JP2001323074A - Injection molded form with fine pattern transferred in high accuracy - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an injection molded form usable as an optical material with high heat resistance and high moist heat resistance by transferring in high accuracy a fine pattern carved on the inner surface of a mold cavity on a molded form by injection molding. SOLUTION: This injection molded form with a fine pattern transferred in high accuracy is obtained by injection molding of a cyclic olefin resin or a thermoplastic resin composition comprising the above cyclic olefin resin and a specific hydrocarbon resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an injection molded article mainly used for optical materials and the like, on which a fine pattern is transferred (highly transferred) on a surface with high precision. By using a specific cyclic olefin-based thermoplastic resin composition, an injection molded article having excellent heat resistance and wet heat resistance and having a pattern transferred with high precision is provided.

[0002]

2. Description of the Related Art Conventionally, in order to form a fine pattern on the surface of an optical material, the surface is mechanically cut, a resist is applied and a pattern is printed, and printing is performed using a heat, ultraviolet or electron beam curable resin. And the like. These methods require very high and complicated processing techniques in mechanical cutting, and the pattern printing method has complicated processes and also has a problem of durability such as peeling of a printed pattern. To solve these,
There is a type in which a fine pattern is formed on a mold and transferred by injection molding. For these, methacrylic resin or polycarbonate resin is used, but the balance between fluidity and material solidification rate is poor, and it has been difficult to perform high transfer. In addition, these resins have problems of heat resistance and dimensional change due to water absorption, and there is a problem in their use in optical materials.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to provide various characteristics of a cyclic polyolefin-based thermoplastic resin or a cyclic polyolefin-based thermoplastic resin composition. Provided is an injection-molded article having high heat transfer and high heat-transferred fine pattern, which can be used as an optical material while maintaining heat resistance and heat and humidity resistance.

[0004]

The present invention relates to (A) a cyclic olefin-based thermoplastic resin, or (A) a cyclic olefin-based thermoplastic resin and (B) a polystyrene equivalent weight average molecular weight of 20,000 or less and a solid at room temperature. An object of the present invention is to provide an injection molded article on which a fine pattern formed by molding a thermoplastic resin composition made of a hydrocarbon resin is transferred with high precision. The present invention also provides the above-mentioned injection-molded article, wherein the (A) cyclic olefin-based thermoplastic resin contains one or more polar groups.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the thermoplastic resin composition of the present invention will be described in detail. <Component (A): Cyclic olefin-based thermoplastic resin> Component (A): cyclic olefin-based thermoplastic resin (hereinafter referred to as component (A)) constituting the resin composition of the present invention includes Coalescence can be mentioned. 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 be integrated 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-based resin [component (A)] obtained from the above specific monomer may contain one or more polar groups in the molecular structure from the viewpoint of improving the processability of injection molding. preferable.

<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, particularly preferably 1). Also, of the specific monomers, the formula - (CH ₂₎ a specific monomer having a polar group represented by n COOR ⁵ has a thermoplastic resin composition obtained high glass transition temperature and low moisture absorption It is preferable in that it becomes a thing. 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 above general formula (I), R ¹ or R ³ is preferably an alkyl group, and the alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2, particularly preferably 1 to 2. It is. In particular, the alkyl group is the above formula - is preferably coupled to (CH ₂₎ the same carbon atom and the carbon atom to which the polar group is bonded, represented by n COOR ^5. 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 tetracyclod
Decene, 6-ethylidene-2-tetracyclododecene,
Trimethanooctahydronaphthalene, pentacyclo
[8.4.0.1^2,5 . 1^9,12. 0^8,13] -3-Hexa
Decene, heptacyclo [8.7.0.1^3,6 . 1
^10,17 . 1^12,15 . 0^2,7 . 0^11,16] -4-Eicose
Heptacyclo [8.8.0.1^4,7 . 1^11,18 . 1
^13,16 . 0^3,8 . 0^12,17] -5-heneicosen, 5
-Ethylidenebicyclo [2.2.1] hept-2-e
8-ethylidenetetracyclo [4.4.0.1
^2,5 . 1^7,10] -3-dodecene, 5-phenylbicyclo
[2.2.1] Hept-2-ene, 8-phenyltetra
Cyclo [4.4.0.1^2,5 . 1^7,10] -3-Dodece
5-fluorobicyclo [2.2.1] hept-2-
Ene, 5-fluoromethylbicyclo [2.2.1] hep
To-2-ene, 5-trifluoromethylbicyclo [2.
2.1] Hept-2-ene, 5-pentafluoroethyl
Bicyclo [2.2.1] hept-2-ene, 5,5-di
Fluorobicyclo [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 (tri
Fluoromethyl) bicyclo [2.2.1] hept-2-
Ene, 5-methyl-5-trifluoromethylbicyclo
[2.2.1] Hept-2-ene, 5,5,6-triff
Fluorobicyclo [2.2.1] hept-2-ene, 5,
5,6-tris (fluoromethyl) bicyclo [2.2.
1] Hept-2-ene, 5,5,6,6-tetrafluoro
Lobicyclo [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 [2.2.1] hept-
2-ene, 5-fluoro-5-pentafluoroethyl-
6,6-bis (trifluoromethyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-difluoro-5-
Heptafluoro-iso-propyl-6-trifluoro
Methylbicyclo [2.2.1] hept-2-ene, 5-
Chloro-5,6,6-trifluorobicyclo [2.2.
1] Hept-2-ene, 5,6-dichloro-5,6-bi
(Trifluoromethyl) bicyclo [2.2.1] hep
To-2-ene, 5,5,6-trifluoro-6-trif
Fluoromethoxybicyclo [2.2.1] hept-2-e
, 5,5,6-trifluoro-6-heptafluorop
Lopoxybicyclo [2.2.1] hept-2-ene, 8
-Fluorotetracyclo [4.4.0.1^2,5 .
1^7,10] -3-Dodecene, 8-fluoromethyltetracy
Black [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-trifluoromethyl
Letetracyclo [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-difluorotetracycline
B [4.4.0.1^2,5 . 1^7,10-3-dodecene,
8,8-bis (trifluoromethyl) tetracyclo
[4.4.0.1^2,5 . 1 ^7,10-3-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 . 1 ^7,10] -3-dodecene, 8,8,9-triff
Fluorotetracyclo [4.4.0.1^2,5 . 1^7,10]-
3-dodecene, 8,8,9-tris (trifluoromethyl
Le) tetracyclo [4.4.0.1^{2, Five} . 1^7,10] -3
-Dodecene, 8,8,9,9-tetrafluorotetracy
Black [4.4.0.1^2,5 . 1^7,10-3-dodecene,
8,8,9,9-tetrakis (trifluoromethyl) te
Toracyclo [4.4.0.1^2,5 . 1^7,10] -3-Dode
Sen, 8,8-difluoro-9,9-bis (trifluoro
Romethyl) 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-trifluoromethyltetracyclo
[4.4.0.1^2,5 . 1^7,10-3-dodecene, 8,
8,9-trifluoro-9-trifluoromethoxytet
Lacyclo [4.4.0.1^2,5 . 1^7,10] -3-Dodece
8,8,9-trifluoro-9-pentafluorop
Lopoxytetracyclo [4.4.0.1^2,5 . 1^7,10]
-3-dodecene, 8-fluoro-8-pentafluoroe
Cyl-9,9-bis (trifluoromethyl) tetracyclyl
B [4.4.0.1^2,5 . 1^7,10-3-dodecene,
8,9-difluoro-8-heptafluoroiso-pro
Pill-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) tetra
Lacyclo [4.4.0.1^2,5 . 1^7,10] -3-Dodece
8-methyl-8- (2,2,2-trifluoroethene
Xycarbonyl) tetracyclo [4.4.0.1^2,5 .
1^7,10] -3-dodecene and the like.

Among these specific monomers, 8-methyl-
8-methoxycarbonyltetracyclo [4.4.0.1
^2,5 . 1^7,10-3-Dodecene, 8-ethylidenetetra
Cyclo [4.4.0.1^2,5 . 1^7,10-3-Dodese
8-ethyltetracyclo [4.4.0.1^2,5 . 1
^7,10] -3-dodecene, pentacyclo [7.4.0.1
^2,5 . 1^9,12. 0^8,13-3-pentadecene 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
Representative examples of the Re compound include WCl6, MoCl
_Five , ReOCl_Three Japanese Patent Application Laid-Open No. 1-240517
The compounds described can be mentioned. (B) Components
For example, nC_Four H₉ Li, (C_Two H_Five )_Three Al,
(C _Two H_Five )_Two AlCl, (C_Two H_Five )_1.5 AlCl
_1.5 , (C_Two H_Five ) AlCl_Two, Methylalumoxane,
Compounds described in JP-A-1-240517 such as LiH
Things can be mentioned. Substitute for component (c) which is an additive
Examples of tables include alcohols, aldehydes, ketones
, Amines and the like can be suitably used.
Uses compounds disclosed in JP-A-1-240517
can do.

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 /
Examples include diethylaluminum monochloride, rhodium acetate, rhodium chlorotris (triphenylphosphine), ruthenium dichlorotris (triphenylphosphine), ruthenium chlorohydrocarbonyltris (triphenylphosphine), and ruthenium dichlorocarbonyltris (triphenylphosphine). 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)_a X_b Or
V (OR)_c X _d (Where R is a hydrocarbon group, 0 ≦ a
≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0 ≦
vanadium compound represented by d ≦ 4, 3 ≦ c + d ≦ 4)
Or an electron donor adduct thereof.
Alcohols, phenols, keto as electron donors
Aldehydes, carboxylic acids, organic or inorganic acids
Stele, ether, acid amide, acid anhydride, alkoxy
Oxygen-containing electron donors such as orchids, ammonia, amines, nitrite
Examples include nitrogen-containing electron donors such as ril and isocyanate.
Can be As an organoaluminum compound catalyst component,
At least one aluminum-carbon bond or aluminum
At least one selected from those having a hydrogen bond
One type is used. The ratio of catalyst components to vanadium atoms
A ratio of aluminum atoms to aluminum (Al / V) of 2 or more
It is preferably in the range of 2 to 50, particularly preferably 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.

<Specific cyclic olefin-based thermoplastic resin composition> The specific cyclic olefin-based thermoplastic resin composition used in the present invention includes, for example, JP-A-9-221577 and JP-A-10-287.
732 is a thermoplastic resin composition containing a specific hydrocarbon resin, and in addition to <(A component)>, the following <(B component): hydrocarbon resin> Including. Such a thermoplastic resin composition has a good balance between heat resistance and moldability.

<Component (B)> The hydrocarbon resin of the present invention has a weight average molecular weight in terms of polystyrene of 20,000 or less, preferably 100 to 20,000, more preferably 200 to 10,000, and particularly preferably 30 to 10,000.
0 to 5000. It is solid at room temperature. Specific examples include C5 resin, C9 resin, C5 / C9 mixed resin, cyclopentadiene resin, vinyl-substituted aromatic compound polymer resin, olefin / vinyl-substituted aromatic compound copolymer resin, cyclopentadiene resin Examples thereof include a copolymer resin of a compound / vinyl-substituted aromatic compound or a hydrogenated product of the resin. Among these, C5 resin, C9 resin, C5 series / C9
Examples thereof include a mixed resin, a cyclopentadiene resin, a polymer resin of a vinyl-substituted aromatic compound, and a mixture thereof. The C5 resin is preferably an aliphatic resin, and the C9 resin is preferably an alicyclic resin. Of these, particularly preferred are C9 resin, cyclopentadiene-based resin, and a mixture thereof.

If the weight average molecular weight of these hydrocarbon resins in terms of polystyrene is too high, the compatibility with a thermoplastic thermoplastic norbornene resin having a polar group becomes poor and the transparency is undesirably reduced. Use of a hydrocarbon compound which is liquid at normal temperature is not preferred because the strength of the resin is easily reduced and bleeds on the surface of the resin. The mixing ratio of the hydrocarbon resin is 0.1 to 100 parts by weight, preferably 1 to 60 parts by weight, more preferably 2 to 50 parts by weight, and particularly preferably 5 to 45 parts by weight with respect to 100 parts by weight of the thermoplastic norbornene resin. Parts by weight. The blending method of the thermoplastic resin composition used in the present invention may be a known apparatus used for processing a thermoplastic resin, for example, a twin-screw extruder, a single-screw extruder, a continuous kneader, a roll kneader, a pressure kneader, a Banbury mixer. And blending a hydrocarbon-based resin with a solution of a norbornene-based resin to form a pellet.

The cyclic olefin-based thermoplastic resin or the specific cyclic olefin-based thermoplastic resin composition used in the injection-molded article of the present invention may further include a known thermoplastic resin within a range that does not impair the transparency and heat resistance of the composition. , A thermoplastic elastomer, a rubbery polymer, organic fine particles, inorganic fine particles, and the like.

The resin composition of the present invention contains a known antioxidant, for example, 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.

The cyclic olefin-based thermoplastic resin and the specific cyclic olefin-based thermoplastic resin composition used in the present invention preferably have a glass transition temperature (Tg) of 110.
C. to 200.degree. C., more preferably 115 to 180.degree. C. are suitable in terms of heat resistance and moldability. The melt viscosity at 260 ° C. was a shear rate of 10 (rad /
s) and the shear rate 10000 (r
ad / s) and the ratio to the melt viscosity η2 (η1 / η2)
Is preferably from 50 to 500, more preferably from 100 to 450, and particularly preferably from 150 to 400. Within this range, the pattern transferability is excellent.

The surface of the injection molded article of the present invention can be subjected to secondary processing by a known method. For example, the surface is cured by electron beam, ultraviolet ray, etc.
Applying organic compounds to the surface to impart functions such as anti-reflection, corrosion resistance, and scratch resistance, depositing metal thin films, imparting functions such as anti-reflection, corrosion resistance, and scratch resistance. Examples thereof include laminating a resin sheet or film containing an olefin-based thermoplastic resin, and applying a paint containing a pigment or a dye. When laminating film sheets, the surface thereof may be subjected to a known surface treatment.

The shape of the molded article of the present invention is not particularly limited. Examples of shapes include circular or polygonal flat plates,
Examples include a wedge, a rod, a hollow circle, a prism, a lens, and a trough. Also, the shape of the fine pattern is not particularly limited. For example, a shape having one or a plurality of parallel or lattice grooves (concave, convex, V-shaped, semicircular, trapezoidal, prismatic) on the surface of the molded body. A shape in which a plurality of polygonal pyramids such as hemispheres, triangular pyramids, and quadrangular pyramids, cones, rectangular parallelepipeds, cylinders, triangular prisms, and quadrangular prisms are arranged in a lattice or staggered pattern. Shapes in which markings such as circles, crosses, polygons, rounded polygons, and the like are provided on the surface of the molded body are given. Examples of fine patterns are shown in FIGS.

The size of the fine pattern is not particularly limited, but it is possible to transfer a pattern having a depth and width of 0.01 to 1000 μm, preferably 0.01 to 1000 μm.
~ 500 μm, more preferably 0.01-100 μm, especially 0.0
It is possible to transfer an image of 1 to 50 μm. When a plurality of fine patterns are formed, the distance between the patterns is not particularly limited.
000-0.02 μm, preferably 500-0.02 μm
m, more preferably 200 to 0.02 μm, particularly preferably 100 to 0.05 μm.

The molded article of the present invention is formed by injection molding. The type of the injection molding machine is not particularly limited. For example, the cylinder system includes an in-line system, a pre-plastic system, the mold clamping system includes a direct pressure system, a toggle system, and the drive system includes a hydraulic system, an electric servo system, and a system combining these. The fine pattern is provided by a metal mold, and the metal mold is usually manufactured from a known steel material. The surface of the cavity may be surface-treated by a known method. The fine pattern of the mold is formed by a known method such as cutting, etching, and electroforming. The fine pattern may be formed on the movable side, the fixed side, or both sides of the mold, and may have a structure with a movable portion such as a slide core.

The gate shape is straight, pin gate, fan gate, film gate, tunnel gate,
A known method such as a method in which an aperture is inserted in the middle of the gate can be used. For the protrusion of the molded product, a known method such as pin protrusion and surface mounting can be used. Normal water or mineral oil can be used as a temperature control medium for the mold. Drying of the resin before molding is performed by a known hot-air method, dehumidification method or vacuum method, usually at 80 ° C. to 120 ° C. for 4 to 6 hours. In addition, from the viewpoint of improving the hue of the molded product or preventing burning, etc., an inert gas such as nitrogen or argon is filled in from the hopper, and for example, “ALFI” marketed by Sumitomo Heavy Industries, Ltd.
A device for vacuuming the plasticizing section such as "N" may be used. The molding conditions are not particularly limited, but usually the cylinder temperature is 260 ° C to 300 ° C, and the mold temperature is the glass transition temperature Tg-1 ° C to Tg-20 ° C of the cyclic olefin resin or the specific cyclic olefin resin composition. It is preferable to mold within the range.

The injection molded article of the present invention is used for various optical materials that require fine pattern processing on the surface, such as prisms, lenses, flat lenses, diffraction gratings, light guide plates, diffusion plates, and various light guides of liquid crystal display devices. Can be used.

[0034]

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”.

A component Table 1 shows a list of the A component used in the front light guide plate of the present invention. As a method for adjusting the component A, a method for synthesizing the component (A-1) will be exemplified. In addition, the following (A-2) is (A-
It was manufactured according to 1).

[0036]

[Table 1]

Method for adjusting component (A-1) 8-Methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
250 parts of 3-dodecene (specific monomer), 41 parts of 1-hexene (molecular weight regulator), and 750 parts of toluene (solvent for ring-opening polymerization reaction) were charged into a reaction vessel purged with nitrogen,
The solution was heated to 60C. Next, a solution of triethylaluminum in toluene (1.5%) was added to the solution in the reaction vessel.
Mol / l) 0.62 parts and tungsten hexachloride modified with t-butanol / methanol (t-butanol: methanol: tungsten = 0.35 mol: 0.3 mol: 1)
Mol) in toluene (concentration 0.05 mol / l) 3.7
And 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 in this polymerization reaction was 97%.

[0038]

Embedded image

The ring-opened polymer solution 4 thus obtained
000 parts were charged into an autoclave, and RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opened polymer solution.
0.48 parts, hydrogen gas pressure 100 kg / cm ² ,
A hydrogenation reaction was performed by heating and stirring for 3 hours at a reaction temperature of 165 ° C. After cooling the obtained reaction solution (hydrogenated polymer solution), the pressure of hydrogen gas was released. The hydrogenated polymer thus obtained (hereinafter, (A-1)
Ingredients. ) Is substantially 100%.

[0040]

[B component] (B-1) component Cyclopentadiene-vinyl aromatic petroleum resin, molecular weight 1130, softening point 125 ° C (B-2) component vinyl aromatic petroleum resin, molecular weight 2440, softening point 14
0 ° C (B-3) component C9 / dicyclopentadiene-based petroleum resin molecular weight 81
8, Softening point 125 ° C (B-4) component Hydrogenated C9 petroleum resin Molecular weight 1590, Softening point 100 ° C Other resins Methacrylic resin: specific gravity 1.19, Tg108 ° C, MFR
(260 ° C., 10 kg) 154 polycarbonate resin: specific gravity 1.20, Tg 146 ° C.
MFR (260 ° C, 10Kg) 34

Preparation Method of Thermoplastic Resin Composition A predetermined amount of the component B was added to and dissolved in the polymerization solution of the component A. After coagulation and isolation of the polymer with a large amount of the polymer solution, the mixture was granulated to obtain pellets. What is the viscosity ratio of the polymer? Using a cone plate type rheometer, the relationship between the shear rate and the melt viscosity at 260 ° C. was determined using a known rheological model (cros
(s model), the melt viscosity η1 at a shear rate of 10 (rad / s) and the melt viscosity η2 at a shear rate of 10,000 (rad / s) were obtained, and the viscosity ratio η1 / η2 was calculated. Viscosity ratio η of polymer or composition used in Examples and Comparative Examples
1 / η2 is shown in Table-2.

[0042]

[Table 2]

Shape of molded article: Shape-1 A flat plate having a size of 100 mm × 100 mm and a thickness of 1 mm, a concave parallel pattern having a width, a depth of 0.5 μm and a space of 5 μm × 100 was formed.・ Shape-2 100mm × 100mm, 1mm thick flat plate, width 250μm, depth 1
100 prisms of 0 μm were formed. Shape-3 A flat plate having a size of 100 mm × 100 mm and a thickness of 1 mm, and 100 × 100 hemispherical dots having a radius of 15 μm were formed in a grid at intervals of 100 μm.・ Shape-4 3mm × 3mm, 60mm long rod shape, 10μm width on one side
100 V-grooves having a height of 15 μm and a length of 3 mm were formed in a convex shape at intervals of 500 μm.・ Shape-5 1mm width, 1μm depth, 15mm diameter on a square surface of a right angle triangular prism with a length of 15mm and height of 15mm.
A μm mark was formed.

Method for Forming Test Specimens Samples used in the following tests were injection molded.
The molding machine is SG75M-2 manufactured by Sumitomo Heavy Industries. Molding conditions are resin temperature 260
~ 300 ℃, mold temperature 80 ~ 140 ℃.

The following items were tested according to the gist of the present invention. * Transferability The fine transferability was measured with a fine shape measuring instrument and evaluated according to the shape as follows.・ Shape-1 ◎ -Transfer of linear part in depth direction is 95% or more ○ -Transfer of linear part in depth direction is 85% to 95% △ -Transfer of linear part in depth direction is 70% to 85% × —Transferability of the linear portion in the depth direction is less than 70%. ・ Shape-2 ◎ −Transferability of the short side of the linear portion is 90% or more. ○ −Transferability of the short side of the linear portion is 80 to 90%. The transferability of the short side of the portion is 70 to 80%. The transferability of the short side of the linear portion is less than 70%. Shape-3 ◎ -Roundness of the hemispherical dot at the longest diameter portion is 98% or more. Roundness at the longest diameter portion of the dot is 95 to 9
8% Δ-Roundness at the longest diameter portion of the hemispherical dot is 85 to 9
5% × −Roundness at the longest diameter portion of the hemispherical dot is less than 85%. ・ Shape-4 ◎ −Average transferability of both sides of V groove is 90% or more. 90% The average transferability of both sides of the -V groove is 70 to 80%. The average transferability of both sides of the -V groove is less than 70%.-Shape-5-The mark is sufficiently transferred without displacement. A shift is seen in a part of the Δ-mark. Multiple transfer of x-mark is seen.

* Durability The following two types of tests were performed, and the pattern shape after the test was evaluated.・ Heat resistance Gear oven, left at 100 ° C. × 500 hours ・ Moisture resistance Heat, left in a high temperature / humidity bath at 85 ° C. × 85 RH% for 500 hours The shape of the sample after the test was evaluated according to the above respective evaluation criteria.

Examples 1 to 24 and Comparative Examples 1 to 10 The performances of the injection molded articles were evaluated based on the compositions shown in Tables 3 to 5. From these comparisons, the injection molded article of the present invention is:
It can be seen that the pattern shape does not change under the environment of actual use because it is excellent in the transferability of the fine pattern on the surface of the molded body and also in the heat resistance and the wet heat resistance.

[0048]

[Table 3]

[0049]

[Table 4]

[0050]

[Table 5]

[0051]

Industrial Applicability The thermoplastic resin composition of the present invention provides an injection-molded article having a fine pattern transferred onto its surface while maintaining the good properties (heat resistance and wet heat resistance) of a cyclic polyolefin resin. can do.

[0052]

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of an injection-molded article to which a fine pattern of the present invention has been transferred, showing a plan view and a sectional view, respectively.

FIG. 2 is a schematic view showing an example of an injection-molded article to which a fine pattern of the present invention has been transferred, showing a plan view and a cross-sectional view, respectively.

FIG. 3 is a schematic view showing an example of an injection-molded article to which a fine pattern of the present invention is transferred, and shows a plan view and a cross-sectional view, respectively.

FIG. 4 is a schematic view showing an example of an injection-molded article to which a fine pattern of the present invention has been transferred, showing a plan view and a sectional view, respectively.

FIG. 5 is a schematic view showing an example of an injection-molded article to which a fine pattern of the present invention has been transferred, showing a plan view and a cross-sectional view, respectively.

FIG. 6 is a schematic view showing an example of an injection-molded article to which a fine pattern of the present invention has been transferred, showing a plan view and a cross-sectional view, respectively.

FIG. 7 is a schematic view showing an example of an injection-molded article to which a fine pattern of the present invention is transferred, showing a plan view and a sectional view, respectively.

FIG. 8 is a schematic view showing an example of an injection-molded article to which a fine pattern of the present invention has been transferred, showing a plan view and a sectional view, respectively.

FIG. 9 is a schematic view showing an example of an injection-molded article to which a fine pattern of the present invention has been transferred, showing a plan view and a sectional view, respectively.

FIG. 10 is a schematic view showing an example of an injection-molded article to which a fine pattern of the present invention is transferred, showing a plan view and a sectional view, respectively.

[Explanation of symbols]

 Dotted line indicates ridgeline of protrusion or bottom of groove

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Takuhiro Ushino F-term (reference) 4J07 AA39 AA69 AF45 AF57 AH19 BB05 BC03 BC04 BC06 4F206 AA12 AF16 AH73 2-1-1-24 Tsukiji, Chuo-ku, Tokyo JA07 JB28 JF01 JQ81 4J002 BA012 CE001 FD070 GP00

Claims (2)

[Claims] 1. A cyclic olefin thermoplastic resin (A) or a cyclic olefin thermoplastic resin (A) and (B)
An injection-molded product obtained by molding a fine pattern formed by molding a thermoplastic resin composition comprising a hydrocarbon resin having a weight average molecular weight in terms of polystyrene of 20,000 or less and solid at ordinary temperature and transferred with high precision. 2. The injection-molded article according to claim 1, wherein the cyclic olefin-based thermoplastic resin contains one or more polar groups.