KR20210075016A - Transparent conductive film, patterned transparent conductive film, optical member, and electronic device - Google Patents

Abstract

The present invention is to provide a transparent conductive film having excellent surface roughness, curling properties and HC properties. The transparent conductive film is formed by laminating a hard coat layer on a single surface (I surface) of a transparent film, and a high-refractive index layer and a transparent conductive layer on the opposite surface (II surface), wherein the hard coat layer is a cured product of a hard coat agent including a film-forming ingredient containing urethane (meth)acrylate (A), a metal oxide (B) and a photopolymerization initiator (C), and the hard coat layer has a surface roughness (Ra) of less than 1.5 nm. In addition, when a square specimen having a size of 10 cm x 10 cm and including a hard coat layer formed by using the hard coat agent to a layer thickness of 2 micrometers is allowed to stand at 100℃ for 1 minute at a time point within 30 minutes after forming the hard coat layer, the average of curl lift heights of four corners of the specimen is 10 mm or less.

Description

Transparent conductive film, pattern-forming transparent conductive film, optical member, and electronic device {TRANSPARENT CONDUCTIVE FILM, PATTERNED TRANSPARENT CONDUCTIVE FILM, OPTICAL MEMBER, AND ELECTRONIC DEVICE}

This invention relates to the transparent conductive film formed using a specific hard-coat agent.

A high refractive index layer (refractive index 1.55 to 1.90) is prepared by coating a high refractive index paint on a crystalline transparent film, and then a material for forming a transparent conductive layer on the high refractive index layer is uniformly formed by sputtering or the like. The film is used as an electrode material of a display device such as a touch panel by patterning the transparent conductive layer into a desired shape again after that.

The material for forming the transparent conductive layer is made of indium tin oxide (hereinafter referred to as ITO), which is an indium-based oxide, silver or copper in view of high visible light transmittance, relatively low surface resistance, and excellent environmental characteristics. , which has nanowires as the main component is widely used.

When manufacturing a transparent conductive film or manufacturing an optical member using a transparent conductive film, industrially, a long transparent conductive film is conveyed at high speed, or a long transparent conductive film is wound in a roll shape, solve or do In such a conveying process, winding process, and winding process, if the contact area between the transparent conductive layer and the surface on which the transparent conductive layer of the crystalline transparent film is not provided (which comes into contact with the transparent conductive layer) is too large, it is blocked. There is a problem that the transparent conductive layer is scratched when it is transported, wound, or unwound against blocking.

In order to solve this problem, it has been proposed to form a hard coat layer for preventing blocking on the surface where the transparent conductive layer of the transparent film is not provided (Patent Document 1 and the like).

In Patent Document 1, (A) an alkylene oxide-modified (meth)acrylate monomer having 3 or more (meth)acryloyl groups, (B) Polyfunctional urethane (meth) having 6 or more (meth)acryloyl groups An ultraviolet curable anti-blocking hard coat resin composition comprising an acrylate oligomer, (C) silica particles having an average primary particle diameter of 5 nm to 20 nm, and an average secondary particle diameter of 100 nm to 300 nm, and (D) a photopolymerization initiator is disclosed.

In addition, in Patent Document 2, in order to impart excellent scratch resistance and substrate adhesion to the cyclic olefin resin substrate, (A) urethane (meth)acrylate having an unsaturated group equivalent of 110 or more and less than 600 and a weight average molecular weight of 600 to 6,000 , (B) a benzophenone-based initiator and/or a thioxanthone-based initiator, and (C) an active energy ray-curable composition comprising silica particles having an average primary particle diameter of 1 nm to 200 nm is disclosed.

Japanese Patent Laid-Open No. 2017-226787 Japanese Patent Laid-Open No. 2018-203887

By the way, the above-mentioned elongate transparent conductive film tends to become elongate in recent years from a viewpoint of productivity or economical efficiency. By producing a longer transparent conductive film, the ratio of the time required for preparation of each process to the total production time is reduced, and the lead part at the start or end of winding (finally unusable part) occupies the entire product. This is because the ratio of can be reduced or made.

However, since the transparent conductive film becomes longer, an excessive load is applied to the portion close to the core, and the hard coat layer for preventing blocking is required to have sufficient hardness so that the hard coat layer itself is not damaged. It is required that the surface does not scratch the surface of the crystalline transparent film or the surface of the transparent conductive layer.

In addition, in response to the demand for miniaturization and weight reduction of electronic devices, reduction in size and weight is also required for the optical member constituting the electronic device, and the transparent conductive film constituting the optical member, and the transparent conductive film constituting the transparent conductive film The demand for thinning the support body and the high refractive index layer is increasing.

However, when a support body becomes thin, Curl|Curl will generate|occur|produce remarkably in the intermediate body before providing a high refractive index layer or a transparent conductive layer by hardening and shrinkage|contraction of the hard-coat layer for blocking. The high refractive index layer or the transparent conductive layer is a layer provided on the opposite side of the hard coat layer for preventing blocking with a support interposed therebetween, and when curls occur in the intermediate body, it becomes difficult to form a uniform high refractive index layer or transparent conductive layer. Alternatively, even if the high refractive index layer or the transparent conductive layer is formed while the intermediate is flattened by pulling the intermediate, the hard coat layer in the transparent conductive film after forming the high refractive index layer or the transparent conductive layer is affected by curing shrinkage. little is left

In addition, by changing the lamination order, a high refractive index layer or a transparent conductive layer is first laminated on the support, and then a hard coat layer for preventing blocking is formed on the opposite side of the support (the surface on which the high refractive index layer or the transparent conductive layer is not provided). In this case, if the curing shrinkage of the hard coat layer is large, the high refractive index layer or the transparent conductive layer prepared earlier is affected by the curing shrinkage of the hard coat layer and shrinks, and the uniformity is impaired, causing malfunction in the touch sensing function after assembly. There is a problem that such defects are likely to occur.

Since the hard coat layer disclosed in Patent Documents 1 and 2 has a large surface roughness Ra, there is a problem in that the surface of the high refractive index layer or the surface of the transparent conductive layer is damaged. A scratch on the surface of the high refractive index layer or the transparent conductive layer may not only impair transparency, but may also impair electrical stability.

Moreover, the hard-coat layer disclosed by patent documents 1 and 2 also has the problem that curl is easy to produce.

The present invention provides a transparent conductive film having a hard coat layer that is small in surface roughness, hardly curled, and sufficiently hard, and a high refractive index layer and a transparent conductive layer on the opposite side to the hard coat layer, with a transparent film as a support therebetween. intended to provide

One embodiment of the present invention is a transparent conductive film in which a hard coat layer is laminated on one side (side I) of a transparent film, and a high refractive index layer and a transparent conductive layer are laminated on the opposite side (side II), wherein the hard coat layer is urethane. It is a cured product of a hard coat agent comprising a film-forming component comprising (meth)acrylate (A), a metal oxide (B), and a photoinitiator (C), and the surface roughness Ra of the hard coat layer is 1.5 A 10 cm x 10 cm square test piece in which a hard coat layer having a thickness of less than nm and a film thickness of 100 µm is formed on a polyethylene terephthalate film having a film thickness of 100 µm using the hard coat agent 30 minutes after forming the hard coat layer into a film It relates to a transparent conductive film having an average of the curl heights of the four corners of the test piece of 10 mm or less when left still in an environment of 100° C. for 1 minute.

Moreover, another one Embodiment of this invention relates to the pattern formation transparent conductive film formed by patterning the transparent conductive layer in said transparent conductive film.

Moreover, another one Embodiment of this invention relates to the optical member provided with the said pattern formation transparent conductive film.

In addition, another embodiment of the present invention relates to an electronic device provided with the optical member.

According to an embodiment of the present invention, a hard coat layer having a small surface roughness, hardly causing curls, and a sufficiently hard hard coat layer with a transparent film as a support therebetween, and a high refractive index layer and a transparent conductive layer on the opposite side to the hard coat layer. A transparent conductive film may be provided.

Furthermore, by using a hard coat agent containing a hydroxyl group-containing solvent, bubbles generated at the time of stirring can be quickly removed. Accordingly, in the process, it is possible to apply immediately after stirring, and also, it is possible to significantly reduce defects in the coating film derived from bubbles, thereby increasing the yield.

<<Transparent conductive film>>

The transparent conductive film of the embodiment of the present invention is formed by laminating a hard coat layer on one side (side I) of a transparent film, and a high refractive index layer and a transparent conductive layer on the opposite side (side II) of the transparent film. In addition, the said transparent conductive film is also called transparent conductive film (alpha).

1. Hard coat layer

The hard-coat layer in embodiment of this invention is hardened|cured material of the hard-coat agent demonstrated below. The surface roughness (Ra) of a hard-coat layer is less than 1.5 nm, Furthermore, it is less than 0.1-1.5 nm. Surface roughness (Ra) represents the arithmetic mean roughness defined in JIS B0601·JIS B0031.

[[hard coat product]]

The hard-coat agent for forming the hard-coat layer in embodiment of this invention, the film-forming component containing at least urethane (meth)acrylate (A), a metal oxide (B), and a photoinitiator (C) include

[film-forming component]

The film-forming component contains at least the urethane (meth)acrylate (A) demonstrated below. The film-forming component may also contain the reaction product of the (meth)acrylate and polyisocyanate which have the hydroxyl group mentioned later, for example. Hereinafter, the reaction product is also described as a product containing urethane (meth) acrylate (A), and the product containing urethane (meth) acrylate (A) is an unreacted product other than urethane (meth) acrylate (A) etc. may be included.

Moreover, the film-forming component may also contain the compound which has a polymerizable unsaturated double bond group, such as a (meth)acrylic-type compound.

<Urethane (meth)acrylate (A)>

Urethane (meth)acrylate (A) can be obtained by the following method, for example.

Method 1; A method of reacting (meth)acrylates (a1) having a hydroxyl group and polyisocyanate (a2).

Method 2; A method of reacting an isocyanate group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate (a2) under conditions of excess isocyanate groups with (meth)acrylates (a1) having a hydroxyl group.

Method 3; A method of reacting a hydroxyl group-containing urethane prepolymer obtained by reacting a polyol and a polyisocyanate (a2) under conditions of excess hydroxyl groups with (meth)acrylates having an isocyanate group.

Method 4; A method of reacting a carboxyl group-containing urethane prepolymer obtained by reacting a polyol having a carboxyl group and a polyisocyanate (a2) under conditions of excess hydroxyl groups with (meth)acrylates having an epoxy group.

Method 1, which is a simple synthesis method, is preferable in view of the number of synthesis steps.

((meth)acrylates having a hydroxyl group (a1))

As the (meth)acrylates (a1) having a hydroxyl group used in the methods 1 and 2, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl ( (meth)acrylates having a hydroxyl group such as meth)acrylate, isocyanuric acid-modified diacrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate are mentioned.

(Polyisocyanate (a2))

Examples of the polyisocyanate (a2) used in the above methods 1 to 4 include tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated products thereof, isophorone diisocyanate, hexamethylene diisocyanate, etc. and these of trimethylolpropane adduct body, trimerized nurate body, allophanate body, biuret body, etc. are mentioned.

Examples of the polyol used in Methods 2 and 3 include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentyl glycol, and neopentyl. In addition to glycol, polytetramethylene glycol, hexanetriol, trimethylolpropane, glycerin, pentaerythritol, etc.,

and polycondensation products of the polyol and polybasic acid or polybasic acid anhydride.

Examples of the polybasic acid and polybasic acid anhydride include aromatic polybasic acids such as phthalic acid and phthalic anhydride, and aliphatic polybasic acids such as adipic acid and sebacic acid.

As (meth)acrylates which have an isocyanate group used by the said method 3, 2-(meth)acryloyloxyethyl isocyanate, (meth)acryloyl isocyanate, etc. are mentioned.

Examples of the polyol having a carboxyl group used in the method 4 include dimethylolbutanoic acid and dimethylolpropionic acid. Furthermore, polyols, such as ethylene glycol and propylene glycol, and polybasic acids, such as dimethylol butanoic acid, and polybasic acid anhydride, polycondensate are mentioned.

As (meth)acrylates which have an epoxy group used by the said method 4, glycidyl (meth)acrylate is mentioned.

The number of (meth)acrylates which have a hydroxyl group, polyisocyanate, polyol, and (meth)acrylates which have an isocyanate group may each be one, respectively, and can use it in combination of 2 or more types.

It is preferable that urethane (meth)acrylate (A) has a ring structure in a molecule|numerator from a viewpoint of curl reduction. For example, by having an alicyclic structure and/or a nurate ring structure, curing shrinkage at the time of irradiation with an active energy ray can be significantly reduced, and thereafter, a dark reaction proceeds and curling becomes difficult even if curing proceeds. It is preferable to have a nurate ring structure especially.

Urethane (meth)acrylate (A) having an alicyclic structure is a polyisocyanate, a hydrogenated product of isophorone diisocyanate or tolylene diisocyanate, a hydrogenated product of xylylene diisocyanate, a hydrogenated product of methylene diphenyl diisocyanate, and It can be obtained by using these derivatives. Alternatively, it can be obtained by using cyclohexanedimethanol mono(meth)acrylate as (meth)acrylates having a hydroxyl group. Alternatively, it can be obtained by using cyclohexanediol as the polyol. Or it can obtain by using cyclohexanedicarboxylic acid or its anhydride as a polybasic acid or a polybasic acid anhydride.

The urethane (meth)acrylate (A) which has a nurate ring structure can be obtained by using the trimer (nurate body) formed from various diisocyanate components as a polyisocyanate in the said methods 1-4.

It is preferable to use what has 6 or more (meth)acryloyl groups from a viewpoint of hardness (HC property) as urethane (meth)acrylate (A), It is to use what has 9 or more (meth)acryloyl groups more preferably. It is preferable to use what has an acryloyl group from a hardenable viewpoint.

And it is preferable to have 3-10 pieces on average, and, as for the film-forming component containing urethane (meth)acrylate (A), it is more preferable to have 4-8 pieces.

When obtaining the urethane (meth)acrylate (A) by the above methods 1 to 4, in addition to the ideal urethane (meth)acrylate (A), the following various components may be included. Method 1 will be described as an example.

For example, some (meth)acrylates having one hydroxyl group, which are raw materials, are provided in a mixed state with (meth)acrylates not having a hydroxyl group. The (meth)acrylates which do not have a hydroxyl group other than the ideal urethane (meth)acrylate (A) will also be contained in a product. In addition, in general, (meth)acrylates having a hydroxyl group are used excessively compared to polyisocyanate, so (meth)acrylates having one unreacted hydroxyl group are also included in the product by method 1.

Furthermore, in those manufactured and sold as (meth)acrylates having one hydroxyl group, (meth)acrylates having two or more hydroxyl groups or (meth)acrylic acid, which is a raw material of (meth)acrylates, contains a small amount. sometimes it becomes

Therefore, in (meth)acrylates having one unreacted hydroxyl group in a part of the (meth)acryloyl group in the ideal urethane (meth)acrylate (A), (meth)acryloyl group or hydroxyl group ( Those in which (meth)acryloyl groups in meth)acrylates react one after another, (meth)acrylates having two or more hydroxyl groups, (meth)acrylates having one hydroxyl group, and polyisocyanates are also reacted, It is included in the product by method 1, and the product by method 1 is an aggregate of molecular species of various structures and molecular weights, and exhibits a relatively broad molecular weight distribution. The same is the case with methods 2 to 4.

Accordingly, a method of obtaining the average number of (meth)acryloyl groups in the film-forming component containing urethane (meth)acrylate (A) is a (meth)acryl group having a hydroxyl group and five (meth)acryloyl groups. Dipentaerythritol pentaacrylate (hereinafter referred to as DPPA. molecular weight: 524) and dipentaerythritol hexaacrylate, which is a (meth)acrylate having 6 (meth)acryloyl groups without a hydroxyl group (hereinafter referred to as DPPA) , called DPHA.Molecular weight: 578) of a composition containing 1:1 (molar ratio): 2103 g, a nurate form of hexamethylene diisocyanate containing 21.8 wt% of isocyanate groups (hereinafter referred to as HDI-nurate). : A case of reacting with 74 g (about 0.38 mol = (74 × 0.218/42) × 100) as an isocyanate (NCO) group) will be described as an example.

Since DPPA has one hydroxyl group per molecule and HDI nurate has three NCO groups per molecule, it is thought that 3 molecules of DPPA react with one molecule of HDI nurate. Accordingly, DPPA contained in 2103 g of the composition is 1000 g (about 1.91 mol), of which about 199 g of DPPA corresponding to about 0.38 mol is considered to react with the HDI nurate (molecular weight: 504), and as a result, the product silver,

Theoretical molecular weight: 2076 (=504+524×3).

Urethane (meth)acrylate (A) having 15 (meth)acryloyl groups: about 273 g;

unreacted DPPA having 5 (meth)acryloyl groups: about 801 g;

DPHA having 6 (meth)acryloyl groups: Assume that it contains about 1103 g.

Therefore, the average number of (meth)acryloyl groups in the film-forming component containing the urethane (meth)acrylate (A) is (273×15+801×5+1103×6)/(2103+74)=6.8 becomes this

That is, the average number of (meth)acryloyl groups which the film-forming component has here is a theoretical value.

On the other hand, it is considered that the whole product is an aggregate of molecular species having various structures and molecular weights as described above, but it is virtually impossible to specify each molecular species and each content ratio.

Accordingly, the properties of the whole product are specified by the above theoretical average number of (meth)acryloyl groups and the mass average molecular weight (Mw).

The mass average molecular weight can be obtained according to the method described later.

It is preferable that it is 1000-6000, as for the mass average molecular weight (Mw) of the film-forming component containing a urethane (meth)acrylate (A), it is more preferable that it is 1200-4000, It is still more preferable that it is 1400-3500. By setting the mass average molecular weight (Mw) to 1000 to 6000, it is easy to make curl properties and HC properties compatible.

200-900 are preferable, as for (meth)acryl equivalent Mw/f of the film-forming component containing urethane (meth)acrylate (A), 300-800 are more preferable, 400-700 are still more preferable. By setting (meth)acryl equivalent Mw/f to 200-900, it is easy to take the balance of curl property, surface roughness, and HC property.

In addition, "f" here is the meaning of the average number of (meth)acryloyl groups of the film-forming component containing the above-mentioned urethane (meth)acrylate (A).

The (meth)acrylic compound that can be added to the film-forming component may be one that does not have a functional group other than a (meth)acryloyl group as in the above DPHA, or a functional group such as a hydroxyl group, an alkoxy group, a carboxyl group, an amide group, and a silanol group. may be to have

Examples of the compound having a polymerizable unsaturated double bond group other than the (meth)acrylic compound include a fatty acid vinyl compound, an alkyl vinyl ether compound, an α-olefin compound, a vinyl compound, and an ethynyl compound.

The content of the urethane (meth) acrylate (A) contained in the product containing the urethane (meth) acrylate (A) is, when the component having a hydroxyl group and the component having an isocyanate group are reacted, the ratio of isocyanate group / hydroxyl group By changing it, it can be changed.

Specifically, in the case of using a diisocyanate component having two isocyanate groups as a component having an isocyanate group, the ratio of isocyanate groups/hydroxyl groups is 0.2 to 0.7, further 0.2 to 0.6, thereby having three isocyanate groups as a component having an isocyanate group. In the case of using an isocyanate component, a product having a large content of urethane (meth)acrylate (A) can be obtained by setting the ratio of isocyanate groups/hydroxyl groups to 0.1 to 0.4 and further to 0.1 to 0.3. Moreover, when using the diisocyanate component which has two isocyanate groups as a component which has an isocyanate group, ratio of an isocyanate group/hydroxyl group may be 0.3-0.7.

After obtaining a product containing urethane (meth)acrylate (A), when a (meth)acrylic compound is further added to form a film-forming component, the average number or average of (meth)acryloyl groups in the film-forming component (meth)acryloyl group equivalent can be calculated|required by carrying out similarly to the case of the product containing the urethane (meth)acrylate (A) mentioned above.

Examples of the (meth)acrylic compound include an alkyl-based (meth)acrylate, an alkylene glycol-based (meth)acrylate, a compound having a carboxyl group and a polymerizable unsaturated double bond, a (meth)acrylic compound having a hydroxyl group, a nitrogen-containing (meth) ) acrylic compounds, benzyl (meth) acrylate, and the like. From a viewpoint of the HC property of a coating film, it is preferable that it is polyfunctional.

As a polyfunctional acrylic compound, it is preferable to have at least 3 or more acryloyl groups, Dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, ditrimethylol propane tetraacrylate, penta and erythritol triacrylate, trimethylolpropane triacrylate, isocyanuric acid modified triacrylate, and ethylene oxide modified product or propylene oxide modified product thereof.

In embodiment of this invention, the acryl-type compound which has two acryloyl groups can also be used. Specifically, polyethylene glycol diacrylate, polypropylene glycol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, nonanediol diacrylate, bisphenol A diacrylate, bisphenol F diacrylate, and these An ethylene oxide modified product, a propylene oxide modified product, etc. are mentioned.

In embodiment of this invention, a monofunctional (meth)acrylic-type compound can also be used further. Specifically, as a monofunctional (meth)acrylic compound, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth) Acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl ( C1-C22 alkyl (meth)acrylates, such as meth)acrylate and docosyl (meth)acrylate, etc. are mentioned.

As monofunctional alkylene glycol-based (meth)acrylate,

Mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, tetramethylene glycol (meth) acrylate having a hydroxyl group at the terminal and having a polyoxyalkylene chain (meth)acrylate;

Methoxyethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxyethylene glycol (meth) acrylate, propoxyethylene glycol (meth) acrylate, n-butoxytetraethylene glycol (meth) Acrylate, n-pentoxytetraethylene glycol (meth) acrylate, tripropylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, methoxytetrapropylene glycol (meth)acrylate, ethoxytetrapropylene glycol (meth)acrylate, propoxytetrapropylene glycol (meth)acrylate, n-butoxytetrapropylene glycol (meth)acrylate, n-pentoxytetrapropylene glycol (meth) ) acrylate, polytetramethylene glycol (meth) acrylate, methoxy polytetramethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate at the terminal mono(meth)acrylate having an alkoxy group and a polyoxyalkylene chain;

Phenoxydiethylene glycol (meth)acrylate, phenoxyethylene glycol (meth)acrylate, phenoxytriethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth) and polyoxyalkylene-based (meth)acrylates having a phenoxy group or an aryloxy group at the terminal, such as acrylate, phenoxypolyethylene glycol (meth)acrylate, and phenoxytetrapropyleneethylene glycol (meth)acrylate. .

Examples of the compound having a carboxyl group and a polymerizable unsaturated double bond include maleic acid, fumaric acid, itaconic acid, citraconic acid, or these alkyl or alkenyl monoesters, phthalic acid beta-(meth)acryloxyethyl monoester, isophthalic acid beta -(meth)acryloxyethyl monoester, succinic acid beta-(meth)acryloxyethyl monoester, acrylic acid, methacrylic acid, a crotonic acid, cinnamic acid, etc. are mentioned.

As the hydroxyl group-containing (meth)acrylic compound (except the mono(meth)acrylate having a hydroxyl group at the terminal and a polyoxyalkylene chain described above), 2-hydroxyethyl (meth)acrylate, 2-hydroxy Propyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc. can be heard

Examples of the nitrogen-containing (meth)acrylic compound include (meth)acrylamide, N-methylol (meth)acrylamide, N-methoxymethyl-(meth)acrylamide, N-ethoxymethyl-(meth)acrylamide, Monoalkylol (meth)acrylamide, such as N-propoxymethyl-(meth)acrylamide, N-butoxymethyl-(meth)acrylamide, N-pentoxymethyl-(meth)acrylamide, N,N- acrylamide-type unsaturated compounds, such as dialkylol (meth)acrylamide, such as di(methylol) acrylamide;

and unsaturated compounds having a dialkylamino group such as dimethylaminoethyl (meth)acrylate.

Further, examples of the monofunctional (meth)acrylic compound include perfluoroalkylalkyl (meth)acrylates having a perfluoroalkyl group having 1 to 20 carbon atoms, such as perfluoromethyl (meth)acrylate. .

Further, examples of the compound having a polymerizable unsaturated double bond group include vinyltrichlorosilane, vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, γ-(meth)acryloxypropyltrimethoxysilane, and the like. alkoxysilyl group-containing vinyl compounds and derivatives thereof;

glycidyl group-containing acrylates such as glycidyl acrylate and 3,4-epoxycyclohexyl acrylate;

and perfluoroalkyl group-containing vinyl monomers such as perfluoroalkylalkylenes such as perfluorobutylethylene, perfluorohexylethylene, perfluorooctylethylene and perfluorodecylethylene.

The compound which has a polymerizable unsaturated double bond group which can further be added to the product containing a urethane (meth)acrylate (A) may be used by 1 type, and may use 2 or more types. The film-forming component contains a urethane (meth)acrylate (A) in a total of 100% by mass of a product containing a urethane (meth)acrylate (A) and a compound having a further addable polymerizable unsaturated double bond group. It is preferable to contain 10 mass % or more, 20 mass % or more is more preferable, and 30 mass % or more is still more preferable. By containing 10 mass % or more of urethane (meth)acrylate (A), it becomes easy to make HC property and curl property compatible.

<Metal oxide (B)>

From the viewpoint of transparency of the hard coat layer, since the refractive index nD of the product containing the urethane (meth)acrylate (A) as the main component of the hard coat agent is about 1.46 to 1.52, the refractive index nD of the metal oxide (B) is 1.46 It is preferable that it is about 1.52. As such a metal oxide (B), silica (nD=1.47) is mentioned, for example. Silica may be used alone, or two or more types including other metal oxides may be mixed and used.

As a commercial item of silica, for example,

Nippon Aerosil Co., Ltd.: AEROSIL series (50, 90G, 130, OX50, TT600),

Nissan Chemical Industry Co., Ltd.: Organosilicasol series (MA-ST-M, MA-ST-L, IPA-ST-L, IPA-ST-ZL, MEK-ST-L, MEK-ST-ZL, MIBK- ST-L, MIBK-ST-M, MEK-AC-4130Y, MEK-AC-5140Z, PGM-AC-4130Y, MIBK-SD-L), Tachiron CIA Chemical Co., Ltd.: Nanotech SiO ₂ etc. are mentioned. .

It is preferable that the average primary particle diameter of these metal oxides (B) is 20 nm or more, More preferably, it is 22 nm or more, More preferably, it is 25 nm or more. By including the metal oxide (B) having an average primary particle diameter of 20 nm or more, a part of the metal oxide protrudes from the surface of the hard coat layer. The protruding metal oxide suppresses and prevents the hard coat layer from being scratched and cut by contact with a pencil or the like. Also, from the viewpoint of relieving stress, suppressing curl, and preventing cracks, the average primary particle diameter of the metal oxide (B) is preferably at least 20 nm as described above.

In addition, the upper limit of the average primary particle diameter of the metal oxide (B) is 80 nm or less, preferably 50 nm or less, in order to prevent aggregation and becoming excessively large secondary particles.

The average primary particle diameter of a metal oxide (B) can be calculated|required by observation with an electron microscope. That is, the average size of 10 particles when observed at a magnification of 20,000 times using a scanning electron microscope (“JEM-2800” manufactured by Nippon Electronics Co., Ltd.) was used as the average primary particle diameter.

As content of the metal oxide (B) contained in a hard-coat agent, 1 mass part or more is preferable with respect to 100 mass parts of film-forming components containing a urethane (meth)acrylate (A), 3 mass parts or more It is more preferable, and 5 mass parts or more are still more preferable. Moreover, 50 mass parts or less are preferable, 30 mass parts or less are more preferable, and 15 mass parts or less are still more preferable. By making the content of the metal oxide (B) within these ranges, it becomes possible to maintain the surface roughness at a certain level or less while obtaining desired HC properties and curl properties.

<Photoinitiator (C)>

The hard-coat agent in embodiment of this invention contains a photoinitiator (C).

As the photopolymerization initiator, if it has a function of initiating polymerization of an active energy ray-curable functional group such as a (meth)acryloyl group in the film-forming component containing the urethane (meth)acrylate (A) by photoexcitation, it is particularly There is no limitation, For example, a monocarbonyl compound, a dicarbonyl compound, an acetophenone compound, a benzoin ether compound, an acylphosphine oxide compound, an aminocarbonyl compound, etc. can be used.

Specifically, examples of the monocarbonyl compound include benzophenone, 4-methyl-benzophenone, 2,4,6-trimethylbenzophenone, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, 3,3', 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 2-iso-propylthioxanthone, 4-iso-propylthioxanthone, 2,4-diethylthioxanthone, 2,4- Dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc. are mentioned.

Examples of the dicarbonyl compound include 2-ethylanthraquinone, 9,10-phenanthrenequinone, and methyl-α-oxobenzeneacetate.

Examples of the acetophenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-phenylpropane-1- One, 1-hydroxy-cyclohexylphenyl ketone, diethoxyacetophenone, dibutoxyacetophenone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 2,2-diethoxy-1, 2-diphenylethan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4 -morpholinophenyl)butan-1-one, 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime, etc. are mentioned.

Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin normal butyl ether etc. are mentioned as a benzoin ether compound.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and 4-n-propylphenyl-di(2,6-dichlorobenzoyl)phosphine oxide.

Examples of the aminocarbonyl compound include ethyl-4-(dimethylamino)benzoate, 2-n-butoxyethyl-4-(dimethylamino)benzoate, isoamyl-4-(dimethylamino)benzoate, 2-( Dimethylamino)ethylbenzoate, 4,4'-bis-4-dimethylaminobenzophenone, 4,4'-bis-4-diethylaminobenzophenone, 2,5'-bis(4-diethylaminobenzal) Cyclopentanone etc. are mentioned.

As a commercial item of a photoinitiator, IGM-Resins B.V. company Omnirad 184, 651, 500, 907, 127, 369, 784, 2959, Esacure One, BASF company lucirin TPO, etc. are mentioned.

In particular, from the viewpoint of yellowing resistance after curing with active energy rays, Omnirad 184 or Esacure One are preferable.

The photopolymerization initiator is not limited to the above compound, and may be any type as long as it has the ability to initiate polymerization by an active energy ray. These photoinitiators can also be used in mixture of 2 or more types other than being used by 1 type.

Although there is no restriction|limiting in particular about the usage-amount of a photoinitiator, It is preferable to use within the range of 1-20 mass parts with respect to 100 mass parts of film-forming components containing a urethane (meth)acrylate (A). As a sensitizer, a well-known organic amine etc. can also be added.

Furthermore, in addition to the photopolymerization initiator, an initiator for cationic polymerization may be used in combination.

The hard-coat agent in embodiment of this invention contains (A)-(C) mentioned above and a solvent as needed at least, Furthermore, the objective and effect of embodiment of this invention are various additives. It can be included in a range that does not damage.

Examples of additives include polymerization inhibitors, photosensitizers, leveling agents, slip agents, defoamers, surfactants, antibacterial agents, anti-blocking agents, plasticizers, ultraviolet absorbers, infrared absorbers, antioxidants, silane coupling agents, conductive polymers. , conductive surfactants, inorganic fillers, pigments, dyes, and the like.

When adding a solvent, it is preferable to perform hardening process by an active energy ray after volatilizing a solvent.

The solvent is not particularly limited, and various known organic solvents can be used. Specifically, for example, cyclohexanone, methyl isobutyl ketone, methyl ethyl ketone, acetone, acetylacetone, toluene, xylene, n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, Methanol, 3-methoxy-1-butanol, 3-methoxy-2-butanol, ethylene glycol monomethyl ether, ethylene glycol mono-n-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, di Acetone alcohol, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, 2-ethoxyethyl acetate, butyl acetate, tetrahydrofuran, methylpyrrolidone, etc. are mentioned. can These organic solvents can also use 2 or more types together.

In particular, when the hydroxyl group-containing solvent contains an additive that lowers surface tension such as silicone or fluorine, it has excellent defoaming properties against bubbles generated during coating or after mixing various materials and stirring. By containing a hydroxyl group-containing solvent in a solvent composition, it is preferable from the point of being very effective in suppressing a coating-film defect and improving a yield.

It is preferable that the hydroxyl-containing solvent content in 100 mass % of all solvents is 5-70 mass %, It is more preferable that it is 10-50 mass %, It is more preferable that it is 15-40 mass %. Specifically, as the hydroxyl group-containing solvent, n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, ethanol, methanol, 3-methoxy-1-butanol, 3-methoxy-2-butanol, ethylene Glycol monomethyl ether, ethylene glycol mono n-butyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, propylene glycol monomethyl ether, etc. are mentioned. In particular, propylene glycol monomethyl ether and ethylene glycol monomethyl ether are preferable at the point which is excellent in antifoaming property and volatility as an earth solvent (solvent with weak volatility), and a drawing becomes more favorable.

The hard coat agent can be obtained by a known manufacturing method, and is not particularly limited. For example, first, a film-forming component including urethane (meth)acrylate (A) and a metal oxide (B) are mixed and dispersed to obtain a stable metal oxide dispersion, and then a photopolymerization initiator (C) and other various additives and a method of manufacturing by adding and preparing.

2. Transparent film

As a transparent film, the film-like glass which is a thin film and can be wound up in roll shape, various plastic films, etc. are mentioned, A thing which can express the HC property of a hard-coat layer at a high level is preferable. Examples of the various plastic films include crystalline plastic films such as polyethylene terephthalate (PET) films, polybutylene terephthalate (PBT) films, polyethylene naphthalate (PEN) films, and polyamide (PA) films, Amorphous films, such as a polyvinyl chloride (PVC) film, a polycarbonate (PC) film, and a polymethyl methacrylate (PMMA) film, are mentioned, Crystalline plastics are preferable. An amorphous film can be used in the range which does not impair the effect of embodiment of this invention.

In the embodiment of the present invention, it is preferable to use a commercially versatile PET film.

In addition, from the viewpoint of the adhesiveness of the hard coat layer to be formed, it is preferable that the easily adhesive layer or the transparent film surface is subjected to an easily adhesive treatment such as corona treatment on the transparent film.

The thickness of the transparent film is preferably 25 µm to 500 µm, more preferably 50 µm to 300 µm, and still more preferably 75 µm to 200 µm.

As a method of coating the hard coat agent on the transparent film, a known method can be used, for example, a method using a rod or a wire bar, micro gravure, gravure, die, curtain, lip, slot or spin, etc. Various coating methods can be used.

In the curing treatment, a hard coat agent is coated on a transparent film, dried naturally or forcibly, and then is cured by irradiating an active energy ray.

As an active energy ray, an ultraviolet-ray, an electron beam, visible light of wavelength 400-500 nm, etc. are mentioned, for example.

As the source (light source) of ultraviolet and visible light having a wavelength of 400 to 500 nm, for example, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp, etc. can be used. As the electron beam source, a thermal electron gun, an electrolytic gun, or the like can be used. The heat treatment by infrared rays, far infrared rays, hot air, high frequency heating, etc. can be used together for these active energy ray irradiation.

On the other hand, in the case of curing with an electron beam, it is more preferable to perform curing treatment after natural or forced drying in order to prevent curing inhibition by water or decrease in strength of the coating film due to residual organic solvent. The timing of the curing treatment may be simultaneous with coating or after coating.

Active energy dose of irradiation is not sufficient capacity exhibited in the hard coat layer curling point of view, the range of 50 ~ 2000mJ / cm ² preferably, 100 ~ 1500mJ / range cm ² I more preferably, 200 ~ 1000mJ / In ^{the range of cm 2} is more preferable.

The thickness of a hard-coat layer becomes like this. Preferably they are 0.5 micrometer - 5 micrometers, More preferably, they are 0.7 micrometer - 4 micrometers, More preferably, they are 1 micrometer - 3 micrometers.

3. High refractive index layer

The high refractive index layer is a layer with a high refractive index that is laminated for the purpose of making the patterned shape invisible after the transparent conductive layer formed on the high refractive index layer is patterned. Specifically, metal oxide particles with high refractive index and active energy A cured product of a composition comprising a pre-curable component. Since the transparent conductive layer is formed of a conductive metal compound as described later, the refractive index thereof is about 1.55 to 1.90. Therefore, it is preferable that the refractive index of the high refractive index layer is as close to that of the transparent conductive layer as possible.

The high refractive index metal oxide particles and active energy ray-curable component can be obtained using a known material. For example, titanium oxide (nD=2.72), zirconium oxide (nD=2.22), aluminum oxide (nD=1.77) etc. are mentioned as a metal oxide particle with a high refractive index. In addition, as an active energy ray-curable component, the urethane (meth)acrylate (A) and other curable components contained in the hard-coat agent mentioned above can be illustrated similarly.

The thickness of the high refractive index layer is preferably 0.03 µm to 30 µm, more preferably 0.05 µm to 10 µm.

4. Transparent conductive layer

A transparent conductive layer is a layer laminated|stacked on the high refractive index layer, Specifically, it is a layer formed by the film-forming method using vacuum. As a film-forming method using vacuum, dry processes, such as a vacuum deposition method (physical vapor deposition method or chemical vapor deposition method), a sputtering method, and an ion plating method, can be used, for example. By these methods, a transparent conductive layer can be formed by attaching a conductive metal compound to the high refractive index layer. After the transparent conductive layer is provided on the entire surface of the high refractive index layer, it can be formed into a circuit or electrode by patterning it into a desired shape by a method such as etching. It is preferable to exist in the range of 1 nm - 1 micrometer, and, as for the thickness of a transparent conductive layer, it is more preferable to exist in the range of 0.01 micrometer - 1 micrometer from a viewpoint of electroconductivity improvement and adhesive improvement with a high refractive index layer.

Examples of the conductive metal compound used for forming the transparent conductive layer include nanowires made of indium tin oxide, tin oxide, zinc oxide, silver or copper.

5. Other Configurations

It can be set as the aspect which arrange|positions an anchor layer between a high refractive index layer and a transparent conductive layer, a high refractive index layer and an anchor layer contact, and an anchor layer and a transparent conductive layer contact.

In the same manner as described above in which the high refractive index layer and the transparent conductive layer are in contact with each other, first, a high refractive index layer is formed on the transparent film. Next, after forming an anchor layer on the high refractive index layer, a transparent conductive layer is formed.

An anchor layer is a layer formed by the film-forming method using vacuum similarly to the case of a transparent conductive layer. A silicon oxide is mentioned as a metal oxide used for formation of an anchor layer, It is preferable at the point which can provide strong adhesiveness.

In addition, the transparent conductive film may contain other layers other than an anchor layer.

<<Pattern forming transparent conductive film>>

The pattern-formed transparent conductive film is formed by patterning the transparent conductive layer in the transparent conductive film α. The pattern-forming transparent conductive film is also called transparent conductive film β.

<<Optical member>>

The optical member is, as described above, at least a hard coat layer, a transparent film, a high refractive index layer, a transparent conductive layer of a laminate having a transparent conductive layer, a pattern-forming transparent conductive film obtained by patterning by etching treatment, etc. A touch sensor comprising a It is an absence of

<<Electronic Equipment>>

Electronic devices refer to various devices equipped with the above-described touch sensors, for example, smart phones, tablets, PCs, televisions, car navigation systems, and devices such as information boards and traffic ticket vending machines in other commercial facilities. In these devices, the above-described touch sensor functions as a touch panel.

In this specification, etc., the range shown using "-" shall include the numerical values described before and after "-", respectively.

The present invention relates to the subject matter of Japanese Patent Application No. 2019-224765 filed on December 12, 2019, the entire disclosure of which is incorporated herein by reference.

[Example]

Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example. On the other hand, in the synthesis examples and examples, the number of mixing parts of the material, excluding the solvent, is in terms of non-volatile matter.

[Measurement of molecular weight]

The mass average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC). The measurement conditions are as follows. In addition, both Mw and Mn are polystyrene conversion values.

Device: SHIMADZU Prominence (Shimadzu Corporation),

Column: 3 SHODEX LF-804 (manufactured by Showa Denko Co., Ltd.) connected in series,

Detector: Differential refractive index detector,

Solvent: tetrahydrofuran (THF),

flow rate: 1.0 mL/min;

Solvent temperature: 40℃,

Sample concentration: 0.2%,

Sample injection volume: 100 μL.

<Synthesis of urethane (meth)acrylate (A)>

(Synthesis Example 1)

(A1): Aronix M403: 2103 g (molecular weight: 524 dipentaerythritol pentaacrylate (DPPA) 1000 g (about 1.91 mol) in a 4-neck flask equipped with a stirrer, reflux condenser, nitrogen introduction tube, thermometer, and dropping funnel) And a composition comprising 1103 g (about 1.91 mol) of dipentaerythritol hexaacrylate (DPHA) having a molecular weight of 578. Toagosei Co., Ltd.), Neostan U-810 (tin catalyst, manufactured by Nitto Kasei Co., Ltd.): 0.1 g , butyl acetate: 815 g was put, the liquid temperature was set to 50 ° C., and then the nurate body of hexamethylene diisocyanate containing about 21.8 mass % of isocyanate groups: 74 g (containing about 0.38 mol of isocyanate groups) from a dropping funnel for 30 minutes was dropped over. After the temperature rise was stopped, the temperature was raised to 80 ° C. and reacted for 3 hours. After confirming that the peak of the isocyanate group disappeared by FT-IR, butyl acetate was added while cooling and diluted, and DPPA and HDI-nurate urethane ( A solution having a solid content of 70% by mass of the product A1 containing meth)acrylate was obtained.

The mass average molecular weight of the product A1 containing the urethane (meth)acrylate of DPPA and HDI-nurate was 1930, the average number of functional groups (f _{C = C} ) obtained by the above method was 6.8, the acrylic equivalent of the product Mw/f was 285. On the other hand, product A1 theoretically contains about 50.7% by mass of DPHA.

(Synthesis Examples 2 to 11)

Synthesis Examples 2 to 11 also synthesized products A2 to A11 containing urethane (meth)acrylate according to the compounding ratio of Table 1 in the same manner as in Synthesis Example 1. In Table 1, f _OH represents the number of hydroxyl _{groups, and f NCO} represents the number of isocyanate groups.

[Table 1]

[material]

The materials used are as follows.

((meth)acrylate (a1) having a hydroxyl group)

(a1-1) Aronix M403 (molecular weight: 524 dipentaerythritol pentaacrylate (DPPA), molecular weight: a composition comprising dipentaerythritol hexaacrylate (DPHA) of 578. DPPA / DPHA = 1/1 ( molar ratio), manufactured by Toagosei Co., Ltd.).

(a1-2) A-TMPT (Molecular weight: 298 pentaerythritol triacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).

(Polyisocyanate (a2))

(a2-1) Sumidul N3300 (hexamethylene diisocyanate-nurate form, NCO% = 21.8 (solid content 100%), Sumika Covestrourethane Co., Ltd. make);

(a2-2) Death module I (isophorone diisocyanate, NCO% = 37.5 (solid content 100%), made by Sumika Kobestro Urethane Co., Ltd.),

(a2-3) Desmodule Z4470BA (Butyl acetate solution of isophorone diisocyanate-nurate form, NCO% = 16.9 (in terms of 100% solid content), made by Sumika Kobestro Urethane Co., Ltd.).

(Example 1)

100 parts by mass (non-volatile content) of the product A1 containing urethane (meth)acrylate synthesized in Synthesis Example 1, 10 parts by mass of (B3) described below having an average primary particle diameter of 30 nm as a metal oxide, and Esacure as a photopolymerization initiator 5 parts by mass of raw material (manufactured by IGM-Resins BV), 0.1 parts by mass of BYK349 (silicone-based additive, manufactured by Bikcheme Japan Co., Ltd.) as a leveling agent, 20 parts of polyethylene glycol monoethyl ether (PGME) in an insufficient amount as a diluting solvent, And 60 parts of butyl acetate were mixed and disperse|distributed, and the hard-coat agent 1 was obtained.

According to the method described later, the defoaming property of the hard coat agent, the curling property of the intermediate laminate provided with the hard coat layer, the surface roughness of the hard coat layer, and the hardness (HC property) of the hard coat layer were evaluated.

(Example 2) to (Example 11)

Except for using the products A2 to A11 containing the urethane (meth) acrylate synthesized in Synthesis Examples 2 to 10 instead of the product A1 containing the urethane (meth) acrylate synthesized in Synthesis Example 1, Example 1 and It carried out similarly, the hard-coat agents 1-11 were obtained, and it evaluated similarly.

(Example 12) to (Example 17)

In the same manner as in Example 3, except that the amount of the metal oxide (B3) having an average primary particle diameter of 30 nm was 1 part by mass, 3 parts by mass, 5 parts by mass, 15 parts by mass, 30 parts by mass, or 50 parts by mass, the hard Coating agents 12 to 17 were obtained and evaluated in the same manner. Table 3 also describes Example 3.

(Example 18) to (Example 21)

Instead of the product A1 containing the urethane (meth)acrylate synthesized in Synthesis Example 1, the product A4 containing the urethane (meth)acrylate synthesized in Synthesis Example 4 was used, and the average primary particle diameter as a metal oxide was 20 nm (B1) of 22 nm, (B2) of 22 nm, (B3) of 30 nm, (B4) of 50 nm, and (B5) of 80 nm, respectively, in the same manner as in Example 4 except that 10 parts by mass were used. Thus, hard coat agents 18 to 21 were obtained and evaluated in the same manner.

(Example 22)

Without using polyethylene glycol monoethyl ether (PGME) as a diluent solvent, except having used 80 mass parts of butyl acetate, it carried out similarly to Example 3, the hard-coat agent 22 was obtained, and it evaluated similarly.

(Example 23)

A hard coat agent 23 was obtained in the same manner as in Example 1 except that Omnirad 184 (manufactured by IGM Resins B.V.) was used as a photopolymerization initiator instead of Esacure One, and the same evaluation was performed.

(Comparative Example 1)

Except not using a metal oxide, it carried out similarly to Example 3, the hard-coat agent was obtained, and it evaluated similarly.

(Comparative Example 2)

A hard coat agent was obtained in the same manner as in Example 3 except that (B3) having an average primary particle diameter of 30 nm was 100 parts by mass as the metal oxide, and evaluated in the same manner.

(Comparative Example 3)

A hard coat agent was obtained in the same manner as in Example 4 except that 10 parts by mass of (B6) described later having an average primary particle diameter of 10 nm was used as the metal oxide, and evaluated in the same manner.

(Comparative Example 4)

In the same manner as in Example 1, except that 100 parts by mass of dipentaerythritol hexaacrylate and 10 parts by mass of (B3) having an average primary particle diameter of 30 nm as a metal oxide were used instead of the product containing urethane (meth)acrylate Thus, a hard coat agent was obtained and evaluated in the same manner.

[material]

The materials used are as follows.

(x'1) DPHA (dipentaerythritol hexaacrylate, manufactured by Daicel Allnex Co., Ltd., molecular weight: 578, Mw/f _C=C =96.3)

<Metal oxide (B)>

The metal oxide used is as follows.

(B1) AEROSIL 130 (silica, average primary particle diameter of 16 nm, manufactured by Nippon Aerosil Co., Ltd.),

(B2) CHO-ST-M (silica, average primary particle diameter of 22 nm, manufactured by Nissan Chemical Corporation);

(B3) AEROSIL 50 (silica, average primary particle diameter of 30 nm, manufactured by Nippon Aerosil Co., Ltd.),

(B4) MEK-AC-4130Y (silica, average primary particle diameter 45 nm, manufactured by Nissan Chemical Corporation);

(B5) MEK-AC-5140Z (silica, average primary particle diameter 85 nm, manufactured by Nissan Chemical Corporation);

(B6) MEK-ST (silica, average primary particle diameter of 10 nm, manufactured by Nissan Chemical Corporation).

<Photoinitiator (C)>

The photoinitiator used is as follows.

(C1) Esacure One (manufactured by IGM Resins B.V.),

(C2) Omnirad 184 (manufactured by IGM Resins B.V.)

(Antifoaming property made of hard coat)

After putting 20 parts by mass of the hard coat agent into a 70 mL container with a lid and sealing it, the entire container was shaken vigorously 10 times and left still on the test bench, and the time until bubbles disappeared was measured. The evaluation criteria are as follows.

<Evaluation criteria>

AA: No bubbles when standing still, excellent.

A: It defoamed within 2 seconds after standing still, good.

B: After standing still, it was defoamed within 2 to 10 seconds, ready to use.

C: Defoaming does not occur even after 10 seconds have elapsed after standing still, defective.

(Curl properties of Intermediate 1)

Each hard coat agent obtained in Examples and Comparative Examples was coated on a 100 μm thick easily-adhesive polyethylene terephthalate film (“Cosmoshine A4100” manufactured by Toyobo Corporation, using a bar coater, and dried to remove the organic solvent. ^{Then, 200 mJ/cm 2} UV light was irradiated using a high-pressure mercury lamp, a 2 μm hard coat layer was formed, and Intermediate 1 was obtained.

The approximately central portion of the intermediate body 1 was cut into a 10 cm×10 cm square (square), and heated at 100° C. for 1 minute within 30 minutes after forming the hard coat layer. The height of the curl float of the edge part at that time was evaluated. The evaluation criteria are as follows.

AA: The height of curl lifting is 0mm, excellent.

A: The curl height is 0-5mm, good.

B: Curl lift height is 5~10mm, easy to use.

C: Curl floating height exceeds 10mm, defective.

(Surface roughness (Ra) of the intermediate body)

The surface roughness of the hard coat surface of the intermediate 1 was measured using a three-dimensional structural analysis microscope (manufactured by ZYGO Systems, Canon Marketing, Japan). Surface roughness (Ra) represents the arithmetic mean roughness defined in JIS B0601·JIS B0031.

AA: Surface roughness (Ra) less than 0.5 nm, excellent.

A: Surface roughness (Ra) is 0.5 nm or more and less than 1.0 nm, good.

B: Surface roughness (Ra) is 1.0 nm or more and less than 1.5 nm, use is possible.

C: Surface roughness (Ra) of 1.5 nm or more, defective.

(HC properties of Intermediate 1)

According to the test method of JIS-K-5600, the hardness of the hard coat surface of the intermediate body 1 was determined. The evaluation criteria are as follows.

AA: 3H, good.

A: 2H, good.

B: H, use it.

C: F, bad.

(Anti-blocking properties of the hard coat layer to the transparent conductive layer)

<Production of transparent conductive film>

On a 25 μm-thick easily-adhesive polyethylene terephthalate film (“Tetron Film HPE25” manufactured by Toyobo Film Solutions Co., Ltd.), the hard coat agent obtained in Examples and Comparative Examples was coated using a bar coater, dried and organic After removing the solvent, 200 mJ/cm ² UV light was irradiated using a high-pressure mercury lamp, a 5 μm hard coat layer was formed, and an intermediate 2 was obtained.

Next, on the polyester film (second side) opposite to the hard coat layer of the obtained intermediate 2 (the side facing the hard coat layer), a coating material containing zirconium oxide (refractive index of the cured product: 1.70) was applied Coating and irradiation were carried out, and the high refractive index layer was obtained.

On the obtained high refractive index layer, indium tin oxide was sputtered with a magnetron sputtering device ("MSP-30T Magnetron Sputter" manufactured by Vacuum Devices Co., Ltd.) to form a 25 nm transparent conductive layer to obtain a transparent conductive film.

<Friction test by Hakjin testing machine>

A transparent conductive film is set on the test piece of the Hakjin testing machine so that the transparent conductive layer becomes the test surface. Separately, a transparent conductive film cut to 1 cm x 1 cm is set on the friction element of the Hakjin testing machine so that the hard coat layer faces the transparent conductive layer set on the test piece.

Under the condition of a load of 200 g, the surface of the transparent conductive layer was reciprocated and rubbed with the hard coat layer 10 times.

The surface resistance value of the transparent conductive layer before and after the surface of the transparent conductive layer was rubbed with the hard coat layer was measured by the following method, and the change in the surface resistance value after the test with respect to the surface resistance value before the test was evaluated.

<Measuring method of surface resistance value of conductive layer>

The surface resistance value of the transparent conductive layer was calculated|required using the probe which has 4 terminals arranged in a line with "Loresta GX MCP-T600" manufactured by Nitto Seiku Analytech Co., Ltd. as a measuring device. After the test, the probe was pressed against the transparent conductive layer so that the terminal group of the probe crossed the rubbing direction, and the surface resistance value of the transparent conductive layer was obtained.

<Evaluation criteria>

A: The surface resistance value after the test is less than 10 times the resistance value before the test, good.

B: The surface resistance value after the test is 10 times or more and less than 100 times the resistance value before the test.

C: The surface resistance value after the test is 100 times or more of the resistance value before the test, poor

[Table 2]

[Table 3]

[Table 4]

As shown in Table 4, Comparative Example 1 containing no metal oxide (B) had a good surface roughness, but did not exhibit stress relaxation properties, so curling easily occurred and HC properties were insufficient. Furthermore, the anti-blocking properties of the transparent conductive layer are also insufficient. In Comparative Example 2, in which the amount of the metal oxide was excessive, the anti-blocking property of the transparent conductive layer was good, but the amount of the metal oxide was too large, and the surface roughness was increased. In Comparative Example 3, in which the metal oxide itself is small, the amount of the metal oxide protruding from the surface of the hard coat layer is small, so the anti-blocking property to the transparent conductive layer is not expressed, and the effect of suppressing curl is not expressed. In Comparative Example 4, which does not contain the urethane (meth)acrylate (A), although the surface roughness and the like are good, the softness of the hard coat layer is insufficient and the curling property cannot be suppressed.

Industrial Applicability

The transparent conductive film of the embodiment of the present invention can be used as a member exhibiting a touch panel function mounted on a notice board or a traffic ticket vending machine in smart phones, tablets, PCs, televisions, car navigation systems, and other commercial facilities. In particular, even when a thin transparent film is used as a support, curling is difficult to occur, so it can contribute to saving of raw materials for transparent films and reducing the thickness of various devices.

Claims (13)

A transparent conductive film in which a hard coat layer is laminated on one side of a transparent film, and a high refractive index layer and a transparent conductive layer are laminated on the opposite side,
The hard coat layer is a cured product of a hard coat agent comprising a film-forming component comprising a urethane (meth)acrylate, a metal oxide, and a photoinitiator, and the surface roughness of the hard coat layer is less than 1.5 nm,
On a polyethylene terephthalate film having a film thickness of 100 µm, a 10 cm × 10 cm square test piece in which a hard coat layer having a film thickness of 2 µm was formed using the hard coat agent was placed at 100 ° C. within 30 minutes after the hard coat layer was formed. The average of the curl lifting heights of the four corners of the test piece when standing for 1 minute in the environment is 10 mm or less,
Transparent conductive film. According to claim 1,
The transparent conductive film in which the said film-forming component has 3-10 (meth)acryloyl groups on average. 3. The method of claim 1 or 2,
The film-forming component includes a reaction product of a (meth)acrylate having a hydroxyl group and a polyisocyanate,
When the polyisocyanate is a diisocyanate having two isocyanate groups, the ratio of isocyanate groups/hydroxyl groups is 0.2 to 0.7,
When the polyisocyanate is a triisocyanate having three isocyanate groups, the ratio of isocyanate groups/hydroxyl groups is 0.1 to 0.4, the transparent conductive film. 3. The method of claim 1 or 2,
The mass average molecular weight of the film-forming component is 1000 to 6000, the transparent conductive film. 3. The method of claim 1 or 2,
The average (meth)acryloyl group equivalent of the film-forming component is 200-900, the transparent conductive film. 3. The method of claim 1 or 2,
The transparent conductive film wherein the urethane (meth)acrylate has 9 or more (meth)acryloyl groups. 3. The method of claim 1 or 2,
The transparent conductive film in which the said urethane (meth)acrylate has an alicyclic structure. 3. The method of claim 1 or 2,
The transparent conductive film in which the said urethane (meth)acrylate has a nurate ring structure. 3. The method of claim 1 or 2,
The amount of the metal oxide is 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the film-forming component, the transparent conductive film. 3. The method of claim 1 or 2,
The average primary particle diameter of the metal oxide is 20 nm or more and 50 nm or less, the transparent conductive film. A pattern-formed transparent conductive film formed by patterning the transparent conductive layer in the transparent conductive film according to claim 1 or 2 . An optical member comprising the pattern-forming transparent conductive film according to claim 11 . An electronic device comprising the optical member according to claim 12.