Water-based printing coating combination, water-based printing process and application

Abstract

The present application relates to the technical field of decorative panels, and specifically to a water-based printing coating combination, a water-based printing process and an application. The water-based printing coating combination provided in the present application includes a water-based white primer, a water-based transparent mid-coat, a water-based inorganic pigment ink and a water-based transparent topcoat. The water-based printing process provided in the present application includes the following steps: first applying a water-based white primer, then applying a water-based transparent mid-coat, then performing inkjet printing with a water-based inorganic pigment ink, and finally applying a water-based transparent topcoat. The decorative panel is prepared by the above-mentioned water-based printing process using a cement decorative panel as a substrate, so that the decorative panel has good weather resistance and mechanical properties. The present application improves the construction process, the spraying process, and the coating and ink formula to make the coating system of inkjet printing more weather-resistant, reduce the drying temperature in the process flow, and improve the inkjet ink and coating formula to make the product color brighter and more vivid.

Description

Technical Field

[0001] The present application relates to the technical field of decorative panels, and in particular to a water-based printing coating combination, a water-based printing process and applications. Background Art

[0002] Cement decorative panels are widely used on exterior walls in different building fields due to their excellent mechanical properties, easy processing, low cost, and multiple functions. Traditional cement decorative panels usually adopt a simple coating method. This can only achieve the effect of pure color or simple lines and patterns, and cannot achieve beautiful complex pattern decoration effects.

[0003] There are also cement decorative panels printed with UV light-curable organic pigment inkjet inks on the market, but they have poor weather resistance and are not suitable for outdoor applications on exterior walls. Therefore, it is necessary to study corresponding technical solutions to solve this problem. Summary of the invention

[0004] The present application provides a water-based printing paint combination, a water-based printing process and an application, so that the prepared cement decorative board has better weather resistance.

[0005] In a first aspect, the present application provides a water-based printing coating combination, which is applied to cement decorative panels, including a water-based white base coating, a water-based transparent middle coating, a water-based inorganic pigment ink, and a water-based transparent face coating;

[0006] The water-based white base coating comprises the following components by weight percentage: 25-30% inorganic silicate resin, 5-10% inorganic hybrid modified latex, 20-25% coated activated micro powder, 15-20% titanium dioxide, 0.2-0.5% film-forming aid, and the balance is other processing aids and water;

[0007] The water-based transparent middle coating comprises the following components by weight percentage: 40-45% of inorganic hybrid modified resin, and the balance is other processing aids and water;

[0008] The aqueous inorganic pigment ink comprises the following components by weight percentage: 20-40% aqueous inorganic pigment paste, and the balance is other processing aids and water;

[0009] The water-based transparent face paint comprises a transparent face paint A agent and a transparent face paint B agent.

[0010] The transparent top coating agent A comprises the following components by weight percentage: 7-10% water-based inorganic resin, 65-70% water-based hydroxy acrylic dispersion resin, and the balance is other processing aids and water;

[0011] The transparent top coating agent B is composed of the following components in percentage by weight: 70-80% of hydrophilic modified polyhexamethylene diisocyanate and 20-30% of propylene glycol diacetate.

[0012] Through the above technical solution, the inorganic silicate resin in the water-based printing paint combination of the present application uses a silicon-based binder, which forms silicate under the action of carbon dioxide. When the water-based printing paint combination of the present application is coated on a fiber cement board, the paint has good bonding strength with the fiber cement board, which may be due to the presence of some uncarbonated lime on the fiber cement board, which will combine with the inorganic acid salt resin in the paint to form calcium silicate hydrate, thereby increasing the bonding strength of the water-based white primer with the substrate.

[0013] On this basis, the bottom coating uses inorganic hybrid modified emulsion, the middle coating uses inorganic hybrid modified resin, the water-based inorganic pigment ink uses water-based inorganic pigment paste, the surface coating A agent uses water-based inorganic resin and water-based hydroxy acrylic dispersion resin, and the transparent top coating B agent uses hydrophilic modified polyhexamethylene diisocyanate. By selecting the above components and the above ratio, a good combination of the base coating, the middle coating, the ink and the top coating can be achieved, and the weather resistance of the water-based printing of the cement decorative board can be further increased. The specific mechanism of action is derived as follows:

[0014] The water-based white base coating of the present application uses an inorganic hybrid modified emulsion in combination with an inorganic silicate resin. On the one hand, it can improve the compatibility of the inorganic silicate resin with the coated activated micropowder and titanium dioxide. On the other hand, the inorganic hybrid modified emulsion has good color retention, transparency, delicate appearance, high gloss and high hardness, which can further promote the inorganic silicate resin to better adhere to the fiber cement board to achieve firm adhesion; the additional titanium dioxide can form coated titanium dioxide under the action of the inorganic hybrid emulsion, and the coated titanium dioxide can effectively ensure that the water-based white base coating has a uniform and stable color presentation with the coated activated micropowder, so that the base layer can have good weather resistance to be suitable for outdoor use.

[0015] Inorganic hybrid modified resins are used in water-based transparent midcoats. On the one hand, the hybrid modified resins have improved compatibility with inorganic silicate resins in water-based white base coatings. On the other hand, the hybrid modified resins have better weather resistance, water resistance and moderate ink absorption capacity for upper printing inks.

[0016] The water-based inorganic resin used in the transparent topcoat A agent has good compatibility with the inorganic hybrid modified resin in the water-based transparent midcoat on the one hand, and can accelerate the drying speed of the coating and increase the hardness on the other hand. The water-based hydroxy acrylic dispersion resin in the transparent topcoat A agent has good flexibility, good water decomposition resistance, and good bonding effect. Propylene glycol diacetate in the transparent topcoat B agent is an excellent solvent, which facilitates the fusion of the transparent topcoat B agent and the transparent topcoat A agent. The hydrophilic modified polyhexamethylene diisocyanate in the transparent topcoat B agent has excellent weather resistance, wear resistance, and corrosion resistance. After cross-linking and curing with the hydroxyl functional group of the transparent topcoat A agent, it can form a coating with excellent mechanical properties, excellent chemical resistance, and weather resistance, which can maintain the long-term durability and stability of the overall printing coating system.

[0017] Preferably, the transparent top coating agent A and the transparent top coating agent B are mixed in a mass ratio of (3-5):1.

[0018] Through the above technical scheme, it has been experimentally verified that after the transparent topcoat A agent and the transparent topcoat B agent are mixed in a ratio range of (3-5):1, it helps to further increase the adhesion ability and long-term durability of the topcoat and effectively reduce the aging and shedding of the topcoat.

[0019] Preferably, the inorganic silicate resin in the water-based white base coating is at least one of COPSFECT-K99 potassium silicate and MOS-1010 stabilized potassium silicate.

[0020] Through the above technical scheme, the present application adopts the above inorganic silicate resin and inorganic hybrid emulsion to be mixed for use so as to be more suitable for combination with cement decorative panels, so as to improve the firmness of the combination between the water-based white primer and the cement decorative panels.

[0021] Preferably, the inorganic hybrid modified latex in the water-based white base coating is prepared as follows:

[0022] Preparation of modified silica sol: adding dipropylene glycol and vinyl triethoxysilane to silica sol, stirring and reacting to obtain modified silica sol;

[0023] Prepare mixed monomer: evenly mix butyl acrylate, methyl acrylate and acrylic acid to prepare mixed monomer;

[0024] Preparation of inorganic hybrid modified latex: adding initiator, pH regulator and water to modified silica sol to prepare initiator buffer solution, adding mixed monomers, keeping warm for reaction and filtering to obtain inorganic hybrid modified latex.

[0025] Through the above technical scheme, the silica sol is modified by adding dipropylene glycol and vinyl triethoxysilane to the inorganic hybrid modified emulsion, wherein the silane coupling agent vinyl triethoxysilane can increase the adhesion of the inorganic hybrid modified emulsion, and at the same time improve the hardness of the inorganic hybrid modified emulsion after drying. The inorganic hybrid modified emulsion thus prepared can have the characteristics of high film transparency, high hardness and strong adhesion after drying, further improving the weather resistance and water resistance of the water-based white primer.

[0026] Preferably, the inorganic hybrid modified resin in the water-based transparent middle coating is prepared according to the following steps:

[0027] Prefabricated resin prepolymers;

[0028] Mix water, silica sol, acetic acid and hydrochloric acid evenly, add methyltriethoxysilane and tetraethoxysilane under stirring, add resin prepolymer and butyl acetate after the reaction is completed, raise the temperature to reflux, and obtain inorganic hybrid modified resin.

[0029] Through the above technical solution, the resin is hybridized with inorganic silica, which changes the disadvantage of pure inorganic film with pores. The addition of polymer resin can close the pores and repair the defects of inorganic coating, so that the coating formed by inorganic hybrid modified resin has good corrosion resistance, salt spray resistance and excellent weather resistance. At the same time, the presence of inorganic components retains some pores in the dry film, which can have moderate ink absorption capacity for inkjet layer ink, and is more conducive to the diffusion and distribution of inkjet layer ink, so as to achieve better inkjet effect.

[0030] Preferably, the inorganic pigment paste in the aqueous inorganic pigment ink is prepared according to the following steps: an inorganic pigment, a dispersing resin, a dispersant and water are mixed into a premix, and the premix is ​​ground to a particle size of ≤0.1 μm.

[0031] Through the above technical solution, the premix is ​​finely ground to make the inkjet printing pattern more bright and vivid.

[0032] Preferably, other processing aids in the water-based white base coating include one or more combinations of thickeners, dispersants, leveling agents, defoamers, wetting agents, and bactericides;

[0033] Other processing aids in the waterborne clear middle coating include fungicides;

[0034] Other processing aids in the aqueous inorganic pigment ink include a combination of one or more of a binder, a cross-linking agent, a viscosity modifier, a surface tension modifier, a pH control agent, and a bactericide;

[0035] Other processing aids in the transparent topcoat A include a combination of one or more of a wetting agent, a defoaming agent, a cosolvent, a bactericide, and a thickener.

[0036] Through the above technical solution, the above processing aid is selected in the water-based white base coating, water-based transparent middle coating and transparent top coating to make the above coating more uniform and stable. The bactericide has a bactericidal effect and can reduce bacterial corrosion. The above processing aid is selected for the water-based inorganic pigment ink, and the inkjet effect of the water-based inorganic pigment ink is better.

[0037] Preferably, in the water-based inorganic pigment ink, the adhesive is a water-based modified self-crosslinking acrylate, the crosslinking agent is a mixture of one or two of water-based blocked isocyanate and water-based blocked carbodiimide, and the adhesive is used in combination with the crosslinking agent.

[0038] Through the above technical scheme, water-based inorganic pigment ink uses water-based modified self-cross-linking acrylate as a binder, and inorganic mineral pigments are used to prepare nano-scale inkjet color paste; on the one hand, the water-based modified self-cross-linking acrylate has good adhesion, adhesion and good weather resistance; on the other hand, the inorganic mineral pigment has excellent weather resistance, and on this basis, it is matched with a water-based blocked isocyanate curing agent and / or a water-based blocked carbodiimide to effectively carry out cross-linking and curing, thereby ensuring that the printing coating layer has good adhesion and color fastness with the transparent mid-coat layer and the surface layer, as well as excellent color stability.

[0039] In a second aspect, the present application provides a water-based printing process, using a fiber cement board as a substrate and applying the above-mentioned water-based printing coating combination, comprising the following steps:

[0040] Primer: Apply water-based white primer to the substrate to form a primer after drying;

[0041] Middle coating: Apply water-based transparent middle coating on the base coating to form middle coating after drying;

[0042] Printing: Spray water-based inorganic pigment ink on the middle coating for inkjet printing, and dry it at 40-50℃ to form a printing layer;

[0043] Top coating: Apply the water-based transparent top coating on the printed layer and dry at 40-50℃ to form the top coating.

[0044] Through the above technical solution, the baking temperature in the whole process is reduced to achieve a substrate that is easily denatured at high temperature (200-300°C), and inkjet printing can also be performed by the above water-based printing coating combination.

[0045] In a third aspect, the present application provides a water-based printed cement decorative board, comprising a substrate and a water-based printing paint combination layer coated on the substrate, wherein the water-based printing paint combination layer is formed by coating the above-mentioned water-based printing paint combination.

[0046] Through the above technical scheme, the cement board is subjected to fiber reinforcement treatment and then is applied to the above process for water-based inkjet printing, so that the water-based printed cement decorative board can achieve the effect of having good weather resistance and mechanical properties at the same time.

[0047] In summary, this application has the following beneficial effects:

[0048] 1. This application improves the composition and ratio of the water-based printing primer to strengthen the firmness of the water-based printing primer and the substrate. At the same time, a four-layer setting of water-based printing primer, water-based printing intermediate coating, inkjet printing coating and water-based printing top coating is adopted to improve the color fastness, printing clarity and outdoor weather resistance of the water-based printing of cement decorative panels.

[0049] 2. This application improves the composition and ratio of each coating of the water-based printing to further improve the bonding strength between the coatings and the water resistance and acid resistance of each coating, so as to improve the overall weather resistance.

[0050] 3. The water-based inorganic pigment ink of the present application adopts inorganic mineral pigments to prepare nano-scale inkjet color paste, and then adopts water-based modified self-cross-linking acrylate and cross-linking agent (water-based blocked isocyanate and / or water-based blocked carbon diimide) for cross-linking and curing. While ensuring the bright and vivid colors of the inkjet printing pattern, it also enhances the firmness of the bonding between the printing coating and other coatings.

[0051] 4. The present application provides a water-based printed cement decorative board having good weather resistance and mechanical properties. DETAILED DESCRIPTION

[0052] 1. Water-based printing coating combination

[0053] The water-based printing coating combination of the present application comprises a water-based white bottom coating, a water-based transparent middle coating, a water-based inorganic pigment ink and a water-based transparent surface coating.

[0054] 1. Water-based white base paint

[0055] The invention comprises the following components by weight percentage: 25-30% of inorganic silicate resin, 5-10% of inorganic hybrid modified latex, 20-25% of coated activated micropowder, 15-20% of titanium dioxide, 0.2-0.5% of film-forming aid, and the balance is other processing aids and water; the other processing aids include a combination of one or more of thickener, dispersant, leveling agent, defoamer, wetting agent and bactericide.

[0056] The water-based white base coating of the present application further preferably includes the following components by weight percentage: 25-30% inorganic silicate resin, 5-10% inorganic hybrid modified latex, 20-25% coated activated micropowder, 15-20% titanium dioxide, 0.2-0.5% film-forming aid; 0.2-0.5% thickener, 0.5-1.0% dispersant, 0.1-0.3% leveling agent, 0.1-0.3% defoamer, 0.1-0.3% wetting agent, 0.1-0.3% bactericide, and the balance is deionized water.

[0057] Among them, the inorganic silicate resin is obtained through market purchase; the present application prefers COPSFECT-K99 potassium silicate of Shanghai Xinshou Additive Co., Ltd. and / or MOS-1010 stabilized potassium silicate of Xiamen Peiteng Material Technology Co., Ltd.

[0058] The inorganic hybrid modified emulsion can be purchased from the market or prepared by oneself. For purchase from the market, AS-121 inorganic hybrid modified emulsion of Shanghai Wobeis New Materials Co., Ltd. and ES2704 inorganic hybrid modified emulsion of Shanghai Xinshou Auxiliary Agent Co., Ltd. can be selected; for preparation by oneself, the emulsion can be prepared according to the following steps:

[0059] ①, preparation of modified silica sol: add 20-5 parts of dipropylene glycol to 80-95 parts of silica sol, stir and react for 2-3 hours at room temperature to obtain modified silica sol; the modified silica sol of the present application is specifically prepared by adding 10 parts of dipropylene glycol to 90 parts of inorganic silica sol, stirring and reacting for 2 hours to obtain modified silica sol;

[0060] ②, prepare mixed monomer: 15-25 parts of butyl acrylate, 15-23 parts of methyl acrylate, and 0.5-1.5 parts of acrylic acid are mixed evenly to prepare a mixed monomer; the mixed monomer of the present application is specifically 20 parts of butyl acrylate, 19 parts of methyl acrylate, and 1 part of acrylic acid are mixed evenly to prepare a mixed monomer;

[0061] ③. Preparation of inorganic hybrid modified latex: Add initiator, pH regulator and 20-30 parts of water to 5-15 parts of modified silica sol to prepare initiator buffer solution, add mixed monomer twice, and keep warm for reaction for 1-3 hours. In this embodiment, 0.2 parts of initiator, pH regulator and 25 parts of deionized water are added to 10 parts of modified silica sol. The prepared initiator buffer solution is added to the mixed monomer twice, and the reaction is kept warm for 2 hours. After filtering, the inorganic hybrid modified latex is obtained.

[0062] The coated activated micropowder is prepared according to the following steps: add the silicon micropowder into the NaHCO3 solution, disperse it ultrasonically, and then slowly add the Al2(S04)3 solution. After the reaction is complete, filter and dry it, and calcine it at 300°C in an air atmosphere for 2 hours to complete the surface treatment of the silicon micropowder.

[0063] In addition, other processing aids can be adjusted as needed. The specific titanium dioxide is rutile titanium dioxide R-996+; the specific film-forming aid is dipropylene glycol butyl ether; the thickener can be hydroxyethyl cellulose ether, such as one or more of Germany's Shin-Etsu TYLOSE HS15000YP2, HS30000YP2 and HS100000YP2; the dispersant can be acrylic homopolymer sodium salt dispersant 3500, Special functional group hydrophobic copolymer dispersion stabilizer 3600 and modified phosphonate dispersion stabilizer 3700. One or more of the following: the leveling agent can be selected from polydimethylsiloxane modified polyacrylate and one or more of polyacrylate; the defoaming agent can be selected from one or more of silicone and polyether; the wetting agent can be selected from fatty alcohol polyoxyethylene ether wetting agents without APEO; the bactericide can be selected from isothiazolinone derivatives.

[0064] 2. Water-based transparent middle coating

[0065] The composition comprises, by weight percentage: 40-45% inorganic hybrid modified resin, 0.1-0.3% bactericide, and the rest deionized water;

[0066] Among them, the inorganic hybrid modified resin can be purchased from the market or made by oneself; for market purchase, AS-728 inorganic hybrid modified resin, AS-940 inorganic hybrid modified resin from Shanghai Wobeis New Materials Co., Ltd., G25 inorganic hybrid modified resin from Anhui Cima New Materials Co., Ltd., etc. can be selected. The homemade inorganic hybrid modified resin is prepared according to the following steps:

[0067] The polycaprolactone polyols CAPA3050 and CAPA2085 were reacted with succinic anhydride, 1-3% of the total mass of dibutyltin dilaurate was added, the reaction was carried out at room temperature for 24 hours, and aminopropyltriethoxysilane was added to react to obtain a polyurethane prepolymer;

[0068] Mix 15 parts of deionized water, 25 parts of inorganic silica sol, 2 parts of acetic acid and 0.3 parts of hydrochloric acid evenly, add 100 parts of methyltriethoxysilane and 20 parts of tetraethoxysilane under stirring, react for 2 hours, add 60 parts of polyurethane prepolymer and 100 parts of butyl acetate, raise the temperature to reflux, evaporate ethanol, and obtain inorganic hybrid modified resin.

[0069] The bactericide may be one or more of chlorophenols, isothiazolinones, and quaternary ammonium salts.

[0070] 3. Water-based inorganic pigment ink

[0071] The composition comprises the following components by weight percentage: 20-40% of water-based inorganic pigment paste, and the balance is other processing aids and water; the other processing aids include a combination of one or more of adhesives, crosslinking agents, viscosity regulators, surface tension regulators, pH control agents, and bactericides.

[0072] The aqueous inorganic pigment ink of the present application further preferably comprises the following components by weight percentage: 20.0-40.0% aqueous inorganic pigment paste, 5.0-20.0% binder, 1.2-5.0% crosslinking agent, 10.0-25.0% viscosity modifier, 0.2-1.0% surface tension modifier, 0.1-5.0% pH control agent, 0.3-1.0% bactericide, and the balance is deionized water;

[0073] The water-based inorganic pigment paste includes 30-50% inorganic pigment, 1.2-5% dispersing resin and 0.5-1% dispersing agent, and the rest is deionized water. After obtaining the above components, they are ground in a vertical sand mill using 0.2 μm zirconium beads, and then filtered using a polypropylene filter element or a glass fiber filter membrane with an absolute accuracy of 1.0 μm to obtain the inorganic pigment paste;

[0074] The inorganic pigment can be one or more of metal oxides, chromates, carbonates, sulfates and sulfides. The dispersing resin can be 7030 water-based acrylic hybrid siloxane resin from Shanghai Nengmo New Materials Co., Ltd. The dispersant can be BASF dispersant. Ultra PX 4585 is either ethylene-acrylic acid copolymer or ethylene-vinyl acetate copolymer or more thereof.

[0075] In addition, the adhesive and the crosslinking agent are used in the water-based inorganic pigment ink of the present application. The adhesive is preferably a water-based modified self-crosslinking acrylate, and the water-based modified acrylate copolymer emulsion (self-crosslinking) of Shanghai Xunda New Materials with the brand name HD-8088 is used as an example for illustration. The crosslinking agent is a mixture of one or two of water-based blocked isocyanate and water-based blocked carbodiimide, and the water-based blocked isocyanate curing agent with the model number LP-811 and the carbodiimide crosslinking agent with the model number UN-557 are used as examples for illustration.

[0076] The viscosity regulator can be selected from one or a mixture of glycerol, ethylene glycol, diethylene glycol, isopropanol, 1,2-hexanediol, 1,2-propylene glycol, 1,5-pentanediol, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol butyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, polyethylene glycol 400; the surface tension regulator can be selected from one or a mixture of Surfynol 465, Dynol 604, Surfynol104, Dynol607, TEGO WET240, TEGO WET280, JFC, carboxylic acid betaine, etc.; the pH control agent can be selected from one or a mixture of triethanolamine, monoethanolamine, triethylamine, diethanolamine, 2-aminoethanol, sodium tartrate, sodium citrate, etc.; the bactericide can be an isothiazolinone derivative.

[0077] 4. Clear face paint

[0078] The transparent topcoat comprises a transparent topcoat A agent and a transparent topcoat B agent, and the transparent topcoat A agent and the transparent topcoat B agent are mixed evenly in a mass ratio of (3-5):1 and then used as a transparent topcoat.

[0079] The transparent topcoat A comprises the following components by weight percentage: 7-10% water-based inorganic resin, 65-70% water-based hydroxy acrylic dispersion resin, and the balance is other processing aids and water; the other processing aids include a combination of one or more of a wetting agent, a defoaming agent, a cosolvent, a bactericide, and a thickener.

[0080] The transparent topcoat A of the present application further preferably comprises the following components by weight percentage: 7-10% aqueous inorganic resin, 65-70% aqueous hydroxy acrylic dispersion resin, 0.5-0.8% wetting agent, 0.1-0.3% defoamer, 2-4% cosolvent, 0.1-0.3% bactericide, 0.1-0.3% thickener, and the remainder deionized water.

[0081] The waterborne inorganic resin is AS-125 from Shanghai Wobeisi New Materials Co., Ltd. and ES2708 from Shanghai Xinshou Additives Co., Ltd. The waterborne hydroxylated acrylic dispersion resin is HD 2439 water-based hydroxy acrylic secondary dispersion resin, the wetting agent can be selected from one or more of acetylene glycol ethylene oxide adducts or acetylene glycol ethoxy compounds, polyether modified silicone resins, the defoaming agent can be selected from one or more of silicones and polyethers, the cosolvent can be selected from one or more of diethylene glycol butyl ether, dipropylene glycol methyl ether, and dipropylene glycol butyl ether, the bactericide can be selected from isothiazolinone derivatives, and the thickener can be selected from hydrophobically modified polyurethane thickeners.

[0082] 2. Coating process

[0083] The present application adopts a combination of a reasonably proportioned coating formula and a coating process to realize the entire water-based printing process at a relatively low temperature, thereby effectively improving the weather resistance of the water-based printing on the cement decorative board.

[0084] The water-based printing process of the present application comprises the following steps:

[0085] Primer: Apply water-based white primer to the substrate to form a primer after drying;

[0086] Middle coating: Apply water-based transparent middle coating on the base coating to form middle coating after drying;

[0087] Printing: Spray water-based inorganic pigment ink on the middle coating for inkjet printing, and dry it at 40-50℃ to form a printing layer;

[0088] Top coating: Apply the water-based transparent top coating on the printed layer and dry at 40-50℃ to form the top coating.

[0089] The present application is further described below in conjunction with specific embodiments and comparative examples.

[0090] Example 1

[0091] 1. A water-based printing paint combination, which consists of a water-based white bottom paint, a water-based transparent middle paint, a water-based inorganic pigment ink and a water-based transparent surface paint; the preparation method of the water-based printing paint combination comprises the following steps:

[0092] ①. Preparation of water-based white primer:

[0093] Take the preparation of 100kg water-based white primer as an example;

[0094] Prepare 28 kg of inorganic silicate resin (COPSFECT-K99 potassium silicate), 8 kg of the self-made inorganic hybrid modified latex, 22 kg of the self-made coated activated micropowder, 17 kg of rutile titanium dioxide (R-996+), 0.4 kg of dodecanol ester, 0.4 kg of gelatin, 0.7 kg of polyisobutylene, 0.2 kg of polydimethylsiloxane, 0.2 kg of polyoxypropylene glycerol ether, 0.2 kg of Tween (80), 0.2 kg of 1,2-benzisothiazol-3-one, and 22.7 kg of deionized water; add the above raw materials into the deionized water in sequence and mix well;

[0095] ②. Preparation of water-based transparent mid-coat:

[0096] Take the preparation of 100kg water-based transparent mid-coat as an example;

[0097] Prepare 43 kg of the self-made inorganic hybrid modified resin, 0.2 kg of 1,2-benzisothiazol-3-one, and the balance of deionized water; add the above raw materials into the deionized water in sequence and mix well.

[0098] ③. Preparation of water-based inorganic pigment ink:

[0099] Take the preparation of 100kg of water-based inorganic pigment ink as an example;

[0100] 45kg of inorganic pigments, plus 2kg of 7030 water-based acrylic hybrid siloxane resin from Heinengmo New Materials Co., Ltd. and BASF dispersant Ultra PX 45851kg, plus 51kg deionized water, ground with a vertical sand mill and 0.2μm zirconium beads, and filtered with a 1.0μm absolute precision polypropylene filter element to obtain a water-based inorganic pigment paste;

[0101] 35 kg of water-based inorganic pigment paste, 15 kg of water-based modified self-crosslinking acrylate (HD-8088), 3 kg of water-based blocked isocyanate (LP-811), 17 kg of ethylene glycol, 0.6 kg of Surfynol 465, 3.2 kg of triethanolamine, and 2 kg of 1,2-benzisothiazol-3-one were added to 24.2 kg of deionized water in sequence. The mixture was stirred evenly until all components were evenly mixed to obtain the water-based inorganic pigment ink.

[0102] ④. Preparation of transparent topcoat:

[0103] Preparation of transparent topcoat A: add 8 kg of 103 water-based inorganic resin, 67 kg of ZF-6101 water-based hydroxy acrylic secondary dispersion, 0.7 kg of propylene glycol, 0.2 kg of polyoxypropylene glycerol ether, 3 kg of n-propyl acetate, 0.2 kg of 1,2-benzisothiazol-3-one, and 0.2 kg of gelatin into 20.7 kg of deionized water in sequence and mix well;

[0104] Preparation of transparent top coating agent B: Obtain 75 kg of hydrophilic modified polyhexamethylene diisocyanate (C13-418005-100ML) and 25 kg of propylene glycol diacetate (111-55-7), and mix the two evenly.

[0105] Mix the transparent topcoat A and the transparent topcoat B in a mass ratio of 4:1.

[0106] 2. The preparation method of the water-based printed cement decorative board of the present application comprises the following steps:

[0107] ① Primer: Apply water-based white primer on the fiber reinforced cement board with a coating amount of 25g / m 2 , leave it at room temperature for 30 minutes to form a base coating after drying;

[0108] ② Middle coating: Apply water-based transparent middle coating on the base coating and leave it at room temperature for 30 minutes. The coating amount is 20g / m 2 , forming a middle coating after drying;

[0109] ③. Printing: Spray water-based inorganic pigment ink on the middle coating for inkjet printing, and dry it at 43°C for 75 minutes to form a printing layer;

[0110] ④. Top coating: Apply the water-based transparent top coating on the printed layer with a coating amount of 20g / m 2 , and dried at 43°C for 75 minutes to obtain a water-based printed cement decorative board.

[0111] Embodiment 2-4

[0112] Example 2-4 is based on Example 1, and the contents of inorganic silicate resin, inorganic hybrid modified latex, coated activated micropowder, titanium dioxide and dodecyl alcohol ester in every 100kg of water-based white base coating are adjusted as shown in Table 1, wherein the content of deionized water is adjusted accordingly to make up 100kg, and the other components are the same as Example 1.

[0113] Table 1 Content of each component per 100kg water-based white primer in Examples 1-4 and Comparative Examples 1-2

[0114]

[0115] Embodiment 5-7

[0116] Based on Example 1, the content of the inorganic hybrid modified resin in every 100 kg of the transparent middle coating is adjusted as shown in Table 2, and the rest is the same as Example 1.

[0117] Table 2 Inorganic hybrid modified resin content per 100 kg transparent middle coating in Examples 5-7 and Comparative Examples 3-4

[0118]

[0119]

[0120] Embodiment 8-10

[0121] Examples 8-10 Based on Example 1, the contents of water-based hydroxylated acrylic dispersion resin, hydrophilic modified polyhexamethylene diisocyanate and propylene glycol diacetate in 100 kg of water-based facial coating were adjusted as shown in Table 3. The rest was the same as Example 1.

[0122] Table 3 Content of each component in 100 kg water-based facial coating in Examples 8-10 and Comparative Examples 5-6

[0123]

[0124] Examples 11-13

[0125] Examples 11-13 are based on Example 1, and the ratio of the transparent facial coating agent A to the transparent facial coating agent A in the water-based facial coating is adjusted as shown in Table 4, and the rest is the same as Example 1.

[0126] Table 4 Ratio of the transparent face coating agent A to the transparent face coating agent B in Examples 11-13 and Comparative Examples 7-8

[0127] Clear face paint A: Clear face paint B Example 1 4:1 Embodiment 11 3:1 Example 12 3.5:1 Embodiment 13 5:1 Comparative Example 7 2:1 Comparative Example 8 6:1

[0128] Examples 14-16

[0129] In Examples 14-16, based on Example 1, the oven baking temperature and time were adjusted as shown in Table 5, and the rest were the same as Example 1.

[0130] Table 5 Baking temperature and baking time in Examples 14-16

[0131] Baking temperature (℃) Baking time (min) Embodiment 14 50 60 Embodiment 15 45 75 Example 16 40 85

[0132] Embodiment 17

[0133] The inorganic silicate resin adopts MOS-1010 stabilized potassium silicate purchased from Xiamen Pei Teng Company, and the rest is the same as in Example 1.

[0134] Embodiment 18

[0135] The inorganic silicate resin adopts Shanghai Xinshou COPSFECT-K99 potassium silicate and Xiamen Peiteng MOS-1010 stabilized potassium silicate purchased from the market, and the two are prepared in a weight ratio of 1:1. The rest is the same as in Example 1.

[0136] Embodiment 19

[0137] The inorganic silicate resin adopts 103 water-based inorganic resin purchased from the market, and has a hardness of 9H. The rest is the same as in Example 1.

[0138] Embodiment 20

[0139] The inorganic hybrid modified emulsion adopts ES2704 inorganic hybrid modified emulsion produced by Shanghai Xinshou, and the rest is the same as Example 1.

[0140] Embodiment 21

[0141] The inorganic hybrid modified resin adopts G25 inorganic hybrid modified resin produced by Anhui Ci Ma New Materials, and the rest is the same as in Example 1.

[0142] Comparative Example 9

[0143] The preparation method of the water-based printed cement decorative board comprises the following steps:

[0144] ① Primer: Apply water-based white primer on the fiber reinforced cement board with a coating amount of 25g / m 2 , leave it at room temperature for 30 minutes to form a base coating after drying;

[0145] ②, Printing: Spray water-based inorganic pigment ink on the middle coating for inkjet printing, and dry it at 43°C for 75 minutes to form a printing layer;

[0146] ④. Top coating: Apply the water-based transparent top coating on the printed layer with a coating amount of 20g / m 2 , and dried at 43° C. for 75 minutes to obtain a water-based printed cement decorative board; the rest is the same as in Example 1.

[0147] The ink is directly sprayed on the fiber reinforced cement board by an inkjet printer, and the water-based printed cement decorative board is obtained after drying.

[0148] Comparative Example 10

[0149] The ink is directly sprayed on the fiber reinforced cement board by an inkjet printer, and the water-based printed cement decorative board is obtained after drying.

[0150] Comparative Example 11

[0151] The preparation method of the water-based printed cement decorative board comprises the following steps:

[0152] ① Primer: Apply water-based white primer on the fiber reinforced cement board with a coating amount of 25g / m 2 , leave it at room temperature for 30 minutes to form a base coating after drying;

[0153] ②, Printing: Spray water-based inorganic pigment ink on the middle coating for inkjet printing, and dry it at 180°C for 15 minutes to form a printing layer;

[0154] ④. Top coating: Apply the water-based transparent top coating on the printed layer with a coating amount of 20g / m 2 , and dried at 180° C. for 15 minutes to obtain a water-based printed cement decorative board; the rest is the same as in Example 1.

[0155] Performance testing

[0156] 1. Carry out preliminary product inspection after processing is completed, and visually observe whether there is obvious deformation of the substrate after printing, and whether there are wrinkles and bubbles on the coating surface.

[0157] Results: After the processes described in Examples 1-21 and Comparative Examples 1-9 were completed, the substrates did not deform, and the coating surface did not wrinkle or bubble.

[0158] After the process described in Comparative Example 10 was completed, the coating surface also had wrinkles or bubbles, and the product was unqualified.

[0159] After the process described in Comparative Example 11 was completed, the substrate was deformed and the product was unqualified.

[0160] 2. Weather resistance test:

[0161] Weathering test standard refers to GB 1865-2009 Paint and varnish artificial weathering and artificial radiation exposure. The sample is subjected to weathering test by filtered xenon arc radiation. The radiation source of this test adopts the method 1 provided in 6.2 of GB 1865-2009. The radiation flux is selected between 300nm-400nm and the average irradiance is 60W / m 2 .

[0162] The measurement and recording standards refer to the "Rating Method for Aging of Paint and Varnish Coatings" (GB 1766-2008).

[0163] Sample preparation: According to the technical solutions described in Examples 1-21 and Comparative Examples 1-9, 10 pieces of each were manufactured and weather resistance tests were carried out under the same environment.

[0164] Recording cycle: Days are used as the time unit for weather resistance testing. Check once every half a day within three days of testing; after three days of testing, check once a day.

[0165] Comprehensive destructive evaluation: record the number of days it takes for each test board to reach the destruction degree level 1, the destruction quantity level 1, and the destruction size S2 for the first time. The recorded days for 10 boards of the same implementation method are summed and averaged.

[0166] Comprehensive color change evaluation: Record the number of days when each test board first reaches the color change level of 2. The sum of 10 boards of the same embodiment is taken as the average value.

[0167] Comprehensive cracking evaluation: record the number of days it takes for each test board to reach the first simultaneous crack quantity level 1 and crack size level S2, and take the average value of 10 boards of the same implementation method.

[0168] Comprehensive spalling evaluation: record the number of days it takes for each test board to reach spalling area level 1 and spalling size level S2 for the first time, and take the average value of 10 boards of the same implementation method.

[0169] Table 6 Weathering resistance test results

[0170]

[0171]

[0172] From the data of the weather resistance test of application examples 1-21, it can be seen that the present application has good weather resistance compared with comparative examples 1-11, among which embodiment 1 has the best comprehensive performance.

[0173] Combining Examples 1, 2, 3 and 4 and Comparative Examples 1 and 2, it can be seen that in the water-based white base coating of the present application, when the inorganic silicate resin is 25-30%, the inorganic hybrid modified emulsion is 5-10%, the coated activated micropowder is 20-25%, and the titanium dioxide is 15-20%, by weight percentage, the corresponding water-based printed cement decorative board is relatively stable in terms of anti-destruction performance, anti-cracking performance and anti-stripping performance. When the weight percentage of the inorganic silicate resin is 28%, the weight percentage of the inorganic hybrid modified emulsion is 8%, the weight percentage of the coated activated micropowder is 22%, and the weight percentage of the titanium dioxide is 17%, the overall water-based printed coating has better comprehensive anti-destruction, anti-cracking, and anti-stripping performance and the overall water-based printed coating has better anti-discoloration performance, so it is further preferred.

[0174] Combining Examples 1, 5, 6 and 7 and Comparative Examples 3 and 4, it can be seen that when the mass fraction of the inorganic hybrid modified resin is 40-45%, the water-based printing coating composite layer has better anti-damage performance, anti-discoloration performance, anti-cracking performance and anti-stripping performance. When the inorganic hybrid modified resin is too high or too low, it will break the balance between the bottom coating, the middle coating, the pigment coating and the surface coating, so that the anti-damage performance, the anti-discoloration performance, the anti-cracking performance and the anti-stripping performance are reduced to a certain extent. When the mass fraction of the inorganic hybrid modified resin is 43%, the anti-damage performance, the anti-discoloration performance, the anti-cracking performance and the anti-stripping performance of the water-based printing coating composite layer are the best.

[0175] Combining Examples 1, 8, 9 and 10 and Comparative Examples 5 and 6, it can be seen that when the weight percentage of the aqueous hydroxy acrylic dispersion resin in the transparent topcoat A is less than 65% and greater than 70%, the anti-cracking performance of the aqueous printing coating composite layer is significantly reduced, and other properties are also reduced. When the weight percentage of the aqueous hydroxy acrylic dispersion resin in the transparent topcoat A is 67%, the weight percentage of the hydrophilic modified polyhexamethylene diisocyanate in the transparent topcoat B is 76%, and the weight percentage of propylene glycol diacetate is 24%, the anti-cracking performance and anti-peeling performance of the aqueous printing coating composite layer are relatively excellent, so it is preferred in this application.

[0176] Combining Examples 1, 11, 12 and 13 and Comparative Examples 7 and 8, it can be seen that when the mixing ratio of transparent topcoat A agent to transparent topcoat B agent is less than 3:1 or greater than 5:1, the anti-cracking performance and anti-stripping performance of the water-based printing coating composite layer are significantly reduced. When the mixing ratio of transparent topcoat A agent to transparent topcoat B agent is 4:1, the anti-cracking performance and anti-stripping performance are better.

[0177] Combining Examples 1, 14, 15 and 16, it can be seen that the process flow of increasing the baking temperature and reducing the baking time will reduce the anti-cracking performance of the water-based printing coating combination layer. The process flow of reducing the baking temperature and increasing the baking time will reduce the anti-stripping performance of the water-based printing coating combination layer. The comprehensive performance of the process of drying the printing layer and the topcoat at 43°C for 75 minutes is better.

[0178] In combination with Examples 17-19, it can be seen that the use of other inorganic silicate resins sold on the market also shows good performance in anti-destruction performance, anti-cracking performance and anti-peeling performance. The inorganic silicate resin of the present application preferably uses COPSFECT-K99 potassium silicate and / or MOS-1010 stabilized potassium silicate. The inorganic silicate resin can be mixed with an inorganic hybrid emulsion to be more suitable for combination with cement decorative panels, thereby improving the firmness of the combination between the water-based white primer and the cement decorative panels.

[0179] In combination with Examples 20 and 21, it can be seen that although the inorganic hybrid modified emulsion and inorganic hybrid modified resin sold on the market can also perform well in terms of anti-destruction performance, anti-cracking performance and anti-peeling performance, the inorganic hybrid modified emulsion and inorganic hybrid modified resin prepared by the process provided in this application achieve better results.

[0180] Therefore, the present application improves the weather resistance of the inkjet printing coating system by improving the construction process, spraying process, coating and ink formula, reduces the drying temperature in the process flow, and improves the inkjet ink and coating formula to make the product color brighter and more vivid.

[0181] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A water-based printing paint combination, applied to cement decorative panels, characterized in that: Including water-based white base paint, water-based transparent middle paint, water-based inorganic pigment ink and water-based transparent face paint; The water-based white base coating comprises the following components by weight percentage: 25-30% inorganic silicate resin, 5-10% inorganic hybrid modified latex, 20-25% coated activated micro powder, 15-20% titanium dioxide, 0.2-0.5% film-forming aid, and the balance is other processing aids and water; The water-based transparent middle coating comprises the following components by weight percentage: 40-45% of inorganic hybrid modified resin, and the balance is other processing aids and water; The aqueous inorganic pigment ink comprises the following components by weight percentage: 20-40% aqueous inorganic pigment paste, and the balance is other processing aids and water; The water-based transparent face paint comprises a transparent face paint A agent and a transparent face paint B agent. The transparent top coating agent A comprises the following components by weight percentage: 7-10% water-based inorganic resin, 65-70% water-based hydroxy acrylic dispersion resin, and the balance is other processing aids and water; The transparent top coating agent B is composed of the following components in weight percentage: 70-80% of hydrophilic modified polyhexamethylene diisocyanate and 20-30% of propylene glycol diacetate; Other processing aids in the water-based white base coating include one or more combinations of thickeners, dispersants, leveling agents, defoamers, wetting agents, and bactericides; Other processing aids in the waterborne clear middle coating include fungicides; Other processing aids in the aqueous inorganic pigment ink include a combination of one or more of a binder, a cross-linking agent, a viscosity modifier, a surface tension modifier, a pH control agent, and a bactericide; Other processing aids in the transparent topcoat A include a combination of one or more of a wetting agent, a defoaming agent, a cosolvent, a bactericide, and a thickener.

2. A water-based printing paint combination according to claim 1, characterized in that: The transparent top coating agent A and the transparent top coating agent B are mixed and used in a mass ratio of (3-5):

1.

3. A water-based printing paint combination according to claim 1, characterized in that: The inorganic silicate resin in the water-based white base coating is at least one of COPSFECT-K99 potassium silicate and MOS-1010 stabilized potassium silicate.

4. A water-based printing paint combination according to claim 1, characterized in that: The inorganic hybrid modified emulsion in the water-based white base coating is prepared according to the following steps: Preparation of modified silica sol: adding dipropylene glycol and vinyl triethoxysilane to silica sol, stirring and reacting to obtain modified silica sol; Prepare mixed monomer: evenly mix butyl acrylate, methyl acrylate and acrylic acid to prepare mixed monomer; Preparation of inorganic hybrid modified latex: adding initiator, pH regulator and water to modified silica sol to prepare initiator buffer solution, adding mixed monomers, keeping warm for reaction and filtering to obtain inorganic hybrid modified latex.

5. A water-based printing paint combination according to claim 1, characterized in that: The inorganic hybrid modified resin in the water-based transparent middle coating is prepared according to the following steps: Prefabricated resin prepolymers; Mix water, silica sol, acetic acid and hydrochloric acid evenly, add methyltriethoxysilane and tetraethoxysilane under stirring, add resin prepolymer and butyl acetate after the reaction is completed, raise the temperature to reflux, and obtain inorganic hybrid modified resin.

6. A water-based printing paint combination according to claim 1, characterized in that: The inorganic pigment paste in the aqueous inorganic pigment ink is prepared by the following method: an inorganic pigment, a dispersing resin, a dispersant and water are mixed into a premix, and the premix is ​​ground to a particle size of ≤0.1 μm.

7. A water-based printing paint combination according to claim 1, characterized in that: In the water-based inorganic pigment ink, the adhesive is a water-based modified self-crosslinking acrylate, the crosslinking agent is a mixture of one or two of water-based blocked isocyanate and water-based blocked carbodiimide, and the adhesive is used in combination with the crosslinking agent.

8. A water-based printing process, characterized in that: Using a fiber cement board as a substrate, coating with the water-based printing coating combination as claimed in any one of claims 1 to 7 comprises the following steps: Primer: Apply water-based white primer to the substrate to form a primer after drying; Middle coating: Apply water-based transparent middle coating on the base coating to form middle coating after drying; Printing: Spray water-based inorganic pigment ink on the middle coating for inkjet printing, and dry it at 40-50℃ to form a printing layer; Top coating: Apply the water-based transparent top coating on the printed layer and dry at 40-50℃ to form the top coating.

9. A water-based printed cement decorative board, characterized in that: The invention comprises a substrate and a water-based printing coating combination layer coated on the substrate, wherein the water-based printing coating combination layer is formed by coating the water-based printing coating combination according to any one of claims 1 to 7.

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