JP2003238774A - Thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition which retains various characteristics possessed by the previously known cyclic olefin type thermoplastic resins and which excels in mold releasability when molding and surface coatability of the molded article, and which gives superior stability at high temperatures. <P>SOLUTION: This resin composition contains a cyclic olefinic thermoplastic resin (A), an ester compound between glyceral and a saturated fatty acid (B), and optionally a hydrocarbon based resin (C) other than the above (A) which has a weight average mol.wt. converted to polystyrene of 20,000 or less and is solid at ordinary temperatures. <P>COPYRIGHT: (C)2003,JPO

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 specifically to a mold release at the time of molding containing a cyclic olefin thermoplastic resin and an ester compound of a glycerin compound and a saturated fatty acid. TECHNICAL FIELD The present invention relates to a thermoplastic resin composition which is excellent in stability and surface coatability of a molded product and is also excellent in stability at high temperatures. Further, the present invention comprises a cyclic olefin-based thermoplastic resin, an ester compound of a glycerin-based compound and a saturated fatty acid, and a hydrocarbon-based resin having a polystyrene-equivalent weight average molecular weight of 20,000 or less and solid at room temperature, The present invention relates to a thermoplastic resin composition which is excellent in mold releasability at the time of molding and surface coatability of a molded product and is also excellent in stability at high temperatures.

[0002]

2. Description of the Related Art Cyclic olefin type thermoplastic resins have excellent transparency and can withstand use under high temperature conditions.
Widely used as various optical components. When such a cyclic olefin thermoplastic resin is used as an optical component, it is processed by a molding method such as injection molding or extrusion molding. This optical component usually needs to have a fine mirror surface or transfer a fine pattern. In this case, since the resin and the surface of the mold and the like are in close contact with each other, problems such as the resin adhering to the surface of the mold are likely to occur. For this reason,
It is usually used as a composition in which a compound containing a fatty acid as a main component such as metal soap is blended with a resin as a release agent. However, since the cyclic olefin-based thermoplastic resin has a high processing temperature, a gel component may be generated in the composition due to the release agent, or a release agent that is stable at high temperature may have less release effect. There's a problem. Further, since these release agents are deposited on the surface of the material and exert a release effect, when coating various chemical substances on the surface of the optical component, various kinds of adhesion such as a decrease in adhesion of the coating film are produced. May cause problems.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object thereof is to retain various characteristics of a conventionally known cyclic olefin thermoplastic resin and The present invention provides a thermoplastic resin composition which is excellent in mold releasability and surface coatability of a molded product and is also excellent in stability at high temperature.

[0004]

Means for Solving the Problems As a result of intensive studies aimed at solving the above problems, the present inventors have found that (A) a cyclic olefin-based thermoplastic resin and (B) glycerin and a saturated fatty acid. A thermoplastic resin composition containing an ester compound is stable and stable even in a high temperature environment such as during molding, and further has excellent releasability and surface coatability of a molded product. The present invention has been completed and the present invention has been completed. In addition, (A) a cyclic olefin-based thermoplastic resin, (B) an ester compound of a glycerin-based compound and a saturated fatty acid, and (C) the component (A) other than the component (A) have a polystyrene-converted weight average molecular weight of 20,000 or less. , And a thermoplastic resin composition containing a hydrocarbon-based resin that is solid at room temperature is stable and suppresses the generation of gel components even under a high temperature environment such as during molding, and further, it has excellent releasability and molded products. They have found that they are also excellent in surface coatability, and have completed the present invention.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. <(A) Cyclic olefin-based thermoplastic resin> As the cyclic olefin-based thermoplastic resin (hereinafter, referred to as “(A) component”) constituting the thermoplastic resin composition of the present invention, the polymers shown in the following (1) to (3) are given. Can be mentioned. Ring-opening copolymer 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 ring-opening (co) polymer was cyclized by Friedel-Crafts reaction, hydrogenated (co) polymer Specific monomer and unsaturated double bond-containing compound Saturated copolymer with

[0006]

[Chemical 1]

[In the formula, 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, which may be the same or different. R ¹ and R ² or R ³ and R ⁴ may combine to form a divalent hydrocarbon group, and R ¹ or R ²
And R ³ or R ⁴ may be bonded to each other to form a monocyclic or polycyclic structure. m is 0 or a positive integer, p
Is 0 or a positive integer. However, when m is 0,
n is also 0. ]

<Specific Monomer> Specific examples of the specific monomer represented by the general formula (i) include the following compounds, but the present invention is not limited thereto. 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, pentacyclo [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-methylbicyclo [2.2.1] hept-2-ene, 5- ethylbicyclo [ 2.2.1] Hept-2-ene, 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2- Ene, 5-cyanobicyclo [2.2.1] hept-2-ene, 8-methoxycarbonyltetracyclo [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-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10 ] -3-dodecene, 8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . ^{17 , 10} ] -3-dodecene,
8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . ^{17 , 10} ] -3-Dodecene, 8-
Methyl -8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-dodecene, 8-
Methyl-8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-dodecene, 8-
Methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 6-
Ethylidene-2-tetracyclododecene, pentacyclo [8.4.0.1 ^2,5 . 1 ^9,12 . 0 ^8,13] -3-hexadecene, heptacyclo [8.7.0.1 ^3,6. 1 ^10,17 .
1 ^12,15 . 0 ^2,7 . 0 ^{11, 16]} -4-eicosene, heptacyclo [8.8.0.1 ^4,7. 1 ^11,18 . 1 ^13,16 .
0 ^3,8 . 0 ^12,17 ] -5- ^heneicosene , 5-ethylidene bicyclo [2.2.1] hept-2-ene, 8-ethylidene tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]-
3-dodecene, 5-phenylbicyclo [2.2.1] hept-2-ene, 8-phenyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 5-fluorobicyclo [2.2.1] hept-2-ene, 5-fluoromethylbicyclo [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-difluorobicyclo [2.2.1] hept-2-ene, 5,5- Bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (trifluoromethyl) bicyclo [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 (fluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,5,6,6-tetrafluorobicyclo [2.
2.1] hept-2-ene, 5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,5-difluoro-6,6-bis ( Trifluoromethyl) bicyclo [2.2.1] hept-2
-Ene, 5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,5,6-trifluoro-5-trifluoromethylbicyclo [2] 1.2.1] hept-2-ene, 5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) 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-ene, 5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,
5,6-Trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene, 5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept- 2-ene, 8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-fluoromethyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 8-difluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-trifluoromethyltetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8-pentafluoroethyltetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-Dodecene, 8,8-difluorotetracyclo [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 (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .
^{17 , 10} ] -3-Dodecene, 8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^{7 , 10} ]
-3-dodecene, 8-methyl-8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . ^{17 , 10} ] -3-Dodecene, 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, 5} . 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-tetrakis (trifluoromethyl) tetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -3-Dodecene, 8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-Difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
- dodecene, 8,8,9- trifluoro-9-trifluoromethyl-tetracyclo [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-trifluoro-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-heptafluoro iso-propyl-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-dodecene, 8-chloro-8,9,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Dodecene, 8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-Dodecene, 8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 8-methyl-8-
(2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and the like can be mentioned. These specific monomers are
They may be used alone or in combination of two or more.

Among these, preferred specific monomers are those in which R ¹ and R ³ are hydrogen atoms or hydrocarbon groups having 1 to 10 carbon atoms and R ² and R ⁴ are those in the general formula (i). A hydrogen atom or a monovalent organic group, wherein 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 and n is 0 to 3 And m + n is 0 to 4, preferably m + n is 0.
2, particularly preferably, m is 1 and n is 0. Further, as the polar group other than the hydrogen atom and the hydrocarbon group, an amino group, an amide group, an imide group,
Carboxyl group, carbonyl group, alkoxy group, allyloxy group, hydroxyl group, silyl group, alkoxysilyl group, allyloxysilyl group, or groups in which a plurality of these polar groups are combined through a linking group such as a methylene group, etc. Is mentioned.

In particular, among the specific monomers, the formula-(CH ₂ ) _p
The specific monomer having a polar group represented by COOR ⁵ is preferable because the obtained cyclic olefin-based thermoplastic resin has a high glass transition temperature and low hygroscopicity. In the above formula for a polar group, R ⁵ is 1 to 1 carbon atoms.
12 hydrocarbon groups, preferably alkyl groups. Further, p is usually 0 to 5, but the smaller the value of p, the higher the glass transition temperature of the obtained cyclic olefin-based thermoplastic resin is, which is preferable, and the specific monomer in which p is 0 is It is preferable because its 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 carbon atom.
Is preferably from 4 to 4, more preferably from 1 to 2,
Particularly preferably, it is 1. In particular, the alkyl group is the above formula - is preferably coupled to (CH _{2) p} COOR ⁵ in the same carbon atom and the carbon atom to which the polar group is bonded represented.

Among the specific monomers, 8-methyl-8
-Methoxycarbonyltetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethylidene tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 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 preferred in that the finally obtained cyclic olefin-based thermoplastic resin has excellent heat resistance, and 8-methyl-8-methoxycarbonyltetracyclo [4.4. 0.1 ^2,5 . 1
^7,10 ] -3-Dodecene is particularly preferable in that it has the above preferable polar group.

<Copolymerizable Monomer> In the ring-opening polymerization step for obtaining the cyclic olefin-based thermoplastic resin of the present invention, the above-mentioned specific monomer may be subjected to ring-opening polymerization alone. The specific monomer and the copolymerizable monomer may be subjected to ring-opening copolymerization. Specific examples of the copolymerizable monomer used in this case include cycloolefins such as cyclobutene, cyclopentene, cyclopentadiene, cycloheptene, cyclooctene, and dicyclopentadiene. Cycloolefin has 4 to 2 carbon atoms
0 is preferable, and 5-12 is more preferable. In this case, the proportion of the copolymerizable monomer used is usually about 1 to 80 mol%, preferably about 3 to 50 mol%, based on all the monomers. Furthermore, in the presence of an unsaturated hydrocarbon-based polymer containing a carbon-carbon double bond in the main chain such as polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-non-conjugated diene copolymer, polynorbornene, etc. The specific monomer (and the copolymerizable monomer) may be subjected to ring-opening polymerization. The ring-opened polymer or hydrogenated product thereof obtained in this case is useful as a raw material for a resin having high impact resistance. In this case, the amount of the monomer [specific monomer (and copolymerizable monomer)] used is usually 1 to 100 parts by weight, preferably 5 to 100 parts by weight of the unsaturated hydrocarbon polymer. It is about 50 parts by weight.

<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) an element of Group IA (for example, Li, Na, K, etc.) of the periodic table of Deming, and an element of Group IIA (for example, Mg, Ca, etc., Group IIB elements (eg Z
n, Cd, Hg, etc.), Group IIIB elements (eg, B, Al)
Etc.), IVA group element (eg Ti, Zr, etc.) or
A catalyst which is a compound of a group IVB element (for example, Si, Sn, Pb, etc.) and is formed by a combination with at least one element selected from the group having at least one element-carbon bond or the element-hydrogen bond. . Further, in this case, in order to enhance the activity of the catalyst, the below-mentioned (c) additive may be added.

Suitable W, Mo or (a) as the component (a)
As a typical example of the compound of Re, WCl₆, MoCl_Five,
ReOCl₃Etc. Described in JP-A-1-240517
Compounds of Specific examples of the component (b) include nC_FourH₉Li, (C₂
H_Five)₃Al, (C₂H_Five) ₂AlCl, (C₂H_Five)_1.5Al
Cl_1.5, (C₂H_Five) AlCl₂, Methylalumoxane,
Compounds such as LiH described in JP-A-1-240517
I can list things. Substitute for component (c) that is an additive
Examples include alcohols, aldehydes, and ketones
And amines can be preferably used.
The compounds disclosed in JP-A-1-240517 are used for
Can be used.

The amount of the metathesis catalyst to be used is "(a) component: specific monomer" in a molar ratio of (a) component to specific monomer of usually 1: 500 to 1: 50,000. Range, preferably 1: 1,000 to 1: 10,000
The range is 0. The ratio of the component (a) to the component (b) is such that “(a) :( b)” is 1: 1 to 1: 1 in terms of metal atom ratio.
The range is 50, preferably 1: 2 to 1:30.
The molar ratio of the component (a) to the component (c) is in the range of 0.005: 1 to 15: 1, preferably 0.05: 1 to 7: 1 for "(c) :( a)". It is said that

<Molecular Weight Control Agent> The molecular weight of the ring-opening polymer can be controlled by the polymerization temperature, the type of catalyst and the type of solvent. In the present invention, the molecular weight control agent is allowed to coexist in the reaction system. Therefore, it is preferable to adjust it. Here, as a suitable molecular weight regulator, for example, ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-
Examples thereof include α-olefins such as decene and styrene, and among these, 1-butene and 1-hexene are particularly preferable. These molecular weight regulators can be used alone or in admixture 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 used in the ring-opening polymerization reaction.

<Solvent for Ring-Opening Polymerization Reaction> Examples of the solvent used in the ring-opening polymerization reaction (solvent for dissolving the specific monomer, the metathesis catalyst and the molecular weight modifier) include pentane, hexane, heptane, octane, nonane, Alkanes such as decane; cyclohexane, cycloheptane,
Cycloalkanes such as cyclooctane, decalin and norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, 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 acid esters such as iso-butyl acetate, methyl propionate and dimethoxyethane; ethers such as dibutyl ether, tetrahydrofuran and dimethoxyethane can be mentioned, and these can be used alone or in combination. Of these, aromatic hydrocarbons are preferred. The amount of the solvent used is such that the "solvent: specific monomer (weight ratio)" is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1. It

<Hydrogenation Catalyst> The ring-opening (co) polymer obtained as described above can be used as it is as the component (A), but when it has an olefinic unsaturated bond in its molecule, It is preferable to use the hydrogenated (co) polymer in which the olefinic unsaturated bond is hydrogenated as the component (A). However, when the unsaturated bond in the molecule forms an aromatic ring, it is not always necessary to hydrogenate the aromatic ring, and the hydrogenation reaction below and the description of the hydrogenation rate are based on the hydrogen of the olefinic unsaturated bond. Regarding addition. The hydrogenation reaction is carried out by a conventional method, that is, a hydrogenation catalyst is added to a solution of a ring-opening (co) polymer,
This is carried out by applying hydrogen gas at atmospheric pressure to 300 atm, preferably 3 to 200 atm at 0 to 200 ° C, preferably 20 to 180 ° C. As the hydrogenation catalyst, those used in ordinary hydrogenation reactions of olefinic compounds can be used. Heterogeneous catalysts and homogeneous catalysts are known as the hydrogenation catalyst.

Examples of the heterogeneous catalyst include solid catalysts in which a noble metal catalyst substance such as palladium, platinum, nickel, rhodium or ruthenium is supported on a carrier such as carbon, silica, alumina or titania. Further, as a homogeneous catalyst, nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium. , Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, and the like. The catalyst may be in the form of powder or particles. In these hydrogenation catalysts, “ring-opening (co) polymer: hydrogenation catalyst (weight ratio)” is 1: 1 ×
It is used in a ratio of 10 ⁻⁶ to 1: 2.

As described above, the hydrogenated (co) polymer obtained by hydrogenation has excellent thermal stability, and its properties are deteriorated by heating during molding and use as a product. There is nothing to do. 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 Saturated Copolymer> In order to obtain the component (A) composed of the saturated copolymer, the unsaturated dicarboxylic acid compound to be copolymerized with the specific monomer is used. 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 when obtaining a saturated copolymer>
As the catalyst used in the copolymerization reaction of the specific monomer and the unsaturated double bond-containing compound, a catalyst composed of a vanadium compound and an organoaluminum compound is used. As the vanadium compound, a compound represented by the general formula: VO (OR) _a X _b or V
(OR) _c X _d (wherein R is a hydrocarbon group, 0 ≦ a ≦ 3,
0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦
4, a vanadium compound represented by 3 ≦ c + d ≦ 4) or an electron donor adduct thereof is used. Examples of the electron donor include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonia, amines, nitriles. , A nitrogen-containing electron donor such as isocyanate, and the like. As the organoaluminum compound catalyst component, at least one selected from those having at least one aluminum-carbon bond or aluminum-hydrogen bond is used. The ratio of the catalyst component is 2 or more in the ratio of aluminum atoms to vanadium atoms (Al / V),
The range is preferably 2 to 50, particularly preferably 3 to 20.

<Solvent Used for Obtaining Saturated Copolymer>
Examples of the solvent used in the copolymerization reaction of the specific monomer and the unsaturated double bond-containing compound include alkanes such as pentane, hexane, heptane, octane, nonane and decane, cycloalkane such as cyclohexane and methylcyclohexane. Examples thereof include aromatic hydrocarbons such as benzene, benzene, toluene, xylene, and halogen derivatives thereof, and of these, cyclohexane is preferable.

The intrinsic viscosity (η _inh ) of the cyclic olefin thermoplastic resin used as the component (A) of the present invention measured in chloroform at 30 ° C. is preferably 0.2 to 5 dl / g, and further Preferably 0.3-4 dl
/ G. As the molecular weight of the component (A), the polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 8,
000-100,000, weight average molecular weight (Mw) is 2
Those in the range of 30,000 to 300,000 are suitable.

The cyclic olefin-based thermoplastic resin used as the component (A) of the present invention, when used as an optical material, contains few foreign substances that cause visual defects and abnormal bright spots, and it is preferable that they are not present as much as possible. The content of such foreign matter is preferably 0 / 10g of foreign matter having a size of 50 μm or more, preferably 0 / 10g of foreign matter having a size of 30 μm or more, and particularly preferably 0 / 10g of foreign matter having a size of 20 μm or more. The amount of foreign matter is measured by dissolving the resin in a solvent having solubility such as toluene and cyclohexane, filtering with a filter, and observing with a microscope to count the size and the number. In addition, the resin solution is measured using a commercially available particle counter based on the principle of light scattering,
It is also possible to count the amount of foreign matter. Further, it is preferable to suppress the content of the fine powder of the cyclic olefin-based thermoplastic resin used as the component (A) of the present invention as much as possible. When the amount of this fine powder is large, it appears as optical fluctuations and causes performance defects such as bright spots and blurring of the focus, which is not preferable.

<Component (B)> Examples of the ester compound of glycerin and saturated fatty acid used as the component (B) of the present invention include those represented by the following general formulas (ii) to (v). However, the present invention is not limited to these.

[0027]

[Chemical 2]

[Chemical 3]

[Chemical 4]

[Chemical 5]

In the formula, R ^{5 to} R ⁷ are each independently a saturated fatty acid residue having 10 to 30 carbon atoms, particularly 16 carbon atoms.
To 26 are preferable, and examples thereof include residues of stearic acid, palmitic acid, behenic acid, oleic acid, lauric acid and the like. R ^{5 to} R ⁷ may be the same or different. Here, the formula (ii) represents a monoester, the formulas (iii) and (iv) represent a diester, and the formula (v) represents a triester. In the present invention, these ester compounds of glycerin and saturated fatty acid may be used alone or in combination of two or more kinds.

Among these, from the viewpoint of heat resistance, the formula (v) in which the hydroxyl group of glycerin is 100% esterified
Preferred is a triester compound of a saturated fatty acid represented by Industrially, the esterification rate of hydroxyl groups of glycerin is preferably 90% or more, more preferably 95%.
Above all, it is particularly preferable to use a mixture of ester compounds of 98% or more. By using a mixture of such ester compounds, even under use under high temperature and high humidity environment or under high temperature molding conditions,
It is possible to suppress the remarkable discoloration and gel generation due to the component (B).

The cyclic olefin-based thermoplastic resin composition of the present invention also contains, in addition to the components (A) and (B),
For example, JP-A-9-221577 and JP-A-10-2
It may be a thermoplastic resin composition described in Japanese Patent Publication 87732, which contains a specific hydrocarbon resin as a component (C). Such a thermoplastic resin composition can provide a light guide plate having a good balance between heat resistance and molding processability and having good hue and surface transferability.

<Component (C)> As the specific hydrocarbon resin used as the component (C) of the present invention, the polystyrene reduced weight average molecular weight measured by gel permeation chromatography (GPC) is 2 × 10 ⁴ or less. , Preferably 2 × 10 ^{4 to} 100, and solid at room temperature. However, the component (C) excludes the component (A). Specific examples of the component (C) include, for example, C ₅ resin, C ₉ resin, C ₅ / C ₉ mixed resin, cyclopentadiene resin, vinyl-substituted aromatic compound polymer resin, and vinyl-substituted aromatic resin. Examples thereof include polymer resins of compounds, copolymer resins of olefin / vinyl-substituted aromatic compounds, copolymer resins of cyclopentadiene compounds / vinyl-substituted aromatic compounds, and hydrogenated products of the above resins. If the polystyrene-converted weight average molecular weight of these hydrocarbon-based resins is too high, the compatibility with the cyclic olefin-based thermoplastic resin having a polar group deteriorates and the transparency decreases, which is not preferable. Further, it is not preferable to use a hydrocarbon compound which is liquid at room temperature, because the strength of the resin is likely to be lowered and the resin bleeds on the surface of the resin. The blending ratio of the component (C) is 0.1 to 100 parts by weight, preferably 1 to 60 parts by weight, and more preferably 10 parts by weight based on 100 parts by weight of the (A) cyclic olefin-based thermoplastic resin.
~ 45 parts by weight.

The compounding method of the thermoplastic resin composition of the present invention is carried out by a known apparatus used for processing the thermoplastic resin, for example,
A method of melt-kneading using a twin-screw extruder, a single-screw extruder, a continuous kneader, a roll kneader, a pressure kneader, a Banbury mixer, (A) a cyclic olefin-based thermoplastic resin, and (B) glycerin and a saturated fatty acid And the method of compounding (C) a specific hydrocarbon-based resin in a solution state and pelletizing it.
Here, the component (B) and / or the component (C) can be added in a solid state such as powder or flakes, or in a known form such as a known solvent and solution state or a slurry state, and is not particularly limited.

Further, a method of blending the components (B) and / or (C) during the process of producing the (A) cyclic olefin-based thermoplastic resin can be adopted. The method of blending (A) the cyclic olefin-based thermoplastic resin in the production step is not particularly limited, but it may be blended with a monomer to be used in a polymerization system, or blended with a reaction solution after polymerization. Examples thereof include a method, a method of blending with a reaction solution after production of a hydrogenated body, a method of blending with a solution after catalyst separation, a method of blending at a solvent separation step such as concentration, a method of blending at pellet granulation and the like. In this case, the component (B) and / or the component (C) is dissolved in a solvent in which the production of the (A) cyclic olefin-based thermoplastic resin is not hindered and the component (B) and / or (C) is soluble. It is possible to add it in the form of a solution or in the form of powder during the manufacturing process. From the viewpoint of the uniformity of the components (B) and / or (C) in the composition of the present invention, it is preferable to add them in the catalyst separation step, the solvent separation step or the pellet granulation step in the step, and (B) and / Or (C)
It is preferred to add the components in solution.

In addition, the component (B) can be blended in the molding process. As a method of blending in the molding process, a method of blending with (A) pellets of a cyclic olefin-based thermoplastic resin in a powder state and molding, a known resin or solvent and a masterbatch to prepare A method of blending with a thermoplastic resin and molding is mentioned, but it is preferable to add it as a masterbatch from the viewpoint of uniform dispersion of the component (B) in the cyclic olefin-based thermoplastic resin (A) during molding. . Here, the resin serving as the base material of the masterbatch is preferably (A) a cyclic olefin-based thermoplastic resin or a composition of the cyclic olefin-based thermoplastic resin to be subjected to molding, but the performance when formed into a molded body It is also possible to use other known thermoplastic resins or thermoplastic elastomers within the range that does not impair the above. As the apparatus used for producing the masterbatch, the apparatus used for processing the above-mentioned known thermoplastic resin can be used. When preparing a masterbatch, the preferred concentration of the component (B) in the masterbatch is usually 0.
01% to 90% by weight, preferably 0.1% to 5%
It is 0% by weight. On the other hand, when the solution is used as a master batch, it is preferable to use the solvent used for producing the (A) cyclic olefin-based thermoplastic resin of the present invention or the composition of the cyclic olefin-based thermoplastic resin. Further, it is preferable that the component (B) is dissolved in the solution to form a uniform layer, but a slurry may be used as long as the uniform dispersibility of the component (B) in the molded product is not impaired. The preferred concentration of component (B) in the masterbatch is usually
0.01% by weight to 90% by weight, preferably 0.1 to 50%
% By weight.

The addition amount of the component (B) in the composition of the present invention is preferably 10 to 50,000 ppm, more preferably 100 to 10,000 ppm, and particularly preferably 500 to 5000 ppm. When the addition amount of the component (B) is less than 10 ppm, the releasability of the molded product is inferior, while when it exceeds 50,000 ppm, the composition becomes turbid and transparency is deteriorated, which is not preferable.

The thermoplastic resin composition of the present invention contains known organic compounds, inorganic compounds and organic-inorganic composites as long as the basic performance of the composition of the present invention such as transparency, heat resistance and easy coating property is not impaired. It is also possible to add an organic polymer, an inorganic polymer or the like. Examples of such additives include 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-dimethyldiphenylmethane, and tetrakis [ Antioxidants such as methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, or benzylmalonate series UV inhibitors such as compounds, glass, silicon compounds, zirconia, calcium carbonate, magnesium carbonate, in the form of fibers, particles, flakes, etc.
Organic / inorganic compounds such as zinc oxide and crosslinked polymer particles,
Colorants such as organic dyes, organic pigments and inorganic pigments, styrene-based, olefin-based, diene-based, acrylic-based or thermosetting or thermoplastic polymers obtained by hydrogenating these, ester-based, mineral oil-based, and silicon-based plastics Examples include agents.

The thermoplastic resin composition of the present invention can be molded into various molded products by a known method. Although not particularly limited, for example, injection molding method, profile extrusion method, fiber spinning, blow molding method, inflation molding method, rotational molding method, melt casting method, solution casting method, etc. can be adopted, and preferably , Injection molding method, melt casting method,
A solution casting method, which will be described in detail below.

The injection molding machine used for the injection molding of the thermoplastic resin composition of the present invention is not particularly specified, but for example, a cylinder system is an in-line system, a pre-plastic system, a drive system is a hydraulic system, an electric system, a hybrid system, As a mold clamping method, a direct pressure type, a toggle type, a horizontal type or a vertical type in the injection direction can be used. Further, with respect to the mold clamping, injection compression and core compression may be used. The cylinder diameter and mold clamping force are determined by the shape of the target molded product. Generally, the larger the projected area of the molded product, the greater the mold clamping force, and when the molded product has a large capacity, it is preferable to select a cylinder with a large cylinder diameter. . The molding conditions should be selected optimally according to the shape of the molded product, and are not particularly limited. The thermoplastic resin composition of the present invention is particularly excellent in releasability when injection molding is performed. Therefore, it is possible to suppress various optical problems due to defective release, mechanical distortion of the molded product, and mold contamination.

The thermoplastic resin composition of the present invention can be used as an optical component to obtain a film or sheet shaped molded article by a melt casting method or a solution casting method. The film and the sheet are usually long molded products having a thickness of 2 mm or less. An optical component is obtained by cutting such a film or sheet into a desired shape by a known method.

Here, the melt casting method means that a thin melt is extruded from a film or sheet die attached to the tip of an extruder, and the film or sheet is cooled and solidified by various rolls or belts to form the film or sheet. Is the way to get. The extruder used for the solution casting method is not particularly limited, and known ones can be used. Usually, a single-screw or twin-screw extruder is used, and preferably a single-screw extruder is used. The cylinder diameter of the extruder is usually 10 to 100 m.
m, and the ratio L / D between the cylinder length and the cylinder diameter is 10 to 150. Well-known screws are used, and in the case of a single screw, for example, full-flight, sub-flight combination, darmage-incorporated screw, and screw pitch or groove depth changing in the same screw can be mentioned. In the case of a twin screw, in the case of a system with two or three threads, different directions or rotations in the same direction, and the method in which screw parts are freely combined, the shape of the screw parts is screw type, reverse feed screw, paddle type screw, helical paddle It is possible to freely select and install using a screw. Extruder is 1
It is possible to operate on a stand, but it is also possible to use one in which two or more extruders are connected, or one in combination with a continuous or batch type kneader.

The solution casting method is a method in which the thermoplastic resin composition of the present invention is dissolved in a soluble solvent, the solution is spread into a film or sheet, and the solvent is separated by a known method. It is a method of making the process, for example, Japanese Patent Laid-Open No. 5-1484.
It can be produced by the method disclosed in Japanese Patent Publication No. 13 or the like. As the solvent used in the solution casting method, benzene,
Toluene, aromatic compounds such as xylene, butyl acetate,
Tetrahydrofuran, dimethoxyethane, chloroform, methylene dichloride, methyl ethyl ketone, cyclohexane and the like which are generally used as a solvent can be mentioned. As a method for casting a solution, the solution is extruded from a die of a certain width onto a metal drum, a steel belt, a polyester film, a polytetrafluoroethylene (trade name Teflon) belt, etc., and dried over a period of time and temperature. . Further, a film having a uniform thickness can be produced by applying the solution by spraying, brushing, rolling, spin coating, dipping or the like, and optionally applying temperature and time.

As the shape of the molding material used in the injection molding method or the melt casting method, it is preferable to supply it in the form of pellets, but in the powder form, flake form, or the melt casting method, it is supplied to the extruder in the form of a solution. It is also possible to do so. When supplied in the form of pellets, the pellets are preferably dried as a pretreatment for molding. Examples of the method include, but are not particularly limited to, a hot air circulation type, a dehumidifying type, a nitrogen circulation type, a vacuum type, and a supply method of a batch type and a continuous type. It is also a preferable method to seal the pellet tank or hopper with an inert gas such as nitrogen.

The molded article made of the thermoplastic resin composition of the present invention can be processed by various known methods. Especially when the surface is coated.
Excellent adhesion between the coating film and molded product and its durability. Here, the type of the coating of the present invention is not particularly limited, but it may impart an optical, mechanical or electromagnetic function to the surface of the molded article such as an antireflection coat, a hard coat, a conductive film, and a specific wavelength light absorption film. is there.

As a hard coat, an organic compound which is hardened by active energy rays or heat is applied and hardened to cover the surface of the light guide plate, whereby functions such as scratch resistance can be imparted. Here, the curable organic compound used for the coating film is not particularly limited as long as it cures the surface of the molded body made of the composition of the present invention, but is not limited to, for example, JP-A No. 11-289489 or JP-A No. 2-289489.
As disclosed in Japanese Patent Application Laid-Open No. 001-110826, an ultraviolet-curable organic compound is excellent and preferable in terms of equipment and industrial productivity, and specifically has the following properties. For example, as the UV-curable organic compound, a polymerizable composition containing an oligomer and / or a monomer having a polymerizable functional group and a UV polymerization initiator as essential components is preferable. Examples of the polymerizable functional group include a radically polymerizable group and a cationically polymerizable group.
More specifically, examples thereof include a vinyl group, a (meth) acryloyl group, an epoxy group, a vinyl ether group, a silyloxy group, and a thiylanyl group. As the oligomer having a polymerizable functional group, a compound having one or more of the above-mentioned functional groups in the molecule is used.
Compounds of 0 to 50,000 are particularly preferred. As the oligomer and / or monomer having these polymerizable functional groups, those having a (meth) acryloyl group are particularly preferable in terms of workability and sensitivity. Examples of the photopolymerization initiator include compounds that generate a chemical species having a polymerization initiation ability such as a radical species and a cation species upon irradiation with ultraviolet rays. Further, a photosensitizer can be added if necessary. From the viewpoint of workability, the UV organic compound is preferably liquid or fluid at room temperature before curing, and can be molded by a method such as brush coating, roll coating, dipping, spin coating or spraying. A surface hardening treatment is possible by applying it to the surface.

The thickness of the surface-cured layer made of an ultraviolet-curable organic compound is preferably 5 μm to 200 μm, more preferably 10 μm to 100 μm, particularly preferably 1 μm.
It is from 0 μm to 50 μm. If the film thickness exceeds 200 μm, it may be difficult to cure uniformly during irradiation with active energy rays, cracks may occur in the coat layer due to large residual stress inside, and the thermal cycle resistance and optical characteristics may be poor. There is a problem. On the other hand, when the film thickness is less than 5 μm, the heat resistance improvement by the coating layer is insufficient. Also,
The transparency of the coating layer made of an ultraviolet-curable organic compound is such that the total light transmittance is 90% or more at a thickness of 3 mm, preferably 92.
% Or more, the reduction of the total light transmittance caused by coating the thermoplastic resin plate is preferably 10% or less, more preferably 5% or less, and particularly preferably 3% or less. If the reduction in the total light transmittance due to coating is larger than 10%, the performance of the molded product as an optical component is deteriorated, which is not preferable.

Antireflection treatment is also preferably used as the coating treatment of the present invention. Examples of the antireflection processing that can be used in the present invention include known dry or wet methods. The dry antireflection treatment is not particularly limited, but for example, JP-A-4-89821,
It is preferable to adopt the method of coating the surface of the norbornene-based resin with an inorganic compound, which is disclosed in JP-A-9-120001. As the inorganic compound used for the antireflection treatment, known oxides, nitrides, fluorides, etc. of silicon, titanium, germanium, aluminum, tantalum, zirconium and the like are used. The vacuum deposition method is not particularly specified, but known PVD and CVD methods are used. Further, the coating layer may have a single layer or a multi-layer structure of two or more layers. Although the thickness per layer is not particularly limited, it is usually laminated in the range of 1 nm to 500 nm. Wet antireflection processing is disclosed, for example, in Japanese Patent Laid-Open No. 9-1200.
No. 02, No. 10-147739, No. 11-189621, and No. 2000-17028.
Known organic compounds as disclosed in Japanese Patent Laid-Open No. 2000-313709, brush coating, roll coating, dipping, spin coating,
It is performed by applying it to the front light surface by a method such as spraying. In the present invention, in order to effectively prevent reflection, the refractive index of the organic compound used is 1.45.
The following is preferable, for example, vinylidene fluoride / hexafluoropropylene polymer, functional group-modified hexafluoropropylene, tetrafluoroethylene / vinylidene fluoride / hexafluoropropylene terpolymer,
A perfluoroalkyl ether-based copolymer, a fluorine-containing methacrylate polymer, a fluorine-containing polysiloxane polymer / a polyfunctional (meth) acrylate compound, etc. can be used. These organic substances can be cured by a method of irradiating with active energy rays such as heat curing, UV curing, electron beam curing. These antireflection treatments may be a single or multi-layered inorganic coating layer, a single or multi-layered organic coating layer, or a combination of an inorganic coating and an organic coating.

The thermoplastic resin composition of the present invention can be used for various optical parts by utilizing its high degree of light transmission and heat resistance. Examples of such optical components include an image display device, an information recording / reproducing device, an information recording medium, an image capturing device, and an optical component of the image reproducing device. Examples of optical components of the image display device include a liquid crystal cell, a polarizing plate, a retardation plate, a light guide plate, a light guide, and a surface protection plate. Examples of optical components of the information recording / reproducing apparatus include a pickup lens, a diffraction grating, and a collimating lens. The optical parts of the information recording medium include CD, MD, M
Examples include recording media such as O and DVD and protective films used for them. As the optical parts of the image capturing device,
Examples include image pickup lenses, finder prisms, protective caps and films for CCD elements, and sealing materials for photosensitive elements. Examples of parts of the image reproducing device include an fθ lens and a pickup lens.

[0048]

EXAMPLES Examples of the present invention will be described below.
The present invention is not limited to these. In the following, "part" means "part by weight".

Component (A) Table 1 shows a list of the component A used in the present invention. The method of synthesizing each A component in the table is illustrated below.

Synthesis Example 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
1 part and 750 parts of toluene (solvent for ring-opening polymerization reaction)
Charge into a reaction vessel purged with nitrogen, and heat this solution to 60 ° C.
Heated. Then, add triethyl acetate to the solution in the reaction vessel.
Luminium solution in toluene (1.5 mol / l) 0.62
And t-butanol / methanol modified hexachloride
Nguzten (t-butanol: methanol: tungsten
(0.3 = 0 mol: 0.3 mol: 1 mol) in toluene
Liquid (concentration 0.05 mol / l) 3.7 parts and
When the system is heated and stirred at 80 ° C for 3 hours, the ring-opening polymerization reaction
To give a ring-opened polymer solution. In this polymerization reaction
The polymerization conversion rate was 97%. Thus obtained
Charge 4,000 parts of ring-opening polymer solution into autoclave
In this ring-opening polymer solution, RuHCl (CO) [P
(C₆H_Five)₃]₃  0.48 parts was added, and the hydrogen gas pressure was 10
0 kg / cm²Under reaction temperature of 165 ℃ for 3 hours
The hydrogenation reaction was carried out by stirring with heat. Obtained anti
After cooling the reaction solution (hydrogenated polymer solution), hydrogen gas
Was released. Hydrogenated polymer thus obtained
[Hereinafter, referred to as (A-1). ] Hydrogenation rate of 400M
Hz¹When measured by 1 H-NMR, it was virtually 100%.
there were.

Synthesis Example 2 A hydrogenated polymer was obtained in the same manner as in Synthesis Example 1 except that the amount of 1-hexene (molecular weight modifier) added was 27 parts. The hydrogenation rate of the obtained hydrogenated polymer [(hereinafter, referred to as (A-2)] was substantially 100%.

Synthesis Example 3 8-Ethylidenetetracyclo [4.
4.0.1 ^2,5 . A hydrogenated polymer was obtained in the same manner as in Synthesis Example 1 except that 250 parts of 1 ^7,10 ] -3-dodecene (specific monomer) and 750 parts of cyclohexane were used as a solvent for the ring-opening polymerization reaction. The resulting hydrogenated polymer [hereinafter referred to as (A-3). ], The hydrogenation rate is substantially 100
%Met.

Synthesis Example 4 8-Methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 225 parts of ^1,7,10 ] -3-dodecene and bicyclo [2.2.1] hept-2-
Using 25 parts of ene, 1-hexene (molecular weight regulator)
A hydrogenated polymer was obtained in the same manner as in Synthesis Example 1, except that the addition amount of was 43 parts. The obtained hydrogenated polymer [hereinafter referred to as (A-4). ] Has a hydrogenation rate of substantially 1
It was 00%.

Synthesis Example 5 A hydrogenated polymer was obtained in the same manner as in Synthesis Example 4 except that the addition amount of 1-hexene (molecular weight modifier) was 33 parts. The obtained hydrogenated polymer [hereinafter referred to as (A-5). ], The hydrogenation rate was substantially 100%.

Synthesis Example 6 8-Methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 225 parts of ^1,7,10 ] -3-dodecene and 5-phenylbicyclo [2.2.1]
A hydrogenated polymer was obtained in the same manner as in Synthesis Example 1 except that 25 parts of hept-2-ene was used and the amount of 1-hexene (molecular weight modifier) added was 25 parts. The obtained hydrogenated polymer [hereinafter referred to as (A-6). ], The hydrogenation rate was substantially 100%.

Synthesis Example 7 A hydrogenated polymer was obtained in the same manner as in Synthesis Example 6 except that the addition amount of 1-hexene (molecular weight modifier) was 18 parts. The obtained hydrogenated polymer [hereinafter referred to as (A-7). ], The hydrogenation rate was substantially 100%.

Component (B) B-1: Glycerin monostearate (Rikemar: Riken Vitamin Co., Ltd.) B-2: Glycerin mono-dipalmilate (Rikemar: Riken Vitamin Co., Ltd.) B-3: Glycerin tristearate ( Rikemar: Riken Vitamin Co., Ltd., esterification rate: 100%)

(C) Component C-1: Hydrogenated C ₉ petroleum resin (ESCOLETS:
Tonex Co., Ltd.), molecular weight 1,590, softening point 100 ° C. C-2: hydrogenated C ₉ petroleum resin (Arcon: Arakawa Chemical Industry Co., Ltd.), molecular weight 750, softening point 125 ° C.

(D) Other components D-1: Zinc stearate (Zinc stearate: manufactured by Sakai Chemical Industry Co., Ltd.) D-2: Amide oleate (fatty acid amide: manufactured by Kao Corporation)

<Preparation Method of Composition> Components (B) and (C) were added to a solution of the component (A) so that the compositions shown in Tables 2 and 3 were obtained.
The component and the component (D) were added and dissolved, and then the composition was solidified and isolated with a large amount of methanol, and then granulated by a twin-screw extruder to obtain pellets.

<Method of molding test piece> Molded product shape: 50 × 50 mm, thickness of 3.0 mm flat plate molding method: In-line injection molding machine (mold clamping 75 ton, cylinder diameter 28 mm) is used and shown in the following examples. Injection molding was performed using the pellets of the composition. Molded product Shape: 0.8 mm thick, 600 mm wide sheet forming method: 600 m wide at the tip of a single screw extruder with a diameter of 50 mm
A T-die of m was attached, the composition was melt-extruded, and cooled on a roll and a belt to obtain a sheet-shaped molded product. Molded product Shape: Film having a thickness of 0.1 mm and a width of 600 mm Molding method: The composition is in toluene and the concentration of the composition is 30.
Dissolved to give a weight percentage, clearance of 0.254
Membranes were made using a mm applicator bar. Further, this film was dried for 24 hours in a vacuum dryer kept at 60 ° C. to obtain a film.

<Method of forming antireflection film> An antireflection film was formed by the following method. On one side of a test piece with a coat of 150 mm x 10 mm and a thickness of 1 mm,
SiO ₂ was deposited by 140 nm, TiO ₂ was deposited by 120 nm, and finally SiO ₂ was deposited by 170 nm by a vapor deposition method. The pressure during vapor deposition was 10 ⁻⁴ Torr. Coat vinylidene fluoride 70 parts, hexafluoropropylene 3
Copolymerization of 0 parts, polystyrene equivalent number average molecular weight 4.5
A polymer of × 10 ⁴ was obtained. 70 parts of this polymer and 30 parts of dipentaerythritol hexaacrylate were added to 2,500 parts of methyl isobutyl ketone, which was a solvent, and mixed by stirring for 1 hour to obtain a coating material having a concentration of 4% by weight. After applying this paint by dipping on the same test piece as the coat,
The solvent was sufficiently evaporated by heating to 60 ° C., and an electron beam was irradiated to this using an electron beam irradiation device so that the dose of 3 Mrad was applied to cure the same.

Each evaluation method in Examples and Comparative Examples is shown below. * Yellowness: YI was measured with a hue spectrophotometer (manufactured by Suga Test Instruments). * Durability (Hue) The test was conducted under the condition of gear oven 100 ° C., and after 500 hours, YI was measured by the above method. * Adhesion of the film The state of film formation was observed. The state of film adhesion after heating at 100 ° C. for 1 hour was observed. As an evaluation method, the surface of the film was wiped with Bencotton (manufactured by Asahi Kasei) 10 times and the surface condition was observed. ◯: No peeling of the film is observed. Δ: Small scratches are noticeable. X: The film peels off in a plane. * Releasability Releasability when injection molding was performed was evaluated. ◯: The molded product can be easily removed from the mold. Δ: A molded product is taken in the mold. X: The exfoliated material of the resin adheres to the mold. * Surface property of the film The surface condition of the film / sheet-shaped molded product was observed. ◯: No die line or scratch originating from the die is observed. Δ: Die lines and scratches originating from the die are recognized. X: Fogging is observed on the film / sheet.

Examples 1 to 20 and Comparative Examples 1 to 12 The thermoplastic resin compositions having the compositions shown in Tables 2 to 3 were evaluated. Comparison between Examples 1 to 20 in Table 2 and Comparative Examples 1 to 12 in Table 3 indicates that the thermoplastic resin composition of the present invention has good coatability without impairing releasability or film surface property, and It can be seen that there is little heat coloring and the heat resistance is excellent.

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

[Table 3]

[0068]

INDUSTRIAL APPLICABILITY The thermoplastic resin composition of the present invention is excellent in releasability, heat resistance and secondary workability, and can be used for a wide range of optical parts. Examples of such optical components include an image display device, an information recording / reproducing device, an information recording medium, an image capturing device, and an optical component of the image reproducing device.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 5/103 C08K 5/103 C08L 45/00 C08L 45/00 G02B 1/04 G02B 1/04 // B29L 11:00 B29L 11:00 (72) Inventor Takuhiro Ushino 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Corporation (72) Inventor Nobuyuki Miyaki 2-11-24 Tsukiji, Chuo-ku, Tokyo Jay In the S-R Co., Ltd. (72) Inventor Kazuo Kasai 2-11-24 Tsukiji, Chuo-ku, Tokyo JR S-F Co., Ltd. F-term (reference) 4F070 AA11 AA12 AA41 AC43 AE17 AE30 FA04 FB04 FC05 4F071 AA14 AA39 AA69 AA81 AC10 AE22 AF01 AF29 AF34 AF53 AF57 AF58 BA01 BB02 BB05 BB06 BC01 4F206 AA03 AA24 AC08 AH73 JA07 4J002 BA012 BK001 CE001 EH046 EH056 FA010 FA040 FD020 FD036 FD050 FD090 FD166 GP00 GS00

Claims (10)

[Claims] 1. A thermoplastic resin composition comprising (A) a cyclic olefin-based thermoplastic resin and (B) an ester compound of glycerin and a saturated fatty acid. 2. Further, in addition to the component (C) other than the component (A),
The thermoplastic resin composition according to claim 1, which has a polystyrene-reduced weight average molecular weight of 20,000 or less and contains a hydrocarbon resin that is solid at room temperature. 3. The thermoplastic resin composition according to claim 1, wherein the cyclic olefin-based thermoplastic resin (A) contains at least one polar group in its molecule. 4. The esterification rate of the ester compound of (B) glycerin and saturated fatty acid is 90% or more.
~ 3 thermoplastic resin composition according to any one of. 5. A molded product obtained by molding the thermoplastic resin composition according to any one of claims 1 to 4. 6. The molded article according to claim 5, which is an injection molded article. 7. The molded article according to claim 5, which is a film or sheet produced by a melt casting method or a solution casting method. 8. The method according to any one of claims 5 to 7, wherein the ester compound (B) of glycerin and saturated fatty acid is supplied in a masterbatch during molding of the molded article according to any one of claims 5 to 7. Or a method for producing a molded article according to item 1. 9. An optical component using the molded product according to claim 5. 10. The optical component according to claim 9, which is used for at least one application selected from an image display device, an information recording / reproducing device, an information recording medium, an image capturing device, and an image reproducing device.