CN101663152A - Film, method for producing the same, and use of the same - Google Patents
Film, method for producing the same, and use of the same Download PDFInfo
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- CN101663152A CN101663152A CN200880013127A CN200880013127A CN101663152A CN 101663152 A CN101663152 A CN 101663152A CN 200880013127 A CN200880013127 A CN 200880013127A CN 200880013127 A CN200880013127 A CN 200880013127A CN 101663152 A CN101663152 A CN 101663152A
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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
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/885—External treatment, e.g. by using air rings for cooling tubular films
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/91—Heating, e.g. for cross linking
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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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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/13363—Birefringent elements, e.g. for optical compensation
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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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
- B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
- B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0037—Other properties
- B29K2995/0072—Roughness, e.g. anti-slip
- B29K2995/0073—Roughness, e.g. anti-slip smooth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2011/00—Optical elements, e.g. lenses, prisms
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08J2323/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
- G02F2201/50—Protective arrangements
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Thermal Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Nonlinear Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mathematical Physics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Polarising Elements (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Abstract
Disclosed is a film composed of a crystalline olefin (co)polymer, which is characterized by having a surface roughness Ra of not more than 5 nm and a haze value of not more than 1%.
Description
Technical field
The present invention relates to film and the manufacture method thereof of using crystallinity alkene (being total to) polymer to obtain, with and uses thereof.
Background technology
The film that is formed by the crystalline polyolefin based polymer has advantages such as high-melting-point, good release property, high transparent, is used to mold release film etc.
Disclose a kind of phase difference compensation thin plate that has enlarged the visual angle in the patent documentation 2, it has the similar character with the variations in temperature institute of the optical characteristics of liquid crystal, by even multiaxis orientation, only changes the refractive index of lamella thickness direction in the face direction of thin plate.
Patent documentation 3 discloses that a kind of birefringence is with low uncertainty, be difficult for producing carbonization deterioration thing during melt molding and then do not have the protective film of polarizing plate of color spot, contrast excellence as the diaphragm of the polarizing coating of LCD the time.
Patent documentation 1: Japanese kokai publication hei 5-302068 communique
Patent documentation 2: Japanese kokai publication hei 4-284402 communique
Patent documentation 3: TOHKEMY 2000-275433 communique
Summary of the invention
The problem that invention will solve
In recent years, in the purposes of transparent optical film, require the transparency further to improve,, seeking that concave-convex surface is few, the film of low haze as one of means that are used to address this problem.Consider from this viewpoint, just be considered to the film that high crystallinity alkene (being total to) polymer such as (be total to) polymer by 4-methyl-1-pentene of the transparency form, common, vitrification point (Tg) is low, the difference of melt temperature and Tg is big.Therefore, the film surface after the moulding is easy to generate concavo-convex.In addition, by the film that crystallinity alkene (being total to) polymer forms, have the interface of crystallization and amorphous, owing to the light scattering at this interface, mist degree increases.
Above-mentioned arbitrary piece of patent documentation all can not be said so and be disclosed film on the viewpoint that realizes this high transparent, and these films also are difficult to use as transparent optical film.
Therefore, the purpose of this invention is to provide the film and the manufacture method thereof that form by crystallinity alkene (being total to) polymer that are suitable for as the purposes of transparent optical film, and the purposes of this film.
The means of dealing with problems
(1) the invention provides a kind of film, this film is to be formed by crystallinity alkene (being total to) polymer, it is characterized in that, surface roughness Ra is below the 5nm and mist degree is below 1%.
Below, each one of preferred implementation of the present invention naturally of (2)~(16).
(2) film of above-mentioned (1) record is characterized in that, described crystallinity alkene (being total to) polymer is to use at least a alkene of selecting from 4-methyl-1-pentene, 3-Methyl-1-pentene, 3-methyl-1-butene to obtain as (being total to) polymerization composition.
(3) film of above-mentioned (1) or (2) record is characterized in that internal haze is below 0.5%.
(4) film of each record in above-mentioned (1)~(3) is characterized in that, the water absorption rate of measuring according to JIS K7209 method is below 0.1%.
(5) film of each record in above-mentioned (1)~(4) is characterized in that, the moisture-vapor transmission of measuring according to JIS Z0208 method is 25g/m
2More than/the sky.
(6) film of each record in above-mentioned (1)~(5) is characterized in that refractive index is below 1.5.
(7) film of each record in above-mentioned (1)~(6), it is characterized in that, refractive index in this face is reached maximum direction be made as X-axis, with in the face and the direction vertical with X-axis be made as Y-axis, refractive index under the wavelength 590nm separately is made as nx, ny, when the thickness of film was made as d, length of delay Re=(the nx-ny) * d in the face under the wavelength 590nm was below the 5nm.
(8) film of each record in above-mentioned (1)~(7), it is characterized in that, refractive index in this face is reached maximum direction be made as X-axis, with in the face and the direction vertical with X-axis be made as Y-axis, the thickness direction of film is made as the Z axle, refractive index under the wavelength 590nm separately is made as nx, ny, nz, and when the thickness of film was made as d, length of delay Rth=| (nx+ny)/2-nz| * d of the thickness direction under the wavelength 590nm was below the 10nm.
(9) manufacture method of the film of each record in above-mentioned (1)~(8), it is characterized in that, for the film that forms by crystallinity alkene (being total to) polymer, more than the vitrification point (Tg) of this crystallinity alkene (being total to) polymer and less than 120 ℃ temperature, stretch.
(10) manufacture method of the film of above-mentioned (9) record is characterized in that when molten resin was formed film, quenching was to below Tg+50 ℃.
(11) manufacture method of film of above-mentioned (9) record is characterized in that, when forming the film that is formed by crystallinity alkene (be total to) polymer by extrusion by melting or pressurize afterwards and compress this film.
(12) protective film of polarizing plate is characterized in that, has used the film of each record in above-mentioned (1)~(8).
(13) optical compensation films is characterized in that, has used the film of each record in above-mentioned (1)~(8).
(14) stripping film is characterized in that, has used the film of each record in above-mentioned (1)~(8).
(15) diaphragm is characterized in that, has used the film of each record in above-mentioned (1)~(8).
(16) display element is characterized in that, has used the film of each record in above-mentioned (1)~(8) and (12)~(15).
According to the present invention, the film and the manufacture method thereof that are formed by crystallinity alkene (being total to) polymer that are suitable for as the purposes of transparent optical film can be provided, and the purposes of this film.
Description of drawings
Above-mentioned purpose, and other purposes, feature and advantage will become clearer and more definite according to suitable embodiment and subsidiary the following drawings of the following stated.
Fig. 1 represents that the film with present embodiment is applied to the example of polarization plates.
Fig. 2 represents the film of present embodiment is applied to the example of the optical compensation films of sandwich construction.
Fig. 3 represents an example as the formation of the liquid crystal indicator of the display unit of present embodiment.
The specific embodiment
Below, embodiments of the present invention are described.
The film of present embodiment is the film that is formed by crystallinity alkene (being total to) polymer, and surface roughness Ra is below the 5nm, and mist degree is below 1%.
The film of present embodiment is formed by crystallinity alkene (being total to) polymer.Here, " by ... ... form " implication comprise following two aspects: the whole of film are made of crystallinity alkene (being total to) polymer; The part of film is made of crystallinity alkene (being total to) polymer.Therefore, film can contain the composition beyond crystallinity alkene (being total to) polymer, also can not contain crystallinity alkene (being total to) polymer composition in addition.Consider that from the viewpoint of effective realization effect of the present invention the content of crystallinity alkene (being total to) polymer in the film is suitably 20~100 weight %, more preferably 50~100 weight %.
Crystallinity alkene (being total to) polymer so long as crystallinity and have the transparency get final product, various crystallinity alkene (being total to) polymer can be used, the film that forms by the co-polymer (α) that for example uses at least a alkene from 4-methyl-1-pentene, 3-Methyl-1-pentene, 3-methyl-1-butene, selected to obtain as the copolymer composition can be preferably used as component of polymer or these alkene.
((being total to) polymer (α))
Specific (being total to) polymer (α) that is preferred for film of the present invention is to use at least a alkene of selecting from 4-methyl-1-pentene, 3-Methyl-1-pentene and 3-methyl-1-butene to obtain as (being total to) component of polymer.This specific alkene (being total to) polymer (α) can routine illustrate the homopolymers of 3-methyl-1-butene, 3-Methyl-1-pentene or 4-methyl-1-pentene; Or their mutual copolymers; And then with other can copolymerization the monomer copolymer of styrene, acrylonitrile, vinyl chloride, vinylacetate, acrylate, methacrylate etc. for example; Perhaps above-mentioned substance each other or with other thermoplastic resins, elastomeric mixture, block copolymer, graft copolymer etc.In the construction unit of (being total to) polymer (α), be generally 20~100 moles of %, be preferably 50~100 moles of %, more preferably 80~100 moles of % from the total of the construction unit of 4-methyl-1-pentene, 3-Methyl-1-pentene or 3-methyl-1-butene.In above-mentioned scope, can access the resin of the balance excellence of various characteristicses such as the transparency, hear resistance from the content of the construction unit of 4-methyl-1-pentene, 3-Methyl-1-pentene or 3-methyl-1-butene, be preferred from this viewpoint.
In (being total to) polymer (α), excellences such as the transparency of 4-methyl-1-pentene (being total to) polymer, fissility are suitable for using with optical element combination, are preferred from this viewpoint.In addition, 3-Methyl-1-pentene (being total to) polymer and 3-methyl-1-butene (being total to) polymer are preferred from the viewpoints such as the free degree of excellent heat resistance, the processing free degree, service condition.
(4-methyl-1-pentene (being total to) polymer)
4-methyl-1-pentene (being total to) polymer that especially preferably uses as (being total to) polymer (α) that preferably uses in the present invention, be the copolymer of other alpha-olefins of the homopolymers of 4-methyl-1-pentene or 4-methyl-1-pentene and ethene or carbon number 3~20 specifically, other alpha-olefins of carbon number 3~20 for example are ethene, propylene, 1-butylene, 1-hexene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid, 1-eicosylene etc.Preferred 4-methyl-1-pentene (being total to) polymer that uses contains the construction unit from 4-methyl-1-pentene with 85 moles more than the %, preferred 90 moles of amounts more than the % usually among the present invention.Constitute 4-methyl-1-pentene (be total to) polymer, from 4-methyl-1-pentene constituent in addition, be not particularly limited, can suitably use can with the various monomers of 4-methyl-1-pentene copolymerization, from buy easily, viewpoint such as copolymerized characteristic considers, can preferably use the alpha-olefin of ethene or carbon number 3~20.Wherein, the alpha-olefin of preferred carbon number 7~20, preferred especially 1-decene, 1-dodecylene, tetradecene, cetene and 1-vaccenic acid.
Melt flow rate (MFR) (MFR) preferred 4-methyl-1-pentene (being total to) polymer that uses, that under the condition of 260 ℃ of loading 5kg, temperature, measure according to ASTM D1238 among the present invention, be defined as various speed according to purposes, but be generally 1~50g/10min, be preferably 2~40g/10min, more preferably the scope of 5~30g/10min.If the melt flow rate (MFR) of 4-methyl-1-pentene (being total to) polymer is in above-mentioned scope, then the outward appearance of film mouldability and gained film is good.In addition, fusing point suits at 100~240 ℃, preferably 150~240 ℃ scope.
In addition, this 4-methyl-1-pentene (being total to) polymer can be made by known method in the past, for example, can be as Japanese kokai publication sho 59-206418 communique record, obtain by polymerization 4-methyl-1-pentene in the presence of catalyst and above-mentioned ethene or alpha-olefin.
(3-Methyl-1-pentene (being total to) polymer)
The preferred comonomer kind of 3-Methyl-1-pentene (being total to) polymer that especially preferably uses as (being total to) polymer (α) that preferably uses in the present invention, co-monomer content, MFR, fusing point etc. are identical with the situation of above-mentioned 4-methyl-1-pentene (being total to) polymer.Preferred 3-Methyl-1-pentene (be total to) polymer that uses can suitably be made by known method in the past among the present invention, for example can make by the method that Japanese kokai publication hei 06-145248 communique is put down in writing.
(3-methyl-1-butene (being total to) polymer)
The preferred comonomer kind of 3-methyl-1-butene (being total to) polymer that especially preferably uses as (being total to) polymer (α) that preferably uses in the present invention, co-monomer content, MFR, fusing point etc. are identical with the situation of above-mentioned 4-methyl-1-pentene (being total to) polymer.Preferred 3-methyl-1-butene (be total to) polymer that uses can suitably be made by known method in the past among the present invention, for example can make by the method that Japanese kokai publication hei 06-145248 communique is put down in writing.
Here, so-called " crystallinity " is meant that this alkene (being total to) crystallinity of polymer is more than 10%.Degree of crystallinity is by the integrated intensity of the diffraction maximum of noncrystalline part that obtains by the X-ray diffraction transmission beam method and crystalline part, uses following formula to calculate.
Degree of crystallinity=(the integrated intensity sum of the integrated intensity/noncrystalline of crystalline part and crystalline part) * 100 (%)
In addition, the surface roughness Ra of film is below the 5nm, is preferably below the 3nm, and mist degree is below 1%, to be preferably below 0.5%.Mist degree can be measured according to JIS K7105 method.Here, think that mist degree is by film surface and the concavo-convex light scattering that causes (outside mist degree) at the back side and light scattering (internal haze) sum that is caused by the variations in refractive index in the film, impurity, defective etc.Therefore, internal haze can be passed through film immersion in the refractive index solvent roughly the same with measuring film, makes film the reflectivity surperficial and back side be actually zero and measures and obtain.
The internal haze of this film is below 0.5%, to be preferably below 0.2%.
What here, the surface roughness Ra of film (center line average roughness) was used is the Ra value of the three-dimensional in certain zone.As assay method, can use three-dimensional surface structure elucidation microscope, sweep type laser microscope, electron ray configuration of surface resolver, scanning type probe microscope, non-contact type three-dimensional light interfere type surface roughometer etc., here, consider from the easiness of measuring, used WYCO NT-2000 as U.S. Wei Yike precision instrument Co., Ltd (veeco) manufacturing of non-contact type three-dimensional light interfere type surface roughometer.The calculating of Ra value is undertaken by following formula (1).That is height Z, by obtaining at each measuring point jk
JkThe absolute value of (height when average height is made as reference surface (highly=0)) carries out arithmetic average, calculates Ra.
Here, M and N are the data numbers on all directions in the sample plane with the short transverse quadrature, if detector is CCD, then are equivalent to vertical and horizontal pixel count.
The film that possesses this surface roughness and mist degree, its transparency is excellent, is particularly suitable for the purposes of transparent optical film described later.
In addition, the refractive index of film is preferably below 1.5.If refractive index is low, then the reflectivity on surface reduces, and therefore considers it also is preferred from the viewpoint that reduces surperficial optical loss.
The thickness of film is preferably 10 μ m~300 μ m, more preferably 20 μ m~200 μ m.By making thickness is more than the 10 μ m, is difficult for producing fold when rolling up to drum, and can suppress to break because mechanical strength increases, thereby preferred.In addition, by being below the 300 μ m, volume is drum easily.In addition, when being used in protective film of polarizing plate, optical compensation films etc., can realize lightweight, filming.
And then, refractive index in this face is reached maximum direction be made as X-axis, with in the face and the direction vertical with X-axis be made as Y-axis, refractive index under the wavelength 590nm separately is made as nx, ny, when the thickness of film is made as d, length of delay Re=(nx-ny) * d in the face under the wavelength 590nm is suitably below the 5nm, is preferably below the 3nm.
In addition, refractive index in this face is reached maximum direction be made as X-axis, with in the face and the direction vertical with X-axis be made as Y-axis, the thickness direction of film is made as the Z axle, refractive index under the wavelength 590nm separately is made as nx, ny, nz, when the thickness of film was made as d, length of delay Rth=| (nx+ny)/2-nz| * d of the thickness direction under the wavelength 590nm was suitably below the 10nm, is preferably below the 3nm.
Value by making length of delay Re, Rth when the polarization plates that will use this film, when optical compensation films is used for liquid crystal indicator, can suppress when vertical direction is observed liquid crystal display face and the contrast when oblique side is observed and the variation of form and aspect in above-mentioned scope.
In addition, the water absorption rate of measuring according to JIS K7209 method of film is preferably below 0.1%, more preferably below 0.05%.If water absorption rate is below 0.1%, then the change in size that is caused by suction can reduce, and for example, during as protective film of polarizing plate, optical compensation films substrate, is difficult for taking place warpage.In addition, can prevent the caused dewfall of the water vapour that from film, discharges.
In addition, in the cyclic polyolefin mesentery as in the past isotropic membrane, also there be change in size and the little film of changes in optical properties that has such water absorption rate and cause by suction.But such cyclic polyolefin mesentery is difficult to permeate water steam usually, and is relative therewith, the film of present embodiment, and for example being easy to make water vapour permeability is 25g/m
2/ day above, be preferably 45g/m
2More than/the sky.Owing to can have the character of easy permeate water steam, therefore, for the purposes of the water system bonding agent that for example the environment for use load is little when bonding with other materials, for example protective film of polarizing plate is useful.Water vapour permeability is measured according to JIS Z0208 method.
That is, the film of present embodiment can be more suitable to the various uses of in the past various isotropic membranes.
In addition, in the film of present embodiment, in the scope of not damaging the object of the invention, also can contain plasticizer.As plasticizer, mineral oil, the oligomer of alpha-olefines, copolymer, the ester that can enumerate paraffin series, naphthene series, aromatic series etc. are plasticizer, each vegetable oil, animal wet goods.Such plasticizer makes the processing and forming when stretching better.
In addition, also can contain other resins in the film of present embodiment, for example TPO, polyamide-based, polyesters etc.
In addition, in the film of present embodiment, also can in the scope of not damaging the object of the invention, add and add various compounding ingredients such as the weather-proof stabilizing agent that uses in the polyolefin, heat-resisting stabilizing agent, slip agent, nucleator, pigment, dyestuff usually to.
The particularly preferred method that is used to make this film is the manufacture method that comprises following operation: the film that is formed by crystallinity alkene (being total to) polymer that will form by extrusion by melting, solution casting method etc. is stretching more than the vitrification point (Tg) of this crystallinity alkene (being total to) polymer and under less than 120 ℃ temperature.Draft temperature is more preferably more than Tg+10 ℃ and below 100 ℃.
If draft temperature is more than the Tg, then film can not break etc., can stretch more equably, thereby preferred.If draft temperature less than 120 ℃, then can reduce the mist degree of film especially effectively, thus preferred.Though draft temperature can't be determined less than 120 ℃ of principles that can reduce the film mist degree especially effectively, but infer and following situation has something to do: because the recrystallization temperature of alkene (being total to) polymer such as poly(4-methyl-1-pentene) is about 120 ℃~170 ℃, in heating under being lower than the temperature of this scope, stretching, the cooling procedure, the degree of crystallinity of mist degree rising or the increase of crystal size are suppressed.Lift an example, be considered to: just with the construction unit of being derived by 4-methyl-1-pentene be alkene (being total to) polymer of principal component, degree of crystallinity, crystal size are about 2 times that stretch preceding when stretching for 200 ℃, and almost do not change when stretching for 40 ℃ or reduce.
When melt extruding moulding, specifically, use single screw extrusion machine, after carrying out moulding with the barrel zone temperature of regulation and the stack temperature of regulation, utilize stretching-machine, more than vitrification point (Tg) and below 120 ℃, preferred temperature below 100 ℃, carry out drawing and forming with draw speed with the corresponding regulation of the multiplying power (preferred below 5 times, preferred especially below 3 times) of regulation.Never make on the meaning that degree of crystallinity, crystal size increases, preferred stretching ratio is the smaller the better and draw speed is the bigger the better.In addition, stretching can be undertaken by uniaxial tension, biaxial stretch-formed etc. any.The viewpoint that degree of crystallinity, crystal size are increased is considered, compares with uniaxial tension, preferably uses biaxial stretch-formed.
At this moment, can when melt extruding moulding, produce the film of master (former anti-) sheet earlier after, again to drawing and forming unit feeding film in the original, also can melt extrude moulding and drawing and forming continuously.
In addition, consider from the viewpoint that reduces degree of crystallinity, crystal size, when molten resin is formed film, also can be in quenching on the stack to below Tg+50 ℃, preferably below Tg+30 ℃.Here, so-called quenching (cooling fast) is meant at short notice temperature is reduced to the temperature of in fact not carrying out crystallization from the temperature of carrying out crystallization.Owing to be difficult to correctly measure the resin temperature of film forming procedure, therefore be difficult to quantize, but preferably with more than 100 ℃/second, more preferably cool off apace with the speed more than 200 ℃/second.
The film that obtains like this can become low surface roughness, low haze.Its reason is also indeterminate, but thinks for example following reason.
By will with the regulation method for example moulding such as extrusion by melting, solution casting method film the regulation temperature range carry out drawing and forming, the thermal deformation meeting of the film that is taken place when causing concavo-convex film moulding is relaxed, is revised along with macromolecular chain reorientation in the drawing and forming, and this is concavo-convex thereby reduced.And then think that by quenching on stack before the film with moulding carries out drawing and forming, degree of crystallinity is minimized and the crystallization particle diameter is reduced, as its result, mist degree further reduces.
And then, by melt extruding moulding when obtaining film, also can be in moulding or after moulding and then, the compression of between the roller of extruder, pressurizeing, thus can further improve the transparency of gained film.
In addition; the film of present embodiment is because its surface roughness and mist degree are transparent high in prescribed limit; therefore can be used for purposes such as transparent optical film, especially protective film of polarizing plate, stripping film, diaphragm, optical compensation films aptly, the invention provides these transparent optical film.Here, optical compensation films can be to use the film of single layer structure of the film of present embodiment, also can be the film of the sandwich construction that is formed by combining of a plurality of films as described later.
Fig. 1 represents that the film with present embodiment is applied to the example of polarization plates.
This polarization plates stacked above one another have protection surface diaphragm 1, to polarization plates give marresistance etc. hard conating 2, second protective film of polarizing plate 3, polariscope 4, first protective film of polarizing plate 5, other elements are played the adhesion coating 6 of adhesive linkage effect, the stripping film 7 of protection adhesion coating 6.
Here, with regard to diaphragm 1 since the display element that polarization plates is installed for example the detection operation of liquid crystal display cells be to carry out having under the state of diaphragm, therefore can use the film of the optical characteristics excellence as present embodiment so aptly.First and second protective film of polarizing plate 5,3, owing to require in protection polariscope 4, to have the high transparency, so can use the film of the optical characteristics excellence as present embodiment so aptly.With regard to stripping film 7, be to be used for when forming display element the adhesion coating 6 of further stacked optical compensation films, phase retardation film (plate) etc.s on this polarization plates and to design in order to cover, because the detection operation of this polarization plates is to carry out under the state that has stripping film 7, so can use the film of the optical characteristics excellence as present embodiment so aptly.
In addition, Fig. 2 represents the film of present embodiment is applied to the example of the optical compensation films of sandwich construction.
This optical compensation films stacked above one another have protection surface diaphragm 8, to optical compensation films give marresistance etc. hard conating 9, have the optical compensation function of regulation liquid crystal layer 10, be used for stacked liquid crystal layer 10 substrate 11, other elements are played the adhesion coating 12 of adhesive linkage effect, the stripping film 13 of protection adhesion coating 12.
In the example of Fig. 2,, consider, can use the film of present embodiment aptly from above-mentioned viewpoint as diaphragm 8 and stripping film 13.
In addition, among the present invention, above-mentioned film, the transparent optical film of having used this film can be used for display element aptly, for example liquid crystal display cells, organic EL etc. the invention provides such display element.
Fig. 3 is the figure of expression as an example of the formation of the liquid crystal indicator of such display element.
With regard to this liquid crystal indicator, stacked above one another has polarization plates 14, polarizer 15, optical compensation films 16, liquid crystal panel 17, polarizer 18, polarization plates 19, back light unit 20.
Here, as polarization plates 14,19, the polarization plates that can use present embodiment as shown in Figure 1 to be suitable for aptly.As optical compensation films 16, can use the film of sandwich construction as shown in Figure 2 aptly, also can use the film of single layer structure of the film of direct application present embodiment aptly.
By such formation, carry out polarization from the incident light of back light unit 20 by polarization plates 19, only see through rectilinearly polarized light, make the phase place unification of polarised light by polarizer 18, incide liquid crystal panel 17.Form output image on the liquid crystal panel 17, generation is used to reappear this visual light and outgoing, and this emergent light carries out viewing angle compensation by optical compensation films 16, makes the phase difference unification by polarizer 15, carries out polarization by polarization plates 14, and adjusts contrast.
The invention is not restricted to above-mentioned embodiment and object lesson, in the scope that does not break away from the object of the invention, can suitably change.
Embodiment
Below, specify optimal way of the present invention with reference to embodiment, comparative example.The present invention is not limited to following embodiment going up in all senses.
In embodiment, the comparative example, each characteristic of the film that obtains is measured by the following method.
(thickness)
Be to utilize the digital display device (model: contact pin type film thickness gauge mensuration ID-F125) of having used three rich companies to make.
(surface roughness Ra)
Use to measure 20 times of multiplying powers, zoning 300 μ m * 230 μ m, is calculated Ra as the WYCO NT-2000 of the U.S. Wei Yike precision instrument Co., Ltd manufacturing of non-contact type three-dimensional light interfere type surface roughometer.Here, it is 736 * 480 that the maximum of this analyzer is measured pixel, and the resolution ratio of vertical direction is below the 0.1nm.
(mist degree)
Be according to JIS K7105 method, with the full-automatic mist degree instrument (model: the TC-HIIIDPK type) measure of (having) Tokyo electricity look company manufacturing.
(internal haze)
During above-mentioned mist degree is measured, fill with in silica dish that (organosilicon company of SHIN-ETSU HANTOTAI makes, trade name KF-96-100CS as the silicone oil with the approaching liquid of the refractive index of film, refractive index 1.403), this silica dish is arranged on the specimen holder, sample is immersed in wherein, measure internal haze.
(moisture-vapor transmission)
According to JIS Z0208 method, use the moisture vapor transmission cup of Φ 60mm, under the condition of 40 ℃ * 90%RH, measure.Use calcium chloride as hygroscopic agent, carry out weighing with 24 hours intervals, utilize two continuous weighings, the quality of obtaining time per unit separately increases, and uses this quality increase to become 5% value when interior and constant.Unit is g/m
2/ day.
As crystallinity alkene (being total to) polymer, use is as Mitsui Chemicals, Inc's system TPX resin (name of product: MX020 of the copolymer that obtains with 4-methyl-1-pentene, MFR:23~30g/10min, refractive index 1.46, fusing point: 230 ℃, vitrification point: 15 ℃, water absorption rate: below 0.01%), with single screw extrusion machine (diameter 40mm), under the condition of 300 ℃ of barrel zone temperatures, 30 ℃ of stack temperature, melt extrude moulding, make the film of thickness 120 μ m.Then, this film is gone up at the flow direction (MD direction) of film 60 ℃ of temperature with stretching-machine and to be stretched about 3 times, make the monadic stretching membrane of thickness 40 μ m.
Surface roughness Ra, the mist degree of the monadic stretching membrane that obtains are shown in table 1.Here, the water absorption rate of film is identical with the water absorption rate of the resin of use.
As crystallinity alkene (being total to) polymer, use is as Mitsui Chemicals, Inc's system TPX resin (name of product: MX020 of the copolymer that obtains with 4-methyl-1-pentene, MFR:23~30g/10min, refractive index 1.46, fusing point: 230 ℃, vitrification point: 15 ℃, water absorption rate: below 0.01%), with single screw extrusion machine (diameter 40mm), under the condition of 300 ℃ of barrel zone temperatures, 80 ℃ of stack temperature, melt extrude moulding, make the film of thickness 120 μ m.Then, this film is gone up at the flow direction (MD direction) of film 80 ℃ of temperature with stretching-machine and to be stretched about 2 times, make the monadic stretching membrane of thickness 60 μ m.
Surface roughness Ra, the mist degree of the monadic stretching membrane that obtains are shown in table 1.Here, the water absorption rate of film is identical with the water absorption rate of the resin of use.
Embodiment 3
As crystallinity alkene (being total to) polymer, use is as Mitsui Chemicals, Inc's system TPX resin (name of product: RT18 of the copolymer that obtains with 4-methyl-1-pentene, MFR:23~30g/10min, refractive index 1.46, fusing point: 239 ℃, vitrification point: 22 ℃, water absorption rate: below 0.01%), under the condition of 300 ℃ of barrel zone temperatures, 30 ℃ of stack temperature, melt extrude moulding, make the film of thickness 120 μ m.At this moment, with stack and relative this film of touch roll cramping.Then, this film is gone up at the flow direction (MD direction) of film 60 ℃ of temperature with stretching-machine and to be stretched about 3 times, make the monadic stretching membrane of thickness 40 μ m.
Surface roughness Ra, the mist degree of the monadic stretching membrane that obtains are shown in table 1.Here, the water absorption rate of film is identical with the water absorption rate of the resin of use.
Comparative example 1
As crystallinity alkene (being total to) polymer, use is as Mitsui Chemicals, Inc's system TPX resin (name of product: MX020 of the copolymer that obtains with 4-methyl-1-pentene, MFR:23~30g/10min, refractive index 1.46, fusing point: 230 ℃, vitrification point: 15 ℃, water absorption rate: below 0.01%), with single screw extrusion machine (diameter 40mm), under the condition of 300 ℃ of barrel zone temperatures, 80 ℃ of stack temperature, melt extrude moulding, make the film of thickness 40 μ m.
Surface roughness Ra, the mist degree of the film that obtains are shown in table 1.Here, the water absorption rate of film is identical with the water absorption rate of the resin of use.
Comparative example 2
As crystallinity alkene (being total to) polymer, use is as Mitsui Chemicals, Inc's system TPX resin (name of product: MX020 of the copolymer that obtains with 4-methyl-1-pentene, MFR:23~30g/10min, refractive index 1.46, fusing point: 230 ℃, vitrification point: 15 ℃, water absorption rate: below 0.01%), with single screw extrusion machine (diameter 40mm), under the condition of 300 ℃ of barrel zone temperatures, 80 ℃ of stack temperature, melt extrude moulding, make the film of thickness 50 μ m.
Surface roughness Ra, the mist degree of the film that obtains are shown in table 1.Here, the water absorption rate of film is identical with the water absorption rate of the resin of use.
Comparative example 3
As crystallinity alkene (being total to) polymer, use is as Mitsui Chemicals, Inc's system TPX resin (name of product: MX020 of the copolymer that obtains with 4-methyl-1-pentene, MFR:23~30g/10min, refractive index 1.46, fusing point: 230 ℃, vitrification point: 15 ℃, water absorption rate: below 0.01%), with single screw extrusion machine (diameter 40mm), under the condition of 300 ℃ of barrel zone temperatures, 80 ℃ of stack temperature, melt extrude moulding, make the film of thickness 120 μ m.
Surface roughness Ra, the mist degree of the film that obtains are shown in table 1.Here, the water absorption rate of film is identical with the water absorption rate of the resin of use.
Comparative example 4
As crystalline polyolefin system (being total to) polymer, use is as Mitsui Chemicals, Inc's system TPX resin (name of product: MX020 of the copolymer that obtains with 4-methyl-1-pentene, MFR:23~30g/10min, refractive index 1.46, fusing point: 230 ℃, vitrification point: 15 ℃, water absorption rate: below 0.01%), with single screw extrusion machine (diameter 40mm), under the condition of 300 ℃ of barrel zone temperatures, 80 ℃ of stack temperature, melt extrude moulding, make the film of thickness 120 μ m.Then, this film is gone up at the flow direction (MD direction) of film 160 ℃ of temperature with stretching-machine and to be stretched about 3 times, making thickness is the monadic stretching membrane of 40 μ m.
Surface roughness Ra, the mist degree of the monadic stretching membrane that obtains are shown in table 1.Here, the water absorption rate of film is identical with the water absorption rate of the resin of use.
Comparative example 5
As crystalline polyolefin system (being total to) polymer, use is as Mitsui Chemicals, Inc's system TPX resin (name of product: MX0020 of the copolymer that obtains with 4-methyl-1-pentene, MFR:18~25g/10min, refractive index 1.46, fusing point: 230 ℃, vitrification point: 10 ℃, water absorption rate: below 0.01%), with single screw extrusion machine (diameter 40mm), under the condition of 300 ℃ of barrel zone temperatures, 80 ℃ of stack temperature, melt extrude moulding, make the film of thickness 120 μ m.Then, this film is gone up at the flow direction (MD direction) of film 190 ℃ of temperature with stretching-machine and to be stretched about 2 times, make the monadic stretching membrane of thickness 60 μ m.
Surface roughness rugosity Ra, the mist degree of the monadic stretching membrane that obtains are shown in table 1.Here, the water absorption rate of film is identical with the water absorption rate of the resin of use.
Table 1
The stack temperature | Stretch or the pressurization compression | Thickness (μ m) | ??Ra | Mist degree | Internal haze | Water | |
Embodiment | |||||||
1 | ??30℃ | 60 ℃, 3 times stretchings | ?40 | ??4nm | ??0.3% | ??0.1% | ??70 |
|
??80℃ | 80 ℃, 2 times stretchings | ?60 | ??5nm | ??0.3% | ??0.1% | ??48 |
Embodiment 3 | ??30℃ | 60 ℃, 3 times stretchings of touch roll | ?40 | ??2nm | ??0.2% | ??0.0% | ??69 |
Comparative example 1 | ??80℃ | Do not have | ?40 | ??18nm | ??1.3% | ??0.0% | ??71 |
Comparative example 2 | ??80℃ | Do not have | ?50 | ??21nm | ??1.6% | ??0.0% | ??56 |
Comparative example 3 | ??80℃ | Do not have | ?120 | ??25nm | ??4.7% | ??0.0% | ??24 |
Comparative example 4 | ??80℃ | 160 ℃, 3 times stretchings | ?40 | ??9nm | ??1.4% | ??0.7% | ??73 |
Comparative example 5 | ??80℃ | 190 ℃, 2 times stretchings | ?60 | ??8nm | ??1.2% | ??0.8% | ??48 |
Claims (16)
1. a film is formed by crystallinity alkene (being total to) polymer, it is characterized in that, surface roughness Ra is below the 5nm and mist degree is below 1%.
2. according to the film of claim 1 record, it is characterized in that described crystallinity alkene (being total to) polymer is to use at least a alkene of selecting to obtain as (being total to) polymerization composition from 4-methyl-1-pentene, 3-Methyl-1-pentene, 3-methyl-1-butene.
3. according to the film of claim 1 or 2 records, it is characterized in that internal haze is below 0.5%.
4. according to the film of each record in the claim 1~3, it is characterized in that the water absorption rate of measuring according to JIS K7209 method is below 0.1%.
5. according to the film of each record in the claim 1~4, it is characterized in that the moisture-vapor transmission of measuring according to JIS Z0208 method is 25g/m
2More than/the sky.
6. according to the film of each record in the claim 1~5, it is characterized in that refractive index is below 1.5.
7. according to the film of each record in the claim 1~6, it is characterized in that, refractive index in this face is reached maximum direction be made as X-axis, with in the face and the direction vertical with X-axis be made as Y-axis, refractive index under the wavelength 590nm separately is made as nx, ny, when the thickness of film was made as d, length of delay Re=(the nx-ny) * d in the face under the wavelength 590nm was below the 5nm.
8. according to the film of each record in the claim 1~7, it is characterized in that, refractive index in this face is reached maximum direction be made as X-axis, with in the face and the direction vertical with X-axis be made as Y-axis, the thickness direction of film is made as the Z axle, refractive index under the wavelength 590nm separately is made as nx, ny, nz, and when the thickness of film was made as d, length of delay Rth=| (nx+ny)/2-nz| * d of the thickness direction under the wavelength 590nm was below the 10nm.
9. the manufacture method of the film of each record in the claim 1~8, it is characterized in that, for the film that forms by crystallinity alkene (being total to) polymer, more than the vitrification point (Tg) of this crystallinity alkene (being total to) polymer and less than 120 ℃ temperature, stretch.
10. according to the manufacture method of the film of claim 9 record, it is characterized in that when molten resin was formed film, quenching was to below Tg+50 ℃.
11. the manufacture method according to the film of claim 9 record is characterized in that, when forming the film that is formed by crystallinity alkene (be total to) polymer by extrusion by melting or pressurize afterwards and compress this film.
12. protective film of polarizing plate is characterized in that, has used the film of each record in the claim 1~8.
13. optical compensation films is characterized in that, has used the film of each record in the claim 1~8.
14. stripping film is characterized in that, has used the film of each record in the claim 1~8.
15. diaphragm is characterized in that, has used the film of each record in the claim 1~8.
16. display element is characterized in that, has used the film of each record in claim 1~8 and the claim 12~15.
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CN115044087A (en) * | 2022-08-15 | 2022-09-13 | 江苏康辉新材料科技有限公司 | Low-haze optical film and preparation method and application thereof |
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JP5548376B2 (en) * | 2009-03-25 | 2014-07-16 | 三井化学株式会社 | Resin film for transverse stretching containing 4-methylpentene-1 (co) polymer and method for producing the same |
KR101073020B1 (en) | 2009-04-27 | 2011-10-12 | 황천남 | Light Diffusion Plate and Method for Manufacturing the Same |
JP5760396B2 (en) * | 2010-11-10 | 2015-08-12 | 三菱瓦斯化学株式会社 | Polarizing plate protective film for flat panel display, retardation film for flat panel display, and methods for using them |
JP2019020718A (en) * | 2017-07-20 | 2019-02-07 | 住友化学株式会社 | Optical sheet |
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JPS61228931A (en) * | 1985-04-03 | 1986-10-13 | Toray Ind Inc | Biaxial stretching of poly(4-methylpentene-1) film |
JP2790330B2 (en) * | 1989-08-15 | 1998-08-27 | 三井化学株式会社 | Release film for manufacturing printed wiring board and method for manufacturing the same |
JPH04284402A (en) * | 1991-03-14 | 1992-10-09 | Asahi Chem Ind Co Ltd | Novel phase difference compensation sheet |
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CN115044087A (en) * | 2022-08-15 | 2022-09-13 | 江苏康辉新材料科技有限公司 | Low-haze optical film and preparation method and application thereof |
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