WO2021132419A1 - 再生樹脂の製造方法 - Google Patents

再生樹脂の製造方法 Download PDF

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Publication number
WO2021132419A1
WO2021132419A1 PCT/JP2020/048331 JP2020048331W WO2021132419A1 WO 2021132419 A1 WO2021132419 A1 WO 2021132419A1 JP 2020048331 W JP2020048331 W JP 2020048331W WO 2021132419 A1 WO2021132419 A1 WO 2021132419A1
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Prior art keywords
resin
waste
molecular weight
waste resin
carbon atoms
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PCT/JP2020/048331
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English (en)
French (fr)
Japanese (ja)
Inventor
伊藤　貴弘
龍展 緒方
紀明 越智
加藤　宣之
Original Assignee
三菱瓦斯化学株式会社
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Application filed by 三菱瓦斯化学株式会社 filed Critical 三菱瓦斯化学株式会社
Priority to KR1020227014126A priority Critical patent/KR20220123375A/ko
Priority to CN202080089597.5A priority patent/CN114846065B/zh
Priority to JP2021567586A priority patent/JPWO2021132419A1/ja
Publication of WO2021132419A1 publication Critical patent/WO2021132419A1/ja

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    • 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
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
    • C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
    • 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
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a method for producing a recycled resin.
  • Synthetic resins such as polycarbonate resins and polyester resins are widely used in various applications such as home appliances, electronic / electrical equipment, OA equipment, optical media, automobile parts, and building materials. Since a large amount of synthetic resin waste material is discharged when the above-mentioned parts / members are manufactured or after the parts / members are used, these waste materials are reused. In particular, after molding a resin product into a mold, waste resin such as spools, runners, and defective molding products is usually generated in addition to the product. Efforts are being made to recycle these waste resins and reuse them in products without discarding them.
  • Material recycling and chemical recycling are known as methods for recycling waste materials.
  • Material recycling is a method in which discarded synthetic resins are crushed and dissolved, and then reused as raw materials for recycled resins.
  • problems such as a decrease in molecular weight, a decrease in physical properties, and coloring are likely to occur.
  • chemical recycling is a method of reusing a discarded synthetic resin as a raw material for a product by chemically decomposing it, and is a recycling method that can be reused for a high-quality product.
  • Patent Documents 1 to 3 disclose methods for recovering a raw material monomer by depolymerizing a polycarbonate resin.
  • Patent Document 4 a method for producing a resin by disintegrating the resin to the stage of oligocarbonate and polycondensing these oligocarbonates instead of completely decomposing the raw material monomer.
  • depolymerization into such a monomer or oligomer requires a large amount of energy, a plurality of treatment steps, and a polycondensation reaction for recovering the molecular weight reduced in the depolymerization step.
  • it may be difficult to control the amount ratio of reactive groups and in the case of a resin having an aliphatic terminal structure, thermal modification of the terminal group occurs at the time of oligomerization, resulting in structural change of the resin. In some cases, physical properties may deteriorate due to heat history.
  • a method for producing a recycled resin which comprises the following steps (A) and (B).
  • a composition containing a waste resin and aryl alcohol in a weight ratio of 1: 0.1 to 1: 4 is heated to a temperature of 140 ° C. or higher and lower than the boiling point of the aryl alcohol, and has a weight average molecular weight of 19,000.
  • Step of producing the above resin A (B) Step of removing aryl alcohol from the composition obtained in the step (A)
  • the waste resin contains an antioxidant, according to [1].
  • R i represents a heteroaryl group having 6 to 20 carbon atoms containing one or more hetero ring atoms selected from an aryl group or an O, N and S 6 to 20 carbon atoms, a, b, c, d, e, and f each independently represent an integer from 0 to 10.
  • h, i, j, k, m, and n each independently represent an integer of 0-4.
  • R g and R h each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • a, b, c, d, e, and f each independently represent an integer of 1 to 10, and any one of [1] to [6].
  • the method described in. [7] The method according to any one of [1] to [6], wherein the waste resin is a spool and / or runner generated during resin molding.
  • the weight average molecular weight of the resin A obtained in the step (A) is the same as or smaller than the weight average molecular weight of the waste resin.
  • the present invention has one or more of the following effects. (1) Since the regeneration treatment of the present invention does not involve decomposition into a resin in the low molecular weight range or the monomer level, it is possible to efficiently recycle the resin without spending extra heat energy for recovering the molecular weight. It is possible. (2) The regeneration treatment of the present invention can prevent denaturation of the resin and obtain a high-quality recycled resin without giving an extra heat history to the resin. (3) It is possible to obtain a high-quality recycled resin even for a resin having an aliphatic terminal structure that is easily heat-denatured.
  • FIG. 1 It is a figure which shows the profile of the temperature and pressure used in the production of the recycled resin of Example 1.
  • FIG. 1 shows the profile of the temperature and pressure used in the production of the recycled resin of Example 1.
  • Alkyl means a linear or branched saturated aliphatic hydrocarbon group having a specified number of carbon atoms.
  • a “cycloalkyl” is a cyclic saturated aliphatic hydrocarbon group having a specified number of carbon atoms.
  • An “alkylene” is a divalent linear or branched hydrocarbon group having a specified number of carbon atoms.
  • a “cycloalkylene” is a divalent cyclic hydrocarbon group having a specified number of carbon atoms.
  • Aryl refers to an aromatic hydrocarbon cyclic ring system.
  • a “heteroaryl” is an aromatic monocyclic ring system having at least one ring heteroatom or a polycycle in which at least one ring present in the ring system is aromatic and has at least one ring heteroatom.
  • cyclic system refers to the cyclic system.
  • Alkoxy is a group in which an oxygen atom (O) is bonded to the end of an alkyl having a specified number of carbon atoms.
  • Aryloxy is a group in which an oxygen atom (O) is bonded to the end of an aryl having a specified number of carbon atoms.
  • the "halogen” is a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I).
  • One embodiment of the present invention relates to a method for producing a recycled resin from waste resin.
  • the method for producing a recycled resin has the following steps. Steps (C) and (D) are optional steps performed as needed. Step (A) A composition containing waste resin and aryl alcohol in a weight ratio of 1: 0.1 to 1: 4 is heated to a temperature of 140 ° C. or higher and lower than the boiling point of the aryl alcohol to have a weight average molecular weight of 19.
  • Step of producing 000 or more resins A Step (B) Step of removing aryl alcohol from the composition obtained in the step (A) Step (C) Before the step (B), in the step (A) Step of removing unmelted matter from the obtained composition Step (D) Step of pelletizing the resin obtained in the step (B) after the step (B)
  • Step (D) Step of pelletizing the resin obtained in the step (B) after the step (B) Each step will be described below.
  • Step (A) is a step of dissolving the waste resin in aryl alcohol and heating it. By heating the composition containing the waste resin and the aryl alcohol, the resin A having a weight average molecular weight of 19,000 or more is produced.
  • the waste resin is dissolved while suppressing the progress of the excessive depolymerization reaction.
  • heating may cause a certain degree of decrease in the molecular weight of the waste resin.
  • the weight average molecular weight of the resin A obtained in the step (A) is usually the same as or smaller than the weight average molecular weight of the waste resin.
  • the present invention is characterized in that the weight average molecular weight of the resin A obtained in the step (A) is 19,000 or more.
  • step (A) By completing the step (A) in the high molecular weight region and proceeding to the step (B), it is possible to prevent the resin from being denatured and obtain a high-quality recycled resin without giving an extra thermal history to the resin. Further, since the decrease in the molecular weight is suppressed, the resin can be efficiently recycled without consuming extra heat energy for recovering the molecular weight.
  • the weight average molecular weight (Mw) of the resin means the polystyrene-equivalent weight average molecular weight by gel permeation chromatography (GPC), and is measured by the method described in Examples described later.
  • the weight average molecular weight of the resin A is preferably 19,400 or more, more preferably 20,000 or more, still more preferably 29,000 or more, still more preferably 30,000 or more, and particularly preferably 30,000 or more. It is over 35,000.
  • the molecular weight retention rate of the resin A is preferably 50% or more, more preferably 75% or more, further preferably 80% or more, and particularly preferably 90% or more.
  • the molecular weight retention rate of the resin A is calculated from the weight average molecular weight (MW1) of the waste resin and the weight average molecular weight (MW2) of the resin A according to the following formula.
  • Molecular weight retention rate of resin A (%) (MW2) / (MW1) ⁇ 100
  • the heating temperature is 140 ° C. or higher and lower than the boiling point of aryl alcohol. If it is less than 140 ° C., it may be about the same as the glass transition temperature (Tg) of the resin or less than Tg, and the solubility of the resin is inferior.
  • the heating temperature of the composition is preferably 140 to 250 ° C, more preferably 140 to 200 ° C, and even more preferably 160 to 200 ° C. In such a temperature range, the resin is excellently soluble in aryl alcohol, the viscosity of the composition is lowered, and the stirring power is reduced.
  • a temperature of 180 ° C. or higher and lower than the boiling point of aryl alcohol preferably 180-200 ° C., more preferable. Is preferably heated to 185 to 195 ° C.).
  • Heating may be performed in three or more steps.
  • the pressure in the step (A) is not particularly limited, but is preferably 90 to 105 kPa, more preferably 95 to 105 kPa, and even more preferably 95 to 102 kPa from the viewpoint of preventing distillation or volatilization of the aryl alcohol from the system. In one embodiment, from the viewpoint of energy saving, the step (A) is performed near the atmospheric pressure.
  • the weight ratio of the waste resin and the aryl alcohol is 1: 0.1 to 1: 4. If it is less than 1: 0.1 (that is, the amount of aryl alcohol is small), it takes a long time to reach the dissolved state, or the dissolution itself tends to be impossible, which is not preferable. When it is larger than 1: 4 (that is, the amount of aryl alcohol is large), the depolymerization reaction is promoted to generate a monomer or a low molecular weight oligomer, and the molecular weight of the resin is lowered, or the subsequent step (B).
  • the weight ratio of the waste resin and the aryl alcohol is more preferable because it can be recycled without using an excessive device, the waste resin has excellent solubility, and / or the aryl alcohol can be efficiently removed. Is in the range of 1: 0.8 to 1: 1.4, more preferably in the range of 1: 0.9 to 1: 1.2.
  • the treatment time (heating time) of the step (A) is not particularly limited, but is preferably 1 to 13 hours, more preferably 1 to 8 hours in that the resin can be uniformly melted without giving an excessive heat history. 1-7 hours is even more preferred.
  • the longer the heating time the higher the solubility of the waste resin in aryl alcohol.
  • the shorter the heating time the more the resin having a smaller heat history can be obtained, which is preferable.
  • a catalyst may be added.
  • heating the waste resin and aryl alcohol in the presence of a catalyst may cause a depolymerization reaction of the waste resin. Therefore, the catalyst is added and heat-treated within a range in which the molecular weight is not excessively reduced.
  • the catalyst is preferably an alkali metal catalyst from the viewpoint of suppressing an excessive depolymerization reaction and being excellent in cost and easily available.
  • the catalyst added in the step (A) is preferably the same as the catalyst used in the production of the waste resin.
  • the catalyst added in step (A) and the catalyst used in the production of the waste resin are both alkali metal catalysts.
  • alkali metal catalyst examples include organic acid salts, inorganic salts, oxides, hydroxides, hydrides and alkoxides of alkali metals. Specifically, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium hydrogencarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, stearer.
  • sodium hydrogen carbonate, sodium carbonate, cesium carbonate and potassium carbonate are preferable, and sodium hydrogen carbonate, sodium carbonate and cesium carbonate are more preferable.
  • One type of catalyst may be used, or a plurality of types may be used in combination.
  • the step (A) is preferably carried out in the absence of a strong alkali.
  • a transesterification catalyst such as a nitrogen-containing compound such as tetramethylammonium hydroxide, a phosphorus-containing compound, titanium tetraisopropoxide, or titanium tetrabutoxide may be used.
  • the catalyst comprises an alkali metal catalyst and a nitrogen-containing compound as a co-catalyst.
  • the catalyst does not contain a nitrogen-containing compound or a phosphorus-containing compound.
  • These catalysts have a relatively low degree of decomposition temperature and are easily decomposed at a high temperature such as in the subsequent step (B), and it is difficult to recover the molecular weight lowered in the step (A) in the step (B).
  • the resin of these catalysts is more likely to be colored than the alkali metal catalyst.
  • the catalyst preferably does not contain a transesterification catalyst. The resin of the transesterification catalyst is more likely to be colored than the alkali metal catalyst.
  • the amount of the alkali metal catalyst added is not particularly limited as long as the molecular weight does not excessively decrease. For example, 10 to 1000 ⁇ mol / kg is preferable, and 10 to 500 ⁇ mol / kg is more preferable with respect to the waste resin. It is more preferably ⁇ 200 ⁇ mol / kg.
  • the waste resin may contain a catalyst used in resin production, and when such waste resin is heated together with aryl alcohol, a depolymerization reaction occurs even when the catalyst is not added in the step (A).
  • the catalyst is preferably an alkali metal catalyst from the viewpoint of suppressing an excessive depolymerization reaction. Specific examples of the alkali metal catalyst that can be used are the same as those exemplified as the catalyst that can be added in the above step (A).
  • the total content of the catalyst (preferably alkali metal catalyst) in the waste resin is preferably in the range of 0.1 to 1000 ppm by weight, more preferably 0, based on the total weight (100% by weight) of the waste resin. It is in the range of 1 to 100 ppm by weight, more preferably 0.1 to 10 ppm by weight.
  • the content of the catalyst contained in the waste resin can be measured by, for example, ICP emission spectroscopic analysis, fluorescent X-ray analysis, atomic absorption spectrometry, or the like.
  • An example of a specific measurement method using ICP mass spectrometry (ICP-MS) is as follows. After carbonizing the sample with sulfuric acid, the metal concentration is measured by ICP-MS.
  • step (A) a carbonic acid diester and / or a dihydroxy compound may be further added to the composition containing the waste resin and the aryl alcohol.
  • the polymerization reaction proceeds in the subsequent step (B), and the molecular weight can be increased and the molecular weight can be adjusted.
  • Examples of the carbonic acid diester include diphenyl carbonate, ditriel carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like. Of these, diphenyl carbonate is particularly preferable.
  • the dihydroxy compound a dihydroxy compound corresponding to a structural unit constituting the waste resin is preferable, but a compound other than the dihydroxy compound may be used.
  • the compound include bisphenol type dihydroxy compounds (for example, bisphenol A, bisphenol AP, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol PH, bisphenol Z, bisphenol TMC, etc.).
  • the total amount of the carbonic acid diester and / or the dihydroxy compound added is preferably 0.01 to 100 g / kg, more preferably 0.1 to 50 g / kg, and further preferably 1.0 with respect to the waste resin. It is ⁇ 10 g / kg.
  • the type of waste resin used in the method of the present invention is not particularly limited, and examples thereof include thermoplastic resins (for example, polycarbonate resin, polyester resin, polyester carbonate resin, acrylic resin, polyolefin resin, etc.).
  • the waste resin may be composed of one kind of single resin or two or more kinds of resins.
  • the waste resin is preferably at least one selected from polycarbonate resin, polyester resin, and polyester carbonate resin from the viewpoint of excellent compatibility with aryl alcohol and / or relatively high price and profitability of recycling. It is preferable to contain one, and it is more preferable to contain a polycarbonate resin.
  • the waste resin comprises an aromatic polycarbonate resin.
  • thermoplastic resin preferably at least one of a polycarbonate resin, a polyester resin, and a polyester carbonate resin, more preferably a polycarbonate resin
  • a thermoplastic resin is preferably 50% by weight or more based on the total weight of the waste resin. It is preferably contained in an amount of 70% by weight or more, more preferably 80% by weight or more.
  • the waste resin includes at least other resin components (for example, synthetic resins such as polyamide, polystyrene, amorphous polyolefin, ABS and AS, and biodegradable resins such as polylactic acid and polybutylene succinate) in addition to the above thermoplastic resins.
  • synthetic resins such as polyamide, polystyrene, amorphous polyolefin, ABS and AS
  • biodegradable resins such as polylactic acid and polybutylene succinate
  • the waste resin has an aliphatic end structure.
  • Resins having an aliphatic end are generally more susceptible to thermal denaturation than resins having an aryl end structure.
  • denaturation of the resin can be suppressed without giving an extra heat history to the resin, so that the present invention is advantageous for regeneration of the waste resin of the embodiment.
  • Waste resin is a molded product that is collected after being used in the market as a part of a product, a defective product that occurs in the molding process, or a molded product that accompanies the molding process (for example, spools and runners), and commercialization. Examples thereof include defective products generated in the process and products derived from unused molded products that are no longer needed.
  • the shape of the waste resin is not limited to powders, pellets, sheets, films, molded products, etc., and discarded lenses, sheets, films; defective products, burrs generated during manufacturing and / or molding processing; manufacturing waste, resin Solids recovered from the waste of products using, crushed products thereof; etc. are used.
  • defective products generated in the molding process and molded products (for example, spools, runners, etc.) generated in the molding process are 5% by weight or more (more preferably 10% by weight or more, more preferably 10% by weight or more) based on the total weight of the waste resin. It is preferable to contain 20% by weight or more).
  • the spool and / or runner generated during resin molding is 80% by weight or more (more preferably 90% by weight or more, further preferably 95% by weight or more, particularly preferably the total amount (100% by weight), based on the total weight of the waste resin. )) It is preferable to include it.
  • the waste resin is a spool and / or runner generated in the injection molding process of the polycarbonate resin for the optical material.
  • a recycled resin having a small heat history can be obtained. Therefore, a high-quality optical material that is easily affected by the heat history is recycled as a waste resin to reproduce a high-quality recycled resin. Is possible.
  • the waste resin a high-quality and high-cost resin such as a resin for an optical lens is preferable from the viewpoint of profitability of recycling and obtaining a high-quality recycled product.
  • the waste resin preferably has high compatibility with aryl alcohol.
  • the waste resin preferably contains any of the structural units of the following general formulas (1) to (5), and substantially from any of the following general formulas (1) to (5). Is more preferable.
  • substantially from means, for example, preferably 90% or more, more preferably 95% or more, still more preferably 98% or more of the constituent units of the resin from the general formula (1) to. It consists of the structural unit represented by (5).
  • the waste resin may be a homopolymer composed of each of the structural units represented by the general formulas (1) to (5), or may be a homopolymer composed of the structural units represented by the general formulas (1) to (5).
  • It may be a copolymer composed of and other structural units other than the formulas (1) to (5).
  • these homopolymers may be used together, or a blend of homopolymers and copolymers.
  • the resin may have a random, block or alternating copolymer structure.
  • X a , X b , X c , X d , X e , and X f each independently represent an alkylene group having 1 to 4 carbon atoms.
  • Ra , R b , R c , R d , Re , and R f are independently halogen atoms, alkyl groups having 1 to 20 carbon atoms, and 1 carbon atom.
  • One or more heterocycles selected from ⁇ 20 alkoxy groups, 5-20 carbon cycloalkyl groups, 5-20 carbon cycloalkoxy groups, 6-20 carbon aryl groups, O, N and S It is selected from a heteroaryl group having 6 to 20 carbon atoms including an atom, an aryloxy group having 6 to 20 carbon atoms, and -C ⁇ C-R i.
  • R a , R b , R c , R d , Re , and R f are independently selected from a hydrogen atom, a phenyl group, a 1-naphthyl group, and a 2-naphthyl group, respectively.
  • Ri 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.
  • Ri is selected from a hydrogen atom, a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • a, b, c, d, e, and f each independently have an integer of 0 to 10 (for example, 0 to 5, 0 to 3, or 0 or 1).
  • a, b, c, d, e, and f each independently represent an integer of 1 to 10 (eg, 1 to 5, 1 to 3, 1 to 2, or 1).
  • Resins having such an aliphatic terminal structure are generally more susceptible to thermal denaturation than resins having an aryl terminal structure. In the method of the present invention, the denaturation of the resin can be suppressed without giving an extra heat history to the resin, so that the present invention is advantageous for the regeneration of the waste resin of the embodiment.
  • h, i, j, k, m, and n each independently represent an integer of 0 to 4.
  • R g and R h each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (preferably a hydrogen atom).
  • the structural unit represented by the formula (1) examples include 2,2'-bis (1-hydroxymethoxy) -1,1'-binaphthalene and 2,2'-bis (2-hydroxyethoxy) -1. , 1'-Binaphthalene, 2,2'-bis (3-hydroxypropyloxy) -1,1'-Binaphthalene, 2,2'-bis (4-hydroxybutoxy) -1,1'-Binaphthalene, etc.
  • a constituent unit can be mentioned.
  • the structural unit represented by the formula (1) is a structural unit derived from 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene (also referred to as "BHEBN"). is there. These may be used alone or in combination of two or more.
  • the structural unit represented by the formula (2) include 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and 9,9-bis [4- (2-hydroxyethoxy) -3. -Methylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-tert-butylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-isopropylphenyl] Fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-cyclohexylphenyl] fluorene, 9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene (hereinafter "BPPEF”)
  • the structural units represented by the formula (2) are 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene and 9,9-bis [4- (2-hydroxyethoxy)-.
  • 3-Phenylphenyl] A structural unit derived from a compound selected from fluorene. These may be used alone or in combination of two or more.
  • the structural unit represented by the formula (3) include a structural unit derived from 9,9-bis (hydroxy (poly) alkoxynaphthyl) fluorenes.
  • 9,9-bis [6- (1-hydroxymethoxy) naphthalene-2-yl] fluorene 9,9-bis [6- (2-hydroxyethoxy) naphthalene-2-yl] fluorene
  • the structural unit represented by the formula (3) is a structural unit derived from 9,9-bis [6- (2-hydroxyethoxy) naphthalene-2-yl] fluorene. These may be used alone or in combination of two or more.
  • the structural unit represented by the formula (4) include a structural unit derived from decahydro-1,4: 5,8-dimethanonaphthalenediols (also referred to as "D-NDM").
  • decahydro-1,4 5,8-dimethanonaphthalene-2,6-diyl
  • dimethanol (decahydro-1,4: 5,8-dimethanonaphthalene-2,7-diyl) dimethanol
  • 2-ethyldecahydro-1,4: 5,8-dimethanonaphthalene-2,6-diyl) dimethanol (2-ethyldecahydro-1,4: 5,8-dimethanonaphthalene-2,
  • the structural unit represented by the formula (5) include a structural unit derived from decahydro-1,4: 5,8-dimethanonaphthalene-2-methoxycarbonyl-6 (7) -methanol. ..
  • decahydro-1,4 5,8-dimethanonaphthalene-2-methoxycarbonyl-6-methanol
  • decahydro-1,4 5,8-dimethanonaphthalene-2-methoxycarbonyl-7-methanol
  • 2- Methyl-decahydro-1,4 5,8-dimethanonaphthalene-2-methoxycarbonyl-6-methanol
  • 2-ethyl-decahydro-1,4 5,8-dimethanonaphthalene-2-methoxycarbonyl-6-methanol
  • 2-ethyl-decahydro-1,4 5,8-dimethanonaphthal
  • the ratio of the constituent units of the above formula (1) in the waste resin is high in market value as a resin having a high refractive index and high total light transmittance, and therefore, with respect to the total weight of the resin component of the waste resin. It is preferably 1 to 100% by weight, more preferably 20 to 90% by weight, and even more preferably 30 to 80% by mass.
  • the ratio of the constituent units of the above formula (2) in the waste resin is high in market value as a resin having a high refractive index and high total light transmittance, and therefore, with respect to the total weight of the resin component of the waste resin. It is preferably 1 to 100% by weight, more preferably 20 to 100% by mass, and even more preferably 30 to 100% by mass.
  • the ratio of the structural unit of the above formula (3) in the waste resin is high in market value as a resin having a high refractive index and a high total light transmittance, and therefore, with respect to the total weight of the resin component of the waste resin. It is preferably 1 to 100% by weight, more preferably 19 to 90% by weight, and even more preferably 20 to 80% by mass.
  • the proportion of the structural unit of the above formula (4) in the waste resin is abolished because it has an appropriate balanced refractive index and Abbe number for optical lenses and has high market value as a resin having high total light transmittance. It is preferably 1 to 100% by weight, more preferably 20 to 100% by mass, and even more preferably 30 to 100% by mass, based on the total weight of the resin component of the resin.
  • the proportion of the structural unit of the above formula (5) in the waste resin is abolished because it has an appropriate balanced refractive index and Abbe number for optical lenses and has high market value as a resin having high total light transmittance. It is preferably 1 to 100% by weight, more preferably 20 to 100% by mass, and even more preferably 30 to 100% by mass, based on the total weight of the resin component of the resin.
  • the total ratio of the constituent units of the above formulas (1) to (5) in the waste resin is 0 with respect to the total weight of the resin components of the waste resin because it has a high market value as a resin having excellent optical characteristics. It is preferably 0.01 to 100% by weight, more preferably 0.1 to 100% by mass, and even more preferably 1 to 100% by mass.
  • resins having the structural units of the above formulas (1) to (5) include, for example, International Publication WO2014 / 073496, JP2010-248445, JP2008-111047, International Publication WO2016 / 052370, It is described in International Publication WO2018 / 016516, PCT / JP2019 / 042232.
  • the weight average molecular weight (Mw) of the waste resin is not particularly limited, but is preferably 19,000 to 7,000, more preferably 25,000 to, for example, from the viewpoint of maintaining appropriate strength as a resin for an optical lens. It is 60,000, more preferably 30,000 to 60,000.
  • waste resins include catalysts, antioxidants, processing stabilizers, light stabilizers, mold release agents, UV absorbers, flame retardants, lubricants, antistatic agents, surfactants, antibacterial agents, plasticizers, etc. It may contain additives such as a compatibilizer, a strengthening agent, and a deactivator.
  • the waste resin comprises an antioxidant.
  • the antioxidant is not particularly limited, but for example, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3].
  • the content of the antioxidant in the waste resin is preferably in the range of 1 to 3000 ppm by weight, more preferably in the range of 300 to 2800 ppm by weight, based on the total weight (100% by weight) of the waste resin. It is more preferably in the range of 500 to 2500 ppm by weight, and particularly preferably in the range of 500 to 2000 ppm by weight.
  • the content of the antioxidant contained in the waste resin can be measured by using, for example, NMR or liquid chromatography-mass spectrometry (LC-MS).
  • LC-MS liquid chromatography-mass spectrometry
  • standard solutions of antioxidants having different concentrations are prepared, analyzed by LC-MS, a calibration curve is prepared, and the analysis sample is quantified by the prepared calibration curve. This is a method of performing analysis.
  • a calibration curve can be prepared using a standard solution of a highly pure compound such as bisphenol A, and quantitative analysis can be performed as a bisphenol A equivalent value.
  • the waste resin comprises a deactivator.
  • the content of the deactivator in the waste resin when the deactivator is contained is preferably in the range of 1 to 3000 ppm by weight, more preferably 300 to 2800, based on the total weight (100% by weight) of the waste resin. It is in the range of ppm by weight, more preferably in the range of 500 to 2500 ppm by weight, and particularly preferably in the range of 500 to 2000 ppm by weight. Even when the waste resin contains a deactivator, a certain degree of depolymerization reaction of the waste resin may occur in the step (A) due to the influence of the catalyst contained in the waste resin, or a step described later. The molecular weight of the resin in (B) may increase.
  • the content of the deactivator contained in the waste resin can be measured by, for example, NMR or liquid chromatography-mass spectrometry (LC-MS) in the same manner as the antioxidant.
  • step (A) an antioxidant may be added.
  • the step (A) may be a step of heating the composition containing the waste resin, the aryl alcohol, and the antioxidant.
  • the content of the antioxidant in the composition is preferably 0.001 to 0.3% by weight, more preferably 0.030 to 0%, based on the total weight (100% by weight) of the waste resin. It is .28% by weight, more preferably 0.050 to 0.25% by weight, and particularly preferably 0.0500 to 0.20% by weight.
  • waste resin generally has environmental substances such as dust and oil attached to it, if necessary, use an air-blown dry cleaning method, water, an organic solvent, or a surfactant before the regeneration process.
  • the surface may be cleaned by the wet cleaning method used.
  • the waste resin is pulverized to a size having a maximum diameter of 5 cm or less (preferably 0.001 to 3 cm, more preferably 0.01 to 2 cm, still more preferably 0.1 to 1 cm). You may. By pulverizing, (1) the solubility in aryl alcohol is increased, (2) the transportability is improved, (3) it is easy to put into the reaction vessel, and (4) the heat history to the waste resin is recorded. It is preferable in that it becomes uniform.
  • Aryl alcohol is a compound in which the hydrogen atom of aryl is substituted with a hydroxy group.
  • Aryl-alcohol has excellent compatibility with waste resin, and is not particularly limited as long as the boiling point of aryl-alcohol has a boiling point equal to or higher than the glass transition temperature of the resin component contained in the waste resin.
  • substituted or unsubstituted phenol can be mentioned.
  • the substituent of phenol can be selected from a wide range of organic groups.
  • the substituent is selected from an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom and the like.
  • arylalcohol is an unsubstituted phenol or mono-, di- or tri-substituted from the viewpoint that the treatment of step (B) is easy to carry out, is inexpensive, and high-purity ones are on the market.
  • Phenols eg, o-, m- or p-cresol, o-, m- or p-ethylphenol, o-, m- or p-chlorophenol, o-, m- or p-methoxyphenol, 2,3 -, 2,4- or 3,4-dimethylphenol, etc.
  • an unsubstituted phenol eg, o-, m- or p-cresol, o-, m- or p-ethylphenol, o-, m- or p-chlorophenol, o-, m- or p-methoxyphenol, 2,3 -, 2,4- or 3,4-dimethylphenol, etc.
  • the unsubstituted phenol is contained in a small amount in the waste resin, and it is possible to avoid the mixing of new impurities and reduce the influence on the physical characteristics of the resin.
  • Aryl alcohol may be used alone or in combination of two or more.
  • Step (B) In the step (B), the aryl alcohol is removed from the composition obtained in the step (A). As a result, a recycled resin can be obtained.
  • the means for removing the aryl alcohol is not particularly limited, but for example, under a pressure of 0.01 to 105 kPa (preferably 0.1 to 105 kPa, more preferably 0.1 to 102 kPa), a temperature of 180 to 260 ° C. (preferably 190).
  • Aryl alcohol is removed by setting the temperature to about 260 ° C., more preferably 190 to 250 ° C.).
  • gradually reducing the pressure for example, reducing the pressure in the range of 90 to 105 kPa to the pressure of 0.01 to 5 kPa
  • the treatment time of the step (B) is not particularly limited, but is preferably 1 to 7 hours, more preferably 1.5 to 5 hours, and even more preferably 2 to 4 hours in terms of suppressing the progress of thermal deterioration of the resin.
  • a catalyst may be further added before the step (B).
  • the alkali metal catalyst described as a catalyst that can be added to the step (A) is similarly preferably used.
  • the molecular weight of the resin can be increased in the step (B).
  • the resin tends to have a reduced molecular weight during molding, but when it contains a catalyst, it has an advantage that the reduced molecular weight at the time of molding can be restored to the original molecular weight of the resin in the step (B).
  • step (B) is performed in the presence of an alkali metal catalyst.
  • a carbonic acid diester and / or a dihydroxy compound may be further added before the step (B).
  • the alkali metal catalyst described as a catalyst that can be added to the step (A) is similarly preferably used.
  • the carbonic acid diester and / or the dihydroxy compound is present in the step (B)
  • the polymerization reaction proceeds in the subsequent step (B), and the molecular weight can be increased and the molecular weight can be adjusted.
  • the total amount of the carbonic acid diester and / or the dihydroxy compound added is preferably 0.01 to 100 g / kg, more preferably 0.1 to 50 g / kg, and further preferably 1.0 with respect to the waste resin. It is ⁇ 10 g / kg.
  • the carbonic acid diester and / or the dihydroxy compound is added in both the step (A) and the step (B)
  • the total amount of the carbonic acid diester and / or the dihydroxy compound added in the step (A) and the step (B) is the above. It is preferably in the range.
  • the weight average molecular weight of the recycled resin obtained in the step (B) is preferably the same as or larger than the weight average molecular weight of the waste resin.
  • the molecular weight retention rate of the regenerated resin is preferably 95% or more, more preferably 100% or more, still more preferably 120% or more.
  • the molecular weight retention rate of the recycled resin is calculated from the weight average molecular weight (MW1) of the waste resin and the weight average molecular weight (MW3) of the recycled resin according to the following formula.
  • Molecular weight retention rate of recycled resin (%) (MW3) / (MW1) ⁇ 100
  • the amount of the alkali metal catalyst added is not particularly limited as long as the molecular weight does not excessively decrease. For example, 10 to 1000 ⁇ mol / kg is preferable, and 10 to 500 ⁇ mol / kg is more preferable with respect to the waste resin. It is more preferably ⁇ 200 ⁇ mol / kg.
  • the total amount of the catalyst added in the step (A) and the step (B) is preferably in the above range.
  • Step (C) In the method of the present invention, there may be a step of removing the unmelted material from the composition obtained in the step (A) before the step (B).
  • the waste resin may contain a plurality of resins, or may contain different materials such as metal materials and foreign substances such as dust mixed from the surroundings during molding.
  • a resin component that dissolves in aryl alcohol can be obtained.
  • polycarbonate resins have high solubility in aryl alcohols, but olefin resins (for example, cycloolefin polymer (COP) resins and cycloolefin copolymers (COC) resins) generally have low solubility in aryl alcohols.
  • the resin component containing the polycarbonate resin can be obtained by separating it from a resin component having poor solubility such as an olefin resin.
  • the removing means is not particularly limited, and can be removed by, for example, filtration using a polymer filter or the like, or adsorption removal using activated carbon.
  • Step (D) After the step (B), there may be a step of pelletizing the resin obtained in the step (B).
  • the regenerated resin obtained above can be used as a molded product as it is or after being pelletized.
  • Recycled resin A recycled resin can be obtained by the above method.
  • Recycled resins include antioxidants, processing stabilizers, light stabilizers, mold release agents, UV absorbers, flame retardants, lubricants, antistatic agents, surfactants, and antibacterial agents, as long as the characteristics of the present invention are not impaired.
  • Plasticizers, compatibilizers, strengthening agents, deactivators and the like may be contained.
  • the regenerated resin obtained by the above method has a reduced thermal history, and a good quality regenerated resin can be obtained. Therefore, the recycled resin obtained by the above method can be used as an optical material.
  • a further embodiment of the present invention is a molded product containing a recycled resin.
  • molded products There are no restrictions on the shape, pattern, color, dimensions, etc. of the molded product, and it may be arbitrarily set according to the intended use. Molded products are useful for various purposes such as optical materials (members), machine parts materials, electrical / electronic parts materials, automobile parts materials, civil engineering and building materials, molding materials, as well as paints and adhesive materials. ..
  • Examples of the molded product include an optical material, for example, an optical lens or an optical film.
  • optical components such as transparent conductive substrates used for liquid crystal displays, organic EL displays, solar cells, optical disks, liquid crystal panels, optical cards, sheets, films, optical fibers, connectors, vapor-deposited plastic reflectors, and displays. It can be advantageously used as an optical molded body suitable for material or functional material applications.
  • Parts and “%” in the examples represent “parts by mass” and “% by mass”, respectively.
  • the molecular weight retention rate was calculated from the weight average molecular weight (MW1) of the waste resin, the weight average molecular weight (MW2) of the resin A, and the weight average molecular weight (MW3) of the regenerated resin according to the following formula.
  • Molecular weight retention rate of recycled resin (%) (MW3) / (MW1) ⁇ 100
  • Molecular weight retention rate of resin A (%) (MW2) / (MW1) ⁇ 100
  • the reaction was carried out by keeping the temperature at 200 ° C. for 20 minutes. Further, the temperature was raised to 230 ° C. at a rate of 75 ° C./hr, and 10 minutes after the completion of the temperature rise, the degree of decompression was reduced to 1 mmHg or less over 2 hours while maintaining the temperature. Then, the temperature was raised to 245 ° C. at a rate of 60 ° C./hr, and stirring was further performed for 40 minutes. After completion of the reaction, nitrogen was introduced into the reactor to return it to normal pressure, and the produced thermoplastic resin was pelletized and taken out.
  • the resin obtained above contains 15 ppm by weight of tert-butylphosphonium dodecylbenzenesulfonic acid (MGA-614, manufactured by Takemoto Oil & Fat Co., Ltd.) as a deactivator and 3,9-bis (2,6-bis) as a release agent.
  • MCA-614 tert-butylphosphonium dodecylbenzenesulfonic acid
  • step iii The weight average molecular weight (Mw) was measured using the partially sampled resin as the resin A.
  • Process (B) Then, at 190 ° C., the pressure in the reaction system was reduced to 250 ° C. and 0.13 kPa over 3 hours to remove phenol to obtain a regenerated resin. Table 1 shows the physical characteristics of the resin A and the recycled resin.
  • step (A) the temperature was raised to 170 ° C. in step i, followed by holding at 170 ° C. for 3 hours in step ii, and then the temperature was raised to 190 ° C. in step iii, as in Example 1. A recycled resin was obtained.
  • Example 3 A recycled resin was obtained in the same manner as in Example 1 except that in step (A), the temperature was raised to 190 ° C. in step iii immediately after the temperature was raised to 170 ° C. in step i without performing step ii. It was.
  • Example 4 100 g of waste resin a obtained in Production Example 1, 100 g of phenol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) as aryl alcohol (ArOH), and 115 ⁇ L of sodium hydrogen carbonate aqueous solution (concentration 0.10 mol / L, sodium hydrogen carbonate) as a catalyst.
  • a recycled resin was obtained in the same manner as in Example 1 except that 115 ⁇ mol / kg of waste resin a) was charged into a 500 mL separable flask with a turbine blade. Table 1 shows the physical characteristics of the resin A and the recycled resin.
  • Example 5 After partially sampling and measuring the weight average molecular weight (Mw) of the resin A, before starting the depressurization, 115 ⁇ L of an aqueous sodium hydrogen carbonate solution (concentration 0.10 mol / L, as sodium hydrogen carbonate for the waste resin a) A recycled resin was obtained in the same manner as in Example 2 except that 115 ⁇ mol / kg) was added. Table 1 shows the physical characteristics of the resin A and the recycled resin.
  • Example 6 The catalyst to be added together with the waste resin a to a 500 mL separable flask with a turbine blade is added to 34.5 ⁇ L of an aqueous sodium hydrogen carbonate solution (concentration 0.10 mol / L, 34.5 ⁇ mol / kg of sodium hydrogen carbonate with respect to the waste resin a).
  • a recycled resin was obtained in the same manner as in Example 4 except for the change. Table 1 shows the physical characteristics of the resin A and the recycled resin.
  • Example 7 100 g of waste resin a obtained in Production Example 1, 100 g of phenol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) as aryl alcohol (ArOH), 115 ⁇ L of aqueous sodium hydrogen carbonate solution (concentration 0.10 mol / L, as sodium hydrogen carbonate)
  • a recycled resin was obtained in the same manner as in Example 3 except that 115 ⁇ mol / kg of waste resin a) and 0.2053 g of diphenyl carbonate (DPC) as a carbonic acid diester were placed in a 500 mL separable flask with a turbine blade.
  • Table 1 shows the physical characteristics of the resin A and the recycled resin.
  • Example 8 The weight ratio of the waste resin a and the aryl alcohol (ArOH) was changed to 1: 0.8.
  • step (A) after the temperature was raised to 170 ° C. in step i, the temperature was maintained at 170 ° C. for 1 hour in step ii, and there was undissolved resin.
  • step ii was extended and kept at 170 ° C. for 3 hours, the resin could be dissolved (total time of step ii: 4 hours). After that, the temperature was raised to 190 ° C. in step iii. Except for this, a recycled resin was obtained in the same manner as in Example 1.
  • Example 9 The weight ratio of the waste resin a and the aryl alcohol (ArOH) was changed to 1: 1.5.
  • step (B) the pressure in the reaction system was increased at 190 ° C. for 3 hours, the set temperature was set to 180 to 250 ° C., and phenol was removed while reducing the pressure to 0.13 kPa, but the amount of phenol was large.
  • the liquid temperature (internal temperature) was in the range of 185 to 240 ° C., and the set temperature could not be followed. Therefore, when the time of the step (B) was extended and held for an additional 1 hour, the liquid temperature rose and the recycled resin could be obtained.
  • Example 2 The treatment was carried out in the same manner as in Example 9 except that the weight ratio of the waste resin a and the aryl alcohol (ArOH) was changed to 1: 5, but since a large amount of phenol was present in the step (B), the treatment was carried out in the same manner as in Example 9. Phenol could not be removed and a recycled resin could not be obtained.
  • Example 10 Except that 20 kg of the waste resin a obtained in Production Example 1 and 20 kg of phenol (phenol distilled in Production Example 1) as aryl alcohol (ArOH) were charged into a 50 L reaction tank with a double helical ribbon wing, the same as in Example 1. It was done in the same way. The recycled resin was drawn out in a strand shape from the extraction port at the bottom of the reaction tank via a gear pump, passed through the water tank, cooled, cut with a pelletizer, and pelletized.
  • phenol phenol distilled in Production Example 1
  • ArOH aryl alcohol
  • the method of the present invention it was possible to recycle the waste resin while suppressing the decrease in molecular weight.
  • the weight average molecular weight of the resin A obtained after the step (A) is 19,000 or more (molecular weight retention rate is 50% or more), and the molecular weight retention rate is 97% or more after the subsequent step (B). It was possible to obtain a recycled resin.
  • a recycled resin having a molecular weight retention rate of 93% or more in the step (A) and finally having a molecular weight retention rate of 100% or more is obtained.
  • the waste resin a contains a catalyst (NaHCO 3 ) used in the production.
  • Example 8 In Comparative Example 1 in which the weight ratio of the waste resin a and the aryl alcohol (ArOH) is smaller than 1: 0.1 (that is, the amount of the aryl alcohol is small), the waste resin cannot be dissolved in the aryl alcohol, and the regeneration treatment is performed. I could't proceed.
  • Example 8 (1: 0.8), in which the weight ratio of the waste resin a to the aryl alcohol (ArOH) is smaller than that of Example 1 (1: 1) (that is, the amount of aryl alcohol is small), the recycled resin is used.
  • the time required to dissolve the aryl alcohol is longer and the energy consumption is higher.
  • Example 10 the recycled resin could be obtained as a pellet as it was in the step (B).
  • Example 9 in which the weight ratio of the waste resin a and the aryl alcohol (ArOH) was 1: 1.5, a regenerated resin was obtained, but the aryl was compared with Example 1 (weight ratio 1: 1).
  • Example 1 in which the weight ratio of the waste resin a and the aryl alcohol (ArOH) is 1: 1 is easier to control the temperature and is suitable for actual production.
  • the present invention can efficiently recycle the resin while suppressing the decrease in molecular weight.

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