JP3520877B2 - Sheet or film with low moisture permeability - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet or film made of a dicyclopentadiene ring-opening polymer hydrogenated product, and more particularly to a sheet or film made of a dicyclopentadiene ring-opening polymer hydrogenated product. Sheet or film.

[0002]

2. Description of the Related Art Thermoplastic norbornene-based resins include, specifically, ring-opening polymers of thermoplastic norbornene-based monomers, hydrogenated products thereof, addition-type polymers of norbornene-based monomers,
Addition-type copolymer of norbornene-based monomer and olefin,
Examples include modified products thereof. All of these are beginning to be used in various fields as transparent resins with excellent moisture resistance, and it is possible to obtain sheets or films with a thickness of 500 μm and moisture permeability up to about 0.15 g / m ² · 24 hr. It has become.

However, in accordance with the rapid progress of technology, a conventional thermoplastic norbornene-based resin sheet or film may have insufficient moisture resistance in some cases, and a resin sheet or film having higher moisture resistance, In particular, a resin sheet or film having a lower water vapor permeability has been demanded.

On the other hand, ring-opening copolymers of dicyclopentadiene-based monomers, which are norbornene-based monomers, and tetracyclododecene-based monomers, which are also norbornene-based monomers, and hydrogenated products thereof are known. (Japanese Patent Laid-Open No. 1-138
No. 257 and Japanese Patent Laid-Open No. 1-168725).
For example, in JP-A-1-138257, a ring-opening copolymer of dicyclopentadiene and methyltetracyclododecene is obtained. Specifically, dicyclopentadiene-derived ring-opening repeating structural unit 85% by weight and methyl Disclosed is a copolymer comprising 15% by weight of a ring-opening repeating structure derived from tetracyclododecene, and a hydrogenated product thereof. However, this polymer is gelled, and the hydrogenated product has a hydrogenation rate of 9%.
It is about 3%, which is problematic for use in applications such as films and sheets that easily deteriorate. Also,
In JP-A-1-168625, the ring-opening repeating structural unit derived from dicyclopentadiene is 10 to 90% by weight and the ring-opening repeating structural unit 90 derived from methyltetracyclododecene is 90.
A copolymer hydrogenated product of 10 to 10% by weight is disclosed, and as a specific example, a dicyclopentadiene-derived ring-opening repeating structural unit of 75% by weight or less is disclosed. It is disclosed that this copolymer hydrogenated product is excellent in optical properties such as low birefringence, but there is no description concerning moisture permeability. Even if a sheet having a thickness of 500 μm is actually formed with a copolymer hydrogenated product consisting of 75% by weight of the ring-opening repeating structural unit derived from dicyclopentadiene and 25% by weight of the repeating ring-opening repeating structural unit derived from methyltetracyclododecene,
Only a water vapor transmission rate of about 0.16 g / m ² · 24 hr was obtained. Thus, the ring-opening repeating structural unit derived from the dicyclopentadiene-based monomer is 80 to 90% by weight and the ring-opening repeating structural unit derived from the tetracyclododecene-based monomer is 20 to 10% by weight. Sheets and films of polymeric hydrogenates have not been specifically known. Further, such a sheet or film is particularly excellent in moisture permeability, and when stretched,
It was unpredictable that a transparent sheet or film having a moisture permeability as low as 0.13 g / m ² · 24 hr or less at a thickness of μm, which is unprecedented, could be obtained.

[0005]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The present inventors have earnestly studied for the purpose of developing a thermoplastic norbornene resin sheet or film having particularly low water vapor permeability, and as a result, dicyclopentadiene monomer and tetracyclo The hydrogenated product of a ring-opening copolymer obtained by copolymerizing a dodecene-based monomer at a specific ratio has a particularly low water vapor transmission rate, and is further stretched to give 5
A sheet or film having a thickness of 00 μm and a moisture permeability of 0.
It was found that a resin having a weight of 13 g / m ² · 24 hr or less can be obtained, and the present invention has been completed.

[0006]

Thus, according to the present invention, a dicyclopentadiene monomer-derived ring-opening repeating structural unit 8
0 to 90% by weight and 20 to 10% by weight of the ring-opening repeating structural unit derived from a tetracyclododecene-based monomer, and the unsaturated bond of the main chain of the copolymer substantially containing no gel has a hydrogenation rate of 98. There is provided a sheet or film produced by stretching a hydrogenated sheet or film hydrogenated at a rate of not less than 100% at a draw ratio of 1.05 to 5.00.

The dicyclopentadiene-based monomer (hereinafter referred to as DCP-based monomer) used in the present invention is dicyclopentadiene, an alkyl or aromatic substituted derivative thereof, or a substituted or unsubstituted dicyclopentadiene thereof. A halogen group, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an amide group, an imide group, a siliu group, and the like, and specifically, dicyclopentadiene, 2-methyldicyclopentadiene, 5- Examples include methyldicyclopentadiene, 7-methyldicyclopentadiene, 2-ethyldicyclopentadiene, 5-methyldicyclopentadiene, 5,5-dimethyldicyclopentadiene. These are used alone or as a mixture of a plurality of monomers. The DCP-based monomer is used so that the repeating structural unit derived therefrom is 80 to 90% by weight, preferably 81 to 88% by weight, more preferably 82 to 87% by weight in the ring-opening copolymer. . If the amount is too small or too large, the water vapor permeability of the sheet or film of the present invention becomes high. Also,
The more the polar groups are, the higher the hygroscopic property of the hydrogenated product is. Therefore, the smaller the amount of the polar group-substituted product is, the more preferable.

The tetracyclododecene-based monomer (hereinafter referred to as TCD-based monomer) used in the present invention is tetracyclododecene, an alkyl, alkylidene, aromatic substituted derivative thereof, or a substituted or unsubstituted product thereof. Is a polar group-substituted product of halogen, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an amide group, an imide group, a siliu group, etc. of dicyclopentadiene, specifically, tetracyclododecene, 6-methyltetra Cyclododecene, 6-ethyltetracyclododecene, 6-ethylidenetetracyclododecene, 6-isopropyltetracyclododecene, 6-
Examples thereof include phenyltetracyclododecene and 6,7-dimethyl-tetracyclododecene. The TCD-based monomer has a repeating structural unit derived therefrom in the ring-opening copolymer in an amount of 10 to 20% by weight, preferably 12 to 19% by weight,
It is more preferably used in an amount of 13 to 18% by weight.
If the amount is too small or too large, the water vapor permeability of the sheet or film of the present invention becomes high. Further, as the number of polar groups increases, the hygroscopicity of the hydrogenated product increases, so it is preferable that the amount of the substituted polar group used is small.

In the present invention, other cycloolefins or the like which can be polymerized may be used in combination within a range that does not substantially prevent the effects of the present invention. Examples of such cycloolefins include those having one or more reactive double bonds in one molecule such as cyclopentene, cyclooctene, 2-norbornene, and 5-methyl-2-norbornene. Such cycloolefins are used so that the repeating structural unit derived from them is 10% by weight or less, preferably 3% by weight or less, more preferably 1% by weight or less in the ring-opening copolymer. If the amount of these used is too large, the water vapor transmission rate becomes high.

The ring-opening polymerization of these monomers may be carried out by a known method. Generally, TiCl ⁴ , WC as a polymerization catalyst is used.
Polymerization is carried out by combining a transition metal compound such as l ₅ , MoCl ₅ , VCl ₅ , NiCl ₂ and PdCl _{2 with} an alkyl compound of a typical metal such as Al, Li, Na and Mg.
The polymerization reaction is carried out in an inert solvent such as cyclohexane, methylcyclohexane or toluene at -20 to 100 ° C.
Done in. However, depending on the type of monomer and the type of catalyst, it may gel because of too high reactivity,
In that case, it is necessary to change the catalyst or lower the temperature to suppress the reaction.

In the present invention, the ring-opening copolymer is hydrogenated. In the hydrogenation reaction, the hydrogenation rate of unsaturated bonds in the main chain of the ring-opening copolymer is 98% or more, preferably 99% or more,
More preferably, it is performed so as to be 99.5% or more. If the hydrogenation rate of the main chain is too low, light deterioration resistance, heat deterioration resistance,
The weather resistance is insufficient. In the present invention, the hydrogenated product is formed into a sheet or film, but the sheet or film is easily affected by transparency due to deterioration, moisture permeability, etc.
It is necessary to increase the hydrogenation rate. The method of hydrogenation is not particularly limited, and a heterogeneous catalyst in which a catalyst metal such as Ni or Pd is supported on a carrier, nickel acetylcetonate,
A known method using a homogeneous catalyst in which a transition metal compound such as cobalt acetylacetonate and a reducing metal compound such as alkylaluminum or alkyllithium are combined is exemplified. Hydrogenation is usually 0-250
℃, when using a homogeneous catalyst, preferably 20 to 10
When using a heterogeneous catalyst at 0 ° C., preferably 200
To 240 ° C., particularly preferably 210 to 230 ° C. If the temperature is too low, the reaction rate will be slow, and if it is too high, the decomposition of the polymer or hydrogenated product or gelation will occur easily, and the energy cost will increase.

In the conventionally known polymerization method, the transition metal derived from the polymerization catalyst remains in the polymer. When the sheet or film of the present invention is used for press-through packaging, food packaging, etc., such as when it is used in contact with foods or chemicals, it is preferable that the transition metal remaining in the hydrogenated product does not elute. It is preferable that substantially no transition metal remains in the hydrogenated product. For that purpose, the pore volume is 0.5 cm ³ / g or more, preferably 0.6 cm ³ / g or more, and preferably the specific surface area is 250 m ² / g.
Hydrogenation of a polymer using a heterogeneous hydrogenation catalyst in which a hydrogenation catalyst metal such as nickel is supported on an adsorbent such as alumina having a weight of g or more, and a hydrogenation solution or hydrogenation using such an adsorbent The transition metal atom in the hydrogenated product can be reduced to 1 ppm or less by treating the reaction solution or repeatedly washing the hydrogenated solution or the hydrogenated reaction solution with acid water in a pure manner. In particular, the method using an adsorbent is efficient and preferable.

Further, a halide may be used as a polymerization catalyst or a hydrogenation catalyst, and halogen atoms are likely to remain. Similar to the transition metal, when the halogen atom is used for the purpose of contacting with foods or chemicals, it is preferable that the halogen atom does not remain in the hydrogenated product. The number of halogen atoms in the hydrogenated product can be reduced to 1 ppm or less by the method using the adsorbent as described above.

The recovery of the hydrogenated product from the hydrogenation reaction liquid or the like is carried out by pouring these solutions into a large amount of a poor solvent to precipitate the resin and sufficiently volatilizing the solvent, a catalyst residue,
After the impurities such as unreacted monomers are sufficiently adsorbed by the adsorbent, the adsorbent and gel are removed by filtration, and the solvent is volatilized. In particular, after treating with an adsorbent, the solution is filtered in a controlled and clean environment using a filter having a pore size of 1 μm or less, preferably 0.5 μm or less, such as a membrane filter or a cartridge filter, and then centrifugal thin film continuous evaporation. 100 torr or less, preferably 50 torr or less, 200 to 300 ° C., preferably 25 using a vessel-type dryer, a high-viscosity reactor-type dryer, or the like.
The method of volatilizing the solvent in an environment of 0 to 270 ° C. is preferable because it is easy to prevent the inclusion of fine foreign matter, and this method is particularly preferable when the sheet or film of the present invention is used for packaging foods, pharmaceuticals and the like. When the solvent is volatilized and removed, it is preferable that the volatile component in the hydrogenated product be 0.2% by weight or less.

The number average molecular weight of the hydrogenated product used in the present invention is 1 in terms of polystyrene measured by gel permeation chromatography using toluene as a solvent.
20,000 to 200,000, preferably 15,000
100 to 100,000, more preferably 20,000 to 5
It is 10,000. From the viewpoint of water vapor permeability and the like, the glass transition temperature (hereinafter referred to as Tg) is 50 to 160 ° C, preferably 60 to 140 ° C, more preferably 70 to 110 ° C. If the Tg is too low, the water vapor transmission rate becomes high, and if the Tg is too high, the molding becomes difficult and the vacuum molding becomes difficult, and the sheet or film is easily curled or wavy during extrusion molding.

In the hydrogenated product used in the present invention, if desired, a phenol-based or phosphorus-based antioxidant; a phenol-based heat deterioration inhibitor; a benzophenone-based ultraviolet absorber; an amine-based antistatic agent Various additives such as agents; lubricants such as esters of aliphatic alcohols, partial esters of high alcohols and partial ethers; and the like may be added. However, as these additives, 20
It is preferable to select and use one having a vapor pressure at 10 ° C of 10 ^-6 Pa or less, and it is also preferable to use the volatile component in the hydrogenated product at 0.2% or less. When the amount of volatile components is large, problems such as foaming, voids and fish eyes are likely to occur in melt molding such as extrusion molding.

When used for packaging, the hydrogenated product used in the present invention is preferably highly transparent so that the object to be packaged can be seen from the outside, and is a sheet or film having a thickness of 500 μm and a wavelength of 430 to 800 nm. Has a light transmittance of 80% or more, preferably 85% or more, more preferably 90% or more. However, when the object to be packaged is deteriorated by visible light or the like, it is preferable to add a dye, dye, pigment or the like as a light-shielding agent to protect the object to be protected from light.

(Molding) The hydrogenated product of the present invention is used as a molding material having a low water vapor transmission rate and is a general molding method for thermoplastic resins such as injection molding, extrusion molding, hot press molding, solvent casting, It can be formed into a sheet or film by inflation or the like. A sheet or film having a thickness of 500 μm and a water vapor transmission rate of up to about 0.15 g / m ² · 24 hr can be obtained by simply molding, but a sheet or film having a lower water vapor transmission rate can be obtained by stretching. Can be obtained. The uniaxial stretching and the biaxial stretching have no great difference in moisture permeability, whereas the biaxial stretching has a complicated working process, and the uniaxial stretching is preferable. The stretching is generally performed at Tg to Tg + 100 ° C., preferably Tg + 10 ° C. to Tg + 80 ° C., and the stretching ratio is 1.05 to 5.00, preferably 1.10 to 3.00.
It is more preferably 1.15 to 2.00. If the temperature during stretching is too low, the sheet or film is likely to break during stretching, resulting in poor processability. If the sheet or film does not break, the strength of the sheet or film after stretching may decrease. If the stretching temperature is too high, workability will be reduced. If the stretching ratio is too low, the decrease in water vapor permeability is small, and if it is too large, the strength of the sheet or film after stretching is decreased, and pinholes are likely to occur. In the case of obtaining a sheet or film by continuously forming a molten hydrogenated product into a sheet or film by extrusion molding or the like and then cooling and solidifying the sheet or film, in the manufacturing process, the sheet or the film solidified against the delivery speed of the molten resin or By increasing the winding speed of the film, the film can be easily and continuously stretched, and a complicated process is not required. The stretching ratio in this case is a value obtained by dividing the thickness at the time when the molten resin is extruded, for example, the size of the die cap when a T die is used, by the thickness of the wound sheet or film. Shown.

(Sheet or Film) The sheet or film of the present invention has a thickness of 10 μm to 10 mm, preferably 50 μm to 5 mm, more preferably 100 μm to 1.
mm, and is excellent in transparency, gas barrier property, impact resistance, low moisture permeability, and the like. For example, transparency is 5
85% or more, preferably 88% or more, more preferably 90% or more, and internal haze of 1.0% or less, preferably 0.8% or less, more preferably 0.5% or less in a 00 μm sheet or film, and , Moisture permeability is 500μ
m sheet or film 0.13g / m ² · 24h
r or less, preferably 0.12 g / m ² · 24 hr or less,
More preferably, it is possible to obtain one having 0.11 g / m ² · 24 hr or less. The water vapor transmission rate and the transparency are different depending on the thickness, and the thinner the transparency is, the better the water vapor transmission rate is. Also, the impact resistance is 50
The 50% breaking energy of a 0 μm sheet or film is 3.0 J or more at 23 ° C., preferably 3.3 J or more, and 1.3 J or more at −20 ° C., preferably 1.5 J or more.

(Use) The sheet or film of the present invention is used for liquid crystal displays such as a polarizing film, a retardation film, a liquid crystal substrate, a light diffusing sheet, and a prism sheet, and a sheet for which low moisture permeability and high optical properties are required, Optical sheets such as transparent glass sheets instead of glass sheets that require strength such as automobile window materials, roof materials, aircraft window materials, vending machine window materials, show window materials, showcase materials;
Packaging sheets used as raw materials for resist solution bags, medical solution bags, infusion bags, etc., and for foods, electronic parts, etc .; electrical insulating sheets, electrical sheets such as film capacitors; exterior materials, roofing materials, etc. It is used as a building sheet;

(Aspect) As an aspect of the sheet or film of the present invention, (1) dicyclopentadiene monomer-derived ring-opening repeating structural unit 80 to 90% by weight and tetracyclododecene-type monomer-derived ring-opening Repeating structural unit 2
It is composed of 0 to 10% by weight, and is composed of a hydrogenated product obtained by hydrogenating the unsaturated bond of the main chain of the copolymer containing substantially no gel at a hydrogenation rate of 98% or more, and a draw ratio of 1.05 to 5.
Sheet or film stretched to 00, (2) the sheet or film according to (1), wherein the hydrogenated product has a hydrogenation rate of unsaturated bonds in the main chain of 99% or more, and (3) the hydrogenated product is in the main chain. The sheet or film according to (2), wherein the hydrogenation rate of the unsaturated bond is 99.5% or more, and (4) the hydrogenated product is a dicyclopentadiene monomer ring-opening polymer-derived ring-opening repeating structural unit 81 to The sheet or film according to (1) to (3), which comprises 88% by weight and 19 to 12% by weight of a repeating structural unit derived from a tetracyclododecene-based monomer ring-opening polymer, and (5) the hydrogenated product is dicyclopentadiene. -Based monomer-derived ring-opening repeating structural units 83 to 87
(4) A sheet or film according to (4), which comprises 17% to 13% by weight of a ring-opening repeating structural unit derived from a tetracyclododecene monomer, and (6) a hydrogenated product is a ring opening derived from a dicyclopentadiene monomer. The sheet or film according to (1) to (5), which has 10% by weight or less of repeating structural units other than the repeating structural unit and the tetracyclododecene-based monomer-derived ring-opening repeating structural unit, (7)
The sheet according to (6), wherein the hydrogenated product has 3 wt% or less of repeating structural units other than the dicyclopentadiene-based monomer-derived ring-opening repeating structural unit and the tetracyclododecene-based monomer-derived ring-opening repeating structural unit. the film,
(8) The hydrogenated product has 1% by weight or less of a repeating structural unit other than the ring-opening repeating structural unit derived from a dicyclopentadiene-based monomer and the tetracyclododecene-based monomer. Sheet or film of (9) Hydrogen permeation gel permeation
The sheet or film according to (1) to (8), which has a number average molecular weight of 10,000 to 200,000 in terms of polystyrene measured by a chromatography method, (10)
The sheet or film according to (9), wherein the hydrogenated product has a number average molecular weight of 15,000 to 100,000 in terms of polystyrene measured by gel permeation chromatography, (11) the hydrogenated product is gel permeation. Number average molecular weight in terms of polystyrene measured by cation chromatography is 20,000 to 50,000
The sheet or film according to (10), which is 0, (1
2) The sheet or film according to (1) to (11), wherein the hydrogenated substance has a glass transition temperature of 50 to 160 ° C., and (13) the hydrogenated substance has a glass transition temperature of 60 to 1.
(12) The sheet or film according to (12), which has a glass transition temperature of 70 to 1 at 40 ° C.
The sheet or film according to (13), which is at 10 ° C., (15) The sheet or film according to (1) to (14), wherein the volatile component is 0.2% by weight or less, (1)
6) Stretching ratio is 1.10 to 3.00 (1) to
(15) The sheet or film, (17) The stretching ratio is 1.15 to 2.00, The sheet or film (16), (18) The thickness is 10 μm to 10 mm.
A sheet or film according to (1) to (17),
(19) The sheet or film according to (18), which has a thickness of 50 μm to 5 mm, (20) the thickness is 100 μm.
The sheet or film according to (1) having a length of ˜1 mm is exemplified.

[0022]

EXAMPLES The present invention will be specifically described below with reference to Reference Examples, Examples and Comparative Examples. The molecular weight is a polystyrene equivalent value measured by gel permeation chromatography using toluene, and the volatile component is thermogravimetric analysis,
The water vapor transmission rate is the method B of JIS Z 0208, the gas permeability is the method of JIS K 7126, and the light transmittance is 7
At 00 nm, the internal haze value was measured by the method of JIS K 7105, and the 50% breaking energy was measured by the method of JIS K 7211.

Reference Example 1 In a 200 l glass reactor under a nitrogen atmosphere, 85 parts by weight of dicyclopentadiene, 15 parts by weight of 6-methyltetracyclododecene, 250 parts by weight of cyclohexane, 1-
Hexene 0.01 parts by weight, isobutyl ether 0.01
60 parts by weight, isobutyl alcohol 0.01 parts by weight, and triisobutyl alcohol 0.01 parts by weight,
While maintaining the temperature at 0 ° C., a total amount of 0.005 parts by weight of a 1% solution of tungsten hexachloride in cyclohexane was continuously added over 1 hour to carry out a polymerization reaction. A part of the polymerization reaction liquid was recovered, and the polymer in the polymerization reaction liquid was analyzed using ¹ H-NMR and ¹³ C-NMR. As a result, about 85% by weight of the ring-opening repeating structural unit derived from dicyclopentadiene, 6- It consisted of about 15% by weight of methyltetracyclododecene.

This polymerization reaction solution was transferred to a 500 l autoclave, and 0.6 part by weight of a heterogeneous catalyst in which palladium was supported on carbon as a carrier (loading amount 5% by weight) was added, and hydrogen pressure was 50 kgf / cm ² . The reaction was carried out at a temperature of 220 ° C. for 5 hours.

This hydrogenation reaction solution was mixed with diatomaceous earth (Radiolite # 800) and activated alumina (pore volume 0.72).
cm ³ / g, specific surface area of 255 m ² / g) was used as a filter aid to remove the catalyst, and the pore size was 0.4 μm.
The solution filtered with the membrane filter of No. 1 was dried in a clean environment (class 10000) using a centrifugal thin film continuous evaporator type dryer at 280 ° C. and 30 torr for 5 hours to obtain a resin, which was then used in a twin-screw extruder. Worked up and pelletized to give 25.3 parts by weight of hydrogenated product.

The number average molecular weight of this hydrogenated product is 27,0.
00, weight average molecular weight 66,000, molecular weight distribution is 2.
44, glass transition temperature 98 ° C., hydrogenation rate 99.7% or more, transition metal atoms were below the detection limit, chlorine atoms were also below the detection limit (100 ppb), and volatile components were below 0.1%.

Example 1 Using the extrusion molding machine with a screw diameter of 65 mm, the hydrogenated product obtained in Reference Example 1 was extruded at a resin temperature of 210 ° C. from a T-die having a width of 400 mm and a die gap of 600 μm at an extrusion speed of 35 kg / hour. , Draw ratio 1.20 times,
The thickness was adjusted to 500 μm by a 90 ° C. roll, and the winding speed was set to 2.8 m / min.

This sheet was free from defects such as voids and fish eyes, and defects in outer shape such as curling, twisting and waviness. The light transmittance of this sheet is 90.5.
%, Internal haze 0.4%, moisture vapor transmission rate 0.10 g / m ²
・ 24 hr, gas permeability is O ₂ 10 cm ³ / m ²・ 24
hr, CO ₂ was 35 cm ³ / m ² · 24 hr, and 50% breaking energy was 3.5 J at 23 ° C and 1.6 J at -20 ° C.

Comparative Example 1 Instead of the hydrogenated product obtained in Reference Example 1, a hydrogenated product of a dicyclopentadiene ring-opening polymer (having a number average molecular weight of 26,000) was prepared.
0, weight average molecular weight 58,000, molecular weight distribution 2.2
3, glass transition temperature 93 ° C., hydrogenation rate 99.5% or more, transition metal atoms are below the detection limit, chlorine atoms are below the detection limit, and volatile components are 0.23%). A sheet having a thickness of 500 μm was prepared.

No curling, twisting, or waviness was observed in this sheet, but voids or fish eyes having a size of 0.5 mm or less were observed at a rate of about 1 per 1 m. The light transmittance of this sheet is 88.4%, the internal haze is 1.7%, and the water vapor transmission rate is 0.16 g / m ² · 24 h.
r, gas permeability of O ₂ is 15 cm ³ / m ² · 24 hr, C
O ₂ was 46 cm ³ / m ² · 24 hr, and 50% breaking energy was 2.8 J at 23 ° C and 10.6 J at -20 ° C.

Comparative Example 2 A sheet having a thickness of 500 μm was prepared in the same manner as in Example 1 except that the extrusion speed was adjusted so that the draw ratio was 1.00 and the T-die had a die gap of 500 μm. did.

This sheet was free from defects such as voids and fish eyes, and defects in outer shape such as curling, twisting and waviness. The light transmittance of this sheet is 89.1.
%, Internal haze 0.4%, moisture vapor transmission rate 0.14 g / m ²
・ 24 hr, gas permeability is O ₂ 14 cm ³ / m ²・ 24
hr, CO ₂ was 45 cm ³ / m ² · 24 hr, 50% breaking energy was 3.4 J at 23 ° C., and 1.4 J at −20 ° C.

[0033]

The sheet of the present invention has excellent moisture permeability. Further, since it is also excellent in gas barrier property, transparency, impact resistance, etc., it has preferable properties as a sheet for packaging foods and chemicals.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-5-287173 (JP, A) JP-A-1-168724 (JP, A) JP-A-1-168725 (JP, A) JP-A-1- 172422 (JP, A) JP-A 1-203425 (JP, A) JP-A 5-132545 (JP, A) JP-A 6-182799 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 61/00-61/12

Claims (4)

(57) [Claims] 1. A dicyclopentadiene-based monomer-derived ring-opening repeating structural unit 80 to 90% by weight and a tetracyclododecene-based monomer-derived ring-opening repeating structural unit 20 to 10
An unsaturated bond in the main chain of the copolymer, which is composed of 1% by weight and does not substantially contain gel, is hydrogenated to a hydrogenation rate of 98% or more.
A sheet or film obtained by stretching a hydrogenated sheet or film having a volatile content of 0.2% by weight or less at a stretching ratio of 1.05 to 5.00. 2. The film or sheet according to claim 1, which has an internal haze of 0.8% or less. 3. The transition metal atomic weight in the hydrogenated product is 1
The film or sheet according to claim 1 or 2, which has a ppm or less. 4. The halogen atom content in the hydrogenated product 1
The film or sheet according to any one of claims 1 to 3, which has a ppm or less.