JP2016169349A - Method fo producing cast film of addition polymer of norbornene compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently producing a cast film of an addition polymer of a norbornene compound which is excellent in transparency and has excellent slipperiness (film-winding properties).SOLUTION: There is provided a method for producing a cast film that includes applying a resin solution in which an addition polymer of a norbornene compound is dissolved in an organic solvent onto a resin film support, forming a flow casting film, evaporating the organic solvent, and then peeling a resin film support, where a substance is used as the resin film support, of which surface roughness (PV) represented by the maximum height difference of the surface is in a range of 0.010 to 0.300 μm and a wet tension is in a range of 50-75 mN/m.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a cast film having excellent transparency comprising a norbornene compound addition polymer. More specifically, the present invention relates to a method for efficiently forming a film for an optical material comprising a norbornene compound addition polymer and excellent in transparency, heat resistance, dimensional stability and the like.

  In the field of optical parts such as lenses, liquid crystal display elements, display substrates such as color filters and EL display element substrates, and optical materials such as backlights and light guide plates, inorganic glass has been generally used. However, inorganic glass has drawbacks such as being easily broken, lacking in flexibility, large specific gravity, and poor workability, and is insufficient to meet the recent demands for weight reduction, size reduction, and density increase. Therefore, there is a strong demand for replacement with transparent resin.

When a transparent resin is used for an optical material, very high performance is required in terms of heat resistance, chemical resistance, low water absorption and the like in addition to transparency. For example, in the manufacture of a display element substrate, processing at a high temperature is required in the process of laminating a metal or metal oxide thin film, but deformation of the substrate due to heat, dimensional variation due to water absorption, and the like are serious problems. However, acrylic resins and polycarbonate resins conventionally used for optical materials have the disadvantage of low heat resistance and high water absorption, and are not satisfactory.
Therefore, a cyclic olefin addition polymer has been proposed as a resin that satisfies transparency, heat resistance, chemical resistance, low water absorption and optical properties, and a liquid crystal display substrate material using this polymer has been proposed (patent) Reference 1).

Cyclic olefin addition polymers, particularly polynorbornene, have a high glass transition temperature of 250 ° C. or higher, and are thus excellent in heat distortion resistance during high-temperature processing. Moreover, since polynorbornene has extremely low hygroscopicity, it has excellent dimensional stability against changes in humidity in the environment of use. Furthermore, since its linear expansion coefficient is as low as about 55 ppm / ° C, it has excellent dimensional stability against thermal fluctuations. ing.
However, polynorbornene has a problem that it cannot be formed into a film by a casting method because of its low solubility in general solvents.

As an improvement measure, an addition polymer with a norbornene compound having a polar group has been proposed (Patent Document 2). By addition polymerization of a norbornene compound having a polar group, the solubility in a general solvent was increased, and film formation by a casting method became possible.
In optical material applications, high transparency is required, and for this reason, highly controlled high surface smoothness is required. On the other hand, in order to efficiently form a film of good quality, it is indispensable to run stably and smoothly in a conveyance line in production and obtain a good winding form. The slipperiness of the film surface must be good. However, when the surface smoothness of the film is increased, there is a problem that the slipperiness of the film is deteriorated.

In order to increase the slipperiness of the film, generally, inorganic particles such as silica and calcium carbonate are added to the resin solution to form fine irregularities on the film surface, thereby improving the slipperiness of the film (Patent Document 3). . However, in this case, there is a problem that the optical properties of the film are deteriorated.
Moreover, the method of laminating | stacking an anti blocking layer on the surface of a film and improving slipperiness is also known (patent document 4). However, since the norbornene compound addition polymer has an alicyclic structure as the main skeleton, the surface energy is small, and the laminated anti-blocking layer peels off without adhering to the norbornene compound addition polymer film. It was.

On the other hand, a method for improving slipperiness by imparting appropriate irregularities to the surface of the film itself is known (Patent Document 5). In particular, when a film is formed by a casting method, the surface shape of the support can be transferred to the film by casting on a support having appropriate unevenness, and a film with efficiently controlled unevenness can be formed ( Patent Document 6).
On the other hand, as described above, the norbornene compound addition polymer is difficult to wet the support surface of the cast film because the main skeleton has an alicyclic structure. For this reason, even if cast on a support having appropriate irregularities, the support is not sufficiently solidified in the process of vaporizing the solvent and concentrating the norbornene compound addition polymer component (resin component). The film peeled off, and there was a problem that the unevenness of the film surface could not be controlled.
Therefore, it has been reported that an easy-adhesion layer is provided on the surface of the support so that the film is in close contact with the support during drying. (Patent Document 7).

In addition, when an easy-adhesion layer is provided, the polar group contained in the norbornene compound addition polymer component often interacts strongly with the easy-adhesion layer, and the film surface becomes extremely rough when the molded cast film is peeled off from the support. There was also a problem that transparency deteriorated.
For this reason, the film forming method of the norbornene compound addition polymer film which has appropriate adhesiveness with respect to a support body, and has good slipperiness after peeling has been demanded.

JP-A-6-202091 Japanese National Patent Publication No. 11-505880 JP-A-55-133431 JP 2007-182519 A JP 2004-130736 A JP 2003-33932 A Japanese Patent No. 4597418

  An object of the present invention is to provide a method for efficiently producing a norbornene compound-added polymer film having excellent transparency and excellent slipperiness (film winding property).

  As a result of intensive studies to solve the above problems, the present inventors have found that a resin solution containing a norbornene compound having a norbornene compound monomer having a specific substituent as a repeating unit as a resin component has an appropriate surface. It has been found that the above-mentioned problems can be solved by casting (casting) a resin film support having roughness and wetting tension, and the present invention has been completed.

（式中、Ｒ¹は炭素数１〜１０のアルキル基を表し、Ｒ²〜Ｒ⁴は、それぞれ独立して水素原子または炭素数１〜１０のアルキル基を表し、Ｒ²〜Ｒ⁴は、互いに結合して環を形成していてもよく、ｎ¹は０または１である。）
で示されるモノマーユニットを含むノルボルネン化合物付加重合体を有機溶媒に溶解した樹脂溶液を、樹脂フィルム支持体上に塗工して流延膜を形成し、有機溶媒を揮発させた後、樹脂フィルム支持体を剥離するキャストフィルムの製造方法であって、樹脂フィルム支持体表面の、最大高低差で表される表面粗さ（ＰＶ）が０．０１０〜０．３００μｍの範囲であり、濡れ張力が５０〜７５ｍＮ／ｍの範囲であることを特徴とするキャストフィルムの製造方法。
［２］ ノルボルネン化合物付加重合体が、前記一般式（１）及び一般式（２）

（式中、Ｒ⁵〜Ｒ⁸は、それぞれ独立して水素原子または炭素数１〜１０のアルキル基を表し、Ｒ⁵〜Ｒ⁸は、互いに結合して環を形成していてもよく、ｎ²は０または１である。）
で示されるモノマーユニットを含む共重合体である前項１に記載のキャストフィルムの製造方法。
［３］ 一般式（１）で示されるユニットが、下記式（Ａ）

で示される前項１または２に記載のキャストフィルムの製造方法。
［４］ 一般式（２）で示されるユニットが、下記構造式（Ｂ）

で示される前項２または３に記載のキャストフィルムの製造方法。
［５］ 樹脂フィルム支持体の最大高低差で表される表面粗さ（ＰＶ）が０．０３〜０．２５０μｍの範囲である、前項１〜４のいずれかに記載のキャストフィルムの製造方法。
［６］ 樹脂フィルム支持体の濡れ張力が５９〜７３ｍＮ／ｍの範囲である前項１〜５のいずれかに記載の製膜方法。
［７］ 樹脂フィルム支持体がポリエチレンテレフタレートフィルムである前項１〜６のいずれかに記載のキャストフィルムの製造方法。
［８］ 樹脂溶液の有機溶媒がトルエンまたはジクロロメタンである前項１〜７のいずれかに記載のキャストフィルムの製造方法。
［９］ 前項１〜８のいずれかに記載のキャストフィルムの製造方法で得られた光学フィルム。
［１０］ 前記光学フィルムが表示素子用部材用である前項９に記載の光学フィルム。
［１１］ 最大高低差で表される表面粗さ（ＰＶ）が、０．０１０μｍ〜０．３００μｍであり、一般式（１）で示されるモノマーユニットを含むノルボルネン化合物付加重合体からなる、厚み２０〜３００μｍのキャストフィルム。 That is, this invention relates to the manufacturing method of the film consisting of the norbornene compound addition polymer of the following [1]-[11], an optical film, and a cast film. In the present invention, the term “film” includes both “film” and “sheet” which are strictly distinguished by their thickness.
[1] General formula (1)

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ^{2 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ^{2 to} R ⁴ are: And may be bonded to each other to form a ring, and n ¹ is 0 or 1.)
A resin solution in which a norbornene compound addition polymer containing a monomer unit represented by is dissolved in an organic solvent is applied onto a resin film support to form a cast film, the organic solvent is volatilized, and then the resin film is supported. A method for producing a cast film for peeling a body, wherein the surface roughness (PV) of the resin film support surface expressed by the maximum height difference is in the range of 0.010 to 0.300 μm, and the wetting tension is 50. A method for producing a cast film, which is in a range of ˜75 mN / m.
[2] The norbornene compound addition polymer is the above general formula (1) or general formula (2).

(Wherein R ^{5 to} R ⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ^{5 to} R ⁸ may be bonded to each other to form a ring; ² is 0 or 1.)
2. The method for producing a cast film as described in 1 above, which is a copolymer containing a monomer unit represented by
[3] The unit represented by the general formula (1) is represented by the following formula (A)

The manufacturing method of the cast film of the preceding clause 1 or 2 shown by these.
[4] The unit represented by the general formula (2) has the following structural formula (B)

4. A method for producing a cast film as described in 2 or 3 above.
[5] The method for producing a cast film according to any one of items 1 to 4, wherein the surface roughness (PV) represented by the maximum height difference of the resin film support is in the range of 0.03 to 0.250 μm.
[6] The film forming method according to any one of items 1 to 5, wherein the wet tension of the resin film support is in the range of 59 to 73 mN / m.
[7] The method for producing a cast film according to any one of items 1 to 6, wherein the resin film support is a polyethylene terephthalate film.
[8] The method for producing a cast film as described in any one of 1 to 7 above, wherein the organic solvent of the resin solution is toluene or dichloromethane.
[9] An optical film obtained by the method for producing a cast film according to any one of 1 to 8 above.
[10] The optical film as described in 9 above, wherein the optical film is for a display element member.
[11] Thickness of 20 having a surface roughness (PV) represented by a maximum height difference of 0.010 μm to 0.300 μm and comprising a norbornene compound addition polymer containing a monomer unit represented by the general formula (1) Cast film of ~ 300μm.

  The film comprising the norbornene compound addition polymer of the present invention has excellent transparency and optical properties and is useful as an optical material.

  The cast film of the present invention is a resin film having a suitable surface roughness and wetting tension obtained by dissolving a resin solution obtained by dissolving a norbornene compound addition polymer having a norbornene compound monomer having a specific substituent as a repeating unit in an organic solvent. It is obtained by pouring (casting) on a support and volatilizing (drying) the solvent of the resin solution. The cast film after drying is peeled off from the resin film substrate. The casting, drying and peeling steps may be batch processing, but industrially preferred is a continuous method. For example, a roll-shaped long resin film support is continuously fed out, and a resin solution is continuously cast on the resin film support, followed by drying, peeling, and winding the cast film into a roll. May be.

一般式（１）中、Ｒ¹は炭素数１〜１０のアルキル基を表し、Ｒ²〜Ｒ⁴はそれぞれ独立に、水素原子または炭素数１〜１０のアルキル基を表し、また、Ｒ²〜Ｒ⁴は、互いに結合して環を形成していてもよい。ｎ¹は０または１である。 [Norbornene compound addition polymer]
The norbornene compound addition polymer used in the present invention is a norbornene compound addition polymer containing a monomer unit represented by the general formula (1).

In General Formula (1), R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ^{2 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² to R ⁴ may be bonded to each other to form a ring. n ¹ is 0 or 1.

The alkyl group having 1 to 10 carbon atoms represented by R ¹ in the general formula (1) may be linear or branched. Examples of the linear alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, and an n-decyl group. . Examples of the branched alkyl group include isopropyl group, isobutyl group, sec-butyl group, neopentyl group, isohexyl group, isooctyl group, and isodecyl group. In these, a C1-C3 linear alkyl group is preferable in terms of economical efficiency. From the viewpoint of monomer production cost, a methyl group is particularly preferable.

R < ² > -R < ⁴ > in General formula (1) represents a hydrogen atom or a C1-C10 alkyl group each independently. In the case of an alkyl group having 3 to 10 carbon atoms, it may be branched. Examples of these alkyl groups include the same alkyl groups as those described above for R ¹ . Among these, a hydrogen atom is preferable from the viewpoint of monomer production cost. R ^{2 to} R ⁴ may be bonded to each other to form a ring. n ¹ is 0 or 1. From the viewpoint of monomer production cost, n ¹ is preferably 0.

When R ^{2 to} R ⁴ are hydrogen atoms and n ¹ is 0, the norbornenes that are the basis of the monomer unit represented by the general formula (1) are as follows when R ¹ is an alkyl group having 1 carbon atom: 2-acetoxymethyl-5-norbornene, when R ¹ is an alkyl group having 2 carbon atoms, 2-[(ethylcarbonyloxy) methyl] -5-norbornene, R ¹ is a linear alkyl group having 3 carbon atoms Sometimes 2-[(propylcarbonyloxy) methyl] -5-norbornene.
Further, the monomer unit represented by the general formula (1) is not limited to one type. You may have 2 or more types of monomer units.

The monomer unit represented by the general formula (1) is preferably one represented by the formula (A) derived from 2-acetoxymethyl-5-norbornene from the viewpoint of production cost.

一般式（２）中、Ｒ⁵〜Ｒ⁸はそれぞれ独立して水素原子または炭素数１〜１０のアルキル基を表し、また、Ｒ⁵〜Ｒ⁸は、互いに結合して環を形成していてもよい。ｎ²は０または１である。 Furthermore, the norbornene compound addition polymer for obtaining the film of the present invention may be a norbornene compound addition polymer containing monomer units represented by the general formulas (1) and (2).

In general formula (2), R ^{5 to} R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ^{5 to} R ⁸ are bonded to each other to form a ring. Also good. n ² is 0 or 1.

R < ⁵ > -R < ⁸ > in General formula (2) represents a hydrogen atom or a C1-C10 alkyl group each independently, and in the case of a C3-C10 alkyl group, you may branch. Examples of these alkyl groups include those similar to the alkyl group represented by R ¹ in the general formula (1). R ^{5 to} R ⁸ may be bonded to each other to form a ring.
Among these, R ^{5 to} R ⁸ are preferably hydrogen atoms from the viewpoint of monomer production cost. n ² is 0 or 1. From the viewpoint of monomer production cost, n ² is preferably 0. When R ^{5 to} R ⁸ are hydrogen atoms and n ² is 0, the norbornenes that form the basis of the monomer unit represented by the general formula (2) are 2-norbornene.

Further, the monomer unit represented by the general formula (2) is not limited to one type. You may have 2 or more types of monomer units.
The monomer unit represented by the general formula (2) is preferably one represented by the formula (B) derived from 2-norbornene from the viewpoint of production cost.

  In the norbornene-based copolymer composed of the monomer units represented by the general formula (1) and the general formula (2), the content of the monomer unit represented by the general formula (1) is preferably 10 to 80 mol%, 15 -70 mol% is more preferable, and 20-60 mol% is further more preferable. In the present invention, a norbornene-based copolymer is used as a resin solution, which is cast on a resin film support and molded into a film, sheet or the like. The content of the monomer unit represented by the general formula (1) is 10 mol% or more. When it is, the solubility to an organic solvent will become favorable. If content is below 80 mol%, adhesiveness with a resin film support body will become moderate.

The content of the monomer unit represented by the general formula (1) is calculated from an integral value obtained by dissolving a powdery or film-like copolymer in an appropriate deuterated solvent, measuring ¹ H-NMR. be able to.

一般式（３）中、Ｒ⁹〜Ｒ¹²は、それぞれ独立して、水素原子；ハロゲン原子；窒素原子、酸素原子、硫黄原子、ハロゲン原子もしくはケイ素原子を含む官能基；ハロゲン原子もしくは前記官能基を有していてもよい炭素数１〜２０の炭化水素基を表す。また、Ｒ⁹〜Ｒ¹²は、互いに結合して環を形成していてもよい。ｎ³は０または１である。ただし、一般式（１）、一般式（２）で示される構造を除く。 Furthermore, as a film comprising a norbornene compound addition polymer containing a monomer unit represented by the general formula (1), a norbornene compound addition polymer further comprising a monomer unit represented by the general formula (3), or a further general formula (2 ) And a norbornene compound addition polymer containing both of the general formula (3) are also preferable.

In general formula (3), R ^{9 to} R ¹² are each independently a hydrogen atom; a halogen atom; a functional group containing a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom or a silicon atom; a halogen atom or the functional group The C1-C20 hydrocarbon group which may have this is represented. R ^{9 to} R ¹² may be bonded to each other to form a ring. n ³ is 0 or 1. However, the structures represented by the general formula (1) and the general formula (2) are excluded.

Specific examples of R ^{9 to} R ¹² in the general formula (3) include a hydrogen atom; a halogen atom such as a chlorine atom, a bromine atom, and a fluorine atom; a hydroxyl group, an alkoxy group, an aryloxy group, a carbonyl group, and a hydroxycarbonyl group. , Functional groups containing oxygen atoms such as alkoxycarbonyl groups and aryloxycarbonyl groups; nitrogen such as amino groups, alkylamino groups, arylamino groups, aminocarbonyl groups, alkylaminocarbonyl groups, arylaminocarbonyl groups, and cyano groups Functional groups containing atoms; functional groups containing sulfur atoms such as mercapto groups, alkoxythio groups, and aryloxythio groups; silicon such as silyl groups, alkylsilyl groups, arylsilyl groups, alkoxysilyl groups, and aryloxysilyl groups Mention may be made of functional groups containing atoms. Moreover, hydrocarbon groups, such as a C1-C20 alkyl group (for example, a hydroxymethyl group, a methoxymethyl group, etc.), an alkenyl group, and an aryl group which may have these functional groups, are also mentioned. Furthermore, R ^{9 to} R ¹² may be bonded to each other to form a ring, and examples of such examples include an acid anhydride structure, a carbonate structure, and a dithiocarbonate structure. The refractive index of the norbornene compound addition polymer of this invention can be adjusted by introduce | transducing a bromine atom etc. as R < ⁹ > -R < ¹² > of General formula (3). In addition, the introduction of a hydroxyl group can improve the water vapor barrier property.

  It is preferable that the norbornene addition polymer to be the film of the present invention is basically composed only of norbornenes. However, even in this case, the presence of a minute amount of the third monomer unit that hardly changes the properties of the norbornene addition polymer of the present invention, for example, 1 mol% or less, is not excluded. Moreover, the norbornene addition polymer manufactured with the manufacturing method of this invention may copolymerize the 3rd monomer in the range which does not impair the effect of this invention for physical property improvement.

  Although there is no restriction | limiting in particular in a 3rd monomer, The monomer which has an ethylenic carbon-carbon double bond is preferable, for example, alpha-olefins, such as ethylene, propylene, 1-butene, 1-pentene, and 1-hexene; Aromatic vinyl compounds such as styrene, α-methylstyrene and divinylbenzene; chain conjugated dienes such as 1,3-butadiene and isoprene; vinyl ethers such as ethyl vinyl ether and propyl vinyl ether; methyl acrylate, ethyl acrylate, 2- Examples thereof include acrylates such as ethylhexyl acrylate; methacrylates such as methyl methacrylate and ethyl methacrylate. Of these, α-olefins such as ethylene, propylene, and 1-hexene, and aromatic vinyl compounds such as styrene are particularly preferable.

  In the norbornene compound addition polymer used in the film of the present invention, the copolymerization mode of each monomer unit can be random, block, or alternating depending on the polymerization conditions, but from the viewpoint of improving the physical properties of the copolymer, It is desirable to be random.

  The number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) of the norbornene compound addition polymer produced by the production method of the present invention is preferably 50,000 to 2,000,000. Furthermore, 100,000 to 1,500,000 is more preferable. If the number average molecular weight in terms of polystyrene is less than 50,000, the mechanical strength is insufficient. When the number average molecular weight in terms of polystyrene exceeds 2,000,000, not only the solubility in a solvent is lowered when a cast film is formed, but also the solution viscosity is increased and the molding processability is lowered. Further, the molecular weight distribution Mw / Mn (weight average molecular weight / number average molecular weight) is preferably 1.00 to 4.00, more preferably 1.30 to 3.50, and still more preferably 1.50 to 3.30. When the molecular weight distribution is wide, the solution at the time of forming the cast film is difficult to be uniform, so that it is difficult to produce a good film.

[Production of norbornene compound addition polymer]
The norbornene compound addition polymer used in the resin solution of the present invention can be produced by addition polymerization of a norbornene-based monomer in the presence of a polymerization catalyst.
The production method includes (i) a method of obtaining a single addition polymer of a norbornene monomer by addition polymerization of only one type of norbornene monomer, and (ii) an addition copolymerization of two or more types of norbornene monomers. A method of obtaining an addition copolymer of a norbornene monomer, (iii) addition copolymerization of one or more norbornene monomers with one or more other vinyl monomers copolymerizable with the norbornene monomers, One of the methods for obtaining an addition copolymer.

一般式（４）中、Ｒ¹は炭素数１〜１０のアルキル基を表し、Ｒ²〜Ｒ⁴はそれぞれ独立に、水素原子または炭素数１〜１０のアルキル基を表し、また、Ｒ²〜Ｒ⁴は、互いに結合して環を形成していてもよい。ｎ¹は０または１である。 In order to produce a polymer having a skeleton represented by the general formula (1), it can be produced by addition polymerization of a norbornene compound represented by the general formula (4).

In General Formula (4), R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ^{2 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ² to R ⁴ may be bonded to each other to form a ring. n ¹ is 0 or 1.

Specifically, bicyclo [2.2.1] having a acetoxymethyl group such as 2-acetoxymethyl-5-norbornene hept-2-enes, 4-acetoxymethyl tetracyclo [6.2.1.1 ^{3 , 6} . Tetracyclo [6.2.1.1 ^3,6 . Having an acetoxymethyl group such as 0 ^2,7 ] dodec-9-ene. ^0,7 ] dodec-9-enes. Of these, 2-acetoxymethyl-5-norbornene is preferred.

一般式（５）中、Ｒ⁵〜Ｒ⁸はそれぞれ独立して水素原子または炭素数１〜１０のアルキル基を表し、また、Ｒ⁵〜Ｒ⁸は、互いに結合して環を形成していてもよい。ｎ²は０または１である。 In order to produce a polymer having a skeleton represented by the general formula (2), it can be produced by addition polymerization of a norbornene compound represented by the general formula (5).

In general formula (5), R ^{5 to} R ⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ^{5 to} R ⁸ are bonded to each other to form a ring. Also good. n ² is 0 or 1.

Specifically, 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-n-butyl-2-norbornene, 5-n-hexyl-2-norbornene, 5-n-decyl 2-norbornene, 5-cyclohexyl-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, 5-phenyl-2-norbornene, 5-benzyl-2-norbornene, dicyclopentadiene, dihydro dicyclopentadiene, tetracyclo [9.2.1.0 ^2,10. 0 ^3,8] tetradec -3,5,7,12- tetraene, tetracyclo [10.2.1.0 ^2,11. Bicyclo [2.2.1] hept-2-enes having an unsubstituted or hydrocarbon group such as 0 ^4,9 ] pentadeca-4,6,8,13-tetraene, tetracyclo [6.2.1.1. ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-n-butyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyclohexyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidenetetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-vinyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-phenyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7] tetracyclo an unsubstituted or a hydrocarbon group such as dodeca-4-ene [6.2.1.1 ^{3, 6.} 0 ^2,7 ] dodec-4-enes.
Of these, 2-norbornene is preferred.

一般式（６）中、Ｒ⁹〜Ｒ¹²は、それぞれ独立して、水素原子；ハロゲン原子；窒素原子、酸素原子、硫黄原子、ハロゲン原子もしくはケイ素原子を含む官能基；ハロゲン原子もしくは前記官能基を有していてもよい炭素数１〜２０の炭化水素基を表す。ただし、Ｒ⁹〜Ｒ¹²すべてが水素原子とはならない。また、Ｒ⁹〜Ｒ¹²は、互いに結合して環を形成していてもよい。ｎ³は０または１である。ただし、一般式（４）、一般式（５）で示されるノルボルネン化合物を除く。 In order to produce a polymer having a skeleton represented by the general formula (3), it can be produced by addition polymerization of a norbornene compound represented by the general formula (6).

In general formula (6), R ^{9 to} R ¹² are each independently a hydrogen atom; a halogen atom; a functional group containing a nitrogen atom, an oxygen atom, a sulfur atom, a halogen atom or a silicon atom; a halogen atom or the functional group The C1-C20 hydrocarbon group which may have this is represented. However, not all R ^{9 to} R ¹² are hydrogen atoms. R ^{9 to} R ¹² may be bonded to each other to form a ring. n ³ is 0 or 1. However, the norbornene compound shown by General formula (4) and General formula (5) is excluded.

  Specifically, methyl 5-norbornene-2-carboxylate, ethyl 5-norbornene-2-carboxylate, n-butyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate 2-ethyl-5-norbornene-2-carboxylate, n-butyl 2-methyl-5-norbornene-2-carboxylate, methyl 5-norbornene-2,3-dicarboxylate, 5-norbornene-2,3 -Bicyclo [2.2.1] hept-2-enes having an alkoxycarbonyl group such as ethyl dicarboxylate;

Tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] methyl dodeca-9-ene-4-carboxylate, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] Dodeca-9-ene-4-carboxylate, 4-methyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] methyl dodeca-9-ene-4-carboxylate, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylate, tetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having an alkoxycarbonyl group such as 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylate. 0 ^2,7 ] dodeca-9-enes;

Bicyclo [2.2.1] hept-2-enes having a hydroxycarbonyl group such as 5-norbornene-2-carboxylic acid and 5-norbornene-2,3-dicarboxylic acid; tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carboxylic acid, tetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a hydroxycarbonyl group such as 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic acid. 0 ^2,7 ] dodeca-9-enes;

Has hydroxyl groups such as 2-hydroxy-5-norbornene, 2-hydroxymethyl-5-norbornene, 2,2-di (hydroxymethyl) -5-norbornene, 2,3-di (hydroxymethyl) -5-norbornene Bicyclo [2.2.1] hept-2-enes; tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-en-4-ol, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-methanol, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4,5-dimethanol and the like tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-enes;

Bicyclo [2.2.1] hept having an acetoxyl group such as 2-acetoxy-5-norbornene, 2,2-di (acetoxymethyl) -5-norbornene, 2,3-di (acetoxymethyl) -5-norbornene -2-enes; 4-acetoxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-acetoxymethyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4,5-di (acetoxymethyl) tetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having an acetoxyl group such as 0 ^2,7 ] dodec-9-ene. 0 ^2,7 ] dodeca-9-enes;

Bicyclo [2.2.1] hept-2-enes having a functional group containing a nitrogen atom such as 5-norbornene-2-carbonitrile and 5-norbornene-2-carboxamide; tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4-carbonitrile, tetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a functional group containing a nitrogen atom such as 0 ^2,7 ] dodec-9-ene-4-carboxamide. 0 ^2,7 ] dodeca-9-enes;

Bicyclo [2.2.1] hept-2-enes having a halogen atom such as 2-chloro-5-norbornene and 2-fluoro-5-norbornene; 4-chlorotetracyclo [6.2.1.1 ^{3 , 6} . 0 ^2,7 ] dodec-9-ene, 4-fluorotetracyclo [6.2.1.1 ^3,6 . ^02,7 ] tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-enes;

Bicyclo [2.2.1 having functional groups containing silicon atoms such as 2-trimethylsiloxy-5-norbornene, 2-trimethoxysilyl-5-norbornene, 2-tris (trimethoxysilyloxy) silyl-5-norbornene ] Hept-2-enes; 4-trimethylsiloxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-trimethoxysilyltetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene, 4-tris (trimethoxysilyloxy) silyltetracyclo [6.2.1.1 ^3,6 . Tetracyclo [6.2.1.1 ^3,6 . Having a functional group containing a silicon atom such as 0 ^2,7 ] dodec-9-ene. 0 ^2,7 ] dodeca-9-enes;

Bicyclo [2] having an acid anhydride structure such as 5-norbornene-2,3-dicarboxylic acid anhydride, 5-norbornene-2,3-carbonate, 5-norbornene-2,3-dithiocarbonate, carbonate structure, dithiocarbonate structure 2.2.1] hept-2-enes; tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodec-9-ene-4,5-dicarboxylic anhydride, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodeca-9-ene-4,5-carbonate, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] tetracyclo [6.2.1.1 ^3,6 . Having acid anhydride structure, carbonate structure, dithiocarbonate structure such as dodeca-9-ene-4,5-dithiocarbonate. 0 ^2,7 ] dodeca-9-enes and the like.

The polymerization catalyst for obtaining the norbornene compound addition polymer used in the present invention is not particularly limited. Specific examples include Group 8 elements, Group 9 elements, and Group 10 transition metals having a π-allyl ligand described in JP 2012-77284 A and bidentate ligands. A polymerization catalyst composed of salicylaldimine, which is: Although the said polymerization catalyst may be used independently, it is preferable to use a co-catalyst and a phosphine-type ligand simultaneously.
The polymerization reaction can be carried out by bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, precipitation polymerization or the like.

[Organic solvent]
The organic solvent for dissolving the norbornene compound addition polymer into a resin solution is not particularly limited as long as it can dissolve the norbornene compound addition polymer and does not affect the surface of the resin film support during casting. Not. Specific examples include aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as chloroform, dichloromethane and orthodichlorobenzene; amides such as dimethylformamide and dimethylacetamide; Among these, toluene or dichloromethane that can be easily vaporized is preferable from the viewpoint of production cost. These solvents may be used alone or in combination of two or more.
[Resin solution]
The means for dissolving the norbornene compound addition polymer in an organic solvent is not particularly limited. Specific examples include a method of adding a norbornene compound addition polymer to an organic solvent and stirring at room temperature, a method of heating and stirring, a method of applying ultrasonic waves; polymerization in an organic solvent; The method of obtaining etc. are mentioned.

  In the present invention, the resin concentration of the resin solution is preferably 5 to 60% by mass, more preferably 10 to 40% by mass, and still more preferably 10 to 30% by mass. If the resin concentration is too low, the viscosity will be too low and it will be difficult to adjust the thickness. In addition, production efficiency deteriorates, leading to increased costs. On the other hand, when the resin concentration is too high, the viscosity becomes high, the film-forming property is poor, and unevenness may be increased. In addition, by filtering the resin solution before casting the resin solution, it is possible to reduce impurities in the film, increasing the transmittance of the film of the present invention, and more suitable for optical film applications.

  In the present invention, the viscosity of the resin solution is preferably 500 to 100,000 mPa · s at 25 ° C. More preferably, it is 1000-50000 mPa * s, More preferably, it is 1000-20000 mPa * s. If the viscosity is too low, the resin solution cast on the resin film support flows, making it difficult to adjust the cast film thickness. In addition, production efficiency deteriorates, leading to increased costs. On the other hand, if the viscosity is too high, the filter may be clogged, or the film forming property may be poor and unevenness may be increased. As for the viscosity of the resin solution, an E type viscometer TV-20 manufactured by Toki Sangyo Co., Ltd. was used. It can be measured under the condition of 1 ° 34 ″.

  It is preferable that the resin component constituting the resin solution of the present invention is basically composed only of a norbornene addition polymer. However, even in this case, a transparent resin (for example, a cyclic olefin addition polymer, a hydrogenated cyclic olefin ring-opening) having a minute amount that does not substantially change the properties of the resin solution of the present invention, for example, 1% by mass or less. Polymer, addition copolymer of α-olefin and cyclic olefin, crystalline α-olefin polymer, copolymer of rubbery ethylene and α-olefin having 3 or more carbon atoms, hydrogenated The presence of butadiene polymers, hydrogenated butadiene / styrene block copolymers, hydrogenated isoprene polymers, etc.) is not excluded.

〔Additive〕
You may mix | blend various additives with a resin solution as needed.
Examples of such additives include antioxidants, fluorescent agents, ultraviolet absorbers, antistatic agents, light stabilizers, near infrared absorbers, colorants such as dyes and pigments, plasticizers, flame retardants, and crosslinking agents. Can be mentioned.
The method for blending these additives is not particularly limited.

Examples of the antioxidant include hindered phenol antioxidants, phosphorus antioxidants, lactone antioxidants, amine antioxidants, and sulfur antioxidants.
It is preferable that the norbornene compound addition polymer used for the film of this invention contains 0.1-5 mass parts antioxidant with respect to 100 mass parts of norbornene compound addition polymers. As for the quantity of antioxidant, it is more preferable that it is 0.2-3 mass parts with respect to 100 mass parts of norbornene compound addition polymers, and it is further more preferable that it is 0.5-2 mass parts. If the amount of the antioxidant is too small, the effects of the present invention may not be sufficiently obtained. On the other hand, if the amount of the antioxidant is too large, the effect of the present invention may be reduced by bleeding at the interface between the film and the resin film support during casting to prevent transfer. In addition, the antioxidant is scattered during the film formation step or the heat treatment after the formation, which may contaminate the film production apparatus or the heat treatment apparatus.

  It is preferable that the antioxidant contains at least a hindered phenol antioxidant. Moreover, in this invention, it is preferable that the quantity of hindered phenolic antioxidant is larger than the quantity of antioxidants other than a hindered phenolic antioxidant. If the amount of antioxidants other than hindered phenolic antioxidants is equal to or greater than the amount of hindered phenolic antioxidants, the amount of bleeds on the surface increases, resulting in a decrease in optical properties and an antioxidant effect. There is a possibility that the problem of lowering may occur.

  In addition, as antioxidant, when 1-99 mass parts of antioxidants other than hindered phenolic antioxidant are used together with respect to 100 mass parts of hindered phenolic antioxidant, a film with high thermal dimensional stability is obtained. It is preferable because it is easy to obtain, and the weight ratio of hindered phenol antioxidant to antioxidant other than hindered phenol antioxidant (oxidation other than hindered phenol antioxidant / hindered phenol antioxidant) The inhibitor is particularly preferably 1.5 or more.

Examples of the hindered phenol antioxidant include alkyl-substituted hindered phenol antioxidants, alkoxy-substituted hindered phenol antioxidants, and triazine group-containing hindered phenol antioxidants.
Among these, alkyl-substituted hindered phenolic antioxidants are preferable, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4, 6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene is particularly preferred.
These hindered phenolic antioxidants may be used alone or in combination of two or more.

Antioxidants other than the hindered phenol-based antioxidant that can be used in the present invention are not particularly limited.
Specific examples thereof include phosphorus antioxidants, lactone antioxidants, amine antioxidants, and sulfur antioxidants. Among these, a phosphorus-based antioxidant is preferable because a film having high thermal dimensional stability is easily obtained.

The phosphorus-based antioxidant is not particularly limited as long as it is usually used. Specific examples thereof include bis- (2,6-di-t-butyl-4-methylphenyl) pentapentaerythritol diester. Phosphite, tris (2,4-di-t-butylphenylphosphite), tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4′-biphenylenediphosphonite, bis- ( 2,6-dicumylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, tris (mixed mono and di-nonylphenyl phosphite), bis ( 2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methoxycarbonylethyl- Phenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-octadecyloxycarbonylethyl-phenyl) pentaerythritol diphosphite, and the like. Among these, monophosphite compounds are preferable, and tris (2,4-di-t-butylphenyl phosphite) is particularly preferable.
These phosphorus antioxidants may be used alone or in combination of two or more.
As an antioxidant having a radical scavenging action and a chain transfer agent transfer action as in the case of a hindered phenol antioxidant, a lactone antioxidant or an amine antioxidant can be used in combination.

  It is preferable that the norbornene compound addition polymer used for the base film of this invention contains 0.1-5 mass parts antioxidant dispersibility improvement agent with respect to 100 mass parts of norbornene compound addition polymers. This antioxidant dispersibility improver is compatible with the norbornene compound addition polymer and improves the dispersibility of the antioxidant.

  The amount of the antioxidant dispersibility improver is more preferably 0.2 to 5 parts by mass, and still more preferably 0.4 to 4 parts by mass with respect to 100 parts by mass of the norbornene compound addition polymer. If this amount is too small, the effects of the present invention may not be sufficiently obtained. When the amount is too large, the antioxidant dispersibility improving agent may be scattered during the film formation step or the heat treatment after the formation, which may contaminate the film production apparatus or the heat treatment apparatus. Furthermore, it acts strongly as a plasticizer for the norbornene compound addition polymer, and there is a possibility that the heat resistance of the molded product is significantly lowered.

  As the antioxidant dispersibility improver, any of carboxylic acid ester, sulfonic acid ester, phosphoric acid ester, aliphatic ether and aromatic ether can be used, and carboxylic acid ester is preferred. These dispersants may be used alone or in combination of two or more.

Specific examples of the carboxylic acid ester that can be used as an antioxidant dispersion improver include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, and phthalic acid. Phthalic acid monoester or diester compounds such as diisononyl, diisodecyl phthalate, di-n-octyl hydrophthalate, 2-ethylhexyl hydrophthalate, isodecyl hydrophthalate, butyl benzyl phthalate; butyl oleate, ethyl oleate, oleic acid Fatty acid ester compounds such as tetrahydrofurfuryl, methyl acetylricinoleate, methyl abietic acid, butyl stearate, methyl pentachlorostearate; diethylene glycol benzoate, triethylene glycol-2-ethyl Glycol ester compounds such as rubutylate and pentaerythritol hexaester; dibutyl malonate, diisopropyl succinate, dibutyl succinate, diisopropyl adipate, dibutyl adipate, diisobutyl adipate, di-n-hexyl adipate, di-2 adipate -Ethylhexyl, dioctyl adipate, di-2-ethylhexyl azelate, dibutyl sebacate, di-2-ethylhexyl sebacate, dibutyl maleate, di-n-hexyl maleate, di-2-ethylhexyl maleate, dibutyl fumarate Aliphatic dibasic acid esters such as trimellitic acid trisbutyl and trimellitic acid tris-2-ethylhexyl trimellitic acid ester compounds.
Among these, ester compounds having an aromatic ring such as phthalic acid monoester or diester compounds and trimellitic acid ester compounds are preferable, and phthalic acid diester compounds are particularly preferable.

  These antioxidant dispersibility improvers may be appropriately selected in consideration of the combination with the antioxidant to be used. However, the antioxidant dispersibility improver should be a liquid having a boiling point of 200 ° C. or higher at room temperature and pressure. preferable.

  Specific examples of satisfying such conditions include carboxylic acid esters such as dibutyl succinate (274 ° C./760 mmHg), dioctyl adipate (230 ° C./760 mmHg), dibutyl adipate (145 ° C./4 mmHg), Aliphatic dibasic acid esters such as diisobutyl adipate (293 ° C./760 mmHg), di-2-ethylhexyl adipate (335 ° C./760 mmHg), di-2-ethylhexyl sebacate (377 ° C./760 mmHg); diethyl phthalate ( 298 ° C / 760 mmHg), diheptyl phthalate (235-245 ° C / 10 mmHg), di-n-octyl phthalate (210 ° C / 760 mmHg), diisodecyl phthalate (420 ° C / 760 mmHg), and the like. it can. Moreover, as a phosphate ester type | system | group, a tributyl phosphate (289 degreeC / 760mmHg) etc. can be mentioned, for example.

  The total amount of the antioxidant and the antioxidant dispersibility improver is preferably 0.2 to 10 parts by mass, more preferably 2 to 9 parts by mass with respect to 100 parts by mass of the norbornene compound addition polymer. If this amount is too small, the effects of the present invention may not be sufficiently obtained. When the amount is too large, the antioxidant or the antioxidant dispersibility improver is scattered during the film forming process or after the heat treatment, and the thermal dimensional change rate is increased or the film production apparatus or the heat treatment apparatus is contaminated. There is a risk of doing so. Furthermore, it acts strongly as a plasticizer for the norbornene compound addition polymer, and there is a possibility that the heat resistance of the molded product is significantly lowered.

  The ultraviolet absorber is not particularly limited and may be those commonly used. Among them, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers are preferable. A UV absorber is preferred. Examples of benzophenone ultraviolet absorbers include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-butylphenyl) benzotriazole and 2- (2-hydroxy-3). '-Tert-butylphenyl) benzotriazole and the like.

[Resin film support]
The material of the resin film as the resin film support is not particularly limited as long as it has high rigidity and high organic solvent resistance. Specifically, polyolefin resin, vinyl chloride resin, polyester resin, polyethylene naphthalate resin, polyamide resin, polyimide resin, polyketone resin, polyphenylene oxide resin, polyphenylene sulfide resin, polysulfone resin, etc. Although it can be used, it is not limited to these. Among them, polyethylene terephthalate (PET) is a particularly preferable material that is easy to use because it is inexpensive and has excellent processability and high chemical resistance.

  The thickness of the film used as the support is preferably 10 μm or more and 500 μm or less, more preferably 100 μm or more and 200 μm or less. If the resin film support film is too thin, it will not be able to withstand the weight of the resin solution, causing sagging and causing unevenness in the thickness of the produced film. On the other hand, if the resin film support film is too thick, the production cost may increase. From the viewpoint of productivity, the length of the long resin film support film when produced by a continuous method is preferably 100 m or more, and more preferably 500 m or more. The width of the resin film support film depends on the size of the production apparatus, but 30 to 200 cm is appropriate.

In the present invention, a resin film support whose surface roughness (PV) represented by the maximum height difference is controlled within a certain range is used. PV is measured with a scanning probe microscope. Specific measurement conditions are as described in the Examples section.
The PV of the resin film support is in the range of 0.010 to 0.300 μm and in the range of 0.020 to 0.270 μm in that a film having good slipperiness can be formed without impairing optical properties. Is preferable, and the range of 0.030 to 0.250 μm is more preferable. When the PV of the support is less than 0.010 μm, the surface of the molded film becomes very smooth, and the slip between the film and the film or between the film and the transport roll is increased, resulting in poor slipping. The film does not travel stably on the transport line, and the winding shape becomes worse. On the other hand, when PV exceeds 0.300 μm, the optical properties of the film are deteriorated due to the roughness of the film surface.

  As a method of controlling the surface roughness of the support while maintaining appropriate adhesion with the norbornene compound addition polymer film, the smooth support is corona treatment, plasma treatment, glow treatment, ozone treatment, flame treatment, A method such as kneading a filler such as silica is performed. Among these, from the viewpoint of production cost, corona treatment and plasma treatment are preferable.

In the present invention, in addition to PV, it is important to control the adhesion between the support and the formed film within an appropriate range in order to form a norbornene addition polymer film having good slipperiness.
The adhesion between the support and the film can be evaluated by the wet tension of the support. The wetting tension is a scale for evaluating the surface energy, and is determined by the method disclosed in JIS K6768.

The wetting tension of the support is 50 to 75 mN / m. It is preferably 55 to 73 mN / m, and more preferably 59 to 73 mN / m. When the wetting tension is less than 50 mN / m, the difference from the wetting tension (30 to 40 mN / m) of the norbornene addition polymer film becomes small, so that the adhesion with the support becomes weak, and the solvent is vaporized after casting. The concentrated film is repelled from the support and the unevenness of the support is not properly transferred. If the wetting tension of the support exceeds 75 mN / m, the contact between the norbornene addition polymer film and the support becomes too strong, and the surface of the film becomes rough when peeling.
Incidentally, the wetting tension of polyethylene terephthalate that has not been surface-treated is about 40 to 45 mN / m, and the adhesion is weak when a norbornene addition polymer film is formed.

[Casting process]
It is preferable to remove foreign substances through a filter before casting the resin solution on the resin film support. The type of filter is not particularly limited. When the filter does not contain a non-dissolving component such as a filler, the opening of the filter is preferably 1 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less. If the aperture of the filter is too large, foreign matter cannot be removed sufficiently, leading to the generation of fish eyes and deterioration of optical properties. On the other hand, if the opening of the filter is too small, the filtration pressure increases and the filter may be clogged.

  The means for casting the resin solution on the resin film support is not particularly limited. Specifically, it can be cast on a resin film support using a comma coater, a lip coater, a bar coater, a slit die, a T die, a T die with a bar, a doctor blade, a roll coat, a die coat or the like. When casting continuously, roll out the long film of the support wound in a roll shape, apply the resin solution continuously, then dry continuously (dry organic solvent), roll Take up around. At this time, after peeling off the resin film of the support, only the cast film may be wound up.

[Volatilization (drying) of organic solvent and peeling process of cast film]
The resin solution cast on the resin film support is peeled off from the resin film support as a cast film having self-supporting properties after volatilizing the solvent. In the continuous process as described above, the cast film is wound into a roll.
The method for volatilizing the solvent is not particularly limited. Specific examples include hot air drying, infrared (IR) heating, and reduced pressure drying. These drying methods may be used alone or in combination.
The volatilization amount of the solvent is not particularly limited, but the solvent content of the cast film at the time of peeling is preferably 0.01 to 20% by mass, more preferably 0.05 to 15% by mass, and 0.1 to 10%. Mass% is particularly preferred. If the solvent is not sufficiently dried, the cast film is soft and does not have a self-supporting property, so that it is difficult to peel from the resin film support. On the other hand, if the solvent is evaporated too much, the energy cost for production tends to increase.

  The transport speed of the resin film support during continuous casting is not particularly limited, but is preferably 1 to 100 m / min, more preferably 2 to 50 m / min, and particularly preferably 5 to 30 m / min. When the conveyance speed is less than 0.1 m / min, the manufacturing cost becomes too high, and when the conveyance speed exceeds 100 m / min, air enters between the films or between the film and the roll, and the film floats. Conveyance tends to be unstable.

The cast film peeled off from the support may be further dried as necessary (secondary drying). The drying method is not particularly limited, and specific examples include hot air drying, infrared (IR) heating, and reduced pressure drying. These drying methods may be used alone or in combination.
The film transport method in the apparatus used for secondary drying is not particularly limited. Specific examples include a roll support, an air float, a clip tenter, and a pin tenter.

[Cast film]
The thickness of the cast film made of the norbornene compound addition polymer of the present invention is preferably 20 to 500 μm, more preferably 30 to 300 μm, and particularly preferably 40 to 150 μm. When the thickness is less than 20 μm, the rigidity of the film is weak, so that wrinkles are easily generated, and it becomes difficult to convey by a roll. On the other hand, if the thickness exceeds 500 μm, the film becomes heavier and sags in the transport line, which makes it difficult to transport by roll.

  The surface roughness (PV) represented by the maximum height difference of the cast film of the present invention is 0.010 to 0.300 μm. This is because the surface roughness (PV) of the resin film support used for production is reversely transferred. PV is preferably in the range of 0.020 to 0.270 μm, and more preferably in the range of 0.030 to 0.250 μm. When the PV is in the range of 0.010 to 0.300 μm, the friction between the film and the film or between the film and the transport roll is appropriate, the slipperiness is good, and the film travels stably on the transport line. Therefore, the roll shape of the roll becomes good. Further, the optical properties of the film due to the roughness of the film surface are not deteriorated, and the total light transmittance and the total haze value are also improved.

The cast film of the present invention has a total light transmittance of preferably 70% or more, more preferably 80% or more, and further preferably 90% or more. Furthermore, since the total haze is preferably 1% or less, more preferably 0.8% or less, and still more preferably 0.5% or less, it can be suitably used as an optical material and a display element member.
Further, since the saturated water absorption is preferably 0.001 to 0.1% by mass, more preferably 0.001 to 0.05% by mass, various optical characteristics such as transparency, phase difference, and phase difference are uniform. Properties and dimensional accuracy are maintained even under conditions such as high temperature and humidity, and excellent adhesion and adhesion to other materials, so that peeling does not occur during use, and additives such as antioxidants Therefore, the degree of freedom of addition is increased. In addition, the said saturated water absorption is a value calculated | required by immersing in 23 degreeC water for 24 hours, and measuring an increase mass based on JISK7209.

  The cast film obtained by the method of the present invention includes a hard coat layer, an antiglare layer, an antireflection layer, an antifouling layer, an antistatic layer, a conductive layer, an optical anisotropic layer, a liquid crystal layer, an alignment layer, an adhesive layer, Various functional layers such as an adhesive layer and an undercoat layer can be provided. These functional layers can be provided by a method such as coating or vapor deposition, sputtering, plasma CVD, or atmospheric pressure plasma treatment.

  In addition, the cast film obtained by the method of the present invention is easily treated with a hydrophilic surface such as acid treatment, alkali treatment, plasma treatment, corona treatment, etc. from the viewpoint of adhesion to a laminated film or a functional layer. You may implement the process which makes it easy to adhere | attach physically, such as an adhesion | attachment process.

Furthermore, a protective film may be laminated on one side or both sides of the obtained film. The protective film can be suitably formed as a polymer coating layer or a laminate of protective films. For the formation thereof, a polymer excellent in transparency, mechanical strength, thermal stability, moisture shielding property, etc. is preferably used. Examples thereof include cellulose resins such as triacetyl cellulose, polyester resins, acetate resins, polyether sulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, acrylic resins, Alternatively, thermosetting resins such as acrylic, urethane, acrylic urethane, epoxy, and silicone, or ultraviolet curable resins may be used. The surface of the transparent protective layer may be formed in a fine concavo-convex structure by containing fine particles.
The slitting process of the film, the laminating process of the protective film, and the surface treatment process may be performed in any order, and are not particularly limited.

[Optical parts]
The film made of the norbornene compound addition polymer of the present invention is a color filter substrate, a light guide plate, a protective film, a polarizing film, a retardation film, a touch panel, a transparent electrode substrate, an optical recording substrate such as a CD, MD, DVD, It can be suitably used as an optical component such as a TFT substrate, a liquid crystal display substrate, an organic EL display substrate, an optical transmission waveguide, optical lenses, a sealing material, or the like.
Among them, members for display elements, specifically, color filter substrates, light guide plates, protective films, polarizing films, retardation films, touch panels, transparent electrode substrates, TFT substrates, liquid crystal display substrates, organic EL display substrates, organic It can be suitably used for an encap substrate for EL.
The film comprising the norbornene compound-added polymer of the present invention can be used not only for optical parts but also for electrical insulation parts, electrical / electronic parts, electronic part sealants, medical equipment, and packaging materials.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, unless otherwise indicated, the part and% in an Example are mass references | standards.
The test and evaluation in an Example and a comparative example were performed with the following method.

(1) Weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer
It is measured as a polystyrene equivalent value by gel permeation chromatography (GPC) using tetrahydrofuran or chloroform as a solvent.
(2) Copolymerization ratio of polymer
Obtained by ¹ H-NMR measurement.
(3) PV
Using a scanning probe microscope (manufactured by Hitachi High-Tech Science Co., Ltd.), a 5 μm × 5 μm range is measured. The measurement is performed three times, and the average value is defined as PV of the support. The cantilever uses SI-DF40P2.

(4) Wetting tension Measured by the method described in JIS K6768. That is, in an environment of a temperature of 23 ° C. and a relative humidity of 50%, predetermined test mixed liquids having different wetting tensions are dropped on the resin film for the support, and the liquid film is wetted after 2 seconds. Determine the tension (mN / m).
(5) Total light transmittance Measured using a haze meter NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.).
(6) All haze It measures using haze meter NDH2000 (made by Nippon Denshoku Industries Co., Ltd.).
(7) Residual solvent ratio Using the weight drying method, the obtained film was dried in an oven at 180 ° C. for 30 minutes, and the following formula:
(Weight before drying-Weight after drying) / (Weight before drying) x 100 (%)
Calculate from

Synthesis Example 1: Synthesis of norbornene-2-acetoxymethyl-5-norbornene copolymer According to the method described in JP 2012-77284-Acetoxymethyl-5-norbornene, norbornene (manufactured by Tokyo Chemical Industry Co., Ltd.), ( π-allyl) {2- [N- (2,6-diisopropylphenyl) iminomethyl] phenolato} palladium, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate [(C ₆ H ₅ ) (CH ₃ ) ₂ NH] [B (C ₆ F ₅ ) ₄ ] (manufactured by Strem Co.) and triisopropylphosphine [P (i-C ₃ H ₇ ) ₃ ] (manufactured by Strem Co.) were used for polymerization reaction in toluene, and norbornene A 2-acetoxymethyl-5-norbornene copolymer polymer was obtained.
The obtained polymer was easily dissolved in a general solvent such as THF and chloroform, the number average molecular weight was Mn = 916,000, and the molecular weight distribution was Mw / Mn = 2.12. The composition of 2-acetoxymethyl-5-norbornene monomer unit in the polymer calculated from the integral value of ¹ H-NMR was 20.4 mol%.

Manufacture example 1: Surface treatment of polyethylene terephthalate film A surface-untreated polyethylene terephthalate film, Lumirror (registered trademark) T60 (manufactured by Toray Industries, Inc., long film with a width of 50 cm), corona treatment device CT-0212 manufactured by Kasuga Electric Co., Ltd. The corona treatment was performed at a distance between electrode films of 1.0 mm, an output of 80 W, and a treatment speed of 1.0 m / min. The wetting tension of the polyethylene terephthalate film before treatment was 46 mN / m and PV was 0.008 μm, but the wetting tension after treatment was 60 mN / m and PV was 0.034 μm.

Production Example 2: Surface treatment of polyethylene terephthalate film Corona treatment was applied to Lumirror T60 using a corona treatment device CT-0212 manufactured by Kasuga Denki Co., Ltd. at a distance between electrode films of 1.0 mm, an output of 160 W, and a treatment speed of 0.5 m / min. went. The wet tension after treatment was 72 mN / m, and PV was 0.094 μm.

Production Example 3: Surface Treatment of Polyethylene Terephthalate Film An electrode film using E5000 (Toyobo Co., Ltd., long film with a width of 50 cm), a surface untreated polyethylene terephthalate film, using a corona treatment device CT-0212 made by Kasuga Electric Co., Ltd. Corona treatment was performed at a distance of 1.0 mm, an output of 60 W, and a treatment speed of 1.0 m / min. The wetting tension of the polyethylene terephthalate film before treatment was 46 mN / m and PV was 0.005 μm, but the wetting tension after treatment was 58 mN / m and PV was 0.006 μm.

Production Example 4: Surface Treatment of Polyethylene Terephthalate Film Sandblasting was performed at a treatment speed of 5.0 m / min using E5000 with an amorphous silica powder having a long side length of 30 μm. After the sandblast treatment, washing with water and drying with warm air were performed. The wetting tension after treatment was 48 mN / m, and PV was 0.230 μm. The film was further subjected to corona treatment using a corona treatment device CT-0212 manufactured by Kasuga Electric Co., Ltd. at a distance between electrode films of 1.0 mm, an output of 80 W, and a treatment speed of 1.0 m / min. The wet tension after treatment was 60 mN / m, and PV was 0.242 μm.

Production Example 5: Surface treatment of polyethylene terephthalate film An amorphous silica powder having a long side length of 50 μm was used for E5000, and a sandblast treatment was performed at a treatment speed of 3.0 m / min. After the sandblast treatment, washing with water and drying with warm air were performed. The wetting tension after treatment was 48 mN / m, and PV was 0.441 μm. The film was further subjected to corona treatment using a corona treatment device CT-0212 manufactured by Kasuga Electric Co., Ltd. at a distance between electrode films of 1.0 mm, an output of 80 W, and a treatment speed of 1.0 m / min. The wet tension after treatment was 60 mN / m, and PV was 0.452 μm.

Example 1:
The norbornene addition copolymer produced in Synthesis Example 1 was dissolved in toluene to obtain a 10% by mass resin solution. Using the polyethylene terephthalate film produced in Production Example 1 as a support, a resin solution was continuously cast on the support using a slit die, and hot air drying was performed. The drying chamber temperature was 60 ° C. and the residence time was 10 minutes. By this step, the solvent was dried to a residual solvent ratio of 10% by mass and wound into a roll. In the subsequent process, the polyethylene terephthalate film was continuously peeled from the cast film of norbornene addition copolymer while unwinding the film from the roll, and the cast film was wound onto the roll. Although the conveyance speed was gradually increased from the conveyance speed of 0.5 m / min, the film traveled stably even at 2 m / min, and a roll film having a length of 200 m and a good winding shape was produced. The produced film (thickness 50 μm) had a total light transmittance of 91%, a total haze of 0.4%, and a PV of 31 nm.

Example 2:
The norbornene addition copolymer produced in Synthesis Example 1 was dissolved in dichloromethane to obtain a 10% by mass resin solution. A cast film was produced in the same manner as in Example 1 except that the polyethylene terephthalate film produced in Production Example 2 was used as a support. Although the conveyance speed was gradually increased from the conveyance speed of 0.5 m / min, the roll film stably traveled even at 5 m / min, and a roll film having a good winding shape with a length of 260 m was produced. The produced film (thickness 50 μm) had a total light transmittance of 91%, a total haze of 0.5%, and a PV of 0.083 μm.

Example 3:
A cast film was produced in the same manner as in Example 1 except that the polyethylene terephthalate film produced in Production Example 4 was used as a support. Although the conveyance speed was gradually increased from the conveyance speed of 0.5 m / min, the roll film stably traveled at 20 m / min, and a roll film having a good winding shape of 310 m was manufactured. The produced film (thickness 50 μm) had a total light transmittance of 90%, a total haze of 0.7%, and a PV of 0.229 μm.

Comparative Example 1:
A film was produced in the same manner as in Example 1 except that the support was changed to untreated T60 (manufactured by Toray Industries, Inc., long film with a width of 50 cm), but the norbornene addition copolymer was being dried. The film was peeled off from the polyethylene terephthalate film as the support and was broken in the furnace, and a roll film could not be produced.

Comparative Example 2:
A film was produced in the same manner as in Example 1 except that the support was changed to the polyethylene terephthalate film produced in Production Example 3, but strong vertical wrinkles were generated on the free roll of the winder, and the winding shape was good. Roll film could not be produced.

Comparative Example 3:
A film was produced in the same manner as in Example 1 except that the support was changed to the polyethylene terephthalate film produced in Production Example 5. At a conveyance speed of 20 m / min, a roll film having a length of 330 m and a good winding shape could be produced. The produced film had a total light transmittance of 89%, a total haze of 1.6%, and a PV of 0.00. It was 410 μm.

Comparative Example 4:
Although it is classified into the same cycloolefin polymer as the norbornene compound addition polymer used in the present invention, Arton (registered trademark; metathesis ring-opening polymer such as tetracyclododecene derivative manufactured by JSR Corporation) having a different chemical structure is toluene. 10% by weight resin solution, cast continuously onto the polyethylene terephthalate film produced in Production Example 4 using a slit die, and dried by continuous hot air drying to a residual solvent ratio of 10% and then peeled off and wound up. However, the cast film was peeled off from the polyethylene terephthalate film as the support during drying, and was broken in the drying apparatus, making it impossible to produce a roll film. From comparison with Example 3, it can be seen that it is important to control the structure of the norbornene-based compound polymer in order to achieve the object of the present invention.

The results of Examples 1 to 3 and Comparative Examples 1 to 4 are summarized in Table 1.

  The film made of a norbornene compound addition (co) polymer having a functional layer of the present invention has excellent heat resistance and solubility in a general solvent in addition to transparency and optical properties, and further has a water absorption coefficient and a linear expansion coefficient. Since it is low, it is useful as an optical material, and can be used as a substrate material for an organic EL display.

Claims (11)

General formula (1)

(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms, R ^{2 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ^{2 to} R ⁴ are: And may be bonded to each other to form a ring, and n ¹ is 0 or 1.)
A resin solution in which a norbornene compound addition polymer containing a monomer unit represented by is dissolved in an organic solvent is applied onto a resin film support to form a cast film, the organic solvent is volatilized, and then the resin film is supported. A method for producing a cast film for peeling a body, wherein the surface roughness (PV) of the resin film support surface expressed by the maximum height difference is in the range of 0.010 to 0.300 μm, and the wetting tension is 50. A method for producing a cast film, which is in a range of ˜75 mN / m. The norbornene compound addition polymer has the general formula (1) and the general formula (2).

(Wherein R ^{5 to} R ⁸ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ^{5 to} R ⁸ may be bonded to each other to form a ring; ² is 0 or 1.)
The manufacturing method of the cast film of Claim 1 which is a copolymer containing the monomer unit shown by these. The unit represented by the general formula (1) is represented by the following formula (A)

The manufacturing method of the cast film of Claim 1 or 2 shown by these. The unit represented by the general formula (2) is represented by the following formula (B)

The manufacturing method of the cast film of Claim 2 or 3 shown by these.   The manufacturing method of the cast film in any one of Claims 1-4 whose surface roughness (PV) represented by the maximum height difference of a resin film support is the range of 0.03-0.250 micrometer.   The film forming method according to claim 1, wherein the wetting tension of the resin film support is in the range of 59 to 73 mN / m.   The method for producing a cast film according to claim 1, wherein the resin film support is a polyethylene terephthalate film.   The method for producing a cast film according to any one of claims 1 to 7, wherein the organic solvent of the resin solution is toluene or dichloromethane.   The optical film obtained by the manufacturing method of the cast film in any one of Claims 1-8.   The optical film according to claim 9, wherein the optical film is for a display element member.   The surface roughness (PV) represented by the maximum height difference is 0.010 μm to 0.300 μm, and consists of a norbornene compound addition polymer containing a monomer unit represented by the general formula (1), having a thickness of 20 to 300 μm. Cast film.