WO2009097600A1 - Filaments amincis constitués de matériaux d’origine biologique et procédés pour leur préparation - Google Patents

Filaments amincis constitués de matériaux d’origine biologique et procédés pour leur préparation Download PDF

Info

Publication number
WO2009097600A1
WO2009097600A1 PCT/US2009/032804 US2009032804W WO2009097600A1 WO 2009097600 A1 WO2009097600 A1 WO 2009097600A1 US 2009032804 W US2009032804 W US 2009032804W WO 2009097600 A1 WO2009097600 A1 WO 2009097600A1
Authority
WO
WIPO (PCT)
Prior art keywords
filaments
treating solution
filament
solution
tapered
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.)
Ceased
Application number
PCT/US2009/032804
Other languages
English (en)
Inventor
Xianqiao Liu
Nanjian Sun
Mingsong Wang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to CA2713825A priority Critical patent/CA2713825A1/fr
Priority to EP09706542A priority patent/EP2257199A4/fr
Priority to CN2009801106138A priority patent/CN102083337A/zh
Priority to JP2010545242A priority patent/JP2011511658A/ja
Publication of WO2009097600A1 publication Critical patent/WO2009097600A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A46—BRUSHWARE
    • A46D—MANUFACTURE OF BRUSHES
    • A46D1/00—Bristles; Selection of materials for bristles
    • A46D1/04—Preparing bristles
    • A46D1/05—Splitting; Pointing
    • A—HUMAN NECESSITIES
    • A46—BRUSHWARE
    • A46D—MANUFACTURE OF BRUSHES
    • A46D1/00—Bristles; Selection of materials for bristles
    • A46D1/02—Bristles details
    • A46D1/0276—Bristles having pointed ends
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
    • D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, e.g. by ultrasonic waves, corona discharge, irradiation, electric currents or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/02—Sonic or ultrasonic waves; Corona discharge
    • 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
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, e.g. by ultrasonic waves, corona discharge, irradiation, electric currents or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/06—Inorganic compounds or elements
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D06M11/13—Ammonium halides or halides of elements of Groups 1 or 11 of the Periodic Table
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
    • 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
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters

Definitions

  • the present application relates to a tapered filament as well as a method for preparing same. More particularly disclosed herein is a tapered filament obtained from a bio-based material and a method for tapering using a multi-step process to achieve uniform tapering within a bundle of filaments.
  • filaments for brushes are made of synthetic materials or animal hair.
  • nylon 612 and nylon 610 are typically used to prepare filaments for toothbrushes.
  • petroleum-based polyesters such as polybutylene terephthlate (PBT), polyethylene terephthalate (PET) and polytrimethylene terephthalate (PTT) are also used to prepare filaments of one-off toothbrushes.
  • PBT polybutylene terephthlate
  • PET polyethylene terephthalate
  • PTT polytrimethylene terephthalate
  • the filaments of toothbrushes have a flat end, which cannot remove tartar embedded between teeth during tooth brushing. Consequently, these flat end filaments are unable to clean each position around teeth.
  • filaments having flat ends are hard, and can be harmful to gums.
  • synthetic materials used for filaments are mainly produced from petroleum products, which are not bio-based, which does not address concerns relating to energy sources and the environment.
  • the paint brush, cosmetic brush, hair pencil and brush pen are often made of animal hair such as pig hair, fell, squirrel hair and weasel hair. They have naturally tapered ends, however, compared to synthetic materials they are expensive. At the same time, they may cause diffusion and cross-infection of some animal diseases and may lead to more and more protest from worldwide animal protection associations.
  • US6673444 has disclosed a filament for brushes, made of petroleum-based polyesters such as polythmethylene terephthalate (PTT) or blends of polyesters with other materials.
  • PTT polythmethylene terephthalate
  • the filaments made of polyesters or blends of polyesters with other materials cannot satisfy all requirements. For example, with respect to nylon, polyester has a higher rigidity and therefore lower applicability. Therefore, the filaments made of polyesters are typically used to prepare cheap one-off toothbrush.
  • US2006/0088711 has disclosed a tapered polyester filament, which has one or two tapered ends formed by a chemical tapering process.
  • the chemical tapering process comprises treating filaments by immersing the filament into strong acid or strong base solution under a temperature of 120 to 180 0 C.
  • the mechanism of chemical tapering process is to corrupt polyester such as PTT or polybutylene terephthalate (PBT) gradually by chemical capillarity.
  • PTT polybutylene terephthalate
  • conventional chemical tapering processes cannot produce uniform tapered filaments, is very rigorous, and the process conditions are harsh. These conventional processes also have a problem of high cost for maintenance of equipment.
  • Disclosed herein is a method to provide a tapered filament obtained from bio-based polyester using a chemical tapering process which has a mild treating condition over the prior art.
  • the present invention discloses tapered polyester monofilament, demonstrated using a bio-based polyester (Sorona® polymer), wherein said tapered filament is produced using ultrasonic energy to achieve improved taper ratio/consistency under milder conditions than achieved using conventional methods.
  • a method for producing a tapered filament comprising the following steps of: a) providing filaments; b) providing a treating solution in a tank, wherein said treating solution comprises NaOH solution, KOH solution, LiOH solution, combinations of basic soutions thereof, sulfuric acid, hydrochloric acid, phosphoric acid solution, or combinations of acidic solutions thereof; c) immersing the filaments in step a) into the treating solution, d) using an auxiliary means for keeping the concentration of the treating solution uniform during the treatment, wherein during step c), the depth of the filaments immersed in the treating solution is varied with time.
  • tapered filament obtained by the above method.
  • tapered filament prepare as disclosed above in toothbrush, paint brush, cosmetic brush, hair pencil and brush pen applications.
  • Figure 1 is a micro-photograph of a filament bundle of example 1.
  • Figure 2 is a partial-enlarged view of a filament bundle of example 1.
  • Figure 3 is a micro-photograph of a filament in the center of the bundle of example 2.
  • Figure 4 is a micro-photograph of a filament in the periphery of the bundle of example 2.
  • Figure 5 is a micro-photograph of a filament in the center of the bundle of example 3.
  • Figure 6 is a partial-enlarged view of a filament in the periphery of the bundle of example 3.
  • Filament prepared from bio-materials and thereby is bio-based and has better applicability, such as better softness.
  • a bio-based polyester filament having tapered ends, and the process for making same.
  • a tapered filament obtained by a method wherein there is uniform taper length and taper ratio from the center of the tapered filament bundle to the peripheral outer edge of the filament bundle.
  • the process disclosed herein is a multi-step process that results in tapered ratio/consistency under relatively mild process conditions.
  • Chemically tapered polyester such as Sorona® polymer (having a main component of PTT) is prepared by bio-based material, wherein said tapering treatment can be practiced under mild condition by dividing the one-step conventional chemical treatment used for tapering into a multi-step chemical treatment . Further, an auxiliary means to maintain concentration uniformity of the treating solutions during the tapering process s disclosed. The resultant filaments have better applicability and more uniformly tapered length.
  • One embodiment of the present invention is a method for producing a tapered filament, comprising the following steps of: a) providing filaments; b) providing a treating solution for tapering filament; and c) immersing the filament of treating solution, using auxiliary means for keeping the concentration of the treating solution uniform during the treatment wherein during step c), the depth of the filaments impregnated in the treating solution varies with time.
  • the filaments comprise a bio-based polymer, such as Sorona® polymer, or blends of bio-based polymers combined with other polymers.
  • the initial depth of the filaments immersed into the treating solution is from 2 to 20 mm.
  • the final depth of the filaments immersed into the treating solution is from 0 to 10 mm, and the total time for treatment is from 5 to 60 min.
  • the initial depth of the filaments immersed in the treating solution is from 0 to 10 mm.
  • the final depth of the filaments immersed into the treating solution is from 2 to 20 mm, and the total time for treatment is from 5 to 60 min.
  • the filament used in the disclosed process has a length of from 16 to 65 mm.
  • the treating solution comprises
  • Step c) is carried out at a temperature of from 60 to 140 0 C.
  • auxiliary means is used to mechanically stirring and/or circulating the treating solution to maintain a uniform concentration of the solution.
  • the filament(s) of the present invention comprise bio-based polymer. It is more preferred that the filament of the present invention comprises bio-based polyester. It is most preferred that the filament of the present invention comprise bio-based Sorona® polymer, which comprises PTT, or blends comprising Sorona® polymer.
  • the filament is conventional in the art.
  • the filament can be prepared from polyesters, such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polythmethylene terephthalate (PTT) and their copolyesters, or their mixtures.
  • the filament is prepared from Sorona® or its mixture with the above-mentioned materials.
  • Sorona® is a bio-based polymer provided by DuPont Company having a main component of polythmethylene terephthalate (PTT). Sorona® is mainly obtained from fermentation of crop such as corn, therefore it is bio-based.
  • PTT polythmethylene terephthalate
  • PTT useful in the invention is of the type made by polycondensation of terephthalic acid or acid equivalent and 1 ,3-propanediol; with the 1 ,3-propane diol preferably being of the type that is obtained biochemically from a renewable source, that is "biologically-derived" 1 ,3-propanediol.
  • the PTT resin composition comprises a predominant amount of a poly(trimethylene terephthalate).
  • Poly(trimethylene terephthalate) suitable for use in the invention are well known in the art, and conveniently prepared by polycondensation of 1 ,3-propane diol with terephthalic acid or terephthalic acid equivalent.
  • terephthalic acid equivalent is meant compounds that perform substantially like terephthalic acids in reaction with polymeric glycols and diols, as would be generally recognized by a person of ordinary skill in the relevant art.
  • Terephthalic acid equivalents include, for example, esters (such as dimethyl terephthalate), and ester-forming derivatives such as acid halides (e.g., acid chlorides) and anhydrides.
  • Methods for preparation of PTT are discussed, for example in US6277947, US6326456, US6657044, US6353062, US6538076, US2003/0220465A1 and commonly owned U.S. Patent Application No. 11/638919 (filed 14 December 2006, entitled "Continuous Process for Producing Poly(trimethylene Terephthalate)").
  • a particularly preferred source of 1 ,3-propanediol is via a fermentation process using a renewable biological source.
  • biochemical routes to 1 ,3-propanediol have been described that utilize feedstocks produced from biological and renewable resources such as corn feed stock.
  • biological and renewable resources such as corn feed stock.
  • bacterial strains able to convert glycerol into 1 ,3-propanediol are found in the species Klebsiella, Citrobacter, Clostridium, and Lactobacillus.
  • US5821092 discloses, inter alia, a process for the biological production of 1 ,3-propanediol from glycerol using recombinant organisms.
  • the process incorporates E. coli bacteria, transformed with a heterologous pdu diol dehydratase gene, having specificity for 1 ,2-propanediol.
  • the transformed E. coli is grown in the presence of glycerol as a carbon source and 1 ,3-propanediol is isolated from the growth media. Since both bacteria and yeasts can convert glucose (e.g., corn sugar) or other carbohydrates to glycerol, the processes disclosed in these publications provide a rapid, inexpensive and environmentally responsible source of 1 ,3-propanediol monomer.
  • the biologically-derived 1 ,3-propanediol such as produced by the processes described and referenced above, contains carbon from the atmospheric carbon dioxide incorporated by plants, which compose the feedstock for the production of the 1 ,3-propanediol.
  • the biologically-derived 1 ,3-propanediol preferred for use in the context of the present invention contains only renewable carbon, and not fossil fuel-based or petroleum-based carbon.
  • the PTT based thereon utilizing the biologically-derived 1 ,3-propanediol therefore, has less impact on the environment as the 1 ,3-propanediol used does not deplete diminishing fossil fuels and, upon degradation, releases carbon back to the atmosphere for use by plants once again.
  • the compositions of the present invention can be characterized as more natural and having less environmental impact than similar compositions comprising petroleum based diols.
  • the biologically-derived 1 ,3-propanediol, and PTT based thereon may be distinguished from similar compounds produced from a petrochemical source or from fossil fuel carbon by dual carbon-isotopic finger printing.
  • This method usefully distinguishes chemically-identical materials, and apportions carbon material by source (and possibly year) of growth of the biospheric (plant) component.
  • the isotopes, 14C and 13C bring complementary information to this problem.
  • the radiocarbon dating isotope (14C) with its nuclear half life of 5730 years, clearly allows one to apportion specimen carbon between fossil (“dead”) and biospheric ("alive”) feedstocks (Currie, L. A.
  • 14C has acquired a second, geochemical time characteristic. Its concentration in atmospheric CO2, and hence in the living biosphere, approximately doubled at the peak of nuclear testing, in the mid-1960s.
  • fM is defined by National Institute of Standards and Technology (NIST) Standard Reference Materials (SRMs) 4990B and 4990C, known as oxalic acids standards HOxI and HOxII, respectively.
  • SRMs Standard Reference Materials
  • HOxI oxalic acids
  • HOxII oxalic acids
  • HOxII oxalic acids
  • HOxII oxalic acids
  • the stable carbon isotope ratio (13C/12C) provides a complementary route to source discrimination and apportionment.
  • the 13C/12C ratio in a given biosourced material is a consequence of the 13C/12C ratio in atmospheric carbon dioxide at the time the carbon dioxide is fixed and also reflects the precise metabolic pathway. Regional variations also occur. Petroleum, C3 plants (the broadleaf), C4 plants (the grasses), and marine carbonates all show significant differences in 13C/12C and the corresponding ⁇ 13C values. Furthermore, lipid matter of C3 and C4 plants analyze differently than materials derived from the carbohydrate components of the same plants as a consequence of the metabolic pathway.
  • 13C shows large variations due to isotopic fractionation effects, the most significant of which for the instant invention is the photosynthetic mechanism.
  • the major cause of differences in the carbon isotope ratio in plants is closely associated with differences in the pathway of photosynthetic carbon metabolism in the plants, particularly the reaction occurring during the primary carboxylation, i.e., the initial fixation of atmospheric CO2.
  • Two large classes of vegetation are those that incorporate the "C3" (or
  • C3 plants such as hardwoods and conifers, are dominant in the temperate climate zones.
  • the primary CO2 fixation or carboxylation reaction involves the enzyme ribulose-1 ,5-diphosphate carboxylase and the first stable product is a
  • C4 plants include such plants as tropical grasses, corn and sugar cane.
  • C4 plants an additional carboxylation reaction involving another enzyme, phosphenol-pyruvate carboxylase, is the primary carboxylation reaction.
  • the first stable carbon compound is a 4-carbon acid, which is subsequently decarboxylated.
  • the CO2 thus released is refixed by the C3 cycle.
  • Both C4 and C3 plants exhibit a range of 13C/12C isotopic ratios, but typical values are ca. -10 to -14 per mil (C4) and -21 to -26 per mil (C3) (Weber et al., J. Agric. Food Chem., 45, 2942 (1997)). Coal and petroleum fall generally in this latter range.
  • the 13C measurement scale was originally defined by a zero set by pee dee belemnite (PDB) limestone, where values are given in parts per thousand deviations from this material.
  • IRMS stable ratio mass spectrometry
  • Biologically-derived 1 ,3-propanediol, and compositions comprising biologically-derived 1 ,3-propanediol therefore, may be completely distinguished from their petrochemical derived counterparts on the basis of 14C (fM) and dual carbon-isotopic fingerprinting, indicating new compositions of matter.
  • the ability to distinguish these products is beneficial in tracking these materials in commerce. For example, products comprising both "new” and “old” carbon isotope profiles may be distinguished from products made only of "old” materials.
  • the instant materials may be followed in commerce on the basis of their unique profile and for the purposes of defining competition, for determining shelf life, and especially for assessing environmental impact.
  • the 1 ,3-propanediol used as a reactant or as a component of the reactant in making PTT will have a purity of greater than about 99%, and more preferably greater than about 99.9%, by weight as determined by gas chromatographic analysis.
  • Particularly preferred are the purified 1 ,3-propanediols as disclosed in US7038092, US7098368, US7084311 and US20050069997A1.
  • the purified 1 ,3-propanediol preferably has the following characteristics:
  • composition having a CIELAB "b*" color value of less than about 0.15 ASTM D6290
  • absorbance at 270 nm of less than about 0.075 ASTM D6290
  • a peroxide composition of less than about 10 ppm; and/or (4) a concentration of total organic impurities (organic compounds other than 1 ,3-propanediol) of less than about 400 ppm, more preferably less than about 300 ppm, and still more preferably less than about 150 ppm, as measured by gas chromatography.
  • PTT useful in this invention can be PTT homopolymers (derived substantially from 1 ,3-propane diol and terephthalic acid and/or equivalent) and copolymers, by themselves or in blends.
  • PTT used in the invention preferably contain about 70 mole % or more of repeat units derived from 1 ,3-propane diol and terephthalic acid (and/or an equivalent thereof, such as dimethyl terephthalate).
  • the initial poly(timethylene terephthalate) resin useful in the process further comprises 0.1 to 30 mole % repeat units, other than poly(trimethylene terephthalate), made from monomers selected from the group consisting of: terephthalic acid, isophthalic acid, 1 ,4-cyclohexane dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1 ,3-cyclohexane dicarboxylic acid, succinic acid, glutahc acid, adipic acid, sebacic acid, 1 ,12-dodecane dioic acid, and the derivatives thereof such as the dimethyl, diethyl, or dipropyl esters of these dicarboxylic acids; and diols ethylene glycol, 1 ,3-propane diol, 1 ,4-butane diol, 1 ,2-propanediol, diethylene glycol, triethylene glycol, 1 ,3-butane
  • the PTT resin composition contains at least about 80 mole %, or at least about 90 mole %, or at least about 95 mole %, or at least about 99 mole %, of repeat units derived from 1 ,3-propane diol and terephthalic acid (or equivalent).
  • the most preferred polymer is poly(trimethylene terephthalate) homopolymer (polymer of substantially only 1 ,3-propane diol and terephthalic acid or equivalent).
  • the filaments of the present invention are useful in toothbrush, paint brush, cosmetic brush, hair pencil and brush pen applications.
  • filaments have advantages over the prior art in that there is provided a tapered filament prepared from a bio-based material , having a rounded or rough tapered end, and uniform tapered length. When used for toothbrushes, these filaments perform better to remove tartar between teeth. When used for paint brush, cosmetic brush, hair pencil and brush pen, applications, it can reduce cost, extend the life of brush and avoid diffusion, and cross-infection of animal diseases.
  • the method for producing filament is conventional in the art, and a skilled person in the art can directly determine which method can be used to form a filament.
  • the method comprises solution spinning, melt spinning, dry spinning, wet spinning and the like.
  • the filament in step (a) of the present invention, can be provided individually or can be provided in a form of filament bundle.
  • the length of a filament is conventional in the art, and a skilled person in the art can adjust its length according to actual usage.
  • the filament has a length of from 16 to 65mm, preferably from 20 to 60mm, more preferably from 30 to 50mm and most preferably 40mm.
  • the shape of the cross area of the filament there are no limitations on the shape of the cross area of the filament, as long as it can be applied to toothbrush, paint brush, cosmetic brush, hair pencil and brush pen.
  • the shape may be, but is not limited to, circular, oval, square, rectangle, triangle, diamond, and the like.
  • the treating solution is conventional, and a skilled person in the art can directly determine which treating solution can be used.
  • the treating solution comprises an acidic treating solution or a basic treating solution.
  • the basic treating solution comprises NaOH solution, KOH solution, LiOH solution; and the acidic treating solution comprises sulfuric acid, hydrochloric acid, or phosphoric acid solution.
  • the treating temperature is from 60 to 140 0 C, preferably from 80 0 C to 140 0 C, more preferably from 100°C to 140 0 C, and most preferably 120°C.
  • the treating time, or the time that the filament is immersed in the treating solution is from 10 minutes to 4 hours, preferably from 30 minutes to 3 hours, more preferably from 30 minutes to 2 hours, and most preferably from 30 minutes to 1.5 hours.
  • the filaments disclosed herein are bio-based, rather than petroleum based. Also, rather then being prepared by one step treatment (i.e., the filament is immerged into a treating solution in a given depth at one time for a given time), the filaments disclosed herein are obtained from a bio-based product which is and is prepared by a method comprising the step of immersing filament into a treating solution successively for carrying out a multi-step treatment process (i.e., the depth of the filament into the treating solution varies with time). Further, the treating solution used in the process of the present invention is milder than solutions used in conventional tapering of filament using caustic solutions. There is also the option of incorporating auxiliary means for agitating the treating solution during treatment to maintain uniform concentration of the treating solution, and achieve uniformity in the tapering.
  • the treating solution since the treating solution substantively remains non-flowing during treatment, the treating solution has different concentrations at different positions within the treating solution.
  • the solution concentration gets depleted as the treating solution makes contact with the immersed filament. Consequently, concentration of the solution near the periphery bundle of filaments is low, while the concentration away from the bundle of filaments is higher.
  • treatment for tapering of filament in center of the bundle is not as effective as in periphery of the bundle.
  • the present invention provides an approach of incorporating auxiliary means for maintaining the uniformity of concentration in the treating solution during the tapering process.
  • the auxiliary means comprises mechanically stirring and circulating the treating solution.
  • the mechanically stirring and circulating the treating solution are conventional in the art, respectively, and a skilled person in the art can determine their specific modes according to the disclosure of the present description.
  • the auxiliary means comprises, but not be limited to, a stirring rod, a magnetic stirring; and the circulation of the treating solution comprises use of a circulating bump.
  • a preferred auxiliary means for maintaining the uniformity of concentration in the treating solution during the tapering process involves the use of ultrasound energy.
  • Total treating time is from 10 minutes to 4 hours, preferably from 30 minutes to 3 hours, more preferably from 30 minutes to 2 hours, and most preferably from 30 minutes to 1.5 hours.
  • the initial depth of a filament immersed into a treating solution is from 2 to 20 mm, preferably from 1 to 15 mm, more preferably from 7 to 15 mm, and the final depth of a filament immersed into a treating solution is from 0 to 10 mm, preferably from 0 to 8 mm, more preferably from 0 to 5 mm, and most preferably 0 mm.
  • the total treating time is from 5 to 60 minutes.
  • the initial depth of a filament immersed into a treating solution is 0 to 10 mm, preferably from 0 to 8 mm, more preferably from 0 to 5 mm, and most preferably 0 mm.
  • the final depth of a filament immersed into treating solution is from 2 to 20 mm, preferably from 5 to 15 mm, more preferably from 7 to 15 mm.
  • Total treating time is from 5 to 60 minutes.
  • the method of varying depth of immersion with time is conventional, and a skilled person in the art can determine directly this method in detail.
  • Other preferred embodiments of the disclosed method comprise:
  • the tapered end of the filament will contain different tapered sections having different tapering slopes such that the tapered end of the filament may have better applicability, such as better softness.
  • the treating solution may be milder than conventional solutions and the filament may have more uniform tapered length.
  • the filament may have one tapered end or two tapered ends. If it has one tapered end, any end of the filament can be tapered. If it has two tapered ends, the two ends of the filament can be treated in the same or similar manner.
  • the tapered filament disclosed herein has uniform taper length and taper ratio from the center of the tapered filament bundle to the peripheral outer edge of the filament bundle.
  • the method for preparing tapered filaments may further comprise a step of washing.
  • the method for washing filaments is conventional in the art, and can be carried out by a skilled person in the art.
  • the step of washing comprises rinsing filaments with water until the pH of the washings is neutral (near or at pH of 7).
  • the method for preparing tapered filaments can further comprise a step of drying.
  • the method for drying filaments is conventional in the art, and can be carried out by a skilled person in the art .
  • the step of drying comprises drying in an oven.
  • Another aspect of the present invention is a tapered, filament prepared according to the present invention.
  • a preferred embodiment of the present invention is tapered filament made from Sorona® polymer, or its mixture.
  • Tapered filament obtained from a bio-based material and the method for preparing same is also described according to the following examples.
  • the unit used in the examples is percentage by weight.
  • Sorona® polymer was melt spun to form filaments and the formed filaments were thermally molded; bundles were formed by wrapping the resultant filaments through a pre-wrapping film. 2. The resultant bundles were cut into a length of 50 mm using a cutting knife.
  • Example 2 was carried out in the same manner as that in Example 1 , except that in step 3 of Example 2, an aqueous solution of 40% NaOH was added into the molding tank as treating solution for tapering, and then the treating solution was heated to 120 0 C. The bundles were immersed into the treating solution at a depth of 4mm one time and a mechanically stir was carried out near the bundles. The treating time was 40 minutes to obtain tapered filaments.
  • Example 3 was carried out in the same manner as that in Example 1 , except that in step 3 of Example 3, an aqueous solution of 40% NaOH was added into a molding tank as treating solution for tapering, and then the treating solution was heated to 120 0 C. The bundles were immersed into the treating solution in a depth of 4mm one time, without any auxiliary means. The bundles were treated in the treating solution for 40 minutes to obtain tapered filaments.
  • Example 4 was carried out in the same manner as that in Example 1 , except that in step 3 of Example 4, an aqueous solution of 60% NaOH was added into a tank as treating solution for tapering filaments, and then the treating solution was heated to 140°C. The treating solution was circulated by a pump to maintain the treating solution as unchanged. The bundles were immersed into the treating solution in a depth of 2mm. After 2 minutes, additional aqueous solution of 60% NaOH was added such that the filaments were immersed at a depth of 4mm. The above steps were repeated. After 10 minutes, the treatment was complete.
  • Example 5 was carried out in the same manner as that in Example 1 , except that in step 3 of Example 5, the concentration of the treating solution was 60%, the treating solution was heated to 60 0 C and the bundles were immersed into in a depth of 20mm. After 10 minutes, the bundles were raised for 5mm such that the filaments were immersed at a depth of 15mm. After another 10 minutes, the bundles were raised again for 5mm. The above steps were repeated until the treating time reached 30 minutes.
  • Example 6 was carried out in the same manner as that in Example 1 , except that the bundles had a length of 65mm.
  • the tapered filaments obtained according to the present invention have a tapered end which varies, thereby increasing the softness and applicability.
  • tapered filaments obtained not according to the present invention have different tapered ends between the filaments in the center of the bundle and those in the periphery of the bundle, thereby reducing qualification rate.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Inorganic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Brushes (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

La présente invention concerne un filament aminci préparé à partir d’un matériau d’origine biologique et un procédé pour la production de celui-ci. La présente invention concerne généralement un procédé destiné à produire un filament aminci, comportant les étapes consistant à : a) procurer des filaments ; b) amener une solution de traitement jusqu’à une cuve de traitement ; c) immerger les filaments de l’étape a) dans la solution de traitement, à l’aide de moyens auxiliaires tels qu’un brassage et / ou une circulation mécanique ou une énergie ultrasonique pour l’agent de traitement afin de renforcer les effets de l’amincissement, la profondeur d’immersion des filaments dans l’agent de traitement variant en fonction du temps au cours de l’étape c).
PCT/US2009/032804 2008-02-02 2009-02-02 Filaments amincis constitués de matériaux d’origine biologique et procédés pour leur préparation Ceased WO2009097600A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CA2713825A CA2713825A1 (fr) 2008-02-02 2009-02-02 Filaments amincis constitues de materiaux d'origine biologique et procedes pour leur preparation
EP09706542A EP2257199A4 (fr) 2008-02-02 2009-02-02 Filaments amincis constitués de matériaux d'origine biologique et procédés pour leur préparation
CN2009801106138A CN102083337A (zh) 2008-02-02 2009-02-02 来自生物基材料的锥形长丝及其制备方法
JP2010545242A JP2011511658A (ja) 2008-02-02 2009-02-02 バイオ材料によるテーパーフィラメントおよびその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CNA2008100058187A CN101496675A (zh) 2008-02-02 2008-02-02 一种来自可再生生物基原料的尖头刷丝及制备方法
CN200810005818.7 2008-02-02

Publications (1)

Publication Number Publication Date
WO2009097600A1 true WO2009097600A1 (fr) 2009-08-06

Family

ID=40913298

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2009/032804 Ceased WO2009097600A1 (fr) 2008-02-02 2009-02-02 Filaments amincis constitués de matériaux d’origine biologique et procédés pour leur préparation

Country Status (6)

Country Link
EP (1) EP2257199A4 (fr)
JP (1) JP2011511658A (fr)
KR (1) KR20100130983A (fr)
CN (2) CN101496675A (fr)
CA (1) CA2713825A1 (fr)
WO (1) WO2009097600A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102912546A (zh) * 2012-11-09 2013-02-06 泉州海天材料科技股份有限公司 一种高密针织衬衫面料及其制备方法
EP2564808A4 (fr) * 2010-04-30 2014-07-02 Lg Household & Health Care Ltd Élément de nettoyage interdentaire et son procédé de fabrication
EP2732724A4 (fr) * 2011-07-11 2015-10-07 Nippon Sanmo Deying Fibre de brosse, brosse utilisant la fibre de brosse, et procédé de fabrication de la fibre de brosse
USD754442S1 (en) 2013-07-17 2016-04-26 Colgate-Palmolive Company Toothbrush
US9320335B2 (en) 2013-12-30 2016-04-26 L'oreal Grooming devices and methods therefor
EP2868226A4 (fr) * 2012-06-27 2016-04-27 Nippon Sanmo Deying Procédé de fabrication d'une base de poils de brosse
CN112568591A (zh) * 2019-09-29 2021-03-30 中山尚洋科技股份有限公司 化妆刷刷毛的磨峰工艺

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101187493B1 (ko) 2011-04-26 2012-10-02 경북대학교 산학협력단 내섬유 분할을 이용한 세섬사 촉감을 갖는 양모섬유의 제조방법 및 이에 의해 제조된 양모섬유
CN103643477B (zh) * 2013-11-07 2016-08-17 聚力高分子材料科技沭阳有限公司 一种聚酯单丝磨尖的生产方法
CN105803563A (zh) * 2014-12-31 2016-07-27 杜邦兴达（无锡）单丝有限公司 化妆刷用单丝
CN105725480A (zh) * 2016-02-23 2016-07-06 无锡市兴达尼龙有限公司 异形刷丝及其制造方法
CN106702532A (zh) * 2017-01-17 2017-05-24 深圳市华之飞科技有限公司 一种3d镜片抛光刷丝的配方及其制作方法
CN111621869A (zh) * 2020-06-05 2020-09-04 广东永锐实业有限公司 一种抗菌刷丝及其制备方法与应用
CN115530520A (zh) * 2022-08-31 2022-12-30 江苏三笑集团有限公司 刷丝毛尖端溶蚀成型方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4285892A (en) * 1979-03-01 1981-08-25 Shinwa Seisakusho Co., Ltd. Process for tapering synthetic fibers at the end portion thereof
US5437918A (en) * 1992-11-11 1995-08-01 Mitsui Toatsu Chemicals, Inc. Degradable non-woven fabric and preparation process thereof
US5722106A (en) * 1995-02-01 1998-03-03 Gillette Canada Inc. Tooth polishing brush
US20060088711A1 (en) * 2004-10-21 2006-04-27 Kenji Nakamura Brush bristle material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4285892A (en) * 1979-03-01 1981-08-25 Shinwa Seisakusho Co., Ltd. Process for tapering synthetic fibers at the end portion thereof
US5437918A (en) * 1992-11-11 1995-08-01 Mitsui Toatsu Chemicals, Inc. Degradable non-woven fabric and preparation process thereof
US5722106A (en) * 1995-02-01 1998-03-03 Gillette Canada Inc. Tooth polishing brush
US5722106B1 (en) * 1995-02-01 2000-06-06 Gillette Canada Tooth polishing brush
US20060088711A1 (en) * 2004-10-21 2006-04-27 Kenji Nakamura Brush bristle material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2257199A4 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2564808A4 (fr) * 2010-04-30 2014-07-02 Lg Household & Health Care Ltd Élément de nettoyage interdentaire et son procédé de fabrication
US9084654B2 (en) 2010-04-30 2015-07-21 Lg Household & Health Care Ltd. Interdental cleaning member and manufacturing method thereof
EP2732724A4 (fr) * 2011-07-11 2015-10-07 Nippon Sanmo Deying Fibre de brosse, brosse utilisant la fibre de brosse, et procédé de fabrication de la fibre de brosse
EP2868226A4 (fr) * 2012-06-27 2016-04-27 Nippon Sanmo Deying Procédé de fabrication d'une base de poils de brosse
CN102912546A (zh) * 2012-11-09 2013-02-06 泉州海天材料科技股份有限公司 一种高密针织衬衫面料及其制备方法
USD754442S1 (en) 2013-07-17 2016-04-26 Colgate-Palmolive Company Toothbrush
US9320335B2 (en) 2013-12-30 2016-04-26 L'oreal Grooming devices and methods therefor
CN112568591A (zh) * 2019-09-29 2021-03-30 中山尚洋科技股份有限公司 化妆刷刷毛的磨峰工艺

Also Published As

Publication number Publication date
EP2257199A1 (fr) 2010-12-08
CA2713825A1 (fr) 2009-08-06
EP2257199A4 (fr) 2011-06-29
KR20100130983A (ko) 2010-12-14
CN101496675A (zh) 2009-08-05
CN102083337A (zh) 2011-06-01
JP2011511658A (ja) 2011-04-14

Similar Documents

Publication Publication Date Title
EP2257199A1 (fr) Filaments amincis constitués de matériaux d'origine biologique et procédés pour leur préparation
JP4908443B2 (ja) 改良ポリエステル射出成形品
US20100261932A1 (en) Polytrimethylene ether glycol esters
CN102245670A (zh) 具有增强的撕裂强度的共聚酯
US20100151165A1 (en) Polyester compositions from biologically-derived materials
CN113874562B (zh) 热粘合纤维用聚酯组合物、由此实现的热粘合复合纤维及无纺布
KR20110112339A (ko) 인열 강도가 증진된 코폴리에스테르
US8759559B2 (en) Processes for preparing polytrimethylene ether glycol esters
US20130129951A1 (en) Polymerization with enhanced glycol ether formation
WO2011062600A1 (fr) Polycondensation avec un réacteur malaxeur
EP2403895A1 (fr) Pastilles de poly(téréphtalate de triméthylène) avec oligomères réduits et procédé de mesure de réduction des oligomères
WO2009020944A1 (fr) Composition ignifuge à base de polytriméthylène téréphtalate
US20100152412A1 (en) Reduction of whitening of poly(trimethylene terephthalate) parts by solvent exposure
JP2012001827A (ja) ポリエステル繊維
KR20090087945A (ko) 용융 방사 엘라스토머 멀티필라멘트사
US8163868B2 (en) Reduction of whitening of polymer parts
CN107418764A (zh) 一种玻璃培养皿洗涤液及其洗涤方法
Ahmed et al. Comparative effects of polycarboxylic acids in sorbitol-based birch wood modification
Lim et al. RSC Sustainability
US8114957B2 (en) Process for preparing poly(trimethylene ether) glycol and copolymers thereof
EP2334726A1 (fr) Composition ignifugeante de poly(triméthylène téréphtalate)
JP2004024520A (ja) 清掃性に優れる高性能ブラシ
JP2004024519A (ja) ２段階のテーパー部を有するフィラメントを含む高性能ブラシ
JP2004024518A (ja) 高機能性歯ブラシ
TH16904A (th) กระบวนการสำหรับการเตรียมโพลีเอสเตอร์และโคโพลีเอสเตอร์

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980110613.8

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09706542

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2713825

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2010545242

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2009706542

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 20107019528

Country of ref document: KR

Kind code of ref document: A