WO2012177483A1 - Esters de cellulose présentant des particules de dioxyde de titane à phases mixtes à dégradation améliorée - Google Patents

Esters de cellulose présentant des particules de dioxyde de titane à phases mixtes à dégradation améliorée Download PDF

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Publication number
WO2012177483A1
WO2012177483A1 PCT/US2012/042451 US2012042451W WO2012177483A1 WO 2012177483 A1 WO2012177483 A1 WO 2012177483A1 US 2012042451 W US2012042451 W US 2012042451W WO 2012177483 A1 WO2012177483 A1 WO 2012177483A1
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Prior art keywords
article
titanium dioxide
mixed
dioxide particles
cellulose ester
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PCT/US2012/042451
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English (en)
Inventor
Steven Anthony Wilson
Jeremy Kenneth STEACH
Jerry Steven Fauver
Original Assignee
Eastman Chemical Company
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Application filed by Eastman Chemical Company filed Critical Eastman Chemical Company
Priority to CN201280030468.4A priority Critical patent/CN103607913A/zh
Priority to BR112013032688A priority patent/BR112013032688A2/pt
Priority to EP12731811.1A priority patent/EP2723202A1/fr
Priority to KR1020147001700A priority patent/KR20140047667A/ko
Priority to JP2014517036A priority patent/JP2014523241A/ja
Priority to CA2838082A priority patent/CA2838082A1/fr
Priority to RU2014101981/12A priority patent/RU2014101981A/ru
Priority to MX2013014676A priority patent/MX2013014676A/es
Publication of WO2012177483A1 publication Critical patent/WO2012177483A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/067—Use of materials for tobacco smoke filters characterised by functional properties
    • A24D3/068—Biodegradable or disintegrable
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/08—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent
    • A24D3/10—Use of materials for tobacco smoke filters of organic materials as carrier or major constituent of cellulose or cellulose derivatives
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/14—Use of materials for tobacco smoke filters of organic materials as additive
    • A—HUMAN NECESSITIES
    • A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
    • A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
    • A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
    • A24D3/06—Use of materials for tobacco smoke filters
    • A24D3/16—Use of materials for tobacco smoke filters of inorganic materials

Definitions

  • the present invention relates to cellulose esters, and specifically, to cellulose esters that exhibit improved degradation.
  • Typical cigarette filters are made from a continuous- filament tow bandof cellulose acetate-based fibers, called cellulose acetate tow, or simply acetate tow.
  • cellulose acetate tow a continuous- filament tow bandof cellulose acetate-based fibers
  • simply acetate tow a continuous- filament tow bandof cellulose acetate-based fibers
  • the use of acetate tow to make filters is described in various patents, and the tow may be plasticized. See, for example, U.S. Patent No. 2,794,239.
  • staple fibers may be used which are shorter, and which may assist in the ultimate degradation of the filters. See, for example, U.S. Patent No. 3,658,626 which discloses the production of staple fiber smoke filter elements and the like directly from a continuous filamentary tow. These staple fibers also may be plasticized.
  • Acetate tow for cigarette fibers is typically made up of Y- shaped, small-filament-denier fibers which are intentionally highly crimped and entangled, as described in U.S. Patent No. 2,953,838.
  • the Y-shape allows optimum cigarette filters with the lowest weight for a given pressure drop compared to other fiber shapes. See U. S. Patent No. 2,829,027.
  • the small-filament-denier fibers typically in the range of 1 .6 - 8 denier per filament (dpf), are used to make efficient filters.
  • the crimp of the fibers allows improved filter firmness and reduced tow weight for a given pressure drop.
  • the conversion of acetate tow into cigarette filters may be accomplished by means of a tow conditioning system and a plugmaker, as described, for example, in U.S. Patent No. 3,017,309.
  • the tow conditioning system withdraws the tow from the bale, spreads and de-registers ("blooms") the fibers, and delivers the tow to the plugmaker.
  • the plugmaker compresses the tow, wraps it with plugwrap paper, and cuts it into rods of suitable length.
  • a nonvolatile solvent may be added to solvent-bond the fibers together.
  • solvent-bonding agents are called plasticizers in the trade, and historically have included triacetin (glycerol triacetate), diethylene glycol diacetate, triethylene glycol diacetate,
  • Waxes have also been used to increase filter firmness. See, for example, U.S. Patent No. 2,904,050.
  • plasticizer fiber-to-fiber bonding agents work well for bonding and selective filtration.
  • plasticizers typically are not water-soluble, and the fibers will remain bonded over extended periods of time.
  • conventional cigarette filters can require years to degrade and disintegrate when discarded, due to the highly entangled nature of the filter fibers, the solvent bonding between the fibers, and the inherent slow degradability of the cellulose acetate polymer. Attempts have therefore been made to develop cigarette filters having improved degradability.
  • U.S. Patent No. 5,947,126 discloses a bundle of cellulose acetate fibers bonded with a water-soluble fiber-to-fiber bonding agent.
  • the bonded fibers are wrapped in a paper having opposing ends secured together with a water-soluble plug wrap adhesive, and a plurality of cuts are made to extend more than one half way through the bundle wrapped fibers.
  • a tobacco smoke filter is thus provided that disintegrates and degrades in a relatively short period of time.
  • U.S. Patent No. 5,947,127 discloses a filter rod produced by adding a water-soluble polymer in the form of an aqueous solution or dispersion, or in a particulate form, to a tow of cellulose ester fiber.
  • the tobacco filter is said to be highly wet-disintegratable and, hence, contributes to mitigation of environmental pollution.
  • the environmental degradability of the fiber can be increased by incorporating a biodegradation accelerator such as citric acid, tartaric acid, malic acid, etc. and/or a photodegradation accelerator such as anatase-form titanium dioxide, or titanium dioxide, preferably anatase-form titanium dioxide, may be provided as a whitening agent.
  • U.S. Patent No. 7,435,208 discloses cigarette filters that comprise an elongate filter component having a longitudinal axis. A plurality of spaced-apart slits, generally perpendicular to the longitudinal axis of the filter component, partially extend into the component. The slits enable the filter to disintegrate and more readily degrade after being used and discarded.
  • U.S. Patent Nos. 5,491 ,024 and 5,647,383 disclose a man-made fiber comprising a cellulose ester and 0.05 to 5.0% by weight of a titanium dioxide having an average particle size of less than 100 nanometers.
  • the titanium dioxide is added to the "dope" (i.e., the solvated cellulose ester) prior to extrusion into the tow. Addition of the titanium dioxide may be at any convenient point prior to extrusion.
  • the titanium dioxide is preferably an uncoated anatase material having an average particle size less than 10 nanometers and a specific surface area of about 250 m 2 /g.
  • U.S. Patent No. 5,512,230 discloses a method for spinning a cellulose acetate fiber having a low degree of substitution per anhydroglucose unit (DS/AGU) of the cellulose acetate.
  • the addition of 5 to 40 weight percent water to cellulose acetate(CA)/acetone spinning solutions (dopes) is said to produce dopes that will allow fibers to be solvent spun using CA with a DS/AGU from 1 .9 to 2.2.
  • U.S. Patent No. 5,970,988 discloses cellulose ester fibers having an intermediate degree of substitution per anhydroglucose unit
  • the fibers are useful as filter materials for tobacco products.
  • the filter materials thus provided are easily dispersible and biodegradable and do not persist in the environment.
  • the pigment may be titanium dioxide and is provided within the fiber, but in amounts greater than are typical for use as a whitening agent.
  • U.S. Patent Publication. No. 2009/0151738 discloses a degradable cigarette filter that includes a filter element of a bloomed cellulose acetate tow, a plug wrap surrounding the filter element, and either a coating or a pill in contact with the tow.
  • the coating and/or pill may be composed of a material adapted to catalyze hydrolysis of the cellulose acetate tow and a water-soluble matrix material such that when water contacts the water-soluble matrix material, the material adapted to catalyze hydrolysis is released and catalyzes the hydrolysis, and subsequent degradation, of the cellulose acetate tow.
  • WO 2010/017989 discloses a photodegradable plastic comprising cellulose esters and also, if appropriate, additives.
  • photodegradable plastic comprises a dispersed photocatalytic carbon- modified titanium dioxide.
  • the photodegradable plastic is said to exhibit a surprisingly high increase in photocatalytic degradability when compared with products in which a conventional or other modified titanium dioxide is used.
  • the photodegradable plastic can, for example, first be further processed to give a filter tow.
  • 201 1 /0023900 disclose a tobacco smoke filter or filter element comprising a cylindrical plug of a substantially homogeneous filtering material of
  • Titanium Dioxide P25 Manufacture— Properties- Applications, Technical Bulletin Fine Particles, Number 80, Degussa Aerosil & Silanes
  • Product Literature discusses commercial uses of mixed- phase titanium dioxide, including use as a photocatalyst and as a photo- semiconductor.
  • U.S. Patent No. 5,720,803 discloses a composition comprising a cellulose ester including at least 10 weight % of a low- substituted cellulose ester having an average degree of substitution not exceeding 2.15 and giving a 4-week decomposition rate of at least 60 weight % as determined using the amount of evolution of carbon dioxide as an indicator in accordance with ASTM 125209-91 .
  • the composition may contain a plasticizer, an aliphatic polyester, a photolysis accelerator such as anatase type titanium dioxide or a biodegradation accelerator such as organic acids and their esters.
  • the low-substituted cellulose ester may be a cellulose ester having an average degree of polymerization from 50 to 250, an average degree of substitution from 1 .0 to 2.15 and a residual alkali metal/alkaline earth metal-to-residual sulfuric acid equivalent ratio of 0.1 to 1 .1 .
  • the biodegradable cellulose ester composition is said to be suitable for the manufacture of various articles including fibrous articles such as tobacco filters.
  • U.S. Patent No. 5,478,386 discloses a composition that includes a cellulose ester including at least 10 weight % of a low-substituted cellulose ester having an average degree of substitution not exceeding 2.15.
  • the composition may contain a plasticizer, an aliphatic polyester, a photolysis accelerator such as anatase-type titanium dioxide, or a biodegradation accelerator such as organic acids and their esters.
  • U.S. Patent No. 5,242,880 discloses novel titania comprising anatase titanium dioxide and sodium, potassium, calcium, magnesium, barium, zinc, or magnesium salts of sulfuric or phosphoric acid.
  • the titania are said to be useful in the pigmentation of oxidizable polymers, while at the same time providing a catalyst system for the photooxidation of the oxidizable polymers.
  • U.S. Patent No. 5,804,296 discloses a composition comprising a cellulose acetate or other cellulose ester, and an anatase-type titanium oxide having a specific surface area of not less than 30 m 2 /g, a primary particle size of 0.001 to 0.07 ⁇ , or a specific surface area of not less than 30 m 2 /g and a primary particle size of 0.001 to 0.07 ⁇ .
  • the surface of the titanium oxide may be treated with a phosphoric acid salt or other phosphorus compound, a polyhydric alcohol, an amino acid or others.
  • the composition may further contain a plasticizer and/or an aliphatic polyester, a biodegradation
  • accelerator e.g. organic acids or esters thereof.
  • WO 1995/29209 discloses pigmented cellulose acetate filaments produced by mixing a dispersion of titanium dioxide in a carboxylate ester of a polyhydric alcohol with cellulose acetate and a solvent for cellulose acetate. The resulting dispersion is dry spun to produce pigmented cellulose acetate filaments.
  • the invention relates to articles comprising a cellulose ester having incorporated therein or thereon mixed-phase titanium dioxide particles.
  • the article may be in the form of a molded article, or in the form of cellulose ester fibers, for example in the form of a yarn or a fabric.
  • the cellulose ester fibers may be in the form of a filter prepared by a process that includes the steps of applying a plasticizer, having the mixed-phase titanium dioxide particles dispersed therein, to the cellulose ester fibers to obtain plasticized cellulose ester fibers; and thereafter forming the plasticized cellulose ester fibers into a filter.
  • the plasticizer may include one or more of: triacetin (glycerol triacetate), diethylene glycol diacetate, triethylene glycol diacetate, methyl phthalyl ethyl glycollate, dibutyl phthalate, tripropionin, acetyl triethyl citrate, triethyl citrate, and mixtures of triacetin and one or more polyethylene glycols.
  • triacetin glycol diacetate
  • triethylene glycol diacetate triethylene glycol diacetate
  • methyl phthalyl ethyl glycollate dibutyl phthalate
  • tripropionin acetyl triethyl citrate
  • triethyl citrate triethyl citrate
  • mixtures of triacetin and one or more polyethylene glycols may be provided with one or more slits, and may be useful, for example, for use in cigarettes.
  • the mixed-phase titanium dioxide particles useful according to the invention may comprise, for example, an anatase phase present in an amount from 50% to 98%, and a rutile phase present in an amount from 2% to 50%, in each case as measured by x-ray crystallography.
  • the particles may have a surface area, for example, from about 10 to about 300 sq. m/g, and may independently have an average particle size from about 1 nm to about 100 nm, or from 5 nm to 50 nm.
  • the amount of mixed-phase titanium dioxide particles provided to the articles according to the invention may vary widely, for example from about 0.01 to about 20 wt.%, based on the weight of the article.
  • the articles of the invention when they are in the form of fibers, for example, they may be dispersed in the cellulose ester fibers, for example by being dispersed in the solvent from which the fibers are spun.
  • the cellulose esters useful according to the invention may comprise one or more of a cellulose acetate, a cellulose propionate, a cellulose butyrate, a cellulose acetate propionate, or a cellulose acetate butyrate, for example a cellulose acetate having a DS/AGU from about 1 .8 to about 2.7, or from about 1 .9 to about 2.5.
  • rutile-based titanium dioxide particles roughly 200 nm in size may be provided to cellulose esters to provide good light scattering and minimal photo activity
  • anatase-type titanium dioxide particles used to enhance the degradation of cigarette filters
  • the present invention relates rather to titanium dioxide particles of mixed phase, hereinafter described as mixed-phase titanium dioxide particles, which provide enhanced degradation under UV radiation compared with those comprised either of anatase or rutile form alone.
  • the mixed-phase titanium dioxide particles of the invention are especially those which are uncoated and have ultrafine particle sizes ( ⁇ 100 nm) to achieve optimum photo activity.
  • titanium dioxide particles having a mixture of anatase and rutile crystal structure that is, mixed-phase particles
  • the invention thus relates to cellulose esters having incorporated therein titanium dioxide particles with mixed phases of anatase and rutile crystals, especially those having uncoated surfaces, and an ultrafine ( ⁇ 100 nm) particle size.
  • the mixed-phase titanium dioxide particles may be provided to the cellulose esters in a variety of manners.
  • rutile phase or "rutile crystalline structure”
  • This phase or crystalline structure may be identified, for example, by x-ray crystallography.
  • anatase phase or “anatase crystalline structure”
  • This phase or crystalline structure may likewise be identified, for example, by x-ray crystallography.
  • Mixed-phase titanium dioxide particles are thus used according to the invention, and are characterized as having both rutile and anatase crystalline structures present in the same particle.
  • mixed-phase we do not intend to include particles having only trace amounts of one or the other of the two structures.
  • the amount of anatase phase present in the mixed phase particles may vary, for example, from about 50% to about 99%, or from 60% to 98%, or from 75% to 95%, in each case as measured by x-ray crystallography.
  • the rutile phase present in the particles may likewise vary in a similar manner, for example from about 1 % to about 50%, or from 2% to 40%, or from 5% to 25%, in each case as measured by x-ray crystallography.
  • the present invention thus relates to the use of mixed phase titanium dioxide particles in cellulose esters such as those used for cigarette filters, without regard to the method of incorporation, that is, whether provided to the plasticizer, within the fiber, or otherwise provided.
  • the mixed-phase titanium dioxide particles useful according to the invention may be prepared, for example, by methods such as the flame hydrolysis of titanium tetrachloride. Relatively high purity mixed- phase titanium dioxide particles may be obtained by this process. See, for example, the Titanium Compounds (Inorganic) entry of Kirk-Othmer,
  • tetrachloride can also be used. Id. Other processes may be used in which the particles obtained have a mixture of anatase and rutile phases in the same particle, as already described.
  • the surface area of the mixed-phase titanium dioxide particles of the invention may vary, for example, from about 10 to about 300 m 2 /g, or from 20 to 200 m 2 /g, or from 40 to 100 m 2 /g, as measured by gas absorption in a BET surface area method.
  • the amount of the mixed-phase titanium dioxide particles provided to the cellulose ester may vary within a wide range, for example, from about 0.01 to about 20 wt.%, or from 0.2 to 10 wt.%, or from 0.2 to 5 wt.%. In some aspects, the amount of titanium dioxide particles provided may depend upon the solution viscosity during fiber manufacturing. A variety of particle sizes of titanium dioxide are useful according to the invention, for example from about 1 nm to about 10 microns, or from 1 nm to 1 micron, or from 1 nm to 500 nm, or from 1 nm to 250 nm, or from 3 nm to 100 nm, or from 5 nm to 50 nm.
  • nanoscale particles are particularly suited for use according to the invention. Not wishing to be bound by any theory, it may be that the use of a smaller particle size provides higher surface area. A second possible reason is that small particle size allows the UV radiation to penetrate further into the cellulose ester, so that the degradation is further from the surface, thus causing degradation deeper within the cellulose ester.
  • the photoactive agent may be present not just in discrete particles, but also in agglomerates. We have found that particles present as agglomerates suitably enhance degradation of the resulting filters, but the particles may be milled, for example, if desired, in order to obtain a more uniform and primary particle size.
  • Coating agents that may be applied to the titanium oxide particles include, for example, carbon coatings.
  • certain coatings for example carbon coatings, may assist in the desired photodegradation of the filters, for example by allowing visual light absorption.
  • Both modified and unmodified titanium particles are suitable for use according to the invention, for example carbon-modified particles.
  • the mixed phase titanium oxide particles according to the invention are predominately rutile and anatase phases, the particles may have carbon modifications into or onto the particles. Carbon modifications or doping may be accomplished, for example, by ethanol carbonization or by the adsorption of dyes.
  • certain embodiments are predominately rutile and anatase phases, the particles may have carbon modifications into or onto the particles. Carbon modifications or doping may be accomplished, for example, by ethanol carbonization or by the adsorption of dyes.
  • modifications for example carbon coatings
  • a second theory is that the carbon modifications, such as carbon doping, may suppress the phase transformation from anatase to rutile during high temperature treatments and reduce the crystal sizes.
  • the mixed-phase titanium dioxide particles of the invention may be provided to the cellulose ester "dope," that is, to the cellulose ester dissolved in acetone from which cellulose ester fibers are spun.
  • the mixed-phase titanium dioxide particles may be provided to the dope in a variety of manners, for example by the inclusion of a mixture of cellulose acetate, triacetin and ⁇ 02.
  • the particles may be provided by mixing the ⁇ 02 in a hydrophilic solvent which would allow optimum particle dispersion.
  • Further examples of dispersing titanium dioxide particles in cellulose ester fibers include those set out in U.S. Pat. Nos.
  • the titanium dioxide particles of the present invention are characterized as being mixed-phase titanium dioxide particles.
  • the mixed-phase titanium dioxide particles of the invention may be provided, for example, by high shear blending with a polymer concentrate.
  • plasticizer is intended to describe a solvent that, when applied to cellulose ester fibers, solvent-bonds the fibers together.
  • Plasticizers useful according to the invention include one or more of: triacetin (glycerol triacetate), diethylene glycol diacetate, triethylene glycol diacetate, tripropionin, acetyl triethyl citrate, triethyl citrate, and mixtures of triacetin and one or more polyethylene glycols.
  • the blends or mixtures may optionally contain polymers, for example water-soluble polymers such as cellulose mono-acetate with a DS/ADU of 0.6 to 0.9, polyesters, such as, methyl cellulose, hydroxyethyl cellulose and
  • hydroxypropyl cellulose polyvinyl acetate (PVA) and polyvinyl alcohol (PVOH).
  • the mixed-phase titanium dioxide particles of the invention are also termed "photoactive agent" and serve as such agents, meaning that, when added to a plasticizer that is applied to a cellulose ester fiber, or to the cellulose ester itself, increases the rate at which the ester degrades upon exposure to UV radiation.
  • the mixed-phase particles may be dispersed in the plasticizer in any of a number of ways, for example by use of high shear mixing devices, such as media mills or ultrasonic probes.
  • the stability of the mixed-phase particles in the plasticizer may be enhanced by adding an amount of cellulose ester to the plasticizer, for example in an amount from about 0.1 % to about 20%, or from 0.2 to 10%, based on the viscosity in the resultant plasticizer solution. Stability may be further enhanced by providing to the plasticizer an amount of a polyethylene glycol, one having a molecular weight, for example, from about 100 to about 400, or from 200 to 1000, in an amount from about 0.1 % to about 20%, or from 0.2% to 10%.
  • a photoactive agent in the plasticizer rather than the fiber allows conventional acetate tows to be used, without any change in the ester or tow formulation.
  • mixed-phase particles in the plasticizer may affect, for example, the viscosity of the plasticizer, especially if stabilizers such as a cellulose ester and/or a polyethylene glycol are incorporated.
  • the stabilizer may best be chosen so as not to affect the viscosity, for example by providing a relatively low molecular weight cellulose ester, or polyethylene glycol, or both.
  • cellulose ester means one or more cellulose esters, such as cellulose acetate, that may be, for example, melt-spun or solvent-spun into fibers.
  • the cellulose esters useful according to the invention thus include, without limitation, cellulose acetates, cellulose propionates, and cellulose butyrates with varying degrees of substitution, as well as mixed esters of these, that is, cellulose acetate propionate, cellulose acetate butyrate, and cellulose acetate propionate butyrate.
  • the cellulose ester of the present invention may be a secondary cellulose ester. Examples of suitable esters thus include cellulose acetates, cellulose acetate
  • esters may be readily used and fibers constructed with a range of acetyl levels, such as from 1 .5 to 2.8, or from 1 .8 to 2.7, or from 1 .9 to 2.5, or for example, an average DS/AGU of about 2.0.
  • DS/AGU anhydroglucose unit
  • the cellulose esters of the present invention can be spun into a fiber, for example by melt-spinning or by spinning from an appropriate solvent (e.g., acetone, acetone/water, tetrahydrofuran, methylene
  • an appropriate solvent e.g., acetone, acetone/water, tetrahydrofuran, methylene
  • a suitable solvent for spinning fiber is acetone containing from 0 to 30% water.
  • a preferred spinning solvent is acetone containing less than 3% water.
  • a preferred spinning solvent is 5-15% aqueous acetone.
  • a preferred solvent is 15-30% aqueous acetone.
  • the cellulose ester or plasticized cellulose ester may have a melt temperature, for example, from 120 Q C to 250 Q C, or from 180 Q C to 220 Q C.
  • suitable plasticizers for use in melt spinning of cellulose esters include, but are not limited to, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, triacetin, dioctyl adipate, polyethylene glycol-200, or polyethylene glycol-200, or polyethylene glycol- 400.
  • Preferred plasticizers for melt-spinning include dibutyl phthalate, dioctyl adipate, or polyethylene glycol-400.
  • the cellulose ester fibers used may be continuous fibers, or may be staple fibers having a shorter length, rendering the fibers more susceptible to degradation.
  • the staple fibers may have a length from about 4 to 20 mm, or from 5 to 18 mm, or from 7 to 16 mm.
  • the cellulose ester fibers useful according to the invention are typically crimped, having, for example, from 4-20 crimps per inch, or from 10 to 15 crimps per inch.
  • the fibers typically have a
  • the fibers may optionally contain lubricants or processing aids such as mineral oil, used in amount from 0.1 to 3%, or from 0.3 to 0.8%.
  • particulate additives are commonly added into fibers to enhance filter whiteness
  • these additives are typically titanium dioxide particles roughly 200 nm in size, a size which provides good light scattering but with minimal photo activity.
  • Such titanium particles commonly have an inorganic coating on the surface to enhance the particles' dispersion in spinning solutions. Titanium dioxides are not traditionally added to the plasticizer, perhaps because it might limit the filter's hardness without enhancing the whiteness.
  • Filters produced according to the invention may further incorporate other features to enhance their degradation, for example by being slit perpendicular to the longitudinal axis, by incorporating staple fibers, or otherwise shorter fibers which tend to increase the rate of degradation in the environment.
  • Further measures to increase the rate of degradation may include incorporating in the plasticizer one or more polymers, for example water-soluble polymers, although this may, in fact, reduce the rate of degradation if this affects the ability of the plasticizer to solubilize the ester such that the photoactive agent does not penetrate the fiber during the plasticizing step.
  • Water-soluble polymers that may nonetheless be useful include cellulose mono-acetate with DS/ADU of 0.6 to 0.9, polyesters, such as, methyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose, polyvinyl acetate (PVA) and polyvinyl alcohol (PVOH).
  • PVA polyvinyl acetate
  • PVOH polyvinyl alcohol
  • the invention is not limited to cellulose esters in the form of fibers for cigarette filters, but may relate also to other cellulose ester fibers, such as those known in the industry as acetate yarn, and used in various textile uses including clothing.
  • the cellulose esters according to the invention may also be in the form of molded articles, or any other known form of cellulose esters in which an increased rate of breakdown in the
  • filter samples were assembled with a conventional filter maker with 10% triacetin applied to the fibers during filter making.
  • the filter samples were placed on the roof of a building in individual wire mesh cages to allow sufficient UV radiation to reach the filters.
  • the cages were positioned approximately four inches from the ground so as to minimize the samples sitting in water puddles present on the roof top.
  • Each roof top study consisted of ten 21 -mm filter tips per example, placed in the mesh cage with the paper removed leaving only the fibers that formed the filter. The paper was removed so the fibers in the filters could be directly exposed to UV radiation and thereby determines the effects of the photoactive agent role in degradability.
  • the filters were collected for weighing periodically to assess the degradation of the fibers in the filter. The results are a comparison of the weight of the ten filter samples at each test point.
  • Examples 1 -4 represent the first set of samples tested and Examples 5-8B represent the second set of samples tested by roof top outdoor weathering. Each set was tested by the degradation testing described above.
  • Example 2 Pigment-size (210 nm) uncoated anatase TiO?
  • Example 4 the fastest degradation was provided by Example 4, in which the ultrafine uncoated TiO 2 particles consisted of a mixed phase of anatase (89%) and rutile (1 1 %).
  • a filter with no Ti0 2 had a remaining weight of 81 % after 10 months; while a filter with the pigment size (210 nm) uncoated anatase (94%) particles had a remaining weight of 38%.
  • the mixed phase ultrafine-size (21 nm) Ti0 2 in Example 4 had a remaining weight of 33%.
  • Note the other mixed phase Ti0 2 in Example 3 had a remaining weight of 72% and shows the importance of the higher blend of rutile to anatase along with the smaller crystal sizes.
  • Filters were constructed from cellulose acetate fibers containing no Ti0 2 pigment.
  • the roof top outdoor weathering results are set out in Table 3.
  • Example 6 Pigment-size (210 nm) coated anatase TiO?
  • TiO 2 pigment had an average particle size of 210 nm and consisted of anatase particles with an inorganic coating.
  • the roof top outdoor weathering results are shown in Table 3.
  • the properties of the TiO 2 (Kronos 1071 ) are listed in Table 4.
  • Example 7A Ten filters were constructed with cellulose acetate fibers containing varying amounts of AEROXIDE ® TiO 2 P 25, an ultrafine-size, uncoated mixed-phase TiO 2 , present in the fibers.
  • the filters of Example 7A were provided with 0.5 wt% of the particles.
  • Example 7B the cellulose acetate fiber was provided with 1 .0 wt% of the particles.
  • Example 7C the cellulose acetate fiber was provided with 2.0 wt% of the same particles.
  • the roof top outdoor weathering results are set out in Table 3.
  • the properties of the TiO 2 (AEROXIDE P25 from Evonik) are listed in Table 4.
  • Example 8A was provided with 0.5 wt.% of the particles, and Example 8B was provided with 1 .0 wt% of the particles.
  • the roof top outdoor weathering results are set out in Table 3.
  • the properties of the TiO 2 (VP P 90 from Evonik) are listed in Table 4.
  • the fastest degradation is provided by the filters in Examples 7 and 8 with the ultrafine uncoated Ti0 2 particles consisting of a mixed phase of anatase and rutile.
  • the filters with no Ti0 2 present had a remaining weight of 83 % after 9 months; while a filter with the pigment-size coated anatase particles had a remaining weight of 79%.
  • the mixed phase Ti0 2 Example #7A - 7C had remaining weights of 31 to 33%. Note that the other mixed phase Ti0 2 in Examples 8A -8B had remaining weights of 51 % and 40%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biodiversity & Conservation Biology (AREA)
  • Inorganic Chemistry (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Cigarettes, Filters, And Manufacturing Of Filters (AREA)

Abstract

La présente invention concerne des esters de cellulose dégradables dans ou sur lesquels sont incorporées des particules de dioxyde de titane à phases mixtes. Les esters peuvent présenter la forme de filtres préparés par application d'un plastifiant, dans lesquels sont dispersées les particules de dioxyde de titane à phases mixtes, sur des fibres d'ester de cellulose pour obtenir des fibres d'ester de cellulose plastifiées, et après cela par formation de fibres d'ester de cellulose plastifiées pour obtenir un filtre. En variante, les particules peuvent être ajoutées à l'additif à partir duquel les fibres sont filées ou mélangées à un ester de cellulose destiné à des articles moulés.
PCT/US2012/042451 2011-06-23 2012-06-14 Esters de cellulose présentant des particules de dioxyde de titane à phases mixtes à dégradation améliorée WO2012177483A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
CN201280030468.4A CN103607913A (zh) 2011-06-23 2012-06-14 具有用于改进降解的混合相二氧化钛颗粒的纤维素脂
BR112013032688A BR112013032688A2 (pt) 2011-06-23 2012-06-14 artigo, e, cigarro
EP12731811.1A EP2723202A1 (fr) 2011-06-23 2012-06-14 Esters de cellulose présentant des particules de dioxyde de titane à phases mixtes à dégradation améliorée
KR1020147001700A KR20140047667A (ko) 2011-06-23 2012-06-14 분해 개선용 혼합상 이산화 티타늄 입자를 갖는 셀룰로오스 에스터
JP2014517036A JP2014523241A (ja) 2011-06-23 2012-06-14 向上した分解性のために混合相二酸化チタン粒子を有するセルロースエステル
CA2838082A CA2838082A1 (fr) 2011-06-23 2012-06-14 Esters de cellulose presentant des particules de dioxyde de titane a phases mixtes a degradation amelioree
RU2014101981/12A RU2014101981A (ru) 2011-06-23 2012-06-14 Сложные эфиры целлюлозы, содержащие частицы смешаннофазного диоксида титана для улучшенного разложения
MX2013014676A MX2013014676A (es) 2011-06-23 2012-06-14 Esteres de celulosa que tienen particulas de dioxido de titanio en fase mezclada para degradacion mejorada.

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US13/167,239 US20120325233A1 (en) 2011-06-23 2011-06-23 Cellulose esters having mixed-phase titanium dioxide particles for improved degradation
US13/167,239 2011-06-23

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JP2015506717A (ja) * 2012-02-16 2015-03-05 アール・ジエイ・レイノルズ・タバコ・カンパニー 喫煙物品のフィルタ構成要素を形成するための装置および関連する方法
JP2015221955A (ja) * 2014-04-30 2015-12-10 三菱レイヨン・テキスタイル株式会社 消臭機能及び抗菌機能を有する繊維及びその製造方法並びに織編物

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US8720450B2 (en) * 2010-07-30 2014-05-13 R.J. Reynolds Tobacco Company Filter element comprising multifunctional fibrous smoke-altering material
JP6648017B2 (ja) * 2013-08-12 2020-02-14 ソルベイ アセトウ ゲーエムベーハー 触媒活性チタン化合物を含有する生成物の製造方法
EP2837296A1 (fr) * 2013-08-12 2015-02-18 Solvay Acetow GmbH Matière plastique catalytiquement dégradable et son utilisation
US20170072391A1 (en) * 2014-07-10 2017-03-16 Sabic Global Technologies B.V. Photocatalytic hydrogen production from water over mixed phase titanium dioxide nanoparticles
EP3039970A1 (fr) * 2014-12-29 2016-07-06 Philip Morris Products S.A. Filtres d'articles à fumer ayant des additifs OXO
CN108103604B (zh) * 2017-12-20 2019-11-12 南通大学 降解醋酸纤维的复合光敏添加剂及其制备方法和用途
JP7217099B2 (ja) * 2018-07-12 2023-02-02 株式会社ダイセル セルロースアセテート繊維、セルロースアセテートトウバンド、及びセルロースアセテートトウバンドの製造方法
WO2021014561A1 (fr) * 2019-07-23 2021-01-28 株式会社ダイセル Procédé de production d'une fibre d'acétate de cellulose et fibre d'acétate de cellulose
KR20220069016A (ko) * 2019-08-27 2022-05-26 아쎄테이트 인터내셔널 엘엘씨 높은 dpf 및 낮은 이산화티탄 함량을 갖는 셀룰로스 아세테이트 토우
CN114521673A (zh) * 2022-03-01 2022-05-24 湖北中烟工业有限责任公司 一种复合增塑剂及其制备方法和应用
CN115005497B (zh) * 2022-07-20 2023-07-25 湖北中烟工业有限责任公司 一种可降解香烟滤棒母料和可降解香烟滤棒

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Publication number Priority date Publication date Assignee Title
JP2015506717A (ja) * 2012-02-16 2015-03-05 アール・ジエイ・レイノルズ・タバコ・カンパニー 喫煙物品のフィルタ構成要素を形成するための装置および関連する方法
US9854833B2 (en) 2012-02-16 2018-01-02 R. J. Reynolds Tobacco Company Apparatus and associated method for forming a filter component of a smoking article
JP2015221955A (ja) * 2014-04-30 2015-12-10 三菱レイヨン・テキスタイル株式会社 消臭機能及び抗菌機能を有する繊維及びその製造方法並びに織編物

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JP2014523241A (ja) 2014-09-11
MX2013014676A (es) 2014-03-27
CA2838082A1 (fr) 2012-12-27
CN103607913A (zh) 2014-02-26
US20120325233A1 (en) 2012-12-27

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