JP2009051021A - Producing method for resin composition molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for molding a film/sheet from a resin composition, which comprises at least one kind of cyclic olefinic polymers and at least one kind of styrene polymers, with low heat energy consumption by a simple process. <P>SOLUTION: In this producing method for resin composition moldings, the resin composition containing cyclic olefin polymers, styrene polymers, and a solvent is introduced into an extruder, and after removing volatile components in the resin composition inside the extruder, melt extrusion molding into a film/strand shaped is carried out by means of a die. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a resin composition molded article containing at least one cyclic olefin polymer and containing at least one styrene polymer.

  Thermoplastic norbornene resin (cyclic olefin resin) has high glass transition temperature and light transmittance, and low birefringence due to low refractive index anisotropy compared to conventional optical films. It has attracted attention as a transparent thermoplastic resin excellent in heat resistance, transparency and optical properties (see Patent Documents 1 to 6).

  In addition, in the fields such as optical disks, optical lenses, optical fibers, transparent plastic substrates, electronic and optical materials such as low dielectric materials, and sealing materials such as optical semiconductor sealing, the above features can be used. Application of resin has been studied.

  The characteristics of the above-mentioned cyclic olefin-based resin can improve the problems of the conventional resin even when viewed as a resin for optical films. For this reason, films made of cyclic olefin-based resins can be used as various optical films. Proposed.

  For example, Patent Documents 7 to 9 describe retardation plates using a cyclic olefin-based resin film. Patent Documents 10 to 12 describe the use of a cyclic olefin resin film as a protective film for a polarizing plate. Further, Patent Document 13 describes a liquid crystal display element substrate made of a cyclic olefin-based resin film.

  By the way, the phase difference film corrects the phase difference (birefringence) generated when light passes through the phase difference of the film, and widens the viewing angle or increases the contrast. Since the birefringence of the retardation film depends on the wavelength (λ) of transmitted light (positive wavelength dependency), in the visible light region (380 to 780 nm), for example, λ / 4 It was very difficult to produce a retardation film having a specific retardation such as that with high accuracy. However, for example, for a reflective or transflective liquid crystal display or optical disk pickup, a retardation film that generates a retardation of λ / 4 at a wavelength (400 to 700 nm) is required. In particular, in the case of a liquid crystal projector, a retardation of λ / 2 is required. However, in order to produce an optical film from a conventional cyclic olefin-based resin, the stretched film must be laminated so as to be orthogonal to the stretching axis. In the case of making a film by laminating, it is difficult to reduce the thickness of the obtained optical film as well as complicated processes such as film bonding, cutting, and adhesion.

In order to solve this problem, as the material whose phase difference increases as the wavelength of the transmitted light becomes longer, it is possible to select whether the average refractive index is larger as the longer wavelength or larger as the shorter wavelength is used. it can. In general, a material having an average refractive index that is longer as the wavelength is longer in the visible light region has an absorption maximum in the visible light region and / or the near infrared region (760 to 900 nm). In many cases, such as coloring causes problems such as coloring. Conversely, it has been found that a material having an average refractive index that is larger as the wavelength is shorter in the visible light region is suitable as a material used for a retardation film that requires transparency. Patent Documents 14 to 15 propose a blend of a retardation film made of a specific cellulose acetate resin and a styrene resin using a material having a larger average refractive index as the wavelength is shorter. However, a film made of a cellulose resin has problems in terms of changes in characteristics due to water absorption and heat resistance. Styrenic resins have good film-forming properties such as methylene chloride during film production. Solvents with high volatility cannot be used because of phase separation, and are limited to specific solvents. There was a problem in obtaining a film with high transparency, such as heating required.

For this reason, the advent of a resin composition capable of easily obtaining a transparent optical film and a method for producing an optical film and a pellet using the resin composition has been strongly desired.
Japanese Patent Laid-Open No. 1-132625 JP-A-1-132626 JP 63-218726 A JP-A-2-133413 JP 61-120816 A Japanese Patent Laid-Open No. 61-115912 JP-A-4-245202 JP-A-5-2108 Japanese Patent Laid-Open No. 5-64865 Japanese Patent Laid-Open No. 5-212828 JP-A-6-511117 JP-A-7-77608 JP-A-5-61026 JP 2000-137116 A JP 2001-337222 A

  The present invention has been made in view of the above problems, and has a low thermal history from a resin composition containing at least one cyclic olefin polymer, at least one styrene polymer, and a solvent. It is an object to provide a method for obtaining a molded body by a simple process.

  The inventors of the present invention have solved the above-mentioned problem, and a method for obtaining a molded body such as a film or a pellet from a resin composition containing at least one cyclic olefin polymer and containing at least one styrene polymer. The present invention was completed by earnest research.

That is, the present invention includes the following matters.
[1] A resin composition containing a cyclic olefin polymer, a styrene polymer and a solvent is introduced into an extruder, and after removing volatile components in the resin composition in the extruder, a film or a strand A method for producing a resin composition molded body that is melt-extruded from a die.
[2] The method for producing a resin composition molded article according to [1], wherein the resin composition contains a polymerization reaction solution containing a cyclic olefin polymer obtained by solution polymerization.
[3] The method for producing a resin composition molded body according to [1] or [2], wherein the cyclic olefin polymer is a polymer containing a structural unit represented by the following formula (1).

(In Formula (1), R < ¹ > -R < ⁴ > is a hydrogen atom, a halogen atom, a C1-C30 hydrocarbon group, or another monovalent organic group, and may be the same or different. ¹ and are integrated and R ² may form a divalent hydrocarbon group, R ³ and R ⁴ and the good .R ¹ also to form a divalent hydrocarbon group integrated in R ² May combine with each other to form a monocycle or polycycle, and R ³ and R ⁴ may combine with each other to form a monocycle or polycycle, and X is —CH═CH— or — CH ₂ CH ₂ — represents a plurality of X which may be the same or different, m is an integer of 0 to 2, and n is 0 or 1.
[4] The styrene-based polymer is a copolymer containing a structural unit represented by the following formula (2-1) and a structural unit represented by the following formula (2-2). [3] The method for producing a molded resin composition according to any one of [3].

(In formula (2-1) or (2-2), R represents a hydrogen atom or a methyl group, R ′ represents a halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, R 'present may be the same or different, p is an integer of 0 to 5, and q is an integer of 0 to 4.)
[5] The content of the cyclic olefin polymer in the resin component in the resin composition is 10 to 90% by weight, and the content of the styrene polymer is 90 to 10% by weight. The molding method of the resin composition in any one.

  ADVANTAGE OF THE INVENTION According to this invention, molded objects, such as a homogeneous high quality film and a pellet, can be manufactured from the resin composition containing at least 1 sort (s) of a cyclic olefin polymer and containing at least 1 sort (s) of a styrene polymer. .

  According to the present invention, since a molded product of a resin composition containing a cyclic olefin polymer and a styrene polymer can be produced with a small thermal history, the obtained molded product has a quality deterioration due to the thermal history. It has a suppressed high quality and can be suitably used for applications that require high optical properties.

Hereinafter, the present invention will be specifically described.
[Cyclic olefin polymer]
The cyclic olefin polymer used in the present invention is preferably a (co) polymer of a compound represented by the following formula (I) (hereinafter also referred to as “specific monomer”).

(In the general formula (I), R ^{1 to} R ⁴ are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or other monovalent organic group, which may be the same or different. Also, any two of R ^{1 to} R ⁴ may be bonded to each other to form a monocyclic or polycyclic structure.
Is 0 or a positive integer, and p is 0 or a positive integer. )
The cyclic olefin polymer used in the present invention includes a ring-opening (co) polymer of a specific monomer and, if necessary, another cycloolefin such as cycloalkene; Examples thereof include hydrogenated products; addition type (co) polymers of specific monomers and, if necessary, other cycloolefins and α-olefins; hydrogenated products of the addition type (co) polymers. Among these, a ring-opening (co) polymer and a hydrogenated product thereof are preferable from the viewpoint of optical properties and processability, and a hydrogenated product of the ring-opening (co) polymer from the viewpoint of long-term light resistance, that is, the above-mentioned In the polymer containing the structural unit represented by the formula (1), a polymer containing a structural unit in which X represents —CH ₂ CH ₂ — is preferable.

<Specific monomer>
Specific examples of the specific monomer include the following compounds, but the present invention is not limited thereto. That is,
Bicyclo [2.2.1] hept-2-ene,
Tricyclo [4.3.0.1 ^2,5 ] -3-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-isopropyl-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-heptafluoroisopropyl-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-dodecentricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene and spiro [fluorene-9,8′-tricyclo [4.3.0.1] ^2.5 ] [3] Decene]
Etc.

These specific monomers can be used alone or in combination of two or more.
Among the specific monomers, R ¹ and R ^{3 in the} general formula (I) are preferably a hydrogen atom or 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably 1 to carbon atoms. 2 and R ² and R ⁴ are a hydrogen atom or a monovalent organic group, and at least one of R ² and R ⁴ is a polar group other than a hydrogen atom and a hydrocarbon group. M is 0
An integer of 3 and n is an integer of 0 to 3, more preferably m + n = 0 to 4, more preferably m + n = 0 to 2, particularly preferably m = 1 and n = 0. The specific monomer in which m = 1 and n = 0 is preferable because the cyclic olefin polymer 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 have a linking group such as a methylene group. It may couple | bond with the cyclic olefin structure via. Among these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, and an allyloxycarbonyl group are preferable, and an alkoxycarbonyl group and an allyloxycarbonyl group are particularly preferable.

Furthermore, the specific monomer in which at least one of R ² and R ⁴ is a polar group represented by the formula — (CH ₂ ) _p COOR ″ has a high glass transition temperature and a low cyclic olefin polymer. It is preferable because it has hygroscopicity and excellent adhesion to various materials. In the above formula relating to the specific polar group, R ″ is 1 to 12 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly preferably carbon number. It is a hydrocarbon group of 1 to 2 and is preferably an alkyl group. Further, p is usually 0 to 5, but the smaller the value of p, the higher the glass transition temperature of the resulting cyclic olefin polymer, which is preferable. Further, when p is 0, synthesis is facilitated. So most preferred.

In the general formula (I), R ¹ or R ³ is preferably an alkyl group, an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and particularly preferably a methyl group. In particular, the fact that the alkyl group is bonded to the same carbon atom as the carbon atom to which the specific polar group represented by the formula — (CH ₂ ) _p COOR ″ is bonded is obtained. This is preferable in that the hygroscopicity of the coalescence can be lowered.

The cyclic olefin polymer used in the present invention is obtained by ring-opening (co) polymerization or addition (co) polymerization of the specific monomer and, if necessary, another monomer by a known method. It can be obtained by hydrogenation according to the above.

The preferred molecular weight of the cyclic olefin polymer used in the present invention is an intrinsic viscosity [η] _inh.
0.2 to 5 dl / g, more preferably 0.3 to 3 dl / g, and the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) is 8,000 to 100,000. More preferably, it is 10,000-80,000, Most preferably, it is 12,000-50,000, and a weight average molecular weight (Mw) is 20,000-300,000, More preferably, it is 30,000-250,000. Especially preferably, it is the range of 40,000-200,000.

  The glass transition temperature (Tg) of the cyclic olefin polymer used in the present invention is usually 100 ° C. or higher, preferably 100 to 350 ° C., more preferably 120 to 250 ° C., and particularly preferably 120 to 200 ° C.

[Styrene polymer]
Specific examples of the styrenic polymer used in the present invention include polystyrene, acrylonitrile-styrene copolymer, maleic anhydride-styrene copolymer, and derivatives thereof. ) And a copolymer containing a structural unit represented by the following formula (2-2) are particularly preferably used.

  R represents a hydrogen atom or a methyl group, R ′ represents a halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and a plurality of R ′ may be the same or different. p is an integer of 0 to 5, and q is an integer of 0 to 4.

  The content rate of a structural unit (2-2) is 0.1-50 mol% normally in 100 mol% of all structural units, Preferably it is 0.2-40 mol%, More preferably, it is 0.3-35 mol%. It is preferable for it to be within the above numerical range because there exists a solvent in which both the cyclic olefin polymer and the styrene polymer contained in the resin composition according to the present invention are well dissolved.

  Furthermore, the styrenic polymer may have a structural unit (3) represented by the following formula (3).

In formula (3), R ^{1 to} R ³ each independently represents a hydrogen atom; a halogen atom; an optionally substituted linking group containing an oxygen atom, a sulfur atom, a nitrogen atom, or a silicon atom. A hydrocarbon group having 1 to 30 carbon atoms; or a polar group. R ¹ and R ² are bonded to each other to form a carbocycle or a heterocycle (the carbocycle or heterocycle may be a monocyclic structure or other rings are condensed to form a polycyclic structure). May also be formed.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as methyl group, ethyl group and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group, allyl group and propenyl group. Groups and the like.

In addition, the substituted or unsubstituted hydrocarbon group may be directly bonded to the ring structure or may be bonded via a linking group. As the linking group, for example, a divalent hydrocarbon group having 1 to 10 carbon atoms (for example, an alkylene group represented by — (CH ₂ ) _m — (wherein m is an integer of 1 to 10)); oxygen , A linking group containing nitrogen, sulfur or silicon (for example, a carbonyl group (—CO—), an oxycarbonyl group (—O (CO) —), a sulfone group (—SO ₂ —), an ether bond (—O—), Thioether bond (-S-), imino group (-NH-
), Amide bonds (—NHCO—, —CONH—) and siloxane bonds (—OSi (R) — (wherein R is an alkyl group such as methyl or ethyl)), and the like, There may be.

  Examples of the polar group include a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, a carbonyloxy group, an alkoxycarbonyl group having 1 to 10 carbon atoms, an aryloxycarbonyl group, a cyano group, an amide group, an imide group, and a triorganosiloxy group. , Triorganosilyl group, amino group, acyl group, C1-C10 alkoxysilyl group, sulfonyl group, carboxyl group and the like. More specifically, examples of the alkoxy group include a methoxy group and an ethoxy group; examples of the carbonyloxy group include an alkylcarbonyloxy group such as an acetoxy group and a propionyloxy group, and an arylcarbonyloxy group such as a benzoyloxy group; Examples of the carbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group; examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a naphthyloxycarbonyl group, a fluorenyloxycarbonyl group, and a biphenylyloxycarbonyl group; Trimethylsiloxy group and triethylsiloxy group; triorganosilyl group such as trimethylsilyl group and triethylsilyl group; amino group such as primary amine Amino group; the alkoxysilyl group, such as trimethoxysilyl group and triethoxysilyl group.

Specific examples of the monomer for deriving the structural unit represented by the formula (3) include (meth) acrylamide, (meth) acrylic acid and derivatives thereof, maleic anhydride, maleimides, maleic acid and derivatives thereof. , Fumaric acid and its derivatives, and p-methoxystyrene. Further, a styrene monomer represented by the formula (II-1) and the formula (II-2), in which the styrene monomer partially remains after the deprotection reaction described later, Included in the monomer. The content of the structural unit (3) is usually 20 mol% or less, preferably 15 mol% or less, more preferably 10 mol in 100 mol% of all structural units.
% Or less.

The molecular weight distribution (Mw / Mn) of the styrenic polymer used in the present invention is usually 1.0 to 10, preferably 1.2 to 5.0, more preferably 1.2 to 4.0. .
<Method for producing styrene polymer>
The styrene polymer containing the structural units represented by the formula (2-1) and the formula (2-2), preferably used in the present invention, is a monomer represented by the following formula (II-1). Produced by converting at least one monomer and at least one monomer represented by the following formula (II-2) in the presence of a radical initiator, and then converting the OR ¹⁴ group into an OH group. Is done.

In formulas (II-1) and (II-2), R represents a hydrogen atom or a methyl group, R ′ represents a halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, and a plurality thereof R ′ may be the same or different. p is an integer of 0 to 5, and q is an integer of 0 to 4. R ¹⁴ represents an acetyl group, a t-butyl group, a t-butoxycarbonyl group, or a group represented by —CH (OR ¹⁵ ) (R ¹⁶ ) or —SiR ¹⁵ ₃ . R ¹⁵ and R ¹⁶ may each independently be an alkyl group having 1 to 6 carbon atoms, and R ¹⁵ and R ¹⁶ are integrated to form a divalent hydrocarbon group having 1 to 6 carbon atoms. You may do it. Among these, R and R ⁰ are preferably hydrogen atoms, and R ¹⁴ is preferably an acetyl group or a t-butyl group.

The monomer represented by the formula (II-1) or the formula (II-2) is preferably styrene alone.
You may polymerize the monomer represented by the said Formula (II-1) and Formula (II-2), and the monomer represented by following formula (III) as needed.

In the formula (III), R ¹ to R ³ have the same meanings as R ¹ to R ³ in the formula (3).
Polymerization Reaction Examples of the radical initiator used in the polymerization reaction include known organic peroxides that generate free radicals and azobis-based radical polymerization initiators. Note that a polyfunctional initiator or an initiator that easily causes a hydrogen abstraction reaction is not preferable because the linearity of the resulting polystyrene copolymer may be lowered.

Organic peroxides include diacetyl peroxide, dibenzoyl peroxide, diisobutyroyl peroxide, di (2,4-dichlorobenzoyl) peroxide, di (3,5,5-trimethylhexanoyl) peroxide, di Diacyl peroxides such as octanoyl peroxide, dilauroyl peroxide, distearoyl peroxide and bis [4- (m-toluoyl) benzoyl] peroxide;
Ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide and acetylacetone peroxide;

Hydrogen peroxide, t-butyl hydroperoxide, α-cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide and t-hexyl hydro Hydroperoxides such as peroxides;
Di-t-butyl peroxide, dicumyl peroxide, dilauryl peroxide, α, α′-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxide Dialkyl peroxides such as oxy) hexane, t-butylcumyl peroxide and 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3;

  t-butyl peroxyacetate, t-butyl peroxypivalate, t-hexyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, 2,5-dimethyl-2 , 5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2 -Ethyl hexanoate, t-butyl peroxyisobutyrate, t-butyl peroxy maleate, t-butyl peroxy 3,5,5-trimethyl hexanoate, t-butyl peroxy laurate, 2,5 -Dimethyl-2,5-bis (m-toluoylperoxy) hexane, α, α'-bis (neodecanoylpa -Oxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylper Oxyneodecanoate, t-butylperoxyneodecanoate, t-butylperoxybenzoate, t-hexylperoxybenzoate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl-2,5 -Peroxyesters such as bis (benzoylperoxy) hexane, t-butylperoxy m-toluoylbenzoate and 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone;

1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) 3,3 , 5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) cyclododecane, 2,2-bis (t-butylperoxy) butane, n Peroxyketals such as butyl 4,4-bis (t-butylperoxy) pivalate and 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane;
peroxymonocarbonates such as t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate and t-butylperoxyallyl monocarbonate;
Di-sec-butyl peroxydicarbonate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate Peroxydicarbonates such as di-2-ethylhexyl peroxydicarbonate, di-2-methoxybutyl peroxydicarbonate and di (3-methyl-3-methoxybutyl) peroxydicarbonate;

  In addition, although t-butyl trimethylsilyl peroxide etc. are mentioned, the organic peroxide used for this invention is not limited to these exemplary compounds.

  As the azobis radical polymerization initiator, azobisisobutyronitrile, azobisisovaleronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2 , 4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, , 2′-azobis [2-methyl-N- {1,1-bis (hydroxymethyl) -2-hydroxyethyl} propionamide], 2,2′-azobis [2-methyl-N- {2- (1 -Hydroxybutyl)} propionamide], 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2,2′-azobi [N- (2-propenyl) -2-methylpropionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) ), 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] Dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2′-azobis [2- (3,4,5,6-tetrahydropyrimidine- 2-yl) propane] dihydrochloride, 2,2′-azobis [2- {1- (2-hydroxyethyl) -2-imidazolin-2-yl} pro Dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methyl-propionamidine], 2,2′-azobis (2-methylpropionamidoxime), dimethyl 2,2′-azobisbutyrate, 4,4′-azobis ( 4-cyanopentanoic acid) and 2,2′-azobis (2,4,4-trimethylpentane), etc., but the azobis radical polymerization initiator used in the present invention is limited to these exemplified compounds. It is not something.

  The amount of these radical initiators used is usually 0.01 to 5 mol%, preferably 0.03 to 3 mol%, more preferably 0.05 to 2 mol% in 100 mol% of the total amount of the styrenic monomer.

  Furthermore, a catalyst may be used for the polymerization reaction of the styrene monomer. The catalyst is not particularly limited, and examples thereof include known anion polymerization catalysts, coordination anion polymerization catalysts, and cationic polymerization catalysts.

  The polymerization reaction of the styrenic monomer is carried out by subjecting the styrenic monomer to a bulk polymerization method, solution polymerization method, precipitation polymerization method, emulsion polymerization method, suspension polymerization method in the presence of the polymerization initiator or catalyst. And copolymerization by a conventionally known method such as a bulk-suspension polymerization method.

The solvent used for the solution polymerization is not particularly limited as long as the monomer and the polymer are dissolved, but a hydrocarbon solvent such as cyclohexane or toluene is preferable. The amount of the solvent used is preferably 0 to 3 times (weight ratio) with respect to the total amount of the styrene monomer.

  The polymerization reaction time is usually 1 to 30 hours, preferably 3 to 20 hours, and the polymerization reaction temperature is not particularly limited because it depends on the type of radical initiator used, but usually 40 to 180 ° C., preferably 50-120 ° C.

Conversion reaction to hydroxyl group In the styrene polymer preferably used in the present invention, the above styrene monomer is polymerized, and then the OR ¹⁴ group in the structural unit derived from the monomer (4) is further converted to a hydroxyl group. Can be obtained. Thereby, for example, R ¹⁴ of the styrene monomer represented by the formula (4) is eliminated, and a styrene polymer containing the structural unit represented by the formula (2-2) is formed.

Examples of the conversion reaction include a method of performing alcoholysis or hydrolysis in the presence of an acid or a base, a method of heating under acidic conditions, a method of performing only heating, and a method of conversion using fluoride ions. It is done. A suitable method among these varies depending on the type of R ¹⁴ in the OR ¹⁴ group, but is generally as follows.

R ¹⁴ in the OR ¹⁴ group can combine with, for example, an acetyl group (—COCH ₃ ), a t-butoxycarbonyl group (—COO ^t Bu), a silyl group (SiR ¹⁵ ₃ ), and an oxygen atom to form an acetal group. In the case of an alkoxyalkyl group (—CH (OR ¹⁵ ) (R ¹⁶ )) or the like, it is preferable to perform hydrolysis or alcoholysis under acidic conditions.

When R ¹⁴ in the OR ¹⁴ group is, for example, an acetyl group (—COCH ₃ ) or a t-butoxycarbonyl group (—COO ^t Bu), it is preferable to perform hydrolysis or alcoholysis under basic conditions.

Examples of R ¹⁴ in the OR ¹⁴ group in the case of performing the conversion reaction include a t-butyl group ( ^-t Bu) and a t-butoxycarbonyl group (-COO ^t Bu). The conversion is performed using fluoride ions. In this case, R ¹⁴ includes a silyl group (SiR ¹⁵ ₃ ), and is preferably used also when heating under acidic conditions or only heating.

Hydrolysis and alcohololysis Acids used for hydrolysis and alcohololysis include hydrohalic acids such as hydrochloric acid and hydrobromic acid, carboxylic acids such as formic acid, oxalic acid, acetic acid and trifluoroacetic acid, sulfuric acid, p -Toluenesulfonic acid, benzenesulfonic acid, sulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid, nitric acid, Bronsted acids such as phenols, heteropolyacids such as phosphotungstic acid and phosphomolybdic acid, sulfated zirconia and zeolites Lewis such as aluminum, titanium, tungsten and boron compounds in which at least one reaction selected from solid acids such as ion exchange resins and polymer electrolytes, halogenated, alkylated and alkoxylated Acid and public It includes the immobilized Lewis acid. As for the usage-amount of an acid, the molar ratio with the usage-amount of the styrene-type monomer represented by Formula (II-1) and Formula (II-2) is usually the styrene represented by an acid / Formula (4). System monomer = 1/1000 to 1/1, preferably 1/300 to 1/5.

Examples of the base include potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide and tetrabutylammonium hydroxide. The amount of the base used requires a number of moles equal to or greater than the number of moles of the styrenic monomer represented by the formula (II-1) and the formula (II-2). Usually, the formula (II-1) and the formula ( The molar ratio of the styrene monomer represented by II-2) to the amount of the styrene monomer represented by base / formula (II-1) and formula (II-2) = 1/1 ~ 5/1. Furthermore, it is necessary to neutralize with an acid after hydrolysis or alcoholysis. As the acid used for neutralization, the same acid as the above acid can be used. As the base, when a water-soluble base such as a metal hydroxide such as potassium hydroxide, sodium hydroxide or lithium hydroxide is used, a quaternary ammonium salt, a quaternary phosphonium salt, a crown ether is further used as a phase transfer catalyst. Poly (oligo) ethylene glycol and the like may also be used.

As reaction temperature, it is 0-180 degreeC normally, Preferably it is 30-150 degreeC, More preferably, it is 40-120 degreeC. As reaction time, it is 1 to 30 hours normally, Preferably it is 1 to 25 hours, More preferably, it is 1 to 20 hours. The reaction solvent is not particularly limited as long as the polymer before the conversion reaction and the polymer after the conversion reaction are dissolved, but the same solvent as the polymerization reaction is preferable. Further, the amount of the solvent used is preferably 1 to 5 times the weight of the solvent used for the polymerization reaction, more preferably 1 to 3 times the weight. The amount of water or alcohol added is preferably 1 to 30 moles, more preferably 1 to 20 moles of the OR ¹⁴ group. Although the kind of alcohol to be used is not specifically limited, It is preferable that it is a C1-C4 alcohol.

Heat conversion reaction under acidic conditions The same conditions as described above apply for the acid used in the heat conversion reaction under acidic conditions and the amount added, reaction temperature, reaction time, solvent type, and amount of solvent used. be able to. Moreover, in order to remove an acid, weak acid salts, such as a base similar to what was mentioned above, carboxylate, and a phenol salt, can also be used as needed. However, in this method, water or alcohol may or may not be added.

When R ¹⁴ in the OR ¹⁴ group of the styrene monomer represented by the conversion reaction formula (II-2) only by heating can be eliminated only by thermal energy, it does not greatly exceed the temperature at which the polymer chain decomposes. A styrene polymer can be obtained by thermal decomposition under temperature conditions. Such temperature is usually 100 to 350 ° C, preferably 120 to 300 ° C.

Conversion reaction using fluoride ions Examples of the reagent used for the conversion reaction using fluoride ions include tetramethylammonium fluoride, tetrabutylammonium fluoride, potassium fluoride, sodium fluoride, and hydrogen fluoride. . The amount of fluoride ion used is the molar ratio of the amount of fluoride ion used and the amount of styrene monomer represented by formula (II-1) and formula (II-2) (fluoride ion / formula The styrene monomer represented by (4) is usually 1/1 to 5/1, preferably 1/1 to 3/1.

<Purification>
A styrene polymer is obtained by refine | purifying after the said conversion reaction. For purification, a conventionally known method can be used. For example, after diluting the obtained reactant solution with a good solvent such as toluene or tetrahydrofuran, methanol, water or a mixed solution thereof is added to moderately polymerize the polymer. And a method of aggregating and extracting. In the extraction process, the weight ratio (good solvent / polymer) of the amount of good solvent to the total amount of the solvent used as the reaction solvent and the solvent added for dilution was 0.5 / 1 to 6 / 1, preferably 0.7 / 1 to 4/1.
Moreover, the usage-amount of poor solvents, such as methanol used for extraction, water, or these mixed solutions, is 0.3-5 by weight ratio (poor solvent / good solvent), Preferably it is 0.5-3. As extraction temperature, it is 40-120 degreeC normally, Preferably it is 50-100 degreeC.

After extraction as described above, the solution is cooled and separated into light multilayers, and the light layers are removed with a centrifuge or the like. After repeating these extraction operations 1 to 10 times, the heavy liquid can be concentrated and desolvated with a desolvating device such as a devolatizer or a ruder. The temperature at the time of solvent removal is 150 to 350 ° C, preferably 200 to 350 ° C, and the degree of vacuum is 0.1 to 50 mmHg, preferably 1 to 40 mmHg. Moreover, you may dilute before solvent removal and may implement circulation filtration. At the time of filtration, one having a pore size of 0.1 to 100 μm may be used alone, or a plurality of filters having different pore sizes may be installed stepwise. Moreover, you may refine | purify by filtering the molten polymer after solvent removal. In this case, the pore size of the polymer filter is preferably 0.1 to 100 μm.

The preferred molecular weight of the styrenic polymer is 0.10 to 5.00 dl in terms of intrinsic viscosity [η] _inh .
/ G, more preferably 0.15 to 3.00 dl / g, particularly preferably 0.20 to 1.50 dl / g, and the number average molecular weight in terms of polystyrene (Mn) measured by gel permeation chromatography (GPC). ) Is 2,000 to 100,000, more preferably 10,000 to 80,000, particularly preferably 12,000 to 50,000, and the weight average molecular weight (Mw) is 5,000 to 300,000, The preferred range is 10,000 to 250,000, and particularly preferred is 10,000 to 200,000. Intrinsic viscosity (η) _inh When the number average molecular weight and the weight average molecular weight are in the above ranges, the heat resistance, chemical resistance, mechanical properties, and moldability during molding of the resin composition are improved.

  The glass transition temperature (Tg) of the polymer used together with the cyclic olefin polymer in the present invention is usually 50 ° C. or higher, preferably 80 to 350 ° C., more preferably 100 to 250 ° C., particularly preferably 100 to 200 ° C. is there.

[solvent]
The solvent used in the present invention is not particularly limited as long as it dissolves each polymer. Specifically, alkanes such as pentane, hexane, heptane, octane, nonane and decane, cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin and norbornane, and fragrances such as benzene, toluene, xylene, ethylbenzene and cumene Group hydrocarbons, chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, halogenated alkanes such as chlorobenzene, chloroform and tetrachloroethylene and aryl halides, ethyl acetate, n-butyl acetate, isobutyl acetate, propionic acid And saturated carboxylic acid esters such as methyl and dimethoxyethane, and ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane. These may be used alone or as a mixture thereof. Of these, aromatic hydrocarbons are preferably used.

[Resin composition]
The resin composition used in the present invention contains a cyclic olefin polymer, a styrene polymer, and a solvent.

The content ratio of the cyclic olefin polymer and the styrene polymer constituting the resin composition used in the present invention is 10 to 90% by weight for the cyclic olefin polymer and 90 to 10% by weight for the styrene polymer. . The content varies depending on the properties required for the obtained molded product. For example, the content of the cyclic olefin polymer is 60 to 80% by weight when obtaining a molded product having reverse wavelength dispersion. More preferably, it is more preferably 40 to 60% by weight when obtaining a low birefringence molded article, and 3 when obtaining a negative retardation film.
More preferably, it is 0 to 40% by weight.

  In the resin composition used in the present invention, a known oxidative degradation inhibitor can be added in order to prevent thermal degradation of the resin during melt extrusion. Specific examples are given below, but the antioxidant used in the present invention is not limited thereto.

That is, 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-tetraoxyspiro [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-tert-butylphenol), 2,5-di-tert-butylhydroquinone, tetrakis [methylene-3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 1,3,5-trimethyl-2,4 Phenolic antioxidants such as 6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, hydroquinone antioxidants, or tris (4-methoxy-3,5-diphenyl) phosphite , Tris (2,4-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite,
Tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene diphosphite, tetrakis (2,4-di-t-butyl-5-methylphenyl) -4,4'-biphenylenediphos Phyto, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,4- Phosphorus antioxidants such as di-cumylphenyl) pentaerythritol diphosphite can be mentioned. By adding one or more of these antioxidants, the stability of thermal and oxidative degradation of cyclic olefin polymers Can be improved.

  The said antioxidant contains 0.01-5 weight part normally with respect to 100 weight part of resin compositions containing at least 1 sort (s) of cyclic olefin type polymers and at least 1 sort (s) of polymers other than a cyclic olefin type polymer, Preferably 0.1 to 3 parts by weight are added. When the addition amount is less than the above range, the effect of imparting thermal stability during melt extrusion is insufficient, and conversely, when the addition amount is more than the above range, the appearance and optical properties are deteriorated due to bleeding out on the film surface. Invite.

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-tert-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
-Benzotriazol-2-yl) phenol]], 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2,4-dihydroxybenzophenone and 2 , 2'-dihydroxy-4,4'-methoxybenzophenone and other UV absorbers, mold release agents, flame retardants, antibacterial agents, wood powder, coupling agents, petroleum resins, plasticizers, colorants, Known additives such as a lubricant, an antistatic agent, a silicone oil and a foaming agent can be used, and 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 cyclic olefin polymer is melted with an extruder, and when extruded from a suitable die, the additive decomposes or volatilizes, producing die lines and fish eyes, etc. However, it may adversely affect the surface properties of the film. Therefore, among the additives used, at least the antioxidant and the ultraviolet absorber have a 5% weight loss temperature of 300 ° C. or higher and a vapor pressure at room temperature and normal pressure of 3 × 10 ⁻⁷ Pa or lower. Preferably, the 5% weight loss temperature is 330 ° C. or higher, and the vapor pressure at normal temperature and normal pressure is 3 × 10 ⁻⁹ Pa or lower.

  The method for preparing the resin composition solution used in the present invention is not particularly limited, and any resin composition solution may be used as long as each resin pellet is dissolved in a solvent so as to have a desired concentration. That is, it is preferable to prepare by mixing a polymerization solution of a cyclic olefin polymer produced by solution polymerization and a polymerization solution of a styrene polymer produced by solution polymerization. Further, this solution is preferably concentrated after separating components such as a catalyst by a known method.

  The viscosity of the resin composition solution used in the present invention is not particularly limited, but the viscosity at a temperature of 100 ° C. is usually 5,000,000 mPa · s or less, preferably 3,000,000 mPa · s or less. More preferably, it is 1,000,000 mPa · s or less.

  The concentration of the total polymer in the resin composition solution used in the present invention is 20 to 80% by weight, preferably 30 to 75% by weight, particularly preferably 40 to 70% by weight. If the polymer concentration is less than 20% by weight, it is difficult to sufficiently volatilize the solvent component. Conversely, if the polymer concentration exceeds 80% by weight, the viscosity of the solution increases and the solution is transferred to an extruder. May be difficult.

  The Tg of the resin composition used in the present invention is usually 120 ° C. or higher, preferably 120 to 350 ° C., more preferably 120 to 250 ° C., and particularly preferably 120 to 200 ° C. When Tg is less than 120 ° C., for example, when used in applications requiring heat resistance such as in-vehicle applications, thermal deformation may occur in the film or sheet. On the other hand, if Tg exceeds 350 ° C., melt extrusion may become difficult, or the resin may be deteriorated by heat during processing.

  When the resin composition used in the present invention is used as an optical material, it is necessary to reduce the content of foreign substances that cause visual defects and abnormal bright spots as much as possible. When used as an optical material, the allowable amount of foreign matter is at least 0/10 g for foreign matters of 50 μm or more, 0/10 g for foreign matters of 30 μm or more, and 0/10 g for foreign matters of 20 μm or more. It is preferable.

  The foreign matter content is measured by dissolving the resin in a solvent such as toluene or cyclohexane, filtering through a filter, and counting the size and number by microscopic observation. Alternatively, the amount of foreign matter in the resin solution may be counted using a commercially available fine particle counter based on the principle of light scattering.

  Moreover, it is preferable to reduce the content of fine powder in the resin composition used in the present invention as much as possible. When the content of this fine powder is large, it appears as optical fluctuations, which is not preferable because it causes defects in performance such as bright spots and blurred focus.

[Molding method]
In this invention, after introducing the said resin composition into an extruder and removing the volatile matter in this resin composition in an extruder, it extrudes from a die | dye and is melt-extruded in the shape of a film or a strand.

  In the present invention, after each polymer is synthesized by solution polymerization, it is mixed as it is without removing the solvent, the solvent is removed under reduced pressure in an extruder, and melt extrusion is performed to obtain a film or pellet of the resin composition. A molded body can be produced. Therefore, compared with the conventional method, the steps of volatilization and re-dissolution of the solvent of each polymer can be omitted, and a film or pellet of the resin composition can be obtained with less energy.

In this invention, the resin composition containing a solvent is introduce | transduced into the extruder which has a vent, and a volatile component is isolate | separated. The method for transferring the resin composition solution to the extruder is not particularly limited, and a known pump or the like can be used. In addition, you may filter a resin composition solution in order to remove a foreign material and an impurity at the time of transfer.

  The extruder used in the present invention is not particularly limited as long as it is an extruder having a vent and a mechanism for melting and kneading a resin, such as a known single-screw, twin-screw or planetary multi-screw extruder. Are preferred. The heating of the extruder is also performed by a known method such as an electric heating type or an oil jacket type. Also, the screw of the extruder is not particularly limited, but in the case of a single shaft, for example, a full flight type, a subflight type and a dull mage type are used, and in the case of a twin shaft, for example, the same direction meshing type, the different direction meshing type Known screws such as a kneader type and a paddle type are used. It is also preferable to use a plurality of melt-kneading screws, kneading discs, paddles, full flights, peak cutouts, and the like having various shapes in combination according to the purpose. Further, it is preferable to subject the barrels and screws of these extruders to surface treatment and coating treatment by a known method.

  It is preferable that at least a part of the screw has a highly dispersed screw configuration. Here, the “highly dispersed screw configuration” refers to a configuration that includes a reverse feed screw and a forward feed screw, and the forward feed screw is sandwiched between the reverse feed screws. Although it does not specifically limit as a screw of a reverse feed, The reverse flight screw with favorable sealing performance is preferable. The progressive screw is not particularly limited, but a kneading disk is preferable. Further, another screw may be inserted between the reverse feed screw and the forward feed screw. It is preferable to use a progressive screw having a low conveying capacity because the effect of dispersion is enhanced. As a forward-feeding screw having a low conveying capacity, a mountaintop notch type screw can be mentioned. By using the highly dispersed screw configuration, the residual solvent in the resin at the exit of the extruder can be greatly reduced.

  The ratio of the cylinder length (L) to the screw diameter (D) (hereinafter referred to as “L / D”) in the extruder used in the present invention is not particularly limited, and the resin properties, product physical properties and Although depending on the solvent removal load, those with L / D of 10 to 80 are usually used, and those with L / D of 10 to 60 are preferably used.

  The resin composition solution introduced into the extruder is gradually concentrated and melt-kneaded in the extruder by removing the solvent, which is a volatile component, and the solvent is almost completely removed near the exit of the extruder. It becomes a thing.

  When producing an extruded film or a strand by the molding method of the present invention, the solvent content of the resin composition at the exit of the extruder is preferably 5000 ppm or less, and more preferably 1000 ppm or less. If it exceeds 5000 ppm, foaming, defects, die lines, dirt, and the like are generated, and molding of the film and the like becomes unstable, which is not preferable.

  The extruder used by this invention has a vent which can discharge | emit the solvent which is a volatile matter in the introduce | transduced resin composition solution out of an extruder. This vent may be singular or plural. When the extruder has a plurality of vents, the removal of the solvent from the resin composition solution in the extruder can be controlled in a stepwise manner depending on temperature conditions and the like, which is preferable in terms of improving efficiency. In addition, when the extruder has a plurality of vents, the solvent can be gradually removed at a relatively low operating temperature, so that the quality deterioration of the resin composition due to heating is more effective than when the solvent is removed at a high temperature. This is preferable because it can be prevented.

Further, when the extruder has a plurality of vents, it is preferable that one of them is a rear vent because the efficiency of solvent removal is improved. That is, in an extruder having only a front vent, when a resin solution having a high solvent concentration is supplied, the solvent load of the first front vent becomes too high and entrainment is likely to occur, but an extruder having a rear vent is used. And the load of the solvent on each vent is reduced, and it becomes easy to control so as not to cause entrainment. In this invention, it is preferable to control 15 to 35 weight% of the solvent in the resin solution supplied to the extruder by the solvent load to a rear vent.

  The operation temperature of the vent is not particularly limited and is determined in consideration of the viscosity of the resin solution to be handled and the melt viscosity after desolvation, but is usually in the range of 150 to 350 ° C, preferably 200 to 300 ° C.

  Further, the operation pressure of the vent is not particularly limited. The operation pressure of the vent may be set so that the solvent vapor in the vent does not cause entrainment, and varies depending on the operation temperature and desolvation load of each vent, but the solvent content in the resin is desolvated to 1000 ppm or less. For this, it is preferable that the operating pressure of each vent is usually 0.5 MPaG or less. Further, when the solvent is removed under a reduced pressure of 0 MPaG or less (atmospheric pressure or less), the thermal energy required for removing the solvent is saved, and the thermal history to the cyclic olefin polymer is preferably suppressed. More preferably, the solvent is removed at 0.05 MPaG or less.

  Moreover, when using the extruder which has multiple vents, it is preferable to have a seal part between each vent port of an extruder. Use of such an extruder is preferable because the operation temperature and operation pressure of each vent can be suitably changed and can be easily controlled so that entrainment due to desolvation load on each vent does not occur.

In addition, the solvent discharged | emitted out of the extruder from the vent can also be collect | recovered and recycled.
The discharge pressure of the extruder of the present invention is preferably constant in order to obtain a film having a uniform thickness because fluctuations in the discharge pressure cause uneven thickness of the film.

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

  From the exit of the extruder, as described above, the resin composition from which the solvent has been sufficiently removed is obtained in a melt-kneaded state. Here, a gear pump having a known mechanism can be used as necessary in order to prevent a decrease in extrusion amount due to stable discharge from the extruder and pressure loss in the die. By using a gear pump, the thickness accuracy of a film or sheet is improved, which is preferable.

Moreover, it is also preferable to install a known filter at the exit of the extruder to remove foreign matters, gelled products, impurities, and the like that cause defects in the film.
A film is obtained by discharging the melted resin composition from a flat die and solidifying the resin composition on a cooling roll. Specific examples of the flat die include a manifold die (T die), a fish tail die, and a coat hanger die. Of these, a coat hanger die and a manifold die are preferable.

Preferred materials for the extruder (cylinder, screw, etc.) and die include, but are not limited to, SCM steel and stainless steel such as SUS. Further, the inner surface of the extruder cylinder, the die and the screw surface of the extruder are plated with chromium, nickel, titanium, etc., PVD (Physical Vapor Deposition) method, etc., TiN, TiAlN, TiCN, CrN and DLC It is preferable to use a film on which a film such as (diamond-like carbon) is formed, a film in which tungsten carbide or other ceramic is sprayed, or a film in which the surface is nitrided. Such a surface treatment is preferable in that a uniform molten state of the resin can be obtained because the coefficient of friction with the resin is small.

  Examples of the method for tightly solidifying the film extruded from the die include a nip roll method, an electrostatic application method, an air knife method, a vacuum chamber method, a calendar method, and a sleeve method, which are suitable for the thickness and application of the film. A method is selected.

  Various surface treatments are preferably performed on the surface of the cooling roll for solidifying the film extruded from the die as well as the extruder cylinder and the inner surface of the die. These surface treatments prevent the adhesion of the extruded film to the roll surface and prevent the occurrence of uneven thickness of the film. Also, the surface accuracy of the cooling roll is increased, and the surface hardness is high, so that the film is not easily damaged. Even if it manufactures, it is preferable since the film surface precision can be maintained stably and a film without a thickness spot can be manufactured.

  In this invention, you may seal the part which contacts an active gas in an extruder and its peripheral device with an inert gas. The inert gas is not particularly limited, but nitrogen or argon having a purity of usually 98% or higher, preferably 99% or higher, particularly preferably 99.9% or higher is used. By introducing such an inert gas, it is possible to suppress the occurrence of film defects.

  Here, as the melt extrusion conditions for obtaining the melt-extruded film of the present invention, for example, the resin temperature (extruder cylinder temperature) is usually 200 to 350 ° C., preferably 240 to 320 ° C., and shear during melt extrusion. The speed is usually 1 to 500 (1 / sec), preferably 2 to 350 (1 / sec), more preferably 5 to 200 (1 / sec). If the resin temperature is less than 200 ° C., the resin cannot be uniformly melted. On the other hand, when it exceeds 350 ° C., the resin is thermally deteriorated at the time of melting, and it becomes difficult to produce a high-quality film having excellent surface properties. Moreover, when the shear rate at the time of extrusion is less than 1 (1 / sec), the resin cannot be melted uniformly, and thus an extruded film with small thickness unevenness cannot be obtained. On the other hand, if it exceeds 500 (1 / sec), the shearing force is too great, the resin and additives are decomposed or deteriorated, and defects such as foaming, die lines and deposits occur on the surface of the extruded film.

  The sheet or film obtained by the present invention can be processed by a known method. For example, stretching processes such as uniaxial stretching and biaxial stretching, embossing to form patterns and fine shapes, stamping, prism processing, printing processing, imparting antireflection and diffusion functions, hard coating, imparting conductivity and A dry or wet coating process for the purpose of providing a reflection function or the like can be performed. In addition, other cyclic olefin-based polymers, known thermoplastic resins, thermosetting resins, films, sheets, plate materials made of the same or other materials such as metals, glass and ceramics, or members formed into different shapes by a known method It is also possible to laminate. In the case of laminating, it is possible to select according to the purpose such as fusion by heat and ultrasonic waves, mechanical bonding using a known thermosetting or photocurable adhesive.

ADVANTAGE OF THE INVENTION According to this invention, the resin composition film or pellet which has the stable property formed from the resin composition from which the solvent which is a volatile matter was fully removed is obtained. In particular, a product obtained from the cyclic olefin polymer solution used in the present invention and a polymer solution other than the cyclic olefin polymer, or a hydrogenated product thereof, or a concentrate thereof has a heat history other than concentration. If not, when these polymers are subjected to melt-kneading in an extruder without undergoing a heating step or cooling step such as pelletization, drying and melting, a film in which quality deterioration such as coloring due to heat history is suppressed is suppressed. Or a pellet is obtained. Moreover, in this invention, since a film or a pellet can be manufactured from a resin composition with few process steps and thermal energy, it is economical in terms of simplification of equipment or energy saving.

  A film or pellet formed from the resin composition according to the present invention includes a retardation film, a polarizing plate, a polarizing plate protective film, a wave plate, a light diffusing plate, a prism sheet, an antireflection film, a liquid crystal, and a display for an electroluminescent device. It is suitably used for applications such as substrates, touch panels, and light guide plates.

〔Example〕
EXAMPLES The present invention will be specifically described below with reference to examples and the like, but is not limited thereto. 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 K7121, a differential scanning calorimeter (DSC) was measured at a heating rate of 10 ° C./min in a nitrogen atmosphere.

<Hydrogen addition rate>
It calculated | required from the ratio of protons, such as a methyl proton of a carbon-carbon double bond of 500 MHz and ¹ H-NMR, and a carboxymethyl group.

<Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)>
Gel permeation chromatography (GPC) (Tosoh Co., Ltd. HLC-8220GPC, column: Tosoh Co., Ltd. guard column H _XL- H, TSK gel G7000H _XL , TSK gel GMH _XL , TSK gel G2000H _XL Connection, solvent: tetrahydrofuran, flow rate: 1 mL / min, sample concentration: 0.7 to 0.8% by weight, injection amount: 70 μL, measurement temperature: 40 ° C., detector: RI (40 ° C.), standard substance: Tosoh The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured using TSK Standard Polystyrene Co., Ltd. Mn is the number average molecular weight.

<Logarithmic viscosity>
Using a Ubbelohde viscometer, the sample concentration is 0.5 g / dL in chloroform, and the temperature is 30.
The logarithmic viscosity at 0 ° C. was measured.

<Polymer molecular structure>
Using a superconducting nuclear magnetic resonance absorber (NMR, manufactured by Bruker, trade name: AVANCE500), ¹³ C-NMR was measured in deuterated chloroform, and the copolymerization composition ratio and the conversion rate of butoxy groups to hydroxyl groups were determined. Calculated.

<Polymer blend ratio in resin composition>
Dissolve the resin composition in tetrahydrofuran, gel permeation chromatograph (HLC-8220GPC manufactured by Tosoh Corporation), columns: Guard column H _XL- H manufactured by Tosoh Corporation, TSK gel G7000H _XL , TSK gel GMH _XL 2 , TSK gel G2000H _XL sequentially connected, solvent: tetrahydrofuran, flow rate: 1 mL / min, sample concentration: 0.7 to 0.8% by weight, injection amount: 100 μL, measurement temperature: 40 ° C., detector: UV (254 nm) ) Was used to quantify the styrene-based polymer in the resin composition from the area intensity of the spectrum obtained by using), and the blend ratio was calculated.

<Yellow Index (YI, Yellowness)>
Using a SM color computer SM-7-CH manufactured by Suga Test Instruments Co., Ltd., the C-light 2 ° visual field transmission measurement was performed three times to obtain an average value (measurement sample: 20 g of a toluene solution containing 10% by weight of resin, Measurement cell: cylindrical glass cell having an inner diameter of 60 mm and a height of 30 mm).

<Phase difference evaluation>
A toluene or methylene chloride solution (concentration: 25%) of the resin composition was cast on a smooth glass plate and then dried to be colorless and transparent with a thickness of 50 to 200 μm and a residual solvent of 0.5 to 0.8%. A film was obtained. Free-width uniaxial stretching or width-constrained uniaxial stretching was performed 1.2 to 3.0 times at a temperature 5 to 10 ° C. higher than the glass transition temperature (Tg) of the film. The retardation of the stretched film was measured using a retardation measuring device (manufactured by Oji Scientific Instruments, trade name: KOBRA21DH).

Synthesis Example 1 Synthesis of Cyclic Olefin Polymer (A) Monomer 12.46 kg represented by the following formula (1a), monomer 0.14 kg represented by the following formula (2a), The reaction vessel was charged with 1.4 kg of the monomer represented by 3a), 1.214 kg of 1-hexene as a molecular weight regulator and 21 kg of toluene, and heated to 80 ° C. To this, 37.7 mL of a toluene solution of triethylaluminum (0.6 mol / L) and a methanol-modified WCl ₆ toluene solution (0.025 mol / L) 131.44
mL was added and reacted at 80 ° C. for 1 hour to obtain a ring-opening polymer. Next, the obtained ring-opening polymer solution was diluted with 17.7 kg of toluene, and RuH (OC
4.69 g of O—Ar—CH ₂ CH ₂ CH ₂ CH ₂ CH ₃ ) (CO) [P (C ₆ H ₅ ) ₃ ] ₂ (wherein Ar represents a paraphenylene group) was added, and 90 After raising the temperature to 0 ° C., the hydrogen gas pressure was adjusted to 9 to 10 MPa, and the temperature was further raised to 160 to 165 ° C. and reacted for 3 hours to obtain a solution of hydrogenated product (A). This solution was diluted with toluene to adjust the solid content concentration to 20%. A part of the obtained solution was precipitated in a large amount of methanol and dried, and then the glass transition temperature, weight average molecular weight, molecular weight distribution, logarithmic viscosity and hydrogenation rate were measured.
Tg: 159 ° C., weight average molecular weight (Mw): 8.8 × 10 ⁴ , molecular weight distribution (Mw / Mn)
: 3.0, logarithmic viscosity (η): 0.65 dL / g, yield: 13 kg (yield 93%).
The hydrogenation rate of the hydrogenated product (A) determined by NMR measurement was 99.0% or more.

Synthesis Example 2 Synthesis of Styrene Polymer (B) In a glass flask equipped with a stirrer, a condenser and a thermometer, 127.87 g (1.23 mol) of styrene and 22.13 g of pt-butoxystyrene (0. 136 mol), 75 g of toluene as a solvent, and 0.67 g (2.7 mmol) of 1,1′-azobis (cyclohexane-1-carbonitrile) as a radical initiator were added, heated to 90 ° C., and reacted for 15 hours. A part of this polymerization solution was taken out and the reaction rate was measured, and it was 85%. Moreover, when molecular weight and molecular weight distribution were measured, Mw was 129,935 and Mw / Mn was 2.00.

To the resulting polymerization reaction solution, 150 g of toluene was added for dilution, and then 43.6 g (1.36 mol) of methanol and 1.338 g (0.0136 mol) of concentrated sulfuric acid were added.
The mixture was heated to 0 ° C. and reacted for 10 hours. To this reaction solution, an aqueous solution in which 1.255 g (0.0299 mol) of lithium hydroxide monohydrate was dissolved in 24 g of water was added and reacted at 60 ° C. for 0.5 hour. Styrene polymer is obtained by adding 0.270 g (0.0030 mol) of lactic acid to this reaction solution, reacting at 60 ° C. for 0.5 hour, diluting the obtained reaction solution with tetrahydrofuran, and coagulating it in a large amount of water. (B) was collected and purified. This polymer (B) was redissolved in toluene to obtain a solution having a solid concentration of 20%.
Mw: 131,910, Mw / Mn: 1.88, η: 0.44 dL / g, yield 80%.
The conversion rate to hydroxyl group was 99%.

[Example 1]
Mix each solution of the cyclic olefin polymer (A) obtained in Synthesis Example 1 and the styrene polymer (B) obtained in Synthesis Example 2 so that the resin mixing ratio is 65/35. And stirred to obtain a uniform resin composition solution. After adding 0.3 part of Irganox 1010 (manufactured by Ciba Specialty Chemicals) as an antioxidant to this solution to 100 parts of the copolymer, a filter having openings of 5 μm and 0.2 μm was connected in series. Filtered. The concentrated solution was supplied to an extruder having a rear vent at a flow rate of 2 kg / hr in terms of resin to remove the solvent. The resin from which the solvent was removed was pressurized with a gear pump and supplied to the die with a residence time of 0.5 hr to produce pellets having a diameter of 1 mm and a length of 5 mm. When the polymer blend ratio in the pellet was measured, the ratio of the cyclic olefin polymer (A) to the styrene polymer (B) was 65:35. The hue was YI = 0.9.

The extruder was operated under the conditions of L / D = 13, screw made of SUS, rotation speed 100 rpm, vacuum degree 50 torr, and heating medium temperature 220 ° C.
[Comparative Example 1]
After adding 0.3 part of Irganox 1010 (manufactured by Ciba Specialty Chemicals) as an antioxidant to the cyclic olefin polymer (A) obtained in Synthesis Example 1 with respect to 100 parts of the copolymer, the mesh is opened. Is filtered through a series of 5 μm and 0.2 μm filters, concentrated to a solids concentration of 50%, the solvent is removed under reduced pressure using a conventional method, and the residence time is 0.5 hr by extrusion molding. A pellet was prepared. For the styrenic polymer (B) obtained in Synthesis Example 2, pellets were produced with a residence time of 0.5 hr using the same method. Each pellet was mixed so that the resin mixing ratio was 65/35, melt-kneaded using a twin screw extruder, and pellets of the resin composition were obtained by extrusion molding with a residence time of 0.2 hr. The hue of the obtained pellet was YI = 1.5.

The operation of the extruder was performed under the conditions of L / D = 13, screw made of SUS, rotation speed 100 rpm, and heat medium temperature 220 ° C.
<Evaluation of film>
18 g of resin composition pellets obtained in Example 1 and Comparative Example 1 were dissolved in 162 g of methylene chloride, and a solution obtained by filtering under reduced pressure (filter medium: GA200 manufactured by ADVANTEC) was a smooth glass bath (inner dimensions: width 260 mm × depth). 380 mm × depth 5 mm). The film was peeled from the bathtub and then dried for 12 hours with a vacuum dryer at 100 ° C. to obtain a film having a thickness of 90 μm.

This film was cut into a width of 10 mm and a length of 70 mm, and stretched by heating with a tensile tester equipped with a thermostatic bath to prepare a stretched film. When the film was stretched twice at a temperature of 143 ° C. and a speed of 220% / min, the maximum stress during stretching was 63 kgf / cm ² . The film thickness of the obtained film was 64 μm and the haze was 0.4. When the phase difference was measured, it was R450 = 77 nm, R550 = 85 nm, R650 = 91 nm. Here, R450, R550, and R650 represent phase differences at wavelengths of 450 nm, 550 nm, and 650 nm, respectively.

  Furthermore, uniaxial stretching was performed using the film obtained by casting to obtain a stretched film in which the retardation (Re) was expressed at 137 to 140 nm. A polarizing plate peeled off a polarizing plate and a retardation film attached to the front surface of a liquid crystal panel of a liquid crystal television (LC-13B1-S, manufactured by Sharp Corporation) adopting an ASV type low reflection black TFT liquid crystal The stretched film obtained in the polarizing plate and the example was pasted again so that the stretched film was on the liquid crystal cell side so that the transmission axes overlapped.

  It is confirmed that in the direction of 45 ° and 60 ° polar angle of the liquid crystal television having this stretched film, there is little coloring in black display, the contrast is good, the visibility is excellent, and a good panel evaluation result is obtained. It was done.

  According to the production method of the present invention, it is possible to produce a molded body such as a film or a pellet with a small heat history and a small number of steps.

  The molded body according to the present invention includes a molded body used for various optical applications, a retardation film, a polarizing plate, a polarizing plate protective film, a wave plate, a light diffusing plate, a prism sheet, an antireflection film, a liquid crystal, and an electroluminescence element. It is suitably used for applications such as display substrates, touch panels, and light guide plates.

Claims (5)

  A resin composition containing a cyclic olefin polymer, a styrene polymer, and a solvent is introduced into an extruder, and volatile components in the resin composition are removed in the extruder. The manufacturing method of the resin composition molded object which carries out melt extrusion molding.   The manufacturing method of the resin composition molded object of Claim 1 in which the said resin composition contains the polymerization reaction solution containing the cyclic olefin type polymer obtained by solution polymerization. The method for producing a resin composition molded article according to claim 1 or 2, wherein the cyclic olefin polymer is a polymer containing a structural unit represented by the following formula (1).

(In Formula (1), R < ¹ > -R < ⁴ > is a hydrogen atom, a halogen atom, a C1-C30 hydrocarbon group, or another monovalent organic group, and may be the same or different. ¹ and are integrated and R ² may form a divalent hydrocarbon group, R ³ and R ⁴ and the good .R ¹ also to form a divalent hydrocarbon group integrated in R ² May combine with each other to form a monocycle or polycycle, and R ³ and R ⁴ may combine with each other to form a monocycle or polycycle, and X is —CH═CH— or — CH ₂ CH ₂ — represents a plurality of X which may be the same or different, m is an integer of 0 to 2, and n is 0 or 1. The styrene polymer is a copolymer containing a structural unit represented by the following formula (2-1) and a structural unit represented by the following formula (2-2). A method for producing a molded resin composition according to claim 1.

(In formula (2-1) or (2-2), R represents a hydrogen atom or a methyl group, R ′ represents a halogen atom; a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, R 'present may be the same or different, p is an integer of 0 to 5, and q is an integer of 0 to 4.)   The content ratio of the cyclic olefin polymer in the resin component in the resin composition is 10 to 90% by weight, and the content ratio of the styrene polymer is 90 to 10% by weight. The manufacturing method of a resin composition molded object.