WO2017131400A1 - Water-repellent agent of silicone-based emulsion and fabric water-repellent processing method using same - Google Patents

Water-repellent agent of silicone-based emulsion and fabric water-repellent processing method using same Download PDF

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WO2017131400A1
WO2017131400A1 PCT/KR2017/000759 KR2017000759W WO2017131400A1 WO 2017131400 A1 WO2017131400 A1 WO 2017131400A1 KR 2017000759 W KR2017000759 W KR 2017000759W WO 2017131400 A1 WO2017131400 A1 WO 2017131400A1
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water
silicone
repellent
water repellent
fabric
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PCT/KR2017/000759
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French (fr)
Korean (ko)
Inventor
최기항
고영대
이민혁
김풍기
신정훈
김민경
최승훈
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주식회사 인실리코
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Publication of WO2017131400A1 publication Critical patent/WO2017131400A1/en

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
    • D06B3/04—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of yarns, threads or filaments
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B15/00—Removing liquids, gases or vapours from textile materials in association with treatment of the materials by liquids, gases or vapours
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
    • D06B3/10—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
    • D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain

Definitions

  • the present invention relates to a silicone-based emulsion water repellent and a water-repellent processing method of the fabric using the same concept to minimize environmental hazards, simultaneously exhibit excellent water repellency and laundry durability using a new concept eco-friendly manufacturing method and materials.
  • PFOS perfluorinated octasulfate
  • the present invention has been made to solve the above problems, and an object of the present invention is to provide a non-fluorinated silicone-based water-repellent agent using a new concept eco-friendly manufacturing method and materials to minimize environmental hazards.
  • the present invention is to provide a water-repellent processing method of the fabric that can exhibit the excellent water-repellent power, water repellent durability, washing durability using the above-described silicone-based water repellent agent.
  • the present invention is a silicone oil;
  • a silicone emulsion water repellent agent comprising an emulsifier and water, wherein the silicone oil comprises: a first alkylalkoxysilane having an alkyl group having 6 to 20 carbon atoms; A second alkylalkoxysilane having 1 to 6 carbon atoms having an acryloyloxyalkyl group or a methacryloyloxyalkyl group; And a silicone emulsion water repellent containing a third siloxane compound.
  • the first alkylalkoxy silane is hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane ,
  • Nonyltrimethoxysilane, nonyltriethoxysilane, decyltriethoxysilane, undecyltriethoxysilane and dodecyltriethoxysilane may be one or more selected from the group consisting of.
  • the second alkyl alkoxysilane is acryloyloxypropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, acryloyloxypropyltriethoxysilane, and methacryloyloxypropyltriethoxysilane It may be one or more selected from the group consisting of.
  • the third siloxane compound is hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dimethyltetramethoxydisiloxane, trimethyltrimethoxydisiloxane, and tetramethyltetramethoxytrisiloxane, hexamethyltetramethoxytetra It may be at least one selected from the group consisting of siloxanes.
  • the silicone oil is based on 100% by weight of the total weight of the silicone oil, 15 to 50% by weight of the first alkyl alkoxysilane, 10 to 40% by weight of the second alkylalkoxysilane, the third siloxane 10 to 30% by weight of the acid-based compound, 5 to 15% by weight of the organic solvent and 100% by weight of the silicone oil may be a composition comprising a residual amount of water.
  • the emulsion may be an oil-in-water (O / W type) emulsion in which silicone oil is granulated in the average particle size of 2.5 ⁇ 3.0 ⁇ m range.
  • O / W type oil-in-water
  • the present invention provides a water-repellent processing method of the fabric using the above-described silicone emulsion water-repellent agent.
  • the water-repellent processing method includes the steps of (i) immersing the fabric in the silicone emulsion water-repellent agent and then padding; And (ii) drying and curing the fabric.
  • Silicone emulsion type water repellent according to the present invention is composed of a material harmless to the human body can improve the stability to environmental hormones, and is a water repellent composition for fibers excellent in water repellency and wash durability.
  • the texture of the fiber after water repellent treatment is excellent, and the touch feeling is excellent, so that the softener process can be omitted.
  • FIG. 1 is a graph showing the average particle size distribution of the silicone emulsion particles prepared in Example 1.
  • Example 2 is a graph showing the results of the water repellency sustainability test according to the number of washing times using the water repellent agent of Example 1 and Comparative Examples 1 to 3.
  • Conventional fluorine-based water repellents are not only harmful to the human body or the environment, but also have a water repellent effect by modifying only the surface of the fiber through the lotus leaf effect to prevent water molecules from passing through the surface.
  • the present invention is to provide a penetration-type silicone emulsion water-repellent agent that is not only harmless to the human body or the environment, but also penetrates to the surface of the fiber and the inside of the fiber.
  • the novel water repellent according to the present invention uses a non-fluorine-based silicone component, it is harmless to a human body or the environment, and thus can completely prevent environmental damage caused by water repellent processing.
  • the silicone component is composed of emulsion particles of several micrometers ( ⁇ m) unit, the fine particles of the emulsion not only remain on the surface of the fiber, but also penetrates deep into the fiber and binds to the fiber, the initial water repellency Excellent degree of water and water repellency
  • the silicone-based water repellent penetrates to the surface and the inside of the fiber and is hardened to bind the fiber firmly, the outflow of the water repellent agent by washing is minimized, and the washing durability is very high.
  • the texture of the fiber after water repellent treatment is superior to that of the conventional fluorine-based, so it has an excellent touch feeling and has the advantage of eliminating the softener process.
  • Silicone emulsion water repellent of the present invention is largely silicone oil;
  • An emulsifier and water wherein the silicone oil comprises: (a) a first alkylalkoxysilane having an alkyl group of 6 to 20 carbon atoms; (b) a second alkylalkoxysilane having 1 to 6 carbon atoms having an acryloyloxyalkyl group or a methacryloyloxyalkyl group; And (c) a third siloxane compound.
  • the first alkylalkoxysilane (a) constituting the silicone oil may use a conventional alkylalkoxysilane known in the art.
  • a compound in which at least one alkyl group having 6 to 20 carbon atoms and at least one alkoxy group selected from methoxy, ethoxy and ethoxy are directly bonded to a silicon atom may be used.
  • a monoalkyl trialkoxy silane is used. Is to use.
  • the first alkylalkoxysilane (a) when at least one alkyl group directly bonded to the silicon atom of the first alkylalkoxysilane (a) has less than 6 carbon atoms, it may exhibit extremely high hydrolyzability and volatility, and the molecular portion of the first alkylalkoxysilane After being applied to the surface of the fibrous base, it reacts too quickly with the surface of the fibrous base so that the permeability of the emulsion is delayed, and a water repellent component can be given only to the surface of the fibrous base.
  • at least one alkyl group directly bonded to a silicon atom has more than 20 carbon atoms, its molecular weight is too large to easily penetrate into the fiber base .
  • Non-limiting examples of usable first alkylalkoxysilane (a) include hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxy silane, heptyltriethoxysilane, octyltrimethoxysilane, octyltrie Methoxysilane, nonyltrimethoxysilane, nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane, undecyltriethoxysilane, dodecyltrimethoxysilane, dodecyl Triethoxysilane and the like. These may be used alone or in combination of two or more thereof.
  • the second alkylalkoxysilane (b) constituting the silicone oil is a conventional alkylalkoxysilane known in the art, and has acryloyloxy group or methacryloyloxy group and carbon number at the terminal.
  • An alkylalkoxysilane having an alkyl group of 1 to 6 can be used without limitation.
  • the second alkylalkoxysilane is added for the purpose of providing a hydrophilic function to facilitate the bonding with the fabric.
  • non-limiting examples of the second alkylalkoxysilane usable in the present invention include acryloyloxypropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, and acryloyloxypropyltriethoxy Silane, methacryloyloxypropyltriethoxysilane, and the like. These may be used alone or in combination of two or more thereof.
  • hydrophilicity can be imparted to the hydrophobic silicone polymer, which is preferable.
  • the third siloxane compound (c) constituting the silicone oil may be used without limitation to conventional siloxane compounds known in the art.
  • the third siloxane compound is preferably a siloxane having a linear structure, and more preferably, linear polydimethylsiloxane.
  • non-limiting examples of the third siloxane compound which can be used include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dimethyltetramethoxydisiloxane, trimethyltrimethoxydisiloxane, and tetramethyltetra Methoxytrisiloxane, hexamethyltetramethoxytetrasiloxane, and the like. These may be used alone or in combination of two or more thereof.
  • hydrophobic first alkylalkoxysilane, second alkylalkoxysilane, and third siloxane compound are the main components, and the active components, alkylalkoxysilane and siloxane, penetrate deeply from the surface through the capillary pores of the fiber base.
  • the active components, alkylalkoxysilane and siloxane penetrate deeply from the surface through the capillary pores of the fiber base.
  • the content of the silicone oil is not particularly limited, but may be in the range of 30 to 70 parts by weight, preferably 30 to 50 parts by weight, relative to 100 parts by weight of the total silicone emulsion water repellent.
  • the content of the silicone oil is smaller than the above range, it is difficult to exhibit a sufficient water repellent effect, the permeability of the water-repellent active ingredient is reduced.
  • the content of the silicone oil exceeds the above-mentioned range, the emulsion particle size in the emulsion can not be optimized and the stability of the emulsion is reduced.
  • Silicone oils of the present invention comprising the aforementioned ingredients can be prepared according to conventional methods known in the art.
  • the first alkyl alkoxysilane, the second alkyl alkoxysilane, the third siloxane compound, the organic solvent, and water are added to the reactor, and the reactor is cooled to remove acid components such as hydrochloric acid at low temperature.
  • Substituted by hydroxysilane (injection), and then heated to about 50 ⁇ 70 °C to carry out hydrolysis and condensation reaction, stirring and refluxing under reduced pressure to proceed the pressureless purification Silicone oil (silicone polymer) can be obtained.
  • the organic solvent which can be used in the process of obtaining the said silicone oil can use the conventional organic solvent known in the art.
  • N-methyl pyrrolidinone dimethylformamide
  • Alcohols such as methanol, ethanol, iso-propanol (IPA), N-butanol, iso-butanol, 2-butanol, 1-pentanol and the like.
  • methanol and isopropyl alcohol (IPA) are mixed.
  • water is not particularly limited, it is preferable to use distilled water, purified water or pure water.
  • composition of the silicone oil in the present invention is not particularly limited, for example, 15 to 50% by weight of the first alkyl alkoxysilane, 10 to 40% by weight of the second alkylalkoxysilane, based on 100% by weight of the total weight of the silicone oil It may include 10 to 30% by weight of the siloxane compound, 5 to 15% by weight of the organic solvent and the remaining amount of water to satisfy the 100% by weight of the silicone oil.
  • the silicone oil Preferably, based on 100% by weight of the total weight of the silicone oil, 15 to 40% by weight of the first alkyl alkoxysilane, 10 to 35% by weight of the second alkylalkoxysilane, 5 to 30% by weight of the third siloxane compound, organic It may be a composition comprising a residual amount of water to satisfy the solvent 5 to 15% by weight and 100% by weight of the silicone oil. At this time, the content of water may be in the range of 5 to 60% by weight.
  • the emulsifier can be used without limitation conventional emulsifier components known in the art.
  • the emulsifier may be selected from anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers or zwitterionic emulsifiers alone or in combination.
  • it is to use a polyvinyl alcohol ((Poly Vinyl Alcohol, PVA) -based emulsifier that can improve the emulsion safety.
  • the content of the emulsifier is not particularly limited, but may be, for example, 10 to 30 parts by weight relative to 100 parts by weight of the total silicone emulsion water repellent, preferably 15 to 25 parts by weight.
  • the content of the emulsifier is less than the above-mentioned range, it is difficult to obtain a stable emulsion, and when it exceeds the above-mentioned range, the water-repellent active ingredient is relatively low, and it is difficult to obtain sufficient water absorption preventing performance by the hydrophilic group of the emulsifier (surfactant). Therefore, the water repellent performance is lowered.
  • the use ratio of the emulsifier and water may be in the range of 1: 8 to 10 weight ratio, and preferably in the range of 1: 8.5 to 9.5.
  • the composition of the silicone emulsion water repellent is based on 100% by weight of the total water repellent, silicone oil 30 to 70% by weight; And a residual amount of water satisfying 10 to 30% by weight of the emulsifier and 100% by weight of the water repellent.
  • Silicone emulsion water repellent agent according to the invention, one or two or more additives selected from the group consisting of conventional additives known in the art, such as emulsion protective colloids, heat stabilizers, pH adjusting agents, fungicides, preservatives, antibacterial agents and antifoaming agents. It may optionally include within the range that does not adversely affect the dispersibility and water repellency performance of the aqueous water-repellent emulsion.
  • the emulsion protective colloids include fumed silica (Fumed Silica) for improving the thickening and viscoelasticity of the emulsion.
  • the emulsion protective colloid agent may be used in consideration of the storage stability of the emulsion, particle diameter, viscosity, viscoelasticity, or the like, or does not require long-term storage stability, and according to the needs of the user.
  • the heat stabilizer is to impart heat resistance to the aqueous water-repellent emulsion to have a storage stability with long-term storage at a high temperature of more than room temperature (20 °C or more), for example urea (urea) may be used.
  • urea urea
  • the pH adjusting agent is added to prevent hydrolysis of the first alkylalkoxysilane, the second alkylalkoxysilane and the third siloxane compound by adjusting the pH of the aqueous water-repellent emulsion.
  • pH adjusting agents may be selected from alkaline compounds, including organic bases and inorganic bases and salts thereof, or buffers such as aqueous sodium acetate solution.
  • the fungicide is selected from conventional fungicides having a bactericidal effect.
  • the preservative is selected from conventional preservatives that prevent the emulsion from deteriorating.
  • 1.2-benzoisothiazoline-3 etc. can be used as an example.
  • the antimicrobial agent is selected from conventional antimicrobial agents having the effect of antibacterial, antifungal and the like.
  • conventional antimicrobial agents having the effect of antibacterial, antifungal and the like.
  • 2-n-octyl-4-isothiazoline-3 or the like can be used.
  • the antifoaming agent may be used a conventional antifoaming agent to suppress the foaming of the emulsion.
  • additives are not particularly limited, but examples thereof include pigments, flame retardants, surface conditioners, curing accelerators, leveling agents, UV absorbers, skinning inhibitors, and dispersants.
  • the addition amount of the additive is not particularly limited and may be added within a range in which the water repellent performance of the silicone emulsion water repellent does not decrease.
  • Silicone emulsion water repellents include silicone oils containing a first alkylalkoxysilane, a second alkylalkoxysilane and a third siloxane-based mixture; Emulsifier, water can be obtained by mixing and then stirring to emulsify.
  • an emulsifier eg, PVA 10
  • a silicone-based water repellent in a white emulsion state may be prepared, in which case the average particle size of the emulsion is 2.5 to 3.0 ⁇ m.
  • the emulsifying method may use a conventional emulsifier known in the art, for example, a homomixer or a high speed stirrer may be used.
  • the silicone emulsion water-repellent agent of the present invention may include oil-in-water (O / W type, oil-in-water type) emulsion particles, preferably silicone oil is an oil-in-water type granulated in the average particle size of 2.5 ⁇ 3.0 ⁇ m range ( O / W type) emulsion.
  • the size of the emulsion particles in the silicone-based emulsion water repellent agent has an average particle size of 2.5 ⁇ 3.0 ⁇ m, the hydrolysis of the silicone compound, which is a water-repellent active ingredient hardly occurs by water, so that the emulsion particles are stably dispersed, even if time passes The emulsion particles remain stable in a uniformly dispersed state. Therefore, the size of the emulsion (emulsion particle) in the silicone-based emulsion water repellent is preferably adjusted to have a uniform diameter of 2.5 ⁇ 3.0 ⁇ m, more preferably has a diameter of 2.8 ⁇ 3.0 ⁇ m.
  • the size of the emulsion particles may be appropriately adjusted according to the emulsification conditions such as the type and amount of the silicone-based compound, the rotational speed of the emulsifier or the time of emulsification.
  • the silicone-based emulsion water repellent prepared as described above may be used as it is or diluted with a certain concentration in an aqueous solvent or water.
  • the dilution concentration may be appropriately adjusted according to the needs of the user, for example, may be 1 to 15%, preferably 3 to 7%.
  • Silicone emulsion water repellent of the present invention can be applied to any product or use that can exhibit a water-repellent effect, and preferably may be used for coating such as fiber, yarn, fabric, film.
  • the water-repellent processing method of the fabric according to the present invention is not limited only by the following method, and the steps of each process may be modified or optionally mixed as necessary.
  • the water-repellent processing method of the present invention can be water-repellent according to conventional methods known in the art, except for using the silicone emulsion water-repellent agent.
  • the water repellent treatment for example, (i) performing a step of immersing the fabric in the above-described silicone-based emulsion water repellent agent and padding ('S10 step'); And (ii) it may comprise a step of drying and curing the fabric ('S20 step').
  • the fabric may use any conventional fabric known in the art without limitation, and for example, a general woven or non-woven fabric may be used.
  • the woven fabric or nonwoven fabric is, for example, a woven fabric or a nonwoven fabric manufactured by using one or two or more kinds of synthetic resin fibers such as polyester fibers, viscose rayon fibers, polyamide fibers, polyurethane fibers, acrylic fibers, polyolefin fibers, or cellulose fibers. ; Woven or nonwoven fabrics made from cotton (e.g., cotton, cotton, etc.); Or it may be a woven or nonwoven fabric prepared by mixing the synthetic resin fibers and cotton. Among the above, it is preferable to use a woven fabric made of polyester fiber, viscose rayon fiber, polyamide fiber, polyester fiber and cotton, or a mixture of polyester fiber and viscose rayon, but is not limited thereto.
  • Polyester woven fabrics are woven fabrics using polyester fibers that have been stretched with little or no elongation, and such polyester fabrics have high tension, low hygroscopicity, and good chemical resistance.
  • stretch fabric materials such as spantex can be used.
  • the thickness of the fabric is not particularly limited.
  • the fabric is immersed in a silicone emulsion water repellent to proceed with coating, wherein the silicone emulsion water repellent may be used as it is, or diluted with a certain concentration in an aqueous solvent or water.
  • the dilution concentration may be appropriately adjusted according to the user's requirements, for example, may be 1 to 15%, specifically 3 to 7%.
  • step S10 the process of immersing the fabric in a silicone-based emulsion water repellent (coating solution) diluted to 3 to 7% and padding at a speed of 1 to 3 rpm under a pressure of 0.1 to 0.3 MPa It can be carried out one or more times.
  • a silicone-based emulsion water repellent (coating solution) diluted to 3 to 7% and padding at a speed of 1 to 3 rpm under a pressure of 0.1 to 0.3 MPa It can be carried out one or more times.
  • the silicone-based emulsion water repellent When using the silicone-based emulsion water repellent, it is preferable to adjust the amount of impregnation or to adjust the degree of curing by adjusting the solids content of the coating solution according to the required physical properties of the final product.
  • the silicone emulsion water-repellent agent is preferably made of 30 to 50% of the solid content, if the solid content is less than 30%, the water content is too high to be impregnated, hardly cured even if dried later, the solid content exceeds 50% If the moisture content is too small, it may be excessively hardened dry.
  • the pick-up rate of the padded fabric is not particularly limited and may be appropriately adjusted according to the type of fabric.
  • the average pick-up rate may be in the range of about 20 to 120%, and is preferably adjusted to about 80%.
  • the silicone emulsion water repellent remaining on the surface of the padding is completed, or penetrated to the inner pore structure of the fabric to harden to bond to the fabric.
  • the curing conditions are not particularly limited, and for example, curing at a temperature of 130 to 180 ° C. for 1 to 10 minutes is preferable.
  • the present invention provides a water-repellent fabric prepared through the above-described water-repellent process.
  • the initial water repellency measured by the method of AATCC 22-1996 is ISO 5 grade
  • the water repellency of 10 washes measured by the AATCC 22-1996 method is preferably ISO 5 grade.
  • the water-repellent fabric of the present invention prepared as described above has a structure in which the web structure of the fabric woven with fibers is maintained as it is processed as a permeable silicone-based emulsion water-repellent agent, the lower the breathability of the final fabric by introducing a water-repellent coating layer Can be minimized.
  • Fabrics prepared as described above can be applied without limitation, such as clothing products, outdoor products, medical products, indoor or outdoor interior products that require water repellent performance. More specifically, there are clothes, tents, bags, covers, cases, medical products, wallpaper, flooring materials, interior materials, exterior materials, surface materials, carpets, interior accessories, and the like.
  • 3- (acryloyloxypropyl) trimethoxysilane (SG007), which is a raw material used to prepare a silicone water repellent, and hexyltriethoxysilane (Hexyltriethoxysilane ( SM008)), [3- (Methacryloyloxy) propyl] trimethoxysilane] ([3- (Methacryloyloxy) propyl] trimethoxysilane (SV002)), Hexamethyldisiloxane (HMDSO) are the Aldrich Company ( Aldrich).
  • Example 1 is a graph showing the average particle size of the silicone emulsion prepared in Example 1-2. As shown in FIG. 1, the silicon emulsion particles maintain the shape of a Gaussian distribution, wherein the average particle size of the silicone emulsion was about 2.9 ⁇ m.
  • T / C 30 male single fabric was prepared by cutting horizontally and vertically 180 ⁇ 180 mm.
  • Example 1 As shown in Table 1, the water repellent composition of Example 1 exhibited an average pick up rate of about 58%. It can be seen that this is a result similar to the average pick up rate of the water repellent composition of Comparative Examples 1 to 3.
  • the fabric was immersed for the same time in a state in which the concentration of the water repellent composition of Example 1 and Comparative Examples 1 to 3 was fixed at 4.5%, and then hardened at 160 ° C. for 10 minutes to obtain a fabric coated with a water repellent. .
  • Water repellency evaluation The initial water repellency was evaluated by AATCC test method 22-1996, water repellency: spray test method using the fabric coated with the water repellent agent.
  • the initial water repellency of the water repellent composition of Example 1 exhibited a characteristic of 100 (ISO 5).
  • Example 1 Using the fabric coated with the water repellent coating of Example 1 and Comparative Examples 1 to 3 was carried out a water-repellent sustainability test according to the number of washing.
  • the fabric was immersed for the same time in a state in which the concentrations of the water repellent compositions of Examples 1 and Comparative Examples 1 to 3 were fixed at 4.5%, and then curing was performed at 160 ° C. for 10 minutes and a water repellency sustainability test was performed. These results are shown in FIG. 2.

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  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The present invention provides a water-repellent agent of a silicone-based emulsion comprising a silicone oil, an emulsifier and water, wherein the silicone oil contains (a) a first alkylalkoxysilane having an alkyl group of 6 to 20 carbon atoms, (b) a second alkylalkoxysilane of 1 to 6 carbon atoms having an acryloyloxyalkyl group or a methacryloyloxyalkyl group, and (c) a third siloxane-based compound; and a water-repellent processing method using the same. The present invention is not only harmless to humans and the environment, but also can exhibit excellent water repellency and excellent water-repellent and washing durability.

Description

실리콘계 에멀젼 발수제 및 이를 이용한 원단의 발수 가공방법Silicone emulsion water repellent and fabric repellent processing method using the same
본 발명은 신개념 친환경 제조공법과 소재를 사용하여 환경 유해를 최소화하고, 우수한 발수력과 세탁 내구성을 동시에 발휘하는 실리콘계 에멀젼 발수제 및 이를 이용한 원단의 발수 가공방법에 관한 것이다. The present invention relates to a silicone-based emulsion water repellent and a water-repellent processing method of the fabric using the same concept to minimize environmental hazards, simultaneously exhibit excellent water repellency and laundry durability using a new concept eco-friendly manufacturing method and materials.
기존 발수가공제로는 C8 타입 (탄소원자 8개 사슬 단위 구조의 고분자 물질)의 불소화 화합물이 사용되고 있다. 특히 과불소화 옥타황산 (PFOS)은 면역 및 생식능력을 저하시키고 갑상선 질환 등의 원인 물질로 판명되어 2009년 스톡홀름 당사자 회의에서 국제 환경 유해 물질로 지정된 바 있다. Conventional water-repellent agents are used fluorinated compounds of the C8 type (high molecular weight 8 carbon carbon chain unit structure). In particular, perfluorinated octasulfate (PFOS) has been identified as a cause of lowering of immunity and fertility, thyroid disease, etc. and was designated as an international environmental hazardous substance at the 2009 Stockholm Party Conference.
전술한 규제를 피하기 위해서, 현재 세계 주요 발수제 메이커들은 기존 C8 타입(탄소 8개) 대신 C6 (탄소 6개) 타입의 물질로 변경한 불소계 제품을 개발해서 판매하고 있다. 그러나 이러한 C6 타입의 불소계 제품도 인체 유해면에서 여전히 안심할 수 없는 실정이며, 실제로 국제 환경보호 단체인 그린피스(Greenpeace)는 C6 타입의 불소화합물도 역시 C8 타입과 유사한 화학구조를 가지고 있다는 보고를 통해 아웃도어 제조용으로 사용되는 불소계 화합물로 인한 환경오염의 심각성을 밝히고, 다국적 의류제조 기업들에게 불소가 포함되지 않은 대체물질 사용을 강력히 촉구하고 있다.In order to circumvent the aforementioned regulations, the world's major water repellent manufacturers are now developing and selling fluorine-based products that have been changed to C6 (6 carbon) type materials instead of C8 (8 carbon) types. However, these C6 fluorine-based products are still unreliable in terms of human health. In fact, Greenpeace, an international environmental protection organization, reported that C6 type fluorine also has a chemical structure similar to that of C8. It reveals the severity of environmental pollution caused by fluorine-based compounds used for door manufacturing and strongly urges multinational apparel companies to use alternatives that do not contain fluorine.
이에 따라, 환경 및 인체에 무해하면서 발수성 및 발수지속성이 우수한 신규 발수제 물질에 대한 연구가 지속적으로 요구되고 있는 실정이다. Accordingly, research on a new water repellent material that is harmless to the environment and the human body and is excellent in water repellency and water repellency sustainability is continuously required.
본 발명은 전술한 문제점을 해결하기 위해서 안출된 것으로서, 신개념 친환경 제조공법과 소재를 사용하여 환경 유해를 최소화하는 비(非)불소 실리콘계 발수제를 제공하는 것을 목적으로 한다. The present invention has been made to solve the above problems, and an object of the present invention is to provide a non-fluorinated silicone-based water-repellent agent using a new concept eco-friendly manufacturing method and materials to minimize environmental hazards.
또한 본 발명은 전술한 실리콘계 발수제를 사용하여 우수한 발수력과 발수지속력, 세탁 내구성을 발휘할 수 있는 원단의 발수가공방법을 제공하는 것을 또 다른 목적으로 한다. In another aspect, the present invention is to provide a water-repellent processing method of the fabric that can exhibit the excellent water-repellent power, water repellent durability, washing durability using the above-described silicone-based water repellent agent.
상술한 목적을 달성하기 위해, 본 발명은 실리콘 오일; 유화제 및 물을 포함하는 실리콘계 에멀젼 발수제로서, 상기 실리콘 오일은 탄소수 6 ~ 20의 알킬기를 갖는 제1알킬알콕시실란; 아크릴로일옥시알킬기 또는 메타크릴로일옥시알킬기를 갖는 탄소수 1 ~ 6의 제2알킬알콕시실란; 및 제3실록산계 화합물을 함유하는 실리콘계 에멀젼 발수제를 제공한다. In order to achieve the above object, the present invention is a silicone oil; A silicone emulsion water repellent agent comprising an emulsifier and water, wherein the silicone oil comprises: a first alkylalkoxysilane having an alkyl group having 6 to 20 carbon atoms; A second alkylalkoxysilane having 1 to 6 carbon atoms having an acryloyloxyalkyl group or a methacryloyloxyalkyl group; And a silicone emulsion water repellent containing a third siloxane compound.
본 발명의 바람직한 일례에 따르면, 상기 제1알킬알콕시 실란은 헥실트리메톡시실란, 헥실트리에톡시실란, 헵틸트리메톡시실란, 헵틸트리에톡시실란, 옥틸트리메톡시실란, 옥틸트리에톡시실란, 노닐트리메톡시실란, 노닐트리에톡시실란, 데실트리에톡시실란, 운데실트리에톡시실란 및 도데실트리에톡실란으로 이루어진 군에서 선택되는 1종 이상일 수 있다. According to a preferred embodiment of the present invention, the first alkylalkoxy silane is hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane , Nonyltrimethoxysilane, nonyltriethoxysilane, decyltriethoxysilane, undecyltriethoxysilane and dodecyltriethoxysilane may be one or more selected from the group consisting of.
또한 상기 제2알킬알콕시실란은 아크릴로일옥시프로필트리메톡시실란, 메타크릴로일옥시프로필트리메톡시실란, 아크릴로일옥시프로필트리에톡시실란, 및 메타크릴로일옥시프로필트리에톡시실란으로 이루어진 군에서 선택되는 1종 이상일 수 있다. In addition, the second alkyl alkoxysilane is acryloyloxypropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, acryloyloxypropyltriethoxysilane, and methacryloyloxypropyltriethoxysilane It may be one or more selected from the group consisting of.
또한 상기 제3실록산계 화합물은 헥사메틸디실록산, 옥타메틸트리실록산, 데카메틸테트라실록산, 디메틸테트라메톡시디실록산, 트리메틸트리메톡시디실록산, 및 테트라메틸테트라메톡시트리실록산, 헥사메틸테트라메톡시테트라실록산으로 이루어진 군에서 선택되는 1종 이상일 수 있다. In addition, the third siloxane compound is hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dimethyltetramethoxydisiloxane, trimethyltrimethoxydisiloxane, and tetramethyltetramethoxytrisiloxane, hexamethyltetramethoxytetra It may be at least one selected from the group consisting of siloxanes.
본 발명의 바람직한 다른 일례에 따르면, 상기 실리콘 오일은 당해 실리콘 오일 전체 중량 100 중량%를 기준으로, 제1알킬알콕시실란 15 ~ 50 중량%, 제2알킬알콕시실란 10 ~ 40 중량%, 제3실록산계 화합물 10 ~ 30 중량%, 유기용제 5 ~ 15 중량% 및 상기 실리콘 오일 100 중량%를 만족시키는 잔량의 물을 포함하는 조성일 수 있다. According to another preferred embodiment of the present invention, the silicone oil is based on 100% by weight of the total weight of the silicone oil, 15 to 50% by weight of the first alkyl alkoxysilane, 10 to 40% by weight of the second alkylalkoxysilane, the third siloxane 10 to 30% by weight of the acid-based compound, 5 to 15% by weight of the organic solvent and 100% by weight of the silicone oil may be a composition comprising a residual amount of water.
본 발명의 바람직한 또 다른 일례에 따르면, 상기 에멀젼은 실리콘 오일이 평균입도 2.5 ~ 3.0 ㎛ 범위로 입자화된 수중유형(O/W type) 에멀젼일 수 있다. According to another preferred embodiment of the present invention, the emulsion may be an oil-in-water (O / W type) emulsion in which silicone oil is granulated in the average particle size of 2.5 ~ 3.0 ㎛ range.
또한 본 발명은 전술한 실리콘계 에멀젼 발수제를 이용한 원단의 발수가공방법을 제공한다. In another aspect, the present invention provides a water-repellent processing method of the fabric using the above-described silicone emulsion water-repellent agent.
보다 구체적으로, 상기 발수가공방법은 (i) 원단을 상기 실리콘계 에멀젼 발수제에 침지한 후 패딩하는 공정을 실시하는 단계; 및 (ii) 상기 원단을 건조 및 경화하는 단계를 포함하여 구성될 수 있다. More specifically, the water-repellent processing method includes the steps of (i) immersing the fabric in the silicone emulsion water-repellent agent and then padding; And (ii) drying and curing the fabric.
본 발명에 따른 실리콘계 에멀젼형 발수제는 인체에 무해한 물질로 구성되어 있으므로 환경호르몬에 대한 안정성을 증진시킬 수 있으며, 발수성과 세탁내구성이 우수한 섬유용 발수제 조성물이다.Silicone emulsion type water repellent according to the present invention is composed of a material harmless to the human body can improve the stability to environmental hormones, and is a water repellent composition for fibers excellent in water repellency and wash durability.
또한 비(非)불소계인 실리콘 성분을 사용하므로, 발수처리 후 섬유 고유의 질감을 유지시켜 터치감이 우수하여 유연제 공정을 생략할 수 있는 장점을 가지고 있다.In addition, since the non-fluorine-based silicone component is used, the texture of the fiber after water repellent treatment is excellent, and the touch feeling is excellent, so that the softener process can be omitted.
도 1은 실시예 1에서 제조된 실리콘계 에멀젼(emulsion) 입자의 평균입도 분포를 나타내는 그래프이다. 1 is a graph showing the average particle size distribution of the silicone emulsion particles prepared in Example 1. FIG.
도 2는 실시예 1 및 비교예 1 ~ 3의 발수제를 이용하여 세탁횟수에 따른 발수성 지속성 테스트 결과를 나타내는 그래프이다. 2 is a graph showing the results of the water repellency sustainability test according to the number of washing times using the water repellent agent of Example 1 and Comparative Examples 1 to 3.
이하 본 발명을 상세히 설명한다. Hereinafter, the present invention will be described in detail.
종래 불소계 발수제는 인체나 환경에 유해할 뿐만 아니라, 연잎 효과를 통해 섬유의 표면만을 개질하여 물 분자가 표면을 통과할 수 없도록 함으로써 발수효과를 나타내었다.Conventional fluorine-based water repellents are not only harmful to the human body or the environment, but also have a water repellent effect by modifying only the surface of the fiber through the lotus leaf effect to prevent water molecules from passing through the surface.
이에, 본 발명에서는 인체나 환경에 무해할 뿐만 아니라 섬유의 표면 및 섬유의 내부까지 침투하여 발수가 가능한 침투형 실리콘계 에멀젼 발수제를 제공하고자 한다. Accordingly, the present invention is to provide a penetration-type silicone emulsion water-repellent agent that is not only harmless to the human body or the environment, but also penetrates to the surface of the fiber and the inside of the fiber.
본 발명에 따른 신규 발수제는 비(非)불소계인 실리콘 성분을 사용하므로, 인체나 환경에 무해하여 발수 가공에 의한 환경 피해를 완벽하게 방지할 수 있다. 또한 상기 실리콘 성분은 수 마이크로미터(㎛) 단위의 에멀젼 입자를 이루고 있는데, 이러한 에멀젼의 미세입자는 섬유의 표면에 잔존할 뿐만 아니라 섬유 속(束)까지 깊숙이 침투하여 섬유와 결합하기 때문에, 초기 발수도 및 발수지속성이 우수하다. 또한 상기 실리콘계 발수제는 섬유의 표면 및 내부까지 침투한 후 경화되어 섬유와 견고하게 결합하고 있으므로, 세탁에 의한 발수제 유출이 최소화되어 세탁 내구성이 매우 높다. Since the novel water repellent according to the present invention uses a non-fluorine-based silicone component, it is harmless to a human body or the environment, and thus can completely prevent environmental damage caused by water repellent processing. In addition, the silicone component is composed of emulsion particles of several micrometers (μm) unit, the fine particles of the emulsion not only remain on the surface of the fiber, but also penetrates deep into the fiber and binds to the fiber, the initial water repellency Excellent degree of water and water repellency In addition, since the silicone-based water repellent penetrates to the surface and the inside of the fiber and is hardened to bind the fiber firmly, the outflow of the water repellent agent by washing is minimized, and the washing durability is very high.
아울러 실리콘계이므로, 종래 불소계에 비해 발수처리 후 섬유 고유의 질감을 유지시켜 터치감이 우수하여 유연제 공정을 생략할 수 있는 장점을 가지고 있다.In addition, since it is silicon-based, the texture of the fiber after water repellent treatment is superior to that of the conventional fluorine-based, so it has an excellent touch feeling and has the advantage of eliminating the softener process.
<실리콘계 에멀젼 발수제><Silicone emulsion water repellent>
본 발명의 실리콘계 에멀젼 발수제는 크게 실리콘 오일; 유화제 및 물을 포함하되, 상기 실리콘 오일은 (a) 탄소수 6 ~ 20의 알킬기를 갖는 제1알킬알콕시실란; (b) 아크릴로일옥시알킬기 또는 메타크릴로일옥시알킬기를 갖는 탄소수 1 ~ 6의 제2알킬알콕시실란; 및 (c) 제3실록산계 화합물을 함유하는 것을 특징으로 한다. Silicone emulsion water repellent of the present invention is largely silicone oil; An emulsifier and water, wherein the silicone oil comprises: (a) a first alkylalkoxysilane having an alkyl group of 6 to 20 carbon atoms; (b) a second alkylalkoxysilane having 1 to 6 carbon atoms having an acryloyloxyalkyl group or a methacryloyloxyalkyl group; And (c) a third siloxane compound.
이하, 본 발명에 따른 실리콘계 에멀젼 발수제의 각 성분 및 이의 조성에 대해 설명한다.Hereinafter, each component and its composition of the silicone emulsion water repellent agent according to the present invention will be described.
본 발명의 실리콘계 에멀젼 발수제에서, 상기 실리콘 오일을 구성하는 제1알킬알콕시실란(a)은, 당 분야에 알려진 통상적인 알킬알콕시실란을 사용할 수 있다. 일례로 6 ~ 20개의 탄소원자를 갖는 적어도 하나의 알킬기와 메톡시, 에톡시 및 프로톡시로부터 선택된 적어도 하나 이상의 알콕시기가 실리콘 원자에 직접 결합된 화합물을 사용할 수 있으며, 바람직하게는 모노알킬 트리알콕시 실란을 사용하는 것이다.In the silicone emulsion water repellent agent of the present invention, the first alkylalkoxysilane (a) constituting the silicone oil may use a conventional alkylalkoxysilane known in the art. For example, a compound in which at least one alkyl group having 6 to 20 carbon atoms and at least one alkoxy group selected from methoxy, ethoxy and ethoxy are directly bonded to a silicon atom may be used. Preferably, a monoalkyl trialkoxy silane is used. Is to use.
이때 제1알킬알콕시실란(a)의 실리콘 원자에 직접 결합되는 적어도 하나의 알킬기가 6개 미만의 탄소원자를 가지는 경우, 극도로 높은 가수분해성 및 휘발성을 보일 수 있으며, 제1알킬알콕시실란의 분자 부분이 섬유기재 표면에 도포된 후 섬유기재 표면과 너무 빠르게 반응하게 되어 에멀젼의 침투성이 지연되고, 발수 성분이 섬유기재의 표면에만 부여될 수 있다. 반면, 실리콘 원자에 직접 결합된 적어도 하나의 알킬기가 20개를 초과하는 탄소원자를 가지는 경우 그 분자량이 너무 크기 때문에 섬유기재 내부로 쉽게 침투할 수 없게 된다. In this case, when at least one alkyl group directly bonded to the silicon atom of the first alkylalkoxysilane (a) has less than 6 carbon atoms, it may exhibit extremely high hydrolyzability and volatility, and the molecular portion of the first alkylalkoxysilane After being applied to the surface of the fibrous base, it reacts too quickly with the surface of the fibrous base so that the permeability of the emulsion is delayed, and a water repellent component can be given only to the surface of the fibrous base. On the other hand, when at least one alkyl group directly bonded to a silicon atom has more than 20 carbon atoms, its molecular weight is too large to easily penetrate into the fiber base .
사용 가능한 제1알킬알콕시실란(a)의 비제한적인 예를 들면 헥실트리메톡시실란, 헥실트리에톡시실란, 헵틸트리메톡시 실란, 헵틸트리에톡시실란, 옥틸트리메톡시실란, 옥틸트리에톡시실란, 노닐트리메톡시실란, 노닐트리에톡시실란, 데실트리메톡시실란, 데실트리에톡시실란, 운데실트리메톡시실란, 운데실트리에톡시실란, 도데실트리메톡시실란, 도데실트리에톡실란 등이 있다. 이들을 단독으로 사용하거나 또는 2종 이상 혼합하여 사용될 수 있다. Non-limiting examples of usable first alkylalkoxysilane (a) include hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxy silane, heptyltriethoxysilane, octyltrimethoxysilane, octyltrie Methoxysilane, nonyltrimethoxysilane, nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane, undecyltriethoxysilane, dodecyltrimethoxysilane, dodecyl Triethoxysilane and the like. These may be used alone or in combination of two or more thereof.
또한 본 발명의 실리콘계 에멀젼 발수제에서, 상기 실리콘 오일을 구성하는 제2알킬알콕시실란(b)은, 당 분야에 알려진 통상적인 알킬알콕시실란으로서, 말단에 아크릴로일옥시기 또는 메타크릴로일옥시기와 탄소수 1 ~ 6의 알킬기를 갖는 알킬알콕시실란을 제한 없이 사용할 수 있다. In the silicone emulsion water repellent agent of the present invention, the second alkylalkoxysilane (b) constituting the silicone oil is a conventional alkylalkoxysilane known in the art, and has acryloyloxy group or methacryloyloxy group and carbon number at the terminal. An alkylalkoxysilane having an alkyl group of 1 to 6 can be used without limitation.
본 발명에서, 상기 제2알킬알콕시실란은 친수성 기능을 부여하여 원단과의 결합을 용이하게 할 목적으로 투입된다.In the present invention, the second alkylalkoxysilane is added for the purpose of providing a hydrophilic function to facilitate the bonding with the fabric.
이에 따라, 본 발명에서 사용 가능한 제2알킬알콕시실란의 비제한적인 예를 들면, 아크릴로일옥시프로필트리메톡시실란, 메타크릴로일옥시프로필트리메톡시실란, 아크릴로일옥시프로필트리에톡시실란, 메타크릴로일옥시프로필트리에톡시실란 등이 있다. 이들을 단독으로 사용하거나 또는 2종 이상 혼합하여 사용될 수 있다. Accordingly, non-limiting examples of the second alkylalkoxysilane usable in the present invention include acryloyloxypropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, and acryloyloxypropyltriethoxy Silane, methacryloyloxypropyltriethoxysilane, and the like. These may be used alone or in combination of two or more thereof.
특히 3-(아크릴로일옥시)프로필트리메톡시실란과, 3-(메타크릴로일옥시)트리메톡시실란을 혼용(混用)하면, 소수성 실리콘 고분자에 친수성을 부여할 수 있으므로 바람직하다. In particular, when 3- (acryloyloxy) propyltrimethoxysilane and 3- (methacryloyloxy) trimethoxysilane are mixed, hydrophilicity can be imparted to the hydrophobic silicone polymer, which is preferable.
또한 본 발명의 실리콘계 에멀젼 발수제에서, 상기 실리콘 오일을 구성하는 제3실록산계 화합물(c)은 당 분야에 알려진 통상적인 실록산계 화합물을 제한 없이 사용할 수 있다. In addition, in the silicone emulsion water repellent of the present invention, the third siloxane compound (c) constituting the silicone oil may be used without limitation to conventional siloxane compounds known in the art.
구체적으로, 상기 제3실록산계 화합물은 선형(linear) 구조의 실록산인 것이 바람직하며, 특히 선형 폴리디메칠실록산 (Linear Polydimethylsiloxane)인 것이 더 바람직하다Specifically, the third siloxane compound is preferably a siloxane having a linear structure, and more preferably, linear polydimethylsiloxane.
본 발명에서, 사용 가능한 제3실록산계 화합물의 비제한적인 예를 들면, 헥사메틸디실록산, 옥타메틸트리실록산, 데카메틸테트라실록산, 디메틸테트라메톡시디실록산, 트리메틸트리메톡시디실록산, 및 테트라메틸테트라메톡시트리실록산, 헥사메틸테트라메톡시테트라실록산 등이 있다. 이들을 단독으로 사용하거나 또는 2종 이상 혼용할 수 있다. In the present invention, non-limiting examples of the third siloxane compound which can be used include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dimethyltetramethoxydisiloxane, trimethyltrimethoxydisiloxane, and tetramethyltetra Methoxytrisiloxane, hexamethyltetramethoxytetrasiloxane, and the like. These may be used alone or in combination of two or more thereof.
본 발명에서는 침투성 발수제로서 소수성의 제1알킬알콕시실란, 제2알킬알콕시실란 및 제3실록산계 화합물을 주성분으로 하는데, 활성성분인 알킬알콕시실란과 실록산은 섬유 기재의 모세 기공을 통하여 표면으로부터 깊이 침투하여 모세기공 내벽의 수분과 반응함으로써, 가수분해에 의하여 히드록시기를 갖는 실라놀 및 실록사놀을 형성하게 되고, 이어서 탈수축합에 의해 고분자로 성장함으로써, 섬유기재의 모세기공 내벽 표면에 소수성 막이 형성되는 메커니즘을 나타내게 된다.In the present invention, as the permeable water repellent, hydrophobic first alkylalkoxysilane, second alkylalkoxysilane, and third siloxane compound are the main components, and the active components, alkylalkoxysilane and siloxane, penetrate deeply from the surface through the capillary pores of the fiber base. To react with water in the capillary inner wall to form silanol and siloxanol having a hydroxy group by hydrolysis, and then grow into a polymer by dehydration condensation, thereby forming a hydrophobic membrane on the surface of the capillary inner wall of the fibrous substrate. Will be displayed.
본 발명의 실리콘계 에멀젼 발수제에서, 상기 실리콘 오일의 함량은 특별히 제한되지 않으나, 일례로 전체 실리콘계 에멀젼 발수제 100 중량부 대비 30 내지 70 중량부일 수 있으며, 바람직하게는 30 내지 50 중량부 범위일 수 있다. 상기 실리콘 오일의 함량이 전술한 범위보다 작을 경우, 충분한 발수효과를 발휘하기 어려우며, 발수 유효성분의 침투성이 감소하게 된다. 또한 상기 실리콘 오일의 함량이 전술한 범위를 초과할 경우, 에멀젼 내의 유화 입자 크기를 최적화할 수 없어 에멀젼의 안정성이 감소하게 된다. In the silicone emulsion water repellent of the present invention, the content of the silicone oil is not particularly limited, but may be in the range of 30 to 70 parts by weight, preferably 30 to 50 parts by weight, relative to 100 parts by weight of the total silicone emulsion water repellent. When the content of the silicone oil is smaller than the above range, it is difficult to exhibit a sufficient water repellent effect, the permeability of the water-repellent active ingredient is reduced. In addition, when the content of the silicone oil exceeds the above-mentioned range, the emulsion particle size in the emulsion can not be optimized and the stability of the emulsion is reduced.
전술한 성분을 포함하는 본 발명의 실리콘 오일은 당 분야에 알려진 통상적인 방법에 따라 제조될 수 있다. Silicone oils of the present invention comprising the aforementioned ingredients can be prepared according to conventional methods known in the art.
일례로, 전술한 제1알킬알콕시실란, 제2알킬알콕시실란과 제3실록산계 화합물, 유기용제와 물을 반응기에 투입한 후, 상기 반응기를 냉각하여 저온에서 염산 등의 산(acid) 성분을 투입함으로써 하이드록시실란(hydroxyl silane)으로 치환하고, 이후 가수분해 (hydrolysis)와 응축반응 (condensation reaction)을 진행하기 위하여 내부온도를 50 ~ 70℃ 정도로 승온시켜 환류교반하고 감압정제를 진행함으로써 무색의 실리콘 오일(실리콘 고분자)를 얻을 수 있다.For example, the first alkyl alkoxysilane, the second alkyl alkoxysilane, the third siloxane compound, the organic solvent, and water are added to the reactor, and the reactor is cooled to remove acid components such as hydrochloric acid at low temperature. Substituted by hydroxysilane (injection), and then heated to about 50 ~ 70 ℃ to carry out hydrolysis and condensation reaction, stirring and refluxing under reduced pressure to proceed the pressureless purification Silicone oil (silicone polymer) can be obtained.
상기 실리콘 오일을 얻는 과정에서 사용 가능한 유기용제는 당 업계에 알려진 통상적인 유기용제를 사용할 수 있다. 일례를 들면, N-메틸 피롤리딘온, 디메틸포름아미드; 메탄올, 에탄올, 이소-프로판올(IPA), N-부탄올, 이소-부탄올, 2-부탄올, 1-펜탄올 등의 알코올류 등이 있다. 바람직하게는 메탄올과 이소프로필알콜(IPA)을 혼용하는 것이다. The organic solvent which can be used in the process of obtaining the said silicone oil can use the conventional organic solvent known in the art. For example, N-methyl pyrrolidinone, dimethylformamide; Alcohols such as methanol, ethanol, iso-propanol (IPA), N-butanol, iso-butanol, 2-butanol, 1-pentanol and the like. Preferably, methanol and isopropyl alcohol (IPA) are mixed.
또한 물은 특별히 제한되지 않으며, 증류수, 정제수 또는 순수 등을 사용하는 것이 바람직하다. In addition, water is not particularly limited, it is preferable to use distilled water, purified water or pure water.
본 발명에서 실리콘 오일의 조성은 특별히 제한되지 않으며, 일례로 실리콘 오일 전체 중량 100 중량%를 기준으로, 제1알킬알콕시실란 15 ~ 50 중량%, 제2알킬알콕시실란 10 ~ 40 중량%, 제3실록산계 화합물 10 ~ 30 중량%, 유기용제 5 ~ 15 중량% 및 상기 실리콘 오일 100 중량%를 만족시키는 잔량의 물을 포함할 수 있다. 바람직하게는, 상기 실리콘 오일 전체 중량 100 중량%를 기준으로, 제1알킬알콕시실란 15 ~ 40 중량%, 제2알킬알콕시실란 10 ~ 35 중량%, 제3실록산계 화합물 5 ~ 30 중량%, 유기용제 5 ~ 15 중량% 및 상기 실리콘 오일 100 중량%를 만족시키는 잔량의 물을 포함하는 조성일 수 있다. 이때 물의 함량은 5 내지 60 중량% 범위일 수 있다. The composition of the silicone oil in the present invention is not particularly limited, for example, 15 to 50% by weight of the first alkyl alkoxysilane, 10 to 40% by weight of the second alkylalkoxysilane, based on 100% by weight of the total weight of the silicone oil It may include 10 to 30% by weight of the siloxane compound, 5 to 15% by weight of the organic solvent and the remaining amount of water to satisfy the 100% by weight of the silicone oil. Preferably, based on 100% by weight of the total weight of the silicone oil, 15 to 40% by weight of the first alkyl alkoxysilane, 10 to 35% by weight of the second alkylalkoxysilane, 5 to 30% by weight of the third siloxane compound, organic It may be a composition comprising a residual amount of water to satisfy the solvent 5 to 15% by weight and 100% by weight of the silicone oil. At this time, the content of water may be in the range of 5 to 60% by weight.
한편 본 발명의 실리콘계 에멀젼 발수제에서, 유화제는 당 분야에 알려진 통상적인 유화제 성분을 제한 없이 사용할 수 있다. On the other hand, in the silicone emulsion water repellent of the present invention, the emulsifier can be used without limitation conventional emulsifier components known in the art.
상기 유화제는 음이온성 유화제, 비이온성 유화제, 양이온성 유화제 또는 양쪽이온성 유화제로부터 선택하여 단독 또는 혼합하여 사용할 수 있다. 바람직하게는 유화 안전성을 높일 수 있는 폴리비닐알콜((Poly Vinyl Alcohol, PVA)계 유화제를 사용하는 것이다.The emulsifier may be selected from anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers or zwitterionic emulsifiers alone or in combination. Preferably it is to use a polyvinyl alcohol ((Poly Vinyl Alcohol, PVA) -based emulsifier that can improve the emulsion safety.
본 발명의 실리콘계 에멀젼 발수제에서, 상기 유화제의 함량은 특별히 제한되지 않으나, 일례로 전체 실리콘계 에멀젼 발수제 100 중량부 대비 10 내지 30 중량부일 수 있으며, 바람직하게는 15 내지 25 중량부 범위일 수 있다. 이때 상기 유화제의 함량이 전술한 범위보다 작을 경우 안정한 에멀젼을 얻기가 어려우며, 전술한 범위를 초과할 경우 상대적으로 발수 유효성분이 적게 되고 유화제(계면활성제)의 친수성기에 의해서 충분한 물 흡수 방지성능을 얻기 어려워지므로, 발수 성능이 저하되게 된다. In the silicone emulsion water repellent of the present invention, the content of the emulsifier is not particularly limited, but may be, for example, 10 to 30 parts by weight relative to 100 parts by weight of the total silicone emulsion water repellent, preferably 15 to 25 parts by weight. At this time, when the content of the emulsifier is less than the above-mentioned range, it is difficult to obtain a stable emulsion, and when it exceeds the above-mentioned range, the water-repellent active ingredient is relatively low, and it is difficult to obtain sufficient water absorption preventing performance by the hydrophilic group of the emulsifier (surfactant). Therefore, the water repellent performance is lowered.
본 발명의 실리콘계 에멀젼 발수제에서, 상기 유화제와 물의 사용 비율은 1 : 8 ~ 10 중량비 범위일 수 있으며, 바람직하게는 1 : 8.5 ~ 9.5 범위일 수 있다. In the silicone emulsion water-repellent agent of the present invention, the use ratio of the emulsifier and water may be in the range of 1: 8 to 10 weight ratio, and preferably in the range of 1: 8.5 to 9.5.
본 발명의 바람직한 일례에 따르면, 상기 실리콘계 에멀젼 발수제의 조성은 전체 발수제 100 중량%를 기준으로, 실리콘 오일 30 ~ 70 중량%; 및 유화제 10 ~ 30 중량% 및 상기 발수제 100 중량%를 만족시키는 잔량의 물을 포함할 수 있다. According to a preferred embodiment of the present invention, the composition of the silicone emulsion water repellent is based on 100% by weight of the total water repellent, silicone oil 30 to 70% by weight; And a residual amount of water satisfying 10 to 30% by weight of the emulsifier and 100% by weight of the water repellent.
본 발명에 따른 실리콘계 에멀젼 발수제는, 당 분야에 알려진 통상적인 첨가제, 예컨대 에멀젼 보호콜로이드제, 내열안정제, pH조절제, 살균제, 방부제, 방균제 및 소포제로 이루어진 군에서 선택되는 1종 또는 2종 이상의 첨가제를 수성 발수 에멀젼의 분산성 및 발수 성능에 역효과를 내지 않는 범위 내에서 선택적으로 포함할 수 있다.Silicone emulsion water repellent agent according to the invention, one or two or more additives selected from the group consisting of conventional additives known in the art, such as emulsion protective colloids, heat stabilizers, pH adjusting agents, fungicides, preservatives, antibacterial agents and antifoaming agents. It may optionally include within the range that does not adversely affect the dispersibility and water repellency performance of the aqueous water-repellent emulsion.
상기 에멀젼 보호콜로이드제는 에멀젼의 증점 및 점탄성 개선용으로서 흄 실리카(Fumed Silica) 등이 있다. 이때, 상기 에멀젼 보호콜로이드제는 에멀젼의 저장안정성, 입자직경, 점도, 점탄성 등을 고려하거나, 또는 장기 저장안정성을 요구하지 않는 경우, 그리고 사용자의 요구에 따라 사용하지 않을 수도 있다.The emulsion protective colloids include fumed silica (Fumed Silica) for improving the thickening and viscoelasticity of the emulsion. At this time, the emulsion protective colloid agent may be used in consideration of the storage stability of the emulsion, particle diameter, viscosity, viscoelasticity, or the like, or does not require long-term storage stability, and according to the needs of the user.
상기 내열안정제는 수성 발수 에멀젼에 내열성을 부여하여 상온 이상 (20℃ 이상)의 고온에서 장기간 보관에 따른 저장안정성을 갖도록 하기 위한 것으로, 일례로 우레아(urea)가 사용될 수 있다.The heat stabilizer is to impart heat resistance to the aqueous water-repellent emulsion to have a storage stability with long-term storage at a high temperature of more than room temperature (20 ℃ or more), for example urea (urea) may be used.
상기 pH조절제는 수성 발수 에멀젼의 pH를 조정함으로써 제1알킬알콕시실란, 제2알킬알콕시실란과 제3실록산 화합물의 가수분해를 방지하기 위하여 첨가된다. 이러한 pH 조절제는 유기염기 및 무기 염기 그리고 이들의 염을 포함한 알칼리성 화합물이나 소디움 아세테이트(Sodium Acetate) 수용액과 같은 완충액으로부터 선택될 수 있다.The pH adjusting agent is added to prevent hydrolysis of the first alkylalkoxysilane, the second alkylalkoxysilane and the third siloxane compound by adjusting the pH of the aqueous water-repellent emulsion. Such pH adjusting agents may be selected from alkaline compounds, including organic bases and inorganic bases and salts thereof, or buffers such as aqueous sodium acetate solution.
상기 살균제는 살균효과를 가지는 통상의 살균제로부터 선택된다.The fungicide is selected from conventional fungicides having a bactericidal effect.
상기 방부제는 에멀젼이 변질되는 것을 막는 통상의 방부제로부터 선택된다. 일례로 1.2-벤조이소티아졸린-3 등을 사용할 수 있다.The preservative is selected from conventional preservatives that prevent the emulsion from deteriorating. 1.2-benzoisothiazoline-3 etc. can be used as an example.
상기 방균제는 항균, 항곰팡이 등의 효과를 갖는 통상의 방균제로부터 선택된다. 일례로, 2-n-옥틸-4-이소티아졸린-3 등을 사용할 수 있다.The antimicrobial agent is selected from conventional antimicrobial agents having the effect of antibacterial, antifungal and the like. For example, 2-n-octyl-4-isothiazoline-3 or the like can be used.
상기 소포제는 에멀젼의 기포발생을 억제하는 통상의 소포제를 사용할 수 있다.The antifoaming agent may be used a conventional antifoaming agent to suppress the foaming of the emulsion.
본 발명에서는 전술한 에멀젼 보호콜로이드제, 내열안정제, pH조절제, 살균제, 방부제, 방균제, 소포제 이외에, 다른 첨가제를 추가로 더 포함할 수 있다. 이러한 첨가제로는 특별히 한정하지는 않으나, 일례로 안료, 난연제, 표면조절제, 경화촉진제, 레벨링제, 자외선흡수제, 스키닝 억제제, 분산제 등을 들 수 있다. 이때 상기 첨가제의 첨가량은 특별히 한정하지는 않으며, 실리콘 에멀젼 발수제의 발수 성능이 저하되지 않는 범위 내에서 첨가될 수 있다.In the present invention, in addition to the above-mentioned emulsion protective colloid, heat stabilizer, pH adjusting agent, fungicide, antiseptic, antiseptic, antifoaming agent may further include other additives. Such additives are not particularly limited, but examples thereof include pigments, flame retardants, surface conditioners, curing accelerators, leveling agents, UV absorbers, skinning inhibitors, and dispersants. At this time, the addition amount of the additive is not particularly limited and may be added within a range in which the water repellent performance of the silicone emulsion water repellent does not decrease.
본 발명에 따른 실리콘계 에멀젼 발수제는 제1알킬알콕시실란, 제2알킬알콕시실란 및 제3실록산계 혼합물을 함유한 실리콘 오일; 유화제, 물을 혼합한 후 교반하여 에멀젼화시킴으로써 얻어질 수 있다. 이와 같이 유화제(예, PVA 10)를 이용하여 유화를 진행하면, 흰색 에멀젼 상태의 실리콘계 발수제가 제조될 수 있는데, 이때 에멀젼의 평균 입도가 2.5 ~ 3.0 ㎛이 되도록 진행한다. Silicone emulsion water repellents according to the present invention include silicone oils containing a first alkylalkoxysilane, a second alkylalkoxysilane and a third siloxane-based mixture; Emulsifier, water can be obtained by mixing and then stirring to emulsify. As such, when emulsifying is performed using an emulsifier (eg, PVA 10), a silicone-based water repellent in a white emulsion state may be prepared, in which case the average particle size of the emulsion is 2.5 to 3.0 μm.
상기 에멀젼화하는 방법은 당 분야에 알려진 통상적인 에멀젼화기를 사용할 수 있으며, 일례로 호모믹서(homomixer), 또는 고속교반기 등을 사용할 수 있다. The emulsifying method may use a conventional emulsifier known in the art, for example, a homomixer or a high speed stirrer may be used.
본 발명의 실리콘계 에멀젼 발수제는 수중유형 (O/W type, oil-in-water type) 에멀젼 입자를 포함할 수 있으며, 바람직하게는 실리콘 오일이 평균입도 2.5 ~ 3.0 ㎛ 범위로 입자화된 수중유형(O/W type) 에멀젼일 수 있다. The silicone emulsion water-repellent agent of the present invention may include oil-in-water (O / W type, oil-in-water type) emulsion particles, preferably silicone oil is an oil-in-water type granulated in the average particle size of 2.5 ~ 3.0 ㎛ range ( O / W type) emulsion.
상기 실리콘계 에멀젼 발수제 내의 에멀젼 입자의 크기가 2.5 ~ 3.0 ㎛의 평균 입도를 갖는 경우, 발수 유효성분인 실리콘 화합물이 물에 의한 가수분해가 거의 일어나지 않아서 에멀젼 입자가 안정적으로 분산되고, 시간이 경과하여도 에멀젼 입자가 균일하게 분산된 상태로 안정하게 유지된다. 따라서, 상기 실리콘계 에멀젼 발수제 내의 에멀젼(유화입자) 크기는 2.5 ~ 3.0 ㎛의 균일한 직경을 갖도록 조절하는 것이 바람직하며, 보다 바람직하게는 2.8 ~ 3.0 ㎛의 직경을 갖는 것이다. When the size of the emulsion particles in the silicone-based emulsion water repellent agent has an average particle size of 2.5 ~ 3.0 ㎛, the hydrolysis of the silicone compound, which is a water-repellent active ingredient hardly occurs by water, so that the emulsion particles are stably dispersed, even if time passes The emulsion particles remain stable in a uniformly dispersed state. Therefore, the size of the emulsion (emulsion particle) in the silicone-based emulsion water repellent is preferably adjusted to have a uniform diameter of 2.5 ~ 3.0 ㎛, more preferably has a diameter of 2.8 ~ 3.0 ㎛.
본 발명에서, 에멀젼 입자의 크기는 실리콘계 화합물의 종류 및 양, 유화기의 회전속도 또는 에멀젼화하는 시간 등의 에멀젼화 조건에 따라 적절히 조절될 수 있다. In the present invention, the size of the emulsion particles may be appropriately adjusted according to the emulsification conditions such as the type and amount of the silicone-based compound, the rotational speed of the emulsifier or the time of emulsification.
상기와 같이 제조된 실리콘계 에멀젼 발수제는 제조된 농도를 그대로 사용하거나 또는 수계 용제나 물에 일정 농도로 희석하여 사용할 수 있다. 이때 희석농도는 사용자의 요구에 따라 적절히 조절될 수 있으며, 일례로 1 내지 15%일 수 있으며, 바람직하게는 3 ~ 7%일 수 있다. The silicone-based emulsion water repellent prepared as described above may be used as it is or diluted with a certain concentration in an aqueous solvent or water. At this time, the dilution concentration may be appropriately adjusted according to the needs of the user, for example, may be 1 to 15%, preferably 3 to 7%.
본 발명의 실리콘계 에멀젼 발수제는 발수 효능을 발휘할 수 있는 제품이나 용도에 제한 없이 적용될 수 있으며, 바람직하게는 섬유, 실, 원단, 필름 등의 코팅 용도일 수 있다. Silicone emulsion water repellent of the present invention can be applied to any product or use that can exhibit a water-repellent effect, and preferably may be used for coating such as fiber, yarn, fabric, film.
<원단의 발수 가공방법><Water repellent processing method of the fabric>
이하, 본 발명에 따른 원단의 발수 가공방법에 대해 설명한다. 그러나 하기 방법에 의해서만 한정되는 것은 아니며, 필요에 따라 각 공정의 단계가 변형되거나 또는 선택적으로 혼용되어 수행될 수 있다. Hereinafter, the water-repellent processing method of the fabric according to the present invention. However, it is not limited only by the following method, and the steps of each process may be modified or optionally mixed as necessary.
본 발명의 발수 가공방법은 상기 실리콘계 에멀젼 발수제를 이용하는 것을 제외하고는, 당 업계에 알려진 통상적인 방법에 따라 발수가공처리될 수 있다. The water-repellent processing method of the present invention can be water-repellent according to conventional methods known in the art, except for using the silicone emulsion water-repellent agent.
상기 발수 가공처리를 위한 바람직한 일 실시예를 들면, (i) 원단을 전술한 실리콘계 에멀젼 발수제에 침지한 후 패딩하는 공정을 실시하는 단계('S10 단계'); 및 (ii) 상기 원단을 건조 및 경화하는 단계('S20 단계')를 포함하여 구성될 수 있다.For one preferred embodiment for the water repellent treatment, for example, (i) performing a step of immersing the fabric in the above-described silicone-based emulsion water repellent agent and padding ('S10 step'); And (ii) it may comprise a step of drying and curing the fabric ('S20 step').
이하, 상기 제조방법을 각 단계별로 나누어 설명하면 다음과 같다. Hereinafter, the manufacturing method will be described by dividing each step as follows.
(1) 원단을 실리콘계 에멀젼 발수제에 침지한 후 패딩한다(이하 'S10 단계'라 함). (1) The fabric is immersed in a silicone emulsion water repellent and then padded (hereinafter referred to as 'S10 step').
상기 원단은 당 분야에 알려진 통상적인 원단을 제한 없이 사용할 수 있으며, 일례로 일반적인 직포(woven) 또는 부직포(non-woven)를 사용할 수 있다.The fabric may use any conventional fabric known in the art without limitation, and for example, a general woven or non-woven fabric may be used.
상기 직포 또는 부직포는, 일례로 폴리에스테르 섬유, 비스코스 레이온 섬유, 폴리아마이드 섬유, 폴리우레탄 섬유, 아크릴 섬유, 폴리올레핀 섬유 또는 셀룰로오스 섬유와 같은 합성 수지 섬유를 단독 또는 2종 이상 이용하여 제조된 직포 또는 부직포; 면 (예, 무명이나 목화솜 등으로 제조된 실)으로 제조된 직포 또는 부직포; 또는 상기 합성 수지 섬유 및 면을 혼합하여 제조된 직포 또는 부직포일 수 있다. 상기 중에서 폴리에스테르 섬유나 비스코스 레이온 섬유, 폴리아마이드 섬유, 폴리에스테르 섬유와 면, 또는 폴리에스테르 섬유와 비스코스 레이온 등의 혼합물로 제조된 직포를 사용하는 것이 바람직하지만, 이에 제한되는 것은 아니다. 폴리에스테르 직물 원단은 연신시켜서 신장률을 거의 없게 하거나 감소시킨 폴리에스테르 섬유를 사용하여 직조된 원단으로서, 이러한 폴리에스테르 원단은 높은 장력, 낮은 흡습성, 우수한 내약품성을 갖는다. 그 외, 스판텍스와 같은 신축성 원단 소재도 사용 가능하다. 이때 원단의 두께 등 역시 특별히 제한되지 않는다.The woven fabric or nonwoven fabric is, for example, a woven fabric or a nonwoven fabric manufactured by using one or two or more kinds of synthetic resin fibers such as polyester fibers, viscose rayon fibers, polyamide fibers, polyurethane fibers, acrylic fibers, polyolefin fibers, or cellulose fibers. ; Woven or nonwoven fabrics made from cotton (e.g., cotton, cotton, etc.); Or it may be a woven or nonwoven fabric prepared by mixing the synthetic resin fibers and cotton. Among the above, it is preferable to use a woven fabric made of polyester fiber, viscose rayon fiber, polyamide fiber, polyester fiber and cotton, or a mixture of polyester fiber and viscose rayon, but is not limited thereto. Polyester woven fabrics are woven fabrics using polyester fibers that have been stretched with little or no elongation, and such polyester fabrics have high tension, low hygroscopicity, and good chemical resistance. In addition, stretch fabric materials such as spantex can be used. At this time, the thickness of the fabric is not particularly limited.
상기 원단을 실리콘계 에멀젼 발수제 내에 침지시켜 코팅을 진행하는데, 이때 실리콘계 에멀젼 발수제는 제조된 발수제를 그대로 사용하거나 또는 수계 용제나 물에 일정 농도로 희석하여 사용할 수도 있다. 이때 희석농도는 사용자의 요구에 따라 적절히 조절될 수 있으며, 일례로 1 내지 15%일 수 있으며, 구체적으로 3 ~ 7%일 수 있다. The fabric is immersed in a silicone emulsion water repellent to proceed with coating, wherein the silicone emulsion water repellent may be used as it is, or diluted with a certain concentration in an aqueous solvent or water. At this time, the dilution concentration may be appropriately adjusted according to the user's requirements, for example, may be 1 to 15%, specifically 3 to 7%.
상기 S10 단계의 바람직한 일례를 들면, 3 ~ 7%로 희석된 실리콘계 에멀젠 발수제(코팅 용액) 내에 원단을 침지하고 0.1 내지 0.3 MPa의 압력 하에서 1 ~ 3 rpm의 속도로 패딩(Padding)하는 공정을 1회 이상 실시할 수 있다. As a preferred example of the step S10, the process of immersing the fabric in a silicone-based emulsion water repellent (coating solution) diluted to 3 to 7% and padding at a speed of 1 to 3 rpm under a pressure of 0.1 to 0.3 MPa It can be carried out one or more times.
상기한 실리콘계 에멀젼 발수제를 이용시, 최종 제품의 요구되는 물성에 따라 코팅 용액의 고형분을 조절함으로써 함침량을 조절하거나 또는 경화 정도를 조절하는 것이 바람직하다. 여기서 상기 실리콘계 에멀젼 발수제는 30 내지 50%의 고형분으로 이루어지는 것이 바람직한데, 고형분이 30% 미만이면 수분의 함량이 너무 많아서 함침되기 어렵고, 나중에 건조되어도 경화되는 정도가 부족하며, 고형분이 50%를 초과하면 수분의 함량이 너무 작아서 과도하게 건조경화될 수 있다. When using the silicone-based emulsion water repellent, it is preferable to adjust the amount of impregnation or to adjust the degree of curing by adjusting the solids content of the coating solution according to the required physical properties of the final product. Here, the silicone emulsion water-repellent agent is preferably made of 30 to 50% of the solid content, if the solid content is less than 30%, the water content is too high to be impregnated, hardly cured even if dried later, the solid content exceeds 50% If the moisture content is too small, it may be excessively hardened dry.
이때 패딩된 원단의 픽업율(Pick up)은 특별히 제한되지 않으며, 원단의 종류에 따라 적절히 조절될 수 있다. 일례로 평균 픽업율은 20 내지 120% 정도의 범위를 가질 수 있으며, 80% 내외로 조절되는 것이 바람직하다. At this time, the pick-up rate of the padded fabric is not particularly limited and may be appropriately adjusted according to the type of fabric. For example, the average pick-up rate may be in the range of about 20 to 120%, and is preferably adjusted to about 80%.
(2) 패딩이 완료된 원단을 건조 및 경화(이하 'S20 단계'라 함). (2) drying and curing the fabric is padding (hereinafter referred to as 'S20 step').
상기 S20 단계에서는, 패딩이 완료된 원단의 표면에 잔류하거나, 또는 원단의 내부 기공구조까지 침투된 실리콘 에멀젼 발수제를 경화시켜 원단과 견고하게 결합하도록 한다. In the step S20, the silicone emulsion water repellent remaining on the surface of the padding is completed, or penetrated to the inner pore structure of the fabric to harden to bond to the fabric.
상기 경화 조건은 특별히 제한되지 않으며, 일례로 130 ~ 180 ℃의 온도에서 1 ~ 10분간 경화하는 것이 바람직하다. The curing conditions are not particularly limited, and for example, curing at a temperature of 130 to 180 ° C. for 1 to 10 minutes is preferable.
상기 단계를 거치게 되면, 우수한 초기 발수도, 발수지속성 및 세탁 내구성을 가진 원단을 얻을 수 있다. Through the above steps, it is possible to obtain a fabric having excellent initial water repellency, water repellency and wash durability.
<발수 원단><Water repellent fabric>
아울러, 본 발명은 전술한 발수가공을 통해 제조된 발수 원단을 제공한다. In addition, the present invention provides a water-repellent fabric prepared through the above-described water-repellent process.
보다 구체적으로, 상기 발수 원단은 AATCC 22-1996의 방법으로 측정된 초기발수도가 ISO 기준 5급이고, AATCC 22-1996 방법으로 측정된 세탁횟수 10회까지의 발수도가 ISO 기준 5급인 것이 바람직하다(하기 표 3 및 도 2 참조). 또한 상기와 같이 제조된 본 발명의 발수 원단은, 침투성 실리콘계 에멀젼 발수제로 가공됨에 따라 섬유로 직조된 원단의 웹 구조가 그대로 유지되는 구조를 가질 뿐만 아니라, 발수제 코팅층 도입에 따른 최종 원단의 통기성 저하가 최소화될 수 있다. 아울러, 발수처리 후 섬유 고유의 질감을 유지시켜 터치감이 우수하므로, 기존 세탁 공정에서 유연제 공정을 생략할 수 있는 장점이 있다. More specifically, in the water-repellent fabric, the initial water repellency measured by the method of AATCC 22-1996 is ISO 5 grade, and the water repellency of 10 washes measured by the AATCC 22-1996 method is preferably ISO 5 grade. (See Table 3 and FIG. 2 below). In addition, the water-repellent fabric of the present invention prepared as described above has a structure in which the web structure of the fabric woven with fibers is maintained as it is processed as a permeable silicone-based emulsion water-repellent agent, the lower the breathability of the final fabric by introducing a water-repellent coating layer Can be minimized. In addition, since the texture of the fiber after the water-repellent treatment to maintain the excellent touch, there is an advantage that can be omitted in the conventional washing process.
상기와 같이 제조된 원단은 발수 성능이 요구되는 의류제품, 아웃도어용 제품, 의료제품, 실내 또는 실외 인테리어용 제품 등에 제한 없이 적용할 수 있다. 보다 구체적으로 옷, 텐트, 가방, 커버, 케이스, 의료제품, 벽지, 바닥재, 내장재, 외장재, 표면재, 카펫, 인테리어 소품 등이 있다. Fabrics prepared as described above can be applied without limitation, such as clothing products, outdoor products, medical products, indoor or outdoor interior products that require water repellent performance. More specifically, there are clothes, tents, bags, covers, cases, medical products, wallpaper, flooring materials, interior materials, exterior materials, surface materials, carpets, interior accessories, and the like.
이하, 본 발명을 실시예를 통해 구체적으로 설명하나, 하기 실시예 및 실험예는 본 발명의 한 형태를 예시하는 것에 불과할 뿐이며, 본 발명의 범위가 하기 실시예 및 실험예에 의해 제한되는 것은 아니다.Hereinafter, the present invention will be described in detail by way of Examples, but the following Examples and Experimental Examples are only illustrative of one embodiment of the present invention, and the scope of the present invention is not limited to the following Examples and Experimental Examples. .
[참조예][Reference Example]
하기 본원 실시예에서 사용된 물질 중에서, 실리콘 발수제 제조에 사용되는 원료인 3-(아크릴로일옥시프로필)트리메톡시실란 (3-Acryloyloxypropyl)trimethoxysilane (SG007)), 헥실트리에톡시실란 (Hexyltriethoxysilane (SM008)), [3-(메타크릴로일옥시)프로필]트리메톡시실란] ([3-(Methacryloyloxy)propyl]trimethoxysilane (SV002)), 헥사메틸디실록산(Hexamethyldisiloxane (HMDSO))는 알드리치사(Aldrich)에서 구매하여 사용하였다. Among the materials used in the examples herein, 3- (acryloyloxypropyl) trimethoxysilane (SG007), which is a raw material used to prepare a silicone water repellent, and hexyltriethoxysilane (Hexyltriethoxysilane ( SM008)), [3- (Methacryloyloxy) propyl] trimethoxysilane] ([3- (Methacryloyloxy) propyl] trimethoxysilane (SV002)), Hexamethyldisiloxane (HMDSO) are the Aldrich Company ( Aldrich).
또한 반응 중에 사용되는 메탄올(Methanol, MeOH), 이소프로필 알코올(Isopropyl Alcohol, (IPA)), 및 35% 염산(HCl)은 대정화금에서 구매하여 사용 하였다. 반응에 사용된 물은 순수(Deionization water, D/I water)를 사용하였다. 유화에 사용되는 유화제는 PVA 205(Kuraray사)를 사용하였으며, 제조는 PVA 205 : D/I water = 1 : 9의 비율로 제조(PVA 10)하여 사용하였다.In addition, methanol (Methanol, MeOH), isopropyl alcohol (IPA), and 35% hydrochloric acid (HCl) used during the reaction were purchased from a large purified gold. Pure water (Deionization water, D / I water) was used for the reaction. The emulsifier used in emulsification was PVA 205 (Kuraray Co., Ltd.), and the preparation was carried out using PVA 205: D / I water = 1: 9 (PVA 10).
[[ 실시예Example 1] One]
1-1. 실리콘 오일 제조1-1. Silicone oil manufacturers
2 L 이중자켓 반응조에 SG007 92.5 g, SM008 216.2 g, SV002 96.6 g, HMDSO 203.7 g, MeOH 26 g, IPA 13 g, 및 D/I water 351.7 g을 투입하였으며, 반응기 내부 온도가 10 ℃가 되도록 냉각하였다. 내부 온도가 10 ℃가 되면 HCl 1 g을 투입하고, 8시간 정도 교반하였다. 8시간 경과한 후, 반응기 내부온도가 60 ℃가 되도록 온도를 승온하고, 내부온도가 60 ℃가 되면 overnight으로 환류교반하였다. 환류교반이 완료된 후, 회전증발기(rotary evaporator)를 이용하여 감압정제를 진행하여 실리콘 오일을 제조하였다. 92.5 g of SG007, 216.2 g, SV002 96.6 g, HMDSO 203.7 g, MeOH 26 g, IPA 13 g, and 351.7 g of D / I water were added to a 2 L double jacket reactor, and the reactor was cooled to 10 ° C. It was. When the internal temperature reached 10 ° C, HCl 1g was added and stirred for about 8 hours. After 8 hours had elapsed, the temperature was raised so that the reactor internal temperature was 60 ° C., and the mixture was stirred under reflux overnight. After the reflux agitation was completed, a vacuum oil was purified using a rotary evaporator to prepare a silicone oil.
1-2. 실리콘 1-2. silicon 에멀젼emulsion 발수제 제조 Water repellent manufacturers
상기 1-1에서 제조된 실리콘 오일 380 g, 유화제 (PVA 10) 430 g, 순수 (D/I water) 190 g을 혼합하여 호모믹서(homomixer)을 사용하여 혼합하였으며, 평균입도 크기가 2.5 ~ 3.0 ㎛일 때 유화를 멈추어 흰색의 실리콘 에멀젼(emulsion, Ecodry-E)을 얻었다. 380 g of the silicone oil prepared in 1-1, 430 g of emulsifier (PVA 10), and 190 g of pure water (D / I water) were mixed and mixed using a homomixer, and the average particle size was 2.5 to 3.0. Emulsion was stopped when the thickness was μm to obtain a white silicone emulsion (emulsion, Ecodry-E).
도 1은 실시예 1-2에서 제조된 실리콘 에멀젼 평균입도를 나타내는 그래프이다. 도 1에서 나타난 바와 같이, 실리콘 에멀젼 입자는 가우시안 분포 (Gaussian distribution)의 형태를 유지하고 있으며, 이때 실리콘 에멀젼(emulsion)의 평균입도 크기는 2.9 ㎛ 정도였다. 1 is a graph showing the average particle size of the silicone emulsion prepared in Example 1-2. As shown in FIG. 1, the silicon emulsion particles maintain the shape of a Gaussian distribution, wherein the average particle size of the silicone emulsion was about 2.9 μm.
상기에서 제조된 실리콘 에멀젼(emulsion) 45 g을 순수(D/I water) 1000 g에 희석하여 실리콘 에멀젼계 발수제 조성물(코팅 용액)을 제조하였다.45 g of the silicone emulsion prepared above was diluted in 1000 g of pure water (D / I water) to prepare a silicone emulsion-based water repellent composition (coating solution).
1-3. 발수제로 코팅된 원단 제조1-3. Fabrics coated with water repellent
(1) 원단 준비: T/C 30수 싱글 원단을 가로, 세로 180 × 180 mm로 잘라서 준비하였다.(1) Fabric Preparation: T / C 30 male single fabric was prepared by cutting horizontally and vertically 180 × 180 mm.
(2) 패딩(Padding): 상기 실시예 1-2에서 제조된 실리콘 발수제 조성물에 원단을 침지시킨 후, 2 MPa 압력에서 2rpm의 속도로 패더(Padder)를 통하여 원단에 발수제를 고착시켰다. (2) Padding: After the fabric was immersed in the silicone water repellent composition prepared in Example 1-2, the water repellent was fixed to the fabric through a padder at a speed of 2 rpm at 2 MPa pressure.
(3) 경화(Curing): 패딩(Padding)이 완료된 원단을 160℃에서 10분 동안 텐터(tenter)에서 경화를 진행하여 발수제가 코팅된 실시예 1의 원단을 얻었다. (3) Curing (Cadding): The fabric was completed by padding (Padding) for 10 minutes at a tenter (tenter) at 160 ℃ to obtain a fabric of Example 1 coated with a water repellent.
[[ 비교예Comparative example 1 ~ 3] 1 to 3]
본 발명을 통해 제조한 실리콘 발수제와 성능을 비교하기 위해서, 현재 시판되고 있는 일본 Nicca社 (NR-158, 불소계 발수제), 독일 Rudolf Chemical社 (Rucodry, 비불소계 발수제), 및 미국 Huntsman 社(PHOBTEX-RHP, 비불소계 발수제) 발수제 제품을 각각 비교예 1 내지 비교예 3의 발수제로 사용하였다. In order to compare the performance with the silicone water repellent produced through the present invention, currently marketed in Japan Nicca (NR-158, fluorine-based water repellent), Germany Rudolf Chemical (Rucodry, non-fluorine-based water repellent), and US Huntsman (PHOBTEX- RHP, non-fluorine-based water repellent) The water repellent product was used as the water repellent of Comparative Examples 1 to 3, respectively .
[[ 실험예Experimental Example 1.  One. 픽업율Pickup rate 평가] evaluation]
실시예 1 및 비교예 1~3의 발수제 조성물에 대해서 픽업(pick up)율을 각각 평가하였다. The pick up rate of each of the water repellent compositions of Example 1 and Comparative Examples 1 to 3 was evaluated.
보다 구체적으로, 실시예 1 및 비교예 1~3의 발수제 조성물에 T/C 원단을 침지한 후, 0.2 MPa의 압력에서 2 rpm의 속도로 원단을 패딩하였다. 전술한 과정을 3회 반복하여 실시한 후, 이들의 평균 픽업(pick up)율을 하기 수학식과 같이 계산하여 표 1에 기재하였다.More specifically, after immersing the T / C fabric in the water repellent composition of Example 1 and Comparative Examples 1 to 3, the fabric was padded at a speed of 2 rpm at a pressure of 0.2 MPa. After repeating the above-described process three times, their average pick-up rate was calculated as shown in Table 1 below.
[수학식] [Equation]
픽업율(P) = {(젖은원단 무게 - 초기원단 무게)/초기원단 무게} X 100%Pickup Rate (P) = {(Wet Fabric Weight-Initial Fabric Weight) / Initial Fabric Weight} X 100%
샘플Sample 실시예 1(Ecodry-E)Example 1 (Ecodry-E) 비교예 1(NR-158)Comparative Example 1 (NR-158) 비교예 2(Rucodry)Comparative Example 2 (Rucodry) 비교예 3(PHOBTEX-RHP)Comparative Example 3 (PHOBTEX-RHP)
픽업율(%)Pickup rate (%) 58%58% 56%56% 55%55% 57%57%
상기 표 1에 나타난 바와 같이, 실시예 1의 발수제 조성물은 58% 정도의 평균 픽업(pick up)율을 나타내었다. 이는 비교예 1 ~ 3의 발수제 조성물의 평균 픽업(pick up)율과 유사한 결과라는 것을 알 수 있다. As shown in Table 1, the water repellent composition of Example 1 exhibited an average pick up rate of about 58%. It can be seen that this is a result similar to the average pick up rate of the water repellent composition of Comparative Examples 1 to 3.
[[ 실험예Experimental Example 2. 발수성 및  2. Water repellency and 발수Water repellent 지속성 평가] Sustainability Assessment]
실시예 1 및 비교예 1 ~ 3에서 제조된 발수제 조성물을 이용하여 원단을 코팅한 후, 하기와 같은 발수성 및 발수지속성 평가를 실시하였다. After coating the fabric using the water repellent composition prepared in Example 1 and Comparative Examples 1 to 3, the water repellency and water repellency sustainability evaluation as follows.
보다 구체적으로, 실시예 1 및 비교예 1 ~ 3의 발수제 조성물의 농도를 4.5%로 고정한 상태에서 동일한 시간 동안 원단을 침지하였으며, 이후 160 ℃에서 10분간 경화를 진행하여 발수제로 코팅된 원단을 얻었다. More specifically, the fabric was immersed for the same time in a state in which the concentration of the water repellent composition of Example 1 and Comparative Examples 1 to 3 was fixed at 4.5%, and then hardened at 160 ° C. for 10 minutes to obtain a fabric coated with a water repellent. .
1) 발수성 평가: 상기 발수제로 코팅된 원단을 이용하여 AATCC 테스트 방법 22-1996, 발수성: 스프레이 테스트법으로 초기 발수도를 평가하였다.1) Water repellency evaluation: The initial water repellency was evaluated by AATCC test method 22-1996, water repellency: spray test method using the fabric coated with the water repellent agent.
2) 발수 지속성 평가: 상기 발수제로 코팅된 원단을 AATCC Guideline for Standardization of Home Laundry Test Condition (AATCC 테크니컬 매뉴얼 p. 362)에 따라 각각 세탁한 후 원단의 발수성을 측정하였다. 이때, 보다 많은 세척 횟수에서 스프레이 등급이 높은 경우, 우수한 발수지속성을 갖는 것으로 평가될 수 있다.2) Water repellency sustainability evaluation: After washing the fabric coated with the water repellent according to the AATCC Guideline for Standardization of Home Laundry Test Condition (AATCC Technical Manual p. 362), the water repellency of the fabric was measured. At this time, when the spray grade is higher in more washing times, it can be evaluated as having excellent water repellency sustainability.
상기 발수성 및 발수지속성의 결과는 각각 하기 표 3에 나타내었으며, 이때 발수성의 평가 기준은 하기 표 2와 같다. The results of the water repellency and water repellency persistence are shown in Table 3, respectively, wherein the evaluation criteria of water repellency are shown in Table 2 below.
AATCC 테스트 22-1996, 발수성 스프레이 등급AATCC Test 22-1996, Water Repellent Spray Grade
100 (ISO 5)100 (ISO 5) 상부 표면에 끈적함(sticking) 또는 젖음이 없는 것을 의미(최상의 발수성)Means no sticking or wetting on the top surface (best water repellency)
90 (ISO 4)90 (ISO 4) 상부 표면에 불규칙적인 약간의 끈적함 또는 젖음이 있는 것을 의미It means that there is some irregular stickiness or wetting on the upper surface
80 (ISO 3)80 (ISO 3) 전체 상부 표면의 스프레이 포인트에 젖음이 있는 것을 의미It means that the spray point on the entire upper surface is wet
70 (ISO 4)70 (ISO 4) 전체 상부 표면에 부분적 젖음이 있는 것을 의미Means partial wetting on the entire upper surface
50 (ISO 3)50 (ISO 3) 전체 상부 표면에 완전한 젖음이 있는 것을 의미Means complete wetting on the entire upper surface
0 (ISO 0) 0 (ISO 0) 전체 상부 표면 및 하부 표면에 완전한 젖음이 있는 것을 의미Means complete wetting on the entire top and bottom surfaces
발수제Water repellent 세탁 횟수 (AATCC 표준)Number of Washes (AATCC Standard)
0 회 (ISO)0 times (ISO) 1회(ISO)1 time (ISO) 5회 (ISO)5 times (ISO) 10회 (ISO)10 times (ISO) 15회 (ISO)15 times (ISO) 20회 (ISO)20 times (ISO)
실시예 1(Ecodry-E)Example 1 (Ecodry-E) 100 (5)100 (5) 100(5)100 (5) 100 (5)100 (5) 100 (5)100 (5) 80 (3)80 (3) 80 (3)80 (3)
비교예 1(NR-158)Comparative Example 1 (NR-158) 100 (5)100 (5) 80 (3)80 (3) 70 (2)70 (2) 70 (2)70 (2) 70 (2)70 (2) 70 (2)70 (2)
비교예 2(Rucodry)Comparative Example 2 (Rucodry) 100 (5)100 (5) 100 (5)100 (5) 90 (4)90 (4) 80 (3)80 (3) 70 (2)70 (2) 70 (2)70 (2)
비교예 3(PHOBTEX-RHP)Comparative Example 3 (PHOBTEX-RHP) 100 (5)100 (5) 100 (5)100 (5) 100 (5)100 (5) 90 (4)90 (4) 70 (2)70 (2) 70 (2)70 (2)
상기 표 3에 나타난 바와 같이, 실시예 1의 발수제 조성물의 초기 발수도는 100 (ISO 5)의 특성을 나타내었다.As shown in Table 3, the initial water repellency of the water repellent composition of Example 1 exhibited a characteristic of 100 (ISO 5).
또한 동일한 농도에서 비슷한 평균 픽업율(pick up)의 특성을 가지는 실시예 1 및 비교예 1 ~ 3의 발수제 조성물의 발수 지속성을 평가한 결과, 실시예 1의 발수 지속성이 우수하다는 것을 알 수 있었다(표 3 참조). In addition, as a result of evaluating the water repellency sustainability of the water repellent compositions of Example 1 and Comparative Examples 1 to 3 having similar average pick-up characteristics at the same concentration, it was found that the water repellency sustainability of Example 1 was excellent ( See Table 3).
[[ 실험예Experimental Example 3. 세탁 횟수에 따른  3. According to the number of washing 발수Water repellent 지속성 평가] Sustainability Assessment]
실시예 1 및 비교예 1 ~ 3의 발수제 코팅물로 코팅된 원단을 이용하여 세탁 횟수에 따른 발수 지속성 테스트를 하기와 같이 실시하였다. Using the fabric coated with the water repellent coating of Example 1 and Comparative Examples 1 to 3 was carried out a water-repellent sustainability test according to the number of washing.
보다 구체적으로, 실시예 1 및 비교예 1 ~ 3의 발수제 조성물의 농도를 4.5%로 고정한 상태에서 동일한 시간 동안 원단을 침지하였으며, 이후 160 ℃에서 10분간 경화를 진행하고 발수성 지속성 테스트를 진행하였다. 이러한 결과를 하기 도 2에 나타내었다. More specifically, the fabric was immersed for the same time in a state in which the concentrations of the water repellent compositions of Examples 1 and Comparative Examples 1 to 3 were fixed at 4.5%, and then curing was performed at 160 ° C. for 10 minutes and a water repellency sustainability test was performed. These results are shown in FIG. 2.
실험 결과, 비교예 1 (NR-158) 및 비교예 2 (Rucodry)의 발수제로 코팅된 원단은 발수 지속성이 유지되지 않았다. 또한 비교예 3의 발수제 (PHOBTEX-RHP)로 코팅된 원단은 세탁 횟수가 5회까지 ISO 기준 발수도가 5급이 유지되었다. As a result, the fabrics coated with the water repellent of Comparative Example 1 (NR-158) and Comparative Example 2 (Rucodry) did not maintain the water repellency sustainability. In addition, the fabric coated with the water repellent agent (PHOBTEX-RHP) of Comparative Example 3 was maintained at the fifth degree of water repellency of the ISO standard up to five times.
이에 비해, 실시예 1의 발수제 조성물로 코팅된 본 발명의 원단은 세탁 횟수를 10회까지 실시하여도 ISO기준 발수도가 5급이 유지되는 것을 확인할 수 있었다(도 2 참조). On the other hand, the fabric of the present invention coated with the water repellent composition of Example 1 was confirmed that even if the number of washing up to 10 times the ISO standard water repellency degree 5 is maintained (see Fig. 2).

Claims (12)

  1. 실리콘 오일; 유화제 및 물을 포함하는 실리콘계 에멀젼 발수제로서, Silicone oils; Silicone emulsion water repellent comprising an emulsifier and water,
    상기 실리콘 오일은 The silicone oil is
    탄소수 6 ~ 20의 알킬기를 갖는 제1알킬알콕시실란; First alkylalkoxysilane having an alkyl group having 6 to 20 carbon atoms;
    아크릴로일옥시알킬기 또는 메타크릴로일옥시알킬기를 갖는 탄소수 1 ~ 6의 제2알킬알콕시실란; 및 A second alkylalkoxysilane having 1 to 6 carbon atoms having an acryloyloxyalkyl group or a methacryloyloxyalkyl group; And
    제3실록산계 화합물을 함유하는 것을 특징으로 하는 실리콘계 에멀젼 발수제. A silicone-based emulsion water repellent, comprising a third siloxane compound.
  2. 제1항에 있어서, The method of claim 1,
    상기 제1알킬알콕시 실란은 헥실트리메톡시실란, 헥실트리에톡시실란, 헵틸트리메톡시 실란, 헵틸트리에톡시실란, 옥틸트리메톡시실란, 옥틸트리에톡시실란, 노닐트리메톡시실란, 노닐트리에톡시실란, 데실트리에톡시실란, 운데실트리에톡시실란 및 도데실트리에톡실란으로 이루어진 군에서 선택되는 1종 이상인 것을 특징으로 하는 실리콘계 에멀젼 발수제. The first alkylalkoxy silane is hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxy silane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, nonyltrimethoxysilane, nonyl Silicone emulsion water repellent, characterized in that at least one selected from the group consisting of triethoxysilane, decyltriethoxysilane, undecyltriethoxysilane and dodecyltriethoxysilane.
  3. 제1항에 있어서, The method of claim 1,
    상기 제2알킬알콕시실란은 아크릴로일옥시프로필트리메톡시실란, 메타크릴로일옥시프로필트리메톡시실란, 아크릴로일옥시프로필트리에톡시실란, 및 메타크릴로일옥시프로필트리에톡시실란으로 이루어진 군에서 선택되는 1종 이상인 것을 특징으로 하는 실리콘계 에멀젼 발수제. The second alkylalkoxysilane is acryloyloxypropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, acryloyloxypropyltriethoxysilane, and methacryloyloxypropyltriethoxysilane Silicone emulsion water repellent, characterized in that at least one member selected from the group consisting of.
  4. 제1항에 있어서, The method of claim 1,
    상기 제3실록산계 화합물은 헥사메틸디실록산, 옥타메틸트리실록산, 데카메틸테트라실록산, 디메틸테트라메톡시디실록산, 트리메틸트리메톡시디실록산, 및 테트라메틸테트라메톡시트리실록산, 헥사메틸테트라메톡시테트라실록산으로 이루어진 군에서 선택되는 1종 이상인 것을 특징으로 하는 실리콘계 에멀젼 발수제. The third siloxane compound is hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dimethyltetramethoxydisiloxane, trimethyltrimethoxydisiloxane, and tetramethyltetramethoxytrisiloxane, hexamethyltetramethoxytetrasiloxane Silicone-based emulsion water repellent, characterized in that at least one member selected from the group consisting of.
  5. 제1항에 있어서, The method of claim 1,
    상기 실리콘 오일은 당해 실리콘 오일 전체 중량 100 중량%를 기준으로, 제1알킬알콕시실란 15 ~ 50 중량%, 제2알킬알콕시실란 10 ~ 40 중량%, 제3실록산계 화합물 10 ~ 30 중량%, 유기용제 5 ~ 15 중량% 및 상기 실리콘 오일 100 중량%를 만족시키는 잔량의 물을 포함하는 것을 특징으로 하는 실리콘계 에멀젼 발수제. The silicone oil is based on 100% by weight of the total weight of the silicone oil, 15 to 50% by weight of the first alkyl alkoxysilane, 10 to 40% by weight of the second alkyl alkoxysilane, 10 to 30% by weight of the third siloxane compound, organic Silicone emulsion water repellent comprising a residual amount of water to satisfy 5 to 15% by weight of solvent and 100% by weight of the silicone oil.
  6. 제1항에 있어서, The method of claim 1,
    상기 실리콘 오일의 함량은 전체 실리콘계 에멀젼 발수제 100 중량부 대비 30 내지 70 중량부인 것을 특징으로 하는 실리콘계 에멀젼 발수제. The content of the silicone oil is silicone emulsion water repellent, characterized in that 30 to 70 parts by weight relative to 100 parts by weight of the total silicone emulsion water repellent.
  7. 제1항에 있어서, The method of claim 1,
    상기 유화제는 폴리비닐알콜(PVA)계 화합물인 것을 특징으로 하는 실리콘 에멀젼 발수제. The emulsifier is a silicone emulsion water repellent, characterized in that the polyvinyl alcohol (PVA) -based compound.
  8. 제1항에 있어서, The method of claim 1,
    상기 유화제와 물의 사용 비율은 1 : 8 ~ 10 중량비인 것을 특징으로 하는 실리콘계 에멀젼 발수제. Silicone emulsion water repellent, characterized in that the ratio of the emulsifier and water is 1: 8 to 10 by weight.
  9. 제1항에 있어서, The method of claim 1,
    상기 에멀젼은 실리콘 오일이 평균입도 2.5 ~ 3.0 ㎛ 범위로 입자화된 수중유형(O/W type) 에멀젼인 것을 특징으로 하는 실리콘계 에멀젼 발수제. The emulsion is a silicone-based emulsion water repellent, characterized in that the silicone oil is an oil-in-water (O / W type) emulsion in which the average particle size is in the range of 2.5 ~ 3.0 ㎛.
  10. 제1항에 있어서, The method of claim 1,
    섬유, 실, 원단, 또는 필름 코팅용인 것을 특징으로 하는 실리콘계 에멀젼 발수제. Silicone emulsion water repellent for fiber, yarn, fabric, or film coating.
  11. (i) 원단을 제1항 내지 제10항 중 어느 한 항에 기재된 실리콘계 에멀젼 발수제에 침지한 후 패딩하는 공정을 실시하는 단계; 및(i) immersing the fabric in the silicone emulsion water repellent according to any one of claims 1 to 10, followed by a step of padding; And
    (ii) 상기 원단을 건조 및 경화하는 단계(ii) drying and curing the fabric.
    를 포함하는 발수 원단의 발수가공방법. Water-repellent method of water-repellent fabric comprising a.
  12. 제11항에 있어서, The method of claim 11,
    상기 단계 (i)는 원단의 평균 픽업율이 20 ~ 120% 범위로 패딩하고, In step (i), the average pickup rate of the fabric is padded in the range of 20 to 120%,
    상기 단계 (ii)는 130 ~ 180 ℃의 온도에서 1 ~ 10분간 경화하는 것을 특징으로 하는 발수 원단의 발수가공방법. The step (ii) is a water-repellent process of water-repellent fabric, characterized in that for 1 to 10 minutes to cure at a temperature of 130 ~ 180 ℃.
PCT/KR2017/000759 2016-01-28 2017-01-23 Water-repellent agent of silicone-based emulsion and fabric water-repellent processing method using same WO2017131400A1 (en)

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