JP2000086870A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which can give a molding freed from discoloration and burn due to heat decomposition even when molded under high-temperature conditions by incorporating a polycycloolefin resin with a specified phosphorus-containing antioxidant. SOLUTION: The phosphorus antioxidant is a compound represented by formula I (wherein R1 to R10 are each H or a hydrocarbon group, provided that 1-3 of the five groups represented by R1 to R5 and R6 to R10 are (substituted) cumenyl groups represented by formula II; and R11 to R15 are each H or a 1-10C hydrocarbon group). Desirably, this antioxidant is one represented by formula III (wherein R16 to R41 are each R11). It is desirable that the polycycloolefin resin is a ring opening (co)polymer of a monomer represented by formula IV with a copolymerizable monomer. In the formula, R42 and R47 are each R11; R43 and R45 are each H or a monovalent organic group, provided that at least either of them is other than H and a hydrocarbon and is a polar group; and m and p are each 0-3, provided that m+p=0-4). It is desirable that 100 pts.wt. polycycloolefin resin is incorporated with 0.01-10 pts.wt. phosphorus-containing antioxidant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition,
More specifically, the present invention relates to a thermoplastic resin composition containing a phosphorus-based antioxidant having a specific chemical structure.

[0002]

2. Description of the Related Art Cyclic polyolefin-based resins have a high glass transition temperature due to the rigidity of the main chain structure, and are amorphous and have high light transmittance because the main chain structure contains bulky groups.
In addition, it has features such as low birefringence due to small anisotropy of polarizability, and has attracted attention as a thermoplastic resin having excellent heat resistance, transparency, and optical properties. Examples of such a cyclic polyolefin-based resin include, for example,
JP-A-132625, JP-A-1-132626,
JP-A-63-218726, JP-A-2-1334
No. 13, JP-A-61-120816 and JP-A-61-115912.

In recent years, application of cyclic polyolefin-based resins in fields such as optical materials such as optical disks, optical lenses and optical fibers, and sealing materials such as optical semiconductor sealing materials has been studied. In order to mold a cyclic polyolefin resin having a high glass transition temperature, it is necessary to process at a high temperature.

However, when molding is performed under such a high temperature condition, the resulting molded article is colored to impair the colorless transparency, or the resin (cyclic polyolefin-based resin) and / or added resin is added to the molded article. There is a problem that burning (black stripes) is caused due to thermal decomposition of the agent (component).

For example, when an optical disk is injection-molded using a cyclic polyolefin-based resin, it is necessary to raise the molding temperature considerably (for example, 300 to 360 ° C.) in order to improve the transferability of the recording groove. In addition, since a small amount of resin is used to obtain a thin molded product such as an optical disk, the residence time of the resin (cyclic polyolefin-based resin) in an injection molding machine becomes long. For this reason, the obtained optical disk becomes yellowish and easily burns (black stripes).

Further, when a molded article obtained from a cyclic polyolefin resin is used in a high-temperature environment, the hue of the molded article changes over time, and the colorless transparency of the cyclic polyolefin resin is impaired. There are also problems.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made based on the above circumstances, and its object is to provide:
While maintaining the good properties (transparency, heat resistance and optical properties) of the cyclic polyolefin resin, the molded product obtained by molding under high temperature conditions can be colored by oxidation deterioration,
It is an object of the present invention to provide a resin composition which does not cause burning (black stripes) due to thermal decomposition. Another object of the present invention is to provide a resin composition capable of maintaining an initial hue (colorless and transparent) even under a high-temperature environment (a resin composition constituting a molded article).
Is to provide.

[0008]

The resin composition of the present invention comprises:
A cyclic polyolefin-based resin (A) (hereinafter also referred to as “component (A)”) and a phosphorus-based antioxidant (B) represented by the following general formula (I) (hereinafter also referred to as “component (B)”) ).

[0009]

Embedded image

[In the general formula (I), R ^{1 to} R ¹⁰ each represent a hydrogen atom or a hydrocarbon group, and may be the same or different. However, among the five groups represented by R ¹ to R ^5, 1 to 3 amino groups are cumenyl group substituted or unsubstituted represented by the following formula (1), R ⁶
Of the five groups represented by to R ^10, 1 to 3 groups are cumenyl group substituted or unsubstituted represented by the following formula (1). ]

[0011]

Embedded image

[In the formula (1), R ^{11 to} R ¹⁵ are each
A hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different. ]

The above-mentioned general formula (I) representing the component (B)
In, R¹~ R^TenOf the groups represented by
Represents a hydrogen atom, methyl other than an unsubstituted cumenyl group
Group, ethyl group, n-propyl group, i-propyl group, n-
Butyl group, sec-butyl group, t-butyl group, n-pen
Chill, i-pentyl group, neo-pentyl group, t-pen
Tyl group, n-hexyl group, n-heptyl group, n-octyl
Group, n-nonyl group, n-decyl group, vinyl group, allyl
And a group selected from the group consisting of i-propenyl group
The above formula representing a substituted or unsubstituted cumenyl group
In (1), R ¹¹~ R^FifteenIs a group represented by the above group
Preferably, it is a group selected more.

In the general formula (I) representing the component (B), two of the five groups represented by R ^{1 to} R ⁵ are substituted or unsubstituted by the formula (1). And two of the five groups represented by R ^{6 to} R ¹⁰ are preferably a substituted or unsubstituted cumenyl group represented by the formula (1).

Further, (B) represented by the following general formula (II)
It is preferable to contain components.

[0016]

Embedded image

[In the general formula (II), R ^{16 to} R ⁴¹ each represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different. ]

In the resin composition of the present invention, the following forms are preferred. [1] 0.01 to 10 parts by weight of component (B) based on 100 parts by weight of component (A). [2] Hindered phenolic antioxidant (C)
(Hereinafter, also referred to as “component (C)”).
[3] 0.01 to 10 parts by weight of component (B) and 0.01 to 10 parts by weight of component (C) based on 100 parts by weight of component (A). [4] The component (A) is a ring-opening (co) polymer of a monomer represented by the following general formula (III) and a copolymerizable monomer.

[0019]

Embedded image

[In the general formula (III), R ⁴² and R ⁴⁴ are
A hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms;
⁴³ and R ⁴⁵ are a hydrogen atom or a monovalent organic group, and at least one of R ⁴³ and R ⁴⁵ represents a polar group other than a hydrogen atom and a hydrocarbon group. m is an integer of 0 to 3, p
Is an integer of 0 to 3, and m + p is 0 to 4. ]

[5] As the component (B), bis (2,4-
(Dicumylphenyl) pentaerythritol diphosphite. [6] The molecular weight of the component (C) is 350 or more.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the resin composition of the present invention will be described in detail. <Component (A)> Examples of the component (A) constituting the resin composition of the present invention include the following polymers. Ring-opening polymer of monomer represented by the above general formula (III) (hereinafter referred to as “specific monomer”) Ring-opening copolymer of specific monomer and copolymerizable monomer Hydrogenated polymer of ring (co) polymer After cyclization of the ring-opened (co) polymer by Friedel-Crafts reaction, hydrogenated (co) polymer Specific monomer and unsaturated double bond-containing compound Saturated copolymer with

<Specific Monomers> Preferred specific monomers are those in which R ⁴² and R ^{44 in} the above formula (III) are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ⁴³ and R ^{43 45} is a hydrogen atom or a monovalent organic group, at least one of R ⁴³ and R ⁴⁵ represents a polar group other than a hydrogen atom and a hydrocarbon group, m is an integer of 0 to 3, p is 0 to 3 And m + p is 0 to 4 (more preferably 0 to 2, especially 1). Further, among the specific monomers, the specific monomer having a polar group represented by the formula-(CH ₂ ) _n COOR ⁴⁶ is one in which the obtained resin composition has a high glass transition temperature and a low hygroscopic property. This is preferred.
In the above formula for the polar group, R ⁴⁶ has 1 carbon atom.
To 12 hydrocarbon groups, preferably alkyl groups. In addition, n is usually 0 to 5, and a smaller value of n is preferable because the glass transition temperature of the obtained resin composition becomes higher. Further, a specific monomer having n of 0 is preferably synthesized. It is preferable because it is easy. Further, the above general formula (II
Preferably in I) is R ⁴² or R ⁴⁴ an alkyl group, preferably the number of carbon atoms of the alkyl group is 1-4, more preferably 1-2, particularly preferably 1. In particular, the formula the alkyl group of the - (CH _{2) n}
It is preferable that the polar group represented by COOR ⁴⁶ be bonded to the same carbon atom as the bonded carbon atom. Further, the specific monomer in which m is 1 in the general formula (III) is preferable in that a resin composition having a high glass transition temperature can be obtained.

The specific monomer represented by the above general formula (III)
Specific examples of the body include the following compounds.
Bicyclo [2.2.1] hept-2-ene, tricyclo
[5.2.1.0^2,6] -8-decene, tetracyclo
[4.4.0.1^2,5. 1^7,10] -3-Dodecene, pen
Tacyclo [6.5.1.1^3,6. 0^2,7. 0^9,13] -4
-Pentadecene, pentacyclo [7.4.0.1^2,5.
1^9,12. 0^8,13] -3-pentadecene, tricyclo
[4.4.0.1^2,5] -3-undecene, 5-methyl
Bicyclo [2.2.1] hept-2-ene, 5-ethyl
Bicyclo [2.2.1] hept-2-ene, 5-methoxy
Cycarbonylbicyclo [2.2.1] hept-2-e
5-methyl-5-methoxycarbonylbicyclo
[2.2.1] Hept-2-ene, 5-cyanobicyclo
[2.2.1] Hept-2-ene, 8-methoxycarbo
Nyltetracyclo [4.4.0.1^2,5. 1^7,10] -3
-Dodecene, 8-ethoxycarbonyltetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, 8-
n-propoxycarbonyltetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8-isopropoxy
Carbonyltetracyclo [4.4.0.1^2,5.
1^7,10] -3-dodecene, 8-n-butoxycarbonyl
Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-do
Decene, 8-methyl-8-methoxycarbonyltetracy
Black [4.4.0.1^2,5. 1 ^7,10-3-dodecene,
8-methyl-8-ethoxycarbonyltetracyclo
[4.4.0.1^2,5. 1 ^7,10] -3-dodecene, 8-
Methyl-8-n-propoxycarbonyltetracyclo
[4.4.0.1^{2, Five}. 1^7,10] -3-dodecene, 8-
Methyl-8-isopropoxycarbonyltetracyclo
[4.4.0.1^{2, Five}. 1^7,10] -3-dodecene, 8-
Methyl-8-n-butoxycarbonyltetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, dime
Tanooctahydronaphthalene, ethyl tetracyclodode
Sen, 6-ethylidene-2-tetracyclododecene,
Limethanooctahydronaphthalene, pentacyclo [8.
4.0.1.^2,5. 1^9,12. 0^8,13] -3-Hexadece
Heptacyclo [8.7.0.1^3,6. 1^10,17. 1
^12,15. 0^2,7. 0^11,16-4-Eicosene, hepta
Cyclo [8.8.0.1^4,7. 1^11,18. 1^13,16. 0
^3,8. 0^12,17] -5-Hen-eicosene, 5-ethylidene
Nbicyclo [2.2.1] hept-2-ene, 8-ethyl
Lidentetracyclo [4.4.0.1^2,5. 1^7,10]-
3-dodecene, 5-phenylbicyclo [2.2.1]
Put-2-ene, 8-phenyltetracyclo [4.4.
0.1^2,5. 1^7,10] -3-dodecene, 5-fluorobi
Cyclo [2.2.1] hept-2-ene, 5-fluoro
Methylbicyclo [2.2.1] hept-2-ene, 5-
Trifluoromethylbicyclo [2.2.1] hept-2
-Ene, 5-pentafluoroethylbicyclo [2.2.
1] Hept-2-ene, 5,5-difluorobicyclo
[2.2.1] Hept-2-ene, 5,6-difluoro
Bicyclo [2.2.1] hept-2-ene, 5,5-bi
(Trifluoromethyl) bicyclo [2.2.1] hep
To-2-ene, 5,6-bis (trifluoromethyl) bi
Cyclo [2.2.1] hept-2-ene, 5-methyl-
5-trifluoromethylbicyclo [2.2.1] hept
-2-ene, 5,5,6-trifluorobicyclo [2.
2.1] Hept-2-ene, 5,5,6-tris (full
Oromethyl) bicyclo [2.2.1] hept-2-e
5,5,6,6-tetrafluorobicyclo [2.
2.1] Hept-2-ene, 5,5,6,6-tetraki
(Trifluoromethyl) bicyclo [2.2.1] hep
To-2-ene, 5,5-difluoro-6,6-bis (to
(Fluoromethyl) bicyclo [2.2.1] hept-2
-Ene, 5,6-difluoro-5,6-bis (trifur
Oromethyl) bicyclo [2.2.1] hept-2-e
, 5,5,6-trifluoro-5-trifluoromethyl
Rubicyclo [2.2.1] hept-2-ene, 5-fur
Oro-5-pentafluoroethyl-6,6-bis (tri
Fluoromethyl) bicyclo [2.2.1] hept-2-
Ene, 5,6-difluoro-5-heptafluoro-is
o-propyl-6-trifluoromethylbicyclo [2.
2.1] Hept-2-ene, 5-chloro-5,6,6-
Trifluorobicyclo [2.2.1] hept-2-e
, 5,6-dichloro-5,6-bis (trifluorome
Tyl) bicyclo [2.2.1] hept-2-ene, 5,
5,6-trifluoro-6-trifluoromethoxybis
Black [2.2.1] hept-2-ene, 5,5,6-to
Trifluoro-6-heptafluoropropoxybicyclo
[2.2.1] Hept-2-ene, 8-fluorotetra
Cyclo [4.4.0.1^2,5. 1^7,10] -3-Dodece
8-fluoromethyltetracyclo [4.4.0.1
^2,5. 1^7,10] -3-dodecene, 8-difluoromethyl
Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-do
Decene, 8-trifluoromethyltetracyclo [4.
4.0.1.^2,5. 1^7,10] -3-dodecene, 8-pentane
Fluoroethyltetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8,8-difluorotetracycline
B [4.4.0.1^2,5. 1^7,10-3-dodecene,
8,9-difluorotetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8,8-bis (tri
Fluoromethyl) tetracyclo [4.4.0.1^2,5.
1 ^7,10] -3-dodecene, 8,9-bis (trifluoro
Methyl) tetracyclo [4.4.0.1^2,5. 1 ^7,10]
-3-dodecene, 8-methyl-8-trifluoromethyl
Tetracyclo [4.4.0.1^2,5. 1 ^7,10] -3-do
Decene, 8,8,9-trifluorotetracyclo [4.
4.0.1.^2,5. 1^7,10] -3-dodecene, 8,8,9
-Tris (trifluoromethyl) tetracyclo [4.
4.0.1.^{2, Five}. 1^7,10-3-dodecene, 8,8,
9,9-tetrafluorotetracyclo [4.4.0.1
^2,5. 1^7,10] -3-dodecene, 8,8,9,9-tetra
Laquis (trifluoromethyl) tetracyclo [4.4.
0.1^2,5. 1^7,10] -3-dodecene, 8,8-diflu
Oro-9,9-bis (trifluoromethyl) tetracycl
B [4.4.0.1^2,5. 1^7,10-3-dodecene,
8,9-difluoro-8,9-bis (trifluoromethyl
Le) tetracyclo [4.4.0.1^2,5. 1^7,10] -3
-Dodecene, 8,8,9-trifluoro-9-trifur
Oromethyltetracyclo [4.4.0.1^2,5.
1^7,10] -3-dodecene, 8,8,9-trifluoro-
9-trifluoromethoxytetracyclo [4.4.0.
1^2,5. 1^7,10] -3-dodecene, 8,8,9-triff
Fluoro-9-pentafluoropropoxytetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, 8-
Fluoro-8-pentafluoroethyl-9,9-bis
(Trifluoromethyl) tetracyclo [4.4.0.1
^2,5. 1^7,10] -3-dodecene, 8,9-difluoro-
8-heptafluoroiso-propyl-9-trifluoro
Romethyltetracyclo [4.4.0.1^2,5. 1^7,10]
-3-dodecene, 8-chloro-8,9,9-trifluoro
Rotetracyclo [4.4.0.1^2,5. 1^7,10] -3-
Dodecene, 8,9-dichloro-8,9-bis (triflu
(Oromethyl) tetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8- (2,2,2-trifluoro)
Roethoxycarbonyl) tetracyclo [4.4.0.1
^2,5. 1^7,10] -3-dodecene, 8-methyl-8-
(2,2,2-trifluoroethoxycarbonyl) tetra
Lacyclo [4.4.0.1^2,5. 1^7,10] -3-Dodece
And the like.

Among these specific monomers, 8-methyl-
8-methoxycarbonyltetracyclo [4.4.0.1
^2,5. 1^7,10-3-Dodecene, 8-ethylidenetetra
Cyclo [4.4.0.1^2,5. 1^7,10-3-Dodese
8-ethyltetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, pentacyclo [7.4.0.1
^2,5. 1^9,12. 0^8,13-3-pentadecene
In that the resulting resin composition has excellent heat resistance
preferable.

<Copolymerizable Monomer> In the ring-opening polymerization step for obtaining the component (A), the above-mentioned specific monomer may be subjected to ring-opening polymerization alone. Ring-opening copolymerization with a copolymerizable monomer may be carried out. Specific examples of the copolymerizable monomer used in this case, cyclobutene, cyclopentene, cycloheptene, cyclooctene, tricyclo [5.2.1.0 ^{2, 6]} -3- decene, 5-ethylidene -2 -Cycloolefins such as norbornene and dicyclopentadiene. The carbon number of the cycloolefin is preferably from 4 to 20, more preferably from 5 to 12. Specified in the presence of unsaturated hydrocarbon-based polymers containing a carbon-carbon double bond in the main chain, such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-nonconjugated diene copolymer, and polynorbornene The monomer may be subjected to ring-opening polymerization.
In these copolymerizable monomers, the “specific monomer / copolymerizable monomer (weight ratio)” is preferably from 100/0 to 50/50, more preferably from 100/0 to 60/50. / 4
It is used at a ratio of 0. The hydrogenated product of the ring-opening polymer obtained in this case is useful as a raw material for a resin having high impact resistance.

<Ring-Opening Polymerization Catalyst> In the present invention, the ring-opening polymerization reaction is carried out in the presence of a metathesis catalyst. This metathesis catalyst comprises (a) at least one selected from compounds of W, Mo, and Re; (b) a group IA element (eg, Li, Na, K, etc.) of the periodic table of deming; and a group IIA element (eg, Mg, Ca, etc.), Group IIB elements (eg, Zn,
Cd, Hg, etc.), Group IIIB elements (eg, B, Al, etc.), Group IVA elements (eg, Ti, Zr, etc.) or IV
A catalyst which is a compound of a group B element (for example, Si, Sn, Pb, etc.) and which is a combination with at least one selected from those having at least one element-carbon bond or element-hydrogen bond. . In this case, in order to increase the activity of the catalyst, an additive (c) described below may be added.

Suitable as component (a) is W, Mo or
As a typical example of the compound of Re, WCl₆, MoC
l_Five, ReOCl_ThreeJP-A-1-240517
Can be mentioned. (B) ingredients
For example, n-C_FourH₉Li, (C_TwoH_Five)_ThreeAl
 , (C _TwoH_Five)_TwoAlCl, (C_TwoH_Five)_1.5AlC
l_1.5, (C_TwoH_Five) AlCl_Two, Methylalumoxa
And LiH described in JP-A-1-240517.
Compounds can be mentioned. Component (c) which is an additive
Representative examples of alcohols, aldehydes, keto
Amines and amines can be preferably used.
Used the compound disclosed in JP-A-1-240517.
Can be used.

The amount of the metathesis catalyst used is such that the molar ratio of the component (a) to the specific monomer is such that "component (a): specific monomer" is usually 1: 500 to 1: 50000. , Preferably in the range of 1: 1000 to 1: 10000. The ratio of the component (a) to the component (b) is such that “(a) :( b)” is in the range of 1: 1 to 1:50, preferably 1: 2 to 1:30 in terms of metal atom ratio. . The ratio of the component (a) to the component (c) is “(c) :( a)” in molar ratio.
Is 0.005: 1 to 15: 1, preferably 0.05: 1
７7: 1.

<Molecular Weight Controlling Agent> The molecular weight of the ring-opened polymer can be controlled by the polymerization temperature, the type of catalyst, and the type of solvent. In the present invention, the molecular weight controlling agent must be present in the reaction system. It is preferable to adjust by.
Here, suitable molecular weight regulators include, for example, α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. Styrene can be mentioned, among which 1-butene and 1-hexene are particularly preferred. These molecular weight regulators can be used alone or in combination of two or more. The amount of the molecular weight modifier used is 0.005 to 0.6 mol, preferably 0.02 to 0.5 mol, per 1 mol of the specific monomer subjected to the ring-opening polymerization reaction.

<Solvent for Ring-Opening Polymerization Reaction> Examples of the solvent (solvent for dissolving the specific monomer, the metathesis catalyst and the molecular weight modifier) used in the ring-opening polymerization reaction include pentane, hexane, heptane, octane, nonane, and the like. Alkanes such as decane; cyclohexane, cycloheptane,
Cycloalkanes such as cyclooctane, decalin and norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; chlorobutane;
Halogenated alkanes such as bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform, tetrachloroethylene;
Compounds such as aryl; ethyl acetate, n-butyl acetate,
Saturated carboxylic esters such as iso-butyl acetate, methyl propionate and dimethoxyethane; ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane can be used, and these can be used alone or in combination. Of these, aromatic hydrocarbons are preferred. The amount of the solvent used is such that “solvent: specific monomer (weight ratio)” is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1. .

<Hydrogenation catalyst> The ring-opened (co) polymer obtained as described above can be used as the component (A) as it is. It is preferred to use as component (A). The hydrogenation reaction is carried out in a usual manner, that is, a hydrogenation catalyst is added to a solution of the ring-opening (co) polymer, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm is added to the solution at 0 to 200 atm.
C., preferably at 20-180.degree. As the hydrogenation catalyst, those used in ordinary hydrogenation reactions of olefinic compounds can be used. As the hydrogenation catalyst, a heterogeneous catalyst and a homogeneous catalyst are known. Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst substance such as palladium, platinum, nickel, rhodium and ruthenium is supported on a carrier such as carbon, silica, alumina and titania. Examples of the homogeneous catalyst include nickel / naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octanoate / n-butyllithium, titanocene dichloride /
Diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium and the like can be mentioned. it can. The form of the catalyst may be powdery or granular. These hydrogenation catalysts are used in such a ratio that the “ring-opening (co) polymer: hydrogenation catalyst (weight ratio)” is 1: 1 × 10 ⁻⁶ to 1: 2. As described above, the hydrogenated (co) polymer obtained by hydrogenation has excellent thermal stability, and its properties are not deteriorated by heating during molding or use as a product. . Here, the hydrogenation rate is usually 50% or more, preferably 70% or more, more preferably 90% or more, further preferably 95% or more, and particularly preferably 97% or more.

<Unsaturated Double Bond-Containing Compound Constituting a Saturated Copolymer> In order to obtain the component (A) composed of a saturated copolymer, the unsaturated dibond used in the copolymerization reaction with a specific monomer is obtained. Examples of the heavy bond-containing compound include olefin compounds having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, such as ethylene, propylene, and butene. As for these unsaturated double bond-containing compounds, “specific monomer / unsaturated double bond-containing compound (weight ratio)” is 90/10 to 40/60.
And more preferably in a ratio of 85/15 to 50/50.

<Catalyst Used for Obtaining Saturated Copolymer>
Copolymerization reaction between specific monomer and unsaturated double bond-containing compound
The catalysts used for vanadium compounds and organic
A catalyst comprising a luminium compound is used. Vanaji
The compound represented by the general formula VO (OR)_aX_bOr
V (OR)_cX _d(Where R is a hydrocarbon group, 0 ≦ a ≦
3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d
≦ 4, 3 ≦ c + d ≦ 4) a vanadium compound represented by the following formula:
Alternatively, these electron donor adducts are used. Electronic
Donors include alcohols, phenols, ketones, and alcohols.
Esters of aldehydes, carboxylic acids, organic or inorganic acids
, Ether, acid amide, acid anhydride, alkoxysilane
Oxygen-containing electron donors such as ammonia, amines, nitrites
And nitrogen-containing electron donors such as isocyanate and the like.
It is. As an organoaluminum compound catalyst component,
At least one aluminum-carbon bond or aluminum
At least one selected from those having an um-hydrogen bond
Seeds are used. The ratio of catalyst components to vanadium atoms
Aluminum atom ratio (Al / V) of 2 or more
From 2 to 50, particularly preferably from 3 to 20.
You.

<Solvent used for obtaining saturated copolymer>
Examples of the solvent used in the copolymerization reaction between the specific monomer and the unsaturated double bond-containing compound include alkanes such as pentane, hexane, heptane, octane, nonane, and decane; cycloalkanes such as cyclohexane and methylcyclohexane. And aromatic hydrocarbons such as benzene, toluene and xylene, and halogen derivatives thereof. Of these, cyclohexane is preferable.

The intrinsic viscosity (ηinh) of the component (A) used in the present invention, measured in chloroform at 30 ° C., is 0.1.
It is preferably from 2 to 5.0 dl / g. Also (A)
As the molecular weight of the component, the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) is 8,000 to 100,000,
Weight average molecular weight (Mw) of 20,000 to 300,00
Those in the range of 0 are preferred.

<Component (B)> The resin composition of the present invention is characterized in that it contains the component (B) which is a phosphorus-based antioxidant having a specific chemical structure. This component (B) is more thermally decomposed and hydrolyzed than other phosphorus-based antioxidants (for example, conventionally known phosphorus-based antioxidants such as tris (2,4-di-t-butylphenyl) phosphite). Therefore, even under high temperature conditions, the effect of preventing oxidation deterioration (coloring of the molded article) and the effect of preventing thermal decomposition (occurrence of burning) can be reliably exhibited.

In the above formula (I) representing the component (B), R ^{1 to} R ¹⁰ each represent a hydrogen atom or a hydrocarbon group, which may be the same or different. However, among the five groups represented by R ^{1 to} R ⁵ , 1 to 3 groups are substituted or unsubstituted cumenyl groups represented by the above formula (1), and R ^{6 to} R ¹⁰ Of the five groups shown, one to three groups are substituted or unsubstituted cumenyl groups represented by the above formula (1).

Among the groups represented by R ^{1 to} R ¹⁰ , examples of the group other than the substituted or unsubstituted cumenyl group include a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms. Among the groups represented by R ^{1 to} R ¹⁰ , preferred as a group other than a substituted or unsubstituted cumenyl group are a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. , Sec-butyl group, t-butyl group, n-pentyl, i-pentyl group, neo-pentyl group, t-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, a n-decyl group, a vinyl group, an allyl group and an i-propenyl group, among which a hydrogen atom, a t-butyl group and a t-pentyl group are particularly preferred, and a hydrogen atom is most preferred.

In the above formula (1) representing a substituted or unsubstituted cumenyl group, R ^{11 to} R ¹⁵ each represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. May be. Preferred as the groups represented by R ^{11 to} R ¹⁵ are groups selected from the above groups, and among these, a hydrogen atom, a t-butyl group, a t-butyl group,
Amyl groups are particularly preferred, and hydrogen atoms are most preferred.

The number of substituted or unsubstituted cumenyl groups in one molecule of the compound (phosphorus antioxidant) constituting the component (B) is usually 2 to 6, preferably 3 to 5,
More preferably, the number is four. When the compound constituting the component (B) has four (substituted) cumenyl groups, two of the five groups represented by R ^{1 to} R ⁵ , and R ^{6 to} R ¹⁰ It is preferable that two of the five groups represented by the general formula (I) are (substituted) cumenyl groups, and the groups represented by R ¹ , R ³ , R ⁸ and R ¹⁰ in the general formula (I) are (substituted) ) A compound which is a cumenyl group [compound represented by the above general formula (II)] is particularly preferable.

In the general formula (II), R ^{16 to} R ⁴¹ each represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different. Here, preferred as the groups represented by R ^{16 to} R ⁴¹ are a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group and a t-butyl group. , N-pentyl, i-pentyl, neo-pentyl, t-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, vinyl, allyl And i-propenyl group,
Of these, a hydrogen atom, a t-butyl group, and a t-amyl group are particularly preferred, and a hydrogen atom is most preferred.

Specific examples of the component (B) represented by the general formula (II) include bis (2,4-dicumylphenyl) pentaerythritol diphosphite and bis (2-cumylphenyl) pentaerythritol diphosphite. , Bis (4-cumylphenyl) pentaerythritol diphosphite, bis (2,6-dicumylphenyl) pentaerythritol diphosphite, bis (2,4,6-tricumylphenyl) pentaerythritol diphosphite and the like. Of these, bis (2,4-
Dicumylphenyl) pentaerythritol diphosphite is particularly preferred.

The content of the component (B) in the resin composition of the present invention is 0.01 to 100 parts by weight of the component (A).
It is preferably from 10 to 10 parts by weight, more preferably from 0.05 to 5 parts by weight. Here, when the content ratio of the component (B) is too small, the effect of preventing oxidative deterioration (coloring of a molded article) and the effect of preventing thermal decomposition (occurrence of burning) of the obtained resin composition are sufficiently improved. Can not demonstrate. On the other hand, when the content ratio of the component (B) is excessive, the mechanical properties of the obtained resin composition may be impaired.

<Component (C)> The resin composition of the present invention comprises:
It is preferable that a hindered phenolic antioxidant is contained as the component (C) together with the component (B).
Thus, by using two kinds of antioxidants together,
Component (C), which is a hindered phenol-based antioxidant, acts as a primary antioxidant that traps radicals,
The component (B), which is a phosphorus-based antioxidant, acts as a secondary antioxidant that reduces and decomposes hydroperoxide generated with deterioration. Further, the component (C) has an excellent effect of preventing oxidative deterioration under normal temperature conditions. The molecular weight of the component (C) is preferably 350 or more, which makes it difficult to be decomposed even under high temperature conditions, and can suppress generation of decomposed gas in a resin composition containing the same.

As the component (C) having a molecular weight of 350 or more,
Those having an alkyl ester structure of 3- (3,5-di-alkyl-substituted-4-hydroxyphenyl) propionic acid are preferred from the viewpoint of preventing coloring of the resin composition. Here, as the alkyl substituent, a methyl group, a t-butyl group, and a t-amyl group are preferable. Further, as the “alkyl ester” constituting the above structure, an alkyl monoester having 30 or less carbon atoms and an ester of a polyhydric alcohol having a molecular weight of 300 or less are preferable.

Preferred specific examples of the component (C) include pentaerythrityl-tetrakis [3- (3,5-di-t
-Butyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-t-butyl-4)
-Hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl 2,4,8,10-tetraoxaspiro [5,5] undecane, octadecyl-3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], and the like.

The content of the component (C) in the resin composition of the present invention is 0.01 to 100 parts by weight of the component (A).
It is preferably from 10 to 10 parts by weight, more preferably from 0.05 to 5 parts by weight. Here, when the content ratio of the component (C) is too small, the combined effect (effect as a primary antioxidant) cannot be sufficiently exhibited. On the other hand, when the content ratio of the component (C) is excessive, the mechanical properties of the obtained resin composition may be impaired.

<Optional Components> The resin composition of the present invention comprises:
A hydrocarbon resin, a polystyrene oligomer, or a rosin resin may be contained as a resin component other than the component (A), the component (B) and the component (C), and the fluidity of the resin composition obtained by these resin components may be reduced. Can be improved. The content of the above resin component is usually 0.01 to 60 parts by weight, preferably 0.1 to 30 parts by weight, per 100 parts by weight of the component (A).

These resin components are solid at ordinary temperature and have a polystyrene equivalent weight average molecular weight (Mw) of 2
It is preferably not more than 0000, preferably 200 to 20,000. Here, if the weight average molecular weight in terms of polystyrene is too large, the compatibility with the component (A) becomes poor, and the transparency is undesirably reduced. It is not preferable to use a hydrocarbon resin or the like which is liquid at room temperature, because the strength of the resin is reduced and the resin bleeds on the surface of the resin.

Examples of such hydrocarbon resins include C ₅ -based resins, C ₉ -based resins, C ₅ / C ₉ -based mixed resins, cyclopentadiene-based resins, polymer resins of vinyl-substituted aromatic compounds, and olefin / vinyl-substituted resins. Copolymer resins of aromatic compounds, copolymer resins of cyclopentadiene compounds / vinyl-substituted aromatic compounds, hydrogenated products of the resins, and hydrogenated products of the resins can be exemplified.

The rosin resin includes, for example, apietic acid, pimaric acid and the like, and derivatives thereof such as hydrogenated products, disproportionated products, polymers and esterified products.

For the purpose of improving mechanical properties, the resin composition of the present invention contains glass fiber, carbon fiber, metal fiber, metal flake, glass bead, wollastonite, rock filler, calcium carbonate, talc, silica, Fillers such as mica, glass flakes, milled fiber, kaolin, barium sulfate, graphite, molybdenum disulfide, magnesium oxide, zinc oxide whiskers, and potassium titanate whiskers can be used alone or as a mixture of two or more. Can also be used.

The resin composition of the present invention may contain additives such as known flame retardants, antibacterial agents, wood flour, coupling agents, antioxidants, plasticizers, coloring agents, lubricants, silicone oil, and foaming agents. Can also be blended.

As a method for producing the resin composition of the present invention, for example, a pellet is prepared by mixing the component (A), the component (B) and an optional component using a twin-screw extruder, a roll kneader or the like. And a method of obtaining a resin composition by mixing the solution of the component (A) and the solution of the component (B) and removing the solvent.

As the above-mentioned production method, for example, a melt kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, a roll, a feeder ruder and the like can be used. The kneading temperature is preferably 100 to 350.
° C, more preferably 150 to 300 ° C. Also,
When kneading the components, the components may be kneaded all at once or may be kneaded while being added in several portions.

According to the resin composition of the present invention, a molded article can be produced by a known molding means such as an injection molding method, a compression molding method, and an extrusion molding method. Here, the shape of the molded product is not particularly limited.

Also, an inorganic compound, an organic silicon compound such as a silane coupling agent, an acrylic resin, a vinyl resin, a melamine resin, an epoxy resin, a fluorine-based resin are formed on the surface of a molded article produced by the resin composition of the present invention. A hard coat layer made of a resin, a silicone resin, or the like can be formed. As a means for forming the hard coat layer, a thermosetting method, an ultraviolet curing method, a vacuum deposition method, a sputtering method,
Known methods such as an ion plating method can be used. As a result, the heat resistance, optical properties,
Chemical resistance, abrasion resistance, water resistance and the like can be improved.

The application of the resin composition of the present invention is not particularly limited and can be used in a wide range. For example, eyeglass lenses, general camera lenses, pickup lenses, video camera lenses, telescope lenses,
Lenses such as laser beam lenses, optical video discs, audio discs, document file discs,
Particularly suitable for use as optical materials such as memory disks, optical materials such as optical films such as OHP films, photointerrupters, photocouplers, optical semiconductor encapsulants such as LED lamps, and IC memory encapsulants such as IC cards. can do.

[0060]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited by these. In the following, “parts” indicates “parts by weight”.

[Preparation Example (A-1)] 8-Methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (specific monomer) 250 parts and 1-hexene (molecular weight regulator) 4
One part and 750 parts of toluene (solvent for ring-opening polymerization reaction) were charged into a nitrogen-purged reaction vessel, and the solution was heated to 60 ° C. Next, a solution of triethylaluminum in toluene (1.5 mol / l) 0.62 was added to the solution in the reaction vessel.
And a toluene solution of tungsten hexachloride (t-butanol: methanol: tungsten = 0.35 mol: 0.3 mol: 1 mol) modified with t-butanol / methanol (concentration: 0.05 mol / l) 3. Then, the mixture was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction to obtain a ring-opened polymer solution. The polymerization conversion rate in this polymerization reaction was 97%, and the obtained ring-opened polymer was 30%.
The intrinsic viscosity (ηinh) measured in chloroform at 0.4 ° C. was 0.45 dl / g.

[0062]

Embedded image

4,000 parts of the ring-opening polymer solution thus obtained was charged into an autoclave, and RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution.
0.48 parts, hydrogen gas pressure 100 kg / cm ² ,
A hydrogenation reaction was performed by heating and stirring for 3 hours at a reaction temperature of 165 ° C. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released, and the reaction solution was poured into a large amount of methanol to coagulate and separate and collect the hydrogenated polymer. The hydrogenation rate of the hydrogenated polymer (hereinafter referred to as “resin (A-1)”) thus obtained was substantially 100%, and the number average molecular weight (Mn) in terms of polystyrene measured by GPC. Is 19,800,
The weight average molecular weight (Mw) was 62,000.

[Preparation Example (A-2)] 8-Methyl-8-me
Toxicarbonyltetracyclo [4.4.0.1^2,5.
1 ^7,108-ethylidentate instead of -3-dodecene
Lacyclo [4.4.0.1 ^2,5. 1^7,10] -3-Dodece
Same as Preparation Example (A-1) except that 200 parts of
Ring-opening polymerization reaction, hydrogenation reaction and coagulation recovery treatment
To obtain a hydrogenated polymer. Obtained in this way
Hydrogenated polymer (hereinafter referred to as “resin (A-2)”)
U. ) Is virtually 100% and measured by GPC.
The determined polystyrene equivalent number average molecular weight (Mn) is 1
9,200, weight average molecular weight (Mw) is 58,000
there were.

[Preparation Example (A-3)] Stirring blade, gas introduction
The reaction vessel, equipped with a tube, thermometer and dropping funnel, is
And replace the reaction system with a molecular sieve.
2,000 parts of cyclohexane dehydrated and dried
And tetracyclo [4.4.0.1 in a nitrogen atmosphere.
^2,5. 1^7,10] 75 parts of dodecene and ethyl aluminum
N-hexane solution of ammonium sesquichloride (1 mol /
l) 6.6 parts were added. Then, the temperature in the reaction vessel
With the temperature kept at 10 ° C., the gas was introduced into the reactor
Mixed gas of ethylene and nitrogen (ethylene flow rate: 10 litres
/ Hr, nitrogen flow rate: 40 liter / Hr) for 10 minutes
Supplied. Then, VO (OC _TwoH_Five) C
l_Two23 parts of n-hexane solution (0.07 mol / l)
From the dropping funnel to start the copolymerization reaction,
The reaction was continued while passing the combined gas. Start the reaction
After 30 minutes, add a small amount of methanol to the reaction solution
To stop the polymerization reaction,
And solidify the polymer (saturated copolymer)
Was. The polymer thus obtained (hereinafter referred to as “resin (A)
-3) ". ) Polystyrene exchange measured by GPC
The calculated number average molecular weight (Mn) is 21,000, weight average
The molecular weight (Mw) was 63,000.

Example 1 According to the formulation shown in Table 1, 100 parts of the resin (A-1) and bis (2,4-dicumylphenyl) pentaerythritol diphosphoric acid as a phosphorus-based antioxidant (component (B)) were used. 0.1 part of phosphite (hereinafter referred to as “phosphorous antioxidant (B-1)”) and pentaerythrityl-tetrakis [3- (3) as a hindered phenolic antioxidant [component (C)] , 5-Di-t-butyl-
4-Hydroxyphenyl) propionate] and 0.5 part of the resulting mixture, and the resulting mixture is fed to an extruder “VS
K40 ”(manufactured by Nakatani Machinery Co., Ltd.) using melt kneading (screw rotation speed: 150 rpm, set temperature: 280 ° C.)
Then, by pelletizing, a resin composition of the present invention was obtained.

[Examples 2 to 3] Pelletization was carried out in the same manner as in Example 1 except that the amount of the phosphorus-based antioxidant (B-1) was changed according to the formulation shown in Table 1 below. The obtained resin composition of the present invention was obtained.

Example 4 According to the recipe shown in Table 1 below, the same operation as in Example 2 was carried out except that 100 parts of resin (A-2) was used instead of resin (A-1). A pelletized resin composition of the present invention was obtained.

Example 5 In the same manner as in Example 2 except that 100 parts of the resin (A-3) was used in place of the resin (A-1) according to the formulation shown in Table 1 below, A pelletized resin composition of the present invention was obtained.

Comparative Example 1 The procedure of Example 1 was repeated except that no phosphorus-based antioxidant (B-1) or a hindered phenol-based antioxidant was used in accordance with the formulation shown in Table 1 below. By performing the same operation as in Example 1, a pelletized thermoplastic resin was obtained.

Comparative Example 2 The same operation as in Example 4 was performed according to the formulation shown in Table 1 below, except that the phosphorus antioxidant (B-1) and the hindered phenol antioxidant were not used. Then, a pelletized thermoplastic resin was obtained.

Comparative Example 3 The same operation as in Example 5 was performed according to the formulation shown in Table 1 below, except that the phosphorus antioxidant (B-1) and the hindered phenol antioxidant were not used. Then, a pelletized thermoplastic resin was obtained.

[Comparative Example 4] The same procedure as in Example 1 was carried out except that the phosphorus-based antioxidant (B-1) was not used in accordance with the formulation shown in Table 1 below. A resin composition was obtained.

Comparative Example 5 According to the formulation shown in Table 1 below, 100 parts of resin (A-1) and tris (2,4-di-t-butylphenyl) as a phosphorus-containing antioxidant for comparison were used.
Phosphite (hereinafter referred to as “phosphorous antioxidant (b-1)”)
That. ) 0.3 parts and 0.5 parts of a hindered phenolic antioxidant are dry-blended, and the resulting mixture is melt-kneaded using an extruder “VSK40” (manufactured by Nakatani Machinery Co., Ltd.). Screw rotation speed: 150 rpm, set temperature: 280 ° C.), and pelletized to obtain a resin composition for comparison.

<Evaluation of Resin Composition> For each of the pellet-shaped resin compositions (resins) obtained in Examples 1 to 5 and Comparative Examples 1 to 5, the hue (colorability) of the molded product and the aging of the hue The evaluation was made on the characteristic change (heat aging test), the degree of burning in the molded product, and the degree of decomposition gas generated in the molding process. Table 1 also shows these results. The evaluation method (measuring method) is as follows.

[1] Hue of molded product: Injection molding machine "IS8
0A "(manufactured by Toshiba Machine Co., Ltd., 5 ounces), injection pressure 900 kg / cm ² , screw rotation speed 80 rpm,
A molded product (80 mm × 40 mm × 3.2 m) is obtained by performing injection molding under the conditions of a cycle of 45 seconds and a mold temperature of 80 ° C.
m) was obtained, and the yellowness (YI value) of this molded product was measured in accordance with JIS K7103.

[2] Temporal change of hue (heat aging test):
After the molded article produced by the above [1] was left in an oven (temperature: 135 ° C.) for 50 hours, the yellowness (YI value) was measured in the same manner as in the above [1].

[3] Degree of burn in the molded article: A molded article was obtained under the same conditions as in the above [1] except that the resin composition (resin) was retained in the injection molding machine for 30 minutes.
About this molded product (80 mm × 40 mm × 3.2 mm), the degree of burn was visually confirmed. The evaluation criteria are as follows. “◎”: No scorch occurred. "O": Burning occurred in 10% by number or less of the molded product. “Δ”: Burning occurred in 10 to 80% by number of molded articles. “×”: Burning occurred in 80% or more of the molded product.

[4] Degree of decomposition gas: Injection molding machine “IS
80A "(manufactured by Toshiba Machine Co., Ltd.), a purging operation (set temperature: 350 ° C., time:
Decomposed gas particles generated during 30 seconds) (1 μm or more)
Was measured using a particle counter (manufactured by Transtech Co., Ltd.).

[0080]

[Table 1]

As is clear from the results shown in Table 1, according to the resin compositions of Examples 1 to 5, the yellowness was small,
A molded product having a very small degree of burn (generation rate) can be obtained, and the amount of generated decomposition gas in the molding process is small. Further, even when a molded article made of the resin composition was left in a high-temperature environment, the change over time in the hue of the molded article was small. On the other hand, the resin (resin composition) according to Comparative Examples 1 to 4 containing no component (B)
The molded product obtained by the above method had a large degree of burning. Further, the molded product obtained from the resin (resin composition) according to Comparative Examples 1 to 3 has a large yellowness. Further, when the molded product made of the resin composition is left in a high-temperature environment, the hue of the molded product becomes The color changed greatly and the yellow color became strong. Furthermore, according to the resin composition according to Comparative Example 5 containing the comparative phosphorus-based antioxidant (b-1), a large amount of decomposition gas was generated in the molding process, and contamination on the mold surface occurred. As a result, there arises a problem that the surface of the molded article is inferior and the like, which is not preferable from the viewpoint of moldability.

[0082]

According to the resin composition of the present invention, even if it is molded and processed under high temperature conditions, the resulting molded article is colored (yellowed) due to oxidative deterioration and burns (black stripes) due to thermal decomposition. )
Does not occur. Further, the molded article obtained from the resin composition of the present invention is excellent in colorless and transparent, and can maintain the initial hue (colorless and transparent) even when used (left) in a high-temperature environment. In addition, in a molding process performed using the resin composition of the present invention, the amount of decomposition gas generated from the resin composition is extremely small. This can contribute to the expansion of applications of cyclic olefin-based resins in the field of optical materials such as semiconductor encapsulation, optical semiconductor encapsulation, optical lenses, optical fibers, optical discs, etc., and the industrial value by this is extremely high. high.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masayuki Sekiguchi 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Co., Ltd. F-term (reference) 4J002 CE001 EJ067 EW086 FD010 FD076 FD077 GJ02 GP00 GP01 GS00 GS02

Claims (8)

[Claims] 1. A resin composition comprising: a cyclic polyolefin resin (A); and a phosphorus antioxidant (B) represented by the following general formula (I). Embedded image [In the general formula (I), R ^{1 to} R ¹⁰ each represent a hydrogen atom or a hydrocarbon group, and may be the same or different. However, ^{1 to 3} of the 5 groups represented by R ^{1 to} R ⁵ are substituted or unsubstituted cumenyl groups represented by the following formula (1), and represented by R ^{6 to} R ¹⁰ 1 to 3 of the five groups are substituted or unsubstituted cumenyl groups represented by the following formula (1). [Chemical formula 2] [In the formula (1), R ^{11 to} R ¹⁵ each represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different. ] 2. The resin composition according to claim 1, wherein in the general formula (I) representing the phosphorus-based antioxidant (B),
Of the groups represented by R ^{1 to} R ¹⁰ , a group other than a substituted or unsubstituted cumenyl group is a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group,
sec-butyl group, t-butyl group, n-pentyl, i-
Pentyl group, neo-pentyl group, t-pentyl group, n
-Hexyl group, n-heptyl group, n-octyl group, n-
Nonyl group, n-decyl group, vinyl group, allyl group and i
- a group selected from the group consisting of propenyl, in the formula (1) represents a substituted or unsubstituted cumenyl group, group represented by R ¹¹ to R ¹⁵ is is a group selected from the group of the A resin composition comprising: 3. The resin composition according to claim 1, wherein in the general formula (I) representing a phosphorus-based antioxidant (B),
Two of the five groups represented by R ^{1 to} R ⁵ are substituted or unsubstituted cumenyl groups represented by the formula (1), and the five groups represented by R ^{6 to} R ¹⁰ Wherein two of the groups are substituted or unsubstituted cumenyl groups represented by the formula (1). 4. The resin composition according to claim 1, further comprising a phosphorus antioxidant (B) represented by the following general formula (II). Resin composition. Embedded image [In the general formula (II), R ^{16 to} R ⁴¹ each represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different. ] 5. The resin composition according to claim 1, wherein the resin is a cyclic polyolefin resin (A).
100 parts by weight, phosphorus-based antioxidant (B) 0.0
A resin composition comprising 1 to 10 parts by weight. 6. The resin composition according to claim 1, further comprising a hindered phenolic antioxidant (C). 7. The resin composition according to claim 6, wherein the phosphorus-based antioxidant (B) is 0.01 to 10 parts by weight based on 100 parts by weight of the cyclic polyolefin-based resin (A).
Hindered phenolic antioxidant (C) 0.01-1
And 0 parts by weight. 8. The resin composition according to claim 1, wherein the cyclic polyolefin resin (A)
Is a ring-opening (co) polymer of a monomer represented by the following general formula (III) and a copolymerizable monomer. Embedded image [In the general formula (III), R ⁴² and R ⁴⁴ represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ⁴³ and R ⁴⁵
Is a hydrogen atom or a monovalent organic group, and at least one of R ⁴³ and R ⁴⁵ represents a polar group other than a hydrogen atom and a hydrocarbon group. m is an integer of 0 to 3, p is an integer of 0 to 3, and m + p is 0 to 4. ]