JPH11323098A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition having further excellent low birefringence while retaining the characteristics inherent in well-known cyclic polyolefin-based resins, and useful for e.g. automotive parts, by including a cyclic polyolefin-based resin and an aromatic vinyl-based (co)polymer. SOLUTION: This thermoplastic resin composition comprises (A) 100 pts.wt. of a cyclic polyolefin-based resin and (B) 0.01-100 pts.wt. of a polar group-contg. aromatic vinyl-based (co)polymer; wherein it is recommended, for example, that the component A is a ring-opened polymer made from a monomer of the formula (R<1> to R<4> are each H, a halogen, 1-10C hydrocar 6 on or the like; (m) and (p) are each 0 or a positive integer), and the component B is a homopolymer of a polar group-contg. monomer such as p-methoxystyrene or a copolymer made from the above monomer and a copolymerizable monomer which is used as appropriate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition, and more particularly, to a thermoplastic resin composition excellent in low birefringence and the like.

[0002]

2. Description of the Related Art Conventionally, a transparent resin has been used as a material for a molded article such as an automobile part, a lighting device, an electric part, etc., which requires ordinary transparency. The application of is progressing. As a transparent resin suitably used for such an application, a polycarbonate resin and an acrylic resin are known. However, although acrylic resins are excellent in transparency, they have problems in heat resistance, water resistance and the like. On the other hand, polycarbonate resins are superior to acrylic resins in heat resistance and water resistance, but have problems such as high birefringence. Recently, cyclic polyolefin-based resins having transparency, water resistance (low water absorption), low birefringence, heat resistance, and the like have been used as transparent resins for optical materials. However, conventionally known cyclic polyolefin-based resins do not have a sufficiently low birefringence, and the development of a transparent resin (thermoplastic resin composition) having a further excellent low birefringence has been desired.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has as its object to improve various characteristics (transparency, transparency, etc.) of a conventionally known cyclic polyolefin resin.
Another object of the present invention is to provide a thermoplastic resin composition having excellent low birefringence while maintaining water resistance and heat resistance.

[0004]

Means for Solving the Problems The thermoplastic resin composition of the present invention comprises a cyclic polyolefin resin (A) (hereinafter referred to as a cyclic polyolefin resin).
Also referred to as “component (A)”. ) 100 parts by weight of a polar group-containing aromatic vinyl (co) polymer (B) (hereinafter referred to as
Also referred to as “component (B)”. ) 0.01 to 100 parts by weight.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the thermoplastic 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 following general formula (I) (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

[0006]

Embedded image

[Wherein, R ^{1 to} R ⁴ are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or another monovalent organic group. You may. R ¹ and R ² or R ³ and R
⁴ may combine to form a divalent hydrocarbon group,
R ¹ or R ² and R ³ or R ⁴ are bonded to each other,
It may form a monocyclic or polycyclic structure. m is 0 or a positive integer, and p is 0 or a positive integer. The cyclic polyolefin resin [component (A)] obtained from the specific monomer preferably contains a polar group in the molecular structure from the viewpoint of improving compatibility with the component (B). .

<Specific monomer> As a preferred specific monomer, R ¹ and R ^{3 in} the above general formula (I) are a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ² and R 3
⁴ is a hydrogen atom or a monovalent organic group, at least one of R ² and R ⁴ 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). Also, among the specific monomers,
The specific monomer having a polar group represented by the formula — (CH ₂ ) _n COOR ⁵ is preferable in that the resulting thermoplastic resin composition has a high glass transition temperature and a low hygroscopic property. In the above formula according to the polar group, R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, preferably an alkyl group. In addition, n is generally 0 to 5, but a smaller value of n is preferable because the glass transition temperature of the obtained thermoplastic resin composition is higher. Further, the specific monomer in which n is 0 is preferable. It is preferable in that the synthesis is easy. Further, in the general formula (I), R ¹ or R ³ is preferably an alkyl group, and the alkyl group has 1 to 4 carbon atoms.
Is more preferable, more preferably 1-2, and particularly preferably 1. In particular, this alkyl group has the formula-
It is preferable that the polar group represented by (CH ₂ ) _n COOR ⁵ 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 (I) is preferable in that a thermoplastic resin composition having a high glass transition temperature can be obtained.

The specific monomer represented by the above general formula (I)
The following compounds may be mentioned as specific examples. Bi
Cyclo [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.

Of 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 is
The thermoplastic resin composition obtained in the above has excellent heat resistance
In particular, particularly, 8-methyl-8-methoxy
Rubonyltetracyclo [4.4.0.1^2,5. 1^7,10]
-3-Dodecene is a cyclic compound having excellent compatibility with the component (B).
It is preferable because a polyolefin resin can be obtained.

<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.
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.

(A) 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
Typical examples of alcohols, aldehydes, keto
Amines and amines can be preferably used.
The compound disclosed in JP-A-1-240517 is used for
Can be used.

The amount of the metathesis catalyst to be used is such that the molar ratio of the component (a) to the specific monomer is such that "component (a): specific monomer" is usually from 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 coexist 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, and more preferably 90% 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 copolymer used for 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.

<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 thermoplastic composition of the present invention is characterized in that a polar group-containing aromatic vinyl (co) polymer is contained as the component (B). . Examples of the polar group contained in the component (B) include a hydroxyl group, an alkoxy group, a carboxyl group, a carboxylate group, a carbonyl group, an amide group, an amino group, a nitro group, and a cyano group.

The component (B) can be prepared by (co) polymerizing a polar group-containing monomer and, if necessary, a copolymerizable monomer.

<Polar group-containing monomer> Here, as the polar group-containing monomer whose polar group is a "hydroxyl group",
p-hydroxystyrene, α-methyl p-hydroxystyrene, 2-methyl-4-hydroxystyrene, 3,4
-Hydroxystyrenes such as dihydroxystyrene and vinylbenzyl alcohols. As the polar group-containing monomer whose polar group is an `` alkoxy group '',
p-methoxystyrene, pt-butoxystyrene, m
And alkoxy-substituted styrenes such as -t-butoxystyrene. Examples of the polar group-containing monomer whose polar group is a “carboxyl group” include vinylbenzoic acids such as 3-vinylbenzoic acid and 4-vinylbenzoic acid, and 2-phenylacrylic acid. As the polar group-containing monomer whose polar group is a “carboxylic acid ester group”, methyl 4-
Vinyl benzoate, ethyl 4-vinyl benzoate,
4-vinylbenzyl acetate, 4-acetoxystyrene and the like. Examples of the polar group-containing monomer whose polar group is a “carbonyl group” include p-butenylacetophenone, m-isopropynylacetophenone, and the like. Examples of the polar group-containing monomer whose polar group is an “amide group” include 2-butylamidostyrene, 4-methylamidostyrene, and p-sulfonamidostyrene. Examples of the polar group-containing monomer whose polar group is an “amino group” include 3-aminostyrene, 4-aminostyrene, and 2-aminostyrene.
Isopropenylaniline, vinylbenzyldimethylamine and the like. Examples of the polar group-containing monomer in which the polar group is a “nitro group” include 3-nitrostyrene, 4-nitrostyrene, and the like. Examples of the polar group-containing monomer whose polar group is a “cyano group” include 3-cyanostyrene,
4-cyanostyrene, vinylphenylacetonitrile and the like. Of these, p-methoxystyrene, pt-butoxystyrene, p-hydroxystyrene, and methyl 4-vinylbenzoate are particularly preferred. These polar group-containing monomers can be used alone or in combination of two or more.

<Copolymerizable Monomer> The copolymerizable monomers used as necessary for constituting the component (B) include styrene, α-methylstyrene, β-methyl Styrene, alkyl-substituted styrenes such as p-methylstyrene, halogen-substituted styrenes such as 4-chlorostyrene and 4-bromostyrene, arylstyrenes such as phenylstyrene, vinylnaphthalene, vinylanthracene, 1,1-diphenylethylene, Acrylic monomers such as methyl acrylate, ethyl acrylate, benzyl acrylate and phenyl acrylate; methacrylic monomers such as methyl methacrylate, ethyl methacrylate, benzyl methacrylate and phenyl methacrylate; 2-hydroxyethyl acrylate;
A hydroxyl group-containing unsaturated compound such as hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, and 3-hydroxypropyl methacrylate can be used.

<Preparation of Component (B)> The ratio of the polar group-containing monomer in the monomer constituting the component (B) is 0.1 to 0.1.
It is preferably 100 mol%, more preferably 2 mol%.
-50 mol%, particularly preferably 5-30 mol%. When the use ratio of the polar group-containing monomer is less than 0.1 mol%, not only the thermoplastic resin composition finally obtained does not have a sufficiently low birefringence but also the thermoplastic resin composition. The molded article may become cloudy due to phase separation or the like.

The polymerization initiator / catalyst used in the (co) polymerization reaction for obtaining the component (B) is not particularly limited, and may be a known radical polymerization initiator, anionic polymerization catalyst, or coordinating anion. Examples thereof include a polymerization catalyst and a cationic polymerization catalyst. As the polymerization method for obtaining the component (B), an appropriate method such as a bulk polymerization method, a solution polymerization method, a precipitation polymerization method, an emulsion polymerization method, a suspension polymerization method, a bulk-suspension polymerization method, or the like is employed. be able to.

The aromatic vinyl (co) polymer particularly suitable as the component (B) includes pt-butoxystyrene-
Examples thereof include a styrene copolymer, a p-hydroxystyrene-styrene copolymer, and a methyl 4-vinylbenzoate-styrene copolymer.

In order to obtain a thermoplastic resin composition having excellent transparency and low birefringence, the components (A) and (B) must be completely compatible. Therefore, it is necessary to select the type of component (B) (the type of polar group), molecular weight and content according to the type of component (A). Here, as the molecular weight of the component (B), the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) is 500.
To 20,000, more preferably 5,000 to 100,000, particularly preferably 20,000.
000-80,000.

The content of the component (B) is as follows:
(A) Usually 0.01 to 100 parts by weight per 100 parts by weight of the component.
Parts by weight, preferably 0.1 to 50 parts by weight, more preferably 2 to 20 parts by weight. If the amount of the component (B) is less than 0.01 part by weight, the resulting thermoplastic resin composition will not have a sufficiently low birefringence. On the other hand, if the compounding amount exceeds 100 parts by weight, the heat resistance and transparency of the obtained thermoplastic resin composition become low, which is not preferable.

The resin composition of the present invention may contain a hydrocarbon resin as a resin component other than the components (A) and (B). Such hydrocarbon resins include C ₅
System resin, C ₉ resins, C ₅ based / C ₉ based mixed resin, cyclopentadiene resin, olefin / vinyl copolymer-based resins of substituted aromatic compounds, co-cyclopentadiene compound / vinyl substituted aromatic compound Examples include a polymer-based resin, a hydrogenated product of the resin, and a hydrogenated product of a vinyl-substituted aromatic resin. Here, the content of the hydrocarbon resin is usually 0.01 to 50 parts by weight, preferably 0.1 to 25 parts by weight, per 100 parts by weight of the component (A).

The resin composition of the present invention contains a known antioxidant such as 2,6-di-tert-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-tert- Butyl-5,5'-dimethyldiphenylmethane, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane; UV absorbers such as 2,4-dihydroxybenzophenone, 2-
It can be stabilized by adding hydroxy-4-methoxybenzophenone or the like. Further, an additive such as a lubricant may be added for the purpose of improving workability.

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. A method for obtaining a resin composition in a form, a method for preparing a solution by dissolving the component (A) in an appropriate solvent, and mixing the component (B) with the solution to obtain a resin composition in a pellet form. Can be.

According to the resin composition of the present invention, a molded article can be produced by a known molding means, for example, an injection molding method, a compression molding method, an extrusion molding method and the like. Here, the shape of the molded product is not particularly limited. Also,
When the component (B) is mixed with the solution of the component (A), a film-shaped molded product can be obtained by a cast molding method.

In addition, 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, general camera lenses, video camera lenses, telescope lenses, spectacle lenses, laser beam Lenses such as lenses, optical video discs, audio discs, document file discs, optical discs such as memory discs, optical materials such as optical fibers, image transfer sheets and various films, sheets, sealants, inorganic or organic compound binders Can be particularly preferably used.

[0037]

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.

[0039]

Embedded image

The ring-opened polymer solution 4 thus obtained
000 parts was charged into an autoclave, and RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃₀ .
48 parts were added, and a hydrogenation reaction was carried out by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and 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 hydrogenated polymer thus obtained (hereinafter referred to as “cyclic polyolefin resin (A-
1) ". ) Has a hydrogenation rate of substantially 100%,
Number average molecular weight in terms of polystyrene measured by GPC (M
n) was 19,800 and the weight average molecular weight (Mw) was 6,200
It was 0.

[Preparation Example (A-2)] 8-Methyl-8-methyl
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 “cyclic polyolefin resin”).
(A-2). " ) Is virtually 100%
Yes, polystyrene equivalent number average molecule measured by GPC
The amount (Mn) is 19200 and the weight average molecular weight (Mw) is 5
8000.

[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.
2000 parts of cyclohexane dehydrated and dried
And tetracyclo [4.4.0.1 under 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 from the gas introduction tube.
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 “cyclic polymer”)
Olefin resin (A-3) ". ) Measured by GPC
The determined number average molecular weight (Mn) in terms of polystyrene is 21.
000, the weight average molecular weight (Mw) was 63,000.
Was.

[Preparation Example (B-1)] 170 parts of pt-butoxystyrene (alkoxy group-containing monomer), 100 parts of styrene (copolymerizable monomer), and AIBN (start of radical polymer) Agent) and toluene (solvent) 200
The reaction mixture was charged into a reaction vessel purged with nitrogen, and solution polymerization was carried out at 90 ° C. for 3 hours to obtain a pt-butoxystyrene / styrene copolymer (copolymer molar ratio: 50/50). The thus obtained polymer (hereinafter, referred to as “aromatic vinyl copolymer (B-1)”) had a weight average molecular weight (Mw) of 70,000 in terms of polystyrene measured by GPC.

[Preparation Example (B-2)] 19 parts of pt-butoxystyrene (alkoxy group-containing monomer), 100 parts of styrene (copolymerizable monomer), and AIBN (start of radical polymer) Agent) and 100 parts of toluene (solvent) were charged into a reaction vessel in which nitrogen was replaced, and solution polymerization was carried out at 90 ° C. for 3 hours to obtain a pt-butoxystyrene / styrene copolymer (copolymerized copolymer). Ratio 10/90). The thus obtained polymer (hereinafter, referred to as “aromatic vinyl copolymer (B-2)”) had a weight average molecular weight (Mw) in terms of polystyrene measured by GPC of 70000.

[Preparation Example (B-3)] 136 parts of p-hydroxystyrene (hydroxyl group-containing monomer), 100 parts of styrene (copolymerizable monomer), and AIBN (radical polymer initiator) 0.2 parts and toluene (solvent) 200
The reaction mixture was charged into a reaction vessel in which the parts were replaced with nitrogen, and solution polymerization was performed at 90 ° C. for 3 hours to obtain a p-hydroxystyrene / styrene copolymer (copolymer molar ratio: 50/50). The thus obtained polymer (hereinafter, referred to as "aromatic vinyl copolymer (B-3)") had a weight average molecular weight (Mw) in terms of polystyrene measured by GPC of 65,000.

[Preparation Example (B-4)] Methyl 4-vinylbenzoate (carboxylic acid ester group-containing monomer) 168
Parts, 100 parts of styrene (copolymerizable monomer), and AI
A reaction vessel in which 0.2 parts of BN (radical polymer initiator) and 200 parts of toluene (solvent) were purged with nitrogen was subjected to solution polymerization at 90 ° C. for 3 hours, and methyl 4-vinylbenzoate / styrene copolymer was added. Coalescence (copolymer molar ratio 50 /
50) was obtained. The polymer thus obtained (hereinafter, referred to as
It is called "aromatic vinyl copolymer (B-4)". ) G
Weight average molecular weight (M
w) was 63,000.

[Preparation Example (B-5)] 130 parts of m-isopropynyl acetophenone (monomer containing a carbonyl group), 100 parts of styrene (copolymerizable monomer), and AIB
9 parts of N (radical polymer initiator) and 200 parts of toluene (solvent) were charged into a reaction vessel purged with nitrogen, and 9
Solution polymerization was carried out at 0 ° C. for 3 hours, and m-isopropynyl acetophenone / styrene copolymer (copolymer molar ratio: 50/5)
0) was obtained. The polymer thus obtained (hereinafter, referred to as
It is called "aromatic vinyl copolymer (B-5)". ) G
Weight average molecular weight (M
w) was 62,000.

[Preparation Example (B-6)] 195 parts of 2-butylamidostyrene (amide group-containing monomer), 100 parts of styrene (copolymerizable monomer), and AIBN (radical polymer initiator) ) Was charged into a reaction vessel in which 0.2 parts of toluene and 200 parts of toluene (solvent) were purged with nitrogen, and solution polymerization was carried out at 90 ° C. for 3 hours to give a 2-butylamidostyrene / styrene copolymer (copolymer molar ratio: 50). / 50). The thus obtained polymer (hereinafter, referred to as "aromatic vinyl copolymer (B-6)") had a weight average molecular weight (Mw) in terms of polystyrene measured by GPC of 64,000.

[Preparation Example (B-7)] 125 parts of 4-aminostyrene (amino group-containing monomer), 100 parts of styrene (copolymerizable monomer), and AIBN (radical polymer initiator) 0.2 parts and 200 parts of toluene (solvent) were charged into a reaction vessel purged with nitrogen, solution polymerization was carried out at 90 ° C. for 3 hours, and a 4-aminostyrene / styrene copolymer (copolymer molar ratio 50/50) was used. ) Got. The polymer thus obtained (hereinafter, referred to as “aromatic vinyl copolymer (B-7)”)
That. ), The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 65,000.

[Preparation Example (B-8)] 155 parts of 4-nitrostyrene (nitro group-containing monomer), 100 parts of styrene (copolymerizable monomer), and AIBN (radical polymer initiator) 0.2 parts and 200 parts of toluene (solvent) were charged into a reaction vessel in which nitrogen was replaced, and solution polymerization was carried out at 90 ° C. for 3 hours to give a 4-nitrostyrene / styrene copolymer (copolymer molar ratio 50/50). ) Got. The polymer thus obtained (hereinafter, referred to as “aromatic vinyl copolymer (B-8)”)
That. ), The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 62,000.

[Preparation Example (B-9)] 135 parts of 4-cyanostyrene (cyano group-containing monomer), 100 parts of styrene (copolymerizable monomer), and AIBN (radical polymer initiator) 0.2 parts and 200 parts of toluene (solvent) were charged into a reaction vessel in which nitrogen was replaced, and solution polymerization was carried out at 90 ° C. for 3 hours to obtain a 4-cyanostyrene / styrene copolymer (copolymer molar ratio 50/50). ) Got. The polymer thus obtained (hereinafter referred to as “aromatic vinyl copolymer (B-9)”)
That. ), The weight average molecular weight (Mw) in terms of polystyrene measured by GPC was 60000.

Example 1 According to the formulation shown in Table 1, the cyclic polyolefin resin (A) obtained in Preparation Example (A-1) was prepared.
-1) 100 parts by weight and 5 parts of the aromatic vinyl copolymer (B-1) obtained in Preparation Example (B-1) are mixed, and the mixture is mixed at 260 ° C. with a twin-screw extruder. By pelletizing, the thermoplastic resin composition of the present invention [hereinafter referred to as “resin composition (C-1)”. ] Was obtained.

Example 2 According to the formulation shown in Table 1, the cyclic polyolefin resin (A) obtained in Preparation Example (A-1) was prepared.
-1) 100 parts by weight and 5 parts of the aromatic vinyl copolymer (B-2) obtained in Preparation Example (B-2) are mixed, and the mixture is mixed at 260 ° C. with a twin-screw extruder. By pelletizing, the thermoplastic resin composition of the present invention [hereinafter referred to as “resin composition (C-2)”. ] Was obtained.

Example 3 According to the formulation shown in Table 1, the cyclic polyolefin resin (A) obtained in Preparation Example (A-1) was prepared.
-1) 100 parts by weight and 5 parts of the aromatic vinyl copolymer (B-3) obtained in Preparation Example (B-3) are mixed, and the mixture is mixed at 260 ° C. with a twin-screw extruder. By pelletizing, the thermoplastic resin composition of the present invention [hereinafter referred to as “resin composition (C-3)”. ] Was obtained.

Example 4 According to the formulation shown in Table 1, the cyclic polyolefin resin (A) obtained in Preparation Example (A-2) was prepared.
-2) 100 parts by weight and 5 parts of the aromatic vinyl copolymer (B-2) obtained in Preparation Example (B-2) are mixed, and this mixture is heated at 240 ° C using a twin-screw extruder. By pelletizing, the thermoplastic resin composition of the present invention [hereinafter referred to as “resin composition (C-4)”. ] Was obtained.

Example 5 According to the formulation shown in Table 1, the cyclic polyolefin resin (A) obtained in Preparation Example (A-3) was prepared.
-3) 100 parts by weight and 5 parts of the aromatic vinyl copolymer (B-2) obtained in Preparation Example (B-2) are mixed, and the mixture is mixed at 220 ° C. with a twin-screw extruder. By pelletizing, the thermoplastic resin composition of the present invention [hereinafter referred to as “resin composition (C-5)”. ] Was obtained.

Example 6 According to the formulation shown in Table 1, the cyclic polyolefin resin (A) obtained in Preparation Example (A-1) was prepared.
-1) 100 parts by weight and 5 parts of the aromatic vinyl copolymer (B-4) obtained in Preparation Example (B-4) are mixed, and the mixture is mixed at 260 ° C. with a twin-screw extruder. By pelletizing, the thermoplastic resin composition of the present invention [hereinafter referred to as “resin composition (C-6)”. ] Was obtained.

Example 7 According to the formulation shown in Table 1, the cyclic polyolefin resin (A) obtained in Preparation Example (A-1) was prepared.
-1) 100 parts by weight and 5 parts of the aromatic vinyl copolymer (B-5) obtained in Preparation Example (B-5) are mixed, and the mixture is heated at 260 ° C. using a twin-screw extruder. By pelletizing, the thermoplastic resin composition of the present invention [hereinafter referred to as “resin composition (C-7)”. ] Was obtained.

Example 8 According to the formulation shown in Table 1, the cyclic polyolefin resin (A) obtained in Preparation Example (A-1) was prepared.
-1) 100 parts by weight and 5 parts of the aromatic vinyl copolymer (B-6) obtained in Preparation Example (B-6) are mixed, and the mixture is heated at 260 ° C. using a twin-screw extruder. By pelletizing, the thermoplastic resin composition of the present invention [hereinafter referred to as “resin composition (C-8)”. ] Was obtained.

Example 9 According to the formulation shown in Table 1, the cyclic polyolefin resin (A) obtained in Preparation Example (A-1) was prepared.
-1) 100 parts by weight and 5 parts of the aromatic vinyl copolymer (B-7) obtained in Preparation Example (B-7) are mixed, and this mixture is heated at 260 ° C. using a twin-screw extruder. By pelletizing, the thermoplastic resin composition of the present invention [hereinafter referred to as “resin composition (C-9)”. ] Was obtained.

Example 10 According to the formulation shown in Table 1, 100 parts by weight of the cyclic polyolefin resin (A-1) obtained in Preparation Example (A-1) and 100 parts by weight of Preparation Example (B-8) were obtained. And 5 parts of the obtained aromatic vinyl copolymer (B-8),
This mixture is pelletized at 260 ° C. with a twin-screw extruder to obtain a thermoplastic resin composition of the present invention [hereinafter referred to as “resin composition (C-10)”. ] Was obtained.

Example 11 According to the recipe shown in Table 1, 100 parts by weight of the cyclic polyolefin resin (A-1) obtained in Preparation Example (A-1) and 100 parts by weight of Preparation Example (B-9) were obtained. And 5 parts of the obtained aromatic vinyl copolymer (B-9),
The mixture is pelletized at 260 ° C. with a twin-screw extruder to obtain a thermoplastic resin composition of the present invention [hereinafter referred to as “resin composition (C-11)”. ] Was obtained.

Comparative Examples 1 to 3 Preparation Examples (A-1) to (A
Cyclic polyolefin resin (A-1) obtained in -3)
To (A-3) were pelletized.

Comparative Example 4 According to the formulation shown in Table 1, the cyclic polyolefin resin (A) obtained in Preparation Example (A-1) was prepared.
-1) 100 parts by weight and polystyrene (Mw = 7000)
0) was mixed with 5 parts, and the mixture was mixed with a twin-screw extruder at 260 ° C.
By pelletizing at a temperature of 0 ° C., a thermoplastic resin composition for comparison [hereinafter referred to as “resin composition (D-1)”. ] Was obtained.

Comparative Example 5 According to the formulation shown in Table 1, the cyclic polyolefin resin (A) obtained in Preparation Example (A-1) was prepared.
-1) 100 parts by weight and a styrene-acrylonitrile copolymer [Mw = 68000, copolymerization molar ratio (styrene /
(Acrylonitrile) = 60/40], and the mixture was pelletized at 260 ° C. with a twin-screw extruder to obtain a thermoplastic resin composition for comparison [hereinafter referred to as “resin composition (D-2)”. ) ". ] Was obtained.

Comparative Example 6 According to the formulation shown in Table 1, the cyclic polyolefin resin (A) obtained in Preparation Example (A-1) was prepared.
-1) 100 parts by weight and 5 parts of a styrene / maleic anhydride copolymer [Mw = 72000, copolymerization molar ratio (styrene / maleic anhydride) = 75/25] are mixed, and the mixture is biaxially extruded. By pelletizing at 260 ° C. with a machine, a thermoplastic resin composition for comparison [hereinafter referred to as “resin composition (D-3)”. ] Was obtained.

Comparative Example 7 According to the formulation shown in Table 1, the cyclic polyolefin resin (A) obtained in Preparation Example (A-1) was prepared.
-1) 100 parts by weight and 5 parts of a styrene / methyl methacrylate copolymer [Mw = 80000, copolymerization molar ratio (styrene / methyl methacrylate) = 40/60] are mixed, and this mixture is biaxially extruded. By pelletizing at 260 ° C. with a machine, a thermoplastic resin composition for comparison [hereinafter referred to as “resin composition (D-4)”. ].

<Evaluation of Resin Composition> (1) Low birefringence (measurement of retardation): Example 1
Pellets of the resin compositions (C-1) to (C-9) obtained in Comparative Examples 1 to 9, and the pellets of the cyclic polyolefin-based resins (A-1) to (A-3) obtained in Comparative Examples 1 to 3. Using each of the pellets of the resin compositions (D-1) to (D-4) obtained in Examples 4 to 7, a pickup lens having a diameter of 5 mm and a maximum thickness of 2 mm was produced by an injection molding machine.

For each of the pickup lenses obtained using the resin compositions (C-1) to (C-9) and the cyclic polyolefin-based resins (A-1) to (A-3), a strain tester " The retardation by the Senarmont method was measured using "LSM-501" (manufactured by Lukeo Corporation). The results are shown in Table 1. Here, "retardation"
Is the biaxial refractive index anisotropy (ΔN) orthogonal to the lens
And the lens thickness (d) (ΔN × d). It can be said that the smaller the retardation value, the better the low birefringence. A preferred retardation value is 50 nm or less. In addition, the resin compositions (D-1) to (D-4)
The pickup lens obtained using the method was cloudy due to phase separation, and the retardation could not be measured.

(2) Transparency (measurement of total light transmittance): pellets of resin compositions (C-1) to (C-9), pellets of cyclic polyolefin resin (A-1) to (A-3) Using each of the pellets of the resin compositions (D-1) to (D-4), a test piece (thickness: 3 mm) for evaluating transparency was prepared by an injection molding machine, and the test piece was prepared according to ASTM D1003. The total light transmittance was measured. The results are shown in Table 1.

(3) Heat resistance (measurement of heat distortion temperature): pellets of resin compositions (C-1) to (C-9), pellets of cyclic polyolefin-based resins (A-1) to (A-3), Using each of the pellets of the resin compositions (D-1) to (D-4), a test piece (0.64 mm x 1.27 mm x 127 mm) for evaluating heat resistance was prepared by an injection molding machine. According to ASTM D648 (18.6 kg / cm
² , 1/4 ") The heat distortion temperature was measured. The results are shown in Table 1.

(4) Water resistance (measurement of water absorption): pellets of resin compositions (C-1) to (C-9), cyclic polyolefin-based resins (A-1) to (A-3), resin Using each of the pellets of the compositions (D-1) to (D-4), a test piece (3) for evaluating water resistance was measured by an injection molding machine.
mm × 40 mm × 80 mm). The weight W _{0 of the} test piece was measured, the weight W ₁ after immersion in water at 23 ° C. for 24 hours was measured, and the water absorption was calculated by the following equation. The results are shown in Table 1.

[0073]

## EQU1 ## Water absorption (%) = [(W ₁ −W ₀ ) / W ₀ ] × 100

[0074]

[Table 1]

[0075]

According to the present invention, the thermoplastic resin composition of the present invention can maintain the various properties (transparency, water resistance, heat resistance) possessed by the cyclic polyolefin-based resin, and can further improve the properties of the conventionally known cyclic polyolefin-based resin. Has excellent low birefringence.

Claims (1)

[Claims] 1. A cyclic polyolefin resin (A) 100
Parts by weight, a polar group-containing aromatic vinyl (co) polymer (B)
A thermoplastic resin composition comprising 0.01 to 100 parts by weight.