EP0123708B1 - Agent d'encollage neutre pour des produits plats comprenant de la cellulose, procédé pour sa fabrication et son utilisation - Google Patents

Agent d'encollage neutre pour des produits plats comprenant de la cellulose, procédé pour sa fabrication et son utilisation Download PDF

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Publication number
EP0123708B1
EP0123708B1 EP83104303A EP83104303A EP0123708B1 EP 0123708 B1 EP0123708 B1 EP 0123708B1 EP 83104303 A EP83104303 A EP 83104303A EP 83104303 A EP83104303 A EP 83104303A EP 0123708 B1 EP0123708 B1 EP 0123708B1
Authority
EP
European Patent Office
Prior art keywords
sizing agent
rosin
neutral sizing
colophonium
agent according
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
Application number
EP83104303A
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German (de)
English (en)
Other versions
EP0123708A1 (fr
Inventor
Wolf-Stefan Dr.-Ing. Schultz
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.)
Klebstoffwerke Collodin Drschultz & Nauth GmbH
Original Assignee
Klebstoffwerke Collodin Drschultz & Nauth GmbH
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.)
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Publication date
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Application filed by Klebstoffwerke Collodin Drschultz & Nauth GmbH filed Critical Klebstoffwerke Collodin Drschultz & Nauth GmbH
Priority to EP83104303A priority Critical patent/EP0123708B1/fr
Priority to AT83104303T priority patent/ATE24559T1/de
Priority to DE8383104303T priority patent/DE3368706D1/de
Publication of EP0123708A1 publication Critical patent/EP0123708A1/fr
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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
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/56—Polyamines; Polyimines; Polyester-imides
    • 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
    • D21H17/22—Proteins
    • 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

Definitions

  • rosin and modified or reinforced rosin have been used primarily for mass sizing and hydrophobization of paper and other cellulose-containing fabrics.
  • the enhancement of rosin by reacting with maleic anhydride or other dienophilic compounds while increasing the number of carboxyl groups in the rosin has been described e.g. B. from Casey in Pulp and Paper, 2nd edition, vol. II, pages 1043 to 1066 and in US Pat. Nos. 2,628,918 and 2,684,300.
  • a typical reinforced rosin should contain about 1 to 30% by weight of maleic anhydride, based on the resin, in a bound form as an adduct (maleinopimaric anhydride).
  • Dispersion glues based on rosin resins which contain casein or other proteins as a dispersant or protective colloid are also known (cf. Pulp and Paper, loc. Cit., DE-B1-1 130 955, DE-B1-1 122 200, US-A-2 401 090, US-A-2 116 768, US-A-2 288 060, DE-C-820 049).
  • these dispersion glues have to be produced with the help of complicated inversion processes in complex devices and with greater energy consumption.
  • a sizing agent for paper in the absence of aluminum sulfate which consists of an aqueous dispersion of a rosin modified with a carboxyl group-containing dienophile resin.
  • This dispersion contains, for example, casein digested with ammonia as a protective colloid and can also contain a polyamine derivative.
  • the dispersed modified rosin must be at least 90% unsaponified. The preparation of this dispersion requires intensive stirring.
  • the object of the invention is to provide a neutral sizing agent for cellulosic fabrics, in particular a paper glue, on the basis of a rosin resin modified with a carboxyl group-containing dienophilic compound, which is simple to produce and is not dependent on use in the acidic pH range and which allows the papermaker to choose the optimal pH range between 4 and 7 for his product.
  • the rosin (a) is saponified and the sizing agent is in the form of a soap solution or a dry glue.
  • the content of the neutral sizing agent in the saponified, mofidified rosin and in the digested protein which surprisingly improves the retention of the glue on the paper and thus serves as a fixing agent, makes the sizing agent very easy to produce in the form of a soap solution or a dry glue and its use of the resin glue in the mass at neutral pH. Corrosion problems are thus reduced to a minimum, and the use of aluminum sulfate or another aluminum salt can be significantly reduced or even avoided.
  • the neutral sizing agent according to the invention is particularly advantageous in paper sizing because it is not dependent on use in the acidic pH range and itself can be mixed with water in any desired ratio. In particular, it is able to compensate for fluctuations in the composition of the material that occur when using waste paper by using it in a wide pH range between 4.5 and 7, and also in borderline cases.
  • the modified rosin used in the neutral sizing agent according to the invention can be made from any of the commercially available rosins, e.g. B. Root resin.Balsam resin.Tall oil resin and mixtures of two or more of these resins in the raw or refined state. Resins with a tendency to crystallize can be treated at elevated temperatures with formaldehyde or paraformaldehyde in the presence of an acidic catalyst, e.g. B. p-toluenesulfonic acid, are treated in a known manner. So resin treated with formaldehyde can be used and falls under the term rosin resin used here.
  • an acidic catalyst e.g. B. p-toluenesulfonic acid
  • a modified or reinforced rosin is a reaction product of rosin with an acidic, dienophilic compound that does the rest contains, which is obtained as an adduct by reacting rosin with a dienophilic compound at elevated temperatures, usually about 150 to 210 "C.
  • the amount of the dienophilic compound used is adjusted so that a modified rosin resin containing 1 to 30% by weight, preferably 5 to 12% by weight, of the added dienophilic compound, based on the weight of the reinforced rosin, is obtained, and processes for making reinforced rosins are described in U.S. Patents 2,628,918 and 2,684,300 .
  • Examples of dienophiles, the rest Compounds containing which can be used to prepare the reinforced rosin are the a, (3-unsaturated organic acids and their accessible anhydrides. Specific examples include maleic anhydride, fumaric acid, acrylic acid, maleic acid, itaconic acid, itaconic anhydride, citraconic acid and citraconic anhydride and citric acid Preferred modifiers are maleic anhydride or fumaric acid, and acid mixtures can optionally be used to prepare the rosin.
  • Mixtures of various reinforced rosins can also be used. It can e.g. B. a mixture of the maleic anhydride adduct with rosin and the fumaric acid adduct with rosin can be used to produce the neutral sizes according to the invention.
  • digested protein can e.g. B. from soy protein, casein or starch protein, which is digested with ammonia, potassium hydroxide, sodium hydroxide, borax, metaborate, triethanolamine, lithium hydroxide or phosphates.
  • starch protein z. B. a waste product of potato flour production can be used.
  • the neutral sizing agent according to the invention can optionally be a polyamine derivative, ie. H. contain a cationic fiction or retention agent.
  • fixatives are polyethyleneimine derivatives.
  • the second fixing agent can be added in amounts of up to 10%, based on the finished neutral sizing agent. In this case, the use of aluminum sulfate or other aluminum salts can be dispensed with entirely.
  • the neutral sizing agent according to the invention can also optionally known additives, for. B. waxes, especially paraffin wax and microcrystalline wax, hydrocarbon resins including those derived from petroleum hydrocarbons and terpenes, spindle oil or polyglycols. These can be added in amounts of up to 95% by weight, preferably about 3 to 20% by weight, of additives, based on the weight of the rosin.
  • extender can also be added.
  • extenders which can be used in amounts of 10 to 50 % by weight, based on the weight of the rosin, are, for. B. Tall oil derivatives in question.
  • the neutral sizing agent according to the invention can also stabilizers, such as. B. isopropanol, methanol, ethanol, glycerol, glycol or polyglycols. These stabilizers can be added in amounts of up to 5%, based on the finished neutral sizing agent.
  • an aqueous solution of the saponified modified rosin (a) is mixed with an aqueous solution of the digested protein (b) and optionally the second fixing agent (c) and / or conventional extenders, additives and / or stabilizers (d).
  • the ingredients can be in diluted or concentrated form, e.g. H. with a solids concentration between 30 and 60%.
  • a melt of the modified rosin (a) is saponified with the addition of a saponifying agent and an aqueous solution of the digested protein (b) and optionally the second fixing agent (c) and / or conventional constituents (d).
  • the finished neutral sizing agent can have a solids content of 10 to 95%.
  • the solids content of the soap solution is preferably 30 to 60% and is only further diluted before use.
  • the solids content of the dry glue is preferably 85 to 95%.
  • the ratio of rosin to protein in the neutral sizing agent according to the invention is 100: 1 to 100:20.
  • 100 parts of the resin from stage a were saponified with 16 parts of sodium hydroxide solution as a 50% solution and adjusted to a dry matter content of 50% with water.
  • casein 29 parts were dispersed with 2 parts of 45% sodium hydroxide solution in 150 parts of water and heated to 60 ° C. for 15 minutes.
  • Example 1 The procedure of Example 1 was repeated, the amount of added casein solution from step c being varied in stage d from 2.5 to 50 parts of casein solution per 100 parts of glue solution from stage b. All glues obtained in this way were used and tested according to the procedure of Example 1d for gluing the spruce sulfite pulp, 2% glue absolutely dry, based on pulp, being used and the pH value in each case with Al 2 (S0 4 ) 3 6.8 was set.
  • Example 4 The procedure of Example 4 was repeated, but instead of the casein solution c used there, a protein solution was used which was obtained by dispersing 18 parts of soy protein with 2.5 parts of KOH in 100 parts of cold water and heating to 70.degree. The glue obtained had an ink swimming time of 145 seconds.
  • This example illustrates the production of a dry glue. 100 parts of resin were melted and saponified with the addition of a mixture of 60 g of 45% NaOH and 20 g of a casein solution according to Example 1c. The ink float was 60 seconds compared to 35 seconds for the 0 sample.
  • Example 1 illustrates the use of different disintegrants for the protein.
  • the procedure of Example 1 was repeated. however, different disintegrants for the casein were used in stage c.
  • the results are shown in Table II.
  • the sheet formation was carried out as in Examples 1 to 7.
  • 100 parts of the reinforced resin from stage a were saponified with 17 parts of NaOH as a 50% solution and adjusted to 50% dryness with water.
  • a glue of 100 parts of the soap solution from stage b and 10 parts of the casein solution from example 1 c gave an ink swimming time of 110 seconds compared to 60 seconds of the 0 sample.
  • Example 2 illustrates the use of a second fixative in the neutral sizing agent.
  • the procedure of Example 1 was repeated, but in step d instead of the 2.5 parts of the casein solution obtained in step c, 5 parts of the casein solution and additionally 5 parts of a polyethyleneimine derivative were mixed with the 100 parts of the soap solution obtained in step b.
  • an ink float of 300 seconds was measured.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Claims (9)

1. Agent d'encollage neutre pour produits plats comportant de la cellulose, contenant
(a) au moins une résine de colophane modifiée avec un composé diénophile contenant des groupes carboxyle,
(b) une protéine animale ou végétale désagrégée,
(c) le cas échéant un dérivé de polyamine comme fixateur et
(d) le cas échéant des diluants, additifs et/ou stabilisateurs habituels.

où le rapport pondéral de (a) à (b) s'élève à 100 : 1 à 100 : 20, caractérisé en ce que la résine de colophane (a) est saponifiée et en ce que l'agent d'encollage se présente sous la forme d'une solution de savon ou d'une colle sèche.
2. Agent d'encollage neutre selon la revendication 1, caractérisé en ce qu'il possède une teneur en substance sèche de 10 à 95%.
3. Agent d'encollage neutre selon la revendication 2, caractérisé en ce qu'il possède une teneur en substance sèche de 30 à 60 %.
4. Agent d'encollage neutre selon la revendication 2, caractérisé en ce qu'il possède une teneur en substance sèche de 85 à 95 %.
5. Agent d'encollage neutre selon l'une des revendications 1 à 4, caractérisé en ce qu'il contient comme protéine (b) de la caséine désagrégée.
6. Agent d'encollage neutre selon l'une des revendications 1 à 5, caractérisé en ce qu'il contient comme résine de colophane (a) une résine de colophane modifiée avec de 8 à 12 % en poids d'anhydride de l'acide maléique.
7. Agent d'encollage neutre selon l'une des revendications 1 à 6, caractérisé en ce qu'il contient comme fixateur (c) un dérivé de polyéthylène-imine.
8. Procédé de préparation de l'agent d'encollage neutre selon l'une des revendications 1 à 7 par mélange d'une solution aqueuse du composant (b) avec les autres composants dans un rapport pondéral de (a) à (b) de 100 1 à 100 : 20, où la résine de colophane modifiée est appliquée le cas échéant dans la masse en fusion, caractérisé en ce qu'on mélange une solution aqueuse de la résine de colophane modifié saponifiée (a) avec la solution aqueuse du composant (b) et le cas échéant les composants (c) et/ou (d) sous forme diluée ou concentrée et en ce que le cas échéant on dilue plus avant avec de l'eau le mélange obtenu, ou en ce qu'on saponifie une masse en fusion de la résine de colophane modifiée (a) avec addition d'un agent de saponification et de la solution aqueuse du composant (b) et le cas échéant les composants (c) et/ou (d).
9. Application de l'agent d'encollage neutre selon l'une des revendications 1 à 7 à l'encollage neutre de produits plats comportant de la cellulose, en particulier à l'encollage en cuve du papier.
EP83104303A 1983-05-02 1983-05-02 Agent d'encollage neutre pour des produits plats comprenant de la cellulose, procédé pour sa fabrication et son utilisation Expired EP0123708B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP83104303A EP0123708B1 (fr) 1983-05-02 1983-05-02 Agent d'encollage neutre pour des produits plats comprenant de la cellulose, procédé pour sa fabrication et son utilisation
AT83104303T ATE24559T1 (de) 1983-05-02 1983-05-02 Neutralleimungsmittel fuer cellulosehaltige flaechengebilde, verfahren zu seiner herstellung und seine verwendung.
DE8383104303T DE3368706D1 (en) 1983-05-02 1983-05-02 Neutral sizing agent for flat cellulose-comprising products, process for its manufacture and its use

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP83104303A EP0123708B1 (fr) 1983-05-02 1983-05-02 Agent d'encollage neutre pour des produits plats comprenant de la cellulose, procédé pour sa fabrication et son utilisation

Publications (2)

Publication Number Publication Date
EP0123708A1 EP0123708A1 (fr) 1984-11-07
EP0123708B1 true EP0123708B1 (fr) 1986-12-30

Family

ID=8190440

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83104303A Expired EP0123708B1 (fr) 1983-05-02 1983-05-02 Agent d'encollage neutre pour des produits plats comprenant de la cellulose, procédé pour sa fabrication et son utilisation

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Country Link
EP (1) EP0123708B1 (fr)
AT (1) ATE24559T1 (fr)
DE (1) DE3368706D1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0200002B2 (fr) * 1985-04-13 1993-10-27 Chemische Fabrik Brühl Oppermann GmbH Agents d'encollage pour papier et leur application

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0037055A1 (fr) * 1980-03-31 1981-10-07 Klebstoffwerke Collodin Dr.Schultz & Nauth GmbH Agent hydrophobe pour substrats cellulosiques plats, procédé pour sa préparation et son utilisation

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2116768A (en) * 1934-12-07 1938-05-10 Paper Chemistry Inst Sizing paper
US2288060A (en) * 1938-09-02 1942-06-30 Gustav Staelin Solid water-in-rosin paper size
US2401090A (en) * 1941-06-14 1946-05-28 Hercules Powder Co Ltd Dry size compositions
GB582157A (en) * 1945-01-05 1946-11-08 Wiggins Teape & Company 1919 L An improved water dispersible urea-formaldehyde composition and its preparation
DE820049C (de) * 1948-11-27 1951-11-08 Hanns Dr Arledter Verfahren zur Herstellung eines Papierleimes
DE1122200B (de) * 1960-07-28 1962-01-18 Eisele & Hoffmann K G Verfahren zur Herstellung besonders stabiler, feindisperser Harzdispersionen von erhoehter Leimkraft zur Leimung von Papier
DE1130955B (de) * 1961-03-28 1962-06-07 Eisele & Hoffmann K G Verfahren zur Herstellung stabiler, nicht kristallisierender Dispersionen aus hydriertem Kolophonium zur Leimung von Papier
US3186900A (en) * 1962-07-13 1965-06-01 Hercules Powder Co Ltd Sizing paper under substantially neutral conditions with a preblend of rosin and cationic polyamide-epichlorohydrin resin
GB1078648A (en) * 1963-11-14 1967-08-09 Catomance Ltd Improvements in or relating to waterproofing paper, board and the like
GB1108035A (en) * 1964-06-02 1968-03-27 American Cyanamid Co Rosin size and paper sized therewith
GB1444751A (en) * 1973-01-22 1976-08-04 Tenneco Chem Paper sizing
US3966654A (en) * 1973-08-06 1976-06-29 Hercules Incorporated Stable rosin dispersions

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0037055A1 (fr) * 1980-03-31 1981-10-07 Klebstoffwerke Collodin Dr.Schultz & Nauth GmbH Agent hydrophobe pour substrats cellulosiques plats, procédé pour sa préparation et son utilisation

Also Published As

Publication number Publication date
DE3368706D1 (en) 1987-02-05
ATE24559T1 (de) 1987-01-15
EP0123708A1 (fr) 1984-11-07

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