KR100732781B1 - Uncombustible polyurethan resin for synthetic leather and manufacturing method thereof - Google Patents
Uncombustible polyurethan resin for synthetic leather and manufacturing method thereof Download PDFInfo
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- 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
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- 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
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- 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
- C08G18/3203—Polyhydroxy compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
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- C08K5/00—Use of organic ingredients
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- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
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Abstract
본 발명은 난연성 합성피혁용 폴리우레탄 수지 및 그 제조방법에 관한 것이다. The present invention relates to a polyurethane resin for flame retardant synthetic leather and a method of manufacturing the same.
본 발명에 따른 난연성 합성피혁용 폴리우레탄 수지는 폴리우레탄의 주왜에 난연성분인 인산 에스테르 디올을 포함하는 것을 특징으로 하여 종래의 방식의 부작용인 비산 및 후공정의 작업능률 저하 등을 일으키지 않으면서도 뛰어난 난연성을 갖는다. The polyurethane resin for flame retardant synthetic leather according to the present invention is characterized in that it contains a phosphate ester diol which is a flame retardant component in the main strain of polyurethane, and is excellent even without causing side effects of conventional methods such as scattering and deterioration of work efficiency of a post process. It is flame retardant.
본 발명에 따른 난연성 합성피혁용 폴리우레탄 수지의 제조방법은 폴리우레탄 중합의 사슬연장반응에서 사슬연장제로서 1,4-부탄디올과 난연성분인 인산 에스테르 디올을 혼합하여 반응시킴으로써 난연제를 첨가하는 추가공정을 필요로 하지 않아 경제적으로 유리하다.The method for preparing a polyurethane resin for flame retardant synthetic leather according to the present invention is an additional step of adding a flame retardant by mixing and reacting 1,4-butanediol as a chain extender and a phosphate ester diol as a flame retardant component in a chain extension reaction of polyurethane polymerization. It does not need to be economically advantageous.
본 발명에 따른 난연제가 첨가된 합성피혁용 폴리우레탄 수지의 제조방법은 상기 합성피혁용 폴리우레탄 수지를 이용함으로써 소량의 난연제만을 첨가하여 부작용을 일으키지 않으면서도 난연성을 현저히 증가시킨다.The method for preparing a polyurethane resin for synthetic leather added with a flame retardant according to the present invention significantly increases flame retardancy without causing side effects by adding only a small amount of flame retardant by using the polyurethane resin for synthetic leather.
인산 에스테르 디올, 난연성, 합성피혁, 폴리우레탄 Phosphate ester diol, flame retardant, synthetic leather, polyurethane
Description
도 1은 본 발명인 인공피혁용 폴리우레탄 수지의 제조방법의 공정도이다.1 is a process chart of the manufacturing method of the polyurethane resin for artificial leather of the present invention.
본 발명은 합성피혁을 제조하는 데 있어 코팅제로 사용되는 폴리우레탄 수지의 난연성을 향상시킨 합성피혁용 폴리우레탄 수지와 그 제조방법에 관한 것이다. 더욱 상세하게는 폴리우레탄의 중합과정에서 난연성을 갖는 단량체를 사용하여 주쇄에 삽입함으로써, 난연성능을 개선하기 위한 것이다.The present invention relates to a polyurethane resin for synthetic leather and a method for producing the same that improve the flame retardancy of the polyurethane resin used as a coating agent in the production of synthetic leather. More specifically, by inserting into the main chain using a monomer having a flame retardancy during the polymerization of polyurethane, it is to improve the flame retardant performance.
폴리우레탄 수지는 비교적 저렴하고 성형이 용이하여 생활 용품 전반에 걸쳐 널리 사용되고 있으며, 특히 합성피혁제품의 중요한 재료이다. 그러나, 폴리우레탄 수지는 가연성이며, 발화시 연소의 제어가 어렵기 때문에 난연성의 부여가 중요하며 특히, 자동차 내장제 등 사용 특성상 난연성의 부가가 반드시 필요한 일부 분야에서는 법률로 난연화가 의무화되어 있다.Polyurethane resins are relatively inexpensive and easy to mold and are widely used throughout household goods, and are particularly important materials for synthetic leather products. However, since polyurethane resins are flammable and it is difficult to control combustion during ignition, imparting flame retardancy is important, and in particular, in some fields in which the use of flame retardant is necessary due to the characteristics of use such as automobile interiors, fire retardancy is mandated by law.
합성피혁용 폴리우레탄의 난연성을 부여하기 위한 일반적인 방법으로는 코팅을 위한 폴리우레탄 배합액의 배합시, 트리아릴포스페이트 등의 인계 난연제 또는할로겐계 난연제를 일정량 첨가하는 방법이 이용되고 있다. As a general method for imparting flame retardancy of a synthetic leather polyurethane, a method of adding a predetermined amount of a phosphorus flame retardant such as triaryl phosphate or a halogen flame retardant when compounding a polyurethane compound for coating is used.
그러나, 상기의 방법에 의한 경우 문제점들이 상당히 있다. 일례로써, 시간의 경과에 따라 난연제가 수분을 흡수하여 제품의 봉제 등 후가공에서 작업능률을 심각하게 저하시키거나, 원단의 색상을 변하게 한다. 또, 이들 난연제는 분자량이 작아 여름철 등 자동차 내부의 온도가 상승할 경우, 비산되어 제품의 난연성이 저하되며, 할로겐화 수소 등 인체에 유해한 성분을 배출하기도 한다.However, there are significant problems with the above method. As an example, the flame retardant absorbs moisture over time to seriously reduce the work efficiency or to change the color of the fabric in post-processing such as sewing of the product. In addition, these flame retardants are small in molecular weight, when the temperature inside the car, such as in the summer rises, they are scattered and the flame retardancy of the product is lowered, and sometimes harmful components such as hydrogen halides are emitted.
상기의 문제점을 해결하기 위한 본 발명의 목적은 난연특성을 영구적으로 유지하며, 환경공해를 일트키지 않는 합성피혁용 폴리우레탄 수지를 제공하는 것이다.An object of the present invention for solving the above problems is to provide a polyurethane resin for synthetic leather that maintains flame retardant properties permanently, does not cause environmental pollution.
본 발명의 다른 목적은 이러한 합성피혁용 폴리우레탄 수지의 제조방법을 제공하는 것이다. Another object of the present invention is to provide a method for producing a polyurethane resin for synthetic leather.
본 발명의 또다른 목적은 더 높은 난연성이 요구되어 난연제를 첨가하여야 할 경우 물성의 저하 또는 후공정의 장애가 발생하지 않으면서도 높은 난연성을 얻을 수 있는 최적의 첨가비를 제공하는 것이다.It is another object of the present invention to provide an optimum addition ratio that can achieve high flame retardance without requiring deterioration of physical properties or failure of a post process when higher flame retardancy is required and a flame retardant should be added.
본 발명은 이소시아네이트기(-OCN)와 히드록시(-OH)가 결합한 우레탄 구조 및 인산계 에스테르를 포함하여 구성되는 것을 특징으로 하는 합성피혁용 난연폴리우레탄수지와 그 제조 방법에 관한 것이다.The present invention relates to a flame retardant polyurethane resin for synthetic leather and a method for producing the same, comprising a urethane structure and a phosphoric acid ester in which an isocyanate group (-OCN) and hydroxy (-OH) are bonded.
본 발명의 폴리우레탄의 중합과정은 폴리올과 디이소시아네이트를 반응시켜 프리폴리머(전구체)를 얻는 제1중합단계 및 프리폴리머를 저분자량의 활성수소를 갖는 화합물(사슬연장제)과 반응시켜 중합도를 높이는 제2중합단계로 구성된다.In the polymerization process of the polyurethane of the present invention, a first polymerization step of reacting a polyol and a diisocyanate to obtain a prepolymer (precursor) and a second polymerization of the prepolymer with a compound having a low molecular weight active hydrogen (chain extender) to increase the degree of polymerization It consists of a polymerization step.
다른 본 발명은 상기 폴리우레탄 수지로 인공피혁을 제조하는 과정에서 인계 난연제와 브롬계 난연제를 혼합 첨가함으로써 인공피혁제품의 난연성능을 향상시키는 것이다.Another embodiment of the present invention is to improve the flame retardant performance of the artificial leather product by mixing the phosphorus-based flame retardant and bromine-based flame retardant in the process of manufacturing artificial leather with the polyurethane resin.
이하에서는 첨부된 도면을 참고로 하여 본 발명의 기술적 특징을 상세하게 설명하기로 한다. 본 발명은 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며, 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.Hereinafter, with reference to the accompanying drawings will be described in detail the technical features of the present invention. The invention can be better understood by the examples, the following examples are for the purpose of illustrating the invention and are not intended to limit the scope of protection defined by the appended claims.
도 1에 나타난 바와 같이 본 발명은 제1중합단계(S 10) 및 제2중합단계(S 20)를 포함한다.As shown in FIG. 1, the present invention includes a first polymerization step S 10 and a second polymerization step S 20.
먼저, 본 발명은 폴리올과 디이소시아네이트가 반응하는 제1중합단계를 포함한다(S 10). 특히, 이소시아네이트기와 히드록시기는 축합반응을 하여 우레탄 결합을 형성하는데 과량의 디이소시아네이트를 반응시킴으로써 양말단에 이소시아네이트기를 갖는 프리폴리머를 얻는다. 제품의 탄성, 촉감 등을 고려시, 폴리올과 디이소시아네이트기의 몰비는 1:4인 것이 바람직하다. 상기 중합단계는 폴리올과 디이소시아네이트를 디메틸포름알데히드 등의 유기용제에 용해하여 용액반응시키는 것이 일반적이다.First, the present invention includes a first polymerization step in which a polyol and a diisocyanate react (S 10). In particular, an isocyanate group and a hydroxyl group are condensed to form a urethane bond, and an excess of diisocyanate is reacted to obtain a prepolymer having an isocyanate group at the sock end. In consideration of the elasticity, feel, and the like of the product, the molar ratio of the polyol and the diisocyanate group is preferably 1: 4. In the polymerization step, polyol and diisocyanate are generally dissolved in an organic solvent such as dimethylformaldehyde and solution-reacted.
상기 폴리올은 폴리카보네이트 디올과 폴리테트라메틸렌에테르글리콜이 혼합된 것을 사용하며 수평균분자량이 1000~3000인 것이 바람직하다.The polyol may be a mixture of polycarbonate diol and polytetramethylene ether glycol, and the number average molecular weight is preferably 1000 to 3000.
디이소시아네이트 화합물로서는 파라페닐 디이소시아네이트, 메타페닐렌 디이소시아네이트, 2,4-토리렌 디이소시아네이트, 2,6-토리렌 디이소시아네이트, 1-클로로-2,1-페닐렌 디이소시아네이트, 1,5-나프탈렌 디이소시아네이트, 1,4-페닐렌 디이소시아네이트, 클로로페닐렌-2,4'-디이소시아네이트, 메틸렌비스-4-페닐디이소시아내이트, 헥사메틸렌 디이소시아네이트, 폴리메틸렌폴리페닐 디이소시아네이트, 메틸사이클로헥시렌 디이소시아네이트, 파라페닐 디이소시아네이트, 파라페닐렌 디이소시아네이트, 4,4'-디페닐이소프로필리딘 디이소시아네이트, 3,3'-디메틸-4, 4'-디페닐 디이소시아네이트, 3,3'-디메톡시-4,4'-디페닐렌 디이소시아네이트, 메틸렌디페닐디이소시아네이트 등으로 이루어진 군에서 하나 이상 선택될 수 있으며, 폴리올과의 반응성과 최종제품의 물성을 고려시, 메틸렌디페닐디이소시아네이트(MDI)가 가장 바람직하다. As the diisocyanate compound, paraphenyl diisocyanate, metaphenylene diisocyanate, 2,4-torylene diisocyanate, 2,6-torylene diisocyanate, 1-chloro-2,1-phenylene diisocyanate, 1,5- Naphthalene diisocyanate, 1,4-phenylene diisocyanate, chlorophenylene-2,4'-diisocyanate, methylenebis-4-phenyldiisocyanate, hexamethylene diisocyanate, polymethylenepolyphenyl diisocyanate, methylcyclo Hexylene diisocyanate, paraphenyl diisocyanate, paraphenylene diisocyanate, 4,4'-diphenylisopropylidine diisocyanate, 3,3'-dimethyl-4, 4'-diphenyl diisocyanate, 3,3 ' At least one selected from the group consisting of -dimethoxy-4,4'-diphenylene diisocyanate, methylenediphenyl diisocyanate, and the like. Given the physical properties of the final product, methylene diphenyl diisocyanate (MDI) is most preferred.
이어서 본 발명은 1단계에서 생성된 양단에 이소시아네이트기를 갖는 프리폴리머를 1,4-부탄디올과 인산 에스테르 디올이 혼합된 사슬연장제와 반응시키는 제2 중합단계(S 20)를 포함한다. 상기 반응을 통하여 폴리우레탄이 완성된다.Next, the present invention includes a second polymerization step (S 20) of reacting a prepolymer having an isocyanate group at both ends generated in step 1 with a chain extender mixed with 1,4-butanediol and phosphate ester diol. The polyurethane is completed through the reaction.
상기 반응단계는 1단계에서 수득된 프리폴리머를 1,4 부탄디올과 인산 에스테르 디올의 혼합물과 디메틸포름알데히드 등 유기용제를 가하여 일정온도에서 일정시간 반응시켜 폴리우레탄 중합체를 얻는다 .In the reaction step, the prepolymer obtained in step 1 is added with a mixture of 1,4 butanediol and phosphate ester diol, and an organic solvent such as dimethylformaldehyde to react at a predetermined temperature for a predetermined time to obtain a polyurethane polymer.
상기 1,4-부탄디올과 인산 에스테르 디올의 비는 97:3 내지 93:7인 것이 바람직하다. 이 이하일 경우 충분한 난연 효과를 얻을 수 없고, 이 이상일 경우, 인공피혁의 촉감이 나빠지며, 사슬연장반응이 충분히 진행되지 않는다.It is preferable that the ratio of the said 1, 4- butanediol and phosphate ester diol is 97: 3-93: 7. If less than this, sufficient flame retardant effect is not obtained, and if it is more than this, the touch of artificial leather worsens, and the chain extension reaction does not proceed sufficiently.
상기 인산 에스테르 디올은 수산기를 갖는 난연성 성분이며 프리폴리머의 이소시아네이트기와 반응하여 폴리우레탄 수지의 골격 내에 삽입되기 때문에, 이후 외부 환경에 의하여 비산되지 않는다.The phosphate ester diol is a flame-retardant component having a hydroxyl group and is reacted with an isocyanate group of the prepolymer to be inserted into the skeleton of the polyurethane resin, which is then not scattered by the external environment.
상기 인산 에스테르의 산가는 2KOHmg/g 이하가 바람직하다. 이것을 초과하면 촉매활성을 잃게 되어 이소시아네이트기와의 반응성이 현저히 저하된다.As for the acid value of the said phosphate ester, 2KOHmg / g or less is preferable. If it exceeds this, catalytic activity will be lost, and reactivity with an isocyanate group will fall remarkably.
난연제를 첨가한 합성피혁용 폴리우레탄 수지의 제조방법은 상기방법에 의하여 중합된 폴리우레탄 수지에 인계 난연제 및 브롬계 난연제를 각각 0.5 내지 1.5중량부 첨가한 다음 유기용제를 가하여 액상의 코팅용 폴리우레탄 수지를 얻는 단계를 포함한다. The method for producing a polyurethane resin for synthetic leather with a flame retardant is added to the polyurethane resin polymerized according to the above method by adding 0.5 to 1.5 parts by weight of a phosphorus flame retardant and a bromine flame retardant, respectively, and then adding an organic solvent to the liquid coating polyurethane. Obtaining a resin.
상기 단계에서는 균일한 액상수지를 얻기 위하여 교반기를 이용하여 교반하는 것이 바람직하다.In this step, it is preferable to use a stirrer to obtain a uniform liquid resin.
하기의 실시예는 본 발명의 효과와 최적의 조성비를 알아보기 위한 것이다.The following example is to find the effect and the optimum composition ratio of the present invention.
[실시예 1]Example 1
수평균 분자량 2000의 폴리카보네이트디올과 수평균 분자량 2000의 폴리테트라메틸렌에테르글리콜이 중량비 1.5:1로 혼합된 폴리올 혼합물을 교반하여 약 70℃로 유지시킨 다음, 폴리올 혼합물에 메틸렌디페닐디이소시아네이트를 첨가하여 약 30분 동안 반응시킨 후 수세하여 고형의 프리폴리머를 얻는다. (상기 폴리올 혼합물과 메틸렌디페닐이소시아네이트의 몰비는 1:4이다.)A polyol mixture, in which a polycarbonate diol having a number average molecular weight of 2000 and a polytetramethylene ether glycol having a number average molecular weight of 2000, was mixed at a weight ratio of 1.5: 1, was stirred and maintained at about 70 ° C, and then methylenediphenyl diisocyanate was added to the polyol mixture. Reaction for about 30 minutes and then washed with water to obtain a solid prepolymer. (The molar ratio of the polyol mixture and methylenediphenylisocyanate is 1: 4.)
상기 프리폴리머에 디메틸포름아미드를 가하여 용해시키고 몰비가 97:3인 1,4-부탄디올과 하기 화학식 1의 인산 에스테르 디올(분자량 360)의 혼합물을 사슬연장제로 투입하여 65 내지 70℃에서 30분 동안 반응시킨 후 수세하여 고형의 폴리우레탄 수지를 합성하였다. (상기 폴리올 혼합물과 사슬연장제의 몰비는 1:3이다.) Dimethylformamide was added to the prepolymer to dissolve it, and a mixture of 1,4-butanediol having a molar ratio of 97: 3 and phosphate ester diol (molecular weight 360) represented by the following Formula 1 was added as a chain extender to react at 65 to 70 ° C. for 30 minutes. After washing with water, a solid polyurethane resin was synthesized. (The molar ratio of the polyol mixture and chain extender is 1: 3.)
<화학식 1><Formula 1>
(상기 화학식 1에서 R1은 C2~C4의 알킬기, R2은 C2~C4의 알킬렌기,R3은 C2~C4의 알킬렌기, m과 n은 각각 1~10의 정수이다.)(The alkyl group in the formula 1 R 1 is C 2 ~ C 4, R 2 is C 2 ~ C 4 alkylene group, R 3 a is a C 2 ~ C 4 alkylene group, m and n is an integer of 1 to 10, respectively to be.)
[실시예 2]Example 2
실시예 1의 방법 중 1,4-부탄디올과 인산 에스테르 디올의 몰비를 95:5로 하여 실시예 1과 동일한 방법으로 폴리우레탄 수지를 합성하였다. Polyurethane resin was synthesize | combined by the method similar to Example 1, with the molar ratio of 1, 4- butanediol and phosphate ester diol in the method of Example 1 being 95: 5.
[실시예 3]Example 3
실시예 1의 방법 중 1,4-부탄디올과 인산 에스테르 디올의 몰비를 93:7로 하여 실시예 1과 동일한 방법으로 폴리우레탄 수지를 합성하였다. The polyurethane resin was synthesize | combined by the method similar to Example 1, with the molar ratio of 1, 4- butanediol and phosphate ester diol being 93: 7 in the method of Example 1.
[실시예 4]Example 4
실시예 1의 방법 중 1,4-부탄디올과 인산 에스테르 디올의 몰비를 9:1로 하여 실시예 1과 동일한 방법으로 폴리우레탄 수지를 합성하였다. A polyurethane resin was synthesized in the same manner as in Example 1, with a molar ratio of 1,4-butanediol and phosphate ester diol being 9: 1 in the method of Example 1.
[실시예 5]Example 5
실시예 1의 방법 중 1,4-부탄디올과 인산 에스테르 디올의 몰비를 7:3로 하여 실시예 1과 동일한 방법으로 폴리우레탄 수지를 합성하였다. A polyurethane resin was synthesized in the same manner as in Example 1, with a molar ratio of 1,4-butanediol and phosphate ester diol being 7: 3 in the method of Example 1.
[실시예 6]Example 6
실시예 1의 방법 중 사슬연장제는 1,4-부탄디올을 사용하고 테트라브로모비 스페놀 아민을 메틸렌디페닐디이소시아네이트에 대하여 3몰% 첨가하여 실시예 1과 동일한 방법으로 폴리우레탄 수지를 합성하였다. In the method of Example 1, a chain extender was used to synthesize a polyurethane resin in the same manner as in Example 1 by using 1,4-butanediol and adding 3 mol% of tetrabromobisphenol amine to methylenediphenyl diisocyanate. .
[실시예 7]Example 7
실시예 1로 합성된 폴리우레탄 수지에 트리아릴포스페이트를 1 중량부 첨가하였다. 1 part by weight of triaryl phosphate was added to the polyurethane resin synthesized in Example 1.
[실시예 8]Example 8
실시예 1로 합성된 폴리우레탄 수지에 트리아릴포스페이트를 3 중량부 첨가하였다. 3 parts by weight of triaryl phosphate was added to the polyurethane resin synthesized in Example 1.
[실시예 9]Example 9
실시예 1로 합성된 폴리우레탄 수지에 트리아릴포스페이트 1 중량부, 트리브로모페놀(TBP) 1 중량부를 첨가하였다. 1 part by weight of triarylphosphate and 1 part by weight of tribromophenol (TBP) were added to the polyurethane resin synthesized in Example 1.
[실시예 10]Example 10
실시예 1로 합성된 폴리우레탄 수지에 트리아릴포스페이트 1.5 중량부, 트리브로모페놀(TBP) 1.5 중량부를 첨가하였다. 1.5 parts by weight of triarylphosphate and 1.5 parts by weight of tribromophenol (TBP) were added to the polyurethane resin synthesized in Example 1.
[비교예][Comparative Example]
실시예 1의 방법 중 인산계 에스테르 디올을 첨가하지 않고, 전체 사슬연장제를 1,4-부탄디올로 하여 합성하였다. The total chain extender was synthesized as 1,4-butanediol without adding the phosphoric acid ester diol in the method of Example 1.
상기 폴리우레탄 수지를 디메틸포름알데히드 40중량부와 혼합하여 만든 배합액을 원단에 0.15mm 도포하여 시험용 시편을 제조한 후, KS K 0583에 의거하여 난연성능테스트를 한후 하기의 결과를 얻었다.After applying the formulation prepared by mixing the polyurethane resin with 40 parts by weight of dimethylformaldehyde was applied 0.15mm to the fabric to prepare a test specimen, the flame retardant performance test according to KS K 0583 and the following results were obtained.
표 1 : 각 실시예의 난연성능Table 1: Flame Retardant Performance of Each Example
상기 표를 통하여 알 수 있듯이,As can be seen from the table above,
실시예 1에서 3까지는 이관능성의 난연물질을 사슬연장제로 한 경우이나 실시예 4의 경우는 일관능성의 난연물질을 반응종결제로 사용한 경우로써, 난연성의 증가가 미약했다.In Examples 1 to 3, when the difunctional flame retardant material was used as the chain extender, and in the case of Example 4, when the flame retardant material having the uniform function was used as the reaction terminator, the increase in the flame retardancy was slight.
실시예 5에서 8까지는 난연성의 보강을 위하여 첨가형 폴리우레탄 수지에 난연제를 첨가한 경우로서 난연성능의 보강에 효과적이었다. Examples 5 to 8 were effective in reinforcing the flame retardant performance when a flame retardant was added to the additive-type polyurethane resin to reinforce the flame retardancy.
이 외에 난연제의 총함량을 5중량부 이상으로 한 경우는 원단에 도포하는 과정에서 균일성이 저하되었다.In addition, in the case where the total content of the flame retardant was 5 parts by weight or more, the uniformity was lowered during the process of coating the fabric.
이상에서 설명한 바와 같이 본 발명에 따른 합성피혁용 폴리우레탄 수지는 폴리우레탄을 중합하는 과정에서 난연성을 갖는 난연성분인 인산 에스테르 디올을 주쇄에 도입함으로써 난연제가 비산되어 난연성능이 저하되거나 인체에 유해한 영향을 끼치는 것을 방지할 수 있다. As described above, the polyurethane resin for synthetic leather according to the present invention introduces a flame retardant component, phosphate ester diol, which is flame retardant in the process of polymerizing polyurethane, into the main chain, so that the flame retardant is scattered and the flame retardant performance is deteriorated or harmful to the human body. Can be prevented.
또, 별도의 난연제를 첨가할 필요가 없기 때문에 경제적으로 유리하며 후공정에서 난연제에 의하여 작업능률이 저하되는 것을 방지할 수 있다. In addition, since it is not necessary to add a separate flame retardant, it is economically advantageous and can prevent the work efficiency from being lowered by the flame retardant in a later process.
또, 더 높은 난연성이 요구되는 경우에 난연제의 첨가를 최소화하여 난연제의 첨가로 인한 부작용을 최소화할 수 있다. In addition, when higher flame retardancy is required, the addition of the flame retardant can be minimized, thereby minimizing the side effects due to the addition of the flame retardant.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3945954A (en) | 1974-01-11 | 1976-03-23 | Uniroyal, Inc. | Flame retardant polyurethanes from polymeric halogenated organo phosphorous diols |
| US5100999A (en) | 1988-09-06 | 1992-03-31 | Daicel Chemical Industries, Ltd. | Polycarbonatediol composition and polyurethane resin |
| JP3334295B2 (en) | 1993-11-30 | 2002-10-15 | 大日本インキ化学工業株式会社 | Method for producing polyurethane resin |
| KR20040071654A (en) * | 2003-02-06 | 2004-08-12 | 가부시키가이샤 구라레 | Stretchable leather-like sheet substrate and process for producing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3945954A (en) | 1974-01-11 | 1976-03-23 | Uniroyal, Inc. | Flame retardant polyurethanes from polymeric halogenated organo phosphorous diols |
| US5100999A (en) | 1988-09-06 | 1992-03-31 | Daicel Chemical Industries, Ltd. | Polycarbonatediol composition and polyurethane resin |
| JP3334295B2 (en) | 1993-11-30 | 2002-10-15 | 大日本インキ化学工業株式会社 | Method for producing polyurethane resin |
| KR20040071654A (en) * | 2003-02-06 | 2004-08-12 | 가부시키가이샤 구라레 | Stretchable leather-like sheet substrate and process for producing same |
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