KR100205201B1 - Biaxial oriented polyester film for fire retardant - Google Patents
Biaxial oriented polyester film for fire retardant Download PDFInfo
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- KR100205201B1 KR100205201B1 KR1019970032613A KR19970032613A KR100205201B1 KR 100205201 B1 KR100205201 B1 KR 100205201B1 KR 1019970032613 A KR1019970032613 A KR 1019970032613A KR 19970032613 A KR19970032613 A KR 19970032613A KR 100205201 B1 KR100205201 B1 KR 100205201B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/065—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids the hydroxy and carboxylic ester groups being bound to aromatic rings
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
- C08G63/6822—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens derived from hydroxy carboxylic acids
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08J2367/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
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Abstract
본 발명은 우수한 난연성과 저올리고머성을 가지는 이축배향 폴리에스테르 필름의 제조방법에 관한 것으로 특히 인화합물에 의한 난연효과와 할로겐 화합물에 의한 난연작용의 상승효과를 이용하여 특정의 인화합물과 할로겐이 함유된 화합물을 병용하여 폴리에스테르 중축합 반응단계에서 첨가하여 얻은 난연성이 뛰어나고 저올리고머성의 이축배향 폴리에스테르로써 그 기술구성은 하기 구조식을 가지는 디아릴포스피닐, 알칼아릴포스피닐, 디알킬포스피닐기를 갖는 포로핀산 공중합단위체를 함유하도록 하고 최종 폴리머내에 인원자 함량이 0.1∼1중량%, 염소원자함량이 0.1∼4.0중량%인 난연성 고분자 전구체를 투입하여 제조한다.The present invention relates to a method for producing a biaxially oriented polyester film having excellent flame retardancy and low oligomer properties, in particular containing a specific phosphorus compound and halogen by using a synergistic effect of the flame retardant effect by the phosphorus compound and halogen compounds Highly flame-retardant, low-oligomeric biaxially oriented polyester obtained by adding the compound in the polyester polycondensation reaction step, and its technical configuration has diarylphosphinyl, alkaliarylphosphinyl and dialkylphosphinyl groups It is prepared by adding a poropin copolymer unit and adding a flame retardant polymer precursor containing 0.1 to 1% by weight of phosphorus atom and 0.1 to 4.0% by weight of chlorine atom in the final polymer.
(즉, R1은 탄소수 1내지 4의 수소, 메틸기, 치환기를 갖거나 또는 가지지 않는 페닐기, 싸이클로 알킬기, 할로 알킬기, 할로 아릴기이며 치환기로는 각종 탄소수 1 내지 5 알킬기, 금속 술포네이트기, 탄소수 1 내지 6을 포함하는 아민기 등을 들 수 있다. R2는 치환기(R3)를 가진 에틸렌기이며 치환기(R3)로는 아릴기에 염소수 1-8개를 함유한 비스-(4-히드록시페닐)메탄, 비스-(4-히드록시페닐)헥사클로로프로판이며, R4로는 염소수 1개를 함유한 프로판디올이나 기타 R3에서 언급되어진 화합물임)(I.e., R1 is a phenyl group, a cycloalkyl group, a haloalkyl group, a haloaryl group, with or without hydrogen, methyl, or a substituent having 1 to 4 carbon atoms, and as substituents, various substituents include 1 to 5 alkyl groups, metal sulfonate groups, and 1 carbon atoms). And an amine group containing 6 to 6. R2 is an ethylene group having a substituent (R3), and the substituent (R3) is a bis- (4-hydroxyphenyl) methane containing 1-8 chlorine groups in an aryl group. , Bis- (4-hydroxyphenyl) hexachloropropane, R4 being propanediol containing one chlorine water or other compounds mentioned in R3)
Description
본 발명은 우수한 난연성 및 저올리고머성을 가지는 이축배향 폴리에스테르 필름의 제조에 관한 것으로, 특히 본 발명은 인화합물에 의한 난연효과와 할로겐 화합물에 의한 난연작용의 상승효과를 이용하여 특정의 인화합물과 할로겐이 함유된 화합물을 병용하여 폴리에스테르 중축합 단계에서 첨가함으로써 난연성이 뛰어난 저올리고머성의 이축배향 폴리에스테르 필름의 제조에 관한 것이다.The present invention relates to the preparation of a biaxially oriented polyester film having excellent flame retardancy and low oligomerism, and in particular, the present invention relates to a specific phosphorus compound by using a synergistic effect of The present invention relates to the production of a low oligomeric biaxially oriented polyester film having excellent flame retardancy by adding a halogen-containing compound in combination in a polyester polycondensation step.
폴리에스테르 중 특히, 폴리에칠렌 테레프탈레이트는 화학적으로 안정하고 물리적 및 기계적강도, 내구성, 내약품성, 전기전열성이 우수하여 의료용, 산업용, 자기테이프용, 모터절연용, 콘텐서용, 포장용, 사진필름용, 라벨용은 물론 그 외에 각종성형가공품으로 폭넓게 사용되고 있다. 그러나, 이러한 폴리에스테르 수지는 구성상 탄소, 수소, 산소의 3원소로만 이루어져 있어 연소가 용이하며, 특히 섬유 및 전기, 전자제품의 성형품에 사용하였을 때 화재에 의한 위험성이 크기 때문에 대형화재 사고의 예방을 위하여 화재 발생시 연소효과를 저해하도록 난연화가 요구되고 있다. 더욱이 사용되어지는 환경이 매우 열악한 모터절연용 분야에 있어서는 접촉되어지는 냉매에 대한 저항성 뿐만아니라 열에의한 발화의 위험성읓 최소화할 수 있는 방법이 필름제조 메이커에서는 계속적으로 연구되어지고 있다.Among the polyesters, the polyethylene terephthalate is chemically stable and has excellent physical and mechanical strength, durability, chemical resistance, and electrical conductivity, so that it can be used in medical, industrial, magnetic tape, motor insulation, condenser, packaging, and photo film. It is widely used in various molding products as well as for labeling. However, these polyester resins are composed of only three elements of carbon, hydrogen, and oxygen, and are easily combustible. Especially, when used in molded products of textiles, electrical and electronic products, the risk of fire is large. For this purpose, flame retardants are required to inhibit the combustion effect in case of fire. Furthermore, in the field of motor insulation where the environment to be used is very poor, not only the resistance to the refrigerant to be contacted but also the method of minimizing the risk of fire ignition by heat are continuously studied in the film maker.
최근까지는 연소하기 쉬운 폴리에스테르 섬유나 필름등에 난연성을 부여하는 방법이 여러모로 연구되어지고 있으며 그 한가지 방법으로 고분자를 합성할 때 난연제, 특히 할로겐 또는 인화합물을 첨가하는 방법이 거론되어왔다. 그러나 일본 공개특허 소48-52834등에 제안된 바와 같이 할로겐을 함유한 화합물을 첨가하는 경우에는 난연성은 부여되나 다량의 난연제를 첨가함으로써 기계적 물성의 저하가 초래될 뿐만아니라 내후성이 심하게 저하되며 황색으로 착색되는 등의 결점이 있다. 또 이를 함유한 화합물은 본질적으로 열안정성이 좋지 못하며 폴리에스테르와의 반응성도 낮아지므로 고분자내의 난연에 충분한 양을 함유하는 것은 매우 어려운 일이었다. 뿐만아니라 본 발명자들이 목표로 하는 저올리고머성의 특성을 갖는 모터절연용의 경우 그 요구특성(저올리고머성)을 달성하기가 매우 어려울 뿐만아니라 제조공정에 있어서도 많은 어려움을 수반하게 된다.Until recently, various methods of imparting flame retardancy to polyester fibers or films which are easy to burn have been studied. One method of adding a flame retardant, particularly halogen or phosphorus compound, has been discussed. However, in the case of adding a compound containing a halogen, as proposed in Japanese Patent Application Laid-Open No. 48-52834, etc., flame retardancy is imparted, but addition of a large amount of flame retardant not only results in deterioration of mechanical properties but also severely degrades weather resistance and color yellowing. It is a defect such as being. In addition, since the compound containing it is inherently poor in thermal stability and also has low reactivity with polyester, it was very difficult to contain a sufficient amount for flame retardation in the polymer. In addition, in the case of the motor insulation for which the present inventors have a low oligomeric characteristic, the present inventors are not only very difficult to achieve the required characteristics (low oligomeric), but also have many difficulties in the manufacturing process.
이러한 결점을 해결하기 위하여 일본국 특허공개 공보 소52-10351, 특허공개 공보 소59-191716, 특허공개 공보 소36-20771, 미국특허 3,941,752, 미국특허4,033,936등에는 유기 인 화합물을 중축합반응이 어느 정도 진행된 후에 투입하면서 중축합 촉매를 추가로 넣어주는 방법, 또는 페닐포스폰산 디알킬에스테르 또는 페닐포스폰산 지방족 글리콜 에스테르를 폴리에스테르의 반응 성분과 같이 중축합시켜 난연성을 부여하는 방법등이 공지되어 있으나 공정이 복잡하거나 실질적으로 인 화합물의 잔존율이 낮아 이러한 방법들을 응용하여 만족할만한 난연성을 나타내는 폴리에스테르 필름은 거의 없는 실정이다.In order to solve this drawback, Japanese Patent Publication No. 52-10351, Patent Publication No. 59-191716, Patent Publication No. 36-20771, US Patent 3,941,752, US Patent 4,033,936, etc. It is known to add a polycondensation catalyst while adding the polycondensation catalyst, or to impart flame retardancy by polycondensing phenylphosphonic acid dialkyl ester or phenylphosphonic acid aliphatic glycol ester with the reaction component of polyester. Due to the complexity of the process or substantially low residual ratio of the phosphorus compound, few polyester films exhibit satisfactory flame retardancy by applying these methods.
따라서 본 발명자들은 기계적 물성의 저하없이 우수한 난연성을 발휘할 뿐만 아니라 저올리고머성의 특성을 갖는 폴리에스테르 필름의 제조를 위하여 노력한 결과 인화합물에 의한 난연효과와 할로겐 화합물에 의한 난연작용이 상승효과를 발휘한다는 점에 착안하여 특정의 인화합물과 할로겐이 함유된 화합물을 병용하여 폴리에스테르 중축합 반응 단계에서 첨가함으로써 화학적, 기계적 물성의 저하없이 난연성이 뛰어난 저올리고머성 폴리머를 개발하게 되었다.Therefore, the present inventors have tried to prepare a polyester film having excellent oligomeric properties as well as excellent flame retardancy without deterioration of mechanical properties, resulting in a synergistic effect of flame retardant effect by phosphorus compounds and flame retardant action by halogen compounds. By focusing on the specific phosphorus compound and halogen-containing compound in combination in the polyester polycondensation reaction step, the low oligomeric polymer with excellent flame retardancy was developed without deteriorating chemical and mechanical properties.
다시말해서, 본 발명의 목적은 종래 폴리에스테르 필름에서 나타나는 재결점을 해결하기 위해서 75중량%이상 폴리에칠렌 테레프탈레이트로 이루어진 극한 점도 0.45∼1dl/g의 폴리에스테르 필름이 있으며, 새로운 조성의 히드록시페닐 포스피닐 프로판산 유도체를 중축합 반응단계에서 적량 첨가함으로써, 난연성, 전기적특성 및 기계적 물성이 우수하면서 특히나 열수축안정성 및 저올리고머성의 특성이 우수한 개량된 이축배향 폴리에스테르 필름을 제공하는데 있다.In other words, an object of the present invention is a polyester film having an intrinsic viscosity of 0.45 to 1 dl / g composed of at least 75% by weight of polyethylene terephthalate in order to solve the red defects of conventional polyester films. By adding an appropriate amount of the pinyl propanoic acid derivative in the polycondensation reaction step, to provide an improved biaxially oriented polyester film excellent in flame retardancy, electrical properties and mechanical properties, in particular excellent in the heat shrinkage stability and low oligomeric properties.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
알킬렌 테레프탈레이트를 주성분으로 하는 폴리에스테르를 얻기 위하여 증축합반응을 행할 때 하기 구조식(1)을 가지는 히드록시페닐포스피닐 프로핀산 유도체 화합물을 직접 에스테르화법 또는 에스테르 교환법에 의하여 중합도 2내지 10의 폴리에스테르 전구물질을 얻고,When the polycondensation reaction is carried out to obtain a polyester containing alkylene terephthalate as a main component, a hydroxyphenylphosphinyl propinic acid derivative compound having the following structural formula (1) is polymerized by a direct esterification method or a transesterification method to obtain a polyolefin having a polymerization degree of 2 to 10 Obtain ester precursors,
상기 구조식에서In the above structural formula
(즉, R1은 탄소수 1내지 5의 수소, 메틸기, 치환기를 갖거나 또는 가지지 않는 페닐기, 싸이클로 알킬기, 할로 알킬기, 할로 아릴기이며 치환기로는 각종 탄소수 1내지 5알칼기, 금속 술포네이트기, 탄소수 1 내지 6을 포함하는 아민기 등을 들 수 있다. R2는 치환기(R3)를 가진 에틸렌기이며 치환기(R3)로는 아릴기에 염소수 1-8개를 함유한 비스-(4-히드록시페닐)프로판, 아릴기에 염소수 1-8개를 함유한 비스-(4-히드록페닐)메탄, 비스-(4-히드록페닐)헥사클로로프로판이며, R4로는 염소수 1개를 함유한 프로판디올이나 기타 R3에서 언급되어진 화합물임)(I.e., R1 is a phenyl group, a cycloalkyl group, a haloalkyl group, a haloaryl group, with or without hydrogen, methyl, or a substituent having 1 to 5 carbon atoms, and as substituents, various substituents include 1 to 5 alkali, metal sulfonate, and carbon atoms). And an amine group containing 1 to 6. R2 is an ethylene group having a substituent (R3), and the substituent (R3) is a bis- (4-hydroxyphenyl) containing 1-8 chlorine groups in an aryl group. Bis- (4-hydroxyphenyl) methane and bis- (4-hydroxyphenyl) hexachloropropane containing 1-8 chlorine groups in propane and aryl groups, and R4 as propanediol containing 1 chlorine Other compounds mentioned in R3)
이를 다시 촉매존재하에서 고중합도로 중축합하여 임의의 단계에서 최종 폴리며내의 인 원자의 함량이 0.1∼1.0중량%, 염소원자함량이 0.1∼4.0중량%가 되도록 투입할시, 공중합체의 용융온도(℃:A로 표시)와 함유된 인원소 함량(ppm:B로 표시)비가 3.985와 20.559사이를 벗어나지 않도록 조성을 유지함으로써 열적으로 안정됨과 동시에 제조되어진 공중합 고분자의 열적거동에 있어서도 일반 비공중합물과 차이점 즉 결정거동에 있어서 거의 유사한 특성을 보여줌으로써 차후 본 공중합 폴리마를 이용하여 진공고상중합이라는 2차 가공공정을 거친후 이축연신된 폴리에스테르 필름을 제조할 시 공정 및 수율상 문제 발생 없이 우수한 물성을 가지며 폴리마 고유점도가 0.65∼0.75dl/g, 비중이 1.365∼1.420, 표면저항이 1014∼1016오옴(Ω), 유전률이 3.1∼3.5이고 난연성이 VTM-2(UL94규격)에 적합한 물성을 특징으로하는 저올리고머성 이축배향 폴리에스테르 필름을 얻을 수 있다.When polycondensation is carried out again in the presence of a catalyst to a high degree of polymerization and the content of the phosphorus atom in the final polygon in an optional step is 0.1 to 1.0% by weight, the chlorine atom content is 0.1 to 4.0% by weight, the melting temperature of the copolymer ( ℃: A) and the content of the content of phosphorus content (ppm: B) by maintaining the composition so as not to deviate between 3.985 and 20.559, and thermally stable at the same time, the difference between the general non-copolymer and the thermal behavior of the copolymer produced By showing almost similar characteristics in crystal behavior, after the second processing process called vacuum solid-state polymerization using this copolymerized polymer, the biaxially stretched polyester film was produced. Do inherent viscosity 0.65~0.75dl / g, a specific gravity of 1.365 to 1.420, a surface resistance of 10 14 ~10 16 ohms (Ω), dielectric constant of 3.1 to 3.5 and the flame retardant In the VTM-2 (UL94 standard), it is possible to obtain a low oligomeric biaxially oriented polyester film characterized by good physical properties.
본 발명에서 폴리에스테르 합성에 사용되는 제1 및 제2성분으로는 탄소수 2∼6의 알킬렌 글리콜과 테레프탈산 또는 이의 에스테르 형성 유도체를 들 수 있으며 제 3성분으로는 이소프탈산, 나프탈렌 디카르본산, 디페닐 디카르본산, 디페닐 에테르 디카르본산등의 방향족 디카르본산, p-하이드록시 안식향산, 하이드록시 에톡시 안식향산 등과 이 화합물들의 아릴기에 염소가 치환된 유도체 또는 이들의 에스테르 형성성유도체, 프로판디울, 클로로프로판디올, 부탄디올, 싸이클로헥산디올, 사이클로헥산 디메탄디올등의 2가 알코울 글리세린 등이 다가 알코올, 폴리에틸렌글리콜, 폴리글리콜렌글리콜 등의 폴리올 등과 같은 화합물등을 한가지 이상 소량 첨가할 수 있다.In the present invention, the first and second components used in the synthesis of polyesters include alkylene glycols having 2 to 6 carbon atoms and terephthalic acid or ester forming derivatives thereof, and the third component isophthalic acid, naphthalene dicarboxylic acid, di Aromatic dicarboxylic acids such as phenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, p-hydroxy benzoic acid, hydroxy ethoxy benzoic acid, and the like, derivatives of which chlorine is substituted in the aryl group of these compounds, or ester-forming derivatives thereof, propanediol , Dihydric alcohol glycerin such as chloropropanediol, butanediol, cyclohexanediol, cyclohexane dimethanediol, and the like can be added one or more small amounts of compounds such as polyols such as polyhydric alcohols, polyethylene glycol, polyglycol glycol, etc. .
한편 포스핀산 유도체로는 3-(히드록시페닐포스피닐)프로판산을 기본 골격으로하여 r-카르복시기에 2-클로로-1,3-프로판디올, 3-클로로-1,2-프로판디올, 아릴기에 염소수 1-8개를 함유한 비스-(4-히드록시페닐)프로판, 아릴기에 염소수 1-8개를 함유한 비스-(4-히드록시페닐)메탄, 1-8개를 함유한 비스-(4-히드록시페닐) 헥사클로로프로판이 에스테르 관능기를 갖도록 치환된 물질을 사용한다.On the other hand, as the phosphinic acid derivative, 3- (hydroxyphenylphosphinyl) propanoic acid is used as a basic skeleton, and 2-chloro-1,3-propanediol, 3-chloro-1,2-propanediol, and aryl groups are used in the r-carboxy group. Bis- (4-hydroxyphenyl) propane containing 1-8 chlorine water, bis- (4-hydroxyphenyl) methane containing 1-8 chlorine water in an aryl group, bis containing 1-8 Substances are used in which-(4-hydroxyphenyl) hexachloropropane is substituted to have an ester function.
본 발명에서는 난연성을 부여하는 물질로 거론되는 화합물인 알킬 또는 아릴 포스핀산 에스테르의 인원자와 그 주위에 존재하도록 고안된 할로겐 원자가 중합촉매로 사용된 삼산화안티몬과 함께 작용하여 난연성에 있어서 소량 첨가시에도 우수한 난연효과를 발휘할 수 있게 하었다. 기존에 알려진 3-(히드록시페닐포스피닐)그로판산 난연 화합물을 혼합하여 공중합함으로써 인의 총함량이 0.1∼1중량%가 되도록 할 수도 있다.In the present invention, the compound of alkyl or aryl phosphinic acid ester, which is a compound which gives flame retardancy, and the halogen atom designed to exist around it work together with the antimony trioxide used as a polymerization catalyst, so it is excellent even in a small amount of flame retardancy. It was able to exert a flame retardant effect. The total content of phosphorus can also be made to be 0.1-1 weight% by mixing and copolymerizing the known 3- (hydroxyphenylphosphinyl) gropanic-acid flame-retardant compound.
이때 사용되어지는 인 원소의 총함량은 하기식(1)을 만족하는 범위에 있어야 하는데 만약 공중합체의 용융온도(Tm)와 함유 인원소향의 비율이 3.985%보다 작을 경우 충분한 난연효과 및 전기적 특성의 달성이 어렵게 되고, 반대로 그 비율이 20.559를 촉과할 경우에는 기본적으로 요구되어지는 폴리에스테르 필름의 기계적 물성 즉, 기계적 강도 및 열수축 안정성등에 좋지 못한 영향을 줄뿐만 아니라 분자량 분포가 매우 넓어서 단량체의 존재가 많아지게 된다. 따라서 제조되어진 공중합 폴리마를 2차 가공 즉, 고상중합을 할 시 제조조건의 선정에 어려움이 따르게 되고 충분한 고상중합의 효과를 얻기가 어려워져 바람직하지 못하게 된다.In this case, the total content of phosphorus element to be used should be in the range satisfying the following formula (1). If the ratio of melting temperature (Tm) of the copolymer and the content of fragrance of fragrance is less than 3.985%, sufficient flame retardant effect and electrical properties On the contrary, when the ratio is 20.559, the ratio of the monomer is not only detrimentally affecting the mechanical properties of the polyester film, that is, the mechanical strength and heat shrinkage stability, but also the molecular weight distribution is very wide. Will increase. Therefore, when the copolymerized polymer prepared is subjected to secondary processing, that is, solid phase polymerization, it is difficult to select the production conditions, and it becomes difficult to obtain the effect of sufficient solid phase polymerization, which is not preferable.
3.985 ≤ M ≤ 20.5593.985 ≤ M ≤ 20.559
M=(B/A)M = (B / A)
여기서, A: 공중합체의 용융온도(Tm, ℃)Where A: melting temperature of the copolymer (Tm, ° C.)
B: 인원소 함량(PPM)B: Personnel Content (PPM)
본 발명에서 사용되는 난연성 전구체 1의 투입시기는 폴리에스테르 중합의 어느단계에서나 투입이 가능하지만 특히 에스테르와 반응 또는 에스테르 교환 반응을 종료한 후 중합도 2 내지 10의 폴리에스테르 전구물질이 생성된 임의의 단계에서 행하는 것이 좋으며 이후 최종 폴리며까지 중축합 반응을 시키기 위하여 추가로 적당한 촉매를 투입하는 것이 적당하다. 이때 사용되어지는 중축합촉매로써는 일반적으로 사용되어지는 안티몬계 화합물 혹은 게르마늄의 산화물, 유기산염, 알킬 및 아릴화합물등이 사용될 수 있다.The timing of the flame retardant precursor 1 used in the present invention may be added at any stage of the polyester polymerization, but in particular any stage in which a polyester precursor having a polymerization degree of 2 to 10 is produced after the reaction with the ester or the transesterification reaction is completed. It is recommended to add a suitable catalyst in order to carry out the polycondensation reaction up to the final poly. In this case, as the polycondensation catalyst used, an antimony compound or an oxide of germanium, an organic acid salt, an alkyl and an aryl compound may be used.
첨가량은 안티몬 원자 및 게르마늄 원자로써 디카르본산의 저급 알킬에스테르에 대해 0.005∼0.15몰%가 바람직하고 0.005몰% 미만일 경우 중축합 반응이 충분히 진행되지 않아 실질적으로 반응을 완료할 수 없으며, 0.15몰%를 초과한 경우는 중축합 반응시간 및 폴리마 물성측면, 즉 색조 및 말단기가 나빠져 좋지 않게 된다.The addition amount is preferably 0.005 to 0.15 mol% with respect to the lower alkyl ester of dicarboxylic acid as the antimony atom and the germanium atom, and when the amount is less than 0.005 mol%, the polycondensation reaction does not proceed sufficiently, so that the reaction cannot be substantially completed, and 0.15 mol%. In the case of exceeding the polycondensation reaction time and the side of the polymer properties, that is, the color tone and the end group worsen.
따라서 이렇게 제조되어진 공중합물의 열적거동, 특히 결정거동이 공중합물임에도 불구하고 기존의 순수 폴리마와 거의 유사하거나 크게 차이가 나지않는 특성을 지니게 되는데 본 발명에서 개발되어진 개질 폴리마는 하기식 (2)를 만족하는 범위이어야 한다.Therefore, although the thermal behavior, in particular the crystallization behavior of the copolymer thus prepared is a copolymer, it has characteristics that are almost similar to or are not significantly different from existing pure polymers. The modified polymers developed in the present invention have the following formula (2) It must be within the range to be satisfied.
0.8 ≤ k ≤ 1.3 ······ (2)0.8 ≤ k ≤ 1.3 (2)
k=(D/C)k = (D / C)
여기서, C; 순수폴리마의 반결정 시간(t1/2) Where C; Semicrystalline time of pure polymer (t 1/2)
D; 공중합물의 반결정시간(t1/2) D; Semicrystallization time of copolymer (t 1/2)
이때, 순수폴리마와 동중합물간의 반결정시간 비(k)가 1보다 작거나 1.3보다 클 경우 상기 폴리마를 이용하여 2차 가공 즉, 진공 고상중합을 행할시 충분한 효과를 볼 수 없어 바라고자 하는 수준의 저오리고머성을 획득하기가 어려울뿐만 아니라 특히나 고상중합의 공정조건을 설정하기가 무척 어렵게 된다. 또한 이렇게 제조된 폴리마로 이축연신 필름을 제조하기는 많은 어려움이 따르게 되는데 예를들어, 제막파단이 빈번하게 발생하거나 성형성이 무척 나빠지제 되 바람직하지 않는 현상이 발생한다.At this time, if the semi-crystallization time ratio (k) between pure polymer and the homopolymer is less than 1 or greater than 1.3, it may be difficult to see a sufficient effect when performing secondary processing, that is, vacuum solid-state polymerization using the polymer. Not only is it difficult to attain a low degree of oligomerism, but it is particularly difficult to set the process conditions for solid state polymerization. In addition, it is difficult to produce a biaxially stretched film using the polyma thus prepared. For example, film breakage occurs frequently or moldability is very poor, which is undesirable.
한편, 본 발명에 따라 폴리에스테르 필름을 제조함에 있어서 상기 첨가제의 첨가시기는 반드시 한정하지는 않으나, 중축합 반응 완결전이면 언제라도 가능하며, 중축합 반응중에 첨가할 경우는 에스테르 교환 반응후나, 중축합 반응 완결 반시간전이 보다 좋다.On the other hand, in the preparation of the polyester film according to the present invention, the addition time of the additive is not necessarily limited, but is possible at any time before the completion of the polycondensation reaction, and when added during the polycondensation reaction, after the transesterification reaction or polycondensation Half an hour before completion of the reaction is better.
이외에 히드록시 페닐 포스피닐 프로판산 유도체의 경우는 고농도의 폴리에스테르 마스터칩을 만들어 이것을 통상의 폴리에스테르에 소정의 농도가 되도록 브렌드하여 용융압출하는 방법도 있다.In addition, in the case of the hydroxy phenyl phosphinyl propanoic acid derivative, there is also a method of making a polyester master chip of high concentration, blending it to a predetermined concentration in ordinary polyester, and melt extrusion.
본 발명의 필름은 인원소의 총함량이 0.1중량%∼4.0중량%이어야만 우수한 난연성과 전기적 특성을 나타낸다. 만일, 인원소 및 염소원소의 함량이 0.1중량%미만인 경우 필름의 난연성이 매우 불량하고, 제시된 함량을 초과할 경우는 필름이 취약해질 뿐만아니라 제막시 빈번한 파단이 발생하여 생산성이 저하된다. 또, 비중이 1.365이하에서는 필름의 열변형이 심하고, 난연성도 불량하며 1.420이상에서는 역시 필름이 취약해져서 생산성이 저하된다. 틋히 인함량이 0.3∼0.8중량%, 염소함량이 0.3∼3.5중량%, 비중1.385∼1.400, 폴리마 고유점도가 0.65∼0.75dl/g의 범위이면 가장 좋다.The film of the present invention exhibits excellent flame retardancy and electrical properties only when the total content of phosphorus element is 0.1% by weight to 4.0% by weight. If the content of elemental element and chlorine element is less than 0.1% by weight, the flame retardancy of the film is very poor, and if the content exceeds the suggested content, the film is not only fragile but also frequently breaks during film formation, resulting in decreased productivity. In addition, when the specific gravity is less than 1.365, the thermal deformation of the film is severe, the flame retardancy is also poor, and at 1.420 or more, the film is also vulnerable and the productivity is lowered. Most preferably, the phosphorus content is 0.3 to 0.8% by weight, the chlorine content is 0.3 to 3.5% by weight, the specific gravity 1.385 to 1.400, and the intrinsic viscosity of the polymer is 0.65 to 0.75 dl / g.
본 발명의 폴리에스테르 필름의 제법은 특별히 한정된 것은 아니지만 상기의 첨가제를 포함한 폴리에스테르를 티이-다이법, 인플레이션법 등에 의해 용융압출된 고유점도 0.65∼1.0dl/g의 미연신 시트를 만든후 이를 이축연신하여 이축배향된 본 발명의 폴리에스테르 필름은 제작한다.Although the manufacturing method of the polyester film of this invention is not specifically limited, It makes a non-stretched sheet | seat of the intrinsic viscosity 0.65-1.0 dl / g which melt-extruded the polyester containing the said additive by the tie-die method, the inflation method, etc. The polyester film of this invention extended | stretched and biaxially oriented is produced.
연신법은 통상의 폴리에스테르 연신과 동일하여 상기의 첨가물에 의한 변화는 없다. 연신온도는 60∼150℃이고, 연신배율은 종방향 205∼6.0배, 횡방향 2.5∼6.0배이다. 연신후 160∼240℃에서 20초간 열고정하여 비중 1.365∼1.420, 표면저항1016∼1014오옴(Ω)인 이축배향된 필름을 제작하였다.The stretching method is the same as ordinary polyester stretching, and there is no change by the above additives. The stretching temperature is 60 to 150 ° C, the stretching ratio is 205 to 6.0 times in the longitudinal direction and 2.5 to 6.0 times in the lateral direction. Open 20 seconds after stretching 160~240 ℃ appointed to prepare a specific gravity from 1.365 to 1.420, a biaxially oriented film, the surface resistance 10 16-10 14 ohms (Ω).
본 발명에 따라 제조된 폴리에스테르 필름을 용도에 따라 적절한 두께의 설계가 가능하고 통상적으로 두께 3.0∼250㎛의 필름으로 필요에 따라 필름표면에 코로나방전처리, 타수지의 코팅 및 라미네이션, 공압출등 모든 종류의 표면처리가 가능하다.The polyester film produced according to the present invention can be designed in an appropriate thickness according to the application, and is usually a film of 3.0 to 250㎛ thick corona discharge treatment, coating and lamination of other resins, coextrusion, etc. All kinds of surface treatments are possible.
본 발명에서 특성치는 다음의 측정법 및 평가기준에 의하여 측정하였고 실시예 및 비교예는 표 1과 같은 조건하에서 실시하였다.In the present invention, the characteristic values were measured by the following measurement methods and evaluation criteria, and the examples and the comparative examples were performed under the conditions shown in Table 1.
[기계적 물성][Mechanical Properties]
인스트론사의 UTM MODEL-4206형을 사용하여 실온, 상대습도 65%에서 길이 50㎜, 폭20㎜, 두께125㎛의 필름을 200㎜/㎝의 속도로 인장하여 하중-신도의 챠트를 작성하여 각각의 데이터를 계산하여 평가하였다.Using Instron's UTM MODEL-4206 model, a 50 mm long, 20 mm wide, 125 μm thick film was stretched at a rate of 200 mm / cm at room temperature and 65% relative humidity to prepare a load-elongation chart. The data was evaluated by calculating.
파단강도; 실온에서 필름을 파단시키는데 필요한 힘을 필름의 단위면적당 가해진 힘으로 표시한 것.Breaking strength; The force required to break a film at room temperature, expressed as the force applied per unit area of the film.
[열수축율][Heat shrinkage rate]
열풍건조기내 100㎜×100㎜의 필름을 위치시키고 150℃, 30분간 열처리후, 상온에서 변형된 필름의 길이를 하기의 식으로부터 구하였다.After placing the film of 100 mm x 100 mm in a hot air dryer and heat-processing for 150 degreeC for 30 minutes, the length of the film deform | transformed at normal temperature was calculated | required from the following formula.
여기서, L0는 처리전 길이이고, L는 처리후의 길이임Where L 0 is the length before treatment and L is the length after treatment
[비중][importance]
사염화탄소와 노말-헵탄으로 이루어진 밀도구배관을 25℃로 유지하고 부침법으로 비중을 측정하였다.The density gradient tube consisting of carbon tetrachloride and normal-heptane was maintained at 25 ° C. and specific gravity was measured by ups and downs.
[극한점도][Extreme viscosity]
각각의 공중합 폴리에스테르 2.0g를 1,1,2,2-테트라크로로에탄/페놀/(60/40중량 퍼센트) 혼합 용매에 용해시켜 25℃에서 측정하였다.2.0 g of each copolyester was dissolved in a 1,1,2,2-tetrachloroethane / phenol / (60/40 weight percent) mixed solvent and measured at 25 ° C.
[표면저항][Surface resistance]
미국 휴레트사의 절연저항 측정기를 이용, 20℃, 상대습도 65%에서 표면저항을 측정했다. 인가전압은 500V이고 단위는 오옴(Ω)이다.Surface resistance was measured at 20 ° C. and 65% RH using an insulation resistance meter manufactured by Hurett, USA. The applied voltage is 500V and the unit is Ohm.
[유전율][permittivity]
미국 표준측정방법(ASTM Dl50-92)에 준하여, 20℃, 1㎑의 조건으로 측정하였다.According to the American standard measurement method (ASTM Dl50-92), it measured on 20 degreeC and the conditions of 1 kPa.
[절연파괴전압][Insulation breakdown voltage]
미국 표준측정방법(ASTM D149-92)에 준하여, 로즈마운트 어낼리티컬사의 기기를 사용하여 측정하였다.According to the American standard measurement method (ASTM D149-92), it measured using the instrument of Rosemount Analytical.
[난연성][Flame retardancy]
UL-94 VTM-C 시험방법 및 합격기준에 따라 평가하였다.Evaluation was made according to the UL-94 VTM-C test method and acceptance criteria.
[반결정시간][Half-determination time]
PERKIN ELMER DSC-7를 활용하여 NITROGEN(10 KPa)의 분위기하에서 -200℃/min의 속도로 200℃에서 등온 결정 거동을 측정후 얻어진 그래프로부터 반 결정화 시간을 구하였다.The semi-crystallization time was determined from the graph obtained after measuring isothermal crystal behavior at 200 ° C. at a rate of −200 ° C./min in an atmosphere of NITROGEN (10 KPa) using PERKIN ELMER DSC-7.
[실시예 및 비교예][Examples and Comparative Examples]
교반장치, 정류탑, 응축기가 갖추어져 있는 에스테르 교환반응기에 디메틸테레프 탈레이트 100부와 에틸렌 글리콜 70부와 초산마그네슘4수화물 0.09부를 넣고 가열하여 메탄올을 유출시키며 에스테르교환반응을 실시하여 4시간에 걸쳐 에스테르교환반응을 완료한후, 난연화합물을 첨가하였다. 그 반응 혼합물에 트리메틸포스페이트 0.02부를 첨가하여 15분간 반응시킨후 삼산화안티몬 0.03부를 첨가한 후 5분간 반응시킨다.100 parts of dimethyl terephthalate, 70 parts of ethylene glycol, and 0.09 parts of magnesium acetate tetrahydrate were added to a transesterification reactor equipped with a stirring device, a rectifying tower, and a condenser, and heated to let methanol out, followed by transesterification. After completion of the transesterification reaction, a flame retardant compound was added. After adding 0.02 parts of trimethyl phosphate to the reaction mixture for 15 minutes, 0.03 parts of antimony trioxide was added and reacted for 5 minutes.
그리고 과잉의 에틸렌글리콜을 유출시켜 비스하이드록시 에틸테레프탈레이트를 얻었다. 이어서 비스하이드록시 에틸테레프탈레이트를 중합반응기로 이향시킨후 서서히 가열감압시키며 중축합 반응을 진행시켜 최종적으로 반응기의 온도를 285℃, 진공도를 0.2㎜Hg이하로 하여 고유점도 0.60의 폴리마를 얻었다. 이렇게 제조되어진 폴리마를 칩상태로 고형화한 후 2차 상태에서 12시간 이상 고상중합을 행하여 부반응물 즉, 미반응 원부재와 저분자량체등을 제거한 후 160℃, 6시간 동안 다시 진공건조 시킨후 295℃에서 용융하여 폴리머를 피드블록을 통하여 압출하고 정전인가 캐스팅법을 이용하여 30℃의 캐스팅드럼에서 냉각고화시켜 비결정성 미연신 필름을 얻었다. 그리고 미연신 필름을 120℃에서 종방향으로 4.3배 연신하고, 이러서 횡방향으로 120℃의 온도에서 4.9배 연신하고, 220℃에서 3초간 열고정하여 난연성이 부여된 저올리고머성 이축재향 폴리에스테르 필름을 얻었다.And excess ethylene glycol was distilled off and bishydroxy ethyl terephthalate was obtained. Subsequently, the bishydroxy ethyl terephthalate was transferred to the polymerization reactor, followed by a slow heating and depressurization, followed by a polycondensation reaction to finally obtain a polymer having an intrinsic viscosity of 0.60 at a temperature of 285 ° C. and a vacuum of 0.2 mmHg or less. The polymer thus prepared was solidified in a chip state, and then subjected to solid phase polymerization in a secondary state for at least 12 hours to remove side reactions, that is, unreacted raw materials and low molecular weight, and then vacuum dried for 2 hours to 160 ° C. for 2 hours. The polymer was melted at and extruded through a feed block and cooled and solidified in a casting drum at 30 ° C. using an electrostatic casting method to obtain an amorphous non-oriented film. And the unstretched film was stretched 4.3 times in the longitudinal direction at 120 ° C., and thus 4.9 times in the transverse direction at a temperature of 120 ° C., and heat-set at 220 ° C. for 3 seconds to give a low oligomeric biaxially oriented polyester film with flame retardancy. Got.
본 발명에서 거론된 화합물(실시예 1 내지 4) 및 공지되어 있는 화합물(비교예1)의 상대적 투입량, 합성된 중합체의 물성과 이축배향 연신된 베이스필름의 각종 물성 실험결과를 (표 1)에 나타내었다.The relative dosages of the compounds (Examples 1 to 4) and known compounds (Comparative Example 1) discussed in the present invention, the physical properties of the synthesized polymer and the results of various physical properties of the biaxially oriented base film are shown in (Table 1). Indicated.
또한, 각 실시예에 사용된 화합물은 하기 식과 같은 구조를 갖는다.(표 2)In addition, the compound used for each Example has a structure like the following formula (Table 2).
본 발명은 난연성분으로 인, 염소원자가 폴리에스테르 중합체에 함유되어 있으나, 특정의 아릴 포스핀산 유도체를 중축합 반응단계에서 첨가함으로써 난연성 및 전기적 특성이 우수하면서 특히 제막성과 저올리고머성의 특성이 우수한 이축배향 폴리에스테르 필름을 제공한다.In the present invention, phosphorus and chlorine atoms are contained in a polyester polymer as a flame retardant component, but by adding a specific aryl phosphinic acid derivative in the polycondensation reaction step, biaxial orientation is excellent in flame retardancy and electrical properties, and in particular in film forming and low oligomer properties. It provides a polyester film.
Claims (4)
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