EP0176479A1 - Process for preparing alkaline or neutral sized paper or cardboard with anionic, hydrophobic sizing agents and cationic retention aids - Google Patents

Abstract

Anhydride group-free, aliphatic, unsaturated sizing agents which contain a single N-C6-C22-alk(en)ylamide group or C6-C22-alk(en)yl ester group as hydrophobic substituent and have at least one anionic group, in particular N-C6-C22-alk(en)ylmonoamides or C6-C22-alk(en)yl monoesters of an aliphatic, unsaturated C2-C6-dicarboxylic acid, or salts thereof - some of the sizing agents being new compounds - are particularly highly suitable for use together with commercial retention aids in a process for pulp sizing paper or board at a fibre suspension pH of at least 6.5 in the presence of, for example, aluminium sulphate or in a process for surface sizing paper.

Description

The present invention relates to a process for the production of paper or cardboard which is sized in alkaline or neutral size and which consists in adding an anionic, hydrophobic sizing agent and a cationic retention agent to the pulp suspension having a pH of at least 6.5, wherein the sizing agent, etc. consists of an unsaturated aliphatic compound, e.g. an N-alkylamide group or alkyl ester group preferably having 6 to 22 carbon atoms and at least one acidic group, e.g. contains a carboxyl group.

oder

entspricht.From German Offenlegungsschrift 2,459,165 a process for the production of acid-sized paper or cardboard is known which consists in that the fiber suspension containing aluminum sulfate, which has a pH of 3.5 to 6.5, contains an anionic, hydrophobic sizing agent and a cationic retention agent is added, the sizing agent consisting inter alia of an unsaturated, aliphatic compound which contains, for example, an N-alkylamide group or alkyl ester group having 8 to 30 carbon atoms in the alkyl radical and an acidic carboxyl group, and in particular of the formula

or

corresponds.

As is known, there are significant disadvantages to being faced when producing acid-sized paper, such as the insufficient storage stability and mechanical strength of the acid-sized paper, the acidic wastewater generated during the manufacturing process and the possible expenditure of relatively expensive fillers such as e.g. Kaolin or montmorillonite, which may have to be used due to the acidic pH of the fiber suspensions. The acidic pH of the fiber suspension can also cause corrosion damage to sensitive paper machines and also excludes the use of inexpensive fillers such as Calcium carbonate, especially chalk. Since chalk causes a high degree of whiteness of the sized paper, if necessary, a disproportionate amount of optical brightener must be used in the process for producing acid-sized paper in order to achieve a sufficiently high degree of whiteness. Finally, it should be mentioned that according to German Offenlegungsschrift 2,459,165, relatively high amounts of the sizing agent, e.g. those of the formula (I) or (II) are required to process acidic fiber suspensions into paper.

These disadvantages are avoided, provided that in the process according to the invention for the production of alkaline or neutral sized paper the pH of the fiber suspension is at least 6.5 in the absence of acids, e.g. Sulfuric or formic acid, or especially latent acidic sulfates such as e.g. Aluminum sulfate (alum) is discontinued. In particular, paper with relatively little sizing agent is obtained which has an increased shelf life.

The subject of the present invention thus relates to a process for the alkaline or neutral gluing of paper or cardboard, i.e. a process for the production of alkaline or neutral sized paper or cardboard, which is characterized in that aqueous, cellulose-containing, optionally filler-containing fiber suspensions, which in the absence of acids or latent acidic sulfates such as e.g. Aluminum sulfate has a pH of at least 6.5, preferably at least 7.0, at least (A) an anhydride group-free, aliphatic, unsaturated sizing agent, which has a single N-alkyl or N-alkenylamide group or alkyl or alkenyl ester group, each with at least 6 Carbon atoms in the alkyl or alkenyl radical as hydrophobic substituents and at least one anionic salt form or acidic, ie has a free group and (B) adds a polymeric, cationic retention agent in any order or simultaneously.

• - die wässrigen Zusammensetzungen zur Durchführung des Papierleimungsverfahrens, die, sofern das Leimungsmittel (A) und das Retentionsmittel (B) in beliebiger Reihenfolge zur Faserstoffsuspension separat gegeben werden, neben fakultativen üblichen Zusätzen das Leimungsmittel (A) allein, das mindestens teilweise in Form von Salzen vorliegt, oder, sofern das Leimungsmittel (A) und das Retentionsmittel (B) zur Faserstoffsuspension gleichzeitig gegeben werden, sowohl das gegebenenfalls mindestens teilweise in Salzform vorliegende Leimungsmittel (A) als auch das Retentionsmittel (B) neben fakultativen, üblichen Zusätzen enthalten.
• - nach dem erfindungsgemässen Verfahren geleimtes Papier oder geleimter Karton und
• - die Verwendung des Leimungsmittels (A) der angegebenen Art zum Leimen von Papier oder Karton.

Form further objects of the invention

• - The aqueous compositions for carrying out the paper sizing process, which, if the sizing agent (A) and the retention agent (B) are added separately in any order to the fiber suspension, in addition to optional conventional additives, the sizing agent (A) alone, which is at least partially in the form of salts is present, or, if the sizing agent (A) and the retention agent (B) are added to the fiber suspension at the same time, contain both the sizing agent (A), which may be at least partially in salt form, and the retention agent (B) in addition to optional, conventional additives.
• - glued paper or glued cardboard according to the inventive method and
• - The use of the sizing agent (A) of the specified type for sizing paper or cardboard.

In part, the specified sizing agents (A) are new compounds which, together with the process for their preparation, also form further objects of the present invention. As an essential feature, the sizing agents (A) used according to the invention generally have an anionic group, which is generally present as acidic carboxyl groups. Such groups are preferably present as salts, for example as amine, ammonium or sodium salts in aqueous medium at the pH values of at least 6.5, preferably at least 7.0, of the fiber suspensions and can optionally form anions during papermaking. On the other hand, under the conditions mentioned, the cationic retention agents (B) can also form cations. The ability of the sizing agents and the retention aids to form anions or cations under the conditions of paper production can also be described as anion-active or cation-active. Thus, the anionic sizing agents and the cationic retention agents can also be called anion-active sizing agents or cation-active retention agents.

As a further characteristic feature, the sizing agents (A) have a single N-alkyl or N-alkenylamide group or alkyl or alkenyl ester group as hydrophobic substituents. The alkyl or alkenyl radicals in these N-alkyl or N-alkenyl groups or alkyl or alkenyl ester groups each independently have at least 6, especially 6 to 22, preferably 11 to 22, in particular 16 to 20 carbon atoms. Alkyl residues are preferred over alkenyl residues. The hydrophobic substituents are generally derived from unsaturated or, above all, saturated, primary fatty amines or fatty alcohols. The fatty amines and fatty alcohols are in turn derived from unsaturated or, above all, saturated C ₆ -C ₂₂ , preferably Cii-C22, in particular C ₁₆ -C ₂₀ fatty acids. These are, for example, capronic, preferably caprylic, capric, lauric, myristic or myristoleic, palmitoleic, elaeostearic, clupanodonic acid, in particular oleic, elaidic, erucic, linoleic and linolenic acid. Here, palmitic, stearic, oleic and behenic acids are of particular importance, with palmitic and especially stearic acids being of primary interest. Also easily accessible, technical mixtures of these Fatty acids come into consideration. Synthetic fatty acids and fatty alcohols that can be produced, for example, by oxosyntheae are also included in the definition given.

The preferred primary fatty amines from which the N-alkyl or N-alkenylamide groups of the sizing agents used according to the invention are derived are, for example Hexylamine, octylamine (also called caprylamine), especially dodecyl, hexadecyl and octadecenylamine (also called lauryl, palmityl and oleylamine) and its good accessibility because of in particular octadecylamine (also called stearylamine).

As preferred fatty alcohols from which the alkyl or alkenyl ester groups of the sizing agents used according to the invention are derived, e.g. Hexanol, n- and i-octanol, especially dodecanol, hexadecanol and octadecenol (also called lauryl, palmityl and oleyl alcohol) and its good accessibility because of especially octadecanol (also called stearyl alcohol) mentioned.

Technical mixtures of the fatty amines or fatty alcohols of the type specified are also particularly suitable.

worin D₁ geradkettiges oder verzweigtes Alkenylen mit 2 bis 6 Kohlenstoffatomen und 1 oder 2 Doppelbindungen oder Ethinylen, R₁ Alkyl oder Alkenyl mit 6 bis 22, vorzugsweise 11 bis 22, insbesondere 16 bis 20 Kohlenstoffatomen und X -NH- oder -0-bedeuten, und insbesondere der Formel

worin D₂ geradkettiges oder verzweigtes Alkenylen mit 2 oder 3 Kohlenstoffatomen, R₂ Alkyl oder Alkenyl mit 16 bis 20 Kohlenstoffatomen bedeuten und X die angegebenen Bedeutungen hat.The sizing agents used according to the invention as component (A), which have a single anionic carboxylate group or acidic carboxyl group and a single N-alkyl or N-alkylene amide group or alkyl or alkenyl ester group of the type indicated, generally represent NC ₆ -C ₂₂ alkyl or NC ₆ -C ₂₂ alkenyl half amides or C ₆ -C ₂₂ alkyl or C ₆ -C ₂₂ alkenyl half esters of an aliphatic, unsaturated dicarboxylic acid with preferably 2 to 6 carbon atoms, such as, for example, maleic, fumaric, itacon, , Citraconic, mesaconic, muconic acid or acetylenedicarboxylic acid, with maleic, itaconic and citraconic acids being the focus of interest. Such half-esters or half-amides of the specified dicarboxylic acids, optionally in salt form, preferably correspond to the formula

wherein D _{1 is} straight-chain or branched alkenylene having 2 to 6 carbon atoms and 1 or 2 double bonds or ethynylene, R _{1 is} alkyl or alkenyl having 6 to 22, preferably 11 to 22, in particular 16 to 20 carbon atoms and X is -NH- or -0- , and especially the formula

wherein D _{2 is} straight-chain or branched alkenylene with 2 or 3 carbon atoms, R _{2 is} alkyl or alkenyl with 16 to 20 carbon atoms and X has the meanings given.

darstellen, worin D₃ einen Alkenylenrest der Formel

oder

bedeutet und R₂ und X die angegebenen Bedeutungen haben.In formula (2), alkenyl radicals having 3 carbon atoms are preferably branched. Accordingly, the focus of interest is sizing agents, the compounds of the formula which may be in salt form

represent, wherein D _{3 is} an alkenylene radical of the formula

or

means and R ₂ and X have the meanings given.

genannt.Specific examples of the sizing agents of the formula (3) are, for example, compounds of the formulas which are optionally present in salt form

called.

The compounds of the formulas (6), (7), (8) and (9) are mixtures of isomers.

Before they are used as component (A) in the paper sizing process according to the invention, the sizing agents generally do not need Recrystallization to be cleaned, but can usually as such, as they arise in their manufacture, i.e. can be used without further processing.

Especially when the sizing agent (A) and the retention agent (B) are added separately (in any order) to the fiber suspension in the process according to the invention for sizing paper or cardboard, it is expedient to use the sizing agent at least partially in salt form. If necessary, such salts can be obtained by adding the sizing agents (A) Manufactured by adding, inter alia, an alkylamine or alkanolamine with a total of at most 6 carbon atoms, for example trimethylamine, triethylamine, monoethanolamine, diethanolamine, especially by adding ammonia or an alkali metal hydroxide, for example potassium or especially sodium hydroxide, generally in an aqueous medium at room temperature (about 15 to about 25 ° C) completely or partially converted into the corresponding salts. An alkali metal hydroxide, for example potassium or especially sodium hydroxide or in particular ammonia, is expediently generally used in the form of its dilute, about 1 to 10 percent by weight, aqueous solutions. As a rule, a maximum of 3 mol, especially 0.1 to 1.5, in particular 0.9 to 1.1 mol, of ammonia or alkali metal hydroxide is expediently used per acidic group of the sizing agent present. The sizing agents present as salts thus have, for example, acidic carboxyl groups which are at least partially converted into the groups -COO ^⊖ M ^⊕ , where M ^denotes the corresponding amine, ammonium or alkali metal cations.

Preferred sizing agents (A) of the type mentioned have molecular weights of about 200 to about 500, preferably about 300 to about 400 and, owing to their content of at least one acidic group of the type mentioned, an acid number (mg KOH / g substance) of about 100 to about 300 , preferably about 130 to about 180.

As already stated, the sizing agents used as component (A) in the paper sizing process according to the invention are compounds which are known per se and those which are new per se, which are prepared by methods known per se.

For example, Chem. Abstr. 61, 4209 g (1964) the compound of formula (6), which is however used as an anti-rust agent. British Patent 1,140,652 discloses the monobutyl half ester of itaconic acid as an additive in plastics, but does not provide any information about the compound of formula (7). Doc. Bolg. Akad. Nauk 29 (4) 539-541 (1976) (Inst. Org. Chem., Sofia, Bulg., Cf. Chem Abstr. 85, 80053n (1976)) the connection of the Formula (9), which is however used as an intermediate for the production of surfactants. Finally, the German Offenlegungsschrift 2,459,165 discussed at the outset discloses compounds of the formulas (4) and (5).

oder

entsprechen, worin R₁ Alkyl oder Alkenyl mit 6 bis 22, vorzugsweise 11 bis 22, inbesondere 16 bis 20 Kohlenstoffatomen bedeutet, wobei sich das Verfahren zu deren Herstellung dadurch auszeichnet, dass man ein Amin der Formel

worin R₁ die angegebenen Bedeutung hat, mit Citraconsäureanhydrid oder den Alkohol der Formel

worin Ri die angegebenen Bedeutungen hat, mit Itaconsäureanhydrid in der Regel in etwa äquimolaren Mengen umsetzt.Thus, the compounds which may be present in salt form are new per se, including those of the formula

or

correspond in which R _{1 is} alkyl or alkenyl having 6 to 22, preferably 11 to 22, in particular 16 to 20 carbon atoms, the process for their preparation being characterized in that an amine of the formula

wherein R _{1 has} the meaning given, with citraconic anhydride or the alcohol of the formula

wherein Ri has the meanings given, is reacted with itaconic anhydride as a rule in approximately equimolar amounts.

In addition to the new anionic or acidic sizing agent (A) described above, a polymeric, cationic retention agent (B), which generally has a molecular weight of at least about 1000, is always used in the paper sizing process according to the invention. preferably has about 2000 to about 2,000,000. Retention agents with molecular weights in the range of 10,000 to 100,000 are particularly preferred. In principle, any commercially available retention agent can be used in the process according to the invention. Examples of conventional retention agents (B) which are particularly suitable for use together with the sizing agent (A) in the paper sizing process according to the invention are polyalkyleneimines; Epihalohydrin adducts of reaction products of polyalkylene polyamines and aliphatic dicarboxylic acids; Epihalohydrin adducts of reaction products of polyalkylene polyamines, dicyandiamide and optionally unesterified or esterified with alkanols, organic dicarboxylic acids; Reaction products of dicyandiamide, formaldehyde, ammonium salts of strong inorganic acids and alkylene diamines or polyalkylene polyamines; cationically modified starches or carbohydrates from locust bean or guar gum; Copolymers based on polyamide amines and reaction products of epihalohydrins and polymerized diallylamines mentioned.

Preferred epichlorohydrin adducts of reaction products from polyalkylene polyamines and aliphatic dicarboxylic acids are described, for example, in British patent specification 865 727, epichlorohydrin adducts from reaction products consisting of dicyandiamide and diethylenetriamine or triethylene tetramine, for example in German Offenlegungsschrift 2,710,061 and 486, Epin. Adducts of reaction products from diethylenetriamine, dicyandiamide and unesterified or preferably esterified with lower alkanols dicarboxylic acids, especially dimethyl adipate, for example in British patent specification 1 125 486 and reaction products from dicyandiamide, formaldehyde, ammonium salts of strong inorganic acids and from ethylenediamine or triethylene tetramethane 491 064. Preferred cationically modified starches or carbohydrates from locust bean or guar gum are, for example, alkylene oxide adducts of these starches or carbohydrates, the alkylene oxide used having 2 or 3 carbon atoms in the alkylene radical and quaternary ammonium groups has or in particular represents, for example, a trimethylglycidylammmonium halide. Copolymers based on polyamide amines have molecular weights of 10 ³ to 10 ⁵ , preferably 10 ³ to 10 '* and are made, for example, of aliphatic, saturated dicarboxylic acids having 2 to 10, preferably 3 to 6 carbon atoms, in particular adipic acid, and polyalkylene polyamines, for example Polypropylene and polyethylene polyamines, especially dimethylaminohydroxypropyldiethylenetriamine, are available. They are described, for example, in the CTFA Cosmetic Ingredient Dictionary, 3rd edition 1982, of the Cosmetic Toiletry and Fragrance Association. Reaction products from epihalohydrins and polymerized diallylamines preferably have molecular weights from 1000 to 2000 and are described, for example, in US Pat. Nos. 3,700,623 and 4,279,794.

As retention agents (B), which are in the foreground of interest for use together with the sizing agents (A) in the paper sizing process according to the invention, is a corn or potato starch modified with a quaternary ammonium group-containing propylene oxide, the 25% suspension of which in distilled water at 20 ° C has a pH of 4.2 to 4.6, a polyethyleneimine which has a molecular weight of 10,000 to 100,000, an epichlorohydrin adduct of a reaction product of triethylene tetramine and dicyandiamide, an epichlorohydrin adduct of a reaction product of diethylene triamine , Dicyandiamide and dimethyl adipate, a reaction product of dicyandiamide, formaldehyde, ammonium chloride and ethylenediamine, an epichlorohydrin adduct of a poly-N-methyldiallylamine and a copolymer of adipic acid and dimethylaminohydroxypropyl-diethylenetriamine.

According to the process, the mass sizing of paper or cardboard is generally 0.02 to 3, preferably 0.05 to 3, in particular 0.1 to 0.8 percent by weight of the sizing agent (A) and 0.02 to 3, preferably 0.05 to 3, in particular 0.1 to 0.4 percent by weight of the retention agent (B), based in each case on dry matter at (A) and (B) and on the solids content of the fiber suspension. 0.02 to about 0.05 weight percent of the sizing agent means (A) and the retention aid (B) are only sufficient for the so-called "size press control", which cannot be determined with conventional sizing tests (see, for example, article "Control and Understanding of Size Press Pickup" by DR Dill in the magazine TAPPI ( Proceedings of the Technical Association of the Pulp and Paper Industry, Volume 57, No. 1 of January 1974, pages 97-100) The pulp suspension, to which the sizing agents (A) and the retention agents (B) are added, is shown in US Pat Usually a solids content of 0.1 to 5, preferably 0.3 to 3, in particular 0.3 to 1 percent by weight and a Schopper-Riegler freeness of about 10 ° to about 60 °, especially 20 to 60 °, preferably 20 to 45 °, in particular 25 to 35 °, It generally contains cellulose, in particular those made from softwood, for example pinewood, or made of hardwood, ie hardwood, for example beech wood, which, according to conventional processes, for example the sulfite or, above all, the sulfate process The fiber also contains toffsuspension, if necessary, sanded wood. Waste paper can also be contained in the fiber suspension. Also pulp suspensions made according to the so-called CMP or CTMP process (Chemimechanical and chemithermomechanical pulping processes, see for example article "Developments in Refiner Mechanical Pulping" by SA Collicutt and co-workers in TAPPI, Volume 64, No. 6 from June 1981, pages 57 to 61) manufactured, come into consideration.

The fiber suspension can also contain organic or mineral fillers. Organic fillers include synthetic pigments, e.g. Polycondensation products made of urea or melamine and forasldehyde with large specific surfaces, which are in highly dispersed form and e.g. in British Patent 043 937 and 1 318 244 are described as mineral fillers, among others, titanium dioxide, calcium sulfate and especially talc and / or chalk (calcium carbonate). As a rule, the fiber suspension contains 0 to 40, preferably 5 to 25, in particular 15 to 20 percent by weight, based on the solids content of the fiber suspension, of dry matter of the fillers of the type specified.

Fibrous suspensions containing no filler can be used in a wide pH range, e.g. 6.5 to 10.0, especially 7 to 10 are present. Fiber suspensions are preferred which, if appropriate by adding talc, especially calcium carbonate, especially chalk, have a pH of about 7 to about 9.

The fibrous suspension can also contain additives such as e.g. Starch or its degradation products that increase fiber / fiber or fiber / filler bonding.

High molecular weight polymers of the acrylic acid series, e.g. Polyacrylamides with molecular weights of more than 1,000,000 can be added to the fiber suspension as an aid to retain the finest pulp fiber particles, with minimal amounts of about 0.005 to 0.02 percent by weight, based on the dry matter of the polymer and the solids content of the fiber suspensions, being sufficient.

In the process according to the invention, the fibrous suspension is processed further in a manner known per se on sheet formers or, preferably, continuously on paper machines of conventional design to give paper or cardboard. After drying at about 100 to 140 ° C. for about 0.5 to 10 minutes, papers with a variable basis weight of, for example, 50 to 200 g / m ² are obtained.

As mentioned at the beginning, the aqueous composition for carrying out the paper sizing process according to the invention contains, in addition to optional customary additives, the sizing agent (A), provided that the sizing agent and the retention agent (B) are added separately to the fiber suspension. In this case, the preparation generally contains the sizing agent in whole or in part in the form of its salts (obtained using, for example, ammonia, an alkyl or alkanolamine or an alkali metal hydroxide of the type specified in the ratios given above). Generally, such compositions contain 5 to 30, preferably 5 to 20 percent by weight of dry matter of the sizing agent, which is at least partially in salt form, based on the weight of the aqueous composition.

• (A) 2 bis 40, vorzugsweise 5 bis 30, insbesondere 5 bis 10 Gewichtsprozent Leimungsmittel (berechnet als Trockensubstanz), bezogen auf das Gesamtgewicht der wässrigen Zusammensetzung, wobei das Leimungsmittel gegebenenfalls in Salzform vorliegt, und
• (B) 0,1 bis 20, vorzugsweise 0,5 bis 10, insbesondere 3 bis 8 Gewichtsprozent Retentionsmittel (berechnet als Trockensubstanz), bezogen auf das Gesamtgewicht der wässrigen Zusammensetzung.

On the other hand, the aqueous composition contains, in addition to the optional optional additives, provided the sizing agent (A) and the retention agent (B) are added to the fiber suspension at the same time.

• (A) 2 to 40, preferably 5 to 30, in particular 5 to 10 percent by weight of sizing agent (calculated as dry substance), based on the total weight of the aqueous composition, the sizing agent optionally being in salt form, and
• (B) 0.1 to 20, preferably 0.5 to 10, in particular 3 to 8 percent by weight retention agent (calculated as dry substance), based on the total weight of the aqueous composition.

The aqueous compositions of the type mentioned may contain surface-active compounds as usual additives, e.g. Dispersants or further emulsifiers and / or water-soluble organic solvents. As dispersants and emulsifiers are e.g. Conventional lignin sulfonates, lignin carboxylates, carboxymethyl cellulose, ethylene oxide adducts of alkylphenols, fatty amines, fatty alcohols or fatty acids, fatty acid esters of polyhydric alcohols, substituted benzimidazoles or condensation products from formaldehyde and aromatic sulfonic acids, especially naphthalenesulfonic acids. Further surface-active compounds are preferably the anionic surfactants, especially sulfate surfactants, e.g. Diethanolamine lauryl sulfate, sodium lauryl sulfate or ethoxylated lauryl sulfates. Possible water-soluble organic solvents are aliphatic ethers with 1 to 10 carbon atoms, e.g. Dioxane, ethylene glycol n-butyl ether or diethylene glycol monobutyl ether or alcohols with 1 to 4 carbon atoms, e.g. Isopropanol, ethanol or methanol.

If the aqueous compositions contain additives of the type specified, the quantitative ratio (component (A)): (additives) in the composition is 1: 0.02 to 1: 0.3, preferably 1: 0.05 to 1: 0.1, based on the dry matter of the sizing agents and additives.

The compositions are prepared in a conventional manner by combining the sizing agent (A) together with the retention agent (B) or the sizing agent (A) usually partly in the form of its salt alone either in the molten state or preferably in the solid state, in particular in powdered form, usually in the presence of glass beads and, if necessary, emulsifiers (in the case of sizing agents in the molten state) or dispersants (in the case of sizing agents in powder form) at a maximum of 90 ° C, preferably about 50 to 85 ° C for emulsions, in particular about 15 up to about 25 ° C. in the case of dispersions, with storage-stable, homogeneous, further dilutable emulsions or preferably dispersions being obtained. Since the sizing agents together with the retention aids or the sizing agents which are present entirely or at least partially as salts are generally self-dispersing or self-emulsifying, the use of dispersants or emulsifiers is generally not absolutely necessary. This also applies to the optional addition of solvents and / or surfactants, which are only used if the dispersions or emulsions have insufficient storage stability.

It is also possible to use, in addition to the process for the production of paper or cardboard with a basic or neutral glue, a process for producing paper with a glued surface, in which a glue liquor which contains the components (A) and (B) for example by spraying, preferably by padding, generally applied to the paper at room temperature (15-25 ° C.) and then the impregnated paper at 60 to 140 ° C., preferably 90 to 110 ° _C. for 0.1 to 10, preferably Is dried for 2 to 6 minutes. After drying, a paper is obtained which has a surface application of sizing and retention agent from 50 to 150, preferably 60 to 120 mg / m ² . The paper to be glued is any type of paper with any basis weight, for example paper and cardboard boxes made from bleached or unbleached sulfite or sulfate cellulose.

For the surface sizing of paper, the glue liquor required for this is prepared by diluting with water the emulsions or dispersions specified above which contain both the sizing agent (A) and the retention agent (B). The emulsions or dispersions are diluted so that a glue liquor is formed which (A) 0.02 to 0.4, preferably 0.05 to 3, in particular 0.05 to 1 percent by weight of sizing agent (calculated as dry matter), based on the total weight the aqueous glue liquor, the sizing agent optionally being in salt form, and (B) 0.01 to 0.2, preferably 0.05 to 0.1, in particular 0.3 to 0.8 percent by weight retention agent (calculated as dry substance) on the total weight of the aqueous glue liquor.

As an advantage of the method according to the invention, it should be mentioned that pulp suspensions of the most varied types can be easily processed into paper in mass sizing with relatively particularly small amounts of sizing and retention agent, which has good sizing properties (alkali drop test, ink floating time and, above all, water absorption according to Cobb ) having. This also applies to surface sizing, where the good sizing effects can be achieved with only small amounts of sizing and retention agent. In particular, the low area applications enable a quick working process, so that good surface sizes can be achieved within 20 to 40 seconds at the drying temperature of 90 to 110 ° C, for example. The paper sized according to the process has good mechanical properties, ie good strengths, in particular good tear strength. Good reproducibility of the process is guaranteed for both mass and surface sizing. In particular, wood pulp can be used for mass sizing Containing fibrous suspensions or those containing waste paper are processed. The compatibility of the sizing agent used according to the invention with various fillers such as chalk and also various additives of the type specified above is also advantageous. The sizing and retention agents used according to the invention have good compatibility with the customary auxiliaries, pigments, binders used in the paper industry, in particular optical brighteners and other additives. Furthermore, the sizing and retention agents used are easily accessible, inexpensive and do not tend to form undesirable foams. In addition, the degree of whiteness of the sized paper is not significantly influenced by the size and can even be improved in both the mass and the surface size under certain circumstances. Above all, the generally surprisingly high storage stability of the size dispersions of the type indicated is of great advantage.

The parts and percentages given in the following manufacturing instructions and working examples relate to the weight.

Manufacturing instructions for known compounds as sizing agents Regulation A:

A solution of 26.9 parts of stearylamine (0.1 mol) in 100 parts of chloroform is added to a solution of 9.8 parts of maleic anhydride (0.1 mol) in 100 parts of chloroform within 40 minutes. The reaction mixture is heated to the reflux temperature of about 62 ° C. and kept at this temperature for 6 hours with stirring. The solvent is then distilled off under reduced pressure. 345 parts of the compound of the formula (4) are obtained as white powder.

M.p .: 90-94 ° C.

Acid number: 158.

Regulation B:

The procedure is as described in instruction A, but 27.0 parts of stearyl alcohol (0.1 mol) (instead of 26.9 parts of stearylamine) are used. 34.7 parts of the compound of the formula (5) are obtained as white powder. M.p .: 57-62 "C.

Acid number: 150.

Regulation C:

The procedure is as described in instruction A, but 11.2 parts of itaconic anhydride (0.1 mol) (instead of 9.8 parts of maleic anhydride) are used. 35.8 parts of the compound of the formula (6) are obtained as white powder.

M.p .: 100-108 ° C

Acid number: 152.

Regulation D:

The procedure is as described in instruction A, but 11.2 parts of citraconic anhydride (0.1 mol) and 27.0 parts of stearyl alcohol (0.1 mol) (instead of 9.8 parts of maleic anhydride and 26.9 parts of stearylamine) are used. 34.2 parts of the compound of the formula (9) are obtained as white powder.

Mp 67-70 ° C.

Acid number: 148.

Production examples of new compounds as sizing agents

EXAMPLE 1 The procedure is as described in instruction A, but 11.2 parts of citraconic anhydride (0.1 mol) are used (instead of 9.6 parts of maleic anhydride). 34.6 parts of the compound of the formula (8) are obtained as white powder.

M.p .: 109-113 ° C.

Acid number: 141.

EXAMPLE 2 The procedure is as described in instruction A, but 11.2 parts of itaconic anhydride (0.1 mol) and 27.0 parts of stearyl alcohol (0.1 mol) (instead of 9.8 parts of maleic anhydride and

26.9 parts of stearylamine). It is obtained as a white powder

36.6 parts of the compound of formula (7).

M.p .: 78-81 ^* C.

Acid number: 144.

Application examples

Examples 3 to 8: A pulp suspension of bleached birch sulfate pulp and pine sulfate pulp in a weight ratio of 1: 1 in water of 10 ° dH (German degrees of hardness), which has a Schopper-Riegler freeness of 35 ° and a solids content of 0.5%, is included 20% chalk as a filler and then with 0.01% PERCOL ^e 292 (cationic, high molecular weight (MW> 1 · 10 ⁷ ) polyacrylamide) as an aid to retain the finest cellulose fiber particles, the pH value given in Table I below changing the Fibrous suspension sets. The percentages relate to dry matter of auxiliaries and fillers, based on the solids content of the fiber suspension.

Formulations of the sizing agent are prepared by in each case 7% of the stated sizing agents in powder form, as are obtained in the production, with 3.5% each of POLYMIN @ P (polyethyleneimine with a molecular weight of 10,000 to 100,000) as the retention agent in the presence of deionized water and glass beads with a diameter of 2 mm at room temperature (15 to 25 ° C). The dispersions obtained are pourable, homogeneous and stable in storage. The percentages indicate the dry matter content of sizing or retention agent, based on the total weight of the formulation.

The aqueous formulation of the sizing agent and the retention agent is now added to the fiber suspension in such a way that the amount used is also given in Table I below Dry substance of the sizing agent, based on the solids content of the fiber suspension, arises. The fiber suspension is then processed in a laboratory sheet former "Formette Dynamique" from Allimand, Grenoble, France, to paper sheets which, after drying at 130 ° C. for 3 minutes, have a basis weight of 80 g / m ² .

Aehnliche Ergebnisse werden erzielt, wenn man anstelle von POLYMIN® P als Retentionsmittel CATO® 110 (kationisch modifizierte Stärke, die mit einem quaternären Ammoniumgruppen enthaltenden Propylenoxyd modifiziert ist und deren pH-Wert der 25 %igen Anschlämmung in destilliertem Wasser bei 20°C 4,2 bis 4,6 beträgt), POSAMYL^e E7 (kationisch modifizierte Stärke mit einem Stickstoffgehalt von 0,4 %), einer mit Trimethylglycidylammoniumchlorid kationisch modifizierten, nativen Kartoffelstärke, deren Stickstoffgehalt 1,3 % beträgt, ein Kondensationsprodukt aus Dicyandiamid und Triethylentetramin, das mit Epichlorhydrin weiter umgesetzt und z.B. gemäss Beispiel 2 der deutschen Offenlegungsschrift 2 710 061 hergestellt wird, ein Epichlorhydranaddukt eines Umsetzungsproduktes aus Diethylendiamin und Adipinsäure, das z.B. gemäss Beispiel 1 der britischen Patentschrift 865 727 hergestellt wird, ein Umsetzungsprodukt aus Dicyandiamid, Formaldehyd, Ammoniumchlorid und Ethylendiamin, das z.B. gemäss Beispiel 1 der US-Patentschrift 3 491 061 hergestellt wird, oder RETAMINOL® K (Polyethylenimin eines Molekulargewichtes von 20'000 bis 40'000) einsetzt. Auch Gemische der Retentionsmittel der vorstehend angegebenen Art kommen hierbei in Betracht. Zur Erzielung guter Ergebnisse ist nötigenfalls ein Zusatz von Dispergatoren, insbesondere von Kondensationsprodukten aus Formaldehyyd und Naphthalinsulfonsäuren oder von Carboxymethylcellulose vorteilhaft. Hingegen wird nur eine schlechte Leimung mit Cobb-Werten von etwa 150 bis etwa 200 erhalten, wenn man ein Leimungsmittel gemäss Vorschrift A, B, C oder D oder gemäss Beispiel 1 oder 2, jedoch kein Retentionsmitel, oder ein Retentionsmittel der vorstehend angegebenen Art, jedoch kein Leimungsmittel einsetzt.Both surfaces of the paper sheets obtained, ie the surface obtained on the screen side of the sheet former and the opposite or top side, are tested for their sizing properties. For this purpose, the water absorption according to Cobb is measured after 30 seconds of exposure (WA Cobb ₃₀ ) according to DIN 53 132. The results of the WA Cobb ₃₀ measurements in g / m ^{2 of} the sieve side (SS) and top side (OS) after drying at 130 ° C and after storage for one day at 23 ° C and a relative humidity of 50% are in given in Table I below. The lower the water absorption, the better the size of the paper. WA Cobb ₃₀ values over 100 correspond to a completely unsatisfactory sizing of the paper.

Similar results are obtained if instead of POLYMIN® P as a retention agent CATO® 110 (cationically modified starch, which is modified with a quaternary ammonium group-containing propylene oxide and its pH value of the 25% suspension in distilled water at 20 ° C. 4, 2 to 4.6), POSAMYL ^e E7 (cationically modified starch with a nitrogen content of 0.4%), a native potato starch cationically modified with trimethylglycidylammonium chloride, the nitrogen content of which is 1.3%, a condensation product of dicyandiamide and triethylene tetramine, the further reacted with epichlorohydrin and produced, for example, according to Example 2 of German Offenlegungsschrift 2,710,061, an epichlorohydran adduct of a reaction product of diethylenediamine and adipic acid, which is produced, for example, according to Example 1 of British Patent 865 727, a reaction product of dicyandiamide, formaldehyde, ammonium chloride and ethylenediamine , for example according to Beis 1 of US Pat. No. 3,491,061 is produced, or RETAMINOL® K (polyethyleneimine with a molecular weight of 20,000 to 40,000) is used. Mixtures of the retention agents of the type specified above are also suitable here. If necessary, to obtain good results, it is advantageous to add dispersants, in particular condensation products of formaldehyde and naphthalenesulfonic acids or carboxymethyl cellulose. On the other hand, only poor sizing with Cobb values of about 150 to about 200 is obtained if a sizing agent according to regulation A, B, C or D or according to example 1 or 2, but not a retention agent, or a retention agent of the type specified above is obtained, but does not use sizing agents.

Bei Verwendung von 10 bis 300 Val % Ammoniak oder Natriumhydroxid (als 5 %ige wässrige Lösung) zur Formulierung des Leimungsmittels werden ähnlich gute Leimungsergebniase wie die in Tabelle II angegebenen erhalten.Examples 9 to 15: The procedure is as given in Examples 5 to 8, but the sizing agent and the retention agent are added separately to the fiber suspension, the stated amount (in%) of sizing agent in powder form at room temperature (15 to 25 ° C.) in the presence of water and glass beads with an aqueous, 5% ammonia solution to a self-emulsifying, also pourable, homogeneous and storage-stable emulsion and the formulations of the sizing agent given in Table II below are formed. The Val% indicated mean the number of equivalents of ammonia for 100 equivalents, based on the number of acidic groups present in the sizes used. 10 seconds after the addition of the specified amount of dry substance POLYMIN® P as a retention agent, the fiber suspension is mixed with the specified amount of dry substance of the sizing agent, the amount of sizing and retention agent being based on the solids content of the fiber suspension. The sizing results are also shown in Table II.

When using 10 to 300 val% ammonia or sodium hydroxide (as a 5% aqueous solution) for the formulation of the sizing agent, similarly good sizing results are obtained as those given in Table II.

Similar results are also achieved if the sizing agent is added to the fiber suspension first and then the retention agent is added for 10 seconds. The same also applies if PERCOL® 292 is not added. Similar results are also achieved if talc is used as filler instead of chalk. Good sizing results are obtained even when using pulp suspensions containing wood pulp.

Claims (13)

1. A process for the production of alkaline or neutral sized paper or cardboard, characterized in that aqueous, cellulose-containing, optionally filler-containing fiber suspensions which have a pH of at least 6.5 in the absence of acids or latent acid sulfates (A) an anhydride group-free, aliphatic, unsaturated sizing agent which has a single N-alkyl or N-alkenylamide group or alkyl or alkenyl ester group each having at least 6 carbon atoms in the alkyl or alkenyl radical as hydrophobic substituents and at least one anionic salt form or acidic Has group and (B) adding a polymeric, cationic retention agent in any order or simultaneously. 2. The method according to claim 1, characterized in that as component (A) the NC ₆ -C ₂₂ alkyl or NC ₆ -C ₂₂ alkenyl hemamide or the C ₆ -C ₂₂ alkyl or C _s -Czz- Alkenyl half-ester of an aliphatic, unsaturated dicarboxylic acid or its salts. 3. The method according to claim 2, characterized in that sizing agent is used as component (A), the compounds of the formula which may be in salt form

represent in which Di is straight-chain or branched alkenylene having 2 to 6 carbon atoms or ethynylene, R _i alkyl or alkenyl having 6 to 22 carbon atoms and 1 or 2 double bonds and X is -NH-or -0-. 4. The method according to claim 3, characterized in that sizing agent is used as component (A), the compounds of the formula which are optionally present in salt form

represent in which D _{2 is} straight-chain or branched alkenylene having 2 or 3 carbon atoms, R _{2 is} alkyl or alkenyl having 16 to 20 carbon atoms and X is -NH- or -0-. 5. The method according to claim 4, characterized in that sizing agent is used as component (A), the compounds of the formula which are optionally present in salt form

represent, wherein D _{3 is} a divalent radical of the formula

or

means and R ₂ and X have the meanings given in claim 4. 6. The method according to any one of claims 1 to 5, characterized in that a polyalkyleneimine as the retention agent (B); Epihalohydrin adducts of reaction products from polyalkylene polyamines and aliphatic dicarboxylic acids or of reaction products from polyalkylene polyamines, dicyandiamide and optionally unesterified or esterified with alkanols, organic dicarboxylic acids; Reaction products of dicyandiamide, formaldehyde, ammonium salts of strong inorganic acids and alkylene diamines or polyalkylene polyamines; cationically modified starches or carbohydrates from carob or guar gum; Copolymers based on polyamide amines; or reaction products of epihalohydrins and polymerized diallylamines. 7. The method according to any one of claims 1 to 6, characterized in that the fibrous suspension has a pH of at least 7.0. 8. Aqueous composition for performing the method according to any one of claims 1 to 7, wherein the sizing agent (A) and the retention agent (B) are added separately in any order to the fiber suspension, characterized in that they, at least partially, the sizing agent (A) in the form of salts, and optionally contains conventional additives. 9. Aqueous composition for carrying out the method according to any one of claims 1 to 7, wherein the sizing agent (A) and the retention agent (B) are added simultaneously to the fiber suspension, characterized in that they (A) 2 to 40 weight percent sizing agent, (B) 0.1 to 20 weight percent retention aid,
based in each case on the dry substance of (A) and (B) and on the total weight of the aqueous composition, and optionally containing customary additives. 10. According to the method according to any one of claims 1 to 7 sized paper or cardboard. 11. Use of component (A) according to one of claims 1 to 5 for gluing paper or cardboard. 12. If appropriate, compounds of the formula present in salt form

or

wherein R _{1 is} alkyl or alkenyl having 6 to 22 carbon atoms. 13. A process for the preparation of the compounds according to claim 12, characterized in that a fatty amine of the formula

wherein R _{1 is} alkyl or alkenyl having 6 to 22 carbon atoms, with citraconic anhydride or a fatty alcohol of the formula

wherein R _{1 has} the meanings given, reacted with itaconic anhydride.