WO2004022841A1 - Polymer article and method for manufacturing the same - Google Patents

Polymer article and method for manufacturing the same Download PDF

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Publication number
WO2004022841A1
WO2004022841A1 PCT/KR2003/001873 KR0301873W WO2004022841A1 WO 2004022841 A1 WO2004022841 A1 WO 2004022841A1 KR 0301873 W KR0301873 W KR 0301873W WO 2004022841 A1 WO2004022841 A1 WO 2004022841A1
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WO
WIPO (PCT)
Prior art keywords
polymer
substance
polymer substrate
cracks
micro
Prior art date
Application number
PCT/KR2003/001873
Other languages
French (fr)
Inventor
Jung-Eun Seo
Original Assignee
Jung-Eun Seo
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Application filed by Jung-Eun Seo filed Critical Jung-Eun Seo
Priority to AU2003261003A priority Critical patent/AU2003261003A1/en
Publication of WO2004022841A1 publication Critical patent/WO2004022841A1/en

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Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/005Compositions containing perfumes; Compositions containing deodorants
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/12Processes in which the treating agent is incorporated in microcapsules
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/35Abrasion, pilling or fibrillation resistance

Definitions

  • the present invention relates to a polymer article and a method of manufacturing the same. More particularly, the present invention relates to a polymer article which is excellent in handle and ability to withstand washing, abrasion, and the like, as a result of filling micro-cracks of the polymer article with a functional additive and finishing the surface of the polymer article with a resin layer, and a method of manufacturing the same.
  • an additive such as a fragrant substance, an antimicrobial substance, an insecticide substance, or a deodorant substance that can chemically decompose or physically adsorb a gaseous odor component is added to a polymer solution or a molten polymer intended for fabrication of fiber products or plastic products, followed by spinning or molding.
  • this method has a problem in that the additive mainly composed of an organic compound is easily thermally or chemically decomposed or modified due to a high temperature or chemicals applied during the fabrication process of polymer articles. Furthermore, this method cannot be applied in the fabrication of natural fiber products that are not made by a spinning process.
  • Another method is a method of forming a polymer film containing a functional additive on the surfaces of fabric or plastic products.
  • fabric or plastic products are in advance formed using conventional weaving, knitting, extrusion molding, injection molding, etc. Then, in a subsequent step, the surfaces of the fabric or plastic products are coated with a resin composition containing the additive to thereby form the polymer film containing the additive.
  • this method provides poor handle and appearance of final products. In addition, the ability to withstand washing, abrasion, and sunlight is poor. Therefore, the present invention provides a polymer article with good handle and good ability to withstand washing, abrasion, and the like.
  • the present invention also provides a method of manufacturing the polymer article with the above-described properties.
  • a polymer article comprising: a polymer substrate having micro-cracks on the surface thereof; a functionality-imparting layer formed on the surface of the polymer substrate and comprising at least one functional additive selected from the group consisting of a fragrant substance, an antimicrobial substance, an insecticide substance, and a deodorant substance; and a resin layer covering the functionality-imparting layer.
  • a method of manufacturing a polymer article comprising: forming micro-cracks on the surface of a polymer substrate; positioning, in the micro-cracks, at least one functional additive selected from the group consisting of a fragrant substance, an antimicrobial substance, an insecticide substance, and a deodorant substance, to form a functionality-imparting layer; and covering the functionality-imparting layer with a resin layer.
  • the micro-cracks are filled with the functional additive and the surface of the polymer article is finished with the resin layer. Therefore, the polymer article has good handle and appearance, as well as the ability to withstand washing and sunlight being good.
  • the functional additive is added in a mild condition, the functional additive is not easily thermally or chemically decomposed or modified.
  • the method of manufacturing the polymer article according to the present invention can also be applied in the fabrication of natural polymer articles that are not made by an extrusion process or a spinning process.
  • polymer article includes all products manufactured by any technologies known to ordinary persons skilled in the art such as weaving, spinning, extrusion molding, or injection molding.
  • the polymer article may be a yarn, a woven fabric, a nonwoven fabric, a knitted fabric, an extrusion-molded product, and an injection-molded product.
  • the polymer article can be used to form, for example, necklaces, rings, bracelets, clothes, bags, glasses frames, golf clubs, gloves, cases for cellular phones, cases for electronic products such as televisions or refrigerators, automobile parts, interior automotive trim, curtains, wall papers, bedclothes, carpets, dolls, towels, hair bands, car seats, and shoes sole.
  • a polymer article according to the present invention comprises: a polymer substrate having micro-cracks on the surface thereof; a functionality-imparting layer formed on the polymer substrate and comprising at least one functional additive selected from the group consisting of a fragrant substance, an antimicrobial substance, an insecticide substance, and a deodorant substance; and a resin layer covering the functionality-imparting layer. That is, the polymer article of the present invention has a laminated structure of the polymer substrate, the functionality-imparting layer, and the resin layer.
  • the surface of the polymer substrate is formed with the micro-cracks and the functional additive is positioned in the micro-cracks.
  • the micro-cracks may have a diameter size ranging from several nanometers to several centimeters.
  • the functional additive is not simply adhered to the surface of the polymer substrate using a binder, but is stably buried in the micro-cracks. Therefore, the ability to withstand washing and sunlight is good. That is, even though the polymer article of the present invention is washed several times or is exposed to sunlight for a long time, the functional additive is not easily removed from the polymer substrate. Therefore, the polymer article of the present invention can continuously provide functionalities such as a fragrant property and/or an antimicrobial property for a long time. In addition, since the surface of the polymer article of the present invention is smoothly finished with the resin layer, handle and appearance are good.
  • the polymer substrate may be a yarn, a fabric, an extrusion-molded plastic product, or an injection-molded plastic product, but is not limited thereto.
  • the polymer substrate may also be a nonwoven fabric, a pulp, a wood, a metal substrate, and a rubber.
  • polystyrene resins such as natural protein, nylon 6, nylon 66, and nylon 610
  • polyesters such as polyethyleneterephthalate, polybutyleneterephthalate, and polynaphthaleneterephthalate
  • polyacrylonitriles acrylic resins
  • polyolefins such as polyethylene and polypropylene
  • halogenated polyolefins celluloses; regenerated celluloses; cellulose acetates; cellulose triacetates
  • polyurethanes polycarbonates; polyacetals
  • vinylic polymers such as polystyrene, polyvinylchloride, polyvinylfluoride, and polyvinylacetate
  • (meth)acrylate resins such as polymethylacrylate and polymethylmethacrylate
  • formaldehyde resins such as urea-formaldehyde resin and melamine-formaldehyde resin
  • phenolic resins and synthetic or natural rubbers such as NBR rubber, SBR rubber
  • the functional additive positioned in the micro-cracks may be a fragrant substance, an antimicrobial substance, an insecticide substance, a deodorant substance, or a mixture thereof.
  • the fragrant substance may be a vegetable fragrant substance, an animal fragrant substance, a synthetic fragrant substance, or a mixture thereof.
  • the vegetable fragrant substance that can be used herein is derived from, but is not limited to, lavender, peppermint, spearmint, turpentine, cinnamon, chamomile, anise, star anise, rosemary, eucalyptus, rose, bergamot, geranium, jasmine, tea tree, lemon, ylangylang, clove bud, coriander, lime, thyme, frankincense, ginger, grapefruit, hyssop, helichrysum, juniper, lemongrass, marjoram, melissa, myrrh, neroli, orange, basil, palmarosa, carrot seed, vetiver, cypress, fennel, sandalwood, patchouli, pine, rosewood, yarrow, angelica, sage, clary sage, birch, black pepper, cedarwood, benzoin, petigrain, lilac, violet, niaouli, Caesalpinia sappan L
  • the animal fragment substance that can be used herein is derived from, but is not limited to, musk, ambergris, civet, castor, and a mixture thereof.
  • Examples of the synthetic fragrant substance that can be used herein include, but are not limited to, synthetic musk, terpene-based synthetic perfume, 2-phenylethyl alcohol, benzyl acetate, ethyl acetate, amyl acetate, octyl acetate, ethyl propionate, and a mixture thereof.
  • the fragrant substance used herein is generally used in the form of an essential oil composition.
  • the essential oil composition generally comprises alcohol, a solubilizing agent, or distilled water, in addition to a fragrant oil. Since there is no particular limitation to the content of each component of the essential oil composition, the amount of each component of the essential oil composition can be any amount conventionally used in the pertinent art.
  • the fragrant substance used herein may also be in the form of a capsule coated with a polymer film.
  • the antimicrobial substance is a chemical additive that is used to prevent contamination and deterioration of polymer articles such as fiber products or plastic products by microorganisms.
  • the antimicrobial substance used herein includes phenolics, halogen compounds, quaternary ammonium compounds, metal derivatives, amines, alkanolamines and nitro derivatives, anilides, organic sulfur compounds and sulfur-nitrogen compounds.
  • the anitimicrobial substance can kill all of microorganisms or prevent propagation of microorganisms so as not to deteriorate polymer articles.
  • Microorganisms as mentioned herein are mainly bacteria and fungi. Bacteria and fungi are generally classified into two groups. That is, bacteria can be classified into gram positive and gram negative and fungi can be classified into filamentous fungi and yeasts.
  • antimicrobial substance examples include, but are not limited to, dimethyl benzyl lauryl ammonium chloride, 3,5-dibromosalicyl anilide, pentachlorophenol, o-phenylphenol, trichloroisocyanuric acid, poly(vinylpyrolidone)-urea complex (PVP-lodine, available from ISP Corp.), 2,4,4'-trichloro-2'-hydroxydiphenylether,
  • 2,2-dibromo-2-cyanoacetamide 2,2-dibromo-2-cyanoacetamide, 2-bromo-2-nitropropane-1 ,3-diol, benzalkonium chloride (Hyamine-3500, available from Rohm & Haas), 10,10'-oxybis-phenoxyarsine (Vinyzene BP-5 or Durotex, available from Ventron), tributyltinoxide (Cotin 300, available from Cosan), 3,4,4'-trichlorocarbanilide, hexahydro-1 ,3,5-tris-(2-hydroxyethyl)-5-triazine, bisthiocyanatemethylenebisthiocyanate (MBT),
  • the antimicrobial substance is selected from drugs capable of controlling target microorganisms to a predetermined level. Further, the antimicrobial substance must be physically and chemically compatible with media used therefor. That is, the antimicrobial substance must not adversely affect the physical and chemical properties of the media and must not be inactivated by the components of the media.
  • Examples of the deodorant substance used herein include, but are not limited to, ⁇ -cyclodextrine, a mixture of polyethyleneimine and nonionic hygroscopic organic material disclosed in Japanese Patent Laid-Open Publication No. Hei. 3-146064, an amino group-containing metal porphyrin-based compounds, chitosan, a modified chitosan, carboxylic acid-containing polymers, zinc oxide, an extract of Caesalpinia sappan L., a zinc oxide particle, a silver particle, a silica particle, and a mixture thereof.
  • the anitimicrobial substance and the deodorant substance may be used in the form of a microcapsule coated with a polymer film.
  • the microcapsule may be made of a urea-formaldehyde resin, a melamine-formaldehyde resin, a polyurethane resin, gelatin, an acrylic resin, an epoxy resin, or a polysiloxane resin, but is not limited thereto.
  • the functionality-imparting layer may further comprise a titanium dioxide photocatalyst.
  • a titanium dioxide photocatalyst in a case where the functional additive such as the fragrant substance, the antimicrobial substance, or the deodorant substance are used in a microcapsule form, using the titanium dioxide photocatalyst is preferred.
  • the titanium dioxide photocatalyst leads to oxidative decomposition of the microcapsule encapsulating the functional additive by a photocatalytic action when the functional additive is exposed to the air due to abrasion of the surface resin layer, thereby gradually releasing the functional additive such as the fragrant substance or the antimicrobial substance into the air.
  • the titanium dioxide photocatalyst can decompose environmental organic materials, fungi, or bacteria, thereby reinforcing antimicrobial and deodorization properties, and can prevent discoloration of a polymer article by sunlight, thereby improving the ability to withstand sunlight.
  • the titanium dioxide photocatalyst is added in the amount of 0.1 to 20 parts by weight, preferably, 0.5 to 10 parts by weight, based on 100 parts by weight of the functional additive. If the content of the titanium dioxide is less than 0.1 parts by weight, the titanium dioxide cannot serve as a photocatalyst. On the other hand, if it exceeds 20 parts by weight, the polymer substrate made of an organic material such as a fiber and a plastic may decompose due to excess oxidation power.
  • the titanium dioxide may be formed in a porous fine powder form to increase the number of active sites, and/or the titanium dioxide may be mixed with a cocatalyst, such as platinum, iron, and silicon, to activate a photocatalytic reaction even at a low energy wavelength.
  • a cocatalyst such as platinum, iron, and silicon
  • the functionality-imparting layer is covered with the resin layer.
  • the resin layer constitutes the surface of the polymer article according to the present invention.
  • a functional additive is adhered to the surface of a polymer article by means of a binder resin.
  • a polymer article is immersed in a mixture solution of a functional additive and the binder resin, followed by drying or heating.
  • the conventional polymer articles have a rough surface and an unsatisfactory appearance.
  • the resin layer since only a polymer resin constitutes the resin layer and the resin layer can be formed by means of various methods such as brushing and doctor blade coating in addition to immersion, the resin layer has a smooth handle and good appearance.
  • the resin layer using the same polymer as used for the polymer substrate to increase adhesion and resistance to delamination.
  • the micro-cracks are formed on the surface of the polymer substrate.
  • the micro-cracks are not intended for simply adhering the functional additive to the surface of the polymer substrate. Rather, the functional additive is buried in the micro-cracks, and thus, the functional additive can be seen as an integral part of the polymer substrate. Therefore, even though the surface of the polymer article of the present invention is abraded in use, functionalities such as fragrant or antimicrobial properties of the functional additive can be maintained for a longer time.
  • the micro-cracks may have a diameter size ranging from several nanometers to several centimeters.
  • micro-cracks on the surface of the polymer substrate can be carried out using the following three methods, but are not limited thereto.
  • a solvent capable of dissolving the polymer substrate is used. According to this method, the surface of the polymer substrate is treated with the polymer substrate-dissolving solvent to provide the polymer substrate with an irregularly dissolved surface.
  • an injection molding is used.
  • an injection molding is carried out using a die having a plurality of fine protrusions.
  • This method can be used when the polymer substrate is formed by means of an injection molding. As a molten polymer solution for the polymer substrate is injected to a die and then cooled, the plurality of fine protrusions are not filled with the molten polymer solution, thereby resulting in a plurality of micro-cracks.
  • a molten or partially molten polymer substrate is subjected to stretching, twisting, or punching during an extrusion, spinning, or twisting process before being solidified, thereby forming a large number of fine micro-cracks in the polymer substrate.
  • Punching used herein includes a complete punching and a partial punching enough to form the micro-cracks.
  • the functional additive such as a fragrant substance, an antimicrobial substance, an insecticide substance, or a deodorant substance is positioned in the micro-cracks to form the functionality-imparting layer.
  • the positioning of the functional additive in the micro-cracks can be carried out as follows, but are not limited thereto.
  • a mixture solution of the functional additive dissolved or dispersed in a solvent or a dispersion medium may be sprayed on the polymer substrate with the micro-cracks, or the polymer substrate may be passed through a vessel containing the mixture solution.
  • these methods may be carried out in a batch or continuous process. In a continuous process, for example, in the middle of spinning or extruding the polymer substrate, the mixture solution may be sprayed on the polymer substrate, or the polymer substrate may be passed through a vessel containing the mixture solution.
  • the temperature of the polymer substrate may be adjusted using a thermostat according to a method known to ordinary persons skilled in the art. It is preferable to adjust the temperature of the polymer substrate so as not to exceed the temperature at which the functional additive thermally decomposes. In order to easily adhere a large amount of the functional additive to the micro-cracks, it is preferable to position the functional additive in the micro-cracks before the polymer substrate is fully solidified, using heat applied to the polymer substrate in the fabrication thereof or an external heat. Therefore, the functional additive can be strongly adhered to the polymer substrate to the extent that the functional additive can substantially be seen as an integral part of the polymer substrate.
  • the fragrant substance used herein may be in the form of a capsule coated with a polymer film, as well as in the form of an essential oil composition.
  • the functional additive in a case where the functional additive is in a liquid phase at a room temperature, the functional additive can be used in liquid form.
  • granules of the functional additive may be applied to the surface of the polymer substrate. The granules of the functional additive may be obtained by cooling the functional additive to a temperature less than 0 degrees to solidify the functional additive and then pulverizing the solidified functional additive into granules of an appropriate size.
  • the functionality-imparting layer is covered with the resin layer.
  • the resin layer may be formed by a method known to ordinary persons skilled in the art, for example, immersion, brushing, or doctor blade coating.
  • the resin layer may be formed using the same polymer as used for the polymer substrate to ensure good adhesion and resistance to delamination.
  • the polymer article according to the present invention may also be manufactured in the form of a covered yarn or a core spun yarn.
  • the functional additive is applied to a polymer substrate made of a filamentous core yarn (mainly, polyurethane elastic fiber yarn) to form the functionality-imparting layer by spraying, or passing through a vessel containing the additive, etc.
  • the functionality-imparting layer is covered with a filament yarn (in the case of using a covered yarn) or a staple yarn (in the case of using a core spun yarn) made of nylon, polyester, acrylic resin, cotton, or wool to form the resin layer.
  • the filament yarn is wound around the surface of the core yarn in the direction of S or Z to form the resin layer.
  • the staple yarn is spun around the surface of the core yarn to form the resin layer.
  • Example 1 Preparation of fragrant composition
  • a vegetable essential oil based fragrant composition was prepared as follows.
  • fragrance microcapsules containing a vegetable essential oil composition were prepared as follows.
  • KOO JOO TEXTILE Co. Ltd., Korea) stained with a dispersion dye was dissolved using an aqueous alkaline solution containing NaOH (25%) and an alkaline penetrating adjuvant (0.5%, KF NEORATE NA-50, NICCA KOREA Co. Ltd., Korea) in a batch weight reducing machine, to remove about 18% of the weight of the polyester fabric, followed by washing with water and drying.
  • YOUNG CHEMICAL Co. Ltd., Korea) was added into water and stirred for 10 hours to obtain an aqueous polyurethane solution.
  • the sprayed polyester fabric was immersed in the aqueous polyurethane solution having a weight about 10 times greater than the sprayed polyester fabric at a pickup rate of about 40 wt.%. Then, the polyester fabric was dried at about 100°C for 3 minutes and then heated at about 130 ° C for 3 minutes, followed by washing with about 20 ° C water and drying.
  • PMMA Polymethylmethacrylate
  • Aldrich Polymethylmethacrylate having a weight average molecular weight of about 350,000 and a glass transition temperature of about 122°C was cast into a PMMA substrate with a standard size of 7 cm x 7 cm x 2 cm.
  • the PMMA substrate was washed with water and dried. Then, acetone was sprayed on one surface of the PMMA substrate while the PMMA substrate was maintained horizontally.
  • the PMMA substrate was washed with water and dried. In this way, the surface of the PMMA substrate was irregularly dissolved by acetone to thereby form micro-cracks in the PMMA substrate.
  • Example 2 1.2 wt.% of the fragrant microcapsules prepared in Example 2 and 0.1 wt% of a surfactant were added into water and stirred for 30 minutes to obtain a fragrant mixed solution.
  • the fragrant mixed solution was sprayed on the PMMA substrate using a nozzle in such a way that the surface of the PMMA substrate having the micro-cracks was uniformly covered with the fragrant mixed solution, and then dried at about 50 °C for 2 hours.
  • the PMMA used in the preparation of the PMMA substrate was added to acetone and stirred for 10 hours to obtain an acetone solution containing 8 wt% of the PMMA. Then, the surface of the above PMMA substrate sprayed was coated with the PMMA-containing acetone solution using a doctor knife to obtain a smooth PMMA substrate.
  • the smooth PMMA substrate was dried at about 90 °C for 3 minutes and then heated at about 110°C for 3 minutes, followed by washing with about 20 ° C water and drying.
  • 0.1 wt% of a surfactant were added into water and stirred for 30 minutes to obtain a fragrant mixed solution.
  • 10 wt% of a water-soluble polyurethane resin SNOTEX UW-250, DAE YOUNG CHEMICAL Co. Ltd., Korea
  • the fragrant mixed solution and the aqueous polyurethane solution were mixed in a weight ratio of 1 : 1 and stirred for 10 hours to obtain a fragrant coating solution.
  • polyester fabric 100% polyester fabric (weight: 106 g/m ⁇ K-6565F, KOO JOO TEXTILE Co. Ltd., Korea) stained with a dispersion dye was immersed in the fragrant coating solution having a weight about 10 times greater than the 100% polyester fabric at a pickup rate of about 40 wt%. Then, the polyester fabric was dried at 100 ° C for 3 minutes and then heated at about 130 ° C for 3 minutes, followed by washing at about 20 ° C water and drying.
  • a plastic substrate directly coated with a fragrant substance was prepared to compare it with the plastic substrate of Example 4 in terms of fragrant property and the ability of fragrance to withstand washing and abrasion.
  • PMMA available from Aldrich
  • having a weight average molecular weight of about 350,000 and a glass transition temperature of about 122 ° C was cast into a PMMA substrate with a standard size of 7 cm x 7 cm x 2 cm.
  • Example 2 1.2 wt% of the fragrant microcapsules prepared in Example 2 and 0.1 wt% of a surfactant were added into water and stirred for 30 minutes to obtain a fragrant mixed solution.
  • the PMMA used in the preparation of the PMMA substrate was added into acetone and stirred for 10 hours to obtain an acetone solution containing 8 wt% of the PMMA.
  • the fragrant mixed solution and the PMMA-containing acetone solution were mixed in a weight ratio of 1 : 1 and stirred for 10 hours to obtain a fragrant coating solution.
  • the surface of the PMMA substrate was coated with the fragrant coating solution using a doctor knife to obtain a smooth PMMA substrate.
  • the smooth PMMA substrate was dried at about 90 ° C for 3 minutes and then heated at about 110 ° C for 3 minutes, followed by washing with about 20 ° C water and drying.
  • Example 5 Evaluation of fragrant property and ability of fragrance to withstand washing
  • the fragrant property and the ability of fragrance to withstand washing of the fabrics prepared in Example 3 and Comparative Example 1 were evaluated.
  • Evaluation of a fragrant property was based on surveys of an evaluation group consisting of 10 men and 10 women (the ratio of the age groups 20-29, 30-39, 40-49, and 50-59 is 4:2:2:2). Evaluation of a fragrant property was carried out after preparation of the fabrics. On the other hand, the ability of fragrance to withstand washing was evaluated after dry-cleaning 30 times in the same manner as in the evaluation of a fragrant property. The results are presented in Table 2 below.
  • Example 3 As shown in Table 2, immediately after the fabric preparation, the fragrant property of the fabric prepared in Comparative Example 1 (a conventional method) was good relative to the fabric prepared in Example 3 (the present invention). However, after the dry-cleaning 30 times, the fabric of Example 3 exhibited a better fragrant property than that of Comparative Example 1. It can be seen from these results that the fabric of Example 3 according to the present invention has an improved ability of fragrance to withstand washing. In addition, the fabric of Example 3 exhibited a better handle, when compared to that of Comparative Example 1.
  • Example 6 Evaluation of fragrant property and ability of fragrance to withstand abrasion
  • Example 3 the fragrant property and the ability of fragrance to withstand abrasion of the PMMA substrates prepared in Example 4 and Comparative Example 2 were evaluated. Evaluation of a fragrant property was based on surveys of an evaluation group consisting of 10 men and 10 women (the ratio of the age groups 20-29, 30-39, 40-49, and 50-59 is 4:2:2:2). The evaluation of a fragrant property was carried out after preparation of the PMMA substrates. On the other hand, the ability of fragrance to withstand abrasion was evaluated after the PMMA substrates were abraded using a sandpaper (#50) attached to a disk sander at the same rotating velocity for 10 minutes. The results are presented in Table 3 below.
  • the fragrant property of the PMMA substrate prepared in Comparative Example 2 was good relative to the PMMA substrate prepared in Example 4 (the present invention).
  • the PMMA substrate of Example 4 exhibited a better fragrant property than that of Comparative Example 2. It can be seen from these results that the PMMA substrate of Example 4 according to the present invention has an improved ability of fragrance to withstand abrasion. Therefore, even when accessories and living necessaries manufactured using the PMMA substrate according to the present invention are abraded in use, they can emit fragrance for a longer time.
  • the PMMA substrate of Example 4 exhibited a better handle, when compared to that of Comparative Example 2.
  • a polymer article according to the present invention micro-cracks are filled with a functional additive and the surface of the polymer article is finished with a resin layer. Therefore, the polymer article has good handle and appearance, as well as ability to withstand washing and abrasion being good.
  • the functional additive is added in a mild condition, the functional additive is not easily thermally or chemically decomposed or modified.
  • the method of manufacturing the polymer article according to the present invention can also be applied in the fabrication of natural polymer articles that are not made by an extrusion process or a spinning process.

Abstract

A polymer article is provided. The polymer article includes a polymer substrate having micro-cracks on the surface thereof, a functionality-imparting layer formed in the micro-cracks of the polymer substrate and comprising at least one functional additive selected from the group consisting of a fragrant substance, an antimicrobial substance, an insecticide substance, and a deodorant substance, and a resin layer covering the functionality-imparting layer. In the polymer article, the functional additive is present in the micro-cracks and the surface of the polymer article is finished with the resin layer. Therefore, the polymer article has good handle and appearance, as well as ability to withstand washing and abrasion being good.

Description

POLYMER ARTICLE AND METHOD FOR MANUFACTURING THE
SAME
Technical Field The present invention relates to a polymer article and a method of manufacturing the same. More particularly, the present invention relates to a polymer article which is excellent in handle and ability to withstand washing, abrasion, and the like, as a result of filling micro-cracks of the polymer article with a functional additive and finishing the surface of the polymer article with a resin layer, and a method of manufacturing the same.
Background Art
As a consumer's desire for higher quality increases with raising of the standard of living, there is an increasing need to add various functionalities to polymer articles such as fiber products and plastic products. Examples of such functionalities include a fragrant property that encourages people to feel comfortable, an antimicrobial property that efficiently controls propagation of fungi, bacteria or the like, and an insecticidal property that prevents infiltration of insects, worms or the like.
Furthermore, an interest has also been made in a process of imparting a deodorization property that allows removal of an offensive odor such as ammonia, hydrogen sulfide, trimethylamine, methyl mercaptan, a tobacco smell, and a sweat smell, to polymer articles. Conventional methods for imparting these functionalities to polymer articles such as fiber products and plastic products are as follows.
In a method, an additive such as a fragrant substance, an antimicrobial substance, an insecticide substance, or a deodorant substance that can chemically decompose or physically adsorb a gaseous odor component is added to a polymer solution or a molten polymer intended for fabrication of fiber products or plastic products, followed by spinning or molding. However, this method has a problem in that the additive mainly composed of an organic compound is easily thermally or chemically decomposed or modified due to a high temperature or chemicals applied during the fabrication process of polymer articles. Furthermore, this method cannot be applied in the fabrication of natural fiber products that are not made by a spinning process. Another method is a method of forming a polymer film containing a functional additive on the surfaces of fabric or plastic products. According to this method, fabric or plastic products are in advance formed using conventional weaving, knitting, extrusion molding, injection molding, etc. Then, in a subsequent step, the surfaces of the fabric or plastic products are coated with a resin composition containing the additive to thereby form the polymer film containing the additive. However, this method provides poor handle and appearance of final products. In addition, the ability to withstand washing, abrasion, and sunlight is poor. Therefore, the present invention provides a polymer article with good handle and good ability to withstand washing, abrasion, and the like.
The present invention also provides a method of manufacturing the polymer article with the above-described properties.
Disclosure of the Invention
According to an aspect of the present invention, there is provided a polymer article comprising: a polymer substrate having micro-cracks on the surface thereof; a functionality-imparting layer formed on the surface of the polymer substrate and comprising at least one functional additive selected from the group consisting of a fragrant substance, an antimicrobial substance, an insecticide substance, and a deodorant substance; and a resin layer covering the functionality-imparting layer.
According to another aspect of the present invention, there is provided a method of manufacturing a polymer article, the method comprising: forming micro-cracks on the surface of a polymer substrate; positioning, in the micro-cracks, at least one functional additive selected from the group consisting of a fragrant substance, an antimicrobial substance, an insecticide substance, and a deodorant substance, to form a functionality-imparting layer; and covering the functionality-imparting layer with a resin layer.
In the polymer article according to the present invention, the micro-cracks are filled with the functional additive and the surface of the polymer article is finished with the resin layer. Therefore, the polymer article has good handle and appearance, as well as the ability to withstand washing and sunlight being good. In the method of manufacturing the polymer article according to the present invention, since the functional additive is added in a mild condition, the functional additive is not easily thermally or chemically decomposed or modified. The method of manufacturing the polymer article according to the present invention can also be applied in the fabrication of natural polymer articles that are not made by an extrusion process or a spinning process. As used herein, the term, "polymer article" includes all products manufactured by any technologies known to ordinary persons skilled in the art such as weaving, spinning, extrusion molding, or injection molding. For example, the polymer article may be a yarn, a woven fabric, a nonwoven fabric, a knitted fabric, an extrusion-molded product, and an injection-molded product. The polymer article can be used to form, for example, necklaces, rings, bracelets, clothes, bags, glasses frames, golf clubs, gloves, cases for cellular phones, cases for electronic products such as televisions or refrigerators, automobile parts, interior automotive trim, curtains, wall papers, bedclothes, carpets, dolls, towels, hair bands, car seats, and shoes sole.
Hereinafter, a polymer article and a fabrication method therefor according to the present invention will be described in detail.
A polymer article according to the present invention comprises: a polymer substrate having micro-cracks on the surface thereof; a functionality-imparting layer formed on the polymer substrate and comprising at least one functional additive selected from the group consisting of a fragrant substance, an antimicrobial substance, an insecticide substance, and a deodorant substance; and a resin layer covering the functionality-imparting layer. That is, the polymer article of the present invention has a laminated structure of the polymer substrate, the functionality-imparting layer, and the resin layer. The surface of the polymer substrate is formed with the micro-cracks and the functional additive is positioned in the micro-cracks. The micro-cracks may have a diameter size ranging from several nanometers to several centimeters. The functional additive is not simply adhered to the surface of the polymer substrate using a binder, but is stably buried in the micro-cracks. Therefore, the ability to withstand washing and sunlight is good. That is, even though the polymer article of the present invention is washed several times or is exposed to sunlight for a long time, the functional additive is not easily removed from the polymer substrate. Therefore, the polymer article of the present invention can continuously provide functionalities such as a fragrant property and/or an antimicrobial property for a long time. In addition, since the surface of the polymer article of the present invention is smoothly finished with the resin layer, handle and appearance are good.
The polymer substrate may be a yarn, a fabric, an extrusion-molded plastic product, or an injection-molded plastic product, but is not limited thereto. The polymer substrate may also be a nonwoven fabric, a pulp, a wood, a metal substrate, and a rubber. Examples of the polymer substrate include, but are not limited to, polyamides such as natural protein, nylon 6, nylon 66, and nylon 610; polyesters such as polyethyleneterephthalate, polybutyleneterephthalate, and polynaphthaleneterephthalate; polyacrylonitriles; acrylic resins; polyolefins such as polyethylene and polypropylene; halogenated polyolefins; celluloses; regenerated celluloses; cellulose acetates; cellulose triacetates; polyurethanes; polycarbonates; polyacetals; vinylic polymers such as polystyrene, polyvinylchloride, polyvinylfluoride, and polyvinylacetate; (meth)acrylate resins such as polymethylacrylate and polymethylmethacrylate; formaldehyde resins such as urea-formaldehyde resin and melamine-formaldehyde resin; phenolic resins; and synthetic or natural rubbers such as NBR rubber, SBR rubber, natural rubber, synthetic polyisoprene rubber, and chloroprene rubber.
The functional additive positioned in the micro-cracks (valleys) may be a fragrant substance, an antimicrobial substance, an insecticide substance, a deodorant substance, or a mixture thereof.
The fragrant substance may be a vegetable fragrant substance, an animal fragrant substance, a synthetic fragrant substance, or a mixture thereof.
The vegetable fragrant substance that can be used herein is derived from, but is not limited to, lavender, peppermint, spearmint, turpentine, cinnamon, chamomile, anise, star anise, rosemary, eucalyptus, rose, bergamot, geranium, jasmine, tea tree, lemon, ylangylang, clove bud, coriander, lime, thyme, frankincense, ginger, grapefruit, hyssop, helichrysum, juniper, lemongrass, marjoram, melissa, myrrh, neroli, orange, basil, palmarosa, carrot seed, vetiver, cypress, fennel, sandalwood, patchouli, pine, rosewood, yarrow, angelica, sage, clary sage, birch, black pepper, cedarwood, benzoin, petigrain, lilac, violet, niaouli, Caesalpinia sappan L., tree essential oil, and a mixture thereof.
The animal fragment substance that can be used herein is derived from, but is not limited to, musk, ambergris, civet, castor, and a mixture thereof.
Examples of the synthetic fragrant substance that can be used herein include, but are not limited to, synthetic musk, terpene-based synthetic perfume, 2-phenylethyl alcohol, benzyl acetate, ethyl acetate, amyl acetate, octyl acetate, ethyl propionate, and a mixture thereof. The fragrant substance used herein is generally used in the form of an essential oil composition. The essential oil composition generally comprises alcohol, a solubilizing agent, or distilled water, in addition to a fragrant oil. Since there is no particular limitation to the content of each component of the essential oil composition, the amount of each component of the essential oil composition can be any amount conventionally used in the pertinent art.
The fragrant substance used herein may also be in the form of a capsule coated with a polymer film.
The antimicrobial substance is a chemical additive that is used to prevent contamination and deterioration of polymer articles such as fiber products or plastic products by microorganisms. The antimicrobial substance used herein includes phenolics, halogen compounds, quaternary ammonium compounds, metal derivatives, amines, alkanolamines and nitro derivatives, anilides, organic sulfur compounds and sulfur-nitrogen compounds. The anitimicrobial substance can kill all of microorganisms or prevent propagation of microorganisms so as not to deteriorate polymer articles. Microorganisms as mentioned herein are mainly bacteria and fungi. Bacteria and fungi are generally classified into two groups. That is, bacteria can be classified into gram positive and gram negative and fungi can be classified into filamentous fungi and yeasts.
Examples of the antimicrobial substance include, but are not limited to, dimethyl benzyl lauryl ammonium chloride, 3,5-dibromosalicyl anilide, pentachlorophenol, o-phenylphenol, trichloroisocyanuric acid, poly(vinylpyrolidone)-urea complex (PVP-lodine, available from ISP Corp.), 2,4,4'-trichloro-2'-hydroxydiphenylether,
2,2-dibromo-2-cyanoacetamide, 2-bromo-2-nitropropane-1 ,3-diol, benzalkonium chloride (Hyamine-3500, available from Rohm & Haas), 10,10'-oxybis-phenoxyarsine (Vinyzene BP-5 or Durotex, available from Ventron), tributyltinoxide (Cotin 300, available from Cosan), 3,4,4'-trichlorocarbanilide, hexahydro-1 ,3,5-tris-(2-hydroxyethyl)-5-triazine, bisthiocyanatemethylenebisthiocyanate (MBT),
2-n-octyl-4-isothiazolin-2-one.(Skane M-8, available from Rohm & Haas), tetrachloroisophthalonitrile, 1 -(3-chloroallyl)-3,5,7-triaza-1 -azonia adamantane chloride, and a mixture thereof.
The antimicrobial substance is selected from drugs capable of controlling target microorganisms to a predetermined level. Further, the antimicrobial substance must be physically and chemically compatible with media used therefor. That is, the antimicrobial substance must not adversely affect the physical and chemical properties of the media and must not be inactivated by the components of the media.
Examples of the deodorant substance used herein include, but are not limited to, β -cyclodextrine, a mixture of polyethyleneimine and nonionic hygroscopic organic material disclosed in Japanese Patent Laid-Open Publication No. Hei. 3-146064, an amino group-containing metal porphyrin-based compounds, chitosan, a modified chitosan, carboxylic acid-containing polymers, zinc oxide, an extract of Caesalpinia sappan L., a zinc oxide particle, a silver particle, a silica particle, and a mixture thereof. Like the fragrant substance, the anitimicrobial substance and the deodorant substance may be used in the form of a microcapsule coated with a polymer film.
The microcapsule may be made of a urea-formaldehyde resin, a melamine-formaldehyde resin, a polyurethane resin, gelatin, an acrylic resin, an epoxy resin, or a polysiloxane resin, but is not limited thereto.
Meanwhile, the functionality-imparting layer may further comprise a titanium dioxide photocatalyst. In particular, in a case where the functional additive such as the fragrant substance, the antimicrobial substance, or the deodorant substance are used in a microcapsule form, using the titanium dioxide photocatalyst is preferred. The titanium dioxide photocatalyst leads to oxidative decomposition of the microcapsule encapsulating the functional additive by a photocatalytic action when the functional additive is exposed to the air due to abrasion of the surface resin layer, thereby gradually releasing the functional additive such as the fragrant substance or the antimicrobial substance into the air. In addition, the titanium dioxide photocatalyst can decompose environmental organic materials, fungi, or bacteria, thereby reinforcing antimicrobial and deodorization properties, and can prevent discoloration of a polymer article by sunlight, thereby improving the ability to withstand sunlight.
The titanium dioxide photocatalyst is added in the amount of 0.1 to 20 parts by weight, preferably, 0.5 to 10 parts by weight, based on 100 parts by weight of the functional additive. If the content of the titanium dioxide is less than 0.1 parts by weight, the titanium dioxide cannot serve as a photocatalyst. On the other hand, if it exceeds 20 parts by weight, the polymer substrate made of an organic material such as a fiber and a plastic may decompose due to excess oxidation power.
In order to increase the photocatalytic efficiency of the titanium dioxide photocatalyst, there is a need to increase the surface area of the titanium dioxide. For this, the titanium dioxide may be formed in a porous fine powder form to increase the number of active sites, and/or the titanium dioxide may be mixed with a cocatalyst, such as platinum, iron, and silicon, to activate a photocatalytic reaction even at a low energy wavelength.
The functionality-imparting layer is covered with the resin layer.
That is, the resin layer constitutes the surface of the polymer article according to the present invention. In conventional functional polymer articles, a functional additive is adhered to the surface of a polymer article by means of a binder resin. For this, a polymer article is immersed in a mixture solution of a functional additive and the binder resin, followed by drying or heating. For this reason, the conventional polymer articles have a rough surface and an unsatisfactory appearance.
However, according to the present invention, since only a polymer resin constitutes the resin layer and the resin layer can be formed by means of various methods such as brushing and doctor blade coating in addition to immersion, the resin layer has a smooth handle and good appearance.
Meanwhile, it is preferable to form the resin layer using the same polymer as used for the polymer substrate to increase adhesion and resistance to delamination.
A method of manufacturing the polymer article according to the present invention will now be described in detail. (1 ) Formation of micro-cracks
First, the micro-cracks are formed on the surface of the polymer substrate. The micro-cracks are not intended for simply adhering the functional additive to the surface of the polymer substrate. Rather, the functional additive is buried in the micro-cracks, and thus, the functional additive can be seen as an integral part of the polymer substrate. Therefore, even though the surface of the polymer article of the present invention is abraded in use, functionalities such as fragrant or antimicrobial properties of the functional additive can be maintained for a longer time. The micro-cracks may have a diameter size ranging from several nanometers to several centimeters.
The formation of the micro-cracks on the surface of the polymer substrate can be carried out using the following three methods, but are not limited thereto.
In a first method, a solvent capable of dissolving the polymer substrate is used. According to this method, the surface of the polymer substrate is treated with the polymer substrate-dissolving solvent to provide the polymer substrate with an irregularly dissolved surface.
In a second method, an injection molding is used. According to this method, an injection molding is carried out using a die having a plurality of fine protrusions. This method can be used when the polymer substrate is formed by means of an injection molding. As a molten polymer solution for the polymer substrate is injected to a die and then cooled, the plurality of fine protrusions are not filled with the molten polymer solution, thereby resulting in a plurality of micro-cracks.
In a third method, a molten or partially molten polymer substrate is subjected to stretching, twisting, or punching during an extrusion, spinning, or twisting process before being solidified, thereby forming a large number of fine micro-cracks in the polymer substrate. Punching used herein includes a complete punching and a partial punching enough to form the micro-cracks.
(2) Formation of functionality-imparting layer
After forming the micro-cracks in the polymer substrate, the functional additive such as a fragrant substance, an antimicrobial substance, an insecticide substance, or a deodorant substance is positioned in the micro-cracks to form the functionality-imparting layer. The positioning of the functional additive in the micro-cracks can be carried out as follows, but are not limited thereto.
That is, in order to position the functional additive in the micro-cracks, a mixture solution of the functional additive dissolved or dispersed in a solvent or a dispersion medium may be sprayed on the polymer substrate with the micro-cracks, or the polymer substrate may be passed through a vessel containing the mixture solution. These methods may be carried out in a batch or continuous process. In a continuous process, for example, in the middle of spinning or extruding the polymer substrate, the mixture solution may be sprayed on the polymer substrate, or the polymer substrate may be passed through a vessel containing the mixture solution.
The temperature of the polymer substrate may be adjusted using a thermostat according to a method known to ordinary persons skilled in the art. It is preferable to adjust the temperature of the polymer substrate so as not to exceed the temperature at which the functional additive thermally decomposes. In order to easily adhere a large amount of the functional additive to the micro-cracks, it is preferable to position the functional additive in the micro-cracks before the polymer substrate is fully solidified, using heat applied to the polymer substrate in the fabrication thereof or an external heat. Therefore, the functional additive can be strongly adhered to the polymer substrate to the extent that the functional additive can substantially be seen as an integral part of the polymer substrate.
As describe above, the fragrant substance used herein may be in the form of a capsule coated with a polymer film, as well as in the form of an essential oil composition.
Meanwhile, in a case where the functional additive is in a liquid phase at a room temperature, the functional additive can be used in liquid form. Alternatively, granules of the functional additive may be applied to the surface of the polymer substrate. The granules of the functional additive may be obtained by cooling the functional additive to a temperature less than 0 degrees to solidify the functional additive and then pulverizing the solidified functional additive into granules of an appropriate size.
(3) Formation of resin layer
After the functional additive is positioned in the micro-cracks, the functionality-imparting layer is covered with the resin layer. The resin layer may be formed by a method known to ordinary persons skilled in the art, for example, immersion, brushing, or doctor blade coating. The resin layer may be formed using the same polymer as used for the polymer substrate to ensure good adhesion and resistance to delamination.
The polymer article according to the present invention may also be manufactured in the form of a covered yarn or a core spun yarn. In this case, the functional additive is applied to a polymer substrate made of a filamentous core yarn (mainly, polyurethane elastic fiber yarn) to form the functionality-imparting layer by spraying, or passing through a vessel containing the additive, etc. Next, the functionality-imparting layer is covered with a filament yarn (in the case of using a covered yarn) or a staple yarn (in the case of using a core spun yarn) made of nylon, polyester, acrylic resin, cotton, or wool to form the resin layer. In the case of using the covered yarn, the filament yarn is wound around the surface of the core yarn in the direction of S or Z to form the resin layer. In the case of using the core spun yarn, the staple yarn is spun around the surface of the core yarn to form the resin layer.
Examples
Hereinafter, the present invention will be described more specifically by examples. However, the following examples are provided only for illustrations and thus the present invention is not limited to or by them.
Example 1 : Preparation of fragrant composition In this Example, a vegetable essential oil based fragrant composition was prepared as follows.
9.0 wt% of ethanol as an evaporation rate controlling agent, 4.0 wt% of propylene glycol as a solubilizing adjuvant, 8.0 wt% of polyoxyethylene phenyl ether as a solubilizing agent, and 2.0 wt% of a fragrant substance made of a mixture of natural essential oils presented in Table 1 below were mixed and gradually dissolved in 69.0 wt% of distilled water. 2.0 wt% of polymer beads were added to the mixture solution at a room temperature, followed by further addition of an ethanol until a total composition reached 100 wt%. Then, the resultant mixture solution was aged by repeatedly stirring, mixing, and standing for 24 hours and then filtered to thereby form a fragrant composition.
Table 1
Figure imgf000015_0001
Example 2: Preparation of fragrant microcapsules
In this Example, fragrant microcapsules containing a vegetable essential oil composition were prepared as follows.
19.16 g of toluene-2,4-diisocyanate and 122.7 mL of cyclohexanone were mixed in a nitrogen atmosphere for 30 minutes. Then, 3.10 g of ethylene glycol was added to the mixture and incubated at 80 °C for 2 hours to obtain a polyurethane prepolymer. 4 g of the polyurethane prepolymer, 4 g of the fragrant composition obtained in Example 1 , and 12 g of cyclohexanone were mixed and dispersed in 100 g of 1.5% aqueous solution of arabic gum. An aqueous solution of 4 g of ethylene glycol and 20 g of water was added to the resultant mixture solution and stirred while heating it to 66 °C , to obtain fragrant microcapsules.
Example 3: Preparation of polyester fabric filled with fragrant substance
First, 1.2 wt% of the fragrant microcapsules obtained in Example 2 and 0.1 wt% of a surfactant were added into water and stirred for 30 minutes to obtain a mixed solution. The surface of 100% polyester fabric (weight: 106 g/πf , K-6565F,
KOO JOO TEXTILE Co. Ltd., Korea) stained with a dispersion dye was dissolved using an aqueous alkaline solution containing NaOH (25%) and an alkaline penetrating adjuvant (0.5%, KF NEORATE NA-50, NICCA KOREA Co. Ltd., Korea) in a batch weight reducing machine, to remove about 18% of the weight of the polyester fabric, followed by washing with water and drying.
Next, the mixed solution was sprayed on both surfaces of the polyester fabric at a pickup rate of about 10% and then dried at about 100°C for 15 minutes. 10 wt% water-soluble polyurethane resin (SNOTEX UW-250, DAE
YOUNG CHEMICAL Co. Ltd., Korea) was added into water and stirred for 10 hours to obtain an aqueous polyurethane solution. The sprayed polyester fabric was immersed in the aqueous polyurethane solution having a weight about 10 times greater than the sprayed polyester fabric at a pickup rate of about 40 wt.%. Then, the polyester fabric was dried at about 100°C for 3 minutes and then heated at about 130°C for 3 minutes, followed by washing with about 20 °C water and drying.
Example 4: Preparation of plastic substrate filled with fragrant substance
Polymethylmethacrylate (PMMA, available from Aldrich) having a weight average molecular weight of about 350,000 and a glass transition temperature of about 122°C was cast into a PMMA substrate with a standard size of 7 cm x 7 cm x 2 cm. The PMMA substrate was washed with water and dried. Then, acetone was sprayed on one surface of the PMMA substrate while the PMMA substrate was maintained horizontally.
At about 15 minutes after the spraying, the PMMA substrate was washed with water and dried. In this way, the surface of the PMMA substrate was irregularly dissolved by acetone to thereby form micro-cracks in the PMMA substrate.
Next, 1.2 wt.% of the fragrant microcapsules prepared in Example 2 and 0.1 wt% of a surfactant were added into water and stirred for 30 minutes to obtain a fragrant mixed solution. The fragrant mixed solution was sprayed on the PMMA substrate using a nozzle in such a way that the surface of the PMMA substrate having the micro-cracks was uniformly covered with the fragrant mixed solution, and then dried at about 50 °C for 2 hours.
The PMMA used in the preparation of the PMMA substrate was added to acetone and stirred for 10 hours to obtain an acetone solution containing 8 wt% of the PMMA. Then, the surface of the above PMMA substrate sprayed was coated with the PMMA-containing acetone solution using a doctor knife to obtain a smooth PMMA substrate. The smooth PMMA substrate was dried at about 90 °C for 3 minutes and then heated at about 110°C for 3 minutes, followed by washing with about 20°C water and drying.
Comparative Example 1 : Preparation of polyester fabric surface-coated with fragrant substance
In this Comparative Example, a fabric directly coated with a fragrant substance was prepared to compare it with the fabric of Example 3 in terms of fragrant property and the ability of fragrance to withstand washing and abrasion.
1.2 wt% of the fragrant microcapsules prepared in Example 2 and
0.1 wt% of a surfactant were added into water and stirred for 30 minutes to obtain a fragrant mixed solution. Then, 10 wt% of a water-soluble polyurethane resin (SNOTEX UW-250, DAE YOUNG CHEMICAL Co. Ltd., Korea) was added into water and stirred for one hour to obtain an aqueous polyurethane solution. The fragrant mixed solution and the aqueous polyurethane solution were mixed in a weight ratio of 1 : 1 and stirred for 10 hours to obtain a fragrant coating solution.
100% polyester fabric (weight: 106 g/m\ K-6565F, KOO JOO TEXTILE Co. Ltd., Korea) stained with a dispersion dye was immersed in the fragrant coating solution having a weight about 10 times greater than the 100% polyester fabric at a pickup rate of about 40 wt%. Then, the polyester fabric was dried at 100°C for 3 minutes and then heated at about 130°C for 3 minutes, followed by washing at about 20 °C water and drying.
Comparative Example 2: Preparation of plastic substrate surface-coated with fragrant substance
In this Comparative Example, a plastic substrate directly coated with a fragrant substance was prepared to compare it with the plastic substrate of Example 4 in terms of fragrant property and the ability of fragrance to withstand washing and abrasion. PMMA (available from Aldrich) having a weight average molecular weight of about 350,000 and a glass transition temperature of about 122°C was cast into a PMMA substrate with a standard size of 7 cm x 7 cm x 2 cm.
Next, 1.2 wt% of the fragrant microcapsules prepared in Example 2 and 0.1 wt% of a surfactant were added into water and stirred for 30 minutes to obtain a fragrant mixed solution. Then, the PMMA used in the preparation of the PMMA substrate was added into acetone and stirred for 10 hours to obtain an acetone solution containing 8 wt% of the PMMA. Then, the fragrant mixed solution and the PMMA-containing acetone solution were mixed in a weight ratio of 1 : 1 and stirred for 10 hours to obtain a fragrant coating solution.
Next, the surface of the PMMA substrate was coated with the fragrant coating solution using a doctor knife to obtain a smooth PMMA substrate. The smooth PMMA substrate was dried at about 90 °C for 3 minutes and then heated at about 110°C for 3 minutes, followed by washing with about 20 °C water and drying.
Example 5: Evaluation of fragrant property and ability of fragrance to withstand washing In this Example, the fragrant property and the ability of fragrance to withstand washing of the fabrics prepared in Example 3 and Comparative Example 1 were evaluated.
Evaluation of a fragrant property was based on surveys of an evaluation group consisting of 10 men and 10 women (the ratio of the age groups 20-29, 30-39, 40-49, and 50-59 is 4:2:2:2). Evaluation of a fragrant property was carried out after preparation of the fabrics. On the other hand, the ability of fragrance to withstand washing was evaluated after dry-cleaning 30 times in the same manner as in the evaluation of a fragrant property. The results are presented in Table 2 below.
Table 2
Example 3 Comparative Example 1
After After dry-cleaning 30 dry-cleaning 30
Rating After preparation times After preparation times
Good 8 8 12 2
Slightly good 6 9 6 3
Average 5 3 2 12
Slightly bad 1 - - 3
Bad - - - -
As shown in Table 2, immediately after the fabric preparation, the fragrant property of the fabric prepared in Comparative Example 1 (a conventional method) was good relative to the fabric prepared in Example 3 (the present invention). However, after the dry-cleaning 30 times, the fabric of Example 3 exhibited a better fragrant property than that of Comparative Example 1. It can be seen from these results that the fabric of Example 3 according to the present invention has an improved ability of fragrance to withstand washing. In addition, the fabric of Example 3 exhibited a better handle, when compared to that of Comparative Example 1.
Example 6: Evaluation of fragrant property and ability of fragrance to withstand abrasion
In this Example, the fragrant property and the ability of fragrance to withstand abrasion of the PMMA substrates prepared in Example 4 and Comparative Example 2 were evaluated. Evaluation of a fragrant property was based on surveys of an evaluation group consisting of 10 men and 10 women (the ratio of the age groups 20-29, 30-39, 40-49, and 50-59 is 4:2:2:2). The evaluation of a fragrant property was carried out after preparation of the PMMA substrates. On the other hand, the ability of fragrance to withstand abrasion was evaluated after the PMMA substrates were abraded using a sandpaper (#50) attached to a disk sander at the same rotating velocity for 10 minutes. The results are presented in Table 3 below.
Table 3
Example 4 Comparative Example 2
After abrasion for After abrasion for
Rating After preparation 10 minutes After preparation 10 minutes
Good 2 8 10 1
Slightly good 3 9 5 2
Average 13 2 3 16
Slightly bad 2 1 2 1
Bad - - - -
As shown in Table 3, after the PMMA substrate preparation, the fragrant property of the PMMA substrate prepared in Comparative Example 2 (conventional method) was good relative to the PMMA substrate prepared in Example 4 (the present invention). However, after the abrasion for 10 minutes, the PMMA substrate of Example 4 exhibited a better fragrant property than that of Comparative Example 2. It can be seen from these results that the PMMA substrate of Example 4 according to the present invention has an improved ability of fragrance to withstand abrasion. Therefore, even when accessories and living necessaries manufactured using the PMMA substrate according to the present invention are abraded in use, they can emit fragrance for a longer time. In addition, the PMMA substrate of Example 4 exhibited a better handle, when compared to that of Comparative Example 2.
Industrial Applicability
As is apparent from the above description, in a polymer article according to the present invention, micro-cracks are filled with a functional additive and the surface of the polymer article is finished with a resin layer. Therefore, the polymer article has good handle and appearance, as well as ability to withstand washing and abrasion being good. In a method of manufacturing the polymer article according to the present invention, since the functional additive is added in a mild condition, the functional additive is not easily thermally or chemically decomposed or modified. Furthermore, the method of manufacturing the polymer article according to the present invention can also be applied in the fabrication of natural polymer articles that are not made by an extrusion process or a spinning process.

Claims

What is claimed is:
1. A polymer article comprising: a polymer substrate having micro-cracks on the surface thereof; a functionality-imparting layer formed on the surface of the polymer substrate and comprising at least one functional additive selected from the group consisting of a fragrant substance, an antimicrobial substance, an insecticide substance, and a deodorant substance; and a resin layer covering the functionality-imparting layer.
10
2. The polymer article according to claim 1 , wherein the polymer substrate is one selected from the group consisting of a yarn, a fabric, an extrusion-molded plastic product, and an injection-molded plastic product.
15
3. The polymer article according to claim 1 , wherein the fragrant substance is at least one selected from the group consisting of a vegetable fragrant substance, an animal fragrant substance, and a synthetic fragrant substance.
20
4. The polymer article according to claim 1 , wherein the antimicrobial substance is at least one selected from the group consisting of dimethyl benzyl lauryl ammonium chloride, 3,5-dibromosalicyl anilide, pentachlorophenol, o-phenylphenol,
25 trichloroisocyanuric acid, poly(vinylpyrolidone)-urea complex, 2,4,4'-trichloro-2'-hydroxydiphenylether, 2,2-dibromo-2-cyanoacetamide, 2-bromo-2-nitropropane-1 ,3-diol, benzalkonium chloride,
10,10'-oxybis-phenoxyarsine, tributyltinoxide, 3,4,4'-trichlorocarbanilide, hexahydro-1 ,3,5-tris-(2-hydroxyethyl)-5-triazine,
30 bisthiocyanatemethylenebisthiocyanate (MBT), 2-n-octyl-4-isothiazolin-2-one, tetrachloroisophthalonitrile, and
1-(3-chloroallyl)-3,5,7-triaza-1-azonia adamantane chloride.
5. The polymer article according to claim 1 , wherein the deodorant substance is at least one selected from the group consisting of β -cyclodextrine, a mixture of polyethyleneimine and nonionic hygroscopic organic material, an amino group-containing metal porphyrin-based compounds, chitosan and modified chitosan, carboxylic acid-containing polymers, zinc oxide, an extract of Caesalpinia sappan L., a zinc oxide particle, a silver particle, and a silica particle.
6. The polymer article according to claim 1 , wherein the functionality-imparting layer further comprises 0.1 to 20 parts by weight of a titanium dioxide-based photocatalyst, based on 100 parts by weight of the functional additive.
7. The polymer article according to claim 1 , wherein the functional additive is in the form of a capsule coated with a polymer film.
8. The polymer article according to claim 7, wherein the polymer film is at least one selected from the group consisting of a melamin-formaldehyde resin, an urea-formaldehyde resin, a polyurethane resin, gelatin, an acrylic resin, an epoxy resin, and a polysiloxane resin.
9. The polymer article according to claim 1 , wherein the resin layer is made of the same polymer as used for the polymer substrate.
10. The polymer article according to any one of claims 1 to 9, which is one selected from the group consisting of accessories, buttons, and outer cases for writing instruments.
11. A method of manufacturing a polymer article, the method comprising: forming micro-cracks on the surface of a polymer substrate; positioning, in the micro-cracks, at least one functional additive selected from the group consisting of a fragrant substance, an antimicrobial substance, an insecticide substance, and a deodorant substance, to form a functionality-imparting layer; and covering the functionality-imparting layer with a resin layer.
12. The method according to claim 11 , wherein in the formation of the micro-cracks on the surface of the polymer substrate, the surface of the polymer substrate is treated with a solvent that can dissolve the surface of the polymer substrate.
13. The method according to claim 12, wherein in the formation of the micro-cracks on the surface of the polymer substrate, the polymer substrate is injection-molded in a die with a plurality of fine protrusions.
14. The method according to claim 12, wherein in the formation of the micro-cracks on the surface of the polymer substrate, a molten or partially molten polymer substrate is stretched, twisted, or punched during an extrusion, spinning, or twisting process, before being solidified.
15. The method according to claim 12, wherein the resin layer is made of the same polymer as used for the polymer substrate.
16. The method according to claim 12, wherein in the positioning of the functional additive in the micro-cracks, a mixture solution of the functional additive dissolved or dispersed in a solvent or a dispersion medium is sprayed on the polymer substrate, or the polymer substrate is passed through a vessel containing the mixture solution.
17. The method according to claim 12, wherein in the positioning of the functional additive in the micro-cracks, the temperature of the polymer substrate is adjusted in such a way not to exceed the temperature at which the functional additive thermally decomposes.
PCT/KR2003/001873 2002-09-09 2003-09-09 Polymer article and method for manufacturing the same WO2004022841A1 (en)

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EP2038473A2 (en) * 2006-06-30 2009-03-25 THOR GmbH Antimicrobial textile
WO2011012935A2 (en) * 2009-07-29 2011-02-03 Universidade Do Minho Photocatalytic coating for the controlled release of volatile agents
CN102619085A (en) * 2012-04-06 2012-08-01 福建锦江科技有限公司 Deodorization polyamide fiber and preparation method thereof
CN104588101A (en) * 2015-01-13 2015-05-06 中国石油大学(华东) Heterogeneous photocatalytic material with pH responsiveness as well as preparation method and application thereof
CN105064010A (en) * 2015-08-03 2015-11-18 湖州吉昌丝绸有限公司 Novel natural antibacterial finishing agent, and preparation method thereof
CN105586252A (en) * 2016-02-03 2016-05-18 江苏丰泽生物工程设备制造有限公司 Fermentation liquid transplantation distributor
WO2017006247A1 (en) 2015-07-05 2017-01-12 Universidade Do Minho Micro- or nanocapsules having photocatalytic properties for controlled release of diffusing agents and respective method of production
CN114605791A (en) * 2022-03-28 2022-06-10 济南际通智能制造有限公司 Ribbon and preparation method thereof

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KR101150517B1 (en) * 2011-09-08 2012-05-31 (주)금강페이버 Functional resin chip and manufacturing method for the same
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2038473A2 (en) * 2006-06-30 2009-03-25 THOR GmbH Antimicrobial textile
WO2011012935A2 (en) * 2009-07-29 2011-02-03 Universidade Do Minho Photocatalytic coating for the controlled release of volatile agents
WO2011012935A3 (en) * 2009-07-29 2011-07-21 Universidade Do Minho Photocatalytic coating for the controlled release of volatile agents
CN102619085A (en) * 2012-04-06 2012-08-01 福建锦江科技有限公司 Deodorization polyamide fiber and preparation method thereof
CN104588101A (en) * 2015-01-13 2015-05-06 中国石油大学(华东) Heterogeneous photocatalytic material with pH responsiveness as well as preparation method and application thereof
WO2017006247A1 (en) 2015-07-05 2017-01-12 Universidade Do Minho Micro- or nanocapsules having photocatalytic properties for controlled release of diffusing agents and respective method of production
CN105064010A (en) * 2015-08-03 2015-11-18 湖州吉昌丝绸有限公司 Novel natural antibacterial finishing agent, and preparation method thereof
CN105586252A (en) * 2016-02-03 2016-05-18 江苏丰泽生物工程设备制造有限公司 Fermentation liquid transplantation distributor
CN105586252B (en) * 2016-02-03 2018-03-09 江苏丰泽生物工程设备制造有限公司 A kind of zymotic fluid culture transferring distributor
CN114605791A (en) * 2022-03-28 2022-06-10 济南际通智能制造有限公司 Ribbon and preparation method thereof

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