EP0013969B1 - Verfahren zur Herstellung von Papier mit hoher Trockenfestigkeit und niedriger Nassfestigkeit - Google Patents
Verfahren zur Herstellung von Papier mit hoher Trockenfestigkeit und niedriger Nassfestigkeit Download PDFInfo
- Publication number
- EP0013969B1 EP0013969B1 EP80100302A EP80100302A EP0013969B1 EP 0013969 B1 EP0013969 B1 EP 0013969B1 EP 80100302 A EP80100302 A EP 80100302A EP 80100302 A EP80100302 A EP 80100302A EP 0013969 B1 EP0013969 B1 EP 0013969B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- paper
- weight
- strength
- acrylic acid
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 33
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 19
- -1 alkaline earth metal salt Chemical class 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 13
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 9
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims abstract description 9
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002148 esters Chemical class 0.000 claims abstract description 7
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 6
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 7
- 159000000003 magnesium salts Chemical class 0.000 claims description 6
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 description 15
- 229920001519 homopolymer Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001447 alkali salts Chemical class 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 229940037003 alum Drugs 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 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 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- XXQBEVHPUKOQEO-UHFFFAOYSA-N potassium superoxide Chemical compound [K+].[K+].[O-][O-] XXQBEVHPUKOQEO-UHFFFAOYSA-N 0.000 description 2
- 238000012673 precipitation polymerization Methods 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 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
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- VFNGKCDDZUSWLR-UHFFFAOYSA-L disulfate(2-) Chemical compound [O-]S(=O)(=O)OS([O-])(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-L 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000012688 inverse emulsion polymerization Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 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
- D21H17/20—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
- Y10T428/31906—Ester, halide or nitrile of addition polymer
Definitions
- FR-A-931 044 it is known to improve the mechanical strength of paper by impregnating paper with an aqueous solution of a polymer containing acid groups.
- the free polycarboxylic acids e.g. Polymethacrylic acid or the alkali or ammonium salts of the polycarboxylic acids.
- the invention has for its object to further improve the mechanical properties of paper, in particular to provide a method for producing paper with high dry strength and low wet strength.
- the viscosity of the polymer salts in a 2 % strength aqueous solution is 5 to 100 mPas (Brookfield viscometer, 20 revolutions / minute) at a temperature of 20 ° C.
- the homopolymers and copolymers are prepared by known processes by polymerizing the monomers, cf. US-A 2 819 189 and US-A 2 999 038.
- the monomers or mixtures thereof are polymerized continuously or discontinuously with the aid of radical polymerization initiators, preferably in water. If the alkali metal or alkaline earth metal salts of acrylic acid or methacrylic acid are already used in the polymerization of the monomers, the copolymer salt solutions to be used according to the invention are obtained directly.
- Acrylic acid and / or methacrylic acid can be polymerized with the corresponding amides or nitriles in water in the manner of a precipitation polymerization.
- the resulting copolymers can be neutralized directly with alkali or alkaline earth metal hydroxides.
- the homopolymers or copolymers obtained in the precipitation polymerization in water can be isolated, dried and mixed with one or more dry, powdered alkaline earth metal hydroxides or oxides. These powdery mixtures can then be easily dissolved in water to give a clear solution.
- the calcium and magnesium salts of the copolymers mentioned above are of particular importance.
- the polymers contain 91 to 100, preferably 95 to 100% by weight of acrylic acid and / or methacrylic acid and 0 to 9, preferably up to 5% by weight of acrylonitrile, methacrylonitrile, acrylamide or methacrylamide, vinyl acetate, maleic anhydride, diisobutene and optionally acrylic ester or methacrylic acid ester.
- the esters are preferably derived from monohydric, primary alcohols having 1 to 4 carbon atoms.
- the calcium and magnesium salts of homopolymers of acrylic acid and methacrylic acid are of particular importance for the process according to the invention.
- Calcium and magnesium salts and, if appropriate, mixtures of alkaline earth and alkali salts of homopolymers of acrylic acid or methacrylic acid and copolymers of acrylic acid and acrylamide, acrylic acid and acrylonitrile, acrylic acid, methacrylic acid and acrylamide, and copolymers of acrylic acid, acrylamide and methacrylamide are preferably used. At least 30% of the carboxyl groups in the polymers are neutralized with alkaline earth metal ions. The degree of neutralization is generally 70 to 100%.
- the mixing ratio of the alkaline earth to alkali salts is preferably 30 to 50 to 70 to 50.
- a 2% aqueous solution of the alkali metal or alkaline earth metal salts to be used according to the invention has a viscosity (Brookfield 20 / min) of 5 to 100, preferably 10 to, at a temperature of 20 ° C. 30 mPas.
- the pH of the copolymer salt solution is in the range between 4.0 and 10.0.
- the water-soluble alkaline earth metal salts of the polymers in question are applied to the paper in the form of a 1 to 10% strength aqueous solution.
- the paper can be impregnated with the alkaline earth metal salt solution of the copolymers, e.g. in a size press, or spray a solution of the copolymer salt onto the paper.
- the absorption of preparation solution depends on the absorbency of the paper used. In relation to the solids, to achieve a good increase in dry strength of the paper, it is sufficient to impregnate the paper with 1 to 4% by weight of the alkaline earth metal salts of the polymers described.
- the increase in the strength of the paper is immediately after drying the paper under usual conditions, e.g. Temperatures of 80 to 110 ° C, obtained. It is not necessary to age the impregnated paper. Also of particular advantage is the fact that it is possible to use the alkaline earth metal salts of the polymers to be used according to the invention together with the starch solutions frequently used in practice, the preparation solutions being 2 to 10% by weight, preferably 2 to 6% by weight. Starch and 1 to 3% by weight of the alkaline earth metal salts of polymers to be used according to the invention.
- All known paper qualities e.g. Writing, printing and packaging papers are impregnated with the products to be used according to the invention.
- the papers can be made from a variety of fiber materials such as sulfite or sulfate pulp (bleached or unbleached), wood pulp or waste paper.
- the use of the alkaline earth metal salts of polymers of acrylic acid and / or methacrylic acid and the comonomers mentioned under b) as surface application agents for paper leads to an unexpected increase in the dry strength of the paper without the wet strength of the paper being appreciably increased.
- the dry strength properties of the paper which are noticeably improved, are e.g. the tear length, burst pressure, pick resistance, tear resistance and the CMT value.
- the invention is illustrated by the following examples.
- the parts given in the examples are parts by weight, the percentages relate to the weight.
- the viscosities stated were measured at a temperature of 20 ° C. in a Brookfield viscometer at 20 revolutions / minute.
- the dry tear length was determined in accordance with DIN 53 112, sheet 1 and the wet tear length in accordance with DIN 53 112, sheet 2.
- the pick resistance of the paper was determined according to the Dennison wax test.
- a homopolymer of acrylic acid which was obtained by polymerizing acrylic acid in aqueous solution using potassium peroxide disulfate as a catalyst, is neutralized with magnesium hydroxide.
- a 2% strength aqueous solution of the magnesium salt of the homopolymer is prepared which has a pH of 5.0.
- a wood-free, unsized offset paper produced on a paper machine with a freeness of 25 ° SR, 14% ash (kaolin) and 2% alum and a weight of 80 g / m 2 is mixed with a 2% aqueous solution of the above-mentioned magnesium salt of the homopolymer impregnated with acrylic acid and then dried at a temperature of 100 ° C.
- Table 1 shows the viscosity of the preparation solution, the amount of pure polymer salt applied to the paper, based on the weight of the paper, and some properties of the paper obtained.
- Example 1 The homopolymer of acrylic acid described in Example 1 is neutralized with ammonia instead of magnesium oxide and used as a 2% solution at a pH of 5.0 as an impregnating agent for the offset paper specified in Example 1 (Table 1).
- Example 1 The homopolymer of acrylic acid described in Example 1 is used in non-neutralized form as a 2% aqueous solution at a pH of 2.5 as an impregnating agent for the offset paper specified in Example 1.
- Table 1 shows the properties of the paper obtained together with those properties of the paper which were measured after treating the paper with water and drying (comparative example 1c).
- a 2% solution of this Copolymers are applied to a wood-free, unsized offset paper with 1% alum, a freeness of 25 ° SR, 10% ash (kaolin) and a weight of 80 g / m 2 .
- the impregnated paper is dried at a temperature of 100 ° C. Further information on the preparation solution and the properties of the impregnated paper can be found in Table 2.
- the copolymer of 95% acrylic acid and 5% acrylamide described in Example 2 is neutralized with ammonia instead of calcium hydroxide and used as a 2% aqueous solution at a pH of 6.0 as an impregnating agent for the offset paper specified in Example 2 (Table 2 ).
- Example 2 The copolymer of 95% acrylic acid and 5% acrylamide specified in Example 2 is used without neutralization in the form of a 2% strength aqueous solution which has a pH of 2.5 for impregnating paper, which is described in Example 2.
- the paper was dried at the same temperature as in Example 2.
- the results are shown in Table 2.
- Table 2 For comparison, the values are also given in Table 2, which are obtained when the paper described in Example 2 is impregnated with water and dried at 100.degree.
- the examples and comparative examples show that the polymer salts to be used according to the invention compared to the corresponding ammonium salts or the polyacids lead to a further increase in the dry strength of the paper without undesirably increasing the wet strength of the paper.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Medicinal Preparation (AREA)
- Diaphragms For Electromechanical Transducers (AREA)
- Developing Agents For Electrophotography (AREA)
- Control Of Motors That Do Not Use Commutators (AREA)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT80100302T ATE1591T1 (de) | 1979-01-27 | 1980-01-22 | Verfahren zur herstellung von papier mit hoher trockenfestigkeit und niedriger nassfestigkeit. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2903218 | 1979-01-27 | ||
DE19792903218 DE2903218A1 (de) | 1979-01-27 | 1979-01-27 | Verfahren zur herstellung von papier mit hoher trockenfestigkeit und niedriger nassfestigkeit |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0013969A1 EP0013969A1 (de) | 1980-08-06 |
EP0013969B1 true EP0013969B1 (de) | 1982-09-22 |
Family
ID=6061575
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP80100302A Expired EP0013969B1 (de) | 1979-01-27 | 1980-01-22 | Verfahren zur Herstellung von Papier mit hoher Trockenfestigkeit und niedriger Nassfestigkeit |
Country Status (10)
Country | Link |
---|---|
US (1) | US4294873A (es) |
EP (1) | EP0013969B1 (es) |
JP (1) | JPS55103393A (es) |
AT (1) | ATE1591T1 (es) |
AU (1) | AU553980B2 (es) |
CA (1) | CA1140819A (es) |
DE (2) | DE2903218A1 (es) |
ES (1) | ES8105058A2 (es) |
FI (1) | FI64964C (es) |
NO (1) | NO157186C (es) |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3506832A1 (de) * | 1985-02-27 | 1986-08-28 | Basf Ag, 6700 Ludwigshafen | Verfahren zur herstellung von papier mit hoher trockenfestigkeit |
US5281306A (en) * | 1988-11-30 | 1994-01-25 | Kao Corporation | Water-disintegrable cleaning sheet |
EP0372388B1 (en) * | 1988-11-30 | 1994-02-16 | Kao Corporation | Water-disintegrable cleaning sheet |
JP2584508B2 (ja) * | 1989-02-28 | 1997-02-26 | 花王株式会社 | 清掃用品用水解紙 |
FR2670516B1 (fr) * | 1990-12-13 | 1993-04-09 | Hoechst France | Procede d'enduction des papiers et son application a la flexographie. |
US5266162A (en) * | 1990-12-13 | 1993-11-30 | Societe Francaise Hoechst | Process for coating papers and its use in flexographic printing |
JP3030976B2 (ja) * | 1991-09-09 | 2000-04-10 | 荒川化学工業株式会社 | 製紙用ロジン系エマルジョンサイズ剤 |
US5741572A (en) * | 1995-02-17 | 1998-04-21 | Lexmark International, Inc. | Heat fixing paper or sheet |
DE19607674A1 (de) * | 1996-02-29 | 1997-09-04 | Basf Ag | Verwendung von hydrolysierten Polymerisaten von N-Vinylcarbonsäureamiden als Mittel zur Erhöhung der Trockenfestigkeit von Papier, Pappe und Karton |
DE19758479C2 (de) * | 1997-07-02 | 2002-07-11 | Koehler Decor Gmbh & Co Kg | Imprägnierflotte |
EP1656335A1 (de) | 2003-08-14 | 2006-05-17 | Basf Aktiengesellschaft | Verfahren zur herstellung von (meth)acrolein und/oder (meth)acryls ure |
US7390846B2 (en) * | 2004-11-30 | 2008-06-24 | Crompton Corporation | Wood sizing agents for PVC composites |
DE102007010422A1 (de) | 2007-03-01 | 2008-09-04 | Basf Se | Verfahren zur Herstellung eines Katalysators bestehend aus einem Trägerkörper und einer auf der Oberfläche des Trägerkörpers aufgebrachten katalytisch aktiven Masse |
DE102009047291A1 (de) | 2009-11-30 | 2010-09-23 | Basf Se | Verfahren zur Herstellung von (Meth)acrolein durch heterogen katalysierte Gasphasen-Partialoxidation |
DE102010048405A1 (de) | 2010-10-15 | 2011-05-19 | Basf Se | Verfahren zum Langzeitbetrieb einer heterogen katalysierten partiellen Gasphasenoxidation von Proben zu Acrolein |
DE102011076931A1 (de) | 2011-06-03 | 2012-12-06 | Basf Se | Wässrige Lösung, enthaltend Acrylsäure und deren konjugierte Base |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR931044A (fr) | 1945-02-09 | 1948-02-11 | Ici Ltd | Procédé de traitement du papier |
GB1216337A (en) | 1967-08-30 | 1970-12-16 | William Nash Ltd | Production of paper base materials |
JPS52132A (en) * | 1975-06-23 | 1977-01-05 | Nec Corp | Memory |
JPS5218803A (en) * | 1975-08-05 | 1977-02-12 | Nippon Zatsuka Shinkou Sentaa | Method of molding wood product |
DE2741753B1 (de) | 1977-09-16 | 1979-03-22 | Basf Ag | Verfahren zur Herstellung von Papier mit hoher Trockenfestigkeit und niedriger Nassfestigkeit |
-
1979
- 1979-01-27 DE DE19792903218 patent/DE2903218A1/de not_active Withdrawn
- 1979-12-18 CA CA000342176A patent/CA1140819A/en not_active Expired
-
1980
- 1980-01-03 US US06/109,315 patent/US4294873A/en not_active Expired - Lifetime
- 1980-01-10 FI FI800072A patent/FI64964C/fi not_active IP Right Cessation
- 1980-01-22 AT AT80100302T patent/ATE1591T1/de not_active IP Right Cessation
- 1980-01-22 EP EP80100302A patent/EP0013969B1/de not_active Expired
- 1980-01-22 DE DE8080100302T patent/DE3060860D1/de not_active Expired
- 1980-01-24 AU AU54898/80A patent/AU553980B2/en not_active Ceased
- 1980-01-25 ES ES488034A patent/ES8105058A2/es not_active Expired
- 1980-01-25 NO NO800183A patent/NO157186C/no unknown
- 1980-01-28 JP JP787680A patent/JPS55103393A/ja active Pending
Also Published As
Publication number | Publication date |
---|---|
AU5489880A (en) | 1980-07-31 |
AU553980B2 (en) | 1986-07-31 |
FI64964B (fi) | 1983-10-31 |
DE3060860D1 (en) | 1982-11-04 |
US4294873A (en) | 1981-10-13 |
ATE1591T1 (de) | 1982-10-15 |
FI64964C (fi) | 1984-02-10 |
NO800183L (no) | 1980-07-28 |
DE2903218A1 (de) | 1980-08-07 |
EP0013969A1 (de) | 1980-08-06 |
NO157186C (no) | 1988-02-03 |
NO157186B (no) | 1987-10-26 |
ES488034A0 (es) | 1981-04-01 |
JPS55103393A (en) | 1980-08-07 |
CA1140819A (en) | 1983-02-08 |
ES8105058A2 (es) | 1981-04-01 |
FI800072A (fi) | 1980-07-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0013969B1 (de) | Verfahren zur Herstellung von Papier mit hoher Trockenfestigkeit und niedriger Nassfestigkeit | |
DE1546369C3 (de) | Verfahren zur Herstellung von Papier, Pappe und dgl. mit verbesserter Naßfestigkeit. Ausscheidung aus: 1177824 | |
EP0216387B1 (de) | Verfahren zur Herstellung von Vinylamin-Einheiten enthaltenden wasserlöslichen Copolymerisaten und deren Verwendung als Nass- und Trockenverfestigungsmittel für Papier | |
EP1999314B1 (de) | Verfahren zur herstellung von papier, pappe und karton mit hoher trockenfestigkeit | |
EP1819877B1 (de) | Verfahren zur herstellung von papier, pappe und karton mit hoher trockenfestigkeit | |
EP0193111B1 (de) | Verfahren zur Herstellung von Papier mit hoher Trockenfestigkeit | |
DE2357165B2 (de) | Oberflächenleim- und -streichmasse für Papier | |
DE1669231A1 (de) | Mischpolymerisat-Pigmentbindemittel | |
DE2425265C2 (de) | Mittel zur Oberflächenleimung von Papier | |
DE69725779T2 (de) | Leimung von Papier mit Latexdispersionen aus Copolymeren aus hydrophoben Monomeren und niedermolecularen Styrol/Maleinanhydride-Polymeren | |
DE3878262T2 (de) | Klebstoff auf der basis von latex fuer papier und wellpappe. | |
CH637714A5 (de) | Verfahren zur herstellung von papier mit hoher trockenfestigkeit und niedriger nassfestigkeit. | |
DE1696221C3 (de) | Bindemittel für Papierstreichmassen auf Polyvinylalkohol-B3 747t | |
DE2741753C3 (es) | ||
DE2339990C2 (de) | Beschichtungsmassen für Papier und ihre Verwendung | |
EP0146000B1 (de) | Verfahren zur Herstellung von Papier, Karton und Pappe mit hoher Trocken-, Nass- und Laugenfestigkeit | |
DE1771367B2 (de) | Verwendung von elektrisch leitfaehigem papier fuer elektrographische druckverfahren | |
CH524015A (de) | Papierstreichmassen | |
DE2040692C3 (de) | Verfahren zur Papierleimung | |
DE1696168C3 (de) | Verfahren zum Leimen von Papier | |
DE2117682C3 (de) | Verfahren zur Oberflächenleimung von Papier | |
DE2161773C3 (de) | Verfahren zur Oberflächenleimung von Papier | |
EP0542125B1 (de) | Verfahren zum Abscheiden eines in Wasser gelösten Bindemittels | |
DE3413447A1 (de) | Verfahren zur herstellung von papier mit hoher trockenfestigkeit und niedriger nassfestigkeit | |
WO2006136556A2 (de) | Verfahren zur herstellung von papier, pappe und karton |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT NL SE |
|
17P | Request for examination filed |
Effective date: 19801206 |
|
ITF | It: translation for a ep patent filed | ||
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Designated state(s): AT BE CH DE FR GB IT NL SE |
|
REF | Corresponds to: |
Ref document number: 1591 Country of ref document: AT Date of ref document: 19821015 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 3060860 Country of ref document: DE Date of ref document: 19821104 |
|
ET | Fr: translation filed | ||
ITTA | It: last paid annual fee | ||
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 19911218 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 19911219 Year of fee payment: 13 Ref country code: CH Payment date: 19911219 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 19920102 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 19920116 Year of fee payment: 13 Ref country code: DE Payment date: 19920116 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 19920124 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 19920131 Year of fee payment: 13 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19930122 Ref country code: AT Effective date: 19930122 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19930123 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19930128 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Effective date: 19930131 Ref country code: BE Effective date: 19930131 |
|
BERE | Be: lapsed |
Owner name: BASF A.G. Effective date: 19930131 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19930801 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 19930122 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Effective date: 19930930 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST |
|
EUG | Se: european patent has lapsed |
Ref document number: 80100302.1 Effective date: 19930810 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |