WO2013170411A1 - Emulsion de copolymère d'acétate de vinyle-éthylène et composition de couchage de papier à base de celle-ci - Google Patents

Emulsion de copolymère d'acétate de vinyle-éthylène et composition de couchage de papier à base de celle-ci Download PDF

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Publication number
WO2013170411A1
WO2013170411A1 PCT/CN2012/075432 CN2012075432W WO2013170411A1 WO 2013170411 A1 WO2013170411 A1 WO 2013170411A1 CN 2012075432 W CN2012075432 W CN 2012075432W WO 2013170411 A1 WO2013170411 A1 WO 2013170411A1
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WIPO (PCT)
Prior art keywords
vinyl acetate
coating composition
paper coating
acid
emulsion
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PCT/CN2012/075432
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English (en)
Inventor
Yi Han
Xiaodong Zhao
Yifang SHI
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Celanese International Corporation
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Application filed by Celanese International Corporation filed Critical Celanese International Corporation
Priority to PCT/CN2012/075432 priority Critical patent/WO2013170411A1/fr
Priority to EP12876890.0A priority patent/EP2850141A4/fr
Priority to CN201280073137.9A priority patent/CN104284954A/zh
Priority to US14/400,636 priority patent/US20150133577A1/en
Publication of WO2013170411A1 publication Critical patent/WO2013170411A1/fr

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • 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
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • 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
    • C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
    • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09D131/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate

Definitions

  • Vinyl acetate-ethylene copolymer emulsion and paper coating composition based on the same
  • the present invention relates to a vinyl acetate-ethylene copolymer emulsion and a paper coating composition based on the same. More specifically, the present invention relates to a vinyl acetate-ethylene copolymer emulsion based paper coating composition with low odor. The present invention also relates to processes for preparing the vinyl acetate-ethylene copolymer emulsion and the paper coating composition, and uses thereof.
  • Aqueous emulsions such as styrene-butadiene copolymer emulsion, styrene-acrylate copolymer emulsion, acrylate copolymer emulsion, vinyl acetate homopolymer emulsion, vinyl acetate-ethylene copolymer emulsion, etc., are commonly used as binder for paper surface coating in paper industry, and styrene-butadiene copolymer emulsion are the most widely used aqueous emulsion among others.
  • the vinyl acetate-ethylene copolymer emulsion according to the present invention is obtained through aqueous emulsion polymerization of vinyl acetate and ethylene. It has been surprisingly found by the present inventors that the package paper made by using the inventive vinyl acetate-ethylene copolymer emulsion as binder for paper surface coating exhibits a extremely low odor after application of Ultra-Violet (UV) curable ink and electron beam radiation curable ink printing techniques, which can meet the low odor requirement sufficiently as needed by the market.
  • UV Ultra-Violet
  • the low odor performances as provided by the vinyl acetate-ethylene copolymer emulsion according to the present invention is partially attributed to following factors, such as the structure/composition properties of the vinyl acetate-ethylene copolymer emulsion and/or its advantages over commonly used styrene-butadiene copolymer emulsion, which could include: the vinyl acetate-ethylene copolymer emulsion is free of organic phenylic monomer, and the polymerization process is carried out without addition of phenylic derived monomer, therefore the residue of volatile phenylic derivative which has special odor such as 4-phenyl cyclohexene is avoided; ethylene, one of the monomers, is gas, thus can hardly retained in the emulsion; the vinyl acetate monomer and other possible volatile organic residues can be further reduced by chemical and physical process during or after the end of the polymerization, whereby the content of residue vinyl acetate monomer
  • one object of the present invention is to provide a low odor vinyl acetate-ethylene copolymer emulsion.
  • Another object of the present invention is to provide a process for preparing said vinyl acetate-ethylene copolymer emulsion.
  • Still another object of the present invention is to provide a use of the vinyl acetate-ethylene copolymer emulsion for low odor paper coating composition.
  • one object of the present invention is to provide a low odor paper coating composition.
  • Another object of the present invention is to provide a process for preparing said low odor paper coating composition.
  • Still another object of the present invention is to provide a use of the low odor paper coating composition in printing packages with high qualities, such as cigarette package and food package.
  • a vinyl acetate-ethylene copolymer-based emulsion for low odor paper coating composition wherein the copolymer comprises, based on the total weight of the copolymer:
  • the copolymer-based emulsion is formed by emulsion polymerization of the monomers in the presence of about 1 -5pphm, preferably about 2-5 pphm, more preferably about 2-4 pphm of a surfactant and about 0-10pphm, preferably about 0-5 pphm of a polymeric protective colloid as emulsifier / protective colloid.
  • the monomers used in emulsion polymerization can be composed of about 65-95pphm of vinyl acetate, about 5-35pphm of ethylene and about 0-10pphm of other comonomers or functional monomers.
  • examples of other comonomers or functional monomers suitable for the present invention include, but not limited to, one or more selected from the group of:
  • each of Ri and R 2 is hydrogen or alkyl group, provided that the total carbon atom number of Ri and R 2 is from 1 to 14;
  • the specific monomer can include: , wherein R 3 is hydrogen or alkyl group with 1 to 16 carbon atom(s); methacrylates, wherein the specific monomer can include: , wherein R is hydrogen or alkyl group with 1 to 16 carbon atom(s);
  • each of R 5 and R 6 is alkyl group with 1 to 16 carbon atom(s);
  • said surfactant can be selected from anionic surfactants, nonionic surfactants or combination thereof.
  • anionic surfactants suitable for the present invention include, but not limited to: alkylsulfates, alkylsulfonates, alkyl benzenesulfonates, alkyl polyoxyethylene ether sulfates, alkylpolyoxyethylene-propylene ether sulfates, sodium fatty alcohol succinic acid mono ester sulfonates, disodium fatty alcohol polyoxyethylene ether sulfosuccinates, disodium fatty alcohol polyoxyethylene-propylene ether sulfosuccinates, alkylpolyoxyethylene phosphates, alkylpolyoxyethylene-propylene phosphates and alkali metal salts of fatty acids.
  • anionic surfactants suitable for the present invention include, but not limited to: sodium dodecylbenzene sulfonate, sodium dodecylsulfonate, sodium dodecylsulfate, disodium dodecyldiphenylether sulfonate, octadecyl sulfosuccinic acid and sodium dioctylsulfosuccinate.
  • the anionic surfactants as mentioned above can be used in the form of aqueous solution.
  • nonionic surfactants suitable for the present invention include, but not limited to: linear alkyl alcohol polyoxyethylene ethers, linear alkyl alcohol polyoxyethylene-propylene ethers, branched alkyl alcohol polyoxyethylene ethers, branched alkyl alcohol polyoxyethylene-propylene ethers, fatty acid polyoxyethylenemonoesters, fatty acid polyoxyethylene-propylenemonoesters.
  • nonionic surfactants suitable for the present invention include, but not limited to: isometric tridecyl alcohol polyoxyethylene monoether, cetyl alcohol polyoxyethylenemonoether, octadecyl alcohol polyoxyethylenemonoether lauroylhydroxylpolyoxyethylene, etc., wherein the EO numbers of polyoxyethylene section are chosen according to the desired HLB value of the surfactant, typically in the range of about 20 to 40.
  • the nonionic surfactants as mentioned above can be used in the form of aqueous solution.
  • the surfactant can be used in an amount of about 1 -5 pphm, preferably about 2-5 pphm, more preferably about 2-4 pphm.
  • the polymeric protective colloid can be selected from partially hydrolyzed polyvinyl alcohols, cellulose ethers and polyvinyl pyrrolidone.
  • polymeric protective colloids suitable for the present invention include, but not limited to: polyvinyl alcohols having a degree of alcoholysis of about 75 to 95%, more preferably about 70 to 92% and a degree of polymerization of about 200 to 4000, more preferably polyvinyl alcohols having a degree of alcoholysis of about 80 to 90% and a degree of polymerization of about 200 to 4000.
  • Cellulose ethers as polymeric protective colloid suitable for the present invention include, but not limited to, hydroxymethyl cellulose ether, hydroxyl ethylcellulose ether and hydroxypropyl cellulose ether.
  • the polymeric protective colloid can be used in an amount of about 0-10 pphm, preferably about 0-5 pphm.
  • a low odor paper coating composition comprising a solid component and a binder, characterized in that said binder comprises:
  • the copolymer-based emulsion is formed by emulsion polymerization of the monomers in the presence of about 1 -5pphm, preferably about 2-5 pphm, more preferably about 2-4 pphm of a surfactant and about 0-10pphm, preferably about 0-5 pphm of a polymeric protective colloid as emulsifier / protective colloid,
  • the low odor paper coating composition comprises the solid component and the binder.
  • the weight ratio of solid component to binder is about 100:6 to 100: 19, preferably about 100:8 to 100: 16.
  • the solid component used in low odor paper coating composition can comprise, but not limited to, kaolin, calcium carbonate or a mixture thereof.
  • the binder used in low odor paper coating composition comprises mainly vinyl acetate-ethylene copolymer-based emulsion and additional water.
  • the binder can have a solid content of about 40 to 70%, more commonly about 50 to 60% by weight.
  • the binder used in low odor paper coating composition essentially consists of vinyl acetate-ethylene copolymer-based emulsion, additional water and other conventional additives.
  • the conventional additives added to the aqueous phase of the binder may include those known in the art which are useful in the emulsion polymerization system or improve the stability or pot life of the final emulsion.
  • those additives can be redox reaction promoter, pH adjusting agents, ion intensity regulators, molecular weight modifiers, defoamers, fungicides, chelating agents, and the like.
  • the emulsion polymerization is conducted in the presence of a redox initiator.
  • the oxidizing agent and reducing agent used to make up of the redox initiator include, but not limited to water soluble oxidizing agents and reducing agents known in the art.
  • oxidizing agents and reducing agents suitable for the present invention may include, but not limited to, ammonium persulfate, sodium persulfate, hydrogen peroxide, tert-butyl peroxide, sodium formaldehyde-sulfoxylate, disodium 2-hydroxyl-2-sulfinatoacetate, ascorbic acid, erythorbic acid, alkali metal salts of ascorbic acid, alkali metal salts of erythorbic acid, sodium bisulfite, sodium sulfite, sodium metabisulfite, sodium thiosulfate, etc.
  • the oxidizing agent and reducing agent can be each added in an amount of about 0.05 to 5 pphm.
  • a process for preparing the low odor paper coating composition comprises
  • the emulsion may be obtained by the following steps: forming an aqueous phase by adding surfactant and protective colloid, as emulsifier, and other additives such as defoamers, pH adjusting agents, ion intensity regulators, molecular weight modifiers, etc.
  • the temperature of the reactor was controlled at about 50-90°C during the emulsion polymerization process. After completion of polymerization, the reactor is cooled to selected temperature, about 50-70°C, and the polymerization product therein was transferred to a post-treatment reactor, while the unreacted ethylene gas was discharged as exhaust gas. Subsequently, certain amount of oxidizing agent and reducing agent were added to the post-treatment reactor, to reduce the amount of residual monomers by further initiating the polymerization of residual monomers. Alternatively, the amount of residual monomers can be further reduced by extraction of water vapor.
  • the emulsion parameters of the copolymer-based emulsion thus obtained can be adjusted by feeding with additional water and/or other conventional additives, such as fungicides, pH adjusting agents, etc..
  • the emulsion thus obtained can have a solid content of about 40 to 70%, most commonly about 50 to 60% by weight, and can be used as binder for the low odor paper coating composition according to the present invention.
  • a vinyl acetate-ethylene copolymer-based emulsion was obtained according to the above mentioned formulation and process, and the vinyl acetate-ethylene copolymer-based emulsion thus obtained can be used to formulate the low odor paper coating composition.
  • the low odor paper coating composition may be obtained by the following steps: forming an slurry by mixing the solid component with water, dispersing agents, defoamers and the like; the slurry thus obtained is added with the binder derived from the vinyl acetate-ethylene copolymer-based emulsion and co-adjuvants such as fluorescent whiteners, rheology modifiers, etc., and mixed under stirring to obtain a homogeneous paper coating composition.
  • the low odor paper coating composition according to the present invention comprises:
  • solid component which comprises kaolin, calcium carbonate or a mixture thereof;
  • dispersing agents suitable examples of which may include, but not limited to: acrylate dispersing agents, such as sodium acrylate, ammonium acrylate, potassium acrylate, etc,; polyphosphate dispersing agents, such as sodium tripolyphosphate, tetrasodium pyrophosphate, sodium hexametaphosphate, etc.; sulfonate dispersing agents, such as lignin sulfonate, aromatic sulfonate, aliphatic sulfonate, sodium succinsulfonate, etc,.; or mixtures thereof;
  • defoamers suitable examples of which may include, but not limited to: polyol defoamers, polyether defoamers, mineral oil defoamers, silicone defoamers, or mixtures thereof;
  • rheology modifiers suitable examples of which may include, but not limited to: associative rheology modifiers, alkali swelling rheology modifiers, cellulosic rheology modifiers, natural polymer rheological modifiers and the like, such as polyurethane thickeners, sodium acrylate thickeners, acrylate thickeners, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropylmethyl cellulose, carrageenin, agar, sodium alginate, etc.; or mixtures thereof;
  • fluorescent whiteners suitable examples of which may include, but not limited to: diaminodistyrenedisulfonate, diaminodistyrenetetrasulfonate, and diaminodistyrenehexasulfonate, or mixtures thereof;
  • pH adjusting agents which is used to keep the pH value of the paper coating composition between 8 to 11 , suitable examples of which may include, but not limited to: sodium hydroxide, potassium hydroxide, ammonia and organic amine modifiers, or mixtures thereof.
  • the present invention comprises the following items:
  • a low odor paper coating composition comprising a solid component and a binder, characterized in that said binder comprises:
  • surfactant is selected from anionic surfactants, nonionic surfactants or combination thereof.
  • anionic surfactants are selected from alkylsulfates, alkylsulfonates, alkyl benzenesulfonates, alkyl polyoxyethylene ether sulfates, alkylpolyoxyethylene-propylene ether sulfates, sodium fatty alcohol succinic acid mono ester sulfonates, disodium fatty alcohol polyoxyethylene ether sulfosuccinates, disodium fatty alcohol polyoxyethylene-propylene ether sulfosuccinates, alkylpolyoxyethylene phosphates, alkylpolyoxyethylene-propylene phosphates, alkali metal salts of fatty acids, or mixtures thereof.
  • nonionic surfactants are selected from linear alkyl alcohol polyoxyethylene ethers, linear alkyl alcohol polyoxyethylene-propylene ethers, branched alkyl alcohol polyoxyethylene ethers, branched alkyl alcohol polyoxyethylene-propylene ethers, fatty acid polyoxyethylenemonoesters, fatty acid polyoxyethylene-propylenemonoesters, or mixtures thereof.
  • polymeric protective colloid is selected from partially hydrolyzed polyvinyl alcohols, cellulose ethers, polyvinyl pyrrolidone, or mixtures thereof.
  • polyvinyl alcohol has a degree of alcoholysis of about 75 to 95%, more preferably about 70 to 92% and a degree of polymerization of about 200 to 4000, preferably a degree of alcoholysis of about 80 to 90% and a degree of polymerization of about 200 to 4000.
  • each of Ri and R 2 is hydrogen or alkyl group, provided that the total carbon atom number of Ri and R 2 is from 1 to 14;
  • the specific monomer can include: , wherein R 3 is hydrogen or alkyl group with 1 to 16 carbon atom(s);
  • the specific monomer can include: , wherein R is hydrogen or alkyl group with 1 to 16 carbon atom(s);
  • each of R 5 and R 6 is alkyl group with 1 to 16 carbon atom(s);
  • the paper coating composition according to any of the preceding items wherein the weight ratio of solid component to binder is bout 100:6 to 100: 19, preferably about 100:8 to 100: 16. 10.
  • a process for preparing the low odor paper coating composition according to any of the preceding items comprises
  • a vinyl acetate-ethylene copolymer-based emulsion for low odor paper coating composition wherein the copolymer comprises, based on the total weight of the copolymer:
  • the copolymer-based emulsion is formed by emulsion polymerization of the monomers in the presence of about 1 -5pphm, preferably about 2-5 pphm, more preferably about 2-4 pphm of a surfactant and about 0-10pphm, preferably about 0-5 pphm of a polymeric protective colloid as emulsifier / protective colloid.
  • the anionic surfactants are selected from alkylsulfates, alkylsulfonates, alkyl benzenesulfonates, alkyl polyoxyethylene ether sulfates, alkylpolyoxyethylene-propylene ether sulfates, sodium fatty alcohol succinic acid mono ester sulfonates, disodium fatty alcohol polyoxyethylene ether sulfosuccinates, disodium fatty alcohol polyoxyethylene-propylene ether sulfosuccinates, alkylpolyoxyethylene phosphates, alkylpolyoxyethylene-propylene phosphates, alkali metal salts of fatty acids, or mixtures thereof.
  • nonionic surfactants are selected from linear alkyl alcohol polyoxyethylene ethers, linear alkyl alcohol polyoxyethylene-propylene ethers, branched alkyl alcohol polyoxyethylene ethers, branched alkyl alcohol polyoxyethylene-propylene ethers, fatty acid polyoxyethylenemonoesters, fatty acid polyoxyethylene-propylenemonoesters, or mixtures thereof.
  • each of Ri and R 2 is hydrogen or alkyl group, provided that the total carbon atom number of Ri and R 2 is from 1 to 14;
  • the specific monomer can include: , wherein R 3 is hydrogen or alkyl group with 1 to 16 carbon atom(s); methacrylates, wherein the specific monomer can include: , wherein R is hydrogen or alkyl group with 1 to 16 carbon atom(s);
  • each of R 5 and R 6 is alkyl group with 1 to 16 carbon atom(s);
  • a process for preparing the vinyl acetate-ethylene copolymer-based emulsion according to any of the preceding items comprises emulsion polymerizing a monomeric composition comprising:
  • the initiator is selected from ammonium persulfate, sodium persulfate, hydrogen peroxide, tert-butyl peroxide, sodium formaldehyde-sulfoxylate, disodium 2-hydroxyl-2-sulfinatoacetate, ascorbic acid, erythorbic acid, alkali metal salts of ascorbic acid, alkali metal salts of erythorbic acid, sodium bisulfite, sodium sulfite, sodium metabisulfite, sodium thiosulfate, or mixtures thereof.
  • the inventive paper coating composition has extraordinary low odor, even after application of Ultra-Violet (UV) curable ink and electron beam radiation curable ink printing techniques.
  • UV Ultra-Violet
  • the term "low odor” means that the inventive paper coating composition pass the odor evaluation test as described hereinafter.
  • the odor evaluation test can be carried out as follows:
  • a paper sample is prepared by the following steps: the binder derived from vinyl acetate-ethylene copolymer-based emulsion produced by aqueous emulsion polymerization as described above is mixed with solid component, dispersing agents, fluorescent whiteners and rheology modifiers to obtain a paper coating composition; the paper coating composition thus obtained is applied to both sides of a raw paper in an amount of 10-15gsm/10-15gsm/10-15gsm for pre-coating/middle coating/top-coating; the coated white paperboard is calendered through a calender and sealed inside a plastic bag for storing.
  • the paper sample thus obtained is withdrawn from the plastic bag, curable in a UV drier, and then sealed again inside a plastic bag for storing.
  • the parameters used in UV radiation are: UV lamp, 6wx4; wavelength, 254 nm; radiation time, 30 min.
  • the odor evaluation is carried out in 12 hours after UV curing.
  • the odor evaluation procedures are as follows: a sealed plastic bag containing the paper sample is placed in front of the nose of an evaluator and then opened; the evaluator breathes in the air released from the plastic bag immediately after the plastic bag is opened, and scores the smell by a value ranging from 1 to 5, with the value of 1 represents the highest odor and the worst score, and the value of 5 represents the lowest odor and the best score.
  • Each paper sample is evaluated by ten random selected persons respectively and the sum of the scores is output as the final result for each paper sample. The sum of the scores of each paper sample is compared with those of other paper samples, whereby a final score evaluation to each paper sample is obtained.
  • a value of 5 represents the lowest odor which cannot be obviously smelled by the evaluator
  • a value of 1 represents the highest odor, which means that the tested sample exhibits severe sour smell, bitter smell or other chemical's smell to the evaluator
  • a value ranging from 4 to 2 represents a slight odor, obvious odor or heavier odor sequentially.
  • the inventive low odor paper coating composition made from vinyl acetate-ethylene copolymer-based emulsion produce by aqueous emulsion polymerization as described above exhibits a final score of greater than 30, more preferably greater than 40 when compared with other paper coating composition made from traditional aqueous emulsions, such as styrene-butadiene copolymer emulsion, styrene-acrylate copolymer emulsion, acrylate copolymer emulsion, vinyl acetate homopolymer emulsion, vinyl acetate-ethylene copolymer emulsion, etc..
  • the pressure of the reactor was equilibrated for 5 mins, and then the reactor was charged with 35 g of 1 .7wt% aqueous solution of disodium 2-hydroxy-2-sulfinatoacetate.
  • the reactor was kept under 55°C and equilibrated for 5 mins.
  • the polymerization reaction was initiated by feeding into the reactor with the following initiators: 1 .5wt% aqueous solution of f-butyl peroxide with a starting feeding rate of 94.5g/h, 1 .7wt% aqueous solution of disodium 2-hydroxy-2-sulfinatoacetate with a starting feeding rate of 94.5g/h.
  • the reaction temperature was controlled by adjusting the flow rates of the initiators so that the reaction temperature increased to 85°C in 20 mins and then was maintained under 85°C.
  • temperature of the reactor reached 72°C, 230 g ethylene gases were added, and the maximum pressure inside the reactor was maintained below 60bar.
  • temperature of the reactor reached 80°C, 1 .24kg vinyl acetates were added into the reactor with a feeding rate of 1 .26kg/h.
  • the reactor was cooled to 55°C.
  • the obtained emulsion was transferred to post-treatment reactor.
  • the post-treatment reactor was stirred at a speed of 200 rpm and charged with 90g of 3.1wt% aqueous solution of disodium 2-hydroxy-2-sulfinatoacetate in 30 mins, then 90g of mixture of 1wt% aqueous solution of f-butyl peroxide and 1wt% aqueous solution of hydrogen peroxide in 30 mins.
  • the post-treatment reactor was kept under a vacuum degree of -0.3bar.
  • a vinyl acetate-ethylene copolymer-based emulsion (Emulsion 2) was prepared according to the procedure in Example 1 , except that the post-treatment reactor has not subjected to water vapor extraction.
  • the obtained vinyl acetate-ethylene copolymer-based emulsion (Emulsion 2) has a residual monomer content of 685 ppm.
  • Example 1 -2 The emulsions as obtained in Example 1 -2 and Comparative Example 1 -2 were used to prepare paper coating compositions respectively according to the formulation as listed in Table 2.
  • the paper coating composition prepared from Emulsion 2 with a high residual monomer content of 685 ppm also passes the odor evaluation test with a value of greater than 30, which suggests that the vinyl acetate-ethylene copolymer-based emulsion according to the present invention can provide low odor to the paper coating composition prepared therefrom, especially after exposure to UV drier according to the procedure of odor evaluation test, therefore is useful as binder for printing packages with high qualities, such as cigarette package, food package and the like.

Abstract

La présente invention porte sur une émulsion de copolymère d'acétate de vinyle-éthylène et sur une composition de couchage de papier à base de celle-ci. Plus précisément, la présente invention porte sur une composition de couchage de papier à base d'émulsion de copolymère d'acétate de vinyle-éthylène présentant une faible odeur. La présente invention porte également sur des procédés pour la préparation de l'émulsion de copolymère d'acétate de vinyle-éthylène et de la composition de couchage de papier et sur leurs utilisations.
PCT/CN2012/075432 2012-05-14 2012-05-14 Emulsion de copolymère d'acétate de vinyle-éthylène et composition de couchage de papier à base de celle-ci WO2013170411A1 (fr)

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PCT/CN2012/075432 WO2013170411A1 (fr) 2012-05-14 2012-05-14 Emulsion de copolymère d'acétate de vinyle-éthylène et composition de couchage de papier à base de celle-ci
EP12876890.0A EP2850141A4 (fr) 2012-05-14 2012-05-14 Emulsion de copolymère d'acétate de vinyle-éthylène et composition de couchage de papier à base de celle-ci
CN201280073137.9A CN104284954A (zh) 2012-05-14 2012-05-14 乙酸乙烯酯-乙烯共聚物乳液和基于其的纸张涂层组合物
US14/400,636 US20150133577A1 (en) 2012-05-14 2012-05-14 Vinyl acetate-ethylene copolymer emulsion and paper coating composition based on the same

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WO2015147352A1 (fr) * 2014-03-27 2015-10-01 Wacker Chemicals Korea Inc. Dispersion aqueuse de copolymère d'acétate de vinyle-éthylène pour revêtement de papier
CN105951513A (zh) * 2016-05-04 2016-09-21 太仓市源创包装材料厂 一种具有夜光效果的包装纸的制备方法
CN112622344A (zh) * 2019-10-09 2021-04-09 大理州祥云大宇包装有限公司 一种节能环保的瓦楞纸箱生产工艺

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CN107793519B (zh) * 2016-09-07 2020-06-09 中国石油化工股份有限公司 一种制备eva弹性体微乳液的方法
CN109234046B (zh) * 2018-10-25 2020-08-04 江南大学 一种非离子型高分子表面活性剂及其合成方法
WO2020175188A1 (fr) * 2019-02-26 2020-09-03 株式会社Moresco Procédé de fabrication d'adhésif thermofusible à base d'acétate de vinyle-éthylène, et adhésif thermofusible

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