US3516956A - Spinnable compositions comprising a fiber forming polyamide,a fiber forming polyester and a spinning aid - Google Patents
Spinnable compositions comprising a fiber forming polyamide,a fiber forming polyester and a spinning aid Download PDFInfo
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- US3516956A US3516956A US568725A US3516956DA US3516956A US 3516956 A US3516956 A US 3516956A US 568725 A US568725 A US 568725A US 3516956D A US3516956D A US 3516956DA US 3516956 A US3516956 A US 3516956A
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- United States
- Prior art keywords
- yarn
- polyester
- polyamide
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- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title description 72
- 238000009987 spinning Methods 0.000 title description 38
- 229920002647 polyamide Polymers 0.000 title description 33
- 239000004952 Polyamide Substances 0.000 title description 32
- 229920000728 polyester Polymers 0.000 title description 29
- 239000000835 fiber Substances 0.000 title description 16
- 229920000642 polymer Polymers 0.000 description 28
- -1 polyethylene terephthalate Polymers 0.000 description 23
- 238000002844 melting Methods 0.000 description 21
- 230000008018 melting Effects 0.000 description 21
- 238000004455 differential thermal analysis Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 239000008188 pellet Substances 0.000 description 18
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 14
- 238000010791 quenching Methods 0.000 description 14
- 230000000171 quenching effect Effects 0.000 description 14
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 14
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 10
- 239000005020 polyethylene terephthalate Substances 0.000 description 10
- 239000004576 sand Substances 0.000 description 8
- 229920002292 Nylon 6 Polymers 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 230000001050 lubricating effect Effects 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 7
- 230000002093 peripheral effect Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 229940045870 sodium palmitate Drugs 0.000 description 5
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-UHFFFAOYSA-M 0.000 description 5
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 238000002076 thermal analysis method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002429 hydrazines Chemical class 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N methyl undecanoic acid Natural products CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N n-hexadecanoic acid Natural products CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- NUGCKKMWDPZJCB-UHFFFAOYSA-N octadecanamide;octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(O)=O NUGCKKMWDPZJCB-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- 239000010965 430 stainless steel Substances 0.000 description 1
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 241001589086 Bellapiscis medius Species 0.000 description 1
- XYSJPPZDIGSWBU-UHFFFAOYSA-N C(CNC(CCCCCCCCCCCCCCCCC)=O)NC(CCCCCCCCCCCCCCCCC)=O.C(CCCCCCCCCCCCCCCCC)(=O)NCCNC(CCCCCCCCCCCCCCCCC)=O Chemical compound C(CNC(CCCCCCCCCCCCCCCCC)=O)NC(CCCCCCCCCCCCCCCCC)=O.C(CCCCCCCCCCCCCCCCC)(=O)NCCNC(CCCCCCCCCCCCCCCCC)=O XYSJPPZDIGSWBU-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003855 acyl compounds Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 150000001470 diamides Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- CQISYTXUORWJSX-UHFFFAOYSA-N n-[4-(octadecanoylamino)phenyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NC1=CC=C(NC(=O)CCCCCCCCCCCCCCCCC)C=C1 CQISYTXUORWJSX-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
Definitions
- Wax-like derivatives of saturated straight-chain carboxylic acids containing between about 12 and about 22 carbon atoms are incorporated into a spinnable composition comprising a fiber-forming polyamide having dispersed therein about to 50 percent by weight of a fiberforming polyester,.
- These wax-like derivatives e.g., metallic salts, amides, and acylated hydrazines
- spinnable compositions are incorporated into the spinnable composition to the extent of between about 0.05 and about 0.6 percent 'by weight and serve to inhibit the formation of drips in the vicinity of spinneret o-rfices and reduce the occurrence of breaks or wraps during drawing of the spun filaments.
- This invention relates to the preparation of textile fbers. More particularly, it relates to the preparation of fibers from compositions comprising polyesters dispersed in polyamides. It also includes within its scope the compositions themselves.
- compositions useful in the production of a ⁇ ariety of textile products including tire cords, drapes, rlothing and the like can be prepared by extruding melt l lended compositions comprising polyesters such as polyethylene terephthalate with polyamides especially nylons such as polycaproamide and polyhexamethylene adipamide.
- the filaments may be formed by first dry blending the polymers suitably in the form of chips and thereafter melt blending the compositions in a screw extruder or analogous device and extruding the molten composition through a spinnerette. @In the molten blend the polyester is dispersed in the polyamide in a fine state of subdivision.
- Such dispersion is normally attained by subjecting the melt to high shearin the extruder or analogous device and forcing the result melt through a pack of screens, a sand bed or similar fine filter.
- the molten dispersion is then extruded through the spinnerette into a cooling zone in which the extrudate solidifies in a filamentary form.
- the cooling one is normally a long stack in which the temperature and humidity are carefully controlled. There is a take-up roll for winding the filaments at the bottom of the stack.
- the filaments are normally gathered together into yarns which may then be subjected to a drawing operation to improve their physical properties.
- the drawing operation is generally carried out by extending the yarns at a temperature below the melting point of either component of the yarns and confers molecular orientation along the filament axis so as to increase the strength of the yarns.
- Draw ratios of from about 3.5 to about 6.5 are normally employed with polyester-polyamide compositions, draw ratio being defined as the ratio of the length of the drawn yarn to the length of the undrawn yarn.
- Lower draw ratios within this range are used in the preparation of textile yarns where high strength is not necessarily a requirement.
- Higher dra w ratios within the range are usually used for the preparation of high strength yarns such as yarns intended for use in tire cords.
- the yarn can be. drawn in either single or successive stages and at least one of the stages is best carried out at a relatively high temperature.
- the drawing operation is preferably carried out with the aid of a drawpin which localizes the region of drawing
- the yarn is taken up on a take up roll or a pirn and is then ready for use.
- the yarn may also be twisted to improve cohesion of the several filaments before use.
- a break is the rupture of the yarn in the draw zone. This requires a shutdown and restarting of the entire drawing operation.
- a wrap occurs when one or more but less than all of the filaments in the yarn rupture in the draw zone. The oncoming ends of the ruptured filaments will wrap around the roll instead of moving ahead to the twister. This situation can sometimes be corrected without shutting down, but the properties of the resulting yarn may be adversely affected.
- the spinning aids employed in this invention have a mold release index of at least 25 when incorporated in pure nylon 6 (polycaprolactam or polycaproamide-, and they do not exert a plasticizing effect on the polyester-polyamide blend, more specifically, they do not reduce the tensile modulus of fibers prepared from the blend.
- Spinning aids having the desired characteristics are generally derivatives of long chain fatty aliphatic acids such as lauric, palmitic, stearic or behenic acid.
- Metallic salts, amides and acylated hydrazines are typical examples of useful spinning aids.
- the following table lists a number of representative wax-like spinning aids found to be useful in accordance with this invention together with their melting points and mold release indices. These representative wax-like spinning aids include diamides derived by the reaction of an aliphatic carboxylic acid and a diamine or hydrazine and alkali or alkaline earth metal salts of aliphatic carboxylic acids.
- nylon 6 (polycaprolactam or polycaproamide) pellets containing, homogeneously blended therein, 0.2% of the additive to be tested are fed to a Van :Dorn injection molding machine operating at a rear cylinder temperature of 365 F. and a mold temperature of 180 F.
- the injection line pressure is maintained at 1100 psi. with an injection forward time of seconds and a mold open time of at least 2 seconds.
- the front cylinder temperature is adjusted to produce the melt viscosity required to fill the mold without flash, i.e., the filmy attachments to the edges of the molded article due to polymer leakage between the halves of the mold.
- the mold employed is a disk of 2 inches diameter and A; inch thickness provided with a inch diameter plunger flush-mounted in the bottom of the mold and centered therein.
- the mold is fabricated of Type 430 stainless steel.
- the melting time is 2 minutes, injection time seconds, and clamp time seconds.
- the force necessary to extricate the disk from its mold is measured via pneumatic pressure applied to the plunger.
- a comparative test is made on a control sample of the same polyamide containing no mold release additive.
- the mold release index is defined as the percentage- Wise decrease in extrication pressure for the test sample in comparison with the control. For example, if the pure polyamide extrication pressure is 110 p.s.i.g. and the extrication pressure of the sample being tested is 60, then the mold release index would be 11060/110 :45. By this test method, spinning aids which are useful in the present invention will have to have a mold release index greater than 25.
- temperatures, pressures, and residence times are observed and recorded to assure consistency and reproducibility of results.
- the molding machine is purged with standard pure polyamide polymer. Then the system is purged (usually 20-30 shots) with the polymer under test until uniform results are obtained. During this period, optimum operating temperatures and injection pressure are determined. After purging, the extrication pressures from 10 consecutive moldings are averaged and recorded as the extrication pressure for the polymer/ additive composition.
- the preferred spinning aids are alkali and alkaline earth metal salts since these compounds are readily and economically available in substantially pure form.
- Sodium palmitate and sodium stearate are particularly preferred because of the excellent results which can be obtained by their use.
- the selected spinning aid can be added at any con venient time during the dry or melt blending of the composition or may be incorporated in the polymers during polymerization. It may be added in solid form or in a solution or slurry employing a low boiling liquid which may be removed by evaporation.
- a Spinning aid in solid particulate form is mixed with the fiber forming polymer components during the dry blending. It is simply added to the dry, particulate blend and the whole mass mixed by stirring or other suitable means. During the mixing the spinning aid is evenly distributed on the surfaces of the polymer particles, thereby assuring its uniform distribution throughout the polymer composition.
- compositions containing as little as parts by weight of polyester or even less can be achieved with compositions containing as little as parts by weight of polyester or even less.
- the difliculties outlined above become progressively more troublesome with increasing concentration of polyester. Accordingly, the invention is especially useful with compositions in which the polyester content is 30 parts by weight or higher.
- a spinning aid is used in association with the fiber forming polyester-polyamide compositions described and claimed in copending patent application Ser. No. 368,028 filed on May 18, 1964, Now U.S. Pat. No. 3,369,057, issued Feb. 13, 1968, which is assigned to the same assignee as this application.
- That application describes filament-forming compositions comprising from about to about 50 parts by weight of filament-forming polyester dispersed as microfibers in a continuous body of from about 50 to about 90 parts by weight of filament-forming polyamide.
- the polyamide is further characterized as having not more than 40% end group species which are reactive with the polyester in the melt.
- the polyester is a long chain polymeric ester having a glass transition temperature when in the amorphous form which is at least 50 C. as measured by differential thermal-analysis and is higher than that of the polyamide component.
- the reduced viscosity of the polyamide component as measured at a concentration of 0.5 gram of polymer per 100 milliliter of solution in ortho-chlorophenol at 25 C. is in the range of 0.9 to 1.4 and the ratio of polyamide reduced viscosity to polyester reduced viscosity is between about 0.9 and 2.0.
- the composition is generally melt blended and extruded through the spinnerette at a temperature of from about 260 C. to about 285 C. which is about 10 C. to 40 C. above the melting point of the higher melting component.
- Polycaproamides and polyhexamethylene adipamides are utilized in preferred embodiments of this invention, although other polyamides prepared from polyamides forming monomers containing from 4 to 14 carbon atoms may be employed.
- Preferred polyesters include the polyethylene phthalates especially polyethylene terephthalates although other condensation products of dibasic acids such as naphthalene-2,6, and 2,7 dicarboxylic acids, and polyhydroxy alcohols such as ethylene or propylene glycol, or sterically hindered glycols maybe employed.
- the molten mixture was pumped through a filter pack including a series of screens and a sand bed under a pressure of 2800 lbs. per square inch at a temperature of 265 C. and was extruded through a spinnerette plate having 204 orifices of circular cross section each of said orifices having the following dimensions-length 0.069 inch, diameter 0.018 inch, entrance angle 60".
- the resulting filaments passed downwardly through a quenching chamber containing air at 27.8 C. and 65% relative humidity flowing concurrently to the filaments at a rate of about 75 cubic feet per minute.
- the yarn was taken up onto a cylindrical package below the quenching chamber at a speed of 1140 feet per minute under a tension of 35 grams.
- a lubricating finish was applied to the yarn to the extent of 4.3% pickup based on the weight of yarn.
- the yarn thus obtained has an approximate denier of 6772 and a birefringence of 0.004.
- the yarn was then subjected to a drawing operation by running the yarn to an upper draw roll from a cot feed roll. It was then passed in one wrap about a stationary ceramic drawpin of 1% inch diameter to a contact surface heater at C. and finally in 5 wraps about a lower draw roll at a peripheral speed of 5.52 times faster than the upper draw roll. The yarn was drawn to 5.3 times its initial length.
- the yarn was subsequently wound onto a pirn at a rate of 840 feet per minute using a ring-traveler device so as to impart 0.5 turn per inch twist to the yarn.
- the yarn thus obtained has the following properties:
- EXAMPLE 2 The process of this example is substantially similar to that of Example 1. Comparison of the two examples 7 clearly establishes the superiority of spinning composition containing sodium stearate.
- the molten mixture was pumped through a filter pack including a series of screens and a sand bed under a pressure of 3500 lbs. per square inch at a temperature of 265 C. and was extruded through a spinnerette plate having 204 orifices of circular cross section each of said orifices having the following dimensionslength 0.069 inch, diameter 0.018 inch, entrance angle 60.
- the resulting filaments passed downwardly through a quenching chamber containing air at 27.8" C. and 65% relative humidity flowing cocurrently to the filaments at a rate of about 75 cubic feet per minute.
- the yarn was taken up onto a cylindrical package below the quenching chamber at a speed of 1178 feet per minute under a tension of 35 grams.
- a lubricating finish was applied to the yarn to the extent of 4.5% pickup based on the weight of yarn.
- the yarn thus obtained had an approximate denier of 6727 and a birefringence of 0.003.
- the yarn was then subject to a drawing operation by running the yarn to an upper draw roll from a cot feed roll. It was then passed in one wrap about a stationary ceramic drawpin of 1 /2 inch diameter to a contact surface heater of 185 C. and finally in 5 wraps about a lower draw roll at a peripheral speed of 5.58 times faster than the upper draw roll. The yarn was drawn to 5.38 times its initial length.
- the yarn was subsequently wound onto a pirn at a rate of 840 feet per minute using a ring-traveler device so as to impart 0.5 turn per inch twist to the yarn.
- the yarn thus obtained had the following properties:
- the molten mixture was pumped through a filter pack including a series of screens and a sand bed under a pressure of 2900 lbs. per square inch at a temperature of 265 C. and was extruded through a spinnerette plate having 204 orifices of circular cross section each of said orifices having the following dimensionslength 0.069 inch, diameter 0.018 inch, entrance angle 20.
- the resulting filaments passed downwardly through a quenching chamber containing air at 27.80 C. and 65% relative humidity flowing cocurrently to the filaments at a rate of about 75 cubic feet per minute.
- the yarn was taken up onto a cylindrical package below the quenching chamber at a speed of 1180 feet per minute under a tension of 35 grams.
- a lubricating finish was applied to the yarn to the extent of 4.4% pickup based on the weight of yarn.
- the yarn thus obtained had an approximate denier of 6712 and a birefringence of 0.00228.
- the yarn was then subjected to a drawing operating by running the yarn to an upper draw roll from a cot feed roll. It was then passed in one wrap about a stationary ceramic drawpin of 1 /2 inch diameter to a contact surface heater at C. and finally in 5 wraps about a lower draw roll at a peripheral speed of 5.58 times its initial length.
- the yarn was subsequently wound onto a pirn at a rate of 840 feet per minute using a ring-traveler device so as to impart 0.5 turn per inch twist to the yarn.
- the yarn thus obtained had the following properties:
- EXAMPLE 4 The process of this example is substantially similar to that of Example 3. Comparison of the results of the two examples clearly establishes the superiority of spinning compositions containing sodium palmitate.
- the molten mixture was pumped through a filter pack including a series of screens and a sand bed under a pressure of 2300 lbs. per squareinch at a temperature of 275 C. and was extruded through a spinnerette plate having 204 orifices of circular cross section each of said orifices having the following dimensions-length 0.069 inch, diameter 0.018 inch, entrance angle 20.
- the resulting filaments passed downwardly through a quenching chamber containing air at 27 .8 C. and 65% relative humidity flowing cocurrently to the filaments at a rate of about "75 cubic .feet per minute.
- the yarn was taken up onto a cylindrical package below the quenching chamber at a speed of 1130 feet per minute under a tension of 35 grams. Just prior to packaging a lubricating finish was applied to the yarn to the extent of 4.5% pickup based on the weight of yarn.
- the yarn thus obtained had an approximate denier of 7026 and a birefringence of 0.0014.
- the yarn was then subjected to a drawing operation by running the yarn to an upper draw roll from a cot feed roll. It was then passed in one wrap about a stationary ceramic drawpin of 1% inch diameter to a contact surface heater at 185 C; and finally in 5 wraps about a lower draw roll at a peripheral speed of 5.78 times faster than the upper draw roll the yarn drawn to 5.72 times its initial length.
- the yarn was subsequently wound onto a pirn at a rate of 840 feet per minute using a ring-traveler device so as to impart 0.5 turn per inch twist to the yarn.
- the yarn thus obtained had the following properties:
- the molten mixture was pumped through a filter pack including a series of screens and a sand bed under a pressure of about 3500 lbs. per square inch at a temperature of 265 C. and was extruded through a spinnerette plate having 204 orifices of circular cross section each of said orifices having the following dimensions-length 0.069 inch, diameter 0.018 inch, entrance angle 20.
- the re- 'sulting filaments passed downwardly through a quenching chamber containing air at 27.8 C. and 65% relative humidity flowing cocurrently to the filaments at a rate of about 75 cubic feet per minute.
- the yarn was taken up onto a'cylindrical package below the quenching chamber at a speed of 1180 feet per minute under a tension of 35 to 45 grams. Just prior to packaging a lubricating finish was applied to the yarn to the extent of 4.5% pickup based on the weight of yarn.
- the yarn thus obtained had an approximate denier of 6666 and a birefringence of 0.0043.
- the yarn was then subjected to a drawing operation by running the yarn to an upper draw roll from a cot feed roll to prevent yarn slippage. Then in one Wrap about a stationary ceramic drawpin of 1%. inch diameter, then to a contact surface heater at C. and finally in five wraps about a lower draw roll and associated at a peripheral speed of 5.48 times faster than the upper draw roll the yarn was drawn to 5.23 times its initial length.
- the yarn was subsequently wound onto a pirn at a rate of 840 feet per minute using a ring-traveler device so as to impart 0.5 turn per inch twist to the yarn.
- the yarn thus obtained had the following properties:
- Example 6 The process of this example is substantially similar to that of Example 5 except that in this example 0.10% sodium stearate is employed as a spinning aid and the extruder is used to feed two positions. It should be noted in comparing the results that the drips per hour in Examples 5 and 6 are substantially the same. However, the throughput per hour in Example 6 is 65.4 lbs. per hour, whereas the total throughput in Example 5 is 32.7 lbs. per hour. It is thus apparent that the use of the spinning aid in accordance with this invention permits the spinning of polyester-polyamide blends at a much higher rate without adversely affecting the drips per hour, which heretofore has not been accomplished.
- the molten mixture was pumped through a filter pack including a series of screens and a sand bed under a pressure of about 3500 lbs. per square inch at a temperature of 265 C. and was extruded through two spinnerette plates each having 204 orifices of circular cross section each of said orifices having the following dimensionslength 0.069 inch, diameter 0.018 inch, entrance angle 20".
- the resulting filaments passed downwardly through a quenching chamber containing air at 27.8" C. and 65% relative humidity flowing cocurrently to the filaments at a rate of about 75 cubic feet per minute.
- the yarn was taken up onto a clyindrical package below the quenching chamber at a speed of 1180 feet per minute under a tension of 35 to 45 grams. Just prior to packaging a lubricating finish was applied to the yard to the extent of 4.5% pickup based on the weight of yarn.
- the yarn thus obtained had an approximate denier of 6616 and a birefringence of 0.0043
- the yarn was then subjected to a drawing operation by running the yarn to an upper draw roll from a cot feed roll. It was then passed in one wrap about a stationary ceramic drawpin of 1% inch diameter, then to a contact surface heater at 135 C. and finally in five wraps about a lower draw roll and associated at a peripheral speed of 5.56 times faster than the the upper draw roll the yarn was drawn to 5.38 times its initial length.
- the yarn was subsequently wound onto a pirn at a rate of 840 feet per minute using a ring-traveler device so as to impart 0.5 turn per inch twist to the yarn.
- the yarn thus obtained had the following properties:
- EXAMPLE 7 The following is a list of a variety of spinning aids which were employed in accordance with this invention utilizing a 30/70 blend of polyester and polyamide in which the polyethylene terephthalate and polycaproamide employed were similar to those utilized in Example 2 and were similarly processed to produce the yarn. In each case less than one drip per hour was observed.
- the granular blend was dried to a moisture content of no more than 0.038% and then melt blended at 265 C. in a 3.5 inch diameter extruder operated at a rotational speed of 23 r.p.m. to produce a pressure of about 3000 lbs. per square inch at the outlet.
- the temperature of the polymer composition on leaving the extruder was 265 C.
- the molten mixture was pumped through a filter pack including a series of screens and a sand bed under a pressure of 2000 lbs. per square inch at a temperature of 265 C. and was extruded through a spinnerette plate having 204 orifices of circular cross section, each of said orifices having the following dimensions-length 0.069 inch, diameter 0.018 inch.
- the resulting filaments passed downwardly through a quenching chamber containlng air at 27.8 C. and 65% relative humidity flowing cocurrently to the filaments at a rate of about 58 cubic feet per minute.
- the yarn was taken up onto a cylindrical package below the quenching chamber at a speed of 1130 feet per minute under a tension of 35 grams. Just prior to packaging a lubricating finish was applied to the yarn to the extent of 4.6% pickup based on the weight of the yarn.
- the yarn thus obtained had an approximate denier of 6844 and a birefringence of 0.0025.
- the yarn was then subjected to a drawing operation by running the yarn to an upper draw roll from a cot to prevent slippage. It was then passed in one wrap about a stationary ceramic draw pin of 1.5 inch diameter to a contact surface heater at 185 C. and finally in five wraps about a lower draw roll at a peripheral speed of 5.73 times faster than the upper draw roll. The yarn was drawn to 5.40 times its initial length.
- the yard was subsequently wound onto a pirn at a rate of 840 feet per minute using a ring traveler device so as to impart 0.5 turn per inch twist to the yarn.
- Table III below' records the results obtained without sodium stearate and with sodium stearate at four different levels of concentration.
- the conditioned specimens are tested as follows:
- the fiat-spot index is taken as the differences in length between the twospecimens afterreapplication of load in step 10, expressed in millimeters and multiplied by ten.
- the fiat spot index of the yarn prepared utilizing 0.11% by weight sodium stearate was 22 and that the flat spot index for a yarn prepared with no sodium stearate was substantially the same. This figure is well within the range of commercial acceptability.
- the adhesion test employed herein is the standard H adhesion test employing two-ply cords of the yarn to be tested, coated with the standard resorcinol-formaldehydelatex or a polyester adhesive finish, and employing natural rubber as the elastomeric substrate.
- the force in pounds is measured for pulling, in the axial direction, one test cord from a laminate of rubber with a quarter inch length of cord embedded therein, said laminate being maintained at 250 F.
- the adhesive-treated cord is placed between two thicknesses of rubber stock in a mold with the cord under a tension of 50 grams.
- the sandwich assembly is then vulcanized in the press for 30 minutes at 280 F. under a 150 p.s.i.g. load.
- a spinnable composition comprising a fiber forming polyamide having dispersed therein about 10 to 50 parts by weight of a fiber forming polyester together with from about 0.05 to about 0.6 part by weight of a wax-like spinning aid having a melting point above C., a mold release index of greater than 25 when incorporated in pure polycaprolactam and further characterized by the presence of a straight chain, saturated acyl group having from 12 to 22 carbon atoms in the hydrocarbon chain, all parts by weight being based on the total weight of the composition.
- Wax-like spinning aid is selected from the group consisting of an alkali or alkaline earth metal salt of an aliphatic carboxylic acid and a diamide derived by the reaction of an aliphatic carboxylic acid and a compound selected from the group consisting of a diamine and hydrazine.
- the spinning aid is a diamide derived by the reaction of an aliphatic carboxylic acid and a compound selected from the group consisting of a diamine and hydrazine.
- a composition comprising a fiber forming polyamide having dispersed therein about 10 to 50 parts by weight of a fiber forming polyester, the step which comprises addding from 0.05 to 0.6 part by weight of a wax-like spinning aid having a melting point above 100 C., a mold release index of greater than 25 when incorporated in pure polycaprolactam and further characterized by the presence of a straight chain, saturated acyl group having from 12 to 22 carbon atoms in the hydrocarbon chain, all parts by weight being based on the total weight of the composition.
- waxlike spinning aid is selected from the group consisting of an alkali or alkaline earth metal salt of an aliphatic carboxylic acid and a diamide derived by the reaction of an aliphatic carboxylic acid and a compound selected from the group consisting of a diamine and hydrazine.
- spinning aid is an alkali or alkaline earth metal salt of an aliphatic carboxylic acid.
- a process as defined in claim 11 spinning aid is sodium stearate.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US56872566A | 1966-07-29 | 1966-07-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3516956A true US3516956A (en) | 1970-06-23 |
Family
ID=24272464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US568725A Expired - Lifetime US3516956A (en) | 1966-07-29 | 1966-07-29 | Spinnable compositions comprising a fiber forming polyamide,a fiber forming polyester and a spinning aid |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3516956A (de) |
| BE (1) | BE702039A (de) |
| CH (1) | CH499632A (de) |
| DE (1) | DE1669373A1 (de) |
| ES (1) | ES343530A1 (de) |
| GB (1) | GB1156251A (de) |
| NL (1) | NL6710464A (de) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3887520A (en) * | 1974-01-30 | 1975-06-03 | Allied Chem | Stabilized polyamide composition |
| US3915912A (en) * | 1970-03-05 | 1975-10-28 | Asahi Chemical Ind | Modified polyamide compositions containing a polyethylene glycol derivative and a fatty acid or fatty acid salt |
| US4115333A (en) * | 1977-03-18 | 1978-09-19 | General Electric Company | Warp-resistant reinforced thermoplastic compositions comprising polyester resins and zinc stearate |
| US5204396A (en) * | 1991-06-14 | 1993-04-20 | Polyplastics Co., Ltd. | Long fiber-reinforced polyamide resin composition and molded articles therefrom |
| US5585056A (en) * | 1993-07-21 | 1996-12-17 | United States Surgical Corporation | Plasticizers for fibers used to form surgical devices |
| US6005019A (en) * | 1993-07-21 | 1999-12-21 | United States Surgical Corporation | Plasticizers for fibers used to form surgical devices |
| US6087427A (en) * | 1995-11-21 | 2000-07-11 | E. I. Du Pont De Nemours And Company | Moldable thermoplastic resin composition |
| US20020177876A1 (en) * | 2001-03-26 | 2002-11-28 | Tyco Healthcare Group Lp | Polyolefin sutures having improved processing and handling characteristics |
| US20020193829A1 (en) * | 2001-03-26 | 2002-12-19 | Tyco Healthcare Group Lp | Oil coated sutures |
| WO2008061723A3 (de) * | 2006-11-22 | 2008-07-31 | Phoenix Contact Gmbh & Co | Verfahren zur verbesserung der benetzbarkeit und/oder des haftvermögens von kunststoffoberflächen, insbesondere zu zwecken der erleichterten bedruckbarkeit |
| KR20190086966A (ko) * | 2018-01-15 | 2019-07-24 | 한국화학연구원 | 알킬 아마이드로 치환된 비스 페닐렌 그룹을 가지는 화합물, 이를 포함하는 폴리페닐렌계 고분자의 유동성 조절용 조성물 및 이를 이용한 폴리페닐렌계 고분자 유동성 조절 방법 |
| US20240309566A1 (en) * | 2021-12-09 | 2024-09-19 | Nantong Qiangsheng New Material Technology Co., Ltd. | Protective glove for electric welding, and manufacturing method therefor |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1170091B (it) * | 1983-12-30 | 1987-06-03 | Snia Fibre | Procedimento per la filatura di materiali polimerici termoplastici per fusione di fibre sintetiche, fibre e manufatti relativi |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2856373A (en) * | 1956-08-06 | 1958-10-14 | Allied Chemcial Corp | Polycaprolactam molding composition and molded articles |
| US3002942A (en) * | 1957-10-19 | 1961-10-03 | Onderzoekings Inst Res Nv | Pigmentation of polyesters |
| US3008908A (en) * | 1956-09-24 | 1961-11-14 | Onderzoekings Inst Res Nv | Plastics molding process and the resulting products |
| GB889403A (en) * | 1957-10-22 | 1962-02-14 | Farbenfabriken Ag | Process for the production of moulded objects from crystallisable plastics |
| US3039895A (en) * | 1960-03-29 | 1962-06-19 | Du Pont | Textile |
| US3260689A (en) * | 1960-05-27 | 1966-07-12 | Eastman Kodak Co | Polyester and polyamide compositions having improved dyeing properties and processesfor the production of such compositions |
| US3280053A (en) * | 1963-06-17 | 1966-10-18 | Allied Chem | Polyamide stabilized with a copper compound and a stannous salt |
-
1966
- 1966-07-29 US US568725A patent/US3516956A/en not_active Expired - Lifetime
-
1967
- 1967-07-25 CH CH1050767A patent/CH499632A/de unknown
- 1967-07-28 ES ES343530A patent/ES343530A1/es not_active Expired
- 1967-07-28 NL NL6710464A patent/NL6710464A/xx unknown
- 1967-07-28 BE BE702039D patent/BE702039A/xx unknown
- 1967-07-28 DE DE19671669373 patent/DE1669373A1/de active Pending
- 1967-07-28 GB GB34918/67A patent/GB1156251A/en not_active Expired
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2856373A (en) * | 1956-08-06 | 1958-10-14 | Allied Chemcial Corp | Polycaprolactam molding composition and molded articles |
| US3008908A (en) * | 1956-09-24 | 1961-11-14 | Onderzoekings Inst Res Nv | Plastics molding process and the resulting products |
| US3002942A (en) * | 1957-10-19 | 1961-10-03 | Onderzoekings Inst Res Nv | Pigmentation of polyesters |
| GB889403A (en) * | 1957-10-22 | 1962-02-14 | Farbenfabriken Ag | Process for the production of moulded objects from crystallisable plastics |
| US3039895A (en) * | 1960-03-29 | 1962-06-19 | Du Pont | Textile |
| US3260689A (en) * | 1960-05-27 | 1966-07-12 | Eastman Kodak Co | Polyester and polyamide compositions having improved dyeing properties and processesfor the production of such compositions |
| US3280053A (en) * | 1963-06-17 | 1966-10-18 | Allied Chem | Polyamide stabilized with a copper compound and a stannous salt |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3915912A (en) * | 1970-03-05 | 1975-10-28 | Asahi Chemical Ind | Modified polyamide compositions containing a polyethylene glycol derivative and a fatty acid or fatty acid salt |
| US3887520A (en) * | 1974-01-30 | 1975-06-03 | Allied Chem | Stabilized polyamide composition |
| US4115333A (en) * | 1977-03-18 | 1978-09-19 | General Electric Company | Warp-resistant reinforced thermoplastic compositions comprising polyester resins and zinc stearate |
| US5204396A (en) * | 1991-06-14 | 1993-04-20 | Polyplastics Co., Ltd. | Long fiber-reinforced polyamide resin composition and molded articles therefrom |
| US5585056A (en) * | 1993-07-21 | 1996-12-17 | United States Surgical Corporation | Plasticizers for fibers used to form surgical devices |
| US6005019A (en) * | 1993-07-21 | 1999-12-21 | United States Surgical Corporation | Plasticizers for fibers used to form surgical devices |
| US6087427A (en) * | 1995-11-21 | 2000-07-11 | E. I. Du Pont De Nemours And Company | Moldable thermoplastic resin composition |
| US20020193829A1 (en) * | 2001-03-26 | 2002-12-19 | Tyco Healthcare Group Lp | Oil coated sutures |
| US20020177876A1 (en) * | 2001-03-26 | 2002-11-28 | Tyco Healthcare Group Lp | Polyolefin sutures having improved processing and handling characteristics |
| US20070265660A1 (en) * | 2001-03-26 | 2007-11-15 | Kennedy John J | Oil coated sutures |
| WO2008061723A3 (de) * | 2006-11-22 | 2008-07-31 | Phoenix Contact Gmbh & Co | Verfahren zur verbesserung der benetzbarkeit und/oder des haftvermögens von kunststoffoberflächen, insbesondere zu zwecken der erleichterten bedruckbarkeit |
| US20100021636A1 (en) * | 2006-11-22 | 2010-01-28 | Joachim Jacke | Method for improving the wettability and/or the adhesivity of plastic surfaces, in particular, to facilitate printing |
| US8501852B2 (en) | 2006-11-22 | 2013-08-06 | Phoenix Contact Gmbh & Co. Kg | Method for improving the wettability and/or the adhesivity of plastic surfaces, in particular, to facilitate printing |
| KR20190086966A (ko) * | 2018-01-15 | 2019-07-24 | 한국화학연구원 | 알킬 아마이드로 치환된 비스 페닐렌 그룹을 가지는 화합물, 이를 포함하는 폴리페닐렌계 고분자의 유동성 조절용 조성물 및 이를 이용한 폴리페닐렌계 고분자 유동성 조절 방법 |
| KR102090166B1 (ko) | 2018-01-15 | 2020-03-18 | 한국화학연구원 | 알킬 아마이드로 치환된 비스 페닐렌 그룹을 가지는 화합물, 이를 포함하는 폴리페닐렌계 고분자의 유동성 조절용 조성물 및 이를 이용한 폴리페닐렌계 고분자 유동성 조절 방법 |
| US10927237B2 (en) * | 2018-01-15 | 2021-02-23 | Korea Research Institute Of Chemical Technology | Compound having bis phenylene group substituted with alkylamide, composition for controlling polyphenylene polymer flowability and method of polyphenylene polymer flowability control using the same |
| US20240309566A1 (en) * | 2021-12-09 | 2024-09-19 | Nantong Qiangsheng New Material Technology Co., Ltd. | Protective glove for electric welding, and manufacturing method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| CH499632A (de) | 1970-11-30 |
| NL6710464A (de) | 1968-01-30 |
| BE702039A (de) | 1968-01-02 |
| GB1156251A (en) | 1969-06-25 |
| DE1669373A1 (de) | 1971-05-06 |
| ES343530A1 (es) | 1968-12-16 |
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