CN113402674A - Aqueous medium for wallpaper printing and preparation method thereof - Google Patents
Aqueous medium for wallpaper printing and preparation method thereof Download PDFInfo
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- CN113402674A CN113402674A CN202110735217.7A CN202110735217A CN113402674A CN 113402674 A CN113402674 A CN 113402674A CN 202110735217 A CN202110735217 A CN 202110735217A CN 113402674 A CN113402674 A CN 113402674A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
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Abstract
The invention relates to an aqueous medium for wallpaper printing and a preparation method thereof, wherein core-shell structure fluorine-containing acrylate emulsion is obtained by reacting a core monomer, a shell monomer, a reactive emulsifier, a buffering agent and an initiator; and fully mixing and dispersing the flatting agent, the wetting agent, the defoaming agent, the pH regulator and the wear-resistant additive into the core-shell structure fluorine-containing acrylate emulsion to obtain the aqueous medium for wallpaper printing. When the aqueous medium is used for wallpaper printing, the coating has good anti-adhesion effect; the paint prepared by adding the pigment and the filler has the advantages that the film forming of a paint film is continuous and smooth, the glossiness is high, and the dispersibility of the filler in a medium and the color fixing effect of the pigment are good; the wallpaper finally coated with the medium coating has good water resistance, strong wiping resistance and high wear resistance.
Description
Technical Field
The invention relates to a printing aqueous medium, in particular to an aqueous medium for wallpaper printing and a preparation method thereof.
Background
With the increasing awareness of environmental protection and the increasing soundness of law, printing media have undergone a transition from solvent-based to aqueous, and aqueous media for printing are called environmentally-friendly new green materials because they do not contain organic solvents and the like.
The aqueous medium is a main component forming the wallpaper printing ink, and needs to have better printing adaptability, better leveling property and transfer property during printing; the coating film has high glossiness and good transparency after being dried; the anti-adhesion effect is good, the plasticizer is prevented from being separated out, and the requirements of various scratch resistance and scuff resistance in the cleaning and maintenance of wallpaper printing products during construction and after construction can be met.
At present, in wallpaper printing aqueous medium products, both imported aqueous media and domestic aqueous media use thermoplastic acrylic resin polymer emulsion as a main film forming substance, the problems of low glossiness, poor blocking resistance, poor water resistance and solvent resistance and the like generally exist, and particularly, when cleaning and maintenance are carried out after construction, the wiping resistance is poor, so that the coating effect is seriously influenced. In order to overcome the defects, some aqueous media with better blocking resistance and water resistance appear in the market, but the media meet the requirements of water resistance and blocking resistance by adding fluorine-containing and silicon-containing auxiliaries, most of the fluorine-containing and silicon-containing auxiliaries are imported products, the synthesis process is generally complex, the yield is lower, the price is extremely high, the compatibility with a system is not very good, and therefore the adding amount is less. The use of the auxiliary agents not only increases the printing cost, but also influences the storage stability of the final product, and restricts the long-term development of the packaging and printing industry in China.
Disclosure of Invention
The invention aims to provide an aqueous medium for wallpaper printing and a preparation method thereof, so as to solve the common problems of low glossiness, poor blocking resistance and poor water resistance in the prior art.
In order to solve the above technical problems, according to an aspect of the present invention, there is provided an aqueous medium for wallpaper printing, the raw materials of which include a core monomer raw material, a shell monomer raw material, and other raw materials; the core monomer raw materials comprise, by mass, 40-70 parts of methyl methacrylate, 5-18 parts of butyl methacrylate, 1-3 parts of dibutyl itaconate, 1.5-3 parts of acrylic acid and 1-3 parts of hydroxyethyl methacrylate; the shell monomer raw materials comprise 30-50 parts of methyl methacrylate, 10-36 parts of butyl methacrylate, 2-5 parts of dibutyl itaconate, 3-6 parts of acrylamide and 3-5 parts of dodecafluoroheptyl methacrylate; the other raw materials comprise 3-5 parts of active emulsifier, 30-55 parts of initiator, 0.2-0.5 part of buffering agent, 90-190 parts of deionized water, 0.5-1 part of defoaming agent, 0.5-1 part of flatting agent, 0.1-0.5 part of wetting agent, 0.25-0.5 part of PH regulator and 0.2-0.6 part of wear-resistant auxiliary agent.
Further, the active emulsifier is sodium alkyl alcohol polyoxyethylene ether sulfate.
Further, the initiator is an ammonium persulfate aqueous solution with the mass percentage concentration of 3%.
Further, the defoaming agent is polyether siloxane copolymer.
Further, the leveling agent is polyether modified polydimethylsiloxane.
Further, the wetting agent is polyether modified silicone oil.
Further, the pH regulator is aminomethyl propanol.
Further, the wear-resistant auxiliary agent is polydimethylsiloxane dispersion.
According to another aspect of the present invention, there is provided a method for preparing the aqueous medium for wallpaper printing, comprising:
step one, preparation of nuclear monomer
Mixing methyl methacrylate, butyl methacrylate, dibutyl itaconate, acrylic acid and hydroxyethyl methacrylate into a nuclear monomer according to a metering ratio;
step two, preparation of shell monomer
Mixing methyl methacrylate, butyl methacrylate, dibutyl itaconate, acrylamide and dodecafluoroheptyl methacrylate into a shell monomer according to a metering ratio;
step three, preparing fluorine-containing acrylate emulsion with core-shell structure
Adding a reactive emulsifier and a buffering agent into deionized water, stirring uniformly, adding 1/2 amounts of nuclear monomers, heating to 75 ℃, adding 1/3 amounts of initiator ammonium persulfate aqueous solution, heating to 80 ℃, reacting for half an hour under heat preservation, and then dropwise adding the rest nuclear monomers; after finishing dropping, beginning to drop shell monomers and 1/2 parts of initiator ammonium persulfate aqueous solution, controlling the dropping to be finished within about 3 hours, heating to 85 ℃, carrying out heat preservation reaction for 1 hour, then adding the rest 1/6 parts of initiator ammonium persulfate aqueous solution, heating to 90 ℃, carrying out curing reaction for 1 hour, cooling, filtering and discharging to obtain the core-shell structure fluorine-containing acrylate emulsion;
in the third step, the purpose of adopting the segmented reaction is to synthesize the acrylic emulsion with the core-shell structure, so that the performance of the emulsion is closer to the initial design, the core part plays an anti-adhesion effect during film formation, and the fluorine-containing monomer can more easily play a water-resistant effect on the shell layer.
Step four, preparing the aqueous medium for wallpaper printing
And (3) fully mixing and dispersing the flatting agent, the wetting agent, the defoaming agent, the pH regulator and the wear-resistant auxiliary agent into the core-shell structure fluorine-containing acrylate emulsion obtained in the step three to obtain the aqueous medium for wallpaper printing.
According to another aspect of the present invention, there is also provided a use of the aqueous medium for wallpaper printing obtained according to the above preparation method in wallpaper printing paint. When the aqueous medium is used for wallpaper printing, the coating has good anti-adhesion effect; the paint prepared by adding the pigment and the filler has the advantages that the film forming of a paint film is continuous and smooth, the glossiness is high, and the dispersibility of the filler in a medium and the color fixing effect of the pigment are good; the wallpaper finally coated with the medium coating has good water resistance, strong wiping resistance and high wear resistance.
Compared with the prior art, the invention has the following technical effects:
according to the water-based medium for wallpaper printing, dibutyl itaconate is introduced into a polymer molecular chain, and the dibutyl itaconate has a moderate glass transition temperature, so that plasticizing acting force in a system can be enhanced, the anti-adhesion effect of a coating film is good, and two butyl ester groups with strong hydrophobicity are contained in molecules, so that the water resistance of the coating film can be effectively improved. The paint prepared by adding the pigment and the filler into the aqueous medium has the advantages of continuous and smooth film formation of a paint film, high glossiness, good dispersibility of the filler in the medium and good color fixing effect of the pigment. After testing, after the aqueous medium for wallpaper printing is dried to form a film, a 5KG weight is pressed on the adhesive film, the adhesive film is placed in a drying oven at 50 ℃, and after 50-60 hours, the adhesive film is inspected at room temperature to be not adhered.
According to the water-based medium for wallpaper printing, the fluorine-containing monomer dodecafluoroheptyl methacrylate is introduced into the polymer molecular chain, the fluorine content in the system is increased, the specific surface area of a coating film of the water-based medium is increased, the surface tension is enhanced, the hydrophobicity of the coating film is improved, and the water resistance effect is obviously enhanced after the coating film is printed on the wallpaper. Through tests, the aqueous medium is coated and soaked in water for 48-55 hours, and does not foam or peel (the coating is tested according to the GB/T1733-. The medium also avoids the effect of reducing the cost by adding expensive fluorine-containing auxiliary agent to improve the water resistance of the coating.
And thirdly, the water-based medium for wallpaper printing provided by the invention contains the wear-resistant additive, so that the friction coefficient can be reduced, and a wallpaper printing coating has coating smoothness and wear resistance. Through tests, the wallpaper coating can be rubbed back and forth under the pressure of 4 pounds for 500-800 hours without scratching and fading (determined according to the test standard GB/T1768-1989 paint film abrasion resistance determination method).
Detailed Description
The claimed solution is further illustrated by the following examples. However, the examples are intended to illustrate embodiments of the invention without departing from the scope of the subject matter of the invention, and the scope of the invention is not limited by the examples. Unless otherwise specifically indicated, all other raw materials used are commercially available raw materials commonly used for resins and coatings.
In the following examples, the reactive emulsifier is sodium alkyl alcohol polyoxyethylene ether sulfate, which is purchased from Guangzhou double bond trade company; the initiator is an ammonium persulfate aqueous solution with the mass percentage concentration of 3%; the defoaming agent is polyether siloxane copolymer which is purchased from Shanghai Kahn chemical Co., Ltd; the leveling agent is polyether modified polydimethylsiloxane, and is purchased from New Material science and technology Limited of Bauer, Hangzhou; the wetting agent is polyether modified silicone oil, which is purchased from New materials of Kening, Foshan City; the pH regulator is aminomethyl propanol, which is purchased from Guangdong Yuebeautification industries, Inc.; the abrasion resistant additive is a polydimethylsiloxane dispersion which is purchased from Soumann chemical Co., Ltd.
Example 1
Composition of raw materials
Raw materials for the core monomer: 45 parts of methyl methacrylate, 7 parts of butyl methacrylate, 1 part of dibutyl itaconate, 2 parts of acrylic acid and 1 part of hydroxyethyl methacrylate.
Raw materials for constituting the shell monomer: 34 parts of methyl methacrylate, 14 parts of butyl methacrylate, 2 parts of dibutyl itaconate, 3 parts of acrylamide and 3 parts of dodecafluoroheptyl methacrylate.
Other raw materials: 3 parts of active emulsifier, 34 parts of initiator, 0.2 part of buffering agent, 135 parts of deionized water, 0.6 part of defoaming agent, 0.6 part of flatting agent, 0.3 part of wetting agent, 0.3 part of PH regulator and 0.2 part of wear-resistant assistant.
Preparation method
(1) Mixing 45 parts of methyl methacrylate, 7 parts of butyl methacrylate, 1 part of dibutyl itaconate, 2 parts of acrylic acid and 1 part of hydroxyethyl methacrylate into a nuclear monomer;
(2) mixing 34 parts of methyl methacrylate, 14 parts of butyl methacrylate, 2 parts of dibutyl itaconate, 3 parts of acrylamide and 3 parts of dodecafluoroheptyl methacrylate into a shell monomer;
(3) adding 3 parts of active emulsifier and 0.2 part of buffering agent into 135 parts of deionized water, stirring uniformly, adding 1/2 parts of core monomer by total weight, heating to 75 ℃, adding 1/3 parts of initiator ammonium persulfate solution, slowly heating to 80 ℃, carrying out heat preservation reaction for half an hour, then dropwise adding the rest of core monomer, after dropwise adding, beginning dropwise adding shell monomer and 1/2 parts of initiator ammonium persulfate aqueous solution, controlling the temperature to be about 3 hours, heating to 85 ℃, carrying out heat preservation reaction for 1 hour, then adding the rest of initiator ammonium persulfate aqueous solution, heating to 90 ℃, carrying out curing reaction for 1 hour, cooling, filtering, and discharging to obtain the core-shell structure fluorine-containing acrylate emulsion;
(4) 0.6 part of flatting agent, 0.3 part of wetting agent and 0.6 part of defoaming agent; and (3) fully mixing and dispersing 0.3 part of pH regulator and 0.2 part of wear-resistant additive in the core-shell structure fluorine-containing acrylate emulsion obtained in the step (3) to obtain the aqueous medium for wallpaper printing.
And drying the obtained water-based medium for wallpaper printing to form a film, pressing a 5KG weight on the adhesive film, placing the adhesive film in a 50-DEG C oven, and inspecting at room temperature after 50 hours to prevent adhesion.
The obtained water-based medium for wallpaper printing is tested according to GB/T1733-1993 paint film water resistance determination method, and a coating film does not bubble or peel after being soaked in water for 48 hours.
The obtained water-based medium for wallpaper printing is tested according to GB/T1768-1989 paint film abrasion resistance determination method, and a coating film is not scratched or faded under the condition of back-and-forth friction of 600 under the pressure of 4 pounds.
Example 2
Composition of raw materials
Raw materials for the core monomer: 50 parts of methyl methacrylate, 8 parts of butyl methacrylate, 1.5 parts of dibutyl itaconate, 1.5 parts of acrylic acid and 2 parts of hydroxyethyl methacrylate.
Raw materials for constituting the shell monomer: 37 parts of methyl methacrylate, 16 parts of butyl methacrylate, 2.5 parts of dibutyl itaconate, 3 parts of acrylamide and 4 parts of dodecafluoroheptyl methacrylate.
Other raw materials: 4 parts of active emulsifier, 36 parts of initiator, 0.5 part of buffering agent, 90 parts of deionized water, 0.6 part of defoaming agent, 0.6 part of flatting agent, 0.1 part of wetting agent, 0.3 part of PH regulator and 0.6 part of wear-resistant assistant.
Preparation method
(1) Mixing 50 parts of methyl methacrylate, 8 parts of butyl methacrylate, 1.5 parts of dibutyl itaconate, 1.5 parts of acrylic acid and 2 parts of hydroxyethyl methacrylate into a nuclear monomer;
(2) mixing 37 parts of methyl methacrylate, 16 parts of butyl methacrylate, 2.5 parts of dibutyl itaconate, 3 parts of acrylamide and 4 parts of dodecafluoroheptyl methacrylate into a shell monomer;
(3) adding 4 parts of active emulsifier and 0.5 part of buffering agent into 90 parts of deionized water, stirring uniformly, adding 1/2 parts of core monomer by total weight, heating to 75 ℃, adding 1/3 parts of initiator ammonium persulfate solution, slowly heating to 80 ℃, carrying out heat preservation reaction for half an hour, then dropwise adding the rest of core monomer, after dropwise adding, beginning dropwise adding shell monomer and 1/2 parts of initiator ammonium persulfate aqueous solution, controlling the dropwise adding to be finished within about 3 hours, adding the rest of initiator ammonium persulfate aqueous solution, heating to 90 ℃, carrying out curing reaction for 1 hour, cooling, filtering and discharging to obtain the fluoroacrylate emulsion with the core-shell structure;
(4) 0.6 part of flatting agent, 0.1 part of wetting agent and 0.6 part of defoaming agent; and (3) fully mixing and dispersing 0.3 part of pH regulator and 0.6 part of wear-resistant additive in the core-shell structure fluorine-containing acrylate emulsion obtained in the step (3) to obtain the aqueous medium for wallpaper printing.
And drying the obtained water-based medium for wallpaper printing to form a film, pressing a 5KG weight on the adhesive film, placing the adhesive film in an oven at 50 ℃, and inspecting at room temperature after 55 hours to prevent adhesion.
The obtained water-based medium for wallpaper printing is tested according to GB/T1733 + 1993 paint film water resistance determination method, and a coating film is soaked in water for 55 hours and does not bubble or peel off.
The obtained water-based medium for wallpaper printing is tested according to GB/T1768-1989 paint film abrasion resistance determination method, and a coating film is not scratched or faded under the pressure of 4 pounds and the back-and-forth friction of 500.
Example 3
Composition of raw materials
Raw materials for the core monomer: 70 parts of methyl methacrylate, 13 parts of butyl methacrylate, 1 part of dibutyl itaconate, 3 parts of acrylic acid and 3 parts of hydroxyethyl methacrylate.
Raw materials for constituting the shell monomer: 50 parts of methyl methacrylate, 28 parts of butyl methacrylate, 2 parts of dibutyl itaconate, 6 parts of acrylamide, 4 parts of dodecafluoroheptyl methacrylate,
Other raw materials: 5 parts of active emulsifier, 55 parts of initiator, 0.5 part of buffering agent, 150 parts of deionized water, 1 part of defoaming agent, 1 part of flatting agent, 0.5 part of wetting agent, 0.5 part of pH regulator and 0.4 part of wear-resistant assistant.
Preparation method
(1) Mixing 70 parts of methyl methacrylate, 13 parts of butyl methacrylate, 1 part of dibutyl itaconate, 3 parts of acrylic acid and 3 parts of hydroxyethyl methacrylate into a nuclear monomer;
(2) mixing 50 parts of methyl methacrylate, 28 parts of butyl methacrylate, 2 parts of dibutyl itaconate, 6 parts of acrylamide and 4 parts of dodecafluoroheptyl methacrylate into a shell monomer;
(3) adding 5 parts of active emulsifier and 0.5 part of buffering agent into 150 parts of deionized water, stirring uniformly, adding 1/2 parts of core monomer by total weight, heating to 70 ℃, adding 1/3 parts of initiator ammonium persulfate solution, slowly heating to 80 ℃, carrying out heat preservation reaction for half an hour, then dropwise adding the rest of core monomer, after dropwise adding, beginning dropwise adding shell monomer and 1/2 parts of initiator ammonium persulfate aqueous solution, controlling the temperature to be about 3 hours, heating to 85 ℃, carrying out heat preservation reaction for 1 hour, then adding the rest of initiator ammonium persulfate aqueous solution, heating to 90 ℃, carrying out curing reaction for 1 hour, cooling, filtering, and discharging to obtain the core-shell structure fluorine-containing acrylate emulsion;
(4) 1 part of flatting agent, 0.5 part of wetting agent and 1 part of defoaming agent; and (3) fully mixing and dispersing 0.5 part of pH regulator and 0.4 part of wear-resistant additive in the core-shell structure fluorine-containing acrylate emulsion obtained in the step (3) to obtain the aqueous medium for wallpaper printing.
And drying the obtained water-based medium for wallpaper printing to form a film, pressing a 5KG weight on the adhesive film, placing the adhesive film in a 50-DEG C oven, and inspecting at room temperature after 60 hours to prevent adhesion.
The obtained water-based medium for wallpaper printing is tested according to GB/T1733-1993 paint film water resistance determination method, and a coating film does not bubble or peel after being soaked in water for 52 hours.
The obtained water-based medium for wallpaper printing is tested according to GB/T1768-1989 paint film abrasion resistance determination method, and a coating film is not scratched or faded under the pressure of 4 pounds and the back-and-forth friction of 800.
Example 4
Composition of raw materials
Raw materials for the core monomer: 40 parts of methyl methacrylate, 5 parts of butyl methacrylate, 1 part of dibutyl itaconate, 1.5 parts of acrylic acid and 2.5 parts of hydroxyethyl methacrylate.
Raw materials for constituting the shell monomer: 30 parts of methyl methacrylate, 10 parts of butyl methacrylate, 2 parts of dibutyl itaconate, 4 parts of acrylamide and 5 parts of dodecafluoroheptyl methacrylate.
Other raw materials: 3 parts of active emulsifier, 30 parts of initiator, 0.2 part of buffering agent, 120 parts of deionized water, 0.5 part of defoaming agent, 0.5 part of flatting agent, 0.2 part of wetting agent, 0.25 part of PH regulator and 0.3 part of wear-resistant assistant.
Preparation method
(1) Mixing 40 parts of methyl methacrylate, 5 parts of butyl methacrylate, 1 part of dibutyl itaconate, 1.5 parts of acrylic acid and 2.5 parts of hydroxyethyl methacrylate into a nuclear monomer;
(2) mixing 30 parts of methyl methacrylate, 10 parts of butyl methacrylate, 2 parts of dibutyl itaconate, 4 parts of acrylamide and 5 parts of dodecafluoroheptyl methacrylate into a shell monomer;
(3) adding 3 parts of active emulsifier and 0.2 part of buffering agent into 120 parts of deionized water, stirring uniformly, adding 1/2 parts of core monomer by total weight, heating to 75 ℃, adding 1/3 parts of initiator ammonium persulfate solution, slowly heating to 80 ℃, carrying out heat preservation reaction for half an hour, then dropwise adding the rest of core monomer, after dropwise adding, beginning dropwise adding shell monomer and 1/2 parts of initiator ammonium persulfate aqueous solution, controlling the temperature to be about 3 hours, heating to 85 ℃, carrying out heat preservation reaction for 1 hour, then adding the rest of initiator ammonium persulfate aqueous solution, heating to 90 ℃, carrying out curing reaction for 1 hour, cooling, filtering, and discharging to obtain the core-shell structure fluorine-containing acrylate emulsion;
(4) 0.5 part of flatting agent, 0.2 part of wetting agent and 0.5 part of defoaming agent; and (3) fully mixing and dispersing 0.25 part of pH regulator and 0.3 part of wear-resistant additive in the core-shell structure fluorine-containing acrylate emulsion obtained in the step (3) to obtain the aqueous medium for wallpaper printing.
And drying the obtained water-based medium for wallpaper printing to form a film, pressing a 5KG weight on the adhesive film, placing the adhesive film in a 50-DEG C oven, and inspecting at room temperature after 52 hours to prevent adhesion.
The obtained water-based medium for wallpaper printing is tested according to GB/T1733-1993 paint film water resistance determination method, and a coating film does not bubble or peel after being soaked in water for 49 hours.
The obtained water-based medium for wallpaper printing is tested according to GB/T1768-1989 paint film abrasion resistance determination method, and a coating film is not scratched or faded under the pressure of 4 pounds and the back-and-forth friction of 700 pounds.
Example 5
Composition of raw materials
Raw materials for the core monomer: 60 parts of methyl methacrylate, 18 parts of butyl methacrylate, 3 parts of dibutyl itaconate, 3 parts of acrylic acid and 2 parts of hydroxyethyl methacrylate.
Raw materials for constituting the shell monomer: 42 parts of methyl methacrylate, 36 parts of butyl methacrylate, 5 parts of dibutyl itaconate, 5 parts of acrylamide and 3 parts of dodecafluoroheptyl methacrylate
Other raw materials: 5 parts of active emulsifier, 54 parts of initiator, 0.3 part of buffering agent, 190 parts of deionized water, 0.9 part of defoaming agent, 0.9 part of flatting agent, 0.4 part of wetting agent, 0.4 part of PH regulator and 0.5 part of wear-resistant assistant.
Preparation method
(1) Mixing 60 parts of methyl methacrylate, 18 parts of butyl methacrylate, 3 parts of dibutyl itaconate, 3 parts of acrylic acid and 2 parts of hydroxyethyl methacrylate into a nuclear monomer;
(2) mixing 42 parts of methyl methacrylate, 36 parts of butyl methacrylate, 5 parts of dibutyl itaconate, 5 parts of acrylamide and 3 parts of dodecafluoroheptyl methacrylate into a shell monomer;
(3) adding 5 parts of active emulsifier and 0.3 part of buffering agent into 190 parts of deionized water, stirring uniformly, adding 1/2 parts of core monomer by total weight, heating to 75 ℃, adding 1/3 parts of initiator ammonium persulfate solution, slowly heating to 80 ℃, carrying out heat preservation reaction for half an hour, then dropwise adding the rest of core monomer, after dropwise adding, beginning dropwise adding shell monomer and 1/2 parts of initiator ammonium persulfate aqueous solution, controlling the temperature to be about 3 hours, heating to 85 ℃, carrying out heat preservation reaction for 1 hour, then adding the rest of initiator ammonium persulfate aqueous solution, heating to 90 ℃, carrying out curing reaction for 1 hour, cooling, filtering, and discharging to obtain the core-shell structure fluorine-containing acrylate emulsion;
(4) 0.9 part of flatting agent, 0.3 part of wetting agent and 0.9 part of defoaming agent; and (3) fully mixing and dispersing 0.4 part of pH regulator and 0.5 part of wear-resistant additive in the core-shell structure fluorine-containing acrylate emulsion obtained in the step (3) to obtain the aqueous medium for wallpaper printing.
And drying the obtained water-based medium for wallpaper printing to form a film, pressing a 5KG weight on the adhesive film, placing the adhesive film in an oven at 50 ℃, and inspecting at room temperature after 58 hours to prevent adhesion.
The obtained water-based medium for wallpaper printing is tested according to GB/T1733-1993 paint film water resistance determination method, and a coating film does not bubble or peel after being soaked in water for 53 hours.
The obtained water-based medium for wallpaper printing is tested according to GB/T1768-1989 paint film abrasion resistance determination method, and a coating film is rubbed back and forth at 650 ℃ under 4 pounds of pressure without scratching and fading.
Comparative example 1
Raw materials for the core monomer: 46 parts of methyl methacrylate, 7 parts of butyl methacrylate, 2 parts of acrylic acid and 1 part of hydroxyethyl methacrylate.
Raw materials for constituting the shell monomer: 36 parts of methyl methacrylate, 14 parts of butyl methacrylate, 3 parts of acrylamide and 3 parts of dodecafluoroheptyl methacrylate.
Dibutyl itaconate is not added in the raw materials of the core monomer and the shell monomer.
The preparation method is the same as example 1.
Comparative example 2
Raw materials for the core monomer: 45 parts of methyl methacrylate, 7 parts of butyl methacrylate, 1 part of dibutyl itaconate, 2 parts of acrylic acid and 1 part of hydroxyethyl methacrylate.
Raw materials for constituting the shell monomer: 37 parts of methyl methacrylate, 14 parts of butyl methacrylate, 2 parts of dibutyl itaconate and 3 parts of acrylamide.
Dodecafluoroheptyl methacrylate is not added to the shell monomer.
The preparation method is the same as example 1.
Comparative example 3
Raw materials for the core monomer: 46 parts of methyl methacrylate, 7 parts of butyl methacrylate, 2 parts of acrylic acid and 1 part of hydroxyethyl methacrylate.
Raw materials for constituting the shell monomer: 39 parts of methyl methacrylate, 14 parts of butyl methacrylate and 3 parts of acrylamide.
Dibutyl itaconate is not added in raw materials of the core monomer and the shell monomer, and dodecafluoroheptyl methacrylate is not added in the shell monomer.
The preparation method is the same as example 1.
TABLE 1
Table 1 shows the results of examination of the aqueous media obtained in example 1 and comparative examples 1 to 3. The test method of the comparative example was the same as that of example 1.
Claims (10)
1. An aqueous medium for wallpaper printing, characterized in that: the raw materials comprise a core monomer raw material, a shell monomer raw material and other raw materials; the core monomer raw materials comprise, by mass, 40-70 parts of methyl methacrylate, 5-18 parts of butyl methacrylate, 1-3 parts of dibutyl itaconate, 1.5-3 parts of acrylic acid and 1-3 parts of hydroxyethyl methacrylate; the shell monomer raw materials comprise 30-50 parts of methyl methacrylate, 10-36 parts of butyl methacrylate, 2-5 parts of dibutyl itaconate, 3-6 parts of acrylamide and 3-5 parts of dodecafluoroheptyl methacrylate; the other raw materials comprise 3-5 parts of active emulsifier, 30-55 parts of initiator, 0.2-0.5 part of buffering agent, 90-190 parts of deionized water, 0.5-1 part of defoaming agent, 0.5-1 part of flatting agent, 0.1-0.5 part of wetting agent, 0.25-0.5 part of PH regulator and 0.2-0.6 part of wear-resistant auxiliary agent.
2. The aqueous medium for wallpaper printing according to claim 1, characterized in that: the active emulsifier is sodium alkyl alcohol polyoxyethylene ether sulfate.
3. The aqueous medium for wallpaper printing according to claim 1, characterized in that: the initiator is an ammonium persulfate aqueous solution with the mass percentage concentration of 3%.
4. The aqueous medium for wallpaper printing according to claim 1, characterized in that: the defoaming agent is polyether siloxane copolymer.
5. The aqueous medium for wallpaper printing according to claim 1, characterized in that: the leveling agent is polyether modified polydimethylsiloxane.
6. The aqueous medium for wallpaper printing according to claim 1, characterized in that: the wetting agent is polyether modified silicone oil.
7. The aqueous medium for wallpaper printing according to claim 1, characterized in that: the pH regulator is aminomethyl propanol.
8. The aqueous medium for wallpaper printing according to claim 1, characterized in that: the wear-resistant auxiliary agent is polydimethylsiloxane dispersoid.
9. The method for producing an aqueous medium for wallpaper printing according to any one of claims 1 to 8, comprising:
step one, preparation of nuclear monomer
Mixing methyl methacrylate, butyl methacrylate, dibutyl itaconate, acrylic acid and hydroxyethyl methacrylate into a nuclear monomer according to a metering ratio;
step two, preparation of shell monomer
Mixing methyl methacrylate, butyl methacrylate, dibutyl itaconate, acrylamide and dodecafluoroheptyl methacrylate into a shell monomer according to a metering ratio;
step three, preparing fluorine-containing acrylate emulsion with core-shell structure
Adding a reactive emulsifier and a buffering agent into deionized water, stirring uniformly, adding 1/2 amounts of nuclear monomers, heating to 75 ℃, adding 1/3 amounts of initiator ammonium persulfate aqueous solution, heating to 80 ℃, reacting for half an hour under heat preservation, and then dropwise adding the rest nuclear monomers; after finishing dropping, beginning to drop shell monomers and 1/2 parts of initiator ammonium persulfate aqueous solution, controlling the dropping to be finished within about 3 hours, heating to 85 ℃, carrying out heat preservation reaction for 1 hour, then adding the rest 1/6 parts of initiator ammonium persulfate aqueous solution, heating to 90 ℃, carrying out curing reaction for 1 hour, cooling, filtering and discharging to obtain the core-shell structure fluorine-containing acrylate emulsion;
step four, preparing the aqueous medium for wallpaper printing
And (3) fully mixing and dispersing the flatting agent, the wetting agent, the defoaming agent, the pH regulator and the wear-resistant auxiliary agent into the core-shell structure fluorine-containing acrylate emulsion obtained in the step three to obtain the aqueous medium for wallpaper printing.
10. Use of the aqueous medium for wallpaper printing obtained by the preparation method according to claim 9 in wallpaper printing paints.
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