WO2014054710A1 - Composition de résine thermoplastique ayant un squelette fluorène, et élément optique - Google Patents

Composition de résine thermoplastique ayant un squelette fluorène, et élément optique Download PDF

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Publication number
WO2014054710A1
WO2014054710A1 PCT/JP2013/076890 JP2013076890W WO2014054710A1 WO 2014054710 A1 WO2014054710 A1 WO 2014054710A1 JP 2013076890 W JP2013076890 W JP 2013076890W WO 2014054710 A1 WO2014054710 A1 WO 2014054710A1
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carbon atoms
thermoplastic resin
group
resin composition
lens
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PCT/JP2013/076890
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English (en)
Japanese (ja)
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輝幸 重松
学 松井
丹藤　和志
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帝人株式会社
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Priority to JP2014539799A priority Critical patent/JP5973587B2/ja
Publication of WO2014054710A1 publication Critical patent/WO2014054710A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses

Definitions

  • the present invention relates to a thermoplastic resin composition having a fluorene skeleton having a high degree of transparency and excellent molding fluidity, molding stability, and wet heat resistance, and an optical member comprising the same.
  • Optical glass or optical transparent resin is used as a material for optical lenses used in optical systems of various cameras such as cameras, film-integrated cameras, and video cameras.
  • Optical glass has excellent heat resistance, transparency, dimensional stability, chemical resistance, etc., and there are many types of materials with various refractive indexes and Abbe numbers. The problem is that the productivity is low and the productivity is low.
  • optical transparent resins in particular thermoplastic optical transparent resins, have the advantage that they can be mass-produced by injection molding, and polycarbonate resins and the like are currently used as materials for camera lenses.
  • the optical performance required for lens resins has become higher as products become lighter and thinner and cameras have higher pixels.
  • Patent Document 1 proposes a method of adding a polycarbonate oligomer and polycaprolactone to a polycarbonate resin.
  • Patent Documents 2 and 3 propose a method of adding a polyether ester resin or a styrene oligomer resin as a method for modifying the molding fluidity of a thermoplastic resin having a fluorene structure.
  • the characteristics required for optical lenses are difficult to use as a lens when the focal length and chromatic aberration are affected by the environment in which the lens is used. It is also an important characteristic for heat and humidity resistance.
  • molding stability such as a low yield during molding is also a very important characteristic.
  • the method using a plasticizer and the compositions of Patent Documents 1 to 3 have problems in high transparency, molding stability, and moist heat resistance.
  • thermoplastic resin using a fluorene derivative has not been obtained which has a high degree of transparency and sufficiently satisfies the moist heat resistance while maintaining the molding fluidity and molding stability.
  • an object of the present invention is to provide a thermoplastic resin composition having a fluorene skeleton having high transparency, molding fluidity, molding stability, and moist heat resistance, and an optical member comprising the same.
  • the present inventors have intensively studied to achieve this purpose. As a result, the inventors have found that the thermoplastic resin having a fluorene skeleton is excellent in high transparency, molding fluidity, molding stability, and moist heat resistance by mixing an appropriate amount of an aliphatic epoxy compound. . That is, the present invention 1.
  • R 1, R 2, R 3 and R 4 are each independently a hydrogen 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, or a carbon number of 5
  • X is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or carbon
  • thermoplastic resin composition having a fluorene skeleton containing 0.1 to 10 parts by weight 2.
  • thermoplastic resin composition having a fluorene skeleton as described in 3 above, wherein the epoxidized vegetable oil is epoxidized soybean oil or epoxy linseed oil. 5.
  • the thermoplastic resin includes a repeating unit composed of a carbonate unit derived from a monomer represented by the general formula (1) and the following general formula (3).
  • R5 to R8 are each independently a hydrogen atom, a hydrocarbon group or a halogen atom which may contain an aromatic group having 1 to 9 carbon atoms, and W is a single bond having 1 to 20 carbon atoms.
  • the thermoplastic resin is represented by the following general formula (4).
  • R13 and R14 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms
  • R15 and R16 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms.
  • the monomer represented by the general formula (1) is 9,9-bis (4-hydroxy-3-methylphenyl) fluorene or 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene.
  • An optical member comprising the thermoplastic resin composition having a fluorene skeleton according to any one of 1 to 8 above.
  • 10. The optical member according to 9, wherein the optical member is an optical lens of a camera lens, a pickup lens, a microarray lens, a projector lens, or a Fresnel lens.
  • 11. The optical member as described in 10 above, wherein the thickness of the optical lens is 0.5 mm or less.
  • the aliphatic epoxy compound of the present invention has the following general formula (2) Where R is CH 3 Or H, o is 1 to 20, p is 1 to 10, and I is 1 to 20. ) Is an aliphatic epoxy compound having a moiety represented by
  • o in the formula is 1 to 20, the molding fluidity can be improved while maintaining transparency due to the effect of the alkylene group. If o is less than 1, the molding fluidity is insufficient, and if it is greater than 20, the compatibility with the resin deteriorates and the transparency cannot be maintained.
  • p in the formula is 1 to 10, the epoxy group traps moisture and suppresses hydrolysis of the thermoplastic resin, thereby improving the heat and moisture resistance.
  • the heat-and-moisture stability decreases.
  • the number is more than 10, the aliphatic epoxy compounds react with each other to form a multimer, and thus the heat and humidity resistance decreases. More preferably, it is 2 to 8, and more preferably 3 to 8.
  • I in the formula is 1 to 20, the molding fluidity while maintaining high transparency and moist heat resistance is improved.
  • I is less than 1, the molding fluidity is insufficient and the heat and humidity resistance deteriorates. Furthermore, bleed out from the resin may occur.
  • I is larger than 20, the compatibility with the resin is deteriorated and the transparency cannot be maintained.
  • the aliphatic epoxy compound used in the present invention is a compound having one or more epoxy groups in the molecular skeleton.
  • the aliphatic epoxy compound used in the present invention is a compound in which a glycerin skeleton and an aliphatic chain having an epoxy group are bonded via an ester, and in particular, a carbonyl group of the above formula (2)
  • the number of methylene groups in the excluded fatty chain is preferably 2 to 20 from the viewpoint of molding stability such as high transparency, molding fluidity, heat and humidity resistance, and suppression of gas generation during molding.
  • aliphatic epoxy compounds having a glycerin skeleton epoxidized vegetable oil is preferable, and epoxidized soybean oil and epoxidized sesame oil are more preferable.
  • epoxidized soybean oil having 2 to 6 epoxy groups and epoxidized linseed oil are preferred from the viewpoint of moist heat resistance.
  • Such an aliphatic epoxy compound needs to be contained in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of a thermoplastic resin having a fluorene skeleton described later. When the content is less than 0.1 parts by weight, the molding fluidity is inferior.
  • the amount when the amount is more than 10 parts by weight, it is incompatible with the resin and cannot maintain transparency, and when used under high temperature and high humidity, the molecular weight of the thermoplastic resin having a fluorene skeleton decreases, and the resin hue and strength The heat-and-moisture stability decreases.
  • the content of the above-mentioned aliphatic epoxy compound used in the present invention is preferably 0.1 to 8 parts by weight, more preferably 0.8 to 100 parts by weight of the thermoplastic resin having a fluorene skeleton. 1 to 5 parts by weight.
  • R 1, R 2, R 3 and R 4 are each independently a hydrogen 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, or a carbon number of 5 A cycloalkoxyl group having 20 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms
  • X is an alkylene group having 2 to 8 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms, or carbon A monomer represented by an arylene group of formula 6 to 20.
  • n and m are integers of 0 to 10) is a fluorene compound.
  • R1, R2, R3 and R4 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, or a cyclohexane having 5 to 10 carbon atoms. An alkoxyl group is preferred.
  • Specific examples of the fluorene compound include 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) fluorene, and 9,9-bis (4-hydroxy-3).
  • the fluorene compound is more preferably 9,9-bis (4-hydroxy-3-methylphenyl) fluorene or 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene.
  • the thermoplastic resin used in the present invention includes a repeating unit composed of a carbonate unit or an ester unit derived from the fluorene compound of the above formula (1), and examples thereof include polycarbonate and polyester carbonate.
  • the polycarbonate used in the present invention has a repeating unit composed of a carbonate unit derived from a dihydroxy compound represented by the following general formula (3) and copolymerizable with the fluorene compound represented by the above formula (1). You may do it.
  • R5 to R8 are each independently a hydrogen atom, a hydrocarbon group or a halogen atom which may contain an aromatic group having 1 to 9 carbon atoms, and W is a single bond having 1 to 20 carbon atoms. Hydrocarbon groups that may contain aromatic groups, O, S, SO, SO 2 , CO or COO groups. )
  • W in the general formula (3) is preferably a group represented by the following formula (6).
  • R9 and R10 are the same or different, a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R11 and R12 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n is 4 It is an integer of ⁇ 7.
  • the dihydroxy compound preferably used include 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane (bisphenol E), 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxy-3-methylphenyl) propane (bisphenol C), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) Pentane, 4,4 '-(p-phen
  • Bisphenol A is particularly preferable. You may use these individually or in combination of 2 or more types. As long as the optical properties are not impaired, aromatic dihydroxy compounds such as hydroquinone and resorcinol that do not fall under the general formula (3), aliphatic diols such as ethylene glycol, tricyclo [5.2.1.02,6] decandi Methanol, cyclohexane-1,4-dimethanol, decalin-2,6-dimethanol, norbornane dimethanol, pentacyclopentadecanedimethanol, cyclopentane-1,3-dimethanol, spiroglycol, 1,4: 3,6 Carbonate units derived from alicyclic diols such as -dianhydro-D-sorbitol, 1,4: 3,6-dianhydro-D-mannitol, 1,4: 3,6-dianhydro-L-iditol may be included.
  • aromatic dihydroxy compounds such as hydroquinone and resorcinol that do not fall under
  • a reaction means known per se for producing an ordinary polycarbonate resin for example, a method of reacting a dihydroxy compound with a carbonate precursor such as phosgene or carbonic acid diester. In a reaction using, for example, phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and a solvent.
  • the acid binder for example, an amine compound such as pyridine is used.
  • the solvent for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used.
  • the reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours.
  • monofunctional phenols that are usually used as a terminal terminator can be used in the polymerization reaction. Particularly in the case of a reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as a terminator for controlling the molecular weight, and the resulting aromatic polycarbonate resin has a terminal monofunctional phenol.
  • the carbonic acid diester is preferably used in a ratio of 0.97 to 1.20 mol, more preferably 0.98 to 1.10 mol, relative to 1 mol of the diol component.
  • the basic compound catalyst include alkali metal compounds, alkaline earth metal compounds, and nitrogen-containing compounds. Examples of such compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides or alkoxides of alkali metals and alkaline earth metals, and quaternary ammonium hydroxides and salts thereof, amines, and the like. Nitrogen-containing compounds are preferably used, and these compounds can be used alone or in combination.
  • alkali metal compounds include sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, sodium acetate, sodium benzoate, disodium salt of bisphenol A, sodium salt of phenol, and the like. Used.
  • alkaline earth metal compound include magnesium hydroxide and calcium hydroxide.
  • nitrogen-containing compounds include quaternary ammonium hydroxides having alkyl, aryl, groups, etc.
  • tetramethylammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, Tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine, secondary amines such as diethylamine and dibutylamine, primary amines such as propylamine and butylamine, 2-methylimidazole, 2-phenylimidazole and benzimidazole Imidazoles such as are used.
  • the transesterification catalyst zinc, tin, zirconium and lead salts are preferably used, and these can be used alone or in combination.
  • transesterification catalyst examples include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin (II) chloride, tin (IV) chloride, tin (II) acetate, tin (IV) acetate, and dibutyltin.
  • Dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, lead (IV) acetate and the like are used. These catalysts are used in an amount of 10 mol per 1 mol of the dihydroxy compound.
  • the melt polycondensation method is a method in which melt polycondensation is performed using the above-described raw materials and catalyst while removing by-products by a transesterification reaction under normal pressure or reduced pressure.
  • the reaction is generally carried out in a multistage process of two or more stages. Specifically, the first stage reaction is carried out at a temperature of 120 to 260 ° C., preferably 180 to 240 ° C. for 0.1 to 5 hours, preferably 0.5 to 3 hours. Next, the reaction temperature is raised while raising the degree of vacuum of the reaction system to react the dihydroxy compound with the carbonic acid diester.
  • polycondensation 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.
  • Perform the reaction Such a reaction may be carried out continuously or batchwise.
  • the reaction apparatus used for carrying out the above reaction is equipped with paddle blades, lattice blades, glasses blades, etc. even with vertical types equipped with vertical stirring blades, Max blend stirring blades, helical ribbon stirring blades, etc. It may be a horizontal type or an extruder type equipped with a screw. In particular, it is preferable to use a reactor in which these are appropriately combined in consideration of the viscosity of the polymer.
  • the catalyst is removed or deactivated after the polymerization reaction in order to maintain thermal stability and hydrolysis stability.
  • a method of deactivating a catalyst by adding a known deactivator is preferably performed.
  • these substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, and aromatic sulfonic acids such as butyl p-toluenesulfonate and hexyl p-toluenesulfonate.
  • esters Preference is given to esters, phosphoric acids such as phosphorous acid, phosphoric acid, phosphonic acid, benzoyl chloride, p-toluenesulfonic acid chloride and the like.
  • deactivators are used in an amount of 0.01 to 50 times mol, preferably 0.3 to 20 times mol for the amount of catalyst. When the amount is less than 0.01 times the amount of the catalyst, the deactivation effect is insufficient. Moreover, when it is more than 50 times mole with respect to the amount of catalyst, heat resistance will fall and it will become easy to color a molded object.
  • a step of devolatilizing and removing the low-boiling compound in the polymer at a pressure of 13.3 to 1133.3 Pa and a temperature of 200 to 350 ° C. may be provided.
  • a horizontal apparatus equipped with a stirring blade excellent in surface renewability, such as a glasses blade, or a thin film evaporator is preferably used.
  • the polycarbonate resin in the present invention is preferably one having 0.7 g of the polymer dissolved in 100 ml of methylene chloride and having a specific viscosity in the range of 0.12 to 0.55 measured at 20 ° C., preferably 0.15 to 0.45. A range is more preferable.
  • the acid component forming the ester unit is a dicarboxylic acid component represented by the general formula (4) and / or the general formula (5), and is represented by the general formula (1).
  • Such a polyester carbonate may be copolymerized with a dihydroxy compound represented by the above general formula (3) that can be copolymerized with the fluorene compound represented by the above formula (1).
  • the dihydroxy compound represented by the general formula (3) preferably used is the same as that described for the polycarbonate. Similarly, other dihydroxy compounds may be used in combination as long as the optical properties are not impaired.
  • the acid component forming the ester unit is represented by the following general formula (4) (Wherein R13 and R14 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aryloxy group having 6 to 20 carbon atoms) And / or the following general formula (5): Wherein R15 and R16 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms.
  • Preferred dicarboxylic acids represented by general formula (4) include terephthalic acid and isophthalic acid, with terephthalic acid being particularly preferred.
  • Examples of the dicarboxylic acid represented by the general formula (5) preferably used include 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 6-Naphthalenedicarboxylic acid is preferred. Of these, terephthalic acid and isophthalic acid, particularly terephthalic acid are preferred as the dicarboxylic acid.
  • dicarboxylic acid components other than the dicarboxylic acid represented by General formula (4) or General formula (5) may be included.
  • the carbonate precursor used for producing the polyester carbonate resin include phosgene, diphenyl carbonate, bischloroformate of the above dihydric phenols, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, and di-p-chlorophenyl carbonate. And dinaphthyl carbonate. Among them, diphenyl carbonate is preferable.
  • a method for producing a polyester carbonate resin a method used for producing a normal polyester carbonate resin is arbitrarily employed.
  • a reaction between a diol and a dicarboxylic acid or dicarboxylic acid chloride and phosgene or a transesterification reaction between a diol and a dicarboxylic acid or dicarboxylic acid dialkyl ester and a bisaryl carbonate is preferably employed.
  • the reaction of diol, dicarboxylic acid or its acid chloride with phosgene the reaction is carried out in the presence of an acid binder and a solvent in a non-aqueous system.
  • the acid binder include pyridine, dimethylaminopyridine, tertiary amine and the like.
  • halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. It is desirable to use a terminal terminator such as phenol or p-tert-butylphenol as the molecular weight regulator.
  • the reaction temperature is usually 0 to 40 ° C., and the reaction time is preferably several minutes to 5 hours.
  • a diol and a dicarboxylic acid or a diester thereof and a bisaryl carbonate are mixed in the presence of an inert gas and reacted at 120 to 350 ° C., preferably 150 to 300 ° C. under reduced pressure.
  • the degree of vacuum is changed stepwise, and finally the alcohols produced at 1 mmHg or less are distilled out of the system.
  • the reaction time is usually about 1 to 4 hours.
  • a polymerization catalyst can be used to promote the reaction.
  • an alkali metal compound, an alkaline earth metal compound or a heavy metal compound may be used as a main component, and a nitrogen-containing basic compound may be used as a subsidiary component if necessary.
  • Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium salt of bisphenol A, and the like.
  • Examples of the alkaline earth metal compound include calcium hydroxide, magnesium hydroxide, calcium carbonate and the like.
  • Examples of the nitrogen-containing basic compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, trimethylamine, triethylamine, dimethylbenzylamine, triphenylamine, dimethylaminopyridine and the like.
  • transesterification catalysts include zinc, tin, zirconium, lead, titanium, germanium, antimony, osmium, and aluminum salts, such as zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride (II ), Tin (IV) chloride, tin (II) acetate, tin (IV) acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxide, zirconium acetylacetonate, zirconium oxyacetate, zirconium tetrabutoxide, lead (II) acetate, acetic acid Lead (IV) titanium tetrabutoxide (IV) or the like is used.
  • These catalysts may be used alone or in combination of two or more.
  • the amount of these polymerization catalysts used is 10 with respect to a total of 1 mol of diol and dicarboxylic acid. -9 ⁇ 10 -3 Used in molar ratios. These may be used alone or in combination of two or more.
  • a diaryl carbonate having an electron-withdrawing substituent may be added at a later stage or after completion of the polycondensation reaction in order to reduce the hydroxy end group.
  • an antioxidant or a heat stabilizer may be added to improve the hue.
  • the catalyst may be removed or deactivated in order to maintain thermal stability and hydrolysis stability.
  • a method of deactivating a catalyst by adding a known deactivator is preferably carried out.
  • these substances include esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid, aromatic sulfonic acid esters such as butyl p-toluenesulfonate, phosphorous acid, Phosphoric acids such as phosphoric acid and phosphonic acid, triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite, di-n-propyl phosphite, di-n-butyl phosphite, phosphoric acid Phosphoric esters such as triphenyl, phosphonic acids such as diphenylphosphonic acid, phosphonic acid esters such as diethyl phenylphosphonate, pho
  • deactivators are used in an amount of 0.01 to 50 times mol, preferably 0.3 to 20 times mol for the amount of catalyst.
  • the amount is less than 0.01 times the amount of the catalyst, the deactivation effect is insufficient.
  • it is more than 50 times mole with respect to the amount of catalyst, heat resistance will fall and it will become easy to color a molded object.
  • a step of devolatilizing and removing the low boiling point compound in the resin at a pressure of 133 to 13.3 Pa and a temperature of 200 to 320 ° C. may be provided.
  • the polyester carbonate resin in the present invention is preferably one having 0.7 g of the polymer dissolved in 100 ml of methylene chloride and having a specific viscosity measured at 20 ° C. in the range of 0.12 to 0.55, preferably 0.15 to 0. A range of .45 is more preferable.
  • the specific viscosity is less than 0.12, the molded product becomes brittle, and when it exceeds 0.55, the melt viscosity and the solution viscosity become high, and handling becomes difficult.
  • the thermoplastic resin composition of the present invention may contain various additives in order to impart various characteristics within a range that does not impair the object of the present invention.
  • Additives such as mold release agents, heat stabilizers, UV absorbers, bluing agents, antistatic agents, flame retardants, heat ray shielding agents, fluorescent dyes (including fluorescent whitening agents), light diffusing agents, other resins and An elastomer or the like can be blended.
  • a mold release agent that whose 90 weight% or more consists of ester of alcohol and a fatty acid is preferable.
  • Specific examples of the ester of alcohol and fatty acid include monohydric alcohol and fatty acid ester and / or partial ester or total ester of polyhydric alcohol and fatty acid.
  • esters stearic acid monoglyceride, stearic acid triglyceride, pentaerythritol tetrastearate, and a mixture of stearic acid triglyceride and stearyl stearate are preferably used.
  • the amount of the ester in the release agent is preferably 90% by weight or more, and more preferably 95% by weight or more when the release agent is 100% by weight.
  • the heat stabilizer include a phosphorus heat stabilizer, a sulfur heat stabilizer, and a hindered phenol heat stabilizer.
  • the phosphorus-based heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid, and esters thereof.
  • Tetrakis (2,4-di-tert-butylphenyl) -4,4 ′ is preferable.
  • -Biphenylene diphosphonite is used.
  • the content of the phosphorus-based heat stabilizer in the thermoplastic resin composition is preferably 0.001 to 0.2 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition.
  • the UV absorber at least one UV absorber selected from the group consisting of benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV absorbers, cyclic imino ester UV absorbers, and cyanoacrylates Is preferred.
  • the blending amount of the ultraviolet absorber is preferably 0.01 to 3.0 parts by weight, more preferably 0.02 to 1.0 parts by weight with respect to 100 parts by weight in the thermoplastic resin composition.
  • the amount is preferably 0.05 to 0.8 parts by weight. If it is the range of this compounding quantity, it is possible to provide sufficient weather resistance in a thermoplastic resin composition according to a use.
  • the bluing agent include Macrolex Violet B and Macrolex Blue RR manufactured by Bayer and polysynthremble-RLS manufactured by Clariant.
  • the blending amount of the bluing agent is preferably 0.05 to 1.5 ppm, more preferably 0.1 to 1.2 ppm with respect to the thermoplastic resin composition.
  • thermoplastic resin composition having a fluorene skeleton of the present invention can be obtained by blending a thermoplastic resin having a fluorene skeleton, an aliphatic epoxy compound, and various additives by any blending method. It is preferable that all or a part of each component is mixed at the same time or separately, for example, with a blender such as a blender, kneader, Banbury mixer, roll, or extruder, and uniformly dispersed.
  • a blender such as a blender, kneader, Banbury mixer, roll, or extruder
  • thermoplastic resin used in the present invention preferably has a glass transition temperature (Tg) measured at a heating rate of 20 ° C./min of 130 ° C. or more and less than 200 ° C. If the Tg is less than 130 ° C., the heat resistance is not sufficient depending on the use of the optical member formed using the thermoplastic resin composition. On the other hand, if the Tg is 200 ° C.
  • Tg glass transition temperature
  • the haze of a molded plate having a thickness of 0.1 mm obtained from the thermoplastic resin composition is preferably 2% or less, and more preferably 1% or less.
  • the amount of resin extruded in 300 ° C., a load of 1.2 kgf for 10 minutes is preferably 30 g or more, and more preferably 40 g or more.
  • the thermoplastic resin composition of the present invention preferably has a molecular weight retention of 95% or more after being left for 400 hours under conditions of 85 ° C. and 85% RH, and has no hue change.
  • the optical member of the present invention can be molded by, for example, injection molding, compression molding, injection compression molding, or casting of the thermoplastic resin composition having the fluorene skeleton of the present invention.
  • Optical lens When an optical lens made of the thermoplastic resin composition of the present invention is produced by injection molding, it is preferably molded under conditions of a cylinder temperature of 260 to 350 ° C. and a mold temperature of 90 to 170 ° C. More preferably, molding is performed under conditions of a cylinder temperature of 270 to 320 ° C. and a mold temperature of 100 to 160 ° C.
  • the optical lens of the present invention is preferably used in the form of an aspheric lens as necessary.
  • the aspherical lens is particularly useful as a camera lens among optical lenses.
  • the thermoplastic resin composition of the present invention has high molding fluidity, it is particularly useful as a material for an optical lens having a thin, small and complicated shape.
  • the upper limit of the thickness of the central portion is preferably 0.5 mm or less, and more preferably 0.4 mm or less.
  • the lower limit of the thickness of the central portion of the lens is preferably 0.05 mm or more, and more preferably 0.1 mm or more.
  • the diameter is 1.0 mm to 20.0 mm, more preferably 1.0 to 10.0 mm, and still more preferably 3.0 to 10.0 mm.
  • it is preferably a meniscus lens having a convex surface on one side and a concave surface on the other side.
  • Molding fluidity Melted in a quantity of resin extruded in 300 minutes at a load of 1.2 kgf and a load of 1.2 kgf using a nozzle with a diameter of 1 mm and a length of 10 mm by CAPIROGRAH1D manufactured by Toyo Seiki Seisakusho. The viscosity was measured.
  • Haze Haze was measured on a molded plate having a thickness of 1 mm using Nippon Denshoku Industries Co., Ltd. Haze Meter NDH2000.
  • Moisture and heat stability Molecular weight retention: After a molded piece having a thickness of 1 mm is allowed to stand for 2000 hours under the conditions of 85 ° C.
  • the specific viscosity retention is retained by the change in specific viscosity described below. Rated as a rate.
  • the specific viscosity ( ⁇ sp ) of the solution at 20 ° C. was measured, and the specific viscosity retention rate (molecular weight retention rate) after the wet heat test was determined.
  • the specific viscosity retention rate (molecular weight retention rate) was used as an index of moisture and heat resistance.
  • ⁇ sp ( ⁇ sp 1 / ⁇ sp 0) ⁇ 100 * ⁇ sp : specific viscosity retention, ⁇ sp 0: specific viscosity before test, ⁇ sp 1: specific viscosity after test (7)
  • Optical lens molding stability poor filling of aspherical lens after molding, each molding Defects, insufficient lens strength, etc. were confirmed visually. The evaluation was performed by performing 100 shot molding, and the probability of being a defective product was less than 1% ( ⁇ ), 1 to 5% ( ⁇ ), 5 to 20% ( ⁇ ), and 20% or less ( ⁇ ). Filling failure is defined as a filling failure due to insufficient resin to form a lens shape.
  • Molding failure is caused by one or more silver stripes / bubbles in one lens, or additive bleeding out. Shall be. Further, the insufficient strength of the lens means that the lens part and the sprue / runner part are broken from the mold during molding and cannot be taken out.
  • Synthesis Polycarbonate 21540 parts by weight of ion-exchanged water and 4930 parts by weight of a 48% aqueous sodium hydroxide solution were placed in a reactor equipped with a thermometer, a stirrer, and a reflux condenser.
  • BCF 9-bis (4-hydroxy-3-methylphenyl) fluorene
  • BPA 2,2-bis (4-hydroxyphenyl) propane
  • PC (2) In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 21540 parts by weight of ion-exchanged water and 4930 parts by weight of a 48% aqueous sodium hydroxide solution were added, and 9,9-bis (4 -Hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) 3231 parts by weight, 1,3-bis ⁇ 2- (4-hydroxyphenyl) propyl ⁇ benzene (hereinafter abbreviated as “BPM”) 2958 parts by weight and 15 parts by weight of hydrosulfite were dissolved, 14530 parts by weight of methylene chloride was added, and then 2200 parts by weight of phosgene was blown in at 15 to 25 ° C.
  • BCF 9,9-bis (4 -Hydroxy-3-methylphenyl) fluorene
  • BPM 1,3-bis ⁇ 2- (4-hydroxyphenyl) propyl ⁇ benz
  • the product was diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and when the conductivity of the aqueous phase became almost the same as that of ion-exchanged water, the methylene chloride was evaporated with a kneader, A white polymer having a molar ratio of BCF to BPM of 50:50, a specific viscosity of 0.297, and a Tg of 156 ° C. was obtained.
  • PC (3) 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene (hereinafter abbreviated as “BPEF”) 1403.2 parts by weight, BPA 182.7 parts by weight, diphenyl carbonate (hereinafter abbreviated as “DPC”) 878.0 parts by weight and sodium hydrogen carbonate 5.0 ⁇ 10 ⁇ 3 parts by weight were placed in a reactor equipped with a stirrer and a distillation apparatus, and after nitrogen substitution three times, a nitrogen atmosphere 101.3 It heated at 215 degreeC under * 10 ⁇ 3 > Pa, and stirred for 20 minutes. After complete dissolution, it was adjusted to 20 ⁇ 10 3 Pa over 15 minutes, and kept for 20 minutes under the conditions of 215 ° C.
  • BPEF 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene
  • PEC (1) Polyester carbonate BPEF 1403.2 parts by weight, dimethyl terephthalate (hereinafter sometimes abbreviated as “DMT”) 155.4 parts by weight, DPC 548.4 parts by weight, titanium tetrabutoxide 13.6 ⁇ 10 ⁇ 4 A part by weight was placed in a reaction kettle equipped with a stirrer and a distillation apparatus, heated to 180 ° C.
  • DMT dimethyl terephthalate
  • a colorless transparent pellet having a molar ratio of BPEF to terephthalic acid of 80:20, a specific viscosity of 0.201, and Tg of 150 ° C.
  • the pelletized resin composition was heat-dried at 120 ° C. for 8 hours. Then, using a SE30DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. at a molding temperature of Tg + 110 ° C. and a mold temperature of Tg ⁇ 10 ° C., a molded piece having a width of 2.5 cm, a length of 5 cm, and a thickness of 1 mm was injected. Molded. Table 1 shows the evaluation results of haze and heat-and-moisture resistance.
  • Optical lens Using a SE30DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., using resin molding temperature Tg + 170 ° C., mold temperature Tg-5 ° C., thickness 0.3 mm, convex curvature radius 5 mm, concave curvature radius 4 mm, diameter A 5 mm aspheric lens was injection molded. Table 1 shows the evaluation of molding stability of the optical lens.
  • Additive 1 Epoxidized soybean oil (number of epoxy groups: 4) Kapox S-6 manufactured by Kao Corporation
  • Additive 2 Epoxidized linseed oil (number of epoxy groups 6)
  • Additive 3 Alkyl monoester, alkyl triglyceride mixture Rikenmar SL-900 manufactured by RIKEN
  • Additive 4 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate
  • Additive 5 Bisphenoxyethanol full orange glycidyl ether
  • Additive 6 Trioctyl trimellitic acid
  • Additive 7 Polyether ester resin Eastman Chemical Company
  • Additive 8 Styrene oligomer FTR2140 manufactured by Mitsui Chemicals, Inc.
  • Stabilizer Tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Mold release agent: Glycerol monostearate
  • Table 1 The unit of Table 1 is parts by weight with respect to the amount. [Examples 1 to 7 and Comparative Examples 1 to 9] After the various components were previously dry-blended uniformly in the proportions shown in Table 1, the KZ-W15-30MG twin-screw extruder manufactured by Technobel Co., Ltd. and manufactured by Technobel Co. were used under the conditions described in Table 1 below. It was melted and pelletized, and a molded product was appropriately prepared and evaluated.
  • Examples 1 to 7 shown in Table 1 can improve molding fluidity while maintaining haze and heat-and-moisture resistance, have good optical lens moldability, and can be usefully used for optical members.
  • Comparative Example 1 is not added with an aliphatic epoxy compound and is inferior in fluidity, so a thin lens cannot be molded.
  • Comparative Example 2 the addition amount is small, the fluidity is poor, and a thin lens cannot be molded.
  • Comparative Example 4 is inferior in heat-and-moisture stability because the additive does not have an epoxy group.
  • Comparative Example 5 is an alicyclic epoxy compound that is inferior in molding fluidity and has many molding defects during molding.
  • Comparative Example 6 is an aromatic epoxy compound and is inferior in molding fluidity.
  • Comparative Example 7 the molding fluidity is improved, but the additive is volatilized at the time of molding, and there are many molding defects. Further, the heat and heat resistance is poor, the environment for use as an optical member is limited, and the versatility is poor. . Comparative Examples 8 and 9 are inferior in moldability and wet heat resistance due to the decomposition of the additive. Since Comparative Example 3 has a large amount of addition and cannot maintain transparency, it cannot be used as an optical member.
  • thermoplastic resin composition having a fluorene skeleton of the present invention has a high degree of transparency, molding fluidity, molding stability, and heat-and-moisture stability. Thus, a thinner optical member can be provided.
  • the thermoplastic resin composition having a fluorene skeleton is particularly suitable for a camera lens for a portable camera, a lens such as a pickup lens microarray lens, a projector lens, and a Fresnel lens.
  • the optical member using the thermoplastic resin composition having a fluorene skeleton of the present invention can be used for various cameras such as digital video cameras, telescopes, binoculars, TV projectors, prisms and the like.
  • it is effective as a thin and small lens such as a camera lens for a mobile phone, a digital camera lens, an in-vehicle camera lens, and a web camera lens.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'objet de cette invention est de pourvoir à : une composition de résine thermoplastique qui présente une transparence élevée, une excellente fluidité au moulage, une excellente stabilité au moulage et une excellente stabilité à la chaleur humide; et un élément optique qui est formé à partir de ladite composition de résine thermoplastique. Pour ce faire, la présente invention porte sur une composition de résine thermoplastique ayant un squelette fluorène, qui contient 100 parties en poids d'une résine thermoplastique ayant un squelette fluorène et contient un motif répétitif constitué d'un motif ester ou d'un motif carbonate dérivé d'un monomère représenté par la formule générale (1) et 0,1 à 10 parties en poids d'un composé époxy aliphatique qui contient un fragment représenté par la formule générale (2).
PCT/JP2013/076890 2012-10-05 2013-09-26 Composition de résine thermoplastique ayant un squelette fluorène, et élément optique WO2014054710A1 (fr)

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WO2017078070A1 (fr) * 2015-11-04 2017-05-11 三菱瓦斯化学株式会社 Composition de résine, et lentille, feuille et film optique la contenant
CN111527125A (zh) * 2017-12-28 2020-08-11 帝人株式会社 聚(酯)碳酸酯和聚(酯)碳酸酯的制造方法
EP3838979A1 (fr) * 2019-12-17 2021-06-23 Covestro Deutschland AG Polycarbonate fusible aux propriétés optiques améliorées
CN113474685A (zh) * 2017-08-30 2021-10-01 帝人株式会社 光学透镜
WO2023100778A1 (fr) * 2021-11-30 2023-06-08 三菱瓦斯化学株式会社 Lentille optique contenant une résine thermoplastique
KR102666254B1 (ko) 2015-11-04 2024-05-14 미츠비시 가스 가가쿠 가부시키가이샤 수지 조성물 그리고 그것을 포함하는 광학 렌즈, 시트 및 필름

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CN108350262B (zh) * 2015-11-04 2021-07-30 三菱瓦斯化学株式会社 树脂组合物以及含有其的光学透镜、片和膜
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CN108350262A (zh) * 2015-11-04 2018-07-31 三菱瓦斯化学株式会社 树脂组合物以及含有其的光学透镜、片和膜
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KR102666254B1 (ko) 2015-11-04 2024-05-14 미츠비시 가스 가가쿠 가부시키가이샤 수지 조성물 그리고 그것을 포함하는 광학 렌즈, 시트 및 필름
WO2017078070A1 (fr) * 2015-11-04 2017-05-11 三菱瓦斯化学株式会社 Composition de résine, et lentille, feuille et film optique la contenant
CN113474685A (zh) * 2017-08-30 2021-10-01 帝人株式会社 光学透镜
EP3733734A4 (fr) * 2017-12-28 2021-01-27 Teijin Limited Poly(ester) carbonate, et procédé de fabrication de celui-ci
CN111527125B (zh) * 2017-12-28 2022-07-22 帝人株式会社 聚(酯)碳酸酯和聚(酯)碳酸酯的制造方法
US11505698B2 (en) 2017-12-28 2022-11-22 Teijin Limited Polyester carbonate and method for producing polyester carbonate
CN111527125A (zh) * 2017-12-28 2020-08-11 帝人株式会社 聚(酯)碳酸酯和聚(酯)碳酸酯的制造方法
EP3838979A1 (fr) * 2019-12-17 2021-06-23 Covestro Deutschland AG Polycarbonate fusible aux propriétés optiques améliorées
WO2023100778A1 (fr) * 2021-11-30 2023-06-08 三菱瓦斯化学株式会社 Lentille optique contenant une résine thermoplastique

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