Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
• • 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
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/181—Acids containing aromatic rings
  • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
  • C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
  • C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
• • 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
  • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/16—Dicarboxylic acids and dihydroxy compounds
  • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
  • C08G63/19—Hydroxy compounds containing aromatic rings
  • C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
  • C08G63/197—Hydroxy compounds containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
• • 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
  • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate groups
• • 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
  • C08G63/66—Polyesters containing oxygen in the form of ether groups
  • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/672—Dicarboxylic acids and dihydroxy compounds
• • 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
  • C08G64/04—Aromatic polycarbonates
  • C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
  • C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
  • C08G64/10—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing halogens
• • 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
  • C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
  • C08G64/1608—Aliphatic-aromatic or araliphatic 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
  • C08G64/307—General preparatory processes using carbonates and phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • 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
• • 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

Definitions

• the present invention relates to a novel polyester carbonate resin composition, and to optical lenses and optical films formed therefrom.
• Optical glass or optical transparent resin is used as the material for the optical elements used in the optical systems of various cameras, including cameras with built-in film and video cameras.
• Optical glass has excellent heat resistance, transparency, dimensional stability, chemical resistance, etc., and there are many types of materials with various refractive indices (nD) and Abbe numbers ( ⁇ D).
• nD refractive indices
• ⁇ D Abbe numbers
• it has problems such as high material costs, poor moldability, and low productivity.
• processing it into aspherical lenses used for aberration correction requires extremely advanced technology and high costs, which is a major obstacle to practical use.
• optical lenses made from optically transparent resins have the advantage that they can be mass-produced by injection molding and that aspherical lenses can be easily manufactured, and are currently used for camera lenses.
• examples include polycarbonate made from bisphenol A, polystyrene, poly-4-methylpentene, polymethyl methacrylate, and amorphous polyolefins.
• optical transparent resins as optical lenses, in addition to the refractive index and Abbe number, transparency, heat resistance, and low birefringence are required, so the balance of the resin's properties limits where it can be used.
• polystyrene has low heat resistance and high birefringence
• poly-4-methylpentene has low heat resistance
• polymethyl methacrylate has a low glass transition temperature, low heat resistance, and a small refractive index, so its areas of use are limited
• polycarbonate made from bisphenol A has high birefringence, so it is not recommended as its areas of use are limited.
• the refractive index of an optical material is high, a lens element with the same refractive index can be realized with a surface with a smaller curvature, so the amount of aberration that occurs at this surface can be reduced, and a high refractive index is useful because it makes it possible to reduce the number of lenses, reduce the sensitivity of the lens to decentering, and reduce the lens thickness, thereby making the lens system smaller and lighter.
• chromatic aberration can be corrected by combining and using multiple lenses with different Abbe numbers.
• those with high Abbe numbers include polymethyl methacrylate (PMMA) and cycloolefin polymer.
• PMMA polymethyl methacrylate
• Cycloolefin polymer in particular has been widely used for optical lenses because of its excellent heat resistance and mechanical properties.
• resins with low Abbe numbers 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 polycarbonate copolymers containing a perhydroxydimethanonaphthalene skeleton, but because the dihydroxymethyl groups are all located at the 2- and 3-positions, the strength is weak and the copolymers are not suitable for optical lens applications. Furthermore, the polycarbonates described in Patent Documents 2 to 4 have a low glass transition temperature (Tg), which causes problems with heat resistance. For example, the HOMO polycarbonate described in Example 1 of Patent Document 4 has a number average molecular weight of 38,000, but a low glass transition temperature (Tg) of 125°C.
• Tg glass transition temperature
• the present invention aims to solve at least one of the above-mentioned problems in the prior art.
• a preferred embodiment of the present invention aims to provide a polyester carbonate resin composition that is excellent in at least one of the dimensional change rate (%), water absorption rate (%), YI, haze (%), and transmittance (%).
• a further aim of the present invention is to provide an optical lens and an optical film manufactured from this resin composition.
• the present invention is as follows.
• X represents a single bond or a fluorene group
• R a and R b when X is a single bond, are each independently selected from a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aryloxy group having 6 to 20 carbon atoms, and -C ⁇ C-R h ;
• R a and R b are each independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, and -C ⁇ C-R
• R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms which may contain a heterocyclic atom selected from O, N, and S, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms.
• a and b each independently represent an integer of 0 to 5.
• n and m each independently represent an integer of 1 to 5.
• R i and R ii each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
• R a and R b each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;
• Y represents -O-, -S-, -SO-, -SO 2 -, -CO-, a cycloalkylene group having 6 to 12 carbon atoms, or a divalent group represented by the following general formula (4) or (5), the cycloalkylene group being optionally substituted with 1 to 12 alkyl groups having 1 to 3 carbon atoms;
• a and B each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a
• R c and R d are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 17 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms;
• the alkyl group, the alkoxy group, the aryl group, the aralkyl group, and the alkenyl group in Rc and Rd may each have a substituent, Rc and Rd may be bonded to each other to form a carbocycle having 3 to 20 carbon atoms or a heterocycle having 1 to 20 carbon atoms, the carbocycle and the heterocycle each may have a substituent, and n represents an integer of 0 to 20.
• R e and R f are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 17 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms, and the alkyl group, alkoxy group, aryl group, aralkyl group, and alkenyl group each optionally have a substituent; R e and R f may be bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms or a heterocyclic ring having 1 to 20 carbon atoms, and the carbocyclic ring and the heterocyclic ring each may have a substituent.
• Y in the general formula (3) is a fluorene group.
• X represents an alkylene group having 1 to 4 carbon atoms.
• R i and R ii each independently represent an alkyl group having 1 to 5 carbon atoms.
• An optical lens comprising the polyester carbonate resin composition according to any one of ⁇ 1> to ⁇ 9> above.
• An optical film comprising the polyester carbonate resin composition according to any one of ⁇ 1> to ⁇ 9> above.
• a polyester carbonate resin composition is obtained that is excellent in at least one of the dimensional change rate (%), water absorption rate (%), YI, haze (%), and transmittance (%). Furthermore, an optical lens and an optical film are produced from this resin composition.
• the polyester carbonate resin composition of the present invention contains a polyester carbonate resin including a structural unit (A) represented by the following general formula (1), a structural unit (B) derived from at least one compound selected from the group consisting of 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol (C12-diol), and a structural unit (i) derived from a dicarboxylic acid or carboxylic acid diester represented by the following general formula (I), and a higher alcohol fatty acid ester.
• the polyester carbonate resin may contain one type of compound represented by the general formula (1) alone, or may contain two or more types of compounds in combination.
• X represents a single bond or a fluorene group
• R a and R b when X is a single bond, are each independently selected from a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aryloxy group having 6 to 20 carbon atoms, and -C ⁇ C-R h ;
• R a and R b are each independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atom
• R a and R b are each independently selected from an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more heterocyclic atoms selected from O, N and S, or an aryloxy group having 6 to 20 carbon atoms, and -C ⁇ C-R h , where R h represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms containing one or more heterocyclic atoms selected from O, N and S.
• the aryl group more preferably has 6 to 18 carbon atoms, more preferably has 6 to 16 carbon atoms, more preferably has 6 to 14 carbon atoms, more preferably has 6 to 12 carbon atoms, and even more preferably has 6 to 10 carbon atoms.
• the heteroaryl group more preferably has 6 to 18 carbon atoms, more preferably has 8 to 16 carbon atoms, and even more preferably has 10 to 14 carbon atoms.
• the aryloxy group more preferably has 6 to 18 carbon atoms, more preferably has 6 to 16 carbon atoms, and even more preferably has 6 to 14 carbon atoms.
• R a and R b when X is a single bond, R a and R b may each independently be selected from a phenyl group, a naphthyl group, or the group consisting of the following: When X is a fluorene group, R a and R b may each independently be selected from a hydrogen atom, a phenyl group, a naphthyl group, or the group consisting of the following:
• the monomer constituting the structural unit (A) represented by the general formula (1) preferably includes at least one monomer represented by the following structural formula:
• the monomer constituting the structural unit (B) is at least one compound selected from the group consisting of 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol (C12-diol).
• the polyester carbonate resin in the present invention may further contain a structural unit (C) represented by the following general formula (3).
• R a and R b each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;
• Y represents -O-, -S-, -SO-, -SO2-, -CO-, a cycloalkylene group having 6 to 12 carbon atoms, or a divalent group represented by the following general formula (4) or the following general formula (5), wherein the cycloalkylene group is optionally substituted with an alkyl group having 1 to 12 carbon atoms and 1 to 3 carbon atoms
• a and B each independently represent an alkyl group having 1 to 12 carbon
• R c and R d are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 5 carbon atoms), an alkoxy group having 1 to 5 carbon atoms (preferably 1 to 3 carbon atoms), an aryl group having 6 to 12 carbon atoms (preferably 6 to 8 carbon atoms), an aralkyl group having 7 to 17 carbon atoms (preferably 7 to 10 carbon atoms), and an alkenyl group having 2 to 15 carbon atoms (preferably 2 to 10 carbon atoms), and are preferably selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, an isobutyl group, and a phenyl group.
• both R c and R d represent a methyl group.
• the alkyl group, the alkoxy group, the aryl group, the aralkyl group, and the alkenyl group in Rc and Rd may each have a substituent.
• Rc and Rd may be bonded to each other to form a carbon ring having 3 to 20 carbon atoms (preferably 5 to 15 carbon atoms) or a hetero ring having 1 to 20 carbon atoms (preferably 5 to 10 carbon atoms), and the carbocycle and the heterocycle may each have a substituent.
• n represents an integer of 0 to 20, preferably an integer of 0 to 5, and more preferably an integer of 0 to 2.
• R e and R f are each independently selected from the group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms (preferably 1 to 3 carbon atoms), an alkoxy group having 1 to 7 carbon atoms (preferably 1 to 3 carbon atoms), an aryl group having 6 to 12 carbon atoms (preferably 6 to 10 carbon atoms), an aralkyl group having 7 to 17 carbon atoms (preferably 7 to 11 carbon atoms), and an alkenyl group having 2 to 15 carbon atoms, preferably selected from the group consisting of a hydrogen atom and a phenyl group.
• R e and R f both represent a hydrogen atom.
• the alkyl group, the alkoxy group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent, and a preferred example of the substituent is a phenyl group.
• R e and R f may be bonded to each other to form a carbocyclic ring having 3 to 20 carbon atoms (preferably 3 to 10 carbon atoms) or a heterocyclic ring having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and the carbocyclic ring and the heterocyclic ring each may have a substituent.
• Y represents a divalent group represented by general formula (4) or a divalent group represented by general formula (5).
• Y is more preferably a fluorene group.
• the monomer constituting the structural unit (C) represented by general formula (3) preferably includes at least one of the monomers represented by the following structural formulas.
• the polyester carbonate resin in the present invention may further contain a structural unit (D) represented by the following general formula (6).
• X is an alkylene group having 1 to 4 carbon atoms.
• the monomer constituting the structural unit (D) represented by general formula (6) is a monomer represented by the following structural formula.
• the polyester carbonate resin in the present invention may contain, for example, a combination of compounds listed in Table 1 below.
• the polyester carbonate resin may contain a structural unit (A) represented by the following general formula (1-1) and the structural unit (B).
• X represents a single bond
• R a and R b are each independently selected from a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aryloxy group having 6 to 20 carbon atoms, and -C ⁇ C-R h ;
• R h represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero
• the general formula (1-1) may be represented by the following general formula (1-1A).
• R a and R b are each independently selected from a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aryloxy group having 6 to 20 carbon atoms, and -C ⁇ C-R h ;
• R h represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S;
• a and B each independently represent an alkylene group having 1 to
• the polyester carbonate resin may contain the structural unit (A) represented by the general formula (1-1), the structural unit (B), and the structural unit (C) represented by the following general formula (3-1):
• R a and R b each independently represent a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms;
• Y represents a fluorene group;
• a and B each independently represent an alkylene group having 1 to 4 carbon atoms;
• m and n each independently represent an integer of 0 to 4;
• a and b each independently represent an integer of 1 to 10.
• the polyester carbonate resin may contain the structural unit (A) represented by the general formula (1-1), the structural unit (B), and the structural unit (D) represented by the general formula (6).
• the polyester carbonate resin may contain the structural unit (A) represented by the general formula (1-1), the structural unit (B), the structural unit (C) represented by the general formula (3-1), and the structural unit (D) represented by the formula (6).
• the polyester carbonate resin may contain a structural unit (A) represented by the following general formula (1-2) and the structural unit (B).
• X represents a fluorene group
• R a and R b are each independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aryloxy group having 6 to 20 carbon atoms, and -C ⁇ C-R h ;
• R h represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms or a heteroaryl group having
• R a and R b are each independently selected from a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S, or an aryloxy group having 6 to 20 carbon atoms, and -C ⁇ C-R h ;
• R h represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from O, N, and S;
• a and B each independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20
• the polyester carbonate resin may contain the structural unit (A) represented by the general formula (1-2), the structural unit (B), and the structural unit (C) represented by the general formula (3-1).
• the polyester carbonate resin may contain the structural unit (A) represented by the general formula (1-2), the structural unit (B), and the structural unit (D) represented by the general formula (6).
• the polyester carbonate resin may contain the structural unit (A) represented by the general formula (1-2), the structural unit (B), the structural unit (C) represented by the general formula (3-1), and the structural unit (D) represented by the formula (6).
• the polyester carbonate resin may contain the structural unit (A) represented by the general formula (1-1) and the general formula (1-2), and the structural unit (B).
• the polyester carbonate resin may contain the structural unit (A) represented by the general formula (1-1) and the general formula (1-2), the structural unit (B), and the structural unit (C) represented by the general formula (3-1).
• the polyester carbonate resin may contain the structural unit (A) represented by the general formula (1-1) and the general formula (1-2), the structural unit (B), and the structural unit (D) represented by the general formula (6).
• the polyester carbonate resin may contain the structural unit (A) represented by the general formula (1-1) and the general formula (1-2), the structural unit (B), the structural unit (C) represented by the general formula (3-1), and the structural unit (D) represented by the formula (6).
• the molar ratio (A/B) of the structural unit (A) to the structural unit (B) is preferably 99.9/0.1 to 0.1/99.9, more preferably 99/1 to 1/99, even more preferably 99/1 to 50/50, particularly preferably 99/1 to 60/40, and most preferably 90/10 to 70/30.
• the molar ratio of the structural unit (B) larger than the above lower limit, the fluidity of the polyester carbonate resin can be improved.
• the optical properties of the molded article using the polyester carbonate resin of the present invention can be maintained within a preferred range for an optical material.
• R 1 and R 2 each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms which may contain a heterocyclic atom selected from O, N, and S, an alkenyl group having 2 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms.
• a and b each independently represent an integer of 0 to 5.
• n and m each independently represent an integer of 1 to 5.
• R i and R ii each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
• the dicarboxylic acid or carboxylic acid diester represented by general formula (I) preferably includes at least one of the dicarboxylic acid or carboxylic acid diester represented by the following structural formula:
• R i and R ii each independently preferably represent an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
• the polyester carbonate resin of the present invention may contain phenol generated during production and unreacted remaining carbonic acid diester as impurities.
• the phenol content in the polyester carbonate resin is preferably 0.1 to 3000 ppm, more preferably 0.1 to 2000 ppm, and particularly preferably 1 to 1000 ppm, 1 to 800 ppm, 1 to 500 ppm, or 1 to 300 ppm.
• the carbonic acid diester content in the polyester carbonate resin is preferably 0.1 to 1000 ppm, more preferably 0.1 to 500 ppm, and particularly preferably 1 to 100 ppm.
• the raw material monomers may remain in the resin.
• the amount of each of the raw material monomers remaining in the resin is preferably 3000 ppm or less, and more preferably 1 to 1000 ppm.
• the polyester carbonate resin in the present invention can be produced by melt polycondensation using the diol compound constituting the above-mentioned structural unit (A), the diol compound constituting the above-mentioned structural unit (B), the dicarboxylic acid or carboxylic acid diester constituting the above-mentioned structural unit (i), and the carbonate diester as raw materials.Furthermore, other diol compounds may be used in combination.
• the polyester carbonate resin can be produced in the presence of a basic compound catalyst, an ester exchange catalyst, or a mixed catalyst consisting of both of them as a polycondensation catalyst.
• 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 preferred from the viewpoint of reactivity and purity.
• the amount of carbonic acid diester added can be determined by assuming that the diol component and the dicarboxylic acid component react in equimolar amounts, and the remainder reacts with the carbonic acid diester.
• the carbonic acid diester is preferably used in a ratio of 0.60 to 1.50 moles per mole difference between the diol component and the dicarboxylic acid component, more preferably 0.80 to 1.40 moles, even more preferably 1.00 to 1.30 moles, even more preferably 1.00 to 1.25 moles, and particularly preferably 1.00 to 1.20 moles.
• the molecular weight of the polyester carbonate resin can be controlled.
• Basic compound catalysts include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds.
• the alkali metal compounds used in the present invention include, for example, organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkali metals. From the viewpoints of catalytic effect, price, distribution volume, and effect on the color of the resin, sodium carbonate and sodium hydrogen carbonate are preferred.
• alkaline earth metal compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, and alkoxides of alkaline earth metal compounds.
• nitrogen-containing compounds examples include quaternary ammonium hydroxides and their salts, amines, etc.
• salts of zinc, tin, zirconium, and lead are preferably used, and these can be used alone or in combination. They may also be used in combination with the above-mentioned alkali metal compounds and alkaline earth metal compounds.
• transesterification catalyst examples include aluminum tris(2,4-pentanedionato)(III), diethyl (4-methylbenzyl)phosphonate, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride(II), tin chloride(IV), tin acetate(II), tin acetate(IV), dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead acetate(II), lead acetate(IV), zirconium acetate, and titanium tetrabutoxide.
• zinc acetate, zirconium acetate, aluminum tris(2,4-pentanedionato)(III), and diethyl (4-methylbenzyl)phosphonate are preferred, and aluminum tris(2,4-pentanedionato)(III) and diethyl (4-methylbenzyl)phosphonate are more preferred.
• catalysts are used so that the metal components in the catalyst are preferably 0.001 ppm to 1000 ppm, more preferably 0.01 ppm to 100 ppm, and particularly preferably 0.1 ppm to 100 ppm, relative to the theoretical amount of resin produced.
• the catalyst was added so that the Al element was 6.5 ppm and the P element was 13.5 ppm.
• the melt polycondensation method uses the above-mentioned raw materials and catalysts to carry out melt polycondensation under heating at normal or reduced pressure while removing by-products through an ester exchange reaction.
• the reaction is carried out at a temperature of 120 to 260°C, preferably 180 to 260°C, for 0.1 to 5 hours, preferably 0.5 to 3 hours.
• the reaction temperature is increased while increasing the degree of vacuum in the reaction system to react the diol compound with the carbonate diester, and finally, the polycondensation reaction is carried out at a temperature of 200 to 350°C for 0.05 to 2 hours under a reduced pressure of 1 mmHg or less.
• Such a reaction may be carried out continuously or batchwise.
• the reaction apparatus used in carrying out the above reaction may be a vertical type equipped with an anchor-type stirring blade, a Max Blend stirring blade, a helical ribbon-type stirring blade, etc., a horizontal type equipped with a paddle blade, a lattice blade, a spectacle blade, etc., or an extruder type equipped with a screw, and it is preferable to use a reaction apparatus that is an appropriate combination of these, taking into account the viscosity of the polymer.
• the catalyst may be removed or deactivated after the polymerization reaction is completed in order to maintain thermal stability and hydrolytic stability.
• a method of deactivating the catalyst by adding a known acidic substance is preferably carried out.
• esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate, phosphoric acids such as phosphorous acid, phosphoric acid, and phosphonic acid, phosphoric acid esters such as triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, and monooctyl phosphite, triphenyl phosphate, diphenyl phosphate, monophenyl phosphate,
• Suitable examples of the deactivating agent include phosphate esters such as monooctyl phosphate and monooctyl phosphate, phosphonic acids such as diphenylphosphonic acid, dioctylphosphonic acid, and dibutylphosphonic acid, phosphonic acid esters such as diethyl phenylphosphonate, phosphines such as triphenylphosphine and bis(diphenylphosphino)ethane, boronic acids such as boric acid and phenylboric acid, aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate, organic halides such as stearic acid chloride, benzoyl chloride, and p-toluenesulfonic acid chloride, alkyl sulfuric acids such as dimethyl sulfate, and organic halides such as benzoyl chloride.
• phosphate esters such as monooct
• aromatic sulfonates such as tetrabutylphosphonium dodecylbenzenesulfonate.
• these deactivators are used in an amount of 0.01 to 50 times by mole, preferably 0.3 to 20 times by mole, relative to the amount of the catalyst. If the amount is less than 0.01 times by mole, the deactivating effect is insufficient, which is not preferable. Furthermore, if the amount is more than 50 times the amount of catalyst, the heat resistance decreases and the molded product becomes more likely to become discolored, which is not preferable.
• a step may be added in which the low-boiling compounds in the polymer are removed by volatilization at a pressure of 0.1 to 1 mmHg and a temperature of 200 to 350°C.
• a horizontal device equipped with stirring blades with excellent surface renewal capabilities such as paddle blades, lattice blades, and spectacle blades, or a thin-film evaporator is preferably used.
• the polyester carbonate resin of the present invention is desired to have as little foreign matter content as possible, and filtration of the molten raw material and the catalyst liquid is preferably carried out.
• the mesh of the filter is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less.
• filtration of the produced resin with a polymer filter is preferably carried out.
• the mesh of the polymer filter is preferably 100 ⁇ m or less, more preferably 30 ⁇ m or less.
• the process of collecting the resin pellets must naturally be in a low-dust environment, and is preferably class 1000 or less, more preferably class 100 or less.
• the polyester carbonate resin composition of the present invention contains the above-mentioned polyester carbonate resin and a higher alcohol fatty acid ester.
• the higher alcohol fatty acid ester used in the present invention means a fatty acid ester of a monohydric alcohol having 6 or more carbon atoms, the lower limit of which is preferably 10 or more carbon atoms, more preferably 15 or more carbon atoms, and the upper limit of which is preferably 24 or less carbon atoms, more preferably 20 or less carbon atoms.
• the higher alcohol fatty acid ester examples include stearyl stearate, 2-ethylhexyl octadecanoate, cetyl 2-ethylhexanoate, and ethylhexyl palmitate, with stearyl stearate being particularly preferred.
• stearyl stearate examples include Rikemal SL-800 (manufactured by Riken Vitamin Co., Ltd.), Rikemal SL-900 (manufactured by Riken Vitamin Co., Ltd.), and Rikemal SL-900A (manufactured by Riken Vitamin Co., Ltd.).
• the amount of the higher alcohol fatty acid ester used is preferably 100 to 10,000 ppm, more preferably 100 to 5,000 ppm, and particularly preferably 500 to 5,000 ppm, based on the polyester carbonate resin.
• the polyester carbonate resin composition of the present invention may contain additives other than the higher alcohol fatty acid ester, such as release agents, antioxidants, catalyst deactivators, UV absorbers, flow modifiers, crystal nucleating agents, reinforcing agents, dyes, antistatic agents, or antibacterial agents.
• additives other than the higher alcohol fatty acid ester such as release agents, antioxidants, catalyst deactivators, UV absorbers, flow modifiers, crystal nucleating agents, reinforcing agents, dyes, antistatic agents, or antibacterial agents.
• the polyester carbonate resin composition of the present invention is excellent in at least one of dimensional change rate (%), water absorption rate (%), YI, haze (%), and transmittance (%).
• the physical properties of the polyester carbonate resin composition can be measured by the methods described in the examples below.
• the upper limit of the dimensional change rate (%) in both MD and TD is preferably 0.5% or less, more preferably 0.3% or less, and particularly preferably 0.1% or less.
• the lower limit of the dimensional change rate (%) is preferably 0% or more, more preferably 0.001% or more, even more preferably 0.01% or more, and particularly preferably 0.05% or more.
• MD means machine direction (flow direction)
• TD means transverse direction (vertical direction).
• the polyester carbonate resin composition of the present invention preferably has an upper limit of water absorption (%) of 1 mass% or less, more preferably 0.7 mass% or less, and particularly preferably 0.5 mass% or less.
• the lower limit of water absorption (%) is preferably 0 mass% or more, more preferably 0.1 mass% or more, and particularly preferably 0.3 mass% or more.
• the polyester carbonate resin composition of the present invention preferably has a YI of 3 to 60, more preferably 10 to 50, and particularly preferably 20 to 40. If it is within the above range, it is preferable for use as an optical lens.
• the polyester carbonate resin composition of the present invention preferably has a haze (%) of 0.2 to 6.0, more preferably 0.5 to 5.0, and particularly preferably 0.5 to 3.0. Within the above range, it is preferable for use as an optical lens.
• the polyester carbonate resin composition of the present invention preferably has a transmittance (%) at 450 nm of 40% to 99%, more preferably 45% to 90%, even more preferably 50% to 80%, and particularly preferably 50% to 70%.
• the optical lens produced by using the polyester carbonate resin composition of the present invention has a high refractive index and excellent heat resistance, and can be used in fields where expensive high refractive index glass lenses have been used in the past, such as telescopes, binoculars, and television projectors, and is extremely useful. If necessary, it is preferable to use it in the form of an aspherical lens. Since an aspherical lens can substantially reduce spherical aberration with one lens, it is not necessary to remove spherical aberration by combining multiple spherical lenses, and it is possible to reduce weight and production costs. Therefore, the aspherical lens is particularly useful as a camera lens among optical lenses.
• the optical lens is molded by any method, such as injection molding, compression molding, injection compression molding, etc. According to the present invention, it is possible to more easily obtain a high refractive index, low birefringence aspheric lens, which is technically difficult to process using glass lenses.
• the molding environment must of course be a low-dust environment, preferably class 6 or less, and more preferably class 5 or less.
• optical film produced using the polyester carbonate resin composition of the present invention has excellent transparency and heat resistance, and is therefore suitably used for liquid crystal substrate films, optical memory cards, and the like.
• the molding environment must also be a low-dust environment, preferably class 6 or less, and more preferably class 5 or less.
• a test piece was obtained in the same manner as in the dimensional change rate (%, MD), and the length of the longest part in the direction perpendicular to the Lm0 was measured with an image dimension measuring instrument and designated as Lt0.
• the test piece was stored for 72 hours in a thermostatic high-humidity chamber set at a temperature of 85 ° C. and a humidity of 85%, and then the length of the longest part in the direction perpendicular to the Lm was measured with an image dimension measuring instrument and designated as Lt.
• the dimensional change rate (%, TD) was calculated from the following formula.
• Water absorption rate (mass%) (Mt-M0)/M0 ⁇ 100 The mass was measured in an environment controlled at 23° C. ⁇ 2° C. (21° C. to 25° C.).
• the mixture was heated to 200°C over 20 minutes under a nitrogen atmosphere of 760 Torr and stirred. After adjusting the degree of vacuum to 300 Torr over 20 minutes, the temperature was raised to 240°C over 40 minutes, and the temperature was held at 240°C and 300 Torr for 10 minutes to carry out an ester exchange reaction. The mixture was returned to normal pressure with nitrogen gas, the trap was replaced, and the pressure was adjusted again to 240°C and 300 Torr and held for 10 minutes.
• Example 1 The polyester carbonate resin (PEC1) obtained in Polymerization Example 1 was added with 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane (ADEGASTABE PEP-36; manufactured by ADEKA CORPORATION); 300 ppm based on the polyester carbonate resin.
• Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Adekastab AO-60: manufactured by ADEKA Corporation); 1000 ppm relative to polyester carbonate resin, Stearyl stearate (Rikemal SL-800; manufactured by Riken Vitamin Co., Ltd.); 1500 ppm relative to polyester carbonate resin, Dodecylbenzenesulfonic acid tetrabutylphosphonium salt (MGA-614; manufactured by Takemoto Oil Co., Ltd.); 15 ppm relative to polyester carbonate resin, The following mixture: a 90:10 mixture of 3,4-dimethyl and 2,4-dimethyl (manufactured by Tokyo Chemical Industry Co., Ltd.); 200 ppm relative to polyester carbonate resin; The components were mixed in a twin-screw extruder to obtain a resin composition. The physical properties of the resulting resin composition are shown in Table 2. The extrusion details are as follows
• Example 2 A resin composition was obtained in the same manner as in Example 1, except that 3,000 ppm of stearyl stearate was used relative to the polyester carbonate resin. The physical properties of the obtained resin composition are shown in Table 2.
• Example 1 A resin composition was obtained in the same manner as in Example 1, except that "stearyl stearate (Rikemal SL-800; manufactured by Riken Vitamin Co., Ltd.); 1500 ppm relative to the polyester carbonate resin” was replaced with "glycerin monostearate (stearic acid monoglyceride, Rikemal S-100A; manufactured by Riken Vitamin Co., Ltd.); 1500 ppm relative to the polyester carbonate resin.”
• the physical properties of the obtained resin composition are shown in Table 2.
• Example 2 A resin composition was obtained in the same manner as in Example 1, except that "stearyl stearate (Rikemal SL-800; manufactured by Riken Vitamin Co., Ltd.); 1500 ppm relative to the polyester carbonate resin” was replaced with "glycerin monostearate (stearic acid monoglyceride, Rikemal S-100A; manufactured by Riken Vitamin Co., Ltd.); 3000 ppm relative to the polyester carbonate resin.”
• the physical properties of the obtained resin composition are shown in Table 2.

Landscapes

• Chemical & Material Sciences (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Optics & Photonics (AREA)
• General Physics & Mathematics (AREA)
• Materials Engineering (AREA)
• Polyesters Or Polycarbonates (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=93519052

Family Applications (1)

Country Status (6)

Citations (9)

• 2024
  • 2024-05-01 JP JP2025520503A patent/JPWO2024237098A1/ja active Pending
  • 2024-05-01 WO PCT/JP2024/016751 patent/WO2024237098A1/ja not_active Ceased
  • 2024-05-01 CN CN202480027417.9A patent/CN121002117A/zh active Pending
  • 2024-05-01 EP EP24807052.6A patent/EP4711417A1/en active Pending
  • 2024-05-01 KR KR1020257026247A patent/KR20260010674A/ko active Pending
  • 2024-05-01 TW TW113116269A patent/TW202449017A/zh unknown

Patent Citations (9)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events