JP2011057864A - Cyclic olefin-based resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cyclic olefin-based resin composition which can be prepared by not necessary using a compatibilizer and is excellent in mechanical characteristics, transparency, and lightness. <P>SOLUTION: The cyclic olefin-based resin composition includes, as a component: a cyclic olefin-based resin having a glass transition point of 50-100°C; and an aliphatic polyamide resin containing at least 50 mol% of a repeating unit represented by formula (I): -NH-(CH<SB>2</SB>)<SB>m</SB>-CO- (where, m is an integer of 9-12), for the whole repeating units, in an amount of 1-100 pts.mass based on 100 pts.mass of the cyclic olefin-based resin. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a cyclic olefin-based resin composition having excellent mechanical properties, transparency, and lightness.

  Cyclic olefin-based resins are excellent in transparency, chemical resistance, moisture resistance, mechanical properties, etc., have low specific gravity and can reduce the weight of products, so they are used as materials for optical applications, pharmaceutical or medical equipment applications, etc. Yes. In addition, the cyclic olefin-based resin is excellent in melt processability and fluidity, and is also used for film-shaped or sheet-shaped molded products and packaging materials. Furthermore, cyclic olefin resin is excellent also in heat shrinkability and printing characteristics. Thus, the cyclic olefin resin is used in various fields.

  However, while the cyclic olefin resin has many excellent properties, it is very brittle, so that impact resistance may be insufficient depending on the application. For this reason, it is desired to improve mechanical properties such as impact resistance without impairing the excellent properties of the cyclic olefin resin.

  For example, as a method for improving the impact resistance of a cyclic olefin resin, a modified cyclic polyolefin resin (modified amorphous polyolefin) having a carboxylic anhydride group and / or a carboxylic acid group in the molecule and a polyamide are used. A method for producing a cyclic olefin-based resin composition by adding a compatibilizing agent obtained by reacting a mixture while being melted, and melt-kneading a mixture of a cyclic polyolefin-based resin (amorphous polyolefin) and polyamide. It has been proposed (Patent Document 1).

  In the examples of Patent Document 1, a compatibilizing agent prepared by reacting a cyclic olefin resin modified with maleic anhydride and having a heat deformation temperature of 70 ° C. with nylon 6/6, 6 is used. A method of melt-kneading a cyclic olefin resin having a temperature of 70 ° C. and nylon 6/6, 6 or a reaction of a cyclic olefin resin having a heat deformation temperature of 110 ° C. modified with maleic anhydride and nylon 12 A method of melt-kneading a cyclic olefin resin having a heat deformation temperature of 110 ° C. and nylon 12 using the prepared compatibilizing agent is disclosed.

JP 07-216149 A

  However, in the method disclosed in Patent Document 1, a modification step of a cyclic olefin resin that modifies a cyclic olefin resin with an unsaturated carboxylic acid or the like, and a compatibilizing agent that reacts the modified cyclic olefin resin with polyamide. There is a problem that a preparation step is necessary and the step for preparing a cyclic olefin resin composition containing a cyclic olefin resin and polyamide is very complicated.

  In the method disclosed in Patent Document 1, depending on the type of polyamide used, the specific gravity of the cyclic olefin resin composition may be higher than the specific gravity of the raw material cyclic polyolefin resin.

  The present invention has been made to solve the above-described problems, and can be prepared without necessarily using a compatibilizing agent, and a cyclic olefin-based resin composition that is excellent in mechanical properties, transparency, and lightness. The purpose is to provide.

As a component of the cyclic olefin-based resin composition, the inventors have a cyclic olefin-based resin having a glass transition point of 50 ° C. or higher and 100 ° C. or lower, and 1 to 100 parts by mass with respect to 100 parts by mass of the cyclic olefin-based resin. By including an aliphatic polyamide resin containing 50 mol% or more of the repeating unit represented by the following formula (I) in all the repeating units, the mechanical properties and transparency are not necessarily used without using a compatibilizer. And it discovered that the cyclic olefin resin composition excellent in lightness was obtained, and came to complete this invention. More specifically, the present invention provides the following.
—NH— (CH ₂ ) _m —CO— (I)
[In the formula (I), m is an integer of 9 or more and 12 or less. ]

(1) A cyclic olefin resin having a glass transition point of 50 ° C. or more and 100 ° C. or less and represented by the following formula (I) of 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the cyclic olefin resin. A cyclic olefin resin composition comprising an aliphatic polyamide resin containing 50 mol% or more of repeating units in all repeating units.
—NH— (CH ₂ ) _m —CO— (I)
[In the formula (I), m is an integer of 9 or more and 12 or less. ]

  (2) Difference between the melt viscosity of the cyclic olefin resin measured at a measurement temperature of 200 ° C. and a shear rate of 1216 / sec and the melt viscosity of the aliphatic polyamide resin measured under the same conditions as the cyclic olefin resin. The cyclic olefin-based resin composition according to (1), wherein the absolute value of is 50 Pa · sec.

  (3) The cyclic olefin-based resin composition according to (1) or (2), wherein the aliphatic polyamide resin is composed only of the repeating unit represented by the formula (I).

  (4) The cyclic olefin resin composition according to any one of (1) to (3), wherein the aliphatic polyamide resin includes a repeating unit represented by the formula (I) wherein m is 10.

  (5) The cyclic olefin resin composition according to any one of (1) to (4), wherein the aliphatic polyamide resin is composed of only a repeating unit represented by the formula (I) wherein m is 10.

  (6) The cyclic olefin resin composition according to any one of (1) to (5), wherein the specific gravity is 1.02 or more and 1.04 or less.

  (7) The cyclic olefin-based resin composition according to any one of (1) to (6), wherein the aliphatic polyamide resin is manufactured using a plant-derived material as at least a part of a raw material.

  ADVANTAGE OF THE INVENTION According to this invention, the cyclic olefin resin excellent in mechanical property, transparency, and lightweight including the cyclic olefin resin and aliphatic polyamide resin is provided without necessarily using a compatibilizing agent.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. . In addition, although description may be abbreviate | omitted suitably about the location where description overlaps, the summary of invention is not limited.

<Cyclic polyolefin resin composition>
The cyclic polyolefin resin composition of the present invention is a cyclic olefin resin having a glass transition point of 50 ° C. or more and 100 ° C. or less, and a lower formula of 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the cyclic olefin resin. An aliphatic polyamide resin containing 50 mol% or more of the repeating units represented by (I) in all repeating units is included.
—NH— (CH ₂ ) _m —CO— (I)
[In the formula (I), m is an integer of 9 or more and 12 or less. ]

  In the cyclic polyolefin resin composition of the present invention, the cyclic polyolefin resin having a glass transition point of 50 ° C. or more and 100 ° C. or less, and the repeating unit represented by the formula (I) are contained in an amount of 50 mol% or more in all repeating units. The total content of the aliphatic polyamide resin is not particularly limited as long as the object of the present invention is not impaired. Typically, it is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more in the cyclic polyolefin resin composition.

[Cyclic olefin resin]
The cyclic olefin resin used in the present invention will be described. The cyclic olefin resin used in the present invention contains a cyclic olefin component as a copolymer component, and is a polyolefin resin containing a cyclic olefin component in the main chain, having a glass transition point of 50 ° C. or higher and 100 ° C. or lower. If it is a thing, it will not specifically limit. As a suitable example of the cyclic olefin resin, for example,
(A1) Cyclic olefin addition polymer or hydrogenated product thereof,
(A2) an addition copolymer of a cyclic olefin and an α-olefin or a hydrogenated product thereof,
(A3) A ring-opening (co) polymer of a cyclic olefin or a hydrogenated product thereof.

  The glass transition point of the cyclic olefin resin used in the present invention is preferably 50 ° C. or higher and 100 ° C. or lower, more preferably 50 ° C. or higher and 90 ° C. or lower, and particularly preferably 50 ° C. or higher and 80 ° C. or lower. preferable. In addition, the glass transition point (Tg) employ | adopts the value measured by DSC method (method of JISK7121) on the temperature increase rate of 10 degree-C / min conditions. By using a cyclic olefin resin having a glass transition point in the present invention, a cyclic olefin resin and an aliphatic polyamide resin, which will be described later, can be blended well, and the resulting cyclic olefin resin composition exhibits excellent properties. .

In addition, as a cyclic olefin resin containing a cyclic olefin component used in the present invention as a copolymer component,
(A4) A resin obtained by grafting and / or copolymerizing an unsaturated compound having a polar group to the resins (a1) to (a3).

  Examples of the polar group include a carboxyl group, an acid anhydride group, an epoxy group, an amide group, an ester group, and a hydroxyl group. Examples of the unsaturated compound having a polar group include (meth) acrylic acid and maleic acid. Acid, maleic anhydride, itaconic anhydride, glycidyl (meth) acrylate, alkyl (meth) acrylate (1 to 10 carbon atoms) ester, alkyl maleate (1 to 10 carbon atoms) ester, (meth) acrylamide, (meta ) 2-hydroxyethyl acrylate.

  In the present invention, the cyclic olefin-based resins (a1) to (a4) containing the cyclic olefin component as a copolymerization component may be used alone or in combination of two or more.

  Moreover, as the cyclic olefin-based resin containing the cyclic olefin component used in the present invention as a copolymerization component, a commercially available resin can be used. Examples of commercially available cyclic olefin-based resins include TOPAS (registered trademark) (Topas Advanced Polymers), Apel (registered trademark) (manufactured by Mitsui Chemicals), Zeonex (registered trademark) (manufactured by Nippon Zeon), Examples include ZEONOR (registered trademark) (manufactured by ZEON Corporation), ARTON (registered trademark) (manufactured by JSR Corporation), and the like.

（式中、Ｒ^１からＲ^１２は、それぞれ同一でも異なっていてもよく、水素原子、ハロゲン原子、及び、炭化水素基からなる群より選ばれるものであり、Ｒ^９とＲ^１０、Ｒ^１１とＲ^１２は、一体化して２価の炭化水素基を形成してもよく、Ｒ^９又はＲ^１０と、Ｒ^１１又はＲ^１２とは、互いに環を形成していてもよい。また、ｎは、０又は正の整数を示し、ｎが２以上の場合には、Ｒ^５からＲ^８は、それぞれの繰り返し単位の中で、それぞれ同一でも異なっていてもよい。） The addition copolymer of (a2) cyclic olefin and α-olefin preferably used in the composition of the present invention is not particularly limited. Particularly preferred examples include a copolymer containing [1] an α-olefin component having 2 to 20 carbon atoms and [2] a cyclic olefin component represented by the following general formula (I).

(In the formula, R ¹ to R ¹² may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group, and R ⁹ and R ¹⁰ , R ¹¹ and R ¹² may be integrated to form a divalent hydrocarbon group, and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other, and n is When 0 or a positive integer is represented and n is 2 or more, R ⁵ to R ⁸ may be the same or different in each repeating unit.

[[1] α-olefin component having 2 to 20 carbon atoms]
The α-olefin having 2 to 20 carbon atoms, which is a copolymer component of an addition polymer of a cyclic olefin component and other copolymer components such as ethylene, preferably used in the present invention is not particularly limited. For example, the thing similar to Unexamined-Japanese-Patent No. 2007-302722 can be mentioned. These α-olefin components may be used alone or in combination of two or more. Of these, ethylene is most preferably used alone.

[[2] Cyclic olefin component represented by formula (I)]
In the addition polymer of the cyclic olefin component preferably used in the present invention and another copolymer component such as ethylene, the cyclic olefin component represented by the general formula (I) serving as the copolymer component will be described.

R ¹ to R ¹² in the general formula (I) may be the same or different and are selected from the group consisting of a hydrogen atom, a halogen atom, and a hydrocarbon group.

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

Specific examples of R ⁹ to R ¹² include, for example, hydrogen atom; halogen atom such as fluorine, chlorine, bromine; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, stearyl. Alkyl group such as cyclohexyl group; cycloalkyl group such as cyclohexyl group; substituted or unsubstituted aromatic hydrocarbon group such as phenyl group, tolyl group, ethylphenyl group, isopropylphenyl group, naphthyl group, anthryl group; benzyl group, phenethyl And an aralkyl group in which an aryl group is substituted with an alkyl group, and the like. These may be different from each other, may be partially different, or all may be the same.

Specific examples of the case where R ⁹ and R ¹⁰ or R ¹¹ and R ¹² are integrated to form a divalent hydrocarbon group include, for example, alkylidene groups such as an ethylidene group, a propylidene group, and an isopropylidene group. Can be mentioned.

When R ⁹ or R ¹⁰ and R ¹¹ or R ¹² form a ring with each other, the formed ring may be monocyclic or polycyclic, or may be a polycyclic ring having a bridge. , A ring having a double bond, or a ring composed of a combination of these rings may be used. Moreover, these rings may have a substituent such as a methyl group.

  Specific examples of the cyclic olefin component represented by the general formula (I) include those similar to those described in JP-A-2007-302722.

  These cyclic olefin components may be used singly or in combination of two or more. Among the specific examples described in the above publication, it is preferable to use bicyclo [2.2.1] hept-2-ene (common name: norbornene) alone.

  [1] A method for polymerizing an α-olefin component having 2 to 20 carbon atoms and a [2] cyclic olefin component represented by the general formula (I) and a method for hydrogenating the obtained polymer are particularly limited. Instead, it can be carried out according to known methods. It may be random copolymerization or block copolymerization.

  The polymerization catalyst used is not particularly limited, and can be obtained by a known method using a conventionally known catalyst such as a Ziegler-Natta, metathesis, or metallocene catalyst. The addition copolymer of cyclic olefin and α-olefin or the hydrogenated product thereof preferably used in the present invention is preferably produced using a metallocene catalyst or a Ziegler-Natta catalyst.

  Examples of the metathesis catalyst include molybdenum or tungsten-based metathesis catalysts (for example, described in JP-A Nos. 58-127728 and 58-129003) as ring-opening polymerization catalysts for cycloolefins. In addition, the polymer obtained by the metathesis catalyst uses an inorganic carrier-supported transition metal catalyst or the like, and 90% or more of the main chain double bond and 98% or more of the carbon-carbon double bond in the side chain aromatic ring are hydrogenated. It is preferable to add.

[Other copolymer components]
The addition copolymer of (a2) cyclic olefin and α-olefin particularly preferably used in the composition of the present invention comprises [1] the α-olefin component having 2 to 20 carbon atoms and [2] the general formula (I In addition to the cyclic olefin component represented by (), other copolymerizable unsaturated monomer components may be contained as necessary within the range not impairing the object of the present invention.

  The unsaturated monomer that may be optionally copolymerized is not particularly limited, and examples thereof include hydrocarbon monomers containing two or more carbon-carbon double bonds in one molecule. Can be mentioned. Specific examples of the hydrocarbon-based monomer having two or more carbon-carbon double bonds in one molecule include those similar to those described in JP-A-2007-302722.

[Other ingredients]
In the present invention, the cyclic olefin-based resin may be used as a composition blended with other thermoplastic resins in the range and type that do not impair the object of the present invention. In the present invention, the cyclic olefin-based resin is a filler, an antioxidant, a weathering stabilizer, an ultraviolet absorber, an antibacterial agent, a flame retardant, and a colorant in a range and type that do not impair the object of the present invention. You may use what contains various additives, such as.

[Aliphatic polyamide resin]
The aliphatic polyamide resin used in the present invention is not particularly limited as long as it is an aliphatic polyamide resin containing 50 mol% or more of the repeating units represented by the following formula (I) in all repeating units. In the present invention, two or more aliphatic polyamide resins can be used in combination.
—NH— (CH ₂ ) _m —CO— (I)
[In the formula (I), m is an integer of 9 or more and 12 or less. ]

  The unit represented by the formula (I) is composed of 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 13-aminotridecanoic acid, their lactam derivatives, or their acid halides as monomers. By using it, it can introduce | transduce into an aliphatic polyamide resin.

  In the aliphatic polyamide resin used in the present invention, the content of the repeating unit represented by the formula (I) is preferably 50 mol% or more with respect to all the repeating units of the aliphatic polyamide resin, and is 70 mol%. More preferably, it is more preferably 90 mol% or more, and most preferably 100%.

  By setting the content of the repeating unit represented by the formula (I) in the aliphatic polyamide resin within such a range, the cyclic polyolefin resin and the aliphatic polyamide resin can be blended with good compatibility and obtained. The cyclic polyolefin resin composition is excellent in mechanical properties such as impact strength and transparency.

  Among the repeating units represented by the formula (I), those having m of 10 can easily obtain a monomer that gives the repeating unit represented by the formula (I), and the obtained cyclic polyolefin resin composition It is more preferable because the physical properties of the material are excellent.

  For this reason, as the aliphatic polyamide resin used in the present invention, it is particularly preferable to use an aliphatic polyamide resin composed of only a repeating unit represented by the formula (I) where m is 10, that is, polyamide 11.

  In the present invention, the aliphatic polyamide resin is 1 to 100 parts by mass, more preferably 5 to 90 parts by mass, and particularly preferably 10 to 80 parts by mass with respect to 100 parts by mass of the cyclic olefin resin. It is used at a ratio of less than part by mass. By using an aliphatic polyamide resin containing a specific amount of the repeating unit represented by the formula (I) at such a ratio, it is excellent in mechanical properties such as impact strength and transparency, and has a specific gravity of 1.02 or more and 1.04. A cyclic polyolefin resin composition excellent in the following and lightweight properties is obtained.

  The aliphatic polyamide resin that can be used in the present invention is a cyclic olefin measured by a capillary rheometer using an orifice having an inner diameter of 1 mm and a length of 10 mm under the conditions of a measurement temperature of 200 ° C. and a shear rate of 1216 / sec. The absolute value of the difference between the melt viscosity of the resin and the melt viscosity of the aliphatic polyamide resin measured under the same conditions as the cyclic olefin resin is 50 Pa · sec or less, more preferably 40 Pa · sec or less. Is good.

  By using the aliphatic polyamide resin having such a melt viscosity, the compatibility between the cyclic olefin resin and the aliphatic polyamide resin can be further improved, and the resulting cyclic polyolefin resin composition has an impact strength and the like. Excellent mechanical properties and transparency.

[Copolymerization component]
The aliphatic polyamide resin used in the present invention is obtained by copolymerizing a monomer that gives a unit represented by the formula (I) with lactam and / or aminocarboxylic acid, or lactam and / or aminocarboxylic acid, and It can be produced by copolymerizing with diamine and dicarboxylic acid.

  Suitable monomers that can be copolymerized with monomers that give units of the formula (I) include lactams or aliphatic aminocarboxylic acids such as ε-caprolactam or 6-aminocaproic acid; tetramethylenediamine, hexamethylenediamine, Examples thereof include aliphatic diamines such as nonamethylene diamine, undecamethylene diamine, and dodecamethylene diamine; and aliphatic dicarboxylic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid.

  The aliphatic polyamide resin used in the present invention includes p-aminobenzoic acid, m-aminobenzoic acid, m-xylylenediamine, p-xylylenediamine, terephthalic acid, isophthalic acid, as long as the object of the present invention is not impaired. Units derived from monomers having an aromatic group such as 2,6-naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, etc. A unit derived from a monomer having an alicyclic group may be included.

  The amount of units derived from a monomer having an aromatic group and / or a unit derived from a monomer having an alicyclic group in the aliphatic polyamide resin used in the present invention is usually based on all repeating units of the aliphatic polyamide resin. On the other hand, it is 10 mol% or less, and more preferably 5 mol% or less.

[Plant-derived material]
As the aliphatic polyamide resin used in the present invention, it is preferable to use a product produced using a plant-derived material as at least a part of the raw material. Since plant-derived raw materials are originally synthesized by plants using carbon dioxide in the atmosphere as a carbon source, compared to aliphatic polyamide resins manufactured using petrochemical products derived from crude oil, etc., aliphatic polyamide resins This is because the influence on the increase in carbon dioxide concentration in the atmosphere during combustion when discarded is small.

  The ratio of the plant-derived material in the raw material of the aliphatic polyamide resin used in the present invention is preferably 50 mol% or more, more preferably 80 mol% or more, particularly 100 mol%, based on the total monomers. preferable.

  In the specification and claims of the present application, the “plant-derived material” is not limited to a compound extracted from a plant as it is, and a biological technique and / or chemistry using a compound extracted from a plant as a raw material. Also included are compounds synthesized by conventional techniques.

  Among the plant-derived materials that can be used as the raw material of the aliphatic polyamide resin used in the present invention, 11-aminoundecanoic acid and 12-, which can be produced from castor oil obtained from castor bean (castor) seeds, are used as raw materials. Examples include aminododecanoic acid. 11-aminoundecanoic acid and 12-aminododecanoic acid may be used as lactams.

  Among these plant-derived materials, 11-aminoundecanoic acid is more preferable because it is not necessary to use a highly toxic cyanide compound in the process for producing plant-derived materials using castor oil as a raw material.

  Hereinafter, a method for producing 11-aminoundecanoic acid from castor oil will be specifically described. First, transglyceride of ricinoleic acid contained in castor oil is transesterified with methanol to obtain methyl ricinoleate, and heptaldehyde and methyl undecylenate can be obtained by thermally decomposing the methyl ricinoleate. The resulting methyl undecylenate is hydrolyzed to undecylenic acid, hydrogen bromide is added to undecylenic acid and then reacted with ammonia to obtain 11-aminoundecanoic acid.

  12-aminododecanoic acid can be produced from castor oil by the following method. First, undecylenic acid is produced in the same manner as in the method for producing 11-aminoundecanoic acid. Next, after adding hydrogen bromide to undecylenic acid, a cyanide compound such as potassium cyanide is reacted to obtain 11-cyanoundecanoic acid. 12-aminododecanoic acid is obtained by hydrogenating the obtained 11-cyanoundecanoic acid using a palladium catalyst or the like.

[Other ingredients]
In the present invention, the aliphatic polyamide resin may be used as a composition blended with other thermoplastic resins in the range and the amount in a range that does not impair the object of the present invention. Further, in the present invention, the aliphatic polyamide resin is a filler, an antioxidant, a weathering stabilizer, an ultraviolet absorber, an antibacterial agent, a flame retardant, and a colorant in a range and type that do not impair the object of the present invention. You may use what contains various additives, such as.

[Other ingredients]
The cyclic olefin-based resin composition of the present invention may contain, in addition to the cyclic olefin-based resin and the aliphatic polyamide resin, other thermoplastic resins of a type and amount that do not impair the object of the present invention.

  The cyclic olefin resin composition of the present invention includes various fillers, antioxidants, weathering stabilizers, ultraviolet absorbers, antibacterial agents, flame retardants, colorants and the like in addition to the cyclic olefin resins and aliphatic polyamide resins. These additives may be included. These additives may be melt-kneaded together with a cyclic olefin resin and an aliphatic polyamide resin to form a cyclic olefin resin composition. The cyclic olefin resin composition processed into pellets, flakes, powders, etc. It may be attached to the surface.

<Method for Producing Cyclic Olefin Resin Composition>
The production method of the cyclic olefin resin composition in the present invention is not particularly limited as long as the cyclic olefin resin and the aliphatic polyamide resin can be satisfactorily kneaded, and various conventionally known methods for kneading various resins are used. Can do.

  As an example of the suitable manufacturing method of the cyclic olefin resin composition in this invention, the melt-kneading method using a single screw extruder or a twin screw extruder is mentioned. In the melt-kneading method using a single screw extruder or twin screw extruder, the cylinder temperature is preferably 170 ° C. or higher and 260 ° C. or lower, and particularly preferably 180 ° C. or higher and 240 ° C. or lower.

<Method for producing molded body>
The manufacturing method of the molded object using the cyclic olefin resin composition of this invention is not specifically limited. The molding conditions and molding method can be appropriately changed according to the physical properties of the cyclic olefin-based resin composition to be used, the shape of the desired molded body, and the like.

  Conventionally known molding methods include, for example, extrusion molding such as extrusion molding and multilayer extrusion molding, injection molding, injection compression molding, and injection molding such as gas assist method injection molding, rotational molding, hot press molding, blow molding, and foaming. Examples of the method include molding. Among these molding methods, it is particularly preferable to use extrusion molding or injection molding.

<Molded body>
The kind of the molded product obtained by molding the cyclic olefin-based resin composition of the present invention is not particularly limited, and for example, it can be molded into an injection molded product, a film, a sheet, a tube, a pipe, a bottle, and the like. The molded product obtained by molding the cyclic olefin-based resin composition of the present invention is excellent in mechanical properties such as impact strength, transparency and lightness, and is inherent in the cyclic olefin resin such as chemical resistance and moisture resistance. The excellent properties are not impaired.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<Material>
Cyclic olefin-based resin A: TOPAS 9506F-04 (manufactured by Topas Advanced Polymers), glass transition point 65 ° C.
Cyclic olefin resin B: TOPAS8007F-04 (Topas Advanced Polymers Polyplastics Co., Ltd.), glass transition point 78 ° C.
Cyclic olefin resin C: TOPAS 6013F-04 (Topas Advanced Polymers), glass transition point 128 ° C.
Cyclic olefin resin D: TOPAS 5013S-04 (Topas Advanced Polymers), glass transition point 138 ° C.
Polyamide A: Polyamide 11 (manufactured by Arkema Co., Ltd., Rilsan BMNO), castor oil derivative polyamide B: Polyamide 6 (manufactured by Ube Industries, Ltd., UBE nylon 6 1015B)

  Melt viscosity of each material measured using a capillary rheometer (manufactured by Toyo Seiki Seisakusho Co., Ltd., Capillograph) using an orifice with an inner diameter of 1 mm and a length of 10 mm under the conditions of a measurement temperature of 200 ° C. and a shear rate of 1216 / sec. Is shown in Table 1.

<Example 1, Example 2, and Comparative Examples 1 to 4>
At the cylinder temperature described in Table 2, the cyclic olefin-based resin and the polyamide described in Table 2 are mixed at a cylinder temperature described in Table 2 using a twin screw extruder (manufactured by Nippon Steel Works, Ltd., TEX-30α). A cyclic olefin resin composition was produced by melt-kneading.

  About the obtained cyclic olefin system resin composition, the measurement of Charpy impact strength, visual evaluation of transparency, and the measurement of specific gravity were performed. Charpy impact strength was measured according to ISO 179 / 1eA. Further, the visual evaluation of the transparency is the visibility when a 10 mm × 80 mm surface of a Charpy impact strength test piece of size 10 mm × 80 mm × 4 mm is placed on a paper surface on which characters (size, 2 mm × 2 mm) are printed. Evaluated. Furthermore, the specific gravity was measured by the volume of the test piece (measured by the increase in immersion in water) and the weight of the test piece. Table 2 shows the evaluation results of Charpy impact strength, visual visibility and specific gravity.

  From Table 2, Examples 1 and 2 using a cyclic polyolefin resin having a Tg of 50 ° C. or more and 100 ° C. or less and a polyamide 11 composed only of repeating units represented by the formula (I) where m is 10 The cyclic polyolefin-based resin composition of the present invention was found to have significantly improved Charpy impact strength, excellent visual transparency, and a low specific gravity of 1.02.

  On the other hand, the cyclic polyolefin resin compositions of Comparative Examples 1, 2, and 4 using a cyclic polyolefin resin having a Tg exceeding 100 ° C. all showed little improvement in Charpy impact strength. Further, in the cyclic polyolefin resin composition of Comparative Example 3 using a cyclic polyolefin resin having a Tg of 50 ° C. or more and 100 ° C. or less and a polyamide 6 not containing the repeating unit represented by the formula (I), Charpy impact strength is obtained. Although somewhat improved, the visual transparency was not sufficient and the specific gravity was as high as 1.05.

Claims (7)

A cyclic olefin resin having a glass transition point of 50 ° C. or more and 100 ° C. or less, and a repeating unit represented by the following formula (I) of 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the cyclic olefin resin. A cyclic olefin-based resin composition comprising an aliphatic polyamide resin containing 50 mol% or more of all repeating units.
—NH— (CH ₂ ) _m —CO— (I)
[In the formula (I), m is an integer of 9 or more and 12 or less. ]   Absolute value of the difference between the melt viscosity of the cyclic olefin resin measured at a measurement temperature of 200 ° C. and a shear rate of 1216 / sec and the melt viscosity of the aliphatic polyamide resin measured under the same conditions as the cyclic olefin resin. The cyclic olefin-based resin composition according to claim 1, wherein is 50 Pa · sec.   The cyclic olefin-based resin composition according to claim 1 or 2, wherein the aliphatic polyamide resin is composed of only a repeating unit represented by the formula (I).   The cyclic olefin resin composition according to any one of claims 1 to 3, wherein the aliphatic polyamide resin includes a repeating unit represented by the formula (I) in which m is 10.   The cyclic olefin resin composition according to any one of claims 1 to 4, wherein the aliphatic polyamide resin is composed of only a repeating unit represented by the formula (I) in which m is 10.   The cyclic olefin resin composition according to any one of claims 1 to 5, wherein the specific gravity is 1.02 or more and 1.04 or less.   The cyclic olefin-based resin composition according to any one of claims 1 to 6, wherein the aliphatic polyamide resin is produced using a plant-derived material as at least a part of a raw material.