KR20140032275A - White porous polyester film with improved moldability and preparing method thereof - Google Patents
White porous polyester film with improved moldability and preparing method thereof Download PDFInfo
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- KR20140032275A KR20140032275A KR1020120098974A KR20120098974A KR20140032275A KR 20140032275 A KR20140032275 A KR 20140032275A KR 1020120098974 A KR1020120098974 A KR 1020120098974A KR 20120098974 A KR20120098974 A KR 20120098974A KR 20140032275 A KR20140032275 A KR 20140032275A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
- B29C55/146—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly transversely to the direction of feed and then parallel thereto
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0004—Use of compounding ingredients, the chemical constitution of which is unknown, broadly defined, or irrelevant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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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
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
Description
본 발명은 백색 다공성 폴리에스테르 필름에 관한 것으로 폴리에스테르계 수지에 MXD-6를 혼합하고 용융압출하여 제조된 성형성이 개선되고 CO2 가스 투과율이 40cc/㎡atm*day이하인 것을 특징으로 하는 백색 다공성 폴리에스테르 필름 및 이의 제조방법에 관한 것이다.
The present invention relates to a white porous polyester film, which is improved in formability produced by mixing MXD-6 in a polyester resin and melt extruding, and has a white porous structure having a CO 2 gas permeability of 40 cc / m 2 atm * day or less. It relates to a polyester film and a method for producing the same.
일반적으로 폴리에스테르수지에 백색 무기입자를 혼합하여 제조된 백색 폴리에스테르 필름은 기계적 성질, 내열성, 수치 안정성 면에서 폴리에스테르 고유의 특성을 유지하면서 빛 차단성과 백색도가 우수하다.In general, a white polyester film prepared by mixing white inorganic particles with a polyester resin is excellent in light blocking properties and whiteness while maintaining polyester properties in terms of mechanical properties, heat resistance, and numerical stability.
백색 다공성 폴리에스테르 필름을 제조하는 방법에는 다양한 방법이 공지되어 있다. 일본 특허공개 소화 58-50625호는 폴리에스테르에 발포제를 첨가하는 방법을 개시하고 있고, 일본 특허공개 소화 57-49648호는 폴리에스테르와 폴리올레핀 수지를 배합하여 필름의 표면 및 내부에 미세 기공을 형성시키는 방법을 개시하고 있다.Various methods are known for producing a white porous polyester film. Japanese Patent Laid-Open No. 58-50625 discloses a method of adding a blowing agent to polyester, and Japanese Patent Laid-Open No. 57-49648 combines polyester and polyolefin resin to form fine pores on the surface and inside of the film. A method is disclosed.
그러나, 종래기술은 제조공정 과정에서 상용성 불량으로 인한 기공균일도가 불량하고 파단이 발생하는 문제가 있다. 또한, 종래기술 중 폴리에스테르 수지를 비상용성 수지와 혼합하여 필름을 제조하는 기술의 경우 비상용성 수지 사용으로 인해 Recycle Chip의 사용이 불가하여 원가가 상승하는 문제가 있다. 또한, 종래기술에 의한 다공성 폴리에스테르 필름의 경우 굴곡 내구성 및 성형성에 대한 개선이 필요하다.
However, the prior art has a problem in that pore uniformity due to poor compatibility during the manufacturing process and poor fracture occurs. In addition, in the prior art, a technique for manufacturing a film by mixing a polyester resin with an incompatible resin has a problem in that the use of the incompatible resin is impossible due to the use of the recycle chip, thereby increasing the cost. In addition, in the case of the porous polyester film according to the prior art, it is necessary to improve the bending durability and formability.
따라서, 본 발명의 목적은 성형성 및 가스 배리어성이 향상된 백색 다공성 폴리에스테르 필름 및 이의 제조방법을 제공하는 것이다.
Accordingly, it is an object of the present invention to provide a white porous polyester film having improved moldability and gas barrier properties and a method of manufacturing the same.
상기한 바와 같은 목적을 달성하기 위하여 본 발명은 폴리에스테르 수지, 무기입자, MXD-6 및 형광증백제를 포함하고 CO2 가스 투과율이 40cc/㎡atm*day이하인 것을 특징으로 하는 백색 다공성 폴리에스테르 필름을 제공한다.In order to achieve the object as described above, the present invention comprises a polyester resin, inorganic particles, MXD-6 and a fluorescent brightener and a white porous polyester film, characterized in that the CO 2 gas permeability is less than 40cc / ㎡atm * day To provide.
본 발명의 적절한 실시형태에 따르면, 상기 백색 다공성 폴리에스테르 필름이 필름 총 중량을 기준으로 폴리에스테르 수지 50 내지 90 중량%, 무기입자 3 내지 20 중량%, 형광증백제 0.01 내지 0.5 중량% 및 MXD-6 1.0 내지 30 중량%를 포함하는 것을 특징으로 하는 백색 다공성 폴리에스테르 필름을 제공한다.According to a preferred embodiment of the invention, the white porous polyester film is 50 to 90% by weight polyester resin, 3 to 20% by weight inorganic particles, 0.01 to 0.5% by weight optical brightener and MXD- based on the total weight of the film It provides a white porous polyester film comprising 6 1.0 to 30% by weight.
본 발명의 또 다른 적절한 실시형태에 따르면, 상기 무기입자가 이산화티탄, 황산바륨, 탄산칼슘, 실리카, 카올린, 탈크, 제올라이트 및 이들의 혼합물로 이루어진 군으로부터 선택되는 것을 특징으로 하는 백색 다공성 폴리에스테르 필름을 제공한다.According to another suitable embodiment of the present invention, the white porous polyester film, characterized in that the inorganic particles are selected from the group consisting of titanium dioxide, barium sulfate, calcium carbonate, silica, kaolin, talc, zeolite and mixtures thereof. To provide.
또한, 본 발명은 폴리에스테르 수지, 무기입자, MXD-6 및 형광증백제를 용융상태에서 혼합한 후 용융 압출하는 단계; 종방향으로 연신하는 단계; 및 횡방향으로 연신하는 단계를 포함하는 백색 다공성 폴리에스테르 필름의 제조방법을 제공한다.
In addition, the present invention comprises the steps of melt extrusion after mixing the polyester resin, inorganic particles, MXD-6 and the optical brightener in a molten state; Stretching in the longitudinal direction; And it provides a method for producing a white porous polyester film comprising the step of stretching in the transverse direction.
본 발명은 종방향(MD) 인장강도가 13.0 ㎏f/㎟, 횡방향(TD) 인장강도가 22.0 ㎏h/㎟이고, CO2 가스 투과율이 40cc/㎡atm*day 이하인 것을 특징으로 하는 백색 다공성 폴리에스테르 필름을 제공하고, 상기 필름은 성형성과 가스 배리어성이 우수하다.
The present invention is characterized in that the longitudinal tensile (MD) tensile strength is 13.0 kgf / mm2, the transverse (TD) tensile strength is 22.0 kgh / mm2, and the CO 2 gas permeability is less than 40 cc / ㎡ atm * day white porous A polyester film is provided, and the film is excellent in formability and gas barrier property.
이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명에 따른 백색 다공성 폴리에스테르 필름은 폴리에스테르 수지, 무기입자, 형광증백제 및 MXD-6를 포함한다.The white porous polyester film according to the present invention includes a polyester resin, inorganic particles, optical brightener and MXD-6.
본 발명의 필름에 사용되는 폴리에스테르 수지는 방향족 다이카복실산을 주성분으로 하는 산성분과 알킬렌글리콜을 주성분으로 하는 글리콜 성분을 중축합하여 제조될 수 있다. 방향족 다이카복실산의 구체적 예로는 다이메틸테레프탈레이트를 들 수 있으며, 이들의 성질을 크게 변화시키지 않는 범위 내에서 이외의 방향족 다이카복실산 성분을 공중합시킬 수 있다. 사용될 수 있는 이외의 방향족 다이카복실산의 구체적인 예로는 테레프탈산, 아이소프탈산, 나프탈렌다이카복실산, 다이메틸 이소프탈레이트 등을 들 수 있다. 알킬렌글리콜의 구체적인 예로는 에틸렌글리콜을 들 수 있으며, 이들의 성질을 크게 변화시키지 않는 범위 내에서 이외의 글리콜 성분을 공중합시킬 수 있다. 사용될 수 있는 이외의 글리콜 성분의 구체적인 예로는 다이에틸렌글리콜, 트리메틸렌글리콜, 테트라메틸렌글리콜, 1,4-시클로헥산다이메탄올, 2,2-다이메틸(-1,3-프로판)디올 등을 들 수 있다.The polyester resin used for the film of this invention can be manufactured by polycondensing the acid component which has aromatic dicarboxylic acid as a main component, and the glycol component which has alkylene glycol as a main component. Specific examples of the aromatic dicarboxylic acid include dimethyl terephthalate, and other aromatic dicarboxylic acid components can be copolymerized within a range that does not significantly change their properties. Specific examples of aromatic dicarboxylic acids other than those that may be used include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, dimethyl isophthalate and the like. Specific examples of the alkylene glycol include ethylene glycol, and other glycol components may be copolymerized within the range of not significantly changing their properties. Specific examples of glycol components other than those which may be used include diethylene glycol, trimethylene glycol, tetramethylene glycol, 1,4-cyclohexanedimethanol, 2,2-dimethyl (-1,3-propane) diol, and the like. Can be.
본 발명의 필름에 사용되는 무기입자는 이산화티탄, 황산바륨, 탄산칼슘, 실리카, 카올린, 탈크, 제올라이트 및 이들의 혼합물을 포함한다.Inorganic particles used in the film of the present invention include titanium dioxide, barium sulfate, calcium carbonate, silica, kaolin, talc, zeolite and mixtures thereof.
이하, 실시예에 의하여 본 발명을 구체적으로 설명한다. 다만, 본 발명은 이들 실시예에만 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail by way of examples. However, the present invention is not limited only to these examples.
이하 본 발명에서 필름의 물성은 다음의 방법에 의해 측정하였다.Hereinafter, the physical properties of the film in the present invention were measured by the following method.
1) 인장강도1) Tensile strength
ASTM D882에 따라 MD와 TD로 측정하였다.It was measured by MD and TD according to ASTM D882.
2) CO2 가스 투과율2) CO 2 gas permeability
ASTM D3985의 표준 측정법에 따라 투기도 측정기(OX-TRAM 2/21, MOCON사, 미국)를 사용하여 CO2의 투과도(cc/㎡.day.atm)를 측정하였다.
Permeability (cc / m 2 .day.atm) of CO 2 was measured using an air permeability meter (OX-TRAM 2/21, MOCON, USA) according to the standard measurement method of ASTM D3985.
[실시예 1]Example 1
디메틸테레프탈레이트와 에틸렌글리콜을 1:2 당량비로 혼합한 뒤, 이 혼합물에 에스테르 교환반응 촉매로 망간아세테이트를 0.03중량%를 첨가하여 폴리에틸렌테레프탈레이트의 단량체로서 비스-2-하이드록시에틸테레프탈레이트를 제조하였다. 여기에 테트라키스-3,5-디-t-부틸하이드록시페닐프로파노일옥시메틸메탄 0.2중량%와 중축합 촉매로 산화안티몬 0.05중량%를 첨가하고 중축합을 완결시켜 극한점도가 0.61dl/gr이고, 유리전이온도가 73℃인 폴리에스테르 수지를 제조하였다Dimethyl terephthalate and ethylene glycol were mixed in a 1: 2 equivalent ratio, and then 0.03% by weight of manganese acetate was added to the mixture as a transesterification catalyst to prepare bis-2-hydroxyethyl terephthalate as a monomer of polyethylene terephthalate. It was. To this, 0.2 wt% of tetrakis-3,5-di-t-butylhydroxyphenylpropanoyloxymethylmethane and 0.05 wt% of antimony oxide were added with a polycondensation catalyst, and the polycondensation was completed to obtain an ultimate viscosity of 0.61 dl /. gr, a polyester resin having a glass transition temperature of 73 ℃ was prepared.
이축압출기에서, 상기에서 제조된 폴리에스테르 수지에, 평균입경이 0.25㎛인 이산화티탄 10중량%, MXD-6 5중량% 및 형광증백제 0.1중량%를 투입하여 용융체로 1분간 혼합한 후 통상의 폴리에스테르 필름 제조방식에 따라 건조, 용융, 압출 하여 Sheet 형태로 형성하였다. 이 때 용융 압출 공정에서 용융체로 체류시간을 2분간 유지하였다. 그리고 나서 120℃에서 종방향으로 3.5배로 연신하고, 이를 다시 230℃에서 횡방향으로 2.7배 연신시켜 이축연신 고분자 필름을 제조하였다.
In the twin screw extruder, 10% by weight of titanium dioxide, 5% by weight of MXD-6 and 0.1% by weight of a fluorescent brightener were added to the polyester resin prepared above, mixed with a melt for 1 minute, and then According to the polyester film production method was dried, melted, extruded to form a sheet. At this time, the residence time was maintained for 2 minutes in the melt in the melt extrusion process. Then, the film was stretched 3.5 times in the longitudinal direction at 120 ° C., and then stretched 2.7 times in the transverse direction at 230 ° C. to prepare a biaxially stretched polymer film.
[실시예 2][Example 2]
MXD-6 첨가량을 10중량% 첨가한 것을 제외하고는 실시예 1과 동일한 방법으로 수행하였다.
The same procedure as in Example 1 was conducted except that the addition amount of MXD-6 was added 10 wt%.
[실시예 3][Example 3]
MXD-6 첨가량을 15중량% 첨가한 것을 제외하고는 실시예 1과 동일한 방법으로 수행하였다.
The same procedure as in Example 1 was conducted except that 15 wt% of MXD-6 was added.
[실시예4]Example 4
MXD-6 첨가량을 20중량% 첨가한 것을 제외하고는 실시예 1과 동일한 방법으로 수행하였다.
The same procedure as in Example 1 was carried out except that the amount of MXD-6 added was added 20% by weight.
[비교예1][Comparative Example 1]
MXD-6를 첨가하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로 수행하였다.
The same procedure as in Example 1 was carried out except that MXD-6 was not added.
측정결과는 다음과 같이 [표1]에 나타내었다.
The measurement results are shown in [Table 1] as follows.
구분
division
MXD-6 함량
(wt%)
MXD-6 content
(wt%)
가시광선 반사율
(%)
Visible light reflectance
(%)
인장강도
(㎏f/㎟)
The tensile strength
(Kgf / mm < 2 &
배리어성, CO2
(cc/㎡atm*day)
Barrier, CO 2
(cc / ㎡atm * day)
MD
MD
TD
TD
실시예1
Example 1
5.0
5.0
95.2
95.2
13.2
13.2
22.3
22.3
35.7
35.7
실시예2
Example 2
10.0
10.0
95.0
95.0
13.7
13.7
22.9
22.9
29.8
29.8
실시예3
Example 3
15.0
15.0
95.1
95.1
14.9
14.9
23.6
23.6
22.9
22.9
실시예4
Example 4
20.0
20.0
95.1
95.1
15.2
15.2
24.3
24.3
14.9
14.9
비교예1
Comparative Example 1
-
-
95.3
95.3
12.3
12.3
21.5
21.5
48.5
48.5
상기 [표1]에서 보이는 바와 같이, 본 발명에 따른 필름은 배리어성이 40cc/㎡atm*day이하인 것을 알 수 있다.As shown in Table 1, it can be seen that the film according to the present invention has a barrier property of 40 cc / m 2 atm * day or less.
Claims (4)
A white porous polyester film comprising a polyester resin, inorganic particles, MXD-6, and a fluorescent brightener, and having a CO 2 gas transmittance of 40 cc / m 2 atm * day or less.
상기 백색 다공성 폴리에스테르 필름이 필름 총 중량을 기준으로 폴리에스테르 수지 50 내지 90 중량%, 무기입자 3 내지 20 중량%, 형광증백제 0.01 내지 0.5 중량% 및 MXD-6 1.0 내지 30 중량%를 포함하는 것을 특징으로 하는 백색 다공성 폴리에스테르 필름.
The method of claim 1,
The white porous polyester film includes 50 to 90% by weight of polyester resin, 3 to 20% by weight of inorganic particles, 0.01 to 0.5% by weight of optical brightener, and 1.0 to 30% by weight of MXD-6 based on the total weight of the film. White porous polyester film, characterized in that.
상기 무기입자가 이산화티탄, 황산바륨, 탄산칼슘, 실리카, 카올린, 탈크, 제올라이트 및 이들의 혼합물로 이루어진 군으로부터 선택되는 것을 특징으로 하는 백색 다공성 폴리에스테르 필름.
The method according to claim 1,
White inorganic polyester film, characterized in that the inorganic particles are selected from the group consisting of titanium dioxide, barium sulfate, calcium carbonate, silica, kaolin, talc, zeolite and mixtures thereof.
종방향으로 연신하는 단계; 및
횡방향으로 연신하는 단계를 포함하는 제 1 항의 백색 다공성 폴리에스테르 필름의 제조방법.
Melting and extruding the polyester resin, the inorganic particles, the MXD-6, and the optical brightener in a molten state;
Stretching in the longitudinal direction; And
A process for producing the white porous polyester film of claim 1, comprising stretching in a lateral direction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020120098974A KR20140032275A (en) | 2012-09-06 | 2012-09-06 | White porous polyester film with improved moldability and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020120098974A KR20140032275A (en) | 2012-09-06 | 2012-09-06 | White porous polyester film with improved moldability and preparing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20140032275A true KR20140032275A (en) | 2014-03-14 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020120098974A KR20140032275A (en) | 2012-09-06 | 2012-09-06 | White porous polyester film with improved moldability and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20140032275A (en) |
-
2012
- 2012-09-06 KR KR1020120098974A patent/KR20140032275A/en not_active Application Discontinuation
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