JP2006011013A - Optical resin lens and method for manufacturing optical resin lens - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical resin lens having high durability free from deterioration in optical characteristics even under the condition of long time laser irradiation or other light energy irradiation. <P>SOLUTION: The lens contains a resin composition having such properties that the difference between the temperature Ta (°C) where the peak value in first order differentiation of a weight reduction curve measured by thermogravimetric analysis in an air environment is maximum and the temperature Tb (°C) where the peak value in first order differentiation of the weight reduction curve measured by thermogravimetric analysis in an air environment is within a predetermined range. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an optical resin lens and a method for manufacturing an optical resin lens.

  Optically transparent resins are widely used in optical products because of their light weight and mass productivity. Various cameras such as cameras, film-integrated cameras (films with lenses), video cameras, optical pickup devices such as CDs, CD-ROMs, CD-Rs, CD-RWs, CD-Videos, MOs, DVDs, copiers and printers High-performance optical lenses used in various devices such as office automation equipment such as OA equipment have been injection-molded using transparent thermoplastic resins such as polymethyl methacrylate (PMMA), polycarbonate (PC), and cyclopolyolefin (CO). Optical resin lenses, etc., have been used in some or all of their optical systems, but have low optical anisotropy, high refractive index, low moisture absorption, high heat resistance, low melt viscosity, and high strength of molded resin From such a viewpoint, the resin material used for the optical resin lens has been improved.

As a resin material used for a high-performance optical resin lens, for example, a resin material made of a cyclopolyolefin polymer having blue transparency, low birefringence, high heat resistance, and high moisture resistance (for example, patent documents) 1) and a resin material whose hue has been improved by hydrogenating the cyclopolyolefin polymer (see, for example, Patent Document 2), and an aromatic ring portion of a block copolymer of styrene and butadiene. Resin material consisting of a copolymer with a specific structure hydrogenated unsaturated bond, excellent in transparency, low birefringence and mechanical strength, and capable of producing a large and thin lens (for example, see Patent Document 3) ), And a resin material containing a fluorene skeleton having a small optical anisotropy and a large refractive index (see, for example, Patent Document 4).
JP-A-11-142645 JP 2002-105131 A JP 2002-148401 A Japanese Unexamined Patent Publication No. 7-198901

  However, when it is applied to high-performance optical lenses for high-density and high-speed recording or imaging, which require strict optical performance and difficult to manufacture, and when applied to small lenses for high-performance optics, the following A problem occurs.

  When processing a resin material using a molding method or the like for a high-performance optical lens, pressure is concentrated on the injection portion of the resin material, so that distortion is likely to occur. Especially when making a small lens, the volume of the lens The area ratio becomes large, and the distortion tends to affect the optical surface. As a result, internal stress is generated, and optical anisotropy (birefringence) is likely to occur. In addition, when the temperature becomes high under long-time laser irradiation or other light energy irradiation conditions, white turbidity occurs in the lens and optical characteristics deteriorate.

  In addition, the “Blue-ray Disc” standard for next-generation high-density optical discs was formulated and announced by nine companies in Japan, Europe and Korea. According to this standard, a blue-violet laser selected from a wavelength range of 390 to 430 nm and a high-aperture lens with NA = 0.85 can be combined to perform high-density recording and reproduction equivalent to a maximum of 27 GB on one side of a 12 cm disk. However, since the blue-violet laser having a high light energy and a wavelength of 390 to 430 nm is concentrated on a specific portion of the high-performance optical lens, the deterioration of the optical characteristics becomes more remarkable.

  Accordingly, an object of the present invention is to provide an optical resin lens exhibiting high durability in which optical characteristics do not deteriorate even under long-time laser irradiation or other light energy irradiation conditions, and a method for manufacturing the optical resin lens.

  The object of the present invention is achieved by the following constitution.

The invention according to claim 1 is an optical resin lens comprising a resin composition that satisfies the following conditions.
50> | Ta-Tb |> 10
(Ta is the temperature (° C.) at which the peak value of the first derivative of the weight loss curve measured by thermogravimetric analysis in an air atmosphere is maximum, and Tb is the weight loss curve measured by thermogravimetric analysis in an air atmosphere. (The temperature at which the peak value of the first derivative is minimized (° C.), and Ta and Tb are 250 ° C. or higher.)
In the invention according to claim 2, the resin composition contains at least one antioxidant having a weight reduction start temperature of 180 ° C. or higher in a weight reduction curve measured by thermogravimetric analysis under an air atmosphere. The optical resin lens according to claim 1.

  The invention according to claim 3 is characterized in that the resin composition contains at least one light-resistant stabilizer having a weight reduction starting temperature of 180 ° C. or higher in a weight reduction curve measured by thermogravimetric analysis under an air atmosphere. The optical resin lens according to claim 1.

  The invention according to claim 4 is the optical resin lens according to any one of claims 1 to 3, wherein the resin composition contains at least one resin having a Tg of 80 ° C or higher. It is.

  The invention according to claim 5 is the optical resin lens according to any one of claims 1 to 4, wherein the resin composition includes at least one olefin resin.

  The invention according to claim 6 is the optical resin lens according to claim 5, wherein the olefin resin is a copolymer synthesized by polymerization of two or more monomers.

The invention according to claim 7 is the optical resin lens according to any one of claims 1 to 6, wherein the resin composition satisfies the following conditions.
0 <b <a / 2
(A is the maximum peak value of the first derivative of the weight loss curve measured by thermogravimetric analysis under air atmosphere, and b is the minimum peak value of the first derivative of the weight loss curve measured by thermogravimetric analysis under air atmosphere. .)
The invention according to claim 8 is a method for producing an optical resin lens, comprising a step of molding a resin composition that satisfies the following conditions.
50> | Ta-Tb |> 10
(Ta is the temperature (° C.) at which the peak value of the first derivative of the weight loss curve measured by thermogravimetric analysis under air atmosphere becomes maximum, and Tb is the weight loss curve measured by thermogravimetric analysis under air atmosphere. (The temperature at which the peak value of the first derivative is minimized (° C.), and Ta and Tb are 250 ° C. or higher.)
The invention according to claim 9 is characterized in that the resin composition contains at least one antioxidant having a weight reduction starting temperature of 180 ° C. or higher in a weight reduction curve measured by thermogravimetric analysis under an air atmosphere. The optical resin lens according to claim 8.

  In the invention according to claim 10, the resin composition contains at least one light-resistant stabilizer having a weight reduction starting temperature of 180 ° C. or higher in a weight reduction curve measured by thermogravimetric analysis under an air atmosphere. The method for producing an optical resin lens according to claim 8.

  The invention according to claim 11 is the optical resin lens according to any one of claims 8 to 10, wherein the resin composition contains at least one resin having a Tg of 80 ° C or higher. It is a manufacturing method.

  The invention according to claim 12 is the method for producing an optical resin lens according to any one of claims 8 to 11, wherein the resin composition includes at least one olefin resin. .

  The invention according to claim 13 is the method for producing an optical resin lens according to claim 12, wherein the olefin resin is a copolymer synthesized by polymerization of two or more monomers. .

The invention according to claim 14 is the method for producing an optical resin lens according to any one of claims 8 to 13, wherein the resin composition satisfies the following conditions.
0 <b <a / 2
(A is the maximum peak value of the first derivative of the weight loss curve measured by thermogravimetric analysis under air atmosphere, and b is the minimum peak value of the first derivative of the weight loss curve measured by thermogravimetric analysis under air atmosphere. .)

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an optical resin lens exhibiting high durability that does not deteriorate optical characteristics even under prolonged laser irradiation or other light energy irradiation conditions, and a method for manufacturing an optical resin lens.

  Hereinafter, details of each component according to the present invention will be sequentially described.

  In the resin composition used in the present invention, the temperature at which the peak value of the first derivative of the weight loss curve measured by thermogravimetric analysis in an air atmosphere is maximum is Ta (° C.), and the temperature at which the peak value is also minimum is the same. When Tb (° C.), 50> | Ta−Tb |> 10, and Ta and Tb are 250 ° C. or higher. Moreover, since adjustment of a resin composition is easy, Preferably it is 50> | Ta-Tb |> 35.

  Preferably, 0 <b <a / 2, where a is the maximum peak value of the first derivative of the weight loss curve measured by thermogravimetric analysis in an air atmosphere, and b is the minimum peak value. Features.

  The thermogravimetric analysis (hereinafter referred to as TGA) according to the present invention heats a sample and measures its mass reduction. The TGA is measured by a TGA apparatus, and any apparatus can be used as long as the TGA apparatus can measure the mass loss by heating the sample on a balance capable of heating the sample. A balance apparatus having a heating furnace capable of controlling the speed is used.

  The amount of the sample used in the TGA device, the balance type, the heating furnace type, and the temperature control method are not particularly limited, but in this embodiment, the temperature measured by the TGA device is taken as the horizontal axis, Considering the shape of the weight change curve (hereinafter also referred to as the TGA curve) plotted with the change in mass as the vertical axis, the mass decreases under an air atmosphere controlled at a rate of temperature increase of 10 ° C./min or less by a temperature controller. Shall be measured. The amount of the sample used for TGA is generally 500 mg or less, but less than 200 mg is preferable from the viewpoint of workability, and more preferably 10 mg or more and less than 100 mg from the viewpoint of measurement accuracy.

  What is measured by TGA is a change in mass under a controlled temperature rise. In the present invention, the mass change with respect to a change in temperature, that is, the absolute value of the first derivative of a TGA curve (hereinafter also referred to as a first derivative). ). It is recommended that the first derivative is calculated simply by connecting a TGA device to a computer, importing the temperature and mass data measured by the TGA into the computer, and calculating with the computer. Even if the mass data is obtained by using an electric circuit for differential calculation, it is possible to manually obtain the temperature and mass data measured by the TGA. In addition, when calculating | requiring a primary differential amount by manual calculation, it is preferable to obtain | require by the increment of 0.5 degrees C or less.

  As shown in FIG. 1, when the TGA curve A obtained by TGA becomes complicated, a large number of peaks are observed in the primary differential amount B with the temperature as the horizontal axis. In the present invention, the maximum peak value of the first derivative of the TGA curve is a, the temperature is Ta (° C.), the minimum peak value is b, and the temperature is Tb (° C.).

  Further, the weight decrease start temperature described later is a temperature Tc (° C.) at which the mass decrease starts in the TGA curve C shown in FIG.

  Although it is not certain about the effect | action of this invention, Ta corresponding to the decomposition temperature of the principal chain of a polymer among resin compositions is moderate with the decomposition temperature Tb of the chain measurement of a polymer or the additive to a resin composition. It is presumed that the generation or decomposition of a specific component in the resin composition that causes the resin material to become cloudy is suppressed by making the ratio different from each other and further making the abundance ratio appropriate.

  The effect of the present invention becomes more prominent as the wavelength of the laser beam to be irradiated becomes shorter, and the most preferable effect is obtained with a short wavelength laser of 500 nm or less.

  The resin composition according to the present invention is any of a resin, a mixture of resins, a mixture of a resin or a mixture of resins with additives such as other polymers, plasticizers, antioxidants, etc. The resin composition according to the present invention can be obtained by adjusting the selection of the agent and the mixing ratio thereof.

"resin"
The resin (also referred to as resin material or plastic material) that can be used in the resin composition according to the present invention is not particularly limited as long as it is a material that can be applied to an optical resin lens. Acrypets such as “Acrypet VH”, Mitsubishi Rayon “Acrypet WF-100”, Hitachi Chemical “Aptrez OZ-1000”, Kuraray “Varapet MI-91”, etc., Nippon Zeon “ZEONEX”, Mitsui Various resin materials such as “APEL” manufactured by Petrochemical Industries and “ARTON” manufactured by Nippon Synthetic Rubber can be used. However, from the viewpoint of improving optical durability, transferability to a mold during injection molding is also possible. ZEONEX made by Nippon Zeon, Mitsui Petrochemical Co., Ltd. is able to easily obtain the desired optical performance and reduce the minimum wall thickness. Industry Co., Ltd., "APEL", Japan Synthetic Rubber Ltd., "ARTON" polyolefin-based resin and the like are preferable.

  In view of heat resistance, the resin composition of the present invention preferably contains at least one olefin resin having a Tg (glass transition temperature) of 80 ° C. or higher. A resin containing a polymer having a formula structure is preferred.

  As a polymer having an alicyclic structure, a repeating unit (a) having an alicyclic structure represented by the following general formula (1) and the following general formula (2) or ( 3) containing the repeating unit (b) having a chain structure represented by 3) such that the total content is 90% by mass or more, and the content of the repeating unit (b) is 1% by mass or more and 10% by mass. An alicyclic hydrocarbon copolymer that is less than 1% is preferred.

In the general formula (1), X is an alicyclic hydrocarbon group. In the general formulas (1) to (3), R _{1 to} R ₁₃ are each independently a hydrogen atom, a chain hydrocarbon group, or a halogen atom. Atoms, alkoxy groups, hydroxy groups, ether groups, ester groups, cyano groups, amide groups, imide groups, silyl groups, or polar groups (halogen atoms, alkoxy groups, hydroxy groups, ether groups, ester groups, cyano groups, amide groups , An imide group, or a silyl group). Among them, 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, and 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 the general 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 general formula (3) represents carbon-carbon saturation or carbon-carbon unsaturated bond in the main chain. However, when transparency and heat resistance are strongly required, The content of saturated bonds is 10% or less of all carbon-carbon bonds constituting the main chain, preferably 5% or less, more preferably 3% or less.

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

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

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

  In the general formulas (4) to (6), Ra, Rb, Rc, Rd, Re, Rf, Rg, Rh, Ri, Rj, Rk, Rl, Rm and Rn are each independently a hydrogen atom or a lower chain. It represents a 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 general formulas (2) and (3), the repeating unit having a chain structure represented by the general formula (3) is stronger in the obtained hydrocarbon polymer. It is preferable in terms of excellent characteristics.

  In the present invention, the repeating unit (a) having an alicyclic structure represented by the general formula (1) in the hydrocarbon copolymer and the chain represented by the general formula (2) or (3) The total content with the repeating unit (b) of the structure is preferably 90% or more, more preferably 95% or more, and still more preferably 97% or more, based on mass. 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) of the 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% on a mass basis, The range is preferably 1% or more and 8% or less, more preferably 2% or more and 6% or less. By setting the content of the repeating unit (b) within 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). Mass average molecular weight), B = (Mass average molecular weight of alicyclic hydrocarbon copolymer (Mw) × (number of repeating units having alicyclic structure / all repeats constituting alicyclic hydrocarbon copolymer) Low birefringence when A is 30% or less of B, more preferably 20% or less, even more preferably 15% or less, particularly preferably 10% or less. Excellent in properties.

  Furthermore, it is preferable that the repeating unit (a) has a specific distribution of chain length. Specifically, when A = (mass 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 preferably When it is in the range of 1.3 or more, more preferably 1.3 to 8, most preferably 1.7 to 6, it has an appropriate block degree and random degree and is excellent in low birefringence.

  The molecular weight of the polymer having an alicyclic structure is 1,000 to 1 in terms of polystyrene (or polyisoprene) converted mass average molecular weight (Mw) measured by gel permeation chromatography (hereinafter referred to as GPC). Strength properties of the molding and low when it is in the range of 50,000 to 250,000, more preferably 10,000 to 300,000, most preferably 50,000 to 250,000. Excellent birefringence.

  The molecular weight distribution of the polymer having an alicyclic structure can be appropriately selected according to the purpose of use, but the weight average molecular weight (Mw) and number average molecular weight (Mn) in terms of polystyrene (or polyisoprene) measured by GPC The ratio (Mw / Mn) is 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 having an alicyclic structure may be appropriately selected according to the purpose of use, but is usually 50 ° C to 250 ° C, preferably 70 ° C to 200 ° C, more preferably 90 ° C. C. to 180.degree.

  Next, a method for producing a polymer having an alicyclic structure according to the present invention will be described.

The method for producing a polymer having an alicyclic structure according to the present invention is as follows.
(1) A method of copolymerizing an aromatic vinyl compound and another monomer copolymerizable to hydrogenate a carbon-carbon unsaturated bond of a main chain and an aromatic ring,
(2) A method of copolymerizing an alicyclic vinyl-based compound with another monomer copolymerizable and hydrogenating as necessary.

  When the polymer having an alicyclic structure according to the present invention is produced according to the above method, the aromatic vinyl compound and / or other monomer copolymerizable with the alicyclic vinyl compound (a ′). In the copolymer with (b ′), the repeating unit derived from the compound (a ′) in the copolymer has a repeating unit chain derived from D = (aromatic vinyl compound and / or alicyclic vinyl compound). Mass average molecular weight), E = (mass 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 and aromatic ring Unsaturated carbon ring cycloalkene ring, - it 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 described in the above item (1) is preferable because an alicyclic hydrocarbon copolymer can be obtained more efficiently.

  The copolymer before hydrogenation further has a constant 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). It is preferable that it is the range of these. Specifically, when the D / F is in the range of preferably 1.3 or more, more preferably 1.3 or more and 8 or less, most preferably 1.7 or more and 6 or less, the resulting alicyclic group is obtained. The low birefringence of the hydrocarbon copolymer is excellent.

  The weight average molecular weight and number average molecular weight of the chain of repeating units derived from the compound (a ′) are, for example, unsaturated double chains in the main chain of the aromatic vinyl copolymer described in the document Macromolecules 1983, 16, 1925-1928. It can be confirmed by a method of measuring the molecular weight of the extracted aromatic vinyl chain after reductive decomposition after adding the 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, when it is in the range of 10,000 to 300,000, the strength property of the molded product of the alicyclic hydrocarbon copolymer obtained therefrom is excellent, and the hydrogenation reactivity is improved.

  Specific examples of the aromatic vinyl compound used in the method described in the above item (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 described in the above item (2) include, for example, cyclobutylethylene, cyclopentylethylene, cyclohexylethylene, cycloheptylethylene, cyclooctylethylene, norbornylethylene, and dicyclohexyl. Ethylene, α-methylcyclohexylethylene, α-t-butylcyclohexylethylene, cyclopentenylethylene, cyclohexenylethylene, cycloheptenylethylene, cyclooctenylethylene, cyclodecenylethylene, norbornenylethylene, α-methylcyclohexenylethylene And α-t-butylcyclohexenylethylene. Among these, cyclohexylethylene and α-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. However, the batch polymerization method (batch method), the monomer sequential addition method (after starting polymerization using a part of the total amount of monomers used, A method in which the remaining monomer is sequentially added to proceed with the polymerization) and the like. 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 value of D is smaller and / or the value of D / F is large. 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. Moreover, 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% to 60% by mass, preferably 0.02% to 20% by mass, more preferably 0.05% to 10% by mass. 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 addition rate of the initial monomer to reach 90% is T, and the ratio (%) of the initial monomer to all the monomers used is I, the relational expression [(100-I) × T / I ] Is determined such 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 ° C to 200 ° C, preferably 20 ° C to 150 ° C. In particular, bulk polymerization and suspension polymerization are desirable when it is necessary to prevent impurities from being mixed into the resin. 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, bulk polymerization, solution polymerization, slurry polymerization, etc. in the temperature range of usually 0 ° C. to 200 ° C., preferably 20 ° C. to 100 ° C., particularly preferably 20 ° C. to 80 ° C. in the presence of an initiator. However, solution polymerization is preferable 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 mass with respect to 100 parts by mass 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. Polyfunctional organolithium compounds 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.

  Next, a method for hydrogenating unsaturated bonds will be described.

  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 in accordance with a known method. However, 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 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 mass, preferably 0.8. It is the range of 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. 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, 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 usually 0.01 to 100 parts, preferably on the mass basis with respect to the polymer. 0.05 to 50 parts, more preferably 0.1 to 30 parts.

  The hydrogenation reaction is usually 10 ° C. to 250 ° C., but preferably 50 ° C. to 200 ° C. because the hydrogenation rate can be increased and the polymer chain scission reaction occurring simultaneously with the hydrogenation reaction can be reduced. More preferably, it is 80 degreeC-180 degreeC. 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 manner is determined by 1H-NMR, as determined by carbon-carbon unsaturated bond of the main chain, carbon-carbon double bond of aromatic ring, carbon-carbon of unsaturated ring. Any of the double bonds is usually 90% or more, preferably 95% or more, more preferably 97% or more. 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.

  As the polymer having an alicyclic structure, a block copolymer having a polymer block [A] and a polymer block [B] is more preferable. The polymer block [A] contains a repeating unit [1] represented by the following general formula (7). The content of the repeating unit [1] in the polymer block [A] is preferably 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 90 mol% or more.

In the general formula (7), R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ^{15 to} R ²⁵ each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a hydroxyl group. , An alkoxy group having 1 to 20 carbon atoms, or a halogen group. R ^{15 to} R ²⁵ represent R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ .

In a preferred structure of the repeating unit [1] represented by the general formula (7), R ¹⁴ is hydrogen or a methyl group, and all of R ^{15 to} R ²⁵ are hydrogen atoms. 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 general formula (8) or the repeating unit [3] represented by the following general formula (9). 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 mole fraction of the repeating unit [2] in the block [B] is m2 (mol%) and the mole fraction of the repeating unit [3] is m3 (mol%), 2 × m2 + m3 is preferable. It is 2 mol% or more, more preferably 5 to 60 mol%, most preferably 10 to 50 mol%.

In the general formula (8), R ²⁶ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. A preferred structure of the repeating unit [2] represented by the general formula (8) is one in which R ²⁶ is hydrogen or a methyl group.

In the general formula (9), R ²⁷ and R ²⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. A preferred structure of the repeating unit [3] represented by the general formula (9) is one in which R ²⁷ is hydrogen and R ²⁸ 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 general formula (10). The content of the repeating unit [X] is an amount that does not impair the properties of the block copolymer according to the present invention, and is preferably 30 mol% or less, more preferably 20 mol%, based on the entire block copolymer. It is as follows.

In the general formula (10), R ²⁹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ³⁰ represents a nitrile group, an alkoxycarbonyl group, a formyl group, a hydroxycarbonyl group, or a halogen group, and R ³¹ Represents a hydrogen atom. Alternatively, R ³⁰ and R ³¹ 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]. When b is set, it is preferable that a> b. Thereby, it is excellent in transparency and mechanical strength.

  Furthermore, the block copolymer according to 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 range specified above, it is preferable in terms of excellent mechanical strength and heat resistance.

  The molecular weight of the block copolymer used in the present invention is a polystyrene (or polyisoprene) -converted mass average molecular weight Mw measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent, preferably 10,000 to The range is 300,000, more preferably 15,000 to 250,000, and 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 according to the purpose of use, but the ratio (Mw) of polystyrene (or polyisoprene) converted Mw and number average molecular weight (hereinafter referred to as Mn) measured by GPC. / 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 Tg of the block copolymer may be appropriately selected according to the purpose of use, but it is a measured value on the high temperature side by a differential scanning calorimeter (DSC), preferably 70 ° C to 200 ° C. Preferably it is 80 to 180 degreeC, Most preferably, it is 90 to 160 degreeC.

  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) are used. A block having a polymer block containing a repeating unit derived from an aromatic vinyl compound and / or an alicyclic vinyl compound, and a polymer block containing a repeating unit derived from a vinyl monomer by polymerizing the monomer mixture A 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 (an aromatic vinyl compound and an alicyclic vinyl compound) A block copolymer having a polymer block containing a repeating unit derived from an alicyclic vinyl compound, and a polymer block containing a repeating unit derived from a vinyl monomer And the like. 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 produce 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. A monomer mixture containing a vinyl monomer (excluding aromatic vinyl compounds and alicyclic vinyl compounds) in an amount of 2 mol% or more and having an aromatic vinyl compound and / or an unsaturated bond in the ring [ a ′] by polymerizing the monomer mixture [b ′] contained in an amount smaller than the proportion in the aromatic vinyl compound or / and the repeating unit derived from the alicyclic vinyl compound and the repeating derived from the vinyl monomer. A polymer block [B ′] containing units is obtained. After at least these steps, a block copolymer having the polymer block [A ′] and the polymer block [B ′] is obtained, and then 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 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 may be used alone or in combination of two or more. In the present invention, any 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 the monomer mixture containing the above monomers is polymerized, 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 usually carried out in the temperature range of 0 ° C. to 200 ° C., preferably 20 ° C. to 100 ° C., particularly preferably 20 ° C. to 80 ° C. in the presence of a polymerization initiator. Examples of the initiator include monoorganolithium such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, and phenyllithium, dilithiomethane, 1,4-diobtan, 1,4-dilithio-2-ethyl. Polyfunctional organolithium compounds such as cyclohexane 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 mass with respect to 100 parts by mass 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 in succession. Specifically, the monomer mixture [a ′] is polymerized in the presence of the living anion polymerization catalyst in an inert solvent 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 ′]. Further, 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 a polymer block [A ′] and a polymer block [B ′] obtained in the method (1) (hereinafter referred to as a pre-hydrogenation block copolymer), the following structure is obtained. Those having a repeating unit are preferred.

  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 general formula (11).

In the above general formula (11), R ³² represents a hydrogen atom or an alkyl group having a carbon number of 1 to 20, R33～R37 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyl group, a carbon The alkoxy group or halogen group of number 1-20 is represented. Note that the [R ³³ to R ^37] represents an ^{R 33, R 34, R 35} , R 36 and R ^37.

  Further, a preferred polymer block [B ′] necessarily contains the repeating unit [4], the repeating unit represented by the following general formula (12) [5] and the repeating unit represented by the following general formula (13). [6] A polymer block containing at least one of any of the above. 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 general formula (12), R ³⁸ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

In the general formula (13), R ³⁹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ⁴⁰ 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 general formula (14).

In the general formula (14), R ⁴¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ⁴² represents a nitrile group, an alkoxycarbonyl group, a formyl group, a hydroxycarbonyl group, or a halogen group, and R ⁴³ Represents a hydrogen atom. Alternatively, R ⁴² and R ⁴³ may be bonded to each other to form an acid anhydride group or an imide group.

  Further, a preferred block copolymer before hydrogenation is obtained 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 ′. 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. Particularly preferably, when it is in the range of 25,000 to 300,000, the mechanical strength is excellent and the hydrogenation rate is improved.

  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 depending on the purpose of use, but is a measured value on the high temperature side by DSC, 70 ° C to 150 ° C, more preferably 80 ° C to 140 ° C, Especially preferably, it is 90 degreeC-130 degreeC.

  In the method and reaction mode of hydrogenating the carbon-carbon unsaturated bond of the unsaturated ring such as the aromatic ring or cycloalkene ring of the block copolymer before hydrogenation and the unsaturated bond of the main chain or side chain There is no special limitation, and it may be performed according to a known method. However, a hydrogenation method that can increase the hydrogenation rate and has less polymer chain cleavage reaction is preferable. For example, in an organic solvent, nickel, cobalt, iron, titanium, The method is performed using a catalyst containing at least one metal selected from 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. The amount of the catalyst supported is preferably 0.01 to 80% by mass, more preferably It is in the range of 0.05 to 60% by 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. 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 mass, more preferably 100 parts by mass of the polymer. It is 0.05-50 mass parts, Most preferably, it is 0.1-30 mass parts.

  The hydrogenation reaction is usually 10 ° C. to 250 ° C., but it is preferably 50 ° C. to 200 ° C., more preferably 80 ° C. 180 ° C. 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 1H-NMR. The main chain and side chain carbon-carbon unsaturated bonds, and the carbon-carbon unsaturation of aromatic rings and cycloalkene rings. When any of the bonds is preferably 90% or more, more preferably 95% or more, and particularly preferably 97% or more, the low birefringence and thermal stability of the resulting copolymer are improved.

  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.

  In addition, a hydrogenated norbornene-based ring-opening polymer that is one of polymers having an alicyclic structure that can be used in the present invention is obtained by adding a norbornene-based monomer and a ring-opening polymerization catalyst. It is obtained by carrying out ring polymerization and adding the catalyst after completion of the monomer addition to complete ring-opening polymerization to obtain a norbornene-based ring-opening polymer, and then hydrogenating in the presence of a hydrogenation catalyst. Is.

  In the present invention, the norbornene-based monomer constituting the norbornene-based ring-opening polymer hydrogenated product includes norbornenes, norbornene derivatives having a ring structure other than the norbornene ring, tetracyclododecenes, hexacycloheptadecenes, and the like. Polycyclic olefins having a norbornene ring and represented by the following general formula (15). In addition, these monomers include hydrocarbon groups such as alkyl groups, alkenyl groups, and alkylidene groups; groups containing nitrogen atoms, oxygen atoms, silicon atoms, phosphorus atoms, or sulfur atoms; other than double bonds of norbornene rings It may further have a double bond.

In the general formula (15), represent respectively R ⁴⁴ to R ⁴⁷ independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen atom, a group containing a silicon atom, an oxygen atom or a nitrogen atom, R ⁴⁴ And R ⁴⁷ may combine to form a ring. p is 0, 1 or 2. q is 0 or 1.

  Norbornenes are norbornene monomers in which p and q in the general formula (15) are 0. Specific examples include unsubstituted or alkyl groups such as norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5-cyclohexylnorbornene, and 5-cyclopentylnorbornene. Norbornenes; norbornenes having an alkenyl group such as 5-ethylidene norbornene, 5-vinyl norbornene, 5-propenyl norbornene, 5-cyclohexenyl norbornene, 5-cyclopentenyl norbornene; norbornenes having an aromatic ring such as 5-phenyl norbornene ; 5-methoxycarbonyl norbornene, 5-ethoxycarbonyl norbornene, 5-methyl-5-methoxycarbonyl norbornene, 5-methyl-5-ethoxycarbonyl Norbornene, norbornenyl-2-methylpropionate, norbornenyl-2-methyloctanoate, norbornene-5,6-dicarboxylic anhydride, 5-hydroxymethylnorbornene, 5,6-di (hydroxymethyl) norbornene, 5,5 Norbornenes having a group containing an oxygen atom such as di (hydroxymethyl) norbornene, 5-hydroxy-i-propylnorbornene, 5,6-dicarboxynorbornene, 5-methoxycarbonyl-6-carboxynorbornene, and the like; 5-cyano And norbornenes having a group containing a nitrogen atom such as norbornene and norbornene-5,6-dicarboxylic acid imide.

The norbornene derivative having a ring structure other than the norbornene ring has a ring structure other than the norbornene ring and the 5-membered ring when p in the general formula (15) is 0, q is 0 or 1, and R ⁴⁴ and R ⁴⁷ are bonded. It is a norbornene-based monomer. Specific examples include dicyclopentadienes having p of 0 and q of 1, and norbornene derivatives having p of 0 and q of 1 and further having an aromatic ring. Specific examples of dicyclopentadiene include tricyclo [4.3.0.12,5] deca-3,7-diene (common name: dicyclopentadiene) having a double bond in a 5-membered ring portion, 5-membered Examples include tricyclo [4.3.12,5.0] dec-3-ene and tricyclo [4.4.12,5.0] under-3-ene saturated with a double bond in the ring portion. it can. Specific examples of norbornene derivatives having p of 0, q of 1, and an aromatic ring include tetracyclo [6.5.12, 5.01, 6.08,13] trideca-3,8,10,12. -Tetraene (also referred to as 1,4-methano-1,4,4a, 9a-tetrahydrofluorene) can be used.

  Tetracyclododecenes are norbornene monomers in which p is 1 and q is 0 in the general formula (15). Specific examples include unsubstituted or alkyl groups such as tetracyclododecene, 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, and 8-cyclopentyltetracyclododecene. Tetracyclododecenes; 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene, 8-propenyltetracyclododecene, 8-cyclohexenyltetracyclododecene, 8- Tetracyclododecenes having a double bond outside the ring such as cyclopentenyltetracyclododecene; tetracyclododecenes having an aromatic ring such as 8-phenyltetracyclododecene; 8-methoxycarbonyltetracyclododecene; 8-Methyl-8-methoxycarboni Oxygen such as tetracyclododecene, 8-hydroxymethyltetracyclododecene, 8-carboxytetracyclododecene, tetracyclododecene-8,9-dicarboxylic acid, tetracyclododecene-8,9-dicarboxylic anhydride Tetracyclododecenes having a group containing atoms; tetracyclododecenes having a group containing nitrogen atoms such as 8-cyanotetracyclododecene, tetracyclododecene-8,9-dicarboxylic imide; 8-chloro Tetracyclododecenes having a group containing a halogen atom such as tetracyclododecene; tetracyclododecenes having a group containing a silicon atom such as 8-trimethoxysilyltetracyclododecene; and the like.

  Hexacycloheptadecenes are norbornene monomers in which p is 2 and q is 0 in the general formula (15). Specific examples include unsubstituted or alkyl groups such as hexacycloheptadecene, 12-methylhexacycloheptadecene, 12-ethylhexacycloheptadecene, 12-cyclohexylhexacycloheptadecene, and 12-cyclopentylhexacycloheptadecene. Hexacycloheptadecenes; 12-methylidenehexacycloheptadecene, 12-ethylidenehexacycloheptadecene, 12-vinylhexacycloheptadecene, 12-propenylhexacycloheptadecene, 12-cyclohexenylhexacycloheptadecene, 12- Hexacycloheptadecenes having a double bond outside the ring such as cyclopentenyl hexacycloheptadecene; hexacycloheptadecene having an aromatic ring such as 12-phenylhexacycloheptadecene 12-methoxycarbonylhexacycloheptadecene, 12-methyl-12-methoxycarbonylhexacycloheptadecene, 12-hydroxymethylhexacycloheptadecene, 12-carboxyhexacycloheptadecene, hexacycloheptadecene 12,13-dicarboxylic acid Hexacycloheptadecenes having an oxygen atom-containing group such as acid and hexacycloheptadecene 12,13-dicarboxylic anhydride; 12-cyanohexacycloheptadecene, hexacycloheptadecene 12,13-dicarboxylic imide and the like Hexacycloheptadecenes having a group containing a nitrogen atom; hexacycloheptadecenes having a group containing a halogen atom such as 12-chlorohexacycloheptadecene; 12-trimethoxysilylhexacycloheptadecene Like hexamethylene cycloheptanone decene compound having a group containing a silicon atom such as. The above norbornene monomers can be used alone or in combination of two or more.

  The norbornene-based ring-opening polymer hydrogenated product according to the present invention may include a repeating unit derived from a monomer copolymerizable with the norbornene-based monomer. The other monomer copolymerizable with the norbornene-based monomer is not particularly limited. For example, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) ) Cycloolefins such as -1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5 -Non-conjugated dienes such as methyl-1,4-hexadiene and 1,7-octadiene;

  The repeating units derived from other monomers copolymerizable with these norbornene monomers are usually 0 to 50% by mass, preferably 0 to 30% by mass, more preferably 0 to 10% by mass.

  The mass average molecular weight (Mw) in terms of polyisoprene measured by gel permeation chromatography (GPC) using cyclohexane as a solvent of the norbornene-based ring-opening polymer according to the present invention is usually 10,000 to 100, 000, preferably 13,000 to 70,000, more preferably 14,000 to 60,000, particularly preferably 15,000 to 50,000. The molecular weight distribution (MWD) expressed as the ratio (Mw / Mn) of the mass average molecular weight (Mw) to the number average molecular weight (Mn) is usually 1.5 to 5.0, preferably 1.7. It is -4.0, More preferably, it is 1.8-3.0.

  The hydrogenated norbornene ring-opening polymer according to the present invention is a component having a mass average molecular weight (Mw) in terms of polyisoprene measured by gel permeation chromatography (GPC) using cyclohexane as a solvent of 75,000 or more. A smaller proportion is preferred. Specifically, it is 15 mass% or less in the total polymer, preferably 10 mass% or less.

  The glass transition temperature (Tg) of the norbornene ring-opening polymer hydrogenated product according to the present invention is appropriately selected according to the purpose of use, but is usually 30 to 300 ° C., preferably 60 to 250 ° C., more preferably 80 to When the temperature is in the range of 200 ° C., the obtained molded article is excellent in heat resistance, light resistance and molding processability.

  The method for producing a hydrogenated norbornene ring-opening polymer according to the present invention comprises adding a norbornene monomer and a ring-opening polymerization catalyst (initial addition catalyst) to perform ring-opening polymerization, and after completion of the monomer addition And adding the catalyst (additionally added catalyst) to terminate ring-opening polymerization to obtain a norbornene-based ring-opening polymer, and then hydrogenating in the presence of a hydrogenation catalyst.

  Examples of the norbornene monomer applicable to the present invention include the norbornene monomers constituting the hydrogenated product of the present invention. The proportion of the norbornene-based monomer is usually 50 to 100% by mass, preferably 70 to 100% by mass, more preferably 90 to 100% by mass, and particularly preferably 100% by mass. By setting the ratio of the norbornene-based monomer within the above range, the mechanical strength of the obtained molded body is improved.

  In the method for producing a norbornene ring-opening polymer according to the present invention, a monomer that can be copolymerized with the norbornene-based monomer may be used. The other monomer copolymerizable with the norbornene-based monomer is not particularly limited. For example, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) ) Cycloolefins such as -1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5 -Non-conjugated dienes such as methyl-1,4-hexadiene and 1,7-octadiene; The ratio of the other monomer copolymerizable with these norbornene-based monomers is usually 0 to 50% by mass, preferably 0 to 30% by mass, and more preferably 0 to 10% by mass.

  In the method for producing a norbornene ring-opening polymer according to the present invention, the polymerization reaction can be performed with or without using a solvent. If it can melt | dissolve in, it will not specifically limit. In particular, it is desirable to perform polymerization in an inert organic solvent.

  Examples of the inert organic solvent include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, hexane and heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; styrene dichloride, And halogenated hydrocarbons such as dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, dichlorobenzene, and trichlorobenzene. Among these, Preferably, aliphatic hydrocarbons, such as n-pentane, hexane, and heptane; Alicyclic hydrocarbons, such as cyclopentane and a cyclohexane; Or these halides are mentioned. These solvents can be used alone or in combination of two or more, and the amount used is usually 10 to 1000 parts by weight, preferably 50 to 700 parts by weight, per 100 parts by weight of the norbornene monomer. More preferably, it is the range of 100-500 mass parts. The present invention includes adding a norbornene monomer and a ring-opening polymerization catalyst (initial addition catalyst) to perform ring-opening polymerization.

  In the method for producing a norbornene ring-opening polymer according to the present invention, a norbornene-based monomer and a ring-opening polymerization catalyst may be mixed and added, or each may be added separately. It is preferable to carry out ring-opening polymerization by charging a part of the body, an inert organic solvent and a cocatalyst into the reaction vessel, and then adding the remainder of the norbornene-based monomer and the ring-opening polymerization catalyst. The amount of the norbornene monomer charged at this time is 50% by mass or less, preferably 40% by mass or less, based on the total amount of the norbornene monomer used in the production method of the present invention.

  Examples of the cocatalyst applicable to the method for producing a norbornene ring-opening polymer according to the present invention include those used as a cocatalyst for the ring-opening polymerization catalyst. Specific examples include organoaluminum compounds and organotin compounds, with organoaluminum compounds being preferred.

  Specific examples of organoaluminum compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum and triisobutylaluminum, and alkyl halide aluminums such as diethylaluminum monochloride and ethylaluminum dichloride. Preferably, triethylaluminum, triisobutylaluminum, diethylaluminum chloride, etc. are mentioned.

  These promoters can be used alone or in combination of two or more. The amount of the cocatalyst added is 0.005 to 10 mol%, preferably 0.02 to 5 mol%, based on the norbornene monomer. By using the cocatalyst within the above range, the generation of gel and high molecular weight components is small, the polymerization activity is high, and the molecular weight can be easily controlled.

  In the method for producing a norbornene ring-opening polymer according to the present invention, in addition to the norbornene monomer, the ring-opening polymerization catalyst and the cocatalyst, a molecular weight regulator or a reaction regulator may be added to the ring-opening polymerization reaction. it can.

  As the molecular weight regulator, chain monoolefins and chain conjugated dienes are usually used. Specific examples include 1-butene, 2-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-dodecene and 1,4-hexadiene. The amount of the molecular weight regulator used is appropriately selected depending on the polymerization conditions, but is usually 0.2 to 10 mol%, preferably 0.4 to 7 mol%, more preferably 0.8 to the norbornene-based monomer. 5 to 4 mol%.

  As the reaction regulator, at least one polar compound selected from active hydrogen-containing polar compounds such as alcohols and amines; polar compounds not containing active hydrogens such as ethers, esters, ketones, and nitriles can be used. The active hydrogen-containing polar compound is effective for preventing the generation of gel and obtaining a polymer having a specific molecular weight, and alcohol is particularly preferable. In addition, polar compounds that do not contain active hydrogen are effective in suppressing the formation of low molecular weight components in the polymer that cause a decrease in mechanical strength. Among them, ethers, esters, and ketones are preferable, and ketones are more preferable. preferable.

  Examples of the alcohol include saturated alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, pentanol, isopentanol, hexanol and cyclohexanol, and unsaturated alcohols such as phenol and benzyl alcohol. Of these, propanol, isopropanol, butanol and isobutanol are preferred.

  Examples of the ester include methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, propyl benzoate, isopropyl benzoate, and the like. Among these, methyl acetate and ethyl acetate are preferable.

  Examples of the ether include dimethyl ether, diethyl ether, dibutyl ether, ethylene glycol dibutyl ether and triethylene glycol dibutyl ether. Among these, diisopropyl ether and diethyl ether are preferable.

  Examples of the ketone include acetone, methyl ethyl ketone, diethyl ketone, methyl phenyl ketone, and diphenyl ketone. Among these, acetone and methyl ethyl ketone are preferable.

  The reaction modifiers can be used alone or in combination of two or more. In particular, in the present invention, it is preferable to combine a polar compound containing active hydrogen and a polar compound having no active hydrogen, and particularly a combination of alcohol and ketone, alcohol and nitrile, alcohol and ether, and alcohol and ester. The usage-amount of a reaction regulator is 0.001-10 mol% normally with respect to a norbornene-type monomer, Preferably it is the range of 0.01-5 mol%.

  The temperature condition of the ring-opening polymerization is usually -20 to 100 ° C, preferably 0 to 100 ° C, more preferably 10 to 80 ° C, and most preferably 10 to 50 ° C. If the temperature is too low, the reaction rate decreases, and if it is too high, it becomes difficult to control the reaction, and the energy cost increases. That is, by adjusting the temperature condition in the range of −20 to 100 ° C., the reaction can be easily controlled, the energy cost can be kept low, and the polymerization can proceed at an appropriate reaction rate.

  The pressure condition of the ring-opening polymerization is usually 0 to 5 MPa, preferably normal pressure to 1 MPa, more preferably normal pressure to 0.5 MPa.

  The ring-opening polymerization may be carried out in an inert gas atmosphere such as nitrogen or argon in order to prevent deterioration or coloring due to oxidation of the resulting polymer.

  The ring-opening polymerization catalyst applicable to the method for producing a norbornene ring-opening polymer according to the present invention is disclosed in JP-B-41-20111, JP-A-46-14910, JP-B-57-17883, JP-B-57-. No. 61044, JP-A-54-86600, JP-A-58-127728, JP-A-1-240517, etc., and known ring-opening polymerization catalysts of norbornene monomers. is there. Specifically, it is a compound of a transition metal belonging to Groups 4 to 10 of the periodic table, and halides, oxyhalides, alkoxyhalides, alkoxides, carboxylates, (oxy) acetylacetonates, carbonyls of these transition metals. Examples include complexes.

Specific examples include TiCl ₄ , TiBr ₄ , VOCl ₃ , VOBr ₃ , WBr ₄ , WBr ₆ , WCl ₂ , WCl ₄ , WCl ₅ , WCl ₆ , WF ₄ , WI ₂ , WOBr ₄ , WOCl ₄ , WOF ₄ , MoBr ₂ , MoBr ₃ , MoBr ₄ , MoCl ₄ , MoCl ₅ , MoF ₄ , MoOCl ₄ , MoOF ₄ , WO ₂ , H ₂ WO ₄ , NaWO ₄ , K ₂ WO ₄ , (NH ₄ ) ₂ WO ₄ , CaWO ₄ , CuWO ₄ , MgWO ₄ , (CO) ₅ WC (OCH ₃ ) (CH ₃ ), (CO) ₅ WC (OC ₂ H ₅ ) (CH ₃ ), (CO) ₅ WC (OC ₂ H ₅ ) (C _{4 H 5), (CO)} 5 MoC (OC 2 H 5) (CH 3), (CO) 5 Mo = C (C 2 H 5), (N (C 2 H 5) 2), tridecyl ammonium molybdate Acid salt, tridecyl ammonium tungstate, etc. It is below.

  Among the above ring-opening polymerization catalysts, W, Mo, Ti, or V compounds are preferable from the viewpoint of polymerization activity, and the halides, oxyhalides, or alkoxy halides are particularly preferable.

  The addition amount of the ring-opening polymerization catalyst is usually 0.001 to 5 mol%, preferably 0.005 to 2.5 mol%, more preferably 0.01 to 1 mol% with respect to the norbornene-based monomer. .

  In the method for producing a norbornene ring-opening polymer according to the present invention, a norbornene-based monomer and a ring-opening polymerization catalyst are added to perform ring-opening polymerization, and the catalyst is added even after completion of the monomer addition (additional addition) Catalyzed). Examples of the timing for additionally adding the ring-opening polymerization catalyst include immediately after the end of addition of the norbornene-based monomer and after the end of the addition of the monomer. In addition, as a method of additionally adding a ring-opening polymerization catalyst, for example, a method of adding a ring-opening polymerization catalyst at once, a method of continuously adding a ring-opening polymerization catalyst, or a method of intermittently adding a ring-opening polymerization catalyst The method of adding continuously is preferable.

  In the method for producing a norbornene ring-opening polymer according to the present invention, the polymerization conversion rate at the end of addition of the norbornene monomer is preferably 90 to 99%, more preferably 93 to 97%, and the amount of additional catalyst added is The amount is preferably 0.00005 mol% or more, more preferably 0.0025 mol% or more with respect to the norbornene-based monomer.

  In the method for producing a norbornene ring-opening polymer according to the present invention, it is preferable to perform ring-opening polymerization by stirring the reaction system. By performing ring-opening polymerization while stirring the reaction system, it is possible to suitably suppress a rapid temperature rise due to the heat of polymerization reaction.

  In the method for producing a norbornene ring-opening polymer according to the present invention, the polymerization is allowed to proceed to a molecular weight or a conversion rate according to the purpose, and then the ring-opening polymerization reaction is terminated. Thereafter, the ring-opening polymerization catalyst is inactivated in order to prevent gelation of the polymerization reaction solution, and then the deactivated ring-opening polymerization catalyst is removed as necessary.

  Examples of the method for inactivating the ring-opening polymerization catalyst include a method for adding a catalyst deactivator to the polymerization reaction solution.

  Preferred examples of the catalyst deactivator include compounds having a hydroxyl group such as water, alcohols, carboxylic acids, and phenols.

  Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 3-methyl-1-butanol, 2-ethyl-1-hexanol, and 2-propen-1-ol. 1,2-ethanediol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, pentaerythritol, 2-ethoxyethanol, 2,2-dichloro-1-ethanol, 2 -Aliphatic, alicyclic, aromatic mono-, di- or polyalcohols such as bromo-1-ethanol and 2-phenyl-1-ethanol.

  Examples of carboxylic acids include formic acid, acetic acid, trichloroacetic acid, acrylic acid, oxalic acid, maleic acid, propanetricarboxylic acid, tartaric acid, citric acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, benzoic acid, phthalic acid, pyromellitic acid And aliphatic, alicyclic and aromatic mono-, di- or polycarboxylic acids.

  Examples of phenols include phenol, cresol, xylenol, and the like. These catalyst deactivators can be used alone or in admixture of two or more.

  Of these compounds having a hydroxyl group, water or a water-soluble compound (for example, a compound having 4 or less carbon atoms) is preferable because it has low solubility in the polymer solution and hardly remains in the polymer. Among them, water or lower alcohols are preferable, but when water and alcohols are used simultaneously, catalyst deactivation efficiency is better than when water is used alone, and when alcohol is used alone. Compared to the above, it is preferable because precipitation of catalyst residue is facilitated. The preferable use ratio of water and alcohol is 0.1 to 5 parts by mass, particularly 0.2 to 2% by mass, based on 1 part by mass of water.

  The amount of the catalyst deactivator may be an amount sufficient to inactivate the polymerization catalyst, and preferably 1 to 20 molar equivalents relative to the stoichiometric amount necessary for inactivation of the polymerization catalyst. More preferably, it is the range of 2-10 molar equivalent. For example, when 1 mol of tungsten hexachloride and 1.5 mol of triethylaluminum are used as a ring-opening polymerization catalyst and methanol is used as a catalyst deactivator, the stoichiometric amount of methanol is 1 mol of tungsten hexachloride. Since 6 moles and 3 moles per mole of triethylaluminum are required, the stoichiometric amount of methanol required to deactivate the ring-opening polymerization catalyst is 10.5 moles.

  Furthermore, as a result of adding a catalyst deactivator to the polymer solution, when the polymerization catalyst is precipitated, active clay, talc, diatomaceous earth, bentonite, synthetic zeolite, Silica gel powder, alumina powder or the like may be added. Although the range of the addition amount is arbitrary, it is preferably about 0.1 to 10 times the mass of the ring-opening polymerization catalyst.

  The catalyst deactivator is added at an arbitrary temperature of −50 ° C. to 100 ° C., preferably 0 to 80 ° C., and an arbitrary pressure of 0 to 0.5 MPa, preferably normal pressure to 0.5 MPa. Under stirring, 0.5 to 10 hours, preferably 1 to 3 hours.

  In the method for producing a norbornene ring-opening polymer according to the present invention, when a transition metal halide is used as the ring-opening polymerization catalyst, hydrogen halide is generated by the addition of the polymerization catalyst deactivator, and the hydrogenation catalyst is covered. Since it is easily poisoned, it is preferable to add an acid scavenger in advance after addition of the polymerization catalyst deactivator after polymerization has proceeded to the molecular weight or conversion rate according to the purpose. Furthermore, it is preferable to add an additional acid scavenger after the addition of the polymerization catalyst deactivator and before the start of the hydrogenation reaction.

Examples of the acid scavenger include metal hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, and aluminum hydroxide; metal oxides such as calcium oxide and magnesium oxide; aluminum and magnesium , Zinc, iron, etc .; calcium carbonate, magnesium carbonate, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, hydrotalcite (Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O), acetic acid Salts such as sodium and magnesium acetate; epoxy compounds such as ethylene oxide, propylene oxide, butylene oxide, butyl glycidyl ether, phenyl glycidyl ether, cyclohexene oxide, 4-vinylcyclohexene oxide and styrene oxide; And the like.

  Salts having an acid scavenging effect are salts showing alkalinity, and strong acid and weak alkali salts are preferred. Among these acid scavengers, as the acid scavenger used before the addition of the polymerization catalyst deactivator, epoxy compounds and salts, and combinations thereof are preferable because of their excellent acid scavenging effect. Salts are preferred as the acid scavenger to be added at the time of hydrogenation. Corrosion of the reactor can be effectively suppressed under the temperature conditions during the hydrogenation reaction.

  The amount of the acid scavenger is 0.5 equivalent or more, preferably 1 to 100 equivalents, more preferably the maximum amount of hydrogen halide that can be generated by hydrolysis of the used ring-opening polymerization catalyst, that is, stoichiometric amount. 2 to 10 equivalents.

  The acid scavenger is added at an arbitrary temperature of -50 ° C to 100 ° C, preferably 0 ° C to 80 ° C, and an arbitrary pressure of 0 to 5 MPa, preferably normal pressure to 0.5 MPa. Subsequent addition and reaction of the polymerization catalyst deactivator are the same as described above.

The addition of an acid scavenger is preferable because the ring-opening polymerization catalyst is not removed before the hydrogenation step, and the activity of the hydrogenation catalyst is maintained even when the polymerization catalyst residue coexists.
In the production method of the present invention, after completion of the ring-opening polymerization reaction, a hydrogenation catalyst is added to perform a hydrogenation reaction. The hydrogenation catalyst is not particularly limited as long as it is generally used for hydrogenation of olefin compounds and aromatic compounds, and a heterogeneous catalyst or a homogeneous catalyst is usually used.

  As the heterogeneous catalyst, for example, nickel, palladium, platinum, or a solid catalyst supported on a carrier such as carbon, silica, diatomaceous earth, alumina, titanium oxide using these metals: nickel / silica, nickel / diatomaceous earth Examples of the catalyst include a combination of earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, palladium / alumina, and the like.

  Examples of the homogeneous catalyst include a catalyst comprising a combination of a transition metal compound and an alkylaluminum metal compound or alkyllithium, such as cobalt acetate / triethylaluminum, cobalt acetate / triisobutylaluminum, nickel acetate / triethylaluminum, nickel acetate / triethyl. Examples thereof include catalysts comprising a combination of isobutylaluminum, nickel acetylacetonate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, titanocene chloride / n-butyllithium, zirconocene chloride / n-butyllithium, and the like.

  The hydrogenation reactions can be used alone or in combination of two or more. The usage-amount of a hydrogenation catalyst is 0.01-100 mass parts normally per 100 mass parts of norbornene-type ring-opening polymers, Preferably it is 0.1-50 mass parts, More preferably, it is the range of 1-30 mass parts. . The hydrogenation reaction is usually carried out under a hydrogen pressure of 0.1 MPa to 30 MPa, preferably 1 MPa to 20 MPa, more preferably 2 MPa to 10 MPa, and a temperature range of 0 to 250 ° C. and a reaction time of 1 to 20 hours.

  In the method for producing a norbornene ring-opening polymer according to the present invention, the norbornene-based ring-opening polymer hydrogenated product is recovered by the following procedure. When a heterogeneous catalyst is used as the hydrogenation catalyst, after the hydrogenation reaction, the hydrogenation catalyst is removed by filtration, and then obtained by a solidification drying method or a direct drying method using a thin film dryer or the like. Can do. The norbornene-based ring-opening polymer hydrogenated product can be usually obtained in a powder form or a pellet form. On the other hand, when a homogeneous catalyst is used as the hydrogenation catalyst, alcohol or water is added after the hydrogenation reaction to deactivate the catalyst, insolubilized in a solvent, and then filtered to remove the catalyst.

  The olefin resin may be a polymer polymerized with one component monomer, but is preferably a copolymer polymerized with two or more monomers, more preferably a polymer polymerized with one component monomer. A block copolymer in which the polymer is further polymerized is preferred. For this copolymer, a monomer having 100 or more components may be used, but the mixing of the monomers is preferably 10 or less in terms of production efficiency and polymerization stability. Furthermore, 5 or less components are preferable.

  Further, the obtained copolymer may be a crystalline polymer or an amorphous polymer, but preferably an amorphous polymer.

"Additive"
The resin composition according to the present invention comprises a resin or a mixture of resins, an antioxidant, a light stabilizer, a UV absorber, a heat stabilizer, a weather stabilizer, a near infrared absorber, a stabilizer such as an oxygen scavenger; a lubricant, Resin modifiers such as plasticizers; colorants such as dyes and pigments; additives such as antistatic agents, flame retardants and fillers can be added. Hereinafter, the additive will be described.

"Antioxidant"
The antioxidant according to the present invention will be described. The antioxidant is a compound having a function of supplementing an oxidation promoting factor such as a free radical, and the weight reduction starting temperature is 180 ° C. or higher in a thermogravimetric analysis under an air atmosphere, that is, a weight loss curve measured by TGA. A compound is preferably used.

  Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, etc. Among them, phenolic antioxidants, particularly alkyl-substituted phenolic antioxidants are preferable. By adding these antioxidants, it is possible to prevent lens coloring and strength reduction due to oxidative degradation during molding without reducing transparency, heat resistance, and the like. These antioxidants can be used alone or in combination of two or more, and the amount added is appropriately selected within a range not impairing the object of the present invention. Preferably it is 0.001-5 mass parts with respect to a part, More preferably, it is 0.01-1 mass part.

  Conventionally known phenolic antioxidants can be used, such as 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 2,4-di-tert-pentylphenyl-3, 5-tert-butyl-4-hydroxybenzate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5.5] undecane, pentaerythritol tetrakis [3- (3,5-di-t-4-hydroxyphenyl) propionate], etc. The temperature is not particularly limited to these compounds as long as the temperature is 180 ° C. or higher.

<Light resistance stabilizer>
The light-resistant stabilizer used in the present invention will be described. A light-resistant stabilizer is a compound having a function of capturing free radicals generated by a photochemical reaction. In a weight loss curve measured by thermogravimetric analysis under an air atmosphere, that is, a weight loss curve measured by TGA, a weight reduction start temperature is 180 ° C. Certain compounds are preferably used.

  The light-resistant stabilizer is not particularly limited as long as the weight reduction starting temperature is 180 ° C. or higher, but examples include a benzophenone-based light-resistant stabilizer, a benzotriazole-based light-resistant stabilizer, a hindered amine-based light-resistant stabilizer, and the like. In the present invention, it is preferable to use a hindered amine light-resistant stabilizer from the viewpoints of transparency of the lens, coloring resistance and the like.

  As the hindered amine light-resistant stabilizer (hereinafter referred to as HALS), it is sufficient that at least one hindered amine structure per molecule such as monofunctional or polyfunctional, or a resin composition in which a hindered amine structure is pendant on a high molecular weight substance. Good. The molecular weight of the high molecular weight HALS is preferably such that the Mn in terms of polystyrene measured by GPC using THF as a solvent is 1000 to 10,000, more preferably 2000 to 5000, and particularly preferably 2800 to 3800. .

  When Mn is 1000 or more, preferably 2000 or more, more preferably 2800 or more, when HALS is added to the block copolymer by heating, melting and kneading, it is difficult to volatilize, so that a predetermined amount can be added. Such as foaming and silver streak are less likely to occur during heat-melt molding such as, thus improving processing stability. Further, when the lens is used for a long time with the lamp turned on, the volatile component is hardly generated as a gas from the lens.

  When Mn is 10,000 or less, preferably 5000 or less, more preferably 3800 or less, the dispersibility in the block copolymer is improved, the transparency of the lens is improved, and the effect of improving the light resistance is improved. That is, in the present invention, a lens excellent in processing stability, low gas generation property, and transparency can be obtained by setting the HALS Mn in the above range.

  Specific examples of such HALS include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6. Mixed esterified products such as 6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5.5] undecane And high molecular weight HALS in which a piperidine ring is bonded via an ester bond.

  The addition amount of the HALS to the resin according to the present invention is preferably 0.01 to 20 parts by mass, more preferably 0.02 to 15 parts by mass, particularly preferably 100 parts by mass of the polymer. 0.05 parts by mass to 10 parts by mass. When the addition amount is 0.01 parts by mass or more, an effect of improving light resistance is obtained, and coloring does not occur even when used outdoors for a long time. On the other hand, when the addition amount of HALS is 20 parts by mass or less, a part thereof is not generated as a gas, dispersibility in the resin is improved, and the transparency of the lens is improved.

<Ultraviolet absorber>
The ultraviolet absorbent used in the present invention will be described.

  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 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, 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′-methyl Benzotriazole-based UV absorbers such as benzyl] benzotriazole and 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] Etc. 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. .

  The amount of the ultraviolet absorber added to the resin according to the present invention is preferably 0.01 parts by mass to 20 parts by mass, more preferably 0.02 parts by mass to 15 parts by mass, particularly 100 parts by mass of the polymer. Preferably they are 0.05 mass part-10 mass parts. When the addition amount is 0.01 parts by mass or more, an effect of improving light resistance is obtained, and coloring does not occur even when used outdoors for a long time.

  However, when the optical resin lens according to the present invention is not used outdoors, that is, when incorporated into a pickup of an optical device such as a CD-ROM or DVD-ROM, it is not essential to add an ultraviolet absorber. , No additives may be used.

《Low glass transition temperature compound》
By adding less than 10% of the compound having the lowest glass transition temperature of 30 ° C. or less as an additive, long-term high temperature and high humidity without reducing various properties such as transparency, heat resistance and mechanical strength Can prevent cloudiness in the environment. Specifically, by adding at least one additive selected from a soft polymer and an alcoholic compound, a long time without deterioration of various properties such as transparency, low water absorption, and mechanical strength. Can prevent white turbidity in high temperature and high humidity environment.

《Soft polymer》
The soft polymer is usually a polymer having a Tg of 30 ° C. or lower, and when there are a plurality of Tg, it is preferable that at least the lowest Tg is 30 ° C. or lower.

  Specific examples of these soft polymers include the following polymers.

  (1) Liquid polyethylene, polypropylene, poly-1-butene, ethylene / α-olefin copolymer, propylene / α-olefin copolymer, ethylene / propylene / diene copolymer (EPDM), ethylene / propylene / styrene copolymer Olefin-based soft polymers such as polymers.

  (2) Isobutylene-based soft polymers such as polyisobutylene, isobutylene / isoprene rubber, and isobutylene / styrene copolymers.

  (3) Polybutadiene, polyisoprene, butadiene / styrene random copolymer, isoprene / styrene random copolymer, acrylonitrile / butadiene copolymer, acrylonitrile / butadiene / styrene copolymer, butadiene / styrene / block copolymer, styrene -Diene-based soft polymers such as butadiene / styrene / block copolymers, isoprene / styrene / block copolymers, and styrene / isoprene / styrene / block copolymers.

  (4) Silicon-containing soft polymers such as dimethylpolysiloxane, diphenylpolysiloxane, and dihydroxypolysiloxane.

  (5) A soft polymer comprising an α, β-unsaturated acid such as polybutyl acrylate, polybutyl methacrylate, polyhydroxyethyl methacrylate, polyacrylamide, polyacrylonitrile, butyl acrylate / styrene copolymer.

  (6) A soft polymer comprising an unsaturated alcohol such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, vinyl acetate / styrene copolymer, and an amine or an acyl derivative or acetal thereof.

  (7) Epoxy soft polymers such as ethylene oxide, polypropylene oxide, and epichlorohydrin rubber.

  (8) Fluorine-based soft polymers such as vinylidene fluoride rubber and tetrafluoroethylene-propylene rubber.

  (9) Other soft polymers such as natural rubber, polypeptide, protein, polyester-based thermoplastic elastomer, vinyl chloride-based thermoplastic elastomer, polyamide-based thermoplastic elastomer.

  The soft polymer may have a cross-linked structure or may have a functional group introduced by a modification reaction.

  Of the above-mentioned soft polymers, diene-based soft polymers are preferable. In particular, hydrides obtained by hydrogenating carbon-carbon unsaturated bonds of the soft polymers are excellent in terms of rubber elasticity, mechanical strength, flexibility, and dispersibility.

《Alcoholic compound》
The alcoholic compound is a compound having at least one non-phenolic hydroxyl group in the molecule, and preferably has at least one hydroxyl group and at least one ether bond or ester bond. Specific examples of such a compound include, for example, a dihydric or higher polyhydric alcohol, more preferably a trihydric or higher polyhydric alcohol, and even more preferably one of the hydroxyl groups of a polyhydric alcohol having 3 to 8 hydroxyl groups. Examples include etherified or esterified alcoholic ether compounds and alcoholic ester compounds.

  Examples of the dihydric or higher polyhydric alcohol include polyethylene glycol, glycerol, trimethylolpropane, pentaerythritol, diglycerol, triglycerol, dipentaerythritol, 1,6,7-trihydroxy-2,2-di (hydroxy). Methyl) -4-oxoheptane, sorbitol, 2-methyl-1,6,7-trihydroxy-2-hydroxymethyl-4-oxoheptane, 1,5,6-trihydroxy-3-oxohexanepentaerythritol, tris (2-Hydroxyethyl) isocyanurate and the like can be mentioned, and in particular, a trihydric or higher polyhydric alcohol, more preferably a polyhydric alcohol having 3 to 8 hydroxyl groups. In the case of obtaining an alcoholic ester compound, glycerol, diglycerol, triglycerol or the like capable of synthesizing an alcoholic ester compound containing α, β-diol is preferable.

  Examples of such alcoholic compounds include glycerol monostearate, glycerol monolaurate, glycerol monobehenate, diglycerol monostearate, glycerol distearate, glycerol dilaurate, pentaerythritol monostearate, and pentaerythritol monolaurate. , Pentaerythritol monobeherate, pentaerythritol distearate, pentaerythritol dilaurate, pentaerythritol tristearate, dipentaerythritol distearate, and the like; 3- (octyloxy) -1,2-propane Diol, 3- (decyloxy) -1,2-propanediol, 3- (lauryloxy) -1,2-propanediol, 3- (4-nonylphenyl) Xy) -1,2-propanediol, 1,6-dihydrooxy-2,2-di (hydroxymethyl) -7- (4-nonylphenyloxy) -4-oxoheptane, p-nonylphenyl ether and formaldehyde Alcoholic ether compounds obtained by reaction of condensates with glycidol, alcoholic ether compounds obtained by reaction of condensates of p-octylphenyl ether and formaldehyde with glycidol, condensates of p-octylphenyl ether and dicyclopentadiene and glycidol And alcoholic ether compounds obtained by the above reaction. These polyhydric alcohol compounds are used alone or in combination of two or more. Although the molecular weight of these polyhydric alcohol compounds is not particularly limited, those having a molecular weight of usually 500 to 2000, preferably 800 to 1500, have little decrease in transparency.

《Organic or inorganic filler》
As the organic filler, ordinary organic polymer particles or crosslinked organic polymer particles can be used, for example, polyolefins such as polyethylene and polypropylene; halogen-containing vinyl polymers such as polyvinyl chloride and polyvinylidene chloride; polyarylate, Polymers derived from α, β-unsaturated acids such as polymethacrylates; Polymers derived from unsaturated alcohols such as polyvinyl alcohol and polyvinyl acetate; Polymers derived from polyethylene oxide or bisglycidyl ether And aromatic condensed polymers such as polyphenylene oxide, polycarbonate and polysulfone; polyurethane; polyamide; polyester; aldehyde / phenolic resin; natural polymer compound particles or crosslinked particles.

  Examples of the inorganic filler include Group 1 element compounds such as lithium fluoride and borax (sodium borate hydrate); Group 2 element compounds such as magnesium carbonate, magnesium phosphate, calcium carbonate, strontium titanate, and barium carbonate; Titania), Group 4 element compounds such as titanium monoxide; Group 6 element compounds of molybdenum dioxide and molybdenum trioxide; Group 7 element compounds such as manganese chloride and manganese acetate; Group 8-10 element compounds such as cobalt chloride and cobalt acetate Group 11 element compounds such as cuprous iodide; Group 12 element compounds such as zinc oxide and zinc acetate; Group 13 such as aluminum oxide (alumina), aluminum fluoride, aluminosilicate (alumina silicate, kaolin, kaolinite) Elemental compounds; silicon oxide (silica, silica gel), graphite Carbon, graphite, Group 14 element compound such as glass; kernal stones, kainite, mica (mica, Kin'unmo) include particles of natural minerals, such as Bairosu ore.

  The addition amount of the soft polymer, alcoholic compound and organic or inorganic filler compound is determined by the combination of the resin and other additives contained in the resin composition according to the present invention, but the resin composition is molded. From the viewpoint of transparency, heat resistance and prevention of white turbidity under high temperature and high humidity, the molded product is 0.01 parts by mass to 10 parts by mass, preferably 0.02 parts by mass to 5 parts by mass with respect to 100 parts by mass of the resin Particularly preferably, it is added at a ratio of 0.05 to 2 parts by mass. Moreover, even if these additives are not added, the object of the present invention can be achieved.

《Other additives》
If necessary, the resin composition according to the present invention includes, as other additives, a near-infrared absorber, a coloring agent such as a dye or a pigment, a lubricant, a plasticizer, an antistatic agent, or a fluorescent brightening agent. These can be used alone or in admixture of two or more, and the amount added is appropriately selected within a range not impairing the object of the present invention.

(Method for preparing resin composition)
The method for preparing the resin composition according to the present invention will be described.

  The resin composition according to the present invention is preferably subjected to a specific processing treatment before the molding step (molding process), and a plasticizer, an antioxidant, and other additives usually added to the resin at the stage of the processing treatment An agent may be added.

  Examples of the method for preparing the resin composition according to the present invention include the following kneading process or a process for obtaining a composition by dissolving the solvent in a solvent, removing the solvent, and drying, and the like. Is a kneading process. Moreover, the process used for the addition of normal resin can be used as a kneading | mixing process. For example, a roll, a Banbury mixer, a twin-screw kneader, a kneader ruder or the like can be used, and a Banbury mixer, a twin-screw kneader, a kneader ruder or the like is preferable.

  In order to prevent the oxidation of the resin, an apparatus capable of kneading in a closed system is preferably used, and more preferably, the kneading process is performed by inert gasification such as nitrogen or argon.

  In addition to the kneading described above, the resin composition according to the present invention can also be adjusted by dissolving a resin composition obtained by mixing a resin and an additive in a solvent, and drying after dissolution. At this time, the solvent that dissolves the resin may be any solvent that can dissolve the resin, and the type thereof is not limited.

<< Method for Producing Optical Resin Lens >>
The manufacturing method of the optical resin lens of this invention is demonstrated.

  The method for producing an optical resin lens according to the present invention includes the steps of preparing the resin composition according to the present invention and then molding the obtained resin composition.

  The molding process of the resin composition according to the present invention will be described.

  The molded product of the resin composition according to the present invention is obtained by molding a molding material made of the resin composition. Although it does not restrict | limit especially as a shaping | molding method, In order to obtain the molding excellent in characteristics, such as low birefringence, mechanical strength, and dimensional accuracy, melt molding is preferable. Examples of the melt molding method include commercially available press molding, commercially available extrusion molding, and commercially available injection molding, and injection molding is preferred from the viewpoints of moldability and productivity.

  Molding conditions are appropriately selected depending on the purpose of use or molding method. For example, the temperature of the resin composition in injection molding (in the case of a resin alone or a mixture of a resin and an additive) can be appropriately controlled during molding. From the viewpoint of preventing the occurrence of silver streaks due to thermal decomposition of the resin, and effectively preventing yellowing of the molded product. The range of ° C is preferred, more preferably 200 ° C to 350 ° C, and particularly preferably 200 ° C to 330 ° C.

  The molded product according to the present invention can be used in various forms such as a spherical shape, a rod shape, a plate shape, a cylindrical shape, a tubular shape, a tubular shape, a fibrous shape, a film shape or a sheet shape, and has a low birefringence and a transparent property. It is used as an optical resin lens of the present invention because of its excellent properties, mechanical strength, heat resistance, and low water absorption, but is also suitable as other optical components.

  In the resin composition preparation step and the resin composition molding step according to the present invention, the above-described various additives can be added as necessary. The additives can be used alone or in combination of two or more, and the addition amount and addition timing are appropriately selected within a range not impairing the effects described in the present invention.

《Optical resin lens》
The optical resin lens of the present invention can be obtained by the above-described manufacturing method. As a specific application example to an optical component, as an optical lens or an optical prism, an imaging system lens of a camera; a microscope, an endoscope, Lenses such as telescope lenses; all light transmissive lenses such as spectacle lenses; CDs, CD-ROMs, WORMs (recordable optical disks), MOs (rewritable optical disks; magneto-optical disks), MDs (minidisks), DVDs ( A pickup lens of an optical disk such as a digital video disk; a laser scanning system lens such as an fθ lens of a laser beam printer or a sensor lens; a prism lens of a camera finder system.

  Examples of optical disc applications include CD, CD-ROM, WORM (recordable optical disc), MO (rewritable optical disc; magneto-optical disc), MD (mini disc), DVD (digital video disc), and the like. Other optical applications include light guide plates such as liquid crystal displays; optical films such as polarizing films, retardation films and light diffusing films; light diffusing plates; optical cards;

<Pickup device>
Among these, it is suitable as a pickup lens or a laser scanning system lens that requires low birefringence, and is most suitably used for a pickup lens.

  As an example of the use of the optical resin lens of the present invention, an example used as an objective lens used in a pickup device for an optical disk will be described with reference to FIG.

  In this embodiment, the target is a “high-density optical disk” using a so-called blue-violet laser light source having a used wavelength of 405 nm. This optical disk has a protective substrate thickness of 0.1 mm and a storage capacity of about 30 GB.

  FIG. 3 is a schematic view showing an example of an optical pickup device to which the optical resin lens according to the present invention is applied.

  In the optical pickup device 1, the laser diode (LD) 2 is a light source, and a blue-violet laser having a wavelength λ of 405 nm is used, but a laser having a wavelength in the range of 390 nm to 420 nm can be appropriately employed.

  The beam splitter (BS) 3 transmits the light source incident from the LD 2 in the direction of the objective lens (OBL) 4, but with respect to the reflected light (returned light) from the optical disk (optical information recording medium) 5, the sensor lens (SL) 6. It has the function to condense to the light receiving sensor (PD) 7 through the above.

  The light beam emitted from the LD 2 is incident on the collimator (COL) 8, collimated into infinite parallel light, and then incident on the objective lens OBL 4 via the beam splitter (BS) 3. Then, a condensing spot is formed on the information recording surface 5 b via the protective substrate 5 a of the optical disc (optical information recording medium) 5. Next, after reflecting on the information recording surface 5b, following the same path, the polarization direction is changed by the quarter wave plate (Q) 9, the path is bent by BS3, and the sensor (SL) 6 is passed through the sensor ( Condensed on PD) 7. This sensor photoelectrically converts it into an electrical signal.

  The objective lens OBL4 is a single lens resin lens for injection according to the present invention, which is injection molded with resin. An aperture (AP) 10 is provided on the incident surface side to determine the beam diameter. Here, the incident light beam is reduced to a diameter of 3 mm. The actuator (AC) 11 performs focusing and tracking.

  The numerical aperture required for the objective lens OBL4 differs depending on the thickness of the protective substrate of the optical information recording medium and the size of the pits. Here, the numerical aperture of the high-density optical disk (optical information recording medium) 5 is 0.85.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

<Preparation of resin A>
60 L of methanol is put into a 100 L stainless steel pot, and stirred with a separately installed stirrer. In this beaker, APEL 5014DP (manufactured by Mitsui Chemicals, Inc .: Tg determined by a differential scanning calorimeter (DSC): 126 ° C. 3 L of 15% cyclohexane solution was added dropwise over 60 minutes. After completion of dropping, the mixture was stirred for 60 minutes, and the precipitated polymer was collected by filtration with a 50 cm Nutsche. Then, 432.8 g of Resin 1 from which the additive was removed was obtained by drying under reduced pressure at 50 ° C. for 6 hours.

<Preparation of resin B>
Resin from which additive was removed by performing the same operation as in <Preparation of Resin 1> except that a 15% cyclohexane solution of ZEONEX 330R (manufactured by Nippon Zeon Co., Ltd .: Tg determined by DSC: 123 ° C.) was used. 436.1g of 2 was obtained.

<< Manufacture of Optical Resin Lens 1 >>: 0.5 parts by mass of 4,4′-butylidenebis (6-tert-butyl-3-methylphenol) is added to 100 parts by mass of the resin A of the present invention. Kneading for 10 minutes at 190 ° C. under a nitrogen atmosphere. Resin composition 1 was produced by pulverizing 10 batches under the same conditions as described above.

  Using a pulverized product of the resin composition 1, an inline injection molding machine was used to perform injection molding under the conditions of a mold clamping pressure of 50 t, a mold temperature of 120 ° C., and an injection pressure of 69.0 MPa to produce a lens having a diameter of 1 cm.

  When 50 mg of the pulverized product of the resin composition 1 was measured using a thermobalance EXSTAR6000 TG / DTA6200 manufactured by Seiko Instruments Inc., the first derivative B of the TGA curve A and the TGA curve A shown in FIG. 1 was obtained. From FIG. 1, the minimum peak value of the first derivative B of the TGA curve A was less than half of the maximum peak value, and the temperature difference was 44.8 ° C.

  FIG. 2 shows a TGA curve C of 4,4′-butylidenebis (6-tert-butyl-3-methylphenol) added to the resin composition used in the production of the optical resin lens 1. The weight loss starting temperature was 185.6 ° C.

<< Manufacture of Optical Resin Lens 2 >>: Dibutylamine and 1,3,5-triazine / N, N′-bis (2,2,6,6-tetramethyl-4-based on 100 parts by mass of the resin A of the present invention Piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate [HALS (A), Mn = 3,000] 0.5 A resin composition 2 was prepared and pulverized in the same manner as in the production of the optical resin lens 1 by adding parts by mass, and a lens having a diameter of 1 cm was produced in the same manner as in the production of the optical resin lens 1.

  When the first derivative of the TGA curve was determined for 50 mg of the pulverized resin composition 2 in the same manner as in the production of the optical resin lens 1, the minimum peak value of the first derivative was less than half of the maximum peak value. The difference between the temperature and the maximum peak temperature was 48.5 ° C. Moreover, the weight decreasing start temperature of the additive mixture added to the resin composition 2 was 221.3 ° C.

<< Production of Optical Resin Lens 3 >>: 0.5 part by mass of 4,4′-butylidenebis (6-tert-butyl-3-methylphenol) and 1,3,5 of dibutylamine with respect to 100 parts by mass of the resin A of the present invention -Triazine N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4- Piperidyl) Butylamine polycondensate [HALS (A), Mn = 3,000] 0.5 parts by mass is added, and resin composition 3 is prepared and pulverized in the same manner as optical resin lens 1 is manufactured. Then, a lens having a diameter of 1 cm was produced by the same method as the production of the optical resin lens 1.

  When the first derivative of the TGA curve was determined for 50 mg of the pulverized resin composition 3 in the same manner as in the production of the optical resin lens 1, the minimum peak value of the first derivative was less than half of the maximum peak value. The difference between the temperature and the maximum peak temperature was 39.9 ° C.

<< Manufacture of optical resin lens 4 >>: 0.5 parts by mass of pentaerythritol tetrakis [3- (3,5-di-t-4-hydroxyphenyl) propionate] is added to 100 parts by mass of the resin B of the present invention. A resin composition 4 was prepared and pulverized in the same manner as in the production of the optical resin lens 1, and a lens having a diameter of 1 cm was produced in the same manner as in the production of the optical resin lens 1.

  When the first derivative of the TGA curve was determined for 50 mg of the pulverized resin composition 4 in the same manner as in the production of the optical resin lens 1, the minimum peak value of the first derivative was less than half of the maximum peak value. The difference between the temperature and the maximum peak temperature was 43.6 ° C. Moreover, the weight reduction start temperature of pentaerythritol tetrakis [3- (3,5-di-t-4-hydroxyphenyl) propionate] added to the resin composition 4 was 249.4 ° C.

<< Manufacture of optical resin lens 5 >>: 0.5 parts by mass of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate is added to 100 parts by mass of the resin B of the present invention, and the optical resin lens 1 A resin composition 5 was prepared and pulverized in the same manner as in the production of No. 1, and a lens having a diameter of 1 cm was produced in the same manner as in the production of the optical resin lens 1.

  When the first derivative of the TGA curve was determined for 50 mg of the pulverized resin composition 5 in the same manner as in the production of the optical resin lens 1, the minimum peak value of the first derivative was less than half of the maximum peak value. The difference between the temperature and the maximum peak temperature was 46.0 ° C. Moreover, the weight reduction start temperature of bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate added to the resin composition 5 was 193.4 ° C.

<< Production of Optical Resin Lens 6 >> Pentaerythritol tetrakis [3- (3,5-di-t-4-hydroxyphenyl) propionate] 0.5 parts by mass and bis (2, 2,6,6-tetramethyl-4-piperidyl) sebacate 0.5 parts by mass is added, and a resin composition 6 is produced and pulverized in the same manner as in the production of the optical resin lens 1 to obtain an optical resin lens. A lens having a diameter of 1 cm was produced in the same manner as in the production of 1.

When the first derivative of the TGA curve was determined for 50 mg of the pulverized resin composition 6 in the same manner as in the production of the optical resin lens 1, the minimum peak value of the first derivative was less than half of the maximum peak value. The difference between the temperature and the maximum peak temperature was 44.5 ° C.
<< Manufacture of optical resin lens 7 >>: 3,3,3 ′, 3′-tetramethyl-5,5 ′, 6,6′-tetrapropoxy-1,1′-spirobiindane relative to 100 parts by mass of Comparative resin A 0.5 parts by mass is added, and a resin composition 7 is produced and pulverized in the same manner as in the production of the optical resin lens 1, and a lens having a diameter of 1 cm is produced in the same manner as in the production of the optical resin lens 1. did.

  When the first derivative of the TGA curve was determined for 50 mg of the pulverized resin composition 7 in the same manner as in the production of the optical resin lens 1, the minimum peak value of the first derivative was less than half the maximum peak value. The difference between the minimum peak temperature and the maximum peak temperature was 56.9 ° C. Moreover, the weight decreasing start temperature of 3,3,3 ′, 3′-tetramethyl-5,5 ′, 6,6′-tetrapropoxy-1,1′-spirobiindane added to the resin composition is 168.6. ° C.

<< Manufacture of optical resin lens 8 >>: 3,3,3 ′, 3′-tetramethyl-5,5 ′, 6,6′-tetrapropoxy-1,1′-spirobiindane relative to 100 parts by mass of Comparative resin B 0.5 parts by mass are added, and the resin composition 8 is prepared and pulverized in the same manner as in the production of the optical resin lens 1, and a lens having a diameter of 1 cm is produced in the same manner as in the production of the optical resin lens 1. did.

  When 50 mg of the pulverized product of the resin composition 8 was determined for the first derivative of the TGA curve in the same manner as in the production of the optical resin lens 1, the minimum peak value of the first derivative was less than half of the maximum peak value. The difference between the minimum peak temperature and the maximum peak temperature was 62.3 ° C. Further, the weight decrease starting temperature of 3,3,3 ′, 3′-tetramethyl-5,5 ′, 6,6′-tetrapropoxy-1,1′-spirobiindane added to the resin composition 8 is 168. It was 6 ° C.

《Lens durability evaluation》
The optical resin lenses 1 to 6 according to the present invention obtained in each of the above production examples and the optical resin lenses 7 to 8 as comparative examples are used as objective lenses of the optical pickup device shown in FIG. In this atmosphere, 15 mW blue laser light (wavelength: 405 nm) was continuously irradiated for 500 hours and continuously irradiated for 2000 hours. The degree of cloudiness of the lens after each continuous irradiation was visually observed, and rank evaluation was performed as follows. The obtained results are shown in Table 1.

(Rank evaluation)
○: No cloudiness is generated (practical use possible)
Δ: Slight cloudiness is observed (practical use possible)
×: The occurrence of cloudiness is clearly observed (not practical)
From Table 1, it is clear that the optical resin lenses 1 to 6 according to the present invention exhibit superior durability compared to the optical resin lenses 7 and 8 which are comparative examples.

It is a graph which shows the 1st derivative of the TGA curve and TGA curve of the resin composition which concerns on this invention. It is a graph which shows the TGA curve of the compound added to the resin composition which concerns on this invention. It is a schematic diagram which shows an example of the pick-up apparatus for optical discs to which the optical resin lens which concerns on this invention was applied as an objective lens.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Optical pick-up apparatus 2 Laser diode 3 Beam splitter 4 Objective lens 5 Optical disk 5a Protection board 5b Information recording surface 6 Sensor lens 7 Sensor 8 Collimator 9 1/4 wavelength plate 10 Aperture 11 Actuator

Claims (14)

An optical resin lens comprising a resin composition that satisfies the following conditions.
50> | Ta-Tb |> 10
(Ta is the temperature (° C.) at which the peak value of the first derivative of the weight loss curve measured by thermogravimetric analysis in an air atmosphere is maximum, and Tb is the weight loss curve measured by thermogravimetric analysis in an air atmosphere. (The temperature at which the peak value of the first derivative is minimized (° C.), and Ta and Tb are 250 ° C. or higher.) The said resin composition contains at least 1 sort (s) of antioxidant whose weight reduction start temperature is 180 degreeC or more in the weight reduction curve measured by the thermogravimetric analysis in an air atmosphere. The optical resin lens described in 1. The said resin composition contains at least 1 sort (s) of light-resistant stabilizer whose weight decreasing start temperature is 180 degreeC or more in the weight decreasing curve measured by the thermogravimetric analysis in an air atmosphere. The optical resin lens described in 1. 4. The optical resin lens according to claim 1, wherein the resin composition contains at least one resin having a Tg of 80 ° C. or higher. 5. The optical resin lens according to claim 1, wherein the resin composition contains at least one olefin-based resin. 6. The optical resin lens according to claim 5, wherein the olefin resin is a copolymer synthesized by polymerization of two or more monomers. The optical resin lens according to claim 1, wherein the resin composition satisfies the following conditions.
0 <b <a / 2
(A is the maximum peak value of the first derivative of the weight loss curve measured by thermogravimetric analysis under air atmosphere, and b is the minimum peak value of the first derivative of the weight loss curve measured by thermogravimetric analysis under air atmosphere. .) The manufacturing method of the optical resin lens characterized by including the process of shape | molding the resin composition which satisfies the following conditions.
50> | Ta-Tb |> 10
(Ta is the temperature (° C.) at which the peak value of the first derivative of the weight loss curve measured by thermogravimetric analysis in an air atmosphere is maximum, and Tb is the weight loss curve measured by thermogravimetric analysis in an air atmosphere. (The temperature at which the peak value of the first derivative is minimized (° C.), and Ta and Tb are 250 ° C. or higher.) The said resin composition contains at least 1 sort (s) of antioxidant whose weight decreasing start temperature is 180 degreeC or more in the weight decreasing curve measured by the thermogravimetric analysis in an air atmosphere. The manufacturing method of the resin lens for optics as described in 2. The said resin composition contains at least 1 sort (s) of light-resistant stabilizer whose weight decreasing start temperature is 180 degreeC or more in the weight decreasing curve measured by the thermogravimetric analysis in an air atmosphere. The manufacturing method of the resin lens for optics as described in 2. 11. The method for producing an optical resin lens according to claim 8, wherein the resin composition contains at least one resin having a Tg of 80 ° C. or more. The method for producing an optical resin lens according to claim 8, wherein the resin composition contains at least one olefin-based resin. The method for producing an optical resin lens according to claim 12, wherein the olefin resin is a copolymer synthesized by polymerization of two or more monomers. The method for producing an optical resin lens according to claim 8, wherein the resin composition satisfies the following conditions.
0 <b <a / 2
(A is the maximum peak value of the first derivative of the weight loss curve measured by thermogravimetric analysis under air atmosphere, and b is the minimum peak value of the first derivative of the weight loss curve measured by thermogravimetric analysis under air atmosphere. .)

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