A broad-spectrum lightfast water-based ink, its preparation method and application

Abstract

The present application belongs to the technical field of ink, and provides a broad-spectrum sun-resistant water-based ink, a preparation method and application thereof, wherein the water-based ink comprises aliphatic polyester water-based polyurethane, hydrophilic composite broad-spectrum sunscreen, temperature-sensitive sustained-release light stabilizer, color paste, additive, and solvent, wherein the hydrophilic composite broad-spectrum sunscreen is a core-shell structure in which the hydrophilic composite broad-spectrum sunscreen is coated on the core of the broad-spectrum sunscreen, and the temperature-sensitive sustained-release light stabilizer is a core-shell structure in which the temperature-sensitive wall material is coated on the core of the light stabilizer; the water-based ink has broad-spectrum sunscreen function, can play a persistent sunscreen under high-temperature conditions such as sun exposure, and has good thermal stability. The ink is further printed on substrates such as PVC, and has good printing color reproducibility, full color, excellent sun resistance, and is especially suitable for printing of PVC and other materials used outdoors.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ink, more particularly, to a broad-spectrum light-fast water-based ink and a preparation method and application thereof. BACKGROUND

[0002] Polyvinyl chloride (PVC) materials are widely used in the fields of construction, packaging and medical and health care due to their good mechanical properties, toughness, chemical corrosion resistance and flame retardance. PVC printing materials are printed with patterns on the surface of PVC by using ink. With the development of PVC film preparation process and ink technology, the patterns on PVC printing materials are more diversified and can be used for indoor wall decoration, such as floor and wallpaper. However, PVC printing materials often face sunlight, high temperature and humidity during outdoor use, especially under high temperature and sunlight (40-60℃), the printed patterns are prone to lose original color, discoloration, deformation and aging, and the product performance and decoration ability are significantly reduced. Therefore, it is an urgent problem to improve the high-temperature light-fastness of printed patterns.

[0003] At present, the main technical solutions to protect PVC printed patterns from sunlight and reduce the damage caused by ultraviolet radiation include: (1) adding ultraviolet absorbers (sunscreen agents) to convert ultraviolet energy into harmless heat energy, thereby reducing the damage caused by ultraviolet radiation; (2) adding light-fast pigments, such as metal oxide pigments, such as titanium dioxide, zinc oxide and iron oxide, to maintain the color and physical and chemical properties of the printed patterns; (3) manufacturing a multi-layer co-extruded film on the surface of PVC printing products to prevent sunlight radiation, reduce direct contact between ultraviolet and infrared rays while maintaining the physical properties of PVC. However, the above technical solutions have the following main problems: (1) the stability of ultraviolet absorbers (common sunscreen agents such as butyl methoxydibenzoylmethane, benzophenone, ethylhexyl salicylate, etc.) is poor, the effective sunscreen time is short, and the protective effect of the product is affected; (2) physical sunscreens such as titanium dioxide and zinc oxide have excellent sunscreen effect and strong durability, but most of them are white particles, which will affect the color performance of the PVC water-based ink and limit the application range of the ink; (3) multi-layer co-extruded film requires multiple composite film structures such as base layer, functional layer and adhesive layer, which has a complex process and high cost. In addition, oily PVC printing ink will cause pollution problems, water-based ink contains almost no harmful substances such as VOC (volatile organic compounds), and will not produce harmful gases during use, which has less environmental pollution, and water-based ink is more widely used.

[0004] Therefore, it is urgent to develop a water-based ink, which has broad-spectrum sunscreen, high-temperature sun resistance, long-term stability, can be used for printing of PVC and other materials, has rich ink color, simple process, and low cost. SUMMARY

[0005] The present application aims to at least solve one of the technical problems existing in the prior art. To this end, the present application provides a broad-spectrum sun-resistant water-based ink and its preparation method and application. The ink provided by the present application has the characteristics of broad-spectrum sun resistance, long-term stable sunscreen effect, and good sunscreen effect at high temperature, can be used for printing of PVC and other materials, has rich ink color, simple process, and low cost, and the printed product can be used in various places, especially for outdoor use.

[0006] The first aspect of the present application provides a broad-spectrum sun-resistant water-based ink.

[0007] Specifically, a broad-spectrum sun-resistant water-based ink comprises the following components:

[0008] (a) aliphatic polyester type water-based polyurethane;

[0009] (b) hydrophilic composite broad-spectrum sunscreen agent;

[0010] (c) temperature-sensitive sustained-release light stabilizer;

[0011] (d) color paste;

[0012] (e) auxiliary agent;

[0013] (f) solvent;

[0014] The (b) hydrophilic composite broad-spectrum sunscreen agent has a core-shell structure, the core is a composite broad-spectrum sunscreen agent, and the shell is a hydrophilic wall material.

[0015] The (c) temperature-sensitive sustained-release light stabilizer has a core-shell structure, the core is a light stabilizer, and the shell is a temperature-sensitive hydrophilic wall material, and the glass transition temperature of the temperature-sensitive hydrophilic wall material is 45-55℃.

[0016] The hydrophilic composite broad-spectrum sunscreen used in the broad-spectrum sun-resistant water-based ink provided by the present application not only has a broad-spectrum sunscreen function, but also can be well dispersed in the water-based ink due to the hydrophilic wall material, thereby reducing the free concentration of the sunscreen, enhancing the sunscreen effect, absorbing UVA / UVB, and achieving excellent broad-spectrum sunscreen. The temperature-sensitive slow-release light stabilizer has a hydrophilic wall material, can be well dispersed in the water-based ink, and is uniformly mixed with the hydrophilic composite broad-spectrum sunscreen. Moreover, the wall material has temperature sensitivity, and is broken after being heated (the glass transition temperature of the temperature-sensitive wall material is 45-53℃, the temperature-sensitive wall material changes from a glass state to a high-elasticity state at a temperature of 45-53℃, and is destroyed under the action of the internal and external osmotic pressure difference, cannot guarantee the spherical structure, and the internal light stabilizer core material is slowly released). The light stabilizer can effectively quench the energy of the excited state of the sunscreen, help the activated sunscreen return to the ground state from the single heavy excited state, avoid the sunscreen from degrading through isomerization reaction, so that the sunscreen can still play a good sunscreen effect under high-temperature conditions, has good high-temperature sun resistance, and prolongs the sunscreen time. The ink of the present application can play a sunscreen effect for a long time under high-temperature conditions. In addition, the ink of the present application also adds an aliphatic polyester type water-based polyurethane, which contains both hydrophobic ester fatty chains and polar hydrophilic ester groups. During the film forming process of the ink, the hydrophilic groups are oriented towards the inside of the film, and the hydrophobic groups migrate to the surface of the film, thereby improving the water resistance of the film. In addition, the long ester fatty chain contains a polar ester group with a large cohesive energy, and has good stability under heating conditions, thereby improving the thermal stability of the film.

[0017] Broad-spectrum sunscreen: indicating the dual protection ability of UVA (near ultraviolet) and UVB (medium ultraviolet).

[0018] Preferably, the glass transition temperature of the temperature-sensitive hydrophilic wall material is 45-53℃.

[0019] Preferably, the broad-spectrum sun-resistant water-based ink comprises the following components by weight:

[0020] (a) aliphatic polyester type water-based polyurethane 25-35 parts;

[0021] (b) hydrophilic composite broad-spectrum sunscreen 5-10 parts;

[0022] (c) temperature-sensitive slow-release light stabilizer 3-8 parts;

[0023] (d) color paste 25-40 parts;

[0024] (e) auxiliary agent 5-12 parts;

[0025] (f) solvent 10-15 parts.

[0026] Further preferably, the broad-spectrum sun-resistant water-based ink, by weight parts, comprises the following components:

[0027] (a) aliphatic polyester type water-based polyurethane 28-32 parts;

[0028] (b) hydrophilic composite broad-spectrum sunscreen 6-9 parts;

[0029] (c) temperature-sensitive slow-release light stabilizer 4-7 parts;

[0030] (d) color paste 28-35 parts;

[0031] (e) auxiliary agent 6-10 parts;

[0032] (f) solvent 11-14 parts.

[0033] Preferably, the (a) aliphatic polyester type water-based polyurethane comprises the following raw material components:

[0034] (a1) aliphatic isocyanate;

[0035] (a2) polyester polyol;

[0036] (a3) hydrophilic chain extender;

[0037] (a4) crosslinking agent;

[0038] (a5) salt-forming agent;

[0039] (a6) catalyst;

[0040] (a7) auxiliary agent.

[0041] Further preferably, the (a) aliphatic polyester type water-based polyurethane comprises the following raw material components, by weight parts:

[0042] (a1) aliphatic isocyanate 10-50 parts;

[0043] (a2) polyester polyol 30-60 parts;

[0044] (a3) hydrophilic chain extender 3-12 parts;

[0045] (a4) crosslinking agent 1-5 parts;

[0046] (a5) salt-forming agent 0.5-8 parts;

[0047] (a6) catalyst 0.0001-0.01 parts;

[0048] (a7) auxiliary agent 0.3-5 parts.

[0049] More preferably, the (a) aliphatic polyester type water-based polyurethane comprises the following raw material components, by weight parts:

[0050] (a1) aliphatic isocyanate 25-40 parts;

[0051] (a2) polyester polyol 35-45 parts;

[0052] (a3) hydrophilic chain extender 5-8 parts;

[0053] (a4) crosslinking agent 0.8-3.5 parts;

[0054] (a5) salt forming agent 4.5-6.3 parts;

[0055] (a6) catalyst 0.005-0.008 parts;

[0056] (a7) auxiliary agent 0.5-1.5 parts.

[0057] Preferably, the (a1) aliphatic isocyanate is selected from at least one of hexamethylene diisocyanate, isophorone diisocyanate, methylcyclohexane diisocyanate, hydrogenated phenylmethane diisocyanate. Further preferably, the aliphatic isocyanate is isophorone diisocyanate.

[0058] Preferably, the (a2) polyester polyol is selected from at least one of polycaprolactone polyol, polyethylene adipate diol, polybutylene adipate diol, polyadipate castor oil polyol, polycarbonate 1,6-hexanediol diol, polyneopentyl glycol-1,6-hexanediol diol. Further preferably, the polyester polyol is polycaprolactone polyol.

[0059] Preferably, the (a3) hydrophilic chain extender is selected from at least one of dimethylolpropionic acid, dihydroxy half ester, sodium ethylenediaminoethane sulfonate, diethylenetriamine, methyldiethanolamine, ethylenediamine. Further preferably, the hydrophilic chain extender is dimethylolpropionic acid, ethylenediamine.

[0060] Preferably, the (a4) crosslinking agent is selected from at least one of glyceryl monostearate trimethylolpropane, triethanolamine, glycerol, diethylenetriamine. Further preferably, the crosslinking agent is glyceryl monostearate.

[0061] Preferably, the (a5) salt forming agent is selected from at least one of triethylamine, ammonia, sodium hydroxide, acetic acid, hydrochloric acid. Further preferably, the salt forming agent is triethylamine.

[0062] Preferably, the (a6) catalyst is selected from at least one of triethylamine, N,N-dimethylcyclohexylamine, triethylenediamine, stannous octoate, butyl tin dilaurate, bismuth isooctoate, potassium acetate. Further preferably, the catalyst is butyl tin dilaurate.

[0063] Preferably, the (a7) co-agent is selected from at least one of acetone, ammonia, butanone, tetrahydrofuran. Further preferably, the co-agent is acetone.

[0064] Preferably, the (b) hydrophilic complex broad-spectrum sunscreen agent comprises the following raw material components:

[0065] (b1) a UVA ultraviolet light absorber;

[0066] (b2) a UVB ultraviolet light absorber;

[0067] (b3) an ultraviolet light absorber solvent;

[0068] (b4) an emulsifier;

[0069] (b5) an initiator;

[0070] (b6) a hydrophilic wall material monomer;

[0071] (b7) water.

[0072] Further preferably, the (b) hydrophilic complex broad-spectrum sunscreen agent comprises the following raw material components by weight parts:

[0073] (b1) a UVA ultraviolet light absorber 4-12 parts;

[0074] (b2) a UVB ultraviolet light absorber 3-10 parts;

[0075] (b3) an ultraviolet light absorber solvent 4-12 parts;

[0076] (b4) an emulsifier 15-40 parts;

[0077] (b5) an initiator 0.1-0.8 parts;

[0078] (b6) a hydrophilic wall material monomer 2-10 parts;

[0079] (b7) deionized water 25-40 parts.

[0080] More preferably, the (b) hydrophilic complex broad-spectrum sunscreen agent comprises the following raw material components by weight parts:

[0081] (b1) a UVA ultraviolet light absorber 8-10 parts;

[0082] (b2) a UVB ultraviolet light absorber 5-8 parts;

[0083] (b3) an ultraviolet light absorber solvent 8-10 parts;

[0084] (b4) an emulsifier 18-23 parts;

[0085] (b5) an initiator 0.3-0.5 parts;

[0086] (b6) 5-8 parts of a hydrophilic wall material monomer;

[0087] (b7) 28-35 parts of deionized water.

[0088] The present application dissolves solid UVA and UVB ultraviolet absorbers by using an ultraviolet absorber solvent to form a broad-spectrum sunscreen system, and coats the system with a hydrophilic wall material to prepare a hydrophilic, biocompatible, hydrophilic composite broad-spectrum sunscreen with improved dispersibility in an aqueous system.

[0089] Preferably, the solid content of the (b) hydrophilic composite broad-spectrum sunscreen is 40%-50%.

[0090] Preferably, the (b1) UVA ultraviolet absorber is selected from at least one of butyl methoxydibenzoylmethane, benzophenone. Further preferably, the UVA ultraviolet absorber is butyl methoxydibenzoylmethane.

[0091] Preferably, the (b2) UVB ultraviolet absorber is selected from at least one of 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl salicylate, ethylhexyl methoxycinnamate, p-aminobenzoic acid, cinnamic acid ester, benzalkonium camphor methyl sulfate. Further preferably, the UVB ultraviolet absorber is 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate.

[0092] Preferably, the (b3) ultraviolet absorber solvent is homosalate (also known as homosalate). Further preferably, the ultraviolet absorber solvent is liquid homosalate. The ultraviolet absorber solvent is used to dissolve oil-soluble ultraviolet absorbers, such as homosalate to dissolve oil-soluble UVA ultraviolet absorber solid butyl methoxydibenzoylmethane.

[0093] Preferably, the (b4) emulsifier is at least one of polyvinyl alcohol, polyol ester fatty acid ester, polyoxyethylene ether, polyoxypropylene ether. Further preferably, the emulsifier is polyvinyl alcohol.

[0094] Preferably, the (b5) initiator is at least one of dibenzoyl peroxide, azobis diisobutyl amide hydrochloride, azobis diisobutyl imidazole hydrochloride, ammonium persulfate. Further preferably, the initiator is dibenzoyl peroxide.

[0095] Preferably, the (b6) hydrophilic wall material monomer is at least one of ethylene glycol dimethacrylate, methyl methacrylate, butyl methacrylate, methyl vinyl ketone, vinyl acetate. Further preferably, the hydrophilic wall material monomer is ethylene glycol dimethacrylate.

[0096] Preferably, the (c) temperature-sensitive slow-release light stabilizer comprises the following raw material components:

[0097] (c1) light stabilizer;

[0098] (c2) temperature-sensitive hydrophilic wall material oligomer;

[0099] (c3) temperature-sensitive wall material monomer;

[0100] (c4) emulsifier;

[0101] (c5) initiator;

[0102] (c6) water.

[0103] Further preferably, the (c) temperature-sensitive slow-release light stabilizer comprises the following raw material components:

[0104] (c1) light stabilizer 3-10 parts;

[0105] (c2) temperature-sensitive hydrophilic wall material oligomer 10-25 parts;

[0106] (c3) temperature-sensitive wall material monomer 12-28 parts;

[0107] (c4) emulsifier 10-35 parts;

[0108] (c5) initiator 0.1-1.2 parts;

[0109] (c6) water 23-42 parts.

[0110] More preferably, the (c) temperature-sensitive slow-release light stabilizer comprises the following raw material components:

[0111] (c1) light stabilizer 4-7 parts;

[0112] (c2) temperature-sensitive hydrophilic wall material oligomer 12-18 parts;

[0113] (c3) temperature-sensitive wall material monomer 15-21 parts;

[0114] (c4) emulsifier 12-26 parts;

[0115] (c5) initiator 0.3-0.7 parts;

[0116] (c6) water 26-33 parts.

[0117] Preferably, the (c1) light stabilizer is selected from at least one of bis- ethylhexyloxyphenol methoxyphenyl triazine, UV-1577, UV1164, UV328, UV-P, UV384-2, UV-1577, UV1164, UV-400, UV405. Further preferably, the light stabilizer is bis-ethylhexyloxyphenol methoxyphenyl triazine.

[0118] Preferably, the (c2) temperature-sensitive hydrophilic wall material oligomer is selected from at least one of polyester acrylate, polyvinyl alcohol, polyurethane, polystyrene. Further preferably, the temperature-sensitive hydrophilic wall material oligomer is polyester acrylate.

[0119] Preferably, the (c3) temperature-sensitive wall material monomer is selected from at least one of 1,6-hexanediol diacrylate, tripropyleneglycol diacrylate, trimethylolpropane triacrylate. Further preferably, the temperature-sensitive wall material monomer is 1,6-hexanediol diacrylate.

[0120] Preferably, the (c4) emulsifier is selected from at least two of polyoxyethylene sorbitol ester fatty acid ester, sorbitan ester fatty acid ester, polyvinyl alcohol, polyol ester fatty acid ester, polyoxyethylene ether, polyoxypropylene ether. Further preferably, the emulsifier is a combination of polyoxyethylene sorbitol ester fatty acid ester and sorbitan ester fatty acid ester in a mass ratio of (7-9):(1-2).

[0121] Preferably, the (c5) initiator is selected from at least one of 2-hydroxy-4'-(2- hydroxyethoxy)-2-methylpropiophenone, bis(1-(2,4-difluorophenyl)-3- pyrryl) titanium dioxide, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide. Further preferably, the initiator is 2-hydroxy-4'-(2-hydroxyethoxy)-2- methylpropiophenone.

[0122] Preferably, the (d) color paste is a red color paste and / or a blue color paste.

[0123] Preferably, the red color paste is BASF Dispers Red 3855 red color paste.

[0124] Preferably, the blue color paste is BASF phthalocyanine blue BK6902 lightfast blue color paste.

[0125] Preferably, the (e) auxiliary agent comprises the following raw material components:

[0126] (e1) a dispersing agent;

[0127] (e2) an antifoaming agent;

[0128] (e3) anhydrous ethanol.

[0129] Further preferably, the (e) auxiliary agent comprises the following raw material components by weight parts:

[0130] (e1) dispersant 1-5 parts;

[0131] (e2) defoaming agent 0.1-1 part;

[0132] (e3) anhydrous ethanol 1-10 parts.

[0133] Preferably, the (e1) dispersant is at least one of BASF Dispex CX 4320AM, BASF Dispex CX 4290AM, BASF Dispex Ultra FA 4484. Further preferably, the (e1) dispersant is BASF Dispex CX 4320AM. BASF Dispex CX 4320AM does not contain volatile organic compounds (VOCs) and can effectively disperse the color paste and microcapsule material.

[0134] Preferably, the (e2) defoaming agent is at least one of TEGO FOAMEX 805, TEGO FOAMEX 822, TEGO FOAMEX 825. Further preferably, the (e2) defoaming agent is TEGO FOAMEX 805.

[0135] Preferably, the (e3) is anhydrous ethanol, industrial grade, effective content 99.9%.

[0136] Preferably, the (f) solvent is water.

[0137] The second aspect of the present application provides a preparation method of a broad-spectrum sun-resistant water-based ink.

[0138] A preparation method of a broad-spectrum sun-resistant water-based ink, comprising the following steps:

[0139] (1) mixing and stirring (a) aliphatic polyester type water-based polyurethane and (d) color paste to obtain a pre-dispersion A;

[0140] (2) adding (b) hydrophilic composite broad-spectrum sunscreen and (c) temperature-sensitive sustained-release light stabilizer to the pre-dispersion A, mixing and stirring to obtain a pre-dispersion B;

[0141] (3) adding (e) auxiliary agent and (f) solvent to the pre-dispersion B, mixing and stirring, filtering to obtain the broad-spectrum sun-resistant water-based ink.

[0142] Preferably, in step (1), the mixing and stirring speed is 800-1200 r / min, and the time is 10-20 min.

[0143] Preferably, in step (2), the speed of the mixing stirring is 1500-1800 r / min, the time is 20-40 min, and the temperature is 30-50℃.

[0144] Preferably, in step (3), the speed of the mixing stirring is 800-1200 r / min, the time is 5-15 min.

[0145] Preferably, the preparation method of the (a) aliphatic polyester type waterborne polyurethane comprises the following steps:

[0146] The aliphatic isocyanate, the polyester polyol and the catalyst are mixed, reacted at 80-100℃ for 1-5h, then the crosslinking agent and the hydrophilic chain extender are added, reacted at 50-70℃ for 1-5h, the viscosity is adjusted by adding the auxiliary agent, the prepolymer is prepared; then the salt forming agent is added, emulsified by adding water, and the hydrophilic chain extender is added, the aliphatic polyester type waterborne polyurethane is prepared.

[0147] The aliphatic polyester type waterborne polyurethane prepared by the present application contains the lipophilic group (long fatty chain), the hydrophilic group (anion group) and the polar group (such as the glycerol hydroxyl group in the glyceryl monostearate molecule, which has the hydrophilic property), can form a film between the oil phase and the water phase to reduce the surface tension. Meanwhile, the polyester polyol reaction is used as the flexible segment in the present application, the main chain contains the ester group with strong polarity, and the cohesive energy is large, which is beneficial to generate more hydrogen bond interaction between the internal flexible segment and the rigid segment, produce uniform physical crosslinking points, and endow the polyester type polyurethane with higher mechanical properties and strength, and the waterborne polyurethane system with long fatty side chain is formed to improve the thermal stability and water resistance of the ink. In addition, the polyester polyol has good hydrophilic property, which is beneficial to prepare the waterborne polyurethane with high solid content.

[0148] Preferably, the solid content of the aliphatic polyester type waterborne polyurethane is 58%-62%.

[0149] Preferably, the NCO mass fraction of the prepolymer is 3.23%-4.65%, and / or the viscosity of the prepolymer is 13-18 seconds (paint No. 4 cup, 25℃).

[0150] Preferably, the polyester polyol and the crosslinking agent are dried before use, the drying temperature is 110-130℃, and the drying time is 0.5-1.5h.

[0151] Preferably, the preparation method of the (b) hydrophilic composite broad-spectrum sunscreen agent comprises the following steps:

[0152] The emulsifier is added into water to obtain an aqueous phase; the UV absorber solvent, the UVA UV absorber and the UVB UV absorber are mixed to obtain a dispersion, and then the hydrophilic wall material monomer is added to obtain an oil phase; the aqueous phase and the oil phase are mixed to obtain a pre-emulsion; and the pre-emulsion and the initiator are mixed in a protective gas atmosphere to obtain the hydrophilic composite broad-spectrum sunscreen.

[0153] Preferably, after the aqueous phase and the oil phase are mixed, ultrasonic treatment is carried out at -5-5°C to obtain the pre-emulsion.

[0154] Preferably, the protective gas is nitrogen.

[0155] Preferably, in the protective gas atmosphere, the pre-emulsion is stirred at 30-50°C at a speed of 1000-1500 r / min for 10-30 min, and then mixed with the initiator.

[0156] Preferably, the preparation method of the (c) temperature-sensitive slow-release light stabilizer comprises the following steps:

[0157] The water, the emulsifier and the temperature-sensitive hydrophilic wall material oligomer are mixed to obtain an aqueous phase; the light stabilizer and the temperature-sensitive wall material monomer are mixed at 40-60°C to obtain an oil phase; the aqueous phase and the oil phase are mixed and homogenized to obtain an oil-in-water emulsion; the emulsifier is added in a protective gas atmosphere, and the reaction is carried out at 75-95°C for 1-3 h, and then the temperature-sensitive slow-release light stabilizer is prepared by drying.

[0158] Preferably, the drying is spray drying.

[0159] The third aspect of the present application provides an application of a broad-spectrum sunscreen water-based ink.

[0160] An application of a broad-spectrum sunscreen water-based ink in preparing a printed product.

[0161] Preferably, the printed product is an outdoor printed product.

[0162] Preferably, the printed product is a decorative PVC wall paper wallboard.

[0163] A method for using a broad-spectrum sunscreen water-based ink, comprising the following steps:

[0164] The water-based ink is printed on a printing substrate, dried and laminated.

[0165] Preferably, the printing is gravure printing.

[0166] Preferably, the printing substrate comprises at least one of polyvinyl chloride (PVC), polypropylene (PP), polyethylene (PE) and polyethylene terephthalate (PET). The PVC material is mostly used outdoors.

[0167] Preferably, the temperature of the drying is 45-60℃, and the time is 30-60s.

[0168] Preferably, the temperature of the pressing is 65-185℃, and the time is 20-35s.

[0169] The oil ink provided by the present application is high-temperature-resistant and does not change color after pressing.

[0170] Preferably, the stretching glue is used for pressing, so that a smooth, matte or skin-feeling PVC is obtained.

[0171] Compared with the prior art, the present application has the following advantages:

[0172] The water-based ink provided by the present application has a wide spectrum of sun resistance, and uses an aliphatic polyester type water-based polyurethane, a hydrophilic composite broad-spectrum sunscreen, a temperature-sensitive slow-release type light stabilizer, a color paste, an additive, and a solvent as main components. The hydrophilic composite broad-spectrum sunscreen is a core-shell structure in which the hydrophilic composite broad-spectrum sunscreen is coated on the core of the broad-spectrum sunscreen, and the temperature-sensitive slow-release type light stabilizer is a core-shell structure in which the temperature-sensitive hydrophilic wall material is coated on the core of the light stabilizer. The hydrophilic composite broad-spectrum sunscreen has a broad-spectrum sunscreen function and good hydrophilicity. The temperature-sensitive slow-release type light stabilizer has temperature sensitivity, and after being heated, the wall material is broken and the light stabilizer is released in an orderly manner, so that the ink has high-temperature resistance and sun resistance, and has hydrophilicity and can be well dispersed in the ink. Therefore, the interaction between the hydrophilic composite broad-spectrum sunscreen and the temperature-sensitive slow-release type light stabilizer can make the ink have a long-term sunscreen effect under high-temperature conditions, and have high-temperature resistance and sun resistance. In addition, the two also have reflection and scattering effects, which can increase the absorption of the compounded sunscreen to ultraviolet rays by lengthening the optical path, thereby improving the sunscreen effect. In addition, the ink of the present application also adds an aliphatic polyester type water-based polyurethane, which contains hydrophobic ester fatty chains and polar hydrophilic ester groups. During the film forming process of the ink, the hydrophilic groups are oriented towards the inside of the film, and the hydrophobic groups migrate to the surface of the film, thereby improving the water resistance of the film. In addition, the long ester fatty chain contains a polar ester group with a large cohesive energy, which has good stability under heating conditions, thereby improving the thermal stability of the film. The water-based ink provided by the present application is particularly suitable for printing on PVC and other materials used outdoors. The ink of the present application is further printed on PVC and other substrates, and has good color reproduction, rich colors, excellent sun resistance, and reaches level 8. DETAILED DESCRIPTION

[0173] In order to make the skilled in the art more clearly understand the technical solutions described in the present application, the following examples are given for illustration. It should be pointed out that the following examples do not limit the scope of protection required by the present application.

[0174] In the following examples, the raw materials, reagents or devices used, unless otherwise specified, can be obtained from conventional commercial channels, or can be obtained by existing known methods.

[0175] Example 1

[0176] A broad-spectrum sun-resistant water-based ink comprises the following components by weight parts:

[0177] (a) 30 parts of aliphatic polyester type water-based polyurethane;

[0178] (b) 8 parts of hydrophilic composite broad-spectrum sunscreen;

[0179] (c) 5 parts of temperature-sensitive slow-release light stabilizer;

[0180] (d) 35 parts of BASF Dispers Red 3855 red paste;

[0181] (e) 10 parts of auxiliary agent (1 part of defoaming agent TEGO FOAMEX 805, 8.5 parts of anhydrous ethanol, and 0.5 parts of BASF Dispex CX4320AM);

[0182] (f) 12 parts of water;

[0183] (b) The hydrophilic composite broad-spectrum sunscreen has a core-shell structure, the core is a composite broad-spectrum sunscreen, and the shell is a hydrophilic wall material;

[0184] (c) The temperature-sensitive slow-release light stabilizer has a core-shell structure, the core is a light stabilizer, and the shell is a temperature-sensitive hydrophilic wall material, and the glass transition temperature of the temperature-sensitive hydrophilic wall material is 45°C.

[0185] The preparation method of the above-mentioned broad-spectrum sun-resistant water-based ink comprises the following steps:

[0186] (1) Preparation of aliphatic polyester type water-based polyurethane: 46 parts of dehydrated polycaprolactone polyol, 23 parts of isophorone diisocyanate, and 2 parts of butyl tin dilaurate are added to a three-necked flask, and the water bath is heated to 90°C. After 2.5 hours of reaction, the water bath is cooled to 60°C. Add 2 parts of glyceryl stearate and 3 parts of dimethylol propionic acid and react for 2.5 hours. During the reaction, add 3 parts of acetone to adjust the viscosity of the system to 18 s (coating 4 cup, 25°C). A polyurethane prepolymer A with a NCO mass fraction of 3.87% is prepared. Add 3 parts of triethylamine and neutralize, add 15 parts of water under high-speed stirring, and at the same time add 3 parts of chain extender ethylenediamine, continue to stir for 30 min, then remove the acetone by reduced pressure distillation, and prepare the aliphatic polyester type water-based polyurethane.

[0187] (2) Preparation of hydrophilic composite broad-spectrum sunscreen: 25 parts of PVA emulsifier solution was placed in a beaker, 28.5 parts of deionized water was added, and stirred uniformly as the water phase for standby. Salicylic acid trimethylcyclohexyl ester, 2-cyano-3,3-diphenyl acrylate-2-ethylhexyl ester and butyl methoxy benzoyl methane (3:2:1 mass ratio, total 40 parts) were added to a beaker and stirred to prepare dispersion A. 6 parts of ethylene glycol dimethacrylate was added and stirred uniformly as the oil phase for standby. Then the two phases were mixed and placed in an ice water bath, and pre-emulsion B was prepared by ultrasonic cell crusher for 25 min. Pre-emulsion B was poured into a three-necked round-bottom flask and stirred at a speed of 1200 r / min, the temperature was kept at 40°C and nitrogen was continuously introduced, 0.5 parts of initiator benzoyl peroxide was added after 20 min, and the temperature was kept constant and stirred for 2 h to prepare the hydrophilic composite broad-spectrum sunscreen, which was a core-shell structure.

[0188] (3) Preparation of temperature-sensitive slow-release light stabilizer: 24.5 parts of deionized water, 15 parts of complex emulsifier and 25 parts of polyester acrylic acid were stirred uniformly as the water phase; 35 parts of bis-ethylhexyloxyphenol methoxyphenyl triazine and 1,6-hexanediol diacrylate (mass ratio 1:2) were added to a beaker and heated and stirred in a 50°C water bath until completely dissolved to obtain a uniform oil phase. The water phase and the oil phase were mixed and homogenized at a shear rate of 5000 r / min for 3 min to form a uniform O / W emulsion. The emulsion was poured into a conical flask, 0.5 parts of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methyl benzophenone emulsifier was added, and the slurry was stirred at 85°C under the protection of nitrogen for 2 h. The microcapsule slurry was spray dried at 190°C to obtain a white powder as the temperature-sensitive slow-release light stabilizer, which was a core-shell structure.

[0189] (4) Preparation of ink: 30 parts of aliphatic polyester type waterborne polyurethane, 35 parts of red paste and 0.5 parts of dispersant were added to a stirring roller at a speed of 1200 r / min and dispersed for 15 min to obtain pre-dispersion A. 8 parts of hydrophilic composite broad-spectrum sunscreen and 5 parts of temperature-sensitive slow-release light stabilizer were added to the pre-dispersion A and dispersed at a speed of 1600 r / min for 30 min to prepare pre-dispersion B, which was prepared by controlling the temperature below 40°C through a cold air machine. 0.5 parts of defoaming agent, 8.5 parts of pH adjuster, leveling agent and 12 parts of water were added to the pre-dispersion in turn, and dispersed uniformly at a speed of 900 r / min for 10 min, and filtered to obtain the broad-spectrum sunscreen water-based PVC ink.

[0190] Example 2

[0191] A broad-spectrum sunscreen water-based ink, by weight parts, includes the following components:

[0192] (a) 35 parts of aliphatic polyester type waterborne polyurethane;

[0193] (b) hydrophilic composite broad-spectrum sunscreen 10 parts;

[0194] (c) temperature-sensitive slow-release light stabilizer 8 parts;

[0195] (d) BASF Dispers Red 3855 red paste 27 parts;

[0196] (e) auxiliary agent (1 part TEGO FOAMEX 805, 8.5 parts anhydrous ethanol, 0.5 parts BASF Dispex CX 4320 AM) 10 parts;

[0197] (f) water 10 parts;

[0198] (b) The hydrophilic composite broad-spectrum sunscreen is a core-shell structure, the core is a composite broad-spectrum sunscreen, and the shell is a hydrophilic wall material;

[0199] (c) The temperature-sensitive slow-release light stabilizer is a core-shell structure, the core is a light stabilizer, and the shell is a temperature-sensitive hydrophilic wall material, and the glass transition temperature of the temperature-sensitive hydrophilic wall material is 45°C.

[0200] The preparation method of the above-mentioned broad-spectrum sun-resistant water-based ink is the same as that in Example 1.

[0201] Example 3

[0202] A broad-spectrum sun-resistant water-based ink, by weight parts, comprises the following components:

[0203] (a) aliphatic polyester type water-based polyurethane 25 parts;

[0204] (b) hydrophilic composite broad-spectrum sunscreen 5 parts;

[0205] (c) temperature-sensitive slow-release light stabilizer 3 parts;

[0206] (d) red paste 40 parts;

[0207] (e) auxiliary agent (2 parts of defoaming agent, 9 parts of pH adjuster, and 1 part of leveling agent) 12 parts;

[0208] (f) water 15 parts.

[0209] (d) BASF Dispers Red 3855 red paste 40 parts;

[0210] (e) auxiliary agent (2 parts of TEGO FOAMEX 805, 9 parts of anhydrous ethanol, and 1 part of BASF Dispex CX 4320 AM) 12 parts;

[0211] (f) water 15 parts;

[0212] (b) the hydrophilic composite broad-spectrum sunscreen agent is a core-shell structure, the core is the composite broad-spectrum sunscreen agent, and the shell is the hydrophilic wall material;

[0213] (c) the temperature-sensitive sustained-release light stabilizer is a core-shell structure, the core is the light stabilizer, and the shell is the temperature-sensitive hydrophilic wall material, and the glass transition temperature of the temperature-sensitive hydrophilic wall material is 45°C.

[0214] The preparation method of the above-mentioned broad-spectrum sun-resistant water-based ink is the same as that of Example 1.

[0215] Comparative Example 1

[0216] A broad-spectrum sun-resistant water-based ink, which is different from Example 1 in that the hydrophilic composite broad-spectrum sunscreen agent of Example 1 is replaced by an equal weight part of a commercially available sunscreen agent without a core-shell structure (Jiali Technology, SYSG-12, the main component is butyl methoxydibenzoylmethane). The preparation method of the above-mentioned water-based ink is the same as that of Example 1.

[0217] Comparative Example 2

[0218] A broad-spectrum sun-resistant water-based ink, which is different from Example 1 in that the temperature-sensitive sustained-release light stabilizer of Example 1 is replaced by an equal weight part of a commercially available light stabilizer without a core-shell structure (Tianxi New Material, model 328, poly(4-hydroxy-2,2,6,6-tetramethyl-1-piperidinethanol) succinate). The preparation method of the above-mentioned water-based ink is the same as that of Example 1.

[0219] Comparative Example 3

[0220] A broad-spectrum sun-resistant water-based ink, which is different from Example 1 in that it does not contain the hydrophilic composite broad-spectrum sunscreen agent and the temperature-sensitive sustained-release light stabilizer. The preparation method of the above-mentioned water-based ink is the same as that of Example 1.

[0221] Comparative Example 4

[0222] A broad-spectrum sun-resistant water-based ink, which is different from Example 1 in that it does not contain the temperature-sensitive sustained-release light stabilizer. The preparation method of the above-mentioned ink is the same as that of Example 1.

[0223] Application Example

[0224] A method for using a broad-spectrum sun-resistant water-based ink, comprising the following steps:

[0225] The water-based ink prepared in Example 1 is used for intaglio printing on PVC, dried at 45°C for 40s, and pressed at 65-185°C for 20s using a stretching glue. The ink provided by the present application does not change color after high-temperature pressing.

[0226] Product effect test

[0227] The water-based inks prepared in each embodiment and comparative example were tested for lightfastness, color difference, viscosity, adhesion, water resistance, and initial dryness. The lightfastness was tested according to the national standard GB / T 22771-2008, with a test temperature of 45℃, a maximum lightfastness level of 8, and the best lightfastness. The short color difference was tested by placing the ink under a 45℃, 50W ultraviolet lamp for 60h, and observing the color change of the ink. The long color difference was tested by placing the ink under a 45℃, 50W ultraviolet lamp for 300h, and observing the color change of the ink. The viscosity was determined according to GB / T1723-93 at a temperature of (23±2)℃ (coating cup No. 4, seconds / 25℃). The adhesion was determined according to GB / T9286-2021. The water resistance was determined by cutting the printed product into 5cm x 5cm samples, placing them in a beaker containing deionized water at room temperature (28℃±2) for 30min, and observing whether they changed color. The initial dryness was determined according to GB / T13217.5-2008. The test results are shown in Table 1 below.

[0228] Table 1 Performance test results of each water-based ink

[0229]

[0230] As can be seen from the above table, the lightfastness of the water-based ink provided by the present application can reach level 8, and the color difference changes little under long-term irradiation of an ultraviolet lamp, indicating excellent high-temperature lightfastness. Moreover, the viscosity, adhesion, water resistance, and initial dryness can all meet the requirements. Further, when the water-based ink of the present application is used on a printing substrate such as PVC, the ink does not change color after high-temperature pressing.

[0231] Comparative Example 1 has decreased lightfastness, and the color difference changes greatly under long-term irradiation of an ultraviolet lamp, indicating that the ink prepared using a commercially available sunscreen has poor lightfastness. In the present application, the sunscreen is modified by hydrophilic coating to improve its dispersibility in the water-based ink, and can work well with the temperature-sensitive, slow-release light stabilizer to provide long-lasting sunscreen effects and long-term stability.

[0232] Comparative Example 2 has decreased lightfastness, and the color difference increases somewhat under long-term irradiation of an ultraviolet lamp, indicating that the ink prepared using a commercially available light stabilizer has poor lightfastness. In the present application, the light stabilizer is coated with a temperature-sensitive hydrophilic wall material, which not only disperses well in the water-based ink, but also contacts the hydrophilic, broad-spectrum sunscreen well under long-term high-temperature irradiation, to work together to ensure the sunscreen ability of the ink under high-temperature conditions.

[0233] Comparative Example 3 has a serious decrease in lightfastness, and the color difference changes greatly under long-term irradiation of an ultraviolet lamp, indicating that the sunscreen and light stabilizer have been lost, greatly reducing the sunscreen performance of the ink.

[0234] Comparative Example 4 has decreased lightfastness compared to Comparative Example 1 and Example 1, and although it has less color difference under short time irradiation of ultraviolet light, it has increased color difference under long time irradiation, indicating that the present application not only improves the sunscreen effect of the hydrophilic composite broad-spectrum sunscreen agent, but also has long-term stability relative to commercially available sunscreens.

Claims

1. A broad spectrum lightfast water-based ink, characterized in that, Comprise the following components: (a) aliphatic polyester type water-based polyurethane; (b) hydrophilic composite broad-spectrum sunscreen agent; (c) temperature-sensitive sustained-release light stabilizer; (d) color paste; (e) auxiliary agent; (f) solvent; The (b) hydrophilic composite broad-spectrum sunscreen agent is a core-shell structure, the core is a composite broad-spectrum sunscreen agent, and the shell is a hydrophilic wall material; The (c) temperature-sensitive sustained-release light stabilizer is a core-shell structure, the core is a light stabilizer, and the shell is a temperature-sensitive hydrophilic wall material, and the glass transition temperature of the temperature-sensitive hydrophilic wall material is 45-55℃; The (b) hydrophilic composite broad-spectrum sunscreen agent comprises the following raw material components: (b1) UVA ultraviolet absorber; (b2) UVB ultraviolet absorber; (b3) ultraviolet absorber solvent; (b4) emulsifier; (b5) initiator; (b6) hydrophilic wall material monomer; (b7) water; The (c) temperature-sensitive sustained-release light stabilizer comprises the following raw material components: (c1) light stabilizer; (c2) temperature-sensitive hydrophilic wall material oligomer; (c3) temperature-sensitive wall material monomer; (c4) emulsifier; (c5) initiator; (c6) water; The (b1) UVA ultraviolet absorber is butyl methoxydibenzoylmethane; The (b2) UVB ultraviolet absorber is selected from at least one of 2-cyano-3,3-diphenylacrylic acid-2-ethylhexyl ester, salicylic acid-2-ethylhexyl ester, methoxycinnamic acid ethylhexyl ester, p-aminobenzoic acid, cinnamic acid ester, and camphor benzalkonium methyl sulfate.

2. The broad spectrum, lightfast, aqueous ink according to claim 1, characterized in that, Comprise the following components by weight: (a) aliphatic polyester type water-based polyurethane 25-35 parts; (b) hydrophilic composite broad-spectrum sunscreen agent 5-10 parts; (c) temperature-sensitive sustained-release light stabilizer 3-8 parts; (d) color paste 25-40 parts; (e) auxiliary agent 5-12 parts; (f) solvent 10-15 parts.

3. The broad spectrum, lightfast, aqueous ink according to claim 1, characterized in that, The (a) aliphatic polyester type water-based polyurethane comprises the following raw material components: (a1) aliphatic isocyanate; (a2) polyester polyol; (a3) hydrophilic chain extender; (a4) crosslinking agent; (a5) salt forming agent; (a6) catalyst; (a7) auxiliary agent.

4. Process for the preparation of a broad-spectrum lightfast aqueous ink according to any one of claims 1 to 3, characterized in that, Comprise the following steps: (1) Mix and stir (a) aliphatic polyester type water-based polyurethane and (d) color paste to obtain pre-dispersion A; (2) Add (b) hydrophilic composite broad-spectrum sunscreen agent and (c) temperature-sensitive sustained-release light stabilizer to pre-dispersion A, mix and stir to obtain pre-dispersion B; (3) Add (e) auxiliary agent and (f) solvent to pre-dispersion B, mix and stir, filter, and prepare the broad-spectrum sun-resistant water-based ink.

5. The production method according to claim 4, characterized by, The preparation method of the (b) hydrophilic composite broad-spectrum sunscreen agent comprises the following steps: Add emulsifier to water to obtain an aqueous phase; mix ultraviolet absorber solvent, UVA ultraviolet absorber, and UVB ultraviolet absorber to obtain a dispersion, then add hydrophilic wall material monomer to obtain an oil phase; mix the aqueous phase and the oil phase to obtain a pre-emulsion; mix the pre-emulsion and initiator in a protective gas atmosphere to obtain the hydrophilic composite broad-spectrum sunscreen agent.

6. The preparation method according to claim 4, characterized in that, The preparation method of the (c) temperature-sensitive sustained-release light stabilizer comprises the following steps: Mixing water, emulsifier and temperature-sensitive hydrophilic wall material oligomer to obtain an aqueous phase; mixing light stabilizer and temperature-sensitive wall material monomer at 40-60℃ to obtain an oil phase; mixing the aqueous phase and the oil phase, homogenizing to obtain an oil-in-water emulsion; adding emulsifier to the oil-in-water emulsion in a protective gas atmosphere, reacting at 75-95℃ for 1-3h, and drying to obtain the temperature-sensitive slow-release light stabilizer.

7. Use of the broad-spectrum lightfast water-based ink according to any one of claims 1-3 for the preparation of a printed article.

8. The method of using the broad spectrum lightfast water-based ink of any one of claims 1-3, characterized in that, comprising the steps of: printing the water-based ink on a substrate, baking and laminating.

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