JP2002012723A - Thermoplastic resin composition and molded article of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition capable of producing moldings excellent in moldability, heat resistance, scratch resistance and in transparency, and moldings of the same. SOLUTION: The thermoplastic resin composition contains (A) a cyclic olefin random copolymer of one or more α-olefins having 2-20 carbons and a cyclic olefin with a specified formula, modified by the graft polymerization of an unsaturated carboxylic acid or its derivative and (B) a polyamide resin. The thermoplastic resin composition is characterized in that the weight ratio of the modified cyclic olefin random copolymer (A) to the polyamide resin (B) or (A)/(B) is 98/2-55/45.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition and a molded article comprising the thermoplastic resin composition. Specifically, the present invention relates to a thermoplastic resin composition containing a modified cyclic olefin random copolymer and a polyamide, capable of producing a molded article excellent in heat resistance, scratch resistance and transparency, and the thermoplastic resin. The present invention relates to a molded article comprising the composition.

[0002]

BACKGROUND OF THE INVENTION Thermoplastic resins, particularly polyamide resins, have been widely used since they can be efficiently processed by extrusion molding, injection molding and the like. Since many polyamide resins are crystalline and have a relatively high melting point, it has been known that a polyamide resin composition having a high heat deformation temperature and excellent heat resistance can be obtained by adding a filler. However, the polyamide resin containing the filler has a problem that the moldability is poor and the physical properties of the molded product are anisotropic.

[0003] On the other hand, a polyamide resin containing no filler has a problem that molding shrinkage is large, heat resistance is inferior, and water absorption is large. By the way, a cyclic olefin having an ethylenic double bond in the ring has polymerizability, and for example, reacts with an α-olefin such as ethylene to obtain a cyclic olefin / α-olefin random copolymer. It has been known.

The applicant of the present application has already reported that the softening temperature (TM
A) has proposed a polyamide resin composition containing a cyclic olefin resin having a temperature of 70 ° C. or higher and having excellent heat resistance and chemical resistance (Patent Nos. 2586598 and 25356).
No. 99, Japanese Patent No. 2692245 and Japanese Patent No. 2975499).

The inventor of the present invention has conducted intensive studies in view of such circumstances, and as a result, a modified cyclic olefin copolymer obtained by modifying a cyclic olefin copolymer having a specific softening temperature, a polyamide, A thermoplastic resin containing
The present inventors have found that a molded article having excellent heat resistance, scratch resistance and transparency can be produced, and have completed the present invention.

[0006]

An object of the present invention is to provide a thermoplastic resin capable of producing a molded article having excellent heat resistance, scratch resistance and transparency, and a molded article obtained by molding the resin. .

[0007]

SUMMARY OF THE INVENTION The thermoplastic resin composition of the present invention comprises (A)
At least one α-olefin having 2 to 20 carbon atoms,
A cyclic olefin-based random copolymer obtained by copolymerizing a cyclic olefin represented by the following formula [1] or [2],
The unsaturated carboxylic acid or its derivative component is used in an amount of 0.0
1 to 30% by weight of graft polymerization, having an intrinsic viscosity [η] of 0.05 to 10 dl measured in decalin at 135 ° C.
/ G, a modified cyclic olefin-based random copolymer (A) containing a modified cyclic olefin-based random copolymer having a softening temperature of 60 ° C. or lower and (B) a polyamide resin.
And the composition ratio of the polyamide resin (B) and (A) / (B)
(Weight ratio) of 98/2 to 55/45;

[0008]

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[In the above formula [1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, R ^{1 to} R ¹⁸ and R ^a and R ^b are Each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group;
R ¹⁵ to R ¹⁸ may also form a monocyclic or polycyclic bonded to each other, and may also be monocyclic or polycyclic have a double bond, also the R ¹⁵ and R ¹⁶ Or R ¹⁷ and R ¹⁸
And may form an alkylidene group],

[0010]

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In the above formula [2], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom, A halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and R ⁹ or R ¹⁰
Is bonded to the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded, either directly or via an alkylene group having 1 to 3 carbon atoms. And when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring].

The cyclic olefin-based random copolymer comprises ethylene and at least one kind having 3 to 20 carbon atoms.
Is a random copolymer of an α-olefin of formula (1) and a cyclic olefin represented by the above formula [1] or [2], wherein 1 to 99 mol% of a structural unit derived from ethylene has 3 to 20 carbon atoms. The structural unit derived from α-olefin is 0
It is also preferable to contain a structural unit derived from a cyclic olefin at a ratio of 1 to 30 mol%.

[0013] In the thermoplastic resin composition of the present invention, the polyamide resin (B) is preferably nylon-6. The molded article of the present invention is characterized by comprising the above-mentioned thermoplastic resin composition of the present invention.

[0014]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the present invention will be described specifically. The thermoplastic resin composition of the present invention contains a modified cyclic olefin-based random copolymer (A) and a polyamide resin (B).

Modified cyclic olefin random copolymer
(A) The modified cyclic olefin-based random copolymer (A) constituting the thermoplastic resin composition of the present invention comprises at least one α-olefin having 2 to 20 carbon atoms and the above-mentioned formula [1] or [2] The unsaturated carboxylic acid or its derivative component is graft-polymerized to a cyclic olefin random copolymer obtained by copolymerizing the cyclic olefin represented by the formula (1).

The modified cyclic olefin random copolymer (A) has at least one structural unit derived from an α-olefin having 2 to 20 carbon atoms. 2 carbon atoms
As the α-olefin of 20, specifically, 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,
2 to 2 carbon atoms such as 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene 20 α-olefins, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1
Cycloolefins such as -cyclohexene, cyclooctene and 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2- Norbornene, 5-isopropyl-2-norbornene, 5-n-butyl-2-norbornene, 5-isobutyl-
Norbornenes such as 2-norbornene, 5,6-dimethyl-2-norbornene, 5-chloro-2-norbornene and 5-fluoro-2-norbornene, 1,4-hexadiene, 4-methyl
-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-
Octadiene, dicyclopentadiene, 5-ethylidene-2
Non-conjugated dienes such as -norbornene and 5-vinyl-2-norbornene.

The modified cyclic olefin-based random copolymer (A) used in the present invention contains structural units derived from these α-olefins alone or in combination of two or more. The modified cyclic olefin-based random copolymer (A) preferably contains at least ethylene among these α-olefins, and has a structural unit derived from ethylene in an amount of 1 to 99 mol% and a carbon number of 3 to 3
The structural units derived from 20 α-olefins are 0 to 69
It is more preferable to contain the structural unit derived from a cyclic olefin described later in a proportion of 1 to 30 mol%.

The modified cyclic olefin-based random copolymer (A) has a structural unit derived from a cyclic olefin represented by the following formula [1] or [2].

[0019]

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In the above formula [1], n is 0 or 1, m is 0 or a positive integer, and q is 0 or 1. When q is 1, the ring represented by q is a 6-membered ring, and when q is 0, the ring is a 5-membered ring.

In addition, R ^{1 to} R ¹⁸ and R ^a and R
^b is each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Examples of the hydrocarbon group usually include an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. be able to.

More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group. These alkyl groups may be substituted with a halogen atom. The cycloalkyl group includes a cyclohexyl group, and the aromatic hydrocarbon group includes a phenyl group and a naphthyl group.

Further, in the above formula [1], R^FifteenAnd R
¹⁶And R¹⁷And R¹⁸And R^FifteenAnd R ¹⁷And R¹⁶And R¹⁸
And R^FifteenAnd R¹⁸And R¹⁶And R¹⁷And each
To form a monocyclic or polycyclic group
It may be formed. Furthermore, formed in this way
Further, the monocyclic or polycyclic ring may have a double bond. here
Specific examples of the monocyclic or polycyclic ring formed by
Such can be mentioned.

[0024]

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In the above examples, carbon atoms numbered 1 or 2 are each represented by R in formula [1].
Represents a carbon atom to which ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) is bonded. Further, R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and examples of such an alkylidene group include:
Ethylidene, propylidene and isopropylidene groups can be mentioned.

[0026]

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In the above formula [2], p and q are 0 or a positive integer, and m and n are 0, 1 or 2. R ^{1 to} R ¹⁹ each independently represent a hydrogen atom,
It is a halogen atom, a hydrocarbon group or an alkoxy group.

Here, the halogen atom has the same meaning as the halogen atom mentioned in the description of the above formula [1]. Examples of the hydrocarbon group usually include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group.

More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group. These alkyl groups may be substituted with a halogen atom. Examples of the cycloalkyl group include a cyclohexyl group, and examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group.Specifically, a phenyl group, a tolyl group, a naphthyl group, a benzyl group and A phenylethyl group can be mentioned.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group. Further, in the formula [2], the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or a carbon atom having 1 carbon atom. And 3 may be bonded via an alkylene group. That is, when the two carbon atoms are bonded via an alkylene group, R ⁹ and R ^{13 represent}
R ¹⁰ and R ^{11 work} together to form a methylene group (—CH
_2- ), ethylene group (-CH ₂ CH _2- ) or propylene group (-
CH ₂ CH ₂ CH ₂ —) to form any alkylene group.

Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Specifically, n = m = 0
In this case, the following aromatic rings formed by R ¹⁵ and R ¹² can be exemplified.

[0032]

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Here, q has the same meaning as q in equation [2]. Specific examples of the cyclic olefin represented by the above formula [1] or [2] include bicyclo [2.
2.1] hept-2-ene derivatives, tetracyclo [4.4.0.1 ^{2, 5} .1
^7,10] -3-dodecene derivatives, hexacyclo [6.6.1.1 ^{3, 6} .1
^10,13 .0 ^2,7 .0 ^9,14] -4-heptadecene derivatives, octacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13,16 .0 3,8 .0 ^12,17] -5-docosene derivatives, pentacyclo ^{[6.6.1.1 3,6 .0 2,7 .0 9,14]} -
4-hexadecene derivative, heptacyclo-5-eicosene derivative, heptacyclo-5-heneicosene derivative, tricyclo [4.3.0.1 ^2,5 ] -3-decene derivative, tricyclo [4.4.0.
1 ^2,5 ] -3-undecene derivative, pentacyclo [6.5.1.1 ^3,6 .
0 ^2,7 .0 ^9,13] -4-pentadecene derivatives, penta cyclopentadiene decadiene derivative, pentacyclo [7.4.0.1 ^2,5 .1 ^9,12.
0 ^8,13] -3-pentadecene derivatives, heptacyclo [8.7.0.1
^3,6 .1 ^10,17 .1 ^12,15 .0 ^2,7 .0 ^11,16] -4-eicosene derivatives, Nonashikuro [10.9.1.1 ^4,7 .1 ^13,20 .1 ^15,18 .0 ^3,8 .0
^2,10 .0 ^12,21 .0 ^14,19] -5-pentacosene derivatives, pentacyclo ^{[8.4.0.1 2,5 .1 9,12 .0 8,13]} -3- hexadecene derivatives, heptacyclo [8.8.0.1 ^4,7 .1 ^11,18 .1 ^13,16 .0 ^3,8 .0
^12,17 ] -5- ^Hyneecocene derivative, nonacyclo [10.10.1.
1 ^5,8 .1 ^14,21 .1 ^16,19 .0 ^2,11 .0 ^4,9 .0 ^{13, 22} .0 ^15,20] -5-hexacosenoic derivatives, 1,4-methano-1,4 , 4a, 9a-tetrahydrofluorene derivatives, 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene derivatives, and cyclopentadiene-acenaphthylene adducts.

More specific examples of the cyclic olefin represented by the above formula [1] or [2] are shown below.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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Among such cyclic olefins, tetracyclododecene, norbornene and derivatives thereof are preferred. The modified cyclic olefin random copolymer (A) has at least one kind of carbon
To an α-olefin and a cyclic olefin-based random copolymer obtained by copolymerizing a cyclic olefin, the unsaturated carboxylic acid or its derivative component is added to 100 parts by weight of the cyclic olefin-based random copolymer before modification. On the other hand, 0.
01 to 30% by weight, preferably 0.01 to 10% by weight,
More preferably, it is obtained by graft polymerization in an amount of 0.1 to 2% by weight.

As the unsaturated carboxylic acid to be graft-polymerized, specifically, acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid,
Citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, nadic acid ^TM (endosis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid), bicyclo [2,2,1] hept And 2-ene-5,6-dicarboxylic acid.

Examples of the unsaturated carboxylic acid derivative to be graft-polymerized include the above-mentioned unsaturated carboxylic acid acid halide compounds, amide compounds, imide compounds, acid anhydrides, and ester compounds. Specifically, maleenyl chloride, maleenyl imide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-
Dicarboxylic anhydride, dimethyl maleate, maleic
Monomethyl dimethyl, dimethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citrate, dimethyl tetrahydrophthalate, dimethyl bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylate, Glycidyl maleate, hydroxyethyl (meth)
Acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate, aminopropyl methacrylate and the like can be mentioned.

Of these, maleic anhydride is particularly preferred. In the above cyclic olefin-based random copolymer,
As a method of obtaining a modified cyclic olefin-based random copolymer (A) by graft-polymerizing these unsaturated carboxylic acids or derivatives thereof, any of conventionally known methods can be used. A method in which the system random copolymer is melted or dissolved in a solvent, and an unsaturated carboxylic acid or the like is added to perform graft polymerization.

In these methods, when the graft polymerization is carried out in the presence of a radical initiator, the above unsaturated carboxylic acid or its derivative component can be efficiently graft-polymerized. In this case, the radical initiator is based on 100 parts by weight of the cyclic olefin-based random copolymer.
Usually, it is used in an amount of 0.001 to 1 part by weight.

As the radical initiator, organic peroxides, azo compounds and the like are used. As such a radical initiator, specifically, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-
Di (peroxidebenzoate) hexyne-3,1,4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperacetate, 2,5-dimethyl-2,5-di- (t-butylperoxide) Hexin-3, 2,
5-dimethyl-2,5-di (t-butyl peroxide) hexane, t-butyl perbenzoate, t-butyl perphenyl acetate, t-butyl perisobutyrate, t-butyl per-sec-octoate, t-butyl per Pivalate, cumyl perpivalate, t-butyl perdiethyl acetate;
Examples include azobisisobutyronitrile and dimethylazoisobutyrate.

Of these, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5
Dialkyl peroxides such as -di (t-butylperoxy) hexane and 1,4-bis (t-butylperoxyisopropyl) benzene are preferably used.

The reaction temperature of the graft polymerization reaction using a radical initiator as described above or the graft polymerization reaction carried out without using a radical initiator is usually 60 to 30.
The temperature is set at 0 ° C, preferably within the range of 80 to 230 ° C.

The modified cyclic olefin-based random copolymer (A) used in the present invention has an intrinsic viscosity [η] measured in decalin at 135 ° C. of 0.05 to 10 dl / g, preferably 0.3 to 4. It is desirably 0 dl / g, and the softening temperature is desirably 60 ° C or lower, preferably -10 to 50 ° C.

In the present invention, by using such a modified cyclic olefin random copolymer (A), it is possible to prepare a thermoplastic resin having excellent heat resistance, scratch resistance and transparency. A composition is obtained.

Polyamide Resin (B) As the polyamide resin (B) constituting the thermoplastic resin composition of the present invention, polymerizable aminocarboxylic acids or their lactams, dicarboxylic acids, diamines and the like are used as raw materials. Any of those obtained by ring-opening polymerization or polycondensation can be used.

Specific examples of the aminocarboxylic acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. In addition, these amino acids are 2
Mixtures of more than one species can also be used.

Examples of the lactam include valerolactam, caprolactam, enantholactam, caprylactam, laurolactam, and the like. Of these, caprolactam and laurolactam are preferably used. Most preferred is the use of caprolactam. In addition, these lactams can also be used in a mixture of two or more.

Examples of the dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, and tridecanedioic acid. acid,
Aliphatic dicarboxylic acids such as tetradecandioic acid, pentadecandioic acid and octadecandioic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; phthalic acid, isophthalic acid;
And aromatic dicarboxylic acids such as terephthalic acid and naphthalenedicarboxylic acid. In addition, these dicarboxylic acids can be used in a mixture of two or more.

Specific examples of the diamines include 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 2-methyl-1,5-diaminopentane (MDP),
1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosan And the like. Aliphatic diamines such as cyclohexanediamine and bis- (4-aminohexyl) methane; aromatic diamines such as xylylenediamine; These diamines can also be used in a mixture of two or more.

The molecular weight of the polyamide resin is not particularly limited, but preferably has a relative viscosity of 2.0 to 4.0 measured at 23 ° C. and 98% sulfuric acid at a concentration of 1 g / 100 ml.
It is more preferably 2.1 to 3.8, and particularly preferably 2.2 to 3.6. 2.0 relative viscosity
If less than the above, mechanical properties may be reduced, while
If it exceeds 4.0, the fluidity during molding tends to decrease.

The polyamide resin may be one whose terminal is blocked by a carboxylic acid compound or an amine compound, if necessary. When the terminal is blocked by a monocarboxylic acid and / or a monoamine, the concentration of the terminal amino group and the terminal carboxyl group of the obtained polyamide resin (hereinafter simply referred to as “terminal group concentration”) is lower than that before the terminal blocking. descend. On the other hand, when the terminal is blocked with a dicarboxylic acid or a diamine, the ratio of the terminal amino group concentration to the terminal carboxyl group concentration changes while the terminal group concentration does not change.

Specific examples of the carboxylic acid compound used for terminal blocking of the polyamide resin include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, undecanoic acid, lauric acid, and tridecanoic acid. Aliphatic monocarboxylic acids such as myristic acid, myristoleic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, and arachiic acid; cycloaliphatic monocarboxylic acids such as cyclohexanecarboxylic acid and methylcyclohexanecarboxylic acid; benzoic acid; Aromatic monocarboxylic acids such as toluic acid, ethylbenzoic acid and phenylacetic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecane diacid Acid, tridecandioic acid, tetradecandioic acid, pentadecandioic acid Aliphatic dicarboxylic acids such as octadecanedioic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, and aromatic dicarboxylic acids such as naphthalene dicarboxylic acid.

Specific examples of the amine compound used for blocking the terminal of the polyamide resin include butylamine, pentylamine, hexylamine, peptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine and tridecyl. Amines, tetradecylamine, pentadecylamine,
Aliphatic monoamines such as hexadecylamine, octadecylamine, nonadecylamine and icosylamine; alicyclic monoamines such as cyclohexylamine and methylcyclohexylamine; aromatic monoamines such as benzylamine and β-phenylethylamine; 1,4-diaminobutane; ,Five-
Diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane , 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentatecan, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19- Aliphatic diamines such as diaminononadecane and 1,20-diaminoeicosane; alicyclic diamines such as cyclohexanediamine and bis- (4-aminohexyl) methane; and aromatic diamines such as xylylenediamine.

As the polyamide resin (B) constituting the thermoplastic resin composition of the present invention, these polyamide resins may be used alone or in combination of two or more. Specific examples of the polyamide resin (B) include aliphatic amide resins such as nylon-6, nylon-66, nylon-10, nylon-12, and nylon-46, and those produced from aromatic dicarboxylic acids and aliphatic diamines. Aromatic amide resin and the like can be preferably used.
Nylon-6 can be particularly preferably used.

Thermoplastic Resin Composition The thermoplastic resin composition of the present invention contains the modified cyclic olefin random copolymer (A) and the polyamide resin (B), and comprises a modified cyclic olefin random copolymer. The composition ratio of the copolymer (A) and the polyamide resin (B) is (A) / (B) (weight ratio): 98/2 to 55/45,
Preferably 95/5 to 60/40, more preferably 90
/ 10 to 65/35.

The thermoplastic resin composition of the present invention comprises a modified cyclic olefin-based random copolymer (A),
In addition to the polyamide resin (B), if necessary, add additives such as antioxidants, ultraviolet absorbers, weather stabilizers, heat stabilizers, antistatic agents, flame retardants, pigments, dyes, fillers, etc. It can be blended within a range that does not impair the object of the invention.

Further, the thermoplastic resin composition according to the present invention may be blended with another polymer such as an unmodified cyclic olefin random copolymer within a range not to impair the object of the present invention. .

Examples of the filler that can be blended in the thermoplastic resin composition of the present invention include carbon black, asbestos, talc, silica, silica alumina and the like.

The thermoplastic resin composition according to the present invention comprises the above-mentioned modified cyclic olefin-based random copolymer (A), polyamide resin (B) and, if necessary, additives and the like. Can be prepared by melt-mixing according to a conventionally known method.

That is, in the thermoplastic resin composition according to the present invention, the above-mentioned components are simultaneously or sequentially charged and mixed in, for example, a Henschel mixer, a V-type blender, a tumbler mixer, a ribbon blender, and the like. It can be prepared by melt-kneading with a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer or the like.

Among these, multi-screw extruders, kneaders,
When a device having excellent kneading performance such as a Banbury mixer is used, a high-quality thermoplastic resin composition in which each component is more uniformly dispersed can be obtained.

At any of these stages, the above additives, such as antioxidants, can be added as necessary. The thermoplastic resin composition according to the present invention obtained as described above preferably has a haze value of 65% or less when the molded article is prepared at a thickness of 1 mm when the molded article is prepared.

The thermoplastic resin composition according to the present invention obtained as described above can be used as a floor material, a wallpaper material, a coating material, a decorative sheet, a pipe, a tube, an artificial leather, a sheet, an agricultural film, a wrap film, a hose. , Bottles and the like.

Molded article The molded article according to the present invention is prepared by using the above-mentioned thermoplastic resin composition according to the present invention and various conventionally known melt molding methods such as extrusion molding, rotational molding, calender molding, injection molding, and the like.
It can be obtained by molding into various shapes by a method such as compression molding or blow molding.

[0086]

The thermoplastic resin according to the present invention is excellent in moldability and can produce a molded article excellent in heat resistance, scratch resistance and transparency. Further, the molded article of the present invention is excellent in heat resistance, scratch resistance and transparency.

[0087]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

In the examples of the present invention, various physical properties were measured by the following methods. (1) Martens hardness (scratch resistance) Using a Martens hardness and scratch hardness tester manufactured by Tokyo Ikki Co., Ltd., a load of 20 g of a scratch indenter was applied to a 3 mm-thick test piece to determine the groove width generated when the sample was scratched. It measured and calculated the reciprocal, and made the value into Martens hardness (1 / mm). (2) TMA: needle penetration temperature (heat resistance) According to JIS K7196, 2 kg / cm is applied to a flat indenter having a diameter of 1.8 mm and a diameter of 1.8 mm using a test piece having a thickness of 2 mm at a heating rate of 5 ° C./min. The pressure of ² was applied, and the needle penetration temperature (° C.) was determined from the TMA curve. (3) Haze (Transparency) The haze (transparency) was measured with a digital turbidimeter “NDH-20D” manufactured by Nippon Denshoku Industries Co., Ltd. using a test piece having a thickness of 1 mm.

The cyclic olefin-based polymer, modified cyclic olefin-based random copolymer and polyamide resin used in Examples and Comparative Examples are as follows. (1) Ethylene-propylene-tetracyclododecene copolymer (COC-1) Tetracyclododecene content: 11.4 mol% Propylene content: 14.5 mol% Ethylene content: 73.7 mol% Intrinsic viscosity [η ]: 1.15 dl / g TMA: 10 ° C (2) Ethylene-propylene-norbornene copolymer (COC-2) Norbornene content: 14.4 mol% Propylene content; 10.5 mol% Ethylene content: 75.1 mol % Intrinsic viscosity [η]: 1.20 dl / g TMA: −5 ° C. (3) Modified ethylene-propylene-tetracyclododecene copolymer (M-COC-1) Tetracyclododecene content: 11.6 mol% Propylene content: 14.7 mol% Ethylene content: 73.7 mol% Intrinsic viscosity [η]: 1.24 dl / g TMA: 12 ° C None Maleic acid (MAH) graft amount: 0.2% by weight (4) Modified ethylene-propylene-norbornene copolymer (M-COC-2) Norbornene content: 14.4 mol% Propylene content; 10.5 mol% Ethylene content : 75.1 mol% Intrinsic viscosity [η]: 1.24 dl / g TMA: -3 ° C Maleic anhydride (MAH) graft amount: 1% by weight (5) Polyamide resin Nylon-6 (Ny-6): Toray ( CM1
007

[0090]

Example 1 70 parts by weight of a modified ethylene-propylene-tetracyclododecene copolymer (M-COC-1) and 30 parts by weight of nylon-6 (Ny-6) were mixed using a small Banbury mixer. And melt kneading at a set temperature of 225 ° C.

Next, using the obtained melt-kneaded material, press molding was performed at 230 ° C. to obtain a test piece having a thickness used in the method for measuring the above-mentioned physical properties. With respect to the obtained molded body (test piece), Martens hardness (index of scratch resistance), TMA (index of heat resistance), and haze (index of transparency) were measured by the methods described above. Table 1 shows the results.

[0092]

Example 2 35 parts by weight of an ethylene-propylene-tetracyclododecene copolymer (COC-1) and a modified ethylene-propylene-tetracyclododecene copolymer (M-
35 parts by weight of COC-1) and nylon-6 (Ny-6)
30 parts by weight were melt-kneaded at a set temperature of 225 ° C. using a small Banbury mixer. Next, the obtained melt-kneaded product was molded in the same manner as in Example 1, and various physical properties were measured. Table 1 shows the results.

[0093]

Example 3 63 parts by weight of an ethylene-propylene-tetracyclododecene copolymer (COC-1) and a modified ethylene-propylene-tetracyclododecene copolymer (M-
7 parts by weight of COC-1) and nylon-6 (Ny-6) 3
0 parts by weight was melt-kneaded at a set temperature of 225 ° C. using a small Banbury mixer. Next, the obtained melt-kneaded product was molded in the same manner as in Example 1, and various physical properties were measured. Table 1 shows the results.

[0094]

Example 4 35 parts by weight of a modified ethylene-propylene-norbornene copolymer (M-COC-2) and ethylene-propylene-norbornene copolymer
Propylene-norbornene copolymer (COC-2) 35
Parts by weight and 30 parts by weight of nylon-6 (Ny-6)
The mixture was melt-kneaded at a set temperature of 225 ° C. using a small Banbury mixer. Next, the obtained melt-kneaded material was used in Example 1
, And various physical properties were measured. Table 1 shows the results
Shown in

[0095]

COMPARATIVE EXAMPLE 1 An ethylene-propylene-tetracyclododecene copolymer (COC-1) was press-molded at 230 ° C. to obtain a test piece having a thickness used in the above-mentioned methods for measuring physical properties. Using the obtained molded body (test piece), various physical properties were measured in the same manner as in Example 1. Table 1 shows the results.

[0096]

Comparative Example 2 An ethylene-propylene-norbornene copolymer (COC-2) was press-molded at 230 ° C. to obtain a test piece having a thickness used in the method for measuring the above-mentioned physical properties. Using the obtained molded body (test piece), various physical properties were measured in the same manner as in Example 1. Table 1 shows the results.

[0097]

Comparative Example 3 70 parts by weight of an ethylene-propylene-tetracyclododecene copolymer (COC-1) and nylon-
6 (Ny-6) and 30 parts by weight were melt-kneaded at a set temperature of 225 ° C. using a small Banbury mixer. Next, the obtained melt-kneaded product was molded in the same manner as in Example 1, and various physical properties were measured. Table 1 shows the results.

[0098]

Comparative Example 4 70 parts by weight of an ethylene-propylene-norbornene copolymer (COC-2) and nylon-6 (Ny
-6) 30 parts by weight were melt-kneaded at a set temperature of 225 ° C. using a small Banbury mixer. Next, the obtained melt-kneaded product was molded in the same manner as in Example 1, and various physical properties were measured. Table 1 shows the results.

[0099]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 232/08 C08F 232/08 255/00 255/00 C08J 5/00 CES C08J 5/00 CES // ( C08L 23/26 (C08L 23/26 77:00) 77:00) F term (reference) 4F071 AA14 AA14X AA15 AA15X AA20 AA20X AA31 AA36 AA76 AA77 AA78 AB03 AB18 AB26 AB30 BA01 BB03 BB04 BB05 BB06 BC05 BC03 BC04 BC05 BC03 BC04 BC05 BB201 BB211 CL002 CL012 CL032 CL052 FD010 4J026 AA11 AA12 AA13 AA14 BA24 BA25 BA26 BA27 BA32. AU21Q BA04Q BA05Q BA06Q BA16H BB01P BB01Q BB03Q BB05Q BB07P BB07Q BC04Q BC43Q BC44Q BC48Q BC49Q BC55H CA04 CA05 CA31 HA57 HA6 1 HC29 HC30 HC34 HC39

Claims (4)

[Claims] (A) A cyclic olefin random copolymer obtained by copolymerizing at least one α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by the following formula [1] or [2]: An unsaturated carboxylic acid or a derivative thereof is added to the polymer in an amount of 0.0
1 to 30% by weight of graft polymerization, having an intrinsic viscosity [η] of 0.05 to 10 dl measured in decalin at 135 ° C.
/ G, a modified cyclic olefin-based random copolymer having a softening temperature of 60 ° C. or lower, and (B) a polyamide resin, wherein the modified cyclic olefin-based random copolymer (A) and the polyamide resin (B) And the composition ratio is (A)
/ (B) (weight ratio): 98/2 to 55/45; thermoplastic resin composition; [In the above formula [1], n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸
And R ^a and R ^b are each independently a hydrogen atom,
R ^{15 to} R ¹⁸ are a halogen atom or a hydrocarbon group,
May combine with each other to form a monocyclic or polycyclic ring,
And the monocyclic or polycyclic ring may have a double bond,
And R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group], [In the above formula [2], p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ^{1 to} R
¹⁹ is each independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and a carbon atom to which R ⁹ or R ¹⁰ is bonded; , R ¹³ is bonded to a carbon atom or R ¹¹
May be bonded directly or via an alkylene group having 1 to 3 carbon atoms. Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ R ¹⁹
May combine with each other to form a monocyclic or polycyclic aromatic ring]. 2. The method according to claim 1, wherein the cyclic olefin-based random copolymer comprises ethylene and at least one kind having 3 to 20 carbon atoms.
Is a random copolymer of an α-olefin of formula (1) and a cyclic olefin represented by the above formula [1] or [2], wherein 1 to 99 mol% of a structural unit derived from ethylene has 3 to 20 carbon atoms. The structural unit derived from α-olefin is 0
2. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition contains 1 to 30 mol% of a structural unit derived from a cyclic olefin. 3. The polyamide resin (B) is a nylon resin.
6. The thermoplastic resin composition according to claim 1, wherein the composition is 6. 4. A molded article comprising the thermoplastic resin composition according to claim 1.