JP4635435B2 - Transparent film, transparent conductive film and manufacturing method thereof, liquid crystal display, organic EL display and touch panel - Google Patents

Description

  The present invention relates to a transparent film for electronic displays having a high ultraviolet transmittance, a transparent film suitable for the substrate material using the transparent film, and a transparent conductive film particularly suitable for the substrate material using these, and The present invention also relates to a liquid crystal display, an organic EL display, and a touch panel to which the transparent conductive film is applied.

  Conventionally, liquid crystal display elements, organic EL display elements, plasma displays, electronic display substrates such as electronic paper, electro-optical element substrates such as CCD and CMOS sensors, solar cell substrates, etc. are thermally stable and transparent. Glass has been used because of its high property and low water vapor permeability. However, with the recent popularization of mobile phones or portable information terminals, there has been a demand for lightweight substrates that are highly flexible and difficult to break against the relatively heavy glass that is easily broken.

  In addition, in these liquid crystal display elements, organic EL display elements, plasma display, electronic paper, touch panel and other electronic display elements, etc., together with these substrates, these electronic display elements are sealed from the outside air (humidity, oxygen, etc.), With regard to sealing films that extend the life of elements, instead of glass and other relatively heavy materials that are easy to break, there is a need for lightweight substrates or transparent films that are resistant to cracking. Various studies have been made on a transparent film (referred to herein as an electronic display film) used as an application.

  Transparent resin substrate materials improved in heat resistance by crosslinking inexpensive and general-purpose resins, for example, acrylate-based crosslinked resins described in JP-A-10-71667, maleimide-based crosslinked resins described in JP-A-5-209067, An α-methylstyrene-based crosslinked resin described in JP-A-8-15682, a polycarbonate-based crosslinked resin described in JP-A-2002-173529, an epoxy-based crosslinked resin described in JP-A-2001-59015, and the like are disclosed. Further, it has been proposed to use polyether sulfone, polycarbonate, or a transparent film obtained by bonding polyether sulfone described in JP-A-5-142525 and an acrylic substrate as a plastic substrate. Yes.

  In the case of electronic devices such as liquid crystal displays, organic EL displays and touch panels, these elements are formed on a transparent film as a plastic substrate, and the elements are sealed as a sealing material in order to seal them from moisture and oxygen in the air. These transparent films are stacked and sealed with an adhesive.

  As an adhesive for sealing, an ultraviolet curable resin is mainly used. After applying this between the substrate to be bonded and the sealing material, actinic rays (ultraviolet rays) are irradiated from the sealing material side, for example. In general, the element is sealed by photocuring.

  Until now, the substrate or sealing material of the electronic display element has been mainly a glass material having excellent moisture resistance. The glass material also has no problem in the sealing process.

  When this glass material is replaced with a transparent film, when a general PET film or PEN film or the above-mentioned polyethersulfone is used, curing of the ultraviolet resin as an adhesive is not promoted, and there is a problem in the sealing process. I found out. In addition to the heat radiation from the irradiation light source itself, it has been found that the film itself generates heat due to ultraviolet absorption, which causes problems such as thermal shrinkage and thermal deterioration of the film.

  Moreover, although the norbornene resin film had no problem regarding the curing of the adhesive, it was found that the film itself was fragile.

  In addition, recently, a metal oxide is mixed and phased with a resin such as polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, polyimide, polyamide, etc. disclosed in Patent Document 1 (Japanese Patent Laid-Open No. 2000-122038). Even in plastic films with improved heat resistance by the technique of dissolving organic-inorganic polymer hybrids, the wavelength dispersion of birefringence is not positive dispersion, and the transmittance in the wavelength region of actinic light is also low, which is used for electronic displays. It did not have sufficient performance as a transparent film.

Thus, as a transparent film for an electronic display, in addition to transmittance in the ultraviolet region, optical properties such as birefringence, gas barrier properties, etc. are required. Transparent resin films that satisfy all of these necessary properties are now available. It was not found so far.
JP 2000-122038 A

  Therefore, the present invention intends to provide a transparent film suitable for a substrate for electronic display, a sealing film, and the like, and further, a transparent conductive film using the same, a method for producing them, and the method, An object of the present invention is to provide a liquid crystal display, an organic EL display and a touch panel to which a transparent conductive film is applied.

The above objects of the present invention are achieved by the following means 1 to 13 .
1. In a transparent film for an electronic display comprising a transparent film having an ultraviolet transmittance of 50% or more in a wavelength region of 250 to 450 nm and a glass transition temperature measured by TMA (stress strain measurement) of 180 ° C. or more,
A transparent film, wherein the main component is a hydrolysis polycondensate of cellulose ester and an alkoxysilane represented by the following general formula (1).
General formula (1) R _4-n Si (OR ′) _n
(In the formula, R and R ′ represent a hydrogen atom or a monovalent substituent, and n is 3 or 4.)
2. 2. The transparent film according to 1, wherein the cellulose ester has a substitution degree of cellulose ester satisfying the following formulas 1 and 2.
Formula 1 0 ≦ Y ≦ 1.5
Formula 2 1.0 <X + Y ≦ 2.9
(Here, X represents the degree of substitution with an acetyl group, and Y represents the degree of substitution with a substituent having an alkoxysilyl group.)
3. The hydrolysis polycondensate is represented by the following general formula (2), and the total mass of the hydrolysis polycondensation product represented by the general formula (2) is less than 20% by mass with respect to the transparent film. 3. The transparent film according to 1 or 2, wherein
General formula (2) R _4-n SiO _{n / 2} (n is a natural number)
4). The transparent film according to any one of 1 to 3, wherein the content of the plasticizer in the transparent film is less than 1%.
5. When the in-plane retardation value at a wavelength of 590 nm is R ₀ (590) and the in-plane retardation value at a wavelength of 480 nm is R ₀ (480), the ratio (R ₀ (480) / R ₀ (590)) The transparent film according to any one of 1 to 4, wherein is 0.8 or more and less than 1.0.
The transparent film according to any one of 6.1 to 5 is used as a sealing film for an electronic display, and the adhesive used for sealing is an actinic ray curable resin. display.
A moisture-proof film containing a metal oxide, a metal nitride, or a metal carbide is provided on at least one surface of the transparent film according to any one of 7.1 to 5, and further on the moisture-proof film or the moisture-proof film A transparent conductive film, wherein a transparent conductive film is provided on the side opposite to the surface on which the film is provided.
8). 8. The transparent conductive film according to 7, wherein the moisture-proof film is mainly composed of silicon oxide.
9. 9. The transparent conductive film according to 8, wherein the moisture-proof film is amorphous.
10. A liquid crystal display using the transparent conductive film according to any one of 10.7 to 9 as a substrate.
An organic EL display using the transparent conductive film according to any one of 11.7 to 9 as a substrate.
A transparent conductive film according to any one of 12.7 to 9 is used as a substrate.
13. A method for producing a transparent film, comprising producing the transparent film according to any one of 1 to 5 by a solvent casting method.
Note that the following (1) to (17) are means to be referred to.

(1 )
The transparent film for electronic displays which consists of a transparent film whose transmittance | permeability of the ultraviolet-ray in the wavelength range of 250-450 nm is 50% or more, and whose glass transition temperature measured by TMA (stress-strain measurement) is 180 degreeC or more.

(2 )
The transparent film according to ( 1 ) , wherein a main component of the transparent film is a cellulose ester.

(3 )
The transparent film as described in ( 1 ) or ( 2 ) above, wherein the main component is a hydrolysis polycondensate of cellulose ester and an alkoxysilane represented by the following general formula (1).

General formula (1) R _4-n Si (OR ′) _n
(In the formula, R and R ′ represent a hydrogen atom or a monovalent substituent, and n is 3 or 4.)
(4 )
The transparent film as described in ( 3 ) above, wherein the substitution degree of the cellulose ester is a cellulose ester satisfying the following formulas 1 and 2.

Formula 1 0 ≦ Y ≦ 1.5
Formula 2 1.0 <X + Y ≦ 2.9
(Here, X represents the degree of substitution with an acetyl group, and Y represents the degree of substitution with a substituent having an alkoxysilyl group.)
(5 )
The hydrolysis polycondensate is represented by the following general formula (2), and the total mass of the hydrolysis polycondensation product represented by the general formula (2) is less than 20% by mass with respect to the transparent film. The transparent film as described in ( 3 ) or ( 4 ) above, wherein

General formula (2) R _4-n SiO _{n / 2} (n is a natural number)
(6 )
Content of the plasticizer of the said transparent film is less than 1%, The transparent film of any one of said ( 1 ) - ( 5 ) characterized by the above-mentioned .

(7 )
When the in-plane retardation value at a wavelength of 590 nm is R ₀ (590) and the in-plane retardation value at a wavelength of 480 nm is R ₀ (480), the ratio (R ₀ (480) / R ₀ (590)) The transparent film as described in any one of ( 1 ) to ( 6 ) , wherein is 0.8 or more and less than 1.0.

(8 )
The transparent film according to any one of ( 1 ) to ( 7 ) is used as a sealing film for an electronic display, and the adhesive used for sealing is an actinic ray curable resin. And electronic display.

(9 )
A moisture-proof film containing a metal oxide, a metal nitride, or a metal carbide is provided on at least one surface of the transparent film according to any one of ( 1 ) to ( 7 ) , and further on the moisture-proof film, Or the transparent conductive film is provided in the opposite side to the surface in which the said moisture proof film was provided, The transparent conductive film characterized by the above-mentioned.

(10 )
The said moisture-proof film | membrane is mainly comprised from the silicon oxide, The transparent conductive film as described in said ( 9 ) characterized by the above-mentioned .

(1 1)
The transparent conductive film as described in ( 10 ) above , wherein the moisture-proof film is amorphous.

(1 2)
The moisture-proof film and the transparent conductive film are discharged by applying a high-frequency voltage between the opposing electrodes under atmospheric pressure or a pressure near atmospheric pressure, thereby changing the reactive gas into a plasma state and reacting in the plasma state. The transparent conductive film according to any one of ( 9 ) to ( 11 ) , wherein the transparent conductive film is a film formed by exposing the transparent film to a gas.

(1 3)
Wherein said high frequency voltage, a range of frequencies 100KHz～150MHz, and a range of supply power ^{1W / cm 2 ~50W / cm 2} , wherein said moisture-proof film and the transparent conductive film is formed The transparent conductive film as described in ( 12 ) .

(14 )
A liquid crystal display using the transparent conductive film according to any one of ( 9 ) to ( 12 ) as a substrate.

( 15)
An organic EL display using the transparent conductive film according to any one of ( 9 ) to ( 12 ) as a substrate.

( 16)
A touch panel using the transparent conductive film according to any one of ( 9 ) to ( 12 ) as a substrate.

( 17)
The manufacturing method of the transparent film characterized by manufacturing the transparent film of any one of said ( 1 ) - ( 7 ) by the solvent cast method.

  A transparent film having a high ultraviolet transmittance suitable as a substrate for electronic display and a sealing film, and a transparent film made of a novel organic-inorganic hybrid polymer suitable for the film can be provided.

  Next, the best mode for carrying out the present invention will be described, but the present invention is not limited thereto.

  The transparent film for an electronic display in the present invention refers to a transparent sealing film or a substrate for sealing an electronic device such as a liquid crystal display, an organic EL display and a touch panel.

  The transparent film for an electronic display according to the present invention needs to have an ultraviolet transmittance of 50% or more in a wavelength region of 250 to 450 nm.

FIG. 1 shows the results of measuring the above-described representative conventional transparent film or glass material and the transparent film of the present invention with respect to ultraviolet transmittance. The thickness of each film is 100 μm.
(A) is a polyethersulfone (PES) film (Sumilite FS1300 manufactured by Sumitomo Bakelite Co., Ltd.), (b) is a norbornene resin film (JSR Arton (R)), and (c) is a diacetylcellulose film (DAC). ) And (d) are data on an organic-inorganic hybrid film made of cellulose-silica described later, and (e) is data on soda glass.

  (A) The transmittance of the polyethersulfone film in the ultraviolet region is low. Also, soda glass, which is usually used as a substrate, does not have a good transmittance in a short wave region shorter than 300 nm, but has extremely high heat resistance (Tg> 500 ° C.), and therefore absorbs ultraviolet light of 250 nm to 300 nm. It is presumed that the problem will not manifest. (B) Arton (R) film also has absorption which seems to be caused by the additive, and it has been confirmed that it becomes brittle by ultraviolet irradiation.

  On the other hand, the transparent film (c) DAC and (d) organic-inorganic hybrid film etc. of the present invention show a transmittance of 50% or more between 250 nm and 450 nm, and in most regions. Although 80% or more, it was confirmed that there was no problem of uncured sealing process in these films. Therefore, in order to sufficiently cure the sealing process, it is presumed that a transmittance of at least 50% is indispensable at a wavelength of 250 nm to 450 nm. If the transmittance of light of 250 nm to 450 nm is 50% or more, it is considered that the higher the transmittance, the more advantageous in the sealing process, and the upper limit of the transmittance is not particularly set, but actually the transparent film and the air interface Therefore, the upper limit is approximately 95%.

  Moreover, the transparent film of this invention needs that a glass transition temperature is 180 degreeC or more. This is because when a transparent conductive film made of ITO (Indium Tin Oxide) is formed on a transparent film, it is necessary to crystallize the ITO in order to obtain a highly conductive ITO. This is because it is said to be around 180 ° C. ITO crystallizes at 180 ° C, but the higher the temperature, the better the heat resistance of the transparent film because crystallization proceeds faster. However, any material expands at higher temperatures, and generally the thermal expansion coefficient of organic matter is that of inorganic matter. Since the coefficient of thermal expansion is more than an order of magnitude larger than the coefficient of thermal expansion, when cooling to room temperature after exposure to high temperatures, cracks and ITO film Since peeling and curling of the film occur, treatment at a very high temperature is not preferable, and 250 ° C. is sufficient as the heat resistance of the transparent film.

  Since the glass transition temperature of the cellulose esters of the present invention is unclear and often not measured by a scanning differential calorimeter (DSC), the inflection point of the temperature-strain curve in thermal stress strain measurement (TMA) is determined. Determine the glass transition temperature.

  As an actual measuring apparatus, a TMA-SS6100 manufactured by Seiko Instruments Inc. was used, a sample having a film thickness of 100 μm and a width of 4 mm was fixed at a distance between chucks of 20 mm, and the temperature was once raised from room temperature to 180 ° C. to remove residual strain. Thereafter, from room temperature to 10 ° C./min. The linear expansion coefficient is obtained from the elongation of the distance between chucks. Further, as described above, the glass transition temperature is obtained from the inflection point of the temperature-strain curve.

  A resin film having a glass transition temperature of 180 ° C. or higher by such a method and having a heat resistance and having a small amount of ultraviolet absorption has relatively few types, for example, as appropriate, Examples thereof include a film made of a cellulose ester-based resin such as diacetyl cellulose (DAC). These are preferable because there is no component having an aromatic group in the resin skeleton.

  Preferred cellulose esters include triacetyl cellulose (TAC), diacetyl cellulose (DAC), acetyl cellulose, cellulose acetate propionate (CAP), cellulose acetate butyrate (CAB), cellulose acetate phthalate, cellulose acetate trimellitate, nitric acid There are cellulose esters such as cellulose, and these cellulose esters have the above-mentioned ultraviolet light transmission characteristics, and among these, those having the above heat resistance are selected. Any material selected according to these selection criteria is suitable for the transparent film for electronic displays of the present invention. In particular, diacetylcellulose (DAC) is preferred because of its heat resistance.

  For these films, for plastic effect, moisture permeability reduction, ultraviolet absorption of 250 nm or less, infrared absorption, hue adjustment, retardation adjustment, surface roughness adjustment, oxidation resistance improvement, etc. Functional low molecular weight compounds such as plasticizers, ultraviolet absorbers, infrared absorbers, dyes, retardation adjusting agents, matting agents, and antioxidants may be added. It is necessary to make the absorption by the additive more than the ultraviolet transmittance. In particular, among these additives, when using aromatic compounds, etc., these have absorption in the ultraviolet region, so when using these, the ultraviolet transmittance is within the range of the above-mentioned numerical value. Use it.

However, the addition of these low molecular weight compounds leads to a decrease in the glass transition temperature and an increase in the linear expansion coefficient of the transparent film. Therefore, it is preferable to suppress these contents to less than 1%, and more preferably not to contain them. . For example, if 1% of EPEG (ethyl phthalyl ethyl glycolate), which is often used as a plasticizer for cellulose esters, is added to triacetyl cellulose (TAC), the glass transition temperature is lowered by 10 ° C. or more.
Therefore, the addition amount of the low molecular compound such as a plasticizer is preferably less than 1%.

  In addition to the above cellulose ester resin, modified resins containing other polymer components that do not have the ability to absorb ultraviolet rays, hybrid resins, and the like are included. Cellulose ester resins having improved heat resistance by these modifications are more preferable. Has characteristics.

  Further, it has been found by researchers that the transparent film having the ultraviolet transmittance and the glass transition point of the present invention has an excellent effect on the linear expansion coefficient. It is highly desirable for an electronic display to have a low linear expansion coefficient in view of the function of displaying a fine image.

  As described above, in the cellulose ester resin according to the present invention, an organic-inorganic hybrid in which main components are cellulose ester and a hydrolyzed polycondensate of alkoxysilane represented by the following general formula (1) is more preferable.

General formula (1)
R _4-n Si (OR ′) _n
In the formula, R ′ represents an alkyl group, R represents a hydrogen atom or a monovalent substituent, and n represents 3 or 4.

  Examples of the alkyl group represented by R ′ include groups such as a methyl group, an ethyl group, a propyl group, and a butyl group, which may have a substituent, and the substituent exhibits properties as an alkoxysilane. If it is, there is no restriction | limiting in particular, For example, although it may be substituted by the halogen atom, the alkoxy group, etc., More preferably, it is an unsubstituted alkyl group, and especially a methyl group and an ethyl group are preferable.

  The monovalent substituent represented by R may be a compound exhibiting properties as an alkoxysilane, and specifically includes an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aromatic heterocyclic group, a silyl group. Group and the like. Of these, an alkyl group, a cycloalkyl group, and an alkenyl group are preferable. These may be further substituted. Examples of the substituent of R include various substituents that do not impair the properties of alkoxysilane, such as halogen atoms such as fluorine atom and chlorine atom, amino group, epoxy group, mercapto group, hydroxyl group, and acetoxy group.

As preferable examples of the alkoxysilane represented by the general formula (1), specifically, tetramethoxysilane, tetraethoxysilane (TEOS), tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetra t-butoxysilane, tetrakis (methoxyethoxy) silane, tetrakis (methoxypropoxy) silane,
Further, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, i-butyltrimethoxysilane, n-hexyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3 -Mercaptopropyltrimethoxysilane, acetoxytriethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, (3, 3, - trifluoropropyl) trimethoxysilane, pentafluorophenyl phenylpropyl trimethoxysilane, further vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, vinyltrimethoxysilane, and vinyltriethoxysilane and the like.

  In addition, a quantification silicon compound such as silicate 40, silicate 45, silicate 48, and M silicate 51 manufactured by Tama Chemical, in which these compounds are partially condensed may be used.

  Since the alkoxysilane has a silicon alkoxide group that can be hydrolyzed and polycondensed, by hydrolytic polycondensation of these alkoxysilanes, a network structure of a polymer compound is formed. By condensing the decomposition polycondensate with the cellulose ester, a transparent film having a dense cross-linked structure between the organic polymer component composed of cellulose ester and the polymer component formed by hydrolysis polycondensation of alkoxysilane is obtained. In addition, silicon alkoxide and silica, which is a polycondensate thereof, do not absorb from the visible region to the ultraviolet region (250 nm to 700 nm). Therefore, the transparent film is resistant to heat without losing the high ultraviolet transmittance of cellulose ester. As a result, it is possible to obtain a surprising effect that the property is improved and the material is not easily deformed even under a high temperature condition.

  The effect of increasing the glass transition temperature by hybridizing silica to cellulose ester has a certain degree of correlation between the amount of silica added and the amount of increase in glass transition temperature in the region where the amount of silica added is low (1 to 10% by mass). However, in the region of 10% by mass or more, the improvement effect is not seen so much, and when it exceeds 20% by mass, there is an adverse effect that the film tends to be brittle due to excessive silica content. If silica is added too much, the organic polymer and silica are phase-separated, and the effect of increasing the glass transition temperature is reduced. When the amount of silica added is less than 1%, the effect of increasing the glass transition temperature is hardly observed. Therefore, the amount of silica added is preferably in the range of 1 to 20% by mass.

  In the present invention, the main component means that the component accounts for 80% or more by mass ratio, and cellulose ester is preferable as the main component. It is preferable that the remaining 20% is mainly hydrolyzed polycondensate of alkoxysilane represented by the general formula (1). Moreover, the ratio of the sum of the hydrolysis polycondensate of the cellulose ester and the alkoxysilane in the transparent film is preferably 99% or more. As 1% other than the hydrolysis polycondensate of cellulose ester and alkoxysilane, functional additives such as a plasticizer and a matting agent as described later may be contained.

  Moreover, as a cellulose ester used in the transparent film whose main component is a condensate during hydrolysis of the cellulose ester and the alkoxysilane, acetyl cellulose is preferable. This is because the glass transition temperature decreases if the acid that replaces cellulose is a long organic acid. The glass transition temperature can be changed by changing the ratio of substitution with an acetyl group and an organic acid longer than the acetyl group. However, substitution with an organic acid having an aromatic group is not preferable because the ultraviolet light transmittance of the cellulose ester is lowered.

  The glass transition temperature can also be changed by changing the substitution degree for substituting the hydroxyl group of the cellulose ester. When all the hydroxyl groups of the cellulose ester are substituted, the glass transition temperature is lowered. Furthermore, since the solubility with respect to the organic solvent is deteriorated, a high-concentration resin solution (hereinafter referred to as “dope”) cannot be produced. Accordingly, the substitution degree for substituting the hydroxyl group of cellulose is preferably 2.9 or less (the glucose unit forming cellulose has three hydroxyl groups that can be bonded. For example, in cellulose triacetate, When all the hydroxyl groups are bonded to acetyl groups, the degree of substitution with acetyl groups is 3.0). However, if it is 1.0 or less, the solubility in an organic solvent is lowered again, so 1.0 or more is preferable.

  Moreover, the organic acid which substitutes a cellulose may have an alkoxy silyl group. Such a cellulose ester is preferable because it can undergo a hydrolysis-condensation reaction with an alkoxysilane, and an organic-inorganic hybrid film having a strong network structure can be obtained. However, when the substituent having an alkoxysilyl group is more than 1.5, the resulting transparent film is brittle and easily cracked, which is not preferable.

  Therefore, as the cellulose ester, when the substitution degree of the cellulose ester is represented by X, the substitution degree by the functional group having an alkoxysilyl group is represented by Y, the following formulas (1) and (2) It is preferable that it is the cellulose ester which satisfy | fills.

Formula (1) 0 <= Y <= 1.5
Formula (2) 1.0 <X + Y ≦ 2.9
The measuring method of the substitution degree of these acyl groups can be measured according to ASTM-D817-96.

  The raw material cellulose of the cellulose derivative used in the present invention is not particularly limited, and examples thereof include cotton linter, wood pulp, and kenaf. Moreover, although the cellulose derivative obtained from these can be used individually or in mixture of arbitrary ratios, it is preferable to use 50 mass% or more of cotton linters.

  The molecular weight of the cellulose derivative is preferably 70,000 to 200,000 in terms of number average molecular weight (Mn) from the viewpoint of the elastic modulus of the film obtained, the viscosity of the dope and the film forming speed, and is preferably 100,000 to 200,000. Are more preferred. The cellulose derivative used in the present invention has an Mw / Mn ratio of less than 3.0, preferably 1.4 to 2.3.

  Since the average molecular weight and molecular weight distribution of the cellulose derivative can be measured using high performance liquid chromatography, the number average molecular weight (Mn) and the weight average molecular weight (Mw) can be calculated using this, and the ratio can be calculated.

  The measurement conditions are as follows.

Solvent: Methylene chloride Column: Shodex K806, K805, K803G (Used by connecting three Showa Denko Co., Ltd.)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Sciences)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0ml / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corp.) Mw = 100000 to 500 samples were used. The 13 samples are preferably used at approximately equal intervals.

  Moreover, as content of the organometallic compound (alkoxysilane hydrolysis polycondensate) in a transparent film, like the following general formula (3) with respect to the total mass of a transparent film, the said general formula (1) It is the mass which assumed that the compound reacted and it took the form which hydrolyzed polycondensation was complete | finished like said general formula (2), and 1-20 mass% is preferable. In order that the transparent film is difficult to soften at high temperature, the addition amount of the organometallic compound is preferably 1% by mass or more, and the network structure of the transparent film is prevented from becoming too dense and becoming a fragile film. It is preferable that the addition amount of the organometallic compound is 20% by mass or less of the transparent film.

General formula (3)
R _4-n Si (OR ′) _n + n / 2H ₂ O → R _4-n SiO _{n / 2}
For example, in tetraethoxysilane (Si (OEt) ₄ , molecular weight 208), silica (SiO ₂ , molecular weight 60) is generated by performing hydrolytic polycondensation with 2 equivalents of water. Ideally, 29 parts by mass of silica are produced from ethoxysilane. Therefore, from 171 parts by mass of triacetyl cellulose (TAC) and 100 parts by mass of tetraethoxysilane, an organic-inorganic hybrid film into which 29 parts by mass of silica has been introduced is obtained, and the silica content is 14.5%. Become.

<Hydrolysis catalyst>
In the transparent film of the present invention, the alkoxysilane represented by the general formula (1) may promote hydrolysis by adding water and a catalyst as necessary to cause hydrolysis.

  However, from the viewpoint of productivity such as film haze, flatness, film forming speed, and solvent recycling, it is preferable that the water content be in the range of 0.01% to 2.0% of the dope concentration.

  When water is added to the hydrophobic alkoxysilane, it is preferable that a hydrophilic organic solvent such as methanol, ethanol, or acetonitrile coexists so that the organometallic compound and water can be easily mixed. Moreover, when adding alkoxysilane or its hydrolysis polycondensate to the dope of the cellulose ester, it is preferable that a good solvent for the cellulose ester is also included so that the cellulose ester does not precipitate from the dope. Alternatively, a dope may be produced by a method in which a solution obtained by previously hydrolyzing an alkoxysilane is diluted with a good solvent for cellulose ester and then flakes of cellulose ester are added.

  Examples of the catalyst include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, 12 tungsto (VI) phosphoric acid, 12 molybdo (VI) phosphoric acid, silicotungstic acid and other inorganic acids, acetic acid, trifluoroacetic acid, levulinic acid, citric acid, Organic acids such as p-toluenesulfonic acid and methanesulfonic acid are used. After the sol-gel reaction has progressed by adding an acid, it may be neutralized by adding a base. When neutralizing by adding a base, the content of alkali metal before the drying step is preferably less than 5000 ppm (herein, the alkali metal includes those in an ionic state). In addition, Lewis acids such as acetates of metals such as germanium, titanium, aluminum, antimony and tin, other organic acid salts, halides, phosphates, acetylacetone complexes, acetoacetate complexes and the like may be used in combination.

  As catalysts, instead of such acids, amines such as ammonia, monoethanolamine, diethanolamine, triethanolamine, diethylamine, triethylamine, aniline, N, N-dimethylaniline, and nitrogen-containing 5-membered materials such as imidazole and pyrazole Bicyclic amines such as ring aromatics, nitrogen-containing 6-membered aromatics such as pyridine and pyrazine, DBU (diazabicycloundecene-1), DBN (diazabicyclononene), phosphine, alkali metal alkoxides, water Bases such as ammonium oxide, tetramethylammonium hydroxide, and benzyltrimethylammonium hydroxide can be used.

  The amount of the acid or alkali catalyst added is not particularly limited, but is preferably 0.01% to 20% by mass with respect to the amount of the reactive metal compound capable of polycondensation. Moreover, you may use together the process of an acid and a base in multiple times. The catalyst may be neutralized, or the volatile catalyst may be removed under reduced pressure, or may be removed by separation water washing or the like. A solid catalyst such as an ion exchange resin that can be easily removed may be used.

  The hydrolysis polycondensation of alkoxysilane may complete the reaction in a solution state before coating, or may be completed after casting into a film, but at least the reaction is in an equilibrium state before coating. Is preferably reached. Depending on the application, the reaction may not be completely completed.

<Additive>
The transparent film in the present invention includes, for example, a plasticizer that imparts processability, flexibility, and moisture resistance to the film as described in JP-A-2002-62430, and an antioxidant that prevents deterioration of the film. Further, fine particles (matting agent) that impart slipperiness to the film, retardation adjusting agents that adjust the retardation of the film, and the like may be contained, but the plasticizer is preferably not contained because it lowers the glass transition temperature of the film. . Further, an ultraviolet absorber or the like that imparts an ultraviolet absorbing function may also be included, but it is necessary that the transmittance in the ultraviolet region be within a range of 50% or more, and ultraviolet absorption having absorption at 250 nm or more. It is preferable not to contain the agent.

<solvent>
In the production of a cellulose-silica hybrid polymer mainly comprising a hydrolysis polycondensate of cellulose ester and alkoxysilane of the present invention, cellulose ester such as acetyl cellulose and alkoxysilane or its hydrolysis polycondensate are both solvents. It is preferable to form a film by a solvent casting method in which a film is cast on a substrate to form a film and the solvent is evaporated after casting. Therefore, a volatile solvent is preferable as a solvent for dissolving them. And what does not react with a catalyst, alkoxysilane, etc., and does not dissolve the base material for casting is preferable. Two or more of these solvents may be mixed and used. Moreover, you may mix, after melt | dissolving a cellulose ester and an alkoxysilane in another solvent, respectively.

  Here, hereinafter, an organic solvent having good solubility with respect to the cellulose ester is referred to as a good solvent, and has a main effect on dissolution, and an organic solvent used in a large amount among them is a main (organic) solvent or a main solvent. It is called (organic) solvent.

  Examples of good solvents include ketones such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethers such as tetrahydrofuran (THF), 1,4-dioxane, 1,3-dioxolane, 1,2-dimethoxyethane, and formic acid. Esters such as methyl, ethyl formate, methyl acetate, ethyl acetate, amyl acetate, γ-butyrolactone, methyl cellosolve, dimethylimidazolinone, dimethylformamide, dimethylacetamide, acetonitrile, dimethylsulfoxide, sulfolane, nitroethane, chloride Examples include methylene and the like, and 1,3-dioxolane, THF, methyl ethyl ketone, acetone, methyl acetate and methylene chloride are preferable.

  The dope preferably contains 1 to 40% by mass of an alcohol having 1 to 4 carbon atoms in addition to the organic solvent. After casting the dope on the metal support, the solvent starts to evaporate and the alcohol ratio increases, so that the web (referred to as the dope film after casting the cellulose derivative dope on the support is called web )), And it is used as a gelling solvent to make the web strong and easy to peel off from the metal support. When these ratios are small, the dissolution of cellulose derivatives of non-chlorine organic solvents is promoted. There is also a role to suppress gelation, precipitation, and viscosity increase of the reactive metal compound.

  Examples of the alcohol having 1 to 4 carbon atoms include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol, and propylene glycol monomethyl ether. Of these, ethanol is preferred because it has excellent dope stability, has a relatively low boiling point, good drying properties, and no toxicity. These organic solvents alone are not soluble in cellulose derivatives and are called poor solvents.

  The most preferable solvent that satisfies such conditions and dissolves the cellulose ester derivative, which is a preferable polymer compound, at a high concentration is a mixed solvent having a ratio of methylene chloride: ethyl alcohol of 95: 5 to 80:20.

  In the present invention, a cellulose ester is exemplified as a resin skeleton having a positive birefringence wavelength dispersion characteristic. Since a hydroxyl group exists in the cellulose ester, these hydroxyl groups are converted to the alkoxysilane or polycondensation thereof. By substituting with a product, a transparent film having low heat resistance and low birefringence, birefringence wavelength dispersion being positive dispersion and high heat resistance can be formed.

The wavelength dispersion of birefringence is positive dispersion. For example, a film is prepared by dissolving the polymer in a soluble solvent and casting and drying on a glass plate so that the thickness when the film is dried is 100 μm. The value obtained by dividing the in-plane retardation value R ₀ (480) at a wavelength of 480 nm of the polymer film by the in-plane retardation value R ₀ (590) at a wavelength of 590 nm is less than 1.

In the present invention, these transparent films are obtained by dividing the in-plane retardation value R ₀ (480) at the wavelength of 480 nm by the in-plane retardation value R ₀ (590) at the wavelength of 590 nm, R ₀ (480) / R _0. (590) is preferably 0.8 or more and less than 1.0.

  In transparent films with positive birefringence wavelength dispersion, polarization can be compensated in the entire visible wavelength range, and there is no color shift in liquid crystal panels that employ a birefringence display method, and organic The EL display element has good contrast.

  In addition to the aforementioned additives, the transparent film in the present invention may contain fine particles (matting agent) that impart slipperiness to the film, a retardation adjusting agent that adjusts the retardation of the film, and the like.

  The transparent film having a high transmittance in the ultraviolet region according to the present invention can be used by forming a moisture-proof film or a transparent conductive film as shown below, for example, as an electronic display film such as organic EL and liquid crystal.

<Dampproof film>
In the transparent film of the present invention, as an electronic display film, in order to seal these electronic displays from atmospheric moisture and oxygen, metal oxides, metal nitrides for the purpose of reducing water vapor permeability, A film made of metal oxynitride, metal carbide, or the like can be formed as a moisture-proof film on at least one surface of the substrate. These may be laminated | stacked and may be formed in both surfaces.

  The metal oxide, metal nitride, metal oxynitride, and metal carbide used in such a film are selected from silicon, zirconium, titanium, tungsten, tantalum, aluminum, zinc, indium, chromium, vanadium, tin, and niobium. Examples include oxides or nitrides, nitrides, oxynitrides, and carbides of more than one element, with silicon oxide, aluminum oxide, and silicon nitride being preferred, and particularly preferred is a metal oxide film in which silicon oxide is the main component. The main component means that the ratio in the moisture-proof film component is 80% by mass or more.

  In addition, since an amorphous (amorphous) inorganic film is less susceptible to cracking and has a higher linear expansion coefficient, an amorphous inorganic film is preferable when it is formed on a flexible plastic film. Whether the formed gas barrier film is amorphous or crystalline can be determined by whether or not scattering from the crystal lattice is observed by XRD measurement.

  In addition, if a component (carbon, nitrogen, etc.) other than the main component of the gas barrier layer is present as a contamination, it is difficult to crystallize and is likely to be amorphous. Therefore, a film having some contamination may be used.

  Metal oxides, metal nitrides, and metal oxynitrides can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like, but an atmospheric pressure plasma discharge treatment method described later is a preferable method. This is because film formation by a PVD method such as a vacuum evaporation method, a sputtering method, or an ion plating method is a vacuum process and has low productivity. Moreover, according to the film forming method by the atmospheric pressure plasma discharge treatment method, the adhesiveness with the plastic film is also good.

  In addition, J.H. Sol-Gel Sci. Tech. , P141-146 (1998), metal oxides, metal nitrides, and metal oxynitride thin films are easily cracked, and water vapor leaks from the cracks. The cracks can be sealed by applying various coating materials on a moisture-proof film of nitride or metal oxynitride to further reduce moisture permeability.

  It is preferable that an inorganic film having a low coefficient of linear expansion and difficult to crack is formed with good adhesion to the transparent plastic film because the dimensional stability of the transparent plastic film itself is improved.

<Transparent conductive film>
Moreover, the transparent film of this invention may have a transparent conductive film. Hereinafter, the transparent conductive film will be described.

  In the present invention, the transparent conductive film is generally well known as an industrial material and is a transparent film that absorbs almost no visible light (400 to 700 nm) and is transparent. Since the free charged material carrying electricity has high transmission characteristics in the visible light region, is transparent, and has high electrical conductivity, it is used as a transparent electrode for organic EL display devices and the like. When the transparent conductive film is used for an organic EL display device as in the present invention, the thickness of the transparent conductive film is preferably about 100 to 140 nm.

As the transparent conductive film, a composite oxide with a metal oxide film such as SnO ₂ , In ₂ O ₃ , CdO, ZnO ₂ , SnO ₂ : Sb, SnO ₂ : F, ZnO: AL, In ₂ O ₃ : Sn, and a dopant is used. There is a material film.

Examples of the composite oxide film using the dopant include an ITO film obtained by doping tin with indium oxide, an FTO film obtained by doping fluorine with tin oxide, an IZO film made of In ₂ O ₃ —ZnO-based amorphous material, and the like. Is mentioned.

  Such a transparent conductive film may be formed by, for example, a wet film forming method typified by coating, or a dry film forming method using a vacuum such as a sputtering method, a vacuum evaporation method, or an ion plating method. However, as a means for forming the transparent conductive film on the conductive film of the present invention, an atmospheric pressure plasma discharge treatment method with a simple film forming process is a preferable method.

<Atmospheric pressure plasma treatment>
Atmospheric pressure plasma treatment means that the reactive gas between the electrodes is turned into a plasma state by generating an electric field between the opposing electrodes under atmospheric pressure or near atmospheric pressure. In this method, a film is formed on a substrate by exposing the substrate to a gas.

  In the present invention, “near atmospheric pressure” represents a pressure of 20 kPa to 110 kPa, but 93 kPa to 104 kPa is preferable in order to obtain the effects described in the present invention.

  An example of the apparatus and method by atmospheric pressure plasma treatment for forming a moisture-proof film and a transparent conductive film of the present invention will be described.

<Atmospheric pressure plasma discharge treatment equipment>
The atmospheric pressure plasma discharge treatment apparatus has a roll electrode that is a ground electrode and a plurality of fixed electrodes that are application electrodes arranged at opposing positions, and a discharge is generated between these electrodes and introduced between the electrodes. A reactive gas containing a rare gas and a reactive gas is put into a plasma state, and a substrate film that is transferred while being wound around the roll electrode is exposed to the reactive gas in the plasma state, whereby a moisture-proof film or a conductive film is formed on the film. A thin film such as a film is formed.

  As another method, there is a jet method in which a base film is placed or transferred in the vicinity of an electrode that is not between electrodes, and a thin film is formed by spraying generated plasma onto the base film.

  FIG. 2 is a view showing an example of a plasma discharge processing apparatus under atmospheric pressure or a pressure in the vicinity thereof according to the present invention. FIG. 2 includes a plasma discharge processing apparatus 30, a gas filling means 50, a voltage applying means 40, and an electrode temperature adjusting means 60. As the roll rotating electrode 35 and the rectangular tube type fixed electrode group 36, the base film CF is subjected to plasma discharge treatment. The base film CF is unwound from the original winding which is unwound and conveyed, or air or the like which is conveyed from the previous process and accompanied by the nip roll 65 through the guide roll 64 via the guide roll 64. Is it cut off and transferred between the rectangular tube-shaped fixed electrode group 36 while being wound while being in contact with the roll rotating electrode 35, passed through the nip roll 66 and the guide roll 67, and taken up by a winder (not shown)? Transfer to the next process. The reaction gas is gas filling means 50, and the reaction gas G generated by the gas generator 51 is flow-controlled and put into the plasma discharge treatment vessel 31 of the discharge treatment chamber 32 through the air supply port 52, and the plasma discharge treatment vessel 31 is filled with the reaction gas G, and the treated exhaust gas G ′ is discharged from the exhaust port 53. Next, the voltage applying means 40 applies a voltage to the rectangular tube-shaped fixed electrode group 36 from the high frequency power supply 41, and the roll rotating electrode 35 is grounded to generate discharge plasma between the electrodes. The roll rotating electrode 35 and the rectangular tube-shaped fixed electrode group 36 are heated or cooled using an electrode temperature adjusting means 60 and fed to the electrodes. The temperature of the medium whose temperature has been adjusted by the electrode temperature adjusting means 60 is adjusted by the liquid feed pump P from the inside of the roll rotating electrode 35 and the rectangular tube-shaped fixed electrode group 36 through the pipe 61.

  During the plasma discharge treatment, the properties and composition of the thin film obtained may vary depending on the temperature of the base film, and it is preferable to appropriately control this. As the medium, an insulating material such as distilled water or oil is preferably used. During the plasma discharge treatment, it is desired to control the temperature inside the rotating electrode using a roll so that the temperature unevenness of the base film in the width direction or the longitudinal direction does not occur as much as possible. Reference numerals 68 and 69 denote partition plates that partition the plasma discharge processing vessel 31 from the outside.

  The reactive gas used for the discharge plasma treatment is introduced into the plasma discharge treatment container 31 from the air supply port 52, and the treated gas is exhausted from the exhaust port 53.

  FIG. 3 is a sketch showing an example of the structure of a conductive base material such as a metal of a roll electrode and a dielectric material coated thereon.

  In FIG. 3, a roll rotating electrode 35a, which is an earth electrode, is subjected to a sealing treatment using an inorganic compound sealing material after thermal spraying ceramics as a dielectric coating layer on a conductive base material 35A such as metal. It is configured by a combination in which a dielectric 35B subjected to ceramic coating is coated. A ceramic-coated dielectric is covered with 1 mm of a single wall and grounded. As the ceramic material used for thermal spraying, alumina, silicon nitride, or the like is preferably used. Among these, alumina is more preferable because it is easily processed.

  Alternatively, the dielectric layer may be a lining treated dielectric provided with an inorganic material by glass lining.

  As the conductive base material 35A such as metal, a metal such as titanium metal or titanium alloy, silver, platinum, stainless steel, aluminum, iron, etc., a composite material of iron and ceramics, or a composite material of aluminum and ceramics is used. Although it can mention, titanium metal or a titanium alloy is preferable from a viewpoint of stability of an electrode.

  Details of the conductive base material and the dielectric will be described later.

  FIG. 4 is a sketch showing an example of the structure of a base material of a rectangular tube-shaped fixed electrode obtained by taking out one of the rectangular tube-shaped fixed electrode groups as an application electrode and the structure of a dielectric material coated thereon.

  In FIG. 4, a rectangular tube electrode 36a has a dielectric coating layer similar to that shown in FIG. 3 with respect to a conductive base material such as metal. That is, a hollow metal pipe is covered with the same dielectric as described above, and can be cooled with cooling water during discharge. In addition, the number of the square tube type fixed electrodes is 14 along the circumference larger than the circumference of the roll electrode.

  Since the rectangular tube electrode 36a shown in FIG. 4 has an effect of widening the discharge range (discharge area) as compared with the cylindrical electrode, it is preferably used in the thin film forming method of the present invention.

  The power source for applying a voltage to the application electrode is not particularly limited. However, the high frequency power source (3 kHz) manufactured by Shinko Electric, the high frequency power source (5 kHz) manufactured by Shinko Electric, the high frequency power source (15 kHz) manufactured by Shinko Electric, and the high frequency power source manufactured by Shinko Electric ( 50 kHz), HEIDEN Laboratory high frequency power supply (continuous mode use, 100 kHz), Pearl Industrial high frequency power supply (200 kHz), Pearl Industrial high frequency power supply (800 kHz), Pearl Industrial high frequency power supply (2 MHz), JEOL high frequency power supply ( 13.56 MHz), high frequency power source (27 MHz) manufactured by Pearl Industry, high frequency power source (150 MHz) manufactured by Pearl Industry, etc. can be used. Alternatively, a power source that oscillates at 433 MHz, 800 MHz, 1.3 GHz, 1.5 GHz, 1.9 GHz, 2.45 GHz, 5.2 GHz, or 10 GHz may be used. Two or more frequencies may be superimposed and used. As a preferable combination at that time, it is preferable to superimpose a power source of 1 kHz to 1 MHz and a power source of 1 MHz to 2500 MHz.

  The distance between the electrodes is determined in consideration of the thickness of the solid dielectric provided on the conductive base material of the electrodes, the magnitude of the applied voltage, the purpose of using plasma, and the like. The shortest distance between the dielectric surface and the electrode when a dielectric is provided on one of the electrodes, and the distance between the dielectric surfaces when a dielectric is provided on both of the electrodes From the viewpoint of performing, it is preferably 0.5 to 20 mm, particularly preferably 1 ± 0.5 mm.

  The value of the voltage applied from the power source 41 to the rectangular tube-shaped fixed electrode group 36 is appropriately determined. For example, the voltage is about 10 V to 10 kV, and the power source frequency is adjusted to more than 100 kHz and not more than 150 MHz. As for the method of applying power, either a continuous sine wave continuous oscillation mode called continuous mode or an intermittent oscillation mode called ON / OFF intermittently called pulse mode may be adopted. A denser and better quality film can be obtained.

  The plasma discharge treatment vessel 31 is preferably a treatment vessel made of Pyrex (R) glass or the like, but can be made of metal as long as it can be insulated from the electrodes. For example, polyimide resin or the like may be attached to the inner surface of an aluminum or stainless steel frame, and the metal frame may be thermally sprayed to obtain insulation.

  Moreover, in order to suppress the influence on the base film at the time of the discharge plasma treatment to a minimum, the temperature of the base film at the time of the discharge plasma treatment is adjusted to a temperature of room temperature (15 ° C. to 25 ° C.) to 300 ° C. or less. It is preferable. In order to adjust to the above temperature range, the electrode and the base film are subjected to discharge plasma treatment while being cooled or heated by a temperature adjusting means as necessary.

<Reaction gas>
The reaction gas that forms the moisture-proof film of the optical film of the present invention will be described. The reaction gas used is basically an inert gas and a reactive gas for forming a thin film. It is preferable to contain 0.01-10 volume% of reactive gas with respect to reactive gas. As the thickness of the thin film, a thin film in the range of 0.1 to 1000 nm is obtained.

  The reaction gas used is a mixed gas containing an inert gas and a reactive gas.

  Examples of the inert gas include Group 18 elements of the periodic table, specifically, noble gases such as helium, neon, argon, krypton, xenon, and radon, or nitrogen, but are described in the present invention. In order to obtain the effect, helium, argon and nitrogen are preferably used. In order to form a dense and highly accurate thin film, it is most preferable to use argon as a rare gas. It is estimated that high-density plasma is likely to be generated when argon is used. The argon gas is preferably contained in an amount of 90.0 to 99.9% by volume with respect to 100% by volume of the reactive gas (a mixed gas of a rare gas and a reactive gas).

  In carrying out thin film formation, the reactive gas used is basically an inert gas and a reactive gas for forming a thin film. It is preferable to contain 0.01-10 volume% of reactive gas with respect to reactive gas. As the thickness of the thin film, a thin film in the range of 0.1 to 1000 nm is obtained.

  The reactive gas is in a plasma state in the discharge space and contains a component that forms a thin film, and includes an organometallic compound, an organic compound, an inorganic compound, and a compound that directly forms a thin film with hydrogen gas, oxygen gas, carbonic acid. There are gases that are used in an auxiliary manner such as gas.

<Reactive gas for moisture barrier film formation>
The reactive gas for forming the moisture-proof film can be used without limitation as long as it is a compound that can obtain appropriate moisture-proof properties, but titanium compounds, tin compounds, silicon compounds, fluorine compounds, silicon compounds having fluorine, or these compounds Although a mixture of these can be preferably used, a silicon compound is most preferable.

  Examples of the silicon compound that can be used for the reactive gas for forming the moisture-proof film include organic silicon compounds, silicon hydrogen compounds, and silicon halide compounds. Examples of the organic silicon compounds include tetraethylsilane, tetramethylsilane, tetra Isopropylsilane, tetrabutylsilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diethylsilanediacetacetonate, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane Examples of the silicon hydrogen compound include tetrahydrogen silane and hexahydrogen disilane, and examples of the halogenated silicon compound include tetrachlorosilane, methyltrichlorosilane, and diethyldichlorosilane. Come.

  Examples of titanium compounds that can be used in the reactive gas for forming a moisture-proof film include organic titanium compounds, titanium hydrogen compounds, and titanium halides. Examples of organic titanium compounds include triethyl titanium, trimethyl titanium, triisopropyl titanium, and tributyl titanium. , Tetraethyl titanium, tetraisopropyl titanium, tetrabutyl titanium, triethoxy titanium, trimethoxy titanium, triisopropoxy titanium, tributoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, methyl dimethoxy titanium, ethyl triethoxy titanium, methyl triiso Propoxy titanium, tetradimethylamino titanium, dimethyl titanium diacetoacetonate, ethyl titanium triacetoacetonate, etc. Emissions hydrogen compound such as titanium halide, trichloro titanium, tetrachloro titanium, and the like.

Examples of tin compounds that can be used in the reactive gas for forming a moisture-proof film include organic tin compounds, tin hydrogen compounds, and tin halides. Examples of organic tin compounds include tetraethyltin, tetramethyltin, and di-n-diacetate. -Butyltin, tetrabutyltin, tetraoctyltin, tetraethoxytin, methyltriethoxytin, diethyldiethoxytin, triisopropylethoxytin, diethyltin, dimethyltin, diisopropyltin, dibutyltin, diethoxytin, dimethoxytin, diiso Propoxy tin, dibutoxy tin, tin dibutyrate, tin diacetoacetonate, ethyl tin acetoacetonate, ethoxytin acetoacetonate, dimethyltin diacetoacetonate, etc., tin hydride compounds, etc., as tin halide, tin dichloride, Examples include tin tetrachloride. Since the tin oxide layer thus formed can reduce the surface specific resistance value to 10 ¹¹ Ω / cm ² or less, it is also useful as an antistatic layer, and not as a moisture-proof film but as a conductive film. You can use it. Two or more of these reactive gases can be mixed and used at the same time.

  The above organosilicon compound, organotitanium compound or organotin compound is preferably a metal hydride compound or metal alkoxide from the viewpoint of handling, and is free from corrosiveness, generation of harmful gases, and less contamination in the process. Alkoxides are preferably used.

<Reactive gas for forming transparent conductive film>
Next, the reactive gas for forming the transparent conductive film is in a plasma state in the discharge space and contains a component that forms the transparent conductive film, and an organic metal compound such as a β-diketone metal complex, a metal alkoxide, or an alkyl metal is included. Used. The reactive gas includes a reactive gas that is a main component of the transparent conductive film and a reactive gas that is used in a small amount for the purpose of doping. Furthermore, there is a reactive gas used to adjust the resistance value of the transparent conductive film.

  In the present invention, the reactive gas used as the main component of the transparent conductive film is preferably an organometallic compound having an oxygen atom in the molecule. For example, indium hexafluoropentanedionate, indiummethyl (trimethyl) acetylacetate, indium acetylacetonate, indium isoporopoxide, indium trifluoropentanedionate, tris (2,2,6,6-tetramethyl 3,5 -Heptanedionate) indium, di-n-butylbis (2,4-pentanedionate) tin, di-n-butyldiacetoxytin, di-t-butyldiacetoxytin, tetraisopropoxytin, tetrabutoxytin, Examples thereof include zinc acetylacetonate. Of these, particularly preferred are indium acetylacetonate, tris (2,2,6,6-tetramethyl-3,5-heptanedionate) indium, tris (2,6-dimethyl-3,5-heptanedioate). Nate) indium, zinc acetylacetonate, di-n-butyldiacetoxytin.

  Examples of the reactive gas used for doping include aluminum isopropoxide, nickel acetylacetonate, manganese acetylacetonate, boron isopropoxide, n-butoxyantimony, tri-n-butylantimony, di-n-butylbis ( 2,4-pentanedionate) tin, di-n-butyldiacetoxytin, di-t-butyldiacetoxytin, tetraisopropoxytin, tetrabutoxytin, tetrabutyltin, zinc acetylacetonate, propylene hexafluoride, A cyclobutane octafluoride, methane tetrafluoride, etc. can be mentioned.

  Examples of the reactive gas used for adjusting the resistance value of the transparent conductive film include titanium triisopropoxide, tetramethoxysilane, tetraethoxysilane, and hexamethyldisiloxane.

  The amount ratio of the reactive gas used as the main component of the transparent conductive film and the reactive gas used in a small amount for the purpose of doping varies depending on the type of the transparent conductive film to be formed. For example, in the ITO film obtained by doping tin with indium oxide, the reactive gas amount is adjusted so that the In / Sn atomic ratio of the obtained ITO film is in the range of 100 / 0.1 to 100/15. To do. Preferably, it adjusts so that it may become the range of 100 / 0.5-100 / 10. The atomic ratio of In / Sn can be determined by XPS measurement.

  In a transparent conductive film (referred to as FTO film) obtained by doping fluorine with tin oxide, the reaction is performed so that the Sn / F atomic ratio of the obtained FTO film is in the range of 100 / 0.01 to 100/50. Adjust the quantity ratio of sex gases. The atomic ratio of Sn / F can be determined by XPS measurement.

In the In ₂ O ₃ —ZnO-based amorphous transparent conductive film (IZO film), the amount ratio of the reactive gas is adjusted so that the In / Zn atomic ratio is in the range of 100/50 to 100/5. The atomic ratio of In / Zn can be determined by XPS measurement.

  Moreover, in the ITO film | membrane, FTO film | membrane, and IZO film | membrane mentioned above, it is preferable that the doping amount of Sn is 5 mass% or less, for example.

  From the viewpoint of forming a uniform thin film on the substrate film by discharge plasma treatment, these reactive gases preferably have a content in the reactive gas of 0.01 to 10% by volume, more preferably 0.01 to 1% by volume.

  Furthermore, by containing 0.01 to 5% by volume of a component selected from oxygen, ozone, hydrogen peroxide, carbon dioxide, carbon monoxide, hydrogen and nitrogen as a reactive gas, the reaction is promoted and dense. A high-quality thin film can be formed. As the film thickness of the transparent conductive film, a transparent conductive film in the range of 0.1 nm to 1000 nm is obtained.

  In order to introduce the above-mentioned organotin compound, organotitanium compound, organosilicon compound, organozinc compound, or organoindium compound between electrodes that are discharge spaces, both are normal temperature and normal pressure, either gas, liquid, or solid You may be in the state. In the case of gas, it can be introduced into the discharge space as it is, but in the case of liquid or solid, it is used after being vaporized by means such as heating, decompression or ultrasonic irradiation. The metal alkoxide may be diluted with a solvent and used. In this case, the metal alkoxide may be vaporized into a rare gas by a vaporizer or the like and used as a reaction gas. As the solvent, organic solvents such as methanol, ethanol, isopropanol, butanol, n-hexane, and mixed solvents thereof can be used.

<Applied voltage>
In the thin film forming method, it is preferable to supply a power (power density) of 1 W / cm ² or more with a high-frequency voltage exceeding 100 kHz between opposing electrodes to excite the reactive gas to generate plasma. .

  The upper limit of the frequency of the high frequency voltage applied between the electrodes is preferably 150 MHz or less. Further, the lower limit value of the frequency of the high-frequency voltage is preferably 200 kHz or more, more preferably 800 kHz or more.

The lower limit value of the power supplied between the electrodes is preferably 1.2 W / cm ² or more, and the upper limit value is preferably 50 W / cm ² or less, more preferably 20 W / cm ² or less. The discharge area (1 / cm ² ) refers to an area in a range where discharge occurs in the electrode. As in the present invention, when a high power voltage is applied at a high frequency and a high output density, the discharge area corresponds to the total area of the discharge surface of the electrode on one side. By dividing the total power (W) supplied from the power source connected to the electrode by this total area, the output density can be calculated.

  Further, in this atmospheric pressure plasma discharge treatment method, in order to obtain a uniform film thickness particularly in a large area, the total power applied to a pair of opposed electrodes is preferably more than 15 kW, more preferably 30 kW or more, More preferably, it is 50 kW or more. From the viewpoint of heat generation, it is preferably 300 kW or less. The total power corresponds to power (W) supplied from a power source connected to the set of electrodes. When two or more power sources are connected to the set of electrodes, the value is a value obtained by adding the power supplied to all the power sources. Specifically, in the atmospheric pressure plasma discharge processing apparatus of FIG. 2 described above, the roll rotating electrode 35 and the rectangular tube-shaped fixed electrode group 36 are used as a pair of opposed electrodes, and the power supplied from the power source 41 connected thereto. It will be. In order to satisfy the total power range, the discharge area needs to be large to some extent.

  The high-frequency voltage applied between the electrodes may be an intermittent pulse wave or a continuous sine wave. However, in order to obtain the effect of the present invention, it is a continuous sine wave. It is preferable.

<Atmospheric pressure plasma treatment: Electrode>
A highly durable electrode that can maintain a uniform discharge state even when such a high-power electric field is applied to a large-area electrode under atmospheric pressure or a pressure near atmospheric pressure is employed in the plasma discharge processing apparatus. There is a need.

  As such an electrode, it is preferable that at least a discharge surface on a conductive base material such as metal is coated with a dielectric. At least one of the opposing application electrode and ground electrode is coated with a dielectric, and preferably both the application electrode and ground electrode are coated with a dielectric.

  A dielectric coated electrode is a composite part of a conductive base material such as metal and a dielectric material such as ceramics or glass. When the supplied power, especially when the total power is large, it breaks down from the vulnerable part of the dielectric. It is difficult to maintain a stable plasma discharge. This is particularly true for dielectric-coated electrodes having a large discharge area. In order to implement the thin film forming method using high power in the present invention, at least one of the electrodes should be a dielectric-coated electrode that can withstand it. It is necessary to be.

  In the present invention, the dielectric used for the dielectric-coated electrode is specifically preferably an inorganic compound having a relative dielectric constant of 6 to 45, and examples of such a dielectric include alumina and nitriding. There are ceramic spray materials such as silicon or glass lining materials such as silicate glass and borate glass. In this, what sprayed the ceramics mentioned later and the thing provided by glass lining are preferable. In particular, a dielectric provided by spraying alumina is preferable.

  In addition, in the dielectric-coated electrode, another preferred specification that can withstand high power is that the heat-resistant temperature is 100 ° C. or higher. More preferably, it is 120 degreeC or more, Most preferably, it is 150 degreeC or more. The heat-resistant temperature refers to the highest temperature that can withstand normal discharge without breakdown. Such heat-resistant temperature is applied within the range of the difference in linear thermal expansion coefficient between the conductive base material and the dielectric below, by applying the ceramics sprayed above and the dielectric material provided with layered glass lining with different foam mixing amount. This can be achieved by appropriately combining means for appropriately selecting the materials.

In addition, in the dielectric-coated electrode according to the present invention, another preferable specification is a combination in which the difference in coefficient of linear thermal expansion between the dielectric and the conductive base material is 10 × 10 ⁻⁶ / ° C. or less. . It is preferably 8 × 10 ⁻⁶ / ° C. or less, more preferably 5 × 10 ⁻⁶ / ° C. or less, and further preferably 2 × 10 ⁻⁶ / ° C. or less. The linear thermal expansion coefficient is a well-known physical property value of a material.

  As a combination of a conductive base material and a dielectric whose difference in linear thermal expansion coefficient is within this range, the conductive base material is titanium metal or titanium alloy containing 70 mass% or more of titanium, and the dielectric is ceramic sprayed. A film or a dielectric with a glass lining is preferably used.

  The titanium metal or titanium alloy can be used without problems as long as it contains 70% by mass or more of titanium, but preferably contains 80% by mass or more of titanium. As the titanium alloy or titanium metal useful in the present invention, those generally used as industrial pure titanium, corrosion resistant titanium, high strength titanium and the like can be used. Examples of pure titanium for industrial use include TIA, TIB, TIC, TID, etc., all of which contain very little iron atom, carbon atom, nitrogen atom, oxygen atom, hydrogen atom, etc. As content, it has 99 mass% or more. As the corrosion-resistant titanium alloy, TI5PB can be preferably used, and it contains lead in addition to the above-mentioned contained atoms, and the titanium content is 98% by mass or more. Further, as the titanium alloy, T64, T325, T525, TA3, etc. containing aluminum and vanadium or tin in addition to the above atoms except lead can be preferably used. As a quantity, it contains 85 mass% or more. These titanium alloys or titanium metals have a thermal expansion coefficient smaller than that of stainless steel, such as AISI 316, by about 1/2, and are described below as dielectric materials applied on the titanium alloy or titanium metal as a metal base material. It can withstand use at high temperatures for a long time.

  In the dielectric-coated electrode of the present invention, another preferred specification that can withstand high power is that the dielectric thickness is 0.5 to 2 mm. The film thickness variation is desirably 5% or less, preferably 3% or less, and more preferably 1% or less.

In order to further reduce the porosity of the dielectric, it is preferable to further seal the sprayed film such as ceramic with an inorganic compound. As the inorganic compound, metal oxides are preferable, and among them, those containing silicon oxide (SiO _x ) as a main component are particularly preferable.

  The inorganic compound for sealing treatment is preferably formed by curing by a sol-gel reaction. In the case where the inorganic compound for sealing treatment contains a metal oxide as a main component, a metal alkoxide or the like is applied as a sealing liquid on the ceramic sprayed film and cured by a sol-gel reaction. When the inorganic compound is mainly composed of silica, it is preferable to use alkoxysilane as the sealing liquid.

  Here, it is preferable to use energy treatment for promoting the sol-gel reaction. Examples of the energy treatment include thermal curing (preferably 200 ° C. or less) and ultraviolet irradiation. Furthermore, as a method of sealing treatment, when the sealing liquid is diluted and coating and curing are sequentially repeated several times, mineralization is further improved and a dense electrode without deterioration can be obtained.

When a ceramic sprayed coating is applied to a ceramic sprayed film using a metal alkoxide or the like of a dielectric-coated electrode as a sealing liquid, the content of the metal oxide after curing is 60 mol% or more when cured by a sol-gel reaction. Preferably there is. When alkoxysilane is used as the metal alkoxide of the sealing liquid, the cured SiO _x (X is 2 or less) content is preferably 60 mol% or more. The content of SiO _x after curing is measured by analyzing a fault of the dielectric layer by XPS.

  Further, the surface roughness Rmax (JIS B 0601) of the electrode is reduced to 10 μm or less by a method such as polishing the dielectric surface of the dielectric coated electrode, so that the thickness of the dielectric and the gap between the electrodes are made constant. It can be maintained, the discharge state can be stabilized, distortion and cracking due to thermal shrinkage difference and residual stress can be eliminated, and durability can be greatly improved with high accuracy. The polishing finish of the dielectric surface is preferably performed at least on the dielectric that is in contact with the substrate film.

<Actinic radiation curable resin layer as antiglare layer or clear hard coat layer>
In the transparent conductive film of the present invention, a metal compound layer such as the above moisture-proof film / transparent conductive film may be directly formed on the transparent film, but it may be formed on at least one other intermediate layer. Also good. As other layers, an antiglare layer, a clear hard coat layer, or the like can be preferably used.

  The active ray curable resin layer of the antiglare layer and the clear hard coat layer is a resin layer formed by polymerizing a component containing a polymerizable unsaturated monomer, and is an actinic ray curable resin layer. Here, the actinic radiation curable resin layer refers to a layer mainly composed of a resin that is cured through a crosslinking reaction by irradiation with actinic rays such as ultraviolet rays and electron beams. Typical examples of the actinic radiation curable resin include an ultraviolet curable resin and an electron beam curable resin, but a resin that is cured by irradiation with an actinic ray other than ultraviolet rays or an electron beam may be used. Examples of the ultraviolet curable resin include an ultraviolet curable acrylic urethane resin, an ultraviolet curable polyester acrylate resin, an ultraviolet curable epoxy acrylate resin, an ultraviolet curable polyol acrylate resin, and an ultraviolet curable epoxy resin. I can do it.

  These ultraviolet curable resins themselves have absorption only up to about 250 nm, but in order to polymerize them, such as 1-hydroxycyclohexyl phenyl ketone, which is a catalyst that initiates photopolymerization with ultraviolet rays of about 250 nm to 400 nm. In many cases, a photoinitiator is included. However, if these are added, the ultraviolet transmittance of the whole film is lowered, which is not preferable. Therefore, it is preferable not to contain a photopolymerization initiator. Since the acrylate-based ultraviolet curable resin itself has absorption below 250 nm, the polymerization of acrylate is directly started by ultraviolet light (Kr-F excimer laser (248 nm), Ar-F excimer laser (193 nm)) shorter than 250 nm. Alternatively, if a thermal polymerization initiator having no absorption from 250 nm to 400 nm is used, or if plasma induced polymerization is performed by introducing a plasma flow into the cured resin coating surface by the plasma jet, there is no absorption at 250 nm to 400 nm. A cured resin layer can be formed.

  Further, the active ray curable resin layer such as the antiglare layer and the clear hard coat layer may contain inorganic and organic fine particles. Silicon oxide, titanium oxide, aluminum oxide can be added as the inorganic fine particles, and polymethacrylic acid methyl acrylate resin powder can be added as the organic fine particles. The average particle size of these fine particle powders is 0.01 to 10 μm, and the ratio of the ultraviolet curable resin composition to the fine particle powder is 0.1 to 20 parts by mass with respect to 100 parts by mass of the resin composition. It is desirable to blend so that

<Layer structure>
The conductive film of the present invention is formed by forming respective thin films of a moisture-proof film and a transparent conductive film. These layers may be laminated with each other, or may be formed on each side of the substrate. The moisture barrier film may be formed on both sides.

  In the case of stacking the moisture-proof film and the conductive film, for example, two plasma discharge treatment apparatuses are connected in series in the order of the moisture-proof film and the conductive film in the reaction gas atmosphere under the atmospheric pressure as shown in FIG. The continuous lamination process can be carried out side by side so that the layers are laminated, and this continuous lamination process is suitable for the production of the conductive film of the present invention from the viewpoint of stability of quality, cost reduction, improvement of productivity, and the like. Of course, instead of laminating at the same time, each layer may be wound after the treatment, and sequentially laminated.

  An antifouling layer may be provided on the back side of the transparent film on which the conductive film is not laminated. When there is a moisture proof film on the back surface, an antifouling layer or an antireflection layer may be laminated on the moisture proof film. Further, the transparent film or transparent conductive film of the present invention may be used by being bonded to another film-like, sheet-like or plate-like molded product.

  The antifouling layer is a layer that hardly adheres dust and fingerprints and is easy to wipe off so that the surface of the transparent substrate is not soiled and the transmitted image is difficult to see. The antifouling layer is formed, for example, by adding isopropyl alcohol to a heat-crosslinkable fluorine-containing polymer to prepare a 0.2% by mass crude dispersion and applying it to the surface of the outermost layer with a bar coater.

The preferable structural example of the transparent conductive film in this invention is as showing below.
(A) Base material / moisture proof film / transparent conductive film (B) Antifouling layer / base material / moisture proof film / transparent conductive film (C) Moisture proof film / base material / transparent conductive film (D) Antifouling layer / moisture proof film / Substrate / Moisture-proof film / Transparent conductive film As described above, the transparent film having such a moisture-proof film and / or transparent conductive film of the present invention is a liquid crystal display element, an organic EL display element, a plasma display, electronic paper, etc. It can be used as a substrate for an electronic display element, a base material, a protective film for sealing, or the like.

  For example, the present invention is applied in a state where a transparent film and a sealing film are disposed on the substrate so as to cover the electronic display element structure, a photo-curing adhesive is placed therebetween, and the both are pressure-bonded. The adhesive is cured by irradiating light in the ultraviolet region from the transparent film (substrate) side, and is integrated and sealed.

  As the ultraviolet curable resin for sealing the electronic display element structure using the transparent film or the like according to the present invention, for example, as an adhesive, specifically, an ultraviolet curable acrylic urethane resin (for example, JP-A-59-59). No. -151110), UV curable polyester acrylate resin (for example, see JP-A-59-151112), UV curable epoxy acrylate resin (see, for example, JP-A-1-105738), trimethylol. UV curable polyol acrylate resins such as propane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, photocurable adhesives with reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, cationic curable type UV It can be exemplified preferably of epoxy resin adhesive or the like. In particular, a cationic curing type ultraviolet curing epoxy resin adhesive is a preferable adhesive because it is not inhibited by oxygen and the polymerization reaction proceeds even after light irradiation.

  Examples of the epoxy type UV curable prepolymer that is polymerized by cationic polymerization include a prepolymer containing two or more epoxy groups in one molecule. Such prepolymers include, for example, cycloaliphatic polyepoxides, polyglycidyl esters of polybasic acids, polyglycidyl ethers of polyhydric alcohols, polyglycidyl ethers of polyoxyalkylene glycols, polyglycidyls of aromatic polyols. Examples include ethers, hydrogenated compounds of polyglycidyl ethers of aromatic polyols, urethane polyepoxy compounds, and epoxidized polybutadienes. One of these prepolymers can be used alone, or two or more thereof can be mixed and used.

  Specific examples of the cationic polymerization initiator include aromatic onium salts. Examples of the aromatic onium salt include a phosphonium salt, a sulfonium salt, and an iodonium salt. These are described in detail in US Pat. Nos. 4,058,401 and 4,069,055. Particularly, sulfonium salts of Group VIa elements are exemplified, such as triphenylsulfonium tetrafluoroborate, sulfonium, and triphenylsulfonium hexafluoroantimonate. Among them, UV-curable and UV-curable compositions are used. From the viewpoint of storage stability, triarylsulfonium hexafluoroantimonate is preferred. In addition, the photopolymerization initiators described in pages 39 to 56 of the photopolymer handbook (published by Photographic Society Committee, 1989), JP-A 64-13142, JP-A-2-4804 Any compound can be used.

An ionizing radiation curable resin can be used without particular limitation as a light source for forming a cured film layer by a photocuring reaction. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp or the like can be used as a light source that generates ultraviolet rays. The irradiation conditions vary depending on individual lamps, but the amount of light irradiated may be any degree 20~10000mJ / cm ^2, preferably from 50~2000mJ / cm ^2. A sensitizer having an absorption maximum in the near ultraviolet region to the visible light region can also be used.

  When a normal plastic substrate or transparent film is used to irradiate UV light over the substrate, the light intensity in the ultraviolet region by the substrate is greatly reduced, so a long curing time is required. When is used, since the transmittance of ultraviolet rays is high, efficient photocuring can be expected.

  After the ultraviolet curable resin composition is applied to a substrate or a transparent film for sealing, the ultraviolet light is irradiated from the light source from the transparent film side according to the present invention, and the irradiation time is from 0.1 second to 5 minutes. Well, 0.1 to 10 seconds is more preferable from the viewpoint of curing efficiency and work efficiency of the ultraviolet curable resin.

  The ultraviolet ray source may be accompanied by heat generation, and the substrate, the sealing transparent film, and the electronic display element itself may be deteriorated by heat. Those that can be cured are preferred. A desiccant may be dispersed in the adhesive. Application | coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print it like screen printing.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, the embodiment of this invention is not limited to these.

Example 1
<Measurement of substitution degree of cellulose ester>
Based on ASTM D817-96, substitution degree DS was calculated | required as follows. 1.90 g of the dried cellulose ester was precisely weighed, 70 ml of acetone and 30 ml of dimethyl sulfoxide were added and dissolved, and then 50 ml of acetone was further added. While stirring, 30 ml of 1 mol / l sodium hydroxide aqueous solution was added and saponified for 2 hours. After adding 100 ml of hot water and washing the side of the flask, it was titrated with 0.5 mol / l sulfuric acid using phenolphthalein as an indicator. Separately, a blank test was performed in the same manner as the sample. The supernatant of the solution after titration was diluted 100 times, and the composition of the organic acid was measured by an ordinary method using an ion chromatograph. From the measurement result and the acid composition analysis result by ion chromatography, the substitution degree was calculated by the following formula.
TA = (B−A) × F / (1000 × W)
DSa = (162.14 × TA) / {1−42.14 × TA + (1−56.06 × TA) × (X / AC)} DSx = DSa × (X / AC)
DS = DSa + DSxA: Sample titration (ml)
B: Blank test titration (ml)
F: titer of sulfuric acid, 0.5 mol / l
W: Mass of sample (g)
TA: Total organic acid amount (mol / g)
X / AC: Acetic acid (AC) and acid other than acetic acid (X) measured by ion chromatography
DSa: Degree of substitution with acetic acid DSx: Degree of substitution with acid other than acetic acid The results of measuring the degree of substitution DS of the commercially available cellulose ester used in the examples of the present invention by the above method are shown below. Diacetylcellulose (Daicel Chemical, L-50), DS = 2.33 Triacetylcellulose (Daicel Chemical, LT-55), DS = 2.80
<Synthesis Example 1>
J. et al. Appl. Polym. Sci. , 58, 1263-1274 (1995) with reference to the synthesis method.

  After dissolving 36.93 g of diacetylcellulose (manufactured by Daicel Chemical Industries, Ltd., L50) in 258.54 g of dehydrated tetrahydrofuran, 3.72 g (15 mmol) of 3-isocyanatopropyltriethoxysilane (hereinafter abbreviated as IPTES) was added dropwise, and further the catalyst As a result, 0.29 g of dibutyltin dilaurate was added dropwise, and the mixture was stirred as it was with refluxing for 5 hours.

When the infrared absorption spectrum of the solution was measured after 5 hours, it was confirmed that the absorption at 2271 cm ⁻¹ originating from the isocyanate group of IPTES had disappeared. And reprecipitated to obtain 40.50 g of a white solid (yield 99.6%). When the ²⁹ Si-NMR spectrum of the obtained white solid was measured, a single absorption was observed at −45.25 ppm. Moreover, when the < ¹³ > C-NMR spectrum was measured, absorption of amide carbonyl was seen by 163.07 ppm and it confirmed that the target cellulose ester 1 was obtained.

  The substitution degree of the obtained cellulose ester 1 was acetyl group = 2.33 and triethoxysilylpropylamidecarbonyl group = 0.10.

<Preparation of transparent film 101 for reference >
After dissolving 10.0 g of triacetyl cellulose (manufactured by Daicel Chemical Industries, LT55) in a mixed solvent of ethanol 6.0 g and methylene chloride 68.5 g, a film was formed on a glass plate with a doctor blade having a gap width of 1000 μm. The film was dried at 120 ° C. for 30 minutes to obtain a transparent film 101. The film thickness was 100 μm.

<Production of Reference Transparent Film 102>
After dissolving 10.0 g of diacetylcellulose (manufactured by Daicel Chemical Industries, L-50) in a mixed solvent of 6.0 g of ethanol and 68.5 g of methylene chloride, a film was formed on a glass plate with a doctor blade having a gap width of 1000 μm. The film was dried at 120 ° C. for 30 minutes to obtain a transparent film 102. The film thickness was 100 μm.

<Preparation of the transparent film 103 of the present invention>
After mixing 3.04 g (20 mmol) of tetramethoxysilane, 1.52 g of methylene chloride, and 1.52 g of ethanol, 0.72 g of 0.5% nitric acid aqueous solution was added for hydrolysis, and stirring was continued for 1 hour at room temperature. It was.

  12.0 g of triacetyl cellulose (LT-55) was dissolved in a mixed solvent of 6.2 g of ethanol and 60.9 g of methylene chloride, and then mixed with the solution obtained by hydrolyzing tetramethoxysilane, and further stirred for 1 hour. Then, a film was formed on a glass plate with a doctor blade having a gap width of 1000 μm, and the obtained film was dried at 120 ° C. for 30 minutes to obtain a transparent film 103. The film thickness was 100 μm.

<Preparation of the transparent film 104 of the present invention>
After mixing tetramethoxysilane (3.04 g, 20 mmol), methyl acetate (1.52 g) and ethanol (1.52 g), 0.52 nitric acid aqueous solution (0.72 g) was added for hydrolysis, and stirring was continued for 1 hour at room temperature. It was.

  12.0 g of diacetylcellulose (L-50) is dissolved in a mixed solvent of 5.3 g of ethanol and 60.9 g of methyl acetate, and then mixed with the solution obtained by hydrolyzing tetramethoxysilane, and further stirred for 1 hour. After performing, it formed into a film with the doctor blade with a gap width of 1000 micrometers on the glass plate, and the obtained film was dried at 120 degreeC for 30 minute (s), and it was set as the transparent film 104. The film thickness was 100 μm.

<Preparation of the transparent film 105 of the present invention>
After mixing 6.08 g (40 mmol) of tetramethoxysilane, 3.04 g of methyl acetate, and 3.04 g of ethanol, 1.44 g of 0.5% nitric acid aqueous solution was added for hydrolysis, and stirring was continued for 1 hour at room temperature. It was.

  12.0 g of diacetylcellulose (L-50) is dissolved in a mixed solvent of 5.3 g of ethanol and 60.9 g of methyl acetate, and then mixed with the solution obtained by hydrolyzing tetramethoxysilane, and further stirred for 1 hour. After performing, it formed into a film with the doctor blade with a gap width of 1000 micrometers on the glass plate, the obtained film was dried at 120 degreeC for 30 minute (s), and it was set as the transparent film 105. The film thickness was 100 μm.

<Preparation of the transparent film 106 of the present invention>
After mixing 3.19 g (18 mmol) of methyltriethoxysilane, 1.60 g of methyl acetate and 1.60 g of ethanol, 0.49 g of 0.5% nitric acid aqueous solution was added for hydrolysis, and the mixture was stirred at room temperature for 1 hour. Continued.

  12.0 g of diacetylcellulose (L-50) is dissolved in a mixed solvent of 5.3 g of ethanol and 60.9 g of methyl acetate, and then mixed with the above solution obtained by hydrolyzing methyltriethoxysilane, and further stirred for 1 hour. Then, a film was formed on a glass plate with a doctor blade having a gap width of 1000 μm, and the obtained film was dried at 120 ° C. for 30 minutes to obtain a transparent film 106. The film thickness was 100 μm.

<Preparation of the transparent film 107 of the present invention>
After mixing tetramethoxysilane (3.04 g, 20 mmol), methyl acetate (1.52 g) and ethanol (1.52 g), 0.52 nitric acid aqueous solution (0.72 g) was added for hydrolysis, and stirring was continued for 1 hour at room temperature. It was.

  12.0 g of the cellulose ester 1 synthesized in Synthesis Example 1 was dissolved in a mixed solvent of ethanol (5.3 g) and methyl acetate (60.9 g), and then mixed with the solution obtained by hydrolyzing tetramethoxysilane, followed by further 1 hour. After stirring, a film was formed on a glass plate with a doctor blade having a gap width of 1000 μm, and the obtained film was dried at 120 ° C. for 30 minutes to obtain a transparent film 107. The film thickness was 100 μm.

<Transparent film 108 of comparative example>
Sumitomo Bakelite Co., Ltd. Sumilite FS-1300, which is a polyethersulfone film having a film thickness of 100 μm, was used as a comparative transparent film 108.

<Transparent film 109 of comparative example>
Pure Ace manufactured by Teijin Limited, which is a polycarbonate film having a film thickness of 100 μm, was used as a comparative transparent film 109.

<Transparent film 110 of comparative example>
Arton made by JSR Co., Ltd., which is a polynorbornene film having a film thickness of 100 μm, was used as a comparative transparent film 110.

<Transparent film 111 of comparative example>
A film was prepared based on Example 1 disclosed in JP-A No. 2000-122038.

  10 g of polyvinylpyrrolidone (hereinafter referred to as PVP) was dissolved in 90 g of ethanol to prepare a 10% ethanol solution of PVP. Further, 4.0 g of tetraethoxysilane was mixed with 6.0 g of ethanol to prepare a 40% ethanol solution of tetraethoxysilane.

  This 10% ethanol solution of PVP and 40% ethanol solution of tetraethoxysilane were mixed, and 5.0 g of water and 1.0 g of 1 mol / liter hydrochloric acid aqueous solution were added. The solution was allowed to stand for 24 hours with stirring, and the resulting solution was applied to a glass plate so that the film thickness upon drying was 100 μm. The film formed on the glass plate was dried and then peeled to obtain a comparative substrate film 111.

<Transparent film 112 of comparative example>
A polyethylene terephthalate (PET) film having a film thickness of 100 μm was used as the film 112 of the comparative example.

Above, the following evaluation was performed on the transparent film 108 to 111 of the transparency film 101-107 and Comparative Examples were prepared. The evaluation results are shown in Table 1 below.

<Measurement of glass transition temperature (Tg) and linear expansion coefficient>
The inflection point of the temperature-strain curve in thermal stress strain measurement (TMA) was taken as the glass transition temperature.

  For thermal stress strain measurement, a TMA-SS6100 made by Seiko Instruments Inc. was used, a sample with a film thickness of 100 μm and a width of 4 mm was fixed at a distance between chucks of 20 mm, and after raising the temperature from room temperature to 180 ° C., the residual strain was removed. From room temperature to 5 ° C./min. The linear expansion coefficient was obtained from the elongation of the distance between chucks. The glass transition temperature was determined from the inflection point of the temperature-strain curve.

<Measurement of birefringence and wavelength dispersion characteristics>
Measured with an automatic birefringence meter KOBRA-21ADH manufactured by Oji Scientific Instruments Co., Ltd., and the value obtained by multiplying the in-plane X-direction and Y-direction refractive index difference by a thickness of 100 μm is defined as birefringence (nm) expressed.

In addition, the retardation value R ₀ (480) at 480 nm and the retardation value R ₀ (590) at 590 nm were similarly measured using KOBRA-21ADH, and the birefringence value at 480 nm and the double refraction value at 590 nm were expressed by the following equations. The ratio of refraction values was calculated and the wavelength dispersion of birefringence was evaluated.

P = R ₀ (480) / R ₀ (590)
<Measurement of total light transmittance>
The measurement was performed with TURBIDITY METER T-2600DA manufactured by Tokyo Denshoku.

<Measurement of UV light transmittance>
Using a Hitachi spectrophotometer U-3310, the transmittance in the range of 450 nm to 250 nm was measured, and the lowest transmittance in the range was defined as the ultraviolet light transmittance.

  The transparent film 108 of the comparative example has the highest glass transition temperature, but also has a low ultraviolet light transmittance and a small in-plane birefringence, but the birefringence wavelength dispersion is negative, which is not preferable. Further, the transparent films 109 and 112 of the comparative examples are not preferable because of low glass transition temperature and poor ultraviolet light transmittance. In-plane birefringence is large and wavelength dispersion characteristics are negative, which is not preferable. Although the film 110 of the comparative example has a relatively high glass transition temperature, it has an absorption near 275 nm, so that the ultraviolet light transmittance is slightly low and the linear expansion coefficient is large, which is not preferable. Further, the film 111 of the comparative example is not preferable because it has a large linear expansion coefficient and is very brittle and easily broken.

This was paired transparent film 102 consisting of diacetyl cellulose has a high glass transition temperature and a high UV transmittance was preferred film. The transparent film 101 made of triacetyl cellulose is also a preferable transparent film having a glass transition temperature lower than that of the transparent film 102 but a small linear expansion coefficient, a small in-plane birefringence, and a positive wavelength dispersion characteristic.

  In the transparent films 103 to 106 in which silica is hybridized with respect to these cellulose esters, the glass transition temperature is improved without significantly reducing the ultraviolet light transmittance and the linear expansion coefficient, and the transparent films 103 to 106 are more preferable transparent films. A hybrid film 107 using cellulose ester 1 obtained by modifying diacetyl cellulose with a silane coupling agent was also a preferable film.

Example 2
Example 1 transparency film obtained in 101-107, in addition to a comparative example of the film 108 to 111 were cured test of the ultraviolet curing resin used as a comparative film PET (polyethylene terephthalate) film 112 of 100μ thickness .

  That is, after each of the obtained transparent films was coated with an ultraviolet curable resin as an adhesive in a thickness of 100 μm, another same transparent film was layered thereon and irradiated with ultraviolet rays using an ultraviolet handy lamp through the film, and sealed. A test was conducted to see the cure rate of the stopper.

<Ultraviolet curing resin curing test>
Three-bond FPD sealing material is used as the UV curable resin, and the handy lamp is irradiated with UV intensity of 45 mW / cm ^{2 through} the film for 5 seconds or 20 seconds. The UV curable resin is cured and the two transparent films are bonded together. What was obtained was represented by ◯, and what was not cured and the two transparent films were not laminated together was represented by x.

<UV durability test>
In addition, the transparent handpiece was irradiated with the ultraviolet handy lamp at an ultraviolet intensity of 45 mW / cm ² for 20 seconds, and then a film bending test was performed. Those that did not break even when bent were represented as ◯, and those that did not crack as x.

In all the transparent films, it was found that the ultraviolet curable resin was cured when irradiated with an ultraviolet handy lamp for 20 seconds. However, in Example 1, the transparent films 108, 109, and 112 had an ultraviolet light transmittance of 0%. It was not cured by irradiation for 5 seconds. Although the film 110 of the comparative example has absorption in the ultraviolet region, it is relatively unfavorable transparent film because it has a relatively high transmittance or is cured even after irradiation with ultraviolet rays for 5 seconds. Met. In one HoToru bright films 101-107, cured even little as 5 seconds, it was the preferred film not brittle even by ultraviolet irradiation. Moreover, the film 111 of the comparative example was an unfavorable film that cracks when bent regardless of the presence or absence of ultraviolet irradiation.

Example 3
Transparent films 201 to 211 in which a moisture-proof film was formed on the transparent films 101 to 111 obtained in Example 1 were produced. In addition, since the film 111 of the comparative example was very brittle and the film 112 of the comparative example had a low glass transition temperature, a moisture-proof film could not be formed.

<Preparation of moisture barrier film>
As the plasma discharge apparatus, a parallel plate type electrode was used, the transparent film was placed between the electrodes, and a mixed gas was introduced to form a thin film.

  In addition, the following thing was used for the electrode. A 200 mm x 200 mm x 2 mm stainless steel plate is coated with a high-density, high-adhesion alumina sprayed coating, and then a solution obtained by diluting tetramethoxysilane with ethyl acetate is applied and dried, and then cured by UV irradiation for sealing treatment. It was. The dielectric surface thus coated was polished, smoothed, and processed to have an Rmax of 5 μm. In this way, an electrode was produced and grounded.

  On the other hand, as the application electrodes, a plurality of hollow rectangular pure titanium pipes coated with the same dielectric material as described above were produced under the same conditions as the opposing electrode group.

The power source used for plasma generation is a high frequency power source JRF-10000 manufactured by JEOL Ltd., which supplies a voltage of 13.56 MHz and a power of 5 W / cm ² , and a reactive gas having the following composition between the electrodes. Shed. The substrate temperature was 135 ° C.

Inert gas: Argon 99.2% by volume
Reactive gas 1: Hydrogen 0.5% by volume
Reactive gas 2: Tetraethoxysilane 0.3% by volume
An atmospheric pressure plasma treatment was performed on the transparent film 101 under the above reaction gas and reaction conditions to produce a silicon oxide film as a moisture-proof film, and a transparent film 201 was obtained. Before forming the film, a calibration curve of the film forming time and the film thickness was prepared and the film forming speed was calculated, and then the film was formed for a time of 100 nm. The film thickness was measured using FE3000 manufactured by Otsuka Electronics.

  Thereafter, under the same conditions, transparent films 202 to 210 were produced by replacing the transparent film with 102 to 110, and the following evaluation was performed.

<Water vapor permeability test>
The moisture permeability (g / m ² / d) was measured with a Model 7000 manufactured by Illinois Instruments. In addition, measurement was performed after a series of cooling cycles of heating at 180 ° C. for 1 hour and then allowing to cool at room temperature for 1 hour 10 times.

<Cross-cut test>
A cross-cut test based on JIS K5400 was performed. On the surface of the formed thin film, 11 single-edged razor blades with 90 ° cuts with respect to the surface were placed 11 by 1 mm vertically and horizontally to make 100 1 mm square grids. A commercially available cellophane tape was affixed on this, and one end of the tape was peeled off vertically by hand, and the ratio of the area where the thin film was peeled to the affixed tape area from the score line was evaluated according to the following rank.

  A: Not peeled off at all.

  B: The peeled area ratio was less than 10%.

  C: The peeled area ratio was 10% or more.

Cellulose esters have had a large problem of high moisture permeability (800 to 1000 g / m ² / d) in the past, but as shown in Table 3, the silicon oxide film provided by atmospheric pressure plasma treatment was used. High moisture resistance was imparted. On the other hand, the comparative films 209 and 210 having low heat resistance were insufficient in gas barrier properties because the surface could not withstand the temperature of the silicon oxide film formation and the surface was softened and could not be formed uniformly.

  Moreover, in the moisture permeability measurement after passing through a cooling-heat cycle, in the transparent films 208-210 of the comparative example whose linear expansion coefficient was high in Example 1, the moisture permeability was greatly reduced, and the gas barrier property was insufficient. Moreover, the adhesiveness of these transparent films was also low.

Example 4
On the silicon oxide film of the transparent films 201-210 obtained in Example 3, a transparent conductive film was formed by the following method to produce transparent conductive films 301-310.

<Preparation of transparent conductive film>
Except that the power supply was changed to 10 W / cm ² , the reactive gas was changed to the following composition under the atmospheric pressure plasma conditions similar to the formation of the moisture-proof film.
Inert gas: Helium 98.7% by volume
Reactive gas 1: Hydrogen 0.05% by volume
Reactive gas 2: Indium acetylacetonate 1.2% by volume
Reactive gas 3: Dibutyltin diacetate 0.05% by volume
An atmospheric pressure plasma treatment was performed on the silicon oxide film of the transparent film 201 under the above reaction gas and reaction conditions to produce a tin-doped indium oxide film (ITO film) as a transparent conductive film, and a transparent conductive film 301 was obtained.

  Hereinafter, transparent conductive films 302 to 310 were produced by changing the transparent film to 202 to 210, and the following evaluation was performed.

<Resistivity>
According to JIS-R-1637, it calculated | required by the four terminal method. In addition, Mitsubishi Chemical Loresta-GP and MCP-T600 were used for the measurement.

<Transmissivity>
The measurement was performed with TURBIDITY METER T-2600DA manufactured by Tokyo Denshoku.

<Measurement of average reflectance variation>
10 samples of each of the transparent conductive films 301 to 310 are sampled, and the reflectance is measured in the range of 400 to 700 nm under the condition of regular reflection at 5 degrees using a spectrophotometer U-4000 type manufactured by Hitachi in reflection mode. The variation of the average reflectance was examined, and the variation was displayed by the difference between the maximum value and the minimum value. In addition, after roughening the film back surface, the light absorption process was performed using the black spray, and reflection of the light of the optical film back surface was prevented.

  Table 4 shows the results of evaluating the variations in specific resistance, transmittance, and average reflectance of the transparent conductive films 301 to 310 provided with the transparent conductive film.

As shown in Table 4, it was provided an ITO film by an atmospheric pressure plasma method, permeable transparent conductive film 301 to 307, none of the transparent conductive film 308 to 310 of the comparison, a high low resistivity transparent It was a good transparent conductive film. However, to assess the variation in in-plane reflectance of the transparent conductive film, the variation in the transparent dispersion of conductive films 308 to 310 in reflectivity but was observed, most reflectance in translucent transparent conductive film 301 to 307 of the comparative It was a preferable transparent conductive film which does not generate | occur | produce. This is because the high power of the transparent conductive film, the high substrate temperature, the low heat resistant base material cannot withstand, or because of the difference in linear expansion coefficient between the ITO film and the transparent film, It is presumed that a minute surface roughness has occurred.

Example 5
Further, Toru described above transparent conductive film 301 to 307, using a transparent conductive film 308 to 310 of the comparative example, was prepared TN liquid crystal display device as shown in FIG. 5 in the following manner.

<Method for manufacturing TN liquid crystal display element>
The transparent conductive film is used as a transparent conductive base material 401, and a smoothing resin layer (omitted) is coated thereon, and a transparent conductive film is formed thereon directly or via a silicon dioxide film or the like. The display electrode 402 is formed by patterning into a stripe shape or the like, the counter substrate is manufactured using the same transparent conductive substrate, that is, the display electrode is formed on the counter substrate side, and the alignment film 403 is further formed. Then, using a UV curable resin XNR5516 (manufactured by NAGASE & CO., LTD) in the surroundings, a sealing material is formed by a printing method (not shown), spacers are dispersed, and both substrates are made to face each other and bonded. Then, after irradiating energy of 6000 mJ from one side using an ultraviolet curing metal halide lamp (made by Ushio), it was treated at 150 ° C. for 1 hour to be cured, and then emptied. It was constructed Le.

  In the liquid crystal display element using the transparent conductive films 301 to 307, the two substrates were bonded to each other by a sealing material made of an ultraviolet curable resin under the above conditions, and the cell could be configured. In ˜310, the bonding was not possible under the same conditions, and the irradiation time of the metal halide lamp was extended, and the bonding was performed by irradiating four times the energy. However, 309 was largely deformed and could not be bonded, and 308 was slightly colored after bonding.

  Next, liquid crystal is injected into this empty cell by a vacuum injection method or the like, and a terminal portion is taken out so that a driving voltage is applied to the opposing display electrode. A liquid crystal display element was formed by combining the above.

Thus, in the liquid crystal display device produced by using the transparent conductive film as a substrate, but good images were obtained in the transmissive transparent conductive film 301 to 307, the transparent conductive film 308 of the comparative example Adhesion was weak and peeling occurred when the liquid crystal was sealed in the cell, and the liquid crystal could not be sealed. For 309 and 310, image distortion and color tone deviation were observed.

Example 6
Further, permeable transparent conductive film 301 to 307, using a transparent conductive film 308 to 310 of the comparative example as a transparent conductive substrate, to produce a passive matrix organic EL device as shown in FIG. 6 in the following manner .

<Method for producing organic EL element>
A transparent conductive film (positive electrode) 502 was patterned on the transparent conductive substrate 501. Then, it ultrasonically cleaned using neutral detergent, acetone, and ethanol, and then pulled up from boiling ethanol and dried. Next, the surface of the transparent conductive film was washed with UV / O ₃ , and N, N′-diphenyl-m-tolyl-4,4′-diamine-1,1′-biphenyl (TPD) was deposited at a deposition rate of 0 using a vacuum deposition apparatus. The film was deposited at a thickness of 55 nm at 2 nm / sec to form a hole injection transport layer.

Furthermore, Alq ₃ : tris (8-quinolinolato) aluminum was deposited to a thickness of 50 nm at a deposition rate of 0.2 nm / sec to form an electron injection transport / light emitting layer.

Next, a negative electrode was formed to a thickness of 200 nm using an Al · Sm alloy (Sm: 10 at%) as a target by DC sputtering with a sputtering apparatus. Ar was used as the sputtering gas at this time, the gas pressure was 3.5 Pa, and the distance between the target and the substrate (Ts) was 9.0 cm. The input power was 1.2 W / cm ² .

Finally, SiO ₂ was sputtered to a thickness of 200 nm to obtain an organic EL light emitting device as a protective layer. In this organic EL element, two parallel striped negative electrodes and eight parallel striped electrodes are orthogonal to each other, and 2 × 2 mm vertical and horizontal single elements (pixels) are arranged at intervals of 2 mm. 8 × 2 16-pixel elements.

When the organic EL element thus obtained was driven at 9 V, the transparent conductive films 301 to 307 of the examples had a luminance of 350 cd / m ² or more, but the transparent conductive film 308 of the comparative example. It was 50 cd / m < ² > or less in -310, and required light emission intensity as an organic EL element was not obtained.

  In addition, spacers are arranged on the base material so as to surround the periphery of the organic EL element (ultraviolet curable adhesive (Lux Track LC0629B manufactured by Toagosei Co., Ltd.) is applied between them), and each organic EL element is adhered. Each corresponding transparent film used as the transparent conductive substrate 501 of the EL element was overlapped and adhered to the spacer using the same ultraviolet curable resin, and then the metal halide used in Example 4 through each transparent film. The organic EL element was sealed by irradiating with a lamp to cure the adhesive.

  As an ultraviolet irradiation condition, energy of 6000 mJ was irradiated. However, in the case of using the transparent conductive film of the present invention, it was possible to seal with sufficient strength by photocuring, but the transparent conductive films 308 to 310 of Comparative Examples were used. What was used was not sufficiently photocured and sufficient adhesive strength could not be obtained.

Example 7
Further, permeable transparent conductive film 301 through 307 described above, by using a transparent conductive film 308 to 310 of the comparative example were assembled in the following manner with a touch panel as shown in FIG.

<Assembly method of touch panel>
A glass ITO touch panel (sputtering film deposition product) on the lower electrode 606 in FIG. 7, a transparent conductive substrate obtained in the above embodiment the upper electrode 605 (Toru transparent conductive film 301 to 307, compared Example transparent conductive films 308-310) were used. And the transparent conductive film surface of a transparent conductive base material was made to face each other, and the touch panel was assembled by using a thermosetting type dot spacer and making it into a panel at intervals of 7 μm.

Thus place the appropriate image under the touch panel was assembled and viewed from obliquely 45 ° C., where the image seen through makes a visible or visibility test without distortion, permeable transparent conductive film 301 In 307, an image could be visually recognized without distortion, but distortion was confirmed in the transparent conductive films 308 to 310 of the comparative example.

It is a figure which shows the result of having measured the transmittance | permeability of the ultraviolet-ray of a typical film. It is a figure which shows an example of the plasma discharge processing apparatus under the atmospheric pressure which concerns on this invention, or the pressure of the vicinity. It is a sketch which shows an example which shows the structure of conductive base materials, such as a metal of a roll electrode, and the dielectric material coat | covered on it. It is a sketch showing an example showing the structure of a base material of a rectangular tube type fixed electrode obtained by taking out one of the rectangular tube type fixed electrode groups as application electrodes and a dielectric material coated thereon. It is a perspective view of a liquid crystal display device for demonstrating a liquid crystal display device. It is a conceptual diagram which shows the structural example of an organic EL element. It is sectional drawing which shows an example of a touch panel.

Explanation of symbols

DESCRIPTION OF SYMBOLS 30 Plasma discharge processing apparatus 31 Plasma discharge processing container 32 Discharge processing chamber 35, 35a Roll rotating electrode 35A, 36A Base material 35B, 36B Dielectric 36 Square tube type fixed electrode group 36a Square tube type electrode 40 Voltage application means 50 Gas filling means DESCRIPTION OF SYMBOLS 51 Gas generator 60 Electrode temperature control means 401 Transparent conductive base material 402 Display electrode 403 Orientation film 404 Liquid crystal 501 Transparent conductive base material 502 Transparent conductive film 503 Hole injection transport layer 504 Electron injection transport / light emitting layer 505 Negative electrode 506 Protective layer 601 Transparent conductive substrate 602 Glass for touch panel 603, 604 Transparent conductive film 605 Upper electrode 606 Lower electrode 607 Thermosetting type dot spacer

Claims (13)

In a transparent film for an electronic display comprising a transparent film having an ultraviolet transmittance of 50% or more in a wavelength region of 250 to 450 nm and a glass transition temperature measured by TMA (stress strain measurement) of 180 ° C. or more ,
A transparent film, wherein the main component is a hydrolysis polycondensate of cellulose ester and an alkoxysilane represented by the following general formula (1) .
General formula (1) R _4-n Si (OR ′) _n
(In the formula, R and R ′ represent a hydrogen atom or a monovalent substituent, and n is 3 or 4.) The transparent film according to claim 1, wherein the substitution degree of the cellulose ester is a cellulose ester satisfying the following formulas 1 and 2 .
Formula 1 0 ≦ Y ≦ 1.5
Formula 2 1.0 <X + Y ≦ 2.9
(Here, X represents the degree of substitution with an acetyl group, and Y represents the degree of substitution with a substituent having an alkoxysilyl group.) The hydrolytic polycondensate is represented by the following general formula (2), the mass of the sum of hydrolytic polycondensate represented by the general formula (2) is less than 20 wt% relative to the transparent film The transparent film according to claim 1, wherein the transparent film is provided.
Formula _{(2) R 4-n Si} O n / 2 (n is a natural number) The transparent film according to any one of claims 1 to 3 , wherein a content of the plasticizer in the transparent film is less than 1% . When the in-plane retardation value at a wavelength of 590 nm is R ₀ (590) and the in-plane retardation value at a wavelength of 480 nm is R ₀ (480), the ratio (R ₀ (480) / R ₀ (590)) The transparent film according to any one of claims 1 to 4 , wherein is 0.8 or more and less than 1.0 . The transparent film of any one of Claims 1-5 is used as a sealing film of an electronic display, The adhesive agent used in the case of sealing is actinic-light curable resin, The electron characterized by the above-mentioned. display. A moisture-proof film containing a metal oxide, a metal nitride, or a metal carbide is provided on at least one surface of the transparent film according to any one of claims 1 to 5, and further on the moisture-proof film or the moisture-proof film. transparency conductive you wherein Rukoto and film surface provided provided a transparent conductive film on the opposite side of the film. The transparent conductive film according to claim 7, wherein the moisture-proof film is mainly composed of silicon oxide. The transparent conductive film according to claim 8 wherein the moisture-proof film, characterized in amorphous der Rukoto. A liquid crystal display using the transparent conductive film according to claim 7 as a substrate. An organic EL display using the transparent conductive film according to claim 7 as a substrate. A touch panel using the transparent conductive film according to claim 7 as a substrate. Either a transparent film according to item 1, method for producing a transparent full Irumu you characterized by producing by the solvent casting method of claims 1-5.

Images