KR101329239B1 - Aqueous acrylic emulsion adhesive composition and its preparation process - Google Patents
Aqueous acrylic emulsion adhesive composition and its preparation process Download PDFInfo
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- KR101329239B1 KR101329239B1 KR1020130004511A KR20130004511A KR101329239B1 KR 101329239 B1 KR101329239 B1 KR 101329239B1 KR 1020130004511 A KR1020130004511 A KR 1020130004511A KR 20130004511 A KR20130004511 A KR 20130004511A KR 101329239 B1 KR101329239 B1 KR 101329239B1
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives 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; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/016—Flame-proofing or flame-retarding additives
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
Description
본 발명은 수성 아크릴 에멀젼 접착제 조성물 및 그 제조방법에 관한 것으로, 더욱 상세하게는 아크릴 수지를 주성분으로 하고 접착강도 조절제인 스틸렌 모노머와 내열성 부여제인 N-메틸올 아크릴아미드 모노머를 아크릴산에 의해 가교시키고, 여기에 산화 및 환원개시제와 중화제, 난연제, 점도조절제 등을 포함한 수성 아크릴 에멀젼 접착제 조성물을 제조함으로써, 본 발명에 의한 접착제 조성물은 상온에서도 과립상 석재(granule stone)가 석재, 콘크리트, 시멘트, 금속, 플라스틱, 부직포 등에 대한 표면 부착이 양호하고 서로 다른 재질 간에도 강한 접착력을 나타내며, 더욱이 내수성, 내마모성, 내광성(耐光性), 내탄성, 내화성, 내화학성은 물론, 방음 및 단열성과 미끄럼방지 기능에 탁월한 효과가 있으며, 그리고 유기용제를 사용하지 않아 환경 친화적이고 용도에 따라 농도 및 점성 조절이 용이하여 작업성이 매우 우수한 수성 아크릴 에멀젼 접착제 조성물 및 그 제조방법에 관한 것이다.The present invention relates to an aqueous acrylic emulsion adhesive composition and a method for producing the same, and more particularly, to a crosslinking of an styrene monomer, which is an acrylic resin as a main component, and an N-methylol acrylamide monomer, a heat resistance imparting agent, with acrylic acid, By preparing an aqueous acrylic emulsion adhesive composition comprising an oxidation and reduction initiator, a neutralizing agent, a flame retardant, a viscosity modifier, and the like, the adhesive composition according to the present invention is a granular stone even at room temperature, such as stone, concrete, cement, metal, Good surface adhesion to plastics, non-woven fabrics, and strong adhesion between different materials. Furthermore, it has excellent effects on water resistance, abrasion resistance, light resistance, elasticity, fire resistance, chemical resistance, as well as sound insulation, insulation and anti-slip function. And do not use organic solvents environmentally friendly And by the density and viscosity adjusted easily according to the application the workability relates to an excellent water-based acrylic emulsion adhesive composition and a method of manufacturing the same.
일반적으로, 유기용제형 접착제는 방출되는 휘발성 유기화합물로 인해 작업자 및 사용자에게 환경적인 측면에서 문제점을 발생시키고 있어 수성 및 수용성 접착제로의 변화가 한창 진행 중이다. 그로 인해 최근 사용되고 있는 수성 접착제로는 주로 비닐계 모노머의 유화중합으로 이루어진 아크릴계 에멀젼이 사용되어지고 있는데, 이는 환경적인 측면에서는 장점이 있으나 도막 강도 및 소지에 대한 부착성, 플럭(flock) 가공성, 내스크래치성 등이 유기용제형 접착제 적용시보다 나은 물성을 나타내지 못한다.
In general, organic solvent-type adhesives are causing environmental problems for workers and users due to the volatile organic compounds released, the transition to aqueous and water-soluble adhesives are in full swing. For this reason, recently used aqueous adhesives are acrylic emulsions composed mainly of emulsion polymerization of vinyl monomers, which have advantages in terms of the environment, but have coating strength and adhesion to the substrate, flock processability, and resistance. Scratchability and the like do not show better physical properties than the application of the organic solvent type adhesive.
위와 같이, 수계(水系) 에멀젼형 접착제는 용매의 증발에 따라 균일한 용액에서 연속 피막을 형성하는 용제형과 달리, 접착력, 응집력, 전단력 및 내열성 등의 성질이 떨어지는데, 에멀젼형은 에멀젼 입자라는 비연속체에서 물의 건조에 의해 피막이 형성되고 제조시에 함유되는 계면활성제나 소포제, 점도조절제 등의 저분자량 화학성분들이 피막의 형성과정에 영향을 주어 내습ㆍ내수성을 저하시키는 문제점이 있다.
As described above, the water-based emulsion adhesive is different from the solvent type in which a continuous film is formed in a uniform solution according to the evaporation of the solvent. However, the water-based emulsion adhesive is inferior in adhesion, cohesion, shear and heat resistance properties. Films are formed by drying water in a continuous body, and low molecular weight chemical components such as surfactants, antifoaming agents, and viscosity modifiers contained in the manufacturing process affect the formation of the film, thereby degrading moisture and water resistance.
그러나 수성 아크릴 에멀젼 접착제의 경우에는 유기용제를 이용한 접착제의 단점을 쉽게 극복할 수 있어 최근의 세계적인 환경규제 문제를 해결할 수 있다. 특히 공업용, 사무용뿐 아니라 의료용으로 사용되어지는 접착제의 경우에는 잔류 용매가 인체에 해를 미칠 수 있어 더욱더 수용성 접착제의 가치가 증대되고 있고 이러한 경향은 미국, 일본 등의 선진국에서 확인할 수 있는 바, 최근에는 용제형 접착제가 사용되던 많은 부분들이 수용성 접착제에 의해 대체되고 있는 현상을 보이고 있다.
However, in the case of an aqueous acrylic emulsion adhesive, it is possible to easily overcome the disadvantages of the adhesive using an organic solvent can solve the recent global environmental control problem. Especially in the case of adhesives that are used not only for industrial and office use, but also for medical use, residual solvents can harm the human body, so the value of water-soluble adhesives is increasing. This trend can be seen in developed countries such as the United States and Japan. Many of the solvent-based adhesives are being replaced by water-soluble adhesives.
한편, 접착제에 난연성을 부가하는 방법으로 할로겐 원소를 도입하거나 할로겐 원소와 인 화합물을 도입, 또는 난연성 충전제를 첨가하는 것이 알려져 있는데, 수계 접착제인 경우에는 충전제를 첨가할 경우, 충전제가 접착제 내에서 응집되거나 침강되어 균일한 접착체층을 형성하기 어려울 뿐 아니라 인 화합물을 도입시키면 접착강도가 현저하게 저하되는 등의 많은 문제가 있어 아직까지 난연성 수계 접착제가 실용화 되고 있지 못하고 있으며, 단지 아크릴고무/브롬화 에폭시계 접착제와 같은 유기용제형 접착제가 난연성을 갖는 접착제로 유용성이 활용되고 있는 실정이다. 그리고 아크릴 고무/브롬화 에폭시계 접착제는 메틸에틸케톤, 톨루엔, 아세톤, 에탄올 등과 같은 강인화성 유기용제에 용해시켜야 하므로 최종단계에서 상기의 유기용제들을 증류시켜 제거하여야 하며, 상기 유기용제들은 인화성이 강하고 유독하여 제거공정이 매우 위험하고 환경오염을 발생시키는 문제점이 있다.
On the other hand, as a method of adding flame retardancy to the adhesive, it is known to introduce a halogen element, a halogen element and a phosphorus compound, or to add a flame retardant filler.In the case of an aqueous adhesive, when the filler is added, the filler aggregates in the adhesive. Not only is it difficult to form a uniform adhesive layer due to the formation or sedimentation, but there are also many problems such as a significant decrease in the adhesive strength when the phosphorus compound is introduced. Thus, a flame-retardant water-based adhesive has not been put to practical use, but only acrylic rubber / brominated epoxy Organic solvent type adhesives, such as adhesives, are being utilized as an adhesive having flame retardancy. The acrylic rubber / brominated epoxy adhesive should be dissolved in tough organic solvents such as methyl ethyl ketone, toluene, acetone, ethanol, etc., so the organic solvents must be removed by distillation in the final step. The organic solvents are highly flammable and toxic. Therefore, there is a problem that the removal process is very dangerous and causes environmental pollution.
본 발명과 관련하여 종래기술을 살펴보면, 대한민국 공개특허공보 제10-2012-0082550호(공개일: 2012. 07. 27)에는 아크릴 수지(acrylic resin)를 주성분으로 하고, 가교역할을 하는 AAEM(Acetoacetoxyethyl methacrylate), 산화 및 환원촉매, 및 SBR(Styrene Butadiene Rubber)-라텍스, NBR(nitrile-butadiene rubber)-라텍스 및 CR(Chloroprolene rubber)-라텍스로 이루어진 군중에서 선택된 내열성의 라텍스를 함유하는 수성 아크릴 에멀젼형 접착제 및 이의 제조방법에 관한 기술이 공지되어 있고, 이는 수분산형으로 우수한 접착성, 내후성, 저온 특성 및 가교기능을 가짐과 동시에 다른 고분자 에멀젼과의 상용성이 우수하고 높은 고형분 함량화, 폭넓은 점도 조정 등의 특성을 발휘하는 것으로 기재되어 있으나, 상기 수성 아크릴 에멀젼 접착제는 아크릴 수지계를 주성분으로 하고 여기에 라텍스를 포함하는 에멀젼형 접착제를 일컫는 수분산형으로, 상기 수성 아크릴 에멀젼은 아크릴 수지계 주위를 이온성 계면활성제(ionic surfactant) 또는 중합체 계면활성제(polymeric surfactant)에 의해 안정화되는 형태이다. 이러한 아크릴 에멀젼 접착제는 가구, 인테리어, 자동차, 건축 등의 내장재용 접착제로 주로 사용될 수 있다.
Looking at the prior art with respect to the present invention, Korean Patent Publication No. 10-2012-0082550 (published: 2012. 07. 27) is based on the acrylic resin (acrylic resin), AAEM (Acetoacetoxyethyl which acts as a crosslinking role Aqueous acrylic emulsion type containing heat resistant latex selected from the group consisting of methacrylate, oxidation and reduction catalyst, and SBR (styrene butadiene rubber)-latex, nitrile-butadiene rubber (NBR)-latex and chloroprolene rubber (CR)-latex There is a known technique for the adhesive and its manufacturing method, which is a water dispersion type, has excellent adhesion, weather resistance, low temperature properties and crosslinking functions, and is compatible with other polymer emulsions, and has a high solid content and a wide range of viscosities. Although it is described as exhibiting properties such as adjustment, the aqueous acrylic emulsion adhesive is based on an acrylic resin system and latex is included therein. The aqueous acrylic emulsion is an emulsion-type adhesive containing, wherein the aqueous acrylic emulsion is stabilized by an ionic surfactant or a polymeric surfactant around the acrylic resin system. Such acrylic emulsion adhesives can be mainly used as interior adhesives for furniture, interiors, automobiles, construction, and the like.
또한, 대한민국 공개특허공보 제10-2010-0026472호(공개일: 2010. 03. 10)를 보면, 친유성 단량체를 많이 사용하거나 계면장력이 적은 단량체를 더 많이 활용하여 내수성의 에멀젼 접착제를 제조하는 대신에, 유리전이온도가 차이가 나는 단량체들을 그룹으로 선택하되, 1, 2단계로 코아쉘 중합을 유도하여, 1단계에서 바깥쪽에 친유성 단량체 성분들을 배치하고 2단계에서는 더욱 더 친유성이 큰 단량체들을 부가중합시킴으로써, 각 에멀젼 입자들의 중심(코아)에서 바깥쪽으로 갈수록 친유성 단량체 성분이 배치되어 친유성이 증가된 내수성 아크릴계 접착제를 제조하는 방법이 기재되어 있는바, 이는 철판에 코팅을 하여 내부식성을 얻는데 주로 사용되어 강한 내수 혹은 내염수성 등과 같은 접착력을 충족시키고 있다.
In addition, the Republic of Korea Patent Publication No. 10-2010-0026472 (published: 2010. 03. 10), using a lot of lipophilic monomers or monomers having a low interfacial tension to prepare a water-resistant emulsion adhesive Instead, select monomers with different glass transition temperature as a group, but induce coashell polymerization in 1st and 2nd stages, arrange lipophilic monomer components in the 1st stage and more lipophilic in 2nd stage By addition polymerization of the monomers, a method of preparing a water-resistant acrylic adhesive having an increased lipophilic property by disposing a lipophilic monomer component from the center (core) of each emulsion particle toward the outside is described. It is mainly used to obtain corrosiveness and meets adhesive strength such as strong water or salt water resistance.
그밖에도, 대한민국 등록특허 제10-0309847호(공고일: 2001. 10. 29)에는 수용성 접착제에 유기용매 대신 수용성 셀룰로오스를 사용하여 빠른 접착강도를 가지며, 접착력이 우수하고 미생물에 대한 항균성을 보강함으로써, 유기용매를 사용한 접착제의 각종 단점을 극복하고 접착제를 사용한 포장지 등을 재생할 때 접착제가 완전하게 제거되어 환경 친화적인 수용성 접착제의 제조방법에 관한 기술이 공지되어 있다.
In addition, the Republic of Korea Patent No. 10-0309847 (published date: Oct. 29, 2001) has a fast adhesive strength by using a water-soluble cellulose instead of an organic solvent in a water-soluble adhesive, excellent adhesion and antibacterial to microorganisms, To overcome various disadvantages of an adhesive using an organic solvent and to regenerate a wrapping paper using the adhesive, a technique for producing an environmentally friendly water-soluble adhesive is known by completely removing the adhesive.
이에 따라, 본 발명에서는 아크릴 수지를 주성분으로 하고 접착강도 조절제인 스틸렌 모노머와 내열성 부여제인 N-메틸올 아크릴아미드 모노머를 아크릴산에 의해 가교시키고, 여기에 산화 및 환원개시제와 중화제, 난연제, 점도조절제 등을 포함한 수성 아크릴 에멀젼 접착제 조성물을 제조함으로써, 그 접착력에 의해 상온에서도 과립상 석재(granule stone)가 석재, 콘크리트, 시멘트, 금속, 플라스틱, 부직포 등에 표면 부착이 양호하게 되고 상기 재질 간에도 강한 접착력을 나타냄으로써, 내수성, 내마모성, 내광성(耐光性), 내탄성, 내화성, 내화학성은 물론, 방음 및 단열성과 미끄럼방지 기능에 탁월한 효과가 있으며, 그리고 유기용제를 사용하지 않아 환경 친화적이고 용도에 따라 농도 및 점성 조절이 용이한 관계로 작업성이 양호하다는 점에 착안하여 본 발명을 완성하였다.Accordingly, in the present invention, the acrylic resin is used as a main component, and the styrene monomer, which is an adhesive strength regulator, and the N-methylol acrylamide monomer, which is a heat resistance imparting agent, are crosslinked with acrylic acid, and an oxidation and reduction initiator, a neutralizing agent, a flame retardant, a viscosity regulator, etc. By producing an aqueous acrylic emulsion adhesive composition comprising a, the granule stone (granule stone) at room temperature due to the adhesive force is good surface adhesion to stone, concrete, cement, metal, plastic, non-woven fabric, and exhibits strong adhesion between the materials It is excellent in water resistance, abrasion resistance, light resistance, elasticity, fire resistance, chemical resistance, soundproofing, heat insulation and anti-slip function, and it is environmentally friendly and does not use organic solvents. It is easy to adjust the viscosity, so pay attention to the good workability The present invention has been completed.
본 발명의 목적은, 상온에서 도포하더라도 초기 접착력과 경화성을 충분히 발현할 수 있고 물과 천연 무기원료를 사용하여 용도에 따라 농도 및 점성 조절이 용이하여 작업성이 우수하며, 또한 유기용제를 전혀 사용하지 않아 환경 친화적인 수성 아크릴 에멀젼 접착제 조성물 및 그 제조방법을 제공하고자 하는 것이다.
An object of the present invention, even when applied at room temperature can be fully expressed in the initial adhesive strength and curability, it is easy to adjust the concentration and viscosity according to the use using water and natural inorganic raw materials, excellent workability, and also use organic solvents at all It is not intended to provide an environmentally friendly aqueous acrylic emulsion adhesive composition and its preparation method.
본 발명의 다른 목적은, 아크릴 수지를 주성분으로 하고 접착강도 조절제인 스틸렌 모노머와 내열성 부여제인 N-메틸올 아크릴아미드 모노머를 아크릴산에 의해 가교시키고, 여기에 산화 및 환원개시제와 중화제, 난연제, 점도조절제 등을 포함하는 수성 아크릴 에멀젼 접착제 조성물을 사용함으로써, 과립상 석재(granule stone)가 석재, 콘크리트, 시멘트, 금속, 플라스틱, 부직포 등에 대한 표면 부착성이 우수하고 각각의 다른 재질 간에도 강한 접착력을 나타내며, 아울러 내수성, 내마모성, 내광성(耐光性), 내탄성, 내화성, 내화학성은 물론, 방음 및 단열성과 미끄럼방지 기능에 탁월한 효과가 있는 수성 아크릴 에멀젼 접착제 조성물 및 그 제조방법을 제공한다.Another object of the present invention is to crosslink an styrene monomer, which is an acrylic resin as a main component, and an N-methylol acrylamide monomer, which is an adhesive strength modifier, with acrylic acid, and an oxidizing and reducing initiator, a neutralizing agent, a flame retardant, and a viscosity regulator. By using an aqueous acrylic emulsion adhesive composition including, etc., the granule stone has excellent surface adhesion to stone, concrete, cement, metal, plastic, nonwoven fabric, etc., and shows strong adhesion between different materials, In addition, the present invention provides an aqueous acrylic emulsion adhesive composition having excellent effects on water resistance, abrasion resistance, light resistance, elasticity, fire resistance, chemical resistance, as well as sound insulation, heat insulation, and anti-slip function, and a method of manufacturing the same.
상기와 같은 과제를 해결하기 위한 본 발명의 수성 아크릴 에멀젼 접착제 조성물은, 물 30 ~ 50중량%, 유화제 0.5 ~ 1.5중량%, 2-에틸 헥실 아크릴레이트 모노머(2-Ethyl hexyl acrylate monomer) 10 ~ 20중량%, 스틸렌 모노머(Stylene monomer) 12 ~ 22중량%, 아크릴산 모노머(Acryl acid monomer) 0.5 ~ 1.5중량%, N-메틸올 아크릴아미드 모노머(N-methylol acrylamide monomer) 1 ~ 3중량%, 암모늄 퍼설페이트(Ammonium persulphate) 0.2 ~ 0.4중량%, 소듐 비설페이트(Sodium bisulphate) 0.1 ~ 0.3중량%, 암모니아수(Ammonium hydroxide water) 0.5 ~ 1.5중량%, 난연제 2 ~ 10중량%, 점도조절제 10 ~ 30중량%의 비율로 포함하여 이루어지는 것을 특징으로 한다.
The aqueous acrylic emulsion adhesive composition of the present invention for solving the above problems is 30 to 50% by weight of water, 0.5 to 1.5% by weight of emulsifier, 2-Ethyl hexyl acrylate monomer 10 to 20 Weight%, Styrene monomer 12-22 weight%, Acrylic acid monomer 0.5-1.5 weight%, N-methylol acrylamide monomer 1-3 weight%, Ammonium per 0.2 to 0.4% by weight of sulfate (Ammonium persulphate), 0.1 to 0.3% by weight of sodium bisulphate, 0.5 to 1.5% by weight of ammonium hydroxide water, 2 to 10% by weight of flame retardant, 10 to 30% by weight of viscosity modifier It is characterized by comprising in the ratio of.
본 발명의 바람직한 특징에 따르면, 상기 유화제는 폴리옥시에틸렌 노닐페닐 에테르(Polyoxyethylene nonylphenyl ether)이고, 상기 난연제는 삼산화물(Sb2O3) 또는 삼염화물(Sb2Cl3) 중에서 선택되는 안티몬(Antimony)계, 수산화알루미늄(Aluminium hydroxide)계, 수산화마그네슘(Magnesium hydroxide)계로 이루어진 군으로부터 선택되는 어느 1종 이상을 사용하며, 상기 점도조절제는 탄산칼슘(Calcium carbonate)을 사용한다.
According to a preferred feature of the invention, the emulsifier is polyoxyethylene nonylphenyl ether (polyoxyethylene nonylphenyl ether), the flame retardant is antimony (Antimony) selected from trioxide (Sb 2 O 3 ) or trichloride (Sb 2 Cl 3 ) ) At least one selected from the group consisting of aluminum hydroxide (aluminum hydroxide), magnesium hydroxide (magnesium hydroxide) system, the viscosity modifier is used calcium carbonate (Calcium carbonate).
상기 수성 아크릴 에멀젼 접착제 조성물의 제조방법은, 하기 제1단계 내지 제3단계로 제조되는 수성 아크릴 에멀젼 접착제 조성물 100중량%를 기준으로 할 때, 1차 배합조에 물 20 ~ 30중량%에 대하여 유화제 0.5 ~ 1.5중량%를 투입한 후 교반하여 용해시킨 다음, 2-에틸 헥실 아크릴레이트 모노머(2-Ethyl hexyl acrylate monomer) 10 ~ 20중량%, 스틸렌 모노머(Stylene monomer) 12 ~ 22중량%, 아크릴산 모노머(Acryl acid monomer) 0.5 ~ 1.5중량%, N-메틸올 아크릴아미드 모노머(N-methylol acrylamide monomer) 1 ~ 3중량%를 투입하고 유화시켜 프리에멀젼 중합체를 제조하는 제1단계; 2차 반응조에 물 10 ~ 20중량%를 넣고 온도를 60 ~ 80℃로 유지하면서 산화개시제인 암모늄 퍼설페이트(Ammonium persulphate) 0.2 ~ 0.4중량%와 환원개시제인 소듐 비설페이트(Sodium bisulphate) 0.1 ~ 0.3중량%를 투입한 다음, 반응조의 온도를 70 ~ 90℃로 유지하면서 상기 프리에멀젼 중합체를 2 ~ 4시간에 걸쳐 적하시킨 후 중화제인 암모니아수(Ammonium hydroxide water) 0.5 ~ 1.5중량%를 투입하고 혼합 및 숙성시켜 수성 아크릴 에멀젼 접착제를 합성하는 제2단계; 상기 합성된 수성 아크릴 에멀젼 접착제에 난연제 2 ~ 10중량%, 점도조절제 10 ~ 30중량%를 첨가하고 혼합 및 냉각시켜 제품화하는 제3단계로 이루어진다.The method of preparing the aqueous acrylic emulsion adhesive composition is based on 100% by weight of the aqueous acrylic emulsion adhesive composition prepared in the following first to third steps. ~ 1.5% by weight, after stirring to dissolve, 10 to 20% by weight of 2-ethyl hexyl acrylate monomer (2-Ethyl hexyl acrylate monomer), 12 to 22% by weight of styrene monomer (Stylene monomer), acrylic acid monomer ( Acryl acid monomer) 0.5 to 1.5% by weight, 1 to 3% by weight of N-methylol acrylamide monomer (N-methylol acrylamide monomer) 1 to 3% by weight to prepare a pre-emulsion polymer; 10 to 20% by weight of water was added to the secondary reactor, and the temperature was maintained at 60 to 80 ° C, while 0.2 to 0.4% by weight of the oxidation initiator ammonium persulphate and 0.1 to 0.3 of sodium bisulphate as a reducing initiator. After adding the weight%, the pre-emulsion polymer was added dropwise over 2 to 4 hours while maintaining the temperature of the reactor at 70 ~ 90 ℃ and 0.5 to 1.5% by weight of ammonium hydroxide water (neutralizing agent) was added and mixed and A second step of aging to synthesize an aqueous acrylic emulsion adhesive; To the synthesized aqueous acrylic emulsion adhesive 2 to 10% by weight of the flame retardant, 10 to 30% by weight of the viscosity modifier consists of a third step of forming a product by mixing and cooling.
본 발명의 수성 아크릴 에멀젼 접착제 조성물은 상온에서 도포되어 초기 접착력과 경화성을 충분히 발현할 수 있고 물과 천연 무기원료를 사용하여 용도에 따라 농도 및 점성 조절이 용이하며, 또한 유기용제를 전혀 사용하지 않고 수용성 또는 수분산성 물질만으로 조성되는 관계로 환경에 친화적일 뿐만 아니라 작업성이 매우 우수한 효과가 있다.
The aqueous acrylic emulsion adhesive composition of the present invention can be applied at room temperature to sufficiently express the initial adhesive strength and curability, it is easy to control the concentration and viscosity according to the use using water and natural inorganic raw materials, and also without using any organic solvent Since it is composed of only water-soluble or water-dispersible materials, it is not only environmentally friendly but also has excellent workability.
본 발명에 따라 제조된 수성 아크릴 에멀젼 접착제 조성물은 아크릴 수지를 주성분으로 하고 접착강도 조절제인 스틸렌 모노머와 내열성 부여제인 N-메틸올 아크릴아미드 모노머를 아크릴산에 의해 가교시키고, 산화 및 환원개시제와 중화제, 난연제, 점도조절제 등을 포함함으로써, 석재, 콘크리트, 시멘트, 금속, 플라스틱, 부직포 등에 대한 표면 부착성이 탁월하고 각각의 서로 다른 재질 간에도 강한 접착력을 나타내며, 그 접착력에 의해 내수성, 내마모성, 내광성(耐光性), 내탄성, 내화성, 내화학성은 물론, 방음 및 단열성과 미끄럼방지 기능에 탁월한 효과가 있다.The aqueous acrylic emulsion adhesive composition prepared according to the present invention is crosslinked by acrylic acid with a styrene monomer, which is an acrylic resin as a main component, and an N-methylol acrylamide monomer, which is an adhesive strength control agent, and a heat resistance imparting agent, and an oxidation and reduction initiator, a neutralizing agent, and a flame retardant. By including a viscosity modifier, etc., it has excellent surface adhesion to stone, concrete, cement, metal, plastic, nonwoven fabric, etc., and shows strong adhesive force between different materials, and it has water resistance, abrasion resistance, and light resistance. ), Elasticity, fire resistance, chemical resistance, as well as excellent soundproofing, insulation and anti-slip function.
이하에서는 본 발명에 의한 수성 아크릴 에멀젼 접착제 조성물 및 그 제조방법에 대하여 설명하기로 하되, 이는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 예시하기 위한 것이지, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.
Hereinafter, the aqueous acrylic emulsion adhesive composition according to the present invention and a method for preparing the same will be described, which is intended to exemplify the self invention having ordinary skill in the art to which the present invention can be easily carried out. This does not mean that the technical spirit and scope of the present invention is limited.
본 발명에 따른 수성 아크릴 에멀젼 접착제 조성물은, 물 30 ~ 50중량%, 유화제 0.5 ~ 1.5중량%, 2-에틸 헥실 아크릴레이트 모노머(2-Ethyl hexyl acrylate monomer) 10 ~ 20중량%, 스틸렌 모노머(Stylene monomer) 12 ~ 22중량%, 아크릴산 모노머(Acryl acid monomer) 0.5 ~ 1.5중량%, N-메틸올 아크릴아미드 모노머(N-methylol acrylamide monomer) 1 ~ 3중량%, 암모늄 퍼설페이트(Ammonium persulphate) 0.2 ~ 0.4중량%, 소듐 비설페이트(Sodium bisulphate) 0.1 ~ 0.3중량%, 암모니아수(Ammonium hydroxide water) 0.5 ~ 1.5중량%, 난연제 2 ~ 10중량%, 점도조절제 10 ~ 30중량%를 포함하여 이루어진다.
The aqueous acrylic emulsion adhesive composition according to the present invention is 30 to 50% by weight of water, 0.5 to 1.5% by weight of emulsifier, 10 to 20% by weight of 2-ethylhexyl acrylate monomer, styrene monomer (Stylene) monomer) 12 to 22% by weight, 0.5 to 1.5% by weight of acrylic acid monomer, 1 to 3% by weight of N-methylol acrylamide monomer, 0.2 to ammonium persulphate 0.4% by weight, sodium bisulphate 0.1 to 0.3% by weight, ammonia water (Ammonium hydroxide water) 0.5 to 1.5% by weight, flame retardant 2 to 10% by weight, viscosity regulator 10 to 30% by weight.
상기 2-에틸 헥실 아크릴레이트 모노머(2-Ethyl hexyl acrylate monomer)에 대한 스틸렌 모노머(Stylene monomer)와 N-메틸올 아크릴아미드 모노머(N-methylol acrylamide monomer)는 가교제인 아크릴산 모노머(Acryl acid monomer)에 의해 유화 공중합되는데, 상기 2-에틸 헥실 아크릴레이트 모노머는 기재에 대한 표면 부착성이 탁월하여 접착력과 내탄성을 부여해 주고, 상기 스틸렌 모노머는 접착강도를 조절하여 접착제의 내수성, 내마모성, 내탄성, 내화성, 내화학성을 유지시켜 준다. 그리고 상기 N-메틸올 아크릴아미드 모노머는 접착제의 내열성을 부여함과 동시에 방음 및 단열성을 부여하는 역할을 하게 된다.
The styrene monomer and the N-methylol acrylamide monomer for the 2-ethylhexyl acrylate monomer are added to the acrylic acid monomer which is a crosslinking agent. Emulsion copolymerization, the 2-ethyl hexyl acrylate monomer is excellent in surface adhesion to the substrate to impart adhesion and elasticity, and the styrene monomer is adjusted to the adhesive strength, water resistance, wear resistance, elasticity, fire resistance of the adhesive Maintains chemical resistance. The N-methylol acrylamide monomer serves to impart heat resistance of the adhesive and to provide sound insulation and heat insulation.
위와 같이, 유화중합되어 제조되는 프리에멀젼 공중합체는 접착제 조성물의 총중량을 기준으로 물 30 ~ 50중량%, 2-에틸 헥실 아크릴레이트 모노머 10 ~ 20중량%, 스틸렌 모노머 12 ~ 22중량%, 아크릴산 모노머 0.5 ~ 1.5중량%, N-메틸올 아크릴아미드 모노머 1 ~ 3중량%의 비율로 함유됨으로써, 최적의 중합도를 유지하여 미반응 단량체의 비율을 줄이고 적당한 점도를 유지하면서 가사시간(可使時間)과 경화시간도 일정하게 하는 효과를 나타낸다. 본 발명에서는 상기 모노머의 사용량에 따라 수많은 실험을 거듭한 결과, 상기 공중합 반응되는 모노머들의 함량을 가장 적합한 범위로 도출할 수 있었음은 물론이다.
As described above, the pre-emulsion copolymer prepared by emulsion polymerization is 30 to 50% by weight of water, 10 to 20% by weight of 2-ethylhexyl acrylate monomer, 12 to 22% by weight of styrene monomer, acrylic acid monomer, based on the total weight of the adhesive composition. 0.5 to 1.5% by weight of N-methylol acrylamide monomer in a ratio of 1 to 3% by weight, maintaining the optimum degree of polymerization, reducing the proportion of unreacted monomers and maintaining a suitable viscosity and Curing time also has the effect of making it constant. In the present invention, as a result of repeated experiments in accordance with the amount of the monomer used, it is a matter of course that the content of the copolymerization reaction monomer can be derived in the most suitable range.
상기의 반응에서 사용되는 유화제는 폴리옥시에틸렌 노닐페닐 에테르(Polyoxyethylene nonylphenyl ether) 등을 0.5 ~ 1.5중량% 정도로 포함하여 우수한 접착력과 내수안정성을 가지지만, 이로 인하여 고분자 물질의 특성을 저하시키는 문제를 방지하기 위해 본 발명에서는 산화개시제로서 암모늄 퍼설페이트(Ammonium persulphate), 환원개시제로서 소듐 비설페이트(Sodium bisulphate)를 사용하였는데, 상기 산화개시제와 환원개시제는 접착제 총중량을 기준으로 각각 0.2 ~ 0.4중량%, 0.1 ~ 0.3중량% 정도의 소량 첨가함에 의해 상기 프리에멀젼 공중합체에 대한 경화반응을 조절하는 역할을 하게 되며, 그로부터 제조되는 접착제 조성물은 인장강도와 신율이 강화되고 내구성과 내광성이 양호하게 될 뿐만 아니라 상온에서도 접착제의 가사시간을 쉽게 조절할 수 있게 된다.
The emulsifier used in the above reaction includes polyoxyethylene nonylphenyl ether and the like about 0.5 to 1.5% by weight to have excellent adhesion and water stability, but this prevents the problem of deteriorating the properties of the polymer material. To this end, in the present invention, ammonium persulphate was used as an oxidation initiator, and sodium bisulphate was used as a reducing initiator. The oxidation initiator and the reducing initiator were 0.2 to 0.4% by weight and 0.1% based on the total weight of the adhesive, respectively. By adding a small amount of about 0.3% by weight to serve to control the curing reaction to the pre-emulsion copolymer, the adhesive composition prepared therefrom is not only enhanced tensile strength and elongation, but also good durability and light resistance as well as room temperature Even the pot life of the adhesive can be easily adjusted.
다음으로, 본 발명에서 사용되는 암모니아수(Ammonium hydroxide water)는 접착제 조성물 총중량을 기준으로 0.5 ~ 1.5중량% 정도로 첨가되어 접착제 용액의 산도를 중성(PH 7 ± 1)으로 만들어 주고, 추가적으로 난연제를 2 ~ 10중량% 정도로 첨가하여 도포된 접착제의 방염성(난연성)을 강화시키며, 점도조절제는 접착제 조성물 총중량을 기준으로 10 ~ 30중량% 정도의 비율로 사용하여 접착제 용액의 점도를 3,000 ± 1,000cps(at 25℃)로 유지하고 접착성능 불량을 방지하게 된다. 아울러 본 발명의 수성 아크릴 에멀젼 접착제 조성물은 물에 희석되어 농도조절이 가능하게 되므로 물의 총사용량은 30 ~ 50중량% 정도로 조절하는 것이 접착제의 제조공정과 작업성 등의 면에서 바람직하다.
Next, ammonia water (Ammonium hydroxide water) used in the present invention is added to about 0.5 to 1.5% by weight based on the total weight of the adhesive composition to make the acidity of the adhesive solution neutral (PH 7 ± 1), additionally flame retardant 2 ~ It is added to about 10% by weight to enhance the flame retardant (flame retardancy) of the applied adhesive, the viscosity modifier is used in a ratio of about 10 to 30% by weight based on the total weight of the adhesive composition to increase the viscosity of the adhesive solution 3,000 ± 1,000 cps (at 25 ℃) to prevent poor adhesion performance. In addition, since the aqueous acrylic emulsion adhesive composition of the present invention is diluted in water to enable the concentration control, it is preferable to adjust the total amount of water to about 30 to 50% by weight in terms of manufacturing process and workability of the adhesive.
그리고 본 발명은 환경 친화적인 수성 아크릴 에멀젼 접착제 조성물로서, 상기 난연제는 삼산화안티몬(Sb2O3) 또는 삼염화안티몬(Sb2Cl3)으로 대표되는 안티몬(Antimony)계 난연제, 수산화알루미늄(Aluminium hydroxide)계, 수산화마그네슘(Magnesium hydroxide)계로 이루어진 군으로부터 선택되는 어느 1종의 난연제를 단독으로 사용하거나 혼합하여 사용하는 것이 바람직한데, 그 이유는 환경규제가 강화됨에 따라서 기존 할로겐계 난연제를 대체하는 새로운 난연제 물질을 개발하려는 노력이 전세계적으로 진행 중이며, 현재 친환경 난연제 원료로 많이 쓰이는 인(P) 화합물은 난연성능이 할로겐계의 절반에 불과하지만 가격은 2배나 높은 실정이다.
And the present invention is an environmentally friendly aqueous acrylic emulsion adhesive composition, the flame retardant is an antimony flame retardant, aluminum hydroxide represented by antimony trioxide (Sb 2 O 3 ) or antimony trichloride (Sb 2 Cl 3 ) It is preferable to use one or a combination of flame retardants selected from the group consisting of a magnesium hydroxide system and a new flame retardant to replace the existing halogen flame retardant as environmental regulations are strengthened. Efforts are being made to develop materials worldwide, and phosphorus (P) compounds, which are widely used as raw materials for eco-friendly flame retardants, are only half the flame-retardant performance but twice the price.
위와 같은 이유로, 본 발명에서 사용하는 난연제는 단순히 난연효과만을 발휘하기 위한 것이 아니라 연소시 발연 및 독성가스의 발생이 적고 베이스 수지와의 혼합성도 좋아야 하는 등 여러 가지 요구조건을 만족시키고 접착제 자체의 물성에도 영향을 끼쳐서는 안된다는 점을 고려하였다. 또한, 본 발명에서 사용되는 점도조절제는 탄산칼슘(Calcium carbonate)을 주로 사용하며, 이는 친수성 무기질 성분으로서 부착성이 양호하고 가격대비 품질이 우수하여 방음 및 단열성과 미끄럼방지 기능에 탁월한 효과가 있는 것으로 조사되었다.
For the above reasons, the flame retardant used in the present invention is not only for showing the flame retardant effect but also satisfies various requirements such as low generation of smoke and toxic gas during combustion and good mixing with the base resin and the physical properties of the adhesive itself. Consideration should not be given to this. In addition, the viscosity modifier used in the present invention mainly uses calcium carbonate, which is a hydrophilic inorganic component, which has good adhesion and excellent price-cost quality, and thus has an excellent effect on sound insulation, heat insulation, and anti-slip function. It was investigated.
본 발명의 수성 아크릴 에멀젼 접착제 조성물의 제조방법은, 하기 제1단계 내지 제3단계로 제조되는 수성 아크릴 에멀젼 접착제 조성물 100중량%를 기준으로 할 때, 1차 배합조에 물 20 ~ 30중량%와 유화제 0.5 ~ 1.5중량%를 투입한 후 교반하여 용해시킨 다음, 2-에틸 헥실 아크릴레이트 모노머(2-Ethyl hexyl acrylate monomer) 10 ~ 20중량%, 스틸렌 모노머(Stylene monomer) 12 ~ 22중량%, 아크릴산 모노머(Acryl acid monomer) 0.5 ~ 1.5중량%, N-메틸올 아크릴아미드 모노머(N-methylol acrylamide monomer) 1 ~ 3중량%를 투입하고 유화시켜 프리에멀젼 중합체를 제조하는 제1단계; 2차 반응조에 물 10 ~ 20중량%를 넣고 온도를 60 ~ 80℃로 유지하면서 산화개시제인 암모늄 퍼설페이트(Ammonium persulphate) 0.2 ~ 0.4중량%와 환원개시제인 소듐 비설페이트(Sodium bisulphate) 0.1 ~ 0.3중량%를 투입한 다음, 반응조의 온도를 70 ~ 90℃로 유지하면서 상기 프리에멀젼 중합체를 2 ~ 4시간에 걸쳐 적하시킨 후 중화제인 암모니아수(Ammonium hydroxide water) 0.5 ~ 1.5중량%를 투입하고 혼합 및 숙성시켜 수성 아크릴 에멀젼 접착제를 합성하는 제2단계; 상기 합성된 수성 아크릴 에멀젼 접착제에 난연제 2 ~ 10중량%, 점도조절제 10 ~ 30중량%를 첨가하고 혼합 및 냉각시켜 제품화하는 제3단계를 순차적으로 포함하여 이루어진다.
The method for producing the aqueous acrylic emulsion adhesive composition of the present invention, based on 100% by weight of the aqueous acrylic emulsion adhesive composition prepared in the first step to the third step, 20 to 30% by weight water and emulsifier in the primary blending tank 0.5 to 1.5% by weight, and then stirred to dissolve, 10 to 20% by weight of 2-ethyl hexyl acrylate monomer, 12 to 22% by weight of styrene monomer (Stylene monomer), acrylic acid monomer (Acryl acid monomer) 0.5 to 1.5% by weight, 1 to 3% by weight of N-methylol acrylamide monomer (N-methylol acrylamide monomer) by adding and emulsifying the first step of preparing a preemulsion polymer; 10 to 20% by weight of water was added to the secondary reactor, and the temperature was maintained at 60 to 80 ° C, while 0.2 to 0.4% by weight of the oxidation initiator ammonium persulphate and 0.1 to 0.3 of sodium bisulphate as a reducing initiator. After adding the weight%, the pre-emulsion polymer was added dropwise over 2 to 4 hours while maintaining the temperature of the reaction tank at 70 ~ 90 ℃ and then 0.5 to 1.5% by weight of the neutralizing agent (Ammonium hydroxide water) was added and mixed and A second step of aging to synthesize an aqueous acrylic emulsion adhesive; It comprises a third step of adding the flame retardant 2 to 10% by weight, the viscosity modifier 10 to 30% by weight to the synthesized aqueous acrylic emulsion adhesive and mixing and cooling to commercialize.
제1단계 공정은, 최종적으로 제조되는 수성 아크릴 에멀젼 접착제 조성물 100중량%를 기준으로 할 때, 1차 배합조에 물 20 ~ 30중량%에 대하여 유화제 0.5 ~ 1.5중량%를 투입한 후 교반하여 용해시킨 다음, 2-에틸 헥실 아크릴레이트 모노머(2-Ethyl hexyl acrylate monomer) 10 ~ 20중량%, 스틸렌 모노머(Stylene monomer) 12 ~ 22중량%, 아크릴산 모노머(Acryl acid monomer) 0.5 ~ 1.5중량%, N-메틸올 아크릴아미드 모노머(N-methylol acrylamide monomer) 1 ~ 3중량%를 투입하고 유화시켜 프리에멀젼 중합체를 제조하는 것으로, 교반기를 이용하여 물과 유화제를 먼저 혼합시키고 2-에틸 헥실 아크릴레이트 모노머, 스틸렌 모노머, 아크릴산 모노머, N-메틸올 아크릴아미드 모노머를 혼합하되, 교반과정에서의 마찰열을 줄이기 위해 가압되지 않은 상태로 교반한다.
In the first step, 0.5 to 1.5% by weight of an emulsifier is added to the primary blending tank with respect to 20 to 30% by weight of water, based on 100% by weight of the finally prepared aqueous acrylic emulsion adhesive composition. Next, 10 to 20% by weight of 2-ethyl hexyl acrylate monomer, 12 to 22% by weight of styrene monomer (Stylene monomer), 0.5 to 1.5% by weight of acrylic acid monomer (Acryl acid monomer), N- 1 to 3% by weight of methylol acrylamide monomer (N-methylol acrylamide monomer) is added to emulsify to prepare a preemulsion polymer, using a stirrer to mix water and an emulsifier first, 2-ethyl hexyl acrylate monomer, styrene The monomer, the acrylic acid monomer, and the N-methylol acrylamide monomer are mixed, but stirred in an unpressurized state to reduce the frictional heat during the stirring process.
제2단계 공정은, 최종적으로 제조되는 수성 아크릴 에멀젼 접착제 조성물 100중량%를 기준으로 할 때, 2차 반응조에 물 10 ~ 20중량%를 넣고 온도를 60 ~ 80℃로 유지하면서 산화개시제인 암모늄 퍼설페이트(Ammonium persulphate) 0.2 ~ 0.4중량%와 환원개시제인 소듐 비설페이트(Sodium bisulphate) 0.1 ~ 0.3중량%를 투입한 다음, 반응조의 온도를 70 ~ 90℃로 유지하면서 상기 프리에멀젼 중합체를 2 ~ 4시간에 걸쳐 적하시킨 후 중화제인 암모니아수(Ammonium hydroxide water) 0.5 ~ 1.5중량%를 투입하고 혼합 및 숙성시켜 수성 아크릴 에멀젼 접착제를 합성하게 된다.
The second step process is based on 100% by weight of the aqueous acrylic emulsion adhesive composition to be finally produced, ammonium peroxide, an oxidation initiator, while putting 10-20% by weight of water in the secondary reactor and maintaining the temperature at 60-80 ° C. 0.2 to 0.4% by weight of sulfate (Ammonium persulphate) and 0.1 to 0.3% by weight of sodium bisulphate as a reducing initiator were added, and then the preemulsion polymer was maintained at 70 to 90 ° C. while maintaining the temperature of the reaction tank at 2 to 4 ° C. After dropping over time, 0.5 to 1.5% by weight of neutralizing ammonium hydroxide water (Ammonium hydroxide water) was added, mixed and aged to synthesize an aqueous acrylic emulsion adhesive.
제3단계 공정은, 최종적으로 제조되는 수성 아크릴 에멀젼 접착제 조성물 100중량%를 기준으로 할 때, 상기 합성된 수성 아크릴 에멀젼 접착제에 난연제 2 ~ 10중량%, 점도조절제 10 ~ 30중량%를 첨가하고 혼합 및 냉각시켜 제품화함으로써 수성 아크릴 에멀젼 접착제 조성물을 제조하게 된다. 이상과 같이 전술한 함량으로 이루어진 접착제 조성물은 수용성의 유백색 졸(sol)상으로 상온 상압에서 안전하게 시공할 수 있으며, 점도는 3,000 ± 1,000cps(at 25℃) 정도로 매우 광범위하게 분포될 수 있으며, PH는 7 ± 1을 나타낸다.
The third step process is based on 100% by weight of the finally prepared aqueous acrylic emulsion adhesive composition, to add 2 to 10% by weight of flame retardant, 10 to 30% by weight of viscosity modifier to the aqueous acrylic emulsion adhesive synthesized and mixed And cooled to commercialize to produce the aqueous acrylic emulsion adhesive composition. As described above, the adhesive composition having the above-described content can be safely installed at room temperature under a water-soluble milky white sol, and the viscosity can be distributed very broadly at about 3,000 ± 1,000 cps (at 25 ° C). Represents 7 ± 1.
이상에서 살펴본 바와 같이 본 발명은 수많은 실험을 거쳐 완성되었으나, 이하에서는 당업자가 용이하게 이해하고 실시할 수 있을 정도의 바람직한 실시예를 통하여 본 발명을 설명한다.
As described above, the present invention has been completed through numerous experiments. Hereinafter, the present invention will be described through preferred embodiments to be easily understood and implemented by those skilled in the art.
<실시예 1>≪ Example 1 >
프리에멀젼Pre-emulsion 중합체의 제조 Preparation of polymer
1000ℓ 배합조에 물 225㎏을 넣고 유화제인 폴리옥시에틸렌 노닐페닐 에테르(NP) 10㎏을 투입하여 용해 교반하면서 2-에틸 헥실 아크릴레이트 모노머(2-EHAM) 150㎏, 스틸렌 모노머(SM) 170㎏, 아크릴산 모노머 10㎏, N-메틸올 아크릴아미드 모노머(N-MAM) 20㎏을 투입하여 유화시킨다.
225 kg of water was added to a 1000-l mixing tank, 10 kg of polyoxyethylene nonylphenyl ether (NP) as an emulsifier was added thereto, 150 kg of 2-ethylhexyl acrylate monomer (2-EHAM), 170 kg of styrene monomer (SM), and dissolved with stirring. 10 kg of acrylic acid monomer and 20 kg of N-methylol acrylamide monomer (N-MAM) are added and emulsified.
<실시예 2><Example 2>
수성 아크릴 Aqueous acrylic 에멀젼emulsion 접착제의 합성 Synthesis of Adhesive
1000ℓ 반응조에 물 150㎏을 넣고 온도를 70℃ 정도로 올리고, 산화개시제인 암모늄 퍼설페이트(APS) 3㎏과 환원개시제인 소듐 비설페이트(SBS) 2㎏을 투입한 다음, 상기 유화된 프리에멀젼 중합체를 3시간에 걸쳐 적하시키고 중화제인 암모니아수 10㎏을 투입하고 2시간 동안 혼합 및 숙성시킨다.
150 kg of water was added to a 1000 L reactor, and the temperature was raised to about 70 ° C., 3 kg of ammonium persulfate (APS) as an oxidation initiator and 2 kg of sodium bisulfate (SBS) as a reducing initiator were added thereto, and then the emulsified preemulsion polymer was added. It is dripped over 3 hours, 10 kg of ammonia water which is a neutralizing agent is added, it mixes and matures for 2 hours.
<실시예 3><Example 3>
수성 아크릴 Aqueous acrylic 에멀젼emulsion 접착제 조성물의 제조 Preparation of adhesive composition
상기 합성된 수성 아크릴 에멀젼 접착제에 난연제인 안티몬 50㎏, 점도조절제인 탄산칼슘 분말 200㎏을 첨가하고 혼합 및 냉각시켜 유백색의 졸(sol)상 수성 아크릴 에멀젼 접착제 조성물을 제조하였다.
50 kg of antimony, a flame retardant, and 200 kg of calcium carbonate powder, a viscosity modifier, were added to the synthesized aqueous acrylic emulsion adhesive, and mixed and cooled to prepare a milky white sol aqueous acrylic emulsion adhesive composition.
<실험예><Experimental Example>
상기 실시예 1 내지 실시예 3에 따라 제조된 수성 아크릴 에멀젼 접착제 조성물과 시중에 유통되는 제품으로 고무아스팔트계 접착제와 용제형 우레탄계 접착제를 비교하여 인장강도, 신장율, 부착강도, 내화학성, 표면 평활성 및 작업성에 대하여 측정한 결과를 아래 [표 1]에 나타내었다. 여기서, 인장강도 및 부착강도는 ASTM D 638-91 및 ASTM D 4541-89 방법으로, 신장율은 ASTM D638-91 방법에 따라 측정하였으며, 내화학성은 ASTM D 543 방법에 의거 측정하였다.
Compared to the aqueous acrylic emulsion adhesive composition prepared according to Examples 1 to 3 and commercially available products, rubber asphalt adhesives and solvent-based urethane adhesives were compared for tensile strength, elongation rate, adhesion strength, chemical resistance, surface smoothness and The results measured for workability are shown in Table 1 below. Here, the tensile strength and the adhesive strength were measured by ASTM D 638-91 and ASTM D 4541-89 methods, the elongation was measured according to the ASTM D638-91 method, and the chemical resistance was measured according to the ASTM D 543 method.
구분
division
실시예 3
Example 3
고무아스팔트계
접착제
Rubber asphalt system
glue
우레탄계
접착제
Urethane-based
glue
인장강도(㎏f/㎠)
Tensile Strength (㎏f / ㎠)
73
73
59
59
36
36
신장률(%)
Elongation (%)
785
785
740
740
710
710
부착강도(㎏f/㎠)
Adhesion Strength (㎏f / ㎠)
24
24
17
17
12.5
12.5
내화학성
Chemical resistance
에틸렌글리콜
Ethylene glycol
이상없음
clear
이상없음
clear
이상없음
clear
칼슘클로라이드
Calcium chloride
이상없음
clear
불량
Bad
불량
Bad
가솔린
Gasoline
이상없음
clear
이상없음
clear
불량
Bad
모터오일
Motor oil
이상없음
clear
이상없음
clear
이상없음
clear
소듐클로라이드
Sodium chloride
이상없음
clear
불량
Bad
불량
Bad
표면 평활성
Surface smoothness
○
○
×
×
○
○
작업성
Workability
양호
Good
불량
Bad
불량
Bad
상기 표면 평활성에서,In the surface smoothness,
○ : 핀홀 등의 표면 불량이 발생되지 않음○: No surface defect such as pinhole occurred
× : 핀홀 등의 표면 불량이 미세하게 발생
X: Surface defects such as pinholes are generated finely
상기 [표 1]의 결과로부터 본 발명의 수성 아크릴 에멀젼 접착제 조성물은 기존 용제형 유성제품에 비하여 인장강도, 신장율, 부착강도, 내화학성 및 표면 평활성이 전반적으로 양호하였고, 점도조절제와 물의 사용량에 따라 농도 및 점성 조절이 용이할 뿐만 아니라 주변 온도의 영향을 받지 않고 상온에서도 작업이 가능하며, 유기용제에 의한 유해성이 전혀 없다는 사실을 확인할 수 있었다.
From the results of the above [Table 1], the aqueous acrylic emulsion adhesive composition of the present invention was generally better in tensile strength, elongation rate, adhesion strength, chemical resistance and surface smoothness than conventional solvent-based oil-based products, depending on the amount of viscosity modifier and water used Not only is it easy to control the concentration and viscosity, but it is also possible to work at room temperature without being influenced by the ambient temperature, and it can be confirmed that there is no harm by organic solvents.
따라서 본 발명의 수성 아크릴 에멀젼 접착제 조성물은 과립상 석재(granule stone)를 석재, 콘크리트, 시멘트, 금속, 플라스틱, 부직포 등에 도포할 시 표면 부착성이 탁월하게 됨은 물론, 상기와 같은 동종(同種) 또는 이종(異種) 재질 간에도 강한 접착력과 내구성, 방화성(난연성)을 나타내며, 그 접착력에 의해 방음 및 단열성과 미끄럼방지 기능에 탁월한 효과가 있기 때문에, 안료 등을 첨가하여 방수코팅재나 광택도료 등에 적용할 수 있는 환경 친화적인 접착제로서, 건축 및 토목구조물의 바닥면이나 내외 벽체, 계단 등에 다양한 용도와 형태로 사용되어 질 수 있다.Therefore, the aqueous acrylic emulsion adhesive composition of the present invention is excellent in surface adhesion when the granule stone (granule stone) is applied to stone, concrete, cement, metal, plastic, non-woven fabric, as well as the same or the like It exhibits strong adhesion, durability, and fire resistance (flame retardancy) even between different materials, and its adhesion is excellent in sound insulation, heat insulation, and anti-slip function, so it can be applied to waterproof coatings or varnish paints by adding pigments. As an environmentally friendly adhesive, it can be used in various uses and forms on floors, interior and exterior walls, stairs, etc. of construction and civil structures.
Claims (6)
상기 유화제는 폴리옥시에틸렌 노닐페닐 에테르(Polyoxyethylene nonylphenyl ether)인 것을 특징으로 하는 수성 아크릴 에멀젼 접착제 조성물.The method of claim 1,
The emulsifying agent is an aqueous acrylic emulsion adhesive composition, characterized in that polyoxyethylene nonylphenyl ether.
상기 난연제는 안티몬(Antimony)계, 수산화알루미늄(Aluminium hydroxide)계, 수산화마그네슘(Magnesium hydroxide)계로 이루어진 군으로부터 선택되는 어느 1종 이상인 것을 특징으로 하는 수성 아크릴 에멀젼 접착제 조성물.The method of claim 1,
The flame retardant is an aqueous acrylic emulsion adhesive composition, characterized in that at least one selected from the group consisting of antimony (Antimony), aluminum hydroxide (Aluminium hydroxide), magnesium hydroxide (Magnesium hydroxide) system.
상기 안티몬(Antimony)계 난연제는 삼산화물(Sb2O3) 또는 삼염화물(Sb2Cl3)인 것을 특징으로 하는 수성 아크릴 에멀젼 접착제 조성물.The method of claim 3,
The antimony-based flame retardant is an aqueous acrylic emulsion adhesive composition, characterized in that trioxide (Sb 2 O 3 ) or trichloride (Sb 2 Cl 3 ).
상기 점도조절제는 탄산칼슘(Calcium carbonate)인 것을 특징으로 하는 수성 아크릴 에멀젼 접착제 조성물.The method of claim 1,
The viscosity modifier is calcium carbonate (Calcium carbonate), characterized in that the aqueous acrylic emulsion adhesive composition.
1차 배합조에 물 20 ~ 30중량%에 대하여 유화제 0.5 ~ 1.5중량%를 투입한 후 교반하여 용해시킨 다음, 2-에틸 헥실 아크릴레이트 모노머(2-Ethyl hexyl acrylate monomer) 10 ~ 20중량%, 스틸렌 모노머(Stylene monomer) 12 ~ 22중량%, 아크릴산 모노머(Acryl acid monomer) 0.5 ~ 1.5중량%, N-메틸올 아크릴아미드 모노머(N-methylol acrylamide monomer) 1 ~ 3중량%를 투입하고 유화시켜 프리에멀젼 중합체를 제조하는 제1단계;
2차 반응조에 물 10 ~ 20중량%를 넣고 온도를 60 ~ 80℃로 유지하면서 산화개시제인 암모늄 퍼설페이트(Ammonium persulphate) 0.2 ~ 0.4중량%와 환원개시제인 소듐 비설페이트(Sodium bisulphate) 0.1 ~ 0.3중량%를 투입한 다음, 반응조의 온도를 70 ~ 90℃로 유지하면서 상기 프리에멀젼 중합체를 2 ~ 4시간에 걸쳐 적하시킨 후 중화제인 암모니아수(Ammonium hydroxide water) 0.5 ~ 1.5중량%를 투입하고 혼합 및 숙성시켜 수성 아크릴 에멀젼 접착제를 합성하는 제2단계;
상기 합성된 수성 아크릴 에멀젼 접착제에 난연제 2 ~ 10중량%, 점도조절제 10 ~ 30중량%를 첨가하고 혼합 및 냉각시켜 제품화하는 제3단계;
로 이루어지는 것을 특징으로 하는 수성 아크릴 에멀젼 접착제 조성물의 제조방법.Based on 100% by weight of the aqueous acrylic emulsion adhesive composition prepared in the following first to third steps,
0.5 to 1.5% by weight of an emulsifier was added to 20-30% by weight of water in the primary blending tank, followed by stirring and dissolving. 10 to 20% by weight of 2-ethylhexyl acrylate monomer, styrene 12 to 22% by weight of monomer (Stylene monomer), 0.5 to 1.5% by weight of acrylic acid monomer, 1 to 3% by weight of N-methylol acrylamide monomer are added and emulsified A first step of preparing a polymer;
10 to 20% by weight of water was added to the secondary reactor, and the temperature was maintained at 60 to 80 ° C, while 0.2 to 0.4% by weight of the oxidation initiator ammonium persulphate and 0.1 to 0.3 of sodium bisulphate as a reducing initiator. After adding the weight%, the pre-emulsion polymer was added dropwise over 2 to 4 hours while maintaining the temperature of the reaction tank at 70 ~ 90 ℃ and then 0.5 to 1.5% by weight of the neutralizing agent (Ammonium hydroxide water) was added and mixed and A second step of aging to synthesize an aqueous acrylic emulsion adhesive;
A third step of adding 2 to 10 wt% of a flame retardant and 10 to 30 wt% of a viscosity modifier to the synthesized aqueous acrylic emulsion adhesive, followed by mixing and cooling to commercialize;
A method of producing an aqueous acrylic emulsion adhesive composition, characterized in that consisting of.
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| KR20200137084A (en) * | 2019-05-28 | 2020-12-09 | 이계영 | Coating composition for non-slip having improving durability |
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