EP0406039B1 - Process for making fibrous sheet products from cellulose by a paper-making process, said products being enriched with elastomeric resins - Google Patents
Process for making fibrous sheet products from cellulose by a paper-making process, said products being enriched with elastomeric resins Download PDFInfo
- Publication number
- EP0406039B1 EP0406039B1 EP19900401474 EP90401474A EP0406039B1 EP 0406039 B1 EP0406039 B1 EP 0406039B1 EP 19900401474 EP19900401474 EP 19900401474 EP 90401474 A EP90401474 A EP 90401474A EP 0406039 B1 EP0406039 B1 EP 0406039B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- impregnation
- elastomer
- resin
- constituted
- process according
- 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 - Lifetime
Links
- 229920005989 resin Polymers 0.000 title claims description 46
- 239000011347 resin Substances 0.000 title claims description 46
- 238000000034 method Methods 0.000 title claims description 17
- 230000008569 process Effects 0.000 title claims description 14
- 239000001913 cellulose Substances 0.000 title claims description 5
- 229920002678 cellulose Polymers 0.000 title claims description 5
- 238000005470 impregnation Methods 0.000 claims description 38
- 239000006185 dispersion Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 20
- 229920001971 elastomer Polymers 0.000 claims description 16
- 239000000806 elastomer Substances 0.000 claims description 16
- 230000015271 coagulation Effects 0.000 claims description 13
- 238000005345 coagulation Methods 0.000 claims description 13
- 239000000123 paper Substances 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 10
- 229920000034 Plastomer Polymers 0.000 claims description 9
- -1 aliphatic polyols Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 9
- 239000011118 polyvinyl acetate Substances 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 6
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 6
- 239000002966 varnish Substances 0.000 claims description 6
- 229920003006 Polybutadiene acrylonitrile Polymers 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 238000007792 addition Methods 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000003349 gelling agent Substances 0.000 claims description 4
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000011111 cardboard Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229910001385 heavy metal Inorganic materials 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 229920000867 polyelectrolyte Polymers 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 239000003995 emulsifying agent Substances 0.000 claims description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 229940015043 glyoxal Drugs 0.000 claims description 2
- 150000004668 long chain fatty acids Chemical class 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920000151 polyglycol Polymers 0.000 claims description 2
- 239000010695 polyglycol Substances 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 230000035939 shock Effects 0.000 claims description 2
- 230000002269 spontaneous effect Effects 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 229920001059 synthetic polymer Polymers 0.000 claims description 2
- 229920001131 Pulp (paper) Polymers 0.000 claims 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims 2
- 229920003051 synthetic elastomer Polymers 0.000 claims 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 claims 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229920000459 Nitrile rubber Polymers 0.000 claims 1
- 239000005062 Polybutadiene Substances 0.000 claims 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 claims 1
- 239000003086 colorant Substances 0.000 claims 1
- 229960001484 edetic acid Drugs 0.000 claims 1
- 238000002955 isolation Methods 0.000 claims 1
- 150000007974 melamines Chemical class 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000004014 plasticizer Substances 0.000 claims 1
- 229920002857 polybutadiene Polymers 0.000 claims 1
- 229920000193 polymethacrylate Polymers 0.000 claims 1
- 239000004800 polyvinyl chloride Substances 0.000 claims 1
- 238000011144 upstream manufacturing Methods 0.000 claims 1
- 229940117958 vinyl acetate Drugs 0.000 claims 1
- 239000000047 product Substances 0.000 description 24
- 239000000835 fiber Substances 0.000 description 13
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 9
- 239000004816 latex Substances 0.000 description 9
- 229920000126 latex Polymers 0.000 description 9
- 239000010410 layer Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000004873 anchoring Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 229960004279 formaldehyde Drugs 0.000 description 2
- 235000019256 formaldehyde Nutrition 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
- 238000010348 incorporation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000009950 felting Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 238000004804 winding 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/76—Processes or apparatus for adding material to the pulp or to the paper characterised by choice of auxiliary compounds which are added separately from at least one other compound, e.g. to improve the incorporation of the latter or to obtain an enhanced combined effect
- D21H23/765—Addition of all compounds to the pulp
-
- 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
- D21H23/76—Processes or apparatus for adding material to the pulp or to the paper characterised by choice of auxiliary compounds which are added separately from at least one other compound, e.g. to improve the incorporation of the latter or to obtain an enhanced combined effect
Definitions
- the present invention relates to a process for the preparation of sheet materials, of fibrous structure and of cellulose base, in particular by wet papermaking and constituting paper, nonwoven or cardboard, ennobled by impregnation of elastomeric resins.
- the present invention thus makes it possible to obtain, from a process using a papermaking production line, fibrous sheets based on cellulose, in particular smooth or creped and ennobled by various synthetic materials of elastomeric or plastomeric nature.
- the process thus makes it possible to obtain cartons having specific properties originating from the impregnation of products made up of said resins and allowing the use of the material thus obtained in numerous applications such as artificial leathers and the production of shoes and leather goods, high value printing sheets, gummed papers or labels as well as abrasive layer supports; the invention also makes it possible to obtain pressure-sensitive adhesive tapes, substrates usable in tapestry (floor or wall coverings); the invention also makes it possible to produce materials for technical uses, in particular for winding and protecting filiform elements such as cables or electrical cables, as well as envelopes of various shapes, in particular sterilization envelopes.
- drying cylinder tends to retain on its surface the sheet during drying therefore having only weak mechanical properties which comes to tear with rupture in the continuity of the course.
- the cylinders are regularly fouled by the deposits of resins, which leads to the need for regular stops for cleaning operations, resulting in a lowering of the general production yield.
- a first solution consisted in coating the drying cylinders and rollers with a non-stick resin with a low coefficient of friction such as fluorocarbon resins.
- the invention makes it possible to manufacture paper products containing a large proportion of finishing composition in the form of polymers and elastomers or plastomers and without any risk of deposition of elements originating from the finishing resin along the machinery and in particular at level of drying rollers.
- the invention relates to a process for wet preparation of cellulose-based fibrous structure sheet materials, such as paper, cardboard or nonwovens in which the fibrous web structure is enriched with finishing materials made of synthetic polymers of elastomeric or plastomeric resins, and in which the wet sheet formed on the endless fabric passes through an impregnation press, to receive there in its mass, before drying on heating rollers, the impregnation of the finishing material constituted by the elastomeric or plastomeric resin, in the form of an aqueous dispersion, characterized in that said aqueous dispersion contains an additive capable of causing spontaneous coagulation of said resin above a given temperature with the release of a quantity of water, thus capable of constituting an interface opposing adhesion of the aqueous dispersion.
- a long fiber paste is used which allows sufficient absorption and resistance adapted to the use for which the product is intended; the long-fiber, bleached, semi-bleached or unbleached pulp is not very refined (16 to 30 ° SR); the medium is maintained at a substantially neutral pH, between 6.5 and 7.5; it will be noted however that all the pastes, including the recycled pastes can be used within the framework of the finishing process according to the invention.
- the fibers in a conventional and conventional manner are disintegrated in the pulper and possibly refined and in the paste thus produced is then introduced a first bonding composition or a first finish constituting a retention product and chosen from the products designated under the registered trademarks Retaminol (Bayer), Cartaretine (Sandoz), Percol (Allied Colloid); this first primer is introduced in a proportion of between 0.1 and 3% of the total.
- a second primer is introduced into this dough consisting of a relatively hard and polar polymer, giving off a fairly large surface energy; preferably this polymer is an elastomer and it is dispersed in the fibrous mass in very fine particles in the form of an aqueous dispersion; a great aptitude for adhesion between the elastomers is thus obtained, or dispersion of elastomers or plastomers with the fibers of the pulp.
- polychloroprene, polybutadiene acrylonitrile, polyacrylate and polyvinyl acetate have been noted.
- This second elastomeric primer is introduced in a proportion of 0.1 to 3% of the total.
- the retention product introduced into the paste lowers the zeta potential and at the same time reduces the degree of refining by fixing the fines and by crosslinking between the long-chain polyelectrolyte molecules and the cellulose fibers of the sheet. .
- the successive additions - at predetermined intervals - of auxiliary products to the dough distribute very finely over the surface of the fiber where they present - in the form of a veil - an adhesive base excellent for "soft" latex subsequent and constituting the main finishing product.
- the prepared and surface-modified dough will be brought to the top of the machine at a concentration of 0.4% in water.
- the necessary quantity of crosslinking resin (4 to 8%) is added thereto continuously.
- the sheet is then formed on the endless canvas to be finally dried.
- the formation of the sheet is done without obstacle to the felting of the fiber, that is to say without hindrance to the formation of water bridges which naturally bind the fibers together.
- the fibrous material leaving the endless fabric is dried to a humidity level of 8 to 15% and it then has an adequate absorption power which can be adjusted initially by refining the dough.
- the sheet is then introduced into the impregnation press, at the aforementioned degree of humidity (8 to 15%) to be introduced into the impregnation bath comprising between 15 and 45% of elastomeric resin or plastomer in the form of an aqueous dispersion.
- the impregnation bath based on elastomeric resin comprises, according to a characteristic element of the invention, the incorporation of a component constituting a gelling agent capable of causing coagulation of the elastomeric resin from a certain thermal level.
- the impregnation bath is maintained at a temperature below said pre-adjusted coagulation temperature so that the dispersion is stable at the level of the impregnation bath.
- the elastomeric polymer or plastomer of the impregnation bath can be chosen from the same family as the elastomers used as a second finish (in the dough preparation phase); however the polymer of the impregnation bath will be different in each case from that already used for the preparation of the surface of the fibers as a second bonding primer.
- the choice of the elastomeric impregnation resin will be determined with a view to good adhesion, that is to say good compatibility from the chemical and physical point of view between the two formulas, that is to say between the elastomer used as a second attachment primer and the elastomer for impregnation in the sheet.
- the pH of the impregnation bath is maintained at an acid value corresponding to a pH between 4 and 5 and preferably between 4 and 4.5, by adding in particular maleic acid or paratoluenesulfonic acid; adjusting the pH to obtain coagulation at the programmed temperature.
- the sheet After passing through the impregnation press and absorption of the quantity of dispersion provided, the sheet is led to the drying devices, in particular by infrared radiation and passage over heating rollers.
- the thermal rise to which the impregnated sheet is subjected then causes coagulation of the dispersion of elastomeric resin within the fibrous structure; this coagulation is accompanied by a release on the two surfaces of the sheet of a certain amount of water; it thus occurs when passing over the heating rollers a wet interface which opposes "dry” contact between the elastomeric resin and the surface of the roller and consequently prevents any parasitic deposition of this resin on the roller.
- the sheet thus formed can then receive surface coatings on one or on two sides.
- These coatings can be a simple protective varnish, but more commonly and more usefully, it will cause the establishment of layers giving antinomic properties from one side to the other, namely on one side a varnish of non-stick and hydrophobic character, while on the other side a layer facilitating the subsequent attachment of an adhesive mass or any other element to obtain a self-adhesive assembly.
- Film forming temperature greater than 10 ° C.
- BASF Polysar products with higher proportions of butyl and octyl esters
- the styrene content is between 50 and 65%.
- the film formation temperature is above 10 ° C.
- products with a styrene content of approximately 30% were chosen, the film formation temperatures of which are less than 5 ° C.
- the surface preparation can be carried out with polychloroprene dispersions having a low tendency to crystallize, the impregnation with an impregnation press compensating for this effect. Very good results are obtained with a subsequent impregnation based on polybutadiene-acrylonitrile latex and polyvinyl acetate latex or blends of these with types of polychloroprene latex (Dupont, Bayer) which do not crystallize.
- Polyvinyl acetate is suitable for surface preparation, not only as a homopolymer but also as a copolymer with acrylates maleinates and other derivatives of polyvinyl alcohol, especially since these are highly polymerized types with film forming temperatures above 10 ° C.
- an impregnating product - with regard to the uses mentioned at the beginning - it is used only as a cutting partner for the latexes of nitril, butadienestyrene or acrylic esters.
- the polyethers of propylene-ethylene, the methylether of polyvinyl alcohol, the polyoxyethylenes are coagulating agents, called “gelling agents” like other products of polycondensation of different aliphatic diols with long chains. They have the property of becoming insoluble in water during a rise in temperature after which, there is spontaneously a general coagulation of the dispersion. At the same time, the whole quantity of water is released. We work at pH values below 5.
- Polyvinyl alcohol polyacrylamide, polyacrylic acid + NH3. They are viscosity regulators and used for the purpose of increasing viscosity. Polyvinyl alcohol also gives hydrophilicity. Polyglycol, triethanolamine, glyoxal have softening, plasticizing and hydrophilic functions.
- Some resins can be used for the physical reinforcement of the fiber to fiber bond (rosin resin, rosin ester) or for the chemical crosslinking of fibers (melamine formaldehyde resins, phenolformaldehyde resins). Under very specific conditions (high temperature, energy-rich rays), the combinations of urea-formaldehyde, melamine-formaldehyde and phenol-formaldehyde also crosslink the impregnation product.
- an integral impregnation of the paper is carried out in order to constitute a pre-anchoring capable of improving the efficiency and the resistance of the adhesive layer deposited subsequently.
- the following basic formulas were used:
- the invention also covers various variants which allow, by the use of elastomeric resins, in particular natural or synthetic latexes, to obtain an impregnation of the sheet while adopting a pH lying in a wider range than previously mentioned and likely to be between 3 and 33.
- the primers generally deposited by the transformers in the form of a coating layer have a tendency over time, because of the migration of the charges, to deplete the adhesive capacity of the adhesive mass. This results in a gain in efficiency of the adhesive mass anchored to the paper having undergone the pre-anchoring impregnation according to the invention.
- the method according to the invention is therefore a factor in improving the quality and efficiency as well as a source of substantial savings; the transformer can indeed obtain identical efficiency while benefiting from a weight saving in the use of the adhesive mass of between 15 and 30%.
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Description
La présente invention concerne un procédé en vue de la préparation de matériaux en feuilles, de structure fibreuse et à base de cellulose, notamment par voie papetière humide et constituant des papiers, non tissés ou cartons, ennoblis par imprégnation de résines élastomères.The present invention relates to a process for the preparation of sheet materials, of fibrous structure and of cellulose base, in particular by wet papermaking and constituting paper, nonwoven or cardboard, ennobled by impregnation of elastomeric resins.
La présente invention permet ainsi d'obtenir à partir d'un procédé utilisant une chaîne de fabrication papetière, des feuilles fibreuses à base de cellulose, notamment lisses ou crêpées et ennoblies par diverses matières synthétiques de nature élastomères ou plastomères.The present invention thus makes it possible to obtain, from a process using a papermaking production line, fibrous sheets based on cellulose, in particular smooth or creped and ennobled by various synthetic materials of elastomeric or plastomeric nature.
Le procédé permet ainsi d'obtenir des cartons présentant des propriétés spécifiques provenant de l'imprégnation de produits constitués desdites résines et permettant l'utilisation du matériau ainsi obtenu dans des applications nombreuses tels les cuirs artificiels et la production de chaussures et articles de maroquinerie, des feuilles d'impression à haute valeur, des papiers gommés ou étiquettes ainsi que des supports de couches abrasives; l'invention permet également d'obtenir des rubans adhésifs sensibles à la pression, des substrats utilisables en tapisserie (revêtements de sols ou de murs); l'invention permet encore de réaliser des matériaux à utilisations techniques notamment pour l'enroulement et la protection d'éléments filiformes tels que cables ou cableries électriques ainsi que des enveloppes de formes diverses notamment des enveloppes de stérilisation.The process thus makes it possible to obtain cartons having specific properties originating from the impregnation of products made up of said resins and allowing the use of the material thus obtained in numerous applications such as artificial leathers and the production of shoes and leather goods, high value printing sheets, gummed papers or labels as well as abrasive layer supports; the invention also makes it possible to obtain pressure-sensitive adhesive tapes, substrates usable in tapestry (floor or wall coverings); the invention also makes it possible to produce materials for technical uses, in particular for winding and protecting filiform elements such as cables or electrical cables, as well as envelopes of various shapes, in particular sterilization envelopes.
On connaît déjà l'incorporation dans la masse de la feuille cellulosique d'une résine élastomère notamment au niveau de la presse d'imprégnation; cette résine présente des avantages au niveau de l'utilisation du produit fini en apportant au papier des qualités de stabilisation, de solidité et de résistance mécanique ainsi que de flexibilité recherchée pour de nombreuses applications.We already know the incorporation into the mass of the sheet cellulosic of an elastomeric resin, in particular at the level of the impregnation press; this resin has advantages in terms of the use of the finished product by providing the paper with qualities of stabilization, solidity and mechanical resistance as well as flexibility sought for many applications.
On sait également que l'utilisation de telles résines présente des difficultés particulières dans la phase de fabrication.It is also known that the use of such resins presents particular difficulties in the manufacturing phase.
En effet les propriétés bien connues (et précisément recherchées dans cette application) des résines élastomères provoquent trop facilement l'adhérence du papier imprégné, lors de la phase de séchage, sur les parois des cylindres sécheurs.Indeed, the well known properties (and precisely sought in this application) of elastomeric resins too easily cause the adhesion of impregnated paper, during the drying phase, on the walls of the drying cylinders.
Il suit que petit à petit, une partie de la résine élastomère présente en surface sur la feuille, lors du séchage, vient à adhérer à la paroi du cylindre de séchage; ceci entraîne par un phénomène cumulatif l'adhérence ultérieure d'une nouvelle couche mince de latex provenant de la feuille successive.It follows that little by little, part of the elastomeric resin present on the surface on the sheet, during drying, comes to adhere to the wall of the drying cylinder; this brings about by a cumulative phenomenon the subsequent adhesion of a new thin layer of latex coming from the successive sheet.
Il suit que le cylindre de séchage tend à retenir à sa surface la feuille en cours de séchage donc ne possédant que des propriétés mécaniques faibles qui vient à se déchirer avec rupture dans la continuité du déroulement.It follows that the drying cylinder tends to retain on its surface the sheet during drying therefore having only weak mechanical properties which comes to tear with rupture in the continuity of the course.
Les cylindres par ailleurs se trouvent régulièrement encrassés par les dépôts de résines, ce qui entraîne la nécessité d'arrêts réguliers en vue d'opérations de nettoyage, entraînant un abaissement du rendement général de la fabrication.The cylinders, moreover, are regularly fouled by the deposits of resins, which leads to the need for regular stops for cleaning operations, resulting in a lowering of the general production yield.
Etant donné l'intérêt des produits papetiers à imprégnation de résines élastomères ou plastomères, on a déjà cherché dans le passé à résoudre cette difficulté, à remédier aux inconvénients ci-dessus, c'est-à-dire à éviter le dépôt partiel de couches de résine lors du séchage depuis la feuille en cours de séchage sur le cylindre sécheur.Given the interest of paper products impregnated with elastomeric or plastomeric resins, efforts have already been made in the past to resolve this difficulty, to remedy the above drawbacks, that is to say to avoid partial deposition of layers. resin when drying from the sheet being dried on the drying cylinder.
Une première solution consistait à revêtir les cylindres et rouleaux de séchage par une résine anti-adhérente et à faible coefficient de frottement telles que les résines fluorocarbonées.A first solution consisted in coating the drying cylinders and rollers with a non-stick resin with a low coefficient of friction such as fluorocarbon resins.
Cette solution connaît cependant des limites dans la mesure où les cylindres de séchage sont nécessairement maintenus à une température permettant de provoquer l'évaporation de l'eau présente dans la feuille en cours de séchage; et la permanence de cette charge thermique au niveau du revêtement fluorocarboné entraîne une dégradation lente mais régulière de cette couche avec la formation de micro fentes et de fissures capillaires amplifiée par l'action des savons présents dans les produits d'imprégnation (en tant qu'agents de surface); de sorte que le latex ou les résines élastomères finissent par se loger dans ces cavités et par entraînement se déposent sur l'ensemble des cylindres sécheurs en provoquant des salissures.This solution, however, has limits insofar as the drying cylinders are necessarily maintained at a temperature making it possible to cause the evaporation of the water present in the sheet during drying; and the permanence of this thermal charge at the fluorocarbon coating causes a slow but regular degradation of this layer with the formation of micro cracks and hair cracks amplified by the action of soaps present in the impregnation products (as surfactants); so that the latex or the elastomeric resins end up being housed in these cavities and by entrainment are deposited on the set of the drying cylinders causing dirt.
Une autre solution a été également préconisée qui consiste à adjoindre à la résine élastomérique des agents anti-adhérents et constitués de polymères à longues molécules ou de polymères contenant des groupements fonctionnels d'acylamides. Ces substances en raison de leur effet anti-adhérent provoqué notamment par les amides d'acides gras, peuvent maintenir la feuille jusqu'à l'enrouleuse sans qu'elle ne colle.Another solution has also been recommended which consists in adding to the elastomeric resin non-stick agents and consisting of polymers with long molecules or of polymers containing functional groups of acylamides. These substances, due to their non-stick effect caused in particular by fatty acid amides, can hold the sheet up to the reel without it sticking.
Cette solution présente cependant également des inconvénients dans la mesure où il a été constaté que des monomères se libèrent par décomposition du produit anti-adhérent lors du vieillissement ultérieur de la feuille ou par suite de défauts lors de la fabrication de l'agent anti-adhérent, notamment s'il s'agit d'un polymérisat à longues chaînes.However, this solution also has drawbacks insofar as it has been observed that monomers are released by decomposition of the non-stick product during the subsequent aging of the sheet or as a result of defects during the manufacture of the non-stick agent. , especially if it is a polymer with long chains.
On a constaté dans de telles conditions qu'au niveau du produit final, les propriétés recherchées de ce dernier se trouvent handicapées et réduites; notamment l'adhérence de la feuille dans le cas d'une feuille adhésive sensible à la pression, se trouve limitée et minorée; et dans le cas de l'utilisation de tels papiers comme support d'impression, l'imprimabilité se trouve également limitée.It was found under such conditions that at the end product, the desired properties of the latter are disabled and reduced; in particular the adhesion of the sheet in the case of an adhesive sheet sensitive to pressure, is limited and reduced; and in the case of the use of such papers as a printing medium, the printability is also limited.
On a également préconisé une solution permettant la fabrication d'une feuille à base de fibres de cellulose contenant une imprégnation élastomérique et dans laquelle on incorpore dans la matière de départ des composés organiques électro-positifs cationiques en vue de réduire le potentiel zeta.A solution has also been recommended which allows the manufacture of a sheet based on cellulose fibers containing an elastomeric impregnation and in which organic electro-positive cationic compounds are incorporated into the starting material in order to reduce the zeta potential.
L'invention permet de fabriquer des produits papetiers contenant une proportion importante de composition d'ennoblissement sous forme de polymères et élastomères ou plastomères et sans aucun risque de déposition d'éléments provenant de la résine d'ennoblissement au long de la machinerie et notamment au niveau des rouleaux de séchage.The invention makes it possible to manufacture paper products containing a large proportion of finishing composition in the form of polymers and elastomers or plastomers and without any risk of deposition of elements originating from the finishing resin along the machinery and in particular at level of drying rollers.
On connait déjà par le brevet EP-A-00 670 76 l'adjonction d'un adjuvant, constitué d'un polyelectrolyte, au produit d'annoblissement, pour améliorer son greffage sur les Fonctions cellulosiques l'invention concerne un procédé de préparation par voie humide de matériaux en feuilles de structure fibreuse à base de cellulose, tels que des papiers, cartons ou non tissés dans lequel la structure fibreuse en nappe est enrichie de matériaux d'ennoblissement constitués de polymères synthétiques de résines élastomères ou plastomères, et dans lequel la feuille humide formée sur la toile sans fin, passe dans une presse d'imprégnation, pour y recevoir dans sa masse, avant séchage sur des rouleaux chauffants, l'imprégnation du matériau d'ennoblissement constitué par la résine élastomère ou plastomère, sous forme d'une dispersion aqueuse,
caractérisé en ce que ladite dispersion aqueuse contient un additif propre à provoquer la coagulation spontanée de ladite résine au-delà d'une température donnée avec relargage d'une quantité d'eau, ainsi apte à constituer une interface s'opposant à l'adhérence du produit élastomère ou plastomère sur le cylindre chauffant de séchage ultérieur et ledit additif de coagulation de la résine élastomère ou plastomères est constitué d'agents gélifiants tels que les produits de polycondensation des polyols aliphatiques à longues chaînes et plus spécialement les polyesters de propylène éthylène, le méthylester de l'alcool polyvinylique, les polyoxyéthylènes.We already know from patent EP-A-00 670 76 the addition of an adjuvant, consisting of a polyelectrolyte, to the ennobling product, to improve its grafting on the cellulosic Functions, the invention relates to a process for wet preparation of cellulose-based fibrous structure sheet materials, such as paper, cardboard or nonwovens in which the fibrous web structure is enriched with finishing materials made of synthetic polymers of elastomeric or plastomeric resins, and in which the wet sheet formed on the endless fabric passes through an impregnation press, to receive there in its mass, before drying on heating rollers, the impregnation of the finishing material constituted by the elastomeric or plastomeric resin, in the form of an aqueous dispersion,
characterized in that said aqueous dispersion contains an additive capable of causing spontaneous coagulation of said resin above a given temperature with the release of a quantity of water, thus capable of constituting an interface opposing adhesion of the elastomeric or plastomeric product on the heating cylinder for subsequent drying and said coagulation additive of the elastomeric or plastomeric resin consists of gelling agents such as the polycondensation products of long-chain aliphatic polyols and more particularly the polyesters of propylene ethylene, polyvinyl alcohol methyl ester, polyoxyethylenes.
Dans une première forme de réalisation on utilise une pâte à fibres longues permettant une absorption suffisante et des résistances adaptées à l'usage auquel le produit est destiné; la pâte à fibres longues, blanchie, demi-blanchie ou écrue est peu raffinée (16 à 30°SR); on maintient le milieu à un pH sensiblement neutre, compris entre 6,5 et 7,5; on notera cependant que toutes les pâtes, y compris les pâtes recyclées peuvent être employées dans le cadre du procédé d'ennoblissement selon l'invention.
Les fibres de façon classiques et conventionnelles sont désintégrées dans le pulper et éventuellement raffinées et dans la pâte ainsi réalisée est alors introduit une première composition d'accrochage ou un premier apprêt constituant un produit de rétention et choisi parmi les produits désignés sous les marques déposées Rétaminol (Bayer), Cartarétine (Sandoz), Percol (Allied Colloid); ce premier apprêt est introduit dans une proportion comprise entre 0,1 et 3% du total.In a first embodiment, a long fiber paste is used which allows sufficient absorption and resistance adapted to the use for which the product is intended; the long-fiber, bleached, semi-bleached or unbleached pulp is not very refined (16 to 30 ° SR); the medium is maintained at a substantially neutral pH, between 6.5 and 7.5; it will be noted however that all the pastes, including the recycled pastes can be used within the framework of the finishing process according to the invention.
The fibers in a conventional and conventional manner are disintegrated in the pulper and possibly refined and in the paste thus produced is then introduced a first bonding composition or a first finish constituting a retention product and chosen from the products designated under the registered trademarks Retaminol (Bayer), Cartaretine (Sandoz), Percol (Allied Colloid); this first primer is introduced in a proportion of between 0.1 and 3% of the total.
Après un intervalle de temps de 15 à 20 minutes, pendant lequel la pâte continue à être travaillée, on introduit dans cette pâte un second apprêt constitué d'un polymérisat relativement dur et polaire, dégageant une énergie de surface assez grande; de préférence ce polymérisat est un élastomère et il est dispersé dans la masse fibreuse en de très fines particules sous forme de dispersion aqueuse; on obtient ainsi une grande aptitude à l'adhésion entre les élastomères, ou dispersion d'élastomères ou de plastomères avec les fibres de la pâte.After a time interval of 15 to 20 minutes, during which the dough continues to be worked, a second primer is introduced into this dough consisting of a relatively hard and polar polymer, giving off a fairly large surface energy; preferably this polymer is an elastomer and it is dispersed in the fibrous mass in very fine particles in the form of an aqueous dispersion; a great aptitude for adhesion between the elastomers is thus obtained, or dispersion of elastomers or plastomers with the fibers of the pulp.
Parmi les élastomères préférés on a noté le polychloroprène, le polybutadiène acrylonitrile, le polyacrylate et le polyacétate de vinyle. Ce second apprêt élastomérique est introduit dans une proportion de 0,1 à 3% du total.Among the preferred elastomers, polychloroprene, polybutadiene acrylonitrile, polyacrylate and polyvinyl acetate have been noted. This second elastomeric primer is introduced in a proportion of 0.1 to 3% of the total.
Ainsi qu'on l'a indiqué le produit de rétention introduit dans la pâte abaisse le potentiel zeta et réduit en même temps le degré de raffinage par fixation des fines et par réticulation entre les molécules polyélectrolytes à longues chaînes et les fibres cellulosiques de la feuille. Il en résulte une stabilisation de la structure de la feuille ou, en d'autres mots, une cohésion de la feuille sans perte du pouvoir absorbant. Les adjonctions succesives - à intervalles déterminés - des produits auxiliaires à la pâte (produit de rétention et dispersion polymère) répartissent très finement sur la surface de la fibre où ils présentent - sous forme de voile - un fond adhésif excellent pour le latex "mou" subséquent et constituant le produit d'ennoblissement principal.As indicated, the retention product introduced into the paste lowers the zeta potential and at the same time reduces the degree of refining by fixing the fines and by crosslinking between the long-chain polyelectrolyte molecules and the cellulose fibers of the sheet. . This results in stabilization of the structure of the sheet or, in other words, cohesion of the sheet without loss of absorbency. The successive additions - at predetermined intervals - of auxiliary products to the dough (retention product and polymer dispersion) distribute very finely over the surface of the fiber where they present - in the form of a veil - an adhesive base excellent for "soft" latex subsequent and constituting the main finishing product.
Après 20 à 30 minutes, il y a absorption par la masse fibreuse des fines et des adjonctions mentionnées. En filtrant la pâte, on constate que l'eau est absolument claire.After 20 to 30 minutes, there is absorption by the fibrous mass of the fines and the additions mentioned. By filtering the dough, we see that the water is absolutely clear.
La pâte préparée et modifiée en surface sera amenée en tête de la machine à la concentration de 0,4% dans l'eau. La quantité nécessaire de résine de réticulation (4 à 8%) y est ajoutée en continu.The prepared and surface-modified dough will be brought to the top of the machine at a concentration of 0.4% in water. The necessary quantity of crosslinking resin (4 to 8%) is added thereto continuously.
La feuille est alors formée sur la toile sans fin pour être finalement séchée.
La formation de la feuille se fait sans obstacle au feutrage de la fibre c'est à dire sans entrave à la formation des ponts hydriques qui lient naturellement les fibres entre elles. Le matériau fibreux sortant de la toile sans fin est séché jusqu'à un degré d'humidité de 8 à 15% et il possède alors un pouvoir d'absorption adéquate réglable au départ par le raffinage de la pâte.The sheet is then formed on the endless canvas to be finally dried.
The formation of the sheet is done without obstacle to the felting of the fiber, that is to say without hindrance to the formation of water bridges which naturally bind the fibers together. The fibrous material leaving the endless fabric is dried to a humidity level of 8 to 15% and it then has an adequate absorption power which can be adjusted initially by refining the dough.
La feuille est alors introduite dans la presse d'imprégnation, au degré d'humidité précité (8 à 15%) pour être introduite dans le bain d'imprégnation comportant entre 15 et 45% de résine élastomère ou plastomère sous forme de dispersion aqueuse.
Le bain d'imprégnation à base de résine élastomère comporte, selon un élément caractéristique de l'invention, l'incorporation d'un composant constituant un agent gélifiant propre à provoquer la coagulation de la résine élastomère à partir d'un certain niveau thermique.The sheet is then introduced into the impregnation press, at the aforementioned degree of humidity (8 to 15%) to be introduced into the impregnation bath comprising between 15 and 45% of elastomeric resin or plastomer in the form of an aqueous dispersion.
The impregnation bath based on elastomeric resin comprises, according to a characteristic element of the invention, the incorporation of a component constituting a gelling agent capable of causing coagulation of the elastomeric resin from a certain thermal level.
Le bain d'imprégnation est maintenu à une température inférieure à ladite température préajustée de coagulation de sorte que la dispersion est stable au niveau du bain d'imprégnation. On précisera que le polymère élastomérique ou plastomère du bain d'imprégnation peut être choisi dans la même famille que les élastomères utilisés à titre de second apprêt (dans la phase de préparation de la pâte); cependant le polymère du bain d'imprégnation sera différent dans chaque cas de celui dejà utilisé pour la prépation de la surface des fibres en tant que second apprêt d'accrochage. Le choix de la résine élastomère d'imprégnation sera déterminé en vue d'une bonne adhésion, c'est-à-dire d'une bonne compatibilité au point de vue chimique et physique entre les deux formules c'est-à-dire entre l'élastomère utilisé à titre de second apprêt d'accrochage et l'élastomère d'imprégnation dans la feuille.The impregnation bath is maintained at a temperature below said pre-adjusted coagulation temperature so that the dispersion is stable at the level of the impregnation bath. It will be specified that the elastomeric polymer or plastomer of the impregnation bath can be chosen from the same family as the elastomers used as a second finish (in the dough preparation phase); however the polymer of the impregnation bath will be different in each case from that already used for the preparation of the surface of the fibers as a second bonding primer. The choice of the elastomeric impregnation resin will be determined with a view to good adhesion, that is to say good compatibility from the chemical and physical point of view between the two formulas, that is to say between the elastomer used as a second attachment primer and the elastomer for impregnation in the sheet.
Selon un cas de mise en oeuvre particulière de l'invention, on précisera que le pH du bain d'imprégnation est maintenu à une valeur acide correspondant à un pH compris entre 4 et 5 et de préférence entre 4 et 4,5, par adjonction notamment d'acide maléique ou d'acide paratoluènesulfonique; l'ajustement du pH permettant d'obtenir la coagulation à la température programmée.According to a particular implementation of the invention, it will be specified that the pH of the impregnation bath is maintained at an acid value corresponding to a pH between 4 and 5 and preferably between 4 and 4.5, by adding in particular maleic acid or paratoluenesulfonic acid; adjusting the pH to obtain coagulation at the programmed temperature.
Après passage dans la presse d'imprégnation et absorption de la quantité de dispersion prévue, la feuille est conduite vers les dispositifs de séchage notamment par radiations infrarouges et passage sur des rouleaux chauffants.After passing through the impregnation press and absorption of the quantity of dispersion provided, the sheet is led to the drying devices, in particular by infrared radiation and passage over heating rollers.
L'élévation thermique à laquelle la feuille imprégnée est soumise provoque alors une coagulation de la dispersion de résine élastomère au sein de la structure fibreuse; cette coagulation s'accompagne d'un relargage sur les deux surfaces de la feuille d'une certaine quantité d'eau; il se produit ainsi lors du passage sur les rouleaux chauffants une interface humide qui s'oppose à un contact "à sec" entre la résine élastomère et la surface du rouleau et empêche par conséquent toute déposition parasite de cette résine sur le rouleau.The thermal rise to which the impregnated sheet is subjected then causes coagulation of the dispersion of elastomeric resin within the fibrous structure; this coagulation is accompanied by a release on the two surfaces of the sheet of a certain amount of water; it thus occurs when passing over the heating rollers a wet interface which opposes "dry" contact between the elastomeric resin and the surface of the roller and consequently prevents any parasitic deposition of this resin on the roller.
On peut ainsi obtenir le déroulement de la feuille, sur les cylindres sécheurs, sans provoquer la formation de dépôt de couches de résine élastomère comme dans la mise des procédés antérieurs.It is thus possible to obtain the unwinding of the sheet, on the drying cylinders, without causing the formation of deposits of layers of elastomeric resin as in the implementation of the previous processes.
La feuille ainsi formée peut recevoir alors des enductions superficielles sur une ou sur deux faces.
Ces enductions peuvent être un simple vernis de protection mais plus courramment et plus utilement on provoquera la mise en place de couches conférent des propriétés antinomiques d'une face à l'autre à savoir sur une face un vernis à caractère anti-adhésif et hydrophobe, tandis que sur l'autre face une couche facilitant l'accrochage ultérieur d'une masse adhésive ou de tout autre élément pour obtenir un ensemble auto-adhésif.
On a donné ci-après une présentation monographique des divers produits et compositions susceptibles d'intervenir dans la mise en oeuvre du procédé selon l'invention.The sheet thus formed can then receive surface coatings on one or on two sides.
These coatings can be a simple protective varnish, but more commonly and more usefully, it will cause the establishment of layers giving antinomic properties from one side to the other, namely on one side a varnish of non-stick and hydrophobic character, while on the other side a layer facilitating the subsequent attachment of an adhesive mass or any other element to obtain a self-adhesive assembly.
We have given below a monographic presentation of the various products and compositions likely to be involved in the implementation of the method according to the invention.
Pour la préparation de la surface des fibres il y a utilisation de polyméthylacrylates connus pour leur dureté. Température de formation du film: supérieure à 10°C. Comme composant pour des bains d'imprégnation, on a choisi des produits avec des parts plus importantes d'esters de butyl et d'octyl (BASF Polysar). Température de formation du film : inférieure à 5°C.For the preparation of the surface of the fibers, use is made of polymethylacrylates known for their hardness. Film forming temperature: greater than 10 ° C. As a component for impregnation baths, products with higher proportions of butyl and octyl esters (BASF Polysar) have been chosen. Film forming temperature: less than 5 ° C.
Il peut être utilisé également dans la préparation de la surface à condition que la teneur en styrène soit comprise entre 50 et 65%. La température de formation du film se situe au dessus de 10°C.
Pour le bain d'imprégnation il a été choisi des produits avec une teneur en styrène d'environ 30% dont les températures de formation du film sont inférieures à 5°C .It can also be used in the preparation of the surface provided that the styrene content is between 50 and 65%. The film formation temperature is above 10 ° C.
For the impregnation bath, products with a styrene content of approximately 30% were chosen, the film formation temperatures of which are less than 5 ° C.
Nous nous sommes servis de types contenant environ 40% d'acrylonitrile, 55% de butadiène et, en outre, de l'acide méthacrylique, de l'acide maléique ou/et de l'acide itaconique (Bayer, Polysar, Synthomer). Température de formation du film: supérieure à 10°C.
Comme produits d'imprégnation sont appropriés: ceux avec une quote-part de butadiène supérieure à 50% le reste étant une partie de styrène et de nitrile. La température de formation du film est inférieure à 5°C.We used types containing about 40% acrylonitrile, 55% butadiene and, in addition, methacrylic acid, maleic acid and / or itaconic acid (Bayer, Polysar, Synthomer). Film forming temperature: greater than 10 ° C.
Suitable impregnation products: those with a share of butadiene greater than 50%, the rest being part of styrene and nitrile. The film forming temperature is less than 5 ° C.
La préparation de surface peut être effectuée avec des dispersions de polychloroprène ayant une faible tendance à la cristallisation, l'imprégnation à la presse d'imprégnation compensant cet effet. On obtient de très bons résultats avec une imprégnation subséquente à base de latex de polybutadiène-acrylonitrile et de latex de polyvinyl-acétate ou des coupages de ceux-ci avec des types de latex de polychloroprène (Dupont, Bayer) qui ne cristallisent pas.The surface preparation can be carried out with polychloroprene dispersions having a low tendency to crystallize, the impregnation with an impregnation press compensating for this effect. Very good results are obtained with a subsequent impregnation based on polybutadiene-acrylonitrile latex and polyvinyl acetate latex or blends of these with types of polychloroprene latex (Dupont, Bayer) which do not crystallize.
L'acétate de polyvinylique est approprié pour la préparation de la surface, non seulement comme homopolymère mais aussi comme copolymère avec des acrylates maléinates et d'autres dérivés de l'alcool polyvinylique, d'autant qu'il s'agit de types hautement polymérisés avec des températures de formation de film supérieure à IO°C . Comme produit d'imprégnation - en ce qui concerne les utilisations mentionnées au début - il est employé uniquement comme partenaire de coupage pour les latex de nitril, butadiènestyrène ou d'esters acryliques.Polyvinyl acetate is suitable for surface preparation, not only as a homopolymer but also as a copolymer with acrylates maleinates and other derivatives of polyvinyl alcohol, especially since these are highly polymerized types with film forming temperatures above 10 ° C. As an impregnating product - with regard to the uses mentioned at the beginning - it is used only as a cutting partner for the latexes of nitril, butadienestyrene or acrylic esters.
Les polyéthers de propylène-éthylène, le méthyléther de l'alcool polyvinylique, les polyoxyéthylènes sont des agents coagulants, dit "agents gélifiants" comme d'autres produits de polycondensation de différents diols aliphatiques à longues chaînes. Ils ont la propriété de devenir insolubles dans l'eau lors d'une élévation de température après quoi, il y a spontanément une coagulation générale de la dispersion. En même temps, toute la quantité d'eau est libérée On travaille à des valeurs de pH inférieures à 5.The polyethers of propylene-ethylene, the methylether of polyvinyl alcohol, the polyoxyethylenes are coagulating agents, called "gelling agents" like other products of polycondensation of different aliphatic diols with long chains. They have the property of becoming insoluble in water during a rise in temperature after which, there is spontaneously a general coagulation of the dispersion. At the same time, the whole quantity of water is released. We work at pH values below 5.
Alcool polyvinylique, polyacrylamide, acide polyacrylique + NH3.
Ce sont des régulateurs de viscosité et utilisés dans le but d'augmenter la viscosité. L'alcool polyvinylique donne également de l'hydrophilie.
Le polyglycol, la triéthanolamine, le glyoxal ont des fonctions adoucissantes, plastifiantes et hydrophiles.Polyvinyl alcohol, polyacrylamide, polyacrylic acid + NH3.
They are viscosity regulators and used for the purpose of increasing viscosity. Polyvinyl alcohol also gives hydrophilicity.
Polyglycol, triethanolamine, glyoxal have softening, plasticizing and hydrophilic functions.
On peut employer certaines résines pour le renforcement physique de la liaison fibre à fibre (résine de colophane, ester de colophane) ou pour la réticulation chimique des fibres (résines de mélamine formaldéhyde, des résines de phénolformaldéhyde). Dans des conditions bien précises (température élevée, rayons riches en énergie), les combinaisons d'urée-formol, de mélamine-formol et de phénol-formol réticulent également le produit d'imprégnation.Some resins can be used for the physical reinforcement of the fiber to fiber bond (rosin resin, rosin ester) or for the chemical crosslinking of fibers (melamine formaldehyde resins, phenolformaldehyde resins). Under very specific conditions (high temperature, energy-rich rays), the combinations of urea-formaldehyde, melamine-formaldehyde and phenol-formaldehyde also crosslink the impregnation product.
- a) Emulgateurs: pour la stabilisation de la dispersion et pour le réglage de la température souhaitée de coagulation.a) Emulsifiers: for stabilizing dispersion and for setting the desired coagulation temperature.
- b) Capteurs de métaux lourds (Fe, Co, Ni, Cu, Mn) comme par exemple éthylènediamine tetr(a)-acide acétique. Les ions de métaux lourds cités ci-dessus sont des poisons du caoutchouc.b) Heavy metal sensors (Fe, Co, Ni, Cu, Mn) such as for example ethylenediamine tetr (a) -acetic acid. The heavy metal ions mentioned above are poisons from rubber.
- c) Colorants et chargesc) Dyes and fillers
Un des aspects de l'invention, qui concourt lui aussi à l'ennoblissement du papier, est l'application du vernis de protection d'une face de la feuille. Ont été utilisés comme produits de base: des dispersions de PVC, de PVDC, de PVAC, d'ester de polyacryl, de polystyrène et d'autres matières polymères en dispersion aqueuse.
Pour l'hydrofugation et l'antiadhésion, on peut utiliser différentes préparations:
- soit celles à base de chrome trivalent complexées avec de l'acide stéarique
- soit celles à base de résines de mélamines et d'acides gras à longues chaînes (Sunsize) qui donnent de bons vernis couvrant. Les résines les mieux adaptées sont les mélamines formol et les urée formol solubles dans l'eau et réticulables. Ces enductions peuvent être appelées des enductions "release" employées couramment pour des rubans adhésifs.
For waterproofing and antiadhesion, different preparations can be used:
- either those based on trivalent chromium complexed with stearic acid
- or those based on melamine resins and long chain fatty acids (Sunsize) which give good covering varnishes. The most suitable resins are formaldehyde melamines and water-soluble crosslinkable ureas. These coatings can be called "release" coatings commonly used for adhesive tapes.
Pour avoir un bon accrochage des substances adhésives sur la feuille imprégnée, on procède à une imprégnation intégrale du papier en vue de constituer in pré-ancrage propre à améliorer l'efficacité et la tenue de la couche adhésive déposée ultérieurement.
Les formules de base suivantes ont été employées:To have a good adhesion of the adhesive substances on the impregnated sheet, an integral impregnation of the paper is carried out in order to constitute a pre-anchoring capable of improving the efficiency and the resistance of the adhesive layer deposited subsequently.
The following basic formulas were used:
L'invention couvre également diverses variantes qui permettent par l'utilisation des résines élastomères notamment des latex naturels ou synthétiques d'obtenir une imprégnation de la feuille tout en adoptant un pH se situant dans une gamme plus large que précédemment évoqués et susceptible de se situer entre 3 et 33.The invention also covers various variants which allow, by the use of elastomeric resins, in particular natural or synthetic latexes, to obtain an impregnation of the sheet while adopting a pH lying in a wider range than previously mentioned and likely to be between 3 and 33.
On peut en outre obtenir le film d'eau d'isolation relarguer depuis la coagulation de la résine, grâce à un choc thermique créé notamment par l'émission d'un rayonnement de longueur d'ondes appropriée.It is also possible to obtain the insulation water film released from the coagulation of the resin, thanks to a thermal shock created in particular by the emission of radiation of appropriate wavelength.
Il est ainsi possible d'enrichir la feuille d'un primer ou pré-ancrage facilitant et optimisant la dépose de la masse adhésive ultérieure.It is thus possible to enrich the sheet with a primer or pre-anchoring facilitating and optimizing the removal of the subsequent adhesive mass.
On a en effet constaté que les primer généralement déposés par les transformateurs sous forme d'une couche d'enduction ont tendance dans le temps, à cause de la migration des charges à appauvrir la capacité adhésive de la masse adhésive. Il en résulte un gain d'efficacité de la masse adhésive ancrée au papier ayant subi l'imprégnation de pré-ancrage selon l'invention.
Le procédé selon l'invention est donc facteur de l'amélioration de la qualité et de l'efficacité en même temps qu'une source d'économie substancielle; le transformateur peut en effet obtenir une efficacité identique tout en bénéficiant d'un gain de poids dans l'utilisation de la masse adhésive compris entre 15 et 30%.It has in fact been found that the primers generally deposited by the transformers in the form of a coating layer have a tendency over time, because of the migration of the charges, to deplete the adhesive capacity of the adhesive mass. This results in a gain in efficiency of the adhesive mass anchored to the paper having undergone the pre-anchoring impregnation according to the invention.
The method according to the invention is therefore a factor in improving the quality and efficiency as well as a source of substantial savings; the transformer can indeed obtain identical efficiency while benefiting from a weight saving in the use of the adhesive mass of between 15 and 30%.
Claims (8)
- Process for preparing by wet method materials in sheet form of fibrous structure based on cellulose, such as papers, cardboards or non-wovens, in which the fibrous structure in lap is enriched with improvement materials constituted by synthetic polymers, elastomer or plastomer resins and in which the wet sheet formed on the endless wire web, passes in an impregnation press to receive in its mass, before drying on heating rollers, the impregnation of the improvement material constituted by the elastomer or plastomer resin, in the form of an aqueous dispersion,
characterized in that said aqueous dispersion contains an additive adapted to provoke spontaneous coagulation of said resin beyond a given temperature with release of a quantity of water, and adapted to constitute an interface opposing adherence of the elastomer or plastomer product on the heating cylinder for subsequent drying and said additive for coagulation of the elastomer or plastomer resin is constituted by gelling agents such as the products of polycondensation of the long-chain aliphatic polyols and more especially the polyesters of propylene ethylene, the methylester of polyvinyl alcohol, the polyoxyethylenes. - Process according to Claim 1,
characterized in that there is incorporated in the preparation of the paper pulp, upstream of the formation of the sheet, a first finish with a view to the subsequent catching of the elastomer resin, and this first finish is constituted by a retention product adapted to lower the zeta potential of the earth, constituted by a long-chain polyelectrolyte polymer, selected from the family including dispersions of polychloroprene, polybutadiene-styrene, polymethacrylate, polyvinyl acetate, a second finish for catching is introduced in the paper pulp after a period of time greater than 15 minutes and preferably of the order of 20 minutes, after introduction of the first finish, this second finish being constituted by a synthetic elastomer resin, selected to be different and compatible with the elastomer resin constituting the improvement or subsequent impregnation product and presented in the form of aqueous dispersion, said second finish is selected from the family including polychloroprene, polybutadiene acrylonitrile, polyacrylate, polyvinyl acetate, polybutadiene styrene, as well as mixture or copolymers thereof. - Process according to one of Claims 1 or 2,
characterized in that the impregnation bath supplying the impregnation press and containing the dispersions of elastomer or plastomer resins is made from an aqueous dispersion of resins selected from natural latex, polybutadiene acrylonitrile, polyvinylacetate styrene, the butadiene acrylonitrile and styrene copolymer, the copolymers of acrylic esters and vinylacetate, as well as mixture or copolymer thereof. - Process according to one of Claims 1 to 3,
characterized in that the release of the isolation water is provoked by a thermal shock obtained by the emission of aradiation of appropriate wave length. - Process according to one of Claims 1 to 4,
characterized in that the impregnation bath supplying the impregnation press comprises additives constituted by viscosity regulators such as polyvinyl alcohols, polyacrymalides, polyacrylic acid with the addition of nitric acid. - Process according to one of Claims 1 to 5,
characterized in that the impregnation bath also carries manufacturing additives selected from the softening, plasticizer and hydrophilic agents, such as polyglycol, triethanolamine or glyoxal, emulgators for adjusting the temperature of coagulation of the elastomer resin, heavy metal sensors such as ethylenediamine tetra acetic acid as well as colorants and fillers. - Process according to one of Claims 1 to 6,
characterized in that it comprises a coating phase after drying and on at least one face, from a protective varnish selected from the family including the dispersions of polyvinyl chloride, polyvinylacetate, polyacryl ester, polystyrene in aqueous dispersion. - Process according to one of Claims 1 to 7,
characterized with a view to giving one face of the material thus produced water-repellant and anti-adhesion properties, the corresponding face of the sheet receives a coating of product selected from the family including the complexes of stearic acid and trivalent chromium, the resins of melamines, of long-chain fatty acids, the malamine-formaldehydes, and the water-soluble and cross-linkable urea-formaldehydes.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8907198A FR2647819B1 (en) | 1989-05-31 | 1989-05-31 | PROCESS FOR THE PREPARATION OF SHEET-LIKE AND CELLULOSE-BASED FIBROUS PRODUCTS BY PAPER AND ENRICHED WITH ELASTOMERIC RESINS |
| FR8907198 | 1989-05-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0406039A1 EP0406039A1 (en) | 1991-01-02 |
| EP0406039B1 true EP0406039B1 (en) | 1993-11-10 |
Family
ID=9382228
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19900401474 Expired - Lifetime EP0406039B1 (en) | 1989-05-31 | 1990-05-31 | Process for making fibrous sheet products from cellulose by a paper-making process, said products being enriched with elastomeric resins |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0406039B1 (en) |
| DE (1) | DE69004499T2 (en) |
| FR (1) | FR2647819B1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR3035082B1 (en) * | 2015-04-16 | 2017-11-24 | Cie Des Gaz De Petrole Primagaz | PACKAGING STRUCTURE |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2887431A (en) * | 1957-01-11 | 1959-05-19 | Armstrong Cork Co | Method of forming a slurry of different filler particles uniformly coated with a binder |
| FR2519663B2 (en) * | 1981-05-12 | 1985-08-16 | Jeandheurs Papeteries | IMPROVEMENTS IN THE PROCESS FOR THE MANUFACTURE IN AQUEOUS MEDIA OF LEAVES OF FIBROUS MATERIALS CONTAINING LATEX OR THE LIKE AND / OR PHENOPLASTS OR AMINOPLASTS, NEW SHEETS THUS OBTAINED AND THEIR REUSE |
| FI77707C (en) * | 1987-06-04 | 1989-04-10 | Valmet Paper Machinery Inc | Procedure for contactless drying of a paper or cardboard web. |
-
1989
- 1989-05-31 FR FR8907198A patent/FR2647819B1/en not_active Expired - Fee Related
-
1990
- 1990-05-31 DE DE1990604499 patent/DE69004499T2/en not_active Expired - Fee Related
- 1990-05-31 EP EP19900401474 patent/EP0406039B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| FR2647819A1 (en) | 1990-12-07 |
| FR2647819B1 (en) | 1991-09-20 |
| EP0406039A1 (en) | 1991-01-02 |
| DE69004499T2 (en) | 1994-06-09 |
| DE69004499D1 (en) | 1993-12-16 |
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