KR20180086325A - Film containing polyethyleneterephthalate copolymer - Google Patents
Film containing polyethyleneterephthalate copolymer Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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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- 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
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- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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- C08J3/00—Processes of treating or compounding macromolecular substances
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- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
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- C08L2310/00—Masterbatches
Abstract
Description
본 발명은 기존 폴리에틸렌테레프탈레이트 결합을 이루는 에틸렌글라이콜(EG, Ethyleneglycol)과 테레프탈산(TPA, Terephthalic acid) 외에 추가로 폴리에틸렌글라이콜(PEG)의 체인수가 1 내지 50개이며 분자량이 800 내지 50,000인 한 방향 말단기 변성 PDMS(Polydimethylsiloxane)를 도입하여 제조된 내마모성이 개선된 공중합 폴리에틸렌테레프탈레이트를 포함하는 폴리에틸렌테레프탈레이트 필름에 관한 것이다. The present invention relates to a polyethylene terephthalate (PEG) resin having a chain number of 1 to 50 and a molecular weight of 800 to 50,000, in addition to ethylene glycol (EG, Ethyleneglycol) and terephthalic acid And more particularly to a polyethylene terephthalate film comprising a copolymerized polyethylene terephthalate having improved abrasion resistance prepared by introducing short-term modified PDMS (Polydimethylsiloxane).
일반적으로, 폴리에스테르 수지, 특히 폴리에틸렌테레프탈레이트 수지는 디카르복실산 또는 이의 에스테르 형성성 유도체 및 디올 또는 이의 에스테르 형성성 유도체로부터 합성되는 선상 고분자로, 가격이 저렴하면서도, 기계적 특성과 화학적 물성이 우수할 뿐만 아니라 가스 차단성 또한 우수하여 각종 용기, 필름, 섬유 등의 제조에 폭 넓게 사용되고 있다. 한편, 폴리에스테르는 축합 중합법으로 제조되는데, 외부 조건에 따른 평형반응으로 고온, 고진공의 조건을 통해 상업적으로 사용 가능한 점도를 얻게 되며, 이때 최종 중합물 내에 일정량의 올리고머가 잔류하게 된다.Generally, polyester resins, especially polyethylene terephthalate resins, are linear polymers synthesized from dicarboxylic acids or ester-forming derivatives thereof and diols or ester-forming derivatives thereof, which are low in cost and excellent in mechanical properties and chemical properties But also has excellent gas barrier properties and is widely used for the production of various containers, films and fibers. On the other hand, the polyester is produced by condensation polymerization method. In the equilibrium reaction according to external conditions, a commercially available viscosity is obtained through high temperature and high vacuum conditions, and a certain amount of oligomer remains in the final polymer.
종래의 폴리에틸렌테레프탈레이트는 타 수지에 비해 내마모성이 약하여 내마모성이 요구되는 분야(수지 사출물, 원사, 필름 등)에 적용하기 어려운 문제점이 있었다.Conventional polyethylene terephthalate has a problem that it is difficult to apply it to a field (resin injection molding, yarn, film, etc.) which requires less abrasion resistance than other resins.
본 발명의 목적은 공중합 폴리에틸렌테레프탈레이트의 제조 시 폴리에틸렌글라이콜(PEG)의 체인수가 1 내지 50개이며 분자량이 800 내지 50,000인 한 방향 말단기 변성 폴리디메틸실록산(PDMS)을 추가로 도입하여 내마모성이 개선된 공중합 폴리에틸렌테레프탈레이트를 이용하여 내마모성 및 이형력이 개선된 폴리에틸렌테레프탈레이트 필름을 제공하는 것이다.It is an object of the present invention to provide a method for producing a copolymerized polyethylene terephthalate by further introducing one-end modified polydimethylsiloxane (PDMS) having a number of chains of polyethylene glycol (PEG) of 1 to 50 and a molecular weight of 800 to 50,000, And to provide a polyethylene terephthalate film having improved abrasion resistance and releasability using the improved copolymerized polyethylene terephthalate.
상술한 목적을 달성하기 위한 본 발명의 하나의 양상은, 폴리에틸렌테레프탈레이트(PET, Polyethylene terephtalate) 50 내지 99.9 중량%; 및 한 방향 말단기 변성 폴리디메틸실록산(PDMS) 0.1 내지 50 중량%를 포함하고, 상기 한 방향 말단기 변성 폴리디메틸실록산(PDMS)는 하기 일반식(I)의 폴리에틸렌글라이콜(PEG)의 체인수가 1 내지 50개이며 분자량이 800 내지 50,000인 바람직하게는 분자량이 1,000내지 15,000인 한 방향 말단기 변성 폴리디메틸실록산(PDMS)을 폴리에틸렌테레프탈레이트 반응에 투입하는 것을 특징으로 하는 공중합 폴리에틸렌테레프탈레이트를 포함하는 내마모성 및 이형력이 개선된 폴리에틸렌테레프탈레이트 필름을 제공한다.According to one aspect of the present invention, there is provided a polyolefin resin composition comprising 50 to 99.9% by weight of polyethylene terephthalate (PET); And 0.1 to 50% by weight of unidirectionally terminated polydimethylsiloxane (PDMS), said unidirectionally terminated polydimethylsiloxane (PDMS) being a chain of polyethylene glycol (PEG) of the general formula (I) Terminated polydimethylsiloxane (PDMS) having a molecular weight of 1 to 50 and a molecular weight of 800 to 50,000, and preferably a molecular weight of 1,000 to 15,000, is added to the polyethylene terephthalate reaction. A polyethylene terephthalate film having improved abrasion resistance and releasability is provided.
(I)
(식 중, R= -(CH2-CH2-O)m-, m=1 내지 50(Wherein R = - (CH2-CH2-O) m-, m = 1 to 50
T= 수산기 또는 카르복실기 또는 아민기)T = a hydroxyl group or a carboxyl group or an amine group)
이 때, 공중합 폴리에틸렌테레프탈레이트를 직접 원사하는 방법과 한 방향 말단기 변성 폴리디메틸실록산(PDMS)를 고농도로 폴리에틸렌테레프탈레이트에 공중합하여 마스터배치로 활용하는 방법으로 제조되는 것을 특징으로 한다. 이 때, 상기 공중합 폴리에틸렌테레프탈레이트는 에틸렌글라이콜(EG, Ethyleneglycol)과 테레프탈산(TPA, Terephthalic acid)의 슬러리(Slurry)화 단계; 상기 슬러리의 에스테르화 반응 단계; 및 중축합 반응 단계;를 포함하고, 상기 중축합 반응 후단에 한 방향 말단기 변성 폴리디메틸실록산(PDMS)을 공중합 폴리에틸렌테레프탈레이트를 투입하는 방법에 의해 제조되는 것을 특징으로 한다.At this time, the method is characterized in that it is produced by a method in which copolymerized polyethylene terephthalate is directly yarn and a method in which short-term modified polydimethylsiloxane (PDMS) in one direction is copolymerized with polyethylene terephthalate at a high concentration and used as a master batch. At this time, the copolymerized polyethylene terephthalate may be prepared by slurrying ethylene glycol (EG, Ethyleneglycol) and terephthalic acid (TPA, Terephthalic acid); An esterification reaction step of the slurry; And a polycondensation reaction step in which monodispersed polydimethylsiloxane (PDMS) in the unidirectional end is introduced into the subsequent stage of the polycondensation reaction by copolymerizing polyethylene terephthalate.
본 발명은 공중합 폴리에틸렌테레프탈레이트를 이용한 폴리에틸렌테레프탈레이트 필름 제조 시 폴리에틸렌글라이콜(PEG)의 체인수가 1 내지 50개이며 분자량이 800 내지 50,000인 한 방향 말단기 변성 PDMS를 추가하여 제조된 공중합 폴리에틸렌테레프탈레이트를 포함하는 내마모성 및 이형력이 개선된 폴리에틸렌테레프탈레이트 필름을 제공한다. The present invention relates to a method for producing a polyethylene terephthalate film using a copolymerized polyethylene terephthalate, which comprises preparing a copolymerized polyethylene terephthalate (PEG) film obtained by adding 1 to 50 chains of polyethylene glycol (PEG) There is provided a polyethylene terephthalate film improved in abrasion resistance and release force including phthalate.
본 발명에 따른 공중합 폴리에틸렌테레프탈레이트의 제조방법은 에틸렌글라이콜(EG, Ethyleneglycol)과 테레프탈산(TPA, Terephthalic acid)의 슬러리(Slurry)화 단계; 에스테르화 반응 단계; 및 중축합 반응 단계;를 포함하고, 상기 중축합 반응 후단에 폴리에틸렌글라이콜(PEG)의 체인수가 1 내지 50개이며 분자량이 800 내지 50,000인 한 방향 말단기 변성 PDMS를 투입하는 것을 특징으로 한다.The method for producing a copolymerized polyethylene terephthalate according to the present invention comprises the steps of slurrying ethylene glycol (EG) and terephthalic acid (TPA); An esterification reaction step; End-modified PDMS having a number of chains of polyethylene glycol (PEG) of 1 to 50 and a molecular weight of 800 to 50,000 is introduced at the end of the polycondensation reaction .
본 발명에서는 상기 변성 PDMS를 폴리에틸렌테레프탈레이트의 내마모 개선 효과를 발현시키기 위하여 중축합 반응 후단에 투입하는 것이 바람직하다. 상기 변성 PDMS를 중축합 반응 후단에 투입할 경우, 결합도 99% 이상을 얻게된다.In the present invention, it is preferable to add the modified PDMS to the end of the polycondensation reaction in order to exhibit the anti-abrasion effect of polyethylene terephthalate. When the modified PDMS is introduced into the subsequent stage of the polycondensation reaction, the degree of bonding is 99% or more.
본 발명에서 추가로 투입되는 폴리디메틸실록산은 하기 일반식(I)의 구조를 갖는 화합물이다.The polydimethylsiloxane further added in the present invention is a compound having the structure of the following general formula (I).
(I)
(식 중, R= -(CH2-CH2-O)m-, m=1 내지 50(Wherein R = - (CH2-CH2-O) m-, m = 1 to 50
T= 수산기 또는 카르복실기 또는 아민기)T = a hydroxyl group or a carboxyl group or an amine group)
변성 PDMS는 말단기가 OH, -COOH 및 NH2로 구성되어 있으며, 본 발명에서는 OH, -COOH를 사용하여 폴리에틸렌테레프탈레이트에 중합시키는 것을 주 대상으로 하며, 가장 바람직하게는 기존 Diol류 (-OH)기의 중합 결합을 활용하여 OH를 가지는 변성 PDMS를 주 대상으로 한다. In the modified PDMS, the terminal groups are composed of OH, -COOH and NH2. In the present invention, the main object of the present invention is to polymerize with polyethylene terephthalate using OH and -COOH, And the modified PDMS having OH is utilized as a main target.
본 발명의 상기 변성 PDMS의 분자량은 800 내지 50,000의 범위인 것이 바람직하고, 더욱 바람직하게는 1,000 내지 15,000일 수 있다. 이 때, 변성 PDMS의 분자량이 800 미만이면 이형력이 떨어지고, 50,000을 초과하면 중축합 반응성이 떨어지게 된다. 또한 상기 변성 PDMS의 폴리에틸렌글라이콜(PEG)의 체인수가 1 내지 50개를 범위로 하는것이 바람직하며, 더욱 바람직하게는 1 내지 20개일 수 있다. 이 때, 변성 PDMS의 폴리에틸렌글라이콜(PEG)의 체인수가 1개 미만이면 중축합 반응성이 떨어지고 되고, 50개를 초과하면 이형력이 떨어지게 된다.The molecular weight of the modified PDMS of the present invention is preferably in the range of 800 to 50,000, more preferably 1,000 to 15,000. At this time, if the molecular weight of the modified PDMS is less than 800, the releasing force is lowered. If the molecular weight exceeds 50,000, the polycondensation reactivity is lowered. The number of chains of polyethylene glycol (PEG) in the modified PDMS is preferably in the range of 1 to 50, more preferably 1 to 20. If the number of chains of the polyethylene glycol (PEG) in the modified PDMS is less than 1, the polycondensation reactivity decreases. If the number of chains exceeds 50, the releasing force decreases.
본 발명은 중축합 반응 후단에 변성 PDMS를 투입하는 것을 특징으로 한다. The present invention is characterized in that denatured PDMS is introduced into the latter stage of the polycondensation reaction.
상기 변성 PDMS는 폴리에틸렌테레프탈레이트의 내마모 개선 효과를 발현시키기 위하여 중축합 반응 후단에 투입하는 것이 바람직하다. 상기 변성 PDMS를 중축합 반응 후단에 투입할 경우, 결합도 99% 이상을 얻게 된다. 중합물에 도입시 슬러리화 단계 및 에스테르화 반응 단계 또는 중축합 초기 단계에서 투입할 경우, 중합물의 점도 상승이 어렵고 변성 PDMS의 반응율이 낮아 기대효과를 확보하기 어려운 문제가 있다. 또한 중축합 반응 후단 투입 시에도 변성 PDMS에 따른 용융점도가 상승하는 문제가 발생되어 기존 폴리에스터 중합 조건과 달리 중축합 반응 조건을 설정하여야 한다. It is preferable that the modified PDMS is introduced into the latter stage of the polycondensation reaction in order to exhibit the anti-wear effect of the polyethylene terephthalate. When the modified PDMS is introduced into the subsequent stage of the polycondensation reaction, the degree of bonding is 99% or more. It is difficult to increase the viscosity of the polymer and the reaction rate of the modified PDMS is low when it is added in the slurrying step and the esterification reaction step or the initial stage of the polycondensation. Also, when the post-polycondensation reaction is carried out, there is a problem that the melt viscosity of the modified PDMS is increased. Therefore, polycondensation reaction conditions should be set differently from the conventional polyester polymerization conditions.
이때 폴리디메틸실록산의 첨가되는 양은, 공중합 폴리에틸렌테레프탈레이트 총중량에 대하여 0.1 내지 50중량%가 바람직하며, 0.5 내지 20중량%가 보다 바람직하다. 폴리디메틸실록산의 함유량이 0.1 중량% 미만이면 표면으로 마이그레이션되는 양이 적어 내마모성의 개선효과가 미미하며, 함유량이 50 중량%를 초과하면 생산성이 떨어지게 된다.The amount of the polydimethylsiloxane added is preferably 0.1 to 50% by weight, more preferably 0.5 to 20% by weight, based on the total weight of the copolymerized polyethylene terephthalate. When the content of the polydimethylsiloxane is less than 0.1% by weight, the amount migrated to the surface is small and the effect of improving the abrasion resistance is insignificant. When the content exceeds 50% by weight, the productivity drops.
이하, 본 발명에 따라 제조된 폴리에틸렌테레프탈레이트 중합체를 이용하여 필름을 제조하는 방법에 대해 상세하게 설명한다.Hereinafter, a method for producing a film using the polyethylene terephthalate polymer produced according to the present invention will be described in detail.
본 발명에 따라 생성되는 필름에는 표면에 메틸기를 갖는 실리카비드를 포함하는 무기입자가 함유된다. 통상 실리카비드는 표면에 친수성을 갖는 히드록시기(OH)를 가지고 있는데, 본 발명에 따라 표면의 히드록시기가 메틸기(CH3)로 치환된 실리카비드는 필름 내에서 윤활 역할을 하여 필름의 마찰계수를 효과적으로 저하시킨다. 기재층에 함유되는 무기입자로는 메틸기를 갖는 실리카비드 이외에, 탄산칼슘이나 콜로이달 실리카 또는 이들의 혼합물이 사용될 수 있다.The film produced according to the present invention contains inorganic particles containing silica beads having a methyl group on its surface. In general, silica beads have hydroxyl groups (OH) having hydrophilicity on the surface. According to the present invention, silica beads in which the hydroxyl group on the surface is substituted with a methyl group (CH3) act as a lubricant in the film and effectively decrease the friction coefficient of the film . As the inorganic particles contained in the base layer, in addition to silica beads having a methyl group, calcium carbonate, colloidal silica, or a mixture thereof may be used.
메틸기를 갖는 실리카비드로는 입경 2㎛ 이하, 좋게는 1㎛ 이하의 것이 사용된다. 이러한 실리카비드를 많이 사용할수록 이형필름의 마찰계수는 적어지나, 실리카비드는 입자 크기가 대체로 커서 과량 넣게 되면 기재층의 표면이 너무 거칠어지는 문제가 있다.As the silica beads having a methyl group, those having a particle diameter of 2 mu m or less, preferably 1 mu m or less, are used. The friction coefficient of the release film is reduced as the silica beads are used more frequently. However, the silica beads have a large particle size so that the surface of the base layer becomes too rough when the silica beads are used in an excessive amount.
메틸기를 갖는 실리카비드 이외의 무기입자로는 탄산칼슘이 선호된다. 입경 2㎛ 이하, 좋게는 1㎛ 이하, 0.4~0.8㎛의 탄산칼슘이 사용되는데, 대체로 작은 입경의 것을 얻을 수 있고 블록킹 방지에 좋을 것으로 생각되나, 탄산칼슘만에 의해서는 효과적이지 못하며 공정상 균일하게 분산시키는 것도 쉽지 않다.As inorganic particles other than silica beads having a methyl group, calcium carbonate is preferred. Calcium carbonate having a particle diameter of 2 탆 or less, preferably 1 탆 or less and 0.4-0.8 탆 is used. Generally, calcium carbonate having a small particle size can be obtained and is effective for preventing blocking. However, calcium carbonate alone is not effective, It is not easy to distribute it.
본 발명에 따르면 위와 같은 무기입자는 기재층에 1,000~3,000ppm 범위 내에서 함유되는 것이 바람직하다. 1,000ppm 미만으로 포함되는 경우 본 발명에서 요구하는 물성의 구현이 어려우며, 3,000ppm을 초과하여 포함되는 경우 무기입자들이 응집되서 공정상 어려움을 초래한다.According to the present invention, it is preferable that the inorganic particles are contained in the base layer in the range of 1,000 to 3,000 ppm. When it is contained in an amount of less than 1,000 ppm, it is difficult to realize the physical properties required in the present invention. When it is contained in an amount exceeding 3,000 ppm, inorganic particles aggregate and cause difficulties in the process.
한편 무기입자들 간의 혼합비율은, 바람직한 예로서 탄산칼슘과 실리카비드는 1:0.3~1:0.6의 비율로 혼합된다. On the other hand, as a preferred example, the mixing ratio of the inorganic particles is 1: 0.3 to 1: 0.6 in the ratio of calcium carbonate and silica beads.
탄산칼슘이 위 비율보다 높게 혼합되는 경우 마찰계수의 저감 효과가 적고 이물혼입이나 스크래치를 방지하는 효과가 적다. 또한 실리카비드가 위 비율보다 높게 혼합되는 경우 마찰계수의 저감 효과가 크고 이물혼입이나 스크래치 저감 효과는 크나 필름의 표면조도가 과하게 높아지는 문제가 발생한다.When the calcium carbonate is mixed at a higher ratio than the above ratio, the effect of reducing the friction coefficient is small and there is little effect of preventing foreign matters and scratching. In addition, when the silica beads are mixed at a higher ratio than the above ratio, the effect of reducing the friction coefficient is large and the effect of incorporation of foreign matter and scratch reduction is large, but the surface roughness of the film becomes excessively high.
본 발명의 필름은 공중합 폴리에틸렌테레프탈레이트와 무기입자를 혼합하여 조성물을 얻는 단계 및 상기 조성물을 용융, 공압출되고 캐스팅에서 냉각 후, 길이방향으로 3.2배 연신 후, 폭방향으로 3.2배 연신하여 188㎛의 필름으로 제조된다.The film of the present invention is obtained by mixing a copolymerized polyethylene terephthalate and an inorganic particle to obtain a composition. The composition is melted and co-extruded, cooled in a casting, stretched 3.2 times in the machine direction in the longitudinal direction, ≪ / RTI >
이하, 본 발명을 하기 실시예에 의거하여 좀더 상세하게 설명한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐 한정하지는 않으며, 본 발명의 실시예 및 비교예에서 제조된 사의 물성 평가는 다음과 같은 방법으로 실시하였다.Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are intended to illustrate the present invention and are not to be construed as limiting the scope of the present invention. The properties of the yarns prepared in Examples and Comparative Examples of the present invention were evaluated in the following manner.
1. 필름의 마찰계수1. Friction coefficient of film
두 물체의 접촉면 사이에 생기는 마찰력과 그 사이에 작용하는 법선 방향의 압력비로 정마찰 수치 및 동마찰 수치를 측정하였다. 상기 분석은 23℃, RH 50%조건에서 실시하였다.The static friction value and the dynamic friction value were measured by the frictional force generated between the contact surfaces of the two objects and the pressure ratio in the normal direction acting therebetween. The analysis was carried out at 23 ° C and RH 50%.
- 정마찰 : 미끄러짐 운동의 시작에서 임계값(threshold value)으로 극복해야 할 마찰 (Static Coefficient of Friction)- Static friction: Static Coefficient of Friction at threshold value at the beginning of slip motion.
- 동마찰 : 주어진 속도에서 미끄러짐 운동 중에 지속되는 마찰 (Kinetic Coefficient of Friction)- Kinetic Coefficient of Friction (Kinetic Coefficient of Friction at a given speed)
- 마찰계수 = (마찰시 발생하중-인가하중)/인가하중- Friction Coefficient = (Friction Generated Load - Applied Load) / Applied Load
2. 이형력(박리력)2. Release force (peeling force)
FINAT test method - 10 방법에 따라, 이형력 평가 샘플을 제조하며, 측정을 위한 기준 점착 Tape로는 Nitto社의 Nitto31B Tape를 사용하였으며, 이형력의 측정은 Peel Tester(ChemInstrument社, AR-1000)를 통해 180도 Peel방식으로 측정하였으며, 박리속도는 300mpm(meters per minute)로 실시한다.FINAT TEST METHOD - The release test sample is prepared according to the 10 method. The Nitto31B tape of Nitto is used as the reference adhesive tape for measurement. The release force is measured by Peel Tester (ChemInstrument, AR-1000) 180 degree peel method, and the peeling speed is 300 mpm (meters per minute).
실시예Example 1 One
테레프탈산 100 중량부에 대하여 에틸렌 글리콜 50 중량부 슬러리를 에스테르화 반응기에 투입하고, 250℃에서 4시간동안 물을 반응기 밖으로 유출시키면서 에스테르화 반응을 진행시켜 비스(2-하이드록시에틸) 테레프탈레이트[bis(2-hydroxyethyl) terephthalate]를 제조하였다. 이때, 인계 내열안정제를 에스테르화 반응 말기에 300ppm 투입하였다. 이후, 중합 촉매로서 안티몬 촉매를 중축합반응 초기에 300ppm을 투입하고, 250℃에서 285℃까지 60℃/hr로 승온함과 동시에, 압력을 0.1torr까지 감압하여 중축합 반응을 진행하였으며, 중축합 반응 후단에 말단기가 수산기이고 폴리에틸렌글라이콜(PEG)의 체인수가 1개이며 분자량이 5,000인 한 방향 말단기 변성 PDMS를 5.0중량% 투입하여 중축합 반응을 진행하여 중합물을 제조하였다. 상기 실시예에서는 JNC사의 FMDA-21 제품을 제조하였다.적용하였다.50 parts by weight of ethylene glycol was added to the esterification reactor to 100 parts by weight of terephthalic acid and the esterification reaction was carried out while allowing water to flow out of the reactor at 250 DEG C for 4 hours to obtain bis (2-hydroxyethyl) terephthalate [bis (2-hydroxyethyl) terephthalate]. At this time, 300 ppm of a phosphorus-based heat stabilizer was added at the end of the esterification reaction. Thereafter, 300 ppm of an antimony catalyst as a polymerization catalyst was added at the initial stage of the polycondensation reaction, the temperature was raised from 250 ° C. to 285 ° C. at 60 ° C./hr, the pressure was reduced to 0.1 torr to conduct a polycondensation reaction, After completion of the reaction, 5.0 wt% of one end of a short-term modified PDMS having a terminal hydroxyl group, a number of chains of polyethylene glycol (PEG) and a molecular weight of 5,000 was added thereto, and the polycondensation reaction was carried out to prepare a polymer. In the above examples, the FMDA-21 product of JNC was prepared.
양방향 말단기 변성 PDMS 공중합 폴리에틸렌테레프탈레이트 중합체와 1.0㎛의 실리카 입자를 표 1의 함량으로 압출기에 투입하여 용융압출하였다. 용융물을 공압출 되도록한 후, 40℃ 캐스팅롤에서 냉각하여 미연신필름을 제조하였다. 상기 미연신 필름을 기계방향(MD)으로 3.2배 연신 후, 종방향(TD)으로 3.2배 연신하여 전체 두께가 25㎛인 다층필름을 제조하였다. Bidirectional, end-group modified PDMS copolymerized polyethylene terephthalate polymer and 1.0 탆 silica particles were put into an extruder in the contents shown in Table 1 and melt-extruded. The melt was coextruded and then cooled in a 40 ° C casting roll to produce an unoriented film. The unstretched film was stretched 3.2 times in the machine direction (MD), and then stretched 3.2 times in the longitudinal direction (TD) to produce a multilayer film having a total thickness of 25 占 퐉.
실시예Example 2 2
말단기가 수산기이고 폴리에틸렌글라이콜(PEG)의 체인수가 1개이며 분자량이 5,000인 한 방향 말단기 변성 PDMS를 10.0중량% 투입하여 중축합 반응을 진행하여 중합물을 제조한 것을 제외하고는 실시예 1과 동일한 방법으로 다층필름을 제조하였다.Except that the end groups were hydroxyl groups and the number of chains of polyethylene glycol (PEG) was 1 and molecular weight was 5,000, 10.0% by weight of short-term modified PDMS in one direction was added to proceed the polycondensation reaction. To prepare a multilayer film.
실시예Example 3 3
말단기가 수산기이고 폴리에틸렌글라이콜(PEG)의 체인수가 1개이며 분자량이 15,000인 한 방향 말단기 변성 PDMS(JNC社를, FMDA-26) 10.0중량% 투입하여 중축합 반응을 진행하여 중합물을 제조한 것을 제외하고는 제외하고는 실시예 1과 동일한 방법으로 다층필름을 제조하였다.The polymerization reaction was carried out by adding 10.0% by weight of one-end modified PET (JNC, FMDA-26) having a terminal hydroxyl group and one chain of polyethylene glycol (PEG) and having a molecular weight of 15,000 Layer film was prepared in the same manner as in Example 1,
비교예Comparative Example 1 One
변성 PDMS를 투입하지 않은 것을 제외하고는 실시예 1과 같은 방법으로 다층필름을 제조하였다.A multi-layer film was prepared in the same manner as in Example 1 except that denatured PDMS was not added.
(gf/inch)Release force
(gf / inch)
표 1에서 나타난 바와 같이 상기 일반식(I)의 폴리에틸렌글라이콜(PEG)의 체인수가 1 내지 20개이며 분자량이 5,000 내지 15,000인 한 방향 말단기 변성 PDMS를 중축합 후단에 투입한 경우, 변성 PDMS를 투입하지 않은 비교예 대비 필름의 마찰계수가 감소하고 이형력이 개선되는 것을 확인할 수 있었다. As shown in Table 1, when one-directionally short-term modified PDMS having 1 to 20 chains of polyethylene glycol (PEG) represented by the general formula (I) and having a molecular weight of 5,000 to 15,000 was added to the post-polycondensation stage, It was confirmed that the friction coefficient of the film was decreased and the releasing force was improved in comparison with the comparative example in which PDMS was not applied.
이상에서 본 발명의 바람직한 실시예에 대하여 상세하게 설명하였으나, 본 발명은 상술한 실시예에 국한되는 것은 아니고, 본 발명의 취지 또는 범위를 벗어나지 않고 본 발명을 다양하게 변경하고 변형할 수 있다는 사실은 당업자에게 자명할 것이다. 따라서, 본 발명의 보호범위는 첨부한 특허청구범위 및 그와 균등한 범위로 정해져야 할 것이다.While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Will be apparent to those skilled in the art. Therefore, the scope of protection of the present invention should be defined in the appended claims and their equivalents.
Claims (3)
한 방향 말단기 변성 폴리디메틸실록산(PDMS) 0.1 내지 50 중량%를 포함하고,
상기 한 방향 말단기 변성 폴리디메틸실록산(PDMS)는 하기 일반식(I)의 폴리에틸렌글라이콜(PEG)의 체인수가 1 내지 50개이며 분자량이 800 내지 50,000인 것을 특징으로 하는 공중합 폴리에틸렌테레프탈레이트를 포함하는 내마모성 및 이형력이 개선된 폴리에틸렌테레프탈레이트 필름.
(I)
(식 중, R= -(CH2-CH2-O)m-, m=1 내지 50
T= 수산기 또는 카르복실기 또는 아민기)
50 to 99.9% by weight of polyethylene terephthalate (PET, polyethylene terephthalate); And
0.1 to 50% by weight of unidirectionally terminated polydimethylsiloxane (PDMS)
Wherein said one-direction-terminated polydimethylsiloxane (PDMS) is a copolymerized polyethylene terephthalate having a number of chains of polyethylene glycol (PEG) represented by the following general formula (I) of 1 to 50 and a molecular weight of 800 to 50,000 A polyethylene terephthalate film having improved abrasion resistance and releasability.
(I)
(Wherein R = - (CH2-CH2-O) m-, m = 1 to 50
T = a hydroxyl group or a carboxyl group or an amine group)
상기 공중합 폴리에틸렌테레프탈레이트를 직접 원사하는 방법 또는 한 방향 말단기 변성 폴리디메틸실록산(PDMS)를 고농도로 폴리에틸렌테레프탈레이트에 공중합하여 마스터배치로 활용하는 방법으로 제조되는 것을 특징으로 하는 내마모성 및 이형력이 개선된 폴리에틸렌테레프탈레이트 필름.
The method according to claim 1,
Characterized in that it is produced by a method in which the copolymerized polyethylene terephthalate is directly yarn or a method in which short-term modified polydimethylsiloxane (PDMS) in one direction is copolymerized with polyethylene terephthalate at a high concentration and used as a master batch. Polyethylene terephthalate film.
상기 공중합 폴리에틸렌테레프탈레이트는 에틸렌글라이콜(EG, Ethyleneglycol)과 테레프탈산(TPA, Terephthalic acid)의 슬러리(Slurry)화 단계;
상기 슬러리의 에스테르화 반응 단계; 및
중축합 반응 단계;를 포함하고,
상기 중축합 반응 후단에 한 방향 말단기 변성 폴리디메틸실록산(PDMS)을 공중합 폴리에틸렌테레프탈레이트를 투입하는 방법에 의해 제조되는 것을 특징으로 하는 폴리에틸렌테레프탈레이트 필름. 3. The method of claim 2,
The copolymerized polyethylene terephthalate may be prepared by slurrying ethylene glycol (EG) and terephthalic acid (TPA) into a slurry;
An esterification reaction step of the slurry; And
A polycondensation reaction step,
Wherein the poly (ethylene terephthalate) film is produced by introducing copolymerized polyethylene terephthalate into the unidirectionally shortened polydimethylsiloxane (PDMS) after the polycondensation reaction.
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| KR1020170009577A KR101949401B1 (en) | 2017-01-20 | 2017-01-20 | Film containing polyethyleneterephthalate copolymer |
| PCT/KR2018/000322 WO2018135787A1 (en) | 2017-01-20 | 2018-01-08 | Copolymerized polyethylene terephthalate polymer, yarn/bcf/film comprising same, and method for producing same |
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| KR1020170009577A KR101949401B1 (en) | 2017-01-20 | 2017-01-20 | Film containing polyethyleneterephthalate copolymer |
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| KR1020170009577A KR101949401B1 (en) | 2017-01-20 | 2017-01-20 | Film containing polyethyleneterephthalate copolymer |
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| Country | Link |
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| KR (1) | KR101949401B1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR950010745B1 (en) * | 1993-07-21 | 1995-09-22 | 주식회사코오롱 | Method for manufacturing an improved polyester fiber |
| KR20090024780A (en) * | 2006-07-04 | 2009-03-09 | 비와이케이-케미 게엠베하 | Polyhydroxy-functional polysiloxanes, method for the production and use thereof |
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2017
- 2017-01-20 KR KR1020170009577A patent/KR101949401B1/en active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR950010745B1 (en) * | 1993-07-21 | 1995-09-22 | 주식회사코오롱 | Method for manufacturing an improved polyester fiber |
| KR20090024780A (en) * | 2006-07-04 | 2009-03-09 | 비와이케이-케미 게엠베하 | Polyhydroxy-functional polysiloxanes, method for the production and use thereof |
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| Publication number | Publication date |
|---|---|
| KR101949401B1 (en) | 2019-02-19 |
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