WO2016052370A1 - ポリカーボネート樹脂および光学レンズ - Google Patents
ポリカーボネート樹脂および光学レンズ Download PDFInfo
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- WO2016052370A1 WO2016052370A1 PCT/JP2015/077245 JP2015077245W WO2016052370A1 WO 2016052370 A1 WO2016052370 A1 WO 2016052370A1 JP 2015077245 W JP2015077245 W JP 2015077245W WO 2016052370 A1 WO2016052370 A1 WO 2016052370A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/02—Aliphatic polycarbonates
- C08G64/0208—Aliphatic polycarbonates saturated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/305—General preparatory processes using carbonates and alcohols
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
- C08L69/005—Polyester-carbonates
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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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- 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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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3083—Birefringent or phase retarding elements
-
- 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
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
Definitions
- the present invention relates to a novel polycarbonate resin and an optical lens formed thereby.
- the present invention also relates to an optical lens having a high Abbe number, low birefringence, high transparency, and a high glass transition temperature (heat resistance).
- Optical glass or optical transparent resin is used as a material for optical elements used in the optical systems of various cameras such as cameras, film-integrated cameras, and video cameras.
- Optical glass has excellent heat resistance, transparency, dimensional stability, chemical resistance, etc., and there are many kinds of materials having various refractive indexes (nD) and Abbe numbers ( ⁇ D).
- nD refractive indexes
- ⁇ D Abbe numbers
- processing to an aspheric lens used for aberration correction is a serious obstacle to practical use because it requires extremely high technology and high cost.
- optical lenses made of transparent optical resins have the advantage that they can be mass-produced by injection molding, and are easy to manufacture aspherical lenses. It is used as For example, polycarbonate, polystyrene, poly-4-methylpentene, polymethyl methacrylate, amorphous polyolefin, etc. made of bisphenol A are exemplified.
- a lens element having the same refractive index can be realized with a surface with a smaller curvature, so that the amount of aberration generated on this surface can be reduced, the number of lenses can be reduced, Since it is possible to reduce the size and weight of the lens system by reducing the decentration sensitivity and the lens thickness, it is useful to increase the refractive index.
- optically transparent resins that have been put to practical use for optical lens applications, those having a high Abbe number include polymethyl methacrylate (PMMA) and cycloolefin polymers.
- PMMA polymethyl methacrylate
- cycloolefin polymers have been widely used in optical lens applications because they have excellent heat resistance and excellent mechanical properties.
- Examples of the low Abbe number resin include polyester and polycarbonate.
- the resin described in Patent Document 1 is characterized by a high refractive index and a low Abbe number.
- Patent Documents 2 to 4 describe a polycarbonate copolymer containing a perhydroxydimethananaphthalene skeleton, but the strength of the dihydroxymethyl group is weak because it is in the 2nd and 3rd positions. Is not suitable. Furthermore, the polycarbonates described in Patent Documents 2 to 4 have a problem in terms of heat resistance because of their low glass transition temperature (Tg). For example, the polycarbonate of HOMO described in Example 1 of Patent Document 4 has a glass transition temperature (Tg) as low as 125 ° C. despite having a number average molecular weight of 38000.
- Tg glass transition temperature
- the problem to be solved by the present invention is to provide a resin having a high Abbe number with a small difference in water absorption expansion coefficient with respect to a polycarbonate resin having a high refractive index and a low Abbe number. Moreover, it is providing the optical lens manufactured from this resin.
- the present invention relates to the following polycarbonate resin and optical lens.
- R is H, CH 3 or C 2 H 5.
- the polycarbonate resin according to ⁇ 1> including a mixture with an isomer bonded to a position (isomers at positions 2 and 7).
- ⁇ 3> The above-mentioned ⁇ 2 wherein the 2,6-position isomer and the 2,7-position isomer are contained in a mass ratio of 1.0: 99.0 to 99.0: 1.0.
- ⁇ 4> The polycarbonate resin according to any one of ⁇ 1> to ⁇ 3>, wherein the polycarbonate resin has a water absorption expansion coefficient of 0.01 to 0.5%.
- ⁇ 5> The polycarbonate resin according to any one of ⁇ 1> to ⁇ 4>, wherein the Abbe number of the polycarbonate resin is 25 or more.
- ⁇ 6> The polycarbonate resin according to any one of ⁇ 1> to ⁇ 5>, wherein the polycarbonate resin has a glass transition temperature of 110 to 160 ° C.
- ⁇ 7> The polycarbonate resin according to any one of ⁇ 1> to ⁇ 6>, wherein the polycarbonate resin has a weight average molecular weight of 5,000 to 50,000.
- ⁇ 9> A method for producing a polycarbonate resin having a step of reacting a diol compound represented by the following general formula (2) and a carbonic acid diester. (In the general formula (2), R is H, CH 3 or C 2 H 5.
- the diol compound includes an isomer in which the —CH 2 OH group in the general formula (2) is bonded to the 6-position (an isomer in the 2,6-position) and —CH 2 OH in the general formula (2).
- a high Abbe number resin having a small difference in water absorption expansion coefficient with respect to a polycarbonate resin having a high refractive index and a low Abbe number can be obtained.
- an optical lens manufactured from this resin is obtained.
- the polycarbonate resin of this invention contains the structural unit (henceforth "structural unit (1)") represented by General formula (1). Examples thereof include structural units derived from decahydro-1, 4: 5, 8-dimethananaphthalenediol (sometimes referred to as D-NDM). As will be described later, the structural unit (1) is obtained by reacting the diol compound represented by the general formula (2) with a carbonic acid diester.
- the polycarbonate resin of the present invention may contain other structural units in addition to the polycarbonate resin consisting only of the structural unit (1).
- diol compounds other than general formula (2) include bisphenol A and bisphenol.
- AP bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, bisphenol Z, 9,9-bis (4- ( 2-hydroxyethoxy) phenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-methylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-tert- Butylphenyl) Luolene, 9,9-bis (4- (2-hydroxyethoxy) -3-isopropylphenyl) fluorene, 9,9-bis (4- (2-hydroxyethoxy) -3-cyclohexylphenyl) fluorene, 9,9-
- the preferred polystyrene-converted weight average molecular weight (Mw) of the polycarbonate resin of the present invention is 5,000 to 300,000.
- a more preferred polystyrene equivalent weight average molecular weight (Mw) is 30,000 to 120,000.
- the polystyrene equivalent weight average molecular weight (Mw) is preferably from 5,000 to 50,000, more preferably from 7,000 to 45,000.
- 35,000 and 41,000 are mentioned as a preferable lower limit of a polystyrene conversion weight average molecular weight (Mw). If Mw is less than 5,000, the optical lens becomes brittle, which is not preferable. If Mw is greater than 300,000, the melt viscosity will be high, and it will be difficult to remove the resin after production, and the fluidity will be poor, making it difficult to injection mold in the molten state.
- the reduced viscosity ( ⁇ sp / C) of the polycarbonate resin of the present invention is 0.20 dl / g or more, preferably 0.23 to 0.84 dl / g.
- an antioxidant it is preferable to add an antioxidant, a release agent, an ultraviolet absorber, a fluidity modifier, a crystal nucleating agent, a reinforcing agent, a dye, an antistatic agent or an antibacterial agent to the polycarbonate resin of the present invention.
- the diol compound represented by general formula (2) is prepared by using, for example, dicyclopentadiene or cyclopentadiene and an olefin having a functional group as a raw material. It is possible to synthesize with the route shown in FIG.
- R is H, CH 3 or C 2 H 5.
- R 1 is COOCH 3 , COOC 2 H 5 , COOC 3 H 7 , COOC 4 H 9 , or CHO.
- the monoolefin having 13 to 19 carbon atoms represented by the formula (C) can be produced by performing a Diels-Alder reaction between an olefin having a functional group and dicyclopentadiene.
- olefins having a functional group used for the Diels-Alder reaction include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, methacrolein, Acrolein etc. are mentioned, More preferable olefins include methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, methacrolein, and acrolein.
- the dicyclopentadiene used in the Diels-Alder reaction preferably has a high purity, and it is desirable to avoid containing butadiene, isoprene and the like as much as possible.
- the purity of dicyclopentadiene is more preferably 90% or more, and still more preferably 95% or more.
- monocyclopentadiene since it is known that dicyclopentadiene is depolymerized under heating conditions to form cyclopentadiene (so-called monocyclopentadiene), it is also possible to use cyclopentadiene instead of dicyclopentadiene.
- the monoolefin having 13 to 19 carbon atoms represented by the formula (C) is substantially a monoolefin having 8 to 14 carbon atoms represented by the following formula (4) (first stage Diels-Alder reaction product).
- the resulting monoolefin of formula (4) is present in the reaction system as a new parent diene compound (Dienophile) and Diels Alder reaction (second stage) It is considered that a monoolefin having 13 to 19 carbon atoms represented by the formula (C) is produced by the Diels-Alder reaction.
- R is H, CH 3 or C 2 H 5.
- R 1 is COOCH 3 , COOC 2 H 5 , COOC 3 H 7 , COOC 4 H 9 , or CHO
- the reaction temperature is preferably 100 ° C or higher, more preferably 120 ° C or higher, and 130 ° C. The above is particularly preferable.
- the reaction is preferably performed at a temperature of 250 ° C. or lower in order to suppress the by-product of the high boiling substance.
- hydrocarbons, alcohols, esters and the like can be used as reaction solvents, such as aliphatic hydrocarbons having 6 or more carbon atoms, cyclohexane, toluene, xylene, ethylbenzene, mesitylene, propanol, butanol and the like. Is preferred.
- the Diels-Alder reaction can be performed in batch systems using a tank reactor, semi-batch systems in which substrates and substrate solutions are supplied to a tank reactor under reaction conditions, and substrates in a tube reactor under reaction conditions. It is possible to adopt various reaction methods such as a continuous flow method for distributing the gas.
- the reaction product obtained by the Diels-Alder reaction can be used as it is as a raw material for the next hydroformylation reaction, but may be used for the next step after being purified by a method such as distillation, extraction or crystallization.
- the bifunctional compound having 14 to 20 carbon atoms represented by the formula (B) in the formula (3) includes a monoolefin having 13 to 19 carbon atoms represented by the formula (C), carbon monoxide, and hydrogen gas. Can be produced by a hydroformylation reaction in the presence of a rhodium compound or an organophosphorus compound.
- the rhodium compound used in the hydroformylation reaction is not limited in the form of its precursor as long as it is a compound that forms a complex with an organophosphorus compound and exhibits hydroformylation activity in the presence of carbon monoxide and hydrogen.
- Catalyst precursors such as rhodium acetylacetonate dicarbonyl (hereinafter referred to as Rh (acac) (CO) 2 ), Rh 2 O 3 , Rh 4 (CO) 12 , Rh 6 (CO) 16 , Rh (NO 3 ) 3
- Rh 2 O 3 Rh 4 (CO) 12
- Rh 6 (CO) 16 Rh (NO 3 ) 3
- the substance may be introduced into the reaction mixture together with the organophosphorus compound to form a rhodium metal hydridocarbonyl phosphorus complex having catalytic activity in the reaction vessel, or a rhodium metal hydridocarbonyl phosphorus complex may be
- Rh (acac) (CO) 2 is reacted with an organophosphorus compound in the presence of a solvent, and then introduced into a reactor together with an excess of organophosphorus compound, and a rhodium-organophosphorus complex having catalytic activity and The method of doing is mentioned.
- the amount of rhodium compound used in the present hydroformylation reaction is preferably 0.1 to 30 micromoles per 1 mol of a monoolefin having 13 to 19 carbon atoms represented by the formula (C) as a substrate for the hydroformylation reaction. 0.2 to 20 micromol is more preferable, and 0.5 to 10 micromol is even more preferable.
- the rhodium catalyst cost can be reduced without providing a rhodium complex recovery and recycling facility. This can reduce the economic burden associated with recovery and recycling equipment.
- an organophosphorus compound that forms a catalyst for the hydroformylation reaction with a rhodium compound may be a phosphine represented by the general formula P (—R 1 ) (— R 2 ) (— R 3 ) or P (— And a phosphite represented by OR 1 ) (— OR 2 ) (— OR 3 ).
- R 1 , R 2 and R 3 include an aryl group which can be substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group, an alicyclic group which can be substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group. An alkyl group etc.
- a triphenyl phosphine and a triphenyl phosphite are used suitably.
- the amount of the organophosphorus compound used is preferably 500 times to 10000 times mol of rhodium metal, more preferably 700 times to 5000 times mol, and still more preferably 900 times to 2000 times mol.
- the amount of the organophosphorus compound used is less than 500 times the amount of rhodium metal, the stability of the rhodium metal hydridocarbonyl phosphorus complex of the catalyst active material is impaired, and as a result, the progress of the reaction is delayed, which is not preferable. .
- there is more usage-amount of an organophosphorus compound than 10000 times mole of a rhodium metal since the cost concerning an organophosphorus compound increases, it is unpreferable.
- the hydroformylation reaction can be carried out without using a solvent, but can be more suitably carried out by using a solvent inert to the reaction.
- the solvent is not particularly limited as long as it dissolves the monoolefin having 13 to 19 carbon atoms represented by the formula (C), dicyclopentadiene or cyclopentadiene, the rhodium compound, and the organophosphorus compound.
- hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, aliphatic esters, alicyclic esters, esters such as aromatic esters, aliphatic alcohols, alicyclic alcohols And other solvents such as alcohols and aromatic halides. Of these, hydrocarbons are preferably used, and alicyclic hydrocarbons and aromatic hydrocarbons are particularly preferably used.
- the temperature for carrying out the hydroformylation reaction is preferably 40 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C.
- the reaction temperature is 40 ° C. or higher, a sufficient reaction rate can be obtained, and the residual monoolefin as a raw material can be suppressed.
- reaction temperature 160 degrees C or less the production
- CO and H 2 gas can be independently introduced into the reaction system, or can be introduced into the reaction system as a mixed gas prepared in advance.
- the reaction activity of the hydroformylation reaction and the selectivity of the target aldehyde may be reduced. Since CO and H 2 gas introduced into the reaction system decrease with the progress of the reaction, there are cases where the reaction control is simple when a mixed gas of CO and H 2 prepared in advance is used.
- the reaction pressure for the hydroformylation reaction is preferably 1 to 12 MPa, more preferably 1.2 to 9 MPa, and even more preferably 1.5 to 5 MPa.
- the reaction pressure is set to 1 MPa or more, a sufficient reaction rate can be obtained, and the residual monoolefin as a raw material can be suppressed.
- the reaction pressure is set to 12 MPa or less, it is economically advantageous because expensive equipment excellent in pressure resistance is not required.
- reaction system for carrying out the present hydroformylation reaction a batch reaction or a semi-batch reaction is suitable.
- the semi-batch reaction involves adding a rhodium compound, an organophosphorus compound, and the solvent to the reactor, pressurizing or warming with CO / H 2 gas, etc. This can be done by feeding the solution to the reactor.
- the reaction product obtained by the hydroformylation reaction can be used as a raw material for the next reduction reaction as it is, but may be used for the next step after purification by distillation, extraction, crystallization or the like.
- the bifunctional compound having 14 to 16 carbon atoms represented by the formula (A) in the formula (3) has a hydrogenating ability compared to the bifunctional compound having 14 to 20 carbon atoms represented by the formula (B). It can manufacture by reducing in presence of the catalyst which has and hydrogen.
- a catalyst containing at least one element selected from the group consisting of copper, chromium, iron, zinc, aluminum, nickel, cobalt, and palladium is used as a catalyst having hydrogenation ability.
- a catalyst having hydrogenation ability examples include a Cu—Cr catalyst, a Cu—Zn catalyst, a Cu—Zn—Al catalyst and the like, as well as a Raney-Ni catalyst and a Raney-Co catalyst.
- the amount of the hydrogenation catalyst used is 1 to 100% by weight, preferably 2 to 50% by weight, more preferably based on the bifunctional compound having 14 to 20 carbon atoms represented by the formula (B) as the substrate. 5 to 30% by weight.
- the hydrogenation reaction can be suitably carried out.
- the amount of catalyst used is small, the reaction is not completed, and as a result, the yield of the target product is lowered.
- the amount of catalyst used is large, an effect of improving the reaction rate corresponding to the amount of catalyst used for the reaction cannot be obtained.
- the reaction temperature of the reduction reaction is preferably 80 to 250 ° C, more preferably 100 to 230 ° C.
- the reaction temperature of the reduction reaction is preferably 80 to 250 ° C, more preferably 100 to 230 ° C.
- the reaction pressure of the reduction reaction is preferably 1 to 20 MPa as hydrogen partial pressure, and more preferably 2 to 15 MPa.
- the reaction pressure of the reduction reaction is preferably 1 to 20 MPa as hydrogen partial pressure, and more preferably 2 to 15 MPa.
- a solvent in the reduction reaction.
- aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, alcohols and the like can be used, and among them, alicyclic hydrocarbons, aromatic hydrocarbons, alcohols are preferable.
- Specific examples include cyclohexane, toluene, xylene, methanol, ethanol, 1-propanol and the like.
- the reaction method of the reduction reaction is a batch type using a tank reactor, a semi-batch type that supplies a substrate or substrate solution to a tank reactor under the reaction conditions, or a tube type reactor filled with a molded catalyst under the reaction conditions. It is possible to adopt various reaction methods such as a continuous flow method in which a substrate or a substrate solution is circulated.
- the reaction product obtained by the reduction reaction can be purified by, for example, distillation, extraction or crystallization.
- the polycarbonate resin of the present invention can be produced by a melt polycondensation method using a diol compound represented by the general formula (2) and a carbonic acid diester as raw materials.
- the polycondensation catalyst can be produced in the presence of a basic compound catalyst, a transesterification catalyst, or a mixed catalyst composed of both.
- Examples of the carbonic acid diester include diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate.
- diphenyl carbonate is particularly preferable from the viewpoints of reactivity and purity.
- the carbonic acid diester is preferably used in a ratio of 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, relative to 1 mol of the diol component. By adjusting this molar ratio, the molecular weight of the polycarbonate resin is controlled.
- Examples of the basic compound catalyst include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.
- alkali metal compound used in the present invention examples include organic acid salts, inorganic salts, oxides, hydroxides, hydrides or alkoxides of alkali metals.
- alkaline earth metal compound examples include organic acid salts, inorganic salts, oxides, hydroxides, hydrides or alkoxides of alkaline earth metal compounds.
- magnesium hydroxide, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium stearate, calcium benzoate, magnesium phenyl phosphate and the like are used.
- nitrogen-containing compound examples include quaternary ammonium hydroxide and salts thereof, amines and the like.
- quaternary ammonium hydroxides having alkyl, aryl groups, etc. such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylamine , Tertiary amines such as dimethylbenzylamine and triphenylamine, secondary amines such as diethylamine and dibutylamine, primary amines such as propylamine and butylamine, 2-methylimidazole, 2-phenylimidazole, benzimidazole, etc.
- Imidazoles or ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tet Phenyl borate, basic or basic salts such as tetraphenyl ammonium tetraphenylborate, or the like is used.
- transesterification catalyst zinc, tin, zirconium and lead salts are preferably used, and these can be used alone or in combination. Moreover, you may use in combination with the alkali metal compound and alkaline-earth metal compound which were mentioned above.
- transesterification catalyst examples include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, and dibutyltin.
- Dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, lead (IV) acetate and the like are used.
- These catalysts are used in a ratio of 1 ⁇ 10 ⁇ 9 to 1 ⁇ 10 ⁇ 3 mol, preferably 1 ⁇ 10 ⁇ 7 to 1 ⁇ 10 ⁇ 4 mol, relative to a total of 1 mol of diol compounds. .
- the melt polycondensation method is a method in which melt polycondensation is carried out using the above-mentioned raw materials and catalyst while removing by-products by a transesterification reaction under normal pressure or reduced pressure.
- the reaction is generally carried out in a multistage process of two or more stages.
- the first stage reaction is carried out at a temperature of 120 to 260 ° C., preferably 180 to 240 ° C. for 0.1 to 5 hours, preferably 0.5 to 3 hours.
- the reaction temperature is raised while raising the degree of vacuum of the reaction system to react the diol compound with the carbonic acid diester.
- polycondensation is carried out at a temperature of 200 to 350 ° C. under a reduced pressure of 1 mmHg or less for 0.05 to 2 hours. Perform the reaction.
- Such a reaction may be carried out continuously or batchwise.
- the reaction apparatus used for carrying out the above reaction is equipped with paddle blades, lattice blades, glasses blades, etc.
- the catalyst may be removed or deactivated after the polymerization reaction in order to maintain thermal stability and hydrolysis stability.
- a method of deactivating a catalyst by adding a known acidic substance is preferably performed.
- these substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, and aromatic sulfonic acids such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate.
- Esters phosphoric acids such as phosphorous acid, phosphoric acid, phosphonic acid, triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, phosphorous acid Phosphorous esters such as di-n-butyl, di-n-hexyl phosphite, dioctyl phosphite, monooctyl phosphite, triphenyl phosphate diphenyl phosphate, monophenyl phosphate, dibutyl phosphate, phosphoric acid Phosphate esters such as dioctyl and monooctyl phosphate, phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid and dibutylphosphonic acid, Phosphonate esters such as diethyl phosphonate, pho
- butyl p-toluenesulfonate From the viewpoint of the deactivation effect, resin hue and stability, it is preferable to use butyl p-toluenesulfonate.
- These deactivators are used in an amount of 0.01 to 50 times mol, preferably 0.3 to 20 times mol for the amount of catalyst. When the amount is less than 0.01 times the amount of the catalyst, the deactivation effect is insufficient, which is not preferable. Moreover, when it is more than 50 times mole with respect to the amount of catalyst, since heat resistance falls and a molded object becomes easy to color, it is unpreferable.
- a step of devolatilizing and removing low boiling point compounds in the polymer at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350 ° C. may be provided.
- paddle blades, lattice blades, glasses A horizontal apparatus provided with a stirring blade having excellent surface renewability such as a blade or a thin film evaporator is preferably used.
- the polycarbonate resin of the present invention is desired to have as little foreign matter content as possible, and filtration of the molten raw material and filtration of the catalyst solution are suitably performed.
- the filter mesh is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less.
- generate is implemented suitably.
- the mesh of the polymer filter is preferably 100 ⁇ m or less, more preferably 30 ⁇ m or less.
- the step of collecting the resin pellets must naturally be a low dust environment, and is preferably class 1000 or less, more preferably class 100 or less.
- the optical lens of the present invention has a high Abbe number, high transparency, an appropriate water absorption rate, and an appropriate water absorption expansion rate.
- the preferred glass transition temperature (Tg) of the polycarbonate resin of the present invention is 95 to 180 ° C., more preferably 110 to 160 ° C., and particularly preferably 120 to 160 ° C.
- 130 degreeC and 140 degreeC are mentioned as a preferable lower limit of glass transition temperature (Tg)
- 150 degreeC is mentioned as a preferable upper limit of glass transition temperature (Tg).
- Tg is lower than 95 ° C., the operating temperature range of the lens and camera is narrowed, which is not preferable.
- it exceeds 180 ° C. the molding conditions at the time of injection molding become severe, which is not preferable.
- the refractive index measured by the method of JIS-K-7142 after molding is preferably 1.50 to 1.65, more preferably 1.52 to 1.55.
- the polycarbonate resin of the present invention has an Abbe number measured by the method of JIS-K-7142 after molding of 25 or more, preferably 40 or more, more preferably 50 or more.
- the upper limit of the Abbe number is about 60.
- the polycarbonate resin of the present invention has a total light transmittance of 85.0% or more, preferably 87.0% or more as measured by an integrating sphere photoelectric photometry after molding.
- the upper limit of the total light transmittance is about 99%.
- the polycarbonate resin of the present invention preferably has a water absorption of 0.2 to 0.5%, more preferably 0.3 to 0.4%, as measured by the method of JIS-K-7209.
- the water absorption expansion coefficient of the polycarbonate resin of the present invention is preferably 0.01 to 0.5%, more preferably 0.03 to 0.4%.
- the measuring method of the water absorption expansion coefficient is performed with a micrometer (accuracy of 1/1000 mm).
- the diameter of the disk used for water absorption measurement is measured, and the change rate (%) of the diameter before and after water absorption is defined as the water absorption expansion coefficient.
- optical lens of the present invention can be obtained by injection molding the above-described polycarbonate resin of the present invention into a lens shape by an injection molding machine or an injection compression molding machine.
- the molding conditions for injection molding are not particularly limited, but the molding temperature is preferably 180 to 280 ° C.
- the injection pressure is preferably 50 to 1700 kg / cm 2 .
- the molding environment In order to avoid contamination of foreign matter in the optical lens as much as possible, the molding environment must naturally be a low dust environment, preferably class 1000 or less, more preferably class 100 or less.
- the optical lens of the present invention is preferably used in the form of an aspheric lens as necessary. Since an aspheric lens can substantially eliminate spherical aberration with a single lens, there is no need to remove spherical aberration with a combination of a plurality of spherical lenses, thus reducing weight and reducing production costs. It becomes possible. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses.
- the astigmatism of the aspheric lens is preferably 0 to 15 m ⁇ , more preferably 0 to 10 m ⁇ .
- the thickness of the optical lens of the present invention can be set in a wide range according to the application and is not particularly limited, but is preferably 0.01 to 30 mm, more preferably 0.1 to 15 mm.
- a coating layer such as an antireflection layer or a hard coating layer may be provided as necessary.
- the antireflection layer may be a single layer or a multilayer, and may be organic or inorganic, but is preferably inorganic. Specific examples include oxides or fluorides such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, cerium oxide, magnesium oxide, and magnesium fluoride.
- the antireflection layer is not particularly limited with respect to the combination of single layer / multilayer, or the combination of the components and thickness thereof, but preferably has a two-layer structure or a three-layer structure, particularly preferably a three-layer structure.
- the antireflection layer as a whole is preferably formed to a thickness of 0.0017 to 3.3% of the thickness of the optical lens, specifically 0.05 to 3 ⁇ m, particularly preferably 1 to 2 ⁇ m.
- Refractive index nD, Abbe number ⁇ D The polycarbonate resin was press-molded into a 40 ⁇ , 3 mm-thick disc (molding conditions: 200 ° C., 100 kgf / cm 2 , 2 minutes), cut out at a right angle, and measured by Kalnew KPR-200.
- Total light transmittance It measured by Nippon Denshoku Industries Co., Ltd. MODEL1001 DP. The total light transmittance was measured on a press-molded disk (thickness 3 mm).
- reaction solution After completion of the reaction, the reaction solution was subjected to gas chromatography analysis, and a reaction solution containing 76 g of a bifunctional compound represented by the following formula (2a) and 1.4 g of a monoolefin represented by the formula (3a) (conversion rate 98) %, Selectivity 97%), and after purification by distillation, a part was subjected to the subsequent reaction.
- reaction solution contained 77 g of the bifunctional compound represented by the following formula (2b) and 1.3 g of the monoolefin represented by the formula (3b) (conversion 98%, selectivity 98%).
- a 300 ml stainless steel reactor 50 g of the bifunctional compound represented by the formula (2b) purified by distillation, 150 g of toluene, and 10 ml of Raney cobalt catalyst were added.
- the inside of the system was pressurized with hydrogen gas and reacted at 4 MPa and 100 ° C. for 5 hours.
- the resulting slurry was diluted with methanol, and the catalyst was filtered with a membrane filter having a pore size of 0.2 ⁇ m.
- the solvent was distilled off using an evaporator, and analysis by gas chromatography and GC-MS confirmed that it contained 49 g of a main product having a molecular weight of 236 (yield 96%). -It was confirmed that the obtained main product was a bifunctional compound represented by the following formula (1b).
- reaction liquid contained 78 g of the bifunctional compound represented by the formula (2a) and 0.73 g of the monoolefin represented by the formula (3a) (conversion 99%, selectivity 99%).
- a diol compound represented by formula (2a) is used as a raw material to carry out a reduction reaction (reaction yield 96%), and further by distillation purification, a diol compound represented by formula (1a) (D-NDM) ).
- reaction solution contained 23.8 g of a bifunctional compound represented by the following formula (2c) (yield 98%).
- a bifunctional compound represented by the following formula (2c) Yield 98%). 1.
- the resulting slurry was diluted with methanol, and the catalyst was filtered with a membrane filter having a pore size of 0.2 ⁇ m.
- the solvent was distilled off using an evaporator, and analysis was performed by gas chromatography and GC-MS under the above conditions. It was confirmed that the main product obtained by GC-MS analysis was a bifunctional compound represented by the formula (1c). It was also confirmed that the amount of the bifunctional compound represented by the formula (1c) was 22 g (yield 96%).
- D-NDM represented by the formula (1a) obtained from Monomer Synthesis Example 1: 23.53 g (0.106 mol), diphenyl carbonate: 23.02 g (0.107 mol), and sodium hydrogen carbonate: 0.0 07 mg (0.8 ⁇ mol) was placed in a 300 mL reactor equipped with a stirrer and a distiller, heated to 215 ° C. over 1 hour under a nitrogen atmosphere of 760 Torr, and stirred. Heating was performed in an oil bath, and a transesterification reaction was started from 200 ° C. Stirring was started 5 minutes after the start of the reaction, and after 20 minutes, the pressure was reduced from 760 Torr to 200 Torr over 10 minutes.
- the temperature was raised to 210 ° C while reducing pressure, the temperature was raised to 220 ° C 70 minutes after the start of the reaction, the pressure was reduced to 150 Torr over 30 minutes after 80 minutes, the temperature was raised to 240 ° C and the pressure was reduced to 1 Torr. Holding for 10 minutes, a polycarbonate resin was obtained.
- the polycarbonate resin had a refractive index of 1.536 and an Abbe number of 55.2.
- the total light transmittance was 90%.
- the saturated water absorption rate was 0.38%, and the water absorption expansion rate at saturation was 0.038%.
- Example 2 D-NDM represented by the formula (1a) obtained from Monomer Synthesis Example 1: 23.20 g (0.104 mol), diphenyl carbonate: 22.62 g (0.106 mol), and sodium hydrogen carbonate: 0.6. 26 mg (3.1 ⁇ mol) was put into a 300 mL reactor equipped with a stirrer and a distillation apparatus, and the same operation as in Example 1 was carried out except for the charged amount to obtain a polycarbonate resin.
- the refractive index was 1.534 and the Abbe number was 56.0.
- the total light transmittance 90%.
- the saturated water absorption was 0.34%, and the water absorption expansion at saturation was 0.036%.
- the refractive index was 1.531 and the Abbe number was 57.3.
- the total light transmittance 90%.
- the refractive index was 1.551 and the Abbe number was 45.5.
- the total light transmittance 90%.
- the saturated water absorption was 0.37%, and the water absorption expansion at saturation was 0.038%.
- the refractive index was 1.626 and the Abbe number was 25.3.
- the total light transmittance was 89%.
- the saturated water absorption was 0.37%, and the water absorption expansion rate at saturation was 0.033%.
- the refractive index was 1.597 and the Abbe number was 30.0.
- the total light transmittance was 89%.
- the saturated water absorption was 0.37%, and the water expansion coefficient at saturation was 0.038%.
- Example 7 A polycarbonate resin was synthesized under the same conditions as in Example 1 except that D-NDM represented by Formula (1a) obtained from Monomer Synthesis Example 3 was used.
- the total light transmittance was 90%.
- the saturated water absorption was 0.34%, and the water expansion coefficient at saturation was 0.033%.
- a polycarbonate resin was synthesized under the same conditions as in Example 1 except that this D-NDM was used.
- the total light transmittance was 90%.
- the saturated water absorption was 0.35%, and the water expansion coefficient at saturation was 0.033%.
- a polycarbonate resin was synthesized under the same conditions as in Example 1 except that this D-NDM was used.
- the disk-shaped molded product molded for refractive index and Abbe number measurement using the obtained polycarbonate resin was found to be clouded due to crystallization, and did not lead to evaluation of the refractive index and Abbe number as an optical material. .
- the saturated water absorption was 0.33%, and the water expansion coefficient at saturation was 0.031%.
- D-NDM obtained from monomer synthesis example 2 and represented by the following formula (1b): 25.05 g (0.106 mol), diphenyl carbonate: 22.78 g (0.106 mol), and sodium hydrogen carbonate: 0 .26 mg (3.1 ⁇ mol) was placed in a 300 mL reactor equipped with a stirrer and a distiller, heated to 215 ° C. over 1 hour under a nitrogen atmosphere of 760 Torr, and stirred. Heating was performed in an oil bath, and a transesterification reaction was started from 200 ° C. Stirring was started 5 minutes after the start of the reaction, and after 20 minutes, the pressure was reduced from 760 Torr to 200 Torr over 10 minutes.
- Example 11 D-NDM obtained from monomer synthesis example 4 and represented by the following formula (1c): 26.54 g (0.104 mol), diphenyl carbonate: 22.78 g (0.106 mol), and sodium hydrogen carbonate: 0 .26 mg (3.1 ⁇ mol) was placed in a 300 mL reactor equipped with a stirrer and a distillation apparatus, and the same operation as in Example 1 was carried out except for the charged amount to obtain a polycarbonate resin.
- the refractive index was 1.534 and the Abbe number was 56.6.
- the total light transmittance 90%.
- the saturated water absorption was 0.32%, and the water absorption expansion at saturation was 0.034%.
- An object of the present invention is to provide a polycarbonate resin having a high Abbe number with a small difference in water absorption expansion coefficient with respect to a polycarbonate resin having a high refractive index and a low Abbe number.
- the water absorption rate (%) and the water absorption expansion rate (%) of the resin (target 1 and target 2) to be bonded at the time of lens formation and the high Abbe number resin are shown.
- the tensile yield elongation of the polycarbonate resin obtained in Comparative Example 2 was 51%, whereas the tensile yield elongation of the polycarbonate resin obtained in Example 3 was 150%.
- an excellent high Abbe number optical lens can be obtained. Since the optical lens of the present invention can be injection-molded and is highly productive and inexpensive, it can be used in fields where expensive high Abbe glass lenses have been used, such as cameras, telescopes, binoculars, and television projectors. Useful. Further, since the difference in water absorption between the high Abbe lens and the low Abbe lens becomes small, it is particularly suitable for a small optical lens unit. Furthermore, according to the present invention, a high Abbe aspherical lens that is technically difficult to process with a glass lens can be easily obtained by injection molding, which is extremely useful.
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Abstract
Description
<1> 下記一般式(1)で表される構成単位を含むポリカーボネート樹脂である。
<2> 前記一般式(1)における-CH2O-基が6位に結合した異性体(2,6位の異性体)と、前記一般式(1)における-CH2O-基が7位に結合した異性体(2,7位の異性体)との混合物を含む、上記<1>に記載のポリカーボネート樹脂である。
<3> 前記2,6位の異性体と前記2,7位の異性体とが、質量比で1.0:99.0~99.0:1.0の割合で含まれる、上記<2>に記載のポリカーボネート樹脂である。
<4> ポリカーボネート樹脂の吸水膨張率が0.01~0.5%である、上記<1>から<3>のいずれかに記載のポリカーボネート樹脂である。
<5> ポリカーボネート樹脂のアッベ数が25以上である、上記<1>から<4>のいずれかに記載のポリカーボネート樹脂である。
<6> ポリカーボネート樹脂のガラス転移温度が110~160℃である、上記<1>から<5>のいずれかに記載のポリカーボネート樹脂である。
<7> ポリカーボネート樹脂の重量平均分子量が5,000~50,000である、上記<1>から<6>のいずれかに記載のポリカーボネート樹脂である。
<8> 上記<1>から<7>のいずれかに記載のポリカーボネート樹脂を成形することにより得られる光学レンズである。
<9> 下記一般式(2)で表されるジオール化合物および炭酸ジエステルを反応させる工程を有するポリカーボネート樹脂の製造方法である。
<10> 前記ジオール化合物が、前記一般式(2)における-CH2OH基が6位に結合した異性体(2,6位の異性体)と、前記一般式(2)における-CH2OH基が7位に結合した異性体(2,7位の異性体)との混合物を含む、上記<9>に記載のポリカーボネート樹脂の製造方法である。
本発明のポリカーボネート樹脂は、一般式(1)で表される構成単位(以下、「構成単位(1)」という)を含む。これにはデカヒドロ-1、4:5、8-ジメタノナフタレンジオール(D-NDMと記載することがある)から誘導される構成単位が例示される。後述するように構成単位(1)は、一般式(2)で表されるジオール化合物と炭酸ジエステルを反応させて得られる。
一般式(2)で表されるジオール化合物は、ジシクロペンタジエンまたはシクロペンタジエンと官能基を有するオレフィンを原料として例えば下記式(3)に示すルートで合成することが可能である。
式(C)で表される炭素数13~19のモノオレフィンは、官能基を有するオレフィンとジシクロペンタジエンのディールスアルダー反応を行うことで製造することが可能である。
前記式(3)中の式(B)で表される炭素数14~20の二官能性化合物は、式(C)で表される炭素数13~19のモノオレフィンと一酸化炭素および水素ガスをロジウム化合物、有機リン化合物の存在下でヒドロホルミル化反応せしめることで製造することが出来る。
前記式(3)中の式(A)で表される炭素数14~16の二官能性化合物は、式(B)で表される炭素数14~20の二官能性化合物を水素化能を有する触媒および水素の存在下で還元することにより製造することが出来る。
本発明のポリカーボネート樹脂は、一般式(2)で表されるジオール化合物と炭酸ジエステルを原料として溶融重縮合法により製造することができる。一般式(2)で表されるジオール化合物には、ヒドロキシメチル基が2,6位の異性体および2,7位の異性体の混合物が存在する。これらの異性体は質量比で、2,6位の異性体:2,7位の異性体=0.1:99.9~99.9:0.1である。樹脂の強度、引張伸度、成形体の外観などの樹脂物性の観点から、2,6位の異性体:2,7位の異性体=1.0:99.0~99.0:1.0であることが好ましく、2,6位の異性体:2,7位の異性体=20:80~80:20であることがより好ましく、2,6位の異性体:2,7位の異性体=50:50~80:20であることが特に好ましい。さらに、他のジオール化合物を併用しても良い。この反応では重縮合触媒として、塩基性化合物触媒、エステル交換触媒もしくはその双方からなる混合触媒の存在下、製造することができる。
また、本発明のポリカーボネート樹脂の好ましいガラス転移温度(Tg)は95~180℃であり、より好ましくは110~160℃であり、特に好ましくは120~160℃である。また、ガラス転移温度(Tg)の好ましい下限値として、130℃および140℃が挙げられ、ガラス転移温度(Tg)の好ましい上限値として、150℃が挙げられる。Tgが95℃より低いと、レンズやカメラの使用温度範囲が狭くなるため好ましくない。また、180℃を超えると射出成形を行う際の成形条件が厳しくなるため好ましくない。
吸水膨張率の測定方法はマイクロメーター(精度1000分の1mm)によって行う。吸水率測定に使用する円板の直径を測定し、吸水前後の直径の変化率(%)を吸水膨張率とする。
本発明の光学レンズは、上述した本発明のポリカーボネート樹脂を射出成形機あるいは射出圧縮成形機によりレンズ形状に射出成形することによって得ることができる。射出成形の成形条件は特に限定されないが、成形温度は好ましくは180~280℃である。また、射出圧力は好ましくは50~1700kg/cm2である。
GPCを用い、テトラヒドロフランを展開溶媒として、既知の分子量( 分子量分布=1)の標準ポリスチレンを用いて検量線を作成した。この検量線に基づいてGPCのリテンションタイムから算出した。
2)ガラス転移温度(Tg):
示差熱走査熱量分析計(DSC)により測定した。
3)屈折率nD、アッベ数νD:
ポリカーボネート樹脂を、40φ、3mm厚の円板にプレス成形(成形条件:200℃、100kgf/cm2、2分)し、直角に切り出し、カルニュー製KPR-200により測定した。
4)全光線透過率:
日本電色工業(株)製MODEL1001 DPにより測定した。なお、全光線透過率は、プレス成形した円板(厚み3mm)について測定した。
5)飽和吸水率
プレス成形した円板(厚み3mm)をJIS-K-7209に準じて測定した。
6)吸水膨張率
吸水率測定に使用したサンプルについて、吸水前と吸水後に、直径をマイクロメーター(Mitutoyo製、精度1000分の1mm)によって測定し、直径の変化率(%)を以下の数式(1)より算出した。
飽和時の吸水膨張率={(飽和吸水時の円板直径)-(吸水率測定前の円板直径)}×100/(吸水率測定前の円板直径)
・・・数式(1)
・500mlステンレス製反応器にアクリル酸メチル173g(2.01mol)、ジシクロペンタジエン167g(1.26mol)を仕込み195℃で2時間反応を行った。下記式(3a)で表されるモノオレフィン96gを含有する反応液を取得し、これを蒸留精製した後、一部を後段の反応に供した。
・300mlステンレス製反応器を使用し、蒸留精製した式(3a)で表されるモノオレフィンのヒドロホルミル化反応をCO/H2混合ガス(CO/H2モル比=1)を用いて行った。反応器に式(3a)で表されるモノオレフィン70g、トルエン140g、亜リン酸トリフェニル0.50g、別途調製したRh(acac)(CO)2のトルエン溶液550μl(濃度0.003mol/L)を加えた。窒素およびCO/H2混合ガスによる置換を各々3回行った後、CO/H2混合ガスで系内を加圧し、100℃、2MPaにて5時間反応を行った。反応終了後、反応液のガスクロマトグラフィー分析を行い、下記式(2a)で表される二官能性化合物76g、式(3a)で表されるモノオレフィン1.4gを含む反応液(転化率98%、選択率97%)であることを確認すると共に、これを蒸留精製した後、一部を後段の反応に供した。
・300mlステンレス製反応器に蒸留精製した式(2a)で表される二官能性化合物50g、Cu-Zn-Al触媒(日揮触媒化成株式会社製:E-01X)10g、トルエン150gを添加し、水素ガスで系内を加圧し、10MPa、215℃で8時間反応を行った。反応後、得られたスラリーをメタノールで希釈し、孔径0.2μmのメンブレンフィルターで触媒をろ過した後、エバポレーターを使用して溶媒を留去し、ガスクロマトグラフィー及びGC-MSで分析し、分子量222の主生成物43gを含有することが確認された(主生成物収率96%)。これをさらに蒸留精製し主生成物を取得した。
モノマー合成例1で取得した成分のNMR分析、ガスクロマトグラフィー分析およびGC-MS分析を行った。NMRスペクトルを図1~3に示す。
1)NMR測定条件
・装置 :日本電子株式会社製,JNM-ECA500(500MHz)
・測定モード :1H-NMR、13C-NMR、COSY-NMR
・溶媒 :CD3OD(重メタノール)
・内部標準物質:テトラメチルシラン
2)ガスクロマトグラフィー測定条件
・分析装置 :株式会社島津製作所製 キャピラリガスクロマトグラフGC-2010 Plus
・分析カラム :ジーエルサイエンス株式会社製、InertCap1(30m、0.32mmI.D.、膜厚0.25μm)
・オーブン温度:60℃(0.5分間保持)-15℃/分にて昇温-280℃(4分間保持)・検出器 :FID、温度280℃
3)GC-MS測定条件
・分析装置 :株式会社島津製作所製、GCMS-QP2010 Plus
・イオン化電圧:70eV
・分析カラム :Agilent Technologies製、DB-1(30m、0.32mmI.D.、膜厚1.00μm)
・オーブン温度:60℃(0.5分間保持)-15℃/分にて昇温-280℃(4分間保持)検出器温度:280℃
・モノマー合成例1のアクリル酸メチルの代わりにメタクロレイン141g(1.93mol/純度96%)を使用して下記式(3b)で表されるモノオレフィン86gを含有する反応液を取得し、これを蒸留精製した後、一部を後段の反応に供した。
・300mlステンレス製反応器を使用し、式(3b)で表されるモノオレフィンのヒドロホルミル化反応をCO/H2混合ガス(CO/H2モル比=1)を用いて行った。反応器に式(3b) で表されるモノオレフィン70g、トルエン140g、亜リン酸トリフェニル0.55g、別途調製したRh(acac)(CO)2のトルエン溶液580μl(濃度0.003mol/L)を加えた。窒素およびCO/H2混合ガスによる置換を各々3回行った後、CO/H2混合ガスで系内を加圧し、100℃、2MPaにて6時間反応を行った。反応終了後、反応液のガスクロマトグラフィー分析を行った。下記式(2b)で表される二官能性化合物77g、式(3b)で表されるモノオレフィン1.3gを含む反応液であることを確認した(転化率98%、選択率98%)
・300mlステンレス製反応器に蒸留精製した式(2b)で表される二官能性化合物50g、トルエン150g、ラネーコバルト触媒10mlを添加した。水素ガスで系内を加圧し、4MPa、100℃で5時間反応を行った。反応後、得られたスラリーをメタノールで希釈し、孔径0.2μmのメンブレンフィルターで触媒をろ過した。エバポレーターを使用して溶媒を留去し、ガスクロマトグラフィー及びGC-MSで分析し、分子量236の主生成物49gを含有することを確認した(収率96%)。
・得られた主生成物は下記式(1b)で表される二官能性化合物であることが確認された。
・モノマー合成例1と同様にして式(3a)で表されるモノオレフィンの合成ならびに蒸留精製を行った。
・300mlステンレス製反応器を使用し、式(3a)で表されるモノオレフィンのヒドロホルミル化反応をCO/H2混合ガス(CO/H2モル比=1)を用いて行った。ステンレス製のタンクに式(3a)で表されるモノオレフィン70gとトルエン100gを加え、窒素およびCO/H2混合ガスによる置換を各々3回行った後、CO/H2混合ガスで系内を微加圧にした。これとは別に、300mlステンレス製反応器にトルエン40g、亜リン酸トリフェニル0.13g、別途調製したRh(acac)(CO)2のトルエン溶液120μl(濃度0.003mol/L)を加え、窒素およびCO/H2混合ガスによる置換を各々3回行った後、CO/H2混合ガスで系内を加圧し、100℃、2MPaに保持した。前述のステンレス製タンクから式(3a)で表されるモノオレフィンのトルエン溶液を2時間掛けて反応器に供給し(その間、反応器は100℃、2MPaに制御)、供給終了後、100℃、2MPaにて3時間熟成を行った。反応終了後、反応液のガスクロマトグラフィー分析を行った。式(2a)で表される二官能性化合物78g、式(3a)で表されるモノオレフィン0.73gを含む反応液であることを確認した(転化率99%、選択率99%)
・モノマー合成例1同様、式(2a)で表されるジオール化合物を原料として還元反応を行い(反応収率96%)、更に蒸留精製により式(1a)で表されるジオール化合物(D-NDM)を取得した。ガスクロマトグラフィーによる分析より、得られたジオール化合物は、ヒドロキシメチル基が2,6位の異性体=52質量%および2,7位の異性体=48質量%の異性体混合物であることが確認された。
モノマー合成例1のアクリル酸メチルの代わりに、エチルアクロレイン52g(0.61mol/純度99%)を使用して下記式(3c)で表されるモノオレフィン14gを含有する反応液を取得した。同反応を2回行い、蒸留精製した後、一部を後段の反応に供した。
300mlステンレス製反応器を使用し、式(3c) で表されるモノオレフィンのヒドロホルミル化反応をCO/H2混合ガス(CO/H2モル比=1)を用いて行った。反応器に式(3c)で表されるモノオレフィン21.3g、トルエン20g、トリフェニルホスフィン518mg、別途調製したRh(acac)(CO)2のトルエン溶液128μl(濃度0.0384mol/L)を加えた。窒素およびCO/H2混合ガスによる置換を各々3回行った後、CO/H2混合ガスで系内を加圧し、110℃、2MPaにて1.5時間反応を行った。反応終了後、上記の条件で反応液のガスクロマトグラフィー分析を行った。その結果、下記式(2c)で表される二官能性化合物23.8gを含む反応液であることを確認した(収率98%)。
300mlステンレス製反応器に式(2c)で表される二官能性化合物22.7gを含む反応液、シクロヘキサノール38g、Cu-Zn-Al触媒(日揮触媒化成株式会社製:E-01X)2.2gを添加した。水素ガスで系内を加圧し、3MPa、140℃で1.5時間反応を行った。反応後、得られたスラリーをメタノールで希釈し、孔径0.2μmのメンブレンフィルターで触媒をろ過した。エバポレーターを使用して溶媒を留去し、上記の条件でガスクロマトグラフィー及びGC-MSで分析を行った。GC-MS分析より得られた主生成物は式(1c)で表される二官能性化合物であることを確認した。また、式(1c)で表される二官能性化合物の生成量が22gであることも確認した(収率96%)。
モノマー合成例1より得られた式(1a)で表されるD-NDM:23.53g(0.106モル)、ジフェニルカーボネート:23.02g(0.107モル)、および炭酸水素ナトリウム:0.07mg(0.8μモル)を攪拌機および留出装置付きの300mL反応器に入れ、窒素雰囲気760Torrの下1時間かけて215℃に加熱し、撹拌した。オイルバスにて加熱を行い、200℃からエステル交換反応を開始した。反応開始から5分後に攪拌を開始し、20分後、10分かけて760Torrから200Torrまで減圧した。減圧しながら温度を210℃まで加熱し、反応開始後70分後で220℃まで昇温、80分後から30分かけて150Torrまで減圧、温度を240℃まで昇温させるとともに1Torrまで減圧したのち10分間保持し、ポリカーボネート樹脂を得た。
得られたポリカーボネート樹脂のMw=8,000、Tg=110℃であった。このポリカーボネート樹脂の屈折率は1.536、アッベ数55.2であった。全光線透過率は90%であった。また飽和吸水率は0.38%、飽和時の吸水膨張率は0.038%であった。結果を表1および2に示す。
モノマー合成例1より得られた式(1a)で表されるD-NDM:23.20g(0.104モル)、ジフェニルカーボネート:22.62g(0.106モル)、および炭酸水素ナトリウム:0.26mg(3.1μモル)を攪拌機および留出装置付きの300mL反応器に入れ、仕込み量以外は実施例1と同様に操作し、ポリカーボネート樹脂を得た。得られたポリカーボネート樹脂はMw=15,000、Tg=127℃であった。また、屈折率は1.534、アッベ数は56.0であった。全光線透過率は90%であった。また、飽和吸水率は0.34%、飽和時の吸水膨張率は0.036%であった。
モノマー合成例1より得られた式(1a)で表されるD-NDM:30.9g(0.139モル)、ジフェニルカーボネート:29.8g(0.139モル)、および炭酸水素ナトリウム:0.09mg(1.1μモル)を攪拌機および留出装置付きの300mL反応器に入れ、仕込み量以外は実施例1と同様に操作し、ポリカーボネート樹脂を得た。得られたポリカーボネート樹脂はMw=42,000、Tg=141℃であった。また、屈折率は1.531、アッベ数は57.3であった。全光線透過率は90%であった。また、飽和吸水率は0.35%、飽和時の吸水膨張率は0.033%であった。
以下の測定条件で、得られたポリカーボネート樹脂のNMR分析を行った。NMRスペクトルを図4に示す。
NMR測定条件
・装置 :日本電子株式会社製,JNM-ECA500(500MHz)
・測定モード :1H-NMR
・溶媒 :重クロロホルム
・内部標準物質:テトラメチルシラン
モノマー合成例1より得られた式(1a)で表されるD-NDM:28.9g(0.130モル)、9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレン:6.3g(0.014モル)、ジフェニルカーボネート:31.5g(0.147モル)、および炭酸水素ナトリウム:0.09mg(1.1μモル)を攪拌機および留出装置付きの300mL反応器に入れ、仕込み量以外は実施例1と同様に操作し、ポリカーボネート樹脂を得た。得られたポリカーボネート樹脂はMw=27,000、Tg=142℃であった。また、屈折率は1.551、アッベ数は45.5であった。全光線透過率は90%であった。また、飽和吸水率は0.37%、飽和時の吸水膨張率は0.038%であった。
モノマー合成例1より得られた式(1a)で表されるD-NDM:4.76g(0.021モル)、9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレン:37.6g(0.086モル)、ジフェニルカーボネート:23.3g(0.109モル)、および炭酸水素ナトリウム:0.07mg(0.9μモル)を攪拌機および留出装置付きの300mL反応器に入れ、仕込み量以外は実施例1と同様に操作し、ポリカーボネート樹脂を得た。得られたポリカーボネート樹脂はMw=32,000、Tg=146℃であった。また、屈折率は1.626、アッベ数は25.3であった。全光線透過率は89%であった。また、飽和吸水率は0.37%、飽和時の吸水膨張率は0.033%であった。
モノマー合成例1より得られた式(1a)で表されるD-NDM:11.3g(0.051モル)、9,9-ビス(4-(2-ヒドロキシエトキシ)フェニル)フルオレン:20.0g(0.046モル)、ジフェニルカーボネート:21.0g(0.098モル)、および炭酸水素ナトリウム:0.05mg(0.6μモル)を攪拌機および留出装置付きの300mL反応器に入れ、仕込み量以外は実施例1と同様に操作し、ポリカーボネート樹脂を得た。得られたポリカーボネート樹脂はMw=35,000、Tg=144℃であった。また、屈折率は1.597、アッベ数は30.0であった。全光線透過率は89%であった。また、飽和吸水率は0.37%、飽和時の吸水膨張率は0.038%であった。
モノマー合成例3より得られた式(1a)で表されるD-NDMを使用した以外は、実施例1と同様の条件にてポリカーボネート樹脂を合成した。得られたポリカーボネート樹脂はMw=38,000、Tg=140℃、屈折率は1.532、アッベ数は57.2であった。全光線透過率は90%であった。また、飽和吸水率は0.34%、飽和時の吸水膨張率は 0.033%であった。
モノマー合成例3より得られた式(1a)で表されるD-NDM(ヒドロキシメチル基が2,6位の異性体=52質量%および2,7位の異性体=48質量%)の異性体混合物の蒸留を行い、2,6位の異性体=22質量%及び2,7位の異性体=78質量%のD-NDMを得た。このD-NDMを使用した以外は、実施例1と同様の条件にてポリカーボネート樹脂を合成した。得られたポリカーボネート樹脂はMw=41,000、Tg=137℃、屈折率は1.531、アッベ数は57.0であった。全光線透過率は90%であった。また、飽和吸水率は0.35%、飽和時の吸水膨張率は0.033%であった。
モノマー合成例1より得られた式(1a)で表されるD-NDM(ヒドロキシメチル基が2,6位の異性体=76質量%および2,7位の異性体=24質量%)の異性体混合物の蒸留を行い、2,6位の異性体=99.5質量%及び2,7位の異性体=0.5質量%のD-NDMを得た。このD-NDMを使用した以外は、実施例1と同様の条件にてポリカーボネート樹脂を合成した。
得られたポリカーボネート樹脂を用いて屈折率およびアッベ数測定用に成形した円板状成形体は結晶化に起因する白濁が認められ、光学材料として屈折率、およびアッベ数を評価するに至らなかった。また、得られたポリカーボネート樹脂はMw=40,000、Tg=143℃であった。飽和吸水率は0.33%、飽和時の吸水膨張率は0.031%であった。
モノマー合成例2より得られた下記式(1b)で表されるD-NDM:25.05g(0.106モル)、ジフェニルカーボネート:22.78g(0.106モル)、および炭酸水素ナトリウム:0.26mg(3.1μモル)を攪拌機および留出装置付きの300mL反応器に入れ、窒素雰囲気760Torrの下1時間かけて215℃に加熱し、撹拌した。オイルバスにて加熱を行い、200℃からエステル交換反応を開始した。反応開始から5分後に攪拌を開始し、20分後、10分かけて760Torrから200Torrまで減圧した。減圧しながら温度を210℃まで加熱し、反応開始後70分後で220℃まで昇温、80分後から30分かけて150Torrまで減圧、温度を240℃まで昇温させるとともに1Torrまで減圧したのち10分間保持し、ポリカーボネート樹脂を得た。
得られたポリカーボネート樹脂のMw=38,000、Tg=135℃であった。このポリカーボネート樹脂の屈折率は1.533、アッベ数は56.8であった。全光線透過率は90%であった。また、飽和吸水率は0.33%、飽和時の吸水膨張率は0.035%であった。
モノマー合成例4より得られた下記式(1c)で表されるD-NDM:26.54g(0.104モル)、ジフェニルカーボネート:22.78g(0.106モル)、および炭酸水素ナトリウム:0.26mg(3.1μモル)を攪拌機および留出装置付きの300mL反応器に入れ、仕込み量以外は実施例1と同様に操作し、ポリカーボネート樹脂を得た。得られたポリカーボネート樹脂はMw=35,000、Tg=133℃であった。また、屈折率は1.534、アッベ数は56.6であった。全光線透過率は90%であった。また、飽和吸水率は0.32%、飽和時の吸水膨張率は0.034%であった。
低アッベ数のビスフェノールA型ポリカーボネート樹脂(分子量Mw=30,000、三菱ガス化学株式会社製 H-4000)を使用して吸水率(%)と吸水膨張率(%)を測定した。結果を表1と2に示す。
高アッベ数のシクロオレフィンポリマー樹脂(分子量Mw=140,000、日本ゼオン株式会社製 ZEONEX 330R)を使用して吸水率(%)と吸水膨張率(%)を測定した。結果を表1と2に示す。
低アッベ数の光学用ポリカーボネート樹脂(分子量Mw=27,000、三菱ガス化学株式会社製 EP5000)を使用して吸水率(%)と吸水膨張率(%)を測定した。結果を表1と2に示す。
オートクレーブにフマル酸ジメチル108g(0.75モル)、ジシクロペンタジエン128g(0.97モル)およびp-キシレン300gを仕込み、窒素ガスで系内を置換した。次いで、オートクレーブの内温を180℃に昇温し、同温度で攪拌下に20時間反応させた。反応終了後、10%のパラジウムを担持させた活性炭6gを添加し、系内を水素ガスで置換したのち、水素ガスを21MPa仕込み、80℃で1時間攪拌下に反応させた。反応混合物を減圧蒸留に付し、次いで、その残渣をエタノールから再結晶することにより、ペルヒドロ-1,4:5,8-ジメタノナフタレンジカルボン酸ジメチルを得た。内容300mLのオートクレーブにペルヒドロ-1,4:5,8-ジメタノナフタレンジカルボン酸ジメチル52g、銅-クロム酸化物(日揮化学(株)製、N-203-SD)5gおよび1,4-ジオキサン100mLを仕込んだ。次いで、系内を水素ガスで置換したのち、水素ガスを仕込み、30MPaの圧力下、200℃で20時間反応させた。反応終了後、1,4-ジオキサンを除去することにより得られた白色粉末を酢酸エチルから再結晶した結果、下記構造式で表されるペルヒドロ-1,4:5,8-ジメタノナフタレン-2,3-ジメタノールが得られた。
日本工業規格K7113に基づき、得られたポリカーボネート樹脂を1号型試験片の形状に成形し、引っ張り降伏伸び率を測定した(引っ張り速度2mm/min.)。比較例2で得られたポリカーボネート樹脂の引っ張り降伏伸び率は51%であったのに対して、実施例3で得られたポリカーボネート樹脂の引っ張り降伏伸び率は150%であった。
Claims (11)
- 前記一般式(1)における-CH2O-基が6位に結合した異性体(2,6位の異性体)と、前記一般式(1)における-CH2O-基が7位に結合した異性体(2,7位の異性体)との混合物を含む、請求項1に記載のポリカーボネート樹脂。
- 前記2,6位の異性体と前記2,7位の異性体とが、質量比で1.0:99.0~99.0:1.0の割合で含まれる、請求項2に記載のポリカーボネート樹脂。
- ポリカーボネート樹脂の吸水膨張率が0.01~0.5%である、請求項1から3のいずれかに記載のポリカーボネート樹脂。
- ポリカーボネート樹脂のアッベ数が25以上である、請求項1から4のいずれかに記載のポリカーボネート樹脂。
- ポリカーボネート樹脂のガラス転移温度が110~160℃である、請求項1から5のいずれかに記載のポリカーボネート樹脂。
- ポリカーボネート樹脂の重量平均分子量が5,000~50,000である、請求項1から6のいずれかに記載のポリカーボネート樹脂。
- 請求項1から7のいずれかに記載のポリカーボネート樹脂を成形することにより得られる光学レンズ。
- 前記2,6位の異性体と前記2,7位の異性体とが、質量比で1.0:99.0~99.0:1.0の割合で含まれる、請求項10に記載のポリカーボネート樹脂の製造方法。
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Cited By (15)
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WO2017175693A1 (ja) * | 2016-04-05 | 2017-10-12 | 三菱瓦斯化学株式会社 | ポリカーボネート共重合体、それを用いた光学レンズ及びフィルム、並びに該共重合体の製造方法 |
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US10605956B2 (en) | 2020-03-31 |
JPWO2016052370A1 (ja) | 2017-07-27 |
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JP2019214727A (ja) | 2019-12-19 |
TW202028293A (zh) | 2020-08-01 |
JP6648696B2 (ja) | 2020-02-14 |
KR102355569B1 (ko) | 2022-01-25 |
EP3202815A4 (en) | 2018-04-11 |
US20170276837A1 (en) | 2017-09-28 |
EP3202815B1 (en) | 2019-01-23 |
KR20170066280A (ko) | 2017-06-14 |
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CN106661216B (zh) | 2018-12-07 |
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US10048404B2 (en) | 2018-08-14 |
TWI711645B (zh) | 2020-12-01 |
EP3415546A1 (en) | 2018-12-19 |
US20190033489A1 (en) | 2019-01-31 |
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