WO2009084308A1 - Alicyclic hydrocarbon random copolymer, method for producing the same, resin composition and molded article - Google Patents
Alicyclic hydrocarbon random copolymer, method for producing the same, resin composition and molded article Download PDFInfo
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- WO2009084308A1 WO2009084308A1 PCT/JP2008/069011 JP2008069011W WO2009084308A1 WO 2009084308 A1 WO2009084308 A1 WO 2009084308A1 JP 2008069011 W JP2008069011 W JP 2008069011W WO 2009084308 A1 WO2009084308 A1 WO 2009084308A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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- the present invention relates to an alicyclic hydrocarbon random copolymer having a high balance of heat resistance, low birefringence, and laser resistance.
- the present invention also provides a method for producing the alicyclic hydrocarbon random copolymer, a resin composition containing the alicyclic hydrocarbon random copolymer as a resin component, and the alicyclic hydrocarbon random copolymer.
- the present invention relates to a combined product or a molded product obtained by molding the resin composition.
- An alicyclic hydrocarbon polymer obtained by hydrogenating an aromatic ring of an aromatic vinyl polymer such as polystyrene is a resin material having high light transmittance, low birefringence, and characteristics suitable for optical materials.
- an aromatic ring of a styrene resin such as polystyrene or a styrene-butadiene-styrene block copolymer is hydrogenated to form a polyvinylcyclohexane resin, and then the polyvinylcyclohexane
- Patent Document 1 an aromatic ring of a styrene resin such as polystyrene or a styrene-butadiene-styrene block copolymer is hydrogenated to form a polyvinylcyclohexane resin, and then the polyvinylcyclohexane
- a method of manufacturing an optical disk substrate by injection molding of a resin has been proposed.
- An alicyclic hydrocarbon polymer obtained by hydrogenating an aromatic ring of an aromatic vinyl polymer is excellent in transparency, low birefringence, low water absorption, and the like. It has been proposed to be applied to use as a signal reading pickup lens.
- the pickup lens is required to have a small birefringence, its shape is complicated, so when molded using a conventional alicyclic hydrocarbon polymer, compared to an optical disk substrate, Birefringence tends to increase.
- the birefringence of optical parts is affected by both the birefringence inherent to the resin material used and the residual stress during molding. It is difficult to reduce the birefringence inherent in the resin material.
- By increasing the resin temperature during molding or by reducing the molecular weight of the resin material to improve the melt fluidity of the resin material during molding the residual stress of the molded product can be reduced.
- the resin temperature at the time of molding is increased, the molded product is likely to be thermally decomposed or thermally deteriorated.
- the molecular weight of the resin material is reduced, the mechanical strength of the molded product is lowered.
- Patent Document 2 discloses an aromatic vinyl copolymer obtained by random copolymerization of an aromatic vinyl monomer, a conjugated diene monomer, and, if desired, another vinyl monomer.
- An alicyclic hydrocarbon copolymer synthesized and then hydrogenated on a carbon-carbon unsaturated double bond containing an aromatic ring of the aromatic vinyl copolymer has been proposed.
- the alicyclic hydrocarbon copolymer disclosed in Patent Document 2 is excellent in transparency and low birefringence, and is also excellent in mechanical strength such as tensile strength. It is a resin material suitable for molding.
- the pickup lens applied to recording and / or reproducing media using a semiconductor laser with a short oscillation wavelength such as a blue laser Therefore, it is required to be excellent in laser resistance and heat resistance.
- Irradiation with a semiconductor laser having a short oscillation wavelength increases the irradiation energy density of the irradiated portion, so that a pickup lens molded from a resin material is susceptible to deterioration.
- a pickup lens deteriorated by laser irradiation has a reduced light transmittance.
- the pickup lens tends to be exposed to a high temperature environment as the recording and / or reproducing apparatus is miniaturized, the wiring density is increased, and the laser transmission wavelength is shortened.
- the heat resistance of the resin material constituting the pickup lens is low, the resin material is likely to be deformed or thermally deteriorated in a high temperature environment. As a result, the performance of the pickup lens decreases with the use of recording and / or playback equipment.
- the alicyclic hydrocarbon copolymer disclosed in Patent Document 2 is a resin material suitable for use as a pickup lens. Although the laser resistance can be improved by selecting the copolymer composition of the alicyclic hydrocarbon copolymer, it has been found that the glass transition temperature tends to decrease. Accordingly, there remains room for further improvement in the alicyclic hydrocarbon copolymer.
- JP-A-1-317728 JP 2001-48924 (corresponding to US 6,686,430 B1)
- An object of the present invention is to provide an alicyclic hydrocarbon random copolymer having a high balance of heat resistance, low birefringence, and laser resistance, and a method for producing the same.
- Another object of the present invention is to mold a resin composition containing the alicyclic hydrocarbon random copolymer, an optical component molded using the alicyclic hydrocarbon random copolymer, or the resin composition. To provide things.
- the present inventors have disclosed an alicyclic hydrocarbon random copolymer obtained by hydrogenating a random copolymer of styrene and isoprene disclosed in Examples of JP-A-2001-48924 (Patent Document 2).
- Patent Document 2 The inventors have found that the glass transition temperature tends to decrease although the laser resistance improves as the content of the repeating unit derived from isoprene is increased.
- Patent Document 2 has a wide disclosure about a method for producing an alicyclic hydrocarbon random copolymer, the repeating unit derived from a conjugated diene monomer such as isoprene is substantially composed only of 1,4-bonds. It does not have a pendant vinyl structure. This is also clear from the structure of the repeating unit derived from the conjugated diene monomer shown as Formula 3 in claim 1 of Patent Document 2.
- the present inventors provide an electron donating agent with an aromatic vinyl monomer, at least one conjugated diene monomer selected from the group consisting of isoprene and 1,3-butadiene, and optionally other vinyl monomers.
- an aromatic vinyl monomer at least one conjugated diene monomer selected from the group consisting of isoprene and 1,3-butadiene, and optionally other vinyl monomers.
- the alicyclic hydrocarbon random copolymer of the present invention is excellent in transparency, low birefringence, mechanical strength, heat resistance, laser resistance, and by increasing the content of repeating units derived from isoprene. Even if the laser resistance is improved, the glass transition temperature is maintained at a high level, and the birefringence tends to be improved.
- the alicyclic hydrocarbon random copolymer of the present invention varies in glass transition temperature, birefringence, and laser resistance as the copolymer composition of the aromatic vinyl monomer and the conjugated diene monomer varies.
- the glass transition temperature is high and the heat resistance is improved.
- Low birefringence and laser resistance tend to be improved.
- the present invention has been completed based on these findings.
- an alicyclic hydrocarbon random copolymer containing a repeating unit [A] having an alicyclic structure and a repeating unit [B] having a chain structure, (1)
- the repeating unit [A] of the alicyclic structure is represented by the following formula 1
- R 1 and R 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.
- n is 0 or an integer of 1 to 5.
- the repeating unit [B] of the chain structure is represented by the following formula 2
- R 3 is a hydrogen atom or a methyl group.
- R 3 is a hydrogen atom or a methyl group.
- Mw weight average molecular weight
- steps I and II (I) 85 to 99% by weight of an aromatic vinyl monomer, 1 to 15% by weight of at least one conjugated diene monomer selected from the group consisting of isoprene and 1,3-butadiene, and other vinyl monomers 0 to 10% by weight is polymerized in the presence of a compound having an electron donor atom, and a random copolymer having a 1,4-bond content of 70 mol% or less in the repeating unit of the conjugated diene monomer.
- the manufacturing method of the said alicyclic hydrocarbon random copolymer containing is provided.
- a resin composition containing the alicyclic hydrocarbon random copolymer and an antioxidant.
- a molded product obtained by molding the alicyclic hydrocarbon random copolymer or the resin composition.
- an alicyclic hydrocarbon random copolymer in which heat resistance, low birefringence, and laser resistance are highly balanced.
- the alicyclic hydrocarbon random copolymer or the resin composition containing the alicyclic hydrocarbon random copolymer of the present invention can be used as a molding material for molded articles such as optical parts. Since the alicyclic hydrocarbon random copolymer of the present invention suppresses the decrease in heat resistance even when the laser resistance is improved, recording using a semiconductor laser having a short oscillation wavelength such as a blue laser and / or It is suitable as a molding material for a pickup lens applied to the use of a reproduction medium.
- the alicyclic hydrocarbon random copolymer of the present invention is an alicyclic hydrocarbon random copolymer containing a repeating unit [A] having an alicyclic structure and a repeating unit [B] having a chain structure.
- the repeating unit [A] of the alicyclic structure is represented by the following formula 1
- R 1 and R 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or an alkylcarbonyl having 1 to 20 carbon atoms.
- n is 0 or an integer of 1 to 5.
- hydrocarbon group examples include an alkyl group having 1 to 20, preferably 1 to 10, and more preferably 1 to 6 carbon atoms; an alkenyl group having 2 to 20, preferably 2 to 10, more preferably 2 to 6 carbon atoms.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- the alkoxy group having 1 to 20 carbon atoms is preferably an alkoxy group having 1 to 6 carbon atoms.
- the alkylcarbonyloxy group having 1 to 20 carbon atoms is preferably an alkylcarbonyloxy group having 1 to 6 carbon atoms.
- hydrocarbon group substituted with a polar group examples include halogenated alkyl groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
- R 1 and R 2 are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms from the viewpoint of heat resistance and low water absorption.
- the repeating unit [B] of the chain structure (non-alicyclic structure) constituting the alicyclic hydrocarbon random copolymer of the present invention is represented by the following formula 2
- R 3 is a hydrogen atom or a methyl group.
- R 3 is a hydrogen atom or a methyl group. It is a repeating unit having a chain structure having a repeating unit [B 2 ] represented by
- the repeating unit [B 1 ] is a repeating unit derived from a 1,4-addition reaction of isoprene and / or 1,3-butadiene. More specifically, the repeating unit [B 1 ] is a main chain carbon-carbon unsaturated double bond in the 1,4-bond of isoprene and / or the 1,4-bond of 1,3-butadiene. Is a hydrogenated repeating unit.
- the repeating unit [B 2 ] is a repeating unit derived from a 3,4-addition reaction of isoprene and / or a 1,2-addition reaction of 1,3-butadiene. More specifically, the repeating unit [B 2 ] represents a pendant carbon-carbon unsaturated double bond in the repeating unit of the 3,4-bond of isoprene and / or the 1,2-bond of 1,3-butadiene. Repeating unit.
- the total content of the alicyclic structure repeating unit [A] and the chain structure repeating unit [B] in the alicyclic hydrocarbon random copolymer is: 90% by weight or more, preferably 95% by weight or more, more preferably 99% by weight or more, and in many cases 99.9% by weight.
- R 3 is a hydrogen atom or a methyl group.
- R 3 is a hydrogen atom or a methyl group.
- R 4 to R 7 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms.
- the content of the repeating unit [B] having a chain structure in the alicyclic hydrocarbon random copolymer of the present invention is 1 to 15% by weight, preferably 2 to 10% by weight. From the viewpoint, 3 to 6% by weight is particularly preferable.
- the content of the repeating unit [B] having a chain structure is too small, birefringence tends to increase and laser resistance also decreases. When there is too much content of this repeating unit [B], heat resistance will fall.
- the content of the repeating unit [B 1 ] in the repeating unit [B] having a chain structure is 70 mol% or less, preferably 60 mol% or less. Preferably it is 55 mol% or less.
- the lower limit of the content of the repeating unit [B 1 ] is usually 40 mol%, and in many cases 45 mol%.
- the content of the repeating unit [B 1] is a value calculated the sum of the repeating units and the repeating unit [B 1] [B 2] being 100 mol%.
- the weight average molecular weight (Mw) of the alicyclic hydrocarbon random copolymer of the present invention measured by gel permeation chromatography (GPC) is 10,000 to 300,000, preferably 30,000 to 250,000. It is preferably 50,000 to 200,000.
- Mw weight average molecular weight of the alicyclic hydrocarbon random copolymer of the present invention measured by gel permeation chromatography
- the glass transition temperature measured using a differential scanning calorimeter (DSC) of the alicyclic hydrocarbon random copolymer of the present invention is preferably 100 ° C. or higher, more preferably 105 ° C. or higher, more preferably 110 ° C. or higher, Especially preferably, it is 120 degreeC or more.
- the upper limit of the glass transition temperature is usually 135 ° C., and in many cases 130 ° C.
- the glass transition temperature is usually 3 ° C. or higher, preferably 4 ° C. or higher, and in many cases 5 ° C. or higher.
- the same tendency occurs when the alicyclic hydrocarbon random copolymer of the present invention is synthesized by hydrogenation of a styrene-1,3-butadiene / random copolymer.
- the alicyclic hydrocarbon random copolymer of the present invention has excellent heat resistance, low birefringence, and excellent resistance to a semiconductor laser having a short oscillation wavelength such as a blue laser. Therefore, the alicyclic hydrocarbon random copolymer of the present invention maintains the heat resistance at a high level even when the content of the repeating unit [B] having a chain structure is increased to improve the laser resistance. And birefringence can be reduced.
- the alicyclic hydrocarbon random copolymer of the present invention is a random copolymer. This is clear from the production method of the alicyclic hydrocarbon random copolymer of the present invention itself. Furthermore, the alicyclic hydrocarbon random copolymer of the present invention is an aromatic vinyl monomer-conjugated diene monomer copolymer obtained by random copolymerization of an aromatic vinyl monomer and a conjugated diene monomer. It can be obtained by hydrogenating the polymer, but the fact that the aromatic vinyl monomer-conjugated diene monomer copolymer is a random copolymer is apparent from the following relational expression. It is.
- D weight average molecular weight (Mw) of the aromatic vinyl monomer chain
- E [weight average molecular weight of aromatic vinyl monomer-conjugated diene monomer copolymer ⁇ number of repeating units derived from aromatic vinyl monomer unit / aromatic vinyl monomer-conjugated diene monomer copolymer weight Total number of repeating units If the value of (D / E) ⁇ 100 is 30% or less, it should be used as an indicator that the aromatic vinyl monomer-conjugated diene monomer copolymer is a random copolymer. Can do.
- the styrene-isoprene copolymers obtained in Examples 1 to 4 of the present invention all have a value of (D / E) ⁇ 100 of 30% or less (within 5 to 20%), and random copolymer weight It is clear that it is a coalescence.
- the molecular weight distribution of the alicyclic hydrocarbon random copolymer of the present invention can be appropriately selected according to the purpose of use, but the weight average molecular weight (Mw) and number average molecular weight in terms of polystyrene (or polyisoprene) measured by GPC.
- the ratio (Mw / Mn) to (Mn) is usually 2.5 or less, preferably 2.3 or less, more preferably 2.0 or less, and in many cases 1.5 or less.
- the lower limit of Mw / Mn is usually 1.1, and in many cases 1.2. When Mw / Mn is in this range, mechanical strength and heat resistance are highly balanced.
- the alicyclic hydrocarbon random copolymer of the present invention comprises an alicyclic vinyl monomer, a conjugated diene monomer, and other vinyl monomers that can be copolymerized as required, with 2 electron-donating atoms. It can be obtained by a method in which solution polymerization is carried out in the presence of a compound having a chelate-forming structure having at least one, and hydrogenated as necessary.
- an aromatic vinyl monomer a conjugated diene monomer, and optionally other vinyl monomers It is preferable to employ a method of copolymerizing the body and then hydrogenating an unsaturated double bond containing an aromatic ring.
- the alicyclic hydrocarbon random copolymer of the present invention includes the following steps I and II: (I) 85 to 99% by weight of an aromatic vinyl monomer, 1 to 15% by weight of at least one conjugated diene monomer selected from the group consisting of isoprene and 1,3-butadiene, and other vinyl monomers 0 to 10% by weight is polymerized in the presence of a compound having an electron donor atom, and a random copolymer having a 1,4-bond content of 70 mol% or less in the repeating unit of the conjugated diene monomer.
- a step I of synthesizing a polymer; and (II) a step II of hydrogenating a carbon-carbon unsaturated double bond of a side chain including a main chain and an aromatic ring of the random copolymer; Can be manufactured.
- R 1 and R 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or an alkyl having 1 to 20 carbon atoms.
- n is 0 or an integer of 1 to 5.
- the aromatic vinyl compound represented by these can be used.
- aromatic vinyl monomer examples include, for example, styrene, ⁇ -methylstyrene, ⁇ -ethylstyrene, ⁇ -propylstyrene, ⁇ -isopropylstyrene, ⁇ -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.
- aromatic vinyl monomers styrene, 2-methylstyrene, 3-methylstyrene, and 4-methylstyrene are preferable, and styrene
- the other vinyl monomer a compound capable of forming a repeating unit represented by Formula 7 is used.
- the vinyl monomer include olefin monomers such as ethylene, propylene, 1-butene, 1-pentene and 4-methyl-1-pentene; 1-cyanoethylene (acrylonitrile), 1-cyano-1 Nitrile monomers such as methylethylene (methacrylonitrile) and 1-cyano-1-chloroethylene ( ⁇ -chloroacrylonitrile); methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate , Acrylate or methacrylic acid ester monomers such as propyl acrylate and butyl acrylate; unsaturated fatty acid monomers such as acrylic acid, methacrylic acid and maleic anhydride; and the like.
- vinyl monomers olefin monomers are preferable, and ethylene, propylene, and 1-butene are more preferable. These vinyl monomers can be used alone or in combination of two or more.
- Step I at least one conjugated diene monomer selected from the group consisting of an aromatic vinyl monomer, isoprene and 1,3-butadiene, and other vinyl monomers as required. Is polymerized in the presence of a compound having an electron donor atom to synthesize a random copolymer having a 1,4-bond content of 70 mol% or less in the repeating unit of the conjugated diene monomer. To do.
- the compound having an electron donor atom a compound having at least one electron donor atom selected from sulfur (S), oxygen (O), phosphorus (P) and the like is preferable.
- a compound having an electron donor atom a compound having a structure capable of forming a chelate having two or more electron donor atoms is preferable.
- a compound having a structure capable of forming a chelate having two or more electron donating atoms a chelate forming having at least two electron donating atoms selected from sulfur (S), oxygen (O), phosphorus (P), etc. Compounds with possible structures are preferred.
- oxygen (O) is more preferable.
- Examples of compounds having a structure capable of forming a chelate having two or more electron donor atoms include ether compounds, tertiary amine compounds, phosphine compounds, alkali metal alkoxide compounds, and the like.
- ether compounds are preferable from the viewpoint of reducing the molecular weight distribution (Mw / Mn) of the random copolymer and not inhibiting the hydrogenation reaction.
- the ether compound examples include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol diisopropyl ether, ethylene glycol dibutyl ether, ethylene glycol methyl phenyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol diisopropyl ether, propylene glycol.
- Bidentate ether compounds such as dibutyl ether and propylene glycol methyl phenyl ether; tridentate ether compounds such as diethylene glycol dibutyl ether and dipropylene glycol dibutyl ether; ethylene glycol alkyl ether and propylene glycol alkyl ether .
- the alkyl moiety usually has 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms.
- a compound having a structure capable of forming a chelate having two or more electron donating atoms is copolymerized with an aromatic vinyl monomer and a conjugated diene monomer, a 3,4-addition reaction of isoprene or 1,1 A 1,2-addition reaction of 3-butadiene is likely to occur, and a random copolymer having a low 1,4-bond content can be obtained.
- the random copolymer has a narrow molecular weight distribution because the molecular weight distribution (Mw / Mn) of the random copolymer tends to be slightly widened.
- randomizers such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and tetrahydrofuran can be used in combination with the compound.
- the compound having an electron donating atom preferably a compound having a structure capable of forming a chelate having two or more electron donating atoms is usually 0.001 to 10 parts by weight, preferably 100 parts by weight based on the total amount of monomers. Is used at a ratio of 0.01 to 1 part by weight.
- the polymerization method is not particularly limited, and examples thereof include a batch polymerization method (batch method) and a monomer sequential addition method.
- the monomer sequential addition method polymerization is performed by sequentially adding a uniformly mixed monomer mixture into a polymerization system in which an initiator is present.
- the sequential monomer addition method a method in which the polymerization is started using a part of the total amount of the monomer mixture used, and then the remaining monomer mixture is sequentially added to proceed with the polymerization.
- a monomer sequential addition method is used, a copolymer having a preferable chain structure is easily obtained.
- the copolymer before hydrogenation has a more random chain structure as the value of (D / E) ⁇ 100 decreases.
- the degree of randomness of the copolymer is determined by the speed ratio between the polymerization rate of the aromatic vinyl monomer and the polymerization rate of the conjugated diene monomer. The smaller this speed ratio, the more random the copolymer is. A copolymer having a simple chain structure can be obtained.
- the uniformly mixed monomer mixture is sequentially added to the polymerization system, so that, unlike the batch method, the polymerization selectivity of the monomer in the growth process by copolymer polymerization. Can be further reduced, and the resulting copolymer has a more random chain structure.
- the polymerization temperature can be kept low and stable.
- the initial monomer is used in a proportion of usually 0.01 to 60% by weight, preferably 0.02 to 20% by weight, more preferably 0.05 to 10% by weight, based on the total amount of monomers used.
- the polymerization is started by adding an initiator in the state of being previously present in the polymerization reactor.
- 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.
- the reaction is continued until the polymerization conversion of the initial monomer is usually 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 taking into account the consumption rate of the monomer in the polymerization system.
- the total monomer polymerization conversion immediately after completion of the monomer addition is usually 80% or more, preferably 85% or more, 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 may be any polymerization method such as radical polymerization, anionic polymerization, and cationic polymerization except that the polymerization reaction is performed in the presence of the specific compound, and there is no particular limitation.
- the anionic polymerization method is preferred in view of various characteristics such as polymerization operation, ease of hydrogenation reaction in the subsequent step, and mechanical strength of the finally obtained alicyclic hydrocarbon random copolymer.
- radical polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization are used in the presence of an initiator and a specific compound, usually at a reaction temperature of 0 to 200 ° C., preferably 20 to 150 ° C. be able to.
- an initiator and a specific compound usually at a reaction temperature of 0 to 200 ° C., preferably 20 to 150 ° C. be able to.
- bulk polymerization and suspension polymerization are desirable when it is necessary to prevent impurities and the like from being mixed into the copolymer.
- organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butyl-peroxy-2-ethylhexanoate; azoisobutyronitrile, 4,4′-azobis-4-cyanopentane
- An azo compound such as acid or azodibenzoyl; a water-soluble catalyst represented by potassium persulfate or ammonium persulfate, a redox initiator, or the like can be used.
- anionic polymerization When anionic polymerization is employed, bulk polymerization, solution polymerization, and polymerization are usually carried out at a polymerization temperature of 0 to 200 ° C., preferably 20 to 100 ° C., particularly preferably 20 to 80 ° C. in the presence of an initiator and a specific compound.
- a method such as slurry polymerization can be used.
- solution polymerization is preferable in view of the removal efficiency of reaction heat.
- Examples of the inert solvent used for the solution polymerization include aliphatic hydrocarbons such as n-butane, n-pentane, iso-pentane, n-hexane, n-heptane, and iso-octane; cyclopentane, cyclohexane, methylcyclo Examples include alicyclic hydrocarbons such as pentane, methylcyclohexane, and decalin; aromatic hydrocarbons such as benzene and toluene. Among these, when aliphatic hydrocarbons or alicyclic hydrocarbons are used, they can be used as they are as an inert solvent in the hydrogenation reaction after copolymerization. These solvents can be used alone or in combination of two or more. The solvent is usually used at a ratio of usually 200 to 10,000 parts by weight with respect to 100 parts by weight of the total amount of monomers.
- anionic polymerization initiator examples include monoorganolithium such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, and phenyllithium; dilithiomethane, 1,4-diobtan, 1,4-dilithio-
- An organolithium compound such as a polyfunctional organolithium compound such as 2-ethylcyclohexane can be used.
- a polymerization accelerator may be used.
- the molecular weight of the copolymer before hydrogenation is in the range of 10,000 to 500,000, preferably 30,000 to 300,000 in terms of weight average molecular weight (Mw) in terms of polystyrene (or polyisoprene) measured by GPC. It is. If the weight average molecular weight (Mw) of the copolymer is excessively small, the weight average molecular weight of the alicyclic hydrocarbon random copolymer obtained by hydrogenation becomes too small, resulting in inferior strength properties of the molded product. If it is too large, the hydrogenation reactivity is poor.
- the random copolymer obtained by radical polymerization or anion polymerization can be recovered from the polymerization reaction system by a known method such as a steam stripping method, a direct desolvation method, or an alcohol coagulation method.
- a solvent inert to the hydrogenation reaction is used during the polymerization, the polymer is not recovered from the polymerization solution and can be used as it is in the hydrogenation step.
- a hydrogenation reaction of an aromatic ring of a random copolymer before hydrogenation or a carbon-carbon unsaturated double bond of a main chain or a side chain there are no particular limitations on the reaction method and reaction form, and according to a known method It can be carried out. Among these, it is preferable to employ a hydrogenation method that can increase the hydrogenation rate and has few polymer chain scission reactions that occur simultaneously with the hydrogenation reaction. Specifically, for example, a method in which hydrogenation is performed using a catalyst containing at least one metal selected from nickel, cobalt, iron, titanium, rhodium, palladium, platinum, ruthenium, and rhenium in an organic solvent. It is done. As the hydrogenation catalyst, either a heterogeneous catalyst or a homogeneous catalyst can be used.
- the heterogeneous catalyst can be used in the form of a metal or a metal compound or supported on a suitable carrier.
- suitable carrier include activated carbon, silica, alumina, calcium carbide, titania, magnesia, zirconia, diatomaceous earth, silicon carbide and the like.
- the supported amount of the catalyst is usually 0.01 to 80% by weight, preferably 0.05 to 60% by weight.
- the homogeneous catalyst is a catalyst in which a nickel, cobalt, titanium or iron compound and an organometallic compound (for example, an organoaluminum compound or an organolithium compound) are combined; an organometallic complex catalyst such as rhodium, palladium, platinum, ruthenium or rhenium; Can be used.
- organometallic complex catalyst such as rhodium, palladium, platinum, ruthenium or rhenium
- the nickel, cobalt, titanium, or iron compound include acetylacetone salts, naphthene salts, cyclopentadienyl compounds, cyclopentadienyl dichloro compounds, and the like of various metals.
- 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.
- organometallic complex catalysts include metal complexes such as ⁇ -dichloro- ⁇ -benzene complex, dichloro-tris (triphenylphosphine) complex, hydrido-chloro-triphenylphosphine) complex of the above metals.
- the hydrogenation catalysts can be used alone or in combination of two or more.
- the amount of the hydrogenation catalyst used is usually 0.01 to 50 parts by weight, preferably 0.05 to 25 parts by weight, more preferably 0.1 to 15 parts by weight with respect to 100 parts by weight of the copolymer.
- the hydrogenation reaction is usually carried out at a temperature of 10 to 250 ° C. Hydrogenation is preferably performed at a temperature of 50 to 200 ° C., more preferably 80 to 180 ° C., because the hydrogenation rate can be increased and the polymer chain scission reaction that occurs simultaneously with the hydrogenation reaction can be reduced. It is desirable to do.
- the hydrogen pressure is usually 0.1 to 30 MPa. In addition to the above reasons, from the viewpoint of operability, the hydrogen pressure is preferably 1 to 20 MPa, more preferably 2 to 10 MPa.
- the hydrogenation rate of the hydride obtained in this way is determined by the measurement by 1 H-NMR of the main chain and / or the side chain carbon-carbon unsaturated bond, the aromatic ring carbon-carbon double bond, etc. Usually, it is 90% or more, preferably 95% or more, more preferably 97% or more, in many cases 99% or more, and further 99.9%.
- the hydrogenation rate is low, the low birefringence, thermal stability, laser resistance and the like of the resulting alicyclic hydrocarbon random copolymer are lowered.
- the method for recovering the hydride after completion of the hydrogenation reaction is not particularly limited.
- a recovery method usually, after removing the hydrogenation catalyst residue by a method such as filtration or centrifugation, the solvent is directly removed from the hydride solution by drying, or the hydride solution is in a poor solvent for the hydride. It is possible to use a method in which the hydride is solidified.
- a resin composition containing an antioxidant in the alicyclic hydrocarbon random copolymer containing an antioxidant in the alicyclic hydrocarbon random copolymer.
- the antioxidant include a phenol antioxidant, a phosphoric acid antioxidant, and a sulfur antioxidant.
- a phenol antioxidant is preferable and an alkyl-substituted phenol antioxidant is more preferable.
- phenol antioxidants include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl- Acrylate compounds such as 6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate; octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate, 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3 , 5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis (methylene-3- (3 ', 5'-di-t- Til-4'-hydroxyphenylpropionate)
- the phosphorylation inhibitor is not particularly limited as long as it is usually used in the general resin industry, and examples thereof include triphenyl phosphite, diphenylisodecyl phosphite, phenyldiisodecyl phosphite, and tris (nonylphenyl) phosphine.
- Tris (dinonylphenyl) phosphite Tris (2,4-di-t-butylphenyl) phosphite, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10- Monophosphite compounds such as dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl phosphite), 4,4'-isopropylidene-bis (phenyl-di-alkyl (C 12 -C 15 ) phosphite ) And the like.
- monophosphite compounds are preferable, and tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite and the like are particularly preferable.
- sulfur antioxidant examples include dilauryl-3,3-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3-thiodipropionate, laurylstearyl-3,3. -Thiodipropionate, pentaerythritol-tetrakis- ( ⁇ -lauryl-thio-propionate, 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane Etc.
- antioxidants can be used alone or in combination of two or more.
- the blending amount of the antioxidant is appropriately selected within a range not impairing the object of the present invention, but is usually 0.001 to 5 parts by weight, preferably 100 parts by weight based on 100 parts by weight of the alicyclic hydrocarbon random copolymer. 0.01 to 1 part by weight.
- a resin composition comprising an alicyclic hydrocarbon random copolymer and at least one compounding agent selected from the group consisting of a soft polymer, an alcoholic compound, an organic filler, and an inorganic filler.
- a compounding agent selected from the group consisting of a soft polymer, an alcoholic compound, an organic filler, and an inorganic filler.
- the soft polymer and the alcoholic compound are excellent in the effect of preventing white turbidity in a high-temperature and high-humidity environment and the transparency of the resulting resin composition.
- the soft polymer used in the present invention is usually a polymer having a Tg of 30 ° C. or lower. When a plurality of Tg are present, at least the lowest Tg may be 30 ° C. or lower.
- soft polymer examples include, for example, liquid polyethylene, polypropylene, poly-1-butene, ethylene- ⁇ -olefin copolymer, propylene- ⁇ -olefin copolymer, ethylene-propylene-diene copolymer (EPDM).
- Olefin soft polymer such as ethylene-propylene-styrene copolymer; isobutylene soft polymer such as polyisobutylene, isobutylene-isoprene rubber, isobutylene-styrene copolymer; polybutadiene, polyisoprene, butadiene-styrene random copolymer Polymer, isoprene-styrene random copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-butadiene-styrene copolymer, butadiene-styrene block copolymer, styrene-butadiene-styrene block copolymer, Diene soft polymers such as soprene-styrene block copolymer, styrene-isoprene-styrene block copolymer; silicon-containing soft polymers such as dimethyl
- Any epoxy soft polymer Fluorine soft polymer such as vinylidene fluoride rubber, tetrafluoroethylene-propylene rubber; natural rubber, polypeptide, protein, polyester thermoplastic elastomer, vinyl chloride thermoplastic elastomer, polyamide thermoplastic elastomer, etc. Examples include other soft polymers. These soft polymers may have a cross-linked structure or may have a functional group introduced by a modification reaction.
- diene soft polymers are preferable, and hydrides obtained by hydrogenating carbon-carbon unsaturated bonds of diene soft polymers are particularly excellent in terms of rubber elasticity, mechanical strength, flexibility, and dispersibility.
- the alcoholic compound is a compound having at least one non-phenolic hydroxyl group in the molecule, and preferably a compound having at least one hydroxyl group and at least one ether bond or ester bond.
- a compound having at least one hydroxyl group and at least one ether bond or ester bond include, for example, a dihydric or higher polyhydric alcohol, more preferably a trihydric or higher polyhydric alcohol, and further 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.
- dihydric or higher polyhydric alcohol examples 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 polyhydric alcohol having a valence of 3 or more, more preferably a polyhydric alcohol having 3 to 8 hydroxyl groups.
- glycerol, diglycerol, triglycerol or the like capable of synthesizing an alcoholic ester compound containing ⁇ , ⁇ -diol is preferable.
- alcoholic compounds include glycerol monostearate, glycerol monolaurate, glycerol monobehenate, diglycerol monostearate, glycerol distearate, glycerol dilaurate, pentaerythritol monostearate, and pentaerythritol monolaurate.
- polyhydric alcohol compounds are used alone or in combination of two or more.
- the molecular weight of these polyhydric alcoholic compounds is not particularly limited, but is usually 500 to 2,000, preferably 800 to 1,500, from the viewpoint of little decrease in transparency.
- organic filler normal organic polymer particles or crosslinked organic polymer particles can be used.
- polyolefins such as polyethylene and polypropylene
- halogen-containing vinyl polymers such as polyvinyl chloride and polyvinylidene chloride
- polymers derived from ⁇ , ⁇ -unsaturated acids such as polyarylate and polymethacrylate.
- Polymers derived from unsaturated alcohols such as polyvinyl alcohol and polyvinyl acetate
- polymers derived from polyethylene oxide or bisglycidyl ether polymers derived from polyethylene oxide or bisglycidyl ether
- aromatic condensation polymers such as polyphenylene oxide, polycarbonate and polysulfone
- polyurethane Polyamide Polyester
- Aldehyde-phenolic resin Natural polymer compound particles or cross-linked particles.
- the inorganic filler examples 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 elements 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; Aluminum oxide (ie, alumina), aluminum fluoride, aluminosilicate (alumina silicate, kaolin, kaolinite), etc.
- 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
- Group 13 element compound silicon oxide (silica, silica Le), graphite, carbon, graphite, Group 14 element compound such as glass; kernal stones, kainite, mica (i.e., mica, Kin'unmo) include particles of natural minerals, such as Bairosu ore.
- the blending amount of at least one compounding agent selected from the group consisting of a soft polymer, an alcoholic compound, and an organic or inorganic filler is determined by the combination of the alicyclic hydrocarbon random copolymer and the compounding agent. If the amount is too large, the glass transition temperature and transparency of the resin composition are greatly lowered, and it is unsuitable for use as an optical material. If the amount is too small, the molded product may become clouded under high temperature and high humidity.
- the blending amount is usually 0.01 to 10 parts by weight, preferably 0.02 to 5 parts by weight, particularly preferably 0.05 to 2 parts by weight with respect to 100 parts by weight of the alicyclic hydrocarbon random copolymer. Is the ratio. When the blending amount is too small, the effect of preventing white turbidity in a high temperature and high humidity environment cannot be obtained. When the blending amount is too large, the heat resistance and transparency of the molded product are lowered.
- ultraviolet absorbers ultraviolet absorbers, light stabilizers, near infrared absorbers, coloring agents such as dyes and pigments, lubricants, plasticizers, antistatic agents, An optical brightener or the like can be blended.
- coloring agents such as dyes and pigments, lubricants, plasticizers, antistatic agents, An optical brightener or the like can be blended.
- These compounding agents can be used alone or in combination of two or more, and the compounding amount is appropriately selected within a range not impairing the object of the present invention.
- the resin composition of the present invention can be obtained by appropriately mixing the above components.
- the mixing method is not particularly limited as long as each component is sufficiently dispersed in the alicyclic hydrocarbon random copolymer.
- a mixer, a twin-screw kneader, a roll, a Brabender, an extruder For example, a method of kneading the mixture in a molten state, a method of dissolving and dispersing in a suitable solvent and solidifying the mixture can be used.
- twin-screw kneader When a twin-screw kneader is used, it is often used as a molding material that is usually extruded after being kneaded into a rod shape in a molten state, cut into an appropriate length with a strand cutter, and pelletized.
- the molded product of the present invention is obtained by molding a molding material comprising an alicyclic hydrocarbon random copolymer or a resin composition.
- melt molding is preferable in order to obtain a molded product having excellent characteristics such as blue laser resistance, low birefringence, mechanical strength, and dimensional accuracy.
- the melt molding method include press molding, extrusion molding, and injection molding. Among these molding methods, injection molding is preferable from the viewpoints of moldability and productivity.
- the molding conditions are appropriately selected depending on the purpose of use or the molding method.
- the resin temperature in injection molding is appropriately selected from the range of usually 150 to 400 ° C., preferably 200 to 350 ° C., more preferably 230 to 330 ° C.
- the molded product of the present invention can be used in various forms such as a spherical shape, a rod shape, a plate shape, a cylindrical shape, a tubular shape, a tubular shape, a fibrous shape, a film shape or a sheet shape.
- the molded product of the present invention is excellent in blue laser resistance, low birefringence, transparency, mechanical strength, heat resistance, and low water absorption, and thus can be used for various applications and is particularly suitable as an optical component.
- optical components include the following.
- Optical lenses and optical prisms include camera imaging lenses; lenses such as microscopes, endoscopes and telescopes; total light transmission lenses such as spectacle lenses; CDs, CD-ROMs, WORM (recordable optical disks), MO (writing Changeable optical discs; magneto-optical discs), MD (mini discs), optical disc pickup lenses such as DVDs (digital video discs); laser scanning lenses such as f ⁇ lenses and sensor lenses for laser beam printers; prisms for camera viewfinders Examples include lenses.
- 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;
- test cells such as medical blood test cells, syringe syringes, pipes and tubes, medical vials and drug solution containers, and insulating films on printed boards.
- the alicyclic hydrocarbon random copolymer and the resin composition of the present invention are suitable as pickup lenses and laser scanning lenses that require blue laser resistance and low birefringence, and are most suitable for pickup lenses. Is preferred.
- Molecular weight The molecular weight of the polymer was measured by GPC using tetrahydrofuran (THF) as a solvent, and the weight average molecular weight (Mw) in terms of standard polystyrene was determined.
- Glass transition temperature (Tg) The glass transition temperature of the polymer was measured using differential scanning calorimetry (DSC) under conditions of a heating rate of 10 ° C./min.
- Binding mode The bonding mode of the conjugated diene monomer was measured by 13 C-NMR.
- Birefringence was measured using a resin molded plate having a thickness of 3 mm, a length of 65 mm, and a width of 65 mm, which was injection-molded at 280 ° C., as a sample.
- the birefringence value at a position 10 mm from the gate at the time of injection molding of the resin molded plate was measured using a polarizing microscope (Nikon Corporation, 546 nm Senarmon Compensator). The closer the birefringence value is to zero, the lower the birefringence.
- the laser resistance is 3 mm in thickness and 65 mm in length from a laser diode (TC35-4030-4.5, manufactured by Neoarc) having a wavelength of 405 ⁇ 10 nm and an output of 400 mW / cm 2 in an environment of 80 ° C. Irradiate a resin molded plate with a width of 65 mm for 480 hours, measure the light transmittance after laser irradiation with a spectrophotometer (manufactured by JASCO Corporation, V-570), and decrease in light transmittance before and after irradiation (%) It was evaluated with. It shows that it is excellent in blue laser resistance, so that the fall amount of the light transmittance of wavelength 400nm before and behind laser irradiation of a shaping
- a laser diode TC35-4030-4.5, manufactured by Neoarc
- the hydrogenation rate of the obtained alicyclic hydrocarbon random copolymer was 99.9%, the weight average molecular weight was 101,000, the number average molecular weight was 76,000, and the glass transition temperature was 128 ° C.
- the alicyclic hydrocarbon random copolymer thus obtained was injection molded to prepare a birefringence measurement sample and a light transmittance measurement sample. The results are shown in Table 1.
- Example 3 As a compound having a chelate-forming structure having two or more electron donor atoms, a polymerization reaction and a procedure similar to those in Example 2 except that 0.69 part of ethylene glycol dimethyl ether was added instead of ethylene glycol dibutyl ether. A hydrogenation reaction was performed, and then the obtained alicyclic hydrocarbon random copolymer was injection-molded to prepare a birefringence measurement sample and a light transmittance measurement sample. The results are shown in Table 1.
- EGDBE ethylene glycol dibutyl ether
- EGDME ethylene glycol dimethyl ether
- n-Bu 2 O dibutyl ether
- Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, and Example 4 and Comparative Example 3 are compared, a compound having an electron-donating atom (preferably an electron) even though the copolymer composition is the same.
- a compound having an electron-donating atom preferably an electron
- a conjugated diene monomer isoprene
- the alicyclic hydrocarbon random copolymer of the present invention is excellent in transparency, low birefringence, mechanical strength, heat resistance, low water absorption, and blue laser resistance, it can be used in various applications.
- the alicyclic hydrocarbon random copolymer of the present invention can be suitably used particularly as a resin material for optical components such as a pickup lens and a laser scanning lens.
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Abstract
Description
(1)該脂環式構造の繰り返し単位〔A〕が、下記式1 According to the present invention, there is an alicyclic hydrocarbon random copolymer containing a repeating unit [A] having an alicyclic structure and a repeating unit [B] having a chain structure,
(1) The repeating unit [A] of the alicyclic structure is represented by the following formula 1
で表される脂環式構造の繰り返し単位であり、
(2)該鎖状構造の繰り返し単位〔B〕が、下記式2 [In Formula 1, R 1 and R 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. Carbonyloxy group, cyano group, amide group, imide group, silyl group, or polar group (halogen atom, hydroxyl group, alkoxy group having 1 to 20 carbon atoms, alkylcarbonyloxy group having 1 to 20 carbon atoms, cyano group, amide group , An imide group or a silyl group) and a hydrocarbon group having 1 to 20 carbon atoms. n is 0 or an integer of 1 to 5. ]
Is a repeating unit of an alicyclic structure represented by:
(2) The repeating unit [B] of the chain structure is represented by the following formula 2
で表わされる繰り返し単位〔B1〕、及び下記式3 (In Formula 2, R 3 is a hydrogen atom or a methyl group.)
A repeating unit [B 1 ] represented by the following formula 3
で表される繰り返し単位〔B2〕を有する鎖状構造の繰り返し単位であり、
(3)該脂環式炭化水素ランダム共重合体中における該脂環式構造の繰り返し単位〔A〕と該鎖状構造の繰り返し単位〔B〕との合計含有量が90重量%以上であり、
(4)該脂環式炭化水素ランダム共重合体中における該鎖状構造の繰り返し単位〔B〕の含有量が1~15重量%であり、
(5)該鎖状構造の繰り返し単位〔B〕中における該繰り返し単位〔B1〕の含有量が70モル%以下であり、並びに
(6)ゲルパーミエーションクロマトグラフィにより測定した該脂環式炭化水素ランダム共重合体の重量平均分子量(Mw)が10,000~300,000の範囲内である、
ことを特徴とする脂環式炭化水素ランダム共重合体が提供される。 (In Formula 3, R 3 is a hydrogen atom or a methyl group.)
A repeating unit of a chain structure having a repeating unit [B 2 ] represented by:
(3) The total content of the alicyclic structure repeating unit [A] and the chain structure repeating unit [B] in the alicyclic hydrocarbon random copolymer is 90% by weight or more,
(4) The content of the repeating unit [B] of the chain structure in the alicyclic hydrocarbon random copolymer is 1 to 15% by weight,
(5) The content of the repeating unit [B 1 ] in the repeating unit [B] of the chain structure is 70 mol% or less, and (6) the alicyclic hydrocarbon measured by gel permeation chromatography The random copolymer has a weight average molecular weight (Mw) in the range of 10,000 to 300,000.
An alicyclic hydrocarbon random copolymer is provided.
(I)芳香族ビニル単量体85~99重量%と、イソプレン及び1,3-ブタジエンからなる群より選ばれる少なくとも一種の共役ジエン単量体1~15重量%と、その他のビニル単量体0~10重量%とを、電子供与原子を有する化合物の存在下で重合して、該共役ジエン単量体の繰り返し単位中での1,4-結合の含有量が70モル%以下のランダム共重合体を合成する工程I;並びに
(II)該ランダム共重合体の主鎖及び芳香環を含む側鎖の炭素-炭素不飽和二重結合を水素化する工程II;
を含む前記脂環式炭化水素ランダム共重合体の製造方法が提供される。 Also according to the present invention, the following steps I and II:
(I) 85 to 99% by weight of an aromatic vinyl monomer, 1 to 15% by weight of at least one conjugated diene monomer selected from the group consisting of isoprene and 1,3-butadiene, and other vinyl monomers 0 to 10% by weight is polymerized in the presence of a compound having an electron donor atom, and a random copolymer having a 1,4-bond content of 70 mol% or less in the repeating unit of the conjugated diene monomer. A step I of synthesizing a polymer; and (II) a step II of hydrogenating a carbon-carbon unsaturated double bond of a side chain including a main chain and an aromatic ring of the random copolymer;
The manufacturing method of the said alicyclic hydrocarbon random copolymer containing is provided.
で表わされる繰り返し単位〔B1〕、及び下記式3 (In Formula 2, R 3 is a hydrogen atom or a methyl group.)
A repeating unit [B 1 ] represented by the following formula 3
で表される繰り返し単位〔B2〕を有する鎖状構造を持つ繰り返し単位である。 (In Formula 3, R 3 is a hydrogen atom or a methyl group.)
It is a repeating unit having a chain structure having a repeating unit [B 2 ] represented by
で表わされる水素化されていない芳香族ビニル単量体の繰り返し単位、下記式5 (R 1 and R 2 in Formula 4 are the same as in Formula 1.)
A repeating unit of an unhydrogenated aromatic vinyl monomer represented by formula 5
で表わされる水素化されていないイソプレン及び/または1,3-ブタジエンの1,4-付加反応による繰り返し単位、下記式6 (In Formula 5, R 3 is a hydrogen atom or a methyl group.)
A repeating unit obtained by 1,4-addition reaction of unhydrogenated isoprene and / or 1,3-butadiene represented by the following formula 6
で表わされる水素化されていないイソプレンの3,4-付加反応及び/または1,3-ブタジエンの1,2-付加反応による繰り返し単位、下記式7 (In Formula 6, R 3 is a hydrogen atom or a methyl group.)
A repeating unit represented by the following formula 7: 3,4-addition reaction of unhydrogenated isoprene and / or 1,2-addition reaction of 1,3-butadiene:
で表わされるその他のビニル単量体の繰り返し単位、またはこれらの2種以上の繰り返し単位の含有量である。 [In formula 7, R 4 to R 7 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 1 to 20 carbon atoms. Carbonyloxy group, cyano group, amide group, imide group, silyl group, or polar group (halogen atom, hydroxyl group, alkoxy group having 1 to 20 carbon atoms, alkylcarbonyloxy group having 1 to 20 carbon atoms, cyano group, amide group , An imide group or a silyl group) and a hydrocarbon group having 1 to 20 carbon atoms. ]
It is content of the repeating unit of the other vinyl monomer represented by these, or these 2 or more types of repeating units.
D=芳香族ビニル単量体連鎖の重量平均分子量(Mw)、かつ、
E=〔芳香族ビニル単量体-共役ジエン単量体共重合体の重量平均分子量×芳香族ビニル単量体単位由来の繰り返し単位数/芳香族ビニル単量体-共役ジエン単量体共重合体の全繰り返し単位数〕
としたとき、(D/E)×100の値が30%以下であることが、芳香族ビニル単量体-共役ジエン単量体共重合体がランダム共重合体であることの指標として用いることができる。本発明の実施例1~4で得られたスチレン-イソプレン共重合体は、いずれも(D/E)×100の値が30%以下(5~20%の範囲内)であり、ランダム共重合体であることが明らかである。 here,
D = weight average molecular weight (Mw) of the aromatic vinyl monomer chain, and
E = [weight average molecular weight of aromatic vinyl monomer-conjugated diene monomer copolymer × number of repeating units derived from aromatic vinyl monomer unit / aromatic vinyl monomer-conjugated diene monomer copolymer weight Total number of repeating units
If the value of (D / E) × 100 is 30% or less, it should be used as an indicator that the aromatic vinyl monomer-conjugated diene monomer copolymer is a random copolymer. Can do. The styrene-isoprene copolymers obtained in Examples 1 to 4 of the present invention all have a value of (D / E) × 100 of 30% or less (within 5 to 20%), and random copolymer weight It is clear that it is a coalescence.
(I)芳香族ビニル単量体85~99重量%と、イソプレン及び1,3-ブタジエンからなる群より選ばれる少なくとも一種の共役ジエン単量体1~15重量%と、その他のビニル単量体0~10重量%とを、電子供与原子を有する化合物の存在下で重合して、該共役ジエン単量体の繰り返し単位中での1,4-結合の含有量が70モル%以下のランダム共重合体を合成する工程I;並びに
(II)該ランダム共重合体の主鎖及び芳香環を含む側鎖の炭素-炭素不飽和二重結合を水素化する工程II;
により製造することができる。 More specifically, the alicyclic hydrocarbon random copolymer of the present invention includes the following steps I and II:
(I) 85 to 99% by weight of an aromatic vinyl monomer, 1 to 15% by weight of at least one conjugated diene monomer selected from the group consisting of isoprene and 1,3-butadiene, and other vinyl monomers 0 to 10% by weight is polymerized in the presence of a compound having an electron donor atom, and a random copolymer having a 1,4-bond content of 70 mol% or less in the repeating unit of the conjugated diene monomer. A step I of synthesizing a polymer; and (II) a step II of hydrogenating a carbon-carbon unsaturated double bond of a side chain including a main chain and an aromatic ring of the random copolymer;
Can be manufactured.
で表わされる芳香族ビニル化合物を用いることができる。 [In Formula 8, R 1 and R 2 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, or an alkyl having 1 to 20 carbon atoms. Carbonyloxy group, cyano group, amide group, imide group, silyl group, or polar group (halogen atom, hydroxyl group, alkoxy group having 1 to 20 carbon atoms, alkylcarbonyloxy group having 1 to 20 carbon atoms, cyano group, amide group , An imide group or a silyl group) and a hydrocarbon group having 1 to 20 carbon atoms. n is 0 or an integer of 1 to 5. ]
The aromatic vinyl compound represented by these can be used.
ポリマーの分子量は、テトラヒドロフラン(THF)を溶媒にしてGPCで測定し、標準ポリスチレン換算の重量平均分子量(Mw)を求めた。 (1) Molecular weight:
The molecular weight of the polymer was measured by GPC using tetrahydrofuran (THF) as a solvent, and the weight average molecular weight (Mw) in terms of standard polystyrene was determined.
ポリマーの分子量分布は、THFを溶媒にしてGPCで測定して、標準ポリスチレン換算の重量平均分子量(Mw)と数平均分子量(Mn)を求め、両者の比(Mw/Mn)を算出した。 (2) Molecular weight distribution:
The molecular weight distribution of the polymer was measured by GPC using THF as a solvent, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene were determined, and the ratio (Mw / Mn) between them was calculated.
ポリマーのガラス転移温度は、示差走査熱量分析(DSC)を用いて、昇温速度10℃/分の条件で測定した。 (3) Glass transition temperature (Tg):
The glass transition temperature of the polymer was measured using differential scanning calorimetry (DSC) under conditions of a heating rate of 10 ° C./min.
共重合体の水素化率は、1H-NMRにより測定した。 (4) Hydrogenation rate:
The hydrogenation rate of the copolymer was measured by 1 H-NMR.
共役ジエン単量体の結合様式は、13C-NMRにより測定した。 (5) Binding mode:
The bonding mode of the conjugated diene monomer was measured by 13 C-NMR.
複屈折は、280℃で射出成形した厚さ3mm、縦65mm、横65mmの樹脂成形板を試料として用いて測定した。樹脂成形板の射出成形時のゲートから10mmの位置における複屈折値を、偏光顕微鏡(ニコン社製、546nmセナルモンコンペンセータ)を用いて測定した。複屈折値がゼロに近いほど、低複屈折であることを示す。 (6) Birefringence:
Birefringence was measured using a resin molded plate having a thickness of 3 mm, a length of 65 mm, and a width of 65 mm, which was injection-molded at 280 ° C., as a sample. The birefringence value at a position 10 mm from the gate at the time of injection molding of the resin molded plate was measured using a polarizing microscope (Nikon Corporation, 546 nm Senarmon Compensator). The closer the birefringence value is to zero, the lower the birefringence.
耐レーザー性は、80℃の環境下で、波長405±10nm、出力400mW/cm2のレーザーダイオード(ネオアーク社製、TC35-4030-4.5)からのレーザ光を、厚さ3mm、縦65mm、横65mmの樹脂成形板に480時間照射し、レーザー照射後の光線透過率を分光光度計(日本分光社製、V-570)で測定し、照射前後の光線透過率の低下量(%)で評価した。成形板のレーザー照射前後における波長400nmの光線透過率の低下量が小さい程、耐ブルーレーザー性に優れることを示す。 (7) Laser resistance:
The laser resistance is 3 mm in thickness and 65 mm in length from a laser diode (TC35-4030-4.5, manufactured by Neoarc) having a wavelength of 405 ± 10 nm and an output of 400 mW / cm 2 in an environment of 80 ° C. Irradiate a resin molded plate with a width of 65 mm for 480 hours, measure the light transmittance after laser irradiation with a spectrophotometer (manufactured by JASCO Corporation, V-570), and decrease in light transmittance before and after irradiation (%) It was evaluated with. It shows that it is excellent in blue laser resistance, so that the fall amount of the light transmittance of wavelength 400nm before and behind laser irradiation of a shaping | molding board is small.
十分に乾燥し、窒素置換した、電磁攪拌装置を備えたステンレス鋼製オートクレーブに、脱水シクロヘキサン1,286部、電子供与原子を2個以上有するキレート形成可能な構造を持つ化合物としてエチレングリコールジブチルエーテル1.34部を仕込み、50℃で攪拌しながらn-ブチルリチウム溶液(15%含有ヘキサン溶液)1.97部を添加し、そこに、組成が重量比で〔スチレン(St)/イソプレン(Ip)〕=(96.4/3.6)である混合モノマーを連続的に添加して重合を開始した。4時間かけて混合モノマーを合計500部滴下した。滴下終了後、同条件下で30分間重合を行った後、イソプロピルアルコール0.46部を添加して反応を停止させ、スチレン-イソプレン・ランダム共重合体を合成した。 [Example 1]
Ethylene glycol dibutyl ether 1 as a compound having a chelate-forming structure having 1,286 parts of dehydrated cyclohexane and two or more electron-donating atoms in a stainless steel autoclave equipped with an electromagnetic stirrer, sufficiently dried and purged with nitrogen .34 parts was added and 1.97 parts of n-butyllithium solution (15% hexane solution) was added while stirring at 50 ° C., and the composition was in a weight ratio [styrene (St) / isoprene (Ip)]. ] = (96.4 / 3.6) was continuously added to start the polymerization. A total of 500 parts of the mixed monomer was added dropwise over 4 hours. After completion of the dropwise addition, polymerization was carried out for 30 minutes under the same conditions, and then 0.46 part of isopropyl alcohol was added to stop the reaction to synthesize a styrene-isoprene random copolymer.
モノマー組成が重量比で(St/Ip)=(95/5)の混合モノマーを使用したこと以外は、実施例1と同様の手順で重合反応及び水素化反応を行い、次いで、得られた脂環式炭化水素ランダム共重合体を射出成形して、複屈折測定用試料と光線透過率測定用試料を作製した。結果を表1に示す。 [Example 2]
A polymerization reaction and a hydrogenation reaction were performed in the same procedure as in Example 1 except that a mixed monomer having a monomer composition of (St / Ip) = (95/5) in weight ratio was used. A cyclic hydrocarbon random copolymer was injection-molded to prepare a birefringence measurement sample and a light transmittance measurement sample. The results are shown in Table 1.
電子供与原子を2個以上有するキレート形成可能な構造を持つ化合物として、エチレングリコールジブチルエーテルの代わりにエチレングリコールジメチルエーテル0.69部を添加したこと以外は、実施例2と同様の手順で重合反応及び水素化反応を行い、次いで、得られた脂環式炭化水素ランダム共重合体を射出成形して、複屈折測定用試料と光線透過率測定用試料を作製した。結果を表1に示す。 [Example 3]
As a compound having a chelate-forming structure having two or more electron donor atoms, a polymerization reaction and a procedure similar to those in Example 2 except that 0.69 part of ethylene glycol dimethyl ether was added instead of ethylene glycol dibutyl ether. A hydrogenation reaction was performed, and then the obtained alicyclic hydrocarbon random copolymer was injection-molded to prepare a birefringence measurement sample and a light transmittance measurement sample. The results are shown in Table 1.
モノマー組成が重量比で(St/Ip)=(90/10)の混合モノマーを使用したこと以外は、実施例1と同様の手順で重合反応及び水素化反応を行い、次いで、得られた脂環式炭化水素ランダム共重合体を射出成形して、複屈折測定用試料と光線透過率測定用試料を作製した。結果を表1に示す。 [Example 4]
A polymerization reaction and a hydrogenation reaction were performed in the same procedure as in Example 1 except that a mixed monomer having a monomer composition of (St / Ip) = (90/10) by weight ratio was used. A cyclic hydrocarbon random copolymer was injection-molded to prepare a birefringence measurement sample and a light transmittance measurement sample. The results are shown in Table 1.
エチレングリコールジブチルエーテルに代えて、ランダマイザーのジブチルエーテル1.00部を添加し、60℃で攪拌しながら重合したこと以外は、実施例1と同様の手順で重合反応及び水素化反応を行い、次いで、得られた脂環式炭化水素ランダム共重合体を射出成形して、複屈折測定用試料と光線透過率測定用試料を作製した。結果を表1に示す。 [Comparative Example 1]
Instead of ethylene glycol dibutyl ether, 1.00 part of randomizer dibutyl ether was added, and the polymerization reaction and the hydrogenation reaction were performed in the same procedure as in Example 1 except that the polymerization was conducted while stirring at 60 ° C. Subsequently, the obtained alicyclic hydrocarbon random copolymer was injection-molded to prepare a birefringence measurement sample and a light transmittance measurement sample. The results are shown in Table 1.
エチレングリコールジブチルエーテルに代えて、ランダマイザーのジブチルエーテル1.00部を添加し、60℃で攪拌しながら重合したこと以外は、実施例2と同様の手順で重合反応及び水素化反応を行い、次いで、得られた脂環式炭化水素ランダム共重合体を射出成形して、複屈折測定用試料と光線透過率測定用試料を作製した。結果を表1に示す。 [Comparative Example 2]
Instead of ethylene glycol dibutyl ether, 1.00 part of randomizer dibutyl ether was added, and the polymerization reaction and the hydrogenation reaction were performed in the same procedure as in Example 2 except that the polymerization was conducted while stirring at 60 ° C. Subsequently, the obtained alicyclic hydrocarbon random copolymer was injection-molded to prepare a birefringence measurement sample and a light transmittance measurement sample. The results are shown in Table 1.
エチレングリコールジブチルエーテルに代えて、ランダマイザーのジブチルエーテル1.00部を添加し、60℃で攪拌しながら重合したこと以外は、実施例4と同様の手順で重合反応及び水素化反応を行い、次いで、得られた脂環式炭化水素ランダム共重合体を射出成形して、複屈折測定用試料と光線透過率測定用試料を作製した。結果を表1に示す。 [Comparative Example 3]
Instead of ethylene glycol dibutyl ether, 1.00 part of randomizer dibutyl ether was added, and the polymerization reaction and the hydrogenation reaction were carried out in the same procedure as in Example 4 except that the polymerization was conducted while stirring at 60 ° C. Subsequently, the obtained alicyclic hydrocarbon random copolymer was injection-molded to prepare a birefringence measurement sample and a light transmittance measurement sample. The results are shown in Table 1.
(1)EGDBE:エチレングリコールジブチルエーテル、
(2)EGDME:エチレングリコールジメチルエーテル、
(3)n-Bu2O:ジブチルエーテル。 (footnote)
(1) EGDBE: ethylene glycol dibutyl ether
(2) EGDME: ethylene glycol dimethyl ether,
(3) n-Bu 2 O: dibutyl ether.
表1の結果から、以下のことが分かる。 <Discussion>
From the results in Table 1, the following can be understood.
Claims (20)
- 脂環式構造の繰り返し単位〔A〕と鎖状構造の繰り返し単位〔B〕とを含有する脂環式炭化水素ランダム共重合体であって、
(1)該脂環式構造の繰り返し単位〔A〕が、下記式1
で表される脂環式構造の繰り返し単位であり、
(2)該鎖状構造の繰り返し単位〔B〕が、下記式2
で表わされる繰り返し単位〔B1〕、及び下記式3
で表される繰り返し単位〔B2〕を有する鎖状構造の繰り返し単位であり、
(3)該脂環式炭化水素ランダム共重合体中における該脂環式構造の繰り返し単位〔A〕と該鎖状構造の繰り返し単位〔B〕との合計含有量が90重量%以上であり、
(4)該脂環式炭化水素ランダム共重合体中における該鎖状構造の繰り返し単位〔B〕の含有量が1~15重量%であり、
(5)該鎖状構造の繰り返し単位〔B〕中における該繰り返し単位〔B1〕の含有量が70モル%以下であり、並びに
(6)ゲルパーミエーションクロマトグラフィにより測定した該脂環式炭化水素ランダム共重合体の重量平均分子量(Mw)が10,000~300,000の範囲内である、
ことを特徴とする脂環式炭化水素ランダム共重合体。 An alicyclic hydrocarbon random copolymer containing a repeating unit [A] having an alicyclic structure and a repeating unit [B] having a chain structure,
(1) The repeating unit [A] of the alicyclic structure is represented by the following formula 1
Is a repeating unit of an alicyclic structure represented by:
(2) The repeating unit [B] of the chain structure is represented by the following formula 2
A repeating unit [B 1 ] represented by the following formula 3
A repeating unit of a chain structure having a repeating unit [B 2 ] represented by:
(3) The total content of the alicyclic structure repeating unit [A] and the chain structure repeating unit [B] in the alicyclic hydrocarbon random copolymer is 90% by weight or more,
(4) The content of the repeating unit [B] of the chain structure in the alicyclic hydrocarbon random copolymer is 1 to 15% by weight,
(5) The content of the repeating unit [B 1 ] in the repeating unit [B] of the chain structure is 70 mol% or less, and (6) the alicyclic hydrocarbon measured by gel permeation chromatography The random copolymer has a weight average molecular weight (Mw) in the range of 10,000 to 300,000.
An alicyclic hydrocarbon random copolymer. - 該脂環式炭化水素ランダム共重合体中における脂環式構造の繰り返し単位〔A〕と鎖状構造の繰り返し単位〔B〕の合計含有量が、90~99.9重量%の範囲内である請求項1記載の脂環式炭化水素ランダム共重合体。 The total content of the alicyclic repeating unit [A] and the chain repeating unit [B] in the alicyclic hydrocarbon random copolymer is in the range of 90 to 99.9% by weight. The alicyclic hydrocarbon random copolymer according to claim 1.
- 該脂環式炭化水素ランダム共重合体中における該鎖状構造の繰り返し単位〔B〕の含有量が、2~10重量%である請求項1記載の脂環式炭化水素ランダム共重合体。 The alicyclic hydrocarbon random copolymer according to claim 1, wherein the content of the repeating unit [B] of the chain structure in the alicyclic hydrocarbon random copolymer is 2 to 10% by weight.
- 前記繰り返し単位〔B1〕が、イソプレンの1,4-結合の繰り返し単位及び1,3-ブタジエンの1,4-結合の繰り返し単位からなる群より選ばれる少なくとも一種の繰り返し単位中の炭素-炭素不飽和二重結合を水素化した繰り返し単位であり、かつ、前記繰り返し単位〔B2〕が、イソプレンの3,4-結合の繰り返し単位及び1,3-ブタジエンの1,2-結合の繰り返し単位からなる群より選ばれる少なくとも一種の繰り返し単位中のペンダント炭素-炭素不飽和二重結合を水素化した繰り返し単位である請求項1記載の脂環式炭化水素ランダム共重合体。 The carbon-carbon in the repeating unit [B 1 ] is at least one repeating unit selected from the group consisting of a repeating unit of 1,4-bond of isoprene and a repeating unit of 1,4-bond of 1,3-butadiene. It is a repeating unit obtained by hydrogenating an unsaturated double bond, and the repeating unit [B 2 ] is a repeating unit of 3,4-bond of isoprene and a repeating unit of 1,2-bond of 1,3-butadiene. The alicyclic hydrocarbon random copolymer according to claim 1, which is a repeating unit obtained by hydrogenating a pendant carbon-carbon unsaturated double bond in at least one repeating unit selected from the group consisting of:
- 前記鎖状構造の繰り返し単位〔B〕中における該繰り返し単位〔B1〕の含有量が、40~70モル%の範囲内である請求項1記載の脂環式炭化水素ランダム共重合体。 The alicyclic hydrocarbon random copolymer according to claim 1, wherein the content of the repeating unit [B 1 ] in the repeating unit [B] of the chain structure is in the range of 40 to 70 mol%.
- 該脂環式炭化水素ランダム共重合体の示差走査熱量計を用いて測定したガラス転移温度が、100℃以上である請求項1記載の脂環式炭化水素ランダム共重合体。 The alicyclic hydrocarbon random copolymer according to claim 1, wherein the alicyclic hydrocarbon random copolymer has a glass transition temperature measured by using a differential scanning calorimeter of 100 ° C or higher.
- 該脂環式炭化水素ランダム共重合体のゲルパーミエーションクロマトグラフィにより測定される標準ポリスチレン換算の重量平均分子量Mwと数平均分子量Mnとの比Mw/Mnで表わされる分子量分布が、2.5以下である請求項1記載の脂環式炭化水素ランダム共重合体。 The molecular weight distribution represented by the ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn in terms of standard polystyrene measured by gel permeation chromatography of the alicyclic hydrocarbon random copolymer is 2.5 or less. The alicyclic hydrocarbon random copolymer according to claim 1.
- 下記工程I及びII:
(I)芳香族ビニル単量体85~99重量%と、イソプレン及び1,3-ブタジエンからなる群より選ばれる少なくとも一種の共役ジエン単量体1~15重量%と、その他のビニル単量体0~10重量%とを、電子供与原子を有する化合物の存在下で重合して、該共役ジエン単量体の繰り返し単位中での1,4-結合の含有量が70モル%以下のランダム共重合体を合成する工程I;並びに
(II)該ランダム共重合体の主鎖及び芳香環を含む側鎖の炭素-炭素不飽和二重結合を水素化する工程II;
を含む請求項1記載の脂環式炭化水素ランダム共重合体の製造方法。 Steps I and II below:
(I) 85 to 99% by weight of an aromatic vinyl monomer, 1 to 15% by weight of at least one conjugated diene monomer selected from the group consisting of isoprene and 1,3-butadiene, and other vinyl monomers 0 to 10% by weight is polymerized in the presence of a compound having an electron donor atom, and a random copolymer having a 1,4-bond content of 70 mol% or less in the repeating unit of the conjugated diene monomer. A step I of synthesizing a polymer; and (II) a step II of hydrogenating a carbon-carbon unsaturated double bond of a side chain including a main chain and an aromatic ring of the random copolymer;
The manufacturing method of the alicyclic hydrocarbon random copolymer of Claim 1 containing this. - 該芳香族ビニル単量体が、スチレンである請求項8記載の製造方法。 The method according to claim 8, wherein the aromatic vinyl monomer is styrene.
- 該電子供与原子を有する化合物が、硫黄原子、酸素原子、及び燐原子からなる群より選ばれる少なくとも一種の電子供与原子を有する化合物である請求項8記載の製造方法。 The production method according to claim 8, wherein the compound having an electron donor atom is a compound having at least one electron donor atom selected from the group consisting of a sulfur atom, an oxygen atom, and a phosphorus atom.
- 該電子供与原子を有する化合物が、硫黄原子、酸素原子、及び燐原子からなる群より選ばれる少なくとも一種の電子供与原子を2個以上有するキレート形成可能な構造を持つ化合物である請求項8記載の製造方法。 The compound having an electron donating atom is a compound having a chelate-forming structure having at least two electron donating atoms selected from the group consisting of a sulfur atom, an oxygen atom, and a phosphorus atom. Production method.
- 該電子供与原子を2個以上有するキレート形成可能な構造を持つ化合物が、エーテル化合物である請求項11記載の製造方法。 The production method according to claim 11, wherein the compound having a structure capable of forming a chelate having two or more electron-donating atoms is an ether compound.
- 該エーテル化合物が、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジイソプロピルエーテル、エチレングリコールジブチルエーテル、エチレングリコールメチルフェニルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールジイソプロピルエーテル、プロピレングリコールジブチルエーテル、及びプロピレングリコールメチルフェニルエーテルから選ばれる二座配位型エーテル化合物;ジエチレングリコールジブチルエーテル、及びジプロピレングリコールジブチルエーテルから選ばれる三座配位型エーテル化合物;エチレングリコールアルキルエーテル(アルキル部分の炭素数1~6);及びプロピレングリコールアルキルエーテル(アルキル部分の炭素数1~6)からなる群より選ばれる少なくとも一種のエーテル化合物である請求項12記載の製造方法。 The ether compound is ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol diisopropyl ether, ethylene glycol dibutyl ether, ethylene glycol methyl phenyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol diisopropyl ether, propylene glycol dibutyl ether, and A bidentate ether compound selected from propylene glycol methyl phenyl ether; a tridentate ether compound selected from diethylene glycol dibutyl ether and dipropylene glycol dibutyl ether; ethylene glycol alkyl ether (carbon number of the alkyl moiety of 1 to 6) ); And propylene glycol At least one is a ether compound according to claim 12 manufacturing method according selected from the group consisting kill ether (having 1 to 6 carbon atoms in the alkyl moiety).
- 該電子供与原子を有する化合物の割合が、単量体の合計量100重量部に対して、0.001~10重量部である請求項8記載の製造方法。 The production method according to claim 8, wherein the proportion of the compound having an electron donor atom is 0.001 to 10 parts by weight with respect to 100 parts by weight of the total amount of monomers.
- 前記ランダム共重合体を合成する工程Iにおいて、単量体混合物の逐次添加法により重合を行う請求項8記載の製造方法。 The production method according to claim 8, wherein in the step I of synthesizing the random copolymer, polymerization is performed by a sequential addition method of a monomer mixture.
- 前記ランダム共重合体を合成する工程Iにおいて、不活性有機溶媒中、有機リチウム化合物からなる開始剤と電子供与原子を有する化合物とが存在する重合系内に、単量体混合物を逐次添加して、0~200℃の重合温度で重合を行う請求項15記載の製造方法。 In Step I of synthesizing the random copolymer, a monomer mixture is sequentially added to a polymerization system in which an initiator composed of an organolithium compound and a compound having an electron donor atom are present in an inert organic solvent. The process according to claim 15, wherein the polymerization is carried out at a polymerization temperature of 0 to 200 ° C.
- 請求項1記載の脂環式炭化水素ランダム共重合体と酸化防止剤とを含有する樹脂組成物。 A resin composition comprising the alicyclic hydrocarbon random copolymer according to claim 1 and an antioxidant.
- 該脂環式炭化水素ランダム共重合体が、30℃以下のガラス転移温度を有する軟質重合体、アルコール性化合物、有機フィラー、及び無機フィラーからなる群より選ばれる少なくとも一種の配合剤をさらに含有する請求項17記載の樹脂組成物。 The alicyclic hydrocarbon random copolymer further contains at least one compounding agent selected from the group consisting of a soft polymer having a glass transition temperature of 30 ° C. or lower, an alcoholic compound, an organic filler, and an inorganic filler. The resin composition according to claim 17.
- 請求項1記載の脂環式炭化水素ランダム共重合体または該脂環式ランダム共重合体と酸化防止剤とを含有する樹脂組成物を成形してなる成形物。 A molded product formed by molding the alicyclic hydrocarbon random copolymer according to claim 1 or a resin composition containing the alicyclic random copolymer and an antioxidant.
- 光学部品である請求項19記載の成形物。 The molded article according to claim 19, which is an optical component.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010143960A (en) * | 2008-12-16 | 2010-07-01 | Nippon Zeon Co Ltd | Alicyclic hydrocarbon random copolymer, method of manufacturing the same, resin composition, and molded matter |
WO2019159672A1 (en) * | 2018-02-14 | 2019-08-22 | 日本ゼオン株式会社 | Acid anhydride group-containing block copolymer, resin composition, resin sheet, and laminated glass |
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JP6780348B2 (en) * | 2016-07-28 | 2020-11-04 | 日本ゼオン株式会社 | Block copolymer hydride |
CN111995712A (en) * | 2020-08-28 | 2020-11-27 | 上海东升新材料有限公司 | High-solid-content styrene-butadiene latex as well as preparation method and application thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001048924A (en) * | 1999-08-12 | 2001-02-20 | Nippon Zeon Co Ltd | Alicyclic hydrocarbon-based copolymer |
JP2001272501A (en) * | 2000-03-28 | 2001-10-05 | Nippon Zeon Co Ltd | Plastic lens |
JP2002025108A (en) * | 2000-07-05 | 2002-01-25 | Teijin Ltd | Optical disk substrate consisting of alicyclic polyolefin |
JP2006189523A (en) * | 2004-12-30 | 2006-07-20 | Nippon Zeon Co Ltd | Light guide plate |
Family Cites Families (4)
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JP3069173B2 (en) * | 1991-11-06 | 2000-07-24 | 旭化成工業株式会社 | Hydrogenated butadiene copolymer composition |
JP3137768B2 (en) * | 1992-03-05 | 2001-02-26 | 旭化成株式会社 | Recycling method of impact-resistant styrenic resin molding |
JP4863566B2 (en) * | 2001-03-26 | 2012-01-25 | 旭化成ケミカルズ株式会社 | Process for producing modified conjugated diene polymer |
CN100497406C (en) * | 2005-05-10 | 2009-06-10 | 中国石油化工集团公司 | Process of controlling 1.2-structure content and distribution in polybutyldiene |
-
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- 2008-10-21 CN CN2008801233938A patent/CN101910213B/en active Active
- 2008-10-21 WO PCT/JP2008/069011 patent/WO2009084308A1/en active Application Filing
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- 2008-10-21 KR KR1020107014176A patent/KR101524893B1/en active IP Right Grant
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001048924A (en) * | 1999-08-12 | 2001-02-20 | Nippon Zeon Co Ltd | Alicyclic hydrocarbon-based copolymer |
JP2001272501A (en) * | 2000-03-28 | 2001-10-05 | Nippon Zeon Co Ltd | Plastic lens |
JP2002025108A (en) * | 2000-07-05 | 2002-01-25 | Teijin Ltd | Optical disk substrate consisting of alicyclic polyolefin |
JP2006189523A (en) * | 2004-12-30 | 2006-07-20 | Nippon Zeon Co Ltd | Light guide plate |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010143960A (en) * | 2008-12-16 | 2010-07-01 | Nippon Zeon Co Ltd | Alicyclic hydrocarbon random copolymer, method of manufacturing the same, resin composition, and molded matter |
WO2019159672A1 (en) * | 2018-02-14 | 2019-08-22 | 日本ゼオン株式会社 | Acid anhydride group-containing block copolymer, resin composition, resin sheet, and laminated glass |
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TWI475065B (en) | 2015-03-01 |
CN101910213A (en) | 2010-12-08 |
CN101910213B (en) | 2012-07-18 |
JPWO2009084308A1 (en) | 2011-05-12 |
KR101524893B1 (en) | 2015-06-01 |
TW200927816A (en) | 2009-07-01 |
KR20100100907A (en) | 2010-09-15 |
JP5440178B2 (en) | 2014-03-12 |
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