KR100744290B1 - Process for producing cycloolefin resin film or sheet - Google Patents

Abstract

The manufacturing method of the cyclic olefin resin film or sheet of this invention contains a cyclic olefin resin and a solvent, and introduce | transduces the cyclic olefin resin solution containing 20-80 weight% of cyclic olefin resin into the extruder which has a vent, The volatile component of the cyclic olefin resin solution is removed in the extruder, and a film- or sheet-shaped molded article is melt-extruded with a die. According to the present invention, a solvent can be sufficiently removed by a simple method, and a cyclic olefin film or sheet having a stable property can be produced. Moreover, according to this invention, the manufacturing method of the cyclic olefin type polymer film or sheet which suppressed the quality deterioration by a heat history can be provided. Moreover, according to this invention, the manufacturing method of the economical cyclic olefin type polymer film or sheet which simplified the installation and saved thermal energy can be provided.

Method for producing cyclic olefin resin film or sheet, vent, extruder, thermal energy, hydrogenated copolymer, antioxidant

Description

Manufacturing method of cyclic olefin resin film or sheet {PROCESS FOR PRODUCING CYCLOOLEFIN RESIN FILM OR SHEET}

The present invention relates to a method for producing a film or sheet containing a cyclic olefin resin, and more particularly, the present invention is a solution produced by solution polymerization containing a cyclic olefin resin and a polymerization solvent (hereinafter referred to as "polymerization A cyclic olefin resin solution containing a cyclic olefin resin and a solvent, and the like, and a method for producing a film or sheet containing a cyclic olefin resin by a simple step.

Molded products such as sheets and films obtained from cyclic olefin resins are excellent in transparency, and also excellent in heat resistance, moisture resistance, chemical resistance, and the like, and are therefore expected to be used in many fields including the optical field.

The cyclic olefin resin can be produced by, for example, polymerizing or copolymerizing a cyclic olefin monomer with other monomers as necessary and hydrogenating them again if desired. When (co) polymerization is carried out by a solution polymerization method, It can obtain as a solution (polymerization solution) dissolved in a polymerization solvent.

For this reason, until manufacture of molded objects, such as a film and a sheet of cyclic olefin resin from a polymerization solution, generally, the solvent contained in a polymerization solution is volatilized, the cyclic olefin resin is isolate | separated from the solution, and the separated cyclic olefin resin is removed. Pelletizing, pellets are heated, melt kneaded, and molded by extrusion or the like. When manufacturing a film or sheet of cyclic olefin resin by such a method, since it is necessary to heat each step, such as volatilization of a solvent, pelletization, and melt kneading | mixing, a process is complicated and requires a lot of energy. In addition, due to the thermal history, impurities mixed in a small amount in the polymer or the polymer may be denatured to cause slight coloring, cloudiness, optical distortion, and the like. For this reason, the emergence of the method of manufacturing molded objects, such as a film and a sheet | seat of cyclic olefin resin from the solution containing cyclic olefin resin by the simple method which solves with little heat energy consumption and has little heat history, is desired. have.

This invention is made | formed in view of the said problem, and provides the method of manufacturing the film or sheet | seat of cyclic olefin resin from the cyclic olefin resin solution by the simple process which solves with little heat energy consumption and has little thermal history. It is.

Summary of the Invention

The manufacturing method of the cyclic olefin resin film or sheet of this invention contains cyclic olefin resin and a solvent, introduces the cyclic olefin resin solution containing 20-80 weight% of cyclic olefin resin into the extruder which has a vent, The volatile component of the cyclic olefin resin solution is removed in the extruder, and a film- or sheet-shaped molded article is melt-extruded with a die.

In this invention, it is preferable to use the extruder which made at least one part of screw structure high dispersion | distribution type. Moreover, it is preferable to use the extruder which has a rear vent, and it is more preferable to use the extruder which has a some vent. That is, in this invention, it is especially preferable to use the extruder which has a some vent and one of which is a rear vent.

Moreover, in this invention, it is preferable that cyclic olefin resin solution contains 40-70 weight% of cyclic olefin resin, and it produces | generates by solution polymerization containing cyclic olefin resin and a polymerization solvent as cyclic olefin resin solution. It is also preferred to use a solution comprising the prepared solution.

In this invention, it is preferable that solvent content of cyclic olefin resin in an extruder exit is 1000 ppm or less. It is also preferable to remove 15 to 35% of the solvent of the cyclic olefin resin solution in the rear vent of the extruder.

Moreover, in this invention, it is preferable to independently control the operation pressure of each vent independently using the extruder which has a sealing part between vent ports, It is also preferable to inject water into one or more between the vent ports of an extruder, It is also preferable to use the extruder whose screw structure of the position which injects this is a highly dispersed screw structure.

In this invention, it is preferable to use that whose water absorption is 0.05 to 0.5 weight% as cyclic olefin resin.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.

The following (co) polymer is mentioned as cyclic olefin resin used by this invention.

(A): Ring-opening polymer of the specific monomer represented by following General formula (1).

(B): Ring-opening copolymer of specific monomer and copolymerizable monomer represented by following General formula (1).

(C): Hydrogenated (co) polymer of said ring-opening (co) polymer of said (A) or (B).

(D): The (co) polymer which hydrogenated after ring-opening (co) polymer of said (A) or (B) by Friedel Craft reaction.

(E): The saturated copolymer of the specific monomer and unsaturated double bond containing compound represented by following General formula (1).

(F): an addition type (co) polymer of at least one monomer selected from specific monomers represented by the following general formula (1), vinyl cyclic hydrocarbon monomers and cyclopentadiene monomers, and hydrogenated (co) polymers thereof.

[In formula, R <^1> -R <^4> is a hydrogen atom, a halogen atom, a C1-C30 hydrocarbon group, or other monovalent organic group, respectively, and may be same or different, respectively. R ¹ and R ² or R ³ and R ⁴ may be integrated to form a divalent hydrocarbon group, and R ¹ or R ² and R ³ or R ⁴ may be bonded to each other to form a monocyclic or polycyclic structure. m is an integer of zero or positive, and p is an integer of zero or positive.]

<Specific monomer>

Although the following compounds are mentioned as a specific example of the said specific monomer, This invention is not limited to these specific examples.

Bicyclo [2.2.1] hepto-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] hepto-2-ene,

5-ethylbicyclo [2.2.1] hepto-2-ene,

5-methoxycarbonylbicyclo [2.2.1] hepto-2-ene,

5-methyl-5-methoxycarbonylbicyclo [2.2.1] hepto-2-ene,

5-cyanobicyclo [2.2.1] hepto-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] hepto-2-ene,

8-ethylidenetetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

5-phenylbicyclo [2.2.1] hepto-2-ene,

8-phenyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene,

5-fluorobicyclo [2.2.1] hepto-2-ene,

5-fluoromethylbicyclo [2.2.1] hepto-2-ene,

5-trifluoromethylbicyclo [2.2.1] hepto-2-ene,

5-pentafluoroethylbicyclo [2.2.1] hepto-2-ene,

5,5-difluorobicyclo [2.2.1] hepto-2-ene,

5,6-difluorobicyclo [2.2.1] hepto-2-ene,

5,5-bis (trifluoromethyl) bicyclo [2.2.1] hepto-2-ene,

5,6-bis (trifluoromethyl) bicyclo [2.2.1] hepto-2-ene,

5-methyl-5-trifluoromethylbicyclo [2.2.1] hepto-2-ene,

5,5,6-trifluorobicyclo [2.2.1] hepto-2-ene,

5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hepto-2-ene,

5,5,6,6-tetrafluorobicyclo [2.2.1] hepto-2-ene,

5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hepto-2-ene,

5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hepto-2-ene,

5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hepto-2-ene,

5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hepto-2-ene,

5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hepto-2-ene,

5,6-difluoro-5-heptafluoro-iso-propyl-6-trifluoromethylbicyclo [2.2.1] hepto-2-ene,

5-chloro-5,6,6-trifluorobicyclo [2.2.1] hepto-2-ene,

5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hepto-2-ene,

5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hepto-2-ene,

5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hepto-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-heptafluoro-iso-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

Etc. can be mentioned.

These specific monomers can be used individually by 1 type, or can use 2 or more types together.

Among the specific monomers, R ¹ and R ^{3 in} the formula (1) are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms, more preferably 1 to 4, particularly preferably 1 to 2 carbon atoms, and R ² and R ^A tetravalent hydrogen atom or a valent monovalent organic group, at least one of R ² and R ⁴ represents a polar group having a polarity other than a hydrogen atom and a hydrocarbon group, m is an integer of 0 to 3, and p is 0 to 3 It is an integer, More preferably, it is m + p = 0-4, More preferably, it is 0-2, Especially preferably, m = 1, p = 0. The specific monomer whose m = 1 and p = 0 is preferable at the point that the glass transition temperature of the cyclic olefin resin obtained is high, and it is excellent also in mechanical strength.

As a polar group of the said specific monomer, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, a cyano group, etc. are mentioned, These polar groups may be couple | bonded through coupling groups, such as a methylene group. Moreover, the hydrocarbon group etc. which the bivalent organic group which has polarities, such as a carbonyl group, an ether group, a silyl ether group, a thioether group, and an imino group, couple | bond and couple | bond are mentioned as a polar group. In these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, or allyloxycarbonyl group is preferable, and an alkoxycarbonyl group or allyloxycarbonyl group is especially preferable.

Additionally, one or more of the R ² and R ⁴ formula - (CH _{2) n} polar group of the monomer represented by COOR, the resulting cyclic olefin based resin is that it has excellent adhesion to the high glass transition temperature and low moisture absorption, a variety of materials It is preferable at the point. In the formula relating to the above specific polar group, R is a hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 4, particularly preferably 1 to 2 carbon atoms, preferably an alkyl group. In addition, n is usually 0 to 5, and the smaller the value of n, the higher the glass transition temperature of the obtained cyclic olefin resin is preferable, and the particular monomer where n is O is preferable in that its synthesis is easy.

In the formula (1), 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 a methyl group, and particularly this alkyl group. Is preferably bonded to the same carbon atom as the carbon atom to which the specific polar group represented by the general formula-(CH ₂ ) _n COOR is bonded, in that the hygroscopicity of the resulting cyclic olefin resin can be lowered.

<Copolymerizable monomer>

Specific examples of the copolymerizable monomer include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene and dicyclopentadiene. As carbon number of a cycloolefin, 4-20 are preferable and 5-12 are more preferable. These can be used individually by 1 type or in combination of 2 or more types.

The preferred use range of the specific monomer / copolymerizable monomer is 100/0 to 50/50 by weight, more preferably 100/0 to 60/40.

<Opening polymerization catalyst>

In this invention, the ring-opening polymerization reaction for obtaining the ring-opening polymer of (A) specific monomer and the ring-opening copolymer of (B) specific monomer and a copolymerizable monomer is performed in presence of a metathesis catalyst.

This metathesis catalyst comprises (a) at least one member selected from compounds of W, Mo, and Re, (b) Deming periodic table Group IA elements (e.g., Li, Na, K, etc.), Group IIA elements ( For example, Mg, Ca, etc., group IIB elements (e.g., Zn, Cd, Hg, etc.), group IIIA elements (e.g., B, Al, etc.), group IVA elements (e.g., Si, Sn, Pb, etc.), or a compound of group IVB elements (e.g., Ti, Zr, etc.), including combinations with one or more selected from those having at least one corresponding element-carbon bond or the corresponding element-hydrogen bond It is a catalyst.

In this case, in order to increase the activity of the catalyst, the additive (c) described later may be added.

Representative examples of the compounds of W, Mo, or Re suitable as the component (a) include WCl ₆ , MoCl ₆ , ReOCl ₃ and the like. The compound described in the row is mentioned.

(b) Specific examples of the component _{nC 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 , methyl alumoxane, LiH, etc. The compound of Unexamined-Japanese-Patent No. 1-32626 page 8 upper right column line 18 to 8th page lower right column 3 can be mentioned.

Alcohols, aldehydes, ketones, amines, and the like can be suitably used as representative examples of the component (c), which is an additive, and in Japanese Patent Application Laid-Open No. 1-32626, page 8, Uharan, line 16 to page 9 The compound shown in line 17 can be used.

As a usage-amount of a metathesis catalyst, in the molar ratio of the said (a) component and a specific monomer, "(a) component: specific monomer" is usually a range which becomes 1: 500-1: 50,000, Preferably it is 1: 1,000-1: It is preferably in the range of 10,000.

The ratio of the component (a) and the component (b) is preferably in the range of 1: 1 to 1:50, preferably 1: 2 to 1:30, in terms of metal atomic ratio.

The ratio of the component (a) and the component (c) is preferably in a molar ratio of (c) :( a) in the range of 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1.

<Solvent for Polymerization Reaction>

As a solvent (solvent which comprises a molecular weight regulator solution, a specific monomer, and / or a metathesis catalyst) used in a ring-opening polymerization reaction, For example, alkanes, such as a pentane, hexane, heptane, an octane, nonane, decane, etc. Cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, chlorobutane, bromohexane, methylene chloride, dichloroethane, Saturated carboxylic acids such as hexamethylene dibromide, chlorobenzene, chloroform, tetrachloroethylene and other compounds such as halogenated alkanes and aryl halides, ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate and dimethoxyethane Ethers such as esters, dibutyl ether, tetrahydrofuran and dimethoxyethane; and the like, and these may be used alone or in combination. Can. Among these, aromatic hydrocarbons are preferable.

As a usage-amount of a solvent, the quantity used as "a solvent: specific monomer (weight ratio)" is usually 1: 1-10: 1, Preferably the quantity used becomes 1: 1-5: 1.

<Molecular weight regulator>

Although the molecular weight of the ring-opening (co) polymer obtained can be controlled by polymerization temperature, the kind of catalyst, and the kind of solvent, in this invention, it adjusts by coexisting a molecular weight modifier in a reaction system.

Suitable molecular weight modifiers include, for example, α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene; Styrene is mentioned among these, 1-butene and 1-hexene are especially preferable.

These molecular weight regulators can be used individually or in mixture of 2 or more types.

As a usage-amount of a molecular weight modifier, it is preferable that it is 0.005-0.6 mol, Preferably it is 0.02-0.5 mol with respect to 1 mol of specific monomers provided for a ring-opening polymerization reaction.

(B) In order to obtain a ring-opening copolymer, in a ring-opening polymerization process, a specific monomer and a copolymerizable monomer can be ring-opened copolymerized, and also conjugated diene compounds, such as polybutadiene and polyisoprene, styrene-butadiene copolymer and ethylene-non-porous A specific monomer can be ring-opened-polymerized in the presence of an unsaturated hydrocarbon-based polymer including two or more carbon-carbon double bonds in a main chain such as a liquid diene copolymer or polynorbornene.

Although the ring-opening (co) polymer obtained as mentioned above is used as it is, the (C) hydrogenated (co) polymer obtained by hydrogenating this again is useful as a raw material of resin with high impact resistance.

<Hydrogenated Catalyst>

The hydrogenation reaction is a conventional method, i.e., a hydrogenation catalyst is added to a solution of a ring-opening polymer, and hydrogen gas at atmospheric pressure to 300 atm, preferably 3 to 200 atm is 0 to 200 캜, preferably 20 to 180 It is carried out by acting at 占 폚.

As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. As this hydrogenation catalyst, a heterogeneous catalyst and a homogeneous catalyst are mentioned.

As a heterogeneous catalyst, the solid catalyst which carried noble metal catalyst substances, such as palladium, platinum, nickel, rhodium, ruthenium, on support | carriers, such as carbon, a silica, alumina, titania, is mentioned. As the homogeneous catalyst, naphthenic acid nickel / triethylaluminum, nickelacetylacetonate / triethylaluminum, cobalt octate / n-butyllithium, titanocenedichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenyl Phosphine) rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium and the like. The form of the catalyst may be powder or grainy.

These hydrogenated catalysts are used in a ratio such that the ring-opening (co) polymer: hydrogenated catalyst (weight ratio) is 1: 1 × 10 ⁻⁶ to 1: 2.

The hydrogenated (co) polymer obtained by the hydrogenation in this way has excellent thermal stability, and its properties are not deteriorated even by heating at the time of molding processing or use as a product. Here, hydrogenation rate is 50% or more normally, Preferably it is 70% or more, More preferably, it is 90% or more.

Further, the hydrogenation rate of the hydrogenated (co) polymer is 50% or more, preferably 90% or more, more preferably 98% or more, most preferably 99% or more, as measured by 500 MHz and ¹ H-NMR. to be. The higher the hydrogenation rate, the better the stability to heat and light, and when used as a wave plate, for example, stable properties can be obtained over a long period of time.

Moreover, it is preferable that the gel content contained in the said hydrogenated (co) polymer is 5 weight% or less, and, as for the hydrogenated (co) polymer used as cyclic olefin resin of this invention, it is especially preferable that it is 1 weight% or less.

As the cyclic olefin resin of the present invention, (D) the ring-opened (co) polymer of (A) or (B) may be cyclized by Friedel Craft reaction, and then a hydrogenated (co) polymer may also be used.

Cyclization by Friedel Craft Reaction

The method of cyclizing the ring-opened (co) polymer of (A) or (B) by Friedel Craft reaction is not particularly limited, but a known method using an acidic compound described in Japanese Patent Application Laid-open No. 50-154399 can be employed. Can be. 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, zeolites, activated clay, and Bronsted acids.

The cyclized ring-opening (co) polymer can be hydrogenated like the ring-opening (co) polymer of (A) or (B).

Moreover, the saturated copolymer of (E) the said specific monomer and unsaturated double bond containing compound can also be used as cyclic olefin resin of this invention.

<Unsaturated double bond containing compound>

As the unsaturated double bond-containing compound, for example, ethylene, propylene, butene, etc., preferably an olefin compound having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms.

The preferred use range of the specific monomer / unsaturated double bond containing compound is 90/10 to 40/60 by weight, and more preferably 85/15 to 50/50.

In this invention, in order to obtain the saturated copolymer of (E) specific monomer and an unsaturated double bond containing compound, a normal addition polymerization method can be used.

<Addition polymerization catalyst>

As a catalyst for synthesizing the saturated copolymer (E), at least one selected from a titanium compound, a zirconium compound and a vanadium compound and an organoaluminum compound as a cocatalyst are used.

Here, titanium tetrachloride, titanium trichloride, etc. are mentioned as a titanium compound, bis (cyclopentadienyl) zirconium chloride, bis (cyclopentadienyl) zirconium dichloride, etc. are mentioned as a zirconium compound.

As the vanadium compound, the formula VO (OR) _a X _b or V (OR) _c X _d [where R is a hydrocarbon group and X is a halogen atom, 0 ≦ a ≦ 3, O ≦ b ≦ 3, 2 ≤ (a + b) ≤ 3, O ≤ c ≤ 4, O ≤ d ≤ 4, 3 ≤ (c + d) ≤ 4.], a vanadium compound, or an electron donating adduct thereof.

As the electron donor, oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, alkoxysilanes, nitrogen-containing compounds such as ammonia, amines, nitriles, and isocyanates Electron donors and the like.

As the organoaluminum compound as a 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, in the case of using a vanadium compound, the ratio of the vanadium compound and the organoaluminum compound (Al / V) of the aluminum atom to the vanadium atom is 2 or more, preferably 2 to 50, particularly Preferably it is the range of 3-20.

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. In addition, adjustment of the molecular weight of the (E) saturated copolymer obtained is normally performed using hydrogen.

As the cyclic olefin resin of the present invention, (F) an addition type copolymer of one or more monomers selected from the above-mentioned specific monomers and vinyl cyclic hydrocarbon monomers or cyclopentadiene monomers, and hydrogenated copolymers thereof may also be used. have.

<Vinyl cyclic hydrocarbon monomer>

Examples of the vinyl cyclic hydrocarbon monomers include vinylcyclopentene monomers such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene, 4-vinylcyclopentane, 4-isopropenylcyclopentane, and the like. Vinylated 5-membered ring hydrocarbon monomers such as vinylcyclopentane monomers, 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-isopropenylcyclohexene, and 2-methyl-4-vinylcyclo Vinylcyclohexene monomers such as hexene and 2-methyl-4-isopropenylcyclohexene, vinylcyclohexane monomers such as 4-vinylcyclohexane and 2-methyl-4-isopropenylcyclohexane, styrene and α- Styrene-based monomers such as methyl styrene, 2-methyl styrene, 3-methyl styrene, 4-methyl styrene, 1-vinyl naphthalene, 2-vinyl naphthalene, 4-phenyl styrene, p-methoxy styrene, d-terpene, 1- Terpene monomers, such as terpene, diterpene, d-limonene, 1-limonene, and dipentene, 4-vinyl city Vinylcycloheptane monomers such as cloheptene and 4-isopropenylcycloheptene, and vinylcycloheptane monomers such as 4-vinylcycloheptane and 4-isopropenylcycloheptane. Styrene and (alpha) -methylstyrene are preferable. These can be used individually by 1 type or in combination of 2 or more types.

<Cyclopentadiene monomers>

As a cyclopentadiene type monomer used for the monomer of the (F) addition type copolymer of this invention, for example, cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, 5 -Methylcyclopentadiene, 5,5-methylcyclopentadiene, etc. are mentioned. Cyclopentadiene is preferred. These can be used individually by 1 type or in combination of 2 or more types.

The addition type (co) polymer of at least one monomer selected from the above-mentioned specific monomer, vinyl cyclic hydrocarbon monomer and cyclopentadiene monomer may be added polymerization method such as saturated copolymer of (E) specific monomer and unsaturated double bond containing compound. You can get

In addition, 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 (C) ring-opening (co) polymer.

It is preferable that cyclic olefin resin used by this invention has a moderate degree of water absorption or hygroscopicity. In the present invention, the cyclic olefin resin has a moderate degree of absorbency or hygroscopicity, so that a known dry or wet coating or a film, sheet, and a known molded body and laminate containing a known organic polymer, an organic compound, and an inorganic compound. Since the adhesiveness and applicability | paintability become favorable in carrying out a secondary process, such as forming a, it is preferable.

Here, the absorbency is a property of absorbing water when the material is in the liquid phase, and the hygroscopicity is a property of absorbing the water vapor component when the water is in the gas phase as water vapor. In the present invention, the ultimate form of hygroscopicity can be regarded as absorbency, and is considered to be equivalent in concept. In the present invention, the absorbency of the appropriate degree is an absorbance measured in accordance with JIS K 7209, 0.05 to 0.5% by weight, more preferably 0.08 to 0.4% by weight, particularly preferably 0.1 to 0.35% by weight, such absorption rate It is preferable to use cyclic olefin resin which shows the following. When the absorptivity of cyclic olefin resin is less than 0.05 weight%, a problem may arise in the said secondary workability of a film or sheet, and when an absorptivity is 0.5 weight% or more, it is a dimension, shape, or optical characteristic by absorption or moisture absorption. Problems may occur in the back.

Preferred molecular weight of the cyclic olefin resin used in the present invention is 0.2 to 5 dl / g, more preferably 0.3 to 3 dl / g, particularly preferably 0.4 to 1.5 dl / g in an intrinsic viscosity [η] ^inh , 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, particularly preferably 12,000 to 50,000, and the weight average molecular weight (Mw) Silver is very suitable in the range of 20,000 to 300,000, more preferably 30,000 to 250,000, particularly preferably 40,000 to 200,000.

The intrinsic viscosity [η] ^inh , the number average molecular weight and the weight average molecular weight are in the above ranges, thereby improving heat resistance, water resistance, chemical resistance, mechanical properties, and molding processability when used as the extruded film of the present invention. .

As glass transition temperature (Tg) of cyclic olefin resin used for this invention, it is 120 degreeC or more normally, Preferably it is 120-350 degreeC, More preferably, it is 120-250 degreeC, Especially preferably, it is 120-200 degreeC. When Tg is less than 120 degreeC, thermal deformation may arise in the obtained film or sheet | seat, and may become a problem, for example in the use required for heat resistance, such as an on-vehicle use. On the other hand, when Tg exceeds 350 degreeC, melt-extruding process becomes difficult and it is unpreferable since the possibility of resin deterioration or deterioration by heat at the time of such processing becomes high.

When the cyclic olefin resin of this invention is an optical material, it is preferable that there are few foreign substances which cause visual defects or an abnormal bright point, and exist as little as possible.

The content of such foreign matters is that at least 50 μm or more of foreign matters are 10 pieces of 10g, preferably 30 μm or more of foreign matters are of 10 pieces of 10g, and particularly preferably 20 or more of foreign matters are of 10 pieces of 10g.

The measurement of the amount of foreign matters is performed by counting the size and number by dissolving the resin in a soluble solvent such as toluene, cyclohexane, filtering with a filter, and observing with a microscope. It is also possible to count the amount of foreign matter by measuring the resin solution using a commercially available particulate counter of the light scattering principle.

Moreover, it is preferable to suppress content of the fine powder of cyclic olefin resin of this invention as much as possible. In the case where a large number of these fine powders are present, they are undesired because they appear in optical fluctuations and cause performance defects such as blurring of light points and focal points.

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 thickness exceeds 5 mm, it may become difficult to extrude a wide film uniformly. On the other hand, when film thickness is less than 0.01 mm, the toughness of a film may run out and a problem, such as a breakage, may arise easily at the time of film manufacture or post-processing.

In order to prevent the thermal deterioration of resin at the time of melt-extrusion, a well-known oxidation deterioration inhibitor can be added to cyclic olefin resin used for this invention. Although the specific example is given to the following, antioxidant used for this invention is not limited to these.

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-t-butylphenol), 2,5-di-t-butylhydroquinone, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl ) Propionate] methane, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3 Phenolic antioxidants such as, 5-di-t-butyl-4-hydroxybenzyl) benzene, hydroquinone antioxidants, or tris (4-methoxy-3,5-diphenyl) phosphite, Tris (2,4-t-butylphenyl) force Ytt, tris (nonylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylenediphosphite, tetrakis (2,4-di-t-butyl-5 -Methylphenyl) -4,4'-biphenylenediphosphite, bis (2,4-di-t-butylphenyl) pentaerythritoldiphosphite, bis (2,6-di-t-butyl-4-methylphenyl) Phosphorus antioxidants, such as pentaerythritol diphosphite and bis (2, 4- di- cumylphenyl) pentaerythritol diphosphite, are mentioned, The addition of these antioxidants 1 type, or 2 or more types of cyclic olefin resin is carried out. Thermal and oxidation deterioration stability can be improved.

Specific examples of the other additives include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 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" -tetrahydrophthalimidemethyl) 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-dihydrate Release agents, flame retardants, antibacterial agents, wood powder, coupling agents, petroleum resins, plasticizers, colorants, lubricants, in addition to ultraviolet absorbers typified by oxybenzophenone, 2,2'-dihydroxy-4,4'-methoxybenzophenone, and the like And well-known additives, such as an antistatic agent, silicone oil, and a foaming agent, These can be mix | blended suitably.

These additives preferably have high weight reduction temperatures and low vapor pressures. When the weight loss temperature is low and the vapor pressure is high, the cyclic olefin resin is melted by an extruder, and when the die is extruded from a suitable die, additives decompose and volatilize, causing die lines, fish eyes, etc. to adversely affect the surface of the film There is. Therefore, among the additives used, at least the antioxidant and ultraviolet absorber have a 5% weight reduction temperature of 300 ° C or higher, preferably a vapor pressure of 3 × 10 ^-7 Pa or lower at normal temperature and normal pressure, and further, a 5% weight reduction temperature thereof. It is especially preferable that it is 330 degreeC or more and the vapor pressure in normal temperature normal pressure is 3 * 10 <^-9> Pa or less.

Among them, as an 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'-biphenylenediphosphite and bis (2,4-di-cumylphenyl) pentaerythritol diphosphite are preferably used.

The antioxidant is usually added in an amount of 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight based on 100 parts by weight of the cyclic olefin resin. When the addition amount is too small, the effect of providing thermal stability at the time of melt extrusion is insufficient, while on the other hand, when the addition amount is too large, the appearance and optical properties are lowered by bleeding out to the film surface.

Method of making a film or sheet

In this invention, a cyclic olefin resin film or sheet is manufactured from the cyclic olefin resin solution containing the above-mentioned cyclic olefin resin.

The cyclic olefin resin solution used in the present invention contains a cyclic olefin resin and a solvent, and the cyclic olefin polymer in the solution is 20 to 80% by weight, preferably 30 to 75% by weight, particularly preferably 40 to 70% by weight. It contains%. If the concentration of the cyclic olefin resin solution is less than 20% by weight, it is difficult to volatilize the solvent component sufficiently. If the concentration of the cyclic olefin resin is more than 80% by weight, the viscosity of the solution becomes high and the transfer to the extruder becomes difficult. Not desirable

Although any solvent which can melt | dissolve cyclic olefin resin can be used as a solvent which comprises a cyclic olefin resin solution, The solvent used when superposing | polymerizing the above-mentioned cyclic olefin resin is preferable.

For example, alkanes such as pentane, hexane, heptane, octane, nonane, decane, cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, norbornane, benzene, toluene, xylene, ethylbenzene, Aromatic hydrocarbons such as cumene, chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylenedibromide, chlorobenzene, chloroform, tetrachloroethylene and other compounds such as halogenated alkanes and halogenated aryl, ethyl acetate, acetic acid n- Saturated carboxylic acid esters such as butyl, iso-butyl acetate, methyl propionate and dimethoxyethane; ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane; It is available. Among these, aromatic hydrocarbons are preferable.

The method for adjusting the cyclic olefin resin solution used in the present invention is not particularly limited, and the cyclic olefin resin pellet may be dissolved in a solvent so as to have a solution having a desired concentration, but the cyclic olefin resin and polymerization solvent produced by solution polymerization It is preferable that it is a solution containing. Moreover, it is especially preferable that this solution is concentrated after separating a component, such as a catalyst, by a well-known method.

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

In the present invention, the cyclic olefin resin solution is introduced into an extruder having a vent to separate volatile components. The conveyance of a cyclic olefin resin solution to an extruder is not specifically limited, A well-known pump etc. can be used. Moreover, at the time of conveyance, a cyclic olefin polymer solution can be filtered in order to remove a foreign material and an impurity.

The extruder of the present invention is not particularly limited as long as it has an vent and is an extruder of a mechanism for melt kneading a resin, and a known single-axis, biaxial, or satellite multiaxial extruder can be preferably used. Heating of an extruder is also performed by well-known methods, such as a heat transfer type and an oil jacket type. Moreover, the screw of an extruder is not specifically limited, either, In the case of a single axis, a full-flight type | mold, a sub-flight type | mold, a Darmage type | mold, etc. are mentioned, for example, In the case of a biaxial | shaft, a cooperative bite-type and a bidirectional bite-type It is possible to use well-known things, such as a kneader type and a paddle type. It is also preferable to use an extruder in which a plurality of shapes of melt kneading screw, kneading disc, paddle, full flight, and calculation notch are combined according to the purpose. Moreover, it is also preferable that the barrels and screws of these extruders carry out surface treatment, a coating process, etc. by a well-known method.

It is preferable that the screw used in this invention is a screw structure of the high dispersion type at least one part. Here, the highly dispersed screw configuration is composed of a screw of reverse feeding and a screw of forward feeding, and is a structure having a screw of forward feeding interposed with a screw of reverse feeding. Although it will not specifically limit, if it is a screw which has the effect as a screw of the backfeed used, The reverse flight screw with favorable sealing performance is especially preferable. The screw for forwarding is not particularly limited as long as it has a screw, but a kneading disc is preferably used.

If another screw can be inserted between the screw of the reverse feed and the screw of the forward feed, and the screw of the forward feed with low conveyance ability is used, the effect of dispersion | distribution becomes high and it becomes a preferable thing. As a screw for forwarding with low carrying capacity, a screw of an estimated notch type is used preferably.

By using such a highly dispersed screw configuration, the residual solvent in the resin at the outlet of the extruder can be greatly reduced. In addition, in the case of injecting water, it is preferable that the screw configuration at the position where the water is injected can be uniformly dispersed in a small amount of water, so that the screw configuration is highly dispersed. It is also preferred that the screw configuration in front of the final vent is a highly dispersed screw configuration even though no water is injected.

The ratio (hereinafter referred to as L / D) of the length L of the cylinder and the diameter D of the screw in the extruder used in the present invention is not particularly limited, and depends on the properties of the resin, product properties and desolvent load. Although different, L / D is 20-80 thing normally, and L / D is 40-60 thing preferably.

In addition, in this invention, although it does not specifically limit about the screw rotation speed of an extruder, Usually, screw rotation speed (rpm): N is ratio of resin throughput (kg / hr): Q (henceforth "Q / N". ) And determined in view of the resin throughput and product physical properties. For example, when the screw diameter is 40 to 60 mm, it is preferable that Q / N is selected from the range of 0.15 to 0.30, and it is more preferable to select from the range of 0.20 to 0.25.

The cyclic olefin resin solution introduced into the extruder is gradually concentrated in the extruder by the removal of the volatile solvent, and melt-kneaded to become the cyclic olefin resin in which the solvent is almost completely removed near the exit of the extruder. The solvent content of the cyclic olefin resin at the exit of the extruder is usually 1000 ppm or less, preferably 700 ppm or less, more preferably 500 ppm or less, particularly preferably 300 ppm or less.

If the solvent content of the cyclic olefin resin at the exit of the extruder exceeds 1000 ppm, foaming, defects, die lines, contamination, and the like may occur, resulting in unstable molding of the sheet or film.

The extruder used by this invention has the vent which can discharge the solvent which is a volatile matter in the cyclic olefin resin solution introduce | transduced out of an extruder. The vent may be singular or plural and is not limited, but it is usually preferred to have two or more vents, preferably three or more vents, and more preferably five or more vents. In the case where the extruder has a plurality of vents, the removal of the solvent from the cyclic olefin resin solution in the extruder can be performed stepwise by temperature conditions or the like, so that the solvent from the cyclic olefin resin solution can be efficiently removed. It becomes possible and becomes desirable. 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 cyclic olefin resin due to heating can be effectively prevented when compared to the case where the solvent is removed at a high temperature. have.

Moreover, when an extruder has a some vent, if one of them is a rear vent, it becomes a preferable thing from a viewpoint of solvent removal efficiency. That is, in the extruder of the front vent only, when a resin solution having a high solvent concentration is supplied, the solvent load of the first front vent is too high to cause entrapment. However, when using an extruder having a rear vent, the solvent in each vent is used. It is preferable because the load can be reduced and the control can be easily controlled so that no entrapment occurs. In this invention, it is especially preferable to control by the solvent load which removes 15-35 weight% from a rear vent among the solvent amount of the resin solution supplied to the extruder.

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, and is usually selected from the range of 150 to 350 ° C, preferably 200 to 300 ° C. .

Moreover, it does not specifically limit also about the operation pressure of a vent. The operating pressure of the vent can be set so that the solvent vapor velocity in the vent does not cause the resin entrapment, and is changed by the operating temperature and the desolvent load in each vent. The solvent content in the resin is desolvated to 1000 ppm or less. In order to operate, it is preferable that the operating pressure of each vent is usually 0.5 MPaG or less. In the case of performing under reduced pressure of 0 MPaG or less (atmospheric pressure or less), thermal energy due to the removal of the solvent can be saved, and the heat history to the cyclic olefin resin can be suppressed, more preferably -0.05 MPaG or less. It is more preferable if it is.

In addition, when using the extruder which has two or more vents, it is preferable that an extruder has a sealing part between each vent port. It is preferable to use such an extruder because it is possible to change the operation temperature and the operation pressure of each vent independently and suitably, and to easily control the load of the desolvent of each vent so that no entrapment occurs.

Moreover, the solvent discharged | emitted out of an extruder from a vent can also be collect | recovered and recycled.

In the present invention, in the case of using an extruder having a plurality of vents, when water is injected into at least one of the vent ports, solvent removal is further promoted. Usually, when inject | pouring water, when the extruder which has a sealing part between the screw and the vent of a water injection position, and the upstream vent port is used, since the effect can fully be obtained, it is preferable, and the screw and the vent of a water injection position are preferable. It is more preferable to use the extruder which has a sealing part between and the vent hole before and behind that. In addition, it is preferable to perform water injection continuously in a fixed ratio.

The injection of water is preferably carried out especially when the solvent is removed from the resin having a low solvent concentration. As a method of removing a solvent again from resin with a low solvent concentration, the method of extending a residence time is mentioned normally, In this method, heat generation of resin is large and it may become a problem in quality. On the other hand, when water is injected, the solvent evaporates together with the water to remove the solvent highly, and the heat generation can be suppressed even when the residence time is extended, which is preferable in terms of quality.

For this reason, in this invention, it is preferable to inject water with respect to the cyclic olefin resin solution which removed at least one part of solvent from the upstream vent through the inlet of water, such as a rear vent.

In addition, the water to be injected is preferably in an amount of 0.5 to 1.5, and more preferably in an amount of 0.8 to 1.2 when the resin processing amount (amount of the cyclic olefin resin) is 100.

If the amount of water injected is less than 0.5, the water dispersing effect is small and the cooling effect is small, so that the water injection effect may not be sufficiently obtained. On the contrary, when the amount of water injected is more than 1.5, the cooling effect by water becomes too large and solvent removal may worsen.

In this invention, when water is inject | poured, it is preferable to use the extruder which the screw of the position which injects water is a screw of a high dispersion type | mold.

The discharge pressure of the extruder of the present invention is preferably constant in order to obtain a film having a uniform thickness because variations in the discharge pressure cause thickness unevenness of the film.

From the extruder outlet, the cyclic olefin resin from which the solvent was fully removed as mentioned above can be obtained by melt-kneading. Here, in order to stabilize the discharge from an extruder and to prevent the fall of the extrusion amount by the pressure loss in the die, it is possible to use the gear pump of a well-known mechanism as needed. By using a gear pump, the thickness precision of the film or sheet obtained improves and becomes a preferable thing.

It is also preferable to provide a known filter at the outlet of the extruder to remove foreign matters, gelling, impurities, etc., which are defects in the film.

The molten cyclic olefin resin is discharged from a flat die, solidified on a cooling roll to obtain a target film. As a specific example of a flat die, a manifold die (T die), a fish tail die, a coat hanger die, etc. are mentioned. Among them, coat hanger dies and manifold dies are preferred.

Examples of the material of the extruder (cylinder, screw, etc.) and the die include stainless steel such as SCM-based steel and SUS, but are not limited thereto. In addition, the inner surface of the extruder cylinder, the die, and the surface of the extruder screw are plated with chromium, nickel, titanium, etc., and TiN, TiAlN, TiCN, CrN, DLC (diamond-like carbon) by PVD (Physical Vapor Deposition) method, or the like. It is preferable to use a film having a coating such as), a tungsten carbide or other ceramic thermally sprayed, or a nitrided surface. Such surface treatment is preferable in that the melt state of the uniform resin can be obtained because the friction coefficient with the resin is small.

Examples of the method for solidifying the film extruded from the die include a nipple roll method, an electrostatic application method, an air knife method, a vacuum chamber method, a calendar method, a sleeve method, and the like, and an appropriate method is selected according to the thickness of the film and the application. .

It is preferable to perform various surface treatments also on the cooling roll surface for solidifying the film extruded from the die like the extruder cylinder, the inner surface of the die, and the like. These surface treatments prevent adhesion of the extruded film to the roll surface to prevent film thickness nonuniformity, increase the surface precision of the cooling roll, and have high surface hardness, thus making it difficult to scratch or stably produce the film stably. It is preferable at the point which can maintain the film surface precision, and can manufacture the film without thickness nonuniformity.

In this invention, the part which contact | connects active gas with an extruder and its peripheral device can be sealed by inert gas. The inert gas is not particularly limited, but nitrogen or argon having a purity of 98% or more, preferably 99% or more, particularly preferably 99.9% or more is used. By introduction of such an inert gas, it becomes possible to suppress generation | occurrence | production of the defect of a film, and it becomes preferable.

Here, as melt extrusion conditions for obtaining the melt extrusion 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 the shear rate at the time of melt extrusion is usually. , 1 to 500 (1 / sec), preferably 2 to 350 (1 / sec), more preferably 5 to 200 (1 / sec). When the resin temperature is less than 200 ° C, the resin cannot be melted uniformly. On the other hand, when the resin temperature is higher than 350 ° C, the resin is thermally deteriorated at the time of melting, making it difficult to manufacture a high quality film having excellent surface properties. Moreover, when the shear rate at the time of extrusion is less than 1 (1 / sec), since an resin cannot be melted uniformly, the extruded film with a small thickness nonuniformity cannot be obtained, On the other hand, when it exceeds 500 (1 / sec), a shear force This is so large that resin and additives decompose and deteriorate, and defects, such as foaming, a die line, and a deposit, arise in the surface of an extruded film, and are unpreferable.

The sheet or film obtained by the present invention can also be subjected to a known process. For example, extending | stretching processes, such as uniaxial stretching or biaxial stretching, embossing for a pattern and micro shape creation, stamping, prism processing, printing processing, antireflection or diffusion function provision, hard coat, electroconductivity provision, reflection function It is possible to perform a dry or wet coating treatment for the purpose of imparting or the like. It is also possible to laminate a film, sheet, sheet, or other member formed in the shape of a mold by a known method including other cyclic olefin resins, known thermoplastic resins, thermosetting resins, metals, glasses, ceramics or the like or other materials. Do. When laminating | stacking, it is possible to select methods, such as fusion | melting, well-known thermosetting, photocurable adhesive agent, and mechanical bonding, etc. by heat, an ultrasonic wave, etc. according to the objective.

ADVANTAGE OF THE INVENTION According to this invention, the cyclic olefin resin film or sheet which has stable property formed from the cyclic olefin resin by which the volatile solvent was fully removed can be obtained. In particular, the cyclic olefin polymer solution used as a raw material in the present invention is a product of solution polymerization or a hydrogenated product or a concentrate thereof containing a cyclic olefin polymer and a polymerization solution, after the cyclic olefin polymer is synthesized, other than concentration. In the case of not having a heat history, the heat history can be suppressed by providing a cyclic olefin polymer to melt kneading in an extruder without undergoing a heating / cooling process such as pelletization, drying and melting. Quality deterioration, such as coloring by a heat history of a film or sheet obtained, can be suppressed. Moreover, in this invention, since a cyclic olefin resin film or sheet can be manufactured with little process and thermal energy, an installation can be simplified and heat energy can be saved and it is economical.

The cyclic olefin-based film or sheet obtained in the present invention is 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 display element substrate for a liquid crystal or an electroluminescence use, a touch panel, a light guide plate. It is applicable suitably to a well-known use as a use of cyclic olefin type polymer etc ..

According to the present invention, it is possible to produce a cyclic olefin-based film or sheet having a stable property by sufficiently removing the solvent by a simple method. Moreover, according to this invention, the manufacturing method of the cyclic olefin type polymer film or sheet which suppressed the quality deterioration by a heat history can be provided. Moreover, according to this invention, the manufacturing method of the economical cyclic olefin type polymer film or sheet which simplified the installation and saved thermal energy can be provided.

Although the specific Example of this invention is described below, this invention is not limited only to these Examples. In addition, "part" and "%" mean "part by weight" and "weight%" unless there is particular notice here. In addition, various measurement items are the values calculated | required as follows.

Glass transition temperature ( Tg )

According to JIS K 7121, it measured by the differential scanning calorimeter (DSC) at the temperature increase rate of 10 degree-C / min in nitrogen atmosphere.

Hydrogenation rate

It calculated | required from proton ratios, such as the proton of 500 MHz and ^1- H-NMR carbon-carbon double bond phase, and the methyl proton of a carboxymethyl group.

Intrinsic viscosity [η] ^inh

The intrinsic viscosity of the chloroform solution of the sample adjusted to the concentration of 0.5 g / dl was measured at 30.0 ° C using a Uberode viscometer.

Water absorption

The water absorption was measured according to the JIS K 7209A method.

Synthesis Example 1

215 parts of 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene (specific monomers), bicyclo [2.2.1] hepto-2-ene 35 To 23 parts of 1-hexene (molecular weight regulator) and 750 parts of toluene were introduced into a reaction vessel substituted with nitrogen, and the solution was heated to 60 ° C. Thereafter, in the solution in the reaction vessel, 0.62 parts of toluene solution of triethylaluminum (1.5 mol / L) as a polymerization catalyst and tungsten hexachloride (tert-butanol: methanol: tungsten = 0.35) modified with tert-butanol and methanol 3.7 parts of toluene solution (concentration 0.05 mol / L) of 0.30: 1.0O molar ratio) were added, and this system was heat-opened-copolymerized by stirring at 80 degreeC for 3 hours, and the ring-opening copolymer solution was obtained.

The polymerization conversion ratio in this polymerization reaction was 97%.

4000 parts of the ring-opening copolymer solution thus obtained were introduced into the autoclave, and 0.48 parts of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening copolymer solution, and the hydrogen gas pressure was 100 kg / cm 2, Under the condition of the reaction temperature of 165 ° C, the mixture was heated and stirred for 3 hours to cause a hydrogenation reaction. After cooling the obtained reaction solution (hydrogenated copolymer solution), hydrogen gas was discharged.

About the hydrogenated copolymer obtained in this way, the hydrogenation rate was measured using <^1> H-NMR and it was substantially 100%. The intrinsic viscosity [η] ^inh of the copolymer was 0.53 dl / g, and the glass transition temperature was 123 ° C. Moreover, when the number average molecular weight (Mn) and weight average molecular weight (Mw) of polystyrene conversion were measured about this resin by GPC method (solvent: tetrahydrofuran), they are 22,000 and 70,000, respectively, and molecular weight distribution (Mw / Mn) was 3.18.

Example  One

To the hydrogenated copolymer solution obtained in Synthesis Example 1, 0.1 part of Irganox 1010 (manufactured by Chiba Specialty Chemicals Co., Ltd.) was added to 100 parts of the copolymer as an antioxidant, and then a filter having a mesh of 5 µm and 0.2 µm was added. It was connected in series, filtered, and concentrated to 50% of solid content concentration, and the solution was used as a sample. The sample of temperature 130 degreeC was supplied to the extruder which has five vents by the flow volume of 80 kg / hr in conversion of resin, and the solvent component was removed in steps by each vent. The resin from which the solvent was removed was boosted by a gear pump, quantitatively supplied to a T die, and an extruded film having a thickness of 100 µm and a width of 650 mm was produced.

The extruder has a L / D of 56, and one of five vents used as a rear vent, which has a sealing part between each vent port, and used the structure which can control the operation pressure of each vent independently. The screw used the thing made from SUS, and was operated by rotation speed 360rpm. The operating pressure and operating temperature of each vent are as shown in Table 1 below.

pressure Temperature Rear Vent # 1 Vent # 2 Vent # 3 Vent Final Vent -0.05 MPaG -0.05 MPaG -0.095 MPaG -0.095 MPaG -0.099 MPaG 240 ℃ 240 ℃ 280 ℃ 280 ℃ 280 ℃

The shaping | molding apparatus used consisted of a twin screw extruder, a gear pump, a T die, a cooling roll, and a winder in order in the whole process.

The screw configuration of the extruder is a screw configuration including a full flight screw and forward kneading disk up to # 3 vent, and a reverse flight screw, a calculated notch screw, forward kneading disk, and calculation from the current side between the # 3 vent and the final vent. It was set as the highly dispersed screw structure arrange | positioned in order of a notch screw and a reverse flight screw.

The T-die used the thing of the coat hanger type of manifold shape, the steel material was SCM435, and the flow path surface was hard chromium plating. The leaf edge is a sharp edge and there are no defects. The surface roughness of the leaf surface was 0.1 S, and the leaf opening was 0.5 mm. The T die heater used the aluminum casting heater, and set the heater temperature to 260 degreeC.

On the other hand, the cooling roll used the roll (made by torqueden) of the outer diameter 400mm provided with the vacuum jacket in roll inside, and the surface roughness of the surface was 0.1S. Roll temperature was controlled to 110 degreeC by the thermal medium oil. In addition, the nip roll was used in order to adhere | attach a film to a cooling roll.

In addition, the film obtained up to 2 hours after the start of operation was disposed of without sampling, and the subsequent film was confirmed to be stable in temperature and pressure such as an extruder and a die. In addition, the sample collected 2 hours after the start of operation was used for various evaluations unless there was particular notice.

Example  2

A thickness of 100 was obtained by the same method as in Example 1, including sampling, except that 1% of water was continuously injected between the # 3 vent and the final vent of the extruder with respect to the amount of resin (the amount of hydrogenated copolymer). The extruded film of micrometer and width 650 mm was produced.

Comparative example  One

To the hydrogenated copolymer solution obtained in Synthesis Example 1, 0.1 part of Irganox 1010 (manufactured by Chiba Specialty Chemicals Co., Ltd.) was added to 100 parts of the copolymer as an antioxidant, and then a filter having a mesh of 5 µm and 0.2 µm in series. The resulting solution was fed to a twin screw extruder by filtration and concentrated to a solid content concentration of 50%, and after removing volatiles, strands were obtained from a strand die. After cooling the obtained strand, it cut by the strand cutter and produced the pellet-shaped resin.

In addition, although the operation conditions were also the same as the extruder using the thing similar to Example 1, the screw structure made it all the screw structure containing a full-flight screw and a forward kneading disk.

The obtained pellet is dehumidified and dried under nitrogen at 80 ° C. for 4 hours, melted using a 65 mmΦ single screw extruder, and the sampling is carried out using a gear pump, a T die, a cooling roll, and a winder used above at its tip. By the same method as in Example 1, an extruded film having a thickness of 100 μm and a width of 650 mm was produced.

(Evaluation of the film)

The amount of residual solvent in resin at the exit of each extruder of Example 1 and Comparative Example 1 was measured by gas chromatography with a FID detector. Moreover, evaluation about the external appearance of the obtained film was also performed. The results are shown in Tables 2 and 3. An evaluation of the appearance of the film was made by using a 650 mm × 1 m sample to install a 150 W halogen lamp at a point 1 m from the film to irradiate the light, and the following image from the image projected on a screen installed 1 m away from the film. I did evaluation.

The distance of the lamp / film / screen is also the distance from the center of the film (intersection of the diagonal).

Luminance

The film was set parallel to the screen to irradiate light, and the number of point defects projected on the screen was measured. The result was shown as the number per square meter.

die  line

The film was set in parallel with the screen to irradiate light, and the linear shades of light projected on the screen were visually observed and evaluated by the following evaluation criteria.

1: The joke on the line cannot be confirmed.

2: I can see a slight joke on the ship.

3: You can check the joke on the line.

bow

10 g of the molded film was dissolved in a solvent (toluene), filtered through a 0.1 μm membrane filter to collect the collected solvent insoluble matters, and the number of foreign matters of 20 μm or more was counted again using a stereo microscope to obtain the number of foreign substances per 10 g of film. .

Durability rating

Yellowness YI of the film was measured with a spectrophotometer (made by Suga test instrument). The film was left to stand in the gear oven heated at 120 degreeC for 500 hours again, and the difference (triangle | delta) YI of yellowness before and behind a test was measured.

Absorption rate (%) Tg (℃) Residual solvent (ppm) Foreign matter YI change (durability) Die line Example 1 0.15 123 550 3 0.6 One Example 2 0.15 123 200 3 0.6 One Comparative Example 1 0.15 123 950 25 1.6 1 to 2

2 hours later 4 hours later 6 hours later 8 hours later 10 hours later  Point Example 1 8 6 4 3 2 Example 2 9 7 5 3 3 Comparative Example 1 51 30 25 23 21

In Table 2 and Table 3, it turns out that the film obtained by the manufacturing method of this invention is an excellent film with few surface defects, such as a bright spot and a die line. Moreover, heat-coloring resistance is also small compared with the film obtained by melt-extruding with a conventional pellet.

According to the production method of the present invention, it is possible to produce a film or sheet with a small process and thermal energy, and to obtain an excellent film or sheet having a low thermal history.

Claims (12)

A cyclic olefin resin solution containing a cyclic olefin resin and a solvent and containing 20 to 80% by weight of a cyclic olefin resin, Having a vent, and introduced into an extruder having a screw in the back feed and a screw in the forward feed, Remove the volatile components of the cyclic olefin resin solution in the extruder, By melt extrusion molding a film or sheet shaped article with a die The manufacturing method of the cyclic olefin resin film or sheet characterized by the above-mentioned. The extruder in which at least one part of screw structure was made into high dispersion type | mold is used, The manufacturing method of the cyclic olefin resin film or sheet of Claim 1 characterized by the above-mentioned. The extruder which has a rear vent is used, The manufacturing method of the cyclic olefin resin film or sheet of Claim 1 or 2 characterized by the above-mentioned. The method for producing a cyclic olefin resin film or sheet according to claim 1 or 2, wherein an extruder having a plurality of vents is used. The method for producing a cyclic olefin resin film or sheet according to claim 1 or 2, wherein the cyclic olefin resin solution contains 40 to 70 wt% of a cyclic olefin resin. The cyclic olefin resin film according to claim 1 or 2, wherein a solution containing a solution produced by solution polymerization containing a cyclic olefin resin and a polymerization solvent is used as the cyclic olefin resin solution. Method of manufacturing the sheet. The solvent content of the cyclic olefin resin at the exit of an extruder is 1000 ppm or less, The manufacturing method of the cyclic olefin resin film or sheet of Claim 1 or 2 characterized by the above-mentioned. The process for producing a cyclic olefin resin film or sheet according to claim 3, wherein 15 to 35% of the solvent of the cyclic olefin resin solution is removed by the rear vent of the extruder. The method for producing a cyclic olefin resin film or sheet according to claim 4, wherein an operating pressure of each vent is arbitrarily controlled using an extruder having a sealing portion between the vent holes. The method for producing a cyclic olefin resin film or sheet according to claim 4, wherein water is injected into at least one of the vent ports of the extruder. The manufacturing method of the cyclic olefin resin film or sheet of Claim 10 whose extruder which is a screw structure of the high dispersion type screw structure of the position which injects water is used. The method for producing a cyclic olefin resin film or sheet according to claim 1 or 2, wherein a water absorption of 0.05 to 0.5% by weight is used as the cyclic olefin resin.