WO2022158123A1 - Résine thermoplastique et élément optique comprenant celle-ci - Google Patents

Résine thermoplastique et élément optique comprenant celle-ci Download PDF

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WO2022158123A1
WO2022158123A1 PCT/JP2021/043914 JP2021043914W WO2022158123A1 WO 2022158123 A1 WO2022158123 A1 WO 2022158123A1 JP 2021043914 W JP2021043914 W JP 2021043914W WO 2022158123 A1 WO2022158123 A1 WO 2022158123A1
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thermoplastic resin
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義弘 石原
高恒 柳田
安彦 友成
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帝人株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
    • 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

  • thermoplastic resins having a high Abbe number and high heat resistance, and optical members and optical lenses formed therefrom.
  • Glass which has been conventionally used as a material for optical systems, can achieve the various optical properties required and has excellent environmental resistance, but has the problem of poor workability.
  • resins which are less expensive than glass materials and have excellent workability, have been used for optical members.
  • the development of resins with a high refractive index and a low Abbe number has been actively carried out, and along with this, the demand for resins with a high Abbe number is increasing.
  • Patent Documents 1 to 3 describe polyester resin compositions containing compounds obtained by hydrogenating bisphenol A.
  • Patent Document 4 describes that a polyester resin containing a dicarboxylic acid having an alicyclic skeleton and a fluorene skeleton compound has an Abbe number of approximately 27 to 45.
  • JP-A-2002-284865 Japanese Patent Application Laid-Open No. 2004-210814 Japanese Patent No. 5867664 Japanese Unexamined Patent Application Publication No. 2020-117706
  • polyester resins described in Patent Documents 1 to 3 are difficult to use as molding materials, especially optical lenses, because of their low molecular weight and insufficient strength.
  • the polyester resin described in Patent Document 4 uses a compound having a fluorene skeleton as a raw material, the Abbe number remains at an intermediate level, leaving room for improvement.
  • an object of the present invention relates to a thermoplastic resin having a high Abbe's number and high heat resistance, and an optical member and an optical lens formed therefrom.
  • the present inventors have made intensive studies to achieve this object, and as a result, have found that a heat treatment using a dihydroxy compound having an alicyclic skeleton and a dicarboxylic acid having an alicyclic skeleton and/or an ester-forming derivative thereof as constituent raw materials.
  • the inventors have found that a plastic resin can solve the above problems, and have completed the present invention.
  • thermoplastic resin of the present invention in the following aspects.
  • thermoplastic resin having a number average molecular weight of 5,000 to 30,000, containing a repeating unit represented by the following formula (1).
  • R 1 to R 4 each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 12 carbon atoms, k represents 0 or 1, L represents a divalent linking group, X is a divalent linking group having an alicyclic skeleton containing no unsaturated bond, W is a single bond or at least one selected from the group represented by the following formula (2), (3) or (4) is.
  • R 5 and R 6 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 9 carbon atoms, or represent a group in which R 5 and R 6 combine to form a carbocyclic ring.
  • j represents an integer of 2 to 10.
  • R 7 and R 8 each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 12 carbon atoms
  • k
  • thermoplastic resin according to aspect 1 wherein in the formula (1), X is at least one selected from a cyclohexyl group, a decalin group, a tricyclodecane group, or a group represented by the following formula (5).
  • thermoplastic resin according to mode 1 or 2 wherein in formula (1), W is at least one selected from the group represented by formula (6), (7) or (8) below.
  • thermoplastic resin according to any one of aspects 1 to 4, which has a glass transition temperature of 110°C to 190°C.
  • thermoplastic resin having a high Abbe number and excellent heat resistance can be obtained. It can be used for optical members such as mobile phones, smartphones, tablet terminals, personal computers, digital cameras, video cameras, in-vehicle cameras, or surveillance cameras. The industrial effect it produces is exceptional.
  • the thermoplastic resin of the present invention is a thermoplastic resin characterized by containing a repeating unit represented by the following formula (1) and having a number average molecular weight of 5,000 to 30,000.
  • R 1 to R 4 each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 12 carbon atoms, k represents 0 or 1, L represents a divalent linking group, X is a divalent linking group having an alicyclic skeleton containing no unsaturated bond, W is a single bond or at least one selected from the group represented by the following formula (2), (3) or (4) is.
  • R 5 and R 6 each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 9 carbon atoms, or represent a group in which R 5 and R 6 combine to form a carbocyclic ring.
  • j represents an integer of 2 to 10.
  • thermoplastic resin containing the repeating unit represented by the formula (1) has a number average molecular weight of 5,000 to 30,000, the strength of the resin is sufficiently guaranteed, and the molding material It was found that it can be effectively used as When an optical lens is molded using such a resin, a material having a high Abbe's number and excellent heat resistance can be obtained.
  • R 1 to R 4 each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 12 carbon atoms, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, t-butyl group, cyclopentyl group and cyclohexyl group are preferred, hydrogen atom, methyl group and cyclohexyl group are more preferred, and hydrogen atom is even more preferred.
  • X represents a divalent linking group having an alicyclic skeleton containing no unsaturated bond, a cyclohexyl group, decalin group, bicyclohexyl group, tricyclodecane group, bidecarin group, the following formula ( 5), groups represented by (9) to (15), and the like.
  • R 5 and R 6 each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 9 carbon atoms, or a group in which R 5 and R 6 combine to form a carbocyclic ring. and this carbocyclic ring may have an alkyl group of 1 to 3 carbon atoms. Examples of the group forming the carbocyclic ring include a group represented by the following formula (7) and a group represented by (16).
  • R 5 and R 6 each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, a group represented by the following formula (7), It is preferably a group represented by formula (16), more preferably a hydrogen atom, a methyl group, an ethyl group, a group represented by formula (7) below, or a group represented by formula (16) below. , a methyl group, and a group represented by the following formula (7) are more preferable because the heat resistance of the resin is excellent.
  • j represents an integer of 2 to 10, preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3.
  • Tg glass transition temperature
  • R 7 and R 8 each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 12 carbon atoms, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl is preferably a group, t-butyl group, cyclopentyl group or cyclohexyl group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
  • W is preferably a group represented by the following formulas (6) to (8) and the following formulas (16) to (23), the following formulas (6) to (8), the following Groups represented by formula (16), formula (17), and formula (19) below are more preferred, and groups represented by formulas (6) to (8) below are more preferred.
  • L represents a divalent linking group, preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 4 carbon atoms, and an ethylene group. More preferred.
  • Tg glass transition temperature
  • k is 0 or 1.
  • thermoplastic resin containing the repeating unit represented by formula (1) of the present invention can be obtained from a dihydroxy compound and a dicarboxylic acid or an ester-forming derivative thereof.
  • the thermoplastic resin of the present invention may contain the repeating unit represented by the formula (1) in an amount of 5 mol% or more, 10 mol% or more, 15 mol% or more, 20 mol% or more, 25 mol% or more, 30 mol% or more. , 100 mol % or less, 90 mol % or less, 80 mol % or less, 70 mol % or less, 60 mol % or less, or 50 mol % or less.
  • the thermoplastic resin of the present invention preferably contains 10 mol% or more and 100 mol% or less, more preferably 20 mol% or more and 100 mol% or less, still more preferably 30 mol% or more and 100 mol% or less, of the repeating unit represented by the formula (1). Particularly preferably, it can be contained at 40 mol % or more and 100 mol % or less. It is preferable that the repeating unit represented by the formula (1) is within the above range, because not only the Abbe number is high, but also the balance between heat resistance and moldability is excellent.
  • thermoplastic resin of the present invention can contain a repeating unit represented by the following formula (24). (In the formula, Y represents a divalent linking group.)
  • the molar ratio of the repeating unit represented by the formula (1) and the repeating unit represented by the formula (24) is 95:5 to 5:95, and 90:10 to 10:90. More preferably, it is 85:15 to 15:85.
  • the molar ratio of the repeating unit represented by the formula (1) to the repeating unit represented by the formula (14) is within the above range, in addition to a high Abbe number, heat resistance and moldability It is preferable because it is also excellent in the balance of
  • thermoplastic resin of the present invention has a number average molecular weight of 5,000 to 30,000, preferably 8,000 to 28,000, more preferably 10,000 to 25,00. It is preferable that the number average molecular weight is within the above range because the balance between moldability and mechanical strength is excellent.
  • the Abbe number of the thermoplastic resin of the present invention is 46.0 or more, preferably 48.0 or more, more preferably 50.0 or more, further preferably 52.0 or more, and 54 0.0 or more is particularly preferred, and 56.0 or more is most preferred.
  • the glass transition temperature (Tg) of the thermoplastic resin of the present invention is preferably 110 to 190°C, more preferably 110 to 175°C, even more preferably 115 to 170°C, and 115 to 165. °C is particularly preferred. When the glass transition temperature is within the above range, the balance between heat resistance and moldability is excellent, which is preferable.
  • the refractive index of the thermoplastic resin of the present invention is 1.450 or more, 1.460 or more, 1.470 or more, 1.480 or more, 1.480 or more, when measured at a temperature of 20° C. and a wavelength of 587.56 nm. .490 or greater, or 1.500 or greater, 1.550 or less, and 1.54 It may be 0 or less, 1.530 or less, 1.520 or less, or 1.510 or less. It is preferably 1.450 to 1.550, more preferably 1.460 to 1.540, even more preferably 1.480 to 1.530.
  • the dihydroxy compound used as the raw material of the formula (1) is mainly a dihydroxy compound represented by the following formula (a), and may be used alone or in combination of two or more.
  • R 1 to R 4 , W, L, and k are the same as in formula (1) above.
  • dihydroxy compounds represented by formula (a) include 4,4′-methylenebis(hydroxycyclohexane), 2,2-bis(4-hydroxycyclohexyl)propane, 3,3-(4-hydroxycyclohexyl) butane, 2,2-bis(3-methyl-4-hydroxycyclohexyl)propane, 1,1-bis(4-hydroxycyclohexyl)cyclohexane, 1,1-bis(4-hydroxycyclohexyl)3,3,5-trimethylcyclohexane , 2,2-bis(4-hydroxycyclohexyl)tricyclo[7.4.0.0 3,8 ]dodecane, 2,2-bis(3-methyl-4hydroxycyclohexyl)tricyclo[7.4.0.0 3,8 ]dodecane, 4,4′-methylenebis[(2-hydroxyethoxy)cyclohexane], 2,2-bis[4-(2-hydroxyethoxy)cyclohexyl]propane, 3,3-bis[4-m
  • the following formula (a-1) represented by the following formulas (a-1) to (a-3): 2,2-bis(4-hydroxycyclohexyl)propane
  • the following formula (a-2) 1,1-bis(4-hydroxycyclohexyl)3,3,5-trimethylcyclohexane
  • the following formula (a-3) 2,2-bis[4-(2-hydroxyethoxy)cyclohexyl]tricyclo[7.4.
  • 0.0 3,8 ]dodecane is preferable because the resin from which 0.0 3,8 ]dodecane is obtained has excellent heat resistance. These may be used alone or in combination of two or more.
  • Dicarboxylic acid component of formula (1) above Dicarboxylic acid represented by the following formula (b) or an ester-forming derivative thereof is preferably used as the dicarboxylic acid serving as a raw material of the formula (1).
  • X is the same as each formula in the above formula (1).
  • Dicarboxylic acids used in the thermoplastic resin of the present invention include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,5-decalinedicarboxylic acid, 1,6- decalindicarboxylic acid, 1,7-decalindicarboxylic acid, 1,8-decalindicarboxylic acid, 2,6-decalindicarboxylic acid, 2,7-decalindicarboxylic acid, 3,7-decalindicarboxylic acid, 2,2-bis[ (4-Carboxymethoxy)cyclohexyl]propane, 2,2′-dicarboxy-1,1′-bicyclohexane, 3,3′-dicarboxy-1,1′-bicyclohexane, 4,4′-dicarboxy- 1,1′-bicyclohexane, 2,2′-bis(carboxymethoxy)-1,1′-bic
  • formulas (b-1) to (b-4) represented by the following formulas (b-1) to (b-4), the following formula (b-1): 1,4-cyclohexanedicarboxylic acid, the following formula (b-2): 2,6-decalin Dicarboxylic acid, formula (b-3) below: 2,2-bis[(4-carboxymethoxy)cyclohexyl]propane, formula (b-4) below: tricyclo[5.2.1.0 2,6 ]decanedicarbonate Acids are particularly preferred due to their excellent reactivity.
  • ester-forming derivatives acid chlorides and esters such as methyl esters, ethyl esters and phenyl esters may be used.
  • thermoplastic resin of the present invention has a repeating unit represented by the formula (1), but may contain a copolymer component separately from it.
  • a copolymer component include dihydroxy compounds other than those represented by the formula (a), repeating units having a carbonate bond, and the like.
  • thermoplastic resin of the present invention examples include ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, tricyclo [5.2.
  • Carbonate esters include esters of optionally substituted aryl groups having 6 to 10 carbon atoms, aralkyl groups, or alkyl groups having 1 to 4 carbon atoms. Specifically, diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, bis(m-cresyl) carbonate, diaryl carbonate such as dinaphthyl carbonate, dialkyl carbonate such as dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, and ethyl carbonate.
  • Examples include alkylaryl carbonates such as phenyl carbonate and cyclohexylphenyl carbonate, and dialkenyl carbonates such as divinyl carbonate, diisopropenyl carbonate and dipropenyl carbonate. Among them, diaryl carbonate is preferred, and diphenyl carbonate is more preferred.
  • thermoplastic resin of the present invention is produced, for example, by a method of reacting a dihydroxy compound with a dicarboxylic acid or an ester-forming derivative thereof, or a method of reacting a dihydroxy compound with a carbonate precursor such as phosgene or a diester carbonate. Specific examples are shown below.
  • thermoplastic resin of the present invention is a polyester resin
  • a reaction means known per se for example, a dihydroxy compound and a dicarboxylic acid or an ester-forming derivative thereof are subjected to an esterification reaction or a transesterification reaction, and the resulting reaction product is A polycondensation reaction may be performed to obtain a high molecular weight product having a desired molecular weight.
  • thermoplastic resin of the present invention is a polyester carbonate resin
  • it can be produced by reacting a dihydroxy compound and a dicarboxylic acid or an ester-forming derivative thereof with a carbonate precursor such as phosgene or a carbonate ester.
  • a carbonate precursor such as phosgene or a carbonate ester.
  • the same method as that for the polyester resin can be used.
  • the optical member of the present invention contains the above thermoplastic resin.
  • Such an optical member is not particularly limited as long as it is an optical application for which the above thermoplastic resin is useful, but optical lenses, optical discs, transparent conductive substrates, optical cards, sheets, films, optical fibers, lenses, prisms, etc. , optical films, substrates, optical filters, hard coat films, and the like.
  • the optical member of the present invention may be composed of a resin composition containing the above thermoplastic resin, and the resin composition may contain a heat stabilizer, a plasticizer, a light stabilizer, a polymerization Additives such as metal deactivators, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, ultraviolet absorbers, release agents, and antioxidants can be added.
  • optical lens As an optical member of the present invention, an optical lens can be mentioned in particular. Examples of such optical lenses include optical lenses for mobile phones, smart phones, tablet terminals, personal computers, digital cameras, video cameras, vehicle-mounted cameras, surveillance cameras, and the like.
  • optical member and optical lens of the present invention can be molded and processed by any method such as injection molding, compression molding, injection compression molding, melt extrusion molding, casting, etc., but injection molding is particularly preferred.
  • the molding conditions for injection molding are not particularly limited, but the cylinder temperature of the molding machine is preferably 180 to 320°C, more preferably 220 to 300°C, and particularly preferably 240 to 280°C.
  • the mold temperature is preferably 70 to 130°C, more preferably 80 to 125°C, even more preferably 90 to 120°C.
  • the injection pressure is preferably 5 to 170 MPa, more preferably 50 to 160 MPa, even more preferably 100 to 150 MPa.
  • ⁇ d (nd-1)/(nF-nC) nd: refractive index at a wavelength of 587.56 nm; nF: refractive index at a wavelength of 486.13 nm; nC: Refractive index at a wavelength of 656.27 nm.
  • Tg Glass transition temperature
  • the obtained resin was measured with a Discovery DSC 25 Auto model manufactured by TA Instruments Japan Co., Ltd. at a temperature increase rate of 20° C./min. Samples were measured at 5-10 mg.
  • ⁇ Number average molecular weight (Mn)> The number average molecular weight was measured by the following method using gel permeation chromatography (GPC). 1.0 mg of the obtained resin was dissolved in 5 mL of chloroform to prepare a solution. For each sample, the molecular weight in terms of polystyrene was calculated using GPC. The analysis was performed under the following measurement conditions.
  • Example 1 32.13 parts by mass (50 mol parts) of 2,2-bis(4-hydroxycyclohexyl)propane (hereinafter sometimes abbreviated as HBPA), diphenyl 1,4-cyclohexanedicarboxylate (hereinafter abbreviated as DPCD ) and 4.45 ⁇ 10 ⁇ 2 parts by mass (4.00 ⁇ 10 ⁇ 4 mol parts) of titanium tetrabutoxide as a catalyst were added and heated to 200° C. in a nitrogen atmosphere. melted. After that, the degree of pressure reduction was adjusted to 20 kPa over 10 minutes.
  • HBPA 2,2-bis(4-hydroxycyclohexyl)propane
  • DPCD diphenyl 1,4-cyclohexanedicarboxylate
  • DPCD diphenyl 1,4-cyclohexanedicarboxylate
  • the temperature is raised to 260°C at a rate of 30°C/hr, and after the outflow of phenol reaches 70%, the pressure is reduced to 60 kPa/hr, and the polymerization reaction is carried out until a predetermined power is reached, and the reaction is completed.
  • the resin was removed from the flask.
  • the obtained polyester resin was analyzed by 1 H NMR, and it was confirmed that the HBPA component was introduced in an amount of 50 mol % with respect to all monomers.
  • the copolymerization ratio, refractive index, Abbe number, Tg and Mn of the polyester resin were evaluated.
  • Example 2 21.42 parts by mass (50 mol parts) of HBPA, 23.47 parts by mass (52 mol parts) of dimethyl 2,6-decalinedicarboxylate (hereinafter sometimes abbreviated as DDMC), and titanium tetrabutoxide as a catalyst. .90 ⁇ 10 ⁇ 2 parts by mass (1.00 ⁇ 10 ⁇ 3 mol parts) were added, and the same procedure as in Example 1 was carried out to obtain a polyester resin. The copolymerization ratio, refractive index, Abbe number, Tg and Mn of the polyester resin were evaluated.
  • DDMC dimethyl 2,6-decalinedicarboxylate
  • Example 3 24.69 parts by mass (40 mol parts) of HBPA, 5.24 parts by mass (10 mol parts) of tricyclo[5.2.1.0 2,6 ]decane dimethanol (hereinafter sometimes abbreviated as TCDDM), 44.91 parts by mass (52 mol parts) of DPCD and 4.45 ⁇ 10 ⁇ 2 parts by mass (4.00 ⁇ 10 ⁇ 4 mol parts) of titanium tetrabutoxide as a catalyst were added, and polyester was prepared in the same manner as in Example 1. The copolymerization ratio, refractive index, Abbe number, Tg and Mn of the polyester resin from which the resin was obtained were evaluated.
  • TCDDM tricyclo[5.2.1.0 2,6 ]decane dimethanol
  • Example 4 24.69 parts by mass (40 mol parts) of HBPA and 3.85 parts by mass (10 mol parts) of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (hereinafter sometimes abbreviated as TMCBD) , 44.91 parts by mass (52 mol parts) of DPCD, and 4.45 ⁇ 10 -2 parts by weight (4.00 ⁇ 10 -4 mol parts) of titanium tetrabutoxide as a catalyst were added, and in the same manner as in Example 1, A polyester resin was obtained. The copolymerization ratio, refractive index, Abbe number, Tg and Mn of the polyester resin were evaluated.
  • TMCBD 2,2,4,4-tetramethyl-1,3-cyclobutanediol
  • Example 5 24.69 parts by mass (40 mol parts) of HBPA, 3.90 parts by mass (10 mol parts) of isosorbide (hereinafter sometimes abbreviated as ISS), 44.91 parts by mass (52 mol parts) of DPCD, and as a catalyst 4.45 ⁇ 10 ⁇ 2 parts by mass (4.00 ⁇ 10 ⁇ 4 mol parts) of titanium tetrabutoxide were added, and in the same manner as in Example 1, a polyester resin was obtained. The copolymerization ratio, refractive index, Abbe number, Tg and Mn of the polyester resin were evaluated.
  • Example 6 32.13 parts by mass (50 mol parts) of HBPA, 36.59 parts by mass (42 mol parts) of DPCD, 4.52 parts by mass (8 mol parts) of diphenyl carbonate (hereinafter sometimes abbreviated as DPC), and a catalyst 4.55 ⁇ 10 ⁇ 2 parts by mass (5.00 ⁇ 10 ⁇ 4 mol parts) of titanium tetrabutoxide was added as a material and heated to 200° C. in a nitrogen atmosphere to melt. After that, the degree of pressure reduction was adjusted to 20 kPa over 10 minutes.
  • DPC diphenyl carbonate
  • the temperature was raised to 250°C at a rate of 30°C/hr, and after the outflow of phenol reached 70%, the pressure was reduced to 60 kPa/hr, and the polymerization reaction was carried out until a predetermined power was reached, and the reaction was completed. After the resin was removed from the flask.
  • the obtained polyester carbonate resin was analyzed by 1 H NMR, and it was confirmed that the HBPA component was introduced in an amount of 50 mol % with respect to all the monomers.
  • the copolymerization ratio, refractive index, Abbe number, Tg and Mn of the polyester carbonate resin were evaluated.
  • Example 7 43.1 parts by mass (50 mol parts) of 1,1-bis(4-hydroxycyclohexyl) 3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as HTMC), 44.91 parts by mass (52 mol parts) of DPCD parts) and 4.45 ⁇ 10 ⁇ 2 parts by mass (4.00 ⁇ 10 ⁇ 4 mol parts) of titanium tetrabutoxide as a catalyst were added in the same manner as in Example 1 to obtain a polyester resin. The copolymerization ratio, refractive index, Abbe number, Tg and Mn of the polyester resin were evaluated.
  • HTMC 1,1-bis(4-hydroxycyclohexyl) 3,3,5-trimethylcyclohexane
  • Example 8 28.7 parts by mass (50 mol parts) of HTMC, 23.47 parts by mass (52 mol parts) of DDMC, and 9.90 ⁇ 10-2 parts by weight (1.00 ⁇ 10-3 mol parts) of titanium tetrabutoxide as a catalyst
  • a polyester resin was obtained. The copolymerization ratio, refractive index, Abbe number, Tg and Mn of the polyester resin were evaluated.
  • Example 9 33.1 parts by mass (40 mol parts) of HTMC, 5.24 parts by mass (10 mol parts) of TCDDM, 44.91 parts by mass (52 mol parts) of DPCD, and 4.45 ⁇ 10-2 titanium tetrabutoxide as a catalyst. Parts by mass (4.00 ⁇ 10 ⁇ 4 mol parts) were added, and the copolymerization ratio, refractive index, Abbe number, Tg, and Mn of the polyester resin obtained in the same manner as in Example 1 were evaluated.
  • Table 1 shows the results of the evaluation of examples for thermoplastic resins.
  • HBPA 2,2-bis(4-hydroxycyclohexyl)propane
  • HTMC 1,1-bis(4-hydroxycyclohexyl)3,3,5-trimethylcyclohexane
  • TCDDM tricyclo[5.2.1.0 2,6 ]
  • TMCBD 2,2,4,4-tetramethyl-1,3-cyclobutanediol
  • ISS isosorbide
  • BPEF 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene
  • TMC 1,1- Bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane
  • DPCD phenyl 1,4-cyclohexanedicarboxylate
  • DDMC dimethyl 2,6-decalinedicarboxylate
  • BCMB 2,2′-bis(carboxymethoxy)-1 , 1′-binaphthyl
  • thermoplastic resins with high Abbe numbers were obtained in Examples 1 to 6 using HBPA. Also in Examples 7 to 9 using HTMC, thermoplastic resins having high Abbe numbers were obtained.
  • Example 1 and Comparative Example 1 use a dicarboxylic acid component having an alicyclic skeleton. .0, and Example 1, which does not contain a dihydroxy compound containing a fluorene skeleton, achieves a higher Abbe number.
  • Example 7 and Comparative Example 1 use a dicarboxylic acid component having an alicyclic skeleton. .0, and Example 7, which does not contain a dihydroxy compound containing a fluorene skeleton, achieves a higher Abbe number.
  • Example 1 and Comparative Example 2 use a dihydroxy compound having an alicyclic skeleton. 5, and Example 1, which does not contain a dicarboxylic acid component containing an unsaturated bond, achieves a higher Abbe number.
  • Example 8 and Comparative Example 4 use a dihydroxy compound having an alicyclic skeleton. 2, and Example 8, which does not contain a dicarboxylic acid component containing an unsaturated bond, achieves a higher Abbe number.
  • thermoplastic resin obtained in the example when an optical lens was produced by injection molding using the thermoplastic resin obtained in the example, it had sufficient strength to be used as a molding material.
  • thermoplastic resin of the present invention is used for optical materials, and is used for optical members such as optical lenses, prisms, optical discs, transparent conductive substrates, optical cards, sheets, films, optical fibers, optical films, optical filters, and hard coat films. It is very useful especially for optical lenses.

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Le but de la présente invention est de fournir une résine thermoplastique ayant un nombre d'Abbe élevé et une résistance thermique élevée. La résine thermoplastique de la présente invention comprend une unité de répétition représentée par la formule (1), et le poids moléculaire moyen en nombre est de 5 000 à 30 000. (Dans la formule (1), R1 à R4 représentent chacun indépendamment un atome d'hydrogène, un atome d'halogène, ou un groupe hydrocarboné ayant de 1 à 12 atomes de carbone, k vaut 0 ou 1, L désigne un groupe de liaison divalent, X est un groupe de liaison divalent ayant un squelette alicyclique et n'ayant pas de liaison insaturée, et W est une liaison simple ou au moins un élément choisi dans le groupe représenté par les formules (2), (3) et (4).)
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003048966A (ja) * 2001-08-09 2003-02-21 New Japan Chem Co Ltd 飽和環状脂肪族２級アルコールを原料とする脂環式ポリエステルの製造方法
JP2003073564A (ja) * 2001-09-04 2003-03-12 Mitsui Chemicals Inc 熱可塑性材料組成物、及びそれを含んで構成される光学部品

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003048966A (ja) * 2001-08-09 2003-02-21 New Japan Chem Co Ltd 飽和環状脂肪族２級アルコールを原料とする脂環式ポリエステルの製造方法
JP2003073564A (ja) * 2001-09-04 2003-03-12 Mitsui Chemicals Inc 熱可塑性材料組成物、及びそれを含んで構成される光学部品

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