KR20100002719A - A manufacturing method of polyvinylalcohol film, a polyvinylalcohol film formed therefrom and a polarizer having the same - Google Patents
A manufacturing method of polyvinylalcohol film, a polyvinylalcohol film formed therefrom and a polarizer having the same Download PDFInfo
- Publication number
- KR20100002719A KR20100002719A KR1020080062719A KR20080062719A KR20100002719A KR 20100002719 A KR20100002719 A KR 20100002719A KR 1020080062719 A KR1020080062719 A KR 1020080062719A KR 20080062719 A KR20080062719 A KR 20080062719A KR 20100002719 A KR20100002719 A KR 20100002719A
- Authority
- KR
- South Korea
- Prior art keywords
- surfactant
- polyoxyethylene
- polyvinyl alcohol
- ether
- film
- Prior art date
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L83/04—Polysiloxanes
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- 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
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
-
- 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
- C08J2483/00—Characterised by the use 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; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Moulding By Coating Moulds (AREA)
- Polarising Elements (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
본 발명은 액정표시장치의 편광필름 등에 사용되는 폴리비닐알코올계 필름의 제조방법, 이로부터 형성된 폴리비닐알코올계 필름 및 이를 구비한 편광판에 관한 것이다.The present invention relates to a method for producing a polyvinyl alcohol-based film used in a polarizing film or the like of a liquid crystal display device, a polyvinyl alcohol-based film formed therefrom and a polarizing plate having the same.
폴리비닐알코올계 필름은 일반적으로 일축 연신후 이색성 염료를 흡착시켜 편광필름으로 제조한 다음, 3-아세트산 셀룰로오스 등으로 된 보호막을 부착시켜 편광판으로 사용된다. 광의 투과 및 차폐기능을 갖는 편광판은 광의 스위칭 기능을 갖는 액정과 더불어 액정표시장치의 기본적인 구성을 이룬다.Polyvinyl alcohol-based film is generally used as a polarizing plate by adsorbing a dichroic dye after uniaxial stretching to prepare a polarizing film, then attach a protective film made of 3-cellulose cellulose. A polarizing plate having a light transmitting and shielding function forms a basic configuration of a liquid crystal display device together with a liquid crystal having a light switching function.
이와 같은 광학 용도로 사용되는 폴리비닐알코올계 필름은 통상적으로 폴리비닐알코올계 고분자와 필름의 연신성을 향상시키기 위한 가소제를 물과 같은 용매에 용해시켜 폴리비닐알코올계 고분자 용액을 제조한 다음, 다이를 통하여 벨트나 금속 드럼과 같은 캐스팅 기재 표면에 솔루션 캐스팅한 후 건조시켜 제막하는 방법으로 제조된다.The polyvinyl alcohol-based film used for such optical applications typically prepares a polyvinyl alcohol-based polymer solution by dissolving a polyvinyl alcohol-based polymer and a plasticizer for improving the stretchability of the film in a solvent such as water. Through solution casting on the surface of the casting substrate, such as a belt or a metal drum through the manufacturing method by drying to form a film.
전술한 제조공정이 반복됨에 따라, 표면장력이 큰 다가 알코올 등으로 된 가소제가 캐스팅 기재 표면에 잔류하여 축적되고, 이렇게 형성된 가소제층은 폴리비닐알코올계 필름의 박리성을 불량하게 하며, 이에 따라 박리된 폴리비닐알코올계 필름이 일부 연신되는 등 물성이 저하되는 결과를 초래한다.As the above-described manufacturing process is repeated, a plasticizer made of polyhydric alcohol or the like having a large surface tension remains and accumulates on the surface of the casting substrate, and the thus formed plasticizer layer deteriorates the peelability of the polyvinyl alcohol-based film, and thus peels. The resulting polyvinyl alcohol-based film is partially stretched, resulting in a decrease in physical properties.
이와 같은 문제점을 해결하기 위하여, 폴리비닐알코올계 필름 제조시 계면활성제를 폴리비닐알코올계 고분자 용액에 첨가하여 솔루션 캐스팅하므로서 필름의 박리성을 개선하고 있다.In order to solve such a problem, in the production of a polyvinyl alcohol-based film, the surfactant is added to the polyvinyl alcohol-based polymer solution to solution casting, thereby improving the peelability of the film.
예를 들어, 대한민국 공개특허 특2001-0104259호, 일본국 공개특허 2002-146139호, 일본국 공개특허 2004-155922호, 일본국 등록특허 2688557호, 일본국 등록특허 2636643호 등에는 계면활성제로서 양이온성 계면활성제, 비이온성 계면활성제, 음이온성 계면활성제 등을 각각 단독으로 또는 이들을 2종 이상 병용하여 사용한 폴리비닐알코올계 필름의 제조방법을 개시하고 있다. 특히 일본국 공개특허 2006-249407호에는 캐스팅 기재로부터의 박리성을 고려하여 HLB가 다른 2종의 비이온성 계면활성제를 동시에 사용한 폴리비닐알코올계 필름의 제조방법을 개시하고 있다.For example, Korean Patent Application Laid-Open No. 2001-0104259, Japanese Patent Laid-Open No. 2002-146139, Japanese Patent Laid-Open No. 2004-155922, Japanese Patent Laid-Open No. 2688557, Japanese Patent Laid-Open No. 2636643, etc. as a surfactant. Disclosed is a method for producing a polyvinyl alcohol-based film in which an active surfactant, a nonionic surfactant, an anionic surfactant, and the like are used alone or in combination of two or more thereof. In particular, Japanese Patent Laid-Open No. 2006-249407 discloses a method for producing a polyvinyl alcohol-based film using two nonionic surfactants having different HLBs in consideration of peelability from a casting substrate.
그러나, 전술한 문헌들에 개시된 계면활성제의 조합으로는 폴리비닐알코올계 필름의 박리성이 충분히 개선되지 않는다. However, the combination of the surfactants disclosed in the aforementioned documents does not sufficiently improve the peelability of the polyvinyl alcohol-based film.
본 발명이 이루고자 하는 기술적 과제는 전술한 문제점을 해결하여, 폴리비 닐알코올계 필름의 반복적인 제조과정을 통하여 필름으로부터 유출된 가소제가 캐스팅 기재 표면에 축적되어 가소제층을 이루는 경우에도, 폴리비닐알코올계 필름의 박리성이 양호하게 유지되어 양호한 물성의 폴리비닐알코올계 필름을 제조하는 방법, 이로부터 형성된 폴리비닐알코올계 필름 및 이를 구비한 편광판을 제공하는데 있다. The technical problem to be solved by the present invention is to solve the above-described problems, even when the plasticizer flowing out of the film is accumulated on the surface of the casting substrate through the repetitive manufacturing process of the polyvinyl alcohol-based film to form a plasticizer layer, polyvinyl alcohol It is to provide a method for producing a polyvinyl alcohol-based film of good physical properties by maintaining the peelability of the system film, a polyvinyl alcohol-based film formed therefrom and a polarizing plate having the same.
상기 기술적 과제를 달성하기 위하여, 본 발명에 따른 폴리비닐알코올계 필름의 제조방법은 (S1) 폴리비닐알코올계 고분자, 가소제 및 플루오로카본계 계면활성제, 폴리실록산계 계면활성제 및 이들의 혼합물로 이루어진 군으로부터 선택된 어느 하나의 제1 계면활성제 및 폴리옥시에틸렌 알킬 에테르계 계면활성제로 된 제2 계면활성제를 용매에 용해시켜 폴리비닐알코올계 고분자 용액을 준비하는 단계 (S2) 상기 폴리비닐알코올계 고분자 용액을 캐스팅 기재 표면에 솔루션 캐스팅하는 단계 및 (S3) 상기 (S2)단계의 결과물로부터 용매를 제거하는 단계를 포함한다. In order to achieve the above technical problem, the method for producing a polyvinyl alcohol-based film according to the present invention is a group consisting of (S1) polyvinyl alcohol-based polymers, plasticizers and fluorocarbon-based surfactants, polysiloxane-based surfactants and mixtures thereof Preparing a polyvinyl alcohol polymer solution by dissolving a second surfactant comprising any one of a first surfactant and a polyoxyethylene alkyl ether surfactant in a solvent (S2) Solution casting on the surface of the casting substrate and (S3) removing the solvent from the product of step (S2).
본발명의 폴리비닐알코올계 필름의 제조방법에 있어서, 제1 계면활성제의 HLB는 1 내지 5이고, 제2 계면활성제의HLB는 10 내지 14인 것이 바람직하다. In the manufacturing method of the polyvinyl alcohol-type film of this invention, it is preferable that HLB of 1st surfactant is 1-5, and HLB of 2nd surfactant is 10-14.
본 발명의 폴리비닐알코올계 필름의 제조방법에 있어서, 플루오로카본계 계면활성제로는 플루오로 에틸 변성 폴리실록산, 플루오로 프로필 변성 폴리실록산, 플루오로 부틸 변성 폴리실록산 등을 들 수 있고, 폴리실록산계 계면활성제로는 아미노 프로필 변성 폴리실록산, 아미노 에틸 아미노 프로필 변성 폴리실록산, 아미노 사이클로헥실 변성 폴리실록산과 같은 아민 변성 폴리실록산과 에폭시 변성 폴 리실록산 등을 들 수 있다. 또한, 폴리옥시에틸렌 알킬 에테르계 계면활성제로는 폴리옥시에틸렌 헥실 에테르, 폴리옥시에틸렌 헵틸 에테르, 폴리옥시에틸렌 옥틸 에테르, 폴리옥시에틸렌 노닐 에테르, 폴리옥시에틸렌 데실 에테르, 폴리옥시에틸렌 라우릴 에테르, 폴리옥시에틸렌 도데실 에테르, 폴리옥시에틸렌 트리데실 에테르, 폴리옥시에틸렌 테트라데실 에테르, 폴리옥시에틸렌 펜타데실 에테르 등을 들 수 있다.In the method for producing a polyvinyl alcohol-based film of the present invention, examples of the fluorocarbon-based surfactants include fluoroethyl-modified polysiloxanes, fluoropropyl-modified polysiloxanes, fluorobutyl-modified polysiloxanes, and the like. The amine modified polysiloxane, such as amino propyl modified polysiloxane, amino ethyl amino propyl modified polysiloxane, amino cyclohexyl modified polysiloxane, epoxy modified polysiloxane, etc. are mentioned. In addition, polyoxyethylene alkyl ether-based surfactants include polyoxyethylene hexyl ether, polyoxyethylene heptyl ether, polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene lauryl ether, poly Oxyethylene dodecyl ether, polyoxyethylene tridecyl ether, polyoxyethylene tetradecyl ether, polyoxyethylene pentadecyl ether, and the like.
전술한 방법으로 얻어진 폴리비닐알코올계필름은 폴리비닐알코올계 고분자, 가소제 및 계면활성제를 포함하는 폴리비닐알코올계 필름으로서, 계면활성제가 플루오로카본계 계면활성제, 폴리실록산계 계면활성제 및 이들의 혼합물로 이루어진 군으로부터 선택된 어느 하나의 제1 계면활성제 및 폴리옥시에틸렌 알킬 에테르계 계면활성제로 된 제2 계면활성제를 포함하게 된다. The polyvinyl alcohol-based film obtained by the above method is a polyvinyl alcohol-based film containing a polyvinyl alcohol-based polymer, a plasticizer and a surfactant, and the surfactant is a fluorocarbon-based surfactant, a polysiloxane-based surfactant, or a mixture thereof. It comprises a first surfactant of any one selected from the group consisting of and a second surfactant of a polyoxyethylene alkyl ether-based surfactant.
이러한 폴리비닐알코올계 필름은 편광필름으로 제조한 후 그 일면또는 양면에 보호막을 부착하여 액정표시장치의 편광판으로 사용될 수 있다. Such a polyvinyl alcohol-based film may be used as a polarizing plate of a liquid crystal display by manufacturing a polarizing film and then attaching a protective film on one or both surfaces thereof.
본 발명에 따라 폴리비닐알코올계 필름 제조시 소정의 제1 계면활성제 및 제2 계면활성제를 동시에 첨가하면, 캐스팅 기재 표면에 축적된 가소제층 내에서 제1 계면활성제는 가소제층 내에서 금속 드럼과 같은 소수성 캐스팅 기재와의 계면쪽으로 이동하여 캐스팅 기재 표면과 가소제층 사이의 장력을 효과적으로 낮추어 준다. 반대로, 제2 계면활성제는 가소제층 내에서 친수성인 폴리비닐알코올계 필름과의 계면쪽으로 이동하여 폴리비닐알코올계 필름과 가소제층 사이의 장력을 효과적으로 낮추어 주게 된다. According to the present invention, when a predetermined first surfactant and a second surfactant are added at the same time in preparing a polyvinyl alcohol-based film, the first surfactant is formed in the plasticizer layer such as a metal drum in the plasticizer layer accumulated on the casting substrate surface. Moving toward the interface with the hydrophobic casting substrate effectively lowers the tension between the casting substrate surface and the plasticizer layer. On the contrary, the second surfactant moves toward the interface with the hydrophilic polyvinyl alcohol-based film in the plasticizer layer to effectively lower the tension between the polyvinyl alcohol-based film and the plasticizer layer.
이에 따라 캐스팅 기재/가소제층 및 가소제층/폴리비닐알코올계 필름의 양 계면 사이의 장력 차이에 따른 문제점이 동시에 효율적으로 개선됨으로서, 폴리비닐알코올계 필름의 박리성이 양호하게 유지되어 양호한 물성의 폴리비닐알코올계 필름을 제조할 수 있다. Accordingly, the problem caused by the difference in tension between both interfaces of the casting substrate / plasticizer layer and the plasticizer layer / polyvinyl alcohol-based film is simultaneously and efficiently improved, so that the peelability of the polyvinyl alcohol-based film is maintained well and the poly Vinyl alcohol-based film can be prepared.
이하, 첨부된 도면을 참조로 본 발명에 대하여 상세히 설명하기로 한다. 이에 앞서, 본 명세서 및 청구범위에 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다. Hereinafter, with reference to the accompanying drawings will be described in detail with respect to the present invention. Prior to this, terms or words used in the specification and claims should not be construed as having a conventional or dictionary meaning, and the inventors should properly explain the concept of terms in order to best explain their own invention. Based on the principle that can be defined, it should be interpreted as meaning and concept corresponding to the technical idea of the present invention.
본 발명은 친수성이 서로 다른 제1 계면활성제와 제2 계면활성제로서, 플루오로카본계 계면활성제, 폴리실록산계 계면활성제 및 이들의 혼합물로 이루어진 군으로부터 선택된 어느 하나의 제1 계면활성제와 폴리옥시에틸렌 알킬 에테르계 계면활성제로 된 제2 계면활성제를 조합하므로서, 폴리비닐알코올계 필름의 박리성 향상을 극대화하였다. The present invention is a first surfactant and a second surfactant having different hydrophilicity, any one of the first surfactant and polyoxyethylene alkyl selected from the group consisting of fluorocarbon surfactant, polysiloxane surfactant and mixtures thereof By combining the second surfactant made of an ether surfactant, the peelability improvement of the polyvinyl alcohol-based film was maximized.
도 1에 도시된 바와 같이, 폴리비닐알코올계 필름 제조시 제1 계면활성제와 제2 계면활성제를 동시에 첨가하면, 캐스팅 기재(3) 표면에 축적된 가소제층(5) 내에서 제1 계면활성제(7)는 가소제층(5) 내에서 금속 드럼과 같은 소수성 캐스팅 기재(3)와의 계면쪽으로 이동하여 캐스팅 기재(3) 표면과 가소제층(5) 사이의 장력 을 효과적으로 낮추어 준다. 반대로, 제2 계면활성제(9)는 가소제층(5) 내에서 친수성인 폴리비닐알코올계 필름(1)과의 계면쪽으로 이동하여 폴리비닐알코올계 필름(1)과 가소제층(5) 사이의 장력을 효과적으로 낮추어 주게 된다. 이에 따라 캐스팅 기재(3)/가소제층(5) 및 가소제층(5)/폴리비닐알코올계 필름(1)의 양 계면 사이의 장력 차이에 따른 폴리비닐알코올계 필름의 박리성 불량의 문제점을 크게 개선할 수 있다.As shown in FIG. 1, when the first surfactant and the second surfactant are simultaneously added during the production of the polyvinyl alcohol-based film, the first surfactant (in the plasticizer layer 5 accumulated on the surface of the casting substrate 3) 7) moves toward the interface with the hydrophobic casting substrate 3 such as a metal drum in the plasticizer layer 5 to effectively lower the tension between the surface of the casting substrate 3 and the plasticizer layer 5. In contrast, the second surfactant 9 moves toward the interface with the hydrophilic polyvinyl alcohol-based film 1 in the plasticizer layer 5 to tension between the polyvinyl alcohol-based film 1 and the plasticizer layer 5. It effectively lowers. Accordingly, the problem of the peelability defect of the polyvinyl alcohol-based film due to the difference in tension between both interfaces of the casting substrate 3 / plasticizer layer 5 and the plasticizer layer 5 / polyvinyl alcohol-based film 1 is greatly increased. It can be improved.
본 발명의 폴리비닐알코올계 필름의 제조방법은 다음과 같다.The manufacturing method of the polyvinyl alcohol-type film of this invention is as follows.
먼저, 폴리비닐알코올계 고분자, 가소제 및 플루오로카본계 계면활성제, 폴리실록산계 계면활성제 및 이들의 혼합물로 이루어진 군으로부터 선택된 어느 하나의 제1 계면활성제 및 폴리옥시에틸렌 알킬 에테르계 계면활성제로 된 제2 계면활성제를 용매에 용해시켜 폴리비닐알코올계 고분자 용액을 준비한다(S1 단계). First, a polyvinyl alcohol-based polymer, a plasticizer and a fluorocarbon-based surfactant, a polysiloxane-based surfactant, and any one of the first surfactant selected from the group consisting of a mixture thereof and a second polyoxyethylene alkyl ether-based surfactant Dissolving the surfactant in a solvent to prepare a polyvinyl alcohol-based polymer solution (step S1).
제1 계면활성제 및 제2 계면활성제로는 HLB가 각각 1 내지 5 및 10 내지 14인 것을 사용하는 것이 바람직한데, 플루오로카본계 계면활성제로는 플루오로 에틸 변성 폴리실록산, 플루오로 프로필 변성 폴리실록산, 플루오로 부틸 변성 폴리실록산 등을 각각 단독으로 또는 이들 중 2종 이상 혼합하여 사용할 수 있고, 폴리실록산계 계면활성제로는 아미노 프로필 변성 폴리실록산, 아미노 에틸 아미노 프로필 변성 폴리실록산, 아미노 사이클로헥실 변성 폴리실록산과 같은 아민 변성 폴리실록산과 에폭시 변성 폴리실록산 등을 각각 단독으로 또는이들을 2종 이상 혼합하여사용할 수 있다. 또한, 폴리옥시에틸렌알킬 에테르계 계면활성제로는 폴리옥시에틸렌 헥실 에테르, 폴리옥시에틸렌 헵틸 에테르, 폴리옥시에틸렌 옥틸 에테르, 폴리 옥시에틸렌 노닐 에테르, 폴리옥시에틸렌 데실 에테르, 폴리옥시에틸렌 라우릴 에테르, 폴리옥시에틸렌 도데실 에테르, 폴리옥시에틸렌 트리데실 에테르, 폴리옥시에틸렌 테트라데실 에테르, 폴리옥시에틸렌 펜타데실 에테르 등을 각각 단독으로 또는 이들을 2종 이상 혼합하여 사용할 수 있다. It is preferable to use HLB of 1-5 and 10-14 as a 1st surfactant and a 2nd surfactant, and a fluorocarbon-type surfactant is fluoro ethyl modified polysiloxane, fluoro propyl modified polysiloxane, fluoro Or butyl modified polysiloxanes may be used alone or in combination of two or more thereof.As the polysiloxane surfactant, amine modified polysiloxanes such as amino propyl modified polysiloxane, amino ethyl amino propyl modified polysiloxane, amino cyclohexyl modified polysiloxane, and the like may be used. Epoxy modified polysiloxane etc. can be used individually or in mixture of 2 or more types, respectively . Also, Polyoxyethylene alkyl ether-based surfactants include polyoxyethylene hexyl ether, polyoxyethylene heptyl ether, polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene Dodecyl ether, polyoxyethylene tridecyl ether, polyoxyethylene tetradecyl ether, polyoxyethylene pentadecyl ether, etc. can be used individually or in mixture of 2 or more types, respectively .
본 발명에 따른 폴리비닐알코올계 필름의 제조방법에 있어서, 제1 계면활성제와 제2 계면활성제는 폴리비닐알코올계 고분자 100 중량부를 기준으로 0.01 내지 2 중량부를 첨가할 수 있는데, 제1 계면활성제 : 제2 계면활성제는 예를 들어 1~10 : 10~1의 함량비(중량%)로 첨가하여 필름의 제조 공정성을 향상시킬 수 있다.In the method for producing a polyvinyl alcohol-based film according to the present invention, the first surfactant and the second surfactant may be added in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the polyvinyl alcohol-based polymer. For example, the second surfactant may be added in an amount ratio (weight%) of 1 to 10: 10 to 1 to improve manufacturing processability of the film.
본 발명의 폴리비닐알코올계 필름의 제조방법에 있어서, 폴리비닐알코올계 고분자는 비닐알코올을 반복단위로서 포함하는 고분자로서, 비닐에스테르계 단량체를 중합하여 얻어진 비닐에스테르계 중합체를 가수분해한 다음 비닐에스테르 단위를 비닐알코올 단위로 검화하여 제조할 수 있다. 비닐에스테르계 단량체로는 예를 들어 포름산비닐, 아세트산비닐, 프로피온산비닐, 발레르산비닐, 라우린산비닐, 스테아르산비닐, 벤조산비닐, 피발린산비닐, 바사틱산비닐 등을 들 수 있으며, 이들 중에서 아세트산 비닐이 선호된다. 비닐에스테르계 단량체를 중합시킬 때, 본 발명의 목적을 저해하지 않는 한도 내에서 에틸렌, 프로필렌 등 공지된 다른 단량체를 공중합시킬 수 있음은 물론이다. In the method for producing a polyvinyl alcohol-based film of the present invention, the polyvinyl alcohol-based polymer is a polymer containing vinyl alcohol as a repeating unit, and hydrolyzed the vinyl ester polymer obtained by polymerizing a vinyl ester monomer. The unit can be prepared by saponifying with vinyl alcohol units. Examples of the vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, and vinyl basatate. Vinyl acetate is preferred. When polymerizing a vinyl ester monomer, it is a matter of course that other known monomers such as ethylene and propylene can be copolymerized within the scope of not impairing the object of the present invention.
또한, 본 발명의 폴리비닐알코올계 필름의 제조방법에 있어서, 가소제로는 다가 알코올을 첨가하는 것이 바람직한데, 다가 알코올로는 에틸렌글리콜, 글리세린, 프로필렌글리콜, 디에틸렌글리콜, 트리에틸렌글리콜, 테트라에틸렌글리콜, 트 리메티롤프로판 등을 들 수 있으며, 이들을 각각 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. 통상적으로 글리세린이나 에틸렌글리콜이 선호된다. 다가 알코올의 함량은 통상적인 함량, 예를 들어 폴리비닐알코올계 고분자 100 중량부를 기준으로 1 내지 30 중량부가 첨가될 수 있다. 용매로는 주로 물이 사용되나 이에 한정되지 않는다. 통상적으로 용매는 50 내지 90중량%가 되도록 용액에 첨가된다.In addition, in the method for producing a polyvinyl alcohol-based film of the present invention, it is preferable to add a polyhydric alcohol as the plasticizer, but as the polyhydric alcohol, ethylene glycol, glycerin, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene Glycol, trimethylolpropane, and the like, and these may be used alone or in combination of two or more thereof. Usually glycerin or ethylene glycol are preferred. The content of the polyhydric alcohol may be added 1 to 30 parts by weight based on conventional content, for example 100 parts by weight of the polyvinyl alcohol-based polymer. Water is mainly used as a solvent, but is not limited thereto. Typically the solvent is added to the solution to be 50-90% by weight.
이어서, 준비한 폴리비닐알코올계 고분자 용액을 캐스팅 기재 표면에 솔루션 캐스팅한다(S2 단계). Subsequently, the prepared polyvinyl alcohol-based polymer solution is solution cast on the casting substrate surface (step S2).
캐스팅 기재로는 벨트나 금속 드럼을 들 수 있는데, 예를 들어 니켈, 크롬, 구리, 스텐레스스틸과 같은 금속으로 된 직경 1 내지 5 m의 드럼을 이용한다.The casting substrate may be a belt or a metal drum. For example, a drum having a diameter of 1 to 5 m made of metal such as nickel, chromium, copper, or stainless steel is used.
그런 다음, 솔루션 캐스팅된 폴리비닐알코올계 고분자 용액에서 용매를 휘발시켜 제거하면 폴리비닐알코올계 필름을 얻을 수 있다(S3 단계). 박리 롤 등을 이용하여 캐스팅 기재 표면으로부터 박리한 폴리비닐알코올계 필름은 필요에 따라 다시 건조 또는 조습할 수 있다.Then, the solvent is evaporated and removed from the solution-cast polyvinyl alcohol-based polymer solution to obtain a polyvinyl alcohol-based film (step S3). The polyvinyl alcohol-type film peeled from the casting base material surface using a peeling roll etc. can be dried or humidified again as needed.
전술한 방법으로 얻은 폴리비닐알코올계 필름은 폴리비닐알코올계 고분자, 가소제 및 계면활성제를 포함하는 폴리비닐알코올계필름으로서, 계면활성제가 플루오로카본계 계면활성제, 폴리실록산계 계면활성제및 이들의 혼합물로 이루어진 군으로부터 선택된 어느 하나의 제1 계면활성제 및 폴리옥시에틸렌 알킬 에테르계 계면활성제로 된 제2 계면활성제를 포함하게 된다. 얻어진 폴리비닐알코올계 필름 내의 계면활성제의 종류 등은 전술한 제조방법에 기재된 바와 동일하다. The polyvinyl alcohol-based film obtained by the above-described method is a polyvinyl alcohol-based film containing a polyvinyl alcohol-based polymer, a plasticizer and a surfactant, and the surfactant is a fluorocarbon-based surfactant, a polysiloxane-based surfactant, or a mixture thereof. It comprises a first surfactant of any one selected from the group consisting of and a second surfactant of a polyoxyethylene alkyl ether-based surfactant. The kind of surfactant in the obtained polyvinyl alcohol-type film, etc. are the same as what was described in the manufacturing method mentioned above.
이러한 폴리비닐알코올계 필름은 공지의 방법에 따라 요오드 혹은 이색성 염 료로 염색 및 연신하여 편광필름으로 제조한 다음, 그 일면 또는 양면에 광학적으로 투명하고 기계적 강도를 갖는 공지의 보호막, 예를 들어 셀룰로오스아세테이트계 필름, 아크릴계 필름, 폴리에스테르계 필름 등의 보호막을 부착하여 액정표시장치의 편광판으로 사용될 수 있다.Such a polyvinyl alcohol-based film is dyed and stretched with iodine or dichroic dye according to a known method to prepare a polarizing film, and then a known protective film, such as cellulose, which is optically transparent and has mechanical strength on one or both surfaces thereof. A protective film such as an acetate film, an acrylic film, or a polyester film may be attached to the polarizing plate of the liquid crystal display device.
이하, 본 발명을 보다 구체적으로 설명하기 위해 실시예를 들어 설명하기로 한다. 그러나, 본 발명에 따른 실시예 들은 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예들에 의해 한정되는 것으로 해석되어서는 안 된다. 본 발명의 실시예들은 당업계에서 평균적인 지식을 가진 자에게 본 발명을보다 완전하게 설명하기 위해서 제공되는 것이다.Hereinafter, examples will be described in order to describe the present invention in more detail. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited by the embodiments described below. Embodiments of the present invention are provided to more fully explain the present invention to those skilled in the art.
<실시예 및 비교예><Examples and Comparative Examples>
중합도 4000, 검화도 99.9 몰%의 폴리비닐알코올 고분자 50 kg과 200 kg의 물을 용해조에 투입한 다음, 글리세린 5 kg 및 하기 표 1에 기재된 종류의 제1 계면활성제와 제2 계면활성제(함량비는 1:1임)를 계면활성제 총량이 50 g이 되도록 첨가하고 탱크하부에서 스팀을 가하여 150 ℃에서 2시간 가열하여 폴리비닐알코올계 고분자 용액을 준비하였다.50 kg of polyvinyl alcohol polymer and 200 kg of water having a degree of polymerization of 4000 and a degree of saponification of 99.9 mol% were added to a dissolution tank, and then 5 kg of glycerin and the first and second surfactants of the type shown in Table 1 below (content ratio 1: 1) is added so that the total amount of the surfactant to 50 g and steam at the bottom of the tank was heated at 150 ℃ 2 hours to prepare a polyvinyl alcohol-based polymer solution.
이어서, 준비한 폴리비닐알코올계 고분자 용액을 기어 펌프로 T형 슬릿다이로 배출하여 금속 드럼형 롤에서 제막하였다. 그런 다음, 얻어진 막의 표면과 이면을 13개의 건조롤에 교대로 접촉시키면서 건조하였다. 건조된 필름은 열처리 조에서 열처리하여 폴리비닐알코올 미연신 필름을 얻었다.Subsequently, the prepared polyvinyl alcohol polymer solution was discharged to a T-type slit die by a gear pump to form a film on a metal drum roll. Then, the surface and the back surface of the obtained film were dried while alternately contacting 13 drying rolls. The dried film was heat treated in a heat treatment bath to obtain a polyvinyl alcohol unstretched film.
표 1에서, X: 불량, △: 보통, ○: 양호, ◎:우수In Table 1, X: poor, △: normal, ○: good, ◎: excellent
명세서 내에 통합되어 있고 명세서의 일부를 구성하는 첨부도면은 발명의 현재의 바람직한 실시예를 예시하며, 다음의 바람직한 실시예의 상세한 설명과 함께 본 발명의 원리를 설명하는 역할을 할 것이다.The accompanying drawings, which are incorporated in and constitute a part of the specification, illustrate the presently preferred embodiments of the invention and, together with the description of the following preferred embodiments, serve to explain the principles of the invention.
도 1은 본 발명의 제조방법에 따라 폴리비닐알코올계 필름 제조시 제1 계면활성제와 제2 계면활성제가 가소제층 내에서 캐스팅 기재/가소제층 및 가소제층/폴리비닐알코올계 필름 사이에 존재하는 계면장력을 낮추는 원리를 설명한 모식도이다. 1 is an interface in which a first surfactant and a second surfactant are present between a casting substrate / plasticizer layer and a plasticizer layer / polyvinyl alcohol-based film in the plasticizer layer when the polyvinyl alcohol film is manufactured according to the manufacturing method of the present invention. It is a schematic diagram explaining the principle of lowering tension.
Claims (18)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020080062719A KR20100002719A (en) | 2008-06-30 | 2008-06-30 | A manufacturing method of polyvinylalcohol film, a polyvinylalcohol film formed therefrom and a polarizer having the same |
| JP2009140116A JP4933581B2 (en) | 2008-06-30 | 2009-06-11 | Production method of polyvinyl alcohol film, polyvinyl alcohol film formed therefrom, and polarizing plate provided with the same |
| CN2009101515235A CN101619138B (en) | 2008-06-30 | 2009-06-29 | Polyvinyl alcohol film, method for preparing the same and polaroid containing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020080062719A KR20100002719A (en) | 2008-06-30 | 2008-06-30 | A manufacturing method of polyvinylalcohol film, a polyvinylalcohol film formed therefrom and a polarizer having the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20100002719A true KR20100002719A (en) | 2010-01-07 |
Family
ID=41512557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020080062719A KR20100002719A (en) | 2008-06-30 | 2008-06-30 | A manufacturing method of polyvinylalcohol film, a polyvinylalcohol film formed therefrom and a polarizer having the same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4933581B2 (en) |
| KR (1) | KR20100002719A (en) |
| CN (1) | CN101619138B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101258571B1 (en) * | 2011-09-21 | 2013-04-29 | 허지승 | Drain trap for preventing backflow |
| KR101399427B1 (en) * | 2012-04-18 | 2014-05-27 | 에스케이씨 주식회사 | Polyvinyl alcohol-based film and polarizing film using same |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432899A (en) * | 2011-08-16 | 2012-05-02 | 深圳市华星光电技术有限公司 | Modified polyvinylalcohol (PVA) base film, preparation method thereof and polarizer |
| US20130045390A1 (en) | 2011-08-16 | 2013-02-21 | Rui Xu | Base Film of Modified Polyvinyl Alcohol and Its Preparation Method and Polarizer |
| KR20160004293A (en) * | 2013-05-01 | 2016-01-12 | 세키스이가가쿠 고교가부시키가이샤 | Polyvinyl alcohol aqueous solution |
| KR101460479B1 (en) * | 2013-06-18 | 2014-11-10 | 주식회사 엘지화학 | Oriented laminate, preparing method for thin polarizer, thin polarizer manufactured by using the same and polarizing plate comprising the same |
| TWI586533B (en) * | 2013-12-25 | 2017-06-11 | 日東電工股份有限公司 | Polarizing plate and method of producing polarizing plate |
| KR102229234B1 (en) * | 2014-02-06 | 2021-03-17 | 주식회사 쿠라레 | Polyvinyl alcohol film |
| JP6668338B2 (en) * | 2015-05-13 | 2020-03-18 | 株式会社クラレ | Polyvinyl alcohol film |
| CN109983074A (en) * | 2016-10-18 | 2019-07-05 | 株式会社可乐丽 | Purposes of the polyol as the plasticizer for polyvinyl alcohol in 3D printing method |
| CN106405715B (en) * | 2016-11-10 | 2019-05-03 | 华侨大学 | A kind of preparation method and applications of the PVA film for polaroid |
| TW201927887A (en) * | 2017-12-27 | 2019-07-16 | 日商三菱化學股份有限公司 | Poly(vinyl alcohol)-based film for producing polarizing film, polarizing film obtained using same, and aqueous solution of poly(vinyl alcohol)-based resin |
| CN108623966A (en) * | 2018-05-02 | 2018-10-09 | 江苏帝摩斯光电科技有限公司 | A kind of liquid crystal display polarisation diaphragm |
| US11999832B2 (en) | 2019-01-30 | 2024-06-04 | Aicello Corporation | Polyvinyl alcohol-based resin film |
| TWI769938B (en) * | 2021-10-08 | 2022-07-01 | 長春石油化學股份有限公司 | Polyvinyl alcohol film, optical film comprising the same, and manufacturing method thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3473838B2 (en) * | 2000-06-28 | 2003-12-08 | 株式会社クラレ | Method for producing polyvinyl alcohol film |
| JP2002317074A (en) * | 2001-04-23 | 2002-10-31 | Fuji Photo Film Co Ltd | Cellulose acylate film and method for producing the same |
| JP4565803B2 (en) * | 2002-11-07 | 2010-10-20 | 日本合成化学工業株式会社 | Polyvinyl alcohol film and method for producing the same |
| US7125504B2 (en) * | 2002-11-13 | 2006-10-24 | Eastman Kodak Company | Optical switch microfilms |
| JP4602777B2 (en) * | 2004-01-26 | 2010-12-22 | 日本合成化学工業株式会社 | Method for producing polyvinyl alcohol film |
| JP4578140B2 (en) * | 2004-04-21 | 2010-11-10 | 株式会社クラレ | Polyvinyl alcohol film |
| JP5089045B2 (en) * | 2005-02-14 | 2012-12-05 | 日本合成化学工業株式会社 | Polyvinyl alcohol film and method for producing the same |
| JP4794206B2 (en) * | 2005-04-28 | 2011-10-19 | 日本合成化学工業株式会社 | Polyvinyl alcohol film and polarizing film and polarizing plate using the same |
| WO2007097303A1 (en) * | 2006-02-27 | 2007-08-30 | Konica Minolta Opto, Inc. | Antireflection film, method for producing antireflection film, polarizing plate and display |
-
2008
- 2008-06-30 KR KR1020080062719A patent/KR20100002719A/en not_active Application Discontinuation
-
2009
- 2009-06-11 JP JP2009140116A patent/JP4933581B2/en active Active
- 2009-06-29 CN CN2009101515235A patent/CN101619138B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101258571B1 (en) * | 2011-09-21 | 2013-04-29 | 허지승 | Drain trap for preventing backflow |
| KR101399427B1 (en) * | 2012-04-18 | 2014-05-27 | 에스케이씨 주식회사 | Polyvinyl alcohol-based film and polarizing film using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010012778A (en) | 2010-01-21 |
| CN101619138A (en) | 2010-01-06 |
| CN101619138B (en) | 2012-07-18 |
| JP4933581B2 (en) | 2012-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR20100002719A (en) | A manufacturing method of polyvinylalcohol film, a polyvinylalcohol film formed therefrom and a polarizer having the same | |
| KR101212424B1 (en) | Polyvinyl alcohol film and method for producing same | |
| KR101257648B1 (en) | Polyvinyl alcohol film, method for producing polyvinyl alcohol film, polarizing film, and polarizing plate | |
| JP5911219B2 (en) | Production method of polyvinyl alcohol film, polyvinyl alcohol film, polarizing film and polarizing plate | |
| JP6185734B2 (en) | Method for producing polyvinyl alcohol polymer film | |
| KR100886322B1 (en) | Preparation method of polyvinyl alcohol polarizer film having good surface uniformity | |
| WO2016060097A1 (en) | Polyvinyl-alcohol-based film, method for manufacturing same, polarizing film, and polarizing plate | |
| JP6685661B2 (en) | Polarizing film manufacturing method | |
| JP6402096B2 (en) | Polyvinyl alcohol film | |
| KR20190119126A (en) | Polarizing Films, Polarizing Plates, and Their Manufacturing Methods | |
| JP3476135B2 (en) | Method for producing polyvinyl alcohol film for polarizing film | |
| JP3997892B2 (en) | Method for producing polyvinyl alcohol film for polarizing film | |
| JP4149200B2 (en) | Manufacturing method of polarizing film | |
| JP2006307058A (en) | Polyvinyl alcohol-based film, and its polarizing film, polarizing plate | |
| TWI676638B (en) | Polyvinyl alcohol film, method for producing polyvinyl alcohol film, and polarizing film | |
| JP2002014224A (en) | Method for manufacturing polarizing film | |
| JP5121952B2 (en) | Polyvinyl alcohol film and use thereof | |
| TW200406444A (en) | A process for producing polarizing film | |
| KR20090096766A (en) | Polyvinyl alcohol based polymeric film, manufacture thereof, and its application to polarizing film | |
| JP4504524B2 (en) | Production method of stretched film | |
| JP4906309B2 (en) | Method for producing polyvinyl alcohol film | |
| KR20080035728A (en) | A manufacturing method of polyvinylalcohol film, a polyvinylalcohol film formed therefrom and a polarizer having the same | |
| JP7196535B2 (en) | POLYVINYL ALCOHOL-BASED FILM FOR MANUFACTURING POLARIZING FILM, AND POLARIZING MEMBRANE AND POLARIZING PLATE USING THE SAME | |
| JP3588308B2 (en) | Method for producing polyvinyl alcohol film | |
| JP4712154B2 (en) | Production method of polyvinyl alcohol film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E601 | Decision to refuse application |