JPH09324082A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition reduced in birefringence and excellent in transparency and flowability. SOLUTION: This composition contains a resin (A) obtained by hydrogenating a cyclic compound produced through the formation of a six-membered ring from a double bond in the main chain and a benzene ring on the side chain of a phenly-norbornene ring-opening (co)polymer and/or a cyclic olefin copolymer (B) obtained by copolymerizing ethylene with a cyclic olefin compound, and a hydrocarbon resin (C) that has a weight-average molecular weight in terms of polystyrene of at most 2×10<4> and is solid at ordinary temperature.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition, and more particularly to a resin composition having low birefringence, transparency and fluidity.

[0002]

2. Description of the Related Art Conventionally, a transparent resin has been used as a material for molded articles such as automobile parts, lighting equipment, and electrical parts, which are required to have ordinary transparency. Particularly, recently, an optical material in which optical properties are considered important. The application as is progressing. Polycarbonate-based resins and acrylic-based resins are known as transparent resins preferably used for such applications. However, although acrylic resins are excellent in transparency, they have problems in heat resistance and water absorption. On the other hand, polycarbonate resins are superior in heat resistance and water absorption to acrylic resins. There is a problem such as large. Recently, a thermoplastic norbornene-based resin that has transparency, low water absorption, low birefringence, high heat resistance, and the like has been used as a transparent resin for optical materials. However, with the progress of technology, there has been a demand for optical materials exhibiting lower birefringence.

[0003]

The present invention has been made in view of the above problems, and shows low birefringence and high fluidity while maintaining the properties of conventional norbornene resins. It is to provide a resin composition.

[0004]

According to the present invention, a six-membered ring is formed by a double bond of the main chain of a ring-opening (co) polymer of [A] phenyl-norbornene and a benzene ring of a side chain. And / or [B] a cyclic olefin-based copolymer obtained by copolymerizing ethylene and (b) a cyclic olefin-based compound, and [C] polystyrene-converted weight average molecular weight Of 2 × 10 ⁴ or less and containing a hydrocarbon resin which is solid at room temperature. The present invention will be described in detail below.
Hydrogenation of a cyclized product obtained by forming a 6-membered ring with a double bond of the main chain of the ring-opening (co) polymer of [A] phenyl-norbornene used in the present invention and a benzene ring of a side chain The phenyl-norbornenes that are the monomers of the obtained resin are at least one compound selected from norbornene derivatives having a phenyl group or a substituted phenyl group at the 2-position and / or the 3-position, and represented by the following general formula 1 expressed.

[0005]

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(In the formula, R ^{1 to} R ⁷ are a hydrogen atom and a carbon number 1
To a polar group such as a hydrocarbon group of 4 to 4, a halogen group, an alkoxy group and a cyano group, or a hydrocarbon group of 1 to 4 carbon atoms substituted with these polar groups. )

Specific examples of the monomer represented by the general formula 1 include 5-phenylbicyclo [2,2,1] hept-
2-ene, 5- (2'-methylphenyl) bicyclo [2,2,1] hept-2-ene, 5-phenyl-6-
Methylbicyclo [2,2,1] hept-2-ene, 5-
Phenyl-5-methylbicyclo [2,2,1] hept-
2-ene, 5- (4'-chlorophenyl) bicyclo [2,2,1] hept-2-ene, 5- (2'-ethoxycarbonylphenyl) bicyclo [2,2,1] hept-2-ene, 5-phenyl-5-cyanobicyclo [2,2
2,1] hept-2-ene and the like can be mentioned. The above-mentioned specific monomers do not necessarily need to be used alone, and a ring-opening copolymerization reaction can be performed using two or more kinds.

<Copolymerizable Monomer> The above-mentioned monomer may be a ring-opening polymerized alone, but the monomer and the copolymerizable monomer may be ring-opening copolymerized. It may be a copolymer. Specific examples of the copolymerizable monomer used in this case include bicyclo [2,2,1] hept-2-ene and 5-
Methylbicyclo [2,2,1] hept-2-ene, 5-
Ethylbicyclo [2,2,1] hept-2-ene, 5-
Isopropenylbicyclo [2,2,1] hept-2-ene, 5,5-dimethylbicyclo [2,2,1] hept-
2-ene, 5-methoxycarbonylbicyclo [2,2,2]
1] hept-2-ene, 5-cyanobicyclo [2,2,2]
1] hept-2-ene, 5-methyl-5-methoxycarbonylbicyclo [2,2,1] hept-2-ene, 5-
Hexylbicyclo [2,2,1] hept-2-ene, its alkyl, alkylidene, alkenyl, halogen, hydroxyl group, ester group, alkoxy group, cyano group, amide group, imide group, polar group substitution product such as silyl group, tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] -3-dodecene, 8
- methyl 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, 8-methoxycarbonyltetracyclo [4,4,0,1 ^2,5, 1 ^7,10]
3-dodecene, 8-ethoxycarbonyl tetracyclo [4,4,0,1 ^2,5, 1 ^7,10] -3-dodecene, 8-
Methyl-8-methoxycarbonyltetracyclo [4,4
4,0,1 ^2,5, 1 ^{7,1 0]} -3-dodecene, 8-methyl-8-ethoxycarbonyl-tetracyclo [4,4,0,
1 ^2,5, 1 ^{7,1 0]} -3-dodecene, cycloolefins of the above and similar derivatives and substitution products, dicyclopentadiene and derivatives thereof, cyclobutene, cyclopentene, cycloheptene, etc. cyclooctene, tricyclo [5 ．
2.1.02,6] -3-decene, 5-ethylidene-2-
Norbornene etc. can be mentioned. Furthermore, polybutadiene, polyisoprene, styrene-butadiene copolymer, ethylene-non-conjugated diene polymer, polynorbornene, etc. in the presence of an unsaturated hydrocarbon polymer containing a carbon-carbon double bond in the main chain, etc. The monomer may be subjected to ring-opening polymerization. The hydrogenated product of the ring-opening copolymer obtained in this case is useful as a raw material for a phenyl-norbornene-based resin having high impact resistance.

<Ring-Opening Polymerization Reaction> In the present invention, the ring-opening polymerization reaction of the monomer may be a ring-opening polymerization reaction using a known metathesis catalyst and is not particularly limited. For example, JP
The method described in, for example, 0-154399 may be used. Specifically, ruthenium, rhodium, palladium, osmium, iridium, or platinum halides, nitrates or acetylacetone compounds and reducing agents such as alcohols, titanium, vanadium, zirconium, tungsten, or molybdenum halides. Alternatively, a system composed of an acetylacetone compound and organic aluminum can be used.

<Ring-Opening (Co) Polymer> In the ring-opening (co) polymer used in the present invention, the repeating structural unit in which the norbornene ring of the phenyl-norbornenes represented by the following general formula 2 is opened is It is 5 to 100 mol% in all repeating structural units.

[0011]

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(In the formula, R ^{1 to} R ⁷ are a hydrogen atom and a carbon number 1
To a polar group such as a hydrocarbon group of 4 to 4, a halogen group, an alkoxy group and a cyano group, or a hydrocarbon group of 1 to 4 carbon atoms substituted with these polar groups. )

<Cyclization Reaction> In the present invention, cyclization means conversion of the repeating structural unit represented by the above general formula 2 into the repeating structural unit represented by the following general formula 3.

[0015]

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(In the formula, R ^{1 to} R ⁷ are hydrogen atoms and carbon atoms 1
To a polar group such as a hydrocarbon group of 4 to 4, a halogen group, an alkoxy group and a cyano group, or a hydrocarbon group of 1 to 4 carbon atoms substituted with these polar groups. )

The method for cyclizing the ring-opening (co) polymer used in the present invention is not particularly limited, and a known method using an acidic compound may be used. The acidic compound is Lewis acid or Bronsted acid. The acidic compound is used in an amount of 0.01 to 1000 parts by weight based on 100 parts by weight of the ring-opening (co) polymer used in the present invention. The cyclization reaction is carried out in a homogeneous system, and the solvent used is a solvent capable of dissolving the ring-opening (co) polymer and is not particularly limited as long as it is an inert solvent for the cyclization reaction.

The cyclization is performed while consuming the double bond in the main chain structure of the polymer so that the residual rate is 0 to 95%. The ring-opened (co) polymer cyclized product has an intrinsic viscosity [η] measured in decalin or toluene at 25 ° C.
It is 0.05 to 30 dl / g. <Hydrogenation Reaction> The method for hydrogenating the cyclized product is not particularly limited, and a known method for hydrogenating a general norbornene ring-opening polymer may be used. For example, a Wilkinson complex, a homogeneous catalyst such as nickel acetylacetonate / triisobutylaluminum, diatomaceous earth, magnesia, alumina,
The cyclized product is contacted with hydrogen gas in the presence of a heterogeneous catalyst in which a catalyst metal such as nickel, palladium or platinum is supported on a carrier such as silica.

In the hydrogenation, hydrogenation is carried out so that the residual rate of double bonds in the polymer main chain structure before cyclization is 10% or less. Generally, the aromatic ring structure in the cyclized structure is also hydrogenated, but depending on the purpose, it may be hydrogenated so that the aromatic ring structure remains. The ring-opened (co) polymer cyclized hydrogenated product has an intrinsic viscosity [η] of 0.05 to 30 dl / g measured in decalin or toluene at 25 ° C. Next, [B] (a) ethylene used in the present invention,
And (b) a cyclic olefin compound which is a monomer of a cyclic olefin copolymer obtained by copolymerizing a cyclic olefin compound, is a compound represented by the following general formula 4,

[0020]

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(In the formula, m is 0 or 1, n is 0 or a positive integer, w is 0 or 1, and R8 to R2
5 and Ra1 and Rb1 are each independently a hydrogen atom, a halogen atom or a hydrocarbon group, and R22 to R25
May be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring may have a double bond, R22 and R23, or R24 and R25; And may form an alkylidene group with a compound represented by the following general formula 5,

[0022]

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(Wherein x and d are 0 or an integer of 1 or more, y and z are 0, 1 or 2, and R26 to
R44 is independently a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or an alkoxy group, and the carbon atom to which R34 and R35 are bonded and R38 are bonded to each other. The carbon atom to which R36 or the carbon atom to which R36 is bonded is directly or the number of carbon atoms is 1
3 to 3 may be bonded via an alkylene group, and when y = z = 0, R40 and R37 or R40 and R44 are bonded to each other to form a monocyclic or polycyclic aromatic ring. May be used) and at least one selected from the group consisting of compounds represented by the following general formula 6.

[0024]

[Chemical 6]

(In the formula, R45 and R46 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1
≦ f ≦ 18) As the monomers represented by the general formulas 4 to 6, specifically, a bicyclo-2-heptene derivative (bicyclohept-
2-ene derivative), tricyclo-3-decene derivative, tricyclo-3-undecene derivative, tetracyclo-3-
Dodecene derivative, pentacyclo-4-pentadecene derivative, pentacyclopentadecadiene derivative, pentacyclo-3-pentadecene derivative, pentacyclo-4-hexadecene derivative, pentacyclo-3-hexadecene derivative, hexacyclo-4-heptadecene derivative, heptacyclo-5-eicosene Derivatives, heptacyclo-4-eicosene derivatives, heptacyclo-5-heneicosene derivatives, octacyclo-5-docosene derivatives, nonacyclo-
5-pentacocene derivative, nonacyclo-6-hexacocene derivative, cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene derivative, 1,4-methano-1,4,4a, 5 , 10,
10a-hexahydroanthracene derivative, carbon number 3 to
20 cycloalkylene derivatives and the like. Among these, bicyclo [2.2.1] -2-heptene derivatives,
Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene derivatives and hexacyclo [6.6.1.1 ^{3, 6.}
1 ^10,13 .0 ^2,7 .0 ^9,14] -4-heptadecene derivative are preferable. Particularly bicyclo [2.2.1] -2-heptene, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene are preferred. These cyclic olefins represented by the general formulas 4 to 6 can be used alone or in combination of two or more kinds. <Polymerization reaction> The catalyst used for the polymerization of the cyclic olefin-based copolymer is (c) (c1) a transition metal compound represented by the following general formula (7).

[0026]

[Chemical 7]

(Wherein M1 is titanium, zirconium, hafnium, vanadium, niobium or tantalum,
R47 and R48 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a carbon atom having 1 to 10 carbon atoms.
Alkoxy group, C 6-10 aryl group, C 6-10 aryloxy group, C 2-10 alkenyl group, C 7-40 arylalkyl group, C 7-40 alkylaryl Group or carbon number 8-40
R49 to R50 each independently represent a mononuclear or polynuclear hydrocarbon group having a cyclopentadienyl skeleton capable of forming a sandwich structure with the central metal M1 and R51 represents ,

[0028]

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= BR52, = AlR52, -Ge-, -Sn
-, -O-, -S-, = SO, = SO2, = NR52, =
CO, = PR52, or = P (O) R52, wherein R52, R53, and R54 are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms,
Fluoroalkyl group having 1 to 10 carbon atoms, fluoroaryl group having 6 to 10 carbon atoms, aryl group having 6 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, alkenyl having 2 to 10 carbon atoms Group, an arylalkyl group having 7 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms or an arylalkenyl group having 8 to 40 carbon atoms, or R52 and R53 or R52 and R54
Each may together with their attached atoms form a ring, and M2 is silicon, germanium, or tin. And (c2) an organoaluminumoxy compound, a compound capable of reacting with a transition metal compound to form an ionic complex, and at least one selected from the group consisting of a combination of at least one of these and an organoaluminum compound. It is a thing. When the transition metal is zirconium, the transition metal compound is specifically isopropylidene (cyclopentadienyl-fluorenyl).
Zirconium dichloride, isopropylidene (methylcyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (isopropylcyclopentadienyl-fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-indenyl)
Examples thereof include zirconium dichloride, isopropylidene (cyclopentadienyl-benzoindenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl-indenyl) zirconium dichloride and the like. Further, as the compound in which the transition metal used in the present invention is titanium, hafnium, vanadium, niobium or tantalum, compounds in which the central metal of the zirconium compound as described above is replaced with each of the above metals can be exemplified. These transition metal compounds may be supported on a carrier. The organoaluminum oxy compound may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy compound. The organoaluminum oxy compound used in the present invention is
It may contain a small amount of an organic compound component of a metal other than aluminum. The organoaluminum oxy compound can also be used by supporting it on a carrier compound. Examples of the compound capable of reacting with a transition metal compound to form an ionic complex include, for example, a compound composed of a cation and an anion having a plurality of groups bound to an element, particularly a cation and an anion having a plurality of groups bound to an element. A coordination complex compound can be preferably used. Further, as a catalyst used for polymerization of the cyclic olefin-based copolymer, a catalyst composed of a vanadium compound soluble in a reaction solvent and an organoaluminum compound can be used. The soluble vanadium compound is represented by the following general formula.

VO (OR) _a X _b or V (OR) _c X _d (wherein R is a hydrocarbon group, and a, b, c and d are 0 ≦ a ≦ 3 and 0 ≦ b ≦ 3, respectively) 2 ≦ a + b ≦ 3, 0 ≦ c
≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4 are satisfied. ) Specific examples of the vanadium compound include VOCl ₃ , VO (OC
_{H 3) Cl 2, VO (} OC 2 H 5) 1.5 Cl 1.5, VOBr 2
And the like. These can be used alone or in combination of two or more. The soluble vanadium compound can also be used as an electron donor adduct obtained by contacting an electron donor as shown below. Such electron donors include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid halides, organic acids or inorganic acid esters, ethers, diethers, acid amides, acid anhydrides. And oxygen-containing electron donors such as alkoxysilanes, and nitrogen-containing electron donors such as ammonias, amines, nitriles, pyridines and isocyanates. The organoaluminum compound is represented by the following general formula.

R ¹ _n AlX _3-n (In the formula, R ¹ is a hydrocarbon group having 1 to 15 carbon atoms, X is a halogen atom or a hydrogen atom, and n is 1 to _3. ) Specific examples of the organoaluminum compound include:
Examples thereof include trialkylaluminums such as trimethylaluminum and triethylaluminum, alkenylaluminums such as isoprenylaluminum, dialkylaluminum halides such as dimethylaluminum chloride, and alkylaluminum sesquihalides such as methylaluminum sesquichloride. When the cyclic olefin-based copolymer is polymerized, the α-olefin having 3 to 20 carbon atoms is added at a molar ratio of α-olefin to ethylene of 0.0.
You may supply in the ratio used as 005-0.2. Specific examples of the α-olefin having 3 to 20 carbon atoms used include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-. Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, styrene,
4-phenyl-1-butene and the like can be mentioned. Among these, propylene, 1-butene, 1-pentene, 1-
Hexene is particularly preferred.

As the polymerization form, any of solution polymerization, bulk polymerization and slurry polymerization can be adopted, and continuous polymerization or batch polymerization can be carried out. Examples of the polymerization solvent used in the above copolymerization include aliphatic hydrocarbons such as hexane, heptane, octane and kerosene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aromatics such as benzene, toluene and xylene. Hydrocarbons can be exemplified. These solvents can be used alone or as a mixture. The polymerization temperature is in the range of -50 to 230 ° C, and the polymerization reaction time is 2 minutes to 5 hours. The pressure during the polymerization reaction is more than 0 and 1000 kg /
The range is cm2. The catalyst may be prepared by separately feeding the transition metal compound and the organoaluminum oxy compound, the compound capable of reacting with the transition metal compound to form an ionic complex, or the organoaluminum compound into the polymerization vessel separately. You may make it contact outside the system of a polymerization vessel. The concentration of the transition metal compound in the polymerization reaction system is preferably 0.00005 to 1.0 mmol / liter, more preferably 0.0001 to 0.3 mmol / liter. The concentration of the compound capable of reacting with the organoaluminum oxy compound and the transition metal compound to form an ionic complex is preferably 1 to 10 ⁴ equivalents of the transition metal compound. Further, the concentration of the organoaluminum compound used together with these is, relative to the aluminum atom of the organoaluminum oxy compound, or to the complex metal atom of the compound capable of reacting with the transition metal compound to form an ionic complex, It is preferable to use 0.01 to 100 equivalents.

In the present invention, the relationship between the liquid supply concentration [b] of the cyclic olefin and the ethylene liquid supply concentration [a] is as follows: 0.30 ≦ [B] / ([A] + [B]) ≦ It is preferably 0.99, and particularly preferably 0.50 ≦ [B] / ([A] + [B]) ≦ 0.98. In the cyclic olefin-based copolymer obtained by the present invention, the repeating unit derived from the ethylene component is preferably present in an amount of usually 5 to 95 mol%, and the cyclic olefin represented by the general formulas 4 to 6 above. The repeating unit derived from the component is usually 95 to 5
It is desirable to be present in an amount in the range of mol%. Further, the repeating unit derived from the α-olefin component having 3 to 20 carbon atoms is preferably in the range of 20 mol% or less. 1
Intrinsic viscosity [η] in decalin at 35 ° C is 0.05 to 1.5
It is preferably in the range of dl / g. The glass transition temperature (Tg) measured by DSC is preferably in the range of 0 to 250 ° C. The iodine value is preferably 1.5 g-iodine / 100 g polymer or less.

Next, the hydrocarbon resin used in the present invention has a polystyrene-reduced weight average molecular weight of 2 × 10 ⁴ or less, preferably 2 × 10 ^{4 to} 100, and is solid at room temperature. . Specific examples include C ₅ resin, C ₉ resin, C ₅ / C ₉ mixed resin, cyclopentadiene resin, vinyl-substituted aromatic compound polymer resin, and olefin / vinyl-substituted aromatic compound Examples thereof include copolymer resins, cyclopentadiene compound / vinyl-substituted aromatic compound copolymer resins, rosin resins, terpene resins, and hydrogenated products of the above resins. Specifically, Escoletz (Tonex Co., Ltd.), Alcon (Arakawa Chemical Industry Co., Ltd.), Imarve (Idemitsu Petrochemical Co., Ltd.), Highletts (Mitsui Petrochemical Co., Ltd.), Petrosine (Mitsui) Petrochemical Co., Ltd.
Company), FTA (Mitsui Petrochemical Co., Ltd.), Quinton (Nippon Zeon Co., Ltd.), Marcarets (Maruzen Petrochemical Co., Ltd.), Coporex (Toho Chemical Industry Co., Ltd.)
Company), Hiresin (Toho Chemical Industry Co., Ltd.), PetroTac (Tosoh Corporation), Petcole (Tosoh Corporation)
Company), neopolymer (Nippon Petrochemical Co., Ltd.), and the like. If the polystyrene-reduced weight average molecular weight of these hydrocarbon resins is too high, a 6-membered ring is formed by the main chain double bond and the side chain benzene ring of the ring-opening (co) polymer of [A] phenyl-norbornenes. A cyclic olefin compound of a cyclic olefin copolymer obtained by copolymerizing a resin and / or [B] (a) ethylene and (b) a cyclic olefin compound obtained by hydrogenating a cyclized product of It is not preferable because the compatibility with and deteriorates the transparency.

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 surface of the resin is bleed. The blending ratio of the hydrocarbon resin is such that the [A] phenyl-norbornene ring-opening (co)
A resin obtained by hydrogenating a cyclized product obtained by forming a 6-membered ring with a double bond of the main chain of a polymer and a benzene ring of a side chain; and [B]
It is usually 0.0 with respect to a total of 100 parts by weight of the cyclic olefin compound of the cyclic olefin copolymer obtained by copolymerizing (a) ethylene and (b) the cyclic olefin compound.
It is 1 to 50 parts by weight, preferably 0.1 to 25 parts by weight. The method for compounding the resin composition of the present invention includes, for example, compounding with a twin-screw extruder, a roll kneader, or the like; Of a cyclized product formed by forming a 6-membered ring with a benzene ring of a chain and / or [B] (a) ethylene and (b) a cyclic olefin obtained by copolymerizing a cyclic olefin compound Examples include a method in which a solution of a hydrocarbon resin is blended with a solution of a cyclic olefin compound of a system copolymer to form pellets.

The resin composition of the present invention includes known antioxidants such as 2,6-di-t-butyl-4-methylphenol and 2,2'-dioxy-3,3'-di-t. -Butyl-5,5'-dimethyldiphenylmethane, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane; UV absorbers such as 2,4-dihydroxybenzophenone, Two
It can be stabilized by adding -hydroxy-4-methoxybenzophenone or the like. Further, additives such as lubricants may be added for the purpose of improving processability. The resin composition of the present invention can be molded into a molded product by using a known molding means such as injection molding, compression molding, extrusion molding or the like. The film can also be produced by a cast molding method.

The surface of the produced molded article is made of an inorganic compound, an organic silicon compound such as a silane coupling agent, an acrylic resin, a vinyl resin, a melanin resin, an epoxy resin, a fluorine resin, a silicone resin, or the like. A hard coat layer can be formed. Examples of the means for forming the hard coat layer include known methods such as a thermosetting method, an ultraviolet curing method, a vacuum deposition method, a sputtering method, and an ion plating method. As a result, the heat resistance, optical characteristics, chemical resistance, abrasion resistance, moisture permeability and the like of the molded product can be improved. The application of the resin composition of the present invention is not limited and can be used in a wide range, for example, lenses such as lenses for general cameras, lenses for video cameras, telescope lenses, spectacle lenses, and lenses for laser beams. , Optical video discs, audio discs, document file discs, optical discs such as memory discs, optical materials such as optical fibers, image transfer sheets and various films, sheets, sealants, and binders of inorganic or organic compounds are particularly suitable. Can be used.

[0038]

The present invention will be described below with reference to examples.
The present invention is not limited to these examples. First, a resin obtained by hydrogenating a cyclized product obtained by forming a 6-membered ring with a main chain double bond and a side chain benzene ring of a [A] phenyl-norbornene ring-opening (co) polymer An example of the synthesis of

Synthesis Example 1 [Ring-Opening Polymerization Reaction] In a glass reaction vessel substituted with nitrogen, 5
-Phenylbicyclo [2,2,1] hept-2-ene 6
0 parts by weight and 300 parts by weight of toluene were charged, and 1 part by weight of 1-hexene was added as a molecular weight modifier. Solution 4
After heating to 0 ° C., 10 parts by weight of a 15 wt% toluene solution of triethylaluminum, 5 parts by weight of triethylamine, and 10 parts by weight of a 20 wt% toluene solution of titanium tetrachloride were added as polymerization catalysts to initiate ring-opening polymerization. . When the reaction was carried out for 1 hour while keeping the temperature of the solution at 40 ° C., 5 parts by weight of methanol was added to stop the reaction. Acetone 5
The reaction solution was poured into a mixed solution of 00 parts by weight and 500 parts by weight of isopropyl alcohol to precipitate the polymer, which was collected by filtration to obtain 50 parts by weight of a ring-opened polymer. [Cyclization reaction] 50 parts by weight of this ring-opening polymer and 45 parts of toluene
Add 0 parts by weight to a new nitrogen-replaced glass reactor,
Warmed to 50 ° C. After adding 5 parts by weight of aluminum chloride with stirring and reacting at a reaction temperature of 50 ° C. for 5 hours,
The reaction solution was put into 1000 parts by weight of isopropyl alcohol, and the precipitated polymer was filtered off to obtain 47 parts by weight of resin. The obtained resin has an intrinsic viscosity of 0.41 dl / g, T
g was 141 ° C., and the residual rate of double bonds in the main chain structure was 79%. [Hydrogenation reaction] 30 parts by weight of this resin was dissolved in 70 parts by weight of toluene, and 0.35 parts by weight of nickel, 0.2 part by weight of nickel oxide and 0 part by volume of pores were contained in an alumina-supported nickel catalyst. 0.8 cm ³ / g, specific surface area 300 m ² /
g) Add 1 part by weight and 2 parts by weight of isopropyl alcohol, 230 ° C. in an autoclave, hydrogen pressure 50 kg / c
The reaction was carried out at m ² for 5 hours. After the reaction was completed, the catalyst was filtered off,
The reaction solution was put into 500 parts by weight of isopropyl alcohol, and the precipitated polymer was filtered off to obtain 28 parts by weight of a colorless resin. The obtained resin has an intrinsic viscosity of 0.41 dl /
The g and Tg were 107 ° C. Hydrogenation rate is practically 10
The residual rate of the double bond in the main chain structure was 0%, and the aromatic ring structure was saturated and did not remain.

Synthesis Example 2 Synthesis Example 1 was repeated except that the reaction temperature of the cyclization reaction was 55 ° C. and the reaction time with aluminum chloride was 12 hours. The obtained resin has an intrinsic viscosity of 0.41 dl / g, Tg
Is 166 ° C., and the residual rate of double bonds in the main chain structure is 3
2%. The resin obtained by further hydrogenation had an intrinsic viscosity of 0.41 dl / g and a Tg of 156 ° C. The hydrogenation rate was substantially 100%, the residual rate of double bonds in the main chain structure was 0%, and the aromatic ring structure was saturated and did not remain. Next, an example of synthesizing the cyclic olefin compound of the cyclic olefin copolymer obtained by copolymerizing [B] (a) ethylene and (b) cyclic olefin compound will be shown.

Synthesis Example 3 [Pre-Activation of Catalyst] 10.0 mg of isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride was weighed in a glass container sufficiently replaced with nitrogen, and methylaluminoxane (hereinafter referred to as MAO). (Abbreviated as)) in toluene solution (4.67 ml) so that aluminum atom becomes 9.25 mmol.
Ultrasonic irradiation was performed at 15 ° C. for 15 minutes. Then this 4
The catalyst solution was diluted with 2.1 ml of cyclohexane. In [pressure batch polymerization] vacuum dried and 1.5 l autoclave which had been purged with nitrogen, tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] at room temperature 3-dodecene (hereinafter T
(Abbreviated as CD) 37.5 g, cyclohexane 170.2 ml, and triisobutylaluminum cyclohexane solution (1.0 mmol / ml) 0.3 ml are added, and subsequently ethylene is stirred at 3 kg / cm 3.
Pressurization up to 2 G and then depressurization were repeated 3 times. After confirming that the atmospheric pressure was reached, 690 ml of propylene was charged into the autoclave. The inside of the system was pressurized with ethylene through an integrating flow meter to 1.5 kg / cm 2 G, and the temperature was started to reach 70 ° C. Then, it was pressurized with ethylene so that the internal pressure became 3 kg / cm 2. After stirring for 15 minutes, 3.03 ml of cyclohexane solution containing isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride and MAO prepared above was added to the system to obtain ethylene,
The TCD copolymerization reaction was initiated. At this time, the catalyst concentration was isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride with respect to the whole system.
005 mmol / l, methylalumoxane 2.
It was 0 mmol / liter. During the polymerization, the internal pressure was maintained at 3 kg / cm 2 by continuously supplying ethylene. After 20 minutes, the polymerization reaction was stopped by adding isopropyl alcohol. The volume of ethylene supplied from the start of pressurization to the end is 10,000 ml at 25 ° C.
Met. That is, the ratio of the supply amount of propylene and the ethylene of the component [d] in this system was 0.0690. After depressurization, the polymer solution was taken out, and the aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water was mixed with the polymerization liquid in a ratio of 1: 1.
The mixture was contacted with a homomixer with strong stirring under strong stirring to transfer the catalyst residue to the aqueous phase. After leaving this contact mixture still, the aqueous phase was separated and removed, and further washed twice with distilled water to purify and separate the polymerization liquid phase. Then, the purified and separated polymerization liquid was contacted with 3 times amount of acetone under strong stirring to precipitate a copolymer, and then a solid portion (copolymer) was collected by filtration and sufficiently washed with acetone. Further, in order to extract unreacted TCD existing in the polymer, this solid part was put into acetone so as to be 40 g / liter, and then extraction operation was performed at 60 ° C. for 2 hours. After the extraction treatment, the solid portion was collected by filtration, and the solid portion was filtered under nitrogen flow to
It was dried at 0 ° C. and 350 mmHg for 12 hours. As described above, the yield of the ethylene / TCD copolymer obtained was 1
7.0 g, [η] is 0.57 dl / g, Tg; 13
The temperature was 0 ° C., the propylene content was 3.1 mol%, and the iodine value was 0.7 g-iodine / 100 g polymer.

Example 1 100 parts by weight of the hydrogenated phenyl-norbornene resin produced in Synthesis Example 1 was mixed with a hydrocarbon resin in the range of 0 to 50 parts by changing the compounding ratio as shown in Table 1. These mixtures were pelletized in a twin-screw extruder at 220-240 ° C. As the hydrocarbon resin, a copolymer resin of cyclopentadiene compound / vinyl-substituted aromatic compound (Imerb manufactured by Idemitsu Petrochemical Co., Ltd.) was used.
This hydrocarbon resin had a molecular weight of 650 and had a softening point of 100 ° C. and was solid at room temperature. 220-
Press molding was performed under the conditions of 240 ° C. to form a transparent plate having a length of 55 mm, a width of 10 mm and a thickness of 0.5 mm. This transparent plate was stretched in an oil bath at Tg + 20 ° C. (stretching ratio: 1.3
Double stretching speed: 1 mm / sec). The physical properties of this transparent plate were measured, and the results are shown in Table 1. The retardation of the transparent plate after stretching was measured by an ellipsometer (Mizojiri Optical Co., Ltd., light source: He-Ne laser).

[0043] * Hydrocarbon resin: Imerb, manufactured by Idemitsu Petrochemical Co., Ltd.

Example 2 100 parts by weight of the hydrogenated phenyl-norbornene-based resin produced in Synthesis Example 1 was used as a hydrocarbon resin, a high-resin resin manufactured by Toho Chemical Industry Co., Ltd. (molecular weight: 850, softening point: 1).
Example 1 except that 25 parts of (solid at room temperature and 00 ° C.) was blended.
When the physical properties were measured in the same manner as in, Tg was 90.
° C, retardation> 10 nm, light transmittance 92%
Met. Example 3 To 100 parts by weight of the hydrogenated phenyl-norbornene-based resin produced in Synthesis Example 1, 25 parts of Escorez resin (molecular weight 420, softening point 105 ° C., solid at room temperature) manufactured by Tonex Co., Ltd. was used as a hydrocarbon resin. Physical properties were measured in the same manner as in Example 1 except that the components were mixed, and Tg was 9
3 ° C., retardation> 10 nm, light transmittance 92
%Met. Example 4 Based on 100 parts by weight of the hydrogenated phenyl-norbornene-based resin produced in Synthesis Example 1, as a hydrocarbon resin, Nippon Oil Chemical Co., Ltd. Nisseki Neopolymer resin (molecular weight 2200,
The physical properties were measured in the same manner as in Example 1 except that 25 parts of a softening point of 145 ° C. and a solid at room temperature) were blended.
Was 100 ° C., the retardation was> 10 nm, and the light transmittance was 92%.

Example 5 100 parts by weight of the hydrogenated phenyl-norbornene-based resin produced in Synthesis Example 1 was used as a hydrocarbon resin, an Alcon resin manufactured by Arakawa Chemical Industry Co., Ltd. (molecular weight: 750, softening point: 125).
Physical properties were measured in the same manner as in Example 1 except that 25 parts of solid (at room temperature and room temperature) was blended. As a result, Tg was 96 ° C., retardation was> 10 nm, and light transmittance was 92%. Example 6 100 parts by weight of the hydrogenated phenyl-norbornene-based resin produced in Synthesis Example 2 was used as a hydrocarbon resin, and Imerb resin manufactured by Idemitsu Petrochemical Co., Ltd. (molecular weight: 650, softening point: 100).
25 parts by weight (solid at room temperature, room temperature). This formulation was pelletized in a twin screw extruder at 250 ° C. Using these pellets, physical properties were measured in the same manner as in Example 1 except that press molding was performed at 250 ° C. Tg was 138 ° C., retardation was> 10 nm, and light transmittance was 92%.

Example 7 Cyclic Olefin Copolymer Resin 10 Produced in Synthesis Example 3
To 0 part by weight, 25 parts of Imerb resin (molecular weight 650, softening point 100 ° C., solid at room temperature) manufactured by Idemitsu Petrochemical Co., Ltd. was blended as a hydrocarbon resin. The formulation was pelletized on a twin screw extruder at 240 ° C. Using these pellets, physical properties were measured in the same manner as in Example 1 except that press molding was performed at 240 ° C. Tg is 115
° C, retardation> 10 nm, light transmittance 92%
Met. Example 8 Cyclic Olefin Copolymer Resin 10 Produced in Synthesis Example 3
Alkane resin (molecular weight 750, softening point 125, manufactured by Arakawa Chemical Industry Co., Ltd., as a hydrocarbon resin, relative to 0 parts by weight.
Physical properties were measured in the same manner as in Example 1 except that 25 parts of solid (at room temperature and room temperature) was added, and Tg was 125 ° C.
The retardation was> 10 nm and the light transmittance was 92%. Example 9 Cyclic Olefin Copolymer Resin 10 Produced in Synthesis Example 3
Physical properties were measured in the same manner as in Example 1 except that 25 parts by weight of Escorez resin (molecular weight 420, softening point 105 ° C., solid at room temperature) manufactured by Tonex Co., Ltd. was blended with 0 part by weight as a hydrocarbon resin. The Tg is 11
6 ° C., retardation> 10 nm, light transmittance 92
%Met.

Example 10 50 parts by weight of the hydrogenated phenyl-norbornene-based resin produced in Synthesis Example 1 and 50 parts by weight of the cyclic olefin-based copolymer resin produced in Synthesis Example 3 were used as a hydrocarbon resin by Arakawa Chemical Industries ( Physical properties were measured in the same manner as in Example 1 except that 25 parts of Alcon resin (Molecular weight: 750, softening point: 125 ° C., solid at room temperature) manufactured by Co., Ltd. was added, and Tg was 128 ° C., retardation was> 10 nm, The light transmittance was 92%.

[Title of Invention] The resin composition of the present invention is excellent in low birefringence, transparency and fluidity.

Claims (1)

[Claims] 1. A hydrogenated cyclized product obtained by forming a 6-membered ring with a double bond of the main chain of a [A] phenyl-norbornene ring-opening (co) polymer and a benzene ring of a side chain. The obtained resin and / or a cyclic olefin copolymer obtained by copolymerizing [B] (a) ethylene and (b) a cyclic olefin compound and [C] a polystyrene-converted weight average molecular weight of 2
A resin composition containing a hydrocarbon resin that is not more than × 10 ⁴ and is solid at room temperature.