JP6374356B2 - Laminated film, method for producing laminated film, transparent conductive film, and organic electroluminescence element - Google Patents

Description

  The present invention relates to a laminated film, a method for producing the laminated film, a transparent conductive film, and an organic electroluminescence element. Specifically, the present invention provides a laminated film having high impact resistance after ultraviolet irradiation and good color tone after ultraviolet irradiation, even when a cyclic olefin polymer film or cyclic olefin copolymer film is used, and this laminated film The manufacturing method of this invention, the transparent conductive film which has this laminated film, and the organic electroluminescent element which has this laminated film.

  In recent years, applications such as organic electroluminescence display devices and touch panels are expanding. In such a device, various resin films are used for a support or a protective film. Among these, a cyclic olefin polymer film or a cyclic olefin copolymer film is preferably used because of its high heat resistance and low water absorption, and thus excellent dimensional stability. Moreover, since the cyclic olefin polymer film or the cyclic olefin copolymer film has a low photoelastic coefficient and can suppress birefringence to a low level, it is a material excellent in optical characteristics.

The cyclic olefin polymer film or the cyclic olefin copolymer film is easily deteriorated by irradiation with sunlight or ultraviolet rays, and as a result, the color tone deteriorates.
In contrast, Patent Document 1 discloses a molding having a coat layer including a step of bulk polymerization of a norbornene-based monomer and a step of applying a weather-resistant stabilizer-containing transparent paint containing 0.5 to 50% by weight of a weather-resistant stabilizer. A body manufacturing method is described. According to Patent Document 1, it is described that, with such a configuration, a molded body that is made of norbornene-based resin and hardly undergoes weather resistance deterioration such as color change can be manufactured. In the example of Patent Document 1, a coating layer containing a polyol-curable polyurethane-based transparent paint and 2,4-dihydroxybenzophenone (maximum absorption wavelength range of 280 to 340 nm) as a weather stabilizer is provided on the surface of the cyclic olefin polymer film. Yes.

  Patent Document 2 discloses that (a) a compound having a trifunctional or higher functional unsaturated group on at least one surface of the cyclic olefin resin film (A), and (b) a monofunctional or higher functional polymerizable unsaturated group and an alicyclic ring. (A) 85 to 20 parts by weight, (b) 10 to 50 parts by weight, (c) 5 to 30 parts by weight of a compound having a structure and (c) a compound having an acidic group and one or more polymerizable unsaturated groups Layered film (I) having a cured layer (B) formed using a curable composition containing a proportion of parts (provided that the total of (a), (b), and (c) is 100 parts by weight) ) Is described. According to Patent Document 2, a laminated film that has a high heat resistance and can form a vapor-deposited film at a high temperature without impairing characteristics such as excellent transparency of the cyclic olefin resin film. It is described that it can be provided. Patent Document 2 exemplifies an ultraviolet absorber as an additive that can be blended in a curable composition for forming a cured layer irradiated with ultraviolet rays.

JP 2003-26834 A JP 2010-89458 A

  When the present inventors examined the performance of the laminated film using the cyclic olefin polymer film or the cyclic olefin copolymer film described in Patent Documents 1 and 2, ultraviolet rays were formed by providing a layer using a weather resistance stabilizer or an ultraviolet absorber. It was found that even if weather resistance deterioration such as color change after irradiation was suppressed, the impact strength after ultraviolet irradiation deteriorated. In Patent Documents 1 and 2, there is no description regarding mechanical properties such as impact strength after ultraviolet irradiation.

  The problem to be solved by the present invention is to provide a laminated film having high impact resistance after ultraviolet irradiation and good color tone after ultraviolet irradiation even when a cyclic olefin polymer film or cyclic olefin copolymer film is used. That is.

As a result of intensive studies to solve the above problems, the present inventors have obtained that the transmittance of ultraviolet rays in a specific wavelength band is below a specific range on the surface of the cyclic olefin polymer film or the cyclic olefin copolymer film. As described above, by making the laminated film provided with a polymer layer and further increasing the breaking elongation of the polymer layer or reducing the breaking stress of the polymer layer, the impact resistance after UV irradiation is high and the color tone after UV irradiation is high. Was found to be good.
The present invention, which is a means for solving the above problems, and a preferred embodiment of the present invention specifically have the following configurations.

[1] A laminated film having a polymer film and a polymer layer A disposed on at least one surface of the polymer film,
The polymer film is a cyclic olefin polymer film or a cyclic olefin copolymer film;
The polymer layer A satisfies at least one of the following conditions a and b:
A laminated film having an average transmittance of light having a wavelength of 290 to 360 nm of the laminated film of 18% or less;
Condition a: The elongation at break of the polymer layer A is 10% or more;
Condition b: The breaking stress of the polymer layer A is 20 MPa or less.
[2] In the laminated film according to [1], the polymer layer A contains an ultraviolet absorber,
The content of the ultraviolet absorber in the polymer layer A is preferably 1 g / m ² or less.
[3] In the laminated film according to [1] or [2], the polymer layer A contains an ultraviolet absorber,
The ultraviolet absorber in the polymer layer A is preferably a triazine-based ultraviolet absorber.
[4] In the laminated film according to any one of [1] to [3], the polymer layer A includes a binder,
The binder in the polymer layer A is preferably a urethane polymer, an olefin polymer, or a styrene butadiene rubber.
[5] In the laminated film according to [4], the binder in the polymer layer A is preferably a urethane polymer.
[6] having a step of arranging the composition for forming the polymer layer A on at least one surface of the polymer film;
The polymer film is a cyclic olefin polymer film or a cyclic olefin copolymer film;
The manufacturing method of the laminated | multilayer film in which the composition for polymer layer A formation contains a ultraviolet absorber and a binder.
[7] In the method for producing a laminated film according to [6], it is preferable that the ultraviolet absorbent in the composition for forming the polymer layer A is a triazine ultraviolet absorbent.
[8] In the method for producing a laminated film according to [6] or [7], the binder in the composition for forming the polymer layer A is preferably a urethane polymer, an olefin polymer, or a styrene butadiene rubber.
[9] In the method for producing a laminated film according to [8], the binder in the composition for forming the polymer layer A is preferably a urethane-based polymer.
[10] A laminated film produced by the method for producing a laminated film according to any one of [6] to [9].
[11] A transparent conductive film having the laminated film according to any one of [1] to [5] and [10].
[12] An organic electroluminescence device having the laminated film according to any one of [1] to [5] and [10].

  According to the present invention, even when a cyclic olefin polymer film or a cyclic olefin copolymer film is used, it is possible to provide a laminated film having high impact resistance after ultraviolet irradiation and good color tone after ultraviolet irradiation.

  Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments and specific examples, but the present invention is not limited to such embodiments. In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

[Laminated film]
The laminated film of the present invention is a laminated film having a polymer film and a polymer layer A disposed on at least one surface of the polymer film,
The polymer film is a cyclic olefin polymer film or a cyclic olefin copolymer film;
The polymer layer A satisfies at least one of the following conditions a and b:
The average value of the transmittance of light having a wavelength of 290 to 360 nm of the laminated film is 18% or less.
Condition a: The elongation at break of the polymer layer A is 10% or more;
Condition b: The breaking stress of the polymer layer A is 20 MPa or less.
With such a configuration, the laminated film of the present invention has high impact resistance after ultraviolet irradiation and good color tone after ultraviolet irradiation even when a cyclic olefin polymer film or a cyclic olefin copolymer film is used.
The breaking elongation of the polymer layer A refers to a value of elongation when the polymer layer A breaks when the polymer layer A is subjected to a tensile test. A higher elongation at break indicates that the polymer layer A is stretched and easily absorbs the shock, and a lower elongation indicates that the polymer layer A is less likely to be stretched and less easily absorbed.
The breaking stress means a value of stress at the time of breaking of the polymer layer A when the polymer layer A is subjected to a tensile test. A higher breaking stress indicates that the polymer layer A is brittle, and a lower breaking stress indicates that the polymer layer A is not brittle.
On the cyclic olefin polymer film or the cyclic olefin copolymer film, a laminated film provided with a polymer layer A having a low breaking stress and not too brittle or a polymer layer A having a high elongation at break and capable of absorbing impact by elongation is obtained. By reducing the UV transmittance of the film, the impact resistance after UV irradiation and the color tone after UV irradiation are improved.
Here, a polymer layer obtained by curing a urethane polymer (acrylic urethane-based clear (product name: NY clear) [Mikuni Paint Co., Ltd. (manufactured))] used in Examples of JP-A-2003-26834, or JP-A-2010 The polymer layer obtained by curing the 6-15 functional urethane acrylate monomer used in the examples of JP-A-89458 was a polymer layer in which the elongation at break and the stress at break did not satisfy the conditions a and b.
Hereinafter, the preferable aspect of the laminated | multilayer film of this invention is demonstrated.

<Characteristic>
In the laminated film of the present invention, the average value of the light transmittance at a wavelength of 290 to 360 nm of the laminated film is 18% or less, and preferably 10% or less from the viewpoint of the color tone after ultraviolet irradiation, and 5% or less. More preferably, it is 2% or less.

<Layer structure>
In the laminated film of the present invention, the polymer layer A may be disposed on at least one surface of the polymer film, and the polymer layer A may be disposed on both surfaces of the polymer film or only on one surface. The arrangement position of the polymer layer A can be selected from one side or both sides according to the application.
The polymer film and the polymer layer A may be laminated via an adhesive layer, or may be directly in contact with each other without an adhesive layer. The polymer film and the polymer layer A are preferably in direct contact with each other without an adhesive layer, from the viewpoint of easily controlling the impact resistance in the case of a laminated film by the mechanical properties of the polymer layer A.

<Polymer film>
In the laminated film of the present invention, the polymer film is a cyclic olefin polymer film or a cyclic olefin copolymer film. The cyclic olefin polymer film or the cyclic olefin copolymer film has a low mechanical strength in a single layer, and is a material in which impact resistance in the case of a laminated film is easily governed by the mechanical strength of other layers.

A cyclic olefin polymer film or a cyclic olefin copolymer film refers to a film containing a cyclic olefin polymer or a cyclic olefin copolymer. The polymer film used in the present invention preferably contains 50% by mass or more, more preferably 80% by mass or more, and more preferably 90% by mass or more of the cyclic olefin polymer or cyclic olefin copolymer among the resin components constituting the polymer film. It is particularly preferable to include it. It is particularly preferable that the resin component constituting the polymer film is only a cyclic olefin polymer or a cyclic olefin copolymer.
The cyclic olefin polymer or the cyclic olefin copolymer is preferably a polymer obtained by polymerizing or copolymerizing a cyclic olefin monomer, and a cyclic olefin monomer having a norbornene unit (a structure derived from a norbornene skeleton) is preferably used. A polymer obtained by polymerization or copolymerization is more preferable, and examples thereof include the following.
(1) A ring-opening polymer of a cyclic olefin monomer.
(2) A ring-opening copolymer of a cyclic olefin monomer and a copolymerizable monomer.
(3) A hydrogenated (co) polymer of the ring-opening (co) polymer of (1) or (2) above.
(4) A (co) polymer obtained by cyclizing the ring-opening (co) polymer of (1) or (2) by Friedel-Craft reaction and then hydrogenating it.
(5) A saturated copolymer of a cyclic olefin monomer and an unsaturated double bond-containing compound.
(6) Addition (co) polymers of cyclic olefin monomers and hydrogenated (co) polymers thereof.
(7) An alternating copolymer of a cyclic olefin monomer and an acrylate.
Of these, (1), (2) and (3) are preferred.
The cyclic olefin polymer preferably contains norbornene units, and the cyclic olefin copolymer preferably contains ethylene units and norbornene units.
There is no restriction | limiting in particular as a cyclic olefin type monomer (preferably norbornene unit) used as a raw material of a cyclic olefin polymer or a cyclic olefin copolymer. As the cyclic olefin monomer, for example, a compound having a norbornene skeleton can be used without particular limitation. [0009] to [0021] of JP 2010-89458 A and [0009] of JP 2003-26834 A ] To [0010] and the compounds described in JP-A-2014-224170, [0019], and the like, the contents of which are incorporated into the present invention. The compounds having a norbornene skeleton may be used alone or in combination of two or more.
Ethylene units, -CH ₂ CH ₂ - is a repeating unit represented by. A cyclic olefin copolymer in which the ethylene unit is vinyl-polymerized with the norbornene unit described above is preferable.
The cyclic olefin copolymer may contain a small amount of repeating units composed of other copolymerizable vinyl monomers in addition to the ethylene unit and norbornene unit as long as the object of the present invention is not impaired. Specific examples of the other vinyl monomers include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1 -C3-C18 alpha olefins such as octadecene, cycloolefins such as cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene and cyclooctene. Such vinyl monomers may be used alone or in combination of two or more, and the repeating unit is preferably 10 mol% or less, more preferably 5 mol% or less.
Examples of the cyclic olefin polymer or the cyclic olefin copolymer include compounds described in JP-A 2010-89458, [0022] to [0031], and JP-A 2014-224170, [0018] to [0028]. The contents of this publication are incorporated into the present invention.

  These cyclic olefin polymers or cyclic olefin copolymers may be synthesized or commercially available. Although there is no restriction | limiting in particular as a synthesis method of a cyclic olefin polymer or a cyclic olefin copolymer, For example, [0031]-[0043] of Unexamined-Japanese-Patent No. 2010-89458 and [0010]-[0013] of Unexamined-Japanese-Patent No. 2003-26834. The contents of this publication are incorporated into the present invention.

  Other additives can be added to the polymer film as long as the object of the present invention is not impaired. Examples of the additive include an antioxidant, an ultraviolet absorber, a lubricant, and an antistatic agent. In particular, when the polymer film is placed on the surface of various devices, an ultraviolet absorber may be included.

There are no particular restrictions on the method for forming the polymer film. For example, a synthesized cyclic olefin polymer or cyclic olefin copolymer, or a commercially available cyclic olefin polymer or cyclic olefin copolymer may be formed by a solution film forming method or a melt film forming method. Can do. Although there is no restriction | limiting in particular as a solution film forming method or a melt film forming method, For example, the method as described in [0039]-[0058] of Unexamined-Japanese-Patent No. 2014-224170 can be mentioned, The content of this gazette is this invention. Embedded in.
The polymer film may be an unstretched film or a stretched film.

  A commercially available polymer film may be used as the polymer film of the laminated film of the present invention. Commercially available polymer film materials preferably used in the present invention include trade name Arton (ARTON (registered trademark)) film (cycloolefin polymer film) manufactured by JSR Corporation, trade name ZEONOR (trade name) manufactured by Nippon Zeon Co., Ltd. (Registered trademark)) film (cycloolefin polymer film), trade name Topas (TOPAS (registered trademark), cycloolefin copolymer film) manufactured by Polyplastics Co., Ltd., and the like.

  The film thickness of the polymer film is preferably 10 to 100 μm, more preferably 10 to 60 μm, and particularly preferably 10 to 50 μm. Thus, the polymer film can be thinned. Here, the film thickness of the polymer film means the average film thickness of the film.

<Polymer layer A>
The laminated film of the present invention has a polymer layer A disposed on at least one surface of the polymer film, and the polymer layer A satisfies at least one of the following conditions a and b.
Condition a: The elongation at break of the polymer layer A is 10% or more;
Condition b: The breaking stress of the polymer layer A is 20 MPa or less.

(Characteristics and film thickness of polymer layer A)
The breaking elongation of the polymer layer A is preferably 10% or more, more preferably 20 to 400%, and particularly preferably 200 to 400%.
The breaking stress of the polymer layer A is preferably 20 MPa or less, more preferably 1 to 15 MPa, and particularly preferably 1 to 8 MPa.

  The film thickness of the polymer layer A is preferably from 0.01 to 10 μm, more preferably from 1 to 6 μm from the viewpoint of the color tone after ultraviolet irradiation, and particularly preferably from 2 to 4 μm.

(binder)
In the laminated film of the present invention, the polymer layer A preferably contains a binder. There is no restriction | limiting in particular as a binder used for the polymer layer A, unless it is contrary to the meaning of this invention, a well-known binder can be used. Examples of the binder used for the polymer layer A include a urethane polymer, an olefin polymer, and a styrene butadiene rubber.
Among these, the laminated film of the present invention uses a cyclic olefin polymer film or a cyclic olefin copolymer film, in which the polymer layer A contains a binder and the binder in the polymer layer A is a urethane polymer or an olefin polymer. Even in the case, it is preferable from the viewpoint of easily increasing the impact resistance after ultraviolet irradiation. The binder in the polymer layer A is more preferably a urethane polymer from the viewpoint of good adhesion between the polymer layer A and the polymer film (cyclic olefin polymer film or cyclic olefin copolymer film).

-Urethane polymer-
A urethane-type polymer means the polymer which has a urethane bond in the principal chain of a repeating unit. Moreover, the copolymer which has this structure may be sufficient, and these are named generically and are called a urethane type polymer below. Urethane polymers are usually obtained by reaction of polyisocyanates and polyols. Examples of the polyisocyanate include TDI (toluene diisocyanate), MDI (diphenylmethane diisocyanate), NDI (naphthalene diisocyanate), TODI (tolidine diisocyanate), HDI (hexamethylene diisocyanate), IPDI (isophorone diisocyanate), and the like. Examples of the polyol include ethylene glycol, propylene glycol, glycerin and hexanetriol. As the isocyanate, a polymer obtained by subjecting a polyurethane polymer obtained by the reaction of polyisocyanate and polyol to chain extension treatment to increase the molecular weight can also be used. The polyisocyanate, polyol, and chain extension treatment described above are described in, for example, “Polyurethane Handbook” (edited by Keiji Iwata, Nikkan Kogyo Shimbun, published in 1987). Polyurethane resins are Superflex 470, 210, 150HS, Elastron H-3 (Daiichi Kogyo Seiyaku Co., Ltd.), Hydran AP-20, AP-40F, WLS-210 (DIC Corp.), Takelac WS5100. , W-6061, Olester UD-350 (Mitsui Chemicals, Inc.) are also commercially available.
From the viewpoint of elongation at break, the urethane polymer is preferably a thermal polymerization type polymer.

-Olefin polymer-
The olefin polymer refers to a polymer obtained by polymerizing an olefin or alkene having an unsaturated double bond group. Moreover, the copolymer which has this structure may be sufficient, and these are named generically and are called an olefin type polymer below.

  The olefin polymer is preferably a polymer obtained by polymerizing an olefin or alkene having an ethylenically unsaturated double bond group. Specifically, the olefin polymer is preferably any of the following.

(1) Homopolymer of ethylene or polypropylene (2) Copolymer comprising ethylene or polypropylene and other olefins such as ethylene vinyl acetate (for example, ethylene vinyl acetate copolymer)
(3) Copolymer comprising ethylene or polypropylene and acrylic monomer or methacrylic monomer (4) Copolymer comprising ethylene or polypropylene and carboxylic acid (including anhydride) (5) Ethylene or polypropylene and acrylic Copolymer comprising monomer or methacrylic monomer and carboxylic acid (including anhydride)

  Preferable examples of the acrylic monomer or methacrylic monomer constituting the olefin polymer include methyl methacrylate, ethyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate and the like.

  The carboxylic acid constituting the olefin polymer is preferably acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride and the like. These may be used alone or in combination of a plurality of types.

  The total of ethylene or polypropylene in the olefin polymer is preferably 80 to 98 mol%, more preferably 85 to 95 mol%. Further, the acrylic monomer or methacrylic monomer is preferably in the range of 0 to 20 mol%, more preferably 3 to 10 mol% in total. Furthermore, the total amount of carboxylic acid is preferably 0 to 15 mol%, more preferably 1 to 10 mol%. By setting the monomer composition within this range, both good adhesion and durability can be achieved.

  The olefin polymer preferably has a water-affinity functional group such as a carboxyl group or a hydroxyl group when the aqueous polymer is in the form of latex. When using olefin polymers in the form of latex, emulsification stability of surfactants (eg anionic and nonionic surfactants), polymers (eg polyvinyl alcohol), etc. to improve stability An agent may be included. Further, if necessary, a pH (power of hydrogengen) adjusting agent (eg, ammonia, triethylamine, sodium hydrogen carbonate, etc.), preservative (eg, 1,3,5-hexahydro- (2-hydroxyethyl) -s-triazine , 2- (4-thiazolyl) benzimidazole, etc.), thickeners (eg, sodium polyacrylate, methylcellulose, etc.), film-forming aids (eg, butyl carbitol acetate, etc.) and the like, known compounds as latex additives May be added.

  Some aqueous latexes of olefin polymers that can be used in the present invention are commercially available. Specific examples of commercially available products include Bondine HX-8210, HX-8290, TL-8030, LX-4110 (manufactured by Sumitomo Chemical Co., Ltd.), Arrow Base SA-1200, SB-1010, SE-1013N, SE-1200 (above, Unitika Ltd.), Nippon UFN1008 (manufactured by Nippon Zeon Co., Ltd.), and the like.

  Commercially available binders preferably used in the present invention include Takelac WS5100 (manufactured by Mitsui Chemicals, thermosetting silanol group-containing polycarbonate urethane resin), Olester UD350 (manufactured by Mitsui Chemicals, polyurethane resin), Arrow Base SE1013N ( Unitika's modified polyolefin), Chemipearl W100 (Mitsui Chemicals, polyethylene), Chemipearl W900 (Mitsui Chemicals, polyethylene), Chemipearl V100 (Mitsui Chemicals, ethylene vinyl acetate copolymer resin) ).

(UV absorber)
In the laminated film of the present invention, the polymer layer A preferably contains an ultraviolet absorber.
An ultraviolet absorber means a compound having a structure capable of absorbing light in the ultraviolet band.
As the UV absorber, known UV absorbers such as benzophenone UV absorbers, triazine UV absorbers, and benzotriazole UV absorbers can be used. Among these, triazine-based ultraviolet absorbers and benzotriazole-based ultraviolet absorbers are preferable from the viewpoint of easily suppressing deterioration in color tone after ultraviolet irradiation and easily increasing impact resistance after ultraviolet irradiation. Triazine-based ultraviolet absorbers Is more preferable from the viewpoint of easily suppressing the deterioration of the color tone after the ultraviolet irradiation and increasing the impact resistance after the ultraviolet irradiation.

More specifically, examples of the ultraviolet absorber that can be used in the present invention include salicylic acid derivatives such as phenyl salicylate and para-tert-butylphenyl salicylate;
2,4-dihydroxy benzophenone, 2-hydroxy-4-methoxy benzophenone, 2,2'-dihydroxy-4-methoxy benzophenone, 2,2'-dihydroxy-4,4'-dimethoxy benzophenone, 2-hydroxy -4-dimethoxy-2'-carboxy benzophenone, 2-hydroxy-4-dimethoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxy benzophenone, 2,2 ', 4,4'-tetra Hydroxybenzophenone, 4-dodecyloxy-2-hydroxy-benzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2-hydroxy-4-benzyloxy-benzophenone and 2-hydroxy-4-methoxybenzophenone- 5-sulfonic acid Benzophenone ultraviolet absorbers;

2- (2′-hydroxy-5′-methyl-phenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) benzotriazole, 2- (2′-hydroxy) -3'-tert-butyl-5'-methyl-phenyl) -5-chloro-benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chloro Benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2- [2 '-Hydroxy-3'-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole and 2,2'-methylenebis [4- 1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl) phenol] benzotriazole ultraviolet absorbers such as;
Succinic acid anilide derivatives such as 2-ethoxy-5-tert-butyl-2′-ethylacetic acid bisanilide and 2-ethoxy-2-ethylsuccinic acid bisanilide;
2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, 1,3-bis- (4-Benzoyl-3-hydroxyphenoxy) -2-propyl acrylate, 1,3-bis- (4-benzoyl-3-hydroxyphenoxy) -2-propyl methacrylate, methyl ortho-benzoylbenzoate and ethyl-2-cyano -An ultraviolet absorber having an aromatic ring and an ester structure such as 3,3-diphenyl acrylate;
[2,2′-thiobis- (4-tert-octylphenolite)]-n-butylamine nickel II, [2,2′-thiobis- (4-tert-octylphenolite)]-n-ethylhexylamine Nickel compound ultraviolet absorbers such as nickel II, dibutyl nickel dithiocarbamate and nickel thiobisphenol complex;

Semicarbamine light stabilizers;
Zinc oxide UV stabilizers;
Zinc oxide synergists;
Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- (3- (3 5-Di-tert-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -4- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) -2,2,6 6-tetramethylpiperidine, 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,2,3-triazaspiro [4,5] undecane-2,4-dione, 4-benzoyloxy- 2,2,6,6-tetramethylpiperidine; dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate;
Poly [[6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl ) Imino] hexamethylene [[2,2,6,6-tetramethyl-4-piperidyl] imino]], 2- (3,5-di-tertbutyl-4-hydroxybenzyl) 2-n-butylmalonic acid Bis (1,2,2,6,6-pentamethyl-4-piperidyl), tetraxy (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1 , 2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and tridecyl alcohol condensate, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetrame Condensation product of ru-4-piperidinol and tridecyl alcohol, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′, β'-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) diethanol condensate, 1,2,2,6,6-pentamethyl-4-piperidyl -Hindered amine light stabilizers such as methacrylate and 2,2,6,6-tetramethyl-4-piperidyl-methacrylate.

The triazine-based ultraviolet absorber that can be used in the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include mono (hydroxyphenyl) triazine compounds, bis (hydroxyphenyl) triazine compounds, and tris. And (hydroxyphenyl) triazine compounds. Among these, a mono (hydroxyphenyl) triazine compound containing Tinuvin 479 DW is preferable.
Examples of mono (hydroxyphenyl) triazine compounds include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl). ) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4) -Isooctyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6 Bis (2,4-dimethylphenyl) -1,3,5-triazine. Examples of the bis (hydroxyphenyl) triazine compound include 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2, 4-bis (2-hydroxy-3-methyl-4-propyloxyphenyl) -6- (4-methylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl-) 4-hexyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2-phenyl-4,6-bis [2-hydroxy-4- [3- (methoxyheptaethoxy) -2-hydroxypropyloxy] phenyl] -1,3,5-triazine and the like. Examples of the tris (hydroxyphenyl) triazine compound include 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2, 4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2,4,6-tris [2-hydroxy-4- (3-butoxy-2-hydroxypropyloxy) Phenyl] -1,3,5-triazine, 2,4-bis [2-hydroxy-4- [1- (isooctyloxycarbonyl) ethoxy] phenyl] -6- (2,4-dihydroxyphenyl) -1, 3,5-triazine, 2,4,6-tris [2-hydroxy-4- [1- (isooctyloxycarbonyl) ethoxy] phenyl] -1,3,5-triazine 2,4-bis [2-hydroxy-4- [1- (isooctyloxycarbonyl) ethoxy] phenyl] -6- [2,4-bis [1- (isooctyloxycarbonyl) ethoxy] phenyl] -1, 3,5-triazine and the like can be mentioned.

Examples of triazine-based or benzotriazole-based ultraviolet absorbers include, in addition to the above-described compounds, JP-A 2012-136919, JP-A 2012-122000, JP-A 2010-514844, and the like. Mention may be made of the triazine-based or benzotriazole-based UV absorbers described.
These may be used alone or in combination of two or more.

Although there is no restriction | limiting in particular in content of the ultraviolet absorber in the polymer layer A, Content of the ultraviolet absorber in the polymer layer A is 0.05 g / m < ² > or more, The deterioration of the color tone after ultraviolet irradiation This is preferable from the viewpoint of easily suppressing the impact and increasing the impact resistance after ultraviolet irradiation.
When using a triazine-based ultraviolet absorber, the content of the ultraviolet absorber polymer layer A is preferably not less than 0.05 g / m ² or more, more preferably 0.1 g / m ² or more, 0 It is particularly preferable that the amount be 0.5 g / m ² or more.
When a benzotriazole-based ultraviolet absorber is used, the content of the ultraviolet absorber in the polymer layer A is preferably 0.20 g / m ² or more, more preferably 0.5 g / m ² or more, It is particularly preferably 1 g / m ² or more.
In the laminated film of the present invention, the polymer layer A contains an ultraviolet absorber, and the content of the ultraviolet absorber in the polymer layer A is 0.8 g / m ² or less. It is preferable from the viewpoint that the precipitation becomes difficult and the transparency of the laminated film becomes good.

  Commercially available ultraviolet absorbers preferably used in the present invention include trade names of BASF: Tinuvin P, 234, 320, 326, 327, 328, 213, 400, 477, Tinuvin 479 DW, Tinuvin 1577 ED, etc., Sumitomo Chemical Product names manufactured by Kogyo Co., Ltd .: SUMISORB 110, 130, 140, 220, 250, 300, 320, 340, 350, 400, etc., NEW coat UVA 204W (manufactured by Shin-Nakamura Chemical Co., Ltd.), ADK STAB LA-31 ( ADEKA Corporation), 2,4-dihydroxybenzophenone (Tokyo Chemical Industry Co., Ltd.) and the like.

[Production method of laminated film]
Although there is no restriction | limiting in particular in the method to manufacture the laminated | multilayer film of this invention, It is preferable to manufacture especially with the following manufacturing methods of the laminated | multilayer film of this invention.
The method for producing a laminated film of the present invention includes a step of arranging a composition for forming a polymer layer A on at least one surface of a polymer film,
The polymer film is a cyclic olefin polymer film or a cyclic olefin copolymer film;
The composition for forming the polymer layer A contains an ultraviolet absorber and a binder.

<Formation of polymer film>
The polymer film used in the present invention can be formed by a known method. The polymer film can be obtained by melting and extruding pellets into a film shape and then cooling and solidifying with a casting drum to form an unstretched film.

<Surface treatment>
Before the step of forming the polymer layer A on the polymer film, a step of performing a surface treatment is preferably provided. Examples of the surface treatment include corona treatment, ultraviolet treatment (ultraviolet; UV treatment), flame treatment, low-pressure plasma treatment, atmospheric pressure plasma treatment, sandblast treatment, and chromium mixed acid treatment. As the flame treatment, a method of adding a silane compound described in Japanese Patent No. 3893394 and Japanese Patent Application Laid-Open No. 2007-39508 can also be used. Among these, corona treatment, flame treatment, atmospheric pressure plasma treatment, and ultraviolet treatment (UV treatment) are preferable from the viewpoint of simplicity and environmental load.

<Formation of polymer layer A>
The polymer layer A can be formed by a known method such as coating or pasting. Especially, the manufacturing method of the laminated | multilayer film of this invention has the process of arrange | positioning (preferably application, more preferably application | coating) the composition for polymer layer A formation on the at least one surface of a polymer film, At least of a polymer film It is preferable to form the polymer layer A on one surface.

First, the process of disposing the composition for forming the polymer layer A on at least one surface of the polymer film will be described. The step of disposing the composition for forming the polymer layer A on at least one surface of the polymer film is preferably a step of applying the composition for forming the polymer layer A on at least one surface of the polymer film. More preferably. As a coating method of the composition for forming the polymer layer A, for example, a known coating method such as a gravure coater or a bar coater can be used.
The composition for forming the polymer layer A used as the coating liquid may be an aqueous system using water as a coating solvent or a dispersion medium, or a solvent system using an organic solvent such as toluene or methyl ethyl ketone. Among these, from the viewpoint of environmental burden, it is preferable to use water as a solvent or a dispersion medium. As the coating solvent or dispersion medium, one kind may be used alone, or a water-miscible organic solvent may be mixed with water and used. Examples of preferable coating solvent or dispersion medium include water, water / ethyl alcohol = 95/5 (mass ratio), water / ethylene glycol monomethyl ether (methyl cellosolve) = 97/3 (mass ratio), and the like.
In the method for producing a laminated film of the present invention, the polymer layer A forming composition contains an ultraviolet absorber and a binder. The composition for forming the polymer layer A is preferably a solution dissolved in the above solvent or a dispersion liquid dispersed in the above dispersion medium.

  The drying temperature of the polymer layer A is preferably a method of drying at 50 to 200 ° C, more preferably a method of drying at 80 to 150 ° C.

[Transparent conductive film]
The transparent conductive film of the present invention has the laminated film of the present invention.
The laminated film of the present invention can be used for a transparent conductive film. The transparent conductive film has a conductive film and a laminated film as a transparent resin film. The conductive layer may be formed in a layer shape, but is preferably formed so as to have an intermittent portion. An intermittent part means the part in which the conductive layer is not provided, and it is preferable that the outer periphery of an intermittent part is surrounded by the conductive layer. In the present invention, forming a conductive layer so as to have an intermittent portion is also referred to as forming a conductive layer in a pattern or mesh. Examples of the conductive layer include JP2013-1009A, JP2012-216550A, JP2012-151095A, JP2012-25158A, JP2011-253546A, and JP2011. -197754, JP2011-34806, JP2010-198799, JP2009-277466, JP2012-216550, JP2012-151095, International Publication 2010/140275. No. pamphlet and the conductive layer described in the international publication 2010/114056 pamphlet.

  The conductive layer used in the present invention more preferably contains silver and a hydrophilic resin. Examples of the water-soluble resin include gelatin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), starch and other polysaccharides, cellulose and derivatives thereof, polyethylene oxide, polyvinylamine, chitosan, polylysine, polyacrylic acid, polyalginic acid, Examples include polyhyaluronic acid and carboxycellulose. These have neutral, anionic, and cationic properties depending on the ionicity of the functional group. Of these, gelatin is particularly preferred.

It is particularly preferable to use a silver halide photographic light-sensitive material for the conductive layer used in the present invention. When a silver halide photographic light-sensitive material is used, the method for producing a conductive layer includes the following three forms depending on the light-sensitive material and the form of development processing.
(1) A mode in which a photosensitive silver halide black-and-white photosensitive material containing no physical development nuclei is chemically developed or thermally developed to form a metallic silver portion on this photosensitive material.
(2) An embodiment in which a photosensitive silver halide black and white photosensitive material containing physical development nuclei in a silver halide emulsion layer is dissolved and physically developed to form a metallic silver portion on the photosensitive material.
(3) A photosensitive silver halide black-and-white photosensitive material containing no physical development nuclei and an image receiving sheet having a non-photosensitive layer containing physical development nuclei are overlapped and developed by diffusion transfer, and the metallic silver portion is non-photosensitive image-receiving sheet. Form formed on top.

The aspect (1) is an integrated black-and-white development type, and a light-transmitting conductive film such as a light-transmitting conductive film is formed on the photosensitive material. The obtained developed silver is chemically developed silver or heat developed silver, and is highly active in the subsequent plating or physical development process in that it is a filament with a high specific surface area.
In the above aspect (2), the light-transmitting conductive film such as a light-transmitting conductive film is formed on the photosensitive material by dissolving silver halide grains close to the physical development nucleus and depositing on the development nucleus in the exposed portion. A characteristic film is formed. This is also an integrated black-and-white development type. Although the developing action is precipitation on physical development nuclei, it is highly active, but developed silver is a sphere with a small specific surface area.
In the above aspect (3), the silver halide grains are dissolved and diffused in the unexposed area and deposited on the development nuclei on the image receiving sheet, whereby a light transmitting conductive film or the like is formed on the image receiving sheet. A conductive film is formed. This is a so-called separate type in which the image receiving sheet is peeled off from the photosensitive material.

  In either case, either negative development processing or reversal development processing can be selected. In the case of the diffusion transfer method, negative development processing can be performed by using an auto-positive type photosensitive material as a photosensitive material. Become.

  The chemical development, thermal development, dissolution physical development, and diffusion transfer development mentioned here have the same meanings as are commonly used in the industry, and are general textbooks of photographic chemistry such as Shinichi Kikuchi, “Photochemistry” (Kyoritsu Publishing) (Published in 1955), C.I. E. K. It is described in "The Theory of Photographic Processes, 4th ed." Edited by Mees (Mcmillan, 1977). Although this case is an invention related to liquid processing, a technique of applying a thermal development system as another development system can also be referred to. For example, the technique described in each specification of Unexamined-Japanese-Patent No. 2004-184893, 2004-334077, 2005-010752 is applicable.

  In the present invention, the silver salt emulsion layer serving as the conductive layer may contain additives such as a solvent and a dye in addition to the silver salt and the binder. Examples of the silver salt include inorganic silver salts such as silver halide and organic silver salts such as silver acetate. In the present invention, it is preferable to use silver halide having excellent characteristics as an optical sensor.

  The solvent used for forming the silver salt emulsion layer is not particularly limited. For example, water, organic solvents (for example, alcohols such as methanol, ketones such as acetone, amides such as formamide, dimethyl sulfoxide, etc. Sulphoxides such as, esters such as ethyl acetate, ethers, etc.), ionic liquids, and mixed solvents thereof.

  A protective layer may be provided on the silver salt emulsion layer. In the present invention, the protective layer means a layer composed of a binder such as gelatin or a high molecular polymer, and is formed on a silver salt emulsion layer having photosensitivity in order to exhibit an effect of preventing scratches and improving mechanical properties. The thickness is preferably 0.5 μm or less. The coating method and forming method of the protective layer are not particularly limited, and a known coating method and forming method can be appropriately selected. For example, with respect to the protective layer, the description in JP-A-2008-250233 can be referred to.

  Furthermore, in the present invention, other functional layers such as an undercoat layer and an antistatic layer may be provided. As the undercoat layer, those described in paragraphs [0021] to [0023] of JP-A-2008-250233 can be applied. As the antistatic layer, those described in paragraphs [0012] and [0014] to [0020] of JP-A-2008-250233 can be applied.

  In addition, the transparent conductive film mentioned above is suitable for a touch-panel use, for example, a touch panel can be produced according to description of Paragraph [0073]-[0075] of Unexamined-Japanese-Patent No. 2009-176608.

[Organic electroluminescence device]
The organic electroluminescent element of the present invention has the laminated film of the present invention.
The laminated film of the present invention can be used as a substrate (base film) such as an organic electroluminescence element or a protective film. When the laminated film of the present invention is used for an organic electroluminescence device or the like, JP-A-11-335661, JP-A-11-335368, JP-A-2001-192651, JP-A-2001-192653, JP-A-2001-192653. JP, JP 2001-335776, JP 2001-247859, JP 2001-181616, JP 2001-181617, JP 2002-181816, JP 2002-181617, JP 2002-056776. It is possible to apply the contents described in each publication. Moreover, it is preferable to use together with the content of each gazette of Unexamined-Japanese-Patent No. 2001-148291, Unexamined-Japanese-Patent No. 2001-221916, and Unexamined-Japanese-Patent No. 2001-231443.

The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below. Examples 1, 6, 10, 11, 14-22, 24-27, 29-31 are reference examples.

[Examples 1 to 32, Comparative Examples 1 to 24]
<Preparation of polymer film>
In each Example and Comparative Example, the following polymer film having a film thickness of 40 μm was used. The specific configuration of the polymer film is described below.
Arton: Product name Arton Film (cycloolefin polymer film) manufactured by JSR Corporation
ZEONOR: Product name ZEONOR film (cycloolefin polymer film) manufactured by ZEON CORPORATION
Topas: Trade name Topas (TOPAS, cycloolefin copolymer film) manufactured by Polyplastics Co., Ltd.

<Surface treatment of polymer film>
Prior to the step of forming the polymer layer A on the polymer film, a step of subjecting the polymer film to a surface treatment was performed. Specific methods and conditions for the surface treatment are described below.
--- Corona treatment conditions ---
・ Apparatus: Corona surface modification evaluation device (TEC-4AX) manufactured by Kasuga Electric Co., Ltd.
・ Processing frequency: 9.6 kHz
・ Processing speed: 5 m / min ・ Processing strength: 0.7 J / m ²

<Formation of polymer layer A>
On the polymer film, the polymer layer A forming composition was applied by the following method and dried to form the polymer layer A. Specifically, the composition for forming polymer layer A having the following composition was applied onto the surface of the polymer film that had been surface-treated using a bar coater, and dried at 100 ° C. for 2 minutes.
The obtained polymer film and the laminated film of the polymer layer A were used as the laminated films of Examples 1 to 32 and Comparative Examples 1 to 24.

(Composition of the composition for forming the polymer layer A)
Binders listed in Table 1 (as solids) 100 parts by weight UV absorbers listed in Table 1 below Additives (surfactant, trade name NAROACTY CL95, Sanyo Chemical Co., Ltd.) as shown in Table 1 below Industrial)
0.14 parts by mass Solvent (water) 546 parts by mass

(Binder of polymer layer A)
Urethane system 1: Takelac WS5100 (Mitsui Chemicals, silanol group-containing polycarbonate urethane)
Urethane system 2: Olester UD350 (Mitsui Chemicals, silanol group-free polyether urethane)
Urethane system 3: According to Example 9 of JP-A-2010-89458, a polymer layer A was prepared by UV curing using KRM8452 (manufactured by Daicel Ornex Co., Ltd., UV curable acrylic urethane).
Olefin system 1: Arrow base SE1013N (manufactured by Unitika Ltd., acid-modified polyolefin)
Olefin type 2: Chemipearl S75N (Mitsui Chemicals, Ionomer type polyolefin)
Olefin system 3: Hitec S3121 (manufactured by Toho Chemical Co., Ltd., acid-modified polyolefin)
Olefin system 4: Chemipearl V100 (Mitsui Chemicals, ethylene vinyl acetate copolymer)
Styrene butadiene rubber: Trade name Nipol SX1105 (manufactured by Nippon Zeon)
Polyester system 1: Finetex ES-650 (manufactured by DIC)
Polyester system 2: Vylonal MD1245 (manufactured by Toyobo)

(UV absorber of polymer layer A)
Triazine 1: Tinuvin 479DW (manufactured by BASF, hydroxyphenyl triazine UV absorber)
Triazine type 2: Tinuvin 400DW (manufactured by BASF, hydroxyphenyl triazine UV absorber)
Benzotriazole series 1: NEW coated UVA 204W (manufactured by Shin-Nakamura Chemical Co., Ltd.)
Benzotriazole series 2: ADK STAB LA-31 (ADEKA Corporation)
Benzophenone series 1,2,4-dihydroxybenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.)

[Evaluation]
<Evaluation of polymer layer A>
(Breaking elongation and breaking stress)
A single layer film having the same film thickness as the polymer layer A used in each example and comparative example was obtained by the following method.
A polymer solution is applied to the therapy (manufactured by Toray Industries, Inc.) and dried in an oven at 100 ° C. for 2 minutes to form a polymer film on the surface of the therapy.
A sample was prepared by cutting out the obtained single layer film of the polymer layer A into a rectangular shape having a length of 3 cm and a width of 0.5 cm.
A fresh sample was oriented in the longitudinal direction (long side direction) and pulled from both sides at a constant speed of 10 mm / min, and elongation [%] and stress [MPa] were measured. The elongation at break is the value of elongation when the polymer layer A is broken, and the break stress is the value of stress at break. Fresh shows the results of each evaluation after film formation of the polymer layer A and standing for 3 hours in an environment of a temperature of 23 ° C. and a relative humidity of 60%.
In addition to the method using the above-mentioned therapy, the breaking elongation and breaking stress are measured by scraping the polymer film with a razor from the surface opposite to the polymer layer A of the laminated film and taking out the single film of the polymer layer A. You can also For example, for Example 1, the breaking elongation measured by the above method was 135% and the breaking stress was 22 MPa, which was in good agreement with the method measured using therapy.
The results obtained are listed in the table below.

<Evaluation of laminated film>
The following evaluation was performed about the laminated | multilayer film of each Example and the comparative example.
Fresh shows the result of each evaluation after film formation of the laminated film of each Example and Comparative Example, and after standing for 3 hours in an environment of a temperature of 23 ° C. and a relative humidity of 60%.
After the ultraviolet irradiation test, after the laminated film of each Example and Comparative Example was formed, after the ultraviolet irradiation was performed under the following conditions, the film was allowed to stand for 3 hours in an environment of a temperature of 23 ° C. and a relative humidity of 60%. The results of each evaluation are shown.
-UV irradiation conditions-
Using a light resistance tester “I Super UV Tester W-151” manufactured by Iwasaki Electric Co., Ltd., ultraviolet light was irradiated at an illuminance of 900 W / m ² for 48 hours. However, the environmental conditions at the time of ultraviolet light irradiation were 63 ° C. and relative humidity 50%.

(Average value of transmittance of light having a wavelength of 290 to 360 nm)
The transmittance at a wavelength of 290 to 360 nm of the laminated films (polymer film and laminated film of polymer layer A) of each example of Fresh and the comparative example was measured using an infrared visible spectrophotometer. Measurements were made at intervals of 290 nm to 10 nm, the sum of the measured transmittances was taken, divided by the number of measurements (8 times in the case of the current wavelength region), and calculated as an average value of transmittance.
The obtained results are shown in the table below as transmittance Ave (290-360 nm).

(Impact strength)
The impact strength of the laminated film of each Example and Comparative Example after the Fresh and UV irradiation tests was measured using a film impact tester (Toyo Seiki Seisakusho).
The measurement results were evaluated according to the following eight evaluation criteria.
-Evaluation criteria-
8 points: 12 kgf · cm (1.18 N · m) or more, less than 15 kgf · cm (1.47 N · m) 7 points: 10 kgf · cm (0.98 N · m) or more, 12 kgf · cm (1.18 N · m) ) Less than 6 points: 8 kgf · cm (0.78 N · m) or more Less than 10 kgf · cm (0.98 N · m) 5 points: 6 kgf · cm (0.59 N · m) or more, 8 kgf · cm (0.78 N) Less than 4 points: 4 kgf · cm (0.39 N · m) or more, less than 6 kgf · cm (0.59 N · m) 3 points: 2 kgf · cm (0.20 N · m) or more, 4 kgf · cm (0 Less than .39 N · m) 2 points: 1 kgf · cm (0.098 N · m) or more, less than 2 kgf · cm (0.20 N · m) 1 point: less than 1 kgf · cm (0.098 N · m) Result obtained Are listed in the table below.

(Close contact)
On the side of the laminated film of each of the examples of Fresh and the comparative example, on the side on which the polymer layer A was formed, 6 pieces of scratches were made in each of the longitudinal and lateral directions at intervals of 3 mm using a razor to form 25 film pieces. A Mylar tape (polyester tape) having a width of 20 mm was pasted thereon and quickly pulled in the 180 ° direction for peeling.
At this time, the adhesion between the polymer film and the polymer layer A was evaluated according to the following evaluation criteria depending on the number of peeled film pieces.
-Evaluation criteria-
5: No peeling occurs 4: The peeled film piece is zero, but the scratch part is slightly peeled 3: The peeled film piece is less than 1 sheet 2: The peeled film piece is 1 sheet or more and less than 5 sheets 1: The results of obtaining 5 or more exfoliated film pieces are shown in the table below.

(Color tone b *)
The b * values of the laminated films of each Example and Comparative Example after the ultraviolet irradiation test were measured by a transmission method using a spectral color difference meter. Here, the b * value represents the b * value in the L * a * b * color system. The b * value is preferably less than 4.
The results obtained are listed in the table below.

(transparency)
The measuring method of the haze value of the laminated film of each example of Fresh and the comparative example is as follows. A laminated film sample of 40 mm × 80 mm was prepared and measured using a turbidimeter (NDH5000, Nippon Denshoku Industries Co., Ltd.) in an environment of 25 ° C. and a relative humidity of 60%. The obtained haze value was evaluated according to the following evaluation criteria.
-Evaluation criteria-
A: Haze value is less than 1.2 B: Haze value is 1.2 or more The results obtained are listed in the table below.

From the above Tables 1 and 2, the laminated film of the present invention has high impact resistance after UV irradiation and good color tone after UV irradiation even when a cyclic olefin polymer film or a cyclic olefin copolymer film is used. I understood it.
On the other hand, from Comparative Examples 1-6, 13-16 and 19-23, when the average value of the light transmittance of the laminated film having a wavelength of 290 to 360 nm exceeds the upper limit defined in the present invention, the impact after ultraviolet irradiation It was found that the resistance was low and the color tone after UV irradiation was poor. From Comparative Examples 7 to 12, 17, 18 and Comparative Examples 20 to 24, it was found that when the breaking elongation condition a of the laminated film did not satisfy the breaking stress condition b, the impact resistance after ultraviolet irradiation was low. .

[Examples 101 to 132]
<Preparation of transparent conductive film>
(Undercoat layer application)
After the corona treatment was performed on one surface of the laminated film of each example formed as described above, a first undercoat layer and a second undercoat layer were applied. The composition and application method of the first undercoat layer and the second undercoat layer were as described in paragraphs [0117] to [0120] of JP2010-256908A.

(Formation of conductive layer containing water-soluble resin and silver)
The following silver halide photosensitive material was coated on the undercoat layer to form a conductive layer.

-Silver halide photosensitive material-
An emulsion containing 10.0 g of gelatin per 150 g of Ag in an aqueous medium and containing silver iodobromochloride grains having an average equivalent sphere diameter of 0.1 μm (I = 0.2 mol%, Br = 40 mol%) was prepared. . In this emulsion, K ₃ Rh ₂ Br ₉ and K ₂ IrCl ₆ were added to a concentration of 10 ⁻⁷ (mol / mol silver), and silver bromide grains were doped with Rh ions and Ir ions. . After adding Na ₂ PdCl ₄ to this emulsion and further performing gold-sulfur sensitization with chloroauric acid and sodium thiosulfate, together with the gelatin hardener, the coating amount of silver is 10 g / m ^2. The transparent resin film was coated on the undercoat layer. At this time, the volume ratio of Ag: gelatin was 2: 1.

  Application was carried out for 500 m with a width of 0.7 m, and both ends were cut off so as to leave 0.5 m of the central part of the application to obtain a roll-shaped silver halide photosensitive material.

(exposure)
The exposure pattern was formed according to the pattern shown in FIG. The arrangement pitch Ps of the small lattices 18 is 200 μm, and the arrangement pitch Pm of the medium lattices 20a to 20h is 2 × Ps. The thickness of the conductive portion of the small lattice 18 was 2 μm, and the width was 10 μm. The exposure was performed using parallel light using a high-pressure mercury lamp as a light source through the photomask having the above pattern.
Moreover, although the conductive pattern was formed also according to FIG. 5 of patent 4820451, the following evaluation result obtained the same result as the case of FIG.

<Development processing>
The formulation of developer 1L is as follows.
Hydroquinone 20g
Sodium sulfite 50g
40g potassium carbonate
Ethylenediamine tetraacetic acid 2g
Potassium bromide 3g
Polyethylene glycol 2000 1g
Potassium hydroxide 4g
The pH was adjusted to 10.3.

The prescription for 1 L of the fixing solution is as follows.
300 ml of ammonium thiosulfate solution (75%)
Ammonium sulfite monohydrate 25g
1,3-diaminopropane tetraacetic acid 8g
Acetic acid 5g
Ammonia water (27%) 1g
The pH was adjusted to 6.2.

Silver halide photosensitive material exposed using the above processing agent is processed using an automatic developing machine FG-710PTS manufactured by Fuji Film Co., Ltd .: development 35 ° C., 30 seconds, fixing 34 ° C., 23 seconds, water washing, running water (5 L / Min) for 20 seconds.
The obtained laminated films of Examples 1 to 32 and patterned conductive layers were used as transparent conductive films of Examples 101 to 132, respectively.

<Production of touch panel>
A touch panel was produced using the transparent conductive film of each Example described above according to paragraphs [0073] to [0075] of JP-A-2009-176608. The touch panel using the transparent conductive film of this invention confirmed that the impact resistance after ultraviolet irradiation was high, and the color tone after ultraviolet irradiation was favorable.

  According to the present invention, even when a cyclic olefin polymer film or a cyclic olefin copolymer film is used, a laminated film having high impact resistance after ultraviolet irradiation and good color tone after ultraviolet irradiation can be obtained. Therefore, the laminated film of the present invention can be used for a polarizing plate, a transparent conductive film, an antireflection film, an organic electroluminescence element, and various display devices, and particularly preferably used for a transparent conductive film and an organic electroluminescence element. Yes, it has high industrial applicability.

Claims (11)

A laminated film having a polymer film and a polymer layer A disposed on at least one surface of the polymer film,
The polymer film is a cyclic olefin polymer film or a cyclic olefin copolymer film;
The polymer layer A satisfies at least one of the following conditions a and b:
Ri Der average value of the transmittance is 18% or less of the light wavelength 290~360nm of the laminated film,
The polymer layer A contains an ultraviolet absorber;
The content of the ultraviolet absorber in the polymer layer A is 0.1 to 0.8 g / m ² ,
The laminated film ultraviolet absorber Ru der triazine-based UV absorber of the polymer layer A;
Condition a: The elongation at break of the polymer layer A is 10% or more;
Condition b: The breaking stress of the polymer layer A is 20 MPa or less. The polymer layer A contains a binder,
The laminated film according to claim 1, wherein the binder in the polymer layer A is a urethane polymer, an olefin polymer, or a styrene butadiene rubber. The laminated film according to claim 2 , wherein the binder in the polymer layer A is a urethane-based polymer. The film thickness of the said polymer layer A is 1-10 micrometers, The laminated | multilayer film as described in any one of Claims 1-3. Having a step of forming the polymer layer A by disposing the composition for forming the polymer layer A on at least one surface of the polymer film;
The polymer film is a cyclic olefin polymer film or a cyclic olefin copolymer film;
The polymer layer A composition for forming seen containing an ultraviolet absorber and a binder,
The content of the ultraviolet absorber in the polymer layer A is 0.1 to 0.8 g / m ² ,
The manufacturing method of the laminated | multilayer film whose said ultraviolet absorber in the said composition for polymer layer A formation is a triazine type ultraviolet absorber . The method for producing a laminated film according to claim 5 , wherein the binder in the composition for forming the polymer layer A is a urethane polymer, an olefin polymer, or a styrene butadiene rubber. The method for producing a laminated film according to claim 6 , wherein the binder in the composition for forming the polymer layer A is a urethane polymer. The film thickness of the said polymer layer A is 1-10 micrometers, The manufacturing method of the laminated | multilayer film as described in any one of Claims 5-7. Laminated film produced by the production method of a multilayer film according to any one of claims 5-8. The transparent conductive film which has a laminated | multilayer film as described in any one of Claims 1-4 and 9 . The organic electroluminescent element which has a laminated | multilayer film as described in any one of Claims 1-4 and 9 .