KR101223461B1 - Packing method of aramid multifilament winding tube - Google Patents
Packing method of aramid multifilament winding tube Download PDFInfo
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- KR101223461B1 KR101223461B1 KR1020080040259A KR20080040259A KR101223461B1 KR 101223461 B1 KR101223461 B1 KR 101223461B1 KR 1020080040259 A KR1020080040259 A KR 1020080040259A KR 20080040259 A KR20080040259 A KR 20080040259A KR 101223461 B1 KR101223461 B1 KR 101223461B1
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- multifilament
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D3/00—Rigid or semi-rigid containers having bodies or peripheral walls of curved or partially-curved cross-section made by winding or bending paper without folding along defined lines
- B65D3/02—Rigid or semi-rigid containers having bodies or peripheral walls of curved or partially-curved cross-section made by winding or bending paper without folding along defined lines characterised by shape
- B65D3/04—Rigid or semi-rigid containers having bodies or peripheral walls of curved or partially-curved cross-section made by winding or bending paper without folding along defined lines characterised by shape essentially cylindrical
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D71/00—Bundles of articles held together by packaging elements for convenience of storage or transport, e.g. portable segregating carrier for plural receptacles such as beer cans or pop bottles; Bales of material
- B65D71/06—Packaging elements holding or encircling completely or almost completely the bundle of articles, e.g. wrappers
- B65D71/12—Packaging elements holding or encircling completely or almost completely the bundle of articles, e.g. wrappers the packaging elements, e.g. wrappers being formed by folding a single blank
- B65D71/14—Packaging elements holding or encircling completely or almost completely the bundle of articles, e.g. wrappers the packaging elements, e.g. wrappers being formed by folding a single blank having the shape of a tube, without, or not being characterised by, end walls
- B65D71/16—Packaging elements holding or encircling completely or almost completely the bundle of articles, e.g. wrappers the packaging elements, e.g. wrappers being formed by folding a single blank having the shape of a tube, without, or not being characterised by, end walls with article-locating elements
- B65D71/18—Tabs inwardly folded tabs from the upper or lower wall
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- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/06—Washing or drying
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- 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
- D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
- D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
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- 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
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/441—Yarns or threads with antistatic, conductive or radiation-shielding properties
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- 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
- D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
- D10B2331/021—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides aromatic polyamides, e.g. aramides
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- 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
- D10B2401/063—Load-responsive characteristics high strength
-
- 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
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Polyamides (AREA)
Abstract
본 발명은 아라미드 멀티필라멘트 권취지관의 포장방법 관한 것으로서, 아라미드 멀티필라멘트가 권취된 권취지관을 하기 계산식 1로 정의되는 평균자외선차단율이 80% 이상인 합성필름으로 포장하는 것을 특징으로 한다.The present invention relates to a packaging method of the aramid multifilament winding tube, characterized in that the aramid multifilament wound wrapped tube wrapped with a synthetic film having an average UV cutoff ratio of 80% or more defined by the following formula (1).
[계산식 1][Equation 1]
(상기식에서, T1은 310~360㎚ 파장영역에서의 최대 투과율이고, T2는 310~360㎚ 파장영역에서의 최소투과 투과율이고, T3는 파장 360㎚에서의 투과율이고, T4는 380㎚에서의 투과율을 나타낸다)Where T 1 is the maximum transmittance in the 310-360 nm wavelength region, T 2 is the minimum transmittance in the 310-360 nm wavelength region, T 3 is the transmittance in the wavelength 360 nm, and T 4 is 380 Transmittance at nm)
본 발명은 권취보빈에 권취된 아라미드 멀티필라멘트가 자외선에 의해 취화되는 것을 효과적으로 차단하여 상기 아라미드 멀티필라멘트의 강도유지율을 80% 이상으로 유지할 수 있다.The present invention can effectively block the aramid multifilament wound on the winding bobbin by the ultraviolet ray to maintain the strength retention of the aramid multifilament to 80% or more.
아라미드, 멀티필라멘트, 권취지관, 포장방법, 합성필름, 자외선차단율 Aramid, Multifilament, Winding Tube, Packing Method, Composite Film, UV Protection Rate
Description
본 발명은 아라미드 멀티필라멘트 권취지관의 포장방법에 관한 것이다.The present invention relates to a method for packaging an aramid multifilament wound tube.
아라미드 멀티필라멘트는 미국특허 제 3,869,429 호 및 미국특허 제 3,869,430 호 등에 게재되어 있는 바와 같이, 방향족 디아민과 방향족 디에시드클로라이드를 N-메틸-2-피롤리돈을 포함하는 중합용매 중에서 중합시켜 아라미드 중합체를 제조하는 공정과, 상기 중합체를 농황산 용매에 용해시켜 방사원액을 제조하는 공정과, 상기 방사원액을 방사 구금으로부터 방사하여 방사된 방사물을 비응고성 유체층을 통해 응고액 욕조내로 통과시켜 필라멘트를 형성하는 공정과, 상기 필라멘트를 수세 및 건조하여 권취하는 거쳐 제조된다.Aramid multifilament is disclosed in U.S. Patent Nos. 3,869,429 and 3,869,430, and the like to polymerize an aramid polymer by polymerizing aromatic diamine and aromatic dieside chloride in a polymerization solvent containing N-methyl-2-pyrrolidone. And a process for producing a spinning stock solution by dissolving the polymer in a concentrated sulfuric acid solvent, and spinning the spinning stock solution from a spinneret to pass the spun spinning material through a non-coagulant fluid layer into a coagulating bath to form a filament. And filaments are washed with water, dried and wound up to produce the same.
상기와 같은 방법으로 제조된 아라미드 멀티필라멘트는 지관에 권취된 상태 그대로 다시말해 자외선 차단을 위한 별도포장 없이 타이어 코오드 제조공정 중 하나인 합연사 공정등과 같은 후공정을 위해 운송된다.The aramid multifilament manufactured by the above method is transported for a post process such as a twisted yarn process, which is one of tire cord manufacturing processes, that is, as it is wound on a branch pipe, that is, a separate packaging for UV protection.
그로인해, 운송 중 아라미드 멀티필라멘트가 자외선에 의해 취화되어 강도유지율이 80% 미만으로 떨어지는 문제가 발생 되었다.As a result, aramid multifilament is embrittled by ultraviolet rays during transportation, resulting in a problem that the strength retention rate drops to less than 80%.
아라미드 멀티필라멘트는 높은 강도와 모듈러스를 구비하여 타이어 코오드용 원사 등으로 유용하지만, 운송 중 자외선에 의해 취화되어 강도 등의 물성이 크게 저하되는 문제가 있었다.Aramid multifilament has a high strength and modulus and is useful as a yarn for tire cords, but has a problem in that physical properties such as strength are greatly degraded due to embrittlement by ultraviolet rays during transportation.
이하, 본 발명에서는 아라미드 멀티필라멘트가 권취되어 있는 지관을 "권취지관"이라고 약칭한다.Hereinafter, in this invention, the paper pipe in which the aramid multifilament is wound is abbreviated as "winding pipe".
한편, 타이어 코오드는 타이어의 구성성분중 하나로서 타이어 고무를 보강하는 역할을 하며, 타이어 내에서 기본 골격 구조를 형성한다.On the other hand, the tire cord serves to reinforce the tire rubber as one of the components of the tire, and forms a basic skeleton structure in the tire.
타이어 보강재로써 코오드에 요구되는 성능은 내피로성, 전단강도, 내구성, 반발탄성 그리고 고무와의 접착력 등이다. 따라서, 타이어에 요구되는 성능에 따라 적절한 코오드를 사용하게 된다.The performance required for the cord as a tire reinforcement is fatigue resistance, shear strength, durability, resilience and adhesion to rubber. Therefore, the appropriate code is used according to the performance required for the tire.
현재 일반적으로 사용되는 코오드용 소재로는 레이온, 나일론, 폴리에스터, 스틸 및 아라미드 등이 사용된다.Currently commonly used cord materials include rayon, nylon, polyester, steel and aramid.
타이어 코오드 제조를 위해서는 타이어 코오드 제조용 원사(멀티필라멘트)에 상연(Z연) 꼬임을 준 다음 상연된 원사 2가닥에 다시 하연(S연) 꼬임을 주면서 합사하여 합연사(Raw cord)를 제조한 후, 이를 타이어 코오드 제조용 접착제 용액에 침지, 건조 및 열처리하는 공정을 거치게 된다.To manufacture tire cord, give twist (Z-lead) twist to yarn (multifilament) for tire cord manufacture, and then ply it while twisting while giving twist (S-lead) twist to two strands of twisted yarn to manufacture raw cord. Then, it is subjected to a process of immersing, drying and heat-treating the adhesive solution for manufacturing a tire cord.
상기 합연사(Raw cord) 제조공정을 "합연사 공정"이라고 한다.The raw cord manufacturing process is called a "ply twisted yarn process".
앞에서 설명한 바와 같이 종래와 같은 방법으로 운송되어온 아라미드 멀티필 라멘트로 아라미드 타이어 코오드를 제조하는 경우, 아라미드 멀티필라멘트의 강력이 자외선에 의해 크게 저하되어 최종제품인 타이어 코오드의 물성도 나빠지는 문제가 발생 되었다.As described above, when the aramid tire cord is manufactured from the aramid multifilament that has been transported in the same manner as in the prior art, the strength of the aramid multifilament is greatly reduced by ultraviolet rays, resulting in a problem that the physical properties of the final product tire cord are also deteriorated.
본 발명은 권취지관에 권취되어 있는 아라미드 멀티필라멘트가 운반 중 자외선에 의해 취화되어 강도가 떨어지는 것을 효과적으로 방지하는 아라미드 멀티필라멘트의 포장방법을 제공한다.The present invention provides a method for packaging aramid multifilament that effectively prevents the aramid multifilament wound on the winding tube is embrittled by the ultraviolet light during transportation to reduce the strength.
본 발명에 따른 아라미드 멀티필라멘트 권취지관의 포장방법은 아라미드 멀티필라멘트가 권취된 권취지관을 하기 계산식 1로 정의되는 평균자외선차단율이 80% 이상인 합성필름으로 포장하는 것을 특징으로 한다.The packaging method of the aramid multifilament wound paper tube according to the present invention is characterized in that the aramid multifilament wound wrapped tube wrapped with a synthetic film having an average UV cutoff rate of 80% or more, defined by the following formula (1).
[계산식 1][Equation 1]
(상기식에서, T1은 310~360㎚ 파장영역에서의 최대 투과율이고, T2는 310~360㎚ 파장영역에서의 최소투과 투과율이고, T3는 파장 360㎚에서의 투과율이 고, T4는 380㎚에서의 투과율을 나타낸다)Where T 1 is the maximum transmittance in the 310-360 nm wavelength region, T 2 is the minimum transmittance in the 310-360 nm wavelength region, T 3 is the transmittance in the wavelength 360 nm, and T 4 is Transmittance at 380 nm)
이하, 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서는 통상의 방법과 같이 도 1에 도시된 공정으로 아라미드 멀티필라멘트를 제조한다.In the present invention, the aramid multifilament is manufactured by the process shown in FIG. 1 as in a conventional method.
도 1은 본 발명에 따른 아라미드 멀티필라멘트를 제조하는 공정개략도이다.1 is a process schematic diagram of preparing aramid multifilament according to the present invention.
구체적으로, 본 발명에서는 도 1에 도시된 바와 같이 방향족 디아민과 방향족 디에시드클로라이드를 N-메틸-2-피롤리돈을 포함하는 중합용매 중에서 중합시켜 폴리(파라-페닐렌테레프탈아미드) 중합체를 제조하고, 상기 중합체를 농황산 용매에 용해시켜 방사원액을 제조하고, 상기 원액을 방사 구금으로부터 방사하여 방사된 방사물을 비응고성 유체층을 통해 응고액 욕조 내로 통과시켜 멀티필라멘트를 형성하고, 상기 멀티필라멘트를 수세 및 건조하고, 건조된 멀티필라멘트를 지관에 권취하여 아라미드 멀티필라멘트를 제조한다.Specifically, in the present invention, a poly (para-phenylene terephthalamide) polymer is prepared by polymerizing an aromatic diamine and an aromatic dieside chloride in a polymerization solvent containing N-methyl-2-pyrrolidone, as shown in FIG. Dissolving the polymer in a concentrated sulfuric acid solvent to form a spinning stock solution, spinning the stock solution from a spinneret, and passing the spun spinning material through a non-coagulating fluid layer into a coagulant bath to form a multifilament, wherein the multifilament Was washed with water and dried, and the dried multifilament was wound on a branch pipe to prepare aramid multifilament.
이때 상기 방향족 디아민은 P-페닐렌디아민 등이고, 방향족 디에시드클로라이드는 테레프탈로일 클로라이드 등이다.In this case, the aromatic diamine is P-phenylenediamine and the like, and the aromatic dieside chloride is terephthaloyl chloride and the like.
또한, 상기의 중합용매는 염화칼슘이 용해되어 있는 N-메틸-2-피롤리돈 등이다.The polymerization solvent is N-methyl-2-pyrrolidone or the like in which calcium chloride is dissolved.
상기 아라미드(전방향족 폴리아미드) 중합체의 고유점도는 5.0 이상인 것이 필라멘트의 강도 및 탄성률 향상에 좋다.The intrinsic viscosity of the aramid (fully aromatic polyamide) polymer is 5.0 or more is good for improving the strength and elastic modulus of the filament.
상기 아라미드 중합체는 미국등록 특허 제 3,869,429 호 등에 게재된 공지의 중합조건들을 사용하여 제조할 수 있으나, 본 발명에서는 상기 아라미드 중합체의 중합조건을 특별하게 한정하는 것은 아니다.The aramid polymer may be prepared using known polymerization conditions disclosed in US Pat. No. 3,869,429, etc., but the present invention does not specifically limit the polymerization conditions of the aramid polymer.
중합체를 제조하는 한가지 예로는 1몰의 파라-페닐렌디아민을 약 1몰의 염화칼슘을 포함하는 N-메틸-2-피롤리돈에 용해시킨 용액과 1몰의 테레프탈로일 클로라이드를 중합용 반응기 내에 투입한 후 교반하여 겔상의 중합체를 제조하고, 이를 분쇄, 수세 및 건조하여 미세 분말상의 아라미드 중합체를 제조한다. 이때 상기 테레프탈로일 클로라이드는 2 단계로 나누어 중합용 반응기 내에 투입할 수도 있다.One example of preparing the polymer is a solution of 1 mole of para-phenylenediamine dissolved in N-methyl-2-pyrrolidone containing about 1 mole of calcium chloride and 1 mole of terephthaloyl chloride in a polymerization reactor. After the addition, it is stirred to prepare a gel polymer, which is ground, washed with water and dried to prepare a fine powder aramid polymer. At this time, the terephthaloyl chloride may be added to the reactor for polymerization divided into two stages.
상기 방사원액 제조시에 사용되는 농황산 농도를 97%∼100%인 것이 바람직하며, 클로로황산이나 플루오로황산 등도 사용될 수 있다.The concentration of concentrated sulfuric acid used in the production of the spinning stock solution is preferably 97% to 100%, and chlorosulfuric acid, fluorosulfuric acid, and the like may also be used.
이때 황산의 농도가 97% 미만인 경우에는 폴리머의 용해성이 저하되고 비등방성 용액의 액정성 발현이 곤란해지며, 따라서 일정한 점도의 방사원액 제조가 어려워져 방사시 공정관리가 힘들고 최종 섬유의 기계적 물성이 저하될 수 있다.At this time, when the concentration of sulfuric acid is less than 97%, the solubility of the polymer is reduced and the liquid crystalline expression of the anisotropic solution becomes difficult. Therefore, it is difficult to manufacture a spinning solution having a constant viscosity, which makes it difficult to control the process during spinning and to provide mechanical properties of the final fiber. Can be degraded.
반대로, 농황산의 농도가 100%를 초과하면, 과리(過離) SO3를 함유하는 발연 황산에서 SO3가 과다해져 취급상 바람직하지 않을 뿐만 아니라 고분자의 부분적 용해가 일어나기 때문에 방사원액으로는 부적당하며, 또한, 비록 방사하여 얻어진 섬유라 할지라도 섬유의 내부구조가 치밀하지 않고 외관상 광택이 없으며 응고용액 내로 확산되는 황산의 속도가 떨어져 섬유의 기계적 물성이 저하되는 문제점이 발생될 수 있다.On the other hand, if the concentration of the concentrated sulfuric acid exceeds 100%, gwari (過離) because in oleum containing SO 3, as well as undesirable phase handled becomes an SO 3 over takes place is partly dissolved in the polymer spinning solution to the inadequate and In addition, even if the fiber is obtained by spinning, there may be a problem that the internal structure of the fiber is not dense, the appearance is not gloss, and the speed of sulfuric acid diffused into the coagulation solution is lowered, thereby lowering the mechanical properties of the fiber.
한편, 방사 원액내 중합체의 농도는 10∼25중량% 인 것이 섬유물성에 바람직 하다.On the other hand, the concentration of the polymer in the spinning stock solution is preferably 10 to 25% by weight for the fiber properties.
그러나, 본 발명에서는 농황산의 농도 및 방사 원액내 중합체의 농도를 특별하게 한정하는 것은 아니다.However, the present invention does not specifically limit the concentration of concentrated sulfuric acid and the concentration of the polymer in the spinning stock solution.
상기의 비응고성 유체층은 주로 공기층이나 불활성 기체층도 사용될 수 있다.The non-coagulating fluid layer may mainly be an air layer or an inert gas layer.
비응고성 유체층의 길이, 다시 말해 방사 구금(40)의 저면과 응고액 욕조(50)내에 담겨져 있는 응고액의 표면까지의 거리는 0.1~15cm인 것이 방사성이나 필라멘트의 물성 향상에 바람직하다.The length of the non-coagulating fluid layer, that is, the distance between the bottom surface of the spinneret 40 and the surface of the coagulating liquid contained in the coagulating
상기의 응고액 욕조(50)내의 응고액은 오버플로우 될 수도 있다. 응고액으로는 물, 염수 또는 농도가 70% 이하인 황산 수용액 등을 사용한다.The coagulant in the
이때 방사 권취 속도는 300~1,500 m/분 수준으로 한다.At this time, the spinning winding speed is set to 300 to 1500 m / min.
본 발명에서는 자외선에 의해 아라미드 멀티필라멘트의 강도 등과 같은 물성이 저하되는 것을 방지하기 위해서 상기와 같이 제조된 권취지관, 다시말해 아라미드 멀티필라멘트가 권취된 지관을 하기 계산식 1로 정의되는 평균자외선차단율이 80% 이상인 합성필름으로 포장한다.In the present invention, in order to prevent the physical properties such as the strength of the aramid multifilament is lowered by the ultraviolet rays, the winding tube manufactured as described above, that is, the branch pipe wound with the aramid multifilament is 80, the average ultraviolet ray blocking rate defined by the following formula 1 is 80 Packed in synthetic film that is more than%.
[계산식 1][Equation 1]
(상기식에서, T1은 310~360㎚ 파장영역에서의 최대 투과율이고, T2는 310~360㎚ 파장영역에서의 최소투과 투과율이고, T3는 파장 360㎚에서의 투과율이고, T4는 380㎚에서의 투과율을 나타낸다)Where T 1 is the maximum transmittance in the 310-360 nm wavelength region, T 2 is the minimum transmittance in the 310-360 nm wavelength region, T 3 is the transmittance in the wavelength 360 nm, and T 4 is 380 Transmittance at nm)
상기 합성필름은 폴리에스테르 수지, 폴리아미드 수지, 폴리에틸렌 수지, 폴리프로필렌 수지 등으로 구성되며, 상기 수지 내에 자외선 안정제 등이 포함될 수도 있다.The synthetic film is composed of a polyester resin, polyamide resin, polyethylene resin, polypropylene resin, and the like, and may include an ultraviolet stabilizer and the like in the resin.
자외선 안정제로는 벤조페논계 화합물, 벤조트리아졸계 화합물, 레솔시놀 모노벤조에이트계 화합물 등이 사용될 수 있다.As the UV stabilizer, a benzophenone compound, a benzotriazole compound, a resorcinol monobenzoate compound, or the like may be used.
상기 아라미드 멀티필라멘트는 폴리(파라-페닐렌테레프탈아미드) 이다.The aramid multifilament is poly (para-phenylene terephthalamide).
상기 권취지관의 포장방법으로는 권취지관에 평균자외선차단율이 80% 이상인 합성필름의 봉투를 덮어씌우는 방법등이 채택될 수 있다.As a packaging method of the winding tube, a method of covering the envelope of the synthetic film having an average UV blocking rate of 80% or more on the winding tube may be adopted.
상기 합성필름의 평균자외선차단율이 80% 미만인 경우에는 자외선 차단효과가 떨어져 아라미드 멀티필라멘트의 강도유지율이 80% 미만으로 떨어진다.When the average UV blocking rate of the synthetic film is less than 80%, the UV blocking effect is lowered, and the strength retention rate of the aramid multifilament falls below 80%.
상기 강도유지율의 측정방법은 후술한다.The method of measuring the strength retention will be described later.
본 발명에 따른 아라미드 멀티필라멘트의 강도는 10~25 g/d로서, 10 g/d 미만인 경우에는 강도가 낮아 타이어 코오드로 적용시 자동차 하중을 지지하기 어려워 타이어의 성능발현이 불가능한 문제가 발생되고, 25 g/d 를 초과하는 경우에는 타이어 성능 발현에는 충분한 물성을 넘어서 효율적이지 못한 문제가 발생될 수 있다.The strength of the aramid multifilament according to the present invention is 10 ~ 25 g / d, less than 10 g / d, the strength is low, it is difficult to support the vehicle load when applied as a tire cord, the problem of the performance of the tire is impossible, If it exceeds 25 g / d, problems may arise that are not efficient enough to develop tire performance.
또한, 상기 아라미드 멀티필라멘트의 절단신도는 2~6%로서, 2% 미만인 경우 에는 낮은 절단신도로 인해 타이어 코오드로 적용되기에는 피로특성이 부족한 문제가 발생되고, 6%를 초과하는 경우에는 형태안정성이 부족한 문제가 발생될 수 있다.In addition, the cut elongation of the aramid multifilament is 2 ~ 6%, if less than 2% due to the low cutting elongation is a problem that the fatigue characteristics are insufficient to be applied to the tire cord, the shape stability of more than 6% This scarce problem can occur.
또한, 상기 아라미드 멀티필라멘트의 모듈러스 400~750 g/d로서, 400 g/d 미만인 경우에는 낮은 모듈러스로 인해 타이어 제조시 고속주행에 대한 지지능력 발현이 부족한 문제가 발생되고, 750 g/d를 초과하는 경우에는 높은 모듈러스로 인해 타이어 성형이 어려운 문제가 발생될 수 있다.In addition, as the modulus of the aramid multifilament 400 ~ 750 g / d, less than 400 g / d, due to the low modulus, the problem of lack of expression of support capacity for high-speed driving during tire production occurs, exceeding 750 g / d In the case of a high modulus may cause a difficult tire molding.
상기 아라미드 타이어 코오드의 총섬도가 800~10,000 데니어인 것이 바람직하고, 상기 아라미드 멀티필라멘트는 총섬도가 400~5,000 데니어이고 500~1,200개의 아라미드 모노필라멘트들로 구성되는 것이 바람직하다. 또한 상기 아라미드 모노필라멘트의 단사섬도는 1~2 데니어인 것이 바람직하다.It is preferable that the total fineness of the aramid tire cord is 800 to 10,000 denier, and the aramid multifilament preferably has a total fineness of 400 to 5,000 denier and is composed of 500 to 1,200 aramid monofilaments. Moreover, it is preferable that the single yarn fineness of the said aramid monofilament is 1-2 denier.
상기 아라미드 멀티필라멘트의 각종 물성들은 아래와 같은 방법으로 측정한다.Various physical properties of the aramid multifilament is measured by the following method.
·강도(g/d) 및 Strength (g / d) and 절단신도Elongation (%)(%)
ASTM D-885 시험방법에 따라, 인스트론 시험기(Instron Engineering Corp, Canton, Mass)에서 길이가 25cm인 샘플사를 이용하여 샘플사가 파단될 때의 강력(g)을 측정한 다음 이를 샘플사의 데니어로 나누어 강도를 구하였다. 절단신도는 샘플사의 원래길이대비 샘플사가 파단될 때까지 늘어난 길이의 비율로 구하였다. 상기 강도 및 절단신도는 5회 테스트한 후 그 평균값으로 하였다. 이때 인장속도는 300 mm/분으로 하였고, 초하중은 섬도×1/30g으로 하였다.According to ASTM D-885 test method, the strength (g) at the time of fracture of the sample yarn was measured using a sample yarn having a length of 25 cm in an Instron Engineering Corp. (Canton, Mass), and then the sample yarn was denier. The strength was calculated by dividing. Elongation at break was calculated as the ratio of the length of the sample yarn to the length of the sample yarn until the sample yarn was broken. The strength and the elongation at break were taken as the average value after five tests. At this time, the tensile speed was 300 mm / min, and the initial load was 1/130 g of fineness.
·· 모듈러스Modulus (g/d)(g / d)
상기의 강도 측정 조건으로 샘플사의 응력-변형 곡선을 구한 다음, 상기 응력-변형율 곡선상의 기울기로부터 계산한다.The stress-strain curve of the sample yarn is obtained under the above-described strength measurement conditions, and then calculated from the slope on the stress-strain curve.
·강도유지율(%)Strength retention rate (%)
자외선 가속장치(미국 THE Q-PANEL COMPANY의 제품명 Q-UV)를 사용하여 본 발명과 같이 평균자외선차단율이 80% 이상인 합성필름으로 포장된 아라미드 멀티필라멘트 권취지관 또는 상기 합성필름으로 포장되지 않은 아라미드 멀티필라멘트 권취지관을 45℃의 온도와 313㎚의 파장하에 100시간 동안 방치한 후 상기 권취지관에 권취된 아라미드 멀티필라멘트의 강도를 앞에서 설명한 ASTM D-885 시험방법으로 측정하고, 이를 방치후 강도(S2)라고 한다.Aramid multifilament winding tube or aramid multi unpacked with synthetic film packaged with a synthetic film having an average UV blocking rate of 80% or more as described in the present invention using an ultraviolet accelerator (product name Q-UV of THE Q-PANEL COMPANY, USA) After leaving the filament wound tube at a temperature of 45 ° C. and a wavelength of 313 nm for 100 hours, the strength of the aramid multifilament wound in the wound tube was measured by the ASTM D-885 test method described above, and the strength after leaving the tube (S 2 ).
한편, 상기 권취보빈을 자외선 가속장치에서 상기와 같이 방치하기 전에 상기 권취지관에 권취된 아라미드 멀티필라멘트의 강도를 앞에서 설명한 ASTM D-885 시험방법으로 측정하고 이를 방치전 강도(S1)이라고 한다.On the other hand, the strength of the aramid multifilament wound on the winding tube before leaving the winding bobbin as described above in the ultraviolet accelerator device is measured by the above-described ASTM D-885 test method and referred to as strength before standing (S 1 ).
상기와 같이 측정된 방치후 강도(S2)와 방치전 강도(S1)을 아래식에 대입하여 강도유지율을 구한다.The strength retention ratio is obtained by substituting the measured strength after leaving (S 2 ) and the strength before leaving (S 1 ) as follows.
본 발명은 권취보빈에 권취된 아라미드 멀티필라멘트가 자외선에 의해 취화되는 것을 효과적으로 차단하여 상기 아라미드 멀티필라멘트의 강도유지율을 80% 이상으로 유지할 수 있다.The present invention can effectively block the aramid multifilament wound on the winding bobbin by the ultraviolet ray to maintain the strength retention of the aramid multifilament to 80% or more.
이하, 본 발명의 바람직한 실시예를 기재한다. 다만, 하기의 실시예는 본 발명의 바람직한 일 실시예일 뿐, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited to the following examples.
실시예Example 1 One
1,000kg의 N-메틸-2-피롤리돈을 80℃로 유지시키고 여기에 염화칼슘 80kg과 48.67kg의 파라-페닐렌디아민을 녹여서 방향족 디아민 용액을 제조하였다.An aromatic diamine solution was prepared by maintaining 1,000 kg of N-methyl-2-pyrrolidone at 80 ° C. and dissolving 80 kg of calcium chloride and 48.67 kg of para-phenylenediamine.
상기의 방향족 디아민 용액을 중합용 반응기(20) 내로 투입함과 동시에 파라-페닐렌디아민 동몰량의 용융 테레프탈로일 클로라이드를 중합용 반응기(20) 내로 동시에 투입한 후 이들을 교반하여 고유점도가 6.8인 폴리(파라-페닐렌테레프탈아미드) 중합체(아라미드 중합체)를 제조하였다.The aromatic diamine solution was introduced into the polymerization reactor 20, and at the same time, a molten terephthaloyl chloride of an equimolar amount of para-phenylenediamine was simultaneously introduced into the polymerization reactor 20, followed by stirring them to have an intrinsic viscosity of 6.8. Poly (para-phenyleneterephthalamide) polymer (aramid polymer) was prepared.
다음으로, 제조된 상기의 아라미드 중합체를 99% 농황산에 용해시켜 중합체 함량이 18중량%인 광학적 비등방성 방사원액을 제조하였다.Next, the prepared aramid polymer was dissolved in 99% concentrated sulfuric acid to prepare an optically anisotropic radiation stock solution having a polymer content of 18% by weight.
다음으로, 상기와 같이 제조된 방사원액을 도 1에 도시된 바와 같이 방사 구금(40)을 통해 1,000m/분의 방사권취속도로 방사한 후, 방사된 방사물을 7 mm의 공 기층(비응고성 유체층)을 통과시킨 후, 계속해서 황산농도가 13%인 황산수용액(응고액)이 담겨져 있는 응고액 욕조(50)내로 통과시켜 아라미드 멀티필라멘트를 제조하였다.Next, after spinning the spinning stock solution prepared as described above at a spinning winding speed of 1,000 m / min through the
다음으로, 상기와 같이 형성된 멀티필라멘트를 수세 및 건조한 후, 이를 지관에 권취하여 아라미드 멀티필라멘트 권취지관을 제조하였다.Next, after washing and drying the multifilament formed as described above, it was wound on a branch pipe to prepare an aramid multifilament wound paper tube.
상기와 같이 제조한 권취보빈에 평균자외선차단율이 85%인 폴리에스테르 필름으로 제조된 봉투를 덮어씌워 포장하였다.The wrapping bobbin prepared as described above was covered with an envelope made of a polyester film having an average UV cut ratio of 85%.
상기와 같이 포장된 권취보빈에 감겨진 아라미드 멀티필라멘트의 강도유지율 및 기타 물성을 평가한 결과는 표 1과 같았다.Table 1 shows the results of evaluating the strength retention and other physical properties of the aramid multifilament wound on the wound bobbin packaged as described above.
실시예Example 2 2
평균자외선차단율이 92%인 폴리아미드 필름으로 제조된 봉투를 실시예 1과 같이 제조된 아라미드 멀티필라멘트의 권취지관에 덮어씌워 포장하였다.An envelope made of a polyamide film having an average UV blocking rate of 92% was packaged by covering the winding tube of the aramid multifilament prepared in Example 1.
상기와 같이 포장된 권취보빈에 감겨진 아라미드 멀티필라멘트의 강도유지율 및 기타 물성을 평가한 결과는 표 1과 같았다.Table 1 shows the results of evaluating the strength retention and other physical properties of the aramid multifilament wound on the wound bobbin packaged as described above.
비교실시예Comparative Example 1 One
평균자외선차단율이 60%인 폴리에틸렌 필름으로 제조된 봉투를 실시예 1과 같이 제조된 아라미드 멀티필라멘트의 권취지관에 덮어씌워 포장하였다.An envelope made of a polyethylene film having an average ultraviolet ray blocking rate of 60% was packaged by covering the winding paper tube of the aramid multifilament prepared in Example 1.
상기와 같이 포장된 권취보빈에 감겨진 아라미드 멀티필라멘트의 강도유지율 및 기타 물성을 평가한 결과는 표 1과 같았다.Table 1 shows the results of evaluating the strength retention and other physical properties of the aramid multifilament wound on the wound bobbin packaged as described above.
비교실시예Comparative Example 2 2
실시예 1과 같이 제조된 아라미드 멀티필라멘트의 권취지관을 합성필름으로 전혀 포장하지 않았다.The winding tube of the aramid multifilament prepared in Example 1 was not packaged at all with a synthetic film.
상기와 같이 포장된 권취보빈에 감겨진 아라미드 멀티필라멘트의 강도유지율 및 기타 물성을 평가한 결과는 표 1과 같았다.Table 1 shows the results of evaluating the strength retention and other physical properties of the aramid multifilament wound on the wound bobbin packaged as described above.
(데니어)A single island
(Denier)
도 1은 본 발명에 따른 아라미드 멀티필라멘트를 제조하는 공정개략도.1 is a process schematic diagram of producing aramid multifilament according to the present invention.
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