WO2016190317A1 - ポリエステル樹脂及びその製造方法 - Google Patents
ポリエステル樹脂及びその製造方法 Download PDFInfo
- Publication number
- WO2016190317A1 WO2016190317A1 PCT/JP2016/065337 JP2016065337W WO2016190317A1 WO 2016190317 A1 WO2016190317 A1 WO 2016190317A1 JP 2016065337 W JP2016065337 W JP 2016065337W WO 2016190317 A1 WO2016190317 A1 WO 2016190317A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reaction
- polyester resin
- acid
- general formula
- hydrogen atom
- Prior art date
Links
Images
Classifications
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
- C07C69/757—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/86—Ring systems containing bridged rings containing four rings
Definitions
- the present invention relates to a polyester resin and a method for producing the same.
- PET Polyethylene terephthalate
- PET has excellent transparency, mechanical strength, melt stability, solvent resistance, fragrance retention, and recyclability.
- Film, sheet, hollow container It is a polyester resin that is widely used for various applications.
- PET does not necessarily have a sufficiently high glass transition temperature, and when a thick molded body is obtained, transparency may be impaired due to its crystallinity. It has been broken.
- a polyester resin using 1,4-cyclohexanedimethanol, tricyclodecane dimethanol or pentacyclopentadecane dimethanol as a polyester copolymerization component has been proposed. Since tricyclodecane dimethanol and pentacyclopentadecane dimethanol are bulky and have a rigid skeleton, the polyester resin using them has a high glass transition temperature, crystallinity is suppressed, and the transparency of the molded product is reduced. Can be improved (for example, see Patent Documents 1 and 2).
- Patent Document 3 discloses an aliphatic polyester composed of 1,4-cyclohexanedimethanol and 1,4-cyclohexanedicarboxylic acid.
- polyesters having a norbornane skeleton have been proposed (see, for example, Patent Documents 4 and 5).
- the polyester resins described in Patent Documents 1 and 2 are inferior not only in UV resistance but also in light transmittance because the dicarboxylic acid component is aromatic. Moreover, although the aliphatic polyester of patent document 3 has favorable transparency, its heat resistance is not so high.
- the polyester resin having a norbornane skeleton disclosed in Patent Documents 4 and 5 exhibits better heat resistance than a polyester resin using 1,4-cyclohexanedimethanol and 1,4-cyclohexanedicarboxylic acid as monomers. However, further improvement is required.
- This invention is made
- the present inventors have found that the above problems can be solved by having a structural unit having a specific alicyclic structure in the main skeleton.
- the present invention is as follows.
- ⁇ 1> The polyester resin containing the structural unit represented by General formula (1).
- R 1 is a hydrogen atom, CH 3 or C 2 H 5
- R 2 and R 3 are each independently a hydrogen atom or CH 3
- ⁇ 2> The manufacturing method of a polyester resin which has the process of polymerizing the compound represented by General formula (2).
- R 1 is a hydrogen atom, CH 3 or C 2 H 5
- R 2 and R 3 are each independently a hydrogen atom or CH 3
- X is a hydrogen atom or carbon number.
- It is a hydrocarbon group that may contain 4 or less hydroxyl groups.
- the polyester resin of the present invention is excellent in heat resistance and transparency.
- the result of 1H-NMR measurement of the main reaction product obtained in the monomer synthesis example is shown.
- the result of 13C-NMR measurement of the main reaction product obtained in the monomer synthesis example is shown.
- the result of the COSY-NMR measurement of the main reaction product obtained in the monomer synthesis example is shown.
- the present embodiment a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.
- the following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents.
- the present invention can be implemented with appropriate modifications within the scope of the gist thereof.
- polyester resin of this embodiment contains the structural unit (henceforth "structural unit (1)") represented by following General formula (1).
- R 1 is a hydrogen atom, CH 3 or C 2 H 5
- R 2 and R 3 are each independently a hydrogen atom or CH 3 .
- the polyester resin of this embodiment is excellent in heat resistance and transparency. Since it is excellent in heat resistance (high glass transition temperature), transparency, etc., the polyester resin of this embodiment is suitable as an optical material, an electronic component, or a medical material.
- R 1 is preferably a hydrogen atom or CH 3
- R 2 and R 3 are preferably a hydrogen atom.
- the polyester resin of this embodiment may contain other structural units in addition to the structural unit (1) as long as the performance is not impaired.
- the other structural units are not particularly limited, but terephthalic acid, isophthalic acid, phthalic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6
- a structural unit derived from an aromatic dicarboxylic acid such as naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2-methylterephthalic acid, biphenyldicarboxylic acid, tetralindicarboxylic acid and / or its derivatives; succinic acid, glutaric acid, adipine Acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, decalindicarboxylic acid, norbornanedicarboxylic acid, tricyclodecanedicarbox
- the molecular weight of the polyester resin of the present embodiment can be appropriately set in consideration of desired performance and handling properties, and is not particularly limited, but the polystyrene equivalent weight average molecular weight (Mw) is 5000 to 300,000. And more preferably 10,000 to 250,000.
- Mw polystyrene equivalent weight average molecular weight
- Mw polystyrene equivalent weight average molecular weight
- Mw is 5,000 or more, better heat resistance tends to be secured, and when Mw is 300,000 or less, excessive increase in melt viscosity is prevented, and the resin after production is easily extracted. Furthermore, since good fluidity can be secured, injection molding in a molten state tends to be facilitated.
- the intrinsic viscosity of the polyester resin of this embodiment is not particularly limited. From the viewpoint of moldability of the polyester resin of the embodiment, it is preferably 0.1 to 2.0 dL / g, more preferably 0.2 to 1.5 dL / g.
- the intrinsic viscosity is 0.1 dL / g or more, there is a tendency that sufficient mechanical strength can be ensured when melt-molding the polyester resin of the present embodiment as a raw material to obtain a molded product such as a film.
- it is 0.5 dL / g or less, good fluidity and moldability at the time of melting can be secured, and a molded product having excellent dimensional stability tends to be obtained.
- an antioxidant when using the polyester resin of this embodiment, an antioxidant, a release agent, an ultraviolet absorber, a fluidity modifier, a crystal nucleating agent, a reinforcing agent, a dye, an antistatic agent, an antibacterial agent, etc. are added. Is preferably carried out.
- R 1 is a hydrogen atom
- R 2 and R 3 are each independently a hydrogen atom or CH 3
- X is a hydrogen atom or carbon It is a hydrocarbon group which may contain a hydroxyl group of several 4 or less.
- R 1 is preferably a hydrogen atom or CH 3
- R 2 and R 3 are preferably a hydrogen atom.
- the hydrocarbon group include, but are not limited to, a methyl group, an ethyl group, a propyl group, a butyl group, a vinyl group, a 2-hydroxyethyl group, and a 4-hydroxybutyl group.
- the compound represented by the general formula (2) in this embodiment can be synthesized by using, for example, the route represented by the following formula (I) using dicyclopentadiene or cyclopentadiene and an olefin having a functional group as a raw material. .
- R 1 is a hydrogen atom, CH 3 or C 2 H 5 , R 2 and R 3 are each independently a hydrogen atom or CH 3 , and X is a hydrogen atom or a carbon number of 4 or less. Which may contain a hydroxyl group of
- the monoolefin having 13 to 21 carbon atoms represented by the general formula (4) can be produced, for example, by performing a Diels-Alder reaction between an olefin having a functional group and dicyclopentadiene.
- olefin having a functional group used in the Diels-Alder reaction include, but are not limited to, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, vinyl methacrylate, methacrylic acid-2 -Hydroxyethyl, 4-hydroxybutyl methacrylate, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, vinyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate , Crotonic acid, methyl crotonate, ethyl crotonate, 3-methyl crotonic acid, methyl 3-methyl crotonate, ethyl 3-methyl crotonate and the like.
- Preferred olefins include methacrylic acid, methyl methacrylate, methacrylate.
- Acid-2-hydroxyethyl, acrylic acid, methyl acrylate, include 2-hydroxyethyl acrylate, methyl methacrylate, methyl acrylate may be mentioned as preferred olefin.
- examples of the olefin having a functional group used for the Diels-Alder reaction include acrylonitrile, methacrylonitrile, acrolein, and methacrolein.
- monoolefins represented by the general formula (4 ′) can be produced via the routes shown in the following formulas (II) and (III).
- R 1 is a hydrogen atom or CH 3.
- R 1 is a hydrogen atom or CH 3.
- the dicyclopentadiene used in the Diels-Alder reaction preferably has a high purity, and it is preferable to reduce the content of butadiene, isoprene and the like.
- the purity of dicyclopentadiene is preferably 90% or more, and more preferably 95% or more. Further, since dicyclopentadiene tends to depolymerize under heating conditions to form cyclopentadiene (so-called monocyclopentadiene), it is also possible to use cyclopentadiene instead of dicyclopentadiene.
- the monoolefin having 13 to 21 carbon atoms represented by the general formula (4) is substantially a monoolefin having 8 to 16 carbon atoms represented by the following general formula (7) (the first stage Diels-Alder reaction product).
- Dienophile Dienophile
- the second stage Diels-Alder reaction is considered to produce a monoolefin having 13 to 21 carbon atoms represented by the general formula (4).
- R 1 represents a hydrogen atom, CH 3 or C 2 H 5
- R 2 and R 3 each independently represent a hydrogen atom or CH 3
- X represents a hydrogen atom or a carbon number of 4 or less.
- the reaction temperature is preferably 100 ° C or higher, more preferably 120 ° C or higher, and 130 ° C. The above is more preferable. On the other hand, it is preferable to perform the reaction at a temperature of 250 ° C. or lower in order to suppress by-product of high boiling substances.
- 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. preferable. If necessary, it may be added to AlCl 3 or the like known catalysts.
- the reaction method of the Diels-Alder reaction is a batch system using a tank reactor, a semi-batch system in which a substrate or a substrate solution is supplied to a tank reactor under reaction conditions, and a substrate type under a reaction condition in a tube reactor. 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 a raw material for the next hydroformylation reaction as it is, but may be used for the next step after being purified by a method such as distillation, extraction or crystallization.
- bifunctional compound having 14 to 22 carbon atoms represented by (3) in formula (I) is, for example, a monoolefin having 13 to 21 carbon atoms represented by the general formula (4) and carbon monoxide.
- 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 may be a compound that forms a complex with an organic phosphorus compound and exhibits hydroformylation activity in the presence of carbon monoxide and hydrogen, and the form of the precursor is not particularly limited. .
- 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, etc.
- the catalyst precursor 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.
- a rhodium metal hydridocarbonyl phosphorus complex may be prepared in advance. It may be introduced into the reactor.
- 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 hydroformylation reaction is preferably 0.1 to 60 micromoles per 1 mol of a monoolefin having 13 to 21 carbon atoms represented by the general formula (4) which is a substrate for the hydroformylation reaction. 0.1 to 30 ⁇ mol is more preferable, 0.2 to 20 ⁇ mol is further preferable, and 0.5 to 10 ⁇ mol is particularly preferable.
- the amount of the rhodium compound used is less than 60 micromoles per 1 mol of the monoolefin having 13 to 21 carbon atoms, it can be evaluated that it is practically not necessary to provide a collection and recycling facility for the rhodium complex. Thus, according to this embodiment, it is possible to reduce the economic burden related to the recovery and recycling equipment, and to reduce the cost for the rhodium catalyst.
- the organophosphorus compound that forms a catalyst for the hydroformylation reaction with the rhodium compound is not particularly limited.
- R a , R b , and R c include, but are not limited to, an aryl group that can be substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group.
- alicyclic alkyl groups that can be substituted with triphenylphosphine and triphenylphosphite are preferably used.
- the amount of the organophosphorus compound used is preferably 300-fold to 10,000-fold mol, more preferably 500-fold to 10,000-fold mol, still more preferably 700-fold to 5000-fold mol, particularly preferably relative to the rhodium atom in the rhodium compound. Is 900 times to 2000 times mol.
- the amount of the organic phosphorus compound used is 300 times mol or more of the rhodium atom, the stability of the rhodium metal hydridocarbonyl phosphorus complex as the catalyst active material tends to be sufficiently secured, and as a result, good reactivity is ensured. It tends to be.
- the usage-amount of an organic phosphorus compound is 10000 times mole or less of a rhodium atom, it is preferable from a viewpoint of fully reducing the cost concerning an organic phosphorus compound.
- the hydroformylation reaction can be carried out without using a solvent, but can be carried out more suitably by using a solvent inert to the reaction.
- Solvents that can be used in the hydroformylation reaction include those that dissolve the monoolefin having 13 to 21 carbon atoms, dicyclopentadiene or cyclopentadiene represented by the general formula (4), the rhodium compound, and the organophosphorus compound. If it does not specifically limit.
- hydrocarbons such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons
- esters such as aliphatic esters, alicyclic esters, and aromatic esters
- Alcohols such as aromatic alcohols and alicyclic alcohols
- solvents such as aromatic halides.
- hydrocarbons are preferably used, and alicyclic hydrocarbons and aromatic hydrocarbons are more preferably used.
- the temperature for 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 tends to be obtained, and the residual monoolefin as a raw material tends to be further suppressed.
- the reaction is performed under pressure with carbon monoxide (hereinafter also referred to as “CO”) and hydrogen (hereinafter also referred to as “H 2” ) gas.
- CO carbon monoxide
- H 2 hydrogen
- the CO and H 2 gases can be independently introduced into the reaction system, or can be introduced into the reaction system as a mixed gas prepared in advance.
- the molar ratio of CO and H 2 gas introduced into the reaction system is preferably 0.2 to 5, more preferably 0.5 to 2, and still more preferably 0.8 to 1.2. .
- the reaction activity of the hydroformylation reaction and the selectivity of the target aldehyde tend to be good. Since CO and H 2 gas introduced into the reaction system decrease with the progress of the reaction, the reaction control may be simple when a previously prepared mixed gas of CO and H 2 is used.
- the reaction pressure of the hydroformylation reaction is preferably 1 to 12 MPa, more preferably 1.2 to 9 MPa, and further preferably 1.5 to 5 MPa.
- the reaction pressure is 1 MPa or more, a sufficient reaction rate tends to be obtained, and the residual monoolefin as a raw material tends to be sufficiently 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.
- a batch reaction or a semi-batch reaction is suitable as a reaction system in the case of performing the hydroformylation reaction.
- the semi-batch reaction is performed by adding a rhodium compound, an organic phosphorus compound, and the above solvent to the reactor, pressurizing or heating 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 subjected to the next step after purification by distillation, extraction, crystallization, or the like.
- the compound having 14 to 22 carbon atoms represented by the general formula (2) in the formula (I) is obtained by converting a compound having 14 to 22 carbon atoms represented by the general formula (3) into a catalyst having hydrogenation ability and It can be produced by reduction in the presence of hydrogen.
- a catalyst containing at least one element selected from the group consisting of copper, chromium, iron, zinc, aluminum, nickel, cobalt, and palladium as a catalyst having hydrogenation ability. More preferred catalysts include a Cu—Cr catalyst, a Cu—Zn catalyst, a Cu—Zn—Al catalyst, and the like, as well as a Raney-Ni catalyst, a Raney-Co catalyst, and the like. Further preferred catalysts include a Cu—Cr catalyst and a Raney catalyst. -Co catalyst.
- the amount of the hydrogenation catalyst used is 1 to 100% by mass, preferably 2 to 50% by mass, more preferably 5 to 5% by mass with respect to the compound having 14 to 22 carbon atoms represented by the general formula (3) as a substrate. 30% by mass.
- the amount of catalyst used is 1% by mass or more, the reaction proceeds sufficiently, and as a result, the yield of the target product tends to be sufficiently secured. Further, when the amount of catalyst used is 100% by mass or less, the balance between the amount of catalyst used for the reaction and the effect of improving the reaction rate tends to be good.
- the reaction temperature for the reduction reaction is preferably 60 to 200 ° C, more preferably 80 to 150 ° C.
- the reaction temperature for the reduction reaction is preferably 60 to 200 ° C, more preferably 80 to 150 ° C.
- the reaction temperature By setting the reaction temperature to 200 ° C. or lower, the occurrence of side reactions and decomposition reactions is suppressed, and the target product tends to be obtained with a high yield.
- the reaction temperature by setting the reaction temperature to 60 ° C. or higher, the reaction can be completed in an appropriate time, and there is a tendency that a decrease in productivity and a decrease in the yield of the target product can be avoided.
- the reaction pressure of the reduction reaction is preferably 0.5 to 10 MPa, more preferably 1 to 5 MPa as a hydrogen partial pressure.
- the hydrogen partial pressure is preferably 0.5 to 10 MPa or less, the occurrence of side reactions and decomposition reactions is suppressed, and the target product tends to be obtained in a high yield.
- the hydrogen partial pressure is set to 0.5 MPa or more, the reaction can be completed in an appropriate time, and a decrease in productivity and a decrease in the yield of the target product tend to be avoided.
- a gas inert to the reduction reaction for example, nitrogen or argon
- a solvent can be used.
- the solvent used for the reduction reaction include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, alcohols, and the like. Among them, alicyclic hydrocarbons, aromatic hydrocarbons, alcohols, etc. Are preferred. Specific examples thereof 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 for supplying a substrate or a substrate solution to a tank reactor under the reaction conditions, a reaction condition in a tube type reactor filled with a molded catalyst. It is possible to adopt various reaction methods such as a continuous flow method in which a substrate and a substrate solution are circulated.
- the reaction product obtained by the reduction reaction can be purified by, for example, distillation, extraction, crystallization, or the like.
- (C) Manufacturing method of polyester resin It does not specifically limit as a method of polymerizing the compound represented by General formula (2) in this embodiment, and setting it as the polyester which has a structural unit represented by General formula (1).
- Conventionally known polyester production methods can be applied. Examples thereof include a melt polymerization method such as a transesterification method and a direct esterification method, or a solution polymerization method.
- a transesterification catalyst, an esterification catalyst, a polycondensation catalyst, or the like used in the production of a normal polyester resin can be used.
- These catalysts are not particularly limited.
- metals such as zinc, lead, cerium, cadmium, manganese, cobalt, lithium, sodium, potassium, calcium, nickel, magnesium, vanadium, aluminum, titanium, antimony, germanium, tin, etc.
- fatty acid salts, carbonates, phosphates, hydroxides, chlorides, oxides, alkoxides can be used alone or in combination of two or more.
- the catalyst compounds of manganese, cobalt, zinc, titanium, calcium, antimony, germanium, and tin are preferable, and compounds of manganese, titanium, antimony, germanium, and tin are more preferable.
- the amount of these catalysts to be used is not particularly limited, but the amount as a metal component with respect to the raw material of the polyester resin is preferably 1 to 1000 ppm, more preferably 3 to 750 ppm, and still more preferably 5 to 500 ppm.
- the reaction temperature in the polymerization reaction depends on the type of catalyst and the amount of the catalyst used, but is usually selected within the range of 150 ° C. to 300 ° C., preferably 180 ° C. to 280 ° C. in consideration of the reaction rate and resin coloring.
- the pressure in the reaction layer is preferably adjusted to 1 kPa or less finally from the atmospheric atmosphere, and more preferably 0.5 kPa or less.
- a phosphorus compound When performing the polymerization reaction, a phosphorus compound may be added if desired.
- the phosphorus compound include, but are not limited to, phosphoric acid, phosphorous acid, phosphoric acid ester, phosphorous acid ester, and the like.
- phosphate esters include, but are not limited to, methyl phosphate, ethyl phosphate, butyl phosphate, phenyl phosphate, dimethyl phosphate, diethyl phosphate, dibutyl phosphate, diphenyl phosphate, trimethyl phosphate, Examples thereof include triethyl phosphate, tributyl phosphate, and triphenyl phosphate.
- phosphites include, but are not limited to, methyl phosphite, ethyl phosphite, butyl phosphite, phenyl phosphite, dimethyl phosphite, diethyl phosphite, dibutyl phosphite, Examples thereof include diphenyl phosphite, trimethyl phosphite, triethyl phosphite, tributyl phosphite, and triphenyl phosphite. These can be used alone or in combination of two or more.
- the concentration of phosphorus atoms in the polyester resin of this embodiment is preferably 1 to 500 ppm, more preferably 5 to 400 ppm, and even more preferably 10 to 200 ppm.
- the polyester resin of the present embodiment may contain other structural units other than the structural unit (1) as long as the performance is not impaired, and a structural unit derived from dicarboxylic acid and / or a derivative thereof, a diol structural unit.
- Polymerization can be carried out by appropriately selecting from units derived from oxyacids and applying a conventionally known polyester production method together with the compound represented by formula (2).
- Examples of conventionally known polyester production methods include, but are not limited to, melt polymerization methods such as transesterification methods and direct esterification methods, and solution polymerization methods.
- polyester resin of the present embodiment when the polyester resin of the present embodiment is produced, various stabilizers such as an etherification inhibitor, a heat stabilizer and a light stabilizer, a polymerization regulator and the like can be used.
- various stabilizers such as an etherification inhibitor, a heat stabilizer and a light stabilizer, a polymerization regulator and the like can be used.
- the polyester resin of the present embodiment includes an antioxidant, a light stabilizer, an ultraviolet absorber, a plasticizer, an extender, a matting agent, a drying regulator, an antistatic agent, as long as the purpose of the present embodiment is not impaired.
- Various additives such as anti-settling agent, surfactant, flow improver, drying oil, wax, filler, colorant, reinforcing agent, surface smoothing agent, leveling agent, curing reaction accelerator, thickener, molding aid Can be added.
- the glass transition temperature of the polyester resin was measured as follows. Using a differential scanning calorimeter (manufactured by Shimadzu Corporation, trade name: DSC / TA-60WS), about 10 mg of polyester resin is placed in an aluminum non-sealed container and heated in a nitrogen gas (30 mL / min) stream. A sample heated and melted to 280 ° C. at a rate of 20 ° C./min was rapidly cooled to obtain a measurement sample. The sample was measured under the same conditions, and the temperature at which the difference between the baselines before and after the transition of the DSC curve changed by 1/2 was taken as the glass transition temperature.
- Photoelastic coefficient (m 2 / N) It calculated from the birefringence measurement with respect to the load change in wavelength 633nm using the optical film produced by the casting method using the ellipsometer (JASCO Corporation M220).
- reaction solution was subjected to gas chromatography analysis, and a reaction solution containing 76 g of the compound represented by the formula (3a) and 1.4 g of the monoolefin represented by the formula (4a) (conversion rate 98%, selectivity) 97%), and after purification by distillation, a part was subjected to the following reaction.
- a reaction solution containing 76 g of the compound represented by the formula (3a) and 1.4 g of the monoolefin represented by the formula (4a) (conversion rate 98%, selectivity) 97%) was subjected to the following reaction.
- To a 300 mL stainless steel reactor 54 g of the compound represented by the formula (3a) purified by distillation, 7 mL of sponge cobalt catalyst (manufactured by Nikko Rika Co., Ltd .: R-400) and 109 g of toluene were added, and the inside of the system was pressurized with hydrogen gas.
- the reaction was performed at 3 MPa and 100 ° C. for 9 hours.
- the catalyst was filtered from the obtained slurry with a membrane filter having a pore size of 0.2 ⁇ m. Thereafter, the solvent was distilled off using an evaporator, and analysis by gas chromatography and GC-MS confirmed that it contained 51 g of the main product represented by the formula (2a) having a molecular weight of 250 (main production). (Product yield 93%). This was further purified by distillation to obtain the main product.
- Example 1 45 g of the compound represented by the formula (2a) obtained from the monomer synthesis example, tetrabutyl, in a 200 mL polyester manufacturing apparatus equipped with a partial condenser, a total condenser, a cold trap, a stirrer, a heating device, and a nitrogen introduction tube 0.007 g of titanate was charged, heated to 230 ° C. under a nitrogen atmosphere, and held for 1 hour. Thereafter, the temperature was increased and the pressure was gradually reduced, and finally polycondensation was performed at 270 ° C. and 0.1 kPa or less. The reaction was terminated when a suitable melt viscosity was reached, and a polyester resin was obtained.
- the obtained polyester resin had a weight average molecular weight of 26000, a glass transition temperature of 167 ° C., and a total light transmittance of 91%.
- Example 2 11.5 g of the compound represented by the formula (2a) obtained from the monomer synthesis example, in a 30 mL polyester production apparatus equipped with a partial condenser, a full condenser, a cold trap, a stirrer, a heating apparatus and a nitrogen introduction tube, After adding 0.005 g of tetrabutyl titanate, the temperature was raised to 230 ° C. under a nitrogen atmosphere, and the temperature was maintained for 1 hour. Thereafter, the temperature was increased and the pressure was gradually reduced, and finally polycondensation was performed at 270 ° C. and 0.1 kPa or less. The reaction was terminated when a suitable melt viscosity was reached, and a polyester resin was obtained.
- the obtained polyester resin had a weight average molecular weight of 46800, a glass transition temperature of 171 ° C., and a total light transmittance of 91%.
- 20 parts by mass of the obtained polyester resin and 80 parts by mass of tetrahydrofuran were mixed to obtain a coating solution having a solid concentration of 20% by mass.
- a stretched polyethylene terephthalate film having a thickness of 50 ⁇ m (Ester film E5100 manufactured by Toyobo Co., Ltd.) was used as the base material.
- a coating film was obtained by applying a coating solution to a substrate using No. 20 and drying at 100 ° C. for 60 minutes. About the obtained coat film, the water vapor transmission rate was evaluated.
- the coat layer thickness was 5.7 ⁇ m, and the water vapor transmission coefficient calculated from the water vapor transmission rate was 1.14 g ⁇ mm / m 2 ⁇ day (40 ° C., 90% RH).
- an optical film was produced by the casting method shown below. That is, the polyester resin was dissolved in dichloromethane so as to have a concentration of 5 wt%, casted on a cast plate whose level was confirmed, and then volatilized while adjusting the evaporation amount of the solvent from the cast solution. An optical film was obtained.
- the resulting optical film was sufficiently dried at a temperature not higher than the glass transition temperature using a dryer, and then a 5 cm ⁇ 1 cm sample was cut out and the photoelastic coefficient was evaluated using an ellipsometer. 4 ⁇ 10 ⁇ 12 (m 2 / N).
- 100 g of monoolefin represented by formula (8) in the reactor 200 g of toluene, 0.614 g of triphenyl phosphite, 200 ⁇ L of a separately prepared toluene solution of Rh (acac) (CO) 2 (concentration 0.0097 mol / L) was added.
- the polyester resin of the present invention is excellent in transparency and heat resistance, and can be suitably used for materials that require transparency and heat resistance.
- the industrial significance of the present invention is great.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、以上の従来技術が有する問題点に鑑みなされたものであり、耐熱性及び透明性に優れたポリエステル樹脂を提供することを目的とする。
本実施形態のポリエステル樹脂は、下記一般式(1)で表される構成単位(以下、「構成単位(1)」という)を含む。
本実施形態のポリエステル樹脂は、例えば、下記一般式(2)で表される化合物を重合することで得られる。
式(2)において、R1は、好ましくは水素原子又はCH3である。R2及びR3は、好ましくは水素原子である。上記炭化水素基としては、以下に限定されないが、例えば、メチル基、エチル基、プロピル基、ブチル基、ビニル基、2-ヒドロキシエチル基、4-ヒドロキシブチル基等が挙げられる。
前記一般式(4)で表される炭素数13~21のモノオレフィンは、例えば、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等で製造することが可能である。
前記式(I)中の一般式(3)で表される炭素数14~22の二官能性化合物は、例えば、一般式(4)で表される炭素数13~21モノオレフィンと一酸化炭素及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させること等で製造することができる。
前記式(I)中の一般式(2)で表される炭素数14~22の化合物は、一般式(3)で表される炭素数14~22の化合物を、水素化能を有する触媒及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。
本実施形態における一般式(2)で表される化合物を重合させて一般式(1)で表される構成単位を有するポリエステルとする方法としては、特に限定されず、従来公知のポリエステルの製造方法を適用することができる。例えば、エステル交換法、直接エステル化法等の溶融重合法、又は溶液重合法等を挙げることができる。
ポリエステル樹脂濃度が0.2質量%になるようにテトラヒドロフランに溶解させ、ゲルパーミエイションクロマトグラフィー(GPC)で測定し、標準ポリスチレンで検量した。GPCは東ソー株式会社製カラムTSKgel SuperHM-Mを用い、カラム温度40℃で測定した。溶離液はテトラヒドロフランを0.6mL/minの流速で流し、RI検出器で測定した。
ポリエステル樹脂のガラス転移温度は、次のように測定した。示差走査熱量計((株)島津製作所製、商品名:DSC/TA-60WS)を使用し、ポリエステル樹脂約10mgをアルミニウム製非密封容器に入れ、窒素ガス(30mL/分)気流中、昇温速度20℃/分で280℃まで加熱、溶融したものを急冷して測定用試料とした。該試料を同条件で測定し、DSC曲線の転移前後における基線の差の1/2だけ変化した温度をガラス転移温度とした。
ポリエステル樹脂をプレス成形した円板(厚み3mm)をサンプルとし、全光線透過率を測定した。測定には、色差/濁度測定機(日本電色工業(株)製、商品名:COH-400)を用いた。
水蒸気透過率測定装置(MOCON社製、商品名:PERMATRAN―W Model 1/50G)を使用して、コーティングを施した基材の水蒸気透過率を40℃、相対湿度90%の条件下で測定し、塗膜の水蒸気透過係数を以下の式を用いて計算した:
1/R1 = 1/R2 + DFT/P
ここで、
R1 = コーティングを施した基材の水蒸気透過率(g/m2・day)
R2 = 基材の水蒸気透過率(g/m2・day)
DFT = 塗膜の厚み(mm)
P = 塗膜の水蒸気透過係数(g・mm/m2・day)
とした。
エリプソメーター(日本分光(株)製、M220)を使用し、流延法により作製した光学フィルムを用い、波長633nmにおける荷重変化に対する複屈折測定から算出した。
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。上記反応により、下記式(4a)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、一部を以下の反応に供した。
300mLステンレス製反応器を使用し、蒸留精製した式(4a)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(4a)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、式(3a)で表される化合物76g、式(4a)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、一部を以下の反応に供した。
300mLステンレス製反応器に蒸留精製した式(3a)で表される化合物54g、スポンジコバルト触媒(日興リカ株式会社製:R-400)7mL、トルエン109gを添加し、水素ガスで系内を加圧し、3MPa、100℃で9時間反応を行った。反応後、得られたスラリーから、孔径0.2μmのメンブレンフィルターで触媒をろ過した。その後、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250の式(2a)で表される主生成物51gを含有することが確認された(主生成物収率93%)。これをさらに蒸留精製し、主生成物を取得した。
モノマー合成例で取得した成分のNMR分析を行った。NMRスペクトルを図1~3に示す。以下に示すGC-MS分析、及び図1~3のNMR分析の結果から、モノマー合成例で得られた主生成物は、前記式(2a)で表される化合物であることが確認された。
<分析方法>
1)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)-15℃/分-280℃(4分間)
・検出器 :FID、温度280℃
2)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)-15℃/分-280℃(4分間)
3)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 :CDCl3(重クロロホルム)
・内部標準物質:テトラメチルシラン
分縮器、全縮器、コールドトラップ、撹拌機、加熱装置及び窒素導入管を備えた200mLのポリエステル製造装置に、モノマー合成例より得られた式(2a)で表される化合物45g、テトラブチルチタネート0.007gを仕込み、窒素雰囲気下で230℃まで昇温後、1時間保持した。その後、昇温と減圧を徐々に行い、最終的に270℃、0.1kPa以下で重縮合を行った。適度な溶融粘度になった時点で反応を終了し、ポリエステル樹脂を得た。得られたポリエステル樹脂の重量平均分子量は26000、ガラス転移温度は167℃、全光線透過率は91%であった。
分縮器、全縮器、コールドトラップ、撹拌機、加熱装置及び窒素導入管を備えた30mLのポリエステル製造装置に、モノマー合成例より得られた式(2a)で表される化合物11.5g、テトラブチルチタネート0.005gを仕込み、窒素雰囲気下で230℃まで昇温後、1時間保持した。その後、昇温と減圧を徐々に行い、最終的に270℃、0.1kPa以下で重縮合を行った。適度な溶融粘度になった時点で反応を終了し、ポリエステル樹脂を得た。得られたポリエステル樹脂の重量平均分子量は46800、ガラス転移温度は171℃、全光線透過率は91%であった。
得られたポリエステル樹脂を20質量部、テトラヒドロフランを80質量部混合し、固形分濃度20質量%の塗布液を得た。基材として厚み50μmの延伸ポリエチレンテレフタレートフィルム(東洋紡(株)製エステルフィルムE5100)を用い、バーコーターNo.20を使用して基材に塗布液を塗布し、100℃で60分乾燥させることでコートフィルムを得た。得られたコートフィルムについて、その水蒸気透過率を評価した。また、コート層厚みは5.7μmであり、水蒸気透過率から計算される水蒸気透過係数は1.14g・mm/m2・day(40℃90%RH)であった。
上記で得られたポリエステル樹脂を用い、以下に示す流延法にて光学フィルムを作製した。すなわち、上記ポリエステル樹脂をジクロロメタンに5wt%濃度になるように溶解させ、水平を確認したキャスト板に流延後、キャスト溶液からの溶媒の蒸発量を調整しながら揮発させ、厚さ50μmの透明な光学フィルムを得た。乾燥機を使用し、得られた光学フィルムをガラス転移温度以下の温度で十分に乾燥させた後、5cm×1cmのサンプルを切り出し、エリプソメーターを使用して光弾性係数を評価したところ、-0.4×10-12(m2/N)であった。
500mLステンレス製反応器にアクリル酸メチル95g(1.10mol)、ジシクロペンタジエン105g(0.79mol)を仕込み195℃で2時間反応を行った。下記式(8)で表されるモノオレフィン127g及び式(2a)で表されるモノオレフィン55gを含有する反応液を取得した。これを蒸留精製することによって、式(8)で表されるモノオレフィンを得、一部を以下の反応に供した。
500mLステンレス製反応器を使用し、蒸留精製した式(8)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(8)で表されるモノオレフィン100g、トルエン200g、亜リン酸トリフェニル0.614g、別途調製したRh(acac)(CO)2のトルエン溶液200μL(濃度0.0097mol/L)を加えた。窒素及び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4.5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、式(9)で表される二官能性化合物113gを含む反応液(転化率100%、選択率94%)であることを確認すると共に、これを蒸留精製した後、一部を以下の反応に供した。
500mLステンレス製反応器に蒸留精製した式(9)で表される二官能性化合物70g、スポンジコバルト触媒(日興リカ株式会社製:R-400)14mL、トルエン210gを添加し、水素ガスで系内を加圧し、3MPa、100℃で3.5時間反応を行った。反応後、得られたスラリーを孔径0.2μmのメンブレンフィルターで触媒をろ過した。その後、エバポレーターを使用して溶媒を留去し、GC-MSで分析し、分子量184の主生成物69gを含有することが確認された(主生成物収率98%)。これをさらに蒸留精製し、主生成物(10)を取得した。
原料モノマーとして比較モノマー合成例で得られた式(10)で表される化合物を用い、重縮合の最終温度を265℃とした以外は、実施例2と同じ方法で反応を行い、ポリエステル樹脂を得、さらに得られた樹脂を用いて実施例2と同じ手順でコートフィルムを作成し水蒸気透過率を測定し、水蒸気透過係数を算出した。得られた樹脂の重量平均分子量、ガラス転移温度、及び水蒸気透過係数を表1に示す。なお、得られたポリエステル樹脂の全光線透過率は91%であった。
Claims (2)
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16800022.2A EP3305827B1 (en) | 2015-05-27 | 2016-05-24 | Polyester resin and production method therefor |
US15/575,150 US10287391B2 (en) | 2015-05-27 | 2016-05-24 | Polyester resin and production method therefor |
CN201680030834.4A CN107614569B (zh) | 2015-05-27 | 2016-05-24 | 聚酯树脂及其制造方法 |
KR1020177036059A KR102569041B1 (ko) | 2015-05-27 | 2016-05-24 | 폴리에스터 수지 및 그의 제조 방법 |
JP2017520723A JP6708210B2 (ja) | 2015-05-27 | 2016-05-24 | ポリエステル樹脂及びその製造方法 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015-107183 | 2015-05-27 | ||
JP2015107183 | 2015-05-27 | ||
JP2016-061737 | 2016-03-25 | ||
JP2016061737 | 2016-03-25 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016190317A1 true WO2016190317A1 (ja) | 2016-12-01 |
Family
ID=57392923
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2016/065337 WO2016190317A1 (ja) | 2015-05-27 | 2016-05-24 | ポリエステル樹脂及びその製造方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US10287391B2 (ja) |
EP (1) | EP3305827B1 (ja) |
JP (1) | JP6708210B2 (ja) |
KR (1) | KR102569041B1 (ja) |
CN (1) | CN107614569B (ja) |
TW (1) | TWI687451B (ja) |
WO (1) | WO2016190317A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018062325A1 (ja) * | 2016-09-28 | 2018-04-05 | 三菱瓦斯化学株式会社 | 共重合ポリエステル樹脂 |
WO2019146575A1 (ja) * | 2018-01-23 | 2019-08-01 | 三菱瓦斯化学株式会社 | 成形体 |
WO2019194117A1 (ja) * | 2018-04-04 | 2019-10-10 | 三菱瓦斯化学株式会社 | ポリエステル樹脂組成物 |
US20200239492A1 (en) * | 2017-10-03 | 2020-07-30 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Continuous Process for Cycloaddition Reactions |
WO2021200613A1 (ja) * | 2020-03-31 | 2021-10-07 | 三菱瓦斯化学株式会社 | 樹脂組成物並びにそれを含む光学レンズ及び光学フィルム |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109791245B (zh) * | 2016-09-28 | 2021-06-15 | 三菱瓦斯化学株式会社 | 光学膜、相位差膜、偏光板 |
JP7240090B2 (ja) * | 2017-10-03 | 2023-03-15 | 日東電工株式会社 | 偏光板、画像表示装置、および偏光板の製造方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6115096B2 (ja) * | 1978-06-23 | 1986-04-22 | Toyo Ink Mfg Co | |
JP2000281613A (ja) * | 1999-03-31 | 2000-10-10 | Arakawa Chem Ind Co Ltd | 脂環式ジオール及びその製造方法 |
WO2011048851A1 (ja) * | 2009-10-22 | 2011-04-28 | 日立化成工業株式会社 | トリシクロデカンモノメタノールモノカルボン酸誘導体の製造方法 |
WO2012035874A1 (ja) * | 2010-09-14 | 2012-03-22 | 日立化成工業株式会社 | ノルボルナン骨格を有するポリエステル及びその製造方法 |
WO2015147242A1 (ja) * | 2014-03-28 | 2015-10-01 | 三菱瓦斯化学株式会社 | ノルボルナン骨格を有する二官能性化合物およびその製造方法 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58174419A (ja) | 1982-04-08 | 1983-10-13 | Japan Synthetic Rubber Co Ltd | 新規なポリエステル共重合体 |
JP2001064374A (ja) | 1999-06-23 | 2001-03-13 | Daicel Chem Ind Ltd | 新規なポリエステル重合体とその製造法 |
JP2001064372A (ja) | 1999-06-23 | 2001-03-13 | Daicel Chem Ind Ltd | 機能性ポリエステル重合体とその製造法 |
JP2003119259A (ja) | 2001-10-12 | 2003-04-23 | Nippon Ester Co Ltd | ポリエステル樹脂 |
KR100948708B1 (ko) * | 2002-04-08 | 2010-03-22 | 니폰 제온 가부시키가이샤 | 노보넨계 개환중합체, 노보넨계 개환중합체 수소화물 및이들의 제조방법 |
US7169880B2 (en) | 2003-12-04 | 2007-01-30 | Eastman Chemical Company | Shaped articles from cycloaliphatic polyester compositions |
JP2007161917A (ja) * | 2005-12-15 | 2007-06-28 | Teijin Ltd | ポリエチレンナフタレート樹脂 |
JP2008133223A (ja) | 2006-11-29 | 2008-06-12 | Honshu Chem Ind Co Ltd | エキソ型ヒドロキシテトラシクロドデカンカルボン酸類及びその製造方法 |
KR20130101008A (ko) * | 2010-09-07 | 2013-09-12 | 니폰 제온 가부시키가이샤 | 수지 조성물 및 그 성형체 |
TWI576336B (zh) | 2015-03-25 | 2017-04-01 | 三菱瓦斯化學股份有限公司 | 含有降莰烷骨架之二官能性化合物及其製造方法 |
-
2016
- 2016-05-24 JP JP2017520723A patent/JP6708210B2/ja active Active
- 2016-05-24 EP EP16800022.2A patent/EP3305827B1/en active Active
- 2016-05-24 US US15/575,150 patent/US10287391B2/en active Active
- 2016-05-24 WO PCT/JP2016/065337 patent/WO2016190317A1/ja active Application Filing
- 2016-05-24 CN CN201680030834.4A patent/CN107614569B/zh active Active
- 2016-05-24 KR KR1020177036059A patent/KR102569041B1/ko active IP Right Grant
- 2016-05-26 TW TW105116367A patent/TWI687451B/zh active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6115096B2 (ja) * | 1978-06-23 | 1986-04-22 | Toyo Ink Mfg Co | |
JP2000281613A (ja) * | 1999-03-31 | 2000-10-10 | Arakawa Chem Ind Co Ltd | 脂環式ジオール及びその製造方法 |
WO2011048851A1 (ja) * | 2009-10-22 | 2011-04-28 | 日立化成工業株式会社 | トリシクロデカンモノメタノールモノカルボン酸誘導体の製造方法 |
WO2012035874A1 (ja) * | 2010-09-14 | 2012-03-22 | 日立化成工業株式会社 | ノルボルナン骨格を有するポリエステル及びその製造方法 |
WO2015147242A1 (ja) * | 2014-03-28 | 2015-10-01 | 三菱瓦斯化学株式会社 | ノルボルナン骨格を有する二官能性化合物およびその製造方法 |
Non-Patent Citations (2)
Title |
---|
T.SUGIMOTO: "Syn Selectivity in Diels-Alder Reactions of Isodicyclopentadiene", J. ORG. CHEM., vol. 41, no. 8, 1976, pages 1457 - 1459, XP055333001 * |
TORU KIKUCHI ET AL.: "Stereostructure and Composition of Products from Hydroformylation of Dicyclopentadiene using Carbon Dioxide as a Reactant", HITACHI KASEI TECHNICAL REPORT, July 2008 (2008-07-01), pages 7 - 12, XP009507624 * |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018062325A1 (ja) * | 2016-09-28 | 2018-04-05 | 三菱瓦斯化学株式会社 | 共重合ポリエステル樹脂 |
JPWO2018062325A1 (ja) * | 2016-09-28 | 2019-07-11 | 三菱瓦斯化学株式会社 | 共重合ポリエステル樹脂 |
US10894859B2 (en) | 2016-09-28 | 2021-01-19 | Mitsubishi Gas Chemical Company, Inc. | Copolymerized polyester resin |
US20200239492A1 (en) * | 2017-10-03 | 2020-07-30 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Continuous Process for Cycloaddition Reactions |
US11725014B2 (en) * | 2017-10-03 | 2023-08-15 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Continuous process for cycloaddition reactions |
US11236198B2 (en) | 2018-01-23 | 2022-02-01 | Mitsubishi Gas Chemical Company, Inc. | Molded article |
JP7318534B2 (ja) | 2018-01-23 | 2023-08-01 | 三菱瓦斯化学株式会社 | 成形体 |
JPWO2019146575A1 (ja) * | 2018-01-23 | 2021-01-07 | 三菱瓦斯化学株式会社 | 成形体 |
WO2019146575A1 (ja) * | 2018-01-23 | 2019-08-01 | 三菱瓦斯化学株式会社 | 成形体 |
EP3744790A4 (en) * | 2018-01-23 | 2020-12-02 | Mitsubishi Gas Chemical Company, Inc. | MOLDED ARTICLE |
KR102655030B1 (ko) * | 2018-01-23 | 2024-04-04 | 미츠비시 가스 가가쿠 가부시키가이샤 | 성형체 |
KR20200110363A (ko) * | 2018-01-23 | 2020-09-23 | 미츠비시 가스 가가쿠 가부시키가이샤 | 성형체 |
EP3778772A4 (en) * | 2018-04-04 | 2021-02-17 | Mitsubishi Gas Chemical Company, Inc. | POLYESTER RESIN COMPOSITION |
WO2019194117A1 (ja) * | 2018-04-04 | 2019-10-10 | 三菱瓦斯化学株式会社 | ポリエステル樹脂組成物 |
JP7307405B2 (ja) | 2018-04-04 | 2023-07-12 | 三菱瓦斯化学株式会社 | ポリエステル樹脂組成物 |
US20210147619A1 (en) * | 2018-04-04 | 2021-05-20 | Mitsubishi Gas Chemical Company, Inc. | Polyester resin composition |
JPWO2019194117A1 (ja) * | 2018-04-04 | 2021-04-08 | 三菱瓦斯化学株式会社 | ポリエステル樹脂組成物 |
WO2021200613A1 (ja) * | 2020-03-31 | 2021-10-07 | 三菱瓦斯化学株式会社 | 樹脂組成物並びにそれを含む光学レンズ及び光学フィルム |
EP4130096A4 (en) * | 2020-03-31 | 2023-08-30 | Mitsubishi Gas Chemical Company, Inc. | COMPOSITION OF RESIN, OPTICAL LENS CONTAINING IT, AND OPTICAL FILM |
Also Published As
Publication number | Publication date |
---|---|
CN107614569B (zh) | 2021-01-15 |
EP3305827B1 (en) | 2020-01-15 |
KR20180012781A (ko) | 2018-02-06 |
TW201704288A (zh) | 2017-02-01 |
US20180142059A1 (en) | 2018-05-24 |
JPWO2016190317A1 (ja) | 2018-03-15 |
JP6708210B2 (ja) | 2020-06-10 |
EP3305827A4 (en) | 2018-12-26 |
KR102569041B1 (ko) | 2023-08-21 |
CN107614569A (zh) | 2018-01-19 |
US10287391B2 (en) | 2019-05-14 |
EP3305827A1 (en) | 2018-04-11 |
TWI687451B (zh) | 2020-03-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2016190317A1 (ja) | ポリエステル樹脂及びその製造方法 | |
CN109791245B (zh) | 光学膜、相位差膜、偏光板 | |
JP2019026738A (ja) | ポリエステル樹脂、及びそれを用いたポリエステル樹脂溶液、塗料、コーティング剤 | |
JP6965888B2 (ja) | 共重合ポリエステル樹脂 | |
JP6041180B1 (ja) | ノルボルナン骨格を有する二官能性化合物、及びその製造方法 | |
JP2019026752A (ja) | 樹脂組成物及び成形体 | |
CN113677734B (zh) | 热塑性树脂、成型体和热塑性树脂用单体 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 16800022 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2017520723 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15575150 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20177036059 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2016800022 Country of ref document: EP |