KR20210132004A - laminated film - Google Patents

Abstract

a first outer layer, an intermediate layer, and a second outer layer in this order, wherein the first outer layer comprises a polymer containing an alicyclic structure and is made of a resin A1 having a glass transition temperature of TgA1 (°C) and the second outer layer comprises a polymer containing an alicyclic structure, and consists of a resin A2 having a glass transition temperature of TgA2 (°C), and the intermediate layer is a polymer containing an alicyclic structure and a UV absorber. comprising, consisting of resin B having a glass transition temperature of TgB (°C), TgA1 and TgA2 are each independently 150°C or higher, (TgA1-TgB) and (TgA2-TgB) are each independently 0°C or higher 60° C. or less, the concentration of the ultraviolet absorber in the resin B is 5 wt% or more and 20 wt% or less, and the thickness of the first outer layer (TA1) and the thickness of the first outer layer (TB) of the intermediate layer (TB) The laminated|multilayer film whose ratio (TB/(TA1 + TA2)) with respect to the sum total of the thickness (TA2) of 2 outer layers is 0.1 or more and 0.35 or less.

Description

laminated film

This invention relates to laminated|multilayer film.

In recent years, the demand of the image display apparatus with a touch panel is increasing, and development of the transparent conductive film which is a member of a touch panel is advancing. As a transparent conductive film, the film in which the transparent conductive layer is laminated|stacked on the resin film which is a base material is disclosed (patent document 1, 2).

The image display apparatus can be used under light including ultraviolet rays, such as sunlight. In order to protect an image display apparatus from deterioration by an ultraviolet-ray, the resin film containing a ultraviolet absorber is used as a base film of a transparent conductive film, a polarizing plate protective film, etc. As a resin film, the laminated|multilayer film of the three-layer structure provided with the layer of resin containing a ultraviolet absorber as an intermediate|middle layer is disclosed (patent documents 3-5).

Japanese Laid-Open Patent Publication No. 2017-061069 International Publication No. 2014/136701 (Corresponding Publication: Specification of U.S. Patent Application Publication No. 2015/0378461) Japanese Laid-Open Patent Publication No. 2005-181615 Japanese Laid-Open Patent Publication No. 2018-161789 Japanese Laid-Open Patent Publication No. 2015-045845

In the laminated film provided with the layer of resin containing a ultraviolet absorber as an intermediate|middle layer, if there exists a dispersion|variation in the thickness of an intermediate|middle layer, the performance of ultraviolet absorption may also become non-uniform|heterogenous. In addition, laminated|multilayer film may be exposed to high temperature in the manufacturing process etc.. When a wrinkle arises in laminated|multilayer film by exposure to high temperature, the optical characteristic of the member or apparatus containing a laminated|multilayer film may not be maintained. In addition, there are cases in which such members or devices cannot be efficiently manufactured.

Therefore, in the intermediate|middle layer containing a ultraviolet absorber, the dispersion|variation in thickness is suppressed, and even if it exposes to high temperature, the laminated|multilayer film which wrinkles are hard to generate|occur|produce is calculated|required.

MEANS TO SOLVE THE PROBLEM This inventor earnestly studied in order to solve the said subject. As a result, in the laminated film including the first outer layer, the intermediate layer, and the second outer layer in this order, the glass transition temperature of each layer, the ratio of the thickness of each layer, and the concentration of the ultraviolet absorber in the intermediate layer are predetermined. By making it fall within the range, it found out that the said subject could be solved, and completed this invention.

That is, the present invention provides the following.

[1] comprising a first outer layer, an intermediate layer, and a second outer layer in this order,

The first outer layer comprises a polymer containing an alicyclic structure and consists of a resin A1 having a glass transition temperature of TgA1 (°C),

The second outer layer comprises a polymer containing an alicyclic structure and consists of a resin A2 having a glass transition temperature of TgA2 (°C),

The intermediate layer comprises a polymer containing an alicyclic structure and a UV absorber, and consists of a resin B having a glass transition temperature of TgB (°C),

TgA1 and TgA2 are each independently 150 ° C. or higher,

The difference between TgA1 and TgB (TgA1-TgB) and the difference between TgA2 and TgB (TgA2-TgB) are each independently 0°C or more and 60°C or less,

The concentration of the ultraviolet absorber in the resin B is 5 wt% or more and 20 wt% or less,

The ratio (TB/(TA1 + TA2)) of the thickness TB of the intermediate layer to the sum of the thickness TA1 of the first outer layer and the thickness TA2 of the second outer layer is 0.1 or more and 0.35 or less , laminated film.

[2] The melt mass flow rate of the resin A1 at 280°C and a load of 2.16 kg is RA1 (g/10 min),

The melt mass flow rate of the resin A2 at 280°C and a load of 2.16 kg is RA2 (g/10 min),

The melt mass flow rate at 280° C. and a load of 2.16 kg of the resin B is RB (g/10 min),

The laminated film according to [1], wherein the ratio of RB to RA1 (RB/RA1) and the ratio of RB to RA2 (RB/RA2) are each independently 3.5 or more and 15.0 or less.

[3] The laminated film according to [1] or [2], wherein the concentration of the ultraviolet absorbent in the resin A1 and the concentration of the ultraviolet absorber in the resin A2 are each independently 0% by weight or more and less than 5% by weight.

[4] Any one of [1] to [3], wherein the first outer layer is formed in direct contact with one surface of the intermediate layer, and the second outer layer is formed in direct contact with the other surface of the intermediate layer The laminated|multilayer film of Claim.

[5] The light transmittance at a wavelength of 320 nm or more and 380 nm or less is 1.0% or less, and the ultraviolet absorber included in the intermediate layer is at least one selected from the group consisting of a benzotriazole-based ultraviolet absorber and a triazine-based ultraviolet absorber. The laminated film according to any one of [1] to [4], comprising:

[6] The laminated film according to any one of [1] to [5], further comprising a transparent conductive layer.

[7] The laminated film according to [6], wherein the transparent conductive layer is a layer containing indium tin oxide, a layer containing silver nanowires, or a layer containing a copper mesh structure.

ADVANTAGE OF THE INVENTION According to this invention, the dispersion|variation in thickness is suppressed in the intermediate|middle layer containing a ultraviolet absorber, and even if it exposes to high temperature, it can provide the laminated|multilayer film which wrinkles do not generate|occur|produce easily.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically the laminated|multilayer film which concerns on one Embodiment of this invention.
It is sectional drawing which shows typically the laminated|multilayer film which concerns on another embodiment of this invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail by showing embodiments and examples. However, this invention is not limited to embodiment and the example shown below, In the range which does not deviate from the range which does not deviate from the Claim of this invention and its equivalent, it can change arbitrarily and can implement it.

In the following description, the "long" film refers to a film having a length of 5 times or more with respect to the width, and preferably has a length of 10 times or more, and specifically, the extent to which it is wound in a roll and stored or transported. A film with a length of There is no restriction|limiting in particular in the upper limit of the length of a film, For example, it can be made into 100,000 times or less with respect to a width|variety.

In the following description, the retardation Re in the in-plane direction of the layer is a value represented by Re = (nx - ny) x d, unless otherwise specified. Here, nx represents the refractive index of the direction which gives the largest refractive index as a direction (in-plane direction) perpendicular to the thickness direction of a layer. ny represents the refractive index of the direction orthogonal to the direction of nx as the said in-plane direction of a layer. d represents the thickness of the layer. The measurement wavelength is 590 nm, unless otherwise stated.

In the following description, the directions of elements are "parallel", "vertical" and "orthogonal", unless otherwise specified, within a range that does not impair the effects of the present invention, for example, ±3°, ±2° Alternatively, an error within the range of ±1° may be included.

In this specification, a single type of substance may be sufficient as "agent", and a multiple type of substance may be included.

[One. laminated film]

[1.1. Overview of Laminated Film]

A laminated film according to an embodiment of the present invention includes a first outer layer, an intermediate layer, and a second outer layer in this order. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically the laminated|multilayer film which concerns on one Embodiment of this invention. 1 , the laminated film 100 includes a first outer layer 110 , an intermediate layer 120 , and a second outer layer 130 in this order. The first outer layer 110 is formed in direct contact with one surface 120U of the intermediate layer 120 . The second outer layer 130 is formed in direct contact with the other surface 120D of the intermediate layer 120 . The first outer layer 110 has a thickness TA1 . The second outer layer 130 has a thickness TA2 . The intermediate layer 120 has a thickness TB.

The first outer layer 110 is made of a resin A1, and is formed using the resin A1 as a material.

The second outer layer 130 is made of resin A2, and is formed using resin A2 as a material.

The intermediate layer 120 is made of resin B, and is formed using the resin B as a material.

The ratio of the thickness TB of the intermediate layer 120 to the sum of the thickness TA1 of the first outer layer 110 and the thickness TA2 of the second outer layer 130 (TB/(TA1 + TA2)) Silver is usually 0.1 or more and 0.35 or less.

When the laminated|multilayer film 100 has the said structure, in the intermediate|middle layer 120, the dispersion|variation in thickness can be suppressed and it can be set as the laminated|multilayer film which wrinkles do not generate|occur|produce easily even if it exposes to high temperature.

[1.2. Resin A1]

Resin A1 forming the first outer layer contains a polymer containing an alicyclic structure, and has a glass transition temperature of TgA1 (°C).

The polymer containing an alicyclic structure is a polymer containing an alicyclic structure in a repeating unit. Hereinafter, the polymer containing an alicyclic structure is also called "a polymer containing an alicyclic structure."

The alicyclic structure-containing polymer is excellent in mechanical strength. Moreover, an alicyclic structure containing polymer is excellent in transparency, low water absorption, moisture resistance, dimensional stability, and light weight normally.

Examples of the alicyclic structure-containing polymer include a polymer obtainable by a polymerization reaction using a cyclic olefin as a monomer, or a hydride thereof. In addition, as said alicyclic structure-containing polymer, either a polymer containing an alicyclic structure in a main chain, and a polymer containing an alicyclic structure in a side chain can be used. Especially, it is preferable that an alicyclic structure containing polymer contains an alicyclic structure in a main chain. As an alicyclic structure, although a cycloalkane structure, a cycloalkene structure, etc. are mentioned, for example, From a viewpoint of thermal stability etc., a cycloalkane structure is preferable.

The number of carbon atoms contained in one alicyclic structure is preferably 4 or more, more preferably 5 or more, particularly preferably 6 or more, preferably 30 or less, more preferably 20 or more. or less, particularly preferably 15 or less. When the number of carbon atoms contained in one alicyclic structure is within the above range, mechanical strength, heat resistance, and moldability are highly balanced.

The proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer is preferably 30% by weight or more, more preferably 50% by weight or more, still more preferably 70% by weight or more, particularly preferably 90% by weight or more. More than that. Heat resistance can be improved by increasing the ratio of the repeating unit which has an alicyclic structure as mentioned above.

In addition, in the alicyclic structure-containing polymer, the remainder other than the repeating unit having an alicyclic structure is not particularly limited, and may be appropriately selected according to the intended use.

Examples of the alicyclic structure-containing polymer include (1) norbornene polymers, (2) monocyclic cyclic olefin polymers, (3) cyclic conjugated diene polymers, (4) vinyl alicyclic hydrocarbon polymers, and hydrides thereof can be heard Among these, a norbornene-type polymer and this hydride are preferable from a viewpoint of transparency and a moldability.

Examples of the norbornene-based polymer include a ring-opened polymer of a monomer having a norbornene structure and a hydride thereof; The addition polymer of the monomer which has a norbornene structure, and its hydride are mentioned. Further, examples of the ring-opened polymer of the monomer having a norbornene structure include a ring-opened homopolymer of one type of monomer having a norbornene structure, a ring-opened copolymer of two or more types of monomers having a norbornene structure, and norbornene A ring-opened copolymer of the monomer which has a nene structure, and the arbitrary monomer which can be copolymerized with this is mentioned. In addition, as an example of the addition polymer of the monomer which has a norbornene structure, the addition homopolymer of one type of monomer which has a norbornene structure, the addition copolymer of two or more types of monomers which have a norbornene structure, and norbornene The addition copolymer of the monomer which has a nene structure, and arbitrary monomers copolymerizable with this is mentioned. Among these, the hydride of the ring-opened polymer of the monomer which has a norbornene structure is especially suitable from a viewpoint of moldability, heat resistance, low moisture absorption, low moisture permeability, dimensional stability, and lightness.

Examples of the monomer having a norbornene structure include bicyclo[2.2.1]hepto-2-ene (common name: norbornene), tricyclo[4.3.0.1 ^2,5 ]deca-3,7- Diene (common name: dicyclopentadiene), 7,8-benzotricyclo[4.3.0.1 ^2,5 ]deca-3-ene (common name: methanotetrahydrofluorene), tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]dodeca-3-ene (common name: tetracyclododecene), and derivatives of these compounds (eg, those having a substituent on the ring). Here, as a substituent, an alkyl group, an alkylene group, and a polar group are mentioned, for example. These substituents may be the same or different, and two or more may couple|bond with the ring. The monomer which has a norbornene structure may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

The ring-opening polymer of the monomer having a norbornene structure can be produced, for example, by polymerizing or copolymerizing the monomer in the presence of a ring-opening polymerization catalyst.

The addition polymer of the monomer having a norbornene structure can be produced, for example, by polymerizing or copolymerizing the monomer in the presence of an addition polymerization catalyst.

The hydrides of the above-mentioned ring-opened polymer and addition polymer, for example, in the solution of the ring-opened polymer and the addition polymer, in the presence of a hydrogenation catalyst containing a transition metal such as nickel or palladium, carbon-carbon unsaturated bonds, preferably Preferably, it can be prepared by hydrogenating at least 90%.

The weight average molecular weight (Mw) of the alicyclic structure-containing polymer contained in the resin A1 is preferably 10,000 or more, more preferably 15,000 or more, still more preferably 20,000 or more, preferably 100,000 or less, more preferably It is 80,000 or less, More preferably, it is 50,000 or less. The alicyclic structure-containing polymer having such a weight average molecular weight is excellent in the balance of mechanical strength, moldability, and heat resistance.

The molecular weight distribution (Mw/Mn) of the alicyclic structure-containing polymer contained in the resin A1 is preferably 1.2 or more, more preferably 1.5 or more, particularly preferably 1.8 or more, preferably 3.5 or less, more preferably is 3.4 or less, particularly preferably 3.3 or less. When molecular weight distribution is more than the lower limit of the said range, productivity of an alicyclic structure containing polymer can be improved and manufacturing cost can be suppressed. Moreover, since the amount of a low molecular component becomes small when it is below an upper limit, stability of a 1st outer side layer can be improved.

The weight average molecular weight Mw and number average molecular weight Mn of the alicyclic structure-containing polymer contained in Resin A1 and the alicyclic structure-containing polymer contained in Resin A2, which will be described later, are determined by gel permeation chromatography (hereinafter referred to as cyclohexane) using cyclohexane as a solvent. , "GPC" is abbreviated). When resin does not melt|dissolve in cyclohexane, it can measure with the value of polystyrene conversion by GPC using toluene as a solvent.

As a resin containing an alicyclic structure containing polymer, since various goods are marketed, among them, what has a desired characteristic can be selected suitably and can be used. Examples of such commercially available products include product lines of product names "ZEONOR" (manufactured by Nippon Zeon Corporation), "Aton" (manufactured by JSR Corporation), "Apel" (manufactured by Mitsui Chemicals Corporation), and "TOPAS" (manufactured by TOPAS Advanced Polymers). can

The amount of the alicyclic structure-containing polymer in the resin A1 is preferably 80% by weight or more, more preferably 90% by weight or more, still more preferably 95% by weight or more, and is usually 100% by weight or less, and 98% by weight. It may be as follows. When the amount of the alicyclic structure-containing polymer in the resin A1 is equal to or more than the lower limit, the resin A1 can have characteristics that the alicyclic structure-containing polymer has.

Resin A1 may contain an alicyclic structure containing polymer individually by 1 type, and may contain it as a combination of 2 or more types of arbitrary ratios.

Resin A1 may contain arbitrary components other than an alicyclic structure containing polymer.

Examples of the optional component include polymers other than the alicyclic structure-containing polymer; inorganic particulates; Stabilizers, such as antioxidant, a heat stabilizer, a ultraviolet absorber, and a near-infrared absorber; resin modifiers such as lubricants and plasticizers; colorants such as dyes and pigments; and antistatic agents. As these arbitrary components, you may use individually by 1 type, and may use it combining two or more types by arbitrary ratios.

Resin A1 may contain the ultraviolet absorber as an arbitrary component. From the viewpoint of suppressing the ultraviolet absorber from bleed out from the first outer layer, the concentration of the ultraviolet absorber in the resin A1 is preferably less than 5% by weight, more preferably 3% by weight or less, still more preferably 1 It is weight % or less, normally 0 weight% or more, and 0 weight% may be sufficient.

Examples of the ultraviolet absorber that the resin A1 may contain include a ultraviolet absorber which will be described later as an example of the ultraviolet absorber contained in the resin B.

[Physical Properties of Resin A1]

The glass transition temperature TgA1 (°C) of the resin A1 is usually 150°C or higher, preferably 155°C or higher, more preferably 160°C or higher, preferably 185°C or lower, and more preferably 175°C or lower. When glass transition temperature TgA1 is more than the said lower limit, generation|occurrence|production of the wrinkles at the time of high temperature exposure in laminated|multilayer film can be suppressed.

The glass transition temperature TgA1 (° C.) of the resin A1, the glass transition temperature TgB (° C.) of the resin B described later, and the glass transition temperature TgA2 (° C.) of the resin A2 described below are based on JIS K7121, differential scanning calorimetry ( Hereinafter, also referred to as DSC).

The measurement of the glass transition temperature by DSC is a sample heated at 20°C/min from room temperature to 200°C, and then cooled to 40°C at 20°C/min, the temperature is increased from 40°C to 200°C at 10°C/min. It can be done under the condition that

The resin A1 has a melt mass flow rate RA1 at 280°C and a load of 2.16 kg, preferably 0.5 g/10 min or more, more preferably 1 g/10 min or more, still more preferably 3 g/10 min or more. and preferably 50 g/10 min or less, more preferably 30 g/10 min or less, still more preferably 20 g/10 min or less. By making melt mass flow rate RA1 of resin A1 into the said range, generation|occurrence|production of the wrinkles at the time of high temperature exposure in laminated|multilayer film can be suppressed more effectively. Melt mass flow rate RA1 of resin A1 is, for example, the method of adjusting the weight average molecular weight of resin A1, a lubricant; resin modifiers such as plasticizers; And it can adjust by the method of adjusting content of additives, such as a ultraviolet absorber.

Melt mass flow rates of Resin A1 and Resin A2 and Resin B described later (hereinafter, also referred to as melt mass flow rate MFR) are based on JIS K7210, using a melt indexer, at a temperature of 280°C and a load of 2.16 kg. conditions can be measured.

[1.3. Resin A2]

Resin A2 forming the second outer layer contains a polymer containing an alicyclic structure, and has a glass transition temperature of TgA2 (°C).

Examples of the alicyclic structure-containing polymer contained in the resin A2 include the same examples as the examples of the alicyclic structure-containing polymer contained in the resin A1. The alicyclic structure-containing polymer contained in the resin A2 can be appropriately selected from suitable examples of the alicyclic structure-containing polymer contained in the resin A1.

The weight average molecular weight of the alicyclic structure-containing polymer contained in Resin A2 can be within the same range as the suitable range of the weight average molecular weight (Mw) of the alicyclic structure-containing polymer contained in Resin A1.

The molecular weight distribution (Mw/Mn) of the alicyclic structure-containing polymer contained in the resin A2 can be within the same range as the suitable range of the molecular weight distribution of the alicyclic structure-containing polymer contained in the resin A1.

The amount of the alicyclic structure-containing polymer in the resin A2 can be within the same range as the suitable amount of the alicyclic structure-containing polymer in the resin A1.

Resin A2 may contain the alicyclic structure containing polymer individually by 1 type, and may contain it as a combination of 2 or more types of arbitrary ratios.

Resin A2 may contain arbitrary components other than an alicyclic structure containing polymer.

Examples of the optional component include the same examples as the optional component that may be included in the resin A1. As an arbitrary component, you may use individually by 1 type, and may use it combining two or more types by arbitrary ratios.

Resin A2 may contain the ultraviolet absorber as an arbitrary component. From the viewpoint of suppressing the ultraviolet absorber from bleed out from the second outer layer, the concentration of the ultraviolet absorber in the resin A2 is preferably less than 5% by weight, more preferably 3% by weight or less, still more preferably 1 It is weight % or less, normally 0 weight% or more, and 0 weight% may be sufficient.

Examples of the ultraviolet absorber that the resin A2 may contain include the ultraviolet absorbers described later as examples of the ultraviolet absorber that the resin B may contain.

[Physical Properties of Resin A2]

The glass transition temperature TgA2 (°C) of the resin A2 is usually 150°C or higher, preferably 155°C or higher, more preferably 160°C or higher, preferably 185°C or lower, and more preferably 175°C or lower. When glass transition temperature TgA2 is more than the said lower limit, generation|occurrence|production of the wrinkles at the time of high temperature exposure in laminated|multilayer film can be suppressed.

The resin A2 has a melt mass flow rate RA2 at 280°C and a load of 2.16 kg, preferably 0.5 g/10 min or more, more preferably 1 g/10 min or more, still more preferably 3 g/10 min or more. and preferably 50 g/10 min or less, more preferably 30 g/10 min or less, still more preferably 20 g/10 min or less. By making MFR of resin A2 into the said range, generation|occurrence|production of the wrinkles at the time of high temperature exposure in laminated|multilayer film can be suppressed more effectively. MFR of resin A2 can be adjusted by the method similar to the method illustrated as a method of adjusting MFR of resin A1.

Resin A2 may be resin different from resin A1. For example, the resin A2 may differ from the resin A1 in the type, weight average molecular weight, molecular weight distribution, content ratio, etc. of the resin A1 and the alicyclic structure-containing polymer, and the type, content ratio, etc. may be different Moreover, for example, resin A2 may differ from resin A1 in physical properties, such as a glass transition temperature and a melt mass flow rate.

However, it is preferable that resin A2 is resin similar to resin A1 from a viewpoint of simplifying manufacture of laminated|multilayer film and suppressing the curl of laminated|multilayer film.

[1.4. Resin B]

Resin B which forms an intermediate|middle layer contains the polymer containing an alicyclic structure, and a ultraviolet absorber, and has a glass transition temperature of TgB (degreeC).

Examples of the alicyclic structure-containing polymer contained in the resin B include the same examples as those of the alicyclic structure-containing polymer contained in the resin A1. The alicyclic structure-containing polymer contained in the resin B can be appropriately selected from suitable examples of the alicyclic structure-containing polymer contained in the resin A1.

The weight average molecular weight of the alicyclic structure-containing polymer contained in the resin B is preferably 10,000 or more, more preferably 15,000 or more, still more preferably 20,000 or more, preferably 100,000 or less, more preferably 80,000 or less, More preferably, it is 50,000 or less. The alicyclic structure-containing polymer having such a weight average molecular weight is excellent in the balance of mechanical strength, moldability, and heat resistance.

The molecular weight distribution (Mw/Mn) of the alicyclic structure-containing polymer contained in Resin B is preferably 1.2 or more, more preferably 1.5 or more, particularly preferably 1.8 or more, preferably 3.5 or less, more preferably is 3.4 or less, particularly preferably 3.3 or less. When molecular weight distribution is more than the lower limit of the said range, productivity of an alicyclic structure containing polymer can be improved and manufacturing cost can be suppressed. Moreover, since the quantity of a low molecular component becomes small by being below an upper limit, stability of an intermediate|middle layer can be improved.

The amount of the alicyclic structure-containing polymer in the resin B is preferably 80% by weight or more, more preferably 82% by weight or more, still more preferably 85% by weight or more, and is usually 95% by weight or less, and 90% by weight or more. It may be as follows.

Resin B may contain an alicyclic structure containing polymer individually by 1 type, and may contain it as a combination of 2 or more types of arbitrary ratios.

Examples of the ultraviolet absorber contained in the resin B include a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, an acrylonitrile-based ultraviolet absorber, a salicylate-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, Organic ultraviolet absorbers, such as an azomethine-type ultraviolet absorber, an indole-type ultraviolet absorber, a naphthalimide-type ultraviolet absorber, and a phthalocyanine-type ultraviolet absorber, are mentioned.

Especially, it is preferable that resin B contains 1 or more types chosen from the group which consists of a benzotriazole type ultraviolet absorber and a triazine type ultraviolet absorber.

A benzotriazole-type ultraviolet absorber contains a benzotriazole structure in a molecule|numerator.

Examples of the benzotriazole-based ultraviolet absorber include 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2 -(2H-benzotriazol-2-yl)-p-cresol, and 2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol are mentioned. .

As an example of the commercial item of a benzotriazole type|system|group ultraviolet absorber, the ADEKA company make "adekastave LA-31", "adekastave LA-32", and "adekastave LA-36" are mentioned.

A triazine-type ultraviolet absorber contains a triazine structure in a molecule|numerator. As the triazine-based ultraviolet absorber, a compound having a 1,3,5-triazine structure in its molecule is preferable.

Examples of the triazine-based UV absorber include 2,4,6-tris(2-hydroxy-3-methyl-4-hexyloxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl) -1,3,5-triazin-2-yl)-5-(2-(2-ethylhexanoyloxy)ethoxy)phenol, and 2,4-diphenyl-6-(2-hydroxy-4 -hexyloxyphenyl)-1,3,5-triazine is mentioned.

As an example of the commercial item of a triazine type|system|group ultraviolet absorber, "adekastave LA-F70" by ADEKA company, "adekastave LA-46", and BASF Japan company "Tinuvin 1577" are mentioned.

As another specific example of a ultraviolet absorber, the ultraviolet absorber of Unexamined-Japanese-Patent No. 2017-154401 is mentioned.

Resin B may contain the ultraviolet absorber individually by 1 type, and may contain 2 or more types by the combination of arbitrary ratios.

The content of the ultraviolet absorber in the resin B is usually 5% by weight or more, preferably 7% by weight or more, more preferably 8% by weight or more, and usually 20% by weight or less, preferably 15% by weight or less, more Preferably, it is 13% by weight or less.

When the content rate of the ultraviolet absorber in resin B is more than the said lower limit, the ultraviolet absorption performance in laminated|multilayer film improves. When the content rate of the ultraviolet absorber in resin B is below the said upper limit, coloring of resin B by a ultraviolet absorber is suppressed, and in resin B, a ultraviolet absorber can be disperse|distributed more favorably.

Resin B may contain arbitrary components other than an alicyclic structure containing polymer and a ultraviolet absorber.

Examples of the optional component include the same examples as the optional component that may be included in the resin A1. As an arbitrary component, you may use individually by 1 type, and may use it combining two or more types by arbitrary ratios.

[Physical Properties of Resin B]

The difference (TgA1-TgB) between the glass transition temperature TgA1 (°C) of the resin A1 and the glass transition temperature TgB (°C) of the resin B is usually 60°C or less, preferably 50°C or less, more preferably 48°C or less and is usually 0°C or higher.

The difference (TgA2-TgB) between the glass transition temperature TgA2 (°C) of the resin A2 and the glass transition temperature TgB (°C) of the resin B is usually 60°C or less, preferably 50°C or less, more preferably 48 °C or lower, and usually 0 °C or higher.

By having the glass transition temperature TgB of the resin B in the above relationship with the glass transition temperatures TgA1 and TgA2, the dimensional change of the laminated film after heating can be suppressed, and wrinkles are less likely to occur even when exposed to high temperatures. can do.

The ratio (RB/RA1) of the melt mass flow rate RB (g/10 min) of the resin B at 280° C. and a load of 2.16 kg to the melt mass flow rate RA1 is usually 3.5 or more, preferably 4.0 or more and is usually 15.0 or less, preferably 14.5 or less, and more preferably 14.0 or less. When ratio (RB/RA1) is more than the said lower limit, the dispersion|variation in the thickness in an intermediate|middle layer can be suppressed, and it can be set as the laminated|multilayer film which wrinkles do not generate|occur|produce easily even if it exposes to high temperature.

In addition, the ratio (RB/RA2) of the melt mass flow rate RB to the melt mass flow rate RA2 is usually 3.5 or more, preferably 4.0 or more, and usually 15.0 or less, preferably 14.5 or less, more preferably 14.0 or more. is below. When ratio (RB/RA2) is more than the said lower limit, the dispersion|variation in the thickness in an intermediate|middle layer can be suppressed, and it can be set as the laminated|multilayer film which wrinkles do not generate|occur|produce easily even if it exposes to high temperature.

The melt mass flow rate RB of resin B can be adjusted by the method similar to the method illustrated as a method of adjusting MFR of resin A1.

[1.5. Composition of laminated film, physical properties, etc.]

In the laminated film, the ratio (TB/(TA1 + TA2)) of the thickness (TB) of the intermediate layer to the sum of the thickness (TA1) of the first outer layer and the thickness (TA2) of the second outer layer is usually 0.1 or more, preferably 0.13 or more, more preferably 0.16 or more, and usually 0.35 or less, preferably 0.32 or less, more preferably 0.30 or less. By making the ratio (TB/(TA1 + TA2)) into the above range, it is possible to obtain a laminated film that does not easily generate wrinkles even when exposed to high temperatures.

Although the thickness of laminated|multilayer film can be suitably set according to the purpose of use of laminated|multilayer film, etc. and is not specifically limited, Preferably they are 30 micrometers or more and 150 micrometers or less.

Although the thickness of an intermediate|middle layer can be suitably set according to the quantity etc. of the ultraviolet absorber contained in an intermediate|middle layer, It is although it does not specifically limit, Preferably they are 5 micrometers or more and 35 micrometers or less.

As for the laminated|multilayer film, the light transmittance in wavelength 320 nm or more and 380 nm or less is 1.0 % or less normally, Preferably it is 0.8 % or less, Ideally, it is 0 %, and 0 % or more may be sufficient as it.

When the light transmittance in wavelength 320 nm or more of laminated|multilayer film 380 nm or less is below the said upper limit, laminated|multilayer film can cut an ultraviolet-ray more effectively.

The light transmittance at a wavelength of 320 nm or more and 380 nm or less can be measured using an ultraviolet-visible near-infrared spectrophotometer.

As for laminated|multilayer film, retardation Re in an in-plane direction becomes like this. Preferably it is 5 nm or less, More preferably, it is 3 nm or less, and is 0 nm or more normally. The retardation Re in the in-plane direction can be measured using a commercially available birefringent meter.

A haze of laminated|multilayer film becomes like this. Preferably it is 5 % or less, More preferably, it is 3 % or less, and is 0 % or more normally. The haze can be measured using a commercially available haze meter.

The laminated film has a total light transmittance of preferably 90% or more, more preferably 91% or more, and is usually 100% or less. The total light transmittance can be measured using a commercially available haze meter.

As for laminated|multilayer film, the absolute value of the dimensional change rate after heating at 145 degreeC for 60 minutes becomes like this. Preferably it is 0.1 % or less, More preferably, it is less than 0.1 %, and is 0 % or more normally.

The absolute value of the dimensional change rate after heating at 145 degreeC for 60 minutes can be calculated|required as the absolute value of the dimensional change rate of the laminated|multilayer film after heating with respect to the dimension of the laminated|multilayer film before a heating.

More specifically, the absolute value of the dimensional change rate can be calculated|required by the method demonstrated in an Example.

[1.6. Any layer that may be included in the laminated film]

The laminated|multilayer film may contain the layer arbitrary other than the said 1st outer side layer, an intermediate|middle layer, and a 2nd outer side layer. Examples of the optional layer include a transparent conductive layer, an adhesive layer, and an adhesive auxiliary layer.

[Transparent conductive layer]

The laminated film may contain the transparent conductive layer.

A conductive layer is formed in the outermost surface of laminated|multilayer film, for example.

2 : is sectional drawing which shows typically the laminated|multilayer film which concerns on another embodiment of this invention. The laminated film 200 includes a transparent conductive layer 240 , a first outer layer 210 , an intermediate layer 220 , and a second outer layer 230 in this order. The laminate 250 including the first outer layer 210 , the intermediate layer 220 , and the second outer layer 230 has the same configuration as the laminate film 100 , and the first outer layer 210 . , the middle layer 220 , and the second outer layer 230 have the same configuration as the first outer layer 110 , the intermediate layer 120 , and the second outer layer 130 , respectively, and thus description thereof will be omitted.

A transparent conductive layer is a layer which has electroconductivity.

A transparent conductive layer contains the electroconductive material which has a high transmittance|permeability in a visible light wavelength normally. Examples of the conductive material included in the transparent conductive layer include ITO (indium tin oxide), IZO (indium zinc oxide), ZnO (zinc oxide), IWO (indium tungsten oxide), ITiO (indium titanium oxide), AZO (aluminum zinc oxide) oxide), conductive metal oxides such as gallium zinc oxide (GZO), special zinc oxide (XZO), and indium gallium zinc oxide (IGZO); conductive nanowires such as carbon nanotubes and silver nanowires; metal nano ink; metal meshes such as copper mesh; conductive polymers; and the like. In addition, these electroconductive materials may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

The transparent conductive layer is preferably a layer containing indium tin oxide, a layer containing silver nanowires, or a layer containing a copper mesh structure.

The transparent conductive layer has a light transmittance in a wavelength range of 400 nm to 700 nm, preferably 85% or more, more preferably 90% or more, still more preferably 95% or more.

The transparent conductive layer may have a predetermined pattern.

In the present embodiment, the transparent conductive layer 240 is formed in direct contact with the first outer layer 210 so as to be outside the first outer layer 210 . However, in the laminated|multilayer film of another embodiment, the transparent conductive layer may be formed in direct contact with the 2nd outer side layer so that it may become outer than the 2nd outer side layer.

The laminated film according to another embodiment may include a first transparent conductive layer formed in direct contact with the first outer layer and a second transparent conductive layer formed in direct contact with the second outer layer.

In the laminated film according to another embodiment, an arbitrary layer may be formed between the first outer layer and the transparent conductive layer or between the second outer layer and the transparent conductive layer.

[1.7. Use of laminated film]

As a result of suppressing the dispersion|variation in the thickness in an intermediate|middle layer, the said laminated|multilayer film has few dispersion|variation in ultraviolet-ray absorption performance. Moreover, it is hard to generate|occur|produce wrinkles even if it is exposed to high temperature. Therefore, it can be used suitably as a polarizing plate protective film, retardation film, and the base film of a touch panel which can be manufactured under high temperature, for example.

[2. Manufacturing method of laminated film]

The said laminated|multilayer film can be manufactured by arbitrary methods. For example, each of the first outer layer, the intermediate layer, and the second outer layer may be separately produced by a known method such as a melt molding method or a solution casting method, and then laminated to manufacture, resin A1, You may manufacture by laminating|stacking resin B and resin A2 by the method of co-extrusion.

The said laminated|multilayer film can be manufactured as a long film.

When a laminated|multilayer film contains a transparent conductive layer, a transparent conductive layer can be formed by the method according to the electroconductive material contained in a transparent conductive layer. For example, a transparent conductive layer can be formed by methods, such as a vapor deposition method, a sputtering method, and a coating method.

Example

Hereinafter, the present invention will be specifically described with reference to Examples. However, this invention is not limited to the Example shown below, In the range which does not deviate from the Claim of this invention and its equivalent range, it can change arbitrarily and implement it.

In the following description, "%" and "part" indicating the quantity are based on weight, unless otherwise specified. In addition, the operation demonstrated below was performed on conditions of normal temperature and normal pressure, unless otherwise indicated.

[Assessment Methods]

(Glass Transition Temperature)

The glass transition temperature of the sample was measured by differential scanning calorimetry based on JIS K7121. The measurement was performed under conditions of heating the sample from room temperature to 200°C at 20°C/min and then cooled to 40°C at 20°C/min at 10°C/min from 40°C to 200°C.

(melt mass flow rate)

The melt mass flow rate of the sample was measured under conditions of a temperature of 280°C and a load of 2.16 kg using a melt indexer (“F-F01” manufactured by Toyo Seiki Corporation) based on JIS K7210.

(Measurement of molecular weight)

The weight average molecular weight and the number average molecular weight of the alicyclic structure-containing polymer were determined using a gel permeation chromatography (GPC) system HLC-8320 (manufactured by Tosoh Corporation) using an H-type column (manufactured by Tosoh Corporation), and cyclohexane was used as a solvent, and measured at 40°C, and calculated as a polyisoprene conversion value.

(Hydrogenation rate of polymer)

The hydrogenation rate of the polymer ^{was measured by 1} H-NMR.

(haze of laminated film)

From the width direction both ends of the laminated|multilayer film, and the width direction center part, the substantially square film piece whose one side is 50 mm was cut out in total of 3 sheets. The haze of each of the obtained three film pieces was measured using the haze meter ("NDH-2000" by Nippon Denshoku Industries Co., Ltd.). The average of the haze of the obtained film piece of 3 sheets was made into the value of the haze of laminated|multilayer film.

(Total light transmittance of laminated film)

From the width direction both ends of the laminated|multilayer film, and the width direction center part, the substantially square film piece whose one side is 50 mm was cut out in total of 3 sheets. The total light transmittance of each of the obtained three film pieces was measured using the haze meter ("NDH-2000" by Nippon Denshoku Industries Co., Ltd.). The average of the total light transmittance of the obtained three film pieces was made into the value of the total light transmittance of laminated|multilayer film.

(Retardation Re in the in-plane direction of the laminated film)

From the width direction both ends of the laminated|multilayer film, and the width direction center part, the substantially square film piece whose one side is 50 mm was cut out in total of 3 sheets. The retardation Re in the in-plane direction of each of the obtained three film pieces was measured with an automatic birefringent meter ("KOBLA-21ADH" by Oji Instruments Co., Ltd.). The measurement wavelength was 590 nm. The average of retardation Re of the obtained three film pieces was made into the value of retardation Re of laminated|multilayer film.

(ultraviolet light transmittance)

The ultraviolet transmittance of the film to be measured was measured in a wavelength range of 200 nm to 400 nm using an ultraviolet-visible near-infrared spectrophotometer ("V-550" manufactured by Nippon Kogyo Co., Ltd.). The ultraviolet transmittance (%) at wavelengths 320 nm, 340 nm, 360 nm, and 380 nm, and the maximum value (%) of the ultraviolet transmittance at wavelengths 320 nm to 380 nm were read from the obtained spectrum.

(TB/(TA1 + TA2) and variation in thickness in the intermediate layer)

The total thickness (micrometer) of the laminated|multilayer film in a certain location was measured using the commercially available contact-type thickness meter.

The laminated film was cut at the surface including the thickness direction, the cross section was observed with an optical microscope, and the total thickness of the intermediate layer was calculated as the sum of the thickness of the first outer layer and the thickness of the second outer layer at the location where the total thickness was measured. The ratio (TB/(TA1 + TA2)) was calculated. The thickness (TB) (micrometer) of an intermediate|middle layer was calculated|required from the total thickness of laminated|multilayer film, and ratio (TB/(TA1 + TA2)).

The above measurements were performed at 10 locations at 50 mm intervals in the width direction (direction perpendicular to the conveyance direction in the production of the laminated film) and 10 locations at 50 mm intervals in the longitudinal direction (the conveying direction in the production of the laminated film). , was carried out in a total of 20 places. However, the range of 50 mm from the edge part in the width direction of laminated|multilayer film was excluded from the measurement location.

The arithmetic mean value of the ratio (TB/(TA1 + TA2)) measured in 20 places was made into the value of the ratio (TB/(TA1 + TA2)) of the laminated|multilayer film.

_{Further, from the arithmetic mean value TB ave} (μm), the minimum value TB _min (μm), and the maximum value TB _max (μm) of the thickness of the intermediate layer measured at 20 places, d1 and d2 are obtained by the following formulas did. d1 and d2 were compared, and when the values of d1 and d2 were the same, when the values were different from each other, the larger value was taken as the variation D (μm) in the thickness of the intermediate layer in the laminated film.

d1 (μm) = TB _ave - TB _min

d2(μm) = TB _max - TB _ave

(Dimensional stability and wrinkle suppression)

From the width direction both ends of the laminated|multilayer film, and the width direction center part, the film piece of 100 mm of one side was cut out in a total of three substantially square film pieces. When cutting out, each side of a film piece was made to become parallel to the width direction or conveyance direction of laminated|multilayer film.

Three film pieces were left to cool after heating at 145 degreeC for 60 minutes. The three film pieces after heat standing to cool were visually observed, and the following criteria evaluated the wrinkle suppression at the time of high temperature exposure.

Good: There is no wrinkle in any of the three film pieces.

Defect: In any one of the three film pieces, there is a wrinkle.

For each of the three film pieces after heating and cooling, the dimension X (mm) of each side (the side in the width direction and the side in the direction parallel to the conveyance direction) is measured, and heated according to the following formula _{The absolute value |R L} |(%) of the dimensional change rate with respect to the previous dimension (100 mm) was calculated|required.

|R _L |(%) = |X - 100|/100 × 100

_{Furthermore, the arithmetic mean value Ave (%) of the absolute value |R L} | (%) of the dimensional change rate obtained with respect to each side of the three film pieces is calculated|required, and the dimensional stability of the laminated|multilayer film at the time of high temperature exposure is calculated|required by the following reference|standard was evaluated. The dimensional stability of the laminated|multilayer film at the time of high temperature exposure is so high that Ave is small.

A: Ave < 0.1%

B: 0.1% ≤ Ave < 0.2%

C: 0.2% ≤ Ave

[Preparation Example 1: Preparation of Polymer C1 containing an alicyclic structure]

tricyclo[4.3.0.1 ^2,5 ]deca-3,7-diene (dicyclopentadiene, hereinafter appropriately abbreviated as "DCP") and 7,8-benzotricyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]deca-3-ene (methanotetrahydrofluorene, hereinafter appropriately abbreviated as "MTF") was mixed at a weight ratio of 87/13. This mixture was subjected to ring-opening polymerization by the method described in Japanese Patent No. 6256353 [Example 1], followed by hydrogenation to obtain a DCP/MTF ring-opening polymer hydride, polymer C1.

As a result of calculating the copolymerization ratio of each norbornene-based monomer in the obtained polymer C1 by gas chromatography analysis from the composition of the norbornene-based monomer remaining in the solution after polymerization, DCP/MTF = 87/13, approximately Equivalent to the input composition.

Moreover, the weight average molecular weight (Mw) of this polymer C1 was 38,000, molecular weight distribution (Mw/Mn; Mn is a number average molecular weight) 2.2, the hydrogenation rate was 99.9 %, and glass transition temperature Tg was 125 degreeC.

[Preparation Example 2: Preparation of Polymer C2 containing an alicyclic structure]

DCP and MTF were mixed in a weight ratio of 85/15. This mixture was subjected to ring-opening polymerization by the known method, followed by hydrogenation, to obtain a polymer C2, which is a DCP/MTF ring-opened polymer hydride.

As a result of calculating the copolymerization ratio of each norbornene-based monomer in the obtained polymer C2 by gas chromatography analysis from the composition of the norbornene-based monomer remaining in the solution after polymerization, DCP/MTF = 85/15, approximately input It was equivalent to the composition.

Moreover, the weight average molecular weight (Mw) of this polymer C2 was 33,000, molecular weight distribution (Mw/Mn) was 2.1, the hydrogenation rate was 99.9 %, and glass transition temperature Tg was 135 degreeC.

[Production Example 3: Preparation of Polymer C3 containing an alicyclic structure]

DCP, MTF, and tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] (hereinafter referred to tetracyclododecene, hereinafter suitably "TCD".) Dodeca-3-en the weight ratio of 5/70/25 mixed with This mixture was subjected to ring-opening polymerization by the known method, followed by hydrogenation to obtain a polymer C3 which is a DCP/MTF/TCD ring-opened polymer hydride.

As a result of calculating the copolymerization ratio of each norbornene-type monomer in the obtained polymer C3 by gas chromatography analysis from the composition of the norbornene-type monomer remaining in the solution after polymerization, DCP/MTF/TCD=5/70/25 , which was approximately equivalent to the input composition. Moreover, the weight average molecular weight (Mw) of this polymer C3 was 35,000, molecular weight distribution (Mw/Mn) was 2.1, the hydrogenation rate was 99.9 %, and glass transition temperature Tg was 162 degreeC.

[Example 1]

(Preparation of Resin B)

91 parts of polymer C1 and 9 parts of ultraviolet absorbers were mixed with the twin screw extruder, and resin B1 was obtained. As a ultraviolet absorber, "LA-31" by ADEKA which contains a benzotriazole structure in a molecule|numerator was used.

(Production of laminated film)

A co-extrusion film forming machine capable of producing a laminated film of two types and three layers having a feed block and a single-layer die connected thereto was prepared. The first outer layer, the intermediate layer, and the second outer layer are discharged from the single-layer die by supplying a molten resin at 280°C as a material for each layer to the feed block so as to be discharged in the form of a film having the second outer layer in this order, Extrusion molded. As materials for the first outer layer and the second outer layer, resin A1 and polymer C3 as resin A2 were supplied. As a material for the intermediate layer, resin B1 was supplied.

The co-extruded film-like resin was cast on a cooling roll temperature-controlled to 100°C, and passed through another cooling roll temperature-regulated to 50°C to cool. Thereby, a long laminated film having a width of 600 mm was obtained. The laminated film has a configuration of two types and three layers (first outer layer made of polymer C3/middle layer made of resin B1/second outer layer made of polymer C3).

About the obtained laminated|multilayer film, the said evaluation method evaluated.

[Example 2]

Except having changed the following matters, it carried out similarly to Example 1, the laminated|multilayer film was obtained and evaluated.

-In the production of resin B, 84 parts of polymer C2 was used instead of 91 parts of polymer C1, and "LA-F70" manufactured by ADEKA was used instead of 9 parts of "LA-31" manufactured by ADEKA as a UV absorber. 16 parts of was used to prepare Resin B2. "LA-F70" contains a 1,3,5-triazine structure in a molecule|numerator.

- Production of the laminated film WHEREIN: Instead of resin B1, resin B2 was supplied, and the conditions of coextrusion were adjusted so that each layer might become the thickness shown in a table|surface.

The laminated film has a configuration of two types and three layers (first outer layer made of polymer C3/middle layer made of resin B2/second outer layer made of polymer C3).

[Example 3]

Except having changed the following matters, it carried out similarly to Example 1, the laminated|multilayer film was obtained and evaluated.

In the production of Resin B, 88 parts of Polymer C3 was used instead of 91 parts of Polymer C1, and the amount of "LA-31" manufactured by ADEKA as a UV absorber was changed from 9 parts to 12 parts, and Resin B3 was prepared.

- In manufacture of a laminated|multilayer film, resin B3 was supplied instead of resin B1, and the conditions of coextrusion were adjusted so that each layer might become the thickness shown in a table|surface.

The laminated film has a configuration of two types and three layers (first outer layer made of polymer C3/middle layer made of resin B3/second outer layer made of polymer C3).

[Comparative Example 1]

Except having changed the following matters, it carried out similarly to Example 1, the laminated|multilayer film was obtained and evaluated.

- Production of the laminated film WHEREIN: Instead of the polymer C3, the polymer C1 was supplied, and the conditions of coextrusion were adjusted so that each layer might become the thickness shown in a table|surface.

The laminated film has a configuration of two types of three layers (the first outer layer made of polymer C1/the middle layer made of resin B1/the second outer layer made of polymer C1).

[Comparative Example 2]

Except having changed the following matters, it carried out similarly to Example 1, the laminated|multilayer film was obtained and evaluated.

- Production of the laminated film WHEREIN: The conditions of coextrusion were adjusted so that each layer might become the thickness shown in a table|surface.

The laminated film has a configuration of two types and three layers (first outer layer made of polymer C3/middle layer made of resin B1/second outer layer made of polymer C3).

[Comparative Example 3]

Except having changed the following matters, it carried out similarly to Example 1, the laminated|multilayer film was obtained and evaluated.

- Production of Resin B WHEREIN: As a ultraviolet absorber, instead of "LA-31" by ADEKA, "LA-F70" by ADEKA was used, and Resin B4 was manufactured.

- Production of the laminated film WHEREIN: Instead of resin B1, resin B4 was supplied, and the conditions of coextrusion were adjusted so that each layer might become the thickness shown in a table|surface.

The laminated film has a configuration of two types and three layers (first outer layer made of polymer C3/middle layer made of resin B4/second outer layer made of polymer C3).

[Comparative Example 4]

Except having changed the following matters, it carried out similarly to Example 1, the laminated|multilayer film was obtained and evaluated.

-In the production of resin B, 84 parts of polymer C2 was used instead of 91 parts of polymer C1, and "LA-F70" manufactured by ADEKA was used instead of 9 parts of "LA-31" manufactured by ADEKA as a UV absorber. 16 parts of was used to prepare Resin B2.

- In the manufacture of a laminated film, the resin B2 was supplied instead of the resin B1, and the polymer C1 was supplied instead of the polymer C3, and the conditions of coextrusion were adjusted so that each layer might have the thickness shown in a table|surface.

The laminated film has a configuration of two types and three layers (first outer layer made of polymer C1/middle layer made of resin B2/second outer layer made of polymer C1).

[Comparative Example 5]

Except having changed the following matters, it carried out similarly to Example 1, the laminated|multilayer film was obtained and evaluated.

- In the production of resin B, the amount of polymer C1 was changed from 91 parts to 76 parts, and the amount of "LA-31" manufactured by ADEKA as a UV absorber was changed from 9 parts to 24 parts, to prepare Resin B5 .

- Production of the laminated film WHEREIN: Instead of resin B1, resin B5 was supplied, and the conditions of coextrusion were adjusted so that each layer might become the thickness shown in a table|surface.

The laminated film has a configuration of two types of three layers (the first outer layer made of polymer C3/the middle layer made of resin B5/the second outer layer made of polymer C3).

[Comparative Example 6]

Except having changed the following matters, it carried out similarly to Example 1, the laminated|multilayer film was obtained and evaluated.

-In the production of resin B, 78 parts of polymer C2 was used instead of 91 parts of polymer C1, and "LA-F70" manufactured by ADEKA was replaced with 9 parts of "LA-31" manufactured by ADEKA as a UV absorber. 22 parts of was used to prepare Resin B6.

- Production of the laminated film WHEREIN: Instead of resin B1, resin B6 was supplied, and the conditions of coextrusion were adjusted so that each layer might become the thickness shown in a table|surface.

The laminated film has a configuration of two types and three layers (first outer layer made of polymer C3/middle layer made of resin B6/second outer layer made of polymer C3).

The structure and evaluation result of laminated|multilayer film are shown to the following table|surface.

The abbreviation in the following table|surface shows the following meaning.

UVA: UV absorber

Benzotriazole type: "LA-31" manufactured by ADEKA

Triazine series: "LA-F70" manufactured by ADEKA

TB: thickness of the intermediate layer

TA1 + TA2: the sum of the thickness TA1 of the first outer layer and the thickness TA2 of the second outer layer

RB: melt mass flow rate of resin B

TgB: glass transition temperature of resin B

TgA: Glass transition temperature of Resin A1 and Resin A2

RA: melt mass flow rate of Resin A1 and Resin A2

C1: Polymer C1 prepared in Preparation Example 1

C2: Polymer C2 prepared in Preparation Example 2

C3: Polymer C3 prepared in Preparation Example 3

Maximum value of ultraviolet transmittance: Maximum value of ultraviolet transmittance at a wavelength of 320 nm or more and 380 nm or less

From the above result, the following can be seen.

In the laminated|multilayer film which concern on Examples 1-3, the dispersion|variation in the thickness in an intermediate|middle layer is small, and after being exposed to the high temperature of 145 degreeC, it turns out that generation|occurrence|production of a wrinkle is suppressed.

On the other hand, it turns out that wrinkle generation is not suppressed in the laminated|multilayer film which concern on Comparative Examples 1-6.

In detail, in the laminated|multilayer film which concern on Comparative Examples 5 and 6, the density|concentration of the ultraviolet absorber in resin B is more than 20 weight%, wrinkle generation is not suppressed, and dimensional stability is inferior to an Example.

In the laminated films according to Comparative Examples 1 and 4, the first outer layer and the second outer layer are formed from a resin having a glass transition temperature of less than 150°C, and wrinkle generation is not suppressed.

As for the laminated|multilayer film which concerns on the comparative example 5, TgA-TgB is higher than 60 degreeC, wrinkle generation is not suppressed, and dimensional stability is inferior to an Example.

In the laminated films according to Comparative Examples 1 and 2, the ratio (TB/(TA1 + TA2)) was larger than 0.35, the thickness variation in the intermediate layer was large, and the generation of wrinkles was not suppressed.

In the laminated film according to Comparative Example 3, the ratio (TB/(TA1 + TA2)) was less than 0.1, and the generation of wrinkles was not suppressed.

RB/RA of the laminated|multilayer film which concerns on Comparative Example 6 is larger than 15.0, the dispersion|variation in thickness in an intermediate|middle layer is large, wrinkle generation is not suppressed, and dimensional stability is inferior to an Example.

The above result is a result which shows that even if the laminated|multilayer film of this invention is suppressed in thickness dispersion|fluctuation in the intermediate|middle layer containing a ultraviolet absorber, and is exposed to high temperature, it is a result which shows that a wrinkle is hard to generate|occur|produce.

100: laminated film
110: first outer layer
120: middle layer
130: second outer layer
120D: Cotton
120U: Cotton
200: laminated film
210: first outer layer
220: middle layer
230: second outer layer
240: transparent conductive layer
250: laminate

Claims (7)

a first outer layer, a middle layer, and a second outer layer in this order;
The first outer layer comprises a polymer containing an alicyclic structure and consists of a resin A1 having a glass transition temperature of TgA1 (°C),
The second outer layer comprises a polymer containing an alicyclic structure and consists of a resin A2 having a glass transition temperature of TgA2 (°C),
The intermediate layer comprises a polymer containing an alicyclic structure and a UV absorber, and consists of a resin B having a glass transition temperature of TgB (°C),
TgA1 and TgA2 are each independently 150 ° C. or higher,
The difference between TgA1 and TgB (TgA1-TgB) and the difference between TgA2 and TgB (TgA2-TgB) are each independently 0°C or more and 60°C or less,
The concentration of the ultraviolet absorber in the resin B is 5 wt% or more and 20 wt% or less,
The ratio (TB/(TA1 + TA2)) of the thickness TB of the intermediate layer to the sum of the thickness TA1 of the first outer layer and the thickness TA2 of the second outer layer is 0.1 or more and 0.35 or less , laminated film. According to claim 1,
The melt mass flow rate at 280° C. and a load of 2.16 kg of the resin A1 is RA1 (g/10 min),
The melt mass flow rate of the resin A2 at 280°C and a load of 2.16 kg is RA2 (g/10 min),
The melt mass flow rate at 280° C. and a load of 2.16 kg of the resin B is RB (g/10 min),
The laminated|multilayer film whose ratio (RB/RA1) of RB with respect to RA1 and ratio (RB/RA2) of RB with respect to RA2 are 3.5 or more and 15.0 or less, respectively independently. 3. The method of claim 1 or 2,
The laminated|multilayer film whose density|concentration of the ultraviolet absorber in the said resin A1 and the density|concentration of the ultraviolet absorber in the said resin A2 are respectively independently 0 weight% or more and less than 5 weight%. 4. The method according to any one of claims 1 to 3,
The laminated film, wherein the first outer layer is formed in direct contact with one surface of the intermediate layer, and the second outer layer is formed in direct contact with the other surface of the intermediate layer. 5. The method according to any one of claims 1 to 4,
The light transmittance at a wavelength of 320 nm or more and 380 nm or less is 1.0% or less, and the UV absorber included in the intermediate layer contains at least one selected from the group consisting of a benzotriazole-based UV absorber and a triazine-based UV absorber. , laminated film. 6. The method according to any one of claims 1 to 5,
The laminated|multilayer film which further includes a transparent conductive layer. 7. The method of claim 6,
The laminated film, wherein the transparent conductive layer is a layer including indium tin oxide, a layer including silver nanowires, or a layer including a copper mesh structure.

Images