CN1720284A - Alkali saponification method for cellulose acylate film, a surface saponified cellulose acylate film and an optical film utilizing the same - Google Patents

Alkali saponification method for cellulose acylate film, a surface saponified cellulose acylate film and an optical film utilizing the same Download PDF

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CN1720284A
CN1720284A CN 200380105046 CN200380105046A CN1720284A CN 1720284 A CN1720284 A CN 1720284A CN 200380105046 CN200380105046 CN 200380105046 CN 200380105046 A CN200380105046 A CN 200380105046A CN 1720284 A CN1720284 A CN 1720284A
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film
alkaline solution
saponification
coating
cellulose acylate
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CN100336850C (en
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川崎博史
加藤荣一
本隆裕
并河均
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Fujifilm Corp
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Fujifilm Corp
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Abstract

The invention is to provide an alkali saponification method for uniformly and stably saponifying a cellulose acylate film, to provide a surface saponified cellulose acylate film adapted for an optical compensation sheet for a large-sized liquid crystal display apparatus without a display defect, and to provide a alkali saponified cellulose acylate film adapted for an optical compensation sheet with an appropriate adhesion between a transparent substrate and an orienting film. There is provided an alkali saponification method for cellulose acylate film characterized by alkali saponification of a cellulose acylate film with an alkali solution, particularly an alkali saponification method for achieving selective saponification by coating the alkali solution on one surface only of the film, and a cellulose acylate film processed by such alkali saponification method.

Description

The alkali soap method of cellulose acylate film, surperficial saponified cellulose acylate film and the optical thin film that uses described saponification film
Technical field
The present invention relates to a kind of alkali soap method, surperficial saponified cellulose acylate film of cellulose acylate film and use the optical thin film of this saponification film.Specifically, the present invention relates to the optical thin film of a kind of light polarization that is used for image display, scattering of light, optical compensation etc.
The invention still further relates to a kind of method that additive liq is provided in the production of alkali soap fluidized polymer film.More particularly, the present invention relates to a kind of method, thereby can use alkaline solution stably to produce alkali saponified polymeric film in a continuous manner by the saponified polymer film surface with additive liq supply alkaline solution.
Background technology
In the various indicating meters of equipping in Personal Computer, TV, mobile telephone or various device, at the bottom of protecting group transparent on the surface, for example glass or plastic plate are observed visual information, for example character or pattern.In addition, in the indicating meter of most of equipment, use liquid-crystal display.Liquid crystal display is made of liquid crystal cell, polaroid and optical compensating gage (polarizer).In transmission type liquid crystal display apparatus, two polaroids are installed on the both sides of liquid crystal cell, and between liquid crystal cell and polaroid, are placed one or two optical compensating gages.Reflective liquid crystal display device is made up of reflector, liquid crystal cell, optical compensating gage and polaroid.
Liquid crystal cell by rod shaped liquid crystal molecule, seal two substrates of these molecules, and the electrode layer formation that is used for applying voltage to rod shaped liquid crystal molecule, and for liquid crystal cell, different orientation according to rod shaped liquid crystal molecule has proposed different display formats, for example TN (twisted nematic), IPS (face internal conversion type), FLC (ferroelectric liquid crystals), OCB (optical-compensation bent), STN (super-twist nematic) are arranged for transmission-type, perhaps VA (vertically aligned), and HAN (mix and arrange nematic) is arranged for reflection-type.
Polaroid is made of polarizing coating and two transparent protective films that are provided at its both sides usually.Polarizing coating obtains by aqueous solution dipping polyvinyl alcohol and the described film of uniaxial extension with iodine or dichroic dye usually.Because its excellent optical, high transmittance and the degree of polarization on wide wavelength region and excellent luminance and contrast gradient, use the polaroid of cellulose acylate film to be often used as the polaroid of various picture displays.
For the color or the expansion visual angle of removal of images, in various liquid crystal displays, all used optical compensating gage.Used the tensile birefringent film as optical compensating gage.
The optical compensating gage that replacement is formed by the tensile birefringent film, the someone has proposed to have the optical compensating gage of the optical anisotropic layer that is formed by liquid crystal molecule (particularly discotic liquid-crystalline molecules) on transparent substrates.Form optical anisotropic layer by aligned liquid-crystal molecule and fixing this state of orientation.
In optical compensating gage, use liquid crystal molecule can be implemented in original tensile birefringent film the optical characteristics that can not obtain.
According to the optical property of liquid crystal cell, more particularly design the optical property of optical compensating gage according to the difference of the display format of above-mentioned liquid crystal cell.By in optical compensating gage, using liquid crystal molecule, particularly discotic liquid-crystalline molecules, can produce optical compensating gage with different optical characteristic corresponding to the liquid crystal cell different display modes.
Corresponding to different display formats, the optical compensating gage of various forms of use discotic liquid-crystalline molecules has been proposed.For example, the optical compensating gage of the liquid crystal cell of in JP-A 6-214116, USP 5,583,679, USP 5,646,703 and GP 3911620A1, describing that is used for the TN pattern; And the optical compensating gage of the liquid crystal cell of in JP-A 10-54982, describing that is used for IPS or FLC pattern; At USP 5,805,253 and W096/37804 in the optical compensating gage of the liquid crystal cell that is used for ocb mode or HAN pattern described; The optical compensating gage of the liquid crystal cell of in JP-A9-26572, describing that is used for the STN pattern; The optical compensating gage of the liquid crystal cell of in Japanese Patent 2866372, describing that is used for the VA pattern.
Form elliptic polarizing piece by laminated optical compensating gage and polaroid, optical compensating gage can also play a part the transparent protective film of polaroid.This elliptic polarizing piece has by laminated transparent protective film, polarizing coating, transparent substrates successively and the laminate structures that formed by the optical anisotropic layer that liquid crystal molecule constitutes.Liquid crystal display will approach and weight wants light, and can make equipment thinner and weight is lighter by the used assembly of shared (co-use) (transparent protective film of polaroid and optical compensating gage) minimizing.In addition, saved the adhesion step that is used for described assembly by the assembly that reduces liquid crystal display, thereby advantageously reduced the possibility that in device assembles, causes problem.Described a kind of integrated polarizing sheet for instance in patent documentation JP-A 7-191217, JP-A8-21996 and JP-A 8-94838, the transparent substrates of optical compensating gage that wherein will use liquid crystal molecule is simultaneously as a protective membrane of polaroid.
Flaky material with optical function; for example polaroid or optical compensating gage are known as optical thin film; and transparent substrates as described optical thin film; use has excellent light transmission, no optics orientation, the physics of excellence and the cellulose acylate film of mechanical characteristics, and the size of described cellulose acylate film is little with the variation of temperature and humidity.
On the transparent substrates that constitutes by cellulose acylate film; provide polarizing coating or optical compensating gage via bonding coat or oriented layer (normally polyvinyl alcohol); and as being used for realization and bonding coat or oriented film adherent method; disclose and a kind of cellulose acylate film has been immersed in the alkali aqueous solution, thus saponification and make the method (for example referring to [0033] section among [0008] among JP-A7-151914 section, the JP-A 8-94838, [0083] section among the JP-A 2001-16614 and [0042] among the JP-A 2001-18813 section) of its surface hydrophilic
But, because used treatment solution is only formed by the aqueous solution of alkaline reagents, so be difficult to the surface of saponification hydrophobic membrane equably.In addition, because treatment process saponification has simultaneously been bathed in the immersion type saponification two sides of cellulose acylate film,, can cause pro and con bonding defective bonded to each other so apply from the teeth outwards under the situation of volume film behind the hydrophilic layer of polyvinyl alcohol for example.For bathe in the treatment process the only situation of saponification one side surface in saponification; a kind of saponified method of implementing after not thinking to carry out WATER REPELLENT on the saponified surface is disclosed; but because increased troublesome steps and produced unnecessary waste material, therefore described method is being worthless aspect productivity and the environment protection.
On the other hand, someone proposed a kind of by in alkali aqueous solution, add neither can dissolve also not can the swollen polymer film the alkali soap solution that forms of organic solvent in the method ([0034] section among the JP-A 2002-82226) of soaking, and comprise the alkali aqueous solution of organic solvent or the method (W002/46809) of one side at least that alkali soap solution comes the saponification film by coating on the film surface.
Compare with alkali aqueous solution, in alkali soap solution, add the activity that organic solvent has increased saponification reaction.On the other hand, because the increase of reactive behavior or according to the kind or the content of organic solvent, can cause the remarkable dissolving of contained additive in the film or compounding substances, perhaps adhering to of concentrated base reagent causes the optical thin film downgrade, for example turbidity increases, the adhesion defective, because defective that foreign matter causes or orientation defective.
On the other hand, to increase and the demand of the increase turnout that the fast development of mobile equipment causes in order satisfying, and to reduce production costs by nearest image display picture size, need be to stablize and the successive mode be produced band shape (web-shaped) film.
On the other hand, in aforesaid method, implement in the situation of saponification process continuously, because the alkaline reagents in the alkaline solution is consumed by saponification reaction, thereby cause for example saponification level to change in time or the inhomogenous problem of saponification level under processing condition (for example technological temperature and process time) maintenance constant situation.In addition, alkaline solution absorbs carbon dioxide in air and causes the alkaline reagents consumption that caused by neutralization reaction, thereby causes the problem similar to above-mentioned situation.
In order to tackle the deterioration of alkaline solution, replace alkaline solution with new solution usually, so that the saponification reaction level keeps within the required range.
But, when the amount of finish of polymeric film is big, then needs to replace alkaline solution continually, thereby reduced operation efficiency, and produced a large amount of waste lyes, spent lye treatment brings new problem again.
Summary of the invention
As previously mentioned, the known alkali soap method that is used for cellulose acylate film is satisfied the demand unsatisfactorily, and needs a kind of method that can stably produce banded film with gratifying productivity.A target of the present invention provide a kind of can be in quick alkali soap processing on whole surface the stable and alkali soap method of saponification cellulose acylate film equably.
Another target of the present invention provides a kind of surperficial saponified cellulose acylate film, and its optical sheet of production big area easily can not bring display defect when described optical sheet is used for image display.
Another target of the present invention provides a kind of being equipped with and uses cellulose acylate film as the optical sheet of substrate and liquid crystal display that can the clear display image.
Another target of the present invention provides a kind of method, and in the process that the saponification of implementing polymeric film is in a continuous manner handled, it can be finished saponification with stable manner and handle, and working efficiency reduces or the problem of liquid waste disposal and do not produce.
Above-mentioned target of the present invention realizes by the optical thin film of alkali soap method, surperficial saponified film and this film of the described use in following (1) to (23):
(1) a kind of usefulness comprises alkaline reagents, water, organic solvent, tensio-active agent and the alkaline solution of solubilising reagent (the mutually solubilizing agent) method of cellulose acylate film being carried out the alkali soap processing mutually.(first embodiment)
(2) according to the method for project (1), the inorganic/organic ratio of wherein said organic solvent (I/O value) is 0.5 or higher, and its solubility parameters is 16 to 40[mJ/m 3] 1/2
(3) according to the method for project (1) or (2), wherein said tensio-active agent is at least a tensio-active agent that is selected from nonionogenic tenside, anion surfactant, cats product and amphoterics.
(4) a kind of usefulness comprises the method that the alkaline solution of alkaline reagents and tensio-active agent carries out the alkali soap processing to cellulose acylate film, and wherein said tensio-active agent is the amphoterics by following general formula (I) expression:
Figure A20038010504600101
Wherein, A represents alkylidene group; L 0Expression connects nitrogen-atoms and X -Group; X -Expression-COO -,-SO 3 -Or-PO 3H -R 0The expression alkyl; R 1Expression hydrogen atom or alkyl; N represents from 1 to 50 integer; P and q represent 1 or 2 integer and p+q=3 respectively.
(second embodiment)
(5) according to any one method of project (1) to (3), wherein said mutual solubilising reagent is at least a many alkylol cpds, and the solubleness of water are 30 grams or higher in 25 ℃ of described mutual solubilising reagent of per down 100 grams.
(6) according to the method for project (4), wherein said alkaline solution comprises the alkaline reagents of 0.1 to 25 weight % and the mixed solvent of water or water and hydrophilic organic solvent.
(7) according to any one method of project (1) to (6), wherein said alkaline solution has alkaline reagents concentration, 45mN/m or lower surface tension and 0.8 to 20mPas the viscosity of 0.1 to 25 weight %.
(8) according to any one method of project (1) to (7), wherein said alkaline solution comprises that at least a boiling point is 120 ℃ or higher hydrophilic compounds, and can dissolve 50 grams or more water in the described hydrophilic compounds of 100 grams.
(9) according to any one method of project (1) to (8), wherein said alkaline solution comprises defoamer.
(10) a kind of method of cellulose acylate film being carried out the alkali soap processing with alkaline solution, it comprises: the step of handling cellulose acylate film with alkaline solution; And with the step of alkali diluent or the neutralising fluid described alkaline solution of flush away from the described film, wherein said alkali diluent or neutralising fluid have 3500mg/L or lower carbonate concentration.(the 3rd embodiment)
(11) according to the method for project (10), wherein said alkali diluent or neutralising fluid have 500mg/L or lower polyvalent metal ion concentration, and chlorine ion concentration is 300mg/L or lower.
(12) according to the method for project (10) or (11), wherein said alkali diluent or neutralising fluid comprise tensio-active agent.
(13) according to any one method of project (10) to (12), the solvent of wherein said alkali diluent or neutralising fluid is the mixture of water or water and organic solvent.
(14) according to any one method of project (10) to (13), wherein said alkali diluent or neutralising fluid comprise defoamer.
(15) according to any one method of project (10) to (14), the wherein said step of handling cellulose acylate film with alkaline solution is included in the step of coating alkaline solution on the cellulose acylate film.
(16) according to any one method of project (1) to (15), it is included under room temperature or the higher temperature step of the described alkaline solution of coating on cellulose acylate film, and from the described cellulose acylate film the step of the described alkaline solution of flush away.
(17) a kind of surperficial saponified cellulose acylate film by obtaining according to any one method of project (1) to (15).
(18) a kind of optical thin film that comprises according to the surperficial saponified cellulose acylate film of project (17).
(19) use alkaline solution continuous saponification polymeric film surface with the process of producing alkali soap fluidized polymer film in the method for the described alkaline solution of additive liq supply, it comprises:
Measure the step of the saponification ability of described alkaline solution;
Based on the saponification ability of being surveyed, determine the supply mode of additive liq, thereby after with described additive liq supply, make the saponification ability of described alkaline solution be in step in the pre-determined range; And
With determined supply mode, with the step of the described alkaline solution of described additive liq supply.
(the 4th embodiment)
(20) according to the method for project (19), it also comprises the step of measuring the processing area of described polymeric film in the unit time, wherein determines described pre-determined range based on the processing area in the measured unit time.
(21), wherein be selected from the saponification ability that following method is measured described alkaline solution: the measurement of the electrode potential between the measurement of the electrode voltage between the electrode of the measurement of the measurement of alkaline solution pH, alkaline solution specific conductivity, the measurement of alkaline solution electric impedance, current control and the electrode of current control by at least a according to the method for project (20).
(22) use alkaline solution continuous saponification polymeric film surface with the process of producing alkali soap fluidized polymer film in the method for the described alkaline solution of additive liq supply, it comprises:
Measure the step of the processing area of described polymeric film in the unit time;
Carry out the pre-storage (pre-memorized amount) that required alkaline solution is processed in saponification according to described polymeric film, by the step of the consumption of alkaline solution in the processing area Units of Account time in the measured unit time to unit surface;
Consumption in the unit time that draws based on aforementioned calculation is determined the supply mode of additive liq, thereby after with described additive liq supply, makes the saponification ability of described alkaline solution be in step in the pre-determined range; And
According to determined supply mode, with the step of the described alkaline solution of described additive liq supply.
(23) according to the method for project (22), wherein said saponification process comprises the step of prior heated polymerizable thing film to 25 ℃ or higher temperature successively; Apply the step of described polymeric film with described alkaline solution; Described polymeric film is remained on step under 25 ℃ or the higher temperature; And from the described polymeric film the step of the described alkaline solution of flush away.
Form oriented film going up according to (1) to (16) any one method surperficial saponified cellulose acylate film (17) by the alkali soap acquisition; coated with liquid crystal molecule on oriented film then; and fixing liquid crystal molecular orientation; thereby the formation optical anisotropic layer forms optical compensating gage thus.
In addition; by polarizing coating and two formed polaroids of transparent protective film that are arranged in its both sides; one of them transparent protective film is an optical compensating gage; the optical anisotropic layer that it is included in the oriented film that stacks gradually on the cellulose acylate film and forms by fixing liquid crystal molecular orientation can be used as this cellulose acylate film effectively according to (1) to (16) any one method surperficial saponified cellulose acylate film (17) by the alkali soap acquisition.
Can use this cellulose acylate film to prepare and have the excellent ply adhesion and the optical thin film (18) of show uniformity.
Alkali soap method of the present invention, comprise in the step of alkali soap solution of the alkaline reagents of high density and precipitate (for example adding material in the described film to) at flush away, concentration, polyvalent ion concentration or the chlorine ion concentration of carbonate in the alkali diluent are remained in the predetermined scope, thereby realized defective or the orientation defective that the alkali soap process increase of film turbidity, adhesion defects does not take place, caused by foreign matter.
Embodiment
[polymeric film]
Polymeric film preferably has 80% or higher transmittance.Preferred described polymeric film is difficult for showing double refraction under external force.
Described polymkeric substance comprises hydrolyzable key (accepting the saponified key), for example ester bond or amido linkage.Ester bond is particularly preferred, and more preferably has ester bond in side chain.As the polymkeric substance that comprises ester bond in the side chain, cellulose ester is preferred.In cellulose ester, cellulose acylate is most preferred, and it is used as substrate as one of purpose of the present invention.
Hereinafter, will provide detailed explanation to cellulose acylate.The starting material Mierocrystalline cellulose comprises velveteen and wood pulp, but can use the cellulose acylate from arbitrary raw material preparing, and can use the cellulose acylate mixture that makes from two kinds of starting material.Cellulose acylate that obtain from described Mierocrystalline cellulose and that use in the present invention have satisfy below the Mierocrystalline cellulose hydroxyl substitution value of all relations (I) to (III):
Relation (I): 2.6≤SA '+SB '≤3.0
Relation (II): 2.0≤S A '≤3.0
Relation (III): 0≤SB '≤0.8
In the above-mentioned relation formula, the SA ' expression substitution value of ethanoyl substituted cellulose hydroxyl hydrogen atom; And the SB ' expression substitution value of acyl substituted Mierocrystalline cellulose hydroxyl hydrogen atom with 3 to 22 carbon atoms.SA represents the ethanoyl of substituted cellulose hydroxyl hydrogen atom; And SB represents the acyl group with 3 to 22 carbon atoms of substituted cellulose hydroxyl hydrogen atom.
Constitute cellulosic glucose unit and have the free hydroxyl at 2-, 3-and 6-position with β-1,4 key.Cellulose acylate is meant the polymkeric substance that forms by with the described hydroxyl of acyl group esterification all or part.The acyl substituted degree means the esterification ratio (for each position, substitution value 1 expression 100% esterification) of Mierocrystalline cellulose on 2-, 3-and 6-position.In the present invention, SA and SB substitution value and (SA '+SB ') more preferably be 2.7 to 2.96, and be preferably 2.80 to 2.95 especially.The substitution value of SB (SB ') is 0 to 0.8 in addition, particularly 0 to 0.6.In addition, preferred 28% or more SB be substituting group on the hydroxyl of 6-position, more preferably 30% or mostly are substituting groups on the hydroxyl of 6-position, more preferably 31% or more, and preferred especially 32% or mostly are substituting groups on the hydroxyl of 6-position.In addition, also preferred in cellulose acylate film on 6 of cellulose acylates the substitution value of SA and SB and be 0.8 or bigger, more preferably 0.85 or bigger, and preferred especially 0.90 or bigger.This cellulose acylate film allows preparation to have the solution of preferred dissolution degree, and particularly prepares satisfied solution in no chlorine organic solvent.
The acyl group (SB) that has 3 to 22 carbon atoms in the cellulose acylate that uses among the present invention can be aliphatic group or aryl, and is not particularly limited.For instance, described cellulose acylate can be cellulosic alkyl-carbonyl ester, alkenyl carbonyl ester, fragrant carbonyl ester, aromatic alkyl carbonyl ester etc., and wherein every kind can also have substituting group.The preferred embodiment of SB comprises propionyl, butyryl radicals, oenanthyl, oenanthyl, caproyl, capryloyl, decanoyl, lauroyl, tridecanoyl, tetradecanoyl, palmitoyl, stearoyl, isobutyryl, uncle's butyryl radicals, hexanaphthene carbonyl, oleoyl, benzoyl, naphthalene carbonyl and cinnamoyl.Wherein, the preferred embodiment of SB comprises propionyl, butyryl radicals, lauroyl, stearoyl, uncle's butyryl radicals, oleoyl, benzoyl, naphthalene carbonyl and cinnamoyl.
Describe among the Mokuzai Kagaku that the ultimate principle of the method for synthetic cellulose acylate is shown at Migita etc., 180-190 page or leaf (Kyoritsu Shuppan, 1968).Representational synthetic method is to use the liquid phase acidylate of carboxylic acid anhydride-acetate-sulfuric acid catalyst.Concrete example is included in disclosed method among JP-A 6-32801,7-70702,10-45804,10-511728 and the 2001-200901.
The cellulose acylate that uses among the present invention preferably has 200 to 700, preferred especially 250 to 550 the polymerization degree (viscosity is average).In order in comprising acidylate film, fiber or the moulded product of cellulose triacetate, to obtain satisfied physical strength; usually needing the polymerization degree is 200 or higher; as " Cellulose Handbook " at Hiroshi Sofue and Nobuhiko Migita; Asakura Shobo (1958); perhaps " the PlasticMaterial Text 17 " of Hiroshi Marusawa and Kazuo Uda is described in the Nikkan Kogyo Shimbun (1970).
According to purpose or the application used, the cellulose acylate film that uses among the present invention can comprise other compound except cellulose acylate.
In using the situation of cellulose acylate film as optical compensating gage, delay (Re delay) in the membrane plane and the delay (Rth delay) on the thickness direction are respectively by following formula (I) and (II) definition:
(I)Re＝|(nx-ny)|×d
(II)Rth＝((nx+ny)/2-nz)×d
In formula (I) with (II), nx represents the specific refractory power on the phase delay direction of principal axis (direction of specific refractory power maximum) in the membrane plane; Ny represents that phase place shifts to an earlier date the specific refractory power on the direction of principal axis (direction of specific refractory power minimum); Nz represents the specific refractory power on the film thickness direction; And d represents thickness, and unit is a nanometer.
The Re length of delay of preferred cellulose acylate film is between 1 to 200 nanometer, and the Rth length of delay is between 70 to 400 nanometers.Concrete value is extrapolated definite according to the observed value that uses vertical face incident measuring light to be obtained.Can use ellipsometers (for example M-150 is produced by Nippon Bunko company) to implement to measure.Use the light (He-Ne laser apparatus) of wavelength 632.8 nanometers during measurement.
In order to regulate the delay of cellulose acylate film, use usually and apply external force, tensile method for example, and can also add in some cases and be used to increase optically anisotropic delay dose.In order to regulate the delay of cellulose acylate film, the preferred aromatics that comprises at least two aromatic rings that uses is as postponing dose.With respect to the cellulose acylate of 100 weight parts, described aromatic compound preferably uses with the amount of 0.01 to 20 weight part.Can also be used in combination two kinds or more of aromatic compounds.Except aromatic carbon ring, the aromatic nucleus of aromatic compound also comprises aromatic heterocycle.For instance, example is included in the compound of describing among EP-A 0911656A2, JP-A 2000-111914 and the 2000-275434.
The cellulose acylate that uses among the present invention can also comprise various additives (for example softening agent, uv-absorbing agent, antideteriorant, fine particle, separating agent, infrared absorbing agents, static inhibitor etc.) according to its purpose, and described additive can be solid matter or oily mater.In the situation that cellulose acylate film is made of multilayer, the kind of additive can be different in every layer with consumption in addition.Can advantageously use special permission public technology report in Japanese innovation association (2001-1745, March 15 calendar year 2001, JIII), the material of describing in detail in the 16-22 page or leaf.The consumption of described additive is not particularly limited, as long as every kind of material can be brought into play its effect, but the consumption of preferred described additive is 0.001 to 20% of a cellulose acylate composition gross weight.
Cellulose acylate film of the present invention is preferably by the preparation of solvent casting method.
Used solvent can be known solvent, the preferred solvent of solubility parameters in 17 to 22 scopes.Example comprise the lower aliphatic hydrocarbon muriate, lower aliphatic alcohols, have 3 to 12 carbon atoms ketone, have 3 to 12 carbon atoms ester, have 3 to 12 carbon atoms ether, have the ester of 3 to 12 carbon atoms, the aromatic hydrocarbon that has the aliphatic hydrocarbon of 5 to 8 carbon atoms and have 6 to 12 carbon atoms.Concrete example is included in the compound of describing in the 12-16 page or leaf of above-mentioned special permission public technology report 2001-1745.
Especially, consider the solubleness of cellulose acylate, preferably use the mixture of the alcohol of the ketone of acetic ester, 5 to 60 weight % of 20 to 90 weight % and 5 to 30 weight %.
In addition, as the not halogenated organic solvent system that does not contain halohydrocarbon, for instance, can use the 2002-146043 at JP-A, [0021] section is to [0025] section and JP-A2002-146045, the solvent systems that [0016] section is described to [0021] section.
When preparation cellulose acylate solution of the present invention (coating fluid), its dissolving method is not particularly limited, and can is room temperature dissolving method, hot-cold lysis method, high-temperature digestion method or its combination etc.The method for preparing cellulose acylate solution is described among 10-45950,2000-53784,11-322946,11-322947,2-276830,2000-273239,11-71463,05-259511,2000-273184,11-323017 and the 11-302388 for instance at JP-A5-163301,61-106628,58-127737,9-95544,10-95854.Above-mentioned in organic solvent the method for dissolving cellulos acylate be applicable to the present invention.The coating fluid of cellulose acylate usually will be through concentrating and filtration treatment, for example reports detailed description in the 25th page of 2001-1745 referring to above-mentioned special permission public technology.In the situation of high-temperature digestion, organic solvent uses under its boiling point or higher temperature mostly, and uses under pressurized state.
Hereinafter, the method for using cellulose acylate solution to produce film will be explained.For the production of cellulose acylate film, can use known solution-cast film and solution-cast film-forming apparatus, it is called drum-type method or belt method, and is used to produce tri cellulose acetate membrane.The film forming step will be explained in the example of belt method.In coating fluid (cellulose acylate solution) holding tank of packing into that will in dissolution equipment (groove), prepare earlier, eliminate contained foam in the coating fluid, and carry out last adjustment.For instance, by pressurize the accurately toothed gear pump of constant speed of the height by rotating speed control charging capacity, adjusted coating fluid is sent in the punch die of pressurization, and coating fluid is cast on the metal support member for no reason of rotating the casting unit from the lip (slit) of pressurization punch die, and after it rotates a circle basically, peel off half-dried coating liquid film (being also referred to as the net width of cloth) from metal support member at the pick-up point of metal support member.The net width of cloth of transmission gained in tenter machine, net width of cloth two ends by fixture support to keep width, then in drying plant by cylinder transmission, and be dry after, use up-coiler to twine the described net width of cloth with predetermined length.According to purposes, the combination of the cylinder of tenter machine and drying plant is variable.These production stages (be divided into casting (comprising common casting), metal support member, drying, peel off, stretching etc.) have a detailed description in above-mentioned special permission public technology is reported the 25th to 30 page of 2001-1745.In casting step, one type the plain acylate solution of single layer fibre of can casting, perhaps simultaneously or two or more cellulose acylate solution of casting altogether continuously.
Can regulate the delay of cellulose acylate film by stretching.Drawing coefficient is preferably 3 to 100%.
Described cellulose acylate film preferably has 15 to 500 microns, more preferably 20 to 200 microns thickness.
In first embodiment of the present invention, use the alkaline solution that comprises alkaline reagents, water, organic solvent, tensio-active agent and mutual solubilising reagent to come saponification surface saponified cellulose acylate film.
In second embodiment of the present invention, use the alkaline solution that comprises alkaline reagents and tensio-active agent to come saponification surface saponified cellulose acylate film.
In the 3rd embodiment of the present invention, can prepare alkaline solution by dissolving alkali in the mixture of water or water and organic solvent.Preferred organic be selected from have 8 or still less carbon atom alcohol, have 6 or still less carbon atom ketone, have 6 or still less carbon atom ester and have 8 or a kind of or two or more organic solvents in the polyhydroxy-alcohol of carbon atom still less.
Alkaline reagents in the alkaline solution of the present invention can be inorganic alkaline agents or organic basic reagent.In order to induce saponification reaction at lower concentration, highly basic is preferred.Preferred examples comprises alkali metal hydroxide (for example NaOH, KOH or LiOH); Alkaline earth metal hydroxides; Sodium phosphate, potassium or ammonium; Sodium phosphate dibasic, potassium or ammonium; Sodium Tetraborate, potassium or ammonium; Ammonium hydroxide; Amine (monomethylamine for example, dimethylamine, Trimethylamine 99, monoethylamine, diethylamine, triethylamine, monoisopropylamine, Diisopropylamine, tri-isopropyl amine, n-Butyl Amine 99, monoethanolamine, diethanolamine, trolamine, one Yi Bingchunan, diisopropanolamine (DIPA), ethylene imine, quadrol, pyridine, DBU (1,8-diazabicyclo [5,4,0]-the 7-undecylene), DBN (1,5-diazabicyclo [4,3,0]-the 5-nonene), tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium, hydroxide triethyl fourth ammonium, perfluor tributylamine or perfluor triethylamine), and complex salts (for example) (Pt (NH 3) 4) (OH) 4Free alkali.More preferably alkali metal hydroxide, and most preferably NaOH or KOH.These alkaline reagentss can use separately or two or more are used in combination.
The concentration of alkaline solution neutral and alkali reagent was determined according to kind, temperature of reaction and the reaction times of used alkaline reagents.In order to finish saponification reaction at short notice, the solution of preferred preparation high density.But too high concentration may reduce the stability of alkali soap solution, thereby causes producing precipitation through long-time back in coating.The preferred concentration of alkali soap solution is 0.1 to 25 weight %, 0.5 to 15 weight % more preferably, and most preferably be 1 to 10 weight %.
For the solvent of alkaline solution of the present invention, can make the mixing solutions of water or water and organic solvent.Can use any organic solvent that can be miscible with water.
In these organic solvents, preferably inorganic/organic ratio (I/O value) is 0.5 or higher, and its solubility parameters is 16 to 40[mJ/m 3] 1/2Organic solvent.0.6 the I/O value and 18 to 10 is to 31[mJ/m 3] 1/2Solubility parameters be preferred.Inorganic nature exceeds the I/O value of described scope or the reduction that lower solubility parameters causes alkali soap speed, and on whole surface the inhomogeneity deficiency of saponification degree.On the other hand, I/O value or higher solubility parameters that organic trait exceeds described scope provide saponification speed faster, but trend towards causing muddiness, therefore at whole lip-deep lack of uniformity.
Have the solubility parameters and the I/O value that are positioned at above-mentioned scope, and the organic solvent example that can advantageously use in the present invention comprises following solvent:
Solubility parameters I/O value
[mJ/m 3] 1/2
Virahol 23.5 2.00
N-propyl alcohol 24.3 1.67
Mierocrystalline cellulose methyl esters 23.3 2.00
2-butanols 22.1 1.25
Ethanol 26.0 2.50
Propylene glycol monomethyl ether 20.7 1.50
Methyl alcohol 29.7 5.00
In addition, organic solvent, particularly organic trait and the solvability organic solvent in above-mentioned scope combines with mutual solubilising reagent and the tensio-active agent mentioned later, can keep high saponification speed, and can improve whole lip-deep saponification degree of uniformity.
Organic solvent with preferred characteristics can be the solvent of describing in following document for instance: Solvent Pocket Book New Edition, Society of Organic SyntheticChemistry compiles (Ohm Sha, 1994).(in addition, the inorganic nature of organic solvent/organic trait value (I/O value) is for instance at document Yuki Gainen-zu, Yukio Tanaka, SankyoShuppan describes in 1983, the 1-31 pages or leaves).
Concrete example comprises the Fatty Alcohol(C12-C14 and C12-C18) (methyl alcohol for example of monohydroxy, ethanol, propyl alcohol, butanols, amylalcohol or hexanol), alicyclic alkanol (hexalin for example, methyl-cyclohexanol, the methoxyl group hexalin, hexahydrobenzyl alcohol, perhaps cyclohexyl propyl alcohol), phenyl alkanol (phenylcarbinol, phenylethyl alcohol, phenylpropyl alcohol, Phenoxyethanol, methoxybenzyl alcohol or BOE), heterocycle alkanol (for example furfuryl alcohol or tetrahydrofurfuryl carbinol), ethylene glycol mono-ether (methylcyclohexane for example, ethyl cellosolve, propyl cellosolve, the methoxy methyl oxyethanol, ethylene glycol butyl ether, the hexyl cellosolve, methyl carbitol, ethyl carbitol, the propyl group Trivalin SF, diethylene glycol monobutyl ether, the methoxyl group triglycol, the oxyethyl group triglycol, propylene glycol monomethyl ether, dihydroxypropane single-ether or propylene glycol monopropyl ether), ketone (acetone for example, butanone or methyl iso-butyl ketone (MIBK)), ester (methyl acetate for example, ethyl acetate or butylacetate), acid amides (N for example, dinethylformamide, dimethyl formamide, N-N-methyl-2-2-pyrrolidone N-or 1, the 3-dimethyl-imidazolinone), sulfoxide (for example dimethyl sulfoxide (DMSO)), and ether (tetrahydrofuran (THF) for example, pyrans, dioxan, trioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, the dipropyl cellosolve, the methylethyl cellosolve, the dimethyl Trivalin SF, diethylene glycol diethyl ether or methylethyl Trivalin SF).Organic solvent can use separately or two or more are used in combination.
Use separately or with two or more form of mixtures situation with an organic solvent in, at least a organic solvent preferably has big solubleness in water.The solubleness of preferred described organic solvent in water is 50 weight % or bigger, and is miscible arbitrarily with water more preferably.Thus, can prepare to the soap by product that produces in alkaline reagents, the saponification process and owing to absorbing the solution that carbonate that Carbon Dioxide in Air produces has abundant solubleness.
The ratio of organic solvent is according to solvent types, determine with compatibility (solvability), temperature of reaction and reaction times of water in the solvent.In order to finish saponification reaction at short notice, the solution of preferred preparation high density.But too high solvent strength may cause the undue swelling of separating out of composition in the acidylate film (for example softening agent) or film, so the concentration of selective solvent suitably.
Can suitably select the ratio of mixture of water and organic solvent, but preferred weight ratio is 3/97 to 85/15, more preferably 5/95 to 60/40, more more preferably 15/85 to 40/60.In described scope, can easily on the whole surface of film, realize uniform saponification processing, and can not reduce the optical characteristics of acidylate film.
The organic solvent that comprises in the alkaline solution of the present invention not only comprises as what the above-mentioned target of the present invention provided having the reduction muddiness and increase the organic solvent that homogeneity and saponification stability etc. act on, and can comprise have tensio-active agent, the mutual organic solvent of solubilising reagent and the dissolving auxiliary function of defoamer in alkaline solution, and because these coexistences of dissolving auxiliarys have strengthened effect of the present invention.Organic solvent with described function can be different with the organic solvent with above-mentioned preferred I/O value.For instance, the preferred organic with described dissolving subsidiary function can be N-phenylethanolamine, N-phenyldiethanol-amine, fluorizated alcohol (C for example nF 2n+1(CH 2) kOH (wherein n is from 3 to 8 integer, and k is 1 or 2 integer), for example 1,2,2,3,3-seven fluorine propyl alcohol, hexafluoro butyleneglycol or perfluor ring ethanol).The content of the organic solvent that uses as the dissolving auxiliary is preferably 0.1 to 5% with respect to the gross weight of used liquid.
For the ease of the coating alkaline solution, preferred organic solvent of selecting to have low surface tension, and alkaline solution preferably has 45mN/m or lower, and more preferably 20 to 40mN/m, and preferred especially 20 to 35mN/m surface tension.
In addition, described organic solvent can be advantageously utilised in alkali diluent and alkali neutralising fluid.In the case, the mixed weight of water and organic solvent ratio is preferably 50/50 to 100/0, and more preferably 70/30 to 97/3, and more preferably 80/20 to 95/5.
For the alkaline reagents of alkaline solution, can use above-mentioned alkaline reagents.
Draw total saponification number of sites by the saponification reaction number of sites on the unit surface cellulose acylate film being multiply by the required saponification degree of depth of adhesion oriented film, provide the required alkali coating amount of saponification reaction as index with total saponification number of sites.Because the consumption of alkali, speed of response reduces along with the carrying out of saponification reaction, and the coating amount in the preferred practical application equals several times of theoretical alkali coating amount.Specifically, be preferably 2 to 20 times of theoretical alkali coating amount, more preferably 2 to 5 times.
The temperature of alkaline solution preferably equals temperature of reaction (temperature of=cellulose acylate film).According to the kind of used organic solvent, temperature of reaction can surpass the boiling point of alkaline solution.In order to realize stable coating, preferably be lower than the temperature of the boiling point of alkaline solution, more preferably hang down 5 ℃ temperature, and most preferably hang down 10 ℃ temperature than alkaline solution boiling point than the boiling point of alkaline solution.
In alkali soap method of the present invention, consider transmission speed, in order to realize stable coat operations, alkaline solution preferably has 0.8 to 20mPas, more preferably 1 to 15mPas viscosity.Alkaline solution preferably has described in front surface tension, and in described scope, can realize fully to film wettability of the surface matter, be coated in the maintain property of the lip-deep solution of film and after saponification reaction alkaline solution from the lip-deep removability of film.
In alkali soap method of the present invention, alkaline solution also preferably has 0.65 to 1.05g/cm 3, more preferably 0.70 to 1.00g/cm 3, and most preferably 0.75 to 0.95g/cm 3Density.Be lower than 0.65g/cm 3Density can cause the air pressure in the transmission course inhomogeneous, thereby the homogeneity of reduce handling.In addition, surpass 1.05g/cm 3Density can be because of liquid weight cause the coating striped that is parallel to transmission direction, and cause the inhomogeneous of oriented film thickness.In addition, in alkali soap method of the present invention, in order to alleviate the load of the rinse step of mentioning later, alkaline solution preferably has 1 to 100mS/cm, and more preferably 2 to 50mS/cm, and preferred especially 3 to 20mS/cm specific conductivity.When specific conductivity during less than 1mS/cm, the existence of residual impurity can cause fleck defect (defective that is caused by foreign matter) or the insufficient adhesion of optical compensating layer.
As the liquid property of alkaline solution, the absorbancy at 400 nano measurement wavelength places preferably is lower than 2.0.In coating is handled, must set the size of liquid feeding system and coating machine, so that the absorbancy of liquid can not increase because of separating out of the additive in the cellulose acylate film.When use has the liquid of high absorbance, be dissolved into cellulose acylate film additive adhesion in the alkaline solution to cellulose acylate film, thereby cause fleck defect (foreign matter defective).In order to control the alkali soap solution absorbency, can use the gac absorption and remove dissolved constituent.Gac only need have the function of coloured component in the saponification solution of removing, on shape and material to it without limits.Can use in the alkali soap solution bath and directly to add process of active carbon, perhaps bathe and be filled with the method for circulation saponification solution between the purifier apparatus of gac in saponification solution.
In the 4th embodiment of the present invention, the component of alkaline solution and additive liq can be similar with the component of those alkaline solutions described in the plain acylate film method for saponification of aforementioned fibers.
But the alkali concn of additive liq preferably is equal to or higher than alkali concn in the described alkaline solution, more preferably in the alkaline solution 1.05 of alkali concn to 3 times, and more preferably in the alkaline solution 1.1 to 2 times of alkali concn.More particularly, preferably 0.52 weight % or higher is more preferably 0.55 weight % or higher, and is more preferably 1.1 weight %.In addition, preferred 40 weight % or lower, more preferably 30 weight % or lower, and more preferably 20 weight % or lower again.
[tensio-active agent]
The used alkaline solution of the present invention comprises tensio-active agent.Add tensio-active agent and reduced surface tension, thereby be convenient to coating, improved the homogeneity of coated film, thereby prevented nonwetting shortcoming, also suppressed the muddiness that in the presence of organic solvent, trends towards taking place, and made saponification reaction evenly to carry out.By using mutual solubilising reagent described later simultaneously, this effect becomes more obvious.Used tensio-active agent is not particularly limited, and can is anion surfactant, cats product, amphoterics, nonionogenic tenside or fluorinated surfactant etc.
Hereinafter, introduce the tensio-active agent that can use in the present invention successively.
(anion surfactant)
The preferred embodiment of anion surfactant comprises soap; sylvate; hydroxyalkylated sulfonic acid salt; alkylsulfonate; dialkyl sulfosuccinates; sulfonated; linear alkylbenzene sulfonate; branch-alkylbenzene sulfonate; sulfonated alkyl naphathalene; alkyl phenoxy polyoxyethylene propanesulfonic acid salt; polyoxyethylene allylic alkylation sulfophenyl ether salt; sodium N methyl N oleyltaurate salt; N-alkyl sulfo-succinic acid monoamide disodium salt; sulfonated petro-leum; the sulfonation fatty oil; the sulfuric ester of fatty alkyl ester; alkyl sulfuric ester salt; the polyethylene oxide alkyl ethers sulfuric acid; lipid acid monoglyceride sulfuric acid; the polyoxyethylene alkyl phenyl ether sulfuric acid; polyoxyethylene styryl phenyl ether sulfuric acid; alkyl phosphate salt; the polyoxyethylene alkyl phenyl ether phosphate ester salt; the partly-hydrolysed product of phenylethylene/maleic anhydride copolymer; the partly-hydrolysed product of alkene/copolymer-maleic anhydride; and naphthalenesulfonate-formalin condenses.
(cats product)
The example of cats product comprises alkylamine salt, quaternary ammonium salt (for example Tetrabutylammonium bromide), polyoxyethylene alkylamine salt and polyethylene polyamine derivative.
(amphoterics)
Examples of amphoteric surfactants comprises carboxybetaine, alkylamino carboxylic acid, sultaine, amidosulphuric acid ester and tetrahydroglyoxaline.
(nonionogenic tenside)
The example of nonsurfactant comprises Voranol EP 2001, the polyoxyethylene alkyl phenyl ether, polyoxyethylene polystyrene phenyl ether, the polyoxytrimethylene alkyl oxide, the glycerin fatty acid partial esters, dehydration sorbose fatty acid partial ester, tetramethylolmethane fat acid partial esters, propylene glycol fatty acid ester, glucose fat acid partial esters, polyoxyethylene dehydration sorbose fatty acid partial ester, polyoxyethylene Sorbitol Powder fatty acid partial ester, cithrol, the polyglycerine fatty acid partial ester, polyoxyethylene castor oil, the polyoxyethylene glycerol fatty acid partial ester, fatty diglycollic amide, N, N-pair-the 2-hydroxyalkyl amine, the polyoxyethylene alkylamine, trolamine fatty acid ester and trialkylamine oxide compound.
The specific examples of nonsurfactant comprises polyoxyethylene glycol, the polyoxyethylene lauryl ether, the polyoxyethylene nonyl ethers, the polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl alcohol ether, polyoxyethylene polyoxytrimethylene cetyl ether, polyoxyethylene polyoxytrimethylene behenyl alcohol ether, the polyoxyethylene phenyl ether, the hot phenyl ether of polyoxyethylene, the polyoxyethylene stearylamine, the polyoxyethylene oleyl amine, the polyoxyethylene stearylamide, polyoxyethylene oleyl acid amides, polyoxyethylene castor oil, polyoxyethylene rosin ether, the polyoxyethylene nonyl ethers, the polyoxyethylene mono-laurate, the polyoxyethylene monostearate ester, the polyoxyethylene XU 61518.10, polyoxyethylene monostearate glyceryl ester, the polyoxyethylene monostearate propylene glycol ester, ethylene oxide-oxypropylene block copolymer, distyryl phenol-polyethylene oxide affixture, tribenzyl phenol-polyoxyethylene affixture, glyceryl monostearate, mono laurate dehydration sorb sugar ester and polyoxyethylene mono laurate dehydration sorb sugar ester.The weight-average molecular weight of these nonionogenic tensides is preferably 300 to 50,000, preferred especially 500 to 5,000.
In the present invention, in above-mentioned nonionogenic tenside, the compound of being represented by following general formula (2) is preferred:
General formula (2): R 1-O (CH 2CHR 2O) 1-(CH 2CHR 3) m-(CH 2CHR 4O) n-R 5
Wherein, R 1To R 5All represent hydrogen atom, have alkyl, thiazolinyl, alkynyl, aryl, carbonyl, carboxyl, alkylsulfonyl or the sulfonic group of 1 to 18 carbon atom.
The specific examples of alkyl comprises methyl, ethyl and hexyl.The specific examples of thiazolinyl comprises vinyl and propenyl.The specific examples of alkynyl comprises ethynyl and proyl, and the specific examples of aryl comprises phenyl and 4-hydroxy phenyl.
Each expression of l, m and n is equal to or greater than 0 integer.But l, m and n are not zero simultaneously.
Comprise the homopolymer of polyoxyethylene glycol for example or polypropylene glycol, the perhaps multipolymer of ethylene glycol or propylene glycol by the specific examples of the compound of general formula (2) expression.Consider the solubleness in alkaline solution, described multipolymer has 10/90 to 90/10 ratio.In these multipolymers, consider the solubleness in alkaline solution and be convenient to the alkali soap processing that graftomer and block polymer are preferred.
(fluorinated surfactant)
Fluorinated surfactant refers to the tensio-active agent that intramolecularly comprises perfluoroalkyl.The example of these fluorinated surfactants comprises anionic, for example perfluoroalkyl carboxylate, fluorinated alkyl sulfonate or perfluoralkyl phosphate; Amphoteric, for example perfluoroalkyl trimethyl-glycine; Cationic, perfluoroalkyl leptodactyline for example; And non-ionic type, for example perfluoroalkyl amine oxide, perfluoroalkyl ethylene oxide adduct, comprise perfluorinated alkyl and hydrophilic radical oligopolymer, comprise perfluorinated alkyl and lipophilic group oligopolymer, comprise the oligopolymer of perfluorinated alkyl, hydrophilic radical and lipophilic group or comprise perfluorinated alkyl and the urethane of lipophilic group.
In above-mentioned tensio-active agent, " polyoxyethylene " part can be replaced by polyoxyalkylene (for example polyoxymethylene, polyoxypropylene, perhaps polyoxy butylene), and these compounds are also included within the described tensio-active agent.These tensio-active agents can use separately or two or more are used in combination, as long as be used in combination not impact effect.
In above-mentioned tensio-active agent of the present invention, preferably use quarternary ammonium salt compound to be cats product; Use polyethyleneglycol derivative and polyoxyethylene deriv (for example polyoxyethylene affixture) as nonionogenic tenside; Perhaps use betaine compound as amphoterics.
In alkaline solution, be used in combination nonionogenic tenside and anion surfactant, perhaps nonionogenic tenside and cats product also are preferred for strengthening effect of the present invention.
The add-on that adds the described tensio-active agent in the alkaline solution is preferably 0.001 to 20 weight %, 0.01 to 10 weight % more preferably, and preferred especially 0.03 to 3 weight %.The add-on that is lower than 0.001 weight % is difficult to obtain to add the effect of tensio-active agent, and can reduce saponification character above 20% addition.
The alkaline solution that uses in the second embodiment of the invention comprises the amphoterics by following general formula (I) expression.A kind of concrete tensio-active agent of the present invention, its stability and solubleness in alkaline solution is gratifying, and has suppressed dissolved constituent and separated out from alkaline solution.
General formula (1):
Figure A20038010504600281
Wherein, A represents alkylidene group; L 0Expression connects nitrogen-atoms and X -Group; X -Expression-COO -,-SO 3 -Or-PO 3H -R 0The expression alkyl; R 1Expression hydrogen atom or alkyl; N represents from 1 to 50 integer; P and q represent 1 or 2 integer and p+q=3 respectively.
In general formula (I), A preferably represents to have the alkylidene group of 2 to 4 carbon atoms, for example-and (CH 2) 1-(1 is 2 to 4 integer) ,-CH 2-C (CH 3)-or-C (CH 3)-CH 2-.R 1Preferred expression hydrogen atom or have the aliphatic group of 1 to 22 carbon atom is more preferably hydrogen atom or has the aliphatic group of 1 to 12 carbon atom.The example of aliphatic group comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, octyl group, nonyl, decyl, undecyl, dodecyl, phenmethyl and cyclohexyl methyl.
R 0Preferred expression has the aliphatic group of 1 to 12 carbon atom.The example and aliphatic group R 1Example identical.
For aliphatic group R 0, preferably by-[L 1-NHCO-R 2] expression the replacement aliphatic group.
L wherein 1The optional substituted alkylidene group of expression, and R with 1 to 5 carbon atom 2Expression has the alkyl of 1 to 20 carbon atom.
[the R that is connected with nitrogen-atoms 1-(O-A) n] group is made of polyoxyalkylene chain, and the addition reaction of the epoxy compounds by being selected from oxyethane, propylene oxide and butylene oxide ring at least forms.
Expression oxyalkylene chain number of repeat unit purpose numeral n is preferably 2 to 20 integer, more preferably 5 to 15 integer.
In addition, [(O-A) n-] chain can be the substituting group that is formed by oxyalkylene addition of the same race, the perhaps substituting group that is shaped as by adding of different oxyalkylenes.Add the oxyalkylene chain that is shaped as by two or more oxyalkylenes and can have random of bonding (random boding type) or block of bonding, but block of bonding preferably.
The add-on of described amphoterics in alkaline solution is preferably 0.001 to 20 weight %, 0.01 to 10 weight % more preferably, and be preferably 0.03 to 3 weight % especially.The add-on that is lower than 0.001 weight % is difficult to obtain to add the effect of tensio-active agent, and can reduce saponification character above 20% addition.
(other tensio-active agent)
In the alkaline solution that the present invention uses, other tensio-active agent can be used with above-mentioned amphoterics.Can use aforesaid nonionogenic tenside, anion surfactant, cats product or fluorinated surfactant.
The alkaline solution that uses in first embodiment of the invention comprises mutual solubilising reagent.In the present invention, mutual solubilising reagent hydrophilic compounds, the solubleness of water are 30 grams or higher in 25 ℃ of described mutual solubilising reagent of per down 100 grams.Water solubility is preferably 50 grams/100 grams or higher, more preferably 100 grams/100 grams or higher.In addition, when mutual solubilising reagent of the present invention was fluid cpds, it preferably had 100 ℃ or higher, more preferably 120 ℃ or higher boiling point.
In the equipment of being furnished with alkaline purification bath of the present invention, solubilising reagent has prevented to adhere to the dry of the lip-deep alkaline solution of wall and solidify mutually, thereby can make solution keep stablizing.From applying alkaline solution up to the whole process that saponification finishes on the film surface, described mutual solubilising reagent can also suppress owing to applying the solid precipitation that film drying produces, and this solid precipitation is difficult to flush away in cleaning step.Described mutual solubilising reagent has also prevented being separated of water and the organic solvent that constitutes solvent.Especially, the coexistence of tensio-active agent, organic solvent and above-mentioned mutual solubilising reagent has reduced the turbidity of processing rear film, even and in long and successive saponification process, also can on whole surface, provide uniform saponification deg with stable manner.
The mutual solubilising reagent that the present invention uses can be any material that can satisfy above-mentioned condition.Solubilising reagent preferred examples comprises polyol compound mutually, and comprises the water-soluble polymers with hydroxyl and/or amide group repeating unit, for example sugar.
Polyol compound can be low-molecular-weight compound, oligomer compounds or polymer compound.The example of aliphatic polyol comprises the glycol (for example ethylene glycol, propylene glycol, butyleneglycol, pentanediol, hexylene glycol, glycerine monomethyl ether, glycerine list ether, cyclohexane diol, cyclohexanedimethanol, Diethylene Glycol or dipropylene glycol) with 2 to 8 carbon atoms, and the alkane with 3 to 18 carbon atoms (for example glycerine, methyltrimethylolmethane, trihydroxymethyl propane, three methyl alcohol butane, hexanetriol, tetramethylolmethane, Glycerol dimer, dipentaerythritol or inositol) that comprises 3 or more a plurality of hydroxyls.The polyalkylene oxide polyvalent alcohol can be in key by identical aklylene glycol or different aklylene glycols and form, but the polyalkylene polyvalent alcohol that is formed by identical aklylene glycol is preferred.In any situation, the quantity of Cheng Jian is preferably 3 to 100, and more preferably 3 to 50.Concrete example comprises polyoxyethylene glycol, polypropylene glycol and poly-(oxygen ethene-oxypropylene).
The example of sugar comprises the water-soluble cpds of for example describing: TennenKobunshi in following document, Japan polymer association, (Kyoritsu Shuppan compiles in Polymer Experimentology editorial board, 1984), the 2nd chapter, and Kindai Kogyo Kagaku 22, Tennenbutsu Kogyo Kagaku II, Ryohei Oda etc. compile (Asakura Shoten, 1967).The preferred sugar that does not contain free aldehydes or ketones base and do not have reducing property.It can be divided into glucose, sucrose, wherein reduce the trehalose type oligose of the mutual bonding of group, wherein sugar and the glycosides of the mutual bonding of reduction group of non-sugar and the sugar alcohol that is formed by sugared hydro-reduction, and all these compounds can advantageously use in the present invention.Trehalose type oligose comprises sucrose and trehalose, and glucosides comprises alkylglycoside, phenolic glycoside and glucosinolate for instance.In addition, sugar alcohol comprises D/L-arabitol, ribitol (ribit), Xylitol, D/L-Sorbitol Powder, D/L-mannitol, D/L-igit, D/L-talitol, galactitol and arodulcit.In addition, can advantageously use multibit that obtains by disaccharides hydrogenation and the reducing substance (reductive maltose) that forms by oligose hydrogenation.Wherein, the preferred nonreducing sugar of the present invention is sugar alcohol or sucrose, and the D-Sorbitol Powder, sucrose and the reductive maltose that have pooling feature in suitable pH scope are preferred especially and are cheap.This nonreducing sugar can use separately or two or more are used in combination.
The example that comprises the water-soluble polymers of the repeating unit with hydroxyl and/or amide group comprises addition reaction product, alkylidene polyol, polyalkylene oxide polyvalent alcohol and the sugar alcohol of natural gum (for example Sudan Gum-arabic, guar gum or tragacanth gum), polyvinyl alcohol, polyvinylpyrrolidone, vinylformic acid dihydroxypropyl ester polymer, Mierocrystalline cellulose or chitosan and ethylene oxide or propylene oxide.
In these alkylidene polyols, polyalkylene oxide polyvalent alcohol and sugar alcohol are preferred.Concrete example comprises that ethylene glycol, propylene glycol, butyleneglycol, Diethylene Glycol, two contract (positive propylene glycol), two contract (Isopropanediol), polyoxyethylene glycol (becoming bond number is 3 to 20), polypropylene glycol (becoming bond number is 3 to 10), glycerine and Glycerol dimers.
The content of these mutual solubilising reagent is preferably 0.5 to 35 weight % in the alkaline solution, more preferably 1 to 25 weight %.
The also preferred defoamer that adds in alkaline solution of the present invention.The content of defoamer in alkaline solution is preferably 0.001 to 5 weight %, more preferably 0.005 to 3 weight %.
In described scope, can remove attached to the lip-deep small bubbles of film, and can carry out the alkali soap processing equably, and can not occur irregular.
The example of defoamer comprises oil, for example Viscotrol C or Toenol 1140; Lipid acid, for example stearic acid or oleic acid; Fatty acid ester, for example native paraffin; Alcohol, for example polyoxyalkylene monohydroxy-alcohol; Ether, for example two-uncle-amylbenzene oxyethanol, heptyl cellosolve, nonyl cellosolve or 3-heptyl Trivalin SF; Phosphoric acid ester, for example tributyl phosphate or tributoxyethyl phosphate; Amine, for example diamyl amine; Acid amides, for example multiamide of polyalkylene amide or acidylate; Metallic soap, for example oleic calcium salt of aluminum stearate, calcium stearate, potassium oleate or wool; Sulphate esters, for example sodium sulfate dodecane ester; Silicone oil, for example multipolymer of dimethicone, tolyl polysiloxane, methylhydrogenpolysi,oxane, fluorine polysiloxane or dimethicone and polyoxyalkylene; And siloxanes, for example solution-type, emulsion-type or paste type silicone oil.
The used alkaline solution of the present invention also preferably comprises mould inhibitor and/or antiseptic-germicide.Mould inhibitor that uses among the present invention and antiseptic-germicide can be any kinds; as long as it does not harm alkali soapization, and its specific examples comprises the thibendole compound; isothiazolone compounds; the chlorophenol compound; the bromophenol compound; thiocyanic acid or rhodan-compound; acyl azide; diazine or triaizine compounds; thiourea compound; the alkyl guanidine compound; quaternary ammonium salt; organotin or zn cpds; the cyclohexyl phenolic compound; imidazoles and benzimidazole compound; sulfonamide compounds; active halogenated compound (for example sodium-chlor isocyanuric acid ester); sequestrant; sulfite compound; with penicillin is the antibiotic of representative.Also can use at L.E.West, " Wagter Quality Criteria ", Photo.Sci.and Eng., the 9th volume, the antiseptic-germicide of describing in the 6th page (1965), the mould inhibitor of in JP-A 57-8542,58-105145,59-126533,55-111942 and 57-157244, describing, and Hiroshi Horiguchi, " Antibacterial-antimold Chemistry " (Sankyo Shuppan, 1982), Bokin-Bokun Gijutu Handbook, Antibacterial-Antimold Society of Japan (Giho-do, 1986).Concrete example provides hereinafter, but these examples are not exclusiveness.
Mould inhibitor and/or the antiseptic-germicide add-on in alkaline solution is preferably 0.01 to 50 grams per liter, more preferably 0.05 to 20 grams per liter.
In the used alkaline solution of the present invention, can be used in combination other additive.For instance, can use alkaline solution stablizer (antiaging agent).In the present invention, the alkaline solution additive is not limited to these materials.
The water that uses in alkaline solution is preferably based on the hot spring regulations (No. 125, decree and superimposed clause thereof that on July 10th, 1948 issued) of the town water regulations (LaW No.177of 1957) of Japan and cabinet's decree based on this (No. the 56th, the decree of promulgation in the Ministry of Health on August 31st, 1978), Japan, and WHO town water standard, wherein defined the element of admixture and the influence of mineral substance in the water.In addition, in order to ensure effect of the present invention, the calcium concn that calculates with lime carbonate is preferably 0.001 to 200mg/L, and more preferably 0.01 to 150mg/L, and in preferred especially 0.05 to 10mg/L the scope.In described scope, can suppress the generation of insoluble substance in the solution.
The alkaline solution that is made of said components preferably has the surface tension of 45mN/m or lower (25 ℃), and the viscosity of 0.8 to 20mPas (25 ℃).Preferred surface tension force is 20 to 40mN/m (25 ℃), and viscosity is 1 to 15mPas (25 ℃).In described scope, with realize fully to film wettability of the surface matter, be coated in the maintain property of the lip-deep solution of film and after saponification reaction alkaline solution from the lip-deep removability of film.
In first and second embodiments of the present invention, use the surface treatment of the cellulose acylate film of above-mentioned alkaline solution can adopt any known method to implement, for example immersion process, spraying method or coating method.
In the situation of the one side of saponification film evenly and entirely, coating method is particularly preferred.Can use following known coating method to apply.
The saponification process is preferably implemented being no more than under 120 ℃ the treatment temp, and this temperature can not cause the distortion of handling film or the modification of treatment liq.Described temperature is more preferably at from 10 to 100 ℃, especially in preferred from 20 to 80 ℃ the scope.
In addition, when handling with coating method, the alkali soap processing is preferably implemented as follows: use surface temperature to equal or be higher than the step of 10 ℃ alkaline solution saponification cellulose acylate film; Cellulose acylate film remained on the step under the temperature that equals 10 ℃ at least; And from the cellulose acylate film the step of flush away alkaline solution.
Under the predetermined surface temperature, use the process of alkaline solution saponification cellulose acylate film can comprise the steps: before coating, to regulate the step of described film to preset temperature; Regulate the step of alkaline solution, perhaps both combination step to preset temperature.Preferably combination is adjusted to the step of preset temperature before coating.
In temperature to 20 of regulating in advance cellulose acylate film ℃ or higher step, can advantageously use the airflow of preset temperature to impact, the radiation heating of hot-rolling contact thermal conduction, microwave induced heating or Infrared heaters.Specifically, be preferred by hot-rolling contact thermal conduction, because it has high heat conduction efficiency, and can under little erection space, implement, and the film temperature at the transmission starting point place that can raise fast.Can use common double fastener laminar roller or electromagnetic induction roller (by producing Tokuden Co.).
In step, preferably limit coating amount and on film horizontal and vertical, be changed to 30% or lower with alkaline solution saponification cellulose acylate film.
As coating process, for instance, can advantageously use mold pressing coating machine (extrusion coating machine or slip coating machine), roll coater (preceding roll coater, reverse roll coater or grooved roll coating machine), rod coater (using the rod that twines with metal wire), perhaps knife coater.Coating method has description (Modern Coating andDrying Technology for example, Edward Cohen and Edgar B.Gutoff compile, VCHPublishers, Inc., 1992) in many documents.Consider the waste disposal in cleaning is subsequently removed, the coating amount of alkaline solution preferably should be as far as possible little.Particularly preferably be rod coater, mold pressing coating machine, grooved roll coating machine or knife coater, even under low coating amount, they also can stably be operated.
The preferred continuously coating method that adopts.
Draw total saponification number of sites by the saponification reaction number of sites on the unit surface cellulose acylate film being multiply by the required saponification degree of depth of adhesion oriented film, provide the required alkali coating amount of saponification reaction as index with total saponification number of sites.Because the consumption of alkali, speed of response reduces along with the carrying out of saponification reaction, and the coating amount in the preferred practical application equals several times of theoretical alkali coating amount.Specifically, be preferably 2 to 20 times of theoretical alkali coating amount, more preferably 2 to 5 times.
The temperature of alkaline solution preferably equals temperature of reaction (=film temperature).
Behind the coating alkaline solution, cellulose acylate film is remained under the temperature that equals 10 ℃ at least, finish until saponification reaction.Described temperature is preferably 15 ℃ or higher.
When selecting type of heating, should be taken into account that the cellulose acylate film surface is moistening by alkaline solution.For instance, can preferably use the radiation heating that blows warm air, contact thermal conduction, microwave induced heating or Infrared heaters to the back side of coated surfaces by hot-rolling.Infrared heaters is preferred, because it can realize heating by the noncontact mode, and does not use airflow, thereby to the minimum that influences on the surface of alkaline solution coating.As Infrared heaters, can make the far-infrared ceramic well heater of electricity consumption, gas, oil or steam-type.In having the environment of organic solvent,, preferably use oil or steam oil or steam type Infrared heaters as heating medium for blast protection.The temperature of cellulose acylate film can be identical or different with the Heating temperature before alkaline solution is handled.In addition, can be continuously during saponification reaction or progressively change temperature.For detect the temperature of film, can use be purchased exempt to contact infrared thermometer, and, can apply feedback control to heating unit for temperature being controlled in the above-mentioned scope.
In the present invention, implementing saponification in the time of particularly preferably in the transmission cellulose acylate film handles.The composition of combined alkali solution and coating method are determined the transmission speed of film.Transmission speed is preferably 10 to 500 meters/minute usually, more preferably 20 to 300 meters/minute.In order to realize stable coat operations, determine physical property (for example proportion, viscosity and surface tension), coating method and coating condition according to transmission speed.
In order to stop the saponification reaction of cellulose acylate film and alkaline solution, can adopt three kinds of methods.First kind is dilution coating alkaline solution, reduces alkali concn, thereby reduces the method for speed of response.Second kind is the temperature that reduces with the cellulose acylate film of alkaline solution coating, thereby reduces speed of response, and the third is to use acidic liquid neutral method.
In order to dilute the coating alkaline solution, can use the method for coating diluent, the method for spray diluent, perhaps cellulose acylate film is immersed in the method in the container that comprises diluent.Wherein, transmitting in the operation of cellulose acylate film the method for preferred coated diluent and spraying method continuously.The method of coating diluent is most preferred, because its required dilution liquid measure is minimum.
Preferred employing can apply diluent (re-applying) implements diluent to the continuously coating method on the cellulose acylate film that scribbles alkaline solution coating again.Coating method can be similar to the method described in the above-mentioned saponification processing.For promptly mixed ammonium/alkali solutions and diluent to reduce alkali concn, becoming streamlined mold pressing coating machine with liquid flow wherein compares, preferred roll coater or rod coater, liquid flow is uneven (to be also referred to as coating crimping (coating bead)) in these two kinds of coating machines in the zonule of coating application of liquid.
Diluent must be the liquid that can dissolve the alkaline reagents in the alkaline solution, because its objective is the reduction alkali concn, and does not dissolve or the swollen cellulose acylate film.Therefore, its mixture that makes water or organic solvent and water is as solvent.Organic solvent can use separately or two or more mix use, and can use in any way, as long as its ratio in diluent can not cause the dissolving or the swelling of cellulose acylate film.
Determine the coating amount of diluent according to the concentration of alkaline solution.Have in the streamlined mold pressing coating machine in the coating crimping, used coating amount is with 1.5 to 10 times of former alkaline solution dilutions, more preferably 2 to 5 times.In roll coater or rod coater, because the inhomogeneous flow in the coating crimping, alkaline solution and dilution liquid-phase mixing, and then coating mixing solutions.Therefore, because can't determine thinning ratio, so need after the coating dilute solution, measure the concentration of alkali from the coating amount of rare solvent.In addition, in roll coater or rod coater, diluted 1.5 to 10 times of preferred former alkali concn, more preferably 2 to 5 times.
In order to stop the saponification reaction of alkali rapidly, can also use acid.In order to finish neutralization with small amount of acid, strong acid is preferred.In addition, for the ease of cleaning, the salt that preferably is chosen in neutralization back and alkali formation has the acid of high-dissolvability in water.Particularly preferably be hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, chromic acid and methylsulfonic acid.
For alkaline solution with acid neutralization coating, can use spreading acid solution method, spray acid solution method or cellulose acylate film is immersed in the container that comprises acid solution.Wherein, transmitting in the operation of cellulose acylate film the method for the method of preferred coated acid solution and spray acid solution continuously.The method of spreading acid solution is most preferred, because its required acid solution amount is minimum.
Preferred employing the continuously coating method on the cellulose acylate film that scribbles alkaline solution of acid solution can being coated to is again implemented the coating of acid solution.Coating method can be similar to the method described in the above-mentioned saponification processing.For promptly mixed ammonium/alkali solutions and acid solution preferably use roll coater or rod coater with the alkali in the neutralization bases solution.
Determine the coating amount of acid solution according to the concentration of the kind of alkali and alkaline solution.Has in the streamlined mold pressing coating machine 0.1 to 5 times of the preferably former alkali coating amount of coating amount of acid, more preferably 0.5 to 2 times in the crimping in coating.In roll-coater or rod coater, because the inhomogeneous flow in the coating crimping, alkaline solution mixes mutually with acid solution, and then the coating mixing solutions.Therefore, can't be from the coating amount of acid solution be determined and speed, so need measure the concentration of alkali in acid solution coating back.In addition, in roll coater or rod coater, preferably determine the coated weight of acid solution, thereby obtain 4 to 9 pH value, more preferably 6 to 8 pH value in acid solution coating back.
Can also stop saponification reaction by the temperature that reduces cellulose acylate film.By reducing enough temperature, can stop saponification reaction basically from the state that remains on for accelerated reaction under room temperature or the higher temperature.When selecting refrigerating unit, should be taken into account that the cellulose acylate film surface is moistening.For instance, can be preferably to the back side of coated surfaces blowing cold air, perhaps by the contact thermal conduction of cooling roller.The temperature of cooling caudacoria is preferably 0 to 60 ℃, and more preferably 5 to 50 ℃, and most preferably be 10 to 30 ℃.The temperature of film is preferably used and is exempted to contact infrared thermometer and measure.Can also regulate cooling temperature by the feedback control on the refrigerating unit based on measured temperature.Heat sink can be used in combination with above-mentioned method or neutralization method with diluted.
In order thoroughly to remove alkaline solution, implement cleaning step.In use with situation about handling under, also need thoroughly to remove the salt component that is produced in for example neutralization.The salt component that the residue of alkaline solution or neutralization produce not only can make saponification reaction proceed, and influences oriented film and the formation of liquid crystal molecule coated film and the orientation of liquid crystal molecule that the back will apply.
Implement to clean by the method for coating water, the method for water spray or the method that polymeric film is immersed in the container that contains water.
Water spray means is implemented by using dispense tip (for example gravity flow coating machine or frog mouth formula coating machine), perhaps uses the nozzle that uses in air humidification, paint or automatic groove jar clean to implement.Can also use at document " All of Coating " coating method of describing among the Masayoshi Araki, KakoGijutsu Kenkyu-kai (1999).Can along film laterally, with the mode of the whole width of water impact film arrange taper or fan nozzle.Can also use the nozzle (for example producing) that is purchased by Ikeuchi Co. or Spraying Systems Inc..
The spray rate of water is high more, and the mixing of logistics more at random.But high speed may influence the transmission stability of cellulose acylate film when transmitting continuously.The impact velocity of spray is preferably 50 to 1000cm/sec, and more preferably 100 to 700cm/sec.
Although relevant with alkali concn, by product and solvent in the used alkalescence coating liquid, the consumption of rinse water can realize diluting at least 100 to 1,000 times, preferred 500 to 10,000 times, and more preferably 1,000 to 100,000 times.
For the rinse water of specified rate, preferably with the dipartite purging method in batches of rinse water, rather than the whole water of applied once.More particularly, rinse water is merotomized, supply with along a plurality of washing units of the transmission direction arranged in series of film.Between washing unit and next washing unit, provide reasonable time (distance), so that promote the dilution of alkali coating liquid by diffusion.More preferably tilt polymeric film in the transmission, thus make on the film water along the film surface flow, thus except spreading, also realize mixed diluting by flowing.In most preferred method, squeezing water is provided between washing unit, thereby further improves the efficient of cleaning and diluting.The specific examples of squeezing water is included in the roller that uses in the air knife that uses in the scraper that uses in the scraper type coating machine, the air-blade type coating machine and the roll coater.
More advantageously with series system a large amount of washing unit of arranging.But, consider installing space and equipment cost, use 2 to 20 grades usually, preferred 2 to 5 grades.
Behind squeezing water, the thickness of moisture film is preferably as far as possible little, but the thickness of moisture film is subjected to the restriction of used squeezing water type.In the method for using solid-state component (for example scraper, rod or roller) contact membrane, need to keep limited moisture film as lubricating fluid, even because when solid-state component is made of the soft elastomeric component of for example rubber, still might cause to the scraping on film surface or the wearing and tearing of elastomeric component.Usually, keep several microns or thicker, preferred 10 microns or thicker moisture film are as lubricating fluid.
As the squeezing water that can greatly reduce moisture film, air knife is preferred.By using enough air capacities and air pressure, the thickness of moisture film can be almost equal to zero.But preferred air-blowing quantity because too high air-blowing quantity may cause the shake or the skew of cellulose acylate film, thereby influences its transmission stability in specified range.Described scope is also relevant with the former water film thickness and the transmission speed of film on the cellulose acylate film, but uses 10 usually to 500m/sec, and preferred 20 to 300m/sec, and more preferably 30 to 200m/sec air velocity.In addition, in order to eliminate moisture film equably, regulate the air blowing aperture or the air supply method of air knife, make the distribution of cellulose acylate film air velocity in a lateral direction usually in 10%, preferably in 5%.Gap between cellulose acylate film surface in the transmission and the air knife gas hole footpath should be controlled in the suitable scope; because the gap is more little; the water squeezing ability is strong more, but causes thus causing that owing to contacting with cellulose acylate film abrasive possibility is high more.Therefore, keep 10 microns to 10 centimetres when usually air knife being installed, preferred 100 microns to 5 centimetres, and more preferably 500 microns to 1 centimetre gap.In addition, preferably on the back side of film clean surface, provide support roll, make it relative, be provided with, and alleviate the influence to film, for example shake, wrinkle or distortion thereby stablize the gap with air knife.
For rinse water, the preferred use purified waste water.Purifying waste water of using among the present invention means resistivity of water and is at least 1M Ω or higher, and metal ion (for example sodium, potassium, magnesium or calcium) content is lower than 1 mg/litre, and negatively charged ion (for example chlorine or nitrate radical) content is lower than 0.1 mg/litre.Can easily be purified water by reverse osmosis membrane, ion exchange resin, distillation or its combination.
The temperature of rinse water is high more, and cleansing power is strong more.But in the method for spraying water on the cellulose acylate film in transmission, water and air have bigger contact area, and evaporation at high temperature is more, thereby have increased the humidity of environment, and cause the danger of dewfall.Therefore, the temperature of rinse water is arranged on 5 to 90 ℃ usually, and preferred 25 to 80 ℃, and more preferably in 25 to 60 ℃ the scope.
When the component of alkali coating liquid or saponification reaction product are not soluble in water,, before or after cleaning step, can increase the solvent wash step in order to remove water-msoluble ingredients.The solvent wash step can use purging method or squeezing water and to solvent similar described in the diluent.
Behind cleaning step, can implement drying step.Because moisture film has been removed fully by for example squeezing water of air knife, thus do not need drying usually, but for before twining on the roller, regulate cellulose acylate film to required water content, can implement heat drying.On the other hand, airflow that can also the selectable humidity of apparatus is implemented moisture control.
[alkali soap process]
Surface treatment process in the third embodiment of the invention comprise with alkaline solution handle the step of cellulose acylate film and from the film the step of flush away alkaline solution, and preferably implement as follows: equaling or be higher than under the surface temperature of room temperature step with alkaline solution saponification cellulose acylate film; Cellulose acylate film remained on equal or be higher than step under the temperature of room temperature; And from the described cellulose acylate film the step of the described alkaline solution of flush away.
Can adopt any known method, for example immersion process, spraying method or coating method implement to handle with alkaline solution the step of cellulose acylate film.
Particularly only needing evenly and entirely in the situation of the one side of saponification film, coating method is particularly preferred.Can adopt the known coating method that to mention below to apply.
Equal or be higher than under the room temperature in that film is remained on after promoting saponification reaction, the step of flush away alkaline solution is the alkaline solution that dilution or neutralization comprise dense alkaline reagents and precipitate (for example film additive) from the film, thereby slow down or the termination saponification reaction, and use a large amount of cleaning liquids its flush away.In this step, deposit on the film surface for fear of concentrated base reagent or precipitate (for example film additive), the step of dilution or neutralization bases solution is very important, and by the carbonate concentration of keeping in alkali diluent and the alkali neutralising fluid is 3500mg/L or lower, can prevent from effectively to deposit on the film surface.Described concentration is preferably 1000mg/L or lower, and is preferably 100mg/L or lower especially.When coated with orientation film on the saponified cellulose acylate film; and form after friction treatment when having the optical anisotropic layer of liquid crystal molecule, the carbonate concentration that is equal to or less than 3500mg/L can reduce defective or the orientation defective that is caused by foreign matter.
The alkaline solution of high density trends towards absorbing the CO in the atmospheric environment 2Thereby, cause reduction and the sedimentary generation of pH.In order to suppress to absorb the CO in the atmospheric environment 2, more preferably the alkaline solution coating machine has semi-enclosed structure, and perhaps the organic solvent saturation steam with dry air, rare gas element or alkali soap solution covers.
In addition; when coated with orientation film on the saponified cellulose acylate film; and after friction treatment, form when having the optical anisotropic layer of liquid crystal molecule; concentration by chlorion and polyvalent metal ion (for example calcium ion or magnesium ion) in maintenance alkali diluent and the alkali neutralising fluid is respectively 300mg/L or lower and 500mg/L or lower; make dense alkaline reagents or precipitate (for example film additive) unlikely deposit on the film surface, adhere to thereby reduced with the defective of optical anisotropic layer.
For alkali diluent and alkali neutralising fluid, the preferred liquid that constitutes by water and organic solvent that uses, this will explain in the back, and the water that uses is preferably purified waste water.For purifying waste water, the calcium concn in the liquid is preferably 0.001 to 100mg/L, and more preferably 0.001 to 50mg/L, and is preferably 0.001 especially to 10mg/L.Magnesium density is preferably 0.001 to 50mg/L, and more preferably 0.001 to 30mg/L, and is preferably 0.001 especially to 10mg/L.Except calcium and magnesium, preferably there is not other polyvalent metal ion, for example Be, Sr, Ba, Al, Sn, Pb, Ti, Cr, Mn, Fe, Co, Ni, Cu (II), Co or Zn.The concentration of polyvalent metal ion is preferably 0.001 to 150mg/L.On the other hand, alkali soap solution does not preferably contain the negatively charged ion of chlorion for example or carbanion.The concentration of chlorion is preferably 0.001 to 100mg/L, and more preferably 0.001 to 50mg/L, and is preferably 0.001 especially to 10mg/L.In addition, preferably there is not carbanion.The concentration of carbanion is preferably 0.001 to 500mg/L, and more preferably 0.001 to 100mg/L, and is preferably 0.001 especially to 20mg/L.These ionic concentration are preferably low as far as possible, and lower limit 0.001mg/L means it and is equal to or less than measuring limit.In these concentration ranges, can be suppressed at and produce insoluble material in the solution.
The alkali soap method of cellulose acylate film is preferably implemented as follows: heat the step of cellulose acylate film to room temperature or higher temperature in advance; The step of coating alkaline solution on described cellulose acylate film; Cellulose acylate film remained on equal or be higher than step under the temperature of room temperature, and preferably in the transmission cellulose acylate film, implement these steps.
Equaling or be higher than under the surface temperature of room temperature, using the process of alkaline solution saponification cellulose acylate film can adopt following steps: before coating, to regulate film to the step that equals or be higher than the temperature of room temperature; Preheat the step of alkaline solution, perhaps make up both steps.Preferred combination is heated to the step that equals or be higher than the temperature of room temperature before coating.
To equaling or be higher than in the step of temperature of room temperature, can advantageously use hot blast to impact the radiation heating that (airs blowing), hot-rolling formula contact thermal conduction, microwave induced heating or Infrared heaters at prior heating cellulose acylate film.Specifically, preferably adopt hot-rolling contact thermal conduction,, and can under little erection space, implement because it has high heat conduction efficiency, and the film temperature at the transmission starting point place that can raise fast.Can use common double fastener laminar roller or electromagnetic induction roller (producing) by Tokuden Co..
Be advantageously to use mold pressing coating machine (extrusion coating machine or slip coating machine), roll coater (preceding roll coater, reverse roll coater or grooved roll coating machine) or rod coater (using the rod that twines with metal wire) in the step of coating alkali soap solution on the cellulose acylate film.Coating method has description (Modern Coatingand Drying Technology for example, Edward Cohen and Edgar B.Gutoff compile, VCHPublishers, Inc., 1992) in many documents.Consider the waste disposal of removing by cleaning subsequently, the coating amount of alkaline solution is preferably as far as possible little, and is preferably 1 to 100cc/cm 3, more preferably 1 to 50cc/cm 3Even particularly preferably be under low coating amount also can stable operation rod coater, grooved roll coating machine or scraper type coating machine.
Preferably alkaline solution is coated on the lower surface of cellulose acylate film, thus after by coating alkaline solution saponification cellulose acylate film, can be easily from the cellulose acylate film the flush away alkaline solution.
Preferred restriction coating amount is changed to 30% or littler on film horizontal and vertical.Can also use the continuously coating method.
In alkali soap method of the present invention, behind the coating alkaline solution, cellulose acylate film remained on equal or be higher than under the temperature of room temperature.In the present invention, room temperature refers to 20 ℃.
Heating means are selected by the moistening fact of alkaline solution in consideration cellulose acylate film surface.For instance, can preferably adopt warm air impact the back side of (blowing) coated surfaces, by the radiation heating of hot-rolling contact thermal conduction, microwave induced heating or Infrared heaters.Infrared heaters is preferred, because it can realize heating by the noncontact mode, and does not use airflow, thereby to the minimum that influences on the surface of alkaline solution coating.As Infrared heaters, can make the far-infrared ceramic well heater of electricity consumption, gas, oil or steam-type.Can use the Infrared heaters (for example by Noritake Co., Ltd. produces) that is purchased.In having the environment of organic solvent,, preferably use oil or steam oil or steam type Infrared heaters as heating medium for blast protection.The temperature of cellulose acylate film can be identical or different with the Heating temperature before alkaline solution is handled.In addition, can be continuously during saponification reaction or progressively change temperature.Film temperature is 20 to 150 ℃, is preferably 25 to 100 ℃, and more preferably 35 to 80 ℃.
For detect the temperature of film, can use be purchased exempt to contact infrared thermometer, and, can apply feedback control to heating unit for temperature being controlled in the above-mentioned scope.
Be variable from coating alkaline solution to holding time of flush away alkaline solution in the said temperature scope, this depends on the transmission speed of explained later, but preferred described holding time is 1 second to 5 minutes, more preferably 2 to 100 seconds, and be preferably 3 to 50 seconds especially.
Preferably enforcement alkali soap treatment step in the transmission film, and the composition of combined alkali solution and coating method are determined the transmission speed of cellulose acylate film.Described speed is preferably 10 to 500 meters/minute usually, more preferably 20 to 300 meters/minute.
In addition; heating cellulose acylate film in advance to the step of room temperature or higher temperature or before coating alkaline solution on the cellulose acylate film; in order to remove dust and on the film surface, to obtain more uniform wet characteristic, can implement electric charge and remove processing, dust removal process or moist curing.These processing can adopt known method to implement, and wherein the electric charge removing method can be the method for describing in JP-A 62-131500, and dust removing method can be the method for describing in JP-A2-43157.
The film temperature is remained on equal or higher temperature under promote saponification reaction after, in order to slow down or to stop the saponification reaction of cellulose acylate film and alkaline solution, mainly can adopt three kinds of methods.First kind is dilution coating alkaline solution, reduces alkali concn, thereby reduces the method for speed of response.Second kind is the temperature that reduces with the cellulose acylate film of alkaline solution coating, thereby reduces speed of response, and the third is to use acidic liquid neutral method.
As previously mentioned, use the method for alkali diluent and to use the method for alkali neutralising fluid also be the part of the step of flush away alkaline solution from the film.
In order to dilute the coating alkaline solution, can adopt the coating diluent method, spray diluent method or cellulose acylate film is immersed in method in the container that comprises diluent.Transmitting continuously in the operation of cellulose acylate film, the method for the method of coating diluent and spray diluent is preferred.The method that wherein applies diluent is most preferred, because its required dilution liquid measure is minimum.
Preferred employing the continuously coating method on the cellulose acylate film that scribbles alkaline solution of diluent can being coated to is again implemented the coating of diluent.In order to carry out described coating, can advantageously use mold pressing coating machine (extrusion coating machine or slip coating machine), roll coater (preceding roll coater, reverse roll coater or grooved roll coating machine) or rod coater (using the rod that twines with metal wire) for instance.Coating method has description (Modern Coating and Drying Technology for example, Edward Cohen and Edgar B.Gutoff compile, VCH Publishers, Inc., 1992) in many documents.For promptly mixed ammonium/alkali solutions and diluent, thereby reduction alkali concn, becoming streamlined mold pressing coating machine with liquid flow wherein compares, preferred roll coater or rod coater, liquid flow is uneven (to be also referred to as coating crimping (coating bead)) in these two kinds of coating machines in the zonule of coating application of liquid.
In order to reduce alkali concn, and avoid precipitate (for example film additive) is deposited on the film, so alkali diluent or neutralising fluid must be the liquid that can dissolve the alkaline reagents in the alkaline solution.Therefore, the mixture that preferably makes water or organic solvent and water is as solvent, and can use two or more organic solvents in mixture.Can preferentially use the organic solvent that uses in the alkaline solution of mentioning later.Water is a kind of preferred solvent.
In addition, for fear of the deposition of precipitate (for example film additive) on film, alkali diluent or neutralising fluid preferably comprise tensio-active agent.Tensio-active agent is not particularly limited, but can advantageously uses the tensio-active agent that uses in the alkaline solution of mentioning in the back.In addition, deposit on the film surface for fear of small bubbles, so that finish the cleaning of alkaline solution and alkali diluent equably, alkali diluent or neutralising fluid preferably comprise the defoamer of mentioning later.
Determine the coating amount of diluent according to the concentration of alkaline solution.Have in the streamlined mold pressing coating machine in the coating crimping, used coating amount is with 1.5 to 10 times of former alkaline solution dilutions, more preferably 2 to 5 times.In roll coater or rod coater, because the inhomogeneous flow in the coating crimping, alkaline solution and diluent mix, and then the coating mixing solutions.Therefore, because can't determine thinning ratio, so need after the coating dilute solution, measure the concentration of alkali from the coating amount of rare solvent.In addition, in roll coater or rod coater, diluted 1.5 to 10 times of preferred former alkali concn, more preferably 2 to 5 times.
In order to stop the saponification reaction of alkali rapidly, can also use acid.In order to finish neutralization with small amount of acid, strong acid is preferred.In addition, for the ease of cleaning, the salt that preferably is chosen in neutralization back and alkali formation has the acid of high-dissolvability in water.Particularly preferably be hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, chromic acid and methylsulfonic acid.
When alkaline solution had the carbonate of high density or chlorion, neutralization reaction may produce precipitation fast, in the case, preferably added the weak acid with shock absorption in the alkali neutralising fluid.These weak acid can be sugar, for example Sorbitol Powder, sucrose, glucose, semi-lactosi, pectinose, wood sugar, fructose, ribose, seminose or L-xitix; Alcohol; Aldehyde; Compound with phenolic hydroxyl group; The material that oxime or nucleic acid are relevant as at Ionization Constans ofOrganic Acids in Aqueous Solution, is described among the Pergamon Press.
For alkaline solution with acid neutralization coating, can use spreading acid solution method, spray acid solution method or cellulose acylate film is immersed in method in the container that comprises the acid solution body.Wherein, transmitting continuously in the operation of cellulose acylate film, the method for the method of spreading acid solution and spray acid solution is preferred.Wherein the method for spreading acid solution is most preferred, because of its acid solution consumption minimum.
Preferred employing the continuously coating method on the cellulose acylate film that scribbles alkaline solution of acid solution can being coated to is again implemented the coating of alkali neutralising fluid.For coating, can advantageously use mold pressing coating machine (extrusion coating machine or slip coating machine), roll coater (preceding roll coater, reverse roll coater or grooved roll coating machine), rod coater (using the rod that twines with metal wire) for instance.Coating method has description (Modern Coating and Drying Technology for example, Edward Cohen and Edgar B.Gutoff compile, VCH Publishers, Inc., 1992) in many documents.For promptly mixed ammonium/alkali solutions and neutralising fluid, thereby reduction alkali concn, becoming streamlined mold pressing coating machine with liquid flow wherein compares, preferred roll coater or rod coater, liquid flow is uneven (to be also referred to as coating crimping (coating bead)) in these two kinds of coating machines in the zonule of coating application of liquid.
Determine the coating amount of neutralising fluid according to the concentration of the kind of alkali and alkaline solution.Have in the streamlined mold pressing coating machine in the coating crimping, the preferably former alkali of the coating amount of neutralising fluid applies 0.5 to 2 times of liquid measure.In roll-coater or rod coater, because the inhomogeneous flow in the coating crimping, alkaline solution and dilution liquid-phase mixing, and then apply mixing solutions.Therefore, because can't be from the coating amount of acid solution be determined and speed, so need behind the coating neutralising fluid, measure the concentration of alkali.In addition, in roll coater or rod coater, preferably determine the coated weight of acid solution, thereby obtain 4 to 9 pH value, more preferably 6 to 8 pH value in acid solution coating back.
In order to reduce alkali concn, and avoid precipitate (for example film additive) is deposited on the film, so the alkali neutralising fluid must be the liquid that can dissolve the alkaline reagents in the alkaline solution.Therefore, the mixture that preferably makes water or organic solvent and water is as solvent, and can use two or more organic solvents in mixture.Can preferentially use the organic solvent that uses in the alkaline solution of mentioning later.Water is a kind of preferred solvent.
In addition, for fear of the deposition of precipitate (for example film additive) on film, the alkali neutralising fluid preferably comprises tensio-active agent.Tensio-active agent is not particularly limited, but can advantageously uses the tensio-active agent that uses in the alkaline solution of mentioning in the back.In addition, in order to improve cleaning efficiency, the alkali neutralising fluid preferably comprises defoamer.
Also can also stop saponification reaction by the temperature that reduces cellulose acylate film.By reducing enough temperature, can stop saponification reaction basically from the state that remains on for accelerated reaction under room temperature or the higher temperature.When selecting refrigerating unit, should be taken into account that the cellulose acylate film surface is moistening.For instance, can be preferably to the back side of coated surfaces blowing cold air, perhaps by the contact thermal conduction of cooling roller.The temperature of cooling caudacoria is preferably 5 to 60 ℃, and more preferably 10 to 50 ℃, and most preferably be 15 to 30 ℃.The temperature of film is preferably used and is exempted to contact infrared thermometer and measure.Can also regulate cooling temperature by the feedback control on the refrigerating unit based on measured temperature.
[cleaning step]
In order to remove alkaline solution, alkali diluent or alkali neutralising fluid, implement cleaning step.The residual saponification reaction that not only can make of alkaline reagents, acid, salt or precipitate (for example film additive) is proceeded, and influences the formation of coated film of oriented film that the back will apply and liquid crystal molecule and the orientation of liquid crystal molecule.
Implement to clean by the method for coating water, the method for water spray or the method that cellulose acylate film is immersed in the container that water is housed.Transmitting continuously in the operation of cellulose acylate film, the method and the spraying method of coating rinse water are preferred.Mix with arbitrarily flowing of alkali coating liquid because in spray water flow, can on cellulose acylate film, realize rinse water, so the method for spray Cleaning for High Capacity water is particularly preferred.
Water spray means is implemented by using dispense tip (for example gravity flow coating machine or frog mouth formula coating machine), perhaps uses the nozzle that uses in air humidification, paint or automatic groove jar clean to implement.Can also use at document " All of Coating " coating method of describing among the Masayoshi Araki, KakoGijutsu Kenkyu-kai (1999).Can along film laterally, with the mode of the whole width of water impact film arrange taper or fan nozzle.Can also use the nozzle (for example producing) that is purchased by Ikeuchi Co. or Spraying Systems Inc..
The spray rate of water is high more, and the mixing of logistics more at random.But high speed may influence the transmission stability of cellulose acylate film when transmitting continuously.The impact velocity of spray is preferably 50 to 1000cm/sec, and more preferably 100 to 700cm/sec, and most preferably is 100 to 500cm/sec.
Preferably be controlled on the vertical and horizontal of cellulose acylate film of transmission in the unit time fluctuation of injection flow rate less than 30%.But at the horizontal two ends of cellulose acylate film, alkali soap solution is bigger usually with the coating amount that is used for the neutral acid solution.In order to guarantee cleaning, can also increase the injection flow rate on the transverse ends to the bigger part of coating amount.In the situation of using dispense tip, can do the gap of water outlet slit wideer, to be increased in the flow at two ends.In addition, for moisture film is provided partly at two ends, can use the coating machine of little width separately.Can in a plurality of unit, use the coating machine of little width.In addition, in the situation of using spray nozzle, can use nozzle to implement local water spray at two ends.
For the rinse water of specified rate, preferably with the dipartite purging method in batches of rinse water, rather than the whole water of applied once.More particularly, rinse water is merotomized, supply with along a plurality of washing units of the transmission direction arranged in series of film.Between washing unit and next washing unit, provide reasonable time (distance), so that promote the dilution of alkali coating liquid by diffusion.More preferably tilt polymeric film in the transmission, thus make on the film water along the film surface flow, thus except spreading, also realize mixed diluting by flowing.In most preferred method, squeezing water is provided between washing unit, thereby further improves the efficient of cleaning and diluting.The specific examples of squeezing water is included in the roller that uses in the air knife that uses in the scraper that uses in the scraper type coating machine, the air-blade type coating machine and the roll coater.
More advantageously with a large amount of washing unit of series system arrangement.But, consider installing space and equipment cost, use 2 to 10 grades usually, preferred 2 to 5 grades.
Behind squeezing water, the thickness of moisture film is preferably as far as possible little, but the thickness of moisture film is subjected to the restriction of used squeezing water type.In the method for using solid-state component (for example scraper, rod or roller) contact membrane, need to keep limited moisture film as lubricating fluid, even because when solid-state component is made of the soft elastomeric component of for example rubber, still might cause to the scraping on film surface or the wearing and tearing of elastomeric component.Usually, keep several microns or thicker, preferred 10 microns or thicker moisture film are as lubricating fluid.
As the squeezing water that can greatly reduce moisture film, air knife is preferred.By using enough air capacities and air pressure, the thickness of moisture film can be almost equal to zero.But preferred air-blowing quantity because too high air-blowing quantity may cause the shake or the skew of cellulose acylate film, thereby influences its transmission stability in specified range.Described scope is also relevant with the former water film thickness and the transmission speed of film on the cellulose acylate film, but uses 10 usually to 500m/sec, and preferred 20 to 300m/sec, and more preferably 30 to 200m/sec air velocity.In addition, in order to eliminate moisture film equably, regulate the air blowing aperture or the air supply method of air knife, make cellulose acylate film air velocity in a lateral direction have usually in 10% the preferably distribution in 5%.Gap between cellulose acylate film surface in the transmission and the air knife gas hole footpath should be controlled in the suitable scope; because the gap is more little; the water squeezing ability is strong more, but causes thus causing that owing to contacting with cellulose acylate film abrasive possibility is high more.Therefore, keep 10 microns to 10 centimetres when usually air knife being installed, preferred 100 microns to 5 centimetres, and more preferably 500 microns to 1 centimetre gap.In addition, preferably on the back side of film clean surface, provide support roll, make it relative, be provided with, and alleviate the influence to film, for example shake, wrinkle or distortion thereby stablize the gap with air knife.
For rinse water, the preferred use purified waste water.Purifying waste water of using among the present invention means resistivity of water and is at least 1M Ω or higher, and metal ion (for example sodium, potassium, magnesium or calcium) content is lower than 1 mg/litre, and negatively charged ion (for example chlorine or nitrate radical) content is lower than 0.1 mg/litre.Can easily be purified water by reverse osmosis membrane, ion exchange resin, distillation or its combination.
The temperature of rinse water is high more, and cleansing power is strong more.But in the method for spraying water on the cellulose acylate film in transmission, water and air have bigger contact area, and evaporation at high temperature is more, thereby have increased the humidity of environment, and cause the danger of dewfall (dewing).Therefore, the temperature of rinse water is arranged on 5 to 90 ℃ usually, and preferred 25 to 80 ℃, and more preferably in 25 to 60 ℃ the scope.
When the component of alkaline solution or saponification reaction product are not soluble in water,, before or after cleaning step, can increase the solvent wash step in order to remove water-msoluble ingredients.The solvent wash step can be used purging method or squeezing water, and can use and solvent like the solvent of the alkaline solution of mentioning later or the solvent phase described in the Solvent Pocket Book New Edition (Ohm-sha, 1994).
Behind cleaning step, can implement drying step.Because moisture film has been removed fully by for example squeezing water of air knife, thus do not need drying usually, but for before twining on the roller, regulate cellulose acylate film to required water content, can implement heat drying.On the other hand, airflow that can also the selectable humidity of apparatus is implemented moisture control.The temperature of dry air is preferably 30 to 200 ℃, and more preferably 40 to 150 ℃, and be in particular 50 to 120 ℃.
In alkaline purification process of the present invention, after above-mentioned saponification step, implement the coating of functional layer.Carry out saponification by coating from the teeth outwards and handle, then apply functional layer in the above, thereby when after functional layer is provided, rolling up film, can prevent the adhesion between the functional layer surface and the film back side.
[replenishing method of additive liq]
First embodiment of the replenishing method of additive liq of the present invention is by using alkaline solution continuous saponification polymeric film surface to produce in the process of alkali soap fluidized polymer film, uses the method for additive liq supply alkaline solution, and it comprises:
Measure the step of alkaline solution saponification ability;
Based on the saponification ability of being surveyed, determine the supply mode of additive liq, thereby after with described additive liq supply, make the saponification ability of described alkaline solution be in step in the pre-determined range; And
With determined supply mode, with the step of the described alkaline solution of described additive liq supply.
In first embodiment of the replenishing method of additive liq of the present invention, at first implement to measure the step of alkaline solution saponification ability.
Generally speaking, " the saponification ability " of alkaline solution is usually relevant with the concentration of hydroxide ion (OH-) in the alkaline solution in the saponification process.Therefore, directly or indirectly measure the index of the concentration of hydroxide ion in the present invention as the saponification ability.
The method of measuring alkaline solution saponification ability is not particularly limited, and is be selected from following method a kind of at least preferably: the measurement of the electrode potential between the measurement of the electrode voltage between the electrode of the measurement of the measurement of alkaline solution pH, alkaline solution specific conductivity, the measurement of alkaline solution electric impedance, current control and the electrode of current control.This be because described method can hold and cheap metering facility in implement, and can provide accurate observed value.
The device of measuring alkaline solution saponification ability can be provided in the alkaline solution.Described device can be provided on two or more positions, and from these DATA REASONING saponification abilities.
The measurement of alkaline solution pH can be used the pH transmitter that is purchased, and for example glass electrode pH transmitter or semi-conductor pH transmitter are implemented.Wherein, semi-conductor pH transmitter is preferred.
Semi-conductor pH transmitter is equipped with potential electrode, reference electrode and temperature compensating electrode, and described potential electrode uses ISFET (ion sensing fet) to respond hydrogen ion.ISFET is made by durable solid state silicon chips, and has excellent response performance.In addition, in pH measured, even always be immersed in the alkaline solution of high basicity, semi-conductor pH transmitter can not corroded yet, and can accurately measure the pH of alkaline solution in long period.
The preferred semi-conductor pH transmitter that uses can be that (Honeywell Inc. produces LQH21 for instance among the present invention, sell at the dealer Yamatake of Japan Co. by it), the 0010-15C and the 1001 pH systems (make by Centron Inc., sell at the dealer Japan of Japan Machinery Co.) that produce by Horiba Seisakusho Co. by it.
The conductance measurement of alkaline solution can use the conductivitimeter that is purchased to measure.More particularly, conductivitimeter can be electrode type or electromagnetic induction type.Preferred conductivitimeter is equipped with temperature-compensation circuit (for example ± 2%/℃).Measuring element with conductivitimeter during measurement immerses in the alkaline solution, for example immerses in the alkaline solution recycle system of saponification equipment.Especially, be preferably placed at the position in the alkaline solution groove or be arranged in circulation tube.
The measurement of alkaline solution electric impedance can be used impedance bioelectrical measurement equipment, and for example AC impedometer, AC electric bridge or other impedometer are implemented.
Measuring the top condition of electric current, the oscillation frequency of impedance bioelectrical measurement equipment etc. decides on the composition of alkaline solution etc.Usually, for protection equipment and prevent the electrolysis of alkaline solution, measure electric current and preferably be in quite low level.Consider and alkaline solution in relation between the static capacity component, oscillation frequency is preferably hundreds of Hz to hundreds of kHz.
Comprise the electric impedance of electrolytical alkaline solution and the temperature correlation of solution.More particularly, solution temperature increases, and electric impedance reduces.Therefore, preferred impedance bioelectrical measurement equipment is equipped with detector unit and temperature-compensation circuit.
When measuring, the measuring element of impedance bioelectrical measurement equipment can be immersed in the alkaline solution, for example immerse in the alkaline solution recycle system of saponification equipment.Especially, preferably immerse in the alkaline solution groove or in the circulation tube.
The electrode voltage between the electrode of current control and/or the measurement of electrode potential can be by installing the current control electrode in the alkaline solution groove, and the electrode voltage between the potential electrode and/or electrode potential are implemented.
The electrode voltage between the electrode of current control and/or the measurement of electrode potential can prevent unusual electrode reaction, because electric current only flows in the scope of control.Therefore, can prevent the electrode voltage that causes by unusual electrode reaction and/or the deterioration of electrode potential measuring apparatus, the deterioration and the pollution of alkaline solution.
Electric current in the electrode is the constant electric current preferably.This is because electric current is controlled easily and had high stability, and electric current preferably is about 5 to 100 milliamperes.
Preferably pass through current sweep method control electrode electric current with potential electrode voltage and/or electrode potential.For the current sweep method, can use known method, for example singly sweep (singlesweeping) method or sweep (multiple sweeping) method more.In this operation, preferably provide the device of measuring the alkaline solution temperature simultaneously, and temperature correction is implemented in the measurement of counter electrode voltage and/or electrode potential.
Be used to measure the electrode voltage between the electrode of current control and/or the preferably alkali proof electro-conductive material of electrode of electrode potential.Preferred examples comprises the titanium electrode of titanium, SUS material (for example SUS316 or SUS316L), platinum, covering platinum, titanium electrode and the carbon dioxide process carbon electrode of using the platinum family oxide compound to cover.
The structure of counter electrode is not particularly limited, and can be cylinder shape, clavate, net form, annular or dish type.In addition, electrode can be fixed electrode or removable electrode, for example rotating electrode.
The measurement of electrode voltage can use the voltampere meter that is purchased to implement.In addition, the measurement of electrode potential can use the potentiometer that is purchased to implement.
In current control, the current waveform of pulse shape is preferred, because it helps preventing the electrode fouling that caused by electrolysis and the pollution that is brought by deposition etc.
As pulse method, can use known method, for example constant current single pulse method or constant current two pulse method.For instance, pulse waveform can be oblique wave, staircase waveform (st prints pedwave), choppy sea, square wave, trapezoidal wave, zigzag wave or sine wave.
The counter-rotating of current polarity in the current control helps preventing the electrode fouling that caused by electrolysis and the pollution that is brought by deposition etc.The time of reversal of poles is preferably 1 to 1000 millisecond, and the reversal of poles ratio preferably be about-: +=1: 1 to 1: 10.
Then,, implement to determine the step of the supply mode of additive liq, thereby make that after with described additive liq supply, the saponification ability of alkaline solution is in the pre-determined range based on the saponification ability that records.
The lasting reduction of saponification ability causes the saponification level on the polymer surfaces to cross low or the uneven shortcoming of saponification level.Therefore, the reduction of saponification ability need be maintained within a certain range, in order to avoid above-mentioned shortcoming occurs.
, for instance, be lower than in the situation of preset value for this reason, determine to increase the degree of saponification ability, and determine the supply mode of required additive liq based on measured saponification ability in the saponification ability that records.The composition, increment, supply that the supply mode of additive liq comprises additive liq at interval etc.
For instance, reduce in the degree condition with higher in the saponification ability that records, improve additive liq alkali concn, increase additive liq increment, shorten additive liq supply at interval or in conjunction with above-mentioned measure.In addition, reduce in the less situation of degree in the saponification ability that records, use the lower additive liq of alkali concn, reduce additive liq increment, prolong additive liq supply at interval or in conjunction with above-mentioned measure.
Hereinafter, will provide concrete explanation according to the method that is used to measure alkaline solution saponification ability.
In the situation of using alkaline solution pH measurement as the method for measuring alkaline solution saponification ability, measure the pH value of alkaline solution, then when the pH value that records is lower than preset value, based on the pH value that records, determine the increasing degree of saponification ability, and correspondingly determine the supply mode of additive liq.
In the situation of using the alkaline solution conductivity measurement, measure the specific conductivity of alkaline solution, when the specific conductivity that records is lower than preset value,, determine the increasing degree of saponification ability then, and correspondingly determine the supply mode of additive liq based on the specific conductivity that records.
In the situation of using the alkaline solution impedance bioelectrical measurement, measure the electric impedance of alkaline solution, when the electric impedance that records is lower than preset value,, determine the increasing degree of saponification ability then, and correspondingly determine the supply mode of additive liq based on the electric impedance that records.
The electric impedance (hereinafter being called " first impedance value ") of alkaline solution and the electric impedance (hereinafter being called " second impedance value ") when being higher than alkaline solution and degrading to beginning and on the polymeric film surface, produce inhomogeneous saponification before selecting above-mentioned preset value to be lower than to use.Preferably set the about intermediate value of described preset value between first impedance value and second impedance value.
In addition, the supply mode of additive liq preferably makes alkaline solution reach the required supply mode of first impedance value.
In case determined the composition of alkaline solution and additive liq and the alkaline solution amount of the alkaline solution groove of packing into, can determine the value of supply mode by simple simulation test.
In the electrode voltage between the electrode that uses current control and/or the measurement of electrode potential the situation as the method for measuring alkaline solution saponification ability, electrode voltage and/or electrode potential between the electrode of measurement current control, then when the electrode voltage that records thus and/or electrode potential are not in the predetermined reference scope, based on electrode voltage that records and/or electrode potential, determine the increasing degree of saponification ability, and correspondingly determine the supply mode of additive liq.
In preferred embodiment of method of the present invention, the processing area of unit of measure's time inner polymer film, and determine above-mentioned pre-determined range based on the processing area of measured unit time inner polymer film.Specifically,, preferably reduce the degradation of preset value if the processing area of unit time inner polymer film is bigger, and if the processing area of unit time inner polymer film is less, then preferably improve the degradation of preset value.
More particularly, for example when the method for alkaline solution saponification ability is measured in the conductivity measurement effect of using alkaline solution, the specific conductivity reference value that big or little according to the processing area of unit time inner polymer film, selected as can be known conduct judge whether to carry out supply has been decided height or is low surely.
For the situation of using pH value to measure to wait as the method for measurement alkaline solution saponification ability, method that can applications similar.
To the measurement of the processing area of unit time inner polymer film be made an explanation in second embodiment of the present invention below.
Then, according to above-mentioned definite supply mode, implement step with additive liq supply alkaline solution.
Replenishing method to additive liq is not particularly limited, and can implement by known method.
For instance, during increment in changing supply mode, can use self-operated measuring unit, for example measure pump automatically.
Second embodiment of the present invention is to use the method for the described alkaline solution of additive liq supply in the process of using alkaline solution continuous saponification polymeric film surface with production alkali soap fluidized polymer film, and it comprises:
Measure the step of the processing area of described polymeric film in the unit time;
Carry out the pre-storage that required alkaline solution is processed in saponification according to described polymeric film, by the step of the consumption of alkaline solution in the processing area Units of Account time in the measured unit time to unit surface;
Consumption in the unit time that draws based on aforementioned calculation is determined the supply mode of additive liq, thereby after with described additive liq supply, makes the saponification ability of described alkaline solution be in step in the pre-determined range; And
According to determined supply mode, with the step of the described alkaline solution of described additive liq supply.
In second embodiment of the replenishing method of additive liq of the present invention, at first implement the step of the processing area of unit of measure's time inner polymer film.
Can adopt known method to come the processing area of unit of measure's time inner polymer film.For instance, can make in the following method: place a plurality of optical detection elements at interval and perpendicular to the polymeric film surface of transmission continuously with constant, based on light, make polymeric film width detection element circuitry detect the width of polymeric film then from the polymeric film reflection; And, use the processing area of polymeric film area integral circuit Units of Account time inner polymer film by handling information and the transmission speed that detects.
Then, carry out the pre-storage that required alkaline solution is handled in saponification, the consumption of alkaline solution in the processing area Units of Account time in the unit time that records based on polymeric film to unit surface.
The polymeric film of unit surface is carried out saponification, and to handle the amount of required alkaline solution be the theoretical quantity of alkali consumption that the back will be explained.Theoretical quantity of alkali consumption multiply by processing area in the unit time that records in previous step is rapid, the consumption of alkaline solution in the Units of Account time.
Then,, determine the supply mode of additive liq, thereby make that the saponification ability of alkaline solution is in the pre-determined range after using the additive liq supply based on the consumption of alkaline solution in the unit time of calculating.
Specifically, the saponification ability when alkaline solution consumes in the time in unit of measure is calculated in alkali concn and the amount of alkaline solution and the consumption of alkaline solution of alkaline solution before handling from saponification.After this, the same in the first embodiment of the invention that coexists, based on the saponification amount that calculates, determine the increasing degree of saponification ability, and determine the supply mode of required additive liq.
After this, according to the supply mode of determining thus, with the described alkaline solution of additive liq supply.Similar in this step and the first embodiment of the invention.
In second embodiment of additive liq replenishing method of the present invention, the alkaline solution deterioration that preferred calculating causes owing to absorbing carbon dioxide gas, and feed back in the calculating that alkaline solution in the unit time is consumed.
Calculating such as the temperature when specifically, handling according to saponification in the atmosphere, humidity, pressure are because the alkaline solution deterioration that absorbing carbon dioxide gas causes.
In second embodiment of the replenishing method of first embodiment of the replenishing method of additive liq of the present invention and additive liq of the present invention,, make the alkaline solution of deterioration recover the saponification ability by using the additive liq supply.Therefore, the hydroxide ion concentration in the alkaline solution increases.
Therefore, the deterioration that causes alkaline solution that saponification is in the present invention handled, and recovered the saponification ability by supply alkaline solution with additive liq, by repeating said process, the saponification ability is maintained in the predetermined scope, even thereby when using alkaline solution saponified polymer film surface in a continuous manner, also can produce alkali saponified polymeric film with stable manner.
[saponification processing]
Hereinafter, with the saponification processing of explaining among the present invention.
Handle for saponification being implemented on the polymeric film surface with alkaline solution, can use any known method, for example polymeric film is immersed method in the alkaline solution, to the method for polymeric film spray alkaline solution or on polymeric film the method for coating alkaline solution.
In the situation of the one side of saponified polymer film only, the method for coating alkaline solution is preferred.For coating, can use known coating method.
In the method for coating alkaline solution, preferably under 25 to 120 ℃, carry out saponification.
Handle in order under 25 ℃ or higher temperature, to implement saponification, can use before the alkaline solution coating, the method for heated polymerizable thing film to 25 ℃ or higher temperature, add the method for hot alkaline solution in advance, perhaps both methods of combining.Wherein, the method for heated polymerizable thing film is preferred in advance.
In the present invention, preferably implement following steps at least successively: the prior step of heated polymerizable thing film to 25 ℃ or higher temperature; Apply the step of described polymeric film with described alkaline solution; Described polymeric film kept equaling at least the step under 25 ℃ the temperature; And from the described polymeric film the step of the described alkaline solution of flush away.These steps will be explained hereinafter in more detail.
Preferably in the transfer polymer film, implement these steps in a continuous manner.The transmission speed of polymeric film is preferably 10 to 500 meters/minute, more preferably 20 to 300 meters/minute.Preferably determine the condition of each step according to transmission speed.For instance, on polymeric film, in the step of coating alkaline solution, preferably determine physical condition (proportion, viscosity and surface tension), coating method and coating condition, to realize stable coat operations.
At first, implement the step of prior heated polymerizable thing film to 25 ℃ or higher temperature.In advance heated polymerizable thing film to 25 ℃ or higher temperature have increased the speed of saponification reaction, and have improved stability.
In the step of prior heated polymerizable thing film to 25 ℃ or higher temperature, heating preferably realizes by the radiation heating of hot blast impact, the contact thermal conduction of hot-rolling, microwave induced heating or Infrared heaters.Especially, be preferred by the contact thermal conduction of hot-rolling because it has high heat conduction efficiency, and can under little erection space, implement, and can be when the transmission beginning temperature of quick rising film.Can use double fastener laminar roller commonly used or electromagnetic induction roller (producing) by Tokuden Co..
Film after the heating preferably has 25 to 100 ℃, and more preferably 25 to 80 ℃, and more preferably 35 to 75 ℃ temperature.
Then, implement the step of coating alkaline solution on polymeric film.In the step of coating alkaline solution on polymeric film, can advantageously use coating machine, for example mold pressing coating machine (extrusion coating machine or slip coating machine), roll coater (preceding roll coater, reverse roll coater or grooved roll coating machine), rod coater (using the rod that twines with metal wire) or knife coater.As concrete coating method, can use the coating method in many documents, described (for example Modern Coating and Drying Technology, Edward Cohen and Edgar B.Gutoff compile, VCH Publishers, Inc., 1992).
Consider the processing of removing waste material in cleaning step subsequently, the coating amount of alkaline solution is preferably as far as possible little.In above-mentioned coating machine, particularly preferably be rod coater, mold pressing coating machine, grooved roll coating machine or knife coater, under low coating amount even they also can stably be operated.
The preferred coated amount is changed to 30% or littler on polymeric film horizontal and vertical.
Saponification reaction number of sites on the unit surface polymeric film be multiply by the required saponification degree of depth such as adhering to oriented film draw total saponification number of sites, determine theoretical quantity of alkali consumption according to total saponification number of sites, use theoretical quantity of alkali consumption to provide the required alkaline solution coating amount of saponification reaction as index.
In fact, coating amount preferably is equal to, or greater than theoretical consumption.Specifically, be preferably 2 to 20 times of theoretical quantity of alkali consumption, more preferably 2 to 5 times amount.
The temperature of alkaline solution preferably equals the temperature of polymeric film.
After the step of polymeric film coating alkaline solution, implement polymeric film is kept equaling at least step under 25 ℃ the temperature.This step is fully carried out saponification reaction.
Preferred consider that the polymeric film surface is selected polymeric film remained on by the moistening fact of alkaline solution and equal or be higher than heating unit under 25 ℃ the temperature.For instance, can preferably use warm air to impact the radiation heating of the back side, contact thermal conduction, microwave induced heating or the Infrared heaters of coated surfaces by hot-rolling.
Infrared heaters is preferred, because it can realize heating by the noncontact mode, and does not use airflow, thereby to the minimum that influences on the surface of alkaline solution coating.As Infrared heaters, can make the far-infrared ceramic well heater of electricity consumption, gas, oil or steam-type.In having the environment of organic solvent,, preferably use oil or steam oil or steam type Infrared heaters as heating medium for blast protection.
The temperature that polymeric film is kept can be identical or different with the Heating temperature before the alkaline solution coating.In addition, described holding temperature may change continuously or progressively.Film temperature is preferably 25 to 100 ℃, and more preferably 25 to 80 ℃, and be preferably 35 to 70 ℃ again.For detect the temperature of film, can use be purchased exempt to contact infrared thermometer.For temperature being controlled in the above-mentioned scope, can apply feedback control to heating unit, and can regulate the temperature that is kept.
In order to stop the saponification reaction of polymeric film, for instance, can use dilution coating alkaline solution, reduce alkali concn, thereby reduce the method for speed of response; Use in the acidic liquid and the method for the alkaline solution of coating; Reduce the temperature of polymeric film, thereby reduce the method for speed of response.The method that can also use the method that will dilute alkaline solution or neutralization bases solution with reduce the method that the polymeric film method of temperature combines.
In order to dilute the coating alkaline solution, for instance, can use the method for coating diluting solvent, the method for spray diluting solvent, perhaps polymeric film is immersed in the method in the container that comprises diluting solvent.Wherein, in the operation of continuous transfer polymer film, the method for the method of coating diluting solvent and spray diluting solvent is preferred.Wherein, the method for coating diluting solvent is most preferred, because its diluting solvent consumption is minimum.
Preferred employing the continuously coating method on the polymeric film that scribbles alkaline solution of diluting solvent can being coated to is again implemented the coating of diluting solvent.
Coating method can be similar to the method described in the above-mentioned saponification processing.For promptly mixed ammonium/alkali solutions and diluting solvent, thereby reduction alkali concn, becoming streamlined mold pressing coating machine with liquid flow wherein compares, preferred roll coater or rod coater, liquid flow is uneven (to be also referred to as coating crimping (coating bead)) in these two kinds of coating machines in the zonule of coating application of liquid.
Diluting solvent must be the liquid that can dissolve alkaline solution neutral and alkali reagent, because its objective is the reduction alkali concn, therefore, preferably makes the mixture of water or organic solvent and water.
The organic solvent that uses in the preferred diluting solvent can not dissolve or the swollen polymer film.Also preferred selection has suitably low capillary material.
Organic solvent can use those that describe in Solvent Pocket Book New Edition (Ohm-sha, 1994).Concrete example comprises single hydroxyl alcohol (for example methyl alcohol, ethanol, propyl alcohol, butanols, hexalin, phenylcarbinol, fluoric alcohol or ethylene glycol monomethyl ether), ketone (for example acetone, methylethylketone or methyl iso-butyl ketone (MIBK)), ester (for example methyl acetate, ethyl acetate, butylacetate or ethylene glycol monomethyl ether monoacetate), polyhydroxy-alcohol (for example ethylene glycol, Diethylene Glycol or propylene glycol), acid amides (for example N, dinethylformamide), sulfoxide (for example dimethyl sulfoxide (DMSO)) and ether (methylcyclohexane).
Can determine the coating amount of diluting solvent according to the concentration of alkaline solution.
Have in the streamlined mold pressing coating machine in the coating crimping, used coating amount is with 1.5 to 10 times of former alkaline solution dilutions, more preferably 2 to 5 times.
In roll coater or rod coater, because the inhomogeneous flow in the coating crimping, alkaline solution and diluent mix, and then the coating mixing solutions.Therefore, because can't determine thinning ratio, so preferably after the coating dilute solution, measure the concentration of alkali from the coating amount of rare solvent.In addition, in roll coater or rod coater, diluted 1.5 to 10 times of preferred former alkali concn, more preferably 2 to 5 times.
In roll-coater or rod coater, because the inhomogeneous flow of coating in the crimping, alkaline solution and diluting solvent are mixed and use blended solution once more.Therefore, because can not determine thinning ratio, so preferably measure the concentration of alkali in diluting solvent coating back from the coating amount of dilute solution.In addition, in roll coater or rod coater, diluted 1.5 to 10 times of the concentration of preferred original alkali, more preferably 2 to 5 times.
As the method that stops the polymeric film saponification reaction, by with stopping saponification reaction apace with coated alkaline solution in the acidic liquid.
In order to realize neutralization with small amount of acid, strong acid is preferred.In addition, for the ease of cleaning, the salt that preferably is chosen in neutralization back and alkali formation has the acid of high-dissolvability in water.Hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid and chromic acid are particularly preferred.
In order to dilute the alkaline solution of coating, for instance, can use the coating diluting solvent method, spray diluting solvent method or polymeric film is immersed in method in the container that fills diluting solvent.Wherein, in the operation of continuous transfer polymer film, the method for the method of coating diluting solvent and spray diluting solvent is preferred.Wherein, the method for coating diluting solvent is most preferred, because its diluting solvent consumption is minimum.
Preferred employing the continuously coating method on the polymeric film that scribbles alkaline solution of diluting solvent can being coated to is again implemented the coating of diluting solvent.
Coating method can be similar to the method described in the above-mentioned saponification processing.For promptly mixed ammonium/alkali solutions and diluting solvent, thereby reduction alkali concn, becoming streamlined mold pressing coating machine with liquid flow wherein compares, preferred roll coater or rod coater, liquid flow is uneven (to be also referred to as coating crimping (coating bead)) in these two kinds of coating machines in the zonule of coating application of liquid.
Can determine the coating amount of acid solution according to the concentration of the kind of alkali and alkaline solution.
Have in the streamlined mold pressing coating machine in the crimping in coating, the coating amount of acid solution is 0.1 to 5 times of alkaline solution coating amount preferably, more preferably 0.5 to 2 times.
In roll-coater or rod coater, because the inhomogeneous flow in the coating crimping, alkaline solution mixes mutually with acid solution, and then the coating mixing solutions.Therefore, can't be from the coating amount of acid solution be determined and speed, so preferably measure the concentration of alkali in acid solution coating back.In addition, in roll coater or rod coater, preferably determine the coated weight of acid solution, thereby obtain 4 to 9 pH value, more preferably 6 to 8 pH value in acid solution coating back.
Can also stop the saponification reaction of polymeric film by the temperature that reduces polymeric film.In the method, by reducing enough temperature, can stop saponification reaction basically from the state that remains on for accelerated reaction under room temperature or the higher temperature.
When selecting refrigerating unit, should be taken into account that the cellulose acylate film surface is moistening.For instance, can be preferably to the back side of coated surfaces blowing cold air, perhaps by the contact thermal conduction of cooling roller.
The temperature of cooling caudacoria is preferably 5 to 60 ℃, and more preferably 10 to 50 ℃, and most preferably be 15 to 30 ℃.
The temperature of film can be used exempting from of being purchased to contact infrared thermometer and measure.Can also implement feedback control with the adjusting cooling temperature to refrigerating unit, thereby temperature is controlled in the above-mentioned scope.
Then, implement the step of flush away alkaline solution from the polymeric film.The residual saponification reaction that not only can make of alkaline solution is proceeded, and influences oriented film and the formation of liquid crystal molecule coated film and the orientation of liquid crystal molecule that the back will apply.
For flush away alkaline solution from polymeric film, it is preferred that water cleans.Can advantageously use coating water method, water spray method or polymeric film is immersed in method in the container that water is housed.
Water spray means can perhaps use the method for the commercially available nozzle (for example being produced by Ikeuchi Co. or Spraying Systems Inc.) that uses in air humidification, paint or automatic groove jar clean to implement by using the method for dispense tip (for example gravity flow coating machine or frog mouth formula coating machine).Can also use at document " All of Coating " coating method of describing among the Masayoshi Araki, Kako Gijutsu Kenkyu-kai (1999).Can be along laterally the arrange taper or the fan nozzle of polymeric film, so that the whole width of water impact film.
The spray rate of water is high more, and the mixing of logistics more at random.But, transmission stability that at a high speed may the impact polymer film when continuous transmission.Spray rate during the flushing polymeric film is preferably 50 to 1000cm/sec, and more preferably 100 to 700cm/sec, and most preferably is 100 to 500cm/sec.
Suppose that the water of the cleaning that is useful on all is used for the dilution of alkaline solution, defines theoretical thinning ratio by following equation:
Amount [the mL/m of theoretical thinning ratio (multiple)=water for cleaning 2Coating amount [the mL/m of]/alkaline solution 2]
Because in fact water and alkaline solution do not mix fully, so the actual used water amount is greater than the water consumption corresponding to theoretical thinning ratio.
Although depend on the concentration, supplementary additive, solvent of alkali in the used alkaline solution etc., it is 100 times or bigger that theoretical thinning ratio preferably is set, more preferably 500 times or bigger, and more preferably 1000 times or bigger.In addition, theoretical thinning ratio is chosen as 100,000 times or littler usually.
For the rinse water of specified rate, preferably with the dipartite purging method in batches of rinse water, rather than the whole water of applied once.More particularly, rinse water is merotomized, supply with along a plurality of washing units of the transmission direction arranged in series of polymeric film.Between washing unit and next washing unit, provide suitable distance, so that promote the dilution of alkali coating liquid by diffusion.
More advantageously use a large amount of washing units.But, consider installing space and equipment cost, use 2 to 20 grades usually, preferred 2 to 5 grades.
In addition, the polymeric film in the preferred angled transmission, thus make water on the polymeric film along the film surface flow, thus except spreading, also realize mixed diluting by flowing.
In addition, in order to eliminate the moisture film on the polymeric film,, can significantly improve the efficient of cleaning between washing unit by squeezing water is provided.The specific examples of squeezing water is included in the roller that uses in the rod that uses in the air knife that uses in the scraper that uses in the scraper type coating machine, the air-blade type coating machine, the rod coater and the roll coater.
Behind squeezing water, the thickness of moisture film is preferably as far as possible little, but the thickness of moisture film is subjected to the restriction of used squeezing water type.In the method for using solid-state component (for example scraper, rod or roller) contact membrane, need to keep limited moisture film as lubricating fluid, even because when solid-state component is made of the soft elastomeric component of for example rubber, still might cause to the scraping on film surface or the wearing and tearing of elastomeric component.Usually, keep several microns or thicker, preferred 10 microns or thicker moisture film are as lubricating fluid.
As the squeezing water that can greatly reduce water film thickness, air knife is preferred.By using enough air capacities and air pressure, the thickness of moisture film is close to zero by air knife.But too high air velocity may cause the shake or the deflection of polymeric film, thereby influences its transmission stability.Therefore, although also depend on the thickness of moisture film and the transmission speed of polymeric film before the extruding, the selection air velocity is 10 to 500m/sec usually, and preferred 20 to 300m/sec and more preferably 30 to 200m/sec.
In addition, in order to eliminate moisture film equably, regulate the air blowing aperture or the air Supply Method of air knife, make polymeric film air velocity in a lateral direction difference average air speed 10% in, in preferred 5%.
Gap between polymeric film surface in the transmission and the air knife gas hole footpath should be controlled in the suitable scope, because the gap is more little, the water squeezing ability is strong more, but causes thus causing that owing to contacting with polymeric film abrasive possibility is high more.Therefore, selecting described gap usually is 10 microns to 10 centimetres, preferred 100 microns to 5 centimetres, and more preferably 500 microns to 1 centimetre.
In addition, preferably on the back side of film cleaning surface, provide support roll, make it relative, be provided with, and alleviate the influence to film, for example shake, wrinkle or distortion thereby stablize the gap with air knife.
Clean for water, the preferred use purified waste water.Purifying waste water of using among the present invention means resistivity of water and is at least 1M Ω or higher, and metal ion (for example sodium, potassium, magnesium or calcium) content is lower than 1 mg/litre, and negatively charged ion (for example chlorine or nitrate radical) content is lower than 0.1 mg/litre.Can easily be purified water by reverse osmosis membrane, ion exchange resin, distillation or its combination.
The temperature of rinse water is high more, and cleansing power is strong more.But in the method for spraying water on the cellulose acylate film in transmission, water and air have bigger contact area, and evaporation at high temperature is more, thereby have increased the humidity of environment, and cause the danger of dewfall.Therefore, the temperature of water is arranged on 5 to 90 ℃ usually, and preferred 25 to 80 ℃, and more preferably in 25 to 60 ℃ the scope.
When the component of alkali coating liquid or saponification reaction product are not soluble in water,, can before or after the step of flush away alkaline solution from polymeric film, increase the solvent wash step in order to remove water-msoluble ingredients.
Can according to the identical mode of step of flush away alkaline solution from polymeric film, use described organic solvent to replace water to implement the solvent wash step as diluting solvent.
After the step of flush away alkaline solution from polymeric film, can implement drying step.
Removing fully in the situation of moisture film by the squeezing water of for example air knife, do not needing drying step usually, but before twining polymeric film on the roller,, can implement drying step in order to be adjusted to required water content.
Can also use the airflow of humidity to implement moisture control with selection.
[application of saponification cellulose acylate film]
[optical compensating gage]
Advantageously use the transparent substrates of saponified cellulose acylate film as optical compensating gage.
Optical compensating gage has laminate structure, wherein stacks gradually by coating alkali soap solution saponified cellulose acylate film, is used to form the resin layer of oriented film and the optical anisotropic layer that forms by fixing liquid crystal molecular orientation.
The formation of oriented film comprise the steps: to heat cellulose acylate film step, to the step of coating alkali soap solution on the oriented film side surface of cellulose acylate film, keep the step of step with the temperature on the surface of alkali soap solution coating, termination reaction and from the film surface the step of flush away alkali soap solution, wherein can also increase the step of coating and dry oriented film.After the step of coating and dry oriented film, can also apply friction treatment on the surface to oriented film, apply then and dry layer of liquid crystal molecule, thereby finish final optical compensating gage.
By adopting the saponification that not only comprises cellulose acylate film to handle but also comprise the integrated operation (integral operation) of the formation of oriented film and layer of liquid crystal molecule, provide high productivity.In addition, integrated operation also has following advantage: eliminated that handle from saponification simultaneously can also be as wet dust removal process to the cleaning step of the pitch time between the coated with orientation film, the deterioration that suppresses activatory saponification surface, saponification process, and avoided owing to repeatedly separate the roller end that winding and winding operation cause and lose.
The transparent substrates that is formed by the saponification cellulose acylate film, the oriented film that provides in the above and the optical anisotropic layer with discotic structure unit that forms on oriented film are provided described optical compensating gage.Described oriented film preferably passes through the crosslinking polymer thin film of friction treatment.
As the compound that in optical anisotropic layer, uses, can use the disc liquid-crystal compounds of lower molecular weight (monomer) or the polymkeric substance that obtains by the disc liquid-crystal compounds polymerization with discotic structure unit.Dish type compound (discotic compound) can be divided into the compound of (being the plate-like nematic phase) that has the plate-like crystalline phase and the compound that does not have the plate-like crystalline phase usually.Discotic compound has negative double refraction usually, and optical anisotropic layer of the present invention has this negative birefringence of discotic compound.Optical anisotropic layer of the present invention has utilized this negative birefringence of discotic compound.
[oriented film]
The oriented film of optical anisotropic layer is preferably formed by the film that cross-linked polymer forms by friction treatment.Oriented film is more preferably by two kinds of crosslinked polymer formation.A kind of in described two kinds of polymkeric substance is self crosslinkable polymkeric substance, or by the crosslinked polymkeric substance of linking agent.Use has the polymkeric substance of functional group or wherein introduces the polymkeric substance that functional group is arranged, and changes or passes through by light, heat or pH and use linking agent, and initiation reaction forms described oriented film between polymkeric substance.Described linking agent is the compound of high activity, and it introduces the connecting key that comes from linking agent between polymkeric substance, thus cross-linked polymer.
After the application of liquid that comprises polymkeric substance or mixture of polymers and linking agent is applied on the transparent substrates, can implement the crosslinked of polymkeric substance by heating.Can be from implementing crosslinking Treatment to any stage of making the optical compensating gage at coated with orientation film on the transparent substrates.Consider the disk-like structure compound (optical anisotropic layer) that on oriented film, forms, can also behind orientation disk-like structure compound, implement last orientation.Therefore, in the application of liquid that will comprise polymkeric substance and linking agent that can cross-linked polymer is coated to situation on the transparent substrates, carry out heat drying, and carry out friction treatment to form oriented film, the application of liquid that will comprise the compound with discotic structure unit then is coated on the oriented film, at least be heated to and be used for forming the nematic temperature of plate-like, cooling forms optical anisotropic layer then.
The polymkeric substance that uses in oriented film can be self crosslinkable polymkeric substance or by crosslinked polymkeric substance of linking agent or their combination.The example of described polymkeric substance comprises for example polymethylmethacrylate, vinylformic acid/Sipacril 2739OF, vinylbenzene/maleimide copolymer, polyvinyl alcohol and modified polyvinyl alcohol, poly-(N hydroxymethyl acrylamide), styrene/ethylene base toluene multipolymer, chlorosulfonated polyethylene, soluble cotton, polyvinyl chloride, chlorinatedpolyolefins, polyester, gelatin, polyimide, vinyl-acetic ester/vinyl chloride copolymer, ethylene, carboxymethyl cellulose, polyethylene, polypropylene or polycarbonate, and silane coupling agent.The preferred embodiment of polymkeric substance comprises water-soluble polymers, for example poly-(N hydroxymethyl acrylamide), gelatin, polyvinyl alcohol and modified polyvinyl alcohol, and gelatin, polyvinyl alcohol and modified polyvinyl alcohol are preferred, polyvinyl alcohol and modified polyvinyl alcohol are preferred, and are used in combination two kinds of polyvinyl alcohol or modified polyvinyl alcohol is particularly preferred.
Polyvinyl alcohol preferably has 70 to 100%, and more preferably 80 to 100%, and 85 to 95% saponification deg most preferably.Polyvinyl alcohol preferably has 100 to 3000 the polymerization degree.The modification group of modified polyvinyl alcohol can be introduced by modification by copolymerization, chain transfer modification or block copolymerization modification.In the situation of modification by copolymerization, introduce examples of groups and comprise COONa, Si (OX) 3, N (CH 3) 3Cl, C 9H 19COO, SO 3, Na and C 12H 25(wherein X represents proton or positively charged ion).In the situation of chain transfer modification, introduce examples of groups and comprise COONa, SH and C 12H 25In the situation of block copolymerization modification, introduce examples of groups and comprise COOH, CONH 2, COOR and C 6H 5(wherein R represents alkyl).
Wherein, saponification deg is that 85 to 95% unmodified polyethylene alcohol or alkylthio modified polyvinyl alcohol are most preferred.
Modified polyvinyl alcohol is preferably by the compound of following general formula (3) expression and the reaction product of polyvinyl alcohol.
General formula (3)
Figure A20038010504600681
Wherein, R 11The alkyl that alkyl that the alkyl that expression unsubstituted alkyl, acryl replace, methacryloyl replace or epoxy replace; W represents halogen atom, alkyl or alkoxyl group; X represents to be used to form the atomic group of active ester, acid anhydrides or acid halide; P is 0 or 1, and n represents from 0 to 4 integer.
Modified polyvinyl alcohol is more preferably the compound of following general formula (4) expression and the reaction product of polyvinyl alcohol.
General formula (4)
Figure A20038010504600682
Wherein, X 1Expression is used to form the atomic group of active ester, acid anhydrides or acid halide; And m is from 2 to 24 integer.
The polyvinyl alcohol that reacts with the compound of being represented by general formula (3) or (4) also can be modified polyethylene alcohol (modification by copolymerization, the chain transfer modification or block copolymerization modification).The method of the method for synthesizing polyethylene alcohol, the method for measuring visible absorption spectra and definite modification group introducing rate has a detailed description in JP-A8-33891.
Be used for polymkeric substance (preferably water soluble polymer; more preferably polyvinyl alcohol or modified polyvinyl alcohol) the example of linking agent comprise aldehyde (formaldehyde for example; oxalic dialdehyde or glutaraldehyde); N-methylol compound (for example dimethylolurea or methylol dimethyl hydantion) dioxane derivatives (for example 2; 3-Er Qiang Ji diox); the compound of activation effect that can be by carboxyl (carbonium ion for example; the 2-naphthalenesulfonate; 1; the two tetramethyleneimine of 1--1-chloropyridine; perhaps 1-morpholine carbonyl-3-(sulfoamino-methyl)); active vinyl-compound (for example 1; 3; 5-triacryl-six hydrogen-s-triazine); two (vinyl sulfone(Remzaol) methane; perhaps N '-methylene-bis [β-(vinyl sulfone(Remzaol) propionic acid amide]); active halogen compound (for example 2,4-two chloro-6-hydroxyl-s-triazines); isoxazole and two dialdehyde starchs.Can be used in combination two kinds or more of linking agents.The preferably aldehyde of high reaction activity, particularly glutaraldehyde.
The add-on of linking agent is preferably 0.1 to 20 weight % with respect to polymkeric substance, and more preferably 0.5 to 15%.The amount of residual unreacted linking agent is preferably 1.0 weight % or lower in the oriented film, more preferably 0.5 weight % or lower.The amount of residual linking agent surpasses 1.0 weight % and causes the wearing quality that can not provide enough in the oriented film.When being used for liquid crystal display, this oriented film uses or can produce reticulate pattern (reticulation) when placing high temperature and high humidity atmosphere for a long time long-time.
Oriented film basically can be by coating on transparent substrates as the above-mentioned polymkeric substance that comprises linking agent of the material that forms oriented film, and then by heat drying (crosslinked), and the enforcement friction treatment forms.As noted earlier, can implement crosslinking reaction in the random time after the coating transparent substrates.In the situation of the water-soluble polymers that uses polyvinyl alcohol for example as the material that forms oriented film, application of liquid is preferably used the mixed solvent that is formed by organic solution with froth breaking effect (for example methyl alcohol) and water.Water: the weight ratio of methyl alcohol is preferably 0: 100 to 99: 1, more preferably 0: 100 to 91: 9.Bubble formation can be suppressed thus, and the surface imperfection in oriented film and the optical anisotropic layer can be significantly reduced.
For the coated with orientation film, use preferably that spin coating, dip-coating, curtain are coated with, extrusion coated, rod is coated with or roller coat.The rod coating method is particularly preferred.Dried thickness is preferably 0.1 to 10 micron.Heat drying can be implemented down at 20 to 100 ℃.Crosslinked fully in order to obtain, preferred temperature is 60 to 100 ℃, preferred especially 80 to 100 ℃.Time of drying is from 1 minute to 36 hours, but preferably from 1 to 30 minute.Preferably according to used linking agent optimum pH value is set, in the situation of using glutaraldehyde, preferably the pH value is 4.5 to 5.5, particularly 5.
Oriented film is provided on the transparent substrates.Behind crosslinked above-mentioned polymer layer, can obtain oriented film by friction treatment to the surface.Provide oriented film that the differently-oriented directivity of its liquid crystal discotic compound that provides above is provided.
For friction treatment, can use the method for the liquid crystal aligning processing that is widely used in LCD.More particularly, can use water, gauze, felt, rubber, nylon fiber or trevira, thereby obtain the method for orientation along fixed-direction friction orientation film surface.In general, by with the cloth friction of the fiber that is implanted with even length and thickness implementation orientation several times.
[optical anisotropic layer]
The optical anisotropic layer of optical compensating gage is provided on oriented film.Optical anisotropic layer preferably by the compound formation with discotic structure unit and negative birefringence the layer.Optical anisotropic layer is the layer of the liquid crystal discotic compound of lower molecular weight (monomer), perhaps the polymer layer that obtains of the polymerization (sclerosis) by the polymerizable liquid-crvstalline discotic compound.The example of dish type (plate-like) liquid crystalline cpd is included in C.Destrade etc., Mol.Cryst., 71, the benzene derivative of describing among the p111 (1981); At C.C.Destrade etc., Mol:Cryst., 122, the toluxene derivative of describing among the p141 (1985); At Physics lett., A78, p.82 the toluxene derivative of describing in (1990); At B.Kohne etc., Angew.Chem.96, p.70 cyclohexane derivant of describing in (1984); And at J.Lehn etc., J.Chem.Commun., p.1794 (1985) and J.Zhang etc., J.Am.Chem.Soc., 116, Azacrown ether containing type and phenylacetylene type macrocylc compound of describing in (1994) p.2655.Plate-like (dish type) compound has with the above-mentioned fouling that is positioned at the branch subcenter usually as nuclear, and in the structure of the benzoyloxy that radially is substituted with straight chained alkyl, alkoxyl group or replacement as straight chain.Discotic compound comprises the discotic compound with liquid crystal property.The optical anisotropic layer that forms from discotic compound also comprises the layer that its polymerization is formed by polymerization or crosslinked lower molecular weight discotic mesogenic with light or heat reactivity group, thus the forfeiture liquid crystal characteristic.Discotic compound has description in JP-A8-50206.
Optical anisotropic layer is the layer by the compound formation with discotic structure unit and negative birefringence, and the plane of preferred discotic structural unit tilts to transparent substrates, and the angle of the plane of discotic structure unit and the formation of transparent substrates plane changes on the depth direction of optical anisotropic layer.
On the depth direction of optical anisotropic layer, discotic structure unit planar angle (pitch angle) is usually along with increasing or reduce with the increase of the distance of oriented film baseplane.The angle of inclination preferably increases along with the increase of described distance.The variation at angle of inclination comprises and increases continuously, reduces continuously, intermittently increases, intermittently reduces, comprises the variation that increases continuously and reduce continuously, and comprises that change the intermittence that increases and reduce.In intermittently changing, be included on the depth direction zone that angle of inclination does not wherein change.Even in the situation that comprises the zone that the angle of inclination does not change, preferred angle is whole to be increased or reduces.More preferably the angle of inclination is whole increases, and special preferred angle increases continuously.
Usually can be by applying on the oriented film and dry solution by dissolving discotic compound and other compound formation in solvent, be heated to then and form the required temperature of plate-like nematic phase, when keeping state of orientation (plate-like nematic phase), cool off then and obtain optical anisotropic layer.Perhaps, can be by also dry by in solvent, dissolving the solution that discotic compound and other compound (also claiming polymerisable monomer and Photoepolymerizationinitiater initiater) form in coating on the oriented film, be heated to then and form the required temperature of plate-like nematic phase, implement polymerization (for example UV irradiation), cooling obtains optical anisotropic layer then.The disc liquid-crystal compounds that uses among the present invention has and is preferably 70 to 300 ℃, and is preferably plate-like nematic liquid crystal phase-solid transformation temperature of 70 to 170 ℃ especially.
Usually, can perhaps select rubbing method to regulate the unitary angle of inclination of plate-like of base side by selecting the material of discotic compound or oriented film.In addition, can be by selecting discotic compound and regulating the unitary angle of inclination of base side (air side) plate-like with other compound (for example softening agent, tensio-active agent, polymerisable monomer and polymkeric substance) of a use of described discotic compound.In addition, can regulate the degree that the angle of inclination changes by described selection.
As long as have suitable mutual solubleness with discotic compound, and the variation at the angle of inclination of liquid crystal discotic compound can be provided, perhaps do not hinder their orientation, described softening agent, tensio-active agent and polymerisable monomer can be any compounds.Wherein, polymerisable monomer (compound that for example has vinyl, vinyloxy group, acryl or methacryloyl) is preferred.The consumption of this compounds is generally 1 to 50 weight % of discotic compound amount, preferred 5 to 30 weight %.
As long as have suitable mutual solubleness with discotic compound, and the variation at the angle of inclination of liquid crystal discotic compound can be provided, can use any polymkeric substance.The example of described polymkeric substance is a cellulose ester.The preferred embodiment of cellulose ester comprises rhodia, cellulose acetate propionate, hydroxy propyl cellulose and cellulose acetate butyrate.Usually with 0.1 to 10 weight % of discotic compound, preferred 0.1 to 8 weight %, and the amount of preferred especially 0.1 to 5 weight % uses described polymkeric substance, in order to avoid hinder the orientation of discotic compound.
[polaroid]
Polaroid has the laminate structure that stacks gradually optical compensating gage, polarizing coating and transparent protective film, and wherein said optical compensating gage comprises oriented film and the optical anisotropic layer that is formed by the liquid crystal molecule that has fixed orientation on polymeric film.For transparent protective film, can use common cellulose acetate membrane.
Polarizing coating can be iodo polarizing coating, the dye-based polarizing film that uses dichroic dye or based on the polyenoid polarizing coating.Usually use PVA-based film to prepare iodo polarizing coating and dye-based polarizing film.
The relation of the phase retardation axle of polymeric film and the light transmission shaft of polarizing coating is according to the kind of employed liquid crystal display and different.In TN, MVA or OCB type liquid crystal display, the phase retardation axle of polymeric film and the light transmission shaft of polarizing coating are substantially parallel.In reflective liquid crystal display device, preferred described phase retardation axle and light transmission shaft are at 45 basically.
[liquid crystal display]
Described optical compensating gage and polaroid can be advantageously used in the liquid crystal display.
The liquid crystal display of TN, MVA or ocb mode is by liquid crystal cell and be positioned at two polaroids in its both sides and form.Between two electrode basement of liquid crystal cell, provide liquid crystal.
Can between described liquid crystal cell and a polaroid, place a described optical compensating gage, also can between described liquid crystal cell and two polaroids, place two optical compensating gages.
In the liquid crystal display situation of ocb mode, on the polymeric film of optical compensating gage, can have the optical anisotropic layer that comprises discotic compound or rod shaped liquid crystal compound.Form optical anisotropic layer by the orientation discotic compound (perhaps rod shaped liquid crystal compound) and the orientation of fixing them.
Discotic compound has big double refraction usually.In addition, discotic compound has various state of orientation.Therefore, the optical compensating gage that uses discotic compound to make can have the optical property that original stretching birefringent film is not had.The optical compensating gage that uses discotic compound is at JP-A 6-214116, USP 5,583,679 and 5,646,703, and among the GP 3911620A1 description arranged.
In polaroid, can use above-mentioned polymeric film as the transparent protective film that places between liquid crystal cell and the polarizing coating.Above-mentioned polymeric film can be used in the transparent protective film (between liquid crystal cell and polarizing coating) of a polaroid, perhaps is used in two transparent protective films (between liquid crystal cell and polarizing coating) of two polaroids.
Described liquid crystal cell is ocb mode or TN pattern preferably.
The ocb mode liquid crystal element is to use the liquid crystal display of the liquid crystal cell of curved orientation pattern, and wherein rod shaped liquid crystal molecule is orientated with opposite basically (symmetric) direction in the upper and lower of liquid crystal cell, and at USP 4,583, in 825 and 5,410,422 description is arranged.Because rod shaped liquid crystal molecule is orientated symmetrically in the upper and lower of liquid crystal cell, so the liquid crystal molecule of curved orientation pattern has self optical compensation function.For this reason, this liquid crystal mode is called as OCB (optical compensation curved) liquid crystal mode.The liquid crystal display of curved orientation pattern has the advantage of quick response.In the liquid crystal cell of TN pattern, under not alive situation, rod shaped liquid crystal molecule essentially horizontally is orientated, and twists 60 to 120 ℃.The liquid crystal cell of TN pattern is widely used in the colored TFT liquid crystal display most, and in many documents description is arranged.
Embodiment
Hereinafter, further explain specific embodiments of the present invention and effect, but the present invention is not limited to these embodiment by embodiment.
[embodiment 1]
(preparation of cellulose ester membrane CF-1)
Composition below in tempering tank, packing into, and pass through each component of heating for dissolving under agitation, obtain cellulose acetate solution A.
The composition of acetate fiber promotor composition A
Cellulose triacetate (substitution value: 2.83,6 acyl substituted degree: 0.93,2, the 3-position always replaces
Degree: 1.90, viscosity average polymerization degree: 320, water content: 0.4%, at two of 6 weight %
Viscosity in the methyl chloride solution: 305mPas) 100 weight parts
Triphenylphosphate (softening agent) 8 weight parts
Biphenyl diphenyl phosphate (softening agent) 4 weight parts
Methylene dichloride (first solvent) 300 weight parts
Methyl alcohol (second solvent) 60 weight parts
The following composition of packing into, and dispersed with stirring mix each component, thus preparation matting agent solution.
The composition of matting agent solution
Median size is the silica dioxide granule of 16 nanometers
(AEROSIL R972 is produced by Nippon Aerosil Co.) 2 weight parts
Methylene dichloride (first solvent) 76 weight parts
Methyl alcohol (second solvent) 12 weight parts
Cellulose acetate solution A 10 weight parts
Composition below in tempering tank, packing into, and pass through each component of heating for dissolving under agitation, obtain postponing the dose solution A.
The composition that postpones the dose solution A
Following delay dose 19.8 weight parts
Following UV absorption agent (A) 0.07 weight part
Following UV absorption agent (B) 0.13 weight part
Methylene dichloride (first solvent) 58.5 weight parts
Methyl alcohol (second solvent) 9.0 weight parts
Cellulose acetate solution A 12.5 weight parts
Postpone dose
UV absorption agent A UV absorption agent B
The cellulose acetate solution A of 95 weight parts, the matting agent solution of 1 weight part and the delay dose solution of 4 weight parts are being filtered the back mixing respectively, and casting by band casting machine.The weight ratio that postpones dose and rhodia is 3.9 weight %.From being 30% film with peeling off the residual solvent amount, and be the film of 15 weight % by tenter machine 130 ℃ of following cross directional stretch residual solvent amounts, extensibility is 30%, and 140 ℃ of width after keeping stretching 30 seconds.After this, film is taken off from anchor clamps, and, obtain cellulose acetate membrane CF-1 140 ℃ of dryings.The cellulose acetate membrane of gained has 80 microns thickness.
(preparation of alkali soap solution (S-1) and alkali diluted liquid (SK-1))
Formulation alkali soap solution and alkali diluted liquid below using.
The prescription of alkali soap solution (S-1)
KOH 560 weight parts
Virahol 6080 weight parts
Diethylene Glycol 1680 weight parts
Following nonionogenic tenside 100 weight parts
Defoamer Surfinol DF110D
(producing) 2 weight parts by Nisshin Chemical Industries Co.
Water 1578 weight parts
C 14H 29O-(CH 2CH 2O) 10-H
The prescription of alkali diluted liquid (SK-1)
Virahol 580 weight parts
Diethylene Glycol 200 weight parts
Following nonionogenic tenside 100 weight parts
Defoamer Surfinol DF110D
(producing) 1 weight part by Nisshin Chemical Industries Co.
9299 weight parts of purifying waste water
(saponification film KF-1)
By being heated to 60 ℃ electromagnetic induction heating roller, cellulose acetate membrane CF-1 is heated to 30 ℃, and uses rod coater with 15cc/m 2Coated weight coating maintain 30 ℃ alkali soap solution (S-1).At Noritake Co., the far infrared steam heater that Ltd. produces kept for 10 seconds down and 110 ℃ of heating (temperature of film is 30 to 50 ℃) down, uses rod coater with 20cc/m then with film 2Consumption coating alkali diluted liquid, and flush away alkali.Under this state, film is remained under 40 to 55 ℃, and the concentration of KOH becomes 0.4N after coating alkali diluted liquid.Then, use the gravity flow coating machine to carry out water and clean, and use the air knife water squeezing, triplicate, the flush away alkaline reagents kept implement drying 15 seconds by the drying zone at 70 ℃ then, thereby made alkali soap film KF-1.
The carbonate concentration of alkali diluted liquid SK-1 is 750mg/L, comprise that total polyvalent metal ion concentration of calcium and magnesium is 30mg/L, and chlorine ion concentration is 18mg/L.
(formation of oriented film)
On the saponification face of saponification film KF-1, use rod coater with 30cc/m 2Consumption coating below the oriented film application of liquid, use 60 ℃ hot-air dry 60 seconds then, and with 90 ℃ hot-air dry 150 seconds, use again with the transmission direction velvet friction roller of placing that meets at right angles and carry out friction treatment, thereby the formation oriented film.
The prescription of oriented film application of liquid
Modified polyvinyl alcohol 100 weight parts
Water 1800 weight parts
Methyl alcohol 60 weight parts
Glutaraldehyde 2.5 weight parts
Modified polyvinyl alcohol
(preparation of optical compensating gage (KHF-1))
Above the oriented film that on KF-1, forms, use #4 line rod coating tool that the discotic compound solution of following prescription is arranged.Then, in 130 ℃ of warm air districts that link to each other with coating element, implement 2 minutes heating, thus the orientation discotic compound.At last,, use high voltage mercury lamp (120W/cm) to carry out the UV irradiation in 0.4 second by being under 100 ℃ the state in the film surface temperature, polymerizable discotic compound in 80 ℃ atmosphere, thus form optical anisotropic layer and make optical compensating gage KHF-1.
The prescription of discotic compound solution
Following discotic compound 2735 weight parts
The Viscoat 295 of oxyethane modification
(V#360 is produced by Osaka Yuki Kagaku Co.) 80 weight parts
Multi-functional acrylate's monomer
(NK ester A-TMMT is by Shin Nakamura
Kgaku Kogyo Co. produces) 190 weight parts
Cellulose acetate butyrate (CAB551-0.2,
Produce by Eastman Chemical Co.) 60 weight parts
Cellulose acetate butyrate (CAB551-1,
Produce by Eastman Chemical Co.) 15 weight parts
Photoepolymerizationinitiater initiater (Irgacure 907,
Produce by Ciba-Geigy Co.) 90 weight parts
Sensitizing agent (Kayacure DETX,
Produce by Nippon Kayaku Co.) 30 weight parts
Methylethylketone 6800 weight parts
In optical compensation films KHF-1, the Re delay that records optical anisotropic layer in 633 nanometers is 38 nanometers.In addition, angle (pitch angle) average out between dish plane and first transparent substrates (the above-mentioned substrate KF-1) surface is 35 °.
Discotic compound
Figure A20038010504600791
(preparation of alkali diluted liquid (SK-2 to SK-9))
Prepare alkali diluted liquid SK-2 to SK-9 according to the mode identical with alkali diluted liquid SK-1, just purified water is made into the deionized water that in semiconducter device equipment, uses, perhaps be mixed with the water of town water or well water, and the ion content in the alkali diluted liquid changes to some extent, and is as shown in table 1.
Table 1
The alkali diluted liquid Carbonate concentration mg/L Polyvalent ion concentration mg/L Chlorine ion concentration mg/L Remarks
SK-1 750 30 18 The present invention
SK-2 32 0.1 0.1 The present invention
SK-3 90 5.2 2.1 The present invention
SK-4 350 28 19 The present invention
SK-5 1530 119 73 The present invention
SK-6 3330 420 289 The present invention
SK-7 3580 428 219 Comparing embodiment
SK-8 3150 509 273 The present invention
SK-9 2830 420 317 The present invention
(preparation of optical compensating gage (KHF-2 to KHF-9))
According to the identical mode of alkali soap film KF-1, the preparation alkali soap film (KHF-2 to KHF-9), and the preparation optical compensation films (KHF-2 to KHF-9).
(evaluation method of saponification film)
Measure the turbidity of gained saponification film KHF-1 to KHF-9 with the optical measuring apparatus NDH-300A of Nippon Denshoku Co. production.The result is as shown in table 2.
(evaluation method of optical compensating gage)
＜foreign matter defective 〉
The optical compensation films KHF-1 to KHF-9 of gained is clipped in respectively between two polaroids of arranging in intersection Nicol mode, and visual inspection foreign matter defective, wherein foreign matter makes the light of transmission become inhomogeneous.The speck quantity of calculating in 17 inches picture frame.Table 2 has provided evaluation result.
＜adhesivity 〉
Every optical compensating gage is cut into 30 * 25 centimetres, under the condition of 25 ℃ temperature and 60% relative humidity, kept 1 day then, pasting 100 width in the optical anisotropic layer side is that 1.2 centimetres and length are 10 centimetres cellophane tape (No. 405, Nichiban Co. produces), in 1 second, peel off then, check the situation of peeling off between film and the oriented film.Estimate adherent level relatively according to the quantity that causes breakdown of coating in the 100 sheet glass paper self-adhesive tapes.Table 2 has provided evaluation result.
Table 2
The alkali diluted liquid Optical compensating gage Turbidity The foreign matter defective The adhesion number that generation is peeled off unusually Remarks
SK-1 KHF-1 0.8 0 0 The present invention
SK-2 KHF-2 0.8 0 0 The present invention
SK-3 KHF-3 0.8 0 0 The present invention
SK-4 KHF-4 0.8 0 0 The present invention
SK-5 KHF-5 0.9 0 0 The present invention
SK-6 KHF-6 0.9 0 0 The present invention
SK-7 KHF-7 1.3 4 3 Comparing embodiment
SK-8 KHF-8 1.4 7 7 The present invention
SK-9 KHF-9 1.4 3 4 The present invention
As shown in table 2, the preferred alkali diluted liquid of the present invention SK-1 to SK-6 can provide the film of the saponification with enough low turbidity, in the cleaning step of alkali soap process, do not adhere to alkaline reagents or soap on the saponification film.In addition, can obtain not have the gratifying optical compensating gage KHF-1 to KHF-6 of foreign matter defective or adhesion defects.On the other hand, when using the alkali diluted liquid SK-7 of sample as a comparison, find to show high turbidity, and cause corresponding optical compensating gage to have foreign matter defective and adhesion defects thus, thereby be inappropriate through the saponification film of alkali dilution and water cleaning acquisition.In addition, but surpassing among the SK-8 of preferable range as embodiment of the invention polyvalent metal ion concentration, and chlorine ion concentration surpasses among the SK-9 of preferable range, the saponification film that dilution of process alkali and water clean the back acquisition has the turbidity poorer than SK-1 to SK-6, and has foreign matter defective and adhesion defects.Even show thus in embodiments of the invention, except carbonate concentration be 3500mg/L or lower, low polyvalent metal ion concentration and chlorine ion concentration are particularly preferred.
[embodiment 2]
(preparation of cellulose ester membrane TF-1)
The composition of table 3 below in tempering tank, packing into, and under agitation dissolve each component and obtain cellulose acetate solution A.
Table 3
The composition of acetate fiber promotor composition A
Rhodia (substitution value: 2.83,6-position acyl substituted degree: 0.93, the acyl substituted of 3-position
Degree: 1.90, viscosity average polymerization degree: 320, water content: 0.4%, at two of 6 weight %
Viscosity in the methyl chloride solution: 305mPas)
100.0 weight part
Triphenylphosphate (softening agent) 8.0 weight parts
Dipentaerythritol six acetic ester (softening agent) 4.0 weight parts
Methylene dichloride (first solvent) 402.0 weight parts
Methyl alcohol (second solvent) 60.0 weight parts
The composition of table 4 below in decollator, packing into, and by each component of stirring and dissolving, thereby preparation matting agent solution.
Table 4
The composition of matting agent solution
Median size is the silica dioxide granule of 16 nanometers
(AEROSIL R972 is produced by Nippon Aerosil Co.) 2.0 weight parts
Methylene dichloride (first solvent) 76.0 weight parts
Methyl alcohol (second solvent) 11.4 weight parts
Cellulose acetate solution A 10.3 weight parts
The composition of table 5 below in tempering tank, packing into, and pass through each component of heating for dissolving under agitation, obtain postponing the dose solution A.
Table 5
The composition that postpones the dose solution A
Following delay dose 19.8 weight parts
Following UV absorption agent (A) 0.07 weight part
Following UV absorption agent (B) 0.13 weight part
Methylene dichloride (first solvent) 58.4 weight parts
Methyl alcohol (second solvent) 8.7 weight parts
Cellulose acetate solution A 12.8 weight parts
Postpone dose UV absorption agent
Figure A20038010504600831
Filtering the cellulose acetate solution A that mixes 94.6 weight parts in the back, part matting agent solution of 1.3 weight and the delay dose solution of 4.1 weight parts respectively, cast by band casting machine then.The weight ratio that postpones dose and rhodia is 4.6 weight %.From being 30% film with peeling off the residual solvent amount, and be the film of 13 weight % by tenter machine 130 ℃ of following cross directional stretch residual solvent amounts, extensibility is 28%, and 140 ℃ of width after keeping stretching 30 seconds.After this, film is taken off from anchor clamps, and, obtain cellulose acetate membrane 140 ℃ of dryings 40 minutes.The cellulose acetate membrane of gained has 80 microns thickness.
(saponification film SF-1)
By being heated to 60 ℃ electromagnetic induction heating roller, it is 30 ℃ that 1000 millimeters wide above-mentioned cellulose acetate membranes of roller are heated to the film surface temperature, and uses rod coater with 15cc/m 2Coating amount coating table 6 shown in the alkaline solution (S-1) of prescription, and be heated to 110 ℃.At Noritake Co., the far infrared steam heater that Ltd. produces kept for 15 seconds down, used rod coater with 3cc/m then with film 2Consumption coating purify waste water.Under this state, the temperature of film is 40 ℃.Then, use the gravity flow coating machine to carry out water and clean, and use the air knife water squeezing, triplicate kept implement drying 5 seconds by the drying zone at 70 ℃ then, thereby made alkali soap film SF-1.
Use the cellulose acetate membrane of 2000 square metres of 35 liters of alkaline solutions (S-1) saponification.
Table 6
The prescription of alkaline solution (S-1)
Potassium hydroxide 8.55 weight %
Water 23.235 weight %
Virahol 54.20 weight %
Tensio-active agent (K-1:C 14H 29O-(CH 2CH 2O) 20H) 1.0 weight %
Dipropylene glycol 13.0 weight %
Defoamer Surfinol DF110D
(producing) 0.015 weight % by Nisshin Chemical Industries Co.
The viscosity of alkaline solution (S-1) is 5.5mPas (25 ℃), and surface tension is 22.5mN/m (25 ℃).
(the relatively preparation of saponification film SFR-1)
Except the tensio-active agent (K-1) of from the prescription of alkaline solution (S-1), removing 1.0 weight %, use the prescription identical to prepare comparison process liquid (SR-1) with alkaline solution (S-1), and use described treatment liq, according to the identical method of saponification film SF-1, preparation is saponification film SFR-1 relatively.The viscosity of alkaline solution (SR-1) is 5.5mPas (25 ℃), and surface tension is 22.6mN/m (25 ℃).
(the relatively preparation of saponification film SFR-2)
By from the prescription of alkaline solution (S-1), removing mutual solubilising reagent, and correspondingly increase the amount of water and organic solvent in proportion, according to the formulation comparison process liquid (SR-2) shown in the table 7, and use described treatment liq, according to the identical method of saponification film SF-1, preparation is saponification film SFR-2 relatively.The viscosity of alkaline solution (SR-2) is 3.5mPas (25 ℃), and surface tension is 22.06mN/m (25 ℃).
Table 7
The prescription of alkaline solution (S-2)
Potassium hydroxide 8.55 weight %
Water 27.135 weight %
Virahol 63.30 weight %
Tensio-active agent (K-1) 1.0 weight %
Defoamer Surfinol DF110D
(producing) 0.015 weight % by Nisshin ChemicalIndustries Co.
Table 8 has been represented the character of used alkaline solution (S-1, SR-1 and SR-2) and the performance of prepared saponification film (SF-1, SFR-1 and SFR-2).In the table, A and B are illustrated respectively in the sample after saponification is handled the sample when just having begun and handled 2000 square metres, and have provided observations and evaluation to each sample in the table.
Table 8
Embodiment 1 Comparing embodiment 1 Comparing embodiment 2
Alkaline solution Sample number S-1 SR-1 SR-2
Character 1) A + + +
B + - --
The saponification film Sample number SF-1 SFR-1 SFR-2
Contact angle (°) 2) A 30 31 30
B 30 30-55 30-50
Turbidity 3) A 0.33 0.34 0.33
B 0.33 Muddy 0.9
The foreign matter muddiness 4) A + + +
B + - -
By in the following mode evaluation table with 1) to 4) assessment item of mark.
1) character of alkaline solution
Judgement criteria below using, naked eyes are estimated the transparency of alkaline solution:
+: transparent fully, without any muddy or precipitation
-: produce muddy
--: produce precipitation
2) with the contact angle of water
In contact angle instrument (CA-X is produced by Kyowa Kaimen Kagaku Co.), under drying regime (20 ℃/65%RH), use is purified waste water and form diameter on needle point is 1.0 millimeters drop, and make itself and film surface contact the formation drop.At solid-liquid point of contact place, the angle that comprises described drop that forms between liquid level positive tangent and solid surface is by tailor-made contact angle.
On every film, select 9 point measurement contact angles in the two ends and the central authorities of 1 square metre thin film planar, and be described as higher limit and lower value.But, have in the measurement ± 1 ° fluctuation, and what provide is intermediate value.
3) turbidity
The optical measuring apparatus NHD101DP that uses Nippon Denshoku Co. to produce measures the turbidity of saponification film.
4) foreign matter, muddiness
The saponification film is cut into 1 meter long overall with film, and under magnifying glass, observes foreign matter and muddiness by the transmitted light on the lamp box with bore hole, and by following standard evaluation.
+: do not observe foreign matter and muddiness (in the evaluation that 10 people participate in, all not observing)
±: slightly produce foreign matter and muddiness (in the evaluation that 10 people participate in, having 2 to 5 people to observe)
-: produce foreign matter and muddiness (in the evaluation that 10 people participate in, having 6 people or more people to observe) strongly
As shown in table 8, in embodiments of the invention, even after having handled 2000 square metres film, alkaline solution is still transparent, and the contact angle on the film surface of saponification after handling is 30 °.In addition, the saponification film shows low muddiness, and does not observe foreign matter or muddiness at all.
Alkaline solution (SR-1) and (SR-2) then after handling 2000 square metres relatively occurs muddy or precipitates.
In addition, relatively alkali soap film SFR-1 has the similar performance to film SF-1 of the present invention with SFR-2 (SFR-1A and SFR-2A) when the saponification processing has just begun, but after handling 2000 square metres (SFR-1B and SFR-2B), the turbidity and the muddiness that show water contact angle fluctuation in the bigger plane, increase, occur more foreign matter on the film surface, and in fact reach unacceptable level.
Then, the SF-1 film of the present invention that all shows satisfactory performance in A that uses in the saponification processing and the B part prepares optical thin film, and this will explain below, and it is carried out performance evaluation.
(formation of oriented film)
On the saponification face of sample SF-1A when saponification just begins and handled on the saponification face of the sample (SF-1B) after 2000 square metres the saponification film SF-1, use rod coater with 30cc/m 2Consumption coated with orientation thin film cladding liquid, described application of liquid is made of the modified polyvinyl alcohol with following structure of 20 weight parts, the water of 360 weight parts, the methyl alcohol of 120 weight parts and the glutaraldehyde of 0.5 weight part, use 60 ℃ hot-air dry 60 seconds then, and with 90 ℃ hot-air dry 150 seconds, use again with the transmission direction velvet friction roller of placing that meets at right angles and carry out friction treatment, thereby form oriented film.
Modified polyvinyl alcohol
Figure A20038010504600881
(preparation of optical anisotropic layer)
Above the oriented film that on sample SF-1A and SF-1B, forms, use the excellent following prescription that applies in the methylethylketone that is dissolved in 102 weight parts of #4 line: the following discotic compound of 41.01 weight parts, 1.22 the Viscoat 295 (V#360 of the oxyethane modification of weight part, produce by Osaka Yuki Kagaku Co.), 2.84 multi-functional acrylate's monomer of weight part (NK ester A-TMMT, produce by Shin Nakamura Kgaku Kogyo Co.), 0.90 the cellulose acetate butyrate (CAB551-0.2 of weight part, produce by Eastman ChemicalCo.), 0.23 the cellulose acetate butyrate (CAB551-1 of weight part, produce by EastmanChemical Co.), 1.35 (Irgacure 907 for the Photoepolymerizationinitiater initiater of weight part, produce by Ciba-Geigy Co.) and the sensitizing agent Kayacure DETX of 0.45 weight part, by Nippon Kayaku Co. production).Then, in 130 ℃ the warm air district that links to each other, implement 2 minutes heating, thus the orientation discotic compound.At last,, use high voltage mercury lamp (120W/cm) to implement the UV irradiation in 0.4 second by being about in the film surface temperature under 100 ℃ the state, polymerizable discotic compound in 80 ℃ atmosphere, thus form optical anisotropic layer.The Re delay that records optical anisotropic layer in 633 nanometers is 45 nanometers.In addition, angle (pitch angle) average out between the dish plane and the first transparent substrates surface is 39 °.
Discotic compound
Figure A20038010504600891
(evaluation method of optical compensating gage)
Turbidity
On film SF-1 to SF-4 that is obtained and SFR-1, use the optical measuring apparatus NHD-101DP that produces by Nippon DenshokuCo. to implement turbidimetry.
Every optical compensation films is clipped in intersecting between two polaroids that the Nicol mode arranges, and makes the irregularity of the transmitted light that detects by an unaided eye and estimate.
+: there be not (in the evaluation that 10 people participate in, all not observing)
±: the slight generation (in the evaluation that 10 people participate in, having 1 to 5 people to observe)
-: the serious generation (in the evaluation that 10 people participate in, having 6 people or more people to observe)
Adhesivity
Every optical compensating gage is cut into 30 * 25 centimetres, under the condition of 25 ℃ temperature and 60% relative humidity, kept 1 day then, in 5 unit of optical anisotropic layer side, paste width and be 1.2 centimetres and length and be 10 centimetres cellophane tape (No. 405, Nichiban Co. produces), in 1 second, peel off then, check the situation of peeling off between film and the oriented film.Estimate adherent level relatively according to the quantity that causes breakdown of coating in the 10 sheet glass paper self-adhesive tapes.Table 9 has provided evaluation result.
Table 9
Sample number The saponified cellulose acylate film Turbidity The irregularity of transmitted light Adhesivity
1 SF-1-A 0.35 + 0 (quantity)
2 SF-1-B 0.35 + 0 (quantity)
As shown in table 9, it is low and do not show irregularity in transmitted light to accept the turbidity of SF-1 that saponification of the present invention handles and SF-2.In addition, their adhesivity is enough and gratifying.
As previously described, have excellent homogeneity and gratifying adhesivity by the saponification cellulose acylate film of the inventive method preparation and the optical thin film of this film of use.
[embodiment 3]
(saponification tri cellulose acetate membrane)
By 100 ℃ warm air, tri cellulose acetate membrane Fujitac TD80UF (being produced by FujiPhoto Film Co.) is heated to 45 ℃, use rod coater with 14cc/m then 2Amount coating maintain 25 ℃ following alkaline solution (S-2), and after 13 seconds, reuse rod coater with 5cc/m 2Amount coating purify waste water.In the case, described film has 45 ℃ temperature.Then, by extrusion coating machine coating 1000cc/m 2Purify waste water, carry out water and clean, and after 5 seconds, by air knife the air of 100m/sec is blowed to the surface that scribbles water.After repeating twice extrusion coating machine cleaning and air knife water squeezing step, carry out the drying in 10 seconds at 80 ℃ drying zones, thereby obtain saponification film SF-2.With the same among the embodiment 2, the film that saponification is 2000 square metres.
Table 10
The prescription of alkaline solution (S-2)
Potassium hydroxide 6.5 weight %
Water 19.49 weight %
N-propyl alcohol 58.5 weight %
Diethylene Glycol 14.5 weight %
Tensio-active agent (K-2: the 1.0 weight % quadrol ethylene oxide adduct)
Defoamer Surfinol 104
(producing) 0.01 weight % by Nisshin ChemicalIndustries Co.
The viscosity of alkaline solution (S-2) is 5.6mPas (25 ℃), and its surface tension is 22.8mN/m (25 ℃).
For the membrane sample (SF-2A and SF-2B) of gained when saponification begins and after handling 2000 square metres, recording surface energy by following method is 60mN/m.
Surface energy adopts at " Basis and application of wetting ", and the contact angle method of describing in (Realize-sha, on December 10th, 1989 published) is measured.Two parts of water and methylene iodide solution with known surface energy are dripped on the cellulose acetate membrane, and at the intersection point place of drop surface with the film surface, the angle that comprises drop that forms between the positive tangent of drop and film surface is by tailor-made contact angle, then by calculating the surface energy that obtains film.
Prepare polaroid by following method: on the tensile polyvinyl alcohol film, adsorb iodine, use poly (vinyl alcohol) binder that the optical compensating gage of preparation among the embodiment 1 is adhered on the side of described polarizing coating then, and use poly (vinyl alcohol) binder that saponification film SF-2A is adhered on the opposite side, then 80 ℃ of dryings 10 minutes.The phase delay axle of the optical compensating gage of preparation among the axis of homology of polarizing coating and the embodiment 1 is arranged in parallel.The vertical phase delay axle of polarizing coating and the phase delay axle of tri cellulose acetate membrane arranged.Prepare polaroid in this manner.
In addition, replace SF-2A, prepare polaroid in an identical manner with SF-2B.
(liquid crystal display)
From using TN liquid crystal cell (6E-A3, produce by Sharp Inc.) liquid crystal display on peel off a pair of polaroid, and use tackiness agent to be stained with the as above polaroid of preparation respectively as an alternative on viewer's side and backlight side, the optical compensating gage with preparation among the embodiment 1 when bonding places the liquid crystal cell side.The axis of homology of viewer's side polaroid and the axis of homology of backlight side polaroid are arranged with the O pattern.
Use surveying instrument (EZ-Contrast 160D is produced by ELDIM Co.) to detect so liquid crystal display of preparation, and observe the irregularity that shows (L1) hypograph in dark attitude.
As a result, use the equipment of saponification film SF-2A by the inventive method preparation or SF-2B that the clear image of high brightness is provided, and the entire image district does not have muddy phenomenon in two kinds of situations.
The visual observation result of front shows that use provides satisfied optical characteristics through the cellulose acylate film of the inventive method saponified fourdrinier wire width of cloth form.
[embodiment 4]
According to the explanation of embodiment 2 among the JP-A 2002-182033, preparation has the cellulose acylate film of antireflective coating.Then, bonding polyethylene terephthalate film on the stain-proofing layer surface of cellulose acylate film (SAT-106TS is produced by Sanei Kaken).Use is used for the mother matrix etching processing machine of electronic plate making system as immersion treatment equipment, and to fill the alkaline solution (S-3) with following prescription and fluid temperature is set in this equipment be 45 ℃.After film was soaked for 10 seconds, it is immersed in the water, fully the flush away alkaline solution.Then, with 10 seconds in the dilution heat of sulfuric acid of its immersion 0.5%, immerse in the water again and thorough washing.Then, dry described film under 100 ℃ obtains saponified cellulose acylate film (SF-3).From tri cellulose acetate membrane, remove the ethylene glycol terephthalate film, obtain first polaroid protective film.
Table 11
The prescription of alkaline solution (S-3)
Potassium hydroxide 4.0 weight %
Water 42.7 weight %
Methylcyclohexane 40.0 weight %
TEG 12.0 weight %
Tensio-active agent (K-2:C 9H 19Ph (OCH 2CH 2) 8SO 3Na)
(Ph: 1.3 weight % phenylene)
Defoamer Purlonic TR70
(producing) 0.1 weight % by Asahi Denka Co.
The viscosity of alkaline solution (S-3) is 2.0mPas (25 ℃), and its surface tension is 35.0mN/m (25 ℃).
(preparation of second polaroid protective film)
Polyethylene terephthalate film (SAT-106TS is produced by Sanei Kaken) is adhered on the surface of another tri cellulose acetate membrane for preparing in aforesaid method.Through with the preparation of first polaroid protective film in after identical saponification handles, remove polyethylene terephthalate film, obtain second polaroid protective film.
(preparation of polaroid)
Be in the aqueous solution of 75 microns polyvinyl alcohol film (the Kuraray Co. production) potassiumiodide that is immersed in the iodine that comprises 7 weight parts in 1000 weight parts waters and 105 weight parts 5 minutes with thickness, thereby iodine is absorbed on the film.Then, in 40 ℃ 4 weight % boric acid aqueous solutions, longitudinally the described film of uniaxial extension is 4.4 times, and dry under tension, obtains polarizing coating.The saponification face that uses poly (vinyl alcohol) binder will constitute the tri cellulose acetate membrane of first polaroid protective film is adhered on the surface of described polarizing coating, and the saponification face that uses poly (vinyl alcohol) binder will constitute the tri cellulose acetate membrane of second polaroid protective film is adhered on another surface of polarizing coating.
(evaluation of polaroid)
Prepare 100 polaroids according to the method described above, and use acryloid cement to be adhered on the sheet glass respectively, then they are placed in the thermostatic constant wet chamber, accept 1000 hours serviceability test altogether, during this period, switched once in per 12 hours between 70 ℃, 93%RH atmosphere and 25 ℃, 93%RH atmosphere in the inside of thermostatic constant wet chamber.In 100 samples that from thermostatic constant wet chamber, take out, check peeling off and the bubble production between polaroid and the sheet glass, and in 100 samples, all do not find to produce to peel off and bubble.
In addition, peel off the polaroid of both sides from thin film transistor (TFT) the type LCD monitor that is purchased, the dark attitude of the bonding above-mentioned polaroid in its both sides, and naked eyes evaluation then shows and bright attitude shows the irregularity that exists down.In the entire image district, do not observe for example dysopia of irregularity.
[embodiment 5]
(saponified tri cellulose acetate membrane)
On the surface of cellulose acylate film, be provided among the embodiment 4 antireflective coating of describing, and the surface of uncoated antireflective coating be heated to 45 ℃, use rod coater then with 5cc/m by 80 ℃ warm air 2Amount coating maintain the alkaline solution (S4-7) of the various prescriptions shown in 35 ℃ the table 12, and after 10 seconds, use rod coater with 5cc/m 2Amount coating purify waste water.In the case, film has 45 ℃ temperature.Then, by extrusion coating machine coating 1000cc/m 2Purify waste water and carry out water and clean, and after 5 seconds, the air of 100m/sec is blowed to the surface that scribbles water by air knife.Extrusion coating machine is cleaned and twice of air knife water squeezing step repetition after, carry out the drying in 10 seconds at 80 ℃ drying zones, thereby obtain saponification film SF-2 to SF-7.
Table 12
Figure A20038010504600951
Annotate: parenthetic numeral weight %.
Organic solvent as in the table 6,7,19,11 and 12 illustrates in front, its solubility parameter ([mJ/m 3] 1/2) and the I/O value representation as follows.
Organic solvent Solubility parameter The I/O value
Virahol 23.5 2.00
N-propyl alcohol 24.3 1.67
Methylcyclohexane 23.3 2.00
The 2-butanols 22.1 1.25
Ethanol 26.0 2.50
Propylene glycol monomethyl ether 20.7 1.50
Methyl alcohol 29.7 5.00
The viscosity of alkaline solution (S-4 to S-7) is 1.8 to 6mPas (25 ℃), and its surface tension is 20 to 30mN/m (25 ℃).
The contact angle of film (SF-4 to SF-7) and water is in 30 to 35 ° scope.
Then, replace the saponification film of embodiment 4 preparations, use saponification film SF-4 to SF-7 to prepare polaroid.Method by embodiment 4 is estimated polaroid, and the result shows the character suitable with embodiment 4.
[embodiment 6 and comparing embodiment]
It is 1000 millimeters tri cellulose acetate membrane (Fujitac TD80UF (by Fuji Photo Film Co. produce) that stripping film (Rintec Co. production) is adhered to roller wide) the surface on.Use is used for the immersion treatment equipment of the mother matrix etching processing machine E-380II of electronic plate making system as film, and the alkaline solution (S-1) with following prescription and to set fluid temperature be 40 ℃ of packing in this equipment.Described film soaked for 45 seconds in alkaline solution after, it is immersed in water, with abundant flush away alkaline solution.Then, with 10 seconds in the dilution heat of sulfuric acid of its immersion 0.5%, immerse in the water again and thorough washing.Then,, and peel stripping film, obtain saponified cellulose acylate film (SF-1) at 100 ℃ of following desciccator diaphragms.
Table 13
The prescription of alkaline solution (S-1)
Potassium hydroxide 6.0 weight %
Water 87.5 weight %
Propylene glycol 5.0 weight %
Tensio-active agent (K-1: structure is as follows) 1.5 weight %
Defoamer Surfinol DF110D
(producing) 0.010 weight % by Nisshin Kagaku Kogyo Co.
Tensio-active agent K-1
Use 30 liters alkaline solution (S-1) to come the above-mentioned cellulose acetate membrane of 1000 square metres of saponification.
(the relatively preparation of saponification film SFR-1)
Except the tensio-active agent (K-1) of from alkaline solution prescription (S-1), removing 1.0 weight %, use with alkaline solution (S-1) same recipe and prepare comparison process liquid (SR-1), and use described treatment liq, prepare comparison saponification film SFR-1 according to the mode identical with saponification film SF-1.
(the relatively preparation of saponification film SFR-2)
The aqueous sodium hydroxide solution of preparation 6.0% is treatment liq (SR-2) as a comparison, replaces alkaline solution (S-1), and uses described treatment liq, prepares saponification film SFR-2 according to the mode identical with saponification film SF-1.
Estimate the character of used alkaline solution (S-1, SR-1 and SR-2) and the performance of prepared saponification film (SF-1, SFR-1 and SFR-2) according to the methods below, and be illustrated in the table 14.In the table, the sample when A and B are illustrated respectively in and just begin saponification and handle and handle 1000 square metres after sample, and provided observations and evaluation in the table to each sample.
(evaluation of saponification film)
Judgement criteria below using is estimated alkali soap solution and saponification film.
1) character of alkaline solution
Judgement criteria below using, naked eyes are estimated the transparency of alkaline solution:
+: transparent fully, without any muddy or precipitation
-: produce muddy
--: produce precipitation
2) with the contact angle of water
In contact angle instrument (CA-X is produced by Kyowa Kaimen Kagaku Co.), under drying regime (20 ℃/65%RH), use is purified waste water and form diameter on needle point is 1.0 millimeters drop, and make itself and film surface contact the formation drop.At solid-liquid point of contact place, the angle that comprises described drop that forms between liquid level positive tangent and solid surface is by tailor-made contact angle.
On every film, select 9 point measurement contact angles in the two ends and the central authorities of 1 square metre thin film planar, and be described as higher limit and lower value.But, have in the measurement ± 1 ° angle fluctuation, and express intermediate value.
3) foreign matter, muddiness
The saponification film is cut into 1 meter long overall with film, and under magnifying glass, observes foreign matter and muddiness by the transmitted light on the lamp box with bore hole, and by following standard evaluation.
+: do not observe foreign matter and muddiness (in the evaluation that 10 people participate in, all not observing)
±: slightly produce foreign matter and muddiness (in the evaluation that 10 people participate in, having 2 to 5 people to observe)
-: produce foreign matter and muddiness (in the evaluation that 10 people participate in, having 6 people or more people to observe) strongly
Table 14
Embodiment 1 Comparing embodiment 1 Comparing embodiment 2
Alkaline solution Sample number S-1 SR-1 SR-2
Character A + + +
B + - --
The saponification film Sample number SF-1 SFR-1 SFR-2
Contact angle (°) A 38 39 40
B 38 40-55 40-50
The foreign matter muddiness A + + +
B + - -
As shown in table 14, in embodiments of the invention, even after having handled 1000 square metres film, alkaline solution is displaing yellow not also, in the treatment trough of alkaline solution, does not observe precipitation or settling after recycling.The surface of saponification film (SF-1) when beginning to handle and the water contact angle after handling 1000 square metres be 38 °.In addition, do not find foreign matter on the saponification film, and transparency is gratifying.
And alkaline solution (SR-1) and (SR-2) after handling 1000 square metres relatively occurs yellow, muddy or precipitates.
In addition, relatively alkali soap film SFR-1 has the similar performance to film SF-1 of the present invention with SFR-2 (SFR-1A and SFR-2A) when the saponification processing has just begun, but after handling 1000 square metres, relatively alkali soap film (SFR-1B and SFR-2B) shows the turbidity and the muddiness of water contact angle fluctuation, increase in the bigger plane, occur more foreign matter on the film surface, and in fact reach unacceptable level.The condition (temperature and time) of embodiment 6 down relatively alkali soap film SFR-2 show insufficient saponification, show as fluctuation in big water contact angle and very large.
(polaroid)
Then, according to hereinafter described, the film SF-1 of the present invention that shows satisfactory performance in A that uses in the saponification processing and the B part prepares optical thin film, and it is carried out performance evaluation.
Use poly (vinyl alcohol) binder (3% aqueous solution, dry-coated deposited thickness is 0.01 micron), saponification film (SF-1) is adhered to the polyvinyl alcohol polarizing coating (mean polymerisation degree: 3500 of 25 micron thickness, average 99.5 moles of % of saponification deg, stretch 5 times) both sides, and drying is 1 minute under 100 ℃, obtains polaroid.
(evaluation of polaroid)
Then, in order to investigate in the polaroid bonding between the tri acetyl cellulose film and polarizing coating, carry out following test.
＜punching test 〉
Polaroid was kept 500 hours under 65 ℃ and 95%RH, uses the cutting unit (TCM-500A is produced by Toko Co.) of circular knife to carry out punching press and the standard evaluation adhesivity below using then with 35 millimeters of diameters:
+: between film (SF-1) and polarizing coating, do not observe and peel off;
-: between film (SF-1) and polarizing coating, observe and peel off.
Found that bonding between tri acetyl cellulose film and the polarizing coating is very gratifying, have+the result.
＜stripping test 〉
Prepare 100 polaroids according to the method described above, and use acryloid cement to be adhered on the sheet glass respectively, then they are placed in the thermostatic constant wet chamber, accept 1000 hours serviceability test altogether, during this period, switched once in per 12 hours between 70 ℃, 93%RH atmosphere and 25 ℃, 93%RH atmosphere in the inside of thermostatic constant wet chamber.In 100 samples that from thermostatic constant wet chamber, take out, check peeling off and the bubble production between polaroid and the sheet glass, and in 100 samples, all do not find to produce to peel off and bubble.
In addition, peel off the polaroid of both sides from thin film transistor (TFT) the type LCD monitor that is purchased, the dark attitude of the bonding above-mentioned polaroid in its both sides, and naked eyes evaluation then shows and bright attitude shows the irregularity that exists down.In the entire image district, do not observe for example dysopia of irregularity.
[embodiment 7]
According to the explanation of embodiment 1 among the JP-A 2002-182033, preparation has the cellulose acylate film of antireflective coating.With cellulose acylate film back to the treated side of antireflection layer by being heated to 60 ℃ electromagnetic induction heating roller, the temperature on film surface is risen to 30 ℃, use rod coater with 10cc/m then 2The coating amount coating tool alkaline solution (S-2) of following prescription is arranged, and by by Noritake Co., the far infrared steam heater that Ltd. produces kept for 15 seconds down, was heated to 110 ℃, used rod coater with 3cc/m then 2Consumption coating purify waste water.At this, the temperature of described film is 40 ℃.Then, use the gravity flow coating machine to carry out water and clean, and use the air knife water squeezing, water is cleaned and water squeezing processing triplicate, kept implement drying 5 seconds by drying zone then, thereby make alkali soap film SF-2 at 70 ℃.
Table 15
The prescription of alkaline purification liquid (S-2)
Potassium hydroxide 5.7 weight %
Water 33.3 weight %
N-propyl alcohol 49.8 weight %
Ethylene glycol 10.0 weight %
Tensio-active agent (K-2: following structure) 1.2 weight %
Defoamer Purlonic TR70
(producing) 0.01 weight % by Asahi Denka Co.
Tensio-active agent (K-2)
In the film of gained, the sample when saponification begins and handle 2000 square metres after sample (SF-2A and SF-2B) all have 33 ° water contact angle.In addition, on the saponification film, do not find foreign matter or do not have muddiness at all, and transparency is gratifying.
According to hereinafter described, the film SF-2 of the present invention that shows satisfactory performance in A that uses in the saponification processing and the B part prepares optical thin film, and it is carried out performance evaluation.
(formation of oriented film)
On the saponification face of sample SF-2A when saponification just begins and handled on the saponification face of the sample (SF-2B) behind 2000 square metres the saponification film SF-1, use rod coater with 30cc/m 2Consumption coated with orientation thin film cladding liquid, described application of liquid comprises the modified polyvinyl alcohol with following structure of 20 weight parts, the water of 360 weight parts, the methyl alcohol of 120 weight parts and the glutaraldehyde of 0.5 weight part, use 60 ℃ hot-air dry 60 seconds then, and with 90 ℃ hot-air dries 150 seconds, carry out friction treatment with the velvet friction roller again, thereby form oriented film.
Modified polyvinyl alcohol
Figure A20038010504601022
(preparation of optical anisotropic layer)
Above the oriented film that on sample SF-2A and SF-2B, forms, use the excellent following prescription that applies in the methylethylketone that is dissolved in 102 weight parts of #4 line: the following discotic compound of 41.01 weight parts, 1.22 the Viscoat 295 (V#360 of the oxyethane modification of weight part, produce by Osaka Yuki Kagaku Co.), 2.84 multi-functional acrylate's monomer of weight part (NK ester A-TMMT, produce by Shin Nakamura Kgaku Kogyo Co.), 0.90 the cellulose acetate butyrate (CAB551-0.2 of weight part, produce by Eastman ChemicalCo.), 0.23 the cellulose acetate butyrate (CAB551-1 of weight part, produce by EastmanChemical Co.), 1.35 (Irgacure 907 for the Photoepolymerizationinitiater initiater of weight part, produce by Ciba-Geigy Co.) and the sensitizing agent (Kayacure DETX is by Nippon Kayaku Co. production) of 0.45 weight part.Then, in 130 ℃ the warm air district that links to each other, implement 2 minutes heating, thus the orientation discotic compound.At last,, use high voltage mercury lamp (120W/cm) to implement the UV irradiation in 0.4 second by under the about 100 ℃ state of film surface temperature, polymerizable discotic compound in 80 ℃ atmosphere, thus form optical anisotropic layer.The Re delay that records optical anisotropic layer in 633 nanometers is 45 nanometers.In addition, angle (pitch angle) average out between the dish plane and the first transparent substrates surface is 39 °.
Discotic compound
(evaluation method of optical compensating gage)
Turbidity
The optical measuring apparatus NHD-101DP that uses Nippon Denshoku Co. to produce carries out turbidimetry to the optical compensating gage that uses film SF-2A and SF-2B preparation.
Irregularity in the transmitted light
Every optical compensation films is clipped in intersecting between two polaroids that the Nicol mode arranges, and the irregularity of visual inspection transmitted light and estimating.
+: totally there be not (in the evaluation that 10 people participate in, all not observing)
±: the slight generation (in the evaluation that 10 people participate in, having 1 to 5 people to observe)
-: the strong generation (in the evaluation that 10 people participate in, having 6 people or more people to observe)
Adhesivity
Every optical compensating gage is cut into 30 * 25 centimetres, under the condition of 25 ℃ temperature and 60% relative humidity, kept 1 day then, in 5 unit of optical anisotropic layer side, paste width and be 1.2 centimetres and length and be 10 centimetres cellophane tape (No. 405, Nichiban Co. produces), in 1 second, peel off then, check the situation of peeling off between film and the oriented film.Estimate adherent level relatively according to the quantity that causes breakdown of coating in the 10 sheet glass paper self-adhesive tapes.
The SF-2A and the SF-2B that handle through saponification of the present invention show low turbidity, and do not show irregularity at transmitted light.Its adhesivity also is enough in addition.
As mentioned above, adopt the saponification cellulose acylate film of the inventive method preparation and the optical thin film of this film of use to have excellent homogeneity and gratifying adhesivity.
[embodiment 8]
(saponified tri cellulose acetate membrane)
By 100 ℃ warm airs (heat release), tri cellulose acetate membrane Fujitac TD80UF (Fuji Photo Film Co. production) is heated to 45 ℃, use rod coater with 14cc/m then 2Amount coating maintain 25 ℃ following alkaline solution (S-3), and after 13 seconds, use rod coater with 5cc/m 2Amount coating purify waste water.In the case, described film has 45 ℃ temperature.Then, by extrusion coating machine coating 1000cc/m 2Purify waste water, implement water and clean, and after 5 seconds, by air knife the air of 100m/sec is blowed to the surface that scribbles water.Extrusion coating machine is cleaned and twice of air knife water squeezing operation repetition after, carry out the drying in 10 seconds at 80 ℃ drying zones, thereby obtain saponification film SF-3.The film that saponification is 2000 square metres.
Table 16
The prescription of alkaline solution (S-3)
Potassium hydroxide 6.5 weight %
Water 32.0 weight %
Virahol 48.3 weight %
Diethylene Glycol 12.0 weight %
Tensio-active agent (K-3: following structure) 1.2 weight %
Defoamer Surfinol 104
(producing) 0.01 weight % by Nisshin ChemicalIndustries Co.
Tensio-active agent (K-3)
Sample when saponification begins and handle 2000 square metres after on the sample (being called SF-3A and SF-3B respectively) of gained, all obtain contact angle with water and be 30 ° surface, and on whole surface, the fluctuation of contact angle is in the scope of measuring error, and this shows that saponification is uniform.
In addition, each membrane sample (SF-3A and SF-3B) all has the surface energy of the 60mN/m that measures by following method.
Surface energy adopts at " Basis and application of wetting ", and the contact angle method of describing in (Realize-sha, on December 10th, 1989 published) is measured.Two parts of water and methylene iodide solution with known surface energy are dripped on the cellulose acetate membrane, and at the intersection point place of drop surface with the film surface, the angle that comprises drop that forms between the positive tangent of drop and film surface is by tailor-made contact angle, then by calculating the surface energy that obtains film.
Do not find foreign matter or muddiness on the described saponification film, and its transparency is gratifying.
(polaroid)
Prepare polarizing coating by following method: on the tensile polyvinyl alcohol film, adsorb iodine, use poly (vinyl alcohol) binder that the optical compensating gage of preparation among the embodiment 7 is adhered on the side of described polarizing coating then, and use poly (vinyl alcohol) binder that saponification film SF-3A is adhered on the opposite side, following dry 10 minutes at 80 ℃ then.The phase delay axle of the optical compensating gage of preparation among the axis of homology of the described polarizing coating of parallel arrangement and the embodiment 7.Make the phase delay axle of the axis of homology of described polarizing coating and tri cellulose acetate membrane perpendicular.Prepare polaroid thus.
In addition, replace saponification film SF-3A, prepare polaroid in an identical manner with saponification film SF-3B.
(liquid crystal display)
From using TN liquid crystal cell (6E-A3, produce by Sharp Inc.) liquid crystal display on peel off a pair of polaroid, and use tackiness agent on viewer's side and backlight side, to be stained with the polaroid of preparation as mentioned above respectively as an alternative, wherein make the optical compensating gage of preparation among the embodiment 7 be positioned at the liquid crystal cell side.The axis of homology of viewer's side polaroid and the axis of homology of backlight side upper polarizer are the O pattern and arrange.
Use surveying instrument (EZ-Contrast 160D is produced by ELDIM Co.) to detect so liquid crystal display of preparation,, and observe the irregularity that shows (L1) hypograph in dark attitude.
As a result, use the clear image that high brightness is provided by the equipment of the saponification film SF-3A of the inventive method preparation or SF-3B, and do not become turbid in the entire image district in two kinds of situations.
The visual inspection result of front shows that use provides satisfied optical characteristics through the cellulose acylate film of the inventive method saponified fourdrinier wire width of cloth form.
[embodiment 9-12]
(saponified tri cellulose acetate membrane)
On the surface of cellulose acylate film, provide 7 described antireflective coatings, and by 80 ℃ warm air (heat release), the surface of uncoated antireflective coating is heated to 45 ℃, use rod coater then with 7cc/m as embodiment 2Amount coating maintain 35 ℃ following alkaline solution (S4 to 7) with prescription shown in the table 17, and after 20 seconds, re-use rod coater with 5cc/m 2Amount coating purify waste water.In the case, described film has 45 ℃ temperature.Then, by extrusion coating machine coating 1000cc/m 2Purify waste water, implements water and clean, and after 5 seconds, the air that blows out 100m/sec from air knife carries out water squeezing to be handled.Extrusion coating machine clean and air knife water squeezing are handled repeat twice after, carry out the drying in 10 seconds at 80 ℃ drying zones, thereby obtain saponification film SF-4 to SF.
Table 17
Figure A20038010504601081
The contact angle of film SF-4 to SF-7 and water is all in 30 to 35 ° scope.
Use saponification film SF-4 to SF-7 to replace the saponification film that uses among the embodiment 8 then, the preparation polaroid.With with embodiment 8 in evaluation method the performance of above-mentioned polaroid is estimated, these polaroids show the sample comparable properties with embodiment 8.
[embodiment 13 and comparing embodiment 3]
Except using the alkaline purification liquid (S-3) that in embodiment 8, uses to replace the alkaline purification liquid (S-1) among the embodiment 6, according to embodiment 6 in identical mode film is carried out saponification (saponification film SF-8).
(the relatively preparation of saponification film SFR-3)
Replace the alkaline purification liquid (S-3) except apparatus has the alkaline purification liquid (SR-3) of following prescription, according to embodiment 13 in identical mode prepare saponification film (SFR-3).
Table 18
The prescription that compares alkaline purification solution (SR-3)
Potassium hydroxide 6.5 weight %
Water 32.0 weight %
Virahol 48.3 weight %
Diethylene Glycol 12.0 weight %
Tensio-active agent (following structure)
Figure A20038010504601091
1.2 weight %
Defoamer Surfinol104
(producing) 0.01 weight % by Nisshin Chemical Industries Co.
Investigate the character of alkaline purification liquid (S-3, SR-3) and the performance of prepared saponification film (SF-8, SFR-3) in the mode identical with embodiment 6.
After handling 1500 square metres from saponification, liquid of the present invention with just begin to keep identical when saponification is handled, in alkaline purification liquid (SR-3) relatively, then occurring muddy and precipitating.
In addition, the saponification film comparative sample (SFR-3) after handling 1500 square metres shows water contact angle fluctuation and bigger turbidity in the bigger face.
As mentioned above, even when increasing treatment capacity, the present invention also can provide the stability and the satisfied saponification film performance of the alkaline purification liquid of satisfaction.
[embodiment 14]
The preparation of 1-1 alkali soap fluidized polymer film
By the electromagnetic induction heating roller that is heated to 60 ℃, it is 40 ℃ that 1000 millimeters wide tri cellulose acetate membranes (Fujitac TD80UF is produced by Fuji Photo Film Co.) of roller are heated to the film surface temperature.Then, use rod coater with 10cc/m 2Coating amount, being used in 40 ℃ of following specific conductivity is the alkaline solution with following prescription (S-1) the coated film surface of 220mS/cm.Continue the described film of transmission, and be heated to 110 ℃ by Noritake Co., the far infrared steam heater that Ltd. produces kept for 15 seconds down.Then, use rod coater with 3cc/m 2Consumption coating purify waste water.Under this state, the temperature of film is 40 ℃.Then, use the gravity flow coating machine to carry out water and clean, and use the air knife water squeezing, water is cleaned and water squeezing processing triplicate, kept implement drying 5 seconds by drying zone then, thereby make alkali soap film SF-1 at 70 ℃.By this way, the tri cellulose acetate membrane of 6000 square metres of saponification.
Alkaline solution is contained in the alkaline solution groove, and is fed in the application processing apparatus by the pump of constant speed.The excessive liquid in coating back is returned in the alkaline solution groove, and recycle.The alkaline solution groove also is equipped with the whipping device that is used for saponification and handles, the conductivitimeter of measuring alkaline solution saponification ability and the device that can add the additive liq with following prescription (H-1) of predetermined amount based on measured specific conductivity automatically.So that alkaline solution is kept the mode of the specific conductivity of 220 ± 10mS/cm, under the supply of additive liq (H-1), implement saponification and handle.
Table 19
The prescription of alkaline solution (S-1)
Sodium hydroxide 4.0 weight parts
Water 90.985 weight parts
Propylene glycol 4.0 weight parts
Tensio-active agent (K-1:C 14H 29O-(CH 2CH 2O) 2H) 1.0 weight parts
Defoamer Surfinol DF110D
(producing) 0.015 weight part by Nisshin Chemical Industries Co.
Table 20
The prescription of supply solution (H-1)
Sodium hydroxide 6.0 weight parts
Water 88.90 weight parts
Propylene glycol 4.0 weight parts
Tensio-active agent (K-1:C 14H 29O-(CH 2CH 2O) 2H) 1.1 weight parts
1-2. the evaluation of alkaline solution and alkali soap fluidized polymer film
Estimate alkaline solution and prepared alkali soap fluidized polymer film after above-mentioned saponification is handled by following mode.
(1) character of alkaline solution
Naked eyes are estimated the transparency of the alkaline solution after saponification is handled.Found that alkaline solution does not have muddiness or precipitation, and be fully transparent.
In addition, handle the back in saponification and from the alkaline solution groove, emit alkaline solution, and the inwall of visual inspection alkaline solution groove.As a result, do not observe precipitation and settling at the inwall of alkaline solution groove.
(2) with the contact angle of water
At contact angle instrument (CA-X, produce by Kyowa Kaimen Kagaku Co.) in, under drying regime (20 ℃/65%RH), using purifies waste water, and to form diameter on needle point be 1.0 millimeters drop, and itself and gained alkali saponified polymeric film surface contact the formation drop.
Will be at solid (film)-liquid (purified water) point of contact place, the angle that comprises liquid that forms between liquid level positive tangent and solid surface is decided to be contact angle.From starting point on a plurality of positions of 1000 meters, downcutting long 1 meter width is the wide square of full film, and selects 9 point measurement contact angles in the two ends and the central authorities of cutting square.
As a result, it is 35 ° at the average contact angle that records every any position of 1000 meters from starting point.
(3) foreign matter of alkali soap fluidized polymer film and muddiness
The alkali soap fluidized polymer film of gained is cut into 1 meter long full width sample piece, and under magnifying glass, observes the foreign matter and the muddiness of cutting sample with bore hole by the transmitted light on the lamp box.
Found that alkali saponified polymeric film does not contain foreign matter or muddiness, and be transparent.
Replace conductivitimeter, when using AC impedance instrument to measure alkaline solution saponification ability, obtained similar result.
[embodiment 15]
2-1. the production of alkali soap fluidized polymer film
According to the embodiment 1 of JP-A 2002-182033, [0020] section is to the explanation of [0026] section, and preparation has the cellulose acylate film of the stain-proofing layer that possesses the antireflective function.Then, bonding polyethylene terephthalate film on the stain-proofing layer surface of gained cellulose acylate film (SAT-106TS is produced by Sanei Kaken).
Use is used for the mother matrix etching processing machine (E-380II of electronic plate making system, produce by Fuji PhotoFilm Co.) as immersion treatment equipment, and the specific conductivity of packing in this equipment is the alkaline solution with following prescription (S-2) of 5.5mS/cm, and solution temperature is set is 30 ℃.
After the cellulose acylate film that will be stained with polyethylene terephthalate film soaked for 10 seconds, it is immersed in the water, fully the flush away alkaline solution.Then, with 10 seconds in the dilution heat of sulfuric acid of its immersion 0.5%, immerse in the water again and thorough washing.Then, dry described film under 100 ℃ obtains alkali saponified polymeric film (SF-2).Alkali soap fluidized polymer film (SF-2) obtains saponification on the surface of the plain acylate film of exposed fibers, but because the provide protection of polyethylene terephthalate film, the band stain-proofing layer side surface of described polymeric film is not had an effect in alkaline solution.Implement the saponification process with 1000 square metres/day speed, finish 4000 square metres treatment capacity in 4 days.
The device that described soaking device is equipped with the device that is used for unit of measure's time inner polymer film processing area that saponification handles, conductivitimeter and has the additive liq (H-2) of following prescription based on measured processing area and measured specific conductivity supply.
Table 12
The prescription of alkaline purification liquid (S-3)
Potassium hydroxide 4.0 weight %
Water 29.0 weight %
Virahol 54.0 weight %
Ethylene glycol 11.7 weight %
Tensio-active agent (K-2:C 9H 19Ph (OCH 2CH 2) 8SO 3Na)
(Ph: 1.3 weight % phenylene)
Defoamer Purlonic TR70
(producing) 0.01 weight % by Asahi Denka Co.
Table 22
The prescription of additive liq (H-3)
Potassium hydroxide 4.8 weight %
Water 29.0 weight %
Virahol 54.0 weight %
Ethylene glycol 11.7 weight %
Tensio-active agent (K-2:C 9H 19Ph (OCH 2CH 2) 8SO 3Na)
(Ph: 1.3 weight % phenylene)
Defoamer Purlonic TR70
(producing) 0.005 weight % by Asahi Denka Co.
2-2. the evaluation of alkaline solution and alkali saponified polymeric film
According to embodiment 1 in identical mode, alkaline solution and alkali saponified polymeric film after saponification that evaluation obtains is above handled.Found that the alkaline solution after saponification is handled is transparent, and in the alkaline solution groove, do not observe stain.
In addition, according to embodiment 1 in identical mode, estimate in the part when beginning is handled in saponification every day on the alkali saponified polymeric film that so obtains and the part when finishing.Found that gained alkali saponified polymeric film does not contain foreign matter or muddiness, and be transparent.
2-3. the production of polaroid
Peel off polyethylene terephthalate film in the alkali saponified polymeric film that obtains from above, obtain first polaroid protective film.Again according to the first polaroid protective film similar methods, obtain second polaroid protective film.
With thickness is that 75 microns polyvinyl alcohol film (being produced by Kuraray Co.) is immersed in the aqueous solution that comprises 7 weight part iodine and 105 weight part potassiumiodides in 1000 weight parts waters 5 minutes, thereby iodine is adsorbed onto on the film.Then, in the boric acid aqueous solution of 40 ℃ 4 weight %, longitudinally the described film of uniaxial extension is 4.4 times, and dry under tension, obtains polarizing coating.
The saponification face that uses poly (vinyl alcohol) binder will constitute the tri cellulose acetate membrane of first polaroid protective film is adhered on the surface of described polarizing coating; and the saponification face that uses poly (vinyl alcohol) binder will constitute the tri cellulose acetate membrane of second polaroid protective film is adhered on another surface of polarizing coating, thereby obtains polaroid.
2-4. the evaluation of polaroid
(1) serviceability test
Prepare 100 polaroids according to the method described above, and use acryloid cement to be adhered on the sheet glass respectively, then they are placed in the thermostatic constant wet chamber, accept 1000 hours serviceability test altogether, during this period, switched once in per 12 hours between 70 ℃, 93%RH atmosphere and 25 ℃, 93%RH atmosphere in the inside of thermostatic constant wet chamber.After from thermostatic constant wet chamber, taking out sample, check peeling off and the bubble production between polaroid and the sheet glass.
As a result, in 100 samples, all do not find to produce to peel off and bubble.
(2) dysopia
In addition, peel off the polaroid of both sides from thin film transistor (TFT) the type LCD monitor that is purchased, the dark attitude of the bonding above-mentioned polaroid in its both sides, and naked eyes evaluation then shows and bright attitude shows the irregularity that exists down.
As a result, in the entire image district, do not observe for example dysopia of irregularity.
[embodiment 16]
3-1. the production of alkali soap fluidized polymer film
By warm air, it is 30 ℃ that rolling (roll form) tri cellulose acetate membrane of 1000 mm wides (Fujitac TD80UF is produced by Fuji Photo Film Co.) is heated to the film surface temperature.Then, use rod coater with 12mL/m 2Coating amount, with maintaining 25 ℃ the alkaline solution with following prescription (S-3) coated film surface.After 20 seconds, use rod coater with 5mL/m 2Consumption coating purify waste water.Under this state, the temperature of film is 30 ℃.Then, by extrusion coating machine coating 1000mL/m 2Purify waste water, implement water and clean, and after 5 seconds, the air that blows out 100m/sec from air knife carries out water squeezing to be handled.After the water squeezing processing of the clean that will use the gravity flow coating machine and use air knife repeats twice, kept implement drying 10 seconds by drying zone, thereby make alkali saponified polymeric film SF-3 at 80 ℃.By this way, the tri cellulose acetate membrane of 6000 square metres of saponification.
Alkaline solution is contained in the alkaline solution groove, and is fed in the application processing apparatus by the pump of constant speed.The excessive liquid in coating back is returned in the alkaline solution groove, and recycle.In applying step, follow closely after the rod coater, be provided for the device of the processing area of unit of measure's time inner polymer film, described alkaline solution groove also is equipped with the whipping device that is used for saponification and handles, the conductivitimeter of measuring alkaline solution saponification ability and the device that can add the additive liq with following prescription (H-1) of predetermined amount based on measured processing area automatically.
Table 23
The prescription of alkaline solution (S-3)
Potassium hydroxide 5.5 weight parts
Water 19.49 weight parts
N-propyl alcohol 59.5 weight parts
Diethylene Glycol 14.5 weight parts
Tensio-active agent (K-3: quadrol ethylene oxide adduct
(20 moles of adducts)) 1.0 weight parts
Defoamer Surifnol DF110D
(producing) 0.01 weight part by Nisshin Chemical Industries Co.
Table 24
The prescription of supply solution (H-3)
Potassium hydroxide 6.5 weight parts
Water 19.49 weight parts
N-propyl alcohol 58.5 weight parts
Diethylene Glycol 14.5 weight parts
Tensio-active agent (K-3: quadrol ethylene oxide adduct
(20 moles of adducts)) 1.0 weight parts
Defoamer Surfinol DF110D
(producing) 0.01 weight part by Nisshin Chemical Industries Co.
3-2. the evaluation of alkaline solution and alkali saponified polymeric film
According to embodiment 14 in identical mode, alkaline solution and alkali saponified polymeric film after saponification that evaluation obtains is above handled.Found that the alkaline solution after saponification is handled is transparent, and in the alkaline solution groove, do not observe stain.
[embodiment 17]
(preparation of alkali soap solution (S-2) and alkali neutralising fluid (ST-10))
Preparation is the alkali soap solution (1.7N) and the alkali neutralising fluid of surface compositions down.
Table 25
The prescription of the alkali soap aqueous solution (S-2)
Sodium hydroxide 680 weight parts
Following cats product 110 weight parts
Defoamer Purlonic TR701 (Asahi Denka Co.) 1 weight part
9209 weight parts of purifying waste water
Table 26
The prescription of alkali neutralising fluid (ST-10)
Acetate 800 weight parts
L-aspartic acid 199 weight parts
Defoamer Surfinol DF110D
(producing) 1 weight part by Nisshin ChemicalIndustries Co.
9000 weight parts of purifying waste water
(preparation of saponification film (KF-10))
By 100 ℃ warm air, tri cellulose acetate membrane Fujitac TD80UF (being produced by FujiPhoto Film Co.) is heated to 45 ℃, then, use rod coater with 8cc/m 2Amount, with alkali soap solution (S-3) coating that maintains 30 ℃, and after 10 seconds, re-use rod coater with 20cc/m 2Consumption coating alkali neutralising fluid (ST-10).Under this state, the temperature of film is 45 ℃.Then, by extrusion coating machine coating 1000cc/m 2Purify waste water, implement water and clean, and after 5 seconds, blow on the face that scribbles water from the air of air knife with 100m/sec.After the water squeezing processing of the clean that will use the gravity flow coating machine and use air knife repeats twice, kept implement drying 10 seconds by drying zone, thereby make alkali soap film KF-10 at 80 ℃.This saponification film has 47 ° water contact angle and the surface energy of 68mN/m.
The carbonate concentration of alkali neutralising fluid (ST-10) is 860mg/L, and polyvalent metal ion (comprising calcium and magnesium ion) total concn is 2.3mg/L, and chlorine ion concentration is 1.1mg/L.
(preparation of optical compensating gage (KFH-10))
Prepare optical compensation films (KFH-10) according to the mode similar to the optical compensation films KFH-1 among the embodiment 1.
As the result of performance evaluation, prepared film shows the excellent properties similar to optical compensation films KHF-1.
[embodiment 18]
(preparation of polaroid (HB-1 to HB-10))
Prepare polarizing coating by following method: on the tensile polyvinyl alcohol film, adsorb iodine, use poly (vinyl alcohol) binder that the optical compensating gage (KFH-1 one KFH-10) of preparation in embodiment 1 or 17 is adhered on the side of described polarizing coating then, and will be as tri cellulose acetate membrane (the Fujitac TD80UF of the commercially available acquisition of embodiment 1 saponified, produce by Fuji Photo Film Co.) be adhered on the opposite side of described polarizing coating, and 80 ℃ of dryings 10 minutes.
With the axis of homology of described polarizing coating and the phase delay axle parallel arrangement of optical compensating gage.Phase delay axle vertical arrangement with the tri cellulose acetate membrane of the axis of homology of described polarizing coating and commercially available acquisition.
Phase delay axle vertical arrangement with the axis of homology and the described tri cellulose acetate membrane of described polarizing coating.Thereby make polaroid (HB-1 to HB-10).
(assembling and the evaluation of TN type liquid crystal display)
From using TN liquid crystal cell (6E-A3, produce by Sharp Inc.) liquid crystal display in peel off a pair of polaroid, and use the tackiness agent bonding as above polaroid of preparation on viewer's side and backlight side respectively as an alternative, wherein optical compensating gage is placed the liquid crystal cell side.Assemble described liquid crystal display so that the axis of homology of the axis of homology of viewer's side polaroid and backlight side polaroid is arranged with the O pattern.
Use surveying instrument (EZ-Contrast 160D is produced by ELDIM Co.) to detect the liquid crystal display that makes thus, and visual inspection show the irregularity of (L1) hypograph in dark attitude.
As a result, shown in table 27, use the liquid crystal display of optical compensation films HB-7 to HB-9 to show muddiness, thereby brightness reduce in the entire image district.Carbonate concentration, polyvalent ion concentration and chlorine ion concentration are higher than prescribed value of the present invention in the used alkali diluent in optical compensation films HB-7 to HB-9 preparation.Use HB-1, HB-2, HB-3, HB-4, HB-5, HB-6 and HB-10 then to obtain high brightness.
Table 27
Polaroid Optical compensating gage Used alkali diluted liquid or alkali neutralising fluid The image irregularity
HB-1 KHF-1 SK-1 Do not have
HB-2 KHF-2 SK-2 Do not have
HB-3 KHF-3 SK-3 Do not have
HB-4 KHF-4 SK-4 Do not have
HB-5 KHF-5 SK-5 Do not have
HB-6 KHF-6 SK-6 Do not have
HB-7 KHF-7 SK-7 Complete muddy
HB-8 KHF-8 SK-8 Complete muddy
HB-9 KHF9 SK-9 Complete muddy
HB-10 KHF-10 SK-10 Do not have
[embodiment 19]
(assembling of homeotropic alignment liquid crystal display equipment and evaluation)
From using homeotropic alignment liquid crystal element (VL-1530S, produce by Fujitsu Inc.) liquid crystal display in peel off a pair of polaroid, and use tackiness agent on viewer's side and backlight side, to be bonded in the polaroid of preparation among the embodiment 18 respectively as an alternative, wherein optical compensating gage is placed the liquid crystal cell side.Assemble described liquid crystal display with the Niccol arrangement mode, wherein the axis of homology of viewer's side polaroid is on the vertical direction, and the axis of homology of backlight side polaroid is on the horizontal direction.
Use surveying instrument (EZ-Contrast 160D is produced by ELDIM Co.) to detect the liquid crystal display that makes thus, and visual inspection show the irregularity of (L1) hypograph in dark attitude.
Use comprises that the liquid crystal display of the polaroid of the optical compensation films that makes through alkali soap aqueous solution processing of the present invention shows high brightness, and can obtain not have the gratifying liquid crystal display of image irregularity thus.
[embodiment 20]
(assembling of curved orientation liquid crystal display and evaluation)
The liquid crystal cell of preparation curved orientation, and use tackiness agent on viewer's side and backlight side, to be bonded in the polaroid of preparation among the embodiment 18 respectively, wherein optical compensating gage is positioned at the liquid crystal cell side.
The frictional direction antiparallel of frictional direction that makes liquid crystal cell and the optical anisotropic layer relative with it.
Use surveying instrument (EZ-Contrast 160D is produced by ELDIM Co.) to detect the liquid crystal display that makes thus, and visual inspection show the irregularity of (L1) hypograph in dark attitude.
Use comprises that the liquid crystal display of the polaroid of the optical compensation films that makes through alkali soap aqueous solution processing of the present invention shows high brightness, and can obtain not have the gratifying liquid crystal display of image irregularity thus.
[embodiment 21]
(preparation of saponification film (KF-11) and polaroid protective film)
According to the explanation of embodiment 1 among the JP-A 2002-182033, preparation provides the cellulose acylate film of antireflective coating.Then, bonding polyethylene terephthalate film on the stain-proofing layer surface of gained cellulose acylate film (SAT-106TS is produced by Sanei Kaken).Use is used for the mother matrix etching processing machine E-380II of electronic plate making system as immersion treatment equipment, and the alkali soap solution (S-1) of packing in this equipment and having following prescription, and solution temperature is set is 50 ℃.After described film was soaked for 30 seconds, it is immersed in the alkali diluted liquid (SK-11) dilution alkali soap solution.Then, it was soaked for 10 seconds in alkali neutralising fluid (ST-12), immerse thorough washing in the purification tank again.Then, dry described film under 100 ℃ obtains 8000 meters alkali soap cellulose acylate film (KF-11) (10000 square metres).Peel off polyethylene terephthalate film from tri cellulose acetate membrane, obtain first polaroid protective film.
Table 28
The prescription of alkali diluted liquid (SK-11)
Nonionogenic tenside (being used among the S-1) 30 weight parts
Defoamer Surfinol DF110D
(producing) 1 weight part by Nisshin ChemicalIndustries Co.
9769 weight parts of purifying waste water
Table 29
The prescription of alkali neutralising fluid (ST-12)
L-aspartic acid 100 weight parts
9900 weight parts of purifying waste water
Prepare 300 liters alkali diluted liquid (SK-11), wherein carbonate concentration is 330mg/L, and the total concn that comprises the polyvalent metal ion of calcium and magnesium is 44mg/L, and the concentration of chlorion is 12mg/L.After processing, the carbonate concentration of described liquid is 3030mg/L, and the total concn that comprises the polyvalent metal ion of calcium and magnesium is 227mg/L, and the concentration of chlorion is 32mg/L.
Prepare 300 liters alkali neutralising fluid (ST-12), wherein carbonate concentration is 360mg/L, and the total concn that comprises the polyvalent metal ion of calcium and magnesium is 52mg/L, and the concentration of chlorion is 18mg/L.After processing, the carbonate concentration of described liquid is 1420mg/L, and the total concn that comprises the polyvalent metal ion of calcium and magnesium is 118mg/L, and the concentration of chlorion is 25mg/L.
The photoabsorption of the alkali soap solution after 400 nanometers are measured the alkali soap solution before saponification is handled and handled 10000 square metres, recording and handling preceding photoabsorption is 0.00, handling the back photoabsorption is 1.88.
With thickness is that 75 microns polyvinyl alcohol film (Kuraray Co. production) is immersed in the aqueous solution that comprises 7 weight part iodine and 105 weight part potassiumiodides in 1000 weight parts waters 5 minutes, thereby iodine is adsorbed onto on the film.Then, in 40 ℃ 4 weight % boric acid aqueous solutions, longitudinally the described film of uniaxial extension is 4.0 times, and dry under tension, obtains polarizing coating.Use poly (vinyl alcohol) binder that one side of described polarizing coating and the saponification face of first polaroid protective film are bonded together; and the cellulose acylate film surface of the optical compensating gage (KHF-1) of preparation among the opposite side of described polarizing coating and the embodiment 1 is bonded together; descended dry 10 minutes at 80 ℃ then, thereby obtain polaroid (HB-11).
(evaluation of polaroid)
(1) serviceability test
Prepare 100 polaroids according to the method described above, and use acryloid cement to be adhered on the sheet glass respectively, then they are placed in the thermostatic constant wet chamber, accept 1200 hours serviceability test altogether, during this period, switched once in per 12 hours between 70 ℃, 93%RH atmosphere and 25 ℃, 93%RH atmosphere in the inside of thermostatic constant wet chamber.Check peeling off and the bubble production between polaroid and the sheet glass, and in 100 samples, all do not find to produce to peel off and bubble.
In addition, peel off the polaroid of both sides from thin film transistor (TFT) the type LCD monitor that is purchased, the dark attitude of the bonding above-mentioned polaroid in its both sides, and naked eyes evaluation then shows and bright attitude shows the irregularity that exists down.In the entire image district, do not observe for example dysopia of irregularity.Prepare 100 polaroids according to the method described above, use acryloid cement to be adhered to it on sheet glass respectively, and they are placed in the thermostatic constant wet chamber, accept 1000 hours serviceability test altogether, during this period, the inside of constant temperature and humidity room was sandwiched between the atmosphere of 70 ℃, the atmosphere of 93%RH and 25 ℃, 93%RH 12 hours.In 100 samples that from constant temperature and humidity room, take out, check peeling off and the bubble production between polaroid and the sheet glass, and in any one of 100 samples, all find to produce to peel off to produce with bubble.
Assembling TN liquid crystal display, and use surveying instrument (EZ-Contrast 160D is produced by ELDIM Co.) to detect the liquid crystal display that makes thus, and visual inspection shows the irregularity of (L1) hypograph in dark attitude.In the entire image district, do not observe for example defective of irregularity at all.
Industrial applicability
Use the method for aqueous slkali alkali soap cellulose acylate film of the present invention can realize film surface uniform and accurate alkali soap, and can not produce for example muddy defective at film, and can high production rate certain surface of saponification optionally. Gained alkali soap film can be readily incorporated in the optical compensating gage, is used for not showing the large scale liquid crystal display device of defective. In addition, can obtain cellulose acylated thing film as transparent substrate by the present invention, the excellent adhesiveness that has between the orientation film of itself and optical compensating gage.
In the situation of continuous saponification process thin polymer film, even in the large situation for the treatment of capacity, method of the present invention also allows to implement saponification in stable mode and processes, and can not reduce operating efficiency, perhaps causes waste disposal problem.

Claims (23)

1. one kind with comprising alkaline reagents, water, organic solvent, tensio-active agent and the alkaline solution of the solubilising reagent method of cellulose acylate film being carried out the alkali soap processing mutually.
2. according to the process of claim 1 wherein that the inorganic/organic ratio (I/O value) of described organic solvent is 0.5 or higher, and its solubility parameters is 16 to 40[mJ/m 3] 1/2
3. according to the method for claim 1 or 2, wherein said tensio-active agent is at least a tensio-active agent that is selected from nonionogenic tenside, anion surfactant, cats product and amphoterics.
4. method of cellulose acylate film being carried out the alkali soap processing with the alkaline solution that comprises alkaline reagents and tensio-active agent, wherein said tensio-active agent are the amphotericses by following general formula (I) expression:
Figure A2003801050460002C1
Wherein, A represents alkylidene group; L 0Expression connects nitrogen-atoms and X -Group; X -Expression-COO -,-SO 3 -Or-PO 3H -R 0The expression alkyl; R 1Expression hydrogen atom or alkyl; N represents from 1 to 50 integer; P and q represent 1 or 2 integer and p+q=3 respectively.
5. according to any one method of claim 1 to 3, wherein said mutual solubilising reagent is at least a many alkylol cpds, and the solubleness of water are 30 grams or higher in 25 ℃ of described mutual solubilising reagent of per down 100 grams.
6. according to the method for claim 4, wherein said alkaline solution comprises the alkaline reagents of 0.1 to 25 weight % and the mixed solvent of water or water and hydrophilic organic solvent.
7. according to any one method of claim 1 to 6, wherein said alkaline solution has alkaline reagents concentration, 45mN/m or lower surface tension and 0.8 to 20mPas the viscosity of 0.1 to 25 weight %.
8. according to any one method of claim 1 to 7, wherein said alkaline solution comprises that at least a boiling point is 120 ℃ or higher hydrophilic compounds, and can dissolve 50 grams or more water in the described hydrophilic compounds of 100 grams.
9. according to any one method of claim 1 to 8, wherein said alkaline solution comprises defoamer.
10. method of cellulose acylate film being carried out the alkali soap processing with alkaline solution, it comprises: the step of handling cellulose acylate film with alkaline solution; And with the step of alkali diluent or the neutralising fluid described alkaline solution of flush away from the described film, wherein said alkali diluent or neutralising fluid have 3500mg/L or lower carbonate concentration.
11. according to the method for claim 10, wherein said alkali diluent or neutralising fluid have 500mg/L or lower polyvalent metal ion concentration, and chlorine ion concentration is 300mg/L or lower.
12. according to the method for claim 10 or 11, wherein said alkali diluent or neutralising fluid comprise tensio-active agent.
13. according to any one method of claim 10 to 12, the solvent of wherein said alkali diluent or neutralising fluid is the mixture of water or water and organic solvent.
14. according to any one method of claim 10 to 13, wherein said alkali diluent or neutralising fluid comprise defoamer.
15. according to any one method of claim 10 to 14, the wherein said step of handling cellulose acylate film with alkaline solution is included in the step of coating alkaline solution on the cellulose acylate film.
16. according to any one method of claim 1 to 15, it is included under room temperature or the higher temperature step of the described alkaline solution of coating on cellulose acylate film, and from the described cellulose acylate film the step of the described alkaline solution of flush away.
17. surperficial saponified cellulose acylate film by obtaining according to any one method of claim 1 to 15.
18. optical thin film that comprises according to the surperficial saponified cellulose acylate film of claim 17.
19. use the method for the described alkaline solution of additive liq supply in the process of using alkaline solution continuous saponification polymeric film surface with production alkali soap fluidized polymer film, it comprises:
Measure the step of the saponification ability of described alkaline solution;
Based on the saponification ability of being surveyed, determine the supply mode of additive liq, thereby after with described additive liq supply, make the saponification ability of described alkaline solution be in step in the pre-determined range; And
With determined supply mode, with the step of the described alkaline solution of described additive liq supply.
20. according to the method for claim 19, it also comprises the step of measuring the processing area of described polymeric film in the unit time, wherein determines described pre-determined range based on the processing area in the measured unit time.
21., wherein be selected from the saponification ability that following method is measured described alkaline solution: the measurement of the electrode potential between the measurement of the electrode voltage between the electrode of the measurement of the measurement of alkaline solution pH, alkaline solution specific conductivity, the measurement of alkaline solution electric impedance, current control and the electrode of current control by at least a according to the method for claim 20.
22. use the method for the described alkaline solution of additive liq supply in the process of using alkaline solution continuous saponification polymeric film surface with production alkali soap fluidized polymer film, it comprises:
Measure the step of the processing area of described polymeric film in the unit time;
Carry out the pre-storage that required alkaline solution is processed in saponification according to described polymeric film, by the step of the consumption of alkaline solution in the processing area Units of Account time in the measured unit time to unit surface;
Consumption in the unit time that draws based on aforementioned calculation is determined the supply mode of additive liq, thereby after with described additive liq supply, makes the saponification ability of described alkaline solution be in step in the pre-determined range; And
According to determined supply mode, with the step of the described alkaline solution of described additive liq supply.
23. according to the method for claim 22, wherein said saponification process comprises the step of prior heated polymerizable thing film to 25 ℃ or higher temperature successively; Apply the step of described polymeric film with described alkaline solution; Described polymeric film is remained on step under 25 ℃ or the higher temperature, and from the described polymeric film the step of the described alkaline solution of flush away.
CNB200380105046XA 2002-12-03 2003-12-02 Alkali saponification method for cellulose acylate film, a surface saponified cellulose acylate film and an optical film utilizing the same Expired - Lifetime CN100336850C (en)

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