JP6780527B2 - the film - Google Patents

Description

The present invention relates to films.

An electrode having a conductive layer formed on a film can be used for a touch panel of a smartphone or a tablet terminal.

Here, as the film, polyethylene terephthalate (PET), polycarbonate (PC), cycloolefin polymer (COP), or the like is generally used from the viewpoints of weight reduction, thinning, and resistance to cracking (for example). , Patent Document 1).

Japanese Unexamined Patent Publication No. 2014-67187

In recent years, smartphones and tablet terminals are required to have heat resistance so that they can be used comfortably in high temperatures such as in summer. Therefore, it is expected that polyarylate having heat resistance will be used as the film.

However, when polyarylate is applied as an electrode film to smartphones and tablet terminals, it has been found that so-called "bone visibility failure" becomes more prominent when exposed to high temperatures for a longer period of time.

Therefore, an object of the present invention to be solved is to provide a film containing polyarylate, which suppresses "bone visibility failure" even when exposed to a high temperature for a long period of time.

The present inventor has conducted diligent research in order to solve the above problems. In the process, we focused on the characteristics of "bone visibility failure" when a film containing polyarylate was used as a base material.

"Bone visibility failure" is said to be a phenomenon that occurs when the difference between the refractive index of the film and the refractive index of the conductive layer becomes large. However, it has been found that when the film containing this polyarylate is used at a high temperature for a long period of time, interference unevenness occurs in the film, which makes "bone visibility failure" stand out.

In the process of investigating the cause of this interference unevenness, we focused on the matte material that can be normally contained in the film. The matte material contained in the film is usually inorganic particles and often has a hydroxyl group on its surface.

The present inventor speculates that the hydroxyl group of the inorganic particles acts on the oxygen atom derived from the aromatic diol at the ester site of the polyarylate, which acts as a crystal nucleating agent for promoting the orientation (crystallization) of the polyarylate. I thought I was doing it. Therefore, if the film is coated with the inorganic particles by containing a small amount of hydrogen-bonding solvent (that is, if the hydrogen-bonding solvent is bonded to the hydroxyl group of the inorganic particles by hydrogen bonding), the inorganic particles can be used as a crystal nucleating agent. I thought that it might be possible to inhibit the action. Therefore, as a result, the present invention was completed by succeeding in suppressing "bone visibility failure" even when exposed to high temperature for a long period of time.

That is, the present invention is a film containing polyarylate and hydroxyl group-containing inorganic particles having a hydroxyl group on the surface, and has a hydrogen bond property of more than 0% by mass and 1% by mass or less with respect to the total mass of the film. A film containing a solvent and having a thickness direction retardation (Rth) of 60 nm or less after heating at 130 ° C. for 300 minutes.

According to the present invention, it is possible to provide a film containing polyarylate, which suppresses "bone visibility failure" even when exposed to a high temperature for a long period of time.

It is a schematic diagram which shows an example of the film manufacturing apparatus. It is the schematic sectional drawing which shows an example of the structure of the transparent conductive film. It is the schematic sectional drawing of the touch panel member including an example of the structure of a transparent conductive film. It is the schematic sectional drawing of the display device which included an example of the structure of a touch panel.

Hereinafter, the present invention will be described. The present invention is not limited to the following embodiments. Further, in the present specification, "X to Y" indicating a range means "X or more and Y or less". Unless otherwise specified, the operation and physical properties are measured under the conditions of room temperature (20 to 25 ° C.) / relative humidity of 40 to 50% RH.

<Film>
The film of the present invention is a film containing polyarylate and hydroxyl group-containing inorganic particles having a hydroxyl group on the surface, and has a hydrogen bond property of more than 0% by mass and 1% by mass or less with respect to the total mass of the film. The thickness direction phase difference (Rth) after heating at 130 ° C. for 300 minutes containing a solvent is 60 nm or less. With such a configuration, "bone visibility failure" is suppressed even when the polyarylate film is exposed to a high temperature for a long period of time.

In the present application, the "bone visibility failure" means that there are a region where electrodes exist and a region where electrodes do not exist on the surface of the film on which the conductive layer is formed, so that the pattern shape of the conductive layer can be seen. It says the phenomenon that it ends up.

(Polyarylate)
Polyarylate, which is the main component of the film of the present invention, contains an aromatic diol component unit and an aromatic dicarboxylic acid component unit.

(Aromatic diol component unit)
The aromatic diol for obtaining the aromatic diol component unit is preferably a bisphenol having a structure represented by the following general formula (1), and more preferably a bisphenol having a structure represented by the following general formula (1'). Kind.

L in the general formula (1) and the general formula (1') represents a divalent organic group. The divalent organic group is preferably a single bond, an alkylene group, -S-, -SO-, -SO _2- , -O-, -C (O)-, -CR ¹ R ^2- (R ¹ and R). ² are attached to each other to form an aliphatic ring or an aromatic ring), or an alkylene-arylene-alkylene group. Preferably, from the viewpoint of mechanical properties, it is -CR ¹ R ^2- (R ¹ and R ² combine with each other to form an aliphatic ring or an aromatic ring), or an alkylene-arylene-alkylene group.

The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, and examples thereof include a methylene group, an ethylene group, and an isopropylene group. The alkylene group may further have a substituent such as a halogen atom or an aryl group. The arylene group is preferably a phenylene group, a naphthalylene group or the like. Similarly, the arylene group may further have a substituent such as a halogen atom or an aryl group.

R of the general formula (1) and the general formula (1') each independently represents a substituent. n represents an integer of 0 to 4 independently of each other, and is preferably an integer of 0 to 3. It is preferable that R is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms independently.

When R ¹ and R ² of −CR ¹ R ² − of the general formula (1) and the general formula (1') form an aliphatic ring, the aliphatic ring is preferably an aliphatic ring having 5 to 20 carbon atoms. It is a hydrocarbon ring, preferably a cyclohexane ring which may have a substituent. The same substituent as R is preferably used. Here, when R ¹ and R ² of −CR ¹ R ² − form an aliphatic ring, it is preferable that they contain a compound having a structure represented by the general formula (2).

R and n are synonymous with the general formula (1). Further, R ³ and R ⁴ independently represent hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and are more preferably hydrogen atoms or methyl groups. When R ³ and R ⁴ are alkyl groups having 4 or less carbon atoms, heat resistance is improved, which is preferable. X represents a carbon atom. m represents an integer of 4 to 7, preferably 4 or 5, and even more preferably 5. When m is an integer of 4 or more, the strain of the ring becomes small and the stability as a compound is improved, which is preferable. Further, when m is an integer of 7 or less, the heat resistance of the obtained polyarylate film is improved, which is preferable.

Examples of the compound having the structure represented by the general formula (2) include 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane [BisTMC] and 1,1-bis- ( 4-Hydroxyphenyl) -3,3,5,5-tetramethylcyclohexane, 1,1-bis- (4-hydroxyphenyl) -3,3,4-trimethylcyclohexane, 1,1-bis- (4-hydroxy) Phenyl) -3,3-dimethyl-5-ethylcyclohexane, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethyl-cyclopentane, 1,1-bis- (3,5-dimethyl) -4-Hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis- (3,5-diphenyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis- (3-Methyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis- (3-phenyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1- Bis- (3,5-dichloro-4-hydroxyphenyl) -3,3,5-trimethyl-cyclohexane, 1,1-bis- (3,5-dibromo-4-hydroxyphenyl) -3,3,5- Trimethylcyclohexane, 1,1-bis (3,5-diphenyl-4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (3-phenyl-4-hydroxyphenyl) -3,3 Examples thereof include 5-trimethylcyclohexane and 1,1-bis (4-hydroxyphenyl) cyclohexane. Among them, BisTMC is preferable from the viewpoint of transparency.

When R ¹ and R ² of −CR ¹ R ² − of the general formula (1) and the general formula (1') form an aromatic ring, the aromatic ring is an aromatic hydrocarbon having 6 to 20 carbon atoms. It is preferably a hydrogen ring. More preferably, it is a fluorene ring which may have a substituent. The same substituent as R is preferably used.

An example of −CR ¹ R ²⁻ forming a fluorene ring which may have a substituent includes a fluoreneyl group having a structure represented by the following general formula (3).

Therefore, more specifically, the residue in which the aromatic diol (divalent phenol component) has a structure represented by the following general formula (4):

It is preferable to include.

When L in the general formula (1) and the general formula (1') is an alkylene-arylene-alkylene group, the alkylene-arylene-alkylene group is an alkylene-arylene having 5 to 7 carbon atoms having 1 to 5 carbon atoms. It is preferably in the form of an alkylene having 1 to 5 carbon atoms, and the alkylene may be linear or branched, but is preferably branched.

Therefore, more specifically, the residue in which the divalent phenol component has a structure represented by the following general formula (5):

R is synonymous with general formula (1),
It is preferable to include.

In the general formula (1) and the general formula (1'), examples of bisphenols in which L is an alkylene group include 1,1-bis (4-hydroxyphenyl) methane and 1,1-bis (4-hydroxyphenyl). ) Ethane, 1,1-bis (4-methyl-2-hydroxyphenyl) methane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) -4-Methylpentane, 2,2-bis (4-hydroxyphenyl) propane (BPA), 2,2-bis (3-methyl-4-hydroxyphenyl) propane (BPC), 2,2-bis (3,) 5-Dimethyl-4-hydroxyphenyl) propane (TMBPA) and the like are included. Among them, 2,2-bis (4-hydroxyphenyl) propane (BPA), 2,2-bis (3-methyl-4-hydroxyphenyl) propane (BPC), 2,2-bis (3,5-dimethyl-). Isopropyridene-containing bisphenols such as 4-hydroxyphenyl) propane (TMBPA) are preferred.

Examples of bisphenols with L of -S-, -SO- or -SO _2- are bis (4-hydroxyphenyl) sulfone, bis (2-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4). -Hydroxyphenyl) sulfone (TMBPS), bis (3,5-diethyl-4-hydroxyphenyl) sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3-ethyl-4-hydroxyphenyl) sulfone, Bis (4-hydroxyphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (3,5-diethyl-4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) It contains sulfide, bis (3-ethyl-4-hydroxyphenyl) sulfide, 2,4-dihydroxydiphenyl sulfone and the like.

Examples of bisphenols with L -O- include 4,4'-dihydroxydiphenyl ethers.

Examples of bisphenols with L -C (O) -include 4,4'-dihydroxydiphenylketone.

The aromatic diol component may be used alone or in combination of two or more, and in particular, L in the general formula (1) and the general formula (1') is alkylene-arylene-. When it is an alkylene group, L may be used in combination with -CR ¹ R ^2- (R ¹ and R ² combine with each other to form an aliphatic ring or an aromatic ring). The mixing ratio is also not limited, but when L in the general formula (1) and the general formula (1') is an alkylene-arylene-alkylene group in an amount of 100 parts by mass, L is −CR ¹ R ² − ( R ¹ and R ² are bonded to each other to form an aliphatic ring or an aromatic ring), preferably 105 to 200 parts by mass, and more preferably 110 to 150 parts by mass. Within this range, the desired physical properties are guaranteed.

(Aromatic dicarboxylic acid component unit)
The aromatic dicarboxylic acids constituting the aromatic dicarboxylic acid component unit are phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, It can be any mixture of them.

A mixture of terephthalic acid and isophthalic acid is preferable from the viewpoint of heat resistance and enhancing the mechanical properties of the film. The content ratio of terephthalic acid and isophthalic acid is preferably terephthalic acid / isophthalic acid = 90/10 to 10/90 (molar ratio), more preferably 70/30 to 30/70, and further preferably 50/50. .. When the content ratio of terephthalic acid is in the above range, a polyarylate having a sufficient degree of polymerization can be easily obtained, and a film having sufficient heat resistance and mechanical properties can be easily obtained.

In a preferred embodiment of the present invention, the composition ratio of the mixture of terephthalic acid and isophthalic acid is preferably 95 mol% or more.

The film of the present invention contains polyarylate as a main component. The inclusion of polyarylate as a main component means that the total amount of polyarylate in the film is 50% by mass or more. It is preferably 80% by mass or more. When the total amount of polyarylate in the film is 50% by mass or more, it is preferable from the viewpoint of good mechanical strength such as bending resistance, heat resistance, and transparency.

The weight average molecular weight of the polyarylate used in the present invention is preferably 10,000 to 500,000, more preferably 20,000 to 300,000, and particularly preferably 30,000 to 200,000. Within such a range, film molding is likely to be easy, and the mechanical properties are not deteriorated. In addition, the molecular weight can be easily controlled in synthesis, and the viscosity of the solution is appropriate to improve the handleability.

As the method for synthesizing the polyarylate used in the present invention, the method of the examples of the present application or a conventionally known synthesis method can be applied. As a conventionally known synthesis method, the synthesis methods described in JP-A-2014-218658, JP-A-2013-173928 and the like can be adopted, but are not limited thereto.

The weight average molecular weight can be measured by gel permeation chromatography. The measurement conditions are as follows.

Solvent: Dichloromethane Column: Shodex K806, K805, K803G (Use by connecting 3 units manufactured by Showa Denko KK)
Column temperature: 25 ° C
Sample concentration: 0.1% by mass
Detector: RI Model 504 (manufactured by GL Science)
Pump: L6000 (manufactured by Hitachi, Ltd.)
Flow rate: 1.0 mL / min
Calibration curve: Standard polystyrene STK standard polystyrene (manufactured by Tosoh Corporation) A calibration curve with 13 samples in the range of Mw = 500 to 2800000 was used. The 13 samples are preferably used at approximately equal intervals.

(Hydroxy group-containing inorganic particles)
The film of the present invention contains hydroxyl group-containing inorganic particles having a hydroxyl group on the surface. By containing the hydroxyl group-containing inorganic particles, the slipperiness and the like are improved, which is suitable from the viewpoint of film production.

As the hydroxyl group-containing inorganic particles, silica, alumina, titanium oxide and ceria are suitable from the viewpoint of ease of production. Therefore, according to a preferred embodiment of the present invention, the hydroxyl group-containing inorganic particles are at least one selected from the group consisting of silica, alumina, titanium oxide and ceria. In the production of the polyarylate film, the hydroxyl group-containing inorganic particles may be dispersed in the solution, and the dispersion medium is an alcohol such as ethanol or a solvent for preparing a dope (polymer solution). Etc. are suitable. For example, the hydroxyl group-containing inorganic particles can be dispersed with alcohol and added to a solvent or the like for preparing a doping (polymer solution). Aggregation can be suppressed by devising the order of addition in this way.

From the viewpoint of suppressing aggregation of the resins, these hydroxyl group-containing inorganic particles preferably form secondary particles having a particle size range of 0.005 to 3 μm and are contained in the polyarylate film, and are preferable average secondary particles. The diameter is in the range of 0.007 to 2 μm, more preferably in the range of 0.008 to 1 μm. The average secondary particle size of the hydroxyl group-containing inorganic particles used in the present invention is measured by observing the particles with a transmission electron microscope (magnification: 500,000 to 2,000,000 times) and observing 100 particles to determine the particle size. The average value is taken as the average secondary particle size.

The hydroxyl group-containing inorganic particles can be contained, for example, in a proportion of 0.05 to 1.0% by mass, and further in a proportion of 0.1 to 0.5% by mass, based on 100 parts by mass of the polyarylate. It is preferably contained, and more preferably 0.1 to 0.3% by mass. Within such a range, it has a technical effect of suppressing the phase difference change after the durability test and suppressing the occurrence of haze.

According to a preferred embodiment of the present invention, at least a part of the surface of the hydroxyl group-containing inorganic particles has a surface treatment layer. By having the surface treatment layer, it is possible to suppress the exposure of hydroxyl groups in the hydroxyl group-containing inorganic particles. That is, it is possible to suppress the action of the exposed hydroxyl group on the oxygen atom derived from the aromatic diol at the ester moiety of the polyarylate. As a result, it is possible to suppress the action like a crystal nucleating agent that promotes the arrangement of polyarylate (suspicious crystallization). In reality, it is not easy to cover the entire surface of the hydroxyl group-containing inorganic particles with a surface treatment layer, and the fact is that a certain amount of hydroxyl groups are exposed even after the surface coating treatment. Therefore, in the present invention, by including a hydrogen-bonding solvent, the hydroxyl groups that could not be covered by the surface treatment layer can be covered with the hydrogen-bonding solvent to prevent the inorganic particles from acting as a crystal nucleating agent. it can. Therefore, even when exposed to a high temperature for a long period of time, "bone visibility failure" can be suppressed.

The hydroxyl group-containing inorganic particles having a surface-treated layer on at least a part of the surface (hereinafter, also referred to as “surface-treated hydroxyl group-containing inorganic particles”) are composed of hydroxyl group-containing inorganic particles and alkylalkoxysilane or arylalkoxysilane as an amine-based catalyst. It can be obtained by reacting in the presence and adjusting the amount, reaction temperature and time of alkylalkoxysilane or arylalkoxysilane.

The alkyl group in the alkylalkoxysilane preferably has 6 or less carbon atoms from the viewpoint of fluidity. Alkyl alkoxysilanes are monomethyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, monoethyltrimethoxysilane, diethyldimethoxysilane, triethylmethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, and isobutyltrimethoxysilane. Is preferable. The arylalkoxysilane is preferably phenylalkoxysilane or naphthalenylalkoxysilane. In particular, when it is phenylalkoxysilane, the occurrence of bone visibility failure can be further suppressed. Therefore, according to a preferred embodiment of the present invention, the surface-treated layer has a benzene ring. The mechanism by which the surface treatment layer has the benzene ring does not necessarily clarify the mechanism, but it is considered that the particle surface is more hydrophobic and bulky, so that it is effective in suppressing the arrangement of the resin.

Surface-treated As the hydroxyl group-containing inorganic particles used as a raw material for the hydroxyl group-containing inorganic particles, those having a BET specific surface area of 20 to 300 m ² / g are preferably used from the viewpoint of modification points. Further, it is preferable to use the hydroxyl group-containing inorganic particles synthesized by the vapor phase method.

The amount of alkylalkoxysilane or arylalkoxysilane with respect to 100 parts by mass of the hydroxyl group-containing inorganic particles is generally 5 to 30 parts by mass from the viewpoint of preventing aggregation.

The surface treatment is preferably carried out in an inert gas atmosphere. For example, after replacing the inside of the system with nitrogen gas or the like, alkylalkoxysilane or arylalkoxysilane is sprayed onto the hydroxyl group-containing inorganic particles. After spraying, aging is performed if necessary, and then the mixture is heated to a boiling point of alkylalkoxysilane or arylalkoxysilane or higher and held for a certain period of time. The residual amount (adhesion amount) of the alkoxy group can be detected by the amount of alcohol generated by the surface treatment. Alcohol detection may be performed by introducing an alcohol concentration meter into the recovery gas line. The reaction temperature is approximately 120 to 170 ° C. The appropriate reaction time is approximately 40 to 120 minutes.

(Hydrogen bond solvent)
In the present invention, a hydrogen-bonding solvent of more than 0% by mass and not more than 1% by mass with respect to the total mass of the film is contained. Inorganic particles are coated with a small amount of hydrogen-bonding solvent contained in the film, that is, by bonding the hydrogen-bonding solvent to the hydroxyl groups of the inorganic particles by hydrogen bonding, the inorganic particles contained in the film serve as a crystal nucleating agent. It is possible to inhibit the action, and it is possible to suppress "bone visibility failure" even when exposed to a high temperature for a long period of time.

The hydrogen-binding solvent is not particularly limited, but alcohol (for example, ethanol, etc.), ketone (for example, acetone, etc.), carboxylic acids (for example, acetic acid, etc.), ethers (for example, tetrahydrofuran, dioxane, etc.), pyrrolidone. Classes (eg, N-methylpyrrolidone, etc.), amines (eg, trimethylamine, pyridine, etc.), ammonia and the like can be exemplified. Of these, alcohol is preferable from the viewpoint of efficiently achieving the intended object of the present invention. Therefore, according to a preferred embodiment of the present invention, the hydrogen-bonding solvent is an alcohol.

The alcohol is not particularly limited, but an alkyl alcohol having 1 to 6 carbon atoms which may have a substituent is preferable. As the substituent, a substituent such as a halogen atom or an aryl group is suitable.

The hydrogen-bonding solvent is contained in an amount of more than 0% by mass and 1% by mass or less based on the total mass of the film. If it is contained in an amount exceeding 1% by mass, the film may become cloudy. On the other hand, if the hydrogen-bonding solvent is not contained, the thickness direction phase difference (Rth) after heating at 130 ° C. for 300 minutes cannot be 60 nm or less, and bone visibility failure occurs.

The hydrogen-binding solvent may be contained in an amount of more than 0% by mass and 1% by mass or less based on the total mass of the film, preferably 0.001 to 1% by mass, more preferably 0.008 to 1% by mass, and further. It is preferably 0.01 to 0.8% by mass, more preferably 0.06 to 0.4% by mass, and particularly preferably 0.08 to 0.2% by mass.

The content of the hydrogen-bonding solvent contained in the film can be measured by applying a conventionally known method for measuring a residual solvent or the like, and for example, it can be measured by the method of the embodiment of the present invention. it can.

Further, the polyarylate film of the present invention may contain two or more kinds of aliphatic compounds having different molecular weights or chemical structures.

<Other additives>
The polyarylate film of the present invention may contain other additives such as an ultraviolet absorber, a peeling accelerator, and a retardation adjuster.

Here, the "phase difference adjuster" is a general term for additives having a function of adjusting the degree of occurrence of the phase difference of the film. The phase difference adjusting agent may be any of a sugar ester compound, a polyester, a non-phosphate ester compound, an acrylic compound, and a vinyl compound. In particular, the vinyl compound is vinyl containing an aryl group such as polystyrene in its structure. It is preferably a system compound.

Preferred examples of the sugar ester compound include sucrose ester having a structure represented by the following general formula (6).

R ^{11 to} R ¹⁸ of the above general formula (6) independently represent a hydrogen atom and a substituted or unsubstituted alkylcarbonyl group. R ^{11 to} R ¹⁸ may be the same as or different from each other.

The substituted or unsubstituted alkylcarbonyl group of R ^{11 to} R ¹⁸ of the general formula (6) is preferably a substituted or unsubstituted alkylcarbonyl group having 2 or more carbon atoms. Examples of substituted or unsubstituted alkylcarbonyl groups include methylcarbonyl groups (acetyl groups).

The average degree of substitution of the acyl group of the sucrose ester is preferably in the range of 3.0 to 7.5. When the average degree of substitution of the acyl group is within this range, sufficient compatibility with the cellulose ester as the film base material can be easily obtained.

Examples of the sugar ester compound include the compounds described in JP-A-62-4-2996 and JP-A-10-237084.

As the polyester, a polyester having a structure represented by the following general formula (7) is more preferable from the viewpoint of the effect of the present invention.

General formula (7) B- (GA) _n -GB
(In the formula, B is a hydroxy group or carboxylic acid residue, G is an alkylene glycol residue having 2 to 12 carbon atoms or an oxyalkylene glycol residue having 4 to 12 carbon atoms, and A is an alkylene dicarboxylic acid having 4 to 12 carbon atoms. It represents an acid residue, and n represents an integer of 1 or more.)
In the general formula (7), it is composed of a hydroxy group or carboxylic acid residue represented by B, an alkylene glycol residue or oxyalkylene glycol residue represented by G, and an alkylene dicarboxylic acid residue represented by A. It is obtained by the same reaction as that of a normal ester compound.

Examples of the carboxylic acid component of the polyester having the structure represented by the general formula (7) include acetic acid, propionic acid, butyric acid, aliphatic acid and the like, and these are used as one kind or a mixture of two or more kinds, respectively. be able to.

Examples of the alkylene glycol component having 2 to 12 carbon atoms of the polyester having the structure represented by the general formula (7) include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, and the like. 1,3-Butanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propane Diol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3 propanediol (3,3-di) Methylol heptane), 3-methyl-1,5-pentanediol 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl There are -1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol and the like, and these glycols are used as one kind or a mixture of two or more kinds.

In particular, alkylene glycol having 2 to 12 carbon atoms is particularly preferable because it has excellent compatibility with the cellulose ester resin.

Examples of the oxyalkylene glycol component having 4 to 12 carbon atoms of the polyester having the structure represented by the general formula (7) include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol. These glycols can be used as one type or a mixture of two or more types.

The polyester having the structure represented by the general formula (7) preferably has a weight average molecular weight in the range of preferably 220 to 1500, more preferably 400 to 1000. The acid value is 0.5 mgKOH / g or less, the hydroxy group value is 25 mgKOH / g or less, more preferably the acid value is 0.3 mgKOH / g or less, and the hydroxy group value is 15 mgKOH / g or less.

Examples of the compound having the structure represented by the general formula (7) include those described below.

7-1: In the general formula (7), the monovalent group of the structure represented by B is derived from 2-ethylhexanoic acid, and the divalent group of the structure represented by G is 1,2-propane. A polyester having a weight average molecular weight of 560 in which a divalent group having a structure represented by diol A is derived from adipic acid.

7-2: In the general formula (7), the monovalent group of the structure represented by B is derived from acetic acid, and the divalent group of the structure represented by G is 1,2-propanediol and A. A polyester having a weight average molecular weight of 489 in which the divalent group of the structure represented is derived from adipic acid.

The polyhydric alcohol ester is an ester derived from a polyhydric alcohol and a fatty acid, and examples thereof include a sorbitan fatty acid ester, a propylene glycol ester, and a sucrose fatty acid ester. Examples of the compound include trimethylolpropane tridecanoate, polyoxyethylene sorbitan trioleate, and the like.

(Thickness direction phase difference (Rth) after heating at 130 ° C. for 300 minutes)
The film of the present invention is a film containing polyarylate and hydroxyl group-containing inorganic particles having a hydroxyl group on the surface, and has a hydrogen bond property of more than 0% by mass and 1% by mass or less with respect to the total mass of the film. Contains solvent. With this configuration, the film has a thickness direction retardation (Rth) of 60 nm or less after being heated at 130 ° C. for 300 minutes.

In the present invention, after heating at 130 ° C. for 300 minutes, the thickness direction retardation (Rth) may be 60 nm or less, preferably 50 nm or less, more preferably 40 nm or less, still more preferably 30 nm or less, still more preferably. Is 20 nm or less, particularly preferably 5 nm or less.

The method for measuring the retardation value Rth in the film thickness direction of the polyarylate film is the method described in the examples of the present invention.

<Film manufacturing method>
As a method for producing a film of the present invention, a hydrogen-bonding solvent of more than 0% by mass and 1% by mass or less is included so that the thickness direction retardation (Rth) after heating at 130 ° C. for 300 minutes is 60 nm or less. Other than that, various conventionally known methods can be applied. In the present invention, it is preferable to produce by the solution casting method from the viewpoint of excellent thinning and mass production suitability.

Therefore, according to a preferred embodiment of the present invention, (1) a step of obtaining a dope by mixing polyallylate, hydroxyl group-containing inorganic particles having a hydroxyl group on the surface, and a hydrogen-bonding solvent; (2) The step of obtaining a film-like substance by casting the dope; (3) having the step of drying the film-like substance, and 0% by mass of the hydrogen-bonding solvent in the film. A method for producing a film, which comprises a drying step of drying so as to be super 1% by mass or less. By having such a configuration, it is a film containing polyarylate and hydroxyl group-containing inorganic particles having a hydroxyl group on the surface, and hydrogen bonds of more than 0% by mass and 1% by mass or less with respect to the total mass of the film. A film containing a sex solvent and having a thickness direction retardation (Rth) of 60 nm or less after heating at 130 ° C. for 300 minutes can be efficiently produced.

The manufacturing process of the polyarylate film can be performed, for example, in the manufacturing apparatus shown in FIG. FIG. 1 is a schematic view showing an example of a film manufacturing apparatus. The film manufacturing apparatus 10 may include a casting apparatus 20 and a drying apparatus 30.

1) Step of obtaining a doping The step of obtaining a doping includes mixing polyallylate, hydroxyl group-containing inorganic particles having a hydroxyl group on the surface, and a hydrogen-bonding solvent.

In the step of obtaining the doping, polyarylate, hydroxyl group-containing inorganic particles having a hydroxyl group on the surface, a hydrogen-bonding solvent, and a retardation adjuster to be added as needed are mixed. This mixing is preferably carried out using a solvent. From the viewpoint of lowering the drying temperature, the solvent is preferably a solvent having a boiling point of 70 ° C. or lower (preferably a good solvent). Examples of good solvents having a boiling point of 70 ° C. or lower include dichloromethane (methylene chloride) (boiling point 40.4 ° C.), chloroform (boiling point 61.2 ° C.), and tetrahydrofuran (boiling point 66 ° C.). From the viewpoint of lowering the drying temperature, a good solvent having a boiling point of 60 ° C. or lower is preferable, and dichloromethane (methylene chloride) is more preferable. The concentration of polyarylate in the dope (polymer solution) is preferably 8% by mass or more, preferably about 10 to 30% by mass. The polymer solution may be filtered to remove insoluble matter, foreign matter, and the like.

2) Step of obtaining a film-like substance The step of obtaining a film-like substance includes casting the doping and obtaining a film-like substance.

For example, the doping obtained above is cast on the metal support 23 from the die 21 of the casting device 20 shown in FIG. 1, and then the casting film is dried to obtain a film-like substance. The metal support 23 can be an endless stainless steel belt carried by the roll 23A. Further, since the film-like material is peeled from the metal support 23 with a peeling roll 25 or the like, it is preferable to dry the cast film. The casting film can be dried by various methods, for example, the surface temperature of the metal support 23 can be adjusted and the casting film can be blown with air. The surface temperature of the metal support 23 can be controlled, for example, by bringing hot water into contact with the back side of the metal support. In the present invention, it is preferable to lower the drying temperature of the casting film on the belt (the surface temperature of the metal support 23 and the temperature of the wind W). By lowering the drying temperature, a film-like material having a high tensile elastic modulus can be obtained. The drying temperature of the casting film, specifically, the surface temperature of the metal support 23 and the temperature of the wind applied to the casting film are preferably less than 70 ° C, preferably 5 to 60 ° C, respectively. It is more preferably ~ 50 ° C., and even more preferably 15-40 ° C. Drying may be carried out all at once, or may be carried out step by step at different temperatures. The film-like material obtained after drying is peeled from the metal support 23 with a peeling roll 25 or the like.

3) Drying step The drying step is a step of drying the film-like substance so that the hydrogen-bonding solvent in the film is more than 0% by mass and 1% by mass or less.

By the way, in the drying step of producing a film by the solution casting method, usually, the solvent remaining in the film is removed as much as possible. On the other hand, the present invention intentionally adds a hydrogen-bonding solvent to the dope (polymer solution) so that the hydrogen-bonding solvent remains in the film in an amount of more than 0% by mass and not more than 1% by mass. It has the characteristics of. That is, the drying step in the present invention is intended to be a hydrogen-bonding solvent of more than 0% by mass and 1% by mass or less based on the total mass of the film by carrying out the drying step at a lower temperature and / or in a shorter time than the conventional drying step. To remain.

The upper limit of the drying temperature may be a temperature at which the hydrogen-bonding solvent is 1% by mass or less, but is preferably less than 150 ° C., more preferably 140 ° C. or lower, further preferably 130 ° C. or lower, and 120 ° C. or lower. Even more preferably, 110 ° C. or lower is even more preferable, and 100 ° C. or lower is even more preferable. The lower limit of the drying temperature may be a temperature at which the hydrogen-bonding solvent is 1% by mass or less, but is preferably more than 50 ° C, more preferably 60 ° C or higher, and more preferably 70 ° C or higher. It is even more preferable that the temperature is 80 ° C. or higher.

The upper limit of the drying time is not particularly limited as long as the time is such that the hydrogen-bonding solvent is more than 0% by mass and 1% by mass or less with respect to the total mass of the film, but it is 120 minutes or less. Is preferable, 90 minutes or less is preferable, 60 minutes or less is preferable, 30 minutes or less is preferable, and 20 minutes or less is preferable. Similarly, the time for the hydrogen-bonding solvent to be more than 0% by mass and 1% by mass or less with respect to the total mass of the film is not particularly limited, but the lower limit is preferably 30 seconds or more. It is more preferably 1 minute or longer, further preferably 3 minutes or longer, further preferably 5 minutes or longer, and even more preferably 7 minutes or longer.

According to a preferred embodiment of the present invention, the drying temperature in the drying step is 70 to 110 ° C., and the drying time is 3 to 20 minutes. According to such drying conditions, the residual amount of the hydrogen-bonding solvent can be more reliably set to more than 0% by mass and 1% by mass or less.

<Electrode>
Like the conventional polyarylate film, the polyarylate film of the present invention has high transparency and heat resistance, and "bone visibility failure" is suppressed even in a high temperature environment. Therefore, the polyarylate film of the present invention has a wide range of applications that require these properties; for example, a transparent substrate or a transparent electrode substrate (glass) in a flexible panel display (organic EL display, liquid crystal display, electronic paper, etc.), a solar cell, or the like. Substrate instead of substrate); Insulating substrate or cover film of flexible printed circuit board (FPC) for applications requiring transparency; Used for transparent conductive film used for touch panels and the like.

Therefore, the film of the present invention is preferably used as a base material for electrodes. Therefore, in the present invention, an electrode including a film and a conductive layer is provided. As the conductive layer, a member that can be used for a so-called transparent electrode such as ITO is suitable. Further, the present invention also provides a method for producing an electrode, which comprises obtaining a film by the above-mentioned production method and forming a conductive layer on the film. With such a configuration, it is possible to provide an electrode that suppresses bone visibility failure.

Hereinafter, typical embodiments of the present invention will be shown and the present invention will be further described, but of course, the present invention is not limited to these embodiments. Unless otherwise specified in the examples, "parts" represents "parts by mass" and "%" represents "% by mass". Unless otherwise specified, the operation and physical properties are measured under the conditions of room temperature (20 to 25 ° C.) / relative humidity of 40 to 50% RH.

<Making inorganic particles>
(Preparation of Inorganic Particle A)
100 g of silica fine powder (average particle diameter: 10 nm) having a BET specific surface area of 50 m ² / g produced by the vapor phase method was placed in a reaction vessel, and 1.5 g of water was sprayed while stirring under a nitrogen atmosphere. To this, 10 g of dimethyldimethoxysilane and 1.0 g of diethylamine as a catalyst were sprayed, heated and stirred at 150 ° C. for 1 hour, and then cooled.

(Preparation of inorganic particles B)
100 g of fine silica powder having a BET specific surface area of 30 m ² / g (average particle diameter: 12 nm) produced by the vapor phase method was placed in a reaction vessel, and 0.5 g of water was sprayed with stirring under a nitrogen atmosphere. To this, 10 g of methyltrimethoxysilane and 1.0 g of diethylamine as a catalyst were sprayed, heated and stirred at 150 ° C. for 1 hour, and then cooled.

(Preparation of Inorganic Particle C)
100 g of silica fine powder (average particle diameter: 20 nm) having a BET specific surface area of 30 m ² / g produced by the vapor phase method was placed in a reaction vessel, and 0.5 g of water was sprayed with stirring under a nitrogen atmosphere. To this, 10 g of phenyltriethoxysilane and 1.0 g of diethylamine as a catalyst were sprayed, heated and stirred at 150 ° C. for 1 hour, and then cooled.

(Preparation of inorganic particles O)
Silica fine powder (average particle size: 7 nm) having a BET specific surface area of 30 m ² / g produced by the vapor phase method was prepared.

<Making polyarylate (PAR)>
(Synthesis of polyarylate 1 (PAR1))
In a reaction vessel equipped with a stirrer, 1,1'-bis (4-hydroxyphenyl) -m-diisopropylbenzene 383.38 parts by mass, 1,1-Biz (4-hydroxyphenyl) -3,3,5- Trimethylcyclohexane ((bisphenol TMC)) 314.69 parts by mass, p-tert-butylphenol (hereinafter abbreviated as PTBP) 9.97 parts by mass, sodium hydroxide 228.51 parts by mass, benzyl-tri-n-butylammonium chloride 4.67 parts by mass was charged and dissolved in 173733.6 parts by mass of water to prepare an aqueous phase. Separately, an organic phase was prepared by dissolving 456.04 parts by mass of a 1/1 mixture (hereinafter abbreviated as MPC) of terephthalic acid / isophthalic acid = (in terms of molars) in 1385.7 parts by mass of methylene chloride. ..

This organic phase was added to the previously prepared aqueous phase under strong stirring, and a polymerization reaction was carried out at 15 ° C. for 2 hours. After that, 41.8 parts by mass of acetic acid was added to stop the polymerization reaction, and the aqueous phase and the organic phase were decanted and separated. For this organic phase, washing and separation were repeated until the organic phase became neutral, using twice the volume of ion-exchanged water for each washing. Then, the washed organic phase is put into warm water at 50 ° C. stirred by a homomixer to evaporate methylene chloride to form a powder, which is further dehydrated and dried to obtain polyarylate 1. Got The weight average molecular weight of this polyarylate 1 was 70,000.

(Synthesis of polyarylate 2 (PAR2))
After adding 2514 parts by mass of water to a reaction vessel equipped with a stirrer, 22.7 parts by mass of sodium hydroxide and 9,9-bis (3,5-dimethyl-4-hydroxyphenyl) fluorene which is a dihydric phenol. 51.3 parts by mass and 0.162 parts by mass of p-tert-butylphenol (PTBP) as a molecular weight modifier were dissolved, 0.34 parts by mass of a polymerization catalyst (tributylbenzylammonium chloride) was added, and the mixture was vigorously stirred. Separately, 25.8 parts by mass of MPC was weighed and dissolved in 945 parts by mass of dichloromethane. This dichloromethane solution was added to the previously prepared alkaline aqueous solution under stirring to initiate polymerization. The polymerization reaction temperature was adjusted to be 15 ° C. or higher and 20 ° C. or lower. The polymerization was carried out for 2 hours, and then acetic acid was added into the system to stop the polymerization reaction, and the organic phase and the aqueous phase were separated. For this organic phase, washing and separation were repeated with twice the volume of ion-exchanged water for one washing. The washing was terminated when the electric conductivity of the washing water became lower than 50 μS / cm. The washed organic phase was put into a warm water tank equipped with a homomixer at 50 ° C. to evaporate dichloromethane to obtain a powdery polymer. Further dehydration and drying were performed to obtain polyarylate 2. The weight average molecular weight of this polyarylate 2 was 90,000.

(Synthesis of polyarylate 3 (PAR3))
In a 2 L reaction vessel equipped with a paddle type double-bladed stirrer, 69.8 parts by mass of BisTMC (bisphenol TMC) as a divalent phenol component and 0.7 of PTBP (4-tert-butylphenol) as an end sealant. 32.7 parts by mass of sodium hydroxide (NaOH) as an alkali, 1.0 part by mass of a 50% by mass aqueous solution of tri-n-butylbenzylammonium chloride [TBBAC] as a polymerization catalyst, and hydrosulfite as an antioxidant. 0.3 parts by mass of sodium was charged and dissolved in 1040 parts by mass of water (aqueous phase). Separately, 23.0 parts by mass of terephthalic acid chloride (TPC) and 23.0 parts by mass of isophthalic acid chloride (IPC) were dissolved in 910 parts by mass of dichloromethane (organic phase) (BisTMC: TPC: IPC). : PTBP: TBBAC: NaOH = 99.0: 50.0: 50.0: 2.0: 0.68: 360 (molar ratio)). The total amount of the aqueous phase and the organic phase was 1 L. The aqueous phase was stirred in advance at 400 rpm, the organic phase was added to the aqueous phase while maintaining the rotation speed, and polymerization was carried out by an interfacial polymerization method at 15 ° C. for 2 hours. After this, stirring was stopped and the aqueous phase and the organic phase were decanted and separated. After removing the aqueous phase, 500 parts by mass of dichloromethane, 2000 parts by mass of pure water and 2 parts by mass of acetic acid were added to stop the reaction, and the mixture was stirred at 15 ° C. for 30 minutes. Then, the organic phase was washed with pure water 10 times, and the organic phase was added to methanol to precipitate the polymer. The precipitated polymer was filtered and dried to give polyarylate 3. The weight average molecular weight of this polyarylate 3 was 80,000.

<Example 1>
(Preparation of Inorganic Particle Additive Solution 1)
Inorganic Particle A 11 parts by mass Ethanol 89 parts by mass or more was stirred and mixed with a dissolver for 50 minutes, and then dispersed with manton gorin to prepare an inorganic particle dispersion liquid 1.

The above-mentioned inorganic particle dispersion 1 was slowly added to the dissolution tank containing methylene chloride while sufficiently stirring. The mass of methylene chloride and the inorganic particle dispersion 1 is as follows:
Methylene chloride 99 parts by mass Inorganic particle dispersion liquid 15 parts by mass.

Further, dispersion was performed with an attritor so that the particle size of the secondary particles had a predetermined size (average secondary particle size: 0.01 μm). This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare an inorganic particle additive solution 1.

(Preparation of doping)
A dope having the following composition was prepared.

Methylene chloride 390 parts by mass Hydrogen-bonding solvent (methanol) 10 parts by mass Polyallylate 1 (PAR1) 100 parts by mass Additive A 10 parts by mass Inorganic particle additive solution 1 (solid content of inorganic particles) 0.15 parts by mass More specifically The above-mentioned components were placed in a closed container and gradually heated to 45 ° C. with stirring to completely dissolve them. The obtained solution was used as Azumi Filter Paper No. The dope was prepared by filtering using 244.

The additive A is as follows:

It is polystyrene having the structure of, and is contained for the purpose of reducing the phase difference.

The additive B is a compound having a structure represented by the general formula (6), where R ^{11 to} R ¹⁸ are hydrogen atoms or methyl groups, and are based on the methyl group among the eight groups. The average degree of substitution is 5.5 (weight average molecular weight 419).

(Film formation)
The prepared dope was uniformly cast on the stainless steel belt of the belt casting device. A stainless steel belt having a length of 20 m was used. The surface temperature of the stainless steel belt is 33 ° C., and the casting film is blown with air at 33 ° C. to evaporate the solvent until the residual solvent amount reaches 39%, and then peeled off from the stainless steel belt to obtain a film-like material. It was.

(Dry)
The obtained film-like material was dried for 10 minutes while being conveyed in a drying device at 90 ° C. with a large number of rolls, and then a polyarylate film 1 having a film thickness of 15 μm was obtained.

(Content of hydrogen-bonding solvent in polyarylate film)
1) Preparation of calibration curve A sample having a known concentration of hydrogen-bonding solvent was placed in a special vial, sealed with a septum and an aluminum cap, and set in a headspace sampler. Then, the vial was heated under the following headspace heating conditions to generate a volatile component, and the volatile component was measured by gas chromatography.

(Headspace sampler)
Equipment: Hewlett-Packard headspace sampler HP7694 type Headspace heating conditions: 300 minutes at 130 ° C (gas chromatography)
Equipment: Hewlett-Packard 5971 type Column: J & W DB-624
Detector: Hydrogen flame ionization detector (FID)
GC temperature rise condition: After holding at 45 ° C for 3 minutes, raise to 100 ° C at 8 ° C / min GC introduction temperature: 150 ° C
Similar measurements were performed for samples with different concentrations of hydrogen-bonding solvents. Then, the peak area of the solvent in the GC chart obtained by each measurement was calculated, a plot of the solvent concentration and the peak area was prepared, and a calibration curve of the hydrogen-bonding solvent was obtained.

2) Measurement of the content of hydrogen-bonding solvent with respect to the total mass of the polyarylate film The same as 1) above, except that the polyarylate film cut into 10 cm squares was finely chopped to about 5 mm and sealed in a special vial. Heat treatment was performed under headspace heating conditions, and the obtained volatile components were measured by gas chromatography.

From the obtained chart, the peak area of each solvent was calculated and collated with the calibration curve obtained in 1) above to determine the content (mass%) of the hydrogen-bonding solvent with respect to the total mass of the polyarylate film.

<Examples 2 to 14, Comparative Examples 1 to 4>
Polyarylate films 2 to 15 were prepared in the same manner as in Example 1 except that the type of polyarylate, the type of hydrogen-bonding solvent, the drying conditions, the type of inorganic particles and their amounts were changed as shown in Table 1. did. Moreover, the content (mass%) of the hydrogen-bonding solvent with respect to the total mass of the polyarylate film was determined.

<Evaluation>
(Heating test)
Each polyarylate film produced above was placed in a constant temperature and humidity chamber (PL-4 manufactured by ESPEC), and a durability test was carried out at 130 ° C. for 300 minutes. After that, it was taken out and the phase difference value Rth (nm) in the film thickness direction was measured.

(Phase difference value Rth (nm) in the film thickness direction)
The phase difference value Rth in the film thickness direction of each polyarylate film is a wavelength of 590 nm under an environment of 23 ° C. and 55% RH using an automatic birefringence meter Axoscan (Axo Scan Mueller Metricx Polarimeter). In, three-dimensional refractive index measurement was performed, and it was calculated from the obtained refractive indexes n _x , _ny , and n _z using the following formula.

Equation (1) Rt = {(n _x + n _y ) /2-n _z } × d
[In the formula, Rt is a phase difference value measured with light having a wavelength of 590 nm in an environment of a temperature of 23 ° C. and a relative humidity of 55%.

n _x is the refractive index in the slow axis direction in the plane of the polyarylate film.
n _y is a refractive index in a direction perpendicular to the slow axis direction in the polyarylate film plane,
_nz is the refractive index in the direction perpendicular to the polyarylate film plane.
d is the thickness (nm) of the polyarylate film.

<Manufacturing of device>
(Preparation of transparent conductive film 1)
Next, a transparent conductive film 1 having the configuration shown in FIG. 2 was produced.

A photoreactive coating liquid containing an acrylate-based resin is applied onto one side of a resin base material 2 (polyarylate film), and after heating and drying, ultraviolet rays are irradiated to form a hard coat layer 3, and the hard coat layer 3 of the present invention is formed. A coated support film was obtained. Next, a layer made of an acrylate-based resin having a thickness of 42 nm containing zirconia particles as a hard coat layer and an optical interference layer (high refractive index interference layer) 3 on the PAR base material 2 on the side where the hard coat layer is not formed. (NC1 = 1.68) is formed, and a layer (nC2 = 1.) of an acrylate-based resin containing silicon oxide having a thickness of 33.5 nm as an optical interference layer (low refractive index interference layer) 4 is formed therein. 49) was formed. Next, a layer (nD = 1.87) made of indium tin oxide as a light-transmitting conductive layer is formed on the film via a SiOx layer for improving adhesion so as to have a thickness of 26 nm, according to the present invention. A light-transmitting conductive film was obtained. As the target material, a sintered material composed of indium oxide: 97% by weight and tin oxide: 3% by weight was used. Further, a SiOx layer was formed by a DC magnetron sputtering method, and an indium tin oxide layer was formed on the SiOx layer.

(Preparation of transparent conductive films 2 to 15)
Similar to the transparent conductive film 1, the transparent conductive films 2 to 15 were produced except that the polyarylate films 2 to 15 were used as the resin base material 2.

<Manufacturing of touch panel members>
As described in Japanese Patent Application Laid-Open No. 2010-541109, the touch panel member 7 was produced using the patterned transparent conductive film 1. That is, the two transparent conductive films 1 were laminated so as to sandwich the adhesive film 5 so as to be in the X direction and the Y direction, and a touch panel member 7 was produced using the polyarylate films 1 to 15 as shown in FIG. .. An ITO etching solution (manufactured by Kanto Chemical Co., Inc., trade name "ITO-06N") is used to form patterns in the X and Y directions.

<Manufacturing of organic EL display device with touch panel>
Using a 3 mm thick 127 cm non-alkali glass, an organic EL cell having the configuration described in FIG. 8 of JP-A-2010-20925 was prepared according to the method described in Examples of JP-A-2010-20925. ..

Then, as shown in FIG. 4, after installing the gas barrier film 109 in the organic EL cell 108, the touch panel member 7 was installed. Further, a film (adhesive film) 5 coated with an adhesive was attached to the surface of the circular polarizing plate 110. A cover glass 106 was placed on the outermost surface to produce an organic EL display device with a touch panel using polyarylate films 1 to 15 having the configuration shown in FIG.

The following evaluations were performed on each organic EL display device with a touch panel manufactured as described above.

<Evaluation>
(Evaluation of bone visibility failure after heating test)
Each device (organic EL display device with each touch panel) produced above was placed in a constant temperature and humidity controller (PL-4 manufactured by ESPEC), and a durability test at 80 ° C. for 30 days was carried out. After that, it was taken out and the bone visibility failure of the device was evaluated by visual inspection. The results are shown in Table 1.

◎: Bone cannot be confirmed,
○: Some bones can be confirmed,
×: Bones can be seen clearly.

In this application, ⊚ and ◯ are acceptable.

1 Transparent conductive film,
2 Polyarylate film (resin base material),
3 Hard coat (hard coat layer and optical interference layer (high refractive index interference layer)),
4 Optical interference layer (low refractive index interference layer),
5 Adhesive film,
7 Touch panel member,
10 Film manufacturing equipment,
20 casting device,
21 dice,
23 metal support,
23A roll w wind,
25 peeling roll,
30 Drying device 31 Roll device,
106 cover glass,
108 Organic EL display device,
109 Gas Barrier Film,
110 circular polarizing plate.

Claims (10)

Polyarylate and
Hydroxy group-containing inorganic particles having a hydroxyl group on the surface and
Is a film, including
Contains a hydrogen-bonding solvent of more than 0.5 % by mass and 1% by mass or less based on the total mass of the film.
The thickness direction retardation in after heating 300 minutes at 130 ° C. (Rth) is Ri der less 60 nm,
A film in which the hydrogen-bonding solvent is an alcohol and at least a part of the surface of the hydroxyl group-containing inorganic particles has a surface treatment layer . Polyarylate and
Hydroxy group-containing inorganic particles having a hydroxyl group on the surface and
Is a film, including
It contains a hydrogen-bonding solvent of more than 0% by mass and 1% by mass or less based on the total mass of the film.
At least a part of the surface of the hydroxyl group-containing inorganic particles has a surface-treated layer, and the surface-treated layer has a benzene ring.
A film having a thickness direction retardation (Rth) of 60 nm or less after heating at 130 ° C. for 300 minutes. The film according to claim 2 , wherein the hydrogen-bonding solvent is an alcohol. The film according to any one of claims 1 to 3, wherein the hydroxyl group-containing inorganic particles are at least one selected from the group consisting of silica, alumina, titanium oxide and ceria. The surface treatment layer has a benzene ring, a film according to claim 1. A step of obtaining a doping by mixing polyarylate, hydroxyl group-containing inorganic particles having a hydroxyl group on the surface, and a hydrogen-bonding solvent;
With the step of obtaining a film-like substance by casting the doping;
With the drying step, which comprises drying the film-like material and drying the hydrogen-bonding solvent in the film so as to be more than 0.5 % by mass and 1% by mass or less;
Have a,
A method for producing a film, wherein the hydrogen-bonding solvent is alcohol, and at least a part of the surface of the hydroxyl group-containing inorganic particles has a surface treatment layer . A step of obtaining a doping by mixing polyarylate, hydroxyl group-containing inorganic particles having a hydroxyl group on the surface, and a hydrogen-bonding solvent;
With the step of obtaining a film-like substance by casting the doping;
With a drying step, which comprises drying the film-like material and drying the hydrogen-bonding solvent in the film so as to be more than 0% by mass and 1% by mass or less;
Have a,
A method for producing a film , wherein at least a part of the surface of the hydroxyl group-containing inorganic particles has a surface-treated layer, and the surface-treated layer has a benzene ring . The production method according to claim 6 or 7 , wherein the drying temperature in the drying step is 70 to 110 ° C., and the drying time is 3 to 20 minutes. An electrode comprising the film according to any one of claims 1 to 5 and a conductive layer. A method for producing an electrode, which comprises obtaining a film by the production method according to any one of claims 6 to 8 and forming a conductive layer on the film.