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EP0008761B1 - Agent d'encollage pour papier et papier encollé obtenu - Google Patents

Agent d'encollage pour papier et papier encollé obtenu Download PDF

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Publication number
EP0008761B1
EP0008761B1 EP79103153A EP79103153A EP0008761B1 EP 0008761 B1 EP0008761 B1 EP 0008761B1 EP 79103153 A EP79103153 A EP 79103153A EP 79103153 A EP79103153 A EP 79103153A EP 0008761 B1 EP0008761 B1 EP 0008761B1
Authority
EP
European Patent Office
Prior art keywords
paper
parts
sizing
sizing agents
water
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
EP79103153A
Other languages
German (de)
English (en)
Other versions
EP0008761A1 (fr
Inventor
Wulf Dr. Von Bonin
Friedhelm Dr. Müller
Heinz Bäumgen
Karl Dr. Leiritz
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
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Priority claimed from DE19782838270 external-priority patent/DE2838270A1/de
Priority claimed from DE19782856858 external-priority patent/DE2856858A1/de
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0008761A1 publication Critical patent/EP0008761A1/fr
Application granted granted Critical
Publication of EP0008761B1 publication Critical patent/EP0008761B1/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
    • D21H17/20—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

Definitions

  • the present invention relates to sizing agents for paper in the form of aqueous preparations of dibasic fatty acid amides quaternized with epichlorohydrin of fatty acids with melting points above 30 ° C. and polyalkylene polyamines and / or their technical mixtures.
  • So-called resin glues based on abietic acid are used as conventional bulk sizes for paper.
  • these sizing agents do not meet all requirements, e.g. B. by requiring alum as an additive, meanwhile other mass sizing agents not dependent on the addition of alum have been developed, such as e.g. B. fatty acid anhydrides or ketenes, isocyanates or chlorocarbonyl derivatives of fatty acids.
  • sizing agents have in common that they are difficult to emulsify, that in most cases cationic additives must be used in order to achieve a satisfactory sizing, and that these sizing agents can only be stored at room temperature to a limited extent in aqueous emulsion, since the ketene, anhydride or isocyanate groups are sensitive to water.
  • Stearic acid or reaction products of aliphatic amines with maleic anhydride can also be used as mass sizing agents, but achieve good efficacies only when used in large quantities or require additions of alum.
  • reaction products of polymeric fatty acids and polyamines if they are reacted with a precisely defined amount of epichlorohydrin, can also be used as mass sizing agents.
  • mass sizing effect is only weakly developed for these substances, while they are well suited for surface sizing.
  • Cio-C2e fatty acids in particular C 12 -C 18 fatty acids, such as lauric, myristic, palmitic and stearic acid are preferred, the latter being preferred.
  • Suitable cyclic or branched amines are e.g. B. tert-aminoalkylamines or aminoalkylpiperazines.
  • the sizing agents are used as aqueous solutions, suspensions or emulsions, optionally in a mixture with other sizing agents.
  • the present invention represents a considerable improvement because the quaternization according to the invention of average dibasic reaction products of crystalline fatty acids with linear polyamines of the general formula H 2 N- (R'NH) " -RNH 2 and / or their technical mixtures in the presence of water with approximately stoichiometric amounts of epichlorohydrin surprisingly leads to products whose effectiveness is significantly improved, ie good sizing effect is achieved with reduced amounts of linear amine applied
  • the concomitant use of electrolyte additives surprisingly leads to a considerably reduced viscosity of the aqueous sizing agent preparation without a substantial loss of activity and thus to improved handling at a given concentration.
  • Suitable fatty acid bases are fatty acids or natural and / or synthetic fatty acid mixtures with 10-26, preferably 12-18 C atoms and melting points above 30 ° C, in particular Stearic acid or stearic acid-containing fatty acids or fatty acid mixtures.
  • other fatty acids such as tallow, coconut, palmitic, abietic, arachidic and behenic acid or hydrogenated oleic acid or others by e.g. B. Oxosynthesis or similar processes accessible fatty acids can be considered.
  • Suitable amines and / or technical amine mixtures for the preparation of the basic fatty acid amides are preferably polyethylene polyamines, for example diethylene triamine, triethylene tetraamine, tetraethylene pentamine and pentaethylene hexamine.
  • the corresponding propylene amines are also suitable.
  • Technical triethylene tetraamine is of particular interest.
  • the fatty acids for the preparation of the amide precursor for the sizing agents according to the invention are used in such amounts that the resulting basic amide contains on average about two basic amino groups per molecule, i. H. e.g. B., about two moles of stearic acid are reacted per mole of triethylene tetraamine.
  • the basic amides can be prepared by various methods familiar to the person skilled in the art, for example very simply by heating stoichiometrically calculated amounts of stearic acid and amine, optionally under nitrogen, to 180 to 220 ° C. and slowly distilling off the water formed during the formation of the amide.
  • the acid numbers of the amidation product should be below 20, preferably below 5.
  • the melt of the resulting basic amides is then cooled to a suitable temperature range, for. B. in the vicinity of the melting points of the amides in water, which are between about 60 and 130 ° C., with the quaternizing agent) and then after 0.5-10 h reaction time, preferably still warm, optionally with a further amount of water with further stirring at 60 -130 ° C over 0.1-10h, converted into a 5-40 wt .-%, preferably 10-25 wt .-%, suspension or emulsion. This is generally done by simple stirring, if necessary also using mechanical emulsifying devices.
  • a variant within the scope of the method according to the invention is that a subordinate, i.e. H. less than 50% by weight of the total amount of epichlorohydrin required of the quaternizing agent was added to the molten basic amide before the first addition of water. This produces an emulsifier in situ which facilitates the distribution of the water added immediately before the main quaternization reaction in the reaction medium.
  • the amount of water present in the quaternization reaction is less than the amount of water subsequently contained in the aqueous sizing agent preparation, since the setting of the desired sizing agent concentration can then be optimally combined with the addition of electrolyte. In many cases, it has proven to be sufficient and technically sensible to add only about 100-900% by weight, based on the amount of the basic amide, of water during the quaternization. Surprisingly, without added water, end products with reduced effectiveness are obtained.
  • the aqueous sizing agent preparations described often have a pulpy consistency which can lead to handling difficulties.
  • the addition of 0.05-5, preferably 0.1-1% by weight (based on solids) of electrolytes according to the invention gives low-viscosity preparations which do not thicken.
  • the addition of electrolyte is most conveniently carried out in the last dilution stage of the size preparation, by dissolving the desired amount of electrolyte in the water intended for the final dilution and thus introducing it.
  • it is also possible to add the electrolyte from the outset or when adding the first or second water this variant has proven to be the most effective.
  • preferred electrolytes are inorganic salts such as ammonium chloride, potassium chloride, calcium chloride, zinc chloride, aluminum chloride or, in particular, sodium chloride, although soluble chlorides, nitrates, sulfates , Phosphates, carbonates of other elements and also the acids or bases themselves are suitable in principle. Hard or mineral tap water often gives sufficient effects.
  • the ready-to-use aqueous preparations of the sizing agents obtained have solids concentrations of 5 to 40, preferably 10 to 25,% by weight. When used, these preparations are further diluted to the concentrations then required, e.g. B. to concentrations below 0.5 wt .-%, as are common in paper sizing.
  • the sizing agents according to the invention have the advantage of being indefinitely stable in storage in the form of their aqueous preparations, and also of no additions of alum or to require a cationic or anionic auxiliary, although an addition of such auxiliary e.g. B.
  • aqueous preparations can also be prepared without emulsifying agents.
  • the sizing agents are particularly well suited for the mass sizing of paper, but can of course also be used for surface sizing. They can be used not only with papers containing chalk or akolin, but also with papers that contain no or a different filler, e.g. B. talc or plaster. They are also suitable for gluing cellulosic materials such as cardboard, textile material, cardboard or chipboard or insulating boards or leather.
  • ink float test is used as an assessment criterion for the sizing agents: one places a paper strip equipped with the agent to be tested on the surface of a bowl filled with standard ink in accordance with DIN 53126 and checks the time it takes for the ink to reach the viewer Strikes through the side of the paper. This test provides a very good assessment option for different sizing agents when standardized.
  • the sizing agents according to the invention have an almost unlimited storage stability in aqueous preparation compared to the reactive sizing agents of the prior art and are therefore technically advantageous.
  • the comparison with resin size (size 1) shows as a further technical advantage of the size according to the invention their good effectiveness.
  • An even more important advantage results from the fact that the sizing agents develop their good effectiveness on paper which is free from alum and contains chalk and optionally contains brighteners and on which resin glue is only slightly effective.
  • the sizing agents according to the invention are therefore also tested, for example, on alum-free, chalk-containing paper.
  • Example 11 The test is carried out as in Example 11, but the paper contains kaolin instead of chalk. An ink swim time of 10 minutes is measured.
  • Example 9 The test is carried out as in Example 9. However, the paper contains talc instead of chalk. An ink swim time of 12 minutes is measured.
  • Example 10 The test is carried out as in Example 10. However, the paper contains groundwood instead of beech sulfate pulp. An ink swim time of 11 minutes is measured.
  • a basic amide is prepared according to Example 2, but in its synthesis the molar ratio of stearic acid to amine is now 3 1. Processing this amide analogously to the production of sizing agents A, B or C leads to emulsions which, when used in accordance with Example 5-11, have less than 1% ink swimming times of less than 2 minutes and are to be regarded as unsuitable.
  • 240 parts of the amide are stirred at about 100 ° C. with 120 parts of water and 65 parts of epichlorohydrin (about 1 mol / amino group) for 1 hour. Then 593 parts of water are added and the mixture is stirred for a further hour with gentle reflux. Then 305 parts of water are added and the mixture is allowed to cool to about 45 ° C. with stirring.
  • a solution of 1.5 parts of NaCl in 203 parts of water is then diluted to a solids content of approximately 18%. This emulsion is used as a sizing agent.
  • a sizing test carried out according to Example 9-11 results in an ink floating time of 16 minutes at 0.45%.
  • the basic amide is prepared from these amines E-K according to Example 2 using the same recipe.
  • the temperature is then reduced to about 40 ° C. and the pulpy material is mixed with a solution of 1.15 parts of NaCl in 92 parts of water while stirring well.
  • a thin, fine-particle suspension is formed, which has a solids content of approx. 15% and can be used as a sizing agent E-K.
  • Example 24 The test is carried out as in Example 24, but the paper contains kaolin instead of chalk. An ink swim time of 12 minutes is measured.
  • Example 23 The test is carried out as in Example 23. However, the paper contains talc instead of chalk. An ink swim time of 12 minutes is measured.
  • Example 24 The test is carried out as in Example 24. However, the paper contains groundwood instead of beech sulfate pulp. An ink swim time of 11 minutes is measured.
  • the sizing test is carried out analogously to Examples 21-25 and gives an ink floating time of 18.5 minutes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Claims (5)

1. Agents d'encollage du papier consistant en une composition aqueuse d'amides dibasiques, dérivés d'acides gras ayant des points de fusion de plus de 30° C et d'amines de formule générale
Figure imgb0007
dans laquelle
R et R' sont identiques ou différents et représentent un reste alkylène en C2 ou C3 et
n a une valeur de 1-6,

et/ou leurs mélanges techniques, quaternisés par 0,5 -1 équivalent dépichiorhydrine (calculé sur les groupes amino dans l'amide basique), et les amines techniques peuvent contenir jusqu'à des quantités de 80% en poids d'additifs qui consistent essentiellement en amines cycliques et/ou ramifiées qui possèdent à peu près le même domaine d'ébullition technique, caractérisés en ce que les agents d'encollage du papier contiennent 0,05 à 1% en poids (rapporté aux matières soiides) d'un électrolyte et en ce que la quaternisation est effectuée en présence d'eau.
2. Agents d'encollage selon la revendication 1, caractérisés en ce que l'on utilise comme amine la triéthylènetétramine technique et comme acide gras l'acide stéarique ou des mélanges contenant de l'acide stéarique.
3. Agents d'encollage selon la revendication 1, caractérisés en ce que l'on utilise comme électrolyte le chlorure de sodium.
4. Agent d'encollage selon la revendication 1, caractérisé en ce qu'il est dilué encore par l'eau jusqu'à la concentration désirée en solides.
5. Papier encollé et contenant éventuellement un azurant, traité avec un agent d'encollage selon la revendication 1.
EP79103153A 1978-09-01 1979-08-27 Agent d'encollage pour papier et papier encollé obtenu Expired EP0008761B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE2838270 1978-09-01
DE19782838270 DE2838270A1 (de) 1978-09-01 1978-09-01 Leimungsmittel fuer papier
DE2856858 1978-12-30
DE19782856858 DE2856858A1 (de) 1978-12-30 1978-12-30 Leimungsmittel fuer papier

Publications (2)

Publication Number Publication Date
EP0008761A1 EP0008761A1 (fr) 1980-03-19
EP0008761B1 true EP0008761B1 (fr) 1981-11-04

Family

ID=25775609

Family Applications (1)

Application Number Title Priority Date Filing Date
EP79103153A Expired EP0008761B1 (fr) 1978-09-01 1979-08-27 Agent d'encollage pour papier et papier encollé obtenu

Country Status (6)

Country Link
EP (1) EP0008761B1 (fr)
CA (1) CA1152243A (fr)
DE (1) DE2961254D1 (fr)
ES (1) ES483786A1 (fr)
FI (1) FI792701A7 (fr)
NO (1) NO792679L (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4530945A (en) * 1982-09-30 1985-07-23 Ppg Industries, Inc. Pigment grinding vehicle
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
EP0221855B1 (fr) * 1985-11-08 1990-07-11 Ciba-Geigy Ag Sels d'ammonium diquaternaire, leur préparation et leur utilisation comme agent de finition pour textiles
DE3620033A1 (de) * 1986-06-13 1987-12-17 Bayer Ag Hydrophobe und oleophobe ausruestungen

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB711404A (en) * 1951-04-18 1954-06-30 American Cyanamid Co Improvements relating to the production of sized paper

Also Published As

Publication number Publication date
CA1152243A (fr) 1983-08-16
DE2961254D1 (en) 1982-01-14
FI792701A7 (fi) 1980-03-02
NO792679L (no) 1980-03-04
ES483786A1 (es) 1980-05-16
EP0008761A1 (fr) 1980-03-19

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