WO1998024972A1 - Rosin emulsion including starch derivative for paper sizing - Google Patents
Rosin emulsion including starch derivative for paper sizing Download PDFInfo
- Publication number
- WO1998024972A1 WO1998024972A1 PCT/GB1997/003197 GB9703197W WO9824972A1 WO 1998024972 A1 WO1998024972 A1 WO 1998024972A1 GB 9703197 W GB9703197 W GB 9703197W WO 9824972 A1 WO9824972 A1 WO 9824972A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- rosin
- paper
- derivative
- starch derivative
- Prior art date
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
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
-
- 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
- D21H17/62—Rosin; Derivatives thereof
-
- 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
- D21H17/63—Inorganic compounds
- D21H17/66—Salts, e.g. alums
Definitions
- the present invention relates to a "one-shot" rosin emulsion incorporating a cationic starch derivative for use in paper sizing and also relates to a method of paper sizing using the one-shot composition.
- a rosin emulsion and a soluble aluminium salt such as aluminium sulphate
- aluminium sulphate e.g. in the form of paper- makers alum [Al 2 (S0 4 ) 3 .16-18H 2 O], aluminium chloride, poly-aluminium chloride or aluminium chlorohydrate.
- emulsion is conventionally used to describe the rosin product it should more properly be called a dispersion since although made as an emulsion, the particles are effectively solid at ambient temperature).
- the rosin emulsion and aluminium salt are generally used as separate additions to the paper making process.
- One-shot composition may be produced by vigorous stirring of an anionic Bewoid rosin emulsion (e.g. stabilised with casein) and an aluminium salt such that agitation is continued beyond formation of an initial precipitate to convert the latter into a cationic emulsion. Production of such emulsions using this technique is disclosed in GB-A-2 050 453.
- Cationic emulsions made by this type of technique are not in very common use although there are a few which are still on the market.
- a limitation of such cationic emulsions is that often they are not as stable as the anionic rosin emulsions from which they are derived, and obtaining reproducibility is not always easy. It has therefore been the practice to include a cationic stabiliser as one component of the emulsion formed from the anionic Bewoid emulsion and the aluminium salt.
- cationic stabilisers include quatemised and other cationised starches.
- a "one-shot" composition for use in paper sizing comprising an admixture of a rosin emulsion, a soluble aluminium salt and a cationic starch derivative which has a charged state of 0.5 to 5.0 m equivalents per gramme and which has been produced by a process in which the starch structure was split prior to the cationising step.
- composition of the invention thus incorporates a cationic polymer derived from a degraded starch and having a charge density (i.e. the average number of milli- equivalents of cationised atoms per gramme of polymer) of 0.5 to 50.
- a charge density i.e. the average number of milli- equivalents of cationised atoms per gramme of polymer
- charge density i.e. the average number of milli- equivalents of cationised atoms per gramme of polymer
- the low viscosity and higher charge of the cationic polymer permits the charge of an anionic rosin emulsion to be reversed at low concentrations of the cationic polymer to produce a useable cationic emulsion and to produce a range of cationicities that may be tailored to meet specific demands of a mill.
- the cationic polymer has a charge density of 0.5 to 4.5 and more preferably 1 to 3.5 m equivalents per gramme.
- Cationic polymers produced from degraded starch for use in the invention may be produced with a range of molar masses and degree of cationisation. Furthermore, it is possible for solutions of such polymers to be produced containing up to 55% by weight of the polymer without being excessively viscous. Therefore it is possible in accordance with the invention to produce a range of "one-shot" cationic compositions which have sufficient cationicity for a particular application without being too viscous.
- the cationic polymer employed in the invention is a quatemised derivative of a degraded starch.
- a derivative has a degree of substitution of at least 0.15, more preferably 0.15 to 1.30 and even more preferably 0.20 to 1.10 quaternary groups per glucose unit. Ideally this degree of substitution is 0.20 to 0.80 and most preferably 0.50 to 0.80.
- the cationic polymers used in the present invention may be produced by treating starch with an agent which will partially "fragment" the polysaccharide chain (e.g. by use of an oxidising agent such as hydrogen peroxide) and subsequently cationising the "fragmented" product in a reaction in which the solids content is a minimum of 50% (more preferably at least 55%) by weight.
- the cationizing agent may be used in an amount of 20 to 160%, most preferably 80 to 120%, by weight of the amount of degraded starch thereby allowing the degree of cationization to be readily controlled.
- the preferred quaternising chemical is 2,3-epoxypropyl trimethyl ammonium chloride although other cationizing agents may be used.
- Preferred cationic polymers for use in the invention have a nitrogen content in the range of approximately 1-5% (for the cationizing chemical being 2,3- epoxypropylene trimethyl ammonium chloride). It is particularly preferred that cationic, oxidised starch derivatives for use in the invention have a nitrogen content of 3-5%, more preferably 3-4%, and ideally about 3.5% (for the cationizing chemical being 2,3-epoxypropylene trimethyl ammonium chloride).
- the cationic polymer for use in the invention has a molecular weight in the range of 100,000 to 500,000 Daltons, more preferably 150,000 to 450,000.
- Particularly suitable quatemised, oxidised starch derivatives for use in formulating the emulsions of the invention are available under the trade mark RAIFIX which designates a range of products of varying cationicity and molecular weight.
- Typical RAIFIX products have a degree of substitution (by the cationizing agent) of 0.1 to 1.1 which corresponds to a nitrogen content in the range of approximately 1-5% (for the cationizing chemical being 2,3-epoxypropylene trimethyl ammonium chloride).
- RAIFIX products are available under the following five figure product codes:
- the first three figures are representative of molecular weight (the higher the number the higher the percentage molecular weight) and the final two figures being approximately ten times the nitrogen content.
- Estimates of the relative molar mass of the RAIFIX products are 100,000 Daltons for the OlOxx designations and 500,000 Daltons for the 250xx designations.
- the rosin used in the emulsion of the invention may be for example be a wood rosin, gum rosin, tall oil rosin or mixtures thereof.
- the rosin may be maleated, fortified, unfortified, hydrogenated or disproportionated.
- the rosin may optionally be esterified. If a tall oil rosin is used then it is preferred that it be pre-treated with paraformaldehyde.
- the preferred rosin for use in the invention is a maleated or fumarated rosin.
- the rosin may be compounded with tall oil fatty acids as proposed in UK-A-2 268 941.
- Tall oil fatty acids are available for example under the designation CENTURY MO6 (ex Union Camp Chemicals Limited). Any other rosin diluent (e.g. a hydrocarbon resin) may alternatively be used.
- the rosin emulsion from which the "one-shot" composition is produced may, for example, have a solids content of 30 to 50% by weight.
- This emulsion may be of a rosin which has been fortified with maleic anhydride or fumaric acid.
- the emulsion may be an anionic rosin emulsion, e.g. a casein stabilised Bewoid rosin emulsion. It is however also within the scope of the invention that the rosin emulsion (from which the one-shot composition is produced) be a cationic rosin emulsion (e.g. as described in EP-A-0 406 461).
- the aluminium salt may, for example, be aluminium sulphate (e.g. paper makers alum), aluminium chloride, polyaluminium chloride or aluminium chlorohydrate.
- the starch derivative is, as indicated, preferably a product as available under the trade mark RAIFIX.
- the "one-shot" composition will generally have a solids content of at least 10% more usually at least 20%. Typically the solids content will be in the range 20% to 35%o, e.g. 27% to 34% by weight.
- the "one shot” composition will be formulated so that the relative amounts of rosin, aluminium salt and starch derivative are in the ratio range 1 :(1-1.5, e.g. ca l.4):(0.1-0.5, e.g. ca ⁇ .3).
- compositions in accordance with the invention may be produced by admixture of the various components followed by homogenisation to produce a smooth, low viscosity emulsion (preferably by initial mixing of rosin and starch derivatives prior to mixing of the aluminium salt).
- One-shot compositions in accordance with the invention may be used for the sizing of paper and therefore according to a second aspect of the present invention there is provided a method of producing paper in which sizing of the fibres of the paper is effected using a "one-shot" composition in accordance with the first aspect of the invention.
- the one-shot composition may be added at the wet-end of the paper making process (i.e. to a dispersion of the paper making fibres before the dispersion is laid onto the paper making wire machine or at a size press after formation of the paper web.
- the amount of composition used for sizing the paper will typically be such that the amount of rosin is 0.2-3% dry basis on the weight of fibres.
- the invention is illustrated by the following non-limiting Example.
- Formulations A-G as identified in Table 1 were produced from the rosin emulsion identified under (1) below, at least one of the aluminium salts identified under (2), and one of the starch derivatives identified under (3).
- the rosin emulsion used was that available under the trade mark NEUSIZE 3 from Roe Lee Paper Chemicals Co. It is a fortified gum rosin emulsion, with casein as a stabiliser, at 30%) solids by weight.
- the aluminium compound used was at least one of
- the starch derivative used was one of
- All formulations (i.e. A-G) were produced by mixing the identified components in the order indicated with a laboratory stirrer and then passing the resultant suspension through a Christisen Scientific Equipment Ltd, H5000, air powered microfluidiser to produce a smooth, low viscosity emulsion.
- the mean particle size of the resultant emulsion and its stability are shown in Table 1. Certain of the formulations were tested for their sizing properties. For this purpose, the 1 minute Cobb value was obtained for the 10th sheet in a series made with recycled backwater. This technique has been shown in other investigations to give results nearer those obtained on a full scale paper machine than single hand sheet results.
- the furnish used was a mixed hardwood, softwood furnish containing 70% birch and 30% bleached craft softwood.
- NEUSIZE 3 For comparison of the efficiency of the tested formulations, a similar test was conducted using NEUSIZE 3 and paper makers alum had a similar level of rosin addition and this resulted in a Cobb value of 20.8. During all of these experiments, a poly-acrylamide (Percol 63) was added at a rate of 300g per tonne.
- formulation B was a stable product which gave a similar Cobb value to the comparative sizing test using NEUSIZE 3 and paper makers alum.
- Formulation B is therefore the preferred formulation of Table 1.
- Formulation A was susceptible to thickening and separation whereas Formulation B was perfectly stable.
- Formulations E and F also displayed some thixotropy but this could be controlled by changing the amount and type of RAIFIX. Table 1. Formulations of various one-shot emulsions and their properties.
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE69728285T DE69728285T2 (en) | 1996-11-30 | 1997-12-01 | STARCH DERIVATIVE COLOPHONIUM EMULSION FOR PAPER LUBRICATION |
US09/319,100 US6290765B1 (en) | 1996-11-30 | 1997-12-01 | Rosin emulsion including starch derivative for paper sizing |
AU54009/98A AU5400998A (en) | 1996-11-30 | 1997-12-01 | Rosin emulsion including starch derivative for paper sizing |
CA002273213A CA2273213C (en) | 1996-11-30 | 1997-12-01 | Rosin emulsion including starch derivative for paper sizing |
EP97947760A EP0941384B1 (en) | 1996-11-30 | 1997-12-01 | Rosin emulsion including starch derivative for paper sizing |
AT97947760T ATE262616T1 (en) | 1996-11-30 | 1997-12-01 | ROSIN EMULSION CONTAINING STARCH DERIVATIVE FOR PAPER SIZING |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9625006.3 | 1996-11-30 | ||
GBGB9625006.3A GB9625006D0 (en) | 1996-11-30 | 1996-11-30 | 'One-shot'rosin emulsion including starch derivative for paper sizing |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998024972A1 true WO1998024972A1 (en) | 1998-06-11 |
Family
ID=10803790
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1997/003197 WO1998024972A1 (en) | 1996-11-30 | 1997-12-01 | Rosin emulsion including starch derivative for paper sizing |
Country Status (11)
Country | Link |
---|---|
US (1) | US6290765B1 (en) |
EP (1) | EP0941384B1 (en) |
AT (1) | ATE262616T1 (en) |
AU (1) | AU5400998A (en) |
CA (1) | CA2273213C (en) |
DE (1) | DE69728285T2 (en) |
ES (1) | ES2218704T3 (en) |
FI (1) | FI117678B (en) |
GB (1) | GB9625006D0 (en) |
PT (1) | PT941384E (en) |
WO (1) | WO1998024972A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6398912B1 (en) * | 1998-07-10 | 2002-06-04 | Raisio Chemicals Ltd. | Additive for paper making |
US6610672B2 (en) | 1999-10-20 | 2003-08-26 | Grain Processing Corporation | Compositions including reduced malto-oligosaccharide preserving agents, and methods for preserving a material |
US6716313B2 (en) * | 1998-07-10 | 2004-04-06 | Raisio Chemicals, Ltd. | Additive for paper making |
US6911114B2 (en) | 2002-10-01 | 2005-06-28 | Kimberly-Clark Worldwide, Inc. | Tissue with semi-synthetic cationic polymer |
EP1023494B1 (en) * | 1997-10-08 | 2006-06-14 | Ciba SC Holding AG | Rosin emulsion |
WO2014006345A1 (en) | 2012-07-06 | 2014-01-09 | Roquette Freres | Mixtures of polyvinylamines and of liquid compositions of cationic amylaceous materials as agents for improving the dry strength of paper and cardboard |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FI113968B (en) * | 2001-05-23 | 2004-07-15 | Raisio Chem Oy | Solution polymer stabilized with a cationic polysaccharide |
MX2009009394A (en) | 2007-03-15 | 2009-09-11 | Basf Se | Heat-sensitive coating compositions based on resorcinyl triazine derivatives. |
WO2009024497A1 (en) * | 2007-08-22 | 2009-02-26 | Basf Se | Laser-sensitive coating composition |
CA2702732A1 (en) * | 2007-11-07 | 2009-05-14 | Basf Se | New fiber products |
US20120045624A1 (en) | 2008-10-27 | 2012-02-23 | Basf Se | Aqueous laser-sensitive composition for marking substrates |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1171724B (en) * | 1959-12-24 | 1964-06-04 | Hercules Powder Co Ltd | Process for gluing or waterproofing paper products |
GB2050453A (en) * | 1979-05-23 | 1981-01-07 | Tenneco Chem | Chemical compositions useful in the manufacture of paper sizing agents |
WO1986002677A1 (en) * | 1984-10-22 | 1986-05-09 | Eka Nobel Aktiebolag | Hydrophobing agent for cellulosic fibers, method of preparing the agent, and use of the agent for stock hydrophobation |
WO1995018157A1 (en) * | 1993-12-27 | 1995-07-06 | Raisio Chemicals Oy | Method for producing of cationic starch |
WO1996035841A1 (en) * | 1995-05-12 | 1996-11-14 | Eka Chemicals Ab | Sizing dispersions |
-
1996
- 1996-11-30 GB GBGB9625006.3A patent/GB9625006D0/en active Pending
-
1997
- 1997-11-28 FI FI974372A patent/FI117678B/en not_active IP Right Cessation
- 1997-12-01 AT AT97947760T patent/ATE262616T1/en not_active IP Right Cessation
- 1997-12-01 CA CA002273213A patent/CA2273213C/en not_active Expired - Fee Related
- 1997-12-01 DE DE69728285T patent/DE69728285T2/en not_active Expired - Lifetime
- 1997-12-01 AU AU54009/98A patent/AU5400998A/en not_active Abandoned
- 1997-12-01 ES ES97947760T patent/ES2218704T3/en not_active Expired - Lifetime
- 1997-12-01 WO PCT/GB1997/003197 patent/WO1998024972A1/en active IP Right Grant
- 1997-12-01 EP EP97947760A patent/EP0941384B1/en not_active Expired - Lifetime
- 1997-12-01 PT PT97947760T patent/PT941384E/en unknown
- 1997-12-01 US US09/319,100 patent/US6290765B1/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1171724B (en) * | 1959-12-24 | 1964-06-04 | Hercules Powder Co Ltd | Process for gluing or waterproofing paper products |
GB2050453A (en) * | 1979-05-23 | 1981-01-07 | Tenneco Chem | Chemical compositions useful in the manufacture of paper sizing agents |
WO1986002677A1 (en) * | 1984-10-22 | 1986-05-09 | Eka Nobel Aktiebolag | Hydrophobing agent for cellulosic fibers, method of preparing the agent, and use of the agent for stock hydrophobation |
WO1995018157A1 (en) * | 1993-12-27 | 1995-07-06 | Raisio Chemicals Oy | Method for producing of cationic starch |
WO1996035841A1 (en) * | 1995-05-12 | 1996-11-14 | Eka Chemicals Ab | Sizing dispersions |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1023494B1 (en) * | 1997-10-08 | 2006-06-14 | Ciba SC Holding AG | Rosin emulsion |
US6398912B1 (en) * | 1998-07-10 | 2002-06-04 | Raisio Chemicals Ltd. | Additive for paper making |
US6716313B2 (en) * | 1998-07-10 | 2004-04-06 | Raisio Chemicals, Ltd. | Additive for paper making |
US7094319B2 (en) | 1998-07-10 | 2006-08-22 | Ciba Specialty Chemicals Corporation | Additive for paper making |
US6610672B2 (en) | 1999-10-20 | 2003-08-26 | Grain Processing Corporation | Compositions including reduced malto-oligosaccharide preserving agents, and methods for preserving a material |
US6911114B2 (en) | 2002-10-01 | 2005-06-28 | Kimberly-Clark Worldwide, Inc. | Tissue with semi-synthetic cationic polymer |
WO2014006345A1 (en) | 2012-07-06 | 2014-01-09 | Roquette Freres | Mixtures of polyvinylamines and of liquid compositions of cationic amylaceous materials as agents for improving the dry strength of paper and cardboard |
US9598820B2 (en) | 2012-07-06 | 2017-03-21 | Roquette Freres | Mixtures of polyvinylamines and of liquid compositions of cationic amylaceous materials as agents for improving the dry strength of paper and cardboard |
Also Published As
Publication number | Publication date |
---|---|
EP0941384A1 (en) | 1999-09-15 |
DE69728285D1 (en) | 2004-04-29 |
ATE262616T1 (en) | 2004-04-15 |
US6290765B1 (en) | 2001-09-18 |
FI974372A (en) | 1998-05-31 |
AU5400998A (en) | 1998-06-29 |
DE69728285T2 (en) | 2005-03-10 |
CA2273213A1 (en) | 1998-06-11 |
GB9625006D0 (en) | 1997-01-15 |
CA2273213C (en) | 2006-08-22 |
ES2218704T3 (en) | 2004-11-16 |
PT941384E (en) | 2004-08-31 |
FI974372A0 (en) | 1997-11-28 |
EP0941384B1 (en) | 2004-03-24 |
FI117678B (en) | 2007-01-15 |
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