EP0200504B1 - Zusammensetzungen für die Papierleimung - Google Patents
Zusammensetzungen für die Papierleimung Download PDFInfo
- Publication number
- EP0200504B1 EP0200504B1 EP86303161A EP86303161A EP0200504B1 EP 0200504 B1 EP0200504 B1 EP 0200504B1 EP 86303161 A EP86303161 A EP 86303161A EP 86303161 A EP86303161 A EP 86303161A EP 0200504 B1 EP0200504 B1 EP 0200504B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyelectrolyte
- size
- weight
- water
- dispersion
- 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.)
- Expired
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
- 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
- D21H17/375—Poly(meth)acrylamide
-
- 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
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; Derivatives thereof
- D21H17/15—Polycarboxylic acids, e.g. maleic acid
-
- 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
-
- 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
-
- 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
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
- D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised
Definitions
- the invention relates to the sizing of cellulosic fibres and to compositions for use in this, and to their manufacture.
- sizing can be carried out by adding a sizing agent to the pulp slurry (usually termed internal sizing) or the sizing agent can be applied to the formed paper sheet.
- This invention is concerned with the internal sizing process.
- sizing agent there are two types in general use. One of these is based on rosin which is used in conjunction with alum. The rosin is added as a soap solution or as an emulsion and alum is added afterwards just prior to sheet formation to precipitate the rosin as a fine particulate which is retained by the sheet.
- the second type of size is a reactive size, such as a ketene dimer or an anhydride-based size, which reacts chemically with the cellulosic fibres.
- a reactive size such as a ketene dimer or an anhydride-based size, which reacts chemically with the cellulosic fibres.
- it is applied in combination with a polyelectrolyte which will help to retain the size in the sheet
- the reactive size is generally added to the pulp in the form of an aqueous emulsion, generally a cationic emulsion.
- the emulsion can be prepared at the mill but this necessitates the mill having emulsifying equipment and so it would be more convenient if a concentrated emulsion could be supplied to the mill ready for dilution and use.
- reactive sizes tend to react with water so that an aqueous emulsion is liable to be rather unstable.
- Anhydride based sizes such as alkenyl succinic anhydride sizes, are so reactive that their emulsions have to be prepared at the mill just prior to use. These sizes are normally supplied to the mill with a cationic starch which generally has to be precooked before emulsification, thus making it even less convenient for the emulsion to be formed at the mill.
- Ketene dimer sizes often are supplied to the mill in the form of an emulsion but these emulsions have only limited shelf-life and the maximum concentration of ketene dimer in the emulsion is rather low, generally below 6 %, so that very large volumes of emulsion have to be supplied to the paper manufacture.
- Emulsification of liquid ketene dimers can be achieved using conventional emulsification equipment but some of the preferred ketene dimers are solids at ambient temperature. As described in U.S. Patent Specification 3,046,186, emulsification of these necessitates initially either melting the solid (so that upon cooling the emulsion is converted to a dispersion) or dissolving the solid in a solvent, generally benzene.
- a typical important ketene dimer is distearyl ketene dimer and this only has relatively low solubility in organic solvents with the result that the solution of it that is emulsified must be rather dilute.
- this dimer precipitates from a 40 % by weight solution in benzene (weight ratio benzene : dimer of 1 : 0.67) and so any solution in benzene must be much more dilute than this. Also this dimer is less soluble in other organic solvents than it is in benzene.
- the emulsions are generally prepared by emulsifying the dimer into an aqueous solution of cationic dispersing agent although that patent does mention that «in certain instances the emulsifying agent may be predispersed in the ketene dimer Colour It is stated that the emulsions may be prepared at any convenient solids content but are used at 1 to 5 % solids by weight.
- Example 1 the initial composition that was prepared and that contained both size and polyelectrolyte was very dilute.
- the initial concentration is about 9 % by weight size based on the total composition.
- compositions comprising a substantially anhydrous dispersion of a polyelectrolyte in an organic liquid comprising a solution of a reactive size in a hydrophobic solvent.
- the reactive size concentration in such compositions is generally above 20 % and although it may be up to, for instance, 85 % it is usually lower.
- a concentrate composition according to the present invention is a substantially anhydrous dispersion of a polyelectrolyte in a liquid reactive size.
- the composition is substantially free of solvent.
- solvent Preferably there is no solvent but if solvent is present its arount is insufficient to contribute significantly to the physical properties of the composition, e. g., below 5 % and usually below 1 % solvent by weight of the composition.
- the size could be solid or liquid and was present in the composition in solution in the hydrophobic solvent
- the size in the present invention the size must be liquid at the temperature at which the composition is to be used and stored, typically ambient temperatures such as 20 to 25 °C.
- the size is liquid at 0 °C.
- the preferred liquid sizes for use in the invention are anhydride reactive sizes, including especially alkenyl succinic anhydride sizes. Suitable materials are described in U.S. Patent No. 3,102,064.
- the concentrate composition must be substantially anhydrous in order that the reactive size does not react in the composition upon storage.
- the amount of water is generally not more than the equilibrium moisture content of the polyelectrolyte (i. e., the water content of the polyelectrolyte if it is exposed in the form of dry powder to the ambient atmosphere) and is preferably below this. Normally the water content is not more than 1 %, or at the most 2 %, by weight of the composition.
- the polyelectrolyte will be water soluble and an advantage of the invention is that it can have a any desired molecular weight and in particular can have a molecular weight that is higher than is conveniently possible with existing compositions.
- the intrinsic viscosity can typically be above 1 and generally above 3, e. g., above 6. Although it is generally below 9 it can be higher, e. g., up to 20 or more.
- the polyelectrolyte may be formed from a water soluble ethylenically unsaturated monomer (or a water soluble blend of ethylenically unsaturated monomers) and may be anionic but the cationic polyelectrolytes are generally preferred.
- Preferred cationic electrolytes include homopolymers or copolymers of diallyl dialkyl (generally dimethyl) ammonium chloride and homopolymers and copolymers of dialkylaminoalkyl acrylates and methacrylates (preferably dimethylaminoethyl acrylates and methacrylates) present as acid addition salts or quaternary ammonium salts, generally quatemised with methyl chloride or dimethyl sulphate.
- Copolymers of such monomers may be formed with acrylamide or methacrylamide and will typically contain at least 10 %, and usually at least 30 %, by weight of the cationic monomer.
- Other cationic acrylamides and methacrylamides can be used.
- Other cationic polymers that can be used are polyamines and polyimines such as polyamine-epi-halohydrin polymers and dicyandiamide condensates and polyethylene imines.
- Suitable anionic polymers include polymers formed from monomers including carboxylic or sulphonic acid groups. These groups may be present as free acid or, more usually, as a water soluble ammonium or alkali metal (generally sodium) salt. Suitable acids are acrylic acid, methacrylic acid and 2-acrylamido-2-methyl-propane sulphonic acid. Sodium allyl sulphonate may be used.
- the anionic polymers may be homopolymers of such acids, or mixtures thereof, or copolymers with, for instance, acrylamide. A suitable polymer if polyacrylamide containing up to 25 % or more acrylic acid groups.
- the particles of polyelectrolyte are generally below 500 pm and preferably below 200 pm in size.
- the novel compositions can be obtained by mixing powdered polyelectrolyte into the liquid reactive size.
- the polyelectrolyte generally has a particle size above 5, and usually above 10 ⁇ m, and often the maximum particle size is within the range 20 to 100 W m.
- composition should be used whilst the polyelectrolyte is substantially uniformly dispersed throughout the liquid reactive size. If the composition has a tendency towards settlement it should therefore be used before serious formation of a non-redispersable sediment occurs. Settlement can be minimised or prevented by the inclusion of an effective amount (e. g. 0.1 to 10 %) of a dispersion promoter.
- a dispersion promoter e. g. 0.1 to 10 %
- dispersion stabilisers that are insoluble in the reactive size, such as the clays and silica based dispersion stabilisers known for stabilising dispersions in oil, may be used.
- Preferred stabilisers for this purpose are organophilic clays such as the materials sold under the trade Mark Bentone. Stabilisers that are soluble in the size may also be used.
- compositions according to the invention however have the polyelectrolyte with a maximum particle size below 10 wm, preferably below 3 pm.
- a dispersion promoter can be added to the composition the required amount is usually low. Deliberate addition of, for instance, clays is generally unnecessary.
- the particles are preferably made by reverse phase polymerisation preferably in the presence of a dispersion stabiliser of the type known for use in reverse phase polymerisation. The presence of residues of this on the polymer particles will generally be sufficient to stabilise the compositions of the invention.
- compositions are made by blending into the liquid size a substantially anhydrous dispersion of polyelectrolyte in a volatile organic liquid and then evaporating this organic liquid.
- the volatility of the liquid must be such that it can be evaporated from the dispersion in liquid reactive size at a temperature below that at which undesired chemical reaction might occur.
- the particle size of this dispersion in organic liquid should be below 10, and often below 3 pm. Preferably it is below 2 wm, often mainly in the range 0.05 to 1 ⁇ m.
- It may be made by reverse phase polymerisation, generally reverse phase suspension polymerisation, of water soluble monomer or monomer blend dispersed in water immiscible organic liquid.
- the reverse phase polymerisation may be conducted in the presence of an oil soluble polymer, generally an amphipathic polymer, as a dispersion stabiliser and this stabiliser may also promote the stability of the final dispersion in the liquid size.
- the reverse phase polymerisation may also be conducted in the presence of a water in oil emulsifier. Materials and processes for reverse phase polymerisation are well known and are described in, for instance, EP 0126528.
- Suitable organic liquids that can be used for the dispersion include volatile aliphatic hydrocarbons.
- the dispersion After making the dispersion of polyelectrolyte in organic liquid by reverse phase polymerisation the dispersion is dehydrated to a substantially anhydrous state in conventional manner, generally by azeotropic distillation.
- the content of continuous organic phase can be altered after polymerisation in known manner in order that the organic liquid (that has to be evaporated from the dispersion of polyelectrolyte in liquid size and organic liquid) has the optimum volatility.
- compositions according to the invention are substantially free of solvent or other diluents and at least 80 %, preferably at least 85 % or at least 90 %, consists of the polyelectrolyte and the liquid size.
- Preferred compositions contain from 45 to 90 %, preferably 60 to 80 %, by weight reactive size, 10 to 50 %, preferably 20 to 40 %, by weight polyelectrolyte and 0 to 15 %, preferably 5 to 10 % of additives such as the described insoluble or soluble stabilisers or water-in-oil emulsifiers.
- the additives include oil-in-water emulsifying agent that serves to facilitate emulsification of the concentrate into water at the point of use.
- oil-in-water emulsifying agent that serves to facilitate emulsification of the concentrate into water at the point of use.
- oil-in-water emulsifying agent may be present in the water into which the concentrate is emulsified. If appropriate mixing apparatus is available, adequate emulsification may be achieved without the use of an oil-in-water emulsifying agent, but this is usually less preferred.
- the concentrate is converted to an emulsion in water prior to use.
- the water in which the emulsion is formed may be the water of the cellulosic pulp suspension that is to be treated but preferably the concentrate is first converted into an aqueous emulsion to give a reactive size concentration of from 0.01 to 5 %, preferably 0.05 to 1 %, based on the weight of the aqueous solution.
- This emulsion may then be added to the aqueous cellulosic pulp, and paper may be made from it, in the usual way.
- the amount of reactive size in the aqueous pulp is generally from about 0.01 to about 1 % by weight based on the dry weight of the pulp.
- the active size/oil droplets are retained by the polymer on the fibres and the size reacts with the fibres.
- the size released from an emulsion in this way produces results at least as good as those obtained with the conventional ketene dimer emulsions.
- a sizing concentrate was prepared, including alkenyl succinic anhydride as the active sizing constituent, by dispersing a powdered polyelectrolyte into the liquid sizing component to which had been added an oil-in-water emulsifying surfactant.
- the chosen alkenyl succinic anhydride was a liquid at ambient temperature and did not require melting to allow the dispersion to take place.
- the polyelectrolyte a copolymer of methyl chloride quatemised dimethyl aminoethylmethacrylate and acrylamide (25.75 by weight), was prepared by bulk solution polymerisation.
- the resulting polymer gel was cut into particles less than 5 mm in dimension dried on a fluid bed drier and then gound down to the required dimension of less than 53 pm.
- the composition comprised 65 g of alkenyl succinic anhydride, 10 g of oil-in-water emulsifying surfactant, 12.5 g of polyelectrolyte to give a 74.3 % active sizing composition.
- the composition was ostensibly free from water.
- Example 2 2.7 g of the concentrate composition made in Example 1 was added to 197.3 g of water with stirring to give a 1 % active alkenyl succinic anhydride emulsion which was used to carry out 1 minute Cobb tests. This emulsion was labelled A.
- handsheets were prepared, from a bleached sulphate/bleached birch stock containing 10 % calcium carbonate loading, on a Standard Laboratory sheet making machine. Prior to sheet formation the required amount of 1 % alkenyl succinic anhydride emulsion as prepared above was added to 600 ml of 1.0 % consistency stock. After stirring, handsheets were prepared on the standard sheet-making machine. The sheets were couched off the sheet-machine in the normal manner placed on glazing plates and pressed at 0.34 MPa (50 psi) for 5 minutes prior to drying on rings at 110 °C for 1 hour. After conditioning at room temperature the degree of sizing achieved was measured by the standard 1 minute Cobb test. The results are shown in the table below.
- Example 1 A concentrate similar of Example 1 is made using, instead of the comminuted gel polymer, a bead polymer made by reverse phase bead polymerisation followed by azeotropic distillation and separation of the beads from the oil in which they were formed.
- a copolymer of 75 parts by weight acrylamide and 25 parts by weight of trimethyl ⁇ -acryloxyethyl ammonium chloride was first prepared in a hydrocarbon liquid of boiling range 154-168 °C (Shell SBP1 1) by conventional reverse phase polymerisation as follows.
- An oil phase was prepared comprising 363.3 g of SBP11, 14,2 g at a 2 to 1 molar copolymer of stearyl methacrylate and methacrylic acid as suspension polymerisation stabiliser (as described in GB 1,482,515) and 7.8 g Span 80.
- Span is a trade mark.
- the aqueous phase was homogenised with the oil phase and deoxygenated with nitrogen gas then polymerised by stirring in 1.5 ml of a 5 % solution of sodium metabisulphite in water followed by a 1 % solution of tertiary butyl hydroperoxide in SBP11 added at a rate of 0.25 ml per minute until polymerisation was complete.
- the resulting aqueous polymer gel dispersion was azeotropically dehydrated under reduced pressure by recycling the SBP11. Part of the SBP11 was then distilled off resulting in an anhydrous polymer dispersion at a concentration of 40 % polymer by weight in SBP11.
- Example 5 The concentrate described in Example 5 was used to prepare a corresponding aqueous emulsion, having a 1 % by weight active size content, by stirring the appropirate amount of dispersion into water. This emulsion was further diluted to 0.1 % by weight active size content and labelled B.
- a conventional alkenyl succinic anhydride emulsion was prepared as follows. A 12 % aqueous dispersion of a cationic starch was cooked at 95 °C for 20 minutes with constant stirring. The cooked starch was cooled and diluted to 9 % activity. 2 parts by weight of alkenyl succinic anhydride was added to 3 parts by weight of cationic starch with agitation. High shear mixing with a Silverson mixer was continued to achieve a fine particle size emulsion. This emulsion was diluted with water to 0.1 % by weight active size content and labelled C.
- handsheets 100 g/m 2 handsheets were-prepared from a bleached sulphate/bleached birch stock containing 10 % calcium carbonate loading on standard laboratory sheet making machine. Prior to sheet formation, the required amount of 0.1 % emulsion labelled B was added to 600 ml to 1.0 % consistency stock. After stirring, handsheets were prepared, pressed at 0.34 MPa (50 p.s.i.) for 5 minutes prior to drying at 11d °C for 1 hour. After conditioning at room temperature, the degree of sizing was determined by the standard 1 minute cobb test
- Control sheets were prepared in the same manner as described above, but with emulsion C replacing emulsion B. The results are shown below :
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- Chemical Kinetics & Catalysis (AREA)
- Chemical & Material Sciences (AREA)
- Paper (AREA)
- Colloid Chemistry (AREA)
- Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
- Saccharide Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Artificial Filaments (AREA)
- Making Paper Articles (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Claims (14)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT86303161T ATE45404T1 (de) | 1985-05-03 | 1986-04-25 | Zusammensetzungen fuer die papierleimung. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB8511379 | 1985-05-03 | ||
GB858511379A GB8511379D0 (en) | 1985-05-03 | 1985-05-03 | Compositions for sizing paper |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0200504A1 EP0200504A1 (de) | 1986-11-05 |
EP0200504B1 true EP0200504B1 (de) | 1989-08-09 |
Family
ID=10578656
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP86303161A Expired EP0200504B1 (de) | 1985-05-03 | 1986-04-25 | Zusammensetzungen für die Papierleimung |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0200504B1 (de) |
JP (1) | JPS61258098A (de) |
AT (1) | ATE45404T1 (de) |
AU (1) | AU593245B2 (de) |
DE (1) | DE3664940D1 (de) |
FI (1) | FI84383C (de) |
GB (1) | GB8511379D0 (de) |
NO (1) | NO172551C (de) |
ZA (1) | ZA863313B (de) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5176748A (en) * | 1988-07-05 | 1993-01-05 | Bercen, Inc. | Alkenyl succinic anhydride emulsion |
EP0840822A1 (de) * | 1995-07-27 | 1998-05-13 | Cytec Technology Corp. | Synthetische kationische polymeren als asa-leimungspromotoren |
EP0981573B1 (de) * | 1998-03-17 | 2004-09-01 | Hutchinson | Stabile emulsionen, verfahren zu deren herstellung und ihre anwendungen |
PL2087171T3 (pl) * | 2006-12-01 | 2012-04-30 | Akzo Nobel Nv | Produkt celulozowy |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3311532A (en) * | 1965-03-17 | 1967-03-28 | American Cyanamid Co | Ketene dimer paper sizing compositions including acyl compound extender and paper sized therewith |
SE361908B (de) * | 1972-07-14 | 1973-11-19 | Kema Nord Ab | |
US4214948A (en) * | 1974-07-31 | 1980-07-29 | National Starch And Chemical Corporation | Method of sizing paper |
USRE29960E (en) * | 1976-05-05 | 1979-04-10 | National Starch And Chemical Corp. | Method of sizing paper |
JPS58120897A (ja) * | 1982-01-05 | 1983-07-18 | 星光化学工業株式会社 | 紙のサイジング方法 |
US4435217A (en) * | 1982-04-22 | 1984-03-06 | Venture Innovations, Inc. | Concentrated hydrophilic polymer suspensions |
JPS59192798A (ja) * | 1983-04-16 | 1984-11-01 | 日本石油化学株式会社 | 紙サイズ剤組成物 |
GB8329655D0 (en) * | 1983-11-07 | 1983-12-07 | Allied Colloids Ltd | Sizing paper |
-
1985
- 1985-05-03 GB GB858511379A patent/GB8511379D0/en active Pending
-
1986
- 1986-04-25 EP EP86303161A patent/EP0200504B1/de not_active Expired
- 1986-04-25 AT AT86303161T patent/ATE45404T1/de not_active IP Right Cessation
- 1986-04-25 DE DE8686303161T patent/DE3664940D1/de not_active Expired
- 1986-04-29 FI FI861796A patent/FI84383C/fi not_active IP Right Cessation
- 1986-05-01 AU AU56898/86A patent/AU593245B2/en not_active Ceased
- 1986-05-02 ZA ZA863313A patent/ZA863313B/xx unknown
- 1986-05-02 NO NO861755A patent/NO172551C/no unknown
- 1986-05-06 JP JP61104573A patent/JPS61258098A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
AU593245B2 (en) | 1990-02-08 |
NO172551C (no) | 1993-08-04 |
EP0200504A1 (de) | 1986-11-05 |
DE3664940D1 (en) | 1989-09-14 |
FI84383B (fi) | 1991-08-15 |
JPS61258098A (ja) | 1986-11-15 |
NO172551B (no) | 1993-04-26 |
AU5689886A (en) | 1986-11-06 |
NO861755L (no) | 1986-11-04 |
FI861796A0 (fi) | 1986-04-29 |
ATE45404T1 (de) | 1989-08-15 |
FI861796A (fi) | 1986-11-04 |
FI84383C (fi) | 1991-11-25 |
GB8511379D0 (en) | 1985-06-12 |
ZA863313B (en) | 1987-07-29 |
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