US3141813A - Process of impregnating paper containing synthetic fibers and an amineformaldehyde resin with copolyamide and polyacrylic acid ester - Google Patents
Process of impregnating paper containing synthetic fibers and an amineformaldehyde resin with copolyamide and polyacrylic acid ester Download PDFInfo
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- US3141813A US3141813A US133305A US13330561A US3141813A US 3141813 A US3141813 A US 3141813A US 133305 A US133305 A US 133305A US 13330561 A US13330561 A US 13330561A US 3141813 A US3141813 A US 3141813A
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- copolyamide
- paper
- aqueous
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- 150000002148 esters Chemical class 0.000 title claims description 36
- 238000000034 method Methods 0.000 title claims description 35
- 229920002994 synthetic fiber Polymers 0.000 title claims description 26
- 239000012209 synthetic fiber Substances 0.000 title claims description 26
- IWLBIFVMPLUHLK-UHFFFAOYSA-N azane;formaldehyde Chemical compound N.O=C IWLBIFVMPLUHLK-UHFFFAOYSA-N 0.000 title claims description 14
- 229920002125 Sokalan® Polymers 0.000 title description 9
- 239000004584 polyacrylic acid Substances 0.000 title description 9
- 229920005989 resin Polymers 0.000 title description 5
- 239000011347 resin Substances 0.000 title description 5
- 239000000470 constituent Substances 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 22
- 230000001476 alcoholic effect Effects 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 239000007900 aqueous suspension Substances 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000000243 solution Substances 0.000 description 66
- 239000000835 fiber Substances 0.000 description 31
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 238000003490 calendering Methods 0.000 description 8
- 238000011282 treatment Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229920001131 Pulp (paper) Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 239000000976 ink Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical compound [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000001164 aluminium sulphate Substances 0.000 description 3
- 235000011128 aluminium sulphate Nutrition 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 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 3
- 239000000839 emulsion Substances 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- MEMUMYCLWQPAEX-UHFFFAOYSA-N n-octadecylaziridine-1-carboxamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)N1CC1 MEMUMYCLWQPAEX-UHFFFAOYSA-N 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical class C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical class OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 241000183024 Populus tremula Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- XTSFUENKKGFYNX-UHFFFAOYSA-N bis(aziridin-1-yl)methanone Chemical compound C1CN1C(=O)N1CC1 XTSFUENKKGFYNX-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000010494 opalescence Effects 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Images
Classifications
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- 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
-
- 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
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
-
- 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
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/47—Condensation polymers of aldehydes or ketones
- D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
-
- 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
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
Definitions
- This invention relates to the production of paper and more particularly to the production of resin-impregnated paper which includes synthetic fibers, is ink-fast, and has a high wet-strength and high tear-propagation resistance.
- paper designates any paper or paper-like material prepared on a paper-making machine, such as paper, bonded fabric, non-Woven fabric and similar flat material.
- synthetic fibers is used in the generally accepted sense of including both fibers made from natural polymers, as for example viscose fibers, and those made from synthetic polymers such as polyamides.
- the synthetic fibers preferably have a titre of 1.5-3 denier and a staple length of 24 mm. in the case of fibers derived from natural polymers, and a titre of 1.5-3 denier and a staple length of 3-6 mm. in the case of fibers made from wholly synthetic polymers, and may be combined with the known substances used in making paper pulps, such as rags, bleached or unbleached wood pulp or the like. Preferred mixtures contain 20-80% by weight of synthetic fibers and 80-20% by weight of such other fibrous materials.
- copolyamides to be used in the aforesaid process should be readily soluble in aqueous alcohol, they should be colourless and, above all, their solutions should be stable and have little gelling tendency at room tempera- 3,l4l,8i3 Patented July 21, 1364 ice ture. Such copoyamides are good film-formers and melt at a relatively low temperature.
- copolyamides those are particularly suitable for use in the said process which can be prepared by polymerising a mixture of a salt of a diamine and a dicarboxylic acid with a lactam of an w-aminocarboxylic acid and/ or with an aminocarboxylic acid.
- the binary copolyamides of hexamethylene diammonium adipate and e-aminocaprolactam Within the range of 35-45% by weight of hexamethylene diammonium adipate and 65-55% by Weight of e-aminocaprolactam are particularly suitable.
- ternary copolyamides there may be used, for example, mixtures of 10-20% by weight of w-aminoundecyclic acid, 40-30% by weight of hexamethylene diammonium adipate and 50% by weight of e-aminocaprolactam.
- Such copolyamides should have, for example, a reduced viscosity of 1.10 to 1.30 and, according to the proportions used, a melting point of 165-185 C. After a preliminary partial swelling at room temperature they dissolve at 60 C. in 67% aqueous ethanol or methanol to give solutions of 8 to 12% strength. These solutions are clear and viscous and do not gel even after standing for several days at room temperature.
- a reagent capable of cross-linking the copolyamide added to the paper base by the impregnation it is of advantage to use a cationic melamineformaldehyde precondensate having alfinity for the fiber, if desired in the presence of a small amount of aluminium sulphate.
- Such precondensates can be obtained by dissolving trirnethylolmelamine in water, adding formic or hydrochloric acid to this solution and letting it ripen for several hours until it displays a bluish opalescence. Such a solution is stable for 12 to 14 hours.
- cross-linking of the substratum with the copolyamide film and/or of the copolyamide alone may be achieved with the application of heat and under superatmospheric pressure.
- a small amount of aluminium sulphate contained in the paper base acts as a mild catalyst.
- a small amount of a cross-linking substance such as 1:6-hexamethylene-N:N- bis-(ethylene-urea) or formaldehyde donors and/or of a hydrophobising agent which likewise reacts chemically with the substratum and the copolyamide, such as octadecyl ethylene-urea, may be added to the impregnating liquor.
- a cross-linking substance such as 1:6-hexamethylene-N:N- bis-(ethylene-urea) or formaldehyde donors and/or of a hydrophobising agent which likewise reacts chemically with the substratum and the copolyamide, such as octadecyl ethylene-urea
- Such additives must be compatible with the dissolved copolyamide, that is to say they must not precipitate from the copolyamide solution or be inactivated by it.
- no acidic catalyst should be present since otherwise the ethyleneimide derivatives would precipitate from the aque
- a process for the production of paper which comprises forming an aqueous suspension of fibers including synthetic fibers, adding thereto an amineforrnaldehyde precondensate, and optionally also a water-soluble polyvalent metal salt, forming a web from such suspension, drying it, impregnating the web with an aqueous alcoholic solution containing a linear copolyarnide of high molecular weight and a polyacrylic acid ester of high molecular weight, drying the web and, if desired, hotcalendering it. Both linear copolyamide and polyacrylic ester must be film-forming.
- the viscosity number of the polyacrylic esters may be between 1.5 and 3.5 as measured by forming a film from the commercial product, drying it in vacuo over phosphorus pentoxide, dissolving the film in a 1:9 mixture of ethanol and tetrachlorethane, determining the viscosities of a series of solutions of concentrations rang ing from 0.05 to 0.4 g. of polymer per 100 ml. of solution at a temperature of 20i0.05 C. using an Ostwald viscometer of 5 cc. capacity and a running time of 70-80 seconds for the solvent used and finally extrapolating the series to zero concentration; viscosity number lin1 (1 spec.)
- the invention further includes paper manufactured by the process just set forth.
- a hydrophobising agent as well as a small amount of crosslinking agent, such as a formaldehyde donor (e.g. melamine resins or a diethylene urea derivative) and to press the impregnated sheet at an elevated temperature, for example on a hot calender.
- a formaldehyde donor e.g. melamine resins or a diethylene urea derivative
- Example 1 In a vat a suspension is prepared from 0.8 kg. of bleached and ground sulphate cellulose, 0.4 kg. of ground aspen wood pulp and 0.8 kg. of staple fiber of polyhexamethylene adipamide (staple length 4 mm., fiber titer 2 denier) and 150 liters of Water by stirring.
- This suspension is treated with a mixture of 40 grams of a melamine-formaldehyde precondensate (39% nitrogen) with 12 grams of formic acid, an aqueous solution of 62 grams of alum is run in, the whole is mixed and then made up with water to 200 liters.
- the pH value of this aqueous suspension in the stuff chest of the paper-making machine ranges from 5 to 6.
- This suspension is converted on a Fourdrinier paper-making machine into a paper web and dried. The moist paper web does not stick to the wet felt roller.
- the first piece (1) is used only for measuring the properties of the paper base and is hot calendered for one second at 165 C.
- the second piece (2) is impregnated at room temperature while travelling at a rate of 3 meters per minute by passing it through a solution of 10% by weight of a copolyamide in 67% by weight aqueous ethanol.
- the copolyamide is prepared from 40% by weight of hexamethylene diarnmonium adipate and 60% of E-aminocaprolactam and has a melting point of 165 C. and a reduced viscosity (as hereinbefore defined) of 1.18.
- the paper is then dried on a drying cylinder under a pressure of 0.9 atmosphere gauge and hot calendered for one second at 165 C.
- the third piece (3) is impregnated according to the present process with a solution of 8.75% of the aforementioned copolyamide, 1.25% (calculated as solids) of a commercial non-ionic polyacrylic acid ester emulsion containing free carboxyl groups and having a solids content of 46.5% (pl-l value 6.0 to 6.5) in 67% by Weight aqueous ethanol, as described above under (12), and then further processed as described above.
- the product used was that sold by Rohm & Haas Company of Philadelphia under the name Rhoplex B15. It was the ethyl ester, had a saponification number of 530 mg. of KOl-I per gram of solids, 0.082 free carboxyl groups per structural (monomer) unit and a viscosity number of 2.55 measured as described above.
- the fourth piece (4) is further treated according to the process of our copending application Serial No. 133,304 filed August 23rd, 1961.
- the paper is impregnated as described above under (15) with a solution of 10% by weight of the aforementioned copolyamide, 1.05% of an alkyl-modified hexamethylolmelamine, 0.5% of a hydrophobising agent based on octadecyl ethylene urea in 67% by weight aqueous ethanol, and then further treated as described above.
- the fifth piece (5) of the paper web is treated by the present process.
- the impregnation, drying and calendering are carried out as described under (b) above, except that the impregnating solution consists of 8.75% by weight of the aforementioned copolyamide, 1.25% of the polyacrylic acid ester emulsion used under (0) above, 1.05% of the hexamethylolmelamine used under (d), 0.5 of the hydrophobising agent used according to (a') in 67% aqueous ethanol.
- Break- Breaking Break- Wet Breaking Specimen ing elongalength, strength elonga- Elmen- N 0. length, tion dry, Wet, in in pen tion Wet, dorf dry, in in perkm. cent 1 insawar 2 km. cent cent 0. 995 1. 66 0. 2 20 77. 5 4. 63 7. 34 1.72 37 8. l 244. 0 4. l1 8. 10 l. 67 40 8. 1 295. 0 5. 041 7. 2. 57 51 10. 2 192. 0 5. 26 8. 1O 2. 49 47 10. 3 275. 5
- the hot calendered paper base has only a restricted dry strength and a wet strength which is so low that it is diflicult to measure it with the available instruments.
- the Elmendorf tear is likewise relatively low.
- the treatment applied to specimen (4) according to the process of our copending application Serial No. 133,304 filed August 23, 1961, aims primarily at improving the wet strength of the paper and this aim is actually achieved, but the Elmendorf tear is substantially reduced.
- the treatment of specimen (5) according to the present invention, with a combination of copolyamide, cross-linking agent and hydrophobising agent and copolyacrylic compound produces a paper of very high wet strength and Elmendorf tear and a relatively high stretchability.
- test sheet obtained by the treatment under (e), containing 40% by weight of polyamide fibers was immersed for 5 hours in alcohol, then rinsed with fresh alcohol and dried at 60 C.
- the change in relative percent in the properties resulting from these treatments was as follows:
- the breaking strength would be expected to show a decrease of at least 50% if the binder had not formed a chemical bond with the fibers.
- the paper produced according to the present invention has excellent heat stability. Thus, the properties were found not to be adversely affected even after heating for several days at 105 C.
- the papers produced according to the present invention may be die-stamped, creped and otherwise embossed.
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- Chemical Kinetics & Catalysis (AREA)
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
July 21, 964 B. s. v. MAREK ETAL 3,141,813
PROCESS OF IMPREGNATING PAPER CONTAINING SYNTHETIC FIBERS AND AN AMINEFORMALDEHYDE RESIN WITH COPOLYAMIDE AND POLYACRYLIC ACID ESTER Filed Aug. 23, 1961 AMlNE-FORMALDEHYDE P 0 AQUEOUS FIBRE SLURRY (WATER 5OLUBLE PQLY. a CONTAINING MAN MADE FIBRES DRYING DRIED WEB (CROSS LINKING AGENT) I AQUEOUS-ALCOHOLIC SOLUTION OF LINEAR COPOLYAMIDE |MPRE(3NF\TlNG-"- POLYACRYLIC ACID ESTER (HYnaoPHolslNc-a SUBSTANCE) IMPREGNATEDWEB DRYING DRIED PAPER (HOT CALENDERING) HNISHED PAPER y m A ttorneys United States Patent 3,141,313 PRQQESS 0F HMPREGNATHNG PAPER CQNTATN- ENG SYNTHETIC FIBERS AND AN AMINE- FQRMALDEHYDE RESIN WHTH (IQPGLYAMEBE AND PULYACRYLEC AtITD ESTER Bruno Stefan Vladimir Marek and Iiosef Gneisz, both of Emmenbruecke, near Lueerne, Switzerland, assignors to Societe de La Viscose Saisse, Emmenhrucire, Switzerland, a Swiss body corporate Filed Aug. 23, 1961, Ser. No. 133,305 Claims priority, application Great Britain Sept. 1, 1960 13 Claims. till. 162-135) This invention relates to the production of paper and more particularly to the production of resin-impregnated paper which includes synthetic fibers, is ink-fast, and has a high wet-strength and high tear-propagation resistance. For the purpose of the present process the term paper designates any paper or paper-like material prepared on a paper-making machine, such as paper, bonded fabric, non-Woven fabric and similar flat material.
Various methods of producing paper wherein synthetic resins are used have been described. Thus, it is known to coat paper with a polyacrylic ester of high molecular weight; such papers however do not have a very high wet-strength. It is also known to size paper with acrylamide polymers. Improved wet strength is achieved by incorporating melamine resins in the paper pulp. German Patent No. 902,967 describes the production of leather-like articles by binding a fiber mixture with polyacrylic acid derivatives. British patent specification No. 797,943 proposes the impregnation of paper with polyesters of dicarboxylic acids and N-aryl-dialkanolamines. In a known process for the manufacture of paper from synthetic fibers the fibers are coated with sparingly soluble cation-active or anion-active agents and a web is formed, the binder used being an N-alkoxypolyamide or a urea-formaldehyde condensate of high concentration. Further, it is known to produce a paper-like substance by coating a web of synthetic fibers with a polyacrylic ester and subjecting it to hot calendering; this process is somewhat expensive.
In our copending application Serial No. 133,304, filed August 23, 1961, a process for the production of paper is described in which the paper includes synthetic fibers, is ink-fast and has a high wet strength. The method employed is to add to an aqueous fiber suspension, which contains synthetic fibers, an amine-formaldehyde precondensate and optionally a water-soluble polyvalent metal salt, forming a web from such suspension, drying it, impregnating the web with an aqueous/alcoholic solution of a linear copolyamide ofhigh molecular weight, drying the web and, if desired, hot-calendering it.
In that application and in the present application the term synthetic fibers is used in the generally accepted sense of including both fibers made from natural polymers, as for example viscose fibers, and those made from synthetic polymers such as polyamides.
The synthetic fibers preferably have a titre of 1.5-3 denier and a staple length of 24 mm. in the case of fibers derived from natural polymers, and a titre of 1.5-3 denier and a staple length of 3-6 mm. in the case of fibers made from wholly synthetic polymers, and may be combined with the known substances used in making paper pulps, such as rags, bleached or unbleached wood pulp or the like. Preferred mixtures contain 20-80% by weight of synthetic fibers and 80-20% by weight of such other fibrous materials.
The copolyamides to be used in the aforesaid process should be readily soluble in aqueous alcohol, they should be colourless and, above all, their solutions should be stable and have little gelling tendency at room tempera- 3,l4l,8i3 Patented July 21, 1364 ice ture. Such copoyamides are good film-formers and melt at a relatively low temperature.
The reduced viscosity mentioned hereinafter is defined by the formula:
' ln 1; rel.
(where ln represents the natural or Napierian logarithm, 1 rel. the relative viscosity and c the concentration of the solution in grams per ccs. of solution), measured at 20 C. in a solution of the copolyamide of a concentration 0:0.2 gram copolyamide per 100 cc. of solution. The solvent is sulphuric acid of 93.7% strength.
Among the aforementioned copolyamides those are particularly suitable for use in the said process which can be prepared by polymerising a mixture of a salt of a diamine and a dicarboxylic acid with a lactam of an w-aminocarboxylic acid and/ or with an aminocarboxylic acid. The binary copolyamides of hexamethylene diammonium adipate and e-aminocaprolactam Within the range of 35-45% by weight of hexamethylene diammonium adipate and 65-55% by Weight of e-aminocaprolactam are particularly suitable. For the preparation of ternary copolyamides there may be used, for example, mixtures of 10-20% by weight of w-aminoundecyclic acid, 40-30% by weight of hexamethylene diammonium adipate and 50% by weight of e-aminocaprolactam. Such copolyamides should have, for example, a reduced viscosity of 1.10 to 1.30 and, according to the proportions used, a melting point of 165-185 C. After a preliminary partial swelling at room temperature they dissolve at 60 C. in 67% aqueous ethanol or methanol to give solutions of 8 to 12% strength. These solutions are clear and viscous and do not gel even after standing for several days at room temperature. On the other hand, a solution of 10% by Weight strength in 95% alcohol gels after a few hours. A film obtained from a 7.5% solution is clear, tough and stretchable; the films have a breaking length of 1.7 to 2.5 kilometers and an elongation at break of to 300%.
It has proved particularly advantageous to add to the paper pulp a reagent capable of cross-linking the copolyamide added to the paper base by the impregnation. For this purpose it is of advantage to use a cationic melamineformaldehyde precondensate having alfinity for the fiber, if desired in the presence of a small amount of aluminium sulphate. Such precondensates can be obtained by dissolving trirnethylolmelamine in water, adding formic or hydrochloric acid to this solution and letting it ripen for several hours until it displays a bluish opalescence. Such a solution is stable for 12 to 14 hours.
The cross-linking of the substratum with the copolyamide film and/or of the copolyamide alone may be achieved with the application of heat and under superatmospheric pressure. In this case a small amount of aluminium sulphate contained in the paper base acts as a mild catalyst.
For the purpose of further improving the wet strength or stability to Water respectively a small amount of a cross-linking substance, such as 1:6-hexamethylene-N:N- bis-(ethylene-urea) or formaldehyde donors and/or of a hydrophobising agent which likewise reacts chemically with the substratum and the copolyamide, such as octadecyl ethylene-urea, may be added to the impregnating liquor. Such additives must be compatible with the dissolved copolyamide, that is to say they must not precipitate from the copolyamide solution or be inactivated by it. When an imine is present no acidic catalyst should be present since otherwise the ethyleneimide derivatives would precipitate from the aqueous alcoholic solution or be inactivated by it.
It has now been discovered that the Elmendorf tear 3 of paper so manufactured is substantially improved by impregnating the web not only with the copolyamide of high molecular weight but also with a polyacrylic acid ester of high molecular weight.
According to the present invention, therefore, there is provided a process for the production of paper which comprises forming an aqueous suspension of fibers including synthetic fibers, adding thereto an amineforrnaldehyde precondensate, and optionally also a water-soluble polyvalent metal salt, forming a web from such suspension, drying it, impregnating the web with an aqueous alcoholic solution containing a linear copolyarnide of high molecular weight and a polyacrylic acid ester of high molecular weight, drying the web and, if desired, hotcalendering it. Both linear copolyamide and polyacrylic ester must be film-forming. (lo-pending application Serial No. 133,304 indicates that a useful range of reduced viscosities, as defined above, for the copolyamides is 1.10 to 1.30. The viscosity number of the polyacrylic esters may be between 1.5 and 3.5 as measured by forming a film from the commercial product, drying it in vacuo over phosphorus pentoxide, dissolving the film in a 1:9 mixture of ethanol and tetrachlorethane, determining the viscosities of a series of solutions of concentrations rang ing from 0.05 to 0.4 g. of polymer per 100 ml. of solution at a temperature of 20i0.05 C. using an Ostwald viscometer of 5 cc. capacity and a running time of 70-80 seconds for the solvent used and finally extrapolating the series to zero concentration; viscosity number lin1 (1 spec.)
where 1 spec. is the specific viscosity and c the concentration.
The invention further includes paper manufactured by the process just set forth.
It is to be understood that the materials used and the specific techniques described in our copending application Serial No. 133,304 filed August 23rd, 1961, and which have been referred to briefly above, may, taking into consideration the specific differences between the two processes, be employed in the process of the present invention.
To achieve a particularly high wet strength it has proved advantageous to add to the aqueous alcoholic solution a hydrophobising agent as well as a small amount of crosslinking agent, such as a formaldehyde donor (e.g. melamine resins or a diethylene urea derivative) and to press the impregnated sheet at an elevated temperature, for example on a hot calender. These measures have been described in our copending application Serial No. 133,304 filed August 23rd, 1961.
The process is illustrated in the accompanying drawing by a flow diagram in which the continuous lines indicate the main features of the invention and the discontinuous lines indicate subordinate features.
The following example illustrates the invention:
Example In a vat a suspension is prepared from 0.8 kg. of bleached and ground sulphate cellulose, 0.4 kg. of ground aspen wood pulp and 0.8 kg. of staple fiber of polyhexamethylene adipamide (staple length 4 mm., fiber titer 2 denier) and 150 liters of Water by stirring. This suspension is treated with a mixture of 40 grams of a melamine-formaldehyde precondensate (39% nitrogen) with 12 grams of formic acid, an aqueous solution of 62 grams of alum is run in, the whole is mixed and then made up with water to 200 liters. The pH value of this aqueous suspension in the stuff chest of the paper-making machine ranges from 5 to 6. This suspension is converted on a Fourdrinier paper-making machine into a paper web and dried. The moist paper web does not stick to the wet felt roller.
The weight in grams per square meter of the paper bases, prepared in the above-mentioned manner, was varied between 54 and 72. These paper bases are treated according to the following specifications to have in all cases a final weight of about 72 grams per square meter in the finished state:
(a) The first piece (1) is used only for measuring the properties of the paper base and is hot calendered for one second at 165 C.
(b) The second piece (2) is impregnated at room temperature while travelling at a rate of 3 meters per minute by passing it through a solution of 10% by weight of a copolyamide in 67% by weight aqueous ethanol. The copolyamide is prepared from 40% by weight of hexamethylene diarnmonium adipate and 60% of E-aminocaprolactam and has a melting point of 165 C. and a reduced viscosity (as hereinbefore defined) of 1.18. The paper is then dried on a drying cylinder under a pressure of 0.9 atmosphere gauge and hot calendered for one second at 165 C.
(c) The third piece (3) is impregnated according to the present process with a solution of 8.75% of the aforementioned copolyamide, 1.25% (calculated as solids) of a commercial non-ionic polyacrylic acid ester emulsion containing free carboxyl groups and having a solids content of 46.5% (pl-l value 6.0 to 6.5) in 67% by Weight aqueous ethanol, as described above under (12), and then further processed as described above. The product used was that sold by Rohm & Haas Company of Philadelphia under the name Rhoplex B15. It was the ethyl ester, had a saponification number of 530 mg. of KOl-I per gram of solids, 0.082 free carboxyl groups per structural (monomer) unit and a viscosity number of 2.55 measured as described above.
(d) The fourth piece (4) is further treated according to the process of our copending application Serial No. 133,304 filed August 23rd, 1961. For this purpose the paper is impregnated as described above under (15) with a solution of 10% by weight of the aforementioned copolyamide, 1.05% of an alkyl-modified hexamethylolmelamine, 0.5% of a hydrophobising agent based on octadecyl ethylene urea in 67% by weight aqueous ethanol, and then further treated as described above.
(2) The fifth piece (5) of the paper web is treated by the present process. The impregnation, drying and calendering are carried out as described under (b) above, except that the impregnating solution consists of 8.75% by weight of the aforementioned copolyamide, 1.25% of the polyacrylic acid ester emulsion used under (0) above, 1.05% of the hexamethylolmelamine used under (d), 0.5 of the hydrophobising agent used according to (a') in 67% aqueous ethanol.
Of all 5 papers, pieces having an identical weight of about 72 grams per square meter were measured. The results of the measurements are shown in the following table:
Break- Breaking Break- Wet Breaking Specimen ing elongalength, strength elonga- Elmen- N 0. length, tion dry, Wet, in in pen tion Wet, dorf dry, in in perkm. cent 1 in pertear 2 km. cent cent 0. 995 1. 66 0. 2 20 77. 5 4. 63 7. 34 1.72 37 8. l 244. 0 4. l1 8. 10 l. 67 40 8. 1 295. 0 5. 041 7. 2. 57 51 10. 2 192. 0 5. 26 8. 1O 2. 49 47 10. 3 275. 5
1 Wet strength= xioo.
breaking length, dry
2 Elmendorf tear, in the longitudinal machine direction, in gramscorreeted for a paper weight of grams per square meter.
As will be seen from the above table, the hot calendered paper base has only a restricted dry strength and a wet strength which is so low that it is diflicult to measure it with the available instruments. The Elmendorf tear is likewise relatively low. By a treatment of the paper with copolymer and polyacrylic compound as eifected for specimen (3), some increase in the wet strength and a considerable increase in the Elmendorf tear is achieved compared to specimen (2) not treated according to the present invention. The treatment applied to specimen (4), according to the process of our copending application Serial No. 133,304 filed August 23, 1961, aims primarily at improving the wet strength of the paper and this aim is actually achieved, but the Elmendorf tear is substantially reduced. The treatment of specimen (5) according to the present invention, with a combination of copolyamide, cross-linking agent and hydrophobising agent and copolyacrylic compound produces a paper of very high wet strength and Elmendorf tear and a relatively high stretchability.
It is remarkable that the treatments according to the present invention produce a chemical bond between the resins and the fibre material in spite of the extremely short condensation period of only one second, without adding any catalyst to the aqueous alcoholic binder solution. This fact is especially important since the polyacrylic acid ester emulsions and the ethylene imine derivatives in alcoholic solution are incompatible with acid catalysts and tend to precipitate when an acid catalyst is present in the impregnating solution.
The fact that the resins have actually entered into a chemical bond with the fibre material is shown by the following experiment:
A test sheet obtained by the treatment under (e), containing 40% by weight of polyamide fibers, was immersed for 5 hours in alcohol, then rinsed with fresh alcohol and dried at 60 C. The change in relative percent in the properties resulting from these treatments was as follows:
Breaking strength dry Increased by 2.7%. Breaking strength wet Increased by 1.0%. Elrnendorf tear Reduced by 8.0%.
Since the binders were applied in the form of an alcoholic solution, the breaking strength would be expected to show a decrease of at least 50% if the binder had not formed a chemical bond with the fibers.
Writing tests with ink, drawing ink, and coloured inks on papers prepared according to the present process as described under (c) and (8) revealed a very high ink fastness. In these tests specimens of extremely porous paper containing 80% of polyamide fibers were treated for 4 hours at room temperature with water, with hydrochloric acid of 4% strength and with sodium hydroxide solution of 4% strength, then washed and dried, after which it was possible to write on them without the ink running, and to print on them. Furthermore, the mechanical properties of the paper were not adversely aifected by such treatments.
It is also to be noted that the paper produced according to the present invention has excellent heat stability. Thus, the properties were found not to be adversely affected even after heating for several days at 105 C.
The papers produced according to the present invention may be die-stamped, creped and otherwise embossed.
We claim:
1. In a process for the production of paper which contains a proportion of synthetic fibers and in which an aqueous suspension of the fiber containing an amineformaldehyde precondensate is formed into a web and dried and the dried web is thereafter impregnated with an aqueous alcoholic solution of a linear copolyamide as filmforming constituent and drying the impregnated sheet, the improvement which consists in including in the said aqueous-alcoholic solution a further film-forming constituent consisting of a polyacrylic ester, the total concentration of film-forming constituent in said solution being about 10% by weight and the concentration of copolyamide being about 8.75%.
2. In a process for the production of paper which contains a proportion of synthetic fibers and in which an aqueous suspension of the fiber containing an amine-formaldehyde precondensate and a water-soluble salt of a polyvalent metal is formed into a web and dried and the dried web is thereafter impregnated with an aqueous alcoholic solution of a linear copolyamide as film-forming constituent and drying the impregnated sheet, the improvement which consists in including in the said aqueous-alcoholic solution a further film-forming constituent consisting of a polyacrylic ester, the concentration of copolyamide being about 8.75% by weight and the concentration of polyacrylic ester being about 1.25% by weight.
3. In a process for the production of paper which contains a proportion of synthetic fibers and in which an aqueous suspension of the fiber containing an amineformaldehyde precondensate is formed into a web and dried and the dried web is thereafter impregnated with an aqueous alcoholic solution of a linear copolyamide as film-forming constituent and a cross-linking agent and drying the impregnated sheet, the improvement which consists in including in the said aqueous-alcoholic solution a further film-forming constituent consisting of a polyacrylic ester, the concentration of said linear copolyamide in said solution being about 8.75% by weight and the concentration of said polyacrylic ester being about 1.25% by weight.
4. In a process for the production of paper which contains a proportion of synthetic fibers and in which an aqueous suspension of the fiber containing an amine-formaldehyde precondensate and aluminium sulphate is formed into a web and dried and the dried web is thereafter impregnated with an aqueous alcoholic solution of a linear copolyamide as film-forming constituent and a cross-linking agent and drying the impregnated sheet, the improvement which consists in including in the said aqueousalcoholic solution a further film-forming constituent consisting of a polyacrylic ester, the concentration of said copolyamide in said solution being about 8.75% by weight and the concentration of said polyacrylic ester being about 1.25% by weight.
5. In a process for the production of paper which contains a proportion of synthetic fibers and in which an aqueous suspension of the fiber containing an amineformaldehyde precondensate is formed into a web and dried and the dried web is thereafter impregnated with an aqueous alcoholic solution of a linear copolyamide as filmforming constituent and a hydrophobising substance and drying the impregnated sheet, the improvement which consists in including in the said aqueous-alcoholic solution a further film-forming constituent consisting of a polyacrylic ester, said polyacrylic ester being about 1.25% by weight of said solution and said copolyamide being about 8.75% by weight of said solution.
6. In a process for the production of paper which contains a proportion of synthetic fibers and in which an aqueous suspension of the fiber containing an amine-formaldehyde precondensate is formed into a web and dried and the dried web is thereafter impregnated with an aqueous alcoholic solution of a linear copolyamide as film-forming constituent and a hydrophobising substance reactive chemically with both the material of the web and the copolyamide and drying the impregnated sheet, the improvement which consists in including in the said aqueousalcoholic solution a further film-forming constituent consisting of a polyacrylic ester, said polyacrylic ester being about 1.25 by weight of said solution and said copolyamide being about 8.75% by weight of said solution.
7. In a process for the production of paper which contains a proportion of synthetic fibers and in which an aqueous suspension of the fiber containing an amine-formaldehyde precondensate is formed into a web and dried and the dried web is thereafter impregnated with an aqueous alcoholic solution of a linear copolyamide as filmforming constituent and a octadecylethylene urea and drying the impregnated sheet, the improvement which consists in including in the said aqueous-alcoholic solution a further film-forming constituent consisting of a poly- 7 acrylic ester, said polyacrylic ester being about 1.25% by Weight of said solution and said copolyamide being about 8.75% by weight of said solution.
8. In a process for the production of paper which contains a proportion of synthetic fibers and in which an aqueous suspension of the fiber containing an amine-formaldehyde precondensate is formed into a web and dried and the dried web is thereafter impregnated with an aqueous alcoholic solution of a linear copolyamide as film-forming constituent and a bifunctional ethylene imine derivative and drying the impregnated sheet, the improvement which consists in including in the said aqueous-ah coholic solution a further film-forming constituent consisting of a polyacrylic ester, the concentration of said copolyamide in said solution being about 8.75% by Weight and the concentration of said polyacrylic ester being about 1.25% by Weight.
9. In a process for the production of paper Which contains a proportion of synthetic fibers and in which an aqueous suspension of the fiber containing an amine-formaldehyde precondensate is formed into a Web and dried and the dried web is thereafter impregnated with an aqueous alcoholic solution of a linear copolyamide as filmiorming constituent and a formaldehyde donor and drying the impregnated sheet, the improvement which consists in including in the said aqueous-alcoholic solution a further film-forming constituent consisting of a polyacrylic ester, the concentration of said copolyamide being about 8.75% and the concentration of said polyacrylic ester being about 1.25%, both by weight, of said solution.
10. Process according to claim 9, wherein the fibers used comprise 20-80% of synthetic fibers.
11. In a process for the production of paper which contains a proportion of synthetic fibers and in which an aqueous suspension of the fiber containing trimethylol melamine is formed into a web and dried and the dried web is thereafter impregnated with an aqueous alcoholic solution of a linear copolyamide as film-forming constituent and drying the impregnated sheet, the improvement which consists in including in the said aqueous-alcoholic solution a further film-forming constituent consisting of a polyacrylic ester, the concentration of said copolyamide being about 8.75% and the concentration of said polyacrylic ester being about 1.25%, both by weight of said solution.
12. In a process for the production of paper which contains a proportion of synthetic fibers and in which an aqueous suspension of the fiber containing an amine-formaldehyde precondensate is formed into a web and dried and the dried web is thereafter impregnated with an aqueous alcoholic solution of a linear copolyamide as film-forming constituent and drying and hot-calendering the impregnated sheet, the improvement which consists in including in the said aqueous-alcoholic solution a further fiim-forming constituent consisting of a polyacrylic ester, the concentration of said copolyamide being about 8.75% and the concentration of said polyacrylic ester being about 1.25 both by Weight, of said solution.
13. In a process for the production of paper which contains a proportion of synthetic fibers and in which an aqueous suspension of the fiber containing, based on the fiber, about 1% by weight of a polymethylol derivative of melamine is formed into a web and dried and the dried web is impregnated with an aqueous-alcoholic solution of a linear copolyamide as film-forming constituent and drying the impregnated sheet, the improvement which consists in including in the said aqueous-alcoholic solution a further film-forming constituent consisting of a polyacrylic ester containing free carboxyl groups, the total concentration of film-forming constituents in said solution being about 10% by Weight of which about seveneighths consists of the linear copolyamide and the remainder of the polyacrylic ester.
References Cited in the file of this patent UNITED STATES PATENTS 2,406,453 Charlton Aug. 27, 1946 2,540,352 Schenck Feb. 6, 1951 2,559,220 Maxwell July 3, 1951 2,983,627 Williams May 9, 1961 3,000,777 Williams Sept. 19, 1961 3,016,325 Pattilloch Jan. 9, 1962 FOREIGN PATENTS 873,700 Great Britain July 26, 1961 874,249 Great Britain Aug. 2, 1961
Claims (1)
- 2. IN A PROCESS FOR THE PRODUCTION OF PAPER WHICH CONTAINS A PROPORTION OF SYNTHETIC FIBERS AND IN WHICH AN AQUEOUS SUSPENSION OF THE FIBER CONTAINING AN AMINE-FORMALDEHYDE PRECONDENSATE AND A WATER-SOLUBLE SALT OF A POLYVALENT METAL IS FORMED INTO A WEB AND DRIED AND THE DRIED WEG IS THEREAFTER IMPREGNATED WITH AN AQUEOUS ALCOHOLIC SOLUTION OF A LINEAR COPOLYAMIDE AS FILM-FORMING CONSTITUENT AND DRYING THE IMPREGNATED SHEET, THE IMPROVMENT WHICH CONSISTS IN INCLUDING IN THE SAID AQUEOUS-ALCOHOLIC SOLUTION A FURTHER FILM-FORMING CONSTITUENT CONSISTING OF A POLYACRYLIC ESTER, THE CONCENTRATION OF COPOLYAMIDE BEING ABOUT 8.75% BY WEIGHT AND THE CONCENTRATION OF POLYACRYLIC ESTER BEING ABOUT 1.25% BY WEIGHT.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB30241/60A GB948749A (en) | 1960-09-01 | 1960-09-01 | Improvements in the production of paper |
GB30242/60A GB948750A (en) | 1960-09-01 | 1960-09-01 | Improvements in the production of paper |
Publications (1)
Publication Number | Publication Date |
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US3141813A true US3141813A (en) | 1964-07-21 |
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US133304A Expired - Lifetime US3141812A (en) | 1960-09-01 | 1961-08-23 | Process of impregnating paper containing synthetic fibers and an amine formaldehyde precondensate with a film forming linear copolyamide |
US133305A Expired - Lifetime US3141813A (en) | 1960-09-01 | 1961-08-23 | Process of impregnating paper containing synthetic fibers and an amineformaldehyde resin with copolyamide and polyacrylic acid ester |
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US133304A Expired - Lifetime US3141812A (en) | 1960-09-01 | 1961-08-23 | Process of impregnating paper containing synthetic fibers and an amine formaldehyde precondensate with a film forming linear copolyamide |
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US (2) | US3141812A (en) |
BE (1) | BE607429A (en) |
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FR (1) | FR1297558A (en) |
GB (2) | GB948749A (en) |
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Cited By (4)
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US4392861A (en) * | 1980-10-14 | 1983-07-12 | Johnson & Johnson Baby Products Company | Two-ply fibrous facing material |
US4425126A (en) | 1979-12-28 | 1984-01-10 | Johnson & Johnson Baby Products Company | Fibrous material and method of making the same using thermoplastic synthetic wood pulp fibers |
US5512618A (en) * | 1993-05-07 | 1996-04-30 | Enviro-Chem, Inc. | Suspension-enhancing adhesive additive for paper manufacturing, liquid adhesive composition using same, and method of preparing liquid adhesive composition |
US6489040B1 (en) | 2000-02-15 | 2002-12-03 | United States Gypsium Company | Wallboard with improved roll-up resistance |
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US4387144A (en) | 1977-05-11 | 1983-06-07 | Tullis Russell & Company Limited | Battery separator material |
US4654100A (en) * | 1985-03-04 | 1987-03-31 | The Dow Chemical Company | Method for preparing random-fiber thermoset composites |
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-
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- 1960-09-01 GB GB30241/60A patent/GB948749A/en not_active Expired
- 1960-09-01 GB GB30242/60A patent/GB948750A/en not_active Expired
-
1961
- 1961-08-16 FR FR870823A patent/FR1297558A/en not_active Expired
- 1961-08-18 NL NL268379D patent/NL268379A/xx unknown
- 1961-08-18 NL NL268380A patent/NL131384C/xx active
- 1961-08-18 NL NL268379A patent/NL129158C/xx active
- 1961-08-18 NL NL268380D patent/NL268380A/xx unknown
- 1961-08-23 BE BE607429A patent/BE607429A/en unknown
- 1961-08-23 US US133304A patent/US3141812A/en not_active Expired - Lifetime
- 1961-08-23 US US133305A patent/US3141813A/en not_active Expired - Lifetime
- 1961-08-25 CH CH991261A patent/CH410615A/en unknown
- 1961-08-25 CH CH991161A patent/CH403466A/en unknown
- 1961-08-29 LU LU40559D patent/LU40559A1/xx unknown
- 1961-08-31 DE DES75537A patent/DE1226409B/en active Pending
- 1961-08-31 DE DES75536A patent/DE1222363B/en active Pending
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US4392861A (en) * | 1980-10-14 | 1983-07-12 | Johnson & Johnson Baby Products Company | Two-ply fibrous facing material |
US5512618A (en) * | 1993-05-07 | 1996-04-30 | Enviro-Chem, Inc. | Suspension-enhancing adhesive additive for paper manufacturing, liquid adhesive composition using same, and method of preparing liquid adhesive composition |
US6489040B1 (en) | 2000-02-15 | 2002-12-03 | United States Gypsium Company | Wallboard with improved roll-up resistance |
Also Published As
Publication number | Publication date |
---|---|
CH410615A (en) | 1966-03-31 |
US3141812A (en) | 1964-07-21 |
DE1226409B (en) | 1966-10-06 |
LU40559A1 (en) | 1961-10-30 |
NL268380A (en) | 1964-06-25 |
NL131384C (en) | |
CH403466A (en) | 1965-11-30 |
NL268379A (en) | 1964-06-25 |
DE1222363B (en) | 1966-08-04 |
GB948750A (en) | 1964-02-05 |
FR1297558A (en) | 1962-06-29 |
GB948749A (en) | 1964-02-05 |
NL129158C (en) | 1970-07-15 |
BE607429A (en) | 1961-12-18 |
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