KR910003588B1 - Preparation of polyester for firm - Google Patents
Preparation of polyester for firm Download PDFInfo
- Publication number
- KR910003588B1 KR910003588B1 KR1019870011314A KR870011314A KR910003588B1 KR 910003588 B1 KR910003588 B1 KR 910003588B1 KR 1019870011314 A KR1019870011314 A KR 1019870011314A KR 870011314 A KR870011314 A KR 870011314A KR 910003588 B1 KR910003588 B1 KR 910003588B1
- Authority
- KR
- South Korea
- Prior art keywords
- polyester
- weight
- silicon dioxide
- titanium dioxide
- film
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/04—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
본 발명은 제도용이나 라벨용등으로 사용하기에 적합한 소광 및 반투명성 필름형성용 폴리에스테르의 제조방법에 관한 것이다.The present invention relates to a method for producing a matte and semitransparent film forming polyester suitable for use in drafting, labeling and the like.
일반적으로, 특히 폴리에틸렌 테레프탈레이트와 같은 폴리에스테르류는 필름형성이 가능한 여러 중합체들 중에서도 비교적 고결정성, 고융점, 고연화점, 내약품성, 내열성, 내후성 및 전기절연성 등의 제반 특성이 우수한 고강도 중합체로서 다양한 용도의 필름류 제조에 가장 널리 사용되고 있다.In general, polyesters such as polyethylene terephthalate are high strength polymers having excellent characteristics such as relatively high crystallinity, high melting point, high softening point, chemical resistance, heat resistance, weather resistance, and electrical insulation, among various polymers capable of forming a film. It is most widely used for the manufacture of films for use.
그런데, 이러한 폴리에스테르를 사용하여 보다 고기능성이 요구되는 필름을 제조하기 위해서는 통상의 폴리에스테르에 여러 종류의 강화 첨가제들을 첨가시켜 그 기능을 개선시킨 것을 사용하여 왔는바, 이때 사용되는 강화 첨가제들의 대부분은 폴리에스테르 필름의 활성이 부족한 점으로부터 활성을 개선시켜주기 위한 활제성분들이었다.However, in order to manufacture a film requiring higher functionality using these polyesters, various kinds of reinforcing additives have been added to conventional polyesters to improve their functions. Silver was a lubricant component to improve the activity from the lack of activity of the polyester film.
특히, 제도용으로 사용하기 위한 폴리에스테르 필름의 경우, 제도시 그 필름의 광택으로인해 사용자의 시각에 영향을 주게되므로 눈의 피로를 방지해주고 화선의 선명도를 더해주어야 하며, 또한 라벨용 폴리에스테르 필름의 경우에는 제품의 품격을 향상 시켜주어야 하는데, 그러기 위해서는 사용되는 폴리에스테르 필름의 소광효과가 우수해야하고 반투명해야만 바람직하다.In particular, in case of polyester film for drafting, it may affect the user's vision due to the gloss of the film. In the case of the product to improve the quality of the product, in order to do so, the matting effect of the polyester film used must be excellent and translucent is desirable.
따라서, 상기와 같이 폴리에스테르 필름에 소광효과 및 반투명성을 부여해주기 위한 통상적인 방법으로는 폴리에스테르 중합반응 중에 불활성 무기활제로서 이산화규소를 첨가하는 방법, 또는 필름형성 후 샌드브라스트나 화학적 에칭처리에 의한 표면처리방법 등이 이용되고 있는데, 특히 전자의 불활성 무기활제를 첨가시키는 방법이 주로 사용되어지고 있다.Therefore, the conventional method for imparting matting effect and translucency to the polyester film as described above is a method of adding silicon dioxide as an inert inorganic lubricant during the polyester polymerization reaction, or sandblasting or chemical etching treatment after film formation. The surface treatment method by, etc. is used, Especially the method of adding the former inert inorganic lubricant is mainly used.
그런데, 불활성 무기활제로서 이산화규소만을 사용할 경우에는 만족스러운 고광효과를 얻을 수는 있으나, 이산화규소가 무기활제류중 투명성이 뛰어난 활제이므로 폴리에스테르 필름의 적정탁도를 얻기가 어려운 문제점이 있으며, 또 이런 문제점 때문에 필름에 충분한 탁도를 주기 위해서 이산화규소를 대량 투입시키게 되면 필름의 기계적 물성이 저하되게 되고 제조원가가 상승하게되는 등의 또다른 문제점이 발생하게 된다.However, when only silicon dioxide is used as an inert inorganic lubricant, a satisfactory high light effect can be obtained. However, since silicon dioxide is a lubricant having excellent transparency in inorganic lubricants, it is difficult to obtain an appropriate turbidity of a polyester film. Due to the problem, when a large amount of silicon dioxide is added to give a sufficient turbidity to the film, another problem occurs such that the mechanical properties of the film are lowered and the manufacturing cost is increased.
또, 후가공으로서 필름에 샌드브라스트처리나 화학적 에칭처리 등을 이용한 표면처리방법을 적용시킬 경우에는 백분이 발생하게되고, 그러한 표면처리 후 물세정과 건조공정을 거치는 동안 필름이 수축됨으로 인하여 필름에 주름이 형성되기 때문에 필름의 품질이 저하될 뿐만아니라, 후가공공정 이후의 공정의 추가에 따른 제조원가의 상승을 초래하게 되므로 바람직하지 못하다.In addition, when the surface treatment method using sand blast treatment or chemical etching treatment is applied to the film as post-processing, white powder is generated, and the film shrinks during the water cleaning and drying process after such surface treatment. Since wrinkles are formed, not only the quality of the film is lowered, but also the increase in manufacturing cost due to the addition of the process after the post-processing process is not preferable.
따라서, 본 발명자들은 상술한 바와 같은 종래의 문제점을 해결하여 보다 우수한 소광 및 반투명성을 갖는 필름 형성용 폴리에스테르를 제조하고자 다각도로 연구검토해 온 결과 본 발명에 이르게 되었다.Therefore, the present inventors have studied and studied in various angles in order to solve the conventional problems as described above to produce a film forming polyester having more excellent quenching and translucency.
이에 본 발명의 목적은 필름에 기계적 물성의 저하나 제조원가의 상승없이 우수한 소광 및 반투명성을 갖는 필름형성용 폴리에스테르를 제조하는 방법을 제공하는데 있다.Accordingly, an object of the present invention is to provide a method for producing a film forming polyester having excellent quenching and translucency without deterioration in mechanical properties or increase in manufacturing cost.
이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 중합물질에 불활성 무기활제로서 이산화규소를 첨가시켜서 소광 및 반투명성 필름형성용 폴리에스테르를 제조함에 있어서, 전체 폴리에스테르에 대하여 불활성 무기활제 성분으로서 이산화티탄 0.05 내지 0.20중량 %와 평균입경이 7 내지 40mμ인 초미립 이산화규소 0.30 내지 0.80중량 %를 함께 첨가시키되, 그 중량비(이산화티탄/이산화규소)가 0.05 내지 0.40이 되도록 첨가시켜서 됨을 특징으로 하는 소광 및 반투명성 필름형성용 폴리에스테르의 제조방법이다.In the present invention, in the production of polyester for matting and semi-transparent film formation by adding silicon dioxide as an inert inorganic lubricant to a polymer, 0.05 to 0.20 weight% of titanium dioxide and an average particle diameter are used as an inert inorganic lubricant component with respect to the total polyester. Preparation of polyester for matting and semi-transparent film formation, characterized in that the addition of 0.30 to 0.80% by weight ultrafine silicon dioxide of 7 to 40mμ is added so that the weight ratio (titanium dioxide / silicon dioxide) is 0.05 to 0.40. Way.
이하 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
통상적으로, 이산화티탄은 탁도를 부여해주는 점에서는 그 효과가 뛰어난 것임에도 불구하고, 광택을 많이나게 하기 때문에 특히 소광성이 요구되는 용도에는 사용될 수 없었다.In general, titanium dioxide, although its effect is excellent in imparting turbidity, is not particularly used for applications requiring quenching because it increases the glossiness.
그러나, 본 발명자들은 오랜 연구결과로서 이산화티탄에 초미립의 이산화규소를 일정비율 범위로 첨가시켜서 2가지 물질을 병용해서 사용하는 경우에는 필름에 우수한 소광효과와 아울러 적정 투명도를 부여시켜 줄 수 있다는 점을 알게되었다.However, the inventors of the present invention have shown that when the two materials are used in combination by adding ultra-fine silicon dioxide in a certain ratio range to titanium dioxide, the present invention can provide an excellent quenching effect and proper transparency to the film. Got to know.
그러므로, 본 발명에서는 폴리에스테르의 제조시 전체 폴리에스테르의 중량에 대하여 0.05 내지 0.20중량 %의 이산화티탄을 0.30 내지 0.80중량 %의 초미립 이산화규소와 함께 첨가시켜서 소광효과를 개선시켜주었으며, 이때 사용하기에 적합한 이산화규소의 평균입경은 7 내지 40mμ인 것이 좋은바, 이는 미크론(μ)단위 크기의 이산화규소에 비하여 상기와 같은 밀리미크론(mμ)단위 크기의 초미립 이산화규소가 소광제로서 그 효과가 탁월하며, 특히 이산화티탄의 광택발현성을 감소시킬 뿐 아니라 입자분산성도 향상시켜주기 때문이다.Therefore, in the present invention, the matting effect was improved by adding 0.05 to 0.20% by weight of titanium dioxide with 0.30 to 0.80% by weight of ultrafine silicon dioxide, based on the total weight of the polyester. It is preferable that the average particle diameter of silicon dioxide suitable for is 7 to 40 mμ, which is the effect of ultrafine silicon dioxide of the above millimeter micron (mμ) size as a matting agent, compared to micron (μ) sized silicon dioxide. It is excellent because it not only reduces the glossiness of titanium dioxide, but also improves particle dispersibility.
본 발명에 따른 소광 및 반투명성 필름형성용, 폴리에스테르의 제조에 있어서, 만약 상기 이산화티탄의 첨가량을 0.05중량 %미만으로 할 경우에는 필름의 목적하는 충분한 불투명성을 얻기 어렵고, 또 이활성이 부족되기 쉬우며, 반면에 그 첨가량을 0.20중량 %이상으로 하게되면 이산화규소의 첨가량을 증가시키더라도 더 이상 충분한 소광효과를 얻을 수 없으며, 반면에 그 첨가량이 0.80중량 %를 초과할 시에는 더 이상의 소광효과없이 제조원가만 상승되게 되므로 바람직하지 못하다.In the manufacture of polyester for matting and semi-transparent film formation according to the present invention, if the addition amount of the titanium dioxide is less than 0.05% by weight, it is difficult to obtain the desired sufficient opacity of the film, and the activity is insufficient. On the other hand, if the addition amount is more than 0.20% by weight, the increase in the amount of addition of silicon dioxide can no longer provide sufficient quenching effect, whereas when the addition amount exceeds 0.80% by weight, the further quenching effect is achieved. It is not preferable because only the manufacturing cost is increased without.
그리고, 본 발명에 따른 이산화티탄과 이산화규소의 첨가량의 중량비(이산화티탄/이산화규소)는 0.05 내지 0.40의 범위로 첨가 사용하는 것이 효과적인데, 만약 상기 중량비를 0.05 미만으로 하게되면 원하는 불투명성을 얻기가 어려우며 때로는 활성이 저하되기도 하고, 또 상기 중량비를 0.40이상으로 할 경우에는 충분한 소광효과를 얻을 수 없을 뿐아니라 입자분산성이 약화되게 되므로 좋지않다.In addition, the weight ratio (titanium dioxide / silicon dioxide) of the added amount of titanium dioxide and silicon dioxide according to the present invention is effective to be used in the range of 0.05 to 0.40. If the weight ratio is less than 0.05, it is difficult to obtain the desired opacity. It is not good because it is difficult and sometimes the activity is lowered, and when the weight ratio is 0.40 or more, sufficient matting effect is not obtained and particle dispersibility is weakened.
본 발명에서의 적정투명도(반 투명도)는 필름의 헤이즈(Haze)가 40 내지 60%의 범위일 때 얻을 수 있고, 적당한 소광효과는 측정각도 60°에서의 측정그로스(Gloss)가 10 내지 30%일 때 얻어지게 된다.Appropriate transparency (semi-transparency) in the present invention can be obtained when the haze of the film is in the range of 40 to 60%, and the suitable matting effect is 10 to 30% of the measurement gloss at the measurement angle of 60 °. Obtained when
이하 본 발명을 실시예에 의거하여 상세히 설명하면 다음과 같으며, 각각의 특성치는 하기의 방법에 따라 측정된 값이다. 또한, 본 실시예에서의 중량 %는 디메틸 테레프탈레이트(DMT)에 대한 비율이다.Hereinafter, the present invention will be described in detail with reference to Examples. Each characteristic value is a value measured according to the following method. In addition, the weight% in this Example is a ratio with respect to dimethyl terephthalate (DMT).
1. 필름 헤이즈(Haze) : ASTM D 1003-61에 의거하여 측정한다.1. Film Haze: Measured according to ASTM D 1003-61.
2. 필름 그로스(Gloss) : ASTM D 1003-61에 의거하여 측정하며, 이때 측정각도는 60°이다.2. Film gloss (Gloss): measured in accordance with ASTM D 1003-61, the measurement angle is 60 °.
3. 마찰계수 : ASTM D 1894-63에 의거하여 측정한다.3. Coefficient of friction: Measured according to ASTM D 1894-63.
[실시예 1]Example 1
에틸렌글리콜과 디메틸 테레프탈레이트(DMT)를 1.8몰 비로 투입시키고 여기에 초산아연 0.052중량 %를 투입시킨후 140℃ 내지 230℃의 온도를 유지시키면서 3시간동안 에스테르교환 반응시켜서 메탄올을 유출시킨다.Ethylene glycol and dimethyl terephthalate (DMT) were added in a 1.8 molar ratio, and 0.052% by weight of zinc acetate was added thereto, followed by transesterification for 3 hours while maintaining a temperature of 140 ° C to 230 ° C to discharge methanol.
메탄올 유출이 종료된 다음, 이산화티탄 0.11중량 %를 30중량 %에틸렌글리콜 슬러리로 제조하여 상기 에스테르 교환 반응관에 투입시키고 10분동안 교반시킨후, 다시 이산화규소 0.54중량 %를 20중량 % 에틸렌글리콜 슬러리로 제조하여 상기 반응관에 투입시키고 10분동안 교반시킨다음, 여기에 트리메틸포스페이트 0.1중량 %를 투입시키고 이를 중축합관으로 이송시킨다.After the methanol distillation was completed, 0.11% by weight of titanium dioxide was prepared into a 30% by weight ethylene glycol slurry, introduced into the transesterification reaction tube, stirred for 10 minutes, and then 0.54% by weight of silicon dioxide was added to 20% by weight ethylene glycol slurry. Prepared into the reaction tube and stirred for 10 minutes, and then 0.1% by weight of trimethyl phosphate was added thereto and transferred to the polycondensation tube.
그후, 삼산화 안티몬 0.045중량 %을 첨가시켜 3시간 30분동안 중축합반응시켜서 고유점도 0.625를 갖는 중합체를 얻고, 이 중합체를 통상적인 방법에 따라 용융 및 압출후 이축연신시켜서 75μ두께의 필름을 얻었다. 이에 대한 특성 평가치는 다음 표1에 나타내었다.Thereafter, 0.045% by weight of antimony trioxide was added to carry out polycondensation reaction for 3 hours and 30 minutes to obtain a polymer having an intrinsic viscosity of 0.625. The polymer was biaxially stretched after melting and extruding according to a conventional method to obtain a film having a thickness of 75 mu. The characteristics evaluation for this is shown in Table 1
[실시예 2]Example 2
이산화티탄을 0.06중량 % 투입시키는 것을 제외하고는 상기 실시예 1과 동일하게 실시한다.The same procedure as in Example 1 was carried out except that 0.06% by weight of titanium dioxide was added.
[실시예3]Example 3
이산화티탄을 0.18중량 % 투입시키는 것을 제외하고는 상기 실시예 1과 동일하게 실시한다.Except for adding 0.18% by weight of titanium dioxide it was carried out in the same manner as in Example 1.
[비교예 1]Comparative Example 1
이산화티탄을 사용하지 않고, 이산화규소로서 Syloid #150을 1.8중량 % 투입시키는 것을 제외하고는 상기 실시예 1과 동일하게 실시한다.The same procedure as in Example 1 was carried out except that 1.8 wt% of Syloid # 150 was added as silicon dioxide without using titanium dioxide.
[비교예 2]Comparative Example 2
이산화티탄을 0.24중량 % 투입시키는 것을 제외하고는 상기 실시예 1과 동일하게 실시한다.The same procedure as in Example 1 was carried out except that 0.24 wt% of titanium dioxide was added.
[표 1]TABLE 1
*Haze:투명도* Haze: Transparency
Gloss:광반사율Gloss: Light reflectance
정 : 정마찰계수Static: coefficient of static friction
동 : 동마찰계수Copper: Coefficient of Friction
Claims (1)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019870011314A KR910003588B1 (en) | 1987-10-13 | 1987-10-13 | Preparation of polyester for firm |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019870011314A KR910003588B1 (en) | 1987-10-13 | 1987-10-13 | Preparation of polyester for firm |
Publications (2)
Publication Number | Publication Date |
---|---|
KR890006699A KR890006699A (en) | 1989-06-15 |
KR910003588B1 true KR910003588B1 (en) | 1991-06-07 |
Family
ID=19265125
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1019870011314A KR910003588B1 (en) | 1987-10-13 | 1987-10-13 | Preparation of polyester for firm |
Country Status (1)
Country | Link |
---|---|
KR (1) | KR910003588B1 (en) |
-
1987
- 1987-10-13 KR KR1019870011314A patent/KR910003588B1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
KR890006699A (en) | 1989-06-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA1056093A (en) | Compositions of 3,3,3-trifluoro-2-trifluoromethyl propene/vinylidene fluoride copolymer and polytetrafluoroethylene | |
US20050154118A1 (en) | Polyester composition comprising carbon black | |
EP0071765A2 (en) | Polybutylene terephthalate molding compositions and articles molded therefrom | |
JP3338330B2 (en) | Polyester resin composite molding | |
EP0213887B1 (en) | Thermoplastic polyester composition for powdered paint | |
US4092289A (en) | Polyester composition | |
KR910003588B1 (en) | Preparation of polyester for firm | |
TWI388601B (en) | Copolyester resin composition for profile extrusion molding and molded articles made from the same | |
JP2848725B2 (en) | Polyester shrink film | |
JPH0730243B2 (en) | Blend of amorphous poly (aryl ether ketone) s and polyarylates | |
Mathur | Testing and evaluation of plastics | |
KR101924774B1 (en) | Polymethylpropylene terephthalate with improved impact strength, preparation method thereof and film using the same | |
JP3151875B2 (en) | polyester | |
DE69403085T2 (en) | METHOD FOR PRODUCING POLYMER MIXTURES CONTAINING POLY (ETHYLENE 2,6-NAPHTHALEDICARBONIC ACID ESTER) WITH REDUCED FLUORESCENCE | |
JP2919539B2 (en) | Polyester production method | |
KR100249485B1 (en) | Transparency copolyester thick sheet | |
KR101868990B1 (en) | Copolymerized polyester resin and preparation method thereof | |
JPH08504469A (en) | Electrical insulation from biaxially oriented PENBB film | |
JP2943183B2 (en) | Laminated molding | |
JP3059819B2 (en) | Polyester thermoformed product | |
KR100249486B1 (en) | Transparency copolyester thick sheet | |
KR20000002226A (en) | Transparent copolyester plate sheet | |
KR0157091B1 (en) | Biaxially oriented polyester film and preparing method thereof | |
CN111363336A (en) | High-performance low-cost PC modified material and preparation method thereof | |
KR0164936B1 (en) | Polymer film for insulating |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A201 | Request for examination | ||
G160 | Decision to publish patent application | ||
GRNT | Written decision to grant | ||
FPAY | Annual fee payment |
Payment date: 20040409 Year of fee payment: 14 |
|
LAPS | Lapse due to unpaid annual fee |