Acrylic water-soluble pattern film, method for preparing the same, and use thereof

Abstract

The present application provides an acrylic water-soluble pattern film, which comprises a printing carrier layer, a pattern layer and a pattern protection layer in sequence; the carrier layer is a gel reversible polyvinyl alcohol film; and the pattern layer is printed by a pattern layer slurry. The acrylic water-soluble pattern film solves the problems existing in the current water printing technology, the current'skin' technology and the thermal transfer printing technology, and can be widely applied to various camouflage patterns on large military instruments in the military industry and has excellent water resistance and adhesion. The solvent used is water (deionized water). Moreover, it is used at room temperature, naturally dried, and has no pollution and carbon emission in the application process. The present application also provides a preparation method and application of the acrylic water-soluble pattern film.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of film printing, and particularly relates to an acrylic water-soluble pattern film, a preparation method thereof and application. BACKGROUND

[0002] At present, most of the surface decorative patterns of the existing plate manufacturing industry, building decoration material industry, furniture industry, building decoration industry, civilian products, industrial products, military vehicles, military equipment, etc. are still made by surface film covering, surface hot skinning with PVC, PP, PE, etc., sublimation ink heat transfer printing, vacuum coating, etc. The building decoration and furniture industry almost universally adopts the technology of pasting paper skin, wood skin and PVC skin with adhesive.

[0003] The furniture made of skin pasting technology and the decorative plate pasted on the wall are afraid of moisture and water bubbles due to containing glue, are not durable, and the skin falls off and cracks quickly when encountering water or being damp. Moreover, there is a long-term environmental pollution problem of harmful gas release of adhesive, and there is pollution problem in the manufacturing and use processes, and even harm to human body of formaldehyde glue.

[0004] In recent years, the new surface decorative pattern technology invented by Sun Huifang and Cao Rentian etc. is an environmental-friendly water printing technology, but the technology only uses environmentally-friendly alcohol-soluble solvent to replace the original toluene, xylene and ketone solvent, improves the harm of organic solvent release to the environment and the harm to human body in the production and use processes, and can be widely used in the building decoration industry to replace the skin pasting technology and vacuum heat transfer printing technology to solve the harm of formaldehyde in the adhesive. However, the biggest problem of the water printing technology is that the printing carrier layer needs to be washed away and discarded during use, only the pattern layer and the pattern protection layer of the printing layer are used, so that the polyvinyl alcohol material is wasted. Moreover, the water-washed and water-dried processes are needed in the processing process, so there is waste of water resources and waste of electric energy in the water-drying process, and finally energy consumption and carbon emission are generated.

[0005] The existing environmental-friendly water printing film must immerse the workpiece or product in water to utilize the tension and pressure of water to transfer and print the pattern on the product, so it cannot be used to make decorative patterns on large workpieces. Moreover, the existing water printing pattern film uses organic solvents such as ethanol, and the cost is much higher than that of water. SUMMARY

[0006] The present application aims to provide an acrylic water-soluble pattern film, a preparation method and application thereof, the acrylic water-soluble pattern film in the present application solves the problems existing in the current water printing technology and the current'skin' technology, thermal transfer printing technology, and the like, and the acrylic water-soluble pattern film in the present application can be widely applied to various camouflage patterns on large military equipment in the military industry, and has excellent water resistance and adhesion. The solvent used is water (deionized water). Moreover, it is used at room temperature, naturally dried, and the application process is pollution-free and carbon emission-free.

[0007] The present application provides an acrylic water-soluble pattern film, which comprises a printing carrier layer, a pattern layer and a pattern protection layer in sequence.

[0008] The carrier layer is a gel reversible polyvinyl alcohol film.

[0009] The pattern layer is printed by a pattern layer slurry, and the pattern layer slurry comprises the following components by mass fraction:

[0010] Water-based acrylic resin binder 60-75%

[0011] Butyl diglycol-ethyl ether 0-5%

[0012] Water-based polyurethane 0.5-1%

[0013] Di (dioctyl phosphor yloxy) titanium diethyl ester 0.5-1.8%

[0014] Polyoxyethylene glycol alkyl ester 1-15%

[0015] Pigment 1-12%

[0016] Polyoxypropylene glycol glyceryl ether 0.01-0.25%

[0017] Solution stabilizer aqueous solution 0-10%

[0018] Film forming agent 0-5%

[0019] Water balance

[0020] The pattern protection layer is printed by a pattern protection layer slurry, and the pattern protection layer slurry comprises the following components by mass fraction:

[0021] Water-soluble acrylic resin binder 75-85%

[0022] Solution stabilizer aqueous solution 0-20%

[0023] Film forming agent 1-5%

[0024] Polyoxypropylene glycol glyceryl ether 0.01-0.8%

[0025] Alkyl dimethyl quaternary ammonium salt 0.05~0.3%

[0026] Polyethylene wax emulsion 2~5%

[0027] Water balance.

[0028] Preferably, the thickness of the printing carrier layer is 20~40μm, the alcoholysis degree of polyvinyl alcohol is 75~80%, and the molecular weight is 170~220 thousand.

[0029] Preferably, the water-soluble acrylic resin binder in the pattern layer slurry is a blend of film-forming acrylic emulsion and hard stearic non-film-forming acrylic acid, and the mass ratio of the film-forming acrylic emulsion to the hard stearic non-film-forming acrylic acid is (65~75):(35~25).

[0030] The water-soluble acrylic resin binder in the pattern protective layer slurry is a blend of film-forming acrylic emulsion and hard stearic non-film-forming acrylic acid, and the mass ratio of the film-forming acrylic emulsion to the hard stearic non-film-forming acrylic acid is (65~75):(35~25).

[0031] Preferably, the viscosity of the water-soluble acrylic resin binder in the pattern layer slurry is 5500~7500MPa·s / (25℃), the solid content is 36±1%, and the PH is 7~7.3; the solid content of the solution stabilizer aqueous solution in the pattern layer slurry is 15~25%, and the solution stabilizer is polyethylene glycol and / or ethylene glycol; the film-forming agent in the pattern layer slurry includes one or more of oxalic acid, phthalic acid, and benzoic acid propylene glycol ester.

[0032] Preferably, the viscosity of the water-soluble acrylic resin binder in the pattern layer slurry is 5500~7500MPa·s / (25℃), the solid content is 36±1%, and the PH is 7~7.3; the solid content of the solution stabilizer aqueous solution in the pattern layer slurry is 15~25%, and the solution stabilizer is polyethylene glycol and / or ethylene glycol; the film-forming agent in the pattern layer slurry includes one or more of oxalic acid, phthalic acid, and benzoic acid propylene glycol ester.

[0033] Preferably, the solid content of the pattern layer slurry is 35~45%, and the viscosity is 13~18 S / 25℃ (coating-4 cup).

[0034] The solid content of the pattern protective layer slurry is 20~40%, and the viscosity is 13~15 S / 25℃ (coating-4 cup).

[0035] The present application provides a preparation method of the above-mentioned acrylic water-soluble pattern film, comprising the following steps:

[0036] The raw materials are mixed according to the proportions above to obtain the pattern layer slurry and the pattern protection layer slurry, respectively, and the pattern layer and the pattern protection layer are sequentially printed on the printing carrier layer by using the intaglio printing process to obtain the acrylic water-soluble pattern film.

[0037] The application provides a method for using the acrylic water-soluble pattern film as described above, which comprises the following steps:

[0038] A) spraying a layer of a water solution of a polyvinyl alcohol insolubilizer with a temperature of 60-70°C on the surface of a workpiece;

[0039] B) attaching the printing carrier layer of the acrylic water-soluble pattern film to the surface of the workpiece quickly, rolling it flat, and removing the air bubbles and wrinkles between the workpiece and the film layer;

[0040] C) after cooling to room temperature, spraying a water solution of diethylamine with a temperature of 5-20°C or a water solution of polyethylene oxide with a temperature of 5-20°C on the surface of the pattern protection layer until the acrylic water-soluble pattern film is completely water-soluble and swollen;

[0041] D) drying to complete film formation, standing for 72-100 hours, and polishing to obtain the acrylic water-soluble pattern film.

[0042] Preferably, the polyvinyl alcohol insolubilizer is one or more of dimethyl urea, dimethyl ethyl urea and trimethyl melamine.

[0043] Preferably, the solid content of the water solution of diethylamine is 0.5-3%.

[0044] The solid content of the water solution of polyethylene oxide is 20-30%, and the molecular weight of the polyethylene oxide is 25000-100000.

[0045] The application provides an acrylic water-soluble pattern film, which sequentially comprises a printing carrier layer, a pattern layer and a pattern protection layer; the carrier layer is a gel reversible polyvinyl alcohol film; and the pattern layer is printed by using a pattern layer slurry.

[0046] 1. The water-based printing ink is creatively printed on the water-soluble polyvinyl alcohol film, water is used as the solvent, no organic solvent is used, and the production process is pollution-free.

[0047] 2. In the use process, without any other organic solvent, only a small amount of low concentration diethylamine neutralizing agent (concentration 0.5%-3%) or polyethylene oxide aqueous solution is used to dissolve and neutralize (or complex) the pattern film, which greatly reduces the original water printing pattern film use cost and environmental pollution.

[0048] 3. In the application process of the pattern film, the carrier layer polyvinyl alcohol film can accept the cold water permeated by the pattern layer and be water soluble, and is organically fused with the pattern layer to become a gel state carrier of the pattern layer for common use. Since the hot water containing insolubilizing agent on the bottom surface of the carrier layer, after the water solubility of the carrier layer, the insolubilizing agent enters the carrier layer with the water, so that after drying, the film is firmly attached to the surface of the workpiece and is no longer soluble in water, becoming a connecting layer of the pattern layer. Under the action of the neutralizing agent (and the complexing agent), the pattern layer becomes a salt type acrylic acid (film) (or a complex film of acrylic acid and polyethylene oxide), which is no longer soluble in water. The effective use of the carrier film is obtained. The waste problem of the original water washing process to the polyvinyl alcohol raw material is solved.

[0049] 4. The whole process of production and use uses "water" as the solvent, which is environmentally friendly, safe and non-polluting. The cost is greatly reduced.

[0050] 5. The problem of the past water printing technology to the product, size, volume and weight limitation and requirement, and the limitation of the operation time in the operation process is solved. The most advanced one can only complete the water printing within 6 minutes, while the acrylic acid type water-soluble pattern film of the present application has no limitation and requirement on the size, shape and weight of the product workpiece. Because the pattern film belongs to normal temperature curing, it can be widely applied to large machinery such as large military vehicles, large military equipment, weapons, etc. camouflage pattern and various pattern decoration, and is also suitable for making camouflage patterns of large tanks, warships, etc.

[0051] The application field of the acrylic acid type water-soluble pattern film of the present application is very wide, which can replace PVC, PE, PP and various plastic skins, and can be widely applied to the pattern making on the surface of furniture and decorative board, which is beneficial to environmental protection, belongs to a new technology of decoration pattern making without glue, harmful gas release and harm, is beneficial to promoting the development of new type of environmentally friendly decorative materials, and has great economic and social value. DETAILED DESCRIPTION

[0052] The present application provides an acrylic acid type water-soluble pattern film, which comprises a printing carrier layer, a pattern layer and a pattern protection layer in sequence.

[0053] The carrier layer is a gel reversible polyvinyl alcohol film.

[0054] The pattern layer is printed by pattern layer slurry, and the pattern layer slurry comprises the following components in mass fraction:

[0055] aqueous acrylic resin binder 60-75%

[0056] butyl diglycol-ethyl ether 0-5%

[0057] aqueous polyurethane 0.5-1%

[0058] di(dioctylphosphoryloxy)ethyl titanate 0.5-1.8%

[0059] polyoxyethylene glycol alkyl ester 1-15%

[0060] pigment 1-12%

[0061] polyoxypropylene ethylene oxide glyceryl ether 0.01-0.25%

[0062] aqueous solution stabilizer 0-10%

[0063] film former 0-5%

[0064] water balance

[0065] The graphic protection layer is printed from a graphic protection layer paste, which comprises the following components in mass fraction:

[0066] water-soluble acrylic resin binder 75-85%

[0067] aqueous solution stabilizer 0-20%

[0068] film former 1-5%

[0069] polyoxypropylene ethylene oxide glyceryl ether 0.01-0.8%

[0070] alkyl dimethyl quaternary ammonium salt 0.05-0.3%

[0071] polyethylene wax emulsion 2-5%

[0072] water balance.

[0073] In the present application, the thickness of the printed carrier layer is preferably 20-40 μm, more preferably 25-35 μm, and the alcoholysis degree of the polyvinyl alcohol is preferably 75-80%, and the molecular weight is 170,000-220,000. In the present application, in order to obtain a cold water-soluble carrier layer, a gel reversible polyvinyl alcohol film with an alcoholysis degree of 75-80% and a molecular weight of 170,000-220,000 is selected, because this polyvinyl alcohol is only soluble in cold water but not in hot water. The use of the polyvinyl alcohol with this alcoholysis degree can ensure that the aqueous printing ink is not dissolved in the carrier film during printing when the aqueous printing ink is heated to 45-50°C, and can also improve the printing drying speed.

[0074] In the present application, the pattern layer is printed from a pattern layer slurry, in which the mass fraction of the aqueous acrylic resin binder is preferably 60-75%, more preferably 65-70%, the viscosity of the water-soluble acrylic resin binder in the pattern layer slurry is 5500-7500 MPa·s / (25℃), the solid content is 36±1%, and the pH is 7-7.3. The aqueous acrylic resin binder is preferably a blend of a coalescing acrylic emulsion and a hard non-coalescing acrylic, and the mass ratio of the coalescing acrylic emulsion to the hard non-coalescing acrylic is preferably (65-75):(35-25), more preferably 70:30.

[0075] In the present application, in order to obtain a water-soluble reversible pattern film, a water-soluble acrylic resin binder is used as a film-forming resin, and a coalescing acrylic emulsion and a non-coalescing acrylic emulsion are mixed in a ratio of 70:30 to obtain a pattern layer with good printability, excellent adhesion, and good gloss. The reason for using a mixture of two emulsions is that:

[0076] (1) The hard non-coalescing acrylic emulsion has a high solid content of 45%-52% and a relatively low viscosity, which is helpful for the rapid drying of ink, and has good solubility, but since this emulsion does not coalesce, it must be mixed with other emulsions.

[0077] 2) The coalescing acrylic emulsion has a high molecular weight and a high solid content, and thus exhibits superior performance, such as excellent water resistance, oil resistance, and good affinity with non-porous printing materials (non-absorbing media). The carrier layer PVA film is a non-absorbing material, which is suitable for printing with an acrylic water-based resin binder.

[0078] Generally, the lower the glass transition temperature (Tg) of the coalescing acrylic emulsion, the better the film-forming property and adhesion. The present application combines the advantages of both coalescing and non-coalescing emulsions to obtain the required printability, drying speed, and water-soluble pattern film.

[0079] In the present application, butyl diglycol-ethyl ether is added as a cosolvent in the pattern layer slurry composition. Butyl diglycol-ethyl ether is a pigment solvent that can improve the solubility of pigments and increase the flowability and smoothness of printing ink. Water-based polyurethane is added as a thickening agent. Polyurethane is a synthetic polymer that has thickening and antimicrobial effects in the formulation. On the other hand, it has no significant water retention and better water resistance than cellulose, which is suitable for the application of the present application. The mass fraction of butyl diglycol-ethyl ether is preferably 0-5%, more preferably 1-4%, and most preferably 2-3%.

[0080] In the present application, the mass fraction of the aqueous polyurethane is preferably 0.5-1%, more preferably 0.6-0.8%.

[0081] In the present application, the coupling agent di(dioctylphosphoryloxy) titanate ethylene glycol in the pattern layer component belongs to chelate type titanate coupling agent. It can reduce the thickness of the ink; increase the affinity of pigments and fillers with the printing material, thereby improving the adhesion of the aqueous ink on the surface of the printing material; and be miscible with water in any proportion, suitable for water-based ink. The coupling agent can be added at any time before and after printing. For aqueous ink, chelate type titanate coupling agent is an essential important functional additive. The coupling agent can make the acrylic emulsion type aqueous ink have thixotropy, facilitate printing operation, not drip, and shorten the ink manufacturing cycle. The mass fraction of the di(dioctylphosphoryloxy) titanate ethylene glycol is preferably 0.5-1.8%, more preferably 1-1.5%.

[0082] In the present application, the mass fraction of the polyoxyethylene glycol alkyl ester is preferably 1-15%, more preferably 3-12%, most preferably 5-8%.

[0083] In the present application, the pigment is preferably an organic pigment and / or an inorganic pigment, and both the organic pigment and / or the inorganic pigment are commonly used in the art, which will not be described here in detail.

[0084] In the present application, the polyoxypropylene glycol glyceryl ether is used as a solution defoaming agent. The defoaming agent can be dissolved in cold water, saving processing temperature and reducing the air bubbles of the aqueous ink. The mass fraction of the polyoxypropylene glycol glyceryl ether is preferably 0.01-0.25%, more preferably 0.05-0.2%, most preferably 0.1-0.15%.

[0085] In the present application, the solid content of the aqueous solution stabilizer is preferably 15-25%, more preferably 20%, and the solution stabilizer is preferably polyethylene glycol and / or ethylene glycol. The solution stabilizer can maintain the stability and oxidative decomposition of the aqueous solution viscosity, and high molecular weight polyethylene glycol is selected. The molecular weight of the polyethylene glycol is 15000-20000. Low molecular weight polyethylene glycol has solubility to polyvinyl alcohol and hygroscopicity, which is not conducive to the anti-adhesion of the pattern layer. Polyethylene glycol higher than 15000 is almost not hygroscopic in the atmosphere, and loses the solubility to PVA.

[0086] In the present application, the film-forming agent is preferably one or more of oxalic acid, phthalic acid and propylene glycol benzoate. The above three film-forming agents belong to ester-ketone type, can be distributed in the shell of the emulsion particles, greatly help to soften the particles and then evaporate quickly, and can also control the interval time of water-based ink printing with solvent. The mass fraction of the film-forming agent is preferably 0-5%, more preferably 1-4%, and most preferably 2-3%.

[0087] In the present application, in order to obtain water-soluble reversibility of the pattern layer and the pattern protection layer after printing, i.e. the pattern layer can be redissolved with water, a neutralizing agent, diethylamine, is added to the water solution, and when the film is attached to the surface of the workpiece, the pattern layer is dissolved into a colloid for the second time with a water solution containing the neutralizing agent. The water solution penetrates the pattern layer and also dissolves the carrier layer polyvinyl alcohol film, so that the purpose of drying at room temperature with water as the solvent is achieved.

[0088] In the present application, the neutralizing agent is preferably diethylamine, because the present application selects a room temperature drying method, and a neutralizing agent with low boiling point and easy evaporation should be selected. The boiling point of diethylamine is only 55℃, and the amount of the neutralizing agent is selected according to the thickness of the film, the amount of water used for dissolution, and the neutralization degree. The amount can be adjusted at any time, and the amount of the water solution is also determined according to the degree of film dissolution.

[0089] In the present application, the solid content of the pattern layer slurry is preferably 35-45%, more preferably 40%, and the viscosity is 13-18 S / 25℃ (coating-4 cup), more preferably 14-17 S / 25℃ (coating-4 cup).

[0090] In the present application, the thickness of the pattern layer is preferably 2-10 μm for single color, 4-20 μm for double color overlap, and 6-35 μm for total thickness of three color overlap after drying and film formation.

[0091] In the present application, the pattern protection layer is obtained by printing the pattern protection layer slurry, and in the pattern protection layer slurry,

[0092] The types of the water-soluble acrylic resin binder, the water solution stabilizer and the film-forming agent in the pattern protection layer are the same as those described above for the pattern layer, and the present application will not be repeated here. The specific types of the water-soluble acrylic resin binder, the water solution stabilizer and the film-forming agent in the pattern layer and the pattern protection layer can be the same or different.

[0093] In the present application, the mass fraction of the water-soluble acrylic resin binder in the pattern protective layer slurry is preferably 75-85%, more preferably 80%; the solid content of the solution stabilizer aqueous solution is preferably 15-25%, more preferably 20%, and the mass fraction of the solution stabilizer aqueous solution is preferably 0-20%, more preferably 5-15%; the mass fraction of the film-forming agent is preferably 1-5%, more preferably 2-4%; and the mass fraction of the polyoxypropylene glycol ethylene glycol ether is preferably 0.01-0.8%, more preferably 0.05-0.7%, and most preferably 0.1-0.6%.

[0094] In the present application, an alkyl dimethyl quaternary ammonium salt is added to the pattern protective layer aqueous ink as a bactericidal and bacteriostatic agent, which has the functions of good water solubility, high efficiency, wide spectrum, low toxicity, good biodegradability, and the like, can be used in combination with commonly used water quality stabilizers, has the advantages of low use concentration, and can inhibit the erosion of microorganisms and mold on the surface of the pattern layer. The mass fraction of the alkyl dimethyl quaternary ammonium salt is preferably 0.05-0.3%, more preferably 0.1-0.2%.

[0095] In the present application, an anti-friction agent polyethylene wax emulsion is further added to the pattern protective layer component, which can improve the wear resistance and smoothness of the surface layer, and also has the functions of waterproofing, gloss enhancement, and anti-blocking after curing. The mass fraction of the polyethylene wax emulsion is preferably 2-5%, more preferably 3-4%.

[0096] In the present application, the solid content of the pattern protective layer slurry is preferably 20-40%, more preferably 25-35%, and the viscosity is 13-15 S / 25℃ (Cup-4).

[0097] In the present application, the thickness of the pattern protective layer is preferably 40 μm.

[0098] The present application also provides a preparation method of the acrylic water-soluble pattern film, which comprises the following steps:

[0099] The raw materials are mixed in the proportions described above to obtain the pattern layer slurry and the pattern protective layer slurry, respectively, and the pattern layer and the pattern protective layer are printed on the printing carrier layer in sequence by using the gravure printing process to obtain the acrylic water-soluble pattern film.

[0100] In the present application, the preparation of the pattern layer slurry and the pattern protective layer slurry, and the gravure printing process are all common processes in the art, which will not be described herein.

[0101] The present application also provides a use method of the acrylic water-soluble pattern film described above, which comprises the following steps:

[0102] A) Spraying a layer of polyvinyl alcohol insolubilizer aqueous solution with a temperature of 60-70℃ on the surface of the workpiece;

[0103] B) Placing the printed carrier layer of the acrylic water-soluble pattern film towards the workpiece and quickly sticking it on the surface of the workpiece, rolling it flat and removing the air bubbles and wrinkles between the workpiece and the film layer;

[0104] C) After cooling to room temperature, spraying a diethylamine aqueous solution with a temperature of 5-20℃ or a polyethylene oxide aqueous solution with a temperature of 5-20℃ on the surface of the pattern protective layer until the acrylic water-soluble pattern film is fully water-soluble;

[0105] D) Drying at room temperature until complete film formation, standing for 72-100 hours and polishing to obtain the product.

[0106] In the present application, the polyvinyl alcohol insolubilizer is preferably one or more of dimethyl urea, dimethyl ethyl urea and trimethyl melamine, and the solid content of the polyvinyl alcohol insolubilizer aqueous solution is preferably 0.5-2%, more preferably 1-1.5%. The spraying thickness of the polyvinyl alcohol insolubilizer aqueous solution is preferably 20-30μm, and the water temperature is preferably 60-70℃, such as 60℃, 65℃, 70℃, preferably a range of upper limit or lower limit of any of the above values.

[0107] In the present application, the solid content of the diethylamine aqueous solution is preferably 0.5-3%, more preferably 1-2.5%, and most preferably 1.5-2%, and the temperature of the diethylamine aqueous solution is preferably 5-20℃, more preferably 10-15℃. The water-insoluble film prepared by this method is an alkali-neutralized salt film.

[0108] In the present application, the molecular weight of the polyethylene oxide is preferably 25000-100000, more preferably 50000-80000, and the solid content of the polyethylene oxide aqueous solution is preferably 20-30%, more preferably 25%. The water-insoluble film prepared by this method is a complex film of acrylic water-based ink and polyethylene oxide, and the reason why the present application adopts their complex film-forming property is that such a complex film is easily formed at room temperature. The generated complex is hard and strong, and is insoluble in water, thereby obtaining a pattern decoration layer that is naturally cured at room temperature.

[0109] The properties and use features of the acrylic water-soluble pattern film of the present application are as follows:

[0110] 1. The carrier layer of the acrylic water-soluble pattern film is only soluble in cold water but not in hot water.

[0111] 2. The printed pattern layer and the pattern layer protective layer are soluble in cold water and have liquid-solid reversibility.

[0112] 3. The neutralization salt agent (film forming aid) or complexing agent of the pattern film can be prepared into a single component aqueous solution for use in film coating.

[0113] 4. When the surface of the pattern is sprayed with an aqueous solution of diethylamine (or an aqueous solution of complexing agent polyethylene oxide), the pattern layer and the pattern protective layer can quickly absorb water and dissolve into a gel state, and the carrier layer polyvinyl alcohol film also dissolves into a gel state, and the pattern stretches slightly enlarged.

[0114] 5. After a second drying (natural room temperature curing) for 75-100 hours, a water-insoluble pattern layer is obtained, which is resistant to water and does not peel or fall off in water at high temperature 80℃ for 120 hours.

[0115] In order to further illustrate the present application, the following examples are provided to describe in detail the acrylic acid type water-soluble pattern film, its preparation method and application provided by the present application, but it should not be understood as limiting the scope of protection of the present application.

[0116] In the following examples, the carrier layer polyvinyl alcohol is selected from gel reversible polyvinyl alcohol film with a molecular weight of 170-220 thousand and an alcoholysis degree of 75-80%, and a cold water soluble type with a thickness of 20-40 μm. The polyvinyl alcohol film in the following examples is purchased from Mudanjiang Shuangxing Chemical Co., Ltd. The model is NJKN-02. The size of the film is length x width = 1000 m x 1 m.

[0117] In the following examples, the water-based acrylic resin binder is a product of Japan Oriental Ink Factory, and the type is a blend of coacervate type acrylic emulsion / hard non-coacervate type acrylic emulsion = 70:30 (mass ratio). The viscosity is 2200-7500 MPa·s / 25℃, the solid content is (36±1)%, and the PH value is 7-7.3.

[0118] In the following examples: di (dioctyl phosphor oxy) titanium ethylene glycol coupling agent is selected from the product of Yangzhou Lida Resin Coating Factory, model LD-212, and other materials are selected from commercially available goods.

[0119] Example 1 Single color, light blue marble pattern film

[0120] The present application provides an acrylic acid type water-soluble pattern film, which comprises a carrier layer, a pattern layer and a pattern protective layer.

[0121] The carrier layer is a gel reversible polyvinyl alcohol film with a thickness of 40 μm, an alcoholysis degree of 76%, and a cold water soluble type with a molecular weight of 200,000.

[0122] The solution stabilizer is polyethylene glycol with a molecular weight of 15,000.

[0123] The viscosity of the acrylic resin binder is preferably 2200 MPa.s / 25°C, the solid content is (36±1)%, and the pH value is 7. The pattern in Example 1 is a light blue marble pattern. (Single color) (the base color is white workpiece)

[0124] Preparation of the pattern layer printing ink

[0125] 1. Water-based acrylic resin binder 75%

[0126] 2. Butyl diglycol-ethyl ether 0%

[0127] 3. Water-based polyurethane 0.5%

[0128] 4. Bis (dioctylphosphoryloxy) titanium acid hexa ester 0.5%

[0129] 5. Polyoxyethylene glycol alkyl ester 1%

[0130] 6. Sky blue pigment 1%

[0131] 7. Polyoxypropylene glycol ethylene oxide glycerol ether 0.01%

[0132] 8. Polyethylene glycol 10%

[0133] 9. Benzoic acid 0%

[0134] 10. Water (deionized water) balance

[0135] The pattern layer printing ink of the water-soluble pattern film is prepared by a water-based printing ink preparation method well known to those skilled in the art, and the process method includes the following steps.

[0136] First, 75 parts of the water-soluble acrylic resin binder is placed in the grinding machine cylinder, the grinding machine is turned on, the number of revolutions is 90 r / min, 0.5 parts of bis (dioctylphosphoryloxy) titanium acid ethylene ester is slowly added, then 1 part of sky blue pigment is slowly added, and grinding is carried out, the grinding speed is adjusted to 300 r / min-500 r / min, the grinding time is 60 min-240 min, preferably 400 r / min, grinding for 90 min, the temperature is 70-80°C, preferably 75°C, after grinding, 10%-15% of the material is discharged first, and stored in a sealed tank for standby.

[0137] The 0.5 parts of water-soluble polyurethane, 1 part of polyoxyethylene glycol alkyl ester, 10 parts of polyethylene glycol solution stabilizer are added into the grinding machine barrel in turn, the amount is 1 / 2 of the volume of the barrel, then add appropriate amount of deionized water to start grinding, the grinding speed is 400 r / min, the grinding temperature is 75℃, the speed is reduced to 90 r / min, 0.01 parts of defoaming agent polyoxypropylene glycol ethylene glycol ether is slowly added, continue to stir at 90 r / min for 10 min, stop for 10 min, then add 10%-15% of the pigment solution, adjust the color, solid content and viscosity while adding, the solid content is 35%-45%, preferably 40%, the viscosity is 13 S / (25℃)-18 S / (25℃) coating-4 cup. The pattern layer printing ink is obtained, which is filled and sealed for standby.

[0138] Preparation of pattern protective layer printing ink

[0139] 1. Water-based acrylic resin binder 80%

[0140] 2. Solution stabilizer; polyethylene glycol (solid content 20%) 12%

[0141] 3. Film forming agent: benzoic acid 1%

[0142] 4. Polyoxypropylene glycol ethylene glycol ether 0.01%

[0143] 5. Alkyl dimethyl quaternary ammonium salt 0.05%

[0144] 6. Polyethylene wax emulsion 5%

[0145] 7. Deionized water balance

[0146] In the pattern protective layer components, the technical indicators of the water-based acrylic resin binder, the molecular weight of polyethylene glycol, and the type of film forming agent are the same as the standard of the pattern layer.

[0147] The preparation method of the pattern protective layer printing ink includes the following steps:

[0148] First, 80 parts of water-based acrylic resin binder is placed in the grinding machine barrel, the amount is 90% of the total amount, the grinding machine is started, the rotation speed is 90 r / min, then 12 parts of polyethylene glycol, 0.01 parts of polyoxypropylene glycol ethylene glycol ether, 0.05 parts of alkyl dimethyl quaternary ammonium salt, 5 parts of polyethylene wax emulsion, and appropriate amount of water are slowly added in turn, then the grinding machine speed is adjusted to 300 r / min-500 r / min, grinding for 60 min-180 min, preferably 400 r / min, grinding for 150 min, the temperature is preferably 75℃. The grinding machine loading amount is 1 / 2 of the volume of the barrel.

[0149] After grinding, the speed is reduced to 90 r / min, the temperature is reduced to 30℃, the remaining aqueous acrylic emulsion, the connecting agent and an appropriate amount of water are slowly added, and after stirring for 10 min, the solid content is adjusted to 20%-40%, and the viscosity is 13 S / 25℃-15 S / 25℃, and the coating-4 cup, preferably the solid content is 35%, and the viscosity is 13 S / 25℃ coating-4 cup, to obtain a pattern protective layer printing ink.

[0150] Pattern layer printing process

[0151] The acrylic water-soluble pattern film of the present application is made by using the gravure printing process well known to those skilled in the art, and the pattern film printing carrier is a gel reversible polyvinyl alcohol film, preferably with an alcoholysis degree of 76%, cold water soluble, and a molecular weight of 200,000, and a film thickness of 40 μm.

[0152] The size of the water-soluble pattern film in this embodiment is preferably 1000 m x 1 m in length x width, the pattern layer printing thickness is 2 μm-10 μm for single color, the pattern protective layer is a transparent layer with a thickness of 40 μm. The ink size of the printing plate roll width is 970 (mm), the pattern protective layer is printed synchronously by double plate rolls, and the printing thickness of each plate roll is 20 μm, the pattern layer is printed by one plate roll, and the printing sequence is that the pattern plate roll is the first plate roll, and the pattern protective layer is the second and third plate rolls.

[0153] 1. First, a printing plate roll is made according to the designed pattern, the roll length is 980 mm, the diameter is based on the length of one cycle of the pattern in the longitudinal direction, the ink hole depth of the pattern layer printing plate roll is 5 μm-30 μm, and the ink hole depth of the pattern protective layer is 30 μm-45 μm, preferably 40 μm.

[0154] The pattern layer and the pattern protective layer are printed synchronously in sequence, wherein the pattern layer can be a single color or multi-color pattern, and more than two color pattern layers cannot be printed synchronously with the pattern protective layer, but the pattern layer can be printed first, and the pattern protective layer can be printed after drying. The pattern protective layer is printed by double plate rolls, and after each plate roll is printed, it is dried for 4-8 seconds (calculated at a line speed of 30 m / min) before the second printing is performed, so as to increase the drying quality of the printing.

[0155] When the pattern layer is single color, the printing line speed is 25 m / min-30 m / min, when the pattern layer is double color, the printing line speed is 20 m / min-25 m / min, and when the pattern layer is three colors, the printing line speed is 15 m / min-20 m / min, and the three colors are printed synchronously, and each color is dried for 4-8 seconds before the next color is printed.

[0156] The printing drying temperature is 50±3℃, the distance between the air port and the film is 100mm-150mm, preferably 120mm, the ambient temperature is 25-30℃, the relative humidity in the room is 35%-40%, and the temperature of the water-based printing ink is 45℃. First, the printing plate roller is prepared, the pattern plate roller is the first plate roller, and the pattern protection layer is the second and third plate rollers.

[0157] During the printing process, the viscosity of the printing ink in the ink fountain needs to be checked at any time. If the viscosity is higher than the specified viscosity, an appropriate amount of water needs to be added for adjustment. Each time, the amount of added water should not exceed 5% of the total amount of ink, and the stirring should be done 3-4 times per hour with an ink stick.

[0158] Before printing, the pattern ink is filtered through an 800-1000 mesh ink filter, left to stand for 2 hours to remove bubbles, and then poured into the ink fountain. First, use PP film to test print, and after the color registration and drying are qualified, proceed with formal printing.

[0159] After all the printing is completed, perform reverse roll drying. The drying temperature is 35-40℃, and the line speed is 30m / min.

[0160] After the film printing is completed, let it stand for 75 hours in an environment with a relative humidity of 35%-40% and an ambient temperature of 25-30℃, and then perform winding, edge cutting, and packaging to obtain the acrylic water-soluble pattern film.

[0161] Pack the acrylic water-soluble pattern film with waxed kraft paper on the inside and PP film on the outside for sealing and packaging.

[0162] Example 2

[0163] In Example 2, the alcoholysis degree of the carrier layer polyvinyl alcohol is preferably 78%, it is cold water soluble, the molecular weight is preferably 170,000, and the thickness of the film is 40μm. The molecular weight of polyethylene glycol is preferably 18,000.

[0164] The viscosity of the acrylic resin binder is preferably 6000 MPa·s / 25℃, the solid content is (36 ±1 )%, and the PH is preferably 7.2. The pattern design is a two-color marble pattern, with orange yellow as the dark color and light yellow as the light color.

[0165] (The base color is white), the ink depth of the pattern printing plate roller is ① the ink depth of the orange yellow color is 5μm-30μm, from light to deep; ② the ink depth of the light yellow color is 2μm-10μm, from light to deep.

[0166] The printing sequence of the two colors is: orange yellow as the first color, as the first plate roller, light yellow as the second color, as the second plate roller, the pattern protection layer as the third and fourth plate rollers, and the printing thickness is 40μm. Single ink contains 20μm, and two roots are printed in overlap.

[0167] Pattern layer formula:

[0168] Table 1 Pattern layer slurry formulation

[0169]

[0170] The preparation method of each single color of the pattern layer printing ink of Example 2 is completely the same as the preparation method and process conditions (mixing speed, temperature, and time) of Example 1, and is not repeated here. (But the grinding time of the first color ink is lengthened to achieve the best grinding effect.) The solid content of the printing ink is 35%, and the viscosity is 16 s / 25°C (co-4 cup).

[0171] Pattern protective layer formulation

[0172] 1. Water-based acrylic resin binder 75%

[0173] 2. Solution stabilizer; polyethylene glycol 20%

[0174] 3. Phthalic acid (film-forming agent) 1.5%

[0175] 4. Polyoxypropylene ethylene oxide ether 0.2%

[0176] 5. Alkyl dimethyl quaternary ammonium salt 0.1%

[0177] 6. Polyethylene wax emulsion 2%

[0178] 7. Water (deionized water) balance

[0179] The preparation method of the pattern protective layer printing ink of Example 2 is completely the same as the preparation method and process conditions (mixing speed, temperature, and time) of Example 1, and is not repeated here. The solid content of the printing ink is 38%, and the viscosity is 15 S / 25°C (co-4 cup).

[0180] The acrylic water-soluble pattern film printing includes the following steps:

[0181] 1. The printing roller:

[0182] ① Orange pattern is the first printing roller, and the printing roller position is the first group (first color), ② Light yellow pattern is the second group of the second printing roller; ③ Pattern protective layer is the third group and the fourth group of printing roller.

[0183] 2. Adjust the printing thickness, adjust the printing temperature, and the hot drying air speed requirements are strictly set according to the process requirements, and the distance between the air port and the printing film is adjusted.

[0184] The pattern ink is filtered by an ink filter screen of 800-1000 mesh, and is left to stand for 2 hours to remove bubbles before being poured into an ink fountain. The distance between the doctor blade and the printed carrier layer film and the printing thickness, viscosity and speed are adjusted, and the machine is started after passing the quality inspection. The machine is first tested with a PP film (40 pm thick) to adjust the accuracy of the double-color overprint and the color difference of the pattern film. The color difference of the single color should be no more than 4 degrees. The color scale is printed on the left side of the pattern film, and the model is printed on the right side of the pattern film.

[0185] The line speed is adjusted to 20 m / min, the drying temperature is 50°C, the ambient humidity is 35-40%, preferably 35%, the distance between the air port and the film is 100 pm, the printing thickness of the one-color pattern is 5-30 pm from light to dark, and the printing thickness of the two-color pattern is 2-10 pm from light to dark. The printing thickness of the pattern protective layer is 40 pm, and the printing ink temperature is 40°C.

[0186] When printing the pattern layer, the first color and the second color are printed with an interval of 4-8 seconds, and then the second color is printed. The drying degree of the water-based ink is observed, and the drying degree of the second color after printing is checked.

[0187] After the first color and the second color are printed, the pattern protective layer is printed. The pattern protective layer is printed synchronously by two plate rollers. The first plate roller and the second plate roller are printed with an interval of 4-8 seconds, the line speed is 20 m / min, the drying temperature is 50±3°C, and the other process is the same as in Example 1.

[0188] After all the printing is completed, the film is dried by unwinding, the drying temperature is 35°C, the line speed is 30 m / min, the film is left to stand for 72 hours (30°C), and then the edges are trimmed. The winding, packaging and packaging materials are the same as in Example 1.

[0189] Example 3

[0190] In Example 3, the carrier layer polyvinyl alcohol film is preferably a gel reversible polyvinyl alcohol film with an alcoholysis degree of 80%, a molecular weight of 220,000, and a film thickness of 40 pm.

[0191] The viscosity of the acrylic water-soluble resin binder used in Example 3 is preferably 6500 MPa·s / 25°C, the solid content is 36 ±1 %), the PH value is 7.3, and the pattern design is a three-color version of military camouflage pattern.

[0192] The printing sequence of Example 3 is as follows: ① first color (first plate roller) olive green; ② second color (second plate roller) grass green; ③ third color (third plate roller) light beige; and ④ fourth and fifth plate rollers for the pattern protective layer.

[0193] The printing thickness of Example 3 is: 5-20 μm for the first color from light to dark, 5-20 μm for the second color from light to dark, 2-10 μm for the third color from light to dark, and 40 μm for the pattern protective layer (the printing thickness of each plate roller is 20 μm).

[0194] The ink hole depth of the plate roller is:

[0195] ① The ink hole depth of the first color plate roller is 5-20 μm

[0196] ② The ink hole depth of the second color plate roller is 5-20 μm

[0197] ③ The ink hole depth of the third color plate roller is 2-10 μm

[0198] ④ The ink hole depth of the pattern protective layer is 20 μm (two plate rollers are overlapped to print)

[0199] The pattern layer paste formula

[0200] Table 2 The pattern layer paste formula

[0201]

[0202] The preparation method of each single color ink of the pattern printing ink of Example 3 is the same as that of Example 1, and other process conditions are also completely the same, and are not repeated here. (But the grinding time of the first color and the second color ink needs to be lengthened to achieve the grinding effect).

[0203] The color difference of each single color ink is less than 4 degrees, and the solid content of each single color ink is 35%, and the viscosity is 15 S / 25℃ (PVC-4 cup).

[0204] The pattern protective layer paste

[0205] 1. Water-based acrylic resin binder 78%

[0206] 2. Solution stabilizer: polyethylene glycol (molecular weight 20,000, solid content 20%) 100%

[0207] 3. Film forming agent: propylene glycol benzoate 4%

[0208] 4. Polyoxypropylene ethylene oxide glycerol ether 0.4%

[0209] 5. Alkyl dimethyl quaternary ammonium salt 0.3%

[0210] 6. Polyethylene wax emulsion 4%

[0211] 7. Deionized water balance

[0212] The preparation method of the graphic protection layer printing ink of Example 3 is completely identical with the preparation method and process conditions (mixing speed, temperature, time) of Example 1, and will not be repeated here. The solid content of the printing ink is 40%, and the viscosity is 16 S / 25℃ (Coat-4 cup).

[0213] Preparation of acrylic water-soluble graphic film by printing

[0214] 1. The printing line speed of the graphic layer of Example 3 is 15 m / min, and the interval between each single color is 12S-16S. The other process conditions are the same as those of Examples 1-2, the width of the film is the same as that of Examples 1-2, and the packaging is also the same. Here, it will not be repeated here.

[0215] 2. The printing process of the protection layer of Example 3 is completely identical with that of Examples 1-2. Here, it will not be repeated here.

[0216] Application of acrylic water-soluble graphic film

[0217] Application of acrylic water-soluble graphic film of Examples 1-3

[0218] (1) Apply a layer of white water-based paint on the surface of the wood-plastic board, and polish, flatten and remove the burrs after drying.

[0219] 1. The substrate is selected as a wood-plastic board

[0220] (1) First, polish the surface of the wood-plastic board, flatten it, remove the burrs on the four edges, and spray a layer of white water-based paint. After drying, polish, flatten and remove the burrs on the four edges.

[0221] (2) Place the wood-plastic board on the platform (the platform requires a flat and non-inclined surface), and spray a layer of polyvinyl alcohol insolubilizer dimethyl ethyl urea aqueous solution with a temperature of 60℃ and a solid content of 0.5% on the surface of the board. The water surface spraying thickness is about 20μm.

[0222] (3) Place the graphic film carrier layer downward on the surface of the workpiece, stretch and straighten it, and gently scrape the graphic film with a rubber scraper to remove the bubbles and wrinkles between the graphic film and the workpiece. Large bubbles can be removed by piercing holes with a needle. Roll the four edges of the film to the back of the board, and cool to room temperature.

[0223] (4) Quickly spray a layer of diethylamine aqueous solution with a solid content of 0.5% on the graphic film protection layer, and the temperature of the aqueous solution is 5℃. The aqueous solution spraying thickness is determined by the complete water absorption and swelling of the graphic film.

[0224] (5) The standard for water absorption and swelling of the film is that the film uniformly absorbs water, expands, and the graphic layer and the carrier layer are completely water-soluble and swollen. The surface presents a flat gel state, and the graphic is slightly enlarged by 0.3-0.8%.

[0225] (6) According to the swelling effect of the pattern film, a proper amount of water solution can be sprayed until the whole film is evenly swollen.

[0226] (7) The coated workpiece is placed horizontally in a static dust-free drying room, and uniformly air-dried at room temperature for 72-100 h, with the relative humidity in the room being 30%-35%. A good dehumidification and air supply system is required. After complete curing, 2000-mesh polishing wax is used to polish the surface to brightness, and a pattern decoration layer of acrylic acid type water-soluble pattern film is obtained.

[0227] (8) The second film forming method is that after the pattern film is pasted with water solution, a layer of polyethylene oxide water solution with a solid content of 25% and a molecular weight of 25000-100000 is sprayed on the pattern layer. The spraying amount is determined according to the complete water absorption and swelling of the pattern film. Uniform air-drying is carried out at room temperature for 72-100 h. The other conditions and methods are the same as above. The method obtained is a complex film of acrylic acid and polyethylene oxide. The complexing effect of the complex film can be improved by multiple spraying of polyethylene oxide water solution to obtain the best film forming property after curing.

[0228] (II) Method for direct application on wood-plastic substrate

[0229] The method is to directly add pigments to wood-plastic, or to make the film itself into a film containing a base color.

[0230] (1) The wood-plastic substrate surface is polished, cleaned, and defects are removed. The surface is free of impurities and oil stains.

[0231] (2) The workpiece is placed on the film coating platform, and the horizontality is required without inclination.

[0232] A layer of polyvinyl alcohol insolubilizer dimethyl ethyl urea water solution with a temperature of 60°C and a solid content of 1% is sprayed on the surface of the board, and the water spraying thickness is about 20 μm.

[0233] (3) The pattern film carrier layer is quickly pasted on the surface of the workpiece with the pattern film carrier layer facing down. The pattern film is stretched and straightened, and the pattern is not skewed longitudinally. A rubber scraper is used to gently scrape the surface of the pattern and remove the bubbles and wrinkles between the workpiece and the pattern film. Large bubbles can be removed by piercing with a needle. The four edges of the film are rolled to the back of the board, and the film is cooled to room temperature.

[0234] (4) A layer of diethylamine water solution with a solid content of 0.5% is quickly sprayed on the surface of the pattern film. The water solution has a temperature of 5°C, and the water solution spraying thickness is determined according to the complete water absorption and swelling of the pattern film. The spraying can be appropriately supplemented.

[0235] 5) The water absorption of the film is the complete and uniform water absorption of the film, and the pattern layer and the carrier layer are completely water-absorbed and swollen. The surface presents a flat gel state, and the pattern is slightly enlarged by 0.3%-0.8. The pattern protective layer has an extended and bright surface.

[0236] (6) According to the swelling effect of the pattern, a proper amount of deionized water can be sprayed until the pattern is completely and evenly swollen.

[0237] 7) The coated workpiece is placed flat in a dry static chamber, and naturally dried at room temperature of 25-30°C for 72-100 hours until the pattern film is completely cured. (Or evenly air dried at room temperature until the film is completely cured, and then placed for 72-100 hours. Then polished with 2000-mesh polishing wax to obtain a pattern decorative layer.)

[0238] The second method for applying the acrylic water-soluble pattern film is:

[0239] After the pattern film is well attached, a layer of polyethylene oxide water solution with a solid content of 15% and a molecular weight of 25000-100000 is sprayed on the pattern layer. The spraying amount of the water solution is determined by the complete swelling of the pattern film. After evenly air dried at room temperature until the film is completely cured, and then placed for 72-100 hours, polished with 2000-mesh polishing wax to obtain a pattern decorative layer of the acrylic water-soluble pattern film. The relative humidity in the drying chamber is 35-40%, and it is dust-free.

[0240] Moisture resistance test:

[0241] 1. Two sample pieces, one for applying the pattern film on the painted surface of wood-plastic material and the other for direct application on the wood-plastic surface.

[0242] 2. Select existing PVC skin sample pieces, PVC hot-melt film sample pieces, and PVC hot-pressing (dry combination) sample pieces, a total of 3 pieces.

[0243] 3. Test method and conditions

[0244] The above sample pieces are tested at temperatures of 30°C and relative humidities of 60% and 85%. The sample pieces are placed in the above temperature and humidity humidifiers, and the changes are observed and tested, as shown in Table 3.

[0245] Test conditions: humidifier constant temperature 30°C, relative humidity 60%, 85%, film-forming additives selected from diethylamine and polyethylene oxide. No change is indicated by Δ.

[0246] Table 3 Moisture resistance test

[0247]

[0248]

[0249]

[0250] As shown in Table 3, the pattern decorative layer prepared by the acrylic water-soluble pattern film provided by the present application can be cured at normal temperature after film formation, becomes a pattern decorative layer resistant to moisture and not easy to fall off, greatly improves the service life of the product, and solves the problem of pattern skin falling off after moisture in the existing adhesive skin technology and hot lamination technology.

[0251] Water resistance test

[0252] 1. The workpiece used in the moisture resistance test is made of the same material as the workpiece

[0253] 2. Test method:

[0254] The sample pieces of Example 1-Example 3 and PVC skin were respectively placed in constant temperature water at 30℃ and 80℃ for immersion, and the water resistance and change of the pattern decorative layer of the sample pieces were observed, and the test results are shown in Table 4. Test conditions: water temperature 30℃ and 80℃, immersion for 120h.

[0255] Table 4 Water resistance test

[0256]

[0257]

[0258] As shown in Table 4, the pattern decorative layer prepared by the acrylic water-soluble pattern film provided by the present application is not bubbled, not cracked and not fallen off on the surface after immersion in water at 30℃ and 80℃ for 120h, has good water resistance, and the existing PVC skin product is bubbled at 40h, cracked at 80h, bubbled at 10h, cracked at 20h and peeled off at 60h under the condition of water temperature of 80℃. It is proved by the test comparison that the pattern decorative layer obtained by coating the acrylic water-soluble pattern film by water-soluble method has good water resistance, the pattern is not fallen off after water immersion, is firmly attached, and has water resistance.

[0259] In the above examples, the application range of the pattern film is only used on wood-plastic materials, and in actual application, it can be applied to various painted products, such as military appliances, military vehicles, weapons, etc., but for the surface of large metal manufacturing, the workpiece surface needs to be preheated before film coating, or the water temperature is increased to above 60~70℃, to avoid the solubility of the pattern film carrier layer at low temperature (below 25℃).

[0260] The acrylic water-soluble pattern film of the present application is preferably applied to various wood-plastic boards, the base color is added to the wood-plastic, and the pattern film is directly used on the board surface. The pattern film can also be evenly air-dried at a low temperature of 50-60 DEG C, so that the adhesion of the film is more firm, and the film has a stronger adhesion to the wood-plastic surface, and the film has a permeable combination.

[0261] The acrylic water-soluble pattern film of the present application can also be directly applied to the surface of a wood board, and has a more firm adhesion. The acrylic water-soluble pattern film of the present application can also be directly applied to stone and plastic products, and has a very wide application field.

[0262] The acrylic water-soluble pattern film of the present application is more suitable for preparing various stone patterns, such as agate patterns, marble patterns, and various non-standard stone patterns, is suitable for preparing various wood patterns, and is more suitable for preparing various military camouflage patterns and other patterns.

[0263] The acrylic water-soluble pattern film of the present application can not be coated with a secondary paint after the film coating, and the product is not subjected to repeated abrasion, so that the paint cost is saved, and the environmental pollution caused by the release of organic solvents in the paint process is reduced.

[0264] The acrylic water-soluble pattern film of the present application can also be sprayed with a layer of water-based acrylic paint on the pattern protective layer after the film coating, so that the surface wear resistance and the decorative property of the pattern layer are improved.

[0265] The present application solves the water washing process of the original water printing technology, the waste of the discarded polyvinyl alcohol film after the water washing, the waste of water, the environmental pollution caused by the use of organic solvents, the problem that the building decoration material manufactured by the existing skin pasting technology is afraid of water, is not water-resistant, the skin is easy to fall off, the product is not durable, and the service life is not reached, the energy consumption in the production and use process is reduced, and the carbon emission problem of electrolytic consumption is solved.

[0266] The above description is only the preferred embodiments of the present application, and it should be pointed out that, for ordinary skilled persons in the art, some improvements and refinements can be made without departing from the principles of the present application, and these improvements and refinements should also be regarded as the protection scope of the present application.

Claims

1. An acrylic water-soluble patterned film, comprising, in sequence, a printing carrier layer, a patterned layer, and a patterned protective layer; The printed carrier layer is a gel-reversible polyvinyl alcohol film; The pattern layer is obtained by printing a pattern layer paste, which comprises the following components by mass fraction: Water-based acrylic resin binder 60-75% Butyl diethylene glycol-ethyl ether 0~5% Waterborne polyurethane 0.5~1% Di(dioctylphosphoyloxy)titanate 0.5~1.8% Polyoxyethylene glycol alkyl ester 1~15% Pigment 1~12% Polyoxypropylene ethylene glycerol ether 0.01~0.25% Solution stabilizer aqueous solution 0~10% Film-forming agent 0~5% Water balance; The pattern protective layer is obtained by printing a pattern protective layer paste, which comprises the following components by mass fraction: Water-soluble acrylic resin binder 75-85% Solution stabilizer aqueous solution 0~20% Film-forming agent 1~5% Polyoxypropylene ethylene glycerol ether 0.01~0.8% Alkyl dimethyl quaternary ammonium salt 0.05~0.3% Polyethylene wax emulsion 2-5% Water balance.

2. The acrylic water-soluble patterned film according to claim 1, characterized in that, The thickness of the printed carrier layer is 20~40μm, the degree of alcoholysis of polyvinyl alcohol is 75~80%, and the molecular weight is 170,000~220,000.

3. The acrylic water-soluble patterned film according to claim 1, characterized in that, The water-based acrylic resin binder in the patterned layer slurry is a blend of film-forming acrylic emulsion and stearic non-film-forming acrylic, wherein the mass ratio of the film-forming acrylic emulsion to the stearic non-film-forming acrylic is (65~75):(35~25). The water-soluble acrylic resin binder in the patterned protective layer slurry is a blend of film-forming acrylic emulsion and stearic non-film-forming acrylic, with the mass ratio of film-forming acrylic emulsion to stearic non-film-forming acrylic being (65~75):(35~25).

4. The acrylic water-soluble patterned film according to claim 3, characterized in that, The water-based acrylic resin binder in the patterned layer slurry has a viscosity of 5500~7500MPa·s at 25℃, a solid content of 36±1%, and a pH of 7~7.

3. The aqueous solution of the solution stabilizer in the patterned layer slurry has a solid content of 15~25%, and the solution stabilizer is polyethylene glycol and / or ethylene glycol. The molecular weight of polyethylene glycol is 15000~20000. The film-forming agent in the patterned layer slurry includes one or more of oxalic acid, phthalic acid, and propylene glycol benzoate.

5. The acrylic water-soluble patterned film according to claim 1, characterized in that, The water-soluble acrylic resin binder in the patterned protective layer slurry has a viscosity of 5500~7500MPa·s at 25℃, a solid content of 36±1%, and a pH of 7~7.

3. The solution stabilizer aqueous solution in the patterned protective layer slurry has a solid content of 15~25%, and the solution stabilizer is polyethylene glycol and / or ethylene glycol. The molecular weight of polyethylene glycol is 15000~20000. The film-forming agent in the patterned protective layer slurry includes one or more of oxalic acid, phthalic acid, and propylene glycol benzoate.

6. The acrylic water-soluble patterned film according to claim 1, characterized in that, The solid content of the patterned layer slurry is 35-45%, and the viscosity measured by the Forecast cup is 13-18 S / 25℃. The solid content of the patterned protective layer slurry is 20-40%, and the viscosity measured using a Ford cup is 13-15 S / 25℃.

7. The method for preparing the acrylic water-soluble patterned film as described in claim 1, comprising the following steps: The raw materials are mixed according to the proportions in claim 1 to obtain pattern layer slurry and pattern protective layer slurry respectively. The pattern layer and pattern protective layer are then printed sequentially on the printing carrier layer using gravure printing process to obtain an acrylic water-soluble pattern film.

8. A method of using the acrylic water-soluble patterned film as described in any one of claims 1 to 6, comprising the following steps: A) Spray a layer of polyvinyl alcohol insoluble agent aqueous solution at a temperature of 60℃~70℃ onto the surface of the workpiece; B) With the printing carrier layer of the acrylic water-soluble patterned film facing the workpiece, quickly apply it to the surface of the workpiece, flatten it, and remove air bubbles and wrinkles between the workpiece and the film layer. C) After cooling to room temperature, spray a diethylamine aqueous solution or a polyethylene oxide aqueous solution at a temperature of 5~20℃ onto the surface of the patterned protective layer until the acrylic water-soluble patterned film has completely absorbed water and swelled. D) Dry until a complete film forms, let stand for 72-100 hours, then polish to obtain the final product.

9. The method of use according to claim 8, characterized in that, The polyvinyl alcohol insoluble agent is one or more of dimethylurea, dimethylethylurea, and trimethylmelamine.

10. The method of use according to claim 9, characterized in that, The solid content of the diethylamine aqueous solution is 0.5-3%; The solid content of the polyethylene oxide aqueous solution is 20-30%, and the molecular weight of the polyethylene oxide is 25,000-100,000.

Images