NO130953B - - Google Patents
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- NO130953B NO130953B NO33170A NO33170A NO130953B NO 130953 B NO130953 B NO 130953B NO 33170 A NO33170 A NO 33170A NO 33170 A NO33170 A NO 33170A NO 130953 B NO130953 B NO 130953B
- Authority
- NO
- Norway
- Prior art keywords
- paper
- fibers
- polypropylene
- epichlorohydrin
- weight
- Prior art date
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- 239000000835 fiber Substances 0.000 claims description 61
- 229920001155 polypropylene Polymers 0.000 claims description 44
- -1 polypropylene Polymers 0.000 claims description 42
- 239000004743 Polypropylene Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 27
- 229920000642 polymer Polymers 0.000 claims description 18
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 13
- 229920003043 Cellulose fiber Polymers 0.000 claims description 9
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims 2
- 239000011593 sulfur Substances 0.000 claims 2
- 239000007900 aqueous suspension Substances 0.000 claims 1
- 150000004982 aromatic amines Chemical class 0.000 claims 1
- HWMMYAWUTCKNKH-UHFFFAOYSA-N n,n'-dicyclohexylhexane-1,6-diamine Chemical compound C1CCCCC1NCCCCCCNC1CCCCC1 HWMMYAWUTCKNKH-UHFFFAOYSA-N 0.000 claims 1
- 150000003139 primary aliphatic amines Chemical class 0.000 claims 1
- 150000005619 secondary aliphatic amines Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 239000000123 paper Substances 0.000 description 52
- 238000000034 method Methods 0.000 description 15
- 239000000725 suspension Substances 0.000 description 13
- 229920002678 cellulose Polymers 0.000 description 12
- 239000001913 cellulose Substances 0.000 description 12
- 239000000976 ink Substances 0.000 description 12
- 238000009987 spinning Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- 229920002994 synthetic fiber Polymers 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 238000003490 calendering Methods 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000007639 printing Methods 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 5
- 239000012209 synthetic fiber Substances 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- 239000004416 thermosoftening plastic Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000002074 melt spinning Methods 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 4
- XDILCINHTMZTGG-UHFFFAOYSA-N 3-(3-dodecoxy-3-oxopropyl)sulfanylpropanoic acid Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(O)=O XDILCINHTMZTGG-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000002530 phenolic antioxidant Substances 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229920006125 amorphous polymer Polymers 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 206010061592 cardiac fibrillation Diseases 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002600 fibrillogenic effect Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920000638 styrene acrylonitrile Polymers 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
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
- D21H5/00—Special paper or cardboard not otherwise provided for
- D21H5/12—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials
- D21H5/20—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of organic non-cellulosic fibres too short for spinning, with or without cellulose fibres
- D21H5/202—Special paper or cardboard not otherwise provided for characterised by the use of special fibrous materials of organic non-cellulosic fibres too short for spinning, with or without cellulose fibres polyolefins
-
- 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
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/12—Organic non-cellulose fibres from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/14—Polyalkenes, e.g. polystyrene polyethylene
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Absorbent Articles And Supports Therefor (AREA)
Description
Papir og papirlignende strukturer. Paper and paper-like structures.
Foreliggende oppfinnelse vedrorer papir og papirlignende fiberstrukturer av den art som er angitt i kravets ingress. The present invention relates to paper and paper-like fiber structures of the type specified in the preamble of the claim.
I den folgende beskrivelse benyttes uttrykket: "papir In the following description, the expression: "paper
og papirlignende fiberstrukturer" for å betegne hvilken SOm helst type papir av fiberholdige papirlignende produkter og lignende mate-rialer, slik som de nutildags fremstilles ved hjelp av konvensjon- and paper-like fiber structures" to denote any type of paper from fiber-containing paper-like products and similar materials, such as are nowadays produced using conventional
ell papirfremstillingsprosess og utstyr som benyttes i papirindu-strien. ell papermaking process and equipment used in the paper industry.
Som kjent benyttes der ved fremstilling av papir og papirlignende strukturer i det vesentlige fibre av cellulose eller av ce1lulosederivater. As is known, in the production of paper and paper-like structures mainly fibers of cellulose or of cellulose derivatives are used.
Likeledes er det kjent at papir og lignende strukturer fremstilles med utgangsmateriale som syntetiske polymere eller blandinger av disse. Likewise, it is known that paper and similar structures are produced with starting material such as synthetic polymers or mixtures thereof.
I US patent nr. 2.971.858 er beskrevet en prosess hvorved syntetisk papir fremstilles ved omdannelse av polypropylen opplost i et egnet opplosningsmiddel, til en film og efterfulgt av fordampning under spesielle forhold. US patent no. 2,971,858 describes a process by which synthetic paper is produced by converting polypropylene dissolved in a suitable solvent into a film and followed by evaporation under special conditions.
I italiensk patent nr. 632.085 er beskrevet en annen fremgangsmåte for fremstilling av syntetisk papir, efter hvilken fremgangsmåte der oppnåes en film eller ark ved ekstrudering av en smel-tet blanding av polypropylen, i det vesentlige bestående av isotaktiske makromolekyler og mineralsk fyllstoff med en spesiell granula-ritet. In Italian patent no. 632,085 another method for the production of synthetic paper is described, according to which method a film or sheet is obtained by extruding a molten mixture of polypropylene, essentially consisting of isotactic macromolecules and mineral filler with a special granula-rite.
Det er også kjent papir og papirlignende produkter som fremstilles efter mere eller mindre konvensjonelle metoder fra kunstige eller naturlige cellulosefibre, eller fra syntetiske fibre. There are also known paper and paper-like products which are produced using more or less conventional methods from artificial or natural cellulose fibres, or from synthetic fibres.
De sistnevnte blir generelt representert av fibre fremstillet fra acrylonitrilpolymere og copolymere, og av polyamider og polyestere. The latter are generally represented by fibers made from acrylonitrile polymers and copolymers, and by polyamides and polyesters.
Ytterligere er en av de seneste års mere avanserte teknikker for fremstilling av papir i det vesentlige fra syntetiske fibre, kjennetegnet ved at der fremstilles "fibriller" ved utfelling fra egntoe oppløsninger av de ovenfor nevnte polymere, og at de erholdte fibriller omformes ved en spesiell teknikk til "textrils", som er produkter som selv ligner papir. Furthermore, one of the more advanced techniques of recent years for the production of paper essentially from synthetic fibers is characterized by the fact that "fibrils" are produced by precipitation from appropriate solutions of the above-mentioned polymers, and that the resulting fibrils are reshaped by a special technique to "textrils", which are products that themselves resemble paper.
Fra britisk patent nr. 980.697 er der kjent et papirpro-dukt omfattende naturlige cellulosefibre og polyolefinfibre, såsom polypropylenfibre, som kan være tilstede i papirproduktet i en meng-de på 20 - 70 vekt%. Papirproduktet i henhold til dette patent er påtenkt anvendt for isolasjonspapir, idet tilstedeværelsen av poly-olef infibrene gir papiret egenskaper som er bedre for elektriske isolasjonsformål enn papir basert på bare cellulosefibre. From British patent no. 980,697 there is known a paper product comprising natural cellulose fibers and polyolefin fibers, such as polypropylene fibers, which can be present in the paper product in an amount of 20 - 70% by weight. The paper product according to this patent is intended to be used for insulation paper, the presence of the polyolefin fibers giving the paper properties that are better for electrical insulation purposes than paper based on cellulose fibers alone.
I fransk patent nr. 1.203.873 er beskrevet et papirlignende materiale omfattende 5 - 75 % syntetiske fibre, og 95 - 25 % cellulosefibre. Ifolge dette patent anvendes syntetiske fibre som er erholdt ved ekstrudering av en blanding av ikke forenelige har-pikser, såsom en blanding av polystyren og polyethylen, en blanding av polystyren og en copolymer omfattende styren-acrylnitril, en copolymer av vinylklorid, vinylacetat og rnaleinsyreanhydrid og polyethylen . French patent no. 1,203,873 describes a paper-like material comprising 5-75% synthetic fibers and 95-25% cellulose fibers. According to this patent, synthetic fibers are used which are obtained by extruding a mixture of incompatible resins, such as a mixture of polystyrene and polyethylene, a mixture of polystyrene and a copolymer comprising styrene-acrylonitrile, a copolymer of vinyl chloride, vinyl acetate and maleic anhydride and polyethylene.
I de franske patenter nr. 1.388.372 og 1.392.767 er hen-. holdsvis omtalt vevede eller ikke vevede strukturer på basis av 10% ustrukne polyolefinfibre og 90 % strukne polyolefinfibre og ikke-vevede strukturer på basis av krympede polyest?rfibre. In the French patents Nos. 1,388,372 and 1,392,767 it is respectively mentioned woven or non-woven structures based on 10% unstretched polyolefin fibers and 90% stretched polyolefin fibers and non-woven structures based on shrunk polyester fibers.
I norsk patent nr. 106.405 beskrives en fremgangsmåte ved hvilken der fremstilles et papirlignende materiale ved en i og for seg konvensjonell papirfremstillingsmetode, hvor der som fibermate-riale kun anvendes syntetiske fibre som er særpreget ved en bestemt geometrisk form. Fibre av polypropylen kan anvendes som fibermate-riale ved utovelse av fremgangsmåten ifolge dette patent. In Norwegian patent no. 106,405, a method is described in which a paper-like material is produced by an inherently conventional paper-making method, where only synthetic fibers that are characterized by a specific geometric shape are used as fiber material. Fibers of polypropylene can be used as fiber material in the extension of the method according to this patent.
Norsk patent nr. 122.573 angir en fremgangsmåte ved fremstilling av varmeforseglbart papir av termoplastiske fibre og ikke-termoplastiske fibre. Som termoplastiske fibre kan anvendes fibre på basis av polypropylen. Ifolge patentet skjer avvanningen under spesielle betingelser, slik at der oppnåes en gruppering av fibrene i det ferdige papirlignende produkt. ""— Norwegian patent no. 122,573 specifies a method for the production of heat-sealable paper from thermoplastic fibers and non-thermoplastic fibers. Fibers based on polypropylene can be used as thermoplastic fibers. According to the patent, the dewatering takes place under special conditions, so that a grouping of the fibers is achieved in the finished paper-like product. ""—
Norsk patent nr. 123.010 vedrorer et arkmateriale som inneholder ikke-strukne termoplastfibre, innbefattende polypropyoen-fibre, og hvor fibrene er kjennetegnet ved en bruddforlengelse storre enn 200 %. Norwegian patent no. 123,010 relates to a sheet material containing non-stretched thermoplastic fibres, including polypropylene fibres, and where the fibers are characterized by an elongation at break greater than 200%.
Alle disse teknikker er blitt realisert og utviklet i den hensikt å eliminere hovedulempene ved tradisjonelt papir, spesielt slik som lav rivstyrke, og lav sprengstyrke og lignende. All these techniques have been realized and developed with the intention of eliminating the main disadvantages of traditional paper, especially such as low tear strength, and low burst strength and the like.
Med de ovenfor nevnte metoder var det i mange tilfelle mu-lig å forbedre disse mindre gode egenskaper ved naturlig papir; imidlertid hadde de produkter som blev oppnådd på denne måte andre ulemper slik som f.eks. deres lave forenelighet med hensyn til blekk og farver samt hoy pris, og fremforalt behovet for å anvende kompleks fremstillings- og "finishing" teknologi. With the methods mentioned above, it was in many cases possible to improve these less good properties of natural paper; however, the products obtained in this way had other disadvantages such as e.g. their low compatibility with regard to inks and colors as well as their high price, and above all the need to use complex manufacturing and "finishing" technology.
Således er hensikten med denne oppfinnelsé å tilveiebringe en ny type papir eller papirlignende produkter som ikke skal ha de ovenfor nevnte ulemper som er kjennetegnet ved en optimal kombinasjon av fysikalske egenskaper og sluttelig at det ikke er nodvendig å benytte spesielle og/eller dyre fremstillingsmåter og teknologi. Thus, the purpose of this invention is to provide a new type of paper or paper-like products which should not have the above-mentioned disadvantages which are characterized by an optimal combination of physical properties and finally that it is not necessary to use special and/or expensive manufacturing methods and technology .
Der er funnet, hvilket er basis for den foreliggende oppfinnelse, at papir og papirlignende strukturer med spesielt hensikts-messige egenskaper, kan oppnåes ved blandinger av fra 1 til 60 vekt% fibre fra propylenpolymere og av fra 35 til 99 vekt% av cellulosefibre eller cellulosederivatfibre samt et polymert bindemiddel, og er særpreget ved det som er angitt i krav l's karakteriserende del. It has been found, which is the basis for the present invention, that paper and paper-like structures with particularly suitable properties can be obtained by mixtures of from 1 to 60% by weight of fibers from propylene polymers and from 35 to 99% by weight of cellulose fibers or cellulose derivative fibers as well as a polymeric binder, and is characterized by what is stated in claim 1's characterizing part.
Med hensyn til bestanddelene i blandingen ifolge oppfinnelsen er de syntetiske fibre basert på propylen homopolymere, i det vesentlige bestående av isotaktiske makromolekyler eller på termoplastiske copolymere i det vesentlige dannet av propylenisk bundne monomere enheter alternert med kombinerte monomere enheter av i det minste én annen monomer. With regard to the components of the mixture according to the invention, the synthetic fibers are based on propylene homopolymers, essentially consisting of isotactic macromolecules or on thermoplastic copolymers essentially formed of propylene-bonded monomeric units alternating with combined monomeric units of at least one other monomer.
De aktuelle fiberdannende propylenpolymere har en smelte-rideks på 0,5 - 50. De kan være tilsatt antioxidantmidler, matter-ingsmidler, pigmenter, farve, stabilisatorer, smoremidler og lignende tilsetningsstoffer. The fibre-forming propylene polymers in question have a melting index of 0.5 - 50. They may have added antioxidants, matting agents, pigments, colour, stabilisers, lubricants and similar additives.
Fibrene fremstilles ved hjelp av en smeltespinningsprosess, fortrinnsvis efterfulgt av en herdning, strekking, dimensjonsstabi-lisering, oppkutning og av andre lignende operasjoner. The fibers are produced by means of a melt spinning process, preferably followed by a hardening, stretching, dimensional stabilization, cutting and by other similar operations.
Til spinningen benyttes der fortrinnsvis spinnedyser som har hull med en enkelt diameter storre enn 0,5 mm og en lengde/dia-meterforhold storre enn 1.1, fortrinnsvis fra IO til 30. Spinnedy-senes hull kan ha et tverrsnitt som- utviser enten sirkulær eller ikke-sirkulær profil. For the spinning, spinning nozzles are preferably used which have holes with a single diameter greater than 0.5 mm and a length/diameter ratio greater than 1.1, preferably from 10 to 30. The spinning nozzles' holes can have a cross-section that is either circular or non-circular profile.
Der kan imidlertid også benyttes polypropylenfibre fremstillet ved hjelp av andre metoder enn dem som er basert på tradi-sjonell spinnemetode gjennom spinnedyser. Mere spesifikt er der funnet at man med fordel kan benytte fibre fra propylenpolymere, fremstillet fra filmer eller ark strukket longidutinalt og underkastet (muligens til samme tid) en fibrilleringsoperasjon, spesielt fibre oppnådd ved oppkutting av fibrillert syntetisk rafia. However, polypropylene fibers produced using methods other than those based on the traditional spinning method through spinning nozzles can also be used. More specifically, it has been found that it is advantageous to use fibers from propylene polymers, produced from films or sheets stretched longitudinally and subjected (possibly at the same time) to a fibrillation operation, especially fibers obtained by cutting up fibrillated synthetic raffia.
Polypropylenfibrene som anvendes i henhold til oppfinnelsen har en lengde som ikke overstiger 20 mm og en finhet under 2,5 dtex. The polypropylene fibers used according to the invention have a length that does not exceed 20 mm and a fineness below 2.5 dtex.
Som en annen bestanddel i blandingene ifolge oppfinnelsen anvendes cellulosefibre; de cellulosefibre som kan anvendes i blan-dina med polypropylenfibrene er alle fibertyper av cellulose, såvel naturfibre som kunstige, slike som oppnåes fra cellulosemasse, fra silkeviskose, bomullslinters og lignende. Cellulose fibers are used as another component in the mixtures according to the invention; the cellulose fibers that can be used in the mixture with the polypropylene fibers are all fiber types of cellulose, both natural and artificial fibers, such as are obtained from cellulose pulp, from silk viscose, cotton linters and the like.
Som anfdrt tidligere er den tredje bestanddel i blandingene ifolge oppfinnelsen et polymert bindemiddel som er en i det vesentlige amorf propylenpolymer (muligens modifisert), og/eller en basisk polymer eller copolymer av epiklorhydrin. As stated previously, the third component in the mixtures according to the invention is a polymeric binder which is an essentially amorphous propylene polymer (possibly modified), and/or a basic polymer or copolymer of epichlorohydrin.
Den amorfe propylenpolymer, modifisert eller ikke, har et grenseviskositetstall fra 0,1 til 0,9 målt i tetrahydronafthaien ved 135°C; polymerene inneholder fortrinnsvis fra 2 til 40 % klor og/eller fra 0,01 til 3 % svovel. The amorphous propylene polymer, modified or not, has an intrinsic viscosity number from 0.1 to 0.9 measured in tetrahydronaphthalene at 135°C; the polymers preferably contain from 2 to 40% chlorine and/or from 0.01 to 3% sulphur.
Amorft polypropylen kan modifiseres ved å opplose polymeren i et- klorert organisk opplosningsmiddel, eksempelvis triklorethylen eller tetraklorethylen, og eventuelt tilfore oppløsningen gassformig klor eller HC1. Amorft polypropylen kan også modifiseres ved å opplose polymeren i hvilket som helst egnet organisk opplosningsmiddel og derefter behandle oppløsningen med gassformige blandinger inneholdende klor og svovel, eksempelvis klor i gassform, og et flyktig mercaptan eller klorsulfonsyre„ Modifisering av amorft polypropylen er nærmere beskrevet i US patenter 3.037.949, 3.043.787, og i de italienske patenter 597,560 og 588..2O0. Amorphous polypropylene can be modified by dissolving the polymer in a chlorinated organic solvent, for example trichlorethylene or tetrachlorethylene, and optionally adding gaseous chlorine or HC1 to the solution. Amorphous polypropylene can also be modified by dissolving the polymer in any suitable organic solvent and then treating the solution with gaseous mixtures containing chlorine and sulphur, for example chlorine in gaseous form, and a volatile mercaptan or chlorosulfonic acid. Modification of amorphous polypropylene is further described in US patents 3,037,949, 3,043,787, and in the Italian patents 597,560 and 588..2O0.
De ovenfor i det vesentlige amorfe propylenpolymere benyttes i mengder fra 0,3 til 15 vekt% av blandingens vekt. The above essentially amorphous propylene polymers are used in amounts from 0.3 to 15% by weight of the weight of the mixture.
I stedet for eller i tillegg til de ovenfor nevnte amorfe propylenpolymere kan som polymert bindemiddel benyttes en basisk polymer eller copolymer fremstillet ved kondensasjon av epiklorhydrin med minst ett primært og/eller sekundært alifatisk, aromatisk og he-terocyclisk amin. Det foretrukne bindemiddel dannes av epiklorhydrin og minst ett amin valgt fra en gruppe bestående av n-dodecylamin, n-octodecylamin, piperazin, N,N'-dicyclohexamethylendiamin og lignende; molforholdet mellom epiklorhydrin og den totale aminmengde er 1:1. Instead of or in addition to the above-mentioned amorphous propylene polymers, a basic polymer or copolymer produced by condensation of epichlorohydrin with at least one primary and/or secondary aliphatic, aromatic and heterocyclic amine can be used as polymeric binder. The preferred binder is formed from epichlorohydrin and at least one amine selected from the group consisting of n-dodecylamine, n-octodecylamine, piperazine, N,N'-dicyclohexamethylenediamine and the like; the molar ratio between epichlorohydrin and the total amount of amine is 1:1.
Polymere og copolymere av denne type er beskrevet i de italienske patenter nr. 611.258, 543.990, 682.346, 799.544 og 809.075. I henhold til disse og andre patenter blev polymerene og copolymere-ne fremstillet fra epiklorhydrin med aminer, innarbeidet for spin-ning til "fiberdannende polymere" og virket til å modifisere farven. Polymers and copolymers of this type are described in Italian Patent Nos. 611,258, 543,990, 682,346, 799,544 and 809,075. According to these and other patents, the polymers and copolymers were prepared from epichlorohydrin with amines, incorporated for spinning into "fiber-forming polymers" and acted to modify the color.
Det er overraskende blitt funnet at de basiske epiklorhyd-rinpolymere utviser en utmerket bindeevne i blandinger bestående av cellulose og polypropylenfibre, uten at de er blitt innarbeidet i It has surprisingly been found that the basic epichlorohydrin polymers exhibit an excellent binding ability in mixtures consisting of cellulose and polypropylene fibers, without having been incorporated into
"Fiberdannende polymere". Tilsetning av disse basiske polymere til blandingene forbedrer i vesentlig grad evnen til å motta blekk og farver, samt forbedrer overraskende den relative limfasthet i papiret ifolge oppfinnelsen. "Fiber-forming polymers". Addition of these basic polymers to the mixtures significantly improves the ability to receive inks and colours, and surprisingly improves the relative adhesive strength of the paper according to the invention.
Papirproduktene ifolge oppfinnelsen er spesielt egnet som omslagspapir for boker, omslagspapir generelt, finere kartpapir, pakningspapir og kartong, filterpapir, papir for bordduker og bleier, som innpaknings- og omslagspapir, papir for hygienisk bruk og for laminater, filter og lignende. The paper products according to the invention are particularly suitable as cover paper for books, cover paper in general, finer map paper, packing paper and cardboard, filter paper, paper for tablecloths and nappies, as wrapping and wrapping paper, paper for hygienic use and for laminates, filters and the like.
Papiret ifolge oppfinnelsen kan underkastes alle de vanlige sluttbehandlingsmetoder. The paper according to the invention can be subjected to all the usual finishing methods.
I det folgende vil der bli gitt en serie eksempler for å illustrere denne oppfinnelse. I eksemplene er sprengstyrken målt ved hjelp av Mullen sprengstyrkeapparat, i henhold til provefor-skriftene angitt i TAPPI, T40 m53, mens rivstyrken blev målt med et Elmendorf rivstyrkeapparat i henhold til TAPPI T141 m49. In the following, a series of examples will be given to illustrate this invention. In the examples, the burst strength was measured using a Mullen burst strength apparatus, according to the test regulations stated in TAPPI, T40 m53, while the tear strength was measured with an Elmendorf tear strength apparatus according to TAPPI T141 m49.
Eksempel 1 Fremstilling av polypropylenfibre Example 1 Production of polypropylene fibres
Polypropylenfibre blev fremstillet på folgende måte: Polypropylene fibers were produced as follows:
99,5 kg polypropylen (med smelteindeks på 14, et askeinnhold. på 0,001 % og med n-heptan ekstraksjonsrest på 97 %), 0,25 kg laurylthiodipropionat og 0,25 kg av en fenolisk antioxidant (2,6-di-tert. butylparacresol. 99.5 kg of polypropylene (with a melt index of 14, an ash content of 0.001% and with an n-heptane extraction residue of 97%), 0.25 kg of laurylthiodipropionate and 0.25 kg of a phenolic antioxidant (2,6-di-tert .butylparacresol.
Blandingen blev granulert i en ekstruder ved 210°C i en oxygenfri atmosfære. Granulatet blev derefter spunnet i et smelte-spinneutstyr under folgende betingelser: Spinnedyse med 60 hull som hvert hadde en diameter på 0,6 mm og en kapillær lengde på 15 mm; The mixture was granulated in an extruder at 210°C in an oxygen-free atmosphere. The granulate was then spun in a melt-spinning equipment under the following conditions: Spinning nozzle with 60 holes each having a diameter of 0.6 mm and a capillary length of 15 mm;
Ekstruderskruens temperatur: 250°C Extruder screw temperature: 250°C
Spinnedysens " : 250°C Spinning nozzle ": 250°C
Opprullingshastighet: 400 m/min. Winding speed: 400 m/min.
De derved oppnådde filamenter blev strukket i en dampatmo-sfære ved 130°C med strekkforhold 1:5, og blev derefter kuttet opp. The filaments thus obtained were stretched in a steam atmosphere at 130°C with a stretch ratio of 1:5, and were then cut up.
De oppkuttede fibre utviste folgende egenskaper: The chopped fibers exhibited the following properties:
Eksempel 2 Fremstilling av polypropylenfibre Polypropylenfibre blev fremstillet på folgende måte: 99,5 kg polypropylen (med smelteindeks på 8, et askeinnhold på 0,001 % og en n-heptan ekstraksjonsrest på 97 %), 0,25 kg laurylthiodipropionat og 0,25 kg fenolisk antioxidant (4,4'-thio-bis-(6-tert.butylmetacresol). Example 2 Production of polypropylene fibers Polypropylene fibers were produced as follows: 99.5 kg of polypropylene (with a melt index of 8, an ash content of 0.001% and an n-heptane extraction residue of 97%), 0.25 kg of laurylthiodipropionate and 0.25 kg of phenolic antioxidant (4,4'-thio-bis-(6-tert.butylmetacresol).
Denne blanding blev granulert og ekstrudert ved 210°C i en oxygenfri atmosfære. Granulatet blev derefter spunnet ved hjelp av et smelte-spinningsutstyr under folgende betingelser: Spinnedysen hadde 60 hull med en individuell diameter på 0, 6 m og med en kapi Hær lengde på 16 mm. This mixture was granulated and extruded at 210°C in an oxygen-free atmosphere. The granulate was then spun using a melt-spinning equipment under the following conditions: The spinning nozzle had 60 holes with an individual diameter of 0.6 m and with a cap length of 16 mm.
Ekstruderskruens temperatur: 250°C Extruder screw temperature: 250°C
Spinnedysens temperatur: 250°C Spinning nozzle temperature: 250°C
Opprullingshastighet: 400 m/min. Winding speed: 400 m/min.
De derved erholdte filamenter blev strukket i en vanndamp-atmosfære ved 130°C og med et strekkforhold på 1:5, hvorefter fila-mentene blev kuttet opp. The filaments thus obtained were stretched in a steam atmosphere at 130°C and with a stretching ratio of 1:5, after which the filaments were cut up.
De oppkuttede fibre utviste folgende egenskaper: The chopped fibers exhibited the following properties:
Eksempel 3 Fremstilling av polypropylenfibre Polypropylenfibrene blev fremstillet på folgende måte: 99,5 kg polypropylen (med smelteindeks på 14, et askeinnhold på 0,001 % og en n-heptan ekstraksjonsrest på 97 %), 0,25 kg laurylthiodipropionat og 0,25 kg fenolisk antioxidant (2,6-di-tert. butylparacresol). Example 3 Production of polypropylene fibers The polypropylene fibers were produced in the following way: 99.5 kg of polypropylene (with a melt index of 14, an ash content of 0.001% and an n-heptane extraction residue of 97%), 0.25 kg of laurylthiodipropionate and 0.25 kg of phenolic antioxidant (2,6-di-tert. butylparacresol).
Denne blanding blev granulert og ekstrudert ved 210°C i en oxygenfri atmosfære. Granulatet blev derefter spunnet med et smelte-spinningsutstyr under folgende betingelser: Spinnedysen hadde 60 hull med en individuell diameter på 0,6 mm og en kapi Hær lengde på 15 mm. This mixture was granulated and extruded at 210°C in an oxygen-free atmosphere. The granulate was then spun with a melt-spinning equipment under the following conditions: The spinning die had 60 holes with an individual diameter of 0.6 mm and a cap length of 15 mm.
Ekstruderskruens temperatur; 250°C Extruder screw temperature; 250°C
Spinnedysens temperatur: 250°C Spinning nozzle temperature: 250°C
Opprullingshastighet: 400 m/min. Winding speed: 400 m/min.
De derved oppnådde filamenter blev strukket i en vanndamp-atmosfære ved 130°C med et strekkforhold på 1:5 og blev derefter kuttet opp. De oppkuttede fibre utviste folgende egenskaper: The filaments thus obtained were drawn in a steam atmosphere at 130°C with a drawing ratio of 1:5 and then cut open. The chopped fibers exhibited the following properties:
Eksempel 4 Example 4
4,65 kg polypropylenfibre fremstillet i henhold til eksempel i, med en fiberlengde på 5 mm og en finhet på 1,7 dtex/filament 4.65 kg of polypropylene fibers produced according to example i, with a fiber length of 5 mm and a fineness of 1.7 dtex/filament
blev blandet med 5,0 kg bleket sulfitcellulose, blev efter en fordes-integrasjon utspedd i 100 liter vann, og som bindemiddel blev til satt 0,35 kg amorf propylenpolymer med ataktisk struktur og med en grenseviskositet (målt i tetralin ved 135°C) på 0,35. was mixed with 5.0 kg of bleached sulphite cellulose, after pre-integration was diluted in 100 liters of water, and 0.35 kg of amorphous propylene polymer with an atactic structure and with a limit viscosity (measured in tetralin at 135°C) was added as a binder. of 0.35.
Den amorfe polymer blev tilsatt i form av en vandig emulsjon. Blandingen blev omrdrt ca. 1 time i en konvensjonell papirblander for å sikre en homogen suspensjon. Ved hjelp av konvensjonell fremgangsmåte blev der fremstillet papirark fra suspensjonen som efter torking efterfulgt av kalandrering i 5 sekunder mellom kalandersylindre, oppvarmet til ca. 165°C, utviste folgende karakteregen-skaper : The amorphous polymer was added in the form of an aqueous emulsion. The mixture was stirred approx. 1 hour in a conventional paper mixer to ensure a homogeneous suspension. Using conventional methods, paper sheets were produced from the suspension which, after drying followed by calendering for 5 seconds between calender cylinders, were heated to approx. 165°C, exhibited the following characteristics:
Det således fremstiilede papir, utviste utmerkede mottag-ningsegenskaper overfor blekk og trykkfarve. The paper thus produced exhibited excellent reception properties towards ink and printing ink.
Eksempel 5 Example 5
2,5 kg polypropylenfibre fremstillet i henhold til eksempel 1, men med en fiberlengde på 6 mm og en finhet på 1,85 dtex/filament blev blandet med 7, 0 kg bleket sulfitcellulose, og efter en fordesintegrering utspedd i lOO liter vann og tilsatt 0,5 kg amorft polypropylen med en ataktisk struktur og en grenseviskositet på 0,45, i en vandig emulsjon. Denne blanding blev omrort ca. 1 time i en vanlig papirblander for å sikre en homogen suspensjon. 2.5 kg of polypropylene fibers produced according to example 1, but with a fiber length of 6 mm and a fineness of 1.85 dtex/filament were mixed with 7.0 kg of bleached sulphite cellulose, and after a pre-disintegration diluted in lOO liters of water and added 0.5 kg of amorphous polypropylene with an atactic structure and an intrinsic viscosity of 0.45, in an aqueous emulsion. This mixture was stirred approx. 1 hour in a regular paper blender to ensure a homogeneous suspension.
Fra suspensjonen blev der fremstillet papirark efter konvensjonell fremgangsmåte, som efter torking blev kalandrert 5 sekunder mellom kalandersylindre oppvarmet til 165°C, hvorefter papiret utviste folgende egenskaper: Paper sheets were produced from the suspension according to a conventional method, which after drying were calendered for 5 seconds between calender cylinders heated to 165°C, after which the paper exhibited the following properties:
Det fremstiilede papir utviste utmerkede mottagningsegen-skaper overfor blekk og trykkfarve. The prepared paper exhibited excellent reception properties towards ink and printing ink.
Eksempel 6 Example 6
4,5 kg polypropylenfibre fremstillet i henhold til eksempel 1, med en fiber lengde på 6 mm og en finhet på 1,7 dtex/filament blev blandet med 5 kg bleket sulfitcellulose, hvorefter blandingen efter en fordesintégrering blev utspedd med lOO liter vann, hvortil blev tilsatt 0,5 kg amorf polymer med propylens ataktiske struktur, med en grenseviskositet på 0,4, og underkastet en forklorinering og inneholdende S % klor. Polymeren blev tilsatt i form av en acetonisk oppldsning. Fiberblandingen blev omrort i ca. 1 time i en konvensjonell papirblander for å sikre en homogen suspensjon. Fra suspensjonen blev der fremstillet papir efter konvensjonell fremgangsmåte, som efter torking efterfulgt av ka landarering i 5 sekunder mellom ka-landervalser oppvarmet til 160°C, utviste folgende egenskaper: 4.5 kg of polypropylene fibers produced according to example 1, with a fiber length of 6 mm and a fineness of 1.7 dtex/filament were mixed with 5 kg of bleached sulphite cellulose, after which the mixture was diluted with 100 liters of water after pre-integrating was added 0.5 kg of amorphous polymer with a propylene atactic structure, with an intrinsic viscosity of 0.4, and subjected to a prechlorination and containing 5% chlorine. The polymer was added in the form of an acetone solution. The fiber mixture was stirred for approx. 1 hour in a conventional paper mixer to ensure a homogeneous suspension. Paper was produced from the suspension according to a conventional method, which after drying followed by calendering for 5 seconds between calender rolls heated to 160°C, exhibited the following properties:
Det derved fremstiilede papir utviste utmerkede mottag-ningsegenskaper overfor blekk og trykkfarve. The paper thus produced exhibited excellent reception properties towards ink and printing ink.
Eksempel 7 Example 7
4,5 kg polypropylenfibre fremstillet i henhold til eksempler 1 og 2, med en fiberlengde på 6 mm og en finhet på 1,7 dtex/fi-lament, blev blandet med 5 kg furusulfatcellulose, hvorefter fiberblandingen blev utspedd med 100 liter vann og fordesintégrert. Til fibersuspensjonen blev tilsatt 0,5 kg av en kondensasjonscopolymer av epiklorhydrin/n-octodecylamin-piperazin (molforhold 1:0.2:0.8). Blandingen blev omrort ca. 1 time i en vanlig papirblander for å sikre en homogen suspensjon. 4.5 kg of polypropylene fibers produced according to examples 1 and 2, with a fiber length of 6 mm and a fineness of 1.7 dtex/filament, were mixed with 5 kg of pine sulfate cellulose, after which the fiber mixture was diluted with 100 liters of water and predisintegrated . To the fiber suspension was added 0.5 kg of a condensation copolymer of epichlorohydrin/n-octodecylamine-piperazine (molar ratio 1:0.2:0.8). The mixture was stirred approx. 1 hour in a regular paper blender to ensure a homogeneous suspension.
Fra suspensjonen blev der fremstillet papirark efter konvensjonell fremgangsmåte, som efter torking og efterfolgende kalandrering i 5 sekunder mellom sylindre oppvarmet til ca. 155°C, utviste følgende egenskaper: Paper sheets were produced from the suspension according to a conventional method, which, after drying and subsequent calendering for 5 seconds between cylinders, were heated to approx. 155°C, exhibited the following properties:
Det derved fremstiilede papir utviste utmerkede mottagnings-egenskaper. The paper thus produced exhibited excellent reception properties.
Eksempel 8 Example 8
2,5 kg polypropylenfibre fremstillet i henhold til eksempel 3, men med en fiberlengde på 6 mm og en finhet på 1,75 dtex/filament blev blandet med 7 kg bleket sulfitcellulose. Fiberblandingen blev utspedd med 100 liter vann og desintegrert; til suspensjonen blev tilsatt en dispersjon inneholdende 0,5 kg kondensasjonspolymer av epiklorhydrin/piperazin (molforhold =1:1). 2.5 kg of polypropylene fibers prepared according to Example 3, but with a fiber length of 6 mm and a fineness of 1.75 dtex/filament were mixed with 7 kg of bleached sulphite cellulose. The fiber mixture was diluted with 100 liters of water and disintegrated; a dispersion containing 0.5 kg condensation polymer of epichlorohydrin/piperazine (molar ratio = 1:1) was added to the suspension.
Blandingen blev omrort ca. 1 time i en konvensjonell papirblander, for å sikre en homogen suspensjon. The mixture was stirred approx. 1 hour in a conventional paper blender, to ensure a homogeneous suspension.
Fra suspensjonen blev der fremstillet papir efter konvensjonelle metoder, som efter torking efterfulgt av kalandrering i 5 sekunder mellom sylindre oppvarmet til ca. 155°C, utviste folgende egenskaper: From the suspension, paper was produced according to conventional methods, which after drying followed by calendering for 5 seconds between cylinders heated to approx. 155°C, exhibited the following properties:
Det derved fremstiilede papir utviste utmerkede mottag-ning segenskaper overfor blekk og trykkfarve. The paper thus produced exhibited excellent reception properties towards ink and printing ink.
Eksempel 9 Example 9
5 kg polypropylenfibre fremstil let i henhold til eksempler 1, 2 og 3 med en fiberlengde på 6 mm og en finhet på 1,7 dtex/fila-ment blev blandet med 4,5 kg bleket sulfitcellulose. Fiberblandingen blev utspedd i 100 liter vann, og efter en fordesintegrering tilsatt en dispersjon inneholdende O,5 kg kondensasjonscopolymer av epiklorhydrin/piperazin/NN'-dicyclohexylhexamethylendiamin (molforhold 1:0,75:0,25). Fiberblandingen blev omrort ca. 1 time i en konvensjonell papirblander for å sikre en homogen suspensjon. Der blev fremstillet papirark,efter konvensjonelle fremstil-lingsmetoder, som efter torking blev kalandrert i 5 sekunder mellom kalandersylindre oppvarmet til ca. 165°C, utviste folgende egenskaper : 5 kg of polypropylene fibers prepared according to examples 1, 2 and 3 with a fiber length of 6 mm and a fineness of 1.7 dtex/filament were mixed with 4.5 kg of bleached sulphite cellulose. The fiber mixture was diluted in 100 liters of water and, after pre-disintegration, a dispersion containing 0.5 kg condensation copolymer of epichlorohydrin/piperazine/NN'-dicyclohexylhexamethylenediamine (molar ratio 1:0.75:0.25) was added. The fiber mixture was stirred approx. 1 hour in a conventional paper mixer to ensure a homogeneous suspension. Paper sheets were produced according to conventional production methods, which after drying were calendered for 5 seconds between calender cylinders heated to approx. 165°C, exhibited the following properties:
Det derved fremstiilede papir utviste utmerkede mottag-ningsegenskaper overfor blekk og trykkfarve. The paper thus produced exhibited excellent reception properties towards ink and printing ink.
Claims (3)
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GB1569417A (en) * | 1976-03-30 | 1980-06-18 | Ici Ltd | Sheet type wall covering or ceiling covering |
US4286030A (en) * | 1980-02-06 | 1981-08-25 | W. R. Grace & Co. | Thermoset resin impregnated web and process of making |
JPS58103610U (en) * | 1982-01-05 | 1983-07-14 | 服部 益造 | A gas table where you can see the gas flame reflected. |
US4426417A (en) * | 1983-03-28 | 1984-01-17 | Kimberly-Clark Corporation | Nonwoven wiper |
IT1254202B (en) * | 1992-02-06 | 1995-09-14 | Himont Inc | COUPLED ITEMS INCLUDING A NON-WOVEN FABRIC AND A FILM IN POLYOLEFINIC MATERIALS AND PROCEDURE FOR THEIR PREPARATION |
US10583977B2 (en) | 2016-08-16 | 2020-03-10 | Mp Global Products, L.L.C. | Method of making an insulation material and an insulated mailer |
US10442600B2 (en) | 2017-04-07 | 2019-10-15 | Pratt Retail Specialties, Llc | Insulated bag |
US10800595B2 (en) | 2017-04-07 | 2020-10-13 | Pratt Retail Specialties, Llc | Box liner |
US10604304B2 (en) | 2017-05-09 | 2020-03-31 | Pratt Retail Specialties, Llc | Insulated bag with handles |
US10954057B2 (en) | 2017-05-09 | 2021-03-23 | Pratt Retail Specialties, Llc | Insulated box |
US10551110B2 (en) | 2017-07-31 | 2020-02-04 | Pratt Retail Specialties, Llc | Modular box assembly |
US10947025B2 (en) | 2017-12-18 | 2021-03-16 | Pratt Corrugated Holdings, Inc. | Insulated block packaging assembly |
US10507968B2 (en) | 2017-12-18 | 2019-12-17 | Pratt Retail Specialties, Llc | Modular box assembly |
US11059652B2 (en) | 2018-05-24 | 2021-07-13 | Pratt Corrugated Holdings, Inc. | Liner |
US11066228B2 (en) | 2018-11-13 | 2021-07-20 | Pratt Retail Specialties, Llc | Insulated box assembly and temperature-regulating lid therefor |
US10858141B2 (en) | 2018-11-13 | 2020-12-08 | Pratt Retail Specialties, Llc | Insulated box assembly with overlapping panels |
US11027875B2 (en) | 2019-05-02 | 2021-06-08 | Pratt Retail Specialties, Llc | Telescoping insulated boxes |
US10882684B2 (en) | 2019-05-02 | 2021-01-05 | Pratt Retail Specialties, Llc | Box defining walls with insulation cavities |
US11230404B2 (en) | 2019-11-26 | 2022-01-25 | Pratt Corrugated Holdings, Inc. | Perforated collapsible box |
US11718464B2 (en) | 2020-05-05 | 2023-08-08 | Pratt Retail Specialties, Llc | Hinged wrap insulated container |
USD968950S1 (en) | 2020-08-10 | 2022-11-08 | Pratt Corrugated Holdings, Inc. | Perforated collapsible box |
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NO130953C (en) | 1975-03-12 |
FR2037342A5 (en) | 1970-12-31 |
NL7001360A (en) | 1970-08-06 |
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