NO865157L - PROCEDURE FOR LIMING PAPER WITH ANIONIC, HYDROPHOBIC LIMITING AGENTS, AND POLYMERIZED MONOALLYLAMINES AS A RECOVERY. - Google Patents

Description

The invention relates to a paper gluing method where common anionic, hydrophobic gluing agents in a new combination together with polymerized monoallyl amines as retention agents produce good gluing effects both in the manufacture of paper from fiber material suspensions (pulp gluing) and also in the manufacture of paper with a glued surface (surface bonding).

Of e.g. European patent application 131 306, polymerized monoallylamines are known, which, however, are not used in papermaking as a retention agent together with sizing agents, but as a dewatering accelerator and filtration aid for fiber suspensions in the absence of sizing agents.

From e.g. European patent application 96 654 is the known anionic, hydrophobic, synthetic sizing agents which, however, are used in the manufacture of paper together with e.g. polyalkylene imines or reaction products of epihalohydrins and polymerized diallylamines as cationic retention agents.

It has now been found that in paper production, both in pulp eqm and in surface sizing, the use of anionic hydrophobic sizing agents together with polymerized monoallylamines or polymerized monoallylamines partially cross-linked by epichlorohydrin as a retention agent in a new combination leads to particularly advantageous sizing effects.

The object of the invention is thus a method for gluing paper or cardboard, the method being characterized by the use of at least

A) an anionic hydrophobic adhesive, and

B) a retention agent containing polymerized, optionally modified, cross-linked monoalkylamine, of formula

in which

T stands for Cl, Br, J, HS04, HS03, H2PC>4, H2PC>3, HCOO, CH3COO

or C„HcCOO,

ZD

z-^etyr a number from 10 to 100,000 , and

z2 means a number from 0 to 100,000.

In the method according to the invention, paper or cardboard components (A) and (B) are mass-glued to aqueous cellulose-containing or possibly filler-containing fiber material suspensions in the desired order or at the same time, while in surface gluing the paper is impregnated with an aqueous glue bath containing components (A) and (B) and dried.

Further subject matter of the invention is thus

- the aqueous composition for carrying out the paper gluing process, which if adhesive (A) and retention agent (B) are added to the fiber suspension at the same time during mass gluing or used as a glue bath for surface gluing of the paper, contains both the adhesive (A) which is present at least partially in salt form as well as retention agent (B), next to optional, common additives, - according to the method according to the invention glued paper or glued cardboard, and - the use of the combination of adhesive agent (A) with retention agent (B) of the specified type for gluing paper or cardboard.

If an adhesive of natural origin is used as component (A), fatty acids with at least 14 carbon atoms and resin adhesives that are available as a raw product (Rosin) or as a formulation (Rosins-Size) come into consideration above all.

The fatty acids with 14 to 35, above all 16 to 28, and especially

18 to 22 carbon atoms are preferred. As representatives of such fatty acids, mention can be made of myristin, myristolein, lignocerin, cerotin, montan, myricin, melissin,

for all palmitin, palmitolein and especially stearin, dioxy-stearin, arachin, behen, oil, elaidin, linol, linolenic, elaeostearin, gadolein, cetaloin, eruca, rizinol and clu-panodonic acid, with oleic, behenic and stearic acids being of particular interest. Well-available technical mixtures of these fatty acids also come into question. In addition to fatty acids of natural origin, synthetic fatty acids can also be used, such as e.g. are 'preparable by oxosynthesis, as component (A).

The resin glue raw products are above all rosin from conifer stems (root resin, Wood Rosin) or from cut traces of conifer wood (balsam resin, Gum Rosin) or tall resin as a by-product of sulphate cellulose production (Tall Oil Rosin). Resin acid which is contained in resin glue raw products has as main components abietic acid or its derivatives such as e.g. neo-, dehydro-, dihydro-, tetrahydro-abietic acid, levopimaric and palustric acid, or pimaric acid or its derivatives such as e.g. isopimaric acid. The ratio between abietic acid and pimaric acid depends on the origin of the raw product. Preferably, the resin acids are the so-called fortified resin adhesives (Fortified Rosin) modified with an aliphatic, unsaturated dicarboxylic acid or their anhydride, such as e.g. citra-con-, mesacon-, itacon-, above all fumaric or maleic acid, especially maleic anhydride by means of a Diels-Adler addition reaction. Formulated resin adhesives are e.g. resin soaps that are partially or completely saponified with e.g. sodium hydroxy or sodium carbonate, and partial saponification can be present as a paste (Paste Rosin Size) by complete saponification with the arbitrary addition of a paraffin wax as a solid substance (Dry Rosin Size) and by saponification to approx. 75 to 90% with the addition of e.g. protective colloids as stabilizers such as dispersion glue (free-rosin-containing emulsions, High Free-Rosin Size Emulsion). Such commercially available resin adhesives are e.g. discussed in Tappi (Technical Ass. of the Pulp and Paper Ind.) Monograph No. 33 (1971).

Fatty acids and resin glues of the aforementioned type have the advantage of their good availability and low acquisition costs. However, high amounts used are necessary to achieve satisfactory gluing effects. Synthetic gluing agents, on the other hand, produce satisfactory gluing effects with significantly lower amounts used and are therefore preferred over fatty acid resins.

If synthetic adhesives are used as component (A), those that have at least one anionic salt-form present or acid group and at least one hydrophobic alkyl or alkenyl residue with 5 to 22 carbon atoms come into consideration above all.

Preferred are adhesives known per se, which have at least one acid or hydroxyl, carboxyl or sulfo group present in salt form, a single N,N-Cg-C22-dialkyl or dialkenyl amide residue or a single Cc-C„„-alkyl - or alkenyl residue and a bridging link -O-CO- or -NH-CO-, if -CO units are linked with the alkyl or alkenyl residue, or have a bridging link -NH-CO-O-, -O-CO-NH- or -NH-CO-NH-.

A single alkyl- or alkenyl-residue-containing aromatic sizing agent of this type corresponds to e.g. formula

in which

A^ and A» each means an anionic, i.e. present in salt form

or acid, i.e. free carboxyl, hydroxyl or sulfo group,

means with halogen, nitro, amino or hydroxyl substituted or unsubstituted phenylene, naphthyl-n, dihydronaphthylene or tetrahydronaphthylene,

R-^ means alkyl or alkenyl of 5 to 22 carbon atoms,

X±means a bridge link of the formulaj-0-CO-, -NH-CO-, -NH-CO-0-,

-0-CO-NH-, -NH-CO-NH-, as end-positioned -CO units of the bridge link are linked to the alkyl or alkenyl residue R-L and

m and n each mean 1 or 2,

above all with formula

in which

D2 means with chlorine, bromine, nitro, amino and/or hydroxyl substituted or unsubstituted phenyl or naphthylene,

R2 means alkyl or alkenyl with 5 to 21 carbon atoms,

R3 means alkyl or alkenyl with 6 to 22 carbon atoms,

X2 means -0- or -NH- and

A-^ and n have the above meaning,

and especially with formula

wherein is chloro, bromo, nitro or amino, is alkyl or alkenyl of 15 to 21 carbon atoms, and A-^ has the indicated formula

with the formulas a

in which A , R^, , m and n have the indicated meaning, and the formulas

wherein R 5 means alkyl or alkenyl with 16 to 22 carbon atoms, and A 1 , R 1 , x , m and n have the indicated meaning.

A single dialkyl- or dialkenyl amide-residual sizing agent corresponds to e.g. formula in which A^, A2 and A^ each means anionic, i.e. present in salt form or acid, i.e. free hydroxyl, carboxyl or sulfo group, D means an aromatic or cycloaliphatic divalent optionally halogen-substituted residue with 5 to 10 carbon atoms , or optionally the branched alkylene or alkenylene of 2 to 6 carbon atoms, R_ and R^<1> each mean alkyl or alkenyl of 6 to 2 2 carbon atoms, and n and m each mean 1 or 2,

above all with formula

in which A4 means a sulfo or carboxyl group, A, and Ag each means a hydroxyl or carboxyl group, which is present? in salt form as anionic groups or as acids, i.e. free groups, C means naphthylene, phenylene, di- or tetrahydrophenylene, cyclohexylene, norbornenylene, i.hexachloronorbornenylene, C^-C^-alkenylene or C-C,-alkylene and R,, n and m has the indicated

2 b j

importance,

and especially formula

in which D,- means a divalent residue with formula

Rj. means alkyl or alkenyl with 16 to 22 carbon atoms and n means 1 or 2, as adhesives of formula (12) are usually present in salt form.

Unsaturated aliphatic sizing agents with a single alkyl or alkenyl residue and a single carboxyl group correspond to e.g. formula

in which

Dg/means straight or branched alkenylene with 2 to 6 carbon atoms and 1 or 2 double bonds or ethynylene, R3 means alkyl or alkenyl with 6 to 22 carbon atoms, and X2 means -NH- or -O-,

above all formula

where D 7 means straight or branched alkenyl with 2 to 4 carbon atoms, R 7 means alkyl or alkenyl with 16 to 22 carbon atoms, and X 2 has the indicated meaning,

as especially formula

in which Dg means an alkenyl radical of formula and R, and X has the indicated meaning, the adhesive with formula (13), (14) and (15) possibly being present in salt form. Aromatic sizing agents with a single dialkyl or dialkenyl residue or alkyl or alkenyl residue and a single carboxyl group which additionally has an anhydride group corresponding above all to the formulas and in which R^ means alkyl or alkenyl with 6 to 22 carbon atoms, X3 means -0-, - NH- or -N(R3')- and R3<1> has the meaning indicated for R3, and R3<1> and R3 are different from each other or preferably are the same and in particular have the formulas in which Rbc means alkyl or alkenyl with 16 to 2 2 carbon atoms and Xb c means -0-, -NH- or -N(RbC)-, the adhesive with formulas (16), (17), (18) and (19) possibly being present in salt form. Compared to the sizing agents of the above-mentioned type which have a single hydrophobic alkyl, alkenyl, dialkylamide or dialkylamide residue, sizing agents with at least two hydrophobic alkyl or alkenyl residues are preferred. Such preferred adhesives have at least one azide or phosphate-carboxyl or sulfo groups present in salt form, or at least one anionic dicarbonylmethylene group - C0-CH2-C0-, dicarbonylmethine group -CO-C1H-CO-' sulfonylcarbonylimide group -SO2-NH-CO -, or disulfonylimide group -S02-NH-S02~, at least two C5-C22~alkyl or -alkenyl residues, with at least one of these residues having at least 8 carbon atoms, and at least one bridge link connecting neighboring alkyl or alkenyl residues and with at least carbon atom and two heteroatoms in the main chain.

The sizing agent with 1 or 2 anionic sulfonylcarbonylimide groups, 2 to 6 C₁-C₂₂ alkyl or alkenyl residues, at least one of which has at least 8 carbon atoms, and a bridging link connecting adjacent alkyl or alkenyl residues and of formula where Dg means a two - or trivalent aliphatic, cycloaliphatic or aromatic residue with a maximum of 10 carbon atoms, and m means 1 or 2, is e.g. mentioned in the European patent application 144 284.

Such adhesives generally correspond to formula

wherein Q^, Q2, and Q3 each mean or

Rg and R7 mean alkyl or alkenyl with preferably 8 to 22, especially 16 to 20 carbon atoms, and and E^ each means propylene or preferably ethylene, p means an integer of 1 to 5, preferably 1, 2 or 3, especially 2, q means an integer from 1 to 9, and Dg and m have the indicated meaning, above all of formula in which Dg, E-^E2, Rg, R , m, p and q have the indicated meaning,

and especially of formula

or

wherein D^q means cycloalkylene, naphthylene, above all methyl-substituted phenylene, preferably toluylene and xylylene, especially unsubstituted phenylene or C^-C^-alkylene, and R^, p and q have the indicated meaning.

The sizing agent with 1 to 6 anionic sulfonylcarbonylamide or disulfonylamide groups and 2 to 6 C^-C22~ alkyl or alkenyl residues, at least one of which has 8 carbon atoms and up to 5 bridge links, connecting two of these alkyl or alkenyl residues, each bridge link having 1 to 10 carbon atoms, 1 to 5 nitrogen atoms, 1 or 2 sulfur atoms and possibly 1 or 2 oxygen atoms in the main chain, is e.g. mentioned in the European patent application 123 763.

Such adhesives generally correspond to formula

or

wherein E, and E_ each means propylene or above all ethylene, E means unsubstituted or with halogen, C-^-C^-alkyl or

-Alkoxy substituted phenyl, Q. means -O-, -NH- or -n' , Q5 means -NH- or -N^ , Rg, Rg and R_, each means alkyl or alkenyl with preferably 8 to 22, especially 16 to 20

carbon atoms, RD and Rn each have that for R_ and R_, indicated be-ts y b /

interpretation, or each means unsubstituted or methyl substituted phenyl, preferably xylyl, especially tolyl, m, n, s and t each means 1 or 2, p means an integer from 1 to 5, preferably 1, 2 or 3, especially 2 , with s and t meaning 2, if Q4 and Q5 mean -N^

above all formula

or

wherein nyi m, u and v each means 1 or 2 and Z2 and Z., each means halogen, preferably bromine, especially chlorine, or above all C-^-C^-alkyl- or -alkoxy, preferably methyl, spe-

is methoxy, and E^, Rg, R^, Rg, p and t have the indicated meaning,

and especially of formula

wherein E 1 , R 2 , R 7 , R 8 , Z 2 and m have the indicated meaning.

Adhesives with 2 to 6 dicarbonyl methine groups, 4 to 12

C5-C12 alkyl or alkenyl residues of which at least one has

8 carbon atoms, and 1 to 5 bridge links, which connect two of these alkyl or alkenyl residues, each bridge link having 4 to 16 carbon atoms and 2 nitrogen atoms in the main chain, are e.g. discussed in the European patent application 105 028. Such sizing agents are obtainable from hydrophobic ketene dimers and di- or oligoamines and generally correspond to the formulas

formula (42) being correct, if diamines are used as starting components, and formula (43) if oligoamines are used as starting components and formulas (42) and (43) G means alkylene, hydroxyalkylene, alkenylene or cycloalkylene with a maximum of 12 carbon atoms, naphthylene, a alkaryl or aryl radical of formula or a heterocyclic radical of formula

E1°^E2 means either propylene or preferably ethylene, R

means hydrogen or an alkyl or alkenyl residue derived from fatty acid with 8 to 12 carbon atoms, and R^ and R-, means alkyl or alkenyl with preferably 8 to 22, especially 16

to 20 carbon atoms, i^, i2, i-j and i^ are each 1,2 or 3,

and y means an integer from 1 to 4.

The sizing agent with 1 or 2 phosphate, carboxyl, sulfo, di-carbonylethylene or dicarbonylmethine groups, 2 to 4 C5~C22~alkyl or -alkenyl residues, at least one of which has at least 8 carbon atoms, and bridge links as connected by 1 or 2 of these alkyl or alkenyl residues in that each bridge link has 1 to 12 carbon atoms, and as heteroatoms in the main chain 2 or 3 oxygen atoms, 2 to 4 nitrogen atoms, 1 or 2 oxygen atoms and 1 nitrogen atom, or 2 nitrogen and 2 oxygen atoms are e.g. mentioned in European patent application 96 654.

Preferably, such adhesives have 1 or 2 phosphate, carboxyl or sulfo groups, 2 to 4 C5-C22 alkyl or alkenyl residues, and 1 or 2 bridging links connecting neighboring alkyl or alkenyl groups, and with 2 to 12 carbon atoms, and either 2 oxygen atoms or 4 nitrogen atoms or 1 or 2 oxygen atoms and 1 nitrogen atom, or 2 oxygen and 2 nitrogen atoms in the main chain usually correspond to formula in which R,, R-, each means alkyl or alkenyl with preferably 8 to 22, especially 16 to 20 carbon atoms and means an acid or group present in salt form -P(O)(0H)2, -SO^H,

-CO-CH=CH-COOH or -CO-CH2-CH2-COOH and m means 1 or 2.

In a further embodiment, the adhesives mentioned in the European patent application 96,654 have a sulfo group or one or two carboxyl groups, two C₁-C₂ alkyl or alkenyl residues, a bridge linking the two alkyl or alkenyl residues and with 4 to 8 carbon atoms and 2 or 3 nitrogen atoms in the main chain, and which generally corresponds to formula

in which Y_ means an acid or group present in salt form of formula Y_ means an acid or group present in salt form of formula

L means ethylene, propylene, ethenylene, 1,2-dimethylethenylene, methyl-ethenylene, prop-1-en-1,2-ylene, cyclohexylene, bicyclo-(2,2,1)-hept-2-enylene, phenylene or carboxyphenylene,

Rg and R7 are each alkyl or alkenyl with preferably 8 more

22, especially 16 to 20 carbon atoms, and

new. m and u each mean 1 or 2.

In the European patent application 9 6 65 4, adhesives are also mentioned which in a further embodiment have one or two anionic dicarbonylmethylene or dicarbonylmethine groups, two or three<Cå-C>22-a1^^1-e-'--1-er alkenyl residues and a bridging link connecting these alkyl or alkenyl residues with 3 to 12 carbon atoms, and 2 or 3 oxygen atoms or 4 nitrogen atoms in the main chain, and generally correspond to the formulas

or in which Rg means alkyl or alkenyl with preferably 8 to 22, especially 16 to 20 carbon atoms and m means 1 or 2. In the European patent application 96 654, adhesives of another preferred embodiment are also mentioned which have one or two optionally present in salt form carboxyl group, 2 to 4 C5-C22 alkyl or alkenyl residues and a bridge linking these alkyl or alkenyl residues with 4 to 6 carbon atoms and either 2 or 3 oxygen atoms or 2 nitrogen atoms or 1 nitrogen atom and 1 or 2 oxygen atoms. which generally corresponds to the formulas

wherein Ro , and R-/, each means alkyl or alkenyl with preferably 8 to 22, especially 16 to 20 carbon atoms, and m, n and u each means 1 or 2.

Adhesive which is at the forefront of interest and is also obvious in the European patent application 96 65 4 has an acid or phosphate, carboxy or sulfo group present in salt form, two or three C 8 -C 8 -alkyl or -alkenyl residues and a bridge link with 2 to 6 carbon atoms and either 2 oxygen atoms or 2 nitrogen atoms or one oxygen atom and one nitrogen atom in the main chain.

Such adhesives generally correspond to formula

in which Rg and R^ each mean alkyl or alkenyl with preferably 8 to 22, especially 16 to 20 carbon atoms and mean an acid or phosphate, carboxyl or especially sulfo groups present in salt form.

The retention agent used as component (B) contains e.g. in the European patent application 131 306 disclosed poly(monoallylamine) of formula (1). If poly(monoallylamine) is obtained in the presence of a maximum of 1 mol% triallylamine according to European patent application 131 306, the retention agent used according to the invention contained a polymerised modified weakly cross-linked mono allylamine. If poly(monoallylamine) is obtained in the presence of a maximum of 0.5% by weight of epichlorohydrin likewise according to European patent application 131 306, then the retention agent contains a polymerized weakly cross-linked monoallylamine. Preferably, however, the retention agent consists of the unmodified or non-crosslinked polymerized monoallylamine of formula (l) which is formed by polymerization of the corresponding monoallylamine salt in a polar solvent in the absence of triallylamine and epichlorohydrin. To produce the polymerized monoallylamine from the monoallylamine salt, a polymerization initiator is required which has an azo group and cationic nitrogen atoms, and e.g. is discussed in US patent no. 4 504 640. In formula (1) hetyr z2null, if after completion of polymerization of the monoallylamine salt the acid H-T e.g. is completely removed by neutralization with a strong base, such as e.g. sodium hydroxide or by a strong basic ion exchanger. If the acid HX is not removed, retention agents are cationic and consist of a polymerized monoallylamine of formula (I), where 10 to 100,000 means. The cationic retention agent of interest in the foreground consists of a polymerized monoallylamine of formula

where zx is a number from 10 to 100,000.

According to the method, when mass gluing paper or cardboard, usually: 0.0 2 to 6% by weight of adhesive (A) and 0.0 2 to 3% by weight of retention agents (B) and when using synthetic gluing agents of the specified type which component (A) usually 0.02 to 3, preferably 0.05 to 3, especially 0.1

to 0.8% by weight of the adhesive (A), and 0.02 to 3, preferably 0.05 to 3, especially 0.1 to 0.4% by weight of the retention agent (B), referred to resp. to the dry matter of (A) and (B) to the solids content of the fiber suspension. 0.02 to approx. 0.05% by weight of the gluing agent (A) and the retention agent (B) is only sufficient for the so-called "size press control" which is not picked up by normal gluing tests (cf. e.g. the articles "Control and Understanding of Size Press Pickup" by D.R. Dill in the journal "Proceedings of the Tappi" Volume 57, Number 1 of January 1974 pages 97-100.

When using a fatty acid or resin glue as a component

(A) however, at least 0.2% by weight, preferably 0.3 to 6, especially 0.5 to 4% by weight of

the sizing agent (A) and at least 0.1% by weight, preferably 0.1 to 2,

in particular 0.15 to 1% by weight of the retention agent (B) referred to or to dry matter (A) and (B) and to the solids content of the fiber suspension.

The fiber suspension, to which adhesive (A) and retention agent (B) are added, usually has a solids content of

0.1 to 5, preferably 0.3 to 3, especially 0.3 to 1% by weight

and a Schopper-Riegler scale of approx. 10° to approx. 60°, above all 20 to 60°, preferably 20 to 45°, especially 25 to 35°. It usually contains cellulose, especially those from conifers, e.g. pine wood, or of hardwood, i.e. hardwoods, e.g. beech wood that is produced according to usual methods, e.g. the sulphite or, above all, the sulphate process. In addition, the fiber material suspension possibly contains wood shavings.

Alum-containing paper can also be contained in fiber suspensions. Also cellulose suspensions which have been produced in the so-called CMP or CTMP method (Chemiemechanical and chemithermomechanical pulping processes, etc., e.g. articles (Development in Refiner Mechanical Pulping" by S.A. Colli-cutt and colleagues in "Proceedings of the Tappi" volume 64,

no. 6 ay June 1981, pages 57 to 61), comes into consideration.

The fiber suspension may also contain organic or mineral fillers. As organic fillers, synthetic pigments, e.g. poly-condensation products of urea or melamine and formaldehyde with large specific surfaces which are available in highly dispersed form and e.g. are mentioned in the British patent 1 0 43 937 and 1 318 244 as mineral fillers including montmorillonite, titanium dioxide, calcium sulphate and above all talc, kaolin and/or chalk (calcium carbonate). Generally, the fibrous material suspension contains 0 to 40, preferably 5 to 25, especially 15 to 20% by weight, referred to the solids content of the fibrous material suspension, and dry matter of any fillers of the aforementioned type.

The pH value of the fiber suspension can lie in a wide range, as it e.g. there may be values of approx. 3.5 to approx.

10. When adding e.g. calcium carbonate produces alkaline fibrous material suspension ions with a pH value of approx. 7 to approx. 9, preferably 7.5 to 8.5. Acidic fiber material suspensions with a pH value of approx. 3.5 to 7, preferably 5 to 7, especially 5 to 6, can be obtained in the absence of calcium carbonate by the addition of acids, e.g. sulfuric or formic acid, or above all of e.g. latent acid sulfates, such as aluminum sulfates (alum) . Preference is given to fiber suspension ion or which, if necessary, with the addition of chalk, has a pH value of approx. > 7 to approx. 9, and are advantageous to the extent that possible corrosion phenomena on the sensitive paper machines are ruled out. Also, the storage capacity of paper or board glued at pH values of 7 to 9 of the fiber suspension is clearly superior to those glued at pH values of 3.5 to ^ 7.

The fiber suspension can also contain additives such as starch or its breakdown products, which increase fibre/fibre or fibre/filler binding.

Also high-molecular polymers of the acrylic acid series, e.g. Polyacrylamides with molecular weights above 1,000,000 can be added to the fiber-substance f-suspension as an aid to retaining the finest cellulose fiber particles, as it is sufficient to use minimal quantities from approx. 0.005 to 0.02% by weight, referred to the dry matter of the polymer and the solids content of the fiber suspension.

The fiber suspension is further processed according to the pulp sizing method of the invention in a manner known per se on sheet formers or preferably continuously on paper machines of the usual construction type into paper or cardboard. After drying at approx. 100 to 140°C for approx. 0.5 to 10 minutes, paper of a variable basis weight of e.g. 50 to 200 g/m2.

For surface gluing of the paper in the method according to the invention, the glue bath containing the components (A) and (B), e.g. by spraying, preferably by filling, usually at room temperature (15-25°C) on the paper. The impregnated paper is then dried at 60 to 140°C, preferably 90 to 110°C for 0.1 to 10, preferably 2 to 6 minutes. After drying, paper is obtained which has a surface application of gluing and retention agent of 50 to 200, preferably 60 to 150, especially 60 to 120 mg/m<2>.

In the case of the papers to be glued according to the invention, it turns

about paper of the desired type with the desired basis weight, e.g. about paper and cardboard from bleached or unbleached sulphite or sulphate cellulose.

As mentioned at the outset, the aqueous compositions for carrying out the paper gluing method according to the invention contain, in addition to desirable common additions, only sizing agent (A) if the sizing agent and retention agent (B) are added separately to the fiber material suspension during mass sizing. In this case, the preparation contains a sizing agent, usually wholly or above all partly in the form of a salt (obtained with the subsequent use of e.g. ammonia, an alkyl or alkanolamine, or an alkali methyl hydroxide of the type indicated, in the conditions indicated above). Generally, such compositions contain 5 to 30, preferably 5 to 20% by weight

of dry matter of the adhesive present at least partially in salt form, referred to the total weight of the aqueous composition.

On the other hand, the aqueous composition contains, in addition to the desirable aqueous additives, if adhesive (A) and retention agent (B) are simultaneously added to the fiber suspension during mass sizing, (A), 20 to 40, preferably 50 to 30, especially 5 to 10 weight-% adhesive (calculated as dry substance), referred to the total weight of the aqueous composition, as the adhesive is possibly present in salt form, and

(B) 0.1 to 20, preferably 0.5 to 10, especially 3 to 8

wt% retention agent (calculated as solids), referenced

to the total weight of aqueous composition.

The aqueous composition of the specified type possibly contains usual additions of surface-active compounds, e.g.

e.g. dispersants, or further emulsifiers and/or water-soluble organic solvents. As dispersants and emulsifiers, there are e.g. considering common 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 of formaldehyde and aromatic sulfonic acids, above all naphthalene sulfonic acids. Further surface-active compounds are preferably anionic surfactants, especially sulfate surfactants, e.g. diethanolamine, lauryl sulfate, sodium lauryl sulfate, or ethoxylated lauryl sulfates. Possible water-soluble organic solvents include 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 specified type, the weight ratio (component (A)): (additives) amounts to 1:0.02, to 1:0.3, preferably 1:0.05 to 1:0.1, referred to the sizing agent and the dry matter of the additives.

The composition is prepared in the usual way, in that adhesive agent (A) is stirred together with retention agent (B) or adhesive agent (A) usually partially in the form of a salt alone either in a molten state or preferably in a solid state, especially in powdered form, usually in presence of glass beads or if necessary in emulsifiers (in the case of adhesives in molten state) or dispersants (in the case of adhesives in powder form) with a maximum of 90°C, preferably approx. 50 to 85°C for emulsions, especially at approx. 15 to approx. 25°C in the case of dispersions, as storage-stable homogeneous further dilutable emulsions, or preferably dispersions, are obtained. As the gluing agents together with the retention agents or with the existing gluing agent alone, which are wholly or at least partially salts, are usually self-dispersing or self-emulsifying, the use of dispersants or emulsifiers is usually not necessary. This also applies to the desired addition of the solvent and/or surfactants, which are only used if the dispersions or emulsions have sufficient storage stability.

When surface gluing paper, the necessary glue bath is prepared by diluting with water the emulsions or dispersions mentioned above, which contain both adhesive (A) and retention agent (B). Thereby, the emulsions or dispersions are diluted so that a glue bath is created which contains (A), -0.02 to 0.4, preferably 0.05 to 3, especially 0.05 to 1% by weight of sizing agent (calculated as dry matter) referred to to the total weight of the aqueous glue bath, the sizing agent possibly being in salt form, and (B), 0.01 to 0.2, preferably 0.05 to 0.1, especially 0.2 to 0.8% by weight retention agent (referred to as solids), referred to the total weight of the aqueous glue bath.

As an advantage of the method according to the invention, it should be mentioned that in mass gluing using synthetic gluing agents, fiber material suspensions of different types can be processed relatively, especially small amounts of gluing and retention agent in a simple way, and into paper that has good gluing properties (alkali drop test, ink swimming time, and above all water absorption according to Cobb). This also applies to the surface bonding, where the good bonding effects are already achieved with small surface applications of bonding and retention agent. In particular, the small surface application enables a quick way of working, so that at increased temperatures of e.g. 90 to 110°C already achieves good surface bonding within 20 to 40 seconds. When using both fatty acids or resin adhesives as well as synthetic adhesives, according to the procedure in pulp-glued paper, it has good mechanical properties, i.e. good strength, especially good tear resistance. A good reproducibility of the method is ensured, both for bulk and surface bonding. In particular, fiber suspensions containing wood shavings and used paper can be processed by mass gluing. Also the compatibility of the combination of the adhesive and the retention agent used according to the invention with different fillers such as e.g. kaolin, and also various additives such as e.g. alum in the acidic area of fiber-substance f -suspension ions in pulp sizing is advantageous. The combination of adhesives and retention agents used according to the invention has good compatibility with the usual auxiliaries used in the paper industry such as dyes, pigments, binders, especially optical brighteners and other additives. Above all, the combination of adhesives and retention agents used does not tend to an unwanted foam formation. Compared to other common retention agents, the use of the retention agent of the specified type in the used combination of adhesive and retention agent leads to clearly reduced foam formation. Moreover, the degree of whiteness of the glued paper is not significantly affected by the gluing, and can even be improved in the meantime both by mass and also by surface gluing. Furthermore, the generally high storage stability of the dispersions of synthetic sizing agents of the indicated type is of great advantage.

The parts and percentages stated in: the following manufacturing regulations and execution examples refer to weight.

Manufacturing instructions and adhesive

Regulation A:

Step I:

270.5 parts of stearyl alcohol (1 mol) and 49 parts of maleic anhydride (0.5 mol) are melted at 70°. To this melt is added 1

part sodium hydrogen sulfate as a catalyst. The reaction mixture is heated to 150°C, and kept at this temperature for 7 hours with stirring, as the water formed during the reaction is removed

from the reaction mixt. After the reaction mixture has cooled to 70°C, 302.4 parts of melted maleic acid distearyl ester are obtained (89% of the theoretical).

Stage II

621 parts according to step I formed molten maleic acid distearyl ester (1 mol), 218.6 parts of sodium pyrosulfite 100% (1.15 mol) and 150 parts of water are heated to the reflux temperature of approx. 98°C, and kept for 20 hours at this temperature with stirring. The reaction mixture is cooled to 30°C and added

8,400 parts of water. The resulting fine suspension is kept for 1 hour at room temperature (15 to 25°C) with stirring. The suspension is filtered off, and the raw product is washed with water until the wash water is sulphite-free. After drying at 8°C under reduced pressure, 717 parts (99% of the theoretical) of the compound with formula are obtained

Melting point: 170-172°C.

Regulation B:

27.5 parts of pyrocatechin (0.25 mol) and 8.7 parts of pyridine (0.11 mol) are dissolved at 50°C in 100 parts of tetrahydrofuran. A solution of 30.3 parts of stearic acid chloride (0.01 mol) in 50 parts of tetrahydrofuran is added to this solution at 50°C within 30 minutes. The reaction mixture is heated to a reflux temperature of approx. 6 7°C, kept for 4 hours at this temperature with stirring, and then cooled to 25°C. 250 parts of an aqueous, 0.5 N hydrochloric acid solution are added to the reaction mixture as the product precipitates out. The product is filtered off, washed with 500 parts of water at 60°C, and dried under reduced pressure at 60°C. 36.4 parts of the compound with formula are obtained as a white powder

sm.p. 62-66°C.

Regulation C:

54.6 parts of o-aminophenol (0.5 mol) are heated in 200 parts of pyridine at 50°C. 151 parts of stearic acid chloride (0.5 mol) are added to this solution over the course of 1 hour, the stearic acid chloride being used as a 40°C hot melt. The temperature of the reaction mixture is raised by itself to 65°C as a suspension is formed which is kept for 4 hours at 50°C with stirring. The reaction mixture is then further heated to 90°C and added to 4000 parts of deionized water with intense stirring. The dark-brown, colored suspension is filtered off and the product is washed with 300 parts of water and dried at 40°C under reduced pressure. Thus, 182 parts of the compound with formula are obtained as a light brown powder

sm.p. 75-77°C.

Manufacturing regulations for a retention agent.

Regulation D:

One proceeds analogously to example 1 in the European patent application 131 306, however, instead of 2,2'-bis-(N-phenyl-amidinyl)-2,2'-azopropane dihydrochloride as polymerization initiator 2,2'-azobis(2- amidinopropane) hydrochloride.

Stage I

Monoallyl hydrochloride

570 parts (10 mol) of monoallylamine are added under cooling to a 35% aqueous hydrochloric acid solution at 5 to 10°C. The colorless clear solution is then dried at 20 torr and 60°C in a rotary evaporator. To remove the water of crystal, the crude product is mixed several times with toluene, dried again with toluene. The formed crystals of the monoallyl hydrochloride are dried with

160 torr and 80°C.

Stage II

Poly(monoallyl hydrochloride)

To a solution of 59.0 parts (0.63 mol) of the dried monoallyl hydrochloride in 21 parts of water is added 0.4 parts (0.0015 mol) of 2,2'-azobis(2-amidinopropane) hydrochloride dissolved in 3 shares water. The yellowish reaction solution is polymerized during 11 hours with stirring, in an inert nitrogen atmosphere at 50°C. The reaction mixture is then mixed again with 0.4 parts of the aforementioned polymerization initiator in 3 parts of water, polymerized for a further 5 hours with stirring. The reaction mixture is then kept under stirring for a further 50 hours at 50°C. To work up the reaction mixture to 800 parts methanol. The precipitate that precipitates as a tough, sticky mass is filtered off and extracted over the course of 22 hours in a Soxhlet with methanol. The sleeve residue is then dried at 50°C and 160 torr. 49 parts of poly(monoallyl hydrochloride) are obtained.

Application examples.

Example, 1

A fibrous material suspension of bleached birch sulfate cellulose and pine sulfate cellulose in a 1:1 weight ratio in water of 10° dH (German hardness) and having a Schopper-Riegler measurement degree of 35°C of a solids content of 0.5% is mixed with 20% chalk as a filler and then with 0.1% "Percol" 292 (cationic high molecular weight (molar weight 1.10 7) polyacrylamide) as an aid for retaining the finest cellulose fiber particles, as a pH value of the fiber suspension is set at 7,8. The percentages refer to dry matter of auxiliaries and fillers, referred to the fiber suspension's solids content.

A formulation of the combination of the gluing agent and the retention agent is prepared, with 25 parts of the gluing agent according to regulation A as a solid, as they appear during the preparation, 1.25 parts of a condensation pyroproduct of a naphthalene sulfonic acid and formaldehyde as a dispersant and 7 3.75 parts of deionized water, is stirred in the presence of glass beads with a diameter of 2 mm and room temperature (15° to 25°C) to 100 parts of a dispersion of the sizing agent. The resulting dispersion is pourable, homogeneous and storage-stable. This dispersion is mixed with 250 parts of a 10% aqueous solution of the retention agent according to regulation D. The dispersion is then diluted with deionized water so that a formulation is created that contains 1% adhesive and 1% retention agent, referred to the dry matter of the adhesive and retention agent to the overall weight of the formulation.

Now the aqueous formulation of the adhesive and retention agent is added to the fiber material suspension so that an applied amount of resp. 0.15% of dry matter and adhesive according to regulation A and retention agent according to regulation D, referred to solids content of the fiber material suspension. The fiber suspension is then processed into paper sheets in a Rapid-Kothen sheet forming apparatus (cf. Zellcheming-Merblatt V/8/76, Darmstadt, Verein derZellstoff- og Papier-Chemiker und

-Ingenieure) which after drying in an ironing press in the absence of steam at 130oC within 3 minutes has a basis weight of 80 g/m<2>.

Both surfaces of the formed paper sheets, i.e. the surface formed on the further side of the sheet former and the opposite or upper side are examined for their gluing properties. For this purpose, the water absorption according to Cobb is measured at 30 seconds exposure time (WA Cobb3^) according to DIN 53 132. The results of the WA Cobb^Q measurement in g/m on the back side (SS) and the top side (OS) after drying at 130°C and after storage of two weeks: at 23°C and 50% relative humidity is indicated in the following table I. The less water absorption, the better the gluing of the paper. WA Cobb^Q values above 100 correspond to a completely unsatisfactory bonding of the paper.

Similar results are also achieved when instead of 25 parts of adhesives according to regulation A, 25 parts of adhesives according to regulation B or 25 parts of adhesives according to regulation C are used.

Example 2

One proceeds as indicated in example 1, however, the retention agent is placed separately in the fiber material suspension. For this purpose, 25 parts of the gluing agent according to regulation A as a solid, 1.25 parts of the specified dispersant are stirred for aqueous 1% sodium hydroxide solution in the presence of deionized water and glass beads, at room temperature, so that 100 parts of a dispersion are formed which has a pH value of 7.0. The resulting dispersion is pourable and homogeneous and stable on storage.

A 10% aqueous solution of the retention agent according to regulation D is first added to the fiber material suspension, and 10 seconds later the formed 25% dispersion of the adhesive so that a used amount of resp. 0.2% of dry matter of sizing and retention agent, referred to the solids content of the fiber suspension. After processing the fiber material suspension into paper as indicated in example 1, the gluing results indicated in the following table II are obtained:

Example 3

One proceeds as indicated in example 1, however, using

as a fiber suspension the term waste (waste paper from a printing press) which contains 35% bleached wood fibres. The fiber suspension has a Schopper-Riegler grinding degree of 34o and a solids content of 2.94%. The fiber suspension is mixed with 5% kaolin as filler and 4% alum as additive, referred to the dry matter of filler and additive and to the solids of the fiber suspension. The pH value of the fibre-fabric suspension is then adjusted by adding an aqueous 1 N sulfuric acid solution of 5.5. The formulation according to example 1, which contains 1% adhesive and 1% retention agent, is added to the fiber suspension so that an amount used of resp. 0.3% of dry matter of the sizing agent according to regulation A, and the retention agent according to regulation D, referred to the solids content of the fiber suspension. After processing the fiber suspension into paper, the gluing results indicated in the following Table III are obtained:

Example 4

To the fiber suspension according to example 3, which has a pH value of 5.5, the sizing agent and the retention agent are added separately. For this purpose, a 25% aqueous dispersion of the sizing agent according to regulation A as specified in example 2 is prepared. To the fiber suspension, first add a 10 % aqueous solution of the retention agent according to regulation D and 10 seconds afterwards a 25% aqueous dispersion of the adhesive so that an applied amount of resp. 0.3% of dry matter of sizing and retention agent, referred to the solids content of the fiber suspension. After processing the fiber suspension into paper as indicated in example 1, the gluing results indicated in the following table IV are obtained:

Example 5

100 parts of a liquid commercial reinforced resin impregnation dispersion which has a solids content of 30% of reinforced tall resin (reinforcement with 6 to 8% fumaric acid) and a very high free resin content (of about 90%), is diluted with 500 parts of deionized water to a homogeneous pourable storage-stable dispersion. This diluted dispersion of the adhesive is mixed with 150 parts of a 10% aqueous solution and retention agent according to regulation D while stirring, and is then diluted with deionized water so that a formulation is created that contains 2% adhesive and 1% retention agent referred to dry matter of a adhesive and retention agent to the total weight of the formulation. It is set thus

formed formulation for the fiber substance suspension according to example 1 which has a pH value of 7.8 that an amount used of 1% of the dry matter of the sizing agent occurs, and of 0.5%

of solids of the retention agent referred to the solids content of the fiber suspension. The fiber material suspension is then processed into paper as indicated in example 1. The achieved gluing results are indicated in the following table V

Example 6

One proceeds as indicated in example 5, however, the gluing agent and the retention agent are added separately to the fiber material suspension. For this purpose, the 10% aqueous solution of the retention agent according to regulation D is first added and 10 seconds later the diluted dispersion of the reinforced resin adhesive specified in example 5 is added to the fiber material suspension according to example 1, which has a pH value of 7.8 , so that there is a used amount of 1% of dry matter of the bonding agent, and of 0.5% of dry matter of the retention agent, referred to the solid matter content of the fiber suspension. The fiber material suspension is then processed into paper as indicated in example 1. The gluing results obtained are indicated in the following table VI.

Example 7

A liquid commercial reinforced resin soap dispersion (with sodium caronate is saponified, as root resin present rosin which is reinforced with about 11% maleic anhydride) and which has a solids content of 50% and a free resin content of 4.5%, is diluted with 10 times the volume of water to a homogeneous storage-stable dispersion. To the fiber material suspension according to example 1, which has a pH value of 7.8, a 10% solution of the retention agent according to regulation D is first added,

and 10 seconds thereafter the diluted dispersion of the reinforced resin soap as sizing agent obtained above, so that there is a use of solids of sizing agent of 1% and of solids of retention agent of 0.5%, referred to the solids content of the fiber suspension. The fiber material suspension is then processed as indicated in example 1 into paper, with the gluing results indicated in the following Table VII being obtained:

Example 8

51 parts of a commercial rosin present as Spanish balsam resin, which has a solids content of 98%, is stirred with 2.5 parts of a condensation pyroproduct of a naphthalene sulfonic acid and formaldehyde as dispersant, 250 parts of a 10% aqueous solution of retention agent according to regulation D, and 196.5 parts of deionized water in the presence of glass beads with a diameter of 2 mm at room temperature. You get 500 parts of a formulation that is available as a homogeneous, pourable and storage-stable dispersion and contains 10% rosin as a sizing agent and 5% retention agent, referred to dry matter and sizing and retention agent, and to the total weight of the formulation. To the fiber material suspension according to example 1, which has a pH value of 7.8, the resulting formulation is now added so that a used amount of dry matter of adhesives of 1% and of dry matter of the retention agent is 0.5%, referred to the solids content of the fiber material suspension . The fiber material suspension is then processed into paper as indicated in example 1, with the gluing results indicated in the following table VIII being obtained:

Example 9

Proceed as indicated in example 8, however, is used

as adhesive 50 parts stearic acid (instead of 51 parts rosin). The formed formulation of adhesive and retention agent is likewise homogeneously swellable and storage-stable, and is added as indicated in example 1 to the fiber suspension. Glue-

the result of the paper produced from this fiber material suspension can be seen in the following table IX:

Claims (11)

1. Procedure for gluing paper or cardboard characterized by the fact that it uses the least (A) an anionic hydrophobic sizing agent, and (B) a retention agent containing a polymerized, even tually modified cross-linked monoallylamine of formula in which T stands for Cl, Br, J, HS04 , HSC>3, H2 PC>4 , H2PO , HCOO, CH3 COO or C2 H5 COO, z1 means a number from 10 to 100,000, and z2 means a number from 0 to 100,000. 2. Method according to claim 1, characterized in that for mass gluing of paper or cardboard, the components (A) and (B) are added to aqueous cellulose-containing or possibly filler-containing fiber material suspensions in the desired order or simultaneously. 3. Method according to claim 1, characterized in that for surface gluing, the paper is impregnated with an aqueous glue bath containing the components (A) and (B), and dried. 4. Method according to one of the claims 1 to 3, characterized in that a fatty acid, a resin adhesive or a synthetic adhesive is used as component (A) which has at least one anionic or present in salt form or acid group and at least one hydrophobic alkyl or alkenyl residue with 5 to 22 carbon atoms. 5. Method according to one of claims 1 to 3, characterized in that a cationic retention agent with the formula is used as component (B) wherein z-^ has the meaning specified in claim 1. 6. Method according to claim 2, characterized in that 0.3 to 6% by weight of adhesive (A) is used, and 0.1 to 2% by weight of retention agent (B), if a fatty acid or resin adhesive is used as adhesive . 7. Method according to claim 2, characterized in that 0.02 to 3% by weight of adhesive (A) and 0.02 to 3% by weight of retention agent (B) are used, if a synthetic adhesive is used. 8. Method according to claim 3, characterized in that the glue bath is used in such a way that there is a surface application of the dry matter of components (A) and (B) on treated paper of 50 to 200 mg/m <2>. 9. Aqueous composition for carrying out the method according to claim 2, wherein the adhesive (A) and the retention agent (B) are simultaneously added to the fibrous material suspension, characterized in that it contains (A) 2 to 40% by weight sizing agent, and (B) 0.1 to 20% by weight retention agent, referred or to dry matter of (A) and (B) to the total weight of the aqueous composition, and any usual additions. 10. Aqueous glue bath as a composition for carrying out the method according to claim 3, characterized in that it contains (A) 0.0 2 to 0.4 wt% sizing agent and (B) 0.01 to 0.2% by weight retention agent. referred or to dry matter (A) and (B), and to the total weight of the aqueous composition and any common additives. 11. Use of the combination of components (A) and (B) according to claim 1 for gluing paper or cardboard.