CN104411488B - The functionalized vinyl acetate-ethylene adhesive coated for paper and hardboard - Google Patents
The functionalized vinyl acetate-ethylene adhesive coated for paper and hardboard Download PDFInfo
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- CN104411488B CN104411488B CN201280074550.7A CN201280074550A CN104411488B CN 104411488 B CN104411488 B CN 104411488B CN 201280074550 A CN201280074550 A CN 201280074550A CN 104411488 B CN104411488 B CN 104411488B
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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
- D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
-
- 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
-
- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
-
- 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
- D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/32—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule
-
- 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
-
- 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
- D21H19/80—Paper comprising more than one coating
- D21H19/82—Paper comprising more than one coating superposed
-
- 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
- D21H21/18—Reinforcing agents
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
Abstract
A kind of paper product; it includes plane fibers cellulosic substrates; with the coating composition on the surface of the base material; it includes interpretations; the interpretation is in (v) stabilization systems; it includes one or more anion and/or nonionic surface active agent, but are less than any protective colloid material of about 1pphm；(v) it in the presence of water, is prepared by the emulsion polymerization of following component：(i) one or more vinyl ester monomers；(ii) ethylene；(iii) unsaturated silane comonomer；(iv) one or more emulsion stabilization ionic comonomers, it includes one or more undersaturated substituted sulfonic acid, the esters of one or more unsaturated phosphonic acids or one of those acid.
Description
Invention field
The present invention relates to aqueous, surfactant stabilization, the functionalized lotion based on vinyl esters/ethylene is interpolymerized
Object, enhancing is shown when being coated in formulation for paper kills a mao intensity.
Background of invention
The paper coating formulation of coloring generally comprises aqueous synthetic polymer binder lotion and pigment, and can be with
Including other additives typically used as in paper coating field.Exemplary polymer adhesive in lotion field is vinyl acetate
Ester copolymer and interpretation, including vinyl acetate/ethylene and vinyl acetate/alkyl acrylate copolymer and interpretation,
With phenylethylene/butadiene and phenylethylene ethylene/propenoic acid ester copolymer.Such copolymer and interpretation can also include other copolymerization
The olefinic unsaturated monocarboxylic of monomer such as copolymerization either dicarboxylic acids or can serve as crosslinking agent other unsaturation copolymerization it is single
Body.
United States Patent (USP) No.4395499 for example discloses the high intensity pigment binder coated for paper, with increased
Water-retaining property and stability.The coating composition includes aqueous synthetic polymer latex, and it includes the dispersions of following component
Interpretation：Vinyl esters；(it can be cyanuric acid alkatriene propyl diester, three allyl of isocyanuric acid to polyene category unsaturated comonomer
Base ester, maleic acid diallyl ester, fumaric acid diallyl ester, divinylbenzene or diallyl phthalate)；Alkene
Belong to unsaturated monocarboxylic either dicarboxylic acid comonomer or its half ester；With optional alkyl acrylate comonomer.
Regardless of the availability of these different types of paper application of adhesive lotions, coated paper and coating hardboard manufacture
Quotient is there is a continuing need for paper coating lotion (that is, paper application of adhesive) is differentiated, when in for paper coating composition, in the composition
When being administered on paper and cardboard product, increased adhesive strength is provided.Most frequently, adhesive strength is by being referred to as
The paper of IGT resistance to picking (pick resistance) test is tested to quantify.In the test of IGT hair loss, IGT values are higher, glue
Mixture is stronger, and vice versa.
A variety of emulsion polymerization components and technology can influence adhesive strength, but it is known that, conventionally, be to be based on vinyl acetate
(such as polyvinyl acetate, vinyl and above-mentioned are based on acetic acid at vinyl acetate-acrylate to the adhesive of ester
The adhesive of vinyl acetate) it provides than the paint adhesive such as styrene butadiene and styrene-acrylate that more generally use more
Low adhesive strength.It is provided in order to compensate for the paper coating composition due to the use of such adhesive based on vinyl esters
Lower IGT resistance to picking needs higher binder content, and this compromises the paint adhesive with these types certainly
The earning rate of manufactured coated paper and cardboard product.
For many years, vinyl acetate/ethylene (VAE) copolymer and interpretation for paper coating application developed are non-
Often few, this is attributed to the problem related to processing ethylene gas.
United States Patent (USP) No.3337482 for example discloses paper coating composition, contains pigment and adhesive agent emulsion, the breast
Liquid includes ethylene, the copolymerization of vinyl acetate and olefinic unsaturated monocarboxylic either dicarboxylic acids such as acrylic acid or maleic acid
Object.The adhesive agent emulsion of the patent of ' 482 is the emulsion polymerization by comonomer, and using nonionic emulsifier, (it includes polyoxies
Ethylene oil base or lauryl phenyl ether) come what is prepared.
EP0140227 discloses the high intensity pigment binder coated for paper, with increased water-retaining property and stabilization
Property.The coating composition includes aqueous synthetic polymer latex and pigment, and can include institute in coating paper coating field
Other additives.The latex includes vinyl esters, organo functional silanes, carboxyl and/or amide functionality and optional
Ethylene and/or other polymerizable object comonomers.
But recently, device and professional technique have been developed, easily to gather with commercial manufacturing scale
Close vinyl esters/ethylene with stable environment close friend, such as vinyl acetate/ethylene (VAE) paint adhesive.Therefore, it is related to
The current situation in emulsion polymerization field for the vinyl esters/ethylene copolymer and interpretation that surfactant is stablized makes such
Polymer material become for paper/hardboard coating application very it is desirable that candidate.If VAE bases in this way are viscous
The adhesive strength that mixture is shown can be with the adhesive based on non-vinyl esters such as styrene-based butadiene and benzene second
The adhesive strength of those of alkene acrylate is suitable, then such business potential for VAE base products may be implemented.
U.S. Patent Publication 2012/0021237 discloses the latex emulsion of surfactant stabilization, can be used as bonding
Agent is used in paper coating composition.Such latex emulsion includes to be formed by mutually by the emulsion polymerization selected from following monomer
Polymers：Vinyl esters such as vinyl acetate；Ethylene；Certain undersaturated monocarboxylic acids and dicarboxyl acid substance such as acrylic acid or
Maleic anhydride；Belong to unsaturated cross-linking comonomer such as diallyl phthalate with certain polyenes.These latex emulsions
It is to be stablized with surfactant, there is no incredible alkylphenol ethoxylate (APE) in terms of environment.Contain this
The paper coating composition of the latex emulsion adhesive of type show especially it is desirable that coating intensity, be in this way
Composition provided kill gross value (as herein defined) come what is quantified.
Conventionally, these copolymers are prepared by polymerizeing comonomer appropriate in aqueous emulsion.Such breast
Liquid can be stablized by the way that conventional surfactant (anion, nonionic, cation) is added as emulsifier.Such breast
Liquid can also be by including protective colloid for example based on polyvinyl alcohol (PVOH), ion modification starch, water soluble starch, starch
Ether, polyacrylic acid, carboxymethyl cellulose, natural gum, gel, synthetic polymer or water-soluble cellulose ether such as hydroxyl second
Those of base cellulose (HEC) is stablized.
From allowing effectively by the lotion and different types of filler (it is used in paper coating composition) compounding
Viewpoint for, vinyl esters/ethylene (VAE) latex emulsion of substantially full surfactant base (that is, containing considerably less or
Person does not have protective colloid as those of emulsion stabilizer) be it is special it is desirable that.Substantially full surfactant is stablized
Adhesive agent emulsion additionally provide in papermaking by such as SBR styrene butadiene rubbers of the other materials used in paper Typical Industrial
(SBR) the excellent compatibility of lotion.
Though matching for such filler mixes compatibility benefit, substantially vinyl esters/ethylene of surfactant base
Lotion can lead to some processing problems when as paper coating composition in paper-making process.Specifically, it lives when with full surface
Property agent adhesive agent emulsion coating paper leave the curing oven at 110 DEG C -120 DEG C, then on a series of deflector rolls advance and can
When can pass through cutter, such processing problems can show.The coating composition that substantially full surfactant is stablized has
It is transferred on roller and generates the trend of accumulation, this can cause maintenance issues.In addition, sometimes, this accumulation can be transferred back to
Paper, this can cause undesirable exception on paper surface.
Trial has been carried out to keep the benefit of substantially full surfactant base latex adhesive, while making above
The processing problems minimize.Such trial for example uses surfactant emulsifiers and protective colloid for example including using
The lotion based on vinyl esters-ethylene that both PVOH stablize.Although some such trials have been achieved for certain successes,
It is emulsifier/colloid system that these are mixed must highly precisely prepare, even and if not carrying in this way, remaining on and having even
For the trend of whole benefits (benefit can be realized by using any type of individual stabiliser system).Therefore,
It continues to need and determines the paper coating composition based on vinyl esters/ethylene copolymer emulsion, show substantially full surface
The whole benefits for the lotion that activating agent is stablized, but it does not lead to the unacceptable hair of processing problems unfavorable in paper-making process
It is raw.
It, can be with it has now been discovered that comonomer and stabilizing surface activating agent by selecting certain types and relative quantity
Prepare especially it is desirable that vinyl esters/ethylene type latex adhesive.Such latex adhesive be it is desirable that, because
It may be used to provide the particularly effective and environmental-friendly coating composition for paper and hardboard for them.
Invention content
On the one hand, the present invention relates to a kind of paper products, and it includes plane fibers cellulosic substrates, and are located at the base
Precoating composition on the surface of material, it includes interpretation, the interpretation be in (v) stabilization systems, it includes a kind of or
A variety of anion and/or nonionic surface active agent, but it is less than any protective colloid material of about 1pphm；(v)
In the presence of water, prepared by the emulsion polymerization of following component：(i) one or more vinyl ester monomers；(ii) ethylene；
(iii) unsaturated silane comonomer；(iv) one or more emulsion stabilization ionic comonomers, it includes a kind of or
A variety of：(a) undersaturated substituted the organic sulfonic acid either undersaturated organic phospho acid of its salt (b) or its salt, (c) insatiable hunger
Substituted organic sulfonic acid ester/salt/acid of sum either sulfuric ester/salt/acid or (d) undersaturated Organophosphonate/salt/acid or
Person's phosphate/salt/acid.
An alternate embodiment of the present invention is related to a kind of method for the paper product forming coating comprising (a), which is used, to be applied
Feed composition coats plane fibers cellulosic substrates, and to form the base material that wet coating is covered, wherein the coating composition includes and passes through
Emulsion polymerization is by the interpretation prepared by following component：(i) one or more vinyl ester monomers；(ii) ethylene；(iii) no
It is saturated silane comonomers；(iv) one or more emulsion stabilization ionic comonomers, it includes at least undersaturated
Substituted organic sulfonic acid either its salt, undersaturated organic phospho acid or its salt, undersaturated substituted organic sulfonic acid ester/salt/
Sour either sulfuric ester/salt/acid or undersaturated Organophosphonate/salt/acid or phosphate/salt/acid；The emulsion polymerization is
It is carried out in the presence of component below：(vi) stabilization systems, it includes one or more anion and/or non-ionic surfaces
Activating agent, but it is less than any protective colloid material of about 1pphm；(vii) water；(b) base material that the dry wet coating is covered
To form the base material of dry coating；(c) roll the base material of the coating of the drying to form the paper product of coating.
Description of the drawings
Fig. 1 is showing the figure of the relatively dry resistance to picking between two embodiments of the present invention and conventional paper coating.
Specific implementation mode
The present invention relates to the latex bonded agent emulsions of interpretation that aqueous, surfactant is stablized, in such bonding
When agent emulsion is mixed into the coating composition for paper product, show excellent to kill a mao intensity.In some cases, should
Coating composition may be used as the pre- coating of paper, and then with top coat combination object plane coating.Such latex bonded agent emulsion packet
The interpretation containing Vinyl ester comonomers is contained, the monomer is copolymerized with the ethylene of selected amount, unsaturated silane
Monomer, one or more emulsion stabilization ionic comonomers (it includes one or more undersaturated substituted sulfonic acid,
The ester of one of unsaturated phosphonic acids or those acid) it is copolymerized, and there are stabilization systems, it includes one or more the moon
Ionically and/or non-ionically type surfactant, but it is less than any protective colloid material of about 1pphm.The emulsion polymerization
It can carry out by conventional methods, to form the adhesive latex containing desired interpretation.
The vinyl esters for being used to form the interpretation of latex bonded agent emulsion here is the ester of alkanoic acid, which has 1-
About 13 carbon atoms.Typical example includes vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, isobutyl
Vinyl acetate, vinyl valerate, 2 ethyl hexanoic acid vinyl esters, isooctyl acid vinyl acetate, vinyl pelargonate ester, caprate are special
Vinyl valerate (vinyl pivalate), tertiary ethylene carbonate etc..In the foregoing, vinyl acetate is preferred monomer, this
It is attributed to its being easy to get property and low cost.
Amount of the vinyl esters preferably in interpretation is that (number per hundred parts, is based on about 67pphm-99pphm
Total monomer in the interpretation).More preferably the vinyl ester content of interpretation used in the paper coating composition will be here
About 70pphm-90pphm.
Second key component of the interpretation formed in the adhesive latex is ethylene.Ethylene will usually account for interpretation
About 1.0pphm-30.0pphm.More preferable amount of the ethylene in interpretation is about 2pphm-25pphm.
The third component of interpretation in the adhesive latex includes the unsaturated silane comonomer of minor amount.It is this total
Polycondensation monomer can correspond generally to the substituted silane of structural formula I：
The undersaturated organic group of alkene and R in ω-position are indicated in wherein R1、R2And R3(it can be identical or not
Halogen is indicated together), and preferably either group-OZ Z indicate hydrogen or primary or secondary alkyl or acyl group to chlorine, are optionally taken with alkoxy
Generation.
The suitable unsaturated silane compound of Formulas I is preferably those, and the group R in the wherein described formula indicates 2-10
Carbon atom, ω-unsaturated chain alkenyl of especially 2-4 carbon atom, or by height to the unsaturated carboxylic acid and height of 4 carbon atoms
ω-the esters of unsaturated carboxylic acids formed to the alcohol with Si groups of 6 carbon atoms.Suitable group R1、R2、R3Preferably group-
OZ, Z represent high to 10 carbon atoms, the uncle of preferably high to 4 carbon atoms and/or secondary alkyl group, or are replaced with alkoxy
Alkyl group (preferably high to 3 carbon atoms), or high to 6 carbon atoms, the preferably high carboxyl groups to 3 carbon atoms,
Or hydrogen.Most preferred unsaturated silane comonomer is vinyl trialkyl oxysilane.
The example of the preferred silane compound of Formulas I includes vinyl trichlorosilane, vinyl methyl dichlorosilane, γ-
Methacryloxypropyl three (2- methoxy ethoxies) silane, vinyl methoxy silane, vinyltrimethoxysilane, second
Alkenyl triethoxysilane, vinyl diethoxy silanol, vinylethoxysilane glycol, allyltriethoxysilane,
Vinyl tripropoxy silane, vinyl silane triisopropoxide, vinyltributoxysilane, vinyl triacetoxy silicon
Alkane, trimethyl glycol vinyl silanes, gamma-methyl allyl acyloxypropyl trimethyl glycol silane, three second of γ-acryloxypropyl
Oxysilane and gamma-methyl allyl acyloxypropyl trimethoxysilane.
Above-mentioned unsaturated silane comonomer is selected and is used to form the interpretation used herein of coating composition,
Its dosage can effectively change interpolymer molecule amount, branched and/or flowing property, such as about 0.1pphm- in some way
About 3pphm, either even about 0.1pphm- about 1.5pphm or about 0.2pphm- about 0.5pphm.
The interpretation includes in addition minor amount, such as about 0.1pphm- about 5pphm, or about 0.1pphm- is big
About 1.0pphm, or about 0.2pphm- about 0.5pphm one or more other comonomer types, contribute to
The stabilisation of the latex emulsion of formation.Such stabilisation comonomer is those, due to containing acid moieties or such
The salt or half ester of acid moieties but ionic nature.Specifically, which should include one or more undersaturated substitutions
The organic sulfonic acid either undersaturated organic phospho acid of its salt or its salt, undersaturated substituted organic sulfonic acid ester/salt/acid or
Person's sulfuric ester/salt/acid either undersaturated Organophosphonate/salt/acid or phosphate/salt/acid.These types it is exemplary
Monomer is disclosed in U.S. Published Application No.2004/0043155 and 2006/0211594, herein using all of which introduce as
With reference to, and include the monomer containing at least one sulfuric ester or sulfonate functional, such as 2- sulfoethyl methacrylates,
2- acrylamido -2- methyl propane sulfonic acids, styrene sulfonic acid, vinyl phosphonic acid, phosphate ester monomer is for example obtained from Rhodia's
PAM-100 and PAM-200 phosphate ester monomers and the corresponding salt of these monomers, 2- sulphur oxygen ethylmethyl acrylates, vinyl benzene
Sulfonic acid, allyl sulphonic acid, 2- acrylamido -2- methyl propane sulfonic acids, sulfoethyl acrylate either methacrylate or
Sulfopropyl acrylate or methacrylate and its water soluble salt, acrylamido methyl propane sulfonic acid, styrene sulfonic acid
Ester, sodium vinyl sulfonate, and the monomer containing at least one phosphonate ester or phosphate functional, such as vinyl phosphonic acid, olefinic is not
Saturation phosphate (such as the phosphate (Empicryl 6835 comes from Rhodia) derived from hydroxyethyl methacrylate and derivative
From those of following：Poly (oxyalkylene) methyl acrylate and its water soluble salt, vinyl phosphonic acid, vinylphosphonate/salt/
Acid, the phosphate of phosphonate ester/salt/acid or polyethylene glycol monomethacrylate based on methacrylic acid) ester.With this
The copolymerization of a little monomers reduces coagulation and improves the mobility of latex in painting color.
In addition, it has now been found that by these sulfonic acid either phosphonic acids or ester monomer and other acid functional group
(functionality) for example those of following to be mixed into together, surprisingly and unexpectedly improve coating performance example
Such as dry resistance to picking.
Other optional ionic comonomers include selected from those of following：α, β-olefinic unsaturation C3-C8Monocarboxylic acid, α, β-
Olefinic unsaturation C4-C8Dicarboxylic acids and its acid anhydrides, α, β-olefinic unsaturation C4-C8The C of dicarboxylic acids4-C8Alkyl half-esters and acrylic acid
And methacrylic acid and maleic acid, maleic anhydride, the C of fumaric acid and itaconic acid4-C8Alkyl half-esters.Acrylic acid is particularly preferred
Optional ionic comonomer.
If using the ionic comonomer of aforementioned type being optionally present, it is added with low-down amount, example
Such as the amount of 0.1pphm-5.0pphm.More preferably if used, the optional ionic comonomer will account for the big of monomer mixture
About 0.2pphm- about 2.0pphm, or about 0.2- about 1.0pphm.
It is optionally possible to prepare the interpretation for paper coating composition here, also used in interpretation non-
Siliceous comonomer.Such non-siliceous comonomer for example can be any undersaturated, polyfunctional copolymerzation with cross-linking list
Body provides improved strength of coating performance when it to be mixed into interpretation in right amount for interpretation.
The suitable non-siliceous multifunctional comonomer of unsaturation may include such as unsaturated compound, and it includes one
Or multiple carbonyl moieties.Such preferred comonomer includes having those of two or more carbonyl moieties.This
The example of the suitable comonomer of sample includes diacetone acrylamide (DiAAA), polymerizable 1,3- dicarbonyl compounds and
Polymerizable 1,3-, bis- keto-amides.
Suitable polymerizable 1,3- dicarbonyl compounds include acrylic acid acetoacetoxyethyl, methacrylic acid second
Acyl acetoxyethyl (AEEM), acetoacetoxyethyl propyl ester, acetoacetoxyethyl butyl ester, first
(acetoacetoxy groups) propyl ester of base acrylic acid -2,3- bis- and allyl acetoacetate base ester.
Suitable polymerizable 1,3-, bis- keto-amides include description compound those of in United States Patent (USP) No.5889098,
The patent is hereby incorporated by reference.The example of such compound includes acylamino- pendant acetoacetonate moieties such as acylamino-
Acetopyruvic acid -3- isopropenyls-alpha, alpha-dimethylbenzyl ester, acylamino- acetopyruvic acid -4- isopropenyl-α, alpha-alpha-dimethyl
Benzyl ester, acylamino- acetopyruvic acid -4- acetenyls-phenylester etc..
The undersaturated multifunctional comonomer containing carbonyl of preferred aforementioned type includes diacetone acrylamide
(DiAAA), acetoacetoxyethyl methacrylate (AEEM), acetoacetoxyethyl propyl ester, metering system
Sour acetoacetoxy groups butyl ester, methacrylic acid 2, (acetoacetoxy groups) propyl ester of 3- bis- and allyl acetoacetate base ester.Dipropyl
Ketone acrylamide and acetoacetoxyethyl methacrylate are most preferred.
Amount of the typical undersaturated carbonyl functional comonomer of these types in polyblend can be
About 0.1-4.0pphm.The amount of more preferably such comonomer will be about 0.5-3.5pphm.
In some cases, when using such carbonyl functional comonomer, in order to realize interpolymer molecule amount, branched
And/or the desired change of flowing property, further include preferably one or more water in the emulsion polymerization reaction mixture
The external crosslinker of dissolubility.The water-soluble external crosslinker that can be used by this method is those, by with non-siliceous, insatiable hunger
The carbonyl functional group of the multifunctional comonomer (it has been aggregated in interpretation main chain) of sum reacts.
A kind of water-soluble cross-linker of preferred type (it optionally can be used in paper coating composition here) includes
Such compound, it includes at least two hydrazine parts.2-10 are particularly suitable to, the aliphatic of special 4-6 carbon atom
Two hydrazine compounds of dicarboxylic acids, such as careless acid dihydrazide, acid dihydrazide, amber acid dihydrazide, glutaric, oneself two
Acid dihydrazide, sebacic dihydrazide, Malaysia acid dihydrazide, two hydrazides of two hydrazides of fumaric acid and/or itaconic acid.2-4 carbon atom
Two hydrazine of water-soluble aliphatic such as bis- hydrazine of ethylene -1,2-, bis- hydrazine of propylene -1,3- or butene-1, bis- hydrazines of 4- are also suitable.
Adipic dihydrazide (ADH) is for the most preferred water-soluble cross-linker in composition here.
The water-soluble cross-linker exists usually in emulsion polymerization reaction mixture with such amount, makes in blend
Middle crosslinking agent diazanyl group and the molar ratio of comonomer carbonyl are about 0.1- about 2.0.Crosslinking agent in the more preferable blend
Diazanyl group and the molar ratio of copolymer carbonyl will be about 0.5-1.5.In order to provide such ratio, two hydrazine is water-soluble cross-linked
Agent can exist in the polyblend with about 0.1-3.0pphm, the amount of more preferably from about 0.2-2.0pphm.
In the interpretation of the adhesive latex lotion of the aforementioned comonomer based on unsaturated carboxylic acid generally also herein with
Specific selected amount exists, the amount be used to assign for the paper coating composition containing such lotion it is desirable that bonding
Agent intensity.Specifically, such comonomer based on unsaturated carboxylic acid usually will be in the interpretation with about
The amount of 0.1pphm-1.0pphm exists.The dosage of more preferably such comonomer based on carboxylic acid will be 0.2pphm-
0.5pphm。
(it may be used as the composition comonomer of interpretation here (that is, crosslinking to a further type of comonomer
One of agent)) comprising selected from following polyene category unsaturated comonomer：Cyanuric acid alkatriene propyl diester, isocyanuric acid triallyl
Ester, maleic acid diallyl ester, fumaric acid diallyl ester, divinylbenzene and diallyl phthalate.Preferably
Such comonomer includes maleic acid diallyl ester, fumaric acid diallyl ester and diallyl phthalate
Ester.Such polyene category unsaturated comonomer will be with the amount of about 0.05pphm-0.5pphm usually in the interpretation
In the presence of.The dosage that more preferably such polyene belongs to unsaturated (one or more) comonomer/(one or more) crosslinking agent will
It is about 0.1pphm-0.3pphm.
It is as shown, the interpretation for being used to form the adhesive latex lotion of paper coating composition here be by will under
The component in face is copolymerized to manufacture：Vinyl esters and ethylene, unsaturated silane comonomer, one or more emulsion stabilizations
(it includes one or more undersaturated substituted sulfonic acid, one of unsaturated phosphonic acids and/or those acid for ionic comonomer
Ester), and there are stabilization systems, it includes one or more anion and/or nonionic surface active agent, but small
In any protective colloid material of about 1pphm.It is preferred that the comonomer of these types of type in interpretation with relative to that
This such amount exists, and is used to assign such IGT for the paper coating composition and kills gross value (as defined below), should
Value is bigger than the paper coated with conventional coating compositions by least about 5%, and the conventional coating compositions are to use styrene-fourth two
What alkene adhesive was prepared, or even those are used without above-mentioned unsaturated silane comonomer and one or more lotions
The VAE latex adhesives for stabilizing the combination of ionic comonomer are prepared.Even more preferably, the comonomer is selected
Relative quantity in interpretation, so that the paper coating composition containing the interpretation base latex lotion shows to kill gross value ratio
Those more conventional formulations are big by least about 10%, or even big by about 15%.
Including the interpretation of basic comonomer described above can be prepared using conventional emulsion polymerization flow, lead
The preparation of the adhesive latex lotion for paper coating composition is caused.Such flow is generally described in such as United States Patent (USP)
In No.5849389, the disclosure of which is incorporated by reference herein in its entirety.
In typical polymerization process, the vinyl esters, ethylene and other comonomers can be in water-bearing medias, not
Under pressure more than 100 atmospheric pressure, it polymerize in the presence of catalyst and at least one emulsifier.The aqueous system can pass through conjunction
It is 2-6 that suitable buffer, which is maintained at pH, and is incrementally added or is continuously added to catalyst.More specifically, vinyl acetate and
Other comonomers of 50%-75% can suspend in water, and in the presence of ethylene, thoroughly be stirred under operating pressure, come
So that under the conditions of existing in the reaction region, the solution of ethylene proceeds to the essence limit until its solubility in the mixture
Degree.Then the vinyl acetate and other comonomers can be progressively heated at polymerization temperature.
The homogenizing phase is the polymerization phase often after, and during this period, by catalyst, (it preferably comprises major catalyst or initiation
Agent, and may include activator) be incrementally added or be continuously added to together with remaining comonomer.Monomer used can conduct
Pure monomer or as premix lotion be added.
Suitable polymerization catalyst includes commonly used in the water-soluble free radical precursor in emulsion polymerization, such as peroxidating
Hydrogen, sodium peroxydisulfate, potassium peroxydisulfate and ammonium persulfate and tert-butyl hydroperoxide, amount be 0.01wt%-3wt%, it is excellent
0.01wt%-1wt% is selected, the total amount based on lotion.They can connect with reducing agent such as formaldehyde sodium sulfoxylate, ferrous salt
Sodium sulfite, sodium hydrogensulfite, sodium sulfite, sodium thiosulfate are used together as oxidation reduction catalyst, and amount is
0.01wt%-3wt%, preferably 0.01wt%-1wt%, the total amount based on lotion.The free based precursor can be added to emulsifier
In aqueous solution or divided dose it can be added in the course of the polymerization process.
The mode for combining the polymeric composition can be carried out by different known monomer feed method, such as continuously
Monomer addition, the monomer addition of increment or the monomer of whole amount add in primary charging.Before introducing monomer, all
The water-bearing media and polymeric additive of amount can reside in aggregation container, either alternatively the water-bearing media or its one
Part can continuously or incrementally be added in the course of the polymerization process.
The emulsion polymerization for being used to prepare the interpretation of aqueous latex form carries out in the presence of stabilising system, described steady
System bag deposit is determined containing one or more certain types of anion and/or nonionic surface active agent as emulsifier.This
The emulsifier of sample is conventional and well known.(it can be used as emulsifier for here to suitable nonionic surface active agent
Coating composition emulsion stabilization system in) include polyethylene oxide condensate.Such various nonionics
Type surfactant is disclosed in United States Patent (USP) No.5849389 mentioned above.Suitable anionic surfactant (its
Can be as emulsifier in the emulsion stabilization system of coating composition here) include alkyl aryl sulfonate/salt/
Acid, alkali metal alkyl sulfate, the Arrcostab and fatty acid soaps of sulfonic acid esterification.Such various anionic tables
Face activating agent is equally disclosed in United States Patent (USP) No.5849389 mentioned above.
Routinely, as the replacement of surfactant emulsifiers or supplement, different protective colloids has been used for
Stablize the vinyl esters/Ethylene emulsion polymerization object latex composition of the type described above.It has, however, been found that in order to realize especially
Useful compatibility and processing benefit, coating composition of the invention should keep there is no such protective colloid such as
Polyvinyl alcohol (PVOH), hydroxyethyl cellulose, styrene acrylic or styrene maleic acid colloid.
Although some very small amount of protective colloid materials are sustainable, and are actually used in and process this
In coating composition used adhesive agent emulsion component, but the adhesive agent emulsion should include no more than about here
1.0pphm and the protective colloid material for being preferably no greater than about 0.5pphm.Equally, emulsion polymerization can be there is no in this way
Protective colloid material in the case of carry out.Using surfactant base stabilization systems and contain the guarantor no more than this tittle
The adhesive agent emulsion of shield property gelatification material is considered as " there is no " protective colloid material for the present invention.Make
Still it is characterized as those of " substantially full surfactant base " lotion herein with the latex emulsion of such stabilization systems.
It after polymerisation, can be by the way that water be added or as distilling aqueous polymer emulsions bonding of the water removal by obtained by
The solid content of agent is adjusted to desired level.In general, the desired level of polymer solids level be about 40wt%- about
70wt% is based on lotion total weight, more preferably from about 50wt%- about 60wt%.
If desired, then conventional additive can be incorporated into used herein of in paper coating composition, to change its property
Energy.May include filler, thickener, catalyst, dispersant, colorant, biocide, antifoaming agent in these additives
Deng.Although as described above, advantageously during emulsion polymerisation process limit or even avoid use protective colloid,
Being suitably can be using similar substance as in the adhesive composition for helping adhesive to polymerize after being added to.It is such to help bonding
Agent substance such as polyvinyl alcohol can be to be added after at least about amount of 1wt% of the paper coating composition.
The coating composition load of the preferred present invention has filler to generate such composition, and it includes about 5- about
The interpretation of 50wt%, preferably approximately 5- about 20wt%, and about 50- about 90wt% filler, based on the composition
Total weight.
Before the drying, here the common total solid content of paper coating composition can be about 50wt%-95wt%.More
It is preferred that before the drying, coating composition here is by the total solid content with about 80wt%-90wt%.
The granularity of the latex can be regulated and controled by quantifying nonionic used or anionic emulsifier.In order to obtain
Smaller granularity is obtained, a greater amount of emulsifiers is used.As usual rule, emulsifier is bigger, and average particle size is smaller.
Here actual paper coating composition includes interpretation latex and pigment such as clay and/or calcium carbonate, and this
Common paper well known to field technology personnel coats additive, may include that other help adhesive such as polyvinyl alcohol, albumen
Matter such as casein or soybean protein or starch.Here the coating composition also by comprising enough alkali by the coating group
The pH for closing object is maintained at 6-10, more preferable 7-9.
Here pigment used in the paper coating composition can be the conventional use of any type of those.Frequently,
The some or all pigment includes clay, and includes any clay coated commonly used in paper for this part,
Include the aluminium hydrosilicate of kaolin group's clay, aqueous silicon dioxide clay, and in " Kaolin Clays and their
The certain kinds recommended in Industrial Uses ", J.M.Huber Corp. (1949), New York, N.Y. 10-16 chapters
The clay of type.
Other than clay itself, or as the complete replacement of clay, other paper pigments such as carbonic acid can also be used
Calcium, titanium dioxide, barium white, lithopone, zinc sulphide or other coating pigments, including plastics such as polystyrene.When with clay
When being used together, which can exist in different ratios, such as high to 50%, preferably high to 35%, be based on clay
Weight.Alternatively, it is the calcium carbonate more than 50% which, which can include relative to clay, is even even with respect to clay
Clay may be not present in calcium carbonate more than 75%, or even 100% calcium carbonate.In addition, the composition can also include it
His additive such as zinc oxide and/or a small amount of dispersant or stabilizer such as tetrasodium pyrophosphate.
In general, the paper coating composition can include 100 parts of pigment, such as pigment here, it includes 65-100 parts of carbonic acid
Calcium and 0-35 parts of secondary pigments；0.01-0.5 parts of dispersants or stabilizer；3-30 parts of interpretation latex (being based on solid)；0-25 parts
Help adhesive；0.02 part of optional antifoaming agent；Desired solid level is provided with enough water.Typically contain about
The coating composition of 40wt%-70wt% solids.It is in this field skill using the variation and preparation of the painting color of these substances
In the knowledge of art personnel.
Here the paper coating composition can be applied on different plane fibers cellulosic substrates, including paper is for example not
Woody paper and grind timber grade；Hardboard；Label；For newspaper, advertisement, poster, books or magazine
Paper product；With construction substrate such as wallpaper, wallboard or ceiling tiles.In one embodiment, the paper coating composition
It can be used for coating the paper for being intended for use in rotogravure printing.
The amount for being administered to the paper coating composition on plane fibers cellulosic substrates is typically about 1g/m2About
30g/m2, and preferably about 3g/m2About 25g/m2, or about 10g/m2About 20g/m2.The paper coating composition can
It is applied with application in a single step or using two or more steps, to establish final coating weight.In addition, the paper
Coating composition can also be simultaneously or as individual coating step, to be administered to the second side of base material.
The paper coating composition can be administered to by technology those of known in this field on base material.Such as the paper coating group
The size press of roller applicator such as metering can be used by closing object；For example short dwell time applicator of knife coating machine；Air knife coaters；
Slit die coating machine for example sprays applicator；Or brush applies.Preferred painting method for high-speed application includes
Use knife coating machine or the size press of metering.
In one embodiment, the invention further relates to a kind of methods forming coating paper product comprising (a) is with above-mentioned
Coating composition plane fibers cellulosic substrates, to form the base material that wet coating is covered；(b) base material that the dry wet coating is covered comes
Form the base material of dry coating；(c) roll the base material of the coating of the drying to form the paper product of coating.
(it includes the specifically adhesive latex breasts based on vinyl esters described here for the paper coating composition of the present invention
Liquid) when being applied on the paper base material of the above-mentioned type as coating, provide improved adhesive strength.This improved adhesiveness
It is able to can be referred to as killing by referred to as the parameter for killing mao intensity quantifying, and in particular by what is defined in detail below
The parameter of gross value quantifies.
Hair loss is defined as coating, film or fiber and is raised from base paper surface in printing process.When print wheel and paper
Sample contacts come when depositing ink, then when the print wheel with ink is removed from paper surface, subsequent negative force is applied to
On the paper.Mao intensity of killing of coated paper is measured with such method, group become in print test machine with acceleration
Rate printing coating paper slip.The viscosity grade of the accelerating velocity and ink that adjust print wheel determines the coated paper sample in specific print
The intensity of swipe part.If the combination for printing wheel speed and ink viscosity is significantly enough, it is formed by negative force generation
Hair loss, can show as：White space on print wheel and coated paper sample surfaces, as coating paper sample surfaces on
It is bubbled and textured ones, the layering (superficial layer removing) or the tearing of base paper sample of such as pattern product of coating is (complete strong
Degree failure).
The hair loss effect that the paper base material that the selected paper coating composition with any given type coats is shown
Evaluation can be used for quantifying the adhesive strength and paintability of the composition.Hair loss evaluation is tested by IGT hair loss, according to
The standards method of measurement of paper pulp well known in the art and paper industry technological associations (TAPPI) carries out.Dry and wet bonding is strong
One measurement of degree be by according to TAPPI Useful Method UM 591, Surface Strength of Paper's
IGT hair loss tests to provide.IGT, which kills mao ionization meter, to be printed using ink roller described in UM591 and standard conditions
When brush, paper and coating is risen into required speed from paper base material surface, unit is cm/s.Higher IGT kills gross value and illustrates
The base material of coating preferably resistance to hair loss and therefore higher intensity paintability.
The binder levels in Inventive Formulations are typically chosen to simulate commercial coating formula.Using wire rod come by
The coated substrate of bleaching is to 12lbs/3000ft2(19.5g/m2) Target coat weight value.This coating weight is selected to simulate
Bleached board market.By the plate of the fresh coating, stove is 30 seconds dry at about 260 ℉ (127 DEG C), then at 600psi (4.14MPa)
Roll-in is nibbled with 170 ℉ (77 DEG C) using 1 to prolong.Before testing IGT resistance to picking, make the plate of the completion in constant temperature and constant humidity item
It is placed 24 hours under part (72 ℉ (22 DEG C), 50%RH).
As employed herein, it is such value to kill gross value, is obtained from and is tested using IGT test system AIC2-5 printings
Machine, including using medium-viscosity oily, above-mentioned coated board under conditions of 2cm/s and 50KgF kills full scale examination.Institute as above
It states, paper coating composition of the invention is shown when using the adhesive agent emulsion of the present invention according at least big of above-mentioned test
About 75, more preferably at least about 90 and even more desirably at least about 100 kill gross value.In general, the paper coating group of the present invention
That closes that object shows about 90-110 kills gross value.
The ink wetability of testing coating is a key property for printing grade paper by ink.One kind by ink is logical
Normal industrial test is K＆N Ink Brightness, is described in TAPPI test method RC19.The group of K＆N ink test
Become：Oil-soluble dyes in varnish base oil ink are excessively applied on the area of 1-2 square inches of test paper.It should be by ink
Property be by when the K＆N ink short time applies and removes, surface brightness declines percentage to measure.It is got over by ink numerical value
Small, the imporosity of coating is bigger, and therefore lower into the degree of the ink of coating.Low numerical value represents higher by ink
Property.
Embodiment
Using description in the comparative example 1 and embodiment 1-4 of United States Patent (USP) No.5576384 (being hereby incorporated by reference)
General polymerization technology, to be prepared for many adhesive agent emulsions for being based on vinyl acetate/ethylene (VAE) interpretation.It is manufactured
Lotion in interpretation contain the other comonomer of relatively small amount comprising some ionics breast used in the present invention
Liquid stabilizes comonomer and unsaturated silane comonomer.By the different amounts of anion of the adhesive agent emulsion manufactured by whole
And/or nonionic emulsifier is emulsified.Some manufactured adhesive agent emulsions further comprise different amounts of protective colloid, base
In polyvinyl alcohol (PVOH), hydroxyethyl cellulose, styrene acrylic or styrene maleic acid colloid.
The each component of manufactured different adhesive agent emulsions describes in table 1.
Table 1
Adhesive agent emulsion
In table 1, following name is used：
VA is vinyl acetate, and E is ethylene.
VAE indicates vinyl acetate/ethylene adhesive agent emulsion.
VTMO silane is vinyltrimethoxysilane.
SVS is sodium vinyl sulfonate, and AA is acrylic acid.
PVOH is polyvinyl alcohol, and HEC is hydroxyethyl cellulose.
SBR is SBR styrene butadiene rubbers.
Digital value is part/hundred part, is based on total VA and E comonomers.
Kill gross value measurement
The adhesive latex lotion of embodiment 6 is formulated into pre-coating composition described in the following table 2, and with containing commercially available
SBR is compared as the conventional pre-coating composition of binder polymer.
Table 2
Precoat formulation
* C60 represents Hydrocarb 60, calcium carbonate
By the pre-coating composition of table 2 with 22g/m2Level be coated on paper base material, roll, be dried in an oven, and use
Conventional face coating combination (containing SBR, as shown in table 3 below to prepare) is with 22g/m2Horizontal plane apply.
Table 3
The faces SBR apply formulation
* C98 represents Hydrocarb 98, calcium carbonate
The paper of the coating is rolled again, be dried in an oven and tests the dry resistance to picking of IGT and other relevant parameters.Knot
Fruit is shown in the following table 4.
Table 4
| Parameter | Conventional SBR precoated shets | 6 precoated shet of embodiment |
| IGT kills hair (cm/s) | 89 | 123 |
| K＆N ink rise rates (%) | 20.8 | 21.4 |
| Sheet gloss (%) | 63.5 | 64 |
| Brightness (%) | 83.5 | 83.5 |
Test result in table 4 shows the painting with the pre-coating composition prepared with the latex adhesive interpretation of the present invention
Cover paper and provide such paper and coating, have especially it is desirable that IGT kill a mao performance.
It is as described below to have prepared three kinds of paper coating compositions：
60 (the CaCO of Hydrocarb of 70 dry parts3)
The Ultrawhite 90 (clay) of 30 dry parts
The Finnfix 10G (CMC) of 0.1 dry part
The Dispex N 40 (dispersant) of 0.1 dry part
The latex (adhesive) of 17 dry parts.
The total solid content target of the coating composition is 64%, and has used three kinds of different adhesives：It is commercially available
The latex adhesive (table 1) of SBR, the latex adhesive of embodiment 5 and embodiment 6.With ammonium hydroxide by the coating composition tune
The whole pH that arrives is 8.0-9.0.With 19.5g/m2Coat weight resulting composition is coated on SBS plates, roll and dry, such as
It is upper described.Fig. 1 shows the dry resistance to picking of comparative IGT between three kinds of coated boards.The test result is shown in the following table 5.
Table 5
| Sample | IGT dry coating intensity | Brightness | Whiteness b values | Glossiness |
| SBR adhesives | 409 | 85.7 | 92.31.5 | 35.4 |
| The latex of embodiment 6 | 364 | 86.6 | 92.61.2 | 36.4 |
| The latex of embodiment 5 | 305 | 87.2 | 92.91.4 | 33.7 |
The data from table as it can be seen that the latex adhesive of embodiment 6 to provide thundering and unexpected high IGT dry
Strength of coating, or even be also such compared with Example 5.With the coating composition of the latex adhesive containing embodiment 6
Plate IGT dry coatings intensity it is bigger than the intensity of the latex adhesive containing embodiment 5 more than 15%, actually close to big
20%.
Although describe and illustrating the present invention by reference to specific embodiment, those skilled in the art will manage
Solution the present invention itself can be changed, need not here it is shown that.For this reason, therefore in order to determine the true model of the present invention
It encloses, only should refer to appended claims.
Claims (21)
1. a kind of paper product, it includes：
Plane fibers cellulosic substrates；With
Coating composition on the surface of the base material, it includes interpretation, which is by below emulsion polymerization
Component prepare：
I) one or more vinyl ester monomers；
Ii) ethylene；
Iii) unsaturated silane comonomer；With
Iv) one or more emulsion stabilization ionic comonomers, it includes one or more：(a) undersaturated substituted
The organic sulfonic acid either undersaturated organic phospho acid of its salt (b) or its salt, (c) undersaturated substituted organic sulfonic acid ester/salt/
Sour either sulfuric ester/salt/acid or (d) undersaturated Organophosphonate/salt/acid or phosphate/salt/acid；
The emulsion polymerization is carried out in the presence of component below：
V) stabilization systems, it includes one or more anion and/or nonionic surface active agent, but are less than 1pphm
Any protective colloid material；With
Vi) water,
The wherein described interpretation is by water-bearing media, under the pressure no more than 100 atmospheric pressure, in catalyst and at least one
It polymerize the vinyl esters, ethylene and other comonomers in the presence of kind anion and/or nonionic surface active agent to prepare,
It is middle by monomer i)-iv) and water vi) in the presence of stabilization systems v) be progressively heated at polymerization temperature.
2. paper product according to claim 1, the wherein interpretation include one or more lotions of 0.1pphm-5pphm
Stabilize ionic comonomer.
3. paper product according to claim 1, wherein one or more emulsion stabilization ionic comonomers are selected from propylene
Acylaminomethyl propane sulfonic acid, styrene sulfonate and sodium vinyl sulfonate.
4. paper product according to claim 1, wherein one or more emulsion stabilization ionic comonomers are selected from ethylene
Base phosphonic acids, vinylphosphonate/salt, phosphonate ester/salt/acid based on methacrylic acid, polyethylene glycol monomethacrylate
Phosphate and (methyl) acrylated phosphate/salt/acid.
5. paper product according to claim 1, wherein the emulsion stabilization ionic comonomer further include a kind of or more
The acrylic acid of kind, the C of methacrylic acid and maleic acid4-C8The C of alkyl half-esters, maleic anhydride4-C8Alkyl half-esters, fumaric acid
C4-C8The C of alkyl half-esters and itaconic acid4-C8Alkyl half-esters.
6. paper product according to claim 1 further includes the acrylic comonomers of 2pphm.
7. the unsaturated silane that paper product according to claim 1, the wherein interpretation include 0.1pphm-3pphm is copolymerized
Monomer.
8. paper product according to claim 1, the wherein vinyl ester monomers are vinyl acetate and unsaturated silane copolymerization
Monomer is vinyl trialkyl oxysilane.
9. paper product according to claim 8, wherein the unsaturated silane comonomer are selected from vinyltrimethoxysilane, second
Alkenyl triethoxysilane, ω-methacryloxypropyl-trimethoxy silane, vinyl three (2- methoxy ethoxies) silicon
Alkane, vinyl silane triisopropoxide, three isopropoxy silane of vinyl propyl, three isobutoxy silane of vinyl propyl, second
Three isobutoxy silane of alkenyl, three tert-butoxy silane of vinyl amyl, vinyl propyl-methyl diamyl oxysilane and ethylene
Three sec-butoxy silane of base propyl.
10. paper product according to claim 1, the wherein stabilization systems include polyethylene oxide condensate.
11. paper product according to claim 1, the wherein stabilization systems include to be selected from following anionic surface activity
Agent：The Arrcostab and fatty acid soaps that alkyl aryl sulfonate/salt/acid, alkali metal alkyl sulfate, sulfonic acid are esterified.
12. paper product according to claim 1, wherein the interpretation component be by emulsion polymerization below component prepare
's：
I) vinyl ester monomers of 67-99pphm；
Ii) the ethylene of 1.0-30.0pphm；
Iii) the unsaturated silane comonomer of 0.1-3.0pphm；With
(iv) at least one of the undersaturated substituted sulfonic acid of 0.1-1pphm, unsaturated phosphonic acids or its ester or salt.
13. paper product according to claim 1, the wherein coating composition further include under being selected from of 50wt%-90wt%
The filler in face：Calcium carbonate, clay, titanium dioxide, barium white, lithopone, zinc sulphide, polystyrene and combinations thereof.
14. paper product according to claim 13, the wherein coating composition include to be more than the calcium carbonate of 50wt% as filler.
15. paper product according to claim 1, wherein before the drying, the total solids content of the coating composition is 50wt%-
95wt%.
16. paper product according to claim 1, the wherein emulsion polymerization include to be selected from following protectiveness less than 0.5pphm
Colloidal materials：Polyvinyl alcohol, hydroxyethyl cellulose, styrene acrylic, styrene maleic acid and carboxymethyl cellulose.
17. paper product according to claim 15, it includes the interpretations of 5wt%-20wt%.
18. paper product according to claim 1 further includes the top coat composition on the coating composition.
19. paper product according to claim 18, the wherein coating composition are provided with such amount, that is, the amount is effective
Top coat composition is adhered on the fibrous fabric element base material by ground, and with containing SBR adhesives or VAE binder and
Coating composition without the comonomer is compared, and it is big by least 5% that IGT kills mao intensity.
20. paper product according to claim 1 is further comprised as and is added to after helping adhesive in the composition extremely
The polyvinyl alcohol of few 1wt%.
21. a kind of method for the paper product forming coating comprising：
(a) coating composition plane fibers cellulosic substrates, to form the base material that wet coating is covered, the wherein Coating material composition are used
Object includes the interpretation by will be prepared by following component emulsion polymerization：
I) one or more vinyl ester monomers；
Ii) ethylene；
Iii) unsaturated silane comonomer；With
Iv) one or more emulsion stabilization ionic comonomers, it includes at least undersaturated substituted organic sulfonic acid or
Person its salt, undersaturated organic phospho acid either its salt, undersaturated substituted organic sulfonic acid ester/salt/acid or sulfuric ester/salt/
Sour or undersaturated Organophosphonate/salt/acid or phosphate/salt/acid；
The emulsion polymerization is carried out in the presence of component below：
Vi) stabilization systems, it includes one or more anion and/or nonionic surface active agent, but are less than 1pphm
Any protective colloid material；With
Vii) water,
Wherein by monomer i)-iv) and water vii) in stabilization systems vi) in the presence of be progressively heated at polymerization temperature；
(b) base material that the wet coating is covered is dried to form the base material of dry coating；With
(c) roll the base material of the coating of the drying to form the paper product of coating.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2012/081200 WO2014036740A1 (en) | 2012-09-10 | 2012-09-10 | Functionalized vinyl acetate ethylene binders for paper and paperboard coatings |
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| CN104411488B true CN104411488B (en) | 2018-08-17 |
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| CN201280074550.7A Active CN104411488B (en) | 2012-09-10 | 2012-09-10 | The functionalized vinyl acetate-ethylene adhesive coated for paper and hardboard |
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| Country | Link |
|---|---|
| US (1) | US20160115649A1 (en) |
| EP (1) | EP2892718A4 (en) |
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| EP3122791B1 (en) | 2014-03-27 | 2018-05-02 | Wacker Chemical Corporation | Binder for paper coating compositions |
| CN106164372B (en) * | 2014-03-27 | 2018-07-27 | 瓦克化学股份公司 | Aqueous acetic acid vinyl acetate ethylene copolymer dispersion for paper coating |
| CN106460342A (en) * | 2014-04-11 | 2017-02-22 | 巴斯夫欧洲公司 | Aqueous polymer dispersion for paper with a copolymer of vinyl acetate and an acrylate monomer |
| SE543736C2 (en) * | 2019-11-04 | 2021-07-06 | Stora Enso Oyj | Coating for reducing oil absorbency of cellulosic webs |
| EP4271720A1 (en) * | 2020-12-30 | 2023-11-08 | Wacker Chemie AG | An aqueous polymer dispersion |
| EP4229142A1 (en) | 2020-12-30 | 2023-08-23 | Wacker Chemie AG | An aqueous polymer dispersion |
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| US8080292B2 (en) * | 2008-10-15 | 2011-12-20 | Hewlett-Packard Development Company, L.P. | Coated paper for pigment-based inkjet printers |
| DE102009008143A1 (en) * | 2009-02-09 | 2010-08-19 | Celanese Emulsions Gmbh | Vinyl acetate-ethylene copolymer dispersions and textile fabrics treated therewith |
| WO2011139267A1 (en) * | 2010-05-03 | 2011-11-10 | Celanese International Corporation | Carpets with surfactant-stabilized emulsion polymer carpet binders for improved processability |
| US20120021237A1 (en) * | 2010-07-20 | 2012-01-26 | Celanese International Corporation | Vinyl ester/ethylene-based binders for paper and paperboard coatings |
-
2012
- 2012-09-10 WO PCT/CN2012/081200 patent/WO2014036740A1/en active Application Filing
- 2012-09-10 EP EP12884053.5A patent/EP2892718A4/en not_active Withdrawn
- 2012-09-10 CN CN201280074550.7A patent/CN104411488B/en active Active
- 2012-09-10 US US14/406,893 patent/US20160115649A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| EP2892718A4 (en) | 2016-06-08 |
| WO2014036740A1 (en) | 2014-03-13 |
| EP2892718A1 (en) | 2015-07-15 |
| US20160115649A1 (en) | 2016-04-28 |
| CN104411488A (en) | 2015-03-11 |
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