WO1994024202A1 - Latex copolymers for paper coating compositions - Google Patents

Latex copolymers for paper coating compositions Download PDF

Info

Publication number
WO1994024202A1
WO1994024202A1 PCT/US1993/003618 US9303618W WO9424202A1 WO 1994024202 A1 WO1994024202 A1 WO 1994024202A1 US 9303618 W US9303618 W US 9303618W WO 9424202 A1 WO9424202 A1 WO 9424202A1
Authority
WO
WIPO (PCT)
Prior art keywords
monomers
latex
present
latex copolymer
ethylene glycol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1993/003618
Other languages
French (fr)
Inventor
Bradley J. Helmer
Shirley J. Loughney
Jon Macdonagh-Dumler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Priority to AU40323/93A priority Critical patent/AU4032393A/en
Priority to PCT/US1993/003618 priority patent/WO1994024202A1/en
Publication of WO1994024202A1 publication Critical patent/WO1994024202A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers

Definitions

  • This invention is related to latexes for use in paper coating formulations to improve and optimize paper properties such as sheet gloss, ink gloss and smoothness, to processes for the preparation of the latexes and paper coating compositions
  • Paper coating formulations which comprise latex copolymers are used extensively by the paper industry Improvements in properties such as sheet gloss, ink gloss and smoothness are continuously sought after through the development of new latexes for inclusion in paper coating formulations
  • Coated cellulosic web or paper web is prepared utilizing a pigment, such as clay, and other components which stabilize and disperse the pigment in a water slurry
  • the slurry is formulated with a binder to produce the coating color, a paper coating composition which is used to coat the web or paper
  • the components of the coating color contribute to the performance of the process of coating the web, and to the performance of the coated paper If the paper is a higher quality grade paper, the finished coated web should have a high degree of brightness, smoothness and gloss, as well as a good finish and feel after the web is calendered.
  • the coating color must have sufficient strength and binding capability to enable printing of the coated paper without "picking ", that is, without the coating separating from either the paper surface or from within the coating.
  • U S Patent No 4,440,896 discloses the use of water-soluble polymers of ethylene glycol in binder formulations comprising a latex
  • U S Patent No 4,717,502 discloses the use of polyethylene glycol in aqueous optical brightener compositions It would be desirable to have new latexes which provide improved physical characteristics for paper coating formulations and coating colors without the prior art disadvantages associated with admixture of polyethylene glycols therein
  • the present invention relates to a latex copolymer comprising in polymerized form one or more ethylenicaUy unsaturated poly(ethylene glycol) monomers represented by the following formula
  • R 1 is an ethylenicaUy unsaturated functional group
  • R is H, OH or OCH 3
  • n is from 3 to 20
  • one or more comonomers selected from monovinyl aromatic monomers, aliphatic conjugated diene monomers, acrylate monomers, vmylidene halide monomers, vinyl halide monomers, vinyl esters of carboxyl acids containing from 1 to 18 carbon atoms, methacrylonitrile, acrylonitrile, ana monoethylenically unsaturated carboxylic acid monomers.
  • a process for the preparation of a latex copolymer comprising emulsion polymerizing a polymerization mixture comD ⁇ sing between 1 and 15 parts per hundred part by weight based on the total weight of monomers present in the latex copolymer of one or more ethylenicaUy unsaturated poly(ethylene glycol) monomers represented by the following formula:
  • R' is an ethylenicaUy unsaturated functional group; R is H, OH or OCH 3 ; and n is from 3 to 20, and one or more comonomers selected from monovmyl aromatic monomers, aliphatic conjugated diene monomers, acrylate monomers, vmylidene halide monomers, vinyl halide c monomers, vinyl esters of carboxyl acids containing from 1 to 18 carbon atoms, methacrylonitrile, acrylonitrile, and monoethylenically unsaturated carboxylic acid monomers.
  • comonomers selected from monovmyl aromatic monomers, aliphatic conjugated diene monomers, acrylate monomers, vmylidene halide monomers, vinyl halide c monomers, vinyl esters of carboxyl acids containing from 1 to 18 carbon atoms, methacrylonitrile, acrylonitrile, and monoethylenically unsaturated carboxylic acid monomers.
  • the instant invention relates to a paper coating composition
  • a paper coating composition comprising latex copolymer comprising in polymerized form one or more ethylenicaUy unsaturated poly(ethylene glycol) monomers represented by the following 0 formula:
  • R' is an ethylenicaUy unsaturated functional group; R is H, OH or OCH 3 ; and n is from 3 5 to 20, and one or more comonomers selected from monovmyl aromatic monomers, aliphatic conjugated diene monomers, acrylate monomers, vmylidene halide monomers, vinyl halide monomers, vinyl esters of carboxyl acids containing from 1 to 18 carbon atoms, methacrylonitrile, acrylonitrile, and monoethylenically unsaturated carboxylic acid monomers; and mixed therewith: one or more pigments; and, optionally, one or more binders; and, optionally, one or more stabilizing agents; ana. optionally, a defoamer.
  • a process for the oreparation of a 5 pa ⁇ e r coating composition comprising emulsion polymerizing a polymerization mixture comD ⁇ sing between 1 and 15 parts per hundred part by weight based on the total weight of monomer present in the latex copolymer of one or more ethylenicaUy unsaturated poly(ethylene glycol) monomers represented by the following formula:
  • R 1 is an ethylenicaUy unsaturated functional group
  • R is H, OH or OCH 3
  • n is from 3 to 20, and one or more comonomers selected from monovmyl aromatic monomers, aliphatic conjugated diene monomers, acrylate monomers, vinylidene halide monomers, vinyl halide 0 monomers, vinyl esters of carboxyl acids containing from 1 to 18 carbon atoms, methacrylonitrile, acrylonitrile, and monoethylenically unsaturated carboxylic acid monomers; and mixing therewith in any order: one or more pigments; and, optionally, one or more binders; and, optionally, r one or more stabilizing agents; and, optionally, a defoamer.
  • R 1 is a vinyl group or a propenyl group, n is from 7 to 15 and R is OH.
  • the ethylenicaUy unsaturated poly(ethylene glycol) monomer 0 be present in the latex copolymer in an amount between 1 and 15 parts per hundred based on the total weight of the monomer and comonomers present in the latex copolymer, preferably between 5 and 10 parts per hundred based on the total weight of the monomer and comonomers present in the latex copolymer.
  • the comonomers and mixtures of comonomers which are suitably employed with c the ethylenicaUy unsaturated poly(ethylene glycol) monomers in the present invention include monovmyl aromatic monomers; aliphatic conjugated diene monomers; acrylate monomers; vinylidene halide or vinyl halide monomers; vinyl esters of carboxylic acids containing from 1 to 18 carbon atoms, such as vinyl acetate or vinyl stearate; methacrylonitrile, and acrylonitrile.
  • a monoethylenically unsaturated carboxylic acid monomer could also be used.
  • onovinyl 0 aromatic monomers and aliphatic conjugated diene monomers are preferred.
  • wnerein R is hydrogen or a lower alkyl such as an alkyl having from 1 to 4 carbon atoms, including those wherein the aromatic nucleus is substituted with alkyl or halogen substituents Examples include styrene, alpha methyl styrene, p-methyl styrene, t-butyl styrene, vinyltoluene, and halogenated styrene
  • the preferred monomer is styrene
  • the effective amount of monovinyl aromatic comonomer present with the ethylenicaUy unsaturated poly(ethylene glycol) monomers will depend on whether (i) the ethylenicaUy unsaturated poly(ethyiene glycol)-conta ⁇ n ⁇ ng latex copolymer is acting alone as a binder or (n) the ethylenicaUy unsaturated poly(ethylene glycol)
  • aliphatic conjugated diene is meant to include comonomer compounds such as isoprene, 1 ,3-butad ⁇ ene, 2-methyl-1 ,3-butad ⁇ ene, piperylene (1,3-pentad ⁇ ene), and other hydrocarbon analogs of 1 ,3-butad ⁇ ene
  • amount of aliphatic conjugated diene monomer present with the poly(ethylene glycol) comonomer will depend on monomers chosen, however, if a monovinyl aromatic monomer is a comonomer, the typical range will be from 30 to 70 weight percent aliphatic conjugated diene based on the total weight of the comonomers present
  • the latexes of the present invention which are mixed with binding latexes have more flexible ranges for aliphatic conjugated diene levels "Vinylidene halide" and "vinyl halide monomers" are also suitable for this invention which can include the preferred vinyl
  • acrylate is meant to include the acrylate or methacrylate comonomers
  • the acrylates can include acids, esters, amides, and substituted derivatives thereof
  • the preferred acrylates are C.-C 3 alkyl acrylates or methacrylates
  • Examples of such acrylates include butyl acrylate, hexyl acrylate, 2-ethyl hexyl acrylate, tert-butyl acrylate, methylmethacrylate, Dutylmethacrylate, ethyl methacrylate, hexylmethacrylate, isobutylmethacrylate, and isoDropylmethacrylate
  • the preferred acrylates are butyl acrylate and methylmethacrylate
  • the amount of acrylate present with the D ⁇ ly(ethylene glycol) comonomer will depend on monomer chosen however, the desirable range will be from 0 to 95 weight percent based on the total weight of monomer present
  • R 1 isan ethylenicaUy unsaturated functional group
  • R is H, OH or OCH 3
  • n is from 3 to 20, and preferably 5 to 10.
  • the preferred ethylenicaUy unsaturated poly(ethylene glycol) monomers are where R 1 is a vinyl group or propenyl and n is 7 to 15 and R is OH. 0
  • the R 1 group is meant to act as the functional group through which the monomers link to form the polymer chain and various options for Ri will be readily ascertained by a skilled artisan.
  • the ethylenicaUy unsaturated poly(ethylene glycol) acts as a 5 functional group which interacts with inorganic pigments such as clay in the coating color.
  • inorganic pigments such as clay in the coating color.
  • the effective qualitative amount of poly(ethylene glycol) monomer present in the latex of the present invention is typically between 1 and 15 parts per hundred based on total 0 monomer present in the latex copolymer
  • a preferred amount of poly(ethylene glycol) monomer present in the latex is between 5 and 10 parts based on total monomer present in the latex
  • binders can be suitably blended with the poly(ethylene glycol)-conta ⁇ n ⁇ ng latexes in paper coating compositions of the instant c invention.
  • binders include the natural binders: starch; modified starch such as oxidized, enzyme converted or hydroxy-ethylated starch; soybean protein, casein as well as the synthetic binders
  • the synthetic binders include the styrene-butadiene latexes
  • the binder may also be a mixture of various binding materials
  • the ethylenicaUy unsaturated poly(ethylene glycol)-conta ⁇ n ⁇ ng latexes can be blended with such conventional binding latexes typically in an amount from 10 weight percent to 50 weight percent poly(ethylene glycol)-conta ⁇ n ⁇ ng latex to binding latex.
  • the preferred amount of poly(ethylene glycol)-conta ⁇ n ⁇ ng latex is from 20 weight percent to 45 weight percent. The most preferred amount is approximately 25 weight percent ethylenicaUy unsaturated poly(ethylene glycol)-conta ⁇ n ⁇ ng latex.
  • the coating color typically comprises 100 parts pigment containing from 65 to 100 parts clay; and 0 to 35 parts secondary pigment; 0.01 to 0.5 parts dispersing or stabilizing agent; 0.5 to 25 parts of ethylenicaUy unsaturated poiy(ethylene glycol)-contain ⁇ ng latex; O to 25 parts co-binder; O to 0.2 parts defoamer and sufficient amounts of water to provide the desired solids level, usually 35 to 70 weight percent solids.
  • the modifications and formulations of the coating color are within the knowledge of a person skilled in the art.
  • the inorganic or mineral pigments with which the poly(ethylene glycol)- containing latex particle interacts can be chosen rom the finely divided clays (particularly kaolin types); calcium carbonate; titanium dioxide; satin white and the like. Pigmentary materials such as talc; blanc fixe; ocre; carbon black; aluminum can also be employed.
  • the paper coating composition also known as a coating color, can be applied to the paper substrate by conventional techniques such as air knife, trailing blade, inverted blade, roll coater and short dwell coater.
  • the substrate is then dried and the paper may then be calendered or super calendered depending on the quality grade of the paper being produced.
  • the paper-coating properties which illustrate the utility of the present invention include, but are not limited to, dry pick and sheet gloss. Sheet gloss is often achieved by sacrificing dry pick (how well the coating is bound to the paper).
  • the present invention enables the paper coating to maintain dry pick and simultaneously increase sheet gloss.
  • the paper is analyzed for the properties of sheet gloss and pick strength using standard methods.
  • the pick resistance of the paper is tested by using the TAPPI standard method T 499-su-64 with a Westvaco Rod Applicator.
  • the specular gloss of Paper at 75 degrees is tested using the TAPPI standard method T 480-os-78.
  • Doiy(ethylene glycol) monomer-containing latex was prepared in the following manner. Into a 1-gallon pressurized stainless steel reactor was added 813 grams (g) of water, 1.23 g of a 45 percent active surfactant solution, 0.89 g of 10 percent sulfu ⁇ c acid, 1 1.1 g of a 1 percent active aqueous pentasodium diethylene t ⁇ amine pentaacetate solution and 26.35 g of a seed latex which will render a particle size having a diameter of approximately 1400 A.
  • the reactor was purged with nitrogen and heated to 90°C and over a 5-hour period was added a monomer stream containing: 530 g of butadiene; 140 g of the ethylenicaUy unsaturated poly(ethylene glycol) monomer which was ⁇ -(2-methyl- 1 -oxo- 2-propenyl)- ⁇ -hydroxy-poly(oxy-1 ,2-ethanediyl), having approximately 20 ethylene oxide units (hereinafter "HEM 20”) commercially available from Alcolac as a poly(ethylene glycol) monomethacrylate; 9.0 g of a mercaptan chain-transfer agent; and 726 g of styrene.
  • HEM 20 ethylene oxide units
  • a paper coating formulation was prepared by the following method. A sufficient amount of water to make a 72 percent slurry of 2000 grams dry No. 1 Coating Clay and 0.1 part sodium polyacrylate as a dispersant was added to a blender. Approximately two thirds of the total clay was added to the blender and the blender was run on low speed until the clay was wetted. The remaining clay was added and run on low speed until all the clay was wetted. The pigment was then dispersed on high speed for one minute.
  • the paper, or basestock to which the coating formulation was applied was a 28 lb. per 3300 ft. 2 groundwood containing publication stock.
  • the basestock was coated on a Dow Bench Blade Coater manufactured by Modern Metaicraft of Midland, Michigan. A 12 inch web was coated at approximately 12 ft. per minute using a puddle blade coater with drying on a heated steel drum. Circulating glycol at 205°F to 215°F through the drum was sufficient for heating. After the paper was dried samples were cut into sizes appropriate for testing.
  • the latex binder was comprised of 75 percent of a carboxylated styrene butadiene latex and 25 percent of the ethylenicaUy unsaturated poly(ethylene glycol) monomer- containing latex prepared above.
  • the sheet gloss for the paper coated with the coating color formulation was 62 and the dry pick was 225. Examples 2-5
  • a similar coating color was prepared using a latex prepared similarly to the latex prepared in Example 1 ; however, the latex was prepared with 5 parts of ⁇ -(2-methyi-1- oxo-2-propenyl)- ⁇ -hydroxy-poly(oxy-1 ,2-ethaned ⁇ yl), having aporoximately 10 ethylene oxide units (hereinafter "HEM 10") commercially available from Alcolac as a poly(ethylene glycol) monomethacrylate, based on weight of total monomer and the coating color was prepared with 75 percent of a carboxylated styrene butadiene latex and 25 percent of the HEM 10 latex.
  • the sheet gloss for the paper coated with the coating color formulation was 61 and the dry pick was 206.
  • a similar coating color was prepared using a latex prepared similarly to the latex prepared in Example 1 ; however, the latex was prepared with 10 parts HEM 10 based on weight of total monomer and the coating color was prepared with 75 percent of a carboxylated styrene butadiene latex and 25 percent of the HEM 10 latex.
  • the sheet gloss for the paper coated with the coating color formulation was 64 and the dry pick was 222
  • a similar coating color was prepared using a latex prepared similarly to the latex prepared in Example 1 ; however, the latex was prepared with 15 parts HEM 10 based on weight of total monomer present and the coating color was prepared with 75 percent of a carboxylated styrene butadiene latex and 25 percent of the HEM 10 latex.
  • the sheet gloss for the paper coated with the coating color formulation was 65 and the dry pick was 195.
  • a similar coating color was prepared using a latex prepared similarly to the latex prepared in Example 1 ; however, the latex was prepared with 10 parts HEM 10 based on weight of total monomer present and the coating color was prepared with 50 percent of a carboxylated styrene butadiene latex and 50 percent of the HEM 10 latex.
  • the sheet gloss for the paper coated with the coating color formulation was 65 and the dry pick was 210. Comparative Example
  • a similar coating color was prepared using a carboxylated styrene butadiene latex alone and therefore the coating color was prepared only with the carboxylated styrene butadiene latex.
  • the sheet gloss for the paper coated with the coating color formulation of the Comparative Example was 57 and the dry pick was 188 as compared to a more desirable sheet gloss of 65 and dry pick of 210 as demonstrated in Example 5

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)

Abstract

The present invention relates to a latex copolymer comprising in polymerized form one or more ethylenically unsaturated poly(ethylene glycol) monomers represented by formula (I) where R1 is an ethylenically unsaturated functional group, R is H, OH or OCH¿3?, and n is from 3 to 20, and one or more comonomers. Paper coating compositions comprising this latex copolymer impart improved sheet gloss and dry pick characteristics to the coated paper. Additional embodiments include a process for the preparation of the ethylenically unsaturated poly(ethylene glycol) monomer-containing latex copolymer and the paper coating composition.

Description

LATEX COPOLYMERS FOR PAPER COATING COMPOSITIONS
This invention is related to latexes for use in paper coating formulations to improve and optimize paper properties such as sheet gloss, ink gloss and smoothness, to processes for the preparation of the latexes and paper coating compositions
Paper coating formulations which comprise latex copolymers are used extensively by the paper industry Improvements in properties such as sheet gloss, ink gloss and smoothness are continuously sought after through the development of new latexes for inclusion in paper coating formulations Coated cellulosic web or paper web is prepared utilizing a pigment, such as clay, and other components which stabilize and disperse the pigment in a water slurry The slurry is formulated with a binder to produce the coating color, a paper coating composition which is used to coat the web or paper The components of the coating color contribute to the performance of the process of coating the web, and to the performance of the coated paper If the paper is a higher quality grade paper, the finished coated web should have a high degree of brightness, smoothness and gloss, as well as a good finish and feel after the web is calendered.
The coating color must have sufficient strength and binding capability to enable printing of the coated paper without "picking ", that is, without the coating separating from either the paper surface or from within the coating.
U S Patent No 4,440,896 discloses the use of water-soluble polymers of ethylene glycol in binder formulations comprising a latex
U S Patent No 4,717,502 discloses the use of polyethylene glycol in aqueous optical brightener compositions It would be desirable to have new latexes which provide improved physical characteristics for paper coating formulations and coating colors without the prior art disadvantages associated with admixture of polyethylene glycols therein
The present invention relates to a latex copolymer comprising in polymerized form one or more ethylenicaUy unsaturated poly(ethylene glycol) monomers represented by the following formula
0
II
R 1 -C- ( 0CH2CH2 ) n-R
where R1 is an ethylenicaUy unsaturated functional group, R is H, OH or OCH3, and n is from 3 to 20, and one or more comonomers selected from monovinyl aromatic monomers, aliphatic conjugated diene monomers, acrylate monomers, vmylidene halide monomers, vinyl halide monomers, vinyl esters of carboxyl acids containing from 1 to 18 carbon atoms, methacrylonitrile, acrylonitrile, ana monoethylenically unsaturated carboxylic acid monomers.
Within the scope of the instant invention is a process for the preparation of a latex copolymer comprising emulsion polymerizing a polymerization mixture comDπsing between 1 and 15 parts per hundred part by weight based on the total weight of monomers present in the latex copolymer of one or more ethylenicaUy unsaturated poly(ethylene glycol) monomers represented by the following formula:
0 II
R 1 -C- ( 0CH2CH2 ) n-R 0
where R' is an ethylenicaUy unsaturated functional group; R is H, OH or OCH3; and n is from 3 to 20, and one or more comonomers selected from monovmyl aromatic monomers, aliphatic conjugated diene monomers, acrylate monomers, vmylidene halide monomers, vinyl halide c monomers, vinyl esters of carboxyl acids containing from 1 to 18 carbon atoms, methacrylonitrile, acrylonitrile, and monoethylenically unsaturated carboxylic acid monomers.
In a further embodiment the instant invention relates to a paper coating composition comprising latex copolymer comprising in polymerized form one or more ethylenicaUy unsaturated poly(ethylene glycol) monomers represented by the following 0 formula:
0
R 1 -C- ( 0CH2CH2 ) n-R
where R' is an ethylenicaUy unsaturated functional group; R is H, OH or OCH3; and n is from 3 5 to 20, and one or more comonomers selected from monovmyl aromatic monomers, aliphatic conjugated diene monomers, acrylate monomers, vmylidene halide monomers, vinyl halide monomers, vinyl esters of carboxyl acids containing from 1 to 18 carbon atoms, methacrylonitrile, acrylonitrile, and monoethylenically unsaturated carboxylic acid monomers; and mixed therewith: one or more pigments; and, optionally, one or more binders; and, optionally, one or more stabilizing agents; ana. optionally, a defoamer.
Within the scope of the instant invention is a process for the oreparation of a 5 paσer coating composition comprising emulsion polymerizing a polymerization mixture comDπsing between 1 and 15 parts per hundred part by weight based on the total weight of monomer present in the latex copolymer of one or more ethylenicaUy unsaturated poly(ethylene glycol) monomers represented by the following formula:
0
II
R 1 -C- ( 0CH2CH2 ) n-R
where R1 is an ethylenicaUy unsaturated functional group; R is H, OH or OCH3; and n is from 3 to 20, and one or more comonomers selected from monovmyl aromatic monomers, aliphatic conjugated diene monomers, acrylate monomers, vinylidene halide monomers, vinyl halide 0 monomers, vinyl esters of carboxyl acids containing from 1 to 18 carbon atoms, methacrylonitrile, acrylonitrile, and monoethylenically unsaturated carboxylic acid monomers; and mixing therewith in any order: one or more pigments; and, optionally, one or more binders; and, optionally, r one or more stabilizing agents; and, optionally, a defoamer.
In preferred embodiments of the latex copolymer of the instant invention and the process for its preparation R1 is a vinyl group or a propenyl group, n is from 7 to 15 and R is OH.
It is desirable that the ethylenicaUy unsaturated poly(ethylene glycol) monomer 0 be present in the latex copolymer in an amount between 1 and 15 parts per hundred based on the total weight of the monomer and comonomers present in the latex copolymer, preferably between 5 and 10 parts per hundred based on the total weight of the monomer and comonomers present in the latex copolymer.
The comonomers and mixtures of comonomers which are suitably employed with c the ethylenicaUy unsaturated poly(ethylene glycol) monomers in the present invention include monovmyl aromatic monomers; aliphatic conjugated diene monomers; acrylate monomers; vinylidene halide or vinyl halide monomers; vinyl esters of carboxylic acids containing from 1 to 18 carbon atoms, such as vinyl acetate or vinyl stearate; methacrylonitrile, and acrylonitrile. A monoethylenically unsaturated carboxylic acid monomer could also be used. onovinyl 0 aromatic monomers and aliphatic conjugated diene monomers are preferred.
The term "monovinyl aromatic monomer", as used herein, is meant to include those monomers with a radical of the formula:
R
CH2 =C- 5
attached directly to an aromatic nucleus containing from 6 to 10 carbon atoms, wnerein R is hydrogen or a lower alkyl such as an alkyl having from 1 to 4 carbon atoms, including those wherein the aromatic nucleus is substituted with alkyl or halogen substituents Examples include styrene, alpha methyl styrene, p-methyl styrene, t-butyl styrene, vinyltoluene, and halogenated styrene The preferred monomer is styrene Typically the effective amount of monovinyl aromatic comonomer present with the ethylenicaUy unsaturated poly(ethylene glycol) monomers will depend on whether (i) the ethylenicaUy unsaturated poly(ethyiene glycol)-contaιnιng latex copolymer is acting alone as a binder or (n) the ethylenicaUy unsaturated poly(ethylene glycol)-contaιπιng latex is blended with a latex conventionally known to be useful as a binder For those latexes of the present invention which are used as binding latexes, the typical range for monovinyl aromatic comonomer present will be from 30 to 70 weight percent based on the total weight of monomer present The latexes of the present invention which are mixed with binding latexes have more flexible ranges for monovinyl aromatic comonomer levels For example, if the latexes of the present invention are intended to function as plastic pigments in a paper coating formulation then the amount of monovinyl aromatic monomer present may be up to 95 percent based on total weight of monomer present
The term "aliphatic conjugated diene", as used herein, is meant to include comonomer compounds such as isoprene, 1 ,3-butadιene, 2-methyl-1 ,3-butadιene, piperylene (1,3-pentadιene), and other hydrocarbon analogs of 1 ,3-butadιene Typically the amount of aliphatic conjugated diene monomer present with the poly(ethylene glycol) comonomer will depend on monomers chosen, however, if a monovinyl aromatic monomer is a comonomer, the typical range will be from 30 to 70 weight percent aliphatic conjugated diene based on the total weight of the comonomers present The latexes of the present invention which are mixed with binding latexes have more flexible ranges for aliphatic conjugated diene levels "Vinylidene halide" and "vinyl halide monomers" are also suitable for this invention which can include the preferred vinylidene chloride and vinyl chloride monomers Vinylidene bromide and vinyl bromide can also be employed
The term "acrylate", as used herein, is meant to include the acrylate or methacrylate comonomers The acrylates can include acids, esters, amides, and substituted derivatives thereof Generally, the preferred acrylates are C.-C3 alkyl acrylates or methacrylates Examples of such acrylates include butyl acrylate, hexyl acrylate, 2-ethyl hexyl acrylate, tert-butyl acrylate, methylmethacrylate, Dutylmethacrylate, ethyl methacrylate, hexylmethacrylate, isobutylmethacrylate, and isoDropylmethacrylate The preferred acrylates are butyl acrylate and methylmethacrylate The amount of acrylate present with the Dθly(ethylene glycol) comonomer will depend on monomer chosen however, the desirable range will be from 0 to 95 weight percent based on the total weight of monomer present The term "monoethylenically unsaturated carboxylic acid monomer", as used herein, is meant to include those monocarboxylic monomers such as acrylic acid and methacrylic acid; dicarboxylic monomers such as itaconic acid, fumaπc acid, maleic acid, and their monoesters The amount of monoethylenically unsaturated carboxylic acid comonomer present is that amount necessary to enhance stability of the latex particle Although the present latex particle may be sufficiently stable without the carboxylic acid comonomer present, atypical stabilizing amount is from 2 to 10 weight percent based on the total weight of monomer present in the copolymer 0 The ethylenicaUy unsaturated poly(ethylene glycol) monomers are represented by the following formula:
0
II
R 1 -C- ( 0CH2CH2 ) n-R
5 where R1 isan ethylenicaUy unsaturated functional group; R is H, OH or OCH3; and n is from 3 to 20, and preferably 5 to 10.
The preferred ethylenicaUy unsaturated poly(ethylene glycol) monomers are where R1 is a vinyl group or propenyl and n is 7 to 15 and R is OH. 0 The R1 group is meant to act as the functional group through which the monomers link to form the polymer chain and various options for Ri will be readily ascertained by a skilled artisan.
Although not wishing to be bound by any particular theory of operation of the instant invention, it isthoughtthat the ethylenicaUy unsaturated poly(ethylene glycol) acts as a 5 functional group which interacts with inorganic pigments such as clay in the coating color. By interacting with the clay, the coating color is thought to improve the gloss of the paper without sacrificing the strength and binding capability.
The effective qualitative amount of poly(ethylene glycol) monomer present in the latex of the present invention is typically between 1 and 15 parts per hundred based on total 0 monomer present in the latex copolymer A preferred amount of poly(ethylene glycol) monomer present in the latex is between 5 and 10 parts based on total monomer present in the latex
Typically, conventionally known binders can be suitably blended with the poly(ethylene glycol)-contaιnιng latexes in paper coating compositions of the instant c invention. Such binders include the natural binders: starch; modified starch such as oxidized, enzyme converted or hydroxy-ethylated starch; soybean protein, casein as well as the synthetic binders The synthetic binders include the styrene-butadiene latexes The binder may also be a mixture of various binding materials The ethylenicaUy unsaturated poly(ethylene glycol)-contaιnιng latexes can be blended with such conventional binding latexes typically in an amount from 10 weight percent to 50 weight percent poly(ethylene glycol)-contaιnιng latex to binding latex. The preferred amount of poly(ethylene glycol)-contaιnιng latex is from 20 weight percent to 45 weight percent. The most preferred amount is approximately 25 weight percent ethylenicaUy unsaturated poly(ethylene glycol)-contaιnιng latex. The Paper Coating Formulation
The coating color typically comprises 100 parts pigment containing from 65 to 100 parts clay; and 0 to 35 parts secondary pigment; 0.01 to 0.5 parts dispersing or stabilizing agent; 0.5 to 25 parts of ethylenicaUy unsaturated poiy(ethylene glycol)-containιng latex; O to 25 parts co-binder; O to 0.2 parts defoamer and sufficient amounts of water to provide the desired solids level, usually 35 to 70 weight percent solids. The modifications and formulations of the coating color are within the knowledge of a person skilled in the art.
The inorganic or mineral pigments with which the poly(ethylene glycol)- containing latex particle interacts can be chosen rom the finely divided clays (particularly kaolin types); calcium carbonate; titanium dioxide; satin white and the like. Pigmentary materials such as talc; blanc fixe; ocre; carbon black; aluminum can also be employed.
The paper coating composition, also known as a coating color, can be applied to the paper substrate by conventional techniques such as air knife, trailing blade, inverted blade, roll coater and short dwell coater.
The substrate is then dried and the paper may then be calendered or super calendered depending on the quality grade of the paper being produced.
The paper-coating properties which illustrate the utility of the present invention include, but are not limited to, dry pick and sheet gloss. Sheet gloss is often achieved by sacrificing dry pick (how well the coating is bound to the paper). The present invention enables the paper coating to maintain dry pick and simultaneously increase sheet gloss. The paper is analyzed for the properties of sheet gloss and pick strength using standard methods.
The pick resistance of the paper is tested by using the TAPPI standard method T 499-su-64 with a Westvaco Rod Applicator. The specular gloss of Paper at 75 degrees is tested using the TAPPI standard method T 480-os-78.
Examples of EthylenicaUy Unsaturated Poly(ethylene glycol) Monomer-Containing Latex Copolymers in Formulations with Binder Latexes Example 1
1 An ethylenicaUy unsaturated Doiy(ethylene glycol) monomer-containing latex was prepared in the following manner. Into a 1-gallon pressurized stainless steel reactor was added 813 grams (g) of water, 1.23 g of a 45 percent active surfactant solution, 0.89 g of 10 percent sulfuπc acid, 1 1.1 g of a 1 percent active aqueous pentasodium diethylene tπamine pentaacetate solution and 26.35 g of a seed latex which will render a particle size having a diameter of approximately 1400 A. The reactor was purged with nitrogen and heated to 90°C and over a 5-hour period was added a monomer stream containing: 530 g of butadiene; 140 g of the ethylenicaUy unsaturated poly(ethylene glycol) monomer which was α-(2-methyl- 1 -oxo- 2-propenyl)-ω-hydroxy-poly(oxy-1 ,2-ethanediyl), having approximately 20 ethylene oxide units (hereinafter "HEM 20") commercially available from Alcolac as a poly(ethylene glycol) monomethacrylate; 9.0 g of a mercaptan chain-transfer agent; and 726 g of styrene. Simultaneously with the monomer stream was added 485 g of water, 24 26 g of a 45 percent active surfactant solution, 24 g of a 10 percent solution of sodium hydroxide and 19 g of sodium persulfate. Following the addition of the monomer and aqueous streams, the reactor was maintained at 90°C for about 1 hour, then cooled.
A paper coating formulation was prepared by the following method. A sufficient amount of water to make a 72 percent slurry of 2000 grams dry No. 1 Coating Clay and 0.1 part sodium polyacrylate as a dispersant was added to a blender. Approximately two thirds of the total clay was added to the blender and the blender was run on low speed until the clay was wetted. The remaining clay was added and run on low speed until all the clay was wetted. The pigment was then dispersed on high speed for one minute.
100 Grams of the pigment slurry was put into an eight ounce bottle to which the latex binder was added. The coating compound was stirred with an air stirrer at a speed which will not induce a vortex, for approximately 3 to 5 minutes. The pH of the formulation was then adjusted to 8.5 to 9 with ammonium or sodium hydroxide while hand stirring the formulation. The paper, or basestock to which the coating formulation was applied was a 28 lb. per 3300 ft.2 groundwood containing publication stock. The basestock was coated on a Dow Bench Blade Coater manufactured by Modern Metaicraft of Midland, Michigan. A 12 inch web was coated at approximately 12 ft. per minute using a puddle blade coater with drying on a heated steel drum. Circulating glycol at 205°F to 215°F through the drum was sufficient for heating. After the paper was dried samples were cut into sizes appropriate for testing.
The latex binder was comprised of 75 percent of a carboxylated styrene butadiene latex and 25 percent of the ethylenicaUy unsaturated poly(ethylene glycol) monomer- containing latex prepared above. The sheet gloss for the paper coated with the coating color formulation was 62 and the dry pick was 225. Examples 2-5
2. A similar coating color was prepared using a latex prepared similarly to the latex prepared in Example 1 ; however, the latex was prepared with 5 parts of α-(2-methyi-1- oxo-2-propenyl)-ω-hydroxy-poly(oxy-1 ,2-ethanedιyl), having aporoximately 10 ethylene oxide units (hereinafter "HEM 10") commercially available from Alcolac as a poly(ethylene glycol) monomethacrylate, based on weight of total monomer and the coating color was prepared with 75 percent of a carboxylated styrene butadiene latex and 25 percent of the HEM 10 latex. The sheet gloss for the paper coated with the coating color formulation was 61 and the dry pick was 206.
3 A similar coating color was prepared using a latex prepared similarly to the latex prepared in Example 1 ; however, the latex was prepared with 10 parts HEM 10 based on weight of total monomer and the coating color was prepared with 75 percent of a carboxylated styrene butadiene latex and 25 percent of the HEM 10 latex. The sheet gloss for the paper coated with the coating color formulation was 64 and the dry pick was 222
4. A similar coating color was prepared using a latex prepared similarly to the latex prepared in Example 1 ; however, the latex was prepared with 15 parts HEM 10 based on weight of total monomer present and the coating color was prepared with 75 percent of a carboxylated styrene butadiene latex and 25 percent of the HEM 10 latex. The sheet gloss for the paper coated with the coating color formulation was 65 and the dry pick was 195.
5. A similar coating color was prepared using a latex prepared similarly to the latex prepared in Example 1 ; however, the latex was prepared with 10 parts HEM 10 based on weight of total monomer present and the coating color was prepared with 50 percent of a carboxylated styrene butadiene latex and 50 percent of the HEM 10 latex. The sheet gloss for the paper coated with the coating color formulation was 65 and the dry pick was 210. Comparative Example
A similar coating color was prepared using a carboxylated styrene butadiene latex alone and therefore the coating color was prepared only with the carboxylated styrene butadiene latex. The sheet gloss for the paper coated with the coating color formulation of the Comparative Example was 57 and the dry pick was 188 as compared to a more desirable sheet gloss of 65 and dry pick of 210 as demonstrated in Example 5
The foregoing data illustrate the desirable increase in sheet gloss and dry pick the paper exhibits when the ethylenicaUy unsaturated poly(ethylene glycol) monomer-containing latexes are incorporated into the coating color.

Claims

WHAT IS CLAIMED IS
1 A latex copolymer comprising in polymerized form one or more ethylenicaUy unsaturated poly(ethylene glycol) monomers represented by the following
5 formula:
0
R 1 -C-(0CH2CH2 ) n-R
J Q where R' is an ethylenicaUy unsaturated functional group, R is H, OH or OCH3; and n is from 3 to 20, and one or more comonomers selected from monovinyl aromatic monomers, aliphatic conjugated diene monomers, acrylate monomers, vinylidene hande monomers, vinyl halide monomers, vinyl esters of carboxyl acids containing from 1 to 18 carbon atoms, methacrylonitrile, acrylonitrile, and monoethylenically unsaturated carboxylic acid monomers
-I c 2 The latex copolymer of Claim 1 wherein R1 1; a vinyl group or a propenyl group, n is from 7 to 15 and R is OH
3 The latex copolymer of Claim 1 or Claim 2 wnerein the ethylenicaUy unsaturated poly(ethylene glycol) monomer is present in the latex copolymer in an amount between 1 and 15 parts per hundred, or wherein the ethylenicaUy unsaturated poly(ethylene 0 glycol) monomer is present in the atex copolymer in an amount between 5 and 10 parts per hundred based on the total weight of the monomer and comonomers present in the latex copolymer
4 A process for the preparation of a latex copolymer comprising emulsion polymerizing a polymerization mixture comprising one or more ethylenicaUy unsaturated 5 poly(ethylene glycol) monomers represented by the following formula •
0
II
R 1 -C-(0CH2CH2 ) n-R
where R is an ethylenicaUy unsaturated functional group; R is H, OH or OCH3; and n is from 3 0 to 20, and one or more comonomers selected from monovinyl aromatic monomers, aliphatic conjugated diene monomers, acrylate monomers, vinylidene halide monomers, vinyl halide monomers, vinyl esters of carboxyl acids containing from 1 to 18 carbon atoms, methacrylonitrile, acrylonitrile, and monoethylenically unsaturated carboxylic acid monomers
5 The process of Claim 4 wherein R1 is a vinyl group or a propenyl group, n is 5
Figure imgf000011_0001
6 The process of Claim 4 or Claim 5 wherein the ethylenicaUy unsaturated poly(ethylene glycol) monomer is present in the polymerization mixture in an amount between
Figure imgf000012_0001
ad based on the total weight of the monomer and comonomers present in the /lymer.
7. A paper coating composition comprising latex copolymer comprising in polymerized form one or more ethylenicaUy unsaturated poly(ethylene glycol) monomers represented by the following formula
0
R 1 -C- ( 0CH2CH2 ) n-R
10
where R1 is an ethylenicaUy unsaturated functional group; R is H, OH or OCH3; and n is from 3 to 20, and one or more comonomers selected from monovinyl aromatic monomers, aliphatic conjugated diene monomers, acrylate monomers, vinylidene halide monomers, vinyl halide - c monomers, vinyl esters of carboxyl acids containing from 1 to 18 carbon atoms, methacrylonitrile, acrylonitrile, and monoethylenically unsaturated carboxylic acid monomers; and mixed therewith: one or more pigments; and, optionally, one or more binders; and, optionally Q one or more stabilizing agents; and, optionally, a defoamer
8. The paper coating composition of Claim 7 wherein the binders are selected from starch, modified starch, oxidized, enzyme converted and hydroxy-ethylated starch, soybean protein, casein, styrene-butadiene copolymer latexes, styrene-butadiene acrylate 5 copolymer latexes, and mixtures thereof
9. The paper coating composition of Claim 7 or Claim 8 wherein, based on the total weight of the composition, from 0.5 to 25 parts of the latex copolymer is present; from 65 to 100 parts clay pigment is present; from 0 to 35 parts secondary pigment selected from calcium carbonate, titanium dioxide and satin white is present; from 0.01 to 0.5 parts 0 stabilizing agent is present; from 0 to 0 2 parts defoamer is present; and the composition has from 35 to 70 weight percent solids
10 The paper coating composition of Claim 7 wherein the latex copolymer is from 10 weight percent to 50 weight percent of the combined latex copolymer and binder, or wherein the latex copolymer is from 20 weight percent to 45 weight percent of the combined 5 latex copolymer and binder
1 1 A process for the preparation of a paper coating composition comprising emulsion polymerizing a polymerization mixture comprising one or more ethylenicaUy unsaturated poly(ethylene glycol) monomers represented by the following formula: 0
II
R 1 -C- ( 0CH2CH2 ) n-R
where R1 is an ethylenicaUy unsaturated functional group; R is H, OH or OCH3; and n is from 3 to 20, and one or more comonomers selected from monovinyl aromatic monomers, aliphatic conjugated diene monomers, acrylate monomers, vinylidene halide monomers, vinyl halide monomers, vinyl esters of carboxyl acids containing from 1 to 18 carbon atoms, methacrylonitrile, acrylonitrile, and monoethylenically unsaturated carboxylic acid monomers; and mixing therewith in any order: one or more pigments; and, optionally, one or more binders; and, optionally, one or more stabilizing agents; and, optionally, a defoamer.
PCT/US1993/003618 1992-04-07 1993-04-16 Latex copolymers for paper coating compositions Ceased WO1994024202A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU40323/93A AU4032393A (en) 1993-04-16 1993-04-16 Latex copolymers for paper coating compositions
PCT/US1993/003618 WO1994024202A1 (en) 1992-04-07 1993-04-16 Latex copolymers for paper coating compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US86474892A 1992-04-07 1992-04-07
PCT/US1993/003618 WO1994024202A1 (en) 1992-04-07 1993-04-16 Latex copolymers for paper coating compositions

Publications (1)

Publication Number Publication Date
WO1994024202A1 true WO1994024202A1 (en) 1994-10-27

Family

ID=25343979

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1993/003618 Ceased WO1994024202A1 (en) 1992-04-07 1993-04-16 Latex copolymers for paper coating compositions

Country Status (1)

Country Link
WO (1) WO1994024202A1 (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1069142A1 (en) * 1999-07-15 2001-01-17 Clariant GmbH Water soluble polymers and their use in cosmetic and pharmaceutic products
US6800682B1 (en) 1995-06-22 2004-10-05 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Gluing, sealing and coating compound
EP2275462A2 (en) 2002-11-08 2011-01-19 Omya Development AG Copolymer having at least one alkoxy- or hydroxy-polyalkylene glycol grafted function, and use thereof
US20110172358A1 (en) * 2006-06-14 2011-07-14 Sivapackia Ganapathiappan Functionalized latex polymer and method of forming the same
US8062630B2 (en) 2000-12-01 2011-11-22 Clariant Produkte (Deutschland) Gmbh Surfactant-free cosmetic, dermatological and pharmaceutical agents
WO2012023010A1 (en) 2010-08-19 2012-02-23 Coatex S.A.S. Use, in paper coating slips, of amphiphilic and non-water-soluble comb (meth)acrylic polymers
WO2012023009A1 (en) 2010-08-19 2012-02-23 Coatex S.A.S. Amphiphilic and non-water-soluble comb (meth)acrylic polymers
US8187581B2 (en) 2000-12-01 2012-05-29 Clariant Produkte (Deutschland) Gmbh Surfactant-containing cosmetic, dermatological and pharmaceutical agents
FR2988396A1 (en) * 2012-03-23 2013-09-27 Coatex Sas USE OF LOW-IONIC POLYMERS AS COMPATIBILIZING AGENTS IN AQUEOUS SUSPENSIONS OF ANIONIC MINERAL FILLS CONTAINING A MINERAL OR ORGANIC SALT

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4265977A (en) * 1979-04-24 1981-05-05 Asahi-Dow Limited Paper coating composition of unsaturated acid and mono-olefin polymerized in the presence of a preformed styrene/butadiene latex
US4613650A (en) * 1983-08-12 1986-09-23 Nippon Zeon Co., Ltd. Copolymer latex

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4265977A (en) * 1979-04-24 1981-05-05 Asahi-Dow Limited Paper coating composition of unsaturated acid and mono-olefin polymerized in the presence of a preformed styrene/butadiene latex
US4613650A (en) * 1983-08-12 1986-09-23 Nippon Zeon Co., Ltd. Copolymer latex

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6800682B1 (en) 1995-06-22 2004-10-05 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Gluing, sealing and coating compound
EP0833864B2 (en) † 1995-06-22 2005-08-10 Henkel Kommanditgesellschaft auf Aktien Gluing, sealing and coating compound
EP1069142A1 (en) * 1999-07-15 2001-01-17 Clariant GmbH Water soluble polymers and their use in cosmetic and pharmaceutic products
US8187581B2 (en) 2000-12-01 2012-05-29 Clariant Produkte (Deutschland) Gmbh Surfactant-containing cosmetic, dermatological and pharmaceutical agents
US8062630B2 (en) 2000-12-01 2011-11-22 Clariant Produkte (Deutschland) Gmbh Surfactant-free cosmetic, dermatological and pharmaceutical agents
EP2275462A2 (en) 2002-11-08 2011-01-19 Omya Development AG Copolymer having at least one alkoxy- or hydroxy-polyalkylene glycol grafted function, and use thereof
US8273933B2 (en) 2006-06-14 2012-09-25 Hewlett-Packard Development Company, L.P. Functionalized latex polymer and method of forming the same
US20110172358A1 (en) * 2006-06-14 2011-07-14 Sivapackia Ganapathiappan Functionalized latex polymer and method of forming the same
WO2012023009A1 (en) 2010-08-19 2012-02-23 Coatex S.A.S. Amphiphilic and non-water-soluble comb (meth)acrylic polymers
WO2012023010A1 (en) 2010-08-19 2012-02-23 Coatex S.A.S. Use, in paper coating slips, of amphiphilic and non-water-soluble comb (meth)acrylic polymers
EP3106483A1 (en) 2010-08-19 2016-12-21 Coatex (meth)acrylic comb polymers that are amphiphilic and water-soluble or water-insoluble
FR2988396A1 (en) * 2012-03-23 2013-09-27 Coatex Sas USE OF LOW-IONIC POLYMERS AS COMPATIBILIZING AGENTS IN AQUEOUS SUSPENSIONS OF ANIONIC MINERAL FILLS CONTAINING A MINERAL OR ORGANIC SALT
WO2013140098A3 (en) * 2012-03-23 2014-01-16 Coatex Slightly ionic polymers for aqueous suspension of mineral fillers for a coating liquid intended for inkjet printing

Similar Documents

Publication Publication Date Title
US5491209A (en) Latex copolymers for paper coating compositions
EP0019716B2 (en) Aqueous polymeric dispersions and paper coating compositions
US4478974A (en) Heterogeneous polymer latex of relatively hard and relatively soft interpolymers of a monovinylidene aromatic monomer and an aliphatic conjugated diene monomer
US3242121A (en) Method of preparing latex binder of styrene, an alkyl acrylate, and an ethylenically unsaturated carboxylic acid
US5563201A (en) Aqueous papercoating compositions comprising a substantially H2 O-insoluble, alkali-soluble latex
EP0040419B1 (en) Heterogeneous polymer latex of relatively hard and relatively soft interpolymers of a monovinylidene aromatic monomer and an aliphatic conjugated diene monomer and paper coating compositions containing said latexes
EP0331143B1 (en) Coating composition and cast-coated paper coated with same
US4521494A (en) Styrene-acrylic latex containing a hetero-unsaturated monomer and paper-coating compositions produced therefrom
US4065423A (en) Paper coating latex compositions containing copolymers of monovinylidene aromatic monomer, aliphatic conjugated diene and an aryloyloxycarboxylic acid monomer
WO1994024202A1 (en) Latex copolymers for paper coating compositions
EP0093206B1 (en) Polymeric compositions useful as binders in coating colours and coating colours prepared therefrom
EP0062338A1 (en) Water resistant paper compositions containing carboxyl group-containing latex and aziridine derivatives
EP0343007B2 (en) Paper coating composition
JPH06211911A (en) Paper coating copolymer latex and paper coating composition containing the latex
JPS60224895A (en) Coating composition for gravure printing paper
JPH08259611A (en) Production of resin latex
EP0109463B2 (en) Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom
JP2607297B2 (en) Composition for paper coating
JPS6261720B2 (en)
JP3177293B2 (en) Composition for coated paper and coated paper
JPS6163795A (en) Paper coating composition
JPS6155290A (en) Coating composition for gravure printed paper
US4631312A (en) Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom
JP3089080B2 (en) Pigment composition
JPH07138900A (en) Coating composition for paper coating and coated paper comprising the same

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA FI JP KR US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA