JP2001009859A - Method for producing cyclic olefin resin sheet - Google Patents

Abstract

(57) [Problem] To provide a method for producing a cyclic olefin resin sheet which is excellent in sheet appearance and applicable to optical applications. SOLUTION: A cyclic olefin resin is heated and melted at a temperature higher by 30 to 150 ° C. than a glass transition temperature of the resin, and the molten resin is rolled side by side in a pair of calender rolls rotating in opposite directions. By the method for producing a cyclic olefin resin sheet which is then drawn out from the roll gap into a sheet, the sheet appearance is excellent without yellow discoloration, etc., so that it is also used for diffusion sheets, light guide sheets, conductive transparent films and the like. An applicable sheet is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a cyclic olefin resin sheet, and more particularly, to a method for producing a cyclic olefin resin sheet having excellent mechanical strength and sheet appearance and applicable to optical applications. .

[0002]

2. Description of the Related Art The calender molding method is widely used for molding rubber or vinyl chloride resin. This molding method has a larger discharge amount per unit time than extrusion molding, and is excellent in productivity. However, resins other than the vinyl chloride resin, for example, linear olefin resins such as polyethylene and polypropylene, were difficult to peel off from the roll surface even when a large amount of lubricant was added to the resin, making it difficult to form a sheet. Therefore, in the case of a linear olefin resin, after a sheet is formed by an extrusion molding method or the like, the sheet is simply rolled with a roll. Also,
JP-A-5-65350 discloses that a random copolymer or a ring-opened polymer of a cyclic olefin or a hydrogenated product thereof is used.
Only a method of producing a film in which a raw film is obtained by extrusion molding, compression molding, or injection molding and the film is rolled through a calendar roll has been proposed. Also,
In calender molding, since the molten resin has stayed for a while in the valley of the gap between the rolls, it has been considered difficult to apply the resin to a resin susceptible to oxidative deterioration.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a sheet made of a cyclic olefin resin, which is excellent in sheet appearance and is applicable to optical applications and the like, by calendering. The present inventors have conducted intensive studies to achieve the above object, and as a result, by heating and melting a cyclic olefin resin to a specific temperature and calender-molding the molten resin, a sheet excellent in sheet appearance can be obtained. Have been found, and the present invention has been completed based on these findings.

[0004]

Thus, according to the present invention, a cyclic olefin resin is heated and melted at a temperature 30 to 150 ° C. higher than the glass transition temperature of the resin, and the molten resins are juxtaposed. Further, a method is provided for producing a cyclic olefin resin sheet which is guided to a roll gap of a pair of calendar rolls rotating in opposite directions, and is then drawn out into a sheet form from the roll gap.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION According to the production method of the present invention, a cyclic olefin resin is used in an amount of 30 to 150 ° C. based on the glass transition temperature of the resin.
This is a method in which the molten resin is heated to a high temperature and melted, and the molten resin is guided to a roll gap between a pair of calendar rolls arranged in parallel and rotating in the opposite direction, and then drawn out into a sheet form from the roll gap.

(Cyclic olefin resin) The cyclic olefin resin used in the present invention is a resin having an alicyclic structure in the main chain and / or side chain, and from the viewpoints of mechanical strength, heat resistance, etc. Preferably contains an alicyclic structure. Examples of the alicyclic structure of the polymer include a cycloalkane structure and a cycloalkene structure.From the viewpoint of mechanical strength and heat resistance, a cycloalkane structure or a cycloalkene structure is preferable, and among them, a cycloalkane structure has Those are most preferred because they have excellent weather resistance and chemical resistance. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, and more preferably 5 to 15, when the mechanical strength, The properties of heat resistance and moldability are highly balanced and suitable.

[0007] The proportion of the repeating unit having an alicyclic structure in the cyclic olefin resin used in the present invention may be appropriately selected according to the purpose of use, but is usually 30% by weight or more, preferably 50% by weight. The content is more preferably 70% by weight or more. If the proportion of the repeating unit having an alicyclic structure in the cyclic olefin resin is too small, the heat resistance is poor, which is not preferable. The remainder other than the repeating unit having an alicyclic structure in the cyclic olefin resin is not particularly limited,
It is appropriately selected according to the purpose of use. As the cyclic olefin resin, a thermoplastic resin is preferable.

Specific examples of the polymer resin having an alicyclic structure include (1) a norbornene-based polymer,
(2) a monocyclic cycloolefin polymer, (3) a cyclic conjugated diene polymer, (4) a vinyl alicyclic hydrocarbon polymer, and hydrogenated products thereof. Among these, norbornene-based polymers and hydrogenated products thereof,
A cyclic conjugated diene-based polymer and a hydrogenated product thereof are preferred, and a norbornene-based polymer and a hydrogenated product thereof are more preferred.

(1) Norbornene-based polymer The norbornene-based polymer is not particularly limited, and is disclosed in, for example, JP-A-3-14882 and JP-A-3-122.
A polymer obtained by polymerizing a norbornene-based monomer (a cyclic olefin monomer having a norbornene ring) by a method disclosed in Japanese Patent No. 137,137 or the like is used. Specific examples include a ring-opening polymer of a norbornene-based monomer and a hydrogenated product thereof, an addition polymer of a norbornene-based monomer, and an addition-type polymer of a norbornene-based monomer and a vinyl compound. Among these, hydrogenated ring-opening polymers of norbornene-based monomers, addition-type polymers of norbornene-based monomers, and addition-type polymers of vinyl compounds copolymerizable with norbornene-based monomers are preferred. In particular, hydrogenated ring-opening polymers of norbornene monomers are particularly preferred. Hydrogenated ring-opening polymer of norbornene-based monomer has a large difference between plasticization temperature and decomposition temperature, and is suitable for calendering with heating, and therefore has excellent mechanical strength and excellent appearance. Can be formed.

As norbornene-based monomers, bicyclo [2.2.1] hept-2-ene (common name: norbornene) and 5-methyl-bicyclo [2.2.1] hepta-2
-Ene, 5,5-dimethyl-bicyclo [2.2.1] hept-2-ene, 5-ethyl-bicyclo [2.2.1]
Hept-2-ene, 5-butyl-bicyclo [2.2.
1] Hept-2-ene, 5-hexyl-bicyclo [2.
2.1] Hept-2-ene, 5-octyl-bicyclo [2.2.1] Hept-2-ene, 5-octadecyl-
Bicyclo [2.2.1] hepta-2-ene, 5-ethylidene-bicyclo [2.2.1] hepta-2-ene, 5-
Methylidene-bicyclo [2.2.1] hepta-2-ene, 5-vinyl-bicyclo [2.2.1] hepta-2-
Ene, 5-propenyl-bicyclo [2.2.1] hepta-2-ene, 5-methoxy-carbonyl-bicyclo [2.2.1] hepta-2-ene, 5-cyano-bicyclo [2.2. 1] Hept-2-ene, 5-methyl-5
Methoxycarbonyl-bicyclo [2.2.1] hepta
2-ene;

5-methoxycarbonylbicyclo [2.
2.1] Hept-2-ene, 5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-ethoxycarbonylbicyclo [2.2.1] hept-2-ene, bicyclo [2.
2.1] Hept-5-enyl-2-methylpropionate, bicyclo [2.2.1] hept-5-enyl-2-
Methyl octanate, bicyclo [2.2.1] hept-
2-ene-5,6-dicarboxylic anhydride, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene,
5,6-di (hydroxymethyl) bicyclo [2.2.
1] Hept-2-ene, 5-hydroxy-i-propylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene;
5-Cyanobicyclo [2.2.1] hept-2-ene, bicyclo [2.2.1] hept-2-ene-5,6
-Dicarboxylic imide; tricyclo [4.3.
^12.5 . 0 ^1,6 ] deca-3,7-diene (commonly used dicyclopentadiene), tricyclo [4.3.1 ^2,5 . 0 ^1,6 ]
Deca-3-ene; tricyclo [4.4.1 ^2,5 .
0 ^1,6 ] undeca-3,7-diene or tricyclo [4.4.1 ^2,5 . [ ^1,6 ] undeca-3,8-diene or a partially hydrogenated product thereof (or an adduct of cyclopentadiene and cyclohexene).
4.1 ^2,5 . 0 ^1,6 ] undec-3-ene;

5-Cyclopentyl-bicyclo [2.2.
1] Hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexenylbicyclo [2.2.1] hept-2-ene, 5-phenyl-bicyclo [ 2.2.1] Hept-2-ene; tetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodeca
3-ene (also simply referred to as tetracyclododecene), 8-
Methyltetracyclo [4.4.1 ^2,5 . ^17,10 . 0]-
Dodeca-3-ene, 8-ethyltetracyclo [4.4.
^12.5 . ^17,10 . 0] -dodec-3-ene, 8-methylidenetetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene, 8-ethylidenetetracyclo [4.
4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene, 8-vinyltetracyclo [[4.4.1 ^2,5 . ^17,10 . 0]-
Dodeca-3-ene, 8-propenyl-tetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene,
8-methoxycarbonyltetracyclo [4.4.
^12.5 . ^17,10 . 0] -dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.1
^2,5 . 1 ^{7,1 0.} 0] - dodeca-3-ene, 8-hydroxymethyl-tetracyclo [4.4.1 ^2, 5. ^17,10 . 0]
-Dodec-3-ene, 8-carboxytetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene;
8-cyclopentyl-tetracyclo [4.4.
^12.5 . ^17,10 . 0] -dodec-3-ene, 8-cyclohexyl-tetracyclo [4.4.1 ^2,5 . ^17,10 .
0] -dodec-3-ene, 8-cyclohexenyl-tetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodeca-3
-Ene, 8-phenyl-cyclopentyl-tetracyclo [4.4.1 ^2,5 . ^17,10 . 0] -dodec-3-ene;
Tetracyclo [7.4.1 ^10,13 . 0 ^1,9 . 0 ^2,7 ] trideca-2,4,6,11-tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydrofluorene), tetracyclo [8.4.1 ^11,14 . 0 ^{1,1 0} . 0
^3,8 ] tetradeca-3,5,7,12-tetraene (1,4-methano-1,4,4a, 5,10,10a-
Also referred to as hexahydro-anthracene), pentacyclo [6.5.1 ^{1,8. 13-6} . 0 ^2,7 . 0 ^9,13] pentadeca-3,10-diene, pentacyclo [7.4.1 ^3,6.
1 ^10,13 . 0 ^1,9 . 0 ^2,7 ] pentadeca-4,11-diene; cyclopentadiene tetramer; and the like.

These norbornene monomers may be used alone or in combination of two or more. Among the norbornene-based monomers, it is preferable that dicyclopentadiene is contained. For example, a combination of dicyclopentadiene and tetracyclododecene, dicyclopentadiene, tetracyclododecene, and ethyltetracyclododecene , A combination of dicyclopentadiene and ethyltetracyclododecene, a combination of dicyclopentadiene and ethylidenetetracyclododecene, a combination of dicyclopentadiene and 1,4-methano-1,4,4a, 9a-
And a combination with tetrahydrofluorene.

Examples of the vinyl compound that can be copolymerized with the norbornene monomer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene,
3-methyl-1-butene, 3-methyl-1-pentene,
3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1
-Hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-
C2-C20 ethylene or α-olefins such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethyl Cycloolefins such as cyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene; Hexadiene, 4-methyl-1,
Non-conjugated dienes such as 4-hexadiene, 5-methyl-1,4-hexadiene and 1,7-octadiene; Each of these vinyl compounds, alone,
Alternatively, two or more kinds can be used in combination.

The method of polymerization and hydrogenation of the norbornene-based monomer or the vinyl compound copolymerizable with the norbornene-based monomer are not particularly limited, and can be carried out according to known methods.

(2) Monocyclic Cyclic Olefin Polymer Examples of the monocyclic cycloolefin polymer include monocyclic cycloolefin polymers such as cyclohexene, cycloheptene and cyclooctene disclosed in JP-A-64-66216. Can be used.

(3) Cyclic conjugated diene polymer As the cyclic conjugated diene polymer, for example, Japanese Patent Application Laid-Open No.
The cyclic conjugated diene-based monomers such as cyclopentadiene and cyclohexadiene disclosed in JP-A-136057 and JP-A-7-258318 are used as 1,2- or 1,2-
4-Polymerized polymers and hydrogenated products thereof can be used.

(4) Hydrocarbon polymers having an alicyclic structure in the side chain Examples of the hydrocarbon polymers include polymers of vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane. And a hydrogenated product thereof, a hydrogenated product of a styrene-based polymer, and the like.

The molecular weight of the cyclic olefin resin used in the present invention is appropriately selected according to the purpose of use, but it is determined by gel permeation chromatography of a cyclohexane solution (a toluene solution when the polymer resin is not dissolved). The number average molecular weight in terms of polyisoprene measured in
5,000 to 500,000, preferably 8,000 to
200,000, more preferably 10,000 to 10
000, and usually 10,000 weight-average molecular weight.
00 to 1,000,000, preferably 15,000 to
500,000, more preferably 20,000 to 20
It is 0000. MWD (= weight average molecular weight / number average molecular weight) is usually 1.0 to 10, preferably 1.0 to 6,
It is more preferably 1.1 to 4. By adjusting the molecular weight to such a range, the mechanical strength of the sheet and the moldability are well balanced.

The glass transition temperature (Tg) of the cyclic olefin resin used in the present invention may be appropriately selected according to the purpose of use, but is preferably 50 to 200 ° C. or more, more preferably 70 to 150 ° C. or more. , Most preferably 80-
120 ° C. When Tg is in this range, yellowing due to oxidative deterioration of the resin during plasticization of the resin during calendering is less likely to occur, and the heat resistance of the obtained sheet is improved.

The 5% loss on heating of the cyclic olefin resin used in the present invention (measured in a nitrogen atmosphere at a heating rate of 5 ° C./min) is preferably at least 280 ° C., particularly preferably at least 350 ° C. is there. It is preferable that the 5% heating loss temperature be in this range because even if the temperature of the resin is increased, decomposition of the resin hardly occurs and molding defects such as inclusion of bubbles in the molded product due to decomposition of the resin can be prevented.

The melt viscosity of the cyclic olefin resin used in the present invention at a temperature of 260 ° C. is usually 1 × 10 ¹ to 1
× 10 ⁵ poise, preferably 1 × 10 ² to 1 × 10 ³ poise. When the melt viscosity is in this range, the formability of the sheet and the mechanical strength are well balanced and suitable.

(Additives) The cyclic olefin resin used in the present invention may contain, if necessary, other polymers, antioxidants, antioxidants, lubricants, light stabilizers, ultraviolet absorbers,
A filler, a colorant, a crosslinking agent, a curing agent, a plasticizer, a foaming agent, and the like can be used alone or in combination of two or more.

When the above-mentioned components (other polymers, compounding agents and fillers) are used, they may be added during the production process of the cyclic olefin resin or after the production of the resin,
The cyclic olefin resin can be added in the step of kneading, mixing or melting.

In the production method of the present invention, the resin is heated and melted at a temperature 30 to 150 ° C., preferably 70 to 120 ° C. higher than its glass transition temperature.
The method of heating and melting the resin can be performed by a known method. For example, it can be performed using an extruder, a kneader, or the like. In the extruder, a strainer is preferable because it can filter foreign substances that may be contained in the resin and can supply the compound to the calender roll at a uniform temperature. The strainer machine itself has the same structure as the extruder, but at its tip, about 20 mesh or more,
Preferably, a wire mesh of 60 mesh or more is attached. As a special strainer, there is a mixer that combines a super mixer and an extruder.

In the production method of the present invention, the molten resin is guided to a roll gap of a pair of calendar rolls which are arranged side by side and rotate in the opposite direction, and is then drawn out of the roll gap into a sheet. There are at least two calender rolls, and an arrangement similar to that performed with rubber or vinyl chloride resin can be used.

There are three arrangement methods: vertical, horizontal, and inclined.
There are basic forms, and by combining them,
There are Z type, inverted L type, U type, camel back type, M type and the like. Further, various combinations are possible by changing the number of rolls from two to more than ten, and a cooling roll, a feed roll, a pressure roll, and the like can be combined as devices attached to the calender roll. Specifically, 2 vertical, 2 tilt, 3 vertical, 4 vertical coating, 2 vertical inverted L4, 2 vertical horizontal 2
3 pairs, 2 vertical inverted L4 cooling, 1 cooling, 5 U-shaped cooling 1
4 pieces, Camel back type 4 pieces, Cooling 1 piece, 3 pieces vertical 1 pair combination, Reverse L 4 pieces crimping 2 pieces, Z type 4 pieces crimping 2 pieces, 2 pieces horizontal,
Three inverted L-shapes, four vertical, four inverted L-shaped, four camel-backed, three vertical cooling, one inverted L-shaped four cooling, one Z-shaped
One main cooling, three vertical feeds, four Z-shaped four cooling, four inverted L-shaped four cooling, and the like.

In the manufacturing method of the present invention, four inverted L-shaped ones as shown in FIG. 1 are preferable when workability is emphasized, and in FIG. 2 when thickness accuracy is emphasized. Four Z-shaped as shown, or inclined Z as shown in FIG.
Four molds are preferred.

The temperature of the calender roll (a set of rolls into which the molten resin is first introduced) is slightly different depending on the rotation speed of the roll, but the upper limit is usually 230 to prevent the production of a yellow discolored sheet. ° C, preferably 210
℃, more preferably 200 ℃, the lower limit is usually 100 ℃, in order to prevent the production of low smoothness sheet
Preferably it is 130 ° C, more preferably 160 ° C.
The temperature of the second and subsequent rolls is not particularly limited.
The temperature is set equal to or slightly lower than the temperature of the set of rolls into which the molten resin is first introduced.

The sheet drawn from the gap between the calender rolls has a thickness of several microns to several millimeters (including a film). The thickness of the sheet can be controlled by calender speed, roll temperature, roll nip distance, and the like. As the sheet is pulled out from the gap between the calender rolls, the sheet can be stretched uniaxially or biaxially by applying tension.

The sheet pulled out from the gap between the calender rolls is then taken off by a take-off roll, a cooling take-off device,
It becomes a product sheet via a winding machine.

An adhesive, a gluing machine, a doctor knife coater, a roll coater or the like is applied to the sheet.
An adhesive or the like can be applied. In addition, using a laminating device, laminating embossing device, metal foil,
Films for coloring and decoration, cloth, paper, etc. can be laminated, desired unevenness can be formed on the sheet surface using an embossing device, etc., and printing can be performed on the sheet surface using a printing device. . When a blowing agent is blended with the cyclic olefin resin, a foamed sheet can be obtained by passing the blowing agent through a foaming device such as a foaming furnace.

The sheet obtained by the present invention has a yellowness of preferably 2 or less, particularly preferably 1 or less. As described above, the sheet obtained by the production method of the present invention does not discolor yellow, and thus can be suitably used for optical applications.

According to the production method of the present invention, a multilayer sheet or a coating sheet can be easily formed. For example, the cyclic olefin resin, a linear olefin resin such as polyethylene, a polyester resin, a polyamide resin, or the like can be formed into a sheet by a calender roll, and both sheets can be pressed by a subsequent roll.

[0035]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. EXAMPLE A cyclic olefin resin (glass transition temperature: 98 ° C., 5% heating loss temperature: 360 ° C.) obtained by hydrogenating ring-opening copolymerization of dicyclopentadiene / tetracyclododecene was heated and melted at 180 ° C. by a kneader. Thus, a molten resin was obtained. Using an 8-inch inverted L-shaped four calender molding machine shown in FIG. 1, the temperature of each roll was set to 190 ° C., and the first roll 1 was rotated at 9 rpm.
12 rpm for the second roll 2 and 20 rpm for the third roll 3
m, the fourth roll 4 is rotated in a predetermined rotation direction at 26 rpm, the molten resin is introduced into the first bank B1 (the valley of the gap between the first roll 1 and the second roll 2), and the molten resin is further The second bank B2 (the gap between the second roll 2 and the third roll 3), the third bank B3 (the third roll 3 and the fourth roll 4)
), And finally peeled off from the fourth roll 4, stretched to a predetermined thickness, and cooled to obtain a sheet. The releasability from the fourth roll 4 was good, and the surface of the obtained sheet was smooth and colorless and transparent.

Comparative Example 1 A sheet was obtained in the same manner as in Example 1 except that the molten resin at 120 ° C. was introduced into the first bank B1 of a calender molding machine having a roll temperature of 125 ° C. The releasability from the fourth roll 4 was slightly poor, and the fourth roll 4 was pulled toward the third bank B3. The obtained sheet had irregularities on its surface and had low transparency.

Comparative Example 2 A sheet was obtained in the same manner as in Example 1 except that the molten resin at 255 ° C. was introduced into the first bank B1 of the calender molding machine having a roll temperature of 260 ° C. Although the releasability from the fourth roll 4 was acceptable, the obtained sheet had irregularities on its surface and was discolored to yellow.

[0038]

The cyclic olefin resin sheet of the present invention has no yellow discoloration, has a smooth surface, and is excellent in sheet appearance. Therefore, it can be applied to applications such as diffusion sheets, light guide sheets, and conductive transparent films. It is possible.

[Brief description of the drawings]

FIG. 1 is a diagram showing a roll arrangement of a four inverted L-type calendar.

FIG. 2 is a diagram showing a roll arrangement of a Z-type four-calender.

FIG. 3 is a view showing a roll arrangement of four inclined Z-type calendars.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 1st roll 2 2nd roll 3 3rd roll 4 4th roll B1 1st bank B2 2nd bank B3 3rd bank 21 1st roll 22 2nd roll 23 3rd roll 24 4th roll B21 1st bank B22 1st roll 2 bank B23 3rd bank 31 1st roll 32 2nd roll 33 3rd roll 34 4th roll B31 1st bank B32 2nd bank B33 3rd bank

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 45:00 (72) Inventor Naoki Shinohara 1-2-1 Yaiko, Kawasaki-ku, Kawasaki-shi, Kanagawa Japan Zeon stock F term in the Company Development Center (reference) 4F071 AA39 AF13 AF30 AF34 AH12 BB04 BC01 4F204 AA12 AD29 AG01 AH73 AK07 AR06 FA07 FA08 FA09 FB02 FE06 FF01 FF23 FF49 FG07 FH06 FJ08 FJ29 FN11 FN15 FQ32

Claims (3)

[Claims] 1. A method for heating a cyclic olefin resin to a temperature 30 to 150 ° C. higher than the glass transition temperature of the resin to melt the molten resin. A method for producing a sheet made of a cyclic olefin resin, which is led to a roll gap and then drawn out into a sheet from the roll gap. 2. The method according to claim 1, wherein the temperature of the calender roll is at least 150 ° C. and less than 230 ° C. 3. A calender roll in which four inverted L-shaped rolls, four Z-shaped rolls or four inclined Z-shaped rolls are arranged.
The method according to claim 1.