KR101534345B1 - Optical component composed of injection-molded object, and resin composition for forming the same - Google Patents

Abstract

The present invention provides an optical component comprising an injection-molded product having a high refractive index and excellent transparency.

(A) 1 to 40 parts of polystyrene having a polystyrene reduced weight average molecular weight (Mw) of 1,000 to 5,000 as measured by gel permeation chromatography (GPC), (B) 1 to 40 parts of polystyrene having a glass transition temperature And 180 parts by weight of a cyclic olefin resin.

Injection molded articles, resin compositions for forming optical parts, polystyrene, cyclic olefin resins

Description

TECHNICAL FIELD [0001] The present invention relates to a resin composition for forming an optical component comprising an optical component comprising an injection-molded article and an injection-

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

Injection molded bodies such as optical parts in which glass has been used have been replaced by plastics having excellent productivity, impact resistance and light weight. For example, a lens for a digital camera, a lens for a mobile phone, a pickup lens for a CD, a blue lens, an optical lens typified by a microlens, a substrate such as a disk, a light guide plate and a prism sheet are also made of polycarbonate, polymethyl methacrylate , The use of cyclic olefin resins has been progressing. However, the polycarbonate has a problem that the birefringence is large, the polymethyl methacrylate has low heat resistance, and the water absorbency is high.

The cyclic olefin resin has characteristics such as high glass transition temperature and high light transmittance and low anisotropy of refractive index and thus exhibits low birefringence compared with conventional optical resins and is excellent in heat resistance and transparency and optical properties . Using these characteristics, a cyclic olefin resin is applied in the field of, for example, an optical disk, an optical lens, an optical fiber, a transparent plastic based material, an electronic or optical material such as a low dielectric material, Is being studied.

However, the cyclic olefin-based resin is excellent in transparency, low water absorption and low birefringence, but has a refractive index lower than that of optical glass in lens applications, so that it can not sufficiently meet the demands for thinning and lightening. Therefore, in addition to the characteristics of the above-mentioned cycloolefin resin, the development of a cycloolefin resin having high refractive index is strongly desired.

Generally, it is known that the refractive index of a resin is improved by increasing the content of aromatic rings, halogen atoms or sulfur atoms, and it is known that introduction of an aromatic ring, a halogen atom, a sulfur atom into a cyclic olefin resin or blending with a heteropolymer containing them Is promising. For example, in Patent Document 1 below, it is described that a ring-opening polymer of a norbornene derivative containing an aromatic ring has a high refractive index. Further, in the following Patent Documents 2 to 5, there is no mention of the refractive index, but a blend of a cyclic olefin resin and a styrene resin is proposed. However, since the former ring-containing aromatic ring-containing norbornene ring-opening polymer has a high cost because of the production of monomers to be used and the ring-opening polymerization catalyst, the latter styrene type resin blend is in most cases, Phase separation occurs at a high temperature of 200 to 300 DEG C, which corresponds to the molding temperature, and therefore it is very difficult to obtain a transparent injection-molded article. Further, if transparency is maintained without phase separation, the addition amount of the styrenic resin is limited, and desired optical characteristics can not be obtained.

Therefore, the appearance of optical components such as a resin composition capable of easily obtaining a transparent optical component by suppressing phase separation and using a molding method under a high temperature and a lens having a high transparency as a main component thereof is strongly desired there was. In particular, a new technique for achieving a high refractive index using a cheap material has been demanded.

[Patent Document 1] Japanese Patent No. 3291857

[Patent Document 2] Japanese Patent No. 3775052

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2006-188555

[Patent Document 4] JP-A-2001-337222

[Patent Document 5] Japanese Patent No. 3018378

An object of the present invention is to provide an optical component comprising an injection-molded product having a high refractive index and excellent transparency.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that the present invention attains the above-mentioned object. That is, the present invention includes the following.

(A) 1 to 40 parts by weight of polystyrene having a polystyrene reduced weight average molecular weight (Mw) of 1,000 to 5,000 measured by gel permeation chromatography (GPC), (B) 1 to 40 parts by weight of polystyrene having a glass transition temperature (Tg) Lt; 0 > C, and 100 parts by weight of a cyclic olefin based resin having a weight-average molecular weight of 100,000 or less.

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

[3] The optical component of the above-mentioned [1] or [2], wherein the weight loss when the component (A) is heated at 250 ° C for 1 hour is 7% or less.

[4] The method according to any one of [1] to [3], wherein the component (A) has a molecular weight distribution (Mw / Mn) of 1.0 to 4.0 as measured by gel permeation chromatography (GPC) Wherein the optical component is made of an injection molded article.

[5] The optical component according to any one of [1] to [4], wherein the component (B) has a structural unit derived from a compound represented by the following formula (1).

(Wherein, R ¹ to R ⁴ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or monovalent other organic group, and each may be the same or different. In addition, any 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)

[6] The resin composition according to any one of [1] to [5] above, wherein when the molded resin having a thickness of 3.2 mm is molded by injection molding at 300 ° C, ) Is 1% or less.

[7] The optical component as set forth in [6] above, wherein the optical component is a lens.

[8] A resin composition comprising: (A) 1 to 40 parts by weight of polystyrene having a polystyrene reduced weight average molecular weight (Mw) of 1,000 to 5,000 as measured by gel permeation chromatography (GPC); (B) Lt; 0 > C.

INDUSTRIAL APPLICABILITY The resin composition according to the present invention can provide an optical component which is obtained by incorporating a specific polystyrene into a cyclic olefin resin and is formed of an injection-molded article having a high refractive index. Further, the resin composition according to the present invention can provide an optical component made of an injection-molded product having high transparency without phase separation even when heated at a high temperature when forming an optical component comprising an injection-molded article.

The optical component made of the injection-molded product of the present invention is a polystyrene (A) (hereinafter simply referred to as "polystyrene (A)") having a polystyrene reduced weight average molecular weight (Mw) of 1,000 to 5,000 measured by gel permeation chromatography (GPC) And 100 parts by weight of a cyclic olefin resin (B) (hereinafter simply referred to as "cycloolefin resin (B)") having a glass transition temperature (Tg) Resin composition for injection-molded product ").

 These will be described below.

[Polystyrene (A)]

The polystyrene (A) used in the present invention is produced by a known method, but a commercially available product is not particularly limited. Commercially available products include, for example, SX100 (manufactured by Yasuhara Chemical Co., Ltd.) and Resit S94 (manufactured by Sanyo Chemical Industries, Ltd.). The polystyrene (A) may be used alone or in combination of two or more.

The polystyrene (A) has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of 1,000 to 5,000, preferably 2,000 to 4,500, and more preferably 2,500 to 4,500. If Mw is less than 1,000, the strength of the optical component made of an injection-molded article is lowered. On the other hand, when the Mw is larger than 5,000, compatibility with the cycloolefin resin (B) is deteriorated, the refractive index can not be improved to an effective range, and the transparency of the optical component made of the injection molded article is lowered.

The molecular weight distribution Mw / Mn of the polystyrene (A) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.1 to 3.5, and still more preferably 1.2 to 2.5. When Mw / Mn is larger than 4.0, compatibility with the cycloolefin resin (B) is deteriorated, and the haze of an optical component made of an injection-molded article may increase.

The polystyrene (A) used in the present invention preferably has a weight loss rate of 7% or less, preferably 6% or less when heated at 250 DEG 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 contaminated.

The blending amount of the polystyrene (A) in the optical component made of an injection molded article is preferably 1 to 40 parts by weight, more preferably 5 to 40 parts by weight, per 100 parts by weight of the cyclic olefin resin (B). When the blending amount of the polystyrene is out of the range of 1 to 40 parts by weight, the compatibility of the polystyrene (A) and the cyclic olefin resin (B) is poor and the optical component comprising the injection molded article becomes cloudy.

[Cyclic Olefin Resin (B)]

Examples of the cycloolefin resin (B) used in 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 a compound represented by the general formula (1) and a copolymerizable monomer.

(iii) a hydrogenated (co) polymer of the ring-opened (co) polymer of (i) or (ii)

(iv) A hydrogenated (co) polymer obtained by cyclizing the ring-opened (co) polymer of (i) or (ii) by a Friedel-Crafts reaction.

(v) A saturated copolymer of a compound represented by the formula (1) and an unsaturated double bond-containing compound.

(vi) an addition-type (co) polymer of a compound represented by the formula (1), at least one monomer selected from vinyl cyclic hydrocarbon monomers and cyclopentadiene monomers, and hydrogenated (co) polymers thereof.

(vii) an alternating copolymer of a compound represented by the general formula (1) and an acrylate.

≪ Formula 1 >

(Wherein R ¹ to R ⁴ are each a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or other monovalent organic groups, and may be the same or different.) Among 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)

Among them, the cyclic olefin resin (B) is preferable from the viewpoint of compatibility with polystyrene (A) and transparency of an optical component made of an injection-molded product obtained.

The compound represented by the formula (1)

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,

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-ethylidenbicyclo [2.2.1] hept-2-ene,

8-ethylidene tetracyclo [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-

5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-

5,5,6-Trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene,

Pentafluoroethyl-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene,

5,6-difluoro-5-heptafluoro-isopropyl-6-trifluoromethylbicyclo [2.2.1] hept-

5-chloro-5,6,6-trifluorobicyclo [2.2.1] hept-2-ene,

5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-

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,

Tetrakis (trifluoromethyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene, 8,8,9,9-tetrakis

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 ]

Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene, 8- (2,2,2-trifluoroethoxycarbonyl)

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

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

As the compound represented by the above formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or other monovalent organic groups. In addition, any two of R ¹ to R ⁴ may combine with each other to form a monocyclic or polycyclic structure. m is 0 or a positive integer, and p is 0 or a positive integer.

Among them, R ¹ and R ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and R ² and R ⁴ are each independently a hydrogen atom or a monovalent organic group, R ² and R ⁴ at least one is preferably a polar group, and m is from 0 to 3 integers, p is an integer from 0 to 3, preferably m + p = 0 More preferably m + p = 0 to 2, particularly preferably m = 1 and p = 0. Among them, when m = 1 and p = 0, the cyclic olefin-based resin (B) to be obtained is particularly preferable because of its high glass transition temperature and excellent mechanical strength.

Examples of the polar group of the compound represented by the formula (1) 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 through a linking group such as a methylene group or may contain a divalent organic group having a polarity such as a carbonyl group, an ether group, a silyl ether group, a thioether group or an imino group in the methylene group. Among these polar groups, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group or an allyloxycarbonyl group is preferable, and an alkoxycarbonyl group or an allyloxycarbonyl group is particularly preferable.

When at least one of R ² and R ⁴ is a polar group represented by the formula - (CH ₂ ) _n COOR, the resulting cycloolefin resin (B) has a high glass transition temperature, low hygroscopicity and excellent adhesion with various materials And is preferable. In the above formula - (CH ₂ ) _n COOR, R is preferably a hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, preferably an alkyl group. Also, n is usually 0 to 5, preferably 0 to 3. The smaller the value of n is, the higher the glass transition temperature of the cyclic olefin based resin (B) obtained is, and when n is 0, the synthesis is also preferable.

In the compound represented by the formula (1), R ¹ and R ³ are preferably an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, particularly preferably a methyl group Do. Particularly, when the alkyl group is bonded to the same carbon atom as the carbon atom bonded to the polar group represented by the formula - (CH ₂ ) _n COOR, the hygroscopicity of the cycloolefin resin (B) to be obtained can be lowered.

Copolymerizable monomer

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

The cycloolefin preferably has 4 to 20 carbon atoms, and preferably 5 to 12 carbon atoms. These may be used alone or in combination of two or more.

The preferable use range of the compound / copolymerizable monomer represented by the general formula (1) is 100/0 to 50/50 by weight, more preferably 100/0 to 60/40.

Ring opening polymerization catalyst

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

(A) at least one element selected from the group consisting of W, Mo and Re, (b) at least one element selected from the group consisting of elements in the group IA of the periodic table of the demethyl (for example, Li, Na and K) (For example, Mg, Ca, etc.), Group IIB elements (e.g., Zn, Cd, Hg), Group IIIA elements (e.g., B and Al) , Pb and the like) or a compound of a group IVB element (for example, Ti, Zr and the like) and at least one of the above-mentioned element-carbon bonds or the element- Catalyst. Further, in order to increase the activity of the catalyst, other additives described later may be added.

Examples of the compound of W, Mo or Re preferable as the component (a) include compounds such as WCl ₆ , MoCl ₆ and ReOCl ₃ , JP-A No. 1-132626, page 8, And the right column on page 8, line 17.

Component (b) roneun, for example, _{nC 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, LiH, etc., JP-A No. 1-132626, page 8, right column, line 18, page 8, page 8, right column, line 3.

Examples of other additives include alcohols, aldehydes, ketones, and amines. In addition, JP-A-1-132626, page 8, right column, line 16 to page 9, left column, May also be used.

The amount of the metathesis catalyst to be used is generally from 1: 500 to 1: 50,000, preferably from 1: 500 to 1:50, as a molar ratio of the component (a) to the compound represented by the formula (1) 1: 1,000 to 1: 10,000.

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

Solvent for polymerization reaction

Examples of the solvent used in the ring-opening polymerization reaction include, but are not limited to, those capable of dissolving the molecular weight modifier, the compound represented by Formula 1, and the metathesis catalyst, and examples thereof include pentane, hexane, heptane, octane, Cyclohexane, decalin and norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; aromatic hydrocarbons such as chlorobutane, bromohexane, methylene chloride, dichloroethane , Halogenated alkanes such as hexamethylene dibromide, chlorobenzene, chloroform and tetrachlorethylene, halogenated aryl and the like, saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate and dimethoxyethane Ethers such as tetrahydrofuran, dibutyl ether, tetrahydrofuran and dimethoxyethane. These may be used alone or in combination. Of these, aromatic hydrocarbons are preferable.

The amount of solvent to be used is usually 1: 1 to 10: 1, and preferably 1: 1 to 5: 1 in terms of "solvent: compound represented by the formula (1)".

Molecular weight regulator

The molecular weight of the ring-opened (co) polymer can be controlled by the polymerization temperature, the kind of the catalyst, and the type of the solvent. In the present invention, the molecular weight regulator is controlled by coexistence in the reaction system.

Examples of the molecular weight regulator include a-olefins such as ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, . Of these, 1-butene and 1-hexene are particularly preferable.

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

The amount of the molecular weight modifier to be used is 0.005 to 0.6 mol, preferably 0.02 to 0.5 mol, based on 1 mol of the compound represented by the formula (1) provided in the ring-opening polymerization reaction.

In order to obtain the ring-opened copolymer of (ii), ring-opening copolymerization of the compound represented by the formula (1) and the copolymerizable monomer may be carried out in a ring-opening polymerization process, but if necessary, a conjugated diene compound such as polybutadiene, polyisoprene, (1) in the presence of an unsaturated hydrocarbon polymer having two or more carbon-carbon double bonds in its main chain, such as styrene-butadiene copolymer, ethylene-non-conjugated diene copolymer and polynorbornene, Ring-opening polymerization may be carried out.

The ring-opened (co) polymer obtained as described above is used as it is, but the hydrogenated (co) polymer obtained by further hydrogenating the hydrogenated (co) polymer is also preferably used as a raw material for a resin having high impact resistance.

Hydrogenation catalyst

The hydrogenation reaction can be carried out by a commonly used method, that is, a hydrogenation catalyst is added to a solution of the ring-opening polymer, and hydrogen gas of atmospheric pressure to 300 atm, preferably 3 to 200 atm, Lt; RTI ID = 0.0 > 180 C. < / RTI >

As the hydrogenation catalyst, those used for the hydrogenation reaction of a common olefinic compound can be used. Examples of the hydrogenation catalyst include heterogeneous catalysts and homogeneous catalysts.

Examples of the heterogeneous catalyst include solid catalysts in which noble metal catalyst materials such as palladium, platinum, nickel, rhodium, and ruthenium are supported on a carrier such as carbon, silica, alumina, or titania. Examples of the homogeneous catalyst include nickel naphthenate / triethyl aluminum, nickel acetyl acetonate / triethyl aluminum, cobalt octenate / n-butyl lithium, titanocene dichloride / diethyl aluminum monochloride, (Phenylphosphine) rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium and the like. The form of the catalyst may be powder or particulate.

These hydrogenation catalysts are used in such a ratio that the ring-opening (co) polymer: hydrogenation catalyst (weight ratio) becomes 1: 1 x 10 ^-6 to 1: 2.

Thus, the hydrogenated (co) polymer obtained by hydrogenation has excellent thermal stability, and its properties are not deteriorated even by heating during molding or use as a product. Here, the hydrogenation rate is usually 50% or more, preferably 70% or more, more preferably 90% or more, particularly preferably 99% or more.

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

The hydrogenated (co) polymer used as the cycloolefin resin (B) according to the present invention preferably has a gel content of 5% by weight or less, more preferably 1% by weight or less, Is particularly preferable.

The cyclic olefin resin (B) according to the present invention may be obtained by cyclizing the ring-opened (co) polymer of (i) or (ii) in the above (iv) by a Friedel- Polymers are also used.

Cycling by Friedel-Craft reaction

A method of cyclizing the ring-opening (co) polymer by Friedel-Crafts reaction is not particularly limited, but a known method using an acidic compound described in JP-A-50-154399 is used. Specific examples of the acidic compound include 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.

The ring-opened (co) polymer that is cyclized by the Friedel-Crafts reaction can be hydrogenated using the same method as the ring-opened (co) polymer of (i) or (ii).

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

Unsaturated double bond-containing compound

Examples of the unsaturated double bond-containing compound (v) include olefin compounds preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms such as ethylene, propylene, and butene.

The compound represented by Formula 1 and the unsaturated double bond-containing compound are preferably used in a weight ratio of 90/10 to 40/60, and more preferably 85/15 to 50/50.

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

Addition polymerization catalyst

As the catalyst for synthesizing the saturated copolymer (v), 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.

V (OR) _a X _b or V (OR) _c X _d wherein R is a hydrocarbon group and X is a halogen atom and 0? A? 3, 0? B? 3, 4, 3 (c + d) 4), or an electron donor adduct of these compounds is used.

Examples of the electron donor include an oxygen-containing electron donor such as an alcohol, a phenol, a ketone, an aldehyde, a carboxylic acid, an ester of an organic acid or an inorganic acid, an ether, an acid amide, an acid anhydride or an alkoxysilane, a nitrogen such as ammonia, amine, nitrile, isocyanate Containing electron donors and the like.

As the organoaluminum compound as the cocatalyst, at least one selected from those having at least one aluminum-carbon bond or aluminum-hydrogen bond is used.

In the above case, for example, in the case of using a vanadium compound, the ratio of the vanadium compound to the organoaluminum compound is 2 or more, preferably 2 to 50, Particularly preferably in the range of 3 to 20.

The polymerization reaction solvent used in the addition polymerization is the same as the solvent used in the ring-opening polymerization reaction. The molecular weight of the saturated copolymer (v) to be obtained is usually adjusted by using hydrogen.

As the cyclic olefin resin (B) according to the present invention, it is also possible to use addition type of at least one monomer selected from the compound represented by the above-mentioned chemical formula (1), the vinyl cyclic hydrocarbon monomer and the cyclopentadiene- Copolymers and hydrogenated copolymers thereof can also be used.

The vinyl-based cyclic hydrocarbon-based monomer

Examples of the vinyl-based cyclic hydrocarbon monomer (vi) include vinylcyclopentene-based monomers such as 4-vinylcyclopentene and 2-methyl-4-isopropenylcyclopentene, 4-vinylcyclopentane, 4- And vinylcyclopentane-based monomers such as isopropenylcyclohexane and isopropenylcyclopentane; vinylidene 5-membered cyclic hydrocarbon monomers such as 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-isopropenylcyclohexene, Vinylcyclohexane monomers such as vinylcyclohexene and 2-methyl-4-isopropenylcyclohexene, vinylcyclohexane monomers such as 4-vinylcyclohexane and 2-methyl-4-isopropenylcyclohexane Styrene monomers such as styrene,? -Methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-phenylstyrene and p- Terpene-based monomers such as terpene, 1-terpene, diterpene, d-limonene, 1-limonene, dipentene, Vinyl cycloheptene monomers such as 4-vinylcycloheptene and 4-isopropenylcycloheptene, vinylcycloheptane monomers such as 4-vinylcycloheptane and 4-isopropenylcycloheptane, and the like. Among them, styrene and? -Methylstyrene are preferable. These may be used singly or in combination of two or more.

The cyclopentadiene-based monomer

Examples of the cyclopentadiene monomer used in the monomer of the addition type (co) polymer of (vi) include cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene , 5-methylcyclopentadiene, 5,5-dimethylcyclopentadiene, and the like. Among them, cyclopentadiene is preferable. These may be used alone or in combination of two or more.

The addition type (co) polymer of at least one monomer selected from the compound represented by the above-mentioned formula (1), the vinyl cyclic hydrocarbon monomer and the cyclopentadiene monomer is obtained by reacting the compound represented by the formula (1) Can be produced by the same addition polymerization method as in the case of a saturated copolymer with a compound.

The hydrogenated (co) polymer of the addition type (co) polymer can be produced by the same hydrogenation process as the hydrogenated (co) polymer of the ring-opened (co) polymer of (iii) Can be manufactured.

As the cyclic olefin resin (B) according to the present invention, an alternating copolymer of the compound represented by the general formula (1) (vii) with acrylate is also used.

Acrylate

Examples of the acrylate used in the preparation of the alternate copolymer of the compound represented by the formula (1) and the acrylate in the above (vii) include methyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate and the like Containing heterocyclic group having 2 to 20 carbon atoms such as linear, branched or cyclic alkyl acrylate, glycidyl acrylate and 2-tetrahydrofurfuryl acrylate having 1 to 20 carbon atoms, benzyl acrylate Acrylate having a polycyclic structure having 7 to 30 carbon atoms such as an aromatic ring-containing acrylate having 6 to 20 carbon atoms, such as isobornyl acrylate and dicyclopentanyl acrylate.

In the present invention, in order to obtain an alternate copolymer of the compound represented by the general formula (1) and the acrylate (vii), in the presence of a Lewis acid, generally 100 mol of the compound represented by the general formula 30 to 70 mol of the compound represented by the formula (1) and 70 to 30 mol of the acrylate, preferably 40 to 60 mol of the compound represented by the formula (1) and 60 to 40 mol of the acrylate, Particularly preferably, radical polymerization is carried out using 45 to 55 moles of the compound represented by the formula (1) and 55 to 45 moles of the acrylate.

The amount of the Lewis acid used to obtain the alternate copolymer of the compound represented by the formula (1) and the acrylate in the above (vii) is 0.001 to 1 mol per 100 moles of the acrylate. Further, a known free radical-generating organic peroxide or an azobis-based radical polymerization initiator may be used, and the polymerization reaction temperature is usually -20 ° C to 80 ° C, preferably 5 ° C to 60 ° C. The same solvent as that used in the ring-opening polymerization reaction may be used as the polymerization reaction solvent.

The term "alternating copolymer " used in the present invention means that the structural unit derived from the compound represented by the formula (1) is not adjacent, that is, the neighboring structural unit derived from the compound represented by the formula (1) Means a copolymer having a derived structural unit and does not deny a structure in which structural units derived from an acrylate exist adjacent to each other.

The preferred molecular weight of the cyclic olefin-based resin (B) according to the present invention, an intrinsic viscosity [η] _inh 0.2 to 5 ㎗ / g, more preferably 0.3 to 3 ㎗ / g, particularly preferably 0.4 to 1.5 ㎗ / g and the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) in tetrahydrofuran is 8,000 to 100,000, more preferably 10,000 to 80,000, particularly preferably 12,000 to 50,000, The weight average molecular weight (Mw) is preferably 20,000 to 300,000, more preferably 30,000 to 250,000, and particularly preferably 40,000 to 200,000. The molecular weight distribution (Mw / Mn) is preferably 2.0 to 4.0, more preferably 2.5 to 3.7, still more preferably 2.8 to 3.5. By using a resin having a small molecular weight distribution, it is possible to obtain a resin composition which hardly causes phase separation at the time of heating, that is, a resin composition having a small fluctuation in melt flow rate (MFR).

When the intrinsic viscosity [?] _Inh , the number average molecular weight and the weight average molecular weight are within the above ranges, the heat resistance, water resistance, chemical resistance and mechanical properties of the cyclic olefin resin (B) The molding processability of the component is improved.

The glass transition temperature (Tg) of the cyclic olefin based resin (B) according to the present invention is usually 100 to 180 占 폚, preferably 110 to 175 占 폚, more preferably 120 to 170 占 폚, particularly preferably 130 to 170 占 폚 / RTI > When the Tg is less than 100 占 폚, it is undesirable because it is deformed by use under high temperature conditions or by secondary processing such as coating and printing. On the other hand, if the TG exceeds 180 ° C, the molding process becomes difficult and the possibility of the resin deteriorating due to heat during molding becomes high.

In addition, as described above, the molecular weight distribution of the cyclic olefin based resin (B) according to the present invention is preferably small. In order to obtain a resin having a small molecular weight distribution in the (co) polymer of (i) to (vii), ring-opening polymerization or addition polymerization is preferably carried out in multiple steps.

For example, the multistage polymerization of the ring-opening (co) polymer of (i) or (ii) can be carried out by arranging polymerization vessels in series and supplying the monomer components and the catalyst components to the polymerization vessel, Or a mixed solution of a polymer component and a polymer component and a catalyst component, which are partially polymerized, in a polymerization vessel at the next stage. The above components are supplied to the polymerization vessel in the next stage, and a new monomer component and a catalyst component are supplied, additional polymerization is carried out, and the mixture liquid component is further fed to the next polymerization vessel. In the third stage polymerization tank, the polymerization is carried out in the same manner as in the second stage. By this method, the conversion to the polymer is at least 80%, preferably at least 85%, more preferably at least 88%, particularly preferably at least 90% .

The multistage polymerization in the case of the addition (co) polymerization of (v) to (vii) can also be carried out in accordance with the above ring-opening polymerization.

The cyclic olefin resin (B) according to the present invention preferably has an logarithmic viscosity (?) Of 0.3 to 1.0 dl / g as measured in a chlorobenzene solution (concentration 0.5 g / dl) at 30 占 폚. The weight average molecular weight (Mw) of the cyclic olefin resin (B) in terms of polystyrene measured by gel permeation chromatography (GPC) is usually 1.1 to 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 an optical component or the like made of an injection-molded product to be obtained may be lowered. On the other hand, if the molecular weight is too large, the solution viscosity becomes excessively high and the productivity and workability of the resin composition according to the present invention may be deteriorated.

[Other additives]

In the optical component made of the injection-molded product of the present invention, an antioxidant, an ultraviolet absorber, or the like may be further added to improve the thermal resistance and light resistance of the resin.

Examples of the hydrocarbon resin include a C5-based resin, a C9-based resin, a C5-based / C9-based mixed resin, a cyclopentadiene-based resin, a copolymer system resin of an olefin / vinyl substituted aromatic compound, a cyclopentadiene-based compound / Copolymer system resins, hydrogenated products of these resins, and hydrogenated products of vinyl-substituted aromatic resins. The content of the hydrocarbon resin is usually 1 to 50 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the cyclic olefin resin (B).

Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di- (Methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,1,3- (3,5-di-t-butyl-4-hydroxybenzyl) benzene, stearyl-? - (3,5- butyl-4-hydroxyphenyl) propionate, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-diethylphenylmethane, 3,9- , 1-dimethyl-2- (β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) ethyl], 2,4,8,10-tetraoxaspiro [5.5] undecane, (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite, cyclic neopentane tetraylbis Di-t-butyl-4-methylphenyl) phosphite, and 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2- (2H-benzotriazole- 2-yl) -4,6-di-t-pentylphenol, 2-benzotriazol-2-yl 4,6-di- Phenol and 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 - [(2H-benzotriazol-2-yl) phenol]].

The content of these additives is usually 0.01 to 10 parts by weight, preferably 0.03 to 5 parts by weight, per 100 parts by weight of the cyclic olefin resin (B).

For the purpose of improving workability, additives such as a lubricant and a dye or a fluorescent whitening agent may be added in order to improve hue.

[Resin composition for optical component comprising injection molded article]

The resin composition for an optical component comprising the injection-molded article of the present invention can be obtained by the following method (I) to (III), for example.

(I) A method of mixing polystyrene (A), cyclic olefin resin (B) and other additives using a twin-screw extruder or a roll kneader.

(II) A method in which polystyrene (A) and other additives are added to a solution prepared by dissolving a cyclic olefin resin (B) in an appropriate solvent, and the mixture is mixed using an appropriate stirrer.

(III) A method of mixing polystyrene (A) or a solution thereof with a cyclic olefin resin (B) or its solution and other additives, followed by desolvation using a devolatilizer or a rudder.

As the solvent to be used at this time, a general solvent such as a polymerization solvent used for production of polystyrene (A) or cycloolefin resin (B) can be used.

[Injection molded article]

The optical component comprising the injection-molded product of the present invention is obtained by injection molding a resin composition containing polystyrene (A), a cyclic olefin resin (B) and other optional additives as an optional component by an injection molding machine.

When the resin composition according to the present invention is molded into a 3.2 mm-thick molded plate by injection molding at a temperature of 300 캜, the soaking of the molded plate is preferably 1% or less, and more preferably 0.6% or less.

The injection molding machine is not particularly limited, but may be an in-line type or a pre-flame type in the cylinder system; Driving methods include hydraulic, electric, hybrid; The clamping method is a direct-press type, toggle type; Examples of the injection direction include a horizontal type and a vertical type. Further, the clamping method may be injection compression. The cylinder diameter and the clamping force are determined according to the shape of the desired injection-molded object. Generally, when the projected area of the injection-molded object is large, the clamping force is preferably increased. When the injection- .

When the cylinder is an in-line type, a screw shape such as a compression ratio, a length / diameter ratio, and the presence or absence of a sub flight can be appropriately selected and the surface of the screw is coated with a known coating such as chromium, titanium, You may. In order to improve the stability of the metering or injection operation, a mechanism for controlling rotation and pressure of the screw may be provided. It is also preferable to reduce the pressure inside the cylinder or the hopper for storing the resin composition, or to seal the cylinder and the hopper with an inert gas such as nitrogen from the viewpoint that an injection-molded article can be stably obtained.

In order to reduce the warpage of the injection-molded article during injection molding or to perform stable continuous molding, a method of reducing the pressure inside the cavity of the mold apparatus or an injection compression method is preferably used.

In the case of injection molding under reduced pressure in the cavity of the mold apparatus, the degree of vacuum is preferably -0.08 MPa or less, more preferably -0.09 MPa or less, and particularly preferably -0.1 MPa or less by gauge pressure. When the amount exceeds the above range, the degree of vacuum is insufficient and an injection molded article excellent in light transmittance and light diffusibility may not be obtained.

The reduced pressure in the above range is achieved by using a known method, for example, a vacuum pump. It is preferable to use a known sealing material such as an O-ring or the like around the cavity or the ejector mechanism portion, and a vacuum grease or the like may be used within a range in which impurities are not mixed in the injection-molded object. The suction port for connecting to the decompression device such as a vacuum pump can be provided at any place in the mold apparatus, but it is usually provided at the ejector mechanism portion, the ends of the spool and runner, the box structure portion, and the like. The vacuum suction sequence may be controlled by an electromagnetic valve or the like in accordance with the opening and closing of the mold apparatus, or may be always operated, and is not particularly limited as long as it is a method capable of reducing the pressure in the cavity of the mold apparatus when the molten resin is charged Do not.

When the inside of the cavity of the mold apparatus is reduced by injection molding, the cavity is closed and the molten resin is injected under reduced pressure, so that the injection delay time is usually set. The injection delay time depends on the capacity of the vacuum pump to be 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, a molten resin is injected into the gap, and the pressure of the resin measured on the cylinder side is set in the range of 200 to 2,000 kgf / It is possible to compress the injection-molded object surface in the mold apparatus while narrowing the interval between the cavities.

The core of the mold apparatus is set to 1.1 to 10 times the thickness of the injection-molded body to be in a movable state, and a molten resin is injected thereinto. After the start of injection or the completion of injection, the movable core is rotated at an average speed of 0.01 mm / / Sec. ≪ / RTI >

For these injection compression molding methods, a known molding machine is used.

Other conditions of the injection molding are not particularly limited, but usually the cylinder temperature is 260 to 350 占 폚, and the mold apparatus temperature is in the range of usually Tg-1 to Tg-40 占 폚 based on the glass transition temperature Tg of the resin composition, Tg-5 to Tg-30 占 폚. The injection speed varies depending on the size of the injection-molded article of the present invention or the cylinder size of the molding machine. For example, when the cylinder diameter is 28 mm, the injection speed is usually 80 mm / sec or more, preferably 90 to 250 mm / sec . It is preferable to appropriately adjust the holding pressure to a minimum pressure and time sufficient to maintain the shape of the injection-molded object.

An optical component comprising an injection-molded product formed from the resin composition according to the present invention is preferably used for an optical component such as a lens.

[Examples]

Hereinafter, the present invention will be described in more detail based on examples, but the present 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) >

A gel permeation chromatograph (HLC-8220GPC manufactured by Tosoh Corporation, column: Guard column H _XL -H, TSK gel G7000H _XL , TSK gel GMH _XL, and TSK gel G2000H _XL manufactured by Tosoh Corporation) , A flow rate of 1 ml / min, a sample concentration of 0.7 to 0.8% by weight, an injection amount of 70 μl, a measurement temperature of 40 ° C, a detector RI (40 ° C), a reference material, TSK standard polystyrene, The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the polystyrene (A) and the cycloolefin resin (B) were measured.

≪ Weight loss ratio (TGA) >

Heating was carried out at 250 占 폚 for 1 hour by using a TGA thermometer (manufactured by SII, TG / DTA6200) to determine the weight reduction rate of polystyrene (A).

≪ Glass transition temperature (Tg) >

(Hereinafter referred to simply as "glass transition temperature (Tg)") of a cyclic olefin based resin according to Japanese Industrial Standard K7121 using a differential scanning calorimeter (DSC6200, manufactured by SII).

<Hydrogen Addition Rate>

The hydrogenation rate of the cyclic olefin resin (B) was calculated by measuring ¹ H-NMR in deuterated chloroform using a superconducting nuclear magnetic resonance absorption apparatus (NMR, AVANCE500, manufactured by Bruker).

[Synthesis Example 1]

&Lt; Synthesis of cyclic olefin resin (B1) >

Methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene (DNM) represented by the following formula 2, 3.6 g of 1-hexene as a molecular weight regulator And 200 g of toluene were placed in a nitrogen-purged reaction vessel, and heated to 80 占 폚. 0.21 ml of a toluene solution of triethyl aluminum (0.6 mol / l) and 0.86 ml of a methanol-modified WCl ₆ toluene solution (0.025 mol / l) were added and reacted at 80 ° C for 1 hour to obtain a ring opening polymer solution. Then, 0.04 g of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added as a hydrogenation catalyst to the obtained ring-opening polymer solution, hydrogen gas pressure was adjusted to 9 to 10 MPa, Lt; / RTI &gt; After completion of the reaction, the resulting product was precipitated in a large amount of methanol to obtain a cycloolefin resin (B1).

The cyclic olefin resin (B1) thus obtained had Mw = 14.4 x 10 ⁴ , Mw / Mn = 3.25, Tg = 167 ° C, and hydrogenation rate = 99.0% or more.

[Synthesis Example 2]

&Lt; Synthesis of cyclic olefin resin (B2) >

585 g (2.518 mol) of 8-methoxycarbonyl-8-methyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene (DNM) , 315 g (1.895 mol) of 5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 35.2 g (0.419 mol) of 1-hexene as a molecular weight regulator and 1350 g of toluene were placed in a nitrogen- , And heated to 80 占 폚. Toluene solution of triethylaluminum was added thereto the (triethylaluminum concentration 0.61 mol / ℓ) 4.70 ㎖, a toluene solution of methanol modified WCl ₆ (methanol modified WCl ₆ concentration of 0.025 mol / ℓ) 17.65 ㎖, and 1 hour at 80 ℃ To obtain a ring-opening copolymer solution.

370 g of the obtained ring-opening copolymer solution was placed in an autoclave, and further 80 g of toluene was added. Then, in the after _{RuH (OCOCH 3) (CO)} [P (C 6 H 5) 3] 0.032 g was added to ₂ as hydrogenation catalyst, the introduction of the hydrogen gas to a gauge pressure that is 10 MPa, and the pressure 10 MPa And maintained at 160 to 165 DEG C for 3 hours. After completion of the reaction, the obtained product was precipitated in a large amount of methanol to obtain a cycloolefin resin (B2).

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

[Synthesis Example 3]

&Lt; Synthesis of cyclic olefin resin (B3) >

71 g of 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] -3-dodecene (DNM) represented by the above-mentioned formula 2, dicyclopentadiene (DCP) 25 hexene and 200 parts of toluene were charged into a reaction vessel purged with nitrogen and reacted at 100 DEG C for 1 hour with use of 1 g of bicyclic [2.2.1] hept-2-ene (NB) as a monomer, Lt; / RTI &gt;

0.005 part of triethylaluminum and 0.005 part of methanol-denatured WCl ₆ (methanol anhydride: PhPOCl ₂ : WCl ₆ = 103: 630: 427 weight ratio) were added and reacted for 60 minutes to obtain a copolymer.

Then, the solution of the obtained copolymer was placed in an autoclave, and 200 parts of toluene was further added. Then, 0.0335 parts by weight of RuH (CO) [P (C ₆ H ₅ )] ₂ (OCO-p-Ph-n C ₅ H ₁₁ ) as a hydrogenation catalyst was added to 100 parts by weight of the solid content of the polymer, After heating, hydrogen gas was introduced into the reactor, and the pressure was set to 10 MPa. Thereafter, the reaction was carried out at 165 DEG C for 3 hours while maintaining the pressure at 10 MPa. After completion of the reaction, 100 parts by weight of toluene, 3 parts by weight of distilled water, 0.72 part by weight of lactic acid and 0.00214 parts by weight of hydrogen peroxide were added and the mixture was heated at 60 DEG C for 30 minutes. Thereafter, 200 parts by weight of methanol is added, and the mixture is heated at 60 DEG C for 30 minutes. When the mixture is cooled to 25 DEG C, it is separated into two layers. 350 parts by weight of toluene and 3 parts by weight of water were added and heated at 60 占 폚 for 30 minutes. Then, 240 parts by weight of methanol was added and the mixture was heated at 60 占 폚 for 30 minutes and cooled to 25 占 폚, . 350 parts by weight of toluene and 3 parts by weight of water were added and heated at 60 DEG C for 30 minutes. After that, 240 parts by weight of methanol was added and the mixture was heated at 60 DEG C for 30 minutes and cooled to 25 DEG C to obtain 2 Layer. Finally, after removing 500 parts by weight of the supernatant, the polymer solution was heated to 50 DEG C and subjected to cyclic filtration using filters of 2.0 mu m, 1.0 mu m, and 0.2 mu m, respectively. When the ratio of methanol to toluene in the solution was checked by gas chromatography, the methanol / toluene ratio was 20/80 wt%, and the dielectric constant of the mixed solvent was 8.429 (the permittivity of methanol = 32.63 and the permittivity of toluene = 2.379). Thereafter, the polymer solid content was concentrated to 55%, subjected to desolvation treatment at 250 DEG C, 4 torr, and a residence time of 1 hour, and passed through a polymer filter of 10 mu m to obtain a cycloolefin resin (B3).

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

[Example 1]

&Lt; Formation of injection-molded article >

0.6 kg of polystyrene A1 (manufactured by Yasuhara Chemical Co., Ltd., trade name: SX100, Mw = 3200, Mw / Mn = 2.11 and weight loss ratio = 3.6%) and 2.4 kg of the cyclic olefin resin (B1) obtained in Synthesis Example 1 were blended And then melt-mixed using a twin-screw extruder (TEM-37BS, manufactured by Toshiba Kikai) to obtain a pellet-shaped resin composition. The cylinder temperature was 280 DEG C, the shaft rotation speed was 100 rpm, and the extrusion rate was 10 to 20 kg / hour. The appearance of the obtained pellet was transparent.

The obtained resin composition was vacuum-dried at 100 占 폚 for 4 hours, returned to normal pressure in a nitrogen atmosphere, and sealed in an aluminum bag filled with nitrogen. The resin composition was injection-molded by an injection molding machine (manufactured by Canon Inc., α2000iB, cylinder diameter 25 mm, clamping 100 ton) using a flat plate having a width of 60 mm, a length of 80 mm and a thickness of 1 mm and one obtained mold, Thereby obtaining a plate-like injection molded article.

The conditions of the injection molding were a cylinder temperature of 305 ° C, a mold temperature of 100 ° C at room temperature on the mold-facing surface, and an injection speed of 120 mm / sec.

<Evaluation>

The following injection molded articles were evaluated.

<Hayes, Compatibility>

The haze was measured according to the ASTM D1003 method. Using an HM-150 haze meter manufactured by Murakami Shikisai Kogetsu Co., Ltd., the haze of arbitrary three portions of the injection molded article was measured, and the average value thereof was adopted. A haze value of less than 0.5% was rated as?, A value of 0.5% to 1.0% was rated as?, And a value of greater than 5.0% was evaluated as?.

<Total light transmittance>

The total light transmittance was measured in accordance with the ASTM D1003 method. Using an HM-150 haze meter manufactured by Murakami Shikisai Gijutsu Kagaku Co., Ltd., the total light transmittance at three arbitrary positions of the injection molded article was measured and the average value thereof was adopted.

<Refractive index>

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

[Examples 2 to 5 and Comparative Examples 1 to 6]

As shown in the following Table 1, the injection molded body was formed and evaluated in the same manner as in Example 1, except that the composition ratio of the resin composition was changed. The results are shown in Table 2 below.

A1: SX100 (polystyrene, produced by Yasuhara Chemical Co., Ltd., Mw = 3,200, Mw / Mn = 2.11, weight loss rate = 3.6%

A2: Resist S94 (polystyrene, manufactured by Sanyo Chemical Industries, Ltd., Mw = 4,050, Mw / Mn = 3.41, weight loss rate = 6.0%

A3: ST-120 (polystyrene, manufactured by Sanyo Chemical Industries, Ltd., Mw = 11,500, Mw / Mn = 2.08, weight loss ratio = 0.4%

A4: GP G210C (polystyrene, Mw = 199,900, Mw / Mn = 2.38, weight loss ratio = 0.2%, manufactured by Toyo Styrene K.K.)

A5: ST-95 (polystyrene, manufactured by Sanyo Chemical Industries, Ltd., Mw = 5,100, Mw / Mn = 2.86, weight loss ratio = 7.3%

A6: SX100 (polystyrene, manufactured by Yasuhara Chemical Co., Ltd., Mw = 2663, Mw / Mn = 2.05, weight loss rate = 3.3%)

&Lt; Industrial Availability >

The optical component made of the injection-molded product of the present invention is preferably 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 because it has high refractive index and excellent transparency. The polystyrene (A) and the cycloolefin resin (B) contained in the resin composition for optical component formation of the injection molded product of the present invention are also compatible with each other even at a high temperature of 200 to 300 DEG C It is possible to obtain an optical component composed of an injection-molded article.

Claims (8)

(A) 1 to 40 parts by weight of polystyrene having a polystyrene-reduced weight average molecular weight (Mw) of 1,000 to 5,000 measured by gel permeation chromatography (GPC) (B) 100 parts by weight of a cyclic olefin resin having a glass transition temperature (Tg) of 100 to 180 占 폚 and having the following (i), (ii) or (iii) Wherein the optical component is formed from a resin composition containing an injection-molded article. (i) a ring-opening polymer of the compound represented by the formula (1) (ii) a ring-opening copolymer of a compound represented by the formula (1) and a copolymerizable monomer (iii) a hydrogenated (co) polymer of the ring-opened (co) polymer of (i) or (ii) &Lt; Formula 1 >

(Wherein R ¹ to R ⁴ are each a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 30 carbon atoms, or other monovalent organic groups, and may be the same or different, and any two of R ¹ to R ⁴ M is 0 or a positive integer, p is 0 or a positive integer, and at least one of R ² and R ⁴ is an alkoxycarbonyl group or allyloxycarbonyl group having a polar group ) The optical component according to claim 1, wherein the component (A) has a weight average molecular weight (Mw) of 2,000 to 4,500. The optical component according to claim 1 or 2, wherein the component (A) has a weight reduction ratio of 7% or less when heated at 250 ° C for 1 hour. The molded article according to claim 1 or 2, wherein the molecular weight distribution (Mw / Mn) of the component (A) in terms of polystyrene measured by gel permeation chromatography (GPC) is 1.0 to 4.0. Optical components. The optical component as claimed in claim 1 or 2, wherein the optical component is a lens. The optical component according to claim 5, wherein the injection molded article is injection molded using a flat plate having a thickness of 1 mm, wherein the total light transmittance obtained by the ASTM D1003 method is 91% or more. The injection molded product according to claim 5, which is injection molded using a flat plate having a thickness of 1 mm, wherein an optical component obtained by the ASTM D1003 method having a haze of 0.8 or less, (A) 1 to 40 parts by weight of polystyrene having a polystyrene-reduced weight average molecular weight (Mw) of 1,000 to 5,000 measured by gel permeation chromatography (GPC) (B) 100 parts by weight of a cyclic olefin resin having a glass transition temperature (Tg) of 100 to 180 占 폚 and having the following (i), (ii) or (iii) Wherein the resin composition comprises an injection-molded article. (i) a ring-opening polymer of the compound represented by the formula (1) (ii) a ring-opening copolymer of a compound represented by the formula (1) and a copolymerizable monomer (iii) a hydrogenated (co) polymer of the ring-opened (co) polymer of (i) or (ii) &Lt; Formula 1 >

(Wherein R ¹ to R ⁴ are each a hydrogen atom, a halogen atom, a hydrocarbon group of 1 to 30 carbon atoms, or other monovalent organic groups, and may be the same or different, and any two of R ¹ to R ⁴ M is 0 or a positive integer, p is 0 or a positive integer, and at least one of R ² and R ⁴ is an alkoxycarbonyl group or allyloxycarbonyl group having a polar group )