KR100343546B1 - Non-yellowing polyurethane resin - Google Patents
Non-yellowing polyurethane resin Download PDFInfo
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- KR100343546B1 KR100343546B1 KR1019940039815A KR19940039815A KR100343546B1 KR 100343546 B1 KR100343546 B1 KR 100343546B1 KR 1019940039815 A KR1019940039815 A KR 1019940039815A KR 19940039815 A KR19940039815 A KR 19940039815A KR 100343546 B1 KR100343546 B1 KR 100343546B1
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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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
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
Abstract
Description
본 발명은 무황변형 폴리우레탄 수지에 관한 것으로서, 더욱 상세하게는 폴리올 등의 원료 성분과 그 함량을 적절히 선택 조절함으로써 최종제품이 실내외의 가시광선 및 자외선 등의 빛에 노출되었을 때 수지로 이하여 황변되는 현상을 방지함으로써 신발용 접착제 및 백색 잉크용 바인더로 유용하게 사용할 수 있는 무황변형 폴리우레탄 수지에 관한 것이다.The present invention relates to a non-yellowing polyurethane resin, and more particularly, by adjusting the raw material components and content thereof, such as polyols appropriately, when the final product is exposed to light such as visible and ultraviolet rays, such as indoors and outdoors, the resin yellowing The present invention relates to a non-yellowing polyurethane resin that can be usefully used as a shoe adhesive and a white ink binder by preventing the phenomenon.
일반적으로 사용되는 우레탄계 신발용 접착제 및 백색 잉크용 바인더는 최종제품이 빛에 노출되었을 때 황변되는 현상이 일어나고, 황변현상을 방지하기 위하여 특별한 첨가제, 예를들면 산화방지제와 자외선 안정제 등을 사용하거나 특별한 원료 성분을 사용하기도 하는데, 이 경우 결과적으로 황변현상이 일어나고 설령, 황변되지 않는다 하더라도 기계적 강도 등이 약화되는 문제가 있다.In general, urethane-based shoe adhesives and binders for white ink are yellowed when the final product is exposed to light, and special additives such as antioxidants and UV stabilizers are used to prevent yellowing. In some cases, raw material components may be used, but in this case, yellowing may occur, and even if not yellowed, mechanical strength may be weakened.
따라서, 본 발명자들은 상기 종래기술의 문제점을 해결하기 위하여 폴리우레탄 수지 제조시 원료성분의 종류 및 함량을 적절히 선택 조절함으로써 내황변성, 기계적 강도, 수지의 광택, 용매에 대한 용해성, 접착력 등이 우수한 무황변형 폴리우레탄 수지를 개발함으로써 본 발명을 완성하였다.Therefore, the inventors of the present invention to solve the problems of the prior art by appropriately adjusting the type and content of the raw material components in the production of sulfur resistance, mechanical strength, gloss of the resin, solubility in solvents, adhesive strength, etc. The present invention has been completed by developing a modified polyurethane resin.
본 발명은 새로운 조성으로서, 내황변성 및 용해성 등 제반물성이 우수한 무황변형 폴리우레탄 수지를 제공하는 데 그 목적이 있다.An object of the present invention is to provide a sulfur-free polyurethane resin having excellent general properties such as yellowing resistance and solubility as a new composition.
본 발명은 폴리올, 폴리이소시아네이트, 단쇄글리콜과 촉매 및 중합용매로 이루어진 무황변형 폴리우레탄 수지에 있어서, 상기 폴리올은 분자량이 400 ~ 1000이며, 폴리이소시아네이트는 폴리올과 단쇄글리콜의 합량 1 몰을 기준으로 0.85 ~ 1.05 몰비 범위를 유지하고, 폴리이소시아네이트는 폴리올 1 몰을 기준으로 1.03 ~ 1.3 몰비 범위로 이루어진 것을 그 특징으로 한다.The present invention provides a polyol, polyisocyanate, short-chain glycol and a sulfur-modified polyurethane resin consisting of a catalyst and a polymerization solvent, the polyol has a molecular weight of 400 ~ 1000, polyisocyanate 0.85 based on the total amount of polyol and short chain glycol of 0.85 Maintaining a ~ 1.05 molar ratio range, the polyisocyanate is characterized by consisting of 1.03 ~ 1.3 molar ratio range based on 1 mole of polyol.
이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명은 새로운 조성으로 폴리올, 폴리이소시아네이트, 단쇄글리콜과 촉매 및 중합용매로 이루어짐으로써 내황변성 등 제반물성이 우수한 무황변형 폴리우레탄 수지에 관한 것이다.The present invention relates to a sulfur-free polyurethane resin having excellent general properties such as yellowing resistance by being made of polyol, polyisocyanate, short-chain glycol and a catalyst and a polymerization solvent in a new composition.
본 발명에서 폴리올은 글리콜과 이염기산의 축합중합반응에 의해 합성된 것으로서 분자량이 400 ~ 1000인 에스테르형 폴리올을 사용한다. 여기서, 폴리올의 분자량이 400 미만이면 용매에 대한 용해성이 불량하고, 1000을 초과하면 용해성은 양호하나 기계적 강도가 불량하다. 폴리올 중합을 위한 글리콜로는 1,4-부탄디올과 1,4-시클로헥산디메탄올을 1 : 1 ~ 1 : 5 몰비로 혼합하여 사용한다. 여기서, 1,4-부탄디올과 1,4-시클로헥산디메탄올의 몰비가 1 : 미만이면 기계적 강도 및 내습성이 약하고 1 : 5를 초과하면 점도가 높은 단점이 있다. 폴리올 중합을 위한 이염기산으로서는 아디프산과 아젤라산을 단독 또는 혼합하여 사용한다.In the present invention, the polyol is synthesized by condensation polymerization of glycol and dibasic acid and uses an ester polyol having a molecular weight of 400 to 1000. Here, when the molecular weight of the polyol is less than 400, the solubility in solvents is poor, and when it exceeds 1000, the solubility is good but the mechanical strength is poor. As the glycol for polyol polymerization, 1,4-butanediol and 1,4-cyclohexanedimethanol are mixed and used in a ratio of 1: 1 to 1: 5. Here, when the molar ratio of 1,4-butanediol and 1,4-cyclohexanedimethanol is less than 1 :, the mechanical strength and moisture resistance are weak, and when the molar ratio is greater than 1: 5, the viscosity is high. As a dibasic acid for polyol polymerization, adipic acid and azelaic acid are used individually or in mixture.
그리고, 폴리이소시아네이트로서는 지방족 폴리이소시아네이트 예를들면, 1,6-헥사메틸디이소시아네이트, 이소포론디이소시아네이트, 크실렌디이소시아네이트, 수소가 첨가된 4,4'-디페닐메탄디아소시아네이트를 사용한다.And as polyisocyanate, aliphatic polyisocyanate, for example, 1, 6- hexamethyl diisocyanate, isophorone diisocyanate, xylene diisocyanate, 4,4'- diphenylmethane diisocyanate to which hydrogen was added is used.
또한, 단쇄글리콜로는 1,6-헥산디올, 네오펜틸글리콜, 1,4-부탄디올을 단독 또는 혼합하여 사용한다.In addition, as short chain glycol, 1, 6- hexanediol, neopentyl glycol, and 1, 4- butanediol are used individually or in mixture.
폴리우레탄 중합을 위한 촉매로는 틴옥토에이트, 디부틸틴디라우레이트를 사용하고, 용액 중합방법의 경우는 중합용매로서 톨루엔, 메틸에틸케톤, 에틸아세테이트, 시클로헥사논, 테트라히드로퓨란 등을 단독 또는 혼합하여 사용한다.Tin octoate and dibutyl tin dilaurate are used as a catalyst for polyurethane polymerization, and in the case of a solution polymerization method, toluene, methyl ethyl ketone, ethyl acetate, cyclohexanone, tetrahydrofuran, etc. are used alone or as a polymerization solvent. Use by mixing.
용액중합 외에 괴상중합이나 반응형 압출중합을 사용하는 경우에는 상기 모든 조건은 동일하나, 중합용매를 사용하지 않는다.In the case of using bulk polymerization or reactive extrusion polymerization in addition to solution polymerization, all of the above conditions are the same, but no polymerization solvent is used.
여기서, 폴리우레탄 중합을 수행함에 있어 폴리올과 단쇄글리콜의 합량 1 몰에 대하여 폴리이소시아네이트는 0.85 ~ 1.05 몰비 범위를 유지하도록 하는 바, 그 몰비가 0.85 미만이면 폴리우레탄 수지의 분자량이 증가하지 못하여 접착력 및 기계적 강도가 약하고, 1.05를 초과하면 후공정중에 경화반응이나 용액점도 등에 악영향을 주고 또한 수지자체의 저장안정성이 떨어진다.Here, the polyisocyanate is to maintain the range of 0.85 ~ 1.05 molar ratio with respect to the total amount of polyol and short chain glycol in the polymerization of the polyurethane, if the molar ratio is less than 0.85, the molecular weight of the polyurethane resin does not increase the adhesion and If the mechanical strength is weak and exceeds 1.05, it will adversely affect the curing reaction, the viscosity of the solution, etc. during the post-process, and the storage stability of the resin itself will be poor.
또한, 폴리올 1 몰에 대하여 폴리이소시아네이트는 1.03 ~ 1.3 몰비로 사용하며, 그 사용 몰비가 1.03 미만이면 기계적 강도가 약하고, 1.3을 초과하면 용매에 대한 용해성이 불량하다.In addition, polyisocyanate is used in 1.03-1.3 molar ratio with respect to 1 mol of polyols, When the use molar ratio is less than 1.03, mechanical strength is weak, and when it exceeds 1.3, solubility to a solvent is bad.
상기의 조성과 조건으로 제조된 폴리우레탄 수지는 용해성, 내황변형성 등제반물성이 우수하여 신발용 접착제 및 백색 잉크용 바인더로 적용이 가능하다.Polyurethane resin prepared under the above composition and conditions is excellent in solubility, yellowing resistance, etc., and can be applied as a binder for footwear and a white ink.
이하, 본 발명을 실시예에 의거 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.
실시예 1Example 1
온도계, 교반기와 히터 및 냉각기가 장치된 500 ㎖ 둥근 사구플라스크에 이 염기산으로서 아디프산과 아젤라산을 5 : 1 몰비로, 글리콜로서 1,4-시클로헥산디메탄올과 1,4-부탄디올을 3 : 1 몰비로 혼합한 후, 축합중합 반응시켜 분자량이 506인 에스테르형 폴리올을 제조하였다. 제조한 폴리올 100 중량부에, 단쇄글리콜로서 1.4-부탄디올 0.71 중량부, 촉매로서 디부틸틴디라우레이트 0.12 중량부와 중합용매로서 톨루엔 216.17 중량부를 넣고 70℃에서 30 ~ 60 분간 교반하였다. 그 다음 폴리이소시아네이트로서 이소포론디이소시아네이트 43.4 중량부를 가하여 70 ~ 80℃에서 4 ~ 6 시간 동안 교반하여 무황변형 폴리우레탄 수지를 제조하였다.In a 500 ml round four-necked flask equipped with a thermometer, a stirrer, a heater, and a cooler, adipic acid and azelaic acid were used as the base acids in a 5: 1 molar ratio, and 1,4-cyclohexanedimethanol and 1,4-butanediol were used as glycols. After mixing at a 1: 1 molar ratio, condensation polymerization was carried out to prepare an ester type polyol having a molecular weight of 506. To 100 parts by weight of the prepared polyol, 0.71 part by weight of 1.4-butanediol as a short chain glycol, 0.12 part by weight of dibutyl tin dilaurate as a catalyst and 216.17 parts by weight of toluene as a polymerization solvent were added and stirred at 70 ° C. for 30 to 60 minutes. Then, 43.4 parts by weight of isophorone diisocyanate was added as polyisocyanate, followed by stirring at 70 to 80 ° C. for 4 to 6 hours to prepare a sulfur-free polyurethane resin.
실시예 2Example 2
온도계, 교반기와 히터 및 냉각기가 장치된 500 ㎖ 둥근 사구플라스크에 이염기산으로서 아디프산, 글리콜로서 1,4-시클로헥산디메탄올과 1,4-부탄디올을 1 : 1 몰비로 혼합한 후, 축합중합 반응시켜 분자량이 843인 에스테르형 폴리올을 제조하였다. 제조된 폴리올 100 중량부에, 단쇄글리콜로서 1,4-부탄디올 2.14 중량부, 촉매로서 디부틸틴디라우레이트 0.11 중량부와 중합용매로서 톨루엔 198.3 중량부를 넣고 70℃에서 30 ~ 60분간 교반하였다. 그 다음 폴리이소시아네이트로서 이소포론디이소시아네이트 30.06 중량부를 가하여 70 ~ 80℃에서 4 ~ 6시간 동안 교반하여 무황변형 폴리우레탄 수지를 제조하였다.In a 500 ml round four-necked flask equipped with a thermometer, a stirrer, a heater and a cooler, adipic acid as a dibasic acid and 1,4-cyclohexanedimethanol as a glycol and 1,4-butanediol were mixed in a 1: 1 molar ratio, and then condensed. The polymerization reaction yielded an ester polyol having a molecular weight of 843. To 100 parts by weight of the prepared polyol, 2.14 parts by weight of 1,4-butanediol as short chain glycol, 0.11 part by weight of dibutyl tin dilaurate as a catalyst and 198.3 parts by weight of toluene as a polymerization solvent were added and stirred at 70 ° C. for 30 to 60 minutes. Then, 30.06 parts by weight of isophorone diisocyanate was added as a polyisocyanate, followed by stirring at 70 to 80 ° C. for 4 to 6 hours to prepare a sulfur-free polyurethane resin.
실시예 3Example 3
온도계, 교반기와 히터 및 냉각기가 장치된 500 ㎖ 둥근 사구플라스크에 이염기산으로서 아디프산과 아젤라산을 5 : 1 몰비로 혼합하고 글리콜로서 1,4-시클로헥산디메탄올과 1,4-부탄디올을 3 : 1 몰비로 혼합한 후, 축합중합 반응시켜 분자량이 506인 에스테르형 폴리올을 제조하였다. 폴리올 100 중량부에, 단쇄글리콜로서 1,4-부탄디올 0.71 중량부, 촉매로서 디부틸틴디라우레이트 0.12 중량부와 중합용매로서 시클로헥사논 216.17 중량부를 넣고 70℃에서 30 ~ 60분간 교반하였다. 그 다음 폴리이소시아네이트로서 이소포론디이소시아네이트 43.4 중량부를 가하여 70 ~ 80℃에서 4 ~ 6시간 동안 교반하여 무황변형 폴리우레탄 수지를 제조하였다.In a 500 ml round four-necked flask equipped with a thermometer, a stirrer, a heater and a cooler, adipic acid and azelaic acid were mixed in a 5: 1 molar ratio as a dibasic acid, and 1,4-cyclohexanedimethanol and 1,4-butanediol were 3 as glycol. After mixing at a 1: 1 molar ratio, condensation polymerization was carried out to prepare an ester type polyol having a molecular weight of 506. To 100 parts by weight of polyol, 0.71 parts by weight of 1,4-butanediol as short chain glycol, 0.12 parts by weight of dibutyl tin dilaurate as catalyst and 216.17 parts by weight of cyclohexanone as polymerization solvent were added and stirred at 70 ° C for 30 to 60 minutes. Then, 43.4 parts by weight of isophorone diisocyanate was added as a polyisocyanate, followed by stirring at 70 to 80 ° C. for 4 to 6 hours to prepare a sulfur-free polyurethane resin.
실시예 4Example 4
온도계, 교반기와 히터 및 냉각기가 장치된 500 ㎖ 둥근 사구플라스크에 이염기산으로서 아디프산과 아젤라산을 5 : 1 몰비로 혼합하고 글리콜로서 1,4-시클로헥산디메탄올과 1,4-부탄디올을 3 : 1 몰비로 혼합한 후, 축합중합 반응시켜 분자량이 506인 에스테르형 폴리올을 제조하였다. 제조한 폴리올 100 중량부에 대하여, 단쇄글리콜로서 1,4-부탄디올 0.71 중량부, 촉매로서 디부틸틴디라우레이트 0.12 중량부와 중합용매로서 메틸에틸케톤 216.17 중량부를 넣고 70℃에서 30 ~ 60 분간 교반하였다. 그 다음 폴리이소시아네이트로서 이소포론디이소시아네이트 43.4 중량부를 가하여 70 ~ 80℃에서 4 ~ 6시간 동안 교반하여 무황변형 폴리우레탄 수지를 제조하였다.In a 500 ml round four-necked flask equipped with a thermometer, a stirrer, a heater and a cooler, adipic acid and azelaic acid were mixed in a 5: 1 molar ratio as a dibasic acid, and 1,4-cyclohexanedimethanol and 1,4-butanediol were 3 as glycol. After mixing at a 1: 1 molar ratio, condensation polymerization was carried out to prepare an ester type polyol having a molecular weight of 506. To 100 parts by weight of the prepared polyol, 0.71 parts by weight of 1,4-butanediol as short chain glycol, 0.12 parts by weight of dibutyl tin dilaurate as catalyst and 216.17 parts by weight of methyl ethyl ketone as polymerization solvent were added and stirred at 70 ° C. for 30 to 60 minutes. It was. Then, 43.4 parts by weight of isophorone diisocyanate was added as a polyisocyanate, followed by stirring at 70 to 80 ° C. for 4 to 6 hours to prepare a sulfur-free polyurethane resin.
실시예 5Example 5
온도계, 교반기와 히터 및 냉각기가 장치된 500 ㎖ 둥근 사구플라스크에 이염기산으로서 아디프산, 글리콜로서 1,4-시클로헥산디메탄올과 1,4-부탄디올을 1 : 1 몰비로 혼합한 후, 축합중합 반응시켜 분자량이 843인 에스테르형 폴리올을 제조하였다. 제조한 폴리올 100 중량부에, 단쇄글리콜로서 1,4-부탄디올 2.14 중량부, 촉매로서 디부틸틴디라우레이트 0.11 중량부와 중합용매로서 시클로헥사논 198.3 중량부를 넣고 70℃에서, 30 ~ 60 분간 교반하였다. 그 다음 폴리이소시아네이트로서 이소포론디이소시아네이트 30.06 중량부를 가하여 70 ~ 80℃에서 4 ~ 6 시간 동안 교반하여 무황변형 폴리우레탄 수지를 제조하였다.In a 500 ml round four-necked flask equipped with a thermometer, a stirrer, a heater and a cooler, adipic acid as a dibasic acid and 1,4-cyclohexanedimethanol as a glycol and 1,4-butanediol were mixed in a 1: 1 molar ratio, and then condensed. The polymerization reaction yielded an ester polyol having a molecular weight of 843. To 100 parts by weight of the prepared polyol, 2.14 parts by weight of 1,4-butanediol as short-chain glycol, 0.11 part by weight of dibutyl tin dilaurate as catalyst and 198.3 parts by weight of cyclohexanone as polymerization solvent were stirred at 70 ° C. for 30 to 60 minutes. It was. Then, 30.06 parts by weight of isophorone diisocyanate was added as a polyisocyanate, followed by stirring at 70 to 80 ° C. for 4 to 6 hours to prepare a sulfur-free polyurethane resin.
실시예 6Example 6
온도계, 교반기와 히터 및 냉각기가 장치된 500 ㎖ 둥근 사구플라스크에 이염기산으로서 아디프산, 글리콜로서 1,4-시클로헥산디메탄올과 1,4-부탄디올을 1 : 1 몰비로 혼합한 후, 축합중합 반응시켜 분자량이 843인 에스테르형 폴리올을 제조하였다. 제조한 폴리올 100 중량부에 대하여, 단쇄글리콜로서 1,4-부탄디올 2.14 중량부, 촉매로서 디부틸틴디라우레이트 0.11 중량부와 중합용매로서 메틸에틸케톤 198.3 중량부를 넣고 70℃에서 30 ~ 60 분간 교반하였다. 그 다음 폴리이소시아네이트로서 이소포론디이소시아네이트 30.06 중량부를 가하여 70 ~ 80℃에서 4 ~ 6 시간 동안 교반하여 무황변형 폴리우레탄 수지를 제조하였다.In a 500 ml round four-necked flask equipped with a thermometer, a stirrer, a heater and a cooler, adipic acid as a dibasic acid and 1,4-cyclohexanedimethanol as a glycol and 1,4-butanediol were mixed in a 1: 1 molar ratio, and then condensed. The polymerization reaction yielded an ester polyol having a molecular weight of 843. To 100 parts by weight of the prepared polyol, 2.14 parts by weight of 1,4-butanediol as short chain glycol, 0.11 part by weight of dibutyl tin dilaurate as catalyst and 198.3 parts by weight of methyl ethyl ketone as polymerization solvent were added and stirred at 70 ° C. for 30 to 60 minutes. It was. Then, 30.06 parts by weight of isophorone diisocyanate was added as a polyisocyanate, followed by stirring at 70 to 80 ° C. for 4 to 6 hours to prepare a sulfur-free polyurethane resin.
비교예 1Comparative Example 1
온도계, 교반기와 히터 및 냉각기가 장치된 500 ㎖ 둥근 사구플라스크에 이염기산으로서 아디프산과 아젤라산을 5 : 1 몰비로, 글리콜로서 1,4-시클로헥산디메탄올과 1,4-부탄디올을 3 : 1 몰비로 혼합한 후, 축합중합 반응시켜 분자량이 506인 에스테르형 폴리올을 제조하였다. 제조한 폴리올 100 중량부에, 단쇄글리콜로서 1,4-부탄디올 0.71 중량부, 촉매로서 디부틸틴디라우레이트 0.12 중량부와 중합용매로서 톨루엔 216.17 중량부를 넣고 70℃에서 30 ~ 60 분간 교반하였다. 그 다음 폴리이소시아네이트로서 톨루엔디이소시아네이트 34.0 중량부를 가하여 70 ~ 80℃에서 4 ~ 6시간 동안 교반하여 무황변형 폴리우레탄 수지를 제조하였다.In a 500 ml round four-necked flask equipped with a thermometer, a stirrer, a heater, and a cooler, adipic acid and azelaic acid as a dibasic acid in a 5: 1 molar ratio, and 1,4-cyclohexanedimethanol and 1,4-butanediol as glycols were 3: After mixing in 1 molar ratio, it carried out condensation polymerization reaction and prepared the ester type polyol whose molecular weight is 506. To 100 parts by weight of the prepared polyol, 0.71 parts by weight of 1,4-butanediol as short chain glycol, 0.12 parts by weight of dibutyl tin dilaurate as catalyst and 216.17 parts by weight of toluene as a polymerization solvent were added and stirred at 70 ° C. for 30 to 60 minutes. Then, 34.0 parts by weight of toluene diisocyanate was added as a polyisocyanate, followed by stirring at 70 to 80 ° C. for 4 to 6 hours to prepare a sulfur-free polyurethane resin.
비교예 2Comparative Example 2
온도계, 교반기와 히터 및 냉각기가 장치된 500 ㎖ 둥근 사구플라스크에 이염기산으로서 아디프산과 아젤라산을 5 : 1 몰비로, 글리콜로서 1,4-시클로헥산디메탄올과 1,4-부탄디올을 3 : 1 몰비로 혼합한 후, 축합중합 반응시켜 분자량이 506인 에스테르형 폴리올을 제조하였다. 제조한 폴리올 100 중량부에 대하여, 단쇄글리콜로서 1,4-부탄디올 0.71 중량부, 촉매로서 디부틸린디라우레이트 0.12중량부와 중합용매로서 톨루엔 216.17 중량부를 넣고 70℃에서 30 ~ 60분간 교반하였다. 그 다음 폴리이소시아네이트로서 4,4'-디페닐메탄디이소시아네이트 48.86 중량부를 가하여 70 ~ 80 ℃에서 4 ~ 6 시간 동안 교반하여 무황변형 폴리우레탄 수지를 제조하였다.In a 500 ml round four-necked flask equipped with a thermometer, a stirrer, a heater, and a cooler, adipic acid and azelaic acid as a dibasic acid in a 5: 1 molar ratio, and 1,4-cyclohexanedimethanol and 1,4-butanediol as glycols were 3: After mixing in 1 molar ratio, it carried out condensation polymerization reaction and prepared the ester type polyol whose molecular weight is 506. To 100 parts by weight of the prepared polyol, 0.71 parts by weight of 1,4-butanediol as short chain glycol, 0.12 parts by weight of dibutylin dilaurate as catalyst and 216.17 parts by weight of toluene as a polymerization solvent were added and stirred at 70 ° C. for 30 to 60 minutes. Then, 48.86 parts by weight of 4,4'-diphenylmethane diisocyanate was added as a polyisocyanate, followed by stirring at 70 to 80 ° C. for 4 to 6 hours to prepare a sulfur-free polyurethane resin.
비교예 3Comparative Example 3
온도계, 교반기와 히터 및 냉각기가 장치된 500 ㎖ 둥근 사구플라스크에 이염기산으로서 아디프산, 글리콜로서 1,4-시클로헥산디메탄올과 1,4-부탄디올을 1 :1 몰비로 혼합한 후, 축합중합 반응시켜 제조된 분자량이 843인 에스테르형 폴리올을 제조하였다. 제조한 폴리올 100 중량부에, 단쇄글리콜로서 1,4-부탄디올 2.14 중량부, 촉매로서 디부틸틴디라우레이트 0.11 중량부와 중합용매로 톨루엔 198.3 중량부를 넣고 70℃에서 30 ~ 60 분간 교반하였다. 그 다음 폴리이소시아네이트로서 톨루엔디이소시아네이트 23.55 중량부를 가하여 70 ~ 80℃에서 4 ~ 6 시간 동안 교반하여 폴리우레탄 수지를 제조하였다.In a 500 ml round four-necked flask equipped with a thermometer, a stirrer, a heater and a cooler, adipic acid as a dibasic acid and 1,4-cyclohexanedimethanol as a glycol and 1,4-butanediol were mixed in a 1: 1 molar ratio, followed by condensation. An ester polyol having a molecular weight of 843 prepared by polymerization was prepared. To 100 parts by weight of the prepared polyol, 2.14 parts by weight of 1,4-butanediol as short-chain glycol, 0.11 part by weight of dibutyl tin dilaurate as a catalyst, and 198.3 parts by weight of toluene as a polymerization solvent were added and stirred at 70 ° C. for 30 to 60 minutes. Then, 23.55 parts by weight of toluene diisocyanate was added as polyisocyanate, followed by stirring at 70 to 80 ° C. for 4 to 6 hours to prepare a polyurethane resin.
비교예 4Comparative Example 4
온도계, 교반기와 히터 및 냉각기가 장치된 500 ㎖ 둥근 사구플라스크에 이염기산으로서 아디프산, 글리콜로서 1,4-시클로헥산디메탄올과 1,4-부탄디올을 1 : 1 몰비로 축합중합 반응시켜 분자량이 843인 에스테르형 폴리올을 제조하였다. 제조한 폴리올 100 중량부에, 단쇄글리콜로서 1,4-부탄디올 2.14 중량부, 촉매로서 디부틸틴디라우레이트 0.11 중량부와 중합용매로서 톨루엔 198.3 중량부를 넣고 70℃에서 30 ~ 60분간 교반하였다. 그 다음 폴리이소시아네이트로서 4,4'-디페닐메탄디이소시아네이트 33.84 중량부를 가하여 70 ~ 80℃에서 4 ~ 6시간 동안 교반하여 폴리우레탄 수지를 제조하였다.A 500 ml round four-necked flask equipped with a thermometer, a stirrer, a heater and a cooler was subjected to condensation polymerization of adipic acid as a dibasic acid and 1,4-cyclohexanedimethanol as a glycol and 1,4-butanediol in a 1: 1 molar ratio by molecular weight. This ester type polyol which was 843 was prepared. To 100 parts by weight of the prepared polyol, 2.14 parts by weight of 1,4-butanediol as short chain glycol, 0.11 part by weight of dibutyl tin dilaurate as catalyst and 198.3 parts by weight of toluene as a polymerization solvent were added and stirred at 70 ° C. for 30 to 60 minutes. Then, 33.84 parts by weight of 4,4'-diphenylmethane diisocyanate was added as a polyisocyanate, followed by stirring at 70 to 80 ° C. for 4 to 6 hours to prepare a polyurethane resin.
실험예Experimental Example
상기 실시예 1 ~ 6 및 비교예 1 ~ 4에 의해 제조된 무황변형 폴리우레탄 수지의 내황변성과 용해성 등의 물성을 측정하였으며, 그 결과는 다음 표 1에 나타낸 바와 같다.The physical properties such as yellowing resistance and solubility of the yellow sulfur-modified polyurethane resin prepared by Examples 1 to 6 and Comparative Examples 1 to 4 were measured, and the results are shown in Table 1 below.
여기서, 내황변성은 제조된 무황변형 폴리우레탄 수지를 옥외에 1개월간 방치한 후 황변 유무로 확인하였으며 이때, 황변하면 내황변성이 불량한 것이고, 황변하지 않으면 내황변성이 양호한 것으로 판단하였다.Here, the yellowing resistance was confirmed by the presence of yellowing after leaving the prepared undeformed polyurethane resin in the outdoors for 1 month, at this time, yellowing resistance is poor when yellowing, yellowing resistance was determined to be good.
또한, 용해성은 메틸에틸케톤 중합용매를 사용하여 고형분 40%로 만든 용액을 톨루엔으로 희석시켰을 때의 용액의 백탁유무로써 확인하였다. 이때, 용액이 투명하면 용해성이 양호한 것이고, 불투명하면 용해성이 불량한 것으로 판단하였다.In addition, the solubility was confirmed by the presence or absence of turbidity of the solution when the solution made to 40% of solid content using the methyl ethyl ketone polymerization solvent was diluted with toluene. At this time, it was judged that the solubility was good when the solution was transparent, and the solubility was poor when it was opaque.
상기 표 1로부터 알 수 있듯이 실시예 1 ~ 6의 경우 내황변성 및 용해성이 모두 우수하나 비교예 1과 3은 용해성은 양호하나 내황변성이 불량하고, 비교예 2와 4의 경우는 내황변성과 용해성 모두 불량하다.As can be seen from Table 1, Examples 1 to 6 are excellent in both yellowing resistance and solubility, but Comparative Examples 1 and 3 have good solubility but poor yellowing resistance, and Comparative Examples 2 and 4 have yellowing resistance and solubility. All are bad.
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| US5130404A (en) * | 1991-06-04 | 1992-07-14 | Azon Usa Inc. | Castable thermosetting polyurethane polymer having improved heat stability |
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|---|---|---|---|---|
| JPS5798577A (en) * | 1980-12-11 | 1982-06-18 | Honny Chem Ind Co Ltd | Vehicle composition for printing ink |
| EP0152049B1 (en) * | 1984-02-16 | 1989-08-30 | Bayer Ag | Process for the preparation of thermoplastic polyurethane elastomers and their use |
| JPH0264174A (en) * | 1988-08-30 | 1990-03-05 | Toyo Ink Mfg Co Ltd | Printing ink composition for plastics |
| JPH03177467A (en) * | 1989-12-06 | 1991-08-01 | Mitsubishi Kasei Corp | Urethane binder for printing ink |
| US5130404A (en) * | 1991-06-04 | 1992-07-14 | Azon Usa Inc. | Castable thermosetting polyurethane polymer having improved heat stability |
Also Published As
| Publication number | Publication date |
|---|---|
| KR960022643A (en) | 1996-07-18 |
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