CN113372500B - Functional acrylic emulsion, preparation method thereof, wear-resistant acrylic coating film and acrylic coating BOPP film - Google Patents
Functional acrylic emulsion, preparation method thereof, wear-resistant acrylic coating film and acrylic coating BOPP film Download PDFInfo
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- CN113372500B CN113372500B CN202110824028.7A CN202110824028A CN113372500B CN 113372500 B CN113372500 B CN 113372500B CN 202110824028 A CN202110824028 A CN 202110824028A CN 113372500 B CN113372500 B CN 113372500B
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000000839 emulsion Substances 0.000 title claims abstract description 91
- 239000011248 coating agent Substances 0.000 title claims description 71
- 238000000576 coating method Methods 0.000 title claims description 71
- 229920006378 biaxially oriented polypropylene Polymers 0.000 title claims description 43
- 239000011127 biaxially oriented polypropylene Substances 0.000 title claims description 43
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000000178 monomer Substances 0.000 claims abstract description 71
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 46
- 229920005792 styrene-acrylic resin Polymers 0.000 claims abstract description 46
- 239000003999 initiator Substances 0.000 claims abstract description 44
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 30
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims abstract description 14
- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 48
- 238000010438 heat treatment Methods 0.000 claims description 37
- 238000002156 mixing Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011527 polyurethane coating Substances 0.000 claims description 10
- 239000004814 polyurethane Substances 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 238000005299 abrasion Methods 0.000 claims description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 3
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 241000238367 Mya arenaria Species 0.000 abstract description 3
- 239000011258 core-shell material Substances 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 67
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- 239000000463 material Substances 0.000 description 16
- 238000001035 drying Methods 0.000 description 12
- 239000002585 base Substances 0.000 description 8
- 239000013530 defoamer Substances 0.000 description 8
- 238000007789 sealing Methods 0.000 description 7
- 239000005033 polyvinylidene chloride Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000779 smoke Substances 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 235000019504 cigarettes Nutrition 0.000 description 3
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 2
- 125000005336 allyloxy group Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012788 optical film Substances 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- WQPMYSHJKXVTME-UHFFFAOYSA-N 3-hydroxypropane-1-sulfonic acid Chemical compound OCCCS(O)(=O)=O WQPMYSHJKXVTME-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 235000017858 Laurus nobilis Nutrition 0.000 description 1
- VFTKIWJJPDJBKD-UHFFFAOYSA-N OCCC[Na] Chemical compound OCCC[Na] VFTKIWJJPDJBKD-UHFFFAOYSA-N 0.000 description 1
- 235000005212 Terminalia tomentosa Nutrition 0.000 description 1
- 244000125380 Terminalia tomentosa Species 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention provides a functional acrylic emulsion, which comprises the following components: 5-20 parts by weight of styrene-acrylic resin emulsion; 66.5 to 73.5 parts by weight of water; 5-10 parts by weight of hard monomer; 5-10 parts by weight of a soft monomer; 1-2 parts by weight of functional monomer; acrylic acid 0.5-1.5 weight portions; 0.5 to 1 weight portion of diacetone acrylamide; 0.25 to 0.5 weight portion of adipic dihydrazide; 0.5 to 2 weight portions of emulsifying agent; 0.5 to 2 weight portions of initiator; 0.1 to 0.2 part by weight of defoaming agent. Compared with the prior art, the invention adopts the design principle of hard core and soft shell, uses styrene-acrylic resin emulsion as seed emulsion, carries out core-shell polymerization on the styrene-acrylic resin emulsion, hard monomer, soft monomer, functional monomer and acrylic acid to obtain self-crosslinking functional acrylic emulsion with good wear resistance, introduces diacetone acrylamide and adipic dihydrazide to crosslink in the polymerization process, and further improves the wear resistance and anti-back adhesion performance.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a functional acrylic emulsion, a preparation method thereof, an abrasion-resistant acrylic acid coating film and an acrylic acid coating BOPP film.
Background
BOPP (biaxially oriented polypropylene) film for cigarette packaging mainly requires good transparency, high laminating property, good heat sealing property and good aroma and water resistance, but the wear resistance of the BOPP film is to be improved, the film surface is easily scratched to influence the appearance due to friction in the boxing transportation process, and higher wear resistance requirements are provided for packaging films of some high-grade cigarettes.
In order to improve the wear resistance of the smoke film, domestic researches are started to solve the problem through a functional coating, and as disclosed in Chinese patent publication No. CN103059193A, PVDC coating latex special for the smoke film and a preparation method and application thereof are disclosed, wherein the method is to polymerize polyvinylidene chloride monomer into polyvinylidene chloride (PVDC) emulsion. The coating formed by coating the emulsion on the BOPP film has certain barrier fragrance retention and wear resistance, but the PVDC coating can yellow, the coating film can not be melted, granulated and recycled, and if the waste is burnt, substances such as hydrogen chloride, dioxin and the like which are toxic and harmful to human bodies and surrounding environments can be generated. In view of the above environmental protection problems, countries such as europe and america are gradually passing through environmental protection materials to replace PVDC coating at present.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a functional acrylic emulsion, a preparation method thereof, a wear-resistant acrylic coating film, and an acrylic coating BOPP film, wherein the acrylic coating film formed by the functional acrylic emulsion has good wear resistance and anti-back adhesion performance.
The invention provides a functional acrylic emulsion, which comprises the following components:
the solid content of the styrene-acrylic resin emulsion is 20% -30%.
Preferably, the styrene-acrylic resin emulsion is prepared according to the following method:
mixing styrene-acrylic resin, water and organic alkali, heating and stirring to obtain styrene-acrylic resin emulsion;
the mass ratio of the styrene-acrylic resin to the water to the organic alkali is (20-30): (60-75): (5-10).
Preferably, the glass transition temperature of the styrene-acrylic resin is 95-110 ℃; the solid content of the styrene-acrylic resin is more than or equal to 98%;
the organic base is selected from one or more of ammonia water, monoethanolamine and triethanolamine.
Preferably, the hard monomer is selected from methacrylate hard monomers and/or acrylate hard monomers;
the soft monomer is selected from one or more of n-butyl acrylate, n-octyl methacrylate and isooctyl acrylate;
the functional monomer is selected from one or more of hydroxyethyl methacrylate, lauryl methacrylate, acrylamide and 2-hydroxypropyl methacrylate;
the emulsifier is selected from sulfonate containing allyl;
the initiator is selected from potassium persulfate and/or ammonium persulfate;
the defoaming agent is an organosilicon defoaming agent.
Preferably, the method comprises the steps of:
s1) mixing a hard monomer, a soft monomer, a functional monomer, acrylic acid and diacetone acrylamide to obtain a mixed monomer;
mixing part of water with an emulsifier to obtain an emulsifier solution;
mixing the other part of water with an initiator to obtain an initiator solution;
s2) mixing the rest water, the styrene-acrylic resin emulsion, part of the emulsifier solution and part of the initiator solution, heating and stirring, simultaneously and continuously adding the mixed monomer, the rest emulsifier solution and the rest initiator solution, continuously heating and reacting, cooling, adding adipic acid dihydrazide, stirring and reacting, and adding a defoaming agent to obtain the functional acrylic emulsion.
Preferably, the mass ratio of the part of water to the other part of water to the rest of water is (10-30): (10-20): (50-80);
the mass ratio of the part of the emulsifier solution to the rest of the emulsifier solution is (1-3): (7-9);
the mass ratio of the partial initiator solution to the rest initiator solution is (2-4): (6-8).
Preferably, the temperature of the heating and stirring is 80-85 ℃; the heating and stirring time is 40-80 min; the rotating speed of the heating and stirring is 80-200 r/min;
the time for continuously adding the mixed monomer, the rest of the emulsifier solution and the rest of the initiator solution is 3-5 h;
the temperature of the continuous heating reaction is 80-85 ℃; continuously heating and reacting for 1-2 h;
after the continuous heating reaction, the pH value of the reaction system is regulated to 7-8, and then the temperature is reduced;
the temperature is reduced to below 40 ℃;
the stirring reaction time is 10-30 min.
The invention also provides a wear-resistant acrylic acid coating film which is formed by the functional acrylic acid emulsion prepared by the preparation method.
The invention also provides an acrylic coated BOPP film comprising a BOPP film;
one or two sides of the BOPP film are sequentially provided with a polyurethane coating film and a wear-resistant acrylic coating film;
the wear-resistant acrylic acid coating film is formed by the functional acrylic acid emulsion prepared by the preparation method.
Preferably, the coating amount of the polyurethane coating film is 0.1 to 0.5g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The coating weight of the wear-resistant acrylic acid coating film is 0.5-1.5 g/cm 3 。
The invention provides a functional acrylic emulsion, which comprises the following components: 5-20 parts by weight of styrene-acrylic resin emulsion; 66.5 to 73.5 parts by weight of water; 5-10 parts by weight of hard monomer; 5-10 parts by weight of a soft monomer; 1-2 parts by weight of functional monomer; acrylic acid 0.5-1.5 weight portions; 0.5 to 1 weight portion of diacetone acrylamide; 0.25 to 0.5 weight portion of adipic dihydrazide; 0.5 to 2 weight portions of emulsifying agent; 0.5 to 2 weight portions of initiator; 0.1 to 0.2 weight portion of defoaming agent; the solid content of the styrene-acrylic resin emulsion is 20% -30%. Compared with the prior art, the invention adopts the design principle of hard core and soft shell, uses styrene-acrylic resin emulsion as seed emulsion, carries out core-shell polymerization on the styrene-acrylic resin emulsion, hard monomer, soft monomer, functional monomer and acrylic acid to obtain self-crosslinking functional acrylic emulsion with good wear resistance, introduces diacetone acrylamide and adipic dihydrazide to crosslink in the polymerization process, and further improves the wear resistance and anti-back adhesion performance.
The test result shows that the heat sealing strength of the acrylic acid coating BOPP film prepared by the invention is more than 2.0N/15mm; the coating has no scratch after being rubbed for 400 times for 4 pounds; the coating film haze was <2.5.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a functional acrylic emulsion, which comprises the following components:
the solid content of the styrene-acrylic resin emulsion is 20% -30%.
In the functional acrylic emulsion provided by the invention, the content of the styrene-acrylic resin emulsion is preferably 8-20 parts by weight, more preferably 10-20 parts by weight; in some embodiments provided by the invention, the styrene-acrylic resin emulsion is specifically 10 parts by weight or 20 parts by weight; in some embodiments provided herein, the styrene-acrylic resin emulsion has a solids content of specifically 20%, 25% or 30%.
According to the present invention, the hard monomer is preferably a methacrylate-based hard monomer and/or an acrylate-based hard monomer, more preferably methyl methacrylate and/or methyl acrylate; in some embodiments provided herein, the hard monomer is specifically present in an amount of 5 parts by weight, 7 parts by weight, or 10 parts by weight.
The soft monomer is preferably methacrylate soft monomer and/or acrylate soft monomer, more preferably one or more of n-butyl acrylate, n-octyl methacrylate and isooctyl acrylate; the content of the soft monomer is preferably 6 to 10 parts by weight; in the examples provided herein, the soft monomer content is specifically 6 parts by weight or 10 parts by weight.
The functional monomer is preferably one or more of hydroxyethyl methacrylate, lauryl methacrylate, acrylamide and 2-hydroxypropyl methacrylate; in the examples provided herein, the functional monomer is specifically contained in an amount of 1 part by weight or 2 parts by weight.
The content of the acrylic acid is preferably 1 to 1.5 parts by weight.
The diacetone acrylamide content is preferably 0.5 to 1 part by weight.
In some embodiments provided herein, the adipic acid dihydrazide is specifically present in an amount of 0.25 parts by weight or 0.5 parts by weight.
The emulsifier used in the invention is preferably sulfonate containing allyl, more preferably one or more of sodium allyloxy hydroxypropyl sulfonate, sodium 3-allyloxy-1-hydroxy-1-propane sulfonate, sodium allylhydroxypropyl sulfonate and sodium allylsulfonate; in the examples provided herein, the emulsifier is specifically present in an amount of 0.5, 1 or 2 parts by weight.
The initiator used in the present invention is preferably persulfate, more preferably potassium persulfate and/or ammonium persulfate; the initiator content is preferably 1 to 2 parts by weight.
The defoamer used in the present invention is preferably a silicone defoamer; in the examples provided herein, the defoamer is present in an amount of specifically 0.1 parts by weight.
The water is preferably used in an amount of 100 parts by weight of the supplementary functional acrylic emulsion.
The invention adopts the design principle of hard core and soft shell, uses styrene-acrylic resin emulsion as seed emulsion, and carries out core-shell polymerization on the styrene-acrylic resin emulsion, hard monomer, soft monomer, functional monomer and acrylic acid to obtain self-crosslinking functional acrylic emulsion with good wear resistance, and simultaneously introduces diacetone acrylamide and adipic dihydrazide to crosslink in the polymerization process, thereby further improving the wear resistance and anti-back adhesion performance.
The invention also provides a preparation method of the functional acrylic emulsion, which comprises the following steps: s1) mixing a hard monomer, a soft monomer, a functional monomer, acrylic acid and diacetone acrylamide to obtain a mixed monomer; mixing part of water with an emulsifier to obtain an emulsifier solution; mixing the other part of water with an initiator to obtain an initiator solution; s2) mixing the rest water, the styrene-acrylic resin emulsion, part of the emulsifier solution and part of the initiator solution, heating and stirring, simultaneously and continuously adding the mixed monomer, the rest emulsifier solution and the rest initiator solution, continuously heating and reacting, cooling, adding adipic acid dihydrazide, stirring and reacting, and adding a defoaming agent to obtain the functional acrylic emulsion.
The source of all the raw materials is not particularly limited, and the raw materials are commercially available. The types and the amounts of the styrene-acrylic resin emulsion, the water, the hard monomer, the soft monomer, the functional monomer, the acrylic acid, the diacetone acrylamide, the adipic acid dihydrazide, the emulsifier, the initiator and the defoamer are all described above, and are not described in detail herein.
In the present invention, the styrene-acrylic resin emulsion is preferably prepared according to the following method: mixing styrene-acrylic resin, water and organic alkali, heating and stirring to obtain styrene-acrylic resin emulsion; the glass transition temperature of the styrene-acrylic resin is preferably 95-110 ℃; the solid content of the styrene-acrylic resin is preferably 98% or more, more preferably 98% or more; the organic base is preferably one or more of ammonia water, monoethanolamine and triethanolamine; the mass concentration of the ammonia water is preferably 25% -28%; the mass ratio of the styrene-acrylic resin, water and organic alkali is preferably (20-30): (60-75): (5-10); in the embodiment provided by the invention, the mass ratio of the styrene-acrylic resin to the water to the organic base is specifically 20:75: 5. 25:68:7 or 30:60:10; the temperature of the heating and stirring is preferably 80-90 ℃, more preferably 85 ℃; the heating and stirring time is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and still more preferably 2 hours; the rotation speed of the heating and stirring is preferably 300-500 r/min.
Mixing a hard monomer, a soft monomer, a functional monomer, acrylic acid and diacetone acrylamide to obtain a mixed monomer; mixing part of water with an emulsifier to obtain an emulsifier solution; mixing the other part of water with an initiator to obtain an initiator solution; the preparation of the mixed monomer, the emulsifier solution and the initiator solution is not sequential.
Mixing the rest water, styrene-acrylic resin emulsion, part of the emulsifier solution and part of the initiator solution; the mass ratio of the part of water to the other part of water to the rest of water is preferably (10-30): (10-20): (50 to 80), more preferably (15 to 25): (12-18): (57 to 73), and more preferably 20:15:65.
sealing and vacuumizing preferably after mixing; in the present invention, the vacuum is preferably applied to-0.1 to-0.0 MPa, more preferably to-0.05 to-0.0 MPa, and still more preferably to-0.01 MPa; then heating and stirring; the temperature of the heating and stirring is preferably 80-85 ℃; the heating and stirring time is preferably 40-80 min, more preferably 50-70 min, and still more preferably 60min; the rotation speed of the heating and stirring is preferably 80-200 r/min.
Heating and stirring, and then continuously adding the mixed monomer, the rest of the emulsifier solution and the rest of the initiator solution; the time for continuously adding the mixed monomer, the rest of the emulsifier solution and the rest of the initiator solution is preferably 3-5 h, namely the mixed monomer, the rest of the emulsifier solution and the rest of the initiator solution are added within 3-5 h, and more preferably within 4-5 h; the mass ratio of the part of the emulsifier solution to the rest of the emulsifier solution is preferably (1-3): (7 to 9), more preferably (1.5 to 2.5): (7.5 to 8.5), and more preferably 2:8, 8; the mass ratio of the partial initiator solution to the rest of the initiator solution is preferably (2 to 4): (6 to 8), more preferably (2.5 to 3.5): (6.5 to 7.5), and more preferably 3:7.
after the feeding is completed, continuing to heat for reaction; the temperature of the continuous heating reaction is preferably 80-85 ℃; the time for continuing the heating reaction is preferably 1 to 2 hours.
Then preferably adjusting the pH value of the reaction system to 7-8 and then cooling; in the invention, ammonia water is preferably adopted to adjust the pH value of the reaction system; the temperature reduction is preferably reduced to below 40 ℃.
Then adipic acid dihydrazide is added and stirred for reaction; the stirring reaction time is preferably 10 to 30 minutes.
And finally adding the defoaming agent, fully stirring, standing and cooling to obtain the functional acrylic emulsion.
The invention also provides a wear-resistant acrylic acid coating film which is formed by the functional acrylic acid emulsion.
The invention also provides an acrylic coated BOPP film comprising a BOPP film; one or two sides of the BOPP film are sequentially provided with a polyurethane coating film and a wear-resistant acrylic coating film; the wear-resistant acrylic coating film is formed from the functional acrylic emulsion described above.
Wherein the thickness of the BOPP film is preferably 19-35 μm.
A polyurethane coating film is arranged on one side or two sides of the BOPP film; the BOPP film is preferably provided with a polyurethane coating film after corona treatment; the corona preferably enables the surface tension of the BOPP film to reach 38dyn/cm; the polyurethane coating film is formed by coating polyurethane emulsion; after drying, the coating amount of the polyurethane coating film is preferably 0.1 to 0.5g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The surface of the BOPP film is precoated by adopting waterborne polyurethane, so that the adhesion of the wear-resistant acrylic acid coating film on the BOPP substrate can be improved.
The surface of the polyurethane coating film is provided with a wear-resistant acrylic coating film; the wear-resistant acrylic coating film is formed by the functional acrylic emulsion; after drying, the coating amount of the abrasion-resistant acrylic coating film is preferably 0.5 to 1.5g/cm 3 。
According to the invention, one layer of polyurethane coating is pre-coated on one or two sides of the BOPP film, and then the functional acrylic emulsion is coated, so that the requirements of heat sealing, transparency and barrier can be met, and the wear resistance and anti-back adhesion performance of the rolled film can be improved.
The invention also provides application of the acrylic acid coating BOPP film as a wear-resistant cigarette packaging film.
In order to further illustrate the present invention, the present invention provides a functional acrylic emulsion, a method for preparing the same, a wear-resistant acrylic coating film, and an acrylic-coated BOPP film, which are described in detail below with reference to examples.
The reagents used in the examples below are all commercially available; the mass concentration of the ammonia water used in the embodiment is 25% -28%; the glass transition temperature of the styrene-acrylic resin is 95 ℃; the organosilicon defoamer is Dow Corning DC-65.
Example 1
1.1 preparing seed emulsion: adding 75% deionized water, 5% ammonia water and 20% styrene-acrylic resin into a reaction kettle in sequence, starting stirring for 300r/min, heating to 85 ℃ and keeping for 2 hours to prepare styrene-acrylic resin emulsion with 20% solid content.
1.2 adding 10 parts by weight of methyl acrylate, 6 parts by weight of isooctyl acrylate, 1 part by weight of hydroxyethyl methacrylate, 1 part by weight of acrylic acid and 1 part by weight of diacetone acrylamide into a material tank A, and uniformly stirring at room temperature to prepare a mixed monomer for later use.
Adding part of deionized water (accounting for 20% of the total amount of the deionized water) and 1 part of emulsifier (sodium allylhydroxypropyl sulfonate and sodium allylsulfonate with the mass ratio of 1:1) into a B material tank, and uniformly stirring at room temperature to prepare an emulsifier solution for later use.
And adding part of deionized water (accounting for 15% of the total amount of the deionized water) and 1 part by weight of ammonium persulfate into the C material tank, and uniformly stirring to prepare an initiator solution for later use.
1.3 adding the rest deionized water (65% of the total amount of deionized water, so that the total amount of the raw materials of the functional acrylic emulsion is 100 parts by weight), 20 parts by weight of seed emulsion, 20% of emulsifier solution and 30% of initiator solution into a reaction kettle. Sealing, vacuumizing to-0.01 MPa, starting a stirring and heating device, setting the stirring speed to 80r/min, keeping the temperature for 1 hour after the temperature reaches 85 ℃, and continuously adding the prepared mixed monomer, 80% of emulsifier solution and 70% of initiator solution through a metering pump. The dropping time was controlled to 4 hours.
1.4 after the addition is completed, continuing to keep the temperature at 85 ℃ for 1 hour, adjusting the pH value to 7 by ammonia water, cooling to below 40 ℃, adding 0.5 part by weight of adipic dihydrazide, stirring for 30 minutes, and finally adding 0.1 part by weight of organosilicon defoamer. After fully stirring, standing and cooling, the functional acrylic emulsion with the solid content of 21.5% is prepared.
1.5 preparation method of the special acrylic acid coating BOPP film for the wear-resistant smoke film comprises the following steps: using 19 μm BOPP light film as base material, using special coater, unwinding the base material, corona, coating one layer of polyurethane emulsion (commercial DSM product, brand R-600) on one side, oven drying at 100deg.C, and coating with a weight of 0.5g/m 2 Then coating the functional acrylic emulsion obtained in 1.4, and drying at 110 ℃ to obtain the coating weight of 1.5g/m 2 Then a layer of polyurethane emulsion (commercially available as DSM product in the Netherlands, brand R-600) is coated on the other side of the BOPP, and the coating weight is 0.5g/m after drying at 100 DEG C 2 Then coating the functional acrylic emulsion obtained in 1.4, and drying at 110 ℃ until the coating weight reaches 1.5g/m 2 An acrylic coated BOPP film was obtained.
The properties of the acrylic-coated BOPP film obtained in example 1 were examined to obtain: (1) heat seal strength 2.5N/15mm; (2) the coating has no scratch after being rubbed for 400 times for 4 pounds; (3) coating film haze 1.9.
Example 2
2.1 preparing seed emulsion: adding 68% deionized, 7% ethanolamine and 25% styrene-acrylic resin into a reaction kettle in sequence, starting stirring for 400r/min, heating to 85 ℃ and keeping for 2 hours to prepare styrene-acrylic resin emulsion with the solid content of 25%.
2.2, 5 parts by weight of methyl methacrylate, 10 parts by weight of butyl acrylate, 1 part by weight of laurel methacrylate, 1 part by weight of acrylamide, 1.5 parts by weight of acrylic acid and 1 part by weight of diacetone acrylamide are added into a tank A, and stirred uniformly at room temperature to prepare a mixed monomer for later use.
Adding part of deionized water (accounting for 20 percent of the total amount of the deionized water) and 0.5 part by weight of emulsifier allyloxy hydroxypropyl sodium sulfonate into a B material tank, and uniformly stirring at room temperature to prepare an emulsifier solution for later use.
Adding part of deionized water (accounting for 15% of the total amount of the deionized water) and 2 parts by weight of potassium persulfate into a C material tank, and uniformly stirring to prepare an initiator solution for later use.
2.3 adding the rest deionized water (65% of the total weight of the deionized water, the total amount of the deionized water makes the total amount of the functional acrylic emulsion raw materials 100 parts by weight), 20 parts by weight of seed emulsion, 20% of emulsifier solution and 30% of initiator solution into a reaction kettle. Sealing, vacuumizing to-0.01 MPa, starting a stirring and heating device, setting the stirring speed to 100r/min, keeping the temperature for 1 hour after the temperature reaches 80 ℃, and continuously adding the prepared mixed monomer, 80% of emulsifier solution and 70% of initiator solution through a metering pump. The dropping time was controlled to 5 hours.
2.4 after the addition is completed, continuing to keep the temperature at 85 ℃ for 2 hours, adjusting the pH value to 8 by ammonia water, cooling to below 40 ℃, adding 0.5 part by weight of adipic dihydrazide, stirring for 10 minutes, and finally adding 0.1 part by weight of organosilicon defoamer. After fully stirring, standing and cooling, the functional acrylic emulsion with the solid content of 22.5 percent is prepared.
2.5 preparation method of the special acrylic acid coating BOPP film for the wear-resistant smoke film comprises the following steps: the BOPP optical film with the thickness of 35 mu m is adopted as a base material, a professional coater is adopted, after the base material is unreeled and corona is carried out, the surface tension reaches 38dyn/cm, one side of the base material is coated with a layer of polyurethane emulsion (commercially available as Dutch DSM product, brand R-600), and after drying at 90 ℃, the coating weight reaches 0.1g/m 2 Then coating the functional acrylic emulsion obtained in 2.4, and drying at 110 ℃ until the coating weight reaches 1.5g/m 2 Then a layer of polyurethane emulsion (commercially available as Dutch DSM product, brand R-600) is coated on the other side of BOPP, and after drying at 90 ℃, the coating weight reaches 0.1g/m 2 Then coating the functional acrylic emulsion obtained in 2.4, and drying at 110 ℃ until the coating weight reaches 1.5g/m 2 An acrylic coated BOPP film was obtained.
The properties of the acrylic-coated BOPP film obtained in example 2 were examined to obtain: (1) heat seal strength 3.4N/15mm; (2) the coating has no scratch after being rubbed for 400 times for 4 pounds; (3) coating film haze 2.2.
Example 3
3.1 preparing seed emulsion: sequentially adding 60% deionized water, 10% ammonia water and 30% styrene-acrylic resin into a reaction kettle, starting stirring for 500r/min, heating to 85 ℃ and keeping for 2 hours to prepare styrene-acrylic resin emulsion with the solid content of 30%.
3.2, 7 parts by weight of methyl methacrylate, 10 parts by weight of isooctyl acrylate, 1 part by weight of hydroxyethyl methacrylate, 1.5 parts by weight of acrylic acid and 0.5 part by weight of diacetone acrylamide are added into a tank A, and stirred uniformly at room temperature to prepare a mixed monomer for later use.
Adding part of deionized water (accounting for 20% of the total amount of the deionized water) and 2 parts by weight of emulsifier 3-allyloxy-1-hydroxy-1-propane sulfonic acid sodium salt into a B material tank, and uniformly stirring at room temperature to prepare an emulsifier solution for later use.
Part of deionized water (accounting for 15 percent of the total amount of the deionized water) and 2 parts of initiator (specific types are given: ammonium persulfate) are added into a C material tank, and uniformly stirred to prepare an initiator solution for later use.
3.3 adding the rest deionized water (accounting for 65% of the total amount of the deionized water, which makes the total amount of the functional acrylic emulsion raw materials 100 parts by weight), 10 parts by weight of seed emulsion, 20% of emulsifier solution and 30% of initiator solution into a reaction kettle. Sealing, vacuumizing to-0.01 MPa, starting a stirring and heating device, setting the stirring speed to 200r/min, keeping the temperature for 1 hour after the temperature reaches 85 ℃, and continuously adding the prepared mixed monomer, 80% of emulsifier solution and 70% of initiator solution through a metering pump. The dropping time was controlled to 5 hours.
3.4 after the addition is completed, continuing to keep the temperature at 85 ℃ for 2 hours, adjusting the pH value to 7 by ammonia water, cooling to below 40 ℃, adding 0.25 weight part of adipic dihydrazide, stirring for 30 minutes, and finally adding 0.1 weight part of organosilicon defoamer. After fully stirring, standing and cooling, the functional acrylic emulsion is prepared, and the solid content is 25%.
3.5 preparation method of special acrylic acid coating BOPP film for abrasion-resistant smoke film comprises the following steps: the BOPP optical film with the thickness of 19 mu m is adopted as a base material, a professional coater is adopted, after the base material is unreeled and corona is carried out, the surface tension reaches 38dyn/cm, one side of the base material is coated with a layer of polyurethane emulsion (commercially available as Dutch DSM product, brand R-600), and after being dried at 110 ℃, the coating weight reaches 0.5g/m 2 Then coating the functional acrylic emulsion obtained in 3.4, and drying at 110 ℃ until the coating weight reaches 1.0g/m 2 Then a layer of polyurethane emulsion (commercially available as Dutch DSM product, brand R-600) is coated on the other side of BOPP, and after drying at 110 ℃, the coating weight reaches 0.5g/m 2 Then coating the functional acrylic emulsion obtained in 3.4, and drying at 110 ℃ until the coating weight reaches 1.0g/m 2 An acrylic coated BOPP film was obtained.
The properties of the acrylic-coated BOPP film obtained in example 3 were examined to obtain: (1) heat seal strength 2.8N/15mm; (2) the coating has no scratch after being rubbed for 400 times for 4 pounds; (3) coating film haze 2.2.
Table 1 comparison of the methods and properties employed in examples 1-2 and comparative examples 1-2
Claims (5)
1. A functional acrylic emulsion comprising:
the solid content of the styrene-acrylic resin emulsion is 20% -30%;
the styrene-acrylic resin emulsion is prepared according to the following method:
mixing styrene-acrylic resin, water and organic alkali, heating and stirring to obtain styrene-acrylic resin emulsion;
the mass ratio of the styrene-acrylic resin to the water to the organic alkali is (20-30): (60-75): (5-10);
the glass transition temperature of the styrene-acrylic resin is 95-110 ℃; the solid content of the styrene-acrylic resin is more than or equal to 98%;
the organic base is selected from one or more of ammonia water, monoethanolamine and triethanolamine;
the hard monomer is selected from methacrylate hard monomers and/or acrylate hard monomers;
the soft monomer is selected from one or more of n-butyl acrylate, n-octyl methacrylate and isooctyl acrylate;
the functional monomer is selected from one or more of hydroxyethyl methacrylate, lauryl methacrylate, acrylamide and 2-hydroxypropyl methacrylate;
the emulsifier is selected from sulfonate containing allyl;
the initiator is selected from potassium persulfate and/or ammonium persulfate;
the defoaming agent is an organosilicon defoaming agent.
2. The method for producing a functional acrylic emulsion according to claim 1, comprising:
s1) mixing a hard monomer, a soft monomer, a functional monomer, acrylic acid and diacetone acrylamide to obtain a mixed monomer;
mixing part of water with an emulsifier to obtain an emulsifier solution;
mixing the other part of water with an initiator to obtain an initiator solution;
s2) mixing the rest water, the styrene-acrylic resin emulsion, part of the emulsifier solution and part of the initiator solution, heating and stirring, simultaneously and continuously adding the mixed monomer, the rest emulsifier solution and the rest initiator solution, continuously heating and reacting, cooling, adding adipic acid dihydrazide and stirring for reacting, and adding a defoaming agent to obtain the functional acrylic emulsion;
the mass ratio of the part of water to the other part of water to the rest of water is (10-30): (10-20): (50-80);
the mass ratio of the part of the emulsifier solution to the rest of the emulsifier solution is (1-3): (7-9);
the mass ratio of the partial initiator solution to the rest initiator solution is (2-4): (6-8);
the temperature of heating and stirring is 80-85 ℃; the heating and stirring time is 40-80 min; the rotating speed of the heating and stirring is 80-200 r/min;
the time for continuously adding the mixed monomer, the rest of the emulsifier solution and the rest of the initiator solution is 3-5 h;
the temperature of the continuous heating reaction is 80-85 ℃; continuously heating and reacting for 1-2 h;
after the continuous heating reaction, the pH value of the reaction system is regulated to 7-8, and then the temperature is reduced;
the temperature is reduced to below 40 ℃;
the stirring reaction time is 10-30 min.
3. An abrasion-resistant acrylic coating film, characterized by being formed from the functional acrylic emulsion according to claim 1 or the functional acrylic emulsion prepared by the preparation method according to claim 2.
4. An acrylic coated BOPP film comprising a BOPP film;
one or two sides of the BOPP film are sequentially provided with a polyurethane coating film and a wear-resistant acrylic coating film;
the wear-resistant acrylic coating film is formed from the functional acrylic emulsion according to claim 1 or the functional acrylic emulsion prepared by the preparation method according to claim 2.
5. The acrylic-coated BOPP film according to claim 4, wherein the coating amount of the polyurethane-coated film is 0.1 to 0.5g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the The coating weight of the wear-resistant acrylic acid coating film is 0.5-1.5 g/cm 3 。
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| CN202110824028.7A CN113372500B (en) | 2021-07-21 | 2021-07-21 | Functional acrylic emulsion, preparation method thereof, wear-resistant acrylic coating film and acrylic coating BOPP film |
| PCT/CN2021/113227 WO2023000420A1 (en) | 2021-07-21 | 2021-08-18 | Functional acrylic emulsion and preparation method therefor, wear-resistant acrylic coated film, and acrylic coated bopp film |
| CA3136565A CA3136565C (en) | 2021-07-21 | 2021-08-18 | Functional acrylic emulsion and preparation method thereof, wear-resistant acrylic coated film and acrylic coated bopp film |
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| CN116396652B (en) * | 2023-06-06 | 2023-08-11 | 广州百能建筑科技有限公司 | Building waterproof coating composition and preparation method thereof |
| CN116716066B (en) * | 2023-06-17 | 2024-01-26 | 广州聚佳新材料科技有限公司 | Anti-corrosion acid-resistant acrylic resin adhesive and preparation method thereof |
| CN117126629B (en) * | 2023-08-07 | 2025-02-28 | 浙江冠豪新材料有限公司 | Acrylate latex pressure-sensitive adhesive for BOPP film labels and preparation method thereof |
| CN117418420A (en) * | 2023-08-24 | 2024-01-19 | 嘉兴市豪能科技股份有限公司 | A kind of water-based double-coated leakage-resistant paper cup white cardboard and its preparation method |
| CN117229448B (en) * | 2023-10-16 | 2024-07-26 | 波司登羽绒服装有限公司 | Aqueous acrylic emulsion for gold stamping |
| CN118978842B (en) * | 2024-07-22 | 2025-03-25 | 浙江佑威新材料股份有限公司 | A wear-resistant and durable one-way isolation material and its preparation method and application |
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| CN110591006A (en) * | 2019-09-29 | 2019-12-20 | 武汉迪赛环保新材料股份有限公司 | Preparation method of high-temperature-resistant film-forming styrene-acrylic emulsion for paper printing |
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| CN102649892A (en) * | 2012-05-10 | 2012-08-29 | 海南必凯水性涂料有限公司 | High thermal-sealing type acrylic coating special for cigarette film and preparation method thereof |
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| CN113105581A (en) * | 2021-04-14 | 2021-07-13 | 海南必凯水性新材料有限公司 | Special acrylic emulsion for wear-resistant smoke film, preparation method of special acrylic emulsion and wear-resistant smoke film |
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