KR100282016B1 - Synthetic leather with photoluminescent properties and its manufacturing method - Google Patents
Synthetic leather with photoluminescent properties and its manufacturing method Download PDFInfo
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Abstract
본 발명은 축광 특성을 갖는 합성피혁 및 이의 제조 방법에 관한 것으로, 산화스트론튬 55 ∼ 62.5중량%, 산화알루미늄 35 ∼ 42.5중량%, 산화디스프로슘 1 ∼ 9중량% 및 산화유로퓸 0.5 ∼ 1.5중량%로 구성되는 축광성 황색 발광체, 산화스트론튬 20 ∼ 68.75중량%, 산화알루미늄 30 ∼ 78.75중량%, 산화칼슘 1 ∼ 49.75%, 산화디스프로슘 0.1 ∼ 49.75중량%, 산화유로퓸 0.1 ∼ 49.75중량% 및 이산화규소 0.05 ∼ 48.8중량%로 구성되는 축광성 청색 변색 발광체 또는 칼슘설파이드 70 ∼ 98.85중량%, 칼슘설페이트 1 ∼ 29.85중량%, 유로퓸 및/또는 톨륨 0.05 ∼ 28.9중량% 및 이산화규소 0.1 ∼ 28.95중량%로 구성되는 축광성 적색 변색 발광체 5 ∼ 25중량%와 액상의 폴리우레탄계 수지 75 ∼ 95중량%를 혼합한 혼합물 중량에 대하여 분산제, 증백제, 안정제 등의 첨가제를 1 ∼ 10중량% 첨가한 혼합물을 통상의 합성피혁용 직물지의 표면에 도포하여 구성된 것으로서, 이형지상에 상기 축광성 발광체 함유 혼합물을 도포하고 건조한 후, 접착제를 도포하고 통상의 직물지와 합지한 다음, 이형지를 제거하여 축광 특성을 갖는 합성피혁을 제조하므로서 발광시간이 길고, 발광시 휘도가 높으며, 여기하는 빛의 파장범위가 넓고, 내광성 및 내후성이 뛰어나며 야외사용이 가능할 뿐만 아니라 화학적 안정성이 높고 환경오염을 유발하지 않으며 인체에도 무해하고 변색도 가능하여 광범위한 용도로 적용 가능한 축광 특성을 갖는 합성피혁을 얻을 수 있었다.The present invention relates to a synthetic leather having a photoluminescent property and a manufacturing method thereof, comprising 55 to 62.5% by weight of strontium oxide, 35 to 42.5% by weight of aluminum oxide, 1 to 9% by weight of dysprosium oxide and 0.5 to 1.5% by weight of europium oxide. Photoluminescent yellow light emitting material, 20 to 68.75% by weight of strontium oxide, 30 to 78.75% by weight of aluminum oxide, 1 to 49.75% of calcium oxide, 0.1 to 49.75% by weight of dysprosium oxide, 0.1 to 49.75% by weight of europium oxide and 0.05 to 48.8% of silicon dioxide Photoluminescent blue discoloration emitter or 70% to 98.85% of calcium sulfide, 1 to 29.85% of calcium sulfate, 0.05 to 28.9% of europium and / or tolium and 0.1 to 28.95% of silicon dioxide A mixture in which 1 to 10% by weight of additives such as a dispersant, a brightener, and a stabilizer are added to the weight of the mixture of 5 to 25% by weight of a red discoloration light-emitting body and 75 to 95% by weight of a liquid polyurethane resin. It is composed by applying to the surface of a conventional synthetic leather textile paper, the mixture containing the photoluminescent emitter containing on a release paper and dried, and then applying an adhesive and laminating with a conventional textile paper, and then remove the release paper to have a photoluminescent property By producing synthetic leather, it has long light emission time, high luminance when emitting light, wide wavelength range of excitation light, excellent light resistance and weather resistance, outdoor use, high chemical stability, no environmental pollution and harmless to human body. Discoloration is also possible, resulting in synthetic leather with photoluminescent properties applicable to a wide range of applications.
Description
본 발명은 축광 특성을 갖는 합성피혁 및 이의 제조방법에 관한 것으로, 좀 더 구체적으로는 산화스트론튬(Strontium Oxide) 55 ∼ 62.5중량%, 산화알루미늄(Aluminum Oxide) 35 ∼ 42.5중량%, 산화디스프로슘(Dysprosium Oxide) 1 ∼ 9중량% 및 산화유로퓸(Europium Oxide) 0.5 ∼ 1.5중량%로 구성되는 축광성 황색 발광체, 산화스트론튬 20 ∼ 68.75중량%, 산화알루미늄 30 ∼ 78.75중량%, 산화칼슘(Calcium Oxide) 1 ∼ 49.75%, 산화디스프로슘 0.1 ∼ 49.75중량%, 산화유로퓸 0.1 ∼ 49.75중량% 및 이산화규소(Silicon Dioxide) 0.05 ∼ 48.8중량%로 구성되는 축광성 청색 변색 발광체 또는 칼슘설파이드(Calcium sulfide) 70 ∼ 98.85중량%, 칼슘설페이트(Calcium sulfate) 1 ∼ 29.85중량%, 유로퓸 및/또는 톨륨(Thulium) 0.05 ∼ 28.9중량% 및 이산화규소 0.1 ∼ 28.95중량%로 구성되는 축광성 적색 변색 발광체 5 ∼ 25중량%와 액상의 폴리우레탄계 수지 75 ∼ 95중량%를 혼합한 혼합물 중량에 대하여 분산제, 증백제, 안정제 등의 첨가제를 1 ∼ 10중량% 첨가한 혼합물을 통상의 합성피혁용 직물지의 표면에 도포하여 구성된 것으로서, 이형지상에 상기 축광성 발광체 함유 혼합물을 도포하고 건조한 후, 접착제를 도포하고 통상의 직물지와 합지한 다음, 이형지를 제거함을 특징으로 하는 축광 특성을 갖는 합성피혁 및 이의 제조방법에 관한 것이다.The present invention relates to a synthetic leather having a photoluminescent property and a manufacturing method thereof, more specifically 55 to 62.5% by weight of strontium oxide, 35 to 42.5% by weight of aluminum oxide, dysprosium oxide Oxide) 1-9% by weight and 0.5-1.5% by weight of Europium Oxide, a photoluminescent yellow light-emitting body, strontium oxide 20-68.75% by weight, aluminum oxide 30-78.75% by weight, calcium oxide (Calcium Oxide) 1 70 to 98.85 weight of a luminescent blue color change light emitting body or calcium sulfide which consists of-49.75%, a dysprosium oxide 0.1-49.75 weight%, europium oxide 0.1-49.75 weight%, and silicon dioxide (0.05-48.8 weight%). %, 5 to 25% by weight of a photoluminescent red color-emitting emitter consisting of 1 to 29.85% by weight of calcium sulfate, 0.05 to 28.9% by weight of europium and / or tolium and 0.1 to 28.95% by weight of silicon dioxide Paul It is composed by applying a mixture of 1 to 10% by weight of an additive such as a dispersant, a brightener, and a stabilizer to the surface of a conventional synthetic leather fabric paper with respect to the weight of the mixture of 75 to 95% by weight of a polyurethane resin. The present invention relates to a synthetic leather having a photoluminescent property and a method of manufacturing the same, wherein the photoluminescent emitter-containing mixture is applied thereto, dried, coated with an adhesive, and then laminated with a conventional textile paper.
산업이 발전함에 따라 각종 기능성제품이 제조, 판매되고 있고, 축광 기능을 갖는 많은 제품 예를 들어, 시계, 전자기기 인테리어, 표식, 방화기기, 조명, 패션제품, 완구 등과 같은 제품들이 연구 개발되고 있는 실정이며, 각종 의류 및 섬유제품에도 응용되고 있다.As the industry develops, various functional products are manufactured and sold, and many products having a luminous function, for example, watches, electronics interiors, markings, fire protection devices, lighting, fashion products, toys, etc. are being researched and developed. The situation is applied to various clothing and textile products.
합성피혁 및 이를 이용한 제품에 축광 특성을 부여하는 방법으로는 합성피혁 및 이를 이용한 제품에 축광안료를 도포하거나 스프레이하는 방법이 주로 이용되고 있으나, 일반적으로는 축광안료가 물에 잘 용해되어 탈리되는 경향이 높고, 발광도가 낮을 뿐만 아니라 발광시간이 짧으며, 여기가 용이하지 못하고 휘도가 낮으며, 축광안료를 많이 사용하여야 하기 때문에 경제적이지 못할 뿐만 아니라 축광안료를 함유하는 표면층에 크랙이 발생하는 등의 단점이 있다.Synthetic leather and the method of imparting the photoluminescent property to the product using the same are mainly used to apply or spray the photoluminescent pigment to the synthetic leather and the product using the same, but generally the photoluminescent pigment is well dissolved in water and tend to detach High luminous intensity, low luminous intensity, short luminous time, low excitation and low luminance, not economical because many phosphorescent pigments must be used, and cracks are generated on the surface layer containing the luminous pigment. There are disadvantages.
또한, 종래에 사용되는 ZnSiCu계 등과 같은 축광안료는 발광시간이 약 5분을 넘지 못하여 실용화에 문제가 있을 뿐만 아니라 발광도가 낮아 문자 등을 식별하기 어려운 문제점이 있으며, 화학적 안정성이 낮고 내광성 및 내후성이 좋지 못한 단점이 있어 고품질의 제품에는 거의 적용되고 있지 못하는 실정이다.In addition, conventionally used photoluminescent pigments such as ZnSiCu-based light emitting time does not have a problem of practical use because the light emission time does not exceed about 5 minutes, there is a problem that it is difficult to identify characters, such as low luminescence, low chemical stability, light resistance and weather resistance This disadvantage has been applied to a high quality product is rarely applied to the situation.
뿐만 아니라, 종래의 대부분의 축광안료들은 황색 계통의 빛을 발현시키고 다른 계통으로 색상을 발현시키지 못하여 다양한 색상을 발현하는 제품을 얻기가 곤란하였다.In addition, most of the conventional photoluminescent pigments it is difficult to obtain a product that expresses a variety of colors because it does not express the light of the yellow line and the color of other lines.
따라서, 본 발명의 목적은 발광시간이 길고, 발광시 휘도가 높으며, 여기하는 빛의 파장범위가 넓고, 내광성 및 내후성이 뛰어나며 야외사용이 가능할 뿐만 아니라 화학적 안정성이 높고 환경오염을 유발하지 않으며 인체에도 무해하고 청색 또는 적색으로 변색이 가능하여 합성피혁 및 이를 이용한 제품에 적용 가능한 축광 특성을 갖는 합성피혁을 제공하는 데 있다.Therefore, the object of the present invention is long emission time, high luminance during light emission, wide wavelength range of excitation light, excellent light resistance and weather resistance, outdoor use, high chemical stability and does not cause environmental pollution, It is to provide a synthetic leather having a photoluminescent property applicable to synthetic leather and products using the same by being harmless and discoloration to blue or red.
본 발명의 다른 목적은 상기 목적의 합성피혁을 용이하게 제조할 수 있는 방법을 제공하는 데 있다.Another object of the present invention is to provide a method which can easily prepare a synthetic leather of the above object.
상기 목적들 뿐만 아니라 용이하게 표출될 수 있는 또 다른 목적을 달성하기 위하여 본 발명에서는 산화스트론튬(Strontium Oxide) 55 ∼ 62.5중량%, 산화알루미늄(Aluminum Oxide) 35 ∼ 42.5중량%, 산화디스프로슘(Dysprosium Oxide) 1 ∼ 9중량% 및 산화유로퓸(Europium Oxide) 0.5 ∼ 1.5중량%로 구성되는 축광성 황색 발광체, 산화스트론튬 20 ∼ 68.75중량%, 산화알루미늄 30 ∼ 78.75중량%, 산화칼슘(Calcium Oxide) 1 ∼ 49.75%, 산화디스프로슘 0.1 ∼ 49.75중량%, 산화유로퓸 0.1 ∼ 49.75중량% 및 이산화규소(Silicon Dioxide) 0.05 ∼ 48.8중량%로 구성되는 축광성 청색 변색 발광체 또는 칼슘설파이드(Calcium sulfide) 70 ∼ 98.85중량%, 칼슘설페이트(Calcium sulfate) 1 ∼ 29.85중량%, 유로퓸 및/또는 톨륨(Thulium) 0.05 ∼ 28.9중량% 및 이산화규소 0.1 ∼ 28.95중량%로 구성되는 축광성 적색 변색 발광체 5 ∼ 25중량%와 액상의 폴리우레탄계 수지 75 ∼ 95중량%를 혼합한 혼합물 중량에 대하여 분산제, 증백제, 안정제 등의 첨가제를 1 ∼ 10중량% 첨가한 혼합물을 통상의 합성피혁용 직물지의 표면에 도포하여 구성된 것으로서, 이형지상에 상기 축광성 발광체 함유 혼합물을 도포하고 건조한 후, 접착제를 도포하고 통상의 직물지와 합지한 다음, 이형지를 제거하여 축광특성을 갖는 합성피혁을 제조하므로서 발광시간이 길고, 발광시 휘도가 높으며, 여기하는 빛의 파장범위가 넓고, 내광성 및 내후성이 뛰어나며 야외사용이 가능할 뿐만 아니라 화학적 안정성이 높고 환경오염을 유발하지 않으며 인체에도 무해하고 변색도 가능하여 광범위한 용도로 적용 가능한 축광 특성을 갖는 합성피혁을 얻을 수 있었다.In order to achieve the above object as well as another object that can be easily expressed in the present invention strontium oxide (Strontium Oxide) 55 to 62.5% by weight, aluminum oxide (Aluminum Oxide) 35 to 42.5% by weight, dysprosium oxide (Dysprosium Oxide) ) Photoluminescent yellow light emitting body consisting of 1 to 9% by weight and 0.5 to 1.5% by weight of europium oxide, 20 to 68.75% by weight of strontium oxide, 30 to 78.75% by weight of aluminum oxide, and 1 to 2% of calcium oxide (Calcium Oxide) 70 to 98.85% by weight of a photoluminescent blue discoloration emitter or calcium sulfide consisting of 49.75%, 0.1 to 49.75% by weight of dysprosium oxide, 0.1 to 49.75% by weight of europium oxide, and 0.05 to 48.8% by weight of silicon dioxide 5 to 25% by weight of a photoluminescent red color-emitting light emitting body comprising 1 to 29.85% by weight of calcium sulfate, 0.05 to 28.9% by weight of europium and / or tolium and 0.1 to 28.95% by weight of silicon dioxide It is configured by applying a mixture of 1 to 10% by weight of an additive such as a dispersant, a brightener, and a stabilizer to the surface of a conventional synthetic leather fabric paper with respect to the mixture weight of 75 to 95% by weight of a polyurethane resin. The light-emitting phosphor-containing mixture is coated on the ground and dried, and then the adhesive is applied and laminated with a conventional textile paper, and then the release paper is removed to prepare synthetic leather having a photoluminescent property. Wide range of wavelength of excitation light, excellent light and weather resistance, outdoor use, high chemical stability, no environmental pollution, harmless to human body and discoloration. Could get
본 발명을 좀 더 구체적으로 설명하면 다음과 같다.The present invention is described in more detail as follows.
본 발명에 따른 축광 특성을 갖는 합성피혁은 산화스트론튬(Strontium Oxide) 55 ∼ 62.5중량%, 산화알루미늄(Aluminum Oxide) 35 ∼ 42.5중량%, 산화디스프로슘(Dysprosium Oxide) 1 ∼ 9중량% 및 산화유로퓸(Europium Oxide) 0.5 ∼ 1.5중량%로 구성되는 축광성 황색 발광체, 산화스트론튬 20 ∼ 68.75중량%, 산화알루미늄 30 ∼ 78.75중량%, 산화칼슘(Calcium Oxide) 1 ∼ 49.75%, 산화디스프로슘 0.1 ∼ 49.75중량%, 산화유로퓸 0.1 ∼ 49.75중량% 및 이산화규소(Silicon Dioxide) 0.05 ∼ 48.8중량%로 구성되는 축광성 청색 변색 발광체 또는 칼슘설파이드(Calcium sulfide) 70 ∼ 98.85중량%, 칼슘설페이트(Calcium sulfate) 1 ∼ 29.85중량%, 유로퓸 및/또는 톨륨(Thulium) 0.05 ∼ 28.9중량% 및 이산화규소 0.1 ∼ 28.95중량%로 구성되는 축광성 적색 변색 발광체 5 ∼ 25중량%와 액상의 폴리우레탄계 수지 75 ∼ 95중량%를 혼합한 혼합물 중량에 대하여 분산제, 증백제, 안정제 등의 첨가제를 1 ∼ 10중량% 첨가한 혼합물을 통상의 합성피혁용 직물지의 표면에 도포한 것을 특징으로 한다.Synthetic leather having a photoluminescent property according to the present invention is strontium oxide (Strontium Oxide) 55 to 62.5% by weight, aluminum oxide (Aluminum Oxide) 35 to 42.5% by weight, dysprosium oxide 1-9% by weight and europium oxide ( Europium Oxide) photoluminescent yellow light emitting body composed of 0.5 to 1.5% by weight, strontium oxide 20 to 68.75% by weight, aluminum oxide 30 to 78.75% by weight, calcium oxide 1 to 49.75%, dysprosium oxide 0.1 to 49.75% by weight , 70 to 98.85% by weight of a photoluminescent blue discoloration emitter or calcium sulfide, consisting of 0.1 to 49.75% by weight of europium oxide and 0.05 to 48.8% by weight of silicon dioxide, and calcium sulfate 1 to 29.85 5 to 25% by weight of a photoluminescent red color fading emitter consisting of 0.05% to 28.9% by weight of europium and / or Thulium and 0.1 to 28.95% by weight of silicon dioxide and 75 to 95% by weight of a liquid polyurethane-based resin One mixture A mixture obtained by adding 1 to 10% by weight of additives such as a dispersant, a brightener and a stabilizer with respect to the weight is applied to the surface of a conventional synthetic leather textile paper.
또한, 본 발명에 따른 축광 특성을 갖는 합성피혁의 제조방법은 산화스트론튬(Strontium Oxide) 55 ∼ 62.5중량%, 산화알루미늄(Aluminum Oxide) 35 ∼ 42.5중량%, 산화디스프로슘(Dysprosium Oxide) 1 ∼ 9중량% 및 산화유로퓸(Europium Oxide) 0.5 ∼ 1.5중량%로 구성되는 축광성 황색 발광체, 산화스트론튬 20 ∼ 68.75중량%, 산화알루미늄 30 ∼ 78.75중량%, 산화칼슘(Calcium Oxide) 1 ∼ 49.75%, 산화디스프로슘 0.1 ∼ 49.75중량%, 산화유로퓸 0.1 ∼ 49.75중량% 및 이산화규소(Silicon Dioxide) 0.05 ∼ 48.8중량%로 구성되는 축광성 청색 변색 발광체 또는 칼슘설파이드(Calcium sulfide) 70 ∼ 98.85중량%, 칼슘설페이트(Calcium sulfate) 1 ∼ 29.85중량%, 유로퓸 및/또는 톨륨(Thulium) 0.05 ∼ 28.9중량% 및 이산화규소 0.1 ∼ 28.95중량%로 구성되는 축광성 적색 변색 발광체 5 ∼ 25중량%와 액상의 폴리우레탄계 수지 75 ∼ 95중량%를 혼합한 혼합물 중량에 대하여 분산제, 증백제, 안정제 등의 첨가제를 1 ∼ 10중량% 첨가한 혼합물을 이형지상에 도포하고 건조한 후, 접착제를 도포하고 통상의 합성피혁용 직물지와 합지한 다음, 이형지를 제거하는 것으로 특징지워진다.In addition, the method for producing a synthetic leather having a photoluminescent property according to the present invention is strontium oxide (Strontium Oxide) 55 to 62.5% by weight, aluminum oxide (Aluminum Oxide) 35 to 42.5% by weight, dysprosium oxide (1-9) % And a phosphorescent yellow light emitting body consisting of 0.5 to 1.5% by weight of europium oxide, 20 to 68.75% by weight of strontium oxide, 30 to 78.75% by weight of aluminum oxide, 1 to 49.75% of calcium oxide, and dysprosium oxide 70 to 98.85% by weight of a photoluminescent blue discoloration emitter or calcium sulfide consisting of 0.1 to 49.75% by weight, europium oxide 0.1 to 49.75% by weight, and silicon dioxide by 0.05 to 48.8% by weight, calcium sulfate (Calcium sulfate) from 5 to 25% by weight of a photoluminescent red color-emitting emitter composed of 1 to 29.85% by weight, 0.05 to 28.9% by weight of europium and / or thorium, and 0.1 to 28.95% by weight of silicon dioxide, and a liquid polyurethane resin 75 to 95 weight The mixture of 1% to 10% by weight of additives such as dispersant, brightener, and stabilizer was added to the release paper, dried, coated with an adhesive, and then laminated with a conventional synthetic leather fabric paper. It is characterized by removing the release paper.
본 발명에서 사용되는 야광안료는 축광성 발광체로서 정확히 구조가 밝혀지지는 않았지만 분석 결과, 축광성 황색 발광체는 산화스트론튬 55 ∼ 62.5중량%, 산화알루미늄 35 ∼ 42.5중량%, 산화디스프로슘 1 ∼ 9중량% 및 산화유로퓸 0.5 ∼ 1.5중량%로 구성되고, 축광성 청색 변색 발광체는 산화스트론튬 20 ∼ 68.75중량%, 산화알루미늄 30 ∼ 78.75중량%, 산화칼슘(Calcium Oxide) 1 ∼ 49.75%, 산화디스프로슘 0.1 ∼ 49.75중량%, 산화유로퓸 0.1 ∼ 49.75중량% 및 이산화규소(Silicon Dioxide) 0.05 ∼ 48.8중량%로 구성되며, 축광성 적색 변색 발광체는 칼슘설파이드(Calcium sulfide) 70 ∼ 98.85중량%, 칼슘설페이트(Calcium sulfate) 1 ∼ 29.85중량%, 유로퓸 및/또는 톨륨(Thulium) 0.05 ∼ 28.9중량% 및 이산화규소 0.1 ∼ 28.95중량%로 구성되는 것이다. 특히, 축광성 황색 발광체는 산화스트론튬 57중량%, 산화알루미늄 39중량%, 산화디스프로슘 3.3중량% 및 산화유로퓸 0.7중량%로 구성되는 것이 효과적이고, 축광성 청색 변색 발광체는 산화스트론튬 43중량%, 산화알루미늄 51중량%, 산화칼슘 4.4중량%, 산화디프로슘 0.6중량%, 산화유로퓸 0.6중량% 및 이산화규소 0.4중량%로 구성되는 것이 효과적이며, 축광성 적색 변색 발광체는 칼슘설파이드(Calcium sulfide) 95중량%, 칼슘설페이트(Calcium sulfate) 5중량%, 유로퓸 및/또는 톨륨(Thulium) 0.1중량% 및 이산화규소 0.25중량%로 구성되는 것이 축광 발현 측면에서 가장 바람직하였다.The luminous pigment used in the present invention was not precisely identified as a phosphorescent light emitter, but the analysis showed that the phosphorescent yellow light emitter was 55-62.5% by weight of strontium oxide, 35-42.5% by weight of aluminum oxide, and 1-9% by weight of dysprosium oxide. And europium oxide 0.5 to 1.5% by weight, and the photoluminescent blue discoloration light emitting body is 20 to 68.75% by weight of strontium oxide, 30 to 78.75% by weight of aluminum oxide, 1 to 49.75% of calcium oxide, and 0.1 to 49.75 of diprosium oxide. Weight%, europium oxide 0.1 to 49.75 weight% and silicon dioxide (Silicon Dioxide) 0.05 to 48.8% by weight, the photoluminescent red discoloration emitter is calcium sulfide (Calcium sulfide) 70 ~ 98.85% by weight, calcium sulfate (Calcium sulfate) It is comprised from 1 to 29.85 weight%, 0.05 to 28.9 weight% of europium and / or thlium, and 0.1 to 28.95 weight% of silicon dioxide. Particularly, the photoluminescent yellow light emitting body is composed of 57% by weight of strontium oxide, 39% by weight of aluminum oxide, 3.3% by weight of dysprosium oxide, and 0.7% by weight of europium oxide. Effectively composed of 51% by weight of aluminum, 4.4% by weight of calcium oxide, 0.6% by weight of dipromium oxide, 0.6% by weight of europium oxide and 0.4% by weight of silicon dioxide, the phosphorescent red discoloration emitter is calcium sulfide 95 It was most preferred in terms of photoluminescence expression, consisting of wt%, 5 wt% Calcium sulfate, 0.1 wt% Europium and / or Thulium, and 0.25 wt% silicon dioxide.
본 발명에서 사용되는 축광성 황색 발광체, 축광성 청색 또는 적색 변색 발광체는 옅은 황색 분말이지만, 발광시 색상은 황색으로 그대로 나타나거나 종래의 축광성 발광체와는 달리 청색 또는 적색으로 변하여 발광되고, 발광은 약 520nm에서 피크(peak)를 이루며, 녹색, 청색 또는 적색 발광으로 인간의 시감도에 잘 부합되고, 200룩스의 조도에서 4분간 조광한 다음 발광시 휘도와 잔광특성을 조사한 결과 종래의 ZnSiCu계 형광체와 비교시 휘도가 10배 이상 밝고 장시간에 걸쳐 잔광을 볼 수 있는 특성을 가지고 있으며, 동기하는 조도가 밝을수록 높은 잔광휘도가 얻어지고, 통상적인 광원을 가지고 200룩스의 조도로 조광시 포화휘도를 얻기 위해서는 약 20 ∼ 30분 정도가 소요되며, 광원으로는 백색형광등과 태양광이 가장 효율적이고, 자외선을 많이 포함한 고압 수은등을 가지고 내구성시험을 행한 결과 내구성이 우수하였다.The photoluminescent yellow light emitter used in the present invention, the photoluminescent blue or red discolored light emitter is pale yellow powder, but when the light is emitted, the color appears as yellow or changes to blue or red light unlike the conventional photoluminescent light emitter. It peaks at about 520nm and meets human visibility with green, blue or red light emission, and after dimming at 200 lux illumination for 4 minutes, the brightness and afterglow characteristics of the light emission are investigated and compared with conventional ZnSiCu-based phosphors. In comparison, the brightness is more than 10 times bright and afterglow can be seen for a long time, and the higher the synchronous illuminance is, the higher the afterglow luminance is obtained. It takes about 20 to 30 minutes, and white fluorescent lamps and sunlight are the most efficient light sources, and include a lot of ultraviolet rays. Durability test with high pressure mercury lamp showed excellent durability.
한편, 본 발명에서 사용되는 직물지로는 통상적으로 합성피혁의 제조에 사용되는 직물지는 모두 사용이 가능하며, 부직포, 폴리에스테르, 폴리에틸렌, 폴리프로필렌, 아크릴로니트릴부타디엔스티렌, 폴리스티렌, 폴리카보네이트, 폴리아미드 등으로 제조된 합성수지 직물이 사용 가능하다.On the other hand, as the woven paper used in the present invention, all can be used conventionally used for the manufacture of synthetic leather, non-woven fabric, polyester, polyethylene, polypropylene, acrylonitrile butadiene styrene, polystyrene, polycarbonate, polyamide Synthetic resin fabrics made of or the like can be used.
먼저, 산화스트론튬 55 ∼ 62.5중량%, 산화알루미늄 35 ∼ 42.5중량%, 산화디스프로슘 1 ∼ 9중량% 및 산화유로퓸 0.5 ∼ 1.5중량%로 구성되는 축광성 황색 발광체, 산화스트론튬 20 ∼ 68.75중량%, 산화알루미늄 30 ∼ 78.75중량%, 산화칼슘 1 ∼ 49.75%, 산화디스프로슘 0.1 ∼ 49.75중량%, 산화유로퓸 0.1 ∼ 49.75중량% 및 이산화규소 0.05 ∼ 48.8중량%로 구성되는 축광성 청색 변색 발광체 또는 칼슘설파이드 70 ∼ 98.85중량%, 칼슘설페이트 1 ∼ 29.85중량%, 유로퓸 및/또는 톨륨 0.05 ∼ 28.9중량% 및 이산화규소 0.1 ∼ 28.95중량%로 구성되는 축광성 적색 변색 발광체 5 ∼ 25중량%와 액상의 폴리우레탄계 수지 75 ∼ 95중량%를 혼합한 혼합물 중량에 대하여 분산제, 증백제, 안정제 등의 첨가제를 1 ∼ 10중량% 첨가하여 발광체 함유 혼합물을 제조한다.First, the photoluminescent yellow light-emitting body which consists of 55-62.5 weight% of strontium oxide, 35-42.5 weight% of aluminum oxides, 1-9 weight% of dysprosium oxides, and 0.5-1.5 weight% of europium oxide, 20-68.75 weight% of strontium oxides, and oxidation A photoluminescent blue color changing emitter or calcium sulfide composed of 30 to 78.75% by weight of aluminum, 1 to 49.75% of calcium oxide, 0.1 to 49.75% by weight of dysprosium oxide, 0.1 to 49.75% by weight of europium oxide, and 0.05 to 48.8% by weight of silicon dioxide. 5 to 25% by weight of a photoluminescent red discoloration emitter consisting of 98.85% by weight, calcium sulfate 1 to 29.85% by weight, europium and / or tolium 0.05 to 28.9% by weight, and silicon dioxide 0.1 to 28.95% by weight, and a liquid polyurethane resin 75 1-10 weight% of additives, such as a dispersing agent, a brightener, and a stabilizer, are added with respect to the mixture weight which mixed -95 weight%, and a light-emitting-containing mixture is manufactured.
축광성 발광체의 사용량이 25중량%를 초과할 경우에는 액상의 폴리우레탄계 수지와의 혼합이 용이하지 못한 문제점이 있고, 15중량% 미만일 경우에는 최종적으로 첨가되는 축광성 발광체의 함유량이 감소되어 축광 특성의 발현이 용이하지 못한 단점이 있다.If the amount of the photoluminescent emitter is more than 25% by weight, it is not easy to mix the liquid with a polyurethane-based resin. If the amount of the photoluminescent emitter is less than 15% by weight, the content of the photoluminescent emitter finally added is reduced, so that the photoluminescent properties are reduced. There is a disadvantage that the expression is not easy.
분산제, 증백제, 안정제 등의 첨가제는 본 발명이 속하는 기술 분야에서 통상적으로 사용되는 것들이 모두 사용 가능하지만, 축광성 발광체의 발광에 영향을 미치지 않는 것을 사용하여야만 한다. 첨가제의 사용량은 특별히 제한되는 것은 아니지만 축광성 발광체와 액상의 폴리우레탄계 수지를 혼합한 혼합물 중량에 대하여 10중량%를 초과하지 않는 것이 효과적이며, 10중량%를 초과할 경우에는 도포층의 형성이 용이하지 못하거나 내구성이 저하되는 문제점이 있고, 첨가제의 사용량은 사용되는 첨가제의 종류 및 특성, 완제품이 적용될 용도 등을 고려하여 적절히 결정될 수 있다.Additives such as dispersants, brighteners, stabilizers and the like can be used all those conventionally used in the technical field to which the present invention belongs, but should be used that do not affect the emission of the photoluminescent emitter. The amount of the additive is not particularly limited, but it is effective not to exceed 10% by weight based on the weight of the mixture of the photoluminescent emitter and the liquid polyurethane-based resin, and when the amount exceeds 10% by weight, the formation of the coating layer is easy. There is a problem that does not or the durability is reduced, the amount of the additive may be appropriately determined in consideration of the type and characteristics of the additive used, the use to which the finished product is applied.
액상의 폴리우레탄계 수지는 합성피혁 제조용으로 광범위하게 사용되는 통상의 직물지 표면상에 도포가 용이하게 이루어질 수 있는 것을 사용하는 것이 효과적이며, 여러 가지 효과를 나타내도록 변성시킨 변성 폴리우레탄 수지도 사용될 수 있다.It is effective to use a liquid polyurethane-based resin that can be easily applied on the surface of a conventional textile paper widely used for the production of synthetic leather, and a modified polyurethane resin modified to exhibit various effects can also be used. .
상술한 바와 같이 축광성 발광체, 액상의 폴리우레탄계 수지 및 각종 첨가제가 혼합된 혼합물을 이형지상에 도포하고 건조한 후, 접착제를 도포하고 통상의 합성피혁용 직물지와 합지한 다음, 이형지를 제거하므로서 본 발명의 축광성 합성피혁이 제조된다. 축광성 발광체, 액상의 폴리우레탄계 수지 및 첨가제의 혼합물과 접착제의 도포는 본 발명이 속하는 기술 분야에서 통상적으로 사용되는 도포 방법이 모두 사용 가능하지만, 본 발명에서는 장치의 설계가 간단하고 공정 운영 비용이 저렴하므로 나이프 코팅(Knife coating) 방법을 주로 사용하였다. 그러나, 디프 코팅(Dip coating), 롤 코팅(Roll coating), 커텐 코팅(Curtain coating), 에어나이프 코팅(Airknife coating) 방법 등도 사용될 수 있다.As described above, the mixture of the photoluminescent emitter, the liquid polyurethane-based resin, and various additives is coated on a release paper, dried, coated with an adhesive, and then laminated with a conventional synthetic leather fabric paper, and then the release paper is removed. Photoluminescent synthetic leather is produced. The application of a mixture of photoluminescent emitters, liquid polyurethane-based resins and additives, and adhesives can be performed using all of the coating methods commonly used in the technical field of the present invention. Knife coating method was mainly used because it is inexpensive. However, dip coating, roll coating, curtain coating, airknife coating, or the like may also be used.
이형지는 적어도 일면에 윤활층이 형성되어 있어 추후에 제거가 용이한 것을 사용하며, 이형지상에 엠보싱 등의 무늬를 형성시키므로서 제조되는 본 발명의 축광성 합성피혁에 무늬를 형성시킬 수도 있다.The release paper is formed of a lubricating layer on at least one surface, so that it can be easily removed later, and the pattern may be formed on the photoluminescent synthetic leather of the present invention produced by forming a pattern such as embossing on the release paper.
이형지상에 축광성 발광체, 액상의 폴리우레탄계 수지 및 첨가제 혼합물의 도포시 도포량은 100 ∼ 400g/㎡ 정도가 되도록 하는 것이 효과적이다. 도포량이 100g/㎡ 미만일 경우에는 발광체의 발광시 휘도 등의 발광 효율이 좋지 못하여 본 발명에서 이루고자 하는 목적을 달성할 수 없으며, 400g/㎡을 초과할 경우에는 도포층에 크랙이 발생하거나 도포층의 두께가 균일하지 않게되는 등의 문제점이 있다.It is effective that the coating amount is about 100 to 400 g / m 2 when the phosphorescent emitter, the liquid polyurethane-based resin, and the additive mixture are applied on the release paper. If the coating amount is less than 100g / ㎡ the luminous efficiency, such as the luminance at the time of light emission of the light emitting body is not good to achieve the object to achieve in the present invention, when it exceeds 400g / ㎡ cracks occur in the coating layer or of the coating layer There is a problem that the thickness is not uniform.
축광성 발광체, 액상의 폴리우레탄계 수지 및 첨가제 혼합물의 도포 후, 건조실에서 115 ∼ 125℃의 온도로 2 ∼ 3분간 건조하여 축광성 발광체 함유 도포층을 고화시킨다.After application of the photoluminescent emitter, liquid polyurethane-based resin and the additive mixture, the film is dried at a temperature of 115 to 125 ° C. for 2 to 3 minutes in a drying chamber to solidify the photoluminescent emitter-containing coating layer.
그 다음에 축광성 발광체 함유 도포층상에 합성수지계의 접착제를 50 ∼ 100g/㎡ 정도의 도포량이 되도록 도포한다. 특히, 접착제는 축광성 발광체 함유 도포층과 통상의 합성피혁 제조용 직물지가 용이하게 합지될 수 있는 것을 사용하는 것이 바람직하며, 특히 폴리우레탄계 수지나 아크릴계 수지 등을 사용하는 것이 바람직하지만, 합지될 통상의 합성피혁 제조용 직물지의 종류에 따라 적절히 선택하여 사용할 수 있다.Then, a synthetic resin adhesive is applied onto the photoluminescent light-emitting coating layer so as to have a coating amount of about 50 to 100 g / m 2. In particular, the adhesive is preferably one that can be easily laminated with a light-emitting phosphor-containing coating layer and a conventional synthetic leather manufacturing fabric paper, it is preferable to use a polyurethane resin, acrylic resin, etc. It can be suitably selected and used according to the type of fabric paper for synthetic leather production.
접착제를 도포 후, 접착제가 흘러내리지 않을 정도로 건조실에서 건조를 한다. 바람직하게는 115 ∼ 125℃의 온도로 2 ∼ 3분간 건조하는 것이 효과적이다.After apply | coating an adhesive agent, it dries in a drying room so that adhesive agent may not flow down. Preferably, it is effective to dry for 2-3 minutes at the temperature of 115-125 degreeC.
건조 후 통상의 합성피혁 제조용 직물지와 3 ∼ 10톤/㎠ 정도의 압력으로 합지하고 자연 건조한 다음, 이형지를 제거하거나 제품으로 적용 후에 이형지를 제거한다.After drying, it is laminated at a pressure of about 3 to 10 ton / cm 2 with normal synthetic leather manufacturing fabric paper and naturally dried, and then the release paper is removed or the release paper is removed after application as a product.
상기와 같은 제조된 본 발명의 축광성 합성피혁은 신발, 가방, 기능성 의류(등산복, 운동복 등) 등의 제품에 적용 가능하다.The photoluminescent synthetic leather of the present invention prepared as described above is applicable to products such as shoes, bags, functional clothing (climbing, sportswear, etc.).
다음의 실시예 및 비교예는 본 발명을 좀 더 상세히 설명하는 것이지만, 본 발명의 범주를 한정하는 것은 아니다.The following examples and comparative examples illustrate the invention in more detail, but do not limit the scope of the invention.
실시예 1Example 1
산화스트론튬 57중량%, 산화알루미늄 39중량%, 산화디스프로슘 3.3중량% 및 산화유로퓸 0.7중량%로 구성되는 축광성 형광체 15중량%와 액상의 폴리우레탄수지 85중량%를 혼합한 혼합물 중량에 대하여 증백제(칼슘클로라이드와 치아염소산칼륨과의 복염과 수산화칼슘의 혼합물)0.5중량%, 열안정제(디옥틸틴 라우레이트) 0.5중량% 및 광안정제(벤젠 트리아졸) 0.5중량%를 첨가하고 균질하게 혼합하여 축광성 발광체 함유 혼합물을 얻는다.Brightener based on the mixture weight of 15% by weight of the phosphorescent phosphor consisting of 57% by weight of strontium oxide, 39% by weight of aluminum oxide, 3.3% by weight of dysprosium oxide, and 0.7% by weight of europium oxide and 85% by weight of the liquid polyurethane resin. (Mixture of double salts of calcium chloride and potassium chlorate with calcium hydroxide) 0.5% by weight, 0.5% by weight of heat stabilizer (dioctyltin laurate) and 0.5% by weight of light stabilizer (benzene triazole) are added and mixed homogeneously A light emitting containing mixture is obtained.
그 다음에 제조된 축광성 발광체 함유 혼합물을 윤활층이 형성된 이형지의 윤활층상에 나이프 코팅 방법으로 250g/㎡의 도포량이 되도록 도포한 후, 건조실로 이송하여 120℃의 온도로 3분간 건조한 다음, 폴리비닐알코올을 접착제로 도포하되 80g/㎡의 도포량이 되도록 도포한 후, 건조실로 이송하여 110℃의 온도로 2분간 건조한다.Then, the prepared photoluminescent phosphor-containing mixture was coated on the lubricating layer of the release paper on which the lubricating layer was formed so as to have a coating amount of 250 g / m 2 by a knife coating method, and then transferred to a drying chamber and dried at a temperature of 120 ° C. for 3 minutes, followed by poly Vinyl alcohol is applied with an adhesive, but applied to a coating amount of 80g / ㎡, and then transferred to a drying chamber and dried for 2 minutes at a temperature of 110 ℃.
그 다음에 부직포와 5톤/㎠의 압력으로 합지하고 하루 동안 자연 건조시키고 이형지를 제거하여 본 발명의 합성피혁을 얻고, 이에 대한 발광특성을 측정 및 평가하여 그 결과를 표 1에 기재하였다.Then, laminated with a non-woven fabric at a pressure of 5 tons / cm 2, and naturally dried for one day to remove the release paper to obtain a synthetic leather of the present invention, the luminescence properties were measured and evaluated for the results are shown in Table 1.
실시예 2 ∼3Examples 2 to 3
산화스트론튬 43중량%, 산화알루미늄 51중량%, 산화칼슘 4.4중량%, 산화디프로슘 0.6중량%, 산화유로퓸 0.6중량% 및 이산화규소 0.4중량%로 구성되는 축광성 청색 변색 발광체와 칼슘설파이드(Calcium sulfide) 95중량%, 칼슘설페이트(Calcium sulfate) 5중량%, 유로퓸 및/또는 톨륨(Thulium) 0.1중량% 및 이산화규소 0.25중량%로 구성되는 축광성 적색 변색 발광체를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 합성피혁을 제조하고, 이에 대한 발광특성을 측정 및 평가하여 그 결과를 표 1에 기재하였다.Photoluminescent blue discoloration emitter and calcium sulfide consisting of 43% by weight of strontium oxide, 51% by weight of aluminum oxide, 4.4% by weight of calcium oxide, 0.6% by weight of diprosium oxide, 0.6% by weight of europium oxide and 0.4% by weight of silicon dioxide (Calcium Example 1, except that a photoluminescent red color fading emitter composed of 95% by weight of sulfide, 5% by weight of calcium sulfate, 0.1% by weight of europium and / or thhulium, and 0.25% by weight of silicon dioxide was used. Synthetic leather was prepared in the same manner as described above, and the luminescence properties thereof were measured and evaluated, and the results are shown in Table 1.
비교예 1Comparative Example 1
축광성 발광체로 ZnSiCu계 축광체를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 직물지를 얻고, 이에 대한 발광특성을 측정 및 평가하여 그 결과를 표 1에 기재하였다.Except for using the ZnSiCu-based photoluminescent material as a photoluminescent light emitting body was obtained in the same manner as in Example 1, the luminescence properties were measured and evaluated for the results are shown in Table 1.
- 표 1 -Table 1
1) 표준광원 200룩스, 4분조사, 20분후의 잔광휘도1) 200 lux standard light, 4 minute irradiation, afterglow luminance after 20 minutes
2) 잔광휘도가 인간의 시인치인 0.32300mcd/m2까지 감쇄되는 데 필요한 시간2) the time required for the afterglow luminance to be attenuated to 0.32300 mcd / m 2, which is the human inch
3) 표준광원 200룩스에서 동기할 경우 얻어지는 잔광휘도가 포화되는 동기시간3) Synchronization time when the afterglow luminance obtained when synchronous at the standard light source of 200 lux is saturated
4) 300왓트의 고압수운등에서 가속시험할 때 잔광휘도가 20%이상 저하되는 데 필요한 시간4) Time required to reduce afterglow brightness by more than 20% when accelerated test in 300W high pressure water lamp.
상술한 바와 같이 본 발명에서는 산화스트론튬 55 ∼ 62.5중량%, 산화알루미늄 35 ∼ 42.5중량%, 산화디스프로슘 1 ∼ 9중량% 및 산화유로퓸 0.5 ∼ 1.5중량%로 구성되는 축광성 황색 발광체, 산화스트론튬 20 ∼ 68.75중량%, 산화알루미늄 30 ∼ 78.75중량%, 산화칼슘 1 ∼ 49.75%, 산화디스프로슘 0.1 ∼ 49.75중량%, 산화유로퓸 0.1 ∼ 49.75중량% 및 이산화규소 0.05 ∼ 48.8중량%로 구성되는 축광성 청색 변색 발광체 또는 칼슘설파이드 70 ∼ 98.85중량%, 칼슘설페이트 1 ∼ 29.85중량%, 유로퓸 및/또는 톨륨 0.05 ∼ 28.9중량% 및 이산화규소 0.1 ∼ 28.95중량%로 구성되는 축광성 적색 변색 발광체 5 ∼ 25중량%와 액상의 폴리우레탄계 수지 75 ∼ 95중량%를 혼합한 혼합물 중량에 대하여 분산제, 증백제, 안정제 등의 첨가제를 1 ∼ 10중량% 첨가한 혼합물을 통상의 합성피혁용 직물지의 표면에 도포하여 구성된 것으로서, 이형지상에 상기 축광성 발광체 함유 혼합물을 도포하고 건조한 후, 접착제를 도포하고 통상의 직물지와 합지한 다음, 이형지를 제거하여 축광 특성을 갖는 합성피혁을 제조하므로서 발광시간이 길고, 발광시 휘도가 높으며, 여기하는 빛의 파장범위가 넓고, 내광성 및 내후성이 뛰어나며 야외사용이 가능할 뿐만 아니라 화학적 안정성이 높고 환경오염을 유발하지 않으며 인체에도 무해하고 변색도 가능하여 광범위한 용도로 적용 가능한 축광 특성을 갖는 합성피혁을 얻을 수 있었다.As described above, in the present invention, a luminescent yellow light-emitting body composed of 55 to 62.5% by weight of strontium oxide, 35 to 42.5% by weight of aluminum oxide, 1 to 9% by weight of dysprosium oxide, and 0.5 to 1.5% by weight of europium oxide, and strontium oxide 20 to Phosphorescent blue discolored light emitting body consisting of 68.75 wt%, aluminum oxide 30-78.75 wt%, calcium oxide 1-49.75%, dysprosium oxide 0.1-49.75 wt%, europium oxide 0.1-49.75 wt% and silicon dioxide 0.05-48.8 wt% Or 5 to 25% by weight of a photoluminescent red discoloring emitter composed of 70 to 98.85% by weight of calcium sulfide, 1 to 29.85% by weight of calcium sulfate, 0.05 to 28.9% by weight of europium and / or tolium and 0.1 to 28.95% by weight of silicon dioxide To the weight of the mixture of 75 to 95% by weight of polyurethane-based resin, a mixture of 1 to 10% by weight of an additive such as a dispersant, a brightener, and a stabilizer was added to the surface of a conventional synthetic leather textile paper. It is configured by applying, the light-emitting phosphor-containing mixture on a release paper, and then dried, coated with an adhesive and laminated with a conventional textile paper, and then removed the release paper to produce a synthetic leather having a photoluminescent property, the light emission time is long, High luminous intensity during light emission, wide wavelength range of excitation light, excellent light resistance and weather resistance, outdoor use, high chemical stability, no environmental pollution, harmless to human body and discoloration. Synthetic leather having the characteristics was obtained.
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