JP5642351B2 - Optical component and resin composition comprising injection-molded body - Google Patents

Description

  The present invention relates to an optical component comprising an injection-molded body formed from a resin composition containing polystyrene and a cyclic olefin resin.

  Conventionally, injection molded articles such as optical parts for which glass has been used are also being replaced with plastics that are excellent in productivity, impact resistance and light weight. For example, lenses for digital cameras, lenses for mobile phones, optical lenses represented by CDs, pickup lenses for Blu-rays and microlenses, substrates such as disks, light guide plates and prism sheets, polycarbonate, polymethyl methacrylate and cyclic olefins The use of resin is progressing. However, polycarbonate has a large birefringence, and polymethyl methacrylate has problems such as low heat resistance and high water absorption.

  Cyclic olefin-based resin has a high glass transition temperature and light transmittance, and also has a low birefringence compared to conventional optical resins because of its low refractive index anisotropy. It attracts attention as a thermoplastic resin excellent in heat resistance, transparency and optical properties. Utilizing such characteristics, for example, in the fields of optical and optical lenses, optical fibers, transparent plastic substrates, electronic and optical materials such as low dielectric materials, and sealing materials such as optical semiconductor sealing, cyclic olefin-based resins Application of is being studied.

  However, although the cyclic olefin resin is excellent in transparency, low water absorption and low birefringence, the refractive index is lower than that of optical glass in lens applications. The current situation is not. Therefore, in addition to the characteristics of the cyclic olefin-based resin described above, development of a cyclic olefin-based resin having high refractive properties is strongly desired.

  In general, it is known that the refractive index of a resin is improved by containing an aromatic ring, a halogen atom or a sulfur atom, and an aromatic ring, a halogen atom and a sulfur atom are introduced into a cyclic olefin resin. It has been studied to blend a heterogeneous polymer containing an aromatic ring, a halogen atom and a sulfur atom into a cyclic olefin resin. For example, Patent Document 1 shows that a ring-opening polymer of a norbornene derivative containing an aromatic ring has a high refractive index. Patent Documents 2 to 5 propose a blend of a cyclic olefin resin and a styrene resin, although there is no mention of the refractive index. However, the former aromatic ring-containing norbornene-based ring-opening polymer has a problem in that it tends to be expensive because the production of the monomer used and the ring-opening polymerization catalyst are expensive. In most cases, the resin blend is very difficult to obtain a transparent injection-molded product because phase separation occurs at a high temperature of 200 to 300 ° C. corresponding to the injection molding temperature. In addition, if it is attempted to maintain transparency without causing phase separation, there is a problem in that the amount of styrene resin added is limited and desired optical characteristics cannot be obtained.

  Therefore, a resin composition that can suppress phase separation and easily obtain a transparent optical component even by using a molding method under high temperature, and a highly transparent lens having the resin composition as a main component, etc. The appearance of optical components has been strongly desired. Moreover, a new method for achieving a high refractive index using an inexpensive material has been desired.

Japanese Patent No. 3291857 Japanese Patent No. 3775052 JP 2006-188555 A JP 2001-337222 A Japanese Patent No. 3018378

  It is an object of the present invention to provide an optical component made of an injection-molded body having a high refractive index and excellent transparency.

  As a result of intensive studies to solve the above problems, the present inventors have found that the present invention achieves the above problems.

  That is, the present invention includes the following matters.

  [1] (A) 1 to 40 parts by weight of polystyrene having a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 1,000 to 5,000, and (B) glass An optical component comprising an injection-molded article formed from a resin composition containing 100 parts by weight of a cyclic olefin resin having a transition temperature (Tg) of 100 to 180 ° C.

  [2] The optical component comprising the injection-molded article according to [1], wherein the polystyrene (A) has a weight average molecular weight (Mw) of 2,000 to 4,500.

  [3] The optical component comprising the injection-molded article according to [1] or [2], wherein a weight reduction rate when the polystyrene (A) is heated at 250 ° C. for 1 hour is 7% or less.

  [4] The polystyrene-converted molecular weight distribution (Mw / Mn) of the polystyrene (A) measured by gel permeation chromatography (GPC) is 1.0 to 4.0 [1] to [1] 3] An optical component comprising the injection-molded article according to any one of the above.

  [5] The injection molding according to any one of [1] to [4], wherein the cyclic olefin resin (B) has a structural unit derived from a compound represented by the following formula (1): An optical component consisting of a body.

In formula (1), R < ¹ > -R < ⁴ > is a hydrogen atom, a halogen atom, a C1-C30 hydrocarbon group, or another monovalent organic group, and may be the same or different. R ¹
Any two of ˜R ⁴ may be bonded to each other to form a monocyclic or polycyclic structure. m is 0 or a positive integer, and p is 0 or a positive integer.

  [6] The fog value of a 3.2 mm thick molded plate formed by injection molding from the resin composition at a heating temperature of 300 ° C. is 1% or less, according to [1] to [5] An optical component comprising the injection molded article according to any one of the above.

  [7] An optical component comprising the injection-molded article according to any one of [1] to [6], which is a lens.

  [8] (A) 1 to 40 parts by weight of polystyrene having a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 1,000 to 5,000, and (B) glass A resin composition comprising 100 parts by weight of a cyclic olefin resin having a transition temperature (Tg) of 100 to 180 ° C.

  The resin composition according to the present invention is obtained by containing polystyrene in a specific cyclic olefin-based resin, and by using the resin composition, an optical component made of an injection-molded body having a high refractive index can be provided.

  The resin composition according to the present invention can provide an optical component made of a highly transparent injection-molded body without phase separation even when heated at a high temperature when processing the optical component made of an injection-molded body.

  The optical component comprising the injection-molded article of the present invention is a polystyrene (A) having a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 1,000 to 5,000 (hereinafter simply referred to as “polystyrene”). 1-40 parts by weight and a cyclic olefin resin (B) having a glass transition temperature (Tg) of 100-180 ° C. (hereinafter simply referred to as “cyclic olefin resin (B)”) It is formed from a resin composition containing 100 parts by weight.

  Hereinafter, the optical component and resin composition comprising the injection-molded body according to the present invention will be described in detail.

[Polystyrene (A)]
As the polystyrene (A) according to the present invention, those produced by a known method or commercially available products can be used without particular limitation. Examples of commercially available products include SX100 (manufactured by Yasuhara Chemical Co., Ltd.) and Regit S94 (manufactured by Sanyo Chemical Industries, Ltd.). Polystyrene (A) may be used individually by 1 type, and 2 or more types may be mixed and used for it.

The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of polystyrene (A) is 1,000 to 5,000, preferably 2,000 to 4,500, more preferably 2, 500-4,500. If Mw is smaller than 1,000, the strength of the optical component made of an injection molded body may be lowered. On the other hand, if Mw is greater than 5,000, the compatibility with the cyclic olefin resin (B) deteriorates, and the improvement in the refractive index cannot be made compatible to the effective range. The transparency of parts may be reduced.

The molecular weight distribution (Mw / Mn) of polystyrene (A) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.1 to 3.5, and particularly preferably 1.2 to 2
. 5. When Mw / Mn is larger than 4.0, the compatibility with the cyclic olefin resin (B) is deteriorated, and the haze of the optical component made of an injection-molded product may be increased.

  The polystyrene (A) has a weight reduction rate of preferably 7% or less, more preferably 6% or less when heated at 250 ° C. for 1 hour. If the weight reduction rate is larger than 7%, gas generation may occur during molding, and the mold of the injection molding machine may be soiled.

  Content of the polystyrene (A) in the resin composition which concerns on this invention is 1-40 weight part with respect to 100 weight part of cyclic olefin resin (B), Preferably it is 5-40 weight part. If the polystyrene (A) content is outside the range of 1 to 40 parts by weight, the compatibility between the polystyrene (A) and the cyclic olefin resin (B) is poor, and the optical component made of the resulting injection-molded product becomes cloudy. There is a case.

[Cyclic olefin resin (B)]
Examples of the cyclic olefin resin (B) according to the present invention include the following (co) polymers.
(I) A ring-opening polymer of the compound represented by the formula (1).
(Ii) A ring-opening copolymer of the compound represented by formula (1) and a copolymerizable monomer.
(Iii) A hydrogenated (co) polymer of the ring-opening (co) polymer of (i) or (ii).
(Iv) A (co) polymer obtained by cyclization of the ring-opening (co) polymer of (i) or (ii) by Friedel-Craft reaction and then hydrogenation.
(V) A saturated copolymer of the compound represented by formula (1) and an unsaturated double bond-containing compound.
(Vi) an addition type (co) polymer of one or more monomers selected from a compound represented by the formula (1), a vinyl cyclic hydrocarbon monomer and a cyclopentadiene monomer, and hydrogen thereof Addition (co) polymer.
(Vii) An alternating copolymer of a compound represented by formula (1) and an acrylate.

  Among these, (iii) is preferable from the viewpoint of the compatibility with polystyrene (A) and the transparency of the optical component made of the obtained injection molded article.

In said formula (1), R < ¹ > -R < ⁴ > is a hydrogen atom, a halogen atom, a C1-C30 hydrocarbon group, or another monovalent organic group, and may respectively be the same or different. Further, any two of R ^{1 to} R ⁴ may be bonded to each other to form a monocyclic or polycyclic structure.

R ¹ and R ³ are preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably an alkyl group having 1 to 2 carbon atoms, and most preferably a methyl group. The alkyl group is - (CH ₂₎ If the polar group represented by _n COOR are attached to the same carbon atom and a carbon atom bonded, since low moisture absorption of the cyclic olefin-based resin (B) preferably.

R ² and R ⁴ are preferably a hydrogen atom or other monovalent organic group, and at least one of R ² and R ⁴ is preferably a polar group.

  Examples of the polar group include a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amino group, an amide group, and a cyano group. These polar groups may be bonded via a linking group such as a methylene group, and further include divalent organic groups such as a carbonyl group, an ether group, a silyl ether group, a thioether group, and an imino group. May be. Among these polar groups, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, and an allyloxycarbonyl group are preferable, and an alkoxycarbonyl group and an allyloxycarbonyl group are more preferable.

When at least one of R ² and R ⁴ is a polar group represented by — (CH ₂ ) _n COOR, the obtained cyclic olefin-based resin (B) has a high glass transition temperature, low hygroscopicity, and various materials. It has excellent adhesion. In — (CH ₂ ) _n COOR, R is a hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, particularly preferably an alkyl having 1 to 2 carbon atoms. N is 0-5, preferably 0-3. The smaller the value of n, the higher the glass transition temperature of the cyclic olefin resin (B), which is preferable. When n = 0, the synthesis is easy and particularly preferable.

  m is 0 or a positive integer, p is 0 or a positive integer, preferably m is an integer of 0 to 3, p is an integer of 0 to 3, more preferably m + p = 0 to 4, Preferably m + p = 0-2, particularly preferably m = 1 and p = 0. When m = 1 and p = 0, the cyclic olefin resin (B) has a high glass transition temperature and is excellent in mechanical strength, which is particularly preferable.

Specific examples of the compound represented by the above formula (1) include the following compounds, but the present invention is not limited to these specific examples.
Bicyclo [2.2.1] hept-2-ene,
Tricyclo [4.3.0.1 ^2,5 ] -8-decene,
Tricyclo [4.4.0.1 ^2,5 ] -3-undecene,
Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene,
5-methylbicyclo [2.2.1] hept-2-ene,
5-ethylbicyclo [2.2.1] hept-2-ene,
5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene,
5-cyanobicyclo [2.2.1] hept-2-ene,
8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,

8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene,
8-methyl-8-ethoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene,
8-methyl-8-n-propoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] -3-dodecene,
8-methyl-8-isopropoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] -3-dodecene,
8-methyl-8-n-butoxycarbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]
-3-dodecene,
5-ethylidenebicyclo [2.2.1] hept-2-ene,
8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
5-phenylbicyclo [2.2.1] hept-2-ene,
8-phenyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
5-fluorobicyclo [2.2.1] hept-2-ene,
5-fluoromethylbicyclo [2.2.1] hept-2-ene,
5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-pentafluoroethylbicyclo [2.2.1] hept-2-ene,
5,5-difluorobicyclo [2.2.1] hept-2-ene,
5,6-difluorobicyclo [2.2.1] hept-2-ene,
5,5-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5-methyl-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5,5,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrafluorobicyclo [2.2.1] hept-2-ene,
5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

5,5-difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-fluoro-5-pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,6-difluoro-5-heptafluoro-isopropyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene,
5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene,
5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene,
5,5,6-trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene,
8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-fluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-difluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-pentafluoroethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene,

8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene,
8-methyl-8-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3
-Dodecene,
8,8,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-tris (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10
] -3-dodecene,
8,8,9,9-tetrafluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9,9-tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5
. 1 ^7,10 ] -3-dodecene,
8,8-difluoro-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluoro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5
. 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-trifluoromethoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,8,9-trifluoro-9-pentafluoropropoxytetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-fluoro-8-pentafluoroethyl-9,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-difluoro-8-heptafluoroisopropyl-9-trifluoromethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-chloro-8,9,9-trifluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
3-dodecene,

8,9-dichloro-8,9-bis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8-methyl-8- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene.

  These can be used alone or in combination of two or more.

Copolymerizable monomer Specific examples of the copolymerizable monomer (ii) above include cycloolefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene, and dicyclopentadiene.

The number of carbon atoms of the cycloolefin is preferably 4-20, more preferably 5-12. These cycloolefins can be used alone or in combination of two or more.

  A preferred use ratio of the compound / copolymerizable monomer represented by the formula (1) is preferably 100/0 to 50/50, more preferably 100/0 to 60/40 in terms of weight ratio.

Ring-opening polymerization catalyst In the present invention, a ring-opening polymer of the compound represented by formula (1) of (i) above, and a compound and a copolymerizable monomer represented by formula (1) of (ii) above The ring-opening polymerization reaction for obtaining a ring-opening copolymer is carried out in the presence of a metathesis catalyst.

  The metathesis catalyst comprises (a) at least one selected from W, Mo and Re compounds, (b) a Deaming Periodic Table Group IA element (for example, Li, Na and K), IIA Group element (for example, , Mg and Ca), Group IIB elements (eg Zn, Cd and Hg etc.), Group IIIA elements (eg B and Al etc.), Group IVA elements (eg Si, Sn and Pb etc.), or Group IVB A catalyst comprising a compound of an element (for example, Ti, Zr, etc.), wherein the compound having at least one of the element-carbon bond and the element-hydrogen bond is used singly or in combination. Moreover, in order to improve catalyst activity, what added the other additive mentioned later may be used.

Suitable compounds of W, Mo and Re as component (a) include, for example, WCl ₆ , M
Examples include oCl ₆ and ReOCl _{3 described} in JP-A No. 1-132626, page 8, lower left column, line 6 to page 8, upper right column, line 17.

As component (b), for _{example, n-C 4 H 9 Li} , (C 2 H 5) 3 Al, (C 2 H 5) 2 AlCl, (C 2 H 5) 1.5 AlCl 1.5, (C 2 H 5 ) AlCl ₂ , methylalumoxane and Li
Examples thereof include compounds described in JP-A No. 1-132626, page 8, upper right column, line 18 to page 8, lower right column, line 3.

  Examples of other additives include alcohols, aldehydes, ketones and amines. For example, JP-A-1-132626, page 8, lower right column, line 16 to page 9, upper left column, line 17 Preferred examples include the compounds described in 1.).

  As a usage-amount of a metathesis catalyst, the ratio (component (a): compound represented by Formula (1)) of the said component (a) and the compound represented by Formula (1) is 1: 500- in molar ratio. It is preferably 1: 50,000, more preferably 1: 1,000 to 1: 10,000.

  The ratio of the component (a) to the component (b) ((a) :( b)) is preferably 1: 1 to 1:50 in terms of metal atom ratio, and is 1: 2 to 1:30. More preferably.

Solvent for polymerization reaction The solvent used in the ring-opening polymerization reaction is not particularly limited as long as it can dissolve the molecular weight regulator, the compound represented by the above formula (1), and the metathesis catalyst. For example, alkanes such as pentane, hexane, heptane, octane, nonane and decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin and norbornane; aromatic carbonization such as benzene, toluene, xylene, ethylbenzene and cumene Hydrogen; chlorobutane, bromohexane, methylene chloride, dichloroethane, hexamethylene dibromide, halogenated alkanes such as chlorobenzene, chloroform and tetrachloroethylene; compounds such as aryl halides; ethyl acetate, n-butyl acetate, vinegar Isobutyl, saturated carboxylic acid esters such as methyl propionate and dimethoxyethane; and dibutyl ether, and the like ethers such as tetrahydrofuran and dimethoxyethane. Of these, aromatic hydrocarbons are preferred. These can be used alone or in admixture of two or more.

  Moreover, as the usage-amount of a solvent, the ratio (solvent: the compound represented by Formula (1)) of the usage-amount of a solvent and the compound represented by Formula (1) is 1: 1-10: 1 is preferable, and 1: 1 to 5: 1 is more preferable.

Molecular Weight Modifier The molecular weight of the ring-opening (co) polymer can be adjusted according to the polymerization temperature, the type of catalyst and the type of solvent. In the present invention, the molecular weight regulator is allowed to coexist in the reaction system. Adjust.

  Here, examples of the molecular weight regulator include α-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene, and styrene. Etc. Of these, 1-butene and 1-hexene are preferable.

  These molecular weight regulators can be used alone or in admixture of two or more.

  The amount of the molecular weight regulator used is preferably 0.005 to 0.6 mol, more preferably 0.02 to 1 mol of the compound represented by the above formula (1) subjected to the ring-opening polymerization reaction. 0.5 mole.

  In order to obtain the ring-opening copolymer of (ii), in the ring-opening polymerization step, the compound represented by the above formula (1) and the copolymerizable monomer may be ring-opening copolymerized, If necessary, two or more carbon-carbon double bonds in the main chain, such as conjugated diene compounds such as polybutadiene and polyisoprene, styrene / butadiene copolymers, ethylene / nonconjugated diene copolymers, and polynorbornene. The compound represented by the above formula (1) may be subjected to ring-opening polymerization in the presence of an unsaturated hydrocarbon polymer or the like.

  The ring-opening (co) polymer obtained as described above can be used as it is, but the hydrogenated (co) polymer (iii) obtained by further hydrogenation of the polymer has an impact resistance. It is also suitably used as a raw material for large resins.

Hydrogenation catalyst The hydrogenation reaction is a commonly used method, that is, a hydrogenation catalyst is added to a solution of a ring-opening polymer, and hydrogen gas at normal pressure to 300 atm, preferably 3 to 200 atm, is added thereto at 0 to 200 ° C. The reaction is preferably carried out at a temperature of 20 to 180 ° C.

  As a hydrogenation catalyst, what is used for the hydrogenation reaction of a normal olefinic compound can be used. Examples of the hydrogenation catalyst include a heterogeneous catalyst and a homogeneous catalyst.

  Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst material such as palladium, platinum, nickel, rhodium and ruthenium is supported on a support such as carbon, silica, alumina and titania.

Examples of homogeneous catalysts include nickel naphthenate / triethylaluminum, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, chlorotris (triphenylphosphine) rhodium. Dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium, and the like. The form of the catalyst may be powder or granular.

In these hydrogenation catalysts, the ratio of the ring-opening (co) polymer and the hydrogenation catalyst is preferably 1: 1 × 10 ⁻⁶ to 1: 2 by weight.

  Thus, the hydrogenated (co) polymer obtained by hydrogenation has excellent thermal stability, and its properties deteriorate due to heating during molding and use as a product. There is no. Here, the hydrogenation rate is usually 50% or more, preferably 70% or more, more preferably 90% or more, and particularly preferably 99% or more.

The hydrogenation rate of the hydrogenated (co) polymer is usually 50% or more, preferably 90% or more, more preferably 98% or more, particularly preferably 99% or more, as measured by 500 MHz and ¹ H-NMR. It is. The higher the hydrogenation rate, the better the stability to heat and light, and when used as an optical component comprising the injection molded article of the present invention, stable characteristics can be obtained over a long period of time.

  The hydrogenated (co) polymer used as the cyclic olefin resin (B) according to the present invention preferably has a gel content of 5% by weight or less contained in the hydrogenated (co) polymer. More preferably, it is 1% by weight or less.

  In addition, as the cyclic olefin resin (B) according to the present invention, the ring-opening (co) polymer of (iv) above (i) or (ii) is cyclized by Friedel-Craft reaction, and then hydrogenated. (Co) polymers are also used.

The method of cyclizing the cyclized ring- opening (co) polymer by Friedel-Craft reaction is not particularly limited, but an acidic compound described in JP-A-50-154399 was used. A known method is used. Specifically, Lewis acids such as AlCl ₃ , BF ₃ , FeCl ₃ , Al ₂ O ₃ , HCl, CH ₂ ClCOOH, zeolite and activated clay, and Bronsted acid are used as the acidic compound.

  The ring-opening (co) polymer cyclized by the Friedel-Craft reaction can be hydrogenated in the same manner as the hydrogenation method for the ring-opening (co) polymer (i) or (ii) described above.

  Furthermore, as the cyclic olefin resin (B) according to the present invention, a saturated copolymer of the compound represented by the above formula (1) of the above (v) and an unsaturated double bond-containing compound is also used.

Unsaturated double bond-containing compound Examples of the unsaturated double bond-containing compound (v) above include olefinic compounds having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, such as ethylene, propylene and butene. It is done.

  The ratio of the compound represented by the formula (1) and the unsaturated double bond-containing compound is preferably 90/10 to 40/60, more preferably 85/15 to 50/50, by weight. preferable.

  The saturated copolymer of the compound represented by the formula (1) and the unsaturated double bond-containing compound can be produced using a commonly used addition polymerization method.

Addition Polymerization Catalyst As the addition polymerization catalyst for synthesizing the saturated copolymer of (v) above, at least one selected from a titanium compound, a zirconium compound and a vanadium compound and an organoaluminum compound as a cocatalyst are used.

Examples of the titanium compound include titanium tetrachloride and titanium trichloride, and examples of the zirconium compound include bis (cyclopentadienyl) zirconium chloride and bis (cyclopentadienyl) zirconium dichloride. As the vanadium compound, the general formula VO (OR) _a X _b or V (OR) _c X _d [wherein R is a hydrocarbon group, X is a halogen atom, and 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ (a + b) ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ (c + d) ≦ 4. Or an electron donor adduct of these compounds.

  Examples of the electron donor include oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides and alkoxysilanes, ammonia, amines, And nitrogen-containing electron donors such as nitrile and isocyanate.

  As the organoaluminum compound as a promoter, an organoaluminum compound having at least one of an aluminum-carbon bond and an aluminum-hydrogen bond is used.

  For example, when the vanadium compound is used, the ratio of the vanadium compound to the organoaluminum compound is 2 or more, preferably 2 to 50, more preferably 3 to 20 in terms of the ratio of aluminum atom to vanadium atom (Al / V).

  As the solvent for the polymerization reaction used for the addition polymerization, the same solvent as that used for the ring-opening polymerization reaction is used. The molecular weight of the resulting saturated copolymer (v) is usually adjusted using hydrogen.

  Further, as the cyclic olefin resin (B) according to the present invention, 1 selected from the compound represented by the formula (1) of (vi), a vinyl cyclic hydrocarbon monomer, and a cyclopentadiene monomer. Addition (co) polymers of more than one monomer and hydrogenated (co) polymers thereof can also be used.

Vinyl Cyclic Hydrocarbon Monomer As the vinyl cyclic hydrocarbon monomer (vi) above, for example, vinyl cyclopentene monomers such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene Vinylated 5-membered ring hydrocarbon monomers such as vinylcyclopentane monomers such as 4-vinylcyclopentane and 4-isopropenylcyclopentane; 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl Vinylcyclohexene monomers such as -4-isopropenylcyclohexene, 2-methyl-4-vinylcyclohexene and 2-methyl-4-isopropenylcyclohexene; such as 4-vinylcyclohexane and 2-methyl-4-isopropenylcyclohexane Vinyl cyclohexane type Styrene monomers such as styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-phenylstyrene and p-methoxystyrene; Terpene monomers such as d-terpenes, 1-terpenes, diterpenes, d-limonene, 1-limonene and dipentene; vinylcycloheptene-based monomers such as 4-vinylcycloheptene and 4-isopropenylcycloheptene And vinyl cycloheptane monomers such as 4-vinylcycloheptane and 4-isopropenylcycloheptane. Of these, styrene and α-methylstyrene are preferable. These may be used alone or in combination of two or more.

Cyclopentadiene monomer The cyclopentadiene monomer used as the monomer of the addition (co) polymer of (vi) above includes, for example, cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene , 2-ethylcyclopentadiene, 5-methylcyclopentadiene, 5,5-dimethylcyclopentadiene, and the like. Of these, cyclopentadiene is preferred. These can be used alone or in combination of two or more.

  An addition type (co) polymer of at least one monomer selected from the compound represented by the above formula (1), a vinyl-based cyclic hydrocarbon-based monomer, and a cyclopentadiene-based monomer is (v) In the same manner as the saturated copolymer of the compound represented by the formula (1) and the unsaturated double bond-containing compound, it can be produced by an addition polymerization method.

  Further, the hydrogenation (co) polymer of the addition type (co) polymer is the hydrogenation of the ring-opening (co) polymer of the above (iii) (i) or (ii). Hydrogenation can be performed in the same manner as in the method.

  Furthermore, as the cyclic olefin resin (B) according to the present invention, an alternating copolymer of a compound represented by the formula (1) in the above (vii) and acrylates is also used.

Acrylates In the above (vii), examples of the acrylates used in the production of the alternating copolymer of the compound represented by the formula (1) and acrylates include methyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate. A linear, branched or cyclic alkyl acrylate having 1 to 20 carbon atoms; a heterocyclic group-containing acrylate having 2 to 20 carbon atoms such as glycidyl acrylate and 2-tetrahydrofurfuryl acrylate; and 6 to 6 carbon atoms such as benzyl acrylate Examples thereof include 20 aromatic ring group-containing acrylates; acrylates having a polycyclic structure having 7 to 30 carbon atoms such as isobornyl acrylate and dicyclopentanyl acrylate.

  In the present invention, in order to obtain an alternating copolymer of the compound represented by formula (1) of the above (vii) and acrylates, the compound represented by formula (1) and acrylates in the presence of a Lewis acid. The amount of the compound represented by the formula (1) is usually 30 to 70 mol, and the amount of the acrylate is 70 to 30 mol, preferably 40 to the compound represented by the formula (1). Radical polymerization is carried out using ˜60 mol, acrylates in an amount of 60 to 40 mol, particularly preferably 45 to 55 mol of the compound represented by the formula (1) and acrylates in an amount of 55 to 45 mol.

  The amount of the Lewis acid used to obtain the alternating copolymer of the compound represented by the above formula (1) and the acrylate in (vii) is usually 0.001-1 with respect to 100 moles of the acrylate. Is a mole. Moreover, you may use the organic peroxide or azo radical polymerization initiator which generate | occur | produces a well-known free radical, and polymerization reaction temperature is -20-80 degreeC normally, Preferably it is 5-60 degreeC.

  As the solvent for the polymerization reaction, the same solvent as that used in the ring-opening polymerization reaction can be used.

  The “alternate copolymer” as used in the present invention is a structure in which the structural unit derived from the compound represented by the above formula (1) is not adjacent, that is, derived from the compound represented by the above formula (1). The unit next to the unit always means a copolymer having a structural unit derived from acrylate, and does not deny the structure in which structural units derived from acrylate are adjacent to each other.

The preferred molecular weight of the cyclic olefin resin (B) according to the present invention is 0.2 to 5 dl / g, more preferably 0.3 to 3 dl / g, particularly preferably 0.4 to 1 in terms of intrinsic viscosity [η] _inh. The polystyrene-reduced number average molecular weight (Mn) measured by gel permeation chromatography (GPC) after being dissolved in tetrahydrofuran is preferably 8,000 to 100,000, more preferably 10,000. -80,000, particularly preferably 12,000-50,000, and the weight average molecular weight (Mw) is preferably 20,000-300,000, more preferably 30,000-250,000, particularly preferably 40,000-200,000. Moreover, molecular weight distribution (Mw / Mn) becomes like this. Preferably it is 2.0-4.0, More preferably, it is 2.5-3.7, Most preferably, it is 2.8-3.5. By using a resin having a small molecular weight distribution (Mw / Mn), a resin composition in which phase separation hardly occurs during heating, that is, a resin composition having a small melt flow rate (MFR) variation can be obtained.

When the intrinsic viscosity [η] _inh , number average molecular weight (Mn), and weight average molecular weight (Mw) are in the above ranges, the cyclic olefin resin (B) has heat resistance, water resistance, chemical resistance and mechanical properties. This improves the moldability of the optical component made of the injection molded article of the present invention.

  The glass transition temperature (Tg) of the cyclic olefin-based resin (B) according to the present invention is usually 100 to 180 ° C, preferably 110 to 175 ° C, more preferably 120 to 170 ° C, and particularly preferably 130 to 170 ° C. It is. When Tg is less than 100 ° C., it may be deformed during use under high temperature conditions or during secondary processing such as coating and printing. On the other hand, if Tg exceeds 180 ° C., the resin deteriorates due to heat during the molding process, and the molding process may be difficult.

  As described above, the cyclic olefin resin (B) preferably has a smaller molecular weight distribution (Mw / Mn). In the (co) polymers of the above (i) to (vii), in order to obtain a resin having a small molecular weight distribution (Mw / Mn), it is preferable to perform ring-opening polymerization or addition polymerization in multiple stages.

  For example, in the multistage polymerization of the ring-opening (co) polymer of the above (i) or (ii), after a polymerization tank is arranged in series and a monomer component and a catalyst component are supplied to the polymerization tank, a certain time is passed. After the lapse of time, a mixed liquid of the monomer component partially polymerized, the polymer component, and the catalyst component is supplied continuously or batchwise to the polymerization vessel of the next stage. While supplying said component to the polymerization tank of the next stage, a new monomer component and a catalyst component are supplied, further polymerization is performed, and the mixed liquid component is supplied to the polymerization tank of the next stage. Polymerization is carried out in the third stage polymerization tank in the same manner as in the second stage. By such a method, the conversion rate to the polymer is at least 80% or more, preferably 85% or more, more preferably 88% or more, particularly preferably. May be 90% or more.

  Moreover, the multistage polymerization in the case of the addition (co) polymerization of (v) to (vii) can also be performed according to the ring-opening polymerization.

The cyclic olefin resin (B) according to the present invention has a logarithmic viscosity [η] measured in a chlorobenzene solution (concentration of 0.5 g / dL) at 30 ° C. of 0.3 to 1.0 dL / g. preferable. Moreover, the weight average molecular weight (Mw) of polystyrene conversion measured by the gel permeation chromatography (GPC) of cyclic olefin resin (B) is 1.1-5.
0, preferably 1.5 to 4.5, more preferably 1.8 to 4.2.

  If the molecular weight is too small, the strength of the optical component made of the obtained injection-molded product may be lowered. On the other hand, when the molecular weight is too large, the solution viscosity becomes too high, and the productivity and workability of the resin composition according to the present invention may be deteriorated.

[Other additives]
If necessary, an antioxidant and an ultraviolet absorber may be added to the optical component comprising the injection-molded article of the present invention in order to improve the hydrocarbon resin or the heat resistance and light resistance.

  Hydrocarbon resins include C5 resin, C9 resin, C5 / C9 mixed resin, cyclopentadiene resin, copolymer resin of olefin and vinyl-substituted aromatic compound, cyclopentadiene compound, and vinyl-substituted aromatic. Examples thereof include copolymer based resins, hydrogenated products of these resins, and hydrogenated products of vinyl-substituted aromatic resins. Content of hydrocarbon resin is 1-50 weight part normally with respect to 100 weight part of cyclic olefin resin (B), Preferably it is 5-30 weight part.

Antioxidants include 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane, tetrakis [methylene -3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) ) Propionate, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-diethylphenylmethane, 3,9-bis [1,1-dimethyl-2- (β- (3- t-butyl-4-hydroxy-5-methylphenyl) propionyl Oxy) ethyl], 2,4,8,10-tetraoxaspiro [5.5] undecane, tris (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4 -Di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,6-di-t-butyl-
4-methylphenyl) phosphite and 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite.

As the UV absorber, 2,4-dihydroxybenzophenone, 2-hydroxy-4-
Methoxybenzophenone, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl)-
4,6-di-t-pentylphenol, 2-benzotriazol-2-yl 4,6-di-t-butylphenol and 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl ) -6- [
(2H-benzotriazol-2-yl) phenol]] and the like.

  Content of these additives is 0.01-10 weight part normally with respect to 100 weight part of cyclic olefin resin (B), Preferably it is 0.03-5 weight part.

  Furthermore, for the purpose of improving processability, an additive such as a lubricant and a dye or a fluorescent brightening agent may be added to improve the hue.

[Resin composition for optical parts comprising injection-molded article]
Examples of the resin composition for optical parts comprising the injection-molded article of the present invention include the following (I) to (III):
It can obtain by the method of.
(I) A method in which polystyrene (A), cyclic olefin resin (B) and other additives are mixed using a twin screw extruder or a roll kneader.
(II) A method in which polystyrene (A) and other additives are added to a solution in which the cyclic olefin resin (B) is dissolved in a suitable solvent, and then mixed using a suitable stirrer.
(III) A method in which polystyrene (A) or a solution thereof, a cyclic olefin resin (B) or a solution thereof, and other additives are mixed, and a solvent is removed using a devolatizer, a ruder, or the like.

  As a solvent used in this case, a general solvent such as a polymerization solvent used for production of polystyrene (A) or cyclic olefin-based resin (B) can be used.

[Optical parts made of injection-molded bodies]
The optical component comprising the injection-molded article of the present invention is injection-molded with an injection molding machine using a resin composition containing polystyrene (A), a cyclic olefin-based resin (B), and other additives as optional components. It is obtained by this.

  The haze value of a molded plate having a thickness of 3.2 mm formed from the resin composition according to the present invention by injection molding under heating at 300 ° C. is preferably 1% or less, more preferably 0.6% or less. .

  The injection molding machine is not particularly limited. For example, the cylinder method is an in-line method and a pre-plastic method; the driving method is hydraulic, electric and hybrid; the clamping method is direct pressure and toggle; the injection direction Examples include horizontal type and vertical type. The mold clamping method is preferably one that can be injection-compressed. The cylinder diameter and clamping force are determined by the shape of the target injection molded body. Generally, it is preferable to increase the clamping force when the projected area of the injection molded body is large, and the cylinder diameter when the capacity of the injection molded body is large. It is preferable to make this larger.

  When the cylinder is an in-line type, the screw shape such as compression ratio, length / diameter ratio, presence / absence of subflight can be selected as appropriate, and the surface of the screw is known such as chromium, titanium, nitride and carbon. The coating may be applied. Further, a mechanism for controlling the rotation and pressure of the screw may be provided in order to improve the stability of measurement and injection operation. Moreover, it is preferable from the viewpoint that the injection molded body can be stably obtained that the inside of the cylinder or the hopper for storing the resin composition is reduced in pressure, or the cylinder and the hopper are sealed with an inert gas such as nitrogen.

  At the time of injection molding, a method of reducing the pressure in the cavity of the mold apparatus or an injection compression method is preferably used in order to reduce warping of the injection-molded body and stable continuous molding.

  When injection molding is performed by reducing the pressure in the cavity of the mold apparatus, the degree of vacuum is a gauge pressure, preferably −0.08 MPa or less, more preferably −0.09 MPa or less, and particularly preferably −0.1 MPa or less. is there. When the above range is exceeded, the degree of reduced pressure is insufficient, and an injection molded article having excellent light transmittance and light diffusibility may not be obtained.

  The degree of vacuum in the above range is achieved using a known method such as a vacuum pump. At this time, it is preferable to use a known sealing material such as an O-ring around the cavity or the ejector mechanism, and it is also preferable to use vacuum grease or the like as long as impurities are not mixed into the injection molded body. In addition, a suction port for connecting to a decompression device such as a vacuum pump may be provided at an arbitrary location in the mold device, but usually in the ejector mechanism, the end of the sprue and runner, the nested structure, etc. Provided. The vacuum suction sequence may be controlled by an electromagnetic valve or the like in conjunction with opening and closing of the mold apparatus, or may be operated at all times, and a method of allowing the inside of the mold apparatus cavity to have a desired degree of pressure reduction when filling with molten resin If it is, it will not be restrict | limited in particular.

  When injection molding is performed by reducing the pressure in the cavity of the mold apparatus, the injection delay time is usually set in order to inject the molten resin in a state where the cavity is closed and the pressure is reduced. The injection delay time depends on the capacity of the vacuum pump used and the cavity size, but is usually about 0.5 to 3 seconds.

On the other hand, in the injection compression molding method, the cavity interval is set to 1.5 to 20 times the thickness of the injection molded body, the molten resin is injected into the gap, and the resin pressure measured on the cylinder side is 200 to 2 The surface of the injection-molded body in the mold apparatus may be compressed while keeping it in the range of 1,000 kgf / cm ² to narrow the interval between the cavities.

  Further, the core of the mold apparatus is set to a movable state by setting it to 1.1 to 10 times the thickness of the injection molded body, and the molten resin is injected there, and after the start of injection or the end of injection, the movable side core is averaged. The compression may be performed at a speed of 0.01 to 1 mm / sec.

  A known molding machine is used for these injection compression molding methods.

  Other conditions for injection molding are not particularly limited, but the cylinder temperature is usually 260 to 350 ° C., and the mold apparatus temperature is usually Tg-1 to 1 based on the glass transition temperature Tg of the resin composition. It is in the range of Tg-40 ° C, preferably Tg-5 to Tg-30 ° C. The injection speed varies depending on the size of the injection-molded article according to the present invention and the cylinder size of the molding machine. For example, when the cylinder diameter is 28 mm, it is usually 80 mm / sec or more, preferably 90 to 250 mm / sec. In the holding pressure, it is preferable to appropriately adjust the minimum pressure and time so that the shape of the injection molded body can be maintained.

  An optical component made of an injection-molded body formed from the resin composition according to the present invention is suitably used for an optical component such as a lens.

〔Example〕
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following Examples and Comparative Examples, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified.

[Evaluation of Cyclic Olefin Resin (B)]
<Weight average molecular weight (Mw)>
Gel permeation chromatograph (manufactured by Tosoh Corporation, HLC-8220GPC, column; guard column H _XL- H, Tosoh Corporation, TSK gel G7000H _XL , TSK gel)
Two GMH _XL and TSK gel G2000H _XL are sequentially connected, solvent: tetrahydrofuran, flow rate: 1 mL / min, sample concentration: 0.7-0.8 wt%, injection volume: 70 μL, measurement temperature: 40 ° C., detector; The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of polystyrene (A) and cyclic olefin-based resin (B) were measured using RI (40 ° C.), standard material; TSK standard polystyrene manufactured by Tosoh Corporation.

<Weight reduction rate (TGA)>
Using a TGA thermobalance (manufactured by SII, TG / DTA6200), heating was performed at 250 ° C. for 1 hour, and the weight reduction rate of polystyrene (A) was determined.

<Glass transition temperature (Tg)>
Using a differential scanning calorimeter (manufactured by SII, DSC6200), an extrapolated glass transition start temperature of the cyclic olefin-based resin (B) (hereinafter simply referred to as “glass transition temperature (Tg)”) is obtained according to Japanese Industrial Standard K7121. It was.

<Hydrogen addition rate>
Using a superconducting nuclear magnetic resonance absorber (NMR, manufactured by Bruker, AVANCE 500), ¹ H-NMR was measured in deuterated chloroform, and the hydrogenation rate of the cyclic olefin resin (B) was calculated.

[Synthesis Example 1]
<Synthesis of Cyclic Olefin Resin (B1)>
8-methyl-8-methoxycarbonyltetracyclo represented by the following formula (2) [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (DNM) 100 g, 1-hexene 3.6 g as a molecular weight regulator, and toluene 200 g were charged into a nitrogen-substituted reaction vessel and heated to 80 ° C. To this, 0.21 mL of a toluene solution of triethylaluminum (0.6 mol / L) and 0.86 mL of a methanol-modified WCl ₆ toluene solution (0.025 mol / L) were added,
Reaction was performed at 80 ° C. for 1 hour to obtain a ring-opening polymer solution. Next, 0.04 g of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ as a hydrogenation catalyst was added to the obtained ring-opening polymer solution, the hydrogen gas pressure was adjusted to 9 to 10 MPa, and 160 to 165 The reaction was carried out at a temperature of 3 ° C. for 3 hours. After completion of the reaction, the obtained product was precipitated in a large amount of methanol to obtain a cyclic olefin resin (B1).

The obtained cyclic olefin resin (B1) has Mw = 14.4 × 10 ⁴ , Mw / Mn = 3.
. 25, Tg = 167 ° C., hydrogenation rate = 99.0% or more.

[Synthesis Example 2]
<Synthesis of Cyclic Olefin Resin (B2)>
8-methyl-8-methoxycarbonyltetracyclo represented by the above formula (2) [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (DNM) 585 g (2.518 mol), 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene 315 g (1.895 mol), molecular weight regulator 1-hexene 35.2 g (0.419 mol) and toluene 1350 g were charged into a reaction vessel purged with nitrogen and heated to 80 ° C. This triethylaluminum in toluene solution (triethyl aluminum concentration 0.61 mol / L) 4.70 mL, toluene solution of methanol-modified WCl ₆ (the methylated WCl ₆ concentration 0.025mol / L) 17.65mL added 1 at 80 ° C. It was made to react for time and the ring-opening copolymer solution was obtained.

370 g of the obtained ring-opening copolymer solution was put in an autoclave, and 80 g of toluene was further added. Next, 0.032 g of RuH (OCOCH ₃ ) (CO) [P (C ₆ H ₅ ) ₃ ] ₂ is added as a hydrogenation reaction catalyst, hydrogen gas is introduced so that the gauge pressure becomes 10 MPa, and the pressure is set to 10 MPa. The reaction was carried out for 3 hours by heating to 160 to 165 ° C. After completion of the reaction, the obtained product was precipitated in a large amount of methanol to obtain a cyclic olefin resin (B2).

  The obtained cyclic olefin resin (B2) had Mw = 74,395, Mw / Mn = 3.10, Tg = 140 ° C., and hydrogenation rate = 99.0% or more.

[Synthesis Example 3]
<Synthesis of Cyclic Olefin Resin (B3)>
8-methyl-8-methoxycarbonyltetracyclo represented by the above formula (2) [4.4.0.1 ^2,5 . Molecular weight control using 71 g of 1 ^7,10 ] -3-dodecene (DNM), 25 g of dicyclopentadiene (DCP) and 1 g of bicyclo [2.2.1] hept-2-ene (NB) as monomers Along with 18 g of the agent 1-hexene and 200 g of toluene, the reaction vessel was charged with nitrogen and heated to 100 ° C.

To this, 0.005 g of triethylaluminum and 0.005 g of methanol-modified WCl ₆ (anhydrous methanol: PhPOCl ₂ : WCl ₆ = 103: 630: 427 weight ratio) were added and reacted for 60 minutes to obtain a copolymer.

Next, the obtained copolymer solution was placed in an autoclave, and 200 g of toluene was further added. Next, RuH (CO) [P (C ₆ H ₅ )] ₂ (OCO-p-Ph-n) which is a hydrogenation catalyst
0.0335 g of -C ₅ H ₁₁ ) was added to 100 g in terms of polymer solids, heated to 100 ° C., hydrogen gas was then charged into the reactor, and the pressure was adjusted to 10 MPa. Thereafter, the reaction was carried out at 165 ° C. for 3 hours while maintaining the pressure at 10 MPa. After completion of the reaction, 100 g of toluene, 3 g of distilled water, 0.72 g of lactic acid and 0.00214 g of hydrogen peroxide were added and heated at 60 ° C. for 30 minutes. Thereafter, 200 g of methanol was added and heated at 60 ° C. for 30 minutes, cooled to 25 ° C., and separated into two layers. After removing 500 g of the supernatant, 350 g of toluene and 3 g of water were added again, and the mixture was heated at 60 ° C. for 30 minutes. Thereafter, 240 g of methanol was added, heated at 60 ° C. for 30 minutes, cooled to 25 ° C., and separated into two layers. The supernatant liquid (500 g) was removed, 350 g of toluene and 3 g of water were further added, and the mixture was heated at 60 ° C. for 30 minutes. Thereafter, 240 g of methanol was added, heated at 60 ° C. for 30 minutes, cooled to 25 ° C., and separated into two layers. Finally, after removing 500 g of the supernatant, the polymer solution was heated to 50 ° C. and subjected to circulation filtration using respective filters of 2.0 μm, 1.0 μm and 0.2 μm. When the ratio of methanol to toluene in the solution was confirmed by gas chromatography, methanol / toluene = 20/80 wt%, the dielectric constant of the mixed solvent was 8.429 (dielectric constant of methanol = 32.63, The dielectric constant was calculated from 2.379). Thereafter, the solid content of the polymer was concentrated to 55%, the solvent was removed at 250 ° C., 4 torr, and a residence time of 1 hour, and the polymer was passed through a 10 μm polymer filter to obtain a cyclic olefin resin (B3).

  The obtained cyclic olefin resin (B3) had Mw = 61,000, Mw / Mn = 3.80, Tg = 146 ° C., and hydrogenation rate = 99.0% or more.

[Example 1]
<Formation of injection-molded body>
0.6 kg of polystyrene (A1) (trade name: SX100, Mw = 3200, Mw / Mn = 2.11, weight reduction rate = 3.6%, manufactured by Yasuhara Chemical Co., Ltd.) and the cyclic olefin resin obtained in Synthesis Example 1 (B1) After 2.4 kg was blended, it was melt-mixed using a twin screw extruder (TEM-37BS, manufactured by Toshiba Machine) to obtain a pellet-shaped resin composition. The cylinder temperature was 280 ° C., the shaft rotation speed was 100 rpm, and the extrusion speed was 10 to 20 kg / hr. The appearance of the obtained pellet was transparent.

The obtained resin composition was vacuum-dried at 100 ° C. for 4 hours, returned to normal pressure in a nitrogen atmosphere, and then sealed and stored in an aluminum bag filled with nitrogen. The resin composition was used in an injection molding machine (manufactured by FANUC, using a flat plate having a width of 60 mm, a length of 80 mm, a thickness of 1 mm, and a single die.
α2000iB, cylinder diameter 25 mm, mold clamping 100 ton) was performed to obtain a plate-like injection molded body.

  The injection molding conditions were a cylinder temperature of 305 ° C., a mold temperature of 100 ° C. as the actual temperature of the mold parting surface, and an injection speed of 120 mm / sec.

<Evaluation>
The following evaluation was performed about the obtained injection molded object.

<Haze, compatibility>
Haze was measured according to ASTM D1003 method. Using an HM-150 type haze meter manufactured by Murakami Color Research Laboratory Co., Ltd., the haze at any three locations of the injection molded article was measured, and the average value was adopted. Those having a haze of less than 0.5% were evaluated as ◎, those having a haze of 0.5% to 1.0% were evaluated as ◯, and those having a haze greater than 5.0% as ×.

<Total light transmittance>
The total light transmittance was measured according to ASTM D1003 method. Using an HM-150 type haze meter manufactured by Murakami Color Research Laboratory Co., Ltd., the total light transmittance at any three locations of the injection molded article was measured, and the average value was adopted.

<Refractive index>
Using a PC-2010 type prism coupler manufactured by Metricon, the refractive index at any five locations of the injection molded product was measured, and the average value of three points excluding the maximum value and the minimum value was adopted. A laser light source of 408 nm, 633 nm, and 830 nm was used as the light source, and the refractive index at 589 nm was calculated from the obtained refractive index by regression calculation using Cauchy's equation.

[Examples 2 to 5 and Comparative Examples 1 to 6]
In Example 1, an injection molded article was formed and evaluated in the same manner as in Example 1 except that the composition ratio of the resin composition was changed as shown in Table 1.

  The results are shown in Table 2.

  Since the optical component made of the injection-molded article of the present invention has a high refractive index and excellent transparency, it is suitably used for an optical lens, a light guide plate, a diffusion plate, a transparent plastic substrate, a microlens, an optical disk substrate, and the like. In addition, the polystyrene (A) and the cyclic olefin resin (B) contained in the resin composition of the present invention are excellent in compatibility with each other even at a temperature of 200 to 300 ° C. corresponding to the injection molding temperature. An optical component made of a body can be suitably obtained.

Claims (8)

(A) 1 to 40 parts by weight of polystyrene having a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 1,000 to 5,000,
(B) Glass transition temperature (Tg) is 100-180 degreeC, and it forms from the resin composition containing 100 weight part of cyclic olefin resin which is the following (i), (ii) or (iii). An optical component comprising an injection-molded body characterized by the above.
(I) A ring-opening polymer of the compound represented by the formula (1).
(Ii) A ring-opening copolymer of the compound represented by formula (1) and a copolymerizable monomer.
(Iii) A hydrogenated (co) polymer of the ring-opening (co) polymer of (i) or (ii).

(In Formula (1), R < ¹ > -R < ⁴ > is a hydrogen atom, a halogen atom, a C1-C30 hydrocarbon group, or another monovalent organic group, and may be the same or different. Further, any two of R ^{1 to} R ⁴ may be bonded to each other to form a monocyclic or polycyclic structure, m is 0 or a positive integer, and p is 0 or a positive integer. And at least one of R ² and R ⁴ is a polar alkoxycarbonyl group or an allyloxycarbonyl group .)   The optical component comprising the injection-molded article according to claim 1, wherein the polystyrene (A) has a weight average molecular weight (Mw) of 2,000 to 4,500.   The optical component comprising the injection-molded article according to claim 1 or 2, wherein the polystyrene (A) has a weight reduction rate of 7% or less when heated at 250 ° C for 1 hour.   The polystyrene-converted molecular weight distribution (Mw / Mn) measured by gel permeation chromatography (GPC) of the polystyrene (A) is 1.0 to 4.0. An optical component comprising the injection-molded article described in 1.   It is a lens, The optical component which consists of an injection molded body in any one of Claims 1-4 characterized by the above-mentioned.   The optical component according to claim 5, wherein the total light transmittance obtained by the ASTM D1003 method is 91% or more in an injection-molded article obtained by injection molding using a flat plate having a thickness of 1 mm.   The optical component according to claim 5 or 6, wherein a haze obtained by the ASTM D1003 method is 0.8 or less in an injection-molded article obtained by injection molding using a flat plate having a thickness of 1 mm. (A) 1 to 40 parts by weight of polystyrene having a polystyrene-reduced weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 1,000 to 5,000,
(B) A resin composition characterized by having a glass transition temperature (Tg) of 100 to 180 ° C. and containing 100 parts by weight of the following cyclic olefin-based resin (i), (ii) or (iii) object.
(I) A ring-opening polymer of the compound represented by the formula (1).
(Ii) A ring-opening copolymer of the compound represented by formula (1) and a copolymerizable monomer.
(Iii) A hydrogenated (co) polymer of the ring-opening (co) polymer of (i) or (ii).

(In Formula (1), R < ¹ > -R < ⁴ > is a hydrogen atom, a halogen atom, a C1-C30 hydrocarbon group, or another monovalent organic group, and may be the same or different. Further, any two of R ^{1 to} R ⁴ may be bonded to each other to form a monocyclic or polycyclic structure, m is 0 or a positive integer, and p is 0 or a positive integer. And at least one of R ² and R ⁴ is a polar alkoxycarbonyl group or an allyloxycarbonyl group .)