WO2020017736A1 - Uv경화형 필름이 코팅된 열효율을 극대화한 보온 단열재 및 그 제조방법 - Google Patents
Uv경화형 필름이 코팅된 열효율을 극대화한 보온 단열재 및 그 제조방법 Download PDFInfo
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- WO2020017736A1 WO2020017736A1 PCT/KR2019/003793 KR2019003793W WO2020017736A1 WO 2020017736 A1 WO2020017736 A1 WO 2020017736A1 KR 2019003793 W KR2019003793 W KR 2019003793W WO 2020017736 A1 WO2020017736 A1 WO 2020017736A1
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- WO
- WIPO (PCT)
- Prior art keywords
- polyol
- acrylate
- coated
- insulating material
- thermal insulation
- Prior art date
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Classifications
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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Definitions
- the present invention relates to an industrial thermal insulation material coated with a UV film maximized thermal efficiency, in detail, petrochemical (Petroleum Chemical Plant), power plant (Power Plant), steel mill (Steel Marking Plant), chemical storage tank, oil tank,
- the present invention relates to a heat insulating material coated with a UV film excellent in preventing moisture penetration, improving thermal efficiency, and using non-combustible materials for ships (ships), building interior and exterior materials, ground or underground pipelines, roofs, lining materials, and the like.
- Thermal insulation is a material for reducing the heat loss or heat inflow to the outside by covering the outside of the part to maintain a constant temperature. If the temperature is less than 100 °C depending on the operating temperature is called a cold insulation material, 100 ⁇ 500 °C It is called heat insulation, 500-1,100 degreeC heat insulation, and 1,100 degreeC or more fireproof insulation.
- the heat insulating material is preferably a small thermal conductivity of the material itself, but most of the thermal conductivity is not so small in most cases to make the porous to reduce the thermal conductivity to improve the thermal insulation using air in the pores.
- the material of the thermal insulation can be divided into organic and inorganic, and organic materials include cork, cotton, felt, cork carbide, foam rubber, etc., and inorganic materials include asbestos, glass wool, quartz cotton, diatomaceous earth, calcium silicate, Pearlite etc. are used.
- heat insulation is applied to the pipe, and in particular, it is transferred from the pipe of power plants, petrochemical plants, and various vessels. Since the fluid generates high heat, it is necessary to mold and manufacture the heat insulating material using a material having excellent heat insulation and non-combustibility to satisfy the heat insulation function and to prevent fire. In particular, the plant industry is always exposed to strong acid or base products, which causes corrosion of metal components, resulting in thermal insulation and various problems.
- E-Glass Fiber As a material of thermal insulation thermal insulation material to satisfy these conditions, asbestos which is excellent in thermal insulation and excellent in electrical insulation, fire resistance, sound absorption, corrosion resistance, water resistance, and the like, rock insulation, ceramic fiber, calcium silicate, pearlite, vermiculite, etc.
- E-Glass Fiber has advantages such as high electrical insulation, excellent radiation resistance, high weathering resistance and heat resistance, and low weight with high porosity. Since it is low, it is limited to the field which requires high strength and high functionality, and it is weak against external physical shocks due to its characteristics, and there is a problem in that the service life is shortened by the impact strength being lowered due to the penetration of moisture and aging and fracture.
- Korean Patent Nos. 274314 and 522568 developed by the present applicant regarding a method for manufacturing a heat insulating pipe using a glass fiber mat are formed of a glass fiber mat that can withstand high heat and have a binder applied thereto due to the characteristics of the glass fiber. By winding the rollers and pressing them, they can be lightened and have high thermal insulation properties with a high density of about 180 ⁇ 220kg / m3.Insulation pipes are required for non-combustibility and sound absorption as well as industrial piping and building structures such as oil companies and power plants. Is disclosed.
- An object of the present invention is to provide an industrial thermal insulation material which is light, low in volume and excellent in heat insulation, in which a thermosetting resin composition comprising a water-soluble acrylic adhesive, a curing agent, and a flame retardant is impregnated into a glass long fiber mat.
- an object of the present invention is to reduce the surface carbonization phenomenon or chlorine (Cl-) ion to a high temperature to prevent metal pipe corrosion and to provide an industrial thermal insulation material having an excellent water-repellent function.
- Insulating heat insulating material (Matt) of the present invention for solving the problems as described above is manufactured by laminating with E-Glass filament.
- a raw material of the glass fiber as described above silica, limestone, borax, etc. form the mainstream, and the physical properties thereof vary depending on the formulation. Therefore, according to the raw material composition can be divided into A-glass, C-glass, E-glass and S-glass, etc.
- E-Glass long fibers are used.
- thermosetting water-soluble acrylic adhesive composition of glass fibers is synthesized.
- Thermosetting adhesive in the present invention is B-Carboxyethyl Acrylate.
- Reactive acrylic monomers selected from Octyl or Decyl Acrylate, Isobonyl Acrylate, 2-Phenoxyethyl Acrylate, Urethane Acrylate, Dipropylene Glycol Diacrylate, and 6-Hexanediol Diacrylate with a combination of reactive acrylic monomers and aliphatic urethane acrylates and aliphatic urethane diacrylates 2, 2-Dlmethoxy-1, 2-dlphenyl-ethan-1-one, 1- as an acrylic oligomer, basic aqueous solution (-OH, SO4) and a thermosetting initiator selected from laterate and aliphatic urethane triacrylate.
- the binder composition of the present invention is 20-40 parts by weight of water, 20-40 parts by weight of bentonite, 1-10 parts by weight of silica, flame retardant material, 1-10 parts by weight of nitrogen based on 100 parts by weight of the thermosetting water-soluble acrylic adhesive , 1 to 10 parts by weight of a water repellent, 1 to 10 parts by weight of a penetrant, 1 to 2 parts by weight of an antifoaming agent, and 1 to 2 parts by weight of a dispersant.
- the flame retardant may be at least one selected from inorganic flame retardant germanium, ceramic, silica, dolomite or natural silica, and the dispersant is a generic term for the surfactant used in the application that requires a dispersing action in general in the present invention
- the dispersant is a generic term for the surfactant used in the application that requires a dispersing action in general in the present invention
- One or more of oxyalkylether naphthalenesulfonate condensates, alkyl diphenyl ether sodium disulfonate, sodium lignin sulfonate can be used.
- the heat insulating material of the present invention can be configured in various forms. That is, it can be manufactured in the form of a tube to cover the pipe or can be manufactured in the form of a sheet.
- the surface of the tube-type thermal insulation is coated with a UV cured film in a dural-cure curing method.
- a raw material for UV curing coating is an acrylic resin having a double bond, and a small amount of photoinitiator is added, and then polymerized due to rapid reactivity when irradiated with ultraviolet rays.
- the curing by UV is primarily performed and the curing by heat secondly.
- Double-curable resin in the present invention is 2-HEA (2-hydroxyethyl acrylate), 2-Ethylhexyl acrylate (2-EHA), 2-hydroxyethyl methacrylate (2-HEMA), 2-HPA (2-hydroxypropyl acrylate)
- 2,2'-azo-bis-isobutylnitrile 2,2'-azo-bis-isobutyrylnitrile (AIBN) photoinitiator and acrylic pyhot
- thermosetting polyols selected from the above-mentioned double-curable resins, polyether polyols, polyester polyols, prolactone polyols, polycarbonate polyols, polybutadiene polyols or alkyl polyols, and toluene diisocynate (TDI),
- MDI Diphenylmethane diisocynate
- MXDI tetramethylxylene diisocynate
- XDI Xylene diisocyanate
- IPDI Isophorone diisocyanate
- HMDI hexamethylene diisocyanate
- the present invention does not simply blend the thermosetting resin and the UV curable resin in order to enable double curing, but by introducing a functional group capable of UV curing in the polymer resin itself, thereby three-dimensional crosslinking. It can induce bonding and improve the problem of not being transmitted through light or uncured when using pigments or paints, and also ensure high chemical resistance, heat resistance and scratch resistance while maintaining excellent moldability. have.
- Thermal insulation according to the present invention by using a thermosetting water-soluble acrylic adhesive to ensure the minimum uniform coating film thickness necessary for reinforcing strength at the time of curing and corrosion protection of the pipe, and easy to install with flexibility and sufficient working time before work
- the surface of the insulation is UV-coated by the dural-cure curing method to cure even parts where light or light cannot be reached, and the thermal insulation material having a vivid color even when dyes and pigments are added to realize various colors.
- FIG. 1 is a block diagram of the thermal insulation of the present invention coated with a UV film on the surface of the protective cover for pipe insulation.
- the reactive acrylic monomer in the thermosetting adhesive composition of the present invention may be a beta-carboxyethyl acrylate (B-Carboxyethyl Acrylate) of formula (1), or an oxyethylated acrylate (Oxyethylated Acrylate) of the formula (2)
- B-Carboxyethyl Acrylate beta-carboxyethyl acrylate
- Oxyethylated Acrylate oxyethylated acrylate
- 2-phenoxyehtyl Acrylate and Urethane Acrylate of Formula (3) may be selected.
- 2,2-dimethoxy-1,2-diphenyl ethan-1-one of the following formula (4) or (dl, 2-Dlmethoxy-1, 2-dlphenyl-ethan-1-one) or 1-Hydroxy-cyclohexylphenyl-ketone of formula (5), or 2-methyl-1- [4- (methylylthio) phenyl-2- of formula (6) Morpholino-propopan-1-one [2-Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one], or (7) Potassium persulfate, A sensitizer, a crosslinking agent and a functional additive may be further added.
- thermosetting adhesive As shown in Table 1, an acrylic monomer, an acrylic oligomer, a basic aqueous solution, and a reaction initiator were added thereto, followed by heating to synthesize a thermosetting adhesive.
- Example 4-6 Composition of Inorganic Material-Containing Binder
- a binder for an E-Glass long fiber mat was prepared by blending a curable adhesive, water, bentonite, silica, a flame retardant, a nitrogen-based resin, a water repellent, a penetrant, and an antifoaming agent.
- Example 4 Composition of binder Ingredients (parts by weight) Example 4 Example 5 Example 6 Thermosetting adhesive Example 1 Adhesive: 100 Example 2 Adhesive: 100 Example 3 Adhesive: 100) water 20 30 40 Bentonite 30 20 40 Silica 5 5 7 Flame Retardant 5 10 15 Nitrogen-based resin 2 4 6 Water repellent 2 4 6 Penetrant 6 4 2 Antifoam One 2 One Dispersant 2 One 2
- Bentonite 20-40 parts by weight with respect to 100 parts by weight of the heat-curing adhesive of the binder component is preferred, when the bentonite is 40 parts by weight or more, the mechanical strength is excellent, but the adhesive strength is inferior, Bentonite is 20 parts by weight or less If there is a disadvantage that the mechanical strength falls.
- polyoxyalkyl ether sodium naphthalene sulfonate-condensate was used as a dispersant
- alkyl diphenyl ether sodium disulfonate was used
- sodium lignin sulfonate was used.
- the water-soluble binder of Example 4 is uniformly coated on the surface of the E-glass long fiber mat, compressed by a roller, and laminated to a cylindrical jig to prepare a glass-fiber fiber insulating material having various thicknesses.
- the tube-shaped E-Glass filament insulation is dried for 2 to 6 hours at a temperature of about 180 ⁇ 250 °C in microwave and hot air drying apparatus.
- 2-HEA 30 mixed% by weight of 2-HEMA 40% by weight, and (2-HEMA) 30 wt% and the optical initiator 2,2' at 60 °C-bis- by the addition of isobutyl nitrile (AIBN) 5
- AIBN isobutyl nitrile
- the product of the comparative example is a thermal cover of an E-Glass long fiber thermal insulating material coated with aluminum foil on the surface.
- Glossiness was measured at a 60 ° angle using a glossmeter.
- Table 3 shows the results of the performance test on the glossiness, surface hardness, scratch resistance and flexibility.
- the insulating heat insulating material cover of the present invention can be seen that the glossiness of 97, it was confirmed that the surface hardness, scratch resistance and flexibility is excellent.
- the present invention relates to a thermal insulation material and a method of manufacturing the same, which maximize the thermal efficiency of a UV-curable film coated with a uniform coating.
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Abstract
본 발명은 보온단열재에 관한 발명으로 열경화 수용성 아크릴 접착제를 사용함으로써 경화시 강도 보강 및 배관의 부식방지에 필요한 최소한의 균일한 코팅 막 두께를 확보하고 작업 전에는 유연성과 충분한 작업시간을 가지고 시공하기 쉽도록 하였고, 또한 단열재 표면을 dural-cure 경화 방식에 의해 UV 및 열경화 코팅시킴으로써 빛 또는 자외선이 관통될 수 없는 부분까지도 경화가 가능하며, 다양한 색상을 구현하기 위해 염료 및 안료를 첨가하는 경우에도 선명한 색상을 갖는 보온단열재의 얻을 수 있음은 물론, 재단 가공성이 좋아 금속, 플라스틱, 유리면, 도자기, 석재, 목재 및 각종 건축물 기재의 다양한 표면상태나 굴곡이 심한 형상에도 균일하게 코팅시킬 수 있는 UV 필름이 코팅된 열효율을 극대화한 보온 단열재에 관한 발명이다.
Description
본 발명은 열효율을 극대화한 UV 필름이 코팅된 산업용 보온 단열재에 관한 것으로, 상세하게는 석유화학(Petroleum Chemical Plant), 발전소(Power Plant), 제철소(Steel Marking Plant), 화학저장탱크, 오일탱크, 조선(선박), 건축물 내외장재, 지상 또는 지하 파이프라인, 지붕, 라이닝재 등의 커버로 사용되는 수분침투 방지, 열효율 개선 및 불연성이 뛰어난 UV 필름이 코팅된 보온 단열재에 관한 발명이다.
보온 단열재는 일정한 온도가 유지되도록 하려는 부분의 바깥쪽을 피복하여 외부로의 열손실이나 열의 유입을 적게 하기 위한 재료로, 사용온도에 따라 100℃ 이하인 경우에는 보냉재라 칭하며, 100∼500℃인 경우, 보온재, 500 ∼1,100℃의 단열재, 1,100℃ 이상의 내화단열재라 부르고 있다. 단열재는 소재 자체의 열전도율이 작은 것이 바람직하나, 대부분 열전도율이 그다지 작지 않으므로 대개의 경우 열전도율을 적게하기 위해서 다공질이 되도록 만들어 기공 속의 공기를 이용하여 단열성을 향상시킨다.
또한, 보온 단열재의 소재는 유기질과 무기질로 구분할 수 있고, 유기질 재료로는 코르크, 면, 펠트, 탄화코르크, 거품고무 등이 있으며, 무기질 재료로는 석면, 유리솜, 석영솜, 규조토, 규산칼슘, 펄라이트 등이 사용되고 있다.
상기와 같이 플랜트 산업 등에서 배관을 통한 유체의 이송시 그 유체의 물성변화를 방지하고, 에너지를 절약하기 위하여 배관 등에 보온 단열재를 씌우고 있으며, 특히 발전소나 석유화학 플랜트 및 각종 선박 등의 배관에서 이송되는 유체는 고열이 발생하므로 단열성 및 불연성이 뛰어난 재료를 이용해 단열재를 성형 제조하여야만 단열기능을 만족하면서도 화재 등을 예방할 수가 있게 된다. 특히 플랜트 산업은 항상 강한 산(acid)나 염기(base)성 제품에 노출이 되어 금속 성분의 부식이 발생하게 되어 단열 및 여러 가지 문제점을 일으키게 된다. 이러한 조건을 만족시키기 위한 단열보온재의 재료로 보온 단열성이 우수하고, 전기 절연성, 내화성, 흡음성, 내식성, 내수성 등이 뛰어난 석면이나, 암면, 세라믹 화이바, 규산칼슘, 펄라이트, 질석 등을 이용한 보온 단열재가 개발되고 있으며, 이들 중, 유리장 섬유(E-Glass Fiber)의 경우, 전기 절연성이 높고 방사성이 뛰어나며 내풍화성 및 내열성이 높으며, 또한, 높은 공극율로 경량화가 가능한 등의 장점이 있으나, 비교적 강도가 낮으므로 고강도, 고기능성을 요구하는 분야에 제한되고 또한, 그 특성상 외부의 물리적 충격에 약하고, 수분의 침투 및 열에 의해 노화되어 부서지는 등 충격강도가 저하됨으로써 사용수명이 단축되는 문제점이 있었다. 따라서 상기와 같은 문제점을 해결하기 위한 선행기술로 국내등록특허 제1403289호에 유리섬유, 폴리프로필렌섬유, 메타-아라미드섬유로 구성되는 니들펀칭 복합부직포를 제조한 후, 니들펀칭 복합부직포 내에 포함된 폴리프로필렌섬유를 용융시키고, 상기 니들펀칭 복합부직포의 양 표면에 불연성 알루미늄박막을 위치시킨 다음, 니들펀칭 복합부직포를 1.5 ~ 4.5mm의 두께로 압착하여 성형화한 니들펀칭 복합부직포를 제조하는 극저온에서 충격방지특성이 우수한 불연성 단열재의 제조방법을 개시하고 있으나 유기 및 무기섬유를 혼용하고 있으므로 단열성이 저하되는 문제점이 있다. 또한, 유리섬유매트를 이용한 단열파이프의 제조방법에 관하여 본 출원인이 개발한 국내등록특허 제274314호 및 제522568호에는 유리섬유가 갖는 특성상 고열에 견딜 수 있고 또 바인더가 도포된 유리섬유매트를 성형롤러에 권취하여 가압 성형함으로써 경량화는 물론 약 180 ~ 220kg/㎥의 고밀도화로 높은 단열성을 지닐 수가 있어 정유회사나 발전소 등의 산업용 배관과 건축 구조물은 물론 불연성, 흡음성 등이 요구되는 보온 단열용 파이프가 개시되어 있다.
그러나, 보온 단열재의 표면을 UV경화 필름으로 1차 자외선 경화공정을 거쳐 2차 열경화를 진행함으로 표면을 이중(Dural-cured) 경화시켜 코팅시키는 기술은 아직 개발된 바 없다.
본 발명은 유리 장섬유 매트(Matt)에 수용성 아크릴 접착제, 경화제 및 난연재를 포함하는 열경화성 수지 조성물이 함침된 가볍고, 부피가 적으며 단열성이 우수한 산업용 보온단열재를 제공함을 목적으로 한다.
또한, 본 발명은 고온에 대한 표면 탄화현상이나 염소(Cl-)이온을 줄임으로서 금속 배관부식을 방지하고 우수한 발수기능을 갖는 산업용 보온 단열재를 제공하는데 그 목적이 있다.
본 발명의 또 다른 목적은 열경화형 관능기와 UV 경화형 관능기를 동시에 갖는 이중경화형 조성물에 의한 이중 경화를 통해 우수한 성형성을 유지하면서 높은 내스크래치성을 확보할 수 있는 이중경화 조성물을 산업용 보온단열재의 표면에 코팅함으로써 강력한 접착력을 발휘할 수가 있어 탄화나 부식을 방지하고 우수한 발수기능을 갖는 산업용 보온단열재를 제공하는데 그 목적이 있다.
상기와 같은 과제를 해결하기 위한 본 발명의 보온 단열재 매트(Matt)는 E-Glass 장섬유로 적층하여 성형 제조하고 있다. 상기와 같은 유리섬유의 원료로는 규사(silica), 석회석(limestone), 붕사 등이 주류를 이루며, 그 배합에 따라서 물성이 달라진다. 따라서, 원료조성에 따라 A-glass, C-glass, E-glass 및 S-glass 등으로 구분할 수 있고 본 발명에서는 E-Glass 장섬유를 사용한다.
본 발명에서는 먼저 유리섬유의 열경화 수용성 아크릴 접착제 조성물을 합성한다. 본 발명에서 열경화 접착제는 B-Carboxyethyl Acrylate. Octyl 또는 Decyl Acrylate, Isobonyl Acrylate, 2-Phenoxyethyl Acrylate, Urethane Acrylate, Dipropylene Glycol Diacrylate 및 6-Hexanediol Diacrylate 중에서 선택된 1종 또는 2종 이상을 조합한 반응성 아크릴 모노머와 알리파틱 우레탄 아크릴레이트, 알리파틱 우레탄 디아크릴레이트, 알리파틱 우레탄 트리아크릴레이트 중에서 선택된 1 종의 아크릴 올리고머, 염기성 수용액(-OH,SO4)과 열경화 반응 개시제로 2, 2-Dlmethoxy-1, 2-dlphenyl-ethan-1-one, 1-Hydroxy-cyclohexylphenyl-ketone -Methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, 2-Hydroxy-2-methyl-1-phenyl-propanone, Potassium persulfate 중에서 선택되며, 증감제, 가교제 및 기능성 첨가제를 첨가할 수 있다.
그리고 본 발명의 바인더 조성물은 상기 열경화 수용성 아크릴 접착제 100중량부에 대하여 물 20-40중량부, 밴토나이트 20- 40중량부, 실리카 1 - 10중량부, 난연재, 질소계 수지 1 - 10중량부, 발수제 1- 10중량부, 침투제 1 - 10중량부, 소포제 1 - 2 중량부, 분산제 1 - 2중량부로 조성된다.
상기의 난연재는 무기계 난연재인 게르마늄, 세라믹, 실리카, 백운암 또는 천연규석 중에서 1종 일종 이상이 선택될 수 있으며, 분산제는 일반적으로 분산작용이 요구되는 용도에 사용되는 계면활성제의 총칭으로 본 발명에서는 폴리옥시알킬에테르 나프탈렌술폰산나트륨 축합물, 알킬 디페닐 에테르 디술폰산 나트륨, 리그닌술폰산 나트륨 중 하나 또는 하나 이상을 사용할 수 있다.
또한, 본 발명의 보온 단열재는 다양한 형태로 구성할 수 있다. 즉, 튜브형태로 구성하여 배관에 씌울 수 있는 형상으로 제조하거나 또는 시트 형태로의 제조가 가능하다.
본 발명에서는 상기와 같은 튜브형태의 보온 단열재의 표면을 dural-cure 경화 방식으로 UV 경화 필름으로 코팅시킨다.
일반적인 UV 경화코팅의 원료로 사용되는 것은 2중 결합을 가지고 있는 아크릴계열 수지로 소량의 광개시제를 첨가한 후 자외선을 방사하였을 때 빠른 반응성으로 인한 고분자(Polymerization)화가 이루어진다.
그러나, 빛 또는 광선이 관통될 수 없는 부분 또는 빛의 반대편, 그리고, 다양한 색상을 구현하기 위해 염료 및 안료를 첨가하는 경우, 이들 부분은 미경화(uncured)가 발생되어 부식, 노화, 피로 또는 박리와 같은 문제점이 발생하여 제품의 원하는 물성을 얻기에는 한계가 있다.
본 발명의 dual-cure 경화 방식은 1차적으로 UV(자외선)에 의한 경화와 2차적으로 열에 의한 경화가 이루어진다.
본 발명에서의 이중경화형 수지는 2-HEA(2-hydroxyethyl acrylate), 2-Ethylhexyl acrylate(2-EHA), 2-hydroxyethyl methacrylate(2-HEMA), 2-HPA(2-hydroxypropyl acrylate)의 아크릴레이트 모노머 및 지방족 우레탄디아크릴레이트(Aliphatic Urethane Diacrylate), 지방족 우레탄 트리아크릴레이트, 지방족우레탄 헥사아크릴레이트의 아크릴레이트 올리고머와 벤조일 퍼옥사이드(benzoyl peroxide) 또는 2,2'-아조-비스-이소부틸니트릴(2,2'-azo-bis-isobutyrylnitrile ; AIBN)인 광개시제 및 Acrylic pyhotoinitiator(4-benwophenone diethyleneglycol acrylate)인 아크릴산으로 합성할 수 있다. 이때, UV-A, UV-B, UV-C파장의 빛으로 경화 가능한 광개시제를 사용할 경우, 경화시 강도 보강 및 부식에 필요한 균일한 코팅막 두께를 확보하고 작업 전에는 유연성을 확보할 수 있다. 또한, 이중 경화 시에는 상기의 이중경화성 수지와 폴리에테르 폴리올, 폴리에스테르 폴리올, 프로락톤 폴리올, 폴리카보네이트 폴리올, 폴리부타디엔 폴리올 또는 알킬 폴리올 중에서 선택된 1종 또는 2 이상의 열경화성 폴리올과 TDI(Toluene diisocynate), MDI(Diphenylmethane diisocynate), MXDI(tetramethylxylene diisocynate), XDI(Xylene diisocyanate), IPDI(Isophorone diisocyanate) 또는 HMDI(hexamethylene diisocyanate) 중에서 선택된 1종의 이소시아네이트와 Acylphophine oxide, benzoyl peroxide, benzophenone계 광개시제에 의해 2차적으로 코팅층의 광경화하는 단계를 포함함을 특징으로 한다.
상기와 같이 본 발명에서는 이중경화를 가능하게 하기 위해 열경화 수지와 UV 경화 수지를 단순히 블렌딩(blending)하는 것이 아니라, 고분자 수지 자체에 UV 경화가 가능한 관능기를 도입함으로써, 3차원적 가교(crosslinked) 결합을 유도 하며 특히 빛이 투과하지 못하는 지점이나 안료나 도료의 사용시 미경화 등의 문제를 개선할 수 있을 뿐만 아니라, 우수한 성형성을 유지하면서 높은 내화학성, 내 열성, 내스크래치성을 확보할 수 있다.
〈UV Dural-cured 경화형 도료 반응 메카니즘〉
본 발명에 따른 보온단열재는 열경화 수용성 아크릴 접착제를 사용함으로써 경화시 강도 보강 및 배관의 부식방지에 필요한 최소한의 균일한 코팅 막 두께를 확보하고 작업 전에는 유연성과 충분한 작업시간을 가지고 시공하기 쉽도록 하였고, 또한 단열재 표면을 dural-cure 경화 방식에 의해 UV 코팅시킴으로써 빛 또는 광선이 도달될 수 없는 부분까지도 경화가 가능하며, 다양한 색상을 구현하기 위해 염료 및 안료를 첨가하는 경우에도 선명한 색상을 갖는 보온단열재의 얻을 수 있음은 물론, 재단 가공성이 좋아 금속, 플라스틱, 유리면, 도자기, 석재, 목재 및 각종 건축물 기재의 다양한 표면상태나 굴곡이 심한 형상에도 균일하게 코팅시킬 수 있는 등의 효과가 있다.
도 1은 배관 단열용 보호커버의 표면에 UV필름이 코팅된 본 발명의 보온 단열재의 구성도이다.
본 발명에 서술된 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련 기술의 문맥 상 가지는 의미와 일치하는 것으로 해석되어야 하며, 본 출원에서 명백하게 정의하지 않는 한, 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다.
이하, 본 발명의 이해를 돕기 위하여 실시예 등을 들어 상세하게 설명하기로 한다. 그러나 본 발명을 실시하기 위한 실시예는 발명에 포함되는 기술적 사상의 일부를 예시적으로 설명하는 것에 불과하다. 따라서, 본 명세서에 개시된 발명의 내용은 본 발명의 기술적 사상을 한정하기 위한 것이 아니라 석명하기 위한 것이므로, 이러한 실시예 등에 의하여 본 발명의 기술사상의 범위가 한정되는 것은 아님은 자명하다. 본 발명의 도면에 포함된 기술적 사상의 범위 내에서 당업자가 용이하게 유추할 수 있는 변형 예와 구체적인 실시예는 모두 본 발명의 권리범위에 포함되는 것으로 해석되어야 할 것이다.
본 발명의 열경화 접착제 조성 중 반응성 아크릴 모노머는 하기 화학식(1)의 베타-카복시에틸 아크릴레이트(B-Carboxyethyl Acrylate), 또는 화기 화학식 (2)의 옥시에틸레이트-아크릴레이트(Oxyethylated Acrylate) 또는 하기 화학식(3)의 2- 페녹시에틸 아크릴레이트(2-Phenoxyehtyl Acrylate), 우레탄아크릴레이트(Urethane Acrylate) 중 어느 하나를 선택할 수 있다. 반응개시제로는 하기 화학식(4)의 2,2- 디메톡시-1,2-디페닐=에탄-1-온(2, 2-Dlmethoxy-1, 2-dlphenyl-ethan-1-one) 또는 하기 화학식(5)의 1-하이드록시-시클로헥실페닐-케톤(1-Hydroxy-cyclohexylphenyl-ketone), 또는 하기 화학식(6)의 2-메틸-1-[4-(메틸일티오)페닐-2-모르폴리노-프포판-1-온〔2-Methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one〕, 또는화학식(7) Potassium persulfate 등으로 이루어져 있으며, 광 증감제, 가교제 및 기능성 첨가제를 더 첨가할 수 있다.
화학식 (1)
화학식 (2)
화학식 (3)
화학식 (4) 화학식 (5) 화학식 (6)
화학식 (7)
<실시예 1-3> 열경화 수용성 아크릴 접착제의 합성
[표 1] 같이 아크릴모노머, 아크릴 올리고머, 염기성 수용액, 반응개시제 투입 후 열을 가하여 열경화성 접착제를 합성하였다.
실시예 1 | 실시예 2 | 실시예 3 | |
아크릴 모노머 | 화학식 1 | 화학식 2 | 화학식 3 |
아크릴 올리고머 | 알리파틱 우레탄-아크릴레이트 아크릴레이트 | 알리파틱 우레탄-아크릴레이트 디아크릴레이트 | 알리파틱 우레탄-아크릴레이트 트리아크릴레이트 |
염기성수용액 | -OH | -OH | -SO4 |
반응 개시제 | 화학식 4 | 화학식 5 | 화학식 6 |
증감제 | partially purified | porfimer sodium | Taporfin sodium |
<실시예 4-6> 무기물 함유 바인더의 조성
[표 2] 같이 경화성 접착제, 물, 벤토나이트, 실리카, 난연재, 질소계 수지, 발수제, 침투제, 소포제 분산제를 배합하여 E-Glass 장섬유 매트용 바인더를 제조하였다.
성분(중량부) | 실시예 4 | 실시예 5 | 실시예 6 |
열경화 접착제 | 실시예1접착제 :100 | 실시예2접착제 :100 | 실시예3접착제 :100) |
물 | 20 | 30 | 40 |
벤토나이트 | 30 | 20 | 40 |
실리카 | 5 | 5 | 7 |
난연재 | 5 | 10 | 15 |
질소계 수지 | 2 | 4 | 6 |
발수제 | 2 | 4 | 6 |
침투제 | 6 | 4 | 2 |
소포제 | 1 | 2 | 1 |
분산제 | 2 | 1 | 2 |
상기의 바인더 성분 중 열경화 접착제 100중량부에 대하여 벤토나이트 20- 40중량부로 함유되는 것이 바람직하며, 벤토나이트가 40중량부 이상일 경우 기계적 강도는 뛰어나나 접착력이 떨어지는 단점이 있고, 벤토나이트가 20중량부 이하일 경우 기계적 강도가 떨어지는 단점이 있다. 또한 실시예 4에서는 분산제로 폴리옥시알킬에테르 나프탈렌술폰산나트륨-축합물을, 실시예 5에서는 알킬 디페닐 에테르 디술폰산 나트륨을 사용하였고 실시예 6에서는 리그닌술폰산 나트륨을 사용하였다. <보온단열재 커버의 성형>
상기의 실시예 4의 수용성 바인더를 E- Glass 장섬유 매트의 표면에 균일하게 도포하여 롤러로 압착한 후 원통형의 지그에 적층 성형하여 다양한 두께인 튜브 형태의 유리장섬유 단열재를 제조한다. 상기의 튜브 형태의 E-Glass 장섬유 단열재를 마이크로파 및 열풍건조 장치에서 약 180 ~ 250℃의 온도로 2~6시간 동안 건조한다.
<실시예 7> 이중경화성 수지의 배합 공정
2-HEA 30중량%와 2-HEMA 40중량% 및 (2-HEMA) 30중량%을 혼합하고 60℃에서 광개시제로 2,2'-아조-비스-이소부틸니트릴(AIBN)을 첨가하여 5시간 반응하여 고형분 40wt%의 중합물을 반응시킨 후, 아크릴산 30 mol%를 혼합하여 고분자화 수지에 아크릴 관능기를 합성하여 최종 고형분 35wt%의 이중경화형 수지를 제조하였다.
<실시예 8> 이중경화성 조성물의 코팅
실시예 7의 이중경화성 수지 50g과 폴리카보네이트 폴리올 25g, MDI 7g과 광개시제로 benzoyl peroxid 7g 용제로 MEK 30g로 혼합한 이중경화형 코팅 조성물을 본 발명의 보온 단열재 커버에 코팅하고 60℃에서 5분 동안 건조한 후, 50℃에서 3시간 열경화 및 숙성시켜 하드 코팅층을 형성하였다.
비교예
비교예의 제품은 표면에 알루미늄 호일을 코팅한 E-Glass 장섬유 보온 단열재의 보온커버이다.
〈기능평가〉
1) 광택도
글로스미터(Glossmeter)를 이용하여 60° 각도에서 광택도를 측정하였다.
2) 표면경도
ASTM D3502에 의거하여 표면경도를 측정하였다.
3) 내스크래치성
하드 코팅층에 대해 5회 왕복하여 숫가락으로 강하게 누르면서 긁은 이후 1분 동안 방치하고, 상기 1분 동안 방치한 이후 코팅층 표면에 남은 자국을 육안으로 관찰하여 우수, 불량의 2단계로 평가하였다.
우수 : ○ (복원됨)
보통 : △ (약간 복원됨)
불량 : X (복원되지 않음)
4) 유연성
보온단열재 커버를 신율 10% 신장시켰을 때 표면에 크랙이 발생하는 지를 육안으로 확인하여 크랙의 발생여부를 확인하였다.
(크랙발생)의 두 개의 등급으로 구분하여 분류하였다.
상기의 광택도, 표면경도, 내스크래치성 및 유연성에 대하여 성능을 검사한 결과를 [표 3]에 나타내었다.
광택도 | 표면경도 | 내스크래치성 | 유연성 | |
실시예 8 | 97 | 매끈함 | ○ | 크랙발생 무 |
비교예 | 82 | 약간 거침 | Ⅹ | 일부 크랙발생 |
[표 3]으로부터 알 수 있듯이 본 발명의 보온 단열재 커버는 광택도가 97임을 알 수 있고 또한, 표면경도, 내스크래치성 및 유연성이 뛰어난 것으로 확인되었다.
석유화학(Petroleum Chemical Plant), 발전소(Power Plant), 제철소(Steel Marking Plant), 화학저장탱크, 오일탱크, 조선(선박), 건축물 내외장재, 지상 또는 지하 파이프라인, 지붕, 라이닝재 등의 커버로 사용되는 수분침투 방지, 열효율 개선 및 불연성이 뛰어난 UV 필름이 코팅된 보온 단열재로서, 재단 가공성이 좋아 금속, 플라스틱, 유리면, 도자기, 석재, 목재 및 각종 건축물 기재의 다양한 표면상태나 굴곡이 심한 형상에도 균일하게 코팅시킬 수 있는 UV경화형 필름이 코팅된 열효율을 극대화한 보온 단열재 및 그 제조방법에 관한 기술이다.
Claims (7)
- a) 하기 화학식 (1) 또는 하기 화학식 (2) 또는 하기 화학식 (3) 중에서 선택된 1 또는 2 이상을 조합한 반응성 아크릴 모노머와 알리파틱 우레탄 아크릴레이트, 알리파틱 우레탄 디아크릴레이트 또는 알리파틱 우레탄 트리아크릴레이트 중에서 선택된 1 종의 아크릴 올리고머와 염기성 수용액과 하기 화학식(4) 또는 하기 화학식(5) 또는 하기 화학식(6) 중에서 1종 또는 2종 이상을 조합한 반응개시제 및 증감제, 가교제 및 기능성 첨가제를 첨가하여 광경화성 접착제를 조합하는 단계;b) 상기의 열경화성 접착제, 물, 벤토나이트, 실리카, 난연재, 질소계 수지, 발수제, 침투제, 소포제 및 분산제를 배합하여 E-Glass 장섬유 매트용 바인더를 제조하는 단계;c) 상기 수용성 바인더를 E-Glass 장섬유 매트의 표면에 균일하게 도포하여 롤러로 압착한 후 원통형의 지그에 적층 성형하여 E-Glass 장섬유 단열재를 제조하는 단계;d) 성형 로울러로부터 분리된 보온 단열재를 150 ~ 200℃에서 10 ~ 30분 건조시키는 단계;e) 아크릴레이트 모노머 및 올리고머 중에서 선택된 1종 또는 2종 이상과 광개시제를 이용하여 이중경화성 수지의 합성한 후 상기 열경화성 수지와 이소시아네이트, 폴리올, 광개시제 및 용제인 메틸에틸케톤을 혼합하여 조성된 이중경화형 코팅 조성물을 단열재 커버의 표면에 코팅하는 단계;로 제조되는 것을 특징으로 하는 UV 필름이 코팅된 열효율을 극대화한 보온 단열재의 제조방법.
- 제1항에 있어서,상기 (e)단계에서의 아크릴레이트 모노머는 2-HEA(2-hydroxyethyl acrylate), 2-Ethylhexyl acrylate(2-EHA), 2-hydroxyethyl methacrylate(2-HEMA), 2-HPA(2-hydroxypropyl acrylate) 중 어느 하나 또는 2 이상을 함유하며, 아크릴레이트 올리고머는 지방족 우레탄디아크릴레이트(Aliphatic Urethane Diacrylate), 지방족 우레탄 트리아크릴레이트, 지방족우레탄 헥사아크릴레이트의 아크릴레이트 중 어느 하나인 것을 특징으로 하는 UV 필름이 코팅된 열효율을 극대화한 보온 단열재의 제조방법.
- 제1항에 있어서,상기 (e)단계에서의 이소시아네이트는 TDI(Toluene diisocynate), MDI(Diphenylmethane diisocynate) 또는 MXDI(tetramethylxylene diisocynate) 또는 XDI(Xylene diisocyanate) 또는 IPDI(Isophorone diisocyanate) 또는 HMDI(hexamethylene diisocyanate) 중에서 선택된 1종 또는 2종 이상인 것을 특징으로 하는 UV 필름이 코팅된 열효율을 극대화한 보온 단열재의 제조방법.
- 제1항에 있어서,상기 (e)단계에서의 폴리올은 폴리에테르 폴리올 또는 폴리에스테르 폴리올 또는 프로락톤 폴리올 또는 폴리카보네이트 폴리올, 또는 폴리부타디엔 폴리올 인 것을 특징으로 하는 UV 필름이 코팅된 열효율을 극대화한 보온 단열재의 제조방법.
- 제1항에 있어서,상기의 (e)단계에서의 분산제는 폴리옥시알킬에테르, 나프탈렌술폰산나트륨 축합물, 알킬 디페닐 에테르 디술폰산 나트륨 또는 리그닌술폰산 나트륨 중에서 선택된 1종 또는 2종 이상인 것을 특징으로 하는 UV 필름이 코팅된 준 불연 및 열효율을 극대화한 보온 단열재의 제조방법.
- a) 하기 화학식 (1)의 반응성 아크릴 모노머와 알리파틱 우레탄 아크릴레이트, 알리파틱 우레탄 디아크릴레이트 또는 알리파틱 우레탄 트리아크릴레이트 중에서 선택된 1종의 아크릴 올리고머와 염기성 수용액과 하기 화학식(4)인 반응개시제 및 증감제를 첨가된 열경화성 접착제를 제조하고,b) 상기 열경화성 접착제에 물, 벤토나이트, 실리카, 난연재, 질소계 수지, 발수제, 침투제, 소포제 및 분산제를 배합하여 E-Glass 장섬유 매트용 바인더를 제조한 후,c) 상기 수용성 바인더를 E-Glass 장섬유 매트의 표면에 균일하게 도포하여 롤러로 압착한 후 원통형의 지그에 적층 성형하여 E-Glass 장섬유 단열재를 성형하여 건조한 후,d) 아크릴레이트 모노머 및 올리고머와 광개시제 및 아크릴산으로 이중경화성 수지를 합성한 후 상기 열경화성 수지에 폴리올과 광개시제 및 용제인 메틸에틸케톤을 혼합하여 조성된 이중경화형 코팅 조성물을 단열재 커버의 표면에 코팅시킨 UV경화 필름이 코팅된 열효율을 극대화한 보온 단열재.
- 제6항에 있어서,상기의 폴리올은 폴리에테르 폴리올 또는 폴리에스테르 폴리올 또는 프로락톤 폴리올 또는 폴리카보네이트 폴리올, 또는 폴리부타디엔 폴리올인 것을 특징으로 하는 UV경화 필름이 코팅된 열효율을 극대화한 보온 단열재.
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