Method for producing polymer regenerator containing alicyclic structure

Abstract

The purpose of the present invention is to provide a method for producing an alicyclic structure-containing polymer regenerant by efficiently and efficiently removing a crystalline polymer from a molded article containing an alicyclic structure-containing polymer and the crystalline polymer, thereby obtaining the alicyclic structure-containing polymer regenerant. The method for producing a polymer regenerant containing an alicyclic structure according to the present invention is a method for producing a polymer regenerant containing an alicyclic structure from a molded body comprising a crystalline polymer and an amorphous polymer containing an alicyclic structure, the production method includes a predetermined dissolution step, a predetermined heating step, a predetermined cooling step, and a predetermined removal step.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a recycled product of a polymer having an alicyclic structure. Background Art

[0002] Since polymers having an alicyclic structure are excellent in properties such as transparency, heat resistance, moisture resistance, chemical resistance, and electrical properties, they are widely used in various fields such as optical materials, medical materials, and electrical component materials. Therefore, a large amount of used waste generated after using a molded article containing the polymer having an alicyclic structure and processing waste generated during the manufacture of the molded article are produced.

[0003] In recent years, recycled plastics obtained by recycling waste of a molded article containing a polymer having an alicyclic structure and, if necessary, pulverizing and granulating them have been widely used. Further, since foreign substances and the like may remain when recycling waste of a molded article containing a polymer having an alicyclic structure, studies are being made to remove foreign substances from the waste and reuse the polymer having an alicyclic structure.

[0004] For example, Patent Document 1 discloses a method for recycling a resin molded article in which a resin molded article containing a polymer having an alicyclic structure is pulverized and the obtained pulverized molded article is dissolved in a predetermined mixed solvent to remove foreign substances from the pulverized molded article.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: International Publication No. 2022 / 163543. Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] Here, among molded articles containing a polymer having an alicyclic structure, there are molded articles in which a crystalline polymer such as polyethylene or polypropylene is kneaded depending on its use. In order to reuse the polymer having an alicyclic structure from waste of such a molded article, it is required to efficiently and effectively remove the crystalline polymer from the molded article.

[0010] Therefore, an object of the present invention is to provide a method for manufacturing a recycled product of a polymer having an alicyclic structure, which efficiently and effectively removes a crystalline polymer from a molded article containing a polymer having an alicyclic structure and a crystalline polymer to obtain a recycled product of a polymer having an alicyclic structure.

[0011] Means for Solving the Problems

[0012] The inventors conducted in-depth research with the aim of solving the above problems. Then, the present inventors found that the above problems can be solved by a method for producing a cycloaliphatic structure polymer regenerate, which involves heating a polymer solution containing an amorphous cycloaliphatic structure polymer and a crystalline polymer to a specified temperature range and then cooling it to a specified temperature range, thereby completing the present invention.

[0013] That is, the present invention aims to advantageously solve the above problems. [1] The present invention is a method for producing a cycloaliphatic structure polymer regenerate, which is a method for producing a cycloaliphatic structure polymer regenerate from a molded article containing a crystalline polymer and an amorphous cycloaliphatic structure polymer. The above production method includes the following steps: a dissolution step of mixing the above molded article with a solvent and dissolving at least the above cycloaliphatic structure polymer in the solvent to obtain a polymer solution; a heating step of heating the above polymer solution to a temperature above Tc1 - 75°C and below Tc1°C when the crystallization temperature of the above crystalline polymer is set to Tc1°C; a cooling step of cooling the above polymer solution after the above heating step to a temperature lower than the heating temperature in the above heating step and 40°C or lower; and a removal step of removing the above crystalline polymer from the above polymer solution after the above cooling step.

[0014] If it is the above method for producing a cycloaliphatic structure polymer regenerate, the crystalline polymer can be efficiently and effectively removed from the molded article to obtain a cycloaliphatic structure polymer regenerate.

[0015] Here, being able to efficiently remove the crystalline polymer from the molded article means that the rate of removing the crystalline polymer from the molded article is fast, and the production (regeneration) rate of the cycloaliphatic structure polymer regenerate is fast. In addition, being able to effectively remove the crystalline polymer from the molded article means that the removal rate of the crystalline polymer from the molded article is high, and the purity of the obtained cycloaliphatic structure polymer regenerate is high.

[0016] In the present specification, the crystallization temperature of the crystalline polymer can be measured by a differential scanning calorimeter (DSC).

[0017] In the present specification, the cycloaliphatic structure polymer being "amorphous" means that the melting point cannot be measured using a differential scanning calorimeter (DSC).

[0018] [2] In the method for producing a cycloaliphatic structure polymer regenerate described in the above [1], it is preferable that the cooling temperature in the above cooling step is 20°C or higher.

[0019] If the cooling temperature in the cooling step is at or above the above lower limit, the crystalline polymer can be removed from the molded article more efficiently.

[0020] [3] In the method for producing a regenerated alicyclic structure-containing polymer according to [1] or [2], the cooling temperature in the cooling step is preferably 30° C. or less.

[0021] When the cooling temperature in the cooling step is not more than the above upper limit, the crystalline polymer can be removed from the molded product more effectively.

[0022] [4] In the method for producing a regenerated product of an alicyclic structure-containing polymer according to any one of [1] to [3], the heating temperature in the heating step is preferably 60° C. or higher and 100° C. or lower.

[0023] When the heating temperature in the heating step is not less than the above lower limit, the crystalline polymer can be removed from the molded product more efficiently.

[0024] On the other hand, when the heating temperature in the heating step is not more than the above upper limit, the crystalline polymer can be removed from the molded product more effectively.

[0025] [5] In the method for producing a regenerated product containing an alicyclic structure polymer according to any one of [1] to [4] above, the heating temperature in the heating step is preferably Tc1-20°C or less.

[0026] When the heating temperature in the heating step is not more than the above upper limit, the crystalline polymer can be removed from the molded product more effectively.

[0027] [6] In the method for producing a regenerated product of an alicyclic structure-containing polymer according to any one of [1] to [5], the solvent is preferably a poor solvent for the crystalline polymer.

[0028] If the solvent is a poor solvent for the crystalline polymer, the crystalline polymer can be removed from the molded product more efficiently and effectively.

[0029] In this specification, the term "poor solvent for crystalline polymers" refers to a solvent having a solubility parameter value (hereinafter, sometimes referred to as "SP value") of 7 (cal / cm 3 ) 1 / 2 Above 9.9 (cal / cm 3 ) 1 / 2 The following solvents. In addition, in this specification, "solubility parameter (SP value)" refers to the Hansen solubility parameter (δ) (unit: (cal / cm 3 ) 1 / 2 ), with “δ 2 =δd 2 +δp 2 +δh 2It is represented by the relational expression of “ ”. In the above relational expression, “δd” represents “the contribution term of the dispersion force between molecules”, “δp” represents “the contribution term of the polar interaction between molecules”, and “δh” represents “the contribution term of the hydrogen bond between molecules”, which are physical property values based on the type of substance (refer to Charles M. Hansen, “Hansen Solubility Parameters: A User’s Handbook, Second Edition”, CRC Press, Boca Raton FL, (2007) (hereinafter, also referred to as the “Handbook”)). For organic solvents not described in the Handbook or the like, estimated values calculated using Hansen Solubility Parameters in Practice (HSPiP) can be used.

[0030] [7] In the method for producing a recycled polymer with an alicyclic structure described in [6] above, it is preferable that the poor solvent is cyclohexane.

[0031] If the poor solvent is cyclohexane, the crystalline polymer can be removed from the molded article more efficiently and effectively.

[0032] [8] In the method for producing a recycled polymer with an alicyclic structure according to any one of [1] to [7] above, it is preferable that the crystalline polymer is polypropylene.

[0033] If the crystalline polymer is polypropylene, the crystalline polymer can be removed from the molded article more efficiently and effectively.

[0034] Advantages of the Invention

[0035] According to the present invention, a method for producing a recycled polymer with an alicyclic structure can be provided, which efficiently and effectively removes the crystalline polymer from a molded article containing a polymer with an alicyclic structure and a crystalline polymer to obtain a recycled polymer with an alicyclic structure. Detailed Embodiments

[0036] Hereinafter, the embodiments of the present invention will be described in detail.

[0037] (Method for Producing a Recycled Polymer with an Alicyclic Structure)

[0038] Method for manufacturing a recycled polymer containing an alicyclic structure (hereinafter, sometimes referred to as "the manufacturing method of the present invention") is a method for manufacturing a recycled polymer containing an alicyclic structure from a molded article containing a crystalline polymer and an amorphous polymer containing an alicyclic structure (hereinafter, sometimes referred to as "amorphous alicyclic polymer"). Moreover, the manufacturing method of the present invention includes the following steps: a dissolution step of mixing the molded article with a solvent and dissolving at least the amorphous alicyclic polymer in the solvent to obtain a polymer solution; a heating step of heating the polymer solution to a temperature above Tc1 - 75°C and below Tc1°C when the crystallization temperature of the crystalline polymer is set to Tc1°C; a cooling step of cooling the polymer solution after the heating step to a temperature lower than the heating temperature in the heating step and 40°C or lower; and a removal step of removing the crystalline polymer from the polymer solution after the cooling step.

[0039] If it is the above-mentioned manufacturing method, the crystalline polymer can be efficiently and effectively removed from a molded article containing an amorphous alicyclic polymer and a crystalline polymer to obtain a recycled polymer containing an alicyclic structure. The reason is presumably that after heating the polymer solution to a temperature above Tc1 - 75°C and below Tc1°C and then cooling it to a temperature lower than the heating temperature and 40°C or lower, the amorphous part of the crystalline polymer crystallizes, and the crystalline polymer becomes a solid mass, which can be easily removed in the removal step, that is, the crystalline polymer can be easily removed as a solid mass.

[0040] In addition, when the above heating step and cooling step are not carried out, the crystalline polymer swells in the polymer solution, and as a result, the removal of the crystalline polymer in the removal step becomes difficult. That is, it is difficult to efficiently and effectively remove the crystalline polymer from a molded article containing an amorphous alicyclic polymer and a crystalline polymer to obtain a recycled polymer containing an alicyclic structure.

[0041] The manufacturing method of the present invention may also optionally include: a step of pulverizing the molded article to obtain a pulverized molded article before mixing the molded article with the solvent (pulverization step), a step of screening the pulverized molded article with a sieve having a specified pore size between the pulverization step and the dissolution step (screening step), a step of drying the polymer solution after the removal step (drying step), and other steps. of the sieve to screen the pulverized molded article (screening step), a step of drying the polymer solution after the removal step (drying step), and other steps.

[0042] <Molded article>

[0043] The molded article used in the manufacturing method of the present invention contains a crystalline polymer and an amorphous alicyclic polymer, and may also optionally contain components other than the crystalline polymer and the amorphous alicyclic polymer (hereinafter, sometimes referred to as "other components").

[0044] Here, the molded article used in the manufacturing method of the present invention is a molded article obtained by various molding methods such as injection molding, extrusion molding, extrusion blow molding, injection blow molding, multi-layer blow molding, continuous blow molding, two-layer blow molding, stretch blow molding, vacuum molding, rotational molding, etc., and there are no particular limitations on the shape, physical properties, etc.

[0045] As specific molded articles, for example, molded articles for optical uses such as lenses, prisms, optical films, optical sheets, optical disc substrates, light guide plates, light guides, optical fibers, mirrors, etc. can be cited; molded articles for medical uses such as disposable syringes, medicine bottles, films for medicine packaging, storage containers for medical equipment, detection units, detection containers, infusion bags, rods for syringes, etc.; sheets, films, plates, containers, insulating materials, etc. for electrical or electronic uses such as wire coating materials, wafer shippers, capacitor films, circuit boards, connectors, etc. Tubes, round bars, bottles, building materials, stationery, etc. In addition, as the molded article, for example, waste of the molded article, processing waste generated during the manufacture of the molded article (for example, ear materials of the film, remaining parts after die cutting), used molded articles, etc. can be cited.

[0046] [Crystalline polymer]

[0047] As the crystalline polymer, polyolefins such as polyethylene and polypropylene, polyamides (nylons), polyesters, celluloses, etc. can be cited, and these polymers are polymers capable of crystallizing. Among these, from the aspect of being able to remove the crystalline polymer from the molded article more efficiently and effectively, polyolefins are preferred, polypropylene and polyethylene are more preferred, and polypropylene is further preferred. The above-mentioned molded article may contain one of these polymers alone, or may contain two or more.

[0048] In addition, the content ratio of the crystalline polymer contained in the molded article varies depending on the shape, use, etc. of the molded article, and there is no particular limitation.

[0049] Here, the crystallization temperature of the crystalline polymer is not particularly limited. For example, it is 80 °C or higher, it can be 100 °C or higher, it can also be 130 °C or higher. For example, it is 170 °C or lower, and it can also be 160 °C or lower.

[0050] [Amorphous alicyclic structure polymer]

[0051] The amorphous alicyclic structure-containing polymer has an alicyclic structure in the main chain and / or side chain. For example, from the viewpoints of the mechanical strength, heat resistance, etc. of the alicyclic structure-containing polymer regenerated product, it is preferably to contain an alicyclic structure in the main chain. As the alicyclic structure of the amorphous alicyclic structure-containing polymer, a saturated cyclic hydrocarbon (cycloalkane) structure, an unsaturated cyclic hydrocarbon (cycloolefin) structure, etc. can be cited. From the viewpoints of the mechanical strength, heat resistance, etc. of the alicyclic structure-containing polymer regenerated product, a cycloalkane structure and a cycloolefin structure are preferred, and a cycloalkane structure is more preferred. The number of carbon atoms constituting the alicyclic structure is not particularly limited. From the viewpoints of maintaining the high mechanical strength, heat resistance and moldability of the alicyclic structure-containing polymer regenerated product, it is preferably 4 or more, more preferably 5 or more, preferably 30 or less, more preferably 20 or less, and further preferably 15 or less.

[0052] The proportion of the repeating unit (monomer unit) having an alicyclic structure in the amorphous alicyclic structure-containing polymer is usually 30% by mass or more, preferably 50% by mass or more, and more preferably 70% by mass or more.

[0053] If the proportion of the repeating unit having an alicyclic structure in the amorphous alicyclic structure-containing polymer is above the above lower limit, the heat resistance of the alicyclic structure-containing polymer regenerated product can be improved, for example. The remainder other than the repeating unit having an alicyclic structure in the amorphous alicyclic structure-containing polymer is not particularly limited, and various units can be used.

[0054] Here, as specific examples of the above amorphous alicyclic structure-containing polymer, for example, (1) norbornene-based polymers, (2) monocyclic cyclic olefin-based polymers, (3) cyclic conjugated diene-based polymers, (4) vinyl alicyclic hydrocarbon polymers and their hydrogenated products, etc. can be cited. Among these, norbornene-based polymers and their hydrogenated products, and cyclic conjugated diene-based polymers and their hydrogenated products are preferred, and norbornene-based polymers and their hydrogenated products are more preferred.

[0055] (1) Norbornene-based polymers

[0056] As the norbornene-based polymer, there is no particular limitation, and examples thereof include polymers obtained by polymerizing norbornene-based monomers by the methods disclosed in, for example, Japanese Patent Laid-Open No. 3-14882 and Japanese Patent Laid-Open No. 3-122137. Specifically, examples include ring-opening polymers of norbornene-based monomers and their hydrogenated products, addition polymers of norbornene-based monomers, addition copolymers of norbornene-based monomers and vinyl compounds, etc. Among these, for example, from the viewpoint of maintaining the high heat resistance and dielectric properties of the alicyclic structure-containing polymer regenerated product, ring-opening polymer hydrogenated products of norbornene-based monomers, addition polymers of norbornene-based monomers, addition copolymers of norbornene-based monomers and vinyl compounds capable of copolymerizing with norbornene-based monomers, etc. are preferred, and ring-opening polymer hydrogenated products of norbornene-based monomers are particularly preferred.

[0057] Examples of the norbornene-based monomer include bicyclo[2.2.1]hept-2-ene (common name: norbornene), 5-methyl-bicyclo[2.2.1]hept-2-ene, 5,5-dimethyl-bicyclo[2.2.1]hept-2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-butyl-bicyclo[2.2.1]hept-2-ene, 5-hexyl-bicyclo[2.2.1]hept-2-ene, 5-octyl-bicyclo[2.2.1]hept-2-ene, 5-octadecyl-bicyclo[2.2.1]hept-2-ene, 5-methylene-bicyclo[2.2.1]hept-2-ene, 5-ethylene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, 5-propenyl-bicyclo[2.2.1]hept-2-ene, 5-methoxy-carbonyl-bicyclo[2.2.1]hept-2-ene, 5-cyano-bicyclo[2.2.1]hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo[2.2.1]hept-2-ene, 5-methoxycarbonyl bicyclo[2.2.1]hept-2-ene, 5-ethoxycarbonyl bicyclo[2.2.1]hept-2-ene, 5-methyl-5-methoxycarbonyl bicyclo[2.2.1]hept-2-ene, 5-methyl-5-ethoxycarbonyl bicyclo[2.2.1]hept-2-ene, bicyclo[2.2.1]hept-5-enyl-2-methyl propionate, bicyclo[2.2.1]hept-5-enyl-2-methyl octanoate, bicyclo[2.2.1]hept-2-ene-5,6-dicarboxylic anhydride, 5-hydroxymethyl bicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl) bicyclo[2.2.1]hept-2-ene, 5-hydroxy-isopropyl bicyclo[2.2.1]hept-2-ene, 5,6-dicarboxy bicyclo[2.2.1]hept-2-ene, 5-cyano bicyclo[2.2.1]hept-2-ene, bicyclo[2.2.1]hept-2-ene-5,6-dicarboximide, tricyclo[4.3.0.1 2,5Deca-3,7-diene (common name: dicyclopentadiene), tricyclo[4.3.0.1 2,5 deca-3-ene, tricyclo[4.3.0.1 2,5 undeca-3,7-diene or tricyclo[4.3.0.1 2,5 undeca-3,8-diene or tricyclo[4.4.0.1 2,5 as a partially hydrogenated product thereof (or an adduct of cyclopentadiene and cyclohexene)] undeca-3-ene, 5-cyclopentyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexyl-bicyclo[2.2.1]hept-2-ene, 5-cyclohexenylbicyclo[2.2.1]hept-2-ene, 5-phenyl-bicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.1 2,5 .1 7,10 -dodeca-3-ene (also simply referred to as "tetracyclododecene"), 8-methyltetracyclo[4.4.0.1 2 ,5 .1 7,10 -dodeca-3-ene, 8-ethyltetracyclo[4.4.0.1 2,5 .1 7,10 -dodeca-3-ene (common name: ethyltetracyclododecene (ETD)), 8-methylenetetracyclo[4.4.0.1 2,5 .1 7,10 -dodeca-3-ene, 8-ethylenetetracyclo[4.4.0.1 2, 5 .1 7,10 -dodeca-3-ene, 8-vinyltetracyclo[4.4.0.1 2,5 .1 7,10 -dodeca-3-ene, 8-propenyl-tetracyclo[4.4.0.1 2,5 .1 7,10 -dodeca-3-ene, 8-methoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 -dodeca-3-ene, 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.1 2,5 .1 7,10 -dodeca-3-ene, 8-hydroxymethyltetracyclo[4.4.0.1 2,5 .1 7,10 -dodeca-3-ene, 8-carboxytetracyclo[4.4.0.1 2,5 .1 7,10 -dodeca-3-ene, 8-cyclopentyl-tetracyclo[4.4.0.1 2,5 .1 7 ,10 -dodeca-3-ene, 8-cyclohexyl-tetracyclo[4.4.0.1 2,5.1 7,10 -dodec-3-ene, 8-cyclohexenyl-tetracyclo[4.4.0.1 2,5 .1 7,10 -dodec-3-ene, 8-phenyl-cyclopentyl-tetracyclo[4.4.0.1 2,5 .1 7,10 -dodec-3-ene; tetracyclo[7.4.0.1 10,13 .0 2,7 trideca-2,4,6,11-tetraene (also known as 1,4-methano-1,4,4a,9a-tetrahydrofluorene), tetracyclo[8.4.0.1 11,14 .0 3,8 tetradeca-3,5,7,12-tetraene (also known as 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene), pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 pentadeca-3,10-diene, pentacyclo[7.4.0.1 3,6 .0 10,13 .0 2,7 pentadeca-4,11-diene; and norbornene-based monomers such as tetramers of cyclopentadiene, etc.

[0058] In addition, these norbornene-based monomers can be used individually or in combination of two or more.

[0059] Examples of vinyl compounds that can copolymerize with these norbornene-based monomers include: ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. ethylene or α-olefins having 2 to 20 carbon atoms; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, cyclooctene, 3a,5,6,7a-tetrahydro-4,7-methano-1H-indene, etc. cycloolefins; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, etc. non-conjugated dienes.

[0060] In addition, these copolymerizable vinyl compounds can be used individually or in combination of two or more.

[0061] Furthermore, as vinyl compounds capable of copolymerization, cyclic olefins can be cited. Examples of such cyclic olefins include monocyclic olefins such as cyclobutene, 1-methylcyclopentene, 3-methylcyclobutene, 3,4-diisopropenylcyclobutene, cyclopentene, 3-methylcyclopentene, cyclohexene, cyclooctene, 1-methylcyclooctene, 5-methylcyclooctene, cyclooctatetraene, cyclododecene, etc.

[0062] The polymerization method and hydrogenation method of norbornene-based monomers or norbornene-based monomers and vinyl compounds capable of copolymerizing with norbornene-based monomers are not particularly limited and can be carried out according to known methods.

[0063] The ring-opening (co)polymer of norbornene-based monomers is obtained by the following method: As a ring-opening polymerization catalyst, a catalyst system composed of halides, nitrates or acetylacetone compounds of metals such as ruthenium, rhodium, palladium, osmium, iridium, platinum, etc. and a reducing agent, or a catalyst system composed of halides or acetylacetone compounds of metals such as titanium, vanadium, zirconium, tungsten, molybdenum, etc. and an organoaluminum compound is used. In a solvent or without a solvent, usually at a polymerization temperature of -50°C to 100°C and a polymerization pressure of 0 to 50 kg / cm 2 The norbornene-based monomer is subjected to ring-opening (co)polymerization under such conditions to obtain the product. By adding a third component such as molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acyl chloride, ester, ketone, nitrogen-containing compound, sulfur-containing compound, halogen-containing compound, molecular iodine, other Lewis acids, etc. to the catalyst system, the polymerization activity and the selectivity of ring-opening polymerization can be improved.

[0064] The addition-type copolymer of norbornene-based monomers and vinyl compounds can be obtained, for example, by the following method: In a solvent or without a solvent, in the presence of a catalyst system composed of a titanium, zirconium or vanadium compound and an organoaluminum compound, usually at a polymerization temperature of -50°C to 100°C and a polymerization pressure of 0 to 50 kg / cm 2 the monomer components are copolymerized.

[0065] The hydrogenated product of the norbornene-based polymer can be obtained by a method of hydrogenating the ring-opening (co)polymer in the presence of a hydrogenation catalyst according to a conventional method.

[0066] (2) Monocyclic cyclic olefin-based polymers

[0067] As monocyclic cyclic olefin-based polymers, addition-type polymers of monocyclic cyclic olefin-based monomers such as cyclohexene, cycloheptene, cyclooctene, etc. disclosed in Japanese Patent Laid-Open No. 64-66216 can be used, for example.

[0068] (3) Cyclic conjugated diene-based polymers

[0069] As the cyclic conjugated diene polymer, polymers obtained by 1,2- or 1,4-addition polymerization of cyclic conjugated diene monomers such as cyclopentadiene and cyclohexadiene, and their hydrogenated products, etc., which are disclosed in, for example, Japanese Patent Laid-Open No. 6-136057 and Japanese Patent Laid-Open No. 7-258318, can be used.

[0070] (4) Vinyl alicyclic hydrocarbon polymer

[0071] As the vinyl alicyclic hydrocarbon polymer, polymers of vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane, and their hydrogenated products, which are disclosed in, for example, Japanese Patent Laid-Open No. 51-59989, and hydrogenated products of the aromatic ring portions of polymers of vinyl aromatic monomers such as styrene and α-methylstyrene, which are disclosed in Japanese Patent Laid-Open No. 63-43910, Japanese Patent Laid-Open No. 64-1706, etc., can be used.

[0072] Herein, the weight average molecular weight (Mw1) of the amorphous alicyclic structure-containing polymer is preferably 5000 or more, more preferably 8000 or more, further preferably 10000 or more, preferably 500000 or less, more preferably 200000 or less, further preferably 100000 or less, and still more preferably 35000 or less.

[0073] If the weight average molecular weight of the amorphous alicyclic structure-containing polymer is above the above lower limit, the physical properties such as the heat resistance of the alicyclic structure-containing polymer recycled material can be improved.

[0074] On the other hand, if the weight average molecular weight of the amorphous alicyclic structure-containing polymer is below the above upper limit, the crystalline polymer can be removed from the molded body more efficiently.

[0075] In this specification, the "weight average molecular weight" of the amorphous alicyclic structure-containing polymer and the alicyclic structure-containing polymer recycled material can be measured according to the method described in the examples.

[0076] The glass transition temperature (Tg1) of the amorphous alicyclic structure-containing polymer is preferably 50 °C or more, more preferably 70 °C or more, further preferably 90 °C or more, preferably 300 °C or less, more preferably 250 °C or less, further preferably 200 °C or less, and still more preferably 130 °C or less.

[0077] If the glass transition temperature is within the above range, the high moldability and heat resistance of the alicyclic structure-containing polymer recycled material can be maintained. In addition, the crystalline polymer can be removed from the molded body more efficiently.

[0078] In this specification, the "glass transition temperature" of the amorphous alicyclic structure polymer and the recycled alicyclic structure polymer can be measured according to the method described in the examples.

[0079] The 5% heat loss temperature of the amorphous alicyclic structure polymer (measured in a nitrogen environment at a heating rate of 5 °C / minute) is preferably 300 °C or higher, more preferably 350 °C or higher.

[0080] If the 5% heat loss temperature of the amorphous alicyclic structure polymer is above the above lower limit, even if the recycled alicyclic structure polymer is molded at a high temperature to obtain a molded article as a recycled product (hereinafter, sometimes referred to as a "regenerated molded article"), molding defects such as the inclusion of air bubbles can be suppressed.

[0081] The melt viscosity of the amorphous alicyclic structure polymer at a temperature of 260 °C is usually 1×10 1 P (poise) or more, preferably 1×10 2 P or more, usually 1×10 5 P or less, preferably 1×10 4 P or less.

[0082] If the melt viscosity is within the above range, the high moldability and mechanical strength of the recycled alicyclic structure polymer can be maintained.

[0083] [Other components]

[0084] As other components, for example, polymers other than crystalline polymers and amorphous alicyclic structure polymers (such as polyvinyl chloride, polystyrene, etc.); additives such as antioxidants, ultraviolet absorbers, light stabilizers, near-infrared absorbers, coloring agents such as dyes and pigments, lubricants, plasticizers, antistatic agents, fluorescent brighteners, etc.

[0085] <Crushing process>

[0086] In the optionally performed crushing process, the molded article is crushed before mixing with the solvent to obtain a crushed molded article.

[0087] The crushing of the molded article can be carried out using, for example, a crusher or a cutting machine. By crushing the molded article, the dissolution time of the amorphous alicyclic structure polymer in the molded article can be shortened and the dissolution efficiency can be improved.

[0088] <Sieving process>

[0089] In the optionally performed sieving process, the crushed molded article is sieved with a sieve having a specified pore size between the crushing process and the dissolution process. The crushed molded article is sieved with a sieve having a specified pore size.

[0090] As the specified pore size Generally, it is 3 mm or more, preferably 4 mm or more, more preferably 5 mm or more, generally 15 mm or less, preferably 12 mm or less, more preferably 10 mm or less.

[0091] By screening the molded body with a sieve having a diameter below the above upper limit, reducing the size of the crushed product of the molded body to be dissolved, the dissolution time can be further shortened and the dissolution efficiency can be improved.

[0092] On the other hand, by making the diameter of the sieve the above lower limit or more, a reduction in the recovery efficiency due to the crushed product of the molded body that does not pass through the sieve can be suppressed.

[0093] <Dissolution step>

[0094] In the dissolution step, the molded body after being arbitrarily crushed and screened is mixed with a solvent, and at least the amorphous alicyclic structure polymer is dissolved in the solvent to obtain a polymer solution.

[0095] The solvent used in the dissolution step is not particularly limited as long as it can dissolve the amorphous alicyclic structure polymer.

[0096] Here, the solvent used in the dissolution step is preferably a poor solvent for the crystalline polymer (hereinafter, sometimes simply referred to as "poor solvent"). If the solvent used in the dissolution step is a poor solvent for the crystalline polymer, the crystalline polymer can exist as an undissolved component in the polymer solution, so that the crystalline polymer can be removed from the molded body more efficiently and effectively after the heating step and the cooling step.

[0097] Examples of the poor solvent include cyclohexane (SP value = about 8.2 (cal / cm 3 )) 1 / 2 , xylene (SP value = about 8.8 (cal / cm 3 )) 1 / 2 , toluene (SP value = about 8.9 (cal / cm 3 )) 1 / 2 ), etc. Among these, from the aspect of being able to further efficiently and effectively remove the crystalline polymer from the molded body, cyclohexane and xylene are preferred, and cyclohexane is more preferred.

[0098] The SP value of the poor solvent is 7 (cal / cm 3 ) 1 / 2 or more, preferably 7.6 (cal / cm 3 ) 1 / 2 or more, more preferably 8.2 (cal / cm 3 ) 1 / 2 or more, and is 9.9 (cal / cm 3 ) 1 / 2Hereinafter, it is preferably 9.1 (cal / cm 3 ) 1 / 2 Hereinafter, it is more preferably 8.8 (cal / cm 3 ) 1 / 2 Hereinafter.

[0099] In the dissolution step, the addition amount of the molded body relative to 100 parts by mass of the solvent is usually 1 part by mass or more and 20 parts by mass or less.

[0100] In the dissolution step, the temperature of the solvent when dissolving the amorphous alicyclic structure polymer is usually 15°C or higher and 35°C or lower.

[0101] In the dissolution step, the dissolution of the amorphous alicyclic structure polymer in the solvent can be carried out while stirring, and the stirring time is usually 0.5 hours or more and 10 hours or less.

[0102] <Heating step>

[0103] In the heating step, when the crystallization temperature of the crystalline polymer is set to Tc1 °C, the polymer solution is heated to a temperature of Tc1 - 75°C or higher and Tc1 °C or lower. Thereby, the amorphous part of the crystalline polymer can be promoted to crystallize.

[0104] Here, the heating temperature in the heating step is preferably Tc1 - 50°C or higher, preferably Tc1 - 20°C or lower, and more preferably Tc1 - 35°C or lower.

[0105] If the heating temperature in the heating step is above the above lower limit, the crystalline polymer can be removed from the molded body more efficiently.

[0106] On the other hand, if the heating temperature in the heating step is below the above upper limit, the crystalline polymer can be removed from the molded body more effectively.

[0107] In addition, the heating temperature in the heating step is preferably 60°C or higher, more preferably 80°C or higher, preferably 100°C or lower, and more preferably 90°C or lower.

[0108] If the heating temperature in the heating step is above the above lower limit, the crystalline polymer can be removed from the molded body more efficiently.

[0109] On the other hand, if the heating temperature in the heating step is below the above upper limit, the crystalline polymer can be removed from the molded body more effectively.

[0110] In the heating step, the heating time is usually 0.5 hours or more and 10 hours or less.

[0111] In addition, in the heating step, the polymer solution can be heated while being stirred, or can be heated in a static state. However, from the viewpoint of uniformly heating the polymer solution and further promoting the crystallization of the amorphous portion of the crystalline polymer, it is preferable to heat the polymer solution while being stirred.

[0112] <Cooling step>

[0113] In the cooling step, the polymer solution after the heating step is cooled to a low temperature lower than the heating temperature in the heating step and 40°C or lower. Thereby, the crystalline polymer in the polymer solution can be precipitated as a solid mass.

[0114] The cooling temperature in the cooling step is preferably 20°C or higher and preferably 30°C or lower.

[0115] If the cooling temperature in the cooling step is at or above the above lower limit, the crystalline polymer can be removed from the molded body more efficiently.

[0116] If the cooling temperature in the cooling step is at or below the above upper limit, the crystalline polymer can be removed from the molded body more effectively.

[0117] In the cooling step, the cooling time is usually 1 hour or more and 3 hours or less.

[0118] In addition, in the cooling step, the polymer solution can be cooled while being stirred, or can be cooled in a static state. However, from the viewpoint of increasing the size of the solid mass of the precipitated crystalline polymer and increasing the removal rate of the crystalline polymer in the removal step, it is preferable to cool the polymer solution in a static state.

[0119] Here, the difference between the heating temperature in the heating step and the cooling temperature in the cooling step ("heating temperature" - "cooling temperature") is not particularly limited as long as the crystalline polymer can be removed in the removal step. For example, it is 20°C or higher, can be 30°C or higher, can be 40°C or higher, can be 50°C or higher. For example, it is 150°C or lower, can be 100°C or lower, can be 70°C or lower.

[0120] In addition, in the cooling step, the cooling rate is usually 1°C / minute or more and 10°C / minute or less.

[0121] <Removal step>

[0122] In the removal step, the crystalline polymer is removed from the polymer solution after the cooling step. Here, the crystalline polymer in the polymer solution after the cooling step can usually exist in the polymer solution in the form of a solid mass, so the crystalline polymer can be easily removed as a solid mass.

[0123] The means for removing the crystalline polymer from the polymer solution after the cooling step is not particularly limited, and known methods such as filtration, extraction, decantation, etc. can be cited. Among these, from the aspect of being able to remove the crystalline polymer from the molded body more efficiently and effectively, it is preferable to remove the crystalline polymer by filtration. That is, the removal step is preferably a filtration step.

[0124] Hereinafter, the filtration step will be exemplified to explain the removal step, but the removal step is not limited thereto.

[0125] In the filtration step, the polymer solution after the cooling step is filtered, and the crystalline polymer is removed as a residue (solid mass). That is, the alicyclic structure polymer regenerate can be obtained in the form of a filtrate.

[0126] In addition, the temperature of the polymer solution in the filtration step is not particularly limited as long as it is a temperature at which the crystalline polymer can be removed, and is usually 20°C or higher and 40°C or lower.

[0127] In the filtration step, from the aspect of being able to further efficiently and effectively remove the crystalline polymer from the molded body, it is preferable to use a filter aid. As the filter aid, for example, diatomaceous earth (e.g., trade name “RADIOLITE”), perlite (e.g., trade name “TOPCO”) can be cited.

[0128] Here, as the method of using the filter aid, there are a main feeding method of pre-adding the filter aid to the polymer solution, a precoating method of depositing the filter aid on a filter medium such as a filter to form a filter bed and then performing filtration, etc. However, from the aspect of being able to effectively suppress the mixing of the filter aid into the filtrate, the precoating method is preferable.

[0129] As the filter medium, a leaf filter having a wire mesh, a cloth filter (filter cloth), a synthetic resin filter, a paper filter, etc. can be cited.

[0130] The filtration of the polymer solution can be carried out by, for example, pressure filtration or vacuum filtration, but from the viewpoint of easily adjusting the differential pressure between the inlet and outlet of the filtration device and increasing the filtration rate of the polymer solution, it is preferable to carry out pressure filtration.

[0131] Here, in pressure filtration, the differential pressure between the inlet and outlet of the filtration device is usually 0.1 MPa or higher, preferably 0.15 MPa or higher, usually 1.0 MPa or lower, preferably 0.5 MPa or lower.

[0132] If the differential pressure of the solution filtration is above the above lower limit, the filtration rate of the polymer solution can be effectively increased.

[0133] On the other hand, if the differential pressure of the solution filtration is below the above upper limit, the load on the equipment can be reduced and the life of the equipment can be extended.

[0134] <Drying process>

[0135] In the optionally implementable drying process, the polymer solution after the removal process is dried. That is, in the drying process, the solvent is removed from the polymer solution to obtain a dried alicyclic structure-containing polymer regenerate.

[0136] The drying of the solvent can be carried out by, for example, heat drying, or can be carried out by reduced pressure drying. In addition, it can also be carried out by heat reduced pressure drying which combines heat drying and reduced pressure drying. From the viewpoint of the rate of removing the solvent from the polymer solution, the drying of the solvent is preferably carried out by heat reduced pressure drying.

[0137] The temperature for carrying out heat drying or heat reduced pressure drying is not particularly limited as long as the solvent can be removed. Usually, it is 150 °C or higher, preferably 180 °C or higher, usually 300 °C or lower, and preferably 250 °C or lower.

[0138] The pressure for carrying out reduced pressure drying or heat reduced pressure drying is usually -0.01 MPa or lower, preferably -0.05 MPa or lower, and more preferably -0.1 MPa or lower in terms of gauge pressure.

[0139] <Alicyclic structure-containing polymer regenerate>

[0140] The alicyclic structure-containing polymer regenerate obtained by the production method of the present invention can be suitably used as a raw material for a regenerated molded body because the crystalline polymer has been removed (in other words, it has high purity). In addition, the alicyclic structure-containing polymer regenerate obtained by the production method of the present invention is usually amorphous.

[0141] Here, the alicyclic structure-containing polymer regenerate can be arbitrarily kneaded with other polymers such as crystalline polymers and used as a raw material for a regenerated molded body.

[0142] As specific molded bodies, for example: molded bodies for optical uses such as lenses, prisms, optical films, optical sheets, optical disc substrates, light guide plates, optical waveguides, optical fibers, and mirrors; molded bodies for medical uses such as disposable syringes, medicine bottles, films for medicine packaging, storage containers for medical equipment, detection units, detection containers, infusion bags, and rods for syringes; molded bodies for electrical or electronic uses such as wire coating materials, wafer shippers, capacitor films, circuit boards, and connectors, sheets, films, plates, containers, insulating materials, etc.; tubes, round rods, bottles, building materials, stationery, etc.

[0143] The repeating units (monomeric units) constituting the alicyclic structure polymer regenerate and their ratios can generally be the same as the repeating units (monomeric units) and their ratios described in the item of "amorphous alicyclic structure polymer".

[0144] Here, the change amount (∣Mw1 - Mw2∣) of the weight-average molecular weight (Mw2) of the alicyclic structure polymer regenerate with respect to the weight-average molecular weight (Mw1) of the amorphous alicyclic structure polymer is preferably less than 2000, more preferably less than 1000.

[0145] If the change amount of the above weight-average molecular weight is less than the above upper limit, it can be said that the physical properties of the amorphous alicyclic structure polymer (before regeneration) in the molded article are well maintained in the alicyclic structure polymer regenerate.

[0146] In addition, the change amount (∣Tg1 - Tg2∣) of the glass transition temperature (Tg2) of the alicyclic structure polymer regenerate with respect to the glass transition temperature (Tg1) of the amorphous alicyclic structure polymer is preferably less than 3°C, more preferably less than 2°C.

[0147] If the change amount of the above glass transition temperature is less than the above upper limit, it can be said that the physical properties of the amorphous alicyclic structure polymer (before regeneration) in the molded article are well maintained in the alicyclic structure polymer regenerate.

[0148] Examples

[0149] Hereinafter, examples and comparative examples are given to illustrate the present invention more specifically. The present invention is not limited to these examples. In the following examples and comparative examples, parts and % are based on mass unless otherwise specified.

[0150] Moreover, in the examples and comparative examples, the measurement and evaluation were carried out by the following methods.

[0151] <Weight-average molecular weight of amorphous alicyclic structure polymer>

[0152] The weight-average molecular weight (Mw1) of the amorphous alicyclic structure polymer (before regeneration) was measured at 40°C as a standard polyisoprene conversion value by gel permeation chromatography (GPC) using cyclohexane as the eluent. As the measurement device, HLC8120GPC manufactured by Tosoh Corporation was used.

[0153] Here, as the standard polyisoprene, a total of 10 standard polyisoprenes manufactured by Tosoh Corporation with Mw = 602, 1390, 3920, 8050, 13800, 22700, 58800, 71300, 109000, and 280000 were used.

[0154] In addition, a sample was prepared by heating and dissolving a test specimen (an amorphous alicyclic structure polymer) in cyclohexane at 40°C at a sample concentration of 4 mg / mL.

[0155] Furthermore, three TSKgel G5000HXL, TSKgel G4000HXL, and TSKgel G2000HXL columns manufactured by Tosoh Corporation were connected in series as the chromatographic column, and the measurement was carried out under the conditions of a flow rate of 1.0 mL / minute, a sample injection volume of 100 μL, and a column temperature of 40°C.

[0156] <Glass transition temperature of amorphous alicyclic structure polymer>

[0157] The glass transition temperature (Tg1) of the amorphous alicyclic structure polymer (before regeneration) was measured using a differential scanning calorimeter in accordance with JIS K7121.

[0158] <Filtration rate>

[0159] First, a filter bed (precoat) composed of a filter aid (Showa Chemical Industry Co., Ltd.'s "RADIOLITE (registered trademark) #1500") was formed on the filter of the filtration device (manufactured by Sartorius) at 1.2 kg / m 2 . Then, 3 parts of a filter aid (Showa Chemical Industry Co., Ltd.'s "RADIOLITE (registered trademark) #1500") (main body feeding) was added to the polymer solution after the cooling step obtained in the examples and comparative examples with respect to a total of 100 parts of the crystalline polymer and the amorphous alicyclic structure polymer. Then, using the above filtration device, the polymer solution containing the filter aid was pressure-filtered under the conditions of a filtration area of 12.56 cm 2 and a pressure of 0.2 MPa, and the amount of the filtrate obtained in 10 minutes was measured and evaluated according to the following criteria. The larger the amount of the obtained filtrate, the more efficiently the crystalline polymer is removed from the molded body.

[0160] A: 80 g or more

[0161] B: 40 g or more and less than 80 g

[0162] C: Less than 40 g

[0163] <Total light transmittance>

[0164] First, using a press manufactured by Iemoto Seisakusho and a metal mold of 1 mm (thickness) × 3 cm (length) × 3 cm (width), the alicyclic structure polymer regenerate obtained in the examples and comparative examples was molded into a test piece with a thickness of 1 mm. In addition, the pressing temperature was "Tg1 + 60°C" and the pressing pressure was 20 MPa.

[0165] Then, the total light transmittance of the above test pieces was measured using a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd., NDH300A) in accordance with the method of JIS K7105, and evaluated based on the following criteria. The higher the total light transmittance, the more effectively the crystalline polymer is removed from the molded body.

[0166] A: 70% or more

[0167] B: 60% or more and less than 70%

[0168] C: Less than 60%

[0169] <Change in glass transition temperature>

[0170] In the same manner as the measurement of the glass transition temperature (Tg1) of the above amorphous alicyclic structure polymer, the glass transition temperature (Tg2) of the alicyclic structure polymer regenerated obtained in the examples and comparative examples was measured, and the change in glass transition temperature (|Tg1 - Tg2|) was evaluated based on the following criteria.

[0171] A: The value of (|Tg1 - Tg2|) is less than 2 °C

[0172] B: The value of (|Tg1 - Tg2|) is 2 °C or more and less than 3 °C

[0173] C: The value of (|Tg1 - Tg2|) is 3 °C or more

[0174] <Change in weight average molecular weight>

[0175] In the same manner as the measurement of the weight average molecular weight (Mw1) of the above amorphous alicyclic structure polymer, the weight average molecular weight (Mw2) of the alicyclic structure polymer regenerated obtained in the examples and comparative examples was measured, and the change in weight average molecular weight (|Mw1 - Mw2|) was evaluated based on the following criteria.

[0176] A: |Mw1 - Mw2| is less than 1000

[0177] B: |Mw1 - Mw2| is 1000 or more and less than 2000

[0178] C: |Mw1 - Mw2| is 2000 or more

[0179] (Example 1)

[0180] <Production of molded body>

[0181] 85 parts of tricyclo[4.3.0.1 2,5Deca-3,7-diene (common name: dicyclopentadiene) and 15 parts of 8-ethyltetracyclo[4.4.0.1 2,5 .1 7,10 -dodec-3-ene (common name: ethyltetracyclododecene (ETD)) to obtain a copolymer (Mw1 = 29000, Tg1 = 98 °C) and polypropylene as a crystalline polymer (manufactured by Japan Polypropylene Corporation, product name "NOVATEC PP", crystallization temperature (Tc1) = 130 °C) were kneaded, and a molded article was produced using this mixture.

[0182] <Dissolution step>

[0183] 11.1 parts (concentration 10%) of the above-obtained molded article was added to 100 parts of cyclohexane as a solvent (SP value = 8.2 (cal / cm 3 ) 1 / 2 , freezing point 6.5 °C, boiling point 81.4 °C), and stirred at 25 °C for 6 hours to dissolve the amorphous alicyclic structure polymer, obtaining a polymer solution.

[0184] <Heating step>

[0185] The obtained polymer solution was heated to 85 °C and stirred at this heating temperature for 1 hour.

[0186] <Cooling step>

[0187] The polymer solution after the above heating step was cooled to 25 °C. Using the polymer solution obtained after the cooling step, the filtration rate was evaluated. The results are shown in Table 1.

[0188] <Removal step>

[0189] A filter bed (precoat) composed of a filter aid (Showa Chemical Industry Co., Ltd. "RADIOLITE (registered trademark) #1500") was formed on the filter of a filtration device (manufactured by Sartorius). Then, 3 parts of a filter aid (Showa Chemical Industry Co., Ltd. "RADIOLITE (registered trademark) #1500") was added to the polymer solution after the above cooling step based on a total of 100 parts of the crystalline polymer and the amorphous alicyclic structure polymer. Then, using the above filtration device, the polymer solution containing the filter aid was pressure-filtered at a pressure of 0.2 MPa to remove the crystalline polymer, obtaining a colorless and transparent solution (filtrate).

[0190] <Drying step>

[0191] Using a high-temperature vacuum dryer (manufactured by Yamato Scientific Co., Ltd.), cyclohexane as a solvent and other volatile components were removed from the solution obtained in the above removal step at a temperature of 200 °C and a pressure of -0.1 MPa (gauge pressure), to obtain a recycled alicyclic structure polymer.

[0192] Using the obtained recycled alicyclic structure polymer, the total light transmittance, the change in glass transition temperature, and the change in weight-average molecular weight were evaluated. The results are shown in Table 1.

[0193] (Example 2)

[0194] In the heating step, the heating temperature was changed from 85 °C to 100 °C, and other than that, various operations, measurements, and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0195] (Example 3)

[0196] In the cooling step, the cooling temperature was changed from 25 °C to 40 °C, and other than that, various operations, measurements, and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0197] (Example 4)

[0198] In the production of the molded body, the crystalline polymer was changed from polypropylene to polyethylene (manufactured by Japan Polyethylene Corporation, product name “NOVATEC HD”, crystallization temperature (Tc1): 130 °C), and in the heating step, the heating temperature was changed from 85 °C to 60 °C, and other than that, various operations, measurements, and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0199] (Example 5)

[0200] In the production of the molded body, the amorphous alicyclic structure polymer was changed to an 8-ethyltetracyclo[4.4.0.1 2, 5 .1 7,10 dodec-3-ene (common name: ethyltetracyclododecene (ETD)) ring-opening polymer hydride (Mw1 = 49000, Tg1 = 140 °C), and other than that, various operations, measurements, and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0201] (Example 6)

[0202] In the dissolution step, the solvent was changed from cyclohexane to xylene (SP value = 8.8 (cal / cm 3 ) 1 / 2 , freezing point 13 °C, boiling point 138 °C), and other than that, various operations, measurements, and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0203] (Comparative Example 1)

[0204] In the heating step, the heating temperature was changed from 85°C to 50°C, and other than that, various operations, measurements, and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0205] (Comparative Example 2)

[0206] In the cooling step, the cooling temperature was changed from 25°C to 50°C, and other than that, various operations, measurements, and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0207] (Comparative Example 3)

[0208] In the dissolution step, the solvent was changed from cyclohexane to xylene, and in the heating step, the heating temperature was changed from 85°C to 160°C, and other than that, various operations, measurements, and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0209] (Comparative Example 4)

[0210] In the dissolution step, the solvent was changed from cyclohexane to tetrahydrofuran (SP value = 9.1, freezing point -108.4°C, boiling point 66°C), and other than that, various operations, measurements, and evaluations were carried out in the same manner as in Example 1.

[0211] In Table 1 below,

[0212] "Polymer A" represents a copolymer obtained from dicyclopentadiene and ethyltetracyclododecene,

[0213] "Polymer B" represents a ring-opening polymer hydride of ethyltetracyclododecene,

[0214] "PP" represents polypropylene,

[0215] "PE" represents polyethylene,

[0216] "CHA" represents cyclohexane,

[0217] "XY" represents xylene,

[0218] "THF" represents tetrahydrofuran,

[0219] "Mw1" represents the weight-average molecular weight of the amorphous alicyclic structure polymer (before regeneration),

[0220] "Tg1" represents the glass transition temperature of the amorphous alicyclic structure polymer (before regeneration),

[0221] "Tc1" represents the crystallization temperature of the crystalline polymer, and "SP value" represents the solubility parameter value.

[0222] [Table 1]

[0223]

[0224] As is clearly seen from Table 1, in Examples 1 to 6, the crystalline polymer can be efficiently and effectively removed from the molded article.

[0225] Industrial applicability

[0226] According to the present invention, there can be provided a method for producing a recycled article of an alicyclic structure-containing polymer, which method efficiently and effectively removes a crystalline polymer from a molded article containing an alicyclic structure-containing polymer and a crystalline polymer to obtain a recycled article of an alicyclic structure-containing polymer.

Claims

1. A method for producing a regenerated product of an alicyclic structure-containing polymer, the method comprising producing a regenerated product of an alicyclic structure-containing polymer from a molded product containing a crystalline polymer and an amorphous alicyclic structure-containing polymer. The manufacturing method comprises the following steps: a dissolving step of mixing the molded body with a solvent to dissolve at least the alicyclic structure-containing polymer in the solvent to obtain a polymer solution; a heating step, when the crystallization temperature of the crystalline polymer is set to Tc1°C, heating the polymer solution to a temperature not less than Tc1-75°C and not more than Tc1°C; a cooling step of cooling the polymer solution after the heating step to a temperature lower than the heating temperature in the heating step and not higher than 40° C.; and The step of removing the crystalline polymer from the polymer solution after the cooling step.

2. The method for producing a regenerant containing an alicyclic structure polymer according to claim 1, wherein: The cooling temperature in the cooling step is 20° C. or higher.

3. The method for producing a regenerant containing an alicyclic structure polymer according to claim 1 or 2, wherein: The cooling temperature in the cooling step is 30° C. or lower.

4. The method for producing a regenerated product containing an alicyclic structure polymer according to any one of claims 1 to 3, wherein The heating temperature in the heating step is 60° C. or higher and 100° C. or lower.

5. The method for producing a regenerated product containing an alicyclic structure polymer according to any one of claims 1 to 4, wherein The heating temperature in the heating step is below Tc1-20°C.

6. The method for producing a regenerated product containing an alicyclic structure polymer according to any one of claims 1 to 5, wherein The solvent is a poor solvent for the crystalline polymer.

7. The method for producing a regenerant containing an alicyclic structure polymer according to claim 6, wherein: The poor solvent is cyclohexane.

8. The method for producing a regenerated product containing an alicyclic structure according to any one of claims 1 to 7, wherein The crystalline polymer is polypropylene.

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