WO2020174975A1 - Lamination film - Google Patents

Abstract

This lamination film includes a first outer layer, an intermediate layer, and a second outer layer in this sequence. The first outer layer is formed of a resin A1 that contains a polymer having an alicyclic structure and has a glass transition temperature of TgA1 (°C). The second outer layer is formed of a resin A2 that contains a polymer having an alicyclic structure and has a glass transition temperature of TgA2 (°C). The intermediate layer is formed of a resin B that contains an ultraviolet ray absorbing agent and a polymer having an alicyclic structure, and has a glass transition temperature of TgB (°C). TgA1 and TgA2 are each independently 150°C or more. (TgA1-TgB) and (TgA2-TgB) are each independently 0-60°C. The concentration of the ultraviolet ray absorbing agent in the resin B is 5-20 wt%. The proportion (TB/(TA1+TA2)) of the thickness TB of the intermediate layer with respect to the total of the thickness TA1 of the first outer layer and the thickness TA2 of the second outer layer is 0.1-0.35.

Description

\¥02020/174975 1 卩 (: 17 2020 /002831 Clarification

Title of invention: Laminated film

Technical field

The present invention relates to a laminated film.

Background technology

[0002] In recent years, the demand for image display devices provided with a touch panel is increasing, and development of a transparent conductive film, which is a member of the touch panel, is progressing. As a transparent conductive film, a film in which a transparent conductive layer is laminated on a resin film as a base material is disclosed (Patent Documents 1 and 2).

[0003] The image display device can be used under light including ultraviolet rays, such as sunlight. In order to protect image display devices from deterioration due to ultraviolet rays, resin films containing ultraviolet absorbers are used as base films for transparent conductive films, polarizing plate protective films, and the like. As the resin film, a laminated film having a three-layer structure is disclosed in which a resin layer containing an ultraviolet absorber is provided as an intermediate layer (Patent Documents 3 to 5).

Prior art documents

Patent literature

[0004] Patent Document 1: Japanese Unexamined Patent Publication No. 201 7 -06 1 069

Patent Document 2: International Publication No. 201 4/1 36701 (Corresponding Publication: US Patent Application Publication No. 201 5/037846 1)

Patent Document 3: JP 2005 _ 1 81 6 1 5 Publication

Patent Document 4: JP 201 8- 1 1 6 789

Patent Document 5: Japanese Patent Laid-Open No. 201 5-045845

Summary of the invention

Problems to be Solved by the Invention

[0005] A laminated film including a resin layer containing an ultraviolet absorber as an intermediate layer may have uneven ultraviolet absorption performance if the thickness of the intermediate layer varies. 〇 2020/174975 2 (:171? 2020/002831

In addition, the laminated film may be exposed to high temperatures during the manufacturing process and the like. If the laminated film is wrinkled by being exposed to high temperatures, the optical characteristics of the member or device including the laminated film may not be retained. In addition, such a member or device may not be efficiently manufactured.

Therefore, there is a demand for a laminated film that suppresses the variation in thickness in the intermediate layer containing the ultraviolet absorber and is less likely to wrinkle even when exposed to high temperatures.

Means for solving the problem

[0006] The present inventors have made extensive studies in order to solve the above problems. As a result, in a laminated film including a first outer layer, an intermediate layer, and a second outer layer in this order, the glass transition temperature of each layer, the thickness ratio of each layer, and the concentration of the ultraviolet absorber in the intermediate layer within a predetermined range. It was found that the above problems can be solved by keeping the content within the range and completed the present invention.

That is, the present invention provides the following.

[0007] [1] includes a first outer layer, an intermediate layer, and a second outer layer in this order,

The first outer layer contains a polymer having an alicyclic structure, and has a glass transition temperature of 9 8 1 (resin 8 1 having a degree of 0°),

It said second outer layer comprises a polymer containing an alicyclic structure made of glass transition temperature from resins eight 2 is Ding ₉ eight 2 (° 〇,

The intermediate layer contains a polymer having an alicyclic structure and an ultraviolet absorber, and is made of a resin having a glass transition temperature of 9° (°°).

Ding 9 8 1 and Ding 9 82 each independently have a temperature of 150°° or more, and the difference between Ding ₉ 8 1 and Ding ₉ M (Ding 9 8 1 -Ding ₉ M) and Ding ₉ 8 2 the difference between the sheets ₉ M. (Ding 9 eight 2 _ sheets ₉ snake) has, is at 0 ° ● as 6 0 ° 〇 less independently, the concentration of the UV absorber in the resin observed, 5 wt% Above 20% by weight,

The ratio of the thickness of the intermediate layer to the total of the thickness of the first outer layer 1 and the thickness of the second outer layer 2 (Chomi / (Choha 1 + Chou 2)) is: . 〇 2020/174975 3 卩 (：171? 2020 /002831

A laminated film having a thickness of 1 or more and 0.35 or less.

（ 9 / 1 0 01 丨 ） であり、 [2] The melt mass flow rate of the resin 81 at 280° and load of 2.1 16 1<9 is

(9/1001 丨)

The melt mass flow rate of the resin 8 2 at 2800° and a load of 2.1 6 1<9 is [¾ 2 (/10 丨n),

Melt mass flow rate of the resin at 280° and load of 2.1 6 1< 9

及び 巳の 八 2に対する割 合 （［¾巳/［¾八2） が、 それぞれ独立して 3 . 5以上 1 5 . 0以下である、

And the ratio of [Minami] to [82] ([¾mi/[¾82] is independently 3.5 or more and 15.0 or less, respectively.

The laminated film according to [1].

[3] The concentration of the ultraviolet absorber in the resin 1 and the concentration of the ultraviolet absorber in the resin 2 are each independently 0% by weight or more and less than 5% by weight, [1] or [2] Laminated film.

[4] The first outer layer is provided in direct contact with one surface of the intermediate layer, and the second outer layer is provided in direct contact with the other surface of the intermediate layer, [1] ~ The laminated film according to any one of [3].

における光線透過率が、 1 . 0 %以下であり、 前記中間層に含まれる前記紫外線吸収剤が、 ベンゾトリア ゾール系紫外線吸収剤及びトリアジン系紫外線吸収剤からなる群から選択さ れる 1種以上を含む、 ［1］ 〜 ［4］ のいずれか 1項に記載の積層フイルム 〇 [Five]

The light transmittance in 1.0% or less, the ultraviolet absorber contained in the intermediate layer contains at least one selected from the group consisting of benzotriazole ultraviolet absorbers and triazine ultraviolet absorbers. , The laminated film according to any one of [1] to [4].

[6] The laminated film according to any one of [1] to [5], further including 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.

Effect of the invention

[0008] According to the present invention, variation in thickness is suppressed in the intermediate layer containing the ultraviolet absorber. 〇 2020/174975 4 卩 (: 171-1? 2020 /002831

It is possible to provide a laminated film which is controlled and which is less likely to wrinkle even when exposed to high temperatures.

Brief description of the drawings

[FIG. 1] FIG. 1 is a cross-sectional view schematically showing a laminated film according to an embodiment of the present invention.

FIG. 2 is a cross-sectional view schematically showing a laminated film according to another embodiment of the present invention.

MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail with reference to embodiments and exemplifications. However, the present invention is not limited to the embodiments and exemplifications shown below, and may be implemented with various modifications without departing from the scope of the claims of the present invention and the scope of equivalents thereof.

[001 1] In the following description, a "long" film means a film having a length of 5 times or more, preferably 10 times or more, with respect to the width. Specifically, it refers to a film having a length such that it is wound into a roll and stored or transported. The upper limit of the length of the film is not particularly limited and may be, for example, 100,000 times or less the width.

、 垂直な方向 （面内方向） であって最大の屈折率を与 える方向の屈折率を表す。

は、 層の前記面内方向であって Xの方向に 直交する方向の屈折率を表す。 ¢1は、 層の厚みを表す。 測定波長は、 別に断 らない限り、 5 9 0 1^ 111である。 [0012] In the following description, the letter size ㊀ in the in-plane direction of the layer is a value represented by another (11 fathers 1^so) 0 1. here,

, Indicates the refractive index in the vertical direction (in-plane direction) and in the direction that gives the maximum refractive index.

Represents the refractive index in the in-plane direction of the layer and in the direction orthogonal to the X direction. ¢1 represents the thickness of the layer. The measurement wavelength is 590 1^111 unless otherwise specified.

In the following description, the directions of the 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° or It may include an error within ± 1 ^° .

[0014] In the present specification, the "agent" may be a single type of substance or may include a plurality of types of substances. 〇 2020/174975 5 卩 (：171? 2020 /002831

[0015] [1. 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. FIG. 1 is a sectional view schematically showing a laminated film according to an embodiment of the present invention. As shown in FIG. 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 provided in direct contact with the one surface 120 II of the intermediate layer 120. The second outer layer 130 is provided in direct contact with the other surface 1200 of the intermediate layer 120. The first outer layer 1 10 has a thickness of 1/8. The second outer layer 1300 has a thickness of 2/8. The intermediate layer 120 has a thickness edge.

The first outer layer 110 is made of a resin 81, and is made of the resin 81.

The second outer layer 1300 is made of a resin 8 2 and is made of the resin 8 2.

The intermediate layer 120 is made of resin and is made of resin. Ratio of the thickness of the middle layer 120 to the total of the thickness 1 of the first outer layer 1 10 and the thickness of the second outer layer 1 30 2 (8) 8)) is usually 0.1 or more and 0.35 or less.

[0016] The laminated film 100 having the above-mentioned constitution can suppress variation in thickness in the intermediate layer 120 and can be a laminated film which is less likely to cause wrinkles even when exposed to high temperature. ..

[0017] [1 .2. resin eight 1]

The resin 1 forming the first outer layer contains a polymer having an alicyclic structure, and has a glass transition temperature of 981 (° ◯).

[0018] The polymer having an alicyclic structure is a polymer having an alicyclic structure in a repeating unit. Hereinafter, the polymer containing an alicyclic structure is also referred to as a “polymer containing an alicyclic structure”.

[0019] The alicyclic structure-containing polymer is excellent in mechanical strength. In addition, the alicyclic structure-containing weight 〇 2020/174975 6 卩 (：171? 2020 /002831

Coalescence is usually excellent in transparency, low water absorption, moisture resistance, dimensional stability and light weight.

[0020] 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. As the alicyclic structure-containing polymer, both a polymer having an alicyclic structure in its main chain and a polymer having an alicyclic structure in its side chain can be used. .. Above all, the alicyclic structure-containing polymer preferably contains an alicyclic structure in the main chain. Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure, and the cycloalkane structure is preferable from the viewpoint of thermal stability and the like.

[0021] The number of carbon atoms contained in one alicyclic structure is preferably 4 or more, more preferably 5 or more, more preferably 6 or more, preferably 30 or less, more preferably Is 20 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.

[0022] The proportion of repeating units having an alicyclic structure in the alicyclic structure-containing polymer is preferably 30% by weight or more, more preferably 50% by weight or more, and further preferably 70% by weight. More preferably, it is 90% by weight or more. By increasing the proportion of repeating units having an alicyclic structure as described above, heat resistance can be improved.

Further, in the alicyclic structure-containing polymer, the balance other than the repeating unit having an alicyclic structure is not particularly limited and may be appropriately selected according to the purpose of use.

[0023] Examples of the alicyclic structure-containing polymer include (1) norbornene-based polymer, (2) monocyclic cycloolefin polymer, (3) cyclic conjugated gen polymer, (4) vinyl alicycle Formula hydrocarbon polymers, and hydrides thereof. Among these, norbornene-based polymers and hydrogenated products thereof are preferable from the viewpoints of transparency and moldability.

[0024] Examples of the norbornene-based polymer include those of monomers having a norbornene structure. 〇 2020/174975 7 卩 (：171? 2020 /002831

Ring-opening polymers and hydrides thereof; addition polymers of monomers having a norbornene structure and hydrides thereof. Further, examples of the ring-opening polymer of a monomer having a norbornene structure include ring-opening homopolymers of one kind of monomer having a norbornene structure and ring-opening polymers of two or more kinds of monomers having a norbornene structure. Examples thereof include a copolymer, and a ring-opening copolymer with a monomer having a norbornene structure and any monomer copolymerizable therewith. Furthermore, examples of addition polymers of monomers having a norbornene structure include addition homopolymers of one type of monomer having a norbornene structure and addition of two or more types of monomers having a norbornene structure. Examples of the copolymer include a monomer having a norbornene structure and an addition copolymer with an arbitrary monomer copolymerizable therewith. Among them, the hydride of a ring-opening polymer of a monomer having a norbornene structure is particularly preferable from the viewpoint of moldability, heat resistance, low moisture absorption, low moisture permeability, dimensional stability and light weight. is there.

[0025] Examples of the monomer having a norbornene structure include, for example, bicyclo [2.2.

... 1] Heputo 2 - E emissions (trivial name: norbornene), tricyclo [4 3 0 1 ^{2, 5]} Deka 3, 7 - Gen (common name: dicyclopentadiene), 7, 8 - benzo tricycloalkyl [... 4 3 〇 1 ^{2, 5]} Deka 3 - E emissions (common name: methano tetrahydrofluorene), tetracyclo [... 4 4 〇 1 ^{2, 5-1 7, 1 0]} Dodeka 3- E down (Common name: tetracyclododecene), and derivatives of these compounds (for example, those having a substituent on the ring). Here, examples of the substituent include an alkyl group, an alkylene group, and a polar group. A plurality of these substituents may be the same or different and may be bonded to the ring. As the monomer having a norbornene structure, one type may be used alone, or two or more types may be used in combination at an arbitrary ratio.

The ring-opening polymer of a 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.

[0027] An addition polymer of a monomer having a norbornene structure can be produced, for example, by polymerizing or copolymerizing the monomer in the presence of an addition polymerization catalyst.

[0028] The hydrides of the ring-opening polymer and addition polymer described above are, for example, 〇 2020/174975 8 卩(：171? 2020/002831

And a solution of the addition polymer, in the presence of a hydrogenation catalyst containing a transition metal such as nickel or palladium, the carbon-carbon unsaturated bond can be produced by preferably hydrogenating 90% or more.

[0029] The weight average molecular weight (!\/!%) of the alicyclic structure-containing polymer contained in the resin 1 is preferably 10,000 or more, more preferably 15,000 or more, and further preferably 20 or more. It is 000 or more, preferably 100,000 or less, more preferably 80,000 or less, and further preferably 50,000 or less. The alicyclic structure-containing polymer having such a weight average molecular weight has an excellent balance of mechanical strength, moldability and heat resistance.

は 、 好ましくは 1. 2以上、 より好ましくは 1. 5以上、 特に好ましくは 1.[0030] Molecular weight distribution of alicyclic structure-containing polymer contained in resin 1

Is preferably 1.2 or more, more preferably 1.5 or more, particularly preferably 1.

It is 8 or more, preferably 3.5 or less, more preferably 3.4 or less, and particularly preferably 3.3 or less. When the molecular weight distribution is at least the lower limit value of the above range, the productivity of the alicyclic structure-containing polymer can be increased and the production cost can be suppressed. Further, when it is at most the upper limit value, the amount of the low molecular weight component becomes small, so that the stability of the first outer layer can be enhanced.

[0031] The weight-average molecular weight IV! and the number-average molecular weight IV! of the alicyclic structure-containing polymer contained in the resin 1 and the alicyclic structure-containing polymer contained in the resin 2 described later are cyclohexane as a solvent. The gel-permeation-chromatography (hereinafter abbreviated as "○○") used can be measured in terms of polyisoprene conversion. If the resin does not dissolve in cyclohexane, the value can be measured in terms of polystyrene by using toluene as the solvent.

株式会社製） 、 「アペル」 （三井化学株式会社 製） 、 「丁〇 八3」 （丁〇 八3 八〇1 3门 06〇1

As the resin containing the alicyclic structure-containing polymer, various products are commercially available, and among them, those having desired characteristics can be appropriately selected and used. Examples of such commercially available products include the product name “2Michi 〇 1\100 ¾” (manufactured by Zeon Corporation), “Arton”

Co., Ltd., “Apel” (Mitsui Chemicals, Inc.), “Cho 83” (Cho 83 830 1 3 门 06 〇 1)

Products). 〇 2020/174975 9 boxes (：171? 2020 /002831

The amount of the alicyclic structure-containing polymer in the resin 1 is preferably 80% by weight or more, more preferably 90% by weight or more, further preferably 95% by weight or more, and usually 100% by weight or more. It is less than or equal to 9% by weight and may be less than or equal to 98% by weight. When the amount of the alicyclic structure-containing polymer in the resin 8 1 is at least the lower limit value, the resin 1 can have the characteristics of the alicyclic structure-containing polymer.

[0034] Resin 1 may include one type of alicyclic structure-containing polymer alone, or may include two or more types of polymers in an arbitrary ratio.

[0035] The resin 1 may contain any component in addition to the alicyclic structure-containing polymer.

Examples of optional components include polymers other than alicyclic structure-containing polymers; inorganic fine particles; antioxidants, heat stabilizers, UV absorbers, stabilizers such as near-infrared absorbers; lubricants, plasticizers. And resin modifiers; colorants such as dyes and pigments; and antistatic agents. As these optional components, one kind may be used alone, or two kinds or more may be used in combination in any ratio.

[0036] The resin 1 may include an ultraviolet absorber as an optional component. From the viewpoint of preventing the ultraviolet absorber from bleeding out from the first outer layer, the concentration of the ultraviolet absorber in the resin 81 is preferably less than 5% by weight, more preferably 3% by weight or less, and further preferably Is 1% by weight or less, usually 0% by weight or more, and may be 0% by weight.

Examples of the ultraviolet absorber that can be contained in the resin 1 include the ultraviolet absorber described below as an example of the ultraviolet absorber contained in the resin.

[0037] [Physical Properties of Resin 1]

The glass transition temperature of the resin 81 is usually 981° or more, preferably 150°° or more, preferably 155°° or more, more preferably 160°° or more, and preferably It is not more than 185° and more preferably not more than 175°. When the glass transition temperature is at least the above-mentioned lower limit, it is possible to suppress the generation of wrinkles in the laminated film during high temperature exposure.

[0038] The glass transition temperature of resin 1 (91) (°○), the glass transition of resin 〇 2020/174975 10 boxes (：171? 2020 /002831

The temperature ( ₉ ° (°)) and the glass transition temperature (9 2 (°)) of resin 2 to be described later are based on “” 3 [< 7 1 2 1 and the differential scanning calorimetry method (hereinafter referred to as mouth 3 ( Also referred to as 3.).

The glass transition temperature measured with the mouth 30 was measured by increasing the temperature from room temperature to 200 ° 〇 at 20 ° 〇 / | and then cooling it to 40 ° 〇 at 20 ° 〇 / 〇 1 丨.

It can be performed under the condition that the temperature is raised from 40°○ to 200°○ at 10°○ / 侨n.

丨 以上、 更に好ましくは 39/1 0〇1 丨 以上であり、 好ましく は 50 g/1 0m i n以下、 より好ましくは

n以下、 更に 好ましくは 20₉ / 1 0

I 门以下である。 樹脂八 1のメルトマスフローレ —卜 八 1 を前記範囲内とすることにより、 より効果的に積層フィルムにお いて高温暴露時のシワの発生を抑制できる。 樹脂八 1のメルトマスフローレ —卜 1は、 例えば、 樹脂 1の重量平均分子量を調整する方法、 滑剤； 可塑剤などの樹脂改質剤；及び紫外線吸収剤などの、 添加剤の含有量を調整 する方法により、 調整しうる。 [0039] Melt mass flow rate of resin 8 at 280° and load of 2.1 61 <9. [¾ 8 is preferably at least 0.5 g/10 m in, more preferably 19/1. 0

Or more, more preferably 39/100 1 or more, preferably 50 g/100 m or less, more preferably

n or less, more preferably 20 _9/1 0

Below I. By setting the melt mass flow rate of the resin 81 to be within the above range, it is possible to more effectively suppress the generation of wrinkles in the laminated film during high temperature exposure. The melt mass flow rate of Resin 81 is, for example, a method of adjusting the weight average molecular weight of Resin 1, a lubricant; a resin modifier such as a plasticizer; and an ultraviolet absorber and the like. It can be adjusted depending on the method.

ともいう。 ） は、 」 丨 3 [< 72 1[0040] The melt mass flow rate of the resin 81 and the resin 82 and the resin to be described later (hereinafter, the melt mass flow rate is

Also called. ) Is ”丨 3 [< 72 1

Based on 0, it can be measured with a melt indexer at a temperature of 280 ^° and a load of 2.1 61 < ₉ .

[0041] [1. 3. Resin 8 2]

The resin 2 forming the second outer layer contains a polymer having an alicyclic structure and has a glass transition temperature of about 982 (° ◯).

[0042] Examples of the alicyclic structure-containing polymer contained in the resin 2 include the same examples as the examples of the alicyclic structure-containing polymer contained in the resin 1. The alicyclic structure-containing polymer contained in the resin 2 can be appropriately selected from suitable examples of the alicyclic structure-containing polymer contained in the resin 1.

[0043] The weight average molecular weight of the alicyclic structure-containing polymer contained in Resin 2 is 〇 2020/174975 1 1 卩(: 171-1? 2020/002831

The weight-average molecular weight (IV!%) in the alicyclic structure-containing polymer contained in can be the same range as the preferable range.

は 、 樹脂 1 に含まれる脂環式構造含有重合体における分子量分布の好適な範 囲と同様の範囲としうる。 [0044] Molecular weight distribution of alicyclic structure-containing polymer contained in Resin 2

Can be in the same range as the preferable range of the molecular weight distribution in the alicyclic structure-containing polymer contained in the resin 1.

[0045] The amount of the alicyclic structure-containing polymer in the resin 2 may be in the same range as the preferable amount of the alicyclic structure-containing polymer in the resin 1.

[0046] The resin 2 may contain one kind of the alicyclic structure-containing polymer alone, or may contain two or more kinds of the polymers having an optional ratio.

[0047] The resin 2 may include any component in addition to the alicyclic structure-containing polymer.

Examples of the optional component include the same examples as the optional component that can be contained in the resin 1. As the optional component, one type may be used alone, or two or more types may be used in combination at any ratio.

[0048] The resin 2 may include an ultraviolet absorber as an optional component. From the viewpoint of suppressing the UV absorber from bleeding out from the second outer layer, the concentration of the UV absorber in the resin 82 is preferably less than 5% by weight, more preferably 3% by weight or less, and further preferably Is 1% by weight or less, usually 0% by weight or more, and may be 0% by weight.

Examples of the ultraviolet absorber that can be contained in the resin 2 include the ultraviolet absorbers described below as examples of the ultraviolet absorber that can be contained in the resin.

[0049] [Physical Properties of Resin 2]

The glass transition temperature of the resin 82 is 982° (° 〇) or more, usually 150°° or more, preferably 155°° or more, more preferably 160°° or more, and preferably It is not more than 185° and more preferably not more than 175°. When the glass transition temperature is at least 982, it is possible to suppress the generation of wrinkles when the laminated film is exposed to high temperatures.

[0050] Melt mass flow rate of resin 82 at 2800° and load of 2.1 6 !< 9 〇 2020/174975 12 boxes (：171? 2020 /002831

n以上、 より好ましくは 1 9 / 1 0

丨 以上、 更に好ましくは 39/1 0〇1 丨 以上であり、 好ましく は 50 g/1 0m i n以下、 より好ましくは

n以下、 更に 好ましくは 20₉/1 〇 丨 n以下である。 樹脂八2の1\/1 を前記範囲内 とすることにより、 より効果的に積層フィルムにおいて高温暴露時のシワの 発生を抑制できる。 樹脂八 2の IV! は、 樹脂八 1の IV! の調整方法とし て例示した方法と同様の方法により、 調整しうる。 -[8] is preferably 〇.

n or more, more preferably 19/10

Or more, more preferably 39/100 1 or more, preferably 50 g/100 m or less, more preferably

It is not more than n, and more preferably not more than 20 ₉ /10 丨n. By setting the ratio 1//1 of the resin 8 to the above range, it is possible to more effectively suppress the generation of wrinkles in the laminated film during high temperature exposure. The IV! of resin 8 2 can be adjusted by the same method as the method exemplified as the method of adjusting IV! of resin 8 1.

The resin eight 2 may be a resin different from the resin eight 1. For example, the resin 8 2 may be different from the resin 1 in the type, weight average molecular weight, molecular weight distribution, content ratio, etc. of the alicyclic structure-containing polymer contained therein, and the type of the optional component contained therein, The content ratio and the like may be different. Further, for example, the resin 82 may have different physical properties from the resin 81 such as glass transition temperature and melt mass flow rate.

However, from the viewpoint of simplifying the production of the laminated film and suppressing the force of the laminated film, the resin 8 2 is preferably the same resin as the resin 8 1.

[0052] [1. 4. Resin]

The resin layer forming the intermediate layer contains a polymer having an alicyclic structure and an ultraviolet absorber, and has a glass transition temperature of just 9 ( ^° ).

Examples of the alicyclic structure-containing polymer contained in the resin matrix include the same examples as the examples of the alicyclic structure-containing polymer contained in the resin 1. The alicyclic structure-containing polymer contained in the resin can be appropriately selected from the preferable examples of the alicyclic structure-containing polymer contained in the resin 1.

[0054] The weight average molecular weight of the alicyclic structure-containing polymer contained in the resin is preferably

10000 or more, more preferably 15,000 or more, more preferably 20 000 or more, preferably 100,000 or less, more preferably 80,000 or less, and further preferably 50000 or less. .. The alicyclic structure-containing polymer having such a weight average molecular weight has an excellent balance of mechanical strength, moldability and heat resistance. 〇 2020/174975 13 卩 (: 171-1? 2020 /002831

は、 好ましくは 1 . 2以上、 より好ましくは 1 . 5以上、 特に好ましくは 1 . 8 以上であり、 好ましくは 3 . 5以下、 より好ましくは 3 . 4以下、 特に好ま しくは 3 . 3以下である。 分子量分布が前記範囲の下限値以上であることに より、 脂環式構造含有重合体の生産性を高め、 製造コストを抑制できる。 ま た、 上限値以下であることにより、 低分子成分の量が小さくなるので、 中間 層の安定性を高めることができる。 [0055] Molecular weight distribution of alicyclic structure-containing polymer contained in resin

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 3.4 or less, and particularly preferably 3.3 or less. Is. When the molecular weight distribution is at least the lower limit value of the above range, the productivity of the alicyclic structure-containing polymer can be increased and the production cost can be suppressed. Further, when it is at most the upper limit value, the amount of low-molecular components becomes small, so that the stability of the intermediate layer can be enhanced.

[0056] The amount of the alicyclic structure-containing polymer in the resin is preferably 80% by weight or more, more preferably 82% by weight or more, further preferably 85% by weight or more, and usually 95% by weight. Or less, and may be 90% by weight or less.

[0057] The resin matrix may contain one kind of the alicyclic structure-containing polymer alone, or may contain two or more kinds of the polymers having an arbitrary ratio.

[0058] Examples of the ultraviolet absorber contained in the resin include benzotriazole ultraviolet absorber, triazine ultraviolet absorber, benzophenone ultraviolet absorber, acrylonitrile ultraviolet absorber, salicylate ultraviolet absorber, Organic UV absorbers such as cyanoacrylate UV absorbers, azomethine UV absorbers, indole UV absorbers, naphthalimide UV absorbers and phthalocyanine UV absorbers can be mentioned.

Among them, it is preferable that the resin resin contains at least one selected from the group consisting of benzotriazole-based UV absorbers and triazine-based UV absorbers.

[0059] The benzotriazole ultraviolet absorber contains a benzotriazole structure in the molecule.

Examples of benzotriazole-based UV absorbers include 2,2'-methylenebis [6— (2 1 ^to 1-benzotriazol-2-yl) 1 4-(1 ,1 ,3,3-tetramethylputyl) phenol], 2 - (2 1 ^~ 1 _ benzotriazol-2-yl) one over cresol and 2- (5-chloro-2 1 ^- 1 - Benzotoria Zoru 2-yl) _ 6 _ ㊀ "butyl-4-methyl phenol is To be mentioned. 〇 2020/174975 14 卩 (：171? 2020 /002831

[0060] Examples of commercially available benzotriazole-based UV absorbers include "Adeka Stab 1_81 1 3 1", "Adeka Stub !_8 1 3 2", and "Adeka Stub !_8 1 3 6”.

[0061] The triazine-based ultraviolet absorber contains a triazine structure in the molecule. As the triazine-based ultraviolet absorber, a compound containing a 1,3,5-triazine structure in the molecule is preferable.

Examples of triazine-based UV absorbers include 2,4,6-tris (2-hydroxy-3-methyl-4-hexyloxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl). 1, 3, 3, 5-triazin-2-yl) 1-5-(2-(2-ethylhexanoyloxy)ethoxy)phenol, and 2,4-diphenyl-6-(2-hydroxy_4-hexyloxyphenyl)-1 1,3,5-triazine is an example.

[0062] Examples of commercially available triazine-based UV absorbers include ^ DE< "Adeka Stab!-Hachi _ 70", "Adeka Stub !_ Hachi_4 6", and Miwahachi 3 Japan. “Tinubin 1 5 7 7” is mentioned.

[0063] As another specific example of the ultraviolet absorber, the ultraviolet absorber described in Japanese Patent Laid-Open No. 2017-155410 can be mentioned.

[0064] The resin composition may contain one kind of the ultraviolet absorber alone, or may contain two or more kinds of the ultraviolet absorber in an arbitrary ratio.

[0065] The content of the ultraviolet absorber in the resin is usually 5% by weight or more, preferably

It is 7% by weight or more, more preferably 8% by weight or more, usually 20% by weight or less, preferably 15% by weight or less, more preferably 13% by weight or less.

When the content of the ultraviolet absorber in the resin is equal to or more than the lower limit value, the ultraviolet absorbing performance of the laminated film is improved. When the content of the ultraviolet absorber in the resin is less than or equal to the upper limit value, the coloring of the resin by the ultraviolet absorber can be suppressed, and the ultraviolet absorber can be better dispersed in the resin.

[0066] The resin resin contains an optional component in addition to the alicyclic structure-containing polymer and the ultraviolet absorber. 〇 2020/174975 15 卩(: 171-1? 2020/002831

May be included.

Examples of the optional component include the same examples as the optional component that can be contained in the resin 1. As the optional component, one type may be used alone, or two or more types may be used in combination at any ratio.

[0067] [Physical Properties of Resin]

The glass transition temperature sheets ₉ 1 resin 1 (° 〇) and the resin snake glass transition temperature sheets 9 M. (difference between ° 〇 (sheets 9 eight 1 - Ding 9 Snake) is usually 60 ° 〇 less, preferably Is not more than 50° 〇, more preferably not more than 48° 〇, and usually not less than 0° 〇 Also, the glass transition temperature of resin 2 is 9 2 (° 〇 and the glass transition temperature of resin 9 is 9 The difference from ° 〇 (Cho 9 82 -Cho 9) is usually 60° 〇 or less, preferably 50° 〇 or less, more preferably 48° 〇 or less, usually 0° 〇 or more. is there.

By having the above-mentioned relationship between the glass transition temperature (9) and the glass transition temperature (9) and (982) of the resin resin, it is possible to suppress the dimensional change of the laminated film after heating, and even when exposed to high temperature. It can be a laminated film that is less likely to wrinkle.

[0068] The ratio of the melt mass flow rate (9/100) of the resin resin at 280° and load of 2.1 61<9 (9/100/11) to the melt mass flow rate [¾1 ((¾// 8 1) is usually 3.5 or more, preferably 4.0 or more, usually 15.0 or less, preferably 14.5 or less, more preferably 14.0 or less. When the ratio ([¾mi/[¾8 1)) is equal to or more than the lower limit value, variation in the thickness of the intermediate layer is suppressed, and wrinkles are less likely to occur even when exposed to a high temperature.

[0069] Further, the ratio of the melt mass flow rate to the melt mass flow rate 8 2 ([¾//¾2 2] is usually 3.5 or more, preferably 4.0 or more, and usually 15.0. The ratio is preferably 14.5 or less, more preferably 14.0 or less. When the ratio ([¾mi/[¾2 2]) is at least the lower limit value described above, it is possible to obtain a laminated film in which variations in the thickness of the intermediate layer are suppressed and wrinkles do not easily occur even when exposed to high temperatures. 〇 2020/174975 16 卩(：171? 2020/002831

[0070] The melt mass flow rate of the resin can be adjusted by a method similar to the method exemplified as the method for adjusting IV! of the resin 81.

[0071] [1.5. Structure of laminated film, physical properties, etc.]

In the laminated film, the ratio of the thickness of the middle layer to the total of the thickness of the first outer layer 1, 8 and the thickness of the second outer layer 2, 2 (Chomi / (Chachi 1 + Chou 2)

) Is usually at least 0.1, preferably at least 0.13, more preferably at least 0.16, usually at most 0.35, preferably at most 0.32, and more preferably at 0.30. It is the following. By setting the ratio (Chomi / (Chohachi 1 + Chouha 2)) within the above range, a wrinkle that is less likely to wrinkle when exposed to high temperatures can be obtained. The thickness of the intermediate layer is preferably not less than 30 and not more than 150 but can be appropriately set depending on the amount of the ultraviolet absorber contained in the intermediate layer, and the like. Although not particularly limited, it is preferably not less than 50! and not more than 3500!

[0072] The laminated film has a light transmittance of usually not more than 1.0%, preferably not more than 0.8%, and ideally 0 at wavelengths of 320°! or more and 380! or less. %, and may be 0% or more.

When the light transmittance of the laminated film at the wavelength of 3201^ ◯ or more and 380 1^ or less is not more than the above upper limit, the laminated film can cut ultraviolet rays more effectively.

紫外可視近赤 外分光光度計を用いて測定されうる。

It can be measured using a UV-Vis near-IR spectrophotometer.

より好ましくは 3 〇!以下であり、 通常 0 〇!以上である。 面 内方向におけるレターデーシヨン[¾ ㊀は、 市販の複屈折計を用いて測定され うる。 〇 2020/174975 17 卩（：171? 2020 /002831 [0073] The laminated film has a letter size [6] in the in-plane direction, preferably

It is more preferably 30! or less, and usually 0!! or more. The letter size in the in-plane direction can be measured using a commercially available birefringence meter. 〇 2020/174975 17 卩(: 171-1? 2020/002831

[0074] The haze of the laminated film is preferably 5% or less, more preferably 3% or less, and usually 0% or more. Haze can be measured using a commercially available haze meter.

[0075] The laminated film has a total light transmittance of preferably 90% or more, more preferably 91% or more, and usually 100% or less. The total light transmittance can be measured using a commercially available haze meter.

[0076] The absolute value of the dimensional change rate of the laminated film after heating at 1 45 ° 〇 for 60 minutes is preferably 0.1% or less, more preferably less than 0.1%, and usually 0% or more. Is.

The absolute value of the dimensional change rate after heating at 150°C for 60 minutes can be obtained as the absolute value of the dimensional change rate of the laminated film after heating with respect to the dimension of the laminated film before heating.

More specifically, the absolute value of the dimensional change rate can be obtained by the method described in the examples.

[0077] [1.6. Any layer that can be included in the laminated film]

The laminated film may include an optional layer in addition to the first outer layer, the intermediate layer, and the second outer layer. Examples of the optional layer include a transparent conductive layer, an adhesive layer, and an adhesion auxiliary layer.

[0078] [Transparent conductive layer]

The laminated film may include a transparent conductive layer.

The conductive layer is provided, for example, on the outermost surface of the laminated film.

FIG. 2 is a sectional view schematically showing a laminated film according to another embodiment of the present 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. A laminated body 250 including the first outer layer 210, the intermediate layer 220, and the second outer layer 230 has a structure similar to that of the laminated film 100, and the first outer layer The layer 210, the intermediate layer 220, and the second outer layer 230 have the same configurations as the first outer layer 110, the intermediate layer 120, and the second outer layer 130, respectively. Since it has, the description is omitted. 〇 2020/174975 18 卩 (: 171-1? 2020 /002831

The transparent conductive layer is a layer having conductivity.

The transparent conductive layer usually contains a conductive material having a high transmittance at a visible light wavelength. Examples of the conductive material contained in the transparent conductive layer are 丨 〇 (indium tin oxide), 丨 〇 (indium zinc oxide), Z n 〇 (zinc oxide), 丨 〇 (indium tungsten oxide),丨 丨 〇 (Indium Titanium Oxide), 8,000 (Aluminum Zinc Oxide), ◦ 〇 (Gallium Zinc Oxide), 〇 (Zinc-based Special Oxide), 〇 〇 〇 (Indium Gallium Zinc Oxide) ) And other conductive metal oxides; conductive carbon nanowires, conductive nanowires such as silver nanowires; metal nanoinks; metal mesh such as copper mesh; conductive polymers; and the like. In addition, one kind of these conductive materials may be used alone, or two or more kinds thereof may be used in combination at an arbitrary ratio.

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.

[0080] The transparent conductive layer has a light transmittance in the wavelength range of 400 nm to 700 nm.

, Preferably 85% or more, more preferably 90% or more, and further preferably 95% or more.

[0081] The transparent conductive layer may have a predetermined pattern.

In the present embodiment, the transparent conductive layer 240 is provided directly in contact with the first outer layer 210 so that it is outside the first outer layer 210. However, in the laminated film of another embodiment, the transparent conductive layer may be provided directly in contact with the second outer layer so that it is on the outer side of the second outer layer.

A laminated film according to another embodiment is a first transparent conductive layer which is provided in direct contact with the first outer layer and a second transparent conductive layer which is provided in direct contact with the second outer layer. It may include a bright conductive layer.

In the laminated film according to still another embodiment, any layer may be provided between the first outer layer and the transparent conductive layer or between the second outer layer and the transparent conductive layer. 〇 2020/174975 19 卩(: 171-1? 2020/002831

[0083] [1.7. Use of laminated film]

The laminated film has little variation in ultraviolet absorption performance as a result of suppressing variation in thickness in the intermediate layer. Also, wrinkles are less likely to occur even when exposed to high temperatures. Therefore, for example, it can be suitably used as a polarizing plate protective film, a retardation film, a base film for a touch panel that can be manufactured at high temperature.

[0084] [2. Method for producing laminated film]

The laminated film may be manufactured by any method. For example, the first outer layer, the intermediate layer, and the second outer layer may be separately manufactured by a known method such as a melt molding method or a solution casting method, and then the layers may be stacked. It may well be produced by laminating resin 81, resin M, and resin 8 2 by a coextrusion method.

The laminated film may be manufactured as a long film.

When the laminated film includes a transparent conductive layer, the transparent conductive layer can be formed by a method according to the conductive material contained in the transparent conductive layer. For example, the transparent conductive layer may be formed by a vapor deposition method, a sputtering method, a coating method, or the like.

Example

[0086] Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited to the examples described below, and may be implemented by being arbitrarily modified within the scope of the claims and equivalents thereof.

[0087] In the following description, "%" and "parts" representing amounts are by weight unless otherwise specified. Further, the operations described below were performed at room temperature and atmospheric pressure unless otherwise specified.

[0088] [Evaluation Method]

(Glass-transition temperature)

The glass transition temperature of the sample was measured by differential scanning calorimetry based on "3 [< 7 1 2 1]. The measurement was carried out from room temperature to 200 ^° 〇 at a temperature of 20 ^° 〇 / 丨n, then up to 40 ° 〇 at a temperature of 20 ° 〇 / 〇 1 〇 2020/174975 20 units (：171? 2020 /002831

It was performed under the condition that the temperature was raised to 0 0 ° 〇 at 10 ° 〇 / 〇 1 侨n.

[0089] (Melt mass flow rate)

The melt mass flow rate of the sample was measured based on "1 3 [< 7 2 1 0, using a melt indexer (" _ 0 1 ", manufactured by Toyo Seiki Seisaku-sho, Ltd.), at a temperature of 280 ^° 〇, and a load of 2 .16 1 It was measured under the condition of <9.

[0090] (Measurement of molecular weight)

The weight average molecular weight and number average molecular weight of the alicyclic structure-containing polymer is a gel permeation Mieshiyon chromatography (manufactured by Tosoh Corporation) (x x) System ^1-1 1_〇 one 8 3 2 0, ^1-1 Using a type column (manufactured by Tosoh Corporation), cyclohexane was used as a solvent and the measurement was carried out at 40 ^° C to obtain a polyisoprene conversion value.

[0091] (Hydrogenation rate of polymer)

The hydrogenation rate of the polymer was determined by ^{1 1 ~ 1} _ IV!.

[0092] (Haze of laminated film)

あ る略正方形のフィルム片を、 合計 3枚切り出した。 得られた 3つのフィルム 片それぞれのヘイズを、 ヘイズメーター （日本電色工業社製

0 0〇」 ） を用いて測定した。 得られた 3枚のフィルム片のヘイズの平均を、 積層フィルムのヘイズの値とした。 From the widthwise both ends of the laminated film and the widthwise center, one side is 5

A total of three pieces of film with a substantially square shape were cut out. The haze of each of the three obtained film pieces was measured by a haze meter (Nippon Denshoku Industries Co., Ltd.).

0 00 ”). The average of the haze of the obtained three pieces of film was used as the value of the haze of the laminated film.

(Total light transmittance of laminated film)

あ る略正方形のフィルム片を、 合計 3枚切り出した。 得られた 3つのフィルム 片それぞれの全光線透過率を、 ヘイズメーター （日本電色工業社製

— 2 0 0 0」 ） を用いて測定した。 得られた 3枚のフィルム片の全光線透過 率の平均を、 積層フィルムの全光線透過率の値とした。 From the widthwise both ends of the laminated film and the widthwise center, one side is 5

A total of three pieces of film with a substantially square shape were cut out. The total light transmittance of each of the three obtained film pieces was measured by a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd.).

-200")). The average of the total light transmittances of the obtained three film pieces was taken as the value of the total light transmittance of the laminated film.

(Letter decision in the in-plane direction of the laminated film ㊀)

あ る略正方形のフィルム片を、 合計 3枚切り出した。 得られた 3つのフィルム 片それぞれの、 面内方向におけるレターデーシヨン[¾ 6を、 自動複屈折計 （ 〇 2020/174975 21 卩（：171? 2020 /002831 From the widthwise both ends of the laminated film and the widthwise center, one side is 5

A total of three pieces of film with a substantially square shape were cut out. An automatic birefringence meter ((6) was used to measure the letter division [¾6] of each of the three obtained film pieces in the in-plane direction. 〇 2020/174975 21 卩(：171? 2020/002831

した。 得られた

"K○B LA_2 1 ADH" manufactured by Oji Scientific Instruments Co., Ltd.). The measurement wavelength is

did. Got

The average of 6 was taken as the value of the letter size [%] of the laminated film.

[0095] (UV transmittance)

おける紫外線透過率 （％） 、 並びに、 波長 320 n

におけ る紫外線透過率の最大値 （％） を、 得られたスペクトルから読み取った。 The ultraviolet transmittance of the film to be measured was measured in the range of wavelength 2001^111 to 4001^111 using an ultraviolet-visible/near-infrared spectrophotometer ("V-550" manufactured by JASCO Corporation). Wavelengths 3201^111, 3401^111, 360 doors!, and 380

UV transmittance (%) and wavelength 320 n

The maximum value (%) of the UV transmittance in the sample was read from the obtained spectrum.

[0096] (Dinomi / (7 A ^ +7 A2) and variation in thickness in the intermediate layer)

The total thickness () of the laminated film at a certain position was measured by using a commercially available contact thickness gauge.

The laminated film was cut along a plane including the thickness direction and the cross section was observed with an optical microscope.At the location where the total thickness was measured, the thickness of the intermediate layer was calculated as The ratio (Chomi / (Chohachi 1 + Chouha 2)) was calculated. From the total thickness of the laminated film and the ratio (Chome / (Chome8 1 + Chome2)), the thickness of the middle layer Chome (01) was obtained.

間隔で 1 0箇所、 長手方向 （積層フィルムの製造における搬 送方向） に 50 間隔で 1 0箇所の、 合計 20箇所で行った。 ただし、 積 層フィルムの幅方向における端部から 50

の範囲を、 測定箇所から除い た。 The above measurement was performed in the width direction (direction perpendicular to the transport direction in the production of laminated film).

A total of 20 locations were performed, with 10 locations at intervals and 10 locations at 50 intervals in the longitudinal direction (transport direction in the production of laminated films). However, 50 from the edge in the width direction of the laminated film

The range of was excluded from the measurement points.

[0097] The arithmetic mean value of the ratio (Chomi / (Chohachi 1 + Chou 8 2)) measured at 20 locations was calculated as the ratio of the laminated film ratio (Chomi / (Chochi 1 + Chou 8 2) ). The value.

（ ） と、 最小値丁巳 „ （ ） と、 最大値

（ ） とから、 下記 の式により、 1及び 2を求めた。 1 と 2とを比較し、 1及び 2 の値が互いに同一である場合はその値を、 値が互いに異なる場合は大きい方 〇 2020/174975 22 卩（：171? 2020 /002831 [0098] In addition, the arithmetic mean value of the thicknesses of the intermediate layers measured at 20 points

() and minimum value □ () and maximum value

From (), 1 and 2 were calculated by the following formula. 1 and 2 are compared, and if the values of 1 and 2 are the same as each other, the value is larger, and if the values are different, the larger 〇 2020/174975 22 卩 (: 171? 2020 /002831

The value of was taken as the variation port () of the thickness of the intermediate layer in the laminated film.

¢ 1 1 () = Ding-Ding-

¢12 () = Ding-Ding-

[0099] (Dimensional stability and suppression of wrinkles)

From the widthwise both ends of the laminated film and the widthwise central portion, a total of three film pieces each having a square shape of 100.times.101 on one side were cut out. At the time of cutting, each side of the film piece was made to be parallel to the width direction or the transport direction of the laminated film.

The three pieces of film were heated at 145° for 60 minutes and then allowed to cool. After heating and cooling, the three film pieces were visually observed, and the wrinkle suppression during high temperature exposure was evaluated according to the following criteria.

Good: No wrinkles on any of the three film pieces.

Bad: Wrinkles on any of the three pieces of film.

） を測り 、 下記式に従い、 加熱前の寸法 （1 00〇!〇〇 に対する寸法変化率の絶対値

[0100] The dimension X of each side (side in the width direction and side in the direction parallel to the transport direction) of each of the three film pieces after heating and cooling.

), and according to the following formula, the absolute value of the dimensional change rate with respect to the dimension before heating (100 00!

（%） を求め、 下記基準により、 高温暴露時 における積層フィルムの寸法安定性を評価した。 八 V ₆が小さい程、 高温暴 露時における積層フィルムの寸法安定性が高い。 Furthermore, the absolute value of the dimensional change rate obtained for each side of the three film pieces | [¾ | | (%) arithmetic mean value

(%) was obtained, and the dimensional stability of the laminated film at the time of high temperature exposure was evaluated according to the following criteria. The smaller the V ₆ is, the higher the dimensional stability of the laminated film during high temperature exposure.

Eight: Eight V 6 <○ 0.1%

Min: 〇.1% £8 V 6<○.2%

0: 0.2% £8 V 6

[0101] [Production Example 1: Production of alicyclic structure-containing polymer 〇 1]

Tricyclo [4. 3. 〇 .1 ^{2, 5} ] Deca 3,7-gen (dicyclopentadiene, hereinafter abbreviated as appropriate 〇 〇) and 7, 8-benzotrisic 〇 2020/174975 23 卩 (：171? 2020 /002831 mouth [4. 4. 〇 .1, 2, 5. 1 7, ₁ 〇] Deca-3-ene (methanotetrahydrofluorene, hereinafter, as appropriate "1\/ 1)” was mixed in a weight ratio of 87/1 3. This mixture was subjected to ring-opening polymerization by the method described in Japanese Patent No. 6256353 [Example 1], and then hydrogenated. A polymer <31, which is a hydrate of a ring-opening polymer, was obtained.

The copolymerization ratio of each norbornene-based monomer in the obtained polymer 01 was calculated from the composition of the norbornene-based monomer remaining in the solution after polymerization by gas chromatograph analysis. Mouth 〇/1\/1 crocodile = 87/1 3, which was almost equal to the composition.

は 38, 000、 分子量

は数平均分子量） は 2. 2、 水素化率は 99. 9% 、 ガラス転移温度丁 9は 1 25 °〇であった。 Also, the weight average molecular weight of this polymer <31

Is 38,000, molecular weight

Was 2.2, the hydrogenation rate was 99.9%, and the glass transition temperature was 25°.

[0102] [Production Example 2: Production of alicyclic structure-containing polymer 02]

開環重合体 水素化物である、 重合体 02を得た。 O and IV! were mixed in a weight ratio of 85/15. The mixture is subjected to ring-opening polymerization by the above-mentioned known method, then hydrogenated,

A ring-opening polymer hydride, Polymer 02 was obtained.

The copolymerization ratio of each norbornene-type monomer in the obtained polymer 02 was calculated from the composition of the norbornene-type monomer remaining in the solution after the polymerization by an analysis by a gas chromatography method. The ratio was /1//1 = 85/1 5, which was almost equal to the composition of the ingredients.

The weight average molecular weight (1\/1) of this polymer 02 is 33,000, the molecular weight distribution (1\/1/1\/^) is 2.1, the hydrogenation rate is 99.9%, the glass transition. Temperature 9 was 135°.

[0103] [Production Example 3: Production of alicyclic structure-containing polymer 03]

〇 〇, IV! Ding, and tetracyclo [4. 4. 〇. 1 2 ^, 5, 1 7 ^, 7 ^, 10] Dode force 1- 3 ene (tetracyclododecene, hereinafter abbreviated as “Dick ”) To do.

) Was mixed in a weight ratio of 5/70/25. This mixture was subjected to ring-opening polymerization by the above-mentioned known method, and then hydrogenated to give a hydrogen ring-opening polymer hydrogen. 〇 2020/174975 24 卩 (：171? 2020 /002831

As a result, polymer 03 was obtained.

は 2 . 1、 水素化率 は 9 9 . 9 %、 ガラス転移温度丁 9は 1 6 2 °〇であった。 The copolymerization ratio of each norbornene-based monomer in the obtained polymer 03 was calculated from the composition of the norbornene-based monomer remaining in the solution after the polymerization by gas chromatography analysis. It was /1\/1chome/chome 0 = 5/70/25, which was almost equal to the composition. In addition, the weight average molecular weight of this polymer 0 3

Was 2.1, the hydrogenation rate was 99.9%, and the glass transition temperature was 962 °.

[0104] [Example 1]

(Manufacturing of resin)

91 parts of the polymer 0 1 and 9 parts of the ultraviolet absorber were mixed by a twin-screw extruder to obtain a resin molding 1. As the UV absorber, 880 [[8_31 ", manufactured by Hachisha, Ltd.] containing a benzotriazole structure in the molecule was used.

[0105] (Production of laminated film)

A coextrusion film forming machine capable of producing a laminated film of two kinds and three layers, which comprises a feed block and a single layer die connected to the feed block, was prepared. The first outer layer, the middle layer, and the second outer layer are provided in this order, and the resin that has been melted to 280 ^° is supplied to the feed block as the material for each layer so that the film is discharged. It was discharged from a single-layer die and coextruded. As the materials for the first outer layer and the second outer layer, the polymer 03 as the resin 1 and the resin 2 was supplied. As a material for the intermediate layer, resin 1 was supplied.

の長尺の積層フィルムを得た。 積層フィルムは、The co-extruded film-like resin was cast into a cooling port whose temperature was adjusted to 100 ^° and cooled through another cooling port whose temperature was adjusted to 50°. This gives a width of 6

A long laminated film of was obtained. Laminated film

(First outer layer made of polymer 03/intermediate layer made of resin/second outer layer made of polymer 03)

The obtained laminated film was evaluated according to the above evaluation method.

[0107] [Example 2]

A laminated film was obtained in the same manner as in Example 1 except that the following items were changed. 〇 2020/174975 25 卩 (：171? 2020 /002831

, evaluated.

を 9部の代 わりに、 八〇巳 八社製 「!_八ー 7 0」 を 1 6部を用いて、 樹脂巳 2を製 造した。 「I -八ー 7 0」 は、 分子内に 1 , 3 , 5 -トリアジン構造を含む 積層フィルムの製造において、 樹脂巳 1の代わりに、 樹脂巳 2を供給し、 各層が表に示す厚みとなるように共押出の条件を調整した。 In the production of resin resin, 84 parts of polymer 0 2 was used in place of 91 parts of polymer 0 1, and as an ultraviolet absorber,

Instead of 9 parts of the resin, 16 parts of “!_8-70” manufactured by 80, Ltd. was used to manufacture resin 2. "I-8-8" means that in the production of laminated film containing 1,3,5-triazine structure in the molecule, resin layer 2 is supplied instead of resin layer 1, and each layer has the thickness shown in the table. The coextrusion conditions were adjusted so that

The laminated film has a structure of 2 types and 3 layers of (first outer layer made of polymer 0 3 / middle layer made of resin 2 / second outer layer made of polymer 0 3 ).

[0108] [Example 3]

A laminated film was obtained and evaluated in the same manner as in Example 1 except that the following items were changed.

In the production of the resin resin, instead of 91 parts of the polymer 0 1, 8 8 parts of the polymer 0 3 was used, and the amount of “1_ _ 3 1” manufactured by Ozumi Co., Ltd. as a UV absorber was used.

Resin part 3 was manufactured by changing from 9 parts to 12 parts.

In the production of the laminated film, the resin mold 3 was supplied in place of the resin mold 1, and the coextrusion conditions were adjusted so that each layer had the thickness shown in the table.

The laminated film has a structure of two types and three layers of (first outer layer made of polymer 03/intermediate layer made of resin 3/second outer layer made of polymer 03).

[0109] [Comparative Example 1]

A laminated film was obtained and evaluated in the same manner as in Example 1 except that the following items were changed.

In the production of the laminated film, the polymer 0 1 was supplied instead of the polymer 0 3, and the coextrusion conditions were adjusted so that each layer had the thickness shown in the table.

The laminated film has a structure of 2 types and 3 layers of (first outer layer made of polymer 0 1, middle layer made of resin 1, and second outer layer made of polymer 0 1 ).

[01 10] [Comparative Example 2] 〇 2020/174 975 26 卩 (：171? 2020 /002831

A laminated film was obtained and evaluated in the same manner as in Example 1 except that the following items were changed.

-In the production of the laminated film, the coextrusion conditions were adjusted so that each layer had the thickness shown in the table.

The laminated film has a structure of 2 layers and 3 layers of (first outer layer made of polymer 03/intermediate layer made of resin 1/second outer layer made of polymer 0 3 ).

[01 1 1] [Comparative example 3]

A laminated film was obtained and evaluated in the same manner as in Example 1 except that the following items were changed.

In the production of resin, as an ultraviolet absorber,

Resin! 4 was manufactured by using “!_8-7 0” manufactured by 80. 8 companies instead of 1”.

In the production of the laminated film, the resin mold 4 was supplied instead of the resin mold 1, and the coextrusion conditions were adjusted so that each layer had the thickness shown in the table.

The laminated film has a structure of 2 types and 3 layers of (first outer layer made of polymer 0 3 / middle layer made of resin 4 / second outer layer made of polymer 0 3 ).

[01 12] [Comparative Example 4]

A laminated film was obtained and evaluated in the same manner as in Example 1 except that the following items were changed.

を 9部の代 わりに、 八〇巳 八社製 「!_八ー 7 0」 を 1 6部を用いて、 樹脂巳 2を製 造した。 In the production of resin resin, 84 parts of polymer 0 2 was used in place of 91 parts of polymer 0 1, and as an ultraviolet absorber,

In place of 9 parts of the resin, 16 parts of “!_8-7 0” manufactured by 80, Ltd. 8 company was used to manufacture resin 2.

In the production of a laminated film, resin (2) was supplied instead of resin (1), polymer (1) was supplied instead of polymer (3), and coextrusion conditions were set so that each layer had the thickness shown in the table. Was adjusted.

The laminated film has a structure of 2 types and 3 layers of (first outer layer made of polymer 0 1, middle layer made of resin 2, and second outer layer made of polymer 0 1 ). 〇 2020/174 975 27 卩 (: 171? 2020 /002831

[01 13] [Comparative Example 5]

A laminated film was obtained and evaluated in the same manner as in Example 1 except that the following items were changed.

-In the production of resin, the amount of polymer 0 1 was changed from 91 to 7 6 parts, and the amount of "1_81 3 1" manufactured by Yatsumi Hachisha Co., Ltd. as an ultraviolet absorber was changed to Resin 9 was manufactured by changing from 9 parts to 24 parts.

In the production of the laminated film, resin 5 was supplied instead of resin 1, and the coextrusion conditions were adjusted so that each layer had the thickness shown in the table.

The laminated film has a structure of 2 types and 3 layers of (first outer layer made of polymer 03/intermediate layer made of resin 5/second outer layer made of polymer 03).

[01 14] [Comparative Example 6]

A laminated film was obtained and evaluated in the same manner as in Example 1 except that the following items were changed.

を 9部の代 わりに、 八〇巳 八社製 「!_八ー 7 0」 を 2 2部を用いて、 樹脂巳 6を製 造した。 In the production of resin resin, 78 parts of polymer 0 2 was used in place of 91 parts of polymer 0 1, and as an ultraviolet absorber,

Instead of 9 parts of resin, resin 2 was manufactured by using 22 parts of "!_8-70" manufactured by 880.

In the production of the laminated film, resin 6 was supplied instead of resin 1, and the coextrusion conditions were adjusted so that each layer had the thickness shown in the table.

The laminated film has a structure of 2 types and 3 layers of (first outer layer made of polymer 03/intermediate layer made of resin 6/second outer layer made of polymer 03).

[0115] The constitution and evaluation results of the laminated film are shown in the table below.

The abbreviations in the table below have the following meanings.

II V: UV absorber

Benzotriazole type: "!_81 1 3" manufactured by 880 Hachisha

Triazine type: Made by Yasumi eight company "!_ eight-seven"

Tingmi: Thickness of the middle layer

Dingha 1 + Dinghai 2: Thickness of the 1st outer layer (Ding 8) and 2nd outer layer (Ding 8 〇 2020/174 975 28 卩 (: 171? 2020 /002831

Eight 2) total

^ Min: Melt mass flow of resin _ Re _

Ding 9: Glass transition temperature of resin

Ding 9: Glass transition temperature of resin 1 and resin 2

8 8: Melt mass flow rate of resin 8 1 and resin 8 2

〇 1: Polymer produced in Production Example 1 〇 1

0 2: Polymer produced in Production Example 2

0 3: Polymer produced in Production Example 3

Maximum value of UV transmittance: Maximum value of UV transmittance in the wavelength range from 320 _{n to} 380 _n

[01 16] [Table 1]

table 1

〇 2020/174975 29 卩（：171? 2020 /002831

〇 2020/174 975 29

[01 17] [Table 2]

Table 2

[01 18] From the above results, the following can be understood.

It can be seen that in the laminated films according to Examples 1 to 3, the variation in the thickness of the intermediate layer is small, and the generation of wrinkles is suppressed after being exposed to the high temperature of 1445°.

On the other hand, it can be seen that the laminated films according to Comparative Examples 1 to 6 do not suppress the generation of wrinkles.

Specifically, the laminated films according to Comparative Examples 5 and 6 had a concentration of the ultraviolet absorber in the resin resin of more than 20% by weight, wrinkles were not suppressed, and the dimensional stability was inferior to the examples. 〇 2020/174 975 30 卩 (：171? 2020 /002831

In the laminated films according to Comparative Examples 1 and 4, the first outer layer and the second outer layer were formed of a resin having a glass transition temperature of less than 150 ^° C., and the occurrence of wrinkles was not suppressed.

In the laminated film according to Comparative Example 5, Ding 9 8 1 Ding 9 is higher than 60°, wrinkles are not suppressed, and the dimensional stability is inferior to that of the example.

The laminated films according to Comparative Examples 1 and 2 have a ratio of (Chomi / (Chohachi 1 + Chouha 2)

) Is larger than 0.35, and there is a large variation in the thickness of the intermediate layer, and wrinkles are not suppressed.

In the laminated film according to Comparative Example 3, the ratio (Chome/(Chome8 1 +Chome 8 2)) was less than 0.1, and wrinkle generation was not suppressed.

1 5. 0より大きく、 中 間層における厚みのばらつきが大きく、 シワ発生が抑制されておらず、 寸法 安定性が実施例よりも劣る。 The laminated film according to Comparative Example 6,

The dimensional stability is inferior to that of the example, since the thickness is larger than 15.0, the thickness variation in the middle layer is large, the occurrence of wrinkles is not suppressed.

[0119] The above results show that the laminated film of the present invention has suppressed variation in thickness in the intermediate layer containing the ultraviolet absorber, and is resistant to wrinkles even when exposed to high temperatures. Is.

Explanation of symbols

[0120] 100: Laminated film

1 1 0: 1st outer layer

1 20: Middle layer

1 30: Second outer layer

1 200: Face

1 20 II: Face

200: Laminated film

2 1 0: 1st outer layer

220: Middle layer

230: Second outer layer

240: Transparent conductive layer \¥02020/174975 31 卩 (: 17 2020 /002831

250: laminate

Claims

\¥02020/174975 32 units (: 17 2020 /002831 The scope of the claims [Claim 1] A first outer layer, an intermediate layer, and a second outer layer are included in this order, The first outer layer contains a polymer having an alicyclic structure, and is made of a resin 81 having a glass transition temperature of 981 (°°), and the second outer layer has an alicyclic structure. Including a polymer containing a polymer having a glass transition temperature of 982 2 (° resin 0 82, the intermediate layer contains a polymer having an alicyclic structure and an ultraviolet absorber, It consists of a resin with a glass transition temperature of 9 mil (° 〇, Ding 9 8 1 and Ding 9 82 each independently have a temperature of 150 ° 〇 or more, and the difference between Ding ₉ 8 1 and Ding ₉ M (Ding 9 8 1 -Ding ₉ M) and Ding 982 2 The difference with Ding 9 M (Ding 9 82_ Ding ₉ M) is 0° or more and 60° or less independently, The concentration of the ultraviolet absorber in the resin is 5 wt% or more and 20 wt% or less, The ratio of the thickness of the intermediate layer to the total of the thickness of the first outer layer 1 and the thickness of the second outer layer 2 (Chomi / (Chohachi 1 + Choha 2)) is: Laminated film that is .1 or more and 0.35 or less. [Claim 2] 280° and load of the resin 81 2.1 The melt mass flow rate at 61<9 is

(9/1001 丨), and the melt mass flow rate of the resin 2 at 280° 〇 and load 2.1 61<9 is [¾2 (9/100 〇1丨1^), and The melt mass rate of the resin at 280° and load of 2.1 61 <9 is

) Is

And the ratio of 8 and 2 (?¾mi/[¾2) are independent of each other. The laminated film according to claim 1, which is 3.5 or more and 15.0 or less. [Claim 3] The concentration of the ultraviolet absorber in the resin 1 and the concentration of the ultraviolet absorber in the resin 2 are independently 0% by weight or more and 5% by weight or less. 〇 2020/174975 33 卩 (: 171-1? 2020 /002831 The laminated film according to claim 1 or 2, which is full. 4. The first outer layer is provided in direct contact with one surface of the intermediate layer, and the second outer layer is provided in direct contact with the other surface of the intermediate layer. The laminated film according to any one of claims 1 to 3. [Claim 5]

Ten % Or less, the ultraviolet absorber contained in the intermediate layer contains at least one selected from the group consisting of benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers, any one of claims 1 to 4. The laminated film according to item 1. [Claim 6] The laminated film according to any one of claims 1 to 5, further comprising a transparent conductive layer. 7. The laminated film according to claim 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.