CN109155166A - Transparent conducting film and its manufacturing method - Google Patents
Transparent conducting film and its manufacturing method Download PDFInfo
- Publication number
- CN109155166A CN109155166A CN201780029395.XA CN201780029395A CN109155166A CN 109155166 A CN109155166 A CN 109155166A CN 201780029395 A CN201780029395 A CN 201780029395A CN 109155166 A CN109155166 A CN 109155166A
- Authority
- CN
- China
- Prior art keywords
- resin film
- dielectric layer
- indium tin
- transparent conducting
- bis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229920005989 resin Polymers 0.000 claims abstract description 89
- 239000011347 resin Substances 0.000 claims abstract description 89
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- 239000002131 composite material Substances 0.000 claims abstract description 71
- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 claims abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
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- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000005416 organic matter Substances 0.000 claims abstract description 20
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- 150000003949 imides Chemical class 0.000 claims abstract description 11
- 238000000605 extraction Methods 0.000 claims description 43
- 238000004544 sputter deposition Methods 0.000 claims description 13
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
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- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical class C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 4
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- 238000001755 magnetron sputter deposition Methods 0.000 description 4
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- LERREUOVCXYKGR-UHFFFAOYSA-N (2-phenoxyphenyl)-phenylmethanone Chemical compound C=1C=CC=C(OC=2C=CC=CC=2)C=1C(=O)C1=CC=CC=C1 LERREUOVCXYKGR-UHFFFAOYSA-N 0.000 description 3
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- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical class C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 description 1
- DFFZOPXDTCDZDP-UHFFFAOYSA-N naphthalene-1,5-dicarboxylic acid Chemical class C1=CC=C2C(C(=O)O)=CC=CC2=C1C(O)=O DFFZOPXDTCDZDP-UHFFFAOYSA-N 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical class C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical class C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 125000002801 octanoyl group Chemical group C(CCCCCCC)(=O)* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000002811 oleoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 235000009165 saligot Nutrition 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 125000003696 stearoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical class NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
The present invention relates to a kind of transparent conducting film (10), it is configured in order dielectric layer (2) and indium tin composite oxide layer (3) on a surface of resin film (1), resin film (1) is selected from by polyester based resin film, one of the group of cellulose-based resin film and imide series resin film composition, dielectric layer (2) is made of the mixture of organic matter or organic matter and inorganic matter, and with a thickness of 0.005 μm or more and 0.100 μm or less, on the surface of the opposite side of the side configured with dielectric layer (2) of indium tin composite oxide layer (3), there are more than 2.1 atom % and 4.0 atom % are below, the active hydrogen-based that can be chemically modified by trifluoroacetic anhydride.Indium tin composite oxide layer (3) can be laminated on the surface of the opposite side of the side configured with resin film (1) of dielectric layer (2) to make by the way that dielectric layer (2) are laminated on a surface of resin film (1) in transparent conducting film (10) of the invention.
Description
Technical field
The present invention relates to the single side in resin film configured with indium tin composite oxide layer transparent conducting film and its
Manufacturing method.
Background technique
The transparent conducting film for being formed with the transparent and electrically conductive films such as indium tin composite oxide layer over the transparent substrate is wide
It is general to be used for the devices such as display and touch panel.In these devices, transparent conducting film require the transparency and electric conductivity this
It is used in the component of the two.
On the other hand, transparent and electrically conductive film usually utilizes extraction electrode and IC controller etc. to be electrically connected.In recent years, due to aobvious
The narrow frame for showing device and touch panel etc. has the tendency that the contact area reduction of extraction electrode and transparent and electrically conductive film, strongly
It is required that improving the adaptation of transparent and electrically conductive film and extraction electrode.Therefore, it is proposed on transparent and electrically conductive film in patent document 1
The adaptation being made of the low metal oxide of crystallinity, which is arranged, improves the technology of layer.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2013-228782 bulletin
Summary of the invention
Problems to be solved by the invention
But the transparency or poorly conductive for the metal oxide layer being usually made of the low metal oxide of crystallinity,
Therefore in patent document 1, having adaptation to improve layer makes the electric conductivity of transparent conducting film or the worry of transparency deterioration.
The present invention in order to solve the problem above-mentioned, provide be not provided with adaptation improve layer and with high electric conductivity and transparent
Property and with the adaptation of extraction electrode improve transparent conducting film and its manufacturing method.
The solution to the problem
The present invention relates to a kind of transparent conducting films, are configured in order dielectric on a surface of resin film
Layer and indium tin composite oxide layer, which is characterized in that resin film is selected from thin by polyester based resin film, cellulose-based resin
One of the group of film and imide series resin film composition, aforementioned dielectric layer are mixed by organic matter or organic matter and inorganic matter
Object is closed to constitute and with a thickness of 0.005 μm or more and 0.100 μm hereinafter, in aforementioned indium tin composite oxide layer configured with electricity
The surface of the opposite side of the side of dielectric layer there are it is more than 2.1 atom % and 4.0 atom % it is below can by trifluoroacetic anhydride into
The active hydrogen-based of row chemical modification.
In addition, the invention further relates to a kind of manufacturing methods of transparent conducting film, which is characterized in that selected from by polyester
One table of one of the group of based resin film, cellulose-based resin film and imide series resin film composition resin film
On face stacking be made of the mixture of organic matter or organic matter and inorganic matter and with a thickness of 0.005 μm or more and 0.100 μm with
Under dielectric layer, on the surface of the opposite side of the side configured with resin film of aforementioned dielectric layer be laminated indium tin it is compound
Oxide skin(coating), obtains transparent conducting film, and the transparent conducting film includes that resin film, dielectric layer and indium tin are compound
Oxide skin(coating), and on the surface of the opposite side of the side configured with dielectric layer of indium tin composite oxide layer, there are 2.1 originals
Sub- % or more and the 4.0 atom % active hydrogen-based below that can be chemically modified by trifluoroacetic anhydride.
The effect of invention
The present invention provides the transparent conductivity that there is the adaptation of high electric conductivity and the transparency and extraction electrode to improve
Film.In addition, manufacturing method according to the invention, can easily make with high electric conductivity and the transparency and draw electricity
The transparent conducting film that the adaptation of pole improves.
Detailed description of the invention
Fig. 1 is the schematic cross-section of the transparent conducting film of an embodiment of the invention.
Fig. 2 is the schematic cross-section of the transparent conducting film of another embodiment of the present invention.
Fig. 3 is the work that can be chemically modified by trifluoroacetic anhydride for showing the surface for being present in indium tin composite oxide layer
The figure of the relationship of the removing ratio of the amount and transparent conducting film and extraction electrode of property hydrogen-based.
Specific embodiment
The inventors of the present invention are high to the electric conductivity and the transparency that keep transparent conducting film and improve and extraction electrode
The case where adaptation, has made intensive studies.Itself as a result, it has been found that, by using selected from by polyester based resin film, cellulose-based tree
One of the group of membrane of lipoprotein and imide series resin film composition resin film uses indium tin combined oxidation as transparent substrate
Nitride layer is as transparent and electrically conductive film, and configuration is between resin film and indium tin composite oxide layer with a thickness of 0.005 μm~0.100
μm the dielectric layer being made of the mixture of organic matter or organic matter and inorganic matter, deposit the surface of indium tin composite oxide layer
More than 2.1 atom % (atomic%) and the 4.0 atom % reactive hydrogen below that can be chemically modified by trifluoroacetic anhydride
Base can obtain having high electric conductivity and the transparency, the transparent conducting film with the adaptation raising of extraction electrode, thus complete
At the present invention.
In addition, the adaptation of transparent conducting film and extraction electrode of the invention is high, therefore for using metal to draw
The touch panel of electrode can more reliably obtain the touch sensor being made of transparent conducting film using extraction electrode
Signal, the reliability of touch sensor improves.Especially because the adaptation with extraction electrode is high, therefore even if heating
After humidification test, the function for the touch sensor being made of transparent conducting film is also kept well, is improved contact and is passed
The durability of sensor.
Hereinafter, the embodiments of the present invention will be described with reference to the drawings.Fig. 1 is the saturating of an embodiment of the invention
The schematic section of bright conductive membrane.As shown in Figure 1, transparent conducting film 10 includes resin film 1, is configured at resin
Dielectric layer 2 on one surface of film 1 and be configured at dielectric layer 2 the side configured with resin film 1 opposite side
Surface on indium tin composite oxide layer 3.It should be noted that in this specification, indium tin composite oxides and ITO
(Indium Tin Oxide) meaning is identical.
(resin film 1)
Resin film 1 is selected from by polyester based resin film, cellulose-based resin film and imide series resin film group
At one of group.By making polyester based resin, cellulose-based resin and imide series resin that there is pole in molecular skeleton
Property group, to show appropriate moisture content (also referred to as moisture rate).Therefore it could be speculated that in transparent conducting film 10,
The moisture as contained in these resin films 1 for being formed of resins in molecular skeleton with polar group is by indium tin composite oxygen
Mobile to the surface of indium tin composite oxide layer 3 when compound layer is film-made, on the surface of indium tin composite oxide layer 3, there are 2.1 originals
The active hydrogen-based that can be chemically modified by trifluoroacetic anhydride of the atom of sub- %~4.0 %, transparent conducting film and extraction electricity
The adaptation of pole improves.
It as above-mentioned polyester based resin, is not particularly limited, the copolymer of dicarboxylic acid component and diol component can be used.
Such polyester based resin for example can make these at distribution by using dicarboxylic acid component and diol component as raw material
Raw esterification, polycondensation reaction obtain.
As above-mentioned dicarboxylic acid component, be not particularly limited, for example, can enumerate malonic acid, succinic acid, glutaric acid, oneself two
Acid, suberic acid, decanedioic acid, dodecanedioic acid, dimeric dibasic acid, eicosane diacid, pimelic acid, azelaic acid, methylmalonic acid, ethyl third
The aliphatic dicarboxylic acids class such as diacid；Adamantane dicarboxylic acids, norbornene dicarboxylic acids, cyclohexane dicarboxylic acid, decahydro naphthalene dicarboxylic acids etc.
Alicyclic dicarboxylic acid's class；Terephthalic acid (TPA), M-phthalic acid, phthalic acid, 1,4- naphthalene dicarboxylic acids, 1,5- naphthalene dicarboxylic acids, 2,
6- naphthalene dicarboxylic acids, 1,8- naphthalene dicarboxylic acids, 4,4 '-diphenyldicarboxylic acids, 4,4 '-diphenyl ether dicarboxylic acids, M-phthalic acid -5- sulphur
Aromatic dicarboxylic acids such as sour sodium, phenyl indane dicarboxylic acid, anthracene dicarboxylic acids, luxuriant and rich with fragrance dicarboxylic acids, 9,9 '-bis- (4- carboxyl phenyl) fluorenic acids etc.
Dicarboxylic acids or its ester derivant.These dicarboxylic acid components can be used a kind, two or more can also be applied in combination.
The case where it is preferable to use at least one kind of aromatic dicarboxylic acids as above-mentioned dicarboxylic acid component.It is further preferred that dicarboxylic acids
Contain aromatic dicarboxylic acid in ingredient as principal component.It should be noted that " principal component " refers to aromatic dicarboxylic acid in dicarboxyl
Shared ratio is 80 mass % or more in sour component.
It as above-mentioned diol component, is not particularly limited, for example, ethylene glycol, 1,2-PD, 1,3- the third two can be enumerated
The aliphatic diols classes such as alcohol, 1,4- butanediol, 1,2- butanediol, 1,3 butylene glycol；Cyclohexanedimethanol, spiral shell glycol, different sorb
The ester ring types glycols such as alcohol；Bisphenol-A, 1,3- benzene dimethanol, Isosorbide-5-Nitrae-benzene dimethanol, 9, the fragrance such as 9 '-bis- (4- hydroxy phenyl) fluorenes
Race's glycols etc..Above-mentioned diol component can be used a kind, two or more can also be applied in combination.
The case where it is preferable to use at least one kind of aliphatic diols as above-mentioned diol component.As aliphatic diol, can wrap
Containing ethylene glycol, ethylene glycol is preferably comprised as principal component.It should be noted that " principal component " refers to ethylene glycol in diol component
Shared ratio is 80 mass % or more.
As described above, being not particularly limited as polyester resin obtained from dicarboxylic acid component and diol component is used, example
Such as, it is preferably selected from by polyethylene terephthalate (PET), poly- 2,6-naphthalenedicarboxylic acid glycol ester (PEN) and gathers to benzene two
One or more of the group of formic acid butanediol ester (PBT) composition, from the viewpoint of cost, more preferably PET.
It as above-mentioned cellulose-based resin, is not particularly limited, for example, it is preferable to cellulose and/or as its derivative
Cellulose esters.The ester of cellulose esters preferred cellulose and fatty acid (including aromatic series fatty acid), preferably with above-mentioned fatty acid
Acyl group will be located at 2 of glucose unit, 3,6 hydroxyls that the β -1,4 for constituting cellulose is bonded and replace and carry out acyl
The cellulose acylate of base.Such as the alkyl oxycarbonyl base ester of cellulose, alkenyl carbonyl ester, aromatic carbonyl ester, virtue can be enumerated
Fragrant race's alkyl oxycarbonyl base ester etc..Even if these cellulose acylates are acyl made of the acyl group of two or more fatty acid is replaced
Compound it is also preferred that.There can also be other substituent groups.
As the acyl group replaced to above-mentioned hydroxyl, it is preferable to use the acetyl group of carbon number 2 and the acyl of carbon number 3~22
Base.Acyl group can be fitted according to required optical characteristics, thermal characteristics, mechanical property, the surface free energy of resin, compatibility etc.
Preferably determine.
The degree of substitution of acyl group in cellulose esters used in the present invention is not particularly limited.Degree of substitution can be according to being wanted
Optical characteristics, thermal characteristics, mechanical property, the surface free energy of resin, compatibility for asking etc. are being suitable for decision.
Above-mentioned acyl group can may be aromatic series for aliphatic, be not particularly limited.For example, can enumerate acetyl group,
Propiono, bytyry, heptanoyl group, caproyl, caprylyl, capryl, dodecane acyl group, tridecane acyl group, tetradecane acyl group, ten
Six alkanoyls, octadecanoyl, isobutyryl, tertiary bytyry, cyclohexane carbo, oleoyl, benzoyl, naphthyl carbonyl, meat
Osmanthus acyl group etc..In these, preferably acetyl group, propiono, bytyry, benzoyl, naphthyl carbonyl etc..
As the cellulose esters replaced by above-mentioned acyl group, for example, cellulose acetate, cellulose propionate, butyric acid can be enumerated
Cellulose, naphthalenedicarboxylic acid cellulose acetate, cellulose benzoate etc..
As above-mentioned imide series resin, be not particularly limited, can be used carried out imidizate, diamine component with
The copolymer of carboxylic acid dianhydride ingredient can be used by using diamine component and carboxylic acid dianhydride ingredient as raw material and make this
Resin obtained from a little ingredient polymerizations, imidizate.
Above-mentioned diamine component is not particularly limited, such as can enumerate p-phenylenediamine, m-phenylene diamine (MPD), o-phenylenediamine, 3, and 3 '-
Diamino-diphenyl ether, 3,4 '-diamino-diphenyl ethers, 4,4 '-diamino-diphenyl ethers, 3,3 '-diamino diphenyl sulfides,
3,4 '-diamino diphenyl sulfides, 4,4 '-diamino diphenyl sulfides, 3,3 '-diamino diphenyl sulfones, 3,4 '-diamino two
Phenylsulfone, 4,4 '-diamino diphenyl sulfones, 3,3 '-diaminobenzophenones, 4,4 '-diaminobenzophenones, 3,4 '-diaminos
Base benzophenone, 3,3 '-diaminodiphenyl-methanes, 4,4 '-diaminodiphenyl-methanes, 3,4 '-diaminodiphenyl-methanes,
2,2- bis- (3- aminophenyl) propane, 2,2- bis- (4- aminophenyl) propane, 2- (3- aminophenyl) -2- (4- aminophenyl) third
Alkane, 1,1- bis- (3- aminophenyl) -1- diphenylphosphino ethane, 1,1- bis- (4- aminophenyl) -1- diphenylphosphino ethane, 1- (3- aminobenzene
Base) -1- (4- aminophenyl) -1- diphenylphosphino ethane, bis- (3- amino-benzene oxygen) benzene of 1,3-, bis- (4- amino-benzene oxygen) benzene of 1,3-,
Bis- (3- amino-benzene oxygen) benzene of 1,4-, bis- (4- amino-benzene oxygen) benzene of 1,4-, bis- (3- amino benzoyl) benzene of 1,3-, 1,3- are bis-
Bis- (3- amino benzoyl) benzene of (4- amino benzoyl) benzene, 1,4-, bis- (4- amino benzoyl) benzene of 1,4-, 1,3- are bis-
Bis- (4- amino-bis (alpha, alpha-dimethylbenzyl) base) benzene of (3- amino-bis (alpha, alpha-dimethylbenzyl) base) benzene, 1,3-, 1,4- bis- (3- amino-α, α-
Dimethyl benzyl) benzene, bis- (4- amino-bis (alpha, alpha-dimethylbenzyl) base) benzene of 1,4-, 2,6- bis- (3- amino-benzene oxygen) benzonitriles, 2,6-
It is bis- (3- amino-benzene oxygen) pyridines, 4,4 '-bis- (3- amino-benzene oxygen) biphenyl, 4,4 '-bis- (4- amino-benzene oxygen) biphenyl, double
[4- (3- amino-benzene oxygen) phenyl] ketone, bis- [4- (4- amino-benzene oxygen) phenyl] ketone, bis- [4- (3- amino-benzene oxygen) phenyl]
Thioether, bis- [4- (4- amino-benzene oxygen) phenyl] thioethers, bis- [4- (3- amino-benzene oxygen) phenyl] sulfones, bis- [4- (4- aminobenzene oxygen
Base) phenyl] sulfone, bis- [4- (3- amino-benzene oxygen) phenyl] ethers, bis- [4- (4- amino-benzene oxygen) phenyl] ethers, the bis- [4- (3- of 2,2-
Amino-benzene oxygen) phenyl] propane, bis- [4- (4- amino-benzene oxygen) phenyl] propane of 2,2-, the bis- [4- (3- amino-benzene oxygen) of 1,3-
Benzoyl] benzene, bis- [4- (4- amino-benzene oxygen) benzoyl] benzene of 1,3-, bis- [4- (3- amino-benzene oxygen) benzoyls of 1,4-
Base] benzene, bis- [4- (4- amino-benzene oxygen) benzoyl] benzene of 1,4-, bis- [4- (3- the amino-benzene oxygen)-bis (alpha, alpha-dimethylbenzyl)s of 1,3-
Base] benzene, bis- [4- (4- the amino-benzene oxygen)-bis (alpha, alpha-dimethylbenzyl) base] benzene of 1,3-, bis- [4- (3- the amino-benzene oxygen)-α, α-of 1,4-
Dimethyl benzyl] benzene, bis- [4- (4- the amino-benzene oxygen)-bis (alpha, alpha-dimethylbenzyl) base] benzene of 1,4-, 4,4 '-bis- [4- (4- aminobenzene oxygen
Base) benzoyl] it is diphenyl ether, 4,4 '-bis- [4- (4- amino-bis (alpha, alpha-dimethylbenzyl) base) phenoxy group] benzophenone, 4,4 '-bis-
[4- (4- amino-bis (alpha, alpha-dimethylbenzyl) base) phenoxy group] diphenyl sulfone, 4,4 '-bis- [4- (4- amino-benzene oxygen) phenoxy group] hexichol
Base sulfone,-two phenoxy benzophenone of 3,3 '-diamino -4,4 ', 3,3 '-diamino -4,4 '-bigeminy phenoxy benzophenone, 3,
3 '-diamino -4- phenoxy benzophenones, 3,3 '-diamino -4-, two phenoxy benzophenone, 6,6 '-bis- (3- aminobenzene oxygen
Base) -3,3,3 ', 3 '-tetramethyls -1,1 '-spirobiindene is full, 6,6 '-bis- (4- amino-benzene oxygen) -3,3,3 ', 3 '-tetramethyl -1,
1 '-spirobiindene is full, 1,3- is bis- (3- aminopropyl) tetramethyl disiloxane, the bis- two silicon oxygen of (4- aminobutyl) tetramethyl of 1,3-
Alkane, α, ω-bis- (3- aminopropyl) dimethyl silicone polymers, α, bis- (3- aminobutyl) dimethyl silicone polymers of ω-, bis- (ammonia
Ylmethyl) ether, bis- (2- amino-ethyl) ethers, bis- (3- aminopropyl) ethers, bis- (2- aminomethoxy) ethyls] ether, bis- [2- (2-
Amino ethoxy) ethyl] ether, bis- [2- (3- amino propoxyl group) ethyl] ethers, bis- (aminomethoxy) ethane of 1,2-, 1,2- be bis-
Bis- [2- (aminomethoxy) ethyoxyl] ethane of (2- amino ethoxy) ethane, 1,2-, bis- [2- (2- amino ethoxy) second of 1,2-
Oxygroup] ethane, bis- (3- aminopropyl) ethers of ethylene glycol, bis- (3- aminopropyl) ethers of diethylene glycol, bis- (the 3- aminopropans of triethylene glycol
Base) ether, ethylenediamine, 1,3- diaminopropanes, 1,4- diaminobutane, 1,5- 1,5-DAP, 1,6- diamino hexane, 1,7-
Diaminoheptane, 1,8- diamino-octane, 1,9- diamino nonane, 1,10- diamino decane, 1,11- diamino undecane, 1,
12- diamino dodecane, 1,2- diaminocyclohexane, 1,3- diaminocyclohexane, 1,4- diaminocyclohexane, anti-form-1,4-
Diaminocyclohexane, 1,2- bis- (2- amino-ethyl) hexamethylene, 1,3- bis- (2- amino-ethyl) hexamethylene, (the 2- amino of 1,4- bis-
Ethyl) hexamethylene, bis- (4- aminocyclohexyl) methane, bis- (amino methyl) two ring [2.2.1] heptane of 2,6-, the bis- (amino of 2,5-
Methyl) two rings [2.2.1] heptane, 1,4- diamino -2- fluorobenzene, 1,4- diamino -2,3- difluorobenzene, 1,4- diamino -2,5-
Difluorobenzene, 1,4- diamino -2,6- difluorobenzene, 1,4- diamino -2,3,5- trifluoro-benzene, 1,4- diamino -2,3,5,6- tetrafluoro
Benzene, 1,4- diamino -2- (trifluoromethyl) benzene, bis- (trifluoromethyl) benzene of 1,4- diamino -2,3-, 1,4- diamino -2,5- are double
Bis- (trifluoromethyl) benzene of (trifluoromethyl) benzene, 1,4- diamino -2,6-, 1,4- diamino -2,3,5- three (trifluoromethyl) benzene, 1,
4- diamino -2,3,5,6- four (trifluoromethyl) benzene, 2- fluorine benzidine, 3- fluorine benzidine, 2,3- DfBP amine, 2,5- difluoro
Benzidine, 2,6- DfBP amine, 2,3,5- trifluoro-biphenyl amine, 2,3,6- trifluoro-biphenyl amine, 2,3,5,6- tetrafluoro benzidine, 2,
2 '-DfBP amine, 3,3 '-DfBP amine, 2,3 '-DfBP amine, 2,2 ', 3- trifluoro-biphenyl amine, 2,3,3 '-trifluoros connection
Aniline, 2,2 ', 5- trifluoro-biphenyl amine, 2,2 ', 6- trifluoro-biphenyl amine, 2,3 ', 5- trifluoro-biphenyl amine, 2,3 ', 6 ,-trifluoro-biphenyl
Amine, 2,2 ', 3,3 '-tetrafluoro benzidine, 2,2 ', 5,5 '-tetrafluoro benzidine, 2,2 ', 6,6 '-tetrafluoro benzidine, 2,2 ', 3,3 ',
6,6 '-hexafluoro benzidine, 2,2 ', 3,3 ', 5,5 ', 6,6 '-octafluorobiphenyl amine, 2- (trifluoromethyl) benzidine, 3- (fluoroform
Base) benzidine, bis- (trifluoromethyl) benzidine of 2,3-, bis- (trifluoromethyl) benzidine of 2,5-, bis- (trifluoromethyl) biphenyl of 2,6-
Amine, 2,3,5- tri- (trifluoromethyl) benzidine, 2,3,6- tri- (trifluoromethyl) benzidine, 2,3,5,6- tetra- (trifluoromethyl) biphenyl
Amine, 2,2 '-bis- (trifluoromethyl) benzidine, 3,3 '-bis- (trifluoromethyl) benzidine, 2,3 '-bis- (trifluoromethyl) benzidine, 2,
2 ', 3- tri- (trifluoromethyl) benzidine, 2,3,3 '-three (trifluoromethyl) benzidine, 2,2 ', 5- tri- (trifluoromethyl) benzidine,
2,2 ', 6- tri- (trifluoromethyl) benzidine, 2,3 ', 5- tri- (trifluoromethyl) benzidine, 2,3 ', 6- tri- (trifluoromethyl) biphenyl
Amine, 2,2 ', 3,3 '-four (trifluoromethyl) benzidine, 2,2 ', 5,5 '-four (trifluoromethyl) benzidine, 2,2 ', 6,6 '-four (three
Methyl fluoride) benzidine etc..Above-mentioned diamine component can be used a kind, two or more can also be applied in combination.
Above-mentioned carboxylic acid dianhydride ingredient is not particularly limited, such as can enumerate ethylene tetracarboxylic dianhydride, butane tetracarboxylic acid two
Acid anhydride, cyclobutane tetracarboxylic dianhydride, pentamethylene tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides, 2,2 ', 3,3 '-
Benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyltetracarboxylic dianhydrides, 2,2- bis- (3,4- dicarboxyphenyi) propane dianhydrides, 2,
Bis- (2,3- dicarboxyphenyi) propane dianhydrides of 2-, bis- (3,4- dicarboxyphenyi) ether dianhydrides, bis- (3,4- dicarboxyphenyi) sulfones two
Bis- (2,3- dicarboxyphenyi) the ethane dianhydrides of acid anhydride, 1,1-, bis- (2,3- dicarboxyphenyi) methane dianhydrides, bis- (3,4- dicarboxyl benzene
Base) methane dianhydride, bis- (3,4- the dicarboxyphenyi) -1,1,1,3,3,3- hexafluoropropane dianhydrides of 2,2-, bis- (the 2,3- dicarboxyls of 2,2-
Phenyl) -1,1,1,3,3,3- hexafluoropropane dianhydride, bis- [(3,4- dicarboxyl) benzoyl] benzene dianhydrides of 1,3-, 1,4- it is bis- [(3,
4- dicarboxyl) benzoyl] benzene dianhydride, bis- { 4- [4- (1,2- dicarboxyl) phenoxy group] phenyl } propane dianhydrides of 2,2-, 2,2- be bis-
{ 4- [3- (1,2- dicarboxyl) phenoxy group] phenyl } propane dianhydride, bis- { 4- [4- (1,2- dicarboxyl) phenoxy group] phenyl } ketone two
Acid anhydride, bis- { 4- [3- (1,2- dicarboxyl) phenoxy group] phenyl } ketone dianhydrides, 4,4 '-bis- [4- (1,2- dicarboxyl) phenoxy group] biphenyl two
Acid anhydride, 4,4 '-bis- [3- (1,2- dicarboxyl) phenoxy group] biphenyl dianhydrides, bis- { 4- [4- (1,2- dicarboxyl) phenoxy group] phenyl } ketone two
Acid anhydride, bis- { 4- [3- (1,2- dicarboxyl) phenoxy group] phenyl } ketone dianhydrides, bis- { 4- [4- (1,2- dicarboxyl) phenoxy group] phenyl } sulfones
Dianhydride, bis- { 4- [3- (1,2- dicarboxyl) phenoxy group] phenyl } sulfone dianhydrides, bis- { 4- [4- (1,2- dicarboxyl) phenoxy group] phenyl }
Thioether dianhydride, bis- { 4- [3- (1,2- dicarboxyl) phenoxy group] phenyl } thioether dianhydrides, bis- { 4- [4- (1,2- dicarboxyl) benzene of 2,2-
Oxygroup] phenyl } -1,1,1,3,3,3- hexafluoropropane dianhydride, bis- { 4- [3- (1,2- dicarboxyl) phenoxy group] phenyl } -1,1 of 2,2-,
1,3,3,3- propane dianhydride, 2,3,6,7- naphthalene tetracarboxylic acid dianhydride, 1,4,5,8- naphthalene tetracarboxylic acid dianhydride, 1,2,5,6- naphthalene tetracarboxylic acid two
Acid anhydride, 1,2,3,4- benzene tertacarbonic acid dianhydride, 3,4,9,10- tetracarboxylic dianhydride, 2,3,6,7- anthracene tetracarboxylic dianhydride, 1,2,7,8- are luxuriant and rich with fragrance
Tetracarboxylic dianhydride etc..Above-mentioned carboxylic acid dianhydride ingredient can be used a kind, two or more can also be applied in combination.
Resin film 1 is selected from by polyester based resin film, cellulose-based resin film and imide series resin film group
At one of group resin film be preferably at least colorless and transparent in visible light region.As resin film 1, do not limit especially
It is fixed, for example, pet film (PET film) can be suitably used.
PET film is not particularly limited, for example, can enumerate non-stretched film, single axle drawn membrane, biaxially oriented film,
Oblique extension film etc..From the viewpoint of mechanical property, excellent heat resistance, in the present invention, make preferably by biaxial stretch-formed
The biaxially oriented film that molecule is orientated.
Preferably 15 μm~250 μm of resin film 1, the thickness such as PET film, it is 20 μm~190 μm more preferable, further
It is preferred that 45 μm~130 μm, it is 45 μm~55 μm particularly preferred.When with a thickness of in above range, the resin films such as PET film 1 have
The flexibility of durability and appropriateness, therefore be able to produce more efficiently by way of roll-to-roll (roll to roll) at it
On make dielectric layer 2, indium tin composite oxide layer 3 form a film.
Resin film 1 is not particularly limited such as PET film, from improving transparent conducting film and extraction electrode
From the perspective of adaptation, preferably the surface of configuration dielectric layer 2 is implemented at the surfaces such as sided corona treatment, corona treatment
Reason.
From the viewpoint of the durability for making resin film 1 have appropriateness, resin film 1 can be fitted such as PET film
Locality is formed with hard conating using the surface of the opposite side in the side configured with dielectric layer 2, indium tin composite oxide layer 3
The resin film of (not shown).If having hard conating, treatability when scratch resistance improves, touch panel is processed is improved.
Hard conating for example can by solidify thermohardening type resin combination or ultraviolet-curing resin composition come
It is formed., it is preferable to use the ultraviolet-curing resin composition of radical polymerization collaboration from the viewpoint of productivity.Ultraviolet light is solid
Change type resin combination generally comprises unsaturated monomer, oligomer, and/or resin and Photoepolymerizationinitiater initiater etc..It can be preferred
Use the ultraviolet curing resin of the acrylic compounds comprising polyfunctional ultraviolet hardening and Photoepolymerizationinitiater initiater
Composition.As the acrylic compounds of polyfunctional ultraviolet hardening, for example, can enumerate with 2 or more functions
Polyfunctional acrylic ester, polyfunctional carbamate acrylate, the multifunctional polyester acrylate etc. of group.Draw as photopolymerization
Agent is sent out, well known Photoepolymerizationinitiater initiater can be used.
For the thickness of hard conating, from the viewpoint of surface hardness and flexibility, preferably 0.5 μm~5.0 μm, more preferably
0.6 μm~2.0 μm.
The formation method of hard conating is not particularly limited, and wet process (rubbing method) can be used to be formed.
(dielectric layer 2)
For transparent conducting film, from raising indium tin composite oxide layer (also referred to as transparency conducting layer or electrically conducting transparent
Film) pattern formed after non-identification from the perspective of, sometimes in the transparent substrate of resin film etc. and indium tin combined oxidation
Setting has the dielectric layer of pH effect function between nitride layer.In contrast, it is believed that in the present invention, dielectric layer 2 has
PH effect function, by pH effect function make indium tin composite oxide layer pattern formed after non-identification improve, and
And as described later, the function that there is the amount to the active hydrogen-based on the surface for being present in indium tin composite oxide layer 3 to be adjusted.This
In specification, " active hydrogen-based " refers to the activity that can be chemically modified by trifluoroacetic anhydride in case of no particular description
Hydrogen-based.
Speculate by a surface configuration in resin film 1, such as polyester based resin film with a thickness of 0.005 μm~
0.100 μm and the dielectric layer 2 that is made of the mixture of organic matter or organic matter and inorganic matter, and in the configuration of dielectric layer 2
There is the surface configuration indium tin composite oxide layer 3 of the opposite side of the side of resin film 1, thus being situated between using sputtering method etc. in electricity
When the surface of matter layer 2 forms indium tin composite oxide layer 3, the moisture from the resin films such as polyester based resin film 1 is to indium tin
The surface of composite oxide layer 3 is mobile, and therefore, on the surface of indium tin composite oxide layer 3, there are 2.1 atom %~4.0 originals
Sub- %, the active hydrogen-based that can be chemically modified by trifluoroacetic anhydride.
Make transparent conducting film 10 as touch sensor and when playing a role, it is necessary to indium tin composite oxide layer
3 progress patterns are formed.It is formed in indium tin composite oxide layer 3 in figuratum transparent conducting film 10, it is multiple that there are indium tin
It closes the part of oxide skin(coating) 3 and the transmissivity for the part being not present, reflectivity and color difference is different, therefore there are electrode patterns to become
It is easy the problem of being identified, but by having the dielectric layer 2 with pH effect function, makes that there are indium tin composite oxide layers
The optical transmittance of 3 part and the part being not present is poor, reflection differences and color difference reduce, so that pattern becomes difficult to recognize.
Dielectric layer 2 is made of the mixture of organic matter or organic matter and inorganic matter.By there is dielectric layer 2
Machine object, to be easy to deposit on the surface for being in opposite side with the side configured with dielectric layer 2 of indium tin composite oxide layer 3
Reactive hydrogen base be adjusted to defined range.As organic matter, can enumerate acrylic resin, carbamate resins,
Melamine resin, alkyd resin, siloxane-based polymers, organosilan condensation product etc..As inorganic matter, controlled from refractive index
Easiness from the perspective of, it is preferable to use silica (also referred to as silica), aluminium oxide, zirconium oxide, titanium oxide etc..Its
In, it can be suitably used selected from the inorganic of one or more of the group being made of silica, aluminium oxide, zirconium oxide and titanium oxide
The mixture or siloxane-based polymers of composition granule and acrylic resin.For particles of inorganic material, if partial size is small, disperse
Property reduce, thus light transmittance is easily reduced, and if partial size becomes larger, possible refractive index adjusts function and is easily reduced or light transmittance
It is easily reduced, therefore average grain diameter is preferably 5nm~100nm, more preferably 10~20nm.As acrylic resin, for example,
It can enumerate and send as an envoy to comprising third made of the solidification of the resin combination of polyfunctional carbamate acrylate and Photoepolymerizationinitiater initiater
Olefin(e) acid resinoid etc..In addition, can be suitably used makes alkoxy silane hydrolysate and organosilicon as siloxane-based polymers
Alkoxy silane hydrolytic condensate made of sol particle condensation etc..Alternatively, it is also possible to by making dielectric layer 2 in organic matter
On the basis of also contain particles of inorganic material, thus be easy the reactive hydrogen base on the surface of indium tin composite oxide layer 3 is adjusted to provide
Range, and the surface roughness of transparent conducting film can be also adjusted to range appropriate to improving durability.
In the present invention, the average grain diameter of particles of inorganic material refers to the particle in the cross-sectional image obtained by transmission electron microscope
Value obtained from diameter is weighted and averaged.
Dielectric layer 2 can be 1 layer, or 2 layers or more of multilayer.From the viewpoint of productivity, preferably 1 layer.
From the viewpoint of the balance of transmissivity, reflectivity and color difference, preferably 2 layers or more.In the case where 2 layers or more of multilayered structure,
From the viewpoint of the balance of transmissivity, reflectivity and color difference, the dielectric layer 2 close to the side of resin film 1 is preferably improved
Refractive index and reduce far from resin film 1 side dielectric layer 2 refractive index.It is good from pH effect function
Viewpoint is set out, and the refractive index of dielectric layer 2 is preferably 1.30~1.80, is more preferably 1.40~1.60, is more preferably
1.50~1.60.
By make dielectric layer 2 with a thickness of 0.005 μm~0.100 μm of range, to be easy to will be present in indium tin multiple
The amount for closing the active hydrogen-based on the surface of oxide skin(coating) 3 is adjusted to defined range.In the present invention, dielectric layer 2 is 2 layers or more
In the case where multilayered structure, using all layers of aggregate thickness as the thickness of dielectric layer 2.In addition, if the thickness of dielectric layer 2
For above-mentioned range, then pH effect function and also become good with the adaptation of extraction electrode.If the thickness of dielectric layer 2 is super
Cross 0.100 μm, then since membrane stress, indium tin composite oxide layer 3 and the adaptation of extraction electrode reduce, if dielectric layer 2
Thickness is less than 0.005 μm, then pH effect function reduces.From the adaptation and optics of indium tin composite oxide layer and extraction electrode
It sets out in terms of the balance for adjusting function, the thickness of dielectric layer 2 is preferably 0.015 μm~0.040 μm, more preferably 0.020 μ
M~0.035 μm, further preferably 0.025 μm~0.030 μm.
Dielectric layer 2 can be by the dry or wets such as vacuum vapour deposition, sputtering method, ion plating method (rubbing method) come shape
At.Wherein, from the viewpoint of productivity, preferred wet process.
(indium tin composite oxide layer 3)
Indium tin composite oxide layer 3 is the metal oxidation being made of indium-tin composite oxides (Indium Tin Oxide)
Object film.For indium tin composite oxide layer 3, from the viewpoint of taking into account the transparency and low resistance, by indium oxide and tin oxide
Overall weight when being set as 100 weight %, preferably comprise 88 weight of weight %~98 % of indium oxide and contain 2 weight of tin oxide
The weight % of %~12 is measured, further preferably 90 weight of weight %~97 % of indium oxide simultaneously contains 3 weight of weight %~10 of tin oxide
% is measured, further preferably 92 weight of weight %~95 % of indium oxide simultaneously contains 5 weight of weight %~8 % of tin oxide.If oxygen
The content for changing tin is then to be easy to take into account the electrical characteristics such as the optical characteristics such as transmissivity, color difference and resistance value in above range.
For indium tin composite oxide layer 3, when being heated 90 minutes at 140 DEG C, sheet resistance be preferably 150 Ω/ with
Under, more preferably 140 Ω/ or less.When indium tin composite oxide layer after heating is low resistance, the sound of capacitive touch panels
It answers speed to improve, can help to saving power consumption of various optical devices etc..It should be noted that indium tin composite oxide layer 3 is logical
It crosses and heats 90 minutes at 140 DEG C to be crystallized.
In indium tin composite oxide layer 3, on the surface for being in opposite side with the side configured with dielectric layer 2, there are 2.1
The active hydrogen-based that can be chemically modified by trifluoroacetic anhydride of the atom of atom %~4.0 %.If there are 2.1 originals for active hydrogen-based
Sub- % or more, the then Interaction enhanced of active hydrogen-based and extraction electrode material, indium tin composite oxide layer 3 and extraction electrode
The adaptation of adaptation, i.e. transparent conducting film 10 and extraction electrode improves.On the other hand, it is more than if active hydrogen-based exists
4.0 atom %, the then electric conductivity, deterioration in optical properties of indium tin composite oxide layer 3 sometimes.From indium tin composite oxide layer 3 with
It, can be by trifluoro from the perspective of the adaptation of extraction electrode and the electric conductivity of indium tin composite oxide layer 3, the balance of optical characteristics
The amount for the active hydrogen-based that acetic anhydride is chemically modified preferably 2.5 atom of atom %~3.5 %, more preferable 2.6 atom %
~3.0 atom %.
In the present invention, the active hydrogen-based that can be chemically modified by trifluoroacetic anhydride is quantified by the following method.
After transparent conducting film to be carried out to heat treatment in 90 minutes at 140 DEG C, the exposure 60 in the steam of trifluoroacetic anhydride immediately
Minute is to be chemically modified processing.To the number of fluorine atoms X-ray on the transparent conducting film surface before and after moditied processing
Electron spectroscopy for chemical analysis (XPS) is quantified, and number of fluorine atoms increased after moditied processing is used as divided by 3 resulting values can be by trifluoro
The amount for the active hydrogen-based that acetic anhydride is chemically modified.
Preferred 15nm~the 40nm of thickness of indium tin composite oxide layer 3, more preferably 18nm~35nm, it is more preferably
20nm~30nm.By making with a thickness of the range, so as to make 3 low resistance of indium tin composite oxide layer after crystallization and
High-transmission rate.
It as the forming method of indium tin composite oxide layer 3, is not particularly limited, known method can be used.
Specifically, vacuum vapour deposition, sputtering method, ion plating method etc. can be enumerated.Wherein, go out from the viewpoint of film thickness monitoring and productivity
It sends out, preferably sputtering method, among sputtering method, from the viewpoint of productivity, particularly preferred DC magnetron sputtering method.
In the present invention, transparent conducting film, the thickness (also referred to as film thickness) of each layer for constituting transparent conducting film can
By utilizing transmission electron microscope (TEM) or scanning electron microscope (SEM) to transparent conducting film laminated body
Section observed to find out.
Fig. 2 is the schematic section of the transparent conducting film of another embodiment of the present invention.As shown in Fig. 2, transparent
Conductive membrane 20 includes resin film 1, the dielectric layer 2 being configured on a surface of resin film 1, in dielectric layer 2
The side configured with resin film 1 opposite side surface on the indium tin composite oxide layer 3 that configures and in indium tin composite oxygen
The extraction electrode 11 of the peripheral part configuration on the surface of the opposite side of the side configured with dielectric layer 2 of compound layer 3.It is right in Fig. 2
Part identical with Fig. 1 marks identical appended drawing reference, and the repetitive description thereof will be omitted.In addition, identical part has in Fig. 2 and Fig. 1
There is same function.
(extraction electrode 11)
Extraction electrode 11 can be formed by metal.Specifically, the material as extraction electrode, can enumerate silver, copper,
Aluminium, nickel, palladium, chromium, iron, molybdenum, titanium or using them as metals such as the alloys of principal component；By silver, copper, aluminium, nickel, palladium, chromium, iron, molybdenum, titanium
Or using they be the metals such as the alloy of principal component as the conducting paste material etc. of principal component.Wherein, preferred conductions such as silver, copper
The high metal of property, the metal dispersion for keeping the electric conductivity such as silver, copper high are formed in curable resins such as epoxy resin, acrylic resins
Conductive metal Paste Materials since extraction electrode can be readily formed by printing, preferably.Wherein, from extraction
It sets out in terms of the balance for the easiness that the electric conductivity of electrode is formed with extraction electrode, particularly preferably using silver as the conduction of principal component
Property silver paste agent material.For metal, from the viewpoint of the fine precision of the resistance of extraction electrode and electrode pattern, average grain diameter
Preferably 0.1~10 μm, more preferably 0.1~3.0 μm.In the present invention, " using metal as the conducting paste material of principal component "
Refer to the metal in terms of solid component concentration comprising 50 weight % or more.In addition, in the present invention, the average grain diameter of metallic particles is
Refer to value obtained from being weighted and averaged as the particle diameter in the cross-sectional image that transmission electron microscope obtains.
In an embodiment of the invention, from the viewpoint of the transparency is excellent, the total light transmission of transparent conducting film
Rate is preferably 80% or more, more preferably 85% or more, further preferably 87% or more.The total light transmission of transparent conducting film
Rate is measured as described later.
In an embodiment of the invention, for transparent conducting film, from electrode pattern formed after non-identification
From the perspective of good, L*a*b*B in colour system*Value preferably 2.5 or less is more preferably 2.4 or less, is further preferred
It is 2.3 or less.The b of transparent conducting film*Value is measured as described later.
In an embodiment of the invention, for transparent conducting film, from the excellent adhesion with extraction electrode
Viewpoint is set out, and the area of release surface is preferably 60% or less, more preferably 55% or less in adaptation evaluation.Transparent conductivity
The adaptation evaluation of film carries out as described later.
In an embodiment of the invention, for transparent conducting film, from the durability including scratch resistance
From the perspective of good, surface roughness Ra is preferably 1.80nm~30.0nm, is more preferably 1.85nm~20.0nm, is further
Preferably 1.90nm~10.0nm.The surface roughness Ra of transparent conducting film refers to arithmetic average roughness, as described later
Ground is measured.
In an embodiment of the invention, transparent conducting film can be used as the devices such as display, touch panel, hair
The transparent electrode of the semiconductor elements such as optical element, photo-electric conversion element uses, and the transparent electrode for being suitable as touch panel makes
With particularly preferably being used in capacitive touch panels.
In an embodiment of the invention, transparent conducting film for example can be by as selected from by Polyester tree
One table of the resin film 1 of one of the group of membrane of lipoprotein, cellulose-based resin film and imide series resin film composition
Dielectric layer 2 is laminated on face, indium tin is laminated on the surface of the opposite side of the side configured with resin film 1 of dielectric layer 2
Composite oxide layer 3 makes.As resin film 1, the surface that the side of configuration dielectric layer 2 can be used passes through at corona
The resin film that reason or corona treatment are surface-treated.In addition, can be used and be configured with as resin film 1
The opposite side of the side of dielectric layer 2 has the resin film of hard conating.As the forming method of indium tin composite oxide layer 3,
From the viewpoint of film thickness monitoring and productivity, preferred sputtering method, in sputtering method, from the viewpoint of productivity, particularly preferably
DC magnetron sputtering method.Sputtering method is not particularly limited, and can carry out under conditions of well known formation indium tin composite oxide layer.
It can speculate: by being formed on a surface of resin film 1 with a thickness of 0.005 μm~0.100 μm, by organic matter
Or after the dielectric layer 2 of the mixture composition of organic matter and inorganic matter, in the side configured with resin film 1 of dielectric layer 2
The surface of opposite side indium tin composite oxide layer 3 is formed by sputtering method etc., so that the moisture from resin film 1 makes indium
It is mobile to the surface of indium tin composite oxide layer 3 when tin composite oxide layer forms a film, it is deposited on the surface of indium tin composite oxide layer 3
In the active hydrogen-based that can be chemically modified by trifluoroacetic anhydride of 2.1 atom of atom %~4.0 %.
Embodiment
Hereinafter, enumerating embodiment, more specifically the present invention will be described.It should be noted that the present invention is not limited to this
A little embodiments.
In Examples and Comparative Examples, various characteristics are evaluated or measured as described below.
<adaptation evaluation>
On the surface of the indium tin oxide layer of the transparent conducting film after 140 DEG C, heat treatment in 90 minutes, utilize
Screen process press is coated with about 75 weight of Argent grain containing 2 μm of average grain diameter with the area of 7 μm of thickness after roasting, 3cm square
Measure the conductive silver paste of %, about 2 weight % of epoxy system resin, about 0.5 weight % of acrylic resin.10 points are stood after coating
Zhong Hou carries out heating in 60 minutes at 140 DEG C and roasts to conductive silver paste, formed on indium tin oxide layer by leading
Electrical silver paste dosage form at extraction electrode.It is relatively wet that the transparent conducting film for foring extraction electrode is put into temperature 60 C
240 hours in the environment chambers of degree 90%, after taking-up, from extraction electrode side, about 30 μm of depth of 100 lattice are cut out with knife
Cut mark, as adaptation sample for evaluation.There is the surface of the side of extraction electrode to attach 25mm's wide in the formation of evaluation sample
Transparent adhesion adhesive tape (3M corporation, #610) was that 90 degree of directions are used about 1 second relative to transparent conducting film after about 1 minute
Clock removes adhesive tape, calculates the stripping area of extraction electrode removing relative to transparent conducting film configured with extraction electrode
The ratio (%) of the entire area on the surface of side.The ratio of stripping area is smaller, and adaptation is the better.
<conducting of release surface is evaluated>
Make the testing machine contact part that extraction electrode is removed in adaptation evaluation, the presence or absence of confirmation conducting.Energy
The part for enough confirming conducting means to be removed between indium tin oxide layer and extraction electrode.
<quantifying for active hydrogen-based>
Carried out at 140 DEG C 90 minutes heat treatment after, immediately by transparent conducting film trifluoroacetic anhydride steam
Middle exposure 60 minutes and be chemically modified processing.To the indium tin oxide layer in the transparent conducting film before and after moditied processing
The number of fluorine atoms on surface quantified with X-ray photoelectron spectroscopy (XPS), number of fluorine atoms increased after moditied processing is removed
Using 3 resulting values as can be by the amount of the active hydrogen-based of trifluoroacetic anhydride chemical modification.
<measurement of total light transmittance>
It is measured using optical profile type nephelometer (Japanese electricity Shi Industrial Co., Ltd system, NDH7000).Light source uses D light
Source makes light from the incidence of indium tin oxide layer side, measures total light transmittance.
<b*The measurement of value >
It is measured using colour difference meter (Japanese electricity Shi Industrial Co., Ltd system, SE2000).Light source uses D light source, makes light
From the incidence of indium tin oxide layer side, b is measured*Value.b*When value is 2.5 or less, the non-identification of pattern is good.
<measurement of sheet resistance>
The transparent conducting film after heating will be carried out 90 minutes at 140 DEG C and cuts out 60mm × 60mm, uses three
Water chestnut Chemical Co., Ltd. Loresta GP, with the sheet resistance of four probe method measurement indium tin oxide layer.
<measurement of surface roughness Ra>
The transparent conducting film after heating will be carried out 90 minutes at 140 DEG C and is cut into 60mm × 60mm, to gained
The two sides of sample calculates 0.1mm × 0.1mm's with surface shape measuring machine (Canon Inc. system, Zygo New View7300)
Arithmetic average roughness Ra in measurement range, as surface roughness Ra.Measurement is in 23 DEG C of temperature, the perseverance of relative humidity 50%
It is carried out in greenhouse.Cutoff value is 0.5mm.
(embodiment 1)
As resin film, 50 μm of pet film of thickness is used.The poly terephthalic acid second
Terephthalate films have 1.0 μm of thickness of hard conating on a surface.Hard conating is made with ultraviolet light comprising multifunctional amino first
The resin combination of acid esters acrylate, silica dioxide granule (average grain diameter 200nm or less) and Photoepolymerizationinitiater initiater solidify and
It is formed.0.030 μm of thickness of dielectric layer is formed on another surface of the pet film.Electricity is situated between
Matter layer is to make the resin comprising polyfunctional carbamate acrylate, silica dioxide granule and Photoepolymerizationinitiater initiater with ultraviolet light
What composition was solidified to form, refractive index 1.5.By the laminated body of the pet film and dielectric layer
Imported into coiling type DC magnetron sputtering film forming apparatus, after being heated 30 seconds at 90 DEG C, by sputtering method dielectric layer table
The indium tin composite oxide layer of face formation thickness 23nm.
Formation for indium tin composite oxide layer, as target, using containing 7.0 weight % of tin oxide and indium oxide 93.0
The tin indium oxide of weight %.For sputtering, while the mixed gas that oxygen/argon ratio is 5/100 is imported into film interior, side
Pressure in device is set as 0.4Pa, is carried out 30 seconds under conditions of input power 18.5kW.Then, 90 are carried out at 140 DEG C
Minute heat treatment, crystallizes indium tin composite oxide layer.
(embodiment 2)
The alkoxy silane hydrolytic condensate as made of being condensed alkoxy silane hydrolysate and organic silica gel is (siloxane-based
Polymer) dielectric layer is formed, and make with a thickness of 0.025 μm, refractive index 1.5, in addition to this, by same with embodiment 1
The method of sample obtains transparent conducting film.
(embodiment 3)
To shape after the surface progress sided corona treatment of the side of the formation dielectric layer of pet film
At dielectric layer, in addition to this, transparent conducting film is obtained by method similarly to Example 2.
(comparative example 1)
Make dielectric layer with a thickness of 1.600 μm, refractive index 1.6, in addition to this, pass through side similarly to Example 1
Method obtains transparent conducting film.
(comparative example 2)
Make operating similarly with example 1 in addition to this with a thickness of 1.600 μm, refractive index 1.6 for dielectric layer, obtains
To the laminated body of pet film and dielectric layer.By the pet film and electricity
The laminated body of dielectric layer is imported into coiling type RF magnetron sputtering film forming apparatus, after heating in 75 seconds is carried out at 90 DEG C, by splashing
It penetrates method and forms the indium tin composite oxide layer of thickness 20nm on the surface of dielectric layer.
Formation for indium tin composite oxide layer, as target, using containing 7.0 weight % of tin oxide, indium oxide 93.0
The tin indium oxide of weight %.For sputtering, while the mixed gas that oxygen/argon ratio is 5/100 is imported into film interior, side
Pressure in device is set as 0.4Pa, is carried out 75 seconds under conditions of input power 6kW.To obtained transparent conducting film
It carries out heating for 90 minutes at 140 DEG C, crystallizes indium tin composite oxide layer.
In Examples 1 to 3 and comparative example 1~2, adaptation, the removing of transparent conducting film are carried out as described above
The conductive evaluation in face.In addition, in Examples 1 to 3 and comparative example 1~2, carry out active the quantitative of hydrogen-based, sheet resistance, it is total thoroughly
Light rate, b*The measurement of value and surface roughness.It the results are shown in following table 1.
[table 1]
In addition, the indium tin for being present in transparent conducting film for showing Examples 1 to 3 and comparative example 1~2 in Fig. 3 is multiple
Close oxide skin(coating) surface the active hydrogen-based that can be chemically modified by trifluoroacetic anhydride amount and transparent conducting film with
The relationship of the removing ratio of extraction electrode.
According to table 1 and Fig. 3 it is found that being 2.1 former for the active hydrogen-based on the surface for being present in indium tin composite oxide layer
The transparent conducting film of the Examples 1 to 3 of sub- % or more, the stripping area in adaptation evaluation are not observed less than 60%
To the conducting of release surface, therefore the adaptation of indium tin composite oxide layer and extraction electrode improves.And then it is found that total light transmittance,
The evaluation of sheet resistance, b* value and surface roughness Ra is good, transparent, non-identification, electric conductivity and excellent in te pins of durability, can
To be suitable for touch panel.Wherein, stripping area of the transparent conducting film of embodiment 3 in adaptation evaluation is insufficient
10%, adaptation is especially excellent.
On the other hand it is found that the active hydrogen-based on the surface for being present in indium tin composite oxide layer is few, is former less than 2.1
The transparent conducting film of the comparative example 1 and 2 of sub- %, the stripping area in adaptation evaluation is more than 60%, observes removing
The conducting in face, therefore transparency conducting layer is low with the adaptation of extraction electrode.
Description of symbols
1 resin film
2 dielectric layers
3 indium tin composite oxide layers
10,20 transparent conducting film
11 extraction electrodes
Claims (7)
1. a kind of transparent conducting film is configured in order dielectric layer on a surface of resin film and indium tin is compound
Oxide skin(coating), which is characterized in that
The resin film is selected from being made of polyester based resin film, cellulose-based resin film and imide series resin film
One of group,
The dielectric layer is made of the mixture of organic matter or organic matter and inorganic matter, and with a thickness of 0.005 μm or more and
0.100 μm hereinafter,
On the surface of the opposite side of the side configured with dielectric layer of indium tin composite oxide layer, there are more than 2.1 atom %
And 4.0 atom % active hydrogen-based below that can be chemically modified by trifluoroacetic anhydride.
2. transparent conducting film according to claim 1, wherein the indium tin composite oxide layer be configured with
The side of dielectric layer is in the peripheral part on the surface of opposite side configured with extraction electrode.
3. transparent conducting film according to claim 2, wherein the extraction electrode is by using silver as the conduction of principal component
Property paste constitute.
4. transparent conducting film described in any one of claim 1 to 3, wherein described to match in the resin film
The surface for being equipped with the side of dielectric layer has carried out sided corona treatment.
5. a kind of manufacturing method of transparent conducting film, which is characterized in that selected from by polyester based resin film, cellulose-based
Dielectric layer is laminated on a surface of resin film in one of the group of resin film and imide series resin film composition, institute
Dielectric layer is stated to be made of the mixture of organic matter or organic matter and inorganic matter and with a thickness of 0.005 μm or more and 0.100 μm
Hereinafter,
Indium tin composite oxide layer is laminated on the surface of the opposite side of the side configured with resin film of the dielectric layer,
Transparent conducting film is obtained, the transparent conducting film includes resin film, dielectric layer and indium tin combined oxidation
Nitride layer, and the surface of the opposite side of the side configured with dielectric layer of indium tin composite oxide layer there are 2.1 atom % with
The upper and 4.0 atom % active hydrogen-based below that can be chemically modified by trifluoroacetic anhydride.
6. the manufacturing method of transparent conducting film according to claim 5, wherein described in the configuration of the resin film
The surface of the side of dielectric layer has carried out sided corona treatment.
7. the manufacturing method of transparent conducting film according to claim 5 or 6, wherein formed by sputtering method described
Indium tin composite oxide layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016097316 | 2016-05-13 | ||
| JP2016-097316 | 2016-05-13 | ||
| PCT/JP2017/004534 WO2017195419A1 (en) | 2016-05-13 | 2017-02-08 | Transparent conductive film and method for producing same |
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| Publication Number | Publication Date |
|---|---|
| CN109155166A true CN109155166A (en) | 2019-01-04 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201780029395.XA Pending CN109155166A (en) | 2016-05-13 | 2017-02-08 | Transparent conducting film and its manufacturing method |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6717934B2 (en) |
| CN (1) | CN109155166A (en) |
| WO (1) | WO2017195419A1 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0279027A (en) * | 1988-09-16 | 1990-03-19 | Hitachi Ltd | Polycrystalline silicon thin film transistor |
| CN1639294A (en) * | 2002-06-28 | 2005-07-13 | 株式会社普利司通 | Anisotropic conductive film |
| JP2009076432A (en) * | 2007-01-18 | 2009-04-09 | Nitto Denko Corp | Transparent conductive film, method for producing the same, and touch panel provided with the same |
| CN102076776A (en) * | 2008-06-30 | 2011-05-25 | 住友化学株式会社 | Composition for insulating layer |
| JP2015032071A (en) * | 2013-07-31 | 2015-02-16 | 王子ホールディングス株式会社 | Method for manufacturing conductive sheet, conductive sheet and touch panel |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013171454A (en) * | 2012-02-21 | 2013-09-02 | Toppan Printing Co Ltd | Electrode panel of display device and method of manufacturing thereof |
-
2017
- 2017-02-08 JP JP2018516348A patent/JP6717934B2/en active Active
- 2017-02-08 CN CN201780029395.XA patent/CN109155166A/en active Pending
- 2017-02-08 WO PCT/JP2017/004534 patent/WO2017195419A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0279027A (en) * | 1988-09-16 | 1990-03-19 | Hitachi Ltd | Polycrystalline silicon thin film transistor |
| CN1639294A (en) * | 2002-06-28 | 2005-07-13 | 株式会社普利司通 | Anisotropic conductive film |
| JP2009076432A (en) * | 2007-01-18 | 2009-04-09 | Nitto Denko Corp | Transparent conductive film, method for producing the same, and touch panel provided with the same |
| CN102076776A (en) * | 2008-06-30 | 2011-05-25 | 住友化学株式会社 | Composition for insulating layer |
| JP2015032071A (en) * | 2013-07-31 | 2015-02-16 | 王子ホールディングス株式会社 | Method for manufacturing conductive sheet, conductive sheet and touch panel |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017195419A1 (en) | 2017-11-16 |
| JP6717934B2 (en) | 2020-07-08 |
| JPWO2017195419A1 (en) | 2019-03-14 |
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