CN118006213A - Preparation method of environment-friendly spray painting printing base coat - Google Patents
Preparation method of environment-friendly spray painting printing base coat Download PDFInfo
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- CN118006213A CN118006213A CN202410098259.8A CN202410098259A CN118006213A CN 118006213 A CN118006213 A CN 118006213A CN 202410098259 A CN202410098259 A CN 202410098259A CN 118006213 A CN118006213 A CN 118006213A
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- Prior art keywords
- spray painting
- water
- environment
- base coat
- printing base
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- 238000007639 printing Methods 0.000 title claims abstract description 64
- 238000007592 spray painting technique Methods 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 239000007787 solid Substances 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 22
- -1 acrylic ester Chemical class 0.000 claims abstract description 20
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000000080 wetting agent Substances 0.000 claims abstract description 14
- 239000008213 purified water Substances 0.000 claims abstract description 13
- 230000001105 regulatory effect Effects 0.000 claims abstract description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 4
- 239000002585 base Substances 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 38
- 239000004925 Acrylic resin Substances 0.000 claims description 17
- 229920000178 Acrylic resin Polymers 0.000 claims description 17
- 239000000805 composite resin Substances 0.000 claims description 16
- 229920005749 polyurethane resin Polymers 0.000 claims description 16
- 239000013339 polymer-based nanocomposite Substances 0.000 claims description 13
- 229920005989 resin Polymers 0.000 claims description 13
- 239000011347 resin Substances 0.000 claims description 13
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- 229920006318 anionic polymer Polymers 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 9
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 6
- 229920005792 styrene-acrylic resin Polymers 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 5
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229920005603 alternating copolymer Polymers 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 239000011858 nanopowder Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 229920003009 polyurethane dispersion Polymers 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- 238000007641 inkjet printing Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000000976 ink Substances 0.000 description 10
- 229920002635 polyurethane Polymers 0.000 description 10
- 239000004814 polyurethane Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 239000004744 fabric Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000004753 textile Substances 0.000 description 6
- 238000007865 diluting Methods 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241001522633 Betula utilis subsp. albosinensis Species 0.000 description 1
- 239000008830 Carthamus tinctorius Honghua extract Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a preparation method of an environment-friendly spray painting printing primer, which comprises the steps of firstly adding a water-based polyurethane dispersion with a solid content of 40% into a reaction kettle, and heating to 60 ℃; then adding the aqueous acrylic ester dispersoid with the solid content of 40%, and stirring and mixing uniformly at 60 ℃; adding nano mesoporous silica, and performing ultrasonic dispersion for 2 hours; then adding a silane coupling agent and purified water, and adjusting the solid content to 25-35%; then cooling to 40 ℃, dropwise adding ammonia water, regulating the pH value to be 8-9, and finally sequentially adding a defoaming agent, a leveling agent and a wetting agent to obtain the environment-friendly spray painting printing base coat.
Description
Technical Field
The invention relates to a polymer-based nanocomposite, in particular to a preparation method of an environment-friendly spray painting printing base coat.
Background
With the development of economy, the world is moving into a new industrialized age, and environmental pollution has become a troublesome problem facing countries around the world. Therefore, the promotion of energy conservation and emission reduction through industrial upgrading and transformation is urgent while the economy is developed and the folk life is improved. The European and American countries have established limit standards for the emission of organic volatile compounds (VOCs) from coating materials, and China is also actively taking the role of promoting industry transformation and upgrading. Therefore, the industries such as traditional solvent-based paint/ink/adhesive must finish industrial upgrading or transformation under the environment-friendly requirement. Therefore, the development of solvent-free or environmentally friendly coating materials is of great practical importance.
The prior patent: the invention name is as follows: a digital spray painting camouflage network and a preparation method thereof (hereinafter referred to as comparison file) have the application number: 202210867145.6, ①, and the ink absorbing layer adopted by the comparison document uses a single resin, namely aqueous polyurethane, so that the cost is high, and when multicolor patterns are printed, the phenomenon of ink stringing among different colors can occur.
② . The inorganic filler (kaolin, titanium white, talcum powder and silicon dioxide) is used in a large amount in the comparison document and the existing patent, and the density of the inorganic filler is far higher than that of the aqueous polyurethane resin, so that the delamination and phase separation easily occur, the stability of a reservoir is poor, the printing color is dim, and the contrast is poor. As shown in fig. 1.
Therefore, there is an urgent need for a preparation method to solve the above problems.
Disclosure of Invention
The invention aims to overcome the defects of the background technology, and provides a preparation method of an environment-friendly spray painting printing base coat, which has good flexibility, weather resistance, wear resistance, scratch resistance and excellent mechanical properties.
The invention is implemented by the following technical scheme: the preparation method of the environment-friendly spray painting printing base coat comprises the following steps:
Step 1, adding 30 to 40 percent of aqueous polyurethane resin with solid content into a reaction kettle or a dispersion container, and heating to a reaction temperature of 55 to 70 ℃;
Step 2, adding 30 to 40 percent of aqueous acrylic resin with solid content into a reaction kettle or a dispersion container, maintaining the reaction temperature, and stirring and mixing for A hours to obtain polymer composite resin;
Step 3, adding nano mesoporous silica into a reaction kettle or a dispersing container, maintaining the reaction temperature, and performing ultrasonic dispersion for B hours to obtain a polymer-based nanocomposite;
Step 4, adding purified water into a reaction kettle or a dispersing container, and blending the polymer-based nanocomposite to the required solid content;
step 5, cooling the reaction kettle or the dispersing container to 35-45 ℃, adding ammonia water, and regulating the pH value to 8-9;
And step 6, adding an auxiliary agent into the reaction kettle or the dispersing container, and stirring and mixing uniformly at the temperature of 35-45 ℃ to obtain the environment-friendly spray painting printing base coat.
In the technical scheme, the method comprises the following steps: the auxiliary agent comprises a water-based defoaming agent, a water-based leveling agent, a water-based wetting agent and a silane coupling agent, wherein the proportions among the water-based defoaming agent, the water-based leveling agent, the water-based wetting agent and the silane coupling agent are as follows: 0.5:0.5:0.5:1.
In the technical scheme, the method comprises the following steps: in the step 1, the aqueous polyurethane resin is an aromatic anionic polymer and comprises toluene diisocyanate type, diphenylmethane diisocyanate type or an alternating copolymer of the toluene diisocyanate type and the diphenylmethane diisocyanate type.
In the technical scheme, the method comprises the following steps: in the step 1, the hydrophilic functional group of the anionic polymer is ammonium carboxylate.
In the technical scheme, the method comprises the following steps: in the step 2, the aqueous acrylic resin is an anionic polymer, and the aqueous acrylic resin comprises aqueous styrene-acrylic resin or aqueous hydroxypropyl resin.
In the technical scheme, the method comprises the following steps: in the step 2, the water-based styrene-acrylic resin comprises a polymer formed by copolymerizing more than two of styrene, methacrylic acid, acrylonitrile, methyl methacrylate, butyl methacrylate and octyl methacrylate.
In the technical scheme, the method comprises the following steps: the water-based hydroxypropyl resin comprises a polymer formed by copolymerizing any one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate and epoxy modified acrylate with any one of methacrylic acid, acrylonitrile, methyl methacrylate, butyl methacrylate and octyl methacrylate.
In the technical scheme, the method comprises the following steps: in the step 3, the nano mesoporous silica is synthesized by a gas phase method, the particle size distribution is 5-10nm, the nano mesoporous silica has a mesoporous structure, and the nano mesoporous silica has hydrophilic nano particles after surface modification;
In the step 3, in the using process, the nano mesoporous silica is directly added into the aqueous resin dispersion in the form of nano powder or in the form of sol, when the sol is adopted, the nano mesoporous silica is directly prepared into silica sol by purified water, the pH value of the silica sol is regulated to 8-10 by alkali liquor, and the solid content is 30% -40%.
In the technical scheme, the method comprises the following steps: in the step 2, A is 0.5-1.5, and B is 1.5-2.5 in the step 3.
In the technical scheme, the method comprises the following steps: in the step 6, the water-based defoaming agent is an oligomer or mineral oil containing ether bonds, the water-based leveling agent is an organosilicon modified oligomer, the water-based wetting agent is a nonionic or anionic oligomer surfactant, and the silane coupling agent is one of gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane or gamma-methacryloxypropyl trimethoxysilane.
The invention has the following beneficial effects:
1. The invention uses purified water as solvent, has no VOC emission problem, and is environment-friendly.
2. The main resin of the spray painting printing prime coat is a compound of water-based acrylic ester and water-based polyurethane.
3. According to the invention, the spray painting printing primer is introduced with silica nanoparticles, so that the hardness and mechanical strength of the material are improved, and the material has good wear resistance and scratch resistance; meanwhile, the coating has good ink absorbency and printing adaptability due to the mesoporous structure of the silicon dioxide.
4. In the invention, a small amount of coupling agent is introduced to promote the cross-linking reaction between polymer molecules, thereby forming a network structure.
5. The polymer-based nanocomposite can be used as an inkjet printing primer to be applied to the fields of fabric impregnation, cloth surface treatment, canvas, inkjet printing primer of PET (polyethylene terephthalate) base materials, digital printing primer of cloth base and PET base materials and printing packaging which have very strict requirements on VOC emission.
6. Compared with the comparison document or the prior patent, the invention adopts the nano mesoporous silica to replace the inorganic filler, and the silica has the advantages of nano-scale particle size, small density and large specific surface area, and can stably suspend in a composite resin system for a long time. In addition, due to the mesoporous structure of the nano silicon dioxide, the ink absorption of the material is greatly improved, and the material can be suitable for spray painting printing of various inks and water ink and has wide printing adaptability.
7. Compared with the comparison document, the invention uses the waterborne polyurethane modified by the waterborne acrylic ester to obtain the polymer-based composite material as the primer, thereby greatly reducing the cost, effectively solving the problem of multicolor printing ink-stringing, and the overall printed pattern has bright and full color.
Drawings
FIG. 1 is a graph showing the effect of inkjet printing using commercial base coat.
Fig. 2 is a graph showing the effect of inkjet printing according to embodiment 1.
Detailed Description
To further illustrate the technology of the present invention, the following detailed description is provided in connection with specific examples, which include but are not limited to the following examples.
Referring to fig. 2, it is shown: the preparation method of the environment-friendly spray painting printing base coat comprises the following steps:
Step 1, adding 30 to 40 percent of aqueous polyurethane resin with solid content into a reaction kettle or a dispersion container, and heating to a reaction temperature of 55 to 70 ℃;
Step 2, adding 30 to 40 percent of aqueous acrylic resin with solid content into a reaction kettle or a dispersion container, maintaining the reaction temperature, and stirring and mixing for A hours to obtain polymer composite resin;
Step 3, adding nano mesoporous silica into a reaction kettle or a dispersing container, maintaining the reaction temperature, and performing ultrasonic dispersion for B hours to obtain a polymer-based nanocomposite;
Step 4, adding purified water into a reaction kettle or a dispersing container, and blending the polymer-based nanocomposite to the required solid content;
step 5, cooling the reaction kettle or the dispersing container to 35-45 ℃, adding ammonia water, and regulating the pH value to 8-9;
Step 6, adding an auxiliary agent into the reaction kettle or the dispersing container, stirring and mixing uniformly at the temperature of 35-45 ℃ to obtain the environment-friendly spray painting printing base coat,
The auxiliary agent comprises a water-based defoaming agent, a water-based leveling agent, a water-based wetting agent and a silane coupling agent.
The raw materials and the auxiliary agent are adopted according to the weight parts, and the contents of the components are as follows:
In the step 1, the aqueous polyurethane resin is an aromatic anionic polymer and comprises toluene diisocyanate type, diphenylmethane diisocyanate type or an alternating copolymer of the toluene diisocyanate type and the diphenylmethane diisocyanate type.
In the step1, the hydrophilic functional group of the anionic polymer is ammonium carboxylate.
In the step 2, the aqueous acrylic resin is an anionic polymer, and the aqueous acrylic resin comprises aqueous styrene-acrylic resin or aqueous hydroxypropyl resin.
In the step 2, the water-based styrene-acrylic resin is a polymer formed by copolymerizing styrene and any one or more than two monomers of methacrylic acid, acrylonitrile, methyl methacrylate, butyl methacrylate and octyl methacrylate;
The water-based hydroxypropyl resin is a polymer formed by copolymerizing one or more of hydroxyethyl methacrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate and epoxy modified acrylate with one or more monomers of methacrylic acid, acrylonitrile, methyl methacrylate, butyl methacrylate and octyl methacrylate.
In the step 3, the nano mesoporous silica is synthesized by a gas phase method, the particle size distribution is 5-10nm, the nano mesoporous silica has a mesoporous structure, and the nano mesoporous silica has hydrophilic nano particles after surface modification;
In the step 3, in the using process, the nano mesoporous silica is directly added into the aqueous resin dispersion in the form of nano powder or in the form of sol, when the sol is adopted, the nano mesoporous silica is directly prepared into silica sol by purified water, the pH value of the silica sol is regulated to 8-10 by alkali liquor, and the solid content is 30% -40%.
In the step 2, A is 0.5-1.5, and B is 1.5-2.5 in the step 3.
In the step 6, the aqueous defoaming agent is an oligomer or mineral oil containing ether bonds, the aqueous leveling agent is an organosilicon modified oligomer, the aqueous wetting agent is a nonionic or anionic oligomer surfactant, and the silane coupling agent is one of gamma-aminopropyl triethoxysilane (KH-550), gamma-glycidoxypropyl trimethoxysilane (KH-560) or gamma-methacryloxypropyl trimethoxysilane (KH-570).
Example 1
The preparation method of the environment-friendly spray painting printing base coat comprises the following components in parts by weight:
The preparation process of the environment-friendly spray painting printing base coat comprises the following steps: metering the waterborne polyurethane resin with the solid content of 40 percent into a reaction kettle, and heating to 60 ℃ while stirring; adding self-made water-based acrylic resin with the solid content of 40% into a reaction kettle according to the metering, and stirring and mixing uniformly at 60 ℃ to obtain the composite resin of the acrylic ester modified polyurethane; adding silica sol with the solid content of 40% into the composite resin, and stirring and dispersing uniformly; adding purified water according to the metering, and diluting the solid content to 30%; then ammonia water is added into the system in a dropwise manner, and the pH value is regulated to be 8-10; and finally, sequentially adding an antifoaming agent, a leveling agent, a wetting agent and other aqueous auxiliary agents according to the metering, stirring and uniformly mixing to obtain the polymer-based nanocomposite, which can be used as an inkjet printing base coat in the field of textiles.
The environment-friendly spray painting printing primer has the greatest advantages that the raw materials used in the invention do not relate to organic solvents, the VOC content of the product is strictly controlled, and the primer is different from the traditional solvent type spray painting printing primer; the composite process is simple, the coating performance is excellent, and the method is suitable for spray painting and printing of various fabrics.
Example 1 environmental friendly inkjet printing primer performance test results:
| Test item | Test method | Test results |
| Appearance of | Observation method | Milky white emulsion |
| Solid content (%) | GB1725-79 2004 | 30±1 |
| PH value | GB/T23769-2009 | 8.5 |
| Adhesion force | GB/T 1720-1979(89) | ≤1 |
| Hardness of | GB/T 1720-1979(89) | ≥2H |
| Viscosity of the mixture | (Coating 4 cup at 25 ℃ C.) | 20+ -1 Seconds |
| Dyne value | Dyne pen | 38 |
Example 2
The preparation method of the environment-friendly spray painting printing base coat comprises the following components in parts by weight:
The preparation process of the environment-friendly spray painting printing base coat comprises the following steps: metering self-made waterborne polyurethane resin with the solid content of 40 percent into a reaction kettle, and heating to 60 ℃ while stirring; adding self-made water-based acrylic resin with the solid content of 40% into a reaction kettle according to the metering, and stirring and mixing uniformly at 60 ℃ to obtain the composite resin of the acrylic ester modified polyurethane; adding silica sol with the solid content of 40% into the composite resin, and stirring and dispersing uniformly; adding purified water according to the metering, and diluting the solid content to 30%; then ammonia water is added into the system in a dropwise manner, and the pH value is regulated to be 8-10; and finally, sequentially adding an antifoaming agent, a leveling agent, a wetting agent and other aqueous auxiliary agents according to the metering, stirring and uniformly mixing to obtain the polymer-based nanocomposite, which can be used as an inkjet printing base coat in the field of textiles.
The environment-friendly spray painting printing primer has the greatest advantages that the raw materials used in the invention do not relate to organic solvents, the VOC content of the product is strictly controlled, and the primer is different from the traditional solvent type spray painting printing primer; the composite process is simple, the coating performance is excellent, and the method is particularly suitable for digital printing of PET cloth as a base material.
Example 2 environmental friendly inkjet print primer performance test results:
| Test item | Test method | Test results |
| Appearance of | Observation method | Milky white emulsion |
| Solid content (%) | GB1725-79 2004 | 30±1 |
| PH value | GB/T23769-2009 | 9 |
| Adhesion force | GB/T 1720-1979(89) | ≤1 |
| Hardness of | GB/T 1720-1979(89) | ≥2H |
| Viscosity of the mixture | (Coating 4 cup at 25 ℃ C.) | 20+ -1 Seconds |
| Dyne value | Dyne pen | 36-38 |
Example 3
The preparation method of the environment-friendly spray painting printing base coat comprises the following components in parts by weight:
The preparation process of the environment-friendly spray painting printing base coat comprises the following steps: metering self-made waterborne polyurethane resin with the solid content of 40 percent into a reaction kettle, and heating to 60 ℃ while stirring; adding self-made water-based acrylic resin with the solid content of 40% into a reaction kettle according to the metering, and stirring and mixing uniformly at 60 ℃ to obtain the composite resin of the acrylic ester modified polyurethane; adding silica sol with the solid content of 40% into the composite resin, and stirring and dispersing uniformly; adding purified water according to the metering, and diluting the solid content to 30%; then ammonia water is added into the system in a dropwise manner, and the pH value is regulated to be 8-10; and finally, sequentially adding an antifoaming agent, a leveling agent, a wetting agent and other aqueous auxiliary agents according to the metering, stirring and uniformly mixing to obtain the polymer-based nanocomposite, which can be used as an inkjet printing base coat in the field of textiles.
The environment-friendly spray painting printing primer has the greatest advantages that the raw materials used in the invention do not relate to organic solvents, the VOC content of the product is strictly controlled, and the primer is different from the traditional solvent type spray painting printing primer; the composite process is simple, the coating performance is excellent, and the composite process is suitable for the base coat of spray painting printing or digital printing of various fabrics.
Example 3 environmental friendly inkjet print primer performance test results:
| Test item | Test method | Test results |
| Appearance of | Observation method | Milky white emulsion |
| Solid content (%) | GB1725-79 2004 | 30±1 |
| PH value | GB/T23769-2009 | 9.5 |
| Adhesion force | GB/T 1720-1979(89) | ≤1 |
| Hardness of | GB/T 1720-1979(89) | ≥2H |
| Viscosity of the mixture | (Coating 4 cup at 25 ℃ C.) | 20+ -1 Seconds |
| Dyne value | Dyne pen | 38-40 |
Example 4
The preparation method of the environment-friendly spray painting printing base coat comprises the following components in parts by weight:
The preparation process of the environment-friendly spray painting printing base coat comprises the following steps: metering self-made waterborne polyurethane resin with the solid content of 40 percent into a reaction kettle, and heating to 60 ℃ while stirring; adding self-made water-based acrylic resin with the solid content of 40% into a reaction kettle according to the metering, and stirring and mixing uniformly at 60 ℃ to obtain the composite resin of the acrylic ester modified polyurethane; adding nano mesoporous silica powder into the composite resin, simultaneously adding purified water according to the metering, diluting the solid content to 30%, and stirring and dispersing for at least 2 hours; then ammonia water is added into the system in a dropwise manner, and the pH value is regulated to be 8-10; and finally, sequentially adding an antifoaming agent, a leveling agent, a wetting agent and other aqueous auxiliary agents according to the metering, stirring and uniformly mixing to obtain the polymer-based nanocomposite, which can be used as an inkjet printing base coat in the field of textiles.
The environment-friendly spray painting printing primer has the greatest advantages that the raw materials used in the invention do not relate to organic solvents, the VOC content of the product is strictly controlled, and the primer is different from the traditional solvent type spray painting printing primer; the composite process is simple, the coating performance is excellent, and the composite material is suitable for the base coat of various textile spray painting printing or digital printing.
The invention provides an environment-friendly spray painting printing primer, which is prepared by adopting any one of the preparation methods and is applied to spray painting printing of fabric impregnation and canvas, spray painting printing or digital printing of cloth and PET (polyethylene terephthalate) base materials.
The main resin of the environment-friendly spray painting printing primer is a composite resin obtained by blending the aqueous polyurethane resin and the aqueous acrylic resin, and has good compatibility, stability and dispersibility because the aqueous polyurethane resin and the aqueous acrylic resin are both anionic polymers. The aqueous acrylic ester blending modified aqueous polyurethane is a polymer composite resin; the resin has a large amount of hydrophilic functional groups, and can form stable dispersion when water is added for dispersion; after a small amount of coupling agent is added into the system to hydrolyze, a crosslinking reaction occurs between molecules, so that an interpenetrating network structure is formed; because of the hydrophilic functional groups and the interpenetrating network structure, the silica nanoparticle has good dispersing and stabilizing effects. Because of the mesoporous structure of the nano silicon dioxide, the nano silicon dioxide has good ink absorption or printing adaptability to different types of ink or water ink.
Example 4 environmental friendly inkjet printing primer performance test results:
| Test item | Test method | Test results |
| Appearance of | Observation method | Milky white emulsion |
| Solid content (%) | GB1725-79 2004 | 30±1 |
| PH value | GB/T23769-2009 | 8.5-9 |
| Adhesion force | GB/T 1720-1979(89) | ≤1 |
| Hardness of | GB/T 1720-1979(89) | ≥2H |
| Viscosity of the mixture | (Coating 4 cup at 25 ℃ C.) | 20+ -1 Seconds |
| Dyne value | Dyne pen | 36-38 |
Example 5
The preparation method of the environment-friendly spray painting printing base coat comprises the following components in parts by weight:
The preparation process of the environment-friendly spray painting printing base coat comprises the following steps: metering self-made waterborne polyurethane resin with the solid content of 40 percent into a reaction kettle, and heating to 60 ℃ while stirring; adding self-made water-based acrylic resin with the solid content of 40% into a reaction kettle according to the metering, and stirring and mixing uniformly at 60 ℃ to obtain the composite resin of the acrylic ester modified polyurethane; adding nano silicon dioxide powder into the composite resin, simultaneously adding purified water according to the metering, diluting the solid content to 30%, and stirring and dispersing for at least 2 hours; then ammonia water is dripped into the system, and the pH value is regulated to be about 10; and finally, sequentially adding an antifoaming agent, a leveling agent, a wetting agent and other aqueous auxiliary agents according to the metering, stirring and uniformly mixing to obtain the polymer-based nanocomposite, which can be used as an inkjet printing base coat in the field of textiles.
The environment-friendly spray painting printing primer has the greatest advantages that the raw materials used in the invention do not relate to organic solvents, the VOC content of the product is strictly controlled, and the primer is different from the traditional solvent type spray painting printing primer; the composite process is simple, the coating performance is excellent, and the composite material is suitable for spray painting printing or printing base coat of various base materials.
Example 5 environmental friendly inkjet printing primer performance test results:
| Test item | Test method | Test results |
| Appearance of | Observation method | Milky white emulsion |
| Solid content (%) | GB1725-79 2004 | 30±1 |
| PH value | GB/T23769-2009 | 10 |
| Adhesion force | GB/T 1720-1979(89) | ≤1 |
| Hardness of | GB/T 1720-1979(89) | ≥2H |
| Viscosity of the mixture | (Coating 4 cup at 25 ℃ C.) | 20+ -1 Seconds |
| Dyne value | Dyne pen | 40 |
It should be noted that, the aqueous polyurethane resin and the aqueous acrylic resin of the present invention can be selected from commercial product brands, such as products publicly sold by the science and technology company of new material of Chinese Honghua, the aqueous polyurethane brands: HY-101; waterborne acrylate brand: HY-201. The aqueous polyurethane resin can be prepared by adopting the technology disclosed by CN 201410246512.6.
The above-mentioned parts which are not described in detail are all prior art.
Claims (10)
1. A preparation method of an environment-friendly spray painting printing base coat is characterized by comprising the following steps of: the method comprises the following steps:
Step 1, adding 30 to 40 percent of aqueous polyurethane resin with solid content into a reaction kettle or a dispersion container, and heating to a reaction temperature of 55 to 70 ℃;
Step 2, adding 30 to 40 percent of aqueous acrylic resin with solid content into a reaction kettle or a dispersion container, maintaining the reaction temperature, and stirring and mixing for A hours to obtain polymer composite resin;
Step 3, adding nano mesoporous silica into a reaction kettle or a dispersing container, maintaining the reaction temperature, and performing ultrasonic dispersion for B hours to obtain a polymer-based nanocomposite;
Step 4, adding purified water into a reaction kettle or a dispersing container, and blending the polymer-based nanocomposite to the required solid content;
step 5, cooling the reaction kettle or the dispersing container to 35-45 ℃, adding ammonia water, and regulating the pH value to 8-9;
And step 6, adding an auxiliary agent into the reaction kettle or the dispersing container, and stirring and mixing uniformly at the temperature of 35-45 ℃ to obtain the environment-friendly spray painting printing base coat.
2. The method for preparing the environment-friendly spray painting printing base coat as claimed in claim 1, which is characterized by comprising the following steps: the auxiliary agent comprises a water-based defoaming agent, a water-based leveling agent, a water-based wetting agent and a silane coupling agent, wherein the proportions among the water-based defoaming agent, the water-based leveling agent, the water-based wetting agent and the silane coupling agent are as follows: 0.5:0.5:0.5:1.
3. The method for preparing the environment-friendly spray painting printing base coat as claimed in claim 2, which is characterized by comprising the following steps: in the step 1, the aqueous polyurethane resin is an aromatic anionic polymer and comprises toluene diisocyanate type, diphenylmethane diisocyanate type or an alternating copolymer of the toluene diisocyanate type and the diphenylmethane diisocyanate type.
4. The method for preparing the environment-friendly spray painting printing base coat according to claim 3, which is characterized by comprising the following steps: in the step 1, the hydrophilic functional group of the anionic polymer is ammonium carboxylate.
5. The method for preparing the environment-friendly spray painting printing base coat as claimed in claim 4, which is characterized in that: in the step 2, the aqueous acrylic resin is an anionic polymer, and the aqueous acrylic resin comprises aqueous styrene-acrylic resin or aqueous hydroxypropyl resin.
6. The method for preparing the environment-friendly spray painting printing base coat as claimed in claim 5, which is characterized in that: in the step 2, the water-based styrene-acrylic resin comprises a polymer formed by copolymerizing more than two of styrene, methacrylic acid, acrylonitrile, methyl methacrylate, butyl methacrylate and octyl methacrylate.
7. The method for preparing the environment-friendly spray painting printing base coat as claimed in claim 6, which is characterized in that: the water-based hydroxypropyl resin comprises a polymer formed by copolymerizing any one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, pentaerythritol triacrylate and epoxy modified acrylate with any one of methacrylic acid, acrylonitrile, methyl methacrylate, butyl methacrylate and octyl methacrylate.
8. The method for preparing the environment-friendly spray painting printing base coat as claimed in claim 7, which is characterized in that: in the step 3, the nano mesoporous silica is synthesized by a gas phase method, the particle size distribution is 5-10nm, the nano mesoporous silica has a mesoporous structure, and the nano mesoporous silica has hydrophilic nano particles after surface modification;
In the step 3, in the using process, the nano mesoporous silica is directly added into the aqueous resin dispersion in the form of nano powder or in the form of sol, when the sol is adopted, the nano mesoporous silica is directly prepared into silica sol by purified water, the pH value of the silica sol is regulated to 8-10 by alkali liquor, and the solid content is 30% -40%.
9. The method for preparing the environment-friendly spray painting printing base coat as claimed in claim 8, which is characterized in that: in the step 2, A is 0.5-1.5, and B is 1.5-2.5 in the step 3.
10. The method for preparing the environment-friendly spray painting printing primer according to claim 8 or 9, which is characterized in that: in the step 6, the water-based defoaming agent is an oligomer or mineral oil containing ether bonds, the water-based leveling agent is an organosilicon modified oligomer, the water-based wetting agent is a nonionic or anionic oligomer surfactant, and the silane coupling agent is one of gamma-aminopropyl triethoxysilane, gamma-glycidoxypropyl trimethoxysilane or gamma-methacryloxypropyl trimethoxysilane.
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