US3776766A - Process for improving the processing properties of polyester filaments and fibres - Google Patents

Process for improving the processing properties of polyester filaments and fibres Download PDF

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US3776766A
US3776766A US00199796A US3776766DA US3776766A US 3776766 A US3776766 A US 3776766A US 00199796 A US00199796 A US 00199796A US 3776766D A US3776766D A US 3776766DA US 3776766 A US3776766 A US 3776766A
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filaments
fibres
polyester
mole
improving
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US00199796A
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A Scharf
P Hess
O Smerz
W Linke
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Hoechst AG
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Hoechst AG
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    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2967—Synthetic resin or polymer
    • Y10T428/2969—Polyamide, polyimide or polyester

Definitions

  • ABSTRACT A process for improving the processing properties of polyester filaments by treating the freshly-spun filaments before being drawn with an aqueous solution or emulsion of a condensation product ot"1 mo]e of a 1,4-butane-diolpolyglycol ether and 2 moles of a fatty acid.
  • Such oligomer compounds which may be contained in amounts of up to about percent in the polyester fibre materials, cause a number of interruptions in the processing of the polyester filaments or staple fibres.
  • the oligomers which appear in form of deposits on the filaments or fibres may lead to bad running properties, de-
  • oligomer constituents in processing operations including -a thermal treatment, such as for example the texturing of polyester filaments.
  • a thermal treatment such as for example the texturing of polyester filaments.
  • the existance of oligomer compounds has also detrimental effects, since any roughness of the surface of the curled material causes interruptions of operation and, moreover, an unsatisfactory appearance of the ready textile material.
  • oligomer constituents also cause difficulties in the usual dyeing processes of polyester fibre materials.
  • Sin'cethe oligomers generally .cannot be dyedfor example with dispersion dyestuffs, they appear on the dyed material as awhite dust, which is to be seen above all in the spinning and subsequent weaving and knitting process.
  • the compounds of formula (I) to be used according to the invention may be prepared for example by esterification of 1' mole of an addition compound of 8 to 24 moles, preferably 10 to moles, of ethylene oxide to l'mole of butane-diol-( 1,4) with 2 moles of a straight Not only the elimination of the'oligomer compounds in the form of very fine dispersions easily to be washed off is obtained to -a' large-extent, but the.
  • present process also causes the lubricating agentsaccording to the invention-to' produce on the-filaments" freed from the oligomersa thin film which ensuresa high sliding cawpacity.-
  • the dynamic friction coefficient between the polyester filaments and fibres is reduced to such adegree that the oligomer portions protruding from the fibre surface in the form of points and elevations do not cause any further interruptions during processing.
  • literof-the aqueous treatingbath there are generally I used about 2- to 18 g, preferably 3 to 12 g of-theseproducts/Acco'rding to the conditions of practice, there may be applied higher or lower concentrations.
  • the prod- 'u'cts it is importantthat after the treatment according to the invention, acertain amount of at. least 0.05 percent of the product according to the invention is to be found onthe polyester fibres or filaments.
  • the concen- 't'ration used of the'products and the way of application are generally chosen in the way thatthe amount applied ranges betweenabout 0.1 and 0.3 percent, calculated on the weight of the polyester filaments.
  • the products according to the invention may be applied one time only or repeatedly, if desiredin different stages of'treatment'of the polyester filaments. lf desired, the products of formula l may be applied once more even'after' drawing, but before drying and before optionally steaming the polyester filaments.
  • auxiliaries for example compounds having an antistatic effect, may be used together with the products of formula I.
  • antistatic agents areabove all cationic products containing nitrogen, such as quarternated fatty acid amides or derivatives thereof.
  • the filament cable was drawn as usual at 170 C in the ratio of 113.7.
  • the cable was curled and cut to give a flock.
  • the staple fibre lubricated thus obtained had an excellent handle and was characterized especially by a very low dynamic friction coefficient, i.e., by a low friction between fibre and metal.
  • EXAMPLE 2 Immediately after leaving the spinning nozzle, a bundle of filaments of polyethylene terephthalate consisting of 300 single capillaries having a single titer of4 deniers were lubricated with an aqueous solution with the aid of rollers at 25 C.
  • the solution contained per liter 0.3 percent by weight of a condensation product of 2 moles of lauric acid and 1 mole of the addition compound of moles of ethylene oxide to 1 mole of 1,4- butane-diol as well as 0.15 percent by weight of a condensation product methylated with dimethyl sulfate consisting of 1 mole of stearic acid and 1 mole of triethylene-tetramine.
  • the film calculated on the anhydrous products was 0.2 percent by weight.
  • the strands of 40 of these cans were jointly passed to a strand line and processed.
  • the strands were passed to a heating zone with a speed of 20 m/min and drawn off with a transport speed of m/min at C. After drawing, the strands were treated once more with the above-mentioned solution of the lubricating agent, the film, calculated on the anhydrous agent, being 0.1 percent by weight.
  • the lubricated staple fibre thus obtained had an excellent handle and permitted excellent processing in cotton spinning.
  • the polyester filaments were lubricated with an aqueous solution, which contained per liter 0.35 percent by weight of a condensation product of 2 moles of oleic acid and 1 mole of an addition compound of 20 moles of ethylene oxide to 1 mole of 1,4-butane-diol as well as 0.15 per cent by weight of a condensation product methylated with dimethyl sulfate consisting of 1 mole of stearic acid and 1 mole of triethylene-tetramine.
  • the film calculated on the anhydrous products was 0.23 percent by weight.
  • a process for improving the processing properties of filaments and fibres made of linear polyesters which comprises treating the freshly-spun polyester filaments before being drawn, with an aqueous solution or emulsion, which contains as essential component a compound of the general formula wherein R,CO and R CO represent radicals of straightchained or branched alkane-or alkenemonocarboxylic acids having 12 to 22 carbon atoms and the total of n and m represent a number of from 8 to 24.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Artificial Filaments (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)

Abstract

A process for improving the processing properties of polyester filaments by treating the freshly-spun filaments before being drawn with an aqueous solution or emulsion of a condensation product of 1 mole of a 1,4-butane-diolpolyglycol ether and 2 moles of a fatty acid.

Description

1' tes If? atent 1191 [111 3,776,766
Smerz et a1. 4, 1973 PROCESS FOR IMPROVING THE PROCESSlNG PROPERTIES OF POLYESTER FILAMENTS AND FIBRES lnventors: Otto Smerz, Kelkheim/Taunus;
Werner Linke, Sulzbachflaunus; Alfred Schari, Frankfurt/Main; Peter Hess, Kelkheim/Iaunus, all of Germany Appl. No.: 199,796
Foreign Application Priority Data Nov. 18, 1970 Germany P 20 56 695.4
.s c1. ..117/13s.s F, 117/139.5 F,
117/139.5 CQ; 25 2/89, eg/4105 rm. iii: .LITII D0611; 13720 306111 13/5 Field 01 Search 117/138.8 F, 139.5 F,
[56] References Cited UNITED STATES PATENTS 3,113,369 12/1963 Barrett et a1 260/410.6
3,423,809 1/1969 Schmitt 260/410 6 3,433,008 3/1969 Gage 1 260/410 6 3,563,892 2/1971 Cooley 117/139 5 2,820,815 1/1958 Matusznk et al. 260/4106 X 3,694,257 9/1972 Dumont 117/139 5 2,920,980 1/1960 Mooberry 117/138 8 3,406,208 10/1968 Blaser et al. 252/89 X 1,970,578 8/1934 Schoeller et al. 252/8.9
Primary Examiner-Wi1liam D. I Martin Assistant ExaminerSadie L. Childs Attorney-Arthur C. Connolly et al.
[5 7 ABSTRACT A process for improving the processing properties of polyester filaments by treating the freshly-spun filaments before being drawn with an aqueous solution or emulsion of a condensation product ot"1 mo]e of a 1,4-butane-diolpolyglycol ether and 2 moles of a fatty acid.
3 Claims, No Drawings '1 PROCESS FOR IMPROVING THE PROCESSING PROPERTIES OF POLYESTER FILAMENTS AND FIBRES When preparing filament-forming synthetic and highmolecular-weight linear polyesters from dicarboxylic acids or their esters and polyfunctional alcohols, for example from terephthalic acid dimethyl ester and ethylene glycol, not only the desired long-chained, filamentforming macromolecules are formed, as expected, but there are also obtained little amounts of short-chained or cyclic reaction products.
Such oligomer compounds, which may be contained in amounts of up to about percent in the polyester fibre materials, cause a number of interruptions in the processing of the polyester filaments or staple fibres. When spinning polyester slubbing, for example, the oligomers which appear in form of deposits on the filaments or fibres may lead to bad running properties, de-
posits on the pieces of the machine and undesirablefor-.
mation of dust. Particularly great difficulties are caused by the oligomer constituents in processing operations including -a thermal treatment, such as for example the texturing of polyester filaments. In the further processing of textural filaments, the existance of oligomer compounds has also detrimental effects, since any roughness of the surface of the curled material causes interruptions of operation and, moreover, an unsatisfactory appearance of the ready textile material.
It is also known that the oligomer constituents also cause difficulties in the usual dyeing processes of polyester fibre materials. Sin'cethe oligomers generally .cannot be dyedfor example with dispersion dyestuffs, they appear on the dyed material as awhite dust, which is to be seen above all in the spinning and subsequent weaving and knitting process.
in spite of many efforts, for example by varyingthe condensation catalysts, the formation of oligomer compounds in the preparation of polyesters could hitherto not be avoided satisfactorily. Therefore, efforst are made in order to eliminate the negative influence of the oligomers in the processing of polyester fibres and filaments by using lubricating agents. The known lubricating agents have above all a smoothing effect covering the roughness of the filaments and fibres. However, the treatment with the known lubricating agents hasnot been sufficient for solving the problems caused bythe oligomers on the surface of the polyester fibres and filaments.
It has now been found that it is possible to eliminate the oligomer compounds contained in fibrematerials made of synthetic linear polyestersand to avoid the detrimental consequences in the further proceeding of the polyester filaments or fibres, when treating the polyester filaments during their preparation process, after leaving the spinning nozzle and before being drawn, with aqueous solutions or emulsions, which contain compounds of the general formula wherein R CO-and R -CO- represent radicals of I straight-chained or branched 'alkane or alkene monocarboxylic acids having 12-22 carbon atoms and the total of n and m represents a number offrom 8 to 24.
2 The compounds of formula (I) to be used according to the invention may be prepared for example by esterification of 1' mole of an addition compound of 8 to 24 moles, preferably 10 to moles, of ethylene oxide to l'mole of butane-diol-( 1,4) with 2 moles of a straight Not only the elimination of the'oligomer compounds in the form of very fine dispersions easily to be washed off is obtained to -a' large-extent, but the. present process also causes the lubricating agentsaccording to the invention-to' produce on the-filaments" freed from the oligomersa thin film which ensuresa high sliding cawpacity.- By this way the dynamic friction coefficient between the polyester filaments and fibres is reduced to such adegree that the oligomer portions protruding from the fibre surface in the form of points and elevations do not cause any further interruptions during processing.
*The concentration of the lubricatingagents of the .general formula (I) may vary within wide limits. Per
literof-the aqueous treatingbath, there are generally I used about 2- to 18 g, preferably 3 to 12 g of-theseproducts/Acco'rding to the conditions of practice, there may be applied higher or lower concentrations.
As concerns the effects to be obtained with the prod- 'u'cts, it is importantthat after the treatment according to the invention, acertain amount of at. least 0.05 percent of the product according to the invention is to be found onthe polyester fibres or filaments. The concen- 't'ration used of the'products and the way of application are generally chosen in the way thatthe amount applied ranges betweenabout 0.1 and 0.3 percent, calculated on the weight of the polyester filaments.
The products according to the invention may be applied one time only or repeatedly, if desiredin different stages of'treatment'of the polyester filaments. lf desired, the products of formula l may be applied once more even'after' drawing, but before drying and before optionally steaming the polyester filaments.
If necessary, other auxiliaries, for example compounds having an antistatic effect, may be used together with the products of formula I. Such antistatic agents areabove all cationic products containing nitrogen, such as quarternated fatty acid amides or derivatives thereof.
The following Examples illustrate the invention.
I EXAMPLE 1 A polycondensation product of terephthalic acid and ethylene glycol were spun in the melt spinning process to give/200 single capillaries of 14.8 deniers each. In the spinning box, immediately after leaving the spinning nozzle,the capillaries were passed over a dip roller and lubricated with an aqueous solution, which contained 0.38 percentby weight of a condensation prodnet of 1 mole of l,4-butane-dioLdeca'glycol ether and 2 moles of stearic acid. This solution of the lubricating agent showed a pH-value'of about 7.5. The film obtained of the condensation product was about 0.15 percent by weight.
The still moist filaments of l of these lubricating rollers were parallely run, joined in a fibre strand and piled in a can. Due to the low dynamic friction and to the marked filament-bonding properties, which imparted the lubricating agent to the filaments, a perfect piling in the cans was possible without the single capillaries being adversely affected.
These strands of 28 cans were joined in a filament cable and processed on a line. At first the cable passed through a bath which was filled with an aqueous solution of the lubricating agent which contained 0.25 percent by weight of the condensation product of 1 mole of l,4-butane-diol-decaglycol ether and 2 moles of stearic acid and 0.15 percent by weight of oleyl sarcoside sodium. The temperature of the solution of the lubrication agent in the bath amounted to 50 C. The polyester cable subsequently passed over a drawing off device. The film of the lubrication agent remaining on the cable was about 0.15 percent by weight.
Then the filament cable was drawn as usual at 170 C in the ratio of 113.7. The cable was curled and cut to give a flock.
The staple fibre lubricated thus obtained had an excellent handle and was characterized especially by a very low dynamic friction coefficient, i.e., by a low friction between fibre and metal.
A comparison showed that the oligomers came out of the filaments to a considerably smaller extent, if the mentioned condensation product of 1 mole of 1,4- butane-diol-decaglycol ether and 2 moles of stearic acid was used during the drawing process than in the case of a usual lubricating oil on the basis of an addition compound of moles of ethylene oxides to 1 mole of stearic acid. Furthermore, the low dynamic friction coefficient of the filaments treated according to the invention permitted to avoid in the subsequent processing an abrasion of the oligomers having partially come out of the surface, which fact appeared especially in a decrease of the known dusting in the spinning process, when the mentioned staple fibre was processed.
EXAMPLE 2 Immediately after leaving the spinning nozzle, a bundle of filaments of polyethylene terephthalate consisting of 300 single capillaries having a single titer of4 deniers were lubricated with an aqueous solution with the aid of rollers at 25 C. The solution contained per liter 0.3 percent by weight of a condensation product of 2 moles of lauric acid and 1 mole of the addition compound of moles of ethylene oxide to 1 mole of 1,4- butane-diol as well as 0.15 percent by weight of a condensation product methylated with dimethyl sulfate consisting of 1 mole of stearic acid and 1 mole of triethylene-tetramine. The film calculated on the anhydrous products was 0.2 percent by weight.
About 40 to 50 of these still moist bundles of filaments were joined in a filament strand having a total titer of 48,000 to 60,000 deniers and piled in a can.
The strands of 40 of these cans were jointly passed to a strand line and processed. The strands were passed to a heating zone with a speed of 20 m/min and drawn off with a transport speed of m/min at C. After drawing, the strands were treated once more with the above-mentioned solution of the lubricating agent, the film, calculated on the anhydrous agent, being 0.1 percent by weight.
Then the filaments were curled, dried and cut to give a flock. The lubricated staple fibre thus obtained had an excellent handle and permitted excellent processing in cotton spinning.
The method of operation being the same, the polyester filaments were lubricated with an aqueous solution, which contained per liter 0.35 percent by weight of a condensation product of 2 moles of oleic acid and 1 mole of an addition compound of 20 moles of ethylene oxide to 1 mole of 1,4-butane-diol as well as 0.15 per cent by weight of a condensation product methylated with dimethyl sulfate consisting of 1 mole of stearic acid and 1 mole of triethylene-tetramine. The film calculated on the anhydrous products was 0.23 percent by weight. In the further proceeding of the filaments, wherein the solution of the lubricating agent on the basis of the oleic acid ester was also employed after drawing, the same before-mentioned advantages were obtained.
What we claim is:
1. A process for improving the processing properties of filaments and fibres made of linear polyesters, which comprises treating the freshly-spun polyester filaments before being drawn, with an aqueous solution or emulsion, which contains as essential component a compound of the general formula wherein R,CO and R CO represent radicals of straightchained or branched alkane-or alkenemonocarboxylic acids having 12 to 22 carbon atoms and the total of n and m represent a number of from 8 to 24.
2. A process as claimed in claim 1, wherein the products of formula (I) are used in a concentration and under conditions under which it is possible to apply an amount of at least 0.05 percent on the filaments, calculated on the weight of the filaments.
3. A process as claimed in claim 1, wherein an aqueous solution or emulsion containing of from 2 to 18 g/l of a compound of the formula (I) is applied.

Claims (2)

  1. 2. A process as claimed in claim 1, wherein the products of formula (I) are used in a concentration and under conditions under which it is possible to apply an amount of at least 0.05 percent on the filaments, calculated on the weight of the filaments.
  2. 3. A process as claimed in claim 1, wherein an aqueous solution or emulsion containing of from 2 to 18 g/l of a compound of the formula (I) is applied.
US00199796A 1970-11-18 1971-11-17 Process for improving the processing properties of polyester filaments and fibres Expired - Lifetime US3776766A (en)

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DE2056695A DE2056695C3 (en) 1970-11-18 1970-11-18 Process for improving the processing properties of polyester threads and fibers

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AT (1) AT331760B (en)
BE (1) BE775508A (en)
BR (1) BR7107657D0 (en)
CA (1) CA964425A (en)
CH (1) CH527282A (en)
DE (1) DE2056695C3 (en)
FR (1) FR2114807A5 (en)
GB (1) GB1357036A (en)
IT (1) IT940629B (en)
NL (1) NL166508C (en)
SU (1) SU436501A3 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929847A (en) * 1974-09-25 1975-12-30 Eastman Kodak Co Ether diester derivatives of p-dioxanone
US3942532A (en) * 1972-11-03 1976-03-09 Ethicon, Inc. Braided suture
US4390647A (en) * 1981-02-27 1983-06-28 Ppg Industries, Inc. Non-starch containing aqueous sizing composition for glass fibers and sized glass fibers for use in reinforcing elastomers
US4461804A (en) * 1981-05-29 1984-07-24 Ppg Industries, Inc. Aqueous sizing composition for glass fibers for use in producing a mat
US20110107526A1 (en) * 2006-05-16 2011-05-12 Nicca Chemical Co., Ltd. Oligomer removing agent for polyester-based fiber material

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2710640C3 (en) * 1977-03-11 1979-08-30 Hoechst Ag, 6000 Frankfurt Process for improving the spinning-technical running properties of linear polyester material
EP0327091A3 (en) * 1988-02-03 1991-05-08 DR. TH. BÖHME KG CHEM. FABRIK GMBH & CO. Process for improving the running properties of synthetic yarns during air jet texturing

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1970578A (en) * 1930-11-29 1934-08-21 Ig Farbenindustrie Ag Assistants for the textile and related industries
US2820815A (en) * 1954-04-08 1958-01-21 Exxon Research Engineering Co Synthetic lubricating compositions and process for their preparation
US2920980A (en) * 1956-03-28 1960-01-12 Du Pont Finishing fabrics
US3113369A (en) * 1960-05-02 1963-12-10 Monsanto Chemicals Yarn manufacture and products obtained thereby
US3406208A (en) * 1962-05-17 1968-10-15 Henkel & Compagnie G M B H Polyglycol ethers suitable for detergent preparations, and process for preparing the same
US3423809A (en) * 1967-11-15 1969-01-28 Du Pont Process for forming differential shrinkage bulked yarn
US3433008A (en) * 1965-11-19 1969-03-18 Du Pont Bulked yarn
US3563892A (en) * 1967-06-12 1971-02-16 Du Pont Textile-treating composition and process
US3694257A (en) * 1970-07-20 1972-09-26 Emery Industries Inc Polyester compositions and their use as textile assistants

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1970578A (en) * 1930-11-29 1934-08-21 Ig Farbenindustrie Ag Assistants for the textile and related industries
US2820815A (en) * 1954-04-08 1958-01-21 Exxon Research Engineering Co Synthetic lubricating compositions and process for their preparation
US2920980A (en) * 1956-03-28 1960-01-12 Du Pont Finishing fabrics
US3113369A (en) * 1960-05-02 1963-12-10 Monsanto Chemicals Yarn manufacture and products obtained thereby
US3406208A (en) * 1962-05-17 1968-10-15 Henkel & Compagnie G M B H Polyglycol ethers suitable for detergent preparations, and process for preparing the same
US3433008A (en) * 1965-11-19 1969-03-18 Du Pont Bulked yarn
US3563892A (en) * 1967-06-12 1971-02-16 Du Pont Textile-treating composition and process
US3423809A (en) * 1967-11-15 1969-01-28 Du Pont Process for forming differential shrinkage bulked yarn
US3694257A (en) * 1970-07-20 1972-09-26 Emery Industries Inc Polyester compositions and their use as textile assistants

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3942532A (en) * 1972-11-03 1976-03-09 Ethicon, Inc. Braided suture
US3929847A (en) * 1974-09-25 1975-12-30 Eastman Kodak Co Ether diester derivatives of p-dioxanone
US4390647A (en) * 1981-02-27 1983-06-28 Ppg Industries, Inc. Non-starch containing aqueous sizing composition for glass fibers and sized glass fibers for use in reinforcing elastomers
US4461804A (en) * 1981-05-29 1984-07-24 Ppg Industries, Inc. Aqueous sizing composition for glass fibers for use in producing a mat
US20110107526A1 (en) * 2006-05-16 2011-05-12 Nicca Chemical Co., Ltd. Oligomer removing agent for polyester-based fiber material
US8324338B2 (en) 2006-05-16 2012-12-04 Nicca Chemical Co., Ltd. Oligomer removing agent for polyester-based fiber material

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BR7107657D0 (en) 1973-03-29
GB1357036A (en) 1974-06-19
DE2056695A1 (en) 1972-05-31
CH1662771A4 (en) 1972-10-13
NL166508B (en) 1981-03-16
FR2114807A5 (en) 1972-06-30
ATA988871A (en) 1975-12-15
NL7115575A (en) 1972-05-23
BE775508A (en) 1972-05-18
SU436501A3 (en) 1974-07-15
DE2056695B2 (en) 1973-05-10
NL166508C (en) 1981-08-17
AT331760B (en) 1976-08-25
CA964425A (en) 1975-03-18
DE2056695C3 (en) 1976-01-08
IT940629B (en) 1973-02-20
CH527282A (en) 1972-10-13

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