KR100901250B1 - Polyurea resin composition with ultraviolet shielding effect - Google Patents

Polyurea resin composition with ultraviolet shielding effect Download PDF

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KR100901250B1
KR100901250B1 KR1020090004923A KR20090004923A KR100901250B1 KR 100901250 B1 KR100901250 B1 KR 100901250B1 KR 1020090004923 A KR1020090004923 A KR 1020090004923A KR 20090004923 A KR20090004923 A KR 20090004923A KR 100901250 B1 KR100901250 B1 KR 100901250B1
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polyurea resin
resin composition
zinc oxide
polyurea
weight
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KR1020090004923A
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Korean (ko)
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채민호
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채민호
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/02—Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/66—Substances characterised by their function in the composition
    • C08L2666/78—Stabilisers against oxidation, heat, light or ozone

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

A polyurea resin composition is provided to ensure excellent UV shielding effects and to be used in various fields due to strength maintenance rate of 90% or greater and low yellow index value. A polyurea resin composition with UV shielding effects comprises zinc oxide 0.1-10 weight% with grain size of 100-1000 nm. The polyurea resin composition comprises pure polyurea resin and hybrid polyurea resin. A method for manufacturing the polyurea resin composition comprises the steps of: manufacturing polyurea resin by polymerizing a polyisocyanate compound and a polyamine compound; and mixing the polyurea resin with zinc oxide in a mixer in order to maintain a particle diameter of the zinc oxide of 100-1000 nm and concentration of 0.05-10 weight%.

Description

자외선 차단 효과를 가진 폴리우레아 수지 조성물{Polyurea Resin Composition with Ultraviolet Shielding Effect}(Polyurea Resin Composition with Ultraviolet Shielding Effect)

본 발명은 자외선 차단 효과가 월등한 폴리우레아 수지 조성물 및 이의 제조방법에 관한 것이다.The present invention relates to a polyurea resin composition having superior ultraviolet shielding effect and a method for producing the same.

지금까지 건축물에는 여러 형태의 방식 방수 물질이 사용되어 오고 있는바, 그 중에서도 에폭시, 폴리우레탄 및 폴리우레아 수지 등이 대표적으로 사용되고 있다. 그러나, 점착성 및 신축성이 탁월한 상기 물질재료의 특성에도 불구하고 종래의 물질재료는 일광노출에 의한 변색성을 가지고 있고 또한 장기간 노출에 따른 내구성 저하의 문제점을 가지고 있다.Up to now, various types of waterproofing materials have been used in buildings, among which epoxy, polyurethane and polyurea resins are typically used. However, in spite of the properties of the above material materials excellent in adhesiveness and stretchability, the conventional material materials have discoloration due to exposure to sunlight and have a problem of durability deterioration due to long-term exposure.

태양광에 노출되는 시트나 판넬 등의 물품에 대한 자외선의 영향에 대한 연구가 현재 크게 관심을 모으고 있는바, 이는 태양광에 항시 또는 반복적으로 노출되는 경우에 물품에 사용된 염료나 안료가 퇴색되고 접착성 등의 물성이 크게 저하되며 또한 내구성이 저하됨으로써 물품 수명이 단축되기 때문이다.Research on the effect of ultraviolet rays on articles such as sheets or panels exposed to sunlight has attracted great interest nowadays because of the fact that when the sunlight is always or repeatedly exposed, the dyes and pigments used in the articles are faded The physical properties such as adhesiveness are largely lowered and durability is lowered, thereby shortening the service life of the product.

폴리우레아는 에폭시 및 폴리우레탄과는 비교할 수 없을 정도로 탁월한 여러 물성을 가지고 있는바, 스프레이 도포 후의 초속경형, 인장강도, 내충격성, 내마모성 및 내구성 등이 탁월하다.Polyurea has excellent physical properties such as epoxy and polyurethane which are superior to epoxy and polyurethane, and it is excellent in quick-setting after application of spray, tensile strength, impact resistance, abrasion resistance and durability.

폴리우레아는 상기와 같은 물성으로 인해, 방식 방수용 재료로서 뿐만 아니라 바닥재 및 각종 조형물에도 사용되고 있다. 특히, 뛰어난 시공성으로 인해 최소 인원으로 단기간내에 대형공사를 완료할 수가 있고 경사면과 수직면에도 흘러내리지 않고 도포할 수가 있다. Due to the above-mentioned physical properties, polyurea is used not only as a method waterproofing material but also as a flooring material and various molding products. In particular, due to its excellent workability, large work can be completed within a short period of time with minimum staffing, and it can be applied without slipping on slopes and vertical surfaces.

자외선 흡수제로는 2-(2-히드록시페놀)벤조트리아졸, 2-히드록시벤조페논, 디페닐시아노아크릴레이트, 포름계 등의 화합물이 이미 공지되어 있는바, 이들은 중합체 물질에 대한 광안정화 효과가 있어서 유용한 물질로 여겨지고 있지만 폴리우레아 수지와의 상용성이 낮고 폴리우레아에 대한 저용해도 및 고이동성으로 인해 부적합하다. 더욱이, 상기한 종래의 자외선 차단제는 내열성, 내후성 및 안정성에 대한 문제가 있어서 사용하는데 많은 제약이 따른다.As the ultraviolet absorber, compounds such as 2- (2-hydroxyphenol) benzotriazole, 2-hydroxybenzophenone, diphenyl cyanoacrylate, formyl and the like are already known, But it is not compatible with polyurea resin and is not suitable due to low solubility and high mobility of polyurea. Furthermore, the above-mentioned conventional ultraviolet screening agents have a problem in heat resistance, weatherability, and stability, and therefore, they are subject to many restrictions.

자외선은 파장이 약 200 nm 내지 400 nm인 전자파를 말하는 것으로, 이를 다시 세분하면 UVC(200~290 nm), UVB(290~320 nm) 및 UVA(320~400 nm)로 구분된다. 이 중에서 UVC는 오존층과 성층권에서 대부분 흡수되고, UVB는 유리창을 통과하지 못하지만 UVA는 유리창 및 대부분의 합성수지를 투과한다. Ultraviolet rays are electromagnetic waves having a wavelength of about 200 nm to 400 nm. Subdividing them into UVC (200 to 290 nm), UVB (290 to 320 nm) and UVA (320 to 400 nm) Of these, UVC is mostly absorbed in the ozone layer and stratosphere, while UVB does not pass through glass windows, but UVA permeates glass windows and most synthetic resins.

특히, UVA는 지구상에 도달하는 양이 UVB의 100배나 많기 때문에 이에 대한 차단효과가 탁월한 재료를 선택하는 것이 요망된다.In particular, since the amount of UVA reaching the earth is 100 times as much as that of UVB, it is desired to select a material having excellent blocking effect.

본 발명은 상기와 같은 종래의 문제점을 해결코자 하는 것으로 자외선 차단성이 탁월한 폴리우레아 수지 조성물을 제공하는 것이다. Disclosure of Invention Technical Problem [8] The present invention provides a polyurea resin composition excellent in ultraviolet shielding property to solve the conventional problems as described above.

본 발명에 있어서는 유기물 자외선 차단제를 사용하지 않고 무기물인 산화아연을 사용함으로써, 재료의 안정성을 향상시킬 뿐만 아니라 재료의 친환경성을 갖도록 하였다.In the present invention, zinc oxide, which is an inorganic material, is used without using an organic UV-screening agent, so that the stability of the material is improved and the material is eco-friendly.

또한, 이산화티타늄에 비해 UVA의 차단효과가 뛰어난 산화아연을 주된 재료로 사용함으로써 그 자외선 차단에 대한 효율성을 높일 뿐만 아니라 산화아연의 항균작용으로 인해서 저수조 등에 유용하게 사용할 수 있도록 하였다.In addition, using zinc oxide, which is superior in UVA blocking effect compared to titanium dioxide, as a main material not only improves the efficiency of UV ray shielding but also makes it useful for the water tank due to the antimicrobial action of zinc oxide.

산화아연은 광투과성이 좋은 다양한 특성을 가지고 있는바, 특히 자외선(UVA) 차단 효과가 뛰어나다. Zinc oxide has various properties with good optical transparency, and is particularly excellent in ultraviolet (UVA) blocking effect.

본 발명에 따라 평균 입자직경이 100 내지 1000 nm가 되는 산화아연을 0.2 내지 5 중량%가 되게 폴리우레아 수지 조성물에 첨가한다.According to the present invention, zinc oxide having an average particle diameter of 100 to 1000 nm is added to the polyurea resin composition in an amount of 0.2 to 5% by weight.

본 발명에 따라 제조된 폴리우레아 수지 조성물은 강력유지율이 90% 이상이고 낮은 황변지수값을 가지게 됨으로써, 방식 방수 재료 뿐만 아니라 다양한 용도 로서 사용가능한 자외선 차단 효과가 탁월한 재료를 제공한다.INDUSTRIAL APPLICABILITY The polyurea resin composition produced according to the present invention has a strength retention rate of not less than 90% and a low yellowing index value, thereby providing a material excellent in ultraviolet blocking effect which can be used for various applications as well as a waterproofing material.

본 발명은 폴리우레아 수지에 자외선차단 물질인 산화아연 물질을 첨가하는 것으로 산화아연은 적절하게는 0.2 내지 5 중량% 함유하는 것으로 한다. 본 발명은 폴리우레아 수지를 예로 들어 설명하고 있으나, 이는 폴리우레탄 수지에도 적용될 수가 있다.In the present invention, a zinc oxide material, which is an ultraviolet ray blocking material, is added to the polyurea resin, and zinc oxide is appropriately contained in an amount of 0.2 to 5 wt%. Although the present invention has been described by taking polyurea resin as an example, it can also be applied to a polyurethane resin.

또한, 본 발명에 따라 자외선차단 효과를 가진 폴리우레아 매트릭스 및 필름을 제공하고, 기재에 본 발명에 따른 자외선 차단 효과를 가진 폴리우레아 수지 조성물을 도포함으로써 자외선의 영향으로부터 기재를 보호하는 방법을 제공한다.Also provided is a method for protecting a substrate from the influence of ultraviolet rays by providing a polyurea matrix and a film having an ultraviolet blocking effect according to the present invention and applying the polyurea resin composition having the ultraviolet blocking effect according to the present invention to the substrate .

또한, 본 발명에 따른 자외선 차단 효과를 가진 폴리우레아 수지 조성물을 포함하는 다층 시트 및 판넬 등을 제공한다. 이러한 하나의 실시 예로서, 최하부에는 우레탄 또는 에폭시 수지로 이루어지고, 중간층에는 우레아, 우레탄, 또는 에폭시 수지로 이루어지며, 최상층에는 본 발명의 자외선 차단 효과를 가진 폴리우레아 수지를 포함하는 시트를 제공하는 것이다.In addition, the present invention provides a multilayer sheet, a panel and the like comprising the polyurea resin composition having an ultraviolet blocking effect according to the present invention. As one such embodiment, there is provided a sheet comprising a urethane or an epoxy resin at the lowermost portion, a urea, urethane or an epoxy resin in the middle layer, and a polyurea resin having the ultraviolet blocking effect of the present invention at the uppermost layer will be.

본 발명의 또 다른 실시 형태로는, 폴리우레아 수지 외에도 하이브리드 폴리우레아 수지(예로서, 폴리우레탄 및 폴리우레아의 혼합물)에 자외선 차단제로서의 산화아연을 첨가하는 방법을 포함한다.Another embodiment of the present invention includes a method of adding zinc oxide as an ultraviolet screening agent to a hybrid polyurea resin (for example, a mixture of polyurethane and polyurea) in addition to a polyurea resin.

폴리우레아 수지는 당업계에 이미 공지된 중합법을 이용하여 제조한다. 즉, 폴리우레아는 이소시아네이트 화합물과 아민 화합물을 중합반응하여 제조하고 폴리 우레탄은 디이소시아네트 화합물과 폴리올 화합물을 중합반응하여 제조한다.The polyurea resin is prepared using polymerization methods well known in the art. That is, the polyurea is produced by polymerization reaction of an isocyanate compound and an amine compound, and the polyurethane is produced by polymerization reaction of a diisocyanate compound and a polyol compound.

본 발명에 따른 폴리우레아 수지 조성물은 자외선 차단 물질 외에도 여러 첨가제를 포함할 수도 있다. 이러한 첨가제의 예로는 산화방지제, 염료, 안료 및 광 안정화제 등이 있다. 사용되는 정확한 유형과 양은 본 발명에 따른 폴리우레아 수지 조성물의 최종 용도에 따라 변형될 수 있다.The polyurea resin composition according to the present invention may contain various additives in addition to the ultraviolet barrier material. Examples of such additives include antioxidants, dyes, pigments and light stabilizers. The exact type and amount used may vary depending on the end use of the polyurea resin composition according to the present invention.

본 발명에 따른 폴리우레아 수지 조성물에 대한 산화아연의 양은 전체 물질의 중량을 기준으로 하여 약 0.05 내지 10 중량%, 바람직하게는 0.1 내지 5 중량%, 가장 바람직하게는 0.2 내지 2 중량%로 존재한다.The amount of zinc oxide for the polyurea resin composition according to the present invention is about 0.05 to 10% by weight, preferably 0.1 to 5% by weight, most preferably 0.2 to 2% by weight, based on the weight of the total material .

본 발명에 따른 자외선 차단 효과를 가진 폴리우레아 수지 조성물의 제조방법은 폴리우레아 중합체와 산화아연 분말을 동시에 분사하고 열을 가하여 용융액을 만들고 이를 판낼 및 다양한 구조물의 표면에 분사한다. 이렇게 제조된 폴리우레아 수지 조성물은 낮은 황변지수를 갖는다.The method for producing a polyurea resin composition having an ultraviolet blocking effect according to the present invention comprises spraying a polyurea polymer and zinc oxide powder at the same time, applying heat to the melt to form a melt, and spraying the melt onto a surface of a plate and various structures. The polyurea resin composition thus prepared has a low yellowing index.

실시예Example

먼저, 폴리아민 화합물과 폴리이소시아네이트 화합물을 용제나 희석제를 사용하지 않고 충돌혼합 스프레이 장치에서 혼합하여 폴리우레아 수지를 제조한다.First, a polyamine resin is prepared by mixing a polyamine compound and a polyisocyanate compound in an impact mixing spray apparatus without using a solvent or a diluent.

다음으로, 용융된 적당한 점도를 가진 폴리우레아 수지를 적당한 크기의 챔버내에서 교반기 등을 이용하여 산화아연 분말을 첨가하여 혼합하되 산화아연의 입경이 100 내지 1000 nm를 이루고 농도는 0.05 내지 10 중량%를 유지하도록 한다.Next, a polyurea resin having a proper viscosity is melted and mixed with a zinc oxide powder by using a stirrer or the like in a chamber of an appropriate size. The zinc oxide has a particle diameter of 100 to 1000 nm and a concentration of 0.05 to 10 wt% .

상기한 산화아연의 첨가량이 0.05 중량% 미만일 경우에는 자외선 차단 효과가 저하될 수 있고 10 중량% 이상을 사용할 경우에는 재료 가격의 상승 원인이 될 수 있으며 조밀한 입자들로 인해 폴리우레아의 물성을 저하할 수가 있다. If the amount of the zinc oxide added is less than 0.05 wt%, the ultraviolet shielding effect may be deteriorated. If the amount of the zinc oxide is more than 10 wt%, the material cost may be increased, and the physical properties of the polyurea may be deteriorated I can do it.

본 발명에 따른 폴리우레아 수지 조성물에는 필요에 따라 산화방지제 및 착색제 등이 첨가될 수도 있다.In the polyurea resin composition according to the present invention, an antioxidant, a coloring agent and the like may be added as necessary.

상기한 바와 같이 산화아연 분말과 혼합된 폴리우레아 수지 조성물을 스프레이건을 통해 원하는 구조물의 표면에 분사한다.As described above, the polyurea resin composition mixed with the zinc oxide powder is sprayed onto the surface of the desired structure through the spray gun.

본 발명에 따른 또 다른 방법으로는 폴리우레아 수지 조성물을 분사장치로 공급하고 산화아연 분말을 또한 분사장치내로 상기한 농도를 유지하면서 분사시킴으로써 혼합하고 이러한 혼합된 폴리우레아 수지 조성물을 스프레이건을 통해 외부로 분사하는 방법이 있다.In another method according to the present invention, a polyurea resin composition is supplied to an injection device and the zinc oxide powder is injected into the injection device while maintaining the above-mentioned concentration, thereby mixing the mixed polyurea resin composition with the outside As shown in FIG.

또한, 필요한 용도에 따라 이산화티타늄과 혼합하여 사용할 수도 있다. 이때에는 산화아연과 이산화티타늄의 혼합된 농도가 전체 중량에 대해서 0.05 내지 10 중량%를 유지하도록 한다.It may also be used in admixture with titanium dioxide according to the required application. At this time, the mixed concentration of zinc oxide and titanium dioxide is maintained at 0.05 to 10 wt% with respect to the total weight.

Claims (4)

폴리우레아 수지 조성물에 있어서, 입경이 100 내지 1000 nm인 산화아연을 0.1 내지 10 중량% 첨가하여 이루어진 자외선 차단효과를 가진 폴리우레아 수지 조성물.A polyurea resin composition having an ultraviolet shielding effect, comprising 0.1 to 10% by weight of zinc oxide having a particle diameter of 100 to 1000 nm in a polyurea resin composition. 제 1항에 있어서,The method according to claim 1, 폴리우레아 수지 조성물은 순수 폴리우레아 수지 및 하이브리드 폴리우레아 수지를 포함하고 있는 자외선 차단효과를 가진 폴리우레아 수지 조성물.The polyurea resin composition comprises a pure polyurea resin and a hybrid polyurea resin. 자외선 차단효과를 가진 폴리우레아 수지 조성물의 제조방법에 있어서,A method for producing a polyurea resin composition having an ultraviolet shielding effect, 폴리이소시아네이트 화합물과 폴리아민 화합물을 충돌혼합장치에서 중합반응시켜 폴리우레아 수지를 제조하는 단계, 이러한 중합반응된 폴리우레아 수지를 혼합기에서 산화아연과 혼합하되 산화아연의 입경은 100 내지 1000 nm를 이루며 농도는 0.05 내지 10 중량%를 유지하도록 하는 단계를 포함하는 자외선 차단효과를 가진 폴리우레아 수지 조성물의 제조방법.Preparing a polyurea resin by polymerization reaction of a polyisocyanate compound and a polyamine compound in a collision-mixing apparatus, mixing the polyurea resin with the zinc oxide in a mixer, wherein the zinc oxide has a particle diameter of 100 to 1000 nm, 0.05 to 10% by weight based on the total weight of the polyurethane resin composition. 제 3항에 있어서,The method of claim 3, 산화아연을 분사장치내에 공급하여 폴리우레아 수지와 혼합하는 단계를 포함하는 자외선 차단효과를 가진 폴리우레아 수지 조성물의 제조방법.And feeding the zinc oxide into the injection device to mix the polyurea resin with the polyurea resin.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103061252A (en) * 2012-12-28 2013-04-24 张庆彬 Anti-corrosion material for piers of sea-crossing bridge
KR20160020817A (en) 2014-08-14 2016-02-24 주식회사 넥스필 Polymer Composites for ultraviolet ray interception and Method for fabricating of coating film using the same
DE102018115503A1 (en) * 2018-06-27 2020-01-02 Carl Freudenberg Kg Shielding composition for electromagnetic radiation

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KR20050075010A (en) * 2002-11-13 2005-07-19 슈반-스타빌로 코스메틱스 게엠베하 운트 콤파니 카게 Cosmetic dressings containing a waxy component, a film-forming agent and a gel-forming substance
KR100706651B1 (en) 2006-12-22 2007-04-13 제일모직주식회사 Electroconductive thermoplastic resin composition and plastic article

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KR100706651B1 (en) 2006-12-22 2007-04-13 제일모직주식회사 Electroconductive thermoplastic resin composition and plastic article

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103061252A (en) * 2012-12-28 2013-04-24 张庆彬 Anti-corrosion material for piers of sea-crossing bridge
KR20160020817A (en) 2014-08-14 2016-02-24 주식회사 넥스필 Polymer Composites for ultraviolet ray interception and Method for fabricating of coating film using the same
DE102018115503A1 (en) * 2018-06-27 2020-01-02 Carl Freudenberg Kg Shielding composition for electromagnetic radiation
WO2020002511A1 (en) 2018-06-27 2020-01-02 Carl Freudenberg Kg Composition for shielding against electromagnetic radiation

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