KR20160077301A - A method for preparing polyurethaneurea elastic fiber with excellent uniformity and work - Google Patents
A method for preparing polyurethaneurea elastic fiber with excellent uniformity and work Download PDFInfo
- Publication number
- KR20160077301A KR20160077301A KR1020140186113A KR20140186113A KR20160077301A KR 20160077301 A KR20160077301 A KR 20160077301A KR 1020140186113 A KR1020140186113 A KR 1020140186113A KR 20140186113 A KR20140186113 A KR 20140186113A KR 20160077301 A KR20160077301 A KR 20160077301A
- Authority
- KR
- South Korea
- Prior art keywords
- polyurethane
- elastic yarn
- yarn
- urea
- urea elastic
- Prior art date
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/04—Dry spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/32—Elastic yarns or threads ; Production of plied or cored yarns, one of which is elastic
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/10—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyurethanes
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/12—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyureas
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/06—Load-responsive characteristics
- D10B2401/061—Load-responsive characteristics elastic
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/22—Physical properties protective against sunlight or UV radiation
Abstract
Description
본 발명은 균일성과 작업성이 우수한 폴리우레탄우레아 탄성사의 제조방법에 관한 것으로서, 더욱 상세하게는 폴리우레탄우레아 탄성사 제조시에 황산바륨을 첨가함으로써 원사의 균제도를 향상시켜 균일성이 우수하고 작업성이 양호하게 개선된 폴리우레탄우레아 탄성사의 제조방법에 관한 것이다.
The present invention relates to a method for producing a polyurethane-urea elastic yarn excellent in uniformity and workability, and more particularly, to a method for producing a polyurethane-urea elastic yarn having excellent uniformity and workability by improving the uniformity of a yarn by adding barium sulphate The present invention relates to a method for producing a polyurethane-urea elastic yarn.
폴리우레탄 우레아는 일반적으로 고분자량의 디올 화합물인 폴리올과 과량의 디이소시아네이트 화합물을 반응시켜 폴리올의 양 말단에 이소시아네이트기를 가지는 예비중합체(prepolymer)를 얻는 1차 중합반응과 상기 예비중합체를 적절한 용매에 용해시킨 후 그 용액에 디아민계 또는 디올계 사슬 연장제 및 모노알코올 또는 모노아민 등과 같은 사슬 종결제 등을 첨가하여 반응시키는 단계를 거쳐, 폴리우레탄 우레아 섬유의 방사액을 만든 후 건식 및 습식 방사에 의해 폴리우레탄 우레아 탄성 섬유로 제조된다.The polyurethaneurea is prepared by a first-stage polymerization reaction in which a polyol, which is a high molecular weight diol compound, is reacted with an excessive diisocyanate compound to obtain a prepolymer having isocyanate groups at both terminals of the polyol, A chain terminator such as a diamine type or a diol type chain extender and a monoalcohol or a monoamine is added to the solution and reacted to prepare a spinning solution of the polyurethane urea fiber followed by dry and wet spinning It is made of polyurethane-urea elastic fiber.
일반적인 폴리우레탄우레아 탄성사는 다른 섬유인 나일론, 실크, 면 등)와 혼용 편직하여 원단으로 사용하는데, 원단 상에 줄무늬가 있을 경우 품위가 저하되어 용도 확대에 제한을 받을 수 있다.The general polyurethane urea elastic yarn is used as a fabric by knitting with other fibers such as nylon, silk, cotton, etc.). If there is a stripe on the fabric, the quality may be lowered, which may restrict the use.
그런데, 원단의 줄무늬는 주로 불균일한 원사에 기인하므로, 균일성이 우수한 폴리우레탄우레아 탄성사의 개발이 절실하게 요구되고 있는 실정이다.However, since the streaks of the fabric are mainly caused by non-uniform yarns, there is a desperate need to develop a polyurethane-urea elastic yarn having excellent uniformity.
폴리우레탄우레아 탄성사의 제조에 관한 종래 기술로서, 한국등록특허 제10-0124963호에서는 폴리우레탄 주성분에 대하여 티오황산 바륨 0.01-10.0중량%, 염기성 알루미늄 마그네슘 카보네이트 하이드레이트 0.01-10.0중량%를 함유시키고 건식 방사하는 것을 특징으로 한 염소수에 대한 내변색성이 우수한 폴리우레탄 탄성섬유의 제조방법에 관하여 기재되어 있다.As a prior art related to the production of polyurethane-urea elastic yarn, Korean Patent Registration No. 10-0124963 discloses a process for producing a polyurethane-urea elastic yarn, which comprises 0.01-10.0 wt% of barium thiosulfate and 0.01-10.0 wt% of basic aluminum magnesium carbonate hydrate, Which is excellent in resistance to discoloration against chlorine water.
또한, 일본특허공표 제1996-511585호에서는 그 표면상에 윤활 마무리제를 가지고 한편 그 체적 내에 분산된 황산 바륨 입자를 갖는 스팬덱스이며, 스팬덱스의 점착성을 저하를 위해, 황산바륨 입자가 0~4의 범위내의 등전점을 갖는 것을 포함한 개량된 스팬덱스가 제안되어있고, EP 0380344 A3에서는 X선 탐지기능을 부여하기 위해 황산바륨을 포함하는 스팬텍스에 관하여 제안되어 있다.Japanese Patent Publication No. 1996-511585 discloses a spandex having a lubrication finish agent on its surface and having barium sulfate particles dispersed in the volume thereof. In order to lower the tackiness of spandex, 4, and EP 0380344 A3 proposes a span-Tex containing barium sulphate for imparting an X-ray detection function.
그러나 이러한 종래의 기술들도 역시 탄성사 제조시 균일성이 제대로 개선되지 아니하고 작업성도 개선되지 않아서 섬유로 제조 시에 줄무늬 발생의 문제가 여전히 개선되지 않고 있다.
However, these conventional techniques also fail to improve the uniformity of the elastic yarn and improve the workability, so that the problem of streaking during production of fibers is still not improved.
상기와 같은 종래기술의 문제점을 해결하기 위해, 본 발명은 폴리우레탄우레아 탄성사 제조시에 중합물에 황산바륨을 첨가함으로써 원사의 균제도를 향상시켜서 탄성사 제조시의 균일성과 작업성을 양호하게 개선하는 것을 해결과제로 한다.In order to solve the problems of the prior art as described above, the present invention improves the homogeneity of the yarn by adding barium sulfate to the polymerizate in the production of the polyurethane-urea elastic yarn, thereby improving the homogeneity and workability in the production of elastic yarn satisfactorily We will do it.
따라서 본 발명의 목적은 균일성과 작업성이 우수한 폴리우레탄우레아 탄성사를 제조하는 개선된 제조방법을 제공하는데 있다.Accordingly, an object of the present invention is to provide an improved method for producing a polyurethane-urea elastic yarn excellent in uniformity and workability.
또한, 본 발명의 다른 목적은 폴리우레탄우레아 제조시에 황산바륨을 적용하여 원사의 균제도가 향상된 폴리우레탄우레아 탄성사를 제공하는데 있다.
Another object of the present invention is to provide a polyurethane-urea elastic yarn in which the uniformity of yarn is improved by applying barium sulfate during the production of polyurethaneurea.
위와 같은 본 발명의 과제 해결을 위해, 본 발명은 폴리우레탄우레아 탄성사를 제조함에 있어서, 폴리우레탄우레아 중합물에 황산바륨을 고형분 대비 0.1 내지 5.0중량%로 첨가하여 건식 방사하는 것을 특징으로 하는 폴리우레탄우레아 탄성사의 제조방법을 제공한다.
In order to solve the above-mentioned problems of the present invention, the present invention provides a polyurethane-urea elastic yarn, which comprises polyurethane-urea polymerized with barium sulfate in an amount of 0.1-5.0 wt% A method for producing elastic yarn is provided.
폴리우레탄우레아 중합물의 건식 방사 중 원사 표면의 용매 건조 속도와 원사 내부에서 표면으로의 용매 확산 속도간의 편차가 작을수록 균일한 건조가 가능하여 원사 균제도 향상에 효과적이나, 사흔들림이 증가하여 작업성이 저하되는 단점이 있다.The smaller the deviation between the solvent drying speed of the yarn surface and the solvent diffusion speed from the inside of the yarn to the surface during the dry spinning of the polyurethane-urea polymer, the more uniform drying is possible to improve the yarn uniformity, .
본 발명에 따르면, 폴리우레탄우레아 중합물에 비중이 큰 황산바륨을 첨가제로 투입하여 방사함으로써, 건식 방사 중 용매의 건조를 위해 공급되는 방사 열풍에 의한 원사의 흔들림을 감소시켜 원사의 작업성과 균일성이 향상되는 효과가 있다.According to the present invention, barium sulfate having a high specific gravity is injected into the polyurethane-urea polymer by an additive to reduce shaking of the yarn by radiant hot wind supplied for drying the solvent during dry spinning, thereby improving workability and uniformity of the yarn There is an effect to be improved.
도 1은 본 발명의 실험예에서 균제도를 측정하는 과정에 대한 개념을 도식화한 도면이다.1 is a diagram illustrating a concept of a process for measuring uniformity in an experimental example of the present invention.
이하, 본 발명을 하나의 구현예로서 더욱 상세하게 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail as an embodiment.
본 발명은 폴리우레탄우레아 제조시에 황산바륨의 사용으로 균제도가 향상되며 각종 물성이 우수하고, 특히 균일성과 작업성이 크게 향상되도록 하는 폴리우레탄우레아 탄성사의 제조에 관한 것이다.The present invention relates to a polyurethane-urea elastic yarn which is improved in uniformity by using barium sulfate in the production of polyurethane urea and is excellent in various physical properties, in particular, in uniformity and workability.
본 발명에서 황산바륨은 방사하기 전에 폴리우레탄우레아 중합물에 고형분 대비 0.1 내지 5.0중량%의 량으로 첨가하는 것을 특징으로 한다. 그 황산바륨의 첨가량이 너무 적으면 균일성이 향상되지 않아서 본 발명의 목적 달성이 불가하고, 그 첨가량이 상기 범위를 벗어나 과량 첨가되면 균제도(U%)는 개선되지만 분산성 미흡으로 인해 강도나 신도 등의 물성이 너무 저하되어 바람직하지 않다. 본 발명의 더욱 바람직한 구현예에 따르면 황산바륨은 1~3중량%를 사용할 수 있다.In the present invention, barium sulfate is added to the polyurethane-urea polymer before spinning in an amount of 0.1 to 5.0% by weight based on the solids content. If the added amount of barium sulfate is too small, the uniformity is not improved and the object of the present invention can not be attained. If the added amount exceeds the above range and added in an excess amount, the uniformity (U%) is improved, And the like. According to a more preferred embodiment of the present invention, 1 to 3% by weight of barium sulfate may be used.
본 발명의 바람직한 구현예에 따르면, 황산바륨은 평균 직경이 2.0 이하인 것, 더욱 바람직하게는 0.5~1.5인 것을 사용하는 것이 좋으며, 기타 다른 첨가제를 포함할 수 있다. 이 경우 다른 첨가제와 혼합하는 경우에는 비드그라인딩(bid grinding) 작업을 30분내지 2시간 수행하여 입자 사이즈를 더욱 균일하게 하고 분산성을 향상시킬 수 있다. 본 발명에 따르면 이때 첨가제로서는 자외선, 대기 스모그 및 스판덱스 가공에 수반되는 열처리 과정 등에 의한 폴리우레탄우레아의 변색과 물성 저하를 방지하기 위해 입체장애 페놀계 화합물, 벤조퓨란-온계 화합물, 세미카바자이드계 화합물, 벤조 트리아졸계 화합물, 중합체성 3급 아민 안정제 등 중에서 선택된 하나 이상을 적절히 조합하여 사용할 수 있다.According to a preferred embodiment of the present invention, it is preferable to use barium sulfate having an average diameter of 2.0 or less, more preferably 0.5 to 1.5, and may include other additives. In this case, when mixing with other additives, a bid-grinding operation can be performed for 30 minutes to 2 hours to make the particle size more uniform and improve dispersibility. According to the present invention, in order to prevent discoloration and deterioration of physical properties of polyurethane urea by heat treatment accompanied by ultraviolet ray, atmospheric smog and spandex processing, additives such as a sterically hindered phenol compound, a benzofuran-based compound, a semicarbazide compound , A benzotriazole-based compound, a polymeric tertiary amine stabilizer, and the like can be appropriately used in combination.
본 발명에서 이러한 황산바륨을 첨가하는 제조공정을 설명하면, 폴리우레탄우레아 탄성사는 폴리올과 과량의 디이소시아네이트 화합물을 반응시켜 폴리올의 양 말단에 이소시아네이트기를 가지는 예비중합체(prepolymer)를 얻는 1차 중합반응과 상기 예비중합체를 적절한 용매에 용해시킨 후 그 용액에 디아민계 또는 디올계 사슬 연장제 및 모노알코올 또는 모노아민 등과 같은 사슬 종결제 등을 첨가하여 반응시키는 단계를 거쳐, 폴리우레탄 우레아 섬유의 방사액을 만든 후 건식 및 습식 방사에 의해 폴리우레탄 우레아 탄성사를 제조할 수 있다.In the present invention, the production process for adding barium sulfate is described. The polyurethane urea elastic yarn is prepared by reacting a polyol and an excessive diisocyanate compound to obtain a prepolymer having isocyanate groups at both ends of the polyol, After dissolving the prepolymer in a suitable solvent, a chain terminator such as a diamine or a diol chain extender and a monoalcohol or a monoamine is added to the solution, and the mixture is reacted to obtain a spinning solution of the polyurethaneurea fiber After the preparation, the polyurethane-urea elastic yarn can be produced by dry and wet spinning.
본 발명의 하나의 구현예에 따르면, 제1 중합물은 고분자량의 디올 화합물인 폴리올과 과량의 디이소시아네이트 화합물을 반응시켜 폴리올의 양 말According to one embodiment of the present invention, the first polymer is obtained by reacting a polyol which is a high molecular weight diol compound with an excessive amount of a diisocyanate compound,
단에 이소시아네이트기를 가지는 예비중합체(prepolymer)를 얻는 중합반응물과 상기 예비중합체를 유기 용매에 용해시킨 후 그 용액에 디아민 및 모노아민을 반응시키는 단계를 거쳐 제조될 수 있다.A polymerization reaction for obtaining a prepolymer having an isocyanate group at an end and a step for dissolving the prepolymer in an organic solvent and then reacting the solution with a diamine and a monoamine.
상기 디이소시아네이트는 4,4'-디페닐메탄디이소시아네이트, 1,5'-나프탈렌디이소시아네이트, 1,4'-페닐렌디이소시아네이트, 헥사메틸렌 디이소시아네이트, 1,4'-시클로헥산디이소시아네이트, 4,4'-디시클로헥실 메탄디이소시아네이트, 이소포론디이소시아네이트 등이 사용될 수 있으며, 상기 열거 군에서 1종 이상이 사용될 수 있다.The diisocyanate may be at least one selected from the group consisting of 4,4'-diphenylmethane diisocyanate, 1,5'-naphthalene diisocyanate, 1,4'-phenylene diisocyanate, hexamethylene diisocyanate, 1,4'-cyclohexane diisocyanate, 4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, and the like, and one or more of them may be used in the above listed groups.
본 발명에 사용되는 폴리올은 폴리테트라메틸렌에테르 글리콜, 폴리프로필렌글리콜, 폴리카보네이트디올, 알킬렌옥사이드와 락톤모노머의 혼합물과 폴리(테트라메틸렌에테르)글리콜의 공중합체, 3-메틸-테트라히드로푸란과 테트라히드로푸란의 공중합체 등에서 1종 또는 이들의 2종 이상의 혼합물로 예시할 수 있으나, 반드시 이들로 제한되는 것은 아니다.The polyols used in the present invention include polytetramethylene ether glycols, polypropylene glycols, polycarbonate diols, copolymers of a mixture of an alkylene oxide and a lactone monomer and poly (tetramethylene ether) glycol, 3-methyl-tetrahydrofuran and tetra And hydrofluorocarbons, or a mixture of two or more thereof, but the present invention is not limited thereto.
본 발명에서 예비중합체의 이소시아네이트 중량 비율은 폴리우레탄우레아 탄성사로서의 적정한 물성 발현을 위하여 1.7 내지 4.1%인 것이 바람직하다. 만약 예비중합체의 이소시아네이트 중량비율이 1.7% 미만이거나 4.1%를 초과하면 탄성사의 심각한 물성 저하가 초래될 수 있다.In the present invention, the weight ratio of the isocyanate of the prepolymer is preferably 1.7 to 4.1% in order to exhibit proper physical properties as a polyurethane-urea elastic yarn. If the weight ratio of isocyanate in the prepolymer is less than 1.7% or exceeds 4.1%, severe degradation of the physical properties of the elastic yarn may result.
상기 사슬연장제로는 디아민류가 사용되며, 그 예로는 에틸렌디아민, 1, 2-디아미노프로판, 1, 3-디아미노프로판, 1,4-디아미노부탄, 2,3-디아미노부탄, 1,5-디아미노펜탄, 1, 6-헥사메틸렌디아민 및 1,4-씨클로헥산디아민 등의 1종 또는 이들의 2종 이상의 혼합물을 예시할 수 있다. Examples of the chain extender include diamines such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 2,3-diaminobutane, 1 , 5-diaminopentane, 1,6-hexamethylenediamine and 1,4-cyclohexanediamine, or a mixture of two or more thereof.
폴리우레탄우레아의 사슬종결제로는 1 관능기를 갖는 아민, 예를 들어 디에틸아민, 모노에탄올아민, 디메틸아민 등이 사용될 수 있다.As the chain terminator of polyurethaneurea, amines having one functional group such as diethylamine, monoethanolamine, dimethylamine and the like can be used.
본 발명에 따르면 폴리우레탄우레아 중합물을 제조하고, 여기에 황산바륨을 상기 함량으로 첨가하여 건식 방사 함으로써 폴리우레탄우레아 탄성사를 제조할 수 있다.According to the present invention, a polyurethane-urea elastic yarn can be produced by preparing a polyurethane-urea polymer, adding barium sulfate thereto in the above-mentioned content, and then dry-spinning.
본 발명에 따르면 이러한 방사 과정에서 원사 표면의 용매 건조 속도와 원사 내부에서 표면으로의 용매 확산 속도간의 편차가 작을수록 균일한 건조가 진행되어 원사의 균일성을 향상시킬 수 있는 것이다.According to the present invention, as the deviation between the solvent drying rate on the surface of the yarn and the solvent diffusion rate from the inside of the yarn to the surface during the spinning process becomes smaller, uniform drying can be progressed and uniformity of the yarn can be improved.
본 발명에 따르면, 상기와 같이 첨가되는 황산바륨은 비중이 큰 물질이기 때문에 폴리우레탄우레아 중합물에 첨가제로 투입하여 방사하게 되면, 건식 방사 중 용매의 건조를 위해 공급되는 방사 열풍에 의한 원사의 흔들림이 크게 감소하게 되어 안정감이 있는 방사상태가 유지되므로 원사의 작업성이 확보되고, 균일한 건조를 위해 방사통 하부로의 열량 공급을 증가시킬 수 있어 균일성이 확보되는 것이다.According to the present invention, since barium sulfate added as described above is a substance having a high specific gravity, when it is added and injected into the polyurethane-urea polymeride as an additive, shaking of the yarn due to radiant hot wind supplied for drying the solvent during dry- It is possible to secure the workability of the yarn, and the uniformity can be secured because the supply of heat to the lower portion of the spinneret can be increased for uniform drying.
본 발명에 따른 바람직한 구현에에 따르면, 본 발명에 따른 폴리우레탄우레아 탄성사는 균일성과 방사 과정에서의 작업성이 우수하고, 강도와 신도 우수한 상태를 유지할 수 있는 것이다.According to a preferred embodiment of the present invention, the polyurethane-urea elastic yarn according to the present invention is excellent in workability in uniformity and spinning process, and can maintain excellent strength and elongation.
본 발명은 상기와 같이 제조된 황산바륨을 0.1~5.0중량% 함유한 폴리우레탄우레아 탄성사를 포함한다.The present invention includes a polyurethane-urea elastic yarn containing 0.1 to 5.0% by weight of barium sulfate prepared as described above.
또한 본 발명은 상기와 같이 제조된 폴리우레탄우레아 탄성사로 제조된 스판덱스를 포함한다.The present invention also includes a spandex made of the polyurethane-urea elastic yarn prepared as described above.
이하, 본 발명을 실시예에 의해 상세하게 설명하겠는 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to the examples.
실시예 1Example 1
캡핑비(CR) 1.75, 4,4'-디페닐메탄디이소시아네이트와 폴리테트라 메틸렌에테르글리콜로 조제하였다. 사슬연장제로는 에틸렌디아민과 1,2-디아미노 프로판을 80몰%와 20몰% 비율로, 사슬종결제로는 디에틸아민을 사용하였다. 사슬연장제와 사슬종결제의 비율은 10:1로 하였고, 사용된 아민은 총 농도 7몰%로 조제하였으며, 용제로는 디메틸아세트아마이드를 사용하였다. And a capping ratio (CR) of 1.75, 4,4'-diphenylmethane diisocyanate and polytetramethylene ether glycol. Ethylene diamine and 1,2-diaminopropane were used in a ratio of 80 mol% and 20 mol%, and diethylamine was used as a chain terminator. The ratio of the chain extender and the chain terminator was 10: 1, the amine used was adjusted to a total concentration of 7 mol%, and dimethylacetamide was used as the solvent.
이러한 중합물의 고형분 대비 첨가제로서 황산바륨을 0.5중량% 첨가 혼합하여 폴리우레탄우레아 방사 용액을 얻었다.As a additive for the solid content of the polymer, 0.5 wt% of barium sulfate was added and mixed to obtain a polyurethane-urea spinning solution.
위와 같이 수득한 방사 원액을 900m/min 속도로 건식 방사하여 20데니아 1 필라멘트의 폴리우레탄우레아 탄성사를 제조하였고, 그 물성을 평가하여 다음 표 1에 나타내었다.The spinning solution thus obtained was spin-dried at a speed of 900 m / min to prepare a 20 denier 1 filament polyurethane-urea elastic yarn.
실시예 2Example 2
중합물의 고형분 대비 첨가제로서 황산바륨을 1.0중량% 첨가 혼합하는 것을 제외하고는 실시예 1과 동일하게 실시하여 폴리우레탄우레아 탄성사를 제조하였고, 그 물성을 평가하여 다음 표 1에 나타내었다.The polyurethane-urea elastic yarn was prepared in the same manner as in Example 1 except that barium sulfate was added in an amount of 1.0 wt% as an additive to the solid content of the polymer, and the physical properties of the result were shown in Table 1 below.
실시예 3Example 3
중합물의 고형분 대비 첨가제로서 황산바륨을 3.0중량% 첨가 혼합하는 것을 제외하고는 실시예 1과 동일하게 실시하여 폴리우레탄우레아 탄성사를 제조하였고, 그 물성을 평가하여 표 1에 나타내었다.The polyurethane-urea elastic yarn was prepared in the same manner as in Example 1 except that 3.0 wt% of barium sulfate was added as an additive to the solids content of the polymer, and the physical properties of the result were shown in Table 1.
실시예 4Example 4
중합물의 고형분 대비 첨가제로서 황산바륨을 5.0중량% 첨가 혼합하는 것을 제외하고는 실시예 1과 동일하게 실시하여 폴리우레탄우레아 탄성사를 제조하였고, 그 물성을 평가하여 표 1에 나타내었다.A polyurethane-urea elastic yarn was produced in the same manner as in Example 1 except that 5.0 wt% of barium sulfate was added as an additive to the solids content of the polymer, and the physical properties of the result were shown in Table 1.
비교예 1Comparative Example 1
중합물의 고형분 대비 첨가제로서 황산바륨을 첨가 혼합하지 않는 것을 제외하고는 실시예 1과 동일하게 실시하여 폴리우레탄우레아 탄성사를 제조하였고, 그 물성을 평가하여 표 1에 나타내었다.The polyurethane-urea elastic yarn was prepared in the same manner as in Example 1 except that barium sulfate was not added as an additive to the solids content of the polymer, and the physical properties of the result were shown in Table 1.
비교예 2Comparative Example 2
방사 열량을 11 공급하는 것을 제외하고는 비교예 1과 동일하게 실시하여 폴리우레탄우레아 탄성사를 제조하였고, 그 물성을 평가하여 표 1에 나타내었다.The polyurethane-urea elastic yarn was produced in the same manner as in Comparative Example 1, except that the amount of radial heat was 11, and the physical properties of the result were shown in Table 1.
이 때 방사 조건은 20de/1fila., 사속 900m/min 기준으로 제조하였다.The spinning conditions were 20de / 1fila and 900m / min.
실험예Experimental Example
상기 실시예와 비교예에서 폴리우레탄우레아 탄성사에 대해 각종 물성을 측정하고 그 결과는 다음 표 1에 나타내었다.Various physical properties of the polyurethane-urea elastic yarn were measured in the above Examples and Comparative Examples, and the results are shown in Table 1 below.
본 실험예서 각 물성의 측정 방법을 다음과 같이 시행하였다.The measurement method of each property was carried out as follows.
(1) NCO% 측정법 (1) NCO% measurement method
NCO% 측정은 다음 수학식 1로 측정하였다.The NCO% measurement was measured by the following equation (1).
[수학식 1][Equation 1]
NCO% = [100*2*NCO 화학식량*(캐핑비-1)]/{(디이소시아네이트 분자량*캐핑비)+폴리올 분자량}NCO% = [100 * 2 * NCO chemical formula * (capping ratio-1)] / {(diisocyanate molecular weight * capping ratio) + polyol molecular weight}
여기서, 캐핑비는 디이소시아네이트 몰비/폴리올의 몰비를 의미한다.Here, the capping ratio means a molar ratio of diisocyanate molar ratio / polyol.
(2) 원사의 강도 및 신도 측정(2) Strength and elongation measurement of yarn
원사의 강도 및 신도는 자동 강신도 측정장치(MEL기, Textechno社)를 이용하여 시료길이 10cm, 인장속도 100 cm/min로 하여 측정하였다. 이때 파단 시의 강도와 신도 값이 측정되며, 원사 200 % 신장 시 원사에 걸리는 하중 200%의 모듈러스(modulus)도 측정하였다.The strength and elongation of the yarn were measured with a sample length of 10 cm and a tensile speed of 100 cm / min using an automatic power measuring device (MEL, Textechno). At this time, the strength and elongation at break were measured, and the modulus of 200% load applied to the yarn at 200% elongation was also measured.
(3) 원사의 균제도(U%) 측정방법(3) Method of measuring uniformity (U%) of yarn
Uster% 측정장치(KET-QT)를 이용하여 Feeding Roller의 Speed를 원사 de에 따라 다르게(20d는 30m/min) 설정하여 측정. 일정 속도로 20초간 해사된 원사의 굵기를 센서가 자동으로 읽어 평균값을 계산해 0% 기준으로 line을 그린 뒤, 평균값 대비 단위 시간당 센서가 읽은 원사의 굵기가 더 굵으면 0% 기준 line 대비 (+)영역에 point를 찍고, 굵기가 얇으면 0% 기준 line 대비 (-) 영역에 point를 찍어 그래프를 그린다. 이때 0% 기준 line에서 벗어나는 정도를 면적으로 계산하여 U%를 나타내며, 값이 작을수록 원사의 균일성이 우수함을 의미한다. 이러한 균제도의 환산식은 다음 수학식 2와 같다.Using a Uster% measuring device (KET-QT), measure the speed of the feeding roller by setting the yarn de (20d: 30m / min) according to de. If the thickness of the yarn read by the sensor per unit time per unit of the average value is larger than 0% of the reference line (+), the sensor automatically reads the thickness of the yarn, If the thickness is thin, draw a point on the area (-) compared to the 0% reference line and draw the graph. In this case, the area deviating from the 0% reference line is calculated as an area to indicate U%, and the smaller the value, the better the uniformity of the yarn. The conversion equation of this uniformity is expressed by the following equation (2).
[수학식 2]&Quot; (2) "
U% = (0% 기준 line을 벗어나는 면적 / 0% 기준 line 아래 면적) ⅹ 100U% = (Area outside of 0% reference line / area below 0% reference line) ⅹ 100
상기와 같이, 균제도(U%)를 구하는 과정을 개념적으로 도시한 모식도는 도 1과 같다.As described above, a schematic diagram conceptually showing the process of obtaining uniformity (U%) is shown in FIG.
도 1에서 보면 0% 기준으로 그 라인에서 벗어나는 정도의 면적을 확인할 수 있어서 균제도의 계산의 개념을 확인할 수 있다.In FIG. 1, the area of the area deviating from the line can be confirmed on the basis of 0%, so that the concept of the uniformity calculation can be confirmed.
한편, 본 실험에서 숙련된 원단 평가 담당자 5명이 상기 제조된 폴리우레탄우레아 탄성사에 나일론을 80% 혼합하여 제조된 스판덱스 원단을 육안으로 관찰하여 일정 범위 내 줄의 종류 및 개수를 체크하고 그 품위를 0~100점으로 채점하여 그 평균치로 평가한 결과로서, 80점 이상일 때 우수한 수준으로 판단한다.In this experiment, five skilled artisan evaluators were able to visually observe the spandex fabric prepared by mixing 80% of nylon with the polyurethane-urea elastic yarn prepared above, to check the type and number of the lines in a certain range, ~ 100 points, and it is judged to be excellent when it is 80 or more.
그리고, 원사의 작업성은 방사기 1Position에서 1일간 생산되는 원사의 이론 cone수 대비 작업 불량(사절, 합사 등)을 제외한 실제 생산 cone수를 나타낸 것으로 95% 이상일 때 양호한 수준으로 판단한다.In addition, the workability of the yarn indicates the actual number of cone produced, excluding working defects (yarn, yarn, etc.) compared to the number of theoretical cones of yarn produced for 1 day in 1 position of the yarn radiator.
[수학식 3]&Quot; (3) "
작업성(%) = (1일 실제 생산량 / 이론 1일 생산량) * 100Workability (%) = (actual production per day / theoretical daily production) * 100
함량[%]Barium sulfate
content[%]
열량radiation
calorie
[g/d]burglar
[g / d]
[%]Shindo
[%]
모듈러스[g]200%
Modulus [g]
(U%)Uniformity
(U%)
품위fabric
elegance
상기 표 1에서 보면, 본 발명의 실시예에 따라 제조된 경우가 비교예에 따라 제조된 경우에 비해 원단의 품위에서 월등하게 우수한 평가를 보이고 있는 것으로 확인되었다.
As shown in Table 1, it was confirmed that the fabricated according to the embodiment of the present invention is superior in terms of the quality of the fabric compared to the fabricated according to the comparative example.
본 발명에 따른 폴리우레탄우레아 탄성사의 제조방법은 원단에 줄무늬가 형성되지 않아서 균일하고 품위가 있는 원단을 위한 폴리우레탄우레아 탄성 섬유인 스판덱스 제조에 매우 유용하다. The method for producing the polyurethane-urea elastic yarn according to the present invention is very useful for producing spandex which is a polyurethane-urea elastic fiber for a uniform and durable fabric since no streaks are formed on the fabric.
Claims (5)
A process for producing polyurethane-urea elastic yarn excellent in uniformity and workability, which comprises adding 0.1 to 5.0% by weight of barium sulfate to the polyurethane-urea polymer in a proportion of 0.1 to 5.0% by weight based on the solids of the polyurethane-urea elastic yarn.
The method for producing a polyurethane-urea elastic yarn according to claim 1, wherein the barium sulfate has an average diameter of 2.0 or less.
The method according to claim 1, wherein the barium sulfate is further mixed with an additive and the bead grinding is performed for 30 minutes to 2 hours.
The polyurethane-urea elastic yarn according to any one of claims 1 to 3, wherein 0.1 to 5.0% by weight of barium sulfate is contained in the solid content of the polyurethane-urea polymer.
A spandex comprising the polyurethane-urea elastic yarn according to claim 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140186113A KR20160077301A (en) | 2014-12-22 | 2014-12-22 | A method for preparing polyurethaneurea elastic fiber with excellent uniformity and work |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140186113A KR20160077301A (en) | 2014-12-22 | 2014-12-22 | A method for preparing polyurethaneurea elastic fiber with excellent uniformity and work |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20160077301A true KR20160077301A (en) | 2016-07-04 |
Family
ID=56500773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020140186113A KR20160077301A (en) | 2014-12-22 | 2014-12-22 | A method for preparing polyurethaneurea elastic fiber with excellent uniformity and work |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20160077301A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0380344A2 (en) | 1989-01-26 | 1990-08-01 | E.I. Du Pont De Nemours And Company | Method for producing X-ray detectable spandex fibers and fibers produced thereby |
| JPH08511585A (en) | 1993-06-11 | 1996-12-03 | イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー | Spandex containing barium sulfate |
| KR0124963B1 (en) | 1993-12-21 | 1997-12-15 | 구창남 | Manufacture of polyurethane elastic fiber having discolored resistance |
-
2014
- 2014-12-22 KR KR1020140186113A patent/KR20160077301A/en not_active Application Discontinuation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0380344A2 (en) | 1989-01-26 | 1990-08-01 | E.I. Du Pont De Nemours And Company | Method for producing X-ray detectable spandex fibers and fibers produced thereby |
| JPH08511585A (en) | 1993-06-11 | 1996-12-03 | イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー | Spandex containing barium sulfate |
| KR0124963B1 (en) | 1993-12-21 | 1997-12-15 | 구창남 | Manufacture of polyurethane elastic fiber having discolored resistance |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101148302B1 (en) | Manufacturing method of polyurethaneurea elastic fiber by high speed spinning method | |
| KR20140096923A (en) | Preparation method spandex fibers having improved tackiness and unwinding property | |
| KR101157335B1 (en) | A Process for Preparing Polyurethaneurea Elastic Fiber having high Power | |
| JP6093090B2 (en) | Polyurethane urea elastic yarn with excellent uniformity and thermosetting | |
| KR101148583B1 (en) | A Process for Preparing Polyurethaneurea Elastic Fiber having high Power and elongation | |
| KR20160077301A (en) | A method for preparing polyurethaneurea elastic fiber with excellent uniformity and work | |
| KR100397704B1 (en) | Stabilized spandex | |
| KR101180508B1 (en) | Polyurethane composition for high tenacity spandex fiber, and spandex fiber prepared using the polyurethane composition | |
| KR101167377B1 (en) | Process for Preparing polyurethaneurea elastic fiber with improved heat settable properties | |
| KR101578156B1 (en) | Polyurethanurea elastic fiber having an excellent indexes of evenness and power and method of manufacturing the same | |
| KR101086744B1 (en) | A Process for Preparing Polyurethaneurea Elastic Fiber with Excellent Heat Settable Property at Low Temperature | |
| KR101396107B1 (en) | Polyurethaneurea elastic fiber with improved heat setting property and manufacturing method thereof | |
| KR20150043906A (en) | Polyurethanurea elastic fiber having a high resilience and method of manufacturing the same | |
| KR100397705B1 (en) | Spandex fiber having improved resistances to discoloration and chlorine | |
| KR101956332B1 (en) | An additive slurry for the production of polyurethane-urea elastic fibers | |
| KR101157327B1 (en) | A Process for Preparing Polyurethaneurea Elastic Fiber having high Power and Heat-resistance and fiber using it | |
| KR101312843B1 (en) | A Process for Preparing Polyurethaneurea Elastic Fiber having high Power and good recovery | |
| KR101913354B1 (en) | Polyurethaneurea elastic fiber | |
| KR101712390B1 (en) | Preparation of chlorine resistant polyurethaneurea fibber with nano size chlorine resistant | |
| KR101395973B1 (en) | Polyurethaneurea elastic fiber with improved heat setting property and manufacturing method thereof | |
| KR101255453B1 (en) | A Process for Preparing Polyurethaneurea Elastic Fiber having high Power and elongation | |
| KR100687034B1 (en) | Spandex fiber having a high tension maintenance | |
| KR20140094357A (en) | Polyurethanurea elastic yarn having improved power and elastic recovery and method for preparing the same | |
| KR101253420B1 (en) | Polyurethaneurea Elastic Fiber having high Power and Process for Preparing it | |
| KR101262775B1 (en) | A polyurethaneurea fibers with stabilization of inorganic materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| WITN | Withdrawal due to no request for examination |