WO2005000948A1

WO2005000948A1 - Process for producing cycloolefin resin film or sheet

Info

Publication number: WO2005000948A1
Application number: PCT/JP2004/006088
Authority: WO
Inventors: Naritsugu Kumai; Kazuyuki Matsunaga; Daisuke Ichinose
Original assignee: Jsr Corporation
Priority date: 2003-06-25
Filing date: 2004-04-27
Publication date: 2005-01-06
Also published as: TW200504129A; CN1813021A; TWI368628B; JP2005015598A; KR100744290B1; KR20060027364A

Abstract

A process for producing a cycloolefin resin film or sheet, characterized by introducing into a vented extruder a cycloolefin resin solution comprising 20 to 80 wt.% cycloolefin resin and a solvent, removing the volatiles from the cycloolefin resin solution in the extruder, and molding the resin into a film or sheet form by melt extrusion through a die. By the process, a cycloolefin film or sheet from which the solvent has been sufficiently removed and which retains stable properties can be produced by a simple procedure. Also provided are: a process for producing a cycloolefin polymer film or sheet inhibited from suffering quality deterioration caused by heat history; and an economical process for producing a cycloolefin polymer film or sheet in which a simplified apparatus is used and heat energy saving is attained.

Description

Description Manufacturing method of cyclic olefin resin film or sheet

The present invention relates to a method for producing a film or sheet made of a cyclic olefin resin, and more specifically, the present invention relates to a solution formed by solution polymerization containing a cyclic olefin resin and a polymerization solvent (hereinafter, referred to as “polymerization solution”). The present invention also relates to a method for producing a film or sheet made of a cyclic olefin resin by a simple process from a cyclic olefin resin solution comprising a cyclic olefin resin, a solvent, and a solvent.

Background art

Molded products such as sheets and films obtained from cyclic olefin resins have excellent transparency, and are also excellent in heat resistance, moisture resistance, chemical resistance, etc., so they can be used in many fields including the optical field. Expected.

Cyclic olefin resin can be produced, for example, by polymerizing or copolymerizing a cyclic olefin monomer and other monomers as necessary, and further hydrogenating if necessary. When the polymerization method is used, it is obtained as a solution (polymerization solution) dissolved in a polymerization solvent.

For this reason, in general, before manufacturing a molded article such as a cyclic olefin resin film or sheet from the polymerization solution, the solvent contained in the polymerization solution is volatilized to separate the cyclic olefin resin from the solution and separate the resin. The pelletized cyclic olefin resin is pelletized, and the pellet is heated, melt-kneaded, and extruded. In such a method, a film or sheet of a cyclic olefin resin is formed. In the case of manufacturing, it was necessary to perform heating at each stage such as solvent volatilization, pelletization, and melt kneading, so the process was complicated and a lot of energy was required. Further, the polymer or impurities mixed in a small amount in the polymer may be denatured due to the heat history, resulting in slight coloring, clouding, optical distortion, and the like. For this reason, a method for producing a molded product such as a film or a sheet of a cyclic olefin resin from a solution containing a cyclic olefin resin by a simple method with a small heat history while consuming less heat energy is required. Appearance was desired.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and requires a small amount of heat energy from a cyclic olefin resin solution to produce a cyclic olefin resin film or sheet by a simple process with a small heat history. It provides a way to do this.

Disclosure of the invention

The method for producing a cyclic olefin resin film or sheet of the present invention comprises a cyclic olefin resin and a solvent, wherein the cyclic olefin resin solution containing 20 to 80% by weight of the cyclic olefin resin has a vent. It is introduced into an extruder, where the volatile components of the cyclic olefin resin solution are removed in the extruder, and a film or sheet-like molded product is melt-extruded from a die.

In the present invention, it is preferable to use an extruder in which at least a part of the screw structure is made highly dispersed. Further, it is preferable to use an extruder having a rear vent, and it is more preferable to use an extruder having a plurality of vents. That is, in the present invention, it is particularly preferable to use an extruder having a plurality of vents, one of which is a rear vent.

In the present invention, the cyclic olefin resin solution preferably contains 40 to 70% by weight of the cyclic olefin resin. It is also preferable to use a solution containing a solution produced by solution polymerization containing a cyclic olefin resin and a polymerization solvent.

In the present invention, the solvent content of the cyclic olefin resin at the outlet of the extruder is preferably 1000 ppm or less. It is also preferable to remove 15 to 35% of the solvent of the cyclic olefin resin solution by a rear vent of the extruder. Further, in the present invention, it is preferable to use an extruder having a seal portion between the vent ports, and to independently control the operating pressure of each vent independently. It is also preferable to inject water, and it is also preferable to use an extruder in which the screw configuration at the position where water is injected is a highly dispersed screw configuration.

In the present invention, as the cyclic Orefin resin, it is preferable to use those having a water absorption rate of 0.05 to 0.5 wt ^_0/0.

Detailed description of the invention

Hereinafter, the present invention will be described specifically.

Examples of the cyclic olefin resin used in the present invention include the following (co) polymers.

(A): a ring-opened polymer of a specific monomer represented by the following general formula (1).

(B): a ring-opening copolymer of a specific monomer represented by the following general formula (1) and a copolymerizable monomer.

(C): a hydrogenated (co) polymer of the ring-opened (co) polymer of (A) or (B).

(D): a (co) polymer obtained by subjecting the ring-opening (co) polymer of the above (A) or (B) to ring-opening by Friedel-Crafts reaction and then hydrogenating.

(E): a saturated copolymer of a specific monomer represented by the following general formula (1) and an unsaturated double bond-containing conjugate. (F): an addition type of one or more monomers selected from a specific monomer represented by the following general formula (1), a vinyl-based cyclic hydrocarbon-based monomer, and a cyclopentene-based monomer ( (Co) polymer and its hydrogenated kamo (co) polymer.

General formula (1)

[Wherein, ¹ to! ^ Are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or another monovalent organic group, which may be the same or different. R ¹ and R ² or R ³ and R ⁴ may be combined to form a divalent hydrocarbon group, and R ¹ or R ² and R ³ or R ⁴ are bonded to each other to form a monocyclic or It may form a polycyclic structure. m is 0 or a positive integer, and p is 0 or a positive integer. ]

Specific monomer>

Specific examples of the specific monomer include the following compounds, but the present invention is not limited to these specific examples.

Bicyclo [2.2.1] hept-2-ene,

Tricyclo [4. 3. 0. I ² ' ⁵ ] —3-decene,

^Tricyclo [4. ^{4.0.1 .5} ] 1-3-undecene,

Tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ · ¹⁰ ] 1-3-dodecene,

Pentacyclo ^{^{[6. 5. 1. I 3 '6}} . O 2' 7. 0 9 '13] -4- pentadecene,

5-methylbicyclo [2.2.1] heptau 2-ene,

5-Ethylbicyclo [2.2.1] heptoe 2-ene, 5-Methoxycanoleponylbicyclo [2.2.1] heptoe 2-ene,

5-methyl-1-5-carboxycarbonylbicyclo [2.2.1] hept-2-ene,

5—Cyanobicyclo [2.2.1] Heptow 2-Yen,

8- main Tokishikarubo two Rutetorashikuro ^{^{[4. 4. 0. I 2 '5}} . I 7 · 10] over 3 dodecene,

8-ethoxycarbonyltetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] — 3-dodecene,

8- n-propoxy carbonylation Rutetorashikuro ^{^{[4. 4. 0. I 2 '5}} I 7.' 10] - 3 - dodecene,

8-isopropoxycarburtetracyclo [4. 4. 0. I ² ' ^5. I ⁷ · ¹⁰ ]-3 1-dodecene,

8—n-butoxycarbonyltetracyclo [4. 4. 0. I ² ' ^5. I ⁷ · ¹⁰ ] —3—dodecene,

8-methyl-8-methoxycarbonyltetracyclo [4.4.0. I ² ' ^5. I ⁷ ' ¹⁰ ] 1-3-dodecene,

8-methyl-8-ethoxycarbonyl two Rutetorashikuro ^{^{[4. 4. 0. I 2 '5}} . I 7' 10] one 3- dodecene,

8-methyl-8-n-propoxy carbonylation Rutetorashikuro ^{^{[4. 4. 0. I 2 '5}} . I 7' 10] one 3- dodecene,

8 Mechinore 8 isopropoxide Shikano Repo - Honoré tetracyclo ^{[4. 4. 0. I 2 '.} 5 I 7' 10] -3- dodecene,

8-methyl-8-n-butoxycarbonyltetracyclo [4. 4.0. I ² ' ^5. I ⁷ · ¹⁰ ] 1-3-dodecene, [5.2.1.1] Heptow 2-en,

8-ethylidenetetracyclic mouth [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] 1-3-dodecene, 5-phenylenobicyclo [2.2.1] hept-2-ene,

8-phenyltetracyclo [4. 4. 0. I ² ' ^5. I ⁷ · ¹⁰ ] _ 3-dodecene, 5-fluorobicyclo [2.2.1] hept-2-ene,

5-funolelomethinolebicyclo [2.2.1] hept-2-ene,

5-Triphnoreo mouth Methylbisic mouth [2.2.1] Heptaw 2-ene,

5-pentafluoroethylbicyclo [2.2.1] heptoe 2-ene,

5,5-diphnoreolobicyclo [2.2.1] heptoe 2-ene,

5, 6—Difluorovish mouth [2.2.1] Hept 1-2—

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

5, 6-bis (trifluoromethylinole) bicyclo [2.2.1] heptoto-2-ene,

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

5, 5, 6—Trifluorobicyclo [2.2.1] heptone 2_

5, 5, 6—tris (fluoromethyl) bicyclo [2.2.1] heptoe 2_

5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene, 5,5,6,6-tetrakis (trifluoromethyl) bis [2.2.1]プ — 2—

5,5-diphneololeo 6,6_bis (trifnoreolomethy / re) bicyclo [2.2.1] heptoe 2_en, 5,6-difluoro-5,6-bis (trifnoreomethyl) bis (2.2.1) heptoe-2-ene,

5, 5, 6-trifluoro-5-trifluoromethylbis [2.2.1] heptoto-2-ene,

5-Henoleolo 5 -Pentafenoleolochinole 6, 6 -Bis (trifnoleolomethyl) bicyclo [2.2.1] heptoe 2-ene,

5, 6-diphnotoleol 5-heptaph / leorol iso-propynole-1-6-triphnoreolomethinolebicyclo [2.2.1] heptoto-2-ene,

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

5, 6-dichloro-5, 6-bis (methynole trifnoreo) bicyclo [2.2.1] heptoe 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 Full O b tetracyclo ^{^{[4. 4. 0. I 2 '5}} . I · 10] one 3-dodecene, 8-Full O b methyl tetracyclo ^{^{[4. 4. 0. I 2' 5}} . I 7 ^'10] -3-dodecene, 8-difluoromethyl O b methyl tetracyclo ^{^{[4. 4. 0. I 2' 5}} . I 7, 1. One-three-dodecene,

8 triflate Ruo Russia methyl tetracyclo ^{^{[4. 4. 0. I 2 '5}} . 1 7> 10] one 3-dodecene,

8-pentafluoroethyl tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] — 3-dodecene, 8,8-difluorotetracyclo [4 • 4.0. I ² ' ^5. I ⁷ ' ¹⁰ ] — 3-dodecene, 8,9-difluorotetracyclo [4.4.0. I ² ' ^{^{^{. 5 I 7 '10] -}}} 3- dodecene, 8, 8- bis (triflate Ruo ii methyl) tetracyclo ^{[4. 4. 0. I 2'.} 5 1 7> 10] one 3- dodecene,

8, 9 one bis (triflate Ruo ii methyl) tetracyclo ^{^{[4. 4. 0. I 2 '5}} . I 7' 10] one 3- dodecene,

8-methyl-one 8-triflate Ruo Russia methyl tetracyclo ^{^{[4. 4. 0. I 2 '5}} I 7.' 10] - 3- dodecene,

8, 8, 9-triflate Ruo b tetracyclo ^{^{[4. 4. 0. I 2 '5}} . I 7' 10] -3- de-decene,

8, 8, 9 Torisu (triflate Ruo ii methyl) tetracyclo ^{^{[4. 4. 0. I 2 '5}} . I 7 · 10] -3- dodecene,

8, 8, 9, 9-tetrafluorotetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] 1-3 1 dodecene,

8, 8, 9, 9-tetrakis (trifluoromethyl) tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ · ¹⁰ ] -3-dodecene,

8, 8-difluoro -9, 9-bis (triflate Ruo ii methyl) tetracyclo ^{^{[4. 4. 0. I 2 '5}} l 7.' 10] - 3- dodecene,

8, 9-difluoro over 8, 9- bis (triflate Ruo ii methyl) tetracyclo ^{[4. 4. 0. 1 2,5. I} 7 '10] -3- dodecene,

8, 8, 9-trifluoro-9-trifluoromethyltetracyclo [4.4.0. I ² ' ^5. I ⁷ · ¹⁰ ] 1-3-dodecene,

8, 8, 9_ Torifunoreoro 9 one Torifunoreorome butoxy tetracyclo ^{^{[4. 4. 0. I 2 '5}} . I 7' 10] one 3- dodecene, 8, 8, 9-Trifluoro-9 one pentagonal full O b propoxy tetracyclo ^{^{[4. 4. 0. I 2 '5}} . I 7' 10] one 3- dodecene,

8 Furuoro 8 penta full O Roe Chiru 9, 9 one bis (Torifuruoromechi Honoré) tetracyclo ^{^{[4. 4. 0. I 2 '5}} I 7.' 10] - 3- dodecene,

8, 9-1-difluoro over 8 _ Heputafuruoro iso _ propyl one 9-Torifunoreo Russia methyl tetracyclo ^{^{[4. 4. 0. I 2 '5}} . I 7' 10] one 3- dodecene,

8 black port _8, 9, 9 one triflumizole Honoré Oro tetracyclo ^{^{[4. 4. 0. I 2 '5}} . 1

7.10] _1-3 —dodecene,

8, 9 Jikuroro 8, 9- bis (triflate Ruo ii methyl) tetracyclo ^{^{[4. 4. 0. I 2 '5}} l 7.' 10] - 3- dodecene,

8- (2, 2, 2-preparative riff Honoré O Roe Toki Shikano levo Nino Les) Tetorashiku port ^{^{[4. 4. 0. I 2 '5}} I 7.' 10] - 3- dodecene,

8-Methinole 8-(2,2,2-Trifluoroethoxycanoleponinole) tetracyclo [4. 4. 0. I ² ' ^5. I ⁷ ' ¹⁰ ] —3-Dodecene

And the like.

One of these specific monomers may be used alone, or two or more thereof may be used in combination.

Among the specific monomers, preferred are those in which R ¹ and R ³ are a hydrogen atom or a hydrocarbon group having 1 to 10, more preferably 1 to 4, and particularly preferably 1 to 2 in the above general formula (1). R ² and R ⁴ are a hydrogen atom or a monovalent organic group, and at least one of R ² and R ⁴ represents a polar group having a polarity other than a hydrogen atom and a hydrocarbon group; Is an integer of 0 to 3, p is an integer of 0 to 3, more preferably m + p = 0 to 4, further preferably 0 to 2, particularly preferably m = l and p = 0. . The specific monomer with m = l, p == 0 is the cyclic cyclic It is preferable in that the resin 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 alkoxyl group, an aryloxycarbonyl group, an amino group, an amide group, and a cyano group. May be bonded via the linking group of In addition, a hydrocarbon group to which a divalent organic group having polarity such as a carbonyl group, an ether group, a silyl ether group, a thioether group, or an imino group is bonded as a linking group is also exemplified as the polar group. Of these, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group or an aryloxycarbyl group is preferred, and an alkoxycarbonyl group or an aryloxycarbyl group is particularly preferred.

Further, a monomer in which at least one of R ² and R ⁴ is a polar group represented by the formula (CH ₂ ) _n COOR has a high glass transition temperature and a low level, Preferred in that it has excellent adhesion to various materials. In the above formula relating to the specific polar group, R is a carbon hydride group having 1 to 12 carbon atoms, more preferably 1 to 4, particularly preferably 1 to 2, and preferably an alkyl group. In addition, n is usually 0 to 5, but a smaller value of n is preferable because the glass transition temperature of the obtained cyclic olefin resin becomes higher, and the specific monomer in which n is 0 is more preferable. It is preferable in that the synthesis is easy.

In the general formula (1), R ¹ or R ³ is preferably an alkyl group, more 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. It is particularly preferable that this alkyl group is bonded to the same carbon atom as the carbon atom to which the specific polar group represented by the above formula (CH ₂ ) _n COOR is bonded. This is preferable in that it can reduce the hygroscopicity. Copolymerizable monomer>

Specific examples of the copolymerizable monomer include cyclobutene, cyclopentene, cycloheptene, cyclootaten, and cycloolefin such as dicyclopentadiene. The number of carbon atoms of cycloolefin is preferably from 4 to 20, and more preferably from 5 to 12. These can be used alone or in combination of two or more.

The preferred use range of the specific monomer Z copolymerizable monomer is from 100/0 by weight.

It is 50/50, more preferably 100Z0 to 60/40.

Ring-opening polymerization catalyst>

In the present invention, the ring-opening polymerization reaction for obtaining (Α) a ring-opening polymer of a specific monomer and (Β) a ring-opening copolymer of a specific monomer and a copolymerizable monomer is carried out by metathesis. It is performed in the presence of a catalyst.

The metathesis catalyst comprises (a) at least one selected from compounds of W, Mo, and Re; (b) a Group IA element of the Deming periodic table (eg, Li, Na, K, etc.); Group II elements (eg, Mg, Ca, etc.), Group IIB elements (eg, Zn, Cd, Hg, etc.), Group IIIA elements (eg, B, Al, etc.), Group IVA elements (eg, Si , Sn, Pb, etc.) or a compound of a group IVB element (eg, Ti, Zr, etc.) selected from compounds having at least one carbon-carbon or hydrogen-bond of the element. It is a catalyst consisting of a combination with at least one kind.

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

(a) Representative examples of the compounds of the appropriate W, Mo or R e as a _{component, WC 16, Mo C l 6} , R e OC 13 Hei 1-132626 Patent Publication No. 8 such as The compounds described in page 6, lower left column, line 6 to page 8, upper right column, line 17 can be mentioned.

(b) As specific examples of the components, n—C ₄ H ₉ L i, (C ₂ H ₅ ) ₃ A l, (C ₂ H ₅ ) ₂ A 1 C 1, (C ₂ H ₅ ) _h5 A 1 _{_{C 1 L5, (C 2 H}} 5) a 1 C 1 2, methyl alumoxane, the L i H Hei 1 one 132 626 JP-page 8, right upper column, line 18 - page 8 line 3, lower right column, etc. The compounds described can be mentioned.

As typical examples of the additive (c) component, alcohols, aldehydes, ketones, amines, and the like can be suitably used. Further, JP-A-11-132626, page 8, right lower column The compounds shown in line 16 to page 9, upper left column, line 17 can be used.

The amount of the metathesis catalyst to be used is such that the molar ratio of the component (a) to the specific monomer is “component (a): specific monomer”, usually in the range of 1: 500 to 1: 50,000, Preferably, it is in the range of 1: 1,000 to 1: 10,000.

The ratio of the component (a) to the component (b) is such that (a) :( b) is 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) to the component (c) is such that the molar ratio of (c) :( a) is 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1. It is desirable. <Polymerization reaction solvent>

Solvents used in the ring-opening polymerization reaction (solvents constituting the molecular weight modifier solution, specific monomers and solvent for Z or metathesis catalyst) include, for example, alkanes such as pentane, hexane, heptane, octane, nonane, and decane. , Cyclohexane, cycloheptane, cyclooctane, cycloalkanes such as decalin, norbornane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, chlorobutane, bromohexane, chloridene methylene, dichloromethane Rohethane, hexamethylene dipromide, benzene, chlorohonolem, tetraethylene, etc., aniolecans such as halogenated anorecan, benzoylamine, rosin lichen, etc., ethyl acetate, n-butyl acetate, iso-butyl acetate And saturated carboxylic esters such as methyl propionate and dimethyloxetane; and ethenoles such as dibutyl ether, tetrahydrofuran and dimethoxetane, and these can be used alone or in combination. Of these, aromatic hydrocarbons are preferred.

The amount of solvent used is “solvent: specific monomer (weight ratio)”） Usually, an amount of 1: 1 to 10: 1, preferably an amount of 1: 1 to 5: 1 desirable. <Molecular weight regulator>

The molecular weight of the obtained ring-opened (co) polymer can be adjusted by the polymerization temperature, the type of catalyst, and the type of solvent. In the present invention, the molecular weight regulator is coexisted in the reaction system. Adjust.

Here, suitable molecular weight regulators include, for example, a-olefins such as ethylene, propene, 1-pentene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonenone, and 1-decene. And styrene. Of these, 1-butene and 1-hexene are particularly preferred.

These molecular weight regulators can be used alone or in combination of two or more.

The amount of the molecular weight modifier used is 0.05 to 0.6 mol, preferably 0.02 to 0.5 mol, per 1 mol of the specific monomer subjected to the ring-opening polymerization reaction. Is preferred.

(B) In order to obtain a ring-opening copolymer, a specific monomer and a copolymerizable monomer may be subjected to ring-opening copolymerization in the ring-opening polymerization step. Unsaturated hydrocarbon polymers containing two or more carbon-carbon double bonds in the main chain, such as conjugated diene compounds such as soprene, styrene-butadiene copolymer, ethylene-non-conjugated diene copolymer, and polynorbornene May be subjected to ring-opening polymerization of a specific monomer.

The ring-opened (co) polymer obtained as described above can be used as it is, but the (C) hydrogenated (co) polymer obtained by further hydrogenation is a resin with high impact resistance. Useful as a raw material for

The hydrogenation reaction is carried out in a usual manner, that is, a hydrogenation catalyst is added to a solution of the ring-opening polymer, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm is added to 0 to 20 atm. It is carried out by operating at 0 ° C, preferably at 20 to 180 ° C. As the hydrogenation catalyst, those used in a hydrogenation reaction of a normal olefinic conjugate can be used. Examples of the hydrogenation catalyst include a heterogeneous catalyst and a homogeneous catalyst.

Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst such as palladium, platinum, nickel, rhodium, and ruthenium is supported on a carrier such as carbon, silica, alumina, and titania. Examples of homogeneous catalysts include nickel naphthenate z triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate Zn-butyllithium, titanocene dichloride nojethyl aluminum monochloride, rhodium acetate, Mouth tris (tripheninolephosphine) Rhodium, dichlorotris (triphenolephosphine) tem, chlorohydrocanoleponinoletris (tripheninolephosphine) norethenium, dichlorocanoleboninoletris (tripheninolephosphine) ruthenium And the like. Catalysts can be in powder or granular form Good.

These hydrogenation catalysts, ring-opening (co) polymer: 7j iodized catalyst (weight ratio) Power 1: 1 X 10- ⁶ ~1: is used in a ratio of two.

As described above, the hydrogenated kamo (co) polymer obtained by hydrogenation has excellent thermal stability, and its properties can be improved by heating during molding or use as a product. Does not deteriorate. Here, the hydrogenation rate is usually 50% or more, preferably 70% or more, and more preferably 90% or more.

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

The hydrogenated (co) polymer used as the cyclic olefin resin of the present invention preferably has a gel content of 5% by weight or less in the hydrogenated (co) polymer. It is particularly preferred that the content is not more than% by weight.

Further, as the cyclic olefin resin of the present invention, (D) a ring-opened (co) polymer of the above (A) or (B), which is cyclized by a Friedel-Crafts reaction, and then hydrogenated (co) polymer is also used. Can be used.

Cyclization by the Friedel Craft Reaction>

The method for cyclizing the ring-opened (co) polymer of (A) or (B) by the Friedel-Crafts reaction is not particularly limited, but is disclosed in Japanese Patent Application Laid-Open No. 50-154399. A known method using the compound can be adopted. The acidic compounds, ^{specifically, A 1 C 1 3, BF} 3, F e C 1 3, A 1 2 O 3, HC 1, CH 3 C 1 C OOH, Zeoraito, Lewis acid activated clay, etc. The Bronsted acid is used It is.

The cyclized ring-opened (co) polymer can be hydrogenated in the same manner as the ring-opened (co) polymer of (A) or (B).

Furthermore, (E) a saturated copolymer of the above-mentioned specific monomer and an unsaturated double bond-containing compound can also be used as the cyclic olefin resin of the present invention.

Examples of the unsaturated double bond-containing compound include ethylene, propylene, butene and the like, 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 Z-unsaturated double bond-containing compound is 90/10 to 40 / Q0 by weight, more preferably 85Z15 to 50Z50.

In the present invention, (iii) a usual addition polymerization method can be used to obtain a saturated copolymer of a specific monomer and an unsaturated double bond-containing compound.

Addition polymerization catalyst>

As the catalyst for synthesizing the saturated copolymer (ii), at least one selected from a titanium compound, a zirconia compound and a vanadium compound, and an organic aluminum compound as a promoter are used.

Here, as the titanium compound, tetrachloride titanium, trisalt ^: titanium, etc., and as the zirconium compound, bis (cyclopentagenenyl) zirconium chloride, bis (cyclopentagenenyl) zirconium dichloride And so on.

Further, as the vanadium compound, a general formula

VO (OR) _a X _b or V (OR) „X _d (However, R is a hydrocarbon group, X is a halogen atom, and 0≤a≤3, 0≤b≤3, 2≤ (a + b) ≤3, 0≤c≤4, 0≤d≤4 3≤ (c + d) ≤4. ]

A vanadium compound represented by the following formula or an electron donating adduct thereof is used. Examples of the electron donor include oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, acid amides, acid anhydrides, and alkoxysilanes, ammonia, amines, and the like. Examples include nitrogen-containing electron donors such as nitrile and isocyanate.

Further, as the organoaluminum compound as the promoter, at least one selected from compounds having at least one aluminum-carbon bond or aluminum-hydrogen bond is used.

In the above, for example, when a vanadium compound is used, the ratio of the vanadium compound to the organic aluminum compound is such that the ratio of the aluminum atom to the vanadium atom (A 1 V) is 2 or more, preferably 2 to 50, Particularly preferably, it is in the range of 3 to 20.

As the solvent for the polymerization reaction used for the addition polymerization, the same solvent used for the ring-opening polymerization reaction can be used. The molecular weight of the obtained (E) saturated copolymer is usually adjusted using hydrogen.

Further, as the cyclic olefin resin of the present invention, (F) the above-mentioned specific monomer, and one or more monomers selected from vinyl-based cyclic hydrocarbon-based monomers and cyclopentene-based monomers The addition type copolymer of the above or a hydrogenated copolymer thereof may be used.

Vinyl-based cyclic hydrocarbon-based monomer>

Examples of vinyl cyclic hydrocarbon monomers include, for example, 4-vinylcyclopentene PT / JP2004 / 006088

18

Vinylation of vinyl-based pentene-based monomers such as 2-methyl-4--2-isopropinolenocyclic pentene, and vinyl-based pentane-based monomers such as 4-vinylinolecyclopentane and 4-isopropininolecyclopentane 5-membered ring hydrocarbon monomer, 4-vinylinone hexene, 4-isopropene / resin hexene, 1-methylinole 4-isopropininolecyclohexene, 2-methinolee 4-vinylinolecyclohexene, 2-methyl- Hexene monomer such as 4-hexinopenylene hexene, hexene monomer such as hexene, 4-vininolecyclohexane, 2-methinolene Vinylcyclohexane monomer such as 4-isopropenylcyclohexane, styrene, α-methino Restyrene, 2-methynolestyrene, 3-methynolestyrene, 4-methylstyrene, 1-bi- Styrene monomers such as lenaphthalene, 2-bininolephthalene, 4-phenylenolestyrene, 4-methoxystyrene, d-tenolene, 1-tenolene, ditenolepen, d-limonene, l-limonene, dipentene, etc. Monomers, vinylcycloheptene monomers such as 4-vinylinolecycloheptene and 4-isopropinolecycloheptene, and vinylcyclohexanes such as 4-butylcycloheptane and 4-isopropenylcycloheptane Heptane monomers and the like. Preferred are styrene and α-methylstyrene. These can be used alone or in combination of two or more.

Examples of the cyclopentadiene monomer used for the monomer of the (F) addition copolymer of the present invention include cyclopentadiene, 1-methylcyclopentadiene, 2-methynolecyclopentadiene, 2 —Ethynolecyclopentadiene, 5-methinolecyclopentadiene, and 5,5-methylcyclopentadiene. Preferably it is cyclopentadiene. These can be used alone or in combination of two or more. The addition type (co) polymer of at least one kind of monomer selected from the above-mentioned specific monomer, butyl-based cyclic hydrocarbon-based monomer and cyclopentadiene-based monomer is the above-mentioned (E) specific monomer It can be obtained by the same addition polymerization method as for a saturated copolymer of a compound and an unsaturated double bond-containing compound.

The hydrogenated (co) polymer of the addition type (co) polymer is obtained by the same hydrogenation method as that of the hydrogenated kamo (co) polymer of the (C) ring-opening (co) polymer. Can be. The cyclic olefin resin used in the present invention preferably has an appropriate water absorbency or moisture absorbency. In the present invention, a known dry or wet coating, or a film or sheet made of a known organic polymer, an organic compound, or an inorganic compound is provided by the cyclic olefin resin having an appropriate water absorption or hygroscopicity. In addition, when performing secondary processing, such as forming a laminate with a known molded body, the adhesiveness and applicability are preferred, which is preferable.

Here, water absorbency is the property of a material absorbing moisture when the material is in the liquid phase, and moisture absorbency is the property of the material absorbing the water vapor component when the moisture is in the gas phase as water vapor However, in both cases, the material essentially absorbs moisture, and the ultimate form of hygroscopicity can be considered to be water-absorbing. Expressed by gender. In the present invention, the above-mentioned appropriate water absorption means a water absorption rate of 0.05 to 0.5 weight as measured according to JISK7209. / _0, more preferably from 0.0 from 8 to 0.4 wt%, and particularly preferably 0.1 to 0.3 5 wt ^_0/0, the use of a cyclic Orefin system resins exhibiting such water absorption Is preferred. If the water absorption of the cyclic olefin resin is less than 0.05% by weight, there may be a problem in the above-mentioned secondary workability of the film or sheet, and if the water absorption is 0.5% by weight or more, the water absorption may be reduced. Alternatively, moisture absorption may cause problems in dimensions, shapes, optical characteristics, and the like. The molecular weight of the cyclic olefin resin used in the present invention is preferably 0.2 to 5 d 1 / g, more preferably 0.3 to 3 dlZg, particularly preferably 0.4 to 1 in intrinsic viscosity [] ^inh. The polystyrene equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 8,000 to 100,000, more preferably 10,000 to 80,000, and particularly preferably 10,000 to 80,000. Is from 12,000 to 50,000, and the weight average molecular weight (Mw) is from 20,000 to 300,000, more preferably from 30,000 to 250,000, particularly preferably from 40,000 to 200,000. Those are preferred.

When the intrinsic viscosity [77] ^inh , the number average molecular weight and the weight average molecular weight are within the above ranges, the cyclic olefin resin was used as the extruded film of the present invention, as well as heat resistance, water resistance, chemical resistance, and mechanical properties. The molding processability at the time becomes good. The glass transition temperature (Tg) of the cyclic olefin resin used in the present invention is usually 120 ° C. or higher, preferably 120 to 350 ° C., more preferably 120 to 250 ° C., and particularly preferably 120 to 200 ° C. ° C. If the _index is less than 120, the obtained film or sheet may be thermally deformed in applications requiring heat resistance, such as in-vehicle applications, which may cause a problem. On the other hand, if the Tg exceeds 350 ° C, the melt extrusion becomes difficult, and the possibility of the resin being deteriorated by the heat during the application increases, which is not desirable.

In the case of using the cyclic olefin resin of the present invention as an optical material, it is preferable that there are few foreign substances that cause visual defects and abnormal bright spots, and it is preferably not present as much as possible.

The content of such foreign matter is at least 0 g for foreign matter having a size of 50 μm or more, preferably 10 g for foreign matter having a size of 30 μπι or more, and particularly preferably 10 g for foreign matter having a size of 20 μm or more. It is preferable that The amount of foreign matter is measured by dissolving the resin in a soluble solvent such as toluene or cyclohexane, filtering through a filter, and observing with a microscope to count the size and number. . It is also possible to measure the resin solution using a commercially available fine particle printer based on light scattering and to count the amount of foreign matter.

It is also preferable that the content of the fine powder of the cyclic olefin resin of the present invention is suppressed as much as possible. A large amount of this fine powder is not preferred because it appears as optical fluctuations and causes performance defects such as bright spots and blurred focus.

The thickness of the film is not particularly limited, but is usually 0.01 mm to 5 mm, preferably 0.03 bandages to 3 restaurants, and more preferably 0.03 band to 2 mm. If the thickness exceeds 5 cm, it may be difficult to extrude a wide film uniformly. On the other hand, when the film thickness is less than 0.01 mm, the toughness of the film is insufficient, and problems such as breakage may occur easily during film production or post-processing.

To the cyclic olefin resin used in the present invention, a known acid deterioration inhibitor can be added in order to prevent the resin from being thermally degraded during melt extrusion. Specific examples are given below, but the antioxidant used in the present invention is not limited to these. That is, 2,6-di-t-butyl-4-methylphenol, 4,4'-thiobis (6-t-butynole-3-methinolephenol / re), 1,1,1-bis (4-hydroxypheninole) Mouth hexane, 1, 1, 3-tris (2-methyl-14-hydroxy-5_t-butynole feninole) butane, 3,9-bis-1 [2-—3— (3-t—petit / ray 4-Hydroxy-5-methinolephenoxy) propioninoleoxy] 1,1,1-dimethynoleethynole] -2,4,8,10-tetraoxyspiro [5,5 '] pentane, 2, 2'-dioxy 3, 3'-Gee t-butyl-butane 1,5,5'-Dimethynolef nilmethane, 2, 2'-Dioxy 3, 3'-t-butyl-butane 5,5 ' Over Jefferies chill phenylalanine methane, 2, 2 'Mechirenbisu (^ 4 Echinore 6-t-Buchinorefu Hainaut lambda), 2, 5-di-t one Puchinorehi Dorokinon, tetrakis [methylene-one ³ - (3, 5 - di one t 1,4-hydroxyphene-propionate] methane, octadecyl-3- (3,5-di-t-butyl-14-hydroxyphenyl) propionate, 1,3,5-trimethynolate 2,4 A phenolic antioxidant such as 6-tris (3,5-di-t-p-tinole-1-hydroxybenzyl) benzene, a hydroquinone-based acid inhibitor or, for example, a tris (4-methoxy-1,3,5 —Diphenyl) phosphite, tris (2,4-t-butylphenyl) phosphite, tris (noyurpheninole) phosphite, tetrakis (2,4-di-butynolephene) 1,4,4'— Biphenylenediphosphite, tetrakis (2,4-g-butynoley 5-methinolefeninole) 1,4,4'-biphenylenediphosphite, bis (2,4-di-t-butynolepheninole) Pentaerythry Phosphoric acids such as Tonoresiphosphite, bis (2,6-dibutylinole 4-methinorefueline) pentaerythritol diphosphite, bis (2,4-dicumylfeline) pentaerythritol diphosphate An anti-dandruff agent can be used, and by adding one or more of these acid-proofing agents, the thermal and acid-proof deterioration stability of the cyclic olefin resin can be improved.

Specific examples of other additives include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2-hydroxy-3, -t-butyl-5, -methynolephenyl) -5- Clozobenzotriazole, 2- (2-hydroxy-3 ', 5, -di-butylbutyl) -5-clozobenzotriazole, 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-methyl-1-phenylphenylphenol, phenol Dihydroxybenzophenone, 2,2'-dihydroxy -4, 4'-Measurement of UV absorbers represented by methoxybenzophenone, etc. \ Release agents, flame retardants, antibacterial agents, wood flour, coupling agents, petroleum resins, plasticizers, coloring agents, lubricants Known additives such as antistatic agents, silicone oils, and foaming agents can be used, and these can be appropriately added.

These additives preferably have a high weight loss temperature and a low vapor pressure. If the weight loss temperature is low and the vapor pressure is high, the extruder melts the cyclic olefin-based resin, and when extruded from an appropriate die, the additives decompose and volatilize to generate die line, fishy, etc. As a result, among the additives used, at least the 5% weight loss temperature of the additive used as an antioxidant and an ultraviolet absorber is 300 °. is a C or higher, preferably has a vapor pressure at ordinary temperature and pressure is less than 3 X 1 0- ⁷ P a, Furthermore, it is the 5% weight loss temperature 3 3 0 ° C or higher, normal temperature and pressure vapor pressure at the 3 X 1 0 - ⁹ P a thing less is particularly preferred.

Among these, acid ^ (as the dangling inhibitor, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyhydroxy / re) propionate] methane, 1,3,5-trimethyl-2,4) , 6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene and tris (2,4-di-butylphenyl) phosphite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) 1,4,4'-biphenylenediphosphite and bis (2,4-sigmylphenol) pentaerythritol diphosphite are preferably used.

These acid inhibitors are 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. If the amount is too small, the effect of imparting thermal stability at the time of melt extrusion is insufficient, while if too large, the appearance and optical properties are deteriorated due to bleed out to the film surface. Invite.

Production method of film or sheet

In the present invention, a cyclic olefin resin film or sheet is produced from a cyclic olefin resin solution containing the above-described cyclic olefin resin.

The cyclic olefin resin solution used in the present invention comprises a cyclic olefin resin and a solvent, and the cyclic olefin polymer is contained in the solution in an amount of 20 to 80% by weight, preferably 30 to 75% by weight. ^_0/0, and particularly preferably those containing 4 0-7 0% by weight. If the concentration of the cyclic olefin resin solution is less than 20% by weight, it is difficult to sufficiently evaporate the solvent component, and the concentration of the cyclic olefin resin is 80% by weight. When the ratio exceeds / ₀ , the viscosity of the solution becomes high, and it is difficult to transfer the solution to an extruder.

As the solvent constituting the cyclic Orefin system榭脂solution, the solvent used for polymerizing the force ^s, annular O Les fins resins as described above which it can be used any solvents which can dissolve the cyclic Orefin resin Is preferred.

For example, alkanes such as pentane, hexane, heptane, octane, nonane, and decane; cycloanolecans such as cyclohexane, cycloheptane, cyclooctane, decalin, and nonolevonenane; benzene, tonolenene, xylene, ethynolebenzene, and cumene Aromatic hydrocarbons such as chlorobutane, bromohexane, chloride methylene, dichloroethane, hexamethylene dibutide, chlorobenzene, chloropho / rem, tetrachloroethylene, etc .; Compounds, saturated carboxylic esters such as ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, and dimethoxyethane, and ethers such as dibutyl ether, tetrahydrofuran, and dimethoxetane And the like, and these can be used alone or as a mixture. Of these, aromatic hydrocarbons are preferred.

The method for preparing the cyclic olefin resin solution used in the present invention is not particularly limited.For example, a cyclic olefin resin pellet may be dissolved in a solvent so as to have a desired concentration. It is preferably a solution comprising a cyclic olefin-based resin produced by solution polymerization and a polymerization solvent. Further, it is particularly preferable that the solution is concentrated after separating components such as a catalyst by a known method.

Although the viscosity of the cyclic olefin resin solution used in the present invention is not particularly limited, the viscosity at a temperature of 100 ° C. is usually 5,000, 000 O m P a -s or less. Preferably, it is not more than 3, 000, 000 OmPas, more preferably not more than 1, 000, OOmPas.

In the present invention, a cyclic olefin resin solution is introduced into an extruder having a vent to separate volatile components. The transfer of the cyclic olefin resin solution to the extruder is not particularly limited, and a known pump or the like can be used. At the time of transfer, the cyclic olefin polymer solution may be filtered for the purpose of removing foreign substances and impurities.

The extruder of the present invention is not particularly limited as long as it is an extruder having a vent and a mechanism for melting and kneading the resin, and is a known single-screw, twin-screw, or satellite multi-screw extruder. Etc. can be suitably used. Heating of the extruder is also performed by a known method such as an electric heating type or an oil jacket type. Furthermore, 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, a dalmage type, and the like, and in the case of a twin shaft, a co-engaging type, a different direction Known types such as a meshing type, a kneader type, and a paddle type can be used. Also, melt-kneading screws, kneading disks, It is also preferable to use an extruder that combines paddles, full flights, notches on the summit, etc. according to the purpose. Further, it is preferable that the barrels and screws of these extruders are subjected to a surface treatment, a coating treatment and the like by a known method.

It is preferable that at least a part of the screw used in the present invention has a highly dispersed screw structure. Here, the high-dispersion screw configuration is composed of a backward-feeding screw and a jet-feeding screw, with a forward-feeding screw sandwiched by a backward-feeding screw. The reverse feed screw to be used is not particularly limited as long as it is a screw having the action, but a reverse flight stallion having good sealing performance is particularly preferable. The progressive screw is not particularly limited as long as the screw has the action, but a kneading disk is preferably used.

Another screw may be inserted between the backward feeding screw and the forward feeding screw. When a low-rate forward feeding screw having a low carrying capacity is used, the effect of dispersion is enhanced, which is preferable. As a progressive screw having a low transfer capacity, a screw with a notch at the top is preferably used.

By using such a highly dispersed screw configuration, the residual solvent in the resin at the outlet of the extruder can be significantly reduced. In addition, when water is injected, the screw configuration at the position where water is injected is desirably a high-dispersion screw configuration because a small amount of water can be uniformly dispersed. Further, it is preferable that the screw configuration before the final vent is a highly dispersive screw configuration regardless of whether water is injected.

The ratio of the length (L) of the cylinder to the diameter (D) of the screw in the extruder used in the present invention (hereinafter referred to as L / D) is not particularly limited, and the properties of the resin, the physical properties of the product, and the solvent removal Depending on the load, LZDs of 20 to 80 are usually used, Those having a D of 40 to 60 are preferably used.

In the present invention, the screw speed of the extruder is not particularly limited. Normally, the screw speed (rpm): N is the ratio of resin throughput (kg / hr): Q (hereinafter, “Q / N It is determined in consideration of the resin processing amount and product properties. For example, when the screw diameter is 40 to 60 mm, the Q / N is preferably selected from the range of 0.15 to 0.30, and the Q / N is preferably selected from the range of 0.20 to 0.25. More preferably, it is selected.

The cyclic olefin resin solution introduced into the extruder is gradually concentrated and melt-kneaded by removing the solvent, which is a volatile component, in the extruder, and is almost completely dissolved near the exit of the extruder. Is removed to obtain a cyclic olefin resin. The solvent content of the cyclic olefin resin at the outlet of the extruder is usually 100 ppm or less, preferably 700 ppm or less, more preferably 500 ppm or less, and particularly preferably 300 ppm or less. .

If the solvent content of the cyclic olefin resin at the outlet of the extruder exceeds 100 ppm, foaming, defects, die lines, stains, etc. are generated, and the molding of the sheet or film becomes unstable, which is not preferable.

The extruder used in the present invention has a vent capable of discharging the solvent, which is a volatile component in the introduced cyclic olefin resin solution, out of the extruder. This vent may be singular or plural, and is not limited, but usually it is desirable to have two or more, preferably three or more, more preferably five or more vents. When the extruder has a plurality of vents, the removal of the solvent from the cyclic olefin resin solution in the extruder can be performed in a stepwise manner depending on temperature conditions or the like. The solvent can be efficiently removed from the solvent, which is preferable. Also, if the extruder has multiple vents, 04 006088

28

In this case, the solvent can be gradually removed at a relatively low operating temperature, so that deterioration of the quality of the cyclic olefin resin due to heating is effectively prevented as compared with the case where the solvent is removed at a high temperature. be able to.

Further, when the extruder has a plurality of vents, it is preferable that one of the vents is a rear vent in terms of solvent removal efficiency. In other words, in the case of an extruder with only a front vent, when a resin solution with a high solvent concentration is supplied, the solvent load on the first front vent becomes too high, which tends to cause entrainment. This is preferable because the solvent load at each vent can be reduced, and it can be easily controlled so that no entrainment occurs. In the present invention, it is particularly preferable to control the solvent load such that 15 to 35% by weight of the solvent amount in the resin solution supplied to the extruder is removed by a reavent. The operating 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, etc., and is usually 150 to 350 ° C, preferably 20 to 100 ° C. It is selected from the range of 0 to 300 ° C.

Further, the operating pressure of the vent is not particularly limited. The operating pressure of the vent may be set so that the solvent vapor velocity in the vent does not cause resin entrainment, and the force that varies depending on the operating temperature and desolvation load at each vent. In order to remove the solvent content to 1000 ppm or less, it is preferable that the operating pressure of each vent is usually 0.5 MPa aG or less. In addition, it is more preferable to perform the treatment under a reduced pressure of OMPaG or less (atmospheric pressure or less), because it is possible to save heat energy for removing the solvent and to suppress the heat history of the cyclic olefin resin. It is more preferably at most 0.05 MPaG. When an extruder having a plurality of vents is used, it is preferable that the extruder has a seal between each vent port. With such an extruder, each vent T JP2004 / 006088

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The operation temperature and the operation pressure can be preferably independently changed and used, and the desolvation load of each vent can be easily controlled so that no entrainment occurs, which is preferable.

The solvent discharged from the vent to the outside of the extruder can be collected and recycled.

In the present invention, when an extruder having a plurality of vents is used, it is preferable to inject water into any one or more of the spaces between the vents, because the removal of the solvent is further promoted. Usually, when water is injected, it is preferable to use an extruder having a seal portion between the screw and the vent at the water injection position and the vent port upstream thereof since the effect can be sufficiently obtained. It is more preferable to use an extruder having a seal portion between the screw and the vent at the water injection position and the vent ports before and after the screw and the vent. Further, it is preferable that water is continuously injected at a constant rate.

The injection of water is preferably performed particularly when removing the solvent from a resin having a low solvent concentration. As a method of further removing the solvent from the resin having a low solvent concentration, a method of generally increasing the residence time can be cited, but this method generates a large amount of heat from the resin, which may cause a problem in quality. On the other hand, when water is injected, the solvent can be removed to a high degree by evaporating the solvent along with the water, and even if the residence time is increased, heat generation can be suppressed and the quality can be reduced. It will be preferable. For this reason, in the present invention, it is preferable to inject water into the cyclic olefin resin solution from which at least a part of the solvent has been removed by a vent upstream of a water inlet such as a rear vent.

The amount of water to be injected is preferably 0.5 to 1.5 when the resin treatment amount (the amount of the cyclic olefin resin) is 100, and the amount of water to be injected is 0.8 to 1.2. More preferably, If the amount of water injected is less than 0.5, the effect of dispersing water is small and the cooling effect is also small, so that the effect of water injection may not be sufficiently obtained. Conversely, if the amount of water injected is greater than 1.5, the cooling effect of the water will be too great and solvent removal may be poor.

In the present invention, when water is injected, it is preferable to use an extruder in which a screw at a position where water is injected is a highly dispersed screw.

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

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

It is also preferable to install a known filter at the outlet of the extruder to remove foreign matter, gelled matter, impurities, and the like that cause defects in the film.

The melted cyclic olefin resin is discharged from a flat die and solidified on a cooling roll to obtain a desired film. 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 preferred.

Examples of extruder (cylinder, screw, etc.) and die materials include SCM steel and stainless steel such as SUS, but are not limited to these. 2004/006088

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is not. The inner surface of the extruder cylinder and die and the surface of the extruder screw are plated with chrome, nickel, titanium, etc., and are coated with TiN, TiAlN, TiCN, CrN, and TiN by PVD (Physical Vapor Deposition). It is preferable to use a material on which a coating such as DLC (diamond-like carbon) is formed, a material on which tungsten carbide or other ceramics are thermally sprayed, or a material whose 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 of 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, a sleeve method, etc., depending on the film thickness and application. Appropriate method is selected.

It is preferable that various types of surface treatment be performed on the surface of the cooling port for solidifying the film extruded from the die, similarly to the extruder cylinder and the inner surface of the die. These surface treatments prevent the extruded film from sticking to the roll surface to prevent uneven thickness of the film, increase the accuracy of the cooling outlet surface, and prevent scratches due to its high surface hardness. This is preferable because the film surface accuracy can be stably maintained even when the film is manufactured, and a film having no uneven thickness can be manufactured.

In the present invention, portions of the extruder and its peripheral devices that come into contact with the active gas may be sealed with an inert gas. The inert gas is not particularly limited, but nitrogen or argon having a purity of usually 98% or more, preferably 99% or more, particularly preferably 99.9% or more is used. By introducing such an inert gas, the occurrence of defects in the film can be suppressed, which is preferable. Here, as the melt extrusion conditions for obtaining the melt extruded film of the present invention, For example, resin temperature (extruder cylinder temperature) 1 Usually, 200 to 350 ° (:, preferably, 240 to 320 ° (, the shear rate during melt extrusion is usually 1 to 5 0 (1 / Sec.), Preferably 2 to 350 (1 / Se), more preferably 5 to 200 (1 / Sec.) When the resin temperature is lower than 200 ° C., The resin cannot be melted uniformly, but if the temperature exceeds 350 ° C, the resin will be thermally degraded during melting, making it difficult to produce a high quality film with excellent surface properties. If the shear rate at the time is less than 1 (1 / Sec.), The resin cannot be melted uniformly, so that an extruded film with a small thickness unevenness cannot be obtained, while 500 (1 / Sec.) Exceeding the range is not preferable because the resin and additives are decomposed and deteriorated due to excessive shearing force, and defects such as foaming, die lines, and deposits are generated on the surface of the extruded film.

The sheet or film obtained by the present invention can be subjected to known processing. For example, stretching processes such as uniaxial stretching and biaxial stretching, embossing to create patterns and fine shapes, stamping, prism processing, printing, anti-reflection and diffusion functions, hard coating, conductivity, reflection functions It is possible to perform a dry or wet coating treatment for the purpose of providing. In addition, other homogeneous resin such as cyclic olefin resin, known thermoplastic resin, thermosetting resin, metal, glass, ceramics, etc. may be used in a film, sheet, plate, or other known method. It is also possible to laminate with a member formed into a shape. In the case of lamination, it is possible to select a method such as fusion by heat or ultrasonic waves, a known thermosetting or photo-curable adhesive, or a method such as mechanical bonding according to the purpose.

According to the present invention, a cyclic olefin resin film or sheet having stable properties and formed from a cyclic olefin resin from which a solvent that is a sufficiently volatile component has been removed is obtained. In particular, the cyclic olefin polymer solution used as a raw material in the present invention contains a cyclic olefin polymer and a polymerization solution, and is formed by solution polymerization. Product or its hydrogenated product or a concentrate thereof, after the synthesis of the cyclic olefin polymer, if it does not have a heat history other than concentration, it may be subjected to heating and cooling such as pelletization, drying, and melting. By subjecting the cyclic olefin polymer to melt kneading in an extruder without going through a process, the heat history can be suppressed, and the heat history of the cyclic olefin polymer and the resulting film or sheet can be reduced. Quality deterioration such as coloring can be suppressed. Further, in the present invention, a cyclic olefin resin film or sheet can be manufactured with a small number of steps and heat energy, so that equipment can be simplified, heat energy can be saved, and it is economical.

The cyclic olefin film or sheet obtained by the present invention is used for retardation film, polarizing plate, polarizing plate protective film, wave plate, light diffusing plate, prism sheet, anti-reflection film, liquid crystal electroluminescence application. The present invention can be suitably applied to known uses of cyclic olefin-based polymers, such as display element substrates, touch panels, and light guide plates.

According to the present invention, a cyclic olefin-based film or sheet having a stable property from which a solvent is sufficiently removed can be produced by a simple method. Further, according to the present invention, it is possible to provide a method for producing a cyclic olefin polymer film or sheet in which quality deterioration due to heat history is suppressed. Further, according to the present invention, it is possible to provide an economical method for producing a cyclic olefin polymer film or sheet which simplifies equipment and saves heat energy.

Example

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. In the following, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified. In addition, various measurements The items are the values obtained as follows.

Glass transition temperature (Tg)

The measurement was carried out by a differential scanning calorimeter (DSC) in accordance with JIS K7121 under a nitrogen atmosphere at a heating rate of 10 ° C./min.

Hydrogenation rate

It was determined from the proton ratio of the proton on the carbon-carbon double bond and the methyl proton of the carboxymethyl group at 50 OMHz and ¾-NMR.

Intrinsic viscosity [7?] _Inh

The intrinsic viscosity of the sample at a concentration of 0.5 g Zd1 was measured at 30.0 ° C. using a Ube-Made viscometer.

Water absorption

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

Synthesis example 1

8-methyl-8-methoxycarbonyltetracyclo [4.4.0. I ² · ^5. I ⁷ · ¹⁰ ] -3-dodecene (specific monomer) 215 parts, bicyclo [2.2.1] hept-2-e In a reaction vessel in which 35 parts of 1-hexene (23 parts of 1-hexene (molecular weight regulator) and 750 parts of toluene were replaced with nitrogen), this solution was heated to 60 ° C. Next, 0.62 parts of a toluene solution of triethyl aluminum (1.5 mol Z 1) as a polymerization catalyst and tungsten hexachloride (tert-butanol) modified with tert-butanol and methanol were added to the solution in the reaction vessel. : Methanol: Tungsten = 0.35: 0.30: 1.00 molar ratio) Toluene solution (concentration 0.05 mol Z1) 3.7 parts was added, and this system was heated and stirred at 80 ° C for 3 hours for ring-opening copolymerization. The reaction was performed to obtain a ring-opening copolymer solution.

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

4000 parts of the ring-opening copolymer solution thus obtained was charged into an autoclave. Seen, in the ring-opening copolymer solution, RuHCl (CO) [P ( C 6 H 5) 3] 3 0. was added 48 parts of a hydrogen gas pressure of 100 kg / cm ^2, the reaction temperature 165. Under the condition of C, the mixture was heated and stirred for 3 hours to carry out a hydrogenation reaction. After cooling the obtained reaction solution (hydrogenated copolymer solution), hydrogen gas was released.

The hydrogenation rate of the thus obtained hydrogenated copolymer was measured by using ¾-Ran R, and was substantially 100%. The intrinsic viscosity [] _inh of the copolymer was 0.53 dl / g, and the glass transition temperature was 123 ° C. The polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin were measured by the GPC method (solvent: tetrahydrofuran), and were 22,000 and 70,000, respectively. (Mw / Mn) was 3.18.

Example 1

To the hydrogenated copolymer solution obtained in Synthesis Example 1 was added 0.1 part of Irganox 1010 (manufactured by Ciba Charity Chemicals) as an antioxidant based on 100 parts of the copolymer. The filter was connected in series with 5 μπι and 0.2 μηι. Filters, concentrated to 50% solids, and the solution was used as a sample. Temperature 130. The sample of C was supplied to an extruder having five vents at a flow rate of 80 kg Zhr in terms of resin, and the solvent was gradually removed at each vent. The resin from which the solvent had been removed was pressurized by a gear pump and supplied quantitatively to the T-die to produce an extruded film 100 μπι thick and 650 mm wide.

The extruder has an L_D of 56, one of the five vents is a rear vent, has a seal between each vent port, and can control the operating pressure of each vent independently. used. Screw one uses made of SUS, it was operated at a rotational number 360 rp _m. The operating pressure and operating temperature of each vent are as shown in Table 1 below.

The molding equipment used consisted of a twin screw extruder, a gear pump, a T-die, a cooling roll, and a winder in order from the previous process.

The screw configuration of the extruder is a screw configuration consisting of a full-flight screw and a progressive kneading disk up to # 3 vent, and between the # 3 vent and the final vent, a reverse flight screw from the upstream side and a notch at the summit. A highly dispersive screw configuration is adopted in which the screw, progressive kneading disk, knurled notch screw, and reverse fly screw are arranged in this order.

For the T-die, use a coat hanger type with a manifold shape, and use s for steel.

CM 435, the surface of the channel is hard chrome plated. The lip edge is a shear pedge and has no defects. The surface roughness of the lip surface was 0.1 S, and the lip opening was 0.5 thigh. For the T-die heater, an aluminum built-in heater was used, and the heater temperature was set at 260 ° C.

On the other hand, the cooling roll used was a 40-Oram outer diameter (manufactured by Tokuden) equipped with a vacuum jacket inside the roll, and the surface roughness was 0.1 S. The mouth temperature was controlled at 110 ° C with a heat transfer oil. In addition, an Ep roll was used to adhere the film to the cooling roll.

The film obtained within 2 hours from the start of operation is processed without sampling. The film was sampled after the temperature and pressure of the extruder and die were confirmed to be stable. Unless otherwise specified, samples collected two hours after the start of operation were used for various evaluations.

Example 2

Except for sampling, except that 1% water was injected continuously to the resin processing amount (amount of hydrogenated copolymer) between the # 3 vent port and the final vent port of the extruder. In the same manner as in 1, an extruded film having a thickness of 100 m and a width of 65 Omm was produced.

Comparative Example 1

To the hydrogenated copolymer solution obtained in Synthetic Example 1 was added 0.1 part of Irganottus 1010 (manufactured by Ciba-Sharability Chemicals) as an antioxidant to 100 parts of the copolymer, and then the aperture was increased. Is connected in series with filters of 5ηι and 0.2μηι., And the solution concentrated to 50% solid content is supplied to the twin-screw extruder, and after removing volatiles, the strand is sieved with a strand die. Obtained. After the obtained strand was cooled, it was cut with a strand cutter to produce a pellet-shaped resin. The same extruder as in Example 1 was used, and the operating conditions were the same. However, the screw configuration was a screw configuration consisting of a full flight screw and a progressive feeding kneading disk.

The pellets obtained were dehumidified and dried under nitrogen at 80 ° C for 4 hours at 80 ° C, melted using a 65-band Φ single-screw extruder, and the gear pump, T-die, cooling roll, winding An extruded film having a thickness of 100111 and a width of 65 Omm was produced in the same manner as in Example 1, including sampling, using a scraper.

(Evaluation of film)

Example 1 and Comparative Example 1 Residual solvent amount in resin at each extruder outlet Was measured by gas chromatography with an FID detector. The appearance of the obtained film was also evaluated. The results are shown in Tables 2 and 3. The evaluation of the appearance of the film was performed using a sample of 65 Omm x 1 m, irradiating a halogen lamp with an output of 150 W at a point 1 m away from the film, and irradiating the light with a distance of 1 m from the film. The following evaluation was performed based on the image reflected on the screen installed at the site.

The distance from the lamp z film z screen is the distance from the center of the film (the intersection of diagonal and 角).

Bright spot

The film was set parallel to the screen and irradiated with light, and the number of point-like defects projected on the screen was counted. The result was expressed as the number per 1 m ² . Die line

The film was set parallel to the screen, irradiated with light, and the linear density projected on the screen was visually observed and evaluated according to the following evaluation criteria. 1: No linear shading can be confirmed.

2: Faint linear shading can be confirmed.

3: Clear linear shading can be confirmed.

Foreign matter

The formed film (1 Og) was dissolved in a solvent (toluene), filtered through a 0.1-im membrane filter, and the collected solvent insolubles were collected. The number of foreign substances described above was counted and defined as the number of foreign substances per 1 Og of the film. Durability evaluation

The yellowness YI of the film was measured with a spectrophotometer (manufactured by Suga Test Instruments). Furthermore, the film was left in a gear oven heated to 120 ° C for 500 hours, before and after the test. 200

39

Was measured for a difference in yellowness Δ.

Table 2

Table 3

From Tables 2 and 3, it can be seen that the film obtained by the production method of the present invention has excellent surface defects such as volatile points and die lines, and is an excellent film. In addition, compared to films obtained by melt extrusion from conventional pellets, f-heat coloring is also small.

According to the production method of the present invention, it is possible to produce a film or a sheet with a small number of steps and a small amount of thermal energy, and it is possible to obtain an excellent film or a sheet with a small heat history.

Claims

The scope of the claims

1. It consists of a cyclic olefin resin and a solvent.

A cyclic olefin resin solution containing 80% by weight is

Introduced into the extruder with vent,

In the extruder, remove the volatile components of the cyclic olefin resin solution,

A method for producing a cyclic olefin-based resin film or sheet, comprising melt-extruding a film-shaped or sheet-shaped molded product from a die.

2. The method for producing a cyclic olefin-based resin film or sheet according to claim 1, wherein an extruder in which at least a part of a screw configuration is a high dispersion type is used.

3. The method for producing a cyclic olefin resin film or sheet according to claim 1, wherein an extruder having a reavent is used.

4. The method for producing a cyclic olefin resin film or sheet according to any one of claims 1 to 3, wherein an extruder having a plurality of vents is used.

5. Annular Orefin resin solution, the production of cyclic Orefin resin film or sheet according to any one of claims 1 to 4, characterized in that 4 0-7 0 weight ^_0/0 containing a cyclic Orefin resin Method.

6. The cyclic olefin resin solution contains the cyclic olefin resin and the polymerization solvent. The method for producing a cyclic olefin resin film or sheet according to any one of claims 1 to 5, wherein a solution containing a solution produced by solution polymerization is used.

7. The cyclic olefin resin film or sheet according to any one of claims 1 to 6, wherein the solvent content of the cyclic olefin resin at the outlet of the extruder is 100 ppm or less. Production method.

8. The method for producing a cyclic olefin resin film or sheet according to any one of claims 3 to 7, wherein 15 to 35% of the solvent of the cyclic olefin resin solution is removed by a reavent of the extruder. .

9. The cyclic olefin resin film according to any one of claims 4 to 8, wherein an operating pressure of each vent is independently and arbitrarily controlled using an extruder having a seal portion between ventros. Sheet manufacturing method.

10. The method for producing a cyclic olefin resin film or sheet according to any one of claims 4 to 9, wherein water is injected into at least one of the vent holes of the extruder. .

11. The method for producing a cyclic resin-based resin film or sheet according to claim 10, wherein an extruder having a highly dispersed screw configuration is used as a screw configuration at a position where water is injected. .

12. The cyclic olefin resin film according to any one of claims 1 to 11, wherein a resin having a water absorption of 0.05 to 0.5% by weight is used as the cyclic olefin resin. Or sheet manufacturing method.