JPH07109419A - Cycloolefinic resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition reduced in water absorption and excellent in transparency, impact resistance, etc., by mixing a specific cycloolefinic resin modified by grafting, a specific elastomer, a polymer obtained by modifying the elastomer by grafting, a polyamide, and an iridescent mica pigment. CONSTITUTION:This resin composition comprises 0.5-50 pts.wt. resin (a) obtained by graft-modifying a cycloolefinic resin selected from a random copolymer of ethylene with a cycloolefin represented by the formula (wherein (n) and (q) each is 0 or 1; (m) is 0 or a positive integer; and R<1> to R<18>, R<a>, and R<b> each independently is H, a hydrocarbon group, etc.), a polymer (A) produced by the ring-opening (co)polymerization of the cycloolefin, and a hydrogenation product of the polymer (A); 0-38 pts.wt. elastomer (b) having a tensile modulus at 23 deg.C of 0.1-2,000kg/cm<2>, a glass transition temp. of 0 deg.C or lower, and a crystallinity of 30% or lower; 0-38 pts.wt. polymer (c) obtained by modifying the elastomer (b) by grafting; and 40-90 pts.wt. polyamide resin (d), provided that the sum of the components (a) to (b) is 100 pts.wt. The resin composition further contains 0.01-10 pts.wt. iridescent mica pigment per 100 pts.wt. the components (a) to (d).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a cyclic olefin resin composition whose surface appearance has a deep and transparent feeling similar to that of a clear topcoat, and which has low water absorption and excellent impact resistance and dimensional stability. Regarding things.

[0002]

2. Description of the Related Art Polyolefins such as polypropylene and polyethylene which have been conventionally used, and polyamide 6
And polyamide resin such as polyamide 66 or AB
Thermoplastic resins such as S may be painted to improve the appearance. At this time, the coating can give a glossy coloring by the paint and can impart a colorless and glossy and deep transparency like a clear top coat.

However, painting requires a lot of steps and requires a solvent, so that special equipment is required.
There is a problem of high cost. Therefore, it is required to devise a resin composition alone to provide a glossy, deep and transparent appearance without applying a paint finish.

By the way, in Japanese Examined Patent Publication No. 4-74384,
A thermoplastic resin composition having a pearl color tone in which a pearl mica pigment is mixed with a thermoplastic resin such as polyethylene, polypropylene and polyamide resin is disclosed. However, although this resin composition exhibits a pearl color tone and has some transparency, it does not provide a deep transparent feeling as when a clear top coat is overcoated, and it has low water absorption and excellent impact resistance. I can't get anything.

Further, Japanese Patent Laid-Open No. 5-93091 discloses a thermoplastic resin composition having a metallic feeling, which is obtained by mixing aluminum powder having an aspect ratio of 10 to 100 and pearl mica pigment in a thermoplastic resin. However, although this resin composition improves the appearance of the resin in a metallic manner, it does not give a transparent appearance, and it does not give a good-looking appearance having a deep transparent appearance like a clear topcoat is overcoated. . Further, it is not possible to obtain a product having low water absorption and excellent impact resistance.

On the other hand, it is known that a resin composition excellent in low water absorption, impact resistance and dimensional stability can be obtained by blending a graft-modified cyclic olefin resin, a polyamide resin and optionally an elastomer. (For example, JP-A-4-226147 and JP-A-5-935.
No. 0). However, it has been necessary to apply a top coat in order to impart a glossy and deep transparent feeling to such a resin composition.

[0007]

DISCLOSURE OF THE INVENTION The present invention has a surface appearance that has a glossy and deep transparent feeling similar to that of a clear topcoat overcoating, has a good appearance, and has low water absorption, impact resistance and size. It is an object of the present invention to provide a cyclic olefin resin composition having excellent stability.

[0008]

The present invention is the following cyclic olefin resin composition. (1) (a) Ethylene comprising a random copolymer of ethylene and a cyclic olefin represented by the following general formula [1]:
Cyclic olefin random copolymer (a-1) and ring-opening (co) of a cyclic olefin represented by the following general formula [1]
A graft-modified cycloolefin resin obtained by graft-modifying one or more cycloolefin resins selected from the group consisting of a polymer or a hydrogenated product thereof (a-2) with a graft monomer, and (b) a tensile modulus at 23 ° C. An elastomer having a glass transition temperature of 0 ° C. or lower and a crystallinity of 30% or lower in the range of 0.1 to 2000 kg / cm ² , and (c) a tensile modulus at 23 ° C. of 0.1 to A graft-modified elastomer obtained by graft-modifying the elastomer (b) having a glass transition temperature of 0 ° C. or lower and a crystallinity of 30% or lower in the range of 2000 kg / cm ² ;
A resin composition comprising (d) a polyamide resin and (e) a pearl mica pigment, comprising: (a) component, (b) component,
0.5 to 50 parts by weight of the component (a) and 0 of the component (b) per 100 parts by weight of the components (c) and (d) in total.
To 38 parts by weight, the component (c) is 0 to 38 parts by weight, the component (d) is 40 to 90 parts by weight, and the total of (a) to (d) is 1
0.01 parts of pearl mica pigment (e) to 100 parts by weight
A cyclic olefin resin composition containing 10 to 10 parts by weight.

[Chemical 2] (In the formula, 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 each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic group. And the monocyclic or polycyclic group may have a double bond, and R ¹⁵ and R
^An alkylidene group may be formed with ¹⁶ or with R ¹⁷ and R ¹⁸ . When q is 0, respective bonds bond to form a 5-membered ring. (2) The softening temperature (TMA) of the graft-modified cycloolefin resin (a) is 70 ° C. or higher, and the intrinsic viscosity [η] measured in decalin at 130 ° C. is 0.01 to 10 dl.
It is in the range of / g, The cyclic olefin resin composition as described in (1) above. (3) The graft-modified cyclic olefin-based resin (a) is a mixture of an unmodified cyclic olefin-based resin and a graft-modified cyclic olefin-based resin, and the cyclic olefin according to (1) or (2) above. -Based resin composition. (4) The total amount of the elastomer (b) and the graft modified elastomer (c) is 0.5 to 38 parts by weight, and the cyclic olefin according to any one of (1) to (3) above. -Based resin composition.

In the present invention, "(co) polymer" means "homopolymer or copolymer". Below (a)
Each component (e) will be described. The graft-modified cyclic olefin resin (a) used in the present invention is (a-
1) Ethylene composed of an ethylene component unit and a component unit derived from the cyclic olefin represented by the above formula [1].
Cyclic olefin random copolymer, and (a-2) Ring-opening polymer or ring-opening copolymer (cyclic olefin ring-opening polymer) of the cyclic olefin represented by the above formula [1], or hydrogenated product thereof ( It is a graft-modified product obtained by modifying one or more cyclic olefin resins selected from hydrogenated ring-opening polymers) with a graft monomer.

As the graft modified cyclic olefin resin (a), the above graft modified products can be used alone or in combination. Further, the graft modified cyclic olefin resin may be a mixture of a graft modified cyclic olefin resin and an unmodified cyclic olefin resin.

Next, the cyclic olefin resin before graft modification will be described. The softening temperature (TMA) of the cyclic olefin-based resin measured by a thermal mechanical analyzer is 70 ° C or higher, preferably 70 to 200 ° C,
More preferably, a temperature of 100 to 180 ° C. is desirable.
The softening temperature (TMA) is 1.0 mm in diameter on the sheet.
The quartz needle is placed, a load of 50 g is applied, the temperature is raised at 5 ° C./min, and the temperature is the temperature at which the needle enters 100 μm.

The cyclic olefin resin has an intrinsic viscosity [η] of 0.01 to 10 measured in decalin at 135 ° C.
dl / g, preferably 0.05 to 10 dl / g, more preferably 0.3 to 2.0 dl / g, still more preferably 0.4 to 1.2 dl / g. Furthermore, this cyclic olefin resin has a glass transition point (Tg) of usually 30 ° C. or higher, preferably 40 to 170 ° C., and a crystallinity measured by an X-ray diffraction method of usually 0 to 20%, preferably 0 to 2% is preferable.

In the cyclic olefin represented by the above formula [1] used for forming the cyclic olefin resin as described above, R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom. Represents an atom or a group selected from the group consisting of a halogen atom and a hydrocarbon group.

Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. As the hydrocarbon group, each independently, usually, the number of carbon atoms is 1 to
Examples thereof include an alkyl group having 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. 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. A group in which at least a part of hydrogen atoms forming an alkyl group as described above is substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom can be given.

Examples of the cycloalkyl group include a cyclohexyl group, and examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Further, in the above formula [1], R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ are R
¹⁵ and R ¹⁷ , R ¹⁶ and R ¹⁸ , R ¹⁵ and R ¹⁸ , or R ¹⁶ and R ¹⁷ are bonded to each other (in cooperation with each other) to form a monocyclic or polycyclic ring. And the monocycle or polycycle thus formed may have a double bond. Specific examples of the monocycle or polycycle formed here include the following.

[0016]

[Chemical 3]

In the above example, the carbon atoms numbered 1 or 2 are each R in the formula [1].
^It 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 specific examples of such an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.

The preferred cyclic olefin of the above formula [1] is a cyclic olefin represented by the following general formula [1-1].

[Chemical 4] (In the formula [1-1], n, m, and R ^{1 to} R ¹⁸ are the same as those in the formula [1].)

Furthermore, examples of the cyclic olefin represented by the above formula [1] include compounds represented by the following general formula [2].

[Chemical 5] (In the formula [2], h is 0 or a positive integer, and j
And k is 0, 1 or 2. m, R ^{7 to} R ¹⁵ and R ^{17 to} R ¹⁸ are the same as those in formula [1]. R ^{19 to} R ²⁷
Each independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and an alkoxy group. )

Here, the halogen atom is the same as the halogen atom in the above formula [1]. Further, R ^{19 of the} formula [2]
The hydrocarbon group for R ²⁷ is usually, independently of each other, 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 or an aromatic group. Examples include hydrocarbon groups. 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. ,
Examples thereof include groups in which at least a part of hydrogen atoms forming an alkyl group as described above are substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine 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. Specific examples include a phenyl group, a tolyl group, a naphthyl group and a benzyl group. , Phenylethyl group and the like.

Examples of the alkoxy group include a methoxy group, an ethoxy group and a propoxy group. Where R ¹⁷
And the carbon atom to which R ¹⁸ is bonded and the carbon atom to which R ²¹ is bonded or the carbon atom to which R ¹⁹ is bonded are bonded directly or via an alkylene group having 1 to 3 carbon atoms. May be. That is, when the above two carbon atoms are bonded via an alkylene group, the groups represented by R ¹⁷ and R ²¹ or the groups represented by R ¹⁸ and R ¹⁹ cooperate with each other. Te, a methylene group (-CH ₂ -), ethylene group (-CH ₂ CH ₂ -) or trimethylene group (-
CH ₂ CH ₂ CH ₂ —) forms any alkylene group.

Further, when j = k = 0, R ²³ and R ²⁰ or R ²³ and R ²⁷ may combine with each other to form a monocyclic or polycyclic aromatic ring. In this case, examples of the monocyclic or polycyclic aromatic ring include R ²³ and R when j = k = 0.
Examples thereof include the groups described below in which ²⁰ further forms an aromatic ring.

[0024]

[Chemical 6]

In the above example, h represents the same as h in the formula [2]. The above formulas [1], [1-
As the cyclic olefin represented by 1] or [2],
Specifically, bicyclo [2. 2. 1] hept-2-ene derivatives, tetracyclo [4.4.1 .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 [8.8.3 .1 ^2,9. 1 ^4,7. 1 ^{11, 18.} 1 ^13,16. 0 ^3,8. 0
^12,17 ] -5-dococene derivative, pentacyclo ( ^6.6.1.1.1 )
^3,6. 0 ^2,7. 0 ^9,14] -4-hexadecene derivative, heptacyclo-5-eicosene derivatives, heptacyclo-5-heneicosene derivatives, tricyclo [4.3.1 0.1 ^2,5] -3- decene derivatives, tricyclo [4.4.1 0.1 ^2,5] -3-undecene derivatives, pentacyclo [6.5.1 1.1 ^3,6. 0 ^2,7. 0 ^9,13] -4-
Pentadecene derivatives, penta cyclopentadiene decadiene derivative, pentacyclo [.. 7.4.1 0.1 ^2,5 1 ^9,12 0 ^8,13] -
3-pentadecene derivative, heptacyclo (8.7.0.0.1 ^3,6 .
1 ^{10, 17.} 1 ^{12, 15.} 0 ^2,7. 0 ^11,16] -4-eicosene derivatives, Nonashikuro [10. 9.1.4 1 ^4,7. 1 ^{13, 20.} 1 ^{15, 18.} 0
..... ^3,8 0 ^2,10 0 ^12,21 0 ^{14,1 9]} -5-pentacosene derivatives, pentacyclo [8.4.1 .1 ^2,5 1 ^9,12 0 ^8,13] - 3-
Hexadecene derivative, heptacyclo 〔8.8.0 0.1 ^4,7 .1
^11,18. 1 ^13,16. 0 ^3,8. 0 ^12,17] -5-heneicosene derivatives, Nonashikuro [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 Examples include a 4,4,4a, 5,10,10a-hexahydroanthracene derivative, a cyclopentadiene-acenaphthylene adduct, and the like.

Below, the above formulas [1], [1-1]
Alternatively, more specific examples of the cyclic olefin represented by [2] will be shown.

[0027]

[Chemical 7]

[0028]

[Chemical 8]

[0029]

[Chemical 9]

[0030]

[Chemical 10]

[0031]

[Chemical 11]

[0032]

[Chemical 12]

[0033]

[Chemical 13]

[0034]

[Chemical 14]

[0035]

[Chemical 15]

[0036]

[Chemical 16]

[0037]

[Chemical 17]

[0038]

[Chemical 18]

[0039]

[Chemical 19]

[0040]

[Chemical 20]

[0041]

[Chemical 21]

[0042]

[Chemical formula 22]

[0043]

[Chemical formula 23]

[0044]

[Chemical formula 24]

[0045]

[Chemical 25]

[0046]

[Chemical formula 26]

[0047]

[Chemical 27]

The cyclic olefin represented by the above general formula [1], [1-1] or [2] is obtained by subjecting cyclopentadiene and an olefin having a corresponding structure to a Diels-Alder reaction. Can be manufactured by.

These cyclic olefins can be used alone or in combination of two or more kinds. The cyclic olefin resin of (a-1) to (a-2) used in the present invention uses the cyclic olefin represented by the above formula [1], [1-1] or [2]. For example, JP-A-60-168708 and JP-A-61-120881.
6, JP-A-61-115912, JP-A-61-159912.
1-115916, JP 61-271308 A, JP 61-272216 A, JP 62-A1.
No. 252406, JP-A-62-252407, JP-A-64-106, and JP-A-1-156630.
It can be produced by appropriately selecting the conditions according to the method proposed by the present applicant in JP-A-8, JP-A-1-197511 and the like.

(A-1) Ethylene / Cyclic Olefin Random Copolymer Used in the present invention as a cyclic olefin resin (a-
1) The ethylene / cyclic olefin random copolymer usually contains a structural unit derived from ethylene in an amount of 52 to 90 mol%, preferably 55 to 80 mol%, and a structural unit derived from a cyclic olefin of 10 to 10. It is contained in an amount of 48 mol%, preferably 20 to 45 mol%. The ethylene composition and the cyclic olefin composition are measured by ¹³ C-NMR.

In this (a-1) ethylene / cyclic olefin random copolymer, the above-mentioned ethylene-derived structural units and cyclic olefin-derived structural units are randomly arranged and bonded, It has a substantially linear structure. The copolymer is substantially linear,
The fact that the copolymer does not substantially have a gel-like crosslinked structure can be confirmed by the fact that this copolymer dissolves in an organic solvent and does not contain an insoluble component. For example, when the intrinsic viscosity [η] is measured as described below, this copolymer is
It can be confirmed by completely dissolving in decalin at ℃.

(A-1) ethylene used in the present invention
In the cyclic olefin random copolymer, at least some of the structural units derived from the cyclic olefin represented by the formula [1], [1-1] or [2] are each represented by the following structural formula [1-a]. , [1-1-a] or [2
-A].

[0053]

[Chemical 28] (In the formulas [1-a] and [1-1-a], n, m,
q, R ^{1 to} R ^18, and R ^a and R ^b are the same as those in formula [1]. In the formula [2-a], m, h, j, k, R ⁷
To R ¹⁵ and R ¹⁷ to R ²⁷ represent the same as the formula (2). )

The ethylene / cyclic olefin random copolymer (a-1) used in the present invention is a structural unit derived from another copolymerizable monomer, if necessary, within a range not impairing the object of the present invention. May be contained.

Examples of such other monomers include olefins other than the above-mentioned ethylene or cyclic olefins, norbornenes, non-conjugated dienoic acids, and the like. Specifically, 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-ethyl-1-hexene, 3-ethyl-1- Hexene, 1-octene, 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-
C3-C20 α-olefins such as octadecene and 1-eicosene, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2 (2-methylbutyl) -1-cyclohexene, cyclooctene, 3a , 5, 6, 7a-
Cycloolefins such as 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-2-norbornene,
5,6-dimethyl-2-norbornene, 5-chloro-2
-Norbornenes, norbornenes such as 5-fluoro-2-norbornene, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene , 5-ethylidene-2-norbornene, 5-vinyl-2
And non-conjugated dienes such as norbornene.

These other monomers may be used alone or in combination of two or more. (A-1)
In the ethylene / cyclic olefin random copolymer,
Structural units derived from other monomers as described above,
It may be contained in an amount of usually 20 mol% or less, preferably 10 mol% or less.

(A-1) ethylene used in the present invention
The cyclic olefin random copolymer can be produced using ethylene and the cyclic olefin represented by the formula [1], [1-1] or [2] by the production method disclosed in the above publication. Among these, the copolymerization is carried out in a hydrocarbon solvent, and a vanadium-based catalyst formed from a vanadium compound and an organoaluminum compound soluble in the hydrocarbon solvent as a catalyst, a titanium compound and a titanium formed from an organoaluminum compound. -Based catalyst, or zirconium-based catalyst formed from aluminoxane and a zirconium complex having a multidentate compound having at least two conjugated cycloalkadienyl groups bonded through a lower alkylene group as a ligand Te (a-
1) It is preferable to produce an ethylene / cyclic olefin random copolymer.

(A-2) Ring-Opening (Co) Polymer of Cyclic Olefin The ring-opening (co) polymer of (a-2) cyclic olefin used in the present invention is represented by the above formulas [1] and [1-1]. Or a structural unit derived from a cyclic olefin represented by [2], and at least a part of this structural unit is represented by the following formula [1-b], [1-1-b] or [2-b] Is a homopolymer or a copolymer.

[0059]

[Chemical 29] (In the formulas [1-b] and [1-1-b], n, m,
q, R ^{1 to} R ^18, and R ^a and R ^b are the same as those in formula [1]. In the formula [2-b], m, h, j, k, R ⁷
To R ¹⁵ and R ¹⁷ to R ²⁷ represent the same as the formula (2). )

Cyclic olefin ring-opening (co) polymer (a-
2) contains the above-mentioned cyclic olefin as an essential component, but may contain other copolymerizable unsaturated monomer component, if necessary, within a range not impairing the object of the present invention. . Examples of the unsaturated monomer optionally copolymerized include a cyclic olefin represented by the following general formula [3].

[0061]

[Chemical 30] (In the formula, R ²⁸ and R ²⁹ are a hydrogen atom, a hydrocarbon group or a halogen atom and may be the same or different. T is an integer of 2 or more, and R ²⁸ and R ²⁹ are plural times. When repeated, these may be the same or different.)

Examples of the monomer component represented by the general formula [3] include cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, methylcyclopentene, methylcyclohexene, methylcycloheptene, methylcyclooctene, methylcyclohexene. Nonene, methylcyclodecene,
Examples thereof include ethylcyclopentene, ethylcyclobutene, ethylcyclooctene, dimethylcyclopentene, dimethylcyclohexene, dimethylcycloheptene, dimethylcyclooctene, trimethylcyclodecene, and 2- (2-methylbutyl) -1-cyclohexene.

The unsaturated monomer which may be optionally copolymerized other than the above-mentioned general formula [3] is specifically 2, 3, 3
Cyclic olefins such as a, 7a-tetrahydro-4,7-methano-1H-indene and 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene can be mentioned. Such unsaturated monomers which may be optionally copolymerized may be used alone or in combination,
Ordinary cyclic olefin ring-opening (co) polymer (a-2)
If it is 00 mol%, it is used in an amount of less than 50 mol%.

Such a ring-opening (co) polymer can be produced by the production method disclosed in the above publication. Specifically, it can be produced by polymerizing or copolymerizing the cyclic olefin represented by the above formula [1], [1-1] or [2] in the presence of a ring-opening polymerization catalyst.
As such a ring-opening polymerization catalyst, a catalyst comprising a metal halide selected from ruthenium, rhodium, palladium, osmium, indium or platinum, a nitrate or an acetylacetone compound, and a reducing agent, or titanium, palladium or zirconium. Alternatively, a catalyst composed of a metal halide selected from molybdenum or the like or an acetylacetone compound and an organoaluminum compound can be used.

(A-2) Ring opening (co) used in the present invention
The hydride of the polymer is obtained as described above (a-
2) It is obtained by hydrogenating a ring-opening (co) polymer in the presence of a conventionally known hydrogenation catalyst.

In the hydride of the ring-opening (co) polymer (a-2), among the structural units derived from the cyclic olefin represented by the formula [1], [1-1] or [2], At least a part is represented by the following formula [1-c], [1-1-c] or [2-c].

[0067]

[Chemical 31] (In the formulas [1-c] and [1-1-c], n, m,
q, R ^{1 to} R ^18, and R ^a and R ^b are the same as those in formula [1]. In the formula [2-c], m, h, j, k, R ⁷
To R ¹⁵ and R ¹⁷ to R ²⁷ represent the same as the formula (2). )

The graft-modified cycloolefin resin (a) used in the present invention includes the above-mentioned (a-1) and (a).
It can be produced by graft-modifying the cyclic olefin resin of -2) with a graft monomer.

An unsaturated carboxylic acid or a derivative thereof is suitable as the graft monomer used for producing the graft-modified cycloolefin resin (a) used in the present invention. Examples of such unsaturated carboxylic acids include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid ^™ (endocis-bicyclo [2.2.1]). ] Hept-5-ene-2,3-dicarboxylic acid) and the like. Examples of the above unsaturated carboxylic acid derivatives include unsaturated carboxylic acid anhydrides, unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides, and ester compounds of unsaturated carboxylic acids. it can. Specific examples of such derivatives include maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, glycidyl acrylate and glycidyl methacrylate.

These graft monomers can be used alone or in combination. Among the above graft monomers, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid ^TM or acid anhydrides thereof, or glycidyl methacrylate and glycidyl acrylate are particularly preferable.

The graft-modified cyclic olefin-based resin (a) used in the present invention can be prepared by various conventionally known methods using the above-mentioned graft monomer and unmodified cyclic olefin-based resin. It can be produced by modification. For example, there is a method of melting a cyclic olefin resin and adding a graft monomer to carry out graft polymerization, or a method of dissolving a cyclic olefin resin in a solvent and adding a graft monomer to carry out graft copolymerization. Further, as a method for producing the graft-modified cyclic olefin-based resin (a), a method in which an unmodified cyclic olefin-based resin is mixed with a graft monomer so as to have a desired graft modification rate, and a high graft modification rate is prepared in advance. A method for preparing a graft-modified cyclic olefin resin having a desired modification ratio by preparing a graft-modified cyclic olefin resin having a high modification ratio and diluting the graft-modified cyclic olefin resin having a high modification ratio with an unmodified cyclic olefin resin. There is. In the present invention, the graft-modified cycloolefin resin produced by any method can also be used. The modification rate of the graft-modified cycloolefin resin (a) used in the present invention is usually 0.01 to 5% by weight, preferably 0.1 to 4% by weight.
Is within the range of.

As the graft-modified cyclic olefin resin (a) of the present invention, the graft-modified cyclic olefin resin obtained as described above may be used as it is. An unmodified cyclic olefin resin can be blended and used.
In this case, the graft modification rate in the mixture of the graft-modified cyclic olefin resin and the unmodified cyclic olefin resin is usually 0.01 to 5% by weight, preferably 0.1 to 4% by weight. Prepared in.

The graft modification reaction of such a cyclic olefin resin is preferably carried out in the presence of a radical initiator. By using a radical initiator, the graft monomer can be efficiently graft-copolymerized. The graft reaction is usually performed at a temperature of 60 to 350 ° C. The radical initiator is usually used in an amount within the range of 0.001 to 5 parts by weight based on 100 parts by weight of the modified cyclic olefin resin.

In the present invention, organic peroxides and organic peresters are preferably used as the radical initiator. Specific examples of such a radical initiator include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne- 3,1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di (tert-
Butylperoxy) hexyne-3,2,5-dimethyl-
2,5-di (tert-butylperoxy) hexane,
tert-butyl perbenzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl perpivalate and tert-butyl perdiethyl acetate. I can give you. Furthermore, in the present invention, an azo compound can be used as a radical initiator. Specific examples of this azo compound include azobisisobutyronitrile and dimethylazoisobutyrate.

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

The elastomer (b) used in the cyclic olefin resin composition of the present invention has a tensile modulus at 23 ° C. of 0.1 to 2000 kg / cm ² , preferably 1 to 1500 kg / cm ² , and a glass transition temperature (Tg). ) Is 0 ° C. or lower, preferably −150 to 0 ° C., more preferably −80 to −20 ° C., and the crystallinity measured by X-ray diffraction is 30% or lower, preferably 25% or lower, and low crystallinity. Alternatively, it is an amorphous copolymer rubber.
This elastomer (b) has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.2 to 10 dl /
g, preferably 1 to 5 dl / g, density is usually 0.82
To 0.96 g / cm ³ , preferably 0.84 to 0.92
It is preferably g / cm ³ .

As the elastomer (b) used in the present invention, an α-olefin copolymer can be used,
Examples thereof include (b-1) ethylene / α-olefin copolymer rubber and (b-2) propylene / α-olefin copolymer rubber. The above ethylene / α-olefin copolymer rubber (b-1) and propylene / α-olefin copolymer rubber (b-2) can be used alone or in combination of both. it can.

The α-olefin constituting the ethylene / α-olefin copolymer rubber (b-1) is usually an α-olefin having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene. , 1-hexene, 4-
Methyl-1-pentene, 1-octene, 1-decene, a mixture thereof and the like can be mentioned. Of these, propylene and / or 1-butene are particularly preferable.

The α-olefin constituting the propylene / α-olefin copolymer rubber (b-2) is usually an α-olefin having 4 to 20 carbon atoms, for example, 1-butene, 1-pentene, 1- Hexene, 4-methyl-1-
Mention may be made of pentene, 1-octene, 1-decene and mixtures thereof. Of these, especially 1
-Butene is preferred.

The elastomer (b) used in the present invention has a repeating unit other than α-olefin such as a repeating unit derived from a diene compound within a range not impairing its properties. Good.

The repeating units that are allowed to be contained in the elastomer (b) used in the present invention include, for example, 1,4-hexadiene, 1,6-octadiene and 2
-Methyl-1,5-hexadiene, 6-methyl-1,5
Chain non-conjugated dienes such as -heptadiene and 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-
Vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene and 6-chloromethyl-5
A cyclic non-conjugated diene such as -isopropenyl-2-norbornene; such as 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene. Examples thereof include repeating units derived from diene compounds. The content of the repeating unit derived from the above diene component in the α-olefin copolymer is usually 10 mol% or less, preferably 5 mol% or less.

Ethylene / α-olefin copolymer (b-
In 1), the molar ratio of ethylene to α-olefin (ethylene / α-olefin) is generally 10/90 to 99/1, preferably 50/50 to 95/5, though it varies depending on the type of α-olefin. Is. The above molar ratio is α-
When the olefin is propylene, 50/50 to
90/10 is preferable, and 80/20 when the α-olefin is an α-olefin having 4 or more carbon atoms.
It is preferably ˜95 / 5.

In the propylene / α-olefin copolymer (b-2), the molar ratio of propylene to α-olefin (propylene / α-olefin) varies depending on the type of α-olefin, but is generally 50. / 50-95
Within the range of / 5. Further, the above molar ratio is 50/50 to 90 when the α-olefin is 1-butene.
/ 10 is preferable, and when the α-olefin has 5 or more carbon atoms, it is preferably 80/20 to 95/5.

In the present invention, among the above α-olefin copolymers, an ethylene / propylene random copolymer or an ethylene / α-olefin having an ethylene content of 35 to 50 mol% and a crystallinity of 10% or less is used. Random copolymers are preferred.

The graft-modified elastomer (c) used in the cyclic olefin resin composition of the present invention is the above-mentioned elastomer (b) graft-modified with a graft monomer. As the graft monomer, the same graft monomer as that used for producing the graft-modified cyclic olefin resin (a) is used.

As the method of graft-modifying the elastomer (b) as described above, the same method as the method of producing the graft-modified cyclic olefin resin is adopted.
The graft modification rate in such a graft modified elastomer (c) is generally expressed by the content of the graft monomer, and the modification rate is 0.01 to 10% by weight, preferably 0.1 to 4% by weight. Is desirable.

Polyamide resin (d) used in the present invention
As the polyamide, which can be produced by subjecting a diamine component and a dicarboxylic acid component to a polycondensation reaction, or a compound capable of forming an amino group and a carboxyl group such as caprolactam or a functional derivative thereof is subjected to ring-opening polymerization. Various polyamides and the like that can be produced by the above are included.

Specific examples of the polyamide resin (d) include nylon-6, nylon-66 and nylon-61.
0, nylon-11, nylon-612, nylon-1
2, co-condensed nylon formed from caprolactam and an aqueous solution of nylon salt, nylon MXD6 formed from metaxylenediamine and adipic acid, nylon-46,
Mention may be made of methoxymethylated polyamide, polyhexamethylenediamine terephthalamide and polyhexamethylenediamine isophthalamide. These can be used alone or in combination.

In the present invention, the polyamide resin (d) is a condensate of the above-mentioned diamine component and dicarboxylic acid component or ε-aminoundecanoic acid, or a ring-opening polymer of the above-mentioned lactams, which is 25 It is preferable to use a resin having [η] measured in 96% sulfuric acid at 96 ° C in the range of 0.2 to 3.5 dl / g. Further, in the present invention, the intrinsic viscosity [η] is 1.0 to 2.5 dl /
It is particularly preferred to use polyamides in the range of g.

The pearl mica pigment (e) used in the present invention is a pearl mica pigment whose surface is coated with a metal oxide having a high refractive index such as titanium oxide or iron oxide. , Pearl mica, pearl pigment or pearl agent.

Particle diameter (major axis) of pearl mica pigment (e),
The coverage and the film thickness with the metal oxide are not particularly limited, but those having a particle size of usually about 5 to 200 μm and the surface of the mica being covered with about 10 to 60% of titanium oxide are preferable. Further, those coated with anatase type or rutile type titanium oxide are preferable. A commercially available product may be used as the pearl mica pigment (e). For example, Iriodi manufactured by Merck Japan Ltd.
n 100 Silver Pearl (trade name) and the like.

The mixing ratios of the components (a) to (e) are as follows: graft-modified cycloolefin resin (a), elastomer (b), graft-modified elastomer (c), and polyamide resin (d). The total amount of the graft-modified cycloolefin resin (a) is 0.5 to 50 per 100 parts by weight.
Parts by weight, preferably 5 to 40 parts by weight, the elastomer (b) is 0 to 38 parts by weight, preferably 3 to 20 parts by weight,
The graft-modified elastomer (c) is 0 to 38 parts by weight, preferably 3 to 20 parts by weight, and the polyamide resin (d) is 40 parts by weight.
To 90 parts by weight, preferably 45 to 85 parts by weight,
0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight of pearl mica pigment based on 100 parts by weight of the total of (a) to (d).
Parts by weight. The total amount of the elastomer (b) and the graft modified elastomer (c) is preferably 0.5 to 38 parts by weight.

In the method for producing the cyclic olefin resin composition of the present invention, the above components are mechanically mixed together and then the mixture is prepared by using a melt-kneading device such as a twin-screw extruder. A method of heating to a molten state and kneading, or after mechanically mixing the respective components as described above, using a melt-kneading device such as a twin-screw extruder, the mixture is heated to a molten state and melted. To the kneaded product in the state,
Examples of the method include adding the components (d) and (e) and kneading. In both manufacturing methods,
The conditions can be set appropriately.

In addition to the components (a) to (e) described above, the cyclic olefin resin composition of the present invention contains an inorganic filler, an organic filler, a heat stabilizer, a weather resistance stabilizer and an antistatic agent. , Anti-slip agent, anti-blocking agent, anti-fog agent,
Additives such as lubricants, pigments, dyes, natural oils, synthetic oils and waxes may be blended, and these additives and fillers can be added at any stage according to a conventional method. It is also possible to add metallic aluminum powder to obtain a metallic appearance.

In the cyclic olefin resin composition of the present invention, a resin composition excellent in low water absorption, impact resistance and dimensional stability is obtained by combining a graft-modified cyclic olefin resin, a polyamide resin and, if necessary, an elastomer. Although the resin composition is opaque, since the graft-modified cycloolefin resin has transparency, by combining with a pearl mica pigment, gloss and transparency are imparted, and the surface layer of the opaque resin is It has the appearance of a transparent layer presenting a deep, transparent feel as if a clear topcoat had been overcoated.

When a pigment is added to such a resin composition, the resin colored by the pigment has a transparent layer formed on the surface thereof, and the colored resin has a glossy and deep transparency. can get.

The cyclic olefin resin composition of the present invention is
Since the resin surface is a thermoplastic resin that has a glossy and deep transparent feeling like a clear top coating, it has a good appearance, low water absorption, and excellent impact resistance and dimensional stability. Fields in which thermoplastics are used,
In particular, in the field where a polyamide resin or a polyamide resin reinforced with a filler is used, it can be suitably used for applications in which the above characteristics are required. In this case, the painting finish to improve the appearance can be omitted. Specifically, it is used for automobile parts such as cowl tops, wheel caps, rearview mirrors, windshield pillar inners, rear roof rails, rear wheel house inners, exterior parts such as side moldings, interior parts such as dashboards and door panels. Further, it is used as a member of various motorbikes, a member of various boats such as a motor boat, and the like. Above all, it is selected as a material such as a wheel cap, which is required to have a lightweight and beautiful appearance.

[0098]

EFFECTS OF THE INVENTION According to the present invention, the components (a) to (e) are blended in a specific amount, so that the surface appearance has a gloss and a deep transparent feeling like a clear top coat. However, a cycloolefin resin composition having low water absorption and excellent impact resistance and dimensional stability can be obtained. This cyclic olefin-based resin composition has low water absorption and excellent impact resistance and dimensional stability as compared with a polyamide resin.

[0099]

EXAMPLES Next, the present invention will be described with reference to examples. However, the present invention should not be limitedly interpreted by these examples. The characteristics of the ethylene / cycloolefin random copolymer, the graft-modified elastomer and the cycloolefin resin composition used in each example are as follows.
It measured as follows. Intrinsic viscosity [η]: Measured at 135 ° C in decalin. Softening temperature (TMA): Temperature rising rate: 5 ° C./min. Load: 50 g; temperature at which flat-bottom needle with a diameter of 1 mm was inserted into 100 μm was taken as TMA. Graft monomer amount: Measured by ¹³ C-NMR. Crystallinity: Measured by an X-ray diffraction method at 23 ° C. Tensile modulus: 2mm according to ASTM D638
It measured at 23 degreeC using the thick press test piece. Melt index (MI): According to JIS-K-6760, it was performed at 260 ° C. under a load of 2.16 kg.

Production Example 1 [Polymerization of Ethylene / Cyclic Olefin Copolymer (a-1)] Using a 1 liter polymerization vessel equipped with a stirring blade, ethylene and tetracyclo [4.4.0.1 ² ] were continuously added. ^{, 5} . 1
^7,10 ] Dodecene-3 (hereinafter abbreviated as “TCD-3”) was subjected to a copolymerization reaction. That is, a cyclohexane solution of TCD-3 was added to the T
0.4 liter / hour so that the CD-3 concentration is 60 g / l
Iter, a cyclohexane solution of VO (OC ₂ H ₅ ) Cl ₂ as a catalyst was added so that the vanadium concentration in the polymerization vessel would be 0.5 mmol / l, 0.5 liter / hour (the supplied vanadium concentration was the polymerization vessel). At a rate of 2.86 times the medium concentration), a solution of ethylaluminum sesquichloride [Al (C ₂ H ₅ ) _1.5 Cl _1.5 ] in cyclohexane has an aluminum concentration of 4.0 mmol / l in the polymerization reactor. Thus, cyclohexane was continuously fed into the polymerization vessel at a rate of 0.4 liter per hour, and cyclohexane at a rate of 0.7 liter per hour, while the polymerization liquid in the polymerization vessel from the lower part of the polymerization vessel was constantly changed to 1 liter. The polymerization reaction liquid was continuously withdrawn so that (that is, the residence time was 0.5 hours).

A bubbling tube was used as the polymerization system, and ethylene was added at 20 liters per hour and nitrogen was supplied at 10 liters per hour.
er, and hydrogen were fed at a rate of 0.5 liter per hour. The copolymerization reaction was carried out at 10 ° C. by circulating a refrigerant through a jacket attached outside the polymerization vessel.

After carrying out the copolymerization reaction under the above-mentioned polymerization conditions, an ethylene / TCD-3 random copolymer was obtained as follows. That is, the polymerization liquid was extracted from the lower part of the polymerization vessel, and a cyclohexane / isopropyl alcohol (volume ratio = 1/1) mixed liquid was added to the polymerization liquid to stop the polymerization reaction. Thereafter, an aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water and the above polymerization solution are brought into contact with each other with strong stirring using a homomixer at a ratio of 1: 1 to transfer the catalyst residue to an aqueous phase. It was

The above mixture was allowed to stand, and after removing the aqueous phase,
Further, the polymer solution was purified by washing twice with distilled water and then separated. The obtained polymerization liquid was contacted with 3-fold amount of acetone under strong stirring, and the precipitated solid part was collected by filtration and thoroughly washed with acetone. Then, the filtered solid was dried at 130 ° C. and 350 mmHg for 24 hours under nitrogen flow.

By continuously carrying out the above-mentioned operation, the ethylene / TCD-3 random copolymer was added at an hourly rate of 76.
It was prepared continuously at a rate of g (38 g / l). ¹³ C-N
The ethylene composition in this copolymer determined from the results of MR analysis was 63 mol%. The intrinsic viscosity [η] of the copolymer measured in decalin at 135 ° C. was 0.5 dl / g, the iodine value was 1.0, and the softening temperature (TMA) was 150 ° C. .

Production Example 2 [Preparation of Graft-Modified Cyclic Olefin Resin (a)] 1 part by weight of maleic anhydride and 2, based on 100 parts by weight of the ethylene / TCD-3 random copolymer obtained in Preparation Example 1. 5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 (manufactured by NOF CORPORATION, trade name; Perhexin 25B) 0.2 parts by weight are mixed, and a twin-screw extruder with a vent device of 30 mm in diameter Was melt-kneaded at 260 ° C. to obtain a graft-modified ethylene / cycloolefin copolymer. Maleic anhydride addition amount (modification rate) of the obtained graft-modified ethylene / cycloolefin copolymer
Was 0.83% by weight.

Production Example 3 [Preparation of graft-modified elastomer (c)] 100 parts by weight of ethylene / propylene copolymer having an ethylene content of 80 mol% and an intrinsic viscosity [η] of 2.2 dl / g measured in decalin at 130 ° C. For maleic anhydride 1
Parts by weight, 0.2 parts by weight of 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 are mixed to obtain a diameter of 3
A graft-modified elastomer was obtained by melt-kneading at 260 ° C. using a twin-screw extruder equipped with a 0 mm vent device. The amount of added maleic anhydride (modification rate) of the obtained graft-modified elastomer was 0.90% by weight. The tensile modulus was 80 kg / cm ² .

Example 1 30 parts by weight of the graft-modified ethylene / cycloolefin copolymer obtained in Production Example 2 and 15 parts by weight of the graft-modified elastomer obtained in Production Example 3 were used, and the diameter was 30 mm. A precursor mixture was prepared by melt-kneading at 230 ° C. using an extruder. Then, as a polyamide resin, nylon 6 (manufactured by Toray Industries, Inc., trade name; Alamin CM100)
7) 55 parts by weight, 45 parts by weight of the above precursor mixture, and pearl mica pigment (manufactured by Merck Japan Ltd., trade name; Irio)
1 part by weight of din 100 Silver Pearl) was kneaded at 250 ° C. using the above extruder to obtain a cyclic olefin resin composition. 100 parts of this resin composition
After drying at ℃ for 8 hours, using an injection molding machine (Toshiba IS, 50EPN) as a molding machine, 250 ℃, the mold temperature 6
A square plate for evaluating the transparency of the surface was prepared by setting the temperature to 0 ° C.
The evaluation results are shown in Table 1.

Comparative Example 1 Instead of the graft-modified ethylene / cycloolefin copolymer used in Example 1, a maleic anhydride graft-modified propylene polymer (intrinsic viscosity [η]: 0.4 dl) was used.
/ G, maleic anhydride graft amount: 0.7% by weight, hereinafter referred to as graft-modified PP), a square plate was produced and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 2 A square plate was produced in the same manner as in Example 1 except that the nylon 6 used in Example 1 was used in place of the graft-modified ethylene / cycloolefin copolymer used in Example 1. ,evaluated. The evaluation results are shown in Table 1.

Comparative Example 3 ABS (manufactured by Toray Industries, Inc., trade name; TOYOLAC 700) 1
Example 1 was prepared by melt-kneading 00 parts by weight and 1 part by weight of the pearl mica pigment used in Example 1 in the same manner as in Example 1.
A square plate was manufactured and evaluated in the same manner as in. Table 1 shows the evaluation results
Shown in.

[0111]

[Table 1] * 1 Graft-modified ethylene / cyclic olefin copolymer obtained in Production Example 2 * 2 Graft-modified elastomer obtained in Production Example 3 * 3 Nylon 6 (manufactured by Toray Industries, Inc., trade name; Amilan CM)
1007) * 4 Pearl mica pigment (manufactured by Merck Japan Ltd., trade name; Iriodin 100 Silver Pear)
l) * 5 Graft-modified propylene polymer * 6 Toray Co., Ltd., trade name; Toyolac 700 * 7 Criteria 5: There is a gloss and depth like clear top coat, and it has a nice and transparent appearance. 4: There is no depth like clear top coat, but there is transparency 3: Somewhat transparent 2: Almost no transparency 1: No transparent circle

As is clear from the results of Table 1, Example 1
In the resin composition of, the surface had gloss and depth as if it had been coated with a clear top coat, and exhibited a nice transparent appearance, whereas the comparative examples did not show such a transparent feeling. Was inferior to that of Example 1.

Claims (4)

[Claims] 1. An ethylene / cycloolefin random copolymer (a-1), which comprises (a) a random copolymer of ethylene and a cycloolefin represented by the following general formula [1]:
And one or more cyclic olefin resins selected from the group consisting of ring-opening (co) polymers of cyclic olefins represented by the following general formula [1] or hydrogenated products (a-2) thereof with a graft monomer. A modified graft-modified cyclic olefin resin, and (b) a tensile modulus at 23 ° C. of 0.1 to 20.
Within the range of 00 kg / cm ² , the glass transition temperature is 0
An elastomer having a degree of crystallinity of 30 ° C. or less and a crystallinity of 30% or less, and (c) a tensile modulus at 23 ° C. of 0.1 to 20.
Within the range of 00 kg / cm ² , the glass transition temperature is 0
A resin composition comprising a graft-modified elastomer obtained by graft-modifying an elastomer (b) having a crystallinity of 30% or less and a crystallinity of 30% or less, (d) a polyamide resin, and (e) a pearl mica pigment. And (a) component, (b) component, (c) component and (d)
From 100 parts by weight of the total of the components, 0.5 to
50 parts by weight, 0 to 38 parts by weight of the component (b), 0 to 38 parts by weight of the component (c), 40 to 90 parts by weight of the component (d), and a total of 100 parts by weight of the components (a) to (d). A cyclic olefin resin composition comprising 0.01 to 10 parts by weight of the pearl mica pigment (e) per part. [Chemical 1] (In the formula, 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,
It represents an atom or group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic group, and The ring or polycyclic group may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. When q is 0, respective bonds bond to form a 5-membered ring. ) 2. The softening temperature (TMA) of the graft-modified cycloolefin resin (a) is 70 ° C. or higher, and the intrinsic viscosity [η] measured in decalin at 130 ° C. is 0.0.
The cyclic olefin resin composition according to claim 1, which is in a range of 1 to 10 dl / g. 3. The cyclic olefin resin according to claim 1, wherein the graft modified cyclic olefin resin (a) is a mixture of an unmodified cyclic olefin resin and a graft modified cyclic olefin resin. Resin composition. 4. The cyclic olefin system according to claim 1, wherein the total amount of the elastomer (b) and the graft-modified elastomer (c) is 0.5 to 38 parts by weight. Resin composition.