CN108779608A - Paper coating composition and preparation method - Google Patents
Paper coating composition and preparation method Download PDFInfo
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- CN108779608A CN108779608A CN201680083682.4A CN201680083682A CN108779608A CN 108779608 A CN108779608 A CN 108779608A CN 201680083682 A CN201680083682 A CN 201680083682A CN 108779608 A CN108779608 A CN 108779608A
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- 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
- C09D125/14—Copolymers of styrene with unsaturated esters
-
- 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
- C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention provides a kind of novel coating composition, and it includes the aqueous dispersions of adhesive；Pigment；Starch；With the alkali swellability lotion of the hydrophobically modified of the structural unit comprising carboxylic acid monomer, acrylate monomer and polyethoxylated aralkylphenol methacrylate.This novel coating composition provides the thickening efficiency improved.
Description
Technical field
The present invention relates to paper coating compositions and the method for preparing the paper coating composition.
Foreword
In paper-making process, usually by coating composition to body paper surface to ensure will be on image printing to paper
Paper surface is smooth and not caused by body paper fiber " peak and valley " before.Paper manufacturer is in a conventional manner by rheology modifier
(i.e. thickener) is added in paper coating as additive to enhance the physical stability of coating and control coating weight.
For this purpose, alkali-soluble emulsion (" HASE ") polymer of hydrophobically modified is typically used as preferred rheology modified
Agent.Conventional HASE compositions are formed usually using the associative monomer with the straight-chain aliphatic alkyl chain as end group with serving as
Conjunction property dredges and keeps away object (associative phobe).The example of this associative monomer is polyoxyethylene lauryl base-stearyl first
Base acrylate, polyoxyethylene laural base-myristyl methacrylate.
However, containing the coating composition and water-soluble additives of this conventional HASE polymer in being applied in precoating
When (such as starch) mixes, coating composition often shows low low-shear viscosity.This phenomenon needs to add more
HASE polymer leads to additional manufacturing cost to reach required levels of viscosity.Accordingly, it is desirable to provide one kind contains
The coating composition of rheology modifier with higher thickening efficiency.
Invention content
The present inventor unexpectedly has found a kind of novel coating composition.In other applications, this novel painting
Feed composition can be coated to during the precoating stage of paper-making process on paper surface.More specifically, the present inventor is logical
A series of experiments discovery is crossed, the HASE polymer made of the specific associative monomer with hydrophobic phenyl radical end group is contained
Coating composition will have better low-shear viscosity and higher thickening efficiency.
Particularly, the present invention is a kind of paper coating composition, and it includes the aqueous dispersions of adhesive；Pigment；Starch and packet
The hydrophobic of structural unit containing carboxylic acid monomer, acrylate monomer and polyethoxylated aralkylphenol (methyl) acrylate changes
The alkali swellability lotion of property.
Specific implementation mode
In one embodiment of the invention, coating composition of the invention is paper coating composition, and it includes adhesives
Aqueous dispersion, starch, pigment and the alkali swellability lotion through polyethoxylated aralkylphenol hydrophobically modified.
The aqueous dispersion of adhesive
The aqueous dispersion of adhesive is preferably selected from pure acrylic acid copolymer, styrene acrylic copolymer, styrene fourth two
The vinyl acetate emulsion mixture of alkene copolymer or vinyl acrylic copolymers polyvinyl acetate, these adhesives.With
It is typically ethylenically unsaturated monomer in forming the suitable unsaturated monomer of above-mentioned copolymer comprising vinyl aromatic chemical combination
Object (such as styrene, α-methylstyrene, ortho-chlorostyrene and vinyltoluene)；1,2- butadiene；Conjugated diene (such as 1,
3- butadiene and isoprene)；α, β-monoethylenically unsaturated monocarboxylic and dicarboxylic acids or its acid anhydrides (such as acrylic acid, methyl-prop
Olefin(e) acid, crotonic acid, dimethacrylate, ethylacrylic acid, allyl acetic acid, vinyl acetic acid, maleic acid, fumaric acid, clothing health
Acid, mesaconic acid, methylene propylmalonic acid, citric acid, maleic anhydride, itaconic anhydride and methylmalonic acid acid anhydride)；With 3 to 6 carbon originals
The α of son, β-monoethylenically unsaturated monocarboxylic and dicarboxylic acids and the alkanol with 1 to 12 carbon atoms ester (such as acrylic acid,
Methacrylic acid, maleic acid, fumaric acid or itaconic acid and C1-C12、C1-C8Or C1-C4The ester of alkanol, such as ethyl acrylate, third
Olefin(e) acid N-butyl, isobutyl acrylate and 2-EHA and ethyl methacrylate, n-BMA,
Isobutyl methacrylate and 2-Ethylhexyl Methacrylate, dimethyl maleate and n-butyl maleate)；Acrylamide and
Alkyl-substituted acrylamides (such as (methyl) acrylamide, N tert butyl acrylamide and N- methyl (methyl) acryloyl
Amine)；(methyl) acrylonitrile；Halogen ethylene and vinylidene halide (such as vinyl chloride and vinylidene chloride)；C1-C18Monocarboxylic acid or dicarboxylic acids
Vinyl esters (such as vinyl acetate, vinyl propionate, vinyl propionate, vinyl laurate and vinyl stearate
Ester)；C3-C6The C of monocarboxylic acid or dicarboxylic acids (especially acrylic acid, methacrylic acid or maleic acid)1-C4Hydroxy alkyl ester or its warp
The alkoxylated derivative of or mixtures thereof 2 to 50 moles of ethylene oxide, propylene oxide, epoxy butane or these acid are arrived with through 2
Ester (such as (methyl) third of the alkoxylated C1-C18 alcohol of or mixtures thereof 50 moles of ethylene oxide, propylene oxide, epoxy butane
Olefin(e) acid hydroxyl ethyl ester, (methyl) hydroxypropyl acrylate and methyl polyethylene glycol acrylate)；With the monomer containing glycidyl
(such as glycidyl methacrylate).As used herein, term " (methyl) acrylate " refers to acrylate, methyl
Acrylate and its mixture, and term as used herein " (methyl) acrylic acid " refer to acrylic acid, methacrylic acid and
Its mixture.
The monomer can also include one or more crosslinking agents, such as α with 3 to 10 carbon atoms, and β-monoene belongs to not
The N- alkanolamides of saturated carboxylic acid and its ester (such as N hydroxymethyl acrylamide and N- hydroxyl with the alcohol with 1 to 4 carbon atoms
Methyl methacrylamide)；Crosslinking agent based on glyoxal；Containing there are two the monomers of vinyl；Containing there are two ethenylidenes
Monomer；With containing there are two the monomers of alkenyl.Exemplary cross-linking monomer includes dihydric alcohol and α, and β-monoene belongs to unsaturated unitary carboxylic
The diester of acid, wherein acrylic acid and methacrylic acid can be used successively.Containing there are two unconjugated ethylenical unsaturated double bonds
The example of this kind of monomer is alkylene glycol diacrylates and dimethylacrylate, such as glycol diacrylate, 1,3-
Butanediol diacrylate, 1,4 butanediol diacrylate and propylene glycol diacrylate, divinylbenzene, methacrylic acid
Vinyl acetate, vinyl acrylate, allyl methacrylate, allyl acrylate, diallyl maleate, two allyl of fumaric acid
Ester and methylene-bisacrylamide.In some embodiments, cross-linking monomer includes alkylene glycol diacrylates and dimethyl
Acrylate and/or divinylbenzene.When in the copolymer in use, the amount of cross-linking monomer can in terms of the weight of total monomer
To be 0.2 weight % to 5 weight %, and it is considered as a part for the total amount monomer used in copolymer.
In addition to cross-linking monomer, a small amount of molecular weight regulator can also be added (such as with total 0.01 weight of dry monomer weight
Measure % to 4 weight %), such as tert-dodecylmercaotan.These substances add preferably in the form of with mixture monomer to be polymerized
Into polymeric area, and it is considered as a part for the total amount unsaturated monomer used in copolymer.
In certain embodiments, the amount of the adhesive dispersion in paper coating composition of the invention is with paper coating composition
In the dry weight meter of total amount of pigment can be with 3 weight % to 20 weight %, preferably 4 weight % to 15 weight % and more preferable 5
The amount of weight % to 10 weight % exists.
Pigment
The coating composition of the present invention further includes pigment.In certain embodiments, pigment is inorganic material, is such as had
The thin clay for arriving coarseness；Calcined clay；Calcium carbonate including winnofil and grinding calcium carbonate；Including anatase and golden red
The titanium dioxide of stone；Talcum；Silica；Alumina silicate；Hydrated alumina；And aluminum trihydrate, in the form of independent or with two kinds
Or a variety of combining forms is scattered in the aqueous medium in slurry form.
In general, dry colour is scattered in water or solvent to form pigment slurry first.The preparation of pigment slurry exists
It is well known that and may include dispersant such as polyacrylic acid or surfactant to contribute to granules of pigments in fields
Dispersion and stabilisation.
The alkali swellability lotion (HASE) of hydrophobically modified
In certain embodiments of the present invention, coating composition includes that the hydrophobic of the structural unit comprising following monomer changes
Alkali swellability lotion (HASE) polymer of property：A) the preferably 35 weight % to 55 weight % in terms of the dry weight of polymer, more preferably
40 weight % to 50 weight % and most preferably 45 weight % are to the α of 49 weight %, β-ethylenically unsaturated carboxylic acids monomer；B) with
The 40 weight % of dry weight meter to 55 weight % of HASE polymer, preferably 42 weight % are to 53 weight % and more preferable 45 weight %
To the α of 50 weight %, β-olefinic unsaturation non-ionic monomer；And c) in terms of the dry weight of HASE polymer 0.5 weight % to 20 weights
Measure the polyethoxylated aralkyl benzene of %, preferably 1.0 weight % to 15 weight % and more preferable 2.5 weight % to 10 weight %
Phenol (methyl) acrylate.
The suitable example of α, β-ethylenically unsaturated carboxylic acids monomer includes monoacid, such as acrylic acid, methacrylic acid, crotonic acid
And propionic；And dicarboxylic acid monomer, such as maleic acid, fumaric acid and itaconic acid.In some embodiments, using binary acid list
Body substitutes a part for monoacid, such as most about 10 weight %.The monoesters that dicarboxylic acid monomer can also be used, such as maleic acid
Mono-n-butylester.Preferably, α, β-ethylenically unsaturated carboxylic acids monomer are acrylic acid, methacrylic acid and a combination thereof.
The example of suitable α, β-olefinic unsaturation non-ionic monomer includes methyl acrylate, ethyl acrylate, acrylic acid
Butyl ester, 2-EHA, decyl acrylate, lauryl acrylate, methyl methacrylate, butyl methacrylate,
Isodecyl methacrylate, lauryl methacrylate, hydroxyethyl methacrylate and hydroxy propyl methacrylate；Metering system
Nitrile；Ethyl acrylonitrile；Methacrylamide；Methacrylamide；The monomer of amino-functional and urea/ureido functional；With acetoacetate
The monomer of ester functional group；Styrene and substituted styrenes；Butadiene；Ethylene, propylene, alpha-olefin (such as 1- decene)；Acetic acid second
Enester, vinyl butyrate, tertiary ethylene carbonate and other vinyl esters；And vinyl monomer, such as vinyl chloride, inclined two chloroethene
Alkene.Preferred embodiment be ethyl acrylate, methyl methacrylate, acrylic acid 2- hydroxybutyls, 2-hydroxyethyl methacrylate,
Methacrylic acid 2- hydroxy propyl esters, vinyl acetate and acrylonitrile and its mixture.Especially preferred non-ionic monomer is propylene
Acetoacetic ester.
Polyethoxylated aralkylphenol (methyl) acrylate has general formula：
H2C=C (R) CO2(CH2CH2O)n(CH(R1)CH2O)mR2
Wherein R is H or CH3；R1It is C1-C2Alkyl；R2It is aralkyl phenyl；N is 6 to 100 integer, and m is 0 to 50
Integer, restrictive condition is n >=m and m+n is 6 to 100.Preferably, m=0, and n is integer 10 to 60；And it is more excellent
Selection of land, m=0, and n are integers 20 to 40.
The example of polyethoxylated aralkylphenol (methyl) acrylate includes coming from Solvay Chemicals, Inc.
Polyethoxylated triphenyl vinyl phenol methacrylate (with commodity SIPOMER SEM-25 (60% activity) and
SIPOMER HPM-400 (50% activity) form is commercially available).
Specifically, in one embodiment of the invention, HASE includes the poly- second with 25 ethylene oxide (EO) units
The structural unit of oxygroup triphenyl vinyl phenol, as represented by following chemical constitution：
HASE polymer is prepared by well-known emulsion polymerization in fields.In certain embodiments of the present invention
In, thermal initiation technique or Redox Initiator method may be used as a part for emulsion polymerisation process.Suitable free radical causes
The example of agent includes hydrogen peroxide, sodium peroxide, potassium peroxide, tert-butyl hydroperoxide, ammonium persulfate and/or alkali metal over cure
The ammonium or alkali metal salt of hydrochlorate, sodium perborate, peroxophosphoric acid and its salt, potassium permanganate and peroxy-disulfuric acid.Radical initiator
Dosage usually can be 0.01 weight % to 3.0 weight % in terms of the dry weight of monomer.
It includes outside initiator as described above plus the oxygen of suitable reducing agent that can also be used in emulsion polymerisation process
Original system is gone back in change.The example of suitable reducing agent includes sodium sulfoxylate formaldehyde, ascorbic acid, arabo-ascorbic acid, the acid containing sulphur
Alkali metal salt and ammonium salt (such as sodium sulfite, bisulfites, thiosulfate, sulfoxylate, sulfide, sulfohydrate or
Dithionite), methyl sulfinate, methylol sulfonic acid, acetone bisulfites, glycolic, glyoxylic acid hydrate, lactic acid,
The salt of glyceric acid, malic acid, tartaric acid and aforementioned acid.Catalytic iron, copper, manganese, silver, platinum, vanadium, nickel, chromium, palladium or cobalt can be used
Metal salt redox reaction.Can before polymerization, during or after add other additives, such as free radical draws
Send out agent, oxidant, reducing agent, neutralizer and dispersant.
In some embodiments it is possible to which neutralizer is added in aqueous emulsion polymer during or after reacting the period
To control pH.Neutralizer can be selected from mineral alkali, such as sodium hydroxide, potassium hydroxide, phosphate；Organic amine, such as alkyl hydroxylamine and
Ammonia.
Preferably, highly filled in order to ensure having in the water-based composition Chain transfer agent of the present invention, such as positive ten
The dosage of dialkyl group mercaptan in terms of the dry weight of monomer mixture should between 0.01 weight % and 0.3 weight %, or more preferably
Ground is between 0.01 weight % and 0.2 weight %, or more preferably between 0.01 weight % and 0.1 weight %.It is total in lotion
In polymers the water-swellable increase of possibility or elongation reduced capability are avoided using this small amount of chain-transferring agent.
Other suitable surfactants may include styrenated phenol sulfate, such as HitenolTMBC-1025 (comes
Montello inc. from the Tulsas Russia carat He Ma Zhou), AerosolTMNPES -930 (polyoxyethylene) nonyl phenol (NP)
Ammonium sulfate (the Cytec Industries from New Jersey Wood orchid Parker)；Ethoxylation styrenated phenol sulfate,
Such as E-SperseTMRS-1596 and E-SperseTMRS-1618 (the Ethox from South Carolina Greeneville
Chemicals)；With sodium dodecyl allyl base sodium sulfosuccinate, such as TREMTMLF-40 is (from Ohio Cincinnati
Section is peaceful (Cognis)).
In certain embodiments, the amount of the HASE in paper coating composition of the invention is with total face in paper coating composition
The dry weight meter of doses can be with 0.01 weight % to 1 weight %, preferably 0.03 weight % to 0.6 weight % and more preferable 0.05
The amount of weight % to 0.4 weight % exists.
Starch
In certain embodiments of the present invention, coating composition further includes starch.As used herein, " starch " is contained
Lid is known as the material of starch or flour, can come from it is one or more in a variety of sources, such as corn, wheat, pea, Ma Ling
Known other sources in potato, rice, cassava and industry.Starch is substituted or is unsubstituted.Two can be used
The combination of kind or more the starch of type.
In one embodiment, starch is thinned starch." thinned starch " refers to the decreased starch of molecular weight, such as
Pass through acid or chemical hydrolysis, enzyme hydrolysis, mechanical force or other means.The starch product being suitable for the invention in some embodiments
An example come from National Starch chemical company (National Starch&Chemical Company).
In one embodiment, the amount of the starch in paper coating composition of the invention is in paper coating composition
The dry weight meter of amount of pigment can be 0.1 weight % to 10 weight % and preferably 1 weight % to 9 weight %, more preferable 3 weight %
To 7 weight %.
Coating composition
The coating composition of the present invention can be prepared by widely-known technique in paper paint field.Implement at one
Example in, prepare the present invention coating composition method can include mixed adhesive aqueous dispersion, pigment slurry, starch it is molten
Liquid, HASE polymer and water.Neutralizer is added in dispersion to control pH.As described above, it can also be added other
Optional component.Component in coating composition can be mixed in any order to provide the coating composition of the present invention.It can be with
During mixing or forward direction composition in add any one of above-mentioned optional components to form coating composition.In certain realities
It applies in example, the amount of the solid in coating composition is with the total weight of coating composition between 30 weight % and 75 weight %.
In certain embodiments, coating composition of the invention can include dispersant, OBA, dyestuff, biocide, cosolvent and table
Face activating agent.
Paper coating composition can be coated in paper substrates by widely-known technique in fields.Citing comes
It says, after forming paper substrates, paper coating composition can be used and roll applicator, such as metered size press (metered
size press)；Knife type coater, such as short residence time applicator；Kohler coater；Slot-die coater, such as spray applicators；
Or brush coats.Preferred coating method for high-speed applications includes knife type coater and metered size press.
As described above, the coating composition of the present invention is particularly useful as the precoated material during paper-making process.In addition, this hair
Bright water-based paint compositions can be used alone or be used with other Coating material compositions to form laminated coating on paper surface.
Example
Following instance illustrates the advantage of the present invention.Unless otherwise stated, otherwise all conditions are normal pressure and room temperature.
Raw materials
The following table 1 lists the adhesive dispersion for being used to prepare coating composition of the present invention and comparing coating composition.Together
Sample, the following table 2 lists the representative for being used to prepare coating composition of the present invention and comparing the HASE polymer in coating composition
Property raw material.The following table 3 shows the additional materials that can be added in adhesive dispersion and HASE polymer to prepare this
Invention coating composition and compare coating composition.Table 1-3 shows the work(of the acronym of these chemicals, each material
It can and can therefrom obtain the commercial supplier of these materials.
Table 1- is used to prepare
The representative inventory of the raw material of adhesive dispersion
| Chemical name | Function | Supplier |
| Styrene butadiene | Adhesive | BASF (BASF) |
Table 2- is used to prepare
The representative inventory of the raw material of the alkali swellability lotion (HASE) of hydrophobically modified
Table 3- is for manufacturing
Compare the representative inventory of the additional source material of coating composition and coating composition of the present invention
| Raw material | Function | Supplier |
| CaCO3Slurries | Pigment slurry | Ou meter Ya companies (Omya Company) |
| Sodium hydroxide (10% activity) | Neutralizer | Chinese Medicine chemical reagent Co., Ltd |
| Starch | Water-soluble binder | GFE Company |
Analysis method
Analysis coating composition sample of the present invention and the viscosity for comparing coating composition sample.Particularly, by can be from
Bo Le flies the Bo Le of engineering experiment room Co., Ltd (Brookfield Engineering Laboratories, Inc.) acquisition
Fly viscosimeter DV-II+Pro EXTRA devices and coating composition is represented to measure with the low shear rate under 50rpm with main shaft 5
The rich Le of low-shear viscosity flies (Brookfield, BF) viscosity (being measured as unit of cps).In general, higher rich strangle flies
Viscosity readings show better thickening efficiency.
Sample preparation
1.Starch solution for comparing coating composition and coating composition of the present invention
100 grams of starch powders were distributed in 186 grams of DI water in 5 minutes by being stirred with 200-1500rpm, then with
500-2000rpm is heated to 90-95 DEG C and continues 20 minutes in the case of continuously stirring.After powder dissolving, amidin is obtained.
2.Prepare the HASE for coating composition of the present invention
500.00 grams of DI water and 16.10 grams of 32 emulsifiers of DISPONIL FES are packed into equipped with mechanical agitator, nitrogen
In five liters of four-neck flasks of purging device, thermocouple and condenser.Flask is heated to 86 DEG C.By 1.12 grams of ammonium persulfates (APS)
It is dissolved in 16 grams of DI water, and is added in flask to cause polymerization process.It waits for two minutes, then into flask, addition includes
Monomer mixture below：291.90 grams of EA, 287.80 grams of MAA, 51.75 grams of SIPOMER SEM-25,16.10 grams be blended in
32 emulsifiers of DISPONIL FES in 600.00 grams of DI water and 0.34 gram of APS by being dissolved in 58.0 grams of DI water are formed
Extra freight initiator mixture, it is fed to jointly within 80 minute period in the flask of monomer mixture,
Flask temperature is maintained at 86 DEG C simultaneously.
Then, flask temperature is maintained at 86 DEG C ten minutes, is then cooled to 60 DEG C.Mixture is tracked by 20.0 grams
FeSO4Solution (0.15%), 0.42 gram of t-BHP and 0.21 gram be blended in 10.00 grams of DI water are blended in 14.00 grams of DI water
IAA composition, be then added in flask.It is maintained at 60 DEG C after 15 minutes, same amount of tracking mixture is again loaded into
In flask.Then flask is cooled to 40 DEG C, and delays the sodium acetate that 1.1 grams are blended in 130.00 grams of DI water in 10 minutes
Fliud flushing solution is added in flask.Then, the KATHON LX that microbiocidal solutions are blended in by 3.71 grams in 12 grams of DI water are killed
Biological agent (1.5% activity) composition, is added in 10 minutes in flask.After the completion of polymerization process, by gained HASE
Lotion is cooled to ambient temperature and filters the sieve of 325 mesh sizes.
Above procedure illustrates the method for being used to prepare the HASE polymer used in coating composition 1 of the present invention, described
Method generates the HASE polymer containing 5%SIPOMER SEM-25 in its composition.
The program for being used to prepare the HASE polymer used in coating composition 2 of the present invention be it is substantially similar, in addition to
It has 7%SEM-25 in forming.
3.Prepare the HASE for comparing coating composition
Several relatively coating compositions are prepared to prove the advantage of the present invention.It is worth noting that, being used to prepare these ratios
It is similar to the above-mentioned program for coating composition of the present invention compared with the program of the HASE polymer used in coating composition.
One significant difference is to use polyoxyethylene cetyl base-tristearin methyl acrylate and EA and MAA systems
Be ready for use on compare coating composition 1 HASE come instead of using SIPOMER SEM-25 as associative monomer prepare HASE.No
SIPOMER SEM-25 as containing multiple hydrophobic alkyl phenyl, polyoxyethylene cetyl base-stearyl (C16-18) metering system
Acid esters is linear alkyl chain.For comparing coating composition 1,5% polyoxyethylene cetyl base-tristearin is contained in its composition
Methyl acrylate.
Similarly, for comparing coating composition 2, polyoxyethylene docosyl-tricosyl metering system is used
Acid esters (commercially available in the form of SIPOMER BEM) and EA and MAA prepare the HASE polymer for coating composition.With
Compare the polyoxyethylene cetyl base-stearyl methyl acrylic ester used in coating composition 1 seemingly, polyoxyethylene 22
Alkyl-tricosyl (C22-23) methacrylate is also straight chained alkyl, the difference is that it is with longer carbochain.It is right
In comparing coating composition 2,3% polyoxyethylene docosyl-tricosane methacrylic acid is contained in its composition
Ester.
4.Prepare coating composition
After preparing starch solution, pigment slurry and HASE polymer, prepares coating composition of the present invention and compare coating
Composition.In order to prepare coating composition 1 of the present invention, by 400 grams of pigment slurries (calcium carbonate serosity) and 55.7 grams of starch solutions
And 36 grams of styrenebutadiene adhesives are mixed into 1L barrels and are stirred continuously with 300rpm at room temperature.Then, will
1.6 grams of sodium hydroxides (10% activity) are added slowly in mixture so that the pH of coating composition is raised to 9 or more.Meanwhile it using
Same amount of DI water dilutes 0.8 gram of HASE, is then added in coating composition the percentage of solids drop so that coating composition
As low as 68%.Finally, before the rich Le of test flies viscosity, coating composition is stirred 8 minutes with 800rpm.
In order to prepare coating composition 2 of the present invention, comparing coating composition 1 and compare coating composition 2, above-mentioned phase is used
Same step.
Analysis result
The following table 4 compares the thickening efficiency of coating composition of the present invention coating composition compared with, just wins and strangles winged viscosity
It is measured for Viscosity readings on meter.
The thickening efficiency for the coating composition that table 4- is analyzed
It as shown in upper table 4, is introduced into coating composition in the case that by the HASE polymer of same percentage, the present invention
Coating composition 1 and 2 shows thickening efficiency much higher compared with the thickening efficiency of coating composition 1 and 2 frequently.These result tables
It is bright, it is proved as compared lower thickening efficiency in coating composition 1 and 2, the carbochain of the associative monomer in HASE polymer
The variation of length does not have any active influence to thickening efficiency.
On the contrary, when HASE polymer is by the associative monomer with the polyethoxylated triphenyl vinyl phenol as end group
When being made (such as the case where coating composition 1 and 2 of the present invention), coating composition shows significantly improving for thickening efficiency.It is this
The raising of thickening efficiency will cause cost savings.
Claims (10)
1. a kind of paper coating composition, it includes the aqueous dispersions of 1) adhesive；2) pigment；3) starch；With 4) include carboxylic acid list
The structural unit of body, acrylate monomer and polyethoxylated aralkylphenol (methyl) acrylate with following formula it is hydrophobic
Modified alkali swellability lotion：
H2C=C (R) CO2(CH2CH2O)n(CH(R1)CH2O)mR2,
Wherein R is H or CH3, R1It is methyl or ethyl；R2It is aralkyl phenyl；N is 6 to 100 integer and m is 0 to 50
Integer, restrictive condition is n >=m and m+n is 6 to 100.
2. paper coating composition according to claim 1, wherein R2It is tristyrylphenyl, n is 20 to 30 integer,
And m is 0.
3. paper coating composition according to claim 1, wherein the amount of the alkali swellability lotion of the hydrophobically modified
It is 0.01 weight % to 1 weight % in terms of the dry weight of total amount of pigment in the paper coating composition.
4. paper coating composition according to claim 1, wherein the pigment is clay, titanium dioxide or calcium carbonate, or
Talcum or silica or alumina silicate or or mixtures thereof hydrated alumina or aluminum trihydrate.
5. paper coating composition according to claim 1, wherein the alkali swellability lotion of the hydrophobically modified is dredged with described
The dry weight meter for the alkali swellability lotion that water is modified includes structural unit, 40 weights of 35 weight % to 55 weight % methacrylic acids
Structural units and 0.5 weight % to 20 weight % polyethoxylated aralkylphenol first of the amount % to 55 weight % ethyl acrylates
Base acrylate.
6. paper coating composition according to claim 1, the aqueous dispersion of wherein described adhesive is a) acrylic acid copolymer
Object, b) styrene acrylic copolymer, c) styrene-butadiene-copolymer or d) vinyl acrylic copolymers and its mixture
Aqueous dispersion.
7. paper coating composition according to claim 1, the wherein aqueous dispersion of described adhesive are with the paper coating group
The dry weight meter for closing the amount of pigment in object accounts for 3 weight % to 20 weight %.
8. paper coating composition according to claim 1, wherein the starch is with the pigment in the paper coating composition
The dry weight meter of amount accounts for 0.1 weight % to 10 weight %, preferably 1.0 weight % to 9.0 weight % and more preferable 3.0 weight % is arrived
7.0 weight %.
9. a kind of coating paper substrates, it includes the coating compositions according to any one of claim 1 to 8.
10. a kind of method forming coating paper substrates, it includes：(a) paper substrates are formed；(b) coating composition is formed, it includes
The aqueous dispersion of mixed adhesive, pigment, the alkali swellability lotion of hydrophobically modified and starch under stiring hydrophobic change wherein described
Property alkali swellability lotion include carboxylic acid monomer, acrylate monomer and polyethoxylated aralkylphenol methacrylate
Structural unit；It (c) will be on one or more surfaces of the coating composition to the paper substrates.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/CN2016/076724 WO2017156769A1 (en) | 2016-03-18 | 2016-03-18 | Paper coating composition and processes of making thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108779608A true CN108779608A (en) | 2018-11-09 |
Family
ID=59851305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680083682.4A Pending CN108779608A (en) | 2016-03-18 | 2016-03-18 | Paper coating composition and preparation method |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP3430201A4 (en) |
| JP (1) | JP2019513194A (en) |
| KR (1) | KR20180126485A (en) |
| CN (1) | CN108779608A (en) |
| AU (1) | AU2016397589A1 (en) |
| BR (1) | BR112018068713A2 (en) |
| CA (1) | CA3017981A1 (en) |
| MX (1) | MX2018011266A (en) |
| WO (1) | WO2017156769A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6744672B1 (en) * | 2019-05-20 | 2020-08-19 | 株式会社Ｔｂｍ | Printing sheet and method for manufacturing printing sheet |
| JP2021046549A (en) * | 2020-11-20 | 2021-03-25 | ダウ グローバル テクノロジーズ エルエルシー | Paper coating composition and processes of making the same |
| KR102396414B1 (en) * | 2020-12-10 | 2022-05-10 | 한국신발피혁연구원 | Biodegradable resin composition using plant fattyacid possible to recycling for coating paper |
| WO2024064582A1 (en) * | 2022-09-20 | 2024-03-28 | Rohm And Haas Company | Method for preparing a microbe resistant acrylic latex |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1283206A (en) * | 1997-12-29 | 2001-02-07 | 罗狄亚化学公司 | Diol assiciative alkaline soluble copolymer and its use as thichkening agent for paper coating |
| CN101522989A (en) * | 2006-10-12 | 2009-09-02 | 高帝斯股份有限公司 | Use of an aqueous suspension and/or dispersion of mineral materials containing a hydrophobic group water-soluble copolymer for making a paper sheet |
| CN102257218A (en) * | 2008-12-18 | 2011-11-23 | 凯米罗总公司 | Coating colour composition and paper or paperboard coated with it |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2766107B1 (en) * | 1997-07-18 | 1999-08-20 | Pluss Stauffer Ag | AQUEOUS SUSPENSIONS OF MINERALS AND USES THEREOF |
| FR2766106B1 (en) * | 1997-07-18 | 2001-09-07 | Coatex Sa | USE OF A COPOLYMER WITH SURFACTORY STRUCTURE AS A DISPERSING AND / OR GRINDING AID |
| GB0304354D0 (en) * | 2003-02-26 | 2003-04-02 | Ciba Spec Chem Water Treat Ltd | Modification of paper coating rheology |
| US20060241209A1 (en) * | 2005-04-22 | 2006-10-26 | Madle Thomas G | Colorants, dispersants, dispersions, and inks |
| US20060266488A1 (en) * | 2005-05-26 | 2006-11-30 | Doherty Erin A S | Hydrophobic polymers and their use in preparing cellulosic fiber compositions |
| JP2006348112A (en) * | 2005-06-14 | 2006-12-28 | Nippon Nsc Ltd | Alkaline thickening agent |
| JP4926547B2 (en) * | 2006-06-07 | 2012-05-09 | ソマール株式会社 | Paper coating liquid and coated paper using the same |
| EP2368923B1 (en) * | 2010-03-23 | 2013-05-01 | Rohm and Haas Company | Method for producing hydrophobically modified acrylic rheology modifiers |
| EP2712898B1 (en) * | 2012-09-28 | 2014-11-26 | Rohm and Haas Company | Hydrophobically modified alkali soluble emulsion composition with polymeric beads |
-
2016
- 2016-03-18 WO PCT/CN2016/076724 patent/WO2017156769A1/en active Application Filing
- 2016-03-18 CA CA3017981A patent/CA3017981A1/en not_active Abandoned
- 2016-03-18 MX MX2018011266A patent/MX2018011266A/en unknown
- 2016-03-18 EP EP16893934.6A patent/EP3430201A4/en not_active Withdrawn
- 2016-03-18 CN CN201680083682.4A patent/CN108779608A/en active Pending
- 2016-03-18 JP JP2018549263A patent/JP2019513194A/en active Pending
- 2016-03-18 BR BR112018068713A patent/BR112018068713A2/en not_active IP Right Cessation
- 2016-03-18 AU AU2016397589A patent/AU2016397589A1/en not_active Abandoned
- 2016-03-18 KR KR1020187027431A patent/KR20180126485A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1283206A (en) * | 1997-12-29 | 2001-02-07 | 罗狄亚化学公司 | Diol assiciative alkaline soluble copolymer and its use as thichkening agent for paper coating |
| CN101522989A (en) * | 2006-10-12 | 2009-09-02 | 高帝斯股份有限公司 | Use of an aqueous suspension and/or dispersion of mineral materials containing a hydrophobic group water-soluble copolymer for making a paper sheet |
| CN102257218A (en) * | 2008-12-18 | 2011-11-23 | 凯米罗总公司 | Coating colour composition and paper or paperboard coated with it |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3430201A4 (en) | 2019-10-30 |
| JP2019513194A (en) | 2019-05-23 |
| AU2016397589A1 (en) | 2018-10-25 |
| WO2017156769A1 (en) | 2017-09-21 |
| CA3017981A1 (en) | 2017-09-21 |
| KR20180126485A (en) | 2018-11-27 |
| BR112018068713A2 (en) | 2019-01-22 |
| MX2018011266A (en) | 2019-02-13 |
| EP3430201A1 (en) | 2019-01-23 |
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Application publication date: 20181109 |