CA2473356A1 - Polymer emulsion coatings for cellulosic substrates with improved barrier properties - Google Patents

Polymer emulsion coatings for cellulosic substrates with improved barrier properties Download PDF

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Publication number
CA2473356A1
CA2473356A1 CA 2473356 CA2473356A CA2473356A1 CA 2473356 A1 CA2473356 A1 CA 2473356A1 CA 2473356 CA2473356 CA 2473356 CA 2473356 A CA2473356 A CA 2473356A CA 2473356 A1 CA2473356 A1 CA 2473356A1
Authority
CA
Canada
Prior art keywords
polymer
ethylene
vinyl acetate
weight
crystalline
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.)
Granted
Application number
CA 2473356
Other languages
French (fr)
Other versions
CA2473356C (en
Inventor
John Joseph Rabasco
Ronald Bernal Jones
Christian Leonard Daniels
Richard Henry Bott
John Joseph Halat
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.)
Wacker Chemical Corp
Original Assignee
Wacker Polymers LP
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 Wacker Polymers LP filed Critical Wacker Polymers LP
Publication of CA2473356A1 publication Critical patent/CA2473356A1/en
Application granted granted Critical
Publication of CA2473356C publication Critical patent/CA2473356C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P11/00—Drugs for disorders of the respiratory system
    • 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
    • C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31884—Regenerated or modified cellulose
    • Y10T428/31891—Where addition polymer is an ester or halide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y10T428/31899—Addition polymer of hydrocarbon[s] only
    • Y10T428/31902—Monoethylenically unsaturated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y10T428/31906—Ester, halide or nitrile of addition polymer

Abstract

A cellulosic product such as paper coating composition is disclosed comprising aqueous-based semi-crystalline vinyl acetate-ethylene polymer emulsions, containing crystalline ethylene segments, which are useful for imparting oil, grease, solvent, water, and moisture vapor resistance. The polymer emulsions are prepared via the direct aqueous-based free radical emulsion polymerization of ethylene with various other comonomers. The semi-crystalline aqueous-based polymer emulsions of this invention have a crystalline melting point and a crystalline heat of fusion ranging from 5 to 100 J/g.
The semi-crystalline aqueous-based emulsion polymers of this invention can be used directly as a paper or paperboard coating for imparting oil, grease, solvent, water, and moisture vapor resistance. Further, the present invention provides a repulpable paper and paperboard.

Claims (18)

1. In a cellulosic product having a polymer coating applied thereto which imparts barrier properties, the improvement which comprises:

said polymer coating comprising an ethylene-vinyl acetate polymer comprised of crystalline ethylene segments prepared by emulsion polymerizing ethylene and vinyl acetate in the presence of a stabilizing system consisting essentially of a surfactant or a protective colloid in combination with a surfactant, said ethylene-vinyl acetate polymer having:

(a) a crystalline melting point ranging from 35 to 110°C measured at a heat rate of 20°C per minute; and, (b) a tensile storage modulus of at least 1 x 10 5 dynes/cm2 at a temperature of 115°C and measured at 6.28 rad/sec.
2. The cellulosic product of claim 1 wherein the polymer is comprised of from 15 to 90% by weight of polymerized units of vinyl acetate and from about 10 to 85% by weight of polymerized units of ethylene based upon the total weight of the polymer.
3. The cellulosic product of claim 2 wherein the polymer is comprised of from 25 to 80% by weight of polymerized units of vinyl acetate and from about 20 to 75% by weight of polymerized units of ethylene based upon the total weight of the polymer.
4. The cellulosic product of claim 2 wherein the polymer is comprised of from 35 to 75% by weight of polymerized units of vinyl acetate and from about 25 to 65% by weight of polymerized units of ethylene based upon the total weight of the polymer.
5. The cellulosic product of claim 4 wherein the polymer is comprised of from 30 to 50% by weight of polymerized units of vinyl acetate and from about 50 to 70% by weight of polymerized units of ethylene based upon the total weight of the polymer
6. The cellulosic product of claim 2 wherein polymerized units of a carboxylic acid or N-methylol acrylamide are present in said polymer in an amount from about 0.2 to about 10% by weight of said polymer.
7. The cellulosic product of claim 3 wherein said polymer has a tensile storage modulus of at least 2 × 10 5 dynes/cm2 at 115 °C measured at 6.28 rad/sec.
8. The cellulosic product of claim 7 wherein the polymer consists essentially of polymerized units of ethylene, vinyl acetate, and acrylic acid.
9. The cellulosic product of claim 8 wherein the crystalline heat of fusion of said polymer is from about 5 to 100 joules per gram as measured at a heat rate of 20 °C
per minute.
10. The cellulosic product of claim 9 wherein the glass transition temperature is from +25 °C to about -40 °C as measured at a heat rate of 20 °C per minute.
11. The cellulosic product of claim 10 wherein crystalline thermal melting point ranges from 50 to 90 °C as measured at a heat rate of 20 °C per minute.
12. The cellulosic product of claim 8 wherein the T g of the polymer is from -to -35 °C.
13. The cellulosic product of claim 12 wherein the crystalline heat of fusion ranges from preferably 15 to 70 joules per gram as measured at a heat rate of 20 °C per minute.
14. In a paper or paperboard product having a polymer coating applied thereto which imparts barrier properties, said polymer coating comprising a polymer emulsion, the improvement which comprises:

the polymer coating comprising a polymer consisting essentially of polymerized units of ethylene, vinyl acetate, and a carboxylic acid or N-methylol acrylamide and containing crystalline ethylene segments, said polymer prepared by emulsion polymerizing ethylene, vinyl acetate and a carboxylic acid or N-methylol acrylamide in the presence of a stabilizing system consisting essentially of a surfactant or a protective colloid in combination with a surfactant, said ethylene-vinyl acetate polymer having:

(a) a crystalline melting point ranging from 50 to 90 °C measured at a heat rate of 20 °C per minute; and, (b) a tensile storage modulus of at least 1 × 10 5 dynes/cm2 at a temperature of 115 °C and measured at 6.28 rad/sec.
15. The paper or paperboard product of Claim 14 wherein the T g of the polymer ranges from -25 to -35 °C.
16. The paper or paperboard product of claim 15 wherein the heat of fusion of said polymer is from 10 to 70 joules per gram as measured at a heat rate of 20 °C per minute.
17. The paper or paperboard product of claim 16 wherein the polymer has from 35 to 75 weight percent vinyl acetate, 25 to 65 weight percent ethylene, and from 0.2 to 10 percent by weight a carboxylic acid or N-methylol acrylamide, based on the total weight of the polymer.
18. The paper or paperboard product of claim 16 wherein the polymer consists essentially of ethylene, vinyl acetate, and acrylic acid.
CA 2473356 2003-07-16 2004-07-09 Polymer emulsion coatings for cellulosic substrates with improved barrier properties Expired - Fee Related CA2473356C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/620,654 US7427444B2 (en) 2003-07-16 2003-07-16 Polymer emulsion coatings for cellulosic substrates with improved barrier properties
US10/620,654 2003-07-16

Publications (2)

Publication Number Publication Date
CA2473356A1 true CA2473356A1 (en) 2005-01-16
CA2473356C CA2473356C (en) 2010-03-23

Family

ID=33477097

Family Applications (1)

Application Number Title Priority Date Filing Date
CA 2473356 Expired - Fee Related CA2473356C (en) 2003-07-16 2004-07-09 Polymer emulsion coatings for cellulosic substrates with improved barrier properties

Country Status (12)

Country Link
US (1) US7427444B2 (en)
EP (1) EP1498544B1 (en)
JP (2) JP2005097547A (en)
KR (1) KR100657370B1 (en)
CN (1) CN1293262C (en)
AT (1) ATE355411T1 (en)
CA (1) CA2473356C (en)
DE (1) DE602004004951T2 (en)
ES (1) ES2278247T3 (en)
MY (1) MY140172A (en)
SI (1) SI1498544T1 (en)
TW (1) TWI261541B (en)

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US20060024338A1 (en) * 2004-07-27 2006-02-02 Hegedus Charles R Cosmetic compositions incorporating vinyl acetate-ethylene polymers
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US7485590B2 (en) * 2006-09-29 2009-02-03 Wacker Chemical Corporation Self-crosslinking vinyl acetate-ethylene polymeric binders for nonwoven webs
US8146902B2 (en) * 2006-12-21 2012-04-03 Lam Research Corporation Hybrid composite wafer carrier for wet clean equipment
JP5131462B2 (en) * 2008-02-15 2013-01-30 株式会社フジコー Water and oil repellent packaging materials
DE102008021247A1 (en) * 2008-04-28 2009-10-29 Tesa Se Adhesive tape for the roll change of flat web materials
US8747955B2 (en) 2008-08-21 2014-06-10 Basf Se Method of producing packaging having fat barrier properties
JP5463641B2 (en) * 2008-09-30 2014-04-09 大日本印刷株式会社 Oil resistant paper packaging material and oil resistant paper packaging container
US9221940B2 (en) * 2008-12-12 2015-12-29 Dow Global Technologies Llc Coating composition, a process of producing a coating composition, a coated article, and a method of forming such articles
DE102010063470A1 (en) * 2010-12-17 2012-06-21 Wacker Chemie Ag Paper coatings containing a combination of styrene-butadiene copolymer and / or styrene-acrylic acid ester copolymer and vinyl acetate-ethylene copolymer
US20170267433A1 (en) * 2012-09-25 2017-09-21 Bradley Farrell Composite Materials for Food Contact Applications
EP2811068B1 (en) * 2013-06-06 2019-05-08 Valmet Technologies, Inc. Method and arrangement for degassing treatment substance of a fiber web
WO2016183314A1 (en) * 2015-05-12 2016-11-17 Basf Se Coated substrate comprising a surface-treated, aqueous-based polymer coating and methods of making and using the same
ES2588261B1 (en) * 2016-04-15 2017-05-10 Universidad Politécnica De Cartagena Cardboard container for active packaging of fresh fruits and vegetables, and its manufacturing process
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Also Published As

Publication number Publication date
US20050014013A1 (en) 2005-01-20
MY140172A (en) 2009-11-30
EP1498544A1 (en) 2005-01-19
ATE355411T1 (en) 2006-03-15
CN1576461A (en) 2005-02-09
JP2009041014A (en) 2009-02-26
KR100657370B1 (en) 2006-12-14
TW200503891A (en) 2005-02-01
CA2473356C (en) 2010-03-23
US7427444B2 (en) 2008-09-23
KR20050009205A (en) 2005-01-24
JP2005097547A (en) 2005-04-14
EP1498544B1 (en) 2007-02-28
CN1293262C (en) 2007-01-03
TWI261541B (en) 2006-09-11
DE602004004951D1 (en) 2007-04-12
JP5032412B2 (en) 2012-09-26
DE602004004951T2 (en) 2007-06-28
ES2278247T3 (en) 2007-08-01
SI1498544T1 (en) 2007-08-31

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