JPH11293030A - Recycling of molded item of polymer resin containing alycyclic structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To give a molded body from a recycled resin showing excellent transparency by dissolving a molded body of a polymer resin having an alicyclic structure in a solvent and bleaching thereof by an adsorbent. SOLUTION: A polymer resin having an alicyclic structure is preferably a resin which has an alicyclic structure in a main chain. The most preferable alicyclic structure is a cycloalkane structure. A treatment with an adsorbent is conducted, for example, in such a way that after the absorbent is added to a resin solution and the solution is stirred for 0.1-10 hours at 100 deg.C, the adsorbent is removed. Another treatment with the adsorbent may be conducted by passing the resin solution through an adsorbent column or these treatments may be combined. The adsorbent may be used as a filtrating co-agent. The adsorbent preferably includes SiO2 or Al2 O3 such as synthetic zeolite, natural zeolite, active alumina, active white clay or the like or a crystalline or non- crystalline mixture thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for reusing an alicyclic structure-containing polymer resin molded product.

[0002]

2. Description of the Related Art When an alicyclic structure-containing polymer resin molded article, particularly an injection molded article, is melt-molded again, a gel or a burn (colored product) is generated due to thermal deterioration, and the transparency of the melt molded article is again reduced. However, it cannot be used for applications requiring transparency. In addition, when melt molding is performed again, foreign matter is mixed in from the outside, and fine irregularities are generated on the surface of the molded body. Therefore, there is a problem that the molten molded body cannot be used again for applications requiring a smooth surface. .

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for reusing an alicyclic structure-containing polymer resin molded article which can give a molded article having excellent transparency.
Another object of the present invention is to provide a molded article of an alicyclic structure-containing polymer resin which can provide a molded article having excellent transparency, particularly a molded article having a low yellow index and a high light transmittance. It is to provide usage.

[0004]

The present invention relates to a method for reusing an alicyclic structure-containing polymer resin molded article, which comprises a step of dissolving the molded article in a solvent and performing a decolorizing treatment with an adsorbent. And a method for reusing an alicyclic structure-containing polymer resin molded article.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Examples of the alicyclic structure-containing polymer resin constituting the alicyclic structure-containing polymer resin molded article to which the recycling method of the present invention can be applied include the following. 1. Alicyclic structure-containing polymer resin The alicyclic structure-containing polymer resin has an alicyclic structure in a main chain and / or a side chain, and for example, a mechanical strength of a molded article related to reuse. From the viewpoints of heat resistance and the like, those containing an alicyclic structure in the main chain are preferred. Examples of the alicyclic structure of the polymer include a saturated cyclic hydrocarbon (cycloalkane) structure and an unsaturated cyclic hydrocarbon (cycloalkene) structure. From the viewpoint of mechanical strength and heat resistance, the cycloalkane structure is preferred. And a cycloalkene structure is preferred, and those having a cycloalkane structure are most preferred.
The number of carbon atoms constituting the alicyclic structure is not particularly limited, but is usually in the range of 4 to 30, preferably 5 to 20, more preferably 5 to 15; The mechanical strength, heat resistance and moldability of the molded article according to the above are highly balanced and suitable.

[0006] The proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer resin used in the present invention may be appropriately selected according to the purpose of use. Preferably at least 50% by weight, more preferably 7% by weight.
0% by weight or more. If the proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer resin is excessively small, for example, the heat resistance of the molded article related to reuse is not preferable. The remainder other than the repeating unit having an alicyclic structure in the alicyclic structure-containing polymer resin is not particularly limited, and various types can be used.

Specific examples of the polymer resin having the alicyclic structure include (1) a norbornene-based polymer,
(2) a monocyclic cycloolefin polymer, (3) a cyclic conjugated diene polymer, (4) a vinyl alicyclic hydrocarbon polymer, and hydrogenated products thereof. Among these, norbornene-based polymers and hydrogenated products thereof,
A cyclic conjugated diene-based polymer and a hydrogenated product thereof are preferred, and a norbornene-based polymer and a hydrogenated product thereof are more preferred.

(1) Norbornene-based polymer There is no particular limitation on the norbornene-based polymer. For example, JP-A-3-14882 and JP-A-3-122.
A polymer obtained by polymerizing a norbornene-based monomer by a method disclosed in, for example, JP-A-137-137 is used. Specific examples include a ring-opening polymer of a norbornene-based monomer and a hydrogenated product thereof, an addition polymer of a norbornene-based monomer, and an addition-type polymer of a norbornene-based monomer and a vinyl compound. Among these, for example, in order to highly balance the heat resistance and the dielectric properties of the molded article related to reuse,
A hydrogenated ring-opening polymer of a norbornene-based monomer, an addition-type polymer of a norbornene-based monomer, and an addition-type polymer of a vinyl compound copolymerizable with a norbornene-based monomer are preferable. Additives are particularly preferred.

The norbornene-based monomer includes bicyclo
[2.2.1] Hept-2-ene (common name norbornene)
), 5-methyl-bicyclo [2.2.1] hepta-2
-Ene, 5,5-dimethyl-bicyclo [2.2.1]
Pt-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] hepta-2-ene, 5-methylyl
Den-bicyclo [2.2.1] hepta-2-ene, 5-
Ethylidene-bicyclo [2.2.1] hepta-2-e
5-vinyl-bicyclo [2.2.1] hepta-2-
Ene, 5-propenyl-bicyclo [2.2.1] hepta
-2-ene, 5-methoxy-carbonyl-bicyclo
[2.2.1] Hept-2-ene, 5-cyano-bisic
B [2.2.1] Hept-2-ene, 5-methyl-5-
Methoxycarbonyl-bicyclo [2.2.1] hepta
2-ene; 5-methoxycarbonylbicyclo [2.2.
1] Hept-2-ene, 5-ethoxycarbonylbisic
B [2.2.1] hept-2-ene, 5-methyl-5-
Methoxycarbonylbicyclo [2.2.1] hept-2
-Ene, 5-methyl-5-ethoxycarbonylbicyclo
[2.2.1] Hept-2-ene, bicyclo [2.2.
1] hept-5-enyl-2-methylpropionate,
Bicyclo [2.2.1] hept-5-enyl-2-methyl
Luoctaneate, bicyclo [2.2.1] hept-2-
Ene-5,6-dicarboxylic anhydride, 5-hydroxymethyl
Cylbicyclo [2.2.1] hept-2-ene, 5,6
-Di (hydroxymethyl) bicyclo [2.2.1] hept
To-2-ene, 5-hydroxy-i-propylbicyclo
[2.2.1] Hept-2-ene, 5,6-dicarboxy
Sibicyclo [2.2.1] hept-2-ene, 5-cia
Nobicyclo [2.2.1] hept-2-ene, bicyclo
[2.2.1] Hept-2-ene-5,6-dicarboxylic
Acid imide, tricyclo [4.3.0.1^2,5] Deca
3,7-diene (common name dicyclopentadiene), tri
Cyclo [4.3.0.1^2,5] Dec-3-ene, Trishi
Black [4.3.0.1^2,5] Undeca-3,7-diene
Or tricyclo [4.3.0.1^2,5] Undeca
3,8-dienes or their partially hydrogenated products (or
Adduct of cyclopentadiene and cyclohexene)
Tricyclo [4.4.0.1^2,5] Undeca-3-D
, 5-cyclopentyl-bicyclo [2.2.1] hep
To-2-ene, 5-cyclohexyl-bicyclo [2.
2.1] Hept-2-ene, 5-cyclohexenylbishi
Black [2.2.1] hept-2-ene, 5-phenyl-
Bicyclo [2.2.1] hept-2-ene, tetracyclic
B [4.4.0.1^2,5. 1^7,10] -Dodeca-3-ene
(Also simply referred to as tetracyclododecene), 8-methyl
Toracyclo [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, 8-methylidene
Toracyclo [4.4.0.1^2,5. 1^7,10]-Dodeca-
3-ene, 8-ethylidenetetracyclo [4.4.0.
1^2,5. 1^7,10] -Dodeca-3-ene, 8-vinyltet
Lacyclo [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-methoxyca
Rubonyltetracyclo [4.4.0.1^2,5. 1^7,10]
-Dodeca-3-ene, 8-methyl-8-methoxycarbo
Nyltetracyclo [4.4.0.1^2,5. 1^7,10] -Do
Dec-3-ene, 8-hydroxymethyltetracyclo
[4.4.0.1^2,5. 1^7,10] -Dodeka-3-ene,
8-carboxytetracyclo [4.4.0.1^2,5. 1
^7,10] -Dodeca-3-ene; 8-cyclopentyl-tet
Lacyclo [4.4.0.1^2,5. 1^7,10] -Dodeca-3
-Ene, 8-cyclohexyl-tetracyclo [4.4.
0.1^2,5. 1^{7, Ten}] -Dodeca-3-ene, 8-cyclo
Hexenyl-tetracyclo [4.4.0.1^2,5. 1
^7,10] -Dodeca-3-ene, 8-phenyl-cyclopen
Tyl-tetracyclo [4.4.0.1^2,5. 1^7,10]-
Dodeca-3-ene; tetracyclo [7.4.0.1
^10,13. 0^2,7] Trideca-2,4,6,11-tetra
Ene (1,4-methano-1,4,4a, 9a-tetrahi
Dolofluorene), tetracyclo [8.4.
0.1^11,14. 0^3,8] Tetradeca-3,5,7,12
-Tetraene (1,4-methano-1,4,4a, 5,1
0,10a-hexahydroanthracene),
Nantacyclo [6.5.1.1^3,6. 0^2,7. 0^9,13]
Ntadeca-3,10-diene, pentacyclo [7.4.
0.1^3,6. 1^10,13. 0^2,7] Pentadeca-4,11
-Diene; and nor such as cyclopentadiene tetramer
Bornene monomers and the like. These norbol
Nene monomers may be used alone or in combination of two or more.
Used together.

Examples of vinyl compounds copolymerizable with these norbornene monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene,
-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,
C2-C20 ethylene or α-olefin such as 1-hexadecene, 1-octadecene, 1-eicosene; cyclobutene, cyclopentene, cyclohexene,
Cycloolefins such as 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene 1,4-hexadiene, 4-methyl-1,4-
Hexadiene, 5-methyl-1,4-hexadiene,
Non-conjugated dienes such as 1,7-octadiene, and the like. These copolymerizable vinyl compounds can be used alone or in combination of two or more.

Further, examples of the copolymerizable vinyl compound include a cyclic olefin. Examples of such a cyclic olefin include cyclobutene, 1-methylcyclopentene, 3-methylcyclobutene, 3,4-diisopropenylcyclobutene, cyclopentene, 3-methylcyclopentene, cyclohexene, cyclooctene,
Monocyclic cycloolefins such as 1-methylcyclooctene, 5-methylcyclooctene, cyclooctatetraene and cyclododecene, and the above-mentioned monomers having a norbornene ring having one unsaturated bond can be mentioned.

The polymerization method and hydrogenation method of the norbornene monomer or the vinyl compound which can be copolymerized with the norbornene monomer are not particularly limited, and can be carried out according to known methods.

The ring-opening (co) polymer of a norbornene-based monomer is prepared by converting a norbornene-based monomer into a ruthenium, rhodium, palladium, osmium,
Iridium, a metal halide such as platinum, a nitrate or acetylacetone compound and a catalyst system comprising a reducing agent, or titanium, vanadium, zirconium, tungsten, a metal halide such as molybdenum or an acetylacetone compound, and an organic aluminum compound Using a catalyst system consisting of: in a solvent or without solvent, usually at a polymerization temperature of -50 ° C to 100 ° C, 0 to 50 kg / c
It can be obtained by ring-opening (co) polymerization at a polymerization pressure of m ² . In the catalyst system, molecular oxygen, alcohol, ether, peroxide, carboxylic acid, acid anhydride, acid chloride, ester, ketone, nitrogen-containing compound, sulfur-containing compound,
By adding a third component such as a halogen-containing compound, molecular iodine, and other Lewis acids, the polymerization activity and the selectivity of ring-opening polymerization can be increased.

The addition copolymer of a norbornene-based monomer and a vinyl-based compound can be prepared, for example, by adding a monomer component in a solvent or without a solvent in the presence of a catalyst system comprising a titanium, zirconium, or vanadium compound and an organoaluminum compound. In general, a polymerization temperature of −50 ° C. to 100 ° C., 0 to 0 ° C.
It can be obtained by a method of copolymerizing at a polymerization pressure of 50 kg / cm ² .

The hydrogenated norbornene-based polymer can be obtained by a conventional method in which a ring-opened (co) polymer is hydrogenated with hydrogen in the presence of a hydrogenation catalyst.

(2) Monocyclic Cyclic Olefin Polymer Examples of the monocyclic cycloolefin polymer include, for example, cyclolohexene, cycloheptene, cyclooctene and the like disclosed in JP-A-64-66216. An addition polymer of a monocyclic cyclic olefin monomer can be used.

(3) Cyclic conjugated diene polymer As the cyclic conjugated diene polymer, for example, Japanese Patent Application Laid-Open No.
The cyclic conjugated diene-based monomers such as cyclopentadiene and cyclohexadiene disclosed in JP-A-136057 and JP-A-7-258318 are used as 1,2- or 1,2-
4-Polymerized polymers and hydrogenated products thereof can be used.

(4) Vinyl alicyclic hydrocarbon-based polymer Examples of the vinyl alicyclic hydrocarbon-based polymer include vinyl alicyclic hydrocarbons such as vinyl cyclohexene and vinyl cyclohexane disclosed in JP-A-51-59989. Polymers of alicyclic hydrocarbon monomers and hydrogenated products thereof, vinyls such as styrene and α-methylstyrene disclosed in JP-A-63-43910 and JP-A-64-1706. A hydrogenated product of the aromatic ring portion of the polymer of the aromatic monomer can be used.

(5) Characteristics of the alicyclic structure-containing polymer resin The molecular weight of the alicyclic structure-containing polymer resin is appropriately selected according to the purpose of reuse. (In the case of toluene solution) in terms of polystyrene-equivalent number average molecular weight measured by gel permeation chromatography, which is 5,000 or more, preferably 5,000 to 500,000, and more preferably 8,000.
0 to 200,000, particularly preferably 10,000 to 1
When it is in the range of 000, for example, the molded article relating to reuse is excellent in mechanical strength and the like, and is suitable.

The glass transition temperature (Tg) of the alicyclic structure-containing polymer resin may be appropriately selected according to the purpose of reuse. For example, the heat resistance of a molded article related to reuse is increased. Is preferably higher, usually 50 to 300 ° C, preferably 70 to 250 ° C, more preferably 100 to 20 ° C.
0 ° C. When Tg is in this range, the moldability of the resin at the time of re-molding and the heat resistance of the molded article related to reuse are preferably highly balanced.

5% loss on heating of polymer resin containing alicyclic structure (measured in nitrogen atmosphere at a heating rate of 5 ° C./min)
Is preferably 300 ° C. or higher, particularly preferably 350 ° C.
That is all. If the 5% weight loss on heating is too low, the resin will be decomposed when the resin temperature is raised for the purpose of improving the fluidity during re-molding, and molding such as inclusion of bubbles in the molded product related to reuse will occur. There is a problem that defects easily occur. When the 5% weight loss on heating is in the above range, molding defects such as the inclusion of bubbles are less likely to occur even when the resin temperature is increased, for the purpose of improving fluidity during remolding, which is preferable.

The temperature of the alicyclic structure-containing polymer resin is 260 ° C.
Is usually 1 × 10 ¹~ 1 × 10^FivePoi
Size, preferably 1 × 10^Two~ 1 × 10^FourPoise.
When the melt viscosity is within this range, the resin composition during remolding is
The balance between the formability and the mechanical strength of the molded product related to reuse
It is suitable.

2. Molded Article Next, a molded article to which the recycling method of the present invention can be applied will be described. In the present invention, the alicyclic structure-containing polymer resin described above may be added, if necessary (depending on the purpose of use of the molded article).
Recycle the molded body made by adding other polymers, compounding agents and fillers.

The method of mixing the alicyclic structure-containing polymer resin and the above-mentioned other components in the molding of the molded article is not particularly limited as long as it is a method commonly used in ordinary thermoplastic resins. For example, a method in which a resin is kneaded in a molten state with a mixer, a twin-screw kneader, or the like, a method in which a resin is dissolved or dispersed in an appropriate solvent, mixed in a solution state, and used as it is, or a coagulation method or direct drying as necessary from the solution state There is a method of removing the solvent by a method or the like. Alternatively, if possible, there is a method in which the resin is previously mixed in the production process of the alicyclic structure-containing polymer resin. The alicyclic structure-containing polymer resin containing necessary components is usually extruded into a rod in a molten state, cut into a suitable length by a strand cutter, and used as a pellet in many cases.

Although a molded article made of the above molding material is used in the present invention, the method for obtaining the molded article is not particularly limited. Any of a known melt molding method and a solution molding method may be used.
Specific methods of the melt molding method include injection molding, extrusion molding, extrusion blow molding, injection blow molding, multilayer blow molding, connection blow molding, double wall blow molding, stretch blow molding, vacuum molding, rotational molding, and the like. Can be In the case of the melt molding method, the melting temperature of the resin at the time of molding the molded article is usually from 200 to 360 ° C., although it varies depending on the kind of the alicyclic structure-containing polymer resin.

As a solution molding method, a solution obtained by dissolving an alicyclic structure-containing polymer resin and, if necessary, a compounding agent or the like in a good solvent for the resin is formed into a film by a solution casting method or the like. Can be dried.
Such a solution may be obtained by dissolving the above molding material in a good solvent again, or a solution obtained in the resin production process may be used as it is.

As the molded article to be reused, a lens,
Molded products for optical applications such as prisms, optical films, optical sheets, optical disk substrates, light guide plates, light guides, optical fibers, mirrors, etc .; disposable syringes, chemical vials, chemical packaging films, inspection cells, inspection containers, infusion bags, and syringes Medical molded articles such as rods; Electric or electronic molded articles such as electric wire coatings, wafer shippers, capacitor films, circuit boards, connectors and other sheets, films, plates, containers, insulating materials, etc .; Plates, pipes, round bars , Bottles, building materials, stationery and the like.

Further, when the above-mentioned molded product is obtained by an injection molding method, a sprue or a runner which is a molded product which is generated as a waste material, or a molding which is generated as a waste material after cutting out a desired shape after extrusion molding or solution casting. A body or the like can also be preferably used in the recycling method of the present invention.

The above-mentioned molded product is preferably colorless and transparent. For colorless and transparent moldings for reuse,
This is because a colored or opaque molded article can be formed by an appropriate compounding agent or the like.

In the recycling method of the present invention, the molded article made of the alicyclic structure-containing polymer resin further contains another polymer, various compounding agents, and fillers (the above are collectively referred to as compounding agents, etc.). They may be used alone or in combination of two or more.

Other Polymers Other polymers include polyolefins such as polyethylene, polypropylene, and poly (4-methyl-1-pentene); polybutadienes, polyisoprenes, and styrene / butadiene / styrene block copolymers (SB).
S), styrene / isoprene / styrene block copolymer (SIS), hydrogenated SBS (SEBS), S
Rubber such as hydrogenated IS (SEPS); polystyrene, poly (meth) acrylate, polycarbonate, polyester, polyether, polyamide, polyimide,
Resins such as polysulfone and polyphenylene sulfide; and the like. These other polymers may be used alone or in combination of two or more. Further, the ratio is appropriately selected within the range of the purpose of using the molded body, and is not particularly limited in the method of the present invention.

Compounding agents The compounding agents are not particularly limited as long as they are commonly used in thermoplastic resin materials. Examples thereof include antioxidants, ultraviolet absorbers, light stabilizers, near infrared absorbers, dyes And colorants such as pigments and the like, compounding agents such as lubricants, plasticizers, antistatic agents and optical brighteners. However, those containing no coloring agents such as dyes and pigments or those having a low content are preferred.

Examples of the antioxidant include a phenolic antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant. Among these, a phenol-based antioxidant is preferable, and an alkyl-substituted phenol-based antioxidant is preferable. Agents are particularly preferably used.

As the phenolic antioxidant, various conventionally known phenolic antioxidants may be used.
-Butyl-6- (3-t-butyl-2-hydroxy-5
-Methylbenzyl) -4-methylphenyl acrylate, JP-A-2,4-di-t-amyl-6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate and the like Acrylate compounds described in JP-A-63-179953 and JP-A-1-168643; octadecyl-3- (3,5-di-t)
-Butyl-4-hydroxyphenyl) propionate,
2,2′-methylene-bis (4-methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4
-Hydroxy-5-t-butylphenyl) butane, 1,
3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis (methylene-3- (3 ′, 5′-di-t-butyl- 4'-hydroxyphenylpropionate) methane [ie, pentaerythrimethyl-tetrakis (3-
(3,5-di-t-butyl-4-hydroxyphenylpropionate)], triethylene glycol bis (3
Alkyl-substituted phenolic compounds such as-(3-t-butyl-4-hydroxy-5-methylphenyl) propionate); 6- (4-hydroxy-3,5-di-t-butylanilino) -2,4-bis Octylthio-1,3,3
5-triazine, 4-bisoctylthio-1,3,5-
Triazine, 2-octylthio-4,6-bis- (3,
5-di-t-butyl-4-oxyanilino) -1,3,
Triazine group-containing phenolic compounds such as 5-triazine;

As the phosphorus-based antioxidant, various substances commonly used in the general resin industry may be used.
For example, triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-
Di-t-butylphenyl) phosphite, 10- (3,
5-di-t-butyl-4-hydroxybenzyl) -9,
Monophosphite compounds such as 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide; 4,4′-butylidene-bis (3-methyl-6-
t-butylphenyl-di-tridecyl phosphite),
Examples thereof include diphosphite compounds such as 4,4 ′ isopropylidene-bis (phenyl-di-alkyl (C12-C15) phosphite). Among these, monophosphite compounds are preferable, and tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite and the like are particularly preferably used. ing.

Examples of the sulfur-based antioxidant include dilauryl 3,3-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,
3-thiodipropionate, laurylstearyl 3,3
Thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate, 3,
9-bis (2-dodecylthioethyl) -2,4,8,1
0-tetraoxaspiro [5,5] undecane and the like.

Each of these antioxidants is used alone.
Alternatively, two or more kinds may be used in combination. The compounding amount of the antioxidant is not particularly limited, but it is usually used in the range of 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight based on 100 parts by weight of the polymer component.

As the ultraviolet absorber, for example, 2- (2
-Hydroxy-5-methylphenyl) 2H-benzotriazole, 2- (3-t-butyl-2-hydroxy-5)
-Methylphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di -T-butyl-2-hydroxyphenyl) -2H-benzotriazole, 5-chloro-2
-(3,5-di-t-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-
benzotriazole ultraviolet absorbers such as t-amyl-2-hydroxyphenyl) -2H-benzotriazole; 4-t-butylphenyl-2-hydroxybenzoate, phenyl-2-hydroxybenzoate, 2,4
-Di-t-butylphenyl-3,5-di-t-butyl-
4-hydroxybenzoate, hexadecyl-3,5-
Di-tert-butyl-4-hydroxybenzoate, 2-
(2H-benzotriazol-2-yl) -4-methyl-6- (3,4,5,6-tetrahydrophthalimidylmethyl) phenol, 2- (2-hydroxy-5-t-octylphenyl) -2H -Benzotriazole, 2-
Bezoate UV absorbers such as (2-hydroxy-4-octylphenyl) -2H-benzotriazole;
2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-
Methoxybenzophenone-5-sulfonic acid trihydrate, 2
-Hydroxy-4-octyloxybenzophenone, 4-
Dodecaloxy-2-fodroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone,
Benzophenone-based ultraviolet absorbers such as 2,2'-dihydroxy-4,4'-dimethoxybenzophenone; ethyl-2-cyano-3,3-diphenylacrylate, 2 '
Acrylate UV absorbers such as -ethylhexyl-2-cyano-3,3-diphenylacrylate; [2,
2'-thiobis (4-t-octylphenolate)]-
Metal complex UV absorbers such as 2-ethylhexylamine nickel are exemplified.

As the light stabilizer, for example, 2, 2, 6,
6-tetramethyl-4-piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-
4-piperidyl) -2- (3,5-di-t-butyl-4
-Hydroxybenzyl) -2-n-butylmalonate,
4- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) -1- (2- (3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Hindered amine light stabilizers such as propionyloxy) ethyl) -2,2,6,6-tetramethylpiperidine can be mentioned.

Examples of the near-infrared absorbing agent include cyanine-based near-infrared absorbing agent; pyrylium-based infrared-absorbing agent; squarylium-based near-infrared absorbing agent; croconium-based infrared absorbing agent; Agent; dithiol metal complex-based near-infrared absorber; naphthoquinone-based near-infrared absorber; anthraquinone-based near-infrared absorber; indophenol-based near-infrared absorber;
Horse mackerel near-infrared absorber; Also, commercially available near-infrared absorbers SIR-103, SIR-114, SIR
IR-128, SIR-130, SIR-132, SI
R-152, SIR-159, SIR-162 (above,
Mitsui Toatsu Dye), Kayasorb IR-750, K
Ayasorb IRG-002, Kayasorb
IRG-003, IR-820B, Kayasorb
IRG-022, Kayasorb IRG-023
Kayasorb CY-2, Kayasorb CY
-4, Kayasorb CY-9 (all manufactured by Nippon Kayaku) and the like.

The dye is not particularly limited as long as it can be uniformly dispersed and dissolved in the alicyclic structure-containing polymer resin, but oil-soluble dyes (various CI solvent dyes) are widely used due to their excellent compatibility. Used. Specific examples of oil-soluble dyes include The Society of Diye
ColorIn, published by s and Colorists
dex vol. Various C.3 described in C.3. I. Solvent dyes.

Examples of the pigment include diarylide pigments such as Pigment Red 38; Pigment Red 48:
2, Pigment Red 53, Pigment Red 57: 1
Pigment Red 144, Pigment Red 166, Pigment Red 220, Pigment Red 221, Pigment Red 248, etc .; Condensed Azo Lake Pigments; Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 1
85, penzimidazolone pigments such as Pigment Red 208; quinacridone pigments such as Pigment Red 122; Pigment Red 149, Pigment Red 17
8, perylene pigments such as Pigment Red 179; and anthraquinone pigments such as Pigment Red 177.

As the lubricant, an organic compound such as an ester of an aliphatic alcohol, an ester or a partial ester of a polyhydric alcohol, or an inorganic fine particle may be used. As the organic compound, for example, glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate,
Pentaerythritol distearate, pentaerythritol tristearate and the like can be mentioned.

Other lubricants using inorganic particles may be used. Here, as the inorganic fine particles, 1 of the periodic table is used.
Oxides, sulfides, hydroxides, nitrides, halides, carbonates, sulfates, acetates, phosphates, phosphites, and organic carboxylate of Group II, IV, 6-14 elements , Silicates,
Examples include particles of titanates, borates and hydrates thereof, composite compounds centered on them, and natural compounds.

As the plasticizer, for example, tricresyl phosphate, trixylyl phosphate, triphenyl phosphate, triethylphenyl phosphate, diphenylcresyl phosphate, monophenyldicresyl phosphate, diphenylmonoxylenyl phosphate Phosphate triester plasticizers such as phosphate, monophenyldixylenyl phosphate, tributyl phosphate and triethyl phosphate; dimethyl phthalate, dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, di-phthalate 2-ethylhexyl, diisononyl phthalate, octyldecyl phthalate,
Phthalate ester plasticizers such as butyl benzyl phthalate; fatty acid monobasic ester plasticizers such as butyl oleate and glycerin monooleate; dihydric alcohol ester plasticizers; oxy acid ester plasticizers
Among these, a phosphoric acid triester plasticizer is preferable, and tricresyl phosphate and tricillyl phosphate are particularly preferably used.

Further, as another or combined softening agent or plasticizer, a hydrocarbon polymer which is liquid at room temperature and whose main skeleton is mainly a CC or C = C structure may be used. Among the liquid hydrocarbon polymers, a preferable example is a linear or branched liquid hydrocarbon polymer having no hydrocarbon ring in the main chain. Further, a molded article that does not substantially have a C = C structure is preferable because the molded article related to reuse has excellent weather resistance. The weight average molecular weight of the liquid hydrocarbon polymer is preferably 10,000 or less, more preferably 200 to 8,000, and particularly preferably 300 to 4,000. Specific examples of the liquid hydrocarbon polymer include squalane (C30H62, M
w = 422.8), liquid paraffin (white oil,
ISO VG10, I specified in JIS K2231
SO VG15, ISO VG32, ISO VG6
8, ISO VG100, VG8 and VG21), polyisobutene, hydrogenated polybutadiene, hydrogenated polyisoprene and the like. Among them, squalane, liquid paraffin and polyisobutene are preferred.

Examples of the antistatic agent include long-chain alkyl alcohols such as stearyl alcohol and behenyl alcohol, and fatty acid esters of polyhydric alcohols such as glycerin monostearate and pentaerythritol monostearate. Stearyl alcohol and behenyl alcohol are particularly preferable. preferable.

These compounding agents may be used singly or as a mixture of two or more kinds, and the ratio is appropriately selected within the range according to the purpose of the molded article. Not done. The compounding amount is the polymer component 10
It is usually in the range of 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight based on 0 parts by weight.

Fillers Organic or inorganic fillers include, for example, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, basic magnesium carbonate, dowamite, calcium oxide, calcium carbonate, sulfuric acid Minerals such as calcium, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos;
Fibers such as glass fiber, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber and polyamide fiber; glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide,
And the like.

These fillers may be used alone or in combination of two or more. The mixing ratio of the filler is appropriately selected within the range according to the purpose of the molded article, and is not particularly limited in the present invention.

Among the above compounding agents, those which are compatible with the alicyclic structure-containing polymer resin and can be in a finely dispersed state,
Or those compatible with each other are preferable. In particular, it is preferable that the molded article is colorless and transparent, because the molded article can be a colorless and transparent molded article or a colored or opaque molded article by recycling.

3. Decolorization Treatment (Adsorbent Treatment) In the present invention, the solution of the alicyclic structure-containing polymer resin molded article is treated with an adsorbent to decolorize. That is, the resin solution is treated with an adsorbent to remove the coloring caused by hot-melt molding of the alicyclic structure-containing polymer resin to make the resin colorless or to improve the color tone.

Solution Preparation The compact is pulverized as it is or is pulverized to a suitable size, mixed with a good solvent and dissolved to form a solution. When the molded body is a lump, the thickness (the length of the shortest side of the particle) is preferably 50 mm or less, more preferably 20 mm, because of easy dissolution.
It is preferable to grind to a size of not more than mm, particularly preferably not more than 10 mm. Good solvent is the type of alicyclic structure-containing polymer resin,
Depending on the structure, an appropriate material is selected from the ease of handling and the ease of subsequent drying. Specifically, aromatic solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chloroform, trichlene and chlorobenzene;
Alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, decalin, and hydrogenated dicyclopentadiene; and cyclic ether solvents such as tetrahydrofuran. The concentration of the solid content during the treatment with the adsorbent is usually 1 to 40% by weight, preferably 5 to 35% by weight,
More preferably, it is 10 to 30% by weight. If the concentration of the solution is too low, it is necessary to process a large amount of the solution, and conversely,
If the solution concentration is excessively high, the effect of the adsorption treatment is reduced.

In the adsorbent treatment, for example, an adsorbent is added to an alicyclic structure-containing polymer resin solution, and the adsorbent is treated at 0 to 100 ° C.
This is performed by stirring for 0.1 to 10 hours to remove the adsorbent. Alternatively, the alicyclic structure-containing polymer resin solution,
This is performed by passing through an adsorbent column. These may be performed in combination. Also, for example, an adsorbent can be used as a filter aid.

The adsorbent is not particularly limited as long as it can colorless or reduce the coloring caused by heating the alicyclic structure-containing polymer resin. Examples of the adsorbent include synthetic zeolites, natural zeolites, activated alumina and activated clay. SiO ₂ , Al
₂ O ₃ or a crystalline or amorphous mixed composition thereof is preferred. The specific surface area of 50 m ² / g or more, preferably 100 m ² / g or more, more preferably 200 meters ² /
g or more, a pore volume of 0.5 cm ³ / g or more, preferably 0.6 cm ³ / g or more, more preferably 0.7 cm ³ /
g or more. If the specific surface area or the pore volume is small, the adsorption capacity is inferior. The size of these adsorbent particles is 0.2μ
m or more, preferably 10 μm to 3 cm, more preferably 1 μm to 3 cm.
It is from 00 μm to 1 cm. If it is too small, removal is difficult.If it is too large, the packing ratio of the column is poor,
The decolorization efficiency of the alicyclic structure-containing polymer resin solution is low, and requires a long time treatment, which is not preferable.

In the method of passing a solution through a column packed with an adsorbent,
Filling rate is ρ (g / m^Three), The specific surface area is S (m^Two/ G),
When the residence time is t (sec), ρSt (second / m) is
10 ⁹The processing may be performed as described above. Usually, S is 1
00-1000m^Two/ G, and ρ is 4 to 8 × 10^Fiveg
/ M^ThreeThe residence time should be at least 30 seconds.
No.

In this case, if a large amount of the polymer resin solution having an alicyclic structure is treated, the adsorbing ability is reduced, so that it is necessary to extend the treatment time and the like. It is necessary to refill with a new one at the time when the degree of coloring starts to increase.

In the method of adding the adsorbent to the resin solution, the specific surface area is S (m ² / g), the amount of the adsorbent is m (g), the stirring time is t (second), and the amount of the solution to be treated is V ( g), when the concentration of the alicyclic structure-containing polymer resin solution is c, Smt / V
c (seconds / m) is 10 ³ or more, preferably 10 ⁴ or more, more preferably 10 ⁵ or more, and Sm / Vc is 1 or more,
It is preferably 5 or more, more preferably 10 or more, and t
(Second) should be 100 or more, preferably 200 or more, more preferably 300 or more. Depending on the efficiency of the stirring, it is necessary to lengthen the stirring time, and it is difficult to control the efficiency of the stirring in practice. Therefore, it is preferable to stir as long as the efficiency of the entire operation allows.

Usually, since S is about 100 to 1000 m ² / g, the concentration of the alicyclic structure-containing polymer resin solution is 10 to 10 m ² / g.
%, For example, 10 g of adsorbent per 1 kg of solution
What is necessary is just to add above and to stir well for 100 seconds or more.

After the treatment with the adsorbent, filtration is carried out to remove the adsorbent and, in some cases, foreign substances contained in the molded product by filtration.

A filter having a charge trapping function is a filter that traps and removes charged foreign substances electrically. Usually, a filter having a charge applied to a filter medium is used. Generally, a zeta potential filtration filter in which the zeta potential is controlled is used.
As the zeta potential filtration filter, generally, for example, cellulose fiber / silica / positive charge modifier (polyamine epichlorohydrin resin, aliphatic polyamine, etc.) described in JP-T-4-504379 A filter in which a positive charge modifying agent is added to a filter medium such as described above is used.

Other filter materials include, for example, fiber or membrane filters such as polypropylene, polyethylene, and PTFE, cellulose fiber filters, glass fiber filters, inorganic filters such as diatomaceous earth, and metal fiber filters. And the like. Examples of other positive charge modifiers include melamine formaldehyde cationic colloid, inorganic cationic colloid silica, and the like. On the market, a positive charge denaturing filter is sold by Cuno under the trademark "Zetaplus".

Since filtration with a filter having a charge trapping function is not necessarily high in processing capacity, usually filtration is carried out.
Performed in combination with a mechanical filtration filter. The order of combination is not particularly limited, but is usually a mechanical filtration filter, and then a charge trapping filter.

The mechanical filtration filter is not particularly limited as long as it is not adversely affected by the solvent.
For example, polypropylene, polyethylene, PTFE
And a filter made of cellulose, such as a filter made of cellulose, a filter made of a fiber made of cellulose, a filter made of a glass fiber, a filter made of an inorganic substance such as diatomaceous earth, and a filter made of a metal fiber. The pore size of the mechanical filtration filter is not particularly limited, but is usually 50 μm or less, preferably 1 μm.
Or less, more preferably 0.3 μm or less. Each of these mechanical filtration filters can be used alone or
More than one species can be used in combination. When a filter having a charge trapping function is not used, the pore size of the mechanical filtration filter is 0.5 μm or less, preferably 0.1 μm or less.
It is also preferable to repeat the filtration operation twice or more using a filter having a size of 3 μm or less.

4. Drying The solution after filtration or unfiltered can be reused as it is. For example, the volatile components are removed in a closed system so that foreign substances do not enter from the external environment, and the solution is removed in a clean room. In an environment with a high degree of cleanliness, pelletization can be performed in an environment where the degree of cleanliness is strictly controlled to class 1000 or less, preferably class 100 or less.

As a method for removing the solvent and other volatile components, known methods such as a coagulation method and a direct drying method can be employed.

The coagulation method is a method in which a resin component is precipitated by mixing a solution with a poor solvent for the alicyclic-containing polymer resin, and the type of the poor solvent depends on the type of the alicyclic-structure-containing polymer resin. Varies, for example, ethyl alcohol, n
Examples thereof include polar solvents such as alcohols such as -propyl alcohol or i-propyl alcohol, ketones such as acetone or MEK, and esters such as ethyl acetate or butyl acetate. The component containing the resin in the form of powder obtained by coagulation is preferably dried by heating, for example, in a vacuum or in nitrogen or air, and further extruded from a melt extruder, if necessary, in the form of pellets. .

The direct drying method is described, for example, in JP-A-4-1704.
No. 25, for example, in which the solution is heated under reduced pressure to remove the solvent. This method can be performed using a known device such as a centrifugal thin film continuous evaporative dryer, a scraped surface heat exchange type continuous reactor type dryer, and a high viscosity reactor device. The degree of vacuum and temperature are appropriately selected depending on the device, and are not limited.

5. Addition of Compounding Agents, etc. A method for reusing the alicyclic structure-containing polymer resin treated with the adsorbent by the above method is not particularly limited. The alicyclic structure-containing polymer resin treated with the adsorbent may be used by mixing the above-mentioned compounding agents and the like, if necessary.

The method of mixing the compounding agents and the like is not particularly limited. Once the above components are dried and pelletized,
Necessary compounding agents or the like can be added by melt-kneading, or the solvent may be dried as needed after adding in a solution state.

As a method of melt-kneading, for example, there is a method of kneading a resin in a molten state with a mixer, a twin-screw kneader, or the like. Since a homogeneous material can be obtained,
The melt kneading method is preferred.

In the case of melt-kneading, the temperature of the resin is raised from a temperature (70 ° C. or more higher than the glass transition temperature of the resin) to 33 ° C.
It is appropriate that the temperature is 0 ° C. or lower, more preferably 300 ° C. or lower, particularly preferably 280 ° C. or lower. By applying sufficient shear, a preferable uniform mixing state can be obtained. If the resin temperature is too low, the viscosity becomes high and kneading is difficult. If it is too high, the alicyclic structure-containing polymer resin and other polymer components deteriorate, and the two cannot be kneaded well due to differences in viscosity and melting point. Screw shape, etc.
The conditions for kneading should be appropriately set according to the type and shape of the kneader. After melt kneading, extrude into a rod in the molten state, cut into appropriate length with a strand cutter,
It is preferable to use a pellet-shaped molded body. The pellet-shaped molded body is preferable because it is easy to handle as a material for subsequent injection molding or extrusion molding.

6. Method for Recycling There is no particular limitation on the method for recycling the above components to which the compounding agent has been added as necessary. For example, pellets of suitable size may be melt-molded, or the pellets may be used as a solution for solution molding, or the above components obtained as a solution may be molded by a solution method. Or these solutions can be used as they are.

6.1. Melt molding method Specific examples of the melt molding method include injection molding, extrusion molding, extrusion blow molding, injection blow molding, multilayer blow molding, connection blow molding, double wall blow molding, and stretching. Blow molding, vacuum molding, rotational molding and the like can be mentioned. Although the melting temperature at the time of molding differs depending on the type of the alicyclic structure-containing polymer resin, it is preferably (a temperature 70 ° C. or more higher than the glass transition temperature of the resin) to 330 ° C. or less, more preferably 240 ° C. to 320 ° C. Particularly preferably 2
The range is from 60 ° C to 310 ° C. When it is in this range, it is excellent in precision moldability and heat deterioration resistance and is suitable.

At the time of melt molding, the resin residence time is preferably within 60 minutes, more preferably within 30 minutes, particularly preferably within 20 minutes. When it is in this range, it is possible to obtain a molded article which is less colored and has excellent properties such as mechanical strength and is used for recycling.

At the time of melt molding, it is preferable that the alicyclic structure-containing polymer resin is melted in a state in which it does not come into contact with air (or oxygen) or has a low oxygen concentration as much as possible. The oxygen concentration in a portion where the resin melts (for example, a screw portion in a melt molding machine) is preferably 10% by volume or less, more preferably 5% by volume or less, and particularly preferably 2% by volume or less. The coloring of the molded article obtained for reuse is small,
This is because they have excellent properties such as mechanical strength. for that purpose,
Specifically, by flowing an inert gas such as nitrogen into a resin injection section (often called a hopper) of a melt molding machine, or by drawing a vacuum with a closed hopper section, the above-mentioned preferable oxygen concentration is obtained. Can be realized.

6.2. Solution Forming Method In the solution forming method, a component containing an alicyclic structure-containing polymer resin is dissolved in a good solvent, and a compounding agent is added as required to form a desired shape. This is a method for obtaining a molded body by drying the product. A cast film forming method capable of obtaining a film or sheet-like molded body is generally used because of its excellent drying efficiency of the solvent, but the recycling method of the present invention is not limited to this. A method of obtaining an article coated with a cyclic structure-containing polymer resin, a method of obtaining fine powder of an alicyclic structure-containing polymer resin by finely spraying, and the like are also included.

The good solvent varies depending on the type and structure of the alicyclic structure-containing polymer resin, and an appropriate solvent is selected from the viewpoint of ease of application and drying. Specifically, aromatic solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chloroform, tricrene and chlorobenzene; alicyclic hydrocarbon solvents such as cyclohexane, methylcyclohexane, decalin, and hydrogenated products of dicyclopentadiene; Solvents: cyclic ether solvents such as tetrahydrofuran and the like can be mentioned.

6.3. Solution casting method In order to carry out the solution casting of the alicyclic structure-containing polymer resin, the resin is dissolved in a solvent. The solvent used preferably has a boiling point of 100 ° C. or higher, more preferably 120 ° C. or higher. In particular, a solvent that can uniformly dissolve the resin even at a solid content of 10% by weight or more at 25 ° C. is preferable.

Examples of such a solvent include toluene, xylene, ethylbenzene, chlorobenzene, trimethylbenzene, diethylbenzene, isopropylbenzene, chlorobenzene and the like, among which xylene, ethylbenzene and chlorobenzene are preferred.

Further, as long as the alicyclic structure-containing polymer resin is dissolved, these solvents may contain a cyclic ether such as cyclohexane, chloroform, benzene, tetrahydrofuran or dioxane or a linear ether such as n-hexane or n-octane. May be contained.

As a material satisfying these conditions favorably, there is a material containing 50% or more of an aromatic solvent such as xylene or ethylbenzene having a boiling point of 100 ° C. or more.

The resin concentration in the solution used for casting is usually 5
６０60% by weight, preferably 10-50% by weight, more preferably 20-45% by weight. If the concentration of the resin is too low, it is difficult to adjust the thickness of the sheet because the viscosity is low, and if the concentration is too high, the film-forming properties are poor due to the high viscosity, and a film with good appearance cannot be obtained.

The method for casting the resin solution is not particularly limited, and a general solution casting method can be used. Specifically, the resin solution is applied to a bar coater, a T-die, a T-die with a bar, a doctor knife, a Meir bar, a roll coat,
Using a die coat or the like, a method of casting on a flat plate or roll such as a heat-resistant material such as polyethylene terephthalate, a steel belt, or a metal foil can be used.

The sheet prepared by the solution casting method is dried to a residual solvent concentration of 2% by weight or less. If the concentration of the residual solvent is too high, the heat resistance is poor, and when used in a high-temperature environment, the residual solvent evaporates, adversely affecting the surroundings and causing deformation.

The sheet is preferably dried in two stages. First, as drying in the first stage, a sheet on a flat plate or a roll is heated at 30 to 100 ° C., preferably 4 to 100 ° C.
It is dried in a temperature range of 0 to 80 ° C. until the residual solvent concentration becomes 10% by weight or less, preferably 5% by weight or less. In this case, if the drying temperature is too high, the sheet foams upon evaporation of the solvent.

Next, the sheet is peeled off from the flat plate or roll, and as a second stage of drying, the temperature is raised to a temperature range from room temperature to 60 ° C. or higher, preferably from 70 ° C. to the glass transition temperature (Tg) of the resin. Solvent concentration of 2% by weight or less,
Preferably not more than 1% by weight, more preferably 0.5% by weight
Dry to the following.

If the drying temperature is too low, drying does not proceed, and if the temperature is too high, foaming occurs. The first stage of drying is performed, and after the drying is completed, the sheet is peeled off from a flat plate or a roll.
Even if the stage drying is performed or after the first stage drying,
The sheet may be cooled once, and the sheet may be peeled off from the flat plate or the roll, and the second-stage drying may be performed.

6.4. Additives The compounding agents and the like used in the above-mentioned "compact" may be further added and reused.

7. Moldings Related to Recycling, etc. By the recycling method of the present invention, molded articles for optical use such as lenses, prisms, deflection films, light guide plates, optical disk substrates, etc .;
Press-through package, disposable syringe,
Molded articles for medical use such as chemical vials and infusion bags; Molded articles for electric or electronic materials such as electric wire coatings, wafer shippers, hard disk substrates, etc .; Building materials such as carports and glazing; Room mirrors, inner lenses, lamp reflectors, etc. Automotive parts; packaging films such as wrap films, stretch films, shrink films, and blister packs; stationery such as ballpoint pen cores;

In particular, a transparent molded article can be obtained by selecting a compounding agent and the like, so that a molded article for optical use such as a lens, a prism, a deflection film, a light guide plate, and an optical disk substrate can be suitably obtained. As another recycling method, a solution obtained by a method similar to the above method can be used as it is for applications such as paints and printing inks.

[Examples] The present invention will be described in more detail with reference to the following examples. Unless indicated otherwise, "parts" are "parts by weight". The methods for producing the polymer and the disk substrate used in the following Examples and Comparative Examples are shown below.

[Polymer 1] 8-methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-ene (common name: methyltetracyclododecene (MTD)) 80
Part, tricyclo [4.3.0.1 ^2,5 ] deca-3,7-
20 parts of diene (common name: dicyclopentadiene (DC
P)) hydrogenated ring-opened polymer Mw: 53,000 (converted to polyisoprene by GPC analysis; solvent: cyclohexane) Tg: 140 ° C. Hydrogenation rate: 99.8% or more (before and after hydrogenation by ¹ H-NMR) Measured by comparison)

[Polymer 2] 8-ethyltetracyclo [4.4.0.1 ^2,5 . [ ^7,10 ] Dodeca-3-ene (common name: ethyltetracyclododecene (ETD)) ring-opening polymer hydride Mw: 49,000 (polyisoprene conversion value by GPC analysis; solvent: cyclohexane) Tg: 140 ° C Hydrogenation rate: 99.8% or more (measured by ¹ H-NMR before and after hydrogenation)

[Molding Example 1] An optical disk substrate was manufactured under the following conditions. Material: Polymer 1 Injection molded article: Optical disk substrate, diameter: 130 mm, thickness: 1.2 mm Molding machine: manufactured by Sumitomo Heavy Industries, Ltd .; DISC-5 Nitrogen supplied to hopper at 500 cc / min Molding condition: Resin temperature: 320 ° C , Mold temperature: 110 ° C, Molding cycle time: 15sec Molding environment: In a clean room of cleanliness class 1000

[Molding Example 2] An optical disk substrate was manufactured in exactly the same manner as in Molding Example 1, except that Polymer 2 was used instead of Polymer 1 as a material.

Example 1 100 parts of the optical disk substrate of the molding example 1 were crushed by a crusher into a square of about 5 mm under a normal indoor environment. The crushed material was dissolved in 400 parts of cyclohexane in a closed tank. Add 10 parts of alumina (manufactured by JGC Chemicals, E1Q1) and add 4 parts at 40 ° C.
The mixture was stirred for a period of time. Using diatomaceous earth (manufactured by Showa Chemical Co., Ltd., Radiolite # 500) as a filter aid, alumina was removed by filtration at a pressure of 2.5 kg / cm ^{2 using a} pressure filter (Fundafilter, manufactured by Ishikawajima-Harima Heavy Industries). From the solution, cyclohexane, a volatile component, was subjected to a cylindrical thin-film concentrator / dryer (manufactured by Hitachi, Ltd., Contro), and the operating conditions were as follows: first step: temperature 270 ° C., pressure 100 Torr, second step: temperature 27
The removal was performed at 0 ° C. and a pressure of 5 Torr. In a molten state, the mixture was melt-extruded from a die into a strand in a class 1000 clean room and cut with a pelletizer to obtain 93 parts of regenerated pellets.

Example 2 100 parts of the optical disk substrate of Molding Example 2 were crushed by a crusher in the same manner as in Example 1. Regenerated pellets were obtained in the same manner as in Example 1 to obtain 92 parts of regenerated pellets.

Example 3 The procedure of Example 2 was repeated, except that 10 parts of talc (Microace, manufactured by Nippon Talc Co.) were used instead of alumina as the adsorbent. Obtained.

Example 4 The same procedure as in Example 1 was carried out except that 10 parts of silica (IMSIL A-15, manufactured by Tatsumori Co.) was used instead of alumina as the adsorbent. Got a part.

Example 5 In Example 2, 93 parts of regenerated pellets were obtained in the same manner as in Example 1, except that 10 parts of activated clay (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of alumina as the adsorbent. Was.

Comparative Example 1 100 parts of the optical disk substrate of Molding Example 1 were crushed by a crusher in the same manner as in Example 1. Cleanliness class 10000
Cylinder temperature of 250 in a clean booth using a single screw extruder (VS-40, manufactured by Tanabe Plastic Machinery Co., Ltd.)
C. and a polymer filter temperature of 250.degree. C., the crushed material was melt-extruded into a strand from a die, and cut with a pelletizer to obtain 98 parts of regenerated pellets.

Comparative Example 2: Using the optical disk substrate of Molding Example 2, the same treatment as in Comparative Example 1 was carried out to obtain 98 parts of regenerated pellets.

Table 1 shows the characteristic values of the regenerated polymer. Molecular weight: determined by GPC analysis (solvent: cyclohexane) in terms of polyisoprene. Tg: By DSC analysis. ΔYI: Measured as a toluene solution (concentration: 13% by weight).

[0105]

[Table 1]

[Molding Example 3] A light guide plate was manufactured under the following conditions. Material: Polymer 2 Injection molded product: Light guide plate, thickness: 3 mm x width: 100 mm x length: 150 mm Molding machine: manufactured by Sumitomo Heavy Industries, Ltd .; Nitrogen is supplied to the DISC-5 hopper at 500 cc / min. Molding conditions: Resin temperature : 300 ° C, Mold temperature: 110 ° C, Molding cycle time: 60sec Molding environment: In a clean room of cleanliness class 1000

Example 6 A light guide plate was manufactured in exactly the same manner as in Molding Example 3, except that the regenerated pellets obtained in Example 3 were used instead of the polymer 2.

Comparative Example 3 A light guide plate was manufactured in exactly the same manner as in Molding Example 3, except that the regenerated pellets obtained in Comparative Example 2 were used instead of the polymer 2.

Table 2 shows the characteristic values (light transmittance and bending strength) of the obtained light guide plate. Light transmittance: Cut out the light guide plate to 50 mm x 50 mm, and use a spectrophotometer (Ubest V-570, manufactured by JASCO Corporation) at a wavelength of 450.
Measured in nm. Bending strength: A light guide plate was cut into a size of 20 mm x 150 mm, and measured by an autograph (AG-250 kN, manufactured by Shimadzu Corporation).

[0110]

[Table 2] Molding material Light transmittance Flexural strength (%) (kg / cm ² ) Molding example 3 Polymer 2 91 630 Example 6 Pellets of Example 3 91 630 Comparative example 3 Pellets of Comparative example 2 84 630

Claims (1)

[Claims] 1. A method for reusing an alicyclic structure-containing polymer resin molded article, comprising a step of dissolving the molded article in a solvent and performing a decolorizing treatment with an adsorbent. A method for reusing a structure-containing polymer resin molded article.