KR101405133B1 - Environmentally friendly poly acryl urethane resin emulsion composition and waterproof ground materials using the same - Google Patents

Environmentally friendly poly acryl urethane resin emulsion composition and waterproof ground materials using the same Download PDF

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KR101405133B1
KR101405133B1 KR1020130089349A KR20130089349A KR101405133B1 KR 101405133 B1 KR101405133 B1 KR 101405133B1 KR 1020130089349 A KR1020130089349 A KR 1020130089349A KR 20130089349 A KR20130089349 A KR 20130089349A KR 101405133 B1 KR101405133 B1 KR 101405133B1
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weight
water
resin composition
ammonium
present
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김학재
민경봉
이하형
박성진
김철기
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미래피앤씨(주)
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04Homopolymers or copolymers of esters
    • C08L33/14Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641Polyacrylates; Polymethacrylates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/07Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from polymer solutions
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • C08L75/14Polyurethanes having carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D133/00Coating 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
    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/14Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/14Polyurethanes having carbon-to-carbon unsaturated bonds

Abstract

The present invention relates to a water-dispersible poly acryl urethane emulsion resin composition having excellent tensile force, elasticity, and adhesive force of concrete mortar-based material and to an acryl urethane rubber-based waterproof paint composition using the same. The present invention provides an environmentally-friendly water-dispersible poly acryl urethane emulsion resin composition and an acryl urethane rubber-based waterproof paint composition using the same, wherein the environmentally-friendly water-dispersible poly acryl urethane emulsion resin composition is produced by mixing and reacting 1.0-20 wt% of diacetone acrylamide, 15-20 wt% of n-buthyl acrylate, 0.5-1.5 wt% of methacrylic acid, 1.0-2.2 wt% of acrylonitrile, 13-18 wt% of buthyl methacrylate, 13.2-17.5 wt% of 2-ethylhexyl acrylate, 2.2-3.0 wt% of styrene, 0.5-2.0 wt% of adipic acid dihydrazide, 0.07-0.2 wt% of ammonium peroxide, 0.06-2.2 wt% of ammonium persulfate, 0.1-0.5 wt% of ammonium hydroxide, 41-52 wt% of ion exchange water, and 0.25-0.75 wt% of non-ionic emulsifiers.

Description

친환경 수분산성 폴리 아크릴우레탄 에멀전 수지 조성물 및 이를 적용한 아크릴우레탄 고무계 방수 도료 조성물{ENVIRONMENTALLY FRIENDLY POLY ACRYL URETHANE RESIN EMULSION COMPOSITION AND WATERPROOF GROUND MATERIALS USING THE SAME}BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an environmentally friendly water-dispersible polyacrylic urethane emulsion resin composition and an acrylic urethane rubber-based waterproof coating composition using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention [0002]

본 발명은 강한 인장력과 탄성 및 콘크리트 모르타르 소지의 부착력이 우수한 수분산성 폴리 아크릴우레탄 에멀전 수지 조성물 및 이를 적용한 아크릴우레탄 고무계 방수 도료 조성물에 관한 것이다.The present invention relates to a water-dispersible polyacrylic urethane emulsion resin composition having excellent tensile strength, elasticity and adhesion to a concrete mortar substrate, and an acrylic urethane rubber-based waterproof coating composition using the same.

일반적으로 방수 도료는 수성 또는 유성의 액상 형태의 방수제를 소지면에 도포하고, 수분 또는 용제를 건조하여 방수성 피막을 형성시키는 제제를 말한다.Generally, a waterproof coating material refers to a preparation which forms a waterproof coating by applying water or oil-based liquid waterproofing agent to the surface and drying the water or solvent.

이중, 유제형 방수 도료는 에멀전 수지형 방수 도료라고도 하는데, 에멀전 수지를 바탕 면에 덧칠하여 방수층을 만드는 방수 도료이다. 하지만, 도료가 경화될 때, 자체 수축으로 인한 균열이 적은 점은 장점이나 재질이 연약하여 면적이 넓은 장소에서는 시공이 어려운 점이 문제점으로 알려져 있다.The emulsion type waterproofing paint is also called an emulsion resin type waterproofing paint, and it is a waterproof paint which forms a waterproof layer by coating the emulsion resin on the base surface. However, when the paint is cured, it is advantageous that there is little crack due to its own shrinkage, but it is known that it is difficult to construct in a place having a large area because of its soft material.

구체적으로 수분산성 아크릴 에멀전 수지 도료 조성물은 유기 용제를 사용하지 않아서 친환경적인 장점이 있다. 하지만, 아크릴 에멀전 방수 도료는 기본적인 방수 성능에는 충족을 시키나 내화학성, 내오염성, 내후성, 내구성, 탄성, 인장력 등의 기능이 떨어지는 단점이 있다.Specifically, the water-dispersible acrylic emulsion resin coating composition does not use an organic solvent and thus has an advantage of being environmentally friendly. However, the acrylic emulsion waterproof coating satisfies the basic waterproofing performance, but has disadvantages such as chemical resistance, stain resistance, weather resistance, durability, elasticity and tensile strength.

용제형 방수 도료는 천연 및 합성고무를 휘발성 용제에 녹인 고무도료를 덧칠하여 방수층을 만드는 방수 도료이나, 휘발성 용제를 사용하여 작업 부주의 시 인화성이 강하여 화재 발생 가능성이 높고, 폐쇄된 공간에서는 환기가 제대로 되지 않을 시에는 작업자의 작업 당시뿐만 아니라, 추후 시공 완료 시에도 사용자나 입주자 등에 두통이나 심한 경우 질식 등을 유발할 수 있는 문제점이 있다. 구체적으로, 톨루엔, 자일렌, 부틸 아세테이트, 메틸 이소부틸 케톤과 같은 발암성 유기용제를 사용할 경우에는 인체 건강에 큰 피해(被害)가 예상된다.The solvent type waterproof paint is a waterproof paint that forms a waterproof layer by applying natural rubber and synthetic rubber dissolved in a volatile solvent. However, since the volatile solvent is used, the flammability is high and the possibility of fire is high. There is a problem that it can cause not only a worker's work but also a user or a tenant to have a headache or severe suffocation even when the construction is completed later. Specifically, when a carcinogenic organic solvent such as toluene, xylene, butyl acetate, or methyl isobutyl ketone is used, significant damage to human health is expected.

이에, 특허 제0666140호는 물을 경화제로 사용하고 친환경적인 원재료 및 기능성 광촉매를 선택 사용하여 환경 친화적인 폴리우레탄 방수 바닥재 수지 조성물에 관한 것으로, 제1폴리올 화합물, 방향족폴리이소시아네이트 화합물, 사슬연장제, 가소제, 충진물 및 첨가제, 착색안료를 혼합하여 주제 성분으로 하고, 여기에 제2폴리올 화합물, 수용성 난연제, 물 및 각색 염료를 주요성분으로 하는 경화제를 배합하는 것을 개시하고 있으나, 상술한 2액형 우레탄 방수 도료의 경우, 현장에서 액상과 파우더를 혼합하는 공정이 포함되어 있어, 고도의 숙련자가 아니면 부정확하게 혼합되어 방수재의 품질이 균일하지 못하는 단점이 있다.Accordingly, Patent No. 0666140 relates to an environmentally friendly polyurethane waterproof flooring resin composition using water as a curing agent and selectively using an environmentally friendly raw material and a functional photocatalyst, wherein the first polyol compound, the aromatic polyisocyanate compound, A filler, a filler, an additive and a coloring pigment are blended as a main component, and a curing agent containing a second polyol compound, a water-soluble flame retardant, water and various coloring dyes as main components is blended therein. However, In the case of paints, there is a disadvantage in that the quality of the waterproofing material is not uniform due to the incorrect mixing of the liquid and the powder in the field.

특허 제0805653호는 저취용이며 비수계인 아크릴우레탄 도료 조성물에 관한 것으로, 저취용 용제 2 중량부 내지 25 중량부, 고분자안정제 10 중량부 내지 20 중량부, 안료 10 중량부 내지 30 중량부, 침강방지제 0.1 중량부 내지 1 중량부, 비수계 분산형 아크릴수지 35 중량부 내지 55 중량부, 소포제 0.1 중량부 내지 1 중량부를 포함하는 주제부와 상기 주제부 100 중량부에 대하여 경화제 8 중량부 내지 30 중량부를 포함하는 아크릴우레탄 도료 조성물을 개시하고 있으나, 지방족 탄화수소 노르말 헥산, 노르말 헵탄, 사이클로헥산, 솔벤트 중에서 선택된 1종 이상의 용제를 3 중량부 내지 30 중량부를 사용해야 하는 문제점이 있다.Patent No. 0805653 relates to an acrylic urethane paint composition which is low in viscosity and which is non-aqueous, comprising 2 to 25 parts by weight of a low-boiling solvent, 10 to 20 parts by weight of a polymer stabilizer, 10 to 30 parts by weight of a pigment, 0.1 to 1 part by weight of a non-aqueous dispersion type acrylic resin, 35 to 55 parts by weight of a non-aqueous dispersion type acrylic resin, and 0.1 to 1 part by weight of a defoaming agent; and 8 to 30 parts by weight However, there is a problem that 3 to 30 parts by weight of at least one solvent selected from aliphatic hydrocarbons, n-hexane, n-heptane, cyclohexane and solvent is required to be used.

이에, 본 발명자는 최근 친환경적인 방수 도료에 관심을 갖고, 유기 용제를 사용하지 않으면서 강인한 인장력, 탄성, 콘크리트 모르타르 소지에 뛰어난 부착력을 부여한 친환경적인 수분산성 1액형 방수 도료를 개발하고자 하였다. Accordingly, the present inventor has recently developed an environmentally friendly, water-dispersible, water-dispersible, one-component waterproof paint that has an interest in environmentally friendly waterproof coatings and imparts a strong tensile force, elasticity, and adhesion to concrete mortar without using organic solvents.

상기와 같은 종래 문제점을 해결하기 위하여, 본 발명의 목적은 강한 인장력과 탄성 및 콘크리트 모르타르 소지에 뛰어난 부착력을 부여한 친환경적인 수분산성 아크릴우레탄 에멀전 수지 조성물을 개발하고, 이를 탄성 충진제, 착색 안료 등과 함께 방수성 도료에 적용함으로써, 유기용제 사용 없이 이음매 없는 탄성 도막으로 내수성, 콘크리트 구조물의 수축팽창에 의해 도막이 갈라지거나 손상되지 않는 특성을 갖는 친환경 1액형 수분산성 아크릴우레탄 고무계 방수 도료를 제공하는 것이다.In order to solve the above-mentioned problems, it is an object of the present invention to develop an environmentally friendly water-dispersible acrylic urethane emulsion resin composition which imparts strong tensile force, elasticity and excellent adhesion to concrete mortar pavement, Water-dispersible acrylic urethane rubber-based waterproof paint having the properties that the coating film is not cracked or damaged by the waterproof property and the expansion and contraction of the concrete structure without using an organic solvent without using an organic solvent.

상기와 같은 목적을 달성하기 위하여, 본 발명은 디아세톤 아크릴아미드(Di Acetone AcrylAmide) 1.0~2.0중량%, n-부틸 아크릴레이트(n-buthyl acrylate) 15~20 중량%, 메타크릴산(methacrylic acid) 0.5~1.5 중량%, 아크릴로니트릴(acrylonitrile) 1.0~2.2중량%, 부틸 메타크릴레이트(buthyl methacrylate) 13~18중량%, 2-에틸헥실 아크릴레이트(2-ethylhexyl acrylate) 13.2~17.5중량%, 스티렌(Styrene) 2.2~3.0 중량%, 아디프산 디히드라지드(Adipic acid Dihydrazide) 0.5~2.0중량%, 암모늄 퍼옥사이드(Ammonium peroxide) 0.07~0.2 중량%, 암모늄 퍼설페이트(Ammonium persulfate) 0.06~2.2 중량%, 암모늄 히드록사이드(Ammonium hydroxide) 0.1~0.5 중량%, 이온교환수 41~52 중량% 및 비이온성 유화제 0.25~0.75 중량%을 혼합하여 반응시켜 이루어지는 친환경 수분산성 폴리 아크릴우레탄 에멀전 수지 조성물을 제공한다.In order to achieve the above-mentioned object, the present invention provides a composition comprising 1.0 to 2.0% by weight of diacetone acrylamide, 15 to 20% by weight of n-buthyl acrylate, By weight of acrylonitrile, 0.5 to 1.5% by weight of acrylonitrile, 1.0 to 2.2% by weight of acrylonitrile, 13 to 18% by weight of butyl methacrylate, 13.2 to 17.5% by weight of 2-ethylhexyl acrylate, 2.2 to 3.0 wt% of styrene, 0.5 to 2.0 wt% of adipic acid dihydrazide, 0.07 to 0.2 wt% of ammonium peroxide, 0.06 to 0.2 wt% of ammonium persulfate, Water-dispersible polyacrylic urethane emulsion resin composition obtained by mixing 2.2 wt% of water, 0.1 to 0.5 wt% of ammonium hydroxide, 41 to 52 wt% of ion-exchanged water, and 0.25 to 0.75 wt% of a nonionic emulsifier .

또한, 다른 목적을 달성하기 위하여, 본 발명은 (a) 반응기에 이온교환수 20~25 중량%와 유화제 0.15~0.25 중량%를 투입하고 70~90 ℃의 온도를 유지시키면서 암모늄퍼옥사이드 0.07~0.2중량%를 투입하여 혼합하는 단계; (b) 상기 (a)의 혼합물에, 이온교환수 18~22중량%, 디아세톤 아크릴아미드 1.0~2.0중량%, n-부틸 아크릴레이트 15~20 중량%, 메타크릴산 0.5~1.5 중량%, 아크릴로니트릴 1.0~2.2중량%, 부틸 메타크릴레이트 13~18중량%, 2-에틸헥실 아크릴레이트 13.2~17.5 중량%, 스티렌 2.2~3.0중량%, 비이온성 유화제 0.1~0.5중량%, 아디프산 디히드라지드 0.5~2.0중량% 및 암모늄 퍼설페이트 0.01~1.0 중량를 혼합한 혼합물을 3~4 시간 동안 드로핑(dropping)하여 반응시키는 단계; (c) 상기 (b)의 반응물에, 암모늄 퍼셀페이트 0.05~1.2 중량% 및 이온교환수 3.0~5.0 중량%를 혼합한 혼합물을 1~2 시간동안 드로핑하여 반응시키는 단계; (d) 상기 (c)의 반응물을 진공 상태에서 5~ 20분간 유지시켜서 미반응 모노머를 제거하는 단계; 및 (e) 상기 (d)의 반응물을 40~50℃로 낮추면서 암모늄 히드록사이드 0.1~0.5 중량%를 투입하여 반응을 시키는 단계;를 거쳐서 수득하는 것을 특징으로 하는 친환경 수분산성 폴리 아크릴우레탄 에멀전 수지 조성물의 제조방법을 제공한다.(A) 20 to 25% by weight of ion-exchanged water and 0.15 to 0.25% by weight of an emulsifier are added to the reactor, and ammonium peroxide 0.07 to 0.2 % By weight; (b) 18 to 22% by weight of ion exchange water, 1.0 to 2.0% by weight of diacetone acrylamide, 15 to 20% by weight of n-butyl acrylate, 0.5 to 1.5% by weight of methacrylic acid, By weight of styrene, from 0.1 to 0.5% by weight of nonionic emulsifier, from 0.1 to 0.5% by weight of acrylonitrile, from 13 to 18% by weight of butyl methacrylate, from 13.2 to 17.5% by weight of 2-ethylhexyl acrylate, 0.5 to 2.0% by weight of dihydrazide and 0.01 to 1.0% by weight of ammonium persulfate is dropped and reacted for 3 to 4 hours; (c) dropping a mixture of 0.05 to 1.2% by weight of ammonium persulfate and 3.0 to 5.0% by weight of ion exchanged water in the reactant of (b) for 1 to 2 hours to react; (d) maintaining the reactant of (c) in a vacuum for 5 to 20 minutes to remove unreacted monomer; And (e) reacting the reaction product of (d) in an amount of from 0.1 to 0.5% by weight of ammonium hydroxide while lowering the temperature of the reaction product to 40 to 50 ° C to obtain an eco-friendly water-dispersible polyacrylic urethane emulsion A method for producing a resin composition is provided.

또한, 또 다른 목적을 달성하기 위하여, 본 발명은 상기 폴리 아크릴우레탄 에멀전 수지 조성물 45.0~55.0 중량%에, 분산제 0.1~0.3중량%, 물 4.0~8.5 중량%, 방부제 0.2~0.5중량%, 이산화티타늄(TiO2) 0.5~3.0중량%, 탄산칼슘 35.0~45.0중량%, 비이온성 증점제 0.5~1.3중량%, 착색 안료 1.0~6.0 중량%, 소포제 0.1~0.3중량%를 혼합하여 이루어지는 친환경 수분산성 아크릴우레탄 고무계 방수 도료 조성물을 제공한다.In another aspect of the present invention, there is provided a polyurethane resin composition comprising 45.0 to 55.0 wt% of the polyacrylic urethane emulsion resin composition, 0.1 to 0.3 wt% of a dispersant, 4.0 to 8.5 wt% of water, 0.2 to 0.5 wt% of a preservative, Soluble water-dispersible acrylic urethane obtained by mixing 0.5 to 3.0 wt% of titanium oxide (TiO 2 ), 35.0 to 45.0 wt% of calcium carbonate, 0.5 to 1.3 wt% of a nonionic thickener, 1.0 to 6.0 wt% of a color pigment, and 0.1 to 0.3 wt% A waterproof coating composition for rubber is provided.

나아가, 본 발명은 (a) 상기 폴리 아크릴우레탄 에멀전 수지 조성물 45.0~55.0 중량%에, 분산제 0.1~0.3중량%, 물 4.0~8.5 중량%, 방부제 0.2~0.5중량%, 이산화티타늄(TiO2) 0.5~3.0중량%, 탄산칼슘 35.0~45.0중량%, 비이온성 증점제 0.5~1.3중량%, 착색 안료 1.0~6.0 중량% 및 소포제 0.1~0.3중량%를 교반기에 투입하고 750~900 rpm 속도로 혼합하는 단계; 및 (b) 상기 (a)의 혼합물을 진공 상태에서 5~ 20분간 유지시켜서 미반응 모노머를 제거하는 단계;를 포함하여 이루어지는 것을 특징으로 하는 친환경 수분산성 아크릴우레탄 고무계 방수 도료의 제조방법을 제공한다.(A) 0.1 to 0.3% by weight of a dispersant, 4.0 to 8.5% by weight of water, 0.2 to 0.5% by weight of an antiseptic agent, and 0.5 to 0.5% by weight of titanium dioxide (TiO 2 ) 0.5 By weight of calcium carbonate, 35.0 to 45.0% by weight of calcium carbonate, 0.5 to 1.3% by weight of a nonionic thickener, 1.0 to 6.0% by weight of a color pigment and 0.1 to 0.3% by weight of an antifoaming agent and mixing at a speed of 750 to 900 rpm ; And (b) maintaining the mixture of (a) in a vacuum for 5 to 20 minutes to remove unreacted monomers. The present invention also provides a process for producing an environmentally water-dispersible acrylic urethane rubber waterproof paint, .

이상과 같이, 본 발명은 본 발명은 강한 인장력과 탄성 및 콘크리트 모르타르 소지에 뛰어난 부착력을 부여한 친환경적인 수분산성 아크릴우레탄 에멀전 수지조성물을 개발하고, 이를 탄성 충진제, 착색 안료 등과 함께 방수성 도료에 적용함으로써, 유기용제 사용 없이 이음매 없는 탄성 도막으로 내수성, 콘크리트 구조물의 수축팽창에 의해 도막이 갈라지거나 손상되지 않는 특성을 갖는 친환경 1액형 수분산성 아크릴우레탄 고무계 방수 도료를 제공하게 한 것이다.As described above, the present invention has developed an environmentally friendly water-dispersible acrylic urethane emulsion resin composition which imparts a strong tensile force, elasticity and excellent adhesion to concrete mortar pavement, and applies it to a waterproof paint together with an elastic filler, The present invention provides an environmentally friendly one-pack type water-dispersible acrylic urethane rubber waterproof paint having a water-resistant elastic coating film without the use of an organic solvent, and a property that the coating film is not cracked or damaged by expansion and contraction of a concrete structure.

구체적으로, 본 발명에 따른 방수 도료는 작업성 측면에서 수성 1액형 타입으로 작업이 용이하여 전문 도장인뿐만 아니라 일반 가정에서도 붓이나 롤러를 사용하여 쉽게 도장할 수 있는 장점, 유기용제가 거의 함유하지 않은 수성타입으로 냄새가 적고 인체에 안전한 친환경적인 장점, 이음매 없는 일체화된 연속적인 탄성 도막을 형성하므로 완벽한 방수성능을 발휘하며 진동과 균열에 저항성이 강하면서 콘크리트 구조물의 수축팽창에 의한 도막의 균일을 강한 탄성과 인장력으로 커버가 가능한 장점 등의 효과를 제공한다.Specifically, the waterproof paint according to the present invention is advantageous in that it is easy to work with an aqueous one-component type in terms of workability, so that it can be easily painted using a brush or roller in a home as well as a professional paint, It is a non-aqueous type and has a low odor and is safe for human body. It has a continuous water-repellent performance due to continuous seamless elastic coating. It is resistant to vibration and cracking, And the advantage of being able to cover with strong elasticity and tensile force.

도 1은 본 발명의 바람직한 일실시예로 제조한 아크릴우레탄 고무계 도료 조성물의 탄성을 나타낸 사진이다.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph showing elasticity of an acrylic urethane rubber coating composition prepared according to a preferred embodiment of the present invention. FIG.

이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.

이때, 사용되는 기술 용어 및 과학 용어에 있어서 다른 정의가 없다면, 이 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 통상적으로 이해하고 있는 의미를 가진다.Here, unless otherwise defined in the technical terms and the scientific terms used, those having ordinary skill in the art to which the present invention belongs have the same meaning as commonly understood by those skilled in the art.

또한, 종래와 동일한 기술적 구성 및 작용에 대한 반복되는 설명은 생략하기로 한다.Repeated descriptions of the same technical constitution and operation as those of the conventional art will be omitted.

본 발명은 강한 인장력과 탄성 및 콘크리트 모르타르 소지에 뛰어난 부착력을 부여한 친환경적인 수분산성 아크릴우레탄 에멀전 수지 조성물을 개발하고, 이를 탄성 충진제, 착색 안료 등과 함께 방수성 도료에 적용함으로써, 유기용제 사용 없이 이음매 없는 탄성 도막으로 내수성, 콘크리트 구조물의 수축팽창에 의해 도막이 갈라지거나 손상되지 않는 특성을 갖는 친환경 1액형 수분산성 아크릴우레탄 고무계 방수 도료를 제공하게 한 것이다.The present invention has developed an environmentally friendly water-dispersible acrylic urethane emulsion resin composition which imparts excellent tensile strength, elasticity and excellent adhesion to concrete mortar pavement, and it is applied to a waterproof paint together with an elastic filler and a color pigment to provide seamless elasticity Soluble one-component water-dispersible acrylic urethane rubber-based waterproof paint having properties such that the coating film is waterproof and the coating film is not cracked or damaged by the expansion and contraction of the concrete structure.

본 발명에 따른 수분산성 아크릴우레탄 고무계 방수 도료는 특히, 신축건물이나 오래된 건물 옥상 또는 지붕 방수 전용 도료로 사용할 수 있다.The water-dispersible acrylic urethane rubber-based waterproofing paint according to the present invention can be used particularly as a paint for a new building, a rooftop of an old building or a roof waterproofing paint.

본 발명에서 이온교환수는 통상의 이온교환법으로 정제하여 양이온, 음이온 외에 유리 탄산, 황화수소, 암모니아 등을 거의 제거한 순수한 물을 말한다.In the present invention, ion-exchanged water refers to pure water which has been purified by a conventional ion exchange method and has been substantially free of free carbonic acid, hydrogen sulfide, ammonia, etc. in addition to cations and anions.

본 발명에서 아크릴우레탄 공중합체 제조에 사용되는 모노머(monomer)는 인장력, 탄성 및 콘크리트 모르타르 소지에 대한 뛰어난 부착력 등을 고려하여 디아세톤 아크릴아미드(Di Acetone AcrylAmide), n-부틸 아크릴레이트(n-buthyl acrylate), 메타크릴산(methacrylic acid), 아크릴로니트릴(acrylonitrile), 부틸 메타크릴레이트(buthyl methacrylate), 2-에틸헥실 아크릴레이트(2-ethylhexyl acrylate) 및 스티렌(Styrene) 2.2~3.0 중량%을 사용한다.In the present invention, the monomer used in the production of the acrylic urethane copolymer is preferably selected from the group consisting of diacetone acrylamide, n-buthyl acrylate, n-butylacrylate, n-butylacrylate, and the like in consideration of tensile strength, elasticity, acrylate, methacrylic acid, acrylonitrile, buthyl methacrylate, 2-ethylhexyl acrylate and styrene in an amount of 2.2 to 3.0% by weight, use.

이때, 본 발명에 따른 수분산성 폴리 아크릴우레탄 수지 조성물 100 중량% 기준으로 디아세톤 아크릴아미드(Di Acetone AcrylAmide) 1.0~2.0 중량%, n-부틸 아크릴레이트(n-buthyl acrylate) 15~20 중량%, 메타크릴산(methacrylic acid) 0.5~1.5 중량%, 아크릴로니트릴(acrylonitrile) 1.0~2.2 중량%, 부틸 메타크릴레이트(buthyl methacrylate) 13~18 중량%, 2-에틸헥실 아크릴레이트(2-ethylhexyl acrylate) 13.2~17.5 중량%, 및 스티렌(Styrene) 2.2~3.0 중량%을 사용하는 데, 이와 같은 혼합비로 중합시킬 경우 종래 우레탄 수지 방수재보다 인장력 및 탄성은 우수하고 콘크리트 소지면의 부착력은 강화시킬 수 있기 때문이다.In this case, 1.0 to 2.0% by weight of diacetone acrylamide, 15 to 20% by weight of n-buthyl acrylate based on 100% by weight of the water-dispersible polyacrylic urethane resin composition according to the present invention, Acrylonitrile, 0.5 to 1.5 wt% of methacrylic acid, 1.0 to 2.2 wt% of acrylonitrile, 13 to 18 wt% of buthyl methacrylate, 2-ethylhexyl acrylate ) And 13.2 to 17.5% by weight of styrene, and 2.2 to 3.0% by weight of styrene are used. When the polymer is polymerized in such a mixing ratio, the tensile strength and elasticity are superior to those of conventional urethane resin waterproofing materials, to be.

본 발명에서 사용되는 아디프산 디히드라지드(Adipic acid Dihydrazide)는 경화제로 사용한다. 이때, 전체 에멀전 수지 조성물 100 중량% 기준으로 0.5 중량% 미만을 사용하면 상술한 효과가 미미하고 2.0 중량%를 초과하여 사용하는 경우에는 다른 필수 구성 성분을 충분하게 사용하지 못하기 때문에, 상술한 사용 범위 내에서 사용하는 것이 바람직하다.The adipic acid dihydrazide used in the present invention is used as a curing agent. At this time, if the total emulsion resin composition is used in an amount of less than 0.5% by weight based on 100% by weight of the total emulsion resin composition, the above-mentioned effect is insignificant, and if it exceeds 2.0% by weight, It is preferable to use it within the range of.

본 발명에 따른 폴리 아크릴우레탄 에멀전 수지 조성물에서 사용하는 암모늄 퍼옥사이드(Ammonium peroxide), 암모늄 퍼설페이트(Ammonium persulfate) 및 암모늄 히드록사이드(Ammonium hydroxide)은 모노머의 가교 결합(cross-link)을 통해 중합 촉진제로 사용하는데, 이는 상술한 다양한 모노머를 결합시키기 위하여 각 모노머의 결합 반응을 촉진할 수 있도록, 암모늄 퍼옥사이드 0.07~0.2 중량%, 암모늄 퍼설페이트 0.06~2.2 중량% 및 암모늄 히드록사이드 0.1~0.5 중량% 사용하는데, 이는 상술한 사용 범위의 최소량 미만을 사용하면 미반응 모노머가 증가하고, 최대량을 초과하여 사용하면 사용량 대비 효율성이 낮고 다른 필수 구성 성분을 충분하게 사용하지 못하기 때문에, 상술한 사용 범위 내에서 사용하는 것이 바람직하다.Ammonium peroxide, ammonium persulfate and ammonium hydroxide used in the polyacrylic urethane emulsion resin composition according to the present invention can be polymerized through cross-linking of monomers, Such as 0.07 to 0.2% by weight of ammonium peroxide, 0.06 to 2.2% by weight of ammonium persulfate and 0.1 to 0.5% by weight of ammonium hydroxide so as to accelerate the binding reaction of the respective monomers to bind the various monomers described above. Weight percent of the total weight of the composition is used because it results in an increase in unreacted monomers when used below a minimum amount of the abovementioned usage range, It is preferable to use it within the range of.

이때, 본 발명에 따른 수분산성 폴리 아크릴우레탄 에멀전 수지 조성물에서 상술한 각 성분이 균일하게 혼합되어 반응이 일어날 수 있도록, 상술한 모노머와 경화제 중량 대비 이온교환수 41~52 중량% 및 비이온성 유화제 0.25~0.75 중량%을 첨가시켜 반응시키는 것이 바람직하다. 이는 충분한 중합 반응을 유도할 수 있도록 이온교환수와 비이온성 유화제를 사용하는데, 상술한 최소 사용범위 미만을 사용할 경우에는 상술한 유도 효과가 저감되어 미반응 모노머가 증가하고 최대 사용범위를 초과하여 사용하면 사용량 대비 효율성이 낮고 다른 필수 구성 성분을 충분하게 사용하지 못하기 때문에, 상술한 사용 범위 내에서 사용하는 것이 바람직하다.In the water-dispersible polyacrylic urethane emulsion resin composition according to the present invention, in order to uniformly mix and react the above components, 41 to 52% by weight of ion-exchanged water and 0.25% by weight of a nonionic emulsifier By weight to 0.75% by weight. This is because ion exchange water and nonionic emulsifier are used so as to induce a sufficient polymerization reaction. When the above-mentioned minimum use range is used, the above-mentioned induction effect is reduced, unreacted monomer increases, It is preferable to use it within the above-mentioned use range, because it is low in efficiency relative to usage amount and can not sufficiently use other essential constituents.

또한, 본 발명에 따른 친환경 수분산성 아크릴우레탄 고무계 방수 도료 조성물은 상기 수분산성 폴리 아크릴우레탄 에멀전 수지 조성물 45.0~55.0 중량%에, 분산제 0.1~0.3 중량%, 물 4.0~8.5 중량%, 방부제 0.2~0.5 중량%, 이산화티타늄(TiO2) 0.5~3.0 중량%, 탄산칼슘 35.0~45.0 중량%, 비이온성 증점제 0.5~1.3 중량%, 착색 착색 안료 1.0~6.0 중량%, 소포제 0.1~0.3 중량%를 혼합하여 제조한다.The waterproof acrylic urethane rubber-based waterproof coating composition according to the present invention comprises 45.0 to 55.0% by weight of the water-dispersible polyacrylic urethane emulsion resin composition, 0.1 to 0.3% by weight of a dispersant, 4.0 to 8.5% by weight of water, , 0.5 to 3.0 wt% of titanium dioxide (TiO 2 ), 35.0 to 45.0 wt% of calcium carbonate, 0.5 to 1.3 wt% of a nonionic thickener, 1.0 to 6.0 wt% of a colored pigment and 0.1 to 0.3 wt% of a defoaming agent .

본 발명의 방수 도료 조성물에서 수분산성 폴리 아크릴우레탄 에멀전 수지 조성물은 본 발명의 목적에 부합되도록 전체 조성물 100 중량%를 기준으로 45.0~55.0 중량%를 사용하는데, 45 중량% 미만을 사용하면 강인한 인장력, 탄성, 콘크리트 모르타르 소지에 뛰어난 부착력 효과가 저감되고 55 중량%를 초과하여 사용하면 작업성이 저하되고 다른 필수 구성 성분을 충분하게 사용하지 못하므로, 상술한 사용 범위 내에서 사용하는 것이 바람직하다. In the waterproof coating composition of the present invention, the water-dispersible polyacrylic urethane emulsion resin composition is used in an amount of 45.0 to 55.0% by weight based on 100% by weight of the total composition to meet the object of the present invention. When less than 45% by weight is used, Elastic and concrete mortar, and when it is used in an amount exceeding 55% by weight, the workability is lowered and other necessary components are not used sufficiently, so that it is preferable to use it within the above-mentioned use range.

또한, 본 발명에 따른 고무계 방수 도료 조성물 100 중량% 기준에서 방부제 0.2~0.5 중량% 및 소포제 0.1~0.3 중량%의 사용은 본 발명의 분야에서 당업자가 일반적으로 사용하는 사용 범위를 사용한 것이다.The use of 0.2 to 0.5% by weight of a preservative and 0.1 to 0.3% by weight of an antifoaming agent on the basis of 100% by weight of the rubber-based waterproof coating composition according to the present invention uses the range of use generally used by those skilled in the art.

또한, 본 발명의 도료 조성물 100 중량%에서 물은 아크릴우레탄 에멀전 수지조성물과 각 필수 구성 성분 간에 균일하게 혼합되고, 일정상 점성을 갖는 유동성을 유지하기 위하여 4.0~8.5 중량% 내에서 사용하는 것이 바람직하다. 이는 4.0 중량% 미만을 사용하면 상술한 효과가 미미하고, 8.5 중량%를 초과하면 도료 조성물의 점도가 너무 높아져서 작업성이 저하되기 때문이다.In addition, in 100% by weight of the coating composition of the present invention, water is uniformly mixed with the acrylic urethane emulsion resin composition and each essential constituent, and is preferably used within 4.0 to 8.5% by weight in order to maintain fluidity having uniform viscosity Do. If the amount is less than 4.0% by weight, the above-mentioned effect is insignificant. If the amount is more than 8.5% by weight, the viscosity of the coating composition becomes too high and workability is deteriorated.

그리고, 본 발명에서 이산화티타늄과 착색 안료는 무기질 안료로서, 상술한 이산화티타늄과 착색 안료의 배합 비율은 본 발명의 방수 도료로서 색채의 명암을 적합하게 하면서 적절한 커버력과 착색력을 제공하는데, 상술한 사용 범위의 최소량 미만을 사용하면 상술한 효능이 저감되고, 최대량을 초과하면 다른 필수 구성성분을 충분하게 사용하지 못하면서 도료 단가를 높이기 때문에, 상술한 사용 범위 내에서 사용하는 것이 바람직하다. 착색 안료는 방수 도료의 특성상 그린(녹색) 계열, 옐로우(노란색) 계열 또는 레드(적색) 계열의 무기질 안료를 사용하는 것이 바람직하고, 보다 더 바람직하게는 산화철 계열을 사용한다. 하지만, 본 발명의 목적에 부합되는 것이라면 그 어느 색의 무기질 안료를 사용해도 무방하다.In the present invention, the titanium dioxide and the color pigment are inorganic pigments. The mixing ratio of the above-mentioned titanium dioxide and the color pigment is suitable as the waterproof paint of the present invention, It is preferable to use it within the above-mentioned use range, because the above-mentioned effect is reduced when the amount is less than the minimum amount, and when the amount exceeds the maximum amount, other necessary components are not sufficiently used and the cost of the paint is increased. The colored pigment is preferably a green pigment, a yellow pigment or a red pigment based on the characteristics of the waterproof paint, more preferably an iron oxide based pigment. However, an inorganic pigment of any color may be used as long as it meets the object of the present invention.

본 발명에서 비이온성 증점제는 도료 조성물에 일정한 점도 유지하여 도료 안정성에 큰 역할을 하는데, 도료 조성물 100 중량% 기준으로 0.5 중량% 미만을 사용하면 도료 점도가 낮아져서 도장 시 도료가 흘러내릴 수 있고, 1.3 중량%를 초과하여 사용하면 점도가 높아 작업성이 나빠지기 때문에, 상술한 범위 내에서 사용하는 것이 바람직하다.In the present invention, the non-ionic thickener plays a significant role in the stability of the coating by maintaining a constant viscosity in the coating composition. When less than 0.5% by weight based on 100% by weight of the coating composition is used, the viscosity of the coating is lowered, If it is used in excess of the weight%, the viscosity is high and the workability is deteriorated. Therefore, it is preferable to use it within the above-mentioned range.

탄산칼슘은 도막의 보강과 증량 목적인 체질 안료로서 사용하는데, 35 중량% 미만을 사용하면 상술한 효과가 미미하고, 45 중량%를 초과하면 오히려 도막의 특성을 변화시키고 다른 필수 구성 성분을 충분하게 사용하지 못하므로, 상술한 범위 내에서 사용하는 것이 바람직하다.When the amount of calcium carbonate is less than 35% by weight, the above effect is insignificant. If it exceeds 45% by weight, the properties of the coating film are changed and other essential constituents are sufficiently used It is preferable to use it within the above-mentioned range.

본 발명에서 바람직한 수분산성 폴리 아크릴우레탄 에멀전 수지 조성물의 제조공정은 다음과 같다.The process for producing the water-dispersible polyacrylic urethane emulsion resin composition preferred in the present invention is as follows.

[제 1 공정] [First Step]

1-1. 1차 반응액 제조1-1. Production of primary reaction solution

반응기에 이온교환수 20~25 중량%와 유화제 0.15~0.25 중량%를 투입하고 70~90 ℃의 온도를 유지시키면서 암모늄 퍼옥사이드 0.07~0.2중량%를 투입하여 혼합한다. 이는 모노머 간 가교 결합의 최적의 중합 온도 조건인 70~90 ℃로 유지하면서 1차 중합 촉진제인 암모늄 퍼옥사이드를 먼저 이온 교환수에 첨가하여, 모노머 간의 중합 반응이 원활하게 이루어질 수 있는 상태를 사전에 조성하기 때문이다.20 to 25% by weight of ion exchange water and 0.15 to 0.25% by weight of an emulsifier are added to the reactor, and 0.07 to 0.2% by weight of ammonium peroxide is added thereto while maintaining the temperature at 70 to 90 ° C. This is because the ammonium peroxide, which is the first polymerization promoter, is first added to the ion-exchanged water while maintaining the optimum polymerization temperature condition of the monomer-to-monomer crosslinking at 70 to 90 ° C, .

1-2. 1-2. 모노머Monomer 혼합액 제조 Mixed liquid manufacturing

이온교환수 18~22중량%에 디아세톤 아크릴아미드 1.0~2.0중량%, n-부틸 아크릴레이트 15~20 중량%, 메타크릴산 0.5~1.5 중량%, 아크릴로니트릴 1.0~2.2중량%, 부틸 메타크릴레이트 13~18중량%, 2-에틸헥실 아크릴레이트 13.2~17.5 중량% 및 스티렌 2.2~3.0중량%로 이루어진 모노머와 비이온성 유화제 0.1~0.5중량%, 경화제인 아디프산 디히드라지드 0.5~2.0중량% 및 중합 반응 촉진제인 암모늄 퍼설페이트 0.01~1.0 중량%를 첨가한 후, 균일하게 혼합한다.1.0 to 2.0% by weight of diacetone acrylamide, 15 to 20% by weight of n-butyl acrylate, 0.5 to 1.5% by weight of methacrylic acid, 1.0 to 2.2% by weight of acrylonitrile, 0.1 to 0.5% by weight of a monomer comprising 13 to 18% by weight of acrylate, 13 to 18% by weight of 2-ethylhexyl acrylate and 2.2 to 3.0% by weight of styrene, 0.1 to 0.5% by weight of a nonionic emulsifier, 0.5 to 2.0% by weight of adipic acid dihydrazide as a curing agent And 0.01 to 1.0% by weight of ammonium persulfate, which is a polymerization reaction promoter, are added and uniformly mixed.

[제 2 공정] [Second Step]

2-1. 1차 중합 반응2-1. Primary polymerization reaction

상기 제 1 공정을 거친 1-1의 혼합물에, 1-2의 모노머 혼합물을 3~4 시간 동안 드로핑(dropping)하여 반응시킨다. 이는 1-2의 모노머 혼합물을 한꺼번에 넣으면 모노머 간의 반응이 충분하게 이루어지지 않기 때문에 3~4 시간에 걸쳐 천천히 혼합물을 떨어뜨려서 반응시키는 것이 바람직하기 때문이다. To the mixture of 1-1 through the first step, 1-2 monomer mixture is dropped and reacted for 3 to 4 hours. This is because it is preferable to slowly drop the mixture over a period of 3 to 4 hours, since the reaction between the monomers is insufficient when the monomer mixture of 1-2 is put together.

이때, 온도는 제 1공정 같이 70~90 ℃로 유지한다.At this time, the temperature is maintained at 70 to 90 DEG C like the first step.

2-2. 2차 반응액 제조2-2. Secondary reaction liquid preparation

암모늄 퍼셀페이트 0.05~1.2 중량% 및 이온교환수 3.0~5.0 중량%를 혼합한 혼합물을 제조한다. 이는 신선한 반응액을 첨가함으로써, 미반응 모노머를 다시 반응시킬 수 있기 때문이다.0.05 to 1.2% by weight of ammonium persulfate and 3.0 to 5.0% by weight of ion-exchanged water is prepared. This is because by adding a fresh reaction solution, the unreacted monomer can be reacted again.

[제 3 공정] [Third Step]

3-1. 2차 중합 반응3-1. Second polymerization reaction

상기 제 2 공정을 거친 2-1의 반응액에 2-1의 혼합물을 1~2 시간 동안 드로핑(dropping)하여 반응시킨다.The mixture of 2-1 is dropped into the reaction solution 2-1 through the second step for 1 to 2 hours to react.

3-1. 미반응 3-1. Unresolved 모노머Monomer 제거 remove

상기 3-1 공정을 거친 반응물을 진공 상태에서 5~ 20분간 유지시켜서 미반응 모노머를 제거한다. 이때, 진공펌프를 사용하는 것이 바람직하다.The reaction product after the 3-1 process is maintained in a vacuum for 5 to 20 minutes to remove unreacted monomer. At this time, it is preferable to use a vacuum pump.

[제 4 공정][Fourth Step]

상기 제 3-1 및 3-2 공정을 거친 반응물을 40~50℃로 낮추면서 암모늄 히드록사이드 0.1~0.5 중량%를 투입하여 마지막 반응을 시킨다. 이때, 반응은 도료의 물리적 특성이 나타날 수 있도록 적어도 1시간 동안 교반하면서 반응시키는 것이 바람직하다.The reactants after the steps 3-1 and 3-2 are lowered to 40 to 50 ° C while 0.1 to 0.5% by weight of ammonium hydroxide is added to the reaction. At this time, it is preferable that the reaction is carried out with stirring for at least 1 hour so that the physical properties of the paint can be exhibited.

이와 같이, 본 발명에 따른 폴리 아크릴우레탄 에멀전 수지 조성물의 점도는 700~1,000 cps(25℃기준), 고형분은 45~60 중량%, 유리전이온도는 약 -20℃ 전후의 특성을 나타낸다.Thus, the viscosity of the polyacrylic urethane emulsion resin composition according to the present invention is 700 to 1,000 cps (based on 25 ° C), the solid content is 45 to 60% by weight, and the glass transition temperature is about -20 ° C.

또한, 본 발명에 따른 바람직한 친환경 아크릴우레탄 고무계 방수 도료의 제조공정은 다음과 같다.The process for producing an environmentally friendly acrylic urethane rubber waterproof paint according to the present invention is as follows.

[제 1 공정][First Step]

본 발명에 따른 폴리 아크릴우레탄 에멀전 수지 조성물 45.0~55.0 중량%에, 분산제 0.1~0.3중량%, 물 4.0~8.5 중량%, 방부제 0.2~0.5중량%, 이산화티타늄(TiO2) 0.5~3.0중량%, 탄산칼슘 35.0~45.0중량%, 비이온성 증점제 0.5~1.3중량%, 착색 안료 1.0~6.0 중량% 및 소포제 0.1~0.3중량%를 교반기에 투입하고 750~900 rpm 속도로 혼합한다. 이는 750~900 rpm 속도로 혼합해야 균일하게 혼합되기 때문이다. The polyacrylic urethane emulsion resin composition according to the present invention is characterized by containing 45.0 to 55.0 wt% of a dispersant, 4.0 to 8.5 wt% of water, 0.2 to 0.5 wt% of a preservative, 0.5 to 3.0 wt% of titanium dioxide (TiO 2 ) 35.0 to 45.0% by weight of calcium carbonate, 0.5 to 1.3% by weight of a nonionic thickener, 1.0 to 6.0% by weight of a color pigment and 0.1 to 0.3% by weight of a defoaming agent are put into a stirrer and mixed at a speed of 750 to 900 rpm. This is because they must be mixed at a speed of 750 to 900 rpm to be uniformly mixed.

이때, 본 발명에서 비이온성 증점제(rheology modifier)는 우레탄 증점제를 사용하는 것이 바람직하다. In the present invention, it is preferable to use a urethane thickener as the non-ionic rheology modifier.

[제 2 공정][Second Step]

상기 제 1 공정을 거친 혼합물을 진공 상태에서 5~ 20분간 유지시켜서 미반응 모노머를 제거하고, 1액형 아크릴우레탄 고무계 방수 도료를 수득한다.The mixture obtained through the first step is maintained in a vacuum for 5 to 20 minutes to remove unreacted monomers to obtain a one-pack type acrylic urethane rubber waterproof paint.

이때, 본 발명의 방수 도료는 주도(KU/25℃)는 100~120의 물성을 나타낸다.At this time, the waterproof paint of the present invention exhibits a physical property (KU / 25 ° C) of 100 to 120.

한편, 본 발명에 따라 제조된 친환경 아크릴우레탄 고무계 방수 도료는 다음과 같은 방법으로 간편하게 시공할 수 있다.Meanwhile, the environmentally friendly acrylic urethane rubber waterproof paint prepared according to the present invention can be easily applied by the following method.

[1 단계] [Stage 1] 시공면Construction site 청소 cleaning

시공면의 먼지나 유분을 완전히 제거한다.Completely remove dust and oil on installation surface.

[2 단계] [Step 2] 프라이머primer 도포 apply

시공면에 아크릴계 프라이머로 먼저 도포한다.First, apply acrylic primer to the construction surface.

[3 단계] 도장[Step 3] Painting

본 발명의 친환경 아크릴우레탄 고무계 방수 도료를 붓, 롤러, 스프레이를 이용하여 도장한다. 이때, 건조 도막 두께는 적어도 1mm가 되도록 하는 것이 바람직하다.The environmentally friendly acrylic urethane rubber waterproof paint of the present invention is painted using a brush, roller and spray. At this time, the dry film thickness is preferably at least 1 mm.

또한, 본 발명에 따른 아크릴우레탄 고무계 방수 도료는 원액 사용을 원칙으로 하나 경우에 따라서는 도료 100 중량% 대비 5% 이내의 물을 첨가하여 사용할 수 있다.The acrylic urethane rubber-based waterproof paint according to the present invention is generally used in the form of undiluted solution. In some cases, water may be added in an amount of 5% or less based on 100% by weight of the paint.

이하, 본 발명을 하기의 실시예로써 더욱 상세히 설명하고자 한다. 하지만 이는 본 발명의 보다 쉬운 이해를 돕기 위한 것이지, 이들을 통하여 본 발명을 한정하고자 하는 것임은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples. It is to be understood, however, that the same is by way of illustration and example only and is not to be taken by way of limitation.

[[ 실시예Example ]]

1. One. 수분산Water dispersion 폴리우레탄 조성물 제조 Preparation of polyurethane composition

본 발명에 따른 수분산 폴리아크릴우레탄 수지 에멀전은 하기 표1의 조성 및 순서에 따라 제조하였다. 이때, 유화제는 NEWCOL 707SF(CAS No.104042-66-2, Sino-Japan chemical)를 사용하였다.
The water-dispersed polyacryl urethane resin emulsion according to the present invention was prepared according to the composition and the procedure of Table 1 below. At this time, NEWCOL 707SF (CAS No. 104042-66-2, Sino-Japan chemical) was used as an emulsifier.

제법 순서Recipe order 성분명Ingredients 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 이온교환수Ion-exchange water 25 중량%25 wt% 20 중량%20 wt% 20 중량%20 wt% 유화제 1Emulsifier 1 0.15 중량%0.15 wt% 0.15 중량%0.15 wt% 0.25 중량%0.25 wt% 암모늄 퍼옥사이드Ammonium peroxide 0.15 중량%0.15 wt% 0.07 중량%0.07 wt% 0.1 중량%0.1 wt% 이온교환수Ion-exchange water 18 중량%18 wt% 18 중량%18 wt% 22 중량%22 wt% 디아세톤 아크릴아미드Diacetone acrylamide 1 중량%1 wt% 1 중량%1 wt% 2 중량%2 wt% n-부틸 아크릴레이트n-butyl acrylate 20 중량%20 wt% 15 중량%15 wt% 15 중량%15 wt% 메타크릴산Methacrylic acid 0.7 중량%0.7 wt% 1.5 중량%1.5 wt% 0.5 중량%0.5 wt% 아크릴로니트릴Acrylonitrile 1 중량%1 wt% 2.2 중량%2.2 wt% 1.3 중량%1.3 wt% 부틸 메타크릴레이트Butyl methacrylate 13 중량%13 wt% 18 중량%18 wt% 13 중량%13 wt% 2-에틸 헥실 아크릴레이트2-ethylhexyl acrylate 13.2 중량%13.2 wt% 14.2 중량%14.2 wt% 17.5 중량%17.5 wt% 스티렌Styrene 2.2 중량%2.2 wt% 2.2 중량%2.2 wt% 3 중량%3 wt% 아디프산 디 하이드라지드Adipic acid dihydrazide 1 중량%1 wt% 2 중량%2 wt% 50.5 중량%50.5 wt% 유화제 2Emulsifier 2 0.1 중량%0.1 wt% 0.5 중량%0.5 wt% 0.14 중량%0.14 wt% 암모늄 퍼설레이트Ammonium persulate 1 중량%1 wt% 0.03 중량%0.03 wt% 0.01 중량%0.01 wt% 이온교환수Ion-exchange water 0.4 중량%0.4 wt% 0.05 중량%0.05 wt% 11.2 중량%11.2 wt% 암모늄 퍼설페이트Ammonium persulfate 3 중량%3 wt% 5 중량%5 wt% 3 중량%3 wt% 암모늄 히드록사이드Ammonium hydroxide 0.1 중량%0.1 wt% 0.1 중량%0.1 wt% 0.5 중량%0.5 wt% 합계Sum 100 중량%100 wt% 100 중량%100 wt% 100 중량%100 wt%

<제조방법><Manufacturing Method>

상기 ①의 성분을 합성반응기에서 투입하고 온도는 80℃로 유지한 후, 상기 ①의 혼합물에 상기 ②의 성분을 투입하였다.The component (1) was added in a synthesis reactor, the temperature was maintained at 80 占 폚, and then the component (2) was added to the mixture of?.

그리고, 상기 ①과 ②의 혼합물에 상기 ③의 성분을 프리믹싱한 모노머 혼합물을 3 시간에 걸쳐 드로핑(Dropping)하여 반응시켰다.Then, the mixture of the above (1) and (2) was subjected to dropping by a monomer mixture pre-mixed with the above component (3) over a period of 3 hours.

그리고, 상기 ①, ② 및 ③의 반응물에 상기 ④의 혼합물을 1시간에 걸쳐서 드로핑하여 2차 합성 반응을 유도하였다. 이때, 2차 반응을 완료한 후에는 진공펌프를 사용하여 진공상태를 10분간 유지하여 미반응 모노머를 제거하였다.Then, the mixture of (4) was dropped to the reactants of (1), (2) and (3) over 1 hour to induce a second synthesis reaction. At this time, after completion of the secondary reaction, the unreacted monomer was removed by maintaining the vacuum state for 10 minutes using a vacuum pump.

그런 다음, 미반응 모노머를 제거한 상기 ①, ②, ③ 및 ④의 반응물의 온도를 40~50℃로 낮춘 후, 상기 ⑤의 성분을 투입하여 마지막 합성 반응을 시키고, 본 발명에 따른 수분산 폴리아크릴우레탄 에멀전 수지 조성물을 수득하였다. 이때, 본 발명의 에멀전의 점도는 700~1,000 cps(Brookfiled 점도계/25℃), 고형분은 약 52.4 중량% 및 유리전이온도(Tg)는 약 -20℃의 특성을 나타내었다.
Then, the temperature of the reactants of the above (1), (2), (3) and (4) from which unreacted monomers are removed is lowered to 40 to 50 ° C, A urethane emulsion resin composition was obtained. At this time, the emulsion of the present invention exhibited a viscosity of 700 to 1,000 cps (Brookfiled viscometer / 25 ° C), a solid content of about 52.4 wt%, and a glass transition temperature (Tg) of about -20 ° C.

2. 친환경 아크릴우레탄 2. Eco-friendly acrylic urethane 고무계Rubber system 방수 도료의 제조 Manufacture of waterproof paint

본 발명에 따른 아크릴우레탄 고무계 방수 도료는 하기 표2의 성분 및 조성에 따라 750~900 rpm 속도로 혼합하여, 본 발명의 아크릴우레탄 고무계 방수 도료를 제조하였다. 이때, 본 실시예에서는 분산제(SHMP-30%), 방부제(proxel xl-2), 탄산칼슘(om-1) 및 증점제(ACRYLSOL RM-825, Rohm and Haas, 미국)를 사용하였다.The acrylic urethane rubber-based waterproof paint according to the present invention was mixed at a speed of 750 to 900 rpm according to the components and composition shown in Table 2 below to prepare an acrylic urethane rubber waterproof paint of the present invention. In this embodiment, dispersant (SHMP-30%), preservative (proxel xl-2), calcium carbonate (om-1) and thickener (ACRYLSOL RM-825, Rohm and Haas, USA) were used in this example.

성분명Ingredients 실시예 4Example 4 실시예 5Example 5 실시예 6Example 6 수분산 아크릴우레탄 에멀전 수지 조성물Water-dispersed acrylic urethane emulsion resin composition 45 중량%45 wt% 55 중량%55 wt% 45 중량%45 wt% 분산제Dispersant 0.3 중량%0.3 wt% 0.1 중량%0.1 wt% 0.1 중량%0.1 wt% water 8.5 중량%8.5 wt% 4 중량%4 wt% 4 중량%4 wt% 방부제antiseptic 0.5 중량%0.5 wt% 0.2 중량%0.2 wt% 0.2 중량%0.2 wt% 이산화티타늄Titanium dioxide 3 중량%3 wt% 0.5 중량%0.5 wt% 0.5 중량%0.5 wt% 탄산칼슘Calcium carbonate 35.1 중량%35.1 wt% 35 중량%35 wt% 45 중량%45 wt% 증점제Thickener 1.3 중량%1.3 wt% 0.8 중량%0.8 wt% 0.5 중량%0.5 wt% 무기안료Inorganic pigments 잉크그린Ink Green 2 중량%2 wt% 1.2 중량%1.2 wt% 1.6 중량%1.6 wt% 잉크산화철황Ink Oxide Yellow 4 중량%4 wt% 3 중량%3 wt% 3 중량%3 wt% 소포제Defoamer 0.3 중량%0.3 wt% 0.2 중량%0.2 wt% 0.1 중량%0.1 wt% 합계Sum 100 중량%100 wt% 100 중량%100 wt% 100 중량%100 wt%

[[ 시험예Test Example ]]

본 시험예에서는 본 발명에 따른 아크릴우레탄 고무계 방수 도료의 효능을 평가하기 위하여, 실시예에서 제조된 실시예 중 대표적으로 실시예 5의 물리적 특성, 건조시간, KS F 3211, KS M ISO 11890-1, ASTM D 3257 및 KS M ISO 3856 방법을 시험하였다.In this test example, in order to evaluate the efficacy of the acrylic urethane rubber waterproof paint according to the present invention, physical properties, drying time, KS F 3211, KS M ISO 11890-1 , ASTM D 3257 and KS M ISO 3856 methods.

1. 물리적 특성1. Physical Characteristics

Figure 112013068344711-pat00001
Figure 112013068344711-pat00001

2. 건조 시간2. Drying time

Figure 112013068344711-pat00002
Figure 112013068344711-pat00002

3. 3. KSKS F 3211 시험 F 3211 exam

Figure 112013068344711-pat00003
Figure 112013068344711-pat00003

4. 친환경 시험4. Eco-friendly examination

Figure 112013068344711-pat00004
Figure 112013068344711-pat00004

이와 같이, 본 발명에 따른 아크릴우레탄 고무계 방수 도료는 친환경적이면서 탄성(도 1 참조), 인장력 및 부착력이 매우 우수함을 확인할 수 있었다.As described above, it was confirmed that the acrylic urethane rubber waterproof paint according to the present invention is eco-friendly and excellent in elasticity (see FIG. 1), tensile strength and adhesion.

또한, 하기 표 7 및 8에 나타난 바와 같이 종래 아크릴 에멀전과 우레탄 방수 도료와 비교해도 매우 우수함을 알 수 있다.In addition, as shown in Tables 7 and 8, it can be seen that the acrylic emulsion and the urethane waterproof paint are excellent in comparison with the conventional acrylic emulsion.

Figure 112013068344711-pat00005
Figure 112013068344711-pat00005

Figure 112013068344711-pat00006
Figure 112013068344711-pat00006

Claims (5)

디아세톤 아크릴아미드(Di Acetone AcrylAmide) 1.0~2.0중량%, n-부틸 아크릴레이트(n-buthyl acrylate) 15~20 중량%, 메타크릴산(methacrylic acid) 0.5~1.5 중량%, 아크릴로니트릴(acrylonitrile) 1.0~2.2중량%, 부틸 메타크릴레이트(buthyl methacrylate) 13~18 중량%, 2-에틸헥실 아크릴레이트(2-ethylhexyl acrylate) 13.2~17.5 중량%, 스티렌(Styrene) 2.2~3.0 중량%, 아디프산 디히드라지드(Adipic acid Dihydrazide) 0.5~2.0 중량%, 암모늄 퍼옥사이드(Ammonium peroxide) 0.07~0.2 중량%, 암모늄 퍼설페이트(Ammonium persulfate) 0.06~2.2 중량%, 암모늄 히드록사이드(Ammonium hydroxide) 0.1~0.5 중량%, 이온교환수 41~52 중량% 및 비이온성 유화제 0.25~0.75 중량%을 혼합하여 반응시켜 이루어지는 친환경 수분산성 폴리 아크릴우레탄 에멀전 수지 조성물.1.0 to 2.0% by weight of diacetone acrylamide, 15 to 20% by weight of n-buthyl acrylate, 0.5 to 1.5% by weight of methacrylic acid, acrylonitrile By weight of styrene, 1.0 to 2.2% by weight of styrene, 13 to 18% by weight of buthyl methacrylate, 13.2 to 17.5% by weight of 2-ethylhexyl acrylate, 2.2 to 3.0% 0.5 to 2.0% by weight of adipic acid dihydrazide, 0.07 to 0.2% by weight of ammonium peroxide, 0.06 to 2.2% by weight of ammonium persulfate, ammonium hydroxide, 0.1 to 0.5% by weight, 41 to 52% by weight of ion-exchanged water, and 0.25 to 0.75% by weight of a nonionic emulsifier are mixed and reacted to prepare an emulsion. 제 1 항에 있어서,
상기 조성물은,
점도는 700~1000cps(25℃), 고형분은 52.4 중량% 및 유리전도온도(Tg)는 -20℃인 것을 특징으로 하는 친환경 수분산성 폴리 아크릴우레탄 에멀전 수지 조성물.
The method according to claim 1,
The composition may comprise,
Wherein the viscosity is 700 to 1000 cps at 25 占 폚, the solid content is 52.4 weight%, and the glass transition temperature (Tg) is -20 占 폚.
(a) 반응기에 이온교환수 20~25 중량%와 유화제 0.15~0.25 중량%를 투입하고 70~90 ℃의 온도를 유지시키면서 암모늄 퍼옥사이드 0.07~0.2중량%를 투입하여 혼합하는 단계;
(b) 상기 (a)의 혼합물에,
이온교환수 18~22중량%, 디아세톤 아크릴아미드 1.0~2.0중량%, n-부틸 아크릴레이트 15~20 중량%, 메타크릴산 0.5~1.5 중량%, 아크릴로니트릴 1.0~2.2중량%, 부틸 메타크릴레이트 13~18중량%, 2-에틸헥실 아크릴레이트 13.2~17.5 중량%, 스티렌 2.2~3.0중량%, 비이온성 유화제 0.1~0.5중량%, 아디프산 디히드라지드 0.5~2.0중량% 및 암모늄 퍼설페이트 0.01~1.0 중량%를 혼합한 혼합물을 3~4 시간 동안 드로핑(dropping)하여 반응시키는 단계;
(c) 상기 (b)의 반응물에,
암모늄 퍼설페이트 0.05~1.2 중량% 및 이온교환수 3.0~5.0 중량%를 혼합한 혼합물을 1~2 시간 동안 드로핑(dropping)하여 반응시키는 단계;
(d) 상기 (c)의 반응물을 진공 상태에서 5~ 20분간 유지시켜서 미반응 모노머를 제거하는 단계; 및
(e) 상기 (d)의 반응물을 40~50℃로 낮추면서 암모늄 히드록사이드 0.1~0.5 중량%를 투입하여 반응을 시키는 단계;
를 거쳐서 수득하는 것을 특징으로 하는 친환경 수분산성 폴리 아크릴우레탄 에멀전 수지 조성물의 제조방법.
(a) adding 20 to 25% by weight of ion exchange water and 0.15 to 0.25% by weight of an emulsifier to the reactor and adding and mixing 0.07 to 0.2% by weight of ammonium peroxide while maintaining the temperature at 70 to 90 ° C;
(b) adding to the mixture of (a)
Acrylic acid, 1.0 to 2.0 wt% of diacetone acrylamide, 15 to 20 wt% of n-butyl acrylate, 0.5 to 1.5 wt% of methacrylic acid, 1.0 to 2.2 wt% of acrylonitrile, By weight of a nonionic emulsifier, from 0.1 to 0.5% by weight of nonionic emulsifier, from 0.5 to 2.0% by weight of adipic acid dihydrazide, and from 0.1 to 5% by weight of an ammonium persulfate And 0.01 to 1.0% by weight of a sulfate is mixed for 3 to 4 hours to effect a reaction;
(c) adding to the reaction product of (b)
0.05 to 1.2% by weight of ammonium persulfate and 3.0 to 5.0% by weight of ion-exchanged water is dropped and reacted for 1 to 2 hours;
(d) maintaining the reactant of (c) in a vacuum for 5 to 20 minutes to remove unreacted monomer; And
(e) lowering the temperature of the reaction product of (d) to 40 to 50 ° C, and adding 0.1 to 0.5% by weight of ammonium hydroxide to the reaction;
Soluble polyacrylic urethane emulsion resin composition of the present invention.
제 1항 또는 제 2항 기재의 폴리 아크릴우레탄 에멀전 수지 조성물 45.0~55.0 중량%에, 분산제 0.1~0.3중량%, 물 4.0~8.5 중량%, 방부제 0.2~0.5중량%, 이산화티타늄(TiO2) 0.5~3.0중량%, 탄산칼슘 35.0~45.0중량%, 비이온성 증점제 0.5~1.3중량%, 착색 안료 1.0~6.0 중량%, 소포제 0.1~0.3중량%를 혼합하여 이루어지는 친환경 수분산성 아크릴우레탄 고무계 방수 도료 조성물.Any one of claims 1 to 45.0 ~ 55.0% by weight polyacrylic urethane emulsion resin composition 2 of the base material, the dispersing agent 0.1% to 0.3% by weight, water 4.0 ~ 8.5% by weight, a preservative 0.2 ~ 0.5% by weight, titanium dioxide (TiO 2) 0.5 Wherein the waterproof coating composition is an aqueous dispersion of an acrylic urethane rubber-based waterproof coating composition comprising a mixture of a water-based pigment, a water-based pigment, and an antifoaming agent in an amount of 0.3 to 3.0 wt%, calcium carbonate 35.0 to 45.0 wt%, nonionic thickener 0.5-1.3 wt%, color pigment 1.0-6.0 wt% (a) 제 1항 또는 제 2항 기재의 폴리 아크릴우레탄 에멀전 수지 조성물 45.0~55.0 중량%에, 분산제 0.1~0.3중량%, 물 4.0~8.5 중량%, 방부제 0.2~0.5중량%, 이산화티타늄(TiO2) 0.5~3.0중량%, 탄산칼슘 35.0~45.0중량%, 비이온성 증점제 0.5~1.3중량%, 착색 안료 1.0~6.0 중량% 및 소포제 0.1~0.3중량%를 교반기에 투입하고 750~900 rpm 속도로 혼합하는 단계; 및
(b) 상기 (a)의 혼합물을 진공 상태에서 5~ 20분간 유지시켜서 미반응 모노머를 제거하는 단계;
를 포함하여 이루어지는 것을 특징으로 하는 친환경 아크릴우레탄 고무계 방수 도료의 제조방법.
(a) 0.1 to 0.3% by weight of a dispersant, 4.0 to 8.5% by weight of water, 0.2 to 0.5% by weight of an antiseptic agent, 0.2 to 0.5% by weight of a titanium dioxide (TiO 2) 2 ) 0.5 to 3.0% by weight of calcium carbonate, 35 to 45% by weight of calcium carbonate, 0.5 to 1.3% by weight of a nonionic thickener, 1.0 to 6.0% by weight of a coloring pigment and 0.1 to 0.3% by weight of an antifoaming agent are fed into a stirrer at a speed of 750 to 900 rpm Mixing; And
(b) maintaining the mixture of (a) in a vacuum for 5 to 20 minutes to remove unreacted monomer;
Wherein the water-repellent paint is a water-based paint.
KR1020130089349A 2013-07-29 2013-07-29 Environmentally friendly poly acryl urethane resin emulsion composition and waterproof ground materials using the same KR101405133B1 (en)

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KR20190030917A (en) 2017-09-15 2019-03-25 미래피앤씨(주) Water-proofing putty composition containing environment affinity type water dispersable poly-acryl urethane emulsion, preparing method thereof and putty coating method using the same
KR102025182B1 (en) * 2019-03-25 2019-09-25 미래피앤씨(주) Water-proofing putty composition and putty coating method using the same
KR102499630B1 (en) * 2023-01-10 2023-02-15 김원갑 Hybrid type waterproofing agent and construction method using the same
KR102548852B1 (en) * 2022-06-22 2023-06-30 한국에이스산업 주식회사 Water-Soluble Urethane Paint Composition

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Publication number Priority date Publication date Assignee Title
KR20190030917A (en) 2017-09-15 2019-03-25 미래피앤씨(주) Water-proofing putty composition containing environment affinity type water dispersable poly-acryl urethane emulsion, preparing method thereof and putty coating method using the same
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KR102548852B1 (en) * 2022-06-22 2023-06-30 한국에이스산업 주식회사 Water-Soluble Urethane Paint Composition
KR102499630B1 (en) * 2023-01-10 2023-02-15 김원갑 Hybrid type waterproofing agent and construction method using the same

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