US3788888A - Fiber-lubricant composition - Google Patents

Fiber-lubricant composition Download PDF

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US3788888A
US3788888A US00134858A US3788888DA US3788888A US 3788888 A US3788888 A US 3788888A US 00134858 A US00134858 A US 00134858A US 3788888D A US3788888D A US 3788888DA US 3788888 A US3788888 A US 3788888A
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fiber
fibers
friction
alkyl
staple
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US00134858A
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H Kawanaka
K Katabe
S Kameda
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Kao Corp
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Kao Corp
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    • 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
    • D06M7/00Treating fibres, threads, yarns, fabrics, or fibrous goods made of other substances with subsequent freeing of the treated goods from the treating medium, e.g. swelling, e.g. polyolefins
    • 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
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/40Reduced friction resistance, lubricant properties; Sizing compositions
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/922Static electricity metal bleed-off metallic stock
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2904Staple length fiber
    • Y10T428/2907Staple length fiber with coating or impregnation
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2933Coated or with bond, impregnation or core
    • Y10T428/2964Artificial fiber or filament
    • Y10T428/2967Synthetic resin or polymer

Definitions

  • This invention relates to a fiber-lubricant composition (or spin finish for staple) suitable for use in high speed spinning. More specifically, it relates to a basic ingredient to be incorporated in a spin finish for staple and its object is to provide a fiber-lubricant composition which can increase the fiber to fiber friction and improve the interfiber cohesion between fibers while preventing the falling-out of fibers during the drawing process.
  • Synthetic fibers such as polyester fibers, acrylic fibers and polyamide fibers are used in large quantities in the spinning instead of natural fibers such as wool and cotton.
  • synthetic fibers there are various problems concerning lubricity, antistatic property, interfiber cohesion, etc. Particularly, the adaptability of the spinning process at a high speed has been a serious problem.
  • the spinning process of synthetic staple fibers composed mainly of polyester or dry-spun acrylic fibers cannot be conducted smoothly as compared with the case of cotton, wool or acrylic fibers made by the wet spinning process, since melt-spun polyester fibers made by the melt spinning process and acrylic fibers made by the dry spinning process have a smooth surface configuration. There occur such troubles as winding up of fibers on cylinders at the carding process and winding up of fibers on the rolls at the drawing, roving and spinning processes. Occurrence of such operational troubles is greatly influenced by not only the surface state of the fibers but also the kind of surface treating agent used for the fibers.
  • Surface treating agents or so-called textile lubricants are generally composed of a lubricating agent and an antistatic agent.
  • the lubricating agent there are used animal oil, vegetable oil, mineral oil, fatty acid esters such as methyl oleate and butyl stearate, non-ionic surface active agents such as ethylene oxide adducts of fatty acids or fatty acid esters of higher or polyhydric alcohols, and anionic surface active agents such as alkyl sulfates, alkyl phosphates and fatty acid salts.
  • non-ionic surface active agents such as ethylene oxide adducts of fatty acids or fatty acid esters of higher or polyhydric alcohols
  • anionic surface active agents such as alkyl sulfates, alkyl phosphates and fatty acid salts.
  • the antistatic agent there are used alkyl phosphates, alkyl sulfates, alkyl amineethylene oxide adducts, cationic surface active agents such as quaternary ammonium salts and alkyl betain'e type amphoteric surface active agents.
  • alkyl phosphate salts there occurs a trouble that fibers fall on and wind up on the drawing rolls. For this reason, alkyl phosphate salts,
  • the object of this invention is to provide a spinning finish or a basic ingredient therefor, which can increase the degree of interfiber cohesion of fibers while reducing the fiber to metal friction and the fiber to rubber friction, whereby falling off of fibers and winding up of fibers on the rolls can be prevented in the drawing process.
  • Compounds of the above General Formula I may be synthesized by sulfonating naphthalene or a naphthalene derivative selected from the group consisting of alphana-phthol, beta-naphthol, a1pha-methyl-naphthalene, alphaethyl-naphthalene, alpha-propybnaphthalene, alpha-butylnaphthalene, beta-methyl-naphthalene, beta-ethyl-naphthalene, beta-propyl-naphthalene and beta-butyl-na-phthalene, with a concentrated sulfuric acid at 120-170 C. and condensing the sulfonated product at 150 C. under acidic conditions with formaldehyde, acetaldehyde, propionaldehyde, iso butylaldehyde or 'butylaldehyde.
  • Compounds of above General Formula II are homopolymers of maleic anhydride or copolymers of maleic anhydride with a polymerizable unsaturated compound such as ethylene, butylene, isobutylene, di-isobutylene, alphaoctene, alpha-decene, alpha-octadecene, styrene, vinyl benzene and vinyl acetate.
  • a polymerizable unsaturated compound such as ethylene, butylene, isobutylene, di-isobutylene, alphaoctene, alpha-decene, alpha-octadecene, styrene, vinyl benzene and vinyl acetate.
  • Compounds of the above Formulas I and II may be optionally neutralized with an alkali metal such as sodium and potassium, ammonia, an amine substituted by an organic group such as ethanolamine, diethanoiamine, methylamine and dimethylamine, or a hydroxide or watersoluble salt thereof.
  • an alkali metal such as sodium and potassium, ammonia
  • an amine substituted by an organic group such as ethanolamine, diethanoiamine, methylamine and dimethylamine, or a hydroxide or watersoluble salt thereof.
  • fiber-lubricant compounds of this invention can exhibit their properties when they are applied to fibers in an amount of ODS-1.0% by weight, preferably 0.1- 0.5 by weight.
  • the treating agent of this invention may be used singly or in combination with another agent which has been used as an ingredient of a spin finish for staple, for instance, an antistatic agent.
  • the following compounds may be preferably used:
  • Alkyl phosphates and olyoxyethylene alkyl phosphates (to be used maily in the form of a sodium salt) (2) Polyoxyethylene alkyl sulfates (to be used mainly in the form of a sodium salt) (3) Fatty acid metal soaps such as potassium oleate (4) Non-ionic surface active agents such as poly0xyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene alkyl ethers and olyoxyethylene alkyl esters ('5) .
  • Betaine type amphoteric surfactants such as alkyl betaines and polyoxyalkyl betaines (6) Alkyl imidazoline type amphoteric surfactants (7) N-alkylaminopropionic acid type amphoteric sur- 30 fibers wind up on rubber rolls.
  • Fiber-metal friction g. 38 57 Fiber-fiber friction, g 156 138 Mixing ratiio gel-cent by 60 Fiber-rubber friction, g 41 40 we g
  • the embodiments of the invention in which an exclup 0011111051- sive property or priviledge is claimed are defined as non I tion II follows: Di-isobutvlene-meleicanhvdfide colwlymer 1.
  • Amount applied (percent R by weight based on fiber weight) 0. 2 0. 3 0. 2 0. 3 surfflilclgeleetrie resistance 3 6X10 1 4X10 1 4 10 4 10 0 M n x x Cardtelectrification voltage, 0 0 o o
  • R and R are H, OH or alkyl having from 1 to 4 carbon atoms
  • R" is H or alkyl having from 1 to 3 cation.
  • n is an average degree of polymerization in the range of from 3 to 10
  • Me is H, alkali metal, ammonium or water-soluble substituted ammonium References Cited UNITED STATES PATENTS Schmidt 260-67 S Hill 260-67 8 Tiefethal et a]. 260--78.5 T

Abstract

A FIBER-LUBRICANT COMPOSITION CONTAINING A COPOLYMER OF A SULFONATED PRODUCT OF NAPHTHALENE OR A NAPHTHALENE DERIVATIVE WITH AN ALDEHYDE, OR A MALEIC ANHYDRIDE POLYMER OR COPOLYMER, WHICH COMPOSITION CAN BE ADVANTAGEOUSLY USED AS THE SPIN FINISH FOR STAPLE IN HIGH SPEED SPINNING OF SYNTHETIC FIBERS.

Description

United States Patent U.S. Cl. 117-1395 A 2 Claims ABSTRACT OF THE DISCLOSURE A fiber-lubricant composition containing a copolymer of a sulfonated product of naphthalene or a naphthalene derivative with an aldehyde, or a maleic anhydride polymer or copolymer, which composition can be advantageously used as the spin finish for staple in high speed spinning of synthetic fibers.
This invention relates to a fiber-lubricant composition (or spin finish for staple) suitable for use in high speed spinning. More specifically, it relates to a basic ingredient to be incorporated in a spin finish for staple and its object is to provide a fiber-lubricant composition which can increase the fiber to fiber friction and improve the interfiber cohesion between fibers while preventing the falling-out of fibers during the drawing process.
Synthetic fibers, such as polyester fibers, acrylic fibers and polyamide fibers are used in large quantities in the spinning instead of natural fibers such as wool and cotton. In the spinning of these synthetic fibers there are various problems concerning lubricity, antistatic property, interfiber cohesion, etc. Particularly, the adaptability of the spinning process at a high speed has been a serious problem.
The spinning process of synthetic staple fibers composed mainly of polyester or dry-spun acrylic fibers cannot be conducted smoothly as compared with the case of cotton, wool or acrylic fibers made by the wet spinning process, since melt-spun polyester fibers made by the melt spinning process and acrylic fibers made by the dry spinning process have a smooth surface configuration. There occur such troubles as winding up of fibers on cylinders at the carding process and winding up of fibers on the rolls at the drawing, roving and spinning processes. Occurrence of such operational troubles is greatly influenced by not only the surface state of the fibers but also the kind of surface treating agent used for the fibers. Surface treating agents or so-called textile lubricants are generally composed of a lubricating agent and an antistatic agent. As the lubricating agent there are used animal oil, vegetable oil, mineral oil, fatty acid esters such as methyl oleate and butyl stearate, non-ionic surface active agents such as ethylene oxide adducts of fatty acids or fatty acid esters of higher or polyhydric alcohols, and anionic surface active agents such as alkyl sulfates, alkyl phosphates and fatty acid salts. As the antistatic agent there are used alkyl phosphates, alkyl sulfates, alkyl amineethylene oxide adducts, cationic surface active agents such as quaternary ammonium salts and alkyl betain'e type amphoteric surface active agents.
In the spinning process where a property concerning the fiber to fiber friction of fibers, usually expressed by the term interfiber cohesion of fibers, is required, nonionic surface active agents have been heretofore used frequently. However, with the recent development of the high speed drawing technique, when non-ionic surface active agents are used in such high speed drawing process,
there occurs a trouble that fibers fall on and wind up on the drawing rolls. For this reason, alkyl phosphate salts,
3,788,888 Patented Jan. 29, 1974 ice polyoxyethylene alkyl phosphates, alkyl sulfate salts and the like are used instead of non-ionic surface active agents. However, each of these compounds does not give a high interfiber friction and the use of such compounds fails to impart a good interfiber cohesion.
More specifically, in conventional surface active agents used as spinning finishes for staple which comprise one hydrophobic group and one hydrophilic group, when the friction among fibers is increased by the use of these agents, the fiber to metal friction and the fiber to rubber friction tend to increase at the same time, which results in winding up the fibers on the rolls. If the prevention of winding up the fibers on the rolls is intended, the interfiber friction and interfiber cohesion properties of fibers should be decreased. The lowering of the interfiber cohesion property is a serious defect when labor-saving is intended by high speed carding, high speed drawing, package enlargement, etc.
Apart from the conventional idea that a surface active agent comprising one hydrophobic group and one hydrophilic group are used as the spin finish for staple or ingredients thereof, we have found that an excellent fiberlubricant composition free of the above-mentioned defects of conventional agents can be provided by the use of specific polymers as mentioned below.
Accordingly, the object of this invention is to provide a spinning finish or a basic ingredient therefor, which can increase the degree of interfiber cohesion of fibers while reducing the fiber to metal friction and the fiber to rubber friction, whereby falling off of fibers and winding up of fibers on the rolls can be prevented in the drawing process.
The above object of this invention can be attained by using as a spinning finish for staple or a basic ingredient thereof a polymer compound which is represented by the following General Formula I or II:
CO OMe (.lOOMo SOsMe n wherein R and R each is H, OH or a lower alkyl .group having up to 4 carbon atoms, R" is H or a lower alkyl group having up to 3 carbon atoms, X is a polymer constituent derived from maleic anhydride or a monomer copolymerizable with maleic acid, n designates an average degree of polymerization ranging from 3 to 10, and Me indicates hydrogen, an alkali metal, ammonium or a water-soluble, substituted ammonium cation.
Compounds of the above General Formula I may be synthesized by sulfonating naphthalene or a naphthalene derivative selected from the group consisting of alphana-phthol, beta-naphthol, a1pha-methyl-naphthalene, alphaethyl-naphthalene, alpha-propybnaphthalene, alpha-butylnaphthalene, beta-methyl-naphthalene, beta-ethyl-naphthalene, beta-propyl-naphthalene and beta-butyl-na-phthalene, with a concentrated sulfuric acid at 120-170 C. and condensing the sulfonated product at 150 C. under acidic conditions with formaldehyde, acetaldehyde, propionaldehyde, iso butylaldehyde or 'butylaldehyde.
Compounds of above General Formula II are homopolymers of maleic anhydride or copolymers of maleic anhydride with a polymerizable unsaturated compound such as ethylene, butylene, isobutylene, di-isobutylene, alphaoctene, alpha-decene, alpha-octadecene, styrene, vinyl benzene and vinyl acetate.
Compounds of the above Formulas I and II may be optionally neutralized with an alkali metal such as sodium and potassium, ammonia, an amine substituted by an organic group such as ethanolamine, diethanoiamine, methylamine and dimethylamine, or a hydroxide or watersoluble salt thereof.
These fiber-lubricant compounds of this invention can exhibit their properties when they are applied to fibers in an amount of ODS-1.0% by weight, preferably 0.1- 0.5 by weight.
The treating agent of this invention may be used singly or in combination with another agent which has been used as an ingredient of a spin finish for staple, for instance, an antistatic agent.
The present invention will now be explained with reference to examples and comparative examples.
COMPARATIVE EXAMPLE TABLE 1 Fiber t0- Conventional Inter- Winding up of fiber-lubricant fiber Metal Rubber Falling off of fibers fibers on rolls composition friction friction friction number (g.) (g.) (g.) Metal Rubber Metal Rubber 85 70 140 Middle... Mueh 6 90 100 Little ..do 0 5 110 60 do.. 10 6 Middle .-do 1 105 100 36 Little Little-.-.. 0 0
As such antistatic agents, the following compounds may be preferably used:
( 1) Alkyl phosphates and olyoxyethylene alkyl phosphates (to be used maily in the form of a sodium salt) (2) Polyoxyethylene alkyl sulfates (to be used mainly in the form of a sodium salt) (3) Fatty acid metal soaps such as potassium oleate (4) Non-ionic surface active agents such as poly0xyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene alkyl ethers and olyoxyethylene alkyl esters ('5) .Betaine type amphoteric surfactants such as alkyl betaines and polyoxyalkyl betaines (6) Alkyl imidazoline type amphoteric surfactants (7) N-alkylaminopropionic acid type amphoteric sur- 30 fibers wind up on rubber rolls.
EXAMPLE 1 Various surface active agents (agents Nos. 10 to 21 are polymer compounds according to this invention and agents Nos. 1 to 9 are conventional surface active agents) were applied to polyester filament yarns in an amount of 0.5% by weight, and the values of the fiber to metal friction and the fiber to rubber friction were measured by an factants Atlab friction tester. Results were as shown m Table 2.
TABLE 2 Inter- Fiber to Fiber to fiber metal rubber Agent friction friction friction number Surface active agent (g-) (g (8-) 1 Potassium oleate 68 42 53 2 Potassium myristyl phosphate 82 52 74 a Polyoxyethylene myristyl phosphate- 80 100 95 4 Potassium lauryl phosphate 86 70 38 Polyoxyethylene(5) oleyl ether 74 90 4 6 Polyoxyethyleneflfii) stearylamine 84 1 0 00 g- ?{y y gyl egz y pi e r---- g2 g2 32 o yoxyet y one s ary ami e 9 Sodium lauryl suecinate 108 146 174 SOtN a n (n=5) 11 I OH; 128 35 24 S0;Na n (n SO NH n (n=5) TABLE 2-Continued Inter- Fiber to Fiber to fiber metal rubber Agent irietion triction friction number Surface active agent (g-) (g-) (E 14 r OH 12s 45 23 SOaNan (n=3) SOaNa n ('n=5) 16 OHS-1 12s 37 25 SOzNa n (n=5) 17 inn-l 132 39 30 SOsNa n ('ll= 1s 114 so 23 CCHz-CH CH OONa JJOONa =0 (!7H: 11 ('Il= 1g CH3 140 34 30 --CHr1-CH--CH HI 00H (300E CH2- -C s OH; 11 (n=10) -I 115 21 CHz( JCHCH H; OOH 50011 n (n=10) EOH CH 1 )0ONa JOONa Jn (n= (The measurement was conducted under an initial load TABLE 3\-C11t1ned of 15 g. and at a running yarn speed of 145 m./m1-n.) Composition I Composition II Item: EXAMPLE 2 Falling on carding cylinder,
M of a polymer q lq according i P w3f%rme:::""':: GOEZ G53 G03 G03? ent invention and an antistatic agent at ratios mdlcated 55 F1 s li vgr compa o t ne sg. Good Good Good Good below were applied to polyester staples as spin fimsh ggg g qg fg 5 3 g? for staple and the splnning test was conducted. Good repi fi ish c0mpos1tlon=p.5%
by weight based on fiber sults shown in Table 3 were obtamed. weight);
Fiber-metal friction, g. 38 57 Fiber-fiber friction, g 156 138 Mixing ratiio gel-cent by 60 Fiber-rubber friction, g 41 40 we g The embodiments of the invention in which an exclup 0011111051- sive property or priviledge is claimed are defined as non I tion II follows: Di-isobutvlene-meleicanhvdfide colwlymer 1. Synthetic staple fiber having coated thereon from 1 h b 000 fi 'giiflfifilgffgfig gfifi ijffiffflj 2% $3 0.05 to 1.0 percent by welght, based on the weight of staple fiber, of a polymer of the formula TABLE 3 u l Composition I Composition II (IJH Item:
Amount applied (percent R by weight based on fiber weight) 0. 2 0. 3 0. 2 0. 3 surfflilclgeleetrie resistance 3 6X10 1 4X10 1 4 10 4 10 0 M n x x Cardtelectrification voltage, 0 0 o o wherein R and R are H, OH or alkyl having from 1 to 4 carbon atoms, R" is H or alkyl having from 1 to 3 cation.
2. A fiber-lubricating and antistatic compositionconcarbon atoms, n is an average degree of polymerization in the range of from 3 to 10, and Me is H, alkali metal, ammonium or water-soluble substituted ammonium References Cited UNITED STATES PATENTS Schmidt 260-67 S Hill 260-67 8 Tiefethal et a]. 260--78.5 T
8 Thomas et a1. 117-139.5 CQ Dickey et a1. 117139.5 CQ Dickey et a1. 117-1395 CQ McCarthy 117139.5 CQ Riley et a1 117138.8 x Thompson et a1.
117139.5 CQ Profiitt 117-138.8 F
10 WILLIAM D. MARTIN, Primary Examiner T. G. DAVIS, Assistant Examiner US. Cl. X.R.
117--138.8 F, 138.8 N, 138.8 UA; 26078.5 R
Johnson et 'al. 260-785 T 15
US00134858A 1970-04-24 1971-04-16 Fiber-lubricant composition Expired - Lifetime US3788888A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3908048A (en) * 1972-04-07 1975-09-23 Kao Corp Method of improving interfiber cohesion of filament yarns
US4210700A (en) * 1978-09-15 1980-07-01 Allied Chemical Corporation Production of polyester yarn
US5607540A (en) * 1992-02-20 1997-03-04 Teijin Seiki Co., Ltd. Photoforming method and apparatus
US6200492B1 (en) 1989-11-30 2001-03-13 Henkel Kommanditgesellschaft Auf Aktien Textile lubricants with improved resistance to slinging

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05502273A (en) * 1989-11-30 1993-04-22 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチェン Textile lubricants containing polymers

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE648508C (en) * 1934-12-29 1937-08-03 I G Farbenindustrie Akt Ges Process for sizing crepe yarn
FR1400556A (en) * 1964-04-16 1965-05-28 Centre Nat Rech Scient New polymers of maleic anhydride, process for their preparation and applications

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3908048A (en) * 1972-04-07 1975-09-23 Kao Corp Method of improving interfiber cohesion of filament yarns
US4210700A (en) * 1978-09-15 1980-07-01 Allied Chemical Corporation Production of polyester yarn
US6200492B1 (en) 1989-11-30 2001-03-13 Henkel Kommanditgesellschaft Auf Aktien Textile lubricants with improved resistance to slinging
US5607540A (en) * 1992-02-20 1997-03-04 Teijin Seiki Co., Ltd. Photoforming method and apparatus

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FR2086310B1 (en) 1974-02-15
JPS4841798B1 (en) 1973-12-08
FR2086310A1 (en) 1971-12-31
DE2118699A1 (en) 1971-11-04

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