CN107850717A - Optical film and image display device - Google Patents
Optical film and image display device Download PDFInfo
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- CN107850717A CN107850717A CN201680041449.XA CN201680041449A CN107850717A CN 107850717 A CN107850717 A CN 107850717A CN 201680041449 A CN201680041449 A CN 201680041449A CN 107850717 A CN107850717 A CN 107850717A
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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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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- 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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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The optical film of the present invention is the optical film that alkaline earth metal carbonate micropowder is dispersed with resin, the optical film is characterised by, the average major diameter of above-mentioned alkaline earth metal carbonate micropowder be 10nm~100nm in the range of, relative to the content of the overall above-mentioned alkaline earth metal carbonate micropowder of above-mentioned optical film be the mass % of 0.1 mass %~50 in the range of, in the surface attachment of above-mentioned alkaline earth metal carbonate micropowder have surfactant.In addition, the image display device of the present invention is the image display device for possessing above-mentioned optical film.
Description
【Technical field】
The present invention relates to optical film and image display device, the more particularly to optics containing alkaline earth metal carbonate micropowder
Film and image display device.
【Background technology】
Strontium carbonate micropowder is used in the various fields such as monolithic ceramic capacitor.In addition, in recent years it has also been found that its with
As the purposes for suppressing or showing birefringent filler in the optical films such as the diaphragm of liquid crystal display device.
Generally there are solution cast film formation and extrusion by melting in the film forming of optical film.Solution cast film formation is will be molten
The resin of liquid status is cast on base material and made the method that solvent volatilizees.In the method, due to not applying certain side to resin
To power, thus be not easy in the optical film after film forming show birefringence, the optical film purposes suitable for non-birefringent.But
It is that in the method, due to the volatilization of solvent to be carried out, thus manufacturing cost increases, also worries solvent to human body not in addition
Good influence etc..
On the other hand, extrusion by melting is the method that the resin of molten condition is carried out to film forming using extrusions such as die heads.By
The volatilization of solvent need not be carried out as above-mentioned solution cast film formation in this method, thus manufacturing cost is low, security
Also it is high.But due to the applying power in one direction in resin melt extrusion, thus the marriage chain (main shaft) of resin is along extrusion side
To being elongated and being orientated, birefringence is shown sometimes in the optical film after film forming.
Therefore, in the past, as the birefringent filler (resin filler) for controlling resin, strontium carbonate micro mist is advocated
End.Strontium carbonate is twin shaft birefringence crystallization, has and shows negative birefringent property.Therefore, with positive intrinsic two-fold
In the case of the resin material penetrated, it is blended in molten resin by regarding the strontium carbonate as filler and is carried out in extrusion by melting
Melting extrusion, along the extrusion direction of resin, the major diameter of strontium carbonate fine particles is orientated in extrusion direction.As a result, resin
Intrinsic birefringence be cancelled, the birefringence of optical film reduces.As optical film in this case, suitable for such as diaphragm
Purposes.
In addition, pass through a large amount of mixed carbonic acid strontiums, additionally it is possible to strengthen birefringence, strengthen the birefringence of optical film.In addition, pass through
Resulting film is further stretched along single shaft direction or biaxially oriented, additionally it is possible to further show birefringence.As this
In the case of optical film, suitable for the purposes such as phase retardation film.
As such phase retardation film, such as the phase retardation film obtained as follows is recorded in the embodiment of patent document 1：
Using as major diameter 200nm, wide 20nm acicular crystal strontium carbonate using relative to ester ring type vistanex as 15 weight %'s
Ratio, which is dissolved in dichloromethane, makes doped solution, will enter line width certainly at 129 DEG C with 1.5 times by the film that doped solution obtains
By uniaxial tension, obtain phase retardation film.
【Prior art literature】
【Patent document】
Patent document 1：Japanese Unexamined Patent Publication 2006-251644 publications (0055 section etc.)
【The content of the invention】
【Invent problem to be solved】
In order to control the birefringence of resin, it is necessary to which strontium carbonate particle high dispersive is blended in resin.But for special
As sharp document 1 for the big strontium carbonate particle of average major diameter, compared with the small strontium carbonate particle of average major diameter, optical film
The transparency reduces, as a result, in the case where such optical film is used for into image display device etc., has poor visibility not
Good situation.
On the other hand, if making strontium carbonate Particle pollution to improve the transparency of optical film, surface area increases, is micro-
Grain easily aggregates with one another.Due to the factor that flocculated particle is light scattering, thus the transparency of optical film is damaged.
It is an object of the invention to provide transparent height, it can arbitrarily control birefringent optical film and image display device.
【The means to solve the problem】
The present inventor has made intensive studies to reach above-mentioned purpose, as a result finds, passes through alkali salt micropowder
Average major diameter and content so pass through surface treatment, even if being the small micropowder of average major diameter, in resin dispersiveness
It can be improved.Its results verification arrives, and can realize that the transparency of optical film improves and control these two aspects with refractive index, so as to complete
Into the present invention.
That is, the present invention relates to a kind of optical film, it is the optics that alkaline earth metal carbonate micropowder is dispersed with resin
Film, the optical film are characterised by that the average major diameter of above-mentioned alkaline earth metal carbonate micropowder is 10nm~100nm scope
It is interior, be the mass % of 0.1 mass %~50 relative to the content of the overall above-mentioned alkaline earth metal carbonate micropowder of above-mentioned optical film
In the range of, in the surface attachment of above-mentioned alkaline earth metal carbonate micropowder have surfactant.
In this case, above-mentioned alkali carbonate is preferably strontium carbonate.Additionally, it is preferred that above-mentioned average major diameter be 20nm~
In the range of 50nm, and mist degree is less than 1%.In addition, in the range of above-mentioned content is preferably the mass % of 1 mass %~35.
In addition, above-mentioned resin be preferably selected from by makrolon, polymethyl methacrylate, cellulose esters, polystyrene,
Styrene acrylonitrile copolymer, poly- dimethyl ester, polyarylate, polyether sulfone, polyolefin, Maleimide copolymer, poly- pair
PET, PEN, polyimides, polyamide, polyurethane composition group in it is a kind of with
On.
Particularly, above-mentioned resin is preferably makrolon, preferably further includes surface modifier in this case.
In addition, in such a situation it is preferred in the range of above-mentioned content is the mass % of 8 mass %~16, mist degree be 1% with
Under, and with birefringence in positive face.Or in the range of preferably above-mentioned content is the mass % of 8 mass %~16, mist degree
For less than 1%, and birefringence is zero in face.
In addition, above-mentioned resin is preferably polymethyl methacrylate.In this case, preferably above-mentioned content is 8 mass %
In the range of~32 mass %, mist degree is less than 1%, and with birefringence in negative face.In addition, thickness is preferably 20 μm
In the range of~150 μm.In addition, above-mentioned optical film is preferably stretched film.Furthermore it is preferred that arithmetic mean surface roughness (Ra) is
Below 20nm, and the image (writing as property) under conditions of light comb width 0.125mm is 75% (according to JIS K 7374)
More than.
Moreover, it relates to a kind of image display device, it is characterised in that it possesses the optics described in any of the above-described
Film.
【The effect of invention】
In accordance with the invention it is possible to provide, a kind of transparency is high, can arbitrarily control birefringent optical film.In addition, according to this
A kind of invention, using the teaching of the invention it is possible to provide image display device for possessing such optical film.
【Embodiment】
The optical film of the present invention is the optical film that alkaline earth metal carbonate micropowder is dispersed with resin, alkaline-earth metal carbon
The average major diameter of hydrochlorate micropowder be 10nm~100nm in the range of, relative to the overall content of above-mentioned optical film be 0.1 matter
There is surfactant in the range of amount %~50 mass %, in surface attachment.The optical film of the present invention can be by will be in resin
In be dispersed with the resin combination of alkaline earth metal carbonate micropowder and manufactured with membranaceous progress film forming.Below for composition resin
Each composition of composition illustrates.
1. alkaline earth metal carbonate micropowder
For alkaline earth metal carbonate micropowder using alkaline earth metal carbonate as principal component, average major diameter is 10nm~100nm,
Surface attachment has surfactant.Thus, even average major diameter is less than conventional alkaline earth metal carbonate particulate, due in table
Face is attached with surfactant, also has polymolecularity when being dispersed in resin.
(1) alkaline earth metal carbonate particulate (before surface treatment)
The average major diameter of alkaline earth metal carbonate particulate before being surface-treated using surfactant be 10nm~
In the range of 100nm, in the range of preferably 15nm~75nm, in the range of more preferably 20nm~50nm.If average major diameter
Less than 10nm, then particle it is too small, it is easy condense, dispersiveness is easily deteriorated.On the other hand, if average major diameter is higher than 100nm,
Then particle is excessive, and when being mixed with resin, the transparency is easily deteriorated.
Herein, average major diameter can pass through scanning electron microscope (SEM) photo for alkaline earth metal carbonate particulate
The visual or automatic method for carrying out image procossing is carried out to determine.The major diameter of alkaline earth metal carbonate particulate can be with by strontium carbonate
The form of the length (length of long side) of length direction when the alkaline earth metal carbonate particle such as particle is regarded as rectangle determines.
Specifically, the minimum rectangle of and area circumscribed with the alkaline earth metal carbonate particle in image is calculated, by its long side
Length obtain major diameter.In addition, " average " refers to for statistically having the alkaline earth of a certain number (N numbers) of reliability gold
Average value obtained from category carbonate is measured as the number is usually more than 300, preferably more than 500, it is more excellent
Elect more than 1000 as.It should be noted that the minor axis of alkaline earth metal carbonate particle can be with by alkaline earth metal carbonate
Grain is judged as the form of the length (length of short side) of short side direction during rectangle to determine.
It is not particularly limited for the average aspect ratio of alkaline earth metal carbonate particulate, usually 1.0~5.0 scope
It is interior, be preferably in the range of 2.0~4.5, particularly preferably in the range of 2.5~4.0.If average aspect ratio is higher than 5.0, micro-
Grain is excessively elongated and easily snaps off, and easily causes particle diameter distribution variation etc..In addition, in the case where draw ratio is too small, two-fold
It may be not easy to have given play to effect in the control penetrated.
It should be noted that described draw ratio refers to " major diameter/minor axis " of particle herein.In addition, average aspect ratio is
Refer to the average value of draw ratio, determine the draw ratio of 1 particle and calculate the average value of multiple particles.
As the alkaline-earth metal for forming alkaline earth metal carbonate particulate, calcium, strontium, barium, radium etc. can be enumerated.As alkaline earth gold
Belong to the example of percarbonate particle, calcium carbonate microparticle, strontium carbonate fine particles, barium carbonate particulate etc. can be enumerated.Among them, from light
With controlled in resin extender purposes etc. it is birefringent from the aspect of, preferred strontium carbonate fine particles.
(2) surfactant
Surfactant has the surface for being attached to alkaline earth metal carbonate particulate and improves particulate in resin or solvent
In dispersed function.Species as surfactant is not particularly limited, can enumerate nonionic surface active agent,
Anionic surfactant.It is sweet with stearic acid list from the transparency etc. of optical film among these surfactants
The nonionic surface active agent of grease etc is compared, more preferably anionic surfactant.Wherein particularly preferably containing parent
Water-based group and hydrophobic group and then the compound with the group that anion is formed in water.Hydrophilic radical preferably contains
There is the polyoxyalkylene for the alkylidene oxide that carbon number is 1~8.Hydrophobic group is preferably alkyl or aryl.Alkyl and
Aryl can carry substituent.The usual carbon number of alkyl be 3~30 in the range of, be preferably 10~18 in the range of.Aryl
In the range of usual carbon number is 6~30.In water formed anion group be preferably selected from by carboxylic acid group (- COOH),
Sulfate (- OSO3H), phosphate (- OPO (OH)2,-OPO (OH) O-) composition group in acidic group.The hydrogen atom of these acidic groups can
To be substituted by the alkali metal ions such as sodium or potassium or ammonium ion.
It is excellent for the reason for favorable dispersibility of the alkaline earth metal carbonate particulate in resin or in solvent among them
Select polycarboxylic acid's series anion type surfactant or the anionic surfactant of polyphosphoric acids system.
As polycarboxylic acid's series anion type surfactant, the compound represented by following formula (I)s can be enumerated.
【Change 1】
(herein, R1Refer to substituted or unsubstituted alkyl or substituted or unsubstituted aryl, E1Refer at carbon number
Alkylidene in the range of 1~8, a refer to the number in the range of 1~20, in the range of preferably 2~6.It should be noted that
R1It is preferred that carbon number is more than 10, the alkyl being preferably in the range of 10~18.)
As polyphosphoric acids series anion type surfactant, it is (single that the compound represented by following formula (II)s can be enumerated
Body) or the compound (disome) or formula (II) that are represented by following formula (III)s and formula (III) mixture.
【Change 2】
(herein, R2Refer to substituted or unsubstituted alkyl or substituted or unsubstituted aryl, E2Refer at carbon number
Alkylidene in the range of 1~8, b refer to the number in the range of 1~20, in the range of preferably 2~6.It should be noted that
R2It is preferred that carbon number is more than 10, the alkyl being preferably in the range of 10~18.)
【Change 3】
(herein, R3With R4Substituted or unsubstituted alkyl or substituted or unsubstituted virtue can be referred to identical or different
Base；E3With E4The alkylidene that carbon number is in the range of 1~8 can be referred to identical or different；C and d refers respectively to 1~20
In the range of, the number in the range of preferably 2~6.It should be noted that R3With R4Preferred carbon number is more than 10, preferably located
Alkyl in the range of 10~18.)
Surfactant can be used alone relative to alkaline earth metal carbonate micropowder, can also be by two or more mixing
Use.In addition, surfactant can only adhere on the surface of alkaline earth metal carbonate micropowder 1 layer, can also adhere to 2 layers with
On.In the case of more than 2 layers of attachment, identical surfactant can be used in layers, can also be used in layers
Different surfactants.It should be noted that whether surfactant is attached to the surface of alkaline earth metal carbonate micropowder
It can be carried out by using the infrared absorption spectroscopy of Fourier transform infrared spectroscopic measurement device (FT-IR) measure particle surface
Confirm.
(3) manufacture method of alkaline earth metal carbonate micropowder
Then the manufacture method of alkaline earth metal carbonate micropowder is illustrated.As alkaline earth metal carbonate micropowder
Manufacture method, as long as prepare as raw material alkaline earth metal carbonate particulate and surface is carried out to it using surfactant
The method of processing is just not particularly limited.Below for the strontium carbonate micropowder of one as alkaline earth metal carbonate micropowder
Manufacture method be specifically described.
(a) reaction process
Reaction process is following processes：While to the strontium hydroxide aqueous solution or waterborne suspension as raw material (hereinafter referred to as
For water paste) be stirred while in the presence of crystal growth inhibitor introducing carbon dioxide gas, make strontium hydroxide carbon
Acidifying, so as to manufacture the low spherical strontium carbonate fine particles of draw ratio.The concentration of strontium hydroxide for containing in water paste does not have
Especially limitation, usually the mass % of 1 mass %~20 scope, be preferably the mass % of 2 mass %~18 scope, more preferably
The mass % of 3 mass %~15 scope.
The preferred carboxyl number of crystal growth inhibitor is 2 and the organic acid for adding up to 3~6 of hydroxyl and carboxyl.As
The preferred embodiment of crystal growth inhibitor, tartaric acid, malic acid and hydroxymalonic acid can be enumerated.As crystal growth inhibitor,
It can use and add up to the organic acid with least three with hydroxyl with 2 carboxyls and hydroxyl and carboxyl, it is manufactured from being attached to
Particle surface come from the aspect of controlling granular grows and improving dispersed under micro situation, more preferably in above-mentioned molecule
Interior dicarboxylic acids or its acid anhydrides containing more than 1 hydroxyl, particularly preferred DL- tartaric acid.The dosage of crystal growth inhibitor is relative
It is usually the scope of the mass parts of 0.1 mass parts~20, is preferably 1 mass parts~10 mass parts in the mass parts of strontium hydroxide 100
Scope.
The flow of carbon dioxide relative to the scope that 1g strontium hydroxides are usually 0.5mL/ minutes~200mL/ minutes,
The preferably scope of 0.5mL/ minutes~100mL/ minutes.By reaction process can obtain for example average aspect ratio less than 1.5,
It is similar to spherical fine spherical strontium carbonate fine particles.It should be noted that the manufacture method of spherical strontium carbonate fine particles is international public
Open on the books in No. 2011/052680.
(b) curing step
Curing step is following processes：The water paste containing spherical strontium carbonate fine particles obtained for reacted process,
Cured with defined temperature, time, so that strontium carbonate fine particles of the granular grows into needle-like.Curing step can be in warm water
Carry out.In the range of curing temperature is 75 DEG C~115 DEG C, in the range of preferably 80 DEG C~110 DEG C, particularly preferably 85 DEG C~
In the range of 105 DEG C.If curing temperature is less than 75 DEG C, the crystalline growth with spherical strontium carbonate fine particles is insufficient, average length
Footpath is than too low tendency；If curing temperature is higher than 115 DEG C, the crystalline growth of the minor axis with spherical strontium carbonate fine particles is promoted
Enter, the tendency of draw ratio step-down.In addition, it is not particularly limited for the curing time, the scope of usually 1 hour~100 hours
It is interior, be preferably in the range of 5 hours~50 hours, particularly preferably in the range of 10 hours~30 hours.
It should be noted that above-mentioned reaction process and curing step are for obtaining needle-like by the strontium hydroxide as raw material
The process of strontium carbonate fine particles.
(c) surface treatment procedure
Surface treatment procedure is following processes：The strontium carbonate fine particles that average major diameter is in the range of 10nm~100nm point
Be dispersed in aqueous solvent, assign shearing force for resulting dispersion liquid so that primary particle scattered while with surface work
Property agent contact, obtain polymolecularity strontium carbonate.As surfactant, above-mentioned material can be used.
On the dispersion liquid used in surface treatment procedure, in the case where carrying out curing step, curing can be used
Water paste after process.Surface treatment procedure can be by applying shearing force while adding surface-active into dispersion liquid
Agent is carried out.The content of strontium carbonate particle in water paste is preferably in the mass % of 1 mass %~30 scope.On surface
Input amount in activating agent hydrotropism's slurry, the total amount of adding of surfactant are usually the mass % of 1 mass %~60 scope
It is interior, be preferably the mass % of 10 mass %~50 in the range of, in the range of the mass % of more preferably 20 mass %~40.Shearing force
Imparting can use stirrer paddle mixer, homomixer, magnetic stirring apparatus, air agitator, ultrasonic homogenizer,
Agitating device known to CLEARMIX, FilMix, wet shotcrete technology formula pulverizer etc. is carried out.
In the case where being surface-treated using two or more surfactants, in each surfactant hydrotropism slurry
Input amount relative to the mass parts of strontium carbonate particle 100 in water paste be usually the mass parts of 1 mass parts~40 scope, excellent
Elect the scope of the mass parts of 3 mass parts~30 as.Surfactant can simultaneously put into or gradually put into.
(d) drying process
Drying process is following processes：For through the water paste that above-mentioned surface treatment procedure obtains at 100 DEG C~300 DEG C
In the range of temperature be thermally dried, obtain the dried object of polymolecularity strontium carbonate micropowder.If drying temperature is less than 100
DEG C, then dry easily insufficient；If drying temperature is higher than 300 DEG C, heat deterioration of surface conditioning agent etc. easily occurs.Dry temperature
In the range of preferably 110 DEG C~180 DEG C of degree, in the range of more preferably 120 DEG C~160 DEG C.Drying process can be by making
Carried out with the known drying means of the heating drier such as spray dryer and heated drum, tray drier.
2. resin combination
The resin combination used in the present invention is that alkaline earth metal carbonate micropowder is dispersed in the resin formed in resin
Composition, the average major diameter of alkaline earth metal carbonate micropowder be 10nm~100nm in the range of, it is whole relative to resin combination
The content of body be the mass % of 1 mass %~50 in the range of, in surface attachment have surfactant.Due to above-mentioned alkaline-earth metal carbon
Hydrochlorate micropowder is surface-treated, thus although average major diameter is small, but the dispersiveness in resin is high, therefore can carry
The high transparency by film obtained from resin combination film forming.In addition, for alkaline earth metal carbonate micropowder, due to it
Originally as the powder of birefringence, it is thus possible to the birefringence for the optical film that control obtains resin combination film forming.That is, this hair
Bright resin combination can be used compatibly as the raw material for requiring transparent high, arbitrarily adjusting birefringent optical film.
As the resin contained in resin combination, as long as just not limited especially for the resin generally used in optical film
It is fixed, various resins can be selected according to purpose.As such resin, can enumerate makrolon, polymethyl methacrylate,
The cellulose esters such as triacetyl cellulose, polystyrene, styrene acrylonitrile copolymer, poly- dimethyl ester, polyarylate, polyethers
The polyolefin such as sulfone, poly- cyclic olefin, Maleimide copolymer, polyethylene terephthalate, poly- naphthalenedicarboxylic acid second two
One or more of group that alcohol ester, polyimides, polyamide, polyurethane form.
Alkaline earth metal carbonate micropowder is the mass %'s of 0.1 mass %~50 relative to the overall content of resin combination
In the range of.It is double based on alkaline earth metal carbonate micropowder when the content of alkaline earth metal carbonate micropowder is less than 0.1 mass %
Refraction control effect becomes too small.Conversely, when the content of alkaline earth metal carbonate micropowder is higher than 50 mass %, alkaline-earth metal carbon
Hydrochlorate micropowder is relatively excessive relative to the ratio of resin, thus the transparent of film that film forming obtains is deteriorated.Alkaline-earth metal carbonic acid
Salt micropowder be preferably the mass % of 0.5 mass %~40 relative to the overall content of resin combination in the range of, particularly preferably
In the range of the mass % of 1 mass %~35.
By the way that above-mentioned resin is mixed with alkaline earth metal carbonate micropowder, resin combination can be made.Alkaline earth gold
The mixing of category carbonate micropowder and resin can enumerate following methods：Resin is dissolved in the dispersion liquid of alkaline earth metal carbonate
In method (solwution method)；Resin is solved homogeneously in the dispersion liquid of alkaline earth metal carbonate, remove solvent, progress thereafter
The method of granulation or powdered；Alkaline earth metal carbonate and resin are carried out to the method (melting of melting mixing using extruder etc.
Method) etc..Furthermore it is also possible to pre-production masterbatch, is kneaded using kneading machine.Masterbatch can utilize above-mentioned solwution method, melt
Melt the making such as method.
Alternatively, it is also possible to prepare the doped solution for mixing resin combination and appropriate solvent to carry out optical film
Film forming.Species as such solvent is not particularly limited, and can properly select use according to property of resin etc..Make
For the example of solvent, preferable organic solvent, as the example of organic solvent, alcohol (such as ethanol, 1- propyl alcohol, 2- third can be enumerated
Alcohol, n-butyl alcohol, ethylene glycol), dichloromethane, NMP, tetrahydrofuran, MEK, ethyl acetate, butyl acetate, PGME, PGMEA,
Hexamethylene, toluene etc..One kind in above-mentioned solvent can be used only, can also be used in combination of two or more.
Resin is preferably 1 by quality ratio relative to the ratio of solvent:10~10:In the range of 1.On doped solution,
Resin and solvent can be mixed and made into mixed resin solution, add alkaline earth metal carbonate micropowder thereto and mixed,
Or alkaline earth metal carbonate micropowder and solvent can be mixed and made into powder mixed solution, resin is added thereto to be mixed
Close.In addition it is also possible to prepare above-mentioned mixed resin solution and powder mixed solution respectively, it is molten that both are mixed into doping
Liquid.Alkaline earth metal carbonate micropowder, resin and solvent can be by using ultrasonic homogenizer, agitating paddle, liquid injection formulas
Method known to method of pulverizer etc. is mixed.
Resin combination, doped solution can carry out film forming optical film is made using known method.It is used as film forming side
Method, membrane formation process known to above-mentioned melting extrusion membrane formation process, solution cast film formation etc. can be enumerated.Melting extrusion membrane formation process is
Fused mass is made in resin combination heating melting and it is cast to the method cooled and solidified on support with membranaceous.Separately
Outside, solution cast film formation is that doped solution is cast on support and solvent evaporation is carried out the method for membranization.
According to the species of resin, convection current is produced sometimes in resin solution when carrying out film forming, forms Bei Nade whirlpools
Structure.When forming Bei Nade eddy structures, alkaline earth metal carbonate micropowder condenses, the transparency variation of optical film.
In addition, the cohesion causes birefringence corrective action caused by alkaline earth metal carbonate micropowder to reduce.Therefore, for raising and branch
Wetability, the purpose for the formation for suppressing Bei Nade whirlpools for holding body, preferably add surface in resin combination or doped solution
Modifying agent.In the case where makrolon is used as resin, due to easily forming Bei Nade whirlpools, thus add surface and change
Property the transparency caused by agent improve and other effects it is big.As surface modifier, ethene base system surfactant, fluorine system can be enumerated
Surfactant, silicone oil etc..
Film after film forming can suitably be stretched according to purposes etc..As drawing process, can enumerate simple tension,
Biaxial tension etc..Biaxial tension can be gradually to stretch or stretch simultaneously.Stretching can use and dress is stretched known to stenter etc.
Put progress.
3. optical film
Because the optical film so obtained contains fine and high dispersive alkaline earth metal carbonate micropowder, thus the transparency
It is excellent, and optical film sheet can be adjusted relative to the overall content of optical film by adjusting alkaline earth metal carbonate micropowder
The birefringence of body.For alkaline earth metal carbonate micropowder, due to itself showing negative birefringence, thus can root
Purposes according to purpose optical film etc. adjusts the birefringence of optical film.
For example, by being added in showing for makrolon or poly- cyclic olefin etc in positive intrinsic birefringent resin
Alkaline earth metal carbonate micropowder, the intrinsic birefringence of resin can be offset, birefringence is made close to zero optical film.As
Such optical film, such as diaphragm can be enumerated.As diaphragm, except common protection of the lamination on polarizer surface etc.
Beyond film, in addition to direct lamination protects the polarizer diaphragm of polarizer on polarizer surface.
Or can be by being added in positive birefringent resin is shown as makrolon or poly- cyclic olefin
A small amount of alkaline earth metal carbonate micropowder and be made with positive birefringent optical film.Further, it is also possible to by these
Show and add substantial amounts of alkaline earth metal carbonate micropowder in positive birefringent resin and be made birefringent with what is born
Optical film.Described " birefringence " refers to the value of birefringence (Δ Nxy) in above-mentioned face herein.Shown just as such
Or in negative face birefringence optical film, phase retardation film can be enumerated.As phase retardation film, 1/4 wavelength plate, 1/ can be enumerated
2 wavelength plates etc..
Conversely, can also by polymethyl methacrylate or polystyrene etc. show negative birefringent resin or
It is made using above-mentioned alkaline earth metal carbonate micropowder in the small resin of birefringence and shows negative birefringent optical film.Make
For such optical film, phase retardation film can be enumerated.As phase retardation film, 1/4 wavelength plate, 1/2 wavelength plate etc. can be enumerated.
As the optical film of the present invention, in phase retardation film, C plates can be especially enumerated as suitable example.Generally, exist
Proposed in image display device using A plates (just：nx>Ny=nz, bear：nx<Ny=nz), C plates are being (just：Nx=ny<Nz, bear：nx
=ny>Nz) method of the optical characteristics such as angle of visibility characteristic, tone is improved.At present, positive (positive) C plates be by
The coating fluid based on liquid crystal material is coated with base material to be made its dry solidification and vertical alignment layer is made to make.
For needle-like strontium carbonate, the refractive index of the length direction of particle is less than short side direction.It is orientated in stretching
In the case of, nx<ny≒nz.By making needle-like strontium carbonate direction random orientation in face, nx=ny is realized<nz.On this
A bit, because the length direction of particle is random in face, thus x directions, the refractive index in y directions are averaged, nx=ny.
But due to being orientated (particle is in film surface accumbency) in thickness direction, thus nz is more than nx, ny.
As the present invention optical film, in addition to phase retardation film, diaphragm, can also enumerate antireflection film, antiglare film,
Briliancy, which improves film, prism film, angle of visibility, improves film etc..
The mist degree of optical film can be less than 10%, preferably less than 5%, more preferably can be less than 1%.Need to illustrate
, intentionally mist degree can also be made to be deteriorated according to the purposes of optical film.For example, by adding glass in resin combination
The light scattering particulate such as pearl, mist degree can be made to be deteriorated antiglare film is made.In addition, the light penetration of optical film can be 85% with
On, preferably more than 88%, more preferably can be more than 90%.In addition, the thickness of optical film is preferably 20 μm~150 μm of model
In enclosing, in the range of more preferably 25 μm~100 μm.
The average major diameter of the alkaline earth metal carbonate micropowder of the present invention is short and dispersed high, thus is not easy due to powder
End it is intergranular interaction or Bei Nade whirlpools formation and produce the cohesion of particle.Therefore, this hair is contained in optical film
During bright alkaline earth metal carbonate micropowder, the number of the flocculated particle protruded by surface tails off, as a result, optical film surface
Flatness is excellent.Specifically, the value of the arithmetic mean surface roughness (Ra) of optical film of the invention can be below 20nm,
More preferably can be below 15nm.Arithmetic mean surface roughness (Ra) then lacks the flatness on surface if higher value,
Easily cause reduction of observability due to concave-convex surface etc..Do not have for the lower limit of the value of arithmetic mean surface roughness (Ra)
There is special limitation, be more than 0nm.
For the alkaline earth metal carbonate micropowder of the present invention, due to not allowing to be also easy to produce the solidifying of particle as described above
It is poly-, thus scattering by the light based on flocculated particle etc., the reduction of the observability of optical film are lacked, the distinctiveness of transmission image is excellent
It is different.Specifically, the image of optical film of the invention under conditions of such as light comb width 0.125mm is (according to JIS K
7374) it can be more than 75%, preferably can be more than 80%, more preferably can be more than 85%.Image is than relatively low
During value, the distinctiveness of transmission image is easily reduced.It should be noted that the upper limit of image is not particularly restricted, with comprising upper
Each light comb width unit for stating light comb width is calculated as less than 100%.
4. optical laminate
Optical laminate can also be made with other optical film laminations in the optical film of the present invention.As other optical films, example
Light polarizing film (also referred to as polarization element), base material film can such as be enumerated.As optical laminate, can enumerate as the present invention
Polarizer that the diaphragm of optical film forms with light polarizing film lamination, using as the phase retardation film of optical film of the present invention and polarisation film layer
Ellipsoidal polarizing plate that product forms, using polarizer formed as the phase retardation film of optical film of the present invention and base material film lamination etc..
5. image display device
The image display device of the present invention is characterised by that it possesses the optical film of the present invention.As image display device
Species, liquid crystal display device (LCD), organic electroluminescence display device and method of manufacturing same etc. can be enumerated.In addition, as image display device
Purposes, portable data assistances such as television set, display of computer, mobile phone, smart mobile phone, PDA etc. can be enumerated.
【Embodiment】
The present invention is specifically described below based on embodiment, but they are not defined to the purpose of the present invention.
<Makrolon (PC) film>
(1) embodiment 1
(surface treatment of nano particle)
The water slurry that concentration by strontium carbonate nanometer particle (average major diameter 35nm, draw ratio 2.1) is 5% is put into
In 300mL beakers, polycarboxylic acid anion type surfactant (A) 5.25g is added, is stirred 5 minutes using agitator.Use
CLEARMIX (manufacture of M-Technique companies), should (equivalent to 30m/s) with 20000rpm in 4 DEG C of cooler design temperature
Pulp solution stirs 20 minutes.Thereafter, device is stopped, slurry is reclaimed, is sprayed onto and is heated on 130 DEG C of iron plate, cut take immediately
The powder of surface attachment, obtain being surface-treated powder 1.
(it is added with SrCO3Doping liquor manufacture method)
Makrolon (hereinafter referred to as " PC ") 6g is added in dichloromethane 25g, is stirred 6 hours, makes PC- dichloromethane
Solution.Then, the addition surface treatment powder 1 (0.48g) in dichloromethane 10g, it is put into ultra sonic bath 30 seconds, directly utilizes
The film filter that 1 μm of aperture is filtered in the case of non-pressurized, makes dispersion liquid 1.By PC- dichloromethane dispersion liquid with dividing
Dispersion liquid 1 mixes, and carries out decentralized processing using ultrasonic homogenizer, has obtained being added with SrCO3Doping liquid A-1.
(PC films film build method)
SrCO will be added with using Bake spreader (baker type applicator)3Doping liquid A-1 with wet coating thickness
11mil is coated on polyethylene terephthalate (hereinafter referred to as " PET ") film.It is dried 2 minutes at 40 DEG C, at 80 DEG C
Dry 4 minutes, dried 30 minutes at 120 DEG C.PC films are peeled off by PET film, obtain PC films A-1.PC films A-1 is filled using film stretching
Put and free end uniaxial tensions are carried out at 160 DEG C to 2.0 times (manufactured by well member making, IMC-1A8D types), obtain PC stretched films A-
1。
(transmitance and mist degree measure)
PC stretched films A-1 visible light transmissivity is carried out using spectrophotometer (light splitting society of Japan manufactures) and mist degree is surveyed
It is fixed.
(the phase difference evaluation of film)
Utilize micrometer measure PC stretched films A-1 thickness.Thereafter using phase determination device, (prince measures machine strain formula
Commercial firm manufactures, KOBRA-WR) phase difference (Δ Nxy) of the film after stretching is measured.Its result is listed in table 1.
(2) embodiment 2
Change except adding ethene base system surface in the mixed liquor that is mixed to PC- dichloromethane dispersion liquid with dispersion liquid 1
Beyond property agent 0.026g, method same as Example 1 is used.Thus PC stretched films B-1 is obtained.It is right similarly to Example 1
The characteristic of resulting film is evaluated.Its result is listed in table 1.
(3) embodiment 3
Except making SrCO3Addition be 0.96g this point beyond, use method same as Example 2.Thus obtain
PC stretched films C-1.The characteristic of resulting film is evaluated similarly to Example 1.Its result is listed in table 1.
(4) embodiment 4
Except making SrCO3Addition be 1.92g this point beyond, use method same as Example 2.Thus obtain
PC stretched films D-1.The characteristic of resulting film is evaluated similarly to Example 1.Its result is listed in table 1.
(5) comparative example 1
Except not adding SrCO3Beyond this point, method same as Example 1 is used.Thus PC stretched films E- is obtained
1.The characteristic of resulting film is evaluated similarly to Example 1.Its result is listed in table 1.
(6) comparative example 2
Except the SrCO for the use of average major diameter being 200nm3Beyond this point, method same as Example 1 is used.Thus
Obtain PC stretched films F-1.The characteristic of resulting film is evaluated similarly to Example 1.Its result is listed in table 1.
(7) comparative example 3
Except making SrCO3Addition be 15wt% this point beyond, using with the identical method of comparative example 2.Thus
To PC stretched films G-1.The characteristic of resulting film is evaluated similarly to Example 1.Its result is listed in table 1.
(8) comparative example 4
Except using the SrCO not being surface-treated3Beyond this point, method same as Example 2 is used.Thus
Obtain PC stretched films H-1.The characteristic of resulting film is evaluated similarly to Example 1.Its result is listed in table 1.
【Table 1】
Embodiment 1 and comparative example 2 are contrasted and understood, the comparative example 2 big compared to average major diameter, the small implementation of average major diameter
The mist degree of example 1 is relatively low, and birefringence (Δ Nxy × 10-3) value it is relatively low.Understood in addition, embodiment 1 and comparative example 4 are contrasted,
Compared to the comparative example 4 not being surface-treated, the mist degree for the embodiment 1 being surface-treated is relatively low, and birefringence is relatively low.From
And understand, from the transparency and birefringent aspect is showed, preferably averagely small fine of major diameter and has carried out surface treatment
Strontium carbonate fine particles.
Understood in addition, embodiment 1 and embodiment 2 are contrasted, the mist degree that with the addition of the embodiment 2 of surface modifier is less than not
Add the embodiment 1 of surface modifier.It is hereby understood that from the aspect of the transparency is improved, surface modifier is preferably added.
Particularly in embodiment 3, mist degree it is low, less than 1%, and birefringence is essentially a zero.It is hereby understood that it is for for example
Diaphragm of polarizer etc. requires that the transparency is high, hardly shows that birefringent film is particularly suitable.
(evaluation of inverse wave length dispersiveness)
The evaluation of inverse wave length dispersiveness is carried out for the film of embodiment 2, embodiment 3, comparative example 1.In evaluation, in following table
The phase difference value of each film is determined under 7 single wavelengths described in 2.The measure of phase difference value utilizes and the above-mentioned " ((phase of film
Potential difference is evaluated)) " progress of identical method.Then, with R589.3Value on the basis of calculate each wavelength phase difference value ratio
(R/R589.3).Its result is listed in table 2.
【Table 2】
From the result, in the comparative example 1 of strontium carbonate is not contained, it is smaller to show the longer phase difference value of wavelength
" normal wavelength dispersiveness ".In addition, similarly show positive ordinary wave in the embodiment 2 that with the addition of 8 mass % strontium carbonates
Long dispersiveness.On the other hand, the longer phase difference value of wavelength is shown more in the embodiment 3 that with the addition of 16 mass % strontium carbonates
Big " inverse wave length dispersiveness ".
Caused by inverse wave length dispersiveness is due to the wavelength dispersibility difference of makrolon and strontium carbonate.In makrolon
In strontium carbonate, intrinsic birefringent sign symbol is opposite.Therefore, the intrinsic birefringence of makrolon and strontium carbonate is intrinsic double
The difference of refraction is the phase difference value of film.In addition, in makrolon, as wavelength increases, phase difference value reduces, wavelength dependency
Greatly.On the other hand, in strontium carbonate, wavelength dependency is small.Therefore, when the addition of strontium carbonate is few (such as in the present embodiment
In be below 8 mass %), the phase difference expression power of makrolon is more than the phase difference expression power of strontium carbonate, so as to trend
In long wavelength side, the subtractive of the birefringence of makrolon and strontium carbonate is small, and film shows that more long wavelength side phase difference value is smaller
" normal wavelength dispersiveness ".On the other hand, in the addition for the phase difference expression power increase of strontium carbonate compared with makrolon
When measuring (being in the present embodiment more than 16 mass %), the difference increase of the birefringence of makrolon and strontium carbonate, film shows " inverse
Wavelength dispersibility ".
In addition, preferably wavelength dispersibility is the situation for the phase difference that same ratio is shown for each wavelength.For example,
In the phase retardation film of phase difference with 1/4 wavelength, the phase difference value at wavelength 400nm is 100nm, the phase at 600nm
Potential difference value is 150nm, the phase difference value at wavelength 800nm is that wavelength dispersibility as 200nm is that desired wavelength is disperseed.If
And the scattered deviation of desired wavelength is big, then cannot get pure black display in display screen, and is in the color with bluish violet, because
And display quality is deteriorated.In embodiment 3, with long wavelength side is intended to, phase difference value increases, thus it may be said that with close
In the characteristic that desired wavelength is disperseed.Phase retardation film with such wavelength dispersibility is using reflective liquid crystal display screen as representative
Organic el display panel etc. antireflection film, briliancy is improved in film etc. is useful.
<Polymethyl methacrylate (PMMA) film>
(9) embodiment 5
(it is added with SrCO3Doping liquor manufacture method)
Polymethyl methacrylate (hereinafter referred to " PMMA ") 6g is added in dichloromethane 25g, is stirred 3 hours, system
Make PMMA- dichloromethane solutions.Then, the addition surface treatment powder 1 (0.48g) in dichloromethane 10g, is put into ultra sonic bath
In 30 seconds, directly filtered using the film filter in 1 μm of aperture in the case of non-pressurized, making dispersion liquid 1.By PMMA-
Dichloromethane dispersion liquid mixes with dispersion liquid 1, carries out decentralized processing using ultrasonic homogenizer, obtains being added with SrCO3Mix
Miscellaneous liquid I-1.
(PMMA film film build method)
SrCO will be added with using Bake spreader3Doping liquid I-1 with wet coating thickness 11mil be coated with a pet film.By its
2 minutes are dried at 40 DEG C, 15 minutes is dried at 80 DEG C, is dried 30 minutes at 85 DEG C.PMMA film is peeled off by PET film, obtains PMMA
Film I-1.PMMA film I-1 is subjected to free ends list at 90 DEG C using film stretching device (manufactured by well member making, IMC-1A8D types)
Axle is stretched to 2.0 times, obtains PMMA stretched films I-1.The characteristic of resulting film is evaluated similarly to Example 1.Will
Its result is listed in table 3.
(10) embodiment 6
Except making SrCO3Addition be 0.96g this point beyond, use method same as Example 5.Thus obtain
PMMA stretched films J-1.The characteristic of resulting film is evaluated similarly to Example 1.Its result is listed in table 3.
(11) embodiment 7
Except making SrCO3Addition be 1.92g this point beyond, use method same as Example 5.Thus obtain
PMMA stretched films K-1.The characteristic of resulting film is evaluated similarly to Example 1.Its result is listed in table 3.
(12) comparative example 5
Except not adding SrCO3Beyond this point, method same as Example 5 is used.Thus PMMA stretched films are obtained
L-1.The characteristic of resulting film is evaluated similarly to Example 1.Its result is listed in table 3.
(13) comparative example 6
Except the SrCO using average major diameter 200nm3Beyond this point, method same as Example 5 is used.Thus
To PMMA stretched films M-1.The characteristic of resulting film is evaluated similarly to Example 1.Its result is listed in table 3.Need
It is noted that for Δ Nxy × 10-3With Δ P × 10-3, because gonorrhoea occurs for film, thus can not determine that (Δ P is expression face
The index of outer phase difference expression power).
(14) comparative example 7
Except using the SrCO not being surface-treated3Beyond this point, method same as Example 5 is used.Thus
Obtain PMMA stretched films N-1.The characteristic of resulting film is evaluated similarly to Example 1.Its result is listed in table 3.
【Table 3】
Embodiment 7 and comparative example 6 are contrasted and understood, it is big that the mist degree of the small embodiment 7 of average major diameter is less than average major diameter
Comparative example 6.Understand in addition, embodiment 5 and comparative example 7 are contrasted, compared to the comparative example 7 not being surface-treated, carry out
The mist degree of the embodiment 5 of surface treatment is relatively low, and birefringence is relatively low.It is hereby understood that go out in terms of the transparency and performance are birefringent
Hair, preferably averagely small fine of major diameter and the strontium carbonate fine particles being surface-treated.
Particularly, the mist degree of embodiment 7 it is low, less than 1%, and birefringence shows very big negative value.It is hereby understood that its is right
Require that transparency height, the optical film of high birefringence are particularly suitable in the phase retardation film such as polarizer.
(the phase difference evaluation of unstretching film)
(15) embodiment 8PMMA unstretching films
The PMMA before stretching is made using combined amount same as Example 6, doping liquor manufacture method, film build method
Film, in an unstretched state phase difference expression power (Δ P=outside phase difference expression power (Δ Nxy=nx-ny) and face in carry out face
Nx+ny/2-nz measure).Its result is listed in table 4.
(16) comparative example 8
The PMMA film before stretching is made using with the identical combined amount of comparative example 5, doping liquor manufacture method, film build method,
In an unstretched state in carry out face outside phase difference and face phase difference measure.Result is listed in table 4.
【Table 4】
In embodiment 8 and comparative example 8, in face phase difference be outside zero and face phase difference show negative value, thus can
Know for+C plates.Further, since phase difference is zero in face, thus cross Nicols method confirms the non-multilated of polarized condition.Wherein,
If the Δ P for foreign minister's potential difference expression power of being appeared to display is compared, understand that phase difference expression power is high outside the face of embodiment 8.This
It is due to, as described above, needle-like strontium carbonate random orientation in film surface, so that nz increases.According to the result, by for
Needle-like strontium carbonate is added in the film of+C plates, phase difference expression power can be strengthened.On the effect, desired phase difference is being obtained
In the case of be useful for the thin layer of film.
In addition, by adding needle-like strontium carbonate in being like that the film of-C plates in PC unstretching films, additionally it is possible to make each to same
The film (nx=ny=nz) of property.They can be useful in the substrate of flexible display screen as the substitute of glass substrate.
<The measure of surface roughness image>
For the PC stretched films made in embodiment 3, comparative example 1~4, commenting for surface roughness and image is carried out as follows
Valency.Result is listed in table 5.In addition, for the PMMA stretched films made in embodiment 5~7, comparative example 5~7, similarly carry out
The evaluation of surface roughness and image.Result is listed in table 6.
(evaluation of surface roughness)
The evaluation of the surface roughness of film is carried out as follows：The probe-type surface profiler manufactured using Bruker companies
Dektak XT, 10000 μm of scannings are carried out under the following conditions, the thick of the ripple due to film is removed using Gaussian function is approximate
After big ripple, arithmetic mean surface roughness (Ra) is calculated, surface roughness is evaluated.When measure is film-made for cast
The face (side opposite with substrate surface) of atmospheric side be measured.
Scan Type：standard scan
Range：65.5μm
Profile：Hills&Valleys
Stylus：2μm
Stylus Force：15mg
Duration：120sec
Cutoff when ripple removes：80μm
(evaluation of image)
The evaluation of the image (writing as property) of film is carried out as follows：Use SUGA TEST INSTRUMENTS Co. Ltd. systems
The image analyzer ICM-1T made, is measured according to JIS K 7374, using value during light comb width 0.125mm as image
The index of property.It should be noted that measure is carried out in a manner of the face of atmospheric side when pouring into a mould film is configured in light source side.
【Table 5】
| Average grain diameter (nm) | Addition (wt%) | Surface treatment | Surface modifier | Ra(nm) | Image (%)：Light comb width 0.125mm | |
| Embodiment 3 | 35 | 8 | Have | Have | 11.2 | 84.6 |
| Comparative example 1 | Nothing | Nothing | Nothing | Nothing | 10.6 | 39.5 |
| Comparative example 2 | 200 | 8 | Have | Nothing | 26.5 | 3.3 |
| Comparative example 3 | 200 | 15 | Have | Nothing | 479.0 | 51.8 |
| Comparative example 4 | 35 | 8 | Nothing | Have | 1356.0 | 2 |
(※ PC films)
【Table 6】
| Average grain diameter (nm) | Addition (wt%) | Surface treatment | Surface modifier | Ra(nm) | Image (%)：Light comb width 0.125mm | |
| Embodiment 5 | 35 | 8 | Have | Nothing | 13.0 | 82.8 |
| Embodiment 6 | 35 | 16 | Have | Nothing | 10.0 | 89.5 |
| Embodiment 7 | 35 | 32 | Have | Nothing | 6.3 | 81.1 |
| Comparative example 5 | Nothing | Nothing | - | Nothing | 13.1 | 94 |
| Comparative example 6 | 200 | 32 | Have | Nothing | 171.0 | 70.5 |
| Comparative example 7 | 35 | 8 | Have | Nothing | 4317.0 | 2.5 |
(※ PMMA films)
As indicated above, it is known that in any embodiment, arithmetic mean surface roughness Ra value be low value, for 15nm with
Under, surface smoothness is good.In addition we know, in any embodiment, the value of image (total) be high level, for 400% with
On, and with not adding SrCO3Comparative example 1,5 compare, be also the value of equal extent, thus the distinctiveness of the transmission image of film
It is excellent.Especially understand, in any embodiment, in the case where light comb width is narrow light comb width as 0.125mm, the value of image
For high level, be more than 80%, thus the distinctiveness of especially fine image is excellent.
＜ triacetyl celluloses (TAC) film ＞
(17) embodiment 9
(it is added with SrCO3Doping liquor manufacture method)
Triacetyl cellulose (hereinafter referred to as " TAC ") 6g is added in dichloromethane 25g, is stirred 3 hours, makes TAC- bis-
Chloromethanes solution.Then, the addition surface treatment powder 1 (0.6g) in dichloromethane 10g, is put into ultra sonic bath 30 seconds, directly
Connect and filtered using the film filter in 1 μm of aperture in the case of non-pressurized, make dispersion liquid 1.By TAC- dichloromethane point
Dispersion liquid mixes with dispersion liquid 1, carries out decentralized processing using ultrasonic homogenizer, obtains being added with SrCO3Doping liquid I-1.
(TAC film film build method)
SrCO will be added with using Bake spreader3Doping liquid I-1 with the coating of 200 μm of wet coating thickness on a pet film.By its
2 minutes are dried at 40 DEG C, 15 minutes is dried at 80 DEG C, is dried 30 minutes at 85 DEG C.TAC film is peeled off by PET film, obtains TAC film
O-1.The characteristic of resulting film is evaluated similarly to Example 8.Its result is listed in table 7.
(18) embodiment 10
Except use polycarboxylic acid anion type surfactant (B) be used as surface conditioning agent this point in addition to, using with reality
Apply the identical method of example 9.Thus TAC film P-1 is obtained.The characteristic of resulting film is evaluated similarly to Example 8.Will
Its result is listed in table 7.
(19) comparative example 9
Except using the SrCO not being surface-treated3Beyond this point, method same as Example 9 is used.Thus
Obtain TAC film Q-1.The characteristic of resulting film is evaluated similarly to Example 8.Its result is listed in table 7.
【Table 7】
Embodiment 9,10 and comparative example 9 are contrasted and understood, in it with the addition of the embodiment 9,10 of strontium carbonate, Δ P value is
Negative value, show negative phase difference.I.e., from the above results, it is optimal by implementing to the fine elongated piece of strontium carbonate
Surface treatment, can have high transparency and can reduce phase difference outside the face of film.
＜ polyethylene terephthalates (PET) film ＞
(20) embodiment 11
The surface treatment powder 1 used in embodiment 1 is kneaded into PET resin using melting mixing method.In mixing,
Using torque rheometer (LABO PLASTOMILL) 4C150 (Toyo Seiki system) 5 points are carried out at 275 DEG C with mixing speed 60rpm
Clock is kneaded.PET after mixing carries out flaking by heating pressurization in 280 DEG C, 40MPa, carries out the measure of phase difference outside face.Will
Its result is listed in table 8.
(21) comparative example 11
Except not being kneaded SrCO3Beyond this point, method same as in Example 10 is used.Its result is listed in table 8.
【Table 8】
| Particle diameter | Surface treatment | Addition/wt% | Into membranization | Thickness | Rth/nm | ΔP·10-3 | |
| Comparative example 11 | Nothing | - | - | Heating pressurization | 150 | 248.2 | 1.65 |
| Embodiment 11 | 35 | Have | 10 | Heating pressurization | 160 | 44 | 0.27 |
From the above results, SrCO with the addition of by melting mixing method3PET film in, phase difference can reduce outside face.
＜ molecular resins orientation inhibition ＞
Utilize transmission X-rayThe PC of the PC films of scanning, Raman spectroscopy for being used in embodiment 2,3 and comparative example 1 divides
Orientation is evaluated in the face of son.
<Transmission X-rayScanning>
The D8ADVANCE X-ray diffraction devices manufactured using Bruker companies, use transmission X-ray2 θ are consolidated in scanning
16.4 ° are scheduled on, while so as to determine the dependence of angle of diffracted intensity, the rotation of 360 ° of sample is passed through into institute while be measured
The half-peak breadth of obtained periodic pattern is evaluated.For resulting measurement result, the result of comparative example 1 is entered as 100
Row standardization.Its result is listed in table 9.
【Table 9】
<Raman spectroscopy>
The LR laser raman light-dividing device NRS-3300 manufactured using Japan Spectroscopy Corporation, is entered to the orientation of PC molecules
Row evaluation.Under conditions of exciting with solid state laser wavelength 532nm, diffraction grating 600L/mm, what is rotated to sample
It is measured simultaneously with every 225 points of 1 determination part, 1 second time for exposure.By the orientation of resulting periodic pattern evaluation PC molecules
Property.For resulting measurement result, the result of comparative example 1 is standardized as 100.Its result is listed in table 9.
From the above results, by adding fine needle-like SrCO3, the orientations of PC molecules can be suppressed.By in PC, PET
Fine SrCO is added in the high film of big etc. intrinsic birefringence, molecular resin orientation3, can suppress as phase difference performance because
The orientation of the molecular resin of son, phase difference is greatly reduced.
Claims (15)
1. a kind of optical film, it is the optical film that alkaline earth metal carbonate micropowder is dispersed with resin, the spy of the optical film
Sign is,
The average major diameter of above-mentioned alkaline earth metal carbonate micropowder be 10nm~100nm in the range of, relative to above-mentioned optical film
The content of overall above-mentioned alkaline earth metal carbonate micropowder in the range of the mass % of 0.1 mass %~50, in above-mentioned alkaline earth
The surface attachment of metal carbonate micropowder has surfactant.
2. optical film as claimed in claim 1, it is characterised in that above-mentioned alkali carbonate is strontium carbonate.
3. optical film as claimed in claim 1, it is characterised in that in the range of above-mentioned average major diameter is 20nm~50nm, and
And mist degree is less than 1%.
4. optical film as claimed in claim 1, it is characterised in that in the range of above-mentioned content is the mass % of 1 mass %~35.
5. optical film as claimed in claim 1, it is characterised in that above-mentioned resin is selected from by makrolon, polymethyl
Sour methyl esters, cellulose esters, polystyrene, styrene acrylonitrile copolymer, poly- dimethyl ester, polyarylate, polyether sulfone, polyene
Hydrocarbon, Maleimide copolymer, polyethylene terephthalate, PEN, polyimides, polyamides
One or more of group that amine, polyurethane form.
6. optical film as claimed in claim 5, it is characterised in that above-mentioned resin is makrolon.
7. optical film as claimed in claim 6, it is characterised in that it further includes surface modifier.
8. optical film as claimed in claim 6, it is characterised in that in the range of above-mentioned content is the mass % of 8 mass %~16,
Mist degree is less than 1%, and with birefringence in positive face.
9. optical film as claimed in claim 6, it is characterised in that in the range of above-mentioned content is the mass % of 8 mass %~16,
Mist degree is less than 1%, and birefringence is zero in face.
10. optical film as claimed in claim 5, it is characterised in that above-mentioned resin is polymethyl methacrylate.
11. optical film as claimed in claim 10, it is characterised in that above-mentioned content is the mass % of 8 mass %~32 scope
Interior, mist degree is less than 1%, and with birefringence in negative face.
12. the optical film as any one of claim 1~11, it is characterised in that thickness is 20 μm~150 μm of scope
It is interior.
13. the optical film as any one of claim 1~12, it is characterised in that it is stretched film.
14. the optical film as any one of claim 1~13, it is characterised in that arithmetic mean surface roughness Ra is
Below 20nm, and the image under conditions of light comb width 0.125mm is more than 75% (according to JIS K 7374).
15. a kind of image display device, it is characterised in that it possesses the optical film any one of claim 1~14.
Applications Claiming Priority (11)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-162408 | 2015-08-20 | ||
| JP2015162408 | 2015-08-20 | ||
| JP2015174082 | 2015-09-03 | ||
| JP2015-174082 | 2015-09-03 | ||
| JP2015-235550 | 2015-12-02 | ||
| JP2015235550 | 2015-12-02 | ||
| JP2016-055048 | 2016-03-18 | ||
| JP2016055048 | 2016-03-18 | ||
| JP2016146014 | 2016-07-26 | ||
| JP2016-146014 | 2016-07-26 | ||
| PCT/JP2016/072811 WO2017029995A1 (en) | 2015-08-20 | 2016-08-03 | Optical film and image display device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107850717A true CN107850717A (en) | 2018-03-27 |
Family
ID=58052154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680041449.XA Pending CN107850717A (en) | 2015-08-20 | 2016-08-03 | Optical film and image display device |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2017029995A1 (en) |
| KR (1) | KR20180037183A (en) |
| CN (1) | CN107850717A (en) |
| TW (1) | TW201726771A (en) |
| WO (1) | WO2017029995A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110969941A (en) * | 2018-09-28 | 2020-04-07 | 住友化学株式会社 | Optical film |
| CN111712463A (en) * | 2018-05-01 | 2020-09-25 | 宇部兴产株式会社 | Strontium carbonate particles, optical film, and image display device |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7196384B2 (en) * | 2017-09-06 | 2022-12-27 | 大日本印刷株式会社 | Polyimide film, optical film and image display device |
| KR20190090224A (en) * | 2018-01-24 | 2019-08-01 | 도레이첨단소재 주식회사 | Highly transparent optical film |
| JP7385987B2 (en) | 2018-05-16 | 2023-11-24 | 大日本印刷株式会社 | Retardation film, optical laminate, display panel, and image display device using the same |
| JP6738946B1 (en) * | 2018-09-28 | 2020-08-12 | 住友化学株式会社 | Optical film |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140093735A1 (en) * | 2012-09-28 | 2014-04-03 | Ube Material Industries, Ltd. | Acicular strontium carbonate fine powder |
| WO2015060438A1 (en) * | 2013-10-25 | 2015-04-30 | 宇部マテリアルズ株式会社 | Needle-like strontium carbonate fine powder and method for producing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4140884B2 (en) * | 2002-07-04 | 2008-08-27 | 独立行政法人科学技術振興機構 | Method for producing strontium carbonate, non-birefringent optical resin material and optical element |
| JP2005306640A (en) * | 2004-04-20 | 2005-11-04 | Fuji Photo Film Co Ltd | Method for manufacturing crystal of alkaline earth metal carbonate and crystal of alkaline earth metal carbonate |
| JP4397037B2 (en) * | 2004-09-21 | 2010-01-13 | 竹本油脂株式会社 | Method for producing spherical silsesquioxane fine particles |
| US20060068128A1 (en) * | 2004-09-30 | 2006-03-30 | Eastman Kodak Company | Optical films and process for making them |
| JP2006251644A (en) * | 2005-03-14 | 2006-09-21 | Teijin Ltd | Retardation film |
| JP6260759B2 (en) * | 2011-02-15 | 2018-01-17 | 宇部興産株式会社 | Alkaline earth metal carbonate fine powder |
| US9187338B2 (en) * | 2011-02-15 | 2015-11-17 | Ube Material Industries, Ltd. | Process for manufacturing needle-shaped strontium carbonate particles |
-
2016
- 2016-08-03 JP JP2017535484A patent/JPWO2017029995A1/en active Pending
- 2016-08-03 KR KR1020187002022A patent/KR20180037183A/en unknown
- 2016-08-03 CN CN201680041449.XA patent/CN107850717A/en active Pending
- 2016-08-03 WO PCT/JP2016/072811 patent/WO2017029995A1/en active Application Filing
- 2016-08-15 TW TW105125989A patent/TW201726771A/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140093735A1 (en) * | 2012-09-28 | 2014-04-03 | Ube Material Industries, Ltd. | Acicular strontium carbonate fine powder |
| WO2015060438A1 (en) * | 2013-10-25 | 2015-04-30 | 宇部マテリアルズ株式会社 | Needle-like strontium carbonate fine powder and method for producing same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111712463A (en) * | 2018-05-01 | 2020-09-25 | 宇部兴产株式会社 | Strontium carbonate particles, optical film, and image display device |
| CN110969941A (en) * | 2018-09-28 | 2020-04-07 | 住友化学株式会社 | Optical film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2017029995A1 (en) | 2018-06-21 |
| KR20180037183A (en) | 2018-04-11 |
| TW201726771A (en) | 2017-08-01 |
| WO2017029995A1 (en) | 2017-02-23 |
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