WO2015060310A1 - βフェランドレン重合体、その製造方法及び成形品 - Google Patents
βフェランドレン重合体、その製造方法及び成形品 Download PDFInfo
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- WO2015060310A1 WO2015060310A1 PCT/JP2014/077979 JP2014077979W WO2015060310A1 WO 2015060310 A1 WO2015060310 A1 WO 2015060310A1 JP 2014077979 W JP2014077979 W JP 2014077979W WO 2015060310 A1 WO2015060310 A1 WO 2015060310A1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
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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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
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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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- 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
- C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F132/02—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
- C08F132/06—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having two or more carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Definitions
- the present invention relates to a ⁇ -ferrandylene polymer, a production method thereof and a molded product.
- the present application includes Japanese Patent Application No. 2013-218510 filed in Japan on October 21, 2013, and Japanese Patent Application Nos. 2014-060269 and 2014-060270 filed in Japan on March 24, 2014. Claim the priority based on, the contents of which are incorporated herein.
- Patent Document 2 discloses cycloolefin copolymers which are copolymers of alicyclic hydrocarbon polymers obtained by copolymerizing a cyclic olefin and a chain olefin in the presence of a predetermined catalyst. The manufacturing method of this is proposed.
- the monomer used as the raw material for the above-described alicyclic hydrocarbon-based polymer is a petroleum-derived compound, it is not a carbon neutral material that suppresses the emission of carbon dioxide.
- carbon-neutral polymer materials compounds that can be produced through biosynthetic pathways in living organisms have attracted attention. For example, a polymer having a glass transition point of 80 ° C. obtained by polymerizing ⁇ -pinene derived from terpene oil extracted from pine or the like has been proposed (Patent Document 3).
- the present invention has been made in view of the above circumstances, and can be obtained as a carbon neutral material from microorganisms, plants, and the like, and optical characteristics using ⁇ -ferrandrene as a monomer having particularly good polymerization characteristics. And ⁇ -ferrandylene polymer having good heat resistance, a method for producing ⁇ -ferrandol polymer, and a molded article comprising ⁇ -ferrandol polymer.
- the ⁇ -ferrandylene of the present invention has a low specific gravity, it is useful as a material for a lightweight molded product having excellent heat resistance and light transmittance. According to the method for producing a ⁇ -ferrandylene polymer of the present invention, a ⁇ -ferrandylene polymer having a high degree of polymerization and excellent heat resistance and light transmittance can be obtained.
- the first aspect of the present invention is a ⁇ -ferrandylene polymer.
- the second aspect of the present invention is a method for producing a ⁇ -ferrandylene polymer.
- the third aspect of the present invention is a molded article comprising the ⁇ -ferrandrene of the first aspect.
- ⁇ -Ferlandene which is a monomer constituting the ⁇ -ferrandylene polymer, may be extracted and purified from a living organism, or may be chemically synthesized from a petroleum-derived compound.
- ⁇ -ferrandrene contained in essential oil obtained by steam distillation from plant seeds and roots may be used, or existing chemical substances are used as raw materials, and ⁇ -ferrandrene obtained by a known chemical synthesis method is used. Also good.
- ⁇ -ferrandrene When chemical substances extracted from living organisms are used as materials, for example, plants or plants containing ⁇ -ferrandrene, such as Todomatsu, Ginger, Fennel, Neroli, Rosewood, Tomato, Lavender, Canadian Balsam, Angelica, etc.
- the extract from may be purified and used.
- the purity (pure content) can be increased by a method such as precision distillation or separation using a silica gel column.
- the reaction system for synthesizing the coalescence it is preferable that the purity of ⁇ -ferrandol in the reaction solution containing ⁇ -ferrandol is as high as possible. Further, the reaction system is more preferably a reaction system in which a compound having a double bond that interferes with the polymerization of ⁇ -ferrandrene is excluded as much as possible.
- a substance that reacts with a cis-type conjugated double bond such as a Diels-Alder reaction reagent is added to remove a cis-type conjugated double bond substance other than ⁇ -ferrandrene as an insoluble substance. It is preferable to increase the purity by combining with precision distillation or separation using a silica gel column.
- the content of ⁇ -ferrandylene represented by the following chemical formulas (I) and (II) with respect to the total mass of the polymerizable compound in the reaction solution that is, the purity of ⁇ -ferrandol is 50 mass. % Or more, more preferably 70% by weight or more, still more preferably 80% by weight or more, particularly preferably 90% by weight or more, and most preferably 95% by weight or more.
- the content may be 100% by mass.
- “purity” does not mean optical purity that distinguishes optical isomers of ⁇ -ferrandolene, but simply chemical purity that does not distinguish optical isomers of ⁇ -ferrandylene.
- the “polymerizable compound” means a compound having a double bond polymerizable with ⁇ -ferrandolene.
- the purity of ⁇ -ferrandol used in the reaction is a value determined by percentage of peak area of ⁇ -ferrandol by gas chromatography (GC) method or GC-MS method.
- GC gas chromatography
- it can be diluted with chloroform so that the reaction solution containing ⁇ -ferrandrene is 1% by mass and measured using a gas chromatograph analyzer.
- the concentration of ⁇ -ferrandylene as a monomer is preferably 1 to 90% by mass, more preferably 10 to 80% by mass, based on the total mass of the reaction solution. More preferably, it can be adjusted to 10 to 50% by mass. When the concentration is less than 1% by mass, productivity is low, and when the concentration exceeds 90% by mass, it is difficult to remove the heat of polymerization.
- the type of organic solvent constituting the reaction solution is not particularly limited as long as it can dissolve ⁇ -ferrandrene, and a solvent used in conventional cationic polymerization can be applied. Among these, a solvent with little chain transfer is preferable.
- a solvent with little chain transfer is preferable.
- examples of such a solvent include halogenated hydrocarbons, aromatic hydrocarbons, and aliphatic hydrocarbons from the viewpoint of solubility and reactivity under polymerization conditions of the polymer. More specifically, for example, halogenated carbonization such as methylene chloride, chloroform, 1,1-dichloroethane, 1,2-dichloroethane, n-propyl chloride, 1-chloro-n-butane, 2-chloro-n-butane and the like.
- Hydrogen solvents aromatic hydrocarbon solvents such as benzene, toluene, xylene, anisole; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, decalin, etc.
- aromatic hydrocarbon solvents such as benzene, toluene, xylene, anisole
- aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, decalin, etc.
- organic solvent one organic solvent may be used alone, or two or more organic solvents may be used in combination.
- the organic solvent may be a nonpolar solvent or a polar solvent.
- a nonpolar solvent In order to further increase the degree of polymerization of the ⁇ -ferrandylene polymer and obtain a tough polymer, it is particularly preferable to use a nonpolar solvent.
- a Lewis acid used in conventional cationic polymerization is applicable.
- EtAlCl 2 , AlCl 3 , Et 2 AlCl, Et 3 Al 2 Cl 3 , BCl 3 , SnCl 4 , TiCl 4 , Ti (OR) 4-y Cl 4 [R represents an alkyl group or an aryl group, and y represents an integer of 1 to 3. ] Is preferable because of high reactivity and selectivity.
- metal halides such as BF 3 , BBr 3 , AlF 3 , AlBr 3 , TiBr 4 , TiI 4 , FeCl 3 , FeCl 2 , SnCl 2 , WCl 6 , MoCl 5 , SbCl 5 , TeCl 2 , ZnCl 2 , (I-Bu) 3 Al, (i-Bu) 2 AlCl, (i-Bu) AlCl 2 , Me 4 Sn, Et 4 Sn, Bu 4 Sn, Bu 3 SnCl, and the like [Me is a methyl group Et represents an ethyl group and Bu represents a butyl group.
- Lewis acid one Lewis acid may be used alone, or two or more Lewis acids may be used in combination.
- an initiator used in combination as a Lewis acid may be used.
- an initiator is a substance that reacts with a Lewis acid to generate a carbon cation, and any initiator having such properties can be used.
- alkyl vinyl ether-hydrogen chloride adduct chloroalkyl vinyl ether-hydrogen chloride adduct, ⁇ -chloroethylbenzene, ⁇ -chloroisopropylbenzene, 1,3-bis ( ⁇ -chloroisopropyl) benzene, 1,4- Bis ( ⁇ -chloroisopropyl) benzene, 1,3-bis ( ⁇ -chloroisopropyl) -5-t-butylbenzene, 1,3,5-tris ( ⁇ -chloroisopropyl) benzene, t-butyl chloride, 2- Chlorine initiators such as chloro-2,4,4-trimethylpentane: alkyl vinyl ether-acetic acid adduct, ⁇ -acetoxyethylbenzene, ⁇ -acetoxyisopropylbenzene, 1,3-bis ( ⁇ -acetoxyisopropyl) benzene,
- ethers such as diethyl ether, methyl-t-butyl ether, dibutyl ether; esters such as ethyl acetate, methyl acetate, isopropyl acetate, butyl acetate, methyl isobutyrate, ethyl isobutyrate, propyl isobutyrate; pyridine, 2-methylpyridine, 2,6-dimethylpyridine, 2,6-di-butylpyridine, 2,6-diphenylpyridine, 2,6-di-t-butylpyridine, 2,6-di-t-butyl-4 -Pyridines such as methylpyridine; Amines such as trimethylamine, triethylamine and tributylamine; Amides such as dimethylacetamide and diethylacetamide; Sulphoxides such
- the concentration of these Lewis acids in the reaction solution is preferably 0.001 to 100 parts by weight, more preferably 0.01 to 50 parts by weight, and more preferably 0 to 100 parts by weight of ⁇ -ferrandolene to be added later. More preferably, it is 1 to 10 parts by mass. If the amount of the Lewis acid catalyst used is too small, the reaction may stop before the completion of the polymerization, and conversely if too large, it is uneconomical.
- the added ⁇ -ferrandylene may be dissolved in advance in the same type of organic solvent as the organic solvent constituting the reaction solution.
- the temperature of the reaction solution during the dropwise addition can usually be set to ⁇ 120 ° C. to 150 ° C., preferably ⁇ 90 ° C. to 100 ° C. If the reaction temperature is too high, it may be difficult to control the reaction and it may be difficult to obtain reproducibility, and if it is too low, the production cost increases.
- the number average molecular weight Mn is 100,000 or more, for example, A ⁇ -ferrandylene polymer of about 140,000 can be easily obtained. Further, the reaction may be carried out at ⁇ 15 to 40 ° C. At this temperature, a ⁇ -ferrandylene polymer having a number average molecular weight Mn of about 50,000 to 100,000 can be easily obtained.
- the reaction time of the cationic polymerization is not particularly limited, and may be appropriately adjusted so as to obtain a ⁇ -ferrandylene polymer having desired characteristics according to the conditions such as the type and amount of the polymerization catalyst, the reaction temperature, and the reaction equipment. it can.
- a ⁇ -ferrandylene polymer having desired characteristics can be obtained by reacting for about 1 second to 100 hours, preferably about 10 seconds to 1 hour, more preferably about 30 seconds to 10 minutes. It is preferable to perform polymerization until the ⁇ -ferrandylene polymer has a number average molecular weight Mn of 40,000 or more.
- the ⁇ -ferrandol polymer of the first aspect may be a homopolymer of ⁇ -ferrandol, or may be a copolymer of ⁇ -ferrandol and one or more other copolymerizable monomers. Good.
- a terminator may be added after the reaction for a predetermined time.
- alcohols such as methanol and ethanol are preferably used.
- the addition amount of the terminator is not strictly defined, but is usually 0.01 to 10 times the volume of the reaction solvent.
- Examples of methods for separating the ⁇ -ferrandylene polymer obtained by polymerization in the reaction solution from the solvent include reprecipitation, evaporation of the solvent by heating, removal of the solvent by reduced pressure, and removal of the solvent by water vapor (coagulation). ), Known methods such as removal of degassed solvent by an extruder can be applied.
- the removal method is not specifically limited, For example, the removal method refine
- the content of the remaining neutralized salt is preferably 100 ppm or less, particularly preferably 10 ppm or less, based on the mass of the polymer.
- the number average molecular weight Mn of the ⁇ -ferrandylene polymer is preferably 10,000 to 1,000,000, more preferably 40,000 or more, from the viewpoint of the viscosity and melt viscosity of the polymerization solution, moldability, strength of the molded product, and heat resistance. preferable.
- the number average molecular weight Mn of the ⁇ -ferrandylene polymer of the first aspect of the present invention can be adjusted to 20,000 to 500,000, 30,000 to 400,000, or 40,000 to 300,000. Can be prepared in the range of 50,000 to 250,000, 60,000 to 200,000, 70,000 to 150,000, 80,000 to It can also be prepared to 120,000.
- the molecular weight of the polymer is too large, the viscosity of the polymerization solution increases and the productivity of the polymer deteriorates, or the melt viscosity of the polymer increases and the moldability may deteriorate.
- the molecular weight is too small, the strength of the molded product obtained using the polymer is lowered, and the glass transition temperature is less than 80 ° C., so that sufficient heat resistance may not be exhibited.
- the preferred weight average molecular weight Mw of the ⁇ -ferrandylene polymer is preferably as large as possible from the viewpoint of improving the mechanical strength, heat resistance, ease of molding, etc. of the molded product, preferably 50,000 or more, more preferably 70,000 or more.
- 50,000 or more preferably 50,000 or more
- 90,000 or more is more preferable, 110,000 or more is further more preferable, 130,000 or more is particularly preferable, and 150,000 or more is most preferable.
- the upper limit of the weight average molecular weight Mw is not particularly limited, but is usually preferably 1 million or less, more preferably 800,000 or less, and still more preferably 600,000 or less from the viewpoint of improving moldability and workability.
- the weight average molecular weight can be calculated from measurement data obtained by the same method as the number average molecular weight.
- the Mw / Mn of the ⁇ -ferrandylene polymer is preferably 1 to 25, more preferably 1.05 to 20, and further preferably 1.1 to 10.
- the glass transition temperature Tg of the ⁇ -ferrandylene polymer is preferably 80 ° C. or higher, preferably about 80 to 350 ° C., more preferably 85 to 250 ° C., from the viewpoint of heat resistance, moldability, and strength of the molded product. 200 ° C. is more preferable.
- the glass transition temperature Tg is too high, the melt viscosity of the ⁇ -ferrandylene polymer becomes high and the moldability may be deteriorated.
- the glass transition temperature Tg is too low, the heat resistant use temperature of the molded product is lowered, which is not practical.
- the glass transition temperature Tg and heat resistance can be improved by increasing the molecular weight of the ⁇ -ferrandylene polymer and by hydrogenating the ⁇ -ferrandylene polymer.
- the number average molecular weight Mn and the weight average molecular weight Mw of ⁇ -ferrandylene polymer are determined according to the size exclusion chromatography method defined in JIS-K-0124-2002. It is obtained from the value of the differential refraction detector measured by GPC and the calibration curve of standard polystyrene.
- the glass transition temperature Tg is measured according to the method defined in JIS-K-7121-1987 “Method for Measuring Plastic Transition Temperature”. More specifically, the glass transition temperature (T The temperature determined as mg ) is the glass transition temperature Tg in the present specification and claims.
- the ⁇ -ferrandylene used as the material for the ⁇ -ferrandol polymer of the first aspect of the present invention is a mixture or racemic mixture of compounds that are optical isomers (enantiomers) represented by the following chemical formulas (I) and (II). It may be present or only one of the optical isomers.
- Chemically synthesized ⁇ -ferrandolene is usually a mixture or a racemate.
- ⁇ -ferrandolene consisting only of one of the optical isomers
- it can be obtained by optical isomerization separation by using a method such as chromatography using a chiral column, diastereomer method using an optical resolving agent, etc. Materials may be used.
- the ⁇ -ferrandol polymer obtained by using the above mixture or racemic ⁇ -ferrandolene as a material includes the following general formulas (I-1), (I-2), (II-1) and (II- Any one or more of the monomer units (repeating units) represented by 2) are included.
- parentheses indicate a bond with an adjacent monomer unit that is polymerized (bonded).
- the ⁇ -ferrandylene polymer of the first aspect of the present invention may have one or two of the monomer units represented by the above chemical formulas, You may have a seed
- the chemical formulas (I-1), (I-2), (II) are contained in a total of 50% by mass or more with respect to the total mass of the ⁇ -ferrandolene polymer.
- the content is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, further preferably 80 to 100% by mass, and most preferably 90 to 100% by mass.
- Hydrogenation can be performed on at least part of the olefinic carbon-carbon double bond of the ⁇ -ferrandylene polymer of the first aspect of the present invention.
- the glass transition temperature Tg rises and a polymer with further improved heat resistance can be obtained.
- a known method of adding hydrogen to a conventional polymer can be applied.
- the hydrogenation catalyst used in this case catalysts generally used for hydrogenation reactions of olefins and aromatic compounds can be applied.
- transition metals such as palladium, platinum, nickel, rhodium, ruthenium and the like are used as carbon.
- the supported metal catalyst is particularly preferable because it can be easily separated and recovered by filtration together with the polymerization catalyst after the hydrogenation reaction.
- the said catalyst may be used individually by 1 type, and may use 2 or more types together.
- the reaction temperature at the time of hydrogenation can usually be from -20 ° C to 250 ° C.
- the hydrogen pressure at the time of hydrogenation can usually be 0.1-100 kgf / cm 2 .
- 1 kgf 9.8 N.
- the solvent for the hydrogenation is not particularly limited as long as it is an organic solvent that dissolves the polymer and is inert to the catalyst. From the viewpoint of the solubility and reactivity of the hydrogenated product of the polymer, examples include aliphatic hydrocarbons, halogenated hydrocarbons, and aromatic hydrocarbons.
- the said organic solvent may be used individually by 1 type, and may use 2 or more types together.
- the reaction time for the hydrogenation can usually be about 0.1 to 20 hours.
- Hydrogenation rate (%) (Ratio (A / B (before hydrogenation))-ratio (A / B (after hydrogenation)) ⁇ 100 ⁇ ratio (A / B (before hydrogenation))
- the glass transition temperature Tg of the polymer obtained by hydrogenating the ⁇ -ferrandylene polymer is preferably about 80 to 350 ° C., preferably 85 to 250 ° C. from the viewpoint of heat resistance, moldability, and strength of the molded product. Is more preferable, and 90 to 200 ° C. is even more preferable.
- ⁇ -ferrandylene polymer of the first aspect of the present invention and the hydrogenated polymer thereof have thermoplasticity, they can be molded by press molding, extrusion molding, injection molding or the like.
- a molded product having a light specific gravity and excellent transparency and heat resistance By molding the ⁇ -ferrandylene polymer of the first aspect of the present invention or a hydrogenated polymer thereof, a molded product having a light specific gravity and excellent transparency and heat resistance can be obtained. Specifically, a molded product having a total light transmittance of 80% or more, preferably 90% or more, more preferably 95% or more, and a glass transition temperature Tg of 80 ° C. or more can be obtained.
- the upper limit value of the glass transition temperature Tg of the molded product is usually the same as the upper limit value of Tg of the polymer constituting the molded product.
- the use of the molded article is not particularly limited, and can be applied to various uses as in the case of a conventional transparent resin. It is preferable that 50 mass% or more of the ⁇ -ferrandylene polymer of the first aspect is contained with respect to the total mass of the molded product. In the molded article, the excellent physical properties of the ⁇ -ferrandylene polymer can be reflected.
- molded articles using ⁇ -ferrandylene polymer examples include optical plastic films and plastic lenses.
- Tg of ⁇ -ferrandylene polymer used in each molded product the glass transition temperature Tg of the polymer obtained by hydrogenating the ⁇ -ferrandylene polymer was assumed to be used in an environment close to a heat source (for example, a light source that generates heat). From the standpoint of ease of surface processing and the like, a higher value is preferable. From the viewpoint of reducing the influence of the heat of the light source, Tg is more preferably 100 ° C. or higher.
- surface processing surface treatment
- the Tg of the hydrogenated ⁇ -ferrandylene polymer is preferably 120 ° C. or higher.
- Tg exceeds about 200 ° C.
- the melt viscosity of the ⁇ -ferrandylene polymer increases, and the moldability may be deteriorated.
- the Tg is less than 80 ° C.
- the method for measuring the glass transition temperature Tg of the hydrogenated ⁇ -ferrandylene polymer may be the same as the method for measuring the glass transition temperature Tg of the non-hydrogenated ⁇ -ferrandylene polymer.
- the total light transmittance of the ⁇ -ferrandylene polymer used in the use of each molded product is preferably as high as the properties usually required for the use, preferably 80% or more, more preferably 85% or more, and 90%. The above is more preferable.
- its total light transmittance is preferably 80% or more, more preferably 85% or more, 90 % Or more is more preferable, and 95% or more is most preferable.
- the total light transmittance is a value measured in accordance with JIS-K-7361: 1997 (ISO13468-1: 1996).
- the ⁇ -ferrandylene polymer used in the use of each molded product has a low water absorption rate.
- the water absorption of the ⁇ -ferrandylene polymer is 0.2 when the mass change of the test piece when the test piece is placed in an atmosphere of 60 ° C. and 90% RH (relative humidity) for 24 hours is measured as the saturated water absorption. % Or less is preferable, 0.1% or less is more preferable, and 0.05% or less is more preferable.
- the specific gravity of the ⁇ -ferrandylene polymer used in the application of each molded article is 0.85 or more and less than 1.0, and preferably 0.85 to 0.98.
- the specific gravity is a numerical value measured according to A method of JIS-K-7112: 1999.
- the photoelastic coefficient of the ⁇ -ferrandylene polymer used in the application of each molded article is preferably small, and even at a temperature equal to or higher than the glass transition temperature Tg, it is more preferable that the photoelastic coefficient is small.
- a suitable photoelastic coefficient at a temperature equal to or higher than Tg (for example, Tg + 20 ° C.) of the ⁇ -ferrandylene polymer used in the application of each molded article cannot be generally specified depending on the application, but is ⁇ 3000 ⁇ 10 ⁇ 13 to 3000 ⁇ . 10 ⁇ 13 cm 2 / dyn is preferable, and ⁇ 1000 ⁇ 1000 ⁇ 13 to 1000 ⁇ 10 ⁇ 13 cm 2 / dyn is more preferable.
- Tg for example, Tg + 20 ° C.
- the bending elastic modulus of the ⁇ -ferrandylene polymer used in the application of each molded article is preferably 2500 MPa or more, and more preferably 2700 MPa or more. When the bending elastic modulus is within this range, deformation due to bending can be suppressed, and the thickness of the plastic lens can be reduced.
- the refractive index nD (25 ° C.) of the ⁇ -ferrandylene polymer used in the application of each molded article is preferably in the range of 1.450 to 1.600.
- the refractive index is within this range, the above-described molded product can be formed in the same manner as the conventional transparent resin (PMMA has a refractive index of 1.49 and PC has a refractive index of 1.59).
- the thickness of the lens can be reduced.
- the refractive index nD (25 ° C.) is a numerical value measured by a method based on JIS-K-7142. At this time, a test piece obtained by molding the ⁇ -ferrandylene polymer into a flat plate having a thickness of 100 ⁇ m, for example, can be used as the test piece.
- the Abbe number of the ⁇ -ferrandylene polymer used in each molded product is preferably in the range of 55 to 65, and more preferably in the range of 57 to 63.
- the chromatic aberration can be suppressed low, and the balance with respect to the above-described preferable refractive index range can be improved.
- the test piece a product obtained by molding the ⁇ -ferrandylene polymer into a flat test piece having a thickness of 100 ⁇ m, for example, can be used.
- the tensile strength of the test piece is preferably 60 MPa or more, more preferably 70 MPa or more, and 80 MPa. The above is more preferable.
- the upper limit of the tensile strength is not particularly limited, and the higher the strength, the better. However, the upper limit is usually about 100 MPa.
- the said tensile strength is a numerical value calculated
- the content of ⁇ -ferrandylene polymer contained in the molded product (resin member) of each embodiment to be described later may be 60 to 100% by mass with respect to the total mass of the molded product, or 70 to 100%. % By mass, 80 to 100% by mass, 90 to 100% by mass, 95 to 100% by mass, or 98 to 100% by mass It may be.
- ⁇ Hydrogenation (hydrogenation) of ⁇ -ferrandylene polymer constituting each molded product From the viewpoint of improving the heat resistance of the ⁇ -ferrandol polymer constituting the molded article of each embodiment described later, at least one of the olefinic carbon-carbon double bonds of the ⁇ -ferrandol polymer used in each embodiment.
- the part is preferably hydrogenated.
- the optical plastic film of the first embodiment is a film in which the above-described ⁇ -ferrandylene polymer is contained in an amount of 50 to 100% by mass with respect to the total mass of the optical plastic film.
- the ⁇ -ferrandylene polymer constituting the film has a glass transition temperature Tg of 80 ° C. or higher and a specific gravity of 0.85 or more and less than 1.0.
- the mechanical strength and heat resistance of the ⁇ -ferrandylene polymer that is the main component of the film may be improved.
- a suitable Tg is preferably 80 to 350 ° C., more preferably 85 to 250 ° C., and still more preferably 90 to 220 ° C. as described above. 90 to 200 ° C is particularly preferable, and 100 to 200 ° C is most preferable.
- the preferred number average molecular weight Mn of the ⁇ -ferrandylene polymer is preferably as large as possible, preferably 40,000 or more, more preferably 60,000 or more, further more preferably 80,000 or more, and even more preferably 100,000 or more. 120,000 or more is more preferable, 140,000 or more is still more preferable, 160,000 or more is particularly preferable, and 180,000 or more is most preferable.
- the upper limit of the number average molecular weight Mn is not particularly limited, but is usually preferably 800,000 or less, more preferably 600,000 or less, and still more preferably 400,000 or less, from the viewpoint of improving moldability and workability.
- the preferred weight average molecular weight Mw of the ⁇ -ferrandylene polymer is preferably as large as possible, preferably 50,000 or more, more preferably 70,000 or more, still more preferably 90,000 or more, and 110,000 or more. Even more preferred is 130,000 or more, most preferred is 150,000 or more.
- the upper limit of the weight average molecular weight Mw is not particularly limited, but is usually preferably 1 million or less, more preferably 800,000 or less, and still more preferably 600,000 or less from the viewpoint of improving moldability and workability.
- the weight average molecular weight can be calculated from measurement data obtained by the same method as the number average molecular weight.
- the Mw / Mn of the ⁇ -ferrandylene polymer is preferably 1 to 25, more preferably 1.05 to 20, and further preferably 1.1 to 10.
- the specific gravity of the optical plastic film of the present embodiment is usually in the range of 0.85 to 1.0 when the ⁇ -ferrandylene polymer constitutes 50 to 100% by mass of the total mass of the film. can do. Since the ⁇ -ferrandylene polymer has a specific gravity lighter than conventional acrylic resins, PET resins, polyvinyl chloride resins, etc., the film according to the present embodiment having the ⁇ -ferrandylene polymer as a main component is the conventional film. It is more lightweight than a film made of resin.
- the total light transmittance of the optical plastic film of the present embodiment is preferably as high as the properties usually required for its use, and specifically, the total light transmittance described above is preferable.
- the water absorption rate of the optical plastic film of the present embodiment is preferably the water absorption rate described above when the ⁇ -ferrandylene polymer constitutes 50 to 100% by mass of the total mass of the film. Since ⁇ -ferrandylene polymer has a lower water absorption than conventional acrylic resins, the plastic film of this embodiment having ⁇ -ferrandylene polymer as the main component is more dimensionally stable than conventional acrylic resins. Excellent in properties.
- the photoelastic coefficient of the optical plastic film of the present embodiment is such that when the ⁇ -ferrandylene polymer described above constitutes 95 to 100% by mass of the total mass of the film, It can be made equal to the photoelastic coefficient.
- a film thickness is 600 micrometers or less over the whole film. As the thickness (film thickness) decreases, the transparency increases and the phase difference of light transmitted through the film decreases.
- the lower limit of the film thickness is not particularly limited, but is preferably about 10 ⁇ m from the viewpoint of maintaining the excellent mechanical strength of the film.
- the numerical value measured by the contact method according to A method of JIS-K-7130: 1999 is employ
- the film thickness variation of the optical plastic film of the present embodiment is preferably 3.0% or less of the film thickness (reference film thickness), and more preferably 2.4% or less.
- the film thickness variation was measured by measuring the thickness at 9 points within the area of 100 cm 2 of the film to be measured by the contact method according to the A method of JIS-K-7130: 1999, and obtained from the data of 9 points.
- the value representing the coefficient in percentage is defined as the film thickness variation (%).
- the tensile strength when measured in a 100 ⁇ m-thick film shape is preferably 60 MPa or more, more preferably 70 MPa or more, and still more preferably 80 MPa or more.
- the upper limit of the tensile strength is not particularly limited, and the higher the strength, the better. However, the upper limit is usually about 100 MPa.
- the said tensile strength is a numerical value calculated
- the film shape used for the measurement is 100 ⁇ m thick.
- the method for producing (molding) the optical plastic film according to the present embodiment is not particularly limited, and for example, a known method for producing a conventional resin molded product such as a solution casting method or a melt extrusion method may be employed. it can.
- a method for producing the optical plastic film according to the present embodiment by a melt extrusion method for example, a predetermined ⁇ -ferrandylene polymer is melted by an extruder, and a ⁇ -ferrandylene polymer is obtained from a die attached to the extruder. After the sheet is extruded into a sheet shape, the sheet is brought into close contact with at least one cooling drum, molded, and taken up.
- a predetermined ⁇ -ferrandylene polymer is used as an appropriate organic solvent, for example, the aforementioned solvent used in a hydrogenation process.
- the polymer solution is cast onto a mirror surface of metal or the like, and then the solvent is evaporated, And a method for obtaining a film.
- optical plastic film according to the present embodiment examples include, for example, a polarizing plate protective film, a retardation film, a surface protective film for an electroluminescence element, and various functional films used in a flat panel display such as a liquid crystal display.
- a polarizing plate protective film examples include a retardation film, a surface protective film for an electroluminescence element, and various functional films used in a flat panel display such as a liquid crystal display.
- Examples thereof include a substrate film.
- the substrate film include a transparent conductive film, an antireflection film, an antistatic film, and a film with a hard coat.
- the optical plastic film of the present embodiment can be used as a surface protective film for protecting the surface to be protected.
- the surface can be protected by disposing the film on the surface to be protected by a known method such as adhesion, sticking, and thermocompression bonding.
- the surface of the optical plastic film of the present embodiment may be subjected to known surface processing such as hard coat processing, water repellent processing, antireflection processing, antistatic processing, conductivity imparting processing, etc.
- the surface treatment may not be performed.
- Examples of the film having the laminated structure include an antireflection film in which a known antireflection layer is laminated on the substrate film, a film with a hard coat in which a known hard coat layer is laminated, and a known light diffusing film.
- the brightness of the image display device can be improved by laminating a diffusion film laminated with a diffusion layer, a transparent conductive film laminated with a known conductive layer, and a layer having a refractive index different from that of the substrate film. Examples include a brightness enhancement film.
- an antireflection film can be obtained by providing an antireflection layer on the substrate film.
- a coating layer on which irregularities are formed is provided, and a configuration in which external light is diffusely reflected by the irregularities, or a coating layer having a low refractive index is provided.
- a diffusion film having improved light diffusibility can be obtained.
- another layer may be provided on the substrate film, and irregularities may be formed on the surface of this layer.
- the shape of the unevenness includes a triangular pyramid shape, a corrugated cross section, and a triangular prism shape having a triangular shape.
- you may provide a light-diffusion layer in the said substrate film surface.
- a transparent conductive film can be obtained by providing a transparent conductive layer on the substrate film.
- a transparent conductive layer transparency is maintained by applying conductivity with inorganic materials such as ITO, FTO, SnO 2 , ZnO 2 , Cu and Ag, and organic materials such as PEDOT-PSS, polyaniline, polypyrrole and polythiophene. It can obtain by providing in such a film thickness and a dispersed state.
- a brightness enhancement film can be obtained by providing a layer for improving brightness on the substrate film.
- a layer for example, a multilayer stack of dielectric materials designed to transmit only linearly polarized light and reflect other light, or a liquid crystal polymer designed to reflect only circularly polarized light and transmit other light Or the like.
- a conventional method can be applied as a method of forming the layer.
- the optical plastic film of the present embodiment As a polarizing plate protective film, for example, to obtain a polarizing film in which the polarizing plate protective film is laminated on one or both sides of the polarizing plate via an appropriate adhesive or the like. Can do. Moreover, the retardation film mentioned later may be further laminated
- the film of the present embodiment is used as a retardation film
- the film is preferably stretched so that a desired retardation is caused.
- the method for stretching the optical plastic film of this embodiment in at least one direction is not particularly limited, and a known method can be employed.
- stretching process is not performed only for the objective of manufacture of retardation film.
- the optical plastic film of this embodiment may be stretched to give the characteristics required when applied to other uses.
- the optical plastic film of the present embodiment can be advantageously used as a functional film of an image display device.
- positioning form in particular of a functional film in an image display device is not restrict
- the optical plastic film of the present embodiment is a conventional petroleum-derived film such as polyolefin resin, acrylic resin, carbonate resin, etc. with respect to light transmittance, heat resistance, water absorption, light resistance, photoelastic coefficient, mechanical strength, etc. Compared to resin, it has the same or better physical properties. In addition, since the specific gravity is lighter than many conventional resins, it is excellent in lightness. In addition, a film made of a conventionally known ⁇ -pinene polymer has excellent lightness equivalent to that of the film of the present embodiment, but the mechanical strength such as tensile strength makes the ⁇ -ferrandylene polymer of the present embodiment The constructed film is superior.
- ⁇ -ferrandylene tends to form a polymer having a large number average molecular weight, and easily forms a film having excellent mechanical strength. Therefore, by using the optical plastic film of this embodiment, a thin and lightweight functional film having the same strength can be produced.
- the plastic lens of the second embodiment is a lens comprising 50 to 100% by mass of the above-described ⁇ -ferrandylene polymer based on the total mass of the plastic lens.
- the ⁇ -ferrandylene polymer constituting the plastic lens has a specific gravity of 0.85 or more and less than 1.0 and a total light transmittance of 90% or more.
- the refractive index of the ⁇ -ferrandylene polymer is preferably in the range of 1.45 to 1.60.
- the ⁇ ferrandylene polymer preferably has an Abbe number in the range of 55 to 65.
- the shape of the plastic lens of the present embodiment is not particularly limited as long as it is a shape capable of diverging or converging incident light, and a conventionally known lens shape can be applied.
- a concave lens, a convex lens, a concavo-convex lens, etc. are mentioned.
- the curved surface of these lenses may be a spherical surface or an aspherical surface.
- the size of the plastic lens of the present embodiment is not particularly limited, and can be appropriately designed according to the use of the lens.
- the method for producing (molding) the plastic lens according to the present embodiment is not particularly limited, and a known method for producing a conventional resin lens, for example, a composition containing ⁇ -ferrandylene polymer in a heating cylinder of an extruder. Further, it is possible to employ a method of uniformly melt-plasticizing with a screw and injecting or extruding an appropriate amount of the resin composition into a mold and cooling and solidifying it.
- the plastic lens of this embodiment may be subjected to known surface treatments such as antireflection, surface hardening, antifogging, water repellency and the like.
- the plastic lens of the present embodiment is a conventional resin derived from petroleum such as polyolefin resin, acrylic resin, carbonate resin, etc. with respect to light transmittance, heat resistance, water absorption, light resistance, photoelastic coefficient and mechanical strength. Compared with the same or better physical properties. In addition, since the specific gravity is lighter than many conventional resins, it is excellent in lightness. In addition, the conventionally known plastic lens made of ⁇ -pinene polymer has excellent lightness equivalent to that of the plastic lens of the present embodiment, but in terms of mechanical strength such as impact resistance, the ⁇ -ferran of the present embodiment. A plastic lens composed of a drain polymer is superior.
- ⁇ -ferrandolene tends to form a polymer having a large number average molecular weight and is likely to be a plastic lens having excellent mechanical strength. Therefore, by using the ⁇ -ferrandylene polymer, a thin and lightweight plastic lens having the same strength can be produced.
- ⁇ Combination agent> In the ⁇ -ferrandylene polymer constituting the molded product of each embodiment described above, the following compounding agents may be mixed singly or in combination of two or more as required for each application.
- the compounding agent is not particularly limited as long as it is usually used in the conventional resin industry.
- an antioxidant an ultraviolet absorber, a light stabilizer, a near infrared absorber, a colorant such as a dye or a pigment.
- Lubricants plasticizers (softening agents), antistatic agents, fluorescent brighteners, fillers and the like.
- the above compounding agents can be used alone or in admixture of two or more.
- the mixing ratio is appropriately selected.
- the amount of each compounding agent is appropriately selected, but is usually about 0.001 to 5 parts by mass, preferably about 100 parts by mass of the ⁇ -ferrandylene polymer for each compounding agent. It is preferably used in the range of 0.01 to 1 part by mass.
- any polymer component> In the ⁇ -ferrandylene polymer constituting the molded article of each embodiment described above, the following polymer components may be mixed singly or in combination of two or more as required for each application, It does not need to be mixed.
- the polymer component include rubbery polymers, specifically, diene rubbers such as natural rubber, polybutadiene rubber, polyisoprene rubber, acrylonitrile / butadiene copolymer rubber; and styrene / butadiene copolymer rubber.
- Styrene / isoprene copolymer rubber styrene / butadiene / isoprene terpolymer rubber; hydrogenated diene rubber; ethylene / ⁇ -olefin copolymer such as ethylene / propylene copolymer, propylene / other Saturated polyolefin rubbers such as ⁇ -olefin copolymers; ethylene-propylene-diene copolymers, ⁇ -olefin-diene copolymers, isobutylene-isoprene copolymers, ⁇ -olefins such as isobutylene-diene copolymers, Diene polymer rubber; urethane rubber, silicone rubber, polyether Rubber, acrylic rubber, propylene oxide rubber, special rubber such as ethylene / acrylic rubber; thermoplastic elastomer such as styrene / butadiene / styrene block copolymer rubber, s
- Example 1 Production of ⁇ -ferrandylene polymer
- 78.6 ml of toluene manufactured by Kanto Chemical Co., Inc.
- the Lewis acid catalyst EtAlCl 2 ethylaluminum dichloride
- EtAlCl 2 ethylaluminum dichloride
- the number-average molecular weight of the obtained ⁇ -ferrandylene polymer was 40,900, and the glass transition temperature was 85 ° C.
- the reaction solution is filtered using a filter made of Teflon (registered trademark) with a pore size of 1 ⁇ m, and after removing the catalyst, it is reprecipitated with methanol, the precipitate is sufficiently dried, and a hydrogenated product of ⁇ -ferrandylene polymer 4.5 g was obtained.
- Teflon registered trademark
- the hydrogenation rate of the obtained polymer was calculated by 1 H-NMR spectrum measurement and found to be 99.9%.
- the number average molecular weight of the polymer was 40,500, the glass transition temperature was 130 ° C., and the total light transmittance was 92%.
- Example 2 A ⁇ -ferrandylene polymer was obtained in the same manner as in Example 1 except that the reaction temperature was set to ⁇ 40 ° C. and the reaction time was set to 5 minutes. The reaction rate of the monomer during the reaction was 100%, the number average molecular weight of the obtained polymer was 40,000, and the glass transition temperature was 82 ° C. Further, the hydrogenation rate of the polymer obtained by hydrogenation in the same manner as in Example 1 was 99.9%, the number average molecular weight of the polymer was 39,500, the glass transition temperature was 125 ° C., and the total light transmittance was 93. %Met.
- Example 3 Except for making reaction time into 10 second in Example 1, it implemented on the same conditions and obtained the beta ferrandylene polymer.
- the reaction rate of the monomer at the time of reaction was 88%
- the number average molecular weight of the obtained polymer was 33,800
- the glass transition temperature was 82 ° C.
- the hydrogenation rate of the polymer obtained by hydrogenation as in Example 1 was 99.9%
- the number average molecular weight of the polymer was 33,500
- the glass transition temperature was 125 ° C.
- the total light transmittance was 93. %Met.
- Example 4 In Example 1, the origin of ⁇ -ferrandol, a monomer, was changed to a mixed material of the optical isomers purified from plants, and the same conditions were used except that the solvent used for the polymerization reaction was hexane. The purity (pure content) of ⁇ -ferrandrene in the above material was 99.3%.
- the above materials are obtained by precision distillation of the essential oil obtained from the Todomatsu (plant) by steam distillation method, adding Diels-Alder reaction reagent to the resulting concentrated liquid, and further removing the trans-conjugated double bond substance. Obtained.
- the reaction rate of the monomer during the reaction was 100%, the molecular weight of the obtained polymer was 80,200, and the glass transition temperature was 84 ° C. Furthermore, the hydrogenation rate of the hydrogenated polymer was 99.7%, the number average molecular weight of the polymer was 80,000, the glass transition temperature was 131 ° C., and the total light transmittance was 93%. It was.
- Example 5 The reaction was conducted under the same conditions as in Example 4, except that the reaction temperature was -78 ° C. The reaction rate of the monomer during the reaction was 100%, the number average molecular weight of the obtained polymer was 139,400, and the glass transition temperature was 88 ° C. Furthermore, the hydrogenation rate of the hydrogenated polymer was 99.6%, the number average molecular weight of the polymer was 138,500, the glass transition temperature was 139 ° C., and the total light transmittance was 92%. It was.
- Example 6 In Example 4, it implemented on the same conditions except having made reaction temperature 20 degreeC.
- the reaction rate of the monomer during the reaction was 100%, the number average molecular weight of the obtained polymer was 57,700, and the glass transition temperature was 81 ° C.
- the hydrogenation rate of the hydrogenated polymer was 99.9%, the number average molecular weight of the polymer was 57,300, the glass transition temperature was 125 ° C., and the total light transmittance was 93%. It was.
- Example 7 In Example 4, after adding ⁇ -ferrandrene as a monomer into the reaction solution, 0.072 g ( ⁇ -di-tert-butylpyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) as an electron donor was further added. It was carried out under the same conditions except that 1.4 parts by mass) was added to 100 parts by mass of ferrandrene.
- the reaction of the monomers during the reaction was 42%, the number-average molecular weight of the obtained ⁇ -ferrandylene polymer was 75,300, and the glass transition temperature was 87 ° C. Furthermore, the hydrogenation rate of the hydrogenated polymer was 99.8%, the number average molecular weight of the polymer was 74,500, the glass transition temperature was 133 ° C., and the total light transmittance was 92%. It was.
- Example 8 In Example 4, it carried out on the same conditions except having used the methyl cyclohexane as the solvent at the time of a polymerization reaction, and obtained the beta ferrandylene polymer.
- the reaction rate of the monomer during the reaction was 100%, the number average molecular weight of the obtained polymer was 82,200, and the glass transition temperature was 84 ° C.
- the hydrogenation rate of the hydrogenated polymer was 99.7%, the number average molecular weight of the polymer was 82,000, the glass transition temperature was 133 ° C., and the total light transmittance was 93%. It was.
- Example 9 In Example 8, it implemented on the same conditions except having set the temperature at the time of a polymerization reaction to 80 degreeC, and obtained the beta ferrandylene polymer.
- the reaction rate of the monomer during the reaction was 80%, the number average molecular weight of the obtained polymer was 20,200, and the glass transition temperature was 81 ° C. Further, the hydrogenation rate of the hydrogenated polymer was 99.7%, the number average molecular weight of the polymer was 20,000, the glass transition temperature was 120 ° C., and the total light transmittance was 93%. It was.
- Example 4 In Example 4, it replaced with (beta) ferrandrene, and it carried out on the same conditions except having used beta pinene (made by Wako Pure Chemical Industries, Inc., purity 95%) which is a commercially available reagent.
- the molecular weight of the obtained polymer was 3,200.
- the reaction rate of the monomer during the reaction was 3%.
- Example 4 it was carried out under the same conditions except that the purity (pure content) of plant-derived ⁇ -ferrandrene was 80% and the reaction time was 24 hours. The number average molecular weight of the obtained polymer was 5,000.
- reaction yield during synthesis of ⁇ -ferrandol polymer By the method using o-dichlorobenzene as an internal standard, calculation was performed based on the reduction rate of the signal area from 5.5 to 6.5 ppm of signal derived from the conjugated double bond of ⁇ -ferrandolene monomer.
- Glass-transition temperature It was measured using a differential heat measuring device according to JIS-K-7121-1987 “Method for measuring transition temperature of plastic”. As the apparatus, DSC-60 manufactured by Shimadzu Corporation was used.
- Total light transmittance Measured according to JIS-K-7361: 1997 (ISO13468-1: 1996).
- a haze meter TC-H3DPK / II manufactured by Tokyo Denshoku Co., Ltd. was used as a measuring device.
- a film having a thickness of 100 ⁇ m made of the prepared ⁇ -ferrandol polymer or a polymer obtained by hydrogenating the ⁇ -ferrandol polymer was prepared by a melt extrusion method and used as a measurement sample.
- Optical plastic films and plastic lenses were produced as follows using hydrogenated ⁇ -ferrandylene polymer as a material.
- reaction solution was transferred to a separatory funnel, 20 parts by mass of 1% sodium hydroxide solution was added and stirred well, and then the aqueous phase was separated and removed. Next, the organic solvent phase was slowly evaporated by an evaporator, and the reaction solution was concentrated. About 40 parts by mass of the concentrated reaction solution was slowly added dropwise to 240 parts by mass of methanol to reprecipitate the polymer. The resulting precipitate was separated from the solution by filtration and sufficiently dried to obtain a ⁇ -ferrandylene polymer. The reaction rate of the monomer during the reaction was 100%.
- the number-average molecular weight of the obtained ⁇ -ferrandylene polymer was 105,300, and the glass transition temperature was 85 ° C.
- the reaction solution is filtered using a filter made of Teflon (registered trademark) with a pore size of 1 ⁇ m, and after removing the catalyst, it is reprecipitated with methanol, the precipitate is sufficiently dried, and a hydrogenated product of ⁇ -ferrandylene polymer 4.5 parts by mass were obtained.
- Teflon registered trademark
- the hydrogenation rate of the obtained ⁇ -ferrandrene polymer was calculated by 1 H-NMR spectrum measurement and found to be 99.9%.
- the number average molecular weight of the hydrogenated polymer was 104,000, the glass transition temperature was 130 ° C., and the specific gravity was 0.93.
- Synthesis Example 2 By the method of Synthesis Example 1, the reaction temperature was changed to ⁇ 78 ° C. to prepare a ⁇ -ferrandylene polymer having a number average molecular weight of 139,400. Further hydrogenation was performed to prepare a hydrogenated ⁇ -ferrandylene polymer having a hydrogenation rate of 99.9%, a number average molecular weight of 138,500, a glass transition temperature of 139 ° C., and a specific gravity of 0.93.
- Example A1 With respect to 100 parts by mass of the hydrogenated product of ⁇ -ferrandylene polymer obtained in Synthesis Example 1 (hereinafter sometimes referred to as “hydrogenated product of ⁇ -ferrandylene polymer”), 2- (2- 0.1 parts by weight of hydroxy-5-t-butylphenyl) -2H-benzotriazole and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate as an antioxidant
- a mixed composition containing 0.1 parts by weight of a powder blender, melted and kneaded using a twin screw extruder (TEX33, manufactured by Nippon Steel), and containing a pellet-like ⁇ -ferrandrene polymer hydrogenated product Got.
- the pellets of the obtained mixed composition were dried with a hot air dryer at 90 ° C. for 5 hours.
- the dried pellets were melt-extruded at 240 ° C. using a twin screw extruder equipped with a T die having a slit width of 10 cm, and then a sheet-like ⁇ -ferrandrene polymer hydrogenated mixture composition was cooled by three chill rolls
- the film having a width of about 70 mm and a thickness of 100 ⁇ m was obtained.
- Each physical property of the obtained film was measured by the methods described later by measuring the total light transmittance, glass transition temperature, water absorption, light resistance, photoelastic coefficient, tensile strength, film thickness variation, and specific gravity. The results are shown in Table 2 below.
- Example A2 By changing the reaction temperature to ⁇ 78 ° C. by the method of Example A1, a ⁇ -ferrandylene polymer having a number average molecular weight of 139,400 was produced. Further hydrogenation was performed to prepare a hydrogenated ⁇ -ferrandylene polymer having a hydrogenation rate of 99.9%, a molecular weight of 138,500, a glass transition temperature of 139 ° C., and a specific gravity of 0.93. A film having a thickness of 100 ⁇ m was prepared by the same method as in Example A1, and the physical properties of the film were measured. The results are shown in Table 2 below.
- Example A1 The pellets of alicyclic polyolefin resin (Zeonor 1060R manufactured by Nippon Zeon Co., Ltd.) were dried at 80 ° C. for 4 hours using a hot air dryer. Subsequently, the dried pellet was melt-extruded at 260 ° C. using the same apparatus as in Example A1. Thereafter, the extruded sheet-like alicyclic polyolefin-based resin was passed through three cooling rolls and cooled to obtain an extruded film having a width of about 70 mm and a thickness of 100 ⁇ m. Each physical property of the produced film was measured in the same manner as in Example A1. The evaluation results are shown in Table 2 below.
- Example A2 The pellets of polymethyl methacrylate resin (Acrypet TF-8, manufactured by Mitsubishi Rayon Co., Ltd.) were dried at 85 ° C. for 6 hours using a hot cloth drier. Next, using the same apparatus as in Example A1, the dried pellets were melt-extruded at 220 ° C., and the extruded sheet-like alicyclic polyolefin resin was cooled through three cooling rolls. An extruded film having a thickness of about 70 mm and a thickness of 100 ⁇ m was obtained. Each physical property of the produced film was measured in the same manner as in Example A1. The evaluation results are shown in Table 2 below.
- the optical plastic films of Examples A1 to A2 have high light transmission, heat resistance, light resistance and tensile strength, low water absorption, excellent photoelasticity and light weight, and little film thickness variation. It is clear that it is a film. It is understood that the films of Examples A1 to A2 have an excellent balance of physical properties as compared with the films of Comparative Examples A1 to A3, and are advantageous in the use of optical plastic films.
- Example B1 Using the hydrogenated ⁇ -ferrandylene polymer obtained in Synthesis Example 1 as a material, an aspherical surface having an outer diameter of 7 mm, a lens thickness of 2.5 mm, and a peripheral portion thickness of 3 mm using an injection molding machine SE-75 manufactured by Sumitomo Heavy Industries An objective lens was manufactured. The evaluation results are shown in Table 3 below.
- Example B2 Using the hydrogenated ⁇ -ferrandylene polymer obtained in Synthesis Example 2 as a material, an aspheric objective lens was manufactured by the same method as Example B1. The evaluation results are shown in Table 3 below.
- Example B1 The pellets of alicyclic polyolefin resin (ZEONEX 480R, manufactured by Nippon Zeon Co., Ltd.) were dried at 80 ° C. for 4 hours using a hot air dryer. Next, using the same apparatus as in Example B1, the dried pellets were injection molded at 260 ° C. to form a plastic lens. Each physical property of the produced plastic lens was measured in the same manner as in Example B1. The evaluation results are shown in Table 3 below.
- Example B2 The pellets of polymethyl methacrylate resin (Acrypet TF-8, manufactured by Mitsubishi Rayon Co., Ltd.) were dried at 85 ° C. for 6 hours using a hot cloth drier. Next, using the same apparatus as in Example B1, the dried pellets were injection molded at 220 ° C. to form a plastic lens. Each physical property of the produced plastic lens was measured in the same manner as in Example B1. The evaluation results are shown in Table 3 below.
- Example B3 A polycarbonate resin (Mitsubishi Engineering Plastics, Iupilon H-3000) was injection molded at 280 ° C. using the same apparatus as in Example B1 to mold a plastic lens. Each physical property of the produced plastic lens was measured in the same manner as in Example B1. The evaluation results are shown in Table 3 below.
- the plastic lenses of Examples B1 and B2 have high light transmittance, heat resistance, light resistance, moisture resistance and impact resistance, low water absorption, and excellent photoelasticity, bending elasticity and lightness. It is clear that it is a plastic lens. It is understood that the plastic lenses of Examples B1 and B2 have an excellent balance of physical properties as compared with the plastic lenses of Comparative Examples B1 and B3, and are advantageous in the use of plastic lenses.
- Total light transmittance Measured according to JIS-K-7361: 1997 (ISO13468-1: 1996).
- a haze meter TC-H3DPK / II manufactured by Tokyo Denshoku Co., Ltd. was used.
- a 100 ⁇ m-thick film made of the hydrogenated ⁇ -ferrandylene polymer synthesized above was prepared by a melt extrusion method and used as a measurement sample.
- Glass-transition temperature The glass transition temperature of the resin used was measured by the method described above.
- a film sample having a thickness of 500 ⁇ m composed of the hydrogenated ⁇ -ferrandylene polymer synthesized above was formed by a melt extrusion method and used as a measurement sample.
- a 3.2 mm-thick test piece composed of the hydrogenated ⁇ -ferrandrene polymer synthesized above was molded by a melt extrusion method and used as a measurement sample. .
- the unit of change is [ ⁇ 10 ⁇ 13 cm 2 / dyn].
- Refractive index (nD) When measuring the refractive index of the plastic lens described above, a 100 ⁇ m-thick test piece composed of the hydrogenated ⁇ -ferrandylene polymer synthesized above was molded, and the refractive index (nD) was measured according to JIS-K-7142. In conformity, the measurement was performed at 25 ° C. An Abbe refractometer DR-M4 (manufactured by Atago Co., Ltd.) was used as a measuring device.
- Abbe number When measuring the Abbe number related to the plastic lens described above, a test piece having a thickness of 100 ⁇ m made of the hydrogenated ⁇ -ferrandylene polymer synthesized above was molded, and the Abbe number was measured at 25 ° C. An Abbe refractometer DR-M4 (manufactured by Atago Co., Ltd.) was used as a measuring device. The obtained measured values were judged according to the following criteria. A: Abbe number ⁇ 57... Good B: 57> Abbe number ⁇ 55... Normal C: 55> Abbe number... Bad
- the present invention can be widely used in the field of molded products such as optical elements, films, optical plastic films, and plastic lenses.
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Abstract
Description
本願は、2013年10月21日に日本に出願された特願2013-218510号、並びに、2014年3月24日に日本に出願された、特願2014-060269号及び特願2014-060270号に基づき優先権を主張し、その内容をここに援用する。
カーボンニュートラルなポリマーの材料として、生物体内の生合成経路で生産されうる化合物が注目されている。例えば、マツ等から抽出したテルペン油由来のβピネンを重合して得られたガラス転移点が80℃の重合体が提案されている(特許文献3)。しかし、βピネンがモノマーである、実用的な強度を発現する高重合度の重合体を得るにためは、2官能性ビニル化合物の存在下において重合せしめる必要があった。さらには重合温度を-80℃~0℃と極低温にする必要があった。環境負荷を少なくして、安価に製造するために重合特性の良好な天然材料の利用が望まれていた。
βフェランドレン重合体を構成するモノマーであるβフェランドレンは、生物から抽出及び精製されていてもよいし、石油由来の化合物から化学合成されていてもよい。例えば植物の種子や根から水蒸気蒸留によって得られたエッセンシャルオイルに含まれるβフェランドレンを用いてもよいし、既存の化学物質を原料として、公知の化学合成法によって得られたβフェランドレンを用いてもよい。
特に好ましくは、例えば、ディールスアルダー反応試薬等のシス型の共役二重結合と反応する物質を添加し、βフェランドレン以外のシス型の共役二重結合物質を不溶性の物質として除去し、更に、精密蒸留やシリカゲルカラムによる分離等と組み合わせることにより純度を高くすることが好ましい。
例えば、βフェランドレンを含む反応液が1質量%となるようにクロロホルムに希釈し、ガスクロマトグラフ分析装置を用いて測定することができる。
前記有機溶媒として、1種の有機溶媒を単独で用いてもよいし、2種以上の有機溶媒を併用してもよい。
βフェランドレン重合体の重合度を一層高めて、高靭性の重合体を得るためには、非極性溶媒を用いる方が特に好ましい。
前記ルイス酸として、1種のルイス酸を単独で用いてもよいし、2種以上のルイス酸を併用してもよい。
βフェランドレン重合体の数平均分子量Mnは、重合溶液の粘度や溶融粘度、成形性、成形品の強度、耐熱性の観点から、1万~100万が好ましく、4万以上であることがより好ましい。本発明の第一態様のβフェランドレン重合体の数平均分子量Mnは、2万~50万に調製することもできるし、3万~40万に調製することもできるし、4万~30万に調製することもできるし、5万~25万に調製することもできるし、6万~20万に調製することもできるし、7万~15万に調製することもできるし、8万~12万に調製することもできる。重合体の分子量が大き過ぎると、重合溶液の粘度が高くなって重合体の生産性が悪くなり、又は、重合体の溶融粘度が高くなって成形性が悪くなる恐れがある。一方、分子量が小さ過ぎると、重合体を用いて得られる成形品の強度が低下すると共に、ガラス転移温度が80℃未満となり、十分な耐熱性を発揮し得ない恐れがある。
また、上記と同様の観点から、βフェランドレン重合体のMw/Mnは、1~25が好ましく、1.05~20がより好ましく、1.1~10がさらに好ましい。
本発明の第一態様のβフェランドレン重合体の材料として用いるβフェランドレンは、下記化学式(I)及び(II)で表される互いに光学異性体(エナンチオマー)である化合物の混合物又はラセミ体であってもよいし、何れか一方の光学異性体のみであってもよい。化学合成されたβフェランドレンは、通常、前記混合物又はラセミ体である。何れか一方の光学異性体のみからなるβフェランドレンの材料を用いる場合、例えばキラルカラムを用いたクロマトグラフィー、光学分割剤を用いたジアステレオマ法等の手法を用いることにより、光学異性分離をして得られた材料を用いてもよい。
本発明の第一態様のβフェランドレン重合体が有するオレフィン性炭素-炭素二重結合の少なくとも一部に対して水素化(水素添加)を行うことができる。水素添加を行うことによって、ガラス転移温度Tgが上昇し、耐熱性が一層向上した重合体を得ることができる。
前記水素添加を行う際の水素圧力は、通常0.1~100kgf/cm2で行うことが可能である。ここで、1kgf=9.8Nである。
(比(A/B(水添前))-比(A/B(水添後))×100÷比(A/B(水添前))
本発明の第一態様のβフェランドレン重合体及びその水素添加された重合体は熱可塑性を有するため、プレス成形、押し出し成形、射出成形などの成形加工が可能である。
本発明の第三態様の成形品には、成形の際に、安定剤、滑剤、顔料、耐衝撃性改良剤、加工助剤、補強剤、着色剤、難燃剤、耐候性改良剤、紫外線吸収剤、酸化防止剤、防カビ剤、抗菌剤、光安定剤、帯電防止剤、シリコンオイル、ブロッキング防止剤、離型剤、発泡剤、香料等の各種添加剤;ガラス繊維、ポリエステル繊維等の各種繊維;タルク、マイカ、モンモリロナイト、シリカ、木粉等の充填剤;各種カップリング剤等の成分を必要に応じて所定量を配合することができる。
前記成形品の総質量に対して、第一態様のβフェランドレン重合体が50質量%以上含まれることが好ましい。当該成形品において、βフェランドレン重合体が有する優れた物性を反映させることができる。
前記成形品として、例えば、光学用プラスチックフィルム、プラスチックレンズ等が挙げられる。
前記各成形品の用途において、βフェランドレン重合体に対して水素添加することにより得られる重合体のガラス転移温度Tgは、熱源(例えば熱を発する光源)に近い環境で使用することを想定した場合や、表面加工が容易になる等の観点から、高い方が好ましい。光源の熱による影響を低減する観点からは、Tgは100℃以上であることがより好ましい。前記各成形品について、その耐溶剤性やガス遮蔽性を向上させたり、帯電防止性を付与したり、導電性を付与したりするために公知の表面加工(表面処理)を行うことができる。これらの表面加工を容易に行うことができるため、水素添加したβフェランドレン重合体のTgは120℃以上であることが好ましい。Tgが200℃程度を超えると、βフェランドレン重合体の溶融粘度が高くなり、成形性が悪くなる恐れがある。一方、Tgが80℃未満であると、各成形品の耐熱使用温度が低くなるために、好ましくない。
水素添加したβフェランドレン重合体のガラス転移温度Tgの測定方法は、水素添加していないβフェランドレン重合体のガラス転移温度Tgの測定方法と同じでよい。
前記各成形品の用途において使用されるβフェランドレン重合体の全光線透過率は、その用途に通常求められる性質として、高いほど好ましく、80%以上が好ましく、85%以上がより好ましく、90%以上がさらに好ましい。例えば、βフェランドレン重合体のみからなる厚さ約100μmの平板状試験片を測定した場合、その全光線透過率が80%以上であることが好ましく、85%以上であることがより好ましく、90%以上であることが更に好ましく、95%以上であることが最も好ましい。ここで、上記全光線透過率は、JIS-K-7361 : 1997 (ISO13468-1:1996)に準拠して測定した数値である。
前記各成形品の用途において使用されるβフェランドレン重合体は、寸法安定性の観点から、吸水率が低い方が好ましい。βフェランドレン重合体の吸水率は、60℃、90%RH(相対湿度)雰囲気下に試験片を24時間置いたときの試験片の質量変化を飽和吸水率として測定したときに、0.2%以下が好ましく、0.1%以下がより好ましく、0.05%以下がさらに好ましい。
前記各成形品の用途において使用されるβフェランドレン重合体の比重は小さいため、軽い成形品を得ることができる。前記各成形品の用途において使用されるβフェランドレン重合体の比重は、0.85以上1.0未満であり、0.85~0.98であることが好ましい。
ここで、上記比重は、JIS-K-7112:1999のA法に準じて測定した数値である。
前記各成形品の用途において使用されるβフェランドレン重合体の光弾性係数は小さいことが好ましく、ガラス転移温度Tg以上の温度においても、その光弾性係数が小さいことがより好ましい。光弾性が小さいβフェランドレン重合体を使用することにより、光学歪みの少ない成形品を得ることができる。
前記各成形品の用途において使用されるβフェランドレン重合体の曲げ弾性率は、2500MPa以上が好ましく、2700MPa以上がより好ましい。この範囲の曲げ弾性率であると、撓みによる変形を抑制し、プラスチックレンズの厚みを薄くすることができる。
前記各成形品の用途において使用されるβフェランドレン重合体の屈折率nD(25℃)は、1.450~1.600の範囲であることが好ましい。この範囲の屈折率であると、従来の透明樹脂(PMMAの屈折率は1.49、PCの屈折率1.59)と同様に前述した成形品を構成することができる。さらに、プラスチックレンズの用途においては、当該レンズの厚みを薄くすることができる。ここで、上記屈折率nD(25℃)は、JIS-K-7142に準拠した方法により測定された数値である。この際、試験片として、上記βフェランドレン重合体を、例えば厚み100μmの平板状に成形した試験片を使用することができる。
前記各成形品の用途、特にプラスチックレンズの用途において使用されるβフェランドレン重合体のアッベ数は、55~65の範囲であることが好ましく、57~63の範囲であることがより好ましい。これら範囲のアッベ数であると色収差を低く抑制することができるとともに、前述の好適な屈折率の範囲に対するバランスを良好にすることができる。この際、試験片として、上記βフェランドレン重合体を、例えば厚み100μmの平板状試験片に成形したものを使用することができる。
前記各成形品の用途において使用されるβフェランドレン重合体を3.2mm厚の板状試験片に成形したとき、その試験片の引張強度は、60MPa以上が好ましく、70MPa以上がより好ましく、80MPa以上が更に好ましい。引張強度の上限値は特に制限されず、その強度が大きい程好ましいが、通常100MPa程度が上限値となる。ここで、前記引張強度は、ASTM D638に準拠した測定方法によって求められた数値である。
後述する各実施形態の成形品(樹脂部材)に含まれるβフェランドレン重合体の含有量は、前記成形品の総質量に対して、60~100質量%であってもよいし、70~100質量%であってもよいし、80~100質量%であってもよいし、90~100質量%であってもよいし、95~100質量%であってもよいし、98~100質量%であってもよい。
後述する各実施形態の成形品を構成するβフェランドレン重合体の耐熱性を向上させる観点から、各実施形態で使用されるβフェランドレン重合体が有するオレフィン性炭素-炭素二重結合の少なくとも一部が水素化されていることが好ましい。
第一実施形態の光学用プラスチックフィルムは、上述したβフェランドレン重合体が、前記光学用プラスチックフィルムの総質量に対して50~100質量%含まれてなるフィルムである。前記フィルムを構成するβフェランドレン重合体は、そのガラス転移温度Tgが80℃以上であり、且つその比重が0.85以上1.0未満である。
また、上記と同様の観点から、βフェランドレン重合体のMw/Mnは、1~25が好ましく、1.05~20がより好ましく、1.1~10がさらに好ましい。
βフェランドレン重合体は、従来のアクリル系樹脂よりも吸水性が低いため、βフェランドレン重合体を主成分として有する本実施形態のプラスチックフィルムは、従来のアクリル系樹脂からなるフィルムよりも寸法安定性に優れる。
本実施形態においては、前記膜厚に関して、JIS-K-7130:1999のA法に準ずる接触法によって測定された数値を採用する。
ここで、前記膜厚変動は、JIS-K-7130:1999のA法に準ずる接触法によって、測定するフィルムの100cm2の面積内で厚みを9点測定し、9点のデータより求めた変動係数を百分率で表した値を膜厚変動(%)とする。
ここで、前記引張強度は、ISO 527に準拠した測定方法によって求められた数値である。測定に使用するフィルム形状は100μm厚である。
本実施形態に係る光学用プラスチックフィルムを製造(成形)する方法は、特に制限されず、例えば、溶液流延法や溶融押出法等の従来の樹脂成形品を製造する公知方法を採用することができる。
本実施形態の光学用プラスチックフィルムを少なくとも一方向に延伸加工する方法は特に制限されず、公知の方法を採用できる。
なお、上記延伸加工は位相差フィルムの製造の目的だけに行われるものではない。本実施形態の光学用プラスチックフィルムを他の用途に適用する場合に求められる特性を付すために延伸加工を施してもよい。
また、従来知られているβピネン重合体からなるフィルムは、本実施形態のフィルムと同等の優れた軽量性を有するが、引張強度等の機械的強度において本実施形態のβフェランドレン重合体によって構成されたフィルムの方が優れる。この要因の一つとして、βフェランドレンの方が、数平均分子量の大きい重合体を形成し易く、機械的強度に優れたフィルムに成り易いことが考えられる。
したがって、本実施形態の光学用プラスチックフィルムを使用することにより、同じ強度を有しながら薄くて軽量な機能性フィルムを製造することができる。
第二実施形態のプラスチックレンズは、上述したβフェランドレン重合体が、前記プラスチックレンズの総質量に対して50~100質量%含まれてなるレンズである。前記プラスチックレンズを構成するβフェランドレン重合体は、その比重が0.85以上1.0未満であり、その全光線透過率が90%以上である。この様に透明性の高いβフェランドレン重合体を主成分として使用することにより、本実施形態のプラスチックレンズの透明性を高くすることができる。前記βフェランドレン重合体の屈折率が、1.45~1.60の範囲にあることが好ましい。前記βフェランドレン重合体のアッベ数が、55~65の範囲にあることが好ましい。
本実施形態に係るプラスチックレンズを製造(成形)する方法は特に制限されず、従来の樹脂製レンズを製造する公知方法、例えば、βフェランドレン重合体を含む組成物を押出機の加熱シリンダー内で、スクリューにより均一に溶融可塑化し、その樹脂組成物の適量を、金型内に射出するか又は押出し、冷却固化して成形する方法、を採用することができる。
また、従来知られているβピネン重合体からなるプラスチックレンズは、本実施形態のプラスチックレンズと同等の優れた軽量性を有するが、耐衝撃性等の機械的強度において、本実施形態のβフェランドレン重合体によって構成されたプラスチックレンズの方が優れる。この要因の一つとして、βフェランドレンの方が、数平均分子量の大きい重合体を形成し易く、機械的強度に優れたプラスチックレンズに成り易いことが考えられる。
したがって、βフェランドレン重合体を使用することにより、同じ強度を有しながら薄くて軽量なプラスチックレンズを製造することができる。
前述した各実施形態の成形品を構成するβフェランドレン重合体には、各用途の必要に応じて、下記の配合剤が、単独で又は2種以上を組み合わせて、混合されても構わない。
前記配合剤としては、従来の樹脂工業で通常使用されるものであれば特に制限されず、例えば、酸化防止剤、紫外線吸収剤、光安定剤、近赤外線吸収剤、染料や顔料等の着色剤、滑剤、可塑剤(柔軟化剤)、帯電防止剤、蛍光増白剤、充填材等の配合剤を挙げることができる。
前述した各実施形態の成形品を構成するβフェランドレン重合体には、各用途の必要に応じて、下記のポリマー成分が、単独で又は2種以上を組み合わせて、混合されても良いし、混合されなくても良い。
前記ポリマー成分としては、例えば、ゴム質重合体があり、具体的には、天然ゴム、ポリブタジエンゴム、ポリイソプレンゴム、アクリロニトリル・ブタジエン共重合体ゴム等のジエン系ゴム;スチレン・ブタジエン共重合体ゴム、スチレン・イソプレン共重合体ゴム、スチレン・ブタジエン・イソプレン三元共重合体ゴム;ジエン系ゴムの水素添加物;エチレン・プロピレン共重合体等のエチレン・α-オレフィン共重合体、プロピレン・その他のα-オレフィンの共重合体等の飽和ポリオレフィンゴム;エチレン・プロピレン・ジエン共重合体、α-オレフィン・ジエン共重合体、イソブチレン・イソプレン共重合体、イソブチレン・ジエン共重合体等のα-オレフィン・ジエン系重合体ゴム;ウレタンゴム、シリコーンゴム、ポリエーテル系ゴム、アクリルゴム、プロピレンオキサイドゴム、エチレン・アクリルゴム等の特殊ゴム;スチレン・ブタジエン・スチレンブロック共重合体ゴム、スチレン・イソプレン・スチレンブロック共重合体ゴム等の熱可塑性エラストマー;水素添加熱可塑性エラストマー;ウレタン系熱可塑性エラストマー;ポリアミド系熱可塑性エラストマー;1,2-ポリブタジエン系熱可塑性エラストマーを挙げることができる。また、その配合量は、適宜に選択されるが、βフェランドレン重合体の100質量部に対して、例えば、3~30質量部程度、好ましくは5~20質量部の範囲で使用されることが好ましい。
乾燥させた300mlガラス製フラスコに、トルエン(関東化学株式会社製)78.6mlを入れ、0℃に冷却した。つぎにルイス酸触媒のEtAlCl2(エチルアルミニウムジクロリド)(17%ヘキサン溶液、約1mol/L、東京化成工業株式会社製)を、モノマーであるβフェランドレン100質量部に対して7.3質量部に相当する量(0.035ml)を投入し、よく分散させたのち、化学合成によって予め得たβフェランドレン(純度83.3質量%)6.0ml(5.1g)をゆっくりと滴下投入した。1分後に、メタノール10mlを加えて反応を停止した。反応溶液を分液ロートに移した後に1%水酸化ナトリウム溶液20mlを加えて、よく撹拌した後、水溶液の相を分離除去した。次に、有機溶媒相をエバポレータによりゆっくりと蒸発させ、反応溶液を濃縮させた。濃縮した反応溶液約40mlをメタノール300mlにゆっくり滴下し、重合物を再沈させた。得られた沈殿物をろ過によって溶液から分離し、十分乾燥させ、βフェランドレン重合体を得た。反応時のモノマーの反応率は100%であった。
十分窒素置換を行った圧力容器に、脱水したヘキサン90mlおよび得られたβフェランドレン重合体4gを投入し十分溶解させた。ついで、パラジウム・アルミナ触媒(和光純薬製、Pd:5%)10gを添加し、8MPaの水素雰囲気下にて、120℃で10時間、水素添加反応を行った。テフロン(登録商標)からなる孔径1μmのフィルターを用いて反応液をろ過し、触媒を除去した後、メタノールにて再沈させ、沈殿を十分に乾燥させて、βフェランドレン重合体の水素添加物4.5gを得た。
実施例1において反応温度を-40℃、反応時間を5分に設定した以外は同一条件で実施し、βフェランドレン重合体を得た。反応時のモノマーの反応率は100%であり、得られ重合体の数平均分子量は40,000であり、ガラス転移温度は82℃であった。
さらに、実施例1と同様に水素添加して得た重合体の水素添加率は99.9%、重合体の数平均分子量は39,500、ガラス転移温度は125℃、全光線透過率は93%であった。
実施例1において反応時間を10秒とした以外は同一条件で実施し、βフェランドレン重合体を得た。反応時のモノマーの反応率は88%であり、得られた重合体の数平均分子量は33,800であり、ガラス転移温度は82℃であった。
さらに、実施例1と同様に水素添加して得た重合体の水素添加率は99.9%、重合体の数平均分子量は33,500、ガラス転移温度は125℃、全光線透過率は93%であった。
実施例1において、モノマーであるβフェランドレンの由来を、植物から精製した前記光学異性体の混合材料に変更し、更に、重合反応に使用する溶媒をヘキサンにした以外は同一条件で実施した。上記材料におけるβフェランドレンの純度(純分)は99.3%であった。上記材料は、トドマツ(植物体)から水蒸気蒸留の方法により得られた精油を精密蒸留し、得られた濃縮液にディールスアルダー反応試薬を添加し、更にトランス共役二重結合物質を除去することによって得た。
反応時のモノマーの反応率は100%であり、得られた重合体の分子量は80,200であり、ガラス転移温度は84℃であった。
さらに、水素添加した重合体の水素添加率は99.7%であり、重合体の数平均分子量は80,000であり、ガラス転移温度は131℃であり、全光線透過率は93%であった。
実施例4において反応温度を-78℃とした以外は同一条件で実施した。
反応時のモノマーの反応率は100%であり、得られた重合体の数平均分子量は139,400であり、ガラス転移温度は88℃であった。
さらに、水素添加した重合体の水素添加率は99.6%であり、重合体の数平均分子量は138,500であり、ガラス転移温度は139℃であり、全光線透過率は92%であった。
実施例4において反応温度を20℃とした以外は同一条件で実施した。
反応時のモノマーの反応率は100%であり、得られた重合体の数平均分子量は57,700であり、ガラス転移温度は81℃であった。
さらに、水素添加した重合体の水素添加率は99.9%であり、重合体の数平均分子量は57,300であり、ガラス転移温度は125℃であり、全光線透過率は93%であった。
実施例4において、反応液中にモノマーであるβフェランドレンを投入した後、さらに電子供与剤である2,6-ジ-t-ブチルピリジン(東京化成工業株式会社製)0.072 g(βフェランドレンの100質量部にたいして1.4質量部)を添加した以外は同一条件で実施した。
反応時のモノマーの反応は42%であり、得られたβフェランドレン重合体の数平均分子量は75,300であり、ガラス転移温度は87℃であった。
さらに、水素添加した重合体の水素添加率は99.8%であり、重合体の数平均分子量は74,500であり、ガラス転移温度は133℃であり、全光線透過率は92%であった。
実施例4において、重合反応時の溶媒をメチルシクロヘキサンにした以外は同一条件で実施し、βフェランドレン重合体を得た。反応時のモノマーの反応率は100%、得られた重合体の数平均分子量は82,200であり、ガラス転移温度は84℃であった。
さらに、水素添加した重合体の水素添加率は99.7%であり、重合体の数平均分子量は82,000であり、ガラス転移温度は133℃であり、全光線透過率は93%であった。
実施例8において、重合反応時の温度を80℃とした以外は同一条件で実施し、βフェランドレン重合体を得た。反応時のモノマーの反応率は80%、得られた重合体の数平均分子量は20,200であり、ガラス転移温度は81℃であった。
さらに、水素添加した重合体の水素添加率は99.7%であり、重合体の数平均分子量は20,000であり、ガラス転移温度は120℃であり、全光線透過率は93%であった。
実施例4において、βフェランドレンに代えて、市販の試薬であるβピネン(和光純薬社製、純度95%)をモノマーとして使用した以外は同一条件で行った。得られた重合体の分子量は3,200であった。また、反応時のモノマーの反応率は3%であった。
実施例4において、植物由来のβフェランドレンの純度(純分)を80%として、反応時間を24時間とした以外は同一条件で行った。
得られた重合体の数平均分子量は5,000であった。
o-ジクロロベンゼンを内部標準とする方法により、β-フェランドレンモノマーの共役二重結合に由来するシグナル5.5~6.5ppmのシグナルの面積の減少率により算出した。
標準ポリスチレン換算で測定した。装置として、島津製作所社製、LC-20AD送液ユニット、RID-10示差屈折率検出器を用いた。カラムは、昭和電工株式会社製のShodex KF803を2本用いた。溶媒は、THF(40℃)を用いた。
溶媒は重水素化クロロホルムを用いた。TMSで0ppm補正を行った。日本電子株式会社製のNMR装置、JNM-ECX400(400MHz)を使用して、1H-NMRスペクトルを測定した。測定は室温で行った。
水素添加前のスペクトルの不飽和結合に起因する5.0~6.0ppmのピークの減少率を求めた。この時、5.0~6.0ppmのオレフィン性二重結合のプロトンに由来するシグナルの積分値Aと、0.5~2.5ppmの飽和炭化水素のプロトンに由来するシグナルの積分値Bとの比 A/Bを用いた。水素添加率(%)は(A/B(Before)-A/B(After))x100/A/B(Before)で算出した。
JIS-K-7121-1987「プラスチックの転移温度測定方法」により、示差熱測定装置を用いて測定した。装置は、島津製作所社製のDSC-60を用いた。
JIS-K-7361 : 1997 (ISO13468-1:1996)に準拠して測定した。測定装置として、東京電色社製のヘーズメーターTC-H3DPK/IIを用いた。
調製したβフェランドレン重合体又はそのβフェランドレン重合体を水素添加して得た重合体からなる厚み100μmのフィルムを、溶融押出法によって作製し、測定試料として用いた。
βフェランドレン重合体の水素添加物を材料として、光学用プラスチックフィルム、プラスチックレンズを以下の様に製造した。
成形品の材料として使用するβフェランドレン重合体の水素添加物を以下の様に合成した。
乾燥させたガラス製フラスコに、ヘキサン(関東化学株式会社製)68質量部を入れ、0℃に冷却した。そこにルイス酸触媒のEtAlCl2(エチルアルミニウムジクロリド)(17%ヘキサン溶液、約1mol/L、東京化成工業株式会社製)0.37質量部を投入し、よく分散させたのち、化学合成によって得たβフェランドレン(純度83.3%)5.1質量部をゆっくりと滴下投入した。1分後に、メタノール8質量部を加えて重合反応を停止した。反応溶液を分液ロートに移した後に1%水酸化ナトリウム溶液20質量部を加えて、よく撹拌した後、水溶液の相を分離除去した。次に、有機溶媒相をエバポレータによりゆっくりと蒸発させ、反応溶液を濃縮させた。濃縮した反応溶液約40質量部をメタノール240質量部にゆっくり滴下し、重合物を再沈させた。得られた沈殿物をろ過によって溶液から分離し、十分乾燥させ、βフェランドレン重合体を得た。反応時のモノマーの反応率は100%であった。
十分窒素置換を行った圧力容器に、脱水したヘキサン61質量部および得られたβフェランドレン重合体4質量部を投入し十分溶解させた。ついで、パラジウム・アルミナ触媒(和光純薬製、Pd:5%)10質量部を添加し、8MPaの水素雰囲気下にて、120℃で10時間、水素添加反応を行った。テフロン(登録商標)からなる孔径1μmのフィルターを用いて反応液をろ過し、触媒を除去した後、メタノールにて再沈させ、沈殿を十分に乾燥させて、βフェランドレン重合体の水素添加物4.5質量部を得た。
合成例1の方法で、反応温度を-78℃に変更して、数平均分子量139,400のβフェランドレン重合体を作製した。さらに水素添加し、水素添加率99.9%、数平均分子量が138,500で、ガラス転移温度が139℃、比重0.93の水素添加βフェランドレン重合体を作製した。
[実施例A1]
合成例1で得られたβフェランドレン重合体の水素添加物(以下、βフェランドレン重合体水添物と呼ぶことがある。)100質量部に対して、紫外線吸収剤として2-(2-ヒドロキシ-5-t-ブチルフェニル)-2H-ベンゾトリアゾールを0.1質量部、および酸化防止剤として、ペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート0.1質量部を粉体ブレンダ―により混合した後、2軸押出機(TEX33、日本製鋼所製)を用いて溶融混練し、ペレット状のβフェランドレン重合体水添物を含む混合組成物を得た。
実施例A1の方法で、反応温度を-78℃に変更して、数平均分子量139,400のβフェランドレン重合体を作製した。さらに水素添加し、水素添加率99.9%、分子量が138,500で、ガラス転移温度が139℃、比重0.93の水素添加βフェランドレン重合体を作製した。これを実施例A1と同様の方法で100μm厚みのフィルムを作成し、フィルムの各物性を測定した。その結果を以下の表2に示す。
脂環式ポリオレフィン系樹脂(日本ゼオン株式会社製ゼオノア1060R)のペレットに対して、熱風乾燥機を用いて、80℃、4時間の乾燥を行なった。次いで、実施例A1と同様な装置を用いて、乾燥したペレットを260℃で溶融押出した。その後、押し出されたシート状の脂環式ポリオレフィン系樹脂を3本の冷却ロールに通して冷却して、幅:約70mm、厚み:100μmの押出成形フィルムを得た。作製したフィルムの各物性を実施例A1と同様に測定した。その評価結果を以下の表2に示す。
ポリメチルメタクリレート樹脂(三菱レイヨン社製、アクリペットTF-8)のペレットに対して、熱布乾燥機を用いて、85℃、6時間乾燥を行った。次いで、実施例A1と同様な装置を用いて、乾燥したペレットを220℃で溶融押出し、押し出されたシート状の脂環式ポリオレフィン系樹脂を3本の冷却ロールに通して冷却して、幅:約70mm、厚み:100μmの押出成形フィルムを得た。作製したフィルムの各物性を実施例A1と同様に測定した。その評価結果を以下の表2に示す。
ポリカーボネート樹脂(三菱エンジニアリングプラスチックス社製、ユーピロンH-3000)を280℃で溶融押出し、押し出されたシート状のポリカーボネート樹脂を3本の冷却ロールに通して冷却して、厚み100μmの押し出し成型フィルムを得た。作製したフィルムの各物性を実施例A1と同様に測定した。その評価結果を以下の表2に示す。
[実施例B1]
合成例1で得た水素添加したβフェランドレン重合体を材料として、住友重機工業製射出成型機SE-75を使用して、外径7mm、レンズ厚み2.5mm、周辺部厚み3mmの非球面対物レンズを製造した。その評価結果を下記の表3に示す。
合成例2で得た水素添加したβフェランドレン重合体を材料として、実施例B1と同じ方法により、非球面対物レンズを製造した。その評価結果を下記の表3に示す。
脂環式ポリオレフィン系樹脂(日本ゼオン株式会社製ZEONEX480R、)のペレットに対して、熱風乾燥機を用いて、80℃、4時間の乾燥を行なった。次いで、実施例B1と同様な装置を用いて、乾燥したペレットを260℃で射出成型してプラスチックレンズを成形した。作製したプラスチックレンズの各物性を実施例B1と同様に測定した。その評価結果を下記の表3に示す。
ポリメチルメタクリレート樹脂(三菱レイヨン社製、アクリペットTF-8)のペレットに対して、熱布乾燥機を用いて、85℃、6時間乾燥を行った。次いで、実施例B1と同様な装置を用いて、乾燥したペレットを220℃で射出成型してプラスチックレンズを成形した。作製したプラスチックレンズの各物性を実施例B1と同様に測定した。その評価結果を下記の表3に示す。
ポリカーボネート樹脂(三菱エンジニアリングプラスチックス社製、ユーピロンH-3000)を、実施例B1と同様な装置を用いて280℃で射出成型してプラスチックレンズを成形した。作製したプラスチックレンズの各物性を実施例B1と同様に測定した。その評価結果を下記の表3に示す。
JIS-K-7361 : 1997 (ISO13468-1:1996)に準拠して測定した。測定装置として、東京電色社製のヘーズメーターTC-H3DPK/IIを用いた。
前述した光学用プラスチックフィルムに関する全光線透過率の測定に際して、上記で合成したβフェランドレン重合体の水素添加物からなる厚み100μmのフィルムを、溶融押出法によって作製し、測定試料として用いた。
前述したプラスチックレンズに関する全光線透過率の測定に際して、溶融押出法により、上記で合成したβフェランドレン重合体の水素添加物からなる厚み3.2mmの試験片を成形して、これを測定試料として用いた。
使用した樹脂のガラス転移温度の測定方法は前述の方法によって測定した。
前述した光学用プラスチックフィルムに関する比重の測定に際して、前述の様に溶融押出法で作製した厚み100μmのフィルムを測定試料として用いた。
前述したプラスチックレンズに関する比重の測定に際して、各成形品を測定試料として用いた。
JIS-K-7112:1999のA法に準じて、以下の判定基準に従って評価した。
A: 比重<1.0 …比重が軽く、良好である。
B: 1.0≦比重<1.1 …比重が重く、不良である。
C: 1.1≦比重 …比重が更に重く、不良である。
前述した光学用プラスチックフィルムに関する引張強度の測定に際して、ISO 527に準拠して、オートグラフ(株式会社島津製作所製)を使用し、上記で作製した厚み100μmのフィルムの23℃における引張強度を測定し、以下の基準で評価した。
A: 60MPa以上 …強い引張強度を有し、良好である。
B: 60MPa未満 …弱い引張強度を有し、不良である。
前述したプラスチックレンズに関する曲げ弾性率の測定に際して、溶融押出法により、上記で合成したβフェランドレン重合体水添物からなる厚さ3.2mmの試験片を成形して、これを測定試料として曲げ弾性率を評価した。
ASTM D790に準拠し、各試料の曲げ弾性率を測定し、以下の基準で評価した。
試料の厚みは3.2mmとした。
A: 2500MPa以上 …良好
B: 2500MPa未満 …不良
前述したプラスチックレンズに関する曲げ弾性率の測定に際して、溶融押出法により、上記で合成したβフェランドレン重合体水添物からなる厚さ3.2mmの平板状の試験片を成形して、ASTM D256に準拠して、ノッチ有の条件にて、アイゾット衝撃強度を測定した。測定装置として万能衝撃試験機(安田精機製作所製)を使用した。
前述した光学用プラスチックフィルムに関する膜厚変動の測定に際して、溶融押出法で作製した厚み100μmのフィルムを測定試料として用い、JIS-K-7130:1999のA法に準じて、前記フィルムの膜厚変動を測定し、以下の判定基準に従って評価した。
A: 膜厚変動≦3.0(%) …膜厚変動が小さく、良好である。
B: 3.0(%)<膜厚変動 …膜厚変動が大きく、不良である。
前述した光学用プラスチックフィルムに関する吸水率の測定に際して、溶融押出法で作製した厚み100μmのフィルムを測定試料として用い、JIS-K-7209-2000に準じて、23℃、24時間の吸水率を測定した。
吸水率(%) = 質量増加分×100/初期質量
前述したプラスチックレンズに関する耐湿性の測定に際して、80℃、90%RHの条件下で、1000時間の耐久試験を行い、その外観変化を目視で観察した。以下の基準で判定した。
A:目視で変化はなく、良好な外観を保った。
B:白濁または変形が見られ、外観が劣化した。
前述した光学用プラスチックフィルムに関する耐光性の測定に際して、溶融押出法により、上記で合成したβフェランドレン重合体水添物からなる厚み500μmのフィルムサンプルを成形して、これを測定試料として用いた。
前述したプラスチックレンズに関する耐光性の測定に際して、溶融押出法により、上記で合成したβフェランドレン重合体水添物からなる厚さ3.2mmの試験片を成形して、これを測定試料として用いた。
上記測定試料を紫外線暴露試験装置に入れ、100時間の促進暴露試験を行い、YI(イエローインデックス)の試験前と試験後における黄変度(ΔYI)を測定した。YIの測定は、以下の判定基準に従って評価した。
ΔYI =(紫外線暴露100時間後のYI)-(紫外線暴露前のYI)
A: ΔYI ≦ 1 …長期の耐光性が非常に良好
B: 1 < ΔYI …長期の耐光性が不良
前述した光学用プラスチックフィルム及びプラスチックレンズの光弾性係数の測定に際して、溶融押出法により、上記で合成したβフェランドレン重合体水添物からなる厚み0.2mmのフィルムサンプルを成形して、これを測定試料として用いた。
上記測定試料を、Tgよりも20℃低い温度で、一晩アニールした後、Tgよりも20℃高い温度で、長軸方向に引っ張り応力をかけ、その際のレターデーションを、エリプソメーターM220(日本分光株式会社製)で測定し、応力に対するレターデーションの変化量から、光弾性係数を算出した。算出した変化量の絶対値を以下の基準に従って分類した。
A:1000未満 …変化量が小さく、非常に良好である。
B:1000以上3000未満 …変化量が許容範囲内であり、良好である。
C: 3000以上 …変化量が大きく、不良である。
変化量の単位は[×10-13cm2/dyn]
前述したプラスチックレンズに関する屈折率の測定に際して、上記で合成したβフェランドレン重合体水添物からなる厚さ100μmの試験片を成形して、その屈折率(nD)を、JIS-K-7142に準拠して、25℃で測定した。測定装置としてアッベ屈折計 DR-M4(株式会社アタゴ製)を使用した。
前述したプラスチックレンズに関するアッベ数の測定に際して、上記で合成したβフェランドレン重合体水添物からなる厚さ100μmの試験片を成形して、そのアッベ数を、25℃で測定した。測定装置としてアッベ屈折計 DR-M4(株式会社アタゴ製)を使用した。得られた測定値を以下の基準で判定した。
A:アッベ数≧57 …良好
B:57>アッベ数≧55 …普通
C:55>アッベ数 …不良
Claims (15)
- 前記βフェランドレン重合体の数平均分子量Mnが4万以上である、請求項1又は2に記載のβフェランドレン重合体。
- オレフィン性炭素-炭素二重結合の少なくとも一部が水素化されている、請求項1~3の何れか一項に記載のβフェランドレン重合体。
- ガラス転移温度Tgが80℃以上である、請求項1~4の何れか一項に記載のβフェランドレン重合体。
- 前記化学式(I)及び(II)で表されるβフェランドレンを、ルイス酸を触媒としてカチオン重合せしめて得られた、請求項1~5の何れか一項に記載のβフェランドレン重合体。
- 前記総質量に対するβフェランドレンの含有量が90質量%以上である、請求項7に記載のβフェランドレン重合体の製造方法。
- 前記βフェランドレン重合体の数平均分子量Mnが4万以上となるまで重合させる、請求項7又は8に記載のβフェランドレン重合体の製造方法。
- 前記カチオン重合の反応温度が-90~100℃である、請求項7~9の何れか一項に記載のβフェランドレン重合体の製造方法。
- 前記カチオン重合の後、得られた重合体中のオレフィン性炭素-炭素二重結合を水素化する、請求項7~10の何れか一項に記載のβフェランドレン重合体の製造方法。
- 請求項1~6の何れか一項に記載のβフェランドレン重合体、又は請求項7~11の何れか一項に記載の製造方法によって得られたβフェランドレン重合体を総質量に対して50質量%以上含有する、成形品。
- 全光線透過率が90%以上である、請求項12に記載の成形品。
- 請求項12に記載の成形品としての光学用プラスチックフィルムであって、ガラス転移温度が80℃以上、且つ比重が0.85以上、1.0未満である前記βフェランドレン重合体が、前記光学用プラスチックフィルムの総質量に対して50~100質量%含まれる、光学用プラスチックフィルム。
- 請求項12に記載の成形品としてのプラスチックレンズであって、比重が0.85以上、1.0未満であり、全光線透過率が90%以上である前記βフェランドレン重合体が、前記プラスチックレンズの総質量に対して50~100質量%含まれる、プラスチックレンズ。
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US15/029,355 US10007029B2 (en) | 2013-10-21 | 2014-10-21 | β-phellandrene polymer, production method for same, and molded article |
CN201480057461.0A CN105658685B (zh) | 2013-10-21 | 2014-10-21 | β水芹烯聚合物、其制造方法及成形品 |
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JP2013-218510 | 2013-10-21 | ||
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JP2014060269A JP2015183072A (ja) | 2014-03-24 | 2014-03-24 | 光学用プラスチックフィルム、偏光フィルム、表面保護フィルム、位相差フィルム、反射防止フィルム、拡散フィルム、透明導電性フィルム、画像表示デバイスの基板フィルム、輝度向上フィルム、及び画像表示デバイス |
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- 2014-10-21 WO PCT/JP2014/077979 patent/WO2015060310A1/ja active Application Filing
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- 2014-10-21 CN CN201480057461.0A patent/CN105658685B/zh not_active Expired - Fee Related
- 2014-10-21 TW TW103136408A patent/TWI639624B/zh not_active IP Right Cessation
- 2014-10-21 KR KR1020167009809A patent/KR20160076518A/ko not_active Application Discontinuation
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US20160223715A1 (en) | 2016-08-04 |
CN105658685A (zh) | 2016-06-08 |
US10007029B2 (en) | 2018-06-26 |
KR20160076518A (ko) | 2016-06-30 |
TW201522396A (zh) | 2015-06-16 |
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