CN104284954A - Vinyl acetate-ethylene copolymer emulsion and paper coating composition based on the same - Google Patents
Vinyl acetate-ethylene copolymer emulsion and paper coating composition based on the same Download PDFInfo
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- CN104284954A CN104284954A CN201280073137.9A CN201280073137A CN104284954A CN 104284954 A CN104284954 A CN 104284954A CN 201280073137 A CN201280073137 A CN 201280073137A CN 104284954 A CN104284954 A CN 104284954A
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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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
Abstract
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.
Description
Background technology of the present invention
1. field of the present invention
The present invention relates to vinyl copolymer emulsion and the paper-coating composition based on it.More specifically, the present invention relates to the paper-coating composition of the vinyl copolymer emulsion base with low smell.The invention still further relates to the method for the preparation of vinyl copolymer emulsion and paper-coating composition, and uses thereof.
2. description of related art
Aqueous emulsion, such as styrene-butadiene copolymer emulsion, latex of copolymer in cinnamic acrylic ester, acrylate copolymer emulsion, leifa emulsion, vinyl copolymer emulsion etc., be typically used as tackiness agent for the paper surface coating in paper industry, and styrene-butadiene copolymer emulsion is wherein the most widely used aqueous emulsion.Along with the modern times print the progress of packing technique, also improving the requirement of the paper for printing and packing, particularly for those printing packagings with high-quality, such as cigarette pack and food Package, it requires that wrapping material itself have low smell.Especially the nearest application along with ultraviolet (UV) curable ink and electron beam radiation curable ink print technology, improve the high requirement to wrapping material smell, and therefore improve the requirement of the smell of the emulsion for top coat.But traditional aqueous emulsion tends to scent of and can not meet the requirement of low smell paper coating, and such as cigarette pack and food Package are packed in the printing especially with high-quality.
Although low smell aqueous emulsion requires in this area, the research carried out the smell reducing the aqueous emulsion being used for paper production industry is little, and the factor directly affecting emulsion smell is still unknown so far.In addition, the smell of the various emulsion polymers solidified under UV and electron beam irradiation is respectively concerning still unpredictable the those skilled in the art based on its past experience.
Therefore, still exist the low smell aqueous emulsion of printing packaging for having high-quality and the needs of the paper-coating composition based on it.
Invention simplified summary
The present inventor it has surprisingly been found that, by use specific vinyl copolymer emulsion according to the present invention substitute conventional aqueous emulsion such as styrene butadiene emulsion as paper-coating composition (in particular for the high-quality paper-coating composition of UV curable ink and electron beam radiation curable ink, such as those of cigarette pack and food Package) tackiness agent, obtain vinyl copolymer emulsion and the paper-coating composition with low especially smell based on it.
Obtained according to vinyl copolymer emulsion of the present invention by aqueous emulsion polymerization vinyl-acetic ester and ethene.The present inventor has been surprisingly found out that packaging paper that the vinyl copolymer emulsion of the application of the invention prepared as the tackiness agent for paper surface coating shows extremely low smell after the application of ultraviolet (UV) curable ink and electron beam radiation curable ink print technology, and it fully can meet the low odor requirements needed for market.Do not wish to be limited to any theory, but applicant believes that the odor properties that low vinyl copolymer emulsion according to the present invention provides is partly due to following factor, structure/the composition and property of such as vinyl copolymer emulsion and/or its be better than the advantage of the styrene-butadiene copolymer emulsion commonly used, it can comprise: vinyl copolymer emulsion is not containing organic phenyl groups monomer, and polymerization technique carries out when not having interpolation to be derived from the monomer of phenyl, therefore the residue such as 4-benzyl ring hexene of the volatility phenyl derivatives with special odor is avoided, ethene (it is one of monomer) is gas, therefore, can be retained in hardly in emulsion, vinyl acetate monomer and other possible volatility organic residue can be reduced by chemistry and physical method in the course of the polymerization process or after terminating further, the content of residual vinyl acetate monomer can be reduced to and be less than about 800ppm thus, preferably be less than about 600ppm, be more preferably less than about 400ppm, in addition, vinyl acetate ethylene copolymers will not discharge material odorous by the further chemical reaction under the exposure to UV or electron beam irradiation.
Therefore, a target of the present invention is to provide low smell vinyl copolymer emulsion.
Another target of the present invention is to provide the method for the preparation of described vinyl copolymer emulsion.
Another target of the present invention is to provide the purposes of the vinyl copolymer emulsion for low smell paper-coating composition.
In addition, a target of the present invention is to provide low smell paper-coating composition.
Another target of the present invention is to provide the method for the preparation of described low smell paper-coating composition.
Another target of the present invention is to provide the printing packaging with high-quality, such as, in cigarette pack and the food Package purposes of low smell paper-coating composition.
Embodiment
In order to the object of this specification sheets, except as otherwise noted, for illustration of whole number comprehensions of the expression composition, reaction conditions etc. of book and claims for be modified by term " about " in all cases.Therefore, unless otherwise contrary explanation, the digital parameters described in following specification sheets and appended claims is approximation, and it can depend on that the present invention seeks the character of the hope obtained and changes.At least, and not as attempting restriction to the application of the instruction of the equivalent of Claims scope, each digital parameters should at least in view of reported significant figure number and by using the common technology of rounding off to explain.
Although the digital scope and the parameter that describe wide region of the present invention are approximations, the digital value described in specific embodiment as far as possible accurately reports.But any digital value, comprises some error inherently, it is that the standard deviation found in representative thermometrically must cause.
Note, as described in this specification and the appended claims, singulative " a ", " an " and " the " include plural referents, unless clearly and be limited to an indicator unambiguously.
According to an aspect of the present invention, provide the copolymer based emulsion of vinyl for low smell paper-coating composition, wherein multipolymer comprises, the gross weight based on multipolymer:
(1) about 65-95pphm (monomer for the preparation of emulsion of weight part/100 weight part), the preferably part being derived from vinyl-acetic ester of about 75-90pphm;
(2) about 5-35pphm, the preferably part being derived from ethene of about 10-20pphm; With
(3) about 0-10pphm, the preferably part being derived from other comonomer or function monomer of about 0-5pphm,
Wherein copolymer based emulsion is passed through at about 1-5pphm; preferably about 2-5pphm; the more preferably from about tensio-active agent of 2-4pphm and about 0-10pphm, under the existence of the preferred polymkeric substance protective colloid as emulsifying agent/protective colloid of about 0-5pphm, the letex polymerization of monomer is formed.
In non-limiting embodiments more of the present invention, the monomer for letex polymerization can be made up of other comonomer of the ethene of the vinyl-acetic ester of about 65-95pphm, about 5-35pphm and about 0-10pphm or function monomer.The example being suitable for other comonomer of the present invention or function monomer includes, but are not limited to be selected from one or more of following material:
The vinyl ester of-polyacid, wherein concrete monomer can comprise:
wherein R
1and R
2each be hydrogen or alkyl group, condition is R
1and R
2total carbon atom number be 1-14;
-acrylate, wherein concrete monomer can comprise:
wherein R
3hydrogen or the alkyl group with 1-16 carbon atom;
Methacrylic ester, wherein concrete monomer can comprise:
wherein R
4hydrogen or the alkyl group with 1-16 carbon atom;
-maleic acid ester, wherein concrete monomer can comprise:
wherein R
5and R
6each be the alkyl group with 1-16 carbon atom;
-vinylformic acid; Methacrylic acid; Toxilic acid; Maleic anhydride; Fumaric acid; β-crotonic acid; Methylene-succinic acid; Vinyl cyanide; Methacrylonitrile; Sodium vinyl sulfonate; Vinylbenzenesulfonic acid sodium; 2-methyl-2-[(1-oxo-2-propenyl) is amino]-1-propanesulfonic acid list sodium; Methacrylic ester ethyl-trimethyl salmiac; Acrylamide; Hydroxymethylacrylamide; Hydroxyethyl acrylamide; Hydroxypropylacrylamide; Vinyltrimethoxy silane; Vinyltriethoxysilane; Vinyl three (2-methoxy ethoxy) silane; Methacryloxypropyl trimethoxy silane; Vinylformic acid glycol ester; Vinylformic acid propylene glycol ester; Glycidyl acrylate; Diallyl maleate; Phthalic acid, diallyl ester; Triallyl cyanurate; Allyl methacrylate(AMA); Vinylformic acid ethylene glycol bisthioglycolate methyl esters; Pentaerythritol triacrylate; Pentaerythritol tetracrylate; Acrylic acid ethyl acetoacetoxy groups methyl esters; Diacetone acrylamide; Allyl group acrylamide; Or its mixture.
In non-limiting embodiments more of the present invention, described tensio-active agent can be selected from anion surfactant, nonionogenic tenside or its combination.
The example being suitable for anion surfactant of the present invention includes, but are not limited to: an alkali metal salt of alkyl-sulphate, alkylsulfonate, alkylbenzene sulfonate, alkyl polyoxyethylene ether sulfate, alkyl polyoxyethylene-propylene ether sulfate, fatty alcohol mono succinate sodium sulfonate, fatty alcohol-polyoxyethylene ether sulfo-succinic acid disodium, aliphatic alcohol polyethenoxy-propylene ether sulfo-succinic acid disodium, alkyl polyoxyethylene phosphoric acid salt, alkyl polyoxyethylene-propene phosphoric acid salt and lipid acid.The concrete example being suitable for anion surfactant of the present invention includes, but are not limited to: Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, sodium lauryl sulphate, dodecyl diphenyl ether sulfonic acid disodium, octadecyl sulfo-succinic acid and dioctyl sodium sulfosuccinate.In non-limiting embodiments more of the present invention, anion surfactant as mentioned above can use with the form of aqueous solution.
The example being suitable for nonionogenic tenside of the present invention includes, but are not limited to: linear alkyl polyoxyethylenated alcohol, linear alkyl alcohol polyoxyethylene-propylene ether, branched-alkyl polyoxyethylenated alcohol, branched-alkyl alcohol polyoxyethylene-propylene ether, aliphatic acid polyethenoxy monoesters, aliphatic acid polyethenoxy-propylene monoesters.The specific examples being suitable for nonionogenic tenside of the present invention includes, but are not limited to: isomery tridecyl alcohol polyoxyethylene monoether, hexadecyl alcohol polyoxyethylene monoether, stearyl alcohol polyoxyethylene monoether lauroyl hydroxyl polyoxyethylene etc., the wherein several HLB value selection wished according to tensio-active agent of the EO of polyoxyethylene segment, it typically is about 20-40.In non-limiting embodiments more of the present invention, nonionogenic tenside as mentioned above can use with the form of aqueous solution.
In non-limiting embodiments more of the present invention, tensio-active agent can with about 1-5pphm, preferably about 2-5pphm, and more preferably from about the amount of 2-4pphm uses.
In non-limiting embodiments more of the present invention, polymkeric substance protective colloid can be selected from the polyvinyl alcohol of partial hydrolysis, ether of cellulose and Polyvinylpyrolidone (PVP).The specific examples being suitable for polymkeric substance protective colloid of the present invention includes, but are not limited to: have about 75-95%; the more preferably from about polyvinyl alcohol of the alcoholysis degree of 70-92% and the polymerization degree of about 200-4000, more preferably has the polyvinyl alcohol of the alcoholysis degree of about 80-90% and the polymerization degree of about 200-4000.Be suitable for the ether of cellulose as polymkeric substance protective colloid of the present invention and include, but are not limited to hydroxy-methyl cellulose ether, hydroxyethyl cellulose ethers and hydroxy propyl cellulose ether.In non-limiting embodiments more of the present invention, polymkeric substance protective colloid can with about 0-10pphm, and preferably the amount of about 0-5pphm uses.
According to an aspect of the present invention, low smell paper-coating composition comprises solid ingredient and tackiness agent, it is characterized in that described tackiness agent comprises:
The copolymer based emulsion of (a) vinyl, wherein multipolymer comprises, the gross weight based on multipolymer:
(1) about 65-95pphm, the preferably part being derived from vinyl-acetic ester of about 75-90pphm;
(2) about 5-35pphm, the preferably part being derived from ethene of about 10-20pphm; With
(3) about 0-10pphm, the preferably part being derived from other comonomer or function monomer of about 0-5pphm,
Wherein copolymer based emulsion is passed through at about 1-5pphm; preferably about 2-5pphm; the more preferably from about tensio-active agent of 2-4pphm and about 0-10pphm, under the existence of the preferred polymkeric substance protective colloid as emulsifying agent/protective colloid of about 0-5pphm, the letex polymerization of monomer is formed
B water that () is extra.
Low smell paper-coating composition comprises solid ingredient and tackiness agent.In non-limiting embodiments more of the present invention, the part by weight of solid ingredient and tackiness agent is about 100:6-100:19, preferably about 100:8-100:16.
Solid ingredient for low smell paper-coating composition can include, but are not limited to kaolin, calcium carbonate or its mixture.
Tackiness agent for low smell paper-coating composition mainly comprises the copolymer based emulsion of vinyl and extra water.In non-limiting embodiments more of the present invention, tackiness agent can have about 40-70wt%, more generally the solids content of about 50-60wt%.
In non-limiting embodiments more of the present invention, the tackiness agent for low smell paper-coating composition is made up of the copolymer based emulsion of vinyl, extra water and other conventional additives usually.
Be added into tackiness agent containing the conventional additives of aqueous phase can comprise as known in the art those, it can be used for emulsion polymerization systems or improves final emulsion intercalation method or storage period.Such as, those additives can be redox reaction promotor, pH adjusting agent, ionic strength adjustor, molecular weight modifying agent, defoamer, sterilant, sequestrant etc.
In non-limiting embodiments more of the present invention, letex polymerization is carried out under the existence of redox initiator.Oxidizing and Reducing Agents for forming redox initiator includes, but are not limited to water-soluble Oxidizing and Reducing Agents as known in the art.The example being suitable for Oxidizing and Reducing Agents of the present invention can include, but are not limited to ammonium persulphate, Sodium Persulfate, hydrogen peroxide, tert-butyl peroxide, formaldehyde-sodium hydrosulfite 90min, 2-hydroxyl-2-sulfinyl acetic acid disodium, xitix, saccharosonic acid, an alkali metal salt of xitix, an alkali metal salt, sodium bisulfite, S-WAT, sodium metabisulfite, Sulfothiorine etc. of saccharosonic acid.Usually, Oxidizing and Reducing Agents can add with the amount of about 0.05-5pphm separately.
According to another aspect of the present invention, the method for the preparation of the copolymer based emulsion of vinyl is provided.Described method comprises letex polymerization monomer composition, and described composition comprises:
(1) part being derived from vinyl-acetic ester of about 65-95pphm;
(2) part being derived from ethene of about 5-35pphm; With
(3) part being derived from other comonomer or function monomer of about 0-10pphm,
Described letex polymerization is at about 1-5pphm, and preferably about 2-5pphm, the more preferably from about tensio-active agent of 2-4pphm and about 0-10pphm, carry out under the existence of the preferred polymkeric substance protective colloid as emulsifying agent/protective colloid of about 0-5pphm.
According to another aspect of the present invention, provide the method for the preparation of low smell paper-coating composition, described method comprises:
A () forms vinyl-vinyl acetate copolymer base emulsion by letex polymerization monomer composition, described composition comprises:
(1) part being derived from vinyl-acetic ester of about 65-95pphm;
(2) part being derived from ethene of about 5-35pphm; With
(3) part being derived from other comonomer or function monomer of about 0-10pphm,
Described letex polymerization is at about 1-5pphm, and preferably about 2-5pphm, the more preferably from about tensio-active agent of 2-4pphm and about 0-10pphm, carry out under the existence of the preferred polymkeric substance protective colloid as emulsifying agent/protective colloid of about 0-5pphm;
B () makes described vinyl-vinyl acetate copolymer base emulsion mix to form tackiness agent with extra water;
C () makes described tackiness agent mix with solid ingredient.
In a preferred embodiment of the present invention, emulsion can be obtained by following steps: by under agitation using tensio-active agent and protective colloid (as emulsifying agent), and other additive such as defoamer, pH adjusting agent, ionic strength adjustor, molecular weight modifying agent etc. are added in water and are formed containing aqueous phase; Reactor will be fed to containing aqueous phase under low stirring; Under vacuo emptying reactor and with nitrogen purge several times to remove any air; The temperature of reactor is increased to about 40-70 DEG C, then increases the speed of stirring, part vinyl acetate monomer or vinyl acetate monomer are added into reactor with the mixture of other comonomer or function monomer together with part ethylene gas; The temperature and pressure of reactor become stable after, dropwise add the Oxidizing and Reducing Agents as polymerization starter, to be polymerized along with the increase of temperature; Reach predetermined value in the temperature of reactor, about add remaining monomer during 50-90 DEG C, until consume monomer.In emulsion polymerization technique process, the temperature of reactor is controlled at about 50-90 DEG C.After the polymerization is complete, by reactor cooling to selected temperature, about 50-70 DEG C, and polymerisate is wherein transferred to aftertreatment reactor, unreacted ethylene gas is as the discharge of discharge gas simultaneously.Thereafter, the Oxidizing and Reducing Agents of specified quantitative being added into aftertreatment reactor, reducing the amount of residual monomer with the polymerization by causing residual monomer further.Alternatively, the amount of residual monomer can reduce further by vapor extraction.Finally, the emulsion parameter of the copolymer based emulsion therefore obtained can by the extra water of charging and/or other conventional additives, the such as adjustment such as sterilant, pH adjusting agent.Therefore the emulsion obtained can have about 40-70%, the most usually the solids content of about 50-60wt%, and can be used as the tackiness agent according to low smell paper-coating composition of the present invention.
In non-limiting embodiments more of the present invention, obtain the copolymer based emulsion of vinyl according to above-mentioned formula and method, and the copolymer based emulsion of the vinyl therefore obtained may be used for preparing low smell paper-coating composition.
In a preferred embodiment of the present invention, low smell paper-coating composition can be obtained by following steps: be mixed to form slurry by making solid ingredient and water, dispersion agent, defoamer etc.; The tackiness agent and adjuvant such as white dyes, rheology modifier etc. that are derived from the copolymer based emulsion of vinyl are added into the slurry therefore obtained, and under agitation mix to obtain uniform paper-coating composition.
In non-limiting embodiments more of the present invention, low smell paper-coating composition according to the present invention comprises:
The solid ingredient of 100 parts, it comprises kaolin, calcium carbonate or its mixture;
-Yue 6-19 part, the preferably tackiness agent of about 8-16 part;
-Yue 0.05-1 part, the preferably dispersion agent of about 0.1-0.5 part, its example be applicable to can include, but are not limited to: acrylate dispersion agent, such as sodium acrylate, ammonium acrylate, potassium acrylate etc.; Poly-phosphate dispersion agent, such as tripoly phosphate sodium STPP, tetrasodium pyrophosphate, Sodium hexametaphosphate 99 etc.; Sulfonate dispersion agent, such as sulfonated lignin, aromatic sulphonate, aliphatic sulfonate, amber sodium sulfonate etc.; Or its mixture;
-Yue 0.05-0.5 part, the preferably defoamer of about 0.1-0.3 part, its example be applicable to can include, but are not limited to: polyvalent alcohol defoamer, polyether antifoam agent, mineral oil antifoam agent, silicone antifoam agent, or its mixture;
-Yue 0.05-1 part, the preferably rheology modifier of about 0.1-0.4 part, its example be applicable to can include, but are not limited to: associating rheology modifier, alkali swelling rheology modifier, Mierocrystalline cellulose rheology modifier, natural polymer rheology modifier etc., such as polyurethane thickener, sodium acrylate thickening material, acrylate/salt thickening material, carboxy methyl cellulose, hydroxy ethyl cellulose, HYDROXY PROPYL METHYLCELLULOSE, carrageenin, agar, sodiun alginate etc.; Or its mixture;
-Yue 0-0.8 part, the preferably white dyes of about 0.3-0.6 part, its example be applicable to can include, but are not limited to: diaminobenzil disulfonate, diaminobenzil tetrasulfonic acid ester, and diaminobenzil six sulphonate, or its mixture;
The pH adjusting agent of-Yue 0.1-0.4 part, it is for remaining 8-11 by the pH value of paper-coating composition, and its example be applicable to can include, but are not limited to: sodium hydroxide, potassium hydroxide, ammonia and organic amine properties-correcting agent, or its mixture.
According to concept of the present invention, the present invention includes following following items:
1. comprise the low smell paper-coating composition of solid ingredient and tackiness agent, it is characterized in that described tackiness agent comprises:
The copolymer based emulsion of (a) vinyl, wherein multipolymer comprises, the gross weight based on multipolymer:
(1) part being derived from vinyl-acetic ester of about 65-95pphm;
(2) part being derived from ethene of about 5-35pphm; With
(3) part being derived from other comonomer or function monomer of about 0-10pphm,
Wherein copolymer based emulsion is passed through at about 1-5pphm; preferably about 2-5pphm; the more preferably from about tensio-active agent of 2-4pphm and about 0-10pphm, under the existence of the preferred polymkeric substance protective colloid as emulsifying agent/protective colloid of about 0-5pphm, the letex polymerization of monomer is formed
B water that () is extra.
2. the paper-coating composition any one of aforementioned project, wherein tensio-active agent is selected from anion surfactant, nonionogenic tenside or its combination.
3. the paper-coating composition any one of aforementioned project, wherein anion surfactant is selected from an alkali metal salt of alkyl-sulphate, alkylsulfonate, alkylbenzene sulfonate, alkyl polyoxyethylene ether sulfate, alkyl polyoxyethylene-propylene ether sulfate, fatty alcohol mono succinate sodium sulfonate, fatty alcohol-polyoxyethylene ether sulfo-succinic acid disodium, aliphatic alcohol polyethenoxy-propylene ether sulfo-succinic acid disodium, alkyl polyoxyethylene phosphoric acid salt, alkyl polyoxyethylene-propene phosphoric acid salt, lipid acid, or its mixture.
4. the paper-coating composition any one of aforementioned project, wherein nonionogenic tenside is selected from linear alkyl polyoxyethylenated alcohol, linear alkyl alcohol polyoxyethylene-propylene ether, branched-alkyl polyoxyethylenated alcohol, branched-alkyl alcohol polyoxyethylene-propylene ether, aliphatic acid polyethenoxy monoesters, aliphatic acid polyethenoxy-propylene monoesters, or its mixture.
5. the paper-coating composition any one of aforementioned project, wherein polymkeric substance protective colloid is selected from polyvinyl alcohol, ether of cellulose, the Polyvinylpyrolidone (PVP) of partial hydrolysis, or its mixture.
6. the paper-coating composition any one of aforementioned project, wherein polyvinyl alcohol has about 75-95%, more preferably from about the alcoholysis degree of 70-92% and the polymerization degree of about 200-4000, preferably the alcoholysis degree of about 80-90% and the polymerization degree of about 200-4000.
7. the paper-coating composition any one of aforementioned project, wherein other comonomer or function monomer are selected from:
The vinyl ester of-polyacid, wherein concrete monomer can comprise:
wherein R
1and R
2each be hydrogen or alkyl group, condition is R
1and R
2total carbon atom number be 1-14;
-acrylate, wherein concrete monomer can comprise:
wherein R
3hydrogen or the alkyl group with 1-16 carbon atom;
-methacrylic ester, wherein concrete monomer can comprise:
wherein R
4hydrogen or the alkyl group with 1-16 carbon atom;
-maleic acid ester, wherein concrete monomer can comprise:
wherein R
5and R
6each be the alkyl group with 1-16 carbon atom;
-vinylformic acid; Methacrylic acid; Toxilic acid; Maleic anhydride; Fumaric acid; β-crotonic acid; Methylene-succinic acid; Vinyl cyanide; Methacrylonitrile; Sodium vinyl sulfonate; Vinylbenzenesulfonic acid sodium; 2-methyl-2-[(1-oxo-2-propenyl) is amino]-1-propanesulfonic acid list sodium; Methacrylic ester ethyl-trimethyl salmiac; Acrylamide; Hydroxymethylacrylamide; Hydroxyethyl acrylamide; Hydroxypropylacrylamide; Vinyltrimethoxy silane; Vinyltriethoxysilane; Vinyl three (2-methoxy ethoxy) silane; Methacryloxypropyl trimethoxy silane; Vinylformic acid glycol ester; Vinylformic acid propylene glycol ester; Glycidyl acrylate; Diallyl maleate; Phthalic acid, diallyl ester; Triallyl cyanurate; Allyl methacrylate(AMA); Vinylformic acid ethylene glycol bisthioglycolate methyl esters; Pentaerythritol triacrylate; Pentaerythritol tetracrylate; Acrylic acid ethyl acetoacetoxy groups methyl esters; Diacetone acrylamide; Allyl group acrylamide; Or its mixture.
8. the paper-coating composition any one of aforementioned project, wherein solid ingredient comprises kaolin, calcium carbonate or its mixture.
9. the paper-coating composition any one of aforementioned project, wherein the part by weight of solid ingredient and tackiness agent is about 100:6-100:19, preferably about 100:8-100:16.
10. the paper-coating composition any one of aforementioned project, wherein the content of residual vinyl acetate monomer is less than about 800ppm, is preferably less than about 600ppm, is more preferably less than about 400ppm.
11. for the preparation of the method for the low smell paper-coating composition any one of aforementioned project, and described method comprises:
A () forms vinyl-vinyl acetate copolymer base emulsion by letex polymerization monomer composition, described composition comprises:
(1) part being derived from vinyl-acetic ester of about 65-95pphm;
(2) part being derived from ethene of about 5-35pphm; With
(3) part being derived from other comonomer or function monomer of about 0-10pphm,
Described letex polymerization is at about 1-5pphm, and preferably about 2-5pphm, the more preferably from about tensio-active agent of 2-4pphm and about 0-10pphm, carry out under the existence of the preferred polymkeric substance protective colloid as emulsifying agent/protective colloid of about 0-5pphm;
B () makes described vinyl-vinyl acetate copolymer base emulsion mix to form tackiness agent with extra water;
C () makes described tackiness agent mix with solid ingredient.
12. for the copolymer based emulsion of vinyl of low smell paper-coating composition, and wherein multipolymer comprises, the gross weight based on multipolymer:
(1) part being derived from vinyl-acetic ester of about 65-95pphm;
(2) part being derived from ethene of about 5-35pphm; With
(3) part being derived from other comonomer or function monomer of about 0-10pphm,
Wherein copolymer based emulsion is passed through at about 1-5pphm; preferably about 2-5pphm; the more preferably from about tensio-active agent of 2-4pphm and about 0-10pphm, under the existence of the preferred polymkeric substance protective colloid as emulsifying agent/protective colloid of about 0-5pphm, the letex polymerization of monomer is formed.
13. copolymer based emulsions of vinyl any one of aforementioned project, wherein tensio-active agent is selected from anion surfactant, nonionogenic tenside or its combination.
14. copolymer based emulsions of vinyl any one of aforementioned project, wherein anion surfactant is selected from an alkali metal salt of alkyl-sulphate, alkylsulfonate, alkylbenzene sulfonate, alkyl polyoxyethylene ether sulfate, alkyl polyoxyethylene-propylene ether sulfate, fatty alcohol mono succinate sodium sulfonate, fatty alcohol-polyoxyethylene ether sulfo-succinic acid disodium, aliphatic alcohol polyethenoxy-propylene ether sulfo-succinic acid disodium, alkyl polyoxyethylene phosphoric acid salt, alkyl polyoxyethylene-propene phosphoric acid salt, lipid acid, or its mixture.
15. copolymer based emulsions of vinyl any one of aforementioned project, wherein nonionogenic tenside is selected from linear alkyl polyoxyethylenated alcohol, linear alkyl alcohol polyoxyethylene-propylene ether, branched-alkyl polyoxyethylenated alcohol, branched-alkyl alcohol polyoxyethylene-propylene ether, aliphatic acid polyethenoxy monoesters, aliphatic acid polyethenoxy-propylene monoesters, or its mixture.
16. copolymer based emulsions of vinyl any one of aforementioned project, wherein polymkeric substance protective colloid is selected from polyvinyl alcohol, ether of cellulose, the Polyvinylpyrolidone (PVP) of partial hydrolysis, or its mixture.
17. copolymer based emulsions of vinyl any one of aforementioned project, wherein polyvinyl alcohol has about 75-95%, the more preferably from about alcoholysis degree of 70-92% and the polymerization degree of about 200-4000, the preferably alcoholysis degree of about 80-90% and the polymerization degree of about 200-4000.
18. copolymer based emulsions of vinyl any one of aforementioned project, wherein other comonomer or function monomer are selected from:
The vinyl ester of-polyacid, wherein concrete monomer can comprise:
wherein R
1and R
2each be hydrogen or alkyl group, condition is R
1and R
2total carbon atom number be 1-14;
-acrylate, wherein concrete monomer can comprise:
wherein R
3hydrogen or the alkyl group with 1-16 carbon atom;
Methacrylic ester, wherein concrete monomer can comprise:
wherein R
4hydrogen or the alkyl group with 1-16 carbon atom;
-maleic acid ester, wherein concrete monomer can comprise:
wherein R
5and R
6each be the alkyl group with 1-16 carbon atom;
-vinylformic acid; Methacrylic acid; Toxilic acid; Maleic anhydride; Fumaric acid; β-crotonic acid; Methylene-succinic acid; Vinyl cyanide; Methacrylonitrile; Sodium vinyl sulfonate; Vinylbenzenesulfonic acid sodium; 2-methyl-2-[(1-oxo-2-propenyl) is amino]-1-propanesulfonic acid list sodium; Methacrylic ester ethyl-trimethyl salmiac; Acrylamide; Hydroxymethylacrylamide; Hydroxyethyl acrylamide; Hydroxypropylacrylamide; Vinyltrimethoxy silane; Vinyltriethoxysilane; Vinyl three (2-methoxy ethoxy) silane; Methacryloxypropyl trimethoxy silane; Vinylformic acid glycol ester; Vinylformic acid propylene glycol ester; Glycidyl acrylate; Diallyl maleate; Phthalic acid, diallyl ester; Triallyl cyanurate; Allyl methacrylate(AMA); Vinylformic acid ethylene glycol bisthioglycolate methyl esters; Pentaerythritol triacrylate; Pentaerythritol tetracrylate; Acrylic acid ethyl acetoacetoxy groups methyl esters; Diacetone acrylamide; Allyl group acrylamide; Or its mixture.
19. copolymer based emulsions of vinyl any one of aforementioned project, wherein copolymer based emulsion has and is about 40-70wt% based on emulsion gross weight, the solids content of about 50-60wt% the most usually.
20. copolymer based emulsions of vinyl any one of aforementioned project, wherein the content of residual vinyl acetate monomer is less than about 800ppm, is preferably less than about 600ppm, is more preferably less than about 400ppm.
21. for the preparation of the method for the copolymer based emulsion of vinyl any one of aforementioned project, and described method comprises letex polymerization monomer composition, and described composition comprises:
(1) part being derived from vinyl-acetic ester of about 65-95pphm;
(2) part being derived from ethene of about 5-35pphm; With
(3) part being derived from other comonomer or function monomer of about 0-10pphm,
Described letex polymerization is at about 1-5pphm, and preferably about 2-5pphm, the more preferably from about tensio-active agent of 2-4pphm and about 0-10pphm, carry out under the existence of the preferred polymkeric substance protective colloid as emulsifying agent/protective colloid of about 0-5pphm.
22. methods any one of aforementioned project, wherein letex polymerization is carried out under the existence of redox initiator.
23. methods any one of aforementioned project, wherein initiator is selected from ammonium persulphate, Sodium Persulfate, hydrogen peroxide, tert-butyl peroxide, formaldehyde-sodium hydrosulfite 90min, 2-hydroxyl-2-sulfinyl acetic acid disodium, xitix, saccharosonic acid, an alkali metal salt of xitix, an alkali metal salt of saccharosonic acid, sodium bisulfite, S-WAT, sodium metabisulfite, Sulfothiorine, or its mixture.
24. copolymer based emulsions of vinyl any one of aforementioned project or be used for the purposes of low smell paper-coating composition by the copolymer based emulsion of the obtainable vinyl of method any one of aforementioned project.
25. low smell paper-coating compositions any one of aforementioned project are used for high-end packaging application, the purposes of such as cigarette pack and food Package.
Paper-coating composition of the present invention has low-down smell, even after application ultraviolet (UV) curable ink and electron beam radiation curable ink print technology.Under the linguistic context of the application, term " low smell " means paper-coating composition of the present invention and have passed the smell assessment test hereinafter described.
Smell assessment test can be carried out as follows:
1. the preparation of outturn.
Outturn is prepared: make the tackiness agent be derived from by the copolymer based emulsion of vinyl of aqueous emulsion polymerization preparation as described above mix to obtain paper-coating composition with solid ingredient, dispersion agent, white dyes and rheology modifier by following steps; Therefore the paper-coating composition obtained is applied to the two sides that body paper opens, for precoated layer/inter coat/finishing coat with the amount of 10-15gsm/10-15gsm/10-15gsm; The white board applied by rolling press press polish and being sealed in plastics bag is used for storing.
2.UV solidifies
From plastics bag, take out the outturn therefore obtained, can solidify in UV drying machine, and and then be sealed in plastics bag for storing.Parameter for UV radiation is: UV lamp, 6wx4; Wavelength, 254nm; Radiated time, 30min.
3. smell assessment
Smell assessment is carried out after uv curing in 12 hours.Smell estimation flow is as follows: then open before the plastics bag of the sealing comprising outturn is placed on evaluator nose; After opening plastics bag, evaluator is breathed immediately in the air discharged from plastics bag, and with the value of 1-5 for smell is marked, wherein the value of 1 represents the highest smell and the poorest scoring, and the value of 5 represents minimum smell and best scoring.Assess each outturn by the people of 10 Stochastic choice respectively and the summation exporting scoring as the net result of just each outturn.Those making the summation of the scoring of each outturn and other outturn compare, and obtain the final scoring assessment to each outturn thus.Usually, the value of 5 represents minimum smell, and it can not evaluated people be smelt significantly, and the value of 1 represents the highest smell, its sample meaning test shows serious tart flavour, bitter taste or other chemical smell to evaluator, and the value of 4-2 represents faint odor, obviously smell or heavier smell successively.
In non-limiting embodiments more of the present invention, with by traditional aqueous emulsion, such as, when other paper-coating composition of the preparation such as styrene-butadiene copolymer emulsion, latex of copolymer in cinnamic acrylic ester, acrylate copolymer emulsion, leifa emulsion, vinyl copolymer emulsion is compared, of the present invention low smell paper-coating composition prepared by the copolymer based emulsion of vinyl of being polymerized production by aqueous emulsion described above shows and is greater than 30, more preferably greater than the final scoring of 40.
Include following examples to show the preferred embodiment of the invention.The technology disclosed in following examples that those skilled in the art should understand that represents the technology that the present inventor finds, it works in the practice of the invention well, and therefore, can think and constitute its preference pattern put into practice.But, multiple change can be made in view of the disclosure of invention those skilled in the art should understand that in disclosed specific embodiments, and still obtain same or similar result, and not deviate from the spirit and scope of the present invention.
Embodiment
Unless otherwise contrary explanation, all parts and per-cent are all by weight.
Test
The smell of paper-coating composition of the present invention and other contrast paper-coating composition is tested according to smell assessment test described above.
Embodiment 1
Under stirring (300rpm), in the aqueous solution 4% of the deionized water of 10L reactor interpolation 2.4kg, 116g, there is at 20 DEG C the polyvinyl alcohol at 20 DEG C in the polyvinyl alcohol of the alcoholysis degree of 88% and the viscosity of 5mPa.s and the aqueous solution 4% of 120g with the alcoholysis degree of 88% and the viscosity of 23mPa.s.Reactor be heated to 99 DEG C and maintain 1 hour to obtain the solution fully dissolved.Then by reactor cooling to 55 DEG C.Successively 85% phosphoric acid solution (using it for the pH of regulator solution) of the Disponil A3065 (Cognis has the concentration of 65%) of 33g, the sodium acetate of 3g and 6g, the silicone antifoam agent of 2g and 40% ferric chloride Solution of 0.2g are added in reactor to be provided for the catalyzer of polyreaction.Three emptying reactors and with nitrogen purge, to remove residual air.Then stirring velocity is increased to 600rpm.Be added in reactor by the vinyl-acetic ester of fresh feed pump by 2.9kg, and the ethylene gas of 550g be fed in reactor simultaneously.By the pressure equilibrium 5 minutes by reactor, and then add the 1.7wt%2-hydroxyl-2-sulphonyl acetic acid disodium aqueous solution of 35g to reactor.5 minutes are balanced at reactor being remained on 55 DEG C.By initiated polymerization in following initiator feed to reactor: the 1.5wt% tert-butyl peroxide aqueous solution with the initial charge speed of 94.5g/h, the 1.7wt%2-hydroxyl-2-sulphonyl acetic acid disodium aqueous solution of initial charge speed with 94.5g/h.When the temperature of reactor reaches 57 DEG C, by regulating the flow rate control temperature of reaction of initiator, so that temperature of reaction was increased to 85 DEG C and at then maintaining 85 DEG C in 20 minutes.When the temperature of reactor reaches 72 DEG C, add the ethylene gas of 230g, and the peak pressure of inside reactor is maintained lower than 60bar.When the temperature of reactor reaches 80 DEG C, by the feeding rate of 1.26kg/h, 1.24kg vinyl-acetic ester is added into reactor.
After the interpolation of initiator completes, by reactor cooling to 55 DEG C.The emulsion of acquisition is transferred to aftertreatment reactor.
Stir aftertreatment reactor with the speed of 200rpm and in 30 minutes, add the 3.1wt%2-hydroxyl-2-sulphonyl acetic acid disodium aqueous solution of 90g, in 30 minutes, then adding the 1wt% tert-butyl peroxide aqueous solution of 90g and the mixture of 1wt% hydrogen peroxide aqueous solution.Under aftertreatment reactor being remained on the vacuum tightness of-0.3bar.When the temperature of aftertreatment reactor reaches 65 DEG C, add the water vapour of total amount 105g backward in treatment reactor for extraction.Finally, by aftertreatment reactor cooling to 40 DEG C.The 1.5%CIT/MIT sterilant of 30g is added in aftertreatment reactor.
The character of the copolymer based emulsion of vinyl (emulsion 1) obtained is listed in table 1.
Table 1, the character of emulsion 1
| Solids content | 56.42wt％ |
| pH | 4.3 |
| Viscosity (BVF, 20rpm) | 5670mPa.s |
| Granularity (D90) | 2.0μm |
| Residual monomer | 291ppm |
Embodiment 2
Except aftertreatment reactor does not stand vapor extraction, prepare the copolymer based emulsion of vinyl (emulsion 2) according to the flow process in embodiment 1.The copolymer based emulsion of vinyl (emulsion 2) obtained has the residual monomer content of 685ppm.
Comparative example 1
Obtain the commercially available styrene-butadiene copolymer emulsion for paper coating (contrast emulsion 1), it has the residual monomer content of 60ppm.
Comparative example 2
Obtain the commercially available latex of copolymer in cinnamic acrylic ester for paper coating (contrast emulsion 2), it has the residual monomer content of 550ppm.
Results and discussions
According to the formula listed in table 2, respectively by the emulsion that obtains in embodiment 1-2 and comparative example 1-2 for the preparation of paper-coating composition.
Table 2, the formula of paper-coating composition
| Component | Amount, weight part |
| Emulsion, dry base | 14 |
| Kaolin | 30 |
| Calcium carbonate C95 | 70 |
| Dispersion agent 5040 | 0.1 |
| Fluorescent whitening agent OB A | 0.75 |
| Thickening material CMC | 0.4 |
| Defoamer Foamaster NXZ | 0.1 |
| Sodium hydroxide | 0.1 |
Test according to smell assessment test described above the paper-coating composition therefore obtained respectively, and the results are summarized in table 3.
Table 3, the result of smell assessment test
According to the result of table 3, although the residual monomer content of emulsion 1 (291ppm) is higher than contrast emulsion 1 (60ppm), the paper-coating composition prepared by emulsion 1 according to the present invention shows the scoring more much higher than the paper-coating composition prepared by contrast emulsion 1.The paper-coating composition prepared by the emulsion 2 of the high residue monomer content with 685ppm also have passed smell assessment test with the value being greater than 30, this points out that the copolymer based emulsion of vinyl according to the present invention can provide low smell for paper-coating composition prepared therefrom, especially after being exposed to UV drying machine according to the flow process of smell assessment test, therefore can be used as tackiness agent, such as, for there is the printing packaging of high-quality, cigarette pack, food Package etc.
In view of the disclosure of invention, can make and perform open and claimed all methods herein when not making undo experimentation.Although describe product of the present invention and method in the mode of preferred embodiment, but be apparent that for a person skilled in the art, when not deviating from concept of the present invention, spirit and scope, can apply to change to present method with the order of the step of method described herein or step.
Claims (23)
1. comprise the low smell paper-coating composition of solid ingredient and tackiness agent, it is characterized in that described tackiness agent comprises:
The copolymer based emulsion of (a) vinyl, wherein said multipolymer comprises, the gross weight based on multipolymer:
(1) part being derived from vinyl-acetic ester of about 65-95pphm;
(2) part being derived from ethene of about 5-35pphm; With
(3) part being derived from other comonomer or function monomer of about 0-10pphm,
Wherein said copolymer based emulsion is passed through at about 1-5pphm; preferably about 2-5pphm; the more preferably from about tensio-active agent of 2-4pphm and about 0-10pphm, under the existence of the preferred polymkeric substance protective colloid as emulsifying agent/protective colloid of about 0-5pphm, the letex polymerization of monomer is formed
B water that () is extra.
2. paper-coating composition according to claim 1, wherein said tensio-active agent is selected from anion surfactant, nonionogenic tenside or its combination.
3. paper-coating composition according to claim 2, wherein said anion surfactant is selected from an alkali metal salt of alkyl-sulphate, alkylsulfonate, alkylbenzene sulfonate, alkyl polyoxyethylene ether sulfate, alkyl polyoxyethylene-propylene ether sulfate, fatty alcohol mono succinate sodium sulfonate, fatty alcohol-polyoxyethylene ether sulfo-succinic acid disodium, aliphatic alcohol polyethenoxy-propylene ether sulfo-succinic acid disodium, alkyl polyoxyethylene phosphoric acid salt, alkyl polyoxyethylene-propene phosphoric acid salt, lipid acid, or its mixture.
4. paper-coating composition according to claim 2, wherein said nonionogenic tenside is selected from linear alkyl polyoxyethylenated alcohol, linear alkyl alcohol polyoxyethylene-propylene ether, branched-alkyl polyoxyethylenated alcohol, branched-alkyl alcohol polyoxyethylene-propylene ether, aliphatic acid polyethenoxy monoesters, aliphatic acid polyethenoxy-propylene monoesters, or its mixture.
5. paper-coating composition according to claim 1, wherein said polymkeric substance protective colloid is selected from polyvinyl alcohol, ether of cellulose, the Polyvinylpyrolidone (PVP) of partial hydrolysis, or its mixture.
6. paper-coating composition according to claim 5, wherein said polyvinyl alcohol has about 75-95%, more preferably from about the alcoholysis degree of 70-92% and the polymerization degree of about 200-4000, preferably the alcoholysis degree of about 80-90% and the polymerization degree of about 200-4000.
7. paper-coating composition according to claim 1, wherein other comonomer or function monomer are selected from:
The vinyl ester of-polyacid, wherein concrete monomer can comprise:
wherein R
1and R
2each be hydrogen or alkyl, condition is R
1and R
2total carbon atom number be 1-14;
-acrylate, wherein concrete monomer can comprise:
wherein R
3hydrogen or the alkyl group with 1-16 carbon atom;
-methacrylic ester, wherein concrete monomer can comprise:
wherein R
4hydrogen or the alkyl group with 1-16 carbon atom;
-maleic acid ester, wherein concrete monomer can comprise:
wherein R
5and R
6each be the alkyl group with 1-16 carbon atom;
-vinylformic acid; Methacrylic acid; Toxilic acid; Maleic anhydride; Fumaric acid; β-crotonic acid; Methylene-succinic acid; Vinyl cyanide; Methacrylonitrile; Sodium vinyl sulfonate; Vinylbenzenesulfonic acid sodium; 2-methyl-2-[(1-oxo-2-propenyl) is amino]-1-propanesulfonic acid list sodium; Methacrylic ester ethyl-trimethyl salmiac; Acrylamide; Hydroxymethylacrylamide; Hydroxyethyl acrylamide; Hydroxypropylacrylamide; Vinyltrimethoxy silane; Vinyltriethoxysilane; Vinyl three (2-methoxy ethoxy) silane; Methacryloxypropyl trimethoxy silane; Vinylformic acid glycol ester; Vinylformic acid propylene glycol ester; Glycidyl acrylate; Diallyl maleate; Phthalic acid, diallyl ester; Triallyl cyanurate; Allyl methacrylate(AMA); Vinylformic acid ethylene glycol bisthioglycolate methyl esters; Pentaerythritol triacrylate; Pentaerythritol tetracrylate; Acrylic acid ethyl acetoacetoxy groups methyl esters; Diacetone acrylamide; Allyl group acrylamide; Or its mixture.
8. paper-coating composition according to claim 1, wherein said solid ingredient comprises kaolin, calcium carbonate or its mixture.
9. paper-coating composition according to claim 1, wherein the part by weight of solid ingredient and tackiness agent is about 100:6-100:19, preferably about 100:8-100:16.
10., for the preparation of the method for low smell paper-coating composition as claimed in one of claims 1-9, described method comprises:
A () forms vinyl-vinyl acetate copolymer base emulsion by letex polymerization monomer composition, described composition comprises:
(1) part being derived from vinyl-acetic ester of about 65-95pphm;
(2) part being derived from ethene of about 5-35pphm; With
(3) part being derived from other comonomer or function monomer of about 0-10pphm,
Described letex polymerization is at about 1-5pphm, and preferably about 2-5pphm, the more preferably from about tensio-active agent of 2-4pphm and about 0-10pphm, carry out under the existence of the preferred polymkeric substance protective colloid as emulsifying agent/protective colloid of about 0-5pphm;
B () makes described vinyl-vinyl acetate copolymer base emulsion mix to form tackiness agent with extra water;
C () makes described tackiness agent mix with solid ingredient.
11. for the copolymer based emulsion of vinyl of low smell paper-coating composition, and wherein said multipolymer comprises, the gross weight based on multipolymer:
(1) part being derived from vinyl-acetic ester of about 65-95pphm;
(2) part being derived from ethene of about 5-35pphm; With
(3) part being derived from other comonomer or function monomer of about 0-10pphm,
Wherein copolymer based emulsion is passed through at about 1-5pphm; preferably about 2-5pphm; the more preferably from about tensio-active agent of 2-4pphm and about 0-10pphm, under the existence of the preferred polymkeric substance protective colloid as emulsifying agent/protective colloid of about 0-5pphm, the letex polymerization of monomer is formed.
The copolymer based emulsion of 12. vinyl according to claim 11, wherein said tensio-active agent is selected from anion surfactant, nonionogenic tenside or its combination.
The copolymer based emulsion of 13. vinyl according to claim 12, wherein said anion surfactant is selected from an alkali metal salt of alkyl-sulphate, alkylsulfonate, alkylbenzene sulfonate, alkyl polyoxyethylene ether sulfate, alkyl polyoxyethylene-propylene ether sulfate, fatty alcohol mono succinate sodium sulfonate, fatty alcohol-polyoxyethylene ether sulfo-succinic acid disodium, aliphatic alcohol polyethenoxy-propylene ether sulfo-succinic acid disodium, alkyl polyoxyethylene phosphoric acid salt, alkyl polyoxyethylene-propene phosphoric acid salt, lipid acid, or its mixture.
The copolymer based emulsion of 14. vinyl according to claim 12, wherein said nonionogenic tenside is selected from linear alkyl polyoxyethylenated alcohol, linear alkyl alcohol polyoxyethylene-propylene ether, branched-alkyl polyoxyethylenated alcohol, branched-alkyl alcohol polyoxyethylene-propylene ether, aliphatic acid polyethenoxy monoesters, aliphatic acid polyethenoxy-propylene monoesters, or its mixture.
The copolymer based emulsion of 15. vinyl according to claim 11, wherein said polymkeric substance protective colloid is selected from polyvinyl alcohol, ether of cellulose, the Polyvinylpyrolidone (PVP) of partial hydrolysis, or its mixture.
The copolymer based emulsion of 16. vinyl according to claim 15, wherein said polyvinyl alcohol has about 75-95%, the more preferably from about alcoholysis degree of 70-92% and the polymerization degree of about 200-4000, the preferably alcoholysis degree of about 80-90% and the polymerization degree of about 200-4000.
The copolymer based emulsion of 17. vinyl according to claim 11, wherein other comonomer or function monomer are selected from:
The vinyl ester of-polyacid, wherein concrete monomer can comprise:
wherein R
1and R
2each be hydrogen or alkyl group, condition is R
1and R
2total carbon atom number be 1-14;
-acrylate, wherein concrete monomer can comprise:
wherein R
3hydrogen or the alkyl group with 1-16 carbon atom;
-methacrylic ester, wherein concrete monomer can comprise:
wherein R
4hydrogen or the alkyl group with 1-16 carbon atom;
-maleic acid ester, wherein concrete monomer can comprise:
wherein R
5and R
6each be the alkyl group with 1-16 carbon atom;
-vinylformic acid; Methacrylic acid; Toxilic acid; Maleic anhydride; Fumaric acid; β-crotonic acid; Methylene-succinic acid; Vinyl cyanide; Methacrylonitrile; Sodium vinyl sulfonate; Vinylbenzenesulfonic acid sodium; 2-methyl-2-[(1-oxo-2-propenyl) is amino]-1-propanesulfonic acid list sodium; Methacrylic ester ethyl-trimethyl salmiac; Acrylamide; Hydroxymethylacrylamide; Hydroxyethyl acrylamide; Hydroxypropylacrylamide; Vinyltrimethoxy silane; Vinyltriethoxysilane; Vinyl three (2-methoxy ethoxy) silane; Methacryloxypropyl trimethoxy silane; Vinylformic acid glycol ester; Vinylformic acid propylene glycol ester; Glycidyl acrylate; Diallyl maleate; Phthalic acid, diallyl ester; Triallyl cyanurate; Allyl methacrylate(AMA); Vinylformic acid ethylene glycol bisthioglycolate methyl esters; Pentaerythritol triacrylate; Pentaerythritol tetracrylate; Acrylic acid ethyl acetoacetoxy groups methyl esters; Diacetone acrylamide; Allyl group acrylamide; Or its mixture.
The copolymer based emulsion of 18. vinyl according to claim 11, wherein said copolymer based emulsion has and is about 40-70wt% based on emulsion gross weight, the most usually the solids content of about 50-60wt%.
19. for the preparation of the method for the copolymer based emulsion of the vinyl any one of claim 11-18, and described method comprises letex polymerization monomer composition, and described composition comprises:
(1) part being derived from vinyl-acetic ester of about 65-95pphm;
(2) part being derived from ethene of about 5-35pphm; With
(3) part being derived from other comonomer or function monomer of about 0-10pphm,
Described letex polymerization is at about 1-5pphm, and preferably about 2-5pphm, the more preferably from about tensio-active agent of 2-4pphm and about 0-10pphm, carry out under the existence of the preferred polymkeric substance protective colloid as emulsifying agent/protective colloid of about 0-5pphm.
20. methods according to claim 19, wherein letex polymerization is carried out under the existence of redox initiator.
21. methods according to claim 20, wherein said initiator is selected from ammonium persulphate, Sodium Persulfate, hydrogen peroxide, tert-butyl peroxide, formaldehyde-sodium hydrosulfite 90min, 2-hydroxyl-2-sulfinyl acetic acid disodium, xitix, saccharosonic acid, an alkali metal salt of xitix, an alkali metal salt of saccharosonic acid, sodium bisulfite, S-WAT, sodium metabisulfite, Sulfothiorine, or its mixture.
22. copolymer based emulsions of vinyl any one of claim 11-18 or the copolymer based emulsion of the obtainable vinyl of the method any one of claim 19-21 are used for the purposes of low smell paper-coating composition.
23. low smell paper-coating compositions as claimed in one of claims 1-9 in high-end packaging application, such as, purposes in cigarette pack and food Package.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2012/075432 WO2013170411A1 (en) | 2012-05-14 | 2012-05-14 | Vinyl acetate-ethylene copolymer emulsion and paper coating composition based on the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104284954A true CN104284954A (en) | 2015-01-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280073137.9A Pending CN104284954A (en) | 2012-05-14 | 2012-05-14 | Vinyl acetate-ethylene copolymer emulsion and paper coating composition based on the same |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20150133577A1 (en) |
| EP (1) | EP2850141A4 (en) |
| CN (1) | CN104284954A (en) |
| WO (1) | WO2013170411A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107567467A (en) * | 2015-04-30 | 2018-01-09 | 阿朗新科德国有限责任公司 | Ethylene copolymer with improved low-temperature characteristics and good oil resistivity, and curable mixtures and curing rubber by its production |
| CN107793519A (en) * | 2016-09-07 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of method for preparing EVA elastomer microemulsions |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015147352A1 (en) * | 2014-03-27 | 2015-10-01 | Wacker Chemicals Korea Inc. | Aqueous vinyl acetate ethylene copolymer dispersion for paper coating |
| CN105951513A (en) * | 2016-05-04 | 2016-09-21 | 太仓市源创包装材料厂 | Production method of wrapping paper with noctilucence effect |
| CN109234046B (en) * | 2018-10-25 | 2020-08-04 | 江南大学 | Nonionic polymer surfactant and synthesis method thereof |
| CN113454179B (en) * | 2019-02-26 | 2023-12-05 | 株式会社Moresco | Method for producing ethylene-vinyl acetate-based hot-melt adhesive, and hot-melt adhesive |
| CN112622344A (en) * | 2019-10-09 | 2021-04-09 | 大理州祥云大宇包装有限公司 | Energy-saving and environment-friendly corrugated carton production process |
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- 2012-05-14 EP EP12876890.0A patent/EP2850141A4/en not_active Withdrawn
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107567467A (en) * | 2015-04-30 | 2018-01-09 | 阿朗新科德国有限责任公司 | Ethylene copolymer with improved low-temperature characteristics and good oil resistivity, and curable mixtures and curing rubber by its production |
| CN107567467B (en) * | 2015-04-30 | 2020-06-05 | 阿朗新科德国有限责任公司 | Ethylene copolymers having improved low temperature properties and good oil resistance, and curable mixtures and cured rubbers produced therefrom |
| CN107793519A (en) * | 2016-09-07 | 2018-03-13 | 中国石油化工股份有限公司 | A kind of method for preparing EVA elastomer microemulsions |
| CN107793519B (en) * | 2016-09-07 | 2020-06-09 | 中国石油化工股份有限公司 | Method for preparing EVA elastomer microemulsion |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013170411A1 (en) | 2013-11-21 |
| EP2850141A1 (en) | 2015-03-25 |
| EP2850141A4 (en) | 2016-01-06 |
| US20150133577A1 (en) | 2015-05-14 |
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