KR940005187B1 - Waterproof agent and producing method thereof - Google Patents
Waterproof agent and producing method thereof Download PDFInfo
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Abstract
Description
제1도는 본 발명의 도막방수제의 제조공정도이다.1 is a manufacturing process diagram of the coating film waterproofing agent of the present invention.
본 발명은 건축분야에 광범위하게 사용되고 있는 도막방수제 및 이의 제조방법에 관한 것으로, 좀더 구체적으로는 보조유화제와 보호콜로이드를 첨가하여 프리믹스(Free-mix)한 아크릭고무계 에멀젼을 교반하면서 가교제를 첨가하여 프리믹스한 우레탄고무계 프레폴리머(pre-polymer)를 첨가하여 유화 분산 반응시킨 다음, 분산제, 물, 무기질, 충진제,소포제,동결안정제,착색제,방오제 등의 기타 첨가제를 첨가하여 분산 교반후 진공탈포공정을 행함을 특징으로 하는 에멀젼형 변성 아크릭우레탄고무계 도막방수제 및 이의 제조방법에 관한 것이다.The present invention relates to a coating film waterproofing agent widely used in the construction field and a method for manufacturing the same, and more specifically, to a premix by adding a crosslinking agent while stirring a free-mixed acrylic rubber-based emulsion by adding an auxiliary emulsifier and a protective colloid. After the urethane rubber-based prepolymer is added to emulsify and disperse the reaction, dispersant, water, inorganic, filler, defoamer, freeze stabilizer, coloring agent, antifouling agent, etc. An emulsion-type modified acrylic urethane rubber coating waterproofing agent characterized by the above-mentioned, and a method for producing the same.
일반적으로 합성고무계 도막방수제는 각종 건축공사의 옥상 및 외벽방수에 광범위하게 사용되기 때문에 콘크리트몰탈 및 피착제에 충분히 접착하여 수밀성을 확보하여야 하고, 유연성이 풍부하여 하절기 온도에 의한 팽창, 동절기의 수축 등에 의한 부피변형이 충분히 이루어져야 하고, 작업성이 우수하여 하며 사용방법이 너무 까다롭지 않아야 하고, 내후성이 우수하여 노출시 자외선에 의한 변색, 노화가 없이 장기간에 걸쳐 방수기능을 유지할 수 있어야 하는 등 우수한 제반물성 및 효과가 요구되지만 종래의 합성고무계 도막방수제들은 상기 요건들을 충족시키지 못하는 문제점이 있었다. 즉, 합성고무를 주로 이용하는 도막방수제에는 여러 종류가 있지만 특히, 우레탄고무계 도막방수제와 아크릭에멀젼고무계 도막방수제로 대별되고 있으며, 이들은 도막방수제로서의 효능을 충분히 만족시키지 못할 뿐만 아니라 여러 가지의 문제점들을 내포하고 있었다.In general, synthetic rubber coating waterproofing agent is widely used for rooftop and exterior wall waterproofing of various construction works, so it must be sufficiently adhered to concrete mortar and adherend to secure watertightness, and it is rich in flexibility to expand due to summer temperature, shrinkage of winter season, etc. Excellent volumetric deformation, excellent workability and use method should not be too demanding, and excellent weatherability to maintain waterproof function for a long time without discoloration by UV rays or aging when exposed. Although physical properties and effects are required, conventional synthetic rubber coating waterproofing agents do not meet the above requirements. That is, there are many kinds of coating waterproofing agent mainly using synthetic rubber, but in particular, it is classified into urethane rubber coating waterproofing agent and acrylic emulsion rubber coating waterproofing agent, and they do not sufficiently satisfy the efficacy as coating waterproofing agent and have various problems. there was.
우레탄고무계 도막방수제는 건축토목계에서 노출방수제로 주로 사용되고 있지만 내후성이 불량하고 자외선에 의해 변색 및 노화되며 작업성이 불량하고 습윤면의 발포로 인한 접착불량의 문제점과 저장안전성이 낮은 결점을 가지고 있으며, 아크릭에멀젼고무계 도막방수제는 우레탄고무계 도막방수제와는 달리 내후성, 자외선에 의한 변색노화 저항성, 습윤면의 접착성, 작업성 등은 우수하지만 에멀젼이 주체로 되어 있으므로 매체인 H2O가 발산하여 경화하기 때문에 약 30% 정도의 수축이 있어 방수층의 두께가 수축하는 문제점이 있었다.Urethane rubber coating waterproofing agent is mainly used as exposure waterproofing agent in construction civil engineering, but it has poor weather resistance, discoloration and aging due to ultraviolet rays, poor workability, poor adhesion due to foaming of wet surface and low storage safety. Unlike urethane rubber coating waterproofing agent, Acryric emulsion rubber waterproofing agent is excellent in weather resistance, resistance to discoloration aging due to ultraviolet ray, adhesion of wet surface, workability, etc., but since emulsion is mainly composed of H 2 O Since there is about 30% shrinkage, there was a problem that the thickness of the waterproof layer shrinks.
또한, 우레탄고무계 도막방수제와 아크릭에멀젼고무계 도막방수제 모두는 디옥틸프탈레이트(D.O.P : dioctyl phthalate), 디부틸프탈레이트(D.B.P : dibutyl phthalate),연소화 파라핀, 폴리부텐 등의 가소제를 통상적으로 사용하므로서 장기간에 걸쳐 가소물질이 휘발되어 고화하여 본래의 고무성능이 상실되는 문제점이 있었다.In addition, both the urethane rubber coating waterproofing agent and the acrylic emulsion rubber coating waterproofing agent generally use plasticizers such as dioctyl phthalate (DOP), dibutyl phthalate (DBP: dibutyl phthalate), burned paraffin, and polybutene. There was a problem in that the plastic material is volatilized to solidify and the original rubber performance is lost.
따라서, 본 발명의 목적은 우레탄고무계 도막방수제에 비해 내후성, 자외선에 의한 변색, 노화저항성, 작업성, 저장안전성이 우수하며 아크릭고무계 도막방수제에 비하여 체적수축율을 향상시키고 역성의 고무성질을 탄성으로 개선시킨 도막방수제를 제공하는데 있다.Therefore, the object of the present invention is better weather resistance, discoloration by UV rays, aging resistance, workability, and storage safety than urethane rubber coating waterproofing agent, and improves the volume shrinkage and reversible rubber property of elasticity compared to acrylic rubber coating waterproofing agent. It is to provide a coating film waterproofing agent.
상술한 목적 뿐만 아니라 용이하게 표출될 수 있는 또다른 목적들을 달성하기 위하여 본 발명에서는 아크릭고무에멀젼에 우레탄 고무계,프레폴리머를 투여하고 교반하여 우레탄고무계 프레폴리머를 유화 분산시킨 후에 분산제, 물, 무기질충진제, 소포제, 동결안전성, 착색제 등의 기타 첨가제를 첨가하므로서 도막방수제에서 요구되는 제반물성이 뛰어난 에멀젼형 변성 아크릭 우레탄고무계 도막방수제를 제조하였다.In order to achieve the above object as well as other objects that can be easily expressed in the present invention, a urethane rubber-based prepolymer is administered and stirred in an acrylic rubber emulsion and stirred to disperse and disperse the urethane rubber-based prepolymer, and then a dispersant, water and inorganic filler. By adding other additives such as antifoaming agent, antifoaming agent, freeze stability, colorant, etc., an emulsion-type modified acrylic urethane rubber coating waterproofing agent having excellent general properties required for coating waterproofing agent was prepared.
즉, 보조유화제, 보호콜로이드를 첨가하여 프리믹스(Free-mix)한 아크릭고무계 에멀젼에 가교제를 첨가하여 프리믹스한 우레탄고무계 프레폴리머를 투여하여 교반시킴으로서 에멀젼형 변성 아크릭 우레탄고무라텍스를 제조하고 이를 도막방수제의 주재로 사용함으로서 우레탄고무계 도막방수제의 단점인 내후성, 자외선에 의한 변색, 노호, 작업성, 습윤면의 발포로 인한 접착불량, 저장안전성 등의 문제를 개선하였으며, 또한 아크릭 에멀젼고무계 방수제의 단점인 체적수축율, 역성의 고무성질을 탄성의 고무성질로 대폭 개선시킨 가소제를 사용하지 않는 새로운 형태의 에멀젼형 변성 아크릭 우레탄고무계 도막방수제를 제조하였다.In other words, the emulsion-modified acryl urethane rubber latex was prepared by adding a crosslinking agent to the pre-mixed acryl rubber-based emulsion by adding an auxiliary emulsifier and a protective colloid, followed by stirring. By using it as a main material, problems such as weather resistance, discoloration caused by ultraviolet ray, discoloration due to ultraviolet rays, roar, workability, poor adhesion due to foaming of wet surface, storage safety, etc. are improved, and volume, which is a disadvantage of acrylic emulsion rubber waterproofing agent, is also used. A new type of emulsion-type modified acryl urethane rubber coating waterproofing agent was prepared, which did not use a plasticizer that greatly improved the shrinkage and reverse rubber properties to elastic rubber properties.
본 발명을 좀더 구체적으로 설명하면 다음과 같다.The present invention will be described in more detail as follows.
먼저, 아크릭고무계 에멀젼 10-30분후에 보조유화제 0.1-1.0부, 보호콜로이드 0.01-0.5부를 첨가하여 약 10분정도 프리믹스한다. 또한 우레탄고무계 프레폴리머 10-30분후에 가교제 0.05-0.5부를 첨가하고 약 10분간 교반하여 프리믹스한다.First, after 10-30 minutes of the acrylic rubber emulsion, 0.1-1.0 parts of the auxiliary emulsifier and 0.01-0.5 parts of the protective colloid are added and premixed for about 10 minutes. In addition, after 10-30 minutes of urethane rubber-based prepolymer, 0.05-0.5 parts of a crosslinking agent is added and stirred for about 10 minutes to premix.
본 발명에서 사용되는 아크릭고무계 에멀젼은 각종 아크릴산에스테르(CH2=CHOOR)공중합 아크릭고무계 에멀젼으로 고형분 함량이 약 60% 정도인 것이며, 우레탄고무계 프레폴리머는 고형분 100%의 NCO 함유량이 2-4% 정도인 것으로서는, 아크릭고무계 에멀젼이나 우레탄고무계 프레폴리머는 아크릭에멀젼고무계 도막방수제나 우레탄고무계 도막방수제의 제조시 통상적으로 사용되는 것으로 시중에 용이하게 구입할 수 있는 것이다.Acrylic rubber emulsion used in the present invention is a variety of acrylic ester (CH 2 = CHOOR) copolymerized acrylic rubber emulsion having a solid content of about 60%, the urethane rubber prepolymer has a NCO content of 100% solids of about 2-4% As such, acryl rubber-based emulsions and urethane rubber-based prepolymers are commonly used in the manufacture of aric emulsion rubber-based coating waterproofing agents and urethane rubber-based coating waterproofing agents, and are readily available on the market.
또한, 보조유화제로는 본 발명의 속하는 기술분야에서 통상적으로 사용되는 비이온계 LS수성 유화제를 사용할 수 있지만 포리옥시에틸렌 즉, HLB(Hydrophilo Lipophile Balance)가 10-16인 것을 사용하는 것이 효과적이며, 보호콜로이드 역시 본 발명이 속하는 기술분야에서 통상적으로 사용되는 것을 모두 사용할 수 있지만 하이드록시에틸셀롤로오즈, PVA(Poly Vinyl Alcohol)이 효과적이고, 가교제로는 실란 커플링제(silane coupling agents)로서 N-(-2-아미노에틸)-3-아미노-프로필트리메톡시실란, 3-글리시톡시 프로 필트리메톡시실란 등을 사용하는 것이 바람직하다.In addition, the co-emulsifier can be used nonionic LS-based emulsifiers commonly used in the art, it is effective to use a polyoxyethylene, that is, a HLB (Hydrophilo Lipophile Balance) of 10-16, The protective colloid may also be used in the art to which all commonly used in the art, but hydroxyethyl cellulose, polyvinyl alcohol (PVA) is effective, as a crosslinking agent N- as a silane coupling agent (silane coupling agents) Preference is given to using (-2-aminoethyl) -3-amino-propyltrimethoxysilane, 3-glycithoxy profiletrimethoxysilane and the like.
아크릭고무계 에멀젼을 10부 이하로 사용하거나 우레탄고무계 프레폴리머를 30부 이상으로 사용할 경우에는 내후성이 저하되며 자외선에 의한 변색 및 노화현상이 발생하는 문제점이 있으며, 아크릭고무계 에멀젼을 30부 이상으로 사용하거나 우레탄고무계 프레폴리머를 10부 이하로 사용할 경우에는 체적수축율이 좋지않고 역성의 고무성질이 두드러지게 발현되는 문제점이 있었다.When the acrylic rubber emulsion is used in 10 parts or less or when the urethane rubber prepolymer is used in 30 parts or more, there is a problem that the weather resistance is deteriorated and discoloration and aging due to ultraviolet rays occur, and the acrylic rubber emulsion is used in 30 parts or more. When the urethane rubber-based prepolymer is used in less than 10 parts, there is a problem in that the volumetric shrinkage is not good and the reverse rubber property is remarkably expressed.
또한, 보조유화제를 0.1부 이하로 사용시에는 아크릭고무계 에멀젼이 유화되지 않는 문제점이 있었으며, 1.0부 이상으로 사용시에는 경제적이지 못하였고, 보호콜로이드를 0.01부 이하로 첨가시에는 첨가효과가 저조하였으며, 0.5부 이상으로 첨가시에는 경제적이지 못하였다. 뿐만 아니라, 가교제를 0.05부 이하로 첨가시에는 우레탄고무계 프레폴리머가 분사도지 않는 문제점이 있었으며 0.5부 이상으로 첨가시에는 점도가 저하되며 경제적이지 못하였다.In addition, when the co-emulsifier was used at 0.1 parts or less, there was a problem that the acrylic rubber emulsion was not emulsified, and when it was used at 1.0 parts or more, it was not economical. It was not economical to add more than a part. In addition, when the crosslinking agent is added to 0.05 parts or less, there is a problem that the urethane rubber-based prepolymer is not sprayed, and when added to 0.5 parts or more, the viscosity decreases and it is not economical.
상술한 방법으로 프리믹스된 아크릭고무계 에멀젼을 교반하면서 프리믹스된 우레탄고무계 프레폴리머를 천천히 투여하여 20분정도 혼합 교반분산시킨다. 아크릭고무에멀젼에 우레탄고무프레폴리머를 투여하여 교반으로서 아크릭고무에멀젼의 매체인 H2O와 우레탄고무계 프레폴리머의 이소시아네이트기가 반응하여 아크릭고무계 에멀젼중에 우레탄고무계 프레폴리머가 유화분산되어짐 도막방수제용으로 적당한 에멀젼형 변성 아크릭우레탄 고무라텍스가 제조된다. 프리믹스한 아크릭고무에멀젼과 프리믹스한 우레탄고무레폴리머와의 배합하는 고형분 대비 100 : 50-100정도가 가장 이상적이다.The premixed urethane rubber-based prepolymer is slowly administered while stirring the premixed rubber-based emulsion in the above-described manner, followed by mixing, stirring, and dispersion for about 20 minutes. Acrylic rubber and urethane rubber frame administration of the polymer as a group is an isocyanate of the acrylic medium of H 2 O and the urethane rubber prepolymer of the rubber emulsion stirred reaction in emulsion urethane rubber prepolymer suitable emulsion for emulsion dispersion doeeojim coat Repellent the acrylic rubber-based emulsion Type modified acrylic urethane rubber latex is produced. 100: 50-100 is most suitable for the solid content of the premixed acrylic rubber emulsion and the premixed urethane rubber polymer.
상기와 같이 제조된 에멀젼형 변성 아크릭우레탄고무에멀젼에 본 발명이 속하는 기술분야에서 통상적으로 사용되는 기타 첨가제 즉, 분산제,물,무기질충제,착색제,소포제,동결방지제,방오제 등을 첨가하고 1200rpm으로 30분 정도, 800rpm으로 20분 정도 교반 분사시킨 후, 60-70cm/Hg의 진공탈포공정을 30분 정도 행하여 반응에 의하여 발생한 CO2및 기포를 제거하여 에멀젼형 변성 아크릭우레탄고무계 도막방수제를 제조한다.To the emulsion-type modified acrylic urethane rubber emulsion prepared as described above, other additives commonly used in the art, namely dispersants, water, inorganic fillers, coloring agents, antifoaming agents, freezing inhibitors, antifouling agents and the like, are added at 1200 rpm. After 30 minutes of stirring and spraying at 800 rpm for about 20 minutes, a vacuum defoaming step of 60-70 cm / Hg is performed for about 30 minutes to remove CO 2 and bubbles generated by the reaction to prepare an emulsion-type modified acrylic urethane rubber coating waterproofing agent. .
다음의 실시예 및 비교예는 본 발명의 에멀젼형 변성아크릭우레탄고무계 도막방수제의 제조방법 및 이의 효과를 좀더 구체적으로 설명하는 것이지만, 본 발명의 범주를 한정하는 것은 아니다.The following examples and comparative examples will be described in more detail the manufacturing method and effects of the emulsion-type modified acrylic polyurethane rubber coating waterproofing agent of the present invention, but is not intended to limit the scope of the present invention.
하기의 실시예 및 비교예와 상술한 내용에 기재된 "부"는 다른 언급이 없는 한 "중량부"를 의미하는 것이다."Parts" described in the following Examples and Comparative Examples and the foregoing description means "parts by weight" unless otherwise indicated.
[실시예 1]Example 1
고형분 함량이 약 60% 정도인 아크릭고무에멀젼 20.5부에 보조 유화제로 폴리옥시에틸렌 0.6부와 보호콜로이드로서 하이드록시에틸 셀룰로오즈 0.2부를 첨가하여 약 10분 정도 프리믹스한다. 또한, 고형분 100% NCO 함유량 3%인 우레탄고무계 프레폴리머 13.7부에 N-(2-아미노에틸)-3-아미노-프로필 트리메톡 시실란 0.1부를 첨가하여 약 10분간 교반하므로서 프리믹스한다.Premix for about 10 minutes by adding 0.6 parts of polyoxyethylene as a co-emulsifier and 0.2 parts of hydroxyethyl cellulose as a protective colloid to 20.5 parts of an acrylic rubber emulsion having a solid content of about 60%. Further, 0.1 parts of N- (2-aminoethyl) -3-amino-propyl trimethoxysilane is added to 13.7 parts of a urethane rubber-based prepolymer having a solid content of 100% NCO and 3%, followed by premixing while stirring for about 10 minutes.
상술한 방법으로 프리믹스된 아크릭고무계 에멀젼을 교반하면서 프리믹스되어진 우레탄고무계 프레폴리머를 천천히 투여하여 20분 정도 혼합 교반 분산시킴으로서 에멀젼형 변성 아크릭우레탄 고무라텍스 35.1부를 얻은 다음, 이에 분산제로서 폴리메타인산소다 0.1부, 물 10.1부, 무기질충진제로서 탄산칼슘 40.1부, 아연화 45부,착색제로서 산화티타늄 6.7부, 합성라텍스용 액상소포제(한국산 노포(주), 제품, 노프코 NXZ)0.7부,동결방지제로 에틸렌글리콜 1.9부, 암모니아수(28%) 0.6부, 합성라텍스용 방균제(미국 다우케미칼사 제품,다우씰 75) 0.2부를 첨가하고 1200rpm에서 30분, 800rpm에서 20분 정도 교반 분산시킨후,70cm/Hgdm 진공탈포공정을 30분 정도 행하여 CO2및 기포를 제거함으로서 본 발명의 에멀젼형 변성 아크릭우레탄고무계 도막방수제 100부를 제조한다.35.1 parts of an emulsion-type modified acryl urethane rubber latex were obtained by slowly administering the premixed urethane rubber-based prepolymer while stirring and dispersing the premixed urethane rubber-based prepolymer while stirring the premixed acrylic rubber emulsion by the above-described method, and then 0.1 part of polymethyl phosphate as a dispersant. , 10.1 parts of water, 40.1 parts of calcium carbonate as a mineral filler, 45 parts of zinc oxide, 6.7 parts of titanium oxide as a coloring agent, 0.7 parts of liquid antifoaming agent for synthetic latex (North Korea Co., Ltd., Nofco NXZ), ethylene glycol as a freezing agent 1.9 parts, ammonia water (28%) 0.6 parts, 0.2 parts of synthetic latex antimicrobial agent (Dow Chemical, Dow Seal 75) was added, stirred and dispersed for 30 minutes at 1200rpm and 20 minutes at 800rpm, and then 70cm / Hgdm vacuum. A defoaming step is performed for about 30 minutes to remove CO 2 and bubbles to prepare 100 parts of the emulsion-type modified acrylic urethane rubber coating waterproofing agent of the present invention.
제조된 도막방수제의 인잔강도, 파단신율, 경도 등의 제반물성을 표 1에 기재된 측정방법으로 측정하고, 그 결과를 하기 표 1에 기재하였다.The overall physical properties of the prepared film waterproofing agent, such as the in-zane strength, elongation at break, hardness, etc. were measured by the measuring method described in Table 1, and the results are shown in Table 1 below.
[표 1]TABLE 1
[비교예 1]Comparative Example 1
본 발명의 도막방수제, 2액형 우레탄고무계 도막방수제(중앙방수(주) 제품,Ryu코트), 1액형 우레탄고무계 도막방수제(미국 마메코사 제품, 몰겜 101). 아크릭고무계 도막방수제(동일화학(주) 제품, 하겐)에 대한 특성 및 물성평가를 본 발명이 속하는 기술분야에서 통상적으로 사용되는 방법으로, 그 결과를 하기의 표 2에 기재하였다.Coating film waterproofing agent of the present invention, two-component urethane rubber-based coating film waterproofing agent (manufactured by Central Waterproofing Co., Ltd., Ryu coat), one-component urethane rubber-based coating film waterproofing agent (Mameko Co., USA, Molm 101). Characteristic and physical property evaluation of the Acrylic rubber-based coating waterproofing agent (product of the same chemical Co., Ltd., Hagen) is a method commonly used in the art to which the present invention belongs, the results are shown in Table 2 below.
[표 2]TABLE 2
상기 표 1 및 표 2로부터 알수 있는 바와 같이 본 발명으 에멀젼형 변성 아크릭우레고무계 도막방수제의 효능 및 효과는 우수하며, 특히 종래의 우레탄고무계 도막방수제의최대 결점인 내후성, 습윤면의 접착성, 작업성의 문제를 해결하였고 사용후 남은 재료를 재사용할 수 있도록 하였고 가소제를 사용하지 않고 세척제로 사용하지 않으므로 공해문제를 해결할 수 있었고, 아크릭고무계 도막방수제의 결점인 체적수축도를 20% 정도로 개선 하였으며 역성의 고무성능을 탄성으로 개선한 새로운 형태의 도막방수제를 제조할 수 있었다.As can be seen from Table 1 and Table 2, the efficacy and effect of the emulsion-type modified acryleureum rubber coating waterproofing agent of the present invention is excellent, in particular weather resistance, wet surface adhesion, workability of the maximum defects of the conventional urethane rubber coating waterproofing agent It solved the problem of the property, and was able to reuse the remaining materials after use, and solved the pollution problem by not using the plasticizer and the cleaning agent, and improved the volume shrinkage, which is the defect of the acrylic rubber film waterproofing agent, by about 20%. A new type of film waterproofing agent with improved rubber performance could be prepared.
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| KR1019910017772A KR940005187B1 (en) | 1991-10-10 | 1991-10-10 | Waterproof agent and producing method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100315715B1 (en) * | 1999-06-04 | 2001-12-12 | 강병우 | The flexible coating water resistant organdzation and manufature method of a water type acrylic |
| KR101405133B1 (en) * | 2013-07-29 | 2014-06-10 | 미래피앤씨(주) | Environmentally friendly poly acryl urethane resin emulsion composition and waterproof ground materials using the same |
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1991
- 1991-10-10 KR KR1019910017772A patent/KR940005187B1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100315715B1 (en) * | 1999-06-04 | 2001-12-12 | 강병우 | The flexible coating water resistant organdzation and manufature method of a water type acrylic |
| KR101405133B1 (en) * | 2013-07-29 | 2014-06-10 | 미래피앤씨(주) | Environmentally friendly poly acryl urethane resin emulsion composition and waterproof ground materials using the same |
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