EP0044604A2 - Heissschmelzbares Schlichtmittel und seine Verwendung zum Schlichten von Textilien - Google Patents

Heissschmelzbares Schlichtmittel und seine Verwendung zum Schlichten von Textilien Download PDF

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Publication number
EP0044604A2
EP0044604A2 EP81301977A EP81301977A EP0044604A2 EP 0044604 A2 EP0044604 A2 EP 0044604A2 EP 81301977 A EP81301977 A EP 81301977A EP 81301977 A EP81301977 A EP 81301977A EP 0044604 A2 EP0044604 A2 EP 0044604A2
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EP
European Patent Office
Prior art keywords
size
melt
weight percent
copolymer
wax
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Granted
Application number
EP81301977A
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English (en)
French (fr)
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EP0044604B1 (de
EP0044604A3 (en
Inventor
Delano Monroe Conklin
John H. Hansen
John B. Hodgin
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Burlington Industries Inc
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Burlington Industries Inc
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Publication of EP0044604A2 publication Critical patent/EP0044604A2/de
Publication of EP0044604A3 publication Critical patent/EP0044604A3/en
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Publication of EP0044604B1 publication Critical patent/EP0044604B1/de
Expired legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10Treating 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 oxygen
    • D06M13/224Esters of carboxylic acids; Esters of carbonic acid
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof

Definitions

  • This invention relates to the hot melt sizing of textile warp yarns, more specifically to a novel class of non-aqueous warp sizes which are applied to yarn in the form of a melt.
  • U.S. Patent No. 3,466,717 describes a method and apparatus for sizing warp yarns, in which size is applied within a sizing chamber provided with a vat containing a quick-solidifying molten size whose predominant component is wax.
  • Exemplified for application in this apparatus is a molten size made with hardened castor oil, 2-ethylhexyl acrylate, and benzoyl peroxide, one of a number of sizes described in Japanese Patent Publication No. 14280/1965. More broadly, the latter publication describes certain classes of polymers or copolymers soluble in specified types of wax, capable of application to yarns by melt means. Three facts in this publication are particularly significant in the context of the present invention.
  • the first is its emphasis upon high compatibility of its various simple or mixed polymer components with its wax components.
  • the second is that at least 20 percent of a hydrophobic vinyl monomer, such as 2-ethylhexyl acrylate, must be present in its polymeric component if compatibility with the wax is to be achieved.
  • the third is that a substantial portion of an ester of a hydroxycarboxylic acid, such as found in hydrogenated castor oil or esters of hydroxyacids such as tartaric acid, must be present.
  • a minimum of 40 percent of this special kind of hydroxy ester wax is required as a component in the size compositions described in the Japanese patent publication.
  • U.S. Patent 4,136,069 describes melt sizes made from a polymeric blend of high molecular weight with low molecular weight ethylene ⁇ , ⁇ -unsaturated carboxylic acid copolymers, such, for example, as blends of high with low molecular weight ethylene/acrylic acid copolymers. These melt blends are employed as sizes either alone or in conjunction with 0-50 percent of one or more C 5 -C 12 dicarboxylic acids or with 0-30 percent, preferably 5-20 percent, of wax, fatty acid, or monoglyceride. With regard to the wax component, the patent makes no mention of animal or vegetable wax. Fischer-Tropsch or predominantly hydrocarbon waxes, the only classes of wax identified by name, are represented as only a minor substituent in a single example, at a level of 2.5 percent, in conjunction with 17.5 percent of a monoglyceride.
  • the present invention is concerned with providing a melt size containing substantially more hydrogenated tallow or equivalent triglyceride wax than hitherto tolerable in textile melt sizes, a melt size that is removable from fabric by either aqueous or organic solvent extraction or scouring means, a melt size exhibiting minimal smoking and fuming during hot melt application to yarn and a melt size giving superior weaving through the enhanced abrasion resistance and fiberlaydown of staple yarns to which it has been applied.
  • approximately equal weight amounts of fully hydrogenated tallow-type triglyceride wax and a specific ethylene/acrylic acid copolymer are melted together to form a superior textile melt size.
  • the lower limit of the copolymer content may be further reduced to as low as about 35 percent by weight by incorporation of from about one to seven percent of a hydrogenated tallow amide or other fatty acid amide, thereby further increasing the tallow-type component.
  • Another embodiment of the invention incorporates from about one to about nine percent of sebacic acid or dodecanedioic acid into blends of various proportions of copolymer and wax.
  • melts of the present invention are thus achieved without loss of either performance or economic merit.
  • Hydrogenated tallow the preferred triglyceride wax of the invention, has long been known, and the art suggests that its potential merit as a melt size component has evidently been recognized for many years. Nonetheless its utilization in high proportions in a melt size in conjunction with a simple and commercially available polymer represents a surprising and commercially important advance in the melt sizing of textile warp yarns.
  • the hot melt size compositions of the present invention comprise preferably an essentially two-component melt blend of about 42 to 58 weight percent of substantially 80/20 by weight ethylene/ acrylic acid copolymer in conjunction with about 58 to 42 weight percent of fully hydrogenated tallow-type triglyceride wax wherein optionally the copolymer content may be reduced to as little as about 35 weight percent by incorporation of one to seven percent of C 16-20 fatty acid amide or one to nine percent of sabacis or dodecanedioic acid, and wherein the copolymer has a standard melt flow rate value of 250-550 when determined by ANSI/ASTM D 1238-79 at Condition D.
  • the melt sizes of the present invention comprises two- or three-component melt blends of about 35 to 58 weight percent of ethylene/acrylic acid copolymer and about 62 to 42 weight percent of a fully hydrogenated triglyceride such as hydrogenated tallow, together with from 0 up to about 7 weight percent of a C 16 -C 20 fatty acide amide or from 0 up to about 9 percent of sebacic acid or dodecanedioic acid.
  • a fully hydrogenated triglyceride such as hydrogenated tallow
  • composition ranges of about 45 to 55 weight percent of substantially 80/20 ethylene/ acrylic acid and about 55 to 45 percent of hydrogenated triglyceride give the best results, with optimum mel sizing properties being centered around substantially 50:50 weight proportions of these components.
  • the preferred triglyceride is tallow.
  • the content of ethylene/acrylic acid copolymer in the size may be reduced below about 45 percent, to as low as about 35 percent, without significant loss of sized yarn performance.
  • the melt size of this embodiment comprises about 35 to 45 percent, preferably about 38 to 42 percent, of substantially 80/20 ethylene/acrylic acid copolymer, about 62 to 54 percent, preferably about 60 to 56 percent, of hydrogenated triglyceride, and about 1 to 7 percent, preferably about 2 to 5 percent, of fatty acid amide. Incorporation of the amide appears to increase the miscibility range of the copolymer and hydrogenated triglyceride, thereby permitting the use of less copolymer in the melt size.
  • compositions of the present invention comprising 40 to 55 percent ethylene/acrylic acid copolymer, 55 to 40 percent hydrogenated triglyceride wax, and 1 to 9 percent sebacic acid or dodecanedioic acid exhibit an expanded range of melt compatibility such that they can be melted and applied to yarn at significantly lower temperatures, i.e., up to around 28°C (50°F) lower, than the two component copolymer/tallow blends. Increased compatibility is closely associated with temperature rise, and the capacity for decreased temperature without component separation of the melt is particularly advantageous.
  • the blends containing sebacic acid or dodecanedioic acid further exhibit greatly improved resistance to smoking at melt temperature, only part of this resistance seeming to be attributable to their lower melting and application temperatures.
  • compositions of this type are those containing 4 to 7 percent sebacic acid or dodecanedioic acid in conjunction with approximately 50:50 proportions of copolymer and hydrogenated triglyceride.
  • various mixtures of sebacic and dodecanedioic acid together constituting the total 1-9 percent component may be used.
  • the low molecular weight ethyl ene/acrylic acid copolymers employed in the melt sizes of the present invention are themselves well known and commercially available materials. They may be made by methods disclosed in U.S. Patents 3, 520,861 and 4, 515, 317 or less preferably be precipitated from emulsion form as in U.S. Patent 3,436,363. The disclosures of these patents are hereby incorporated by reference. Polymers containing substantially 80/20 weight proportions of ethylene to acrylic acid are best suited to the sizes of the present invention. Commercial Polymers of this type are defined in terms of both composition and melt viscosity, which latter is expressed herein as determined by ANSI/ASTM Test Method D 1238-79 at Condition D. Polymers having a melt flow rate value of 250-550 grams per ten minutes according to this standard test are useful in our invention, with a polymer having a melt value of about 300 being preferred.
  • Hydrogenated or hardened tallow is a widely available by-product of the meat-packing industry made principally by hydrogenation of beef tallow. As such it is principally comprised of glyceryl tristearate, with lesser inclusions of mixed glycerides of C- 14-20 saturated fatty acids. Principally because of its currently favorable price and availability, what is conventionally known as "fully hydrogenated" beef tallow (iodine number less than one ) is the preferred triglyceride of the invention.
  • castor wax Expressly excluded from the category of triglycerides of the invention is castor wax, the fully hydrogenated derivative of castor oil. Because of the very high proportion of ricinoleic acid in castor oil, castor wax, with its correspondingly high content of 12-hydroxystearic acid moieties, is unsuitable for use as a major component in the melt sizes of the invention.
  • the fatty acid amides also commercially known as hydrogenated tallow amides, and commonly made by reaction of free acids or hydrogenated tallow with ammonia, are typically mixtures of C 14 - 20 acid amides, principally stearamide. More chemically specific fatty acide amides may of course be employed in the invention, but will naturally be more expensive.
  • a size block is then pushed against and into the grooves of a heated applicator roll , typically at 177°-204°C (350°-400°F), from which grooves size is taken up as the yarn passes tangentially or along an arc of the turning roll. Further details will be found in the subsequent examples of the invention.
  • Desizing can be effected by either conventional alkaline aqueous scours or organic solvents, as with mixtures of petroleum solvents and methanol as described in our U.S. Patent No. 4,253,840, dated March 3, 1981.
  • the lower end of the preferred application temperature range offers greater protection against fuming and smoking, and in particular it markedly reduces the rate of thermally-induced reactions which otherwise might lead to gelling or other premature solidification of the size at the point of application.
  • Heating the applicator roll at about 177°C(350°F) is thus preferred at start-up times and at other times where unscheduled delays might cause molten size to remain longer than desired on the applicator roll.
  • the canpositional parameters of our invention have been established in view of the performance characteristics of our melt sizes. Based upon our observations and date it appears that above about 60 weight percent of ethylene/acrylic acid copolymer, having the prescribed 250-550 melt flow rate value, the compatibility of the molten components is if anything excessive. In any case the melt has become so viscous at and above this high percentage of polymer as to be almost unusable as a melt size. In a two-component melt system, when the polymer content drops below about 40 weight percent, the compatibility in the molten state is insufficient, leading to erratic and uneven sizing performance.
  • the lower limit of copolymer content may be somewhat extended, i.e., to about 35 weight percent, by incorporation of small amounts of fatty acid amides without upsetting the precarious balance of the high-tallow melts. It is believed that the tallow serves within a few degrees of the application temperature as a dispersant for the polymer, but as cooling begins, enough phase separation occurs that the yarn becomes coated with a size film having a higher polymer content and more strength and flexibility than would be expected of such a high total tallow content if all the tallow had remained in a single blend phase on cooling.
  • a significant merit of the present invention which is thought to be related to the limited compatibility of the size components is that the size yarn performs so well in the loom. Its lack of tendency to build up deposits on heddles and other loom parts is uncommonly good, especially in a size with such high wax content. This characteristic, which applicants associate with lack of tackiness of the sized yarn over wider than usual temperature ranges, is far more significant in a yarn sizing context than mere measurements of size film strengths and elongations.
  • the sizes of the present invention can be applied successfully at much higher add-on than most melt sizes, without adverse effect upon either sizing or weaving performance.
  • the aforementioned Japanese patent publication describes doubling, weaving, knitting, etc. difficulties encountered when application of its sizes exceeded 4 weight percent.
  • the sizes of the present invention have been applied successfully to yarns of various types and dimensions in amounts ranging from 8 to 18 percent. Lower add-ons can be applied to less demanding yarns than the hairy spun yarns which have mostly been tested in the course of the invention. Loom performance has been superior.
  • melt size composition preparation for initial laboratory screening, small samples of 80/20 ethyl ene/acrylic acid copolymer, having an indicated standard melt flow rate value .(hereinafter referred to as SMFR), as determined by ANSI/ASTM D 1238-79 at Condition D, were melt- blended with designated amounts of hydrogenated tallow and tallow amide.
  • SMFR standard melt flow rate value
  • Brookfield viscosity measurements A simple measurement useful in screening the sizes of the invention is the Brookfield viscosity, and more particularly the calculated coefficient of variation (COV) of a succession of Brookfield (Model LVF) viscosity measurements on the same melt.
  • COV coefficient of variation
  • a 10-gm portion of the molded size stick is melted in a constant- temperature bath, and the viscosity is measured at 204°C (400°F), with a No. 4 spindle, at 60 rpm.
  • Ten successive measurements are taken, and then analyzed to determine their COV. Since the melts were known to gel if held molten overnight, it was recognized that the viscosity was moderately time- dependent; hence the measurements were taken as rapidly as possible, at about 30 seconds each.
  • Abrasion test As a screening means for estimating the relative resistance of the sized yarns to abrasion in a shuttle loom, a rapid abrasion test was applied to most of the test specimens.
  • the device used consists of a vertically-mounted heddle eye affixed to the top of a short rod, the bottom of which rod is in turn clamped to the shaft of a horizontally-mounted air cylinder.
  • the thrust of the cylinder is controlled to impart a horizontal reciprocating motion,10.16 cm (4 inches) in each direction along a straight line, to the heddle eye.
  • a yarn clamp and a 0.32 cm (1/8-inch) rod Above and parallel to the path of the cylinder shaft, and about one inch below the bottom of the heddle eye hole, are fixed a yarn clamp and a 0.32 cm (1/8-inch) rod, clamp and rod being 25.4 cm (ten inches) apart with the heddle eye between them.
  • Each yarn sample, for testing is fixed in the clamp, passed through the heddle eye, and hung over the rod with a 90-gm weight attached to put tension on the yarn.
  • the yarn forms an isosceles triangle, one inch high, with the 25.4 cm (10-inch) line between yarn clamp and drape rod.
  • the plane of the heddle eye is set about 20° away from normal to the yarn line, as heddles are set in a loom.
  • the device operates at a rate of about 150 reciprocations per minute.
  • a counter records the number of reciprocations.
  • the 90-gn weight on the yarn makes the test a very rigorous one.
  • Each counted reciprocation or stroke of the heddle eye ccmprises a trip over and back to the starting point.
  • the operator watches the yarn very carefully as testing begins, and when the yarn begins to deteriorate, which with a poor size is practically at once, the counter reading is recorded. If the number of steokes to break are desired, the device continues until the yarn breaks. At least 20 specimens of each yarn are tested to reach an average, which typically is in the 3. 0 to 5.0 range for a "good" yarn. Steokes-to-break for such yarns are in the range of 200-250.
  • Deterioration is judged to represent a point, considerably short of formation of fuzz balls, where the roughed-up and hairy yarn surfaces of adjacent yarns in a warp would be likely to cause intra-warp friction and snagging under the action of a loom.
  • the 90-gm weight with its attendant low but imprecise test numbers, has been retained in the interest of speed and efficiency in screening out likely failures among a large number of samples. Good correlation has been observed between a relatively high rating in the test and actual performance in a commercial loom.
  • the apparatus comprises a 0.32 x30.48cm (1/8 x 12 inch) stainless steel rod, mounted essentially horizontal (bowed 1.27 in 15.24 cm (0.5 inch in six) towards the center) on a reciprocating wooden platform, whereby a 10.16 cm (4-inch) movement of the rod in each direction along its axis is produced.
  • a thermocouple is attached to the bottom of the rod at its center, for the purpose of determining temperature changes in the rod.
  • Friction of the warp on the test rod is judged by recording the rod temperature, which typically rises from room temperature to about 40.5°C (105°F)during testing of an effective size, to as high as 51.6°C (125°F) with a marginal or poor size.
  • Other evidence of poor size performance is lateral or rolling action of the warp, which indicates its sticking or seizing on the rod, in which event the test usually is terminated early.
  • the rod is carefully examined for evidence of size sticking to it, and if none is found, "no deposit” is recorded and the size is regarded as a candidate for a full weaving test. Note is taken of the possible presence of loose dust on the wooden platform, as an indication of the dusting potential of the size in a loom.
  • Equal portions of hydrogenated tallow and 80/20 by weight ethylene/acrylic acid (EAA) copolymer having an SMFR of 500 were melted together.
  • the Brookfield viscosity of the size was 825-850 cps.
  • Size add-on to 25/1 65/35 polyester/cotton yarn with the 2.54 cm (1-inch) grooved roll at 204°C (400 0 F) was 15.7 percent, the sizing operation being smooth throughout.
  • the sized yarn gave a favorable reading of 5.2 strokes to deterioration, 202 strokes to break.
  • the sized warp went the entire 27.42 m (30 yards) and there was no deposit on the test rod at the end of the test.
  • the 40/60 EAA/tallow combination suffers from an opposite fault, exemplified in its excessive C07 of 12.7.
  • Such a high level of variation in the successive Brookfield measurements is indicative of a very non-uniform melt and of poor miscibility of the components.
  • this high-tallow composition excessively hazy at 204°C (400°F) in comparison with the other melts, but on close examination it was apparent that the melt was distinctly non-uniform, with visible evidences of insufficiently dispersed polymer.
  • Example 4 The range of compositions evaluated in Example 4 was extended by lowering the EAA content to 35 percent, and then to 30 percent. The results are shown in Table 3.
  • SMFR 80/20 ethyl ene/acrylic acid copolymer with hydrogenated tallow in the form of blocks 2.2 cm (7/8- inch) thick.
  • the yarn was taken up on section beams until each of ten beams contained 2925 m (3200 yards) of sized yarn.
  • the section beams were then rewound onto two Sulzer loom beams, each containing 3992 warp ends.
  • the beams were mounted on a double-warp Sulzer loom for weaving of 304.8cm (120-inch sheeting fabric.
  • the weaving performance based on the number of warp stops and on loom efficiencies, was compared with weaving of other conventionally aqueous-sized warp weaving the same style in the same weave area.
  • the hot-melt-sized warp averaged only 46.3% of the warp-related loom stops of the conventional warps, and its loom efficiency was about 5% higher than those of the conventionally- sized warps.
  • A' mel t blend composed of 45% of 300 SMFR 80/20 ethylene/acrylic acid copolymer, 48% hydrogenated tallow, and 7% sebacic acid was heated until the melt became compatible, as defined above, at about 138°C (280°F), a temperature about 39°C (70°F) lower than the temperatures generally observed for a variety of proportions of copolymer and tallow in the 2-component sizes of the invention.
  • the size was preliminarily screened by application to yarn as in Example 1, at a level of 12.5%. On the abrasion tester the sized yarn gave favorable results, comparable to those of the 2- component sizes of the invention.
  • a melt blend of 32% copolymer, 59% hydrogenated tallow, and 9% sebacic acid became compatible somewhat later, at 149°C (300°F), but a film cast from the melt was judged too brittle to indicate utility as a melt size.
  • a melt blend of 47.5% copolymer, 47% hydrogenated tallow, and 5.5% dodecanedioic acid became compatible at 138°C (280°F) , and showed resistance to gelatin comparable to the melts of Examples 8 and 9.
  • the melt temperature was 182°C (360°F)
  • the initial B rookfield viscosity of 1326 cps rose to only 1598 cps in 24 hours, to 1748 cps in 32 hours, and to 2894 cps in 56 hours.
  • melt sizes of the invention are also suited to the sizing of other natural and synthetic yarns, such as 100% cotton, 100% wool, wool/cotton, wool/polyester, and others.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP81301977A 1980-05-06 1981-05-05 Heissschmelzbares Schlichtmittel und seine Verwendung zum Schlichten von Textilien Expired EP0044604B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US14733580A 1980-05-06 1980-05-06
US147335 1980-05-06
US25731581A 1981-04-17 1981-04-17
US257315 1981-04-17

Publications (3)

Publication Number Publication Date
EP0044604A2 true EP0044604A2 (de) 1982-01-27
EP0044604A3 EP0044604A3 (en) 1982-11-10
EP0044604B1 EP0044604B1 (de) 1985-10-02

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EP81301977A Expired EP0044604B1 (de) 1980-05-06 1981-05-05 Heissschmelzbares Schlichtmittel und seine Verwendung zum Schlichten von Textilien

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EP (1) EP0044604B1 (de)
CA (1) CA1193404A (de)
DE (1) DE3172481D1 (de)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1360634A (fr) * 1962-06-19 1964-05-08 Union Carbide Corp Composition comprenant des mélanges d'une cire avec des polymères d'éthylène et d'acide acrylique
US3466717A (en) * 1966-11-19 1969-09-16 Kawamoto Ind Method of and apparatus for sizing warps
US4253840A (en) * 1979-03-20 1981-03-03 Burlington Industries, Inc. Hot-melt size compositions and process for textiles

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3004636C2 (de) * 1980-02-08 1985-10-31 Walter 7500 Karlsruhe Gehmann Ringkorn für Sportgewehre

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1360634A (fr) * 1962-06-19 1964-05-08 Union Carbide Corp Composition comprenant des mélanges d'une cire avec des polymères d'éthylène et d'acide acrylique
US3466717A (en) * 1966-11-19 1969-09-16 Kawamoto Ind Method of and apparatus for sizing warps
US4253840A (en) * 1979-03-20 1981-03-03 Burlington Industries, Inc. Hot-melt size compositions and process for textiles

Also Published As

Publication number Publication date
CA1193404A (en) 1985-09-17
EP0044604B1 (de) 1985-10-02
EP0044604A3 (en) 1982-11-10
DE3172481D1 (en) 1985-11-07

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