JP2011048877A - Optical element and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve adhesiveness of a resin surface with a first layer and also to prevent or suppress a change of the surface shape and a white cloudiness inside the resin. <P>SOLUTION: An objective lens 37 is the optical element for an optical pickup device arranged in an optical path of luminous flux with the wavelength of 380 to 420 nm, and it includes a resin molding section 50 molding the resin and an anti-reflection film 60 formed on a surface of the resin molding section 50. The anti-reflection film 60 has a three-layered structure laminating a first layer 62, second layer 64 and third layer 66, and the first layer 62 coming into contact with the resin molding section 50 among these layers is a mixed layer in which a metal oxide material and a hindered amine based light stabilizer are contained. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an optical element and a method for manufacturing the same.

  2. Description of the Related Art Conventionally, an optical pickup device is used as a device for reading information in an optical information recording medium such as a CD or a DVD or recording information on the optical information recording medium. With a CD, it is possible to record 700 megabytes of information on a disk with a diameter of approximately 15 cm by using an optical pickup device having a light source that emits light with a wavelength of around 780 nm. By using an optical pickup device having a light source that emits light, information of 4.7 gigabytes can be recorded on a disc of the same size. In recent years, with the spread of digital broadcasting and the like, there has been a demand for further increasing the capacity of recording media, and a Blu-ray Disc (hereinafter referred to as BD) capable of recording approximately 25 gigabytes of information on a single disc. A so-called optical information recording medium standard has been developed. In BD, in order to further increase the capacity, an objective lens having a large image-side numerical aperture (NA) is used by using a light source having a wavelength of 380 to 420 nm.

  On the other hand, in an optical pickup device, an optical element such as a collimator lens or an objective lens is used. As the optical element, a glass molded product or a plastic molded product is used. In particular, since an optical element made of plastic is easy to mold and can be manufactured at low cost, it is desired to manufacture the optical element from plastic. In particular, in BD, further precision is required for optical information recording media of conventional standards, and in order to sufficiently cope with optical characteristics due to temperature changes and wavelength changes of light sources, diffraction is performed on the surfaces of those optical elements. In some cases, a fine structure such as a structure needs to be provided, and there is a strong demand for an optical element made of plastic with high moldability.

However, since the wavelength of the light source has been shortened compared to the conventional one, the light transmitted through the optical element or the energy of light is increased. When a plastic optical element is used, a resin is used during recording and reproduction. Deterioration due to deterioration and deformation and white turbidity are prominent.
Therefore, it has been proposed to use a resin having a relatively high light resistance and an alicyclic structure as the material of the optical element. However, when recording information on an optical information recording medium, the light intensity of the light source is reduced. It was difficult to obtain sufficient light resistance.
In order to further improve the light resistance, a technique for mixing an antioxidant into the resin for the optical element (the resin molded part of the lens) is also being studied. Among these antioxidants, a hindered amine light stabilizer ( HALS) has been found to be particularly effective.

However, it has been found that when a functional film such as an antireflection film is provided on the lens surface, the resin deteriorates or becomes cloudy at the interface between the resin molded portion and the functional film, affecting the optical performance. On the other hand, it is conceivable to add a large amount of antioxidant in the resin, but if a large amount of antioxidant is added, the bleed out of the antioxidant from the resin when using an optical pickup device or forming a functional film. There is a problem that the phenomenon of “out” occurs and the function of the optical element is deteriorated.
Regarding such a problem, in order to reduce the amount of the antioxidant added to the resin and to suppress the photodegradation of the resin surface, in particular, the photodegradation problem is remarkable, the first layer (underlayer) with respect to the resin surface A technique for forming a HALS layer has been studied (see Patent Document 1).

JP 2005-259302 A

However, when a HALS layer is formed on the resin surface, the HALS layer floats from the resin surface as the optical element is left in a high-temperature, high-humidity environment at 85 ° C. and RH 50%. It was found that the phenomenon of peeling occurs on the resin surface.
Here, when laser light with a wavelength of 405 nm is irradiated to an optical element in which the HALS layer has floated, the HALS layer does not function sufficiently on the resin surface, so that a shape change occurs on the resin surface or white turbidity occurs inside the resin. Problems occur.

  Therefore, the main object of the present invention is to improve the adhesion between the resin surface and the first layer, and to prevent or suppress the change in the surface shape and the white turbidity inside the resin, and a method for producing the same. Is to provide.

According to one aspect of the invention,
In an optical element for an optical pickup device arranged in an optical path of a light beam having a wavelength of 380 to 420 nm,
A resin molded part obtained by molding a resin;
A functional film formed on the surface of the resin molded portion;
With
The functional film has a layer structure in which a single layer or a plurality of layers are laminated,
An optical element is provided in which the first layer in contact with the resin molding portion among the layers constituting the functional film is a mixed layer containing a metal oxide material and a hindered amine light-resistant stabilizer. The

According to another aspect of the invention,
In the method for manufacturing an optical element for an optical pickup device arranged in an optical path of a light beam having a wavelength of 380 to 420 nm,
Forming a resin molded part by molding a resin;
A step of forming a functional film having a layer structure in which a single layer or a plurality of layers are laminated by a vapor deposition method on the surface of the resin molded portion;
With
In the step of forming the functional film, when forming the first layer in contact with the resin molding portion among the layers constituting the functional film, the metal oxide material and the hindered amine light resistance stabilizer are used as separate vapor deposition sources. Provided is a method for manufacturing an optical element characterized by performing multi-position deposition.

  ADVANTAGE OF THE INVENTION According to this invention, the adhesiveness of the resin surface and a 1st layer can improve, and the change of a surface shape and the cloudiness inside resin can be prevented or suppressed.

It is drawing which shows schematic structure of the optical pick-up apparatus used by preferable embodiment of this invention.

  Next, preferred embodiments of the present invention will be described in more detail with reference to the drawings.

As shown in FIG. 1, the optical pickup device 30 includes a semiconductor laser oscillator 32. The semiconductor laser oscillator 32 is an example of a light source, and emits blue laser light (blue-violet laser) having a specific wavelength (for example, 405 nm) having a wavelength of 380 to 420 nm for BD (Blu-ray Disc).
On the optical axis of the blue laser light emitted from the semiconductor laser oscillator 32, a collimator 33, a beam splitter 34, a quarter wavelength plate 35, a diaphragm 36, and an objective lens 37 are arranged in a direction away from the semiconductor laser oscillator 32. Are sequentially arranged.

  A sensor lens group 38 and a sensor 39 each including two sets of lenses are sequentially arranged at a position close to the beam splitter 34 and in a direction orthogonal to the optical axis of the blue-violet light described above.

  The objective lens 37 is disposed at a position on the optical path of the light beam of the blue laser light and facing the high-density optical disk D (BD optical disk). The objective lens 37 receives the blue laser light emitted from the semiconductor laser oscillator 32. The light is condensed on one surface of the optical disk D. The objective lens 37 is an example of an optical element, and the image-side numerical aperture NA is 0.7 or more. A flange portion is formed on the periphery of the objective lens 37, and a two-dimensional actuator 40 is mounted on the flange portion. The objective lens 37 is movable on the optical axis by the operation of the two-dimensional actuator 40.

As shown in the enlarged view in FIG. 1, the objective lens 37 is mainly composed of a resin molding portion 50, and an antireflection film 60 is formed on the surface 37 a of the objective lens 37. The antireflection film 60 is an example of a functional film that adds a function to the objective lens 37.
In the present embodiment, the antireflection film 60 may also be formed on the opposite surface (surface 37b) of the surface 37a of the objective lens 37.

The resin molding part 50 is mainly composed of a cycloolefin-based resin (a resin made of a polymer having an alicyclic structure).
As the resin, the following resins 1 and 2 can be preferably used. Specifically, ZEONEX manufactured by Nippon Zeon, APEL manufactured by Mitsui Chemicals, Arton manufactured by JSR, TOPAS manufactured by Chicona, etc. are preferably used.

[Resin 1]
Resin material 1 has a repeating unit (a) having an alicyclic structure represented by the following formula (1) in a polymer all repeating unit having a weight average molecular weight (Mw) of 1,000 to 1,000,000. ) And a repeating unit (b) having a chain structure represented by the following formula (2) and / or the following formula (3) so that the total content is 90% by weight or more, and further the repeating unit The content of (b) is preferably 1% by weight or more and less than 10% by weight, and the chain of the repeating unit (a) preferably contains an alicyclic hydrocarbon copolymer that satisfies the following relational formula (Z).
A ≦ 0.3 × B (Z)
In relational formula (Z), A = (weight average molecular weight of a chain of repeating units having an alicyclic structure), and B = (weight average molecular weight (Mw) of alicyclic hydrocarbon-based copolymer × (aliphatic). The number of repeating units having a cyclic structure / the total number of repeating units constituting the alicyclic hydrocarbon-based copolymer).

  R1 to R13 in formula (1), formula (2), and formula (3) are each independently a hydrogen atom, chain hydrocarbon group, halogen atom, alkoxy group, hydroxy group, ether group, ester group, cyano group. Chain carbonization substituted with groups, amide groups, imide groups, silyl groups, and polar groups (halogen atoms, alkoxy groups, hydroxy groups, ether groups, ester groups, cyano groups, amide groups, imide groups, or silyl groups) Represents a hydrogen group or the like. Among these, a hydrogen atom or a chain hydrocarbon group having 1 to 6 carbon atoms is preferable because of excellent heat resistance and low water absorption. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the chain hydrocarbon group substituted with a polar group include halogenated alkyl groups having 1 to 20, preferably 1 to 10, more preferably 1 to 6 carbon atoms. As the chain hydrocarbon group, for example, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms; 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 2 carbon atoms. 6 alkenyl groups.

  X in Formula (1) represents an alicyclic hydrocarbon group, and the number of carbon atoms constituting the group is usually 4 to 20, preferably 4 to 10, and more preferably 5 to 7. . Birefringence can be reduced by setting the number of carbon atoms constituting the alicyclic structure within this range. The alicyclic structure is not limited to a monocyclic structure, and may be a polycyclic structure such as a norbornane ring or a dicyclohexane ring.

  The alicyclic hydrocarbon group may have a carbon-carbon unsaturated bond, but its content is 10% or less, preferably 5% or less, more preferably 3% or less of the total carbon-carbon bonds. is there. By setting the carbon-carbon unsaturated bond of the alicyclic hydrocarbon group within this range, transparency and heat resistance are improved. The carbon constituting the alicyclic hydrocarbon group includes a hydrogen atom, a hydrocarbon group, a halogen atom, an alkoxy group, a hydroxy group, an ether group, an ester group, a cyano group, an amide group, an imide group, a silyl group, and A chain hydrocarbon group or the like substituted with a polar group (halogen atom, alkoxy group, hydroxy group, ether group, ester group, cyano group, amide group, imide group, or silyl group) may be bonded. A hydrogen atom or a chain hydrocarbon group having 1 to 6 carbon atoms is preferred in terms of heat resistance and low water absorption.

  In addition, “...” In the formula (3) represents carbon-carbon saturation or carbon-carbon unsaturated bond in the main chain, but unsaturated bond is required when transparency and heat resistance are strongly required. The content of is usually 10% or less, preferably 5% or less, more preferably 3% or less, of all the carbon-carbon bonds constituting the main chain.

  Among the repeating units represented by the formula (1), the repeating unit represented by the following formula (4) is excellent in terms of heat resistance and low water absorption.

  Among the repeating units represented by the formula (2), the repeating unit represented by the following formula (5) is excellent in terms of heat resistance and low water absorption.

  Among the repeating units represented by the formula (3), the repeating unit represented by the following formula (6) is excellent in terms of heat resistance and low water absorption.

  In formula (4), formula (5) and formula (6), Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, Rl, Rm and Rn are each independently a hydrogen atom. Alternatively, it represents a lower chain hydrocarbon group, and a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms is excellent in terms of heat resistance and low water absorption.

  Among the repeating units having a chain structure represented by the formulas (2) and (3), the repeating unit having a chain structure represented by the formula (3) is stronger in the obtained hydrocarbon polymer. Excellent characteristics.

  In the present invention, a repeating unit (a) having an alicyclic structure represented by the formula (1) and a chain represented by the formula (2) and / or the formula (3) in the hydrocarbon copolymer. The total content with the repeating unit (b) of the shape structure is usually 90% or more, preferably 95% or more, more preferably 97% or more, on a weight basis. By setting the total content within the above range, low birefringence, heat resistance, low water absorption, and mechanical strength are highly balanced.

  The content of the repeating unit (b) having a chain structure in the alicyclic hydrocarbon copolymer is appropriately selected according to the purpose of use, but is usually 1% or more and less than 10%, preferably 1% on a weight basis. It is 8% or less, more preferably 2% or more and 6% or less. When the content of the repeating unit (b) is in the above range, low birefringence, heat resistance, and low water absorption are highly balanced.

  Further, the chain length of the repeating unit (a) is sufficiently shorter than the molecular chain length of the alicyclic hydrocarbon copolymer, specifically, A = (repeating unit chain having an alicyclic structure). Weight average molecular weight), B = (Weight average molecular weight of alicyclic hydrocarbon copolymer (Mw) × (number of repeating units having alicyclic structure / all repeats constituting alicyclic hydrocarbon copolymer) A) is 30% or less of B, preferably 20% or less, more preferably 15% or less, and particularly preferably 10% or less. When A is outside this range, the low birefringence is poor.

  Furthermore, it is preferable that the chain length of the repeating unit (a) has a specific distribution. Specifically, when A = (weight average molecular weight of repeating unit chain having an alicyclic structure) and C = (number average molecular weight of repeating unit chain having an alicyclic structure), A / C is preferable. Is 1.3 or more, more preferably 1.3 to 8, and most preferably 1.7 to 6. When A / C is excessively small, the degree of block increases, and when it is excessively large, the degree of randomness increases, and in any case, low birefringence is inferior.

  The molecular weight of the alicyclic hydrocarbon copolymer of the present invention is 1,000 in terms of polystyrene (or polyisoprene) converted weight average molecular weight (Mw) measured by gel permeation chromatography (hereinafter, GPC). In the range of ˜1,000,000, preferably 5,000 to 500,000, more preferably 10,000 to 300,000, and most preferably 50,000 to 250,000. If the weight average molecular weight (Mw) of the alicyclic hydrocarbon-based copolymer is excessively small, the strength characteristics of the molded article are inferior.

  The molecular weight distribution of such a copolymer can be appropriately selected according to the purpose of use, but the ratio (Mw) of polystyrene (or polyisoprene) -converted weight average molecular weight (Mw) and number average molecular weight (Mn) measured by GPC. / Mn), usually 2.5 or less, preferably 2.3 or less, more preferably 2 or less. When Mw / Mn is in this range, mechanical strength and heat resistance are highly balanced.

  The glass transition temperature (Tg) of the copolymer may be appropriately selected depending on the purpose of use, but is usually 50 to 250 ° C, preferably 70 to 200 ° C, more preferably 90 to 180 ° C.

  Next, a method for producing the “polymer having an alicyclic structure” will be described.

  The method for producing an alicyclic hydrocarbon-based copolymer is as follows: (1) copolymerizing an aromatic vinyl compound with another monomer that can be copolymerized, and hydrogenating the carbon-carbon unsaturated bonds of the main chain and aromatic ring. And (2) a method of copolymerizing an alicyclic vinyl compound with another monomer copolymerizable and hydrogenating as necessary.

  When the alicyclic hydrocarbon-based copolymer of the present invention is produced by the above-described method, the aromatic vinyl compound and / or other monomer copolymerizable with the alicyclic vinyl compound (a ′) ( b ′), the repeating unit derived from the compound (a ′) in the copolymer is D = (weight of the repeating unit chain derived from the aromatic vinyl compound and / or the alicyclic vinyl compound) Average molecular weight), E = (Weight average molecular weight of hydrocarbon copolymer (Mw) × (Number of repeating units derived from aromatic vinyl compound and / or alicyclic vinyl compound / Hydrocarbon copolymer) Of the copolymer having a chain structure in which D is 30% or less of E, preferably 20% or less, more preferably 15% or less, and most preferably 10% or less. Main chain, aromatic ring and cycloalkene ring Carbon of the unsaturated ring - can be obtained efficiently by a method for hydrogenating carbon-carbon unsaturated bond. When D is out of the above range, the low birefringence of the resulting alicyclic hydrocarbon copolymer is poor.

  In the present invention, the method (1) is preferable because an alicyclic hydrocarbon copolymer can be obtained more efficiently.

  The copolymer before hydrogenation further has a D / F when F = (number average molecular weight of a chain of repeating units derived from an aromatic vinyl compound and / or an alicyclic vinyl compound). A certain range is preferable. Specifically, D / F is preferably 1.3 or more, more preferably 1.3 or more and 8 or less, and most preferably 1.7 or more and 6 or less. When D / F is outside this range, the low birefringence of the resulting alicyclic hydrocarbon copolymer is poor.

  The weight average molecular weight and number average molecular weight of the chain of repeating units derived from the above compound (a ′) are, for example, unsaturated two in the main chain of the aromatic vinyl copolymer described in the document Macromolecules 1983, 16, 1925-1928. It can be confirmed by, for example, a method of measuring the molecular weight of the aromatic vinyl chain taken out by reductive decomposition after adding a heavy bond with ozone.

  The molecular weight of the copolymer before hydrogenation is 1,000 to 1,000,000, preferably 5,000 to 500,000 in terms of polystyrene (or polyisoprene) equivalent weight average molecular weight (Mw) measured by GPC. More preferably, it is in the range of 10,000 to 300,000. When the weight average molecular weight (Mw) of the copolymer is excessively small, the strength characteristics of the molded product of the alicyclic hydrocarbon copolymer obtained therefrom are inferior. Conversely, when the copolymer is excessively large, the hydrogenation reactivity is inferior.

  Specific examples of the aromatic vinyl compound used in the method (1) include, for example, styrene, α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-isopropylstyrene, α-t-butylstyrene. 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, monochlorostyrene , Dichlorostyrene, monofluorostyrene, 4-phenylstyrene and the like, and styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene and the like are preferable.

  Specific examples of the alicyclic vinyl compound used in the method (2) include, for example, cyclobutylethylene, cyclopentylethylene, cyclohexylethylene, cycloheptylethylene, cyclooctylethylene, norbornylethylene, dicyclohexylethylene, α -Methylcyclohexylethylene, α-t-butylcyclohexylethylene, cyclopentenylethylene, cyclohexenylethylene, cycloheptenylethylene, cyclooctenylethylene, cyclodecenylethylene, norbornenylethylene, α-methylcyclohexenylethylene, and α -T-butylcyclohexenylethylene etc. are mentioned, Among these, cyclohexylethylene and (alpha) -methylcyclohexylethylene are preferable.

  These aromatic vinyl compounds and alicyclic vinyl compounds can be used alone or in combination of two or more.

  Other monomers that can be copolymerized are not particularly limited, but chain vinyl compounds and chain conjugated diene compounds are used. When chain conjugated dienes are used, the operability in the production process is excellent. The resulting alicyclic hydrocarbon copolymer is excellent in strength properties.

  Specific examples of the chain vinyl compound include chain olefin monomers such as ethylene, propylene, 1-butene, 1-pentene and 4-methyl-1-pentene; 1-cyanoethylene (acrylonitrile), 1-cyano- Nitrile monomers such as 1-methylethylene (methacrylonitrile) and 1-cyano-1-chloroethylene (α-chloroacrylonitrile); 1- (methoxycarbonyl) -1-methylethylene (methacrylic acid methyl ester), 1- (Ethoxycarbonyl) -1-methylethylene (methacrylic acid ethyl ester), 1- (propoxycarbonyl) -1-methylethylene (methacrylic acid propyl ester), 1- (butoxycarbonyl) -1-methylethylene (methacrylic) Acid butyl ester), 1-methoxycarboni (Meth) acrylic acid such as ethylene (acrylic acid methyl ester), 1-ethoxycarbonylethylene (acrylic acid ethyl ester), 1-propoxycarbonylethylene (acrylic acid propyl ester), 1-butoxycarbonylethylene (acrylic acid butyl ester) Ester monomers, 1-carboxyethylene (acrylic acid), 1-carboxy-1-methylethylene (methacrylic acid), unsaturated fatty acid monomers such as maleic anhydride, and the like are mentioned, among which chain olefin monomers are preferable, Most preferred are ethylene, propylene and 1-butene.

  Examples of the chain conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. Of these chain vinyl compounds and chain conjugated dienes, chain conjugated dienes are preferable, and butadiene and isoprene are particularly preferable. These chain vinyl compounds and chain conjugated dienes can be used alone or in combination of two or more.

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

  The method for polymerizing the compound (a ′) is not particularly limited, but after the polymerization is started using a batch polymerization method (batch method), a monomer sequential addition method (a part of the total amount of monomers used), And a method of proceeding polymerization by successively adding monomers). In particular, when the monomer sequential addition method is used, a hydrocarbon copolymer having a preferable chain structure can be obtained. The copolymer before hydrogenation has a more random chain structure, so that the above-mentioned D value is smaller and / or the D / F shows a larger value. The degree of randomness of the copolymer is determined by the speed ratio between the polymerization rate of the aromatic vinyl compound and the polymerization rate of other copolymerizable monomers, and the smaller this speed ratio, the more It has a random chain structure.

  According to the monomer sequential addition method, since the uniformly mixed monomer is sequentially added into the polymerization system, unlike the batch method, the polymerization selectivity of the monomer is further lowered during the growth process by polymer polymerization. The resulting copolymer has a more random chain structure. In addition, since the accumulation of polymerization reaction heat in the polymerization system is small, the polymerization temperature can be kept low and stable.

  In the case of the monomer sequential addition method, first, the total amount of monomers used is usually 0.01 wt% to 60 wt%, preferably 0.02 wt% to 20 wt%, more preferably 0.05 wt% to 10 wt%. Polymerization is started by adding an initiator in the state in which the monomer is present in the polymerization reactor as an initial monomer. When the initial monomer amount is in such a range, the reaction heat generated in the initial reaction after the initiation of polymerization can be easily removed, and the resulting copolymer can have a more random chain structure.

  When the reaction is continued until the polymerization conversion of the initial monomer is 70% or more, preferably 80% or more, more preferably 90% or more, the chain structure of the resulting copolymer becomes more random. Thereafter, the remainder of the monomer is continuously added, and the rate of addition is determined in consideration of the consumption rate of the monomer in the polymerization system.

  Usually, when the time required for the polymerization rate of the initial monomer to reach 90% is T, and the ratio (%) of the initial monomer to the total used monomer is I, the relational expression [(100−I) × T / I ] Is determined so that the addition of the remaining monomer is completed within a range of 0.5 to 3 times, preferably 0.8 to 2 times, more preferably 1 to 1.5 times the time given by Specifically, the initial monomer amount and the rate of addition of the remaining monomer are determined so that it is usually in the range of 0.1 to 30 hours, preferably 0.5 to 5 hours, more preferably 1 to 3 hours. Further, the total monomer polymerization conversion immediately after completion of the monomer addition is usually 80% or more, preferably 85% or more, and more preferably 90% or more. When the total monomer polymerization conversion rate immediately after the completion of monomer addition is within the above range, the chain structure of the resulting copolymer becomes more random.

  The polymerization reaction is not particularly limited, such as radical polymerization, anionic polymerization, and cationic polymerization. However, the polymerization operation, the ease of the hydrogenation reaction in the post-process, and the mechanical properties of the finally obtained hydrocarbon copolymer are not limited. In view of strength, the anionic polymerization method is preferable.

  In the case of radical polymerization, methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used in the presence of an initiator, usually at 0 to 200 ° C, preferably 20 to 150 ° C. In the case where it is necessary to prevent the contamination of impurities, etc., bulk polymerization and suspension polymerization are desirable. As radical initiators, benzoyl peroxide, lauroyl peroxide, organic peroxides such as t-butyl-peroxy-2-ethylhexanoate, azoisobutyronitrile, 4,4-azobis-4-cyanopentanoic acid An azo compound such as azodibenzoyl, a water-soluble catalyst typified by potassium persulfate and ammonium persulfate, a redox initiator, and the like can be used.

  In the case of anionic polymerization, a method such as bulk polymerization, solution polymerization, slurry polymerization is usually performed in the temperature range of 0 to 200 ° C., preferably 20 to 100 ° C., particularly preferably 20 to 80 ° C. in the presence of an initiator. Although it can be used, solution polymerization is preferred in view of removal of reaction heat. In this case, an inert solvent capable of dissolving the polymer and its hydride is used. Examples of the inert solvent used in the solution reaction include aliphatic hydrocarbons such as n-butane, n-pentane, iso-pentane, n-hexane, n-heptane, and iso-octane; cyclopentane, cyclohexane, methylcyclopentane, Examples include alicyclic hydrocarbons such as methylcyclohexane and decalin; aromatic hydrocarbons such as benzene and toluene. Among them, when aliphatic hydrocarbons and alicyclic hydrocarbons are used, hydrogenation reaction is also performed. It can be used as it is as an inert solvent. These solvents can be used alone or in combination of two or more, and are usually used at a ratio of 200 to 10,000 parts by weight with respect to 100 parts by weight of all the monomers used.

  Examples of the initiator for the anionic polymerization include monoorganolithium such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, and phenyllithium, dilithiomethane, 1,4-diobane, and 1,4-dilithio. A polyfunctional organolithium compound such as 2-ethylcyclohexane can be used.

  In the polymerization reaction, a polymerization accelerator, a randomizer (an additive having a function of preventing a long chain of one component) from being used, and the like can be used. In the case of anionic polymerization, for example, a Lewis base compound can be used as a randomizer. Specific examples of the Lewis base compound include ether compounds such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, diphenyl ether, ethylene glycol diethyl ether, ethylene glycol methyl phenyl ether; tetramethylethylenediamine, trimethylamine, triethylamine, pyridine Tertiary amine compounds such as potassium; t-amyl oxide, alkali metal alkoxide compounds such as potassium t-butyl oxide; and phosphine compounds such as triphenylphosphine. These Lewis base compounds can be used alone or in combination of two or more.

  The polymer obtained by the above radical polymerization or anion polymerization can be recovered by a known method such as a steam stripping method, a direct solvent removal method, or an alcohol coagulation method. In addition, when an inert solvent is used in the hydrogenation reaction during the polymerization, the polymer is not recovered from the polymerization solution and can be used as it is in the hydrogenation step.

(Method of hydrogenating unsaturated bonds)
When conducting hydrogenation reactions such as carbon-carbon double bonds of unsaturated rings such as aromatic rings and cycloalkene rings of the copolymer before hydrogenation, and unsaturated bonds of the main chain, the reaction method and reaction form are special. There is no particular limitation, and it may be carried out according to a known method, but a hydrogenation method that can increase the hydrogenation rate and has little polymer chain scission reaction that occurs simultaneously with the hydrogenation reaction is preferable, for example, in an organic solvent, nickel, The method is performed using a catalyst containing at least one metal selected from cobalt, iron, titanium, rhodium, palladium, platinum, ruthenium, and rhenium. As the hydrogenation catalyst, either a heterogeneous catalyst or a homogeneous catalyst can be used.

  The heterogeneous catalyst can be used in the form of a metal or a metal compound or supported on a suitable carrier. Examples of the carrier include activated carbon, silica, alumina, calcium carbide, titania, magnesia, zirconia, diatomaceous earth, silicon carbide and the like. The supported amount of the catalyst is usually 0.01 to 80% by weight, preferably 0. The range is from 05 to 60% by weight. The homogeneous catalyst is a catalyst in which a nickel, cobalt, titanium or iron compound and an organometallic compound (for example, an organoaluminum compound or an organolithium compound) are combined, or an organometallic complex catalyst such as rhodium, palladium, platinum, ruthenium or rhenium. Can be used. Examples of the nickel, cobalt, titanium, or iron compound include acetylacetone salts, naphthene salts, cyclopentadienyl compounds, cyclopentadienyl dichloro compounds, and the like of various metals. As the organic aluminum compound, alkylaluminum such as triethylaluminum and triisobutylaluminum, aluminum halide such as diethylaluminum chloride and ethylaluminum dichloride, alkylaluminum hydride such as diisobutylaluminum hydride and the like are preferably used.

  As an example of the organometallic complex catalyst, a metal complex such as a γ-dichloro-π-benzene complex, a dichloro-tris (triphenylphosphine) complex, a hydrido-chloro-triphenylphosphine) complex of each of the above metals is used. These hydrogenation catalysts can be used alone or in combination of two or more, and the amount used is usually 0.01 to 100 parts, preferably on the basis of weight with respect to the polymer. 0.05 to 50 parts, more preferably 0.1 to 30 parts.

  The hydrogenation reaction is usually 10 to 250 ° C., but preferably 50 to 200 ° C., more preferably, because the hydrogenation rate can be increased and the polymer chain scission reaction occurring simultaneously with the hydrogenation reaction can be reduced. Is 80-180 ° C. The hydrogen pressure is usually 0.1 MPa to 30 MPa, but in addition to the above reasons, from the viewpoint of operability, it is preferably 1 MPa to 20 MPa, more preferably 2 MPa to 10 MPa.

The hydrogenation rate of the hydride obtained in this way was measured by ¹ H-NMR,
All of the carbon-carbon unsaturated bond of the main chain, the carbon-carbon double bond of the aromatic ring, and the carbon-carbon double bond of the unsaturated ring are usually 90% or more, preferably 95% or more, more preferably 97%. That's it. When the hydrogenation rate is low, the low birefringence, thermal stability, etc. of the resulting copolymer are lowered.

  The method for recovering the hydride after completion of the hydrogenation reaction is not particularly limited. Usually, after removing the hydrogenation catalyst residue by a method such as filtration or centrifugation, the solvent is removed directly from the hydride solution by drying, the hydride solution is poured into a poor solvent for the hydride, and the hydride A method of coagulating can be used.

  More specifically, the “resin containing a polymer having an alicyclic structure” includes a polymer block [A] containing a repeating unit [1] represented by the following formula (11) and the following formula (11). A polymer block [B] containing a repeating unit [1] represented by the following formula (12) and / or a repeating unit [3] represented by the following formula (13): And a mole fraction a (mol%) of the repeating unit [1] in the polymer block [A] and a mole fraction b (mol) of the repeating unit [1] in the polymer block [B]. %) Is preferable to contain a block polymer in which a> b.

In Formula (11), R ¹ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^{2 to} R ¹² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, or a carbon number. 1 to 20 alkoxy groups or halogen groups.

In Formula (12), R ¹³ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

In Formula (13), R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

A preferred structure of the repeating unit [1] represented by the above formula (11) is ^{one in} which R ¹ is hydrogen or a methyl group and R ² -R ¹² are all hydrogen. When the content of the repeating unit [1] in the polymer block [A] is in the above range, transparency and mechanical strength are excellent. The remainder other than the repeating unit [1] in the polymer block [A] is a hydrogenated repeating unit derived from a chain conjugated diene or a chain vinyl compound.

  The polymer block [B] contains the repeating unit [1] and the repeating unit [2] represented by the following formula (12) or / and the repeating unit [3] represented by the following formula (13). The content of the repeating unit [1] in the polymer block [B] is preferably 40 to 95 mol%, more preferably 50 to 90 mol%. When the content of the repeating unit [1] is in the above range, transparency and mechanical strength are excellent. When the molar fraction of the repeating unit [2] in the block [B] is m2 (mol%) and the molar fraction of the repeating unit [3] is m3 (mol%), 2 × m2 + m3 is preferably It is 2 mol% or more, more preferably 5 to 60 mol%, most preferably 10 to 50 mol%.

A preferred structure of the repeating unit [2] represented by the above formula (12) is one in which R ¹³ is hydrogen or a methyl group.

A preferred structure of the repeating unit [3] represented by the above formula (13) is one in which R ¹⁴ is hydrogen and R ¹⁵ is a methyl group or an ethyl group.

  If the content of the repeating unit [2] or the repeating unit [3] in the polymer block [B] is too small, the mechanical strength is lowered. Therefore, when the content of the repeating unit [2] and the repeating unit [3] is in the above range, transparency and mechanical strength are excellent. The polymer block [B] may further contain a repeating unit [X] represented by the following formula (X). The content of the repeating unit [X] is an amount that does not impair the properties of the block copolymer of the present invention, and is preferably 30 mol% or less, more preferably 20 mol% or less, based on the entire block copolymer. It is.

In the formula (X), R ²⁵ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ²⁶ represents a nitrile group, an alkoxycarbonyl group, a formyl group, a hydroxycarbonyl group, or a halogen group, and R ²⁷ represents Represents a hydrogen atom. Alternatively, R ²⁶ and R ²⁷ may be bonded to each other to form an acid anhydride group or an imide group.

  In addition, the block copolymer used in the present invention has a molar fraction of the repeating unit [1] in the polymer block [A] and a molar fraction of the repeating unit [1] in the polymer block [B]. In the case of b, there is a relationship of a> b. Thereby, it is excellent in transparency and mechanical strength.

  Further, the block copolymer used in the present invention has a ratio when the number of moles of all repeating units constituting the block [A] is ma and the number of moles of all repeating units constituting the block [B] is mb. (Ma: mb) is preferably 5:95 to 95: 5, more preferably 30:70 to 95: 5, and particularly preferably 40:60 to 90:10. When (ma: mb) is in the above range, the mechanical strength and heat resistance are excellent.

  The molecular weight of the block copolymer used in the present invention is a weight average molecular weight in terms of polystyrene (or polyisoprene) measured by gel permeation chromatography (hereinafter referred to as “GPC”) using tetrahydrofuran (THF) as a solvent. (Hereinafter referred to as “Mw”), preferably in the range of 10,000 to 300,000, more preferably 15,000 to 250,000, particularly preferably 20,000 to 200,000. When the Mw of the block copolymer is in the above range, the balance of mechanical strength, heat resistance, and moldability is excellent.

  The molecular weight distribution of the block copolymer can be appropriately selected depending on the purpose of use, but is the ratio of Mw in terms of polystyrene (or polyisoprene) measured by GPC and the number average molecular weight (hereinafter referred to as “Mn”) ( Mw / Mn), preferably 5 or less, more preferably 4 or less, particularly preferably 3 or less. When Mw / Mn is in this range, the mechanical strength and heat resistance are excellent.

  The glass transition temperature (hereinafter referred to as “Tg”) of the block copolymer may be appropriately selected according to the purpose of use, but it is determined on the high temperature side by a differential scanning calorimeter (hereinafter referred to as “DSC”). The measured value is preferably 70 to 200 ° C, more preferably 80 to 180 ° C, and particularly preferably 90 to 160 ° C.

  The block copolymer used in the present invention has a polymer block [A] and a polymer block [B], and is a ([A]-[B]) type diblock copolymer. [A]-[B]-[A]) type or ([B]-[A]-[B]) type triblock copolymer, polymer block [A] and polymer block [ B] may be a block copolymer in which a total of 4 or more are alternately connected. Moreover, the block copolymer which these blocks couple | bonded with radial type may be sufficient.

  The block copolymer used in the present invention can be obtained by the following method. As the method, a monomer mixture containing an aromatic vinyl compound or / and an alicyclic vinyl compound having an unsaturated bond in the ring, and a vinyl monomer (excluding an aromatic vinyl compound and an alicyclic vinyl compound). A polymer block containing a repeating unit derived from an aromatic vinyl compound or / and an alicyclic vinyl compound, and a polymer block containing a repeating unit derived from a vinyl monomer A block copolymer is obtained. And a method of hydrogenating an aromatic ring and / or an aliphatic ring of the block copolymer, a monomer mixture containing a saturated alicyclic vinyl compound, and a vinyl monomer (aromatic vinyl compound and alicyclic vinyl compound) A polymer block containing a repeating unit derived from an alicyclic vinyl compound, and a block copolymer having a polymer block containing a repeating unit derived from a vinyl monomer. Examples include a method for obtaining a coalescence. Especially, what is more preferable as a block copolymer used for this invention can be obtained with the following method, for example.

  (1) As a first method, first, a monomer mixture [a ′] containing 50 mol% or more of an aromatic vinyl compound and / or an alicyclic vinyl compound having an unsaturated bond in the ring is polymerized to obtain an aromatic A polymer block [A ′] containing a repeating unit derived from an aliphatic vinyl compound or / and an alicyclic vinyl compound having an unsaturated bond in the ring is obtained. Monomer mixture of vinyl monomer (excluding aromatic vinyl compound and alicyclic vinyl compound) of 2 mol% or more, and aromatic vinyl compound and / or alicyclic vinyl compound having an unsaturated bond in the ring The monomer mixture [b ′], which is contained in an amount smaller than the proportion in [a ′], is polymerized to repeat the aromatic vinyl compound or / and the alicyclic vinyl compound-derived repeating unit and the vinyl monomer. A polymer block [B ′] containing repeating units is obtained. After obtaining the block copolymer having the polymer block [A ′] and the polymer block [B ′] through at least these steps, the aromatic ring and / or the aliphatic ring of the block copolymer is hydrogenated. Turn into.

  (2) As a second method, first, a polymer containing a repeating unit derived from a saturated alicyclic vinyl compound by polymerizing a monomer mixture [a] containing 50 mol% or more of a saturated alicyclic vinyl compound. A block [A] is obtained. Contains 2 mol% or more of vinyl-based monomers (excluding aromatic vinyl compounds and alicyclic vinyl compounds), and contains saturated alicyclic vinyl compounds in a proportion smaller than the proportion in the monomer mixture [a]. The monomer mixture [b] is polymerized to obtain a polymer block [B] containing a repeating unit derived from a saturated alicyclic vinyl compound and a repeating unit derived from a vinyl monomer. At least through these steps, a block copolymer having the polymer block [A] and the polymer block [B] is obtained.

  Among the above methods, the method (1) is more preferable from the viewpoints of availability of monomers, polymerization yield, ease of introduction of the repeating unit [1] into the polymer block [B ′], and the like. .

  Specific examples of the aromatic vinyl compound in the method (1) include styrene, α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-isopropylstyrene, α-t-butylstyrene, and 2-methylstyrene. 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, monochlorostyrene, dichlorostyrene, mono Examples include fluorostyrene, 4-phenylstyrene, and the like, and those having a substituent such as a hydroxyl group or an alkoxy group. Of these, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene and the like are preferable.

  Specific examples of the unsaturated alicyclic vinyl compound in the method (1) include cyclohexenylethylene, α-methylcyclohexenylethylene, α-t-butylcyclohexenylethylene, and the like, and a halogen group and an alkoxy group. Or those having a substituent such as a hydroxyl group.

  These aromatic vinyl compounds and alicyclic vinyl compounds can be used alone or in combination of two or more. In the present invention, any one of the monomer mixtures [a ′] and [b ′] In addition, it is preferable to use an aromatic vinyl compound, and it is more preferable to use styrene or α-methylstyrene.

  The vinyl monomer used in the above method includes a chain vinyl compound and a chain conjugated diene compound.

  Specific examples of the chain vinyl compound include chain olefin monomers such as ethylene, propylene, 1-butene, 1-pentene and 4-methyl-1-pentene. Among these, chain olefin monomers are preferable, and ethylene Most preferred are propylene, 1-butene.

  Examples of the chain conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. Of these chain vinyl compounds and chain conjugated dienes, chain conjugated dienes are preferable, and butadiene and isoprene are particularly preferable. These chain vinyl compounds and chain conjugated dienes can be used alone or in combination of two or more.

  When polymerizing a monomer mixture containing the above monomers, the polymerization reaction may be carried out by any method such as radical polymerization, anionic polymerization, cationic polymerization, etc., but preferably by anionic polymerization in the presence of an inert solvent. Most preferably, living anionic polymerization is performed.

  Anionic polymerization is carried out in the presence of a polymerization initiator in the temperature range of usually 0 to 200 ° C, preferably 20 to 100 ° C, particularly preferably 20 to 80 ° C. Examples of the initiator include monoorganolithium such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, and phenyllithium, dilithiomethane, 1,4-diobane, 1,4-dilithio-2-ethylcyclohexane. A polyfunctional organolithium compound such as can be used.

  Examples of the inert solvent used include aliphatic hydrocarbons such as n-butane, n-pentane, isopentane, n-hexane, n-heptane, and isooctane; cyclopentane, cyclohexane, methylcyclopentane, methylcyclohexane, decalin And alicyclic hydrocarbons such as benzene, toluene and the like, and the use of aliphatic hydrocarbons and alicyclic hydrocarbons is an inert solvent for hydrogenation reaction. Can be used as is. These solvents can be used alone or in combination of two or more, and are usually used at a ratio of 200 to 10,000 parts by weight with respect to 100 parts by weight of all the monomers used.

  When polymerizing each polymer block, a polymerization accelerator, a randomizer, or the like can be used in order to prevent a chain of a certain component from becoming long in each block. In particular, when the polymerization reaction is performed by anionic polymerization, a Lewis base compound or the like can be used as a randomizer. Specific examples of Lewis base compounds include ether compounds such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, diphenyl ether, ethylene glycol diethyl ether, ethylene glycol methyl phenyl ether; tetramethylethylenediamine, trimethylamine, triethylamine, pyridine, etc. Tertiary amine compounds; alkali metal alkoxide compounds such as potassium-t-amyl oxide and potassium-t-butyl oxide; phosphine compounds such as triphenylphosphine. These Lewis base compounds can be used alone or in combination of two or more.

  Examples of the method for obtaining a block copolymer by living anionic polymerization include conventionally known sequential addition polymerization reaction method and coupling method. In the present invention, it is preferable to use sequential addition polymerization reaction method.

  When the block copolymer having the polymer block [A ′] and the polymer block [B ′] is obtained by the sequential addition polymerization reaction method, a step of obtaining the polymer block [A ′], and a polymer block The process of obtaining [B ′] is performed sequentially and continuously. Specifically, in the presence of the living anion polymerization catalyst in an inert solvent, the monomer mixture [a ′] is polymerized to obtain a polymer block [A ′], and then the monomer mixture [b ′] is added to the reaction system. To continue the polymerization to obtain a polymer block [B ′] connected to the polymer block [A ′]. Furthermore, if desired, the monomer mixture [a ′] is added again for polymerization, the polymer block [A ′] is connected to form a triblock body, and the monomer mixture [b ′] is added again for polymerization. Then, a tetrablock body in which the polymer blocks [B ′] are connected is obtained.

  The obtained block copolymer is recovered by a known method such as a steam stripping method, a direct desolvation method, or an alcohol coagulation method. In the polymerization reaction, when an inert solvent is used in the hydrogenation reaction, the polymerization solution can be used as it is in the hydrogenation reaction step, so that the block copolymer need not be recovered from the polymerization solution. .

  Of the block copolymer having the polymer block [A ′] and the polymer block [B ′] obtained in the method (1) (hereinafter referred to as “pre-hydrogenation block copolymer”), the following structure is provided. Those having a repeating unit of

  The polymer block [A ′] constituting the preferred pre-hydrogenation block copolymer is a polymer block containing 50 mol% or more of the repeating unit [4] represented by the following formula (14).

In the formula (14), R ¹⁶ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^{17 to} R ²¹ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, An alkoxy group having 1 to 20 carbon atoms or a halogen group. Note that the [R ¹⁷ -R ^21] represents an R ^17, R ^18, · · and R ^21.

  A preferred polymer block [B ′] necessarily contains the repeating unit [4], and includes a repeating unit [5] represented by the following formula (15) and a repeating unit [6] represented by the following formula (16). ] A polymer block containing at least one of the above. Further, when the mole fraction of the repeating unit [4] in the polymer block [A ′] is a ′ and the mole fraction of the repeating unit [4] in the block [B ′] is b ′, a ′> b ′.

In the formula (15), R ²² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

In Formula (16), R ²³ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ²⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an alkenyl group.

  Further, the block [B ′] may contain a repeating unit [Y] represented by the following formula (Y).

In the formula (Y), R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ²⁹ represents a nitrile group, an alkoxycarbonyl group, a formyl group, a hydroxycarbonyl group, or a halogen group, and R ³⁰ represents Represents a hydrogen atom. Alternatively, R ²⁹ and R ³⁰ may be bonded to each other to form an acid anhydride group or an imide group.

  Furthermore, a preferable block copolymer before hydrogenation is a case where the number of moles of all repeating units constituting the block [A ′] is ma ′ and the number of moles of all repeating units constituting the block [B ′] is mb ′. The ratio (ma ′: mb ′) is 5:95 to 95: 5, more preferably 30:70 to 95: 5, and particularly preferably 40:60 to 90:10. When (ma ′: mb ′) is in the above range, the mechanical strength and heat resistance are excellent.

  The molecular weight of the block copolymer before hydrogenation is preferably 12,000 to 400,000, more preferably 19,000 to 350,000, in terms of polystyrene (or polyisoprene) equivalent Mw measured by GPC using THF as a solvent. Especially preferably, it is the range of 25,000-300,000. When the Mw of the block copolymer is excessively small, the mechanical strength decreases, and when it is excessively large, the hydrogenation rate decreases.

  The molecular weight distribution of the block copolymer before hydrogenation can be appropriately selected depending on the purpose of use, but is the ratio (Mw / Mn) of Mw and Mn in terms of polystyrene (or polyisoprene) measured by GPC, It is 5 or less, more preferably 4 or less, and particularly preferably 3 or less. When Mw / Mn is in this range, the hydrogenation rate is improved.

  The Tg of the block copolymer before hydrogenation may be appropriately selected according to the purpose of use, but it is 70 to 150 ° C., more preferably 80 to 140 ° C., particularly preferably as measured on the high temperature side by DSC. Is 90-130 ° C.

  Method and reaction for hydrogenating the carbon-carbon unsaturated bonds of unsaturated rings such as aromatic rings and cycloalkene rings, and unsaturated bonds of main chains and side chains of the block copolymer before hydrogenation There is no particular limitation on the form, and it may be performed according to a known method. However, a hydrogenation method that can increase the hydrogenation rate and has a low polymer chain scission reaction is preferable. For example, in an organic solvent, nickel, cobalt, iron, Examples thereof include a method performed using a catalyst containing at least one metal selected from titanium, rhodium, palladium, platinum, ruthenium, and rhenium. As the hydrogenation catalyst, either a heterogeneous catalyst or a homogeneous catalyst can be used.

  The heterogeneous catalyst can be used in the form of a metal or metal compound or supported on a suitable carrier. Examples of the support include activated carbon, silica, alumina, calcium carbide, titania, magnesia, zirconia, diatomaceous earth, silicon carbide and the like, and the supported amount of the catalyst is preferably 0.01 to 80% by weight, more preferably It is in the range of 0.05 to 60% by weight. The homogeneous catalyst is a catalyst in which a nickel, cobalt, titanium or iron compound and an organometallic compound (for example, an organoaluminum compound or an organolithium compound) are combined, or an organometallic complex catalyst such as rhodium, palladium, platinum, ruthenium or rhenium. Can be used. As the nickel, cobalt, titanium, or iron compound, for example, acetylacetone salt, naphthenic acid salt, cyclopentadienyl compound, cyclopentadienyl dichloro compound and the like of various metals are used. As the organic aluminum compound, alkylaluminum such as triethylaluminum and triisobutylaluminum, aluminum halide such as diethylaluminum chloride and ethylaluminum dichloride, alkylaluminum hydride such as diisobutylaluminum hydride and the like are preferably used.

  As an example of the organometallic complex catalyst, metal complexes such as γ-dichloro-π-benzene complex, dichloro-tris (triphenylphosphine) complex, hydrido-chloro-triphenylphosphine complex of the above metals are used. These hydrogenation catalysts can be used alone or in combination of two or more, and the amount used is preferably 0.01 to 100 parts by weight, more preferably 100 parts by weight of the polymer. 0.05 to 50 parts by weight, particularly preferably 0.1 to 30 parts by weight.

  The hydrogenation reaction is usually 10 to 250 ° C., but preferably 50 to 200 ° C., more preferably 80 to 180 ° C., because the hydrogenation rate can be increased and the polymer chain scission reaction can be reduced. is there. The hydrogen pressure is preferably 0.1 MPa to 30 MPa, but in addition to the above reasons, it is more preferably 1 MPa to 20 MPa, and particularly preferably 2 MPa to 10 MPa from the viewpoint of operability.

The hydrogenation rate of the block copolymer obtained in this way is determined by ¹ H-NMR as measured by carbon-carbon unsaturated bonds of the main chain and side chains, carbon-carbon unsaturation of aromatic rings and cycloalkene rings. Any of the saturated bonds is preferably 90% or more, more preferably 95% or more, and particularly preferably 97% or more. When the hydrogenation rate is low, the low birefringence, thermal stability, etc. of the resulting copolymer are lowered.

  After completion of the hydrogenation reaction, the block copolymer is prepared by removing the hydrogenation catalyst from the reaction solution by a method such as filtration or centrifugation, and then removing the solvent directly by drying. It can be recovered by a method such as pouring into a poor solvent and solidifying.

[Resin 2]
Resin 2 is a resin comprising a copolymer of an α-olefin and a cyclic olefin represented by the following general formula (I) or (II).

…式（I）

... Formula (I)

In the formula (I), n is 0 or 1, m is 0 or a positive integer, k is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom. Represents a halogen atom or a hydrocarbon group.

…式（II）

... Formula (II)

In the formula (II), p and q are each independently 0 or a positive integer, r and s each independently represent 0, 1 or 2, and R ^{21 to} R ³⁹ are each independently a hydrogen atom. Represents a halogen atom, a hydrocarbon group or an alkoxy group.

[Cyclic olefins represented by general formulas (I) and (II)]
In the above general formula (I), n is 0 or 1, m is 0 or a positive integer, and k is 0 or 1. When k is 1, the ring represented by k is a 6-membered ring, and when k is 0, this ring is a 5-membered ring.

R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

  Moreover, as a hydrocarbon group, a C1-C20 alkyl group, a C1-C20 halogenated alkyl group, a C3-C15 cycloalkyl group, or an aromatic hydrocarbon group is mentioned normally. It is done. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. These alkyl groups may be substituted with a halogen atom.

Examples of the cycloalkyl group include a cyclohexyl group, and examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. Further, in the general formula (I), R ¹⁵ and R ¹⁶ are R ¹⁷ and R ¹⁸ , R ¹⁵ and R ¹⁷ are R ¹⁶ and R ¹⁸ , R ¹⁵ and R ¹⁸ are R ¹⁶ and R ¹⁷ may be bonded to each other (in cooperation with each other) to form a monocyclic or polycyclic group, and the monocyclic or polycyclic ring thus formed is a double bond You may have. Specific examples of the monocyclic or polycyclic ring formed here include the following.

In the above-exemplified monocyclic or polycyclic ring, the carbon atom numbered 1 or 2 is carbon bonded to R ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) in the general formula (I), respectively. Represents an atom.

R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group, and an isopropylidene group.

In general formula (II), p and q are each independently 0 or a positive integer, and r and s are each independently 0, 1 or 2. R ^{21 to} R ³⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group.

  Here, the halogen atom is the same as the halogen atom in the general formula (I). Moreover, as a hydrocarbon group, a C1-C20 alkyl group, a C3-C15 cycloalkyl group, or an aromatic hydrocarbon group is mentioned normally. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. These alkyl groups may be substituted with a halogen atom.

  Examples of the cycloalkyl group include a cyclohexyl group. Examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group. Specifically, the phenyl group, the tolyl group, the naphthyl group, the benzyl group, and the phenylethyl group. Etc.

Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. Here, the carbon atom to which R ²⁹ and R ³⁰ are bonded and the carbon atom to which R ³³ is bonded or the carbon atom to which R ³¹ is bonded are directly or an alkylene group having 1 to 3 carbon atoms. It may be connected via. That is, when the two carbon atoms are bonded via an alkylene group, R ²⁹ and R ³³ , or R ³⁰ and R ³¹ jointly form a methylene group (—CH ₂ -), Ethylene group (—CH ₂ CH ₂ —) or propylene group (—CH ₂ CH ₂ CH ₂ —) of any alkylene group is formed.

Further, when r = s = 0, R ³⁵ and R ³² or R ³⁵ and R ³⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Specifically, when r = s = 0, the following aromatic rings formed by R ³⁵ and R ³² are exemplified.

  Here, q is synonymous with q in the general formula (II).

  Specific examples of the cyclic olefin represented by the general formula (I) or (II) according to the present invention include bicyclo-2-heptene derivatives (bicyclohept-2-ene derivatives), tricyclo-3-decene derivatives, tricyclo -3-undecene derivative, tetracyclo-3-dodecene derivative, pentacyclo-4-pentadecene derivative, pentacyclopentadecadiene derivative, pentacyclo-3-pentadecene derivative, pentacyclo-3-hexadecene derivative, pentacyclo-4-hexadecene derivative, hexacyclo- 4-heptadecene derivative, heptacyclo-5-eicosene derivative, heptacyclo-4-eicosene derivative, heptacyclo-5-heneicosene derivative, octacyclo-5-docosene derivative, nonacyclo-5-pentacocene derivative, nonacyclo-6 Xacocene derivative, cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene derivative, 1,4-methano-1,4,4a, 5,10,10a-hexahydroanthracene derivative Etc.

  Specific examples of the cyclic olefin represented by the general formula (I) or (II) according to the present invention are shown below, but the present invention is not limited to these exemplified compounds.

<< Bicyclo [2.2.1] hept-2-ene derivative >>
1) Bicyclo [2.2.1] hept-2-ene 2) 6-Methylbicyclo [2.2.1] hept-2-ene 3) 5,6-Dimethylbicyclo [2.2.1] hept- 2-ene 4) 1-methylbicyclo [2.2.1] hept-2-ene 5) 6-ethylbicyclo [2.2.1] hept-2-ene 6) 6-n-butylbicyclo [2. 2.1] Hept-2-ene 7) 6-Isobutylbicyclo [2.2.1] hept-2-ene 8) 7-Methylbicyclo [2.2.1] hept-2-ene, etc.

<< Tetracyclo [4.4.0.1 ^2,5 . ^1,7,10 ] -3-dodecene derivative >>
9) Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 10) 8-Methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 11) 8-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 12) 8-propyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 13) 8-Butyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 14) 8-isobutyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 15) 8-hexyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 16) 8-cyclohexyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 17) 8-stearyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 18) 5,10-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 19) 2,10-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 20) 8,9-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 21) 8-ethyl-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 22) 11,12-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 23) 2,7,9-trimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 24) 9-ethyl-2,7-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 25) 9-isobutyl-2,7-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 26) 9,11,12-trimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 27) 9-ethyl-11,12-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 28) 9-isobutyl-11,12-dimethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 29) 5,8,9,10-tetramethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 30) 8-ethylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 31) 8-ethylidene-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 32) 8-ethylidene-9-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 33) 8-ethylidene-9-isopropyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 34) 8-ethylidene-9-butyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 35) 8-n-propylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 36) 8-n-propylidene-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 37) 8-n-propylidene-9-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 38) 8-n-propylidene-9-isopropyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 39) 8-n-propylidene-9-butyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 40) 8-isopropylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 41) 8-isopropylidene-9-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 42) 8-isopropylidene-9-ethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 43) 8-isopropylidene-9-isopropyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 44) 8-isopropylidene-9-butyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 45) 8-chlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 46) 8-Bromotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 47) 8-fluorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene 48) 8,9-dichlorotetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, etc.

<< Hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene derivative "
49) Hexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene 50) 12-methyl hexa cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14 ] −
4-Heptadecene 51) 12-ethylhexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene 52) 12-isobutyl hexamethylene cyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14
] -4-heptadecene 53) 1,6,10-trimethyl-12-isobutylhexacyclo [6.6.1.1 ^3,6 . 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene, etc.

<< Octacyclo [8.8.0.1 ^2,9 . 1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5-docosene derivative >>
54) Octacyclo [8.8.0.1 ^2,9 . 1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5-docosene 55) 15-methyloctacyclo [8.8.0.1 ^2,9 . 1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5-docosene 56) 15-ethyloctacyclo [8.8.0.1 ^2,9 . 1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5-docosene, etc.

<< Pentacyclo [6.6.1.1 ^3,6 . 0 ^2,7 . 0 ^9,14 ] -4-hexadecene derivative >>
57) Pentacyclo [6.6.1.1 ^3,6 . 0 ^2,7 . 0 ^9,14 ] -4-hexadecene 58) 1,3-dimethylpentacyclo [6.6.1.1 ^3,6 . 0 ^2,7 . 0 ^9,14 ] -4-hexadecene 59) 1,6-dimethylpentacyclo [6.6.1.1 ^3,6 . 0 ^2,7 . 0 ^9,14 ] -4-hexadecene 60) 15,16-dimethylpentacyclo [6.6.1.1 ^3,6 . 0 ^2,7 . 0 ^9,14 ] -4-hexadecene, etc.

<Heptacyclo-5-eicosene derivative or heptacyclo-5-heneicosene derivative>
61) Heptacyclo [8.7.0.1 ^2,9 . 1 ^4,7 . 1 ^11,17 . 0 ^3,8 . 0 ^12,16 ] -5
Eicosene 62) Heptacyclo [8.8.0.1 ^2,9 . 1 ^4,7 . 1 ^11,18 . 0 ^3,8 . 0 ^12,17 ] -5
Henikosen, etc.

<< Tricyclo [4.3.0.1 ^2,5 ] -3-decene derivative >>
63) Tricyclo [4.3.0.1 ^2,5 ] -3-decene 64) 2-Methyltricyclo [4.3.0.1 ^2,5 ] -3-decene 65) 5-Methyltricyclo [ 4.3.0.1 ^2,5 ] -3-decene, etc.

<< Tricyclo [4.4.0.1 ^2,5 ] -3-undecene derivative >>
66) Tricyclo [4.4.0.1 ^2,5 ] -3-undecene 67) 10-Methyltricyclo [4.4.0.1 ^2,5 ] -3-undecene, etc. << Pentacyclo [6.5 1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene derivative >>
68) Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene 69) 1,3-dimethylpentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene 70) 1,6-dimethylpentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene 71) 14,15-dimethylpentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene, etc.

<Diene compound>
72) Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 9,13] -4, ^10- pentadecadien, etc.

<< Pentacyclo [7.4.0.1 ^2,6 . 1 ^9,12 . 0 ^8,13 ] -3-pentadecene derivative >>
73) Pentacyclo [7.4.0.1 ^2,6 . 1 ^9,12 . 0 ^8,13] -3-pentadecene 74) methyl-substituted pentacyclo [7.4.0.1 ^2,6. 1 ^9,12 . 0 ^8,13 ] -3-pentadecene, etc.

<< Heptacyclo [8.7.0.1 ^3,6 . 1 ^10,17 . 1 ^12,15 . 0 ^2,7 . 0 ^11,16 ] -4-eicosene derivative >>
75) Heptacyclo [8.7.0.1 ^3,6 . 1 ^10,17 . 1 ^12,15 . 0 ^2,7 . 0 ^11,16 ] -4
-Eicosene 76) Dimethyl-substituted heptacyclo [8.7.0.1 ^3,6 . 1 ^10,17 . 1 ^12,15 . 0 ^2,7 . 0 ^11,16 ] -4-Eicosen, etc.

<< Nonacyclo [10.9.1.1 ^4,7 . 1 ^13,20 . 1 ^15,18 . 0 ^3,8 . 0 ^2,10 . 0 ^12,21 .
0 ^{14, 19]} -5-pentacosenoic derivative "
77) Nonacyclo [10.9.1.1 ^4,7 . 1 ^13,20 . 1 ^15,18 . 0 ^3,8 . 0 ^2,10 . 0 ^12,21 . 0 ^14,19] -5-pentacosene 78) trimethyl-substituted Nonashikuro [10.9.1.1 ^{4, 7.} 1 ^13,20 . 1 ^15,18 . 0 ^3,8 . 0 ^2,10 . 0 ^12,21 . 0 ^{14, 19]} -5-pentacosenoic, etc.

<< Pentacyclo [8.4.0.1 ^2,5 . 1 ^9,12 . 0 ^8,13 ] -3-hexadecene derivative >>
79) Pentacyclo [8.4.0.1 ^2,5 . 1 ^9,12 . 0 ^8,13 ] -3-hexadecene 80) 11-methyl-pentacyclo [8.4.0.1 ^2,5 . 1 ^9,12 . 0 ^8,13 ] -3-hexadecene 81) 11-ethyl-pentacyclo [8.4.0.1 ^2,5 . 1 ^9,12 . 0 ^8,13 ] -3-hexadecene 82) 10,11-dimethyl-pentacyclo [8.4.0.1 ^2,5 . 1 ^9,12 . 0 ^8,13 ]
-3-hexadecene, etc.

<< Heptacyclo [8.8.0.1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5- ^Heneicosene derivative >>
83) Heptacyclo [8.8.0.1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5
Haneicosene 84) 15-Methyl-heptacyclo [8.8.0.1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5- ^Heneicosene 85) Trimethyl-heptacyclo [8.8.0.1 ^4,7 . 1 ^11,18 . 1 ^13,16 . 0 ^3,8 . 0 ^12,17 ] -5- ^Haneikosen , etc.

<< Nonacyclo [10.10.1 ^5,8 . 1 ^14,21 . 1 ^16,19 . 0 ^2,11 . 0 ^4,9 . 0 ^13,22
. 0 ^15,20] -5-hexacosenoic derivative "
86) Nonacyclo [10.10.1 ^5,8 . 1 ^14,21 . 1 ^16,19 . 0 ^2,11 . 0 ^4,9 . 0 ^13,22 . 0 ^15,20] -5-hexacosenoic, etc.

<Others>
87) 5-Phenyl-bicyclo [2.2.1] hept-2-ene 88) 5-Methyl-5-phenyl-bicyclo [2.2.1] hept-2-ene 89) 5-Benzyl-bicyclo [ 2.2.1] hept-2-ene 90) 5-tolyl-bicyclo [2.2.1] hept-2-ene 91) 5- (ethylphenyl) -bicyclo [2.2.1] hept-2 -Ene 92) 5- (isopropylphenyl) -bicyclo [2.2.1] hept-2-ene 93) 5- (biphenyl) -bicyclo [2.2.1] hept-2-ene 94) 5- ( β-naphthyl) -bicyclo [2.2.1] hept-2-ene 95) 5- (α-naphthyl) -bicyclo [2.2.1] hept-2-ene 96) 5- (anthracenyl) -bicyclo [2.2.1] Hept-2-ene 97) 5,6 Diphenyl-bicyclo [2.2.1] hept-2-ene 98) Cyclopentadiene-acenaphthylene adduct 99) 1,4-methano-1,4,4a, 9a-tetrahydrofluorene 100) 1,4-methano-1 4,4a, 5,10,10a-hexahydroanthracene 101) 8-phenyl-tetracyclo [4.4.0.0 ^3,5 . 1 ^7,10 ] -3-dodecene 102) 8-methyl-8-phenyl-tetracyclo [4.4.0.0 ^3,5 . 1 ^7,10 ] −
3-dodecene 103) 8-benzyl-tetracyclo [4.4.0.0 ^3,5 . 1 ^7,10 ] -3-dodecene 104) 8-Tolyl-tetracyclo [4.4.0.0 ^3,5 . 1 ^7,10 ] -3-dodecene 105) 8- (ethylphenyl) -tetracyclo [4.4.0.0 ^3,5 . 1 ^7,10 ] -3-dodecene 106) 8- (Isopropylphenyl) -tetracyclo [4.4.0.0 ^3,5 . 1 ^7,10 ] -3-dodecene 107) 8,9-diphenyl-tetracyclo [4.4.0.0 ^3,5 . 1 ^7,10 ] -3-dodecene 108) 8- (biphenyl) -tetracyclo [4.4.0.0 ^3,5 . 1 ^7,10 ] -3-dodecene 109) 8- (β-naphthyl) -tetracyclo [4.4.0.0 ^3,5 . 1 ^7,10 ] -3-dodecene 110) 8- (α-naphthyl) -tetracyclo [4.4.0.0 ^3,5 . 1 ^7,10 ] -3-dodecene 111) 8- (anthracenyl) -tetracyclo [4.4.0.0 ^3,5 . 1 ^7,10 ] -3-dodecene 112) (cyclopentadiene-acenaphthylene adduct) and cyclopentadiene further added 113) 11,12-benzo-pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13 ] -4-pentadecene 114) 11,12-benzo-pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] -4-hexadecene 115) 11-phenyl - hexacyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene 116) 14,15-benzo - heptacyclo [8.7.0.1 ^2,9. 1 ^4,7 . 1 ^11,17 .
0 ^3,8 . 0 ^12,16 ] -5-Eicosen

[Α-olefin]
Examples of the α-olefin constituting the copolymer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, Examples include linear α-olefins such as 1-octadecene and 1-eicosene; branched α-olefins such as 4-methyl-1-pentene, 3-methyl-1-pentene and 3-methyl-1-butene. . An α-olefin having 2 to 20 carbon atoms is preferable. Such a linear or branched α-olefin may be substituted with a substituent, and may be used singly or in combination of two or more.

  Examples of the substituent include various substituents, but typical examples include alkyl, aryl, anilino, acylamino, sulfonamido, alkylthio, arylthio, alkenyl, cycloalkyl, cycloalkenyl, alkynyl, heterocycle, Alkoxy, aryloxy, heterocyclic oxy, siloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, hydroxyl and mercapto As well as spiro compound residues, bridged hydrocarbon compound residues, sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, phosphoryl, carbamoyl, acyl, acyloxy, Alkoxycarbonyl, carboxyl, cyano, nitro, halogen-substituted alkoxy, halogen-substituted aryloxy, pyrrolyl, and the like each group and a halogen atom tetrazolyl, and the like.

  As said alkyl group, a C1-C32 thing is preferable and may be linear or branched. As the aryl group, a phenyl group is preferable.

  As acylamino group, alkylcarbonylamino group, arylcarbonylamino group; as sulfonamide group, alkylsulfonylamino group, arylsulfonylamino group; alkylthio group, alkyl component in arylthio group, aryl component is the above alkyl group, aryl group Is mentioned.

  The alkenyl group preferably has 2 to 23 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. The alkenyl group may be linear or branched. The cycloalkenyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms.

  The ureido group is preferably an alkylureido group or an arylureido group; the sulfamoylamino group is preferably an alkylsulfamoylamino group or an arylsulfamoylamino group; 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, etc .; the saturated heterocyclic ring is preferably a 5- to 7-membered one, specifically tetrahydropyranyl, tetrahydrothiopyranyl, etc .; heterocyclic oxy The group preferably has a 5- to 7-membered heterocyclic ring, such as 3,4,5,6-tetrahydropyranyl-2-oxy, 1-phenyltetrazol-5-oxy, etc .; 5- to 7-membered heterocyclic thio groups are preferred, for example 2-pyridylthio, 2-benzothiazolylthio, 2,4-diphenoxy-1 3,5-triazole-6-thio, etc .; as siloxy group, trimethylsiloxy, triethylsiloxy, dimethylbutylsiloxy, etc .; as imide group, succinimide, 3-heptadecyl succinimide, phthalimide, glutarimide, etc .; remaining spiro compound As the group, spiro [3.3] heptan-1-yl and the like; as the bridged hydrocarbon compound residue, bicyclo [2.2.1] heptan-1-yl, tricyclo [3.3.1.13.7 Decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl, and the like.

  As the sulfonyl group, an alkylsulfonyl group, an arylsulfonyl group, a halogen-substituted alkylsulfonyl group, a halogen-substituted arylsulfonyl group, etc .; As a sulfinyl group, an alkylsulfinyl group, an arylsulfinyl group, etc .; As a sulfonyloxy group, an alkylsulfonyloxy group , Arylsulfonyloxy groups, etc .; as sulfamoyl groups, N, N-dialkylsulfamoyl groups, N, N-diarylsulfamoyl groups, N-alkyl-N-arylsulfamoyl groups, etc .; as phosphoryl groups, alkoxy A phosphoryl group, an aryloxyphosphoryl group, an alkylphosphoryl group, an arylphosphoryl group, etc .; examples of the carbamoyl group include an N, N-dialkylcarbamoyl group, an N, N-diarylcarbamoyl group, and an N-alkyl-N group. An arylcarbamoyl group and the like; an acyl group such as an alkylcarbonyl group and an arylcarbonyl group; an acyloxy group such as an alkylcarbonyloxy group and the like; an oxycarbonyl group such as an alkoxycarbonyl group and an aryloxycarbonyl group; a halogen-substituted alkoxy group Α-halogen-substituted alkoxy group and the like; halogen-substituted aryloxy groups such as tetrafluoroaryloxy group and pentafluoroaryloxy group; pyrrolyl group such as 1-pyrrolyl and the like; tetrazolyl group such as 1-tetrazolyl and the like Groups.

  In addition to the above substituents, groups such as trifluoromethyl, heptafluoro-i-propyl, nonylfluoro-t-butyl, tetrafluoroaryl groups, pentafluoroaryl groups and the like are also preferably used. Furthermore, these substituents may be substituted with other substituents.

  Further, the acyclic monomer content in the copolymer is preferably 20% by mass or more from the viewpoint of moldability, more preferably 25% or more and 90% or less, and 30% or more and 85% or less. More preferably.

  The glass transition temperature Tg of the copolymer in the present invention is preferably in the range of 80 to 250 ° C, more preferably 90 to 220 ° C, and most preferably 100 to 200 ° C. The number average molecular weight (Mn) is a polystyrene conversion value measured by gel permeation chromatography (GPC), preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, most preferably. Is in the range of 50,000 to 300,000. The molecular weight distribution is preferably 2.0 or less when expressed as a ratio (Mw / Mn) between the above Mn and a polystyrene-reduced mass average molecular weight (Mw) similarly measured by GPC.

  When Mw / Mn is too large, the mechanical strength and heat resistance of the molded product are lowered. In particular, in order to improve mechanical strength, heat resistance, and moldability, Mw / Mn is more preferably 1.8 or less, and particularly preferably 1.6 or less.

  The temperature at the time of polymerization is selected from the range of 0 to 200 ° C, preferably 50 to 150 ° C, and the pressure is selected from the range of atmospheric pressure to 100 atm. Moreover, the molecular weight of the produced | generated polymer can be easily adjusted by making hydrogen exist in a polymer zone | band.

  The olefin resin according to the present invention may be a polymer synthesized from one-component cyclic monomer, but preferably a copolymer synthesized using two or more cyclic monomers or a cyclic monomer and an acyclic monomer. Is selected. This copolymer may be produced using monomers having 100 or more components, but the mixing of monomers is preferably 10 or less from the viewpoint of production efficiency polymerization stability. More preferred is 5 components or less. Further, the obtained copolymer may be a crystalline polymer or an amorphous polymer, but preferably an amorphous polymer.

  As a method for hydrogenating the carbon-carbon unsaturated bond (including the aromatic ring) of the copolymer according to the present invention, known methods can be used. Among them, the hydrogenation rate is increased and the hydrogenation reaction is performed. In order to reduce the simultaneous polymer chain scission reaction, hydrogen is removed using a catalyst containing at least one metal selected from nickel, cobalt, iron, titanium, rhodium, palladium, platinum, ruthenium and rhenium in an organic solvent. An addition reaction is preferably performed. As the hydrogenation catalyst, either a heterogeneous catalyst or a homogeneous catalyst can be used. The heterogeneous catalyst can be used in the form of a metal or metal compound or supported on a suitable carrier. Examples of the support include activated carbon, silica, alumina, calcium carbide, titania, magnesia, zirconia, diatomaceous earth, silicon carbide and the like. The supported amount of the catalyst is a metal content with respect to the total mass of the catalyst, usually 0.01. It is -80 mass%, Preferably it is the range of 0.05-60 mass%. The homogeneous catalyst is a catalyst in which a nickel, cobalt, titanium or iron compound and an organometallic compound (for example, an organoaluminum compound or an organolithium compound) are combined, or an organometallic complex catalyst such as rhodium, palladium, platinum, ruthenium or rhenium. Can be used. These hydrogenation catalysts can be used alone or in combination of two or more, and the amount used is usually 0.01 to 100 parts by mass, preferably 0, per 100 parts by mass of the polymer. 0.05 to 50 parts by mass, more preferably 0.1 to 30 parts by mass.

  The hydrogenation reaction temperature is usually from 0 to 300 ° C, preferably from room temperature to 250 ° C, particularly preferably from 50 to 200 ° C.

  Moreover, hydrogen pressure is 0.1MPa-30MPa normally, Preferably it is 1MPa-20MPa, More preferably, it is 2MPa-15MPa. From the viewpoint of heat resistance and weather resistance, the hydrogenation rate of the obtained hydrogenated product is usually 90% or more, preferably 95% or more of the carbon-carbon unsaturated bond of the main chain, as measured by 1H-NMR. Preferably it is 97% or more. When the hydrogenation rate is low, optical properties such as transmittance, low birefringence, and thermal stability of the resulting polymer are lowered.

  The solvent used in the hydrogenation reaction of the copolymer according to the present invention may be any solvent as long as it dissolves the copolymer according to the present invention and the solvent itself is not hydrogenated. Ethers such as tetrahydrofuran, diethyl ether, dibutyl ether and dimethoxyethane, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, aliphatic hydrocarbons such as pentane, hexane and heptane, cyclopentane, cyclohexane, methylcyclohexane and dimethyl Examples include aliphatic cyclic hydrocarbons such as cyclohexane and decalin, halogenated hydrocarbons such as methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, and trichlorobenzene. These may be used as a mixture of two or more. .

  The copolymer hydrogenated product according to the present invention can be produced by isolating the copolymer hydrogenated product from the polymer solution and then dissolving it again in the solvent. A method of performing a hydrogenation reaction by adding a hydrogenation catalyst comprising a metal complex and an organoaluminum compound can also be employed.

  After completion of the hydrogenation reaction, the hydrogenation catalyst remaining in the polymer can be removed by a known method. For example, an adsorption method using an adsorbent, a method in which an organic acid such as lactic acid, a poor solvent, and water are added to a solution using a good solvent, and the system is extracted and removed at room temperature or under heating. Acetic acid, citric acid, benzoic acid after contact treatment of a solution or polymer slurry with a basic compound such as trimethylenediamine, aniline, pyridine, ethanediamide, sodium hydroxide, etc. in an atmosphere of nitrogen or hydrogen gas. And a method of washing and removing an acidic compound such as hydrochloric acid after contact treatment.

  The method for recovering the polymer hydride from the copolymer hydrogenated solution according to the present invention is not particularly limited, and a known method can be used. For example, the reaction solution is discharged into a poor solvent under stirring to solidify the polymer hydride, and recovered by filtration, centrifugation, decantation, etc., and steam is blown into the reaction solution to remove the polymer hydride. Examples thereof include a steam stripping method for precipitation and a method for directly removing the solvent from the reaction solution by heating.

  In the present invention, when a hydrogenation method is used, the hydrogenation rate can be easily achieved at 90% or more, and can be 95% or more, particularly 99% or more. The polymer or copolymer thus obtained The hydrogenated product is not easily oxidized and becomes an excellent polymer or copolymer hydrogenated product.

[Hindered amine light stabilizer (HALS) mixed in resin]
A small amount of a hindered amine light stabilizer (HALS; Hindered Amine Light Stabilizer) may be contained in the resin (resin made of a polymer having an alicyclic structure) constituting the resin molded portion 50.
As HALS contained in the resin molded part 50, those having a Mn in terms of polystyrene measured by GPC using THF as a solvent are preferably 1000 to 10,000, more preferably 2000 to 5000, and more preferably 2800 to 3800. Some are particularly preferred.
If Mn is too small, when HALS is blended by heat-melting and kneading into a block copolymer, a predetermined amount cannot be blended due to volatilization, or foaming or silver streak occurs during heat-melt molding such as injection molding. Processing stability decreases. Further, when the lens is used for a long time with the lamp turned on, a volatile component is generated as a gas from the lens.
Conversely, if Mn is too large, the dispersibility in the block copolymer is lowered, the transparency of the lens is lowered, and the effect of improving light resistance is reduced. Therefore, in the present invention, a lens excellent in processing stability, low gas generation and transparency can be obtained by setting the HALS Mn in the above range.

  Specific examples of such HALS include N, N ′, N ″, N ′ ″-tetrakis- [4,6-bis- {butyl- (N-methyl-2,2,6,6-tetra). Methylpiperidin-4-yl) amino} -triazin-2-yl] -4,7-diazadecane-1,10-diamine, dibutylamine and 1,3,5-triazine and N, N′-bis (2,2 , 6,6-tetramethyl-4-piperidyl) butylamine, poly [{(1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl } {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], 1,6-hexanediamine- N, N′-bis (2,2,6,6-tetramethyl-4 Polypiperidyl) and morpholine-2,4,6-trichloro-1,3,5-triazine, poly [(6-morpholino-s-triazine-2,4-diyl) (2,2, 6,6, -tetramethyl-4-piperidyl) imino] -hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] and other piperidine rings are bonded via a triazine skeleton High molecular weight HALS; a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, 1,2,3,4-butanetetracarboxylic acid and 1,2, Between 2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane Such engagement ester, piperidine ring and the like high molecular weight HALS attached through an ester bond.

  Among these, polycondensates of dibutylamine, 1,3,5-triazine and N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{(1, 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2 , 2,6,6-tetramethyl-4-piperidyl) imino}], a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and the like. 5,000 to 5,000 are preferred.

The blending amount of HALS with respect to the block copolymer according to the present invention is preferably 0.01 to 20 parts by weight, more preferably 0.02 to 15 parts by weight, and particularly preferably 0.8 to 100 parts by weight of the polymer. 05 to 10 parts by weight.
If the amount added is too small, the effect of improving light resistance cannot be obtained sufficiently, and coloring occurs when used outdoors for a long time.
On the other hand, when the HALS content is too large, a part of the HALS is generated as a gas, or the dispersibility in the block copolymer is lowered, and the transparency of the lens is lowered.

As shown in the enlarged view of FIG. 1, the antireflection film 60 has a three-layer structure in which a first layer 62, a second layer 64, and a third layer 66 are laminated.
Of the three layers of the antireflection film 60, the first layer 62 is a layer in contact with the resin molding portion 50 and is formed directly on the surface 52. The second layer 64 is formed on the first layer 62, and the third layer 66 is formed on the second layer 64.

The first layer 62 is a layer mainly composed of a metal oxide material.
The metal oxide material is selected from SiO ₂ , Al ₂ O ₃ , HfO ₂ , ZrO ₂ , LaO ₂ , ZrO ₂ , Ta ₂ O _x (x is an integer), a single material or mixed material of SiO, preferably Are SiO ₂ and Al ₂ O ₃ .

The first layer 62 contains a hindered amine light resistance stabilizer (HALS; Hindered Amine Light Stabilizer). That is, the first layer 62 is specifically a mixed layer of a metal oxide material and HALS.
The HALS content in the constituent material of the first layer 62 is 0.1 to 50 wt%, preferably 0.1 to 10 wt%.
The first layer 62 is a layer in contact with the resin molded portion 50 and greatly affects the adhesion of the antireflection film 60 to the resin molded portion 50. Therefore, the thickness of the first layer is preferably (film floating does not occur). Thicken in range).

In the first layer 62, the content of HALS relative to the metal oxide material decreases along the thickness direction of the first layer 61 from the resin molded portion 50 toward the second layer 64 on the first layer 62, HALS content has a certain distribution.
For example, in the case where the first layer 62 is equally divided into six regions along the thickness direction, when each region is viewed in cross-section from the resin molded portion 50 toward the second layer 64, the metal oxide material The HALS content is decreased stepwise with a constant distribution, such as 10 wt% → 8 wt% → 6 wt% → 4 wt% → 2 wt% → 0 wt%.
The distribution is an example, and the number of regions for dividing the first layer 62 in the thickness direction may be two or more, and the first layer 62 is uniformly divided for each region along the thickness direction. The distribution may not have a certain relationship, and the HALS content only needs to decrease linearly or in a curved line.
Of course, in the first layer 62, HALS may be simply dispersed in the metal oxide material without having a constant distribution.

The first layer 62 may contain at least one additive selected from an ultraviolet absorber, a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant. That is, among these additives, one kind of additive may be contained, or two or more kinds of additives may be contained in combination.
In particular, the antioxidant has a functional group different from that of HALS, so the mechanism for preventing photodegradation and the mechanism for capturing oxygen radicals and oxygen-containing compounds are also different. Can be obtained.

  HALS, ultraviolet absorbers and various antioxidants that can be used as the constituent material of the first layer 62 are as follows.

[Hindered amine light stabilizer (HALS)]
As HALS, as shown below, low molecular weight (C) or high molecular weight (D) may be used alone or in combination.
The low molecular weight HALS (C) has a molecular weight of 1000 or less, preferably 900 or less. For example, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6 -Tetramethylpiperidine, 4-acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexanoyloxy-2,2,6 , 6-tetramethylpiperidine, 4- (o-chlorobenzoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenoxyacetoxy) -2,2,6,6-tetramethylpiperidine, 1, 3,8-triaza-7,7,9,9-tetramethyl-2,4-dioxo-3-noctyl-spiro [4,5] decane, bis 2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, bis (1,2,2,6,6-pentamethyl- 4-piperidyl) sebacate, tris (2,2,6,6-tetramethyl-4-piperidyl) benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4- Piperidyl) -2-acetoxypropane-1,2,3-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -2-hydroxypropane-1,2,3-tricarboxylate , Tris (2,2,6,6-tetramethyl-4-piperidyl) triazine-2,4,6-tricarboxylate, tris (2,2,6,6-tetramethyl-4-pi Lysine) phosphite, tris (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3-tricarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) ) Propane-1,1,2,3-tetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate it can. More specifically, those commercially available under trade names such as Sanol LS770, Tinuvin 144, Adekastab LA-57, Adekastab LA-62, Adekastab LA-67, Goodlight UV-3034 can be used.

  The high molecular weight HALS (D) has a molecular weight of more than 1000, preferably about 1200 to 5000, and examples thereof include a high molecular weight hindered amine represented by the following formula.

  As the HALS, chemical substances listed in each column of the following table can be used (reference, “photostabilization technology of polymer” (written by Zenjiro Osawa, published by CMC Publishing Co., Ltd.)).

[Ultraviolet absorber]
Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2 -Hydroxy-4-methoxy-2'-benzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone trihydrate, 2-hydroxy-4-n-octoxybenzophenone, 2,2 ', 4,4'- Benzophenone ultraviolet absorbers such as tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane; 2- (2′-hydroxy-5′-methyl-) Phenyl) benzotriazole, 2- (2H-benzoto Azol-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, 2- (2H-benzotriazol-2-yl) -4-6-bis (1 -Methyl-1-phenylethyl) phenol, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) benzotriazole, 2- (2'-hydroxy-3'-tertiary- Butyl-5′-methyl-phenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di -Tertiary-amylphenyl) benzotriazole, 2- [2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] benzo Triazole, 2,2'-me Renbisu [4- (1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl) phenol] and the like benzotriazole ultraviolet absorbents such as.
Among these, 2- (2′-hydroxy-5′-methyl-phenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4-methyl-6- (3,4,5,6- Tetrahydrophthalimidylmethyl) phenol, 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1-phenylethyl) phenol and the like are preferable from the viewpoints of heat resistance and low volatility. .

[Antioxidant]
A conventionally well-known thing can be used as a phenolic antioxidant, for example, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2 , 4-di-t-amyl-6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate and the like, and JP-A Nos. 63-179953 and 1-168643. Acrylate compounds described in Japanese Patent Publication No. 1; octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,2′-methylene-bis (4-methyl-6-tert-butylphenol) ), 1,1,3-tris (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, pentaerythrmethyl-tetrakis] (3- (3,5-di-t-butyl-4-hydroxyphenylpropionate)], triethylene glycol bis (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate) and the like Alkyl substituted phenol compounds; 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bisoctylthio-1,3,5-triazine, 4-bisoctylthio-1,3 5-triazine, 2-octylthio-4,6-bis- (3,5-di-t-butyl-4-oxyanilino) -1,3,5-triazine, etc. Triazine group-containing phenol compound; and the like.

  The phosphorus antioxidant is not particularly limited as long as it is usually used in the general resin industry. For example, triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) Phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10 Monophosphite compounds such as dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl phosphite ), 4,4′isopropylidene-bis (phenyl-di-alkyl (C12-C15) phosphite) What diphosphite compounds and the like. Among these, monophosphite compounds are preferable, and tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite and the like are particularly preferable.

  Examples of the sulfur-based antioxidant include dilauryl 3,3-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3-thiodipro Pionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate, 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane It is done.

  These antioxidants can be used alone or in combination of two or more, and the blending amount thereof is appropriately selected within a range not impairing the object of the present invention, but has an alicyclic structure. The amount is usually 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight based on 100 parts by weight of the polymer.

The second layer 64 and the third layer 66 are made of MgF ₂ , SiO ₂ , Al ₂ O ₃ , HfO ₂ , ZrO ₂ , LaO ₂ , ZrO ₂ , Ta ₂ O _x (x is an integer), a single material of SiO, or Consists of mixed materials.
Similarly to the first layer 62, the second layer 64 and the third layer 66 may contain the HALS, or the HALS content distribution may be inclined so as to decrease in the layer. In addition, ultraviolet absorbers and various antioxidants may be contained.

The antireflection film 60 may be configured with a single-layer structure (only the first layer 62 may be configured), or may be configured with a two-layer structure (the first layer 62 and the second layer 62). It may be composed of the layer 64), or may be composed of a layer structure of four or more layers in which layers are further laminated on the third layer 66.
When the antireflection film 60 has a single-layer structure, the antireflection function is sufficiently exerted, but a multi-layer structure composed of two or more layers is more desirable for enhancing the antireflection effect.

  Then, the manufacturing method of the objective lens 37 is demonstrated.

  First, a constituent material containing the resin and HALS is injection-molded into a mold under a certain condition to form a resin molded portion 50 having a predetermined shape.

  When a small amount of HALS is mixed in the resin molded part 50, the resin molded part 50 is then annealed at a constant temperature for a fixed time (for example, heated at 90 ° C. for 24 hours), and the HALS in the resin molded part 50 is resinated. Bleed out on the surface 52 of the molded part 50.

Thereafter, an antireflection film 60 is formed on the surface 52 of the resin molded portion 50 by a known method. Known methods include a vapor deposition method, a spin coating method, a casting method, and the like, but a vacuum vapor deposition method or a spin coating method is particularly preferable because a homogeneous film is easily obtained and pinholes are hardly generated.
In this case, a different film forming method may be applied for each layer.

When the vapor deposition method is employed in the formation of the antireflection film 60, the vapor deposition conditions vary depending on the type of compound used, the target crystal structure of the molecular deposition film, the association structure, etc., but generally the boat heating temperature is 50 to 450. It is desirable to appropriately select the temperature within a range of 10 ° C., a vacuum degree of 10 ⁻⁶ to 10 ⁻³ Pa, a deposition rate of 0.01 to 50 nm / second, a substrate temperature of −50 to 300 ° C., and a film thickness of 5 nm to 5 μm.

In particular, in the formation of the first layer 62, since the first layer 62 is a mixed layer of a metal oxide material and HALS, the metal oxide material and the HALS are separately arranged on a plurality of boats in the same chamber. (Various deposition sources are used), and vapor deposition is performed in multiple ways.
In this case, the HALS deposition rate is appropriately controlled (for example, heating of the deposition source is temporarily stopped), and the HALS content is decreased stepwise.

In addition, when adding an ultraviolet absorber and various antioxidants to the 1st layer 62, another boat is filled with these additives, and metal oxide material, HALS, and an additive are vapor-deposited in multiple ways. .
As a means for obtaining a gas phase from a metal oxide material, any method that can be performed in the same chamber, such as heating by an electron gun and sputtering, can be used.

  Next, the operation of the optical pickup device 30 will be described.

Blue laser light is emitted from the semiconductor laser oscillator 32 during an operation of recording information on the optical disc D or an operation of reproducing information recorded on the optical disc D. The emitted blue laser light passes through the collimator 33 and is collimated into infinite parallel light, then passes through the beam splitter 34 and passes through the quarter wavelength plate 35. Furthermore, after passing through the blue laser beam aperture 36 and the objective lens 37, forms a converged spot on an information recording surface D ₂ through the protective substrate D ₁ of the optical disc D.

Blue laser light that formed the concentrated light spot is modulated by the information recording surface D ₂ of the optical disk D by the information bits, is reflected by the information recording surface D _2. Then, the reflected light is sequentially transmitted through the objective lens 37 and the diaphragm 36, and then the polarization direction is changed by the 1 / wavelength plate 35 and reflected by the beam splitter 34. Thereafter, the reflected light passes through the sensor lens group 38 to be given astigmatism, is received by the sensor 39, and finally is photoelectrically converted by the sensor 39 to become an electrical signal.

  Thereafter, such an operation is repeatedly performed, and the operation of recording information on the optical disc D and the operation of reproducing information recorded on the optical disc D are completed.

  According to the above embodiment, since the first layer 62 of the layers constituting the antireflection film 60 is a mixed layer of a metal oxide material and HALS, the surface 52 and the first layer 62 of the resin molded part 50 are used. And the change in the surface shape of the objective lens 37 and the white turbidity inside the resin (inside the resin molding portion 50) can be prevented or suppressed (see the following examples).

Further, when HALS is contained in the resin molded part 50 in the manufacturing process of the objective lens 37, the thermal molding process is performed on the resin molded part 50 to bleed out the HALS in the resin molded part 50 to the surface 52. Therefore, it is considered that the HALS that has been bleed out and the HALS of the first layer 62 of the antireflection film 60 combine to exert an anchor effect.
As a result, the adhesion between the surface 52 of the resin molded portion 50 and the first layer 62 is further improved, and the change in the surface shape of the objective lens 37 and the cloudiness inside the resin can be reliably prevented or suppressed.

  In this embodiment, an example in which the antireflection film 60 is formed on the objective lens 37 (resin molding portion 50) has been disclosed. However, such a configuration includes a collimator 33 and a beam splitter 34 other than the objective lens 37. The present invention can also be applied to resin optical lenses.

(1) Preparation of sample Using ZEONEX340R manufactured by Nippon Zeon Co., Ltd. and APEL manufactured by Mitsui Chemicals as a cycloolefin resin, these two types of resins were respectively injection molded to prepare plates.
After that, a three-layer or four-layer multilayer film (antireflection film) composed of a combination of SiO, SiO ₂ , ZrO ₂ , and Al ₂ O ₃ is basically added to the prepared plate, and additives are appropriately added depending on the layer. A mixed layer was prepared, and the configuration of each layer was as shown in Table 2.
The antireflection film was produced by a vacuum deposition method, and a resistance overheating method using a tungsten boat was used as a means for obtaining a gas phase.
At this time, the mixed layer was separately deposited with materials and additives in a plurality of boats in the same chamber, and multiple deposition was performed.

Each substance in Table 2 (“wt%” in parentheses indicates the weight ratio of the substance in the layer) is as follows.
“LA57 (Adeka Stub LA57)”: Hindered amine light stabilizer (HALS)
“LA36”… UV absorber “Irganox 1098”… Phenolic antioxidant “SumilizerGP”… Phosphorus antioxidant “SumilizerTPS”… Sulfuric antioxidant

In particular, with respect to the samples of Examples 5 and 6, LA57 was mixed in the first layer in the vicinity of the interface contacting the resin with a content ratio of 10 wt%, and mixed so that the mixing ratio gradually decreased as the distance from the resin increased (first (The mixing ratio of LA57 in one layer was approximately 5 wt% by weight.)
In the sample of Example 6, LA57 was mixed in the second layer in the vicinity of the interface in contact with the resin at a content ratio of 10 wt%, and mixed so that the mixing ratio gradually decreased as the distance from the resin was increased (in the entire first layer). The mixing ratio of LA57 was approximately 5 wt% by weight.)
Table 3 shows conceptually the mixture distribution (the material distribution of the film with the mixture ratio inclined) as in Examples 5 and 6.

(2) Sample evaluation Each sample of Examples 1 to 11 and Comparative Examples 1 and 2 was irradiated with a laser (wavelength: 405 nm, irradiation intensity: 100 mW / cm ² ) for 168 hours in an environment with an atmospheric temperature of 80 ° C. The change in the shape of each sample, the appearance of the resin in the resin molded part, and the adhesion of the antireflection film were examined.
In each sample of Examples 1 to 11 and Comparative Examples 1 and 2, the antireflection film is adjusted to a spectral characteristic such that the single-sided reflectance is 2% or less with respect to light having a wavelength of 405 nm.

(2.1) Adhesion of antireflection film The adhesion (adhesion area, adhesion rate%) of the antireflection film to the resin-molded portion was evaluated using a stereomicroscope. The evaluation results are shown in Table 4.
In Table 4, the criteria for ◎, ○, × were as follows.
“◎”: No anti-reflection film floating (peeling) is observed, and the anti-reflection film is in close contact with almost the entire surface of the resin molded part. “◯”: The adhesion area of the anti-reflection film is 60% or more. × ”: The adhesion area of the antireflection film is less than 60%.

(2.2) Measurement of shape change The amount of change in wavefront aberration before and after laser irradiation was measured using an interferometer, and thereby each sample was evaluated. The evaluation results are shown in Table 4.
In Table 4, the criteria for ◎, ○, × were as follows.
“◎”: The amount of change in wavefront aberration is within 10 mλ. “O”: The amount of change in wavefront aberration exceeds 10 mλ, but within 20 mλ. “X”: The amount of change in wavefront aberration exceeds 20 mλ.

(2.3) Observation of appearance of resin Using a stereomicroscope, the irradiation marks (presence and absence of the white turbidity of the resin and the extent thereof) were observed. Since the degree of white turbidity in the irradiated part on the appearance is largely related to the transparency as an optical element, the degree of deterioration due to irradiation can be quantified by measuring the transmittance in the irradiated part. The transmissivity was measured using a U-4100 spectrophotometer (Hitachi High-Tech) with a light beam having a spot diameter and a central axis equal to the laser incident on the irradiated part.
The results are shown in Table 4.
In Table 4, the criteria for ◎, ○, × were as follows.
“◎”: The decrease in transmittance before and after the irradiation is less than 1% “◯”: The decrease in the transmittance before and after the irradiation is 1% or more and less than 3% “×”: The decrease in the transmittance before and after the irradiation is 3 % Or more

(3) Evaluation results and discussion (3.1) Example 1
In the film configuration of Example 1, the adhesion between the resin molded portion and the antireflection film was good, and the effect was shown in the change in the surface shape resulting from the photodegradation and the white turbidity of the resin.

(3.2) Example 2
In the film configuration of Example 2, the adhesion between the resin molded portion and the antireflection film was very good, and the effect was shown on the change in the surface shape and the white turbidity of the resin as a result of light degradation.
In the sample of Example 2, the SiO itself is a material that is easily oxidized, and the optical shape in consideration of the refractive index fluctuation becomes unstable, but by including HALS, the optical deterioration in the film could be reduced. .

(3.3) Example 3
In the film configuration of Example 3, the adhesiveness between the resin molded portion and the antireflection film was good, and the effect was shown in the change in the surface shape and the white turbidity of the resin as a result of light degradation.
In particular, regarding the shape change, it is considered that the effect of reducing this was increased by increasing the number of layers containing HALS.

(3.4) Example 4
In the film configuration of Example 4, the adhesion between the resin molded portion and the antireflection film was good, and the effect was shown in the change in the surface shape resulting from the photodegradation and the white turbidity of the resin.

(3.5) Example 5
In the film configuration of Example 5, the adhesion between the resin molded portion and the antireflection film was very good, and the effect was shown in the change in the surface shape resulting from the photodegradation and the white turbidity of the resin.
This is because HALS is unevenly distributed in the vicinity of the interface between the resin molded portion and the multilayer film (first layer), and the interface between the first layer (SiO ₂ ) and the second layer (ZrO ₂ ) does not mix the additive. This is considered to be due to the optimization of the entire interface structure including between the layers and the improvement of the adhesion between the films.

(3.6) Example 6
In the film configuration of Example 6, the adhesiveness between the resin molded portion and the antireflection film was extremely good, and the effect was shown in the change in the surface shape resulting from the photodegradation and the white turbidity of the resin.
This is considered to be due to the fact that the overall HALS content was increased in addition to the enhancement of the adhesion force by the same effect as in Example 5.

(3.7) Example 7
In the film configuration of Example 7, the adhesion between the resin molded portion and the antireflection film was very good, and the effect was shown in the change in the surface shape resulting from the photodegradation and the white turbidity of the resin.
At the same time, good adhesion was maintained even when other additives were mixed in addition to HALS.
Since LA36 is an ultraviolet absorber, when the wavelength of light (or naturally exposed light) emitted from the device light source includes an ultraviolet component, the action of LA36 acts more significantly. Light resistance is expected.

(3.8) Example 8
In the film configuration of Example 8, the adhesiveness between the resin molded portion and the antireflection film was good, and the effect was shown in the change in the surface shape resulting from the photodegradation and the white turbidity of the resin.
In the sample of Example 8, it is considered that the ultraviolet absorber (LA57) and the phenolic antioxidant (Irganox 1098) exhibited a synergistic effect in preventing oxidation due to light.

(3.9) Example 9
In the film configuration of Example 9, the adhesiveness between the resin molded portion and the antireflection film was good, and the effect was exhibited on the change in the surface shape resulting from the photodegradation and the white turbidity of the resin.
Even in the sample of Example 9, it is considered that the ultraviolet absorber (LA57) and the phosphorus-based antioxidant (SumilizerGP) exhibited a synergistic effect in preventing oxidation by light.

(3.10) Example 10
In the film configuration of Example 10, the adhesion between the resin molded portion and the antireflection film was good, and the effect was shown in the change in the surface shape and the white turbidity of the resin as a result of light degradation.
Even in the sample of Example 10, it is considered that the ultraviolet absorber (LA57) and the sulfur-based antioxidant (Sumilizer TPS) exhibited a synergistic effect in preventing oxidation by light.

(3.11) Example 11
In the film configuration shown in Example 11, the adhesion between the resin molded portion and the antireflection film was good, and the effect was shown in the change in the surface shape resulting from the photodegradation and the white turbidity of the resin.
The sample of Example 11 indicates that the material candidate for forming the mixed layer (first layer) is not limited to silica (SiO ₂ ).

(3.12) Comparative Example 1
In the film configuration of Comparative Example 1, although there was no problem in the adhesion between the resin molded portion and the antireflection film, there was no effect on light resistance, and the resin was rapidly deteriorated by the irradiated laser light.

(3.13) Comparative Example 2
The film configuration of Comparative Example 2 was effective against changes in the optical shape resulting from photodegradation and white turbidity of the resin, but extremely poor results were obtained in terms of the adhesion between the resin molded part and the antireflection film.

(4) Summary From the above results, providing a mixed layer in which HALS (and other additives) are mixed as the first layer on the resin molded part impairs the adhesion between the resin molded part and the antireflection film. Without being found to be an effective means of reducing the photodegradation of the resin.

DESCRIPTION OF SYMBOLS 30 Optical pick-up apparatus 32 Semiconductor laser oscillator 33 Collimator 34 Beam splitter 35 1/4 wavelength plate 36 Aperture 37 Objective lens 37a, 37b Surface 38 Sensor lens group 39 Sensor 40 Two-dimensional actuator 50 Resin molding part 52 Surface 60 Antireflection film 62 1st 1 layer 64 2nd layer 66 3rd layer D optical disk D ₁ protective substrate D ₂ information recording surface

Claims (7)

In an optical element for an optical pickup device arranged in an optical path of a light beam having a wavelength of 380 to 420 nm,
A resin molded part obtained by molding a resin;
A functional film formed on the surface of the resin molded portion;
With
The functional film has a layer structure in which a single layer or a plurality of layers are laminated,
The optical element, wherein the first layer in contact with the resin molding portion among the layers constituting the functional film is a mixed layer containing a metal oxide material and a hindered amine light-resistant stabilizer. The optical element according to claim 1,
The optical element, wherein the mixed layer contains at least one additive selected from an ultraviolet absorber, a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant. The optical element according to claim 1 or 2,
In the mixed layer, the content of the hindered amine light resistance stabilizer with respect to the metal oxide material is along the thickness direction of the first layer from the resin molded portion toward the second layer on the first layer. An optical element characterized by being reduced. In the optical element as described in any one of Claims 1-3,
An optical element, wherein the metal oxide material is SiO ₂ or Al ₂ O ₃ . In the optical element as described in any one of Claims 1-4,
An optical element, wherein the functional film is an antireflection film. In the method for manufacturing an optical element for an optical pickup device arranged in an optical path of a light beam having a wavelength of 380 to 420 nm,
Forming a resin molded part by molding a resin;
A step of forming a functional film having a layer structure in which a single layer or a plurality of layers are laminated by a vapor deposition method on the surface of the resin molded portion;
With
In the step of forming the functional film, when forming the first layer in contact with the resin molding portion among the layers constituting the functional film, the metal oxide material and the hindered amine light resistance stabilizer are used as separate vapor deposition sources. A method of manufacturing an optical element, characterized by vapor deposition in a plural manner. In the manufacturing method of the optical element according to claim 6,
When forming the first layer in contact with the resin molding part among the layers constituting the functional film, the deposition of the hindered amine light resistance stabilizer is controlled, and the hindered amine light resistance stabilizer of the metal oxide material is controlled. A method of manufacturing an optical element, wherein the content rate in the first layer is decreased along the thickness direction of the first layer from the resin molded portion toward the second layer on the first layer.

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