JP6611292B2 - Method for producing laminated film, laminated film, transparent conductive film, retardation film, and organic electroluminescence element - Google Patents

Description

  The present invention relates to a method for producing a laminated film, a laminated film, a transparent conductive film, a retardation film, and an organic electroluminescence element. Specifically, the present invention provides a laminated film having excellent adhesion between the cyclic olefin film and the coating layer even when the coating layer is formed on the cyclic olefin film using an aqueous coating material. The present invention relates to a method for producing a laminated film that can be produced. Moreover, this invention relates also to the laminated film manufactured with this manufacturing method of a laminated film, and the transparent conductive film, retardation film, and organic electroluminescent element which have 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, a protective film, a retardation film, and the like. Among these, a cyclic olefin film (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.

  By the way, since the cyclic olefin film does not have a polar group or is a nonpolar film having very few polar groups as compared with a polyester film or the like, the cyclic olefin film itself does not have much adhesiveness. Therefore, a coating layer such as an easy-adhesion layer is laminated on the cyclic olefin polymer film or the cyclic olefin copolymer film, and the film is bonded to another film via the coating layer.

Usually, the coating layer is formed by an off-line coating method or an in-line coating method. In particular, the use of an in-line coating method for water-based coating materials has been studied from the viewpoint of reducing environmental burden and cost.
For example, Patent Document 1 discloses (A) polyurethane, (B) epoxy compound, (C) on the surface of a base film having a layer made of a resin containing an alicyclic structure-containing polymer or acrylic polymer on the surface. One or both of primary amine and secondary amine, and (D) 1.4 equivalent to 2.7 equivalent of tertiary amine, imidazole compound and imidazoline to 1 equivalent of epoxy group of (B) epoxy compound described above A method for producing a multilayer film is described which comprises applying and curing a resin containing at least one compound selected from the group consisting of compounds. According to Patent Document 1, such a structure is a multilayer film including a base film having a layer made of a resin containing an alicyclic structure-containing polymer or an acrylic polymer, and is bonded to a polarizer. It is described that it is possible to provide a multi-layer film that has a high strength and that does not easily lower its adhesive strength even in a high humidity environment. Patent Document 1 also describes that a base film is stretched and an aqueous urethane resin is used at the same time as the applied resin is cured.

On the other hand, after applying and drying a solvent-based coating liquid on a cyclic olefin-based film, it is known to perform stretching and heat setting from the viewpoint of improving various properties.
For example, Patent Document 2 discloses a step of obtaining an optical film B having an average orientation angle β _{1 in} the range of 10 to 80 ° with respect to the width direction at the stretching end position in this step, and a polyamide on the optical film B. And a step of drying a coating film formed by applying a solution of at least one polymer selected from the group consisting of polyimide, polyester, polyetherketone, polyamide-imide, and polyesterimide, and the average orientation angle β is in the width direction. The manufacturing method of the long optical compensation film which is in the range of 10 to 80 ° and whose Nz coefficient value is 1.3 or more or −0.3 or less is described. Patent Document 2 also describes that oblique stretching is performed using a tenter stretching machine that includes a preheating zone, a stretching zone, and a fixed zone, and the stretching zone is linear without changing the film running direction. Has been.
In Patent Document 3, an oxidizing agent is applied to at least one surface of a base film sheet to form an oxidizing agent layer, a monomer is supplied and brought into contact with the oxidizing agent, and then the surface of the base film sheet is applied. A method for producing an antistatic film sheet is described in which a film sheet is stretched after forming a conductive polymer layer.

The cyclic olefin used for the cyclic olefin-based film may be used by being mixed with another main binder. For example, Patent Document 4 discloses an opaque biaxially stretched polyester film in which a cycloolefin copolymer is contained in a polyester film for uses other than optical films.
Patent Document 4 discloses an opaque biaxially stretched polyester film comprising at least one polyester layer containing 2 to 60% by weight of a cycloolefin copolymer having a glass transition temperature of 70 to 270 ° C. An opaque biaxially stretched polyester film having adhesion promoting properties on one side is described. Patent Document 4 discloses a method for producing the above film, in which a melt corresponding to each layer of the film is extruded and / or co-extruded from a flat-film-die (slot die), and the drawn melt film is 1 Also described is a method of producing a film that is cooled and solidified by two or more rolls, biaxially stretched, heat set, applied between extrusion and heat set and / or corona or flame treated on the desired surface after heat setting. Yes.

JP 2012-206343 A JP 2011-197683 A JP 2006-224517 A JP-T-2004-50459

  When this inventor formed the coating layer using the water-system coating material on the cyclic olefin type film, it came to discover that there exists a subject in which the adhesiveness of a cyclic olefin type film and a coating layer is insufficient.

  The problem to be solved by the present invention is that even when a coating layer is formed on a cyclic olefin film using an aqueous coating material, the adhesion between the cyclic olefin film and the coating layer (the initial An object of the present invention is to provide a method for producing a laminated film capable of producing a laminated film having excellent adhesion.

Here, Patent Document 1 using the in-line coating method of the water-based coating material has no description regarding heat setting.
Patent Documents 2 and 3 in which stretching and heat setting are performed after the solvent-based coating solution is dried did not suggest that the heat setting temperature is higher than the stretching temperature. For example, Patent Document 2 describes controlling the preheating temperature Tg to Tg + 30 ° C., the stretching temperature Tg to Tg + 20 ° C., and the heat fixing temperature Tg to Tg + 15 ° C., but the heat fixing temperature is higher than the stretching temperature. Was not suggested, and there was no description about improvement in adhesion. Patent Document 3 describes that the stretching temperature is controlled to Tg-30 ° C to Tg + 30 ° C and the heat setting temperature Tg-20 ° C to Tg ° C, but it is suggested that the heat setting temperature is higher than the stretching temperature. It wasn't.
Under such circumstances, the present inventors have conducted intensive studies to solve the above problems, and as a result, when using an in-line coating method using an aqueous coating material on a cyclic olefin polymer film, a stretching temperature is used. Higher and higher than the glass transition temperature Tg of the cyclic olefin polymer film, by carrying out heat setting to form a coating layer on the cyclic olefin film using an aqueous coating material. Moreover, it discovered that the manufacturing method of the laminated | multilayer film which can manufacture the laminated | multilayer film which is excellent in the adhesiveness between a cyclic olefin type film and a coating layer can be provided, and came to complete this invention.
Patent Document 4 discloses a surface coating material, a surface protective material, a packaging film, a hot stamping foil or a label film for interior products, a laminated member, an image receiving paper, a printer supply paper, or an opaque biaxially stretched polyester for magnetic recording cards. This is a document related to a film, and the content of the cycloolefin copolymer is too small to make use of optical properties such as excellent transparency of the cyclic olefin film. Furthermore, an opaque biaxially stretched polyester film obtained by the method described in Patent Document 4 rather than a laminated film obtained by forming a coating layer using a water-based coating material on a cyclic olefin film in the configuration of the present invention. Was inferior in adhesion between the base film and the coating layer, and inferior in moisture and heat resistance.

Specifically, the present invention and preferred embodiments of the present invention have the following configurations.
[1] A method for producing a laminated film having a base film and a coating layer laminated on at least one surface of the base film,
The main binder of the base film is a cyclic olefin polymer or a cyclic olefin copolymer,
An in-line coating step of applying an aqueous coating solution for forming a coating layer to an unstretched substrate film being conveyed;
A stretching process that stretches while conveying an unstretched base film while maintaining an inline state after the inline coating process;
After the stretching process, hold both ends of the base film so that the width is within the range of expansion or contraction within 10% at a heat setting temperature higher than the stretching temperature and higher than the glass transition temperature Tg of the base film. The manufacturing method of a laminated | multilayer film including the heat setting process which heat-processes, carrying out.
[2] In the method for producing a laminated film according to [1], the heat setting temperature is preferably higher than the glass transition temperature Tg of the base film and is Tg + 10 ° C. or lower.
[3] In the method for producing a laminated film according to [1] or [2], the wet coating amount of the aqueous coating solution for forming a coating layer in the in-line coating process is preferably 10 ml / m ² or less.
[4] In the method for producing a laminated film according to any one of [1] to [3], the glass transition temperature Tg (2) of the main binder of the coating layer is less than the glass transition temperature Tg of the base film. Thus, it is preferably 50 ° C. or lower.
[5] In the method for producing a laminated film according to any one of [1] to [4], the SP value of the coating layer is preferably 9 to 11 (cal / cm ³ ) ^1/2 .
[6] In the method for producing a laminated film according to any one of [1] to [5], the main binder of the coating layer is preferably a urethane polymer or an acrylic polymer.
[7] In the method for producing a laminated film according to any one of [1] to [6], the stretching temperature is preferably equal to or higher than the glass transition temperature Tg of the base film.
[8] A laminated film produced by the method for producing a laminated film according to any one of [1] to [7].
[9] A transparent conductive film having the laminated film according to [8].
[10] A retardation film having the laminated film according to [8].
[11] An organic electroluminescence device having the laminated film according to [8].

  ADVANTAGE OF THE INVENTION According to this invention, even when it is a case where a coating layer is formed on a cyclic olefin type film using a water-system coating material, the laminated | multilayer film which is excellent in the adhesiveness between a cyclic olefin type film and a coating layer can be manufactured. A method for producing a laminated film can be provided.

FIG. 1 is a cross-sectional view showing an example of the laminated film of the present invention.

  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.

[Production method of laminated film]
The method for producing a laminated film of the present invention is a method for producing a laminated film having a base film and a coating layer laminated on at least one surface of the base film,
The main binder of the base film is a cyclic olefin polymer or a cyclic olefin copolymer,
An in-line coating step of applying an aqueous coating solution for forming a coating layer to an unstretched substrate film being conveyed;
A stretching process that stretches while conveying an unstretched base film while maintaining an inline state after the inline coating process;
After the stretching process, hold both ends of the base film so that the width is within the range of expansion or contraction within 10% at a heat setting temperature higher than the stretching temperature and higher than the glass transition temperature Tg of the base film. And a heat setting step in which heat treatment is performed.
With such a configuration, according to the method for producing a laminated film of the present invention, even when a coating layer is formed on a cyclic olefin film using an aqueous coating material, the cyclic olefin film and the coating layer It is possible to produce a laminated film having excellent adhesion between the two. Although not bound by any theory, by stretching after the in-line coating process and further heat setting in a specific temperature range, the cyclic olefin-based film relaxes entropy, and the width is expanded or reduced within 10%. It is presumed that it is mixed with the coating layer adjacent in the film thickness direction. Therefore, the present inventor presumes that a laminated film having extremely excellent adhesion between the cyclic olefin film and the coating layer can be produced. However, since it is impossible or completely difficult to determine that a mixed layer is present at the present time, the laminated film is described by product-by-process claims.
In addition, the laminated film produced by the method for producing a laminated film of the present invention is excellent in adhesion between the initial cyclic olefin film and the coating layer, and further, the cyclic olefin film and the film after wet heat aging. It is preferable that the adhesiveness between the layers is also excellent.
Hereinafter, preferred embodiments of the present invention will be described.

<Base film>
In the method for producing a laminated film of the present invention, the main binder of the base film is a cyclic olefin polymer or a cyclic olefin copolymer.
The film in which the main binder is a cyclic olefin polymer or a cyclic olefin copolymer refers to a film containing more than 60% by mass of a cyclic olefin polymer or a cyclic olefin copolymer as a binder component. When the base film contains the cyclic olefin polymer or the cyclic olefin copolymer in excess of 60% by mass as the binder component, the transparency is excellent, the adhesion between the base film and the coating layer is excellent, and the heat and humidity resistance ( A laminated film having excellent adhesion between the base film and the coating layer after wet heat aging can be obtained. The higher the ratio of the cyclic olefin polymer or cyclic olefin copolymer of the binder component of the base film, the better. The base film preferably contains 80% by mass or more, more preferably 95% by mass or more, of a cyclic olefin polymer or a cyclic olefin copolymer as a binder component.
In the present invention, the cyclic olefin polymer may contain an organic group or may not contain an organic group. However, it is preferable from the viewpoint of adhesion between the cyclic olefin polymer layer and the coating layer. Examples of the organic group that the cyclic olefin polymer can contain include the following organic groups.
Examples of the organic group include a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, and a cyano group. These organic groups may be bonded via a linking group such as a methylene group. Good. In addition, a hydrocarbon group in which a divalent organic group having a polarity such as a carbonyl group, an ether group, a silyl ether group, a thioether group, or an imino group is bonded as a linking group can also be exemplified. Moreover, as said organic group, what was described in the paragraph 0037 of patent 5009512 can be illustrated.
Among them, a carboxy group, a carboxyalkyl group (the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 6 carbon atoms), a carboxyaryl group ( The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms.

  Preferred examples of norbornene resins (norbornene units) used as the raw material for the cyclic olefin polymer or cyclic olefin copolymer include saturated norbornene resin-A and saturated norbornene resin-B described below. Any of these base films in which the main binder is a saturated norbornene resin can be formed by the solution film forming method and the melt film forming method described later, but the base film in which the main binder is a saturated norbornene resin-A. Is more preferably formed by a melt film forming method, and the base film whose main binder is a saturated norbornene resin-B is more preferably formed by a melt and solution film forming method.

(Saturated norbornene resin-A)
As the saturated norbornene resin-A, (1) a ring-opening (co) polymer of a norbornene-based monomer is subjected to polymer modification such as maleic acid addition or cyclopentadiene addition as necessary, and then further hydrogenated. Obtained resin, (2) Resin obtained by addition polymerization of norbornene monomer, (3) Obtained by addition copolymerization of norbornene monomer and olefin monomer such as ethylene and α-olefin Examples thereof include resins. The polymerization method and the hydrogenation method can be performed by conventional methods.

  Examples of the norbornene-based monomer include norbornene and alkyl and / or alkylidene substituted products thereof (for example, 5-methyl-2-norbornene, 5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl- 2-norbornene, 5-ethylidene-2-norbornene, etc.), polar group substituents such as halogens thereof; dicyclopentadiene, 2,3-dihydrodicyclopentadiene, etc .; dimethanooctahydronaphthalene, alkyl and / or alkylidene thereof Substituents and polar group substituents such as halogen (for example, 6-methyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6- Ethyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octa Dronaphthalene, 6-ethylidene-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-chloro-1,4: 5,8-dimethano -1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-cyano-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a -Octahydronaphthalene, 6-pyridyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, 6-methoxycarbonyl-1,4: 5 8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene, etc.); adducts of cyclopentadiene and tetrahydroindene, etc .; 3-pentamers of cyclopentadiene (for example, 4, 9: 5,8-dimethano-3a, 4,4a, , 8,8a, 9,9a-octahydro-1H-benzoindene, 4,11: 5,10: 6,9-trimethano-3a, 4,4a, 5,5a, 6,9,9a, 10,10a, 11, 11a-dodecahydro-1H-cyclopentanthracene) and the like. These norbornene monomers may be used alone or in combination of two or more.

(Saturated norbornene resin-B)
Examples of the saturated norbornene resin-B include those represented by the following general formulas (1) to (3). Among these, those represented by the following general formula (1) are particularly preferable.

In general formulas (1) to (3), R ^{1 to} R ¹² each independently represent a hydrogen atom or a monovalent substituent (preferably an organic group), and at least one of them is a polar group. Is preferred. The mass average molecular weight of these saturated norbornene resins is usually preferably 5,000 to 1,000,000, more preferably 8,000 to 200,000.

  Examples of the substituent include those described in paragraph [0036] of Japanese Patent No. 5009512. Moreover, as said polar group, what was described in the paragraph [0037] of the patent 5009512 gazette can be illustrated.

Examples of the saturated norbornene resin include, for example, JP-A-60-168708, JP-A-62-252406, JP-A-62-2252407, JP-A-2-133413, JP-A-63-145324. Examples thereof include resins described in JP-A-63-264626, JP-A-1-240517, and JP-B-57-8815.
Among these resins, a hydrogenated polymer obtained by hydrogenating a ring-opening polymer of a norbornene monomer is particularly preferable.

  As a saturated norbornene resin, at least one tetracyclododecene derivative represented by the following general formula (5) is used alone, or a tetracyclododecene derivative and an unsaturated cyclic compound copolymerizable therewith are subjected to metathesis polymerization. A hydrogenated polymer obtained by hydrogenating a polymer obtained in this manner can also be used.

In General Formula (5), R ^{13 to} R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent (preferably an organic group), and at least one of these is preferably a polar group. Specific examples and preferred ranges of the substituents and polar groups herein are the same as those described for the general formulas (1) to (4).
In the tetracyclododecene derivative represented by the general formula (5), when at least one of R ^{13 to} R ¹⁶ is a polar group, a polarizing film excellent in adhesion to other materials, heat resistance, etc. Can be obtained. Further, the polar group is a group represented by — (CH ₂ ) _n COOR (where R is a hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 0 to 10). The resulting hydrogenated polymer (polarizing film substrate) is preferred because it has a high glass transition temperature. In particular, the polar substituent represented by — (CH ₂ ) _n COOR is preferably contained in one molecule of the tetracyclododecene derivative of the general formula (5) from the viewpoint of reducing the water absorption rate. In the above polar substituent, it is preferable in that the hygroscopicity of the obtained hydrogenated polymer decreases as the number of carbon atoms of the hydrocarbon group represented by R increases, but the balance with the glass transition temperature of the obtained hydrogenated polymer is good. From this point, the hydrocarbon group is preferably a linear alkyl group having 1 to 4 carbon atoms or a (poly) cyclic alkyl group having 5 or more carbon atoms, and particularly preferably a methyl group, an ethyl group, or a cyclohexyl group. .

Furthermore, the tetracyclododecene derivative of the general formula (5) in which a hydrocarbon group having 1 to 10 carbon atoms is bonded as a substituent to a carbon atom to which a group represented by — (CH ₂ ) _n COOR is bonded, This is preferable because the resulting hydrogenated polymer has low hygroscopicity. In particular, the tetracyclododecene derivative of the general formula (5) in which the substituent is a methyl group or an ethyl group is preferable in terms of easy synthesis. Specifically, 8-methyl-8-methoxycarbonyltetracyclo [4,4,0,1 ^2.5, 1 ^7.10] dodeca-3-ene are preferred. These tetracyclododecene derivatives and mixtures of unsaturated cyclic compounds copolymerizable therewith are described, for example, in JP-A-4-77520, page 4, upper right column, line 12 to page 6, lower right column, line 6. Metathesis polymerization and hydrogenation can be carried out by the prepared method.
These norbornene resins preferably have an intrinsic viscosity (η _inh ) measured at 30 ° C. in chloroform of 0.1 to 1.5 dl / g, more preferably 0.4 to 1.2 dl / g. g. The hydrogenation rate of the hydrogenated polymer is preferably 50% or more, more preferably 90% or more, more preferably 60 MHz, a value measured by ¹ H-NMR (nuclear magnetic resonance). Is 98% or more. The higher the hydrogenation rate, the more the saturated norbornene film obtained has better stability to heat and light. The gel content contained in the hydrogenated polymer is preferably 5% by mass or less, more preferably 1% by mass or less.

(Other ring-opening polymerizable cycloolefins)
In the present invention, other cycloolefins capable of ring-opening polymerization can be used in combination as raw materials for cyclic olefin polymers or cyclic olefin copolymers other than norbornene-based monomers. Specific examples of such cycloolefins include compounds having one reactive double bond such as cyclopentene, cyclooctene, and 5,6-dihydrodicyclopentadiene. The content of these ring-opening polymerizable cycloolefins is preferably 0 mol% to 50 mol%, more preferably 0.1 mol% to 30 mol%, relative to the norbornene-based monomer. , 0.3 mol% to 10 mol% is particularly preferable.

The cyclic olefin resin may be a cyclic olefin copolymer (cyclic olefin copolymer) containing an ethylene unit and a norbornene unit. Ethylene units, -CH ₂ CH ₂ - is a repeating unit represented by. A cyclic olefin copolymer is obtained by vinyl polymerization of the ethylene unit with the norbornene unit described above. The copolymer molar ratio of norbornene units and ethylene units is preferably 80:20 to 20:80, more preferably 80:20 to 50:50, and more preferably 80:20 to 60:40. preferable.

  In addition, 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 the norbornene unit. 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.

  The cyclic olefin-based resin includes an addition polymerization type and a ring-opening polymerization type, and any of them may be used. Examples of the ring-opening polymerization type cyclic olefin resin include, for example, WO2009 / 041377, WO2008 / 108199, WO2007 / 001020, WO2006 / 112304, JP2008-037932, WO2007 / 043573, WO2007 / 010830, Japanese Patent Nos. 5233280, WO2007 / 001020, JP2007-063356, JP2009-210756, JP2008-1558088, JP2001-356213, JP2004-212848, JP 2003-014901, JP 2000-219752, JP 2005-008698, WO 2007/13587, JP 2012-056322, JP 7-19762. JP, 2005-215333, JP 2006-235085, JP 2005-173072, JP 4292993, JP 2004-258188, JP 2003-136635, JP 2003. -236915, JP-A-10-130402, JP-A-9-263627, JP-A-4-361230, JP-A-4-36312, JP-A-4-170425, JP-A-3-223328 Ring-opening polymerization type cyclic olefin resin described in Japanese Patent Publication No. Gazette and the like.

  Examples of the addition polymerization type cyclic olefin-based resin include, for example, WO2009 / 139293, WO2006 / 0307077, Patent 4493660, JP2007-232874A, JP2007-009010A, WO2013 / 179817, WO2012 / 114608, WO2008 / 078812, JP-A-11-142645, JP-A-10-287713, JP-A-5220616, JP-A-11-142645, JP-A-10-258025, JP-A-2001-2001 No. 026682, JP-A-5-025337, JP-A-3-270433, and the like.

(Other additives)
Other additives can be added to the cyclic olefin resin 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 cyclic olefin-based resin is installed on the surface of various devices, it is preferable to include an ultraviolet absorber. As the ultraviolet absorber, a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, an acrylonitrile-based ultraviolet absorber, or the like can be used.

  Commercially available products can be used as the cyclic olefin film used as the base film, or the cyclic olefin polymer or cyclic olefin copolymer used as the main binder of the base film. As commercial products, ZEONOR 1420R (manufactured by Nippon Zeon Co., Ltd.), ARTON R-5000, ARTON D4540 (all manufactured by JSR Corporation), TOPAS 6013, TOPAS 6015, and TOPAS 6017 (all manufactured by Polyplastics Co., Ltd.) ) And the like.

(Glass transition temperature Tg of base film)
The glass transition temperature Tg of the base film is preferably 60 to 200 ° C, more preferably 100 to 180 ° C, and particularly preferably 130 to 180 ° C.
The preferable range of the glass transition temperature of the cyclic olefin polymer or cyclic olefin copolymer used as the main binder of the base film is the same as the preferable range of the glass transition temperature Tg of the base film.
The glass transition temperature Tg of the substrate film can be measured by, for example, differential scanning calorimetry (DSC). Specifically, the glass transition temperature Tg of the base film used in the examples of the present specification is a value determined according to JIS (Japan Industrial Standards) standard K-7121-1987 using TA Instruments 2920 type DSC. is there.

(Thickness of base film)
The thickness of the unstretched substrate film before in-line coating is preferably 40 to 200 μm, more preferably 40 to 160 μm, and still more preferably 60 to 100 μm.
As thickness of the base film after extending | stretching, 20-100 micrometers is preferable, 20-80 micrometers is more preferable, and 30-50 micrometers is further more preferable.

<Coating layer>
In the manufacturing method of the laminated film of this invention, a coating layer is formed using the aqueous coating liquid for coating layer formation.
In this specification, an aqueous coating material refers to a material that can be dissolved or dispersed in an aqueous coating solution.
In this specification, the aqueous coating liquid refers to a coating liquid containing water, and includes a coating liquid whose solvent is an aqueous solvent and a coating liquid whose dispersion medium is an aqueous dispersion medium.
Examples of the aqueous solvent and the aqueous dispersion medium include water and a mixture of water and a polar solvent. In the present invention, it is preferable to use water.

(Main binder for coating layer)
Examples of the main binder of the coating layer include resins selected from olefin polymers, acrylic polymers, modified silicone polymers, ester polymers, urethane polymers, styrene butadiene rubber, polyvinylidene chloride, and the like.
In the method for producing a laminated film of the present invention, from the viewpoint of adhesion, the main binder of the coating layer is preferably a urethane polymer or an acrylic polymer, and particularly preferably a urethane polymer.

  The olefin polymer that can be used in the present invention is a resin having a polyolefin such as polyethylene or polypropylene in the main chain skeleton. Specific examples of the main chain include ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester- (meth) acrylic acid copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate- ( (Meth) acrylic acid copolymer, ethylene-propylene- (meth) acrylic acid copolymer, ethylene-propylene- (meth) acrylic ester- (meth) acrylic acid copolymer, ethylene-maleic anhydride copolymer, Ethylene- (meth) acrylic acid ester-maleic anhydride copolymer, ethylene-butene-maleic anhydride and / or-(meth) acrylic acid copolymer, propylene-butene-maleic anhydride and / or-(meth) Examples thereof include acrylic acid copolymers, ethylene-vinyl chloride copolymers, and ethylene- (meth) acrylic acid copolymers. Commercially available olefin polymers include, for example, Arrow Base SE-1010, SE-1013N, SD-1010, TC-4010, TD-4010 (manufactured by Unitika Ltd.), Hitech S3148, S3121, S8512 ( As mentioned above, Toho Chemical Co., Ltd.), Chemipearl S-120, S-75N, V100, EV210H (manufactured by Mitsui Chemicals, Inc.) and the like can be mentioned. Among them, in the present invention, it is preferable to use Arrow Base SE-1013N, manufactured by Unitika Ltd.

  The acrylic polymer that can be used in the present invention is a polymer obtained by polymerizing acrylic monomers such as polymethyl methacrylate, polyethyl methacrylate, and polymethyl acrylate, and is obtained by copolymerizing acrylic acid, methacrylic acid, and the like as necessary. There may be. Examples of commercially available acrylic polymers include AS-563A (Dai Self Einchem Co., Ltd.), Jurimer ET410, Jurimer SEK301, Jurimer FC30 (Nihon Pure Chemicals Co., Ltd.), Bonlon PS001 (Mitsui Chemicals). Co., Ltd., water-dispersed acrylic), Epocros WS700 (manufactured by Nippon Shokubai Co., Ltd., oxazoline group-containing, water-soluble acrylic) and the like.

  Examples of modified silicone polymers that can be used in the present invention include composite resins of acrylic and silicone. Specific examples of commercially available modified silicone polymers include Ceranate WSA1060 and WSA1070 (both manufactured by DIC Corporation) and H7620, H7630 and H7650 (both manufactured by Asahi Kasei Chemicals Corporation).

  Examples of the ester polymer (polyester resin) that can be used in the present invention include polyesters such as polyethylene terephthalate (PET) and polyethylene-2,6-naphthalate (PEN). Commercially available polyester resins include Vylonal MD1400, MD1480, MD1245, MD1500 (manufactured by Toyobo Co., Ltd.), Plus Coat Z-221, Z-561, Z-730, RZ-142, Z-687 (corresponding chemistry) Kogyo Co., Ltd.).

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).
As the urethane-based polymer (polyurethane resin) that can be used in the present invention, carbonate-based, ether-based, and ester-based urethane polymers can be preferably used. preferable. Commercially available urethane-based polymers include Superflex 830, 460, 870, 420, 420NS (Polyurethane from Daiichi Kogyo Seiyaku Co., Ltd.), Hydran AP-40F, WLS-202, HW-140SF (Dainippon) Ink Chemical Industry Co., Ltd. polyurethane), Olester UD500, UD350 (Mitsui Chemicals Co., Ltd. polyurethane), Takelac W-615, W-6010, W-6020, W-6061, W-405, W-5030, W-5661, W-512A-6, W-635, WPB-6601 are mentioned, and self-crosslinking type WS-6021, WS-5000, WS-5100, WS-4000, WSA-5920, WF-764 ( Mitsui Takeda Chemical Co., Ltd.).

  Styrene butadiene rubber that can be used in the present invention includes styrene, butadiene, acrylonitrile, and methyl methacrylate. Examples of commercially available styrene butadiene rubbers include NIPOL LX415, NIPOL LX407, NIPOL V1004, NIPOL MH8101, and SX1105 (manufactured by Nippon Zeon Co., Ltd.).

  Known polyvinylidene chloride can be used as the polyvinylidene chloride that can be used in the present invention. Examples of commercially available polyvinylidene chloride include Saran Latex L509 (manufactured by Asahi Kasei Co., Ltd., vinylidene chloride binder).

  When the aqueous coating solution is an aqueous dispersion, the method for obtaining the aqueous dispersion is not particularly limited. For example, as exemplified in JP-A No. 2003-119328 and the like, a method of heating and stirring each component described above, preferably in a sealable container can be employed. According to this method, an aqueous dispersion can be satisfactorily obtained without substantially adding a non-volatile aqueous additive.

  The resin solid content concentration in the aqueous coating solution is not particularly limited. However, from the viewpoint of ease of coating, ease of adjusting the wet coating amount of the aqueous coating solution for forming the coating layer and the Dry film thickness of the coating layer, and the like. 1-60 mass% is preferable with respect to the coating liquid total mass, 2-50 mass% is more preferable, and 3-30 mass% is further more preferable.

In the production method of the laminated film of the present invention, the glass transition temperature Tg (2) of the main binder of the coating layer is preferably lower by 50 ° C. or more than the glass transition temperature Tg of the base film from the viewpoint of improving the adhesion. 50 to 200 ° C. is more preferable, and 70 to 150 ° C. is particularly preferable. The reason why the glass transition temperature Tg (2) of the main binder of the coating layer is lower by 50 ° C. or more than the glass transition temperature Tg of the base film is that the adhesion is enhanced, because the mixed layer is easily formed. Presumed.
The glass transition temperature Tg (2) of the coating layer can be measured by, for example, differential scanning calorimetry (DSC). Specifically, the glass transition temperature Tg (2) of the coating layer used in the examples of the present specification was determined in accordance with JIS (Japan Industrial Standards) K-7121-1987 using TA Instruments 2920 type DSC. Value.

Method for producing a laminated film of the present invention, SP (Solubility Parameter) value of the coating layer is preferably ^{8~13 (cal / cm 3) 1/2} , 9~13 (cal / cm 3) 1 / ² is more preferable, 9 to 12 (cal / cm ³ ) ^1/2 is particularly preferable, and 9 to 11 (cal / cm ³ ) ^1/2 is particularly preferable. Adhesiveness with a cyclic olefin polymer improves that SP value is 9-11 (cal / cm < ³ >) ^<1/2 >. As the main binder of the coating layer, urethane polymer (SP value is about 10.0 (cal / cm ³ ) ^1/2 ), acrylic polymer (SP value is about 9.5 (cal / cm ³ ) ^1/2 ) ) Is preferable from the viewpoint of excellent adhesion.

(Non-volatile aqueous additive)
In the present invention, the aqueous coating solution for forming a coating layer may contain a non-volatile aqueous agent such as a surfactant or an emulsifier in order to increase the productivity (that is, the film forming speed) in the in-line coating method. preferable. By selecting an appropriate non-volatile water-based auxiliary, productivity and various performances can be achieved more effectively.
Here, the nonvolatile aqueous auxiliary agent means a nonvolatile compound that contributes to the dispersion and stabilization of the resin. Non-volatile aqueous additives include cationic surfactants, anionic surfactants, nonionic (nonionic) surfactants, amphoteric surfactants, fluorosurfactants, reactive surfactants, water-soluble surfactants In addition to those generally used for emulsion polymerization, emulsifiers are also included. In particular, an anionic surfactant is preferable. As a commercially available anionic surfactant, for example, Lapisol A-90 (manufactured by NOF Corporation) can be preferably used.

  The amount of the non-volatile aqueous additive such as a surfactant is preferably 1 to 1000 ppm (parts per million), more preferably 5 to 500 ppm, particularly preferably based on the aqueous coating solution. 10 to 200 ppm.

<Method for producing unstretched base film>
The base film (unstretched base film) used in the present invention can be produced by the following method. When manufacturing a base film, first, it is preferable that the resin mixture for base film formation is dried in a drying process. A drying process is a process heated by drying a resin mixture, and the temperature of drying has more preferable 80-120 degreeC, More preferably, it is 90-120 degreeC, More preferably, it is 100-110 degreeC.

  Thereafter, the resin mixture is preferably put into a single-screw or twin-screw extruder and heated and melted there. In this case, the heating and melting temperature is preferably 220 ° C. or higher and 300 ° C. or lower, more preferably 240 to 290 ° C., and further preferably 250 to 280 ° C. The kneading atmosphere may be any of air, vacuum, and inert gas flow, but more preferably an inert gas flow that can suppress thermal degradation of the polymer. The melting time is preferably 1 to 30 minutes, more preferably 1 to 20 minutes, and further preferably 3 to 15 minutes. Thereafter, the molten resin mixture is preferably discharged from the die into a soft sheet.

  The resin mixture discharged from the die is preferably passed through a melt pipe, a gear pump, and a filter. It is also preferable to provide a static mixer in the melt pipe to promote mixing of the resin and additives.

The resin mixture discharged from the die is extruded onto a casting roll, cooled and solidified, and formed into a film. The film thus obtained becomes an unstretched base film.
The temperature of the casting roll is preferably Tg-20 to Tg ° C, more preferably Tg-10 to Tg ° C, and still more preferably Tg-10 to Tg-5 ° C. At this time, in order to improve the adhesion between the melt and the cooling drum and improve the flatness, it is also preferable to use an electrostatic application method, an air knife method, water coating on the cooling drum, or the like. Further, in order to efficiently perform cooling, cold air may be blown from above the cooling drum.

<Inline coat>
The manufacturing method of the laminated | multilayer film of this invention includes the in-line coating process of apply | coating the aqueous coating liquid for film layer formation with respect to the unstretched base film currently conveyed.
The in-line coating method is a manufacturing method in which a film is continuously formed without winding a film in a series of film forming processes such as a resin extrusion process, an in-line coating (application) process, and a stretching process. The in-line coating method is distinguished from an off-line coating method in which a film is wound in the middle of the film forming process and then separately applied.
In the inline coating method, a stretching process is provided after the inline coating (application) process. When a plurality of stretching processes are provided, the stretching process may be provided before the inline coating process. However, in the inline coating method, the stretching process is always provided once after the inline coating process. For example, a longitudinal stretching process may be provided after the inline coating process, followed by a lateral stretching process, or an inline coating process may be provided after the longitudinal stretching process, followed by a lateral stretching process. In addition, a transverse stretching process may be provided before the longitudinal stretching process, and each stretching process may be provided in a plurality of steps.

The coating layer is formed on the surface of the film by coating before or during the stretching process. When the inline coating process is provided in the process between the stretching processes, at least one stretching process is provided after the inline coating process.
The in-line coating process and the stretching process are performed in the order of in-line coating and longitudinal stretching, and in-line coating and transverse stretching.
When an in-line coating process is provided before stretching in the longitudinal and lateral directions, the in-line coating, longitudinal stretching, and transverse stretching may be performed sequentially in the order of in-line coating, transverse stretching, and longitudinal stretching. You may extend | stretch in two directions simultaneously after a process. It is also preferable to stretch in multiple stages.
In the present invention, it is preferable that the inline coating step and the stretching step are performed in the order of inline coating and transverse stretching.

It is preferable to apply an aqueous solution or an aqueous dispersion (latex) as an aqueous coating solution for forming a coating layer to the unstretched substrate film being conveyed. The coating method is not particularly limited, and known methods such as bar coater coating and slide coater coating can be used, and bar coater coating is preferred.
The area | region which apply | coats the aqueous | water-based coating liquid for film-layer formation with respect to an unstretched base film may be the whole unstretched base film, or a part in the base film surface. From the viewpoint of preventing the tenter clip from being contaminated by the coating liquid, the area where the aqueous coating liquid for forming the coating layer is applied to the unstretched base film is part of the surface of the base film. preferable. For example, an aqueous coating for forming a coating layer on the center width portion so that 5 to 20% of the both ends of the unstretched base film are uncoated portions and 40 to 90% of the center in the width direction are coating portions. It is preferable to apply a liquid.

In the production method of the laminated film of the present invention, the wet coating amount of the aqueous coating liquid for forming the coating layer in the in-line coating process is 10 ml / m ² or less, indicating that there is a temperature difference between the coated part and the uncoated part in the stretching zone. Is less likely to occur, and the occurrence of stretching unevenness can be suppressed, which is preferable from the viewpoint of improving adhesion. Wet coating amount of the aqueous coating liquid for coating layer formation in-line coating step is more preferably at 9 ml / m ² or less, and particularly preferably 1~8ml / m ^2.

  The coating layer is formed by applying a coating solution on a base film and then drying it. In the present invention, the coating layer is dried by heating in the stretching step or heat setting step without providing a drying step after in-line coating. May be performed. When the coating layer has a two-layer structure, it is preferable to dry after coating the second layer.

<Extension>
The manufacturing method of the laminated | multilayer film of this invention includes the extending | stretching process extended | stretched, conveying an unstretched base film, maintaining an inline state after an inline coating process.
Although there is no restriction | limiting in a extending | stretching direction, it is preferable to extend | stretch at least to a horizontal direction, and it is more preferable to extend | stretch only to a horizontal direction. In the present specification, the horizontal direction means a direction orthogonal to the film conveyance direction. Further, the vertical direction means the film transport direction.
The film may be sent to a longitudinal stretching machine and stretched longitudinally.
It is preferable that both ends are gripped by gripping members such as left and right clips of a transverse stretching machine such as a tenter and the sheet is stretched laterally while being conveyed to the winder side.

When performing transverse stretching, transverse stretching is preferably performed using a tenter. In the tenter, lateral stretching can be performed by expanding the gripping member in the width direction while conveying the heat treatment zone while gripping both ends of the base film with the gripping member.
In the production method of the laminated film of the present invention, the stretching temperature is preferably not less than the glass transition temperature Tg of the base film from the viewpoint of uneven thickness of the film. A preferred stretching temperature is Tg to Tg + 100 ° C., more preferably Tg to Tg + 10 ° C., further preferably Tg + 1 to Tg + 10 ° C., particularly preferably Tg + 2 to Tg + 7 ° C., and particularly preferably Tg + 3 to Tg + 5 ° C. The draw ratio is preferably 1.3 to 5.5 times, more preferably 1.5 to 3 times, and still more preferably 1.8 to 2.5 times.

  Prior to the stretching step, a base film preheating step may be provided. The preferable range of the preheating temperature is the same as the preferable range of the stretching temperature. Such preheating may be brought into contact with a heating roll, a radiant heat source (IR (infrared heater) heater, halogen heater, etc.) may be used, or hot air may be blown.

<Heat setting>
The method for producing a laminated film of the present invention includes a range of expansion or reduction within 10% in width at a heat setting temperature higher than the stretching temperature after the stretching step and higher than the glass transition temperature Tg of the base film. It includes a heat setting step in which heat treatment is performed while holding both ends of the base film.
The heat setting temperature is preferably 1 ° C. or more higher than the stretching temperature, more preferably 1 to 10 ° C. higher than the stretching temperature, and particularly preferably 2 to 5 ° C. higher than the stretching temperature.
In the method for producing a laminated film of the present invention, the heat setting temperature is preferably higher than the glass transition temperature Tg of the base film and is Tg + 10 ° C. or lower. The heat setting temperature is more preferably the glass transition temperature Tg + 1 ° C. or higher and Tg + 10 ° C. or lower of the base film, and particularly preferably Tg + 3 ° C. or higher and Tg + 8 ° C. or lower. When the heat setting temperature is Tg + 1 ° C. or higher, it is difficult to break during stretching, and it is easy to produce a laminated film. Moreover, adhesiveness can be improved more when heat setting temperature is Tg + 10 degrees C or less.
The purpose of the heat setting in the present invention is different from that of the polyester or polyamide film. In the in-line coating method using a polyester film or a polyamide film, heat setting is performed at a temperature higher than the crystallization temperature (for example, Tg + 150 ° C.), the crystallinity is increased, and film performance is improved. The cyclic olefin polymer or cyclic olefin copolymer used as the main binder of the base film of the laminated film of the present invention is preferably not heat-set at such a high temperature, and is heat-set in the range of Tg + 10 ° C. or less as described above. Is preferable from the viewpoint of further improving the adhesion.

In heat setting, heat treatment is performed while holding the both end portions of the base film so that the width is within a range of 10% (preferably within 5%, more preferably within 3%).
“Holding both ends of the base film” so that the width is within the range of expansion or reduction within 10% means that the gap between the gripping members at both ends of the base film is not actively changed. As long as it does not violate the purpose, a minute width variation caused by vibration of the stretching apparatus or the like is allowed.
In the present invention, the heat setting step may be performed continuously in-line after the stretching step, or the heat fixing step may be performed in a batch manner by fixing four sides after cutting off the film, for example, off-line. In this invention, it is preferable from a viewpoint of manufacturing cost to perform a heat setting process in-line continuously after an extending process. In particular, it is preferable to carry out in a state in which the gripping member is gripped in the tenter following the lateral stretching, and the spacing between the gripping members may be performed at the width at the end of the lateral stretching, further expanded, or reduced in width. Also good.

Subsequent to heat setting, heat relaxation treatment may be performed.
Lateral relaxation can be performed by reducing the width of the gripping member of the tenter. Further, the longitudinal relaxation can be performed by narrowing the interval between the gripping members adjacent to the tenter. This can be achieved by connecting adjacent gripping members in a pantograph shape and shrinking the pantograph. Moreover, after taking out from a tenter, it can also heat-process and relieve | moderate, conveying with low tension.

<Winding>
The laminated film after heat setting (preferably the laminated film coming out of the tenter) is trimmed at both ends gripped by the gripping member and subjected to knurling (embossing) at both ends, and then wound up. Is preferred. The preferable width of the laminated film after trimming is 0.8 to 10 m, more preferably 1 to 6 m, and still more preferably 1.5 to 4 m.
The thickness of the laminated film is preferably 30 to 300 μm, more preferably 40 to 280 μm, still more preferably 45 to 260 μm. Such adjustment of the thickness can be achieved by adjusting the discharge amount of the extruder or adjusting the film forming speed (adjusting the speed of the cooling roll, the stretching speed linked to this).

  It is preferable that the film for reproduction such as the trimmed film edge is collected and recycled as a resin mixture. The film for reproduction becomes a film raw material for the laminated film of the next lot, and the manufacturing process may be repeated sequentially by returning to each process described above.

[Laminated film]
The laminated film of the present invention is a laminated film produced by the laminated film production method.
As shown in FIG. 1, the present invention relates to a laminated film 3 including a base film 1 and a coating layer 2 laminated on at least one surface of the base film 1. The laminated film 3 of the present invention can be obtained by forming the coating layer 2 on the substrate film 1 by the method for producing a substrate film of the present invention.

  The coating layer is formed by applying an aqueous coating solution for forming a coating layer on the base film and stretching.

  The base film may contain a compound contained in the coating layer. Usually, that the base film contains a compound contained in the coating layer indicates that the laminated film is recycled and reused.

  A release layer may be further formed on the surface of the film layer of the laminated film. In order to physically and chemically protect the coating layer, a release layer is provided on the surface of the coating layer, and in use, the release layer is peeled off to expose the coating layer, and then another member is laminated. Can be made.

  Examples of the release layer include those in which a release agent layer such as silicone is applied to various plastic films to form a release agent layer, and a polypropylene film alone, which is used as a release sheet for ordinary pressure-sensitive adhesive sheets Can be used.

  Further, another functional layer may be provided on the surface of the coating layer of the laminated film. For example, functional layers such as a hard coat layer, an antireflection layer, an antifouling layer, an electric resistance layer, and a barrier layer can be laminated. Thereby, the laminated | multilayer film of this invention can be used for various uses.

(Coating layer)
A coating layer means the thing of the layer structure formed in the surface of a base film. The coating layer preferably functions as an easy-adhesion layer that adheres the base film and another functional layer.

  The dry film thickness of the coating layer is preferably 10 to 1000 nm. The dry film thickness of the coating layer is preferably 20 nm or more, more preferably 30 nm or more, and further preferably 50 nm or more. Further, the thickness of the coating layer is preferably 300 nm or less from the viewpoint of improving the adhesion, more preferably 250 nm or less, and further preferably 200 nm or less. The coating layer may have a structure of two or more layers, and in the case of a structure of two or more layers, the total thickness is preferably within the above range. By setting the thickness of the coating layer within the above range, it is possible to obtain a coating layer that has excellent adhesion and does not impair the functionality of the laminated film.

[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, polyvinyl pyrrolidone, starch and other polysaccharides, cellulose and derivatives thereof, polyethylene oxide, polyvinylamine, chitosan, polylysine, polyacrylic acid, polyalginic acid, polyhyaluronic acid, carboxycellulose. Etc. 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 silver halide photographic 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). As another development method, a technique of applying a thermal development method 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.

[Phase difference film]
The retardation film of the present invention has the laminated film of the present invention.
The laminated film of the present invention can be used as a retardation film for optical compensation of a liquid crystal display device. Specifically, a retardation film in which a laminated film is used as a support and an optically anisotropic layer is formed on the support is exemplified.
As the optically anisotropic layer, a known optically anisotropic layer can be used. For example, JP-A-2012-215704 and JP-A-2013-231955 include a case where a hard coat layer is laminated on a retardation film. Examples include an optically anisotropic layer and a hard coat layer described in the publication.

[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 present invention will be described more specifically with reference to the following 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 is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

[Materials Used in Examples and Comparative Examples]
The materials used in the examples and comparative examples are as follows.

<Main binder of base film>
(Cyclic olefin polymer or cyclic olefin copolymer)
・ Zeonor 1420R:
Made by Nippon Zeon Co., Ltd., cyclic olefin polymer (not containing organic group), Tg = 137 ° C.
・ ARTON R-5000:
JSR Co., Ltd., cyclic olefin polymer (containing methyl ester group), Tg = 137 ° C.
・ TOPAS 6013:
Polyplastic Co., Ltd., cyclic olefin copolymer (no organic group), Tg = 137 ° C.
・ TOPAS 6015:
Polyplastic Co., Ltd., cyclic olefin copolymer (no organic group), Tg = 158 ° C.
・ TOPAS 6017:
Polyplastic Co., Ltd., cyclic olefin copolymer (no organic group), Tg = 178 ° C.
The Tg of the resin was measured in accordance with JIS standard K-7121-1987 using a TA Instruments 2920 type DSC.

<Main binder of coating layer>
・ Water-dispersed urethane:
Olestar UD350 (manufactured by Mitsui Chemicals, polyether urethane, solid content 38% by mass, Tg (2) = 33 ° C., SP value = 10.5 (cal / cm ³ ) ^1/2 )
・ Water-dispersed olefin:
Arrow Base SE1010 (manufactured by Unitika Ltd., acid-modified olefin, solid content 20% by mass, Tg (2) = − 35 ° C., SP value = 8.5 (cal / cm ³ ) ^1/2 )
・ Water-dispersed acrylic:
Bonron PS001 (Mitsui Chemicals Co., Ltd., acrylic, solid content 50% by mass, Tg (2) = 23 ° C., SP value = 9.0 (cal / cm ³ ) ^1/2 )
・ Water-soluble acrylic:
Epocros WS700 (manufactured by Nippon Shokubai Co., Ltd., oxazoline group-containing acrylic, solid content 25% by mass, Tg (2) = 50 ° C., SP value = 9.5 (cal / cm ³ ) ^1/2 )
・ Water-dispersed polyester:
Byronal MD1500 (manufactured by Toyobo Co., Ltd., polyester, solid content 30% by mass, Tg (2) = 77 ° C., SP value = 11.3 (cal / cm ³ ) ^1/2 )
Water dispersion SBR (abbreviation for styrene butadiene rubber):
NIPOL SX1105 (manufactured by Zeon Corporation, styrene-butadiene copolymer, solid content 45% by mass, Tg (2) = 0 ° C., SP value = 8.7 (cal / cm ³ ) ^1/2 )
-Water-dispersed PVDC (polyvinylidene chloride):
Saran latex L509 (manufactured by Asahi Kasei Co., Ltd., vinylidene chloride binder, solid content 50 mass%, Tg (2) = − 39 ° C., SP value = 12.2 (cal / cm ³ ) ^1/2 )

Tg (2) of the main binder of the coating layer was measured in accordance with JIS (Japan Industrial Standards) standard K-7121-1987 using TA Instruments 2920 type DSC.
The SP value was determined according to the Okitsu method (Toshinao Okitsu, Journal of the Adhesion Society of Japan, vol. 29, No. 5, 204-211 (1993)). The conversion formula of (cal / cm ³ ) ^1/2 , which is a conventional unit of SP value, and (MPa) ^1/2 of the SI unit system is 1 (cal / cm ³ ) ^1/2 ≈2.05 (MPa ) ^1/2 .
In addition, the value of SP value as a mixture can be calculated | required from the mass ratio using a following formula.
SP value as a mixture = W1 · SP1 + W2 · SP2
(W1: mass ratio of mixture 1, W2: mass ratio of mixture 2, SP1: SP value of mixture 1, SP2: SP value of mixture 2)

[Example 1]
<Preparation of aqueous coating solution for forming coating layer>
A solid content concentration of 3% by mass was prepared by adding distilled water to the main binder of the coating layer described in Table 1 below.
Next, 0.01 mass% of surfactant (Lapisol A-90, manufactured by NOF Corporation, solid content: 80 mass%) is added to the prepared liquid with respect to the aqueous coating liquid for forming the coating layer. The aqueous coating solution for forming a coating layer used in Example 1 was prepared.

<Preparation of laminated film>
(Extrusion molding)
The cyclic olefin polymers listed in Table 1 below were dried at 100 ° C. for 2 hours or more, and melt extruded at 280 ° C. using a biaxial kneading extruder. At this time, a screen filter, a gear pump, and a leaf disk filter are arranged in this order between the extruder and the die, and these are connected by a melt pipe and extruded from a T die having a width of 1000 mm and a lip gap of 1 mm. The film was cast on a triple cast roll set to Tg-10 ° C. to obtain an unstretched base film having a width of 900 mm and a thickness of 80 μm.

(Inline coating, stretching, heat setting)
The unstretched substrate film being conveyed was subjected to an inline coating step, a stretching step, and a heat setting step by the following method to obtain a laminated film having a thickness of 40 μm.

(A) In-line coating On the unstretched substrate film being conveyed, 5 ml / m of the above-mentioned aqueous coating solution for forming the coating layer is applied to a portion having a central width of 800 mm so that both ends 50 mm are uncoated portions. The coating amount was ² using a bar coater.

(B) Transverse stretching The in-line state was maintained after the inline coating step, and the unstretched substrate film was stretched laterally under the following conditions while being conveyed using a tenter.
<Conditions>
Preheating temperature: 142 ° C
Stretching temperature: 142 ° C
Stretch ratio: 2.0 times

(C) Heat setting Subsequent to the stretching step, the stretched film is held at both ends with a tenter clip so that the width is constant (range of expansion or contraction within 3%). However, heat setting was performed by heat treatment under the following conditions.
Heat setting temperature: 143 ° C
Heat fixing time: 30 seconds Note that the preheating temperature, stretching temperature, and heat fixing temperature were measured at five points in the width direction using a radiation thermometer at the portion where the aqueous coating liquid for forming the coating layer was applied. The average value.

(Take-up)
After heat setting, both ends were trimmed by 150 mm and wound with a tension of 25 kg / m to obtain a film roll having a width of 1500 mm and a winding length of 2000 m.
The obtained film roll was used as the laminated film of Example 1.

<Evaluation>
(Dry film thickness of the coating layer)
The dry film thickness of the coating layer of the laminated film obtained in Example 1 was measured using a dot-type film thickness meter.
The obtained results are shown in Table 1 below.

(Initial adhesion: peel strength (base film / coating layer))
The laminated film of Example 1 was cut into a width of 100 mm and a length of 150 mm to prepare one sample piece. EVA (ethylene-vinyl acetate copolymer) sheet (EVA sheet manufactured by Hangzhou First PV Material Co., Ltd .: F806) cut to 100 mm width × 150 mm length on the coating layer side of this sample piece, 100 mm width × A PEN (polyethylene naphthalate) film (Teijin Limited, Teonex Q51) cut to a length of 150 mm was disposed in this order. Using a vacuum laminator (vacuum laminator PVL0505S manufactured by Nisshinbo Co., Ltd.), after evacuating at 120 ° C. for 5 minutes, pressurizing for 10 minutes, the 100 mm portion from one end of the sample piece is not bonded to the EVA sheet, An evaluation sample having an EVA sheet adhered to the remaining 50 mm portion was obtained.
After the obtained sample for evaluation was cut to a width of 15 mm, the EVA non-adhered portion on the PEN film side was bent at 180 degrees, and the laminated film side was sandwiched between the upper clip and Tensilon (made by ORIENTEC, RTC-1210A). Measure the peel strength between the base film and the coating layer by making a notch with the cutter at the interface between the base film and the coating layer of the laminated film while conducting a tensile test at a peeling angle of 180 ° and a pulling speed of 30 mm / min. did. The peel strength was measured in an environment of 25 ° C. and a relative humidity of 60%.
The obtained results are shown in Table 1 below.

(Adhesion after wet heat aging: peel strength (base film / coating layer))
The laminated film of Example 1 was subjected to a wet heat test at 120 ° C., 100% relative humidity, and 30 hours, then cut to a width of 100 mm × 150 mm to prepare one sample piece.
Thereafter, peel strength after wet heat aging between the base film and the coating layer was measured by the same method as described above.
The obtained results are shown in Table 1 below.

[Examples 2 to 8]
A laminated film of each example was produced in the same manner as in Example 1 except that the heat setting temperature was changed as shown in Table 1 below. Evaluation of the film of each obtained Example was performed similarly to Example 1. The obtained results are shown in Table 1 below.

[Examples 9 to 13]
A laminated film of each example was prepared in the same manner as in Example 1 except that the wet coating amount of the aqueous coating solution for forming the coating layer in in-line coating was changed as shown in Table 1 below. Evaluation of the film of each obtained Example was performed similarly to Example 1. The obtained results are shown in Table 1 below.

[Examples 14 to 18]
The aqueous coating solution for forming the coating layer was prepared by changing the solid content concentration of the aqueous coating solution for forming the coating layer prepared in Example 1 to the Dry film thickness of the coating layer shown in Table 1 below. A laminated film of each example of the dry film thickness of the coating layer described in Table 1 was prepared in the same manner as in Example 1 except that the obtained aqueous coating solution for forming the coating layer was changed. Evaluation of the film of each obtained Example was performed similarly to Example 1. The obtained results are shown in Table 1 below.

[Examples 19 to 24]
A coating layer forming aqueous coating solution was prepared by changing the main binder of the coating layer forming aqueous coating solution prepared in Example 1 as shown in Table 1 below. The laminated film of each Example was produced like Example 1 except having changed the aqueous coating liquid for film layer formation obtained. Evaluation of the film of each obtained Example was performed similarly to Example 1. The obtained results are shown in Table 1 below.

[Examples 25 to 28]
The laminated film of each Example was produced like Example 1 except having changed the main binder of the base film as described in Table 1 below. Evaluation of the film of each obtained Example was performed similarly to Example 1. The obtained results are shown in Table 1 below.

[Comparative Examples 1-5]
A laminated film of each comparative example was produced in the same manner as in Example 1 except that the preheating temperature, the stretching temperature, and the heat setting temperature in the stretching process were changed as shown in Table 2 below. The film of each comparative example obtained was evaluated in the same manner as in Example 1. The obtained results are shown in Table 2 below.

[Comparative Examples 6-7]
A laminated film of each comparative example was prepared in the same manner as in Example 1 except that the wet coating amount of the aqueous coating solution for forming the coating layer in in-line coating and the heat setting temperature were changed as shown in Table 2 below. . The film of each comparative example obtained was evaluated in the same manner as in Example 1. The obtained results are shown in Table 2 below.

[Comparative Examples 8 to 13]
A coating layer forming aqueous coating solution was prepared by changing the main binder of the coating layer forming aqueous coating solution prepared in Example 1 as shown in Table 2 below. A laminated film of each comparative example was produced in the same manner as in Example 1 except that the obtained aqueous coating solution for forming a coating layer and the heat setting temperature were changed as shown in Table 2 below. The film of each comparative example obtained was evaluated in the same manner as in Example 1. The obtained results are shown in Table 2 below.

[Comparative Example 14]
A laminated film of Comparative Example 14 was produced in the same manner as Example 1 except that heat treatment was performed at the free end at the temperature shown in Table 2 below instead of heat setting. The film of Comparative Example 14 obtained was evaluated in the same manner as in Example 1. The obtained results are shown in Table 2 below.

From Table 1 and Table 2, according to the method for producing a laminated film of the present invention, even when a coating layer is formed on a cyclic olefin film using a water-based coating material, the cyclic olefin film and the coating film are formed. It turned out that the laminated | multilayer film which is excellent in the adhesiveness between layers can be provided. In addition, the laminated | multilayer film of each Example was excellent also in the adhesiveness between the cyclic olefin-type film after a heat-and-heat aging and the coating layer.
On the other hand, from Comparative Examples 1 to 13, when the heat setting temperature is lower than the lower limit specified in the present invention, when a coating layer is formed on the cyclic olefin film using an aqueous coating material, the cyclic olefin film and the coating film are formed. It was found that the adhesion between the layers was poor.
From Comparative Example 14, when the heat treatment was carried out at the free end without holding the both ends of the base film so that the width would be within the range of expansion or reduction within 10%, It was found that when the coating layer was formed using an aqueous coating material, the adhesion between the cyclic olefin film and the coating layer was poor.
In addition, the effect that the wet coating amount of the aqueous coating liquid contributes to the improvement of the adhesion is shown by comparing the examples 9 to 13 showing the wet coating amount dependency with the examples 14 to 18 showing the film thickness dependency. It has been suggested that there is.

  ADVANTAGE OF THE INVENTION According to this invention, even when it is a case where a coating layer is formed on a cyclic olefin type film using a water-system coating material, the laminated | multilayer film which is excellent in the adhesiveness between a cyclic olefin type film and a coating layer can be provided. . Furthermore, according to the present invention, a laminated film having excellent adhesion between the cyclic olefin film and the coating layer even when the coating layer is formed on the cyclic olefin film using an aqueous coating material. Since it can be formed by an in-line coating method, it is easy to use for tenter stretching, is good for the environment, and can reduce the cost for manufacturing a laminated film. Therefore, the present invention has high industrial applicability.

1 base film 2 coating layer 3 laminated film

Claims (5)

A laminated film having a base film and a coating layer having an SP value of 8.5 to 12.2 laminated on at least one surface of the base film,
The main binder of the base film is a cyclic olefin polymer or a cyclic olefin copolymer,
While performing a tensile test at a peeling angle of 180 ° and a tensile speed of 30 mm / min, by cutting into the interface between the base film and the coating layer of the laminated film with a cutter, the environment is 25 ° C. and the relative humidity is 60%. The peel strength measured between the base film and the coating layer is 8 N / cm to 20 N / cm,
The dry thickness of the coating layer is 60 to 330 nm,
The main binder glass transition temperature Tg of the coating layer (2) is the glass transition temperature Tg of the substrate film, low or 50 ° C., layered fill beam. The base film and the coating layer of the laminated film were peel strength after 30 hours of wet heat aging at 120 ° C., relative humidity 100%, with a peeling angle of 180 ° and a tensile speed of 30 mm / min. The peel strength between the base film and the coating layer measured in an environment of 25 ° C. and a relative humidity of 60% is 6 N / cm to 18 N / cm by cutting the interface with a cutter. A laminated film according to 1. A transparent conductive film comprising the laminated film according to claim 1 . A retardation film comprising the laminated film according to claim 1 . The organic electroluminescent element which has a laminated | multilayer film of Claim 1 or 2 .

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