KR0139357B1 - Polyurethane Elastic Fiber Manufacturing Method - Google Patents
Polyurethane Elastic Fiber Manufacturing MethodInfo
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- KR0139357B1 KR0139357B1 KR1019950020279A KR19950020279A KR0139357B1 KR 0139357 B1 KR0139357 B1 KR 0139357B1 KR 1019950020279 A KR1019950020279 A KR 1019950020279A KR 19950020279 A KR19950020279 A KR 19950020279A KR 0139357 B1 KR0139357 B1 KR 0139357B1
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Abstract
본 발명은 분자량이 1000∼3000인 폴리에테르 디올 및 분자량이 500∼3000인 폴리카보네이트 디올로 구성된 장쇄 디올과 제3급 아미노기를 최소한 1개 가지는 아미노기 2∼7개를 갖고 탄소수 3∼12개인 폴리올을 디이소시아네이트와 함께 예비중합시킨 다음 쇄성장제인 디아민 화합물을 예비중합물에 대하여 0.5∼0.98몰% 첨가하고 쇄정지제인 모노아민 화합물을 전체 아민 사용량의 1∼30몰% 첨가하여 중합을 완료한후 디에스테르 금속염계의 내염소성 향상 첨가제를 폴리머 고형분에 대하여 0.01∼4.5중량% 첨가하여 방사함을 특징으로 하는 폴리우레탄계 탄성섬유의 제조방법.The present invention relates to a polyol having 3 to 12 carbon atoms having 2 to 7 amino groups having at least one tertiary amino group and a long chain diol composed of a polyether diol having a molecular weight of 1000 to 3000 and a polycarbonate diol having a molecular weight of 500 to 3000. After prepolymerization with diisocyanate, 0.5 ~ 0.98 mol% of a chain growth agent diamine compound is added to the prepolymer and 1-30 mol% of the total amine used as a chain stopper is added to complete the polymerization. A method for producing a polyurethane-based elastic fiber, characterized in that spinning by adding a metal salt-based chlorine resistance improving additive 0.01 to 4.5% by weight based on the polymer solids.
Description
본 발명은 탄성섬유의 고유한 물성을 유지하면서도 내염소성과 내열성이 우수한 폴리우레탄계 탄성섬유의 제조방법에 관한 것이다.The present invention relates to a method for producing a polyurethane-based elastic fiber excellent in chlorine resistance and heat resistance while maintaining the inherent physical properties of the elastic fiber.
폴리우레탄계 탄성섬유는 탄성율과 탄성회복력이 우수함으로써 스타킹이나 여성용 속옷류, 수영복 등 신축성 직물에 많이 이용되고 있다.Polyurethane-based elastic fibers have been widely used in stretch fabrics such as stockings, women's underwear and swimwear due to their excellent elastic modulus and elastic recovery.
그러나 폴리우레탄계 탄성섬유는 내열성이 취약하여 폴리에스테르 섬유 등 타소재와 혼방하여 사용시 130℃ 정도의 고온염색이 불가능하여 염색이 어려울뿐 아니라 후처리 공정에서 열처리에 의해 폴리우레탄계 탄성섬유가 손상되어 섬유의 강도 및 탄성회복력이 저하되고 변색현상이 일어나는 등 각종 문제를 초래하게 되어 용도에 제한이 따르는 단점이 있다.However, polyurethane-based elastic fibers are poor in heat resistance, so they can not be dyed at a high temperature of about 130 ° C when mixed with other materials such as polyester fibers, making dyeing difficult, and in addition, the polyurethane-based elastic fibers are damaged by heat treatment in the post-treatment process. The strength and elastic recovery force is lowered, causing a variety of problems such as discoloration phenomenon has a disadvantage in that the use is limited.
폴리우레탄계 탄성섬유의 내열성을 향상시키기 위한 종래의 방법으로는 별도의 내열성 향상첨가제를 투입하거나 고분자 디올화합물의 일부분을 저분자량의 디올화합물 예를 들면 에틸렌글리콜, 디에틸렌글리콜, 프로필렌글리콜 1,4-부탄디올 등으로 대체하여 사용하는 방법이 알려져 있다. 또한 폴리테트라메틸렌글리콜과 과잉의 4,4'-디페닐메탄디이소시아네이트와 반응시킨 후 1,2-프로필렌디아민과 디에틸렌아민으로 쇄성장시킨 폴리머를 방사하여 제조한 탄성사를 일정한 온도에서 가열처리하여 탄성회복율을 향상시키는 방법이 일본특공 평4-74457에 개시되어 있으나, 이러한 방법으로 제조시 탄성사의 가열처리공정이 추가됨으로써 작업이 어려울뿐만 아니라 내열성은 향상되지 않는다.Conventional methods for improving the heat resistance of polyurethane-based elastic fibers include a separate heat-resistant improving additive, or a portion of the high molecular weight diol compound is a low molecular weight diol compound, for example ethylene glycol, diethylene glycol, propylene glycol 1,4- It is known to substitute butanediol and the like. In addition, the elastic yarn prepared by reacting polytetramethylene glycol with excess 4,4'-diphenylmethane diisocyanate and spinning the polymer chain-grown with 1,2-propylenediamine and diethyleneamine was heated at a constant temperature. Although a method for improving the elastic recovery rate is disclosed in Japanese Patent Application Laid-Open No. Hei 4-74457, in addition to the heat treatment step of the elastic yarn in manufacturing in this way, not only the work is difficult but also the heat resistance is not improved.
폴리우레탄계 탄성섬유의 내염소성을 향상시키기 위한 방법으로는 일본특개소 60-36560에 폴리테트라메틸렌글리콜과 과잉의 4,4'-디페닐메탄디이소시아네이트를 예비중합후 아민으로 쇄연장 및 쇄정지시키고 이 중합물에 제3급 질소함유 우레탄 폴리머를 첨가하는 방법이 개시되어 있고, 일본특개소 56-107010에는 폴리에스테르 글리콜과 과잉의 4,4'-디페닐메탄디이소시아네이트를 예비중합후 아민을 사용하여 쇄연장시켜서 일정한 점도의 폴리머를 제조하고 방사전에 지방산 금속계 화합물을 첨가시켜 내염소성을 향상시키는 방법이 공지되어 있으나 이 경우 내염소성 향상은 만족스러운 수준이 아니고 더구나 폴리우레탄계 탄성체의 고유물성인 탄성회복율과 강도저하를 초래하는 단점이 있었다.As a method for improving the chlorine resistance of polyurethane-based elastic fibers, polytetramethylene glycol and excess 4,4'-diphenylmethane diisocyanate are prepolymerized in Japanese Patent Application No. 60-36560, followed by chain extension and chain stop with amine. A method of adding a tertiary nitrogen-containing urethane polymer to the polymer is disclosed. In Japanese Patent Laid-Open No. 56-107010, a polyester glycol and an excess of 4,4'-diphenylmethane diisocyanate are prepolymerized and then amine is used. It is known to improve the chlorine resistance by producing a polymer of constant viscosity by chain extension and adding a fatty acid metal compound before spinning, but in this case, the improvement of the chlorine resistance is not satisfactory, and moreover, the elastic recovery rate, which is inherent to the polyurethane-based elastomer, It has the disadvantage of causing excessive strength degradation.
따라서 본 발명은 폴리우레탄계 탄성섬유의 고유한 물성을 유지하면서도 내열성 및 내염소성이 우수한 폴리우레탄계 탄성섬유의 제조방법을 제공함을 그 목적으로 한다.Accordingly, an object of the present invention is to provide a method for producing a polyurethane-based elastic fiber having excellent heat resistance and chlorine resistance while maintaining the inherent physical properties of the polyurethane-based elastic fiber.
이에 본 발명에서는 탄성성능이 우수한 폴리에테르디올과 내열성이 우수한 폴리카보네이트디올을 혼합 반응시킨 장쇄디올을 폴리올 및 디이소시아네이트와 예비 중합하고 내염소성 화합물을 첨가함으로써 내열성과 내염소성을 현저하게 향상시킨 폴리우레탄계 탄성섬유를 얻게되어 본 발명에 이르게 되었다.Accordingly, in the present invention, a polyurethane-based polymer having a remarkably improved heat resistance and chlorine resistance by prepolymerizing a long chain diol mixed with a polyether diol having excellent elastic performance and a polycarbonate diol having excellent heat resistance with a polyol and a diisocyanate and adding a chlorine resistant compound Elastic fibers were obtained, which led to the present invention.
이하, 본 발명을 좀더 구체적으로 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
폴리에테르디올(A-1), 폴리카보네이트디올(A-2)을 혼합시킨 장쇄디올(A)과 제3급 아미노기를 최소한 1개 가지는 아미노기수 2∼7개, 탄소수 3∼12개의 폴리올(B)을 과잉의 디이소시아네이트(C)와 예비 중합하여 용제와 일정비율을 혼합시킨 후 말단의 이소시아네이트를 디아민 화합물(D)을 사용하여 쇄성장을 시켜서 방사에 적당한 점도를 얻은 후 모노아민 화합물(E)을 사용하여 말단을 봉쇄시키고 내염소성 화합물(F)를 첨가하여 중합물을 얻고 이를 방사하여 폴리우레탄계 탄성섬유를 제조하였다.Long-chain diol (A) mixed with polyetherdiol (A-1) and polycarbonate diol (A-2) and polyol (B) having 2 to 7 amino groups and 3 to 12 carbon atoms having at least one tertiary amino group ) Is prepolymerized with excess diisocyanate (C) to mix a solvent and a certain ratio, and then the terminal isocyanate is chain-grown with diamine compound (D) to obtain a viscosity suitable for spinning, followed by monoamine compound (E) The terminal was sealed using and a chlorine resistant compound (F) was added to obtain a polymer, which was then spun to prepare a polyurethane-based elastic fiber.
본 발명에서 사용한 폴리우레탄계 탄성섬유는 소프트세그먼트 역할을 하는 장쇄 디올(A)성분으로써 폴리에테르 디올(A-1)과 내열성이 우수한 폴리카보네이트 디올(A-2)을 몰비(A-2/A-1)가 0.2∼10, 바람직하기는 0.5∼7이 되도록 혼합하고, 제3급 아미노기를 갖는 폴리올(B)을 장쇄 디올(A)과의 몰비(A/B)가 5∼50, 바람직하기는 12∼35가 되도록 혼합한 후 4,4'-디페닐메탄디이소시아네이트 1.23∼2.7몰과 예비중합하였다. 이 예비중합물에 디메틸틸아세트아미드를 적당량 혼합하여 예비중합물 용액을 제조한 후 디아민 화합물(D)을 예비중합물에 대해 0.50∼0.98몰 사용하여 말단의 이소시아네이트를 쇄성장시켜서 방사에 적당한 점도인 500∼3800포아즈를 얻는다. 이후 쇄정지제로 모노아민 화합물(E)을 전체아민 사용량에 대해 1∼30몰% 사용하여 쇄정지를 시킨후 점도안정제를 사용하여 방사에 적당한 점도를 유지시킨다.Polyurethane-based elastic fibers used in the present invention is a long-chain diol (A) component that acts as a soft segment, the molar ratio (A-2 / A-) of polyether diol (A-1) and polycarbonate diol (A-2) having excellent heat resistance. 1) is 0.2 to 10, preferably 0.5 to 7, and the polyol (B) having a tertiary amino group is 5 to 50, preferably a molar ratio (A / B) to the long chain diol (A). The mixture was mixed to 12 to 35 and then prepolymerized with 1.23 to 2.7 moles of 4,4'-diphenylmethane diisocyanate. A suitable amount of dimethyltylacetamide was mixed with the prepolymer to prepare a prepolymer solution. Then, 0.5 to 0.98 moles of the diamine compound (D) was used for the prepolymer to chain grow the terminal isocyanate to obtain a suitable viscosity for spinning. Get Poise. Thereafter, the chain stop is used as a chain stopper by using 1 to 30 mol% of the monoamine compound (E) with respect to the total amount of amine, and then a viscosity stabilizer is used to maintain a suitable viscosity for spinning.
본 발명에 사용된 폴리에테르 디올(A-1)로는 폴리에틸렌글리콜, 폴리프로필렌글리콜, 폴리테트라메틸렌글리콜 등이 사용될 수 있으며, 분자량은 1000∼3000 특히 1500∼2500의 범위가 적합하다.As the polyether diol (A-1) used in the present invention, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or the like may be used, and the molecular weight is suitably in the range of 1000 to 3000, particularly 1500 to 2500.
내열성을 향상시키기 위해 사용된 폴리카보네이트 디올(A-2)로는 에틸렌글리콜, 디에틸렌글리콜, 트리에틸렌글리콜, 프로필렌글리콜 1,4-부탄디올, 1,3-부탄디올, 1,5-펜탄디올, 1,6-헥산디올, 1,4-사이클로헥산디올, 1,4-사이클로헥산디메탄올, 2,2-디메닐-1,3-프로판디올, 1,8-옥탄디올 등의 글리콜 단독 또는 이들의 혼합물과 디아릴 카보네이트, 디알킬 카보네이트, 포스겐 등과의 축합반응에 의해 합성된 분자량 500∼3000 특히 1000∼2200의 디올이 사용될 수 있다.Polycarbonate diols (A-2) used to improve heat resistance include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1, Glycols alone or mixtures thereof such as 6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2-dimenyl-1,3-propanediol, 1,8-octanediol And diols having a molecular weight of 500 to 3000, in particular 1000 to 2200, synthesized by condensation with diaryl carbonate, dialkyl carbonate, phosgene and the like can be used.
상기 언급된 폴리에테르 디올(A-1)과 폴리카보네이트 디올(A-2)의 분자량 및 몰비를 벗어나면 탄성사의 고유한 물성인 강,신도 및 내열성이 등이 저하되는 문제가 있다.When the molecular weight and molar ratio of the above-mentioned polyether diol (A-1) and polycarbonate diol (A-2) are out of the range, there is a problem in that strength, elongation, heat resistance, etc., which are inherent physical properties of elastic yarn, are lowered.
또한 상기 폴리우레탄계 탄성섬유는 제3급의 아미노기를 최소한 1개 이상 가지는 아미노기수 2∼7개, 탄소수 3∼12개의 폴리올(B)을 사용하여 양 말단 이외의 위치에 측쇄로써 제3급의 아미노기를 도입시킴으로써 이소시아네이트와의 우레아 결합에 의한 망상구조를 가지게 되어 강고한 결합이 형성되며 이로인해 내열성과 탄성회복력을 향상시키고 중합물의 점도안정성을 향상시켜 방사에 적당한 점도를 유지시킨다.In addition, the polyurethane-based elastic fiber is a tertiary amino group by side chain at positions other than both ends using 2 to 7 amino groups and 3 to 12 carbon atoms (B) having at least one or more tertiary amino groups. By introducing a has a network structure by the urea bond with the isocyanate to form a strong bond, thereby improving heat resistance and elastic recovery ability and improve the viscosity stability of the polymer to maintain a suitable viscosity for spinning.
상기 제3급 아미노기를 가지는 폴리올(B) 성분으로는 R-NH2(R:CnH2n+1, n=1∼30)로 표시된 제1급 아민류에 에틸렌옥사이드, 프로필렌옥사이드, 부틸렌옥사이드 등을 2∼55몰 부가시켜 만든 디올류 및 이들의 유도체가 사용될 수 있다. 예를 들면 메틸아민, 에틸아민, 이소프로필아민, n-부틸아민, 이소부탄아민 등의 제1급 아민류에 에틸렌옥사이드를 2몰 부가시켜 얻은 N-메틸디에탈올아민, N-에틸디에탈올아민, N-이소프로필 디에탄올아민 등의 N-알킬디에탈올아민과 라우릴아민, 스테아릴아민, 올레일아민 등에 에틸렌옥사이드를 20∼55몰 부가시킨 폴리옥시에틸렌 올레일아민과 같은 알킬아민류에 에틸렌옥사이드, 프로필렌옥사이드 등을 부가시킨 디올류가 사용될 수 있다.Examples of the polyol (B) component having the tertiary amino group include ethylene oxide, propylene oxide and butylene oxide in primary amines represented by R-NH 2 (R: C n H 2n + 1 , n = 1 to 30). Diols and derivatives thereof made by addition of 2 to 55 moles or the like can be used. For example, N-methyl diethanolamine, N-ethyl diethanol amine obtained by adding 2 mol of ethylene oxide to primary amines, such as methylamine, ethylamine, isopropylamine, n-butylamine, and isobutanamine, Ethylene oxide to alkylamines such as polyoxyethylene oleylamine, in which 20 to 55 moles of ethylene oxide is added to N-alkyl diethanolamine such as N-isopropyl diethanolamine and laurylamine, stearylamine, and oleylamine. And diols to which propylene oxide and the like are added can be used.
상기 장쇄디올(A)과 제3급 아미노기를 가지는 폴리올(B)과의 사용몰비는 A/B=5∼50 특히, 12∼35가 적당하다. 만일 몰비(A/B)가 5 미만에서는 용제에 잘 용해되지 않아 방사에 문제가 되며, 50초과에서는 내열성 및 탄성회복력 등의 향상 정도가 미미하다.As for the use molar ratio of the said long-chain diol (A) and the polyol (B) which has a tertiary amino group, A / B = 5-50 especially 12-35 are suitable. If the molar ratio (A / B) is less than 5, it is difficult to dissolve in the solvent, which is a problem in spinning.
쇄성장제인 아민화합물과 결합하여 하드 세그먼트(hard segment)의 역할을 하는 디이소시아네이트(C)로서는 파라페닐 디이소시아네이트, 메타페닐렌디이소시아네이트, 2,4-토리렌 디이소시아네이트, 2,6-토리렌 디이소시아네이트, 1-클로르-2,1-페닐렌 디이소시아네이트, 1,5-나프탈렌 디이소시아네이트, 1,4-페닐렌 디이소시아네이트, 클로로페닐렌-2,4'-디이소시아네이트, 메틸렌비스-4-페닐디이소시아네이트, 헥사메틸렌 디이소시아네이트, 폴리메틸렌 폴리페닐 디이소시아네이트, 메틸사이클로 헥시렌 디이소시아네이트, 파라페닐 디이소시아네이트, 파라페닐렌 디이소시아네이트, 4,4'-디페닐 이소프로필리딘 디이소시아네이트, 4,4'-디페닐메탄 디이소시아네이트 등이 있는데 디올 화합물과의 반응성과 탄성체의 물성을 고려시 4,4'-디페닐메탄디이소시아네이트가 가장 좋다.Examples of the diisocyanate (C) which combines with an amine compound which is a chain growth agent to serve as a hard segment include paraphenyl diisocyanate, metaphenylene diisocyanate, 2,4-torylene diisocyanate, and 2,6-torylene di Isocyanate, 1-chlor-2,1-phenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,4-phenylene diisocyanate, chlorophenylene-2,4'- diisocyanate, methylenebis-4-phenyl Diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl diisocyanate, methylcyclo hexylene diisocyanate, paraphenyl diisocyanate, paraphenylene diisocyanate, 4,4'-diphenyl isopropylidine diisocyanate, 4,4 ' -Diphenylmethane diisocyanate, etc., considering the reactivity with the diol compound and the physical properties of the elastomer, 4,4'-diphenylmethanediisocyane It is the best.
디이소시아네이트(C)의 사용량은 장쇄 디올(A)과 제3급 아미노기를 가지는 폴리올(B)을 혼합한 화합물(A+B)에 대하여 C/(A+B)=1.23∼2.7몰이 바람직하며 1.23몰 미만에서는 중합물의 신도는 우수하나 강도가 저하되고 탄성회복력이 부족하며 2.7몰 초과시는 강도와 탄성회복율은 우수하나 신도가 불량하여 탄성중합체로서의 고유한 물성의 저하를 초래한다.As for the usage-amount of diisocyanate (C), C / (A + B) = 1.23-2.7 mol is preferable with respect to the compound (A + B) which mixed the long-chain diol (A) and the polyol (B) which has a tertiary amino group, and is 1.23. If it is less than mole, the polymer has excellent elongation, but its strength is low and its elastic recovery is insufficient. If it exceeds 2.7 moles, its strength and elastic recovery rate are excellent, but its elongation is poor, resulting in inherent degradation of physical properties as an elastomer.
장쇄디올(A)과 폴리올(B), 디이소시아네이트(C)가 결합된 예비중합물은 디아민 화합물에 의해 쇄성장되며 일정한 분자량으로 쇄성장시킨 후 모노아민으로 쇄정지를 시킴으로서 적당한 분자량의 중합물을 얻을 수 있다.The prepolymer obtained by combining long-chain diol (A), polyol (B), and diisocyanate (C) is chain-grown by a diamine compound and chain-grown at a constant molecular weight, and then chain-stopped with monoamine to obtain a polymer having an appropriate molecular weight. have.
예비중합물을 쇄성장시키는 디아민화합물(D)로서는 메틸이미노비스프로필아민, 2,5-디메틸피페라진, 1,2-프로필렌디아민, 2,3-부틸렌디아민, 메타자이렌디아민, 파라자이렌디아민, 2-메틸피페라진, 에틸렌디아민, 에탄올디아민, 테트라메틸렌디아민, 펜타메틸렌디아민, 헥사메틸렌디아민, 1-메틸-2,4-디아민벤젠, 1,2-사이클로헥산디아민, 1,3-사이클로헥산디아민, 1,4-사이클로헥산디아민, 옥타메틸렌디아민, 파라페닐렌디아민 등의 화합물이 사용되며 이의 사용범위는 예비중합물에 대해 0.5∼0.98몰로써 이 범위를 벗어나면 본 발명에서 요구되는 특성이 얻어지지 않는다.As diamine compound (D) which chain-grows a prepolymer, methyliminobispropylamine, 2, 5- dimethyl piperazine, 1, 2- propylene diamine, 2, 3- butylene diamine, meta xylene diamine, and para xylene diamine , 2-methylpiperazine, ethylenediamine, ethanoldiamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1-methyl-2,4-diaminebenzene, 1,2-cyclohexanediamine, 1,3-cyclohexane Compounds such as diamine, 1,4-cyclohexanediamine, octamethylenediamine, paraphenylenediamine and the like are used, and the range of use thereof is 0.5 to 0.98 moles with respect to the prepolymer, and the characteristics required by the present invention are obtained when outside this range. I do not lose.
이러한 쇄성장 화합물중 중합물의 점도안정성과 방사후 탄성사의 물성을 향상시키기 위해서는 선형의 아민과 환형의 아민을 적정비율로 혼합하여 사용하여야 한다.In order to improve the viscosity stability of the polymer in the chain growth compound and the properties of the elastic yarn after spinning, a linear amine and a cyclic amine should be mixed in an appropriate ratio.
선형의 디아민(D-1)과 환형의 디아민(D-2)의 사용몰비(D-1)/(D-2)는 2∼18의 범위가 적당하며 만일 (D-1)/(D-2)의 몰비가 2 미만일 경우는 저분자량의 폴리머가 생성되므로 강도, 신도, 탄성회복율 등 기계적인 물성의 저하를 초래하며, (D-1)/(D-2)의 몰비가 18을 초과할 경우는 반응속도가 지나치게 빨라서 부반응물이 다량으로 발생되어 폴리머의 안정성이 저하되고 내열성도 저하된다.The molar ratio (D-1) / (D-2) of linear diamine (D-1) and cyclic diamine (D-2) is in the range of 2 to 18, and if (D-1) / (D- When the molar ratio of 2) is less than 2, a low molecular weight polymer is produced, resulting in deterioration of mechanical properties such as strength, elongation and elastic recovery rate, and the molar ratio of (D-1) / (D-2) exceeds 18. In this case, the reaction rate is too fast to generate a large amount of side reactants, thereby degrading the stability of the polymer and lowering the heat resistance.
쇄성장된 예비중합물의 말단을 봉쇄시키는 쇄정지제인 모노아민 화합물(E)로서는 모노에탄올아민, 디에탄올아민, 프로필아민, 이소프로필아민, 디이소프로필아민, 2-에틸헥실아민, 디(2-에틸헥실)아민, 부틸아민 등의 화합물이 있는데, 상기 쇄성장 디아민 화합물과의 반응성을 고려할때 이소프로필아민이 쇄정지 효과가 우수하여 중합물의 분자량을 적당하에 유지시키며 2차적인 부반응을 억제하여 중합물의 안정성을 부여한다. 이소프로필 아민의 사용량은 전체아민 사용량의 1∼30몰%가 적당하며, 1몰% 미만에서는 쇄정지효과가 불량하여 중합물의 점도가 급상승하고 점도의 경시변화도 심하여 점도가 계속 상승함으로써 방사에 부적절하고 30몰%를 초과하면 중합물의 쇄성장을 방해하여 적정 분자량의 중합물로 성장되지 않아서 방사에 적당한 점도를 얻을 수가 없을 뿐만 아니라 중합물의 물리적인 물성인 강도, 신도, 탄성회복율이 불량하다.As monoamine compound (E) which is a chain stopper which blocks the terminal of the chain-grown prepolymer, monoethanolamine, diethanolamine, propylamine, isopropylamine, diisopropylamine, 2-ethylhexylamine, di (2- There are compounds such as ethylhexyl) amine and butyl amine. In consideration of the reactivity with the chain growth diamine compound, isopropylamine has an excellent chain stop effect, thereby maintaining the molecular weight of the polymer moderately and suppressing secondary side reactions. Gives stability. The amount of isopropyl amine is 1 to 30 mol% of the total amine usage, and less than 1 mol% is poor in the chain stop effect, the viscosity of the polymer rapidly rises, the viscosity changes over time and the viscosity continues to rise, making it unsuitable for spinning. If it exceeds 30 mol%, the chain growth of the polymer may be prevented from being grown into a polymer having an appropriate molecular weight, and thus, a viscosity suitable for spinning may not be obtained, and the strength, elongation, and elastic recovery of the polymer may be poor.
중합물의 고형분을 조절하므로서 방사성을 좋게 하기 위한 용제로서는 디메틸아세트아미드, 디메틸포름아미드, 헥사메틸포스포름아미드, 디메틸니트로소아민, 디메틸프로피온아미드, 메톡시디메틸아세트아미드, N-메틸피로리딘, 디메틸설폭시드, 테트라메틸렌설폰 등의 화합물이 있는데 디메틸아세트아미드 또는 디메틸포름아미드가 중합물과의 상용성, 방사성, 용제회수성면에서 유리하다. 용제의 사용량은 중합물의 고형분이 15∼43%되게 조정하여 사용하는 것이 좋으며, 15% 미만이거나 43% 초과에서는 방사성에 악영향을 미친다.Examples of solvents for improving radioactivity by controlling the solid content of the polymer include dimethylacetamide, dimethylformamide, hexamethylphosphoramide, dimethylnitrosoamine, dimethylpropionamide, methoxydimethylacetamide, N-methylpyrrolidine, and dimethyl sulfoxide. There are compounds such as seeds and tetramethylenesulfone, and dimethylacetamide or dimethylformamide is advantageous in terms of compatibility with the polymer, radioactivity and solvent recovery. The amount of the solvent to be used is preferably adjusted to 15 to 43% of the solid content of the polymer, and less than 15% or more than 43% adversely affects radioactivity.
이렇게 제조한 폴리우레탄 중합체는 기계적인 물성과 내열성은 우수하나 내염소성이 불량하여 수영복으로 착용시 수영장의 염소에 의해 손상을 받아서 섬유의 강도와 탄성회복율이 저하되고 변색되는 경우가 있으므로 염소에 의한 손상을 방지하기 위하여 아래와 같은 내염소성 화합물을 첨가한다.Polyurethane polymer prepared in this way has excellent mechanical properties and heat resistance, but is poor in chlorine resistance, so it is damaged by chlorine in the swimming pool when worn as a swimsuit, and the strength and elastic recovery rate of the fiber may be reduced and discolored. In order to prevent the addition of the following chlorine resistant compounds.
염소에 의한 손상을 방지하는 화합물로서는 아연스테아레이트, 아연라우레이트, 아연리시노레이트, 아연옥토에이트, 아연벤조에이트 등 지방족 금속염이나 산화아연, 산화알미늄, 산화지르코늄, 산화마그네슘, 산화제2주석, 산화세리움 등 금속산화물이나 안하이드라이드계 화합물을 알콜과 반응시켜서 디에스테르 화합물을 생성시킨후 말단의 수소를 금속으로 치환한 금속염계 화합물이 사용되며 이러한 안하이드라이드계 화합물은 벤조익 안하이드라이드, 아세틱벤조익 안하이드라이드, 아세틱 안하이드라이드, 프탈릭 안하이드라이드, 숙시닉 안하이드라이드, 말레익 안하이드라이드, 아세틱프타노익 안하이드라이드 화합물 등이 있는데, 이들 화합물은 탄성중합체의 고유한 물성을 저해하지 않으면서도 염소에 대한 견뢰도를 향상시키는데 특히 안하이드라이드계 화합물로부터 제조된 디에스테르 화합물의 말단 수소를 금속으로 치환한 금속염계 화합물이 더 좋은 효과를 나타낸다.Examples of compounds that prevent damage by chlorine include aliphatic metal salts such as zinc stearate, zinc laurate, zinc licinolate, zinc octoate and zinc benzoate, zinc oxide, aluminum oxide, zirconium oxide, magnesium oxide, tin oxide, and oxidation. Metal salts such as cerium, or anhydride-based compounds are reacted with alcohols to form diester compounds, and metal salt-based compounds in which hydrogen at the terminal is substituted with metals are used. These anhydride-based compounds are benzoic anhydrides, Aceticbenzoic anhydrides, acetic anhydrides, phthalic anhydrides, succinic anhydrides, maleic anhydrides, aceticptanoic anhydride compounds, and the like. Specially designed to improve fastness to chlorine without compromising its inherent properties The anhydride-based metal salt-based compound substituted by a terminal hydrogen of the prepared diester compound of a metal from a compound shows a better effect.
이러한 디에스테르 금속염계 화합물의 적정 사용량은 중합물 고형분에 대하여 0.01∼4.5중량%가 바람직하며 0.01중량% 미만일 경우 내염소성 효과가 불충분하고 4.5중량% 초과될 경우 내염소성의 상승효과가 미미할 뿐만 아니라 탄성중합체의 고유한 물성을 저해하고 방사성에도 악영향을 미치게 된다.The proper amount of the diester metal salt compound is preferably 0.01 to 4.5% by weight relative to the polymer solid content, and less than 0.01% by weight of the chlorine resistance effect is insufficient. Inhibit the inherent physical properties of and adversely affect radioactivity.
상기 방법으로 제조한 중합체 용액을 통상의 건식방사법을 이용하여 방사후 70데니어의 폴리우레탄 탄성사를 제조하고 각종 물성을 측정하였다. 실시예와 비교예에 나타난 인장강도, 신도 및 탄성회복율은 KSK 0219에 준하고, 내염소성은 유효염소농도가 20ppm이고 pH가 7인 용액을 제조후 용액의 온도를 25℃로 유지시키고 이 용액내에 탄성사를 일정시간 처리후 인장강도 및 신도의 변화를 측정하였으며 내열성은 탄성사를 130℃의 열풍건조기에서 60분간 처리한 후 강도유지율 및 색상변화(Gray scale; ISO international standard를 이용하여 급수판정)로 평가하였다.The polymer solution prepared by the above method was prepared using a conventional dry spinning method to prepare a polyurethane elastic yarn of 70 denier after spinning and measured various physical properties. Tensile strength, elongation and elastic recovery rate shown in Examples and Comparative Examples are in accordance with KSK 0219, chlorine resistance is 20ppm effective chlorine concentration and pH 7 after the preparation of the solution to maintain the solution temperature of 25 ℃ in this solution After the elastic yarns were treated for a certain time, the changes in tensile strength and elongation were measured, and the heat resistance was evaluated by strength retention and color change (Gray scale; water supply determination using ISO international standard) after the elastic yarns were treated for 60 minutes in a hot air dryer at 130 ° C. It was.
다음의 실시예 및 비교예는 본 발명을 좀 더 구체적으로 설명하는 것으로 본 발명의 범주를 한정하는 것은 아니다.The following examples and comparative examples illustrate the present invention in more detail and do not limit the scope of the present invention.
[실시예 1]Example 1
1,4-부탄디올과 디페닐카보네이트와의 축합반응에 의해 합성된 분자량 2000의 폴리헥사메틸렌카보네이트디올 1몰, 분자량이 1800인 폴리테트라메틸렌글리콜 1몰, N-이소프로필디에탄올아민 0.1몰을 82℃에서 감압하에 교반시켜 수분을 제거한 후 50℃에서 미리 가열된 4,4'-디페닐메탄디이소시아네이트 4.2몰을 첨가하여 질소가스 분위기하에서 80℃에서 60분간 중합하여 예비중합물을 제조하였다. 이 예비중합물을 디메틸아세트아미드에 용해시켜 용액의 온도를 5℃까지 냉각후 쇄성장제로서 선형아민인 에틸렌디아민 1몰과 1,2-프로필렌디아민 0.8몰 및 환형아민인 메타자이렌 디아민 0.2몰과 1,4-사이클로헥산디아민 0.1몰을 디메틸 아세트아미드에 15% 농도로 용해시킨 쇄성장제 용액을 예비중합물에 서서히 첨가하여 점도가 3200포아즈인 중합물을 얻었다.1 mol of polyhexamethylene carbonate diol having a molecular weight of 2000 synthesized by condensation reaction of 1,4-butanediol with diphenyl carbonate, 1 mol of polytetramethylene glycol having a molecular weight of 1800, and 0.1 mol of N-isopropyl diethanolamine were used. After stirring under reduced pressure at 0 ° C. to remove moisture, 4.2 mol of 4,4′-diphenylmethane diisocyanate preheated at 50 ° C. was added thereto, followed by polymerization at 80 ° C. for 60 minutes in a nitrogen gas atmosphere to prepare a prepolymer. The prepolymer was dissolved in dimethylacetamide, and the solution was cooled to 5 DEG C, followed by 1 mole of ethylenediamine as linear amine, 0.8 mole of 1,2-propylenediamine as a chain growth agent, and 0.2 mole of metastyrene diamine as cyclic amine. A chain growth agent solution in which 0.1 mol of 1,4-cyclohexanediamine was dissolved in dimethyl acetamide at a concentration of 15% was gradually added to the prepolymer to obtain a polymer having a viscosity of 3200 poise.
이 중합물에 이소프로필아민 0.2몰을 디메틸아세트아미드에 15% 농도로 용해시킨 용액을 서서히 첨가하여 점도가 3200포아즈인 중합물을 얻었다.To the polymer was slowly added a solution obtained by dissolving isopropylamine 0.2 mol in 15% concentration in dimethylacetamide to obtain a polymer having a viscosity of 3200 poise.
중합완료후 내염소성 향상첨가제인 디에스테르 금속염계 화합물을 디메틸아세트아미드에 2%의 농도로 용해시킨 용해액을 내염소성 첨가제가 최종 폴리머 고형분의 0.5중량% 되게 첨가하여 최종 중합물의 고형분을 30%로 조정하였다. 이때의 점도는 2800포아즈(45℃)이다. 이 중합물을 통상의 건식방사법을 이용하여 방사후 70데니어의 폴리우레탄계 탄성사를 제조하였으며, 물성을 평가한 결과는 표 1과 같다.After the completion of the polymerization, a dissolution solution of a diester metal salt compound, a chlorine resistance improving additive, was dissolved in dimethylacetamide at a concentration of 2%, so that a chlorine-resistant additive was added to 0.5% by weight of the final polymer solids, and the solid content of the final polymer was 30%. Adjusted. The viscosity at this time is 2800 poise (45 degreeC). The polymer was prepared by spinning a 70 denier polyurethane elastic yarn after spinning using a conventional dry spinning method, and the results of the evaluation of the physical properties are shown in Table 1.
[비교예 1]Comparative Example 1
분자량 2000의 폴리헥사메틸렌카보네이트디올 0.3몰, 분자량 1800의 폴리테트라메틸렌글리콜 1.7몰을 사용한 것 이외에는 실시예 1과 동일하게 탄성사를 제조하였으며, 물성을 평가한 결과는 표 1과 같다.An elastic yarn was prepared in the same manner as in Example 1 except that 0.3 mol of polyhexamethylene carbonate diol having a molecular weight of 2000 and 1.7 mol of polytetramethylene glycol having a molecular weight of 1800 were used. The results of the evaluation of the physical properties are shown in Table 1.
[비교예 2]Comparative Example 2
제3급 아미노기를 가지는 N-이소프로필디에탄올아민을 사용하지 않은것 외에는 실시예 1과 동일하게 탄성사를 제조하였으며, 물성을 평가한 결과는 표 1과 같다.An elastic yarn was prepared in the same manner as in Example 1 except that N-isopropyldiethanolamine having a tertiary amino group was not used. The results of the evaluation of the physical properties are shown in Table 1 below.
[비교예 3]Comparative Example 3
내염소성 향상 첨가제인 디에스테르 금속염계 화합물을 사용하지 않은것 이외에는 실시예 1과 동일하게 탄성사를 제조하였으며 물성을 평가한 결과는 표 1과 같다.Except not using a diester metal salt-based compound of the chlorine resistance improving additives was prepared in the same manner as in Example 1 and the results of the evaluation of the physical properties are shown in Table 1.
Claims (7)
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| KR100646647B1 (en) * | 2001-04-19 | 2006-11-17 | 주식회사 코오롱 | A process of preparing polyurethane type elastic fiber |
| KR100719044B1 (en) * | 2001-04-19 | 2007-05-16 | 주식회사 코오롱 | A polyurethane type elastic fiber, and a process of preparing for the same |
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| KR100521039B1 (en) * | 1999-01-19 | 2005-10-12 | 주식회사 효성 | Process for preparing polyurethane e1astomer of good eveness |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100646647B1 (en) * | 2001-04-19 | 2006-11-17 | 주식회사 코오롱 | A process of preparing polyurethane type elastic fiber |
| KR100719044B1 (en) * | 2001-04-19 | 2007-05-16 | 주식회사 코오롱 | A polyurethane type elastic fiber, and a process of preparing for the same |
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