EP0088272B1 - Agent d'encollage - Google Patents

Agent d'encollage Download PDF

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Publication number
EP0088272B1
EP0088272B1 EP83101622A EP83101622A EP0088272B1 EP 0088272 B1 EP0088272 B1 EP 0088272B1 EP 83101622 A EP83101622 A EP 83101622A EP 83101622 A EP83101622 A EP 83101622A EP 0088272 B1 EP0088272 B1 EP 0088272B1
Authority
EP
European Patent Office
Prior art keywords
carboxylic acids
acid
products according
sizing
amide
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
EP83101622A
Other languages
German (de)
English (en)
Other versions
EP0088272A1 (fr
Inventor
Wulf Dr. Von Bonin
Peter Dr. Mummenhoff
Ulrich Dr. Beck
Heinz Bäumgen
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.)
Bayer AG
Original Assignee
Bayer AG
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
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0088272A1 publication Critical patent/EP0088272A1/fr
Application granted granted Critical
Publication of EP0088272B1 publication Critical patent/EP0088272B1/fr
Expired legal-status Critical Current

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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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y10T428/31779—Next to cellulosic
    • Y10T428/31783—Paper or wood

Definitions

  • the present invention relates to new products with a sizing effect.
  • the new products are obtainable by reacting a, ⁇ -unsaturated carboxylic acids or their reactive derivatives (such as esters, acid anhydrides) with amidamines of higher carboxylic acids at temperatures above 120 ° C, with higher carboxylic acids being used as amidamines by reaction of 2 moles of carboxylic acid with 1 mole of diethylene triamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine, which are preferably used in the form of their technical qualities.
  • FR-A 2225572 describes N-alkyl-substituted asparagineimides of the formula From this prior art, there is the teaching that reaction products of maleic acid or anhydride are required to achieve good sizing, which, as expected, are present in the relatively hydrophobic and already known for good sizing effect, cyclic imide form (see also DE-A 1 621 693) should.
  • the invention further relates to a process for the preparation of the aforementioned products and to size preparations (preferably aqueous-alkaline dispersions) which contain the aforementioned reaction products.
  • the invention relates to sizing processes using the sizing agent preparations according to the invention.
  • a sizing agent and in particular a paper sizing agent in general cannot fulfill all of them at the same time, so that all previous sizing agents represent compromises in that they may excellently glue, but are, however, difficult to store or handle by only using pre-sized, unfilled or alum-containing paper, only on regenerated paper, on sanded paper or clay-containing paper each have a particularly good or particularly unsatisfactory effect and the sizing effect may only occur after a certain ripening period or immediately, the influence of brightener can be observed more or less strongly, the yellowing that Foam formation in the liquor or the sensitivity to water hardness can be observed.
  • the provision of the products according to the invention makes it possible to produce sizing preparations which have a surface effect, do not tend to foam and which are not only effective on alum-free and / or chalk-containing paper, but also on alum and / or kaolin and / or wood-containing paper.
  • the new size preparations were obtained by reacting ⁇ , ⁇ -unsaturated carboxylic acids or their reactive derivatives with amidamines of higher carboxylic acids at temperatures above 120 ° C.
  • Amidamines of higher carboxylic acids used are those which are obtainable by reacting 2 moles of carboxylic acid with 1 mole of diethylene triamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine, which are preferably used in the form of their technical qualities.
  • sizes for paper are understood to be those which can be used in bulk and / or in the surface, the use in surface sizing from the size press preferably being considered.
  • the paper or cardboard or cardboard can be made from a wide variety of pulps, for example from sulfite, sulfate, anthraquinone, wood pulp, regenerated, softwood, hardwood pulp or with the addition of synthetic pulps.
  • the papers can also contain various fillers such as Contain chalk, kaolin, talc, as well as other customary auxiliaries and dyes corresponding to the state of the art, such as disperse or solution or pigment dyes, other sizing agents, starches, wet strength or retention agents or other additives such as e.g. Alum, gypsum, etc.
  • Amidamines are those acid amides which, in addition to at least one amide group, also contain at least one amino group in the molecule, which should be primary, tertiary or preferably secondary.
  • Aromatic, aliphatic, cyclic and in particular aliphatic carboxylic acids with 10-26 carbon atoms are referred to as higher carboxylic acids.
  • the resin acids but especially the aliphatic fatty acids or the natural fatty acids with 10-26, preferably 12-18, carbon atoms or mixtures thereof are suitable.
  • such fatty acids with melting points above 30 ° C are of particular value.
  • fatty acid mixtures containing stearic acid in particular, talc, coconut, palmitic, abietic, arachinic, ernca, behenic, ricinoleic, oleic acid, hydrogenated oleic acid, talc oil fatty acids or their hydrogenation products or other, e.g. fatty acids accessible by oxosynthesis.
  • amidamines are prepared by reacting the higher carboxylic acids with diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, and these can preferably be used in the form of their technical qualities.
  • Technical triethylene tetramine is of particular interest.
  • amidamine from approx. 1 mol of technical triethylene tetramine and approx. 2 mol of technical stearic acid has proven to be particularly suitable.
  • Suitable ⁇ , ⁇ -unsaturated carboxylic acids are mono- and polycarboxylic acids, which can also be used in the form of their derivatives, e.g. Halides, esters or partial esters with lower aliphatic alcohols with 1-6 C atoms, but especially in the case of dicarboxylic acids in the form of their anhydrides.
  • Such acids are used e.g. Methacrylic acid, acrylic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, acrylic acid and in particular maleic acid or maleic anhydride being particularly suitable.
  • the ⁇ , ⁇ -unsaturated carboxylic acids are reacted with the amidamines in amounts of 0.5-1.8, in particular 0.8-1.3 mol, per amino group of the amidamine.
  • the reaction takes place at temperatures from 120 ° C. to 250 ° C., preferably 130-170 ° C., the exclusion of oxygen, ie working under protective gases such as N 2 or CO 2 to avoid discoloration, having proven effective.
  • the reaction can be carried out in the melt, in a solution or dispersion medium, if appropriate under pressure. It has proven to be advantageous first to use water as the dispersing medium and then, e.g. when working without pressure, to distill off in the course of the reaction at increasing temperatures, if appropriate also using defoamers.
  • reaction products of amidamines and ⁇ , ⁇ -unsaturated carboxylic acids require reaction times between 0.5 and about 8 hours, usually reaction times of 1 to 5 hours are selected.
  • the amidamines of higher carboxylic acids used are those which are accessible by reacting technical triethylenetetramine with fatty acid mixtures essentially containing stearic acid.
  • the ⁇ , ⁇ -unsaturated carboxylic acid used is acrylic acid and / or methacrylic acid and / or maleic acid and / or fumaric acid and / or their reactive derivatives, such as, for example, carboxylic acid esters, acid chlorides or optionally anhydrides, the reaction is carried out in the presence of water, under protective gas and under Use of maleic anhydride is made An aqueous ammonia solution is used as the basic dispersion medium.
  • reaction products of ⁇ , ⁇ -unsaturated carboxylic acids (or their reactive derivatives) with amidamines of higher carboxylic acids are dispersed in an aqueous basic medium, temperatures from 5 to 95 ° C, preferably 15 to 80 ° C being used.
  • the dispersions have solids concentrations between 5 and 40, preferably 10-25% by weight. It is surprising that the type of sizing agent according to the invention can have low viscosities at room temperature than at elevated temperatures. This fact makes it easier to dose the sizing agent in practice.
  • inorganic or organic bases such as NaOH, KOH, Na 2 CO 3 , triethylamine, mono-, di-, triethanolamine or the corresponding propanolamines are used to adjust the aqueous alkaline dispersions.
  • Ammonia which is also preferably used, is particularly suitable.
  • the bases are used in amounts such that the pH of the dispersions is between 6 and 11, preferably 7 and 9.
  • the sizing preparations according to the invention have the advantage of being very difficult to size, e.g. papers containing wood or regenerate, in the form of their aqueous preparations, to have unlimited storage stability.
  • the sizing agent preparations according to the invention can be used without but also with conventional additives.
  • additives may be considered: alum, cationic or anionic auxiliaries, e.g. based on cationic starch, quaternized polyamines, quaternized polyamide amines, quaternized basic formaldehyde resins, methyl cellulose, carboxymethyl cellulose, lignin sulfonic acids, starches and polysaccharides of various origins, xanthan, pullulan, chitosan, polymers or copolymers of (meth) acrylic acid, mal (meth) acrylamide, (meth) acrylamide Fumaric acid, itaconic acid or other polymers and copolymers with carboxyl or sulfonic acid groups or collagen, gelatin, alginates and caragenates optionally present in salt form.
  • auxiliaries e.g. based on cationic starch
  • quaternized polyamines quaternized poly
  • the effectiveness of the sizing agents according to the invention is not impaired by white toners.
  • the aqueous preparations can also be prepared without emulsifying aids, although the use of such aids may need to be considered.
  • the sizing agents alone or in combination with other sizing agents are particularly well suited for the surface sizing of paper, but can of course also be used for mass sizing. They can be used not only with papers containing chalk or kaolin, but also with papers that contain no or a different filler, e.g. Talc or plaster. They are also suitable for gluing cellulosic materials such as cardboard, textile material, leather, cardboard or chipboard or insulating boards.
  • the wax has a melting point of c 98 ° C.
  • the wax has a melting point of approx. 89 ° C.
  • the wax has a melting point of approx. 79 ° C.
  • the sizing agent A of DE-C-2304586 is used, which is the ammoniacal aqueous preparation of a subsequently imidized copolymer of maleic acid ester, styrene and acrylic acid.
  • the foaming behavior of the sizing agents according to the invention were examined in a laboratory foam testing apparatus which roughly reproduces the conditions on the size press of a paper machine.
  • the sizing liquor which contains the sizing agent to be tested, starch and possibly other additives, is sucked out of a thermostatted beaker at a constant conveying speed through a line located at the bottom of this beaker and through a steel tube which is guided through the lid of the beaker. pumped back into the same.
  • This steel tube ends 150 mm above the surface of the liquid, so that the glue liquor hits the liquid surface in a direct jet, which can cause foaming.
  • the foam volume measured in ml after a certain test time above the surface of the sizing liquor thus represents a measure of the tendency of the liquid to be examined to foam.
  • the following table provides an overview of the foam behavior of the surface sizing agents 1-4 described with the aid of the above-mentioned test apparatus in comparison to the product produced according to DE-C-2304586.
  • 700 ml each of an aqueous sizing agent liquor were prepared, which contained 5% by weight of a commercially available starch and 0.19% by weight of the sizing agent to be examined.
  • the solutions were pumped through the test apparatus at 60 ° C. and at a speed of 200 l / h.
  • the foam volume building up over the surface of the liquid in ml was measured at intervals of 5 min.
  • the application examples are intended to demonstrate the good sizing effect of the sizing agents according to the invention on papers of different material composition.
  • the Cobb value (according to DIN 53132) was determined as a measure of the special sizing.
  • the papers used had the following composition:
  • the papers were sized on a La Borle size press from Mathis, Zurich / Schwei; Type HF.
  • a solution of 5% by weight of commercial starch and 0.2 to 0.4% by weight of the sizing agent to be tested (calculated as 100% active substance) in water was used as the sizing liquor.
  • the surface-sized papers were dried on a drying cylinder within half a minute at approx. 100 ° C. Before the sizing test, the papers were air-conditioned for 2 hours at room temperature.
  • the Cobb values are given in g / m 2 , 60 seconds determined in accordance with DIN 53132. A lower Cobb value means better sizing effect.
  • the TSP value is the assessment in the ink float sample at the application concentrations used.
  • the papers are equipped with the sizing liquor of a predetermined concentration, dried as described above, conditioned and placed on test ink (DIN 53126).
  • the test papers have the dimensions 7 cm x 3 cm.
  • the ink is allowed to act on the underside of the paper for a predetermined time (60 seconds) and then the ink penetration on the top of the test piece is assessed. No penetration is graded with 1, complete penetration with 5.
  • the transition values are proportionally between.

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  • Paper (AREA)

Claims (10)

1. Produits à effet de collage, pouvant être obtenus par réaction d'acides carboxyliques à insaturation α,ß ou de leurs dérivés réactifs avec des amidamines d'acides carboxyliques supérieurs à des températures de plus de 120°C, caractérisés en ce qu'on utilise comme amidamines d'acides carboxyliques supérieurs des amidamines qui peuvent être obtenues par réaction de 2 moles d'acide carboxylique avec 1 mole de diéthylène- triamine, de triéthylènetétramine, de tétraéthy- lènepentamine et de pentaéthylènehexamine que l'on utilise de préférence sous la forme de leurs qualités techniques.
2. Produits suivant la revendication 1, caractérisés en ce qu'on utilise comme amidamines d'acides carboxyliques supérieurs des amidamines qui peuvent être obtenues par réaction des polyéthylène-polyamines mentionnées avec des acides carboxyliques aromatiques, aralipha- tiques, cycliques ou aliphatiques ayant 10 à 26 atomes de carbone par mole.
3. Produits suivant les revendications 1 et 2, caractérisés en ce qu'on utilise comme acides carboxyliques à insaturation α,β ou leurs dérivés réactifs, des acides monocarboxyliques ou poly- carboxyliques ou leurs esters, des esters partiels ou des anhydrides d'acides carboxyliques à insaturation α,ß ayant 3 à 10 atomes de carbone.
4. Produits suivant les revendications 1 à 3, caractérisés en ce qu'ils peuvent être obtenus par réaction d'acides carboxyliques à insaturation a,ß ou de leurs dérivés réactifs avec des amidamines d'acides carboxyliques supérieurs, à des températures de 120 à 250°C, de préférence de 130 à 170°C, éventuellement sous gaz protecteur.
5. Produits suivant les revendications 1 à 4, caractérisés en ce qu'on utilise come acides carboxyliques à insaturation α,ß ou leurs dérivés réactifs, l'acide acrylique et/ou l'acide méthacrylique et/ou l'acide maléique et/ou l'anhydride d'acide maléique et/ou l'acide fumarique et/ou des esters d'acide maléique.
6. Produits suivant la revendication 2, caractérisés en ce qu'on utilise comme polyéthylène-polyamines la triéthylènetétramine et comme acide carboxylique aliphatique, l'acide stéarique ou des mélanges d'acides carboxyliques contenant principalement de l'acide stéarique.
7. Produits suivant la revendication 1, pouvant être obtenus en utilisant comme amidamine le produit de réaction d'environ 1 mole de triéthylènetétramine technique et d'environ 2 moles d'acide stéarique technique.
8. Préparations d'agents de collage contenani des produits suivant les revendications 1 à 7 en dispersion alcaline aqueuse et notamment alcaline ammoniacale aqueuse.
9. Préparations d'agents de collage suivant la revendication 8, caractérisées en ce que les dis. persions contiennent des concentrations en sub. stance active de 5 à 40, de préférence 10 à 25% er poids.
10. Procédé de collage du papier, caractérisa en ce qu'on utilise des préparations d'agents d collage suivant les revendications 8 et 9.
EP83101622A 1982-03-06 1983-02-21 Agent d'encollage Expired EP0088272B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3208139 1982-03-06
DE19823208139 DE3208139A1 (de) 1982-03-06 1982-03-06 Leimungsmittel

Publications (2)

Publication Number Publication Date
EP0088272A1 EP0088272A1 (fr) 1983-09-14
EP0088272B1 true EP0088272B1 (fr) 1986-06-04

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ID=6157517

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EP83101622A Expired EP0088272B1 (fr) 1982-03-06 1983-02-21 Agent d'encollage

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US (1) US4499153A (fr)
EP (1) EP0088272B1 (fr)
DE (2) DE3208139A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0201761B1 (fr) * 1985-04-30 1989-05-31 Bayer Ag Utilisation d'amides basiques pour augmenter la porosité de papier ou de matériaux semblable au papier
US6673205B2 (en) * 2001-05-10 2004-01-06 Fort James Corporation Use of hydrophobically modified polyaminamides with polyethylene glycol esters in paper products

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2149273A (en) * 1937-01-13 1939-03-07 Du Pont Polyamides
US2272466A (en) * 1937-11-22 1942-02-10 Gen Aniline & Film Corp Production of waxlike substances
DE1771293B1 (de) * 1968-04-30 1971-11-11 Sp K Bjuro Poluprowodnikowych Verfahren zur metallisierung der oberflaeche von erzeugnissen aus halbleiterwerkstoffen durch stromlose abscheidung von nickel und oder kobalt
DE1771814C2 (de) * 1968-07-16 1974-05-09 Bayer Ag, 5090 Leverkusen Hilfsmittel-Verwendung für die Papierfabrikation
US3816366A (en) * 1972-12-04 1974-06-11 Gen Mills Chem Inc Acrylic adducts of amino-amides of monomeric fatty compounds
DE2318894C3 (de) * 1973-04-14 1976-06-16 Akzo Gmbh Leimungsmittel fuer papier

Also Published As

Publication number Publication date
EP0088272A1 (fr) 1983-09-14
DE3208139A1 (de) 1983-09-08
DE3363864D1 (en) 1986-07-10
US4499153A (en) 1985-02-12

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