TW201704330A - Polymer composition, pellets, and molded article - Google Patents

Abstract

An embodiment of the invention relates to a polymer composition containing a cyclic olefin polymer (I) having a glass transition temperature of 60 DEG C or higher and a cyclic olefin polymer (i) having a glass transition temperature of 10 DEG C or lower where the tensile modulus measured according to ISO 527-2/1A is 800 MPa or higher.

Description

Polymer composition, tablet and molded article

The present invention relates to a polymer composition, a tablet, and a molded article containing a cycloolefin polymer.

The cycloolefin polymer is widely used in packaging materials such as foods, pharmaceuticals, medical supplies, daily necessities, and electronic parts because of its excellent heat resistance, transparency, and water vapor barrier properties. Moreover, since it has excellent formability, it is also possible to use a diagnostic instrument in the medical field, or a device or a part used in a manufacturing process such as a pharmaceutical or a semiconductor.

For example, in Patent Documents 1 and 2, a cycloolefin-based resin composition suitable for use in containers, packaging, and the like has been disclosed. In the case of the cycloolefin-based resin composition disclosed in Patent Document 1, it is a problem of improving the slidability and providing a molded article having good transparency and surface gloss, and is composed of (A) a cycloolefin-based resin (A1) or The cycloolefin-based resin (A1) and (b) a resin composition (A2) composed of a polyolefin and (B) a guanamine-based compound. At the same time, in the case of the cycloolefin-based resin composition disclosed in Patent Document 2, in order to improve the slidability and to provide a molded article having good transparency and surface gloss, (A) a cycloolefin resin (A1) Or a resin composition (A2) composed of the cycloolefin resin (A1) and (b) a polyolefin, and (B) at least one cycloolefin resin having a chemical structure different from the above (A1) (B1) ) constitutes.

[Previous Technical Literature]

[Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. 2001-26692

Patent Document 2: Japanese Patent Laid-Open Publication No. 2001-26693

The cycloolefin polymer generally used is characterized by excellent heat resistance and low permittivity. However, since the modulus of elasticity is high and the toughness is low, it may be difficult to use the cycloolefin polymer alone depending on the application, the molding method, and the like.

Accordingly, an object of the present invention is to provide a polymer composition which can maintain high heat resistance and has excellent toughness, and a tablet for obtaining the polymer composition. Meanwhile, an embodiment of the present invention has an object of providing a molded article which can maintain high heat resistance and has excellent toughness.

The present inventors have found that the above problems can be solved by using a combination of specific cycloolefin polymers, and the present invention has been completed.

The present invention relates to a polymer composition, and the embodiment comprises a cycloolefin polymer (I) having a glass transition temperature of 60 ° C or higher and a cycloolefin polymer (i) having a glass transition temperature of 10 ° C or lower. The tensile elasticity measured according to ISO 527-2/1A is 800 MPa or more.

Furthermore, another embodiment of the present invention includes a tablet (I) containing the cycloolefin polymer (I) and a tablet (i) containing the cycloolefin polymer (i). Used to obtain the foregoing embodiment A tablet of the polymer composition.

Still another embodiment of the present invention relates to a molded article formed from the polymer composition of the above embodiment.

According to an embodiment of the present invention, a polymer composition which can maintain high heat resistance and excellent toughness, and a tablet for obtaining the polymer composition can be provided. Further, in another embodiment of the present invention, it is possible to provide a molded article which can maintain high heat resistance and has excellent toughness.

The present invention is related to the subject matter contained in Japanese Patent Application No. 2015-024323, filed on Jan.

Hereinafter, embodiments of the present invention will be described.

[Polymer Composition]

The embodiment of the present invention relates to a cycloolefin polymer (I) having a glass transition temperature of 60 ° C or higher and a cycloolefin polymer (i) having a glass transition temperature of 10 ° C or lower, and according to ISO 527. The composition having a tensile elasticity measured at -2/1A of 800 MPa or more.

When the cycloolefin polymer (I) having a glass transition temperature of 60 ° C or higher is used alone, the toughness of the polymer tends to be low, and the toughness and impact resistance of the obtained molded article tend to be poor. In the embodiment of the present invention, the cycloolefin polymer (I) and the cyclic olefin having a glass transition temperature of 10 ° C or less are used in combination. It is a polymer (i) which improves toughness.

The cycloolefin polymer (I) and the cycloolefin polymer (i) (hereinafter, referred to as "cycloolefin polymer" in some cases) may be polymerized with a polymerization component containing at least a cycloolefin component. And the polymer obtained. A cycloolefin polymer having a structure in which a cycloolefin is contained at least in the main chain.

In one embodiment of the present invention, the cycloolefin polymer contains at least one selected from the group consisting of the following cyclic olefin structure (A1) and the following cyclic olefin structure (A2), and the following linear olefin structure. (B).

Cycloolefin structure (A1)

Wherein R ¹ to R ^{12 are} each selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and may be the same or different from each other; R ⁹ and R ¹⁰ , and R ¹¹ and R ¹² may each be combined. A divalent hydrocarbon group is formed; R ⁹ or R ¹⁰ , and R ¹¹ or R ¹² , each of which may be bonded to form a ring.

n represents 0 or a positive integer. When n is 2 or more, R ⁵ to R ⁸ and each repeating unit may be the same or different from each other. The upper limit of n is not particularly limited, and may be, for example, 3 or less.

[Chemical 2]

Cycloolefin structure (A2)

Wherein R ¹ , R ² and R ⁹ to R ^{12 are} each selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and may be the same or different from each other; R ⁹ and R ¹⁰ and R ¹¹ and R ¹² may each be combined to form a divalent hydrocarbon group; R ⁹ or R ¹⁰ , and R ¹¹ or R ¹² may each bond to form a ring.

Linear olefin structure (B)

R ¹ to R ¹² each independently may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group. It is preferred to use a hydrogen atom.

Specific examples of R ¹ to R ⁸ include a hydrogen atom; a halogen atom such as fluorine, chlorine or bromine; and a lower alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group. R ¹ to R ⁸ may be different or partially different. Moreover, they may all be the same.

Specific examples of R ⁹ to R ¹² include a hydrogen atom; a halogen atom such as fluorine, chlorine or bromine; and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, and a stearyl group. An alkyl group; a cycloalkyl group such as a cyclohexyl group; a substituted or unsubstituted aromatic hydrocarbon group such as a phenyl group, a tolyl group, an ethylphenyl group, an isopropylphenyl group, a naphthyl group or an onion group; a benzyl group or a phenyl group; An arylalkyl group or the like in which an aryl group is substituted on an alkyl group. R ⁹ to R ¹² may be different or partially different, and may be all the same.

When R ⁹ and R ¹⁰ or R ¹¹ and R ^{12 are} combined to form a divalent hydrocarbon group, specific examples thereof include an alkylene group such as an ethylene group, a propylene group or an isopropylidene group.

When R ⁹ or R ¹⁰ , and R ¹¹ or R ¹² form a ring, the ring formed may be a single ring or a polycyclic ring. Further, the ring formed may be a polycyclic ring containing a crosslink or a polycyclic ring containing a double bond. At the same time, the ring formed by the combination of the rings can also be used. Further, the ring formed may also contain a substituent such as a methyl group.

The cycloolefin polymer also contains a polymer derived from a structure containing a polar unsaturated compound.

Examples of the polar group include a carboxyl group, an acid anhydride group, an epoxy group, a decylamino group, an ester group, and a hydroxyl group. Examples of the unsaturated group-containing unsaturated compound include (meth)acrylic acid, maleic acid, maleic anhydride, itaconic anhydride, glycidyl (meth)acrylate, and (methyl). Acrylic acid alkyl (preferably having a carbon number of 1 to 10) ester, maleic acid alkyl group (preferably having a carbon number of 1 to 10) ester, (meth) acrylamide, (meth)acrylic acid-2- Hydroxyethyl ester and the like.

Further, "(meth)acrylyl" means "acrylic" or "methacryl", and "(meth)acrylate" means "acrylate" or "methacrylate".

The cycloolefin polymers (I) and (i) each preferably contain at least one selected from the group consisting of a cycloolefin structure (A1) and a cycloolefin structure (A2), and a linear olefin structure (B). .

The cycloolefin polymer (I) and the cycloolefin polymer (i) may contain a cycloolefin structure (A1) at the same time, and may also contain a cycloolefin structure (A2). Meanwhile, the cycloolefin polymer (I) may contain a cycloolefin structure (A1), and the cycloolefin polymer (i) may contain a cycloolefin structure (A2). At least in the cycloolefin polymerization The compound (i) preferably has a cycloolefin structure (A1), and more preferably a cycloolefin polymer (I) and a cycloolefin polymer (i), and a cycloolefin structure (A1).

Specific examples of the cycloolefin polymer include a polymer having the following structure (P1) or the following structure (P2).

Construction (P1)

In the formula, R ¹ to R ¹² and n, and the cycloolefin configuration (A1) in the R ¹ to R ¹² and n are the same. p and q each represent a number of 1 or more. The upper limits of p and q are not particularly limited. For example, p may be 800 or less, and q may be 2,500 or less.

Construction (P2)

Wherein, R ^1, R ² and R ⁹ to R ^12, the aforementioned cycloolefin configuration (A2), the R ^1, identical to R ¹² R ^{2 9} and R. r, indicating a number of 2 or more. The upper limit of r is not particularly limited, and may be, for example, 400 or less.

Further, the cycloolefin polymer (I) and (i) are preferably each contained in the structure (P1) or the structure (P2).

The cycloolefin polymer (I) and the cycloolefin polymer (i) may contain the structure (P1) or the structure (P2) at the same time. Further, the cycloolefin polymer (I)-containing structure (P1) may be used, and the cycloolefin polymer (i) may have a structure (P2). Further, at least the cycloolefin polymer (I) contains a structure (P1), and the cycloolefin polymer (I) and the cycloolefin polymer (i) preferably contain a structure (P1).

The method for producing the cycloolefin polymer is not particularly limited, and it can be obtained by any production method from the viewpoint of a cycloolefin polymer. For example, it may be a copolymer of a cycloolefin component and an α-olefin component, a ring-opening (co)polymer of a cycloolefin component, a hydrogenated product of a ring-opening (co)polymer of a cycloolefin component, or the like. The copolymer may be a random copolymer, a block copolymer, or a graft copolymer, and a random copolymer is preferred.

In terms of the cycloolefin polymer, it is preferred to use a copolymer of a cycloolefin component and an α-olefin component from the viewpoint of easily adjusting the glass transition temperature and tensile elasticity.

The α-olefin component is not particularly limited, and an α-olefin having 2 to 20 carbon atoms is preferred. For example: 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-B 1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1- Octadecene, 1- 20 carbon Alkene and the like. Further, the α-olefin components may be used singly or in combination of two or more kinds. Further, it is easy to obtain the α-olefin component, and it is preferable to use ethylene alone in terms of ease of handling.

The cycloolefin component is preferably a compound (C) as described below.

Compound (C)

In the formula, R ¹ to R ¹² and n, and the cycloolefin configuration (A1) in the R ¹ to R ¹² and n are the same.

Specific examples of the cycloolefin component include cyclopentene, cyclohexene, cyclooctene, a cyclopentene such as cyclopentadiene or 1,3-cyclohexadiene; and a bicyclo ring [2.2.1] Hept-2-ene (common name: norbornene), 5-methyl-bicyclo[2.2.1]-hept-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-ethylene- 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]-hept-2-ene, 5-methylene-bicyclo[2.2.1]-hept-2-ene, 5-vinyl-bicyclo [2.2.1] a 2-membered cyclic olefin such as hept-2-ene, 5-propenyl-bicyclo[2.2.1]-hept-2-ene; tricyclo[4.3.0.1 ^2,5 ]-癸-3,7-diene (common name: dicyclopentadiene), tricyclo[4.3.0.1 ^2,5 ]-indol-3-ene; tricyclo[4.4.0.1 ^2,5 ]- eleven carbon- 3,7-diene or tricyclo [4.4.0.1 ^2,5] - undec-3,8-diene or a hydrogenated portion (with cyclopentadienyl or cyclohexene of adduct) ter Ring [4.4.0.1 ^2,5 ]-undec-3-ene; 5-cyclopentyl-bicyclo[2.2.1]-hept-2-ene, 5-cyclohexyl-bicyclo[2.2.1] -hept-2-ene, 5-cyclohexenyl-di a 3-membered cyclic olefin such as cyclo[2.2.1]-hept-2-ene, 5-phenyl-bicyclo[2.2.1]-hept-2-ene; tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] ^-dodeca -3-ene (also known as tetracyclododecene alone), 8-methyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-dode carbon 3-ene, 8-ethyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-dodec-3-ene, 8-methylene-tetracyclo[4.4.0.1 ^2,5 . ^1,7,10 ] ^-dodeca -3-ene, 8-ethylene-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-dodeca-3-ene, 8-vinyl-tetra Ring [4.4.0.1 ^2,5 .1 ^7,10 ]-dodec-3-ene, 8-propenyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-dodeca-3- a 4-membered cyclic olefin such as alkene; 8-cyclopentyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-dodeca-3-ene, 8-cyclohexyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ] ^-dodeca -3-ene, 8-cyclohexenyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-dodeca-3-ene, 8 -phenyl-cyclopentyl-tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-dodeca-3-ene; tetracyclo[7.4.1 ^3,6 .0 ^1,9 .0 ^{2, 7]} - tetradecene -4,9,11,13- tetraene (also called 1,4-methyl -1,4,4a, 9a- tetrahydro-fluorene), tetracyclo [8.4.1 ^{4, 7.1 1,10} .0 ^3,8 ]-pentadeca-5,10,12,14-tetraene (also known as 1,4-methyl-1,4,4a,5,10,10a - hexahydroquinone); Ring ^{[6.6.1.1 3,6 .0 2,7 .0 9,14]} -4- hexadecene, pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- Pentadecene, pentacyclo[7.4.0.0 ^2,7 .1 ^3,6 .1 ^10,13 ]-4-pentadecene; hepta[8.7.0.1 ^2,9 .1 ^4,7 .1 ^{11 ,17} .0 ^3,8 .0 ^12,16 ]-5-eicene, seven rings [8.7.0.1 ^2,9 .0 ^3,8 .1 ^4,7 .0 ^12,17 .1 ^13,16 a heptane olefin having a polycyclic ring such as a tetramer of a cyclopentadiene.

The cycloolefin component may be used singly or in combination of two or more kinds. For the cycloolefin component, the bicyclo[2.2.1]-hept-2-ene is used alone. (Customary name: norbornene) is preferred.

Further, as the optional component, a polar group-containing unsaturated compound can be used. Examples of the polar group and the polar group-containing unsaturated compound can be as described above.

The method of copolymerizing the cycloolefin component and the α-olefin component is, for example, a method of ring-opening (co)polymerization of a cycloolefin component or a method of hydrogenating a ring-opening (co)polymer of a cycloolefin component, and is not particularly limited. It can be operated in accordance with generally known methods.

The polymerization catalyst to be used is not particularly limited, and a generally known catalyst such as a Ziegler-Natta catalyst (Ziegler-Natta catalyst), a disubstituted system or a metallocene catalyst can be used. For example, a copolymer of a cycloolefin component and an α-olefin component is preferably produced by using a metallocene catalyst. Further, the ring-opening (co)polymer of the cycloolefin component is preferably produced by using a disubstituted catalyst. Meanwhile, it is preferred that the polymer obtained by using the double-substituted catalyst is hydrogenated by using an inorganic carrier-adsorbing transition metal catalyst or the like.

The glass transition temperature of the cycloolefin polymer (I) is preferably 60 ° C or more, more preferably 70 ° C or more, and still more preferably 100 ° C or more, from the viewpoint of suiting the use environment for various uses. At the same time, since it is more brittle than 220 ° C, and there is a tendency to be difficult to process, the glass transition temperature of the user is usually 220 ° C or less. It is preferably 200 ° C or less.

The glass transition temperature of the cycloolefin polymer (i) is 10 ° C or lower. When it exceeds 10 ° C, the effect of imparting toughness is insufficient. On the other hand, when the glass transition temperature is less than -50 ° C, there is a problem that adhesion between the ingots occurs during storage at room temperature, and therefore it is preferably -50 ° C or higher. More preferably -10 ° C or more, and more preferably 0 ° C or more.

The tensile elasticity of the cycloolefin polymer (I) is preferably 1,500 MPa or more, more preferably 2,000 MPa or more, and still more preferably 2,500 MPa or more. At the same time, the tensile elasticity is preferably 5,000 MPa or less, more preferably 4,000 MPa or less, and more preferably 3,500 MPa or less.

The tensile elasticity of the cycloolefin polymer (i) is preferably 1 MPa or more, more preferably 10 MPa or more, and still more preferably 30 MPa or more. At the same time, the tensile elasticity is preferably 300 MPa or less, more preferably 100 MPa or less, and even more preferably 60 MPa or less.

As the cycloolefin polymer, a commercially available polymer can also be used. For example, TOPAS (registered trademark) (manufactured by TOPAS Advanced Polymers Co., Ltd.), APEL (registered trademark) (manufactured by Mitsui Chemicals, Inc.), and ZEONEX (registered trademark) (manufactured by Japan ZEON Co., Ltd.) ZEONOR (registered trademark) (manufactured by Japan ZEON Co., Ltd.), ARTON (registered trademark) (manufactured by JSR Co., Ltd.), and the like.

More specifically, the cycloolefin polymer (I) may, for example, be TOPAS 8007S-04 (78 ° C, 2600 MPa), 6013 S-04 (138 ° C, 2900 MPa), 6015 S-04 (158 ° C, 3000 MPa), 6017S-04 (178 ° C, 3000 MPa) and so on.

Further, examples of the cycloolefin polymer (i) include TOPAS Elastomer E-140 (6 ° C, 44 MPa).

In the above, the parentheses indicate the glass transition temperature (°C) and the tensile elasticity (MPa) of the cycloolefin polymer.

When the cycloolefin polymer contains a cycloolefin component and an α-olefin component, the glass transition temperature and tensile elasticity of the cycloolefin polymer can be adjusted by, for example, changing the copolymerization ratio of the cycloolefin component and the α-olefin component. . Raising the ring When the ratio of the olefin component is increased, the glass transition temperature and the tensile elasticity tend to be increased, and when the ratio of the α-olefin component is increased, the glass transition temperature and the tensile elasticity tend to be lowered.

In the present invention, the glass transition temperature can be measured in accordance with ISO 11357-1, -2, and -3. At the same time, the tensile elasticity can be determined in accordance with ISO 527-2/1A.

The tensile elasticity of the polymer composition is preferably 800 MPa or more, more preferably 1300 MPa or more, and still more preferably 1,500 MPa or more, from the viewpoint of the strength of the use of the processed product of the polymer composition. Further, the tensile strength of the polymer composition is not particularly limited, and is preferably 3,800 MPa or less, more preferably 3,500 MPa or less, and still more preferably 3,300 MPa or less. For example, in the case of a composite component in which a part is deformed, such as a snap-fit, when the tensile elasticity is too high, there is a tendency that the stress is too strong when combined, and the upper limit of the tensile elasticity is The foregoing range is preferred.

In order to increase the tensile elasticity of the polymer composition, for example, the content of the cyclic olefin-based polymer having a large tensile elasticity can be increased, and at the same time, the tensile elasticity of the polymer composition can be reduced to increase the cyclic olefin having a small tensile elasticity. The content of the polymer.

In the DSC curve prepared by differential scanning calorimetry, the polymer composition showed two glass transition temperatures from the cycloolefin polymer (I) and the cycloolefin polymer (i). When the polymer composition exhibits two glass transition temperatures, it is preferable to maintain the heat resistance of the cycloolefin polymer (I). In addition, the differential scanning calorimetry can be performed according to ISO 11357-1, -2, and -3.

a cycloolefin polymer (I) and a cycloolefin polymer (i), Non-miscibility is preferred. When it is non-miscible, even if a cycloolefin-based polymer (i) having a low glass transition temperature is added and mixed, the glass transition temperature is not changed, so that the glass of the cycloolefin-based polymer (I) is not lowered. The state transitions temperature while maintaining heat resistance. When the cycloolefin polymer (I) and the cycloolefin polymer (i) are mutually miscible, the polymer composition may have a structure in which they are separated from each other. The polymer composition has a separate structure and can be determined by scanning electron microscopy (SEM). The polymer composition preferably has a sheath-core phase separation structure in which the outer phase is formed of the cycloolefin polymer (I) and the core phase is formed of the cycloolefin polymer (i).

The content of the cycloolefin polymer (I) in the polymer composition is preferably 50% by mass or more, more preferably 55% by mass or more, based on the total mass of the polymer composition, from the viewpoint of maintaining high modulus of elasticity. More than 60% by mass. Meanwhile, the content of the cycloolefin polymer (I) is preferably 99% by mass or less, more preferably 95% by mass or less, and 90% by mass based on the total mass of the polymer composition. The following is even better.

The content of the cycloolefin polymer (i) in the polymer composition is preferably 1% by mass or more, more preferably 5% by mass or more, based on the total mass of the polymer composition, from the viewpoint of improvement in toughness. 10% by mass or more is even better. Meanwhile, the content of the cycloolefin polymer (i) is preferably 50% by mass or less, more preferably 45% by mass or less, based on the total mass of the polymer composition, from the viewpoint of maintaining a high modulus of elasticity. Less than or equal to the mass%.

The polymer composition is preferably a cycloolefin polymer (I) in an amount of from 50 to 99% by mass based on the total mass of the polymer composition, and the cycloolefin polymer (i) is relative to the entire polymer composition. The mass is preferably from 1 to 50% by mass.

The polymer composition may further contain any other components other than the cycloolefin polymer. Examples of the optional components include thermoplastic resins and additives.

Examples of the thermoplastic resin include high-density polyethylene (HDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and polypropylene, which are widely used in cycloolefin resins; polystyrene and polyacrylic acid. Vinyl resins such as esters and polymethacrylates; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; and polyamide resins such as nylon 6, nylon 66, and the like. The thermoplastic resins may be used singly or in combination of two or more kinds.

When the polymer composition contains any thermoplastic resin, it is preferred that the content of the polymer composition is not pure.

The additive is not particularly limited as long as it is a usual user on the thermoplastic resin material. For example, a heat stabilizer, a light stabilizer, an antistatic agent, a slip agent, an anti-caking agent, a deodorant, a lubricant, a synthetic oil, a natural oil, an inorganic and organic filler, a dye, a pigment, and the like can be exemplified.

When the polymer composition contains any of the additives, the content of the additive is preferably such that the content of the polymer composition is not pure.

The method for producing the polymer composition is not particularly limited. The cycloolefin polymer (I), the cycloolefin polymer (i), and any optional components as needed may be blended and mixed. The method of mixing is not limited to a specific method. The mixing method is specifically, for example, mixing in a molten state of a cycloolefin polymer in a mixer, a uniaxial mixer, a twin-shaft mixer, a drum, a Brabender mixer, an extrusion molding machine, or the like. Method; after the cycloolefin polymer is dissolved in a suitable solvent, it is solidified, then allowed to flow, or A method of directly drying the solvent, and the like.

The form of the polymer composition is not particularly limited, and may be in the form of a tablet, a powder or a solution. It is preferably in the form of a tablet. The polymer composition may be obtained by mixing a cycloolefin polymer (I) and (i) in a kneader, and extruding it into a rod shape in a molten state, and then cutting it into a suitable shape by a cutter. The length can be made into tablets.

When the polymer composition is used in the medical field, the semiconductor field, or the like, the polymer composition is excellent in purity. From this point of view, the content of the metal contained in the polymer composition is preferably 20 ppm or less, more preferably 10 ppm or less, and still more preferably 5 ppm or less. Examples of the metal include Al, Ca, Fe, Mg, Mn, Na, Ti, and the like.

The content of the metal can be determined by inductively coupled plasma (ICP) mass spectrometry.

It is preferred to use a purified cycloolefin polymer in reducing the metal content in the polymer composition. For the purification method, for example, a method of filtration, adsorption, or the like can be used. Specifically, Japanese Patent Publication No. 05-317411, paragraph 0010, Japanese Patent Laid-Open Publication No. 2003-183361, paragraph 0009, and JP-A-2009 The method and the like contained in paragraphs 0038 to 0054 of the Japanese Patent Publication No. 227840.

[slices]

Another embodiment of the present invention relates to a tablet (a group of tablets containing two or more kinds of tablets) in which a polymer composition is obtained. Further, the tablet contains at least a tablet (I) containing a cycloolefin polymer (I) and a tablet (i) containing a cycloolefin polymer (i).

A method for improving the toughness of a polymer composition, comprising: a method of mixing a cycloolefin polymer with a cycloethylene, and adding a cycloolefin polymer A method of adding synthetic rubber, and the like. However, when other kinds of compounds are added, there is a case where the impurities are reduced and the purity is lowered. Therefore, from the viewpoint of the purity of the polymer composition, the content of the metal contained in each of the tablets is preferably low. The total content of aluminum, calcium, iron, magnesium, manganese, sodium, and titanium contained in each of the tablets is preferably 20 ppm or less, more preferably 10 ppm or less, and still more preferably 5 ppm or less. Meanwhile, the content of the metal contained in each of the tablets is preferably 20 ppm or less, more preferably 10 ppm or less, and still more preferably 5 ppm or less.

The olefinic polymer product having a low metal content may, for example, be TOPAS (registered trademark) (manufactured by TOPAS Advanced Polymers Co., Ltd.). Such a cycloolefin polymer is suitable for producing a highly pure polymer composition because the metal content is lower than that of a polyethylene product or the like. On the other hand, a tablet having a low mixed metal content can easily produce a purely pure polymer composition.

[Molded product]

Still another embodiment of the present invention relates to a molded article formed from a polymer composition. For molded products, it can be used for food film, pharmaceutical film, agricultural film, packaging materials, medical infusion bags, medical instruments, daily necessities, toys, auto parts, home appliance parts, various filter materials, etc. Cloth, various filter sleeves, piping hoses or fittings, etc.

The molding may be, for example, a tablet (composite) obtained from the polymer composition, or a tablet obtained from the cycloolefin polymer (I) and a tablet obtained from the cycloolefin polymer (i). Use after dry mixing.

For the forming method, it can be used as follows: single-axis extruder, open-hole extruder, twin-screw extruder, conical twin-screw extruder, twin-shaft kneading extruder, plunger extruder, Mixing extruder, twin-shaft conical screw extruder, planetary snail A bar extruder, a gear type extruder, and a screwless extruder are used for extrusion molding, injection molding, blow molding, rotational molding, melt spinning, long fiber nonwoven processing, and the like. Further, a film or a sheet may be formed by a T-die molding method, an inflation molding method, or the like. In the forming process, heat stabilizers, light stabilizers, antistatic agents, slip agents, anti-caking agents, deodorants, lubricants, synthetic oils, natural oils, inorganic and organic fillers, dyes may also be added. , pigments, etc.

Example

Hereinafter, the present invention will be specifically described by way of Examples and Comparative Examples, but the present invention is not limited to the Examples.

[Cycloolefin polymer]

In the examples and comparative examples, a commercially available tablet was used as the cycloolefin polymer. The cycloolefin polymer used is shown in Table 1.

[Polymer Composition]

First, the cycloolefin polymer shown in Table 1 was subjected to a biaxial extruder ("Steel 30α" manufactured by Nippon Steel Works Co., Ltd., barrel temperature 280 ° C, screw rotation speed 150 rpm, extrusion amount 15 kg, as shown in Table 2). /hr) Melt mixing to obtain a polymer composition.

Then, the obtained polymer composition was subjected to evaluation of heat distortion temperature, tensile test, and the like. The results are shown in Table 2.

As shown in Table 2, it is understood that the polymer composition containing the cycloolefin polymer (I) having a glass transition temperature of 60 ° C or higher and the cycloolefin polymer (i) having a glass transition temperature of 10 ° C or lower can be maintained. High heat distortion temperature and excellent softness. Moreover, purity is also good.

[Measurement method]

The evaluation of the cycloolefin polymer and the polymer composition can be carried out as follows.

(tensile elasticity)

The tensile elasticity of the cycloolefin polymer and the polymer composition is determined in accordance with ISO 527-2/1A.

(glass transition temperature of cycloolefin polymer)

The glass transition temperature of the cycloolefin polymer was measured in accordance with ISO 11357-1, -2, and -3 at a temperature increase rate of 10 ° C/min.

(metal content)

The metal content of the cycloolefin polymer and the polymer composition was measured by an inductively coupled plasma mass spectrometer ("CIROSCCD-120" manufactured by Spectro Corporation). For the standard product, the "ICP Wide Mixture XSTC-22" manufactured by SPEX Corporation is used.

First, 1 g of the sample washed with ultrapure water was weighed in a platinum crucible, and after being carbonized by heating in a small electric heating furnace, it was ashed by an electric furnace (600 ° C × 1 hr). Thereafter, the ashed sample was dissolved in 5 mL of a 3.5% by mass aqueous hydrochloric acid solution, and the resulting solution was further added with ultrapure water to adjust a volume of 25 mL. The solution of the adjusted volume was used as an analytical sample, and quantitative analysis of the target metal (Al, Ca, Fe, Mg, Mn, Na, Ti) was carried out by ICP mass spectrometry. The lower limit of detection is 0.25 ppm (μg/g). Table 2 shows the total content of the target metals. "<5" means "less than 5ppm".

(glass transition temperature of the polymer composition)

Thereafter, the polymer composition was subjected to differential scanning calorimetry according to ISO 11357-1, -2, and -3 at a temperature increase rate of 10 ° C/min, and a DSC curve was prepared. In the DSC curve, it was determined that two of the glass transition temperatures from the cycloolefin polymers (I) and (i) were judged as "Yes", and those which could not be determined were "None".

(heat distortion temperature (DTUL))

The heat distortion temperature of the polymer composition was measured in accordance with ISO 75-1, -2 and at a load of 0.45 MPa.

(tensile fracture test)

The polymer composition was subjected to a tensile test in accordance with ISO 527-2/1A. It is judged as "ductile" fracture by the necker, and "brittle" fracture is not caused by necking.

(resistant test)

First, a polymer composition was used to prepare a film having a thickness of 50 μm. The production conditions of the film are as follows.

Membrane forming machine

Extrusion machine: ø32mm single-axis extruder (manufactured by Plastic Engineering Research Institute)

Mode: 300mm wide frame die

Film forming conditions

Screw: Feeding groove depth = 6mm, measuring section groove depth = 2.6mm, C.R. = 2.0, front end with Unimelt

Screw speed: 50 rpm (extrusion ≒ 10 kg / hr)

Feeding method: full feed

Drill lip clearance angle: 0.6mm

Film thickness: The winding speed was adjusted, and a film having a thickness of 50 μm was used.

Thereafter, the films obtained in Example 7 and Comparative Example 3 were evaluated in accordance with a folding test (MIT) (JISP 8115). The evaluation conditions are as follows. The number of repetitions until the breakage is shown in Table 2.

Measuring machine: manufactured by Toyo Seiki Co., Ltd., MIT Fatigue Tester "MIT-DA"

Angle: 135°

Test speed: 175 cpm

Load: 9.8N

Clip: curvature 0.38, gap 0.25mm

Test piece: 15mm wide

Measurement environment: 23 ° C, 50% RH

Zigzag direction

MD: The film is folded toward the resin flow direction. The pleats are perpendicular to the flow direction of the resin.

TD: The film is folded toward the vertical resin flow direction. The crease is in the direction of the resin flow.

[Possibility of industrial use]

The polymer composition, the tablet, and the molded article of the present invention are suitable for use in packaging materials for foods, pharmaceuticals, medical supplies, daily necessities, electronic parts, and the like, diagnostic instruments in the medical field, or manufacturing of pharmaceuticals, semiconductors, and the like. The use of equipment or parts used in the project. In particular, a polymer composition having a low metal content is suitable for use in medical applications (pharmaceutical engineering, machine piping, joints, etc.), and semiconductor applications (semiconductor manufacturing engineering).

Claims (11)

A polymer composition comprising: a cycloolefin polymer (I) having a glass transition temperature of 60 ° C or higher, and a cycloolefin polymer (i) having a glass transition temperature of 10 ° C or less, and according to ISO 527-2/ The tensile elasticity measured by 1A was 800 MPa or more. The polymer composition according to claim 1, which has two glass transition temperatures derived from the cycloolefin polymer (I) and the cycloolefin polymer (i). The polymer composition according to claim 1 or 2, wherein the cycloolefin polymer (I) contains 50 to 99% by mass based on the total mass of the polymer composition, and the cycloolefin polymer (i) is 1 to 50% by mass based on the total mass of the polymer composition. The polymer composition according to any one of claims 1 to 3, wherein the cycloolefin polymers (I) and (i) each contain a cycloolefin structure (A1) selected from the group consisting of At least one of the group consisting of the following cycloolefin structure (A2) and the following linear olefin structure (B): Cycloolefin structure (A1) wherein R ¹ to R ^{12 are} each selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and may be the same or different from each other; R ⁹ and R ¹⁰ and R ¹¹ and R ¹² , each may be combined to form a divalent hydrocarbon group; R ⁹ or R ¹⁰ , and R ¹¹ or R ¹² may each bond to form a ring; n represents 0 or a positive integer, and when n is 2 or more, R ⁵ to R ^8. Each repeating unit may be the same or different from each other; In the formula of the cycloolefin structure (A2), R ¹ , R ² and R ⁹ to R ^{12 are} each selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and may be the same or different from each other; R ⁹ and R ^And R ¹¹ and R ¹² may each be combined to form a divalent hydrocarbon group; R ⁹ or R ¹⁰ , and R ¹¹ or R ¹² may each bond to form a ring; Linear olefin structure (B). The polymer composition according to claim 4, wherein the cycloolefin polymer (i) contains the cycloolefin structure (A1). The polymer composition according to any one of claims 1 to 5, wherein the cycloolefin polymers (I) and (i) each have the following structure (P1) or the following structure ( P2): In the formula (P1), R ¹ to R ^{12 are} each selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and may be the same or different from each other; R ⁹ and R ¹⁰ , and R ¹¹ and R ¹² , each may be combined to form a divalent hydrocarbon group; R ⁹ or R ¹⁰ , and R ¹¹ or R ¹² may also each bond to form a ring; n, representing 0 or a positive integer, when n is 2 or more, R ⁵ to R ⁸ , each repeating unit may be the same or different from each other; p and q, each representing a number of 1 or more; In the formula (P2), R ¹ , R ² and R ⁹ to R ^{12 are} each selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and may be the same or different from each other; R ⁹ and R ¹⁰ And R ¹¹ and R ¹² each may be combined to form a divalent hydrocarbon group; R ⁹ or R ¹⁰ , and R ¹¹ or R ¹² may each bond to form a ring; r represents a number of 2 or more. The polymer composition according to claim 6, wherein the cycloolefin polymer (i) contains the above structure (P1). A tablet composition according to any one of claims 1 to 7, wherein the tablet (I) containing the cycloolefin polymer (I) is contained, And a tablet (i) containing the aforementioned cycloolefin polymer (i). The tablet according to claim 8, wherein the tablet (I) and (i) have a metal content of 5 ppm or less. The tablet according to claim 8 or 9, wherein the total amount of aluminum, calcium, iron, magnesium, manganese, sodium, and titanium contained in the tablets (I) and (i) is Each is 5 ppm or less. A molded article formed by the polymer composition according to any one of claims 1 to 7.