JP2016008302A - Resin composition and resin molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having excellent transparency, a high refractive index, a high Abbe number, and a low coefficient of linear expansion, and a resin molded body and an optical member obtained by using the resin composition.SOLUTION: The resin composition comprises: a cyclic olefin resin having each specific range of a weight average molecular weight (Mw) and a ratio of the number of carbon atoms to the number of hydrogen atoms in a repeating unit having a cyclic structure; and a cyclic structure-containing hydrocarbon oligomer having each specific range of a weight average molecular weight (Mw) and a ratio of the number of carbon atoms to the number of hydrogen atoms in a repeating unit having a cyclic structure, with a weight ratio ((cyclic olefin resin):(cyclic structure-containing hydrocarbon oligomer)) ranging from 99:1 to 30:70. The resin composition shows a refractive index of 1.530 to 1.600 for light at a wavelength of 587.6 nm and an Abbe number (ν) of 45 to 60. A resin molded article and an optical member are obtained by using the resin composition.

Description

  The present invention relates to a resin composition having excellent transparency and having a high refractive index, a high Abbe number, and a low linear expansion coefficient, and a resin molded product obtained using the resin composition.

Cyclic olefin resins are widely used as molding materials for optical members such as optical lenses because they are excellent in transparency, low moisture absorption, heat resistance, insulation, chemical resistance, and the like.
In recent years, optical members have been required to be further reduced in size and performance, and the resin used as the molding material has excellent transparency, high refractive index, high Abbe number, and low linear expansion coefficient. It is demanded.
However, the conventional cyclic olefin resin does not sufficiently satisfy all of these characteristics.

In relation to the present invention, Patent Document 1 describes a cyclic olefin resin composition composed of a high molecular weight cyclic olefin resin and a cyclic olefin resin having a number average molecular weight of 10,000 or less. Patent Document 1 also describes that a resin molded body having a smooth surface can be obtained when this resin composition is melt-molded.
However, this document does not describe a combination of cyclic olefin resins that can provide a resin composition that satisfies all of excellent transparency, high refractive index, high Abbe number, and low linear expansion coefficient.

WO2007 / 132641 pamphlet

  The present invention has been made in view of the above-described conventional technology, and is excellent in transparency and has a high refractive index, a high Abbe number, a low linear expansion coefficient, and a resin composition using the resin composition. It aims at providing the resin molding obtained.

  In order to solve the above problems, the present inventors have intensively studied a resin composition containing a cyclic olefin resin and a ring structure-containing hydrocarbon oligomer. As a result, the cyclic olefin resin in which the weight average molecular weight (Mw) and the ratio of the number of carbon atoms and the number of hydrogen atoms of the repeating unit having a ring structure are within a specific range, the weight average molecular weight (Mw), The resin composition in which the value of the ratio of the number of carbon atoms and the number of hydrogen atoms of the repeating unit having a ring structure is appropriately combined with the ring structure-containing hydrocarbon oligomer each having a specific range is excellent in transparency, and It has been found that it has a high refractive index, a high Abbe number, and a low linear expansion coefficient, and has completed the present invention.

Thus, according to the present invention, the following [1] to [4] resin compositions, [5] to [6] resin molded articles, and [7] optical members are provided.
[1] The weight average molecular weight (Mw) is more than 15,000 and not more than 150,000, and the ratio of the number of carbon atoms to the number of hydrogen atoms of the repeating unit having a ring structure (number of carbon atoms / number of hydrogen atoms) is The ratio of the number of carbon atoms and the number of hydrogen atoms of a repeating unit having a cyclic structure of 0.60 to 0.70 and a weight average molecular weight (Mw) of more than 500 and not more than 15,000 and having a ring structure ( The ring structure-containing hydrocarbon oligomer having a carbon atom number / hydrogen atom number of 0.65 to 1.00 is 99: 1 to 30:70 in a weight ratio (cyclic olefin resin: ring structure-containing hydrocarbon oligomer). The refractive index of light having a wavelength of 587.6 nm is 1.530 to 1.600, and the Abbe number (ν _d ) is 45 to 60. A resin composition.
[2] The resin composition according to [1], wherein the cyclic olefin resin is a hydride of a ring-opening polymer of a cyclic olefin monomer.
[3] The resin composition according to [1] or [2], wherein the ring structure-containing hydrocarbon oligomer is a hydrocarbon oligomer having an alicyclic structure in the main chain and / or side chain.

[4] The resin composition according to any one of [1] to [3], wherein the ring structure-containing hydrocarbon oligomer is a homooligomer obtained by addition polymerization of a cyclic olefin monomer.
[5] A resin molded body obtained by molding the resin composition according to any one of [1] to [4].
[6] The resin molded body according to [5], wherein the molding method is injection molding.
[7] An optical member comprising the resin molded body according to [5] or [6].

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which is excellent in transparency and has a high refractive index, a high Abbe number, and a low linear expansion coefficient, and a resin molding obtained using this resin composition are provided.

  Hereinafter, the present invention will be described in detail by dividing it into 1) a resin composition, and 2) a resin molded body and an optical member.

1) Resin Composition The resin composition of the present invention has a weight average molecular weight (Mw) of more than 15,000 and not more than 150,000, and a value of the ratio of the number of carbon atoms and the number of hydrogen atoms of a repeating unit having a ring structure. A cyclic olefin resin having (carbon atom number / hydrogen atom number) of 0.60 to 0.70, a weight average molecular weight (Mw) of more than 500 and not more than 15,000, and a carbon atom of a repeating unit having a ring structure The ratio of the number of hydrogen atoms to the number of hydrogen atoms (number of carbon atoms / number of hydrogen atoms) is from 0.65 to 1.00, and the weight ratio (cyclic olefin resin: ring structure-containing hydrocarbon oligomer) ) In the range of 99: 1 to 30:70, the refractive index of light having a wavelength of 587.6 nm is 1.530 to 1.600, and the Abbe number (ν _d ) Is 45 to 60 .
The refractive index and Abbe number (ν _d ) of the resin composition are both measured values in a resin molded body obtained by molding the resin composition. The same applies to transparency and linear expansion coefficient. In addition, regarding these physical property values, the difference in molding conditions usually has little influence.

[Cyclic olefin resin]
The cyclic olefin resin used has a weight average molecular weight (Mw) of more than 15,000 and not more than 150,000, and the ratio of the number of carbon atoms to the number of hydrogen atoms of the repeating unit having a ring structure (number of carbon atoms / hydrogen atoms). Number) is 0.60 to 0.70.
The cyclic olefin resin is a polymer having an alicyclic structure in the molecule, and is a polymer obtained by performing a polymerization reaction using a cyclic olefin as a monomer or a hydride thereof.
Examples of the alicyclic structure of the cyclic olefin resin include a cycloalkane structure and a cycloalkene structure. Among these, a cycloalkane structure is preferable because a resin molded body excellent in light resistance and the like can be easily obtained. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, and more preferably 5 to 15.

The cyclic olefin resin used has a weight average molecular weight (Mw) of more than 15,000 and not more than 150,000, preferably 20,000 to 100,000, more preferably 23,000 to 50,000. It is considered that the weight average molecular weight (Mw) of the cyclic olefin resin does not significantly affect the effect of the present invention. However, if the weight average molecular weight (Mw) is too small, the strength of the resin molding may be reduced. On the other hand, if the weight average molecular weight (Mw) is too large, the compatibility between the cyclic olefin resin and the ring structure-containing hydrocarbon oligomer may decrease.
Here, “A to B” means A or more and B or less, that is, includes A and B as boundary values (the same applies hereinafter).

Although molecular weight distribution (Mw / Mn) of cyclic olefin resin is not specifically limited, Preferably it is 1-5, More preferably, it is 1-4.
When the molecular weight distribution of the cyclic olefin resin is within the above range, a resin molded article having sufficient mechanical strength can be obtained.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the cyclic olefin resin are standard polyisoprene conversion values by gel permeation chromatography (GPC) using cyclohexane as an eluent.

The ratio of the number of carbon atoms to the number of hydrogen atoms (number of carbon atoms / number of hydrogen atoms) of the repeating unit having a cyclic structure in the cyclic olefin resin to be used is 0.60 to 0.70, preferably 0.61 to 0.68, more preferably 0.62 to 0.67. When the value of this ratio is too small, it becomes difficult to obtain a resin composition having a high refractive index. Moreover, when the value of this ratio is too large, the compatibility between the cyclic olefin resin and the ring structure-containing hydrocarbon oligomer may be lowered.
The value of the ratio of the number of carbon atoms and the number of hydrogen atoms of the repeating unit having a cyclic structure in the cyclic olefin resin can be adjusted by appropriately selecting a monomer used for the synthesis of the cyclic olefin resin.

As the cyclic olefin resin to be used, a ring-opened polymer of a cyclic olefin monomer (hereinafter sometimes referred to as “polymer (α)”), a hydride thereof, an addition polymer using a cyclic olefin monomer ( Hereinafter, it may be referred to as “polymer (β)”) and hydrides thereof.
As will be described later, the cyclic olefin resin is preferably a hydride of a polymer (α) because various properties are excellent in balance and an intended resin composition is easily obtained.

(1) Polymer (α) and its hydride The cyclic olefin monomer used for the synthesis of the polymer (α) and its hydride has a ring structure formed of carbon atoms, and carbon is contained in the ring. -A compound having a carbon double bond. Specific examples include norbornene monomers. Moreover, when a polymer ((alpha)) is a copolymer, a monocyclic cyclic olefin can also be used as a cyclic olefin monomer.

The norbornene monomer is a monomer containing a norbornene ring.
The norbornene-based monomer includes bicyclo [2.2.1] hept-2-ene (common name: norbornene), 5-ethylidene-bicyclo [2.2.1] hept-2-ene (common name: ethylidene). Norbornene) and derivatives thereof (those having a substituent in the ring);
Tricyclo [4.3.0 ^1,6 . 1 ^2,5 ] deca-3,7-diene (common name: dicyclopentadiene) and derivatives thereof;
7,8-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene (common name: methanotetrahydrofluorene: also referred to as 1,4-methano-1,4,4a, 9a-tetrahydrofluorene) ) And its derivatives, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (common name: tetracyclododecene), 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and tetracyclic monomers such as derivatives thereof; and the like.

  Examples of substituents for these monomers include alkyl groups such as methyl and ethyl groups; alkenyl groups such as vinyl groups; alkylidene groups such as propan-2-ylidene; aryl groups such as phenyl groups; hydroxy groups; A carboxyl group; an alkoxycarbonyl group such as a methoxycarbonyl group; and the like.

Examples of the monocyclic olefin include cyclomonoolefins such as cyclobutene, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cycloheptene, and cyclooctene; cyclohexadiene, methylcyclohexadiene, cyclooctadiene, methylcyclooctadiene, phenylcyclooctadiene Cyclic diolefins such as; and the like.
These cyclic olefin monomers can be used alone or in combination of two or more.
When two or more cyclic olefin monomers are used, the polymer (α) may be a block copolymer or a random copolymer.

The polymer (α) can be synthesized according to a known method using a metathesis polymerization catalyst.
The metathesis polymerization catalyst is not particularly limited and known ones are used. As a metathesis polymerization catalyst, a catalyst system comprising a metal halide, nitrate or acetylacetone compound selected from ruthenium, rhodium, palladium, osmium, iridium and platinum and a reducing agent; from titanium, vanadium, zirconium, tungsten and molybdenum A catalyst system comprising a selected metal halide or acetylacetone compound and a co-catalyst organoaluminum compound; a Schrock-type or Grubbs-type living ring-opening metathesis polymerization catalyst (JP-A-7-179575, J. Am. Chem. Soc., 1986, 108, p.733, J. Am.Chem.Soc., 1993, 115, p.9858, and J.Am.Chem.Soc., 1996, 118, p.100); Etc.

  These metathesis polymerization catalysts can be used alone or in combination of two or more. The amount of the metathesis polymerization catalyst used may be appropriately selected depending on the polymerization conditions and the like, but is usually 0.000001 to 0.1 mol, preferably 0.00001 to 0.01 with respect to 1 mol of the cyclic olefin monomer. Is a mole.

When performing ring-opening polymerization of a cyclic olefin monomer, a linear α-olefin having 4 to 40 carbon atoms such as 1-butene, 1-hexene, 1-decene and the like can be used as a molecular weight regulator.
The addition amount of the linear α-olefin is usually 0.001 to 0.030 mol, preferably 0.003 to 0.020 mol, more preferably 0.005 to 0, per 1 mol of the cyclic olefin monomer. .015 mole.

  The ring-opening polymerization of the cyclic olefin monomer can be performed in an organic solvent. The organic solvent is not particularly limited as long as it is inert to the polymerization reaction. Examples of the organic solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; fats such as cyclohexane, methylcyclohexane, decalin and bicyclononane. And cyclic hydrocarbon solvents; halogenated hydrocarbon solvents such as dichloroethane, chlorobenzene, dichlorobenzene, and trichlorobenzene;

  Although superposition | polymerization temperature is not specifically limited, Usually, -50-250 degreeC, Preferably it is -30-200 degreeC, More preferably, it is -20-150 degreeC. The polymerization time is appropriately selected depending on the polymerization conditions, but is usually 30 minutes to 20 hours, preferably 1 to 10 hours.

A hydride of the polymer (α) can be obtained by subjecting the polymer (α) obtained by the above method to a hydrogenation reaction.
The hydrogenation reaction of the polymer (α) can be performed by bringing the polymer (α) into contact with hydrogen in the presence of a hydrogenation catalyst according to a conventional method.

The hydrogenation catalyst may be a homogeneous catalyst or a heterogeneous catalyst.
The homogeneous catalyst can be easily dispersed in the hydrogenation reaction solution, so that the amount of catalyst added can be suppressed. In addition, the polymer (α) and its hydride are not easily decomposed or gelled because they have sufficient activity even without high temperature and pressure. For this reason, it is preferable to use a homogeneous catalyst from the viewpoint of cost and product quality.
On the other hand, the heterogeneous catalyst exhibits particularly excellent activity under high temperature and high pressure, and therefore can polymerize the polymer (α) in a short time. Further, the catalyst residue can be easily removed after the hydrogenation reaction. For this reason, it is preferable to use a heterogeneous catalyst from the viewpoint of production efficiency.

  As homogeneous catalysts, Wilkinson complex [chlorotris (triphenylphosphine) rhodium (I)]; cobalt acetate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene dichloride / n-butyllithium, zirconocene dichloride / sec-butyl A catalyst comprising a combination of a transition metal compound and an alkyl metal compound, such as a combination of lithium, tetrabutoxytitanate / dimethylmagnesium, and the like.

  Examples of the heterogeneous catalyst include those in which a metal such as Ni, Pd, Pt, Ru, and Rh is supported on a carrier. In particular, when reducing the amount of impurities in the hydride obtained, it is preferable to use an adsorbent such as alumina or diatomaceous earth as the carrier.

The hydrogenation reaction is usually performed in an organic solvent. The organic solvent is not particularly limited as long as it is inert to the hydrogenation reaction. As the organic solvent, a hydrocarbon solvent is usually used because it easily dissolves the hydride produced. Examples of the hydrocarbon solvent include aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; cyclohexane, methylcyclohexane, decalin, bicyclononane and the like. Alicyclic hydrocarbon-based solvents; and the like.
These organic solvents can be used alone or in combination of two or more. In general, the solvent used in the ring-opening polymerization reaction is also suitable as a solvent for the hydrogenation reaction. Therefore, after adding a hydrogenation catalyst to the ring-opening polymerization reaction solution, it can be used for the hydrogenation reaction.

The hydrogenation reaction can be performed according to a conventional method.
The hydrogenation rate varies depending on the type of hydrogenation catalyst and the reaction temperature. Therefore, when the polymer (α) has an aromatic ring, the residual ratio of the aromatic ring can be controlled by selecting a hydrogenation catalyst, adjusting the reaction temperature, or the like. For example, in order to leave an unsaturated bond in the aromatic ring more than a certain amount, control such as lowering the reaction temperature, lowering the hydrogen pressure, or shortening the reaction time may be performed.

  After completion of the hydrogenation reaction, the catalyst residue can be removed by performing a treatment such as centrifugation or filtration. If necessary, a catalyst deactivator such as water or alcohol may be used, or an adsorbent such as activated clay or alumina may be added.

(2) Polymer (β) and its hydride The cyclic olefin monomer used for the synthesis of polymer (β) and its hydride is shown as the cyclic olefin monomer used for the synthesis of polymer (α). The same thing is mentioned.
In the synthesis of the polymer (β), other monomers copolymerizable with the cyclic olefin monomer can be used as the monomer.
Examples of other monomers include α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene and 1-hexene; aromatic vinyl compounds such as styrene and α-methylstyrene; Non-conjugated dienes such as 4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene; and the like. Among these, α-olefin is preferable and ethylene is more preferable.
Other monomers can be used alone or in combination of two or more.

  In the case of addition copolymerization of a cyclic olefin monomer and another monomer, the ratio of the amount used of the cyclic olefin monomer and the other monomer is a weight ratio (cyclic olefin monomer: other The monomer is usually 30:70 to 99: 1, preferably 50:50 to 97: 3, and more preferably 70:30 to 95: 5.

  When two or more cyclic olefin monomers are used, or when a cyclic olefin monomer and other monomers are used, the polymer (β) may be a block copolymer or a random copolymer. It may be a coalescence.

The polymer (β) can be synthesized according to a known method using an addition polymerization catalyst.
Examples of addition polymerization catalysts include vanadium catalysts formed from vanadium compounds and organoaluminum compounds, titanium catalysts formed from titanium compounds and organoaluminum compounds, zirconium catalysts formed from zirconium complexes and aluminoxanes, and the like. It is done.
These addition polymerization catalysts can be used singly or in combination of two or more. The addition amount of the addition polymerization catalyst may be appropriately selected depending on the polymerization conditions and the like, but is usually 0.000001 to 0.1 mol, preferably 0.00001 to 0.01 mol with respect to 1 mol of the monomer. is there.

  The addition polymerization of the cyclic olefin monomer is usually performed in an organic solvent. Examples of the organic solvent include the same solvents as those used for the ring-opening polymerization of the cyclic olefin monomer.

  The polymerization temperature is usually −50 to 250 ° C., preferably −30 to 200 ° C., more preferably −20 to 150 ° C. The polymerization time is appropriately selected depending on the polymerization conditions, but is usually 30 minutes to 20 hours, preferably 1 to 10 hours.

By subjecting the polymer (β) obtained by the above method to a hydrogenation reaction, a hydride of the polymer (β) can be obtained.
The hydrogenation reaction of the polymer (β) can be carried out by the same method as that shown above as the method for hydrogenating the polymer (α).

[Ring structure-containing hydrocarbon oligomer]
The ring structure-containing hydrocarbon oligomer used in the present invention has a weight average molecular weight (Mw) of more than 500 and not more than 15,000, and a value of the ratio of the number of carbon atoms and the number of hydrogen atoms of a repeating unit having a ring structure (carbon atoms Number / number of hydrogen atoms) is 0.65 to 1.00.
The “hydrocarbon oligomer” refers to an oligomer obtained by polymerizing a hydrocarbon compound having a carbon-carbon double bond in the molecule or a hydride thereof.
The “ring structure-containing hydrocarbon oligomer” refers to a hydrocarbon oligomer having an aromatic ring structure or an alicyclic structure in the main chain and / or side chain.

  The weight average molecular weight (Mw) of the cyclic structure-containing hydrocarbon oligomer used is more than 500 and not more than 15,000, preferably 600 to 10,000, more preferably 700 to 6,000. When the weight average molecular weight (Mw) is too large, it becomes difficult to obtain a resin composition having excellent transparency. On the other hand, a resin molded body of a resin composition containing a ring structure-containing hydrocarbon oligomer having a weight average molecular weight (Mw) that is too small tends to increase birefringence.

The molecular weight distribution (Mw / Mn) of the ring structure-containing hydrocarbon oligomer is not particularly limited, but is preferably in the range of 1 to 5, more preferably 1 to 4.
When the molecular weight distribution of the ring structure-containing hydrocarbon oligomer is within the above range, a resin molded article having sufficient mechanical strength can be obtained.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the ring structure-containing hydrocarbon oligomer are standard polyisoprene equivalent values determined by gel permeation chromatography (GPC) using cyclohexane as an eluent.

The ratio of the number of carbon atoms and the number of hydrogen atoms (the number of carbon atoms / the number of hydrogen atoms) of the repeating unit having a ring structure in the cyclic structure-containing hydrocarbon oligomer to be used is 0.65 to 1.00, preferably 0. .66 to 0.95, more preferably 0.67 to 0.90. When the value of this ratio is too small, it becomes difficult to obtain a resin composition having a high refractive index. On the other hand, if the value of this ratio is too large, it is difficult to obtain a resin composition having a high Abbe number (ν _d ).
The value of the ratio between the number of carbon atoms and the number of hydrogen atoms of the hydrocarbon oligomer can be adjusted by appropriately selecting the monomer used for the synthesis of the ring structure-containing hydrocarbon oligomer.

The ring structure-containing hydrocarbon oligomer to be used is not particularly limited as long as it satisfies the above requirements. However, since the target resin composition is easily obtained, carbonization having an alicyclic structure in the main chain and / or side chain. Hydrogen oligomers (hereinafter sometimes referred to as “alicyclic structure-containing oligomers”) are preferred.
Examples of the alicyclic structure of the alicyclic structure-containing oligomer include a cycloalkane structure and a cycloalkene structure. Among these, a cycloalkane structure is preferable because a resin molded body excellent in light resistance and the like can be easily obtained. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually 4 to 30, preferably 5 to 20, and more preferably 5 to 15.

The alicyclic structure-containing oligomer is sometimes referred to as an oligomer obtained by a ring-opening polymerization reaction of a cyclic olefin monomer [hereinafter referred to as “oligomer (α)”. And hydrides thereof; oligomers obtained by an addition polymerization reaction using a ring structure-containing monomer [hereinafter referred to as “oligomer (β)”. And hydrides thereof; and the like.
As will be described later, since various properties are excellent in balance and the desired resin composition is easily obtained, the alicyclic structure-containing oligomer is a homo-oligomer obtained by addition polymerization of a cyclic olefin monomer. preferable.

(1) Oligomer (α) and its hydride The cyclic olefin monomer used for the synthesis of the oligomer (α) is the same as that shown above as the cyclic olefin monomer used for the synthesis of the polymer (α). Things.
Moreover, the catalyst and organic solvent used for the synthesis | combination of an oligomer ((alpha)) can also be performed using what was shown previously as a catalyst and an organic solvent used for the synthesis | combination of a polymer ((alpha)).

  That is, the amount of the cyclic olefin monomer and the catalyst, the amount of the molecular weight regulator, the reaction conditions, etc. are appropriately determined to synthesize an oligomer having a predetermined weight average molecular weight (Mw). The oligomer (α) can be synthesized by the same method as the synthesis method.

The obtained oligomer (α) may be used as a ring structure-containing hydrocarbon oligomer as it is, or may be subjected to a hydrogenation reaction to carry out a hydrogenation reaction of the oligomer (α).
The hydrogenation reaction of the oligomer (α) can be carried out by the same method as described above as the method for hydrogenating the polymer (α).

(2) Oligomer (β) and its hydride The cyclic structure-containing monomer used for the synthesis of the oligomer (β) includes a cyclic olefin monomer, an aromatic vinyl compound monomer, and a vinylcycloalkane monomer. And vinylcycloalkene monomers.

As a cyclic olefin monomer, the thing similar to what was shown previously as a cyclic olefin monomer used for the synthesis | combination of a polymer ((alpha)) is mentioned.
Examples of the aromatic vinyl compound monomer include styrene, α-methylstyrene, divinylbenzene, vinyl naphthalene, and vinyl toluene.
Examples of the vinylcycloalkane monomer include vinylcyclopentane, 2-methyl-4-vinylcyclopentane, vinylcyclohexane, vinylcyclooctane and the like.
Examples of the vinylcycloalkene monomer include vinylcyclopentene, 2-methyl-4-vinylcyclopentene, vinylcyclohexene and the like.

Moreover, in the synthesis | combination of an oligomer ((beta)), the other monomer copolymerizable with this can also be used with a ring structure containing monomer as a monomer.
Other monomers include α-olefins having 2 to 20 carbon atoms such as ethylene, propylene, 1-butene, 1-pentene and 1-hexene; 1,4-hexadiene, 4-methyl-1,4-hexadiene , Non-conjugated dienes such as 5-methyl-1,4-hexadiene and 1,7-octadiene; Among these, α-olefin is preferable and ethylene is more preferable.
Other monomers can be used alone or in combination of two or more.

  In the case of addition copolymerization of a ring structure-containing monomer and another monomer, the ratio of the amount used of the ring structure-containing monomer and the other monomer is expressed by weight ratio (single amount containing the ring structure). Body: other monomers), usually 30:70 to 99: 1, preferably 50:50 to 97: 3, more preferably 70:30 to 95: 5.

  When two or more ring structure-containing monomers are used, or when a ring structure-containing monomer and other monomers are used, the oligomer (β) may be a block copolymer or a random copolymer. It may be a polymer.

  Examples of the catalyst and organic solvent used for the synthesis of the oligomer (β) include the same catalysts and organic solvents used for the synthesis of the polymer (β).

  That is, by appropriately determining the amount of the monomer and catalyst, reaction conditions, etc., and synthesizing an oligomer having a predetermined weight average molecular weight (Mw), the same method as the method for synthesizing the polymer (β), An oligomer (β) can be synthesized.

The obtained oligomer (β) may be used as a ring structure-containing hydrocarbon oligomer as it is, or may be subjected to a hydrogenation reaction to carry out a hydrogenation reaction of the oligomer (β).
The hydrogenation reaction of the oligomer (β) can be carried out by the same method as that shown above as the method for hydrogenating the polymer (α).

(Resin composition)
The resin composition of the present invention contains the cyclic olefin resin and the ring structure-containing hydrocarbon oligomer. The content ratio is 99: 1 to 30:70, preferably 98: 2 to 40:60, more preferably 95: 5 to 50:50 in weight ratio (cyclic olefin resin: ring structure-containing hydrocarbon oligomer). It is. When there is too little content of a ring structure containing hydrocarbon oligomer, it will become difficult to obtain a resin composition with a high refractive index and a low coefficient of linear expansion. Moreover, the resin molding obtained using the resin composition tends to increase birefringence. On the other hand, when there is too much content of a ring structure containing hydrocarbon oligomer, it will become difficult to obtain the resin composition excellent in transparency.

The resin composition of the present invention may contain other components such as additives as long as the effects of the present invention are not impaired.
Examples of other components include an antioxidant, an ultraviolet absorber, a light stabilizer, a near infrared absorber, a plasticizer, and an antistatic agent.
Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.

  Examples of phenolic antioxidants include 3,5-di-t-butyl-4-hydroxytoluene, dibutylhydroxytoluene, 2,2′-methylenebis (6-t-butyl-4-methylphenol), 4,4 ′. -Butylidenebis (3-t-butyl-3-methylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), α-tocophenol, 2,2,4-trimethyl-6-hydroxy -7-t-butylchroman, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, and the like.

  Examples of phosphorus antioxidants include distearyl pentaerythritol diphosphite, bis (2,4-ditertiarybutylphenyl) pentaerythritol diphosphite, tris (2,4-ditertiarybutylphenyl) phosphite, tetrakis (2 , 4-ditertiary butylphenyl) 4,4′-biphenyl diphosphite, trinonylphenyl phosphite and the like.

  Examples of sulfur-based antioxidants include distearyl thiodipropionate and dilauryl thiodipropionate.

Examples of the UV absorber include benzotriazole UV absorbers, bezoate UV absorbers, benzophenone UV absorbers, acrylate UV absorbers, and metal complex UV absorbers.
Examples of the light stabilizer include hindered amine light stabilizers.

Near-infrared absorbers are cyanine-based near-infrared absorbers; pyrylium-based infrared absorbers; squarylium-based near-infrared absorbers; croconium-based infrared absorbers; azulenium-based near-infrared absorbers; phthalocyanine-based near-infrared absorbers; Examples include near infrared absorbers; naphthoquinone near infrared absorbers; anthraquinone near infrared absorbers; indophenol near infrared absorbers;
Examples of the plasticizer include a phosphoric acid triester plasticizer, a fatty acid monobasic acid ester plasticizer, a dihydric alcohol ester plasticizer, and an oxyacid ester plasticizer.
Examples of the antistatic agent include fatty acid esters of polyhydric alcohols.

  The content of these components can be appropriately determined according to the purpose. Content is 0.001-5 weight part normally with respect to a total of 100 weight part of cyclic olefin resin and ring structure containing hydrocarbon oligomer, Preferably it is the range of 0.01-1 weight part.

  The resin composition of this invention can be obtained by mixing each component in accordance with a conventional method. Examples of the mixing method include a method of mixing each component in an appropriate solvent and a method of kneading in a molten state.

  Kneading can be performed using a melt kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, or a feeder ruder. The kneading temperature is preferably 200 to 400 ° C, more preferably 240 to 350 ° C. In kneading, the components may be added together and kneaded, or may be kneaded while adding in several times.

The resin composition of the present invention has a refractive index of light having a wavelength of 587.6 nm of 1.530 to 1.600, preferably 1.535 to 1.590, more preferably 1.540 to 1.580. is there.
In the present invention, the refractive index can be made higher than that of the cyclic olefin resin alone by blending the cyclic olefin resin with the cyclic olefin resin into the resin composition.
In addition, the ratio of the number of carbon atoms and the number of hydrogen atoms of the cyclic olefin resin (number of carbon atoms / number of hydrogen atoms) and the ratio of the number of carbon atoms and the number of hydrogen atoms of the ring structure-containing hydrocarbon oligomer (number of carbon atoms) As the number of (/ hydrogen atoms) increases, the refractive index of the resin composition tends to increase.
Therefore, for example, the resin composition having a high refractive index of 1.530 to 1.600 is a value of the ratio of the number of carbon atoms to the number of hydrogen atoms in the cyclic olefin resin or ring structure-containing hydrocarbon oligomer used. In addition to determining the type and amount of the ring structure, the content ratio of the cyclic olefin resin and the ring structure-containing hydrocarbon oligomer is adjusted according to the cyclic olefin resin and the ring structure-containing hydrocarbon oligomer to be used. It can be obtained by adjusting.

The resin composition of the present invention has an Abbe number (ν _d ) of 45 to 60, preferably 50 to 59, more preferably 53 to 58.
The Abbe number is a numerical value indicating the degree of refractive index (wavelength dispersion of refractive index) for each wavelength of light. The refractive index of the material for light of the F line (wavelength: 486.1 nm), d line (wavelength: 587.6 nm), and C line (wavelength: 656.3 nm) of the Fraunhofer line is expressed as n _F , n _d , respectively. When n _C , the Abbe number (ν _d ) is defined by the following formula (1).

As the Abbe number (ν _d ), the larger the value of the material, the smaller the chromatic dispersion of the refractive index, and the smaller the variation in the emission angle of light for each wavelength. The smaller the value, the chromatic dispersion of the refractive index. And the variation of the emission angle of light for each wavelength increases.
A resin composition having an Abbe number (ν _d ) of 45 to 60 is preferably used as a raw material for producing an optical member.

In the resin composition of the present invention, the Abbe number (ν _d ) increases as the ratio of the number of carbon atoms to the number of hydrogen atoms (number of carbon atoms / number of hydrogen atoms) of the ring structure-containing hydrocarbon oligomer used increases. Tend to be lower. Therefore, for example, the resin composition having a high Abbe number of 45 to 60 has a ring structure type and its amount so that the ratio of the number of carbon atoms to the number of hydrogen atoms in the hydrocarbon oligomer to be used does not become too high. Can be obtained.

As described above, the value of the ratio of the number of carbon atoms to the number of hydrogen atoms (number of carbon atoms / number of hydrogen atoms) of the ring structure-containing hydrocarbon oligomer is preferably larger with respect to the refractive index, and the Abbe number (ν _d ) Is preferably smaller. Therefore, in the resin composition of the present invention, it is important to properly balance the two.
In this respect, the ring structure-containing hydrocarbon oligomer is preferably an oligomer having an alicyclic structure in the main chain and / or side chain, and more preferably a homo-oligomer obtained by addition polymerization of a cyclic olefin monomer.
When these ring structure-containing hydrocarbon oligomers are used in combination with the cyclic olefin resin, both characteristics can be improved in a balanced manner, and the resin composition of the present invention can be obtained more efficiently.

The transparency of the resin composition of the present invention is mainly affected by the weight average molecular weight (Mw) of the ring structure-containing hydrocarbon oligomer and its content. The weight average molecular weight (Mw) of the ring structure-containing hydrocarbon oligomer used in the present invention is 15,000 or less, and the upper limit of the amount of the ring structure-containing hydrocarbon oligomer contained in the resin composition is the weight ratio (cyclic olefin resin: ring Structure-containing hydrocarbon oligomer).
In order to satisfy these requirements, the resin composition of the present invention is excellent in transparency. The light transmittance of light having a wavelength of 650 nm of the sheet-like molded product having a thickness of 3 mm obtained using the resin composition of the present invention is preferably 88% or more, more preferably 90% or more, and 92% or more. Is more preferable.

The linear expansion coefficient of the resin composition of the present invention is mainly affected by the content of the ring structure-containing hydrocarbon oligomer. The lower limit of the amount of the ring structure-containing hydrocarbon oligomer contained in the resin composition of the present invention is 99: 1 by weight ratio (cyclic olefin resin: ring structure-containing hydrocarbon oligomer).
In order to satisfy this requirement, the linear expansion coefficient of the resin composition of the present invention is low. The linear expansion coefficient at 30 to 120 ° C. of a 5 mm × 5 mm × 10 mm molded body obtained using the resin composition of the present invention is preferably 30 to 80 ppm / ° C., more preferably 40 to 65 ppm / ° C. is there.

As described above, the resin composition of the present invention contains the cyclic olefin resin and the ring structure-containing hydrocarbon oligomer in an appropriate combination, is excellent in transparency, and has a high refractive index and high. Abbe number, low coefficient of linear expansion.
As will be described later, the resin composition of the present invention is useful as a molding material for optical members.

2) Resin molded body The resin molded body of the present invention is obtained by molding the resin composition of the present invention.
The molding method is not particularly limited, and examples thereof include injection molding, press molding, and extrusion molding. Among these, when a molded object is an optical member etc., since the target molded object can be obtained with sufficient precision, injection molding is preferable.

  Although the melting temperature at the time of molding varies depending on the resin composition to be used, it is usually 200 to 400 ° C, preferably 210 to 350 ° C. The mold temperature in the case of using a mold is usually 20 ° C. to (Tg + 15) ° C., preferably (Tg−30) ° C. to (Tg + 10) ° C., more preferably, when the glass transition temperature of the resin composition is Tg. Is a temperature from (Tg−20) ° C. to (Tg + 5) ° C.

Since the resin molded body of the present invention is obtained by molding the resin composition of the present invention, it is excellent in transparency, has a high refractive index, a high Abbe number, and a low coefficient of linear expansion.
Moreover, even if the resin molded body of the present invention is molded by a normal injection molding method, it tends to exhibit low birefringence.
In the resin molded body of the present invention, the retardation value in light having a wavelength of 650 nm is preferably 80 nm or less, more preferably 70 nm or less, and further preferably 60 nm or less.
A resin molded article excellent in low birefringence can be obtained by using a resin composition that contains a hydrocarbon oligomer having a relatively large weight average molecular weight and whose blending ratio is not too low.

  The resin molded body of the present invention is suitably used as an optical member such as an optical lens, a prism, or a light guide because these characteristics are sufficiently utilized.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to these examples. In the following, “part” and “%” are based on weight unless otherwise specified, and the pressure is a gauge pressure.

Various physical properties were measured according to the following methods.
(1) Molecular weight The weight average molecular weight (Mw) of the cyclic olefin resin and the cyclic structure-containing hydrocarbon oligomer is measured by gel permeation chromatography (GPC) using cyclohexane as an eluent, and obtained as a standard polyisoprene conversion value. It was.
As the standard polyisoprene, standard polyisoprene (Mw = 602, 1390, 3920, 8050, 13800, 22700, 58800, 71300, 109000, 280000) manufactured by Tosoh Corporation was used.
The measurement was carried out using three Tosoh columns (TSKgel G5000HXL, TSKgel G4000HXL and TSKgel G2000HXL) connected in series under the conditions of a flow rate of 1.0 ml / min, a sample injection amount of 100 μml, and a column temperature of 40 ° C.

(2) Hydrogenation rate The hydrogenation rate in the hydrogenation reaction was determined by measuring a ¹ H-NMR spectrum.
(3) Refractive index The resin composition was molded into a sheet having a thickness of 5 mm, and left in an atmosphere of [glass transition temperature (Tg) -15] ° C. of the resin composition for 20 hours as a measurement sample.
About the obtained measurement sample, using a precision refractometer (manufactured by Shimadzu Corporation, product name: KPR-200, light source = He lamp (587.6 nm), H2 lamp (656.3 nm, 486.1 nm) at 25 ° C. The refractive index (n _d , n _C , n _F ) was measured.
Tables 1 and 2 show the refractive index of light having a wavelength of 587.6 nm.
In addition, the glass transition temperature (Tg) was measured on the conditions of the temperature increase rate of 10 degree-C / min based on JISK6911 using the differential scanning calorimeter (Nanotechnology company make, product name: DSC6220SII).

(4) Abbe number (ν _d )
The Abbe number (ν _d ) was calculated according to the following formula (1) using the refractive indexes at 25 ° C. (n _d , n _C , n _F ) obtained by refractive index measurement.

In the formula (1), n _d , n _C , and n _F represent refractive indexes at wavelengths of 587.6 nm, 656.3 nm, and 486.1 nm, respectively.

(5) Transparency The resin composition was molded into a sheet shape having a thickness of 3 mm and used as a measurement sample.
About the obtained measurement sample, the light transmittance (light path length 3 mm) in the light with a wavelength of 650 nm is measured using an ultraviolet visible spectrophotometer (product name: UV-VIS V570 manufactured by JASCO Corporation), and the resin composition The transparency of the object was evaluated according to the following criteria.
◎: Transmittance is 92% or more ○: Transmittance is 90% or more and less than 92% Δ: Transmittance is 88% or more and less than 90% ×: Transmittance is less than 88%

(6) Linear expansion coefficient The resin composition was molded into a shape of 5 mm × 5 mm × 10 mm and used as a measurement sample.
About the obtained measurement sample, the linear expansion coefficient in 30-120 degreeC was measured using the thermomechanical analyzer (the Seiko Instruments company make, product name: TMA / SS-6000).

(6) Birefringence (retardation value)
The resin composition was molded into a shape of 60 mm × 60 mm × 2 mm, and this was used as a measurement sample.
About the obtained measurement sample, the retardation value of the measurement sample center part in the light with a wavelength of 650 nm was measured using the birefringence meter (the product name: KOBRA-CCD / X by Oji Scientific Instruments).

[Production Example 1]
In a polymerization reactor in which the interior was replaced with nitrogen, 7 parts of a monomer mixture (methanotetrahydrofluorene 65%, tetracyclododecene 30%, norbornene 5%), dehydrated cyclohexane 1,600 parts, 1-hexene 0.6 parts, 1.3 parts of diisopropyl ether, 0.33 parts of isobutyl alcohol, 0.84 parts of triisobutylaluminum, 30 parts of a cyclohexane solution of tungsten hexachloride (concentration: 0.66%) were added and stirred at 55 ° C. for 10 minutes. .
Subsequently, 693 parts of the monomer mixture and 72 parts of a cyclohexane solution of tungsten hexachloride (concentration: 0.77%) were continuously added dropwise over 55 minutes at 55 ° C. while stirring was continued. After completion of the dropwise addition, stirring was continued for another 30 minutes, and then 1.0 part of isopropyl alcohol was added to stop the polymerization reaction. When the polymerization reaction solution was measured by gas chromatography, the conversion ratio of the monomer to the polymer was 100%.

Next, 300 parts of the polymerization reaction solution containing the above polymer was transferred to an autoclave equipped with a stirrer, and 100 parts of cyclohexane, a diatomaceous earth-supported nickel catalyst (product name: T8400RL, nickel support rate 58%) 2.0 Part was added. After replacing the inside of the autoclave with hydrogen, a hydrogenation reaction was performed at 180 ° C. under a hydrogen pressure of 4.5 MPa for 6 hours.
After completion of the hydrogenation reaction, a diatomaceous earth (made by Showa Chemical Industry Co., Ltd., product name: Radiolite (registered trademark) # 500) is used as a filter bed, and a pressure filter (made by Ishikawajima Harima Heavy Industries Co., Ltd., product name: Fundafilter) is used. Used and pressure filtered at a pressure of 0.25 MPa to obtain a clear and colorless solution.

Subsequently, 0.5 parts of an antioxidant [manufactured by BASF Japan, product name: Irganox (registered trademark) 1010, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane] was added.
This solution is filtered through a filter (Kyunoh Filter, product name: Zeta Plus (registered trademark) 30H, pore size 0.5-1 μm) and a metal fiber filter (Nichidai, pore size 0.4 μm). , Removed foreign matter.
Next, after removing the solvent (cyclohexane) and other volatile components from the filtrate under the conditions of a temperature of 260 ° C. and a pressure of 1 kPa or less using a cylindrical concentration dryer (manufactured by Hitachi, Ltd.), The melt was extruded as a strand from a directly connected die. This melt was cooled with water and then cut with a pelletizer (manufactured by Nagata Seisakusho, product name: OSP-2) to obtain a pellet of the cyclic olefin resin (1).
The weight average molecular weight of the cyclic olefin resin (1) was 29,000. The hydrogenation rate in the hydrogenation reaction was 99% or more.

[Production Example 2]
In a dry glass polymerization reactor, 50 parts of tetracyclododecene, 250 parts of nitromethane, and 0.5 part of tetrakis (acetonitrile) palladium (II) bis (tetrafluoroborate) are placed in a nitrogen atmosphere at room temperature for 24 hours. The mixture was stirred to conduct an oligomerization reaction. When the reaction solution was examined by gas chromatography, the conversion ratio of the monomer to the oligomer was 50%.
The reaction solution was dropped into a large amount of isopropyl alcohol to precipitate oligomers, and then applied under a pressure of 0.25 MPa using a pressure filter (Ishikawajima-Harima Heavy Industries, product name: Fundafilter). Pressure filtration was performed to obtain 20 parts of a gray powder.

Next, the obtained gray powder was dissolved in 200 parts of cyclohexane, 20 parts of an adsorbent (product name: Galeon Earth V2 manufactured by Mizusawa Chemical Co., Ltd.) was added to the obtained solution, and the mixture was stirred at 65 ° C. for 6 hours. . Then, using a pressure filter (Ishikawajima-Harima Heavy Industries Co., Ltd., product name: Fundafilter), and using diatomaceous earth (Showa Chemical Industry Co., Ltd., product name: Radiolite (registered trademark) # 500) as a filter bed. The solution was filtered under pressure at a pressure of 0.25 MPa to obtain a colorless and transparent solution.
Next, 0.5 parts of an antioxidant [manufactured by BASF Japan, product name: Irganox (registered trademark) 1010, tetrakis [methylene-3- (3 ′, 5 '-Di-t-butyl-4'-hydroxyphenyl) propionate] methane] was added.
This solution is filtered through a filter (Kyunoh Filter, product name: Zeta Plus (registered trademark) 30H, pore size 0.5-1 μm) and a metal fiber filter (Nichidai, pore size 0.4 μm). , Removed foreign matter.
Next, after removing the solvent (cyclohexane) and other volatile components from the filtrate under the conditions of a temperature of 260 ° C. and a pressure of 1 kPa or less using a cylindrical concentration dryer (manufactured by Hitachi, Ltd.), The melt was extruded as a strand from a directly connected die. The melt was cooled with water and then cut with a pelletizer (product name: OSP-2, manufactured by Nagata Seisakusho Co., Ltd.) to obtain a ring structure-containing hydrocarbon oligomer (1) pellet.
The weight average molecular weight of the ring structure-containing hydrocarbon oligomer (1) was 4,000.

[Production Example 3]
In Production Example 2, a pellet of the ring structure-containing hydrocarbon oligomer (2) was obtained in the same manner as in Production Example 2 except that 2,3-dihydroxydicyclopentadiene was used instead of tetracyclododecene. .
The weight average molecular weight of the ring structure-containing hydrocarbon oligomer (2) was 3,200.

[Production Example 4]
In Production Example 2, a ring-structure-containing hydrocarbon oligomer (3) pellet was obtained in the same manner as in Production Example 2 except that norbornene was used instead of tetracyclododecene.
The weight average molecular weight of the ring structure-containing hydrocarbon oligomer (3) was 5,000.

[Production Example 5]
In Production Example 2, a pellet of the ring structure-containing hydrocarbon oligomer (4) was obtained in the same manner as in Production Example 2 except that 25 parts of 1-hexene was added to carry out the oligomerization reaction.
The weight average molecular weight of the ring structure-containing hydrocarbon oligomer (4) was 1,100.

[Production Example 6]
In Production Example 1, a hydride of a ring-opened polymer [ring is obtained in the same manner as in Production Example 1 except that the addition amount of 1-hexene, which is a molecular weight regulator, is changed to 100 parts and a polymerization reaction is performed. A pellet of structure-containing hydrocarbon oligomer (5)] was obtained.
The weight average molecular weight of the ring structure-containing hydrocarbon oligomer (5) was 4,000.

[Production Example 7]
A ring structure-containing hydrocarbon oligomer (Production Example 2) was prepared in the same manner as in Production Example 2 except that the amount of tetrakis (acetonitrile) palladium (II) bis (tetrafluoroborate) used was changed to 0.05 part. The pellet of 6) was obtained.
The weight average molecular weight of the ring structure-containing hydrocarbon oligomer (6) was 15,500.

[Example 1]
70 parts of the cyclic olefin resin (1) obtained in Production Example 1 and 30 parts of the ring structure-containing hydrocarbon oligomer (1) obtained in Production Example 2 were mixed into a biaxial kneader (manufactured by Toshiba Machine Co., Ltd., product name: TEM- 35B) and extruded into a strand shape. This was cooled with water and cut with a pelletizer to obtain pellets.
After the obtained pellets were dried at 100 ° C. for 4 hours, a sheet-like resin molded body was obtained using an injection molding machine (manufactured by FANUC, ROBOSHOT (registered trademark) -2000i100A). Went.

[Example 2]
In Example 1, the resin composition was prepared in the same manner as in Example 1 except that the ring structure-containing hydrocarbon oligomer (2) obtained in Production Example 3 was used instead of the ring structure-containing hydrocarbon oligomer (1). It prepared and the resin molding was obtained using this.

Example 3
The resin composition was obtained in the same manner as in Example 1 except that the ring structure-containing hydrocarbon oligomer (3) obtained in Production Example 4 was used in place of the ring structure-containing hydrocarbon oligomer (1). It prepared and the resin molding was obtained using this.

Example 4
The resin composition was obtained in the same manner as in Example 1 except that the ring structure-containing hydrocarbon oligomer (4) obtained in Production Example 5 was used in place of the ring structure-containing hydrocarbon oligomer (1). It prepared and the resin molding was obtained using this.

Example 5
In Example 1, a resin composition was prepared in the same manner as in Example 1 except that 95 parts of the cyclic olefin resin (1) and 5 parts of the ring structure-containing hydrocarbon oligomer (1) were used. A resin molding was obtained.

[Comparative Example 1]
In Example 1, instead of the cyclic olefin resin (1), a commercially available cyclic olefin resin [ZEONEX 480R, manufactured by Nippon Zeon Co., Ltd.] was used, and the ring obtained in Production Example 6 was used instead of the ring structure-containing hydrocarbon oligomer (1). A resin composition was prepared in the same manner as in Example 1 except that the structure-containing hydrocarbon oligomer (5) was used, and a resin molded product was obtained using the resin composition.

[Comparative Example 2]
In Example 1, a resin composition was prepared in the same manner as in Example 1 except that a polystyrene oligomer (Mw: 3300) was used instead of the ring structure-containing hydrocarbon oligomer (1), and a resin composition was prepared using this resin composition. A molded body was obtained.

[Comparative Example 3]
In Example 1, the resin composition was obtained in the same manner as in Example 1 except that the ring structure-containing hydrocarbon oligomer (6) obtained in Production Example 7 was used instead of the ring structure-containing hydrocarbon oligomer (1). It prepared and the resin molding was obtained using this.

[Comparative Example 4]
In Example 1, a resin composition was prepared in the same manner as in Example 1 except that a commercially available cyclic olefin resin (manufactured by Zeon Corporation, ZEONEX 330R) was used instead of the cyclic olefin resin (1). A resin molding was obtained.

  The test results in Examples 1 to 5 and Comparative Examples 1 to 4 are shown in Tables 1 and 2.

From Tables 1 and 2, the following can be understood.
The resin compositions of Examples 1 to 5 are excellent in transparency and have a high refractive index, a high Abbe number, and a low linear expansion coefficient.
On the other hand, the resin composition of Comparative Example 1 has a low refractive index, the resin composition of Comparative Example 2 has a low Abbe number, and the resin composition of Comparative Example 3 has poor transparency. Moreover, the resin composition of Comparative Example 4 has a low refractive index and a high linear expansion coefficient.

Claims (7)

The weight average molecular weight (Mw) is more than 15,000 and not more than 150,000, and the ratio of the number of carbon atoms to the number of hydrogen atoms (number of carbon atoms / number of hydrogen atoms) of the repeating unit having a ring structure is 0.00. 60-0.70 cyclic olefin resin;
The weight average molecular weight (Mw) is more than 500 and not more than 15,000, and the ratio of the number of carbon atoms to the number of hydrogen atoms (number of carbon atoms / number of hydrogen atoms) of the repeating unit having a ring structure is 0.65 to A 1.00 ring structure-containing hydrocarbon oligomer,
It is a resin composition contained in a weight ratio (cyclic olefin resin: ring structure-containing hydrocarbon oligomer) in the range of 99: 1 to 30:70,
A resin composition having a refractive index of light having a wavelength of 587.6 nm of 1.530 to 1.600 and an Abbe number (ν _d ) of 45 to 60.   The resin composition according to claim 1, wherein the cyclic olefin resin is a hydride of a ring-opening polymer of a cyclic olefin monomer.   The resin composition according to claim 1 or 2, wherein the ring structure-containing hydrocarbon oligomer is a hydrocarbon oligomer having an alicyclic structure in the main chain and / or side chain.   The resin composition according to any one of claims 1 to 3, wherein the ring structure-containing hydrocarbon oligomer is a homo-oligomer obtained by addition polymerization of a cyclic olefin monomer.   The resin molding obtained by shape | molding the resin composition in any one of Claims 1-4.   The resin molding according to claim 5, wherein the molding method is injection molding.   The optical member which consists of a resin molding of Claim 5 or 6.