EP0351397B1 - Use of a polyamide-polyamine-epichlor hydrine precondensate as an impregnation agent for paper - Google Patents
Use of a polyamide-polyamine-epichlor hydrine precondensate as an impregnation agent for paper Download PDFInfo
- Publication number
- EP0351397B1 EP0351397B1 EP19890890186 EP89890186A EP0351397B1 EP 0351397 B1 EP0351397 B1 EP 0351397B1 EP 19890890186 EP19890890186 EP 19890890186 EP 89890186 A EP89890186 A EP 89890186A EP 0351397 B1 EP0351397 B1 EP 0351397B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- paper
- polyamine
- polyamide
- precondensate
- impregnation agent
- 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
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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/18—Paper- or board-based structures for surface covering
- D21H27/20—Flexible structures being applied by the user, e.g. wallpaper
-
- 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
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
-
- 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
-
- 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
Definitions
- the invention relates to the use of a polyamide-polyamine-epichlorohydrin precondensate as an impregnating agent for paper.
- thermosetting resin A curable aqueous solution of a thermosetting resin has become known from US Pat. No. 4,336,835, which has a relatively high solids content and allows improved wet strength of paper to be achieved.
- the solution is prepared by reacting an aliphatic dicarboxylic acid with a polyalkylene polyamine to form a polyamide polyamine, which is then reacted with epichlorohydrin.
- the first reaction is present at a molar ratio between aliphatic dicarboxylic acid and polyalkylene polyamine of 1: 1.0 to 1.2 executed until a viscosity of 50% aqueous solution at 25 ° ° C of polyamide-polyamine 4-10 dyn.s.cm ⁇ 2 (400 to 1000 cP) is reached, and the second reaction, in which epichlorohydrin is used in an amount of 1.6 to 1.7 moles per mole of the polyamide secondary amine, is as long continued until the viscosity of the 15% solution of the resulting product at 25 ° C reaches a value of 0.3 to 1.5 dyn.s.cm ⁇ 2 (30 to 150 cP).
- Adipic acid recommended and as polyalkylene-polyamine triethylene tetramine.
- polyamide-polyamine-epichlorohydrin precondensate the degree of condensation of which is 500 and corresponds to an active content of 12%
- lignosulfonic acid optionally as the calcium salt of sulfonic acid
- Additive to the impregnation liquid for the surface treatment of paper, in particular corrugated raw paper is used.
- the measure according to the invention mentioned above as an additive to the impregnation liquid, it was possible to achieve adequate swelling resistance and an increase in the strength values of the paper, in particular the CMT value (DIN 53143).
- the chlorine component of the pre-condensate does not pose any difficulties with regard to environmental pollution, because chlorine reacts with the calcium contained in the sulfite waste liquor to form CaCl2 and no free chlorine or hydrochloric acid is formed.
- the polyamide-polyamine-epichlorohydrin precondate can be constructed from the basic materials adipic acid, triethylene tetramine and epichlorohydrin so that an average molecular weight of 20,000 with a chlorine content of 16-18%, preferably 17%, a condensation temperature of 180 ° C. and a reaction time of 45 min results.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
Description
Die erfindung bezieht sich auf die Verwendung eines Polyamid-Polyamin-Epichlorhydrin-Vorkondensates als Imprägniermittel für Papier.The invention relates to the use of a polyamide-polyamine-epichlorohydrin precondensate as an impregnating agent for paper.
Es ist bekannt, zur Oberflächenbehandlung von Papier, insbesondere von Rohpapieren für die Wellpappenfabrikation, vorwiegend Stärke in gelöster Form einzusetzen, um auf diesem Wege die geforderten Festigkeitseigenschaften zu erreichen. Der Einsatz erfolgt dabei bei der Papierherstellung vor der Nach-Trockenpartie in der Leimpresse.It is known to primarily use starch in dissolved form for the surface treatment of paper, in particular raw paper for the manufacture of corrugated cardboard, in order to achieve the required strength properties in this way. They are used in paper production before the after-dryer section in the size press.
Durch die DE-A-29 51 507 wurde es bekannt, in Papierleimstoffen aus einer Ketendimerdispersion, die im wesentlichen aus dem Dimeren, einem anionischen Dispersionsmittel aus der Gruppe Natriumligninsulfonat, Kondensationsprodukt von Formaldehyd und Natriumnaphthalinsulfonat und deren Gemischen besteht, ein kationisches Harz als Reaktionsprodukt von Epichlorhydrin mit einem Polymer der Gruppe eines Aminopolyamids, das aus einer Dicarbonsäure und einem Polyalkylenpolyamin mit zwei primären Amingruppen und wenigstens einer sekundären oder tertiären Aminogruppe besteht, einzusetzen.From DE-A-29 51 507 it was known in paper sizes from a ketene dimer dispersion, which consists essentially of the dimer, an anionic dispersant from the group sodium lignin sulfonate, condensation product of formaldehyde and sodium naphthalenesulfonate and mixtures thereof, a cationic resin as a reaction product of Epichlorohydrin with a polymer from the group of an aminopolyamide, which consists of a dicarboxylic acid and a polyalkylene polyamine with two primary amine groups and at least one secondary or tertiary amino group.
Durch die US-A-4 336 835 wurde eine härtbare wässerige Lösung eines duroplastischen Harzes bekannt, welche einen relativ hohen Feststoffanteil besitzt und eine verbesserte Naßfestigkeit von Papier erzielen läßt. Die Lösung wird dabei durch Umsetzung einer aliphatischen Dicarbonsäure mit einem Polyalkylen-Polyamin zwecks Bildung eines Polyamid-Polyamins hergestellt, welches danach mit Epichlorhydrin umgesetzt wird. Die erste Reaktion wird dabei bei einem molaren Verhältnis zwischen aliphatischer Dicarbonsäure und Polyalkylen-Polyamin von 1:1,0 bis 1,2 ausgeführt, bis eine Viskosität der 50%igen wässerigen Lösung bei 25°°C an Polyamid-Polyamin von 4 - 10 dyn.s.cm⁻² (400 bis 1000 cP) erreicht wird, und die zweite Umsetzung, bei der Epichlorhydrin in einem Ausmaß von 1,6 bis 1,7 Mol pro Mol des Polyamid sekundären Amins eingesetzt wird, wird solange fortgesetzt, bis die Viskosität der 15 %igen Lösung des sich ergebenden Produktes bei 25°C einen Wert von 0,3 bis 1,5 dyn.s.cm⁻² (30 bis 150 cP) erreicht.A curable aqueous solution of a thermosetting resin has become known from US Pat. No. 4,336,835, which has a relatively high solids content and allows improved wet strength of paper to be achieved. The solution is prepared by reacting an aliphatic dicarboxylic acid with a polyalkylene polyamine to form a polyamide polyamine, which is then reacted with epichlorohydrin. The first reaction is present at a molar ratio between aliphatic dicarboxylic acid and polyalkylene polyamine of 1: 1.0 to 1.2 executed until a viscosity of 50% aqueous solution at 25 ° ° C of polyamide-polyamine 4-10 dyn.s.cm⁻² (400 to 1000 cP) is reached, and the second reaction, in which epichlorohydrin is used in an amount of 1.6 to 1.7 moles per mole of the polyamide secondary amine, is as long continued until the viscosity of the 15% solution of the resulting product at 25 ° C reaches a value of 0.3 to 1.5 dyn.s.cm⁻² (30 to 150 cP).
Als aliphatische Dicarbonsäure wird u.a. Adipinsäure empfohlen und als Polyalkylen-Polyamin Triäthylentetramin.As an aliphatic dicarboxylic acid, i.a. Adipic acid recommended and as polyalkylene-polyamine triethylene tetramine.
Zur Steigerung der Festigkeitseigenschaften wurde auch bereits empfohlen, Kombinationen von Naßlestmitteln mit Kunststoffdispersionen einzusetzen. Alle diese Mittel haben jedoch bei ihrer Verwendung den Nachteil, daß Feststoffgehalte von höchstens 10 % in der Leimpresse zur Anwendung kommen konnten, da sonst das erforderliche Fließverhalten der Imprägnierflüssigkeit nicht erreicht werden konnte.To increase the strength properties, it has already been recommended to use combinations of wet solvents with plastic dispersions. However, all of these agents have the disadvantage, when used, that solids contents of at most 10% could be used in the size press, since otherwise the required flow behavior of the impregnation liquid could not be achieved.
Nun kann durch Einsatz von Sulfitablauge in der Leimpresse ein wesentlich höherer Feststoffgehalt erreicht werden. Versuche, anstelle von Stärke andere Substanzen einzusetzen, scheiterten jedoch an der hohen Wasserlöslichkeit der in der Sulfitablauge enthaltenen Ligninsulfonate. Die hohe Wasserlöslichkeit führte nämlich bei der Verarbeitung des Wellpappenrohpapieres an den Riffelwalzen der Wellpappenanlage zu klebrigen Ablagerungen, was Abrißfolgen nach sich zog.A much higher solids content can now be achieved by using sulfite waste liquor in the size press. Attempts to use other substances instead of starch failed due to the high water solubility of the lignin sulfonates contained in the sulfite waste liquor. The high water solubility in the processing of the corrugated base paper led to sticky deposits on the corrugated rollers of the corrugated board plant, which resulted in tearing consequences.
Die Probleme, die durch die Anwendung von Salzen der Ligninsulfonsäure bei der Herstellung von Pappe entstehen, werden in DE-A-2 018 088 beschrieben.The problems which arise from the use of salts of lignosulfonic acid in the production of cardboard are described in DE-A-2 018 088.
Überraschenderweise wurde nun gefunden, daß die vorerwähnten Probleme dadurch einer Lösung zugeführt werden können, daß Polyamid-Polyamin-Epichlorhydrin-Vorkondensat, dessen Kondensationsgrad bei 500 liegt und einem Aktivgehalt von 12 % entspricht, im Gemisch mit Ligninsulfonsäure, gegebenenfalls als Calciumsalz der Sulfonsäure, als Zusatz zur Imprägnierflüssigkeit für die Oberflächenbehandlung von Papier, insbesondere von Wellpapperohpapier, verwendet wird. Durch die vorstehend erwähnte erfindungsgemäße Maßnahme als Zusatz zur Imprägnierflüssigkeit konnte eine ausreichende Quellfestausrüstung und eine Steigerung der Festigkeitswerte des Papiers, insbesondere des CMT-Wertes (DIN 53143) erzielt werden. Die Chlorkomponente des Vorkondensats läßt hinsichtlich Umweltbelastung keine Schwierigkeiten erwarten, weil Chlor mit dem in der Sulfitablauge enthaltenen Calzium zu CaCl₂ reagiert und kein freies Chlor oder Salzsäure gebildet wird.Surprisingly, it has now been found that the aforementioned problems can be solved by a solution that polyamide-polyamine-epichlorohydrin precondensate, the degree of condensation of which is 500 and corresponds to an active content of 12%, in a mixture with lignosulfonic acid, optionally as the calcium salt of sulfonic acid, as Additive to the impregnation liquid for the surface treatment of paper, in particular corrugated raw paper, is used. With the measure according to the invention mentioned above as an additive to the impregnation liquid, it was possible to achieve adequate swelling resistance and an increase in the strength values of the paper, in particular the CMT value (DIN 53143). The chlorine component of the pre-condensate does not pose any difficulties with regard to environmental pollution, because chlorine reacts with the calcium contained in the sulfite waste liquor to form CaCl₂ and no free chlorine or hydrochloric acid is formed.
Das Polyamid-Polyamin-Epichlorhydrin-Vorkondenat kann aus den Grundstoffen Adipinsäure, Triäthylentetramin und Epichlorhydrin so aufgebaut sein, daß ein mittleres Molekulargewicht von 20000 bei einem Chlorgehalt von 16 - 18%, bevorzugt 17 %, einer Kondensationstemperatur von 180°C und einer Reaktionszeit von 45 min resultiert.The polyamide-polyamine-epichlorohydrin precondate can be constructed from the basic materials adipic acid, triethylene tetramine and epichlorohydrin so that an average molecular weight of 20,000 with a chlorine content of 16-18%, preferably 17%, a condensation temperature of 180 ° C. and a reaction time of 45 min results.
Eine Beeinträchtigung der Umweltbelastung durch den großen Anteil von Ligninsulfonaten ist bei Wiederauflösung der mit Ligninsulfonaten behandelten Papiere nicht zu befürchten. Versuche haben gezeigt, daß zwar ein verlangsamter CBS-Abbau (chemischer Sauerstoffbedarf) in der Kläranlage festgestellt wurde, daß insgesamt jedoch bei der biologischen Abwasserreinigung keine Schwierigkeiten zu erwarten sind. Die Ursache hiefür dürfte der Umstand sein, daß die Ligninsulfonate auf die Faser aufziehen und durch die dabei auftretende Vernetzung eine sehr hohe Faserretention erzielt wird.There is no reason to fear that the large proportion of lignin sulfonates will impair the environmental impact if the papers treated with lignin sulfonates are redissolved. Experiments have shown that although slower CBS degradation (chemical oxygen demand) was found in the sewage treatment plant, overall no difficulties are to be expected in biological wastewater treatment. The reason for this is probably the fact that the lignin sulfonates are drawn onto the fiber and that the resulting crosslinking results in very high fiber retention.
Claims (1)
- Use of a polyamide-polyamine-epichlor-hydrine precondensate mixed with lignin sulphonic acid, if appropriate as calcium salt of said sulphonic acid, as addition to the impregnating liquid for surface treatment of paper, particularly of corrugated cardboard base paper, the degree of condensation of the precondensate being at 500.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT180388A AT392809B (en) | 1988-07-12 | 1988-07-12 | IMPREGNATING AGENT FOR PAPER AND METHOD FOR IMPREGNATING PAPER |
| AT1803/88 | 1988-07-12 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0351397A2 EP0351397A2 (en) | 1990-01-17 |
| EP0351397A3 EP0351397A3 (en) | 1991-05-15 |
| EP0351397B1 true EP0351397B1 (en) | 1993-12-22 |
Family
ID=3521313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19890890186 Expired - Lifetime EP0351397B1 (en) | 1988-07-12 | 1989-07-12 | Use of a polyamide-polyamine-epichlor hydrine precondensate as an impregnation agent for paper |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0351397B1 (en) |
| AT (1) | AT392809B (en) |
| DE (1) | DE58906478D1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8118976B2 (en) | 2007-05-23 | 2012-02-21 | Akzo Nobel N.V. | Process for the production of a cellulosic product |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113690062B (en) * | 2021-07-28 | 2022-11-18 | 华南理工大学 | MXene/polypyrrole paper-based electrode material and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL231136A (en) * | 1957-09-05 | |||
| GB1301100A (en) * | 1969-04-18 | 1972-12-29 | Unilever Nv | Treatment of paperboard |
| JPS54159496A (en) * | 1978-06-07 | 1979-12-17 | Sumitomo Chem Co Ltd | Preparation of aqueous solution of cationic thermosetting resin |
| US4240935A (en) * | 1978-12-22 | 1980-12-23 | Hercules Incorporated | Ketene dimer paper sizing compositions |
-
1988
- 1988-07-12 AT AT180388A patent/AT392809B/en not_active IP Right Cessation
-
1989
- 1989-07-12 DE DE89890186T patent/DE58906478D1/en not_active Expired - Fee Related
- 1989-07-12 EP EP19890890186 patent/EP0351397B1/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8118976B2 (en) | 2007-05-23 | 2012-02-21 | Akzo Nobel N.V. | Process for the production of a cellulosic product |
Also Published As
| Publication number | Publication date |
|---|---|
| DE58906478D1 (en) | 1994-02-03 |
| EP0351397A2 (en) | 1990-01-17 |
| EP0351397A3 (en) | 1991-05-15 |
| AT392809B (en) | 1991-06-25 |
| ATA180388A (en) | 1990-11-15 |
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