CN104254791A - Method for producing polarizing plate - Google Patents

Method for producing polarizing plate Download PDF

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Publication number
CN104254791A
CN104254791A CN201380021480.3A CN201380021480A CN104254791A CN 104254791 A CN104254791 A CN 104254791A CN 201380021480 A CN201380021480 A CN 201380021480A CN 104254791 A CN104254791 A CN 104254791A
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China
Prior art keywords
cellulose ester
acid
film
ester membrane
polaroid
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CN201380021480.3A
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Chinese (zh)
Inventor
笠原睦美
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Konica Minolta Inc
Konica Minolta Opto Inc
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Konica Minolta Opto Inc
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Publication of CN104254791A publication Critical patent/CN104254791A/en
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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
    • 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
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/056—Forming hydrophilic coatings
    • 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
    • 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
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/02—Cellulose; Modified cellulose

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Polarising Elements (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)

Abstract

The problem of the present invention is to obtain excellent adhesiveness between a thin film as a polarizing film and a thin film as a protective film and thereby provide a method for producing a thin film polarizing plate by means of which adhesiveness with the polarizing film is excellent but there is no wrinkling or curling during polarizing plate production, generation of air bubbles due to curling or deformation when the polarizing film panels are bonded, or rise in haze or accompanying reduction in front surface contrast of the liquid crystal display device. The method for producing a polarizing plate of the present invention is a method for producing a polarizing plate whereby a polarizing film (A) having a hydrophilic polymer layer dyed by a dichroic substance and a cellulose ester film (B) are laminated via an adhesive agent on at least one surface of the polarizing film (A), characterized in that the cellulose ester film (B) is subjected to hydrophilization by either plasma treatment or corona treatment, and the surface free energy before and after hydrophilization treatment of the cellulose ester film (B) is a value within a predetermined range.

Description

The manufacture method of polaroid
Technical field
The present invention relates to a kind of manufacture method of polaroid.More specifically, a kind of manufacture method of the polaroid through filming is related to.
Background technology
In recent years, liquid crystal display and utilize the market of the thin display of organic electroluminescent to expand just rapidly.Particularly be called that the expansion in the middle-size and small-size mobile device market of smart mobile phone and Pad is remarkable.
Middle-size and small-size mobile device, while the contrast improving display image, requires the slimming of equipment, lightweight.Therefore, the thin-walled property forming each parts of display device becomes larger problem.
As one of the method solving above-mentioned problem, expect to carry out filming to the polaroid as component parts, require the filming of polarizing coating as the inscape of polaroid and polarizing coating diaphragm.
For this requirement, as the filming of polarizing coating, disclose by being coated with hydrophilic macromolecule and stretching, dye on matrix material, then peel off the method (such as with reference to patent documentation 1 and 2) that matrix material manufactures the polarizing coating of film.According to the method recorded in patent documentation 1 and 2, think that the filming of the polarizing coating that existing stretching polyethylene alcohol mesentery also dyes exists boundary, relative to thickness more than 20 μm, the polarizing coating of the ultrathin membrane of less than 10 μm can be obtained.
On the other hand, as polaroid protective film, there will be a known the thermoplastic resin films such as cellulose esters, polyethylene terephthalate (PET), cyclic olefin polymer (COP), polycarbonate (PC).
Wherein, the cellulose ester membrane as thermoplastic resin film successfully carries out, with the bonding drying of polarizing coating, more widely using than other thermoplastic resin film by the moisture-penetrability of its appropriateness.
But, due to cellulose esters self display hydrophobicity, therefore, with the bonding process of polarizing coating before, need hydrophilicity-imparting treatment, as hydrophilicity-imparting treatment, widely use saponification process most.Saponification process, owing to using the aqueous alkali of high-temperature high concentration, therefore, exists owing to carrying out saponification and makes a part for film stripping in saponification liquid, and film strength (rigidity) disappears such problem points.Particularly consider from the expectation of described filming, if by below cellulose ester membrane filming to 40 μm, then there are the following problems: during the saponification process of described high-temperature high concentration, film strength (rigidity) disappears, when the polarizing coating via bonding agent and filming to above-mentioned less than 10 μm is fitted, the generation of fold (wrinkle) and warpage is remarkable, decrease in yield.
Therefore, expect the surface hydrophilic process replacing saponification process, research in the past has (such as with reference to patent documentation 3 and 4) such as such as corona treatment Cement Composite Treated by Plasma.
But, above-mentioned disclosed method is give hydrophilic technology to the cellulose ester membrane of thick film, if give sufficient water wettability to the cellulose ester membrane of the film of less than 40 μm expected, then there is following problem: find that film strength (rigidity) declines along with the thermal decomposition of film, fold and warpage is produced when polaroid manufactures, in addition, warpage and the bubble caused by distortion is produced when panel attachment, and then, mist degree rises along with the thermal decomposition of film, rise with this mist degree, the front contrast in liquid crystal indicator declines.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2011-100161 publication
Patent documentation 2: Jap.P. No. 4815544 publications
Patent documentation 3: Japanese Unexamined Patent Publication 2000-356714 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2002-82226 publication
Summary of the invention
Invent technical matters to be solved
The present invention's situation and completing in view of the above problems; its technical matters that will solve is; a kind of manufacture method of the polaroid through filming is provided; the method can obtain cementability excellent between film polarizing coating and thin protective film; fold and warpage can not be produced when manufacturing polaroid; can not produce bubble due to warpage and distortion when fitting panel, the front contrast that mist degree rising and thing followed liquid crystal indicator can not occur declines.
For the technical scheme of technical solution problem
The present inventor is studied the reason etc. of the problems referred to above to solve the problems of the technologies described above, in this process, find the manufacture method by a kind of polaroid, pass through the method, fold and warpage can not be produced when manufacturing polaroid, bubble can not be produced due to warpage and distortion when fitting panel, the polaroid through filming that the front contrast obtaining mist degree rising and thing followed liquid crystal indicator can not occur declines, the manufacture method of described polaroid comprises and being laminated on together in the face after hydrophilicity-imparting treatment of polarizing coating (A) with cellulose ester membrane (B), described polarizing coating (A) comprises the hydrophilic macromolecule layer with dichroic substance dyeing, wherein, this cellulose ester membrane (B) carries out hydrophilicity-imparting treatment by any one in Cement Composite Treated by Plasma or corona treatment, and there is specific surface free energy.
That is, above-mentioned problem of the present invention solves by following technical scheme.
1. the manufacture method of a polaroid, the method comprises and polarizing coating (A) and cellulose ester membrane (B) being laminated on together via bonding agent, described cellulose ester membrane (B) is stacked at least one side of this polarizing coating (A) via bonding agent, described polarizing coating (A) has the hydrophilic macromolecule layer with dichroic substance dyeing
Wherein, this cellulose ester membrane (B) has carried out hydrophilicity-imparting treatment by arbitrary process of Cement Composite Treated by Plasma or corona treatment, this cellulose ester membrane (B) surface free energy before hydrophilicity-imparting treatment meets following formula (SI), and this cellulose ester membrane (B) surface free energy after hydrophilicity-imparting treatment meets following formula (SII)
Formula (SI): 0.25≤γ sh/ γ sp<1.5
Formula (SII): 1.5≤γ sh/ γ sp≤4.0
Wherein, the hydrogen bond composition of γ sh presentation surface free energy, γ sp represents dipole component.
2. the manufacture method of the polaroid as described in Section 1, wherein, described cellulose ester membrane (B) is containing the diacetyl cellulose of degree of substitution with acetyl group in 2.0 ~ 2.5 scopes.
The manufacture method of the polaroid 3, as described in Section 1 or Section 2, wherein, the thickness of described polarizing coating (A) is in the scope of 0.5 ~ 10 μm, and the thickness of described cellulose ester membrane (B) is in the scope of 5 ~ 40 μm.
4. the manufacture method of the polaroid as described in Section 3, wherein, the thickness of described cellulose ester membrane (B) is in the scope of 5 ~ 20 μm.
5. the manufacture method of the polaroid according to any one of Section 1 ~ Section 4, wherein, by described polarizing coating (A) the i.e. face contrary with the face be colored of hydrophilic macromolecule layer and described cellulose ester membrane (B) meet described formula (SI) and (SII) formula and the face implementing hydrophilicity-imparting treatment fits together.
6. the manufacture method of the polaroid as described in Section 5, wherein, manufactures polaroid via following operation:
(1), after being coated with described hydrophilic macromolecule layer on thermoplastic resin, the laminated body be made up of this thermoplastic resin and this hydrophilic macromolecule layer is stretched;
(2) by dichroic substance, described hydrophilic macromolecule layer is dyeed;
(3) via bonding agent, barrier film is fitted on the face be colored of described hydrophilic macromolecule layer;
(4) described thermoplastic resin is peeled off from described hydrophilic macromolecule layer; And
(5) face of described hydrophilicity-imparting treatment with the carrying out of laminating septate contrary face and described cellulose ester membrane (B) of described hydrophilic macromolecule layer is fit together.
Invention effect
By technique scheme of the present invention; a kind of manufacture method of the polaroid through filming can be provided; pass through the method; cementability excellent between film polarizing coating and thin protective film can be obtained; fold and warpage can not be produced when manufacturing polaroid; can not produce bubble due to warpage and distortion when fitting panel, the front contrast that can not produce mist degree rising and thing followed liquid crystal indicator declines.
About the performance mechanism of effect of the present invention and the mechanism of action not yet clear and definite, but to be presumed as follows.
According to the research of the present inventor, if find to carry out hydrophilicity-imparting treatment by Cement Composite Treated by Plasma or corona treatment to described cellulose ester membrane (B), and the ratio (γ sh/ γ sp) of the hydrogen bond composition (γ sh) of surface free energy and dipole component (γ sp) is controlled in the scope meeting described relational expression (SII), then can give sufficient water wettability while maintenance film strength (stiffness), fold and warpage can not be produced, good with the cementability of film polarizing coating.
The hydrogen bond composition (γ sh) of described surface free energy and the ratio (γ sh/ γ sp) of dipole component (γ sp) represent the size of hydrogen bond component ratio in surface free energy, usually become large along with carrying out hydrophilicity-imparting treatment.
But, the hydrogen bond composition (γ sh) of surface free energy before treatment and ratio (γ sh/ γ sp) the low film of dipole component (γ sp) have found following problem: before reaching the scope meeting above-mentioned relation formula (SII), damage can be caused to matrix material due to heat etc., there is fold and warpage, mist degree rises, but as long as the ratio of the hydrogen bond composition of surface free energy before treatment (γ sh) and dipole component (γ sp) (γ sh/ γ sp) meets the film of above-mentioned relation formula (SI), then find out can when matrix material does not occur to decompose hydrophilicity-imparting treatment to the surface free energy state same with saponification (namely, meet the state of above-mentioned relation formula (SII)).
In addition, by carrying out Cement Composite Treated by Plasma to the surface that the hydrogen bond composition that diacetyl cellulose is such is abundant in advance, the intensity of Cement Composite Treated by Plasma can being relaxed, the hydrophiling expected can be carried out when keeping film physical property.In addition, because Cement Composite Treated by Plasma has the effect of the concave-convex surface increasing film, therefore, contribute to improving the cementability with polarizing coating surface by anchoring effect.
In addition, when sticking with paste laminating polarizing coating and cellulose ester membrane by water, the boric acid added in the process dyeed to polarizing coating is from this polarizing coating to cellulose ester membrane surface diffusion, and the hydroxyl of the carboxyl that water is stuck with paste and film is cross-linked by boron particles, is undertaken bonding by this effect.
According to above-mentioned opinion, the amount of the boric acid of diffusion can affect bonding, and polarizing coating is thinner, and the content of this boric acid more reduces, thus forms not easily bonding environment.Can infer thus: in the combination of the cellulose ester membrane of film polarizing coating and film, more easily produce poor attachment, encouraged the generation of fold and warpage etc.
The present inventor infers: controlled within the scope of the invention by the ratio (γ sh/ γ sp) of the hydrogen bond composition (γ sh) of the surface free energy after described process and dipole component (γ sp), thus, due to the existence of anchoring effect, even if also can realize carrying out bonding surface state with less boric acid amount, even if use film polarizing coating also can improve its cementability.
Accompanying drawing explanation
Figure 1A has dripped the state of glycerine on microslide;
Figure 1B is the state that placed sample film on glycerine;
Fig. 1 C has dripped the state of glycerine in sample film;
Fig. 1 D is the state that placed cover glass on glycerine;
Fig. 2 illustrates that single-frequency HF voltage used in the present invention applies the skeleton diagram of an example of the plasma processing apparatus of mode;
Fig. 3 illustrates that double frequency HF voltage used in the present invention applies the skeleton diagram of an example of the plasma processing apparatus of mode.
Embodiment
The manufacture method of polaroid of the present invention comprises and polarizing coating (A) and cellulose ester membrane (B) being laminated on together via bonding agent, described cellulose ester membrane (B) is stacked at least one side of this polarizing coating (A) via bonding agent, described polarizing coating (A) has the hydrophilic macromolecule layer with dichroic substance dyeing, wherein, this cellulose ester membrane (B) has carried out hydrophilicity-imparting treatment by arbitrary process of Cement Composite Treated by Plasma or corona treatment, this cellulose ester membrane (B) surface free energy before hydrophilicity-imparting treatment meets above-mentioned formula (SI), and this cellulose ester membrane (B) surface free energy after hydrophilicity-imparting treatment meets above-mentioned formula (SII), utilize this scheme, a kind of polaroid through filming is provided, it can not produce fold and warpage when polaroid manufactures, bubble can not be produced due to warpage and distortion when fitting panel, the front contrast that can not produce mist degree rising and thing followed liquid crystal indicator declines.
This is characterized as Section 1 to the total technical characteristic of the invention of Section 6.
As embodiment of the present invention; from the viewpoint of manifesting effect of the present invention; particularly from the viewpoint of meeting above-mentioned formula (I), preferred above-mentioned cellulose ester membrane (B) is containing the diacetyl cellulose of total acyl substitution in the scope of 2.0 ~ 2.5.In addition, from the viewpoint of the polaroid obtaining not easily warpage, the thickness of preferred above-mentioned polarizing coating (A) is in the scope of 0.5 ~ 10 μm, and the thickness of above-mentioned cellulose ester membrane (B) is in the scope of 5 ~ 40 μm.Particularly preferably the thickness of above-mentioned cellulose ester membrane (B) is in the scope of 5 ~ 20 μm.
As polaroid manufacture method of the present invention, the boron ion used from the viewpoint of dyeing process more easily spreads and improves cementability, preferably by the face contrary with the face be colored of the hydrophilic macromolecule layer of above-mentioned polarizing coating (A) and above-mentioned cellulose ester membrane (B) meet above-mentioned formula (SI) and (SII) formula and the face implementing hydrophilicity-imparting treatment fits together.
Now, at the dyeing face of above-mentioned polarizing coating (A) laminating barrier film, thermoplastic resin is peeled off under the state of laminating barrier film, fit in face after this stripping cellulose ester membrane (B) hydrophilicity-imparting treatment after this manufacture method of face produce fold and warpage when can suppress to manufacture polaroid, therefore preferably.
Below, to the present invention and inscape thereof and be described in detail for implementing mode scheme of the present invention.It should be noted that, in this application, " ~ " is to use containing the implication of numerical value described before and after it as lower limit and higher limit.In addition, by the polaroid manufactured by polaroid manufacture method of the present invention in this manual also referred to as " polaroid of the present invention ".
First polarizing coating of the present invention (A) is described.
< polarizing coating (A) >
Polarizing coating of the present invention (A) obtains as follows: with coating method at thermoplastic resin superimposed layer hydrophilic macromolecule layer, then, preferred enforcement stretch processing forms stretch laminate body, then, by dichroic substance, dyeing process is carried out to this hydrophilic macromolecule layer, give polarization function, then, peel off this thermoplastic resin and obtain polarizing coating (A).Therefore, polarizing coating of the present invention (A) finally refers to above-mentioned hydrophilic macromolecule layer, owing to peeling off above-mentioned thermoplastic resin, therefore can carry out filming and reach less than 10 μm to its thickness.Preferred thickness is the scope of 0.5 ~ 10 μm.
[thermoplastic resin]
The thermoplastic resin used in the present invention plays a role as the matrix material forming hydrophilic macromolecule layer.The thermoplastic resin used in the present invention can use the film same with the diaphragm forming polaroid.
The thermoplastic resin used in the present invention can be roughly divided into the regularly arranged crystalline thermoplastic resin of macromolecule and macromolecule irregular alignment or only some is in amorphism thermoplastic resin that is amorphous or noncrystalline state, and any one all can use.
In addition, no matter be crystalline resin or amorphous resin, all the resin not being in crystalline state or the resin that do not reach crystalline state be called amorphous or amorphous resin.At this, amorphous or amorphous resin is distinguished with the amorphous resin of the character not forming crystalline state and is used.
As crystalline thermoplastic resin, such as can enumerate, comprise tygon (PE), polypropylene (PP) olefine kind resin, comprise the esters resin of polyethylene terephthalate (PET), polybutylene terephthalate (PBT).One of feature of crystalline thermoplastic resin is, usually has following character: by heating and stretch orientation, macromolecule carries out arranging and crystallization occurring.Various change is there is in the physical property of resin according to the degree of crystallization.On the other hand, even the crystalline thermoplastic resin that such as polypropylene (PP), polyethylene terephthalate (PET) are such, also by suppressing to be arranged by the macromolecule heated and stretch orientation causes to suppress crystallization.Repressed for crystallization these polypropylene (PP), polyethylene terephthalate (PET) are called amorphism polypropylene, amorphism polyethylene terephthalate, these are generically and collectively referred to as respectively amorphism olefine kind resin, amorphism esters resin.Such as when polypropylene (PP), there is no the irregular structure of stereoregularity to make by being formed the amorphism polypropylene (PP) that inhibit crystallization.In addition, such as when polyethylene terephthalate (PET), by the m-phthalic acid, 1 of copolymerization as polymerization single polymerization monomer, the modified group that 4-cyclohexanedimethanol is such, that is, copolymerization suppresses the molecule of polyethylene terephthalate (PET) crystallization to make the amorphism polyethylene terephthalate (PET) that inhibit crystallization.
In addition, in the condensed polymer formed at polybasic carboxylic acid (dicarboxylic acid) and polyvalent alcohol (glycol) and ester system resin, as the crystallinity ester system resin used in the present invention, such as, can enumerate: polyethylene terephthalate (PET), polybutylene terephthalate (PBT), PTT (PTT), PEN (PEN), PBN (PBN) etc.These crystallinity ester system resins have the character of the easy crystallization when making membranaceous, but when being prepared at the temperature maintaining amorphous state, can not crystallization rapidly, have stretchability, therefore can be used as thermoplastic resin.If there is crystallization when film forming, then the stretchability of film obviously can decline.In order to ensure the stretchability of film, preferably use crystallization when suppressing masking, thus the material of film forming under the state of amorphous (noncrystalline).
In order to improve processability, the stretchability of film, in the crystallinity ester system resin that can use in the present invention, coordinate plastifier and elastic body.As plastifier, such as, can enumerate: phthalate and the fatty acid ester such as condensed polymer, hexane diacid and condensed polymer, polyesters plastifier, epoxy plasticiser, styrenic polymer, acrylic polymers, terphenyl compounds and substitutive derivative thereof etc.In addition, as elastic body, can enumerate: phenylethylene, olefines, acrylic compounds, polyvinyl chloride-base, ammonia ester class, ester class and nylon-type etc.
The thickness of thermoplastic resin (before stretching) can be suitable for determining, but from the viewpoint of the workability such as intensity and operability, thin layer etc., is generally about 1 ~ 500 μm.Particularly preferably 1 ~ 300 μm, more preferably 5 ~ 200 μm.The thickness of thermoplastic resin when 5 ~ 150 μm particularly preferably.On the other hand, from the viewpoint of the workability such as intensity and operability, the thickness of the thermoplastic resin (after stretching) in stretch laminate body is about 1 ~ 400 μm, is preferably 1 ~ 200 μm, is more preferably 5 ~ 100 μm.In stretch laminate body, the thickness of thermoplastic resin is determined by the thickness of thermoplastic resin (before stretching) and stretching ratio.
[hydrophilic macromolecule layer]
Above-mentioned stretch laminate body has hydrophilic macromolecule layer.Hydrophilic macromolecule layer is containing the layer of hydrophilic macromolecule as principal ingredient, and this hydrophilic macromolecule layer is by dyeing process absorption dichroic substance described later.Thus, hydrophilic macromolecule layer plays a role as polarizing coating (A) in polaroid of the present invention.
About the hydrophilic macromolecule forming hydrophilic macromolecule layer, be not particularly limited, can preferably illustrate polyvinyl alcohol material.As polyvinyl alcohol material, such as, can enumerate polyvinyl alcohol (PVA) and derivant thereof.As the derivant of polyvinyl alcohol (PVA), can polyvinyl formal, Pioloform, polyvinyl acetal etc. be enumerated, can enumerate in addition: the polyvinyl alcohol material obtained by the modification such as Arrcostab, acrylamide of the unsaturated carboxylic acids such as the alkene such as ethene, propylene, acrylic acid, methacrylic acid, butenoic acid.The degree of polymerization of polyvinyl alcohol (PVA) preferably about 100 ~ 10000, more preferably 1000 ~ 10000.Usually saponification degree can be used to be the material of about 80 ~ 100 % by mole.Than that described above, as hydrophilic macromolecule, can enumerate: the processed thing of the partly-hydrolysed thing of ethylene vinyl acetate copolymer class, polyvinyl alcohol (PVA) and the desalination acid treatment thing etc. of Polyvinylchloride.As above-mentioned hydrophilic macromolecule, preferably use the polyvinyl alcohol (PVA) in polyvinyl alcohol material.
Hydrophilic macromolecule layer can also contain the adjuvant such as plastifier, surfactant except above-mentioned hydrophilic macromolecule.As plastifier, can enumerate: polyvalent alcohol and condensation product etc. thereof, such as, can enumerate: glycerine, two glycerine, triglycerin, ethylene glycol, propylene glycol, polyglycol etc.The use amount of plastifier etc. is not particularly limited, but is preferably set to below 20 quality % relative to the solid constituent total amount (100 quality %) of hydrophilic macromolecule layer.
[manufacture method of polarizing coating (A)]
Enumerate the preferable production process of polarizing coating of the present invention (A) below, but the present invention is not limited thereto.
With regard to polarizing coating of the present invention (A), form laminated body at thermoplastic resin superimposed layer hydrophilic macromolecule layer, then carry out stretch processing formation stretch laminate body.This stretch processing can be carried out or process with dyeing carrying out after dyeing process simultaneously, but from the viewpoint of the uniform polarization characteristic of imparting, before dyeing process, carry out this stretch processing can dye along the molecule of the hydrophilic macromolecule of orientation, therefore preferably.
Therefore, in the manufacture method of polarizing coating of the present invention (A), preferably, by coating method at thermoplastic resin superimposed layer hydrophilic macromolecule layer, then, stretch along TD direction (Width) or MD direction (length direction), form the stretch laminate body with polarizing coating through above-mentioned operation.
About the manufacture method of above-mentioned stretch laminate body, be not particularly limited, the record that can refer to existing known opinion and aftermentioned embodiment hurdle suitably manufactures.
If enumerate an example of stretch laminate manufacturing method, then such as can be coated with the aqueous solution containing hydrophilic macromolecule on thermoplastic resin, then carry out drying, stretching and obtain stretch laminate body.As the formation method of stretch laminate body, thermoplastic resin and hydrophilic macromolecule layer directly or be laminated on together via light solidity bond layer, can obtain the laminated body of thermoplastic resin and hydrophilic macromolecule layer integration state thus.
Stretch processing can be implemented to the thermoplastic resin for making stretch laminate body in advance before the aqueous solution of coating containing hydrophilic macromolecule.
The stretch processing forming stretch laminate body can implement unilateral stretching, two-way stretch, oblique extension etc.Unilateral stretching can be any one in the longitudinal stretching carried out along the MD direction of above-mentioned laminated body, the cross directional stretch carried out along the TD direction of laminated body.In cross directional stretch, also can carry out the contraction of stretching edge length direction in edge width direction.As cross directional stretch mode, such as, can enumerate: fix the stiff end unilateral stretching method of one end via stenter and do not fix the free end unilateral stretching method etc. of one end.As longitudinal stretching mode, can enumerate: the pulling method etc. of drawing process, compression stretching method, use stenter between roller.Stretch processing also can be carried out with the multistage.It should be noted that, when the stretch processing carried out laminated body is unilateral stretching, preferred longitudinal stretching.
In addition, about the temperature of laminated body when stretch processing, be not particularly limited, but preferably in the scope of 130 ~ 200 DEG C, more preferably in the scope of 150 ~ 180 DEG C.In addition, in the stretch processing of laminated body, carry out in the mode counting the scope of 1.1 ~ 10 times with the total stretching ratio in whole direction relative to the raw footage of laminated body.Be preferably 2 ~ 6 times, preferred in the scope of 3 ~ 5 times further.
Aqueous solution (coating fluid for the formation of hydrophilic macromolecule) containing hydrophilic macromolecule can be prepared in the water (hot water) of heating by the crushed material of the powder of hydrophilic macromolecule (such as polyvinyl alcohol (PVA)) or hydrophilic macromolecule film, cut-out thing etc. being suitably dissolved in.As the method that will coat containing the aqueous solution of this hydrophilic macromolecule on thermoplastic resin, such as can suitable rolling method, spin-coating method, silk screen rubbing method, spraying process, infusion process, spray-on process, ink-jet method etc. such as choice for use line rod rubbing method, reverse coating, intaglio plate coating.
Carry out drying after thermoplastic resin is coated with the coating fluid for the formation of hydrophilic macromolecule, as baking temperature, be generally the scope of 50 ~ 200 DEG C, be preferably the scope of 80 ~ 150 DEG C.Be generally about 5 ~ 30 minutes drying time.
In addition, as other laminating method of above-mentioned laminated body, by the coetrusion of the formation material of thermoplastic resin and the formation material of aqueous high molecular layer, laminated body can be formed from above-mentioned formation materials of supply such as moulds with an operation.When coextrusion, preferably the formation material of thermoplastic resin and the formation material of hydrophilic macromolecule layer are respectively charged into coextrusion machine, control co-extrusion output and make the thickness of thermoplastic resin and hydrophilic macromolecule layer be expected range.
Next, utilize dichroic substance to carry out dyeing process to stretch laminate body obtained above, thus in hydrophilic macromolecule layer, adsorb dichroic substance and play a role as polarizing coating (A).
Dyeing process is undertaken by making dichroic substance be adsorbed in the hydrophilic macromolecule layer of laminated body.Dyeing processing example is as carried out in the solution (staining solution) by laminated body being impregnated in containing dichroic substance.As staining solution, solution dichroic substance be dissolved in solvent can be used.As solvent, usually can use water, organic solvent having a miscibility with water can also be added.
About the concrete structure of the dichroic substance be adsorbed in hydrophilic macromolecule layer, be not particularly limited, such as, can enumerate iodine and organic dyestuff etc.As organic dyestuff, such as can use Red BR, Red LR, Red R, Pink LB, Rubin BL, Bordeaux GS, Sky Blue LG, lemon yellow, Blue BR, Blue 2R, Navy RY, Green LG, Violet LB, Violet B, Black H, Black B, Black GSP, Yellow 3G, Yellow R, Orange LR, Orange 3R, Scarlet GL, Scarlet KGL, Congo Red, Brilliant Violet BK, Supra Blue G, Supra Blue GL, Supra Orange GL, Direct Sky Blue, Direct Fast Orange S, Fast Black etc.Wherein, from the viewpoint of water-soluble, operation adaptability is such, preferably use iodine as dichroic substance, but from the viewpoint of can further improve staining efficiency, preferably adds iodide further.As these iodide, such as, can enumerate: potassium iodide, lithium iodide, sodium iodide, zinc iodide, silver iodide, lead iodide, cupric iodide, barium iodide, calcium iodide, stannic iodide, titanium iodide etc.The adding proportion of these iodide is preferably 0.01 ~ 10 quality % in above-mentioned staining solution, is more preferably 0.1 ~ 5 quality %.Wherein, preferably add potassium iodide, the ratio (mass ratio) of iodine and potassium iodide preferably in the scope of 1:5 ~ 1:100, more preferably in the scope of 1:6 ~ 1:80, particularly preferably in the scope of 1:7 ~ 1:70.
The dip time of stretch laminate body in staining solution is not particularly limited, usually preferably 15 second ~ scope of 5 minutes, be more preferably 1 ~ 3 minute.In addition, the temperature of staining solution preferably the scope of 10 ~ 60 DEG C, more preferably the scope of 20 ~ 40 DEG C.
After dyeing process, above-mentioned laminated body be impregnated in successively the destainer containing potassium iodide and contain in the crosslinked fluid of boric acid or boron compound and potassium iodide, to being fixed of dichroic substance.Then, if utilize dryer to carry out drying, then the polarizing coating (A) of application type can be obtained.
< cellulose ester membrane (B) >
Then, the cellulose ester membrane (B) that the diaphragm as polaroid of the present invention plays a role is described in detail.In order to represent the function of cellulose ester membrane (B), it is called " diaphragm " or " polaroid protective film " sometimes.In addition, be sometimes called simply " cellulose ester membrane ".
The feature of cellulose ester membrane of the present invention (B) is, carried out hydrophilicity-imparting treatment by arbitrary process of Cement Composite Treated by Plasma or corona treatment, the surface free energy of this cellulose ester membrane (B) before and after hydrophilicity-imparting treatment is in following particular range.
[surface free energy of cellulose ester membrane (B)]
Cellulose ester membrane of the present invention (B) has carried out the diaphragm after hydrophilicity-imparting treatment by arbitrary process of Cement Composite Treated by Plasma or corona treatment; it is characterized in that; the surface free energy of this cellulose ester membrane before hydrophilicity-imparting treatment meets following formula (SI), and the surface free energy of this cellulose ester membrane after hydrophilicity-imparting treatment meets following formula (SII).
Formula (SI): 0.25≤γ sh/ γ sp<1.5
Formula (SII): 1.5≤γ sh/ γ sp≤4.0
Wherein, the hydrogen bond composition of γ sh presentation surface free energy, γ sp represents dipole component.
In the present invention, the hydrogen bond composition of the surface free energy before hydrophilicity-imparting treatment and the ratio (γ sh/ γ sp) of dipole component are preferably in the scope of 0.28 ~ 1.0, preferred in the scope of 0.30 ~ 0.50 further.
The hydrogen bond composition of the surface free energy before hydrophilicity-imparting treatment and the ratio (γ sh/ γ sp) of dipole component are less than 0.25, in order to obtain the sufficient cementability with polarizing coating, need to implement the hydrophilicity-imparting treatment such as Cement Composite Treated by Plasma and corona treatment under stronger condition, now, fire damage etc. is caused to film surface, physical characteristics, the transparency of film are significantly impaired, produce film strength decline, mist degree rises, the front contrast of following liquid crystal indicator declines.
In addition, in order to obtain the sufficient cementability with polarizing coating, the hydrogen bond composition of the surface free energy after hydrophilicity-imparting treatment and the ratio (γ sh/ γ sp) of dipole component are preferably in the scope of 1.8 ~ 3.5, preferred in the scope of 2.0 ~ 3.0 further.
As changing the method for the hydrogen bond composition of surface free energy with the ratio (γ sh/ γ sp) of dipole component, the degree of substitution of change cellulose ethanoate can be enumerated, change structure and addition that substituent carbon number is, changes adjuvant.Can by combinationally using these because of usually the hydrogen bond composition of various change surface free energy and the ratio of dipole component.
The hydrogen bond composition of the surface free energy after hydrophilicity-imparting treatment and the ratio (γ sh/ γ sp) of dipole component are less than 1.5, insufficient to the cementability of hydrophilic polarizing film, in fact cannot manifest effect of the present invention fully.
Before hydrophilicity-imparting treatment or after the hydrogen bond composition of surface free energy and the ratio (γ sh/ γ sp) of dipole component be greater than formula (SI), (SII) higher limit, find that the hydroscopicity of film becomes large, film strength (stiffness) declines, and occurs the problem producing fold and warpage.In addition, produce following problem: temperature and humidity cause the discrepancy of moisture to become large, the environmental change of length of delay and size becomes large.When loading liquid crystal indicator, the change producing visual angle and fascia color becomes problem so greatly.
Therefore, in order to prevent the problems referred to above, need by selecting the raw material type of cellulose ester membrane (B) and hydrophilized surface treatment conditions etc. to control, to make this cellulose ester membrane (B) surface free energy before hydrophilicity-imparting treatment meet above-mentioned formula (SI), and this cellulose ester membrane (B) surface free energy after hydrophilicity-imparting treatment meets above-mentioned formula (SII).
[mensuration of surface free energy]
Surface free energy is obtained with the tack of this reagent by using the known reagent of the dipole component of surface free energy, dispersion component and hydrogen bond composition to measure.
In the present invention, the surface free energy of cellulose ester membrane (B) is measured as follows.
Determinator: solid-liquid surface analytical equipment (DropMaster500, consonance Surface Science Co., Ltd. manufacture)
Assay method: sessile drop method
Environment: temperature 23 DEG C, 55%RH
Normal fluid is dripped on film about 3 μ l, utilize solid-liquid surface analytical equipment (DropMaster 500, consonance Surface Science Co., Ltd. system) for 3 kinds of described normal fluids: the contact angle determination of pure water, nitromethane, diiodomethane and determined solid (cellulose ester membrane (B)) 5 times, on average obtain average contact angle by measured value.With regard to the time of contact angle determination, measure after 60 seconds at dropping reagent.
Then, these three compositions of surface free energy of solid are calculated based on the Fowkes formula of Young-Dupre formula and expansion.
Now, surface free energy analysis software EG-11 (consonance Surface Science Co., Ltd. manufactures) can be used to calculate.
Young-Dupre formula: WSL=γ L (1+cos θ)
WSL: the energy of attachment between liquid/solid
γ L: the surface free energy of liquid
θ: the contact angle of liquid/solid
The Fowkes formula of expansion:
WSL＝2{(γsdγLd) 1/2+(γspγLp) 1/2+(γshγLh) 1/2}
γ L=γ Ld+ γ Lp+ γ Lh: the surface free energy of liquid
γ Ld, γ Lp, γ Lh: the dispersion component of surface free energy, dipole component and hydrogen bond composition
γ s=γ sd+ γ sp+ γ sh: the surface free energy of solid
γ sd, γ sp, γ sh: the dispersion component of surface free energy, dipole component and hydrogen bond composition
Each signal component value (mN/m) of the surface free energy of normal fluid is as known in table 5, therefore can by being obtained each signal component value (γ sd, γ sp, γ sh) of the surface free energy of solid surface by value solution 3 yuan of equations of contact angle.
[cellulose esters]
Cellulose ester membrane of the present invention (B) is preferably containing cellulosic low-grade fatty acid ester.Lower fatty acid in cellulosic low-grade fatty acid ester refers to that carbon number is the fatty acid of less than 6, such as, can use cellulose ethanoate, cellulose diacetate, cellulosic triacetate, cellulose propionate, cellulose butylate etc. and the mixed aliphatic ester such as cellulose acetate propionate, cellulose acetate butyrate.
In above-mentioned; the cellulosic low-grade fatty acid ester particularly preferably used is the diacetyl cellulose of degree of substitution with acetyl group in the scope of 2.1 ~ 2.5; from easily carrying out adjusting and the surface free energy making film before hydrophilicity-imparting treatment meets above-mentioned formula (SI); and the viewpoint that the surface free energy after hydrophilicity-imparting treatment meets above-mentioned formula (SII) is considered, preferably uses this diacetyl cellulose.
As the cellulose of cellulose esters raw material of the present invention, be not particularly limited, can enumerate: cotton linter, wood pulp, mestha etc.In addition, the cellulose esters obtained from them can be used in combination with arbitrary ratio respectively.
The cellulose esters used in the present invention can utilize known method manufacture.Specifically, the method synthesis can recorded with reference to Japanese Unexamined Patent Publication 10-45804 publication.
As commercially available product, can enumerate: LM80, L20, L30, L40, L50 of Daicel company; The acetylcellulose such as Ca398-3, Ca398-6, Ca398-10, Ca398-30, Ca394-60S of Eastman Chemical company.
As cellulose esters, be preferably more than 125000 and lower than 180000 containing number-average molecular weight (Mn), weight-average molecular weight (Mw) is more than 225000 and is the cellulose esters of the scope of 1.8 ~ 2.0 lower than 360000, Mw/Mn.
Number-average molecular weight (Mn) and the molecular weight distribution (Mw) of cellulose esters can use high-performance liquid chromatogram determination.Condition determination is as described below.
Solvent: methylene chloride
Post: Shodex K806, K805, K803G
(Showa electrician (strain) manufactures, and connects use 3)
Column temperature: 25 DEG C
Sample solution concentration: 0.1 quality %
Detecting device: RI Model 504 (manufacture of GL Sciences company)
Pump: L6000 (Hitachi (strain) manufactures)
Flow: 1.0ml/min
Calibration curve: polystyrene standard STK standard uses the calibration curve by 13 sample makings of polystyrene (eastern Cao (strain) manufacture) Mw=1000000 ~ 500.13 samples preferably use at substantially equal intervals.
[adjuvant of cellulose ester membrane]
As long as the surface free energy before hydrophilicity-imparting treatment meets above-mentioned formula (SI) and the surface free energy of surface after hydrophilicity-imparting treatment after hydrophilicity-imparting treatment meets above-mentioned formula (SII), then can add the various adjuvants (plastifier, ultraviolet light absorber, antioxidant, sour agent for capturing, particulate etc.) corresponding with purposes in cellulose ester membrane of the present invention (B).
From the viewpoint of the physical characteristics in the surface free energy controlled before and after hydrophilicity-imparting treatment, raising environmental change and dimensional stability, cellulose ethanoate film (B) of the present invention is preferably containing the ester shown in following general formula (X) or sugar ester.Can improve the physical strength worried during cellulose ester membrane (B) filming declined and moisture permeability increase caused by dimensional stability deterioration etc., particularly preferably.
First, the ester shown in mutual-through type (X) is described.
General formula (X) B-(G-A) n-G-B
(in formula, B represents aliphatics or aromatic monocarboxylate's residue.G represent carbon number be 2 ~ 12 aklylene glycol residue, carbon number be 6 ~ 12 aryl-diol residue or carbon number be 4 ~ 12 oxygen base aklylene glycol residue.A represent carbon number be 4 ~ 12 alkylene dicarboxylic acids residue or carbon number be 6 ~ 12 aryl dicarboxylic acid's residue.N represents the integer of more than 1.)
Above-mentioned ester is the polyester containing making dicarboxylic acid and glycol react the repetitive obtained, and A represents the carboxylic acid residues in ester, and G represents alcohol residue.
The dicarboxylic acid forming polyester is aromatic dicarboxylic acid, aliphatic dicarboxylic acid or ester ring type dicarboxylic acid, is preferably aromatic dicarboxylic acid.Dicarboxylic acid can be a kind of, also can be the potpourri of more than two kinds.
The glycol forming polyester is aromatic diol, aliphatic diol or ester ring type glycol, is preferably aliphatic diol, is more preferably the glycol that carbon number is 1 ~ 4.Glycol can be a kind of, also can be the potpourri of more than two kinds.
Wherein, preferably containing making the glycol being at least 1 ~ 8 containing the dicarboxylic acid of aromatic dicarboxylic acid and carbon number react the repetitive obtained, the glycol being more preferably 1 ~ 8 containing the dicarboxylic acid made containing aromatic dicarboxylic acid and aliphatic dicarboxylic acid and carbon number reacts the repetitive obtained.
Two ends of polyester molecule can end-blocking, also can not end-blocking, but changes the cellulose ester membrane retardation variation caused, preferred end-blocking from the viewpoint of reduction humiture.
As the concrete example of the alkylene dicarboxylic acids of the A of formation general formula (X), comprise by 1,2-ethane dicarboxylic acid (succinic acid), 1,3-propane dicarboxylic acid (glutaric acid), 1,4-butane dicarboxylic acid (hexane diacid), 1, the divalent group that 5-pentanedicarboxylic acid (heptandioic acid), 1,8-octane dicarboxylic acid (decanedioic acid) etc. are derived.As the concrete example of the alkenylene dicarboxylic acids of formation A, can enumerate: maleic acid, fumaric acid etc.As the concrete example of the aryl dicarboxylic acid of formation A, can enumerate: 1,2-benzenedicarboxylic acid (phthalic acid), 1,3-benzene dicarboxylic acid, Isosorbide-5-Nitrae-benzene dicarboxylic acid, 1,5-naphthalene dicarboxylic acids etc.
A can be a kind of, also can be two or more combinations.Wherein, the preferred carbon number of A be 4 ~ 12 alkylene dicarboxylic acids and carbon number be the combination of the aryl dicarboxylic acid of 8 ~ 12.
The divalent group that the aklylene glycol that it is 2 ~ 12 that G in general formula (X) represents by carbon number is derived, by carbon number be 6 ~ 12 the divalent group that is derived of aryl-diol or the divalent group that is derived of the oxygen base aklylene glycol that is 4 ~ 12 by carbon number.
The example of the divalent group that the aklylene glycol being 2 ~ 12 by carbon number in G derives comprises: by ethylene glycol, 1, 2-propylene glycol, 1, ammediol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 2-propylene glycol, 2-methyl isophthalic acid, ammediol, 1, 4-butylene glycol, 1, 5-pentanediol, 2, 2-dimethyl-1, ammediol (neopentyl glycol), 2, 2-diethyl-1, ammediol (3, 3-dihydroxymethyl pentane), 2-normal-butyl-2-ethyl-1, ammediol (3, 3-dihydroxymethyl heptane), 3-methyl isophthalic acid, 5-pentanediol, 1, 6-hexanediol, 2, 2, 4-trimethyl-1, 3-pentanediol, 2-ethyl-1, 3-hexanediol, 2-methyl isophthalic acid, 8-ethohexadiol, 1, 9-nonanediol, 1, 10-decanediol and 1, the divalent group that 12-octadecanol etc. is derived.
The example of the divalent group that the aryl-diol being 6 ~ 12 by carbon number in G is derived comprises: by 1,2-dihydroxy benzenes (catechol), 1, the divalent group that 3-dihydroxy benzenes (resorcinol), Isosorbide-5-Nitrae-dihydroxy benzenes (p-dihydroxy-benzene) etc. are derived.In G by carbon number be 4 ~ 12 the example of divalent group that is derived of oxygen base aklylene glycol comprise: the divalent group be derived by diethylene glycol, triethylene glycol, TEG, dipropylene glycol, tripropylene glycol etc.
G can be a kind of, also can be two or more combinations.Wherein, G is preferably the aklylene glycol that carbon number is 2 ~ 12.
The B of general formula (X) is by the 1 valency group be derived containing aromatic rings monocarboxylic acid or aliphatic monocarboxylic acid.
By being carboxylic acid containing aromatic rings in molecule containing aromatic rings monocarboxylic acid in the 1 valency group be derived containing aromatic rings monocarboxylic acid, can be not only the carboxylic acid of aromatic rings and carboxyl Direct Bonding, also comprise aromatic rings via the carboxylic acid with carboxylic-bond such as alkylidene.Comprised by the example of the 1 valency group be derived containing aromatic rings monocarboxylic acid: by benzoic acid, p-tert-butyl benzoic acid, adjacent toluic acid, a toluic acid, the 1 valency group that is derived toluic acid, mesitylenic acid, ethyl benzoate, n-propylbenzene formic acid, aminobenzoic acid, acetoxy-benzoic acid, phenylacetic acid, 3-phenylpropionic acid etc.
The example of the 1 valency group be derived by aliphatic monocarboxylic acid comprises: the 1 valency group be derived by acetic acid, propionic acid, butyric acid, sad, caproic acid, capric acid, dodecoic acid, stearic acid, oleic acid etc.Wherein, preferably by the carbon number of moieties be 1 ~ 3 the 1 valency group that is derived of alkyl monocarboxylate, more preferably acetyl group (the 1 valency group be derived by acetic acid).
The weight-average molecular weight of above-mentioned polyester is preferably the scope of 500 ~ 3000, is more preferably the scope of 600 ~ 2000.Weight-average molecular weight can be passed through gel permeation chromatography (GPC) and measure.
As the concrete example of the ester shown in general formula (X), the compound that Japanese Unexamined Patent Publication 2009-192681 publication paragraph [0123] ~ [0124] is recorded can be enumerated, but be not limited to these.
In addition, in order to control cellulose ester membrane (B) surface free energy before and after hydrophilicity-imparting treatment, preferably containing sugar ester.
Sugar ester is the sugar ester beyond cellulose esters, namely carries out esterification to whole or a part of OH bases of the sugar such as following monose, disaccharides, trisaccharide or oligosaccharides and the compound that obtains.As sugar, such as, can enumerate: glucose, galactose, mannose, fructose, wood sugar, arabinose, lactose, sucrose, Nystose, 1F-GF4, stachyose, maltitol, lactitol, lactulose, cellobiose, maltose, cellotriose, maltotriose, gossypose and ketose.In addition, also can enumerate: gentiobiose, gentianose, rough gentian tetrose, xylotriose, galactosyl sucrose etc.In these compounds, particularly preferably there is the compound of furanose structure and/or pyranose structure.Wherein, preferably sucrose, ketose, Nystose, 1F-GF4, stachyose etc., more preferably sucrose.In addition, as oligosaccharides, also can preferably use Fructus Hordei Germinatus oligose, isomaltulose, FOS, galactooligosacchari(es, wood oligose.
Monocarboxylic acid for esterified saccharides is not particularly limited, and can use known aliphatic monocarboxylic acid, cycloaliphatic monocarboxylic, aromatic monocarboxylate etc.The carboxylic acid used can be a kind, also can be mixing of more than two kinds.As preferred aliphatic monocarboxylic acid, can enumerate: acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, sad, the saturated fatty acid such as n-nonanoic acid, capric acid, 2-ethyl-hexanoic, undecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, Heptadecanoic acide, stearic acid, nonadecylic acid, arachidic acid, behenic acid, lignoceric acid, cerinic acid, carboceric acid, montanic acid, melissic acid, lacceroic acid; The unsaturated fatty acids etc. such as undecenoic acid, oleic acid, sorbic acid, linoleic acid, leukotrienes, arachidonic acid, octenoic acid.As the example of preferred cycloaliphatic monocarboxylic, can enumerate: sad or their derivant of ring valeric acid, cyclohexylenedinitrilotetraacetic acid, ring.As the example of preferred aromatic monocarboxylate, can enumerate: benzoic acid, benzoic phenyl ring imports the aromatic monocarboxylate of alkyl, alkoxy, cinnamic acid, diphenylglycollic acid, biphenyl carboxylic acids, naphthalene-carboxylic acid, naphthane carboxylic acid etc. have the aromatic monocarboxylate of more than 2 phenyl ring, or their derivant, more specifically, can enumerate: mesitylenic acid, 2, 3-mesitylenic acid, 3, 5-mesitylenic acid, 2, 3, the acid of 4-1,2,3-trimethylbenzene, γ-different Du's acid, Du's acid, 2, 4, 6-trimethylbenzoic acid, α-Yi Du acid, cumfrey, α-toluic acid, hydratropic acid, atropic acid, hydrocinnamic acid, salicylic acid, adjacent, between, paraanisic acid, creosotic acid, adjacent, between, to homosalicylic acid, pyrocatechuic acid, beta-resorcylic acid, vanillic acid, isovanillic acid, veratric acid, adjacent veratric acid, gallic acid, asarylic acid, mandelic acid, to methoxybenzyl formic acid, homovanillic acid, homoveratric acid, adjacent homoveratric acid, phthalonic acid, p-Coumaric Acid, but particularly preferably benzoic acid.In above-mentioned esterification, preferably import the acetyl compounds of acetyl group.
The concrete example of sugar ester used in the present invention can enumerate the compound recorded Japanese Unexamined Patent Publication 2012-230154 publication paragraph [0130] ~ [0138], but is not limited to these.
In addition, the compound shown in the preferred following general formula (Y) of sugar ester.
[chemical formula 1]
General formula (Y)
In formula, R 1~ R 8represent that hydrogen atom, replacement or the carbon number without replacement are alkyl-carbonyl or the replacement of 2 ~ 22 or are the aryl carbonyl of 2 ~ 22 without the carbon number replaced, R 1~ R 8can be identical, also can be different.
The concrete example of the sugar ester shown in general formula (Y) can enumerate exemplary compounds (1-1) ~ (1-23) recorded Japanese Unexamined Patent Publication 2012-230282 publication paragraph [0077] ~ [0078], but is not limited to these.
R 1~ R 8average substitution degree be adjusted to target degree of substitution by regulating reaction time of esterification or the different compound of mixing degree of substitution.
Ester shown in general formula (X) or sugar ester preferably contain the scope of 1 ~ 30 quality % relative to cellulose esters, the scope more preferably containing 5 ~ 25 quality %, particularly preferably containing 5 ~ 20 quality %.
(plastifier)
Cellulose ester membrane of the present invention (B), in order to improve dimensional stability etc., can contain plastifier as required.
Plastifier is not particularly limited, and preferably selects from polybasic carboxylic acid ester plasticizer, glycollic acid ester plasticizer, phthalic ester plasticizer, fatty acid ester plasticiser and polyalcohol ester plasticizer, polyesters plastifier, Acrylic Plasticizer etc.
Wherein, when using two or more plastifier, preferably at least a kind is polyalcohol ester plasticizer.
The plastifier that polyalcohol ester plasticizer is formed for the ester formed by aliphatic polyol more than divalent and monocarboxylic acid, has aromatic rings or cycloalkyl ring in preferred molecule.Be preferably the aliphatic polybasic alcohol ester of 2 ~ 20 yuan.
The polyvalent alcohol that the present invention preferably uses such as following general formula (a) represents.
General formula (a) R1-(OH) n
Wherein, R1 represents the organic group of n valency, and n represents the positive integer of more than 2, OH basis representation alcoholic and/or phenolic hydroxyl group.
As the example of preferred polyvalent alcohol, such as, can enumerate following polyvalent alcohol.
Can enumerate: ribitol, arabite, ethylene glycol, diethylene glycol, triethylene glycol, TEG, 1,2-propylene glycol, 1, ammediol, dipropylene glycol, tripropylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, dibutylene glycol, 1,2,4-butane triol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol, sweet mellow wine, 3-methylpentane-1,3,5-triol, pinacol, D-sorbite, trimethylolpropane, trimethylolethane, xylitol etc.
Particularly preferably triethylene glycol, TEG, dipropylene glycol, tripropylene glycol, D-sorbite, trimethylolpropane, xylitol.
As the monocarboxylic acid used in polyol ester, be not particularly limited, known aliphatic monocarboxylic acid, cycloaliphatic monocarboxylic, aromatic monocarboxylate etc. can be used.From the viewpoint of improving moisture-penetrability, retention, preferably use cycloaliphatic monocarboxylic, aromatic monocarboxylate.
The carboxylic acid used in polyol ester can be a kind, also can be mixing of more than two kinds.In addition, the OH base in polyvalent alcohol can all esterifications, also a part can be retained with the form of OH base.
The concrete compound of polyol ester can enumerate the compound recorded Japanese Unexamined Patent Publication 2009-192681 publication paragraph [0087] ~ [0090], but is not limited to these.
Glycollic acid ester plasticizer is not particularly limited, but preferably can use alkyl phthalyl base alkyl alcohol esters of gallic acid.
As alkyl phthalyl base alkyl alcohol esters of gallic acid, such as can enumerate: methyl phthalyl ylmethyl ethyl glycolate, ethyl phthalyl base ethyl hexanol acid esters, propyl group phthalyl base propyl group ethyl glycolate, butyl phthalyl base butyl alcohol acid esters, octyl group phthalyl Ji Xinji ethyl glycolate, methyl phthalyl base ethyl hexanol acid esters, ethyl phthalyl ylmethyl ethyl glycolate, ethyl phthalyl base propyl group ethyl glycolate, methyl phthalyl base butyl alcohol acid esters, ethyl phthalyl base butyl alcohol acid esters, butyl phthalyl ylmethyl ethyl glycolate, butyl phthalyl base ethyl hexanol acid esters, propyl group phthalyl base butyl alcohol acid esters, butyl phthalyl base propyl group ethyl glycolate, methyl phthalyl Ji Xinji ethyl glycolate, ethyl phthalyl Ji Xinji ethyl glycolate, octyl group phthalyl ylmethyl ethyl glycolate, octyl group phthalyl base ethyl hexanol acid esters etc.
As phthalic ester plasticizer, can enumerate: diethyl phthalate, DMEP, repefral, dioctyl phthalate, dibutyl phthalate, phthalic acid two 2-Octyl Nitrite, dioctyl phthalate, dicyclohexyl phthalate, terephthalic acid (TPA) dicyclohexyl maleate etc.
As citric acid ester plasticizer, can enumerate: citric acid acetyl three methyl esters, acetyl triethyl citrate, acetyl tributyl citrate etc.
As fatty acid ester plasticiser, can enumerate: butyl oleate, methyl acetyl ricinoleate, dibutyl sebacate etc.
As phosphate plasticizer, can enumerate: triphenyl phosphate, tricresyl phosphate, tricresyl phosphate base diphenyl ester, octyl diphenyl phosphate, diphenyl phosphate Biphenyl Ester, trioctyl phosphate, tributyl phosphate etc.
As multi-carboxylate, by more than 2 yuan, preferably the polybasic carboxylic acid of 2 ~ 20 yuan and the ester of alcohol formation formed.In addition, aliphatic polycarboxylic acid is preferably 2 ~ 20 yuan, when aromatic polycarboxylic acid, ester ring type polybasic carboxylic acid, is preferably 3 ~ 20 yuan.
Polybasic carboxylic acid is represented by following general formula (b).
General formula (b) R2 (COOH) m(OH) n
(wherein, the organic group of R2 represents (m+n) valency, m represents the positive integer of more than 2, and n represents the integer of more than 0, COOH basis representation carboxyl, OH basis representation alcoholic or phenolic hydroxyl group.)
The molecular weight of multi-carboxylate is not particularly limited, but is preferably the scope of molecular weight 300 ~ 1000, the more preferably scope of 350 ~ 750.From the viewpoint of improving retention, preferred molecular weight the greater, from the viewpoint of moisture-penetrability, and the compatibility of cellulose esters, preferred molecular weight smaller.
The alcohols used in multi-carboxylate can, for a kind of, also can be the mixing of more than two kinds.
The acid number of multi-carboxylate is preferably below 1mgKOH/g, more preferably below 0.2mgKOH/g.By acid number is set to above-mentioned scope, length of delay can be suppressed with the change of environment, therefore preferably.
It should be noted that, the milligram number of the potassium hydroxide required for acid (carboxyl existed in sample) contained during so-called acid number refers to and in sample 1g.Acid number measures according to JIS K0070.
As particularly preferred multi-carboxylate, can enumerate: triethyl citrate, tributyl citrate, acetyl triethyl citrate (ATEC), acetyl tributyl citrate (ATBC), citric acid benzoyl tributyl, citric acid acetyl three phenyl ester, citric acid acetyl three benzyl ester, dibutyl tartrate, tartrate diacetyl dibutyl ester, tributyl trimellitate, pyromellitic acid four butyl ester etc.
When containing above-mentioned plastifier, with regard to its use amount, the such as preferred scope containing 1 ~ 50 quality % relative to cellulose esters, the scope more preferably containing 5 ~ 35 quality %, the scope particularly preferably containing 5 ~ 25 quality %.
(ultraviolet light absorber)
Ultraviolet light absorber improves permanance by absorbing the ultraviolet of below 400nm, and the transmitance particularly preferably under wavelength 370nm is less than 10%, is more preferably less than 5%, and more preferably less than 2%.
The ultraviolet light absorber used is not particularly limited, such as, can enumerate: oxygen benzophenone compound, benzotriazole compound, salicylate compounds, benzophenone compound, cyanoacrylate compound, compound in triazine class, nickel complex salt compounds, inorganic particle etc.
Such as there is the chloro-2-(3 of 5-, 5-di-t-butyl-2-hydroxy phenyl)-2H-benzotriazole, (2-2H-benzotriazole-2-base)-6-(straight chain and side chain dodecyl)-4-sylvan, 2-hydroxyl-4-behzyloxybenzophenone, 2,4-behzyloxybenzophenone etc., in addition, there are the Tinuvin classes such as Tinuvin 109, Tinuvin 171, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 928, these are the commercially available product that BASF Japanese firm manufactures, and can preferably use.
The ultraviolet light absorber preferably used in the present invention is Benzotriazole Ultraviolet Stabilizer, benzophenone ultraviolet absorbing agent, triazine-based ultraviolet absorbing agent, is particularly preferably Benzotriazole Ultraviolet Stabilizer, benzophenone ultraviolet absorbing agent.
In addition, there is the discotic compounds such as the compound of 1,3,5-triazines ring and also can be preferably used as ultraviolet light absorber.
Polaroid protective film of the present invention also can contain two or more ultraviolet light absorber.
In addition, as ultraviolet light absorber, also preferably polymeric UV absorber can be used, can the particularly preferably ultraviolet light absorber of polymer type recorded of No. 6-148430, Japanese Unexamined Patent Publication.
With regard to the adding method of ultraviolet light absorber, add in preparation liquid or directly add in preparation liquid component after ultraviolet light absorber can being dissolved in the organic solvent such as the alcohol such as methyl alcohol, ethanol, butanols and methylene chloride, methyl acetate, acetone, dioxolanes or their mixed solvent.
Be insoluble to as inorganic particle after the substance migration dissolver of organic solvent and sand mill are scattered in organic solvent and cellulose esters and add in preparation liquid.
The use amount of ultraviolet light absorber is different according to the difference such as kind, service condition of ultraviolet light absorber; but when the dry film thickness of polaroid protective film is 30 ~ 200 μm; be preferably 0.5 ~ 10 quality % relative to cellulose esters, more preferably 0.6 ~ 4 quality %.
(antioxidant)
Antioxidant is also referred to as anti-deterioration agent.When liquid crystal image display device etc. is placed in the high humidity condition of high temperature, sometimes there is the deterioration of cellulose ester membrane.
Antioxidant has the effect such as delaying or prevent cellulose ester membrane from decomposing because of the halogen of the residual solvent amount in cellulose ester membrane and the phosphoric acid of phosphoric acid class plastifier etc., therefore, preferably in above-mentioned cellulose ester membrane (B), contains antioxidant.
As such antioxidant, preferably can use hindered phenol compound, such as can enumerate: 2, 6-BHT, pentaerythrite-four [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester], triethylene glycol-bis-[3-(3 tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester], 1, 6-hexanediol-bis-[3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester], 2, 4-pair-(n-octylthio)-6-(4-hydroxyl-3, 5-di-tert-butyl amido)-1, 3, 5-triazine, 2, 2-sulfo--di ethylene bis [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester], octadecyl-3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester, N, N '-hexa-methylene two (3, 5-di-t-butyl-4-hydroxyl-hydrogen cinnamamide), 1, 3, 5-trimethyl-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) benzene, three-(3, 5-di-tert-butyl-4-hydroxyl benzyl)-isocyanuric acid ester etc.
Particularly preferably BHT, pentaerythrite-four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester], triethylene glycol-bis-[3-(the 3-tert-butyl group-5-methyl-4-hydroxy phenyl) propionic ester].In addition, such as, N can be combinationally used, the Phosphorus processing stabilizers such as the metal passivator of the hydrazine classes such as N '-bis-[3-(3,5-di-tert-butyl-hydroxy phenyl) propiono] hydrazine and three (2,4-di-tert-butyl-phenyl) phosphite ester.
The addition of these compounds is preferably preferred is by quality ratio the scope of 1ppm ~ 1.0% relative to cellulose esters, the more preferably scope of 10 ~ 1000ppm.
(sour agent for capturing)
Cellulose esters at high temperature also can promote because of acid to decompose, therefore, when for cellulose ester membrane of the present invention (B), preferably containing sour agent for capturing.
As spendable sour agent for capturing, as long as make the compound of sour deactivation with acid reaction, can use ad lib, wherein, the compound with epoxy radicals described in preferred United States Patent (USP) No. 4137201 instructions.Epoxy compound as so sour agent for capturing is known in this technical field, comprises the diglycidyl ether of various polyglycols, is particularly carried out the diglycidyl ether etc. of polyglycols that condensation is derived, glycerine by every 1 mole of polyglycols and the oxirane etc. of about 8 ~ 40 moles.In addition, can enumerate, used in vinyl chloride polymer composition in the past, or the becket oxygen compound in the past together used with vinyl chloride polymer composition, epoxidation ether condensation product, the diglycidyl ether of bisphenol-A (namely, 4, 4 '-dihydroxydiphenyl dimethylmethane), epoxidation unsaturated fatty acid ester (particularly the alkyl of the fatty acid of carbon atom 2 ~ 22 and the carbon atom of about 4 ~ 2 formed ester (such as butyl epoxy stearate) etc.) and be representative with the composition of (such as epoxidised soybean oil etc.) such as various epoxidation long-chain fatty acid glyceryl esters and the epoxidized vegetable oil that can list and other unsaturated natural oil (these are sometimes referred to as epoxidation natural glycerin ester or unsaturated fatty acid, these fatty acid are usually containing 12 ~ 22 carbon atoms).In addition, as the commercially available epoxide resin compound containing epoxy radicals, also EPON 815C can preferably be used.
In addition, as spendable sour agent for capturing beyond above-mentioned, comprising: oxetane compound Ji the acylate of oxazoline compound or alkaline-earth metal and pendant acetoacetonate moieties complex compound, material described in 68 ~ 105 sections of Japanese Unexamined Patent Publication 5-194788 publication.
It should be noted that, sour agent for capturing sometimes also referred to as acid scavenger, sour trapping agent, acid binding agent etc., but in the present invention, when using these to exhale title and indifference.
(particulate)
In order to give slipping, preferably in cellulose ester membrane of the present invention (B), add particulate.
As a mean grain size of particulate, preferred below 20nm, the more preferably scope of 5 ~ 16nm, be particularly preferably the scope of 5 ~ 12nm.
These particulates are preferably formed the offspring of the particle diameter of the scope of 0.1 ~ 5 μm and are included in cellulose ester membrane, and preferred mean grain size is the scope of 0.1 ~ 2 μm, more preferably the scope of 0.2 ~ 0.6 μm.Thus, concavo-convex at film surface height of formation about 0.1 ~ 1.0 μm, can give suitable slipping to film surface thus.
The mensuration infiltration type electron microscope (multiplying power 500,000 ~ 2,000,000 times) of a mean grain size of particulate carries out the observation of particle, observes 100 particles, measures particle diameter, asks its mean value, as a mean grain size.
As the apparent specific gravity of particulate, more than preferred 70g/ rises, more preferably the scope of 90 ~ 200g/ liter, is particularly preferably the scope that 100 ~ 200g/ rises.Apparent specific gravity is larger, more can make the dispersion liquid of high concentration, and mist degree, condensation product improve, therefore preferably.In addition, when preparing the preparation liquid of higher-solid concentration as the present invention, can particularly preferably use.
Particulate is preferably the scope of 0.01 ~ 5.0 mass parts relative to cellulose esters 100 mass parts relative to the addition of cellulose esters, and the more preferably scope of 0.05 ~ 1.0 mass parts, most preferably is the scope of 0.1 ~ 0.5 mass parts.When addition is many, kinetic friction coefficient is excellent, and when addition is few, condensation product tails off.
[manufacture method of cellulose ester membrane (B)]
Then, the manufacture method of cellulose ester membrane of the present invention (B) is described.
Cellulose ester membrane of the present invention (B) preferably can use the film manufactured with solution casting method, also preferably can use the film dissolving the tape casting manufacture.
In solution casting method, the manufacture of cellulose ester membrane of the present invention (B) is undertaken by following operation: make cellulose esters and adjuvant be dissolved in solvent the operation preparing rubber cement; By the operation of rubber cement curtain coating on the annular metal supporting mass of loopy moving; The rubber cement of curtain coating is dried to the operation of wet film; From the operation that metal support is peeled off; The operation that stretching or width keep; The operation of further drying; The operation of the film reeled.
The operation preparing rubber cement is described.The concentration of the cellulose esters in preferred rubber cement is denseer, because the drying load of curtain coating after metal support can be reduced, if but the concentration overrich of cellulose esters, then load when filtering increases, and filtering accuracy is deteriorated.As the concentration taking into account above-mentioned situation, the preferably scope of 10 ~ 35 quality %, the more preferably scope of 15 ~ 25 quality %.
The solvent used in rubber cement can be used alone, also can be combinationally used two or more, but from the viewpoint of production efficiency, the good solvent of preferred cellulose esters used in combination and poor solvent, deliquescent from the viewpoint of cellulose esters, preferred good solvent is more.
For the preferable range of the blending ratio of good solvent and poor solvent, good solvent is the scope of 70 ~ 98 quality %, and poor solvent is the scope of 2 ~ 30 quality %.So-called good solvent, poor solvent refer to, the solvent dissolving separately the cellulose esters that will use is defined as good solvent, and swelling or undissolved solvent is separately defined as poor solvent.
The good solvent used in the present invention is not particularly limited, and can enumerate: the organohalogen compounds such as methylene chloride and dioxolanes class, acetone, methyl acetate, methyl acetoacetate etc.Can particularly preferably enumerate methylene chloride or methyl acetate.
In addition, the poor solvent used in the present invention is not particularly limited, such as, can preferably use methyl alcohol, ethanol, normal butyl alcohol, cyclohexane, cyclohexanone etc.In addition, preferably in rubber cement, water is contained with the scope of 0.01 ~ 2 quality %.
In addition, for the solvent for dissolving cellulos ester, the dry solvent removed from film can be passed through in reclamation film manufacturing process, be recycled.
The adjuvant made an addition in cellulose esters sometimes also containing trace in recycling design, such as plastifier, ultraviolet light absorber, polymkeric substance, monomer component etc., even if but also can preferably recycle containing these, recycle after also can carrying out purifying as required.
As the dissolving method of cellulose esters during the rubber cement that preparation is above-mentioned, usual way can be used.If combined heated and pressurization, then can be heated to more than the boiling point under normal pressure.
If add the following heating edge stirring and dissolving of temperature of scope that pressure solvent do not seethe with excitement more than the atmospheric boiling point of solvent, then can prevent the non-dissolved matter of bulk being called as gel and agglomerate, therefore preferably.
In addition, also preferably can use after cellulose esters mixed with poor solvent making it wetting or swelling, add the method that good solvent carries out dissolving further.
Pressurization by the method for the inactive gass such as press-in nitrogen and can be undertaken by heating the method making the vapour pressure of solvent increase.Heating is preferably carried out from outside, the such as easy control of temperature of the device of chuck type, therefore preferably.
Consider from the deliquescent viewpoint of cellulose esters, the heating-up temperature of adding solvent is preferably higher, if but heating-up temperature is too high, then and required pressure becomes large, and throughput rate is deteriorated.
Preferred heating-up temperature is the scope of 45 ~ 120 DEG C, is more preferably the scope of 60 ~ 110 DEG C, more preferably the scope of 70 ~ 105 DEG C.In addition, pressure adjusting is the solvent pressure that can not seethe with excitement at a set temperature.
Or, preferably use hot-cold lysis method, thus, cellulose esters can be made to be dissolved in methyl acetate equal solvent.
Then, the suitable filtering materials such as filter paper are used to filter this cellulose ester solution.As filtering material, in order to remove insolubles etc., the filtering material that preferred filtering precision is less, if but filtering precision is too small, then and there is easily generation filtering material and block such problem.
Therefore, preferred filtering precision is the filtering material of below 0.008mm, more preferably the filtering material of the scope of 0.001 ~ 0.008mm, further the filtering material of the preferred scope of 0.003 ~ 0.006mm.
The material of filtering material is not particularly limited, and can use common filtering material, and the metal filtering materials such as plastic filtering material and stainless steel such as polypropylene, Teflon (registered trademark) do not have coming off of fiber, thus preferably.
Filter, reduce impurity, particularly bright spot foreign matter contained in the cellulose esters of raw material preferably by crossing.
So-called bright spot foreign matter, refer to and 2 polaroids are configured with crossed Nicol state, place blooming etc. betwixt, light is irradiated in the polaroid side from side, when observing from the polaroid side of opposite side, the point (foreign matter) can seen owing to revealing from the light of opposition side, preferred diameter is the bright spot number of more than 0.01mm is 200/cm 2below.
Be more preferably 100/cm 2below, more preferably 50/m 2below, more preferably 0 ~ 10/cm 2below.In addition, the bright spot of preferred below 0.01mm is also less.
The filtration of rubber cement can be undertaken by usual way, but more than the atmospheric boiling point of solvent and add method that the following heating edge of temperature of scope that pressure solvent do not seethe with excitement filters due to the rising of the difference (being called differential pressure) of the filter pressure after before filtration less, thus preferably.
Preferred temperature is the scope of 45 ~ 120 DEG C, is more preferably the scope of 45 ~ 70 DEG C, more preferably the scope of 45 ~ 55 DEG C.
The side that filter pressure is preferably less.Filter pressure is preferably below 1.6MPa, is more preferably below 1.2MPa, more preferably below 1.0MPa.
At this, the curtain coating of rubber cement is described.
The preferred effects on surface of metal support in curtain coating (cast) operation has carried out the supporting mass of mirror finish, as metal support, preferably can use stainless steel band or carry out with foundry goods effects on surface the drum that plating processes.
The width of curtain coating can be set to the scope of 1 ~ 4m.In curtain coating operation the surface temperature of metal support be-50 DEG C ~ lower than the temperature of solvent boiling point, due to temperature higher time, the rate of drying of wet film can be accelerated, therefore preferably, if but too high, then wet film foaming sometimes or planarity are deteriorated.
Preferred supporting mass temperature is the scope of 0 ~ 55 DEG C, further the preferred scope of 25 ~ 50 DEG C.Or, make wet film generation gelation and peel off from drum under the state containing a large amount of residual solvent to be also preferred method by cooling.
The method controlling the temperature of metal support is not particularly limited, and can enumerate, the method for the method of blowing warm braw or cold wind and the rear-face contact making warm water and metal support.Owing to using warm water method effectively can carry out heat trnasfer, it is shorter that the temperature of metal support reaches constant time, therefore preferably.When using warm braw, sometimes use the wind higher than target temperature than temperature.
Good planarity is demonstrated in order to make cellulose ester membrane, when peeling off wet film from metal support, the scope of preferred 10 ~ 150 quality % of residual solvent amount, the more preferably scope of 20 ~ 40 quality % or the scope of 60 ~ 130 quality %, is particularly preferably the scope % of 20 ~ 30 quality or the scope of 70 ~ 120 quality %.
In the present invention, residual solvent amount defines with following formula.
Residual solvent amount (quality %)={ (M-N)/N} × 100
It should be noted that, any time when M is employing manufacture or after manufacturing, N carried out the quality of heating after 1 hour to M at 115 DEG C to the quality of the sample that wet film or film collect.
In addition, in the drying process of cellulose ester membrane, preferably wet film is carried out drying again after metal support peels, residual solvent amount is adjusted to below 1 quality %, more preferably below 0.1 quality %, be particularly preferably the scope of 0 ~ 0.01 quality %.
In film drying process, usually can adopt roller drying mode (making wet film lead to alternately through the multiple rollers configured up and down thus make the mode of its drying) or carry dry mode on one side in stenter mode.
In order to make cellulose ester membrane of the present invention (B), particularly preferably with the stenter mode at the two ends by the clamping such as fixture wet film in the width direction (transverse direction) stretch.Preferably peel off to peel off tension force for below 300N/m.
The method of wet film drying is not particularly limited, hot blast, infrared ray, warm-up mill, microwave etc. usually can be adopted to carry out, but from the viewpoint of simplicity, preferably adopt hot blast to carry out drying.
In the drying process of wet film, baking temperature preferably raises at the scoping phase of 40 ~ 200 DEG C.
For the thickness of cellulose ester membrane of the present invention (B), from the viewpoint of the polaroid obtaining thin and light weight, preferably in the scope of 5 ~ 40 μm, more preferably in the scope of 5 ~ 20 μm.The preferred scope at 10 ~ 20 μm further.If be the thickness of this scope, even if then carry out hydrophilicity-imparting treatment of the present invention and Cement Composite Treated by Plasma or corona treatment also can maintain film physical property.In addition, technical matters once of the present invention can be solved: combine with the polarizing coating (A) of the thickness of less than 10 μm, the generation of warpage can be suppressed, when can prevent polaroid from manufacturing, produce fold, and because warpage and distortion produce bubble when preventing from fitting panel.
In the present invention, cellulose ester membrane can use the film of the scope of width 1 ~ 4m.Particularly preferably can use the film of the scope of width 1.4 ~ 4m, be particularly preferably the scope of 1.6 ~ 3m.If more than 4m, then not easily carry.
In order to give length of delay Ro, Rt of following expectation to cellulose ester membrane, preferably by the control controlling conveyance tension, stretched operation carries out refractive index.
Tension force such as by reducing or improve length direction changes length of delay.
In addition, preferably along length direction (film forming direction) and the direction vertical with this direction in face of film, namely Width successively or simultaneously carries out two-way stretch or unilateral stretching.
Mutually perpendicular two-way stretch multiplying power is preferably final is the scope of 0.8 ~ 1.5 times on curtain coating direction, be the scope of 1.1 ~ 2.5 times in the direction of the width, be preferably the scope of 0.8 ~ 1.0 times on curtain coating direction, be that the scope of 1.2 ~ 2.0 times is carried out in the direction of the width.
The draft temperature preferably scope of 120 ~ 200 DEG C, the more preferably scope of 150 ~ 200 DEG C, stretches below 190 DEG C preferably greater than 150 DEG C further.
Residual solvent preferably in film preferably 20 ~ 0% scope, the preferred scope 15 ~ 0% stretches further.
Specifically, preferably at 155 DEG C and residual solvent be 11% time stretch or at 155 DEG C and residual solvent be 2% time stretch.Or preferably at 160 DEG C and residual solvent is stretch for 11% time, or preferably at 160 DEG C and residual solvent stretch lower than 1% time.
The method of stretching wet film is not particularly limited.Such as can enumerate: give difference to multiple roller, the method utilizing the difference of roller longitudinally to stretch betwixt, the two ends fixing wet film with fixture or pin, by the interval of fixture and pin along working direction expansion thus the method longitudinally stretched, similarly transversely expansion thus the method transversely stretched or the method etc. that stretches along expansion in length and breadth thus along two directions in length and breadth simultaneously.Certainly, these methods can combinationally use.
In addition, when so-called tenter frame process, if drive holder part with linear drive mode, then the stretching that can be well on, can reduce the danger such as fracture, therefore preferably.
The maintenance of these width of film making process or the stretching of transverse direction are carried out preferably by stenter, pin stenter and fixture stenter.
Slow axis or the fast axle of the cellulose ester membrane (B) used in the present invention are present in face, if θ 1 will be set to angle formed by masking direction, then θ 1 is preferably more than-1 ° and less than+1 °, be more preferably more than-0.5 ° and less than+0.5 °, more preferably more than-0.1 ° and less than+0.1 °.
This θ 1 may be defined as the angle of orientation, and the mensuration of θ 1 can use automatic birefringence meter KOBRA-WPR (prince's measuring equipment) to carry out.θ 1 meets above-mentioned each relation and can contribute to obtaining higher brightness, suppress or preventing light leak in display image, also contributes in color liquid crystal display arrangement, obtain loyal chromatic rendition.
The physical property > of < cellulose ester membrane (B)
Preferred 300 ~ 1800g/m when the moisture permeability of cellulose ester membrane of the present invention (B) measures and is scaled thickness 80 μm under temperature 40 DEG C, humidity 90%RH 224h, further preferred 400 ~ 1500g/m 224h, particularly preferably 40 ~ 1300g/m 224h.Moisture permeability can measure according to the method recorded in JIS Z 0208.
Breaking elongation is preferably 5 ~ 80%, more preferably the scope of 10 ~ 50%.Measured by the determination method according to JIS-C-2151, ASTM-D-882.Specifically, use cupping machine to stretch with speed 200mm/min, obtain the intensity (value that tension load value obtains divided by the sectional area of test film) when sample cuts off (fracture) and length growth rate.Tensile elongation is calculated by following formula.
Length growth rate (%)=(L-Lo)/Lo
Lo: the specimen length before test
L: specimen length during fracture
Visible light transmissivity is preferably more than 90%, and more preferably more than 93%.Transmitance such as 25 DEG C, adopt spectrophotometer (U-3210, (strain) Hitachi) transmitance to the Specimen Determination visible ray (615nm) of 13mm × 40mm under 60%RH.
[length of delay]
In the face of cellulose ester membrane of the present invention (B), the length of delay (Rt) of length of delay (Ro) and thickness direction is preferably 0≤Ro, Rt≤70nm when being used as polarizing coating diaphragm.Be more preferably the scope of 0≤Ro≤30nm and the scope of 0≤Rt≤50nm, be more preferably the scope of 0≤Ro≤10nm and the scope of 0≤Rt≤30nm.
Cellulose ester membrane of the present invention (B) also can be used as phase retardation film, and now, length of delay is the scope of 30≤Ro≤100nm and the scope of 70≤Rt≤400nm, is more preferably the scope of 35≤Ro≤65nm and the scope of 90≤Rt≤180nm.
In order to obtain these length of delays, can control with the kind of the kind of cellulose esters, adjuvant, plastifier and amount and stretch processing condition etc.
It should be noted that, length of delay Ro and Rt can be obtained by following formula.
Ro＝(n x-n y)×d
Rt＝((n x+n y)/2-n z)×d
At this, d is the thickness (nm) of film, refractive index n x(refractive index also referred to as largest refractive index, slow-axis direction in the face of film), n y(refractive index in direction at a right angle with slow axis in face), n z(refractive index of the film of thickness direction).
Length of delay Ro and Rt can use automatic birefraction instrument to measure.Such as, can use KOBRA-WPR (prince's measuring equipment (strain)) 23 DEG C, obtain with wavelength 590nm under the environment of 55%RH.
[internal haze]
Cellulose ester membrane (B) after hydrophilicity-imparting treatment of the present invention preferably internal haze value is less than 0.1, is more preferably less than 0.05, more preferably less than 0.03.So-called internal haze refers to the mist degree produced by the dispersion factor of film inside, and so-called inside is the part on more than 5 μm, span film surface.
In order to improve the front contrast of liquid crystal indicator, needing the mist degree reducing cellulose ester membrane, but when mist degree being separated into film internal haze and Surface haze, improving effect to it, inner mist degree impact is larger.
Cement Composite Treated by Plasma or corona treatment condition can be adjusted and surface free energy after making hydrophilicity-imparting treatment of the present invention meets formula (SII), thus internal haze value is adjusted to above-mentioned scope.
This internal haze measures as follows: dripped by the solvent of the refractive index with film refractive index ± 0.05 in film surface, make it form the state of the mist degree can ignoring film surface as far as possible, utilize haze meter to measure.
< internal haze determinator >
Haze meter (nephelometer) (model: NDH 2000, Japanese electric look industry (strain) manufacture)
Light source uses 5V9W halogen lamp, and light receiver uses silicon photocell (band is than looking sensitivity filtrator).
In the present invention, in the mensuration that the mist degree of the film when adopting this device the solvent by refractive index being film refractive index ± 0.05 to be set to film surface carries out, its value is less than 0.05.Measure according to JIS K-7136.
Internal haze is determined as follows carries out.Be described with reference to Figure 1A ~ Fig. 1 D.
First, the blank mist degree 1 of the measuring instrument beyond film is measured.
1. on the microslide of cleaning, drip (0.05ml) glycerine.Now note to be mixed into bubble in drop.Even if glass surface is seen totally, sometimes also can be polluted, therefore, the glass after being cleaned by clean-out system (with reference to Figure 1A) must be used.
2. load cover glass thereon.Even if not according to gland slide, glycerine also can be expanded.
3. be arranged on haze meter and measure blank mist degree 1.
Then, the mist degree 2 of sample is comprised by following step measurements.
4. on microslide, drip glycerine (0.05ml) (with reference to Figure 1A).
5. load sample film to be determined thereon and guarantee not to be mixed into bubble (with reference to Figure 1B).
6. in sample film, drip glycerine (0.05ml) (with reference to Fig. 1 C).
7. load cover glass (with reference to Fig. 1 D) thereon.
8. the laminated body as above made (being followed successively by cover glass/glycerine/sample film/glycerine/microslide from above) is arranged at haze meter, measures mist degree 2.
9. calculate (mist degree 2)-(mist degree 1)=(internal haze of cellulose ester membrane of the present invention (B)).
It should be noted that, cellulose ester membrane (B) is used in the sample of damping after more than 5 hours under 23 DEG C of 55%RH, and in addition, the mensuration of above-mentioned mist degree is all carried out under 23 DEG C of 55%RH.
In addition, as described below for the glass of said determination, glycerine.
Glass: MICRO SLIDE GLASS S9213 MATSUNAMI
Glycerine: Northeast chemistry manufactures deer superfine (purity >99.0%) refractive index 1.47
< surface hydrophilic process >
The feature of cellulose ester membrane of the present invention (B) is, has carried out hydrophilicity-imparting treatment by any one of Cement Composite Treated by Plasma or corona treatment.
The method of Cement Composite Treated by Plasma or corona treatment can adopt existing known various method.In the present invention, particularly preferably using plasma process.
[Cement Composite Treated by Plasma]
Below, Cement Composite Treated by Plasma, the particularly atmospheric plasma treatment of the surface hydrophilic process that can be used for polaroid protective film of the present invention are described.
As Cement Composite Treated by Plasma used in the present invention, technology disclosed in Japanese Unexamined Patent Publication 11-133205 publication, Japanese Unexamined Patent Publication 2000-185362 publication, Japanese Unexamined Patent Publication 11-61406 publication, Japanese Unexamined Patent Publication 2000-147209 publication and Japanese Unexamined Patent Publication 2000-121804 publication etc. can be enumerated.
The atmospheric plasma treatment used in the present invention refers to, to discharge space (between opposite electrode) supply gas under pressure near atmospheric pressure or its, HF voltage is applied to this discharge space, energizing gas forms plasmoid, cellulose ester membrane (B) is exposed in the gas of the plasmoid that this excites, carries out surface treatment thus.Also comprise and cellulose ester membrane (B) surface is directly exposed to the situation in the gas of plasmoid or the stimulating activity kind that formed by plasma discharge and blows situation to cellulose ester membrane (B) surface.The HF voltage putting on the discharge space formed between opposite electrode can be the high frequency of a frequency, also can be the high frequency of two or its above frequency.In the present invention, so-called high frequency refers to the frequency at least with more than 0.5kHz.In the present invention, the frequency of preferred high frequency electric source is more than 50kHz and below 27MHz.
So-called atmospheric pressure or the pressure near it are about 20 ~ 110kPa, in order to obtain the good effect that the present invention records, the preferably scope of 93 ~ 104kPa.
Make by extending the plasma irradiating time input plasma physical efficiency increase and carry out hydrophilicity-imparting treatment fully, if but only increase plasma physical efficiency, then sometimes fire damage etc. is produced to cellulose ester membrane, therefore determine condition preferably by suitable experiment etc.
On the contrary, if the plasma irradiating time is short, then can suppress the damage to cellulose ester membrane, but insufficient with the cementability of polarizing coating, need saponification treatment process (such as with reference to patent documentation: Japanese Unexamined Patent Publication 2009-25603 publication after plasma processing.)。
Electrode when (be sometimes referred to as single-frequency HF voltage apply mode) or the HF voltage process with two frequencies when processing with the HF voltage of a frequency (being sometimes referred to as double frequency HF voltage and applying mode) can use identical electrode, and device itself does not have large difference.
Difference is the wave filter that high frequency electric source has two to follow it, in addition, applies HF voltage by two side's electrodes of opposite electrode.
When single-frequency HF voltage used in the present invention applies mode, a side of opposite electrode is ground-electrode, and the opposing party is for applying electrode, and applying Electrode connection has high frequency electric source, and ground-electrode is ground wire grounded.
The plasma processing apparatus (atmospheric plasma treatment device) using accompanying drawing single-frequency HF voltage to be applied to the mode of mode and double frequency HF voltage applying mode is described respectively.
Fig. 2 represents that single-frequency HF voltage used in the present invention applies the skeleton diagram of an example of the plasma processing apparatus of mode.
The roll shape ground-electrode 135 of the applying electrode (square tubular electrode) 136 being positioned at the applying HF voltage of plasma discharge container 130 inside and the coiled fiber cellulose ester film F be positioned on the downside of it is used to form opposite electrode.Applying electrode 136 can be side by side multiple.Gas G is supplied by the gas supply port 152 of plasma discharge container 10, and by the net by gas G homogenising, edge applies between electrode 136 and applies the inwall circulation of electrode and plasma discharge container 131, is full of the discharge space 13 between opposite electrode with gas G.Utilize high frequency electric source 21 to apply HF voltage to applying electrode 136, cellulose ester membrane F is exposed in the gas G excited in discharge space 132, this cellulose ester membrane F forms film.The frequency of the HF voltage applied is the scope of 50kHz ~ 150MHz.In the present invention, the frequency of preferred high frequency electric source is more than 50kHz and below 27MHz.
If lower than 50kHz, be then difficult to obtain effect of the present invention.In addition, be difficult to form electric discharge more than the frequency of 150MHz and the equipment of needs complexity, in addition, cause owing to producing Potential distribution process uneven, be unsuitable for large area process, from the viewpoint of these, be unsuitable for the present invention.
In hydrophilicity-imparting treatment, via pipe arrangement electrode to be heated by electrode temperature regulating device 160 or cool.As thermoregulator medium, distilled water, wet goods Ins. ulative material preferably can be used.When Cement Composite Treated by Plasma, expect the internal temperature regulating electrode in the mode of the temperature inequality not producing matrix material as far as possible on Width or length direction equably.
Fig. 3 represents that double frequency HF voltage used in the present invention applies the skeleton diagram of an example of the plasma processing apparatus of mode.Between its opposite electrode in the same manner as Fig. 1 between roller electrode (the first electrode) 135 and square tubular electrode group (the second electrode) 136, (discharge space) 132 couples of cellulose ester membrane F carry out Cement Composite Treated by Plasma.
Discharge space 132 between roller electrode 135 and square tubular electrode group 136, HF voltage V1 is applied with frequencies omega 1 pair roller electrode 135 by the first power supply 141, in addition, HF voltage V2 is applied by second source 142 with frequencies omega 2 pairs of square tubular electrode groups (the second electrode) 136.
Between roller electrode 135 and the first power supply 141, arrange the first wave filter 143 with the electric current from the first power supply 141 to the mode that roller electrode 135 flows, this first wave filter is to not easily pass through electric current from the first power supply 141 but easily by the patten's design from the electric current of second source 142.In addition, between square tubular electrode group 136 and second source 142, to the mode that the second electrode flows, the second wave filter 144, second wave filter 144 is set to not easily pass through electric current from second source 142 but easily by the patten's design from the electric current of the first power supply 141 with the electric current from second source.At this, what is called not easily passs through and refers to preferably by means of only less than 20% of electric current, more preferably by means of only less than 10%.On the contrary, so-called easily by refer to preferably by electric current more than 80%, more particularly by more than 90%.
In the present invention, as long as just can use ad lib for the wave filter with character described above.Such as, as the first wave filter, can according to the capacitor of frequency usage number 10 ~ tens thousand of pF of second source or the coil counting μ about H.As the second filtrator, can according to the coil of frequency usage 10 more than the μ H of the first power supply, via these coils or capacitor ground wire grounded, can be used as wave filter thus.
It should be noted that, any one of roller electrode 135 and square tubular electrode group 136 can be set to the first electrode, the first Electrode connection has the first power supply, and in addition, the second Electrode connection has second source.In addition, as long as the first power supply has the ability that can apply the HF voltage (V1>V2) larger than second source.In addition, as long as have the ability that frequency reaches ω 1< ω 2.
The gas G produced in the gas supply device 151 of gas supply device 150 imports in container for plasma treatment 131 from air intake opening 152 after controlling flow.Be full of in discharge space 132 and container for plasma treatment 131 with gas G.
Cellulose ester membrane F be never illustrated film volume extract out and transport or transport from last operation, block thing followed air etc. via deflector roll 164 at nip rolls 165 place, reel while move between square tubular electrode group 136 with the state contacted with roller electrode 135.Apply voltage by both roller electrode 135 and square tubular electrode group 136, between opposite electrode, 132 produce discharge plasma.Cellulose ester membrane F is while contact with roller electrode 135 and reel while be exposed in the gas of plasmoid.Cellulose ester membrane F is wound on not shown up-coiler or also can be delivered to subsequent processing via nip rolls 166, deflector roll 167.Discharge gas body G is excited after process exdischarge from exhausr port 153.
In Cement Composite Treated by Plasma, in order to heat or chill roll electrode 135 and square tubular electrode group 136, the medium liquid-feeding pump P that be have adjusted temperature be sent into two electrodes via pipe arrangement 161, inside electrode, regulate temperature by electrode temperature regulating device 160.It should be noted that, 165 and 166 is the dividing plates be isolated from the outside by container for plasma treatment 131.
In the present invention, the HF voltage of applying can be discontinuous pulsating wave, also can be that continuous print is sinusoidal wave.Can adopt any one, but the continuous print of at least the second electrode side sine wave can carry out the finer and close and Cement Composite Treated by Plasma of high-quality, therefore preferably.
In the present invention, the frequency preferably putting on the HF voltage of the first electrode is the scope of 1 ~ 200kHz and the frequency putting on the HF voltage of above-mentioned second electrode is more than 800kHz.
Preferably 1 ~ the 50W/cm of power density now 2(at this, the cm of denominator 2for producing the area of electric discharge), be more preferably 1.2 ~ 30W/cm 2.Particularly preferably the second electrode is supplied to the power density of above-mentioned scope.
As the high frequency electric source of the plasma processing apparatus that can be used for using in the present invention, such as, can be divided into the first power supply (high frequency electric source) and second source (high frequency electric source) as follows according to frequency.
As the first power supply, can enumerate:
It should be noted that, * is labeled as Haiden research institute pulsed high-frequency power supply (continuous mode and 100kHz).
In addition, as second source (high frequency electric source), can enumerate
Etc. commercially available power supply, all can preferably use.
With regard to the discharging condition in the present invention, preferably apply HF voltage to the discharge space of the first opposed electrode and the second electrode, this HF voltage at least has the composition overlapped by the voltage component of the voltage component of first frequency ω 1 and the second frequency ω 2 higher than above-mentioned first frequency ω 1.
Above-mentioned HF voltage is the composition overlapped by the voltage component of the voltage component of first frequency ω 1 and the second frequency ω 2 higher than above-mentioned first frequency ω 1, and its waveform is the overlapping waveform having the sine wave of the ω 1 of the sine wave of the frequencies omega 2 higher than it on the sine wave of frequencies omega 1.Be not limited to the waveform of sinusoidal wave overlap, both can be pulsating wave, also can one for sinusoidal wave and another is pulsating wave.In addition, tertiary voltage composition can also be contained.But in the present invention, to apply mode same with single-frequency HF voltage, when at least the second electrode side is continuous sine wave, the finer and close and film of high-quality can be obtained.
In addition, as other discharging condition, HF voltage is applied between the first opposed electrode and the second electrode, first HF voltage V1 and the second HF voltage V2 is formed by stacking by this HF voltage, when discharge ionization voltage is set to IV, meet V1 >=IV>V2 or V1>IV >=V2.Preferably meet V1>IV>V2 further.
Applying the such discharging condition of high voltage by adopting, even the discharge gas that the such discharge ionization voltage of such as nitrogen is very high, also starting electric discharge, can high density be maintained and stable plasmoid, high performance film can be formed.
When utilizing said determination and discharge gas is set to nitrogen, its discharge ionization voltage IV is about 3.7kV/mm, therefore, in above-mentioned relation, applying can be carried out excite nitrogen and form plasmoid by the first HF voltage being set to V1 >=3.7kV/mm.
As discharge gas, the rare gas such as nitrogen, helium, argon, air, carbon monoxide, ammonia, hydrogen etc. can be used, these can be used alone as discharge gas, also can be used in combination, but compared with using nitrogen and using the situation of the rare gas such as helium or argon, the high economy of discharge gas can be obtained, therefore particularly preferably.The content of discharge gas is preferably the scope of 70 ~ 100 volume % relative to the total gas flow be supplied in discharge space.
< corona treatment >
In surface hydrophilic process, corona treatment is (also referred to as " Corona discharge Treatment ".) method disclosed in existing known either method, such as Japanese Patent Publication 48-5043 publication, Japanese Patent Publication 47-51905 publication, Japanese Laid-Open Patent Publication 47-28067 publication, Japanese Laid-Open Patent Publication 49-83767 publication, Japanese Laid-Open Patent Publication 51-41770 publication and Japanese Laid-Open Patent Publication 51-131576 publication etc. can be utilized to realize.As the corona treatment for corona treatment, can use at present as the commercially available various corona treatments that the device of the surface modification of plastic foil etc. uses, wherein, the corona treatment with multi-blade electrode of SOFTAL (SOFTAL) company is made up of many electrodes, and, adopt the structure of carrying air between electrode, the heating of film and the low molecule etc. except striping surface spilling can be prevented, therefore energy efficiency is very high, can carry out high corona treatment, be therefore the particularly preferred corona treatment of the present invention.
As the condition of corona treatment, different according to the kind of the corona treatment of the kind of film used, the kind of bonding agent and use etc., but energy density when processing as every 1 time, preferably 20 ~ 400Wmin/m 2left and right.With compared with high-energy process, during with alap energy process, filling material in the deterioration of pending diaphragm, diaphragm can be suppressed to surface spilling etc., effective to raising bonding force.When single treatment is insufficient, carry out the repeatedly process of more than secondary, bonding force improves further.
< polaroid >
Face after the hydrophilicity-imparting treatment of above-mentioned cellulose ester membrane (B) is stacked at least one side of this polarizing coating (A) via bonding agent and is formed by polaroid of the present invention, and described this polarizing coating (A) is made up of the hydrophilic macromolecule layer dyeed through dichroic substance.
When the above-mentioned polarizing coating of lamination (A) and above-mentioned cellulose ester membrane (B); be not particularly limited; but from the viewpoint of preventing the generation of fold and warpage; preferably when above-mentioned thermoplastic resin and the above-mentioned hydrophilic macromolecule layer of the above-mentioned polarizing coating of unstripped formation (A) this hydrophilic macromolecule layer of lamination and above-mentioned cellulose ester membrane (B) hydrophilicity-imparting treatment after face; then this thermoplastic resin is peeled off, at the face laminating polaroid protective film that polarizing coating (A) exposes.
Can to fit above-mentioned cellulose ester membrane (B) at the another side of above-mentioned polarizing coating (A), in addition, other polaroid protective film of also can fitting.
Such as preferably can use commercially available cellulose ester membrane (such as Konica Minolta tuck KC8UX, KC5UX, KC8UCR3, KC8UCR4, KC8UCR5, KC8UY, KC4UY, KC4UE, KC8UE, KC8UY-HA, KC8UX-RHA, KC8UXW-RHA-C, KC8UXW-RHA-NC, KC4UXW-RHA-NC, be Konica Minolta Opto (strain) system above) etc.
Wherein, the polaroid protective film of less than 40 μm is preferably used.
In addition, in the polaroid protective film that the face side of liquid crystal indicator uses, except antiglare layer or transparent hard-coating layer, preferably there is anti-reflection layer, antistatic layer, stain-proofing layer, back coating.
As the bonding agent for fit polaroid protective film and polarizing coating; preferably can use and there is sufficient cementability; transparent and do not suppress the material of polarization function, such as can enumerate: the polyvinyl alcohol bonding agents etc. such as polyesters bonding agent, polyacrylic based adhesives, epoxies bonding agent, cyanoacrylate bonding agent, polyurethanes bonding agent, polyvinyl alcohol (PVA), polyvinyl butyral.In the present invention, the water such as preferred fully saponified type polyvinyl alcohol water solution is stuck with paste.
As another enforcement embodiment of polaroid of the present invention, from the viewpoint of improving cementability further and preventing fold and warpage, also the preferred face through hydrophilicity-imparting treatment by the face contrary with the face be colored of the hydrophilic macromolecule layer of above-mentioned polarizing coating (A) and above-mentioned cellulose ester membrane (B) fits together.
As mentioned above, that thinks for polarizing coating and cellulose ester membrane is bonding, polarizing coating is being dyeed, and the boric acid added in the process of stabilization is diffused into cellulose ester membrane surface from this polarizing coating, the effect that the carboxyl stuck with paste by water and the hydroxyl of film are undertaken being cross-linked by boron ion can promote bonding.Therefore, the amount participating in bonding boron ion has impact, but polarizing coating of the present invention (A) dyes from the face side dichroic substance of hydrophilic macromolecule layer, therefore, there is following concentration gradient: dichroic substance and iodide ion are present in the face side of hydrophilic macromolecule layer in a large number, on the contrary, the side connected with thermoplastic resin of hydrophilic macromolecule layer is then less.Therefore, think that the concentration of the face side iodide ion at hydrophilic macromolecule layer is higher, therefore boron ion is caught by iodide ion and is difficult to be diffused into film side in face side, but it is lower at the relative concentration of this iodide ion of side connected with thermoplastic resin, therefore, boron ion can not be captured and easily be diffused into film side.
Therefore, face after the hydrophilicity-imparting treatment of the face contrary with the face be colored of the hydrophilic macromolecule layer in above-mentioned polarizing coating (A) and above-mentioned cellulose ester membrane (B) is fit together, the boron ionic weight of diffusion is increased relatively, therefore, there is the effect improving cementability further, therefore preferably.
Now, polaroid is manufactured preferably by following operation.
The manufacture method of polaroid is preferably manufactured via following operation:
(1) be coated with above-mentioned hydrophilic macromolecule layer at thermoplastic resin, then, the laminated body be made up of this thermoplastic resin and this hydrophilic macromolecule layer stretched;
(2) by dichroic substance, above-mentioned hydrophilic macromolecule layer is dyeed;
(3) to fit barrier film via bonding agent in the face be colored of above-mentioned hydrophilic macromolecule layer;
(4) above-mentioned thermoplastic resin is peeled off from above-mentioned hydrophilic macromolecule layer; And
(5) above-mentioned hydrophilic macromolecule layer with the face implementing above-mentioned hydrophilicity-imparting treatment of above-mentioned cellulose ester membrane (B) of fitting in laminating septate contrary face.
As above to fit barrier film, the physical strength of polarizing coating can be kept thus to fit on the face contrary with the face of dyeing through dichroic substance cellulose ester membrane (B), therefore, the generation of fold and warpage can be prevented.
Above-mentioned barrier film refers to so-called diffusion barrier, but is not particularly limited, preferably with low cost and maneuverable biaxial stretch-formed polyester film.
< liquid crystal indicator >
Various visual excellent liquid crystal indicator can be made by polaroid of the present invention being used for liquid crystal indicator.
Polaroid of the present invention may be used for the liquid crystal indicator of STN, TN, OCB, HAN, VA (MVA, PVA), the various type of drive such as IPS, OCB.
Be preferably VA (MVA, PVA) type liquid crystal indicator.
Particularly be called as the liquid crystal indicator of the middle-size and small-size mobile device of smart mobile phone and Pad, also can obtain the liquid crystal indicator of the observability excellences such as environmental change is few, light leak reduction, tone inequality, front contrast.
Embodiment
Below, enumerate embodiment and the present invention is described particularly, but the present invention is not limited to these embodiments.It should be noted that, in an embodiment, use the expression of " part " or " % ", but unless otherwise specified, then represent " mass parts " or " quality % ".
Embodiment 1
< has the making > of the stretch laminate body 1 of polarizing coating (A)
The making > of < laminated body
(thermoplastic resin A)
Prepare following film, it can be used as thermoplastic resin A.
As crystallinity ester analog thermoplastic resin, use the amorphous polyethylene terephthalate film (A-PET) (Nobakuria, glass temperature 80 DEG C that Resins Corporation of Mitsubishi manufactures) of thickness 200 μm, length 1000m.
(hydrophilic macromolecule layer)
The pva powder (Japanese VAM POVAL (strain) manufacture, average degree of polymerization 2500, saponification degree more than 99.0 % by mole, trade name: JC-25) as hydrophilic macromolecule is made to be dissolved in the hot water of 95 DEG C, the polyvinyl alcohol water solution of preparation concentration 8 quality %.Used by the polyvinyl alcohol water solution obtained lip to be coated with machine and coat lamination with on above-mentioned thermoplastic resin A, at 80 DEG C, drying 20 minutes, makes the laminated body 1 be made up of thermoplastic resin A and hydrophilic macromolecule layer.It should be noted that, the thickness of hydrophilic macromolecule layer is 12.0 μm.
(stretching process)
Above-mentioned laminated body is implemented at 160 DEG C the free end unilateral stretching of 5.3 times along throughput direction (MD direction).It should be noted that, the thickness of the hydrophilic macromolecule layer after stretching is 5.6 μm.
(dyeing process)
Then, stretch laminate body be impregnated in 60 seconds in the hot bath of 60 DEG C, and containing in the aqueous solution of iodine 0.05 mass parts and potassium iodide 5 mass parts respectively relative to water 100 mass parts, at temperature 28 DEG C, flooded for 60 seconds.Then, under the state keeping anxiety, containing in the boric acid aqueous solution of boric acid 7.5 mass parts and potassium iodide 6 mass parts respectively relative to water 100 mass parts, at temperature 73 DEG C, flooded for 300 seconds.Then, cleaned for 10 seconds with the pure water of 15 DEG C.Under the film after washing is kept nervous state, in dry 300 seconds at 70 DEG C, obtain the stretch laminate body 1 after the dyeing be made up of thermoplastic resin A and hydrophilic macromolecule layer.
The making > of < cellulose ester membrane (B)
The making > of < cellulose ester membrane 101
< particle dispersion liquid >
Particulate (Aerosil R812 Japan Aerosil (strain) manufactures) 11 mass parts
Ethanol 89 mass parts
After above material dissolver is uniformly mixed 50 minutes, carry out (Menton Gorlin) dispersion with Manton-Gaulin mill.
< particulate annex solution >
CE-1 (Daicel company, diacetyl cellulose is added in the dissolution vessel putting into methylene chloride; L20; Degree of substitution with acetyl group 2.41), heating makes it dissolve completely, and the peace then using the long-pending filter paper (strain) of peace to manufacture is amassed filter paper No.244 and filtered it.Cellulose ester solution on one side fully after agitation and filtration, adds particle dispersion liquid wherein at leisure.In addition, carry out disperseing with masher and make the particle diameter of offspring reach prescribed level.With the Finemet NF that Japan's smart line (strain) makes, it is filtered, prepare particulate annex solution.
Methylene chloride 99 mass parts
CE-1 4 mass parts
Particle dispersion liquid 11 mass parts
CE-1 is used to prepare the main preparation liquid of following composition.
First, in dissolved under pressure container, methylene chloride and ethanol is added.Stir while drop into CE-1 at the dissolved under pressure container having put into solvent.It is heated, stirs and make it dissolve completely, then add the adjuvant recorded in 2 kinds of tables 1, make it dissolve.The peace using the long-pending filter paper (strain) of peace to manufacture is amassed filter paper No.244 and is filtered it, prepares main rubber cement.
Particulate annex solution 2 mass parts is added in main rubber cement 100 mass parts, fully mix with online mixer (in Toray silent oscillation pipe mixer Hi-Mixer, SWJ), then, use bandcast device equably curtain coating in the stainless steel band supporting mass of width 1.7m.On stainless steel band supporting mass, making solvent be evaporated to residual solvent amount is 110%, peels off from stainless steel band supporting mass.Apply tension force to stretch in the mode that longitudinal direction (MD) stretching ratio is 1.05 times when peeling off, then, with the stenter clamping wet film both ends being set as 160 DEG C, stretch in the mode that the stretching ratio in width (TD) direction is 1.1 times, residual solvent when this stretching starts is 30%.After stretching, number clock is kept under the state maintaining its width, the tension force of lax Width, then discharge width to keep, be set as that in the dry section of 125 DEG C, conveying carries out drying in 30 minutes again, then cut film end, make the thickness 40 μm of embossing, the cellulose ester membrane 101 of length 1000m that width 1.5m and end have width 1cm, height 5 μm.
The composition > of the main preparation liquid of <
The making > of < cellulose ester membrane 102 ~ 107
As recorded in table 1, change adjuvant and thickness, in addition, make cellulose ester membrane 102 ~ 107 in the same manner as cellulose ester membrane 101.
Adjuvant all respectively adds 7 mass parts relative to cellulose esters 100 mass parts.
It should be noted that, the compound of the following abbreviation in table is as described below.
TPP: triphenyl phosphate
BDP: biphenyl diphenyl ester
PETB: pentaerythritol tetrabenzoate
EPEG: ethyl phthalyl base ethyl hexanol acid esters
B-4: polyalcohol ester plasticizer
X-1, X-15: the ester shown in general formula (X)
Y-11: the sugar ester shown in general formula (Y)
[chemical formula 2]
The making > of < cellulose ester membrane 108
The cellulose esters of use changed to CE-2 (Ca394-60S of Eastman Chemical company: degree of substitution with acetyl group 2.43) and change thickness as was the case with table 1, in addition, making cellulose ester membrane 108 in the same manner as cellulose ester membrane 101.
The making > of < cellulose ester membrane 109
The cellulose esters of use changed to CE-3 (Ca398-30 of Eastman Chemical company: degree of substitution with acetyl group 2.48) and change thickness as was the case with table 1, in addition, making cellulose ester membrane 109 in the same manner as cellulose ester membrane 101.
The making > of < cellulose ester membrane 110
The cellulose esters of use is changed to CE-4 (Ca394-60S and Ca398-6 of Eastman Chemical company 50 to 50 potpourri: degree of substitution with acetyl group 2.28) and change thickness as was the case with table 1; in addition, cellulose ester membrane 110 is made in the same manner as cellulose ester membrane 101.
The making > of < cellulose ester membrane 111
The cellulose esters of use changed to CE-5 (LM80 of Daicel company: degree of substitution with acetyl group 2.15) and change thickness as was the case with table 1, in addition, making cellulose ester membrane 111 in the same manner as cellulose ester membrane 101.
The making > of < cellulose ester membrane 112
The cellulose esters of use changed to CE-6 (LT35 of Daicel company: degree of substitution with acetyl group 2.88) and change thickness as was the case with table 1, in addition, making cellulose ester membrane 112 in the same manner as cellulose ester membrane 101.
The making > of < cellulose ester membrane 113
The cellulose esters of use changed to CE7 (CAP141-20 of Eastman Chemical company: the cellulose acetate propionate of degree of substitution with acetyl group 1.92, propiono degree of substitution 0.74, total degree of substitution 2.66) and change thickness as was the case with table 1; in addition, cellulose ester membrane 113 is made in the same manner as cellulose ester membrane 101.
The making > of < cellulose ester membrane 114
The cellulose esters of use changed to CE8 (cellulose acetate propionate of degree of substitution with acetyl group 1.56, propiono degree of substitution 0.90, total degree of substitution 2.46) and change thickness as was the case with table 1; in addition, cellulose ester membrane 114 is made in the same manner as cellulose ester membrane 101.
The making > of < polaroid
< hydrophilicity-imparting treatment >
(saponification process)
In following each operation, dip treating is carried out to the cellulose ester membrane 101 and 105 of above-mentioned making, implements saponification process thus.
After alkali treatment, carry out successively washing, neutralize, wash, then, dry at 100 DEG C.
(Cement Composite Treated by Plasma)
Use the device recorded in Fig. 2, under the condition shown in table 2 ~ table 4, Cement Composite Treated by Plasma is carried out to the cellulose ester membrane 101 ~ 114 of above-mentioned making.
(corona treatment)
Under the condition shown in table 2 and table 3, corona treatment is carried out to the cellulose ester membrane 105 and 114 of above-mentioned making.
The making > of < polaroid 201 ~ 227
Then, use the cellulose ester membrane after hydrophilicity-imparting treatment, fit with polarizing coating (A) under the condition of following operation 1 ~ 6, make polaroid 201 ~ 227.
To fit in reel-to-reel mode in the hydrophilic macromolecule layer side with the stretch laminate body 1 of polarizing coating (A) of above-mentioned making the face through hydrophilicity-imparting treatment of above-mentioned cellulose ester membrane (B), then, peel off the thermoplastic resin A of stretch laminate body 1, to fit with the combination of identical type in this face the face through hydrophilicity-imparting treatment of above-mentioned cellulose ester membrane (B), make the polaroid of strip and reel.
Operation 1: under the condition of table 2 ~ table 4, carries out hydrophilicity-imparting treatment to cellulose ester membrane 101 ~ 114.
Operation 2: the above-mentioned stretch laminate body 1 with polarizing coating (A) is flooded 1 ~ 2 second in the polyvinyl alcohol (PVA) bonding agent groove of solid constituent 2 quality %.
Operation 3: wipe in operation 2 the excessive bonding agent being attached to stretch laminate body 1 gently, is configured on the face after the hydrophilicity-imparting treatment of the cellulose ester membrane (B) having carried out hydrophilicity-imparting treatment in operation 1.
Operation 4: by the film of lamination in operation 3 with pressure 20 ~ 30N/cm 2, transporting velocity is about laminating in 2m/ minute.
Operation 5: in the dryer of 80 DEG C, by the samples dried 2 minutes made in operation 4, then, peels off the thermoplastic resin A of stretch laminate body 1.Thermoplastic resin A can easily peel off.
Operation 6: the face through hydrophilicity-imparting treatment of above-mentioned cellulose ester membrane (B) of fitting via polyvinyl alcohol (PVA) bonding agent with the combination of identical type on the face of above-mentioned stripping, makes polaroid 201 ~ 227.
The making > of < liquid crystal indicator
Following making for measuring the liquid crystal panel of front contrast, the characteristic of evaluating liquid crystal device.
The polaroid fitting in two sides in advance of the 40 inch display KLV-40V2500 manufactured by SONY is peeled off, and the polaroid 201 ~ 227 of above-mentioned making is fitted in respectively the two sides of the glass surface of liquid crystal cells.
Now, for the laminating direction of its polaroid, make absorption axle towards the direction identical with the polaroid of fitting in advance, make liquid crystal indicator respectively.
[table 3]
[table 4]
High frequency electric source Power Manufacturer
1 100kHz Haiden research institute manufactures
2 13.56MHz Pearl industry manufactures
3 27MHz Pearl industry manufactures
<< assessment item, evaluation method >>
The cellulose ester membrane (B) obtained is used to carry out following evaluation.
(surface free energy)
With the method described above, the surface free energy of film before and after hydrophilicity-imparting treatment is measured.
[table 5]
(internal haze value)
Above-mentioned method is utilized to evaluate internal haze value to the cellulose ester membrane (B) made.
(evaluation of fold/warpage)
The wound condition of visualization strip polaroid, evaluates whether produce fold.
In addition, to each polaroid 201 ~ 227 obtained, the rectangle of Width 30cm × length direction 20cm is cut respectively in substantially central portion, 23 DEG C, under the environment of relative humidity 80%, horizontal base plate is placed 24 hours, then the warped shapes of visualization polaroid, carries out the evaluation of fold/warpage according to following standard.
, there is not the generation of fold/warpage in ◎: the state of general planar;
Zero: do not produce fold, only 4 angles are floated, and confirm the generation of more weak warpage, but its quality is no problem in practical;
△: the generation confirming the generation of fold, significantly warpage is unworkable warpage;
×: the generation of fold is obvious, and the state of warpage is compact, and its quality is extremely unworkable.
(with the cementability of polarizing coating)
The polaroid obtained is placed 24 hours under the environment of 23 DEG C of relative humidity 55%, then, peels bonding plane with hand, the degree of visualization material damage and fissility, with following standard evaluation cementability.
Zero: material (matrix material) destroys
△: a part of material (matrix material) destroys, but there is the area of the interface peel of polaroid protective film and polarizing coating
×: peel off at the interface of polaroid protective film and polarizing coating
The situation that interface is not peeled off is that cementability is good.
(bubble)
Air adsorption type polaroid laminating apparatus is used the polaroid of above-mentioned making to be fitted in the glass surface of liquid crystal cells.With following standard, difficulty evaluation is entered to bubble now.After laminating, 45 DEG C, 0.45MPa, under 15 points of such conditions, carry out autoclave (pressure debubble) process.With following standard, bubble is evaluated.
◎: unconfirmed to bubble
Zero: there is bubble end, but become not obvious after autoclave process
△: have 1 ~ 3 bubble, also can confirm bubble after autoclave process
×: there are more than 4 bubbles, after autoclave process, also can confirm bubble
As long as bubble is the evaluation of more than zero, then practical no problem.
(front contrast ratio of liquid crystal indicator)
Respectively the front contrast of liquid crystal indicator is measured.The mensuration of front contrast utilizes the front contrast determinator (EZ-contrast) of ELDIM Inc. to carry out, when measuring white display and black display time light quantity.Measurement result utilized the value of front contrast to distinguish quality as follows, carry out classification.
Zero: front contrast ratio=more than 3000:1
△: front contrast ratio=2999:1 ~ 2000:1
×: front contrast ratio=below 1999:1
Above various evaluation results are gathered and is shown in table 1 and table 2.
Result is as shown in Table 2 clearly known, polaroid of the present invention relative to comparative example, the generation of the bubble when generation of internal haze value, fold/warpage, cementability, panel attachment with polarizing coating and the evaluation result of front contrast excellent.Namely, based on this result, knownly utilize said method of the present invention, can provide as follows through the manufacture method of the polaroid of filming, by the method, can obtain with polarizing coating excellent in adhesion, fold and warpage can not be produced when manufacturing polaroid and warpage can not be produced when polarizing coating panel attachment and bubble caused by being out of shape, the polaroid that mist degree rises and the front contrast of thing followed liquid crystal indicator declines can not be produced.
Embodiment 2
The making > of < polaroid 301 and 302
Following operation is utilized to make polaroid 301 and 302.
Operation 1: in the hydrophilic macromolecule layer side with the stretch laminate body 1 of polarizing coating (A) of above-mentioned making via bonding agent laminating thickness be that the PET film of 100 μm is as barrier film.
Operation 2: peel off thermoplastic resin A from stretch laminate body 1.
Operation 3: the polarizing coating (A) of band barrier film is flooded 1 ~ 2 second in the polyvinyl alcohol (PVA) bonding agent groove of solid constituent 2 quality %.
Operation 4: the excessive bonding agent wiping in operation 3 polarizing coating (A) being attached to band barrier film gently, then, the face through hydrophilicity-imparting treatment of the cellulose ester membrane 105-3 and 107 through hydrophilicity-imparting treatment made in embodiment 1 is configured at polarizing coating (A).
Operation 5: by the film of lamination in operation 4 with pressure 20 ~ 30N/cm 2, transporting velocity is about laminating in 2m/ minute.
Operation 6: in the dryer of 80 DEG C, by the samples dried 2 minutes made in operation 5, then, peels off barrier film from the polaroid being fitted with polarizing coating (A) and cellulose ester membrane.
Operation 7: with the face through hydrophilicity-imparting treatment of the combination of identical type via polyvinyl alcohol (PVA) bonding agent laminating cellulose ester membrane 105-3 and 107 on the face after above-mentioned stripping, make polaroid 301 and 302.
<< assessment item, evaluation method >>
(with the cementability (loop test) of polarizing coating)
By the polaroid that obtains under the environment of 23 DEG C of relative humidity 10% and the environment of 40 DEG C of relative humidity 80%, repeat the loop tests that 10 times are respectively placed 24 hours respectively.Then, peel bonding plane with hand, the degree of visualization material damage and fissility, with following standard evaluation cementability.
Zero: the surface of cellulose ester membrane and polarizing coating is not peeled off, material (matrix material) destroys
△: a part of material (matrix material) destroys, but there is the area of stripping in the interface that there is polaroid protective film and polarizing coating
×: the interface of polaroid protective film and polarizing coating is peeled off
Surface does not have situation about peeling off to be that cementability is good.
Show the result in table 6.
[table 6]
As shown in Table 6, cellulose ester membrane 105-3 and 107 after the hydrophilicity-imparting treatment meeting formation of the present invention is fitted in the face contrary with the face of dyed process of polarizing coating (A) and the polaroid 301 and 302 made compared with the polaroid of the present invention 208 made in embodiment 1, improve further with the result of the cementability (loop test) of polarizing coating.
Industrial applicibility
By the manufacture method of polaroid of the present invention, can provide with polarizing coating excellent in adhesion, fold and warpage can not be produced when polaroid manufactures and warpage can not be produced when polarizing coating panel attachment and bubble caused by being out of shape, the polaroid through filming that mist degree rises and the front contrast of thing followed liquid crystal indicator declines can not be produced, preferably in liquid crystal indicator, possess this polaroid.
Symbol description
GL glass
Gr glycerine
SF sample film
F cellulose ester membrane
G discharge gas
G exexcite discharge gas
P liquid-feeding pump
130 atmospheric plasma treatment devices
131 atmospheric plasma treatment containers
132 discharge spaces
135 roller electrodes (the first electrode)
136 square tubular electrode groups (the second electrode)
140 electric field bringing devices
141 first power supplys
142 second sources
143 first wave filters
144 second wave filters
150 gas supply devices
151 gas generation apparatus
152 air intake openings
153 exhausr ports
160 electrode temperature regulating devices
161 pipe arrangements
164,167 deflector rolls
165,166 nip rolls
168,169 dividing plates

Claims (6)

1. the manufacture method of a polaroid, the method comprises: polarizing coating (A) and cellulose ester membrane (B) are laminated on together via bonding agent, described cellulose ester membrane (B) is stacked at least one side of this polarizing coating (A) via bonding agent, described polarizing coating (A) has the hydrophilic macromolecule layer dyeed by dichroic substance
Wherein, this cellulose ester membrane (B) has carried out hydrophilicity-imparting treatment by arbitrary process of Cement Composite Treated by Plasma or corona treatment, this cellulose ester membrane (B) surface free energy before hydrophilicity-imparting treatment meets following formula (SI), and this cellulose ester membrane (B) surface free energy after hydrophilicity-imparting treatment meets following formula (SII)
Formula (SI): 0.25≤γ sh/ γ sp<1.5
Formula (SII): 1.5≤γ sh/ γ sp≤4.0
In formula, hydrogen bond composition, the γ sp of γ sh presentation surface free energy represent dipole component.
2. the manufacture method of polaroid as claimed in claim 1, wherein, described cellulose ester membrane (B) is containing the diacetyl cellulose of degree of substitution with acetyl group in 2.0 ~ 2.5 scopes.
3. the manufacture method of polaroid as claimed in claim 1 or 2, wherein, the thickness of described polarizing coating (A) is in the scope of 0.5 ~ 10 μm, and the thickness of described cellulose ester membrane (B) is in the scope of 5 ~ 40 μm.
4. the manufacture method of polaroid as claimed in claim 3, wherein, the thickness of described cellulose ester membrane (B) is in the scope of 5 ~ 20 μm.
5. the manufacture method of the polaroid according to any one of Claims 1 to 4, wherein, by described polarizing coating (A) the i.e. face contrary with the face of dyeing of hydrophilic macromolecule layer and described cellulose ester membrane (B) meet described formula (SI) and formula (SII) and the face implementing hydrophilicity-imparting treatment fits together.
6. the manufacture method of polaroid as claimed in claim 5, wherein, manufactures polaroid via following operation:
(1), after being coated with described hydrophilic macromolecule layer on thermoplastic resin, the laminated body be made up of this thermoplastic resin and this hydrophilic macromolecule layer is stretched;
(2) by dichroic substance, described hydrophilic macromolecule layer is dyeed;
(3) via bonding agent, barrier film is fitted on the face of having dyeed of described hydrophilic macromolecule layer;
(4) described thermoplastic resin is peeled off from described hydrophilic macromolecule layer; And
(5) face of described hydrophilicity-imparting treatment with the carrying out of laminating septate contrary face and described cellulose ester membrane (B) of described hydrophilic macromolecule layer is fit together.
CN201380021480.3A 2012-04-24 2013-04-18 Method for producing polarizing plate Pending CN104254791A (en)

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CN105247395B (en) * 2014-03-26 2018-09-14 Lg化学株式会社 The method of polarization element of the manufacture containing local bleached area, the method for manufacturing the method for polarization element roller and manufacturing monolithic polarizing element
CN107076901B (en) * 2014-09-09 2019-08-16 住友化学株式会社 The manufacturing method of polarization plates and liquid crystal display panel
JP6075424B2 (en) * 2014-09-30 2017-02-08 住友化学株式会社 Polarizing plate, liquid crystal display device, and organic electroluminescence display device
JP2016071349A (en) * 2014-09-30 2016-05-09 住友化学株式会社 Production method of polarizing laminate film and polarizing plate
JP6776566B2 (en) * 2015-05-29 2020-10-28 三菱ケミカル株式会社 Polyvinyl alcohol-based film, polarizing film, and method for producing polyvinyl alcohol-based film
JP6798109B2 (en) 2016-01-21 2020-12-09 横浜ゴム株式会社 Method of surface treatment of members and method of manufacturing laminated members
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JP7411520B2 (en) * 2020-09-02 2024-01-11 日東電工株式会社 Polarizing plate, polarizing plate with retardation layer, and organic electroluminescent display device

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JPWO2013161647A1 (en) 2015-12-24

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Application publication date: 20141231