Classifications

• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
  • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
  • D21H17/45—Nitrogen-containing groups
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
  • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
  • D21H17/43—Carboxyl groups or derivatives thereof
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
  • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
  • D21H17/45—Nitrogen-containing groups
  • D21H17/455—Nitrogen-containing groups comprising tertiary amine or being at least partially quaternised

Definitions

• the present invention relates to a paper sizing process in which conventional anionic, hydrophobic sizing agents in a novel combination, together with polymerized monoallylamines as retention agents, produce good sizing effects both in the manufacture of paper from fiber suspensions (bulk sizing) and in the production of paper with a sized surface (surface sizing).
• European patent application 131 306 discloses polymerized monoallylamines which, however, are not used in paper manufacture as retention aids together with sizing agents, but rather as drainage accelerators and filter aids for fiber suspensions in the absence of sizing agents.
• the components (A) and (B) are added to aqueous, cellulose-containing, optionally filler-containing fiber suspensions in any order or simultaneously, while in the case of surface sizing the paper is mixed with an aqueous liquor solution which contains the components ( A) and (B) contains, impregnated and dried.
• component (A) fatty acids with at least 14 carbon atoms and resin glues, which are present as a crude product (rosin) or as a formulation (rosin size), are particularly suitable.
• Fatty acids with 14 to 34, especially 16 to 28 and in particular 18 to 22 carbon atoms are preferred.
• Representatives of such fatty acids include myristin, myristole, lignocerin, cerotin, montan, myricine, melissin, especially palmitin, palmitolein and especially stearin, dioxystearin, arachine, behen, oil, Elaidin, linole, linolen, elaeostearin, gadolein.
• synthetic fatty acids e.g. can be produced by oxosynthesis, are used as component (A).
• the resin glue raw products are mainly rosin made from softwood stems (Root resin, wood rosin) or from cut bark of softwood (balsam resin, gum rosin) or around tall resin as a by-product in the production of sulfate cellulose (tall oil rosin).
• the resin acids contained in the resin glue raw product have as main components abietic acid or its derivatives such as neo-, dehydro-, dihydro-, tetrahydroabietic acid, levopimaric and palustric acid, or pimaric acid or its derivatives such as isopimaric acid.
• the ratio of abietic acid to pimaric acid depends on the origin of the raw product.
• the resin acids in the so-called reinforced resin glue are modified with an aliphatic, unsaturated dicarboxylic acid or its anhydride such as citraconic, mesaconic, itaconic, especially fumaric or maleic acid, especially maleic anhydride, by a Diels-Adler addition reaction.
• an aliphatic, unsaturated dicarboxylic acid or its anhydride such as citraconic, mesaconic, itaconic, especially fumaric or maleic acid, especially maleic anhydride
• Formulated resin glues are, for example, resin soaps that are partially or completely saponified with, for example, sodium hydroxide or sodium carbonate and with partial saponification as paste (paste rosin size), with complete saponification with optional addition of paraffin wax as solid substance (dry rosin size) and with saponification to about 75 up to 90% with the addition of, for example, protective colloids as stabilizers as dispersion glue (free resin-containing emulsions, high free-rosin size emulsion).
• resin soaps that are partially or completely saponified with, for example, sodium hydroxide or sodium carbonate and with partial saponification as paste (paste rosin size), with complete saponification with optional addition of paraffin wax as solid substance (dry rosin size) and with saponification to about 75 up to 90% with the addition of, for example, protective colloids as stabilizers as dispersion glue (free resin-containing emulsions, high free-rosin size emulsion).
• TAPPI Technical Association of the Pulp and
• Fatty acids and resin glue of the specified type have the advantage of their good accessibility and low procurement costs. However, higher amounts are necessary in order to achieve satisfactory sizing effects. In contrast, synthetic sizing agents produce satisfactory sizing effects with significantly lower amounts used and are therefore preferred over fatty acids and resin glue.
• component (A) If synthetic sizing agents are used as component (A), those which have at least one anionic, salt-form or acidic group and at least one hydrophobic alkyl or alkenyl radical having 5 to 22 carbon atoms are particularly suitable.
• Sizing agents known per se are preferred, the at least one acidic or salt-form hydroxyl, carboxyl or sulfo group, a single N, N-Cs-C 22 dialkyl or dialkenylamide residue or a single Cs-C 22 alkyl or alkenyl residue and a bridge member -O-CO-or -NH-CO-, whose -CO units are linked to the alkyl or alkenyl radical, or a bridge member -NH-CO-O-, -O-CO-NH- or - Have NH-CO-NH-.
• Aromatic sizing agents of this type having a single alkyl or alkenyl radical correspond, for example, to the formula wherein A 1 and A 2 each have an anionic, ie salt or acidic, ie free carboxyl, hydroxyl or sulfo group, D 1 substituted by halogen, nitro, amino or hydroxyl or unsubstituted phenylene, naphthylene, dihydronaphthylene or tetrahydronaphthylene, R 1 Alkyl or alkenyl having 5 to 22 carbon atoms, Xi is a bridge member of the formula -O-CO-, -NH-CO-, -NH-CO-O-, -O-CO-NH-, -NH-CO-NH-, terminal -CO units of the bridge member are linked to the alkyl or alkenyl radical R 1 , and m and n each represent 1 or 2, especially of the formula and wherein D 2 is substituted by chlorine, bromine,
• X 2 denotes -O- or -NH- and A 1 and n have the meanings indicated, and in particular of the formula wherein Z 1 is chlorine, bromine, nitro or amino, R 4 is alkyl or alkenyl having 15 to 21 carbon atoms and Ai has the meanings given.
• Sizing agents containing a single dialkyl or dialkenylamide radical correspond, for example, to the formula wherein A 1 , A 2 and A 3 each have an anionic, ie salt or acidic, ie free hydroxyl, carboxyl or sulfo group, D 3 an aromatic or cycloaliphatic, divalent, optionally substituted by halogen radical having 5 to 10 carbon atoms or optionally branched alkylene or alkenylene with 2 to 6 carbon atoms.
• Unsaturated aliphatic sizing agents with a single alkyl or alkenyl radical and a single carboxyl group correspond, for example, to the formula wherein D 6 straight-chain or branched alkenylene with 2 to 6 carbon atoms and 1 or 2 double bonds or ethynylene, R 3 alkyl or alkenyl with 6 to 22 carbon atoms and X 2 -NH- or -O-, especially the formula wherein D 7 is straight-chain or branched alkenylene having 2 to 4 carbon atoms, R 5 is alkyl or alkenyl having 16 to 22 carbon atoms and X 2 has the meanings indicated, and in particular the formula wherein D 8 is an alkenylene radical of the formula or and R 5 and X 2 have the meanings given, the sizing agents of the formulas (13), (14) and (15) optionally being in salt form.
• Aromatic sizing agents with a single dialkyl or dialkenyl radical or alkyl or alkenyl radical and a single carboxyl group, which additionally have an anhydride group, correspond above all to the formulas and wherein R 3 is alkyl or alkenyl having 6 to 22 carbon atoms, X 3 -O-.
• R 3 ' has the meanings given for R 3 and R 3 'and R 3 are different from one another or preferably identical and in particular of the formulas and wherein Rs is alkyl or alkenyl having 16 to 22 carbon atoms and X 5 is -O-, -NH- or -N (R 5 ) -, the sizing agents of the formulas (16), (17), (18) and (19) optionally in salt form.
• sizing agents which have a single hydrophobic alkyl, alkenyl, dialkylamide or dialkenylamide residue
• sizing agents with at least two hydrophobic alkyl or alkenyl residues are preferred.
• Such preferred sizing agents have at least one acidic or salted phosphate, carboxyl or sulfo group or at least one anionic dicarbonylmethylene group -CO-CH 2 -CO-, dicarbonylmethylene group -CO- CH-CO-, sulfonylcarbonylimide group -S0 2 -NH-CO- or disulfonylimide group -SO 2 -NH-SO 2 -, at least two C 5 -C 22 alkyl or alkenyl radicals, where at least one of these radicals has at least 8 carbon atoms, and at least one bridge member connecting adjacent alkyl or alkenyl radicals with at least 1 carbon atom and 2 heteroatoms in the main chain.
• Such sizing agents generally correspond to the formula where Q 1 , Qz and Q 3 each -OR 6 , -NH-R 6 , or R 6 and R 7 are alkyl or alkenyl with preferably 8 to 22, in particular 16 to 20 carbon atoms and E 1 and E2 per propylene or preferably ethylene, p is an integer from 1 to 5, preferably 1, 2 or 3, in particular 2, q an integer from 1 to 9 and D 9 and m have the meanings given, especially the formula or wherein D 9 , E 1 , E2, Rs, R 7 , m, p and q have the meanings given, and in particular of the formula or in which D 10 denotes cycloalkylene, naphthylene, especially phenylene substituted by methyl, preferably toluylene and xylylene, in particular unsubstituted phenylene or C 2 -C 6 alkylene and R 6 , p and q have the meanings given.
• Such sizing agents generally correspond to the formula or wherein E i and E2 each propylene or especially ethylene E3 phenyl unsubstituted or substituted by halogen, Ci-C 4 alkyl or alkoxy, Q 4 -O-. -NH- or -N. Q 5 -NH- or -N.
• R 6 R ' 6 and R 7 each alkyl or alkenyl with preferably 8 to 22, in particular 16 to 20 carbon atoms
• R 8 and R 9 each for R 6 and R 7 have the meanings indicated or each unsubstituted or methyl-substituted phenyl, preferably xylyl, in particular tolyl, m, n, s and t each 1 or 2.
• p is an integer from 1 to 5, preferably 1, 2 or 3. in particular 2 , where s and t are 2 if Q 4 and Q 5 are -N.
• n, m, u and v each represent 1 or 2 and Z 2 and Z 3 each halogen, preferably bromine, especially chlorine, or especially C 1 -C 4 alkyl- or alkoxy, preferably methyl, especially methoxy and E 1 , R 5 , R 7 , R 8 , p and t have the meanings given, and in particular the formula or wherein E 1 , R 6 , R 7 , R 8 , Z 2 and m have the meanings given.
• Sizing agents with 2 to 6 dicarbonylmethylene groups, 4 to 12 C 5 -C 12 alkyl or alkenyl residues, at least one of which has at least 8 carbon atoms, and 1 to 5 bridging members which connect two of these alkyl or alkenyl residues, each bridging member having 4 to Has 16 carbon atoms and 2 nitrogen atoms in the main chain, are described for example in European patent application 105 028.
• Such sizing agents are obtainable from hydrophobic ketene dimers and di- or oligoamines and generally correspond to the formula or where formula (42) applies if diamines are the starting component and formula (43) applies if oligoamines are used as the starting component, and in formulas (42) and (43) G alkylene, hydroxyalkylene.
• the sizing agents described in European patent application 96 654 have a sulfo group or one or two carboxyl groups, two C S -C 22 alkyl or alkenyl radicals, a bridge member with 4 having 8 carbon atoms and 2 connecting the two alkyl or alkenyl radicals or 3 nitrogen atoms in the main chain, which are generally of the formula or correspond in which Y 2 is an acidic or salified group of the formula (58) - (CH 2 ) 3 -SO 3 H, (59) -CH 2 -COOH, (60) -CO-L-COOH.
• Y 3 is an acidic or salt group of the formula L ethylene, propylene, ethenylene, 1,2-dimethylethenylene, methylethenylene, prop-1-en-1,2-ylene, cyclohexylene, biscyclo- (2,2,1) -hept-2-enylene, phenylene or carboxyphenylene, R 6 and R 7 each represent alkyl or alkenyl with preferably 8 to 22, in particular 16 to 20 carbon atoms, and n, m and u each represent 1 or 2.
• the European patent application 96 654 also discloses sizing agents, which in a further embodiment, one or two anionic Dicarbonylmethylen- or Dicarbonylmethin phenomenon, two or three Cs-C 22 alkyl or alkenyl radicals and these alkyl or alkenyl groups connecting bridge member having 3 to 12 carbon atoms and have 2 or 3 oxygen atoms or 4 nitrogen atoms in the main chain and generally of the formula or correspond in which R 6 is alkyl or alkenyl with preferably 8 to 22, in particular 16 to 20 carbon atoms and m is 1 or 2.
• European patent application 96 654 also describes sizing agents of another preferred embodiment which also have one or two carboxyl groups which may be in salt form, 2 to 4 C 5 -C 22 alkyl or alkenyl radicals and a bridge member connecting these alkyl or alkenyl radicals
• sizing agents of another preferred embodiment which also have one or two carboxyl groups which may be in salt form, 2 to 4 C 5 -C 22 alkyl or alkenyl radicals and a bridge member connecting these alkyl or alkenyl radicals
• Sizing agents which are of primary interest and are also disclosed in European patent application 96 654 have an acidic or salted phosphate, carboxy or sulfo group, two or three Ca-C22-alkyl or alkenyl residues and a bridge member 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 sizing agents generally correspond to the formula or wherein R 6 and R 7 each represent alkyl or alkenyl with preferably 8 to 22, in particular 16 to 20 carbon atoms and Y 4 is an acidic or salt-form phosphate, carboxyl or in particular sulfo group.
• the retention agent used as component (B) contains the poly (monoallylamine) of the formula (1) disclosed, for example, in European patent application 131 306. If the poly (monoallylamine) is obtained in the presence of at most 1 mol% triallylamine according to European patent application 131 306, the retention aid used according to the invention contains a polymerized, modified, slightly crosslinked monoallylamine. If the poly (monoallylamine) is also obtained in accordance with European patent application 131 306 in the presence of at most 0.5 percent by weight epichlorohydrin, the retention agent contains a polymerized, slightly crosslinked monoallylamine.
• the retention aid preferably consists of the unmodified and uncrosslinked, polymerized monoallylamine of the formula (1) which is obtained by polymerizing the corresponding monoallylamine salt in a polar solvent in the absence of triallylamine and epichlorohydrin.
• a polymerization initiator is required to produce the polymerized monoallylamine from the monoallylamine salt. which has an azo group and cationic nitrogen atoms and is described, for example, in US Pat. No. 4,504,640.
• z 2 stands for zero, provided that after the polymerization of the monoallylamine salt has ended, the acid HT is completely removed, for example by neutralization with a strong base such as sodium hydroxide or by a strongly basic ion exchanger.
• the retention agent is cationic and consists of the polymerized monoallylamine of the formula (1).
• z 2 stands for 10 to 100,000.
• the cationic retention agent of primary interest consists of a polymerized monoallylamine of the formula where Z1 is a number from 10 to 100,000.
• a fatty acid or resin size as component (A) in the mass sizing when using a fatty acid or resin size as component (A) in the mass sizing, however, at least 0.2% by weight, preferably 0.3 to 6, in particular 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 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, are used.
• the fiber suspension to which the sizing agents (A) and the retention agents (B) are added generally has 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 usually contains cellulose, especially softwood, e.g. Pinewood, or hardwood, i.e. Hardwood, e.g. Beech wood, which, e.g. the sulfite or especially the sulfate process is produced. In addition, the fiber suspension may contain groundwood. Waste paper containing alum can also be contained in the fiber suspension.
• the fiber suspension can also contain organic or mineral fillers.
• Organic fillers include synthetic pigments, e.g. Polycondensation products made from urea or melamine and formaldehyde with large specific surfaces, which are in highly dispersed form and e.g. in British patents 1,043,937 and 1,318,244 are described as mineral fillers, among others. Montmorillonite, titanium dioxide, calcium sulfate and especially talc, colin and / or chalk (calcium carbonate).
• the fibrous suspension contains 0 to 40, preferably 5 to 25, in particular 15 to 20 percent by weight, based on the solids content of the fibrous suspension, of dry matter of the optional fillers of the type specified.
• the pH of the pulp suspension can be in a wide range, e.g. Values from about 3.5 to about 10 can be present.
• alkaline fiber suspensions When adding e.g. Calcium carbonate, alkaline fiber suspensions are obtained with a pH of about 7 to about 9, preferably 7.5 to 8.5. Acidic fiber suspensions with a pH of about 3.5 to about 7, preferably 5 to 7, especially 5 to 6, can be added in the absence of calcium carbonate by adding acids, e.g. Sulfuric or formic acid or especially from e.g. latent acidic sulfates, e.g. Aluminum sulfate (alum) can be obtained.
• acids e.g. Sulfuric or formic acid or especially from e.g. latent acidic sulfates, e.g. Aluminum sulfate (alum) can be obtained.
• fiber suspensions which, if appropriate by adding chalk, have a pH of about> to about 9 and are advantageous in this respect. that possible signs of corrosion on the sensitive paper machines are excluded.
• shelf life of paper or cardboard which has been sized at pH values of 7 to 9 of the fiber suspension is clearly superior to those which have been sized at pH values of 3.5 to ⁇ 7.
• 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 over 1,000,000 can be added to the fiber suspension as an aid to retain the finest pulp fiber particles. with minimum 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.
• the pulp suspension is further processed in the mass sizing process according to the invention in a manner known per se on sheet formers or preferably continuously on paper machines of the usual type to 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.
• the glue liquor which contains components (A) and (B), is applied to the paper, for example by spraying on, preferably by padding, generally at room temperature (15-25 ° C.).
• 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, a paper is obtained which has a surface application of sizing and retention agent 50 to 200, preferably 60 to 150, in particular 60 to 120 mg / m 2 .
• the paper to be sized according to the invention is any type of paper with any basis weight, e.g. paper and cardboard made from bleached and unbleached sulfite or sulfate cellulose.
• the aqueous composition for carrying out the paper sizing process according to the invention contains, in addition to optional customary additives, only the sizing agent (A), provided that the sizing agent and the retention agent (B) are added separately to the fiber suspension in the course of the mass sizing.
• 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).
• such compositions contain 5 to 30, preferably 5 to 20 percent by weight of dry substance of the sizing agent, which is at least partially in salt form, based on the total weight of the aqueous composition.
• (A) contains 2 to 40, preferably 5 to 30, in particular 5 to 10 percent by weight Sizing agent (calculated as dry matter), based on the total weight of the aqueous composition, the sizing agent possibly 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 matter ), based on the total weight of the aqueous composition.
• the aqueous compositions of the type indicated optionally contain surface-active compounds, e.g. Dispersants or further emulsifiers and / or water-soluble organic solvents.
• surface-active compounds e.g. Dispersants or further emulsifiers and / or water-soluble organic solvents.
• 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.
• Other surface-active compounds are preferably anionic surfactants, especially sulfate surfactants, e.g. Diethanolamine lauryl sulfate, sodium lauryl sulfate or ethoxylated lauryl sulfates.
• sulfate surfactants e.g. Diethanolamine lauryl sulfate, sodium lauryl sulfate or ethoxylated lauryl sulfates.
• Possible water-soluble, organic solvents include aliphatic ethers having 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.
• the weight ratio (component (A)): (additives) is 1: 0.02 to 1: 0.3, preferably 1: 0.05 to 1: 0.1, based on dry substance sizing agents and additives.
• 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 at most 90 ° C., preferably about 50 to 85 ° C. for emulsions, in particular about 15 up to about 25 ° C.
• dispersions resulting in storage-stable, homogeneous, further dilutable emulsions or preferably dispersions
• 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-dispersing on their own. are emulsifying, the use of dispersants or Em ulgators generally not required. 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.
• 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). based on the total weight of the aqueous glue liquor.
• fiber suspensions of the most varied types with relatively particularly small amounts of sizing and retention aids can be processed in a simple manner to paper, which has good sizing properties (alkali drop test, ink floating time and especially water absorption according to Cobb).
• This also applies to surface sizing, in which the good sizing effects can be achieved even with small area applications of sizing and retention agents.
• the small area orders enable a quick working process, so that at Drying temperature of, for example, 90 to 110 C, good surface sizes can be achieved within approximately 20 to 40 seconds.
• the paper sized according to the process has good mechanical properties. ie. good strengths, especially good tensile strength. Good reproducibility of the process is guaranteed for both mass and surface sizing.
• pulp suspensions containing wood pulp or waste paper can be processed for mass sizing.
• the compatibility of the combination of sizing agents and retention agents used according to the invention with different fillers such as kaolin and also various additives. such as alum in the acidic area of the fiber suspensions in bulk sizing is advantageous.
• the combination of sizing and retention agents used according to the invention has good compatibility with the customary auxiliaries such as dyes used in the paper industry. Pigments. Binders.
• the combination of sizing and retention agents used does not tend to form undesirable foams.
• the use of the retention agent of the specified type in the combination of sizing and retention agents used leads to significantly reduced foaming.
• the degree of whiteness of the sized paper is not significantly influenced by the sizing and can even be improved in both the mass and the surface sizing.
• the generally high storage stability of the dispersions of synthetic sizing agents of the type indicated is of great advantage.
• the precipitate which has precipitated as a viscous, sticky mass is filtered off and extracted with methanol in Soxhlet for 22 hours.
• the sleeve residue is then dried at 50 C and 160 Torr. 49 parts of poly (monoallyl hydrochloride) are obtained.
• Example 1 a fiber 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 0.50%, with 20% chalk as Filler and then with 0.01% PERCOL® 292 (cationic. High molecular weight (MW> 1 • 10 7 ) polyacrylamide) as auxiliary to Retain the finest cellulose fiber particles, resulting in a pH value of 7.8 for the pulp suspension. The percentages relate to dry matter of auxiliaries and fillers. based on the solids content of the fiber suspension.
• a formulation of the combination of the sizing agent and the retention aid is prepared by deionizing 25 parts of the sizing agent according to regulation A as a solid, as is obtained in the production, 1.25 parts of a condensation product of a naphthalenesulfonic acid and formaldehyde as a dispersant and 73.75 parts Water in the presence of glass beads with a diameter of 2 mm at room temperature (15 to 25 C) stirred to 100 parts of a dispersion of the sizing agent. The dispersion obtained is pourable, homogeneous and stable in storage. This dispersion is mixed with 250 parts of a 10%. mixed aqueous solution of the retention aid according to regulation D. The dispersion is then diluted with deionized water. that a formulation is created that is 1% sizing agent and 1% retention aid. based on the dry substance of sizing and retention agent and on the total weight of the formulation. contains.
• the aqueous formulation of the sizing agent and the retention aid is added to the fiber suspension in such a way that an amount of 0.15% each of dry substance of the sizing agent according to regulation A and of the retention agent according to regulation D, based on the solids content of the fiber suspension. arises.
• the fibrous suspension is then processed in a Rapid-Köthen sheet-forming device (see Zellcheming leaflet V / 8/76, Darmstadt, Association of Pulp and Paper Chemists and Engineers) into sheets of paper, which after drying in an ironing press are absent of steam at 130 ° C for 3 minutes have a basis weight of 80 g / m 2 .
• 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.
• the water absorption according to Cobb is measured after 30 seconds exposure (WA Cobb 3 ⁇ ) according to DIN 53 132.
• the results of the measurements in WA Cobb 3 g / m 2 on the wire side (SS) and upper side (OS) after drying at 130 ° C and after storage for two weeks at 23 ° C and 50 0/0 relative humidity are given in Table I below.
• WA Cobb 30 values over 100 correspond to a completely unsatisfactory sizing of the paper.
• Example 2 One proceeds as in 3 Eispie! 1, but gives the retention agent separately to the fiber suspension.
• 25 parts of the sizing agent according to regulation A as a solid, 1.25 parts of the stated dispersant and an aqueous, 1% sodium hydroxide solution in the presence of deionized water and glass beads are stirred at room temperature so that 100 parts of a dispersion are formed has a pH of 7.0.
• the dispersion obtained is pourable, homogeneous and stable in storage.
• a 100% aqueous solution of the retention agent according to regulation D is added to the fibrous suspension first and 10 seconds afterwards the 250% dispersion of the sizing agent obtained is added in such a way that an amount of 0.2% of the dry matter of the sizing and retention agent is used, based on the solids content of the fiber suspension.
• Example 3 The procedure described in Example 1 is followed, however, unused waste (waste paper from a printing house) containing 35% bleached wood fibers is used as the fiber suspension.
• the fiber suspension has a Schopper-Riegler freeness of 34 ° and a solids content of 3.94%.
• the fibrous suspension is mixed with 5% kaolin as a filler and 4% alum as an additive, based on the dry matter of the filler and the additive and on the solids content of the fibrous suspension.
• the pH of the fiber suspension is then adjusted to 5.5 by adding an aqueous 1N sulfuric acid solution.
• Example 1 which contains 1% sizing agent and 1% retention aid, is added to the fiber suspension in such a way that an amount of 0.3% dry matter each of the sizing agent according to regulation A and the retention agent according to regulation D, based on the solids content of the Fibrous suspension arises.
• Table 111 After processing the fiber suspension into paper, the sizing results given in Table 111 below are achieved:
• Example 4 The sizing agent and the retention agent are added separately to the fiber suspension according to Example 3, which has a pH of 5.5.
• a 25 0/0 strength, aqueous dispersion of the sizing agent according to Procedure A is prepared as indicated in Example 2.
• Fig. To the fiber suspension aqueous dispersion is first a 10 o / o-strength aqueous solution of retention agent according to Procedure D and 10 seconds thereafter, strength 25%, if the sizing agent such that an application amount of 0.3% of dry substance of the sizing and retention agent, based on the solids content of the fiber suspension.
• the sizing results given in Table IV below are achieved:
• Example 5 100 parts of a liquid, commercially available, reinforced resin glue dispersion which has a dry matter content of 30% of reinforced tall resin (reinforcement with 6 to 8% fumaric acid) and a very high free resin content (of approx. 90%) are 500 Dilute parts of deionized water to a homogeneous, pourable, storage-stable dispersion.
• This diluted dispersion of the sizing agent is D mixed with 150 parts of a 10 0 / o by weight aqueous solution of retention agent according to Procedure with stirring and then diluted with deionized water to give a formulation is produced containing 2% sizing agent and 1% retention agent, based on dry matter on sizing and retention agent and on the total weight of the formulation.
• Example 1 which has a pH of 7.8, is given such that an amount of 1% dry matter of the sizing agent and 0.5% of dry matter of the retention agent, based on the Solids content of the fiber suspension arises.
• the fiber suspension is then processed into paper as indicated in Example 1.
• the sizing results obtained are given in Table V below:
• Example 6 The procedure is as described in Example 5, but the sizing agent and the retention agent are added separately to the fiber suspension. For this purpose, first the 10% aqueous solution of the retention agent according to regulation D and 10 seconds afterwards the diluted dispersion of the reinforced resin size specified in Example 5 for the fiber suspension according to Example 1, which has a pH of 7.8, given such that an amount of 1% dry matter of the sizing agent and 0.5% dry matter of the retention agent, based on the solids content of the fiber suspension, is used. The fiber suspension is then processed into paper as indicated in Example 1. The sizing results obtained are given in Table VI below.
• Example 7 A liquid, commercially available, reinforced resin soap dispersion (rosin saponified, rosin present as root resin which is reinforced with about 11% maleic anhydride), which has a dry matter content of 50% and a free resin content of 4.5%, is included diluted 10 times the volume of water to a homogeneous, storage-stable dispersion.
• Example 8 a commercially available 51 parts commercially as a Spanish gum rosin present rosin, having a dry matter content of 98%, are 2.5 parts of a condensation product of a naphthalenesulfonic acid and formaldehyde as dispersant, 250 parts of a 10 0 / o by weight, aqueous solution of the retention aid according to regulation D and 196.5 parts of deionized water in the presence of glass beads with an average of 2 mm at room temperature.
• Example 1 To the fiber suspension in accordance with Example 1, having a pH value of 7.8, the resulting formulation will now be given so that a required quantity of dry substance of the sizing agent of 1% and the dry matter of the retention agent of 0.5 o / o, based on the solids content of the fiber suspension arises.
• the pulp suspension is then processed into paper as indicated in Example 1, the sizing results given in Table VIII below being achieved:
• EXAMPLE 9 The procedure is as described in Example 8, but 50 parts of stearic acid (instead of 51 parts of rosin) are used as the sizing agent.
• the formulation of the sizing and retention agent obtained is likewise homogeneous, pourable and stable in storage and is added to the fiber suspension as indicated in Example 8.
• the sizing results of the paper produced from this fiber suspension are shown in Table IX below:

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Paper (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=4293769

Family Applications (1)

Country Status (4)

Cited By (1)

Citations (3)

• 1986
  • 1986-12-15 EP EP86810585A patent/EP0227600A1/fr not_active Withdrawn
  • 1986-12-15 FI FI865107A patent/FI865107A/fi not_active Application Discontinuation
  • 1986-12-18 NO NO865157A patent/NO865157L/no unknown
  • 1986-12-19 JP JP30185686A patent/JPS62156390A/ja active Pending

Patent Citations (3)

Also Published As

Similar Documents

Legal Events