WO2016153102A1 - Water-repellent coating agent and moisture-permeable and water-proof textile product using same - Google Patents

Water-repellent coating agent and moisture-permeable and water-proof textile product using same Download PDF

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Publication number
WO2016153102A1
WO2016153102A1 PCT/KR2015/004573 KR2015004573W WO2016153102A1 WO 2016153102 A1 WO2016153102 A1 WO 2016153102A1 KR 2015004573 W KR2015004573 W KR 2015004573W WO 2016153102 A1 WO2016153102 A1 WO 2016153102A1
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Prior art keywords
water
acrylate
meth
repellent
urethane
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PCT/KR2015/004573
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French (fr)
Korean (ko)
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김유선
최동일
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(주)마이폴리머
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Publication of WO2016153102A1 publication Critical patent/WO2016153102A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1681—Antifouling coatings characterised by surface structure, e.g. for roughness effect giving superhydrophobic coatings or Lotus effect
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
    • 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

Definitions

  • the present invention relates to a water-repellent coating agent and a fiber product having moisture permeability and water resistance using the same, and more particularly, a urethane acrylate oligomer having an epoxy functional group at the end as a polymerized unit is contained in the copolymer, and when the membrane is coated on the fiber product
  • the present invention relates to a water-repellent coating agent having excellent forming ability and excellent adhesion to a urethane coating that imparts moisture permeability and water resistance, and a textile product manufactured using the same, which has improved moisture resistance and water resistance.
  • Textile products having moisture permeability and water resistance are usually manufactured in a manner of imparting moisture permeability and water resistance with a urethane coating after a water repellent treatment (KR2014-0059855A, JP2012-201042A), and impart water repellency to textile products for this purpose.
  • Paraffin-based water repellents, siloxane-based water repellents, fluorine-based water repellents and the like are conventionally known as water repellent coatings coated on the surface thereof.
  • paraffin-based and siloxane-based water repellents have problems in washing durability, and are rarely used.
  • fluorine-based water repellents are the mainstream.
  • the fluorine-based water repellent is a polymer obtained by using (meth) acrylate, which contains an alkyl substituent having 4 to 8-(CF 2 )-units at its end, as part of monomers (KR2003-0097200A, JP2011-0099077A) , KR2001-0094738A, KR2010-0074206A).
  • these fluorine-based water repellents are decomposed during the heat treatment process or washing process accompanying the coating of the water repellent agent, which is a burden on the environment such as perfluorooctane sulfonate (PFOS) or perfluorooctanoic acid (PFOA).
  • PFOS perfluorooctane sulfonate
  • PFOA perfluorooctanoic acid
  • JP2006-328624A discloses a non-fluorine-based water repellent that does not include a fluorine-substituted alkyl substituent.
  • the non-fluorine-based water repellent is an acrylic polymer containing 80% by weight or more of (meth) acrylate (specifically, stearyl acrylate) monomer units having 12 or more carbon atoms in the ester portion.
  • the adhesive force with the urethane coating which is additionally performed for the purpose of moisture permeation and waterproofing after the water repellent agent coating is not sufficient.
  • the insufficient adhesion is one of the causes of the rapid deterioration of the moisture permeability and waterproof performance when washing is performed several times.
  • the inventors of the present invention in the polymerization of the acrylate copolymer constituting the non-fluorine-based water-repellent agent, focusing on the problem that can be solved when including a monomer having a functional group that reacts with the urethane coating layer or chemically affinity
  • the present invention has been completed.
  • An object of the present invention is to provide a water-repellent coating agent that has excellent film forming ability when coated on a textile product, and excellent adhesion to a urethane coating that imparts moisture permeability and water resistance.
  • Another object of the present invention relates to a textile product manufactured using the water-repellent coating agent having improved moisture permeability and water resistance.
  • A 100 parts by weight of the water-repellent acrylate monomer;
  • B 1 to 10 parts by weight of the urethane acrylate oligomer having an epoxy functional group at the end; provides a water-repellent coating comprising a non-fluorine-based acrylic copolymer prepared by copolymerizing.
  • the (A) water repellent acrylate monomer may be decyl (meth) acrylate, isodecyl (meth) acrylate, 4-methyl-2-propylhexyl (meth) acrylate, isobornyl (meth) acrylate, dodecyl ( Meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, isooctadecyl (meth) acrylate and 2-heptyl undecyl (meth) acrylate It is preferably at least one selected from the group.
  • the epoxy compound having a hydroxyl group or a carboxyl group (B-3) is glycidyl alcohol (2,3-epoxy-1-propanol), 1- (oxirane-2-yl) -ethanol (1- (oxiran-2 -yl) ethanol), 2- (oxirane-2yl) -1,2-diphenyl-ethanol (2- (oxiran-2-yl) -1,2-diphenyl-ethanol, CAS 87141-85-3) , 4- (oxirane-2-ylmethoxy) phenol (4- (oxiran-2-ylmethoxy) phenol, CAS 20731-08-2), oxirane-2-carboxylic acid (CAS 503-11 -7) and 4- (oxirane-2-ylmethoxy) -benzoic acid) (4- (oxiran-2-ylmethoxy) benzoic acid, CAS 35217-95-9).
  • the weight average molecular weights of the urethane acrylate oligomer which has an epoxy functional group at the said (B) terminal are 1,000-50,000.
  • the present invention provides a textile product having moisture permeability and water resistance which is prepared by further urethane coating after the above-described water-repellent coating agent is treated.
  • A 100 parts by weight of the water-repellent acrylate monomer;
  • B 1 to 10 parts by weight of a urethane acrylate oligomer having an epoxy functional group at the end; provides a water-repellent coating comprising a non-fluorine-based acrylic copolymer prepared by copolymerizing. It may include a polymer unit represented by.
  • each R 1 is independently hydrogen or methyl;
  • R 2 is an alkyl substituent having 10 to 24 carbon atoms;
  • R 3 is a unit obtained by reacting a urethane prepolymer with an epoxy compound having a hydroxy group or a carboxyl group;
  • m and n are each an integer of 1 or more.
  • the front unit is a unit formed by (A) a water-repellent acrylic monomer or a polymer thereof
  • the rear unit is a unit formed by a urethane acrylate oligomer having an epoxy functional group at the terminal (B) or a polymer thereof.
  • (A) water-repellent acrylate monomer refers to a monomer that functions to impart water repellency when coated on a fiber product as a polymer. Specifically, it is an alkyl (meth) acrylate monomer which has a C10-C24 alkyl substituent.
  • the urethane acrylate oligomer unit having an epoxy functional group at the end is a unit added for the purpose of improving the coating property of the urethane coating, which is additionally performed for the purpose of moisture permeation and waterproofing after the water repellent is coated.
  • the urethane acrylate oligomer is characterized in that it has an epoxy functional group at the terminal as shown in the formula (2) below.
  • R 1 is hydrogen or methyl and 'PU' indicates the part obtained from the urethane prepolymer.
  • the urethane acrylate oligomer (B) is an urethane prepolymer having an isocyanate functional group at the (B-1) terminal, an acrylate having a hydroxyl group (B-2) and an epoxy compound having a (B-3)) hydroxy group or a carboxyl group. It can be obtained by reacting.
  • the urethane prepolymer which has an isocyanate functional group at the terminal (B-1) refers to the urethane prepolymer of the isocyanate terminal obtained by making a polyol compound and a polyvalent isocyanate compound react.
  • polystyrene resin such as polyethyleneglycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol; Polyester polyols obtained by condensation reaction of polybasic acids and glycols; 1,4-tetramethylenecarbonatediol, 1,5-pentamethylenecarbonatediol, 1,6-hexamethylenecarbonatediol, 1,2-propylenecarbonatediol, 1,3-propylenecarbonatediol, 2,2-dimethylpropylenecarbonate Polycarbonate polyols such as diol, 1,7-heptamethylene carbonate diol, 1,8-octamethylene carbonate diol, 1,9-nonane methylene carbonate diol, and 1,4-cyclohexane carbonate diol; Any of these is possible.
  • the polyol may be a difunctional diol, a trifunctional triol or more polyfunctional polyol. It is preferable
  • polyisocyanate compound (B-2) examples include 4,4'-dicyclohexyl methane diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3 Xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, norbornane diisocyanate, dicyclo Hexylmethane-2,4'-diisocyanate and the like can be used alone or in combination of two or more.
  • the (B-1) urethane prepolymer is obtained by reacting the polyol compound with a polyvalent isocyanate compound. Usually, the polyol and the diisocyanate compound are reacted in an equivalent ratio, and in order to form an isocyanate group at both ends, an excess of diisocyanate compound (1.01 to 1.1 equivalent ratio relative to one equivalent of polyol) is used.
  • (B-2) It will not specifically limit, if it is a compound which has a hydroxyl group and a (meth) acryloyl group in 1 molecule as a (meth) acrylate which has a hydroxyl group.
  • the epoxy compound having a hydroxy group or a carboxyl group (B-3) is not particularly limited as long as it is a compound having an epoxy functional group and a hydroxyl group or a carboxyl functional group simultaneously in one molecule.
  • some of the commercially available compounds are listed below:
  • the non-fluorine-based acrylic copolymer of the present invention forms a coating on the surface of the fiber product. It is understood that the properties are improved. Thereby, the wash durability of the product treated with the water repellent agent can be improved.
  • An additional effect of the introduction of the urethane acrylate oligomer is that when the urethane coating is carried out in a post process to improve the water resistance, the uniformity and adhesion of the coating can be improved.
  • the uniformity and adhesion of the coating may be improved when the urethane acrylate oligomer is polymerized together with the non-fluorine-based acrylic copolymer, in which the epoxy functional group not participating in the polymerization reacts directly with one component forming the urethane coating layer described later or is compatible. It is understood that this is because it functions as an augmentation.
  • the weight average molecular weight of the urethane acrylate oligomer which is preferably used in the present invention is in the range of 1,000 to 50,000, more preferably 2,000 to 40,000.
  • Said urethane acrylate oligomer can be used individually by 1 type or in combination of 2 or more type.
  • the content of the urethane acrylate oligomer polymer unit is used in a ratio of 1 to 10 parts by weight based on 100 parts by weight of the water repellent polymer unit.
  • the amount is less than 1 part by weight, the adhesion with the urethane coating layer and the coating property cannot be improved.
  • the water repellency of the acrylic copolymer is remarkably decreased.
  • ethylenic monomer For example, styrene, methyl styrene, (alpha) -methylstyrene, vinyl naphthalene, (meth) acrylonitrile, acetone acrylamide, vinyl chloride, vinylidene chloride, chloroethyl vinyl ether, C1-C4 Hydroxyalkyl vinyl ethers having an alkyl group, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and the like, and other diene compounds such as isoprene, pentadiene and butadiene may be copolymerized.
  • vinyl chloride or vinylidene chloride is used.
  • epoxy group containing monomers such as allyl glycidyl ether and glycidyl (meth) acrylate, N-methylol (meth) acrylamide, N-butoxymethyl, for example.
  • N-methylol group containing monomers such as all (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-chloro Azides, such as hydroxyalkyl group containing monomers, such as propyl (meth) acrylate, amide group containing monomers, such as (meth) acrylamide, N-methyl acrylamide, diacetone acrylamide, and aziridinyl ethyl (meth) acrylate
  • Polyol poly (meth) acrylates such as a lidinyl-group containing monomer, ethylene glycol di (meth) acrylate, polyoxyethylene di (meth) acrylate, and polyoxypropyl glycol di (meth) acrylate, etc. are mentioned.
  • High, preferably hydrophilic monomers are used.
  • An acryl-type copolymer can be manufactured by radical polymerization methods, such as emulsion polymerization and dispersion polymerization, for example. Specifically, after preparing a mixed solution containing a (meth) acrylate monomer having an alkyl substituent of 10 to 24 carbon atoms and a urethane acrylate monomer, an emulsifier and / or dispersing agent, a polymerization initiator and the necessary additives, known dispersion means, for example For example, a water repellent according to the present invention is prepared by emulsifying or dispersing with a dispersing means such as a homo mixer, a high pressure emulsifier or an ultrasonic wave and polymerizing.
  • a dispersing means such as a homo mixer, a high pressure emulsifier or an ultrasonic wave and polymerizing.
  • emulsifier one or more selected from nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants can be used.
  • content of an emulsifier or a dispersing agent 0.5-30 weight part with respect to 100 weight part of all monomers, Preferably 1-20 weight part is used.
  • the amount of the emulsifier or dispersant is less than 0.5 part by weight, the dispersion stability of the mixed solution tends to be lowered, and when it exceeds 30 parts by weight, the water repellency of the copolymer obtained tends to be lowered.
  • water is preferable and a mixed solvent of water and an organic solvent can be used as needed.
  • the organic solvent is not particularly limited as long as it is an organic solvent compatible with water.
  • examples of the organic solvent include alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, and diethyl.
  • Ethers such as ether, glycols such as propylene glycol, dipropylene glycol, tripropylene glycol, and the like can be used.
  • the ratio of water and an organic solvent is not specifically limited.
  • the temperature of a polymerization reaction 20 degreeC-150 degreeC is preferable.
  • the polymerization temperature is less than 20 ° C, the polymerization becomes insufficient, and when the temperature exceeds 150 ° C, control of the heat of reaction becomes difficult.
  • the weight average molecular weight of the copolymer obtained by the above-mentioned method is 100,000 or more.
  • the weight average molecular weight of the obtained non-fluorine acrylate copolymer can be adjusted by increasing or decreasing the content of the polymerization initiator, the chain transfer agent, and the polymerization inhibitor described above.
  • the content rate of a non-copolymer is adjusted to 10-50 weight%, Preferably it is 20-40 weight%.
  • water repellent agent of this invention it is also possible to add an additive etc. to the water repellent agent of this invention as needed.
  • an additive another water repellent, a crosslinking agent, an antibacterial deodorant, a flame retardant, an antistatic agent, a softening agent, etc. are mentioned.
  • the fiber product treated with the water repellent agent according to the present invention is not particularly limited, and for example, synthetic fibers such as polyester, polyurethane, polyacrylonitrile, polyvinyl alcohol, polyvinylidene chloride, polypropylene, nylon fibers; Natural or naturally derived fiber products such as cotton, hemp, silk, rayon and acetate fibers; Or a product mixed with these; the water repellent may be applied.
  • the water repellent can be treated directly on the fibers, and can be treated on fabrics, knits, nonwovens and the like.
  • the method of treating the water repellent agent to the textile product for example, coating the water repellent agent according to a known method such as dipping, spraying or coating, and then drying and curing (cure) the textile product treated with the water repellent coating. You can get it.
  • the amount to be coated can be adjusted according to the degree of water repellency required.
  • the amount of the water repellent coating agent is adjusted in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the textile product. If the coating amount is less than 0.1 part by weight, the water repellency is not sufficient, and if the coating amount is more than 10 parts by weight, the properties of the raw material may be lost.
  • Drying method A method of drying and curing a textile product treated with a water-repellent coating agent by applying pressure with a press or the like at a high temperature of 100 to 150 ° C.
  • the urethane coating liquid is usually applied in two to three times by applying and curing the pressure and drying.
  • the O / W type polyurethane emulsion was applied to the water-repellent fabrics using a comma coater at a coating amount of 180 g / m 2 , and then dried at 80 ° C. for 3 minutes to form a polyurethane coating film. Thereafter, the mixture was solidified in a 30 ° C. H 2 O / DMF (80/20 vol.%) Coagulation bath, washed in a 60 ° C. water bath, and dried at 130 ° C. to prepare a fiber product having moisture permeability and water resistance. At this time, the thickness of the coating film was about 50 ⁇ m.
  • composition of O / W Type Polyurethane Emulsion 100 parts by weight of an O / W type polyurethane resin having a solid content of 26% by mass (manufactured by Daiichi Seika Co., Ltd., ATX-10), 2 parts by weight of an isocyanate-based crosslinking agent (manufactured by Daiichi Seika Co., Ltd.) , Rezamin X), 20 parts by weight of methyl ethyl ketone / toluene / 25 parts by weight, 25 parts by weight of water / methyl ethyl ketone / 5 parts by weight]
  • Water repellency was evaluated according to the spray method specified in AATCC 22 (Washing conditions: AATCC 135, Test No. (2) (III) A (ii), normal cycle, washing temperature 41 ⁇ 3 °C, About tumble conditions). Urethane coated water-repellent fabrics were evaluated for fabrics after initial and 20 washes, respectively.
  • the peel strength between the fabric and the urethane coating while showing no significant difference in water vapor transmission rate and water resistance compared to conventional products It can be seen that the significantly increased. Specifically, it can be seen that the peel strength is improved by at least 85% or more in the case of a polyester fabric and at least 100% in the case of a nylon fabric, compared to a fabric treated with a conventional non-fluorine-based water repellent (Comparative Example 1). In addition, compared to the conventional fluorine-based water repellent (Comparative Example 2), it can be confirmed that more than 30% for polyester fabric, 40% or more for nylon fabric.
  • the initial water repellency of the non-washing was maintained at 100 as in the conventional products, while the water repellency was improved compared to the conventional products after washing, as well as the water repellency of the five washing treatments, as well as the water repellency after 20 washings.
  • the water repellency was improved compared to the conventional products after washing, as well as the water repellency of the five washing treatments, as well as the water repellency after 20 washings.

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Abstract

The present invention provides a water-repellent coating agent containing a fluorine-free acryl-based copolymer manufactured by copolymerizing, (A) with regard to 100 parts by weight of water-repellent acrylate monomer, (B) 1 to 10 parts by weight of urethane acrylate oligomer having an epoxy functional group at the terminal; and a moisture-permeable and water-proof textile product prepared using the same. The water-repellent coating agent of the present invention has an excellent film forming ability in the case of being coated on a textile product, and has excellent adhesion with urethane coating that provides moisture-permeable and water-resistant properties. Accordingly, a moisture-permeable and water-proof textile product prepared using the water-repellent coating agent has improved wash durability.

Description

발수 코팅제 및 이를 이용한 투습·방수성을 갖는 섬유제품Water repellent coating and textile products with moisture permeability and water resistance
본 발명은 발수 코팅제 및 이를 이용한 투습·방수성을 갖는 섬유제품에 관한 것으로, 보다 상세하게는 공중합체 내에 중합단위로서 말단에 에폭시 관능기를 가지는 우레탄아크릴레이트 올리고머가 포함되어, 섬유제품에 코팅되는 경우 막형성 능력이 우수하고, 또한 투습·방수성을 부여하는 우레탄 코팅과의 접착력이 우수한 발수 코팅제와, 이를 이용하여 제조되어 세탁내구성이 향상된 투습·방수성을 갖는 섬유제품에 관한 것이다.The present invention relates to a water-repellent coating agent and a fiber product having moisture permeability and water resistance using the same, and more particularly, a urethane acrylate oligomer having an epoxy functional group at the end as a polymerized unit is contained in the copolymer, and when the membrane is coated on the fiber product The present invention relates to a water-repellent coating agent having excellent forming ability and excellent adhesion to a urethane coating that imparts moisture permeability and water resistance, and a textile product manufactured using the same, which has improved moisture resistance and water resistance.
투습·방수성을 갖는 섬유제품은 통상적으로 선발수 처리 후에, 우레탄 코팅으로 투습·방수성을 부여하는 방식으로 제조되는 것이 보통으로(KR2014-0059855A, JP2012-201042A), 이 목적으로 섬유제품에 발수성을 부여하기 위하여 그 표면에 코팅되는 발수 코팅제로서 종래로부터 파라핀계 발수제, 실록산계 발수제, 불소계 발수제 등이 알려져 있다.Textile products having moisture permeability and water resistance are usually manufactured in a manner of imparting moisture permeability and water resistance with a urethane coating after a water repellent treatment (KR2014-0059855A, JP2012-201042A), and impart water repellency to textile products for this purpose. Paraffin-based water repellents, siloxane-based water repellents, fluorine-based water repellents and the like are conventionally known as water repellent coatings coated on the surface thereof.
이들 중, 파라핀계 및 실록산계 발수제는 세탁내구성에 문제가 있어 거의 사용되지 않고 있으며, 현재는 불소계 발수제가 주류를 이루고 있다.Among these, paraffin-based and siloxane-based water repellents have problems in washing durability, and are rarely used. Currently, fluorine-based water repellents are the mainstream.
한편, 상기 불소계 발수제는 통상적으로 말단에 4 내지 8개의 -(CF2)- 단위를 가지는 알킬 치환체를 포함하는 (메타)아크릴레이트를 단량체의 일부로 사용하여 얻어진 중합체이다 (KR2003-0097200A, JP2011-0099077A, KR2001-0094738A, KR2010-0074206A). 그러나, 이들 불소계 발수제는 발수제의 코팅에 수반되는 열처리공정 또는 세탁과정에서 분해되어 과불화옥탄설폰산(perfluorooctane sulfonate, PFOS) 또는 과불화옥탄산(perfluorooctanoic acid, PFOA)과 같은 환경에 부담을 주는 물질이 발생할 수 있다는 문제점이 있어 규제의 대상이 되고 있다. 또한, 이와 같은 단량체들은 가격적으로도 비싸므로 경제적이지 못하다.On the other hand, the fluorine-based water repellent is a polymer obtained by using (meth) acrylate, which contains an alkyl substituent having 4 to 8-(CF 2 )-units at its end, as part of monomers (KR2003-0097200A, JP2011-0099077A) , KR2001-0094738A, KR2010-0074206A). However, these fluorine-based water repellents are decomposed during the heat treatment process or washing process accompanying the coating of the water repellent agent, which is a burden on the environment such as perfluorooctane sulfonate (PFOS) or perfluorooctanoic acid (PFOA). There is a problem that can occur, which is a target of regulation. In addition, such monomers are expensive and are not economical.
불소계 발수제의 상술한 단점을 극복하고자 개발된 것으로, JP2006-328624A에는 불소치환 알킬 치환체를 포함하지 않는 비불소계 발수제가 개시되어 있다. 상기 비불소계 발수제는 에스테르 부분의 탄소수가 12 이상인 (메타)아크릴레이트(구체적으로는 스테아릴아크릴레이트) 단량체 단위를 80중량% 이상 포함하는 아크릴계 중합체이다.Developed to overcome the above drawbacks of the fluorine-based water repellent, JP2006-328624A discloses a non-fluorine-based water repellent that does not include a fluorine-substituted alkyl substituent. The non-fluorine-based water repellent is an acrylic polymer containing 80% by weight or more of (meth) acrylate (specifically, stearyl acrylate) monomer units having 12 or more carbon atoms in the ester portion.
그러나, 상기 비불소계 발수제의 경우는, 발수제 코팅후 추가적으로 투습·방수의 목적으로 행하여지는 우레탄 코팅과의 접착력이 충분하지 않다는 문제점이 있다. 상기 불충분한 접착은 세탁이 수회 진행되는 경우 투습·방수 성능의 급격한 저하가 발생하는 원인 중 하나가 된다.However, in the case of the non-fluorine-based water repellent agent, there is a problem that the adhesive force with the urethane coating, which is additionally performed for the purpose of moisture permeation and waterproofing after the water repellent agent coating is not sufficient. The insufficient adhesion is one of the causes of the rapid deterioration of the moisture permeability and waterproof performance when washing is performed several times.
이에, 본 발명자들은, 비불소계 발수제를 구성하는 아크릴레이트 공중합체를 중합함에 있어, 우레탄 코팅층과 반응하거나 또는 화학적으로 친화력이 있는 관능기를 가지는 단량체를 포함시키는 경우 상술한 문제점을 해결할 수 있음에 착안하여 본 발명을 완성하였다.Accordingly, the inventors of the present invention, in the polymerization of the acrylate copolymer constituting the non-fluorine-based water-repellent agent, focusing on the problem that can be solved when including a monomer having a functional group that reacts with the urethane coating layer or chemically affinity The present invention has been completed.
본 발명의 목적은 섬유제품에 코팅되는 경우 막형성 능력이 우수하고, 또한 투습·방수성을 부여하는 우레탄 코팅과의 접착력이 우수한 발수 코팅제를 제공하는 것이다.An object of the present invention is to provide a water-repellent coating agent that has excellent film forming ability when coated on a textile product, and excellent adhesion to a urethane coating that imparts moisture permeability and water resistance.
본 발명의 다른 목적은 상기 발수 코팅제를 이용하여 제조되어 세탁내구성이 향상된 투습·방수성을 갖는 섬유제품에 관한 것이다.Another object of the present invention relates to a textile product manufactured using the water-repellent coating agent having improved moisture permeability and water resistance.
본 발명에서는 (A) 발수성 아크릴레이트 단량체 100 중량부에 대하여; (B) 말단에 에폭시 관능기를 가지는 우레탄아크릴레이트 올리고머 1 내지 10중량부;를 공중합하여 제조되는 비불소계 아크릴계 공중합체를 포함하는 발수 코팅제를 제공한다.In the present invention (A) 100 parts by weight of the water-repellent acrylate monomer; (B) 1 to 10 parts by weight of the urethane acrylate oligomer having an epoxy functional group at the end; provides a water-repellent coating comprising a non-fluorine-based acrylic copolymer prepared by copolymerizing.
상기 (A) 발수성 아크릴레이트 단량체는 탄소수 10 내지 24의 알킬 치환체를 갖는 알킬 (메타)아크릴레이트인 것이 바람직하다.It is preferable that the said (A) water-repellent acrylate monomer is an alkyl (meth) acrylate which has a C10-C24 alkyl substituent.
상기 (A) 발수성 아크릴레이트 단량체는 데실 (메타)아크릴레이트, 이소데실 (메타)아크릴레이트, 4-메틸-2-프로필헥실 (메타)아크릴레이트, 이소보르닐 (메타)아크릴레이트, 도데실 (메타)아크릴레이트, 펜타데실 (메타)아크릴레이트, 헥사데실 (메타)아크릴레이트, 옥타데실 (메타)아크릴레이트, 이소옥타데실(메타)아크릴레이트 및 2-헵틸운데실(메타)아크릴레이트로 구성된 군으로부터 선택되는 하나 이상인 것이 바람직하다.The (A) water repellent acrylate monomer may be decyl (meth) acrylate, isodecyl (meth) acrylate, 4-methyl-2-propylhexyl (meth) acrylate, isobornyl (meth) acrylate, dodecyl ( Meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, isooctadecyl (meth) acrylate and 2-heptyl undecyl (meth) acrylate It is preferably at least one selected from the group.
상기 (B) 말단에 에폭시 관능기를 가지는 우레탄아크릴레이트 올리고머는 (B-1) 말단에 이소시아네이트 관능기를 가지는 우레탄 예비중합체와 (B-2) 히드록시기를 기지는 아크릴레이트 및 (B-3) 히드록시기 또는 카르복실기를 가지는 에폭시계 화합물을 반응시켜 얻어지는 화합물일 수 있다.The urethane acrylate oligomer which has an epoxy functional group at the said (B) terminal is a urethane prepolymer which has an isocyanate functional group at the (B-1) terminal, an acrylate based on (B-2) a hydroxy group, and (B-3) a hydroxyl group or a carboxyl group It may be a compound obtained by reacting an epoxy compound having a compound.
상기 (B-3) 히드록시기 또는 카르복실기를 가지는 에폭시계 화합물은 글리시딜알코올(2,3-epoxy-1-propanol), 1-(옥시란-2-일)-에탄올(1-(oxiran-2-yl)ethanol), 2-(옥시란-2일)-1,2-디페닐-에탄올(2-(oxiran-2-yl)-1,2-diphenyl-ethanol, CAS 87141-85-3), 4-(옥시란-2일메톡시)페놀(4-(oxiran-2-ylmethoxy)phenol, CAS 20731-08-2), 옥시란-2-카르복시산(oxiran-2-carboxylic acid:CAS 503-11-7) 및 4-(옥시란-2-일메톡시)-벤조산)(4-(oxiran-2-ylmethoxy)benzoic acid, CAS 35217-95-9)로 구성된 군으로부터 선택되는 하나 이상일 수 있다.The epoxy compound having a hydroxyl group or a carboxyl group (B-3) is glycidyl alcohol (2,3-epoxy-1-propanol), 1- (oxirane-2-yl) -ethanol (1- (oxiran-2 -yl) ethanol), 2- (oxirane-2yl) -1,2-diphenyl-ethanol (2- (oxiran-2-yl) -1,2-diphenyl-ethanol, CAS 87141-85-3) , 4- (oxirane-2-ylmethoxy) phenol (4- (oxiran-2-ylmethoxy) phenol, CAS 20731-08-2), oxirane-2-carboxylic acid (CAS 503-11 -7) and 4- (oxirane-2-ylmethoxy) -benzoic acid) (4- (oxiran-2-ylmethoxy) benzoic acid, CAS 35217-95-9).
상기 (B) 말단에 에폭시 관능기를 가지는 우레탄아크릴레이트 올리고머는 중량평균 분자량이 1,000 내지 50,000인 것이 바람직하다.It is preferable that the weight average molecular weights of the urethane acrylate oligomer which has an epoxy functional group at the said (B) terminal are 1,000-50,000.
또한 본 발명에서는 상술한 발수 코팅제가 처리된 다음, 추가로 우레탄 코팅되어 제조되는 투습·방수성을 갖는 섬유제품을 제공한다.In addition, the present invention provides a textile product having moisture permeability and water resistance which is prepared by further urethane coating after the above-described water-repellent coating agent is treated.
비제한적 의도로 설명하자면, 본 발명에 따르는 발수 코팅제의 주성분인 비불소계 아크릴계 공중합체에 상기 우레탄아크릴레이트 올리고머가 도입됨에 따라, 본 발명의 비불소계 아크릴계 공중합체가 섬유제품의 표면에 피막을 형성하는 성질이 향상되는 것으로 이해된다. 그에 따라, 발수제가 처리된 제품의 세탁내구성이 향상될 수 있다.As a non-limiting intention, as the urethane acrylate oligomer is introduced into the non-fluorine acrylic copolymer which is the main component of the water-repellent coating according to the present invention, the non-fluorine-based acrylic copolymer of the present invention forms a coating on the surface of the fiber product. It is understood that the properties are improved. Thereby, the wash durability of the product treated with the water repellent agent can be improved.
우레탄아크릴레이트 올리고머의 도입에 따른 추가적인 효과는, 방수성 향상을 위해서 후공정으로 우레탄 코팅이 수행되는 경우, 코팅의 균일성과 접착성이 향상될 수 있다는 점이다. 코팅의 균일성과 접착성의 향상은 우레탄아크릴레이트 올리고머가 비불소계 아크릴계 공중합체에 함께 중합되는 경우, 중합에 참여하지 않은 에폭시 관능기가, 후술하는 우레탄코팅층과 직접 반응하거나 또는 상용성 증대의 기능을 하기 때문인 것으로 이해된다.An additional effect of the introduction of the urethane acrylate oligomer is that when the urethane coating is carried out in a post process to improve the water resistance, the uniformity and adhesion of the coating can be improved. The uniformity and adhesion of the coating are improved because when the urethane acrylate oligomer is polymerized together with the non-fluorine acrylic copolymer, an epoxy functional group that does not participate in the polymerization reacts directly with the urethane coating layer described later or increases the compatibility. It is understood that.
발수코팅제Water repellent coating
본 발명에서는 (A) 발수성 아크릴레이트 단량체 100 중량부에 대하여; (B) 말단에 에폭시 관능기를 가지는 우레탄아크릴레이트 올리고머 1 내지 10중량부;를 공중합하여 제조되는 비불소계 아크릴계 공중합체를 포함하는 발수코팅제를 제공한다.상기 발수 코팅제는 예를 들어, 아래의 화학식 1로 표시되는 중합체 단위를 포함할 수 있다.In the present invention (A) 100 parts by weight of the water-repellent acrylate monomer; (B) 1 to 10 parts by weight of a urethane acrylate oligomer having an epoxy functional group at the end; provides a water-repellent coating comprising a non-fluorine-based acrylic copolymer prepared by copolymerizing. It may include a polymer unit represented by.
[화학식 1][Formula 1]
Figure PCTKR2015004573-appb-I000001
Figure PCTKR2015004573-appb-I000001
상기 식 중, R1은 각각 독립적으로 수소 또는 메틸이고; R2는 탄소수 10 내지 24의 알킬 치환체이며; R3는 우레탄 예비중합체와 히드록시기 또는 카르복실기를 가지는 에폭시계 화합물을 반응시켜 얻어지는 단위이고; m, n은 각각 1 이상의 정수이다.In the above formula, each R 1 is independently hydrogen or methyl; R 2 is an alkyl substituent having 10 to 24 carbon atoms; R 3 is a unit obtained by reacting a urethane prepolymer with an epoxy compound having a hydroxy group or a carboxyl group; m and n are each an integer of 1 or more.
상기 식에서, 앞쪽의 단위는 (A) 발수성 아크릴 단량체 또는 그 중합체가 이루는 단위이고, 뒤쪽의 단위는 (B) 말단에 에폭시 관능기를 가지는 우레탄아크릴레이트 올리고머 또는 그 중합체가 이루는 단위이다.In the above formula, the front unit is a unit formed by (A) a water-repellent acrylic monomer or a polymer thereof, and the rear unit is a unit formed by a urethane acrylate oligomer having an epoxy functional group at the terminal (B) or a polymer thereof.
(A) 발수성 아크릴레이트 단량체(A) Water repellent acrylate monomer
본 발명에서, (A) 발수성 아크릴레이트 단량체라 함은 중합체로서 섬유 제품에 코팅되는 경우 발수성을 부여하는 기능을 하는 단량체를 말한다. 구체적으로는, 탄소수 10 내지 24의 알킬 치환체를 갖는 알킬 (메타)아크릴레이트 단량체이다.In the present invention, (A) water-repellent acrylate monomer refers to a monomer that functions to impart water repellency when coated on a fiber product as a polymer. Specifically, it is an alkyl (meth) acrylate monomer which has a C10-C24 alkyl substituent.
이때, 상기 알킬 치환체는 직쇄상, 분지상이거나 또는 환을 포함하는 치환체일 수 있다. 상기 알킬 (메타)아크릴레이트 단량체는 예를 들어, 데실 (메타)아크릴레이트, 이소데실 (메타)아크릴레이트, 4-메틸-2-프로필헥실 (메타)아크릴레이트, 이소보르닐 (메타)아크릴레이트, 도데실 (메타)아크릴레이트, 펜타데실 (메타)아크릴레이트, 헥사데실 (메타)아크릴레이트, 옥타데실 (메타)아크릴레이트, 이소옥타데실(메타)아크릴레이트, 2-헵틸운데실(메타)아크릴레이트 등으로서, 이들은 단독으로 또는 2 이상의 조합으로 사용될 수 있다. 가장 바람직하게는 옥타데실 (메타)아크릴레이트(스테아릴 (메타)아크릴레이트)를 사용한다.In this case, the alkyl substituent may be a linear, branched or a substituent containing a ring. The alkyl (meth) acrylate monomers are, for example, decyl (meth) acrylate, isodecyl (meth) acrylate, 4-methyl-2-propylhexyl (meth) acrylate, isobornyl (meth) acrylate , Dodecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, isooctadecyl (meth) acrylate, 2-heptyl undecyl (meth) As acrylates and the like, these may be used alone or in combination of two or more. Most preferably octadecyl (meth) acrylate (stearyl (meth) acrylate) is used.
발수성 중합체 단위에 관하여 추가적으로는 JP2006-0328624A에 개시된 것을 추가로 참조할 수 있으며, 상기 특허문헌에 개시된 탄소수 12 내지 24의 알킬 치환체를 갖는 (메타)아크릴레이트 단량체는 본 발명의 발수성 중합체 단위로서 적용될 수 있다.With regard to the water repellent polymer unit, further reference may be made to those disclosed in JP2006-0328624A, wherein the (meth) acrylate monomer having an alkyl substituent having 12 to 24 carbon atoms disclosed in the patent document may be applied as the water repellent polymer unit of the present invention. have.
(B) 말단에 에폭시 관능기를 가지는 우레탄아크릴레이트 올리고머(B) urethane acrylate oligomer which has an epoxy functional group at the terminal
말단에 에폭시 관능기를 가지는 우레탄아크릴레이트 올리고머 단위는 발수제가 코팅된 후, 추가적으로 투습, 방수를 목적으로 수행되는 우레탄 코팅의 코팅성 향상을 목적으로 추가되는 단위이다. 본 발명에서, 상기 우레탄아크릴레이트 올리고머는 아래의 화학식 2로 표시되는 것처럼 말단에 에폭시 관능기를 가지는 것을 특징으로 한다.The urethane acrylate oligomer unit having an epoxy functional group at the end is a unit added for the purpose of improving the coating property of the urethane coating, which is additionally performed for the purpose of moisture permeation and waterproofing after the water repellent is coated. In the present invention, the urethane acrylate oligomer is characterized in that it has an epoxy functional group at the terminal as shown in the formula (2) below.
[화학식 2][Formula 2]
Figure PCTKR2015004573-appb-I000002
Figure PCTKR2015004573-appb-I000002
상기 식에서, R1은 수소 또는 메틸이고, `PU`는 우레탄 예비중합체로부터 얻어지는 부분을 표시한다.Wherein R 1 is hydrogen or methyl and 'PU' indicates the part obtained from the urethane prepolymer.
상기 (B) 우레탄아크릴레이트 올리고머는 (B-1) 말단에 이소시아네이트 관능기를 가지는 우레탄 예비중합체와 (B-2) 히드록시기를 기지는 아크릴레이트 및 (B-3)) 히드록시기 또는 카르복실기를 가지는 에폭시계 화합물을 반응시켜 얻을 수 있다.The urethane acrylate oligomer (B) is an urethane prepolymer having an isocyanate functional group at the (B-1) terminal, an acrylate having a hydroxyl group (B-2) and an epoxy compound having a (B-3)) hydroxy group or a carboxyl group. It can be obtained by reacting.
이때, (B-1) 말단에 이소시아네이트 관능기를 가지는 우레탄 예비중합체는 폴리올 화합물과 다가 이소시아네이트 화합물을 반응시켜 얻어지는, 이소시아네이트 말단의 우레탄 예비중합체를 말한다.At this time, the urethane prepolymer which has an isocyanate functional group at the terminal (B-1) refers to the urethane prepolymer of the isocyanate terminal obtained by making a polyol compound and a polyvalent isocyanate compound react.
이때, 상기 폴리올 화합물로서는 예를 들어, 폴리에틸렌글리콜, 폴리프로필렌글리콜, 폴리부틸렌글리콜, 폴리테트라메틸렌글리콜과 같은 폴리에테르 폴리올; 다염기산과 글리콜류의 축합 반응에 의해 얻어지는 폴리에스테르 폴리올; 1,4-테트라메틸렌카보네이트디올, 1, 5-펜타메틸렌카보네이트디올, 1,6-헥사메틸렌카보네이트디올, 1,2-프로필렌카보네이트디올, 1,3-프로필렌카보네이트디올, 2,2-디메틸프로필렌카보네이트디올, 1,7-헵타메틸렌카보네이트디올, 1,8-옥타메틸렌카보네이트디올, 1,9-노난메틸렌카보네이트디올, 1,4-시클로헥산카보네이트디올 등의 폴리카보네이트 폴리올; 중 어느 것도 가능하다. 또, 상기 폴리올은 2 관능의 디올, 3 관능의 트리올 또는 그 이상의 다관능 폴리올일 수 있다. 입수의 용이성, 범용성, 반응성 등의 관점에서, 디올을 사용하는 것이 바람직하다.At this time, as said polyol compound, For example, Polyether polyol, such as polyethyleneglycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol; Polyester polyols obtained by condensation reaction of polybasic acids and glycols; 1,4-tetramethylenecarbonatediol, 1,5-pentamethylenecarbonatediol, 1,6-hexamethylenecarbonatediol, 1,2-propylenecarbonatediol, 1,3-propylenecarbonatediol, 2,2-dimethylpropylenecarbonate Polycarbonate polyols such as diol, 1,7-heptamethylene carbonate diol, 1,8-octamethylene carbonate diol, 1,9-nonane methylene carbonate diol, and 1,4-cyclohexane carbonate diol; Any of these is possible. In addition, the polyol may be a difunctional diol, a trifunctional triol or more polyfunctional polyol. It is preferable to use a diol from a viewpoint of ease of availability, versatility, reactivity, etc.
다가 이소시아네이트 화합물로(B-2)는, 예를 들어 4,4'-디시클로헥실메탄디이소시아네이트, 이소포론디이소시아네이트, 2,4-톨릴렌디이소시아네이트, 2,6-톨릴렌디이소시아네이트, 1,3-자일릴렌디이소시아네이트, 1,4-자일릴렌디이소시아네이트, 디페닐메탄-4,4'-디이소시아네이트, 헥사메틸렌디이소시아네이트, 테트라메틸렌디이소시아네이트, 트리메틸헥사메틸렌디이소시아네이트, 노르보르난디이소시아네이트, 디시클로헥실메탄-2,4'-디이소시아네이트 등이 단독으로 또는 2 이상의 조합으로 사용될 수 있다.Examples of the polyisocyanate compound (B-2) include 4,4'-dicyclohexyl methane diisocyanate, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3 Xylylene diisocyanate, 1,4-xylylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, norbornane diisocyanate, dicyclo Hexylmethane-2,4'-diisocyanate and the like can be used alone or in combination of two or more.
상기 폴리올 화합물과 다가 이소시아네이트 화합물을 반응시켜 (B-1)우레탄 예비중합체가 얻어진다. 통상, 상기 폴리올과 디이소시아네이트계 화합물은 당량비로 반응되며, 양 말단에 이소시아네이트기를 형성하기 위해서는 과량의(폴리올 1당량에 대하여 1.01 내지 1.1당량비) 디이소시아네이트계 화합물을 사용한다.The (B-1) urethane prepolymer is obtained by reacting the polyol compound with a polyvalent isocyanate compound. Usually, the polyol and the diisocyanate compound are reacted in an equivalent ratio, and in order to form an isocyanate group at both ends, an excess of diisocyanate compound (1.01 to 1.1 equivalent ratio relative to one equivalent of polyol) is used.
이어서, 말단 이소시아네이트 말단의 (B-1) 우레탄 예비중합체와 (B-2) 하이드록실기를 갖는 (메타)아크릴레이트 및 (B-3) 히드록시기 또는 카르복실기를 가지는 에폭시계 화합물을 반응시켜 (B) 말단에 에폭시 관능기를 가지는 우레탄아크릴레이트 올리고머를 얻을 수 있다.Subsequently, the (B-1) urethane prepolymer of the terminal isocyanate terminal, the (meth) acrylate which has the (B-2) hydroxyl group, and the epoxy type compound which has the (B-3) hydroxyl group or carboxyl group are made to react, and (B) The urethane acrylate oligomer which has an epoxy functional group at the terminal can be obtained.
(B-2) 하이드록실기를 갖는 (메타)아크릴레이트로서는, 1 분자 내에 하이드록실기 및 (메타)아크릴로일기를 갖는 화합물이면 특별히 한정되지 않는다. 예를 들어, 2-하이드록시에틸 (메타)아크릴레이트, 2-하이드록시프로필 (메타)아크릴레이트, 2-하이드록시부틸 (메타)아크릴레이트, 4-하이드록시시클로헥실 (메타)아크릴레이트, 5-하이드록시시클로옥틸 (메타)아크릴레이트, 2-하이드록시-3-페닐옥시프로필 (메타)아크릴레이트, 펜타에리트리톨트리 (메타)아크릴레이트 등의 하이드록실알킬 (메타)아크릴레이트, 폴리에틸렌글리콜 (메타)아크릴레이트, 폴리프로필렌글리콜 (메타)아크릴레이트 등이 사용될 수 있다.(B-2) It will not specifically limit, if it is a compound which has a hydroxyl group and a (meth) acryloyl group in 1 molecule as a (meth) acrylate which has a hydroxyl group. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 5 Hydroxylalkyl (meth) acrylates such as -hydroxycyclooctyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, polyethylene glycol ( Meta) acrylate, polypropylene glycol (meth) acrylate, and the like can be used.
한편, (B-3) 히드록시기 또는 카르복실기를 가지는 에폭시계 화합물로서는, 하나의 분자내에 에폭시 관능기 및 히드록시기 또는 카르복실기 관능기를 동시에 가지는 화합물이면 특별히 제한되지 않는다. 본 발명에 적용 가능한 것들로서, 상업적으로 입수가 가능한 화합물들에 관하여 몇 개를 다음에 열거하였다:On the other hand, the epoxy compound having a hydroxy group or a carboxyl group (B-3) is not particularly limited as long as it is a compound having an epoxy functional group and a hydroxyl group or a carboxyl functional group simultaneously in one molecule. As applicable to the present invention, some of the commercially available compounds are listed below:
Figure PCTKR2015004573-appb-I000003
Figure PCTKR2015004573-appb-I000003
글리시딜알코올(2,3-epoxy-1-propanol)Glycidyl Alcohol (2,3-epoxy-1-propanol)
Figure PCTKR2015004573-appb-I000004
Figure PCTKR2015004573-appb-I000004
1-(옥시란-2-일)-에탄올(1-(oxiran-2-yl)ethanol)1- (oxirane-2-yl) -ethanol (1- (oxiran-2-yl) ethanol)
Figure PCTKR2015004573-appb-I000005
Figure PCTKR2015004573-appb-I000005
2-(옥시란-2일)-1,2-디페닐-에탄올(2-(oxiran-2-yl)-1,2-diphenyl-ethanol, CAS 87141-85-3)2- (oxirane-2yl) -1,2-diphenyl-ethanol (2- (oxiran-2-yl) -1,2-diphenyl-ethanol, CAS 87141-85-3)
Figure PCTKR2015004573-appb-I000006
Figure PCTKR2015004573-appb-I000006
4-(옥시란-2-일메톡시)페놀(4-(oxiran-2-ylmethoxy)phenol, CAS 20731-08-2)4- (oxirane-2-ylmethoxy) phenol (4- (oxiran-2-ylmethoxy) phenol, CAS 20731-08-2)
Figure PCTKR2015004573-appb-I000007
Figure PCTKR2015004573-appb-I000007
옥시란-2-카르복시산(oxiran-2-carboxylic acid, CAS 503-11-7)Oxirane-2-carboxylic acid (CAS 503-11-7)
Figure PCTKR2015004573-appb-I000008
Figure PCTKR2015004573-appb-I000008
4-(옥시란-2-일메톡시)-벤조산)(4-(oxiran-2-ylmethoxy)benzoic acid, CAS 35217-95-9).4- (oxirane-2-ylmethoxy) -benzoic acid) (4- (oxiran-2-ylmethoxy) benzoic acid, CAS 35217-95-9).
(B-1), (B-2) 및 (B-3)의 반응은 예를 들어, 각각 1:1:1 몰비에 해당하는 양으로 반응을 시키되, (B-1) 및 (B-2), 또는 (B-1) 및 (B-3)의 조합을 먼저 반응시킨 다음, 나머지 성분을 추가로 반응시키는 방법으로 제조될 수 있다.The reactions of (B-1), (B-2) and (B-3) are, for example, reacted in amounts corresponding to 1: 1: 1 molar ratio, respectively, but (B-1) and (B-2). ), Or a combination of (B-1) and (B-3) may be reacted first, and then the remaining components may be further reacted.
비제한적 의도로 설명하자면, 본 발명에 따르는 발수 코팅제의 주성분인 비불소계 아크릴계 공중합체에 상기 우레탄아크릴레이트 올리고머가 도입됨에 따라, 본 발명의 비불소계 아크릴계 공중합체가 섬유제품의 표면에 피막을 형성하는 성질이 향상되는 것으로 이해된다. 그에 따라, 발수제가 처리된 제품의 세탁내구성이 향상될 수 있다.As a non-limiting intention, as the urethane acrylate oligomer is introduced into the non-fluorine acrylic copolymer which is the main component of the water-repellent coating according to the present invention, the non-fluorine-based acrylic copolymer of the present invention forms a coating on the surface of the fiber product. It is understood that the properties are improved. Thereby, the wash durability of the product treated with the water repellent agent can be improved.
우레탄아크릴레이트 올리고머의 도입에 따른 추가적인 효과는, 방수성 향상을 위해서 후공정으로 우레탄 코팅이 수행되는 경우, 코팅의 균일성과 접착성이 향상될 수 있다는 점이다. 코팅의 균일성과 접착성 향상은 우레탄아크릴레이트 올리고머가 비불소계 아크릴계 공중합체에 함께 중합되는 경우, 중합에 참여하지 않은 에폭시 관능기가, 후술하는 우레탄코팅층을 형성하는 일 성분과 직접 반응하기나 또는 상용성 증대의 기능을 하기 때문인 것으로 이해된다.An additional effect of the introduction of the urethane acrylate oligomer is that when the urethane coating is carried out in a post process to improve the water resistance, the uniformity and adhesion of the coating can be improved. The uniformity and adhesion of the coating may be improved when the urethane acrylate oligomer is polymerized together with the non-fluorine-based acrylic copolymer, in which the epoxy functional group not participating in the polymerization reacts directly with one component forming the urethane coating layer described later or is compatible. It is understood that this is because it functions as an augmentation.
본 발명에서 바람직하게 사용되는 우레탄아크릴레이트계 올리고머의 중량평균 분자량은 1,000 내지 50,000, 더욱 바람직하게는 2,000 내지 40,000의 범위에 있다. 상기의 우레탄아크릴레이트계 올리고머는 1 종 단독으로, 또는 2 종 이상을 조합하여 사용할 수 있다.The weight average molecular weight of the urethane acrylate oligomer which is preferably used in the present invention is in the range of 1,000 to 50,000, more preferably 2,000 to 40,000. Said urethane acrylate oligomer can be used individually by 1 type or in combination of 2 or more type.
한편, 우레탄아크릴레이트 올리고머 중합체 단위의 함량은 발수성 중합체 단위의 함량 100 중량부에 대하여 1 내지 10 중량부의 비율로 사용된다. 1중량부 미만인 경우에는 우레탄 코팅층과의 접착성 및 코팅성의 향상을 기대할 수 없고, 반면, 10중량부를 초과하는 비율로 사용되면 아크릴계 공중합체의 발수성 저하가 현저하게 된다.On the other hand, the content of the urethane acrylate oligomer polymer unit is used in a ratio of 1 to 10 parts by weight based on 100 parts by weight of the water repellent polymer unit. When the amount is less than 1 part by weight, the adhesion with the urethane coating layer and the coating property cannot be improved. On the other hand, when used in a ratio exceeding 10 parts by weight, the water repellency of the acrylic copolymer is remarkably decreased.
한편, 본 발명에 따르는 비불소계 아크릴계 공중합체는 세탁내구성의 추가적 향상이나 내드라이클리닝성, 경우에 따라서는 유화중합시의 중합 안정도를 향상시킬 목적으로 C9 이하의 에틸렌성 단량체 또는 가교성 관능기 함유 단량체가 추가로 첨가되어 공중합된 것일 수 있다.On the other hand, the non-fluorine-based acrylic copolymer according to the present invention is a C9 or less ethylenic monomer or a crosslinkable functional group-containing monomer for the purpose of further improving laundry durability or dry cleaning resistance, in some cases, polymerization stability during emulsion polymerization. May be further added and copolymerized.
상기 에틸렌성 단량체로서, 예를 들어, 스티렌, 메틸스티렌, α-메틸스티렌, 비닐나프탈렌, (메타)아크릴로니트릴, 아세톤아크릴아미드, 염화비닐, 염화비닐리덴, 클로로에틸비닐에테르, 탄소수 1∼4의 알킬기를 갖는 히드록시알킬비닐에테르, 폴리에틸렌글리콜모노(메타)아크릴레이트, 폴리프로필렌글리콜모노(메타)아크릴레이트 등을 들 수 있고, 이밖에 이소프렌, 펜타디엔, 부타디엔 등의 디엔 화합물을 공중합 시킬 수도 있다. 바람직하게는 염화 비닐 또는 염화 비닐리덴을 사용한다.As said ethylenic monomer, For example, styrene, methyl styrene, (alpha) -methylstyrene, vinyl naphthalene, (meth) acrylonitrile, acetone acrylamide, vinyl chloride, vinylidene chloride, chloroethyl vinyl ether, C1-C4 Hydroxyalkyl vinyl ethers having an alkyl group, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and the like, and other diene compounds such as isoprene, pentadiene and butadiene may be copolymerized. have. Preferably vinyl chloride or vinylidene chloride is used.
상기 에틸렌성 단량체로부터 얻어지는 도막형성 중합단위의 발수성 중합단위 100 중량부에 대하여 1 내지 50중량부 이하의 비율로 사용된다.It is used in the ratio of 1-50 weight part or less with respect to 100 weight part of water repellent polymerization units of the coating-film forming polymer unit obtained from the said ethylenic monomer.
한편, 가교성 관능기 함유 중합성 단량체로서는, 예를 들면, 알릴글리시딜에테르, 글리시딜(메타)아크릴레이트 등의 에폭시기 함유 단량체, N-메틸올(메타)아크릴아미드, N-부톡시메틸올(메타)아크릴아미드 등의 N-메틸올기 함유 단량체, 2-히드록시에틸(메타)아크릴레이트, 2-히드록시프로필아크릴레이트, 4-히드록시부틸아크릴레이트, 2-히드록시-3-클로로프로필(메타)아크릴레이트 등의 히드록시알킬기 함유 단량체, (메타)아크릴아미드, N-메틸아크릴아미드, 디아세톤 아크릴아미드, 등의 아미드기 함유 단량체, 아지리디닐에틸(메타)아크릴레이트 등의 아지리디닐기 함유 단량체, 에틸렌글리콜디(메타)아크릴레이트, 폴리옥시에틸렌디(메타)아크릴레이트, 폴리옥시프로필글리콜 디(메타)아크릴레이트 등의 폴리올폴리(메타)아크릴레이트 등을 들 수 있고, 바람직하게는 친수성 단량체가 사용된다.On the other hand, as a crosslinkable functional group containing polymerizable monomer, epoxy group containing monomers, such as allyl glycidyl ether and glycidyl (meth) acrylate, N-methylol (meth) acrylamide, N-butoxymethyl, for example. N-methylol group containing monomers, such as all (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-chloro Azides, such as hydroxyalkyl group containing monomers, such as propyl (meth) acrylate, amide group containing monomers, such as (meth) acrylamide, N-methyl acrylamide, diacetone acrylamide, and aziridinyl ethyl (meth) acrylate Polyol poly (meth) acrylates, such as a lidinyl-group containing monomer, ethylene glycol di (meth) acrylate, polyoxyethylene di (meth) acrylate, and polyoxypropyl glycol di (meth) acrylate, etc. are mentioned. High, preferably hydrophilic monomers are used.
상기 단량체들이 추가되는 경우 그 함량은 통상적으로 발수성 단량체로서 탄소수 12 내지 24의 알킬기를 갖는 (메타)아크릴산에스테르 단량체 100 중량부에 대하여 20중량부 미만이다.When the monomers are added, the content thereof is usually less than 20 parts by weight based on 100 parts by weight of the (meth) acrylic acid ester monomer having an alkyl group having 12 to 24 carbon atoms as a water repellent monomer.
발수 코팅제의 제조방법Manufacturing method of water repellent coating
다음은, 본 발명에 따르는 발수제의 제조 방법에 대해 설명한다.Next, the manufacturing method of the water repellent which concerns on this invention is demonstrated.
아크릴계 공중합체는, 예를 들어, 유화중합이나 분산중합과 같은 라디칼 중합법에 의해 제조할 수 있다. 구체적으로, 탄소수 10 내지 24의 알킬 치환체를 갖는 (메타)아크릴레이트 단량체 및 우레탄 아크릴레이트 단량체, 유화제 및/또는 분산제, 중합개시제 및 필요한 첨가제를 포함하는 혼합용액 준비한 다음, 공지의 분산수단, 예를 들어, 호모 믹서, 고압 유화기 또는 초음파 등의 분산수단으로 유화 또는 분산시키고 중합하여 본 발명에 따르는 발수제가 제조된다.An acryl-type copolymer can be manufactured by radical polymerization methods, such as emulsion polymerization and dispersion polymerization, for example. Specifically, after preparing a mixed solution containing a (meth) acrylate monomer having an alkyl substituent of 10 to 24 carbon atoms and a urethane acrylate monomer, an emulsifier and / or dispersing agent, a polymerization initiator and the necessary additives, known dispersion means, for example For example, a water repellent according to the present invention is prepared by emulsifying or dispersing with a dispersing means such as a homo mixer, a high pressure emulsifier or an ultrasonic wave and polymerizing.
상기 유화제로서는 비이온 계면활성제, 양이온 계면활성제, 음이온 계면활성제 및 양성 계면활성제로부터 선택되는 1 이상을 사용할 수 있다. 유화제 또는 분산제의 함유량은, 모든 단량체 100중량부 대해 0.5~30중량부, 바람직하게는 1~20중량부를 사용한다. 유화제 또는 분산제의 양이 0.5중량부 미만인 경우에는 혼합용액의 분산 안정성이 저하하는 경향이 있고, 30중량부를 초과하면 얻어지는 공중합체의 발수성이 저하하는 경향이 있다.As the emulsifier, one or more selected from nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants can be used. As content of an emulsifier or a dispersing agent, 0.5-30 weight part with respect to 100 weight part of all monomers, Preferably 1-20 weight part is used. When the amount of the emulsifier or dispersant is less than 0.5 part by weight, the dispersion stability of the mixed solution tends to be lowered, and when it exceeds 30 parts by weight, the water repellency of the copolymer obtained tends to be lowered.
유화 중합 또는 분산 중합의 매체는 물이 바람직하고, 필요에 따라 물과 유기용제의 혼합용매를 사용할 수 있다. 이때의 유기용제로서는, 물과 상용성이 있는 유기용제이면 특별히 제한은 없어, 예를 들어, 메탄올, 에탄올 등의 알코올류, 초산에틸 등의 에스테르류, 아세톤이나 메틸에틸케톤 등의 케톤류, 디에틸 에테르등의 에테르류, 프로필렌글리콜, 디프로필렌글리콜, 트리프로필렌 글리콜 등의 글리콜류 등이 사용될 수 있다. 덧붙여 물과 유기용제의 비율은 특히 한정되는 것은 아니다.As a medium of emulsion polymerization or dispersion polymerization, water is preferable and a mixed solvent of water and an organic solvent can be used as needed. The organic solvent is not particularly limited as long as it is an organic solvent compatible with water. Examples of the organic solvent include alcohols such as methanol and ethanol, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, and diethyl. Ethers such as ether, glycols such as propylene glycol, dipropylene glycol, tripropylene glycol, and the like can be used. In addition, the ratio of water and an organic solvent is not specifically limited.
상기 중합 개시제로서는, 아조계, 과산화물계, 또는 레독스계 등의 공지의 중합개시제 중에서 선택하여 사용할 수 있다. 이때, 중합 개시제의 함유량은, 중합되는 공중합체의 분자량을 고려하여 정하여지고, 통상적으로 사용되는 사용량은 모든 단량체 100중량부에 대해 중합 개시제 0.01 내지 2중량부의 범위이다.As said polymerization initiator, it can select from well-known polymerization initiators, such as an azo system, a peroxide system, or a redox system, and can use. At this time, content of a polymerization initiator is determined in consideration of the molecular weight of the copolymer to be polymerized, and the usage-amount normally used is the range of 0.01-2 weight part of polymerization initiators with respect to 100 weight part of all monomers.
또한, 중합 반응에 있어서, 분자량 조정을 목적으로 하고, 도데실 메르캅탄, t-부틸 알코올 등의 연쇄 이동제를 이용할 수 있다. 연쇄 이동제의 함유량은, 모든 단량체 100중량부에 대해 0.1중량부 이하인 것이 바람직하다. 연쇄 이동제의 함유량이 0.1중량부를 초과하면, 분자량의 저하가 심해져 중량평균 분자량이 10만 이상인 비불소계 아크릴레이트 공중합체를 효율적으로 제조하는 것이 곤란해지는 경향이 있다. 덧붙여 분자량 조정을 위해서는 중합 금지제를 사용할 수 있다. 중합 금지제의 첨가에 의해 원하는 수준의 분자량을 가지는 비불소계 아크릴레이트 공중합체를 용이하게 얻을 수 있다.In addition, in the polymerization reaction, for the purpose of molecular weight adjustment, chain transfer agents such as dodecyl mercaptan and t-butyl alcohol can be used. It is preferable that content of a chain transfer agent is 0.1 weight part or less with respect to 100 weight part of all monomers. When content of a chain transfer agent exceeds 0.1 weight part, there exists a tendency for the fall of molecular weight to become severe and to manufacture a non-fluorine acrylate copolymer with a weight average molecular weight of 100,000 or more efficiently. In addition, a polymerization inhibitor can be used for molecular weight adjustment. By the addition of a polymerization inhibitor, a non-fluorine acrylate copolymer having a desired molecular weight can be easily obtained.
중합 반응의 온도는, 20℃ 내지 150℃이 바람직하다. 중합온도가 20℃ 미만인 경우에는 중합이 불충분하게 되고, 온도가 150℃을 넘으면, 반응열의 제어가 곤란하게 된다.As for the temperature of a polymerization reaction, 20 degreeC-150 degreeC is preferable. When the polymerization temperature is less than 20 ° C, the polymerization becomes insufficient, and when the temperature exceeds 150 ° C, control of the heat of reaction becomes difficult.
상술한 방법에 따라 얻어지는 공중합체의 중량 평균 분자량은 10만 이상인 것이 바람직하다. 중합 반응에 있어서, 얻을 수 있는 비불소계 아크릴레이트 공중합체의 중량평균 분자량은, 상술한 중합 개시제, 연쇄 이동제, 중합 금지제의 함유량의 증감에 의해 조정할 수 있다.It is preferable that the weight average molecular weight of the copolymer obtained by the above-mentioned method is 100,000 or more. In the polymerization reaction, the weight average molecular weight of the obtained non-fluorine acrylate copolymer can be adjusted by increasing or decreasing the content of the polymerization initiator, the chain transfer agent, and the polymerization inhibitor described above.
한편, 유화 또는 분산 중합에 의해 비불소계 아크릴레이트 공중합체를 제조하는 경우, 비공중합체의 함유 비율은 10~50중량%, 바람직하게는 20 내지 40중량%로 조정된다.On the other hand, when manufacturing a non-fluorine acrylate copolymer by emulsion or dispersion polymerization, the content rate of a non-copolymer is adjusted to 10-50 weight%, Preferably it is 20-40 weight%.
본 발명의 발수제에는 필요에 따라 첨가제 등을 더하는 것도 가능하다. 첨가제로서는, 다른 발수제, 가교제, 항균 방취제, 난연제, 대전 방지제, 유연제 등을 들 수 있다.It is also possible to add an additive etc. to the water repellent agent of this invention as needed. As an additive, another water repellent, a crosslinking agent, an antibacterial deodorant, a flame retardant, an antistatic agent, a softening agent, etc. are mentioned.
발수제 처리Water repellent treatment
본 발명에 따르는 발수제가 처리되는 섬유제품에는 특별히 제한이 없어 예를 들어, 폴리에스터, 폴리우레탄, 폴리아클릴로나이트릴, 폴리비닐알콜, 폴리염화비닐리덴, 폴리프로필렌, 나일론 섬유 등의 합성섬유; 면, 마, 견, 레이온, 아세테이트 섬유 등의 천연 또는 천연 유래의 섬유제품; 또는 이들을 혼방한 제품;에 상기 발수제가 적용될 수 있다. 또한, 섬유에 직접 상기 발수제가 처리될 수 있고, 직물, 편물, 부직포 등에 처리될 수 있다.The fiber product treated with the water repellent agent according to the present invention is not particularly limited, and for example, synthetic fibers such as polyester, polyurethane, polyacrylonitrile, polyvinyl alcohol, polyvinylidene chloride, polypropylene, nylon fibers; Natural or naturally derived fiber products such as cotton, hemp, silk, rayon and acetate fibers; Or a product mixed with these; the water repellent may be applied. In addition, the water repellent can be treated directly on the fibers, and can be treated on fabrics, knits, nonwovens and the like.
섬유제품에 발수제를 처리하는 방법에도 특별한 제한이 없어, 예를 들어, 침지, 스프레이, 도포 등 공지의 방법에 따라 발수제를 코팅한 다음 건조, 경화(큐어링)하여 발수 코팅제가 처리된 섬유제품을 얻을 수 있다.There is no particular limitation on the method of treating the water repellent agent to the textile product, for example, coating the water repellent agent according to a known method such as dipping, spraying or coating, and then drying and curing (cure) the textile product treated with the water repellent coating. You can get it.
상기 섬유제품에 본 발명에 따르는 발수 코팅제를 처리함에 있어, 코팅되는 양은 요구되는 발수성의 정도에 따라 조정될 수 있다. 통상적으로는 섬유제품 100중량부에 대하여 발수 코팅제의 양이 0.1 내지 10중량부의 범위에서 조절된다. 코팅량이 0.1중량부 미만인 경우에는 발수성이 충분치 않고, 10중량부를 초과하는 경우에는 원소재의 특성이 상실될 수 있다.In treating the fiber product with the water repellent coating according to the invention, the amount to be coated can be adjusted according to the degree of water repellency required. Usually, the amount of the water repellent coating agent is adjusted in the range of 0.1 to 10 parts by weight based on 100 parts by weight of the textile product. If the coating amount is less than 0.1 part by weight, the water repellency is not sufficient, and if the coating amount is more than 10 parts by weight, the properties of the raw material may be lost.
한편, 발수 코팅제를 코팅한 다음에는 열처리하여 경화시킨다. 열처리의 온도조건에는 특별한 제한은 없으며, 통상적으로는 100 내지 150℃의 온도에서 수행된다.On the other hand, after the water-repellent coating is coated, it is cured by heat treatment. There is no particular limitation on the temperature condition of the heat treatment, and is usually carried out at a temperature of 100 to 150 ℃.
우레탄 코팅Urethane coating
우레탄 코팅은 투습·방수의 목적으로 수행된다. 상기 우레탄 코팅은 우레탄 코팅액을 준비한 다음 이를 섬유제품에 코팅하고, 건조 및/또는 경화시켜 코팅막을 형성시키는 방법으로 수행된다.Urethane coating is performed for the purpose of moisture permeation and waterproofing. The urethane coating is carried out by preparing a urethane coating solution and then coating it on a textile product, drying and / or curing to form a coating film.
상기 우레탄 코팅액은 친수성 폴리우레탄 수지를 주성분으로 하는 코팅액으로, 상기 친수성 폴리우레탄 수지는 종래의 것을 사용할 수 있다.The urethane coating liquid is a coating liquid containing a hydrophilic polyurethane resin as a main component, and the hydrophilic polyurethane resin may be a conventional one.
예를 들어, 상기 폴리우레탄 수지는 폴리이소시아네이트 성분과 폴리올 성분을 반응시켜 얻어지는 폴리우레탄 수지를 들 수 있다.For example, the said polyurethane resin can mention the polyurethane resin obtained by making a polyisocyanate component and a polyol component react.
이때, 상기 폴리이소시아네이트 성분으로서는, 방향족 디이소시아네이트, 지방족 디이소시아네이트, 지환족 디이소시아네이트 등을 들 수 있다.구체적으로는, 톨릴렌-2,4-디이소시아네이트, 4,4＇-디페닐 메탄 디이소시아네이트, 1,6-헥사메틸렌 디이소시아네이트 또는1,4-사이클로헥산 디이소시아네이트 등을 들 수가 있다. 3 관능 이상의 폴리이소시아네이트를 사용할 수 있으며, 이들은 단독으로, 혹은 2종 이상의 조합으로 사용될 수 있다.At this time, examples of the polyisocyanate component include aromatic diisocyanate, aliphatic diisocyanate and alicyclic diisocyanate. Specifically, tolylene-2,4-diisocyanate, 4,4'-diphenyl methane diisocyanate And 1,6-hexamethylene diisocyanate or 1,4-cyclohexane diisocyanate. Trifunctional or higher polyisocyanates can be used, and these can be used alone or in combination of two or more.
한편, 폴리올 성분으로서는, 예를 들면, 폴리에테르 폴리올이나 폴리에스테르 폴리올 등을 들 수 있다. 폴리에테르 폴리올로서는, 폴리에틸렌글리콜, 폴리프로필렌글리콜 또는 폴리테트라에틸렌글리콜 등을 들 수 있다. 폴리에스테르 폴리올로서는, 에틸렌글리콜이나 프로필렌 글리콜 등의 디올과 아디프산이나 세바틴산 등의 이염기산과의 반응 생성물이나, 카프로락톤 등의 개환 중합물, 옥시산 모노머 혹은 그 프레폴리머 등이 사용될 수 있다.On the other hand, as a polyol component, polyether polyol, polyester polyol, etc. are mentioned, for example. Examples of the polyether polyols include polyethylene glycol, polypropylene glycol, polytetraethylene glycol, and the like. As polyester polyol, the reaction product of diol, such as ethylene glycol and propylene glycol, and dibasic acids, such as adipic acid and sebacic acid, ring-opening polymers, such as caprolactone, an oxyacid monomer, its prepolymer, etc. can be used.
코팅막은 폴리우레탄 코팅액을 준비한 다음, 공지의 수단을 이용하여 코팅한 다음 섬유제품에 도포하고 건조하는 방법으로 형성된다.The coating film is prepared by preparing a polyurethane coating solution, coating it using a known means, and then applying it to a textile product and drying it.
이때, 상기 코팅액은 메틸에틸 케톤이나 톨루엔 등의 유기용제에 친수성 폴리우레탄 수지 등을 필요한 경우 유화제와 함께 분산시킨 O/W형 에멀젼 등을 사용할 수 있다. 상기 코팅액에는 코팅막에 미세기공을 형성시키기 위한 특정의 용출성분이나 가스 발포제 등이 추가로 첨가될 수 있으며, 추가적으로, 형성되는 코팅막의 강도향상을 위하여 이소시아네이트계열의 가교제가 추가로 첨가될 수도 있다.In this case, the coating solution may be an O / W emulsion or the like dispersed with an emulsifier when a hydrophilic polyurethane resin is required in an organic solvent such as methyl ethyl ketone or toluene. The elution component or gas blowing agent may be additionally added to the coating solution to form micropores in the coating film. In addition, an isocyanate-based crosslinking agent may be additionally added to increase the strength of the coating film.
상기 방법으로 발수코팅층 상에 형성되는 우레탄 코팅막의 두께는 바람직하게는 1 내지 100㎛이다. The thickness of the urethane coating film formed on the water repellent coating layer by the above method is preferably 1 to 100㎛.
발수제가 처리된 섬유제품에 우레탄 코팅을 수행하는 통상적인 방법으로는 예를 들어, 습식, 건식 및, 라미네이팅법 등이 있다.Conventional methods for carrying out urethane coatings on textile products treated with water repellents include, for example, wet, dry, and laminating methods.
습식방법: 발수 코팅제가 처리된 섬유제품에 우레탄 코팅액을 코팅한 다음, 물/DMF 혼합용매와 같이 용매/비용매 혼합용매에 투입하여 응고시킨 다음 수세, 건조하여 코팅막을 형성하는 방법이다. 통상적으로 은조조의 온도는 상온~50℃, 수세조는 50~80℃로 유지되면 건조는 100~150℃에서 수행된다. Wet method: A method of coating a urethane coating solution on a fiber product treated with a water-repellent coating, and then coagulating by adding it to a solvent / non-solvent mixed solvent like water / DMF mixed solvent, followed by washing with water and drying to form a coating film. Typically, the temperature of the silver bath is maintained at room temperature ~ 50 ℃, water washing tank 50 ~ 80 ℃ drying is carried out at 100 ~ 150 ℃.
건식방법: 발수 코팅제가 처리된 섬유제품을 100~150℃의 고온에서 프레스 등으로 압력을 가하면서 건조, 경화시키는 방법이다. 건식방법에서는 우레탄 코팅액의 도포 및 가압경화, 및 건조가 2~3회로 나뉘어 수행되는 것이 보통이다.Drying method: A method of drying and curing a textile product treated with a water-repellent coating agent by applying pressure with a press or the like at a high temperature of 100 to 150 ° C. In the dry method, the urethane coating liquid is usually applied in two to three times by applying and curing the pressure and drying.
라미네이팅법: 우레탄 코팅액을 PET 등의 고분자 필름이나 종이 등의 적절한 이형지에 코팅한 다음, 이를 그대로 또는 예비건조시킨 후에, 발수 코팅제가 처리된 섬유제품으로 전사시키는 방법이다. 전사 후에는 상술한 습식 또는 건식방법과 결합될 수 있다.Laminating method: A method of transferring a urethane coating solution onto a suitable release paper such as a polymer film or paper such as PET, and then drying it as it is or preliminarily, and then transferring the water-repellent coating to a textile product treated with a water repellent coating. After the transfer can be combined with the wet or dry method described above.
상기 방법들 중, 습식방법의 경우, 우레탄 코팅에 의한 투습·방수성능은 우수하나, 우레탄 코팅과 섬유제품간의 접착력이 충분치 않다. 반대로, 건식방법의 경우 접착력은 통상적으로 15N/5cm 이상으로 우수하나, 투습·방수성능이 저하될 우려가 있다. 본 발명에 따르는 발수 코팅액을 적용하는 경우 우레탄 코팅액이 상기 습식방법으로 코팅되는 경우에도, 발수 코팅된 섬유제품과 우레탄 코팅과의 접착력이 우수한 투습·방수성을 갖는 섬유제품을 얻을 수 있다는 장점이 있다.Among the above methods, in the wet method, the moisture permeability and waterproof performance by the urethane coating are excellent, but the adhesion between the urethane coating and the fiber product is not sufficient. On the contrary, in the dry method, the adhesive strength is generally superior to 15 N / 5 cm or more, but there is a fear that the moisture permeability and waterproof performance are lowered. In the case of applying the water repellent coating liquid according to the present invention, even when the urethane coating liquid is coated by the wet method, there is an advantage that a fiber product having excellent moisture permeability and water resistance can be obtained.
이하, 실시예를 통하여 본 발명을 보다 상세히 설명하고자 한다. 본 실시예는 본 발명을 보다 구체적으로 설명하기 위한 것이며, 본 발명의 범위가 이들 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. This embodiment is intended to illustrate the present invention in more detail, and the scope of the present invention is not limited by these examples.
(1) 말단에 에폭시 관능기를 가지는 우레탄아크릴레이트 올리고머의 합성(1) Synthesis of urethane acrylate oligomer having epoxy functional group at the terminal
환류 냉각기와 온도계 및 교반기를 설치한 반응기에 분자량 Mw~2,000의 폴리프로필렌디올을 투입하고, 용액의 온도를 60℃로 상승시킨 후, DBTDL(디부틸틴디라울레이트)을 촉매량으로 투입하였다. 첨가한 DBTDL이 모두 용해된 것을 확인하고, 폴리프로필렌디올에 대하여 1.05몰비의 이소포론디이소시아네이트를 적하펀넬을 이용하여 30분간 서서히 투입한 후 반응기의 온도를 60℃로 유지하면서 4시간 동안 반응하였다. 이후에 1몰비의 2-히드록시에틸아크릴레이트(HEA)와 글리시딜알코올을 순차적으로 투입하고, 동일온도에서 추가적으로 4시간 동안 반응시켰다. 반응의 종료시점은 반응 혼합물의 IR 분석결과 NCO 피크가 사라지는 것으로 판단하였다.Polypropylene diols having a molecular weight of Mw to 2,000 were added to a reactor provided with a reflux condenser, a thermometer, and a stirrer, and after raising the temperature of the solution to 60 ° C, DBTDL (dibutyl tin dilaurate) was added as a catalytic amount. After confirming that all the added DBTDL was dissolved, 1.05 molar ratio of isophorone diisocyanate was slowly added to the polypropylene diol for 30 minutes using a dropping funnel, followed by reaction for 4 hours while maintaining the temperature of the reactor at 60 ° C. Thereafter, 1 mole ratio of 2-hydroxyethyl acrylate (HEA) and glycidyl alcohol were sequentially added thereto, and the reaction was performed for an additional 4 hours at the same temperature. At the end of the reaction, it was determined that the NCO peak disappeared through IR analysis of the reaction mixture.
(2) 발수 코팅제의 제조(2) Preparation of Water Repellent Coating
실시예1 Example 1
먼저, 다음 조성비로 혼합한 용액을 초음파분산시켜 혼합용액 A, B를 준비하였다.First, the mixed solution A and B were prepared by ultrasonic dispersion of the mixed solution in the following composition ratio.
혼합용액 A:Mixed Solution A:
물 75중량부, 디프로필렌글리콜 50중량부  75 parts by weight of water, 50 parts by weight of dipropylene glycol
스테아릴 아크릴레이트 100중량부(발수성 중합체 단위)  100 parts by weight of stearyl acrylate (water repellent polymer unit)
폴리옥시에틸렌 라우릴에테르 5중량부 (비이온 계면활성제)  5 parts by weight of polyoxyethylene lauryl ether (nonionic surfactant)
라우릴트리메틸암모늄클로라이드 20중량부 (양이온 계면활성제)   20 parts by weight of lauryltrimethylammonium chloride (cationic surfactant)
혼합용액 B:Mixed solution B:
물 50중량부(용매)  50 parts by weight of water (solvent)
합성된 우레탄아크릴레이트 올리고머 5중량부  Synthetic urethane acrylate oligomer 5 parts by weight
비닐클로라이드 18중량부 (추가 에틸렌성 단량체)  18 parts by weight of vinyl chloride (additional ethylenic monomer)
2,2-아조비스(2-아미디노프로판)디하이드로클로라이드 1중량부(개시제)  1 part by weight of 2,2-azobis (2-amidinopropane) dihydrochloride (initiator)
N-도데실머캡탄 2.5중량부 (연쇄이동제)  N-dodecyl mercaptan 2.5 parts by weight (chain transfer agent)
준비된 상기 혼합용액 A에 상기 혼합용액 B를 가한 다음, 질소 분위기하에서 60℃에서 6시간 동안 라디칼 중합시켜, 비불소계 아크릴계 공중합체를 포함하는 발수 코팅제를 제조하였다.The mixed solution B was added to the prepared mixed solution A, followed by radical polymerization at 60 ° C. for 6 hours under a nitrogen atmosphere, thereby preparing a water-repellent coating comprising a non-fluorine-based acrylic copolymer.
실시예 2Example 2
혼합용액 B를 준비함에 있어, 우레탄 아크릴레이트 올리고머 10중량부를 첨가한 것을 제외하고는 실시예 1과 동일한 방법으로 비불소계 아크릴계 공중합체를 포함하는 발수 코팅제를 제조하였다.In preparing the mixed solution B, a water-repellent coating comprising a non-fluorine-based acrylic copolymer was prepared in the same manner as in Example 1 except that 10 parts by weight of the urethane acrylate oligomer was added.
실시예 3Example 3
혼합용액 B를 준비함에 있어, 우레탄 아크릴레이트 올리고머 20중량부를 첨가한 것을 제외하고는 실시예 1과 동일한 방법으로 비불소계 아크릴계 공중합체를 포함하는 발수 코팅제를 제조하였다.In preparing the mixed solution B, a water-repellent coating comprising a non-fluorine-based acrylic copolymer was prepared in the same manner as in Example 1 except that 20 parts by weight of the urethane acrylate oligomer was added.
실시예 4Example 4
혼합용액 A를 준비함에 있어, 발수성 중합체 단위로서 아크릴레이트 단위로서 스테아릴 아크릴레이트 90중량부 및 라우릴아크릴레이트 10중량부를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 비불소계 아크릴계 공중합체를 포함하는 발수 코팅제를 제조하였다.In preparing the mixed solution A, a non-fluorinated acrylic copolymer was prepared in the same manner as in Example 1 except that 90 parts by weight of stearyl acrylate and 10 parts by weight of lauryl acrylate were used as the acrylate unit as the water repellent polymer unit. A water repellent coating was prepared.
비교예 1Comparative Example 1
혼합용액 B를 준비함에 있어, 우레탄 아크릴레이트 올리고머를 첨가하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로 비불소계 아크릴계 공중합체를 포함하는 발수 코팅제를 제조하였다.In preparing the mixed solution B, a water-repellent coating including a non-fluorine-based acrylic copolymer was prepared in the same manner as in Example 1 except that the urethane acrylate oligomer was not added.
비교예 2Comparative Example 2
혼합용액 B를 준비함에 있어, 발수성 단량체로서 우레탄 아크릴레이트 올리고머를 대신하여 퍼플루오로알킬에틸 아크릴레이트 40중량부를 첨가하는 것을 제외하고는 실시예 1과 동일한 방법으로 불소계 아크릴계 공중합체를 포함하는 발수 코팅제를 제조하였다.In preparing the mixed solution B, a water-repellent coating agent comprising a fluorine-based acrylic copolymer in the same manner as in Example 1, except that 40 parts by weight of perfluoroalkylethyl acrylate was added instead of the urethane acrylate oligomer as the water-repellent monomer. Was prepared.
(3) 발수코 팅제 처리(3) water repellent coating
폴리에스테르 및 나일론-6 직물들에 대하여 상기 실시예 및 비교예들에서 제조된 발수 코팅제를 처리하여 발수성을 평가하였다.Polyester and nylon-6 fabrics were treated with the water repellent coatings prepared in the Examples and Comparative Examples to evaluate water repellency.
폴리에스테르(PET) 직물: 경사, 위사 밀도가 각각 187본, 98본, 75d/144f  Polyester (PET) fabrics: 187, 98, 75d / 144f warp and weft densities, respectively
나일론-6 직물: 경사, 위사 밀도가 각각 115본, 95본, 78d/68f  Nylon-6 fabric: warp and weft density 115, 95, 78d / 68f, respectively
실시예 및 비교예들에서 제조된 아크릴레이트 공중합체의 함유량이 4중량%가 되도록 물로 희석한 다음, 상기 원단들을 침지처리한 후(픽업율 50중량%), 120℃으로 2분간 건조 및 열처리하였다. After diluting with water so that the content of the acrylate copolymer prepared in Examples and Comparative Examples was 4% by weight, the fabrics were immersed (pickup rate of 50% by weight), and then dried and heat treated at 120 ° C for 2 minutes. .
(4) 우레탄 코팅(4) urethane coating
상기 발수처리된 직물들에 대하여 O/W형 폴리우레탄 에멀젼을 콤마코터를 이용하여 도포량 180g/m2으로 도포하고, 이후, 80℃으로 3분간 건조하여 폴리우레탄 코팅막을 형성하였다. 이후, 30℃의 H2O/DMF(80/20vol.%) 응고조에서 응고시킨 다음, 60℃의 수조에서 세척하고, 130℃에서 건조하여 투습·방수성을 갖는 섬유제품을 제조하였다. 이때, 상기 코팅막의 두께는 약 50㎛이었다.The O / W type polyurethane emulsion was applied to the water-repellent fabrics using a comma coater at a coating amount of 180 g / m 2 , and then dried at 80 ° C. for 3 minutes to form a polyurethane coating film. Thereafter, the mixture was solidified in a 30 ° C. H 2 O / DMF (80/20 vol.%) Coagulation bath, washed in a 60 ° C. water bath, and dried at 130 ° C. to prepare a fiber product having moisture permeability and water resistance. At this time, the thickness of the coating film was about 50㎛.
[O/W형 폴리우레탄 에멀젼의 조성: 고형분 26 질량%의 O/W형 폴리우레탄 수지 100중량부(다이이치세이카공업 사제,ATX-10), 이소시아네이트계 가교제 2중량부(다이이치세이카공업 사제, 레자민 X), 메틸에틸케톤/톨루엔 20중량부/25중량부, 물/메틸에틸케톤 25중량부/5중량부][Composition of O / W Type Polyurethane Emulsion: 100 parts by weight of an O / W type polyurethane resin having a solid content of 26% by mass (manufactured by Daiichi Seika Co., Ltd., ATX-10), 2 parts by weight of an isocyanate-based crosslinking agent (manufactured by Daiichi Seika Co., Ltd.) , Rezamin X), 20 parts by weight of methyl ethyl ketone / toluene / 25 parts by weight, 25 parts by weight of water / methyl ethyl ketone / 5 parts by weight]
평가evaluation
(1) 발수도 : AATCC 22에서 정하는 스프레이법에 따라 발수도를 평가하였다 (세탁조건: AATCC 135, Test No. (2)(Ⅲ)A(ii), 정상 사이클, 세탁온도 41±3℃, 약 텀블조건). 우레탄 코팅된 발수-방수 직물에 대하여 초기 및 20회 세탁 후의 직물에 대하여 각각 평가하였다. (1) Water repellency: Water repellency was evaluated according to the spray method specified in AATCC 22 (Washing conditions: AATCC 135, Test No. (2) (III) A (ii), normal cycle, washing temperature 41 ± 3 ℃, About tumble conditions). Urethane coated water-repellent fabrics were evaluated for fabrics after initial and 20 washes, respectively.
(2) 투습도 : ASTM E 96 평가방법(inverted cup water법)에 의거하여 측정하였다. 투습컵의 면적 38.465cm2, 높이 53mm, 온도 32±1℃/상대습도 50±2%의 조건에서 실험이 수행되었다. (2) Water vapor permeability: It was measured according to ASTM E 96 evaluation method (inverted cup water method). The experiment was carried out under the conditions of an area of 38.465 cm 2 , height 53 mm, and temperature of 32 ± 1 ° C./relative humidity of 50 ± 2%.
(3) 내수도 : ISO 811(E) 방법(저수압법)에 의거하여 수압 600mmH20/분의 조건에서 평가되었다.(3) Domestic Province: evaluated at ISO 811 (E) Hydraulic method 600mmH 2 0 / min in accordance with the conditions of the (low water pressure method).
(4) 박리강도 : ASTM D2724의 방법에 따라 평가되었다.(4) Peel strength: evaluated according to the method of ASTM D2724.
표 1
발수코팅제 발수도:초기 발수도:5회 세탁후 발수도:20회 세탁후 투습도(g/m2/24h) 내수도(cmH20) 박리강도(N/5cm)
폴리에스테르 실시예 1 100 90 90 7,437 >10,000 17.5
실시예 2 100 90 90 6,726 9,800 16.5
실시예 3 100 90 90 6,077 9,500 18.0
실시예 4 100 90 90 5,900 9,400 16.6
비교예 1 100 80 80 5,622 >10,000 8.9
비교예 2 100 80 80 7,011 9,450 12.5
나일론 실시예 1 100 80 80 7,921 >10,000 15.0
실시예 2 100 80 80 6,900 8,025 16.5
실시예 3 100 80 80 6,020 7,837 15.5
실시예 4 100 90 80 6,100 8,250 15.7
비교예 1 100 60 60 4,522 >10,000 7.5
비교예 2 100 70 70 5,090 8,050 10.4
Table 1
Water repellent coating Water repellency: Initial Water repellency: After washing five times Water repellency: After washing 20 times Moisture permeability (g / m 2 / 24h) Water resistance (cmH 2 0) Peel Strength (N / 5cm)
Polyester Example 1 100 90 90 7,437 > 10,000 17.5
Example 2 100 90 90 6,726 9,800 16.5
Example 3 100 90 90 6,077 9,500 18.0
Example 4 100 90 90 5,900 9,400 16.6
Comparative Example 1 100 80 80 5,622 > 10,000 8.9
Comparative Example 2 100 80 80 7,011 9,450 12.5
nylon Example 1 100 80 80 7,921 > 10,000 15.0
Example 2 100 80 80 6,900 8,025 16.5
Example 3 100 80 80 6,020 7,837 15.5
Example 4 100 90 80 6,100 8,250 15.7
Comparative Example 1 100 60 60 4,522 > 10,000 7.5
Comparative Example 2 100 70 70 5,090 8,050 10.4
상기 표로부터, 본 발명에 따르는 발수 코팅제를 처리한 다음 우레탄코팅된 투습·방수성을 갖는 섬유제품의 경우 투습도 및 내수압에서는 종래의 제품에 비하여 큰 차이를 보이지 않으면서도, 원단과 우레탄 코팅 사이의 박리강도가 현저하게 상승하였음을 확인할 수 있다. 구체적으로, 종래의 비불소계 발수제(비교예 1)가 처리된 원단에 비하여 박리강도가 폴리에스테르 원단의 경우 최소 85%이상, 나일론 원단의 경우 최소 100% 이상 향상됨을 확인할 수 있다. 또한 종래의 불소계 발수제(비교예 2)에 비하여, 폴리에스테르 원단의 경우 30%이상, 나일론 원단의 경우 40% 이상 향상되었음을 확인할 수 있다.From the table, in the case of the fiber product having a water-repellent coating according to the present invention after the urethane-coated moisture-permeable and water-resistant, the peel strength between the fabric and the urethane coating, while showing no significant difference in water vapor transmission rate and water resistance compared to conventional products It can be seen that the significantly increased. Specifically, it can be seen that the peel strength is improved by at least 85% or more in the case of a polyester fabric and at least 100% in the case of a nylon fabric, compared to a fabric treated with a conventional non-fluorine-based water repellent (Comparative Example 1). In addition, compared to the conventional fluorine-based water repellent (Comparative Example 2), it can be confirmed that more than 30% for polyester fabric, 40% or more for nylon fabric.
아울러, 세탁 하지 아니한 초기 발수도는 종래 제품과 마찬가지로 100을 유지한 반면에 세탁후에는 종래제품에 대비하여 발수도가 개선되었는데, 5회 세탁 처리의 발수도는 물론, 20회 세탁 후의 발수도도 폴리에스테르에 대하여 90, 나일론에 대하여 80을 유지하여, 세탁내구성이 향상되었음을 확인할 수 있다.In addition, the initial water repellency of the non-washing was maintained at 100 as in the conventional products, while the water repellency was improved compared to the conventional products after washing, as well as the water repellency of the five washing treatments, as well as the water repellency after 20 washings. By maintaining 90 for polyester and 80 for nylon, it can be seen that washing durability is improved.

Claims (7)

  1. (A) 발수성 아크릴레이트 단량체 100 중량부에 대하여; (B) 말단에 에폭시 관능기를 가지는 우레탄아크릴레이트 올리고머 1 내지 10중량부;를 공중합하여 제조되는 비불소계 아크릴계 공중합체를 포함하는 발수 코팅제.(A) based on 100 parts by weight of the water repellent acrylate monomer; (B) 1 to 10 parts by weight of a urethane acrylate oligomer having an epoxy functional group at the terminal; a water-repellent coating comprising a non-fluorine-based acrylic copolymer prepared by copolymerizing.
  2. 제 1항에 있어서, 상기 (A) 발수성 아크릴레이트 단량체는 탄소수 10 내지 24의 알킬 치환체를 갖는 알킬 (메타)아크릴레이트인 것을 특징으로 하는 발수 코팅제.The water-repellent coating agent according to claim 1, wherein the (A) water-repellent acrylate monomer is an alkyl (meth) acrylate having an alkyl substituent having 10 to 24 carbon atoms.
  3. 제 1항에 있어서, 상기 (A) 발수성 아크릴레이트 단량체는 데실 (메타)아크릴레이트, 이소데실 (메타)아크릴레이트, 4-메틸-2-프로필헥실 (메타)아크릴레이트, 이소보르닐 (메타)아크릴레이트, 도데실 (메타)아크릴레이트, 펜타데실 (메타)아크릴레이트, 헥사데실 (메타)아크릴레이트, 옥타데실 (메타)아크릴레이트, 이소옥타데실(메타)아크릴레이트 및 2-헵틸운데실(메타)아크릴레이트로 구성된 군으로부터 선택되는 하나 이상인 것을 특징으로 하는 발수 코팅제.The method of claim 1, wherein the (A) water-repellent acrylate monomer is decyl (meth) acrylate, isodecyl (meth) acrylate, 4-methyl-2-propylhexyl (meth) acrylate, isobornyl (meth) Acrylate, dodecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, isooctadecyl (meth) acrylate and 2-heptyl undecyl ( Water repellent coating, characterized in that at least one selected from the group consisting of methacrylate.
  4. 제1항에 있어서, 상기 (B) 말단에 에폭시 관능기를 가지는 우레탄아크릴레이트 올리고머는 (B-1) 말단에 이소시아네이트 관능기를 가지는 우레탄 예비중합체와 (B-2) 히드록시기를 기지는 아크릴레이트 및 (B-3) 히드록시기 또는 카르복실기를 가지는 에폭시계 화합물을 반응시켜 얻어지는 화합물인 것을 특징으로 하는 발수 코팅제.The urethane acrylate oligomer according to claim 1, wherein the urethane acrylate oligomer having an epoxy functional group at the terminal (B) has a urethane prepolymer having an isocyanate functional group at the terminal (B-1), an acrylate based on the hydroxyl group (B-2), and (B) -3) A water-repellent coating agent, characterized in that the compound is obtained by reacting an epoxy compound having a hydroxy group or a carboxyl group.
  5. 제4항에 있어서, 상기 (B-3) 히드록시기 또는 카르복실기를 가지는 에폭시계 화합물은 글리시딜알코올(2,3-epoxy-1-propanol), 1-(옥시란-2-일)-에탄올(1-(oxiran-2-yl)ethanol), 2-(옥시란-2일)-1,2-디페닐-에탄올(2-(oxiran-2-yl)-1,2-diphenyl-ethanol, CAS 87141-85-3), 4-(옥시란-2일메톡시)페놀(4-(oxiran-2-ylmethoxy)phenol, CAS 20731-08-2), 옥시란-2-카르복시산(oxiran-2-carboxylic acid:CAS 503-11-7) 및 4-(옥시란-2-일메톡시)-벤조산)(4-(oxiran-2-ylmethoxy)benzoic acid, CAS 35217-95-9)로 구성된 군으로부터 선택되는 하나 이상인 것을 특징으로 하는 발수 코팅제.The epoxy compound of claim 4, wherein the epoxy compound having a hydroxyl group or a carboxyl group is glycidyl alcohol (2,3-epoxy-1-propanol), 1- (oxirane-2-yl) -ethanol (6). 1- (oxiran-2-yl) ethanol), 2- (oxirane-2yl) -1,2-diphenyl-ethanol (2- (oxiran-2-yl) -1,2-diphenyl-ethanol, CAS 87141-85-3), 4- (oxirane-2-ylmethoxy) phenol (4- (oxiran-2-ylmethoxy) phenol, CAS 20731-08-2), oxirane-2-carboxylic acid (oxiran-2-carboxylic acid: CAS 503-11-7) and 4- (oxirane-2-ylmethoxy) -benzoic acid) (4- (oxiran-2-ylmethoxy) benzoic acid, CAS 35217-95-9) At least one water repellent coating.
  6. 제1항에 있어서, 상기 (B) 말단에 에폭시 관능기를 가지는 우레탄아크릴레이트 올리고머는 중량평균 분자량이 1,000 내지 50,000인 것을 특징으로 하는 발수 코팅제.The water-repellent coating agent according to claim 1, wherein the urethane acrylate oligomer having an epoxy functional group at the (B) terminal has a weight average molecular weight of 1,000 to 50,000.
  7. 제1항의 방수 코팅제가 처리된 다음, 추가로 우레탄 코팅되어 제조되는 투습·방수성을 갖는 섬유제품. A water-permeable and waterproof textile product produced by urethane coating after the waterproof coating of claim 1 is further processed.
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