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WO2018163884A1 - Substrat de film d'électrode transparente et son procédé de production - Google Patents

Substrat de film d'électrode transparente et son procédé de production Download PDF

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Publication number
WO2018163884A1
WO2018163884A1 PCT/JP2018/006962 JP2018006962W WO2018163884A1 WO 2018163884 A1 WO2018163884 A1 WO 2018163884A1 JP 2018006962 W JP2018006962 W JP 2018006962W WO 2018163884 A1 WO2018163884 A1 WO 2018163884A1
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Prior art keywords
bis
film
base film
transparent electrode
acid
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English (en)
Japanese (ja)
Inventor
康敏 伊藤
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Konica Minolta Inc
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Konica Minolta Inc
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Priority to JP2019504480A priority Critical patent/JP7172981B2/ja
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • G—PHYSICS
    • G06—COMPUTING OR CALCULATING; COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Definitions

  • the present invention relates to a transparent electrode substrate film and a method for producing the same.
  • a resin such as polyethylene terephthalate or cycloolefin polymer has been often used (see, for example, JP-A-2014-67187).
  • a film made of ITO or the like as an electrode material is formed on the electrode base film for such use through a vacuum film forming process.
  • the maximum temperature may be 250 ° C. or higher. Therefore, the electrode substrate film is required to have high heat resistance and dimensional stability. The electrode substrate film is also required to have high bending resistance.
  • an object of the present invention is to provide a transparent electrode substrate film that can suppress color unevenness and can maintain the keystroke performance of a touch panel even when used for a long period of time. To do. Furthermore, this invention aims at providing the manufacturing method of the said base film for transparent electrodes.
  • the inventor has intensively studied the above problems. In the process, it has been found that, when a vacuum film formation process is performed on a base film containing a heat resistant resin or the like, minute wrinkles are generated in the base film, causing the above problem.
  • a more specific cause is estimated as follows. That is, when the base film is processed in a vacuum state and at a high temperature, a non-uniform force is generated between the base film and the can roll (cooling roll) of the vacuum film forming apparatus. It is thought that minute twisting occurs on the base film. And it is thought that when this electrode is formed on the base film, the deposited film of the electrode material becomes non-uniform and color unevenness occurs due to this minute change. In addition, after the touch panel has been used for a long period of time, the base film and the electrode are peeled off due to this fine pulling, and it is considered that the keystroke performance of the touch panel is lowered.
  • the present inventor uses a base film containing a heat resistant resin having a glass transition temperature equal to or higher than a predetermined value and having Ra on at least one surface in a predetermined range.
  • a fine float can be formed on the contact surface between the can roll and the base film, and the problem of color unevenness of the base film and deterioration of keystroke performance after long-term use has been successfully improved.
  • the present inventor includes a heat-resistant resin having a glass transition temperature (Tg) of 180 ° C. or higher, and has an arithmetic average roughness Ra of at least 0.5 nm to 4.0 nm at least on one side. It has been found that the above-mentioned problems can be solved by using an electrode substrate film, and the present invention has been completed.
  • Tg glass transition temperature
  • FIG. 1 It is a schematic diagram which shows an example of the manufacturing apparatus of a film. It is a figure which shows the process of the stamping process of a base film. It is a figure which shows some embossing processing apparatuses of a base film.
  • One embodiment of the present invention includes a heat-resistant resin having a glass transition temperature of 180 ° C. or higher, and has an arithmetic average roughness Ra of at least one surface of 0.5 nm or more and 4.0 nm or less. It is.
  • X to Y indicating a range means “X or more and Y or less”. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.
  • the transparent electrode substrate film of the present invention includes a heat-resistant resin having a glass transition temperature (Tg) of 180 ° C. or higher, and has an arithmetic average roughness Ra of at least one side. It is 0.5 nm or more and 4.0 nm or less. With this configuration, the color unevenness of the base film can be suppressed, and the touching performance of the touch panel can be maintained even when used for a long time.
  • Tg glass transition temperature
  • a vacuum film formation process may be performed in a process of producing an electrode by being exposed to a high temperature exceeding 150 ° C.
  • a process temperature high temperature exceeding 150 ° C.
  • the process temperature high temperature exceeding 150 ° C.
  • the elastic modulus of the base film decreases rapidly. Therefore, there is a concern that the base film is stretched and the base film is damaged.
  • the base film according to the present invention includes a heat resistant resin having a glass transition temperature of 180 ° C. or higher.
  • the arithmetic average roughness Ra of at least one side of the base film is within a specific range, so that the fineness is between the base film and the can roll (cooling roll) of the apparatus. It was found that the problem described above can be solved by creating a float and eliminating minute drift. Specifically, the arithmetic average roughness Ra of at least one surface of the base film of the present invention is 0.5 nm or more and 4.0 nm or less.
  • the base film according to the present invention includes a heat resistant resin having a glass transition temperature of 180 ° C. or higher.
  • a heat resistant resin having a glass transition temperature of 180 ° C. or higher.
  • a known resin can be used without particular limitation.
  • Specific examples of the heat-resistant resin include polyarylate, polyimide, polyetherimide, polyamideimide, and resins having a silsesquioxane having an organic-inorganic hybrid structure as a basic skeleton.
  • the heat-resistant resin according to the present invention preferably contains polyarylate, polyamideimide or polyimide, and more preferably contains polyarylate. Below, a polyarylate and a polyimide are demonstrated.
  • the polyarylate that can be used in the base film of the present invention contains an aromatic diol component unit and an aromatic dicarboxylic acid 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), more preferably a bisphenol having a structure represented by the following general formula (1 ′). It is kind.
  • L in general formula (1) and general formula (1 ′) each independently represents a single bond or a divalent organic group.
  • the divalent organic group is preferably an alkylene group, —S—, —SO—, —SO 2 —, —O—, —C (O) —, —CR 1 R 2 — (R 1 and R 2 are To form an aliphatic ring or an aromatic ring), or an alkylene-arylene-alkylene group.
  • —CR 1 R 2 — R 1 and R 2 are bonded to each other to form an aliphatic ring or an aromatic ring
  • an alkylene-arylene-alkylene group Preferably, from the viewpoint of providing flexibility, —CR 1 R 2 — (R 1 and R 2 are bonded to 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.
  • a substituent such as a halogen atom or an aryl group.
  • an arylene group Preferably a phenylene group, naphthalenylene group, etc. are mentioned.
  • the arylene group may further have a substituent such as a halogen atom or an aryl group.
  • R in general formula (1) and general formula (1 ') each independently represents a substituent.
  • Each n independently represents an integer of 0 to 4, preferably an integer of 0 to 3.
  • R is preferably independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • the aliphatic ring is preferably an aliphatic group having 5 to 20 carbon atoms. It is a hydrocarbon ring, preferably a cyclohexane ring which may have a substituent. Such substituent is preferably the same as R.
  • the compound represented by the general formula (1) is a compound having a structure represented by the general formula (2). Preferably there is.
  • R and n are synonymous with General formula (1).
  • R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a methyl group. It is preferable that R 3 and R 4 are alkyl groups having 4 or less carbon atoms because heat resistance is improved.
  • X represents a carbon atom.
  • m represents an integer of 4 to 7, preferably 4 or 5, and more preferably 5. When m is an integer of 4 or more, ring distortion is reduced, and stability as a compound is improved, which is preferable. Moreover, when m is an integer of 7 or less, the heat resistance of the resulting 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], 1,1-bis- (4-hydroxyphenyl) -3,3,5,5-tetramethylcyclohexane, 1,1-bis- (4-hydroxyphenyl) -3,3,4-trimethylcyclohexane, 1,1-bis- (4- Hydroxyphenyl) -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-tri Tylcyclohexane, 1,1-bis- (3-methyl-4-hydroxyphenyl) -3,3,5-trimethyl
  • the aromatic ring is an aromatic carbon atom having 6 to 20 carbon atoms. It is preferably a hydrogen ring. More preferably, it is a fluorene ring which may have a substituent. Such substituent is preferably the same as R.
  • Examples of —CR 1 R 2 — that forms a fluorene ring that may have a substituent include a fluorenediyl group having a structure represented by the following general formula (3).
  • the alkylene-arylene-alkylene group is an alkylene having 1 to 5 carbon atoms and an arylene having 5 to 7 carbon atoms.
  • the alkylene is preferably in the form of an alkylene having 1 to 5 carbon atoms.
  • the alkylene may be linear or branched, but is preferably branched.
  • R is synonymous with the general formula (1). Is preferably included.
  • Examples of the bisphenols in which L is an alkylene group in the general formula (1) and the general formula (1 ′) include 1,1-bis (4-hydroxyphenyl) methane, 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.
  • BPA 2,2-bis (4-hydroxyphenyl) propane
  • BPC 2,2-bis (3-methyl-4-hydroxyphenyl) propane
  • TMBPA 2,2-bis (3 5-dimethyl-4-hydroxyphenyl) propane
  • BPA 2,2-bis (4-hydroxyphenyl) propane
  • BPC 2,2-bis (3-methyl-4-hydroxyphenyl) propane
  • TMBPA isopropylidene-containing bisphenols such as 4-hydroxyphenyl) propane
  • Examples of bisphenols wherein L is —S—, —SO— or SO 2 — include 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) sulfide Bis (3-ethyl-4-hydroxyphenyl) sulfide, 2,4-dihydride Carboxymethyl diphenyl sulfone and the like.
  • Examples of bisphenols in which L is —O— include 4,4′-dihydroxydiphenyl ether.
  • Examples of bisphenols in which L is —C (O) — include 4,4′-dihydroxydiphenyl ketone.
  • the aromatic diol component may be used singly or in combination of two or more.
  • L in the general formula (1) and the general formula (1 ′) is alkylene-arylene- When it is an alkylene group, it may be used in combination with a compound in which L is —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 not limited, but when L in the general formula (1) and the general formula (1 ′) is an alkylene-arylene-alkylene group is 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.
  • the amount of the compound is preferably 105 to 200 parts by mass, more preferably 110 to 150 parts by mass. Within such a range, it has a technical effect on physical property guarantees.
  • the aromatic dicarboxylic acid constituting the aromatic dicarboxylic acid component unit is phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, tert-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, It can be any mixture thereof.
  • a mixture of terephthalic acid and isophthalic acid is preferable from the viewpoints of improving heat resistance and mechanical properties of the film.
  • terephthalic acid / isophthalic acid 90/10 to 10/90 (mol ratio), more preferably 70/30 to 30/70, and even more preferably 50/50.
  • the constituent ratio of the mixture of terephthalic acid and isophthalic acid is preferably 95 mol% or more.
  • 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. If it is this range, film formation will become easy and a mechanical characteristic will not fall. In addition, the molecular weight can be easily controlled in the synthesis, and the viscosity of the solution is moderate and the handling property is improved.
  • the method of the examples of the present application or a conventionally known synthesis method can be applied.
  • a conventionally known synthesis method a synthesis method described in JP2014-218659A, JP2013-173928A, or the like can be employed, but is not limited thereto.
  • the weight average molecular weight of the heat resistant resin can be measured by gel permeation chromatography.
  • the measurement conditions are as follows.
  • the polyimide of the present invention can be obtained by preparing a polyamic acid by reacting an aromatic, aliphatic or alicyclic tetracarboxylic acid or a derivative thereof with a diamine or a derivative thereof, and imidizing the polyamic acid.
  • aliphatic or alicyclic tetracarboxylic acid derivatives examples include aliphatic or alicyclic tetracarboxylic acid esters, aliphatic or alicyclic tetracarboxylic dianhydrides, and the like. Of the aliphatic or alicyclic tetracarboxylic acids or derivatives thereof, alicyclic tetracarboxylic dianhydrides are preferred.
  • diamine derivatives include diisocyanates and diaminodisilanes. Of the diamines or derivatives thereof, diamines are preferred.
  • Examples of the aliphatic tetracarboxylic acid include 1,2,3,4-butanetetracarboxylic acid.
  • Examples of the alicyclic tetracarboxylic acid include 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,4,5-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid.
  • Bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid, etc. Can be mentioned.
  • Examples of the aliphatic tetracarboxylic acid esters include monoalkyl esters, dialkyl esters, trialkyl esters, and tetraalkyl esters of the above aliphatic tetracarboxylic acids.
  • Examples of the alicyclic tetracarboxylic acid esters include monoalkyl esters, dialkyl esters, trialkyl esters, and tetraalkyl esters of the above alicyclic tetracarboxylic acids.
  • the alkyl group site is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
  • Examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride.
  • Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5-cyclopentanetetracarboxylic dianhydride, , 4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2]
  • Examples include octane-2,3,5,6-tetracarboxylic dianhydride and 2,3,5-tricarboxycyclopentylacetic acid dianhydride.
  • 1,2,4,5-cyclohexanetetracarboxylic dianhydride is particularly preferred.
  • a polyimide having an aliphatic diamine as a constituent component forms a strong salt between the polyamic acid, which is an intermediate product, and the diamine. Therefore, in order to increase the molecular weight, a solvent having a relatively high salt solubility (for example, Cresol, N, N-dimethylacetamide, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, etc.) are preferably used.
  • aromatic tetracarboxylic acid examples include 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA), 4,4′-oxydiphthalic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3 4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,4′-oxydiphthalic anhydride, 3,4,9,10 Perylenetetracarboxylic dianhydride (Pigment Red 224), 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,2-bis (4
  • 1,2,3,4-cyclopentanetetracarboxylic dianhydride 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, Tricyclo [6.4.0.02,7] dodecane-1,8: 2,7-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene- 1,2-dicarboxylic acid anhydride and the like can be used.
  • Aromatic, aliphatic or alicyclic tetracarboxylic acids or derivatives thereof may be used alone or in combination of two or more. Further, other tetracarboxylic acids or derivatives thereof (particularly dianhydrides) may be used in combination as long as the solvent solubility of the polyimide, the flexibility of the film, the thermocompression bonding property, and the transparency are not impaired.
  • the diamine may be an aromatic diamine, an aliphatic diamine, or a mixture thereof.
  • aromatic diamine refers to a diamine in which an amino group is directly bonded to an aromatic ring, and an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or any other part of its structure.
  • a substituent for example, a halogen atom, a sulfonyl group, a carbonyl group, an oxygen atom, etc. may be contained.
  • aliphatic diamine refers to a diamine in which an amino group is directly bonded to an aliphatic hydrocarbon group or an alicyclic hydrocarbon group, and an aromatic hydrocarbon group or other substituent (for example, it may contain a halogen atom, a sulfonyl group, a carbonyl group, an oxygen atom, etc.).
  • aromatic diamines examples include p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, benzidine, o-tolidine, m-tolidine, bis (trifluoromethyl) benzidine ( TFMB), octafluorobenzidine, 3,3′-dihydroxy-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diamino Biphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2,6-diaminonaphthalene, 1,5-diaminonaphthalene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4 '-Diaminodipheny
  • aliphatic diamine examples include ethylene diamine, hexamethylene diamine, polyethylene glycol bis (3-aminopropyl) ether, polypropylene glycol bis (3-aminopropyl) ether, 1,3-bis (aminomethyl) cyclohexane (cis form and mixture of trans isomers), 1,4-bis (aminomethyl) cyclohexane (mixture of cis isomer and trans isomer), isophorone diamine, norbornane diamine, siloxane diamine, 4,4′-diaminodicyclohexyl methane, 3,3′-dimethyl -4,4'-diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodicyclohexylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, 2,
  • diisocyanate that is a diamine derivative examples include diisocyanate obtained by reacting the above aromatic or aliphatic diamine with phosgene.
  • the above diamines and derivatives thereof may be used in an arbitrary mixture, but the amount of diamine in them is preferably 50 to 100 mol%, more preferably 80 to 100 mol%.
  • Polyamic acid can be obtained by polymerizing at least one of the tetracarboxylic acids and at least one of the diamines in a suitable solvent.
  • the polyamic acid ester is diesterified by ring-opening the tetracarboxylic dianhydride with an alcohol such as methanol, ethanol, isopropanol, or n-propanol, and the obtained diester is converted into the above-mentioned diester in an appropriate solvent. It can be obtained by reacting with a diamine compound. Furthermore, the polyamic acid ester can also be obtained by esterification by reacting the carboxylic acid group of the polyamic acid obtained as described above with an alcohol as described above.
  • the reaction between the tetracarboxylic dianhydride and the diamine compound can be carried out under conventionally known conditions. There are no particular limitations on the order or method of addition of tetracarboxylic dianhydride and diamine compound.
  • a polycarboxylic acid can be obtained by sequentially adding a tetracarboxylic dianhydride and a diamine compound to a solvent and stirring at an appropriate temperature.
  • the amount of the diamine compound is usually 0.8 mol or more, preferably 1 mol or more with respect to 1 mol of tetracarboxylic dianhydride. On the other hand, it is usually 1.2 mol or less, preferably 1.1 mol or less.
  • the yield of the polyamic acid obtained can be improved by making the quantity of a diamine compound into such a range.
  • the concentration of tetracarboxylic dianhydride and diamine compound in the solvent is appropriately set according to the reaction conditions and the viscosity of the polyamic acid solution.
  • the total mass of the tetracarboxylic dianhydride and the diamine compound is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more with respect to the total amount of the solution, while usually 70%. It is not more than mass%, preferably not more than 30 mass%.
  • the reaction temperature is not particularly limited, but is usually 0 ° C. or higher, preferably 20 ° C. or higher, and is usually 100 ° C. or lower, preferably 80 ° C. or lower.
  • the reaction time is not particularly limited but is usually 1 hour or longer, preferably 2 hours or longer, and is usually 100 hours or shorter, preferably 24 hours or shorter.
  • polymerization solvent used in this reaction examples include hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene and mesitylene; carbon tetrachloride, methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, diethylene Halogenated hydrocarbon solvents such as chlorobenzene and fluorobenzene; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, methoxybenzene, alkylene glycol monoalkyl ether and alkylene glycol dialkyl ether; ketone solvents such as acetone and methyl ethyl ketone Amide systems such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide and N-methyl-2-pyrrolidone (NMP); Medium;
  • the polyimide is prepared by heating the polyamic acid solution to imidize the polyamic acid (thermal imidization method), or adding a ring-closing catalyst (imidation catalyst) to the polyamic acid solution to imidize the polyamic acid. It can be obtained by a method (chemical imidization method).
  • the polyamic acid in the polymerization solvent is heated for 1 to 200 hours in a temperature range of, for example, 80 to 300 ° C. to advance imidization.
  • the temperature range is preferably 150 to 200 ° C., and by setting the temperature range to 150 ° C. or higher, imidization can be reliably progressed and completed. It is possible to prevent an increase in resin concentration due to oxidation of unreacted raw materials and volatilization of the solvent solvent.
  • an azeotropic solvent can be added to the polymerization solvent in order to efficiently remove water generated by the imidization reaction.
  • the azeotropic solvent for example, aromatic hydrocarbons such as toluene, xylene and solvent naphtha, and alicyclic hydrocarbons such as cyclohexane, methylcyclohexane and dimethylcyclohexane can be used.
  • the amount added is about 1 to 30% by mass, preferably 5 to 20% by mass, based on the total amount of organic solvent.
  • a known ring closure catalyst is added to the polyamic acid in the polymerization solvent to advance imidization.
  • pyridine may generally be used, but other than this, for example, a substituted or unsubstituted nitrogen-containing heterocyclic compound, an N-oxide compound of a nitrogen-containing heterocyclic compound, a substituted or unsubstituted amino acid compound, Examples thereof include aromatic hydrocarbon compounds or aromatic heterocyclic compounds having a hydroxy group, and in particular 1,2-dimethylimidazole, N-methylimidazole, N-benzyl-2-methylimidazole, 2-methylimidazole, 2-ethyl- Lower alkyl imidazoles such as 4-methylimidazole and 5-methylbenzimidazole, imidazole derivatives such as N-benzyl-2-methylimidazole, isoquinoline, 3,5-dimethylpyridine, 3,4-dimethylpyridine, 2,5-
  • the addition amount of the ring closure catalyst is preferably about 0.01 to 2 times equivalent, particularly about 0.02 to 1 time equivalent to the amic acid unit of the polyamic acid.
  • a dehydrating agent may be added to the polyamic acid solution.
  • a dehydrating agent include aliphatic acid anhydrides such as acetic anhydride, phthalates, and the like. Examples thereof include aromatic acid anhydrides such as acid anhydrides, and these can be used alone or in combination.
  • it is preferable to use a dehydrating agent because the reaction can proceed at a low temperature.
  • it is possible to imidize the polyamic acid simply by adding a dehydrating agent to the polyamic acid solution it is preferable to imidize by heating or adding a ring-closing catalyst as described above because the reaction rate is slow. .
  • the polyimide is subjected to a heat treatment (thermal imidization method) on a film in which a polyamic acid solution is cast, or a polyamic acid solution mixed with a ring closure catalyst is cast on a support. Then, it can be obtained in a film state by imidization (chemical imidization method).
  • the ring-closing catalyst include aliphatic tertiary amines such as trimethylamine and triethylenediamine, and heterocyclic tertiary amines such as isoquinoline, pyridine and picoline, which are selected from heterocyclic tertiary amines. It is preferred to use at least one amine.
  • the content of the ring-closing catalyst with respect to the polyamic acid is preferably in a range where the content (mol) of the ring-closing catalyst / the content (mol) of the polyamic acid is 0.5 to 8.0.
  • polyamic acid or polyimide constituted as described above those having a weight average molecular weight of 30,000 to 1,000,000 are used from the viewpoint of easy film formation.
  • the polyamideimide of the present invention is produced by reacting an aromatic, aliphatic or alicyclic tetracarboxylic acid or a derivative thereof with a diamine or a derivative thereof to form a polyamide acid, and ring-closing the polyamide acid to produce a polyamideimide. Obtained by the method.
  • the reaction of the aromatic, aliphatic or alicyclic tetracarboxylic acid or a derivative thereof with a diamine or a derivative thereof is usually in a substantially anhydrous state while adding a tetracarboxylic acid or a derivative thereof to the diamine.
  • the reaction is performed at a temperature of about 70 ° C. or lower, preferably 40 ° C. or lower.
  • the polyamic acid solution When recovering the polyamic acid from the polyamic acid solution, the polyamic acid solution is poured into a poor solvent of the polyamic acid such as water or methanol to precipitate the polyamic acid in water or methanol (reprecipitation) and then collect it. Can do.
  • the precipitated polyamic acid can be recovered as polyamic acid by filtration and / or dehydration or liquid removal.
  • the recovered polyamic acid is dried and subjected to heat ring closure by treating at a temperature of 80 to 370 ° C. for 0.1 to 100 hours to obtain a polyamideimide.
  • Examples of the aromatic, aliphatic or alicyclic tetracarboxylic acid or derivative thereof, and diamine or derivative thereof that can be used for the synthesis of polyamideimide include the same compounds as those used for the synthesis of polyimide described above.
  • polyamideimide constituted as described above those having a weight average molecular weight of 30,000 to 1,000,000 are used from the viewpoint of easy film formation.
  • the base film of the present invention preferably contains the heat resistant resin as a main component.
  • Containing a heat resistant resin as a main component means that the content of the heat resistant resin in the base film is 50% by mass or more.
  • the content of the heat resistant resin in the base film is preferably 80% by mass or more.
  • the content of the heat resistant resin in the base film is 50% by mass or more, it is preferable from the viewpoint that mechanical strength such as bending resistance, heat resistance, and transparency are good.
  • the content of the heat-resistant resin in the base film is 50% by mass or more, the base film has an elastic modulus even at a relatively high process temperature (for example, a high temperature exceeding 150 ° C.). It is thought that damage due to tension can be reduced because it does not decrease too much.
  • the glass transition temperature of the heat resistant resin according to the present invention is 180 ° C. or higher. When the glass transition temperature is less than 180 ° C., vacuum film formation becomes difficult.
  • the glass transition temperature is preferably 180 ° C. or higher and 350 ° C. or lower, and more preferably 265 ° C. or higher and lower than 300 ° C.
  • the glass transition temperature of the heat resistant resin can be measured according to JIS K7121 (1987). Specifically, for example, using a DSC6220 manufactured by Seiko Instruments Inc. as a measuring device, measurement can be performed under the conditions of a 10 mg polyarylate sample and a heating rate of 20 ° C./min.
  • the glass transition temperature of the heat resistant resin can be adjusted depending on the type of units constituting the heat resistant resin.
  • the glass transition temperature of polyarylate can be adjusted by the type of aromatic diol component that is a constituent unit thereof.
  • a “unit derived from a bisphenol having a sulfur atom in the main chain” may be contained as an aromatic diol component unit.
  • the base film according to the present invention has an arithmetic average roughness Ra of 0.5 nm or more and 4.0 nm or less at least on one side in addition to the Tg of the heat resistant resin being 180 ° C. or higher. It is essential. If Ra is 0.5 nm or more, generation
  • the arithmetic average roughness Ra can be measured by the method described in the examples.
  • the base film of the present invention can achieve a desired effect as long as Ra on at least one side is within the above range, but Ra on both sides may be within the above range.
  • Ra on both sides may be within the above range.
  • the base film In order to set at least one surface of the base film to a predetermined Ra range, it can be realized by manufacturing the base film using various known methods. For example, in the base film production process, a matting agent is added to the dope and a stretching process or the like is performed. After the film is formed, a method such as an excimer light irradiation method or a resoftening press transfer method is used. Examples include a method in which at least one surface of the material film has a predetermined Ra.
  • the base film of the present invention may contain other additives such as an ultraviolet absorber, a peeling accelerator, and a phase difference adjusting agent.
  • phase difference adjusting agent is a generic term for additives having a function of adjusting the degree of expression of retardation of a film.
  • phase difference adjusting agent any of a sugar ester compound, a non-phosphate ester compound, an acrylic compound, and a vinyl compound may be used.
  • vinyl compound a vinyl compound containing an aryl group such as polystyrene in the structure. It is preferable that
  • a step of obtaining a dope by mixing a heat resistant resin, a matting agent, and a solvent comprising: a step of obtaining a film-like material by stretching; and (3) a drying step of drying the film-like material.
  • a re-softening press comprising: (3) drying the film-like material; and (5) drying the film-like material; and (5) re-softening press transferring at least one surface of the film-like material.
  • a substrate film production method (Method C) having a transfer step can be employed.
  • the method for producing a base film of the present invention may be a method in which two or more of the above methods A to C are combined.
  • the base film can be manufactured using, for example, a manufacturing apparatus shown in FIG.
  • the film manufacturing apparatus 10 illustrated in FIG. 1 can include a casting apparatus 20 and a drying apparatus 30. Each step will be described below.
  • Step of obtaining a dope includes mixing a heat-resistant resin and a solvent. You may have adding a mat agent and a hydrogen bondable solvent as needed.
  • the solvent is preferably a solvent having a boiling point of 70 ° C. or less (preferably a good solvent) from the viewpoint of lowering the drying temperature.
  • the good solvent 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 the heat-resistant resin in the dope is 8% by mass or more, preferably about 10 to 30% by mass.
  • the polymer solution may remove insoluble matters and foreign matters by filtration.
  • the matting agent is added to adjust Ra on at least one side of the base film within a predetermined range.
  • the matting agent fine particles such as silica, alumina, titanium oxide or ceria can be used.
  • the average primary particle size of the matting agent in the present invention is preferably 5 nm or more and less than 300 nm. When the average primary particle size of the matting agent is 5 nm or more, Ra of at least one side of the base film can be more easily set within a predetermined range. When the average primary particle size is less than 300 nm, The effect which suppresses peeling of the electrode originating in unevenness etc. is acquired.
  • the matting agent dispersed in a dispersion medium may be used.
  • the dispersion medium examples include alcohols such as ethanol, solvents for preparing a dope (polymer solution), and the like. Is preferred.
  • the matting agent can be dispersed with alcohol and added to a solvent or the like for preparing a dope (polymer solution). By devising the order of addition in this way, an effect of uniformly dispersing the matting agent can be expected.
  • the matting agent may exist as primary particles in the base film, or may exist as a plurality of particles aggregate to form secondary particles (secondary aggregates).
  • the average secondary particle size of the matting agent is preferably in the range of 0.005 to 3 ⁇ m, more preferably in the range of 0.005 to 2 ⁇ m, A range of 0.005 to 1 ⁇ m is particularly preferable.
  • the average primary particle size of the matting agent used in the present invention can be measured by a laser diffraction / scattering method or the like. For example, it can be measured using a particle size distribution analyzer Microtrac (manufactured by Nikkiso Co., Ltd.). When the silica particles are surface modified, the particle diameter of the particles including the surface modification is defined as the particle diameter in the present invention.
  • the average secondary particle size of the matting agent is measured by observing particles with a transmission electron microscope (magnification of 500,000 to 2,000,000 times), observing 100 particles, measuring the particle size, and calculating the average value. Is the average secondary particle size.
  • the hydrogen bonding solvent is not particularly limited, and in addition to the above alcohol, ketones (for example, acetone), carboxylic acids (for example, acetic acid), ethers (for example, tetrahydrofuran, dioxane, etc.), pyrrolidones (For example, N-methylpyrrolidone and the like), amines (for example, trimethylamine, pyridine and the like), ammonia and the like can be exemplified.
  • ketones for example, acetone
  • carboxylic acids for example, acetic acid
  • ethers for example, tetrahydrofuran, dioxane, etc.
  • pyrrolidones for example, N-methylpyrrolidone and the like
  • amines for example, trimethylamine, pyridine and the like
  • ammonia and the like can be exemplified.
  • the matting agent can be contained, for example, in a proportion of 0.05 to 1.0 part by mass, and further in a proportion of 0.1 to 0.5 part by mass with respect to 100 parts by mass of the heat resistant resin. It is preferably contained, more preferably 0.1 to 0.3 parts by mass. Within such a range, there are technical effects of both transparency and slipperiness.
  • Step of obtaining a film-like material comprises casting the dope and obtaining a film-like material.
  • the cast film is dried to obtain a film-like material.
  • the metal support 23 can be an endless stainless steel belt conveyed by a roll 23A.
  • the casting membrane can be dried by various methods, for example, by adjusting the surface temperature of the metal support 23 and applying air to the casting membrane.
  • the surface temperature of the metal support 23 can be controlled by, for example, a method in which hot water is brought into contact with the back side of the metal support.
  • the drying temperature of the cast film on the belt (the surface temperature of the metal support 23 and the temperature of the wind W).
  • the drying temperature of the cast film specifically, the surface temperature of the metal support 23 and the temperature of the wind applied to the cast film are each preferably less than 70 ° C., preferably 5 to 60 ° C. More preferably, it is ⁇ 50 ° C., and further preferably 15 ⁇ 40 ° C. Drying may be performed at a time, or may be performed stepwise by changing the temperature.
  • the surface where the film-like material and air come into contact with each other by the casting operation described above is a surface where Ra is within the scope of the present invention, and the surface which contacts the metal support 23 is a mirror surface. It remains. That is, a film-like product in which only Ra on one side is within the scope of the present invention is obtained.
  • Ra of both surfaces is to be within a predetermined range
  • Ra in a predetermined range can be realized by performing a stretching operation after obtaining a film-like material. For example, the obtained film-like material is stretched 1.2 times at 170 ° C.
  • the Ra on both sides can be adjusted within a predetermined range by stretching 1.2 times at 230 ° C.
  • the drying process is a process of drying the film-like material.
  • a known drying apparatus can be used and is not particularly limited.
  • the drying temperature is preferably 70 to 140 ° C.
  • the drying time is preferably 3 to 60 minutes.
  • a base film having Ra of at least one side within a predetermined range can be obtained after the drying step.
  • a base film having Ra of at least one side within a predetermined range can be obtained after the drying step.
  • no matting agent is added in the step of obtaining the dope, by performing excimer light irradiation treatment or resoftening press transfer after the drying step, at least Ra on one side is within a predetermined range.
  • a substrate film can be obtained.
  • the film-like material obtained in the above (3) drying step may be treated by excimer light irradiation treatment so that at least one surface Ra is within a predetermined range.
  • the illumination intensity of the excimer light in terms of making the lifting of the film-like material is in the range of 30 ⁇ 300 mW / cm 2, and more preferably in the range of 50 ⁇ 200 mW / cm 2 . If it is 30 mW / cm 2 or more, Ra can be efficiently contained in the above range, and 300 mW / cm 2 or less is preferable because it hardly damages the film-like material.
  • the cumulative amount of excimer light on the surface that makes the film-like object float is preferably in the range of 200 to 10000 mJ / cm 2 , and more preferably in the range of 500 to 7000 mJ / cm 2 . If it is this range, a crack generation and the thermal deformation of a base material can be suppressed.
  • a rare gas excimer lamp such as Xe, Kr, Ar, Ne or the like is preferably used.
  • the Xe excimer lamp emits ultraviolet light having a short wavelength of 172 nm at a single wavelength, and thus has excellent luminous efficiency. Since this light has a large oxygen absorption coefficient, it can generate radical oxygen atom species and ozone at a high concentration with a very small amount of oxygen.
  • the energy of light having a short wavelength of 172 nm has a high ability to dissociate organic bonds. Due to the high energy possessed by the active oxygen, ozone and ultraviolet radiation, it is possible to realize a treatment for imparting a predetermined Ra to the surface of the base film in a short time.
  • the oxygen concentration at the time of excimer light irradiation is preferably in the range of 1 to 10000 volume ppm, more preferably in the range of 3 to 5000 volume ppm, and still more preferably in the range of 5 to 4000 volume ppm.
  • a dry inert gas is preferable, and dry nitrogen gas is particularly preferable from the viewpoint of cost.
  • the oxygen concentration can be adjusted by measuring the flow rate of oxygen gas and inert gas introduced into the irradiation chamber and changing the flow rate ratio.
  • the film-like material obtained in the above (3) drying step may be subjected to resoftening press transfer (embossing treatment) so that Ra on at least one side has a predetermined range.
  • the re-softening press transfer has a transfer step of transferring the concavo-convex pattern of the mold onto the entire surface or a part of the base film.
  • FIG. 2A is a schematic cross-sectional view showing the base film 1 and the mold 2 immediately before the transfer step in an example of the method of manufacturing the base film in the present invention
  • FIG. It is a schematic sectional drawing which shows the material film 1 and the casting_mold
  • FIG.2 (C) is a schematic sectional drawing which shows the base film 1 and the casting_mold
  • the viscosity of the base film is 1 to 1200 Pa ⁇ s. When the viscosity is within the above range, the uneven height is uniform, and the transfer rate can be appropriate.
  • the viscosity of the base film is preferably 1 to 1000 Pa ⁇ s, more preferably 5 to 500 Pa ⁇ s, from the viewpoint of more effectively suppressing the remaining peeling on the mold.
  • the viscosity is a value measured using a dynamic viscoelasticity measuring apparatus (TA Instruments Co., Ltd.) by a method defined in JIS-K7117.
  • the load on the base material film of the mold is 1 to 350 N / mm.
  • the load on the base film is set to 1 to 350 N / mm, particularly 1 to 300 N / mm from the viewpoint of further improving the uniformity of the unevenness height and further effectively suppressing the peeling residue on the mold. Is preferred.
  • the time for which the load within the above range is continuously applied to the base film is not particularly limited as long as the object of the present invention is achieved, and is preferably 10 ⁇ 4 to 10 ⁇ 1 seconds.
  • the conveyance speed of the base film is 25 to 170 m / min. If the conveyance speed is too low, the processing time is too long, and the transfer rate becomes too high. If the conveyance speed is too high, the processing time is too short, so that the transfer shape is not stable or the transfer rate is too low.
  • the conveyance speed of the base film is set to 30 to 150 m / min, particularly 30 to 100 m / min, from the viewpoint of further improving the uniformity of the unevenness height and further effectively suppressing the peeling residue on the mold. It is preferable.
  • the transfer processing conditions such as the load on the base film and the conveyance speed of the base film are employed.
  • the re-softening method of the base film only needs to be soft enough to achieve the above-described base film viscosity.
  • a heat softening method in which softening is performed by heating may be employed, or softening by swelling with a solvent.
  • a swelling softening method may be employed.
  • a transfer device shown in FIG. 3 can be used.
  • the base film 1 is transported at a predetermined transport speed, passes through between the mold roll 2 and the back roll 3 after reaching the predetermined base film viscosity by heating in the heating chamber 10. As a result, transfer with a predetermined load is performed. As a result, a base film having Ra within the above range is obtained.
  • the base film of the present invention has high transparency and heat resistance like the conventional base film, it can be used in a wide range of applications that require these characteristics; for example, flexible panel displays (organic EL displays, liquid crystals) Transparent substrates or transparent electrode substrates (substrates instead of glass substrates) in displays, electronic paper, etc.) and solar cells; insulating substrates and cover films for flexible printed circuit boards (FPC) for applications where transparency is required; Used for transparent conductive film and the like.
  • FPC flexible printed circuit boards
  • a vacuum film forming process may be performed under a high temperature condition in a vacuum state using a vacuum film forming apparatus equipped with a can roll.
  • production of the force between a base film and the can roll (cooling roll) of an apparatus will be suppressed, and the minute change on a base film will be suppressed.
  • Can do Thereby, the color nonuniformity of a base film and the keystroke performance of a touch panel can be improved.
  • this invention provides the manufacturing method of a transparent electrode including forming a transparent electrode by the vacuum film-forming method on the at least one surface of the base film for transparent electrodes of this invention. More specifically, in the present invention, the surface having the arithmetic average roughness Ra of the transparent electrode substrate film of 0.5 nm or more and 4.0 nm or less is brought into contact with the outer peripheral surface of the can roll and conveyed.
  • a method for producing a transparent electrode is provided, which includes forming the transparent electrode by a vacuum film formation method.
  • this invention also provides the manufacturing method of a touch panel including producing a transparent electrode with the manufacturing method of the said transparent electrode.
  • polyimide 1 (PI1) Under a nitrogen atmosphere, NMP 1062.5 kg was charged with 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) 107.0 kg (0.26 kmol), 4, 40.81 kg (0.13 kmol) of 4′-oxydiphthalic anhydride (ODPA) and 37.15 kg (0.13 kmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) The resulting mixture was stirred and reacted at room temperature and atmospheric pressure for 3 hours to obtain a polyamic acid solution (polyamic acid composition).
  • BAPP 2,2-bis [4- (4-aminophenoxy) phenyl] propane
  • ODPA 4′-oxydiphthalic anhydride
  • BPDA 4,4′-biphenyltetracarboxylic dianhydride
  • the obtained polyamic acid was heated and stirred while removing condensed water from the system at 100 ° C. for 1 hour and then at 200 ° C. for 1 hour to obtain a polyimide solution.
  • the resulting polyimide solution is allowed to cool and then poured into methanol to precipitate the polyimide.
  • substrate films A1 to A9 and C1 to C4 were produced using the above components.
  • Aerosil registered trademark
  • R812 11 parts by mass
  • Ethanol 89 parts by mass
  • the above components were stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin to prepare a matting agent dispersion 1.
  • the matting agent dispersion 1 was slowly added to the dissolution tank containing methylene chloride with sufficient stirring.
  • the amounts used of methylene chloride and matting agent dispersion 1 are as follows: Methylene chloride 99 parts by mass Matting agent dispersion 1 5 parts by mass Further, dispersion was performed with an attritor so that the particle diameter of the secondary particles was a predetermined size (average secondary particle diameter: 0.01 ⁇ m). This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a matting agent addition liquid 1.
  • a dope 1 having the following composition was prepared: Methylene chloride 390 parts by mass Hydrogen bonding solvent (ethanol) 10 parts by mass Polyarylate (PAR) 100 parts by mass Matting agent addition solution 1 (as solid content of matting agent) 0.15 parts by mass More specifically, the above components was gradually heated to 45 ° C. while stirring to completely dissolve the resin component. The obtained liquid was used as Azumi Filter Paper No. The dope 1 was prepared by filtration using 244.
  • the obtained dope 1 was uniformly cast on a stainless steel belt of a belt casting apparatus.
  • a stainless steel belt having a length of 20 m was used.
  • the surface temperature of the stainless steel belt is 35 ° C. and 35 ° C. wind is applied to the casting film to evaporate the solvent until the residual solvent amount is 38%, and then the film is peeled off from the stainless steel belt to obtain a film-like material. It was.
  • the obtained film-like product was dried for 30 minutes while being conveyed in a drying apparatus at 125 ° C. by a number of rolls, and then subjected to knurling with a width of 15 mm and a height of 10 ⁇ m at both ends in the width direction of the film.
  • a base film A1 having a thickness of 20 ⁇ m was obtained.
  • Substrate films A2 to A4 were prepared in the same manner as the substrate film A1, except that the addition amount of the matting agent was as described in Table 1 in the preparation of the substrate film.
  • Base film A5 In the production of the base film, a base film A5 was produced in the same manner as the base film A1, except that the type of matting agent was Aerosil (registered trademark) NAX50 (manufactured by Nippon Aerosil Co., Ltd.).
  • Aerosil registered trademark
  • NAX50 manufactured by Nippon Aerosil Co., Ltd.
  • a dope 2 having the following composition was prepared in the same manner as described above (preparation of dope 1): Methylene chloride 390 parts by mass Hydrogen bonding solvent (ethanol) 10 parts by mass Polyarylate (PAR) 100 parts by mass Except for using the obtained dope 2, film formation, stretching, and drying treatment were performed in the same manner as in Example 1. It was. Thereafter, one side of the obtained film was subjected to excimer treatment with the following apparatus and conditions to form irregularities, wound up in a roll shape, and a base film A6 was produced.
  • Excimer light irradiation device MECL-M-1-200 (MDM Co., Ltd.) Excimer light irradiation condition Lamp filled gas: Xe Wavelength: 172nm Excimer light intensity: 130 mW / cm 2 (172 nm) Distance between sample and light source: 2mm Oxygen concentration in irradiation device: 0.3% (nitrogen purge) Integrated light quantity: 3550 mJ / cm 2 (Base film A7) Except for using the obtained dope 2, film formation, stretching, and drying treatment were performed in the same manner as in Example 1. Thereafter, using the apparatus shown in FIG. 1, while carrying the obtained film at a conveyance speed of 25 m / min, the embossing process (resoftening press transfer method) shown below is performed to form irregularities, and the substrate Film A7 was obtained.
  • Lamp filled gas Xe Wavelength: 172nm
  • Excimer light intensity 130 mW / cm 2 (172 nm)
  • Distance between sample and light source 2
  • the film was transferred onto the entire first surface 1a of the film 1 at a transfer rate of 80% (FIG. 2B). Thereafter, the film was released from the mold (FIG. 2C), and the convex flat film was wound up to obtain a base film A7.
  • Substrate films A8 and A9 were produced by the same method as the substrate film A1, except that the types of resin described in Table 1 were used in the production of the substrate film.
  • Base film C1 In the production of the base film, a base film C1 was produced in the same manner as the base film A1, except that the dope 2 was used.
  • Base film C2 In the production of the base film, a base film C2 was produced in the same manner as the base film A1, except that the addition amount of the matting agent was as described in Table 1.
  • Base film C3 In the production of the base film, a base film C2 was produced in the same manner as the base film A7, except that the surface Ra of the base film was 50 nm.
  • Base film C4 A base film C4 was prepared in the same manner as the base film A1, except that in the preparation of the base film, the type of matting agent was silica particles (Seahoster (registered trademark) KE-S30, manufactured by Nippon Shokubai Co., Ltd.).
  • the type of matting agent was silica particles (Seahoster (registered trademark) KE-S30, manufactured by Nippon Shokubai Co., Ltd.).
  • ⁇ Measurement of physical properties of substrate film Measurement of arithmetic average roughness (Ra)
  • Example 1 A surface of the base film A1 with Ra of 0.5 nm is brought into contact with the outer peripheral surface of the can roll, and an ITO film with a thickness of 50 nm is formed on the base film A1 by a sputtering method, and patterned by a photolithography method.
  • a transparent electrode was formed. Specifically, sputtering was performed as follows.
  • pre-sputtering of ITO target> Under vacuum conditions, pre-sputtering was performed on the ITO oxide target that had been set in advance on the electrodes of the high magnetic field RF superimposed DC sputter deposition apparatus under the following conditions. This was performed until the in-line resistance value became stable.
  • DC power density 1.1 W / cm 2
  • Horizontal magnetic field on target surface 100mT Temperature: 150 ° C
  • the main sputtering was performed under the following conditions using the same high magnetic field RF superimposed DC sputtering film forming apparatus as described above to form an ITO film having a thickness of 28 nm.
  • each transparent electrode was produced in the same manner as in Example 1 except that the type of the base film was as described in Table 1.
  • b * value was measured by the transmission mode using the spectrocolorimeter (CM-3600d, Konica Minolta Co., Ltd.), and it evaluated according to the following evaluation rank.
  • the b * value indicates that the L * a * b * represents the value of b * in the color system, transmitted light as the substrate film is large values are yellowish.
  • the evaluation results are shown in Table 2.
  • ⁇ 0 or more and less than 1.0 ⁇ : 1.0 or more.
  • Each touch panel member was produced using each of the transparent electrodes patterned as described in JP-T-2010-541109.
  • the touch panel member bonded in advance of 21.5-inch VAIOTap 21 (SVT212219DJB) made by SONY was peeled off, and the prepared touch panel member was bonded to prepare each touch panel display device.
  • the input touch panel display device was touched with an input pen from above the cover glass side under the conditions of a keystroke speed of 2 Hz and a load of 150 g Pressed 15,000 times.
  • the pen tip material of the input pen was rubber (polyacetal), and R was 0.8 mm.
  • the measuring board laid below is a glass substrate, and the conductive mesh is placed on the glass substrate, and the input pen is pressed from above with a load of 300 g, sliding distance is 5 cm, reciprocating 1 second (5 cm.
  • the experiment was conducted using an experimental apparatus that can be repeatedly slid under the condition of reciprocation in 1 second.
  • ⁇ The increase rate of the surface resistance value before and after the keying test shows a value of less than 1.5%.
  • X The increase rate of the surface resistance value before and after the keying test shows a value of 1.5% or more.

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Abstract

Le problème décrit par la présente invention est de fournir un substrat de film d'électrode transparente capable de supprimer une irrégularité de couleur et de maintenir les performances de manipulation d'un panneau tactile même après une utilisation à long terme. La solution selon l'invention porte sur un substrat de film d'électrode transparente contenant une résine résistante à la chaleur ayant une température de transition vitreuse supérieure ou égale à 180 °C, et la rugosité moyenne arithmétique Ra d'au moins une surface du substrat de film d'électrode transparente étant de 0,5 à 4,0 nm.
PCT/JP2018/006962 2017-03-10 2018-02-26 Substrat de film d'électrode transparente et son procédé de production Ceased WO2018163884A1 (fr)

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