CN114316722A - High-wear-resistance water-based gloss oil and preparation method thereof - Google Patents
High-wear-resistance water-based gloss oil and preparation method thereof Download PDFInfo
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Abstract
The application relates to the technical field of water-based varnish, and particularly discloses high-wear-resistance water-based varnish and a preparation method thereof, wherein the high-wear-resistance water-based varnish comprises modified acrylate emulsion, acrylic resin, wax emulsion, a film forming auxiliary agent, a wetting agent, a leveling agent, a defoaming agent, a thickening agent, a cross-linking agent and deionized water; the high-wear-resistance water-based gloss oil prepared by the scheme has the characteristics of high strength, high wear resistance and good toughness. The application also provides a preparation method of the high-wear-resistance water-based gloss oil, which comprises the steps of adding the wetting agent, the flatting agent, the defoaming agent, the cross-linking agent and the acrylic resin into deionized water, dispersing and uniformly mixing, then adding the modified acrylate emulsion and the wax emulsion, continuously mixing, finally adding the film-forming assistant and the thickening agent, uniformly mixing, and adjusting the pH value to obtain the high-wear-resistance water-based gloss oil; the process is simple to operate, the preparation efficiency is high, and the obtained water-based gloss oil is good in performance stability.
Description
Technical Field
The application relates to the technical field of water-based gloss oil in the printing and packaging industry, in particular to high-wear-resistance water-based gloss oil and a preparation method thereof.
Background
The paper package has the advantages of easy processing, low cost, suitability for printing, light weight, foldability, no toxicity, no smell, no pollution and the like, is widely applied to packages in the fields of food, medicine, electronics and the like, and is one of the higher types of packaged products. In practical applications, paper packaging is frequently reprocessed by a film coating process and a glazing process to achieve the purposes of better product protection, decoration effect increase and the like, wherein the glazing process is more and more widely applied due to the characteristics of simple process, low cost and the like.
Glazing processing is an effective method for improving the surface performance of printed matters, gloss oil is coated on the surface of the printed matters, so that the glossiness, water resistance and wear resistance of the printed matters are increased, the printed matters are more gorgeous, a certain protection effect on the printed matters can be achieved, and meanwhile, the subsequent processing of the printed matters is facilitated. Gloss oil can be broadly divided into: solvent-based gloss oil, water-based gloss oil, and UV gloss oil. With the development of the trend of environmental protection of printing, the aqueous gloss oil has the advantages of low cost, environmental protection, no pollution and the like, and is more and more widely applied to the packaging industries of food, medicine, cigarettes and the like.
However, compared with a film, the water-based varnish has poor wear resistance and toughness, the water-based varnish in the related technology cannot simultaneously have high wear resistance and good toughness, the water-based varnish is easy to generate line explosion in the die cutting or finished product folding process of a packaging product, and the laser coding part is easy to rub and discolor during the laser coding operation.
Disclosure of Invention
In order to solve the problems that the aqueous gloss oil is poor in wear resistance and toughness, easy to generate line explosion and color fading due to laser coding and the like, the application provides the high-wear-resistance aqueous gloss oil and the preparation method thereof, and the obtained aqueous gloss oil is effectively ensured to have high wear resistance and good toughness through raw material selection, formula design and preparation process control.
In a first aspect, the application provides a high wear-resistant water-based gloss oil, which adopts the following technical scheme:
a high wear-resistant water-based gloss oil comprises the following raw materials in percentage by weight: 40-60% of modified acrylate emulsion, 10-20% of acrylic resin, 4-8% of wax emulsion, 0.5-2% of film-forming assistant, 0.5-2% of wetting agent, 0.5-2% of flatting agent, 0.5-2% of defoaming agent, 1-3% of thickening agent, 1-2% of cross-linking agent and 10-20% of deionized water.
Preferably, the high-wear-resistance water-based gloss oil comprises the following raw materials in percentage by weight: 45-55% of modified acrylate emulsion, 12-18% of acrylic resin, 5-7% of wax emulsion, 0.8-1.5% of film-forming assistant, 0.8-1.5% of wetting agent, 0.8-1.5% of flatting agent, 0.8-1.5% of defoaming agent, 1.5-2.5% of thickening agent, 1.2-1.8% of cross-linking agent and 12-18% of deionized water.
Preferably, the high-wear-resistance water-based gloss oil comprises the following raw materials in percentage by weight: 55% of modified acrylate emulsion, 15% of acrylic resin, 6% of wax emulsion, 1.2% of film-forming assistant, 1.4% of wetting agent, 1.4% of flatting agent, 1.5% of defoaming agent, 2% of thickening agent, 1.5% of cross-linking agent and 15% of deionized water.
By adopting the technical scheme, the formula is scientific, the proportion is strict, the high bonding strength among the raw materials is ensured through the synergistic effect among the raw materials, the obtained water-based gloss oil is low in porosity after film forming, high in compactness, high in strength and hardness, excellent in wear resistance and good in toughness, is used for polishing the base material, is good in surface permeability and high in adhesion firmness, and can effectively solve the problems of line explosion in the process of die cutting or folding of a packaged product, friction fading at a laser coding position and the like.
Preferably, the modified acrylate emulsion is an emulsion with a core-shell structure, the core is an acrylate emulsion with a glass transition temperature of 80-100 ℃, and the shell is an acrylate emulsion with a glass transition temperature of 15-30 ℃.
Preferably, the modified acrylate emulsion is prepared by the following method:
(1) dissolving an emulsifier and sodium bicarbonate in deionized water, adding core layer monomers of methyl methacrylate and isooctyl acrylate, stirring for 8-15min, and slowly dropwise adding an initiator aqueous solution with the concentration of 10% to obtain a seed emulsion, wherein the mass ratio of the emulsifier to the sodium bicarbonate to the deionized water to the methyl methacrylate to the isooctyl acrylate to the initiator aqueous solution is 0.8:1.5:30:5:7: 1;
(2) continuously dropwise adding core layer methyl methacrylate and isooctyl acrylate into the seed emulsion obtained in the step (1), simultaneously dropwise adding an initiator aqueous solution with the concentration of 10%, and stirring at the temperature of 80-90 ℃ for 50-80min to obtain core layer emulsion, wherein the mass ratio of the seed emulsion, the methyl methacrylate, the isooctyl acrylate and the initiator aqueous solution is 18:3:4: 0.5;
(3) dropwise adding methyl methacrylate, butyl acrylate, isooctyl acrylate, methacrylic acid, a chain transfer agent, a modified monomer and an initiator aqueous solution with the concentration of 10% into the nuclear layer emulsion obtained in the step (2), preserving the heat for 1.5-2.5h at the temperature of 85-95 ℃, then cooling to below 40 ℃, adding ammonia water to adjust the pH value to 8-9, stirring for 10-20min, and filtering to obtain a modified polyacrylate emulsion; wherein the mass ratio of the core layer emulsion to the methyl methacrylate to the butyl acrylate to the isooctyl acrylate to the methacrylic acid to the chain transfer agent to the modified monomer to the aqueous solution of the initiator is 27:8:4:3:5:0.5:2: 1.
By adopting the technical scheme, the hydrophilic functional groups in the monomers synthesized by the acrylate emulsion are reacted or sealed, so that the hydrophobic capacity of the obtained acrylate emulsion is improved, good waterproof and moistureproof effects are achieved, the core-shell structure emulsion is obtained through reaction, the core-shell structure emulsion is used as the main raw material of the water-based varnish, the high wear resistance and high scratch resistance of the obtained water-based varnish are ensured, the flexibility and the film forming property of the water-based varnish are improved, and the film forming temperature of the water-based varnish is reduced.
Preferably, the emulsifier is a reactive emulsifier, and can be one or a mixture of two of sodium acrylamide stearate, sodium styrene sulfonate, sodium acrylamido isopropyl sulfonate, sodium 2-methyl allyl sulfonate or sodium 2-acrylamide-2, 2-dimethyl ethyl sulfonate.
By adopting the technical scheme, the addition of the emulsifier can obviously reduce the free energy between incompatible interfaces, thereby forming stable and uniform emulsion; the emulsifier with reactivity is adopted, so that the problem of back adhesion caused by floating up and water absorption of the emulsifier after the aqueous gloss oil is formed into a film can be effectively solved.
Preferably, the initiator is one of potassium persulfate, sodium persulfate and ammonium persulfate.
By adopting the technical scheme, the persulfate initiator which is easily soluble in water is adopted, and after the persulfate initiator is heated and decomposed, the monomer polymerization can be effectively initiated, the cross-linking reaction is promoted to be carried out, the polymerization reaction rate is high, and the reaction conversion rate is high.
Preferably, the chain transfer agent is a combination of n-pentanol and dodecyl mercaptan.
By adopting the technical scheme, the molecular weight of the obtained polymer can be effectively controlled by adding the chain transfer agent, so that the modified acrylate emulsion with the required performance is obtained, and the n-amyl alcohol and the dodecyl mercaptan are matched to be used as the chain transfer agent, so that the method has the characteristics of small using amount, low residual quantity and remarkable chain transfer effect.
Preferably, the modifying monomer is a compound of octadecyl acrylate and glycidyl methacrylate.
By adopting the technical scheme, the octadecyl acrylate and the glycidyl methacrylate are matched as the modified monomers to prepare the modified acrylate emulsion, so that the hardness, the glossiness, the adhesive force, the weather resistance and the like of the finally prepared water-based gloss oil coating can be effectively improved.
Preferably, the acrylic resin is obtained by ammoniating solid acrylic resin with 10% of ammonia water.
By adopting the technical scheme, the wear resistance, the adhesive force and the viscosity reduction effect of the acrylic resin aminated by ammonia water are further improved.
Preferably, the wax emulsion is an aqueous polyethylene wax emulsion having a solids content of 50-65%.
By adopting the technical scheme, the addition of the wax emulsion can obviously improve the waterproof performance of the water-based gloss oil, can improve the friction resistance and scratch resistance of the water-based gloss oil, and increase the smoothness and glossiness of the water-based gloss oil.
Preferably, the film forming auxiliary agent is one or more of alcohol ester twelve, propylene glycol butyl ether, ethylene glycol, propylene glycol, dipropylene glycol monobutyl ether or propylene glycol methyl ether acetate.
By adopting the technical scheme, the film forming auxiliary agent is prepared from the high-boiling-point solvent, so that the lowest film forming temperature of the water-based gloss oil can be obviously reduced, the film forming auxiliary agent slowly volatilizes after the gloss oil is formed into a film, the plastic flow and elastic deformation fusion of gloss oil raw material particles are promoted, and the coalescence performance of the gloss oil is improved, thereby forming a finished continuous film; the addition and use of the film forming additive can further improve the waterproof, anti-corrosion and other performances of the water-based gloss oil.
Preferably, the leveling agent is at least one of polydimethylsiloxane, polymethylphenylsiloxane, polyether polyester modified organosiloxane, alkyl hydroxyl modified organosiloxane or acrylate leveling agent.
By adopting the technical scheme, the water-based varnish has holes after forming a film, and the holes of the water-based varnish can be sealed by adding the leveling agent, so that a flat, smooth and uniform coating film is formed in the film forming process, and the water-resistant and anti-sticking properties of the water-based varnish are further improved.
Preferably, the thickener is an associated polyurethane thickener, and can be one or more of RM 8W, RM 2020, U902 or PUR 62.
By adopting the technical scheme, the thickener selected by the application has a high-efficiency thickening effect, is good in thickening and leveling property and low in thixotropy, is used for adding the water-based gloss oil, can improve the shear viscosity, the fluidity, the compatibility and the film forming property of the water-based gloss oil, and improves the strength, the adhesive force and the stability of a coating film.
Preferably, the wetting agent is one or any combination of sodium dodecyl sulfate, ethoxy polydimethylsiloxane or alkylphenol polyoxyethylene.
By adopting the technical scheme, the addition of the wetting agent can effectively improve the dispersion stability of the water-based gloss oil, and simultaneously improve the surface tension and permeability of the water-based gloss oil, so that the water-based gloss oil can fully wet and permeate the base material, and further improve the adhesive force to the base material.
Preferably, the defoaming agent is a BYK organic silicon defoaming agent, and one or more of BYK-019, BYK-024 and BYK-028 can be selected.
By adopting the technical scheme, the organic silicon defoamer has small surface tension and good defoaming efficiency, can play good defoaming and defoaming roles when being used for adding the water-based gloss oil, further improves the mixing efficiency of the water-based gloss oil, and improves the appearance of a coating film.
Preferably, the crosslinking agent is N-methylolacrylamide.
By adopting the technical scheme, the N-methylolacrylamide has the advantages of small addition amount, high crosslinking efficiency, stable crosslinking structure and proper crosslinking time, the strength and the wear resistance of a film layer formed by the water-based gloss oil are further improved, and the price construction performance of the water-based gloss oil is improved.
In a second aspect, the application provides a preparation method of high-wear-resistance water-based gloss oil, which adopts the following technical scheme:
a preparation method of high-wear-resistance water-based gloss oil specifically comprises the following steps:
s1, weighing the raw materials of modified acrylate emulsion, acrylic resin, wax emulsion, film-forming auxiliary agent, wetting agent, flatting agent, defoaming agent, thickening agent, cross-linking agent and deionized water according to weight percentage for later use;
s2, adding deionized water into the mixing device, starting stirring, adding the wetting agent, the flatting agent, the defoaming agent, the crosslinking agent and the acrylic resin in sequence while stirring, and uniformly stirring and mixing to obtain a mixed solution A;
s3, sequentially adding the modified acrylate emulsion and the wax emulsion into the mixed solution A, and continuously stirring and uniformly mixing to obtain a mixed solution B;
and S4, finally adding the film-forming aid and the thickening agent into the mixed solution B, continuously stirring and uniformly mixing, adding ammonia water to adjust the pH value to 8-9, and filtering to obtain the required high-wear-resistance water-based gloss oil.
By adopting the technical scheme, the water-based gloss oil raw materials are sequentially stirred and mixed by controlling the mixing sequence of the raw materials, and the final product is prepared by filtering after the pH is adjusted; the preparation method is simple, the preparation conditions are mild, the preparation cost is low, the preparation efficiency is high, the obtained water-based gloss oil is good in dispersion uniformity and stable in performance, and has the characteristics of good toughness, water resistance, moisture resistance, anti-after-tack, good appearance leveling property, good glossiness and the like while having the mechanical properties of high strength, high wear resistance, scratch resistance and the like.
In summary, the present application has the following beneficial effects:
the preparation method comprises the steps of preparing an acrylate emulsion with the glass transition temperature of 80-100 ℃ as a core layer, preparing an acrylate emulsion with the glass transition temperature of 15-30 ℃ as a shell layer, compounding the two to form a modified acrylate emulsion with a core-shell structure, and mixing the modified acrylate emulsion as a main raw material of the aqueous gloss oil with the residual raw materials such as solid acrylic resin, wax emulsion, film-forming assistant and the like after ammoniation of ammonia water to prepare the required high-wear-resistance aqueous gloss oil; the preparation method is simple, the preparation efficiency is high, the obtained water-based gloss oil has good processability, film-forming property and leveling property, excellent wear resistance, good toughness, good dry-wet tack resistance, good water resistance, safety, environmental protection and low cost.
Detailed Description
The present application will be described in further detail with reference to examples.
Example 1
The application provides high wear-resistant water-based gloss oil, which adopts the following technical scheme:
a high wear-resistant water-based gloss oil comprises the following raw materials in percentage by weight: 40% of modified acrylate emulsion, 20% of acrylic resin, 7% of wax emulsion, 2% of film-forming assistant, 2% of wetting agent, 2% of flatting agent, 2% of defoaming agent, 3% of thickening agent, 2% of cross-linking agent and 20% of deionized water;
wherein: the modified acrylate emulsion is an emulsion with a core-shell structure, the core is an acrylate emulsion with a glass transition temperature of 80 ℃, and the shell is an acrylate emulsion with a glass transition temperature of 15 ℃, and is prepared by the following method:
(1) dissolving an emulsifier and sodium bicarbonate in deionized water, adding core layer monomers of methyl methacrylate and isooctyl acrylate, stirring for 8min, and slowly dropwise adding an initiator aqueous solution with the concentration of 10% to obtain a seed emulsion, wherein the mass ratio of the emulsifier to the sodium bicarbonate to the deionized water to the methyl methacrylate to the isooctyl acrylate to the initiator aqueous solution is 0.8:1.5:30:5:7: 1;
(2) continuously dropwise adding core layer methyl methacrylate and isooctyl acrylate into the seed emulsion obtained in the step (1), simultaneously dropwise adding an initiator aqueous solution with the concentration of 10%, and stirring for 50min at the temperature of 80 ℃ to obtain core layer emulsion, wherein the mass ratio of the seed emulsion, the methyl methacrylate, the isooctyl acrylate and the initiator aqueous solution is 18:3:4: 0.5;
(3) dropwise adding methyl methacrylate, butyl acrylate, isooctyl acrylate, methacrylic acid, a chain transfer agent, a modified monomer and an initiator aqueous solution with the concentration of 10% into the nuclear layer emulsion obtained in the step (2), preserving the heat for 1.5h at the temperature of 85 ℃, then cooling to 38 ℃, adding ammonia water to adjust the pH value to 8, stirring for 10min, and filtering to obtain a modified polyacrylate emulsion; wherein the mass ratio of the core layer emulsion to the methyl methacrylate to the butyl acrylate to the isooctyl acrylate to the methacrylic acid to the chain transfer agent to the modified monomer to the aqueous solution of the initiator is 27:8:4:3:5:0.5:2: 1;
wherein: the emulsifier is acrylamide sodium stearate;
the initiator is potassium persulfate;
the chain transfer agent is a compound of n-amyl alcohol and dodecyl mercaptan in a mass ratio of 3: 1;
the modified monomer is a compound of octadecyl acrylate and glycidyl methacrylate in a mass ratio of 1: 1.8;
the acrylic resin is obtained by adding 10% ammonia water into solid acrylic resin for ammoniation;
the wax emulsion is aqueous polyethylene wax emulsion with solid content of 50 percent;
the film-forming additive is alcohol ester twelve;
the flatting agent is polydimethylsiloxane;
the thickening agent is RM 8W;
the wetting agent is sodium dodecyl sulfate;
the defoaming agent is BYK-019;
the cross-linking agent is N-methylol acrylamide.
The application also provides a preparation method of the high-wear-resistance water-based gloss oil, which specifically comprises the following steps:
s1, weighing the raw materials of modified acrylate emulsion, acrylic resin, wax emulsion, film-forming auxiliary agent, wetting agent, flatting agent, defoaming agent, thickening agent, cross-linking agent and deionized water according to weight percentage for later use;
s2, adding deionized water into the mixing device, starting stirring, adding the wetting agent, the flatting agent, the defoaming agent, the crosslinking agent and the acrylic resin in sequence while stirring, and uniformly stirring and mixing to obtain a mixed solution A;
s3, sequentially adding the modified acrylate emulsion and the wax emulsion into the mixed solution A, and continuously stirring and uniformly mixing to obtain a mixed solution B;
and S4, finally adding the film-forming aid and the thickening agent into the mixed solution B, continuously stirring and uniformly mixing, adding ammonia water to adjust the pH value to 8, and filtering to obtain the required high-wear-resistance water-based gloss oil.
Example 2
The application provides high wear-resistant water-based gloss oil, which adopts the following technical scheme:
a high wear-resistant water-based gloss oil comprises the following raw materials in percentage by weight: 55% of modified acrylate emulsion, 16% of acrylic resin, 5% of wax emulsion, 1.5% of film-forming assistant, 1% of wetting agent, 0.8% of flatting agent, 1% of defoaming agent, 1.5% of thickening agent, 1.2% of cross-linking agent and 17% of deionized water;
wherein: the modified acrylate emulsion is an emulsion with a core-shell structure, wherein the core is an acrylate emulsion with a glass transition temperature of 85 ℃, and the shell is an acrylate emulsion with a glass transition temperature of 18 ℃, and is prepared by the following method:
(1) dissolving an emulsifier and sodium bicarbonate in deionized water, adding core layer monomers of methyl methacrylate and isooctyl acrylate, stirring for 10min, and slowly dropwise adding an initiator aqueous solution with the concentration of 10% to obtain a seed emulsion, wherein the mass ratio of the emulsifier to the sodium bicarbonate to the deionized water to the methyl methacrylate to the isooctyl acrylate to the initiator aqueous solution is 0.8:1.5:30:5:7: 1;
(2) continuously dropwise adding core layer methyl methacrylate and isooctyl acrylate into the seed emulsion obtained in the step (1), simultaneously dropwise adding an initiator aqueous solution with the concentration of 10%, and stirring at the temperature of 82 ℃ for 60min to obtain core layer emulsion, wherein the mass ratio of the seed emulsion, the methyl methacrylate, the isooctyl acrylate and the initiator aqueous solution is 18:3:4: 0.5;
(3) dropwise adding methyl methacrylate, butyl acrylate, isooctyl acrylate, methacrylic acid, a chain transfer agent, a modified monomer and an initiator aqueous solution with the concentration of 10% into the nuclear layer emulsion obtained in the step (2), preserving the heat for 1.8h at the temperature of 88 ℃, then cooling to 39 ℃, adding ammonia water to adjust the pH value to 8.2, stirring for 12min, and filtering to obtain a modified polyacrylate emulsion; wherein the mass ratio of the core layer emulsion to the methyl methacrylate to the butyl acrylate to the isooctyl acrylate to the methacrylic acid to the chain transfer agent to the modified monomer to the aqueous solution of the initiator is 27:8:4:3:5:0.5:2: 1;
wherein: the emulsifier is sodium styrene sulfonate;
the initiator is sodium persulfate;
the chain transfer agent is a compound of n-amyl alcohol and dodecyl mercaptan in a mass ratio of 3: 1;
the modified monomer is a compound of octadecyl acrylate and glycidyl methacrylate in a mass ratio of 1: 1.8;
the acrylic resin is obtained by adding 10% ammonia water into solid acrylic resin for ammoniation;
the wax emulsion is an aqueous polyethylene wax emulsion with the solid content of 54 percent;
the film-forming auxiliary agent is propylene glycol butyl ether;
the leveling agent is polymethylphenylsiloxane;
the thickener is RM 2020;
the wetting agent is ethoxy polydimethylsiloxane;
the defoaming agent is BYK-024;
the cross-linking agent is N-methylol acrylamide.
The application also provides a preparation method of the high-wear-resistance water-based gloss oil, which specifically comprises the following steps:
s1, weighing the raw materials of modified acrylate emulsion, acrylic resin, wax emulsion, film-forming auxiliary agent, wetting agent, flatting agent, defoaming agent, thickening agent, cross-linking agent and deionized water according to weight percentage for later use;
s2, adding deionized water into the mixing device, starting stirring, adding the wetting agent, the flatting agent, the defoaming agent, the crosslinking agent and the acrylic resin in sequence while stirring, and uniformly stirring and mixing to obtain a mixed solution A;
s3, sequentially adding the modified acrylate emulsion and the wax emulsion into the mixed solution A, and continuously stirring and uniformly mixing to obtain a mixed solution B;
and S4, finally adding the film-forming aid and the thickening agent into the mixed solution B, continuously stirring and uniformly mixing, adding ammonia water to adjust the pH value to 8.2, and filtering to obtain the required high-wear-resistance water-based gloss oil.
Example 3
The application provides high wear-resistant water-based gloss oil, which adopts the following technical scheme:
a high wear-resistant water-based gloss oil comprises the following raw materials in percentage by weight: 55% of modified acrylate emulsion, 15% of acrylic resin, 6% of wax emulsion, 1.2% of film-forming assistant, 1.4% of wetting agent, 1.4% of flatting agent, 1.5% of defoaming agent, 2% of thickening agent, 1.5% of cross-linking agent and 15% of deionized water;
wherein: the modified acrylate emulsion is an emulsion with a core-shell structure, wherein the core is an acrylate emulsion with a glass transition temperature of 90 ℃, and the shell is an acrylate emulsion with a glass transition temperature of 24 ℃, and is prepared by the following method:
(1) dissolving an emulsifier and sodium bicarbonate in deionized water, adding core layer monomers of methyl methacrylate and isooctyl acrylate, stirring for 12min, and slowly dropwise adding an initiator aqueous solution with the concentration of 10% to obtain a seed emulsion, wherein the mass ratio of the emulsifier to the sodium bicarbonate to the deionized water to the methyl methacrylate to the isooctyl acrylate to the initiator aqueous solution is 0.8:1.5:30:5:7: 1;
(2) continuously dropwise adding core layer methyl methacrylate and isooctyl acrylate into the seed emulsion obtained in the step (1), simultaneously dropwise adding an initiator aqueous solution with the concentration of 10%, and stirring at the temperature of 85 ℃ for 65min to obtain core layer emulsion, wherein the mass ratio of the seed emulsion to the initiator aqueous solution to the methyl methacrylate to the isooctyl acrylate to the initiator aqueous solution is 18:3:4: 0.5;
(3) dropwise adding methyl methacrylate, butyl acrylate, isooctyl acrylate, methacrylic acid, a chain transfer agent, a modified monomer and an initiator aqueous solution with the concentration of 10% into the nuclear layer emulsion obtained in the step (2), preserving the heat for 2 hours at the temperature of 90 ℃, then cooling to 35 ℃, adding ammonia water to adjust the pH value to 8.5, stirring for 15min, and filtering to obtain a modified polyacrylate emulsion; wherein the mass ratio of the core layer emulsion to the methyl methacrylate to the butyl acrylate to the isooctyl acrylate to the methacrylic acid to the chain transfer agent to the modified monomer to the aqueous solution of the initiator is 27:8:4:3:5:0.5:2: 1;
wherein: the emulsifier is acrylamide isopropyl sodium sulfonate;
the initiator is ammonium persulfate;
the chain transfer agent is a compound of n-amyl alcohol and dodecyl mercaptan in a mass ratio of 3: 1;
the modified monomer is a compound of octadecyl acrylate and glycidyl methacrylate in a mass ratio of 1: 1.8;
the acrylic resin is obtained by adding 10% ammonia water into solid acrylic resin for ammoniation;
the wax emulsion is an aqueous polyethylene wax emulsion with the solid content of 58 percent;
the film-forming assistant is glycol;
the leveling agent is polyether polyester modified organic siloxane;
the thickening agent is U902;
the wetting agent is alkylphenol polyoxyethylene;
the defoaming agent is BYK-028;
the cross-linking agent is N-methylol acrylamide.
The application also provides a preparation method of the high-wear-resistance water-based gloss oil, which specifically comprises the following steps:
s1, weighing the raw materials of modified acrylate emulsion, acrylic resin, wax emulsion, film-forming auxiliary agent, wetting agent, flatting agent, defoaming agent, thickening agent, cross-linking agent and deionized water according to weight percentage for later use;
s2, adding deionized water into the mixing device, starting stirring, adding the wetting agent, the flatting agent, the defoaming agent, the crosslinking agent and the acrylic resin in sequence while stirring, and uniformly stirring and mixing to obtain a mixed solution A;
s3, sequentially adding the modified acrylate emulsion and the wax emulsion into the mixed solution A, and continuously stirring and uniformly mixing to obtain a mixed solution B;
and S4, finally adding the film-forming aid and the thickening agent into the mixed solution B, continuously stirring and uniformly mixing, adding ammonia water to adjust the pH value to 8.5, and filtering to obtain the required high-wear-resistance water-based gloss oil.
Example 4
The application provides high wear-resistant water-based gloss oil, which adopts the following technical scheme:
a high wear-resistant water-based gloss oil comprises the following raw materials in percentage by weight: 47% of modified acrylate emulsion, 18% of acrylic resin, 7% of wax emulsion, 1.2% of film-forming assistant, 1.5% of wetting agent, 1.5% of flatting agent, 1.5% of defoaming agent, 2.5% of thickening agent, 1.8% of cross-linking agent and 18% of deionized water;
wherein: the modified acrylate emulsion is an emulsion with a core-shell structure, wherein the core is an acrylate emulsion with a glass transition temperature of 95 ℃, and the shell is an acrylate emulsion with a glass transition temperature of 27 ℃, and is prepared by the following method:
(1) dissolving an emulsifier and sodium bicarbonate in deionized water, adding core layer monomers of methyl methacrylate and isooctyl acrylate, stirring for 14min, and slowly dropwise adding an initiator aqueous solution with the concentration of 10% to obtain a seed emulsion, wherein the mass ratio of the emulsifier to the sodium bicarbonate to the deionized water to the methyl methacrylate to the isooctyl acrylate to the initiator aqueous solution is 0.8:1.5:30:5:7: 1;
(2) continuously dropwise adding core layer methyl methacrylate and isooctyl acrylate into the seed emulsion obtained in the step (1), simultaneously dropwise adding an initiator aqueous solution with the concentration of 10%, and stirring at the temperature of 88 ℃ for 70min to obtain core layer emulsion, wherein the mass ratio of the seed emulsion, the methyl methacrylate, the isooctyl acrylate and the initiator aqueous solution is 18:3:4: 0.5;
(3) dropwise adding methyl methacrylate, butyl acrylate, isooctyl acrylate, methacrylic acid, a chain transfer agent, a modified monomer and an initiator aqueous solution with the concentration of 10% into the nuclear layer emulsion obtained in the step (2), preserving the heat for 2.2h at the temperature of 92 ℃, then cooling to 30 ℃, adding ammonia water to adjust the pH value to 8.8, stirring for 18min, and filtering to obtain a modified polyacrylate emulsion; wherein the mass ratio of the core layer emulsion to the methyl methacrylate to the butyl acrylate to the isooctyl acrylate to the methacrylic acid to the chain transfer agent to the modified monomer to the aqueous solution of the initiator is 27:8:4:3:5:0.5:2: 1;
wherein: the emulsifier is sodium 2-methyl allyl sulfonate;
the initiator is potassium persulfate;
the chain transfer agent is a compound of n-amyl alcohol and dodecyl mercaptan in a mass ratio of 3: 1;
the modified monomer is a compound of octadecyl acrylate and glycidyl methacrylate in a mass ratio of 1: 1.8;
the acrylic resin is obtained by adding 10% ammonia water into solid acrylic resin for ammoniation;
the wax emulsion is an aqueous polyethylene wax emulsion with the solid content of 60 percent;
the film-forming assistant is propylene glycol;
the flatting agent is alkyl hydroxyl modified organic siloxane;
the thickener is PUR 62;
the wetting agent is sodium dodecyl sulfate;
the defoaming agent is BYK-019;
the cross-linking agent is N-methylol acrylamide.
The application also provides a preparation method of the high-wear-resistance water-based gloss oil, which specifically comprises the following steps:
s1, weighing the raw materials of modified acrylate emulsion, acrylic resin, wax emulsion, film-forming auxiliary agent, wetting agent, flatting agent, defoaming agent, thickening agent, cross-linking agent and deionized water according to weight percentage for later use;
s2, adding deionized water into the mixing device, starting stirring, adding the wetting agent, the flatting agent, the defoaming agent, the crosslinking agent and the acrylic resin in sequence while stirring, and uniformly stirring and mixing to obtain a mixed solution A;
s3, sequentially adding the modified acrylate emulsion and the wax emulsion into the mixed solution A, and continuously stirring and uniformly mixing to obtain a mixed solution B;
and S4, finally adding the film-forming aid and the thickening agent into the mixed solution B, continuously stirring and uniformly mixing, adding ammonia water to adjust the pH value to 8.8, and filtering to obtain the required high-wear-resistance water-based gloss oil.
Example 5
The application provides high wear-resistant water-based gloss oil, which adopts the following technical scheme:
a high wear-resistant water-based gloss oil comprises the following raw materials in percentage by weight: 60% of modified acrylate emulsion, 10% of acrylic resin, 5% of wax emulsion, 1% of film-forming assistant, 1% of wetting agent, 0.5% of flatting agent, 0.5% of defoaming agent, 1% of thickening agent, 1% of cross-linking agent and 20% of deionized water;
wherein: the modified acrylate emulsion is an emulsion with a core-shell structure, wherein the core is an acrylate emulsion with a glass transition temperature of 100 ℃, and the shell is an acrylate emulsion with a glass transition temperature of 30 ℃, and is prepared by the following method:
(1) dissolving an emulsifier and sodium bicarbonate in deionized water, adding core layer monomers of methyl methacrylate and isooctyl acrylate, stirring for 15min, and slowly dropwise adding an initiator aqueous solution with the concentration of 10% to obtain a seed emulsion, wherein the mass ratio of the emulsifier to the sodium bicarbonate to the deionized water to the methyl methacrylate to the isooctyl acrylate to the initiator aqueous solution is 0.8:1.5:30:5:7: 1;
(2) continuously dropwise adding core layer methyl methacrylate and isooctyl acrylate into the seed emulsion obtained in the step (1), simultaneously dropwise adding an initiator aqueous solution with the concentration of 10%, and stirring for 80min at the temperature of 90 ℃ to obtain core layer emulsion, wherein the mass ratio of the seed emulsion, the methyl methacrylate, the isooctyl acrylate and the initiator aqueous solution is 18:3:4: 0.5;
(3) dropwise adding methyl methacrylate, butyl acrylate, isooctyl acrylate, methacrylic acid, a chain transfer agent, a modified monomer and an initiator aqueous solution with the concentration of 10% into the nuclear layer emulsion obtained in the step (2), preserving the heat for 2.5h at the temperature of 95 ℃, then cooling to 33 ℃, adding ammonia water to adjust the pH value to 9, stirring for 20min, and filtering to obtain a modified polyacrylate emulsion; wherein the mass ratio of the core layer emulsion to the methyl methacrylate to the butyl acrylate to the isooctyl acrylate to the methacrylic acid to the chain transfer agent to the modified monomer to the aqueous solution of the initiator is 27:8:4:3:5:0.5:2: 1;
wherein: the emulsifier is 2-acrylamide-2, 2-dimethyl sodium ethanesulfonate;
the initiator is sodium persulfate;
the chain transfer agent is a compound of n-amyl alcohol and dodecyl mercaptan in a mass ratio of 3: 1;
the modified monomer is a compound of octadecyl acrylate and glycidyl methacrylate in a mass ratio of 1: 1.8;
the acrylic resin is obtained by adding 10% ammonia water into solid acrylic resin for ammoniation;
the wax emulsion is aqueous polyethylene wax emulsion with the solid content of 65 percent;
the film-forming auxiliary agent is propylene glycol methyl ether acetate;
the leveling agent is an acrylate leveling agent;
the thickening agent is RM 8W;
the wetting agent is alkylphenol polyoxyethylene;
the defoaming agent is BYK-028;
the cross-linking agent is N-methylol acrylamide.
The application also provides a preparation method of the high-wear-resistance water-based gloss oil, which specifically comprises the following steps:
s1, weighing the raw materials of modified acrylate emulsion, acrylic resin, wax emulsion, film-forming auxiliary agent, wetting agent, flatting agent, defoaming agent, thickening agent, cross-linking agent and deionized water according to weight percentage for later use;
s2, adding deionized water into the mixing device, starting stirring, adding the wetting agent, the flatting agent, the defoaming agent, the crosslinking agent and the acrylic resin in sequence while stirring, and uniformly stirring and mixing to obtain a mixed solution A;
s3, sequentially adding the modified acrylate emulsion and the wax emulsion into the mixed solution A, and continuously stirring and uniformly mixing to obtain a mixed solution B;
and S4, finally adding the film-forming aid and the thickening agent into the mixed solution B, continuously stirring and uniformly mixing, adding ammonia water to adjust the pH value to 9, and filtering to obtain the required high-wear-resistance water-based gloss oil.
Examples test sample Performance testing
The properties of the highly wear-resistant aqueous gloss oils prepared in examples 1 to 5 of the present application were tested, respectively, wherein:
(1) storage stability of aqueous gloss oil:
the high abrasion resistant aqueous gloss oil prepared in examples 1 to 5 above was allowed to stand at 60 ℃ for 9 days, which means that the storage stability of the aqueous gloss oil was good without precipitation or delamination.
(2) Anti-tack property of aqueous gloss oil:
the highly abrasion-resistant aqueous gloss oil prepared in the above examples 1 to 5 was printed on the gray cardboard using a gravure printing machine, with a gloss oil layer thickness of 20 μm, dried under an infrared lamp with a power of 15kW, and at a dryer speed of 5000 sheets/h, to obtain a printed matter.
Superposing the printing surface of the printed matter with the back surface of another grey paperboard, placing a weight of 20Kg on the printed matter, and observing whether the printed matter is adhered or not after placing for 15 days in an environment with the temperature of 22 ℃ and the relative humidity of 68%; if the water-based gloss oil is not adhered, the water-based gloss oil proves to have good anti-tack property.
(3) Abrasion resistance of aqueous gloss oil:
and (3) carrying out reciprocating friction on the printed matter in the step (2) under the load of 4 pounds, accumulating the friction times (one reciprocating friction is one time), judging the quality of the water-based gloss oil according to the currently accumulated friction times (namely the wear-resistant times) when the printed matter begins to fade, wherein the quality is better when the wear-resistant times are more.
(4) Toughness of the aqueous gloss oil:
the prepared gloss oil layer of the aqueous gloss oil was formed into a standard bar according to the 5B bar standard of ISO527/2-1993(E), and the elongation at break and tensile strength of the gloss oil layer were measured by drawing at a rate of 2mm/min on a micro-controlled electronic universal tester model WDW 3020.
The above test results are shown in table 1 below:
table 1 examples 1-5 test sample performance test results
| Detecting items | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Stability of | Good taste | Good taste | Good taste | Good taste | Good taste |
| Leveling property | Good taste | Good taste | Good taste | Good taste | Good taste |
| Redissolution property | Good taste | Good taste | Good taste | Good taste | Good taste |
| Viscosity/s | 45 | 52 | 68 | 57 | 48 |
| Gloss degree/° C | 60 | 65 | 68 | 64 | 70 |
| Wear resistance/time | 643 | 655 | 687 | 649 | 662 |
| Slide angle/° | 29 | 25 | 27 | 28 | 30 |
| Anti-tack property | Non-adhesion | Non-adhesion | Non-adhesion | Non-adhesion | Non-adhesion |
| Tensile strength/MPa | 6.17 | 6.50 | 7.21 | 5.36 | 5.05 |
| Elongation at break/% | 32.8 | 33.5 | 48.3 | 38.9 | 41.3 |
As can be seen from table 1 above: the high-wear-resistance water-based gloss oil prepared in the embodiments 1-5 has excellent comprehensive performance and has the characteristics of outstanding stability, leveling property, wear resistance, flexibility, anti-tack property and the like; the properties of example 3 are most pronounced, which combines high abrasion resistance with good flexibility.
Comparative example 1
The same preparation method as that of the application example 3 is adopted, and only the difference is that the modified acrylic emulsion consists of acrylic ester emulsion with the glass transition temperature of 90 ℃ and acrylic ester emulsion with the glass transition temperature of 24 ℃ in the mass ratio of 27: 23.5; compared with example 3, the wear resistance and toughness of the aqueous gloss oil obtained in comparative example 1 are obviously reduced, the wear resistance times are reduced to 533 times, the tensile strength is reduced to 5.95MPa, the elongation at break is reduced to 37.4%, and the other properties are not obviously changed.
Comparative example 2
The same preparation method as that of example 3 of the present application was employed except that the modified acrylic emulsion was only an acrylic emulsion having a glass transition temperature of 90 ℃; compared with example 3, the aqueous gloss oil obtained in comparative example 2 has poor film forming property and long film forming time, although the wear resistance times and strength measured after film forming are improved compared with example 3, the wear resistance times reach 732, and the tensile strength reaches 7.90MPa, the aqueous gloss oil has poor flexibility, poor folding resistance and explosion-proof linearity and poor elongation at break of only 4.9%, and has poor anti-return viscosity and serious adhesion among printed matters.
Comparative example 3
The same preparation method as that of example 3 of the present application was used except that the modified acrylic emulsion was only an acrylic emulsion having a glass transition temperature of 24 ℃; compared with example 3, the aqueous gloss oil obtained in comparative example 3 has low film-forming temperature, good film-forming property, good flexibility after film forming, strong folding resistance and elongation at break up to 79.8%; but the abrasion resistance times are reduced to 376 times, and the tensile strength is reduced to 4.41 MPa.
Comparative example 4
The same preparation method as that of example 3 of the present application was employed except that the acrylic resin was a solid acrylic resin; the aqueous varnish obtained in comparative example 4 also had a reduced abrasion resistance compared to example 3, with an abrasion number of 452.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (10)
1. The high-wear-resistance water-based gloss oil is characterized by comprising the following raw materials in percentage by weight: 40-60% of modified acrylate emulsion, 10-20% of acrylic resin, 4-8% of wax emulsion, 0.5-2% of film-forming assistant, 0.5-2% of wetting agent, 0.5-2% of flatting agent, 0.5-2% of defoaming agent, 1-3% of thickening agent, 1-2% of cross-linking agent and 10-20% of deionized water.
2. The high-wear-resistance water-based gloss oil according to claim 1, which is characterized by comprising the following raw materials in percentage by weight: 45-55% of modified acrylate emulsion, 12-18% of acrylic resin, 5-7% of wax emulsion, 0.8-1.5% of film-forming assistant, 0.8-1.5% of wetting agent, 0.8-1.5% of flatting agent, 0.8-1.5% of defoaming agent, 1.5-2.5% of thickening agent, 1.2-1.8% of cross-linking agent and 12-18% of deionized water.
3. The high-wear-resistance water-based gloss oil according to claim 1, which is characterized by comprising the following raw materials in percentage by weight: 55% of modified acrylate emulsion, 15% of acrylic resin, 6% of wax emulsion, 1.2% of film-forming assistant, 1.4% of wetting agent, 1.4% of flatting agent, 1.5% of defoaming agent, 2% of thickening agent, 1.5% of cross-linking agent and 15% of deionized water.
4. The high-wear-resistance water-based varnish according to claim 1, wherein the modified acrylate emulsion is an emulsion with a core-shell structure, the core is an acrylate emulsion with a glass transition temperature of 80-100 ℃, and the shell is an acrylate emulsion with a glass transition temperature of 15-30 ℃.
5. The high-wear-resistance water-based gloss oil according to claim 4, wherein the modified acrylate emulsion is prepared by the following method:
(1) dissolving an emulsifier and sodium bicarbonate in deionized water, adding core layer monomers of methyl methacrylate and isooctyl acrylate, stirring for 8-15min, and slowly dropwise adding an initiator aqueous solution with the concentration of 10% to obtain a seed emulsion, wherein the mass ratio of the emulsifier to the sodium bicarbonate to the deionized water to the methyl methacrylate to the isooctyl acrylate to the initiator aqueous solution is 0.8:1.5:30:5:7: 1;
(2) continuously dropwise adding core layer methyl methacrylate and isooctyl acrylate into the seed emulsion obtained in the step (1), simultaneously dropwise adding an initiator aqueous solution with the concentration of 10%, and stirring at the temperature of 80-90 ℃ for 50-80min to obtain core layer emulsion, wherein the mass ratio of the seed emulsion, the methyl methacrylate, the isooctyl acrylate and the initiator aqueous solution is 18:3:4: 0.5;
(3) dropwise adding methyl methacrylate, butyl acrylate, isooctyl acrylate, methacrylic acid, a chain transfer agent, a modified monomer and an initiator aqueous solution with the concentration of 10% into the nuclear layer emulsion obtained in the step (2), preserving the heat for 1.5-2.5h at the temperature of 85-95 ℃, then cooling to below 40 ℃, adding ammonia water to adjust the pH value to 8-9, stirring for 10-20min, and filtering to obtain a modified polyacrylate emulsion; wherein the mass ratio of the core layer emulsion to the methyl methacrylate to the butyl acrylate to the isooctyl acrylate to the methacrylic acid to the chain transfer agent to the modified monomer to the aqueous solution of the initiator is 27:8:4:3:5:0.5:2: 1.
6. The high abrasion resistant aqueous gloss oil of claim 5, wherein said emulsifier is a reactive emulsifier;
the initiator is one of potassium persulfate, sodium persulfate and ammonium persulfate;
the chain transfer agent is a compound of n-amyl alcohol and dodecyl mercaptan;
the modified monomer is a compound of octadecyl acrylate and glycidyl methacrylate.
7. The high-wear-resistance aqueous gloss oil according to claim 1, wherein the acrylic resin is obtained by adding 10% ammonia water into solid acrylic resin for ammoniation;
the wax emulsion is water-based polyethylene wax emulsion with solid content of 50-65%.
8. The high-wear-resistance water-based gloss oil of claim 1, wherein the film forming auxiliary agent is one or more of alcohol ester twelve, propylene glycol butyl ether, ethylene glycol, propylene glycol, dipropylene glycol monobutyl ether or propylene glycol methyl ether acetate;
the leveling agent is at least one of polydimethylsiloxane, polymethylphenylsiloxane, polyether polyester modified organic siloxane, alkyl hydroxyl modified organic siloxane or acrylate leveling agent.
9. The high abrasion resistant aqueous gloss oil of claim 1, wherein said thickener is an associative polyurethane thickener;
the wetting agent is one or any combination of lauryl sodium sulfate, ethoxy polydimethylsiloxane or alkylphenol polyoxyethylene;
the defoaming agent is a BYK organic silicon defoaming agent;
the cross-linking agent is N-methylol acrylamide.
10. The preparation method of the high-wear-resistance water-based gloss oil disclosed by any one of claims 1 to 9 is characterized by comprising the following steps of:
s1, weighing the raw materials of modified acrylate emulsion, acrylic resin, wax emulsion, film-forming auxiliary agent, wetting agent, flatting agent, defoaming agent, thickening agent, cross-linking agent and deionized water according to weight percentage for later use;
s2, adding deionized water into the mixing device, starting stirring, adding the wetting agent, the flatting agent, the defoaming agent, the crosslinking agent and the acrylic resin in sequence while stirring, and uniformly stirring and mixing to obtain a mixed solution A;
s3, sequentially adding the modified acrylate emulsion and the wax emulsion into the mixed solution A, and continuously stirring and uniformly mixing to obtain a mixed solution B;
and S4, finally adding the film-forming aid and the thickening agent into the mixed solution B, continuously stirring and uniformly mixing, adding ammonia water to adjust the pH value to 8-9, and filtering to obtain the required high-wear-resistance water-based gloss oil.
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