement of the application, the liquid crystal microcapsule is one or more of different liquid crystal microcapsules with the temperature change range within 0-60 ℃.
As a further improvement of the application, the liquid crystal microcapsule is one or more of different liquid crystal microcapsules with the temperature change interval within 40-60 ℃.
As a further improvement of the application, the aqueous resin is one or more of aqueous polyurethane resin, organic silicon modified aqueous polyurethane resin, methylated aqueous amino resin, high imino methylated melamine resin, high imino resin, methylated melamine resin and high methylated melamine resin.
As a further refinement of the present application, the dark auxiliary material is a single component or at least two components.
As a further improvement of the application, the single component is any one of dark auxiliary materials of iron black, carbon black, copper chromium black, iron chromium black, cobalt black and dark dyes.
As a further improvement of the application, the dispersing agent is one or more of polyethylene glycol 200 and polyethylene glycol 400.
As a further improvement of the application, the temperature-change liquid crystal microcapsule ink further comprises one or more of a defoaming agent, a wetting agent, a leveling agent, a bactericide, a preservative and a thickening agent.
As a further development of the application, the defoaming agent is of the non-silicon type and/or of the silicone type.
As a further improvement of the application, the non-silicon type is one or more of alcohols, fatty acids, fatty acid esters, phosphate esters, mineral oils and amides.
As a further development of the application, the wetting agent is a nonionic surfactant and/or an anionic surfactant.
As a further improvement of the present application, the nonionic surfactant is one or more of polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene polyoxypropylene block copolymer, silanol; the anionic surfactant is one or more of alkyl sulfate, sulfonate, fatty acid ester sulfate, carboxylic acid soap and phosphate.
As a further improvement of the application, the leveling agent is one or more of organic silicon and acrylic acid.
As a further improvement herein, the bactericide is an isothiazolinone and/or benzisothiazolinone.
As a further improvement of the present application, the preservative is one or more of benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, calcium propionate.
As a further development of the present application, the thickener is a natural thickener and/or a synthetic thickener.
As a further improvement of the present application, the natural thickening agent is one or more of starch, gum arabic, gelatin, seaweed gum, guar gum, and dextrin; the synthetic thickener is one or more of carboxymethyl cellulose, methyl cellulose, sodium starch phosphate, sodium carboxymethyl cellulose, sodium alginate, sodium polyacrylate, polyoxyethylene, and polyvinylpyrrolidone.
In order to achieve the above object, the present application further provides a method for preparing a temperature-variable liquid crystal microcapsule ink, which is suitable for the above temperature-variable liquid crystal microcapsule ink, and comprises the following steps: s1, fully stirring the liquid crystal microcapsule and the water-based resin, and uniformly mixing to obtain a liquid crystal microcapsule emulsion; s2, dispersing a dispersing agent, a deep color auxiliary material, and/or a defoaming agent, and/or a wetting agent, and/or a leveling agent, and/or a bactericide, and/or a preservative into water, fully stirring, and uniformly mixing to obtain a mixed solution A; s3, adding the mixed solution A obtained in the step S2 into the liquid crystal microcapsule emulsion obtained in the step S1, fully stirring and uniformly mixing to obtain a mixed solution B; s4, adding a thickening agent into the mixed solution B in the step S3, fully stirring and uniformly mixing to obtain the temperature-change liquid crystal microcapsule ink.
As a further improvement of the application, the temperature-change liquid crystal microcapsule ink comprises the following components in percentage by mass: 15-65% of liquid crystal microcapsule, 30-75% of water-based resin, 1-5% of deep color auxiliary material, 0.1-2% of dispersing agent, 0.1-1% of defoaming agent, 0.05-1% of wetting agent, 0.05-1% of flatting agent, 0.1-2% of bactericide, 0.05-3% of preservative, 0.1-5% of thickening agent and the balance of water.
As a further improvement of the present application, in step S1, the stirring temperature is 20 ℃ to 50 ℃, and the stirring time is 0.5h to 2 h; in step S3, the stirring speed is 100 r/min-500 r/min, and the stirring time is 1 h-4 h; in step S4, the stirring speed is 100 r/min-500 r/min, and the stirring time is 0.5 h-2 h.
The temperature-sensitive color-changing liquid crystal microcapsule ink and the preparation method thereof have the beneficial effects that the ink realizes the color richness of temperature-sensitive color changing, overcomes the limitation of using base materials of common temperature-sensitive color-changing liquid crystal microcapsule ink, solves the color development problem of the temperature-sensitive color-changing liquid crystal microcapsule ink on different base color base materials, and greatly improves the application range of the temperature-sensitive color-changing liquid crystal microcapsule ink. The ink can keep excellent color rendering property when used on various base materials, has good corrosion resistance, good hardness, good water resistance, excellent acid and alkali resistance, no toxicity and no pollution, and meets the requirements of environmental protection.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the following description of the embodiments of the present application will be made in detail and completely with reference to 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.
In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the illustrative example embodiments are set forth only and are not intended to limit the present invention. Therefore, it is intended that the scope of the invention be limited not by this detailed description, but rather by the claims appended hereto.
The components used in the following examples can be synthesized by a known method or obtained commercially. These synthetic techniques are conventional and the resulting compounds are tested for compliance with electronic compound standards.
According to an object of the present invention, there is provided a temperature-sensitive liquid crystal microcapsule ink comprising the following components: the liquid crystal microcapsule comprises a liquid crystal microcapsule, water-based resin, a dark auxiliary material and a dispersing agent, wherein the liquid crystal microcapsule is mainly used for color development and temperature-sensitive color change of printing ink. As a preferred embodiment, the temperature-change liquid crystal microcapsule ink comprises the following components in percentage by mass: the liquid crystal microcapsule accounts for 15-65%, the water-based resin accounts for 30-75%, the deep color auxiliary material accounts for 1-5%, and the dispersing agent accounts for 0.1-2%. In a preferred embodiment, the liquid crystal microcapsule is one or more of different liquid crystal microcapsules with temperature change interval within 0-100 ℃. In a further preferred embodiment, the liquid crystal microcapsule is one or more of different liquid crystal microcapsules with temperature change interval within 0-60 ℃. In a further preferred embodiment, the liquid crystal microcapsule is one or more of different liquid crystal microcapsules having a temperature-change range within 40 ℃ to 60 ℃.
In the present application, as a preferred embodiment, the aqueous resin is one or more of an aqueous polyurethane resin, an organosilicon-modified aqueous polyurethane resin, a methylated aqueous amino resin, a high imino methylated melamine resin, a high imino resin, a methylated melamine resin, and a high methylated melamine resin. As a further preferable embodiment, the aqueous resin is selected from the group consisting of waterborne polyurethane resins PU-6696, PU-6635D, PU-6638, PU-7735, PU-3738, PU-3737, PU-2851K, PU-3946, PU-3627, and organosilicon modified waterborne polyurethane resins IPU-8331 and SIPU-8333 in Jiangxi Hunan-K chemical industry; partially methylated waterborne amino resins W13-80 and W14-80 of national chemical Limited; aqueous polyurethane resins HUX-282, HUX-550 and HUX-1029 from Shanghai Hua Jia trade company Limited; sivor chemical water-based polyurethane resin PUE-991F, PUD-9051; aqueous polyurethane resin AH-1701 of Andai Huatai, AH-1702, AH-1704B, AH-1601B, AH-1728, AH-1730 and AH-1802; one or more of 385 high imino methylated melamine resin, 323 high imino resin, 373 partially methylated melamine resin and 350 high methylated melamine resin in cyanogen special chemical industry.
According to different densities of the dark auxiliary materials, when the density is higher than that of the liquid crystal microcapsule, the dark auxiliary materials sink to the bottom due to the action of gravity in the curing process; when the density is lower than that of the liquid crystal microcapsule, the liquid crystal microcapsule is positioned above the liquid crystal microcapsule due to buoyancy during the curing process; when the density is equal to that of the liquid crystal microcapsule, the dark auxiliary material and the liquid crystal microcapsule are uniformly dispersed. As a preferred embodiment, the dark auxiliary material is a single component or at least two components. As a further preferred embodiment, the single component is any one of iron black, carbon black, copper chromium black, iron chromium black, cobalt black and dark dyes. As a further preferred embodiment, said dark color auxiliary materials are selected from the group consisting essentially of iron blacks 722, 723, 740, 790; iron black of bayer, 318M, 303T, 360, 4330; carbon blacks 234N220, 234N330, 234N550, 234N660 from the bang chemical industry; cabot carbon black M900; mitsubishi high-color carbon black MCF 88; carbon black N330, N220 of source-wetting mineral products; g160 dye for ocean pigment; 9001 dye of hao vast chemical industry; one or more of VSFs 600 in the golden color workshop fine chemical industry.
In the present application, the dispersant is mainly used for uniformly dispersing solid and liquid particles of inorganic and organic pigments which are difficult to dissolve in liquid, and can prevent the particles from settling and coagulating to form stable suspension. As a preferred embodiment, the dispersant is one or more of polyethylene glycol 200, polyethylene glycol 400 and other polymeric dispersants. As a further preferred embodiment, the dispersing agent is selected from the group consisting of polyethylene glycol 200, polyethylene glycol 400; polymer dispersants K-350, K355, K366 and 8010N in the Koming chemical industry; macromolecular dispersing agents DH-6000, DH6163 and DH-6520S of the new green field materials; lubrium polymeric dispersant 24000 and the like.
In the present application, as a preferred embodiment, the temperature-variable liquid crystal microcapsule ink further includes a defoaming agent, a wetting agent, a leveling agent, a bactericide, a preservative, and a thickener. The antifoaming agent is mainly used to reduce the surface tension of water, solutions, suspensions, etc., to prevent foam formation, or to reduce or eliminate the original foam. As a preferred embodiment, the defoaming agent is of a non-silicon type and/or a silicone type. In a further preferred embodiment, the non-silicone type is one or more of organic substances such as alcohols, fatty acids, fatty acid esters, phosphoric acid esters, mineral oils, and amides; the organic silicon type is one or more of Nanhui CI-1734, CI-1648, CI-1210, CI-1660, Federal B-0518 and the like.
In this application, the wetting agent is primarily used to lower the surface energy of the solid material, making it more wettable by water. As a preferred embodiment, the wetting agent is a nonionic surfactant and/or an anionic surfactant. As a further preferred embodiment, the nonionic surfactant is one or more of polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene polyoxypropylene block copolymer, silanol; the anionic surfactant is one or more of alkyl sulfate, sulfonate, fatty acid ester sulfate, carboxylic acid soap and phosphate.
In the application, the leveling agent is mainly used for promoting the coating to form a flat, smooth and uniform coating film in the drying film-forming process, and can effectively reduce the surface tension of the coating liquid and improve the leveling property and uniformity of the coating liquid. As a preferred embodiment, the leveling agent is one or more of silicones, acrylics. In a more preferred embodiment, the silicone is one or more of WA-7326, WA-7410, WA-7333, WA-7307, WA-7435, WA-7450, JZ-456 in Jiazhong chemical industry, TEGO450 in Kanjin chemical industry, etc.; the acrylic acid is one or more of BYK-333, 346, 345, 300, 310, 381 of Bick Germany, Acomat FLOW-200 and the like.
In the present application, the biocide is primarily used to effectively control or kill microorganisms in the ink. As a preferred embodiment, the bactericide is an isothiazolinone and/or benzisothiazolinone.
In this application, the antiseptic mainly be used for inhibiting bacterial growing, increase of service life. As a preferred embodiment, the preservative is one or more of benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, calcium propionate.
In the present application, the thickener is mainly used to increase the viscosity of the system and keep the system in a uniform and stable suspension state or an emulsion state. As a preferred embodiment, the thickener is a natural thickener and/or a synthetic thickener. As a further preferred embodiment, the natural thickener is one or more of polysaccharide derivatives such as starch, gum arabic, gelatin, alginate jelly, guar gum, dextrin, and the like; the synthetic thickener is one or more of carboxymethyl cellulose, methyl cellulose, sodium starch phosphate, sodium carboxymethyl cellulose, sodium alginate, sodium polyacrylate, polyoxyethylene, and polyvinylpyrrolidone.
In order to achieve the object of the present invention, the present application further provides a method for preparing a temperature-variable liquid crystal microcapsule ink, which is suitable for the above temperature-variable liquid crystal microcapsule ink, and comprises the following steps: s1, fully stirring the liquid crystal microcapsule and the water-based resin, and uniformly mixing to obtain a liquid crystal microcapsule emulsion; s2, dispersing a dispersing agent, a dark auxiliary material, and/or a defoaming agent, and/or a wetting agent, and/or a leveling agent, and/or a bactericide, and/or a preservative into water, fully stirring, and uniformly mixing to obtain a mixed solution A; s3, adding the mixed solution A obtained in the step S2 into the liquid crystal microcapsule emulsion obtained in the step S1, fully stirring, and uniformly mixing to obtain a mixed solution B; s4, adding a thickening agent into the mixed solution B in the step S3, fully stirring and uniformly mixing to obtain the temperature-change liquid crystal microcapsule ink. The defoaming agent, the wetting agent, the leveling agent, the bactericide, the preservative and the like are functional auxiliary materials and can be selectively added according to the estimated application of the prepared ink.
As a further preferred embodiment, the temperature-change liquid crystal microcapsule ink comprises the following components in percentage by mass: 15-65% of liquid crystal microcapsule, 30-75% of water-based resin, 1-5% of deep color auxiliary material, 0.1-2% of dispersing agent, 0.1-1% of defoaming agent, 0.05-1% of wetting agent, 0.05-1% of flatting agent, 0.1-2% of bactericide, 0.05-3% of preservative, 0.1-5% of thickening agent and the balance of water.
As a further preferable embodiment, the liquid crystal microcapsule is a liquid crystal microcapsule with a temperature change range of 40 ℃ to 60 ℃, the aqueous resin is an aqueous polyurethane resin, the dark color auxiliary material is iron black, the dispersing agent is polyethylene glycol 200, the defoaming agent is an organosilicon type, the wetting agent is polyoxyethylene alkylphenol ether, the leveling agent is an organosilicon type, the bactericide is benzisothiazolinone, the preservative is potassium sorbate, the thickener is methylcellulose, and the temperature change liquid crystal microcapsule ink comprises the following components in percentage by mass: 35% of liquid crystal microcapsule, 50% of waterborne polyurethane resin, 2% of iron oxide black, 2000.5% of polyethylene glycol, 0.4% of organosilicon, 0.4% of polyoxyethylene alkylphenol ether, 0.2% of organosilicon, 0.1% of benzisothiazolinone, 0.1% of potassium sorbate, 0.6% of methyl cellulose and the balance of water.
As a further preferred embodiment, the liquid crystal microcapsule is a liquid crystal microcapsule with a temperature change range of 0 to 60 ℃, the aqueous resin is an aqueous polyurethane resin, the dark color auxiliary material is carbon black, the dispersing agent is polyethylene glycol 200, the defoaming agent is an organosilicon type, the wetting agent is polyoxyethylene alkylphenol ether, the leveling agent is an organosilicon type, the bactericide is benzisothiazolinone, the preservative is potassium sorbate, the thickener is methylcellulose, and the liquid crystal microcapsule ink with a temperature change range comprises the following components in percentage by mass: 50% of liquid crystal microcapsule, 40% of waterborne polyurethane resin, 3% of carbon black, 2000.5% of polyethylene glycol, 0.4% of organosilicon, 0.4% of polyoxyethylene alkylphenol ether, 0.2% of organosilicon, 0.1% of benzisothiazolinone, 0.1% of potassium sorbate, 0.6% of methyl cellulose and the balance of water.
As a further preferable embodiment, the liquid crystal microcapsule is a liquid crystal microcapsule with a temperature change range of 0-60 ℃, the aqueous resin is an aqueous polyurethane resin, the deep color auxiliary material is a deep color dye, the defoaming agent is an organic silicon type, the wetting agent is polyoxyethylene fatty alcohol ether, the leveling agent is an organic silicon type, the bactericide is benzisothiazolinone, the preservative is potassium sorbate, the thickener is methylcellulose, and the temperature change liquid crystal microcapsule ink comprises the following components in percentage by mass: 35% of liquid crystal microcapsule, 50% of aqueous polyurethane resin, 4% of dark color dye, 0.5% of dispersant, 0.4% of organic silicon, 0.5% of polyoxyethylene fatty alcohol ether, 0.2% of organic silicon, 0.1% of benzisothiazolinone, 0.1% of potassium sorbate, 0.6% of methyl cellulose and the balance of water.
As a preferable embodiment, in step S1, the stirring temperature is 20 ℃ to 50 ℃, and the stirring time is 0.5h to 2 h; in step S3, the stirring speed is 100 r/min-500 r/min, and the stirring time is 1 h-4 h; in step S4, the stirring speed is 100 r/min-500 r/min, and the stirring time is 0.5 h-2 h.
The properties and preparation method of the temperature-variable liquid crystal microcapsule ink described in the present application will be described in detail with reference to the following specific examples.
Comparative example
Preparing the liquid crystal microcapsule with the temperature change range of 40-60 ℃, wherein the wall material of the liquid crystal microcapsule is polyurea resin, and the core material is cholesterol ester liquid crystal (20% of cholesterol propionate: 80% of cholesterol pelargonate). Fully stirring the liquid crystal microcapsule and the waterborne polyurethane resin PU-6638 for 0.5h at 25 ℃ until the components are uniform according to the using amount of each component in the table 1 to obtain uniform liquid crystal microcapsule emulsion, dispersing polyethylene glycol 200, polyoxyethylene alkylphenol ether, BYK-333, CI-1734, potassium sorbate, benzisothiazolinone and the like into water according to different proportions, then adding into the liquid crystal microcapsule emulsion, and continuously stirring for 2h under the condition of keeping the stirring speed at 300r/min until all the components are uniformly dispersed. Adding a certain amount of methylcellulose, and continuously stirring for 1h at a stirring speed of 300r/min until the mixture is uniformly dispersed, thereby obtaining the colorful temperature-change liquid crystal microcapsule ink.
TABLE 1 temperature-sensitive liquid-crystalline microcapsule ink formulation
The temperature-change liquid crystal microcapsule ink prepared by the comparative example is respectively coated on a black PET film and a white PET film, and after curing and drying, the reflectivity on the black PET film can reach 30 percent and can be seen by naked eyes as the temperature is changed at 40-60 ℃ through a colorimeter (YS 3060), while the contrast reflectivity (the total reflectivity minus the reflectivity of a substrate) on the white PET film is lower than 10 percent, and the color change can not be observed by naked eyes basically.
Example 1
Preparing the liquid crystal microcapsule with the temperature change range of 40-60 ℃, wherein the wall material of the liquid crystal microcapsule is polyurea resin, and the core material is cholesterol ester liquid crystal (20% of cholesterol propionate: 80% of cholesterol pelargonate). Fully stirring the liquid crystal microcapsule and the waterborne polyurethane resin PU-6638 for 0.5h at 25 ℃ until the components are uniform according to the using amount of each component in the table 2 to obtain uniform liquid crystal microcapsule emulsion, dispersing iron oxide black 722, polyethylene glycol 200, polyoxyethylene alkylphenol ether, WA-7326, CI-1734, potassium sorbate, benzisothiazolinone and the like into water according to different proportions, then adding into the liquid crystal microcapsule emulsion, and continuously stirring for 2h under the condition of keeping the stirring speed at 300r/min until all the components are uniformly dispersed. Adding a certain amount of methylcellulose, and continuously stirring for 1h at a stirring speed of 300r/min until the mixture is uniformly dispersed, thereby obtaining the colorful temperature-change liquid crystal microcapsule ink.
TABLE 2 formula of temperature-variable liquid crystal microcapsule ink
| Composition (I) | Mass percent |
| Waterborne polyurethane resin PU-6638 | 50％ |
| Liquid crystal microcapsule | 35％ |
| Dark auxiliary material iron black 722 | 2％ |
| Dispersant polyethylene glycol 200 | 0.5％ |
| Wetting agent polyoxyethylene alkyl phenol ether | 0.4％ |
| Leveling agent WA-7326 | 0.2％ |
| Defoaming agent CI-1734 | 0.4％ |
| Thickening agent methyl cellulose | 0.6％ |
| Antiseptic potassium sorbate | 0.1％ |
| Bactericidal agent benzeneAnd isothiazolinone | 0.1％ |
| Water (I) | 10.7％ |
The prepared temperature-change liquid crystal microcapsule ink is respectively coated on a black PET film and a white PET film, and after curing and drying, the color detector (YS 3060 in san En) detects that the reflectivity on the black PET film can reach 33%, the film is changed at 40-60 ℃ along with the temperature, the film is bright and glaring, the contrast reflectivity (the total reflectivity minus the reflectivity of a substrate) on the white PET film can reach 29%, and the film is changed in red-yellow-green-blue and can be seen by naked eyes. The ink is poured into the inkstone and is fully stirred, a writing brush is used for dipping the ink to write and draw on white drawing paper, and after the ink is naturally dried, the colorful color-changing drawings and the color-changing characters can be clearly observed by naked eyes along with the change of temperature.
Example 2
Preparing a liquid crystal microcapsule with a temperature change interval of 0-60 ℃, wherein the wall material of the liquid crystal microcapsule is polyurea resin, the core material is cholesterol ester liquid crystal (cholesterol oleic acid carbonate 35%: cholesterol pelargonate 45%: cholesterol benzoate 20%), fully stirring the liquid crystal microcapsule and aqueous polyurethane resin AH-1704B at 25 ℃ for 0.5h until the mixture is uniform according to the dosage of each component in the table 3 to obtain a uniform liquid crystal microcapsule emulsion, dispersing carbon black 234N220, polyethylene glycol 200, polyoxyethylene alkylphenol ether, WA-7326, B-0518, potassium sorbate, benzisothiazolinone and the like into water according to different proportions, then adding the mixture into the liquid crystal microcapsule emulsion, and continuously stirring for 1.5h under the condition of keeping the stirring speed at 300r/min until all the components are uniformly dispersed. Adding a certain amount of methylcellulose, and continuously stirring for 1h at a stirring speed of 300r/min until the mixture is uniformly dispersed, thereby obtaining the colorful temperature-change liquid crystal microcapsule ink.
TABLE 3 temperature-sensitive liquid-crystalline microcapsule ink formulation
| Composition (I) | Mass percent |
| Aqueous polyurethane resin AH-1704B | 40％ |
| Liquid crystal microcapsule | 50％ |
| Dark auxiliary material carbon black 234N220 | 3％ |
| Dispersant polyethylene glycol 200 | 0.5％ |
| Wetting agent polyoxyethylene alkyl phenol ether | 0.4％ |
| Leveling agent WA-7326 | 0.2％ |
| Defoaming agent B-0518 | 0.4％ |
| Thickening agent methylcellulose | 0.6％ |
| Antiseptic potassium sorbate | 0.1％ |
| Bactericidal benzisothiazolinone | 0.1％ |
| Water (W) | 9.7％ |
The prepared temperature-change liquid crystal microcapsule ink is respectively coated on a black PET film and a white PET film, and after curing and drying, the color measuring instrument (YS 3060 in san En) detects that the reflectivity on the black PET film can reach 35%, the film is changed at 0-60 ℃ along with the temperature, the film is bright and glaring, the contrast reflectivity (the total reflectivity minus the reflectivity of a substrate) on the white PET film can reach 30%, and the film is changed in red-yellow-green-blue and can be seen by naked eyes. The ink is poured into the inkstone and is fully stirred, a writing brush is used for dipping the ink to write and draw on white drawing paper, and after the ink is naturally dried, the colorful color-changing drawings and the color-changing characters can be clearly observed by naked eyes along with the change of temperature.
Example 3
Preparing a liquid crystal microcapsule with a temperature change interval of 0-60 ℃, wherein the wall material of the liquid crystal microcapsule is polyurea resin, the core material is cholesterol ester liquid crystal (cholesterol oleic acid carbonate 35%: cholesterol pelargonate 45%: cholesterol benzoate 20%), fully stirring the liquid crystal microcapsule and aqueous polyurethane resin PU-6638 at 25 ℃ for 0.5 hour until the mixture is uniform according to the dosage of each component in table 4 to obtain a uniform liquid crystal microcapsule emulsion, dispersing G160, K-350, polyoxyethylene fatty alcohol ether, TEGO450, CI-1734, potassium sorbate, benzisothiazolinone and the like into water according to different proportions, then adding the mixture into the liquid crystal microcapsule emulsion, and continuously stirring for 2 hours under the condition of keeping the stirring speed at 300r/min until all the components are uniformly dispersed. Adding a certain amount of methylcellulose, and continuously stirring for 1h at a stirring speed of 400r/min until the mixture is uniformly dispersed, thereby obtaining the colorful temperature-change liquid crystal microcapsule ink.
TABLE 4 formula of temperature-variable liquid crystal microcapsule ink
| Composition (A) | Mass percent of |
| Waterborne polyurethane resin AH-1704B, PUD-9051 | 50％(25％、25％) |
| Liquid crystal microcapsule | 35％ |
| Dark auxiliary material G160 | 4％ |
| Dispersant K-350 | 0.5％ |
| Wetting agent polyoxyethylene fatty alcohol ethers | 0.5％ |
| Leveling agent TEGO450 | 0.2％ |
| Defoaming agent CI-1734 | 0.4％ |
| Thickening agent methyl cellulose | 0.6％ |
| Antiseptic potassium sorbate | 0.1％ |
| Bactericidal benzisothiazolinone | 0.1％ |
| Water (W) | 8.6％ |
The prepared temperature-change liquid crystal microcapsule ink is respectively coated on a black PET film and a white PET film, and after curing and drying, the color detector (YS 3060 in san En) detects that the reflectivity on the black PET film can reach 30%, the film is changed at 0-60 ℃ along with the temperature, the film is bright and glaring, the contrast reflectivity (the total reflectivity minus the reflectivity of a substrate) on the white PET film can reach 28%, and the film is changed in red-yellow-green-blue and can be seen by naked eyes. The ink is poured into the inkstone and is fully stirred, a writing brush is used for dipping the ink to write and draw on white drawing paper, and after the ink is naturally dried, the colorful color-changing drawings and the color-changing characters can be clearly observed by naked eyes along with the change of temperature.
According to the specific embodiment, the temperature change liquid crystal microcapsule ink provided by the invention takes the liquid crystal microcapsule as a color development basis, and is uniformly mixed by adding various auxiliaries and specific dark auxiliary materials, so that the colorful temperature change liquid crystal microcapsule ink which is excellent in color development, good in corrosion resistance, good in hardness, good in water resistance, excellent in acid and alkali resistance, non-toxic, pollution-free and not influenced by the color of a base material is obtained.
To sum up, the application provides a temperature change liquid crystal microcapsule printing ink and preparation method thereof, overcome the problem that the printing ink that discolours on the market is single to discolour, and temperature change liquid crystal microcapsule printing ink can reach the effect of multiple discolouring, the temperature change liquid crystal microcapsule printing ink of this application preparation can reach excellent dispersed effect with the liquid crystal microcapsule through adding specific dark auxiliary material, after coating liquid crystal microcapsule printing ink to the substrate surface, in the dry in-process of printing ink, its dark auxiliary material can be because its different density or sink, or evenly disperse, or come up, thereby reach the effect that the coating acts as another layer of substrate material on the substrate surface. Therefore, the multicolor development effect of the temperature-variable liquid crystal microcapsule ink is ensured, the application space of the temperature-variable liquid crystal microcapsule ink is not limited by a substrate material, the application range of the temperature-variable liquid crystal microcapsule ink is expanded, and the temperature-variable liquid crystal microcapsule ink can be applied to color-variable ink, color-variable labels, color-variable colored pens, oil painting pigments and the like.
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 (16)
1. The temperature-change liquid crystal microcapsule ink is characterized by comprising the following components: liquid crystal microcapsules, water-based resin, deep color auxiliary materials and dispersing agents;
the temperature-change liquid crystal microcapsule ink comprises the following components in percentage by mass: the liquid crystal microcapsule accounts for 15-65%, the water-based resin accounts for 30-75%, the deep color auxiliary material accounts for 1-5%, and the dispersing agent accounts for 0.1-2%;
the water-based resin is one or more of water-based polyurethane resin, organic silicon modified water-based polyurethane resin, methylated water-based amino resin, high-imino methylated melamine resin, high-imino resin, methylated melamine resin and high-methylated melamine resin;
the dispersing agent is one or more of polyethylene glycol 200 and polyethylene glycol 400;
the dark auxiliary materials are single components or at least two components;
the single component is any one of iron black, carbon black, copper-chromium black, iron-chromium black, cobalt black and dark dye.
2. The temperature-sensitive liquid crystal microcapsule ink according to claim 1, wherein the liquid crystal microcapsules are one or more of different liquid crystal microcapsules having a temperature-sensitive range of 0 to 100 ℃.
3. The temperature-variable liquid crystal microcapsule ink according to claim 2, wherein the liquid crystal microcapsules are one or more of different liquid crystal microcapsules having a temperature-variable range within 0 to 60 ℃.
4. The temperature-sensitive liquid crystal microcapsule ink according to claim 3, wherein the liquid crystal microcapsules are one or more of different liquid crystal microcapsules having a temperature-sensitive range of 40 ℃ to 60 ℃.
5. The temperature-sensitive liquid crystal microcapsule ink according to any one of claims 1 to 4, wherein the temperature-sensitive liquid crystal microcapsule ink further comprises one or more of a defoaming agent, a wetting agent, a leveling agent, a bactericide, a preservative, and a thickener.
6. A temperature-sensitive liquid-crystalline microcapsule ink according to claim 5, wherein said defoaming agent is of a non-silicon type and/or a silicone type.
7. The temperature-sensitive liquid crystal microcapsule ink according to claim 6, wherein the non-silicone type is one or more of alcohols, fatty acids, fatty acid esters, phosphoric acid esters, mineral oils, and amides.
8. A temperature-sensitive liquid crystal microcapsule ink as claimed in claim 5, wherein said wetting agent is a nonionic surfactant and/or an anionic surfactant.
9. The temperature-sensitive liquid crystal microcapsule ink according to claim 8, wherein the nonionic surfactant is one or more of polyoxyethylene alkylphenol ether, polyoxyethylene fatty alcohol ether, polyoxyethylene polyoxypropylene block copolymer, silanol; the anionic surfactant is one or more of alkyl sulfate, sulfonate, fatty acid ester sulfate, carboxylic acid soap and phosphate.
10. The temperature-sensitive liquid crystal microcapsule ink according to claim 5, wherein the leveling agent is one or more of silicones and acrylics.
11. The temperature-sensitive liquid crystal microcapsule ink according to claim 5, wherein the bactericide is isothiazolinone and/or benzisothiazolinone.
12. The temperature-sensitive liquid crystal microcapsule ink according to claim 5, wherein the preservative is one or more of benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, and calcium propionate.
13. A temperature-sensitive liquid crystalline microcapsule ink according to claim 5, wherein said thickener is a natural thickener and/or a synthetic thickener.
14. The temperature-sensitive liquid crystal microcapsule ink according to claim 13, wherein the natural thickener is one or more of starch, gum arabic, gelatin, alginate jelly, guar gum, and dextrin; the synthetic thickener is one or more of carboxymethyl cellulose, methyl cellulose, sodium starch phosphate, sodium carboxymethyl cellulose, sodium alginate, sodium polyacrylate, polyoxyethylene, and polyvinylpyrrolidone.
15. A method for preparing a temperature-sensitive liquid crystal microcapsule ink, which is suitable for the temperature-sensitive liquid crystal microcapsule ink according to any one of claims 5 to 14, and comprises the following steps:
s1, fully stirring the liquid crystal microcapsule and the water-based resin, wherein the stirring temperature is 20-50 ℃, the stirring time is 0.5-2 h, and uniformly mixing to obtain a liquid crystal microcapsule emulsion;
s2, dispersing a dispersing agent, a deep color auxiliary material, and/or a defoaming agent, and/or a wetting agent, and/or a leveling agent, and/or a bactericide, and/or a preservative into water, fully stirring, and uniformly mixing to obtain a mixed solution A;
s3, adding the mixed solution A obtained in the step S2 into the liquid crystal microcapsule emulsion obtained in the step S1, fully stirring at the stirring speed of 100 r/min-500 r/min for 1 h-4 h, and uniformly mixing to obtain a mixed solution B;
s4, adding a thickening agent into the mixed solution B obtained in the step S3, fully stirring at the stirring speed of 100 r/min-500 r/min for 0.5 h-2 h, and uniformly mixing to obtain the temperature-change liquid crystal microcapsule ink.
16. The method for preparing the temperature-sensitive liquid crystal microcapsule ink as claimed in claim 15, wherein the components in the temperature-sensitive liquid crystal microcapsule ink are as follows by mass percent:
the balance being water.
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