EP0512038B1 - Reduzierung von schaum bei der papierherstellung - Google Patents

Reduzierung von schaum bei der papierherstellung Download PDF

Info

Publication number
EP0512038B1
EP0512038B1 EP91903705A EP91903705A EP0512038B1 EP 0512038 B1 EP0512038 B1 EP 0512038B1 EP 91903705 A EP91903705 A EP 91903705A EP 91903705 A EP91903705 A EP 91903705A EP 0512038 B1 EP0512038 B1 EP 0512038B1
Authority
EP
European Patent Office
Prior art keywords
paper
water
calcium carbonate
salt
sizing
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 - Lifetime
Application number
EP91903705A
Other languages
English (en)
French (fr)
Other versions
EP0512038A1 (de
Inventor
Alberto Malatesta
Christian Pierre
René COHARD
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.)
ExxonMobil Chemical Patents Inc
Original Assignee
Exxon Chemical Patents Inc
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 GB909001438A external-priority patent/GB9001438D0/en
Priority claimed from GB909008336A external-priority patent/GB9008336D0/en
Application filed by Exxon Chemical Patents Inc filed Critical Exxon Chemical Patents Inc
Publication of EP0512038A1 publication Critical patent/EP0512038A1/de
Application granted granted Critical
Publication of EP0512038B1 publication Critical patent/EP0512038B1/de
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
    • 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
    • D21H17/17—Ketenes, e.g. ketene dimers
    • 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
    • D21H17/16—Addition products thereof with hydrocarbons
    • 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
    • D21H17/65—Acid compounds
    • 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
    • D21H21/06—Paper forming aids
    • D21H21/12—Defoamers

Definitions

  • the present invention is concerned with reducing the problems caused by foam formation during the production of paper produced under alkaline or neutral conditions using cyclic acid anhydrides, especially alkyl or alkenyl succinic anhydrides (ASA) as sizes.
  • cyclic acid anhydrides especially alkyl or alkenyl succinic anhydrides (ASA) as sizes.
  • Sizing paper with alkenyl succinic anhydrides (ASA) at or about a neutral pH, using paper stock containing calcium carbonate as a neutral whitening filler is a well known process, but it is known to produce an unacceptable amount of foam in the paper machine white water recycle.
  • the foam accumulates as white pitches in the white water recycle and is transported with the paper stock to the paper machine head box. Although silicones and other anti-foam additives are sometimes added they do not give adequate foam reduction.
  • the sizing is carried out by metering ASA as an emulsion into the paper stock in the wet end of the paper machine just before feeding the diluted paper stock to the Fourdrinier table.
  • the paper stock contains 20-30% (on dry cellulose) calcium carbonate as an inert filler. More recently it has been proposed in EP-A-0348127 that the ASA may be applied neat or as a solution.
  • Suitable technologies have been developed to produce emulsion involving both dynamic and static mixing (US-E-29960), ancillary materials, classified as activators, promoters and stabilizers, to optimise ASA emulsions with respect to sizing, retention and paper machine runnability.
  • the place to introduce the ASA emulsion in the paper machine can be chosen according to various plant needs, it is customary to select a position to minimize hold time and where the fluid is turbulent to facilitate ASA mixing with the paper stock.
  • ASA are easily hydrolysable compounds which produce alkenyl succinic acid on reaction with water.
  • the acid is not active in sizing paper (TAPPI Journal 70, 12, pages 117-121, 1987). Moreover, it builds up in the white water recycle to a point when the production of foam and of white pitches occurs with the appearance of dark spots in the paper. Plating out of the white pitches also occurs on several critical places of the paper machine (such as the Fourdrinier net, the drying section's felts, the head box and in the piping system) with a consequent productivity decrease mainly due to press picking, felt soilage and lowered drainage.
  • ASA's hydrolysis kinetics indicate a rapid reaction whose rate increases with temperature and pH and it is a function of the emulsion's particle size (TAPPI Alkaline Papermaking 1985, pages 17-20).
  • the ASA emulsion in water is therefore generally produced on site just before its introduction in the paper machine to minimize hydrolysis.
  • ASA emulsions A number of formulations are available to the paper industry to prepare ASA emulsions see (TAPPI Alkaline Papermaking 1985, pages 113-133, TAPPI Sizing short course 1987, pages 89-91). They are based on an emulsifier compound (such as sulfosuccinates, nonylphenol adducts with ethylene and propylene oxides and the like) and natural and synthetic organic compounds bearing positive charges (such as cationized starch, polyamines and the like).
  • an emulsifier compound such as sulfosuccinates, nonylphenol adducts with ethylene and propylene oxides and the like
  • natural and synthetic organic compounds bearing positive charges such as cationized starch, polyamines and the like.
  • An improved sizing process which maximizes ASA first pass retention, involves metering ASA neat or in solution, as a fine spray, directly into the paper stock through a nozzle is described in EP-A-0348127.
  • the improved retention obtainable with the spray-mixing technique depends on several parameters including: ASA particle diameter distribution, presence of ASA-soluble, inert compounds, absence of emulsifiers, a 2-3 orders of magnitude lower contact time with water compared with the emulsion process, etc.
  • EP-A-0041056 describes the use of a complex of cationic starch and colloidal silica as a binder in papermaking.
  • the main purpose of the present invention is to eliminate the technical and cost problems, as previously described, encountered due to foam formation in the ASA-based paper sizing technology.
  • the foam is composed of calcium carbonate mixed with small amounts of fines and traces of calcium succinate, an ionic surfactant. It includes also moderate to large amounts of air.
  • air microbubbles when brought into contact with a calcium carbonate surface, do not spontaneously adhere thereto.
  • a hydrophobic material such as an alkenyl succinic moiety, coats the surface of the calcium carbonate particle the air microbubbles may attach readily to it floating the calcium carbon particles typically of diameter 0.2-0.5 micrometers to the surface so that they accumulate as a frothy foam on top of the process liquid.
  • ASA hydrolysates are essentially alkyl or alkenyl succinic acid dissolved in or dissolving unhydrolysed ASA. They produce a hydrophobic material adhering by chemisorption to calcium carbonate and in part reacting with the production of calcium succinate.
  • foam in the paper making process may be depressed by addition to the paper stock of water soluble salts of a polybasic acid such as sodium hydroxide-treated polymerised silica of the general formula NA 2 O.mSiO 2 nH 2 O where m and n are the number of SiO2 and H2O moles relative to one mole of Na2O.
  • a polybasic acid such as sodium hydroxide-treated polymerised silica of the general formula NA 2 O.mSiO 2 nH 2 O where m and n are the number of SiO2 and H2O moles relative to one mole of Na2O.
  • salts which may be used as foam depressants include sodium derivatives of polyacids such as polyphosphoric acids, polyphosphonic acids, ethylene tetracetic acid, polyacrylic acids, hydrocolloids, polysaccarides, etc.
  • the present invention therefore provides the use of a water soluble or dispersible salt of a polybasic acid or a water colloidal dispersion of said salt as a foam suppressant in alkaline or neutral paper making employing an alkyl or alkenyl succinic acid anhydride sizing agent and calcium carbonate filler.
  • the invention also provides a process for making paper under alkaline or neutral conditions employing an alkyl or alkenyl succinic acid anhydride sizing agent and calcium carbonate filler, characterized in that the formation of foam is depressed by addition to the stock of a water soluble or dispersible salt of a polybasic acid or a water colloidal dispersion of said salt.
  • the treatment of the calcium carbonate with the foam depressant is carried out either batchwise or preferably on-line when the pigment slurry is added to the paper stock. While the foam suppressant and calcium carbonate introduction points could be different, we prefer they are the same and are preferably positioned downstream of the position at which the size is added to the paper stock.
  • foam depression by surface blocking occurs because the depressants preferably bind themselves to the calcium carbonate surface thus preventing air microbubbles from adhering to calcium carbonate particles and floating them upward (A.T. Taggart, Elements of ore dressing, John Wiley & Sons Inc., New York 1951 pages 263 to 281).
  • This invention may be applied to the production of paper or similar products, such as board, cardboard etc., based on cellulose or synthetic fibres.
  • Paper, board, cardboard and other similar products are produced by first dispersing the cellulose or synthetic fibres in large quantities of water and the dispersion passed to a paper making machine where the water is removed to form the continuous paper web.
  • the product is treated with various chemicals which may be injected into the aqueous dispersion of the fibres.
  • One particular treatment common to most paper making processes is sizing.
  • alkyl-ketene dimers and alkenyl succinic anhydrides. These products are generally used in emulsion form as described in, for example, JP-A 62-231099; 61-146898; 61-160495; 52-25102; 60-20905. Whilst the present invention is concerned with sizing in general it is particularly concerned with sizing with alkenyl succinic anhydrides, and alkyl ketene dimers.
  • GB-A-1492104 describes the use of polyoxyalkylene alkyl or arylalkyl ethers, or the corresponding mono- and di-esters derivatives to produce emulsions of cyclic acid anhydrides with a low input of shear energy. Such emulsions are used to disperse intimately the anhydrides into the cellulose stock to produce sized paper.
  • the sizing emulsion can be produced in-situ, within the cellulose stock, or prior to introduction into the cellulose stock.
  • the emulsions are preferably prepared in the presence of cationized stabilisers such as cationized starches, polyaminoethyl acrylate resins, polyamide resins having free amino groups, reacted or not with epichlorohydrin etc.
  • cationized stabilisers such as cationized starches, polyaminoethyl acrylate resins, polyamide resins having free amino groups, reacted or not with epichlorohydrin etc.
  • cationic stabilizers The main function of these cationic stabilizers is to charge positively the emulsion's particles favouring their absorption by Coulombic attraction on the negatively charged surface of the cellulose fibres.
  • the size is introduced in admixture with water.
  • water generally at 30 to 50°C is used as the vehicle to transport the synthetic size in subdivided form.
  • the reactive synthetic sizing compound is continuously dispersed in the form of fine droplets into the wet-end of the paper machine, preferably in places where the cellulose stock water slurry is under high turbulence, to obtain rapid and complete contact of the sizing compound with the paper stock. If necessary turbulence can be controlled by the provision of baffles and stirrers in the flow of the slurry.
  • the absorption of the sizing compound droplets on the cellulosic fibres is aided by a cationizing treatment either the fibres may have undergone such treatment either on-line or in the paper stock preparation tubs alternatively the size may be cationised by for example, addition together with a cationising compound.
  • a cationizing treatment is a standard technique in paper production to favour the retention of wet-strength resins, of mineral charges, etc, which otherwise would be in large part lost.
  • the cationization is generally carried out with long chain fatty amines, synthetic polymers containing amines, cationic modified starches, polyamide-amine resins and other cationized products. Typically 0.02 to 3.50 wt% of cationizing agent based on the weight of dry fibre is used.
  • the contact time with the process water of the reactive synthetic sizing compound in dispersed droplet form is very small, depending on the turbulence of the machine wet-end and on the cationizing treatment of the cellulose fibre. These factors can be varied at will until high deposition rates of the size droplets on the fibres are achieved.
  • the combined action of the extremely low contact time with the process water and the natural hydrophobicity of the sizing compound prevent its hydrolytic degradation and the resulting waste. Moreover, by lowering the droplets diameter to very low values, the interactions with the cellulose fibres and the sizing compound absorption can be improved thus increasing the sizing yield to a level beyond that which can be achieved with the current emulsion technology.
  • the solutions of certain gases, such as methane, propane, butane, chlorofluoro hydrocarbons, carbon dioxide, etc., in the synthetic sizing compound are sprayed in form of fine droplets directly into the wet-end of the paper machine or onto the formed paper web before the machine drying section, or in the size press.
  • a range of gas-sizing compound compositions may be used.
  • a preferred composition could be experimentally determined because it may depend from the type of paper produced in a given machine and from the process parameters.
  • the dissolved gas concentration may be in the range 20 to 50% on the sizing compound although for economic reasons it is preferable that gas concentrations be kept in the range 1 to 19% if the cost factor is very important.
  • the sizing compound gas solutions could also be obtained by previously mixing gas types with low and high solubility into the sizing compound, such as nitrogen and carbon dioxide, nitrogen and methane.
  • the reactive synthetic sizing compound is first dissolved in an anhydrous, aprotic, water-soluble, inert solvent.
  • the solution is sprayed with one or more nozzles as fine droplets directly into the water-cellulose slurry at the paper machine wet-end.
  • the inert solvent is dissolved by the process water thus protecting the reactive sizing compound droplets from water's hydrolytic action and generating in-situ a fresh surface in the presence of cellulose.
  • inert gases dissolved in the aprotic solvent as previously specified (for example carbon dioxide), is claimed also for this type of procedure.
  • aprotic compounds examples include ketones, esters, ethers, aromatic and aliphatic hydrocarbons, (for example acetone, methylethyl ketone, acetonyl acetone, methyl acetate, ethylene glycol diacetate, dioxane, etc).
  • a range of solvent concentrations in the solutions with the sizing compound can be considered. The preferred composition will be determined by experiment depending on the process parameters. Cost considerations would indicate that solvent concentrations in the range 1 to 19% may be preferred to concentrations in the range 20 to 50% or higher, also to avoid the solvents accumulation in the water recycle system.
  • the reactive sizing compound is dissolved in an anhydrous, protic, water soluble compound immediately before being sprayed and transformed into fine droplets.
  • Preferred concentrations of the protic anhydrous solvent with the reactive sizing compound are as previously disclosed in the case of the aprotic solvents.
  • Classes of such solvents include alcohols, etheralcohols, esteralcohols (e.g. methyl alcohol, ethyl alcohol, 2-butoxyethanol, ethylene glycol monoacetate, 2-(2 butoxyethanol), etc.
  • the paper web is dried by heating to temperatures in the range 90 to 120°C thus favouring the reaction between the reactive sizing compound and the hydroxyl groups of the cellulose. This may be performed by the heated cylinders which provide also the pressure needed to impregnate the paper web surface and thickness with the reactive sizing compound.
  • the preferred synthetic reactive sizing compounds are cyclic acid anhydrides of the general formula where R1 is an organic hydrophobic group. More preferred are the liquid cyclic acid anhydrides in which R1 is a branched chain C8-C16 alkenyl group.
  • Typical examples of cellulose that may be treated with the sizing compounds are derived from hardwoods and softwoods, bleached or not bleached, semi-chemical, groundwood and combinations thereof. Synthetic rayon or regenerated cellulose fibres may also be used as well as waste paper and cardboard.
  • An amount of the paper stock A previously treated with 0.25% alum is fed to a 5 m3 feed tub and it is treated with 0.5% cooked cationic potato starch B.
  • the paper stock amount is limited to about 1 hour of machine feed to prevent unwanted ageing effects.
  • a piston metering pump connected to a spraying nozzle is used to spray-mix neat FIBRAN (RTM) 76 D into a stream of tap water at 40-50°C and the mixture is fed at the rate of 0.5m3 Ton ⁇ 1 dry cellulose to the suction side of the pump feeding the alum-treated paper stock to the paper machine.
  • FIBRAN (RTM) 76 is fed at the rate of 0.35% to maximize foaming effects, if any.
  • the paper machine is constructed by SICMA, Terni, Italy. It is fitted with a Fourdrinier net width 0.56m and a series of 22 steam-heated drying cylinders, running at the speed of 40m.min ⁇ 1 and producing about 100 kg paper per hour. The grammage is kept at about 80-85 g.m2.
  • polyacrylamide F 0.038% polyacrylamide F is finally added to the paper stock just before it enters the head box.
  • the paper web is dried in the machine drying section, whose steam-heated cylinders are programmed to reach temperatures in the range 50-110°C, before being wound up.
  • Comparative Example 1 is repeated by using a branched chain C12 alkenyl succinic anhydride D (EXXON CHEMICAL CO) as the sizing agent.
  • a branched chain C12 alkenyl succinic anhydride D EXXON CHEMICAL CO
  • Comparative Example 2 is repeated in runs 1, 2, 3 and 4.
  • Sodium polysilicate G is metered on-line into the paper stock on the suction side of the fan pump together with calcium carbonate slurried in water.
  • the paper stock pH after addition is in the range 7.2 to 7.6.
  • Runs 3 and 4 were carried out with a paper stock pretreated with 0.5% alum and Run 4 with 0.3% of the size to maximize foaming and white pitches, if any.
  • Comparative Example 2 is repeated in Runs 5, 6, 7, 8 and 10.
  • Run 9 is carried out with FIBRAN RTM 76 as sizing agent for comparison. In all cases, the size concentration is 0.25%.
  • Sodium Polysilicate G or polyphosphonic acid H are metered on-line into the paper stock on the suction side of the fan pump together with calcium carbonate slurried in water. The paper stock pH after addition is in the range 7.2 to 7.6.
  • Runs 6, 7, 8, 9 and 10 are carried out with decreasing amount of polyacrylamide (from 0.038% as in Comparative Example 1 to 0.019 and 0.0%).
  • Example 2 is repeated in runs 11 and 12 by using respectively branched chain C12 alkenyl succinic anhydride D (EXXON Chemical Company) and mixture of 92.7% wt of the same with 7.3% wt alkyl ketene dimer E as sizing agents both at the concentration of 0.15%.
  • paper stock A is not previously treated with alum and cationized potato starch B.
  • a piston metering pump connected to a spraying nozzle, is used to spray-mix neat C12 alkenyl anhydride D or its mixture with alkyl ketene dimer E into a stream of cationized potato starch in demineralized water at the concentration of 1.3% at the rate of 0.38 m3.Ton ⁇ 1 dry cellulose.
  • Sodium polysilicate G (COMPOZIL (RTM)) is metered on-line into the paper stock at the rate of 0.33 parts of commercial material per 100 parts of cellulose on the suction side of the fan pump together with calcium carbonate slurried in water.

Claims (6)

  1. Verwendung eines in Wasser löslichen oder dispergierbaren Salzes einer mehrbasigen Säure oder einer in Wasser kolloidalen Dispersion des Salzes als Schaumunterdrückungsmittel bei der alkalischen oder neutralen Papierherstellung unter Verwendung von Alkyl- oder Alkenylbernsteinsäureanhydrid als Leimungsmittel und Calciumcarbonat als Füllstoff.
  2. Verwendung nach Anspruch 1 von 0,2 bis 2 Gew.% des Salzes der mehrbasigen Säure, bezogen auf das Gewicht der trockenen Cellulose.
  3. Verwendung nach Anspruch 1, bei dem das Papier zusätzlich durch die Zugabe von Alkylketen-Dimer während der Papierherstellung geleimt wird.
  4. Verfahren zur Herstellung von Papier unter alkalischen oder neutralen Bedingungen unter Verwendung von Alkyl- oder Alkenylbernsteinsäureanhydrid als Leimungsmittel und Calciumcarbonat als Füllstoff, dadurch gekennzeichnet, daß die Bildung von Schaum durch die Zugabe eines in Wasser löslichen oder dispergierbaren Salzes einer mehrbasigen Säure oder einer in Wasser kolloidalen Dispersion dieses Salzes zu dem Papierrohstoff vermindert wird.
  5. Verfahren nach Anspruch 4, bei dem 0,2 bis 2 Gew.% des Salzes der mehrbasigen Säure, bezogen auf das Gewicht der trockenen Cellulose, zugesetzt werden.
  6. Verfahren nach Anspruch 4 oder Anspruch 5, bei dem das Papier zusätzlich durch die Zugabe von Alkylketen-Dimer zu dem wäßrigen Papierherstellungsrohstoff geleimt wird.
EP91903705A 1990-01-22 1991-01-21 Reduzierung von schaum bei der papierherstellung Expired - Lifetime EP0512038B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB909001438A GB9001438D0 (en) 1990-01-22 1990-01-22 Reducing foaming in paper manufacture
GB9001438 1990-01-22
GB909008336A GB9008336D0 (en) 1990-04-12 1990-04-12 Reducing foaming in paper manufacture
GB9008336 1990-04-12
PCT/GB1991/000089 WO1991010776A1 (en) 1990-01-22 1991-01-21 Reducing foaming in paper manufacture

Publications (2)

Publication Number Publication Date
EP0512038A1 EP0512038A1 (de) 1992-11-11
EP0512038B1 true EP0512038B1 (de) 1995-02-22

Family

ID=26296538

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91903705A Expired - Lifetime EP0512038B1 (de) 1990-01-22 1991-01-21 Reduzierung von schaum bei der papierherstellung

Country Status (12)

Country Link
EP (1) EP0512038B1 (de)
JP (1) JPH10502134A (de)
AT (1) ATE118848T1 (de)
CA (1) CA2074066A1 (de)
DE (1) DE69107611T2 (de)
DK (1) DK0512038T3 (de)
ES (1) ES2068570T3 (de)
FI (1) FI923316A (de)
NO (1) NO922782L (de)
PT (1) PT96547B (de)
WO (1) WO1991010776A1 (de)
YU (1) YU39791A (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3814707C1 (de) * 1988-04-30 1989-10-05 Henkel Kgaa, 4000 Duesseldorf, De
US6133703A (en) * 1998-03-12 2000-10-17 The Chamberlain Group, Inc. Bi-directional pass-point system for controlling the operation of movable barriers
US6172475B1 (en) 1998-09-28 2001-01-09 The Chamberlain Group, Inc. Movable barrier operator
FI20060670A0 (fi) * 2006-07-10 2006-07-10 Mikko Kaira Menetelmä kuitutuotteen bulkin lisäämiseksi ja muodostettu kuitutuote

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1069742A (en) * 1978-01-03 1980-01-15 Edwin H. Flaherty Pulp sheet formation

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA69742A (en) * 1900-10-23 1900-12-22 David E. Smith Oil cup
US3573222A (en) * 1969-07-02 1971-03-30 Pennwalt Corp Defoaming composition,its use and process for its preparation
AU546999B2 (en) * 1980-05-28 1985-10-03 Eka A.B. Adding binder to paper making stock
US4443357A (en) * 1981-01-12 1984-04-17 Economics Laboratory, Inc. Hydrophobic silica or silicate, compositions containing the same and methods for making and using the same
IT1163643B (it) * 1983-07-01 1987-04-08 Prodeco Spa Procedimento per la collatura di carta, in particolare in presenza di una carica sensibile ad ambiente acido
FR2612961B1 (fr) * 1987-03-23 1989-10-13 Atochem Procede de fabrication du papier par adjonction a la suspension fibreuse d'une charge minerale, d'un agent de collage, d'amidon cationique et de polychlorure d'aluminium

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1069742A (en) * 1978-01-03 1980-01-15 Edwin H. Flaherty Pulp sheet formation

Also Published As

Publication number Publication date
ATE118848T1 (de) 1995-03-15
FI923316A0 (fi) 1992-07-21
YU39791A (sh) 1993-11-16
NO922782D0 (no) 1992-07-14
CA2074066A1 (en) 1991-07-23
DE69107611T2 (de) 1995-06-14
EP0512038A1 (de) 1992-11-11
DK0512038T3 (da) 1995-07-24
PT96547A (pt) 1991-10-15
PT96547B (pt) 1998-07-31
FI923316A (fi) 1992-07-21
DE69107611D1 (de) 1995-03-30
WO1991010776A1 (en) 1991-07-25
JPH10502134A (ja) 1998-02-24
NO922782L (no) 1992-09-18
ES2068570T3 (es) 1995-04-16

Similar Documents

Publication Publication Date Title
US6306255B1 (en) Sizing of paper
EP0235893B2 (de) Herstellung von Papier und Pappe
US5270076A (en) Process for coating alkyl ketene dimer on titanium dioxide
JP2004514796A (ja) 紙のサイジング方法
US3409500A (en) Method of sizing paper with cationic polyamine and carboxylic anhydride
EP0963485B1 (de) Papierleimung
US5114538A (en) Process for sizing paper and similar products
EP0512038B1 (de) Reduzierung von schaum bei der papierherstellung
US5407537A (en) Process for sizing paper and similar products
GB2252984A (en) Novel compositions and their use for sizing paper
CN109790685B (zh) 用于提高纸张或纸板产品的尺寸稳定性的方法
CA2500545A1 (en) Cationised polysaccharide product
JPH0667467B2 (ja) 安定な置換無水コハク酸／乳化剤組成物
US3930932A (en) Process for sizing cellulose fibre containing material
JP3304584B2 (ja) ロジン系エマルション組成物、その製造方法、サイズ剤、サイジング方法
Carter The chemistry of paper preservation: part 4. Alkaline paper
JP3491325B2 (ja) ロジン系エマルション組成物、その製造方法、サイズ剤、サイジング方法及びサイズされた紙
FI67736B (fi) Aemneskomposition foer limning av papper
WO2004022850A1 (en) Method for sizing of paper or paperboard.
JP3477932B2 (ja) 製紙用ロジン系エマルジョンサイズ剤および紙サイジング方法
US20040138438A1 (en) Cationised polysaccharide product
WO1991010777A1 (en) Process for sizing paper and similar products
IE46377B1 (en) Filled paper
US20040104004A1 (en) Cationised polysaccharide product
JPH07119076A (ja) ロジン系エマルション組成物、その製造方法、サイズ剤、サイジング方法及びサイズされた紙

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19920817

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

17Q First examination report despatched

Effective date: 19931005

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LI LU NL SE

REF Corresponds to:

Ref document number: 118848

Country of ref document: AT

Date of ref document: 19950315

Kind code of ref document: T

ITF It: translation for a ep patent filed

Owner name: BARZANO' E ZANARDO MILANO S.P.A.

REF Corresponds to:

Ref document number: 69107611

Country of ref document: DE

Date of ref document: 19950330

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2068570

Country of ref document: ES

Kind code of ref document: T3

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19950426

Year of fee payment: 6

ET Fr: translation filed
REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3016093

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 19951115

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19951220

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 19951222

Year of fee payment: 6

Ref country code: CH

Payment date: 19951222

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19960101

Year of fee payment: 6

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19960117

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19960121

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19960131

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19960207

Year of fee payment: 6

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19960319

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19960528

Year of fee payment: 6

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19960121

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970121

Ref country code: DK

Effective date: 19970121

Ref country code: AT

Effective date: 19970121

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19970122

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19970122

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19970131

Ref country code: CH

Effective date: 19970131

Ref country code: BE

Effective date: 19970131

BERE Be: lapsed

Owner name: EXXON CHEMICAL PATENTS INC.

Effective date: 19970131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19970731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19970801

REG Reference to a national code

Ref country code: GR

Ref legal event code: MM2A

Free format text: 3016093

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19970930

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19970801

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19971001

EUG Se: european patent has lapsed

Ref document number: 91903705.1

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19990405

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050121