GB2029725A - Process for improving the adhesion of polyvinyl chloride to a woven or knitted fabric, web or other macromolecular polymethylene terephthalate product composed of threads, yarns or fibres - Google Patents
Process for improving the adhesion of polyvinyl chloride to a woven or knitted fabric, web or other macromolecular polymethylene terephthalate product composed of threads, yarns or fibres Download PDFInfo
- Publication number
- GB2029725A GB2029725A GB7928219A GB7928219A GB2029725A GB 2029725 A GB2029725 A GB 2029725A GB 7928219 A GB7928219 A GB 7928219A GB 7928219 A GB7928219 A GB 7928219A GB 2029725 A GB2029725 A GB 2029725A
- Authority
- GB
- United Kingdom
- Prior art keywords
- polyvinyl chloride
- product
- polyethylene imine
- weight
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 42
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 32
- -1 polymethylene terephthalate Polymers 0.000 title claims abstract description 18
- 239000004744 fabric Substances 0.000 title claims abstract description 16
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 34
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 22
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 18
- 229920000728 polyester Polymers 0.000 claims description 16
- 239000012141 concentrate Substances 0.000 claims description 11
- 239000004014 plasticizer Substances 0.000 claims description 8
- 239000008199 coating composition Substances 0.000 claims 3
- 238000007598 dipping method Methods 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 description 8
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910000004 White lead Inorganic materials 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical group O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- RTOSJSSWYMWLIG-UHFFFAOYSA-J C(CCCCCCCCCCC)(=O)[O-].[Ba+2].[Cd+2].C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-] Chemical compound C(CCCCCCCCCCC)(=O)[O-].[Ba+2].[Cd+2].C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCC)(=O)[O-] RTOSJSSWYMWLIG-UHFFFAOYSA-J 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001944 Plastisol Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 241000779819 Syncarpia glomulifera Species 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- VJWZMMQQHZMGGR-UHFFFAOYSA-N hypochlorous acid titanium Chemical compound [Ti].OCl VJWZMMQQHZMGGR-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 239000004999 plastisol Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010944 pre-mature reactiony Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 229940036248 turpentine Drugs 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06N3/06—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/48—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing the ethylene imine ring
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
A process for improving the adhesion of polyvinyl chloride to a woven or knitted fabric, web or other macromolecular polymethylene terephthalate product composed of threads, yarns or fibres, which process comprises treating a product with a solution of polyethylene imine and, if required, subjecting the product so treated to a drying treatment, and applying to the so treated product a coating containing a polyvinyl chloride, a plasticizing agent and a polyisocyanate, and subsequently gelatinizing the coating. The polyethylene imine may be applied to the macromolecular polymethylene terephthalate from a spin finish or by dipping the product in an aqueous solution thereof.
Description
SPECIFICATION
Process for improving the adhesion of polyvinyl chloride to a woven or knitted fabric, web or other macro molecular polymethylene terephthalate product composed of threads, yarns or fibres
The present invention relates to a process for improving the adhesion of polyvinyl chloride to a woven or knitted fabric, web or other macromolecular polymethylene terephthalate product composed of threads, yarns or fibres, in which process a coating containing a polyvinyl chloride, a plasticizing agent and a polyisocyanate is applied to the products and subsequently gelatinized. The invention also relates to the products thus treated.
A process in which a coating containing a polyvinyl chloride, a plasticizing agent and a polyisocyanate is applied to a product is described in, for example, British Patent Specification 1,119,949.
We have now developed a process which permits the percentage of polyisocyanate in the polyvinyl chloride-containing coating to be considerably reduced while maintaining the adhesion and, in many cases, improving the tearing strength.
Accordingly, the present invention provides a process for improving the adhesion of polyvinyl chloride to a woven or knitted fabric, web or other macromolecular polymethylene terephthalate product composed of threads, yarns or fibres, which process comprises treating a product with a solution of polyethylene imine and, if required, subjecting the product so treated to a drying treatment, and applying to the so treated product a coating containing a polyvinyl chloride, a plasticizing agent and a polyisocyanate, and subsequently gelatinizing the coating.
It should be added that the use of polyethylene imine for improving the adhesion of a yarn, cord, or fabric of a macromolecular polymethyiene terephthalate to a polymer is described in Netherlands Patent
Specification No. 260,385. However, the polymer to which the macromolecular polymethylene terephthalate is adhered is a rubber. Moreover, before the products are embedded in the rubber, they are treated with a dispersion of a latex of a copolymer of a vinyl pyridine and a diene in a solution of a precondensation product of a phenol and an aldehyde in water and subsequently dried under tension.
Japanese Patent Application No. 49/92163 (laid open to public inspection) describes the use of polyethylene imine in combination with a latex dispersion for the purpose of improving the adhesion of textile products to rubber or polyvinyl chloride. However, the polyvinyl chloride is already in the form of a sheet material and does not contain any polyisocyanate.
French Patent Specification No. 1,106,707 describes the use of polyethylene imine for obtaining improved adhesion between rayon or cotton and a polyvinyl chloride coating. Both the nature of the treated fabric and the composition of the coating differ essentially from those used in the process of the present invention.
By the term "macromolecular polymethylene terephthalate" as used herein is meant all polymeric esters that contain a high proportion of esters, which may be obtained by subjecting glycols of the series HO(CH2)nOH, where n is an integer of from 2 to 10, to a heat treatment in the presence of terephthalic acid, or a mixture of terephthalic acid and isophthalic acid, under conditions that yield high-molecular weight polyesters. Instead of terephthaiic acid our a mixture of terephthalic acid and isophthalic acid an ester-forming derivative thereof may be used, fcr example aliphatic (including cycloaliphatic) or aromatic esters or half esters, an acid halide or an ammonium salt or amine salt. Instead of the aliphatic glycol a cycloaliphatic glycol may be used.
By the term "yarns" is meant both threads composed of continuousfilaments and threads spun from staple fibres.
By the term "polyvinyl chloride" as used herein is meant not only all possible homopolymers of vinyl chloride and post-chlorinated polyvinyl chloride, but also copolymers whose main constituent is vinyl chloride, such as copolymers of vinyl chloride and vinyl acetate, copolymers of vinyl chloride and vinylidene chloride, copolymers of vinyl chloride and acrylonitrile, copolymers of vinyl chloride and maleic orfumaric esters and copolymers of vinyl chloride and styrene, and also mixtures of a high proportion of polyvinyl chloride resin and a small proportion of some other synthetic resin, such as chlorinated polyethylene or copolymers of acrylonitrile, butadiene and styrene.
The pretreatment with a solution of polyethylene imine may be effected in a separate step, with the threads, cords or fabrics being in a relaxed or in a tensioned state. For example, the yarns or cords may be treated while in skein form. Or they may be continuously passed through a bath of polyethylene imine solution for example with the aid of rolls. If necessary, the excess solution may be removed by, for example, centrifuging or squeezing. It has been found that it is also possible for the polyethylene imine to be applied to the polymethylene terephthalate from the spin finish. This eliminates the need for a separate step, which may result in considerable economy. The temperature at which the treatment with polyethylene imine takes place is not critical. For economical reasons it is therefore generally carried out at room temperature.The polyethylene imine used may be a commercially available polyethylene imine such as that sold under the name "Polymin P" (registered trade name).
It has been found that favourable results are obtained if the products are dipped in an aqueous solution containing 0.0005 to 0.05% by weight of polyethylene imine, and after the excess solution has been squeezed out, subjected to a drying treatment. Optimum results are obtained if the aqueous solution contains 0.005 to 0.01% by weight of polyethylene imine.
The polyethylene imine may also be applied from a spin finish and in this case it is usually present in the spin finish in the form of an aqueous emulsion. It is also possible, however, to use an anhydrous polyethylene imine which may optionally be mixed with a solvent and added to the finish concentrate.
Turpentine may be used as the solvent. The finish concentrate is generally applied to the yarn in an amount of 0.5 to 1.5% by weight, calculated on the yarn weight. Favourable results are obtained if the amount of polyethylene imine in the spin finish is at least 0.05% by weight, calculated on the finish concentrate. Optimum results are obtained if the concentration of the polyethylene imine in the spin finish is between 0.2 and 0.3% by weight, calculated on the finish concentrate.
After the treatment with an aqueous solution of polyethylene imine it is necessary for the products to be dried. This may be done with the products being kept under tension or in a tension-free state. The temperature will then generally be at least 1 O00C.
Applying the polyvinyl chloride-containing coating is effected in the usual manner. During this process the product to which the polyvinyl chloride is applied may be kept under tension or in a tensionless state. As mentioned before, the adhesive composition contains a plasticizer and polyisocyanate as well as a polyvinyl chloride. The polyisocyanate may be entirely or partially blocked, for example as a result of the presence of uretdione rings, as described in British Patent Specification
No. 1,1 9,949. Also use may be made of a mixture of an organic polyisocyanate free of isocyanur rings and an isocyanurate/polyisocyanate polymer, as described in French Patent Specification No.
1,511,163.
To obtain even better adhesion a reactive polyester may be incorporated into the polyvinyl chloride-containing coating. By preference this polyester should contain free hydroxyl groups. The reactive polyesters may be obtained in a manner known per se by condensation of polycarboxylic acids and polyalcohols, preferably ,es-dicarboxylic acids and a,o-diols. Polyesters obtained by condensation of adipic acid with 1,4-butanediol, by condensation of adipic acid with 1,4-butanediol and trimethylol propane, or by esterification of adipic acid with 1 ,6-hexanediol may also advantageously be used.Under some circumstances, for instance if the "pot life" of the polyvinyl chloride- and polyisocyanatecontaining composition for the coating is to be increased, it may be advisable to apply the reactive polyester to the products treated with polyethylene imine prior to applying the polyvinyl chloridecontaining coating thereto. The amount of reactive polyester used generally varies from 1 to 20 per cent by weight, based on the weight of the mixture of plasticizer and polyvinyl chloride to be applied to the product. The amount of polyisocyanate used may vary from 0.5 to 10, preferably from 1 to 6 per cent by weight, based on the weight of the mixture of plastizer and polyvinyl chloride.
Examples of plasticizers that may be used in the adhesive compositions of the invention are organic esters of phosphoric acid or phthalic acid, such as dibutylphthalate, dioctylphthalate and tricresyl Dhosphate.
The adhesive compositions used in the present invention may furthermore contain stabilizers for polyvinyl chloride, such as basic lead carbonate, fillers, pigments and antistatic agents such as carbon black. When blocked polyisocyanates are used, the polyvinyl chloride-containing coatings may also contain catalysts which accelerate the de-blocking process, such as di-n-butyl tin oxide, stannous octoate, zinc acetate, pyridine, triethylene diamine or titanium hydroxy chloride. In particular, when a reactive polyester is incorporated into the polyvinyl chloride-containing coating, it is necessary to include a retarder in order to inhibit as much as possible premature reaction between reactive polyester and polyisocyanate. For this purpose an acid chloride such as phthaloyl chloride may be used.The preparation of the polyvinyl chloride-containing coatings used in the present invention is usually carried out as follows. The polyisocyanate, which may optionally be blocked, is dissolved in a solvent or suspended as a powder in a plasticizer for the polyvinyl chloride, such as dioctylphthalate.
Subsequently, the reactive polyester and the polyisocyanate-containing solution or suspension is mixed with a plastisol of polyvinyl chloride, i.e. a suspension of finely divided polyvinyl chloride in a plasticizer, or with an organosol of polyvinyl chloride, i.e. a suspension of polyvinyl chloride in a mixture of plasticizer and solvent. The whole is thoroughly mixed. The resulting composition may be applied to the product of macromolecular polymethylene terephthalate treated with polyethylene imine in the usual manner, such as by spreading, brushing, impregnating or dipping.
It will generally be desirable to apply two or more polyvinyl chloride-containing coatings. The second and possibly further coatings do not contain reactive polyester and polyisocyanate.
After the first coating or ground coating has been applied, it is pregelatinized at a temperature in the range of from 1000 to 1 50 C. The duration of heating partly depends on the type of polyisocyanate, the coating thickness and the temperature used.
An important advantage of the process of the invention is that it is possible to obtain the same adhesion with the use of a smalleramountofpolyisocyanate in the first coating than would be possible if no polyethylene imine were used.
The invention will be further illustrated in but not limited by the following Examples.
EXAMPLE I
A polyvinyl chioride-containing coating was applied to a fabric of polyethylene terephthalate (cloth weight about 200 g/cm2, with 9 threads/cm both for the warp and the weft). The threads (dtex 1 off2 10 Z60) were provided with 1% spin finish, calculated on the yarn weight. The concentration of the polyethylene imine in the spin finish was 0; 0.25; and 0.5% by weight, calculated on the finish concentrate.The composition of the polyvinyl chloride-containing coating was as follows:
Parts by weight
Polyvinyl chloride paste 60
Dioctylphthalate 40
Basic lead carbonate 1.2
Barium-cadmium laurate 0.6
Parts by weight
70 wt % solution of a hydroxyl
group containing polyester in a
1:1 mixture of ethyl acetate and
methylene chloride (hydroxyl
number 110: acid number < 4) 6
50 wt % dispersion of dimerized
2,4-toluene diisocyanate in
dioctylphthalate 6.1
The first coating applied had a weight of 100 g/m2. This coating was pregelatinized for 1 minute at 1 400C, after which two coatings not containing an adhesive were applied at a weight each of 70 g/m2.
Before applying the third coating, the second coating was also pregelatinized for 1 minute at 1400C.
Subsequently, post-gelatinization was carried out for 2 minutes at 19000.
The adhesion was determined by measuring the force required for a 5 cm wide PVC-film to be pulled off from the polyester fabric over a distance of 10cm at a rate of 10 cm per minute. The results in
Newton/S cm are given in the following table.
Polyethylene imine in spin finish wt % based Adhesion in N/5 cm on finish concentrate O 95 0.25 124 0.5 142 EXAMPLE II
The procedure of Example I was repeated, except that the post-gelation was carried out for 3 minutes at 1 900 C. The results are given in the following table.
Polyethylene imine in spin finish wt % based Adhesion in N/5 cm on finish concentrate O 114 0.25 168 0.5 164 EXAMPLE Ill
The procedure of Example I was repeated, except that a polyfunctional aliphatic isocyanate of the formula:
was used.
The number of parts by weight of polyisocyanate was 3.4 per 100 parts by weight of polyvinyl chloride.
The results are given in the following table.
Polyethylene imine in spin finish wt % based Adhesion in N/5 cm on finish concentrate O 88 0.25 130 0.5 140 EXAMPLE IV
The procedure of Example Ill was repeated, except that the amount by weight of polyisocyanate was 4.5 parts per 100 parts by' weight of polyvinyl chloride paste and the number of parts by weight of the hydroxyl group-containing polyester was 8. The results are given in the following table.
Polyethylene imine in spin-finish wt % based Adhesion in N/5 cm on finish concentrate o 92 0.25 149 0.5 150 EXAMPLE V
In this Example the polyethylene imine was not applied to the yarn from the spin finish, but a similar fabric to that described in Example I was immersed in aqueous solutions containing 0; 0.005 and 0.01% by weight of polyethylene imine, respectively. The fabric was subsequently mangled to a 50% moisture absorption, based on the weight of the fabric. After the fabric had been dried at a temperature of 1 100C to 1 50C, the adhesive composition given in Example I was applied thereto at a weight of 100 g/m2. Gelatinization was carried out for 1 minute at 1 400C and a post-heat treatment was carried out for 3 minutes at 1900C.
The results are given in the following table.
Polyethylene mine in Adhesion in N/s cm bath wt % O 135 0.005 159 0.01 162
Claims (11)
1. A process for improving the adhesion of polyvinyl chloride to a woven or knitted fabric, web or other macromolecular polymethylene terephthalate product composed of threads, yarns or fibres, which process comprises treating a product with a solution of polyethylene imine and, if required, subjecting the product so treated to a drying treatment, and applying to the so treated product a coating containing a polyvinyl chloride, a plasticizing agent and a polyisocyanate, and subsequently gelatinizing the coating.
2. A process as claimed in claim 1 , wherein the polyethylene imine is applied to the macromolecular polymethylene terephthalate product from a spin finish.
3. A process as claimed in claim 2, wherein the amount of polyethylene imine contained in the spin finish is at least 0.05 per cent by weight based on the finish concentrate.
4. A process as claimed in claim 3, wherein the concentration of the polyethylene imine in the spin finish is in the range of from 0.2 to 0.3 per cent by weight based on the finish concentrate.
5. A process as claimed in claim 1, wherein the macromolecular polymethylene telephthalate product is dipped in an aqueous solution containing 0.0005 to 0.05 per cent by weight of polyethylene imine, the excess solution is removed therefrom and the product subjected to a drying treatment.
6. A process as claimed in claim 4, wherein the aqueous solution contains 0.005 to 0.01 per cent by weight of polyethylene imine.
7. A process as claimed in any one of the preceding claims, wherein the polyisocyanate contained in the coating composition is entirely or partially blocked.
8. A process as claimed in any one of the preceding claims, wherein a reactive polyester is incorporated into the polyvinyl chloride-containing coating composition.
9. A process as claimed in claim 8, wherein the amount of reactive polyester is from 1 to 20 per cent by weight based on the weight of the mixture of polyvinyl chloride and plasticizer to be applied to the product.
1 0. A process as claimed in any one of the preceding claims, wherein the polyisocyanate is contained in the polyvinyl chloride coating composition in an amount of from 1 to 6 per cent by weight based on the weight of the mixture of polyvinyl chloride and plasticizer to be applied to the product.
11. A process as claimed in any one of the preceding claims, wherein two or more polyvinyl chloride-containing coatings are applied to the treated product.
1 2. A process as claimed in any one of the preceding claims, wherein the first or ground coating is pre-gelatinized at a temperature in the range of from 1000 to 1 500C.
1 3. A process as claimed in claim 1 substantially as hereinbefore described with reference to any one of the Examples.
1 4. A product of macromoiecuiar polymethylene terephthalate having a polyvinyi chloridecontaining coating adhered thereto, whenever prepared by a process as claimed in any one of the preceding claims.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL7809025A NL7809025A (en) | 1978-09-04 | 1978-09-04 | A PROCESS FOR IMPROVING THE ADHESION OF POLYVINYL CHLORIDE TO A FABRIC, KNITTLE, FLEEC OR OTHER PRODUCTS OF MACROMOLECULAR POLYMETHYLENE PERHALATE MADE FROM THREADS, YARNS OR FIBERS. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2029725A true GB2029725A (en) | 1980-03-26 |
| GB2029725B GB2029725B (en) | 1982-07-14 |
Family
ID=19831479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7928219A Expired GB2029725B (en) | 1978-09-04 | 1979-08-14 | Process for improving the adhesion of polyvinyl chloride to a woven or knitted fabric web or other macromolecular polymethylene terephthalate product composed of threads yarns or fibres |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5536398A (en) |
| DE (1) | DE2932873C2 (en) |
| FR (1) | FR2434889A1 (en) |
| GB (1) | GB2029725B (en) |
| IT (1) | IT1122377B (en) |
| NL (1) | NL7809025A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0710683A1 (en) * | 1994-11-03 | 1996-05-08 | Hospal Industrie S.A. | Adhesion promoter for polyurethane adhesive compositions |
| FR2738847A1 (en) * | 1995-09-18 | 1997-03-21 | Adp Amenagement & Decoration D | CANVAS MATERIAL AND USE THEREOF TO REALIZE A FALSE CEILING |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1068987B1 (en) * | 1995-06-23 | 2004-09-01 | Fuji Kiko Co., Ltd. | Adjustable hinge mount for reclinable seat |
| DE19637305A1 (en) * | 1996-09-13 | 1998-03-19 | Happich Gmbh Gebr | Folding roof covering for convertible |
| CN109628010B (en) * | 2018-12-25 | 2021-05-11 | 宁波六麦新材料科技有限公司 | Non-woven fabric-based adhesive tape and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1106707A (en) * | 1954-05-14 | 1955-12-22 | Comptoir Textiles Artificiels | Manufacturing process for coated fabrics |
| NL103985C (en) * | 1961-01-23 | 1900-01-01 |
-
1978
- 1978-09-04 NL NL7809025A patent/NL7809025A/en not_active Application Discontinuation
-
1979
- 1979-07-31 IT IT24809/79A patent/IT1122377B/en active
- 1979-08-14 DE DE2932873A patent/DE2932873C2/en not_active Expired
- 1979-08-14 GB GB7928219A patent/GB2029725B/en not_active Expired
- 1979-08-28 FR FR7921518A patent/FR2434889A1/en active Pending
- 1979-09-03 JP JP11271879A patent/JPS5536398A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0710683A1 (en) * | 1994-11-03 | 1996-05-08 | Hospal Industrie S.A. | Adhesion promoter for polyurethane adhesive compositions |
| FR2726567A1 (en) * | 1994-11-03 | 1996-05-10 | Hospal Ind | USE OF POLYETHYLENEIMINE AS AN ADHESION PROMOTER OF AN ADHESIVE POLYURETHANE COMPOSITION |
| FR2738847A1 (en) * | 1995-09-18 | 1997-03-21 | Adp Amenagement & Decoration D | CANVAS MATERIAL AND USE THEREOF TO REALIZE A FALSE CEILING |
| WO1997011221A1 (en) * | 1995-09-18 | 1997-03-27 | A.D.P. Amenagement & Decoration Du Plafond | Web material and use thereof for making a false ceiling |
Also Published As
| Publication number | Publication date |
|---|---|
| GB2029725B (en) | 1982-07-14 |
| FR2434889A1 (en) | 1980-03-28 |
| DE2932873A1 (en) | 1980-03-13 |
| IT1122377B (en) | 1986-04-23 |
| IT7924809A0 (en) | 1979-07-31 |
| DE2932873C2 (en) | 1982-04-22 |
| NL7809025A (en) | 1980-03-06 |
| JPS5536398A (en) | 1980-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2955958A (en) | Process of treating woven textile fabric with a vinyl chloride polymer | |
| US2314968A (en) | Process of impregnating textile materials and the material thus obtained | |
| US3098755A (en) | Coated rubber articles and method of producing same | |
| US3085027A (en) | Polyurethane coated fabric filled with isocyanate free elastomer and method of making same | |
| US3639154A (en) | Process for manufacturing fibrous structure having excellent recovery from extension by treatment with polyorganosiloxane and a polyethylene glycol or derivative thereof | |
| US3639157A (en) | Process for finishing textile materials with a polymer of a vinyl compound and the reaction product of a polyol and an organic polyisocyanate | |
| US3962054A (en) | Process for the treatment of cellulosic textile materials | |
| US3705823A (en) | Method of coating fibrous structure with a mixture of polyurethane pre-polymer and polyorganosiloxane | |
| GB2029725A (en) | Process for improving the adhesion of polyvinyl chloride to a woven or knitted fabric, web or other macromolecular polymethylene terephthalate product composed of threads, yarns or fibres | |
| US2981637A (en) | Coating of fabrics | |
| US3300431A (en) | Non-woven fabric and adhesive composition therefor | |
| US3460973A (en) | Process for rendering glass and polyesters adhesive to rubber | |
| US4066397A (en) | Textile materials having improved elasticity and method for producing same | |
| US2981978A (en) | Process of shrinking solid polymethylene terephthalate with halogenated methanes | |
| US3285798A (en) | Chemical composition, process using same and resulting product | |
| US2776223A (en) | Method of producing a pile fabric of cellulose acetate | |
| US4121901A (en) | Size composition for improving the adherence of multifilament polymeric yarns to substrates such as rubber, and methods using same | |
| US3272676A (en) | Method of effecting the adhesion of polyester materials to rubbers | |
| JP2687131B2 (en) | Flame-retardant synthetic leather and its manufacturing method | |
| US2428453A (en) | Process for making elastic vinyl copolymer resin textile articles | |
| US3240620A (en) | Adhesion of vinyl resins to nylon or other synthetic fibrous materials | |
| US2955954A (en) | Process for treating shaped articles prepared from synthetic linear polyesters | |
| US4041001A (en) | Wash-resistant antistatic coating compositions | |
| Sen | Coated textiles | |
| US3690926A (en) | Polyester fibres coated with an n-glycidyl compound embedded in a rubber matrix |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |