CN103614946A - Preparation method of epoxy resin-modified high-glossiness aqueous paint for precoating - Google Patents
Preparation method of epoxy resin-modified high-glossiness aqueous paint for precoating Download PDFInfo
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- CN103614946A CN103614946A CN201310485857.2A CN201310485857A CN103614946A CN 103614946 A CN103614946 A CN 103614946A CN 201310485857 A CN201310485857 A CN 201310485857A CN 103614946 A CN103614946 A CN 103614946A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003973 paint Substances 0.000 title abstract description 17
- 239000004593 Epoxy Substances 0.000 title abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003822 epoxy resin Substances 0.000 claims abstract description 20
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 20
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 16
- 239000000057 synthetic resin Substances 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 11
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 10
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 5
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical compound CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 claims abstract description 3
- -1 acrylic ester Chemical class 0.000 claims description 24
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 8
- 125000003700 epoxy group Chemical group 0.000 claims description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 8
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 238000004017 vitrification Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- MORMPWNLQJTSOT-UHFFFAOYSA-L disodium;4-dodecyl-2-(4-sulfonatophenoxy)benzenesulfonate Chemical compound [Na+].[Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C(OC=2C=CC(=CC=2)S([O-])(=O)=O)=C1 MORMPWNLQJTSOT-UHFFFAOYSA-L 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 229920001225 polyester resin Polymers 0.000 claims description 4
- 239000004645 polyester resin Substances 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 229940043237 diethanolamine Drugs 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 3
- QPSVFNQMURAADJ-UHFFFAOYSA-N 1,4-dicyclohexyloxy-1,4-dioxobutane-2-sulfonic acid Chemical compound C1CCCCC1OC(=O)C(S(=O)(=O)O)CC(=O)OC1CCCCC1 QPSVFNQMURAADJ-UHFFFAOYSA-N 0.000 claims description 2
- YOIZTLBZAMFVPK-UHFFFAOYSA-N 2-(3-ethoxy-4-hydroxyphenyl)-2-hydroxyacetic acid Chemical compound CCOC1=CC(C(O)C(O)=O)=CC=C1O YOIZTLBZAMFVPK-UHFFFAOYSA-N 0.000 claims description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 2
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 229940049964 oleate Drugs 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 239000001384 succinic acid Substances 0.000 claims description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 8
- 230000001070 adhesive effect Effects 0.000 abstract description 8
- 239000003999 initiator Substances 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000002518 antifoaming agent Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 239000003643 water by type Substances 0.000 description 8
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 description 6
- 150000002170 ethers Chemical class 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002924 oxiranes Chemical group 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- UELAIMNOXLAYRW-UHFFFAOYSA-M sodium;1,4-dicyclohexyloxy-1,4-dioxobutane-2-sulfonate Chemical compound [Na+].C1CCCCC1OC(=O)C(S(=O)(=O)[O-])CC(=O)OC1CCCCC1 UELAIMNOXLAYRW-UHFFFAOYSA-M 0.000 description 1
- WQQPDTLGLVLNOH-UHFFFAOYSA-M sodium;4-hydroxy-4-oxo-3-sulfobutanoate Chemical class [Na+].OC(=O)CC(C([O-])=O)S(O)(=O)=O WQQPDTLGLVLNOH-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
A provided preparation method of epoxy resin-modified high-glossiness aqueous paint for precoating comprises the following steps: adding diglycol, acrylic resin, 5-40% by weight of an emulsifier, 10-70% by weight of an initiator, 20-80% by weight of water into a kettle, heating to 70-95 DEG C; then uniformly mixing epoxy resin, a (methyl) acrylate monomer, (methyl) styrene and the residual emulsifier, initiator and water, dropwise adding into the kettle; reacting at 75-90 DEG C, neutralizing with an organic alkali, adjusting the pH value to 7-9, cooling and taking out to obtain a self-synthetic resin; and taking 5-45 parts by weight of the self-synthetic resin, 100 parts by weight of acrylate resin, 0.3-0.7 part by weight of a levelling agent, 0.1-1.0 part by weight of a defoaming agent and 125-300 parts by weight of water and stirring uniformly to obtain the high-glossiness aqueous paint for precoating. The epoxy resin-modified high-glossiness aqueous paint for precoating has the advantages of being strong in adhesive force after a film is forming, good in stability and high in glossiness.
Description
Technical field
The present invention relates to the preparation method of high-gloss for a kind of epoxy resin modification primary coat, the functional aid of mainly processing as beer label paper primary coat.
Background technology
In papermaking coating technique; in order to beautify the practical value of printed matter, protection printed matter, the effect of publicity of strengthening printed matter and raising printed matter; we need to carry out glazing processing to paper; at printed matter surface, be coated with (or spray, print) water white coating of last layer; after levelling, dry, press polish, at printed matter surface, form the thin and uniform transparent bright layer of one deck, make the printed matter surface after glazing seem Paint Gloss; make incident light produce evenly reflection, ink layer is brighter.
Glazing processing is to improve printed matter surface performance, improves the effective way of print quality and class.Along with the raising of printed apcksging material glazing requirement and the enhancing of people's environmental consciousness, paper water paint is because it has high glaze, good caking property and the advantage such as weatherability and low VOC, the fineness packing that has been widely used in the products such as cigarette, wine, bottle sticker, tealeaves, food, cosmetics, daily use chemicals, general merchandise, gift, handicraft, the market demand of water paint also constantly rises.
At present, the glazing paint of domestic production has solvent-borne type, ethanol-soluble type, water-based (emulsion-type) coating, wherein in solvent-borne type and ethanol-soluble type coating, contains a large amount of organic solvents, and smell is large, operation and social environment are had a great impact, and very big to the mankind's healthy infringement; High-gloss is to replace grease with synthetic resin, and a kind of environment-friendly aqueous coating with water to replace organic solvent, not only has high gloss, and is conducive to the reclaiming of paper product, has become one of main development direction of coatings industry.
Applicant discloses by adding the vacuum aluminium-plated paper painting coating of the preparations such as acrylate, neutralizer, levelling agent and anti-wear agent in Chinese patent CN101250834, there is excellent transparency and ABRASION RESISTANCE, yet adhesive force, stability, glossiness after this coating film forming still needs further to be improved.
Summary of the invention
The object of this invention is to provide the preparation method of high-gloss for a kind of epoxy resin modification primary coat, the above-mentioned defect existing to overcome prior art.
The preparation method of high-gloss for epoxy resin modification primary coat of the present invention, comprises the steps:
(1) at the bottom of diethylene glycol (DEG) and acrylic resin, the emulsifying agent that accounts for emulsifying agent gross weight 5-40%, the initator that accounts for initator gross weight 10-70%, the water that accounts for water gross weight 20-80% are added to still, be warming up to 70-95 ℃, then emulsifying agent, initator, the water of epoxy resin, (methyl) acrylic ester monomer, (methyl) styrene and surplus are mixed, in 1.0-4.0 hour, be added dropwise in reactor, at 75-90 ℃, react 2.5-4.0 hour, with organic base, neutralize again, regulating pH value is 7-9, cooling discharge, obtains from synthetic resin;
(2) get step (1) from synthetic resin 5-45 part, 100 parts of acrylates, levelling agent 0.3-0.7 part, defoamer 0.1-1.0 part, water 125-300 part, stirs and makes primary coat high-gloss.
In step (1), each component weight content is as follows:
Described epoxy resin is selected from least one in the bisphenol A epoxide resin that epoxy group content is 0.20mol/100g (E-20), bisphenol A epoxide resin (E-44) that epoxy group content is 0.44mol/100g, bisphenol A epoxide resin (E-42) that epoxy group content is 0.42mol/100g, bisphenol A epoxide resin (E-51) that epoxy group content is 0.51mol/100g.
Described (methyl) acrylic ester monomer is selected from least one in ethyl acrylate, n-butyl acrylate, ethyl methacrylate, n-BMA, methyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, EHMA.
The acid number of described acrylic resin is 150-400mgKOH/g, and molecular weight is 1000-5000.
Described emulsifying agent is selected from least one in anion surfactant or non-ionic surface active agent;
Described anion surfactant is selected from least one in neopelex, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, alkylol polyethers sulfo group succinic acid monoester sodium salt or dicyclohexyl sulfosuccinate;
Described non-ionic surface active agent is selected from least one in rosin acid polyoxyethylene ester, polyoxyethylene nonylphenol ether, dibenzyl cumenyl phenol polyethenoxy ether or glycerin polyoxyethylene ether polyoxypropylene ether fatty acid ester;
Described initator is selected from least one in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate;
Described defoamer is selected from least one in dimethyl silicone polymer, tributyl phosphate, acetic acid bay alcohol ester, benzyl carbinol oleate or polyoxyethylene polyoxy propyl alcohol amidogen ether;
The vitrification point Tg of described acrylate is-15-30 ℃ that acid number is 5-20mgKOH/g.
Described levelling agent is selected from least one in dimethyl silicone polymer, polyester resin change properties of organic silicon or silicone modified polyacrylate.
Described organic base is selected from least one in triethanolamine, ethylenediamine, diethanol amine or diethylenetriamine.
High-gloss prepared by the present invention improves patent CN101250834, by when from synthetic resin, add that epoxy resin and diethylene glycol (DEG) make that high-glaze aqueous glazing paint has advantages of that film forming rear stability is good, strong adhesion and glossiness high.Wherein add diethylene glycol (DEG), can with acrylic resin in carboxyl produce slight crosslinkedly, and form network structure to a certain degree, make polymerization enter acrylic acid carboxylic ions of strand, form hydrophilic one end, one end hydrophobic, surfactant-like, makes system more stable.When adding epoxy resin and styrene and acrylic ester monomer graft copolymerization, by being cross-linked with each other, increase the degree of cross linking of filming, between macromolecular chain, form network structure, thereby effectively made up water-base resin material due to the low defect of the little glossiness causing of linear structure degree of branching; After epoxide group being incorporated on copolymer molecule chain, in emulsion coating process thereafter, epoxide group can react with the hydroxyl on paper fibre surface and generate cross-bond, and adhesive force is improved simultaneously.
Primary coat high-glaze aqueous glazing paint prepared by the present invention, weight solid content is 25-50%, pH value is 5-8, can effectively overcome the shortcoming of existing technique, and adhesive force after coating film forming, stability and glossiness are all improved.
The specific embodiment
Embodiment 1
With condenser, agitator, in the 1000mL four-hole boiling flask of thermometer and Dropping feeder, add 4 grams of diethylene glycol (DEG)s, (acid number is 220mgKOH/g to 40 grams of acrylic resins, molecular weight is 5000), 3.2 grams of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonates, 3.2 grams of dibenzyl cumenyl phenol polyethenoxy ethers, 8.4 grams of ammonium persulfates and 316 grams of deionized waters, stirring is warming up to 95 ℃, then drip following all phase emulsions: 120 grams of E-20, 160 grams of butyl acrylates and 48 grams of styrene, 4.8 grams of disodium 4-dodecyl-2,4 '-oxydibenzenesulfonates, 4.8 grams of dibenzyl cumenyl phenol polyethenoxy ethers, 3.6 grams of ammonium persulfates and 79 grams of deionized waters, mix monomer, in 4.0 hours, add, holding temperature was 90 ℃ of reactions 2.5 hours, with triethanolamine, neutralize again, regulating pH value is 7.5, cooling discharge, obtain making by oneself synthetic resin, weight solid content is 50.0%.Then by 50 grams from synthetic resin, 100 grams of acrylates (vitrification point Tg is 30 ℃), 1 gram of tributyl phosphate, 0.7 gram of silicone modified polyacrylate and 125 grams of water mix and blends 30 minutes, make high-glaze aqueous glazing paint, pH value is 8.0, weight solid content 49.8%.
Embodiment 2
With condenser, agitator, in the 2000mL four-hole boiling flask of thermometer and Dropping feeder, add 8 grams of diethylene glycol (DEG)s, (acid number is 400mgKOH/g to 24 grams of acrylic resins, molecular weight is 5000), 0.04 gram of polyoxyethylene nonylphenol ether, 0.16 gram of potassium peroxydisulfate and 161 grams of deionized waters, stirring is warming up to 70 ℃, then drip following mix monomer: 40 grams of E-44, 32 grams of methyl methacrylates, 98 grams of styrene mix monomers and 0.76 gram of polyoxyethylene nonylphenol ether, 1.44 gram potassium peroxydisulfate, 646 grams of deionized waters, in 1.0 hours, add, holding temperature was 75 ℃ of reactions 4.0 hours, with ethylenediamine, neutralize again, regulating pH value is 7.0, cooling discharge, obtain making by oneself synthetic resin, weight solid content is 19.8%.Then by 25 grams from synthetic resin, 100 grams of acrylates (vitrification point Tg is-15 ℃), 0.1 gram of dimethyl silicone polymer, 0.3 gram of polyester resin change properties of organic silicon and 294 grams of water mix and blends 30 minutes, make high-glaze aqueous glazing paint, pH value is 5.0, weight solid content 25.0%.
Embodiment 3
With condenser, agitator, in the 1000mL four-hole boiling flask of thermometer and Dropping feeder, add 7 grams of diethylene glycol (DEG)s, (acid number is 270mgKOH/g to 80 grams of acrylic resins, molecular weight is 3000), 0.8 gram of dicyclohexyl sodium sulfosuccinate, 0.4 gram of dibenzyl cumenyl phenol polyethenoxy ether, 4.0 grams of sodium peroxydisulfates and 292 grams of deionized waters, stirring is warming up to 85 ℃, then drip following mix monomer: 60 grams of E-42, 36 grams of Isooctyl acrylate monomers, 54 grams of styrene mix monomers and 7.2 grams of dicyclohexyl sodium sulfosuccinates, 3.6 grams of dibenzyl cumenyl phenol polyethenoxy ethers, 4.0 grams of sodium peroxydisulfates and 423 grams of deionized waters, in 2.5 hours, add, holding temperature was 85 ℃ of reactions 3.0 hours, with diethanol amine, neutralize again, regulating pH value is 9.0, cooling discharge, obtain making by oneself synthetic resin, weight solid content is 31.0%.Then by 145 grams from synthetic resin, 100 grams of acrylates (vitrification point Tg is 0 ℃), 0.5 gram of dimethyl silicone polymer, 0.5 gram of dimethyl silicone polymer and 182 grams of water mix and blends 30 minutes, make high-glaze aqueous glazing paint, pH value is 6.2, weight solid content 33.6%.
Embodiment 4
With condenser, agitator, in the 1000mL four-hole boiling flask of thermometer and Dropping feeder, add 5 grams of diethylene glycol (DEG)s, (acid number is 150mgKOH/g to 60 grams of acrylic resins, molecular weight is 1000), 0.5 gram of neopelex, 1.0 grams of dibenzyl cumenyl phenol polyethenoxy ethers, 4.0 grams of sodium peroxydisulfates and 355 grams of deionized waters, stirring is warming up to 80 ℃, then drip following mix monomer: 90 grams of E-51, 40 grams of methyl methacrylates and 200 grams of styrene and 1.17 grams of neopelexes, 2.34 grams of dibenzyl cumenyl phenol polyethenoxy ethers, 4.0 grams of sodium peroxydisulfates and 355 grams of deionized waters, in 3.5 hours, add, holding temperature was 80 ℃ of reactions 3.5 hours, with triethanolamine, neutralize again, regulating pH value is 8.2, cooling discharge, obtain making by oneself synthetic resin, weight solid content is 36.5%.Then by 41 grams from synthetic resin, 100 grams of acrylates (vitrification point Tg is 20 ℃), 0.6 gram of phenylacetic acid bay alcohol ester, 0.8 gram of polyester resin change properties of organic silicon and 185 grams of water mix and blends 30 minutes, make high-glaze aqueous glazing paint, pH value is 7.6, weight solid content 35.4%.
Embodiment 5
Comparative example: the method according to CN101250834 is prepared water paint.
Use the coating of embodiment 1～4 formulated.
Use embodiment 1～4 and comparative example to apply detection, the results are shown in following table:
After Paper Coating, adhesive force testing result is as follows, and adhesive force is pressed GB/T4677.7-1984 method and detected.Wherein judgment criteria adopts ISO classification standard, and 0 grade peels off for the smooth nothing in edge and crossing; 1 grade for peeling off intersection, is no more than 5% in region; 2 grades for peeling off crossing, and its area is greater than 5%, is less than 5%; 3 grades peel off for there are part or sheet in crossing, but are no more than 35%.
| Sample | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Adhesive force | 2 grades | 1 grade | 2 grades | 0 grade | 1 grade |
Embodiment 6
Comparative example: the method according to CN200810035264 is prepared water paint.
Use the coating of embodiment 1～4 formulated.
Use embodiment 1～4 and comparative example to apply detection, the results are shown in following table:
After Paper Coating, glossiness testing result is as follows, and glossiness is pressed GB/T8941-2007 method and detected, and wherein numerical value is larger, shows that glossiness is higher.
| Sample | Blank | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Glossiness/Gs | 65.0 | 91.7 | 96.5 | 95.2 | 97.1 | 97.9 |
Embodiment 7
Comparative example: the method according to CN200810035264 is prepared water paint.
Use the coating of embodiment 1～4 formulated.
Use embodiment 1～4 and comparative example to apply detection, the results are shown in following table:
Storage stability testing result is as follows, storage stability detects (storage requirement: store at 50 ± 2 ℃ 30 days) by the method for GB6753.3-1986, viscosity records with NDJ-1 rotation viscometer, storage stability is evaluated measurement according to viscosity changing value, the ratio percentage of viscosity and original viscosity after storing, when viscosity changing value is less, show that coating storage stability is better.
| Sample | Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Viscosity changing value (%) | 8.86 | 5.43 | 5.21 | 4.37 | 4.68 |
From above-mentioned application result, can find out, compare with comparative example, use the primary coat high-gloss of the embodiment of the present invention 1～4 preparation, can improve preferably adhesive force and glossiness after coating film forming, and there is good stability.
Claims (9)
1. the preparation method of high-gloss for epoxy resin modification primary coat, is characterized in that, comprises the steps:
(1) at the bottom of diethylene glycol (DEG) and acrylic resin, the emulsifying agent that accounts for emulsifying agent gross weight 5-40%, the initator that accounts for initator gross weight 10-70%, the water that accounts for water gross weight 20-80% are added to still, be warming up to 70-95 ℃, then emulsifying agent, initator, the water of epoxy resin, (methyl) acrylic ester monomer, (methyl) styrene and surplus are mixed, in 1.0-4.0 hour, be added dropwise in reactor, at 75-90 ℃, react 2.5-4.0 hour, with organic base, neutralize again, regulating pH value is 7-9, cooling discharge, obtains from synthetic resin;
(2) get step (1) from synthetic resin 5-45 part, 100 parts of acrylates, levelling agent 0.3-0.7 part, defoamer 0.1-1.0 part, water 125-300 part, stirs and makes primary coat high-gloss.
2. method according to claim 1, is characterized in that, in step (1), each component weight content is as follows:
3. method according to claim 1, it is characterized in that, described epoxy resin is selected from least one in the bisphenol A epoxide resin that epoxy group content is 0.20mol/100g (E-20), bisphenol A epoxide resin (E-44) that epoxy group content is 0.44mol/100g, bisphenol A epoxide resin (E-42) that epoxy group content is 0.42mol/100g, bisphenol A epoxide resin (E-51) that epoxy group content is 0.51mol/100g.
4. method according to claim 1, it is characterized in that, described (methyl) acrylic ester monomer is selected from least one in ethyl acrylate, n-butyl acrylate, ethyl methacrylate, n-BMA, methyl acrylate, Isooctyl acrylate monomer, methyl methacrylate, EHMA.
5. method according to claim 1, is characterized in that, the acid number of described acrylic resin is 150-400mgKOH/g, and molecular weight is 1000-5000.
6. method according to claim 1, is characterized in that, described emulsifying agent is selected from least one in anion surfactant or non-ionic surface active agent.
7. method according to claim 6, it is characterized in that, described anion surfactant is selected from least one in neopelex, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, alkylol polyethers sulfo group succinic acid monoester sodium salt or dicyclohexyl sulfosuccinate; Described non-ionic surface active agent is selected from least one in rosin acid polyoxyethylene ester, polyoxyethylene nonylphenol ether, dibenzyl cumenyl phenol polyethenoxy ether or glycerin polyoxyethylene ether polyoxypropylene ether fatty acid ester.
8. method according to claim 1, is characterized in that, described initator is selected from least one in ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate.
9. method according to claim 1, is characterized in that, described defoamer is selected from least one in dimethyl silicone polymer, tributyl phosphate, acetic acid bay alcohol ester, benzyl carbinol oleate or polyoxyethylene polyoxy propyl alcohol amidogen ether; The vitrification point Tg of described acrylate is-15-30 ℃ that acid number is 5-20mgKOH/g; Described levelling agent is selected from least one in dimethyl silicone polymer, polyester resin change properties of organic silicon or silicone modified polyacrylate; Described organic base is selected from least one in triethanolamine, ethylenediamine, diethanol amine or diethylenetriamine.
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| CN112012046A (en) * | 2020-08-18 | 2020-12-01 | 嘉兴市豪能科技股份有限公司 | Method for manufacturing aluminum-plated paper without blackening after beer label is pasted on bottle |
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| CN102875740A (en) * | 2012-09-29 | 2013-01-16 | 上海东升新材料有限公司 | Epoxy resin modified styrene-acrylic emulsion for coated paper and preparation method thereof |
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