KR101042933B1 - Eco-composite fire retardant compounds for coating polyurethane synthetic leather - Google Patents
Eco-composite fire retardant compounds for coating polyurethane synthetic leather Download PDFInfo
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- KR101042933B1 KR101042933B1 KR1020110021767A KR20110021767A KR101042933B1 KR 101042933 B1 KR101042933 B1 KR 101042933B1 KR 1020110021767 A KR1020110021767 A KR 1020110021767A KR 20110021767 A KR20110021767 A KR 20110021767A KR 101042933 B1 KR101042933 B1 KR 101042933B1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/06—Properties of the materials having thermal properties
- D06N2209/067—Flame resistant, fire resistant
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Abstract
Description
본 발명은 폴리우레탄 합성피혁 코팅용 친환경 복합 난연제 조성물에 관한 것으로, 더욱 상세하게는 인산에스테르계 화합물, 멜라민계 화합물, 징크보레이트(ZnBorate, 2ZnO·B2O3·5H20) 및 수산화마그네슘의 혼합물로 이루어진 복합 난연제로서, 용제형 타입으로 폴리우레탄 합성피혁의 코팅용에 적합하고, 난연 성능이 우수하며, 할로겐계 난연제를 사용하지 않은 친환경적인 것을 특징으로 하는 폴리우레탄 합성피혁 코팅용 친환경 복합 난연제 조성물에 관한 것이다.
The present invention relates to an environment-friendly composite flame retardant composition for polyurethane synthetic leather coatings, and more particularly, to phosphate ester compounds, melamine compounds, zinc borate (ZnBorate, 2ZnO.B 2 O 3 .5H 2 0) and magnesium hydroxide. Composite flame retardant consisting of a mixture, it is a solvent type, suitable for coating polyurethane synthetic leather, excellent flame retardant performance, eco-friendly composite flame retardant for polyurethane synthetic leather coating, characterized in that it is eco-friendly without using halogen-based flame retardant It relates to a composition.
일반적으로 난연제는 유기 난연제와 무기 난연제로 분류되어 진다. 유기난연제는 브롬계, 염소계 등과 같은 할로겐계 화합물 및 인산에스테르계 등과 같은 인계 화합물이 주성분인 난연제이고, 무기난연제는 삼산화안티몬, 오산화안티몬 등과 같은 산화안티몬계, 수산화알루미늄 등과 같은 수산화화합물계, 중비금속화합물계, 탄산칼슘(CaCO3), 탄산마그네슘(MgHCO3), 클레이, 탈크 등과 같은 화합물이 주성분인 난연제로서 무기난연제는 주로 보조난연제로 사용되고 있다.
Flame retardants are generally classified into organic flame retardants and inorganic flame retardants. Organic flame retardants are flame retardants whose main components are halogen-based compounds such as bromine and chlorine, and phosphorus compounds such as phosphate esters, and inorganic flame retardants are antimony oxides such as antimony trioxide and antimony pentoxide, hydroxide compounds such as aluminum hydroxide, and heavy metals. Compound-based, calcium carbonate (CaCO3), magnesium carbonate (MgHCO3), clay, talc and the like as a main component flame retardant, inorganic flame retardant is mainly used as auxiliary flame retardant.
최근 유럽의회는 전기·전자제품에 적용되는 유독성물질 함유금지 지침(RoHS : Restriction of Hazardous Substance in electrical and electronic equipment)의 적용대상인 전자 및 전기제품에 대해 브롬계 난연제 사용을 제한하는 방침에 따라 대체 난연제의 개발이 다양하게 진행되고 있다.
In recent years, the European Parliament has replaced alternative flame retardants in accordance with a policy to restrict the use of bromine-based flame retardants for electronic and electrical products subject to the Restriction of Hazardous Substance in electrical and electronic equipment (RoHS). Development is underway.
한편, 합성피혁용 난연제는 대부분 그 성상이 분말 상이기 때문에 주성분이 폴리우레탄 성분인 합성피혁용 합성수지액에 배합 작업시 난연제가 비산되어 작업장의 환경이 오염될 뿐만 아니라 배합액의 불량이 야기되고, 또한 난연제가 분말 상이므로 함침액과의 배합시 폴리우레탄 성분의 주 배합액에 잘 분산되지 아니하여 합성피혁의 가공을 위한 염색, 코팅 등의 공정시에 문제가 발생할 소지가 많은 우려가 있다.
On the other hand, since most of the flame retardant for synthetic leather is in the form of powder, the flame retardant is scattered during the blending operation to the synthetic resin for synthetic leather whose main component is a polyurethane component, which not only contaminates the environment of the workplace but also causes a defect of the blending liquid. In addition, since the flame retardant is in the form of a powder, it may not be well dispersed in the main compound solution of the polyurethane component when blended with the impregnation solution, which may cause a lot of problems in the process of dyeing and coating the synthetic leather for processing.
상기와 같은 문제점들을 해결하기 위한 방안으로 비할로겐계 난연제에 대한 연구개발들이 활발하게 진행되고 있다. 국내 등록특허 제652331호에 수평균분자량 100,000 내지 200,000의 폴리우레탄 100 중량부; 유기 용제 50 내지 250 중량부; 및 안료 0.1 내지 30 중량부를 포함하여 구성된 함침용 폴리우레탄 조성물이 알려져 있고, 국내 등록특허 제881945호에 폴리올에 반응성 난연제를 첨가하여 우레탄 용액을 합성하고, 상기 합성한 우레탄 용액에 사이클로포스페이트계 난연제를 첨가하여 제조하는 것을 특징으로 하는 인공피혁용 액상 난연제 조성물이 알려져 있다.
In order to solve the above problems, research and development on non-halogen flame retardants have been actively conducted. 100 parts by weight of polyurethane having a number average molecular weight of 100,000 to 200,000 in Korean Patent No. 652331; 50 to 250 parts by weight of an organic solvent; And the impregnated polyurethane composition comprising 0.1 to 30 parts by weight of a pigment is known, to synthesize a urethane solution by adding a reactive flame retardant to a polyol in Korean Patent No. 881945, to a cyclophosphate flame retardant to the synthesized urethane solution There is known a liquid flame retardant composition for artificial leather, which is prepared by addition.
본 출원인도 상기와 같은 문제점들을 해결하기 위한 방안으로, 비할로겐계 합성피혁용 난연제를 개발하여 국내 등록특허 제613631호로 주성분이 데카브로모디페닐에탄(DBDPE), 헥사브로모디페닐옥사이드(HBCD) 및 삼산화안티몬으로 이루어지고, 균일성, 분산성, 침투성 및 작업성이 좋기 때문에 난연성능이 우수하고, 친환경적인 것을 특징으로 하는 합성피혁용 액상 난연제를 개발하여 이미 특허등록 받은 바 있고, 또한 국내 등록특허 제755893호로 수용성 폴리우레탄 수지 6~9중량%, 수용성 메틸메타아크릴레이트 수지 6~9중량%, 비할로겐계 난연제 28~32중량%, 용매인 물 45~57중량%, 점증제인 폴리에틸렌옥사이드 1.5~3.5중량% 및 안정제인 에틸렌디프로필렌계계 블록공중합체 구조의 계면활성제 1.5~3.5중량%로 이루지는 것을 특징으로 하는 합성피혁용 비할로겐계 난연제 조성물도 개발하여 특허등록 받은 바 있다.
In order to solve the above problems, the present applicant has also developed a flame retardant for non-halogen-based synthetic leather, and the main components thereof are Korean Patent No. 613331, decarbromodiphenylethane (DBDPE), hexabromodiphenyl oxide (HBCD) and Since it is made of antimony trioxide, and has good uniformity, dispersibility, permeability and workability, it has already been patented by developing liquid flame retardant for synthetic leather, which is characterized by excellent flame retardant performance and eco-friendliness. No.755893 6-9% by weight of water-soluble polyurethane resin, 6-9% by weight of water-soluble methyl methacrylate resin, 28-32% by weight of non-halogen-based flame retardant, 45-57% by weight of solvent water, polyethylene oxide 1.5- by thickener Non-halogen-based synthetic leather, comprising 3.5% by weight and 1.5 to 3.5% by weight of a surfactant having an ethylene dipropylene-based block copolymer structure as a stabilizer. A flame retardant composition has also been developed and patented.
따라서, 상기에서 설명한 바와 같이 유럽에서 유독성물질 함유금지 지침(RoHS)에 의한 브롬계 난연제 사용을 제한하는 방침에 따라 대체 난연제의 개발이 시급한 실정이다.
Therefore, as described above, it is urgent to develop alternative flame retardants in accordance with the policy of restricting the use of bromine flame retardants in accordance with the RoHS Directive.
상기와 같은 문제점을 해결하기 위한 방안으로 본 발명은 인산에스테르계 화합물과 멜라민계 화합물이 혼합된 복합 난연제로서, 산소의 차단과 불꽃의 확대를 저지하고, 특히 열분해에 의한 라디칼 트랩 효과에 의해 난연성이 우수한 비할로겐계 난연제로서 친환경적이며, 용제형 타입으로 폴리우레탄 합성피혁 코팅용에 적합한 것을 특징으로 하는 폴리우레탄 합성피혁 코팅용 친환경 복합 난연제 조성물을 제공함을 과제로 한다.
In order to solve the above problems, the present invention is a composite flame retardant mixed with a phosphate ester compound and a melamine compound, to prevent the blocking of oxygen and the expansion of the flame, in particular flame retardancy due to the radical trap effect by thermal decomposition It is an object of the present invention to provide an environment-friendly composite flame retardant composition for polyurethane synthetic leather coating, which is environmentally friendly as an excellent non-halogen-based flame retardant and is suitable for coating a polyurethane synthetic leather in a solvent type.
그리고 본 발명은 인산에스테르계 화합물과 멜라민계 화합물이 혼합된 복합 난연제에 징크보레이트(ZnBorate, 2ZnO·B2O3·5H20)를 첨가하여 불꽃 및 잔염을 억제시켜 유독가스 및 연기발생을 억제하는 억연(抑煙) 효과가 우수하고, 또한 수산화마그네슘을 첨가하여 탈수반응에 의한 흡열 작용에 의해 연소를 지연시킴으로써, 난연성과 억연성의 성능이 우수한 것을 특징으로 하는 폴리우레탄 합성피혁 코팅용 친환경 복합 난연제 조성물을 제공함을 다른 과제로 한다.
In the present invention, zinc borate (ZnBorate, 2ZnO · B 2 O 3 · 5H 2 0) is added to a composite flame retardant mixed with a phosphate ester compound and a melamine compound to suppress the generation of toxic gases and smoke by suppressing flame and residual flame. Eco-friendly composite for polyurethane synthetic leather coating, which has excellent anti-depressive effect and delays combustion by endothermic action by dehydration reaction by adding magnesium hydroxide. Another object is to provide a flame retardant composition.
본 발명은 인산에스테르계 화합물 34~38 중량%, 멜라민계 화합물 10~12 중량%, 징크보레이트(ZnBorate, 2ZnO·B2O3·5H20) 12~15 중량%, 수산화마그네슘 3~5 중량%, 안정제 1~2 중량% 및 용제 32~36 중량%로 이루어지는 것을 특징으로 하는 폴리우레탄 합성피혁 코팅용 친환경 복합 난연제 조성물을 과제 해결 수단으로 한다.
The present invention is 34 to 38% by weight of the phosphate ester compound, 10 to 12% by weight of the melamine compound, zinc borate (ZnBorate, 2ZnO · B 2 O 3 · 5H 2 0) 12 to 15% by weight, magnesium hydroxide 3 to 5% by weight An environmentally friendly composite flame retardant composition for polyurethane synthetic leather coating, comprising%, stabilizer 1 to 2% by weight and solvent 32 to 36% by weight as a means for solving the problem.
그리고 본 발명에서 상기 인산에스테르계 화합물은 아래 화학식 (1)과 같은 구조인 것을 특징으로 한다.
And in the present invention, the phosphate ester compound is characterized in that the structure as shown in the formula (1) below.
또한 상기 멜라민계 화합물은 피로인산멜라민염(Melamine Pyrophosphate)이고, 상기 안정제는 나노 클레이이며, 상기 용제는 디메틸포름아미드(DMF), 톨루엔 또는 메틸에틸케톤(MEK) 중에서 1종 또는 그 이상을 선택하여 사용하는 것이 바람직하다.
In addition, the melamine-based compound is melamine pyrophosphate (Melamine Pyrophosphate), the stabilizer is nano clay, the solvent is selected from one or more of dimethylformamide (DMF), toluene or methyl ethyl ketone (MEK) It is preferable to use.
본 발명은 인산에스테르계 화합물과 멜라민계 화합물이 혼합된 복합 난연제에 의해 산소의 차단과 불꽃의 확대를 저지하고, 특히 열분해에 의한 라디칼 트랩 효과에 의해 난연성이 우수한 비할로겐계 난연제로서 친환경적이며, 용제형 타입으로 폴리우레탄 합성피혁 코팅용에 적합하고, 또한 인산에스테르계 화합물과 멜라민계 화합물이 혼합된 복합 난연제에 징크보레이트(ZnBorate, 2ZnO·B2O3·5H20)를 첨가하여 유독가스 및 연기발생을 억제하는 억연(抑煙) 효과가 우수하고, 또한 수산화마그네슘을 첨가하여 탈수반응에 의한 흡열 작용에 의해 연소를 지연시킴으로써, 난연성과 억연성의 성능이 우수한 것이 장점이다.
The present invention is an eco-friendly, non-halogen flame retardant having excellent flame retardancy due to a radical trap effect by thermal decomposition by preventing the oxygen blocking and expansion of the flame by a composite flame retardant mixed with a phosphate ester compound and a melamine compound. ZnBorate (ZnBorate, 2ZnO · B 2 O 3 · 5H 2 0) is added to the composite flame retardant mixed with phosphate ester compound and melamine compound, and is suitable for polyurethane synthetic leather coating. It is an advantage that it is excellent in the depressive effect of suppressing smoke generation, and retards combustion by the endothermic action by the dehydration reaction by adding magnesium hydroxide, which is excellent in flame retardancy and deterrent performance.
이하, 본 발명의 기술적 구성을 아래의 실시 예에 의해 상세히 설명하며, 본 발명을 실시하기 위한 구체적인 내용에서 일반적인 난연제 조성물 제조분야의 종사자들이 용이하게 알 수 있는 구성에 대한 언급은 간략히 하거나 생략하였다.
Hereinafter, the technical configuration of the present invention will be described in detail by the following examples, and reference to a configuration that can be easily understood by those skilled in the art of manufacturing a general flame retardant composition in the detailed description for carrying out the present invention will be briefly or omitted.
본 발명은 인산에스테르계 화합물 34~38 중량%, 멜라민계 화합물 10~12 중량%, 징크보레이트(ZnBorate, 2ZnO·B2O3·5H20) 12~15 중량%, 수산화마그네슘 3~5 중량%, 안정제 1~2 중량% 및 용제 32~36 중량%로 이루어지는 것을 특징으로 하는 폴리우레탄 합성피혁 코팅용 친환경 복합 난연제 조성물(이하, '복합 난연제 조성물'라 한다)에 관한 것이다.
The present invention is 34 to 38% by weight of the phosphate ester compound, 10 to 12% by weight of the melamine compound, zinc borate (ZnBorate, 2ZnO · B 2 O 3 · 5H 2 0) 12 to 15% by weight, magnesium hydroxide 3 to 5% by weight It relates to an environmentally friendly composite flame retardant composition (hereinafter, referred to as a "composite flame retardant composition") for polyurethane synthetic leather coating, characterized in that consisting of%, 1 to 2% by weight stabilizer and 32 to 36% by weight solvent.
본 발명은 인산에스테르계 화합물과 멜라민계 화합물이 혼합된 복합 난연제조성물로서, 산소의 차단과 불꽃 확대의 저지가 우수하고, 특히 열분해에 의한 라디칼 트랩 효과에 의해 난연성이 우수하다.
The present invention is a composite flame retardant composition in which a phosphate ester compound and a melamine compound are mixed. The present invention is excellent in blocking oxygen and preventing flame expansion, and is particularly excellent in flame retardancy due to a radical trap effect by thermal decomposition.
또한 브롬계 화합물을 사용하지 않는 비할로겐계 난연제로서 친환경적이며, 용제형 타입으로 주로 자동차, 기차, 항공기 등과 같은 교통수단의 시트용이나 또는 가구 또는 소파 등의 외피용으로서 사용되는 합성피혁의 코팅용에 적합한 것이 특징이다.
In addition, it is a non-halogen flame retardant that does not use bromine compounds, which is environmentally friendly, and is a solvent type for coating of synthetic leather, which is mainly used for seats of transportation such as automobiles, trains, airplanes, or for the exterior of furniture or sofas. It is suitable for.
본 발명에서 상기 인산에스테르계 화합물은 본 발명에 따른 복합 난연제의 주성분으로, 산소의 차단과 불꽃의 확대를 저지하고, 특히 열분해에 의한 라디칼 트랩 효과에 의해 난연성이 우수한 것이 특징이다.
In the present invention, the phosphate ester-based compound is a main component of the composite flame retardant according to the present invention, which blocks the blocking of oxygen and the expansion of the flame, and is particularly characterized by excellent flame retardancy due to the radical trap effect by thermal decomposition.
또한 본 발명에서 인산에스테르계 화합물의 혼합량은 34~38 중량%인 것이 바람직하며, 인산에스테르계 화합물의 혼합량이 상기에서 한정한 범위 미만으로 혼합될 경우에는 산소의 차단 등의 성능이 약해져서 난연 성능이 저하할 우려가 있고, 인산에스테르계 화합물의 혼합량이 상기에서 한정한 범위를 초과할 경우에는 인산에스테르계 화합물의 혼합량에 비해 상대적으로 멜라민계 화합물의 혼합량이 적어짐에 따라 난연 특성이 보완되지 아니하여 오히려 난연 성능이 저하할 우려가 있다.
In addition, in the present invention, the mixing amount of the phosphate ester compound is preferably 34 to 38% by weight, and when the mixing amount of the phosphate ester compound is mixed below the range defined above, the performance such as blocking of oxygen is weakened, so that the flame retardant performance is poor. If the mixing amount of the phosphate ester compound exceeds the above-defined range, the amount of the melamine compound is decreased relative to the mixing amount of the phosphate ester compound. There is a fear that the flame retardant performance is lowered.
본 발명에서 사용하는 인산에스테르계 화합물은 아래 화학식 (1)과 같은 구조인 것을 사용한다.
The phosphate ester compound used in the present invention uses a structure having the same structure as in the following formula (1).
그리고 본 발명에 따른 복합 난연제는 부성분으로 멜라민계 화합물을 혼합하며, 멜라민계 화합물은 연소시 다이옥신 발생의 이론적 가능성이 이슈가 돼서 문제시되고 있는 불소계 난연제의 대체 난연제로서, 난연소재의 연소시 불연성 가스를 발생시켜 난연소재인 합성피혁에 공급되는 산소를 차단하여 연소를 억제시켜 난연성의 효과를 상승시키는 작용을 한다.
In addition, the composite flame retardant according to the present invention mixes the melamine-based compound as a secondary component, and the melamine-based compound is an alternative flame retardant of the fluorine-based flame retardant, which is problematic because of the theoretical possibility of dioxin generation during combustion. It generates and blocks the oxygen supplied to the synthetic leather, which is a flame retardant material, and suppresses combustion to increase the effect of flame retardancy.
또한 본 발명에서 멜라민계 화합물의 혼합량은 10~12 중량%인 것이 바람직하며, 멜라민계 화합물의 혼합량이 상기에서 한정한 범위 미만으로 혼합될 경우에는 멜라민계 화합물의 혼합량 부족으로 인해 난연소재의 연소시 충분한 불연성 가스가 발생되지 아니하여 난연소재인 합성피혁에 공급되는 산소를 제대로 차단하지 못해 난연성능이 저하할 우려가 있고, 멜라민계 화합물의 혼합량이 상기에서 한정한 범위를 초과할 경우에는 멜라민계 화합물의 혼합량 증가에 비례하여 불연성 가스의 발생량이 증가하나 멜라민계 화합물의 혼합량에 비해 상대적으로 인산에스테르계 화합물의 혼합량이 적어짐에 따라 도리어 난연 성능이 저하되면서 유독가스와 연기의 다량 발생할 우려가 있다.
In addition, in the present invention, the mixing amount of the melamine-based compound is preferably 10 to 12% by weight, and when the mixing amount of the melamine-based compound is mixed below the range defined above, when the flame retardant material is burned due to the lack of the mixing amount of the melamine-based compound. If there is not enough incombustible gas generated, the oxygen supply to synthetic leather, which is a flame retardant material, may not be properly blocked, and the flame retardant performance may be reduced. If the amount of the melamine compound is exceeded, the melamine compound is used. Although the amount of incombustible gas is increased in proportion to the increase in the amount of the mixture, the amount of the phosphate ester compound is relatively lower than the amount of the melamine compound, so that the flame retardant performance is lowered, thereby causing a large amount of toxic gas and smoke.
본 발명에서 사용하는 멜라민계 화합물은 피로인산멜라민염(Melamine Pyrophosphate)인 것이 바람직하다.
The melamine-based compound used in the present invention is preferably melamine pyrophosphate.
그리고 본 발명에서 징크보레이트(ZnBorate, 2ZnO·B2O3·5H20)는 불꽃 및 잔염을 억제시켜 유독가스 및 연기발생을 억제하는 억연(抑煙) 작용을 한다.
In the present invention, zinc borate (ZnBorate, 2ZnO.B 2 O 3 · 5H 2 0) has a depressing effect of suppressing toxic gas and smoke by suppressing flame and residual flame.
또한 징크보레이트의 혼합량은 12~15 중량%인 것이 바람직하며, 징크보레이트의 혼합량이 상기에서 한정한 범위 미만으로 혼합될 경우에는 불꽃 및 잔염을 제대로 억제하지 못해 유독가스 및 연기발생을 억제하는 억연(抑煙) 기능이 저하할 우려가 있고, 징크보레이트의 혼합량이 상기에서 한정한 범위를 초과할 경우에는 징크보레이트의 혼합량에 비해 상대적으로 인산에스테르계 화합물 또는 멜라민계 화합물의 혼합량이 적어짐에 따라 멜라민계 화합물에서 발생되는 불연성가스의 발생량이 적어지거나 또는 불꽃 및 잔염의 발생이 많아짐에 따라 난연 성능이 저하되고, 유독가스 및 연기가 다량 발생할 우려가 있다.
In addition, the mixing amount of the zinc borate is preferably 12 to 15% by weight, and when the mixing amount of the zinc borate is mixed below the range defined above, it does not properly suppress the flame and residual flames and thus suppresses the generation of toxic gas and smoke ( Iii) If there is a possibility that the function decreases, and the mixing amount of the zinc borate exceeds the above-defined range, the melamine type may be reduced as the mixing amount of the phosphate ester compound or the melamine compound is relatively smaller than the mixing amount of the zinc borate. As the amount of incombustible gas generated from the compound decreases or the generation of sparks and residual flames increases, the flame retardant performance is lowered, and there is a possibility that a large amount of toxic gas and smoke are generated.
그리고 본 발명에서 수산화마그네슘은 탈수반응에 의한 흡열 작용에 의해 연소를 지연시키는 작용을 한다.
In the present invention, the magnesium hydroxide acts to delay combustion by the endothermic action by the dehydration reaction.
또한 수산화마그네슘의 혼합량은 3~5 중량%인 것이 바람직하며, 수산화마그네슘의 혼합량이 상기에서 한정한 범위 미만으로 혼합될 경우에는 탈수반응에 의한 흡열 작용 효과가 저하할 우려가 있고, 수산화마그네슘의 혼합량이 상기에서 한정한 범위를 초과할 경우에는 수산화마그네슘의 혼합량의 증가에 비례하여 탈수반응에 의한 흡열 작용 효과가 증가하지 않고, 오히려 다른 구성성분들의 화합물들의 혼합량 부족으로 인해 난연 성능이 저하하거나 또는 유독가스 및 연기가 다량 발생할 우려가 있다.
In addition, it is preferable that the mixing amount of magnesium hydroxide is 3 to 5% by weight, and when the mixing amount of magnesium hydroxide is mixed below the range defined above, there is a possibility that the endothermic effect due to the dehydration reaction may decrease, and the mixing amount of magnesium hydroxide In the case of exceeding the above-defined range, the endothermic effect of the dehydration reaction does not increase in proportion to the increase of the amount of magnesium hydroxide mixed, but rather, the flame retardant performance is deteriorated or toxic due to the insufficient amount of the compound of other components. There is a fear that a large amount of gas and smoke are generated.
그리고 본 발명에서 상기 안정제는 인산에스테르계 화합물과 멜라민계 화합물을 복합 난연제 조성물 내에서 균일하게 분산시켜 안정되게 저장시키는 작용을 한다.
In the present invention, the stabilizer functions to stably disperse the phosphate ester compound and the melamine compound in the composite flame retardant composition.
또한 안정제의 혼합량은 1~2 중량%인 것이 바람직하며, 안정제의 혼합량이 상기에서 한정한 범위 미만으로 혼합될 경우에는 인산에스테르계 화합물과 멜라민계 화합물을 복합 난연제 조성물 내에서 조성물이 균일하도록 안정되게 저장되지 않을 우려가 있고, 안정제의 혼합량이 상기에서 한정한 범위를 초과할 경우에는 안정제 혼합량에 비례하여 안정효과가 증가하지 않으며, 오히려 다른 구성성분들의 화합물들의 혼합량 부족으로 인해 난연 성능이 저하하거나 또는 유독가스 및 연기가 다량 발생할 우려가 있다.
In addition, the mixing amount of the stabilizer is preferably 1 to 2% by weight, and when the mixing amount of the stabilizer is mixed below the range defined above, the phosphate ester compound and the melamine compound may be stably stabilized in the composite flame retardant composition. There is a fear that it will not be stored, if the amount of the stabilizer mixture exceeds the above-defined range, the stabilization effect does not increase in proportion to the amount of stabilizer mixture, but rather the flame retardant performance is deteriorated due to insufficient mixing of the compounds of the other components or There is a risk of generating toxic gases and smoke.
본 발명에서 사용하는 안정제는 입자의 크기가 5~10 ㎛인 나노 클레이인 것이 바람직하며, 입자의 크기가 상기에서 한정한 범위를 벗어날 경우에는 인산에스테르계 화합물과 멜라민계 화합물이 복합 난연제 조성물 내에서의 안정 효과가 저하할 우려가 있다.
The stabilizer used in the present invention is preferably a nano clay having a particle size of 5 to 10 μm, and when the particle size is out of the above-defined range, the phosphate ester compound and the melamine compound may be used in the composite flame retardant composition. There is a fear that the stabilizing effect of the deteriorates.
그리고 본 발명에서 용제의 혼합량은 32~36 중량%인 것이 바람직하며, 용제의 혼합량이 상기에서 한정한 범위 미만으로 혼합될 경우에는 복합 난연제 조성물의 점성이 높아짐에 따라 합성피혁에 복합 난연제 조성물의 도포 작업의 작업성 효율이 저하될 우려가 있고, 난연제의 혼합량이 상기에서 한정한 범위를 초과할 경우에는 용제의 혼합량에 비해 상대적으로 인산에스테르계 화합물과 멜라민계 화합물이나 또는 다른 구성성분들의 화합물들의 혼합량 부족으로 인해 난연 성능이 저하하거나 또는 유독가스 및 연기가 다량 발생할 우려가 있다.
In addition, in the present invention, the mixing amount of the solvent is preferably 32 to 36% by weight, and when the mixing amount of the solvent is mixed below the range defined above, as the viscosity of the composite flame retardant composition increases, the application of the composite flame retardant composition to the synthetic leather If the workability of the work is lowered and the mixing amount of the flame retardant exceeds the range defined above, the mixing amount of the phosphate ester compound and the melamine compound or the compounds of the other components is relatively higher than the mixing amount of the solvent. Due to the lack of flame retardant performance or the toxic gas and smoke may occur a lot.
또한 본 발명에서 사용하는 용제는 디메틸포름아미드(DMF), 톨루엔 또는 메틸에틸케톤(MEK) 중에서 1종 또는 그 이상을 선택하여 사용하는 것이 바람직하다.
The solvent used in the present invention is preferably selected from one or more of dimethylformamide (DMF), toluene or methyl ethyl ketone (MEK).
이하 본 발명의 구성을 하기 실시 예를 통해 상세히 설명하면 다음과 같으며, 본 발명의 구성은 반드시 하기의 실시 예에만 한정하지는 않는다.
Hereinafter, the configuration of the present invention will be described in detail through the following examples, and the configuration of the present invention is not necessarily limited to the following embodiments.
1. 복합 난연제 조성물의 제조1. Preparation of Composite Flame Retardant Composition
인산에스테르계 화합물, 멜라민계 화합물, 징크보레이트(ZnBorate, 2ZnO·B2O3·5H20), 수산화마그네슘, 안정제 및 용제를 사용하여 아래 [표 1]의 조성비에 따라 실시 예 1, 2 및 비교 예 1, 2의 복합 난연제 조성물을 제조하였다.
Example 1, 2 and the phosphorus ester compound, melamine compound, zinc borate (ZnBorate, 2ZnO · B 2 O 3 · 5H 2 0), magnesium hydroxide, stabilizers and solvents according to the composition ratio of the following [Table 1] Composite flame retardant compositions of Comparative Examples 1 and 2 were prepared.
2) 피로인산멜라민염(Melamine Pyrophosphate)
3) 입자의 크기가 5~10 ㎛인 나노 클레이
4) 디메틸포름아미드(DMF)1) Phosphate ester compound having the structure of formula (1) according to the present invention
2) Melamine Pyrophosphate
3) Nanoclay with particle size of 5 ~ 10 ㎛
4) Dimethylformamide (DMF)
2. 복합 난연제 조성물의 평가2. Evaluation of Composite Flame Retardant Composition
상기 [표 1]의 구성성분 및 구성비에 따라 제조한 실시 예 1, 2 및 비교 예 1, 2의 복합 난연제 조성물을 두께가 1mm인 폴리우레탄계 합성피혁에 0.1mm의 두께(건조기준)으로 코팅하여 시험용 시편을 제조한 다음 난연성, 일광견뢰도의 물성을 시험한 결과는 아래 [표 2]의 내용과 같다.
The composite flame retardant compositions of Examples 1 and 2 and Comparative Examples 1 and 2 prepared according to the components and composition ratios of [Table 1] were coated on a polyurethane-based synthetic leather having a thickness of 1 mm with a thickness of 0.1 mm (drying basis). After the test specimens were prepared, the results of testing the properties of flame retardancy and daylight fastness are shown in Table 2 below.
그리고 복합 난연제 조성물의 평가를 위한 시험방법에서 난연성은 KS K 0582(천의 연소도 시험 방법：수평법)에 의해 시험하였으며, 일광견뢰도는 일광견뢰도시험장치(Fade-O-meter)에 폴리우레탄계 합성피혁 시료를 걸어 탄소봉을 태워 나오는 빛이나 Xenon 등에서 나오는 빛(자외선)으로 조사하여 시험하였다. 자외선을 시험용 시편에 조사하여 5시간이 지난 후 원래의 색에서 변화가 감지되면 1급, 10시간 쪼여서 변화가 감지되면 2급, 20시간은 3급, 40시간은 4급, 80시간은 5급, 160시간에도 변화가 감지되지 않으면 6급이라고 한다.
In the test method for evaluating the composite flame retardant composition, the flame retardancy was tested by KS K 0582 (Combustion Test Method of Horizontal: Horizontal Method), and the daylight fastness was synthesized by polyurethane in a Fade-O-meter. The leather samples were tested by irradiating with light emitted from carbon rods or light emitted from Xenon (ultraviolet). After 5 hours of irradiation with UV light on the test specimen, if a change in the original color is detected, it is classified as Class 1, 10 hours.If a change is detected, Class 2, 20 hours are Class 3, 40 hours are Class 4, 80 hours are 5 If no change is detected in class and 160 hours, it is called class 6.
상기 [표 2]에 나타난 바와 같이, 실시 예 1, 2는 비교 예 1, 2에 비해 난연성이 우수하고, 일광견뢰도의 성능은 동등한 것으로 평가되었다. 비교 예 1의 경우에는 실시 예 1, 2에 비해 인산에스테르계 화합물과 멜라민계 화합물의 혼합량이 더 많이 혼합되었음에도 불구하고, 징크보레이트가 혼합되지 않아 난연성 시험에서 불꽃과 잔염을 제대로 억제하지 못해 실시 예 1, 2에 비해 난연성이 떨어지는 것으로 추정되며, 비교 예 2의 경우에는 실시 예 1, 2에 비해 인산에스테르계 화합물과 멜라민계 화합물의 혼합량이 더 많이 혼합되었지만 징크보레이트와 수산화마그네슘이 실시 예 1, 2에 비해 적게 혼합됨에 따라 징크보레이트의 불꽃과 잔염의 억제 작용과 수산화마그네슘의 흡열 작용이 저하하여 실시 예 1, 2에 비해 난연성이 떨어지는 것으로 추정된다.
As shown in Table 2, Examples 1 and 2 were superior in flame retardancy compared to Comparative Examples 1 and 2, and the performance of daylight fastness was evaluated to be equivalent. In the case of Comparative Example 1, although the mixing amount of the phosphate ester compound and the melamine compound was higher than that of Examples 1 and 2, the zinc borate was not mixed so that the flame and the residual flame were not properly suppressed in the flame retardant test. It is estimated that the flame retardancy is inferior to that of 1 and 2, and in Comparative Example 2, although the mixed amount of the phosphate ester compound and the melamine compound was mixed more than that of Examples 1 and 2, zinc borate and magnesium hydroxide were used in Example 1, It is estimated that the amount of flame retardancy is lower than that of Examples 1 and 2 due to the decrease of the mixing and the inhibition of the flame and afterflaming of zinc borate and the endothermic action of magnesium hydroxide.
그리고 상기 [표 1]의 내용과 같이 구성성분과 구성비가 상이함에도 실시 예 1, 2 및 비교 예 1, 2의 일광견뢰도의 성능에 있어서는 그 성능이 대등한 것이 확인되었다.
And as shown in the said Table 1, although the component and the composition ratio differ, it was confirmed that the performance was the same in the performance of the daylight fastness of Example 1, 2 and Comparative Examples 1, 2.
상기의 평가 결과에 따르면, 본 발명에 따른 복합 난연제 조성물은 주난연제인 인산에스테르계 화합물과 멜라민계 화합물의 난연성도 중요하지만 이 난연성의 기능을 보조하는 징크보레이트와 수산화마그네슘의 혼합량도 난연 성능에 미치는 영향이 큰 것을 확인할 수 있었다.
According to the above evaluation results, the composite flame retardant composition according to the present invention is important for the flame retardancy of the phosphate ester compound and the melamine compound as the main flame retardant, but the amount of zinc borate and magnesium hydroxide that assists the flame retardant function also affects the flame retardant performance. The influence was large.
상기에서 설명 드린 바와 같이 본 발명은 상기의 실시 예를 통해 그 물성의 우수성이 입증되었지만 본 발명은 상기의 실시 예에 의해서만 반드시 한정되는 것이 아니고, 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 여러 가지 치환, 변형 및 변경이 가능하다.As described above, the present invention has been proven to be superior in physical properties through the above embodiments, but the present invention is not necessarily limited only to the above embodiments, and various modifications may be made without departing from the technical spirit of the present invention. Substitutions, modifications and variations are possible.
Claims (6)
34 to 38 wt% of phosphate ester compounds, 10 to 12 wt% of melamine compounds, 12 to 15 wt% of zinc borate (ZnBorate, 2ZnO · B 2 O 3 · 5H 2 0), magnesium hydroxide 3 to 5 wt%, stabilizer Eco-friendly composite flame retardant composition for polyurethane synthetic leather coating, characterized in that composed of 1 to 2% by weight and 32 to 36% by weight of the solvent.
상기 인산에스테르계 화합물은 아래 화학식 (1)과 같은 구조인 것을 특징으로 하는 폴리우레탄 합성피혁 코팅용 친환경 복합 난연제 조성물.
The method of claim 1,
The phosphate ester compound is an environmentally friendly composite flame retardant composition for polyurethane synthetic leather coating, characterized in that the structure as shown in the formula (1) below.
상기 멜라민계 화합물은 피로인산멜라민염(Melamine Pyrophosphate)인 것을 특징으로 하는 폴리우레탄 합성피혁 코팅용 친환경 복합 난연제 조성물.
The method of claim 1,
The melamine-based compound is an eco-friendly composite flame retardant composition for polyurethane synthetic leather coatings, characterized in that the melamine pyrophosphate (Melamine Pyrophosphate).
상기 안정제는 나노 클레이인 것을 특징으로 하는 폴리우레탄 합성피혁 코팅용 친환경 복합 난연제 조성물.
The method of claim 1,
The stabilizer is an environmentally friendly composite flame retardant composition for polyurethane synthetic leather coating, characterized in that the nano clay.
상기 용제는 디메틸포름아미드(DMF), 톨루엔 또는 메틸에틸케톤(MEK) 중에서 1종 또는 그 이상을 선택하여 사용하는 것을 특징으로 하는 폴리우레탄 합성피혁 코팅용 친환경 복합 난연제 조성물.
The method of claim 1,
The solvent is an environment-friendly composite flame retardant composition for polyurethane synthetic leather coating, characterized in that one or more selected from dimethylformamide (DMF), toluene or methyl ethyl ketone (MEK).
상기 나노 클레이는 입자의 크기가 5~10 ㎛인 것을 특징으로 하는 폴리우레탄 합성피혁 코팅용 친환경 복합 난연제 조성물. The method of claim 4, wherein
The nano clay is an eco-friendly composite flame retardant composition for polyurethane synthetic leather coating, characterized in that the particle size of 5 ~ 10 ㎛.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000160031A (en) | 1998-12-01 | 2000-06-13 | Chisso Corp | Flame retardant thermoplastic resin composition |
| KR20010057665A (en) * | 1999-12-23 | 2001-07-05 | 성재갑 | Flame resistant thermoplastic polybutylene terephthalate resin compositions |
| KR20050075688A (en) * | 2004-01-16 | 2005-07-21 | 다이쿄 케미칼 컴퍼니, 리미티드 | Flame-retardant metal-coated cloth |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000160031A (en) | 1998-12-01 | 2000-06-13 | Chisso Corp | Flame retardant thermoplastic resin composition |
| KR20010057665A (en) * | 1999-12-23 | 2001-07-05 | 성재갑 | Flame resistant thermoplastic polybutylene terephthalate resin compositions |
| KR20050075688A (en) * | 2004-01-16 | 2005-07-21 | 다이쿄 케미칼 컴퍼니, 리미티드 | Flame-retardant metal-coated cloth |
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