CA2347202A1 - Improved paper sizing agents and methods of making the agents and sizing paper - Google Patents

Improved paper sizing agents and methods of making the agents and sizing paper

Info

Publication number
CA2347202A1
CA2347202A1 CA002347202A CA2347202A CA2347202A1 CA 2347202 A1 CA2347202 A1 CA 2347202A1 CA 002347202 A CA002347202 A CA 002347202A CA 2347202 A CA2347202 A CA 2347202A CA 2347202 A1 CA2347202 A1 CA 2347202A1
Authority
CA
Canada
Prior art keywords
sizing agent
sizing
acrylate
amount
styrene
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
CA002347202A
Other languages
French (fr)
Other versions
CA2347202C (en
Inventor
Michael P. O'toole
Otto S. Depierne
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.)
Kemira Oyj
Original Assignee
Individual
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 Individual filed Critical Individual
Publication of CA2347202A1 publication Critical patent/CA2347202A1/en
Application granted granted Critical
Publication of CA2347202C publication Critical patent/CA2347202C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • 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
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • 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
    • C08F220/12—Esters of monohydric alcohols or phenols
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • 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
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D21H17/29—Starch cationic
    • 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
    • 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
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D21H17/43—Carboxyl groups or derivatives thereof

Abstract

Sizing agents comprised of dispersed synthetic polymers in an aqueous solution are provided, as well as methods for making these sizing agents and methods for using these sizing agents to size paper. The polymers are prepared by copolymerizing styrene which optionally may be substituted and certain acrylates in the presence of a stabilizing agent. Improved sizing is obtained by including recurring units of methyl acrylate, ethyl acrylate, and/or propyl acrylate in the synthetic polymers.

Claims (15)

We claim:
1. A method for making a sizing agent comprising (I) forming a mixture comprised of (A) 5-40%, by weight based on total weight, of ethylenically unsaturated monomers comprised of (1) 20-80%, by mole based on total moles of monomers, of at least one monomer selected from the group consisting of styrene, C1-C4 alkyl substituted styrene, alpha-methyl styrene and ring-halogenated styrene, (2) 0-80%, by mole based on total moles of monomers, of at least one C4-C12 alkyl (meth)acrylate monomer, (3) 5-50%, by mole based on total moles of monomers, of at least one monomer selected from the group consisting of methyl acrylate, ethyl acrylate, and propyl acrylate, and (B) a stabilizing agent selected from the group consisting of polysaccharide, polyvinyl alcohol, and polyacrylamide, wherein the weight ratio of said (A) to said {B) in said mixture is in the range of about 0.6:1 to about 1.7:1 and wherein said mixture is substantially free of both (i) ethylenically unsaturated carboxylic and sulfonic acids and salts thereof and (ii) emulsifier or surfactant having a molecular weight of less than 1,000, and (II) copolymerizing said ethylenically unsaturated monomers in the presence of water to form a dispersion.
2. A method as claimed in Claim 1 wherein said (1) is styrene, said (2) is butyl acrylate, and said (3) is methyl acrylate.
3. A method as claimed in Claim 1, wherein said weight ratio of said (A)to said (B) in said mixture is in the range of about 0.8:1 to about 1.5:1.
4. A method as claimed in Claim 1 wherein the amount of said (1) is 40-60%, the amount of said (2) is 20-50%, and the amount of said (3) is 10-20%, by mole based on total moles of monomers.
5. A method as claimed in Claim 1 wherein said stabilizing agent is a polysaccharide.
6. A method as claimed in Claim 1 which further comprises adding a polymerization initiator at or near the end of said copolymerizing to reduce the residual monomer content of said aqueous dispersion.
7. A sizing agent obtainable by the method of Claim 1, comprised of (A) 5-40%, by weight based on total weight, of a water-insoluble polymer comprised of recurring units of (1) 20-80%, by mole based on total moles of recurring units, of at least one recurring unit selected from the group consisting of styrene, C1-C4 alkyl substituted styrene, alpha-methyl styrene and ring-halogenated styrene, (2) 0-80%,by mole based on total moles of recurring units, of at least one C4-C12 alkyl (meth)acrylate recurring unit, (3) 5-50%,by mole based on total moles of recurring units, of at least one recurring unit selected from the group consisting of methyl acrylate, ethyl acrylate, and propyl acrylate, and (B) a stabilizing agent selected from the group consisting of polysaccharide, polyvinyl alcohol, and polyacrylamide, wherein the weight ratio of said (A) to said (B) in said sizing agent is in the range of about 0.6:1 to about 1.7:1, wherein said sizing agent is substantially free of emulsifier or surfactant having a molecular weight of less than 1,000, and wherein said water-insoluble polymer is substantially free of acidic recurring units.
8. A sizing agent as described in Claim 7, wherein said (1) is styrene, said (2) is butyl acrylate, and said (3) is methyl acrylate.
9. A sizing agent as described in Claim 7, wherein said stabilizing agent is a cationic waxy maize starch.
10. A sizing agent as described in Claim 7, wherein said weight ratio of said (A) to said (B) in said sizing agent is in the range of about 0.9:1 to about 1.2:1.
11. A sizing agent as described in Claim 7, wherein the amount of said (1) is 75%, the amount of said (2) is 10-60%, and the amount of said (3) is 8-30%, by mole based on total moles of monomers.
12. A sizing agent as described in Claim 7, wherein said weight ratio of said (A) to said (B) in said sizing agent is in the range of about 0.8:1 to about 1.5:1, and wherein the amount of said (1) is 40-60%, the amount of said (2) is 20-50%, and the amount of said (3) is 10-20%, by mole based on total moles of recurring units.
13. A method of sizing paper, comprising (a) providing paper stock;
(b) providing the sizing agent of Claim 7;
(c) forming a web from said paper stock; and (d) mixing said sizing agent with said paper stock, or applying said sizing agent to said web by a method selected from the group consisting of spraying and size pressing, in an amount effective to size paper that is formed from said web.
30
15. A method as claimed in Claim 13 wherein said paper that is formed from said web has a degree of sizing that is greater than the degree of sizing obtained when a sizing agent that does not contain recurring units selected from the group consisting of methyl acrylate, ethyl acrylate, and propyl acrylate is used in place of the sizing agent of Claim 7.
CA002347202A 1998-10-16 1999-09-22 Improved paper sizing agents and methods of making the agents and sizing paper Expired - Fee Related CA2347202C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US09/174,076 1998-10-16
US09/174,076 US6114417A (en) 1998-10-16 1998-10-16 Paper sizing agents and methods
PCT/US1999/022030 WO2000023479A1 (en) 1998-10-16 1999-09-22 Improved paper sizing agents and methods of making the agents and sizing paper

Publications (2)

Publication Number Publication Date
CA2347202A1 true CA2347202A1 (en) 2000-04-27
CA2347202C CA2347202C (en) 2010-01-12

Family

ID=22634721

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002347202A Expired - Fee Related CA2347202C (en) 1998-10-16 1999-09-22 Improved paper sizing agents and methods of making the agents and sizing paper

Country Status (13)

Country Link
US (1) US6114417A (en)
EP (1) EP1155045A1 (en)
JP (1) JP2002527643A (en)
KR (1) KR20010099696A (en)
CN (1) CN1323318A (en)
AR (1) AR020840A1 (en)
AU (1) AU6058499A (en)
BR (1) BR9914514A (en)
CA (1) CA2347202C (en)
CO (1) CO5100978A1 (en)
ID (1) ID29280A (en)
PL (1) PL347273A1 (en)
WO (1) WO2000023479A1 (en)

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JP6090657B2 (en) * 2013-02-22 2017-03-08 荒川化学工業株式会社 Paper-making surface sizing agent and paper coated with the sizing agent
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CN106554465A (en) * 2016-06-29 2017-04-05 宁夏海诚电化信息科技有限公司 A kind of top sizing agent producing process
CN108383944B (en) * 2018-01-17 2020-07-03 寿光美伦纸业有限责任公司 Preparation method of cationic starch/nano-cellulose-based water-resistant reinforced composite emulsion
CN109400809A (en) * 2018-09-11 2019-03-01 郑州林海环保材料有限公司 Different monooctyl ester surface water resistant sizing agent of styrene-t and preparation method thereof
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CN114163569A (en) * 2021-12-10 2022-03-11 上海东升新材料有限公司 Water-resistant surface sizing agent and preparation method and application thereof

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Also Published As

Publication number Publication date
CA2347202C (en) 2010-01-12
PL347273A1 (en) 2002-03-25
US6114417A (en) 2000-09-05
WO2000023479A1 (en) 2000-04-27
CN1323318A (en) 2001-11-21
ID29280A (en) 2001-08-16
CO5100978A1 (en) 2001-11-27
AR020840A1 (en) 2002-05-29
BR9914514A (en) 2001-06-26
KR20010099696A (en) 2001-11-09
EP1155045A1 (en) 2001-11-21
JP2002527643A (en) 2002-08-27
AU6058499A (en) 2000-05-08

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