JP2015059145A - Cycloolefin sheet resin and package - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel cycloolefin resin sheet having high transparency and moistureproofness, a package manufactured by molding the sheet and suitable for medical use such as PTP packaging and an infusion bag or food packaging use such as blister packaging.SOLUTION: There is provided a cycloolefin resin sheet containing the following (A) and (B) with percentage of (A) in the sheet of 75 mass% or more and less than 95 mass%. (A) a crystalline cycloolefin resin having a crystal melting temperature measured with a heating rate of 10°C/min. in a differential scanning calorimetry of 120°C to 140°C and a crystal fusion heat of 20 J/g to 50 J/g. (B) a petroleum resin having the softening point of 120°C to 145°C.

Description

  The present invention relates to a cycloolefin resin sheet excellent in moisture resistance, transparency and impact resistance, and a package formed by molding the sheet.

  So-called transparent moisture-proof sheets are widely used in press-through packaging (hereinafter abbreviated as “PTP”) packaging for containing contents such as solid agents such as capsules and tablets in the pharmaceutical and medical fields. In the field of food packaging, it is also routinely used as a blister package.

With PTP packaging, a transparent resin sheet is formed by pressure forming, vacuum forming, thermoforming, etc. to produce a bottom material having a pocket portion for storing contents, and after storing the contents in the pocket portion, for example, It is a packaging in an integrated form, which is bonded to a lid material such as an aluminum foil to close the pocket portion. Since the bottom material is made of a transparent sheet, contents such as a solid agent accommodated in the pocket portion can be directly confirmed. Moreover, the said cover part can be broken by pressing this pocket part through the contents, and the contents can be easily taken out.
Similarly, a blister package is a packaging in which a transparent resin sheet is molded to produce a bottom material having a pocket portion, and a cover material such as paper or a resin film is bonded to close the pocket portion. And the contents can be confirmed directly.

  As the material of the resin sheet used for such PTP packaging and blister package, polyvinyl chloride (hereinafter abbreviated as “PVC”) resin and polyolefin resin such as polyethylene and polypropylene are good moldability at room temperature. Has been used because of its rigidity, impact resistance, moderate moisture resistance, and transparency.

  However, PVC resin has been regarded as a problem from the viewpoint of environment because there is a possibility that a gas containing chlorine is generated when incinerated after use. In addition, the polyolefin-based resin may have insufficient transparency and moisture resistance in packaging materials in the medical field and food field, and a molding material having high transparency and high moisture resistance has been demanded.

  In contrast, cycloolefin resins (hereinafter abbreviated as “COP”) and cycloolefin copolymers (hereinafter abbreviated as “COC”), which are materials excellent in moisture resistance and transparency, are attracting attention. It has been used for PTP, infusion bags, packaging materials, etc. in the medical field.

  For example, Patent Document 1 discloses a film obtained by hydrogenating a norbornene-based ring-opening polymer obtained by ring-opening polymerization of a norbornene-based monomer in the presence of an α-olefin, and is moisture-proof and transparent. It has an excellent balance of heat resistance and is said to be used for applications such as packaging materials and electronic device sealing materials. However, such a film is not sufficient for a field requiring further high moisture resistance while maintaining high transparency.

  Patent Document 2 discloses a material excellent in transparency, moisture resistance, moldability, and the like by blending amorphous polyolefin and styrene-based elastomer and reducing the dispersed particle diameter. However, because of blending in an incompatible system, it is considered that appearance defects such as bending whitening may occur when an impact is applied to a molded product during transportation.

  In Patent Document 3, as a bottom material for PTP packaging, a film or sheet made of a cyclic polyolefin resin alone or a blend composition of a cyclic polyolefin resin and a polyolefin resin, or a film or sheet of a cyclic polyolefin resin is used. PTP packaging using a laminate of a film and a sheet of polyolefin resin or sheet is disclosed. Such a PTP package has moisture resistance but does not meet the requirements for higher levels of moisture resistance, and when a cyclic polyolefin resin and a polyolefin resin are blended, The required high transparency could not be maintained.

  Thus, with rapid changes in technology and needs, in the medical and food packaging fields, the moisture resistance of conventional films may be insufficient, and a highly moisture-proof and highly transparent material is required. Therefore, research and development of a crystalline COP imparted with crystallinity by controlling the primary structure of the amorphous COP has been conducted. For example, in Patent Document 4, it is obtained by hydrogenating 80% or more of the main chain carbon-carbon double bond of a ring-opening polymer obtained by ring-opening polymerization of 2-norbornene, and the crystal melting temperature is 110 to 110%. A norbornene-based ring-opening polymer hydride at 145 ° C. is disclosed.

  Patent Document 5 discloses ring-opening polymerization and hydrogenation of a polymerizable monomer comprising 90 to 100% by mass of 2-norbornene and 10 to 0% by mass of a substituent-containing norbornene monomer. A film containing 10 to 100 parts by mass of an amorphous norbornene-based ring-opening polymer and 0.01 to 5 parts by mass of a sorbitol-based crystal nucleating agent with respect to 100 parts by mass of the crystalline norbornene-based ring-opening polymer obtained Is disclosed.

JP 2012-57122 A JP-A-7-276590 JP-A-8-1928713 WO2008 / 026733 JP 2011-6498 A

  Crystalline COPs as disclosed in Patent Document 4 are superior in oxygen barrier properties, water vapor barrier properties, heat resistance, oil resistance, and the like as compared with amorphous COPs and COCs. This material is expected to be applied in a wide range of fields. However, since it is a crystalline resin, it tends to cause a decrease in transparency due to crystallization depending on molding conditions, and there may be a problem in the visibility of the contents, especially when used as packaging for pharmaceuticals, foods, etc. There is.

  On the other hand, when a crystalline COP, an amorphous COP, and a crystal nucleating agent are blended as in the film disclosed in Patent Document 5, the transparency reduction is improved to some extent, but the thickness is still 200 μm. The haze value was 8 to 40%, and there was a problem in practical use. Further, although the moisture-proof property is extremely high, when the crystallinity is lowered or the amorphous COP is increased, the moisture-proof property tends to be lowered, and it is difficult to achieve both high transparency and high moisture-proof property.

  Accordingly, an object of the present invention is to provide a new cycloolefin resin sheet excellent in the balance between high transparency and high moisture resistance, and formed from the sheet, for medical use such as PTP packaging or infusion bag, or blister package, etc. Another object of the present invention is to provide a package suitable for food packaging.

As a result of intensive investigations in view of the problems of the prior art as described above, the present inventors have found that a cycloolefin resin sheet containing a specific crystalline cycloolefin resin and a specific petroleum resin has high moisture resistance. The present inventors have found that the balance of high transparency is extremely excellent and have completed the present invention.
That is, the present invention is as follows.

[1] A cycloolefin resin sheet comprising the following (A) and (B), wherein the proportion of (A) in the sheet is 75% by mass or more and less than 95% by mass Cycloolefin resin sheet.
(A) A crystal having a crystal melting temperature of 120 ° C. or more and 140 ° C. or less measured at a heating rate of 10 ° C./min in differential scanning calorimetry and a crystal melting heat of 20 J / g or more and 50 J / g or less. Petroleum cycloolefin resin (B) Petroleum resin having a softening point of 120 ° C. or higher and 145 ° C. or lower [2] Furthermore, (C) a crystal nucleating agent is included, and the proportion of (C) in the sheet is 0.00. It is 01 mass% or more and 3 mass% or less, The cycloolefin type resin sheet as described in [1] characterized by the above-mentioned.
[3] The cycloolefin resin sheet according to [2], wherein the (C) crystal nucleating agent is a sorbitol compound.
[4] The total haze value and the internal haze value at a thickness of 0.30 mm as measured in accordance with JIS K7105 are both 10.0% or less, and any one of [1] to [3] The cycloolefin resin sheet described.
[5] The water vapor permeability measured at a temperature of 40 ° C. and a relative humidity of 90% based on the JIS K7129B method at a thickness of 0.30 mm is 0.30 g / (m 2 · 24 hours) or less. The cycloolefin resin sheet according to any one of [1] to [4].
[6] The storage elastic modulus (E ′) at a temperature of 25 ° C. measured at a vibration frequency of 10 Hz based on JIS K7244-4 is 1000 MPa or more and 2500 MPa or less and a temperature of 110 ° C. ) Is 5 MPa or more and 100 MPa or less, The cycloolefin resin sheet according to any one of [1] to [5].
[7] A package formed by molding the cycloolefin-based resin sheet according to any one of [1] to [6].

  The cycloolefin-based resin sheet of the present invention is extremely excellent in the balance between high moisture resistance and high transparency. For example, packaging materials such as pharmaceuticals and foods, especially PTPs (press-through packs) for pharmaceuticals, infusion bags, and foods. It can be suitably used as a material such as a blister package for packaging.

  Hereinafter, a cycloolefin-based resin sheet (hereinafter also referred to as “this sheet”) as an example of an embodiment of the present invention will be described.

<Material constituting this sheet>
[Crystalline cycloolefin resin (A)]
The crystalline cycloolefin resin (A) used in the present invention has a crystal melting temperature of 120 ° C. or higher and 140 ° C. or lower as measured at a heating rate of 10 ° C./min in differential scanning calorimetry, and has a crystal melting heat of heat. It is important that it is 20 J / g or more and 50 J / g or less.

The crystal melting temperature of the crystalline cycloolefin resin (A) is more preferably 125 ° C. or more and 140 ° C. or less, and further preferably 130 ° C. or more and 140 ° C. or less.
A crystal melting temperature of 120 ° C. or higher is preferable because the sheet has heat resistance. In addition, it is preferable that the crystal melting temperature is 140 ° C. or lower because the sheet is excellent in formability.
The crystal melting temperature can be measured at a heating rate of 10 ° C./min according to JIS K7121 using a differential scanning calorimeter.

Further, the heat of crystal fusion of the crystalline cycloolefin resin (A) is more preferably in the range of 25 J / g or more and 45 J / g or less, and in the range of 30 J / g or more and 40 J / g or less. Further preferred.
It is preferable that the heat of crystal fusion is 20 J / g or more because this sheet has high moisture resistance. Further, it is preferable that the heat of crystal fusion is 50 J / g or less because this sheet can maintain high transparency.
The heat of crystal fusion can be measured at a heating rate of 10 ° C./min according to JIS K7122 using a differential scanning calorimeter.

The crystalline cycloolefin-based resin (A) is not particularly limited as long as it has the crystal melting temperature and the heat of crystal melting described above. For example, a norbornene-based ring-opening polymer as described in WO2008 / 026733 A hydride or the like can be used.
More specifically, hydrogenated norbornene-based ring-opening polymer obtained by hydrogenating 80% or more of the main chain carbon-carbon double bond of the ring-opening polymer obtained by ring-opening polymerization of 2-norbornene. Or norbornene obtained by hydrogenating 80% or more of carbon-carbon double bonds of a ring-opening copolymer obtained by ring-opening copolymerization of 2-norbornene and a substituent-containing norbornene monomer. The ring-opening polymer hydride has a proportion of 90 to 99% by weight of repeating units derived from 2-norbornene based on all repeating units, and a proportion of repeating units derived from substituent-containing norbornene monomers based on all repeating units. What is 1-10 weight% etc. can be used suitably.

  Examples of the commercially available crystalline cycloolefin resin (A) include “ZEONEX” manufactured by Nippon Zeon Co., Ltd.

The proportion of the crystalline cycloolefin resin (A) in the sheet is important to be 75% by mass or more and less than 95% by mass, and more preferably 80% by mass or more and less than 95% by mass. More preferably, it is 85 mass% or more and less than 95 mass%.
If the ratio of (A) in this sheet is 75% by mass or more, this sheet is preferable because it has high moisture resistance. Moreover, if it is less than 95 mass%, since this sheet can maintain high transparency, it is preferable.

[Petroleum resin (B)]
It is important that the petroleum resin (B) used in the present invention has a softening point of 120 ° C. or higher and 145 ° C. or lower, and more preferably 125 ° C. or higher and 140 ° C. or lower.
When the softening point is 120 ° C. or higher, blocking of pellets during molding, bleeding out to the film surface during secondary processing, transportation, and use will not occur. If the softening point is 145 ° C. or lower, the degree of freedom of the petroleum resin (B) molecule is high in the crystallization process of the crystalline cycloolefin resin (A), and the crystalline cycloolefin resin (A) Is not inhibited, fine crystals are formed, and a cycloolefin resin sheet excellent in transparency is obtained.
In addition, the softening point of petroleum resin (B) is measured by the ring and ball method.

  The petroleum resin (B) is not particularly limited as long as it has the above-mentioned softening temperature, but usually C4 to C10 aliphatic olefins and diolefins obtained from by-products such as naphtha pyrolysis. C8 or more aromatic compounds having an olefinically unsaturated bond, and aliphatic, aromatic and copolymer obtained by singly or copolymerizing one or more of the compounds contained therein Among them, aliphatic petroleum resins whose main raw material is C5 fraction, aromatic petroleum resins whose main raw material is C9 fraction, their copolymer petroleum resins, alicyclic petroleum oil, among others A resin can be preferably mentioned.

  In particular, when mixed with the crystalline cycloolefin polymer (A), it exhibits relatively good compatibility. From the viewpoint of color tone, thermal stability, compatibility, moisture resistance, etc., hydrogenated derivatives of petroleum resins (water (Petroleated resin), particularly those having a hydrogenation rate of 95% or more and substantially free of a polar group such as a hydroxyl group, a carboxyl group, or a halogen, or an unsaturated bond such as a double bond are more preferred.

  Hydrogenated petroleum resin is obtained by hydrogenating petroleum resin by a conventional method. Examples thereof include hydrogenated aliphatic petroleum resins, hydrogenated aromatic petroleum resins, hydrogenated copolymer petroleum resins, hydrogenated alicyclic petroleum resins, and hydrogenated terpene resins. Among hydrogenated petroleum resins, hydrogenated alicyclic petroleum resins obtained by copolymerizing and hydrogenating a cyclopentadiene compound and an aromatic vinyl compound are particularly preferable.

  Specific examples of commercially available petroleum resins include the “Arcon” series manufactured by Arakawa Chemical Industry Co., Ltd., the “Clearon” series manufactured by Yashara Chemical Co., Ltd., the “Imabe” series manufactured by Idemitsu Petrochemical Co., Ltd., and Tonex Corporation. "Escollets" series made by, etc. are mentioned.

The proportion of the petroleum resin (B) in the sheet can be adjusted as appropriate based on the proportion of the crystalline cycloolefin-based resin (A), but is 5% by mass or more and 25% by mass or less. Preferably, it is 5 mass% or more and 20 mass% or less, More preferably, it is 10 mass% or more and 20 mass% or less.
If the ratio of (B) in this sheet is 5% by mass or more, this sheet is preferable because it has high transparency. Moreover, if it is 25 mass% or less, since the fall of the mechanical physical property and blocking of this sheet | seat can be suppressed, it is preferable.

[Crystal nucleating agent (C)]
This sheet may contain a crystal nucleating agent (C) in addition to the above (A) and (B). By including the crystal nucleating agent (C), the above (A) can form a fine crystal structure in the present sheet, and the transparency and moisture resistance of the present sheet are improved.

  The crystal nucleating agent (C) that can be used in the present invention is not particularly limited as long as it exhibits the above-described effects without inhibiting the transparency and moisture resistance of the sheet, and various crystal nucleating agents can be used. Among them, a sorbitol compound is preferable because it easily disperses in the crystalline cycloolefin resin (A) and also facilitates control of crystallization. 4-bis-O- (m-methylbenzylidene) -D-sorbitol is particularly preferred.

  Specific examples of commercially available sorbitol compounds that can be used as the crystal nucleating agent (C) include “Gelall MD” and “Gelall MD LM-30G” of “Gelall MD” series manufactured by Shin Nippon Chemical Co., Ltd. Can be mentioned.

The ratio of the crystal nucleating agent (C) in the sheet can be adjusted as appropriate based on the ratio of the crystalline cycloolefin resin (A) and the petroleum resin (B), but 0.01% by mass or more. It is preferably 3% by mass or less, more preferably 0.1% by mass or more and 2% by mass or less, and further preferably 0.5% by mass or more and 1% by mass or less.
A ratio of (C) in the sheet of 0.01% by mass or more is preferable because the transparency and moisture resistance of the sheet can be improved. Moreover, if it is 3 mass% or less, since there is little possibility of causing the transparency fall of this sheet | seat, it is preferable.

[Others]
Furthermore, the present sheet has a polyolefin resin other than (A), a polystyrene resin, a polyester resin, a resin such as a polyolefin-based or polystyrene-based thermoplastic elastomer, and a heat as long as the effects of the present invention are not impaired. It can contain additives such as stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, antibacterial and antifungal agents, antistatic agents, lubricants, pigments, dyes and the like.

<Method for producing this sheet>
The manufacturing method of this sheet | seat is not specifically limited. For example, the crystalline cycloolefin resin (A), the petroleum resin (B), and if necessary, the crystal nucleating agent (C) and other resins / additives are uniaxially or twin screw extruders, etc. A non-stretched sheet can be produced by melting and kneading with a die, extruding into a sheet form with a T die (die), quenching and solidifying with a casting roll.

  The molding temperature is appropriately adjusted because the flow characteristics change depending on the type and mixing ratio of the resin, and the presence and type of the additive. For example, the set temperature of the extruder and the T die is usually 180 to 260 ° C., preferably 200 to 200 ° C. It is 240 degreeC, and the temperature of the casting roll for cooling the extruded sheet-like resin is 20-80 degreeC normally, Preferably it is 30-60 degreeC. Here, the non-stretched sheet means a sheet that is not actively stretched for the purpose of increasing the strength of the sheet. For example, a non-stretched sheet includes a film that has been stretched to less than 2 times in the process of winding while being cooled with a roll during extrusion molding.

  Furthermore, the roll is stretched in a uniaxial direction or a biaxial direction by using a roll method, a tenter method, a tubular method, etc. for the purpose of further improving heat resistance and moisture resistance within a range that does not impair the secondary workability of the sheet. You can also.

<Thickness of this sheet>
The thickness of the sheet is not particularly limited, but is preferably 0.10 mm or more and 1.0 mm or less when considering workability and practicality, for example, 0.20 mm or more and 0.80 mm or less. More preferably. If the thickness of this sheet is 0.10 mm or more, suitable sheet rigidity will be exhibited, and processability and curl resistance will be excellent. On the other hand, if the thickness of this sheet is 1.0 mm or less, excellent secondary processability can be maintained without causing problems in taking out the medicine when used as a packaging material such as PTP.

<Physical properties of this sheet>
When this sheet is used for packaging applications, from the viewpoint of preventing deterioration of the contents due to moisture, the water vapor transmission rate at a thickness of 0.30 mm measured at a temperature of 40 ° C. and a relative humidity of 90% based on the JIS K7129B method is 0.30 g. / (M ² · 24 hours) or less, more preferably 0.25 g / (m ² · 24 hours) or less. If this sheet has a water vapor transmission rate of 0.30 g / (m ² · 24 hours) or less at a thickness of 0.30 mm, it can be suitably used as a packaging material, particularly as a packaging material for chemicals requiring moisture resistance. .

  Furthermore, from the viewpoints of design properties, contents visibility, and the like, it is preferable that the total haze value and the internal haze value at a thickness of 0.30 mm measured based on JIS K7105 are both 10.0% or less, and 8.0. % Or less is more preferable, and 6.0% or less is particularly preferable. If the total haze value and the internal haze value at a thickness of 0.30 mm of this sheet are within the ranges, a cycloolefin resin sheet excellent in the visibility of the contents and a packaging material formed by molding the sheet can be obtained.

  This sheet has a storage elastic modulus (E ′) at a temperature of 25 ° C. measured under conditions of a vibration frequency of 10 Hz in accordance with JIS K7244-4 from the viewpoint of secondary workability such as vacuum forming and pressure forming, etc. ) Is 1000 MPa to 2500 MPa, and the storage elastic modulus (E ′) at a temperature of 110 ° C. is preferably 5 MPa to 100 MPa.

The storage elastic modulus (E ′) at a temperature of 25 ° C. is more preferably 1200 MPa or more and 2300 MPa or less, and particularly preferably 1400 MPa or more and 2000 MPa or less.
If the storage elastic modulus (E ′) at a temperature of 25 ° C. is within such a range, a cycloolefin-based resin sheet excellent in both handleability at normal temperature and secondary processability can be obtained.

The storage elastic modulus (E ′) at a temperature of 110 ° C. is more preferably 10 MPa or more and 90 MPa or less, and further preferably 20 MPa or more and 80 MPa or less.
If the storage elastic modulus (E ′) at a temperature of 110 ° C. is within such a range, a cycloolefin-based resin sheet excellent in secondary workability can be obtained.

<Use of this sheet>
This sheet can be formed into a molded body of various shapes by vacuum forming, pressure forming, pressure forming, press forming, and other thermoforming, for example, a forming body for packaging, particularly PTP packaging, blister package, etc. A packaging material can be suitably manufactured and used.

  For example, when producing a molded sheet for PTP packaging, the cycloolefin-based sheet of the present invention is heated and softened by contacting with a flat plate heating plate of a compressed air / vacuum forming machine, and the sheet is sent to a molding die to be compressed / Obtained by vacuum forming.

  In addition to performing the above thermoforming, aluminum foil, aluminum vapor deposition film, plastic film (for example, biaxially oriented polypropylene film, nylon film, ethylene-vinyl alcohol copolymer film, polyvinylidene chloride film on the sheet surface, back surface or both surfaces Etc.) can also be laminated. In addition, after forming a composite sheet | seat by laminating | stacking aluminum foil, the said various film, etc. on the sheet | seat surface or the back surface or both surfaces, this can also be thermoformed.

  Since this sheet is excellent in transparency and moisture resistance, it is a PTP packaging for packaging solid agents such as capsules and tablets, granular foods, etc. in the packaging field of pharmaceuticals and foods, and a blister package in the packaging field of foods, etc. Etc. can be used suitably.

  Examples are shown below, but the present invention is not limited by these. In addition, the various measured value and evaluation about the raw material and test piece which are displayed in this specification were performed as follows.

<Various evaluation methods>
(1) Crystal melting temperature (Tm)
Using a differential scanning calorimeter ("Diamond DSC" manufactured by Perkin Elmer), according to JIS K7121, about 10 mg of the sample was heated from -40 ° C to 200 ° C at a heating rate of 10 ° C / min. After holding for a minute, the temperature was lowered to −40 ° C. at a cooling rate of 10 ° C./min, and again from the thermogram measured when the temperature was raised to 200 ° C. at a heating rate of 10 ° C./min, the crystal melting temperature (Tm) (° C.) Asked.

(2) Heat of crystal melting (ΔHm)
Using a differential scanning calorimeter ("Diamond DSC" manufactured by Perkin Elmer), according to JIS K7122, about 10 mg of the sample was heated from -40 ° C to 200 ° C at a heating rate of 10 ° C / min. After holding for a minute, the temperature was lowered to −40 ° C. at a cooling rate of 10 ° C./min, and again from the thermogram measured when the temperature was raised to 200 ° C. at a heating rate of 10 ° C./min, the heat of crystal melting (ΔHm) (J / g) was determined.

(3) Transparency (total haze value, internal haze value)
All haze values and internal haze values were measured by applying dioctyl phthalate (DOP) to both surfaces of a 0.30 mm thick sheet (sample) and adjusting the external haze value to zero based on JIS K7105. .
All haze values and internal haze values of 10.0% or less were regarded as acceptable.

(4) Moisture resistance (water vapor transmission rate)
Based on JIS K7129B method, using a water vapor transmission rate measuring device ("PERMATRAN W 3/31" manufactured by MOCON), a water vapor transmission rate was measured for a sample having a thickness of 0.30 mm in an atmosphere of 40 ° C and 90% RH. .
A water vapor transmission rate of 0.30 g / (m ² · 24 hours) or less was accepted.

(5) Storage elastic modulus (E ')
Using a dynamic viscoelasticity measuring device (product name: Viscoelastic Spectrometer DVA-200, manufactured by IT Measurement Co., Ltd.), vibration frequency: 10 Hz, temperature rising rate: 3 ° C./min according to JIS K7244-4 The storage elastic modulus (E ′) was measured from −100 ° C. to 150 ° C. under the condition of strain 0.1%, and the storage elastic modulus (E ′) of the sheet at 25 ° C. and 110 ° C. from the obtained data. I read.
A storage elastic modulus (E ′) at a temperature of 25 ° C. of 1000 MPa to 2500 MPa and a storage elastic modulus (E ′) at a temperature of 110 ° C. of 5 MPa to 100 MPa was regarded as acceptable.

<Materials used>
[Crystalline cycloolefin resin (A)]
(A) -1: crystalline cycloolefin-based resin (manufactured by Nippon Zeon Co., Ltd., ZEONEX 2010), Tm = 134 ° C., ΔHm = 37 J / g)

[Petroleum resin (B)]
(B) -1: Hydrogenated petroleum resin (Arakawa Chemical Industries, Alcon P125, softening point = 125 ° C.)
(B) -2: Hydrogenated petroleum resin (Arakawa Chemical Industries, Alcon P140, softening point = 140 ° C.)
(B) -3: Hydrogenated petroleum resin (Arakawa Chemical Industries, Alcon P115, softening point = 115 ° C.)

[Crystal nucleating agent (C)]
(C) -1: Sorbitol-based crystal nucleating agent (Shin Nippon Rika Co., Ltd., Gelol MD-LM30G, 1,3: 2,4-bis-O- (4-methylbenzylidene) -D-sorbitol)

Example 1
After dry blending (A) -1 and (B) -1 at a mixing mass ratio of 90:10, the mixture was kneaded at 210 ° C. using a 25 mmφ co-directional twin screw extruder, and from a T die (die). The sheet was extruded into a sheet and then rapidly cooled with a casting roll at about 25 ° C. to produce a sheet having a thickness of 0.30 mm. About the obtained sheet | seat, transparency, moisture resistance, and storage elastic modulus (E ') evaluation were performed. The results are shown in Table 1.

(Example 2)
A sheet was prepared and evaluated in the same manner as in Example 1 except that (A) -1 and (B) -2 were dry blended at a mixing mass ratio of 90:10. The results are shown in Table 1.

(Example 3)
A sheet was prepared and evaluated in the same manner as in Example 1 except that (A) -1 and (B) -2 were dry blended at a mixing mass ratio of 80:20. The results are shown in Table 1.

Example 4
Production of a sheet in the same manner as in Example 1 except that (A) -1, (B) -1 and (C) -1 were dry blended at a mixing mass ratio of 94.5: 5: 0.5. And evaluation. The results are shown in Table 1.

(Comparative Example 1)
Using (A) -1 alone, a sheet was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
A sheet was prepared and evaluated in the same manner as in Example 1 except that (A) -1 and (B) -1 were dry blended at a mixing mass ratio of 95: 5. The results are shown in Table 1.

(Comparative Example 3)
A sheet was prepared and evaluated in the same manner as in Example 1 except that (A) -1 and (B) -1 were dry blended at a mixing mass ratio of 70:30. The results are shown in Table 1.

(Comparative Example 4)
Sheets were prepared and evaluated in the same manner as in Example 1 except that (A) -1 and (B) -3 were dry blended at a mixing mass ratio of 90:10. The results are shown in Table 1.

(Comparative Example 5)
After dry blending (A) -1 and crystal nucleating agent (C) -1 at a mixing mass ratio of 99.5: 0.5 without using petroleum resin (B), the same as in Example 1 The sheet was prepared and evaluated by the method described above. The results are shown in Table 1.

As is clear from Table 1, the cycloolefin-based resin sheets described in the examples were excellent in the balance between high moisture resistance and high transparency, and excellent in mechanical properties (storage elastic modulus).
On the other hand, the sheets described in Comparative Examples 1, 2, 4, and 5 had good moisture resistance, but all had poorer transparency than the examples. In addition, the sheet described in Comparative Example 3 has good transparency, but the moisture resistance is inferior to that of the Examples, and the sample cannot be measured when the storage elastic modulus is measured. It was inferior.

  The cycloolefin resin sheet of the present invention is particularly suitable for uses in the medical field, food field and the like. In the medical field, it can be used in PTP packaging sheets, blister package sheets, infusion bags, infusion bags, medicine plugs, and the like. In the food sector, packaging sheets for ham and sausages, processed foods such as retort foods, frozen foods, dried foods, specified insurance foods, cooked rice, confectionery, meat, wrap film, shrink film, etc. for blister packages Can be used as a sheet or the like.

Claims (7)

A cycloolefin resin sheet comprising the following (A) and (B), wherein the ratio of (A) in the sheet is 75% by mass or more and less than 95% by mass Resin sheet.
(A) A crystal having a crystal melting temperature of 120 ° C. or more and 140 ° C. or less measured at a heating rate of 10 ° C./min in differential scanning calorimetry and a crystal melting heat of 20 J / g or more and 50 J / g or less. Cycloolefin resin (B) Petroleum resin having a softening point of 120 ° C or higher and 145 ° C or lower   The cycloolefin according to claim 1, further comprising (C) a crystal nucleating agent, wherein the proportion of (C) in the sheet is 0.01% by mass or more and 3% by mass or less. Resin sheet.   The cycloolefin resin sheet according to claim 2, wherein the (C) crystal nucleating agent is a sorbitol compound.   The cyclohaze according to any one of claims 1 to 3, wherein the total haze value and the internal haze value at a thickness of 0.30 mm, both measured based on JIS K7105, are 10.0% or less. Olefin resin sheet. The water vapor transmission rate at a thickness of 0.30 mm measured at a temperature of 40 ° C. and a relative humidity of 90% based on JIS K7129B method is 0.30 g / (m ² · 24 hours) or less. The cycloolefin resin sheet according to any one of 1 to 4.   The storage elastic modulus (E ′) at a temperature of 25 ° C. measured at a vibration frequency of 10 Hz based on JIS K7244-4 is 1000 MPa or more and 2500 MPa or less, and the storage elastic modulus (E ′) at a temperature of 110 ° C. is 5 MPa. The cycloolefin resin sheet according to any one of claims 1 to 5, wherein the cycloolefin resin sheet is 100 MPa or less. The package formed by shape | molding the cycloolefin type resin sheet of any one of Claims 1-6.