TWI533015B - An optical component formed by injection molding and an optical component forming resin composition formed by injection molding - Google Patents

Description

The optical component formed by the injection molded body and the resin component for forming an optical component formed by the injection molded body

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

In the prior art, an injection molded body such as an optical component using glass has been developed to be replaced by a plastic which is excellent in productivity, impact resistance, and light weight. For example, a lens for a digital camera, a lens for a mobile phone, a CD, a reading lens for a blue light, an optical lens typified by a microlens, a substrate such as a light disc, a light guide plate, a prismatic sheet, and the like are also developed to utilize a carbonate or a polymethyl group. Methyl acrylate or a cyclic olefin resin. However, carbonates have a large birefringence, and polymethyl methacrylate has a problem of low heat resistance and high water absorption.

The cyclic olefin-based resin has a glass transition temperature and a high light transmittance, and exhibits a characteristic of low birefringence or the like in comparison with the optical resin of the prior art because of the small anisotropy of the refractive index. Thermoplastic resins excellent in transparency and optical properties are attracting attention. According to the above-described features, for example, a cyclic olefin resin is used in the fields of optical materials such as optical disks, optical lenses, optical fibers, transparent plastic substrates, and low dielectric materials, such as electronic materials, optical semiconductors, and the like.

However, the cyclic olefin resin is excellent in transparency, low water absorbability, and low birefringence, but the refractive index is lower than that of the optical glass in the lens application. Therefore, the demand for thinning and weight reduction cannot be sufficiently achieved. Therefore, it has been strongly desired to develop a cyclic olefin-based resin having high refractive index in addition to the above-described characteristics of the cyclic olefin-based resin.

In general, the refractive index of the resin is known to be increased by increasing the content of the aromatic ring, the halogen atom or the sulfur atom, and the aromatic olefin resin, the halogen atom, the sulfur atom or the like is introduced into the cyclic olefin resin. Blends of heterogeneous polymers are hopefully achieved. For example, Patent Document 1 discloses that a ring-opening polymer containing a norbornene derivative of an aromatic ring has a high refractive index. Further, in Patent Documents 2 to 5, although a refractive index is not mentioned, a blend of a cyclic olefin resin and a styrene resin is proposed. However, the former norbornene-based ring-opening polymer containing an aromatic ring has a problem that the cost of the monomer used for the production or the ring-opening polymerization catalyst is high, and the latter is styrene. In the case of a resin blend, since phase separation occurs at a high temperature of 200 to 300 ° C corresponding to the injection molding temperature, it is extremely difficult to obtain a transparent injection molded body. Further, in order to maintain transparency without phase separation, the amount of the styrene-based resin to be added is limited, and the problem of desired optical characteristics cannot be obtained.

Therefore, it is strongly desired to suppress the phase separation and to easily obtain a resin component such as a transparent optical component and an optical component such as a lens having a high transparency as a main component of the resin composition, even when a molding method at a high temperature is used. It has emerged, in particular, a new approach to achieving high refractive index in order to use inexpensive materials.

[Patent Document 1] Patent No. 3291857

[Patent Document 2] Patent No. 3775552

[Patent Document 3] JP-A-2006-188555

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

[Patent Document 5] Patent No. 3018378

An object of the present invention is to provide an optical component formed by an injection molded body having a high refractive index and excellent transparency.

The inventors of the present invention have conducted intensive studies on the problems to be solved as described above, and have found that the present invention can achieve the above problems. That is, the present invention contains the following matters.

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

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

[3] The optical component formed by the injection molded body according to [1] or [2], wherein the weight of the component (A) heated at 250 ° C for 1 hour is reduced to 7% or less.

[4] The optical component formed by the injection molded body according to any one of [1] to [3], wherein the component (A) measured by a gel permeation chromatography (GPC) is converted into polystyrene The molecular weight distribution (Mw/Mn) is from 1.0 to 4.0.

[5] The optical component formed by the injection molded body 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).

(In the formula (1), R ¹ to R ⁴ are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or another monovalent organic group, and each of them may be the same or different; and further, R ¹ to R ⁴ Any two of them may be bonded to each other to form a single-ring or polycyclic structure; m is 0 or a positive integer, and p is 0 or a positive integer).

[6] The optical component formed by the injection molded body according to any one of [1] to [5] wherein the resin composition is formed into a thickness of 3.2 by heating at 300 ° C by an injection molding method. In the case of a molded plate of mm, the molded plate has a haze of 1% or less.

[7] The optical component formed by the injection molded body according to [6], wherein the optical component is a lens.

[8] A resin composition for an optical component formed by injection molding, characterized in that (A) a polystyrene-equivalent weight average molecular weight (Mw) measured by a gel permeation chromatograph (GPC) is 1,000 to 5,000. 1 to 40 parts by weight of polystyrene and (B) 100 parts by weight of a cyclic olefin resin having a glass transition temperature (Tg) of 100 to 180 °C.

The resin composition according to the present invention is obtained by containing a specific polystyrene in a cyclic olefin resin, and can provide an optical component formed by an injection molded body having a high refractive index. Further, in the resin composition according to the present invention, when the optical component formed by the injection molded body is formed, even if it is heated at a high temperature, an optical component formed by an injection molded body which does not phase separate and has high transparency can be provided. .

[Best Mode for Carrying Out the Invention]

The optical component formed by the injection molding of the present invention is a polystyrene (A) having a polystyrene equivalent weight average molecular weight (Mw) of 1,000 to 5,000 as measured by a gel permeation chromatography (GPC) (hereinafter also A cyclic olefin resin (B) having a glass transition temperature (Tg) of 100 to 180 ° C (hereinafter referred to as "polystyrene (A)")) (hereinafter referred to as "polystyrene (A)") (hereinafter also referred to as "cyclic olefin resin" (B)") 100 parts by weight of a resin composition (hereinafter also referred to as "resin composition for injection molded body").

Hereinafter, these substances will be described.

[Polystyrene (A)]

The polystyrene (A) used in the present invention, a manufacturer of a conventional method, or a commercially available product can be used without particular limitation. For example, SX100 (manufactured by YASUHARA CHEMICAL), NVC S94 (manufactured by Sanyo Chemical Industries Co., Ltd.), and the like can be mentioned. The polystyrene (A) may be used alone or in combination of two or more.

The polystyrene (A) has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 1,000 to 5,000, preferably 2,000 to 4,500, more preferably 2,500 to 4,500. When Mw is less than 1,000, the strength of the optical component formed by the injection molded body is lowered. On the other hand, when Mw is more than 5,000, the compatibility with the cyclic olefin-based resin (B) is deteriorated, and the refractive index cannot be dissolved to the refractive index. The improvement is in an effective range, and the transparency of the optical component formed by the injection molded body is lowered.

Further, the molecular weight distribution Mw/Mn of the polystyrene (A) is not particularly limited, but is usually preferably 1.0 to 4.0, more preferably 1.1 to 3.5, still more preferably 1.2 to 2.5. When the Mw/Mn is more than 4.0, the compatibility with the cyclic olefin-based resin (B) is deteriorated, and the haze of the optical component formed by the injection molded body is increased.

Further, the polystyrene (A) used in the present invention has a weight loss rate of 7% or less, preferably 6% or less, by heating at 250 ° C for 1 hour. When the weight reduction rate is more than 7%, there is a case where gas is generated during molding, and the mold is injected into the mold of the molding machine.

The blending amount of the polystyrene (A) in the optical component formed by the injection molding is preferably from 1 to 40 parts by weight, more preferably from 5 to 100 parts by weight based on 100 parts by weight of the cyclic olefin resin (B). 40 parts by weight. When the blending amount of the polystyrene is in the range of 1 to 40 parts by weight, the compatibility between the polystyrene (A) and the cyclic olefin resin (B) is inferior, and the optical component formed by the injection molded body is cloudy.

[Cyclic olefin resin (B)]

The cyclic olefin-based resin (B) used in the present invention may, for example, be a (co)polymer as described below.

(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 the above (i) or (ii).

(iv) a hydrogenated (co)polymer obtained by subjecting the ring-opened (co)polymer of the above (i) or (ii) to cyclization by a Friedel-Clartz reaction.

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

(vi) an addition (co)polymer selected from the group consisting of a compound represented by the formula (1), a vinyl cyclic hydrocarbon monomer, and a cyclopentadiene monomer, and hydrogenation thereof (total) )polymer.

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

(In the formula (1), R ¹ to R ⁴ are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or another monovalent organic group, and each of them may be the same or different; and further, R ¹ to R ⁴ Any two of them may be bonded to each other to form a single-ring or polycyclic structure; m is 0 or a positive integer, and p is 0 or a positive integer).

Among these, as the cyclic olefin-based resin (B), from the viewpoint of compatibility with the polystyrene (A) and the transparency of the optical component formed by the obtained injection molded body, ) better.

a 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 specific examples. A bicyclo[2.2.1]hept-2-ene, a tricyclo[4.3.0.1 ^2,5 ]-8-decene, a tricyclo[4.4.0.1 ^2,5 ]-3-undecene, a tetra Ring [4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene, pentacyclic [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 - alkene, 5-methyl-5-methoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyanobicyclo[2.2.1]hept-2-ene, 8-methoxycarbonyl Tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene, 8-ethoxycarbonyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodeca Alkene, 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-isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- ten Dodecene, 8-methyl -8-n- butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 5-ethylidene-bicyclo [2.2.1 Hept-2-ene, 8-ethylenetetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene, 5-phenylbicyclo[2.2.1]hept-2- Alkene, 8-phenyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene, 5-fluorobicyclo[2.2.1]hept-2-ene, 5-fluoromethyl Bicyclo[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-cis (fluoromethyl)bicyclo[2.2.1 Hept-2-ene, 5,5,6,6-tetrafluorobicyclo[2.2.1]hept-2-ene, 5,5,6,6-fluorene (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)di Ring [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 - alkene, 5,5,6-trifluoro-6-trifluoromethoxybicyclo[2.2.1]hept-2-ene, 5,5,6-trifluoro-6-heptafluoropropoxybicyclic [2.2.1] Hept-2-ene, 8-fluorotetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene, 8-fluoromethyltetracycline [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-trifluoromethyl Tetracycline [4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene, 8-pentafluoroethyltetracycline [4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodeca Alkene, 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-para (trifluoromethyl)tetracyclic [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-indole (trifluoromethyl)tetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene, 8,8-difluoro-9,9-double (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-trifluoro Methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene, 8-chloro-8,9,9-trifluorotetracycline [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 and the like.

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

Examples of the compound represented by the above formula (1) include R ¹ to R ⁴ each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or another monovalent organic group; and R ¹ to R ⁴ may be in any two mutually bonded to form a monocyclic or polycyclic ring structure; m is 0 or a positive integer, p is 0 or a positive integer).

Wherein R ¹ and R ³ are each independently a hydrogen atom or a hydrocarbon group having a carbon number of 1 to 10, preferably 1 to 4, more preferably 1 to 2; and it is desirable that each of R ² and R ^{4 is} independently a hydrogen atom. Or a monovalent organic group, at least one of R ² and R ⁴ is a polar group; m is desirably an integer of 0 to 3, p is an integer of 0 to 3, preferably m + p = 0 to 4, more preferably m+p=0~2, particularly preferably m=1, p=0. In particular, when m = 1 and p = 0, the obtained cyclic olefin-based resin (B) is particularly preferable because it has a high glass transition temperature and excellent mechanical strength.

The polar group of the compound represented by the above formula (1) may, for example, be a carboxyl group, a hydroxyl group, an alkoxycarbonyl group, an allyloxycarbonyl group, an amine group, a decylamino group or a cyano group. These polar groups may be bonded via a linking group such as a methylene group, and the methylene group may also have a polar group such as a carbonyl group, an ether group, a carboxyalkyl ether group, a thioether group or an imido group. Divalent organic group. Among these polar groups, a carboxyl group, a hydroxyl group, an alkoxycarbonyl group or an allyloxycarbonyl group is preferred, and an alkoxycarbonyl group or an allyloxycarbonyl group is more preferred.

Further, when at least one of R ² and R ⁴ is a polar group represented by the formula -(CH ₂ ) _n COOR , the obtained cyclic olefin-based resin (B) has a high glass transition temperature and low hygroscopicity. And excellent adhesion to various materials is preferred. 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, and more preferably an alkyl group. Further, n is usually 0 to 5, but preferably 0 to 3. The smaller the value of n, the higher the glass transition temperature of the obtained cyclic olefin-based resin (B) is, and the more preferable, and the fact that n is 0 is preferable from the viewpoint of easy synthesis.

Further, in the compound represented by the above formula (1), R ¹ and R ³ are preferably an alkyl group, and an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, particularly preferably methyl. In particular, when the alkyl group is bonded to the same carbon atom as the carbon atom to which the polar group represented by the above formula -(CH ₂ ) _n COOR is bonded, the obtained cyclic olefin resin (B) can be lowered. It is hygroscopic and preferred.

Copolymerizable monomer

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

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

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

Ring-opening polymerization catalyst

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

The replacement catalyst is at least one selected from the group consisting of (a) compounds of W, Mo, and Re, and (b) the elements of Group IA of the periodic law (eg, Li, Na, K, etc.), and Group IIA elements. (eg, Mg, Ca, etc.), Group IIB elements (eg, Zn, Cd, Hg, etc.), Group IIIA elements (eg, B, Al, etc.), Group IVA elements (eg, Si, Sn, Pb, etc.), or Group IVB elements ( For example, a compound of Ti, Zr, or the like, and a catalyst formed by a combination of at least one selected from the group consisting of at least one element-carbon bond or the element-hydrogen bond. Further, in order to increase the activity of the catalyst, other additives described later may be added.

Examples of the compound (W), which are preferably W, Mo or Re, include, for example, WCl ₆ , MoCl ₆ , ReOCl _{3 ,} etc., JP-A-1-132626, page 8 of the lower left column, line 6 to page 8, upper right column The compound described in the 17th line.

Examples of the component (b) include 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 , and (C ₂ H ₅ ) AlCl. ₂ , methyl aluminum tetrahydrofuran, LiH, etc., JP-A-1-132626, page 8 of the upper right column, line 18 to page 8, the lower right column, the third line of the compound.

Examples of the other additives include alcohols, aldehydes, ketones, amines, and the like, and it is also possible to use the above-mentioned line 16 of the lower right column of the eighth page of the first page of the first page of the Kaiping 1-132626. The compound shown.

The molar ratio of the component (a) to the compound represented by the above formula (1), the "component (a): the compound represented by the formula (1)" is usually 1: as the amount of the substitution catalyst. 500 to 1:50,000, preferably in the range of 1:1,000 to 1:10,000.

Further, 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 the metal atomic ratio.

Solvent for polymerization

The solvent to be used in the ring-opening polymerization reaction is not particularly limited as long as it is a compound capable of dissolving the molecular weight modifier, the compound represented by the above formula (1), and a substitution catalyst, and examples thereof include pentane and hexane. Alkane such as heptane, octane, decane or decane, cycloalkane such as cyclohexane, cycloheptane, cyclooctane, decalin or norbornane, benzene, toluene, xylene and Halogenated alkane such as aromatic hydrocarbon such as benzene or cumene, chlorobutane, bromohexane, dichloromethane, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform or tetrachloroethylene, halogenated a compound such as an aryl group, ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate, dimethoxyethane, etc., saturated carboxylic acid esters, dibutyl ether, tetrahydrofuran, dimethoxy Ethers such as ethane and the like. These may be used singly or in combination; among these, aromatic hydrocarbons are preferred.

In addition, as the solvent, the "solvent: the compound represented by the above formula (1)" is usually 1:1 to 10:1, preferably 1:1 to 5:1 by weight.

Molecular weight regulator

The molecular weight of the ring-opening (co)polymer can be adjusted by the polymerization temperature, the type of the catalyst, and the type of the solvent. However, in the present invention, the molecular weight modifier is adjusted by coexisting in the reaction system.

In addition, examples of the molecular weight modifier include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-decene, and the like. Α-olefins and styrene. Among these, 1-butene and 1-hexene are particularly preferred.

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 the mole of the compound 1 represented by the above formula (1) supplied to the ring-opening polymerization reaction.

In order to obtain the ring-opening copolymer of the above (ii), the compound represented by the above formula (1) and the copolymerizable monomer may be subjected to ring-opening copolymerization in a ring-opening polymerization step, and if necessary, in the polybutylene. a conjugated diene compound such as a diene or a polyisoprene, a styrene-butadiene copolymer, an ethylene-nonconjugated diene copolymer, a polynorbornene or the like, and contains two or more carbons in the main chain. The compound represented by the above formula (1) is subjected to ring-opening polymerization in the presence of an unsaturated hydrocarbon polymer such as a double bond between carbons.

The ring-opening (co)polymer obtained as described above can be used as it is, but the hydrogenated (co)polymer of the above (iii) obtained by rehydrogenation is also suitable as a raw material for a resin having high impact resistance. use.

Hydrogenation catalyst

Hydrogenation reaction, usually used, that is, by adding a hydrogenation catalyst to a solution of a ring-opening polymer, and adding hydrogen gas at a normal pressure of -300 atmospheres, preferably 3 to 200 atmospheres, at 0 to 200 ° C. It is carried out at a temperature of 20 to 180 ° C.

As the hydrogenation catalyst, a hydrogenation reaction of a usual 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 such as palladium, platinum, nickel, rhodium or ruthenium is supported on a carrier such as carbon, ceria, alumina or titania. Further, as the homogeneous catalyst, nickel naphthenate/triethylaluminum, nickel acetonitrile acetone/triethylaluminum, cobalt octylate/n-butyllithium, dichlorotitanium dichloride/monochlorinated dichloride may be mentioned. Ethyl aluminum, barium acetate, chloroform (triphenylphosphine) ruthenium, dichloro ginseng (triphenylphosphine) ruthenium, chlorohydrocarbonyl carbonyl (triphenylphosphine) ruthenium, dichlorocarbonyl ginseng (triphenylphosphine) Hey. The form of the catalyst may be powder or granular.

These hydrogenation catalysts are used in a ratio of a ring-opening (co)polymer: a hydrogenation catalyst (weight ratio) of 1:1 × 10 ^-6 to 1:2.

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

Further, the hydrogenation ratio of the hydrogenated (co)polymer is 50% or more, preferably 90% or more, more preferably 98% or more, and most preferably 99% or more, as measured by 500 MHz and ¹ H-NMR. The higher the hydrogenation rate, the more excellent the stability to heat or light, and when used as an optical component formed by the injection molded body of the present invention, it is possible to obtain characteristics that are stable over a long period of time.

In addition, as the hydrogenated (co)polymer used in the cyclic olefin resin (B) according to the present invention, the gel content of the hydrogenated (co)polymer is preferably 5% by weight or less, and preferably 1 part by weight. % below is especially good.

Further, as the cyclic olefin resin (B) according to the present invention, the ring-opening (co)polymer of the above (i) or (ii) may be used by the Friedel-Clartz reaction. After cyclization, the hydrogenated (co)polymer.

Cyclization by the Friedel-Krats reaction

The method of cyclizing the ring-opening (co)polymer by the Friedel-Clartz reaction is not particularly limited, but a conventional one using the acidic compound described in JP-A-50-154399 can be used. method. Specific examples of the acidic compound include Lewis acid and Bronsted acid such as AlCl ₃ , BF ₃ , FeCl ₃ , Al ₂ O ₃ , HCl, CH ₂ ClCOOH, zeolite, and activated clay.

The ring-opened (co)polymer which is cyclized by the Friedel-Clartz reaction can be hydrogenated in the same manner as the ring-opened (co)polymer of (i) or (ii) above.

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

Compound containing an unsaturated double bond

The compound containing an unsaturated double bond in the above (v) may, for example, be ethylene, propylene or butylene, and is preferably an olefin-based compound having 2 to 12 carbon atoms and more preferably 2 to 8 carbon atoms.

The compound represented by the above formula (1) and the compound containing an unsaturated double bond are preferably used in a weight ratio of 90/10 to 40/60, preferably 85/15 to 50/50.

Further, a saturated copolymer of a compound represented by the above formula (1) and a compound containing an unsaturated double bond is produced by an addition polymerization method which is usually used.

Addition polymerization catalyst

As the catalyst for synthesizing the saturated copolymer of the above (v), at least one selected from the group consisting of a titanium compound, a zirconium compound, and a vanadium compound, and an organoaluminum compound as a promoter can be used.

Here, 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. Wait.

Further, as the vanadium compound, a general formula of VO(OR) _a X _b or V(OR) _c X _d may be used. [R, R is a hydrocarbon group, and X is a halogen atom; 0≦a≦3, 0≦b≦3, 2 ≦ (a + b) ≦ 3, 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ (c + d) ≦ 4] The vanadium compound represented by these, or such an electron donor addition.

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

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

In the above, the ratio of the vanadium compound to the organoaluminum compound when the vanadium compound is used, for example, the ratio of the aluminum atom to the vanadium atom (Al/V) is 2 or more, preferably 2 to 50, particularly preferably 3 to 20. .

The solvent for the polymerization reaction used for the addition polymerization can be the same as the solvent used for the ring-opening polymerization reaction. Further, the adjustment of the molecular weight of the obtained saturated copolymer of (v) is usually carried out using hydrogen.

In addition, as the cyclic olefin resin (B) according to the present invention, the compound represented by the above formula (1), the ethylene cyclic hydrocarbon monomer, and the cyclopentadiene series may be used. An addition copolymer of one or more kinds of monomers selected by the body and a hydrogenated copolymer thereof.

Ethylene cyclic hydrocarbon monomer

The vinyl cyclic hydrocarbon-based monomer of the above (vi) may, for example, be a vinylcyclopentene monomer such as 4-vinylcyclopentene or 2-methyl-4-isopropenylcyclopentene. a vinylated 5-membered cyclic hydrocarbon monomer such as a vinylcyclopentane monomer such as 4-vinylcyclopentane or 4-isopropenylcyclopentane, 4-vinylcyclohexene or 4-iso Vinyl such as propylene cyclohexene, 1-methyl-4-isopropenylcyclohexene, 2-methyl-4-vinylcyclohexene, 2-methyl-4-isopropenylcyclohexene Vinylcyclohexane monomer such as cyclohexene monomer, 4-vinylcyclohexane or 2-methyl-4-isopropenylcyclohexane, styrene, α-methylstyrene, 2 -styrene of methylstyrene, 3-methylstyrene, 4-methylstyrene, 1-vinylnaphthalene, 2-vinylnaphthalene, 4-phenylstyrene, p-methoxystyrene, etc. Monomer, d-fluorene, 1-fluorene, dioxane, d-limonene, 1-limonene, dipentene, etc., fluorene monomer, 4-vinylcycloheptene, 4-isopropenylcycloheptene, etc. A vinyl cycloheptene monomer such as a vinylcycloheptene monomer, 4-vinylcycloheptane or 4-isopropenylcycloheptane. Among them, styrene and α-methylstyrene are preferred. These may be used alone or in combination of two or more.

Cyclopentadiene monomer

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

The addition (co)polymer of one or more kinds of monomers selected from the compound represented by the above formula (1), the ethylene cyclic hydrocarbon monomer, and the cyclopentadiene monomer can be used and (v) The compound represented by the formula (1) is produced by the same addition polymerization method as the saturated copolymer of the compound containing an unsaturated double bond.

Further, the hydrogenated (co)polymer of the above-mentioned addition (co)polymer may be hydrogenated in the same manner as the hydrogenated (co)polymer of the ring-opened (co)polymer of (iii) (i) or (ii) above. The law is manufactured.

Further, as the cyclic olefin resin (B) according to the present invention, an interpolymer of a compound represented by the above formula (1) (vi) and an acrylate may be used.

Acrylate

Examples of the acrylate used in the production of the cross-copolymer of the compound represented by the above formula (1) and the acrylate in the above (vii) include methacrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate. a heterocyclic ring having 2 to 20 carbon atoms such as a linear, divalent or cyclic alkyl acrylate, glycidyl acrylate or 2-tetrahydrofurfuryl acrylate having 1 to 20 carbon atoms such as an ester The aromatic ring group having 6 to 20 carbon atoms such as an acrylate or a benzyl acrylate has a carbon number of 7 to 30, such as an acrylate, an isophorone acrylate or a dicyclopentyl acrylate. The acrylate of the ring structure.

In the present invention, in order to obtain the cross-copolymer of the compound represented by the formula (1) (vii) and the acrylate, in the presence of a Lewis acid, the total of the compound represented by the above formula (1) and the acrylate are combined. 100 mol, usually 30 to 70 moles of the compound represented by the above formula (1), 70 to 30 moles of the acrylate, preferably 40 to 60 moles of the compound represented by the above formula (1), The amount of the acrylate is 60 to 40 moles, and it is particularly preferable to carry out radical polymerization using the compound represented by the above formula (1) in an amount of 45 to 55 moles and the acrylate in an amount of 55 to 45 moles.

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

In addition, the term "interactive copolymer" as used in the present invention means that the structural units derived from the compound represented by the above formula (1) are not adjacent to each other, that is, the structure derived from the compound represented by the above formula (1). The copolymer must have a copolymer of structural units derived from acrylates next to the unit; it is not a structure in which the structural units derived from the 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, preferably 0.3 to 3 dl/g, particularly preferably 0.4 to 1.5 dl, in terms of intrinsic viscosity [η] _inh . g; dissolved in tetrahydrofuran, the polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 8,000 to 100,000, preferably 10,000 to 80,000, particularly preferably 12,000 to 50,000; weight average molecular weight (Mw) is 20,000 to 300,000, preferably 30,000 to 250,000, particularly preferably in the range of 40,000 to 200,000. Further, the molecular weight distribution (Mw/Mn) is preferably from 2.0 to 4.0, more preferably from 2.5 to 3.7, still more preferably from 2.8 to 3.5. By using a resin having a small molecular weight distribution, it is possible to obtain a resin composition which is less likely to cause phase separation during heating, that is, a resin composition having a small variation in melt flow rate (MFR).

When the intrinsic viscosity [η] _inh , the number average molecular weight, and the weight average molecular weight are in the above range, the heat resistance, water resistance, chemical resistance, and mechanical properties of the cyclic olefin resin (B) are improved, and the injection molding of the present invention is improved. The forming workability of the optical component formed by the body is excellent.

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

In addition, as described above, the cyclic olefin resin (B) according to the present invention has a small molecular weight distribution. In the (co)polymer of the above (i) to (vii), in order to obtain a resin having a small molecular weight distribution, it is preferred to carry out ring-opening polymerization or addition polymerization in a plurality of stages.

For example, the multistage polymerization of the ring-opening (co)polymer of the above (i) or (ii) may be carried out by arranging the polymerization tanks in series, and after supplying the monomer component and the catalyst component to the polymerization tank, after a certain period of time, continuous or divided Next, a part of the polymerized monomer component and a mixture of the polymer component and the catalyst component are supplied to the polymerization tank of the second stage. In the polymerization tank of the next stage, a new monomer component and a catalyst component are supplied simultaneously with the supply of the above components, and polymerization is carried out, and the mixed liquid component is supplied to the polymerization tank of the next stage. The polymerization tank of the third stage is also polymerized in the same manner as the second stage, and by such a method, the conversion ratio of the polymer to be converted is at least 80% or more, preferably 85% or more, more preferably 88% or more, particularly Good for more than 90% of the method.

Further, in the addition (co)polymerization of the above (v) to (vii), the multistage polymerization may be carried out in accordance with the above ring-opening polymerization.

The cyclic olefin resin (B) according to the present invention preferably has a logarithmic viscosity (η) of 0.3 to 1.0 dL/g as measured in a chlorobenzene solution (concentration: 0.5 g/dL) at 30 °C. Further, it is desirable that the polystyrene-equivalent weight average molecular weight (Mw) measured by a gel permeation chromatography (GPC) of the cyclic olefin resin (B) is usually from 1.1 to 5.0, preferably from 1.5 to 4.5, more preferably It is 1.8~4.2.

When the molecular weight is too small, the strength of the optical component or the like formed by the injection molded body may be lowered. On the other hand, when the molecular weight is too large, the solution viscosity becomes too high and the productivity or workability of the resin composition according to the present invention is deteriorated.

[Other additives]

In the optical component formed by the injection molded body of the present invention, a hydrocarbon resin or an antioxidant or an ultraviolet absorber for improving heat deterioration resistance or light resistance may be added as necessary.

Examples of the hydrocarbon resin include a C5 resin, a C9 resin, a C5 based/C9 hybrid resin, a cyclopentadiene resin, a copolymer resin of an olefin/vinyl substituted aromatic compound, and a cyclopentadiene compound. / Vinyl-substituted aromatic copolymer copolymer resin, hydride of these resins, and hydride of vinyl-substituted aromatic resin. 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-based resin (B).

As the antioxidant, 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-dimethyl Diphenylmethane, hydrazine [methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 1,1,3-parade (2-methyl- 4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-paran (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-methylbenzene) Propionyloxy)ethyl], 2,4,8,10-tetraoxaspiro[5.5]undecane, ginseng (2,4-di-t-butylphenyl) phosphite, Cyclopentane tetrakis(2,4-di-t-butylphenyl)phosphite, cyclopentane tetrakisyl double (2) , 6-di-t-butyl-4-methylphenyl)phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-(2H-benzotriazol-2-yl)-4,6. -bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-di-t-pentylphenol, 2-benzotriazole -2-yl 4,6-di-t-butylphenol, 2,2'-methylene bis[4-(1,1,3,3-tetramethylbutyl)-6-[(2H-benzene) And triazol-2-yl)phenol]] and the like.

The content of the additive 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-based resin (B).

Further, for the purpose of improving workability, an additive such as a slip agent, a dye for improving the color tone, or a fluorescent whitening agent may be added.

[Resin composition for optical parts formed by injection molding]

The resin composition for an optical component formed by the injection molding of the present invention can be obtained, for example, by the following methods (I) to (III).

(I) A method in which polystyrene (A) and a cyclic olefin resin (B) and other additives are mixed using a two-axis extruder or a roll kneader.

(II) A method in which a cyclic olefin resin (B) is dissolved in a solution of a suitable solvent, polystyrene (A) and other additives are added, and mixed using a suitable agitator.

(III) mixing polystyrene (A) or a solution thereof, and a cyclic olefin resin (B) or a solution thereof, and other additives, using a devolatilizer or a ruder to carry out solvent removal The method of mixing.

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

[Injection molded body]

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

When the resin composition according to the present invention is formed into a molded plate having a thickness of 3.2 mm by an injection molding method under heating at 300 ° C, the molded article preferably has a haze of 1% or less, preferably 0.6% or less.

The injection molding machine is not particularly limited. Examples of the cylinder include an in-line method and a pre-molding method. The driving method includes a hydraulic type, an electric type, and a hybrid type. The mold clamping method may be a direct pressure. Type, toggle type; the direction of the shot can be listed as horizontal, vertical and the like. In addition, the mold clamping method can also be a launcher. The cylinder diameter and the mold clamping force are determined depending on the shape of the injection molded body. However, when the projected area of the injection molded body is large, the mold clamping force is preferably increased, and when the capacity of the injection molded body is large, the cylinder diameter is increased. Preferably.

When the cylinder is in-line type, the spiral shape such as the compression ratio, the length/diameter ratio, and the presence or absence of the sub flight can be appropriately selected, and the spiral surface can also be applied with chromium, titanium, or nitride. Conventional coatings such as carbon and carbon. Further, in order to improve the stability of the metering or injection operation, a mechanism for controlling the rotation or pressure of the spiral can be designed. Further, it is preferable that the cylinder and the hopper are sealed with an inert gas such as nitrogen by decompressing the inside of the hopper or the hopper in which the resin composition is stored, and the injection molded body can be stably obtained.

At the time of injection molding, a method of reducing the pressure in the cavity of the mold or an injection compression method is preferably applied in order to reduce the warpage of the molded body or to continuously form a stable shape.

When the inside of the cavity of the mold is reduced in pressure and then injection molded, the degree of pressure reduction is by gauge, preferably -0.08 MPa or less, more preferably -0.09 MPa or less, and particularly preferably -0.1 MPa or less. When the amount is more than the above range, the degree of pressure reduction is insufficient, and the molded article having excellent light transmittance and light diffusibility cannot be obtained.

The degree of pressure reduction in the above range is achieved by a conventional method such as a vacuum pump. It is preferable to use a conventional sealing material such as an O-ring or the like around the cavity or the ejector mechanism, and it is possible to use a grease for vacuum or the like in a range in which impurities or the like are not mixed in the injection molded body. Further, the suction port for the pressure reducing device such as the vacuum pump may be provided at any position in the mold, but is usually provided at the injector mechanism portion, the injection port and the end portion of the flow path, the sleeve structure portion, and the like. In addition, the vacuum suction program can be combined with the opening and closing of the mold to control by a solenoid valve or the like, or can be operated frequently, as long as the molten resin is filled, the method can achieve the desired degree of decompression in the mold cavity, and there is no Special restrictions.

When the inside of the cavity of the mold is depressurized and injection-molded, in order to eject the molten resin in a state where the mold groove is closed and the pressure is reduced, the injection delay time is usually set. The injection delay time is related to the capacity of the vacuum pump used and the size of the cavity, but it is usually about 0.5 to 3 seconds.

On the other hand, in the injection compression molding method, the groove interval is set to 1.5 to 20 times the thickness of the injection molded body, and the molten resin is injected in the gap, and the pressure of the resin measured on the cylinder side is maintained at 200~. In the range of 2,000 kgf/cm ² , the injection molding surface in the mold can be compressed to narrow the interval between the cavities.

Further, the core of the mold is set to be 1.1 to 10 times the thickness of the injection molded body, and is in a movable state, in which the molten resin is emitted, and after the injection or the end of the injection, the movable side core may have an average speed of 0.01 mm/ Sec~1mm/sec for compression.

As such an injection compression molding method, a conventional molding machine can be used.

The other conditions for injection molding are not particularly limited, but the cylinder temperature is usually 260 to 350 ° C, and the mold temperature is based on the glass transition temperature Tg of the cyclic olefin polymer, and is usually Tg-1 to Tg - 40 ° C. It is preferably in the range of Tg-5 to Tg-30 °C. Further, the injection speed differs depending on the size of the injection molded body of the present invention or the cylinder size of the molding machine. However, for example, when the cylinder diameter is 28 mm, it is usually 80 mm/sec or more, preferably 90 to 250 mm/sec. The pressure-retaining system is preferably adjusted as appropriate depending on the shape of the injection molded body to maintain the minimum pressure and time.

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

[Examples]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to the examples. In the following examples and comparative examples, "parts" and "%" indicate "parts by weight" and "% by weight" without special restrictions.

[Evaluation of Cyclic Olefin Resin (B)] <weight average molecular weight (Mw)>

A gel permeation chromatograph (manufactured by Tosoh Corporation, HLC-8220GPC, column); serially connected to the CARD column H _XL -H, TSK gel G7000H _XL , TSK gel GMH _XL 2 and TSK gel G2000H _XL manufactured by Tosoh Corporation. Solvent; tetrahydrofuran, flow rate; 1mL/min, sample concentration; 0.7~0.8% by weight, injection amount; 70μL, measuring temperature; 40°C, detector; RI (40°C), standard substance; TSK standard compound made by Tosoh Corporation Styrene), the weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the polystyrene (A) and the cyclic olefin resin (B) were measured.

<weight reduction rate (TGA)>

The weight loss rate of the polystyrene (A) was calculated by heating at 250 ° C for 1 hour using a TGA heat balance (manufactured by SII Co., Ltd., TG/DTA 6200).

<Glass transition temperature (Tg)>

The extrapolation glass transition start temperature of the cyclic olefin resin (hereinafter referred to simply as "glass transition temperature (Tg)") was calculated by using a differential scanning calorimeter (manufactured by SII Co., Ltd., DSC6200) in accordance with Japanese Industrial Standard K7121.

<hydrogenation rate>

The hydrogenation rate of the cyclic olefin resin (B) was calculated by measuring ¹ H-NMR in a hydrogenated chloroform using a superconducting nuclear magnetic resonance absorption apparatus (NMR, manufactured by Bruker Co., Ltd., AVANCE 500).

[Synthesis Example 1] <Synthesis of cyclic olefin resin (B1)>

8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene (DNM) represented by the following formula (2), as molecular weight The regulator 3.6 g of 1-hexene and 200 g of toluene were placed in a reaction vessel purged with nitrogen and heated to 80 °C. 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 thereto, and reacted at 80 ° C for 1 hour to obtain a ring-opened polymer. Solution. Next, to the obtained ring-opening polymer solution, 0.05 g of RuHCl(CO)[P(C ₆ H ₅ ) ₃ ] ₃ as a hydrogenation catalyst was added, and the hydrogen gas was pressed at 9 to 10 MPa to 160 to 165. The temperature was allowed to react for 3 hours at a temperature of °C. 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-based resin (B1) had Mw = 14.4 × 10 ⁴ , Mw / Mn = 3.25, Tg = 167 ° C, and hydrogenation ratio = 99.0% or more.

[Synthesis Example 2] <Synthesis of cyclic olefin resin (B2)>

8-methoxycarbonyl-8-methyltetracyclo[4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene (DNM) 585 g (2.518 mol) represented by the above formula (2) 5-methyl-5-methoxycarbonylbicyclo[2.2.1]hept-2-ene 315 g (1.895 mol), 1-hexene as a molecular weight regulator, 35.2 g (0.419 mol) and toluene 1350 g The reaction vessel was replaced with nitrogen and heated to 80 °C. Adding toluene solution of triethylaluminum (triethylaluminum concentration 0.61 mol/L) 4.70 mL, methanol-modified WCl ₆ in toluene solution (methanol-modified WCl ₆ concentration 0.025 mol/L) 17.65 mL, at 80 ° C This was allowed to react for 1 hour to obtain a ring-opened copolymer solution.

370 g of the obtained ring-opening copolymer solution was placed in an autoclave, and then 80 g of toluene was added. Next, 0.032 g of RuH(OCOCH ₃ )(CO)[P(C ₆ H ₅ ) ₃ ] ₂ as a hydrogenation catalyst was added, and then hydrogen gas was introduced to make the gauge pressure 10 MPa, and the pressure was maintained at 10 MPa and heated to 160 MPa. The reaction was carried out for 3 hours at ~165 °C. After the 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-based resin (B2) was Mw = 74,395, Mw/Mn = 3.10, Tg = 140 ° C, and hydrogenation ratio = 99.0% or more.

[Synthesis Example 3] <Synthesis of cyclic olefin resin (B3)>

8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ]-3-dodecene (DNM) 71 g, dicyclopentane represented by the above formula (2) 25 g of diene (DCP), and 1 g of dicyclo[2.2.1]hept-2-ene (NB) as a monomer, and 18 parts of 1-hexene of a molecular weight regulator, and 200 parts of toluene were charged with nitrogen. The displaced reaction vessel was heated to 100 °C.

0.005 parts of triethylaluminum and 0.005 parts of methanol-modified WCl ₆ (anhydrous methanol: PhPOCl ₂ :WCl ₆ =103:630:427 by weight) were added thereto, and a copolymer was obtained by allowing the reaction to proceed for 60 minutes.

Next, the solution of the obtained copolymer was placed in an autoclave, and then 200 parts of toluene was further added. Next, RuH(CO)[P(C ₆ H ₅ )] ₂ (OCO-p-Ph-nC ₅ H ₁₁ ) added with 0.0335 parts by weight of a hydrogenation catalyst is converted with respect to 100 parts by weight of the polymer solid fraction, and heated. After reaching 100 ° C, hydrogen gas was introduced into the reactor, and the pressure was set at 10 MPa. Then, the reaction was carried out at 165 ° 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 parts by weight of lactic acid, and 0.00214 parts by weight of hydrogen peroxide were added, and the mixture was heated at 60 ° C for 30 minutes. Then, 200 parts by weight of methanol was added and heated at 60 ° C for 30 minutes, and the mixture was cooled to 25 ° C to separate into two layers. 500 parts by weight of the supernatant liquid was removed, 350 parts by weight of toluene and 3 parts by weight of water were added, and heated at 60 ° C for 30 minutes, then 240 parts by weight of methanol was added thereto, heated at 60 ° C for 30 minutes, and then cooled to 25 ° C, and separated into 2 layers. . 500 parts by weight of the supernatant liquid was removed, 350 parts by weight of toluene and 3 parts by weight of water were added, and heated at 60 ° C for 30 minutes, then 240 parts by weight of methanol was added thereto, heated at 60 ° C for 30 minutes, and then cooled to 25 ° C, and separated into 2 layers. . After finally removing 500 parts by weight of the supernatant liquid, the polymer solution was heated to 50 ° C, and subjected to cycle filtration using filters of 2.0 μm, 1.0 μm, and 0.2 μm. The ratio of methanol to toluene in the solution was confirmed by gas chromatography, methanol/toluene = 20/80% by weight, and the dielectric ratio of the mixed solvent was 8.429 (dielectric ratio of methanol = 32.63, dielectric ratio of toluene = 2.379 calculated). Then, the polymer solid content was concentrated to 55%, and the solvent was removed by a solvent removal treatment at 250 ° C, 4 torr, and residence time for 1 hour, and passed through a 10 μm polymer filter to obtain a cyclic olefin resin (B3).

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

[Example 1] <Formation of injection molded body>

Polystyrene (A1) (manufactured by YASUHARA CHEMICAL, trade name: SX100, Mw = 3200, Mw/Mn = 2.11, weight reduction ratio = 3.6%) 0.6 kg, and the cyclic olefin resin obtained in Synthesis Example 1 (B1) 2.4 kg was melt-mixed using a two-axis extruder (TEM-37BS, Toshiba Machine Co., Ltd.) 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 resulting granules was transparent.

The obtained resin composition was vacuum-dried at 100 ° C for 4 hours, returned to normal pressure in a nitrogen atmosphere, and sealed in an aluminum bag sealed with nitrogen gas for storage. The resin composition was subjected to injection molding using a flat plate or a single-cavity mold having a width of 60 mm, a length of 80 mm, and a thickness of 1 mm by an injection molding machine (manufactured by FANUC Co., Ltd., α2000iB, cylinder diameter: 25 mm, and mold clamping 100 tons) to obtain a plate-like injection. Shaped body.

The conditions for the injection molding were a cylinder temperature of 305 ° C and a mold temperature of 100 ° C in terms of the solid 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 body.

<Haze, compatibility>

The haze was measured in accordance with the ASTM D1003 method. The haze of any three places of the injection molded body was measured using a HM-150 haze meter manufactured by Murakami Color Research Laboratory Co., Ltd., and the average value thereof was used. Those having a haze of less than 0.5% are ◎, those of 0.5% to 1.0% are ○, and those of more than 5.0% are ×.

<Full light transmittance>

The total light transmittance was measured in accordance with the ASTM D1003 method. The HM-150 haze meter manufactured by Murakami Color Technology Research Institute was used to measure the total light transmittance of any three places of the injection molded body, and the average value thereof was used.

<refractive index>

Using a PC-2010 type 稜鏡 coupling manufactured by Metricon Co., Ltd., the refractive index of any five places of the injection molded body was measured, and the maximum value and the minimum value were removed, and the values of the three average values were used. Further, the light source used 408, 633, and 830 nm laser light sources, and the refractive index obtained from the obtained refractive index was calculated by regression calculation using a formula of 589 nm.

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

As shown in Table 1, the formation and evaluation of the injection molded body were carried out 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.

A1: SX100 (polystyrene, manufactured by YASUHARA CHEMICAL, Mw = 3,200, Mw/Mn = 2.11, weight reduction rate = 3.6%)

A2: NVC S94 (polystyrene, Sanyo Chemical Industry Co., Ltd., Mw = 4,050, Mw / Mn = 3.41, weight reduction rate = 6.0%)

A3: ST-120 (polystyrene, Sanyo Chemical Industry Co., Ltd., Mw=11,500, Mw/Mn=2.08, weight reduction rate = 0.4%)

A4: GP G210C (polystyrene, manufactured by Toyo Styrene Co., Ltd., Mw = 199,900, Mw/Mn = 2.38, weight reduction rate = 0.2%)

A5: ST-95 (made by polystyrene, Sanyo Chemical Industry Co., Ltd., Mw = 5,100, Mw/Mn = 2.86, weight reduction rate = 7.3%)

A6: SX100 (polystyrene, manufactured by YASUHARA CHEMICAL, Mw = 2663, Mw / Mn = 2.05, weight reduction rate = 3.3%)

[Industrial availability]

The optical component formed by the injection molding of the present invention is excellent in transparency and transparency, and is suitable for use in an optical lens, a light guide plate, a diffusion plate, a transparent plastic substrate, a microlens, a disk substrate, and the like. In addition, the polystyrene (A) and the cyclic olefin-based resin (B) contained in the resin composition for forming an optical component formed by the injection molding of the present invention are at 200 to 300 ° C corresponding to the injection molding temperature. At high temperatures, optical components formed by injection molding can be obtained because of their excellent mutual compatibility.

Claims (8)

An optical component formed by injection molding, characterized by a resin composition comprising: (A) a polystyrene-equivalent weight average molecular weight (Mw) measured by a gel permeation chromatograph (GPC) 1 to 40 parts by weight of polystyrene of 1,000 to 5,000, and (B) 100 parts by weight of the cyclic olefin resin (i), (ii) or (iii) having a glass transition temperature (Tg) of 100 to 180 ° C (i) a ring-opening polymer of the compound represented by the formula (1), (ii) a ring-opening copolymer of the compound represented by the formula (1) and a copolymerizable monomer, (iii) the aforementioned (i) or (ii) a hydrogenated (co)polymer of a ring-opened (co)polymer; In the formula (1), R ¹ to R ⁴ are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or another monovalent organic group, and each of them may be the same or different; and any of R ¹ to R ⁴ The two may be bonded to each other to form a monocyclic or polycyclic structure; 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 a polar alkoxy group Carbonyl or allyloxycarbonyl. An optical component formed by the injection molding of the first aspect of the invention, wherein the component (A) has a weight average molecular weight (Mw) of 2,000 to 4,500. The optical component formed by the injection molding of the first or second aspect of the patent application, wherein the weight reduction rate of the component (A) heated at 250 ° C for 1 hour is 7% or less. An optical component formed by the injection molding of the first or second aspect of the patent application, wherein the polystyrene-equivalent molecular weight distribution (Mw/Mn) of the component (A) measured by a gel permeation chromatography (GPC) is 1.0~4.0. An optical component formed by projecting a molded body according to claim 1 or 2, wherein the optical component is a lens. The optical component formed by the injection molded body of the fifth aspect of the patent application, wherein the total light transmittance measured by the ASTM D1003 method is 91% or more in the injection molded body formed by using a flat plate having a thickness of 1 mm. An optical component formed by the injection molding of the fifth aspect of the invention, wherein the haze of the injection molding formed by using a flat plate having a thickness of 1 mm is 0.8 or less according to the ASTM D1003 method. A resin composition for forming an optical component formed by injection molding, characterized in that (A) polystyrene-equivalent polystyrene having a polystyrene-equivalent weight average molecular weight (Mw) of 1,000 to 5,000 measured by a gel permeation chromatography (GPC) 100 parts by weight of the cyclic olefin resin of the following (i), (ii) or (iii) having 1 to 40 parts by weight of ethylene and (B) a glass transition temperature (Tg) of 100 to 180 ° C; (1) a ring-opening polymer of the compound represented, (ii) a ring-opening copolymer of a compound represented by the formula (1) and a copolymerizable monomer, (iii) an open ring of the above (i) or (ii) a hydrogenated (co)polymer of (co)polymer; In the formula (1), R ¹ to R ⁴ are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or another monovalent organic group, and each of them may be the same or different; and any of R ¹ to R ⁴ Two of them may be bonded to each other to form a monocyclic or polycyclic structure; m is 0 or a positive integer, p is 0 or a positive integer; and at least one of R2 and R4 is a polar alkoxycarbonyl group or Allyloxycarbonyl.