JP2008174679A - Resin composition and optical molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which has satisfactorily low birefringent properties and transparency as an optical lens and mechanical properties having no fear of causing a fissure in a sprue, a runner and the like in producing molded articles and an optical molded article prepared by molding the resin composition. <P>SOLUTION: The resin composition comprises a hydrogenated product (A) of an open-ring polymer of a norbornene monomer containing a repeating unit (a) derived from a norbornene monomer having an aromatic ring and a hydrogenated product (B) of an addition copolymer of a norbornene monomer having a repeating unit (b) derived from a norbornene monomer having an aromatic ring and an α-olefin, and the optical molded article is prepared by molding the resin composition. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

 The present invention relates to a resin composition and an optical molded product obtained by molding the resin composition. More specifically, the present invention has sufficient birefringence and transparency as an optical lens and produces a molded product. In particular, the present invention relates to a resin composition having mechanical characteristics that do not cause cracks in sprues, runners, and the like, and an optically molded product formed by molding the resin composition.

Conventionally, norbornene polymers have excellent properties such as transparency, low birefringence, heat resistance, and low water absorption, so they are mainly optical lenses such as pickup lenses and camera lenses, optical films, light guide plates, and light diffusion plates. It is used in the optical field.
2. Description of the Related Art In recent years, optical lenses, particularly pickup lenses, in the optical field have been required to have extremely low birefringence with the recent increase in recording density of optical recording media. In addition, if cracks occur in sprues, runners, etc. in the production of molded products, the production line must be stopped and the broken sprues, runners, etc. must be removed, leading to reduced productivity. There is a need for optical materials that are highly balanced in mechanical properties.
By the way, as the main norbornene polymer used in the optical field, a ring-opening polymer hydrogenated product of norbornene monomer and an addition copolymer of norbornene monomer and α-olefin are known.
Examples of the ring-opening polymer hydrogenated product of norbornene monomer include, for example, Patent Document 1 and Patent Document 2, which describe the opening of tetracyclododecenes and 1,4-methano-1,4,4a, 9a-tetrahydrofluorene. Although a cyclic polymer hydrogenated product has been proposed, although it has excellent mechanical properties, it sometimes fails to satisfy the low birefringence required for recent optical lenses.
In addition, as an addition copolymer of a norbornene monomer and an α-olefin, for example, Patent Document 3 discloses an addition copolymer obtained by copolymerizing an α-olefin having 2 to 20 carbon atoms and a norbornene monomer. Polymers obtained by hydrogenating a polymer and a pre-treatment polymer selected from graft-modified products thereof have been proposed, but these are excellent in low birefringence but molded because of poor mechanical properties. During production, sprue and runner cracks occurred, and productivity was inferior.
On the other hand, in Patent Document 4, addition copolymer (I) of norbornene monomer and α-olefin, ring-opening (co) polymer of norbornene monomer or hydrogenated product (II) thereof, and (I) Or at least one cyclic olefin resin selected from the group consisting of the graft-modified product (III) of (II), or a resin composition comprising the cyclic olefin resin and polyolefin, and the above (I) to (III) There has been proposed a cyclic olefin-based resin composition selected from the group consisting of at least one cyclic olefin-based resin having a chemical structure different from that of the cyclic olefin-based resin. It is described that the composition is excellent in transparency. However, what is specifically disclosed is only a resin composition obtained by blending the norbornene monomer and the addition copolymer (I) of α-olefin with each other. A resin composition obtained by blending an addition copolymer (I) of a monomer and an α-olefin with a ring-opening (co) polymer of a norbornene monomer or a hydrogenated product thereof (II) is inferior in transparency, There have been problems in using the resin composition in optical applications.

Japanese Patent Publication No. 2-9619 WO96 / 10596 Publication JP 2002-105131 A JP 2001-26693 A

  The present invention has been made in view of such a state of the art, and has a sufficiently low birefringence and transparency as an optical lens, and is suitable for sprues, runners and the like when producing molded products. It is an object of the present invention to provide a resin composition having mechanical properties that do not cause cracks, and an optical molded product formed by molding the resin composition.

  As a result of diligent research to solve the above problems, the present inventors have found that a ring-opening polymer hydrogenated product of a norbornene monomer having a specific structure and an addition copolymer of a norbornene monomer having a specific structure and an α-olefin. A resin composition containing a polymer hydrogenated product was found to be excellent in low birefringence, transparency, and mechanical properties, and based on this finding, the present invention was completed.

Thus, according to the present invention, a ring-opening polymer hydrogenated product (A) of a norbornene monomer containing a repeating unit (a) derived from a norbornene monomer having an aromatic ring, and a norbornene monomer having an aromatic ring There is provided a resin composition comprising a norbornene monomer containing the derived repeating unit (b) and an α-olefin addition copolymer hydrogenated product (B).
Moreover, according to this invention, the molded article for optics formed by shape | molding the said resin composition is provided.

  Since the resin composition of the present invention is excellent in low birefringence, mechanical properties, and transparency, it can be suitably used for optical molded products and cracks in sprues, runners, etc. when producing molded products. Therefore, a molded product can be produced with high productivity.

  The resin composition of the present invention comprises a norbornene monomer ring-opening polymer hydrogenated product (A) containing a repeating unit (a) derived from a norbornene monomer having an aromatic ring, and a norbornene monomer having an aromatic ring And a norbornene monomer containing a repeating unit (b) derived from a body and an addition copolymer hydrogenated product (B) of an α-olefin.

  Here, the ring-opening polymer hydrogenated product (A) of a norbornene monomer containing a repeating unit (a) derived from a norbornene monomer having an aromatic ring constituting the resin composition of the present invention and an aromatic ring The norbornene monomer containing the repeating unit (b) derived from the norbornene monomer and the α-olefin addition copolymer hydrogenated product (B) will be described.

(Ring-opening polymer hydrogenated product of norbornene monomer containing repeating unit (a) derived from norbornene monomer having aromatic ring (A))
The norbornene monomer hydride (A) of the norbornene monomer used in the present invention (hereinafter sometimes simply referred to as “ring-opened polymer hydride (A)”) is a norbornene monomer having an aromatic ring. The derived repeating unit (a) is essential. The ring-opening polymer hydrogenated product (A) is obtained by hydrogenating a ring-opening polymer obtained by ring-opening polymerization of a norbornene monomer containing a norbornene monomer having an aromatic ring. . When a norbornene monomer containing a norbornene monomer having an aromatic ring is subjected to ring-opening polymerization, the norbornene ring is opened to form a ring-opened polymer having a carbon-carbon double bond in the main chain and an aromatic ring in the side chain. can get. By the hydrogenation reaction, the carbon-carbon double bond of the main chain of the ring-opening polymer and the carbon-carbon double bond of the aromatic ring of the side chain are hydrogenated. When a norbornene monomer (for example, dicyclopentadiene) having a carbon-carbon double bond in a substituent or ring is used as the norbornene monomer, the main-chain carbon-carbon double bond, and the side chain During the hydrogenation of the carbon-carbon double bonds of the aromatic ring, these carbon-carbon double bonds are also hydrogenated.
Here, the repeating unit derived from a norbornene monomer having an aromatic ring (a) is a repeating unit derived from a norbornene monomer having an aromatic ring obtained by ring-opening polymerization of a norbornene monomer having an aromatic ring. In which the carbon-carbon double bond of the main chain and the carbon-carbon double bond of the aromatic ring of the side chain are hydrogenated, and when the hydrogenation rate is less than 100%, It includes a structure in which a carbon-carbon double bond and a carbon-carbon double bond derived from an aromatic ring remain in an unreacted state.

  The hydrogenation rate is usually 80% or more, preferably 90% or more, more preferably 95% or more, and still more preferably 99% or more of all carbon-carbon double bonds in the ring-opening polymer. Within this range, a resin composition excellent in low birefringence and transparency, and also excellent in heat resistance, light resistance, weather resistance and the like can be obtained.

  As the norbornene monomer having an aromatic ring used in the present invention, typically, a compound represented by the following formula (I) can be used.

式（Ｉ）中、各記号の意味は、次の通りである。
ｍ：０、１または２である。
ｈ：０、１または２である。
ｊ：０、１または２である。
ｋ：０、１または２である。
Ｒ^１〜Ｒ^１１：それぞれ独立に、水素原子、炭化水素基、及びハロゲン原子、アルコキシ基、水酸基、エステル基（例、アルキルエステル基）、シアノ基、アミド基、イミド基、シリル基などの極性基よりなる群より選ばれる原子または基、並びにこれらの極性基が置換した炭化水素基を表す。
Ｒ^１２〜Ｒ^２０：それぞれ独立に、水素原子、炭化水素基、及びハロゲン原子、アルコキシ基、水酸基、エステル基（例、アルキルエステル基）、シアノ基、アミド基、イミド基、シリル基などの極性基よりなる群より選ばれる原子または基、並びにこれらの極性基が置換した炭化水素基を表す。

In formula (I), the meaning of each symbol is as follows.
m: 0, 1 or 2.
h: 0, 1 or 2.
j: 0, 1 or 2.
k: 0, 1 or 2.
R ^{1 to} R ¹¹ : Independently polar such as hydrogen atom, hydrocarbon group, halogen atom, alkoxy group, hydroxyl group, ester group (eg, alkyl ester group), cyano group, amide group, imide group, silyl group An atom or group selected from the group consisting of groups, and a hydrocarbon group substituted with these polar groups are represented.
R ^{12 to} R ²⁰ : each independently a polarity of a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, a hydroxyl group, an ester group (eg, an alkyl ester group), a cyano group, an amide group, an imide group, a silyl group An atom or group selected from the group consisting of groups, and a hydrocarbon group substituted with these polar groups are represented.

In the formula (I), the carbon atom to which R ¹⁰ and R ¹¹ are bonded and the carbon atom to which R ¹⁴ is bonded or the carbon atom to which R ¹² is bonded are directly or from 1 to 3 carbon atoms. It may be bonded via an alkylene group. When j = k = 0, R ¹⁶ and R ¹³ or R ¹⁶ and R ²⁰ may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 2 carbon atoms. 6 alkenyl groups, 2-20 carbon atoms, preferably 2-10, more preferably 2-6 alkynyl groups, 2-20 carbon atoms, preferably 2-10 carbon atoms, more preferably 2-6 carbon atoms. An alkylidene group, a cycloalkyl group having 3 to 15 carbon atoms, preferably 3 to 8, more preferably 5 to 6 carbon atoms, and an aromatic group having 6 to 20 carbon atoms, preferably 6 to 16 carbon atoms, more preferably 6 to 10 carbon atoms. A hydrocarbon group etc. can be mentioned. Examples of the hydrocarbon group substituted with a polar group include halogenated alkyl groups having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms.

Such norbornene monomers having an aromatic ring include those having an aromatic ring bonded as a substituent to the alicyclic ring and those having an aromatic ring condensed as a substituent on the alicyclic ring. Among these, the latter can be preferably used because of its superior low birefringence.
Examples of those having an aromatic ring bonded to the alicyclic ring as a substituent include 5-phenyl-bicyclo [2.2.1] hept-2-ene and 5-o-tolyl-bicyclo [2.2.1]. Hept-2-ene, 5-m-tolyl-bicyclo [2.2.1] hept-2-ene, 5-p-tolyl-bicyclo [2.2.1] hept-2-ene, 5-o- Ethylphenyl-bicyclo [2.2.1] hept-2-ene, 5-m-ethylphenyl-bicyclo [2.2.1] hept-2-ene, 5-p-ethylphenyl-bicyclo [2.2 .1] Hept-2-ene, 5-p-isopropylphenyl-bicyclo [2.2.1] hept-2-ene, 8-phenyltetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] dodec-3-ene, 5- (naphthalen-1-yl) bicyclo [2.2.1] hept-2-ene, and the like.

Examples of the condensed alicyclic aromatic ring as the substituent include 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-8-methyl-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-8-chloro-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-8-bromo-1,4,4a, 9a-tetrahydrofluorene, 1,4 -Methano-1,4,4a, 9a-tetrahydrodibenzofuran, 1,4-methano-1,4,4a, 9a-tetrahydrodibenzothiazine, 1,4-methano-1,4,4a, 9a-tetrahydrocarbazole, 1,4-methano-9-phenyl-1,4,4a, 9a-tetrahydrocarbazole, 7,10-methano-6b, 7,10,10a-tetrahydrofluorane 7,10-methano-6b, 7,10,10a-a compound obtained by adding cyclopentadiene to tetrahydrofluorane, a compound obtained by adding cyclopentadiene to acanthrylene, a compound obtained by adding cyclopentadiene to acephenanthrylene, 11,12-benzo-pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] -4-pentadecene, 11,12-benzo - pentacyclo [6.6.1.1 ^{3, 6.} 0 ^2,7 . 0 ^9,14] -4-hexadecene, 14,15-benzo - heptacyclo [8.7.0.1 ^2,9. 1 ^4,7 . 1 ^{11, 17} . 0 ^3,8 . 0 ^12,16 ] -5-eicosane, 5,6-benzo-bicyclo [2.2.1] hept-2-ene and the like. Among these, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene is particularly preferable because of its superior low birefringence.

  In addition, norbornene monomers other than norbornene monomers having an aromatic ring that can be used in combination with norbornene monomers having an aromatic ring (hereinafter sometimes referred to as “other norbornene monomers”). For example, known monomers disclosed in JP-A-2-227424, JP-A-2-276842, JP-A-8-72210 and the like can be used. The other norbornene monomer is typically a compound represented by the following formula (II).

式（ＩＩ）中、各記号の意味は、次のとおりである。
ｎ：０または１である。
ｓ：０または１である。
ｐ：０または１〜４の整数である。
ｑ：０または１である。
ｒ：０または１である。
Ｒ_１〜Ｒ_２０：それぞれ独立に、水素原子、炭化水素基、及びハロゲン原子、水酸基、エステル基、アルコキシ基、シアノ基、アミド基、イミド基、シリル基等の極性基よりなる群より選ばれる原子または基、並びにこれらの極性基が置換した炭化水素基を表す。
Ｒ_a〜Ｒ_d：それぞれ独立に、水素原子、炭化水素基、及びハロゲン原子、水酸基、エステル基、アルコキシ基、シアノ基、アミド基、イミド基、シリル基等の極性基よりなる群より選ばれる原子または基、並びにこれらの極性基が置換した炭化水素基を表す。

In formula (II), the meaning of each symbol is as follows.
n: 0 or 1.
s: 0 or 1.
p: 0 or an integer of 1 to 4.
q: 0 or 1.
r: 0 or 1
R _{1 to} R ₂₀ : each independently selected from the group consisting of hydrogen atoms, hydrocarbon groups, and polar groups such as halogen atoms, hydroxyl groups, ester groups, alkoxy groups, cyano groups, amide groups, imide groups, silyl groups, and the like. An atom or group and a hydrocarbon group substituted by these polar groups are represented.
R _{a to} R _d are each independently selected from the group consisting of a hydrogen atom, a hydrocarbon group, and a polar group such as a halogen atom, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an amide group, an imide group, and a silyl group. An atom or group and a hydrocarbon group substituted by these polar groups are represented.

In the formula (II), R _{15 to} R ₁₈ may be bonded to each other to form an unsaturated bond, a monocycle or a polycycle, and the monocycle or polycycle has a double bond It may be. R ₁₅ and R ₁₆ , or R ₁₇ and R ₁₈ may form an alkylidene group. When q or r is 0, each bond joins to form a 5-membered ring.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 2 carbon atoms. 6 alkenyl groups, 2-20 carbon atoms, preferably 2-10, more preferably 2-6 alkynyl groups, 3-15 carbon atoms, preferably 3-8 carbon atoms, more preferably 5-6 cyclohexanes. Examples thereof include an alkyl group and an aromatic hydrocarbon group having 6 to 20, preferably 6 to 16, more preferably 6 to 10 carbon atoms. Examples of the alkylidene group include a lower alkylidene group having 1 to 6 carbon atoms such as a methylidene group, an ethylidene group, a propylidene group, and a butylidene group. Examples of the hydrocarbon group substituted with a polar group include halogenated alkyl groups having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms.

  Specific examples of other norbornene monomers include, for example, norbornene, its alkyl, alkylidene, and halogens, hydroxyl groups, ester groups, alkoxy groups, cyano groups, amide groups, imide groups, silyl groups of these substituted or unsubstituted norbornene. And polar group substitution products such as groups. More specifically, for example, 2-norbornene [ie, bicyclo [2.2.1] hept-2-ene], 5-methyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-ethyl 2-norbornene, 5-ethylidene-2-norbornene, 5-methoxycarbonyl-2-norbornene, 5-cyano-2-norbornene, 5-methyl-5-methoxycarbonyl-2-norbornene, 5-hexyl-2-norbornene 2-tetracyclododecene, 5-ethylidene-2-tetracyclododecene, 5-methoxycarbonyl-2-tetracyclododecene, and the like.

Other specific examples include monomers obtained by adding one or more cyclopentadiene to norbornene, derivatives and substitutes similar to those described above, and more specifically, for example, 1,4: 5,8-dimethano- 1,2,3,4,4a, 5,8,8a-octahydro-2,3-cyclopentadienonaphthalene, 6-methyl-1,4: 5,8-dimethano-1,4,4a, 5 6,7,8,8a-octahydronaphthalene, 1,4: 5,10: 6,9-trimethano-1,2,3,4,4a, 5,5a, 6,9,9a, 10,10a- Dodecahydro-2,3-cyclopentadienoanthracene and the like; a monomer of a polycyclic structure which is a multimer of cyclopentadiene, its derivatives and substitutes similar to the above, more specifically, dicyclopentadiene, 2, 3-dihydrodicyclopentadi Adducts of cyclopentadiene and tetrahydroindene, etc., derivatives and substitutes similar to those mentioned above, more specifically 1,4-methano-1,4,4a, 4b, 5,8,8a, 9a-octahydrofluorene, 5,8-methano-1,2,3,4,4a, 5,8,8a-octahydro-2,3-cyclopentadienonaphthalene and the like.

The ratio of the norbornene monomer having an aromatic ring is usually 10 mol% or more, preferably 30 mol% or more, more preferably 50 mol% or more, based on all monomers used.
Further, if desired, a norbornene monomer and another monomer capable of ring-opening copolymerization can be used in combination. Examples of other monomers include monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and substituted derivatives thereof; cyclic dienes such as cyclohexadiene and cycloheptadiene and substituted derivatives thereof; and the like. The amount of other monomers used is usually 5 mol% or less based on the total norbornene monomer.

  The ring-opening polymer of the norbornene monomer can be obtained by a known polymerization method. As the ring-opening polymerization catalyst, a catalyst comprising a metal halide, nitrate or acetylacetone compound selected from ruthenium, rhodium, palladium, osmium, iridium and platinum and a reducing agent; or titanium, vanadium, zirconium, tungsten And a metal halide or acetylacetone compound selected from molybdenum and an organoaluminum compound can be used.

  A third component can be added to the catalyst system to enhance polymerization activity and ring-opening polymerization selectivity. Specific examples include molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound, sulfur-containing compound, halogen-containing compound, molecular iodine, other Lewis An acid etc. are mentioned. As the nitrogen-containing compound, an aliphatic or aromatic tertiary amine is preferable, and specific examples include triethylamine, dimethylaniline, tri-n-butylamine, pyridine, α-picoline and the like.

  Ring-opening polymerization can be carried out without using a solvent, but can also be carried out in an inert organic solvent. Examples of the solvent include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as n-pentane, hexane and heptane, alicyclic hydrocarbons such as cyclohexane, styrene dichloride, dichloroethane, dichloroethylene, And halogenated hydrocarbons such as tetrachloroethane, chlorobenzene, dichlorobenzene, and trichlorobenzene. The polymerization temperature is usually −50 ° C. to 100 ° C., preferably 0 ° C. to 80 ° C., more preferably 20 ° C. to 60 ° C., and the polymerization pressure is usually 0 to 5 MPa, preferably 0 to 1 MPa.

  The ring-opened polymer hydrogenated product (A) can be obtained by a method in which the obtained ring-opened polymer is hydrogenated with hydrogen in the presence of a hydrogenation catalyst according to a conventional method. As the hydrogenation catalyst, any one of a homogeneous catalyst and a heterogeneous catalyst can be used as long as it is generally used for hydrogenation of olefin compounds. Considering the removal of residual metals in the resulting polymer, a heterogeneous catalyst is preferable.

  Among the hydrogenation catalysts, homogeneous catalysts include, for example, cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyllithium, tetrabutoxytitanate / dimethyl. Catalyst system comprising a combination of transition metal compound such as magnesium and alkali metal compound; noble metal complex such as dichlorobis (triphenylphosphine) palladium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, chlorotris (triphenylphosphine) rhodium Catalyst; and the like.

  Among the hydrogenation catalysts, examples of the heterogeneous catalyst include nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina, nickel, palladium, Examples thereof include platinum, rhodium, ruthenium, or a solid catalyst system in which these metals are supported on a support such as carbon, silica, diatomaceous earth, alumina, and titanium oxide.

  The amount of the hydrogenation catalyst used is usually in the range of 0.05 to 10 parts by weight with respect to 100 parts by weight of the ring-opening polymer of the norbornene monomer.

  The hydrogenation reaction is usually carried out in an inert organic solvent. The organic solvent is preferably a hydrocarbon-based solvent and more preferably a cyclic hydrocarbon-based solvent because of the excellent solubility of the resulting hydrogenated product. Examples of such hydrocarbon solvents include aromatic hydrocarbons such as benzene and toluene; aliphatic hydrocarbons such as n-pentane and hexane; alicyclic hydrocarbons such as cyclohexane and decalin; tetrahydrofuran, ethylene glycol dimethyl ether, and the like. Ethers; and the like, and a mixture of two or more of these may be used. Usually, it may be the same as the polymerization reaction solvent, and the hydrogenation catalyst may be added to the polymerization reaction solution as it is and reacted. The reaction temperature is usually 0 to 300 ° C., preferably 50 to 250 ° C., more preferably 100 to 230 ° C., and the hydrogen pressure is usually 0.1 to 20 MPa, preferably 1 to 10 MPa, more preferably 2-5 MPa.

  After completion of the hydrogenation reaction, the hydrogenation catalyst and the like are filtered off from the reaction solution, and by removing volatile components such as a solvent from the polymer solution after the filtration, the desired norbornene monomer ring-opening polymer A hydrogenated product can be obtained. As a method for removing volatile components such as a solvent, a known method such as a coagulation method or a direct drying method can be employed.

  The coagulation method is a method in which a polymer is precipitated by mixing a polymer solution with a poor solvent for the polymer. Examples of the poor solvent to be used include polar solvents such as alcohols such as ethyl alcohol, n-propyl alcohol and isopropyl alcohol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and butyl acetate; The particulate component obtained by coagulation can be dried, for example, by heating in vacuum, nitrogen or air, and dried, or, if necessary, extruded from a melt extruder into pellets. it can.

  The direct drying method is a method in which the polymer solution is heated under reduced pressure to remove the solvent. This method can be carried out using a known apparatus such as a centrifugal thin film continuous evaporation dryer, a scratched heat exchange type continuous reactor type dryer, a high viscosity reactor device or the like. The degree of vacuum and temperature are appropriately selected depending on the device and are not limited.

  The ratio of the repeating unit (a) derived from the norbornene monomer having an aromatic ring in the ring-opening polymer hydrogenated product (A) obtained as described above is usually based on the repeating units of all monomers, It is 10 mol% or more, preferably 30 mol% or more, more preferably 50 mol% or more, and further preferably 80 mol% or more. When it is in this range, the resin composition of the present invention is excellent in low birefringence and mechanical properties and is suitable.

  The weight average molecular weight (Mw) of the ring-opened polymer hydrogenated product (A) is standard polystyrene equivalent (cyclohexane is determined by gel permeation chromatography (GPC) using tetrahydrofuran (cyclohexane when the polymer is not dissolved) as an eluent. When used as an eluent, it is usually 10,000 to 200,000, preferably 20,000 to 100,000, more preferably 30,000 to 50,000 in terms of standard isoprene. When it is in this range, the resin composition of the present invention is excellent in low birefringence and mechanical properties and is suitable.

  The molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the ring-opening polymer hydrogenated product (A) is usually 1.0 to 5.0, Preferably it is 1.5-4.0, More preferably, it is 2.0-3.5. When it is in this range, the resin composition of the present invention is excellent in low birefringence and mechanical properties and is suitable.

  The glass transition temperature of the ring-opened polymer hydrogenated product (A) is usually 100 to 200 ° C, preferably 120 to 180 ° C, more preferably 130 to 170 ° C. Within this range, the resin composition of the present invention is excellent in heat resistance and is suitable.

  Various compounding agents generally used for synthetic resins may be added to the ring-opening polymer hydrogenated product (A) as long as the object of the present invention is not impaired. Examples of such compounding agents include antioxidants, rubbery polymers, ultraviolet absorbers, antistatic agents, slip agents, antifogging agents, dyes, pigments, colorants, natural oils, synthetic oils, plasticizers, Examples thereof include organic or inorganic fillers.

(Addition copolymer hydrogenated product of norbornene monomer and α-olefin containing repeating unit (b) derived from norbornene monomer having aromatic ring (B))
The norbornene monomer and α-olefin addition copolymer hydrogenated product (B) used in the present invention (hereinafter sometimes simply referred to as “addition copolymer hydrogenated product (B)”) is an aromatic ring. The recurring unit (b) derived from a norbornene monomer having an essential component is contained. The addition copolymer hydrogenated product (B) is obtained by hydrogenating an addition copolymer obtained by addition copolymerization of a norbornene monomer containing an aromatic ring-containing norbornene monomer and an α-olefin. It is what Addition copolymerization of a norbornene monomer containing a norbornene monomer having an aromatic ring and an α-olefin gives an addition copolymer having an aromatic ring. By the hydrogenation reaction, the carbon-carbon double bond of the aromatic ring in the addition copolymer is hydrogenated. When a norbornene monomer having a substituent or a carbon-carbon double bond in the ring (for example, dicyclopentadiene) is used as the norbornene monomer, or a carbon-carbon double as a substituent for an α-olefin. When an α-olefin having a bond is used, these carbon-carbon double bonds are also hydrogenated when the aromatic carbon-carbon double bonds are hydrogenated.
Here, the repeating unit (b) derived from a norbornene monomer having an aromatic ring is a norbornene unit having an aromatic ring obtained by addition polymerization of a norbornene monomer containing a norbornene monomer having an aromatic ring. This refers to a repeating unit obtained by hydrogenating a carbon-carbon double bond of an aromatic ring of a repeating unit derived from a monomer. When the hydrogenation rate is less than 100%, a carbon-carbon double bond derived from an aromatic ring is not yet present. Also includes structures that remain in the reaction state.

  The hydrogenation rate is usually 80% or more, preferably 90% or more, more preferably 95% or more, and further preferably 99% or more of all carbon-carbon double bonds in the addition copolymer. Within this range, a resin composition excellent in low birefringence and transparency, and excellent in heat resistance, light resistance, weather resistance and the like can be obtained.

As the norbornene monomer having an aromatic ring and other norbornene monomers, those similar to those that can be used in the ring-opening polymer hydrogenated product (A) can be used. Among these, from the viewpoint of excellent low birefringence, those in which an aromatic ring is condensed as a substituent on an alicyclic ring are preferable, and 1,4-methano-1,4,4a, 9a-tetrahydrofluorene can be more preferably used.
The ratio of the norbornene monomer having an aromatic ring is usually 10 mol% or more, preferably 30 mol% or more, more preferably 50 mol% or more, and still more preferably 80 mol with respect to the total norbornene monomer used. % Or more.

  The α-olefin may be linear or branched and has 2 to 2 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-eicosene. 20 linear α-olefins such as 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 3-ethyl-1-hexene, etc. Examples thereof include branched α-olefins having 4 to 20 carbon atoms. Among these, linear α-olefins having 2 to 4 carbon atoms are preferable, and ethylene is particularly preferable. Such linear or branched α-olefins can be used singly or in combination of two or more.

  An addition copolymer of norbornene monomer and α-olefin is soluble in an inert organic solvent using norbornene monomer and α-olefin, for example, as described in JP-A No. 05-310845. By copolymerizing in the presence of a catalyst system formed from a vanadium compound and an organoaluminum compound, or a catalyst system formed from a metallocene compound of a transition metal selected from Group IVB of the periodic table and an organoaluminum oxy compound Can be manufactured.

As an inert organic solvent, what can be used for the synthesis | combination of a ring-opening polymer hydrogenated substance (A) can be used.
The polymerization temperature is usually −50 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., more preferably 20 ° C. to 70 ° C., and the pressure is usually 0 to 5 MPa, preferably 0 to 1 MPa. Done in
The reaction time is usually 5 minutes to 5 hours, preferably 10 minutes to 1 hour, although it varies depending on the type of monomer used, catalyst concentration, polymerization temperature and the like.

  The method of hydrogenating the addition copolymer of norbornene monomer and α-olefin follows the above-described method of hydrogenating the ring-opening polymer of norbornene monomer.

  The method for recovering the addition copolymer hydrogenated product (B) follows the method for recovering the ring-opening polymer hydrogenated product (A).

The copolymer composition of the addition copolymer hydrogenated product (B) obtained as described above has a molar ratio of repeating units derived from all norbornene monomers to repeating units derived from α-olefin (total amount of norbornene units). Body-derived repeating unit / α-olefin-derived repeating unit), usually 10/90 to 90/10, preferably 20/80 to 80/20, more preferably 30/70 to 70/30, and even more preferably. 40/60 to 60/40.
The ratio of the repeating unit (b) derived from the norbornene monomer having an aromatic ring in the repeating units derived from all norbornene monomers is usually 10 mol% or more, preferably based on the repeating units of all norbornene monomers. Is 30 mol% or more, more preferably 50 mol% or more, still more preferably 80 mol% or more. When it is in this range, the resin composition of the present invention is excellent in low birefringence and mechanical properties and is suitable.

  The weight average molecular weight (Mw) of the addition copolymer hydrogenated product (B) is standard polystyrene equivalent (cyclohexane is determined by gel permeation chromatography (GPC) using tetrahydrofuran (cyclohexane when the polymer is not dissolved) as an eluent. When used as an eluent, it is usually 30,000 to 200,000, preferably 40,000 to 150,000, more preferably 50,000 to 100,000 in terms of standard isoprene. When it is in this range, the resin composition of the present invention is excellent in low birefringence and mechanical properties and is suitable.

  The molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the addition copolymer hydrogenated product (B) is usually 1.0 to 5.0, Preferably it is 1.5-4.0, More preferably, it is 1.5-3.5. When it is in this range, the resin composition of the present invention is excellent in low birefringence and mechanical properties and is suitable.

  The glass transition temperature of the addition copolymer hydrogenated product (B) is usually 100 to 300 ° C, preferably 120 to 200 ° C, and more preferably 130 to 180 ° C. Within this range, the resin composition of the present invention is excellent in heat resistance and is suitable.

  Various compounding agents that can be used for the ring-opening polymer hydrogenated product (A) may be added to the addition copolymer hydrogenated product (B) within a range not impairing the object of the present invention.

(Resin composition)
The ratio of the ring-opening polymer hydrogenated product (A) and the addition copolymer hydrogenated product (B) in the resin composition of the present invention is the same as that of the ring-opening polymer hydrogenated product (A) and the addition copolymerization weight. The weight ratio ((A) / (B)) with the combined hydrogenated product (B) is usually 10/90 to 90/10, preferably 20/80 to 80/20, more preferably 30/70 to 70. / 30, more preferably 40/60 to 60/40. Within this range, the resin composition of the present invention is preferable because low birefringence and mechanical properties are highly balanced and excellent in transparency.

  The method for producing the resin composition of the present invention is not particularly limited, and a known mixing method can be employed. For example, the ring-opening polymer hydrogenated product (A) pellets and the addition copolymer hydrogenated product (B) A method of melt-kneading the pellets with a Henschel mixer, V-blender, ribbon blender, tumbler blender, etc., and further melt-kneading with a single screw extruder, twin screw extruder, kneader, roll, etc., or ring-opening polymer hydrogenated product (A) And a method of removing a volatile component such as a solvent by a known method after mixing the resin solution of the above and the resin solution of the addition copolymer hydrogenated product (B).

  Various compounding agents that can be used for the ring-opening polymer hydrogenated product (A) may be added to the resin composition of the present invention within a range that does not impair the object of the present invention.

  The method for molding the resin composition of the present invention is not particularly limited, and is appropriately selected depending on the application, the shape of the molded product, and the like. For example, the molded product is molded using an injection molding method, a compression molding method, an extrusion molding method, or the like. can do.

  The glass transition temperature of the resin composition of this invention is 100-250 degreeC normally, Preferably it is 120-200 degreeC, More preferably, it is 130-180 degreeC. In the resin composition of the present invention, since the ring-opening polymer hydrogenated product (A) and the addition copolymer hydrogenated product (B) are usually compatible, one point of glass transition temperature is observed. . Within this range, the resin composition of the present invention is excellent in heat resistance.

 The resin composition of the present invention is excellent in transparency. The excellent transparency of the resin composition of the present invention can be evaluated, for example, by measuring the total light transmittance of a plate-shaped molded product having a thickness of 3 mm obtained from the resin composition. The transmittance is usually 80% or more, preferably 85% or more, more preferably 90% or more. Within this range, the resin composition of the present invention is excellent in transparency and can be suitably used for optical applications.

 The resin composition of the present invention is excellent in low birefringence. The resin composition of the present invention is excellent in low birefringence because, for example, a central portion of an injection molded product having a thickness of 3 mm, a length of 65 mm, and a width of 65 mm is formed by a birefringence meter (manufactured by Oji Scientific Instruments: KOBRA-CCD / X ) To measure the retardation value at a measurement wavelength of 650 nm, and the birefringence is usually 30 nm or less, more preferably 25 nm or less. Within this range, the resin composition of the present invention is excellent in low birefringence and can be suitably used for optical applications.

 The resin composition of the present invention is excellent in bending strength. The resin composition of the present invention has excellent bending strength, for example, based on ISO 178 using an injection molded product having a thickness of 3 mm, a length of 80 mm, and a width of 10 mm and a thickness of 4 mm, an autograph (AGS-10 kND, Shimadzu Corporation). The bending strength is usually 50 MPa or more, preferably 60 MPa or more. Within this range, the resin composition of the present invention is excellent in mechanical properties. For example, when the resin composition is molded, there is no possibility that sprues, runners and the like are cracked, and the molded product is excellent in productivity.

(Use)
The use of the molded product obtained by molding the resin composition of the present invention is not particularly limited, but it is used in various applications such as the optical field, food field, medical field, consumer field, automobile field, and electric / electronic field. be able to. In particular, since the resin composition of the present invention is excellent in low birefringence, transparency and mechanical properties, it is suitably used for optical molded articles in the optical field. Specifically, optical lenses such as pickup lenses, camera lenses, and laser beam fθ lenses; optical video disks, audio disks, document file disks, memory disks, and other optical disks; optical films such as retardation films; Optical semiconductor sealing materials such as raptors, photocouplers and LED lamps, IC memory sealing materials such as IC cards; retardation plates for liquid crystal display devices, light diffusion plates, light guide plates, polarizing plate protective films, condensing sheets Among them, among these, it is particularly suitable for an optical lens.

EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated more concretely, it is not limited only to these Examples. In the following examples and comparative examples, parts and% are by weight unless otherwise specified. In the following Examples and Comparative Examples, various physical properties are measured as follows.
(1) Hydrogenation rate and composition ratio The hydrogenation rate of the carbon-carbon double bond of the main chain and the carbon-carbon double bond of the aromatic ring, and the composition ratio of the polymer were ¹ H-NMR (in deuterated chloroform solvent). , TMS standard).
(2) Glass transition temperature The glass transition temperature of the polymer was measured with a differential scanning calorimeter (DSC 6220, manufactured by SII Nanotechnology) at a temperature increase rate of 10 ° C / min based on JIS K7121.
(3) Molecular Weight The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer are gel permeation chromatography (GPC) using tetrahydrofuran at 40 ° C. as an eluent when the polymer is soluble in tetrahydrofuran. When the polymer is insoluble in tetrahydrofuran and soluble in cyclohexane, it was measured as a standard isoprene conversion value by gel permeation chromatography (GPC) using cyclohexane as an eluent at 40 ° C. .
(4) Total light transmittance The total light transmittance is an turbidimeter (NDH-2000, manufactured by Nippon Denshoku Industries Co., Ltd.) based on JIS K7105, using an injection molded product having a thickness of 3 mm, a length of 65 mm, and a width of 65 mm. ).
(5) Bending strength The bending strength was measured by an autograph (AGS-10 kND, manufactured by Shimadzu Corporation) based on ISO 178 using an injection molded product having a thickness of 4 mm, a length of 80 mm, and a width of 10 mm.
(6) Birefringence Birefringence is measured at a measurement wavelength of 650 nm using a birefringence meter (manufactured by Oji Scientific Instruments: KOBRA-CCD / X) at the center of an injection molded product having a thickness of 3 mm, a length of 65 mm, and a width of 65 mm. Comparison was made according to the retardation value.

[Production Example 1]
In an autoclave equipped with a stirrer substituted with nitrogen, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene (hereinafter sometimes abbreviated as “MTF”) 400 parts by weight, cyclohexane 600 parts by weight, toluene 300 parts, -Add 1.55 parts by weight of hexene. After the solution was heated to 45 ° C., 3.7 parts by weight of a 15% toluene solution of triisobutylaluminum as a ring-opening polymerization catalyst, 0.20 parts by weight of isobutyl alcohol, 0.86 parts by weight of diisopropyl ether, and tungsten hexachloride 56.3 parts by weight of a 0.65 wt% cyclohexane solution was added and reacted at 45 ° C. for 1 hour. Thereafter, 0.7 parts by weight of isopropyl alcohol was added to stop the reaction.
20 parts by weight of a nickel-silica supported catalyst (E22U, manufactured by JGC Chemical Co., Ltd.) was added to the reaction solution, and a hydrogenation reaction was performed at a hydrogen pressure of 4.5 MPa and a temperature of 180 ° C. for 6 hours.
After completion of the reaction, this solution was filtered through a filter having a pore size of 2 μm to remove the hydrogenation catalyst. The filtrate was poured into 5000 parts by weight of stirred isopropyl alcohol to precipitate a hydrogenated product, which was collected by filtration.
The obtained hydrogenated product was dried at 100 ° C. for 24 hours at 1 mmHg or less to obtain 300 parts by weight of a ring-opened polymer hydrogenated product (A). The ring-opening polymer hydrogenated product (A) has a weight average molecular weight (Mw) of 32,000, a molecular weight distribution (Mw / Mn) of 2.1, a glass transition temperature of 156 ° C., and hydrogenation of the main chain. The rate was 99% or more, and the hydrogenation rate of the aromatic ring was 99% or more.

[Production Example 2]
In Production Example 1, the same procedure as in Production Example 1 was performed, except that a mixture consisting of 240 parts by weight of MTF and 160 parts by weight of tetracyclododecene (hereinafter sometimes abbreviated as “TCD”) was used as the monomer. A ring polymer hydrogenated product (B) was obtained. The ring-opening polymer hydrogenated product (B) had a weight average molecular weight (Mw) of 44,000, a molecular weight distribution (Mw / Mn) of 2.4, and a glass transition temperature of 161 ° C. Further, the hydrogenation rate of the main chain is 99% or more, the hydrogenation rate of the aromatic ring is 99% or more, and the composition ratio of the ring-opened polymer hydride (B) is MTF / TCD = 57/43 (mol). % / Mol%).

[Production Example 3]
A pressure-resistant reactor equipped with a stirrer was charged with a solution prepared by dissolving 0.84 parts by weight of triethylaluminum in 860 parts by weight of toluene, 200 parts by weight of MTF, and 5.18 parts by weight of toluene.
A glass container is charged with 43.5 parts by weight of toluene, rac-ethylenebis (1-indenyl) zirconium dichloride 0.04 parts by weight, and a solution of 0.51 parts by weight of methylaluminoxane in 2.7 parts by weight of toluene. , Mixed. This mixed solution was added to the pressure resistant reactor. Immediately thereafter, 0.2 MPa of ethylene gas was introduced into the pressure-resistant reactor, and a polymerization reaction was started at 40 ° C. After 36 minutes, the pressure was released, and 5 parts by weight of methanol was added to stop the polymerization reaction. This solution was filtered through Radiolite # 800, and then poured into a large amount of hydrochloric acid-methanol to precipitate a polymer. The precipitated polymer was separated by filtration, washed, and dried under reduced pressure at 100 ° C. for 15 hours to obtain 180 parts by weight of an addition polymer (C). The weight average molecular weight (Mw) of the addition polymer (C) was 82,000, the molecular weight distribution (Mw / Mn) was 2.0, and the glass transition temperature was 176 ° C. The composition ratio of the addition copolymer was MTF / Et = 44/56 (mol% / mol%).

[Production Example 4]
A solution prepared by dissolving 150 parts by weight of addition polymer (C) in a mixed solution of 283 parts by weight of toluene and 567 parts by weight of cyclohexane is added to a stainless steel autoclave, and a nickel-silica supported catalyst (E22U, manufactured by JGC Chemical Co., Ltd.) 50 Part by weight and 15 parts by weight of a palladium-silica supported catalyst (carrier: silica, 5% by weight of Pd supported) were added and stirred. Thereafter, a hydrogenation reaction was carried out at a hydrogen pressure of 4.5 MPa and a temperature of 180 ° C. for 12 hours. The reaction solution was filtered through Radiolite # 800 to obtain a colorless and transparent solution. This solution was poured into a large amount of methanol to precipitate a hydrogenated product. The precipitated hydrogenated product was separated by filtration, washed, and dried under reduced pressure at 100 ° C. for 15 hours to obtain an addition polymer hydrogenated product (D).
The weight average molecular weight (Mw) of the addition polymer hydrogenated product (D) was 65,600, the molecular weight distribution (Mw / Mn) was 1.9, and the glass transition temperature was 148 ° C. Moreover, the hydrogenation rate of the aromatic ring was 99% or more.

[Production Example 5]
In Production Example 3, an addition polymer (E) was obtained in the same manner as in Production Example 3 except that 200 parts by weight of TCD was used instead of MTF as a monomer. The weight average molecular weight (Mw) of the addition polymer (E) was 100,000, the molecular weight distribution (Mw / Mn) was 2.5, and the glass transition temperature was 136 ° C. The composition ratio of the addition copolymer was TCD / Et = 33/67 (mol% / mol%).

[Example 1]
To 50 parts by weight of the ring-opening polymer hydrogenated product (A) and 50 parts by weight of the addition polymer hydrogenated product (D), tetrakis- [methylene-3- (3 ′, 5′-di-tarsha Lee-Butyl-4′-hydroxyphenyl) propionate] 0.1 parts by weight of methane (Irganox 1010, manufactured by Ciba Specialty Chemicals), 0.5 part by weight of 12-hydroxystearic acid triglyceride as a release agent, Using a twin-screw kneader (TEM-35B, manufactured by Toshiba Machine Co., Ltd.), kneaded under the conditions of screw diameter 37 mm, L / D = 32, screw rotation speed 100 rpm, resin temperature 230 ° C., feed rate 10 Kg / hour, strand shape Extruded to. This was cooled with water and cut with a pelletizer, and then dried at 100 ° C. for 4 hours using a hot air dryer in which nitrogen was circulated to obtain a resin composition (1).
When the glass transition temperature of the resin composition (1) was measured, a one-point glass transition temperature was observed at 150 ° C.
The resin composition (1) was molded using an injection molding machine (AUTOSHOTC MODEL 30A, manufactured by FANUC) using a mold having a mirror surface roughness (Ra) of 0.006 μm, a mold clamping force of 30 t, a resin temperature of 280 ° C., and a mold temperature. Molding was performed under molding conditions of 140 ° C. and an injection pressure of 700 kg / cm ² to obtain an injection molded product having a length of 65 mm, a width of 65 mm, and a thickness of 3 mm. Table 1 shows the results of measuring total light transmittance and birefringence using this molded product. Further, an injection molded product having a thickness of 4 mm, a length of 80 mm, and a width of 10 mm obtained under the same conditions as described above was obtained. The results of measuring the bending strength using this molded product are shown in Table 1.

[Example 2]
In Example 1, except that the ring-opening polymer hydrogenated product (A) was replaced by 70 parts by weight and the addition polymer hydrogenated product (D) was replaced by 30 parts by weight, the resin composition (2 ) When the glass transition temperature of the resin composition (2) was measured, a one-point glass transition temperature was observed at 153 ° C.
An injection molded product was obtained in the same manner as in Example 1 except that the resin composition (2) was used and the injection molding conditions were a resin temperature of 285 ° C. and a mold temperature of 145 ° C. The total light transmittance, birefringence and bending strength of this injection molded product were measured, and the results are shown in Table 1.

[Example 3]
In Example 1, a resin composition (3) is obtained by kneading in the same manner as in Example 1 except that the ring-opening polymer hydride (B) is used instead of the ring-opening polymer hydride (A). It was. When the glass transition temperature of the resin composition (3) was measured, a one-point glass transition temperature was observed at 154 ° C.
An injection molded product was obtained in the same manner as in Example 1 except that the resin composition (3) was used and the injection molding conditions were a resin temperature of 285 ° C. and a mold temperature of 145 ° C. The total light transmittance, birefringence and bending strength of this injection molded product were measured, and the results are shown in Table 1.

[Comparative Example 1]
In Example 3, a resin composition (4) was obtained in the same manner as in Example 3, except that the addition polymer (E) was used instead of the addition polymer hydrogenated product (D). When the glass transition temperature of the resin composition (4) was measured, two-point glass transition temperatures were observed at 136 ° C. and 161 ° C.
An injection molded product was obtained in the same manner as in Example 3 except that the resin composition (4) was used and the injection molding conditions were a resin temperature of 290 ° C. and a mold temperature of 130 ° C. The total light transmittance, birefringence and bending strength of this injection molded product were measured, and the results are shown in Table 1.

[Comparative Example 2]
A resin composition (5) was obtained in the same manner as in Example 1, except that the addition polymer (C) was used in place of the addition polymer hydrogenated product (D). When the glass transition temperature of the resin composition (5) was measured, two-point glass transition temperatures were observed at 156 ° C. and 176 ° C.
An injection molded product was obtained in the same manner as in Example 1 except that the resin composition (5) was used and the injection molding conditions were a resin temperature of 305 ° C. and a mold temperature of 145 ° C. The total light transmittance, birefringence and bending strength of this injection molded product were measured, and the results are shown in Table 1.

[Comparative Example 3]
In Example 1, kneading was carried out in the same manner as in Example 1 except that 100 parts by weight of the ring-opening polymer hydrogenated product (A) was used without using the addition polymer hydrogenated product (D), and the resin composition ( 6) was obtained. When the glass transition temperature of the resin composition (6) was measured, a one-point glass transition temperature was observed at 156 ° C.
An injection molded product was obtained in the same manner as in Example 1 except that the resin composition (6) was used and the injection molding conditions were a resin temperature of 285 ° C. and a mold temperature of 145 ° C. The total light transmittance, birefringence and bending strength of this injection molded product were measured, and the results are shown in Table 1.

[Comparative Example 4]
In Example 1, kneading was carried out in the same manner as in Example 1 except that 100 parts by weight of the addition polymer hydrogenated product (D) was used without using the ring-opening polymer hydrogenated product (A), and the resin composition ( 7) was obtained. When the glass transition temperature of the resin composition (7) was measured, a one-point glass transition temperature was observed at 148 ° C.
An injection molded product was obtained in the same manner as in Example 1 using the resin composition (7). The total light transmittance, birefringence and bending strength of this injection molded product were measured, and the results are shown in Table 1.

From the results of Table 1, the resin compositions (Examples 1 to 3) each containing a ring-opening polymer hydrogenated product and an addition-type copolymer hydrogenated product as defined in the present application are transmittance, bending strength, Excellent birefringence.
On the other hand, the resin composition (Comparative Examples 1 and 2) containing the ring-opening polymer hydrogenated product and the addition-type copolymer was inferior in transmittance. Further, the resin composition containing only the ring-opening polymer hydrogenated product (Comparative Example 3) is inferior in birefringence, and the resin composition containing only the addition-type copolymer hydrogenated product (Comparative Example 4) is bent. It was inferior in strength.

Claims (4)

 A ring-opening polymer hydrogenated product of a norbornene monomer containing a repeating unit (a) derived from a norbornene monomer having an aromatic ring (A), and a repeating unit (b) derived from a norbornene monomer having an aromatic ring A resin composition comprising a norbornene monomer containing an α-olefin addition copolymer hydrogenated product (B).  The resin composition according to claim 1, wherein the norbornene monomer having an aromatic ring is a norbornene monomer in which an aromatic ring is condensed as a substituent on an alicyclic ring.  The resin composition according to claim 1, wherein the norbornene monomer having an aromatic ring is 1,4-methano-1,4,4a, 9a-tetrahydrofluorene.  An optical molded article obtained by molding the resin composition according to any one of claims 1 to 4.