TW200927816A - Alicyclic hydrocarbon random copolymer, method for producing the same , resin composition , and the moldings - Google Patents

Abstract

It is provided an alicyclic hydrocarbon random copolymer, which comprises repeated units of alicyclic structure and repeated units of chain structure. The repeated units of alicyclic structure are specific repeated units of alicyclic structure, and the repeated units of chain structure have specific repeated unit [B1] and specific repeated unit [B2], and the total content of each repeated unit is 90wt% and more, in which the content of repeated units of chain structure is from 1 to 15wt% and the content of repeated units [B1] in repeated units of chain structure is 70 mol% and less. Further, the weight average molecular weight of alicyclic hydrocarbon random copolymer is from 10, 000 to 300, 000. It also provided the method of producing the said copolymer.

Description

200927816 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to an alicyclic hydrocarbon random copolymer having high heat resistance, low birefringence, and high laser resistance. Further, the present invention relates to a process for producing the alicyclic hydrocarbon random copolymer, a resin composition containing the alicyclic hydrocarbon random copolymer as a resin component, and molding the alicyclic hydrocarbon random copolymer or the like A molded product obtained by a resin composition. [Prior Art] An alicyclic hydrocarbon polymer obtained by hydrogenating an aromatic ring of an aromatic vinyl polymer such as polystyrene, in addition to a high light transmittance, is known to have a small birefringence and is suitable for an optical material. Resin material. For example, JP-A No. 1-317728 (Patent Document 1) proposes an aromatic ring of a styrene resin such as a hydrogenated polystyrene or a styrene-butadiene-styrene block copolymer to form a polyethylene ring. Hexane resin Next, a method of producing the optical disk substrate by injection molding the polyethylene cyclohexane resin is carried out. The alicyclic hydrocarbon polymer obtained by the aromatic ring of the hydrogenated aromatic vinyl polymer is excellent in transparency, low birefringence, low water absorption, and the like, and is not only used as a disc substrate, but also is suitable for reading signals as a disc or the like. Use the read lens. However, although the reading lens system requires a small complex refractive index, since the shape is complicated, in the case of molding using a conventional alicyclic hydrocarbon polymer, the birefringence tends to become larger as compared with the optical disk substrate. The birefringence of an optical component is affected by both the inherent birefringence and the residual stress at the time of molding in the resin material used. It is difficult to reduce the inherent birefringence in the resin material. On the one hand, when the resin is formed at the time of molding -4-200927816, the molecular weight of the resin material is made small on the one hand to improve the melt fluidity of the resin material during molding, and the residual stress of the molded article can be reduced. However, when the resin temperature at the time of molding is increased, the molded article is liable to be thermally decomposed or thermally deteriorated. When the molecular weight of the resin material becomes small, the mechanical strength of the molded article is lowered. JP-A-200-48924 (Patent Document 2) proposes a random copolymerized aromatic vinyl monomer, a conjugated diene monomer, and other ethylene monomers as desired to synthesize an aromatic ethylene copolymer. Next, an alicyclic hydrocarbon copolymer comprising a carbon-carbon unsaturated double bond of an aromatic ring of the fluorene aromatic ethylene copolymer is hydrogenated. The alicyclic hydrocarbon copolymer disclosed in Patent Document 2 is excellent in transparency and low birefringence, and is excellent in mechanical strength such as tensile strength, and is a resin material suitable for molding optical parts such as lenses. In recent years, the development of semiconductor lasers with short vibration wavelengths has been developed, with the development of high-density recording and/or rewritable media using wavelengths of 35 0 to 5 3 nm blue lasers with laser vibrations of shorter wavelengths. It is progressing rapidly. Therefore, it is required to have a © reading lens suitable for high-density recording and/or rewritable media. In the reading lens suitable for recording and/or rewritable media applications using semiconductor lasers having short vibration wavelengths such as blue lasers, in addition to excellent transparency, small birefringence, and good mechanical strength, laser resistance is required. Excellent in properties and heat resistance. When a semiconductor laser having a short vibration wavelength is irradiated, the irradiation energy density of the irradiated portion becomes high. The reading lens formed of the resin material is easily deteriorated. A reading lens that deteriorates due to laser irradiation reduces the light transmittance. The reading lens tends to be exposed to high temperatures due to miniaturization of recording and/or rewritable devices, high density of wiring, and short wavelength of laser emission signal wavelength. When the heat resistance of the resin material constituting the reading lens is low, it is likely to cause deformation or thermal deterioration in a high temperature environment. The result is a reduction in the performance of the read lens as the recording and/or rewritable machine is used. The alicyclic hydrocarbon copolymer disclosed in Patent Document 2 is a resin material suitable for the purpose of reading a lens. It is known that the laser resistance can be improved by selecting the copolymerization composition of the alicyclic hydrocarbon copolymer, and on the contrary, the glass transition temperature enthalpy shows a tendency to decrease. Therefore, in the alicyclic hydrocarbon copolymer, a space for further improvement is left. [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A highly balanced alicyclic hydrocarbon random copolymer and a process for the preparation thereof. Another object of the present invention is to provide a molded article using an optical composition containing the alicyclic hydrocarbon random copolymer, the alicyclic hydrocarbon random copolymer, or the resin composition. The present inventors have found that an alicyclic hydrocarbon random copolymer of a hydrogenated random copolymer of styrene and isoprene is disclosed in the example of JP-A No. 2001-48924 (Patent Document 2). Increasing the content of repeating units derived from isoprene increases the laser resistance and shows a tendency to lower the glass transition temperature. -6-200927816 In Patent Document 2, a process for producing an alicyclic hydrocarbon random copolymer is widely disclosed, and a repeating unit derived from a conjugated diene monomer such as isoprene is substantially only 1,4- The bond is a structure having no side chain vinyl structure. It is also known from the structure of the repeating unit of the co-shaved bis-ene monomer of the formula 3 in the first application of Patent Document 2. The present inventors have found that a total of at least one selected from the group consisting of isoprene and 1,3-butadiene is polymerized in the presence of a compound having an electron donor atom. a conjugated diene monomer and a random copolymer having a 1,4-bonding content of 70 mol% or less in a repeating unit of a conjugated diene monomer, followed by other ethylene monomers as desired A method of producing an alicyclic hydrocarbon hydrocarbon copolymer by hydrogenating a carbon-carbon unsaturated bond of the aromatic ring of the random copolymer is effective. The alicyclic hydrocarbon random copolymer of the present invention is excellent in transparency, low birefringence, mechanical strength, heat resistance, and laser resistance, and also improves laser resistance by increasing the repeating unit content from isoprene. The glass transition temperature is maintained at a high level and there is a tendency to improve the complex refraction. The alicyclic hydrocarbon random copolymer of the present invention varies with the copolymerization composition of the aromatic vinyl monomer and the conjugated diene monomer, and the glass transition temperature, the birefringence, and the laser resistance also fluctuate, or A recognized alicyclic hydrocarbon random copolymer having the same copolymerization composition (disclosed in Patent Document 2) has a tendency to improve low birefringence or laser resistance in addition to high glass transition temperature and improved heat resistance. The present invention arrives at the completion based on the knowledge found by them. According to the present invention, there is provided an alicyclic hydrocarbon random copolymer which is a 200927816 alicyclic hydrocarbon random copolymer containing a repeating unit [A] of an alicyclic structure and a repeating unit [B] of a chain structure, which The characteristic is that (1) the repeating unit [A] of the alicyclic structure has the following formula 1

❹ (In Formula 1, R1 and R2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, a carbonyloxy group having 1 to 20 carbon atoms, and cyanogen. Alkyl, hydrazino, fluorenylene, decyl, or a polar group (halogen atom, hydroxyl group, alkoxy group having 1 to 20 carbon atoms, alkylcarbonyloxy group having 1 to 20 carbon atoms, cyano group, decylamine) a repeating unit of an alicyclic structure represented by a thiol structure represented by a hydrazide or a hydrazinyl group substituted with a carbon number of 1 to 20; n is an integer of 0 or 1 to 5; (2) the chain The repeat unit [B] of the structure has the following formula 2 (2) .CH /CH2, CH/CH2'

Λ» I R: (in the formula 2, R3 is a hydrogen atom or a methyl group), the repeating unit [B,], and the following formula 3

(3) The repeating unit of the chain structure of the repeating unit [B 2] represented by (in the formula 3, R3 is a hydrogen atom or a methyl group); 8-200927816 (3) In the alicyclic hydrocarbon random copolymer The total content of the repeating unit [A] of the alicyclic structure and the repeating unit [B] of the chain structure is 9% by weight or more; (4) the chain structure in the alicyclic hydrocarbon random copolymer The content of the repeating unit [B] is 1 to 15% by weight; (5) the content of the repeating unit [B,] in the chain structure repeating unit [B] is 70 mol% or less; and (6) The alicyclic hydrocarbon random copolymer has a weight average molecular weight (Mw) in the range of 10,000 to 300,000 as determined by gel permeation chromatography. Further, according to the present invention, there is provided a process for producing the aforementioned alicyclic hydrocarbon random copolymer comprising the following steps I and II: (I) polymerizing an aromatic vinyl monomer 85 in the presence of a compound having an electron donor atom 1 to 15% by weight of conjugated diene monomer selected from the group consisting of at least one of isoprene and 1,3-butadiene, and 0 to 10% by weight with other ethylene monomers a step of synthesizing a random copolymer having a 1,4 -bonding content of 70% by mole or less in a repeating unit of the conjugated diene monomer; and (II) hydrogenating the random copolymer Step II of the main chain and the carbon-carbon unsaturated double bond comprising the side chain of the aromatic ring. Further, according to the present invention, there is provided a resin composition containing the above-mentioned alicyclic hydrocarbon random copolymer and an antioxidant. Further, according to the present invention, there is provided a molded article obtained by molding the above-mentioned alicyclic hydrocarbon random copolymer or resin composition. According to the present invention, an alicyclic hydrocarbon random copolymer having high heat resistance, low birefringence, and high laser resistance can be provided. The alicyclic hydrocarbon of the present invention is not a -9-200927816 copolymer or a resin composition containing the alicyclic hydrocarbon random copolymer, and a molding material which is a molded article of an optical component or the like can be used. Since the alicyclic hydrocarbon random copolymer of the present invention improves the laser resistance and suppresses the decrease in heat resistance, it is suitable as a recording and/or rewritable medium for use in a semiconductor laser having a short vibration wavelength such as a blue laser. The reading lens is formed from a material. [Embodiment] The alicyclic hydrocarbon random copolymer of the present invention is an alicyclic hydrocarbon random copolymer containing a repeating unit [A] having an alicyclic structure and a repeating unit [B] having a chain structure. The repeating unit [A] of the alicyclic structure is represented by the following formula 1

(The repeat unit represented by Μη with an alicyclic structure.

In Formula 1, R1 and R2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkylcarbonyloxy group having 1 to 2 carbon atoms, and a cyano group. , amidino, fluorenylene, decyl, or a polar group (halogen atom, hydroxyl group, alkoxy group having 1 to 20 carbon atoms, alkylcarbonyloxy group having 1 to 20 carbon atoms, cyano group, decylamino group) A hydrazine group having a carbon number of 1 to 20 substituted with a quinone imine group or a decyl group. η is an integer of 0 or 1 to 5. The hydrocarbon group is exemplified by an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10, preferably 1 to 6 carbon atoms; 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms; base. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom, and an iodine atom. The alkoxy group having 1 to 20 carbon atoms is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxycarbonyl group having 1 to 20 carbon atoms is preferably an alkylcarbonyloxy group having 1 to 6 carbon atoms. The hydrocarbon group substituted with a polar group is exemplified by a halogenated alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and preferably 1 to 6 carbon atoms. From the viewpoint of heat resistance and low water absorption, R1 and R2 are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The chain structure (non-alicyclic structure) repeating unit [B] constituting the alicyclic hydrocarbon random copolymer of the present invention has the formula 2 ❹ <, CH2\^.ΟΗ, ΓΙ, ch2' 2 , CH〆2, (2) - R3 - (in the formula 2, R3 is a hydrogen atom or a methyl group), the repeating unit [B,], and the following formula 3

(3) 重复 (The repeating unit of the chain structure of the repeating unit [b2] represented by (wherein R3 is a hydrogen atom or a methyl group). The repeating unit [BJ is the repeating unit of the addition reaction from isoprene and/or i,3-butadiene. More specifically, the repeating unit [^^ is the 1,4-bond of hydrogenated isoprene and/or the carbon-carbon of the main chain in the repeating unit of 1,4-bonded ι,3-butadiene The repeating unit of the unsaturated double bond. The repeating unit [B2] is a repeating unit of the addition reaction of 3,4·addition reaction and/or hydrazine, 3 -butadiene from isoprene. More specifically, the repeating unit [82] is hydrogenated isoprene-11-200927816 3,4·bonding and/or hydrazine, 3-butadiene i,2-bonding repeating unit side carbon- Repeating unit of carbon unsaturated double bonds. In the alicyclic hydrocarbon random copolymer of the present invention, the total content of the alicyclic structural repeating unit [A] and the chain-like structural repeating unit [B]* in the 'alicyclic hydrocarbon random copolymer is 90% by weight The above is preferably 95% by weight or more, preferably 99% by weight or more, and in many cases, 99.9% by weight. The remainder is as shown in the following formula 4

The repeating unit of the unhydrogenated aromatic vinyl monomer represented by (wherein R1 and R2 in the formula 4 are the same as those in the formula 1) is represented by the following formula: 5 • CH,

CH

C CH. (5) R3 (in the formula 5, R3 is a hydrogen atom or a methyl group), the unhydrogenated 1,4-addition reaction of isoprene and/or 1,3 butadiene The repeating unit obtained is given by the following formula 6 CH,

CH (6)

I C-

II

CH (in the formula 6, R3 is a hydrogen atom or a methyl group), the unhydrogenated 3,4-addition reaction of isoprene and/or 1,2 -addition of 1,3 -butadiene In response, the repeat unit of -12- (7) 200927816 is obtained by the following formula

4/5 R — C 丨R

6 ' 7 RIC 丨 R ❹

G

[In the formula 7, R4 to R7 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an alkylcarbonyloxy group having 1 to 20 carbon atoms, or a cyano group. , amidino, fluorenylene, decyl, or a polar group (halogen atom, hydroxyl group, alkoxy group having 1 to 20 carbon atoms, alkylcarbonyloxy group having 1 to 20 carbon atoms, cyano group, decylamino group) The repeating unit of the other ethylene monomer represented by the hydrocarbyl group having 1 to 20 carbon atoms substituted with a quinone imino group or a decyl group), or the content of two or more repeating units thereof. . The repeating unit [B] content of the chain structure in the alicyclic hydrocarbon random copolymer of the present invention is from 1 to 15% by weight, preferably from 2 to 10% by weight, from the viewpoint of balance of characteristics. It is particularly preferably from 3 to 6% by weight. When the content of the repeating unit [B] of the chain structure is too small, the tilting resistance of the increase in the birefringence is also lowered. When the content of the repeating unit [B] is too large, the heat resistance is lowered. In the alicyclic hydrocarbon random copolymer of the present invention, the repeating unit [Bl] content in the repeating unit [B] of the chain structure is 7 〇 mol% or less, preferably 6 〇 mol% or less. The best is 55% or less. The lower limit of the content of the repeating unit [61] is usually 40 mol%, and in most cases, 45 mol%. The content of the repeating unit [Bi] is a enthalpy in which the total of the repeating unit [Βι] and the repeating unit 2] is 100 mol%. In the case where /, the conjugated monoene monomer is isoprene (in the case where R3 is a methyl group in the formulas 2, 3, 5 and 6 representing the repeating unit-13-200927816), 1,4-addition occurs. The reaction and the 3,4-addition reaction are carried out without substantially causing a 1,2-addition reaction. When the content of the repeating unit in the repeating unit [B] of the chain structure is too large, the tendency of the glass transition temperature of the alicyclic hydrocarbon random copolymer to decrease is lowered, particularly maintaining high heat resistance and improving laser resistance. difficult. This repeating unit [an alicyclic hydrocarbon random copolymer having a too small BJ content is difficult to synthesize. The alicyclic hydrocarbon random copolymer of the present invention has a weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) φ of 10,000 to 300,000, preferably 30,000 to 250,000, preferably 50,000 to 200,000. . When the weight average molecular weight of the alicyclic hydrocarbon random copolymer of the present invention is too low, the mechanical strength is lowered. When the weight average molecular weight of the alicyclic hydrocarbon random copolymer of the present invention is too high, in addition to difficulty in synthesis, the residual stress of the molded article tends to increase during melt molding. When the residual stress of the molded article becomes large, the birefringence tends to become large. The glass transition temperature of the alicyclic hydrocarbon random copolymer of the present invention measured by a differential scanning calorimeter © (DSC) is preferably 1 oo ° C or more, preferably 1 0 5 ° C or more. 1 1 〇°c or more 'extra good is 1 2 〇t: above. The upper limit of the glass transition temperature is usually 1351: in most cases 130 °C. In the case of synthesizing the alicyclic hydrocarbon random copolymer of the present invention by, for example, amination of the present ethylene-isoamyl burnt/random copolymer, a recognized alicyclic ring corresponding to the same copolymerized composition is obtained. In the hydrocarbon-based random copolymer (Patent Document 2), the glass transition temperature is usually increased by 3 t: or more, preferably more than 5 C or more. In the case of synthesizing the alicyclic hydrocarbon random copolymer of the present invention by hydrogenation of a styrene-1,3-butadiene-random copolymer, there is also a tendency of the same -14-200927816. The alicyclic hydrocarbon random copolymer of the present invention is excellent in heat resistance and has low birefringence and excellent resistance to semiconductor lasers having a short vibration wavelength such as a blue laser. Therefore, the alicyclic hydrocarbon random copolymer of the present invention can maintain high level of heat resistance even if the repeating unit [B] content of the chain structure is increased to improve the laser resistance, and the birefringence can be made small. The alicyclic hydrocarbon random copolymer of the present invention is a random copolymer. This is known from the process for producing the alicyclic hydrocarbon random copolymer of the present invention. Further, the alicyclic hydrocarbon random copolymer of the present invention can be obtained by hydrogenating an aromatic vinyl monomer-conjugated diene obtained by random copolymerization of an aromatic vinyl monomer and a conjugated diene monomer. The copolymer of the aromatic vinyl monomer-conjugated diene monomer is a random copolymer which is known from the following relationship. Ozone addition of an unsaturated double bond in the main chain of the aromatic vinyl monomer-conjugated diene monomer copolymer, followed by reduction decomposition, and measurement of the weight average molecular weight (Mw) of the chain of the extracted aromatic vinyl monomer Number average molecular weight (Μη). © wherein D = the weight average molecular weight (Mw) of the chain of the aromatic vinyl monomer, and E = [the weight average molecular weight of the aromatic vinyl monomer-conjugated diene monomer copolymer X is derived from the aromatic vinyl monomer unit When the number of repeating units/the number of repeating units of the aromatic vinyl monomer-conjugated diene monomer copolymer is 4% or less, (D/E) x 100 is 30% or less, and it can be used as an aromatic vinyl monomer. The conjugated diene monomer copolymer is an indicator of a random copolymer. The styrene-isoprene copolymers obtained in Examples 1 to 4 of the present invention were all less than 30% (in the range of 5 to 20%) of (D/E) x 100, and were found to be absent. Regulations -15- 200927816. The molecular weight distribution of the alicyclic hydrocarbon random copolymer of the present invention can be appropriately selected depending on the purpose of use, but the weight average molecular weight (Mw) in terms of polystyrene (or polyisoprene) measured by GPC. The ratio (Mw/Mn) to the number average molecular weight (?n) is usually 2.5 or less, and is preferably 2.3 or less, preferably 2.0 or less, and most of them is 1.5 or less. The lower limit of Mw/Mn is usually 1.1, and in most cases it is 1.2. When Mw/Mn is in this range, mechanical strength and heat resistance are highly balanced. φ The alicyclic hydrocarbon random copolymer of the present invention can be solution-polymerized by hydrogenating an alicyclic ethylene monomer, if necessary, in the presence of a compound having two or more electrons to form a chelate structure with atoms. A method of conjugated diene monomer and, if necessary, other ethylene monomers copolymerizable. In order to obtain an alicyclic hydrocarbon random copolymer which is highly polymerized and excellent in various properties as described above, it is preferred to use a copolymerized aromatic vinyl monomer, a conjugated diene monomer, and a desired one. Other ethylene monomers, followed by hydrogenation of a method comprising an unsaturated double bond of an aromatic ring. Specifically, the alicyclic hydrocarbon random copolymer of the present invention can be polymerized by the following steps I and Π: (I) in the presence of a compound having an electron donor atom, to polymerize the aromatic vinyl monomer 85 to 99% by weight, from 1 to 15% by weight of the conjugated diene monomer selected from at least one of the group consisting of isoprene and 1,3-butadiene, and from 10% by weight to the other ethylene monomer, a step I for synthesizing a random copolymer having a 1,4-bond content of 70 mol% or less in a repeating unit of the conjugated diene monomer; and (II) hydrogenating the main chain of the random copolymer And a carbon-carbon-16-200927816 unsaturated double bond comprising a side chain of an aromatic ring. In terms of aromatic vinyl monomer, the following formula can be used

Ri (8) C=CH„ )n [In the formula 8, R1 and R2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 2 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, and a carbon number. 1 to 2 烷 alkyleneoxy, cyano, decylamino, quinone imine, decyl, or a polar group (_ atom, hydroxyl group, alkoxy group having 1 to 20 carbon atoms, carbon number 1 to An aromatic vinyl compound represented by a 20-alkylcarbonyloxy group, a cyano group, a decylamino group, a guanidino group, or a decyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms; n is an anthracene or an integer of 1 to 5] Preferred specific examples of the aromatic ethylenic monomer are styrene, α-methylstyrene, α-ethylstyrene, α·propylstyrene, α-isopropylstyrene, α-. Tert-butyl styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4- Tertiary butyl styrene, 5-t-butyl-2-methyl styrene, monochlorostyrene, dichlorostyrene, monofluorostyrene, 4-phenylstyrene, etc. Among them, styrene, 2-methylstyrene, 3-methylbenzene Alkene and 4-methylstyrene are preferred, and styrene is particularly preferred. For other ethylene monomers, a compound which can form a repeating unit represented by the above formula 7 is used. Examples are ethylene, propylene, 1-butene '1-pentene, 4-methyl-1-pentene, etc., alkene-17-200927816 hydrocarbon monomer; cyanoethylene (acrylonitrile), 1-cyano- a nitrile group monomer such as 1-methylethylene (methenenitrile) or 1-cyano-1-chloroethylene (α-chloroacrylonitrile); methyl acrylate, ethyl methacrylate, propyl methacrylate, An acrylate or methacrylate monomer such as butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate or butyl acrylate; or an unsaturated fatty acid monomer such as acrylic acid, acrylic acid or maleic anhydride. Among the ethylene monomers, olefin monomers are preferred, and olefins, propylene, and 1-butene are preferred. The vinyl monomers may be used singly or in combination of two or more kinds. In the step I, in the presence of a compound having an electron donor, by polymerizing an aromatic vinyl monomer, a conjugated monomer of at least one of the group consisting of pentadiene and 1,3-butadiene, and if necessary, other ethylene monomers, synthesized in the 1,4-denier unit of the conjugated diene A random anthracene having a bonding content of 70 mol% or less. In terms of a compound having an electron donor atom, it is preferred to have an electron selected from at least one of (S), oxygen (0), phosphorus (phosphonium), and the like. A compound having an electron and an atom, preferably a compound having a chelate structure having the above electrons and atoms, and a compound having two or more electrons and an atom to form a chelate structure. Preferably, the surface has a compound having a chelate structure in which at least electrons are supplied to the atom, such as sulfur (S), oxygen (0), phosphorus (phosphonium) or the like. In the case of an electron donor, oxygen (〇) is preferred. The compound having two or more electrons and an atom to form a chelate compound is exemplified by an ether compound, a third amine compound, a phosphonium propyl propyl propyl propylene methyl group, and an original isoprene. Each of the polysulfonation compounds has a square-type and original composition, -18-200927816 alkoxylated alkali metal compounds. Among these compounds, an ether compound is preferred from the viewpoint of reducing the molecular weight distribution (M w / Mn) of the random copolymer and preventing the hydrogenation reaction. Preferred specific examples of the ether compound include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol diisopropyl ether, ethylene glycol dibutyl ether, and ethylene glycol methyl group. Bis-coordinated ether compound such as phenyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol diisopropyl ether, propylene glycol dibutyl ether, propylene glycol methyl propyl ether: diethylene glycol dibutyl a tricoordinate ether compound such as a phenyl ether or a dipropylene glycol dibutyl ether; an ethylene glycol alkyl ether, a propylene glycol alkyl ether or the like. In the compounds, the alkyl moiety has a carbon number of usually from 1 to 6, preferably from 2 to 4. These ether compounds may be used singly or in combination of two or more kinds. When the aromatic vinyl monomer and the conjugated diene monomer are copolymerized by using a compound having two or more electrons to form a chelate structure with atoms, 3,4-addition of isoprene is likely to occur. The reaction or the 1,2-addition reaction of 1,3-butadiene gives a random copolymer having a small content of 1,4-bonded. Further, when a compound having a chelate structure having two or more electron donor atoms is used, the molecular weight distribution (Mw/Mn) of the random copolymer tends to be slightly widened, and the molecular weight distribution is narrow. In the case of a copolymer, a randomizing agent such as a dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether or tetrahydrofuran can be used at the same time. The compound having an electron donor atom is preferably a compound having a chelate structure of two or more electrons supplied to the atom, and is preferably from 0. 001 to 10 parts by weight with respect to 100 parts by weight of the monomer. It is used in a ratio of 0.01 -19 to 200927816 to 1 part by weight. The polymerization method is not particularly limited, and examples thereof include a batch polymerization method (batch method), a monomer sequential addition method, and the like. In the monomer sequential addition method, a uniformly mixed monomer mixture is successively added to carry out polymerization in a polymerization system in which an initiator is present. In the monomer sequential addition method, it is preferred to carry out the polymerization by sequentially adding the remaining monomer mixture after using a part of the total amount of the monomer mixture and starting the polymerization. In particular, when a monomer sequential addition method is used, a copolymer having a preferred linked structure is easily obtained.共聚物 The copolymer before hydrogenation has a smaller random structure than the aforementioned (D/E)x100. The degree of randomness of the copolymer is determined by the ratio of the polymerization rate of the aromatic vinyl monomer to the polymerization rate of the conjugated diene monomer. The smaller the ratio, the more irregular the ratio is. A copolymer of a chain structure. According to the foregoing monomer addition method, since the uniformly mixed monomer mixture is successively added to the polymerization system, unlike the batch method, the polymerization of the monomer can be reduced during the growth of the polymerization by the copolymer. Since the selectivity is selected, the resulting copolymer becomes a more random chain structure. Further, according to the present method, since the accumulation of heat of polymerization in the polymerization system becomes small, the low polymerization temperature can be stably maintained. In the monomer sequential addition method, the total amount of the monomers used is usually from 至1 to 60% by weight, preferably from 0.02 to 20% by weight, preferably from 〇5 to 10% by weight. As the initial monomer, the monomer is added to the polymerization reactor in advance, and the polymerization is started. When the initial monomer amount is in the above range, the removal of the generated reaction heat can be facilitated in the initial reaction after the start of the polymerization, and the resulting copolymer can be made into a relatively irregular structure of -20-200927816. The reaction is continued until the polymerization conversion ratio of the initial monomer is usually 70% or more, preferably 80% or more, and preferably 90% or more. The resulting chain structure of the copolymer becomes relatively irregular. Thereafter, the remaining portion of the monomer is continuously added, and the rate of addition is determined in consideration of the rate of consumption of the monomer in the polymerization system. Usually, the time required for the polymerization conversion ratio of the initial monomer to reach 90% is T, and when the ratio (%) of all the monomers used for the initial monomer is 1, it is determined to be in the relationship [(ΙΟΟ-Ι)ΧΤΠ]. The addition of the remaining monomer is ended in the range of 0.5 to 3 times the time given, and preferably in the range of 0.8 to 2 times, preferably 1 to 1.5 times. Specifically, the rate of addition of the initial monomer to the remaining monomer is determined to be usually from 0.1 to 30 hours, preferably from 0.5 to 7 hours, preferably from 1 to 5 hours. The polymerization conversion ratio of the entire monomer after completion of the monomer addition is usually 80% or more, preferably 85% or more, and more preferably 90% or more. When the polymerization conversion ratio of the entire monomer after completion of the monomer addition is in the above range, the chain structure of the obtained copolymer becomes relatively irregular. The polymerization reaction is carried out in the presence of the specific compound described above, and may be any polymerization method such as radical polymerization, anionic polymerization or cationic polymerization, and is not particularly limited. However, in consideration of various characteristics such as the ease of hydrogenation reaction in the polymerization operation and the subsequent step, and the mechanical strength of the finally obtained alicyclic hydrocarbon random copolymer, an anionic polymerization method is preferred. In the case of radical polymerization, in the presence of a starter and a specific compound, it is usually from 0 to 200 ° C, preferably from 20 to 150. (At the reaction temperature: 'It is possible to use a method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. In particular, in the case where it is necessary to prevent the incorporation of impurities or the like in the copolymer, it is desirable to carry out the overall polymerization and suspension polymerization. As the free radical initiator-21-200927816, an organic peroxide such as benzoyl peroxide, lauroyl peroxide, peroxy-2-ethylhexanoic acid or the like; azoisobutyronitrile may be used. An aqueous azo compound such as nitrogen bis-4-cyanovaleric acid or azodiphenyl fluorenyl, a water-soluble catalyst represented by ammonium persulfate or redox, etc. In the case of anionic polymerization, at the beginning In the presence of a specific agent, at a polymerization temperature of usually from 0 to 200 ° C, preferably from 20 to 100 ° C of from 20 to 80 ° C, a method of bulk polymerization, sol-gel polymerization, etc. may be used. In the polymerization method, when the reaction heat efficiency is also considered, solution polymerization is preferred. In the solution polymerization, an inert solvent for dissolving the resulting copolymer and its hydride is preferred. Examples of the inert solvent used in the solution include Butane, n-pentane, #正己An aliphatic hydrocarbon such as an alkane, n-heptane or isooctane; an alicyclic hydrocarbon such as cyclopentane, methylcyclopentane, methylcyclohexane or decalin; an aromatic hydrocarbon such as benzene; In the case of using an aliphatic hydrocarbon or a lipid, a solvent may be used as it is in the hydrogenation reaction after the copolymerization. The solvent may be used alone or in combination of two or more solvents. The total amount of the monomer is 100 parts by weight, and is usually used in a proportion of 10,000 parts by weight. For the anionic polymerization initiator, for example, n-butyldibutyllithium, t-butyllithium, hexyllithium, phenyllithium, or the like can be used. The organic lithium compound such as an organic lithium compound such as dilithium methane, 1,4-dilithium butane or 1,4-dilithium-2-ethylcyclohexane may be used alone. A polymerization accelerator is used in the polymerization reaction. The molecular weight of the copolymer before hydrogenation, using tributyl, 4,4'-: as a trans-initiator compound by GPC, special polymerization, removal using liquid-polymerizable i-pentane, i-hexane, Toluene cyclic hydrocarbons are used as inerts. 200 to lithium, lithium for the first machine; 〖multi-functional, also: polyphenylene -22-200927816 amount <fnT. Sexual aggregation, etc., also has a state of appearance. 5. The olefinic (or polyisoprene) converted weight average molecular weight (Mw) is 10,000 to 500,000, preferably 30,000 to 300,000. range. When the weight average molecular weight (Mw) of the copolymer is too small, the weight average molecular weight of the alicyclic hydrocarbon-based copolymer obtained by hydrogenation becomes too small, and the strength of the molded product is extremely poor; when it is too large, the hydrogenation reactivity becomes variable. difference. The random mixture obtained by the above-mentioned radical polymerization or anionic polymerization can be recovered from the polymerization reaction system by, for example, a steam stripping method, a direct solvent removal method, or an alcohol solidification method. In the case of polymerization, in the case where the hydrogenation reaction is carried out using an inert solvent, the polymer is not recovered from the polymerization solution, and it can be used as it is in the hydrogenation step. In the case of performing a hydrogenation reaction of a random copolymer or a main chain or a side chain carbon-carbon unsaturated double bond before hydrogenation, the reaction method and reaction form are not particularly limited and can be carried out in accordance with an accepted method. Among them, the hydrogenation rate can be increased, and it is preferred to use a hydrogenation method which causes a small amount of polymer chain cleavage reaction at the same time as the hydrogenation reaction. Specifically, a method of hydrogenating using a catalyst containing at least one metal selected from the group consisting of nickel, cobalt, iron, titanium, rhodium, palladium, ruthenium, and iridium is used in an organic solvent. Hydrogen catalysts can also use any non-uniform catalyst and uniform catalyst. The uneven catalyst can be used as a metal or a metal compound or as a suitable support. Examples of the support include activated carbon, cerium oxide alumina, calcium carbide, titanium oxide, magnesium oxide, zirconium oxide, alumina, and carbonium. The amount of the catalyst supported is usually from 0.01 to 80% by weight, preferably from 〇 to 60% by weight. The homogeneous catalyst system may be a combination of a nickel, cobalt, titanium or iron compound with a metal compound (for example, an organoaluminum compound, an organolithium compound), a catalyst -23-200927816, an organic metal such as palladium, uranium, ruthenium or a chain. Material catalyst, etc. As the nickel, cobalt, titanium or iron compound, for example, an acetoacetone salt, a sulfonate salt, a cyclopentadienyl compound, a cyclopentadiene dichloride compound or the like of various metals is used. As the organoaluminum compound, an aluminum alkyl such as triethylaluminum or triisobutylaluminum; an aluminum halide such as diethylaluminum chloride or aluminum dichloride: a hydrogenated aluminum alkyl such as hydrogenated diisobutylaluminum or the like is preferably used. Wait. An exemplary aspect of the organometallic complex catalyst is the use of the above-mentioned respective metals of r-dichloro-π-benzene complex, dichloro-tris(triphenylphosphine) complex, hydride ruthenium-chloro-triphenyl. A metal complex such as a phosphine complex. These hydrogenation catalysts may be used singly or in combination of two or more kinds. The hydrogenation catalyst is used in an amount of usually 0.01 to 50 parts by weight, preferably 0.05 to 25 parts by weight, based on 100 parts by weight of the copolymer, preferably 0.1 to 15 parts by weight. The hydrogenation reaction is usually carried out at a temperature of from 10 to 250 °C. From the standpoint of increasing the hydrogenation rate and reducing the polymer chain cleavage reaction caused by the hydrogenation reaction, it is preferably 50 to 200 ° C, preferably 80 to 180 ° C. Hydrogenation is carried out at temperature. The hydrogen pressure is usually from 0.1 to 3 OMPa. In addition to the above reasons, the hydrogen pressure is desirably from 1 to 20 MPa, preferably from 2 to 10 MPa, from the viewpoint of workability. The hydrogenation rate of the hydride thus obtained is usually 90% or more in the carbon-carbon unsaturated bond of the main chain and/or the side chain, and the carbon/carbon double bond of the aromatic ring in the measurement by 1H-NMR. It is preferably 95% or more, preferably 97% or more, and in most cases, it is 99% or more, and 99.9%. When the hydrogenation rate is low, the obtained alicyclic hydrocarbon random copolymer has low birefringence, thermal stability, and lightning resistance. -24- 200927816 The method of recovering the hydride after completion of the hydrogenation reaction is not particularly limited. In the recovery method, after the hydrogenation catalyst residue is removed by filtration, centrifugation or the like, a method of removing the solvent from the hydride solution by direct drying can be used; and the hydride solution is injected into a weak solvent for the hydride. Medium, a method of solidifying a hydride. According to the invention, there is provided a resin composition containing an antioxidant in the above-mentioned alicyclic hydrocarbon random copolymer. Examples of the antioxidant include a phenol antioxidant, a phosphorus antioxidant, and a sulfur antioxidant. Among them, a phenol anti- φ oxidizing agent is preferred, and an alkyl-substituted phenol antioxidant is preferred. By blending an antioxidant with an alicyclic hydrocarbon random copolymer, it is possible to prevent coloring or strength reduction of a molded article which is oxidatively deteriorated during molding without lowering transparency and low water absorption. As the phenol antioxidant, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-tolyl acrylate, 2,4-di- An acrylate compound such as tripentyl-6-[l-(3,5-di-third amyl-2-hydroxyphenyl)ethyl]phenyl acrylate; octadecyl-3-(3, 5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 1,1,3-three Bismuth(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl 4-hydroxybenzyl)benzene, tetrakis(methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenylpropionate) methane [ie, isopentenol tetraol [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]], triethylene glycol-bis[3-(3-tert-butyl-4-hydroxy-5- Alkyl-substituted phenolic compound such as tolyl)propionate; 6-(4-hydroxy-3,5-di-t-butylanilino)-2,4-dioctylthio-1,3,5 - three tillage, 4 · dioctylthio-1,3,5-tripper, 2-octylthio-4,6-bis(3,5-di-t-butyl-4-oxoanilinyl)- 1,3,5-three tillage, etc., containing a trimethyl phenol compound, etc. Phosphorus antioxidant In terms of the general use in the resin industry, there is no particular limitation on the use of -25-27827816, and examples include triphenyl phosphate, diphenylisodecyl phosphate, phenyl diisodecyl phosphate, and tris(R). Phenyl)phosphate, tris(phenylene phosphate), tris(2,4-di-t-butylbenzene vinegar), 1〇-(3,5---t-butyl-4-hydroxybenzyl) a monophosphate compound such as -9,10-dihydro-9-oxa-10-phosphinophenanthryl-10_oxide; 4,4,-butylene-bis(3-methyl-6- a diphosphonate compound such as a third butyl-ditridecylphosphonate or a 4,4,-isopropylidene-bis(phenyl-dialkyl (C. to C15) phosphate) Among them, monophosphate compounds are preferred, and tris(p-phenylphenyl phosphate), tris(phenylene carbonate) and tris(2,4-di-t-butylphenyl) phosphate are preferred. In terms of sulfur antioxidants, examples include dilauryl 3,3-thiodipropionate, dimyristyl 3,3'-thiodipropionate, and distearyl 3,3-thiodipropionate. , 3,3 · lauric acid lauric stearyl ester, pentaerythritol tetra (/S-lauryl thiopropionate), 3,9-double (2-ten Alkylthioethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, etc. These antioxidants may be used singly or in combination of two or more. Although it is suitably selected insofar as it does not impair the object of the present invention, it is usually 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight, per 100 parts by weight of the alicyclic hydrocarbon random copolymer. In the present invention, there is provided a resin composition comprising an alicyclic hydrocarbon random copolymer and a compounding agent selected from at least one selected from the group consisting of a soft polymer, an alcohol compound, an organic cerium and an inorganic cerium. . In the alicyclic hydrocarbon random copolymer, by blending with these compounding agents, it is possible to prevent white turbidity in a long-time high-temperature and high-humidity environment without deteriorating various characteristics such as transparency, low water absorption, and mechanical strength. . In addition to the above-mentioned compounding agent, the resin composition preferably contains an antioxidant. Among them, the soft polymer and the alcohol compound are excellent in the anti-white turbidity effect in the high-temperature and high-humidity ring -26-200927816, and the obtained resin composition is excellent in transparency. The soft polymer used in the present invention is a polymer which usually has a Tg of 30 ° C or less, and in the case where a plurality of Tg are present, at least the minimum Tg may be 30 ° C or less. Specific examples of the soft polymer include liquid polyethylene, polypropylene, poly-1-butene, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, and ethylene-propylene-diene copolymer (EPDM). ), an olefin soft polymer such as an ethylene-propylene/styrene copolymer; an isobutylene soft polymer such as polyisobutylene, isobutylene-isoprene rubber φ, isobutylene-styrene copolymer; polybutadiene, polyiso Pentadiene, butadiene-styrene/random copolymer, isoprene-styrene random copolymer, acrylonitrile-. Butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, butadiene-styrene block copolymer, styrene-butadiene-styrene block copolymer, isoprene-styrene a diene soft polymer such as a block copolymer or a styrene-isoprene-styrene block copolymer; dimethyl polyoxane, diphenyl polyoxyalkylene, dihydroxy polyoxyalkylene, etc.矽 soft polymer; polybutyl acrylate, polybutyl methacrylate, 聚 polyhydroxyethyl methacrylate, polyacrylamide, polyacrylonitrile, butyl acrylate-styrene copolymer, etc. a soft polymer composed of a /3-unsaturated acid; a polyvinyl alcohol, a polyvinyl acetate, a polyvinyl polystearate, a vinyl acetate-styrene copolymer, or the like derived from an unsaturated alcohol and an amine or a mercapto group thereof Soft polymer composed of material or acetal; epoxy soft polymer such as polyethylene oxide, polypropylene oxide, epichlorohydrin rubber; fluorine soft rubber such as difluoroethylene rubber or tetrafluoroethylene-propylene rubber Polymer; natural rubber, polypeptide, protein, polyester thermoplastic elastomer, vinyl chloride Other soft polymers such as thermoplastic elastomers and polyamide thermoplastic elastomers. These soft -27-200927816 polymers may also be those having a cross-linking structure or may be introduced into a functional group by a modification reaction. The soft polymer is preferably a diene soft polymer, in particular, a hydrogenated product of a carbon-carbon unsaturated bond of a hydrogenated soft polymer, which is excellent in rubber elasticity, mechanical strength, flexibility, and dispersibility. The alcoholic compound is a compound having at least one non-reactive hydroxyl group in the molecule, and is preferably a compound having at least one hydroxyl group and at least one ether bond or ester bond. Specific examples of the compounds include, for example, a divalent or higher polyhydric alcohol, preferably a trivalent or higher polyhydric alcohol, more preferably one of the hydroxyl groups of a polyhydric alcohol having 3 to 8 hydroxyl groups, which is etherified or esterified. An alcoholic ether compound or an alcoholic ester compound. . Examples of the polyvalent alcohol having a valence of 2 or more include polyethylene glycol, glycerin, trimethylolpropane, isovaerythritol, diglycerin, triglycerin, diisopentaerythritol, 1,6,7·trihydroxy-2. ,2-bis(hydroxymethyl)-4-oxoheptane, sorbitol, 2-methyl-1,6,7-trihydroxy-2-hydroxymethyl-4-oxoheptane, 1,5, 6-trihydroxy-3-oxohexaneisopentyltetraol, tris(2-hydroxyethyl)isocyanate, etc., particularly preferably a trivalent or higher polyvalent alcohol, more preferably a polyol having 3 to 8 hydroxyl groups . When an alcoholic ester compound is obtained, it is preferred to synthesize glycerin, diglycerin, triglycerin or the like containing an alcohol ester compound of α, /3-diol. Examples of the alcoholic compound include glycerin monostearate, glycerol monolaurate, glycerol monobehenate, diglycerin monostearate, glyceryl distearate, glycerol dilaurate, Pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol monobehenate, pentaerythritol distearate, pentaerythritol dilaurate, isovalerate Polyol esterified product of tetraol tristearate diisopentaerythritol distearate; 3-(octyloxy)-1,2-propanediol, -28- 200927816 3-(decyloxy) -1,2 propanediol, 3-(lauryloxy)-1,2-propylene glycol phenoxy)-1,2-propanediol, 1,6-dihydroxy-2,2-bis(hydroxymethyl)oxy) 4-oxoheptane, an alcoholic ether compound obtained by the reaction of a condensation sale of decyl phenyl ether and formaldehyde, an alcoholic ether compound obtained by reacting a octanoic acid condensate with dehydrin A condensate of phenyl ether and dicyclopentadiene, a reactive ether compound of dehydroglycerin, and the like. These polyol compounds may be used singly or in combination of two or more. The molecular weight of the polyol compound is not particularly limited to 500 to 2,000, preferably 800 to 1,500, and is preferred from the viewpoint of transparency. As the organic dip, a usual organic polymer can be used. In this specific example, a polyolefin such as propylene or the like; a 5-olefin polymer such as polyvinyl chloride or polyvinylidene chloride; a polymer derived from a saturated acid such as polyacrylate or polymethacrylate; a polymer derived from polyvinyl alcohol, polyacetic acid ethylenic unsaturated alcohol; polyethylene oxide, or a polymer derived from ether; polyoxyalkylene phenyl, polycarbonate, aromatic condensation polymer; Ethyl carbamate; polyamidamine; polyresin; particles of natural high molecular weight compound or the like or crosslinked particles 3 Inorganic tanning materials, for example, lithium fluoride, borax (antimonic acid: a group 1 element compound; magnesium carbonate, a group 2 element compound such as magnesium phosphate or calcium carbonate strontium carbonate; titanium dioxide (titanium oxide: a group 4 element compound such as titanium; molybdenum dioxide, molybdenum trioxide; compound; a group 7 element compound such as manganese chloride or manganese acetate; ; 3-(4-壬-7-(4-indenebenzene|with dehydrated and formaldehyde) by the alcohol obtained from sim, but usually less reduced: sub or cross-linking: ethylene, poly. Glycidyl glycerol Ester; aldehyde-phenolic aqueous salt), barium titanate, I, mono-oxidation: Group 6 element cobalt chloride, -29-200927816 Cobalt acetate and other 8 to 10 element compound; Group 11 of cuprous iodide Elemental compound; Group 12 element compound such as zinc oxide, zinc acetate, etc.; Group 13 element compound such as alumina (ie, Alumina), fluorinated Ming, Ming sand (salic acid, kaolin, kaolinite); Group 14 elemental compounds such as stone, tannin, graphite, carbon, graphite (Graphite), glass, etc.; natural mineral particles such as blue diopside, potassium magnesium strontium, mica (S卩, mica, phlogopite), coke ore The compounding amount of at least one compounding agent selected from the group consisting of a soft polymer, an alcoholic compound, and an organic or inorganic material © depending on the combination of the alicyclic hydrocarbon random copolymer and the compounding agent, However, when the amount is too large, the glass transition temperature or transparency of the resin composition is greatly lowered, and it is not suitable for use as an optical material. When the amount is too small, there is a white turbidity of the molded product under high temperature and high humidity. Situation The surface is usually from 0.01 to 10 parts by weight, preferably from 0.02 to 5 parts by weight, particularly preferably from 5% to 2 parts by weight, based on 100 parts by weight of the alicyclic hydrocarbon random copolymer. When the amount is too small, the white turbidity preventing effect in a high-temperature and high-humidity environment is not obtained, and when the amount is too large, the heat resistance and transparency of the molded article are lowered. In the resin composition of the present invention, If necessary, it can be used as a coloring agent, a slip agent, a plasticizer, an antistatic agent, a fluorescent whitening agent, etc. as a blending agent, such as a UV absorber, a light stabilizer, a near-infrared absorber, a dye or a pigment, etc. The agent may be used singly or in combination of two or more kinds. The compounding amount is appropriately selected insofar as it does not impair the object of the present invention. The resin composition of the present invention can be obtained by suitably mixing the above respective components. In the mixing method, there is no particular limitation on the method of sufficiently dispersing the components in the alicyclic hydrocarbon random -30-200927816 copolymer, and examples thereof include a mixer, a biaxial kneader, a roll, a kneader, an extruder, and the like. A method of kneading a mixture in a molten state; a method of dissolving in a suitable solvent to disperse and solidify, and the like. In the case of using a biaxial kneader, it is usually cut into a rod shape in a molten state after kneading, and is cut into a suitable length by a linear pelletizer to be used as a pelletized material. The molded article of the present invention is obtained by molding a molding material composed of an alicyclic hydrocarbon random copolymer or a resin composition. Although there is no particular limitation on the molding method, it is preferably melt-molded in a molded article excellent in characteristics such as high-light-resistant laser light resistance, low birefringence, mechanical strength, and dimensional accuracy. Examples of the melt forming method include cast molding, extrusion molding, and injection molding. In the case of their forming methods, it is preferable to form the shape by the viewpoint of formability and productivity. The molding conditions are appropriately selected depending on the purpose of use or the molding method. For example, the temperature of the resin for injection molding is suitably selected from the range of usually 150 to 400 ° C, preferably 200 to 350 ° C, preferably 230 to 3301. When the resin temperature is too low, the fluidity is deteriorated, and shrinkage or skew occurs in the molded product. When the resin temperature is too high, silver streaks due to thermal decomposition of the resin are generated on the one hand, and yellowing of the molded product may occur on the other hand. Bad production. The molded article of the present invention can be used in various forms such as a spherical shape, a rod shape, a plate shape, a cylindrical shape, a cylindrical shape, a tubular shape, a fibrous shape, a film shape or a sheet shape. Since the molded article of the present invention is excellent in blue light-resistant laser light, low complex refractive index, transparency, mechanical strength, heat resistance, and low water absorbability, it can be used in various applications, and is particularly suitable as an optical component. Specific examples of optical components include the following. Optical lens or optical lens, camera lens; microscope, endoscope, lens of -31-200927816 telescope, etc.; full-light lens for glasses lens; CD, CD-ROM, WORM (replenishment CD) , M〇 (rerecordable optical disc; optical disc), MD (mini disc), DVD (digital video disc) and other optical disc reading lens; laser beam printer f0 lens, sensor lens, etc. Laser scanning lens; lens of the filter of the camera, etc. For the use of optical discs, there are CD, CD-ROM, WORM (Complementary Disc), MO (Rerecordable Disc; Optical Disc), MD (Mini Disc), DVD (Digital Video Disc), and the like. Other optical applications include a light guide plate such as a liquid crystal display, an optical film such as a polarizing film, a phase φ difference film, and a light diffusion film; a light diffusing plate; an optical card; and a liquid crystal display element substrate. For other applications, there are five types of inspection members such as medical blood test members, syringe syringes, hard tubes or hoses, medical bottles or liquid medicine containers, and insulating films for printed substrates. Among them, the alicyclic hydrocarbon random copolymer and the resin composition of the present invention are also suitable as a reading lens or a laser scanning lens which requires blue laser resistance and low birefringence, and is preferably a reading lens. . EMBODIMENT Hereinafter, the present invention will be specifically described by way of examples and comparative examples. The weight and percentage of the examples and the percentages without special prior notice are the weight basis. The measurement of various physical properties was carried out in accordance with the following method. (1) Molecular weight: The molecular weight of the polymer is measured by GPC using tetrahydrofuran (THF) as a solvent, and the weight average molecular weight (Mw) in terms of standard polystyrene is obtained. (2) Molecular weight distribution: The molecular weight distribution of the polymer is determined by GPC using THF as a solvent, and -32-200927816, the weight average molecular weight (Mw) and the number average molecular weight (?η) in terms of standard polystyrene are calculated. Ratio (Mw/Mn). (3) Glass transition temperature (Tg): The glass transition temperature of the polymer was measured by differential scanning calorimetry (DSC) at a temperature increase rate of 10 ° C /min. (4) Hydrogenation rate: The hydrogenation ratio of the copolymer was measured by 1H-NMR. (5) Bonding type: 键 The bonding type of the conjugated diene monomer is determined by 13c-nmr. (6) Birefringence: The birefringence was measured by using a resin molded plate having a thickness of 3 mm, a length of 65 mm, and a width of 65 mm which was injection-molded at 280 ° C as a sample. A birefringence enthalpy at a position 10 mm from the gate at the time of injection molding of the resin formed plate was measured using a polarizing microscope (Nikon Corporation, 546 nm Senarmont Compensator). The birefringence is closer to zero and the lower the refraction is shown. Ο (7) Laser resistance: The laser resistance is irradiated by a laser diode with a wavelength of 405±10 nm and a power of 400 mW/cm 2 in an environment of 80 ° C (made by Nio Yake Co., Ltd., TC3 5-4030- 4.5) Laser light emitted from a resin molded plate having a thickness of 3 mm, a length of 65 mm, and a width of 65 mm for 480 hours, and the light transmittance after laser irradiation was measured by a spectrophotometer (manufactured by JASCO Corporation, V-570) before and after irradiation. The amount of light transmittance reduction (%) was evaluated. The smaller the decrease in the light transmittance at a wavelength of 400 nm before and after the laser irradiation of the formed plate, the more excellent the blue light-resistant laser is exhibited. -33-200927816 [Example 1] 1,286 parts of dehydrated cyclohexane and 1.34 parts of ethylene glycol dibutyl ether were placed in a stainless steel autoclave equipped with an electromagnetic stirring device which was sufficiently dried and replaced with nitrogen. a compound having a chelate structure having two or more electrons supplied to an atom, stirred at 50 ° C and adding 1.97 parts of a n-butyllithium solution (containing 15% hexane solution), wherein the composition is continuously added in a weight ratio of [Styrene (St) / Isoprene (Ip)] = (96.4 / 3.6) mixed monomers and began to polymerize. A total of 500 parts of the mixed monomer was added dropwise over 4 hours. After the completion of the dropwise addition, Φ was polymerized under the same conditions for 30 minutes, and then 0.46 parts of isopropanol was added to stop the reaction to synthesize styrene-isoprene/random copolymerization. Things. Adding a mixing solution, obtaining 358 parts of a reaction solution, 96.5 parts of cyclohexane, and 8 parts of a stabilized nickel hydrogenation catalyst E22U (manufactured by Rikai Chemical Industry Co., Ltd.; 60% nickel-supported cerium oxide-alumina support), It is placed in a stainless steel autoclave provided with an electrothermal heating device and an electromagnetic stirring device for adjusting the hydrogenation reaction temperature. After the completion of the filling, the inside of the autoclave was replaced with hydrogen, stirred, and hydrogen was supplied at a pressure of 4.5 MPa at 160 ° C while maintaining the pressure inside the autoclave, and hydrogenation was carried out for 6 hours. After the completion of the reaction, the hydrogenation catalyst was removed by filtration, and 1,8 18 parts of cyclohexane was added, and then separated by filtering an alicyclic hydrocarbon random copolymer which had been injected into 11 liters of isopropyl alcohol. It was dried by a vacuum dryer. The obtained alicyclic hydrocarbon random copolymer had a hydrogenation rate of 99.9%, a weight average molecular weight of 101,000, a number average molecular weight of 76,000, and a glass transition temperature of 12 8 °C. The alicyclic hydrocarbon random copolymer thus obtained was injection-molded, and a sample for measurement of the refractive index and a sample for measuring the light transmittance were prepared. The results are shown in Table 1. -34-200927816 [Example 2] Polymerization reaction and hydrogenation reaction were carried out in the same order as in Example 1 except that the monomer composition was used in a weight ratio of (St/Ip) = (95/5). Then, the alicyclic hydrocarbon random copolymer obtained by the injection molding was injected to prepare a sample for birefringence measurement and a sample for measuring light transmittance. The results are shown in Table [Example 3] except that 0.69 parts of ethylene glycol dimethyl ether was added, and ethylene glycol dibutyl ketone was substituted as a compound having a chelate structure having two or more electron donor atoms. The polymerization reaction and the hydrogenation reaction were carried out in the same manner as in Example 2, and the alicyclic hydrocarbon random copolymer obtained by the molding was injected to prepare a sample for birefringence measurement and a sample for measuring light transmittance. The results are shown in Table 1. [Example 4] The polymerization reaction and the hydrogenation reaction were carried out in the same manner as in Example 1 except that the monomer composition was used in a weight ratio of (St/Ip) = (90/10). The alicyclic hydrocarbon random copolymer obtained by injection molding was injected to prepare a sample for birefringence measurement and a sample for measuring light transmittance. The results are shown in Table 1. [Comparative Example 1] The same procedure as in Example 1 except that 1.00 part of a dibutyl ether of a randomizer was substituted with ethylene glycol dibutyl ether, stirred at 60 ° C and polymerized. The polymerization reaction and the hydrogenation reaction were carried out in this order, and the alicyclic hydrocarbon random copolymer obtained by the molding was injected to prepare a sample for birefringence measurement and a sample for measuring light transmittance. The results are shown in Table 1. -35-200927816 [Comparative Example 2] In the same order as in Example 2, except that 1.00 part of a dibutyl ether of a randomizer was substituted with ethylene glycol dibutyl ether, and stirred at 60 ° C and polymerization was carried out. The polymerization reaction and the hydrogenation reaction were carried out, and the alicyclic hydrocarbon random copolymer obtained by the molding was injected to prepare a sample for birefringence measurement and a sample for measuring light transmittance. The results are shown in Table 1. [Comparative Example 3] The polymerization reaction was carried out in the same manner as in Example 4 except that 1.00 part of a dibutyl ether of a randomizer was substituted with ethylene glycol dibutyl ether, and the mixture was stirred and polymerized at 60 °C. The hydrogenation reaction is followed by injection molding to obtain an alicyclic hydrocarbon random copolymer to prepare a sample for birefringence measurement and a sample for measuring light transmittance. The results are shown in Table 1. [Table 1]

St/Ip (W Weight W randomizer bond type desert %) Hydrogenation rate {%) Mw Μη Mw/Mn Tg 〇c) Complex refraction (nm) Laser resistance (%) 1,4- 3,4- Example 1 96.4/3.6 EGDBE 49.2 50.8 99.9 101,000 76,000 1.33 128 38 -2.75 Example 2 95/5 EGDBE 49.8 50.2 99.9 96,000 74,000 1.30 123 23 -1.86 Example 3 95/5 EGDME 50.6 49.4 99.9 106,000 81,000 1.31 121 23 - 1.93 Example 4 90/10 EGDBE 49.5 50.5 99.9 109,000 83,000 1.31 110 7 •1.28 Comparative Example 1 96.4/3.6 n-Bu20 95.6 4.4 99.9 104,000 81,000 1.28 122 40 -2.89 Comparative Example 2 95/5 n-Bu20 95.2 4.8 99.9 98,000 76,000 1.29 117 26 -1.90 Comparative Example 3 90/10 n-Bu20 95.0 5.0 99.9 103,000 81,000 1.27 97 8 -1.29 (Remarks) (l) EGDBI: ethylene glycol dibutyl ether (2) EGDME: ethylene glycol Ether ether (3) n-Bu2 oxime: dibutyl ether (reference) The following is known from Table 1. -36- # 200927816 (1) Comparative Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, and Example 4 and Comparative Example 3 'Even if the individual copolymerization composition is the same, ethylene glycol dibutyl ether is used as having A conjugated diene monomer (in the case of an example in which the electron is supplied to a compound of an atom (preferably a compound having a chelate structure having two or more electrons supplied to the atom) to carry out polymerization (Examples 1, 2 and 4). The content of 1,4-bonding in the repeating unit of isoprene is 70 mol% or less. As a result, it is known that the glass transition temperature is high, heat resistance is improved, and the birefringence is also improved. 〇(2) When the results of Examples 1 to 4 were observed, it was found that as the content of the repeating unit derived from the conjugated diene monomer (isoprene) became larger, the laser resistance was improved, and comparison was made. Examples 1 to 3 maintain heat resistance at a high level. In particular, when the results of Example 4 and Comparative Example 3 were compared, it was found that the original glass transition temperature was maintained at a high level, and the laser resistance was improved. (3) In the case where ethylene glycol dimethyl ether is used instead of ethylene glycol dibutyl ether, as a compound having two or more electron donor atoms and a chelate-forming structure (Example 3), The same excellent results. © Industrial Applicability The alicyclic hydrocarbon random copolymer of the present invention is excellent in transparency, low birefringence, mechanical strength, heat resistance, low water absorption, and high-light-resistant laser resistance, and can be utilized in various types. use. The alicyclic hydrocarbon random copolymer of the present invention is particularly suitable for use as a resin material for optical parts such as a reading lens or a laser scanning lens. [Simple diagram] /fnr No 0 -37- 200927816 [Main component symbol description] 4ίΠ- 〇

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Claims (1)

200927816 VII. Patent application scope: 1. An alicyclic hydrocarbon random copolymer which contains a random copolymer of an alicyclic structure [A] and a repeating unit of a chain structure [B] And characterized by (1) the repeating unit [A] of the alicyclic structure is represented by the following formula 1 In the formula 1, R1 and R2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, and a carbon number! Alkoxycarbonyloxy group, cyano group, decylamino group, oxime imido group, decyl group, or a polar group (halogen atom, hydrocarbon group, alkoxy group having 1 to 20 carbon atoms, alkane having 1 to 20 carbon atoms) a repeating alicyclic structure represented by a carbonyloxy group, a cyano group, a decylamino group, a fluorenylene group, or a fluorenyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms; η is an integer of 0 or 1 to 5] Unit; Ο (2) The repeating unit of the chain structure [Β] has the following formula 2 (in the formula 2, R3 is a hydrogen atom or a methyl group) represents a repeating unit [BJ, and is represented by the following formula (In the formula 3, R3 is a hydrogen atom or a methyl group) -39-200927816 represents a repeating unit of a chain structure of the repeating unit [b2]; (3) the alicyclic ring in the alicyclic hydrocarbon random copolymer The total content of the structural repeat unit [A] and the chain structure repeat unit [B] is 90% by weight or more; (4) the chain structure repeat unit in the alicyclic hydrocarbon random copolymer [B] The content is 1 to 15% by weight; (5) the repeating unit in the chain structure repeating unit [B] [the content of cerium is 70 mol% or less; and φ (6) by gel permeation chromatography The alicyclic hydrocarbon random copolymer was determined to have a weight average molecular weight (Mw) in the range of 10,000 to 300,000. 2. An alicyclic hydrocarbon random copolymer as claimed in claim 1, wherein the alicyclic structural repeat unit [A] and the chain structure repeat unit [B] in the alicyclic hydrocarbon random copolymer The total content is in the range of 90 to 99.9% by weight. 3. The alicyclic hydrocarbon random copolymer of claim 1, wherein the chain-structure repeating unit [B] has a Q content of 2 to 10 by weight in the alicyclic hydrocarbon random copolymer %. 4. The alicyclic hydrocarbon random copolymer of claim 1, wherein the repeating unit [hydrazine is a hydrogenation selected from the group consisting of 1,4-bonded repeating units of isoprene and 1,3-butane a repeating unit of a carbon-carbon unsaturated double bond in at least one repeating unit of the group consisting of repeating units of 1,4-bonded groups of olefins, and the repeating unit [B2] is hydrogenated from the group consisting of isoprene A pendant carbon/carbon unsaturated double bond in at least one repeating unit of a group consisting of a repeating unit of 3,4-bonding and a repeating unit of 1,2-bonding of 1,3-butadiene Repeat unit. The alicyclic hydrocarbon random copolymer of claim 1, wherein the repeating unit in the repeating unit [Β] of the chain structure is 40 to 70 m. Within the range of %. 6. The alicyclic hydrocarbon random copolymer according to claim 1, wherein the alicyclic hydrocarbon random copolymer has a glass transition temperature of 1 Torr or more as measured by a differential scanning calorimeter. An alicyclic hydrocarbon random copolymer as claimed in claim 1, wherein the alicyclic hydrocarbon random copolymer has a weight average molecular weight Mw in terms of standard polyphenylenevinylene determined by gel permeation chromatography The molecular weight distribution represented by the ratio Mw/Mn of the number average molecular weight Μη is 2.5 or less. 8. The method for producing an alicyclic hydrocarbon random copolymer according to claim 1, which comprises the following steps I and II: (I) 85 to 99% by weight of a polymerized aromatic vinyl monomer in the presence of a compound having an electron donor atom, selected from at least one of the group consisting of isoprene and i,3-butadiene 1 to 15% by weight of the conjugated diene monomer, and 0 to 10% by weight with the other ethylene monomer, and the content of 1,4 -bonding in the repeating unit of the conjugated diene monomer is 70 mol % Step I of the following random copolymer; and (II) hydrogenating the main chain of the random copolymer and Step II of a carbon-carbon unsaturated double bond containing a side chain of an aromatic ring. 9. The process of claim 8 wherein the aromatic vinyl monomer is styrene. 10. The scope of claim 8 The method of the present invention, wherein the compound having an electron donor atom is a compound having an electron supplied from at least one selected from the group consisting of a sulfur atom, an oxygen atom, and a pity atom. -41- 200927816 11. The method of claim 8, wherein the compound having an electron donor atom has a chelate body capable of forming at least one electron having at least one electron selected from the group consisting of a sulfur atom, an oxygen atom, and a phosphorus atom. A compound of the formula, wherein the compound having a chelate structure having two or more electron donor atoms is an ether compound, as in the method of claim 11, 13. The method of claim 12 Wherein the ether compound is selected from the group consisting of Q ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol diisopropyl ether, ethylene glycol dibutyl ether, ethylene glycol methylbenzene a dicoordinate ether compound of ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol diisopropyl ether, propylene glycol dibutyl ether, and propylene glycol methyl phenyl ether; selected from diethylene glycol dibutyl a tri-coordinating ether compound of an ether and dipropylene glycol dibutyl ether; selected from the group consisting of ethylene glycol alkyl ethers (carbon number 1 to 6 of the alkyl moiety) and propylene glycol alkyl ether (carbon number of the alkyl moiety 1 </ RTI> </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> </ RTI> <RTIgt; 0.001 to 10 parts by weight. 15. The method of claim 8, wherein in the step I of synthesizing the random copolymer, the polymerization is carried out by a sequential addition of the monomer mixture. 16) The method of claim 15, wherein in the step I of synthesizing the random copolymer, in an inert organic solvent, an initiator composed of an organolithium compound and a compound having an electron donor atom are present. In the polymerization system, the monomer mixture is successively added, and polymerization is carried out at a polymerization temperature of 0 to 200 ° C, -42 to 200927816. A resin composition comprising an alicyclic hydrocarbon random copolymer and an antioxidant as in the first aspect of the patent application. 18. The resin composition of claim 17, wherein the alicyclic hydrocarbon random copolymer further comprises a soft polymer, an alcoholic compound, an organic terpene selected from the group consisting of a glass transition temperature of 30 ° C or lower, And a compounding agent of at least one of the group consisting of inorganic materials. A molded article obtained by molding an alicyclic Q hydrocarbon random copolymer according to claim 1 or a resin composition comprising the alicyclic random copolymer and an antioxidant; . 20. The shaped article of claim 19, which is an optical component. ❹ -43- 200927816 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 〇 5. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: