JP2012218163A - Transparent conductive film, laminate, touch panel, and display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transparent conductive film excellent in light transmittance, heat resistance, and mechanical strength and a touch panel including the film.SOLUTION: The transparent conductive film has a transparent conductive membrane on at least one side of a base material. The base material contains an aromatic polyether polymer having a glass transition temperature (Tg) of 230-350°C by differential scanning calorimetry (DSC, temperature rise speed 20°C/min).

Description

  The present invention relates to a transparent conductive film, a laminate, a touch panel, and a display device.

Conventionally, so-called conductive glass in which a transparent conductive film is formed on glass has been used as the transparent conductive member.
However, the conductive glass is inferior in flexibility and workability because the base material is glass, it is difficult to form a transparent conductive film, and further, it is difficult to reduce the weight of the touch panel.

  Therefore, in recent years, in addition to flexibility and workability, it has excellent impact resistance and light weight, so that it is a transparent conductive film based on various plastic films including polyethylene terephthalate film and polycarbonate. Are used (Patent Documents 1 and 2).

JP 2010-20473 A JP 2007-308675 A

However, these plastic films were inferior in heat resistance. Therefore, it has been difficult to form a transparent conductive film on the film.
This invention is made | formed in view of such a problem, and it aims at providing the transparent conductive film excellent in light transmittance, heat resistance, and mechanical strength.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a transparent conductive film obtained from a base material containing an aromatic polyether polymer having a specific glass transition temperature can solve the above problems. The present inventors have found that the film can be obtained, and further found that the retardation of the film is small, thereby completing the present invention.
That is, the present invention provides the following [1] to [19].

[1] A transparent conductive film having a transparent conductive film on at least one surface of a base material, the base material having a glass transition temperature (Tg) determined by differential scanning calorimetry (DSC, heating rate 20 ° C./min). A transparent conductive film comprising an aromatic polyether polymer having a temperature of 230 to 350 ° C.
[2] On at least one surface of a substrate containing an aromatic polyether polymer having a glass transition temperature (Tg) of 230 to 350 ° C. by differential scanning calorimetry (DSC, heating rate 20 ° C./min), After forming a transparent conductive film, the transparent conductive film formed by annealing at the temperature below (Tg minus 20 degreeC of a base material).
[3] The transparent conductive film according to [1] or [2], wherein the transparent conductive film includes indium oxide and 2 to 18% by weight of tin oxide (provided that the entire transparent conductive film is 100% by weight). Transparent conductive film.
[4] The transparent conductive film according to any one of [1] to [3], wherein the film thickness of the transparent conductive film is 20 to 50 nm.
[5] Any one of [1] to [4], having at least one inorganic layer formed on at least one surface of the substrate without heating or by sputtering at a temperature of (Tg minus 20 ° C. of the substrate) or lower. The transparent conductive film described in 1.
[6] The transparent conductive film according to any one of [1] to [5], wherein the inorganic layer has a refractive index of 1.4 to 2.5.
[7] The transparent conductive film according to any one of [1] to [6], wherein the inorganic layer has a thickness of 3 to 70 nm.

  [8] The aromatic polyether polymer has at least one structural unit (i) selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). , [1] to [7] The transparent conductive film according to any one of [7].

（式（１）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に炭素数１〜１２の１価の有機基を示し、ａ〜ｄは、それぞれ独立に０〜４の整数を示す。）

(In Formula (1), R < ¹ > -R < ⁴ > shows a C1-C12 monovalent organic group each independently, and ad shows the integer of 0-4 each independently.)

（式（２）中、Ｒ¹〜Ｒ⁴およびａ〜ｄは、それぞれ独立に前記式（１）中のＲ¹〜Ｒ⁴およびａ〜ｄと同義であり、Ｙは、単結合、−ＳＯ₂−または＞Ｃ＝Ｏを示し、Ｒ⁷およびＲ⁸は、それぞれ独立にハロゲン原子、炭素数１〜１２の１価の有機基またはニトロ基を示し、ｇおよびｈは、それぞれ独立に０〜４の整数を示し、ｍは０または１を示す。但し、ｍが０の時、Ｒ⁷はシアノ基ではない。）

(In Formula (2), R < ¹ > -R < ⁴ > and ad are respectively synonymous with R < ¹ > -R < ⁴ > and said ad in said Formula (1), Y is a single bond, -SO _2- or> C = O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and g and h each independently represent 0 to 4 represents an integer of 4 and m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group.

  [9] The aromatic polyether polymer further includes at least one structural unit (ii) selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4): The transparent conductive film according to any one of [1] to [8].

（式（３）中、Ｒ⁵およびＲ⁶は、それぞれ独立に炭素数１〜１２の１価の有機基を示し、Ｚは、単結合、−Ｏ−、−Ｓ−、−ＳＯ₂−、＞Ｃ＝Ｏ、−ＣＯＮＨ−、−ＣＯＯ−または炭素数１〜１２の２価の有機基を示し、ｅおよびｆは、それぞれ独立に０〜４の整数を示し、ｎは０または１を示す。）

(In formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and Z represents a single bond, —O—, —S—, —SO ₂ —, > C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, e and f each independently represent an integer of 0 to 4, and n represents 0 or 1 .)

（式（４）中、Ｒ⁷、Ｒ⁸、Ｙ、ｍ、ｇおよびｈは、それぞれ独立に前記式（２）中のＲ⁷、Ｒ⁸、Ｙ、ｍ、ｇおよびｈと同義であり、Ｒ⁵、Ｒ⁶、Ｚ、ｎ、ｅおよびｆは、それぞれ独立に前記式（３）中のＲ⁵、Ｒ⁶、Ｚ、ｎ、ｅおよびｆと同義である。）

(In the formula ^{(4), R 7, R} 8, Y, m, g and h are each R ⁷ in independent to the formula ^{(2), R 8, Y} , m, synonymous with g and h, R ^5, R ^6, Z, n, e and f are as defined each R ⁵ in the formula (3) independently, R ^6, Z, n, e and f.)

[10] In any one of [1] to [9], in the aromatic polyether polymer, a molar ratio of the structural unit (i) to the structural unit (ii) is 50:50 to 100: 0. The transparent conductive film of crab.
[11] The aromatic polyether polymer according to any one of [1] to [10], wherein a polystyrene-reduced weight average molecular weight by gel permeation chromatography (GPC) is 5,000 to 500,000. Transparent conductive film.
[12] The transparent conductive film according to any one of [1] to [11], wherein the total light transmittance according to a JIS K7105 transparency test method at a thickness of 30 μm of the substrate is 85% or more.
[13] The transparent conductive film according to any one of [1] to [12], wherein a YI value (yellow index) at a thickness of 30 μm of the substrate is 3.0 or less.
[14] The transparent conductive film according to any one of [1] to [13], wherein a thickness direction retardation (Rth) at a thickness of 30 μm of the substrate is 200 nm or less.
[15] The transparent conductive film according to any one of [1] to [14], which is for a capacitive touch panel.

[16] At least one surface of the transparent conductive film according to any one of [1] to [15] is selected from the group consisting of a polarizing plate, an antireflection film, a hard coat film, an antistatic film, and an antifouling film. A laminate comprising at least one kind of layer.
[17] A touch panel comprising the transparent conductive film according to any one of [1] to [15] or the laminate according to [16].
[18] The touch panel according to [17], which is a capacitive touch panel.
[19] A display device including the touch panel according to [17] or [18].

  The transparent conductive film of the present invention is excellent in light transmittance, heat resistance, heat resistance coloring property and mechanical strength, and has a small retardation. Therefore, the transparent conductive film of the present invention is easily manufactured and can be suitably used for touch panels, particularly for low reflection touch panels and capacitive touch panels.

≪Transparent conductive film≫
The transparent conductive film of the present invention has a transparent conductive film on at least one surface of a base material, and the base material has a glass transition temperature (Tg) by differential scanning calorimetry (DSC, heating rate 20 ° C./min). ) Includes an aromatic polyether polymer (hereinafter also referred to as “polymer (I)”) having a temperature of 230 to 350 ° C.
In addition, the transparent conductive film of the present invention is annealed at a temperature of (base material Tg minus 20 ° C.) or lower after forming a transparent conductive film on at least one surface of the base material containing the polymer (I). It is obtained by processing.

<Base material>
The base material used in the present invention contains the polymer (I).
The glass transition temperature of the polymer (I) is preferably 240 to 330 ° C, more preferably 250 to 300 ° C.
Since the base material comprising such a polymer (I) has excellent heat resistance and heat resistance coloring property, it is suitably used for a touch panel. In addition, when the transparent conductive film is formed, the temperature range at which the substrate can be heated is widened. Therefore, the film forming method is not limited, and a transparent conductive film can be easily produced. .
Further, the base material on which the transparent conductive film is formed is not colored and maintains high light transmittance even when annealed at a high temperature (temperature of Tg minus 20 ° C. or lower). can do.
In the present invention, “heat resistant colorability” refers to the difficulty of coloring when heat-treated in the atmosphere at a high temperature (230 ° C.) for about 1 hour.

  The polymer (I) includes a structural unit represented by the following formula (1) (hereinafter also referred to as “structural unit (1)”) and a structural unit represented by the following formula (2) (hereinafter referred to as “structural unit (2)”. It is preferably a polymer having at least one structural unit (i) selected from the group consisting of (also referred to as “polymer (II)” hereinafter). When the polymer has the structural unit (i), an aromatic polyether polymer having a glass transition temperature of 230 to 350 ° C. can be obtained. Since such a polymer (II) is excellent in transparency and heat-resistant colorability, a base material comprising the polymer has high light transmittance and excellent heat-resistant colorability. Since the base material comprising the polymer (II) has these excellent properties in a well-balanced manner, even if it is annealed at a high temperature (temperature below (Tg minus 20 ° C. of the base material)), There is no coloring and it can maintain high light transmittance, and it is suitably used for a touch panel, particularly a capacitive touch panel.

In said formula (1), R < ¹ > -R < ⁴ > shows a C1-C12 monovalent organic group each independently. a to d each independently represent an integer of 0 to 4, preferably 0 or 1.
The monovalent organic group having 1 to 12 carbon atoms includes a monovalent hydrocarbon group having 1 to 12 carbon atoms and 1 to 1 carbon atoms containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. And 12 monovalent organic groups.

  Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and 6 to 12 carbon atoms. An aromatic hydrocarbon group etc. are mentioned.

  The linear or branched hydrocarbon group having 1 to 12 carbon atoms is preferably a linear or branched hydrocarbon group having 1 to 8 carbon atoms, and the linear or branched carbon group having 1 to 5 carbon atoms. A hydrogen group is more preferable.

  Preferable specific examples of the linear or branched hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and n-pentyl. Group, n-hexyl group, n-heptyl group and the like.

  As said C3-C12 alicyclic hydrocarbon group, a C3-C8 alicyclic hydrocarbon group is preferable, and a C3-C4 alicyclic hydrocarbon group is more preferable.

  Preferable specific examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group; cyclobutenyl group, cyclopentenyl group, and cyclohexenyl group. And the like. The bonding site of the alicyclic hydrocarbon group may be any carbon on the alicyclic ring.

  Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, and a naphthyl group. The bonding site of the aromatic hydrocarbon group may be any carbon on the aromatic ring.

  Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom include an organic group consisting of a hydrogen atom, a carbon atom and an oxygen atom, and among them, a total carbon consisting of an ether bond, a carbonyl group or an ester bond and a hydrocarbon group. Preferable examples include organic groups of formulas 1 to 12.

  Examples of the organic group having 1 to 12 carbon atoms having an ether bond include an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, an alkynyloxy group having 2 to 12 carbon atoms, and 6 to 12 carbon atoms. And an aryloxy group having 1 to 12 carbon atoms and the like. Specific examples include a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, a butoxy group, a phenoxy group, a propenyloxy group, a cyclohexyloxy group, and a methoxymethyl group.

Moreover, as a C1-C12 organic group which has a carbonyl group, a C2-C12 acyl group etc. can be mentioned. Specific examples include an acetyl group, a propionyl group, an isopropionyl group, and a benzoyl group.
As a C1-C12 organic group which has an ester bond, a C2-C12 acyloxy group etc. are mentioned. Specific examples include an acetyloxy group, a propionyloxy group, an isopropionyloxy group, and a benzoyloxy group.

  Examples of the organic group having 1 to 12 carbon atoms including a nitrogen atom include an organic group consisting of a hydrogen atom, a carbon atom and a nitrogen atom, and specifically, a cyano group, an imidazole group, a triazole group, a benzimidazole group and a benzine. A triazole group etc. are mentioned.

  Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom and a nitrogen atom include an organic group consisting of a hydrogen atom, a carbon atom, an oxygen atom and a nitrogen atom. Specifically, an oxazole group, an oxadiazole group, Examples include a benzoxazole group and a benzoxadiazole group.

As R < ¹ > -R < ⁴ > in said Formula (1), a C1-C12 monovalent hydrocarbon group is preferable, a C6-C12 aromatic hydrocarbon group is more preferable, and a phenyl group is further more preferable.

In the formula (2), R ¹ to R ⁴ and a~d are the same as R ¹ to R ⁴ and a~d each independently the formula (1), Y represents a single bond, -SO _2- or> C = O, R ⁷ and R ⁸ each independently represents a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group. g and h each independently represent an integer of 0 to 4, preferably 0.
Examples of the monovalent organic group having 1 to 12 carbon atoms include the same organic groups as the monovalent organic group having 1 to 12 carbon atoms in the formula (1).

The polymer (II) has a molar ratio of the structural unit (1) to the structural unit (2) (however, the sum of the structural unit (1) and the structural unit (2) is 100). However, from the viewpoint of optical properties, heat resistance and mechanical properties, it is preferable that the structural unit (1): structural unit (2) = 50: 50 to 100: 0, and the structural unit (1): structural unit (2). = 70: 30 to 100: 0 is more preferable, and structural unit (1): structural unit (2) is more preferably 80:20 to 100: 0.
Here, the mechanical properties refer to properties such as the tensile strength, breaking elongation and tensile elastic modulus of the polymer.

  The polymer (II) further has at least one structural unit (ii) selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). May be. It is preferable that the polymer (II) has such a structural unit (ii) because the mechanical properties of the substrate having the polymer (II) are improved.

In the formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, Z represents a single bond, —O—, —S—, —SO ₂ —, > C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, and n represents 0 or 1. e and f each independently represent an integer of 0 to 4, preferably 0.
Examples of the monovalent organic group having 1 to 12 carbon atoms include the same organic groups as the monovalent organic group having 1 to 12 carbon atoms in the formula (1).

  The divalent organic group having 1 to 12 carbon atoms includes a divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, an oxygen atom, and a nitrogen atom. A divalent organic group having 1 to 12 carbon atoms containing at least one atom selected from the above, and a divalent organic group having 1 to 12 carbon atoms containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom. And halogenated organic groups.

  Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and Examples thereof include a bivalent aromatic hydrocarbon group having 6 to 12 carbon atoms.

  Examples of the linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a trimethylene group, an isopropylidene group, a pentamethylene group, a hexamethylene group, and a heptamethylene group.

  Examples of the divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkylene groups such as cyclopropylene group, cyclobutylene group, cyclopentylene group and cyclohexylene group; cyclobutenylene group, cyclopentenylene group and And cycloalkenylene groups such as a cyclohexenylene group.

  Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenylene group, a naphthylene group, and a biphenylene group.

  Examples of the divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include a linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms and a divalent halogenated fat having 3 to 12 carbon atoms. Examples thereof include a cyclic hydrocarbon group and a divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms.

  Examples of the linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include a difluoromethylene group, a dichloromethylene group, a tetrafluoroethylene group, a tetrachloroethylene group, a hexafluorotrimethylene group, and a hexachlorotrimethylene group. Group, hexafluoroisopropylidene group, hexachloroisopropylidene group and the like.

  As the divalent halogenated alicyclic hydrocarbon group having 3 to 12 carbon atoms, at least a part of the hydrogen atoms exemplified in the divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms is a fluorine atom. And a group substituted with a chlorine atom, a bromine atom or an iodine atom.

  As the divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms, at least a part of the hydrogen atoms exemplified in the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms is a fluorine atom, chlorine And a group substituted with an atom, a bromine atom or an iodine atom.

  Examples of the organic group having 1 to 12 carbon atoms including at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom include an organic group consisting of a hydrogen atom and a carbon atom and an oxygen atom and / or a nitrogen atom. And a divalent organic group having 1 to 12 carbon atoms and having an ether bond, a carbonyl group, an ester bond or an amide bond and a hydrocarbon group.

  The divalent halogenated organic group having 1 to 12 carbon atoms containing at least one kind of atom selected from the group consisting of oxygen atom and nitrogen atom is specifically selected from the group consisting of oxygen atom and nitrogen atom Examples include a group in which at least a part of the hydrogen atoms exemplified in the divalent organic group having 1 to 12 carbon atoms containing at least one atom is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. .

Z in the formula (3) is preferably a single bond, —O—, —SO ₂ —,> C═O or a divalent organic group having 1 to 12 carbon atoms, and a divalent organic group having 1 to 12 carbon atoms. A hydrocarbon group, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, or a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms is more preferable.

In the formula (4), R ⁷ , R ⁸ , Y, m, g and h are each independently synonymous with R ⁷ , R ⁸ , Y, m, g and h in the formula (2), R ^5, R ^6, Z, n, e and f are the R ⁵ of each of the formulas (3), R ^6, Z, and n, e and f synonymous. When m is 0, R ⁷ is not a cyano group.

In the polymer (II), the molar ratio of the structural unit (i) to the structural unit (ii) (however, the sum of both ((i) + (ii)) is 100) is an optical property. From the viewpoint of heat resistance and mechanical properties, (i) :( ii) = 50: 50 to 100: 0 is preferable, and (i) :( ii) = 70: 30 to 100: 0. More preferably, (i) :( ii) = 80: 20 to 100: 0 is more preferable.
Here, the mechanical properties refer to properties such as the tensile strength, breaking elongation and tensile elastic modulus of the polymer.

The polymer (II) preferably contains 70 mol% or more of the structural unit (i) and the structural unit (ii) in the total structural units from the viewpoint of optical properties, heat resistance and mechanical properties. It is more preferable to contain 95 mol% or more.
The polymer (II) includes, for example, a compound represented by the following formula (5) (hereinafter also referred to as “compound (5)”) and a compound represented by the following formula (7) (hereinafter referred to as “compound (7)”). A component containing at least one compound selected from the group consisting of (hereinafter also referred to as “component (A)”) and a component containing a compound represented by the following formula (6) (hereinafter referred to as “component (B)”) Can be obtained by reaction.

  In said formula (5), X shows a halogen atom independently and a fluorine atom is preferable.

In the formula (7), R ^7, R ^8, Y, m, g and h are the R ⁷ of each of the formulas (2), R ^8, Y, m, and g and h synonymous, X is And are independently synonymous with X in the formula (5). However, when m is 0, R ⁷ is not a cyano group.

In the formula (6), each R ^a independently represents a hydrogen atom, a methyl group, an ethyl group, an acetyl group, a methanesulfonyl group or a trifluoromethylsulfonyl group, and among them, a hydrogen atom is preferable. In the formula (6), R ¹ to R ⁴ and a~d have the same meanings as R ¹ to R ⁴ and a~d each independently the formula (1).

  Specific examples of the compound (5) include 2,6-difluorobenzonitrile (DFBN), 2,5-difluorobenzonitrile, 2,4-difluorobenzonitrile, 2,6-dichlorobenzonitrile, 2, Mention may be made of 5-dichlorobenzonitrile, 2,4-dichlorobenzonitrile and its reactive derivatives. In particular, 2,6-difluorobenzonitrile and 2,6-dichlorobenzonitrile are preferably used from the viewpoints of reactivity and economy. These compounds can be used in combination of two or more.

  Specific examples of the compound represented by the above formula (6) (hereinafter also referred to as “compound (6)”) include 9,9-bis (4-hydroxyphenyl) fluorene (BPFL) and 9,9-bis. (3-phenyl-4-hydroxyphenyl) fluorene, 9,9-bis (3,5-diphenyl-4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9, Examples thereof include 9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene, and reactive derivatives thereof. Among the above-mentioned compounds, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene are preferably used. These compounds can be used in combination of two or more.

  Specific examples of the compound (7) include 4,4′-difluorobenzophenone, 4,4′-difluorodiphenylsulfone (DFDS), 2,4′-difluorobenzophenone, 2,4′-difluorodiphenylsulfone, 2,2′-difluorobenzophenone, 2,2′-difluorodiphenylsulfone, 3,3′-dinitro-4,4′-difluorobenzophenone, 3,3′-dinitro-4,4′-difluorodiphenylsulfone, 4, 4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl sulfone, 2,4'-dichlorobenzophenone, 2,4'-dichlorodiphenyl sulfone, 2,2'-dichlorobenzophenone, 2,2'-dichlorodiphenyl sulfone, 3 , 3′-dinitro-4,4′-dichlorobenzophenone and 3,3′-dinitro-4, 4'-dichlorodiphenyl sulfone and the like can be mentioned. Among these, 4,4′-difluorobenzophenone and 4,4′-difluorodiphenyl sulfone are preferable. These compounds can be used in combination of two or more.

It is preferable that at least one compound selected from the group consisting of compound (5) and compound (7) is contained in 80 mol% to 100 mol% in 100 mol% of component (A), and 90 mol% to More preferably, it is contained at 100 mol%.
Moreover, it is preferable that (B) component contains the compound represented by following formula (8) as needed. Compound (6) is preferably contained in 100 mol% of component (B) in an amount of 50 mol% to 100 mol%, more preferably 80 mol% to 100 mol%, and more preferably 90 mol%. More preferably, it is contained in an amount of ˜100 mol%.

In the formula (8), R ⁵ , R ⁶ , Z, n, e and f are each independently synonymous with R ⁵ , R ⁶ , Z, n, e and f in the formula (3), R ^a has the same meaning as R ^a each independently in the formula (6) in.

  Examples of the compound represented by the formula (8) include hydroquinone, resorcinol, 2-phenylhydroquinone, 4,4′-biphenol, 3,3′-biphenol, 4,4′-dihydroxydiphenylsulfone, and 3,3′-dihydroxy. Diphenylsulfone, 4,4′-dihydroxybenzophenone, 3,3′-dihydroxybenzophenone, 1,1′-bi-2-naphthol, 1,1′-bi-4-naphthol, 2,2-bis (4-hydroxy) Phenyl) propane, 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane and reactive derivatives thereof. Among the above-mentioned compounds, resorcinol, 4,4′-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy) Phenyl) -1,1,1,3,3,3-hexafluoropropane is preferred, and 4,4′-biphenol is suitably used from the viewpoint of reactivity and mechanical properties. These compounds can be used in combination of two or more.

More specifically, the polymer (II) can be synthesized by the method (I ′) shown below.
Method (I ′):
The alkali metal salt obtained after reacting the component (B) with an alkali metal compound in an organic solvent to obtain an alkali metal salt of the component (B) (compound (6) and / or compound (8), etc.) And (A) component are made to react. In addition, the alkali metal salt of (B) component and (A) component can also be made to react by performing reaction with (B) component and an alkali metal compound in presence of (A) component.

  Examples of the alkali metal compound used in the reaction include alkali metals such as lithium, potassium and sodium; alkali hydrides such as lithium hydride, potassium hydride and sodium hydride; lithium hydroxide, potassium hydroxide and sodium hydroxide And alkali metal carbonates such as lithium hydrogen carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate. These can be used alone or in combination of two or more.

In the alkali metal compound, the amount of metal atoms in the alkali metal compound is usually 1 to 3 times equivalent, preferably 1.1 to 2 times equivalent to all —O—R ^a in the component (B). Preferably it is used in an amount of 1.2 to 1.5 times equivalent.

  Examples of the organic solvent used in the reaction include N, N-dimethylacetamide (DMAc), N, N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ- Butyllactone, sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, diisopropyl sulfone, diphenyl sulfone, diphenyl ether, benzophenone, dialkoxybenzene (1 to 4 carbon atoms of alkoxy group) and trialkoxybenzene (carbon number of alkoxy group) 1-4) etc. can be used. Among these solvents, polar organic solvents having a high dielectric constant such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, diphenylsulfone, and dimethylsulfoxide are particularly preferably used.

  Further, in the reaction, a solvent azeotropic with water such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole and phenetole can be further used.

  The proportion of component (A) and component (B) used is preferably 45 mol% or more and 55 mol% or less when component (A) is 100 mol% when the total of component (A) and component (B) is 100 mol%. More preferably, it is 50 mol% or more and 52 mol% or less, More preferably, it exceeds 50 mol% and is 52 mol% or less, and (B) component becomes like this. Preferably it is 45 mol% or more and 55 mol% or less, More preferably, it is 48 mol%. It is at least 50 mol%, more preferably at least 48 mol% but less than 50 mol%.

  Moreover, reaction temperature becomes like this. Preferably it is 60 to 250 degreeC, More preferably, it is the range of 80 to 200 degreeC. The reaction time is preferably in the range of 15 minutes to 100 hours, more preferably 1 hour to 24 hours.

  Since the polymer (I) does not require high-temperature treatment for imidization necessary for the synthesis of the polyimide polymer, the production process load of the polymer is low, and the polymer can be easily produced.

  The polymer (I) has a polystyrene-equivalent weight average molecular weight (Mw) measured with a TOSOH HLC-8220 GPC apparatus (column: TSKgel α-M, developing solvent: tetrahydrofuran (hereinafter also referred to as “THF”). , Preferably it is 5,000-500,000, More preferably, it is 15,000-400,000, More preferably, it is 30,000-300,000.

  The polymer (I) has a thermal decomposition temperature measured by thermogravimetric analysis (TGA) of preferably 450 ° C. or higher, more preferably 475 ° C. or higher, and further preferably 490 ° C. or higher.

  Although it does not restrict | limit especially as a manufacturing method of the said base material, The resin composition containing the said polymer (I) is apply | coated on a support body, a coating film is formed, and then an organic solvent is removed from this coating film. And a method for producing a substrate.

  As the resin composition, a mixture of the polymer (II) and the organic solvent obtained by the method (I ′) can be used as it is. By using such a resin composition, a substrate can be easily produced at a low cost.

The resin composition is prepared by isolating (purifying) the polymer (II) as a solid content from the mixture of the polymer (II) obtained by the method (I ′) and an organic solvent, The resin composition can also be prepared by re-dissolving in a solvent.
The method of isolating (purifying) the polymer (II) as a solid component is, for example, reprecipitation of the polymer in a poor solvent of the polymer (II) such as methanol, and then filtering and then drying under reduced pressure. Can be performed.

  As the organic solvent for dissolving the polymer (II), for example, methylene chloride, tetrahydrofuran, cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and γ-butyrolactone are preferable. From the viewpoint of coating properties and economy, methylene chloride, N, N-dimethylacetamide and N-methylpyrrolidone are preferably used. These solvents can be used alone or in combination of two or more.

  The concentration of the polymer (I) in the resin composition is usually 5 to 40% by mass, preferably 7 to 25% by mass, although it depends on the molecular weight of the polymer. When the concentration of the polymer (I) in the composition is in the above range, it is possible to form a base material that can be thickened, hardly causes pinholes, and has excellent surface smoothness.

  The viscosity of the resin composition depends on the molecular weight and concentration of the polymer, but is preferably 50 to 100,000 mPa · s, more preferably 500 to 50,000 mPa · s, and still more preferably 1000 to 20,000 mPa · s. s. When the viscosity of the composition is in the above range, the composition is excellent in retention during film formation, hardly flows down from the support, and the thickness can be easily adjusted, so that the substrate can be easily molded.

The base material is preferably essentially composed only of the polymer (I), but an anti-aging agent can be further blended if necessary, and the base material obtained by blending the anti-aging agent. The durability of can be further improved.
Preferred examples of the antiaging agent include hindered phenol compounds.

Examples of hindered phenol compounds that can be used in the present invention include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) proonate], 1,6-hexanediol- Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert- Butylanilino) -3,5-triazine, pentaerythritol tetrakis [3- (3,5-tert-butyl-4-hydroxyphenyl) propionate], 1,1,3-tris [2-methyl-4- [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] butane 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate), N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-tert-butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate and 3,9-bis [2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro 5.5] undecane, and the like.
In this invention, it is preferable to use an anti-aging agent in the quantity of 0.01-10 weight part with respect to 100 weight part of polymers (I).

  Examples of the method for forming the coating film by applying the resin composition on a support include a roll coating method, a gravure coating method, a spin coating method, and a method using a doctor blade.

Although the thickness of a coating film is not specifically limited, For example, it is 1-250 micrometers, Preferably it is 2-150 micrometers, More preferably, it is 5-125 micrometers.
Examples of the support include a polyethylene terephthalate (PET) film and a SUS plate.

  Further, the method for removing the organic solvent from the coating film is not particularly limited, and examples thereof include a method of heating the coating film. By heating the coating film, the organic solvent in the coating film can be evaporated and removed. The heating conditions may be determined as long as the organic solvent evaporates, and may be appropriately determined according to the substrate and the polymer. For example, the heating temperature is preferably 30 ° C to 300 ° C, and preferably 40 ° C to 250 ° C. Is more preferable, and it is still more preferable that it is 50 to 230 degreeC.

  Further, the heating time is preferably 10 minutes to 5 hours. Note that heating may be performed in two or more stages. Specifically, after drying at a temperature of 30 to 80 ° C. for 10 minutes to 2 hours, heating is further performed at 100 to 250 ° C. for 10 minutes to 2 hours. Further, if necessary, drying may be performed under a nitrogen atmosphere or under reduced pressure.

  The obtained substrate is preferably used after being peeled off from the support, but when a transparent support is used, it can be used as it is without being peeled off.

Although the thickness of the said base material is suitably selected according to a desired use, Preferably it is 1-250 micrometers, More preferably, it is 2-150 micrometers, More preferably, it is 10-125 micrometers.
When manufacturing a touch panel using the base material, it is preferable that the base material has a thin film thickness in consideration of the retardation of the base material, weight reduction and low profile of the resulting touch panel, and the like.

The base material preferably has a glass transition temperature (Tg) of 230-350 ° C., 240-330 ° C., measured by Rigaku 8230 DSC measuring device (temperature increase rate 20 ° C./min). Is more preferable, and it is more preferable that it is 250-300 degreeC.
When the base material has such a glass transition temperature, when the transparent conductive film is formed, the temperature range at which the base material can be heated is widened. A transparent conductive film can be easily produced.

Further, when the substrate has a thickness of 30 μm, the total light transmittance in the JIS K7105 transparency test method is preferably 85% or more, and more preferably 88% or more. The total light transmittance can be measured using a haze meter SC-3H (manufactured by Suga Test Instruments Co., Ltd.).
When the substrate has a thickness of 30 μm, the light transmittance at a wavelength of 400 nm is preferably 70% or more, more preferably 75% or more, and further preferably 80% or more. The light transmittance at a wavelength of 400 nm can be measured using an ultraviolet / visible spectrophotometer V-570 (manufactured by JASCO).
When the transmittance of the substrate is in such a range, the transparent conductive film obtained from the substrate is excellent in light transmittance and can be suitably used for a touch panel or the like.

  When the substrate has a thickness of 30 μm, the YI value (yellow index) is preferably 3.0 or less, more preferably 2.5 or less, and 2.0 or less. Further preferred. The YI value can be measured using an SM-T color measuring device manufactured by Suga Test Instruments Co., Ltd. When the YI value is in such a range, a substrate that is difficult to be colored can be obtained, and can be suitably used as a transparent conductive film.

  Further, when the substrate has a thickness of 30 μm, the YI value after heating for 1 hour at 230 ° C. in the air with a hot air dryer is preferably 3.0 or less. Or less, more preferably 2.0 or less. When the YI value is in such a range, a substrate that is difficult to be colored even at high temperatures can be obtained, and a transparent conductive film having excellent optical properties and high conductivity can be obtained.

  The substrate preferably has a refractive index of 1.55 to 1.75, more preferably 1.60 to 1.70 with respect to light having a wavelength of 633 nm. The refractive index can be measured using a haze meter SC-3H (manufactured by Suga Test Instruments Co., Ltd.).

The base material preferably has a tensile strength of 50 to 200 MPa, and more preferably 80 to 150 MPa. The tensile strength can be measured using a tensile tester 5543 (manufactured by INSTRON).
The base material has an elongation at break of preferably 5 to 100%, more preferably 15 to 100%. The elongation at break can be measured using a tensile tester 5543 (manufactured by INSTRON).
The base material preferably has a tensile modulus of 2.5 to 4.0 GPa, more preferably 2.7 to 3.7 GPa. The tensile elastic modulus can be measured using a tensile tester 5543 (manufactured by INSTRON).

When the substrate has a thickness of 30 μm, the thickness direction retardation (Rth) is preferably 200 nm or less, more preferably 50 nm or less, and even more preferably 10 nm or less. The phase difference can be measured using a RETS spectrometer manufactured by Otsuka Electronics.
When the substrate has such a low retardation, an optically isotropic transparent conductive film can be obtained. When the substrate is used for a touch panel or the like, coloring or interference fringes appear on the display surface. Therefore, it is possible to suitably prevent the display quality from deteriorating. Therefore, the said base material can be used conveniently as a base material of the transparent conductive film used for a touch panel.

The base material has a linear expansion coefficient of 80 ppm / K or less, more preferably 75 ppm / K or less, measured using an SSC-5200 type TMA measuring device manufactured by Seiko Instruments.
The substrate preferably has a humidity expansion coefficient of 15 ppm /% RH or less, and more preferably 12 ppm /% RH or less. The humidity expansion coefficient can be measured using MA (SII Nanotechnology, TMA-SS6100) humidity control option. When the expansion coefficient of the base material is within the above range, it indicates that the base material has high dimensional stability (environmental reliability), and thus can be more suitably used as a touch panel. In particular, it can be suitably used for an in-car car navigation that requires high environmental reliability.

<Transparent conductive film>
The transparent conductive film is formed on at least one surface of the substrate. In the present invention, “formed on at least one surface of a substrate” means that it is formed on at least one surface of the substrate without any other layer, and / or at least one of the substrate. It is a case where it is formed through another layer on the surface. That is, the transparent conductive film may be formed directly on the base material or may be formed through an inorganic layer described later, but may be formed through an inorganic layer described later or the like. It is preferable from the viewpoints of obtaining a transparent conductive film having a high degree of conversion and a transparent conductive film having a high light transmittance.

  The transparent conductive film is not particularly limited as long as it is transparent and exhibits conductivity. However, tin oxide, indium oxide, antimony oxide, zinc oxide, cadmium oxide, indium tin oxide (ITO), and indium zinc oxide are not limited. Examples thereof include metal oxide films such as (IZO), composite films mainly composed of these metal oxides, and metal films such as gold, silver, copper, tin, nickel, aluminum, and palladium.

  When a film made of indium tin oxide (ITO) is used as the transparent conductive film, the transparent conductive film is used to increase the mechanical strength, to crystallize the obtained thin film, to reduce the resistance of the thin film, and the like. As a forming material, a material preferably containing indium oxide and 2 to 18% by weight tin oxide, more preferably a material containing 82 to 98% by weight indium oxide and 2 to 18% by weight tin oxide, more preferably 85 to 85%. It is desirable to use a material comprising 96 wt% indium oxide and 4-15 wt% tin oxide. However, the entire transparent conductive film forming material is 100% by weight.

  The method for forming the transparent conductive film is not particularly limited, and examples thereof include known methods such as a vacuum deposition method, a sputtering method, a physical vapor deposition method such as an ion plating method, and a chemical vapor deposition (CVD) method. From the viewpoint of the uniformity of the film and the adhesion of the thin film to the substrate, it is preferable to form the transparent conductive film by a sputtering method.

  When forming the transparent conductive film, various additives and stabilizers known in advance on the surface of the substrate, for example, an antistatic agent, an anti-ultraviolet agent, a plasticizer, and a lubricant, as long as the effects of the present invention are not impaired. Alternatively, an easy adhesive may be applied. In order to improve the adhesion between the substrate and the transparent conductive film, the surface of the substrate may be previously subjected to corona treatment, plasma treatment, ion bombardment treatment, chemical treatment, etc., unless the effects of the present invention are impaired. .

Further, the transparent conductive film of the present invention has a transparent conductive film formed on at least one surface of the substrate (Tg minus 20 ° C. of the substrate) or less, preferably (Tg minus 130 ° C. of the substrate) to It can be obtained by annealing at (Tg minus 30 ° C. of base material). By this annealing treatment, a transparent conductive film having a low resistance transparent conductive film can be obtained.
Since the base material contains the polymer (I), the annealing treatment can be performed at a high temperature. For this reason, the transparent conductive film which has a transparent conductive film with smaller resistance can be obtained.
The annealing treatment may be performed in the air, but may be performed in a desired gas atmosphere or under pressure if necessary.

When the transparent conductive film of the present invention is used for a capacitive touch panel, the transparent conductive film is preferably patterned.
As a patterning method, a resist is applied on the transparent conductive film, a pattern is formed by exposure / development, and then the transparent conductive film is chemically dissolved, a method of vaporizing by a chemical reaction in vacuum, or a laser transparent Although the method of sublimating a conductive film is mentioned, it can select suitably by the shape of a pattern, precision, etc.

  The thickness of the transparent conductive film is preferably 20 to 50 nm, more preferably 20 to 40 nm. When the thickness of the transparent conductive film is in the above range, a transparent conductive film excellent in balance between low resistance and high transparency can be obtained.

  Since the base material contains the polymer (I), the glass transition temperature is high. Therefore, a transparent conductive film can be formed on a substrate even in a method that requires high-temperature heating.

Alternatively, a transparent conductive film may be formed by applying a polythiophene-based or polyaniline-based conductive polymer on the substrate and forming a film.
The transparent conductive film may be a single layer or a multilayer. In the case of multiple layers, it is preferable to adjust the total film thickness to be in the above range. When the transparent conductive film is composed of multiple layers, it may be a multilayer film made of the same material or a multilayer film made of different materials.

The transparent conductive film of the present invention preferably has a specific resistance value (volume resistance value) of 2 × 10 ⁻³ Ω · cm or less measured using a low resistivity meter “Loresta-GP” manufactured by Mitsubishi Chemical Corporation. More preferably, it is 5 × 10 ⁻⁴ Ω · cm or less. When the specific resistance value is in the above range, a film having excellent conductivity is obtained, and a touch panel including such a film is preferable because it can accurately and quickly react to a fine movement. The surface resistance value is preferably 300Ω / □ or less, more preferably 150Ω / □ or less, and particularly preferably 100Ω / □ or less. A touch panel including such a film is preferable because it can accurately and quickly react to a fine movement.

<Inorganic layer>
The transparent conductive film of the present invention preferably has at least one inorganic layer on at least one surface of the substrate from the viewpoint of obtaining a transparent conductive film having a high degree of crystallinity and high light transmittance. More preferably, it is formed directly on the substrate.
The inorganic layer refers to a layer made of a material different from that of the transparent conductive film.

The inorganic layer is preferably a layer having a refractive index in the range of 1.4 to 2.5, and such an inorganic layer includes inorganic substances such as oxides, sulfides, fluorides, and nitrides. The layer which consists of is mentioned.
Examples of the inorganic substance include magnesium oxide (1.6), silicon dioxide (1.5), magnesium fluoride (1.4), calcium fluoride (1.3 to 1.4), and cerium fluoride (1.6). ), Aluminum fluoride (1.3), titanium oxide (2.4), zirconium oxide (2.4), zinc sulfide (2.3), tantalum oxide (2.1), zinc oxide (2.1) Indium oxide (2.0), niobium oxide (2.3), tantalum oxide (2.2), and the like. In addition, the numerical value in the said parenthesis represents a refractive index.

The method for forming the inorganic layer is not particularly limited, and may be a known method such as a vacuum deposition method, a sputtering method, a physical vapor deposition method such as an ion plating method, or a chemical vapor deposition (CVD) method. From the viewpoint of the uniformity of the layer (film) and the adhesion of the thin film to the substrate, it is preferable to form the inorganic layer by a sputtering method.
The conditions for forming the inorganic layer by sputtering are preferably no heating or (Tg minus 20 ° C. of base material) or lower, and if necessary, under an atmosphere of argon gas, oxygen or the like, under reduced pressure. May be.
In the case of sputtering under heating, 40 ° C. to (Tg minus 30 ° C. of base material) is more preferable.

  When the inorganic layer is formed, various known additives and stabilizers may be applied to the surface of the base material in advance, as long as the effects of the present invention are not impaired. Or the like may be previously subjected to corona treatment, plasma treatment, ion bombardment treatment, chemical treatment or the like.

  The inorganic layer preferably has a thickness of 3 to 70 nm, more preferably 5 to 65 nm. When the thickness of the inorganic layer is in the above range, a transparent conductive film with high light transmittance can be obtained.

≪Laminated body≫
The laminate is selected from the group consisting of a polarizing plate, an antireflection film, a hard coat film, an antistatic film, and an antifouling film on at least one surface of the transparent conductive film, as long as the effects of the present invention are not impaired. At least one layer.
The polarizing plate is preferably laminated on the surface opposite to the surface on which the transparent conductive film of the substrate is laminated.

The polarizing plate may be a circularly polarizing plate or a linear polarizing plate, but when the laminate of the present invention is used for a touch panel, a circularly polarizing plate is used for improving the visibility. It is preferable.
The circularly polarizing plate preferably includes one linearly polarizing plate and one or more retardation plates. Although the method in particular of laminating | stacking a polarizing plate and a transparent conductive film is not restrict | limited, It can laminate | stack using the adhesive agent which does not impair the effect of this invention, the property as a touch panel, etc.

Also, for the purpose of improving the surface hardness of transparent conductive film, improving chemical resistance, preventing antistatic, scratching and preventing dirt such as fingerprints, antireflection film, hard coat film, antistatic film and antifouling film A functional film such as can be provided as appropriate. Furthermore, an anti-Newton ring process may be performed.
When the transparent conductive film of the present invention is used for a touch panel, the antireflection film, the hard coat film, the antistatic film and the antifouling film are preferably formed on a surface touched by a finger or a pen. It is preferable to be formed on the surface opposite to the surface on which the base material is laminated.

  The method for laminating the functional film is not particularly limited, but a solution containing a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent is melt-molded and cast on the transparent conductive film in the same manner as described above. In addition, a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent is applied on the transparent conductive film with a bar coater or the like, and then cured by ultraviolet irradiation or the like. Can be manufactured.

  The antireflection film is not particularly limited, and is a dielectric multilayer film formed by vapor deposition, a single antireflection film made of a fluorine compound or hollow silica by wet coating, or a reflection made of a plurality of layers having different refractive indexes. Examples include a film formed by laminating a prevention layer.

  Examples of the hard coating agent include ultraviolet (UV) / electron beam (EB) curable resins and thermosetting resins, and examples thereof include urethane, urethane acrylate, acrylate, epoxy, and epoxy acrylate resins. . Examples of commercially available products include LCH and LAS manufactured by Toyo Ink Manufacturing Co., Ltd., Beam Set manufactured by Arakawa Chemical Industry Co., Ltd., EBECRYL manufactured by Daicel-Cytec Co., Ltd., UVACURE, Opstar manufactured by JSR Co., Ltd., and the like.

  These hard coating agents and other coating agents may be used alone or in combination of two or more. These coating agents may be coated only on one side of the transparent conductive film or on both sides. When coating on both surfaces, different surfaces may be coated on both surfaces, or the same material may be coated on both surfaces.

The antifouling film is a film made of any material as long as it is water-repellent and / or oil-repellent, can protect the surface and further enhance the antifouling property, and does not impair the effects of the present invention. Although not limited, a layer composed of an organic compound, preferably a fluorine-containing organic compound, is suitable.
For example, a compound having a hydrophobic group is preferable as a material exhibiting water repellency, and a polymer compound such as fluorocarbon or perfluorosilane is suitable. It is also possible to impart antifouling performance to the UV curable resin.

  The antifouling film can be formed by using various coating methods such as a vacuum film forming process such as a vacuum deposition method and a plasma CVD method, and a wet process such as microgravure and screen printing depending on the material.

  When the functional film is formed on the transparent conductive film of the present invention, the surface of the transparent conductive film is subjected to surface treatment such as corona treatment or plasma treatment for the purpose of improving the adhesion between the transparent conductive film and the functional film. May be.

≪Touch panel≫
The touch panel includes the transparent conductive film or the laminate. Since the touch panel includes the transparent conductive film, the touch panel has high light permeability, is colorless, has high durability and water resistance, and has a wide operable temperature range. For this reason, it can be used for various display devices.
According to the present invention, it is possible to manufacture any type of touch panel such as a resistive film type, a surface acoustic wave type, an infrared type, an electromagnetic induction type, and a capacitance type.
The touch panel includes the transparent conductive film that is excellent in light transmittance, heat resistance, heat resistance coloring property, and the like. Therefore, a resistive film type or capacitive type touch panel is preferable, and a capacitive type touch panel is more preferable.

As the resistive film type touch panel, for example, the transparent conductive film of the present invention or the laminate of the present invention and the transparent conductive of the film or the laminate from the side (external) where a finger or a pen is contacted. Examples include a touch panel including a transparent conductive film facing the film while maintaining a gap.
It is preferable that the touch panel includes the laminate because a low reflection touch panel in which the amount of reflected light from the outside such as sunlight or a fluorescent lamp is suppressed.
A low-reflection touch panel essentially consists of these elements, but in order to actually realize the operation of the touch panel, a member that supports a transparent conductive film, a coating material, a spacer that forms a gap, and the like are used. The member that supports the transparent conductive film needs controlled optical characteristics, and the polymer (I) and the like are preferable.

  In addition, as the capacitive touch panel, for example, a surface capacitive touch panel including the transparent conductive film or the laminate, in which electrodes are provided at four corners of the base material, or the base The transparent conductive film of the present invention or the present invention, wherein an IC is mounted on a material and the transparent conductive film is patterned, and is laminated so that extending directions of the patterns are orthogonal to each other And a projected capacitive touch panel composed of the above laminate.

≪Display device≫
The display device includes the touch panel.
Since the display device includes a touch panel having the excellent characteristics, the display device can be used without limitation on a mobile phone, a smartphone, a portable information terminal, a car navigation system, a tablet PC, a sales device, an ATM, an FA device, and the like.

  Hereinafter, the present invention will be specifically described by way of examples.

(1) Structural analysis The structural analysis of the polymers obtained in the following Examples and Comparative Examples was performed by IR (ATR method, FT-IR, 6700, manufactured by NICOLET) and NMR (ADVANCE500 type, manufactured by BRUKAAR). .

(2) Weight average molecular weight (Mw), number average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
The weight average molecular weight (Mw), number average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the polymers obtained in the following Examples and Comparative Examples were measured by a TLCOH HLC-8220 GPC apparatus (column: TSKgelα-M). , Developing solvent: THF).

(3) Glass transition temperature (Tg)
The glass transition temperatures of the polymers or evaluation films obtained in the following examples and comparative examples were measured using a Rigaku 8230 type DSC measuring apparatus with a temperature increase rate of 20 ° C./min.

(3 ') Thermal decomposition temperature The thermal decomposition temperature of the polymers obtained in the following examples and comparative examples was determined by thermogravimetric analysis (TGA: temperature increase rate of 10 ° C / min under nitrogen atmosphere, 5% weight loss temperature). It was measured.

(4) Mechanical strength Tensile strength, breaking elongation, and tensile modulus at room temperature of the films for evaluation obtained in the following examples and comparative examples were measured in accordance with JIS K7127 using a tensile tester 5543 (manufactured by INSTRON). Measured.

(5) Environmental stability The linear expansion coefficient of the film for evaluation obtained in the following examples and comparative examples was measured using an SSC-5200 type TMA measuring apparatus manufactured by Seiko Instruments. After the temperature of the obtained film for evaluation was once raised to Tg minus 20 ° C., the linear expansion coefficient was calculated from the gradient of the TMA curve at 200 to 100 ° C. when the temperature was lowered at 3 ° C./min.
The humidity expansion coefficients of the evaluation films obtained in the following examples and comparative examples were measured under the following conditions using MA (manufactured by SII Nanotechnology, TMA-SS6100) humidity control option.
Humidity condition: humidified from 40% RH to 70% RH (tensile method: weight 5 g) Temperature: 23 ° C.

(6) Optical characteristics About the film for evaluation obtained by the following Example and comparative example, the total light transmittance and the yellow index (YI value) were measured according to the JISK7105 transparency test method. Specifically, the total light transmittance was measured using a haze meter SC-3H manufactured by Suga Test Instruments Co., Ltd., and the YI value was measured using a SM-T type color measuring instrument manufactured by Suga Test Instruments Co., Ltd. (before heating). YI).
Moreover, after heating the film for evaluation obtained by the following Example and the comparative example at 230 degreeC in air | atmosphere for 1 hour with a hot air dryer, YI value is SM-T type color measuring device by Suga Test Instruments Co., Ltd. (YI after heating). The measurement was performed according to JIS K 7105 conditions.

  The light transmittance at a wavelength of 400 nm of the film for evaluation obtained in the following Examples and Comparative Examples was measured using an ultraviolet / visible spectrophotometer V-570 (manufactured by JASCO), and the refraction of the film for evaluation obtained. The rate was measured using a prism coupler model 2010 (made by Metricon). The refractive index was measured using a wavelength of 633 nm.

  The retardation (Rth) of the evaluation films obtained in the following Examples and Comparative Examples was measured using a RETS spectrometer manufactured by Otsuka Electronics. In addition, the reference wavelength at the time of measurement was 589 nm, and the evaluation film thickness of the retardation was shown as a value normalized to 30 μm.

(7) Specific Resistance Value Using a low resistivity meter “Loresta-GP” manufactured by Mitsubishi Chemical Corporation, the specific resistance value of the transparent conductive film of the transparent conductive film obtained in the following Examples and Comparative Examples (Ω · cm).

[Example 1]
In a 3 L four-necked flask, component (A): 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile (hereinafter also referred to as “DFBN”), component (B): 9,9-bis (4- Hydroxyphenyl) fluorene (hereinafter also referred to as “BPFL”) 70.08 g (0.200 mol), resorcinol (hereinafter also referred to as “RES”) 5.51 g (0.050 mol), potassium carbonate 41.46 g (0.300 mol) ), 443 g of N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-Stark tube and a cooling tube were attached to the four-necked flask.

Next, after the atmosphere in the flask was replaced with nitrogen, the obtained solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. When no more water was observed, the temperature was gradually raised to 160 ° C. and reacted at that temperature for 6 hours.
After cooling to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum dried at 60 ° C. overnight to obtain a white powder (polymer) (yield 95.67 g, yield 95%).

Table 1 shows the physical properties of the obtained polymer. The obtained polymer was subjected to structural analysis and measurement of the weight average molecular weight. As a result, the characteristic absorption of the infrared absorption spectrum is 3035 (C—H stretching), 2229 cm ⁻¹ (CN), 1574 cm ⁻¹ , 1499 cm ⁻¹ (aromatic ring skeleton absorption), 1240 cm ⁻¹ (—O—). The weight average molecular weight was 130,000. The obtained polymer had the structural units (1) and (3).

Next, the obtained polymer was redissolved in DMAc to obtain a resin composition having a polymer concentration of 20% by mass. The resin composition is applied onto a substrate made of polyethylene terephthalate (PET) using a doctor blade, dried at 70 ° C. for 30 minutes, and then dried at 100 ° C. for 30 minutes to form a film. It peeled. Thereafter, the film was fixed to a metal frame and further dried at 230 ° C. for 2 hours to obtain an evaluation film having a thickness of 30 μm.
Table 1 shows the physical properties of the obtained film for evaluation.
Furthermore, using a sputtering apparatus, a transparent conductive film was formed on one side of the obtained film for evaluation under film forming conditions at 230 ° C. for 5 minutes in an argon atmosphere. In addition, ITO was used as a target material. The specific resistance value of the obtained transparent conductive film was 2 × 10 ⁻⁴ (Ω · cm).

[Example 2]
The same procedure as in Example 1 was performed except that 11.41 g (0.050 mol) of 2,2-bis (4-hydroxyphenyl) propane was used instead of RES. Table 1 shows the physical properties of the obtained polymer, evaluation film and transparent conductive film.

[Example 3]
As component (B), instead of 70.08 g of BPFL and 5.51 g of RES, 78.84 g (0.225 mol) of BPFL and 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3- The same operation as in Example 1 was carried out except that 8.41 g (0.025 mol) of hexafluoropropane was used. Table 1 shows the physical properties of the obtained polymer, evaluation film and transparent conductive film.

[Example 4]
Example 1 except that 125.65 g (0.250 mol) of 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene was used as the component (B) instead of 70.08 g of BPFL and 5.51 g of RES. The same was done. Table 1 shows the physical properties of the obtained polymer, evaluation film and transparent conductive film.

[Example 5]
(B) It carried out like Example 1 except having used BPFL87.60g (0.250mol) instead of BPFL70.08g and RES5.51g as a component. Table 1 shows the physical properties of the obtained polymer, evaluation film and transparent conductive film.

[Example 6]
(B) Instead of using 70.08 g of BPFL and 5.51 g of RES, 78.84 g (0.225 mol) of BPFL and 6.71 g (0.025 mol) of 1,1-bis (4-hydroxyphenyl) cyclohexane were used. Was carried out in the same manner as in Example 1. Table 1 shows the physical properties of the obtained polymer, evaluation film and transparent conductive film.

[Example 7]
(A) It carried out like Example 5 except having used DFBN28.10g (0.202 mol) and 4,4-difluorobenzophenone 11.02g (0.051 mol) instead of DFBN35.12g. Table 1 shows the physical properties of the obtained polymer, evaluation film and transparent conductive film.

[Example 8]
(A) It carried out similarly to Example 7 except having changed the compounding quantity of the component into DFBN 17.56g (0.126mol) and 4,4-difluorobenzophenone 27.55g (0.126mol). Table 1 shows the physical properties of the obtained polymer, evaluation film and transparent conductive film.

[Example 9]
The same procedure as in Example 5 was performed except that 78.84 g (0.250 mol) of 4,4-difluorodiphenyl sulfone (DFDS) was used as the component (A) instead of 35.12 g of DFBN. Table 1 shows the physical properties of the obtained polymer, evaluation film and transparent conductive film.

[Example 10]
The evaluation film obtained in Example 5 was placed in a sputtering apparatus, and an inorganic thin film layer having a thickness of 50 Å composed of Nb ₂ O ₅ was formed by sputtering using Nb ₂ O ₅ as a target. An inorganic thin film layer having a thickness of 60 angstroms made of SiO ₂ is formed by sputtering using Si as a target, and oxidation of In ₂ O ₃ / SnO ₂ = 90/10 (weight ratio) as a target is formed thereon. A transparent conductive film made of ITO and having a thickness of 270 angstroms was formed by sputtering using a material mixture. In addition, all the said sputtering was performed on the conditions of non-heating under argon gas and oxygen gas inflow.

  The laminated film was taken out into the atmosphere, and then annealed at 200 ° C. for 10 minutes in the atmosphere to obtain a transparent conductive film 1. When the sheet resistance value of the obtained transparent conductive film 1 was measured by the 4-probe method, it showed a low sheet resistance value of 95Ω / □. Moreover, when the total light transmittance of the transparent conductive film 1 was measured with a haze meter (based on JIS-7361), it showed a high total light transmittance of 90%. Furthermore, even after the transparent conductive film 1 was immersed in 1N hydrochloric acid for 10 minutes, the sheet resistance value did not change, indicating that a transparent conductive film having high crystallinity was obtained.

[Comparative Example 1]
As component (B), instead of 70.08 g of BPFL and 5.51 g of RES, 84.06 g of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (0. A polymer and a film for evaluation were obtained in the same manner as in Example 1 except that 250 mol) was used. Table 1 shows the physical properties of the obtained polymer and the film for evaluation.
Furthermore, using a sputtering apparatus, a transparent conductive film was formed on one side of the obtained film for evaluation under film forming conditions at 150 ° C. for 5 minutes in an argon atmosphere. In addition, ITO was used as a target material. The specific resistance value of the obtained transparent conductive film was 5 × 10 ⁻³ (Ω · cm). When the film formation temperature was 230 ° C. as in Example 1, the film was deformed and a uniform transparent conductive film was not formed.

[Comparative Example 2]
Polyethylene naphthalate film manufactured by Teijin Ltd .: Neotex was used, and evaluation was performed in the same manner as in Example 1 (film thickness 125 μm). The physical properties of the film are shown in Table 1.
Further, using a sputtering apparatus, a transparent conductive film was formed on one side of the film under a film forming condition of 150 ° C. for 5 minutes in an argon atmosphere. In addition, ITO was used as a target material. The specific resistance value of the obtained transparent conductive film was 7 × 10 ⁻³ (Ω · cm). When the film formation temperature was 230 ° C. as in Example 1, the film was deformed and a uniform transparent conductive film was not formed.

[Comparative Example 3]
9.70 g (23.6 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane was added to a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube. did. Next, after the atmosphere in the flask was replaced with nitrogen, N-methyl-2-pyrrolidone (NMP) (60 ml) was added and stirred until uniform. To the resulting solution, 5.30 g (23.6 mmol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride was added at room temperature, and the reaction was continued for 12 hours at the same temperature to obtain a solution containing polyamic acid. Obtained.

  After diluting the resulting polyamic acid-containing solution with NMP (75 ml), pyridine (7.5 ml) and acetic anhydride (6.7 ml) were added, and the mixture was stirred at 110 ° C. for 6 hours for imidization. . Then, after cooling to room temperature, it poured into a lot of methanol, and the filtrate was isolated by filtration. The obtained filtrate was vacuum dried at 60 ° C. overnight to obtain a white powder (polymer) (yield 13.5 g, yield 95.3%).

  Next, the obtained polymer was redissolved in DMAc to obtain a 20% by mass resin solution. The resin solution is applied onto a substrate made of polyethylene terephthalate (PET) using a doctor blade (100 μm gap), dried at 100 ° C. for 30 minutes, and then dried at 150 ° C. for 60 minutes to form a film. Peeled from the substrate. Thereafter, the film was further dried at 150 ° C. under reduced pressure for 3 hours to obtain an evaluation film having a thickness of 30 μm. Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

Furthermore, using a sputtering apparatus, a transparent conductive film was formed on one side of the obtained film for evaluation under film forming conditions at 230 ° C. for 5 minutes in an argon atmosphere. In addition, ITO was used as a target material. The specific resistance value of the obtained conductive film was 2 × 10 ⁻⁴ (Ω · cm).

  From the above results, it can be seen that the base material containing the polymer (I) is excellent in heat resistance and heat coloration resistance. Moreover, since the base material containing the polymer (I) is excellent in heat resistance, the film forming method for forming the transparent conductive film on at least one surface thereof is not limited, and the transparent conductive film having a small surface resistance value. Can be obtained. Therefore, it can be suitably used for a touch panel or the like.

Claims (19)

  A transparent conductive film having a transparent conductive film on at least one surface of a substrate, and the substrate has a glass transition temperature (Tg) of 230 by differential scanning calorimetry (DSC, heating rate of 20 ° C./min). A transparent conductive film comprising an aromatic polyether polymer having a temperature of ˜350 ° C.   A transparent conductive film is formed on at least one surface of a substrate containing an aromatic polyether polymer having a glass transition temperature (Tg) of 230 to 350 ° C. by differential scanning calorimetry (DSC, heating rate 20 ° C./min). A transparent conductive film formed by annealing at a temperature equal to or lower than (Tg minus 20 ° C. of the base material) after forming.   The transparent conductive film according to claim 1 or 2, wherein the transparent conductive film comprises indium oxide and 2 to 18% by weight of tin oxide (provided that the entire transparent conductive film is 100% by weight).   The transparent conductive film of any one of Claims 1-3 whose film thickness of the said transparent conductive film is 20-50 nm.   5. The inorganic material layer according to claim 1, which has at least one inorganic layer formed on at least one surface of the substrate without heating or by sputtering at a temperature of (Tg minus 20 ° C. of the substrate) or less. Transparent conductive film.   The transparent conductive film of any one of Claims 1-5 whose refractive index of the said inorganic substance layer is 1.4-2.5.   The transparent conductive film of any one of Claims 1-6 whose film thickness of the said inorganic substance layer is 3-70 nm. The aromatic polyether polymer has at least one structural unit (i) selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2). The transparent conductive film of any one of 1-7.

(In Formula (1), R < ¹ > -R < ⁴ > shows a C1-C12 monovalent organic group each independently, and ad shows the integer of 0-4 each independently.)

(In Formula (2), R < ¹ > -R < ⁴ > and ad are respectively synonymous with R < ¹ > -R < ⁴ > and said ad in said Formula (1), Y is a single bond, -SO _2- or> C = O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and g and h each independently represent 0 to 4 represents an integer of 4 and m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group. The aromatic polyether polymer further has at least one structural unit (ii) selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). The transparent conductive film of any one of Claims 1-8.

(In formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and Z represents a single bond, —O—, —S—, —SO ₂ —, > C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, e and f each independently represent an integer of 0 to 4, and n represents 0 or 1 .)

(In the formula ^{(4), R 7, R} 8, Y, m, g and h are each R ⁷ in independent to the formula ^{(2), R 8, Y} , m, synonymous with g and h, R ^5, R ^6, Z, n, e and f are as defined each R ⁵ in the formula (3) independently, R ^6, Z, n, e and f.)   10. The aromatic polyether polymer according to claim 1, wherein a molar ratio of the structural unit (i) to the structural unit (ii) is 50:50 to 100: 0. Transparent conductive film.   The transparent conductive of any one of Claims 1-10 whose weight average molecular weight of polystyrene conversion by the gel permeation chromatography (GPC) of the said aromatic polyether type polymer is 5,000-500,000. Sex film.   The transparent conductive film of any one of Claims 1-11 whose total light transmittance by the JISK7105 transparency test method in thickness of 30 micrometers of the said base material is 85% or more.   The transparent conductive film of any one of Claims 1-12 whose YI value (yellow index) in the thickness of the said base material of 30 micrometers is 3.0 or less.   The transparent conductive film of any one of Claims 1-13 whose retardation (Rth) of the thickness direction in the thickness of 30 micrometers of the said base material is 200 nm or less.   The transparent conductive film of any one of Claims 1-14 which is an object for capacitive touch panels.   The at least one surface selected from the group consisting of a polarizing plate, an antireflection film, a hard coat film, an antistatic film and an antifouling film on at least one surface of the transparent conductive film according to claim 1. A laminate comprising a seed layer.   A touch panel comprising the transparent conductive film according to claim 1 or the laminate according to claim 16.   The touch panel according to claim 17, which is a capacitive touch panel.   A display device comprising the touch panel according to claim 17.