JP2005144771A - Surface decorative film or sheet and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To precisely and stably manufacture a film or sheet, which has a three-dimensional pattern for imparting an optical function at least on one side thereof, with high productivity. <P>SOLUTION: In a method for casting a cyclic olefinic resin having a polar group extruded from a die in a molten state using a metal endless belt and a metal roll, the metal endless belt having a three-dimensional pattern formed at least on its casting surface and/or the metal roll having a three-dimensional pattern on its surface is used to transfer the three-dimensional pattern at least to one side of the film or sheet to obtain the surface decorative film or sheet. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is produced by a method for producing a film or sheet comprising a cyclic olefin resin having a three-dimensional pattern on the surface and imparted optical functions such as light refraction, scattering, reflection, polarization, and interference, and the production method. Related to a film or sheet.

Due to recent technological innovations such as liquid crystal display elements, plasma light emitting elements or organic EL elements, displays using these have come to be widely used as monitor screens for televisions, personal computers or mobile phones. In these display devices, a light guide plate having an optical function such as light refraction, scattering, and reflection, a light scattering plate, and the like are used in order to effectively use the generated light. Since these optical functional materials have complicated surface shapes and the like, they are manufactured by injection molding that can take a long mold transfer time, solvent cast molding, or the like.
However, performing mold transfer for a long time by injection molding leads to a deterioration in productivity, and injection molding is a batch type, which increases the price of the obtained molded product. In addition, solvent cast molding can be continuously formed into a film, so the productivity is good, but the incidental equipment such as solvent recovery becomes large, so the initial investment becomes enormous and finally It will be passed on to the price of the product. In addition, there is a problem that the thickness of a product that can be manufactured is limited because there is a limitation on the solvent to be removed by the drying process and it is difficult to dry.

On the other hand, for example, as disclosed in Patent Document 1 (Japanese Patent Laid-Open No. 8-211205), a mold release film having a shape for transferring a desired three-dimensional pattern by melting and extruding a resin and a metal roll are used. A method for transferring a three-dimensional pattern using the same is disclosed. However, in this method, it is necessary to prepare a film for shape transfer in advance, which makes the operation complicated, and it is necessary to peel off the shape transfer film, which makes it difficult to reduce the labor and cost of manufacturing.
On the other hand, a method of transferring a three-dimensional pattern by sandwiching a melt-extruded resin with a roll having a three-dimensional pattern formed on the surface and a pressing roll is also disclosed, but it is difficult to adjust the pressure between the roll and the roll. Problems can arise when precise shape transfer is desired. For this reason, in order to obtain transfer accuracy, a method of increasing the transfer pressure during transfer by so-called bank molding or the like is generally known. However, in this method, a large residual stress (internal stress) is generated in the obtained film or sheet, so that optical distortion occurs in the film or sheet and birefringence does not become constant in the plane. Sometimes.
Further, when surface transfer is performed without using bank forming, the transfer time is too short, so that the surface cannot be transferred sufficiently, and a desired three-dimensional pattern cannot be obtained.
Japanese Patent Laid-Open No. 8-211205

  The present invention has been made in view of the above problems, and a film or sheet having a three-dimensional pattern for imparting an optical function to at least one surface can be manufactured stably with high productivity and high accuracy. It is providing the manufacturing method of a sheet | seat, and the film or sheet | seat manufactured by the manufacturing method which concerns.

  As a result of intensive studies to solve the above problems, the inventors of the present invention, in the production of a surface design film or sheet made of a cyclic olefin resin, the formation of the design on one or both sides of the film or sheet is cyclic. It is found that it is effective to perform surface transfer using a metal endless belt with a three-dimensional pattern on the surface and / or a metal roll with a three-dimensional pattern on the surface after the olefin resin is melt extruded from a die. The invention has been completed.

  According to the present invention, a target shape can be accurately formed on the surface, and a surface designable film or sheet having such a shape can be obtained with high productivity.

Hereinafter, the present invention will be described in detail.
In the present invention, as a film or sheet (hereinafter referred to simply as “sheet” unless otherwise specified), the resin can be melt-extruded from a die as a manufacturing apparatus, and further includes a metal endless belt and a metal roll. It is necessary to use an apparatus equipped with a casting process.
Drawing 1 is an explanatory view showing an outline in an example of a manufacturing device used for a manufacturing method of a cyclic olefin system resin sheet of the present invention. In this figure, 1 is an extruder, 2 is a gear pump, 3 is a polymer filter, 4 is a T-die attached to the tip of the extruder 1, and this T-die 4 is arranged so that its discharge port 52 faces downward. Has been.

  As the extruder 1 used in the present invention, a known one can be used. For example, a uniaxial or biaxial apparatus including a screw, a paddle, a disk, a rotor, etc. for plasticizing pellets or particulate or powdery raw materials can be used. Furthermore, you may use the apparatus which can be extruded while making it melt | dissolve from the solution which dissolved the raw material in the soluble solvent. Furthermore, a known type of gear pump 2 for stabilizing the amount of extrusion and extrusion pressure, and a known polymer filter 3 for removing foreign substances and gels may be provided at the outlet of the extruder.

  As the T die 4, a manifold die, a fish tail die, a coat hanger die, or the like can be used, and among these, a coat hanger die is preferable. Examples of the material of the T die 4 include, but are not limited to, SCM steel and stainless steel such as SUS. Further, as the T die 4, the surface thereof is plated with chromium, nickel, titanium, etc., TiN, TiAlN, TiC, CrN, DLC (diamond-like carbon), etc. by PVD (Physical Vapor Deposition) method or the like. Those having a coating formed thereon, those having other ceramics sprayed thereon, those having the surface nitrided, and the like can be used. Such a T-die has high surface hardness and low friction with the resin, so that it is possible to prevent burnt dust and the like from being mixed into the obtained cyclic olefin resin sheet, and to generate a die line. It is preferable in that it can be prevented.

Below the T die 4, a transfer belt 7 made of a metal transfer roll 6 and a metal endless belt is in pressure contact with each other, and the contact end E of both is directly below the discharge port 5 of the T die 4. It is arranged in the state that is located in. A three-dimensional pattern is formed on the transfer roll 6 and / or the transfer belt 7 depending on the purpose.
The transfer roll 6 has a heating means and a cooling means inside. When the transfer roll 6 is not provided with a three-dimensional pattern, or when it is used as a base material before forming the three-dimensional pattern, the surface roughness is preferably 0.5 μm or less, particularly 0.3 μm or less. As the transfer roll 6, a metal roll plated may be used depending on the purpose, and preferred examples of the plating include those plated with chrome plating, electroless nickel plating, and the like.

  It is preferable to use a seamless belt as the transfer belt 7. When a cooling belt having a seam is used, a seam mark is formed on the obtained cyclic olefin resin sheet, which is not preferable. The transfer belt 7 is formed with a three-dimensional pattern according to the purpose. When using a three-dimensional pattern as a base material for formation or as a mirror surface, it is preferable to use a mirror surface finish having a surface roughness of 0.3 μm or less. Further, the thickness of the transfer belt 7 is preferably 0.3 mm to 1.2 mm. When the thickness is less than 0.3 mm, the belt is easily deformed, which is not preferable. On the other hand, when the thickness exceeds 1.2 mm, the belt is not preferable because the flexibility becomes small. As a material constituting the transfer belt 7, stainless steel or the like can be used.

  The transfer belt 7 is held in a state in which the transfer belt 6 is pressed against the transfer roll 6 by a first support roll 8 and a second support roll 9 provided in contact with the inner surface of the transfer belt 7 and tension is applied. ing.

  The first support roll 8 is arranged so as to be parallel to the transfer roll 6 slightly spaced apart from the transfer roll 6 at a substantially same height level. The surface of the first support roll 8 is preferably coated with silicon rubber or another heat-resistant elastomer, and the thickness of the coating layer is more preferably 5 to 15 mm. By providing such a coating layer, when the cyclic olefin resin is sandwiched between the transfer roll 6 and the transfer belt 7, the compressive stress acting on the resin is relieved, so that the obtained cyclic olefin resin is obtained. An increase in phase difference due to residual distortion in the sheet can be prevented. Moreover, it is preferable that the 1st support roll 8 has a heating means or a cooling means inside. The heating means for the first support roll 8 is not particularly limited, and a known method such as oil, steam, high-pressure water, or electric heating can be used depending on the purpose. The cooling means includes water, air, inert gas, etc. in addition to the method used for the heating means.

The second support roll 9 is arranged below the transfer roll 6 so as to be arranged in parallel with the transfer roll 6. The second support roll 9 is a contact distance adjusting roll for adjusting the contact distance between the transfer roll 6 and the transfer belt 7. For example, the second support roll 9 is provided so as to be movable in an arc shape with reference to the central axis of the transfer roll 6. It has been.
As with the first support roll 8, the surface of the second support roll 9 is preferably covered with silicon rubber or other heat-resistant elastomer, and has heating means or cooling means inside. It is preferable that Also, the second support roll 9 can be heated or cooled in the same manner as the first support roll 8, and a temperature difference can be provided between the two in order to achieve both the transferability of the three-dimensional pattern and the optical characteristics. It is preferable.

  In the above, the transfer roll 6 and the transfer belt 7 are preferably arranged as close to the T die 4 as possible. For example, the contact between the transfer roll 6 and the transfer belt 7 from the discharge port 5 of the T die 4. It is preferable that the distance of the perpendicular line connecting to the end E is 300 mm or less, particularly 250 mm or less. When this distance exceeds 300 mm, the molten cyclic olefin-based resin discharged from the discharge port 5 of the T die 4 is remarkably cooled before being sandwiched between the transfer roll 6 and the cooling belt 7. The three-dimensional pattern is not sufficiently transferred, and a phase difference due to residual distortion is likely to occur. Further, the contact distance between the transfer roll 6 and the transfer belt 7 is preferably 20 cm or more, and particularly preferably 25 cm or more. When the contact distance is less than 20 cm, the three-dimensional pattern cannot be sufficiently transferred by the transfer roll 6 and the transfer belt 7, or the resin cannot be sufficiently cooled.

The present invention is characterized in that a three-dimensional pattern is formed on at least one or both of the transfer belt 7 and the transfer roll 6 and transferred.
The three-dimensional pattern of the present invention is not particularly limited. For example, prism shape, semicircular shape, elliptical shape, rectangular shape, V-shaped groove or mountain shape, hemispherical shape, semi-elliptical shape, cone, polygonal pyramid, truncated cone, polygonal truncated pyramid shape, etc., random Non-concave / convex shapes, lattice shapes, branched groove shapes, arbitrary pattern shapes, and the like, and their functions are not limited, but those that provide optical functions such as light collection, scattering, diffraction, and polarization are preferable. .

  A method for forming a three-dimensional pattern on the transfer belt 7 or the transfer roll 6 is not particularly limited, and a known method can be used. For example, a cutting method, a method by electric discharge machining, a laser machining, a method by electroforming, a method by etching, a method of printing a curable resin, a method by sandblasting, and the like can be mentioned. In addition, these processes can be performed directly on the base material. After plating a known metal such as nickel or copper or a compound thereof, a process is performed after applying a curable organic compound such as light or heat. It is also possible. It is also possible to manufacture as a stamper and to make a multilayer with a metal endless belt or a metal roll.

  The processing temperature of the cyclic olefin-based resin, that is, the set temperature of the extruder 1, the gear pump 2, the polymer filter 3, and the T-die 4 can discharge a molten resin with uniform fluidity from the T-die 4, From the viewpoint of suppressing deterioration, when the glass transition temperature of the resin is Tg, it is preferably Tg + 100 ° C. or higher and Tg + 200 ° C. or lower. When the processing temperature is less than Tg + 100 ° C., the fluidity of the resin is non-uniform, and therefore, the resin is not stably discharged from the T die 4, and the resulting cyclic olefin-based resin sheet is likely to have uneven thickness, etc. Absent. On the other hand, when the processing temperature exceeds Tg + 200 ° C., the resin may easily deteriorate due to the molecular chain of the resin being cut or being oxidized when discharged from the T die 4.

  The surface temperature of the transfer roll 6 is preferably Tg-30 ° C. or higher, where Tg is the glass transition point of the cyclic olefin resin used. When the surface temperature of the transfer roll 6 is less than Tg−30 ° C., the resin R is rapidly cooled by the transfer roll 6, making it difficult to transfer the target shape. For the same reason, the surface temperature of the first support roll 8 is preferably Tg-30 ° C. or higher.

  The take-up speed of the surface designable sheet is preferably lower than the rotation peripheral speed of the transfer roll 6, specifically, when the rotation peripheral speed of the transfer roll 6 is V1, and the take-up speed of the surface design sheet is V2, The ratio V2 / V1 is preferably 0.7 to 0.99, more preferably 0.75 to 0.9, and particularly preferably 0.8 to 0.85. If this ratio V2 / V1 is less than 0.7, the sheet is likely to sag. On the other hand, if this ratio V2 / V1 exceeds 0.99, excessive tension acts on the sheet, The sheet may break.

According to such a method, by extruding the molten cyclic olefin resin from the T die 4 downward in the vertical direction, the extruded cyclic olefin resin is prevented from being bent by gravity, and In addition, since the cyclic olefin-based resin pressure-bonded to the transfer belt 7 is peeled at a temperature equal to or lower than the glass transition temperature, it is possible to manufacture a sheet in which the target shape is sufficiently transferred.
In addition, since the molten cyclic olefin-based resin extruded from the T-die 4 does not come into contact with either the transfer roll 6 or the transfer belt 8, the transfer uniformity or mirror surface is created. Can produce a surface-designable sheet having surface characteristics with excellent surface uniformity.

In the present invention, examples of the cyclic olefin resin to be used include the following (co) polymers.
(1) A ring-opening polymer of a specific monomer represented by the following general formula (I).
(2) A ring-opening copolymer of a specific monomer represented by the following general formula (I) and a copolymerizable monomer.
(3) A hydrogenated (co) polymer of the ring-opening (co) polymer of (1) or (2) above.
(4) A (co) polymer obtained by cyclizing the ring-opening (co) polymer of the above (1) or (2) by Friedel-Craft reaction and then hydrogenating it.
(5) A saturated copolymer of a specific monomer represented by the following general formula (I) and an unsaturated double bond-containing compound.
(6) Addition type (co) of one or more monomers selected from a specific monomer represented by the following general formula (I), a vinyl-based cyclic hydrocarbon-based monomer, and a cyclopentadiene-based monomer Polymers and their hydrogenated (co) polymers.
(7) An alternating copolymer of a specific monomer represented by the following general formula (I) and an acrylate.
Among these, a cyclic olefin resin having a polar group in the molecule is preferable because it is excellent in adhesiveness and adhesion to other materials and can be easily post-processed. The polar group may be present in a structural unit derived from the following general formula (I), or may be present in a structural unit derived from a copolymerized monomer.

[In formula, R < ¹ > -R < ⁴ > is a hydrogen atom, a halogen atom, a C1-C30 hydrocarbon group, or another monovalent organic group, respectively, and may be same or different, respectively. R ¹ and R ² or R ³ and R ⁴ may be combined to form a divalent hydrocarbon group, and R ¹ or R ² and R ³ or R ⁴ are bonded to each other to form a single ring or A polycyclic structure may be formed. m is 0 or a positive integer, and p is 0 or a positive integer. ]

<Specific monomer>
Specific examples of the specific monomer include the following compounds, but the present invention is not limited to these specific examples.
Bicyclo [2.2.1] hept-2-ene,
Tricyclo [4.3.0.1 ^2,5 ] -8-decene,
Tricyclo [4.4.0.1 ^2,5 ] -3-undecene,
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-cyanobicyclo [2.2.1] hept-2-ene,
8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
5-ethylidenebicyclo [2.2.1] hept-2-ene,
8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
5-phenylbicyclo [2.2.1] hept-2-ene,
8-phenyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
5-fluorobicyclo [2.2.1] hept-2-ene,
5-fluoromethylbicyclo [2.2.1] hept-2-ene,
5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-pentafluoroethylbicyclo [2.2.1] hept-2-ene,
5,5-difluorobicyclo [2.2.1] hept-2-ene,
5,6-difluorobicyclo [2.2.1] hept-2-ene,
5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,5,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5-heptafluoro-iso-propyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene,
8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-fluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-difluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-pentafluoroethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9,9-tetrafluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9,9-tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluoro-8-heptafluoroiso-propyl-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-chloro-8,9,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene.
These can be used alone or in combination of two or more.

Among the specific monomers, in general formula (I), R ¹ and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 2 carbon atoms. R ² and R ⁴ are a hydrogen atom or a monovalent organic group, and at least one of R ² and R ⁴ represents a polar group having a polarity other than a hydrogen atom or a hydrocarbon group, and m is 0 An integer of ˜3, p is an integer of 0 to 3, more preferably m + p = 0 to 4, more preferably 0 to 2, particularly preferably m = 1 and p = 0. The specific monomer with m = 1 and p = 0 is preferable in that the cyclic olefin resin obtained has a high glass transition temperature and excellent mechanical strength.
Examples of the polar group of the specific monomer include a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, and a cyano group. These polar groups are connected via a linking group such as a methylene group. May be combined. In addition, a hydrocarbon group in which a divalent organic group having a polarity such as a carbonyl group, an ether group, a silyl ether group, a thioether group, or an imino group is bonded as a linking group can also be exemplified. Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group or an allyloxycarbonyl group is preferable, and an alkoxycarbonyl group or an allyloxycarbonyl group is particularly preferable.

Furthermore, a monomer in which at least one of R ² and R ⁴ is a polar group represented by the formula — (CH ₂ ) _n COOR is obtained by using a cyclic olefin-based resin having a high glass transition temperature, a low hygroscopic property, and various materials. It is preferable at the point from which it has the outstanding adhesiveness. In the formula relating to the specific polar group, R is a hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 4, particularly preferably 1 to 2, and preferably an alkyl group. In addition, n is usually 0 to 5, but the smaller the value of n, the higher the glass transition temperature of the resulting cyclic olefin resin, which is preferable, and the specific monomer having n of 0 is It is preferable in that the synthesis is easy.

In the general formula (I), R ¹ or R ³ is preferably an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, particularly preferably a methyl group. In particular, the fact that this alkyl group is bonded to the same carbon atom as that to which the specific polar group represented by the formula — (CH ₂ ) _n COOR is bonded is that of the obtained cyclic olefin-based resin. It is preferable at the point which can make hygroscopicity low.

<Copolymerizable monomer>
Specific examples of the copolymerizable monomer include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene. The number of carbon atoms of the cycloolefin is preferably 4-20, and more preferably 5-12. These can be used alone or in combination of two or more.
A preferred use range of the specific monomer / copolymerizable monomer is 100/0 to 50/50, more preferably 100/0 to 60/40, in weight ratio.

<Ring-opening polymerization catalyst>
In the present invention, (1) a ring-opening polymer of a specific monomer, and (2) a ring-opening polymerization reaction for obtaining a ring-opening copolymer of a specific monomer and a copolymerizable monomer are metathesis It is carried out in the presence of a catalyst.
This metathesis catalyst comprises (a) at least one selected from W, Mo and Re compounds, (b) Deming periodic table group IA elements (for example, Li, Na, K, etc.), IIA group elements (for example, , Mg, Ca, etc.), Group IIB elements (eg, Zn, Cd, Hg, etc.), Group IIIA elements (eg, B, Al, etc.), Group IVA elements (eg, Si, Sn, Pb, etc.), or Group IVB A catalyst comprising a combination of at least one element selected from compounds having elements (for example, Ti, Zr, etc.) and having at least one element-carbon bond or the element-hydrogen bond.
In this case, in order to increase the activity of the catalyst, an additive (c) described later may be added.

Representative examples of W, Mo or Re compounds suitable as component (a) include WCl ₆ , MoCl ₆ , ReOCl _3, etc. JP-A-1-132626, page 8, lower left column, line 6 to page 8, upper right page. The compounds described in column 17th line can be mentioned.
(B) Specific examples of the _{component, n-C 4 H 9 Li} , (C 2 H 5) 3 Al, (C 2 H 5) 2 AlCl, (C 2 H 5) 1.5 AlCl 1.5, (C 2 H ₅ ) AlCl ₂ , methylalumoxane, LiH and the like can be mentioned compounds described in JP-A No. 1-132626, page 8, upper right column, line 18 to page 8, lower right column, line 3.
As typical examples of the component (c) which is an additive, alcohols, aldehydes, ketones, amines and the like can be suitably used, but further, JP-A-1-132626, page 8, lower right column, The compounds shown in line 16 to page 9, upper left column, line 17 can be used.

The amount of the metathesis catalyst used is a range in which “(a) component: specific monomer” is usually 1: 500 to 1: 50,000 in terms of the molar ratio of the component (a) to the specific monomer. The range is preferably 1: 1,000 to 1: 10,000.
The ratio of the component (a) to the component (b) is such that (a) :( b) is 1: 1 to 1:50, preferably 1: 2 to 1:30 in terms of metal atomic ratio.
The ratio of the component (a) to the component (c) is such that the molar ratio (c) :( a) is in the range of 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1. The

<Solvent for polymerization reaction>
Examples of the solvent used in the ring-opening polymerization reaction (solvent constituting the molecular weight modifier solution, solvent for the specific monomer and / or metathesis catalyst) include alkanes such as pentane, hexane, heptane, octane, nonane, decane, Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, Compounds such as halogenated alkanes and aryl halides such as chloroform and tetrachloroethylene, saturated carbohydrates such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, and dimethoxyethane Esters, dibutyl ether, tetrahydrofuran, and the like can be illustrated ethers such as dimethoxyethane, they can be used singly or in combination. Of these, aromatic hydrocarbons are preferred.
As the amount of the solvent used, “solvent: specific monomer (weight ratio)” is usually in an amount of 1: 1 to 10: 1, preferably in an amount of 1: 1 to 5: 1. The

<Molecular weight regulator>
The molecular weight of the resulting ring-opening (co) polymer can be adjusted by the polymerization temperature, the type of catalyst, and the type of solvent. In the present invention, the molecular weight is adjusted by allowing the molecular weight regulator to coexist in the reaction system. To do.
Here, suitable molecular weight regulators include, for example, α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. Styrene can be mentioned, and among these, 1-butene and 1-hexene are particularly preferable.
These molecular weight regulators can be used alone or in admixture of two or more.
The amount of the molecular weight regulator used is 0.005 to 0.6 mol, preferably 0.02 to 0.5 mol, per 1 mol of the specific monomer subjected to the ring-opening polymerization reaction.

  (2) In order to obtain a ring-opening copolymer, a specific monomer and a copolymerizable monomer may be subjected to ring-opening copolymerization in the ring-opening polymerization step, and further, polybutadiene, polyisoprene, etc. In the presence of unsaturated hydrocarbon polymers such as conjugated diene compounds, styrene-butadiene copolymers, ethylene-nonconjugated diene copolymers, polynorbornene and the like containing two or more carbon-carbon double bonds in the main chain. The specific monomer may be subjected to ring-opening polymerization.

Although the ring-opening (co) polymer obtained as described above can be used as it is, (3) the hydrogenated (co) polymer obtained by further hydrogenation is a resin having high impact resistance. It is useful as a raw material.
<Hydrogenation catalyst>
In the hydrogenation reaction, a hydrogenation catalyst is added to a usual method, that is, a solution of a ring-opening polymer, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, is added thereto at 0 to 200 ° C., preferably 20 It is carried out by operating at ~ 180 ° C.
As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. Examples of the hydrogenation catalyst include heterogeneous catalysts and homogeneous catalysts.

  Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania. The homogeneous catalysts include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium. Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, and the like. The form of the catalyst may be powder or granular.

These hydrogenation catalysts are used in such a ratio that the ring-opening (co) polymer: hydrogenation catalyst (weight ratio) is 1: 1 × 10 ⁻⁶ to 1: 2.
As described above, the hydrogenated (co) polymer obtained by hydrogenation has excellent thermal stability, and its characteristics deteriorate due to heating during molding and use as a product. There is no. Here, the hydrogenation rate is usually 50% or more, preferably 70% or more, and more preferably 90% or more.

The hydrogenation rate of the hydrogenated (co) polymer is 50% or more, preferably 90% or more, more preferably 98% or more, and most preferably 99% or more, as measured by 500 MHz and ¹ H-NMR. is there. The higher the hydrogenation rate, the better the stability to heat and light.
The hydrogenated (co) polymer used as the cyclic olefin resin of the present invention preferably has a gel content contained in the hydrogenated (co) polymer of 5% by weight or less. It is particularly preferable that the amount is not more than% by weight.

In addition, as the cyclic olefin-based resin used in the present invention, (4) the (1) or (2) ring-opening (co) polymer is cyclized by Friedel-Craft reaction and then hydrogenated (co) heavy. Merges can also be used.
<Cyclization by Friedel-Craft reaction>
The method for cyclizing the ring-opened (co) polymer of (1) or (2) by Friedel-Craft reaction is not particularly limited, but the acidic compound described in JP-A-50-154399 is used. Any known method can be employed. Specific examples of the acidic compound include Lewis acids such as AlCl ₃ , BF ₃ , FeCl ₃ , Al ₂ O ₃ , HCl, CH ₃ ClCOOH, zeolite, activated clay, and Bronsted acid.
The cyclized ring-opening (co) polymer can be hydrogenated in the same manner as the ring-opening (co) polymer (1) or (2).

Further, as the cyclic olefin resin used in the present invention, (5) a saturated copolymer of the specific monomer and an unsaturated double bond-containing compound can also be used.
<Unsaturated double bond-containing compound>
As an unsaturated double bond containing compound, ethylene, propylene, butene etc., Preferably it is C2-C12, More preferably, C2-C8 olefin type compound can be mentioned.
The preferred use range of the specific monomer / unsaturated double bond-containing compound is 90/10 to 40/60, more preferably 85/15 to 50/50, in weight ratio.

In the present invention, in order to obtain a saturated copolymer of (5) a specific monomer and an unsaturated double bond-containing compound, a usual addition polymerization method can be used.
<Addition polymerization catalyst>
As the catalyst for synthesizing the (5) saturated copolymer, at least one selected from a titanium compound, a zirconium compound and a vanadium compound and an organoaluminum compound as a promoter are used.
Here, examples of the titanium compound include titanium tetrachloride and titanium trichloride, and examples of the zirconium compound include bis (cyclopentadienyl) zirconium chloride and bis (cyclopentadienyl) zirconium dichloride.

Furthermore, as a vanadium compound, general formula VO (OR) _a X _b or V (OR) _c X _d
[Wherein R is a hydrocarbon group, X is a halogen atom, and 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ (a + b) ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3, ≦ (c + d) ≦ 4. ]
Or an electron-donating adduct of these compounds.
Examples of the electron donor include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonia, amines, Examples thereof include nitrogen-containing electron donors such as nitrile and isocyanate.

Furthermore, as the organoaluminum compound as the promoter, at least one selected from those having at least one aluminum-carbon bond or aluminum-hydrogen bond is used.
In the above, for example, when the vanadium compound is used, the ratio of the vanadium compound to the organoaluminum compound is such that the ratio of aluminum atom to vanadium atom (Al / V) is 2 or more, preferably 2 to 50, particularly preferably 3 to 20. Range.

  As the solvent for the polymerization reaction used for the addition polymerization, the same solvent as that used for the ring-opening polymerization reaction can be used. Moreover, adjustment of the molecular weight of the (5) saturated copolymer obtained is normally performed using hydrogen.

Further, as the cyclic olefin resin used in the present invention, (6) one or more monomers selected from the above specific monomer and a vinyl cyclic hydrocarbon monomer or a cyclopentadiene monomer. Addition copolymers and their hydrogenated copolymers can also be used.
<Vinyl cyclic hydrocarbon monomer>
Examples of the vinyl cyclic hydrocarbon monomer include vinyl cyclopentene monomers such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene, 4-vinylcyclopentane, 4-isopropenylcyclopentane and the like. Vinylated 5-membered hydrocarbon monomers such as vinylcyclopentane monomers, 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-isopropenylcyclohexene, 2-methyl-4-vinyl Vinylcyclohexene monomers such as cyclohexene and 2-methyl-4-isopropenylcyclohexene, vinylcyclohexane monomers such as 4-vinylcyclohexane and 2-methyl-4-isopropenylcyclohexane, styrene, α-methylstyrene, 2-methylstyrene, 3- Styrenic monomers such as styrene styrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-phenylstyrene, p-methoxystyrene, d-terpene, 1-terpene, diterpene, d-limonene, 1- Terpene monomers such as limonene and dipentene, vinylcycloheptene monomers such as 4-vinylcycloheptene and 4-isopropenylcycloheptene, 4-vinylcycloheptane, 4-isopropenylcycloheptane, etc. And vinyl cycloheptane monomers. Styrene and α-methylstyrene are preferable. These can be used alone or in combination of two or more.

<Cyclopentadiene monomer>
Examples of the cyclopentadiene monomer used as the monomer of the addition copolymer (6) of the present invention include, for example, cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, Examples include 5-methylcyclopentadiene and 5,5-methylcyclopentadiene. Cyclopentadiene is preferred. These can be used alone or in combination of two or more.

The addition type (co) polymer of at least one monomer selected from the above specific monomer, vinyl cyclic hydrocarbon monomer and cyclopentadiene monomer is the above (5) specific monomer. It can be obtained by the same addition polymerization method as the saturated copolymer of the unsaturated double bond-containing compound.
The hydrogenated (co) polymer of the addition type (co) polymer can be obtained by the same hydrogenation method as the hydrogenated (co) polymer of the above (3) ring-opening (co) polymer. .

Furthermore, as the cyclic olefin-based resin used in the present invention, (7) an alternating copolymer of the specific monomer and acrylate can also be used.
<Acrylate>
Examples of the acrylate used in the production of the (7) alternating copolymer of the specific monomer and acrylate of the present invention include straight chain having 1 to 20 carbon atoms such as methyl acrylate, 2-ethylhexyl acrylate and cyclohexyl acrylate. C2-C20 heterocyclic group-containing acrylates such as chain, branched or cyclic alkyl acrylates, glycidyl acrylates, 2-tetrahydrofurfuryl acrylates, and aromatic ring groups containing 6-20 carbons such as benzyl acrylates Examples thereof include acrylates having a polycyclic structure having 7 to 30 carbon atoms such as acrylate, isobornyl acrylate, and dicyclopentanyl acrylate.

In the present invention, (7) In order to obtain an alternating copolymer of the specific monomer and acrylate, when the total of the specific monomer and acrylate is 100 mol in the presence of Lewis acid, The specific monomer is 30 to 70 mol, the acrylate is 70 to 30 mol, preferably the specific monomer is 40 to 60 mol, and the acrylate is 60 to 40 mol, particularly preferably the specific monomer. The polymer is radically polymerized at a ratio of 45 to 55 mol and acrylate of 55 to 45 mol.
(7) The amount of Lewis acid used to obtain the alternating copolymer of the specific monomer and acrylate is 0.001 to 1 mol per 100 mol of acrylate. Also, known organic peroxides or azobis radical polymerization initiators that generate free radicals can be used, and the polymerization reaction temperature is usually -20 ° C to 80 ° C, preferably 5 ° C to 60 ° C. . Moreover, the same solvent as used for the ring-opening polymerization reaction can be used as the solvent for the polymerization reaction.
The “alternate copolymer” as used herein refers to a structure in which the structural unit derived from the specific monomer is not adjacent, that is, the structural unit derived from the acrylate is always adjacent to the structural unit derived from the specific monomer. It means a copolymer having a structure as a unit, and does not deny a structure in which structural units derived from acrylate are adjacent to each other.

The preferred molecular weight of the cyclic olefin resin used in the present invention is 0.2 to 5 dl / g in intrinsic viscosity [η] inh, more preferably 0.3 to 3 dl / g, and particularly preferably 0.4 to 1.5 dl. The polystyrene-reduced number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 8,000 to 100,000, more preferably 10,000 to 80,000, and particularly preferably 12, The weight average molecular weight (Mw) is 20,000 to 300,000, more preferably 30,000 to 250,000, particularly preferably 40,000 to 200,000. It is.
Inherent viscosity [η] inh, number average molecular weight and weight average molecular weight are in the above ranges, so that the heat resistance, water resistance, chemical resistance, mechanical properties of the cyclic olefin resin and the extruded film of the present invention were used. The molding processability at the time becomes good.

  The glass transition temperature (Tg) of the cyclic olefin resin used in the present invention is usually 120 ° C. or higher, preferably 120 to 350 ° C., more preferably 130 to 250 ° C., and particularly preferably 140 to 200 ° C. When Tg is less than 120 ° C., for example, in an application requiring heat resistance such as in-vehicle use, the obtained film or sheet may be thermally deformed, which may be a problem. On the other hand, when Tg exceeds 350 ° C., melt extrusion processing becomes difficult, and the possibility that the resin deteriorates due to heat during the processing is not preferable.

When the cyclic olefin-based resin used in the present invention is an optical material, it is preferable that there are few foreign substances that cause visual defects and abnormal bright spots, and they do not exist as much as possible.
The content of such foreign matter is preferably 0/10 g of foreign matters of at least 50 μm or more, preferably 0/10 g of foreign matters of 30 μm or more, particularly preferably 0/10 g of foreign matters of 20 μm or more.
The amount of foreign matter is measured by dissolving the resin in a solvent having solubility such as toluene and cyclohexane, filtering with a filter, and observing with a microscope to count the size and number. It is also possible to measure the resin solution using a commercially available fine particle counter based on the principle of light scattering and to count the amount of foreign matter.
Moreover, it is preferable to suppress the content of the fine powder of the cyclic olefin resin used in the present invention as much as possible. A large amount of fine powder is not preferable because it appears as optical fluctuations and results in performance defects such as bright spots and blurred focus.

  Although it does not specifically limit regarding film thickness, Usually, it is 0.01 mm-5 mm, Preferably it is 0.03 mm-3 mm, More preferably, it is 0.03 mm-2 mm. When the thickness exceeds 5 mm, it may be difficult to extrude a wide film uniformly. On the other hand, when the film thickness is less than 0.01 mm, the toughness of the film is insufficient, and problems such as breakage may easily occur during film production or post-processing.

In order to prevent thermal degradation of the resin during melt extrusion, a known oxidation degradation inhibitor can be added to the cyclic olefin resin used in the present invention. Specific examples are given below, but the antioxidant used in the present invention is not limited thereto.
2,6-di-t-butyl-4-methylphenol, 4,4'-thiobis- (6-t-butyl-3-methylphenol), 1,1'-bis (4-hydroxyphenyl) cyclohexane 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 3,9-bis- [2- [3- (3-t-butyl-4-hydroxy-5 -Methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxospiro [5,5 '] undecane, 2,2'-dioxy-3,3'-di-t -Butyl-5,5'-dimethylphenylmethane, 2,2'-dioxy-3,3'-t-butyl-5,5'-diethylphenylmethane, 2,2'-methylenebis (4-ethyl-6- t-butylphenol), 2,5-di-t-butylhydroquinone, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Tan, 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) phenolic antioxidants such as benzene, hydroquinone antioxidants, or for example, tris (4-methoxy-3,5-diphenyl) phosphite, tris (2,4-t-butylphenyl) phosphite , Tris (nonylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol di Phosphi And phosphorous antioxidants such as bis (2,4-di-cumylphenyl) pentaerythritol diphosphite, and by adding one or more of these antioxidants, a cyclic olefin It is possible to improve the thermal / oxidative deterioration stability of the resin.

  Specific examples of other additives include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2-hydroxy-3′-t-butyl-5′-methylphenyl) -5- Chlorobenzotriazole, 2- (2-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- [2'-hydroxy-3'-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) 5'-methylphenyl] benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazole- 2-yl) phenol]], 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2,4-dihydroxybenzophenone, 2,2'- In addition to UV absorbers such as dihydroxy-4,4'-methoxybenzophenone, release agents, flame retardants, antibacterial agents, wood powder, coupling agents, petroleum resins, plasticizers, colorants, lubricants, antistatic agents There may be mentioned silicone oil, known additives such as foaming agents, it can be appropriately blended.

These additives preferably have a high weight loss temperature and a low vapor pressure. When the weight loss temperature is low and the vapor pressure is high, the copolymer is melted with an extruder, and when extruded from an appropriate die, the additive decomposes and volatilizes to produce die lines, fish eyes, etc. May adversely affect the surface properties of the skin. Therefore, among the additives used, at least as an antioxidant and an ultraviolet absorber, the 5% weight loss temperature is 300 ° C. or higher, and the vapor pressure at room temperature and normal pressure is 3 × 10 ⁻⁷ Pa or lower. Further, those having a 5% weight loss temperature of 330 ° C. or higher and a vapor pressure at room temperature and normal pressure of 3 × 10 ⁻⁹ Pa or lower are particularly preferable.

Among these, as the antioxidant, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6- Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and tris (2,4-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylene diphosphite and bis (2,4-di-cumylphenyl) pentaerythritol diphosphite are preferably used.
These antioxidants are usually added in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight, with respect to 100 parts by weight of the cyclic olefin resin. When the addition amount is too small, the effect of imparting thermal stability during melt extrusion is insufficient. On the other hand, when the addition amount is too large, appearance and optical properties are deteriorated due to bleeding out on the film surface.

In the present invention, it is preferable that the cyclic olefin-based resin gradually supplies moisture and oxygen components dissolved by a known method. In the case where the raw material is in a solid form such as particles or pellets, it is achieved by drying by a known method. As a known drying apparatus, a hot air dryer, a dehumidifying dryer, a nitrogen circulation dryer, a dehumidification nitrogen circulation dryer, a vacuum dryer, or the like can be used.
The drying temperature and drying time are not particularly limited, but can usually be arbitrarily set within the range of Tg-100 ° C to Tg-20 ° C, and the drying time is usually 2 to 6 hours. Set by range.
In addition, it is also effective to seal the portion that comes into contact with air with nitrogen in the extrusion device. That is, it is possible to use a method of sealing each part such as a hopper, a vent, and a die.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to a following example, unless the summary is exceeded.
In the following, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified.
Various measurement items are values obtained as follows.

Glass transition temperature (Tg)
According to JIS K 7121, it was measured with a differential scanning calorimeter (DSC) in a nitrogen atmosphere at a heating rate of 10 ° C./min.
Hydrogenation rate
^It was determined from the proton ratio of the proton on the carbon-carbon double bond of ¹ H-NMR and the methyl proton of the carboxymethyl group.
Intrinsic viscosity (η _inh )
The intrinsic viscosity of the chloroform solution of the sample prepared to a concentration of 0.5 g / dl was measured at 30.0 ° C. using an Ubbelohde viscometer.

Synthesis example 1
8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (specific monomer) 250 parts, 1-hexene (molecular weight regulator) 41 parts, toluene (ring-opening polymerization solvent) 750 parts in a reaction vessel in which nitrogen was substituted The solution was heated to 60 ° C. Next, 0.62 parts of a toluene solution of triethylaluminum (1.5 mol / l) and tungsten hexachloride modified with t-butanol / methanol (t-butanol: methanol: tungsten = 0.20) were added to the solution in the reaction vessel. 37 parts of a toluene solution (concentration 0.05 mol / l) of 35 mol: 0.3 mol: 1 mol) was added, and this system was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction. Thus, a ring-opening polymer solution was obtained.
The polymerization conversion rate in this polymerization reaction was 97%.
The autoclave was charged with 4,000 parts of the ring-opening polymer solution thus obtained, and RuCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. 0.48 parts was added, and the hydrogenation reaction was carried out by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C.
After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released.
The hydrogenated polymer thus obtained [hereinafter referred to as (A-1). ] Was measured by ¹ H-NMR at 400 MHz to be substantially 100%.
The intrinsic viscosity (η _inh ) of the polymer was 0.50 dl / g, and the glass transition temperature was 164 ° C.

Synthesis example 2
As a specific monomer, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1, ¹⁰ ] -3-dodecene 225 parts and bicyclo [2.2.1] hept-2-ene 25 parts, except that the amount of 1-hexene (molecular weight regulator) added was 43 parts Obtained a hydrogenated polymer in the same manner as in Synthesis Example 1. The obtained hydrogenated polymer [hereinafter referred to as (A-2). ] Was substantially 100%.
The intrinsic viscosity (η _inh ) measured in chloroform at 30 ° C. of the polymer was 0.50 dl / g, and the glass transition measured by a scanning calorimeter (DSC) at a heating rate of 10 ° C./min in a nitrogen atmosphere. The temperature was 141 ° C.

Example 1
An outline of the structure of the take-up device is shown in FIG.
The metal endless belt (transfer belt 7) used was a stainless steel belt having a surface roughness of 0.1 s (maximum scratch height of 0.1 μm), an average roughness Ra of 0.007 μm, and a thickness of 0.5 mm. Using. Further, a V-shaped groove shown in FIG. 3 is formed on the metal endless belt.

The take-up speed of the take-up machine is 9 m / min, the temperature of the transfer roll 6 and the transfer belt support roll 8 is adjusted with oil, the surface temperature of the transfer roll 6 is 115 ° C., and the surface temperature of the transfer belt support roll 8 is 130. Set to ° C. The transfer belt support roll 9 was cooled with cold water adjusted to 23 ° C.
The cyclic olefin-based resin A-1 obtained in Synthesis Example 1 was dried with a dehumidifying dryer at 100 ° C. for 4 hours. This resin was put into a 65 mmφ single-screw extruder and melt-extruded at 270 ° C. under nitrogen. While this molten resin was metered with a gear pump at a rate of 60 kg / hr, it was guided to a die while filtering foreign matter with a leaf disk polymer filter, and extruded from a 700 mm wide die having a coat hanger type manifold. The gap of the die lip part at this time was 0.5 mm. The gap at the lip portion at the tip of the die was 0.5 mm, and the air gap was 100 mm.
Further, by using the above-described take-up device, a groove-shaped transferred film having a thickness of 100 μm was obtained.

Example 2
A film having a groove shape having a thickness of 100 μm was obtained in the same manner as in Example 1 except that the cyclic olefin-based resin obtained in Synthesis Example 2: A-2 was used as the resin used for the extruded film.

Example 3
A film having a 100 μm-thick quadrangular pyramid shape transferred was obtained in the same manner as in Example 1 except that a metal endless belt (transfer belt 7) having the shape shown in FIG. 4 was used.

Example 4
A groove shape having a thickness of 100 μm is transferred in the same manner as in Example 1 except that a mirror end is used for the metal endless belt (transfer belt 7) and a transfer roll 6 having the pattern shown in FIG. 5 is used. Film was obtained.

Example 5
A transfer shape having a thickness of 100 μm is obtained in the same manner as in Example 1 except that the pattern shown in FIG. 4 is formed on the metal endless belt (transfer belt 7) and the pattern shown in FIG. 5 is formed on the transfer roll 6. Was obtained.

Comparative Example 1
A film on which a transfer shape having a thickness of 100 μm was transferred was obtained in the same manner as in Example 1 except that the apparatus shown in FIG. 6 was used as the take-up apparatus and the roll shown in FIG. 5 was used as the transfer roll.

Comparative Example 2
A film on which a transfer shape having a thickness of 100 μm is transferred in the same manner as in Example 1 except that the apparatus shown in FIG. 7 is used as the take-up apparatus, and the roll having the pattern shown in FIG. Got.

The obtained film was analyzed by the following method.
(Surface shape observation)
The film was sampled in a state of being sufficiently stable after being operated for 2 hours from the start of extrusion, and the transfer shape was measured at any 50 points of the film using Foam Talysurf (made by Taylor Hobson). The transfer rate when the groove depth d1 formed on the endless belt or the transfer roll and the height of the groove formed on the film were d2 was calculated based on the following formula.
Transfer rate (%) = d2 / d1 x 100
◎: Transfer rate is 95% or more ◯: Transfer rate is 90% or more and less than 95% △: Transfer rate is 80% or more and less than 90% ×: Transfer rate is less than 80%
To measure the maximum and minimum values of the residual phase difference of the inner surface by using a phase difference birefringence analyzer "KOBRA-21ADH" (manufactured by Oji Scientific Co.), and the difference was calculated.
The results of Examples 1 to 5 and Comparative Examples 1 and 2 are shown below.

  By comparing films of Examples 1 to 5 and Comparative Examples 1 and 2, a film is produced by the production method of the present invention, whereby the pattern is transferred well and the internal distortion is small (the birefringence is low). It can be seen that a film can be produced.

  Films and sheets obtained by the present invention are used in fields that require excellent optical properties, heat distortion resistance, and film thickness unevenness, such as display optical films (retardation films, polarizing films, polarizing plate protective films, diffusion films). , Antireflection film, liquid crystal substrate, PDP front plate, touch panel substrate, EL substrate, electronic paper substrate, etc.), film for optical recording disk, light guide plate, prism sheet, hologram element, medical inspection substrate, food inspection substrate, sustained release It can be suitably used for a chemical film, a circuit board application such as a hard printed board / flexible printed board / multilayer printed wiring board, a transparent conductive film, and the like.

It is the schematic in an example of the manufacturing apparatus used for the manufacturing method of the cyclic olefin resin sheet of this invention. It is the schematic of the structure of the take-up apparatus used in Example 1. FIG. 3 is an enlarged schematic diagram of a three-dimensional pattern on the surface of a metal endless belt (transfer belt 7) used in Example 1. FIG. FIG. 6 is an enlarged schematic diagram of a three-dimensional pattern on the surface of a metal endless belt (transfer belt 7) used in Example 4; 6 is an enlarged schematic diagram of a three-dimensional pattern on the surface of a transfer roll used in Example 5. FIG. It is the schematic of the take-up apparatus used in the comparative example 1. It is the schematic of the take-up apparatus used in the comparative example 2.

Explanation of symbols

1: Extruder 4: T die 6: Transfer roll 7: Transfer belt 8: Transfer belt support roll 9: Transfer belt support roll

Claims (4)

  In a method of casting a cyclic olefin resin having a polar group melt-extruded from a die using a metal endless belt and a metal roll, at least a metal endless belt having a three-dimensional pattern formed on the surface of the casting surface and / or a three-dimensional pattern on the surface A method for producing a surface-designable film or sheet, wherein a three-dimensional pattern is transferred to at least one surface of the film or sheet using a metal roll on which is formed.   The manufacturing method of the surface designable film or sheet | seat of Claim 1 using the metal endless belt and mirror surface metal roll which formed the solid pattern in the surface of the casting surface.   The manufacturing method of the surface designable film or sheet | seat of Claim 1 using the metal endless belt with which the casting surface is a mirror surface, and the metal roll which formed the solid pattern on the surface. The surface designable film or sheet manufactured by the manufacturing method in any one of Claims 1-3.