EP0112525A1 - Agent and process for neutral sizing - Google Patents
Agent and process for neutral sizing Download PDFInfo
- Publication number
- EP0112525A1 EP0112525A1 EP83112302A EP83112302A EP0112525A1 EP 0112525 A1 EP0112525 A1 EP 0112525A1 EP 83112302 A EP83112302 A EP 83112302A EP 83112302 A EP83112302 A EP 83112302A EP 0112525 A1 EP0112525 A1 EP 0112525A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- agent
- sizing
- weight
- activation
- aqueous suspension
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004513 sizing Methods 0.000 title claims abstract description 81
- 230000007935 neutral effect Effects 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 82
- 230000014759 maintenance of location Effects 0.000 claims abstract description 23
- 239000000123 paper Substances 0.000 claims abstract description 21
- 239000000835 fiber Substances 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000004645 aluminates Chemical class 0.000 claims abstract description 9
- 229920002678 cellulose Polymers 0.000 claims abstract description 8
- 239000001913 cellulose Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 6
- 150000007514 bases Chemical class 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 18
- 125000002091 cationic group Chemical group 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000007900 aqueous suspension Substances 0.000 claims description 15
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 12
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 10
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 10
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 10
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 10
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 10
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 229920003043 Cellulose fiber Polymers 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 5
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 229920002472 Starch Polymers 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 150000008043 acidic salts Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 3
- 239000000194 fatty acid Substances 0.000 claims description 3
- 229930195729 fatty acid Natural products 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 3
- 150000002830 nitrogen compounds Chemical group 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims 2
- QISOBCMNUJQOJU-UHFFFAOYSA-N 4-bromo-1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1NN=CC=1Br QISOBCMNUJQOJU-UHFFFAOYSA-N 0.000 claims 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000003292 glue Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 239000010893 paper waste Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- -1 aluminum ions Chemical class 0.000 description 4
- 239000011436 cob Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007127 saponification reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 241000218657 Picea Species 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000010897 cardboard waste Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 235000007173 Abies balsamea Nutrition 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004857 Balsam Substances 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000018716 Impatiens biflora Species 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/14—Carboxylic acids; 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
- D21H17/62—Rosin; 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
- D21H17/63—Inorganic compounds
- D21H17/64—Alkaline compounds
-
- 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
- D21H17/63—Inorganic compounds
- D21H17/66—Salts, e.g. alums
-
- 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
Definitions
- the present invention relates to a mass sizing agent for paper, cardboard, cardboard and other cellulose-containing materials in the neutral range, as well as a one-step process for mass sizing with this agent.
- the partial or complete replacement of the aluminum sulfate with sodium aluminate leads to the desired increase in the pH value, without a deterioration in the size being observed.
- Aluminum sulfate is therefore no longer required to flocculate resin glue and fix it to the cellulose fibers; it can be substituted by adding sodium aluminate and then changing the pH.
- the object of the present invention is to find a means and a method for the neutral sizing of paper, cardboard and other cellulose-containing materials, in which the above difficulties and disadvantages are eliminated.
- the solution to the problem is based on the knowledge that the known sizing process can thereby be improved, in particular carried out more cost-effectively, if the sizing is carried out with an agent which contains both the aluminate and the resin glue, in such a way that the precipitation of the Glue resin as aluminum resinate in the sizing agent is excluded.
- the precipitation should only take place after the sizing agent and the cationic retention agent have been mixed into the fiber suspension.
- a sizing agent consisting of water, an organic solvent that is immiscible with water, a basic compound, an alkali aluminate and a sizing resin.
- Water-soluble alcohols for example methanol, ethanol and isopropanol, can be used as the organic solvent, but water-soluble ketones, for example acetone and others, can also be used.
- the alcohol: sizing component weight ratio should advantageously be between 10: 1 and 1:: 2 however 5: 1 to 0.5: 1.
- the amount of the organic solvent depends on the solubility and amount of the organic sizing component which must be completely dissolved in the sizing agent according to the invention.
- Sodium or potassium hydroxide is expediently used as the base-reacting compound, in such amounts that the pH in the sizing agent is about 12, so that the precipitation of aluminum hydroxide is avoided.
- the amount of alkali added also serves to saponify the sizing component, which should be 100%, for example saponification of a saturated or unsaturated fatty acid with 12 to 23 carbon atoms.
- the sizing component can be a rosin or tall resin, a resin soap or a dry resin glue. Fatty acids with 12 to 23 carbon atoms can also be used.
- the rosins and tall resins can of course also be present as adducts of maleic or fumaric acid (Diels-Alder'sche diene synthesis).
- the preparation of the new sizing agent can be carried out in a very simple manner by mixing the components at room temperature, in such a way that softened or hardness-stabilized water, initially solid alkali aluminate or an aqueous alkali aluminate solution, is introduced into a water reservoir. To avoid precipitation and possibly saponification of the sizing component, sodium hydroxide is introduced in solid or dissolved form. Finally, alcohol and sizing component are added with stirring. It is stirred until it is complete solution of the sizing component has occurred. Based on the total active ingredient content, the alkali content of the new sizing agent is between 5 and 30% by weight, the sodium aluminate content between 10 and 50% by weight and the content of the sizing component between 40 and 85% by weight.
- Softening or hardness stabilization is necessary to avoid precipitation and is carried out according to known processes (e.g. with ethylenediaminetetraacetic acid and nitrilotriacetic acid).
- the new sizing agent can be added directly to the fiber suspension to be sized. After mixing in the pulper or in a downstream chest, the sizing agent is activated by means of acids and / or acid-reacting salts, the amount of acid and / or salt being measured so that a pH of about 7 is reached.
- Cationic retention agents significantly improve the fixation of fiber and filler as well as sizing agents. The amount depends on the type of retention aid. 0.02 to 0.2% by weight, based on the amount of substance, should, however, suffice.
- so much sizing agent can be introduced into the aqueous suspension of cellulose fibers until a pH of at most 9 is reached.
- cation-active retention agent in particular a cation-active polymer retention agent, is introduced, homogeneously distributed therein and the sizing agent is activated by adjusting the pH to 7.2 to 7.5.
- so much sizing agent is added to the aqueous suspension until a pH of 7.5 to 8 or 7.6 to 8 is reached.
- polyethyleneimine, cationic starch derivatives, polyacrylamide, polymethacrylamide can be introduced into the aqueous suspension, as in the process version already described.
- Quaternary nitrogen compounds can be used as well as cation-active polymers. Amounts of 0.1 to 0.5% by weight, based on the fiber content of the aqueous suspension, are sufficient to achieve good mass sizing, while the sizing agent in amounts of 0.1 to 10% by weight, based on the fiber content of the suspension and calculated as the solids content. In some cases, amounts of retention agent from 0.02% by weight, based on the amount of substance, should suffice.
- the sizing agent can be activated by means of acids and / or acid-reacting salts.
- Organic and inorganic acids that do not form insoluble salts or complex compounds with the aluminum ions are suitable.
- sulfuric acid and aluminum sulfate formic acid and acetic acid have proven their worth.
- the new process can also be carried out by first introducing a cationic polymeric retention agent into the aqueous suspension of cellulose fibers with a pE value of less than 7, in particular 6.5 to 6.8, and then homogeneously distributed. Subsequently, so much sizing agent is added until a pH greater than 7 is reached. Sufficient sizing agent should be added to the aqueous suspension until a pH of 7.5 to 8 is reached. The pH of the cellulose fiber suspension should not be below 6.
- the aforementioned agents can be used as cationic retention agents, in amounts of 0.02 to 0.5% by weight, based on the fiber content of the aqueous suspension.
- Example 2 As in Example 1, 645 parts by weight of water are placed in a stirred vessel. After 50 parts by weight of 50% sodium hydroxide solution and 45 parts by weight of solid sodium aluminate in powder form have been introduced, the mixture is stirred until completely dissolved. Then 135 parts by weight of isopropanol are run in and 125 parts by weight of reinforced powder resin glue are distributed therein. After the powder glue has completely dissolved, a slightly yellow colored solution is present, to which 1 part by weight of sorbitol is added for stabilization. The active ingredient content of the sizing agent is about 20% by weight.
- 365 parts by weight of process water (city water) with a hardness of 25 ° dE are pumped into a stirred vessel and mixed with 1 part by weight of ethylenediaminetetraacetic acid or nitrilotriacetic acid.
- 200 parts by weight of a sodium aluminate solution with an Al 2 O 3 content of 19% by weight, 35 parts by weight of sodium hydroxide in flake form and 200 parts by weight of ethanol are then introduced with stirring. Stir until a clear solution has formed.
- 160 parts by weight of ground rosin and 40 parts by weight of ground rosin and reacted with maleic acid are then introduced and stirred until all solids have dissolved.
- the end product is a red-brown clear solution with a solids content of 30%.
- the fibrous batch for the sizing process carried out in this example consists of 85% by weight cellulose (50% spruce sulphite cellulose, 50% bleached pine sulphate cellulose), 10% by weight chalk (filler) and 5% by weight water-soluble starch.
- the grinding degree of the mixture is about 30 o SR.
- the sizing is carried out on a 3% fiber insert.
- the amount of sizing agent according to Example 1 is added to this batch until the effective amount of sizing agent in the batch is 2.5% by weight, based on the fiber.
- the suspension is pumped into the mixing chest and brought to a pH of 6.8 with dilute sulfuric acid (50%). A cationic retention agent is then metered in in the usual way.
- the basis weight range of the sized paper is between 110 and 120 g / m 2 .
- a wood-containing fabric batch is processed into a semi-sized printing paper.
- the pulp is first processed in a pulper, then ground and fed to a mixing chest.
- the 3.5% batch is mixed with a sizing agent according to Example 2 with constant stirring, namely 5 parts by weight of the 20% sizing agent are added to every 100 parts by weight of batch.
- the suspension is pumped into an intermediate chest and there using 10% hydrochloric acid activated. Activation is complete at pH 6.8.
- a cationic retention agent, as in Example 7, is then added to improve the fixation of the fiber and filler as well as sizing agent.
- the sized mass is processed into paper which has an ash content of 15% by weight (kaolin content) and a weight per unit area of 70 g / cm 2 .
- the Cobb (60) is 45.
- Packaging paper is produced in a waste paper processing plant that works with a very tightly closed water cycle. Dirt load and degree of hardness are therefore high (degrees of hardness greater than '100 ° d.H.)
- Sizing agent according to Example 2 is introduced into a mixing chest and mixed there well with the waste paper batch. For every 100 g of waste paper there are 2.25 wt. The activation is carried out in an intermediate chest with dilute sulfuric acid (50%) or aluminum sulfate. The pH is 6.7 or 6.8 when activated and the consistency is 3.0%; a cationic retention agent is also added.
- the fully sized wrapping paper has a basis weight of 110 or 120 g / m 2 .
- the neutral mass sizing is demonstrated with a fabric batch consisting of 50% bleached spruce sulfite pulp and 50% bleached wood pulp.
- a strongly cationic retention agent (a polyethyleneimine, namely the commercial product Polyimin SK) is added to the batch, which is located in a mixing chest, has a consistency of 4% and a pH of 6.5, in amounts of 0.2% by weight .%, based on the fiber content, entered. After thorough mixing, 2% of sizing agent (100%) is added, produced according to Example 3. Then the mass is pumped around in the machine chest and diluted with about five times the amount of water (based on volume) and to the necessary emergence consistency of about Brought 0.8%. After dewatering and drying the paper web, an excellently sized paper is available.
- the mass sizing is carried out as in Example 7, but without the addition of starch.
- With the sizing Medium according to Example 4 gives a fully sized paper with a Cobb (60) value of less than 30 with a basis weight of the paper of 70 g / m2 .
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Abstract
Mittel zur Neutralleimung von Papier, Karton, Pappen und anderen cellulosehaltigen Materialien, bestehend aus Wasser, einem mit Wasser unbegrenzt mischbaren Lösungsmittel, insbesondere Alkohol, einer basisch reagierenden Verbindung, Alkalialuminat und einer Leimungskomponente. Bei der Leimung mit diesem Mittel wird die faserhaltige Suspension vor oder nach Zugabe des Leimungsmittels mit einem Retentionsmittel vermischt, wobei das Leimungsmittel durch Neutralisation aktiviert wird.Agent for neutral sizing of paper, cardboard, cardboard and other cellulose-containing materials, consisting of water, a water-immiscible solvent, especially alcohol, a basic compound, alkali aluminate and a sizing component. When sizing with this agent, the fiber-containing suspension is mixed with a retention agent before or after the addition of the sizing agent, the sizing agent being activated by neutralization.
Description
Gegenstand der vorliegenden Erfindung ist ein Masseleimungsmittel für Papier, Karton, Pappe und andere cellulosehaltige Materialien im neutralen Bereich, sowie ein einstufiges Verfahren zur Masseleimung mit diesem Mittel.The present invention relates to a mass sizing agent for paper, cardboard, cardboard and other cellulose-containing materials in the neutral range, as well as a one-step process for mass sizing with this agent.
Ein wichtiges und seit langem eingesetztes Zusatzmittel bei der Leimung in der Papierindustrie ist bekanntlich Aluminiumsulfat, das die Ausfällung und Fixierung der Leimungskomponente, z.B. Kolophoniumharz, auf der Cellulosefaser bewirkt. Der sich aufgrund der hydrolytischen Spaltung einstellende pH-Wert liegt hierbei jedoch - in Abhängigkeit von der Aluminiumsulfatkonzentration - zwischen 4,2 und etwa 4,8, also im deutlich sauren Bereich. Das kann zu Korrosionserscheinungen an Sieben und Maschinenteilen führen. Außerdem weist so gefertigtes Papier eine geringe Alterungsbeständigkeit und verminderte mechanische Festigkeit auf. Besonders nachteilig wirkt sich der saure pH-Bereich dann aus, wenn Papiere erzeugt werden sollen, die im Strich oder in der Masse Calciumcarbonat, z.B. durch Altpapiereintrag, enthalten, da die Zersetzung des Calciumcarbonates bereits in der Nähe des Neutralpunktes (pH 6,51 wenn auch schwach, beginnt. Sowohl die Kohlensäureentwicklung als auch die in Lösung gehende Calciumionen können zu erheblichen Störungen in der Papiererzeugung führen und die Papierleimung verschlechtern.An important and long-used additive in the sizing in the paper industry is known to be aluminum sulfate, which precipitates and fixes the sizing component, e.g. Rosin resin on which cellulose fiber effects. Depending on the aluminum sulphate concentration, however, the pH that arises due to the hydrolytic cleavage is between 4.2 and approximately 4.8, ie in the clearly acidic range. This can lead to signs of corrosion on screens and machine parts. In addition, paper made in this way has low aging resistance and reduced mechanical strength. The acidic pH range is particularly disadvantageous when papers are to be produced which contain calcium carbonate, e.g. through waste paper input, since the decomposition of the calcium carbonate already begins near the neutral point (pH 6.51, albeit weakly). Both the carbon dioxide development and the calcium ions dissolving can lead to considerable disruptions in paper production and worsen paper sizing.
Es hat aus diesem Grunde nicht an Versuchen gefehlt, die in der Papierleimung bei Verwendung von Aluminiumsulfat als Flockungs- und Fixierungsmittel zu beobachtenden Nachteile und Schwierigkeiten zu beheben. Versuche, durch Anhebung des pH-Bereiches, etwa durch Verminderung der Aluminiumsulfatmenge und Ersatz des "eingesparten".Aluminiumsulfats durch ein kationisches Retentionsmittel, haben jedoch nicht den angestrebten Erfolg gezeigt. Der pH-Wert der Fasersuspension konnte damit lediglich auf Werte von ca. 5,0 angehoben werden, da Mindestmengen an Aluminiumsulfat für eine gute Leimung unabdingbar sind.For this reason, there has been no lack of attempts in paper sizing when using aluminum sulfate as a flocculating and fixing agent to remedy the disadvantages and difficulties observed. Attempts to increase the pH range, for example by reducing the amount of aluminum sulfate and replacing the "saved" . Aluminum sulfate by a cationic retention agent, however, have not shown the desired success. The pH of the fiber suspension could only be raised to around 5.0, as minimum amounts of aluminum sulfate are essential for good sizing.
Aus der US-PS 3 540 980 ist weiterhin auch bekannt geworden, daß das Aluminiumsulfat ganz oder teilweise durch wasserlösliches Aluminat ersetzt werden kann. Dabei wird die zu leimende wäßrige Fasersuspension zunächst mit so viel Aluminatlösung versetzt, bis sich ein pH-Wert von mindestens 9 einstellt. Anschließend wird der pH-Wert mittels einer anorganischen Säure oder eines sauer reagierenden Salzes, z.B. Schwefelsäure oder Aluminiumsulfat, auf einen pH-Wert nicht kleiner als 4,5 gesenkt. Das während der Neutralisation erzeugte Aluminiumhydroxid bewirkt nach Zugabe des Harzleimes die Ausflockung des Aluminiumresinates und die gebildeten Aluminiumionen fixieren das Resinat auf der Faser. Unter den angegebenen Bedingungen führt der teilweise oder vollständige Ersatz des Aluminiumsulfates durch Natriumaluminat zu der gewünschten Erhöhung des pH-Wertes, ohne daß eine Leimungsverschlechterung beobachtet wird. Aluminiumsulfat ist demnach zur Ausflockung von Harzleim und dessen Fixierung an den Cellulosefasern nicht mehr erforderlich, es kann durch Natriumaluminatzugabe und anschließende pH-Wert-Änderung substituiert werden.From US Pat. No. 3,540,980 it has also become known that all or part of the aluminum sulfate can be replaced by water-soluble aluminate. The aqueous fiber suspension to be sized is first mixed with as much aluminate solution until a pH of at least 9 is established. Then the pH is adjusted using an inorganic acid or an acidic salt, e.g. Sulfuric acid or aluminum sulfate, lowered to a pH not less than 4.5. The aluminum hydroxide produced during neutralization causes the resin resin to flocculate after the resin glue has been added, and the aluminum ions formed fix the resinate on the fiber. Under the specified conditions, the partial or complete replacement of the aluminum sulfate with sodium aluminate leads to the desired increase in the pH value, without a deterioration in the size being observed. Aluminum sulfate is therefore no longer required to flocculate resin glue and fix it to the cellulose fibers; it can be substituted by adding sodium aluminate and then changing the pH.
Ein Nachteil des vorstehenden Verfahrens wird nun darin gesehen, daß es zweistufig ist und beide Verfahrensstufen in hochverdünnten Stoffsuspensionen ablaufen müssen, Nebenreaktionen und Betriebsstörungen sind bei abgeänderten Verfahrensparametern unvermeidlich.A disadvantage of the above process is now seen in the fact that it has two stages and that both process stages have to take place in highly dilute material suspensions. Side reactions and operational disruptions are unavoidable when the process parameters are changed.
Aufgabe der vorliegenden Erfindung ist es, ein Mittel und ein Verfahren zur Neutralleimung von Papier, Karton und anderen cellulosehaltigen Materialien zu finden, bei denen die vorstehenden Schwierigkeiten und Nachteile eliminiert sind.The object of the present invention is to find a means and a method for the neutral sizing of paper, cardboard and other cellulose-containing materials, in which the above difficulties and disadvantages are eliminated.
Die Lösung der gestellten Aufgabe basiert auf der Erkenntnis, daß das bekannte Leimungsverfahren dadurch verbessert, insbesondere kostengünstiger ausgeführt werden kann, wenn die Leimung mit einem Mittel durchgeführt wird, das sowohl das Aluminat als auch den Harzleim enthält, und zwar derart, daß die Ausfällung des Leimharzes als Aluminiumresinat in dem Leimungsmittel ausgeschlossen ist. Die Ausfällung soll erst nach Einmischung des Leimungsmittels und kationischen Retentionsmittels in die Fasersuspension erfolgen.The solution to the problem is based on the knowledge that the known sizing process can thereby be improved, in particular carried out more cost-effectively, if the sizing is carried out with an agent which contains both the aluminate and the resin glue, in such a way that the precipitation of the Glue resin as aluminum resinate in the sizing agent is excluded. The precipitation should only take place after the sizing agent and the cationic retention agent have been mixed into the fiber suspension.
Gelöst wird die gestellte Aufgabe mit einem Leimungsmittel, das aus Wasser, einem mit Wasser unbegrenzt mischbaren organischen Lösungsmittel, einer basisch reagierenden Verbindung, einem Alkalialuminat und einem Leimharz besteht. Als organisches Lösungsmittel sind wasserlösliche Alkohole , beispielsweise Methanol, Äthanol und Isopropanol, einsetzbar, jedoch können auch wasserlösliche Ketone, z.B. Aceton u.a., eingesetzt werden. Das Gewichtsverhältnis Alkohol : Leimungskomponente sollte zwischen 10 : 1 und 1 : : 2 liegen, beträgt vorteilhafterweise jedoch 5 : 1 bis 0,5 : 1. Die Menge des organischen Lösungsmittels ist abhängig von Löslichkeit und Menge der organischen Leimungskomponente, die im Leimungsmittel gemäß der Erfindung vollständig gelöst sein muß.The task is solved with a sizing agent consisting of water, an organic solvent that is immiscible with water, a basic compound, an alkali aluminate and a sizing resin. Water-soluble alcohols, for example methanol, ethanol and isopropanol, can be used as the organic solvent, but water-soluble ketones, for example acetone and others, can also be used. The alcohol: sizing component weight ratio should advantageously be between 10: 1 and 1:: 2 however 5: 1 to 0.5: 1. The amount of the organic solvent depends on the solubility and amount of the organic sizing component which must be completely dissolved in the sizing agent according to the invention.
Als basisch reagierende Verbindung werden zweckmäßigerweise Natrium- oder Kaliumhydroxid eingesetzt, und zwar in solchen Mengen, daß der pH-Wert im Leimungsmittel bei etwa 12 liegt, die Ausfällung von Aluminiumhydroxid also vermieden wird. Gegebenenfalls dient die zugesetzte Alkalimenge auch zur Verseifung der Leimungskomponente, die 100%ig sein sollte, beispielsweise Verseifung einer gesättigten oder ungesättigten Fettsäure mit 12 bis 23 C-Atomen.Sodium or potassium hydroxide is expediently used as the base-reacting compound, in such amounts that the pH in the sizing agent is about 12, so that the precipitation of aluminum hydroxide is avoided. Optionally, the amount of alkali added also serves to saponify the sizing component, which should be 100%, for example saponification of a saturated or unsaturated fatty acid with 12 to 23 carbon atoms.
Die Leimungskomponente kann ein Kolophonium- oder Tallharz, eine Harzseife oder ein Trockenharzleim sein. Auch Fettsäuren mit 12 bis 23 C-Atomen sind einsetzbar. Die Kolophonium- und Tallharze können selbstverständlich auch als Addukte von Malein-oder Fumarsäure vorliegen (Diels-Alder'sche-Dien- synthese).The sizing component can be a rosin or tall resin, a resin soap or a dry resin glue. Fatty acids with 12 to 23 carbon atoms can also be used. The rosins and tall resins can of course also be present as adducts of maleic or fumaric acid (Diels-Alder'sche diene synthesis).
Die Herstellung des neuen Leimungsmittels kann in sehr einfacher Weise durch Mischung der Komponenten bei Raumtemperatur durchgeführt werden, und zwar derart, daß in eine Wasservorlage, verwendet wird enthärtetes oder härtestabilisiertes Wasser, zunächst festes Alkalialuminat oder eine wäßrige Alkalialuminatlösung eingetragen wird. Zur Vermeidung von Ausfällungen und gegebenenfalls Verseifung der Leimungskomponente wird Natriumhydroxid in fester oder gelöster Form eingetragen. Abschließend werden Alkohol und Leimungskomponente unter Rühren eingetragen. Es wird so lange gerührt, bis vollständige Lösung der Leimungskomponente eingetreten ist. Bezogen auf den gesamten Wirkstoffgehalt, liegt der Alkaligehalt des neuen Leimungsmittels zwischen 5 und 30 Gew.%, der Natriumaluminatgehalt zwischen 10 und 50 Gew.% und der Gehalt der Leimungskomponente zwischen 40 und 85 Gew.%.The preparation of the new sizing agent can be carried out in a very simple manner by mixing the components at room temperature, in such a way that softened or hardness-stabilized water, initially solid alkali aluminate or an aqueous alkali aluminate solution, is introduced into a water reservoir. To avoid precipitation and possibly saponification of the sizing component, sodium hydroxide is introduced in solid or dissolved form. Finally, alcohol and sizing component are added with stirring. It is stirred until it is complete solution of the sizing component has occurred. Based on the total active ingredient content, the alkali content of the new sizing agent is between 5 and 30% by weight, the sodium aluminate content between 10 and 50% by weight and the content of the sizing component between 40 and 85% by weight.
Die Enthärtung oder Härtestabilisierung ist zur Vermeidung von Ausfällungen erforderlich und erfolgt nach bekannten Verfahren (z.B. mit Ethylendiamintetraessigsäure und Nitrilotriessigsäure).Softening or hardness stabilization is necessary to avoid precipitation and is carried out according to known processes (e.g. with ethylenediaminetetraacetic acid and nitrilotriacetic acid).
Das neue Leimungsmittel kann unmittelbar in die zu leimende Faserstoffsuspension eingetragen werden. Nach Vermischung im Pulper oder in einer nachgeschalteten Bütte erfolgt die Aktivierung des Leimungsmittels mittels Säuren und/oder sauer reagierenden Salzen, wobei die Säure- und/oder Salzmenge so bemessen wird, daß ein pH-Wert von etwa 7 erreicht wird.The new sizing agent can be added directly to the fiber suspension to be sized. After mixing in the pulper or in a downstream chest, the sizing agent is activated by means of acids and / or acid-reacting salts, the amount of acid and / or salt being measured so that a pH of about 7 is reached.
Als Aktivator können alle organischen und anorganischen Säuren eingesetzt werden, die mit den Aluminiumionen weder unlösliche Salze noch Komplexverbindungen bilden. Bei Neutralisation auf einen pH-Wert von 6,8 - 7,2 werden mit dem neuen Leimungsmittel vorzügliche Ergebnisse erhalten. Neben Schwefelsäure und Aluminiumsulfat haben sich auch Ameisensäure und Essigsäure in den durchgeführten Versuchen bestens bewährt. Kationische Retentionsmittel verbessern die Fixierung von Faser- und Füllstoff sowie Leimungsmittel erheblich. Die Menge ist abhängig von der Art des Retentionsmittels. 0,02 bis 0,2 Gew.%, bezogen auf Stoffansatz, sollten jedoch genügen.All organic and inorganic acids which do not form insoluble salts or complex compounds with the aluminum ions can be used as activators. When neutralized to a pH of 6.8 - 7.2, excellent results are obtained with the new sizing agent. In addition to sulfuric acid and aluminum sulfate, formic acid and acetic acid have also proven their worth in the tests carried out. Cationic retention agents significantly improve the fixation of fiber and filler as well as sizing agents. The amount depends on the type of retention aid. 0.02 to 0.2% by weight, based on the amount of substance, should, however, suffice.
Nach einer anderen Verfahrensversion kann in die wäßrige Suspension von Cellulosefasern soviel Leimungsmittel eingetragen werden, bis ein pH-Wert von maximal 9 erreicht ist. Anschließend wird kationenaktives Retentionsmittel, insbesondere ein kationenaktives polymeres Retentionsmittel, eingetragen, darin homogen verteilt und das Leimungsmittel durch pH-Wert-Einstellung auf 7,2 bis 7,5 aktiviert. Zweckmäßigerweise trägt man soviel Leimungsmittel in die wäßrige Suspension ein, bis ein pH-Wert von 7,5 bis 8 bzw. 7,6 bis 8 erreicht ist.According to another version of the process, so much sizing agent can be introduced into the aqueous suspension of cellulose fibers until a pH of at most 9 is reached. Subsequently, cation-active retention agent, in particular a cation-active polymer retention agent, is introduced, homogeneously distributed therein and the sizing agent is activated by adjusting the pH to 7.2 to 7.5. Advantageously, so much sizing agent is added to the aqueous suspension until a pH of 7.5 to 8 or 7.6 to 8 is reached.
Als kationenaktive Retentionsmittel können wie bei der bereits beschriebenen Verfahrensversion Polyäthylenimin, kationische Stärkederivate, Polyacrylamid, Polymethacrylamid in die wäßrige Suspension eingetragen werden. Quartäre Stickstoffverbindungen können ebenso eingesetzt werden wie kationaktive Polymere. Mengen von 0,1 bis 0,5 Gew.%, bezogen auf den Fasergehalt der wäßrigen Suspension, reichen zur Erzielung einer guten Masseleimung aus, während das Leimungsmittel in Mengen von 0,1 bis 10 Gew.%, bezogen auf den Fasergehalt der Suspension und berechnet als Feststoffgehalt, eingesetzt wird. In manchen Fällen dürften Retentionsmittelmengen ab 0,02 Gew.%, bezogen auf den Stoffansatz, genügen.As for the cationic retention agent, polyethyleneimine, cationic starch derivatives, polyacrylamide, polymethacrylamide can be introduced into the aqueous suspension, as in the process version already described. Quaternary nitrogen compounds can be used as well as cation-active polymers. Amounts of 0.1 to 0.5% by weight, based on the fiber content of the aqueous suspension, are sufficient to achieve good mass sizing, while the sizing agent in amounts of 0.1 to 10% by weight, based on the fiber content of the suspension and calculated as the solids content. In some cases, amounts of retention agent from 0.02% by weight, based on the amount of substance, should suffice.
Die Aktivierung des Leimungsmittels kann wie bei dem vorstehenden Verfahren mittels Säuren und/oder sauer reagierenden Salzen erfolgen. Organische und anorganische Säuren, die mit den Aluminiumionen weder unlösliche Salze noch Komplexverbindungen bilden, sind geeignet. Neben Schwefelsäure und Aluminiumsulfat haben sich Ameisensäure und Essigsäure bestens bewährt.As in the above method, the sizing agent can be activated by means of acids and / or acid-reacting salts. Organic and inorganic acids that do not form insoluble salts or complex compounds with the aluminum ions are suitable. In addition to sulfuric acid and aluminum sulfate, formic acid and acetic acid have proven their worth.
Wie sich weiterhin gezeigt hat, kann man das neue Verfahren auch derart ausüben, daß man in die wäßrige Suspension von Cellulosefasern mit einem pE-Wert kleiner als 7, insbesondere 6,5 bis 6,8, zunächst ein kationaktives polymeres Retentionsmittel einträgt und dann homogen verteilt. Anschliessend trägt man soviel Leimungsmittel ein, bis ein pH-Wert größer 7 erreicht ist. Es sollte soviel Leimungsmittel in die wäßrige Suspension eingetragen werden, bis ein pH-Wert von 7,5 bis 8 erreicht ist. Der pH-Wert der Cellulosefasersuspension sollte nicht unterhalb 6 liegen.As has also been shown, the new process can also be carried out by first introducing a cationic polymeric retention agent into the aqueous suspension of cellulose fibers with a pE value of less than 7, in particular 6.5 to 6.8, and then homogeneously distributed. Subsequently, so much sizing agent is added until a pH greater than 7 is reached. Sufficient sizing agent should be added to the aqueous suspension until a pH of 7.5 to 8 is reached. The pH of the cellulose fiber suspension should not be below 6.
Als kationaktives Retentionsmittel können die vorerwähnten Mittel eingesetzt werden, und zwar in Mengen von 0,02 bis 0,5 Gew.%, bezogen auf den Fasergehalt der wäßrigen Suspension.The aforementioned agents can be used as cationic retention agents, in amounts of 0.02 to 0.5% by weight, based on the fiber content of the aqueous suspension.
Anhand der nachstehenden Beispiele soll der Erfindungsgegenstand noch näher erläutert werden.The subject of the invention is to be explained in more detail with the aid of the examples below.
In einem Rührgefäß werden 570 Gewichtsteile enthärtetes Wasser vorgelegt. In diese Vorlage rührt man 145 Gewichtsteile Natriumaluminat-Lösung mit einem Al203-Gehalt von 19 % und 25 Gewichtsteile Natriumhydroxid ein. Sobald die Komponenten gelöst sind, werden 135 Gewichtsteile Isopropanol zugegeben, anschließend 125 Gewichtsteile einer Mischfettsäure, deren Titer 19, Säurezahl 200, Verseifungszahl 200 und Jodzahl 105 beträgt. Es wird so lange gerührt, bis eine klare Lösung vorliegt. Der Wirkstoffgehalt des Neutralleimungsmittels beträgt 20 Gew.%.570 parts by weight of softened water are placed in a stirred vessel. 145 parts by weight of sodium aluminate solution with an Al 2 O 3 content of 19% and 25 parts by weight of sodium hydroxide are stirred into this template. As soon as the components are dissolved, 135 parts by weight of isopropanol are added, then 125 parts by weight of a mixed fatty acid, whose titer is 19, acid number 200, saponification number 200 and iodine number 105. The mixture is stirred until a clear solution is obtained. The active substance content of the neutral sizing agent is 20% by weight.
Wie im Beispiel 1 werden in einem Rührgefäß 645 Gewichtsteile Wasser vorgelegt. Nach Eintrag von 50 Gewichtsteilen 50%iger Natriumhydroxidlösung und 45 Gewichtsteilen festen Natriumaluminat in Pulverform wird bis zur vollständigen Lösung gerührt. Dann läßt man 135 Gewichtsteile Isopropanol zulaufen und verteilt 125 Gewichtsteile verstärkten Pulverharzleimes darin. Nach vollständiger Auflösung des Pulverleimes liegt eine schwach gelb gefärbte Lösung vor, der zur Stabilisierung 1 Gewichtsteil Sorbitol beigemischt wird. Der Wirkstoffgehalt des Leimungsmittels beträgt etwa 20 Gew.%.As in Example 1, 645 parts by weight of water are placed in a stirred vessel. After 50 parts by weight of 50% sodium hydroxide solution and 45 parts by weight of solid sodium aluminate in powder form have been introduced, the mixture is stirred until completely dissolved. Then 135 parts by weight of isopropanol are run in and 125 parts by weight of reinforced powder resin glue are distributed therein. After the powder glue has completely dissolved, a slightly yellow colored solution is present, to which 1 part by weight of sorbitol is added for stabilization. The active ingredient content of the sizing agent is about 20% by weight.
In einem Rührgefäß werden 630 Gewichtsteile enthärtetes Wasser vorgelegt. Dann werden in das Wasser 100 Gewichtsteile Natriumaluminatlösung mit einem Gehalt von 19% Al203 und 25 Gewichtsteile festes Natriumhydroxid eingetragen. Nachdem sich die Komponenten gelöst und verteilt haben, erfolgt die Zugabe von 160 Gewichtsteilen Isopropanol. Anschließend wird ein Gemisch aus 100 Gewichtsteilen Balsamharz und 10 Gewichtsteilen eines mit Maleinsäure umgesetzten Kolophoniumharzes in das Rührgefäß eingetragen. Es wird solange weitergerührt, bis sämtliche Komponenten in Lösung gegangen sind.630 parts by weight of softened water are placed in a stirred vessel. Then 100 parts by weight of sodium aluminate solution containing 19% Al203 and 25 parts by weight of solid sodium hydroxide are introduced into the water. After the components have dissolved and been distributed, 160 parts by weight of isopropanol are added. A mixture of 100 parts by weight of balsam resin and 10 parts by weight of a rosin resin reacted with maleic acid is then introduced into the stirred vessel. Stirring continues until all components have gone into solution.
In einem Rührgefäß, in welchem sich 75 Gewichtsteile Ethanol befinden, werden 50 Gewichtsteile zerkleinertes Kolophoniumharz und 5 Gewichtsteile mit Maleinsäure umgesetztes Kolophoniumharz solange gerührt, bis sich die Festbestandteile völlständig gelöst haben. Dann trägt man unter Rühren 50 Gewichtsteile Natriumaluminatlösung mit einem Al2O3-Gehalt von 19 Gew.% und 25 Gewichtsteile einer 50%igen Natri-In a stirred vessel in which there are 75 parts by weight of ethanol, 50 parts by weight of ground rosin and 5 parts by weight of rosin reacted with maleic acid are stirred until the solid components have completely dissolved. Then 50 parts by weight of sodium aluminate solution with an Al 2 O 3 content of 19% by weight and 25 parts by weight of a 50% sodium
umhydroxidlösung ein. Zuletzt gibt man noch 101 Gewichtsteile enthärtetes Wasser zu. Man erhält eine rotbraune Lösung mit einem Feststoffgehalt von 27,4 %.hydroxide solution. Finally, 101 parts by weight of softened water are added. A red-brown solution with a solids content of 27.4% is obtained.
365 Gewichtsteile Brauchwasser (Stadtwasser) mit einem Härtegrad von 25°d.E. werden in ein Rührgefäß gepumpt und mit 1 Gewichtsanteil Ethylendiamintetraessigsäure bzw. Nitrilotriessigsäure versetzt. Unter Rühren trägt man dann 200 Gewichtsteile einer Natriumaluminatlösung mit einem Al2O3-Gehalt von 19 Gew.%, 35 Gewichtsteile Natriumhydroxid in Schuppenform und 200.Gewichtsteile Ethanol ein. Man rührt solange, bis sich eine klare Lösung gebildet hat. 160 Gewichtsteile gemahlenes Kolophonium und 40 Gewichtsteile gemahlenes und mit Maleinsäure umgesetztes Kolophoniumharz werden anschließend eingetragen und solange gerührt, bis alle Feststoffe gelöst sind. Als Endprodukt liegt eine rotbraune klare Lösung mit einem Feststoffgehalt von 30 % vor.365 parts by weight of process water (city water) with a hardness of 25 ° dE are pumped into a stirred vessel and mixed with 1 part by weight of ethylenediaminetetraacetic acid or nitrilotriacetic acid. 200 parts by weight of a sodium aluminate solution with an Al 2 O 3 content of 19% by weight, 35 parts by weight of sodium hydroxide in flake form and 200 parts by weight of ethanol are then introduced with stirring. Stir until a clear solution has formed. 160 parts by weight of ground rosin and 40 parts by weight of ground rosin and reacted with maleic acid are then introduced and stirred until all solids have dissolved. The end product is a red-brown clear solution with a solids content of 30%.
In ein Rührgefäß werden 365 Gewichtsteile härtestabilisiertes Leitungswasser eingetragen und mit 200 Gewichtsteilen Natriumaluminatlösung (19% Al2O3-Gehalt) versetzt. Dann trägt man 35 Gewichtsteile Natriumhydroxid in Schuppenform ein. In die Lösung wird ein Alkoholgemisch, bestehend aus 160 Gewichtsteilen Ethanol und 40 Gewichtsteilen Methanol, eingebracht und solange gerührt, bis eine klare Lösung entstanden ist. Dann erfolgt die Zugabe von 200 Gewichtsteilen gemahlenem Kolophonium mit einem Maleinierungsgrad von etwa 10 %. Das Endprodukt ist eine rotbraune durchsichtige Flüssigkeit mit einem Feststoffgehalt von 30 %.365 parts by weight of hard-stabilized tap water are introduced into a stirred vessel and 200 parts by weight of sodium aluminate solution (19% Al 2 O 3 content) are added. Then you enter 35 parts by weight of sodium hydroxide in flake form. An alcohol mixture consisting of 160 parts by weight of ethanol and 40 parts by weight of methanol is introduced into the solution and stirred until a clear solution has formed. Then 200 parts by weight of ground rosin are added with a degree of maleinization of about 10%. The end product is a red-brown, transparent liquid with a solids content of 30%.
Der Faserstoffansatz für den in diesem Beispiel vorgenommenen Leimungsvorgang besteht aus 85 Gew.% Zellstoff (50% Fichtesulfitzellstoff, 50% gebleichter Kiefernsulfatzellstoff), 10 Gew.% Kreide (Füllstoff) und 5 Gew.% wasserlöslicher Stärke. Der Mahlgrad der Mischung liegt bei etwa 30oSR. Die Leimung wird an einem 3 %igen Faserstoffeinsatz vorgenommen. Zu diesem Ansatz gibt man so viel Leimungsmittel nach Beispiel 1, bis die wirksame Leimungsmittelmenge im Ansatz 2,5 Gew.%, bezogen auf den Faserstoff, beträgt. Nach Vermischung wird die Suspension in die Mischbütte gepumpt und mit verdünnter Schwefelsäure (50 %ig) auf einen pH-Wert von 6,8 gebracht. Sodann wird in üblicher Weise ein kationisches Retentionsmittel zudosiert.The fibrous batch for the sizing process carried out in this example consists of 85% by weight cellulose (50% spruce sulphite cellulose, 50% bleached pine sulphate cellulose), 10% by weight chalk (filler) and 5% by weight water-soluble starch. The grinding degree of the mixture is about 30 o SR. The sizing is carried out on a 3% fiber insert. The amount of sizing agent according to Example 1 is added to this batch until the effective amount of sizing agent in the batch is 2.5% by weight, based on the fiber. After mixing, the suspension is pumped into the mixing chest and brought to a pH of 6.8 with dilute sulfuric acid (50%). A cationic retention agent is then metered in in the usual way.
Nach Blattbildung und Trocknung erhält man ein vollgeleimtes Papier mit einer Tintenschwimmdauer von über 8 Minuten und einen Cobb (60)-Wert von kleiner als 30. Der Flächengewichtsbereich des geleimten Papieres liegt zwischen 110 und 120 g/m2.After sheet formation and drying, a fully sized paper with an ink floating time of over 8 minutes and a Cobb (60) value of less than 30 are obtained. The basis weight range of the sized paper is between 110 and 120 g / m 2 .
Ein holzhaltiger Stoffansatz wird zu einem halbgeleimten Druckpapier verarbeitet. Zu diesem Zweck wird der Zellstoff zunächst in einem Pulper aufbereitet, dann gemahlen und einer Mischbütte zugeführt. In der Mischbütte wird der 3,5 %ige Stoffansatz unter ständigem Rühren mit einem Leimungsmittel nach Beispiel 2 versetzt, und zwar gibt man auf jeweils 100 Gewichtsteile Stoffansatz 5 Gewichtsteile des 20 %igen Leimungsmittels. Nach guter Durchmischung wird die Suspension in eine Zwischenbütte gepumpt und dort mittels 10 %iger Salzsäure aktiviert. Die Aktivierung ist bei pH 6,8 beendet. Zur Verbesserung der Fixierung von Faser- und Füllstoff sowie Leimungsmittel wird dann noch ein kationisches Retentionsmittel, wie in Beispiel 7, zugesetzt.A wood-containing fabric batch is processed into a semi-sized printing paper. For this purpose, the pulp is first processed in a pulper, then ground and fed to a mixing chest. In the mixing chest, the 3.5% batch is mixed with a sizing agent according to Example 2 with constant stirring, namely 5 parts by weight of the 20% sizing agent are added to every 100 parts by weight of batch. After thorough mixing, the suspension is pumped into an intermediate chest and there using 10% hydrochloric acid activated. Activation is complete at pH 6.8. A cationic retention agent, as in Example 7, is then added to improve the fixation of the fiber and filler as well as sizing agent.
Die geleimte Masse wird zu Papier verarbeitet, das einen Aschegehalt von 15 Gew.% (Kaolingehalt) und ein Flächengewicht von 70 g/cm2 aufweist. Der Cobb(60)-Wert beträgt 45.The sized mass is processed into paper which has an ash content of 15% by weight (kaolin content) and a weight per unit area of 70 g / cm 2 . The Cobb (60) is 45.
In einem Altpapier verarbeitenden Betrieb, der mit sehr eng geschlossenen Wasserkreislauf arbeitet, wird Verpackungspapier hergestellt. Schmutzfracht und Härtegrad liegen demnach hoch (Härtegrade größer '100°d.H. )Packaging paper is produced in a waste paper processing plant that works with a very tightly closed water cycle. Dirt load and degree of hardness are therefore high (degrees of hardness greater than '100 ° d.H.)
In eine Mischbütte wird Leimungsmittel nach Beispiel 2 eingetragen und dort mit dem Altpapieransatz gut vermischt. Auf 100 g Altpapier kommen jeweils 2,25 Gew.% Wirkstoff des Leimungsmittels. Die Aktivierung wird in einer Zwischenbütte mit verdünnter Schwefelsäure (50 %ig) bzw. Aluminiumsulfat durchgeführt. Der pH-Wert beträgt bei der Aktivierung 6,7 bzw. 6,8 und die Stoffdichte 3,0 %; auch wird ein kationisches Retentionsmittel zugegeben. Das vollgeleimte Packpapier weist ein Flächengewicht von 110 bzw. 120 g/m2 auf.Sizing agent according to Example 2 is introduced into a mixing chest and mixed there well with the waste paper batch. For every 100 g of waste paper there are 2.25 wt. The activation is carried out in an intermediate chest with dilute sulfuric acid (50%) or aluminum sulfate. The pH is 6.7 or 6.8 when activated and the consistency is 3.0%; a cationic retention agent is also added. The fully sized wrapping paper has a basis weight of 110 or 120 g / m 2 .
In einer Mischbütte mit einem Inhalt von 25 m3 Fassungsvermögen liegt vor eine Stoffsuspension von 4 % Stoffdichte. Es handelt sich in diesem Fall um einen aufgelösten Faserstoff, bestehend aus 55 % Mischpapierabfällen, 25 % Wellpappeabfällen und 20 % Kartonabfällen. Der pH-Wert der Suspension liegt bei 6,9. In diese trägt man nun 125 kg des 20 %igen Neutralleimungsmittels nach Beispiel 3 ein. Damit steigt der pH-Wert auf 8,35 an. Nachdem der Leimungsstoff sich gut mit der Faserstoffsuspension vermischt hat, werden 1,5 kg Polyäthylenimin zudosiert und gleichmäßig in der Stoffmasse verteilt. der pH-Wert der Suspension ändert sich dabei nicht. Nun läßt man den Aktivator (verdünnte Schwefelsäure) langsam in die Bütte zulaufen, bis sich ein pH-Wert im Bereich von 7,3 eingestellt hat. Die Weiterverarbeitung auf der Maschine erfolgt in üblicher Weise, und man erhält am Ende eine Pappe, die einen Cobb-Wert (60 Sek.) zwischen 50 und 75 aufweist.In a mixing chest with a capacity of 25 m 3 there is a stock suspension of 4% consistency. In this case, it is a dissolved fibrous material consisting of 55% mixed paper waste, 25% corrugated cardboard waste and 20% cardboard waste. The pH of the suspension is 6.9. In this you now carry 125 kg of 20% Neutral sizing agent according to Example 3. This increases the pH to 8.35. After the sizing material has mixed well with the fiber suspension, 1.5 kg of polyethyleneimine are metered in and distributed evenly in the material. the pH of the suspension does not change. Now the activator (dilute sulfuric acid) is slowly run into the chest until a pH in the range of 7.3 has been established. Further processing on the machine is carried out in the customary manner, and at the end a cardboard is obtained which has a Cobb value (60 seconds) between 50 and 75.
Die neutrale Masseleimung wird mit einem Stoffansatz vorgeführt, der aus 50 % gebleichtem Fichtesulfitzellstoff und 50 % angebleichtem Holzschliff besteht. Zu dem Stoffansatz, der sich in einer Mischbütte befindet, eine Stoffdichte von 4 % und einen pH-Wert von 6,5 aufweist, wird ein stark kationisches Retentionsmittel (ein Polyäthylenimin, und zwar das Handelsprodukt Polyimin SK) in Mengen von 0,2 Gew.%, bezogen auf den Fasergehalt, eingetragen. Nach guter Durchmischung erfolgt die Zugabe von 2 % Leimungsmittel (100 %ig),hergestellt nach Beispiel 3. Anschließend wird die Masse in der Maschinenbütte umgepumpt und dabei mit etwa der fünffachen Wassermenge (bez.auf Volumen) verdünnt und auf die notwendige Auflaufkonsistenz von etwa 0,8 % gebracht. Nach Entwässerung und Trocknung der Papierbahn liegt ein vorzüglich geleimtes Papier vor.The neutral mass sizing is demonstrated with a fabric batch consisting of 50% bleached spruce sulfite pulp and 50% bleached wood pulp. A strongly cationic retention agent (a polyethyleneimine, namely the commercial product Polyimin SK) is added to the batch, which is located in a mixing chest, has a consistency of 4% and a pH of 6.5, in amounts of 0.2% by weight .%, based on the fiber content, entered. After thorough mixing, 2% of sizing agent (100%) is added, produced according to Example 3. Then the mass is pumped around in the machine chest and diluted with about five times the amount of water (based on volume) and to the necessary emergence consistency of about Brought 0.8%. After dewatering and drying the paper web, an excellently sized paper is available.
Die Masseleimung wird wie im Beispiel 7 durchgeführt, jedoch ohne Zusatz von Stärke. Mit dem Leimungsmittel nach Beispiel 4 erhält man ein vollgeleimtes Papier mit einem Cobb(60)-Wert von kleiner als 30 bei einem Flächengewicht des Papieres von 70 g/m2.The mass sizing is carried out as in Example 7, but without the addition of starch. With the sizing Medium according to Example 4 gives a fully sized paper with a Cobb (60) value of less than 30 with a basis weight of the paper of 70 g / m2 .
Claims (30)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT83112302T ATE26005T1 (en) | 1982-12-08 | 1983-12-07 | MEANS AND METHOD OF NEUTRAL SIZING. |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3245390 | 1982-12-08 | ||
| DE19823245390 DE3245390C1 (en) | 1982-12-08 | 1982-12-08 | Agent and process for neutral sizing |
| DE3338088 | 1983-10-20 | ||
| DE3338087 | 1983-10-20 | ||
| DE19833338088 DE3338088C1 (en) | 1982-12-08 | 1983-10-20 | Process for neutral sizing of paper, cardboard, paperboard and other cellulose-containing materials |
| DE19833338087 DE3338087C1 (en) | 1982-12-08 | 1983-10-20 | Process for neutral sizing of paper, cardboard, paperboard and other cellulose-containing materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0112525A1 true EP0112525A1 (en) | 1984-07-04 |
| EP0112525B1 EP0112525B1 (en) | 1987-03-18 |
Family
ID=27190556
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83112302A Expired EP0112525B1 (en) | 1982-12-08 | 1983-12-07 | Agent and process for neutral sizing |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4591412A (en) |
| EP (1) | EP0112525B1 (en) |
| DE (1) | DE3370360D1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003000992A2 (en) * | 2001-06-22 | 2003-01-03 | Universidade Federal de Viçosa | Paper sizing agent |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4842691A (en) * | 1986-03-19 | 1989-06-27 | Arakawa Chemical Industries, Ltd. | Sizing agents in neutral range and sizing methods using the same |
| US4699663A (en) * | 1986-06-24 | 1987-10-13 | Reichhold Chemicals, Inc. | Sizing composition and method |
| SE8700058L (en) * | 1987-01-09 | 1988-07-10 | Skogsindustriens Tekniska Fors | PAPER |
| WO1989012035A1 (en) | 1988-06-06 | 1989-12-14 | The Dow Chemical Company | Manufacture of non-whiteware ceramic articles |
| EP0560265B1 (en) * | 1992-03-09 | 1998-01-21 | Canon Kabushiki Kaisha | Recycled paper for electrophotography and image forming method making use of the same |
| US5411639A (en) * | 1993-10-15 | 1995-05-02 | Westvaco Corporation | Process for enhancing sizing efficiency in filled papers |
| ATE217659T1 (en) | 1994-12-28 | 2002-06-15 | Hercules Inc | METHOD FOR SIZING PAPER USING A COLOPHONYUM/HYDROCARBON RESIN SIZING AGENT |
| US6033526A (en) | 1994-12-28 | 2000-03-07 | Hercules Incorporated | Rosin sizing at neutral to alkaline pH |
| EP0808944A3 (en) * | 1996-05-21 | 1998-04-15 | BECKER GROUP EUROPE GmbH | Production of thermoformable articles |
| US6572736B2 (en) | 2000-10-10 | 2003-06-03 | Atlas Roofing Corporation | Non-woven web made with untreated clarifier sludge |
| US7758719B2 (en) * | 2005-12-16 | 2010-07-20 | Fiberight Management Llc | Wet pulping system and method for producing cellulosic insulation with low ash content |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1929205A (en) * | 1932-04-04 | 1933-10-03 | Nat Aluminate Corp | Paper making |
| US2680073A (en) * | 1951-01-10 | 1954-06-01 | Allied Chem & Dye Corp | Method of sizing paper |
| US2749316A (en) * | 1951-08-17 | 1956-06-05 | Ici Ltd | Stabilised sodium aluminate |
| DE1028077B (en) * | 1952-05-27 | 1958-04-17 | Gen Electric | Stable aqueous solutions of siliconates for waterproofing all kinds of solid objects |
| DE1036429B (en) * | 1957-02-04 | 1958-08-14 | Schneider G M B H A | Process for producing a dry glue, especially for paper sizing |
| FR1279460A (en) * | 1960-11-10 | 1961-12-22 | Centre Nat Rech Scient | Improvements in the manufacture of paper and cardboard |
| DE1136044B (en) * | 1961-12-13 | 1962-09-06 | Chem Fab Bruehl Gottfried Kent | Process for the production of thin liquid resin glue |
| US3433658A (en) * | 1964-11-24 | 1969-03-18 | American Cyanamid Co | Warm water-dilutable paste rosin size and process for the manufacture thereof |
| US3540980A (en) * | 1968-10-30 | 1970-11-17 | Int Paper Co | Process of rosin sizing paper |
| US3577402A (en) * | 1968-07-24 | 1971-05-04 | American Cyanamid Co | Paste rosin size containing viscosity depressant |
| DE2031293A1 (en) * | 1970-06-24 | 1971-12-30 | Hercules Inc., Wilmington, Del. (V.StA.) | Method for gluing paper |
| DE2321680A1 (en) * | 1973-04-28 | 1974-11-21 | Giulini Gmbh Geb | Hydrophobic compsn. for paper and cardboard - contg. saponified fatty acid, polyelectrolyte, esp. cellulose deriv., and alkali aluminate |
| DE2924947A1 (en) * | 1979-06-21 | 1981-01-22 | Giulini Chemie | Neutral surface size paper, board and other cellulosic material - prepd. by mixing starch soln. contg. aluminium sulphate with alkaline size |
| EP0058818A1 (en) * | 1981-02-24 | 1982-09-01 | Hüls Troisdorf Aktiengesellschaft | Impregnation agent for cellulosic material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB335902A (en) * | 1929-07-01 | 1930-10-01 | Bruno Wieger | Improvements in and relating to the sizing of paper and to compositions therefor |
| GB1412254A (en) * | 1972-01-14 | 1975-10-29 | English Clays Lovering Pochin | Sizing of cellulosic fibres |
| JPS53103003A (en) * | 1977-02-18 | 1978-09-07 | Rei Tech Inc | Paper making method |
| DD144577A1 (en) * | 1979-06-28 | 1980-10-22 | Klaus Granich | PROCESS FOR PREPARING AN EFFECTANT FOR PAPER, CARTON AND PAPER |
-
1983
- 1983-12-07 EP EP83112302A patent/EP0112525B1/en not_active Expired
- 1983-12-07 DE DE8383112302T patent/DE3370360D1/en not_active Expired
- 1983-12-08 US US06/559,961 patent/US4591412A/en not_active Expired - Fee Related
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1929205A (en) * | 1932-04-04 | 1933-10-03 | Nat Aluminate Corp | Paper making |
| US2680073A (en) * | 1951-01-10 | 1954-06-01 | Allied Chem & Dye Corp | Method of sizing paper |
| US2749316A (en) * | 1951-08-17 | 1956-06-05 | Ici Ltd | Stabilised sodium aluminate |
| DE1028077B (en) * | 1952-05-27 | 1958-04-17 | Gen Electric | Stable aqueous solutions of siliconates for waterproofing all kinds of solid objects |
| DE1036429B (en) * | 1957-02-04 | 1958-08-14 | Schneider G M B H A | Process for producing a dry glue, especially for paper sizing |
| FR1279460A (en) * | 1960-11-10 | 1961-12-22 | Centre Nat Rech Scient | Improvements in the manufacture of paper and cardboard |
| DE1136044B (en) * | 1961-12-13 | 1962-09-06 | Chem Fab Bruehl Gottfried Kent | Process for the production of thin liquid resin glue |
| US3433658A (en) * | 1964-11-24 | 1969-03-18 | American Cyanamid Co | Warm water-dilutable paste rosin size and process for the manufacture thereof |
| US3577402A (en) * | 1968-07-24 | 1971-05-04 | American Cyanamid Co | Paste rosin size containing viscosity depressant |
| US3540980A (en) * | 1968-10-30 | 1970-11-17 | Int Paper Co | Process of rosin sizing paper |
| DE2031293A1 (en) * | 1970-06-24 | 1971-12-30 | Hercules Inc., Wilmington, Del. (V.StA.) | Method for gluing paper |
| DE2321680A1 (en) * | 1973-04-28 | 1974-11-21 | Giulini Gmbh Geb | Hydrophobic compsn. for paper and cardboard - contg. saponified fatty acid, polyelectrolyte, esp. cellulose deriv., and alkali aluminate |
| DE2924947A1 (en) * | 1979-06-21 | 1981-01-22 | Giulini Chemie | Neutral surface size paper, board and other cellulosic material - prepd. by mixing starch soln. contg. aluminium sulphate with alkaline size |
| EP0058818A1 (en) * | 1981-02-24 | 1982-09-01 | Hüls Troisdorf Aktiengesellschaft | Impregnation agent for cellulosic material |
Non-Patent Citations (1)
| Title |
|---|
| TAPPI JOURNAL, Band 65, Nr. 11, November 1982, Seiten 105-109, Atlanta, GA., US * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003000992A2 (en) * | 2001-06-22 | 2003-01-03 | Universidade Federal de Viçosa | Paper sizing agent |
| WO2003000992A3 (en) * | 2001-06-22 | 2003-02-20 | Univ Fed Vicosa | Paper sizing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0112525B1 (en) | 1987-03-18 |
| US4591412A (en) | 1986-05-27 |
| DE3370360D1 (en) | 1987-04-23 |
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