CN103890266A - Paper coating compositions comprising a polymer dispersion from room temperature liquid and gaseous monomers - Google Patents
Paper coating compositions comprising a polymer dispersion from room temperature liquid and gaseous monomers Download PDFInfo
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- CN103890266A CN103890266A CN201280052663.7A CN201280052663A CN103890266A CN 103890266 A CN103890266 A CN 103890266A CN 201280052663 A CN201280052663 A CN 201280052663A CN 103890266 A CN103890266 A CN 103890266A
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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
- D21H19/36—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
- D21H19/36—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
- D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
-
- 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
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/08—Copolymers of ethene
- C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09D123/0853—Vinylacetate
-
- 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
- C09D125/00—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 aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/10—Copolymers of styrene with conjugated dienes
-
- 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
- C09D125/00—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 aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/08—Copolymers of styrene
- C09D125/12—Copolymers of styrene with unsaturated nitriles
-
- 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
- D21H21/50—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 form
- D21H21/52—Additives of definite length or shape
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/54—Aqueous solutions or dispersions
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/254—Polymeric or resinous material
Abstract
Paper coating compositions comprise inorganic pigments and an aqueous polymeric dispersion comprising dispersed polymeric particles. The polymers are obtainable by polymerization of a first monomer that is liquid at room temperature, has a boiling point of at least 50 DEG C and a glass transition temperature of at least 20 DEG C as homopolymer, and a second monomer that is gaseous at room temperature, has a boiling point of below 0 DEG C and a glass transition temperature of below -30 DEG C as homopolymer. The dispersed polymeric particles have an average size of below 150 nm and a glass transition temperature in the range from -10 to +30 DEG C.
Description
The present invention relates to paper coating compositions, the aqueous polymer dispersion that described composition comprises inorganic pigment and comprises dispersed polymeres particle.Polymer can obtain by some room temperature liquid monomer and some room temperature air monomer polymerization.The polymer beads disperseing has the glass transition temperature of particle mean size below 150nm and-10 ℃ to+30 ℃.
Outside dewatering, paper coating compositions for example comprises pigment, adhesive and assistant, conventionally to set up essential rheological property, thickener.Paper coating compositions is given the required machinery of body paper and visual performance.Adhesive is intended to pigment is fixed on paper and guarantees the cohesive force in gained coating.Therefore it is desirable, having the very adhesive of high adhesion.And the polymer adhesive that exists some to there is high adhesion, but they tend to jaundice, and this is undesirable in many application of paper.Existence has other polymer adhesive of high adhesion and/or high resistance jaundice property, but due to the component for the preparation of them, they have unjoyful smell.So far for the adhesive of paper coating agent aspect all ideal performances, be still undesirable.
The object of this invention is to provide the paper coating compositions with very high anti-jaundice in conjunction with very high bonding force.
The invention provides paper coating compositions, described composition comprises:
(i) inorganic pigment, and
(ii) aqueous polymer dispersion that comprises dispersed polymeres particle, wherein polymer obtains by following monomer polymerization:
(a) at least one first monomer, it is lower in room temperature (20 ℃) is liquid, has the boiling point of at least 50 ℃ and the glass transition temperature of at least 20 ℃ as homopolymers, and
(b) at least one second monomer, it is lower in room temperature (20 ℃) is gas, has 0 ℃ of following boiling point and the glass transition temperatures below-30 ℃ as homopolymers,
The polymer beads wherein disperseing has the glass transition temperature of particle mean size below 150nm and-10 ℃ to+30 ℃.
The present invention also provides the method for coated paper or cardboard, and described method comprises:
-paper coating compositions of the present invention is provided; With
-paper coating compositions is applied at least one surface of paper or cardboard.
The present invention also provides the paper or the cardboard that apply with paper coating compositions of the present invention.
The polymer beads disperseing has according to the present invention below 150nm, the preferably particle mean size below 80nm to 150nm.The average diameter of polymer beads can be measured by fluid dynamic force chromatography (HDC).In HDC, by colloidal state sample wash-out from the granularity exclusion fractionating column of classifying according to hydrodynamic radius.Eluent comprises salt, non-ionic surface active agent and anion surfactant.PS calibration latex calibration for elution time.Measurement category extends to 1200nm-larger component from 15nm and is filtered off and does not detect.Can measure the accuracy of diameter and weight fraction to 3%.Use UV absorption under 254nm and by mark weighting.
In polymerization, 100 weight portion total monomers used comprise for example 4.8-95 weight portion, preferably 9.8-75 weight portion, especially at least one group of 14.8-60 weight portion (a) monomer and 4.8-95 weight portion, preferably 24.8-90 weight portion, especially at least one group of 39.8-85 weight portion (b) monomer.
The first monomer (a) is preferably selected from vinyl aromatic compounds and vinyl acetate.The example of vinyl aromatic compounds is styrene, α-methyl styrene and vinyltoluene.Styrene, methyl styrene and composition thereof are preferred.Particularly preferably use styrene.Vinyl acetate is the example of suitable vinyl acetate.
That the second monomer (b) is preferably selected from is single-or polyenoid belong to unsaturated C
2-C
4hydrocarbon, for example 1,3-butadiene, isoprene and ethene.In this group monomer, preferably use 1,3-butadiene or ethene.
In a preferred embodiment of the present invention, at least one first monomer (a) is selected from styrene and vinyl acetate, and at least one second monomer (b) is selected from 1,3-butadiene and ethene.Preferably, polymer is selected from least 60 % by weight, the polymer that preferably at least 80 % by weight degree are formed by ethene and vinyl acetate, and at least 60 % by weight, the polymer that preferably at least 80 % by weight degree are formed by styrene and butadiene, and composition thereof.
Useful other monomer of preparing polymer optionally comprises based on the preferred 0.1-10 weight portion of 100 weight parts monomers, preferably the ethylenic unsaturated acid of the amount of 0.2-8 weight portion or 1-6 weight portion.The example of ethylenic unsaturated acid is ethylenically unsaturated carboxylic acids, olefinic unsaturated sulfonic acid and vinyl phosphonate.Ethylenically unsaturated carboxylic acids used is preferably the α in molecule with 3-6 carbon atom, and β-monoene belongs to unsaturated list-and dicarboxylic acids.The example is acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinyl acetic acid and vinyl lactic acid.Useful olefinic unsaturated sulfonic acid comprises for example vinyl sulfonic acid, styrene sulfonic acid, acrylamido methyl propane sulfonic acid, acrylic acid sulfo group propyl ester and methacrylic acid sulfo group propyl ester.Ethylenic unsaturated acid can be used as free acid and after partially or completely neutralizing by appropriate base for polymerization.Preferably use sodium hydrate aqueous solution, potassium hydroxide aqueous solution or ammonia as neutralizer.
Can optionally use and be different from other alefinically unsaturated compounds of described monomer above.Other monomer can be with the amount of every 100 weight parts monomers mixture 0-15 weight portions, and the amount of for example 0.1-15 weight portion or 0.5-10 weight portion is used.The example of other monomer is unsaturated nitrile, for example acrylonitrile and methacrylonitrile, the unsaturated carboxylic acid amides of olefinic, for example acrylamide and Methacrylamide, saturated C
1-C
18the vinyl acetate of carboxylic acid, acrylic acid and methacrylic acid and monobasic C
1-C
18the ester of alcohol, for example methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, acrylic acid n-propyl, n propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-BMA, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, the secondary butyl ester of methacrylic acid, tert-butyl acrylate, Tert-butyl Methacrylate, acrylic acid pentyl ester, methacrylic acid pentyl ester, 2-EHA, 2-Ethylhexyl Methacrylate, the allyl ester of saturated carboxylic acid, vinyl ethers, vinyl copper, the diallyl ester of ethylenically unsaturated dicarboxylic, NVP, N-ethenyl pyrrolidone, N-vinyl formamide, N, N-dialkyl aminoalkyl acrylamide, N, N-dialkyl aminoalkyl Methacrylamide, acrylic acid N, N-dialkyl aminoalkyl ester, methacrylic acid N, N-dialkyl aminoalkyl ester, vinyl chloride and vinylidene chloride.Other monomer is preferably monoene and belongs to undersaturated.But, also can use many unsaturated monomers, especially there is the cross-linking monomer of two or more olefinic double bonds, for example alkanediol diacrylate, for example butanediol diacrylate.
An embodiment is used:
(a) 4.8-95 weight portion, preferably 9.8-75 parts by weight of styrene or methyl styrene,
(b) 4.8-95 weight portion, preferably 24.8-90 weight parts of butadiene,
(c) at least one ethylenic unsaturated acid of 0.1-10 weight portion, it is preferably selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, vinyl acetic acid, vinyl lactic acid, vinyl sulfonic acid, styrene sulfonic acid, acrylamido methyl propane sulfonic acid, acrylic acid sulfo group propyl ester and methacrylic acid sulfo group propyl ester, and
(d) at least one other single ethylenically unsaturated monomer of 0-15 weight portion,
Wherein the weight portion of monomer amounts to 100 separately.
An embodiment is used:
(a) 4.8-95 weight portion, preferably 39.8-85 weight portion vinyl acetate,
(b) 4.8-95 weight portion, preferably 14.8-60 parts by weight of ethylene, and
(c) at least one other single ethylenically unsaturated monomer of 0-10 weight portion,
Wherein the weight portion of monomer amounts to 100 separately.
Polymer for example can obtain by emulsion polymerisation.This can be by originally pack some initators and some in water-bearing media, for example the treating polymerization total monomer of 1-10 % by weight and carrying out.Then in the time that polymerization starts, under polymerizing condition, respectively all the other monomers and all the other initators are metered in initial charge.Polymerization also can be at protecting colloid, and for example polyvinyl alcohol or degradable starch for example have the intrinsic viscosity η of 0.02-0.06dl/g
ithe existence of degraded native starch under carry out.Term polymerizing condition is to be understood that the essential temperature while meaning the reactant mixture in initial charge to be heated to carry out polymerization.These temperature are for example 80-130 ℃, preferably 90-120 ℃.Polymerization preferably under super-atmospheric pressure, for example, is carried out under the pressure of 60 bar at the most, but the polymerization under 2-10 bar pressure conventionally of the copolymer of butadiene, the copolymer of ethene is polymerization under the pressure of 40-60 bar preferably.
The inventive method is used the initator that forms free radical under reaction condition conventionally.The example of suitable polymerization initiators is peroxide, hydroperoxides, hydrogen peroxide, sodium peroxydisulfate, potassium peroxydisulfate, oxidation reduction catalyst and azo-compound, for example 2, two (4-methoxyl group-2 of 2-azo, 4-methyl pentane nitrile), 2,2-azo two (2,4-methyl pentane nitrile) and two (2-amidine propane) dihydrochlorides of 2,2-azo.The example of other initiator appropriate is dibenzoyl peroxide, cross neopentanoic acid tertiary butyl ester, cross-2 ethyl hexanoic acid tertiary butyl ester, di-t-butyl peroxide, peroxidating diamyl, dioctanoyl peroxide, peroxidating two-dodecanoyl, dilauroyl peroxide, peroxidating two (o-toluoyl), succinyl peroxide, peracetic acid tertiary butyl ester, cross maleic acid tertiary butyl ester, cross isobutyric acid tertiary butyl ester, cross neopentanoic acid tertiary butyl ester, cross sad tertiary butyl ester, t-butyl perbenzoate, tert-butyl hydroperoxide, azobis isobutyronitrile, 2, 2 '-azo two (2-methylbutyronitrile), 2, 2 '-azo two (2, 4-methyl pentane nitrile) and 2, two (the N of 2 '-azo, N '-dimethylene NSC 18620) dihydrochloride.Be preferably selected from the initator of peracetic dithionite, peroxysulphate, azo initiator, organic peroxide, organic hydroperoxide and hydrogen peroxide.Particularly preferably use water soluble starter, for example sodium peroxydisulfate, potassium peroxydisulfate, ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate and/or peroxo disulfate acid ammonium.Polymerization also can be used high-energy ray as electron beam ray or by causing with UV irradiation.
Initator for example, with 2 % by weight at the most, is preferably not less than 0.9 % by weight, and for example 1.0-1.5 % by weight treats that the amount of polymerization single polymerization monomer is used.Preferably, first the initator of at least 30 % by weight is optionally packed in water-bearing media together with protecting colloid, and monomer and all the other initators are metered in this initial charge under polymerizing condition.
Polymeric dispersions by first for example to be equipped with mixing arrangement can reactor heating in pack into and be preferably not less than any aqueous solution in required total amount of initiator of 30 % by weight and optional above-mentioned protecting colloid and prepare.In initial charge, the amount of initator is preferably no more than 90 % by weight of the required total amount of monomer polymerization, conventionally no more than 60 % by weight.Protecting colloid is carried out the stabilisation of the fine dispersion of monomer and the polymer in small, broken bits of formation.Protecting colloid stands at least part of grafting and becomes in the polymer that firmly mixes formation in emulsion polymerisation.
Monomer in water-bearing media disperses to strengthen by the emulsifying agent that uses protecting colloid and/or be commonly used for dispersant.The detailed description of other appropriate protection colloid is shown in Houben-Weyl, Methoden der organischen Chemie, and XIV/1 volume, Makromolekulare Stoffe, Georg-Thieme-Verlag, Stuttgart, in 1961, the 411-420 pages.Suitable emulsifying agent comprises that number-average molecular weight is generally below 2000g/mol; or the preferably surface reactive material below 1500g/mol; the number-average molecular weight of protecting colloid is more than 2000g/mol simultaneously, for example 2000-100000g/mol, especially 5000-50000g/mol.
Suitable emulsifying agent comprises the ethoxylation C of the ethoxylation degree for example with 3-50
8-C
36fatty alcohol, have the ethoxylation list of the ethoxylation degree of 3-50-, two-and three-C
4-C
12alkylphenol, the alkali metal salt of the dialkyl of sulfosuccinic acid, sulfuric acid C
8-C
12the alkali metal of Arrcostab and ammonium salt, C
12-C
18the alkali metal of alkyl sulfonic acid and ammonium salt, and C
9-C
18the alkali metal of alkyl aryl sulphonic acid and ammonium salt.The example of cation activity emulsifying agent is for having at least one amino or ammonium group and at least one C
8-C
22the compound of alkyl.When emulsifying agent and/or protecting colloid as assistant with dispersed monomer, their consumption is for example 0.1-5 % by weight based on monomer.
Initial charge can further comprise polystyrene crystal seed, has the aqueous dispersion of the polystyrene in small, broken bits of the particle diameter of 20-40nm.
For improving the performance of polymer, emulsion polymerisation can optionally be carried out under the existence of at least one chain-transferring agent.The example of chain-transferring agent is the organic compound of the sulphur that comprises combining form, for example lauryl mercaptan, thiodiglycol, ethylthioethanol, di-n-butyl sulphur, two-n-octyl sulphur, diphenyl sulfide, diisopropyl disulfide, 2 mercapto ethanol, 1,3-mercaprol, 3-sulfydryl propane-1,2-glycol, Isosorbide-5-Nitrae-Mercaptobutanol, TGA, 3-mercaptopropionic acid, mercapto succinic acid, thioacetic acid and thiocarbamide.Other chain-transferring agent is aldehyde, for example formaldehyde, acetaldehyde and propionic aldehyde, and organic acid, for example formic acid, sodium formate or ammonium formate, alcohol, for example more particularly, isopropyl alcohol and phosphorus compound are as sodium hypophosphite.In the time that chain-transferring agent is used for polymerization, in its every kind of situation of consumption, be for example 0.01-5% based on monomer used in polymerization, preferably 0.1-1 % by weight.Chain-transferring agent is preferably metered into together with monomer.But they also can be included in initial charge whole or in part.They also can add in the stage with respect to monomer biasing.
Emulsion polymerisation is carried out in water-bearing media.Water-bearing media can comprise for example complete deionized water or water and water miscibility solvent as the mixture of methyl alcohol, ethanol or oxolane.For making monomer polymerization, first step is the aqueous solution of preparing degradable starch.This solution can optionally comprise protecting colloid and/or the emulsifying agent of dissolved form, and optional polystyrene crystal seed.Before preferably in required total amount of initiator of at least 30 % by weight is added to initial charge, the aqueous solution as initial charge is heated to the temperature of carrying out the temperature of monomer polymerization or being heated to 5-20 below polymerization temperature ℃.In the time reaching required specific aggregation temperature or reaching 1-15 minute after polymerization temperature, preferably, in the time interval of 5-15 minute, carry out being metered into of monomer.Can be for example by them for example in 60 minutes to 10 hours, conventionally in 2-4 hour, pump into continuously in reactor.
It is also possible that the classification of monomer adds.In a preferred embodiment of the inventive method, what first pack 1-10 % by weight into always treats polymerization single polymerization monomer.In this case, preferably before reactor content being heated to polymerization temperature, first monomer is packed in reactor together with said components, preferably reaching polymerization temperature described above to be not long ago added to the amount of initiator of few 30 % by weight, then add as mentioned above all the other monomers simultaneously.After polymerization finishes, can optionally other initator be added in reactant mixture with the secondary polymerization at the temperature identical with main polymerization or under lower or higher temperature.For completing polymerisation, after adding all monomers, it 1-3 hour is enough in many cases that reactant mixture is stirred in addition under polymerization temperature.
PH can be for example 1-5 between polymerization period.After polymerization, pH is adjusted to the value of for example 6-7.
In one embodiment, the solids content of aqueous polymer dispersion of the present invention is more than 55 % by weight, for example at least 60 % by weight.This solids content can for example realize by institute's water consumption and/or amount of monomer in suitable adjustment emulsion polymerisation.
Aqueous polymer dispersion of the present invention as adhesive for the preparation of paper coating compositions.
Outside dewatering, paper coating compositions for example comprises pigment, adhesive and optional assistant, conventionally to set up essential rheological property, thickener.Pigment is generally the state of the dispersion in water.Paper coating compositions for example comprises, based on preferably at least 80 % by weight of total solids content, the pigment of the amount of 80-95 % by weight or 80-90 % by weight.Special expection Chinese white.Suitable pigment comprises for example slaine pigment, for example calcium sulfate, calcium sulphoaluminate, barium sulfate, magnesium carbonate and calcium carbonate, wherein preferred carbonate pigment, especially calcium carbonate.Calcium carbonate can be calcium carbonate (GCC), winnofil (PCC), lime or the chalk of natural ground.The for example conduct of suitable calcium carbonate pigment
60,
60 or
90ME obtains.The example of other suitable pigments is silica, alumina, aluminium hydroxide, silicate, titanium dioxide, zinc oxide, kaolin, clay, talcum or silica.Other for example conduct of suitable pigment
mP50 (clay),
90 (clays) or Talcum C10 obtain.
Paper coating compositions comprises at least one in above-mentioned adhesive.The polymeric dispersions obtaining according to the present invention can be used as unique adhesive or with other binder combination for paper coating compositions.The most important functions of adhesive in paper coating compositions is pigment to be bonded on paper and by bonded to each other pigment and the space between filler pigment particle to a certain extent.For every 100 weight portion pigment, the amount of organic bond used (with regard to adhesive solids, not having water or at 21 ℃, lower other solvent for liquid of 1 bar) be for example 1-50 weight portion, preferred 1-25 weight portion or 5-20 weight portion.
Useful adhesive further comprises natural based adhesive, especially starch-based adhesive, and be different from the polymer obtaining according to the present invention, the composite adhesives of the emulsion polymer that more particularly can obtain by emulsion polymerisation.Starch-based adhesive is to be understood that in this article and means any natural modified or degradable starch.Native starch can be by amylose, amylopectin or its compositions of mixtures.Modified starch can be oxidized starch, starch ester or starch ether.Can use hydrolysis to reduce the molecular weight (to obtain degradable starch) of starch.Useful catabolite comprises low sugar or dextrin.Preferred starch is cereal starch, cornstarch and farina.Particularly preferably cereal starch and cornstarch, very particularly preferably cereal starch.
Be different from other composite adhesives of the polymer obtaining according to the present invention preferably by least 40 % by weight degree, preferably at least 60 % by weight degree, the more preferably so-called main monomer composition of at least 80 % by weight degree.Main monomer is selected from (methyl) acrylic acid C
1-C
20arrcostab, the vinyl acetate that comprises the carboxylic acid of 20 carbon atoms at the most, the vinyl aromatic compounds with 20 carbon atoms at the most, olefinically unsaturated nitriles, vinyl halide, comprise 1-10 carbon atom alcohol vinethene, there is the aliphatic hydrocarbon of 2-8 carbon atom and one or two pair of key or its mixture.Example is for having C
1-C
10(methyl) alkyl acrylate of alkyl, for example methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl acrylate and 2-EHA.The mixture of (methyl) alkyl acrylate is also specially suitable.The example with the vinyl acetate of the carboxylic acid of 1-20 carbon atom is vinyl laurate and stearic acid vinyl ester.The example of nitrile is acrylonitrile and methacrylonitrile.Vinyl halide is the alefinically unsaturated compounds of chloro-, fluoro-or bromo-replacement, preferably vinyl chloride and vinylidene chloride.The example of vinyl ethers comprises vinyl methyl ether and vinyl isobutyl ether.Preferably comprise the vinyl ethers of the alcohol of 1-4 carbon atom.Preferred main monomer is (methyl) acrylic acid C
1-C
10arrcostab, and (methyl) alkyl acrylate and vinyl aromatic compounds, especially cinnamic mixture.
Except main monomer, can comprise other monomer as the emulsion polymer of adhesive, for example there is the monomer of carboxylic acid, sulfonic acid or phosphonyl group.Optimization acid's group.Example comprises acrylic acid, methacrylic acid, itaconic acid, maleic acid and fumaric acid.In emulsion polymer, the content of ethylenic unsaturated acid is generally below 10 % by weight, preferably below 8 % by weight, and at least 0.1 % by weight or at least 1 % by weight.Other monomer also comprises for example hydroxyl monomer, especially (methyl) acrylic acid C
1-C
10arrcostab, or acid amides is as (methyl) acrylamide.
In the time using composite adhesives, can use natural glue as starch, but they are not absolute demands yet.
Paper coating compositions of the present invention also can comprise other additive and assistant material, for example filler, help adhesive and thickener further to make viscosity and water-retaining property optimization, fluorescent whitening agent, dispersant, surfactant, slipping agent (such as calcium stearate and wax), neutralizer (such as NaOH or ammonium hydroxide) such as, to adjust pH, defoamer, degasifier, preservative agent (biocide), flow improver, dyestuff (especially soluble dye) etc.For example, except synthetic polymer (crosslinked polyacrylate), useful thickener more particularly comprises cellulose, preferably carboxymethyl cellulose.The example of fluorescent whitening agent is fluorescence or phosphorescent coloring, especially stilbene.
Paper coating compositions is preferably moisture paper coating compositions; Water is especially because the supplementary form (aqueous polymer dispersion, aqueous pigment slurry) of component is present in wherein; Required viscosity can be by further adding water to set.The conventional solids content of paper coating compositions is 30-70 % by weight.Preferably paper coating compositions pH is adjusted to 6-10, especially the value of 7-9.5.
In one embodiment, the invention provides paper coating compositions, wherein the Polymers of aqueous polymer dispersion uses with the amount of 1-50 weight portion in the total amount of pigment, and pigment is included with the amount of 80-95 weight portion based on total solids content.
Preferred pigments is selected from calcium sulfate, calcium sulphoaluminate, barium sulfate, magnesium carbonate, calcium carbonate, silica, alumina, aluminium hydroxide, silicate, titanium dioxide, zinc oxide, kaolin, clay, talcum and silica.
Preferably paper coating compositions further comprises at least one assistant, and described assistant is selected from thickener, other polymer adhesive, helps adhesive, fluorescent whitening agent, filler, flow control agent, dispersant, surfactant, slipping agent, neutralizer, defoamer, degasifier, preservative agent and dyestuff.
The present invention also provides by the paper of paper coating compositions coating of the present invention or the method for cardboard and coated paper or cardboard, and described method comprises:
-paper coating compositions of the present invention is provided; With
-paper coating compositions is applied at least one surface of paper or cardboard.
Preferably paper coating compositions is applied over without coating body paper or without in coated board.Amount be generally 1-50g, be preferably 5-30g (with regard to solid, at 21 ℃, not thering is water or other solvent under 1 bar)/square metre.Coating can be passed through conventional method of application, for example, undertaken by sizing applicator, molding machine, knife type coater, air-brush, scraper, curtain coating or flush coater.Depend on pigments system, paper coating compositions of the present invention can be used for priming coat and/or top coat.
Paper coating compositions of the present invention has good performance characteristic.They have high adhesion and high resistance jaundice property.In conventional printing process, can easily print for example letterpress, intaglio printing, hectographic printing, digital printed, ink jet printing, flexographic printing, newsprint printing, typographic printing, sublimation printing, laser printing and electrophotographic printing or its combination with the paper that paper coating compositions applies.
Embodiment
Unless pointed out in addition in context, percentage is weighing scale always.The content of the content of report based in the aqueous solution or dispersion.
Solids content is measured by the particular polymers aqueous dispersion of specified amount (about 5g) is dried to constant weight in drying box at 140 ℃.In every kind of situation, carry out two measurements that separate and average.
The average diameter of polymer beads can be measured by fluid dynamic force chromatography (HDC).In HDC, by colloidal state sample wash-out from the granularity exclusion fractionating column of classifying according to hydrodynamic radius.Eluent comprises salt, non-ionic surface active agent and anion surfactant.PS calibration latex calibration for elution time.Measurement category extends to 1200nm-larger component from 15nm and is filtered off and does not detect.Can measure the accuracy of diameter and weight fraction to 3%.Use UV absorption under 254nm and by mark weighting.
Polymeric dispersions D1
50% aqueous polymer dispersion of styrene-based/butadiene/acrylic acid/acrylamide/itaconic acid (52.8/41.8/3.5/1.3/0.6); Granularity: 85nm; Tg0 ℃
Polymeric dispersions D2
50% aqueous polymer dispersion of styrene-based/butadiene/acrylic acid/acrylamide/itaconic acid (52.8/41.8/3.5/1.3/0.6); Granularity: 95nm; Tg0 ℃
Polymeric dispersions D3
50% aqueous polymer dispersion of styrene-based/butadiene/acrylic acid/acrylamide/itaconic acid (52.8/41.8/3.5/1.3/0.6); Granularity: 130nm; Tg0 ℃
Polymeric dispersions D4
50% aqueous polymer dispersion of styrene-based/butadiene/acrylic acid/itaconic acid (59/38/2/1); Granularity: 215nm; Tg4 ℃
Polymeric dispersions D5
Paper coating compositions:
Be coated with slip stirring preparation in equipment (Deliteur), wherein each component adjoining land fed in this equipment.Pigment adds using pre-dispersed form (as slurry).Other component adds after pigment, and order is corresponding to the order in the coating slurry formula of report.Final solids content is by adding water setting.
Use 5 kinds of polymeric dispersions D1-D5 to be prepared as follows 5 kinds of coating for paper paste composition P1-P5 of composition:
100 weight portions
60 slurry (calcium carbonate in small, broken bits)
0.35 weight portion
fS (acrylate-based thickener)
One in the polymeric dispersions D1-D5 of 8 weight portions.
Solids content: 65 % by weight.
Will
58g/m
2paper applies and rolls with being coated with slip one side in half business coating machine.The weight of the slurry coating applying is 11g/m
2.
Use the surperficial resistance of method of testing test coated paper well known by persons skilled in the art.Use following test method:
IGT does picking resistance
The IGT picking resistance that wets
Offset printing test
Anti-jaundice
The results are summarized in table 1 and 2.
use IGT testing machine to measure dry picking resistance (IGT is dry)
Cut bar and use the printing of IGT testing machine from test paper.Printing-ink used is the specialty test ink of the tension force different from the transmission of Lorillieux.Test bar is passed through to press with the speed (maximal rate 200cm/s) improving continuously.For assessment, the point when being determined at printing occurring 10 trichobothriums after starting in sample printed strip on paper surface.That this point exists and the speed representing with cm/s of test ink used during printing about the tolerance of dry picking resistance report.The 10th this print speed printing speed that plays trichobothrium is higher, and the performance rating of paper surface is better.
by the wet picking resistance of IGT testing machine measurement (IGT is wet)
Cut bar and use the printing of IGT testing machine from test paper.Before printing, testing machine being set makes the water-wet of examination bar.Printing-ink used is the specialty test ink (No.3807) of the tension force different from the transmission of Lorillieux.Printing is carried out with the constant speed of 0.6cm/s.The trichobothrium that rises from paper surface is considered as not printing area.For measuring wet picking resistance, use ink density instrumentation to have the ink density into the % of panchromatic tune made to order.The ink density of report is higher, and wet picking resistance is better.
offset printing test:
The longitudinally upper sample that cuts the size with 240 × 46mm from testing paper.Appropriate printing-ink is applied on upper inking roller and keeps operation 1 minute.Then insert printing dish inking 30 seconds.Print speed printing speed is 1m/s.Paper slip is returned and there is the enable position on the printing test bracket that prints paper slip.At the appointed time, after interval, again start printing process and do not replace printing dish.Repeat this operation more than once.After each print cycle, the trichobothrium on visually rank paper slip printing surface.Statistical tables and reports have been accused the number of cycles before fluffing occurs for the first time.To having occurred that the number of cycles of trichobothrium is higher, paper is better to the well-formedness of hectographic printing.
the test of anti-jaundice
UV jaundice
The test paper originally all with similar CIE whiteness is exposed under the light of UV lamp.After moment, again measure the whiteness of paper.Be reported in and be exposed to light 8 hours later CIE whiteness.Heat jaundice
The test paper originally all with similar CIE whiteness is suspended in the drying box of 120 ℃.After moment, again measure the whiteness of paper.Be reported in 120 ℃ and store 48 hours later CIE whiteness.
Table 1 bonding force is measured
| Embodiment | Granularity [nm] | Dry picking resistance [cm/s] | Wet picking resistance [%] | Offset printing journey |
| P1 | 85 | 61 | 80 | 6.5 |
| P2 | 95 | 55 | 74 | 6.25 |
| P3 | 130 | 54 | 73 | 5.5 |
| P4 | 215 | 49 | 65 | 4.5 |
| P5 | 770 | 19 | 7 | 2.0 |
Use has painting slip P1-P3 prepared by the polymeric dispersions of the particle mean size below 150nm and causes higher bonding force.
Table 2: jaundice result of the test
| Embodiment | Irradiate the CIE whiteness after 8 hours | Be heated to 120 ℃ of CIE whiteness after 48 hours |
| P1 | 67 | 45 |
| P2 | 68 | 49 |
| P3 | 68 | 45 |
| P4 | 68 | 49 |
| P5 | 72 | 60 |
The painting slip (P5) that uses the polymeric dispersions based on vinyl-vinyl acetate copolymer to prepare causes higher anti-jaundice.
Claims (12)
1. paper coating compositions, it comprises:
(i) inorganic pigment, and
(ii) aqueous polymer dispersion that comprises dispersed polymeres particle, wherein polymer obtains by following monomer polymerization:
(a) at least one first monomer, it is lower in room temperature (20 ℃) is liquid, has the boiling point of at least 50 ℃ and the glass transition temperature of at least 20 ℃ as homopolymers, and
(b) at least one second monomer, it is lower in room temperature (20 ℃) is gas, has 0 ℃ of following boiling point and the glass transition temperatures below-30 ℃ as homopolymers,
The polymer beads wherein disperseing has the glass transition temperature of particle mean size below 150nm and-10 ℃ to+30 ℃.
2. according to the paper coating compositions of claim 1, wherein said polymer beads has the particle mean size below 80nm to 150nm.
3. according to the paper coating compositions of any one in aforementioned claim, wherein said at least one first monomer (a) be selected from vinyl aromatic compounds and vinyl acetate and described at least one second monomer (b) be selected from single-or polyenoid belong to unsaturated C2-C4 hydrocarbon.
4. according to the paper coating compositions of any one in aforementioned claim, wherein said at least one first monomer (a) is selected from styrene and vinyl acetate and described at least one second monomer (b) and is selected from 1,3-butadiene and ethene.
5. according to the paper coating compositions of any one in aforementioned claim, wherein said polymer is selected from the polymer that at least 60 % by weight degree are formed by ethene and vinyl acetate, the polymer that at least 60 % by weight degree are formed by styrene and vinyl acetate, and composition thereof.
6. according to the paper coating compositions of any one in aforementioned claim, wherein said polymer is formed by following monomer:
(a) 4.8-95 parts by weight of styrene or methyl styrene,
(b) 4.8-95 weight parts of butadiene,
(c) at least one ethylenic unsaturated acid of 0.1-10 weight portion, and
(d) at least one other single ethylenically unsaturated monomer of 0-15 weight portion,
Or
(a) 4.8-95 weight portion vinyl acetate,
(b) 4.8-95 parts by weight of ethylene, and
(c) at least one other single ethylenically unsaturated monomer of 0-10 weight portion,
Wherein the weight portion of monomer amounts to 100 separately.
7. according to the paper coating compositions of any one in aforementioned claim, wherein said polymer is formed by following monomer:
(a) 9.8-75 parts by weight of styrene or methyl styrene,
(b) 24.8-90 weight parts of butadiene,
(c) at least one ethylenic unsaturated acid of 0.1-10 weight portion, and
(d) at least one other single ethylenically unsaturated monomer of 0-15 weight portion,
Or
(a) 39.8-85 weight portion vinyl acetate,
(b) 14.8-60 parts by weight of ethylene, and
(c) at least one other single ethylenically unsaturated monomer of 0-10 weight portion,
Wherein the weight portion of monomer amounts to 100 separately.
8. according to the paper coating compositions of any one in aforementioned claim, the Polymers of wherein said aqueous polymer dispersion uses with the amount of 1-50 weight portion in the total amount of pigment, and pigment is included with the amount of 80-95 weight portion based on total solids content.
9. according to the paper coating compositions of any one in aforementioned claim, wherein said pigment is selected from calcium sulfate, calcium sulphoaluminate, barium sulfate, magnesium carbonate, calcium carbonate, silica, alumina, aluminium hydroxide, silicate, titanium dioxide, zinc oxide, kaolin, clay, talcum and silica.
10. according to the paper coating compositions of any one in aforementioned claim, wherein said paper coating compositions further comprises at least one assistant, and described assistant is selected from thickener, other polymer adhesive, helps adhesive, fluorescent whitening agent, filler, flow control agent, dispersant, surfactant, slipping agent, neutralizer, defoamer, degasifier, preservative agent and dyestuff.
Paper or cardboard that 11. use apply according to the paper coating compositions of any one in aforementioned claim.
The method of 12. coated papers or cardboard, described method comprises:
-provide according to the paper coating compositions of any one in claim 1-10; With
-paper coating compositions is applied at least one surface of paper or cardboard.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161551951P | 2011-10-27 | 2011-10-27 | |
| EP11186860 | 2011-10-27 | ||
| EP11186860.0 | 2011-10-27 | ||
| US61/551,951 | 2011-10-27 | ||
| PCT/IB2012/055902 WO2013061286A1 (en) | 2011-10-27 | 2012-10-26 | Paper coating compositions comprising a polymer dispersion from room temperature liquid and gaseous monomers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103890266A true CN103890266A (en) | 2014-06-25 |
Family
ID=48167212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280052663.7A Pending CN103890266A (en) | 2011-10-27 | 2012-10-26 | Paper coating compositions comprising a polymer dispersion from room temperature liquid and gaseous monomers |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20140302309A1 (en) |
| EP (1) | EP2771509A4 (en) |
| JP (1) | JP2014530968A (en) |
| KR (1) | KR20140092367A (en) |
| CN (1) | CN103890266A (en) |
| BR (1) | BR112014009970A2 (en) |
| CA (1) | CA2854354A1 (en) |
| WO (1) | WO2013061286A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2814850B1 (en) | 2012-02-14 | 2017-04-12 | Basf Se | Aqueous polymer dispersion obtainable by free-radically initiated emulsion polymerization in the presence of lignosulfonate |
| EP3585942A1 (en) * | 2017-02-27 | 2020-01-01 | WestRock MWV, LLC | Heat sealable barrier paperboard |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4258104A (en) * | 1979-04-27 | 1981-03-24 | The Dow Chemical Company | Aqueous polymeric dispersions, paper coating compositions and coated paper articles made therewith |
| CN1188449A (en) * | 1995-06-21 | 1998-07-22 | 巴斯福股份公司 | Use of paper-coating materials with high butadiene content in offset printing |
| CN1233260A (en) * | 1996-09-09 | 1999-10-27 | 巴斯福股份公司 | Process for producing aqueous polymer dispersions |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2698892B1 (en) * | 1992-12-04 | 1995-01-20 | Rhone Poulenc Chimie | Latex binder composition for paper coating. |
| ATE171492T1 (en) * | 1993-10-19 | 1998-10-15 | Basf Ag | USE OF PAPER COATED WITH CERTAIN BINDER MIXTURES FOR OFFSET PRINTING |
| DE19522399A1 (en) * | 1995-06-21 | 1997-01-02 | Basf Ag | Use of paper coating slips with high butadiene content in offset printing |
| EP0764739B1 (en) * | 1995-09-22 | 2001-01-24 | Oji Paper Co., Ltd. | Moisture-proof paper sheet |
| AU2003292605A1 (en) * | 2002-12-25 | 2004-07-29 | Jsr Corporation | Copolymer latex for noncontact coating and composition comprising the same, and coated paper and method for production thereof |
| JP2005105467A (en) * | 2003-09-30 | 2005-04-21 | Nippon Paper Industries Co Ltd | Converting paper |
| KR101041304B1 (en) * | 2006-12-07 | 2011-06-14 | 재단법인서울대학교산학협력재단 | Styrene-butadiene latex binder for ink-jet paper, preparation method thereof and coating liquid containing the same |
| CN101558084A (en) * | 2006-12-15 | 2009-10-14 | 巴斯夫欧洲公司 | Production of polymer dispersions in the presence of organic polymer particles |
| BRPI0818356B1 (en) * | 2007-10-08 | 2019-09-10 | Basf Se | aqueous polymeric dispersions, process for preparing aqueous polymeric dispersions, and use of aqueous polymeric dispersions |
-
2012
- 2012-10-26 US US14/351,463 patent/US20140302309A1/en not_active Abandoned
- 2012-10-26 KR KR1020147014161A patent/KR20140092367A/en not_active Application Discontinuation
- 2012-10-26 EP EP12844209.2A patent/EP2771509A4/en not_active Withdrawn
- 2012-10-26 WO PCT/IB2012/055902 patent/WO2013061286A1/en active Application Filing
- 2012-10-26 CN CN201280052663.7A patent/CN103890266A/en active Pending
- 2012-10-26 CA CA2854354A patent/CA2854354A1/en not_active Abandoned
- 2012-10-26 BR BR112014009970A patent/BR112014009970A2/en not_active IP Right Cessation
- 2012-10-26 JP JP2014537795A patent/JP2014530968A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4258104A (en) * | 1979-04-27 | 1981-03-24 | The Dow Chemical Company | Aqueous polymeric dispersions, paper coating compositions and coated paper articles made therewith |
| CN1188449A (en) * | 1995-06-21 | 1998-07-22 | 巴斯福股份公司 | Use of paper-coating materials with high butadiene content in offset printing |
| CN1233260A (en) * | 1996-09-09 | 1999-10-27 | 巴斯福股份公司 | Process for producing aqueous polymer dispersions |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2013061286A1 (en) | 2013-05-02 |
| EP2771509A1 (en) | 2014-09-03 |
| CA2854354A1 (en) | 2013-05-02 |
| KR20140092367A (en) | 2014-07-23 |
| EP2771509A4 (en) | 2015-08-12 |
| US20140302309A1 (en) | 2014-10-09 |
| JP2014530968A (en) | 2014-11-20 |
| BR112014009970A2 (en) | 2017-05-30 |
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