JPH11293029A - Recycling of molded body 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 adding hydrogen to a molded item of a polymer resin containing an alicyclic structure. SOLUTION: A polymer resin containing an alicyclic structure is preferably a resin having an alicyclic structure in a main chain. The most preferable alicyclic structure is a cycloalkane structure. A hydrogen addition treatment is conducted preferably by making a resin, preferably in a state of a solution of a formed item, contact hydrogen in the presence of a catalyst for hydrogen addition. The catalyst may be a homogeneous catalyst comprising a transition metal compound and a reductive metal compound or an inhomogeneous catalyst having a catalyst metal supported on a carrier. The inhomogeneous catalyst is removed as an in homogeneous component by adding a small amount of an deactivating agent the hydrogen treatment and the homogeneous catalyst is removed by filtration together with fine particle of compounding agents which was included in the formed item.

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 hydrogenation treatment step. An object of the present invention is to provide a method for reusing a united resin molded product.

[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 product varies depending on the kind of the polycyclic polymer or the like.
Performed at 60 ° C.

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, IS specified in JISK2231
O VG15, ISO VG32, ISO VG68,
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. Hydrogenation The present invention is characterized by including a step of hydrogenation. The molded article to be reused in the present invention may be composed of an alicyclic structure-containing polymer resin which does not substantially contain an unsaturated bond, or may be composed of, for example, a hydrogenated ring-opening polymer of a norbornene. Since the molded article may be made of an alicyclic structure-containing polymer resin which has already undergone a hydrogenation step, it is not necessary to perform a hydrogenation treatment at the time of reuse. However, the present inventors have found that by including a hydrogenation treatment step at the time of reuse, the colorless and transparent properties of a molded article or the like to be reused can be significantly improved, and have completed the present invention. It is not clear why such an effect occurs, but the effect of the present invention can be obtained by performing the treatment under the conditions corresponding to the hydrogenation reaction (each condition such as catalyst, temperature, hydrogen pressure, and stirring). The term “hydrogenation treatment” as used herein means a treatment under conditions equivalent to the hydrogenation reaction, regardless of whether a hydrogenation reaction is actually occurring (consumption of hydrogen).

In order to carry out the hydrogenation treatment, the molded body is preferably brought into a solution state, and it is preferable to carry out the hydrogenation treatment under known conditions in the production process of a known hydrogenated product of a ring-opening polymer such as a norbornene.

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 in the hydrogenation treatment step 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 hydrogenated cyclohexane, methylcyclohexane, decalin and dicyclopentadiene; cyclic ether solvents such as tetrahydrofuran; . Among these, a solvent having no unsaturated bond is preferable from the viewpoint of the efficiency of the hydrogenation treatment. The concentration of the solid content in the hydrogenation treatment is usually 1 to 40% by weight, preferably 5 to 35% by weight, more preferably 10 to 30% by weight. If the concentration of the solution is excessively low, it is necessary to treat a large amount of the solution. Conversely, if the concentration of the solution is excessively high, the effect of the hydrogenation treatment is reduced.

The hydrogenation treatment is performed by bringing the resin into contact with hydrogen, preferably in the presence of a hydrogenation catalyst. Preferably,
Hydrogenate in solvent. The hydrogenation catalyst may be a homogeneous catalyst composed of (c) a transition metal compound and (d) a reducing metal compound, or a heterogeneous catalyst having a catalytic metal supported on a carrier. The homogeneous catalyst is easy to disperse in the hydrogenation treatment liquid, so that the addition amount may be small. In addition, since the catalyst is active even without high temperature and high pressure, the treatment equipment is simple and low cost. Heterogeneous catalysts are highly active at high temperatures and pressures, can be hydrogenated in a short time, and are excellent in production efficiency such as being easily removed. In the present invention, heterogeneous catalysts are preferred.

The homogeneous catalysts are disclosed in JP-A-58-43412, JP-A-60-26024, and JP-A-64-2.
No. 4,826, JP-A-1-138257 and the like. (C) Examples of the transition metal compound include Group I or Groups IV to VII of the Deming periodic table.
A compound of a transition metal belonging to any of Group I, for example, C
transition metal halides such as r, Mo, Fe, Mn, Co, Ni, Pd, and Ru, alkoxides, acetylacetonates, sulfanates, carboxylates, naphthenates, trifluoroacetates, and stearate; Examples of the compound include manganese (III) acetylacetonate, cobalt (III) acetylacetonate, bis- (triphenylphosphine) -cobalt dichloride, nickel (II) acetylacetonate, bis- (tributylphosphine) -palladium and the like. Can be

Further, (d) the reducing metal compound includes:
Deming Periodic Table IA, IIA, IIB, III
Group A or IVA metal compound having at least one metal element-carbon bond or metal element-hydrogen bond, such as an Al compound, a Li compound, a Zn compound, and a Mg compound. Specifically, trimethylaluminum, triphenylaluminum, diethylaluminum chloride, ethylaluminum sesquichloride, diethylaluminum hydride, n
-Propyl lithium, sec-butyl lithium, p-tolyl lithium and the like. Specifically, as a combination of the component (c) and the component (d), M is used as the component (c).
n, an organometallic compound of Fe, Co, or Ni, a halide, an alkoxide, an acetylacetonate, a sulfonate, or a naphthenate;
l, Li, Zn, a catalyst obtained by combining an organic compound such as Mg, or a hydride is preferable because it has high activity, and the influence of impurities on the reaction inhibition / activity decrease is small.
A catalyst combining an organometallic compound, halide, alkoxide, or acetylacetonate of Ti, Fe, Co, or Ni as the component (c), and an alkylaluminum or alkyllithium as the component (d) has particularly high activity. In addition, the influence of impurities on the inhibition of the reaction and the decrease in the activity is particularly small, so that it is more preferable. Although the quantitative relationship of these components depends on the type of each component, generally, the metal element of the component (d) is 0.5 mol or more, preferably 1 mol or more, per 1 mol of the metal element of the component (c). It is 50 mol or less, preferably 8 mol or less. If the amount is too large or too small, the activity of the hydrogenation treatment is insufficient. If the amount is particularly large, gelation and side reactions may occur.

Heterogeneous catalysts are also known,
For example, a material in which a hydrogenation catalyst metal such as Ni or Pd is supported on a carrier may be used. In particular, when mixing the less preferred of such impurities, as a carrier, it is preferable to use an adsorbent such as alumina or diatomaceous earth, and a pore volume 0.5 cm ³ / g or more, preferably 0.6 cm ³ / g
It is preferable to use alumina having a specific surface area of at least 0.7 cm ³ / g or more, a specific surface area of 50 cm ² / g or more, preferably 100 cm ² / g or more, more preferably 200 cm ² / g or more. When such a carrier is used, a transition metal atom or the like derived from the catalyst used for the polymerization can be adsorbed, and a hydrogenated product with less impurities can be obtained.

In the case of a homogeneous catalyst, the amount of the hydrogenation catalyst used in the hydrogenation treatment varies depending on the type and combination of each component.
The transition metal compound of the component (c) is 0.001 mmol or more, preferably 0.1 mmol or more, and 1000 mmol or less, preferably 100 mmol or less. Also, in the case of a heterogeneous catalyst, the amount of the hydrogenation catalyst used for the hydrogenation treatment varies depending on the type of catalyst metal, the state of being supported on a carrier, and the like. Metal content is 0.1 g or more, preferably 1.0 g or more, 2
0 g or less, preferably 15 g or less. Excessive addition of the hydrogenation catalyst to the hydrotreating solution is costly, and it is difficult to perform post-treatment such as removal of the hydrogenation catalyst, and too little results in poor reaction efficiency.

The hydrogenation treatment is performed by stirring the resin solution or introducing hydrogen into the hydrogenation treatment solution. For example, a method of bringing the introduced hydrogen into sufficient contact with the resin under stirring is used. preferable. The hydrogen pressure is usually between 0.
1 kgf / cm ² or more, preferably 2 kgf / cm ² or more, 100 kgf / cm ² or less, preferably 50 kgf / cm ²
/ Cm ² or less. If the hydrogen pressure is too low, the hydrogenation treatment does not proceed. If the hydrogen pressure is too high, the amount of hydrogen used increases and the economic efficiency deteriorates.

The hydrogenation treatment is usually performed at 0 ° C. to 250 ° C.
Preferably 20 ° C to 200 ° C, more preferably 50 ° C
~ 180 ° C, 0.1 ~ 10 hours, preferably 0.5 ~
It progresses by stirring for 5 hours, more preferably 1-2 hours. When a homogeneous catalyst is used, the mixture is preferably stirred at 20 ° C. to 200 ° C. for 0.5 to 5 hours.
It is carried out by stirring at 0 ° C or more, more preferably at 100 ° C to 200 ° C, most preferably at 120 ° C to 180 ° C for 0.5 to 10 hours. If the temperature is too low, the processing effect is low, and if it is too high, the energy cost increases. In the present invention, there is no need to increase the actual hydrogenation rate. Some alicyclic structure-containing polymer resins originally have no unsaturated bond, and some have no definition of hydrogenation rate itself.

After the hydrogenation treatment, in the case of a heterogeneous catalyst, a small amount of a deactivator such as water or alcohol is added, and if necessary, an inorganic adsorbent such as silica or alumina is added to homogenize the catalyst. After the treatment, in the case of a homogeneous catalyst, the mixture is filtered as it is, and removed together with the fine particle compounding agent and the like contained in the molded article. The removal of the catalyst and the like can be carried out in advance by a centrifugal separation step, followed by a filtration treatment with a filter, whereby clogging of the filter can be prevented. The centrifugation method and the filtration method are not particularly limited as long as the used catalyst can be removed. Removal by filtration is preferred because it is simple and efficient. In the case of filtration, pressure filtration or suction filtration may be used. From the viewpoint of efficiency, it is preferable to use a filter aid such as diatomaceous earth and perlite.

The filter having a charge trapping function is a filter that traps and removes charged foreign matter electrically. Usually, a filter in which a charge is 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 media 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".

Filtration with a filter having a charge trapping function is not always high in processing capacity.
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.

Drying The solution after filtration or unfiltered can be reused as it is. For example, the volatile components are removed in a closed system to prevent foreign substances from entering from the external environment, and the solution in a clean room or the like is removed. It can be pelletized and used in an environment in which the cleanness is strictly controlled to a class 1000 or less, preferably a class 100 or less under a high degree environment.

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.

4. Addition of Compounding Agents, etc. The method for reusing the alicyclic structure-containing polymer resin hydrogenated by the above method is not particularly limited. The hydrogenated alicyclic structure-containing polymer resin 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 by 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 set to a value which is higher than the glass transition temperature of the resin by 70 ° C. or more.
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.

5. Method for Recycling The method for recycling the above components to which the compounding agent has been added if necessary is not particularly limited. 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. Alternatively, these solutions can be used as they are.

5.1. 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 inflation. Molding, stretch blow molding, vacuum molding, rotational molding and the like. Although the melting temperature at the time of molding varies 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 3 ° C.
20 ° C, particularly preferably in the range of 260 ° 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. There is little coloring of the resulting molded article for reuse,
This is because they have excellent properties such as mechanical strength. For this purpose, specifically, an inert gas such as nitrogen is supplied to a resin injection section (often referred to as a hopper) of a melt molding machine, or the above-mentioned hopper is hermetically sealed by drawing a vacuum with the hopper as a closed structure. A favorable oxygen concentration can be achieved.

5.2. Solution Forming Method In the solution forming method, a component containing an alicyclic structure-containing polymer resin is dissolved in a good solvent, a compounding agent and the like are added as needed to form a desired shape, and then a solution is formed. 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 ease of 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.

5.3. 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.

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.

It is generally preferable that the sheet is 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 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. Moldings Related to Recycling Moldings for optical applications such as lenses, prisms, deflecting films, light guide plates, optical disk substrates, etc., according to the recycling method of the present invention;
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, and thus a molded article for optical use such as a lens, a prism and a deflection film can be suitably obtained.

[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 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 Molding Example 1 were crushed into about 5 mm squares with a crusher. The crushed product was dissolved in 400 parts of cyclohexane. Diatomaceous earth-supported nickel catalyst (manufactured by JGC Chemicals, N11
3) Add 2 parts, and at 190 ° C, 40 kg / cm with hydrogen
^The mixture was pressurized to 2 and stirred for 2 hours. After cooling to 70 ° C., the pressure was released, and the obtained solution was subjected to pressure 2. using a diatomaceous earth (manufactured by Showa Chemical Co., Ltd., Radiolite # 500) as a filter aid with a pressure filter (Fundafilter, manufactured by Ishikawajima-Harima Heavy Industries). 5kg /
Filtered through cm ² to remove the nickel catalyst. The cyclohexane, a volatile component, was removed from the solution using a cylindrical thin film concentrator / dryer (manufactured by Hitachi, Ltd., Control), and the operating conditions were adjusted to the first condition.
Step: temperature 270 ° C., pressure 100 Torr, second step: temperature 270 ° C., pressure 5 Torr. The polymer in the molten state obtained by removing cyclohexane was 27
The mixture was melt-extruded from a die into a strand in a class 1000 clean room through a polymer filter (manufactured by Fuji Filter) at 0 ° C., and cut with a pelletizer to obtain 93 parts of regenerated pellets.

Example 2 The same processing as in Example 1 was carried out except that the optical disk substrate of Molding Example 2 was used instead of the optical disk substrate of Molding Example 1, and 94 parts of regenerated pellets were obtained.

Example 3 The optical disk substrate of molding example 2 was used in place of the optical disk substrate of molding example 1, and 2 parts of a nickel catalyst supported on alumina (manufactured by JGC Chemicals, N163A) were used instead of the nickel catalyst supported on diatomaceous earth. Except for the treatment at ℃, the same treatment as in Example 1 to obtain 93 parts of regenerated pellets.

Example 4 Instead of the nickel catalyst supported on alumina, a palladium catalyst supported on alumina (manufactured by NE Chemcat, 5% Pd
Alumina powder (1 part) was treated in the same manner as in Example 1 except that the mixture was treated at 140 ° C. to obtain 95 parts of regenerated pellets.

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. Cylinder temperature 25 with a single screw extruder (VS-40, manufactured by Tanabe Plastic Machinery Co., Ltd.)
At 0 ° C., the crushed material is melt-extruded from a die into a strand,
By cutting with a pelletizer, 98 parts of regenerated pellets were obtained.

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). Foreign substance content: As a toluene solution (concentration: 2% by weight)
Measured by a light scattering type fine particle detector (KS-58, manufactured by Rion).

[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; DISC-5 Molding conditions: resin temperature: 300 ° C, mold temperature: 110
℃, molding cycle time: 60sec

Example 5 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 5 Pellets of Example 3 91 630 Comparative example 3 Pellets of Comparative example 2 84 630

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Claims (1)

[Claims] 1. A method for reusing an alicyclic structure-containing polymer resin molded article, comprising a step of performing a hydrogenation treatment. .