US1773969A - Process of and apparatus for making artificial filaments - Google Patents

Process of and apparatus for making artificial filaments Download PDF

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Publication number
US1773969A
US1773969A US304808A US30480828A US1773969A US 1773969 A US1773969 A US 1773969A US 304808 A US304808 A US 304808A US 30480828 A US30480828 A US 30480828A US 1773969 A US1773969 A US 1773969A
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filaments
orifice
cellulose
orifices
indentations
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US304808A
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Dreyfus Camille
Whitehead William
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Celanese Corp
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Celanese Corp
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Priority to US304808A priority Critical patent/US1773969A/en
Priority to GB27045/29A priority patent/GB318631A/en
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/253Formation of filaments, threads, or the like with a non-circular cross section; Spinnerette packs therefor
    • AHUMAN NECESSITIES
    • A46BRUSHWARE
    • A46DMANUFACTURE OF BRUSHES
    • A46D1/00Bristles; Selection of materials for bristles
    • 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
    • Y10T428/2973Particular cross section

Definitions

  • This invention relates to process of and apparatus for the production of artificial fi aments such as artificial silk, bristles, horse hair and the like from solutions containing 5 cellulosic material[
  • An object of our invention is to provide a process of and apparatus for the production of artificial filaments that have more regular cross section than have artificial filaments that have heretofore been made.
  • Another object of our invention is to spin solutions of cellulosic material through orifices having squat shapes and which have indentations therein, whereby filaments of more uniform rigidity and pliability in all directions may be produced.
  • the practice has been to extrude the solutions through circular orifices into a precipitating bath or evaporative atmosphere.
  • the outer layer of the filament or stream of cellulosic material which is at first circular in cross section, hardens or solidifies first, forming a skin that is tougher and less fluid than the interior of the filament.
  • the interior of the filament is precipitated or dried and thereby shrinks, While the outer layer has further hardened.
  • the outer shell of the filament is tough er and more determined in shape than the interior, the contraction of the volume of the interior causes the outer film or layer to col lapse, and assume a very irregular cross section which is in the form of a figure of manyindentations of varying sizes and shapes, and which is often quite flat. Because of the irregularity of shape and the flatness of-the cross section of such filaments, their covering power, their pliability and their lustre are quite irregular. We have found that if instead of using circular orifices for spinning, holes having predetermined indentations therein are employed, more uniform filaments may be formed.
  • filaments by extrusion of solutions of cellulosic material in a suitable solvent through orifices of squat shape having indentations in the form of reentrant angles or cus s into a recipitating or cvaporative atmosp 'ere.
  • filaments of say 1 to 10 denier, such as are used for making artificial yarns may be made by our process. These filaments may be used as such, or they may be associated or twisted together to form yarns that are useful for making woven or knitted fabrics.
  • the filaments formed by our invention may be heavier, say of 20 to 2000 denier or more, and'may be used as artificial bri'stlesin themaking of various brushes, for making braids, or for making artificial furs, etc.
  • the cellulosic materials employed in our precess may be any suitable ones that are used for making artificial filaments.
  • our process may be used in the making of reconstituted cellulose from viscose or by the cuprammonium or Chardonet process.
  • This invention is particularly applicable for making filaments from organic derivatives of cellulose such as organic esters of cellulose and cellulose ethers.
  • organic esters of cellulose are cellulose acetate, cellulose formate, cellulose propionate and cellulose butyrate; while examples of cellulose ethers are ethyl cellulose, methyl cellulose and benzyl cellulose.
  • the orifices may be wholly symmetriployed, the filaments are extruded into a recipitating aqueous bath containing aci .or
  • the solutions may be 1 extruded into a bath containing a liquid that forms a solution with the solvent, which solution is a non-solvent for thecellulosic deriva-' tive.
  • a solution of an acetone soluble cellulose acetate in acetone is spun, the precipitating bath may consist of water.
  • the filaments are extruded into a dry evaporative atmosphere such as air, carbon dioxide, nitrogen or other gas that has no deleterious ao-efl'ect upon the filaments formed. This atmosphere is preferably maintained at a temperature at or near the boiling point of the solvent employed. 1
  • Figures 1', 2 and 3 show the cross section on an enlarged scale of filaments formed to explain our invention
  • Fig. 1 is shown an orifice in the form of a regular polygon having right angles, in which all of the sides are equal in length and having the four reentrant angles indicatedvat 2.
  • the cross section of the filament formed by such orifices is shown in Fig. 1. While we prefer to make the sides of the figure equal, they may be madefunequal, provided that the side 1 is not more than twice or ⁇ less than one-half of the side 3.
  • the orifice is shown in the form of a symmetrical curved figure having the reentrant cusps 5.
  • the cross section of the filament formed by extrusion through such an orifice is shown in Fig. 2.
  • the orifices are in the form of a regular polygon having sides of equal length and having apices 8 in the form of acute angles, and having the obtuse reentrant angles 9.
  • the cross section of a fila ment formed by such an orifice is shown in Fig. 3.
  • Fig. 4 a cluster of four small round holes 10 placed close together so that the filamentsafter extrusion coalesce to form a single filament.
  • This cluster of orifices operates under the same principle as the single orifice shown in Fig. 2, and forms a single filament much like the filament formed by extrusion through such single orifice.
  • Fig. 5 is shown an orifice of polygonal form having reentrant angles 12, and is a combination of the forms shown in Figures 1 and 3.
  • Fig. 6 shows an orifice having the reentrant cusps 14, and is a combination of the forms shown in Figures 1 and 2.
  • Fig. 7 shows an orifice having reentrant cusps 16 and is a combination of the forms shown in Figures 2 and 3.
  • Method of forming filaments comprising extruding a solution of an organic derivative of cellulose in a volatile solvent through an orifice in the form of a squat figure having indentations therein into a heated evaporative atmosphere.
  • Method of forming filaments comprising extruding a solution of cellulose acetate in a volatile solvent through an orifice in the form of a squat figure having indentations therein into a heated evaporative atmoshere.
  • Method of forming filaments comprising extruding a solution of an organic derivative of cellulose in a volatile solvent through an orifice in the form of a squat figure having reentrant angles or cusps therein, whereby filaments of substantially uniform covering power and substantially uniform rigidit and pliability in all directions is for'medl 6.
  • Method of forming filaments comprising extruding a solution of cellulose acetate in a volatile solvent through an orifice in the form of a squat figure having reentrant angles or cusps therein, whereby filaments of substantially uniform covering power and substantially uniform rigidity and pliability in all directions is formed.
  • Filaments of cellulose acetate havin substantially uniform covering ower and substantially uniform rigidity an liability in all directions, such as is formed y extrusion through an orifice of squat form having indentations therein.
  • a spinnerette having an orifice in the form of a squat figure having indentations therein.
  • a spinnerette having an orifice in the form of a squat figure having reentrant angles or cusps therein.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Multicomponent Fibers (AREA)
  • Artificial Filaments (AREA)

Description

Aug. 26, 1930. c, us ET AL 1,773,969
PROCESS OF AND APPARATUS FOR MAKING ARTIFICIAL FILAMENTS Filed Sept. 8, 1928 1 321.1? Tifia 31? O O INVENTORS CAMILLE DREYFUS HITEHEAD 8 BY WILLIAZ W ATTORNEYS Patented Aug. 26, 1930 UNITED STATES OAIILLE DBEYI'US, NEW YORK, N. Y., AND WILLIAM LAND, MARYLAND, ASSIGNORS TO CELANESE CORPORATION 01 AMERICA, A COB- POBATION OF DELAWARE PROCESS 01 AND APPARATUS FOR MAKING ARTJJICIAL IILAmTB Application fled September 8, 1928. Serial 10. 304,808.
This invention relates to process of and apparatus for the production of artificial fi aments such as artificial silk, bristles, horse hair and the like from solutions containing 5 cellulosic material[ An object of our invention is to provide a process of and apparatus for the production of artificial filaments that have more regular cross section than have artificial filaments that have heretofore been made.
Another object of our invention is to spin solutions of cellulosic material through orifices having squat shapes and which have indentations therein, whereby filaments of more uniform rigidity and pliability in all directions may be produced. Other objects of our invention will appear in the following detailed description.
In the spinning of filaments from cellulosic material, the practice has been to extrude the solutions through circular orifices into a precipitating bath or evaporative atmosphere. In such process, the outer layer of the filament or stream of cellulosic material, which is at first circular in cross section, hardens or solidifies first, forming a skin that is tougher and less fluid than the interior of the filament. After the initial hardening of the outer surface, the interior of the filament is precipitated or dried and thereby shrinks, While the outer layer has further hardened. Since the outer shell of the filament is tough er and more determined in shape than the interior, the contraction of the volume of the interior causes the outer film or layer to col lapse, and assume a very irregular cross section which is in the form of a figure of manyindentations of varying sizes and shapes, and which is often quite flat. Because of the irregularity of shape and the flatness of-the cross section of such filaments, their covering power, their pliability and their lustre are quite irregular. We have found that if instead of using circular orifices for spinning, holes having predetermined indentations therein are employed, more uniform filaments may be formed.
In accordance with our invention, we form filaments by extrusion of solutions of cellulosic material ina suitable solvent through orifices of squat shape having indentations in the form of reentrant angles or cus s into a recipitating or cvaporative atmosp 'ere.
ilaments of any suitable size may be formed by our invention. Thus filaments of say 1 to 10 denier, such as are used for making artificial yarns, may be made by our process. These filaments may be used as such, or they may be associated or twisted together to form yarns that are useful for making woven or knitted fabrics. The filaments formed by our invention may be heavier, say of 20 to 2000 denier or more, and'may be used as artificial bri'stlesin themaking of various brushes, for making braids, or for making artificial furs, etc.
The cellulosic materials employed in our precess may be any suitable ones that are used for making artificial filaments. Thus our process may be used in the making of reconstituted cellulose from viscose or by the cuprammonium or Chardonet process. This invention is particularly applicable for making filaments from organic derivatives of cellulose such as organic esters of cellulose and cellulose ethers. Examples of organic esters of cellulose are cellulose acetate, cellulose formate, cellulose propionate and cellulose butyrate; while examples of cellulose ethers are ethyl cellulose, methyl cellulose and benzyl cellulose.
When employing organic derivatives of cellulose in our process, the same may be dissolved in any suitable volatile solvent such as acetone, mixtures of acetone and ethyl or The orifices through which the solutions of cellulosic material is extruded should be of squat shape having indentations therein.
They may be in the form of polygons having reentrant angles, or they may be in the form of curved figures having reentrant cusps therein. Moreover they maybe in the form having some straight sides and some curved sides. The orifices may be wholly symmetriployed, the filaments are extruded into a recipitating aqueous bath containing aci .or
any other precipitating agent. If organic derivatives are used, the solutions may be 1 extruded into a bath containing a liquid that forms a solution with the solvent, which solution is a non-solvent for thecellulosic deriva-' tive. For instance, when a solution of an acetone soluble cellulose acetate in acetone is spun, the precipitating bath may consist of water. If'a dry spinning process is employed, the filaments are extruded into a dry evaporative atmosphere such as air, carbon dioxide, nitrogen or other gas that has no deleterious ao-efl'ect upon the filaments formed. This atmosphere is preferably maintained at a temperature at or near the boiling point of the solvent employed. 1
By employing orifices of the shape de- 2 scribed, what probably takes place is that the solution of the cellulosic material, when extruded through the orifices assumes approximately the shape of such orifices. At the indentations, or reentrant angles or cusps, the solution does not dry as rapidly as the outermost portions, due to the fact that the precipitatingbath or the heated evaporative atmosphere does not have as strong effect at the interior portions as they do at the exterior points. This is because the precipitating bath is more saturated with the products of reaction or the evaporative atmosphere is more saturated with the vapors of the solvent at the interior points, since it is w more confined at these places and less open to the main precipitating bath or drying atmosphere. When upon further exposure to the precipitating bath or drying atmosphere, the interior of the filament hardens and shrinkage occurs, collapse takes place only at the weaker or softer places corresponding to the indentations. Thus b suitably positioning these indentations, t e shape of the filament formed may be controlled. It will thus be seen that the filaments formed by our process have more uniform covering power and more uniform rigidity and pliability in all directions than have filaments formed. by extrusion through circular holes, and have a cross section whose shape is more regular than the cross section of filaments formed by the old process. In order further reference is hadto the accompanying drawing wherein Figures 1 to 8 are views on an enlarged scale of various forms of orifices that may be employed in our invention, and
Figures 1', 2 and 3 show the cross section on an enlarged scale of filaments formed to explain our invention,
gy extrusion through the orifices shown in ig. 1, 2 and 3 respectively. a I
In Fig. 1 is shown an orifice in the form of a regular polygon having right angles, in which all of the sides are equal in length and having the four reentrant angles indicatedvat 2. The cross section of the filament formed by such orifices is shown in Fig. 1. While we prefer to make the sides of the figure equal, they may be madefunequal, provided that the side 1 is not more than twice or\less than one-half of the side 3.
- In Fig. 2, the orifice is shown in the form of a symmetrical curved figure having the reentrant cusps 5. The cross section of the filament formed by extrusion through such an orifice is shown in Fig. 2.
In Fig. 3, the orifices are in the form of a regular polygon having sides of equal length and having apices 8 in the form of acute angles, and having the obtuse reentrant angles 9. The cross section of a fila ment formed by such an orifice is shown in Fig. 3.
In Fig. 4 is shown a cluster of four small round holes 10 placed close together so that the filamentsafter extrusion coalesce to form a single filament. This cluster of orifices operates under the same principle as the single orifice shown in Fig. 2, and forms a single filament much like the filament formed by extrusion through such single orifice.
In Fig. 5 is shown an orifice of polygonal form having reentrant angles 12, and is a combination of the forms shown in Figures 1 and 3.
Fig. 6 shows an orifice having the reentrant cusps 14, and is a combination of the forms shown in Figures 1 and 2.
Fig. 7 shows an orifice having reentrant cusps 16 and is a combination of the forms shown in Figures 2 and 3.
Thus it will be seen that the number of orifices that may be employed in accordance with our invention is ractically unlimited. Instead of employing t e form shown in Fig. 1, which is wholly symmetrical, a form shown in Fig. 8 may be employed, wherein the area of the portion 18 is less than that of the portion 19.
It is to be understood that the foregoing detailed description is given merely by way of illustration and that many variations may be made therein without departing from the spirit of our invention.
Havin described our invention what we claim and desire to secure by Letters Patent 1. In the method of forming filaments from solutions of cellulosic materlal, the step of extruding such filaments through an orifice in the form of a squat figure having indentations therein.
2. In the method of forming filaments from solutions of oellulosic material, the step of extruding such filaments throu h an orifice in the form of a squat figure aving reentrant angles or cusps therein.
3. Method of forming filaments comprising extruding a solution of an organic derivative of cellulose in a volatile solvent through an orifice in the form of a squat figure having indentations therein into a heated evaporative atmosphere.
4. Method of forming filaments comprising extruding a solution of cellulose acetate in a volatile solvent through an orifice in the form of a squat figure having indentations therein into a heated evaporative atmoshere.
5. Method of forming filaments comprising extruding a solution of an organic derivative of cellulose in a volatile solvent through an orifice in the form of a squat figure having reentrant angles or cusps therein, whereby filaments of substantially uniform covering power and substantially uniform rigidit and pliability in all directions is for'medl 6. Method of forming filaments comprising extruding a solution of cellulose acetate in a volatile solvent through an orifice in the form of a squat figure having reentrant angles or cusps therein, whereby filaments of substantially uniform covering power and substantially uniform rigidity and pliability in all directions is formed.
7. Filaments of cellulosic material havin substantially uniform covering ower and substantially uniform rigidity an liability in all directions, such as is formed y extrusion through an orifice of squatform having indentations therein.
8. Filaments of organic derivative of cellulose having substantially uniform cover ing power substantiall uniform rigidity and pliability in all directions, such as is formed y extrusion through an orifice of squat form having indentations therein.
9. Filaments of cellulose acetate havin substantially uniform covering ower and substantially uniform rigidity an liability in all directions, such as is formed y extrusion through an orifice of squat form having indentations therein.
10. A spinnerette having an orifice in the form of a squat figure having indentations therein. I
11. A spinnerette having an orifice in the form of a squat figure having reentrant angles or cusps therein.
In testimony whereof, we have hereunto subscribed our names.
OAMILLE DREYFUS. I WILLIAM WHITEHEAD.
US304808A 1928-09-08 1928-09-08 Process of and apparatus for making artificial filaments Expired - Lifetime US1773969A (en)

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Cited By (66)

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Publication number Priority date Publication date Assignee Title
US2433325A (en) * 1942-08-19 1947-12-23 Extruded Plastics Inc Extruded resinous bristles
US2443055A (en) * 1944-03-02 1948-06-08 Pittsburgh Plate Glass Co Brush embodying synthetic bristles
US2508799A (en) * 1944-12-28 1950-05-23 Pittsburgh Plate Glass Co Paintbrush and synthetic bristles for the same
US2614288A (en) * 1947-03-28 1952-10-21 Chavannes Synthetic Fibres Inc Apparatus and method for producing thermoplastic fibers
US2637893A (en) * 1949-03-12 1953-05-12 Shaw Gilbert Artificial filament
US2666976A (en) * 1950-06-10 1954-01-26 Allied Chem & Dye Corp Synthetic bristle and process for its production
US2743511A (en) * 1952-11-05 1956-05-01 Nat Plastic Products Company Scouring pad and filament
US2804645A (en) * 1953-05-12 1957-09-03 Du Pont Spinneret plate for melt spinning
US2828752A (en) * 1954-08-16 1958-04-01 Eastman Kodak Co Fibrous tobacco smoke filters
US2831748A (en) * 1952-02-26 1958-04-22 British Celanese Process for melt spinning crimped filaments
US2843449A (en) * 1954-04-13 1958-07-15 Eastman Kodak Co Dry spinning process
US2848737A (en) * 1952-07-18 1958-08-26 Firestone Tire & Rubber Co Extrusion die
US2876477A (en) * 1955-12-08 1959-03-10 George G Stewart Brush
US2939202A (en) * 1959-12-31 1960-06-07 Du Pont Synthetic polymer textile filament
US2945739A (en) * 1955-06-23 1960-07-19 Du Pont Process of melt spinning
US3023483A (en) * 1959-02-19 1962-03-06 Steiner Walter Rope made from synthetic thermoplastics
US3049751A (en) * 1952-12-02 1962-08-21 Owens Corning Fiberglass Corp Method and apparatus for forming fibers
US3059260A (en) * 1959-11-16 1962-10-23 Lester R Peilet Spring actuated self-cleaning retractable brush or the like
US3077633A (en) * 1958-05-15 1963-02-19 Eastman Kodak Co Apparatus for spinning synthetic filaments and fibers of increased bulk and stiffness
US3109220A (en) * 1960-08-19 1963-11-05 Du Pont Tetralobal cross-sectioned filaments
US3109768A (en) * 1960-01-06 1963-11-05 Du Pont Textile filament
US3122960A (en) * 1964-03-03 stohlen
US3128488A (en) * 1961-08-24 1964-04-14 Valden Company Plastic brush
US3131427A (en) * 1958-10-17 1964-05-05 Celanese Corp Spinnerette
US3169089A (en) * 1960-04-22 1965-02-09 Celanese Corp Filaments
US3238553A (en) * 1964-04-09 1966-03-08 E B & A C Whiting Company Filamentary articles
US3239867A (en) * 1963-11-04 1966-03-15 Osborn Mfg Co Brush and brush material
US3302230A (en) * 1964-10-30 1967-02-07 Poppelmann Ake Toothbrush
US3308504A (en) * 1965-07-22 1967-03-14 Us Rubber Co Spinnerets
US3325845A (en) * 1965-02-26 1967-06-20 Int Playtex Corp Nylon bristle resembling natural bristle
US3419936A (en) * 1967-01-31 1969-01-07 Monsanto Co Spinneret for melt spinning filaments
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US4860531A (en) * 1987-12-16 1989-08-29 Wells D Phillips Racquet strings
US4872979A (en) * 1987-04-22 1989-10-10 The Perkin-Elmer Corporation Chromatography column
US5360165A (en) * 1992-09-28 1994-11-01 Singhal Tara C Spray paint nozzle and nozzle shroud
US5677059A (en) * 1995-05-10 1997-10-14 Kanegafuchi Kagaku Kogyo Kabushiki Kaisha Fiber for artificial hair having excellent bulkiness
US5993784A (en) * 1997-07-24 1999-11-30 Whitehill Oral Technologies Low foaming therapeutic toothpastes with improved cleaning and abrasion performance
US6093491A (en) * 1992-11-30 2000-07-25 Basf Corporation Moisture transport fiber
DE10212701A1 (en) * 2002-03-21 2003-10-02 Coronet Werke Gmbh Bristle, method and device for its manufacture and bristle goods
US6805730B2 (en) * 2002-01-29 2004-10-19 Amersham Biosciences Membrane Separations Corp. Convoluted surface hollow fiber membranes
US20070089795A1 (en) * 2005-10-17 2007-04-26 Jacob Jamey D Plasma actuator
US20070289078A1 (en) * 2006-06-16 2007-12-20 Georges Driesen Toothbrush, toothbrush head and tooth cleaning bristle
AT503803B1 (en) * 2006-06-14 2008-01-15 Chemiefaser Lenzing Ag LYOCELL STAPLE FIBER
US20080090076A1 (en) * 2004-12-10 2008-04-17 Lenzing Aktiengesellschaft Cellulosic staple fiber and its use
US20080127543A1 (en) * 2005-07-16 2008-06-05 Fly Fishing Technology Limited Fly Fishing Line
AT504704B1 (en) * 2006-06-14 2008-12-15 Chemiefaser Lenzing Ag FIBER-CONTAINING OBJECT
AT505978B1 (en) * 2007-07-31 2009-08-15 Lenzing Plastics Gmbh MONOFIL WITH NON-CIRCULAR CROSS-SECTION, THE PRODUCTION THEREOF, AND YARN MANUFACTURED THEREOF
EP2165012A1 (en) * 2007-05-23 2010-03-24 Kolon Industries Inc. A cellulose-based filament for tire cord, a bundle comprising the same, a twisted yarn comprising the same, and a tire cord comprising the same
US20100306944A1 (en) * 2009-03-04 2010-12-09 Braun Gmbh Toothbrush bristle and method for manufacturing such a bristle
DE10361820B4 (en) * 2003-12-30 2013-05-29 Jovica Vukosavljevic toothbrush bristle
USD756592S1 (en) * 2013-11-08 2016-05-24 Fam Shred
US20180021611A1 (en) * 2016-07-25 2018-01-25 Awg Fittings Gmbh Nozzle for water, in particular for a water cannon
WO2019055368A1 (en) * 2017-09-15 2019-03-21 Colgate-Palmolive Company Bristle for an oral care implement
US10251470B1 (en) 2017-10-10 2019-04-09 The Procter & Gamble Company Head for an oral care implement and oral care implement
US10856646B2 (en) 2014-07-15 2020-12-08 The Procter & Gamble Company Oral-care implement having color-communicative element
US11206916B2 (en) 2016-06-03 2021-12-28 The Procter & Gamble Company Head for an oral care implement and oral care implement
US11219302B2 (en) 2017-10-10 2022-01-11 The Procter & Gamble Company Head for an oral care implement and oral care implement
US11284707B2 (en) 2016-06-03 2022-03-29 The Procter & Gamble Company Filament for an oral care implement and oral care implement
US11425991B2 (en) 2014-03-11 2022-08-30 The Procter & Gamble Company Head for an oral care implement
USD1020655S1 (en) * 2023-11-01 2024-04-02 Hanwu Liu Toothbrush head
USD1031275S1 (en) * 2023-10-31 2024-06-18 Xiaohong Wu Toothbrush head

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JPS5418389Y2 (en) * 1975-08-01 1979-07-11

Cited By (82)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3122960A (en) * 1964-03-03 stohlen
US2433325A (en) * 1942-08-19 1947-12-23 Extruded Plastics Inc Extruded resinous bristles
US2443055A (en) * 1944-03-02 1948-06-08 Pittsburgh Plate Glass Co Brush embodying synthetic bristles
US2508799A (en) * 1944-12-28 1950-05-23 Pittsburgh Plate Glass Co Paintbrush and synthetic bristles for the same
US2614288A (en) * 1947-03-28 1952-10-21 Chavannes Synthetic Fibres Inc Apparatus and method for producing thermoplastic fibers
US2637893A (en) * 1949-03-12 1953-05-12 Shaw Gilbert Artificial filament
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