EP0889992A1 - Collage en surface de produits a base de cellulose - Google Patents

Collage en surface de produits a base de cellulose

Info

Publication number
EP0889992A1
EP0889992A1 EP97916695A EP97916695A EP0889992A1 EP 0889992 A1 EP0889992 A1 EP 0889992A1 EP 97916695 A EP97916695 A EP 97916695A EP 97916695 A EP97916695 A EP 97916695A EP 0889992 A1 EP0889992 A1 EP 0889992A1
Authority
EP
European Patent Office
Prior art keywords
group
monomer
weight
monomers
ethylenically unsaturated
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
EP97916695A
Other languages
German (de)
English (en)
Other versions
EP0889992B1 (fr
Inventor
Yi-Guan Tsai
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.)
Nouryon Pulp and Performance Chemicals AB
Original Assignee
Eka Chemicals AB
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
Priority claimed from US08/625,616 external-priority patent/US6087457A/en
Priority claimed from SE9601744A external-priority patent/SE9601744D0/xx
Application filed by Eka Chemicals AB filed Critical Eka Chemicals AB
Publication of EP0889992A1 publication Critical patent/EP0889992A1/fr
Application granted granted Critical
Publication of EP0889992B1 publication Critical patent/EP0889992B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • 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
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to surface sizing of cellulose based products and more particularly to a method of sizing which comprises applying an aqueous dispersion of emul ⁇ sion polymerized monomers to the surface of such products
  • the invention further relates to an aqueous sizing composition comprising a dispersion of emulsion polymerized monomers
  • an object of the present invention to provide an improved method of surface sizing cellulose based products
  • Another object of the invention to provide an aqueous dispersion containing emulsion polymerized monomers resulting in improved sur- face sizing
  • It is another object of the invention to provide an aqueous sizing composition comprising a dispersion of emulsion polymerized monomers which has beneficial application characteristics in surface sizing and, in particular high performance in the presence of electrolytes and bases
  • the present invention generally relates to a method of sizing cellulose based products by applying to the surface thereof an aqueous sizing composition comprising a dispersion of emulsion polymerized monomers, and to an aqueous sizing composition comprising such a dispersion More specifically, the method of the invention comprises apply ⁇ ing to the surface of cellulose based products an aqueous dispersion of a copolymer obtai ⁇ nable by free-radical emulsion polymerization of a monomer mixture containing
  • (a2) at least one monomer selected from the group consisting of esters of - ethylenically unsaturated carboxylic acids and aikanols,
  • paper and similar cellulose based products having a very high resistance to penetration by aqueous liquids can be pro- vided by surface sizing such products with an aqueous dispersion of finely divided particles of a copolymer comprising in emulsion polymerized form a monomer mixture based on styrene alkyl acrylates and carboxy and/or sulfo group containing monomers
  • the present invention renders possible production of cellulose based products with improved sizing results as com ⁇ pared to methods using conventional aqueous dispersions of copolymers based on styrene and alkyl acrylates It was surprisingly found that improvements could be achieved by incor ⁇ porating carboxy and/or sulfo group containing monomers into the copolymer Accordingly, the present invention enables the use of a lower polymer dosage to give the same sizing effect, thereby leading to cost reduction and economic benefits
  • the term "sizing" refers a lower polymer dosage to give the
  • the monomers of group (a) compnse (a1) at least one monomer selected from the group consisting of styrene and derivatives thereof Styrene is preferred
  • the styrene derivatives are uncharged and suitable styrene derivatives encompassed by group (a1) include C C alkyl substituted styrenes such as ⁇ -methylstyrene and vinyltoluenes, but other types of de ⁇ vatives can also be used, e g. halogen substituted styrenes such as chloro- styrenes
  • esters of ethylenically unsaturated carboxylic acids and alkanols Monoethylenically unsaturated esters are preferred
  • the esters are suitably de ⁇ ved from carboxylic acids containing from 3 to 6, preferably from 3 to 4, carbon atoms, and alkanols containing from 1 to 18, suitably from 1 to 8 and preferably from 1 to 4, carbon atoms
  • the alkanols are preferably monohyd ⁇ c saturated alcohols.
  • Suitable esters include fully esterified carboxylic acids, e.g.
  • monoesters of monocarboxylic acids such as alkyl acrylates and alkyl methacrylates
  • diesters of dicarboxylic acids such as dialkyl maleates, dialkyl fumarates
  • trialkyl esters of t ⁇ carboxy c acids such as t ⁇ alkylesters of aconitic acid
  • alkyl acrylates and alkyl methacrylates are preferred
  • Suitable alkyl acrylates and alkyl methacrylates include those of C C 18 , suitably C C 8 and preferably C C 4 alkyls
  • suitable alkyl acrylates include methyl, ethyl, n- propyl, n-butyl, iso-butyl, tert-butyl, neopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, octyl, decyl, palmityl and stearyl acrylates
  • Butyl acrylates and mixtures including butyl acrylates are particularly preferred
  • suitable alkyl methacrylates include methyl, isopropyl, n- butyl, iso-butyl and tert-butyl methacrylates
  • the monomers of group (a) can be used in an amount of from about 70 to 99 5% by weight, suitably at least about 80% by weight, preferably at least about 85%
  • the monomers of group (b) comprise ethylenically unsaturated carboxyl acids and salts thereof as well as ethylenically unsaturated sulfonic acids and salt thereof, mono- ethylenically unsaturated monomers being preferred
  • the group (b) monomers thus contain at least one carboxy group or sulfo group, either in the form of free acid or salt, i e., carboxylic acids, carboxylates, sulfonic acids and sulfonates
  • Carboxylates and sulfonates can be prepared from the corresponding acids by treating the monomers with a solution of base such as sodium hydroxide, potassium hydroxide, ammonia or amines, resulting in monomers being complete ⁇ ly or partially neutralized Among these, ammonia is generally preferred
  • carboxylic acid monomers include C 3 -C 6 , preferably C 3 -C carboxylic acids, e.g. monocarboxylic acids such as acrylic acid, methacrylic acid and half esters of di- and tncarboxylic acids, e g C C 4 alkyl monoesters of maleic and fumaric acids, dicarboxylic acids, such as maleic acid, fumaric acid and itaconic acid, and tncarboxylic acids such as aconitic acid and its C C alkyl mono- and diesters.
  • monocarboxylic acids such as acrylic acid, methacrylic acid and half esters of di- and tncarboxylic acids, e g C C 4 alkyl monoesters of maleic and fumaric acids
  • dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid
  • tncarboxylic acids such as aconitic acid and its C C alkyl mono- and diesters.
  • Suitable sulfonic acid monomers include C 2 -C 10 sulfonic acids, e g vinyl sulfonic acid (ethylene sulfonic acid), allyl sulfonic acid, styrene sulfonic acid, 2-sulfoethyl methacrylate, 2-acrylam ⁇ dopropane sulfonic acid, and 2-acrylam ⁇ doethane sulfonic acid
  • carboxylic acids and salts thereof are preferred monomers of group (b) since, inter alia, they normally are more readily accessible and less expensive than the sulfonic acids
  • the monomer of group (b) can be used in an amount of from about 0 5 to 15% by weight, suitably at least about 1% up to about 10%, preferably less than 7%, a preferred range being from about 1 % to 5% by weight, based on the weight of monomers used in the polymerization
  • the subject dispersion may contain, in emulsion polymerized form, other ethylenically unsaturated copolyme ⁇ zable monomers of group (c)
  • suitable monomers comprised in group (c) include olefins, such as ethylene, propylene, 1 -butene, isobutene, 1-hexene and 1-octene, aliphatic conjugated dienes, such as 1 3-butad ⁇ ene and isoprene, vinyl carboxylates, such as vinyl acetate, vinyl propionate, vinyl butyrate vinyl laurate and vinyl stearate, vinyl chloride viny dene chloride, (meth)acrylam ⁇ des, such as acrylamide, methacrylamide, C C 18 alkyl acrylamides and C C 18 alkyl methacrylamides, and hydroxy functional monomers
  • Preferred monomers comprised in group (c) are hydroxy functional monomers, i e monomers containing at least one hydroxyl group
  • the monomer of group (c) may consist of one or more hydroxy functional monomers as well as one or more hydroxy functional mono ⁇ mers in combination with other ethylenically unsaturated copolyme ⁇ zable monomer(s), e g any of the monomers of group (c) defined above
  • suitable hydroxy functional monomers are selected from N-alkanol amides and hydroxyalkylesters of monoethylenically unsaturated carboxylic acids in which the N-alkanol and hydroxyalkyl groups suitably contain from 1 to 18 carbon atoms, preferably C C 4
  • Suitable hydroxy functional monomers include hydroxyalkyl acrylates, such as 2-hydroxyethyl acrylate and 3-hydroxypropyl acrylate, hydroxyalkyl methacrylates, such as 2-hydroxyethyl methacrylate and 3-hydroxypropyl meth
  • the monomer of group (c) can be used in an amount of up to about 15% by weight, suitably from 0 5% to about 10%, preferably up to about 5%, and a preferred range is from 1% to about 5% by weight, based on the weight of monomers used in the polymerization, the sum of percentages of (a) + (b) + (c) being 100
  • group (c) monomers comprising at least one hydroxy functional monomer its amount is suitably from 0 5 to 5% by weight and preferably from 1 0 to 5.0% by weight, based on the weight of monomers used in the polymerization
  • the dispersion according to the invention can be prepared by copolyme ⁇ zing monomers of groups (a), (b) and (c) in conventional manner Emulsion polymerization processes are known in the art and reference is made to Encyclopedia of Polymer Science and Engineering, Vol 6, Emulsion Polyme ⁇ zation, pp 1-51, John Wiley & Sons, Inc , 1986, which is hereby incorporated herein by reference
  • the polymerization is suitably initiated in an aqueous phase containing monomers, emulsifier and free-radical initiator, added in arbi- trary order, in the absence of oxygen and in an inert gas atmosphere, for example under nitrogen
  • the emulsion polymerization suitably takes place under stirring at temperatures between 20°C and 100°C, preferably between 60°C to 90°C
  • Suitable free-radical polymerization initiators are all those capable of initiating free- radical polymerizations, e g conventional thermal initiators, such as potassium and ammo- nium persulfate, organic peroxides and hydroperoxides, and hydrogen peroxide, and redox systems, such as ⁇ ron(il)/perox ⁇ de, ⁇ ron(ll)/persulfate, peroxide/metabisulfate and persul- fate/metabisulfate Chain-transfer agents, such as conventional alkyl mercaptans or alkan thiols, are suitably used in the polymerization process in known manner for modifying the molecular weight of the copolymers
  • the polymerization can be carried out as a batch process or in the form of a feed process or a combination thereof Suitably a part of the monomers to be used are initially polymerized and the remainder of the monomers are subsequently fed to the polymerization zone, either continuously or in steps, optionally in conjunction with additional free-radical initiator
  • the polymer dispersion is preferably obtained by the steps of (i) initial polymerization of at least one monomer of group (a), and
  • the initial polymerization step (i) is carried out in the substantial absence of monomers of groups (b) and (c), and at least a part of the total weight of group (a) monomers to be used is present during the subsequent polymerization step (n)
  • the amount of group (a) monomers used in the subsequent polyme ⁇ zation step (n) can be from 5% to 95% and suitably from 10% to 75% by weight, based on the total weight of group (a) monomers used in the overall polymerization process
  • This embodiment of the invention using a polymer dispersion prepared by means of the initial and subsequent polymerization steps may result in polymer particles with a pronounced core/shell structure, the core being more hydrophobic and the shell being less hydrophobic, i e , more hydrophilic
  • the degree of core/shell structure obtained will depend on, inter alia, the types of monomers used and their weight ratios and the manner they and the initiator are introduced into the polyme ⁇ zation zone, as will be easily appreciated by a person skilled in the art
  • the polymer dispersion suitably contains at least one emulsifier or dispersing agent the amount of which may be from 0 25 to 20%, preferably from 0 5 to 10% and most prefer ⁇ ably from 0 75 to 5% by weight, based on the weight of monomers used in the polymerization
  • Anionic, cationic amphoteric and nonionic emulsifiers can be used and preference is given for anionic emulsifiers such as those commonly used for anionic disper ⁇ sions or emulsions
  • Suitable anionic emulsifiers can be selected from alkyl and alkylaryl sulfates, sulfonates, ethersulfates phosphates and etherphosphates, and dialkyl sulfo- succinates suitably in the form of an alkali metal or ammonium salt, such as for example sodium laurylsulphate, sodium laurylsulphonate and sodium dodecylbenzenesulfonate Poly ⁇ acrylic
  • the present dispersion have high stability both in the presence of bases and electrolytes and at extended storage, even when prepared from low levels of emulsifiers and also in the absence of protective colloids
  • the polymer dispersion can thus be prepared in the absence of protective colloids such as starches and de ⁇ vatives thereof, which are commonly used in the polymenzation process and, usually, in high levels
  • the dispersion according to the invention can have a solids content of from 0 01 to 60%, suitably from 10 to 50% by weight, based on the aqueous dispersion
  • High solids content dispersions can of course be diluted with water or mixed with aqueous solutions prior to use, e g aqueous solutions of starch and/or derivatives thereof, and suitable copolymer solids contents for surface sizing is within the range of from about 0 01 to 10 0% by weight
  • the method of sizing according to the invention comprises applying the aqueous polymer dispersion to the surface of cellulose based products such as paper, board and paper board, and the polymer dispersion can of course be applied in conjunction with compo ⁇ nents conventionally used in surface sizing such as starch and de ⁇ vatives thereof Applica ⁇ tion of the dispersion to cellulosic surfaces is usually effected by means of a size press It is of course also possible to apply the dispersion to cellulosic surfaces by means of spraying or immersion
  • the product treated with the polymer dispersion is normally dned at elevated tem ⁇ peratures
  • the amount of dispersion applied to the surface is from 0 05 to 5%, prefer ⁇ ably from 0 1 to 1% by weight, calculated as dry polymer on dry cellulose based product
  • electrolytes that can be added to the aqueous sizing composition present in the size press include inorganic electrolytes, preferably salts of alkali metals such as sodium chloride and sodium sulphate Usually, the content of electrolyte is from 0 1% to 2% and suitably from about 0 3% to 1% by weight, based on the sizing composition
  • the aqueous sizing composition according to the present invention comprises an aqueous poly ⁇ mer dispersion, as defined hereinabove, and an electrolyte
  • the sizing composition can have a copolymer solids content of from about 0 01 to 10 0% by weight Starch and/or derivatives thereof can also be present in the sizing composition and suitable solids contents of starch- based material are from about 1 to 10% by weight and preferably from 3 to 8% by weight
  • the invention thus relates to an aqueous sizing composition as further defined in the claims
  • An aqueous dispersion according to the invention was prepared as follows In a stirred reactor equipped with a stirrer, a reflux condenser and addition means, 1 part of a sodium alkyl sulfonate and 50 parts of deionized water were initially introduced, the reactor contents heated to a temperature of 80°C, and 20% of a mixture (I) containing of 25 parts of styrene, 8 parts of n-butyl acrylate and 0 2 parts of n-dodecane thiol was subse ⁇ quently introduced while purging the reactor with nitrogen gas The copolyme ⁇ zation was initiated by addition of a solution of 0 1 parts of potassium persulfate in deionized water After 15 minutes, the addition was commenced of the remainder of mixture (I) and a mixture (II) containing 0 2 parts of potassium persulfate in deionized water The mixtures were continuously fed to the reactor, mixture (I) for 100 minutes and mixture (II) for 120
  • dispersion 1 The dispersion of copolymer particles obtained, hereafter dispersion 1 , had a solids content of about 37% and a mean particle diameter of about 65 nm, measured by means of a Malvern Zetasizer 3.
  • Dispersions to be used according to the invention and for comparison purposes were prepared according to the procedure of Example 1 with the difference that the monomers of mixture (III) were replaced with the monomers and amounts thereof (wt %, based on the total weight of monomers used in the polymerization) set forth in Table I Table I
  • Dispersion 1 of Example 1 was used for surface sizing of paper according to the method of the invention and the liquid penetration properties of the paper sheets obtained were tested A comparison was made with an aqueous dispersion of a copolymer prepared by emulsion polymerization of styrene and n-butyl acrylate in the presence of starch as a protective colloid, hereafter dispersion 9
  • Paper sheets with a basis weight of 80 g/m 2 were treated with dilute dispersion (solids content about 0 2% by weight), passed through a two roll size press and then dried on a drum drier at a temperature of 105°C
  • Dispersion Cobb (60) values (g/m 2 ) at dry polymer dosage used 0.05% 0.10% 0 15% 0 20% 0 25% 0 30%
  • Dispersions 1 to 8 according to Example 2 were tested and their surface sizing efficiency was evaluated Tests were also made with dispersions containing electrolytes which were prepared by adding aqueous sodium chloride to the dispersions followed by dilu- tion with water The sodium chloride content was 2% by weight, based on the dispersion
  • HST (seconds) 320 330 310 320 350 260

Landscapes

  • Paper (AREA)
  • Graft Or Block Polymers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
EP97916695A 1996-03-29 1997-03-26 Collage en surface de produits a base de cellulose Expired - Lifetime EP0889992B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US625616 1996-03-29
US08/625,616 US6087457A (en) 1996-03-29 1996-03-29 Surface sizing of cellulose based products
SE9601744A SE9601744D0 (sv) 1996-05-07 1996-05-07 Surface sizing of cellulose based products
SE9601744 1996-05-07
PCT/SE1997/000542 WO1997037078A1 (fr) 1996-03-29 1997-03-26 Collage en surface de produits a base de cellulose

Publications (2)

Publication Number Publication Date
EP0889992A1 true EP0889992A1 (fr) 1999-01-13
EP0889992B1 EP0889992B1 (fr) 2001-05-16

Family

ID=26662605

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97916695A Expired - Lifetime EP0889992B1 (fr) 1996-03-29 1997-03-26 Collage en surface de produits a base de cellulose

Country Status (7)

Country Link
EP (1) EP0889992B1 (fr)
JP (1) JP3181060B2 (fr)
AT (1) ATE201246T1 (fr)
AU (1) AU2525297A (fr)
CA (1) CA2250235A1 (fr)
DE (1) DE69704859D1 (fr)
WO (1) WO1997037078A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6114417A (en) * 1998-10-16 2000-09-05 Cytec Technology Corp. Paper sizing agents and methods
GB9901597D0 (en) 1999-01-26 1999-03-17 Ciba Spec Chem Water Treat Ltd Sizing compositions
JP4803425B2 (ja) * 2005-11-24 2011-10-26 Ｄｉｃ株式会社 紙加工用樹脂エマルジョンの製造方法
WO2015103029A1 (fr) * 2013-12-31 2015-07-09 Johnson & Johnson Consumer Companies, Inc. Processus de formation de produit de film intégré
FI128940B (en) * 2015-09-04 2021-03-31 Kemira Oyj Core / shell polymer particles as surface sizing agent

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2939657A1 (de) * 1979-09-29 1981-04-16 Basf Ag, 6700 Ludwigshafen Bindemittel fuer papierstreichmassen
DE3423765A1 (de) * 1984-06-28 1986-01-09 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von stabilen waessrigen polymerdispersionen, die eine alkenylaromatische verbindung einpolymerisiert enthalten
JP3304642B2 (ja) * 1994-09-16 2002-07-22 荒川化学工業株式会社 スチレン／（メタ）アクリル系多元共重合体の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9737078A1 *

Also Published As

Publication number Publication date
EP0889992B1 (fr) 2001-05-16
AU2525297A (en) 1997-10-22
WO1997037078A1 (fr) 1997-10-09
DE69704859D1 (de) 2001-06-21
CA2250235A1 (fr) 1997-10-09
ATE201246T1 (de) 2001-06-15
JP3181060B2 (ja) 2001-07-03
JP2000507652A (ja) 2000-06-20

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