JP2008143018A - Resin mold regenerated resin for curable resin molding - Google Patents

Abstract

A resin-type regenerated resin formed from a resin material containing an alicyclic structure-containing thermoplastic resin and used for molding a curable resin, wherein the resin mold formed from the regenerated resin mold is curable. To provide a recycled resin that can be repeatedly used and can form a curable resin molded product with low PI error when reused for resin molding.
A resin mold for curable resin molding, wherein the resin mold is formed from a resin material containing an alicyclic structure-containing thermoplastic resin, and is contained in the recycled resin. A regenerated resin for a resin mold for forming a curable resin, wherein the number of foreign matters having a size of 5 μm or more is 100 / g or less.
[Selection figure] None

Description

  The present invention relates to a regenerated resin for a resin mold for curable resin molding, and more specifically, a resin mold formed from a resin composition containing an alicyclic structure-containing thermoplastic resin is used as a resin mold for curable resin molding. Then, the present invention relates to a regenerated resin obtained by regenerating the resin mold.

  Molded body made of alicyclic structure-containing thermoplastic resin is excellent in heat distortion resistance and moisture absorption deformation resistance, and also has excellent mold releasability from curable resin. It is used as The resin mold can transfer a concavo-convex shape with high surface accuracy to a curable resin. Therefore, the resin mold can be suitably used as, for example, a resin stamper used for manufacturing an optical disk using a photocurable resin.

  For example, Japanese Patent Application Laid-Open No. 2000-108137 (Patent Document 1) has a cavity inner surface shape for transferring the concavo-convex shape on the surface of the molded body in a method for producing a concavo-convex shape on the surface, and In addition, a method for producing a molded article having a concavo-convex shape on the surface, in which a curable resin is filled into a resin mold made of an alicyclic structure-containing thermoplastic resin and cured, is disclosed.

  Japanese Unexamined Patent Application Publication No. 2004-39136 (Patent Document 2) discloses a transparent stamper for forming an optical multilayer recording medium made of an amorphous polyolefin resin, and a method for producing an optical multilayer recording medium using the transparent stamper. Yes. The manufacturing method described in Patent Document 2 includes a step of laminating an uncured photocurable resin layer and a transparent stamper made of an amorphous polyolefin resin in this order on a substrate; by light transmitted through the transparent stamper. A step of curing the uncured photocurable resin layer; and a step of removing the transparent stamper. Patent Document 2 discloses a cycloolefin polymer (that is, a kind of thermoplastic resin containing an alicyclic structure) as an amorphous polyolefin-based resin.

  A resin mold made of an alicyclic structure-containing thermoplastic resin can be used as a resin mold and then pulverized into a recycled resin. The recycled resin can be reused as a raw material for the resin molding. However, the resin mold (recycled resin mold) obtained by molding the recycled resin has a problem in its practical performance. Specifically, when this recycled resin mold is used as a resin mold for curable resin molding, cracks occur in the recycled resin mold when the curable resin molded article and the resin mold are separated after molding. easy.

  Japanese Unexamined Patent Publication No. 2006-96032 (Patent Document 3) discloses a recycled resin molded article obtained by molding a resin material obtained by pulverizing a resin molded article made of an alicyclic structure-containing thermoplastic resin. A recycled resin molded body in which the number of foreign matters having a major axis of 30 μm or more in the molded body is 100/10 g or less is disclosed. Patent Document 3 shows a recycled resin stamper as a recycled resin molded body, and as a method for producing the recycled resin stamper, a resin stamper made of an alicyclic structure-containing thermoplastic resin is used one or more times. , Crushing in an ambient environment of air cleanliness class 6 or higher, the obtained pulverized material is plasticized by passing it through a transport pipe having an inner surface roughness Rmax of 1.8 μm or less using a metal material A method is disclosed in which a pulverized product in a molding machine is molded after being transported to a molding machine in which an inert gas is injected into the part.

  For example, when the recycled resin molded article described in Patent Document 3 is used as a resin stamper for molding a photocurable resin molded article, cracks do not occur when it is peeled off from the cured photocurable resin molded article. It can be reused three or more times. However, the resin stamper formed from the alicyclic structure-containing thermoplastic resin is excellent in releasability from the cured photocurable resin, but a part of the cured photocurable resin is not removed on the surface. Tend to remain. Therefore, the recycled resin molded product contains a photocurable resin component (photocured resin after curing) attached to the surface of the resin stamper before regeneration. In the method described in Patent Document 3, the photocurable resin component in the recycled resin cannot be removed. Therefore, when the recycled resin molded product is used as a resin stamper for producing an optical recording medium, the obtained optical recording medium has a high PI (Parity of Inner-code) error, and it is difficult to exhibit sufficient practical performance. Met.

JP 2000-108137 A Japanese Unexamined Patent Application Publication No. 2004-039136 JP 2006-096032 A

  An object of the present invention is a resin-type regenerated resin formed from a resin material containing an alicyclic structure-containing thermoplastic resin and used for molding a curable resin, the resin mold formed from the regenerated resin mold It is an object of the present invention to provide a recycled resin that can be repeatedly used and can form a curable resin molded product having a low PI error when it is reused for molding a curable resin.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have used a resin mold formed from a resin material containing an alicyclic structure-containing thermoplastic resin at least once for molding a curable resin molded body. After that, it was found that a recycled resin suitable for molding of the recycled resin mold can be obtained by arranging a step of removing the adhering curable resin component at the time of recycling. The present invention has been completed based on these findings.

  According to the present invention, there is a regenerated resin of a resin mold for curable resin molding, wherein the resin mold is formed from a resin material containing an alicyclic structure-containing thermoplastic resin, and in the regenerated resin The number of foreign matters having a size of 5 μm or more contained in the resin is 100 / g or less.

  According to the present invention, a resin-type regenerated resin formed from a resin material containing an alicyclic structure-containing thermoplastic resin and used for molding a curable resin, wherein the resin mold formed from the regenerated resin is When reused for molding a curable resin, it is possible to provide a recycled resin that can be repeatedly used and can mold a curable resin molded product having a low PI error.

  The resin mold for curable resin molding used for the reuse of the present invention is formed from a resin material containing an alicyclic structure-containing thermoplastic resin as a resin component. The alicyclic structure-containing thermoplastic resin used in the present invention is a polymer containing a repeating unit having an alicyclic structure. The polymer is a polymer having an alicyclic structure in the main chain and / or side chain. The resin material may be only an alicyclic structure-containing thermoplastic resin, but may contain various additives such as an antioxidant.

  The alicyclic structure-containing thermoplastic resin can form a fine structure with high accuracy. A resin mold formed from a resin material containing an alicyclic structure-containing thermoplastic resin is excellent in heat resistance, moisture absorption deformation resistance, and durability, and can be used repeatedly. The resin mold is also excellent in releasability from a curable resin molded body of a curable resin (thermosetting resin, photocurable resin, etc.).

<Aricyclic structure-containing thermoplastic resin>
Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure, and a cycloalkane structure is preferable from the viewpoint of thermal stability. Although there is no restriction | limiting in particular in carbon number which comprises an alicyclic structure, Usually, 4-30 pieces, Preferably it is 5-20 pieces, More preferably, it is 5-15 pieces. When the number of carbon atoms constituting the alicyclic structure is in this range, heat resistance and flexibility are excellent.

  The proportion of the repeating unit having an alicyclic structure in the alicyclic structure-containing thermoplastic resin may be appropriately selected according to the purpose of use, but is usually 50% by weight or more, preferably 70% by weight or more, more preferably. Is 90% by weight or more. If the number of repeating units having an alicyclic structure is too small, the heat resistance is undesirably lowered. In addition, repeating units other than the repeating unit which has an alicyclic structure in an alicyclic structure containing polymer resin are suitably selected according to the intended purpose.

  Specific examples of the alicyclic structure-containing thermoplastic resin include (i) a norbornene polymer, (ii) a monocyclic olefin polymer, (iii) a cyclic conjugated diene polymer, and (iv) a vinyl alicyclic carbonization. Examples thereof include hydrogen polymers and hydrides thereof. Among these, norbornene-based polymers are preferable from the viewpoints of transparency and moldability.

  (I) Specific examples of the norbornene-based polymer include a ring-opening polymer of a norbornene-based monomer, a ring-opening copolymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization, and These hydrides, addition polymers of norbornene monomers, addition copolymers with other monomers copolymerizable with norbornene monomers, and the like can be mentioned. Among these, from the viewpoint of transparency, a ring-opening (co) polymer hydride of a norbornene monomer is particularly preferable.

  In the present invention, the norbornene monomer is represented by the formula (I)

It is a compound which has the norbornene structure represented by these.

Examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene), tricyclo [4.3.0.1 ² , ⁵ ] deca-3,7-diene. (common name: dicyclopentadiene), 7,8-tricyclo [4.3.0.1 ^{2, 5]} dec-3-ene (common name: methanolate tetrahydrofluorene), tetracyclo [4.4.0. 1 ² , ⁵ . 1 ⁷ , ¹⁰ ] dodec-3-ene (common name: tetracyclododecene), derivatives of these compounds (for example, those having a substituent in the ring), and the like. Here, examples of the substituent include an alkyl group, an alkylene group, an alkoxycarbonyl group, and a carboxyl group.

  In addition, these substituents may be the same or different and a plurality may be bonded to the ring. Norbornene monomers can be used alone or in combination of two or more.

  Other monomers capable of ring-opening copolymerization with norbornene monomers include, for example, monocyclic olefins such as cyclohexene, cycloheptene, and cyclooctene and derivatives thereof; cyclic conjugated dienes such as cyclohexadiene and cycloheptadiene; Derivatives thereof; and the like.

Ring-opening polymers of norbornene monomers and ring-opening copolymers of norbornene monomers and other monomers copolymerizable therewith are polymerized in the presence of a ring-opening polymerization catalyst. Can be obtained.
As the ring-opening polymerization catalyst, a commonly used known catalyst can be used.

  A hydride of a ring-opening copolymer of a norbornene monomer and a ring-opening copolymer of the norbornene monomer and another monomer capable of ring-opening copolymerization is prepared by adding a known hydrogenation catalyst. The carbon-carbon unsaturated bond can be obtained by hydrogenating preferably 90% or more, more preferably 99% or more.

  Examples of other monomers that can be addition-copolymerized with norbornene-based monomers include, for example, α-olefins having 2 to 20 carbon atoms such as ethylene and propylene, and derivatives thereof; cycloolefins such as cyclobutene and cyclopentene, and these Derivatives; non-conjugated dienes such as 1,4-hexadiene and the like. These monomers can be used alone or in combination of two or more. In these, an alpha olefin is preferable and ethylene is more preferable.

  Norbornene monomer addition polymers and addition copolymers of norbornene monomers and other monomers copolymerizable therewith are obtained by polymerizing the monomers in the presence of an addition polymerization catalyst. Obtainable. As the addition polymerization catalyst, a commonly used known catalyst can be used.

  (Ii) Examples of the monocyclic olefin polymer include addition polymers such as cyclohexene, cycloheptene, and cyclooctene.

  Examples of the cyclic conjugated diene polymer include polymers obtained by 1,2-addition polymerization or 1,4-addition polymerization of cyclic conjugated diene monomers such as cyclopentadiene and cyclohexadiene, and hydrides thereof. be able to.

  (Iii) The vinyl alicyclic hydrocarbon polymer is a polymer having a repeating unit derived from vinyl cycloalkane or vinyl cycloalkene. Examples of the vinyl alicyclic hydrocarbon polymer include polymers of vinyl alicyclic hydrocarbon compounds such as vinyl cycloalkanes such as vinyl cyclohexane, vinyl cycloalkenes such as vinyl cyclohexene, and hydrides thereof; styrene, α-methyl Examples thereof include hydrides of aromatic moieties of polymers of vinyl aromatic hydrocarbon compounds such as styrene.

  (Iv) The vinyl alicyclic hydrocarbon polymer is a random copolymer of a vinyl alicyclic hydrocarbon compound or a vinyl aromatic hydrocarbon compound and other monomers copolymerizable with these monomers. Further, it may be a copolymer such as a block copolymer and a hydride thereof. Examples of the block copolymerization include diblock, triblock, or more multiblock and gradient block copolymerization, but are not particularly limited.

  These alicyclic structure-containing thermoplastic resins can be used alone or in combination of two or more.

  The molecular weight of the alicyclic structure-containing thermoplastic resin is calculated as standard polyisoprene (eluent) measured by gel permeation chromatography (GPC) using cyclohexane (but toluene is used when the resin is not dissolved) as an eluent. Is toluene, the weight average molecular weight (Mw) measured by standard polystyrene conversion is usually 1,000 to 1,000,000, preferably 5,000 to 500,000, more preferably 10,000 to It is in the range of 200,000. When the weight average molecular weight (Mw) of the alicyclic structure-containing thermoplastic resin is in this range, the balance between the mechanical strength of the resin mold and the moldability is preferred.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the alicyclic structure-containing thermoplastic resin is not particularly limited, but is usually 1.0 to 10.0, preferably 1.0 to 6. 0.0, more preferably in the range of 1.1 to 4.0. By adjusting the molecular weight distribution in such a range, the mechanical strength and moldability of the resin mold are well balanced.

  The glass transition temperature (Tg) of the alicyclic structure-containing thermoplastic resin may be appropriately selected according to the purpose of use, but is usually 50 to 400 ° C, preferably 70 to 350 ° C, more preferably 90 to 300 ° C. It is a range. The higher the Tg of the resin, the higher the durability because it can withstand deformation due to heat generation during curing of the polymerizable monomer, for example. On the other hand, if the Tg of the resin is too high, it may be difficult to process a fine shape. Accordingly, when the Tg of the resin is within the above range, the durability and molding processability of the resin mold are highly balanced and suitable.

  The melt flow rate (MFR) measured according to JIS K7210 at a temperature of 280 ° C. and a load of 2.16 kg of the alicyclic structure-containing thermoplastic resin may be appropriately selected according to the purpose of use, but is usually 1 to 200 g / 10 min. When the thickness is in the range of preferably 2 to 180 g / 10 minutes, more preferably 3 to 150 g / 10 minutes, and most preferably 50 to 100 g / 10 minutes, the moldability of the resin mold having a fine shape is optimal and preferable. .

  A resin mold containing an alicyclic structure-containing thermoplastic resin to be reused in the present invention is an alicyclic structure-containing thermoplastic resin, or a known molding method using a resin composition containing an additive in the resin. It can manufacture by shape | molding by.

  In the alicyclic structure-containing thermoplastic resin, a lubricant such as a hydroxyl group-containing fatty acid ester compound, an anti-aging agent such as a phenol type or a phosphorus type, a benzophenone type, if desired, as long as the effect of the present invention is not substantially inhibited. Various additives such as UV stabilizers such as benzotriazole, antistatic agents such as amines, and weathering stabilizers such as hindered amines may be added.

<Resin type>
The resin mold used for the reuse of the present invention is used for molding a curable resin, and usually has a cured resin component attached thereto. The resin mold used for the reuse of the present invention is not particularly limited as long as it is used for molding a curable resin. For example, an optical recording medium, an optical lens, a spectacle lens, a contact lens, a light guide plate, a light diffusion plate, etc. The resin mold for manufacture of this is mentioned. The resin mold here is not particularly limited, and may be a plate having a concavo-convex surface even if it has a cavity provided with a frame.

  For example, in the manufacture of an optical recording medium, for example, in the case of a multilayer optical recording medium, first, first phase change recording is performed on a part of a substrate having a recording pit forming convex portion formed on one side by resin molding or etching. A layer is formed as a base layer. Next, an uncured curable resin is applied onto the base layer by means such as spin coating to form a curable resin layer, and a resin stamper (corresponding to a resin mold) is pressed against the uncured curable resin layer. Next, the curable resin layer is cured by ultraviolet rays or heat to form a curable resin layer, and then the resin stamper is peeled off. Thereafter, a multilayer optical recording medium can be obtained by laminating the second phase change recording layer and then laminating the cover layer.

  As described above, in the production of the optical recording medium, the resin stamper is pressed against the curable resin layer, and after the curable resin layer is cured, the resin stamper is peeled off. Usually attached.

<Curable resin>
The curable resin is not particularly limited, and examples thereof include a thermosetting resin and an active energy ray curable resin. Among these, an active energy ray curable resin is preferable, and an ultraviolet curable resin is more preferably used.

  Examples of the thermosetting resin include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation resin, silicon resin, polyresin Examples thereof include siloxane resins. Further, these resins can be used by adding a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier and the like, if necessary.

  The active energy ray-curable resin is a resin obtained by curing a prepolymer, an oligomer and / or a monomer having a polymerizable unsaturated bond or an epoxy group in a molecule by irradiation with energy rays. An active energy ray refers to an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or crosslinking molecules, and usually an ultraviolet ray or an electron beam is used.

  Prepolymers or oligomers having a polymerizable unsaturated bond or epoxy group in the molecule include unsaturated polyesters such as unsaturated dicarboxylic acid and polyhydric alcohol condensates; polyester methacrylate, polyether methacrylate, polyol methacrylate, melamine Examples include methacrylates such as methacrylate, polyester acrylates, epoxy acrylates, urethane acrylates, polyether acrylates, polyol acrylates, acrylates such as melamine acrylate, and cationic polymerization type epoxy compounds.

  Examples of the monomer having a polymerizable unsaturated bond or an epoxy group in the molecule include styrene monomers such as styrene and α-methylstyrene; methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, Acrylic esters such as butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, and phenyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, Methacrylic acid esters such as lauryl methacrylate; acrylic acid-2- (N, N-diethylamino) ethyl, acrylic acid-2- (N, N-dimethylamino) ethyl, acrylic acid-2- (N, N-di) Benzylamino) methyl Unsaturated substituted amino alcohol esters such as acrylic acid-2- (N, N-diethylamino) propyl; unsaturated carboxylic acid amides such as acrylamide and methacrylamide; ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl Glycol diacrylate, 1,6-hexanediol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, 2-hydroxy acrylate, 2-hexyl acrylate, phenoxy Ethyl acrylate, ethylene glycol diacrylate, 1,6-hexanediol diacrylate, trimethylol Multifunctional acrylates such as propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate; trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, pentaerythritol tetrathioglycolate And the like, polythiols having two or more thiol groups in the molecule, and the like. In the present invention, prepolymers, oligomers and / or monomers having a polymerizable unsaturated bond or an epoxy group in these molecules can be used alone or in combination of two or more.

  The active energy ray-curable resin usually contains a polymerization initiator together with a prepolymer and an oligomer having a polymerizable unsaturated bond or an epoxy group in the molecule.

<Reuse of resin mold>
The method for obtaining the recycled resin of the present invention is not particularly limited. For example, (1) a method of mechanically removing a curable resin component (cured curable resin) adhering to a resin mold in advance (hereinafter referred to as “mechanical removal method”). And a resin mold such as a resin stamper (2) in a solution state (hereinafter sometimes referred to as “solution method”) or (3) in a molten state (hereinafter sometimes referred to as “melting method”) And passing through a suitable filter, respectively.

(1) Mechanical removal method The method for mechanically removing the curable resin component adhering to the resin mold is not particularly limited. For example, when the resin mold is a resin stamper used for manufacturing an optical recording medium, the optical recording medium When the curable resin is applied on the base layer in the manufacturing process, the amount is excessive. Therefore, when the resin stamper is pressed against the curable resin layer, the excess curable resin tends to collect on the outer peripheral portion of the base layer. As a result, a large amount of the curable resin adheres to the portion corresponding to the outer periphery of the base layer at the position overlapping with the base layer of the resin stamper. Therefore, the portion corresponding to the outer periphery of the base layer overlapping with the base layer of the resin stamper is cut off with a blade or the like. It is done. The cut portion of the resin stamper is usually 3% or more, preferably 5% or more, more preferably 10% or more of the inside of the substrate layer diameter at a position corresponding to the periphery of the substrate layer at a position overlapping the substrate layer.

  After mechanically removing the curable resin component adhering to the resin mold, it can be used in the form of pellets by extruding from a melt extruder if necessary, but can be used in combination with the melting method or solution method shown below. Further, it is preferable because the amount of foreign matter can be further reduced.

(2) Solution method The method for removing the curable resin component by the solution method is not particularly limited. For example, an alicyclic structure-containing thermoplastic resin-containing solution in which a resin mold is dissolved is used. (I) The pore size is usually 50 μm or less. And a method of filtering with a mechanical filter of preferably 1 μm or less, particularly preferably 0.3 μm or less, and (ii) a method of filtering with a filtration filter having a charge trapping function. Among these methods, the method (ii) using a filtration filter having a charge trapping function has a high ability to remove fine foreign matter, and filtration with a mechanical filter using an opening can remove fine foreign matter that passes therethrough. Is preferred.

  In the case of a resin stamper, the resin stamper is directly or pulverized to an appropriate size, mixed with a good solvent and dissolved to obtain a solution. In view of easiness of dissolution, the size (the length of the shortest side of the particles) is preferably 50 mm or less, more preferably 20 mm or less, and particularly preferably 10 mm or less. The good solvent varies depending on the type and structure of the alicyclic structure-containing thermoplastic resin, and an appropriate solvent is selected from the viewpoint of ease of handling and ease of drying. Specifically, aromatic solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chloroform, trichrene and chlorobenzene; alicyclic hydrocarbons such as hydrogenated products of cyclohexane, methylcyclohexane, decalin and dicyclopentadiene Examples of the solvent include cyclic ether solvents such as tetrahydrofuran. The density | concentration of the solid content in the case of filtration is 1-40 weight% normally, Preferably it is 5-35 weight%, More preferably, it is 10-30 weight%. If the concentration of the solution is excessively low, it is necessary to process a large amount of the solution. Conversely, if the concentration of the solution is excessively high, the filterability is deteriorated.

  A filter having a charge trapping function electrically traps and removes charged foreign substances. Usually, a filter medium having a charge applied thereto is used. In general, a zeta potential filtration filter in which the zeta potential is controlled is used. As a 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, etc. A filter in which a positive charge modifier is added to the filter medium is used.

  Examples of other filter media include fibers 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. It is done. Examples of other positive charge modifiers include melamine formaldehyde cation colloid, inorganic cation colloidal silica, and the like. In the market, positively charge-denaturing filtration filters are sold by Cuno under the trademark “Zetaplus”.

  Filtration with a filtration filter having a charge trapping function is usually performed in combination with a mechanical filtration filter because the processing capacity is not necessarily high. The order of combination is not particularly limited, but is usually used in the order of mechanical filtration filter and then charge trapping function filter.

  The mechanical filtration filter is not particularly limited as long as it is not adversely affected by the solvent. For example, a fiber or membrane filter made of polypropylene, polyethylene, PTFE, or the like, a fiber filter made of cellulose, or glass fiber. Filter, inorganic filter such as diatomaceous earth, and metal fiber filter. The pore size of the mechanical filter is not particularly limited, but is usually 50 μm or less, preferably 1 μm or less, more preferably 0.3 μm or less. These mechanical filtration filters can be used alone or in combination of two or more. When a filter having a charge trapping function is not used, it is also preferable to repeat the filtration operation twice or more using a mechanical filter having a pore size of 0.5 μm or less, preferably 0.3 μm or less.

  The solution after filtration can be reused as it is.For example, the volatile components are removed in a closed system so that foreign matters do not enter from the outside environment, and the solution is concretely used in a clean environment such as a clean room. In general, it is preferable to pelletize in an environment in which the cleanliness specified in ISO 14644-1 is normally strictly controlled to class 6 or less, preferably class 5 or less.

  As a method for removing the solvent and other volatile components, a known method such as (i) a coagulation method or (ii) a direct drying method can be employed.

  (I) The coagulation method is a method of precipitating the resin component by mixing the solution with a poor solvent of the alicyclic structure-containing polymer resin, and the kind of poor solvent is the kind of the alicyclic structure-containing polymer resin. For example, polar solvents such as alcohols such as ethyl alcohol, n-propyl alcohol or i-propyl alcohol, ketones such as acetone or MEK, and esters such as ethyl acetate or butyl acetate can be used. . The component containing the powdered resin obtained by solidification can be dried by heating, for example, in vacuum, nitrogen or air, and further extruded from a melt extruder as necessary to be used in the form of pellets. .

  (Ii) The direct drying method is a method disclosed in, for example, Japanese Patent Application Laid-Open No. 4-170425, and the like, and is a method of removing the solvent by heating the solution under reduced pressure. This method can be carried out using a known apparatus such as a centrifugal thin film continuous evaporation dryer, a scratched heat exchange type continuous reactor type dryer or a high viscosity reactor device. The degree of vacuum and temperature are appropriately selected depending on the device and are not limited. Furthermore, it can be extruded from a melt extruder and used in the form of pellets if necessary.

(3) Melting method The melting method comprises a metal filter having a pore size of 0.5 to 50 μm, which is heated and melted by pressing a resin mold as it is or pulverized to an appropriate size, and is usually pressurized. It is performed by filtering with a filter called a polymer filter. When the resin mold is in a lump shape, the size (length of the longest side of the particles) is preferably 20 mm or less, more preferably 10 mm or less, and particularly preferably 8 mm or less because of easy melting. It is preferable.

The heat melting is performed by a melt extruder having a mechanism for heating the resin in a molten state, such as a single screw extruder or a twin screw extruder or a combination of these and a gear pump. The temperature for heating and melting is not particularly limited, but is preferably in the range of 200 ° C to 320 ° C, more preferably 220 ° C to 300 ° C, and particularly preferably 240 ° C to 280 ° C. When it is in this range, there is no heat deterioration of the obtained molten resin after filtration, and the filtration efficiency is high and preferable. The pressure for pressurizing is particularly but not limited preferably 5 to 100 kg / cm ^2, more preferably 10~90kg / cm ^2, particularly preferably from 15~80kg / cm ^2. When it is in this range, there is no heat deterioration of the obtained molten resin after filtration, and the filtration efficiency is high and preferable.

  A foreign substance can be removed by attaching a polymer filter to the outlet of the melt extruder and passing the resin component in a molten state. The polymer filter has a structure in which, for example, fine mesh filters are stacked in multiple stages so as to increase the contact area, and can be obtained from Fuji Filter, Nichidai, etc. The pore diameter is 50 μm or less, preferably 10 μm or less, particularly preferably 5 μm or less.

  At the time of melting for filtration, the resin residence time is preferably within 60 minutes, more preferably within 40 minutes, and particularly preferably within 20 minutes. At the time of melt molding, the alicyclic structure-containing thermoplastic resin is preferably melted in a state where it is not exposed to 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. For this purpose, specifically, an inert gas such as nitrogen is allowed to flow into the resin component charging part (often referred to as a hopper) of the melt extruder, or the hopper part is evacuated to a vacuum by the above structure. The preferable oxygen concentration can be realized.

  After passing through a filter in a molten state and filtering, it is usually drawn into a rod shape and cut with a strand cutter to form a pellet-shaped molding material. In that case, in order to prevent foreign matter from entering from the outside environment, the cleanliness specified in ISO 14644-1 is usually class 6 or less, preferably class 6 in a clean environment such as a clean room. 5 or less is preferable.

<Adsorption treatment>
In the present invention, it is preferable to perform the adsorption treatment before and / or preferably before the step of removing the curable resin component adhering to the resin mold. This treatment is usually performed by bringing the alicyclic structure-containing thermoplastic resin into a solution state. By performing the adsorption treatment, uncured components in the curable resin component can also be removed.

The adsorbent is not particularly limited, but is a hydrogenation in which a metal such as Ni, Pd or the like is supported on SiO ₂ , Al ₂ O ₃ such as synthetic zeolite, natural zeolite, activated alumina, activated clay, diatomaceous earth, or the like. The well-known heterogeneous catalyst used for reaction is mentioned. When the heterogeneous catalyst used for the hydrogenation reaction is used as the adsorbent, the heterogeneous catalyst used for the hydrogenation reaction can be reduced in advance or during the adsorption treatment.

The specific surface area of the adsorbent is usually 50 m ² / g or more, preferably 100 m ² / g or more, more preferably 200 m ² / g or more, and the pore volume is usually 0.5 cm ³ / g or more, preferably 0. .6cm ³ / g or more, more preferably not less than 0.7 cm ³ / g. If the specific surface area and pore volume are small, the adsorption capacity is inferior. The size of these adsorbent particles is usually 0.2 μm or more, preferably 10 μm to 3 cm, more preferably 100 μm to 1 cm. If it is too small, the processing speed may be slow, and if it is too large, the packing rate of the column may be deteriorated and the processing time may be prolonged.

  The temperature at which the adsorption treatment is performed is appropriately selected depending on the adsorbent to be used, but is usually 0 to 200 ° C, preferably 20 to 150 ° C, and more preferably 30 to 100 ° C.

  Examples of the adsorption treatment include (i) a method of passing a solution through an adsorbent packed column, (ii) a method of adding an adsorbent, stirring, removing the adsorbent by filtration and the like as described above. .

(I) In a method in which a solution in which a resin mold is dissolved is passed through an adsorbent packed column, the packing rate is ρ (g / m ³ ), the specific surface area is S (m ² / g), and the residence time is t (sec). Processing may be performed so that ρSt (seconds / m) sometimes becomes 10 ⁹ or more. Usually, S is about 100 to 1000 m ² / g and ρ is about 4 to 8 × 10 ⁵ g / m ³ , so the residence time may be 30 seconds or more.

(Ii) In the method of adding an adsorbent to a solution in which a resin mold is dissolved, the specific surface area is S (m ² / g), the adsorbent addition amount is m (g), the stirring time is t (seconds), and the solution to be treated When the amount is V (g) and the solution concentration is c, Smt / Vc (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, preferably May be 5 or more, more preferably 10 or more, and t (seconds) may be 100 or more, preferably 200 or more, more preferably 300 or more.

  Filtration is performed after the adsorbent treatment to remove foreign substances such as the adsorbent and the curable resin component contained in the alicyclic structure-containing thermoplastic resin.

<Recycled resin>
In the recycled resin of the present invention, other synthetic resins and various compounding agents (hereinafter sometimes referred to as “compounding agents”) can be mixed and used depending on the purpose of use.

  Other synthetic resins include polyethylene, polypropylene, polyolefins such as poly (4-methyl-1-pentene); polybutadiene, polyisoprene, styrene / butadiene / styrene block copolymer (SBS), and styrene / isoprene / styrene. Rubber such as block copolymer (SIS), SBS hydrogenated product (SEBS), SIS hydrogenated product (SEPS); polystyrene, poly (meth) acrylate, polycarbonate, polyester, polyether, polyamide, polyimide, polysulfone, And resins such as polyphenylene sulfide. These other synthetic resins may be used alone or in combination of two or more. Moreover, the ratio is suitably selected according to the purpose of use.

  The compounding agent is not particularly limited as long as it is usually used in thermoplastic resin materials, and is appropriately selected according to the purpose of use. For example, known antioxidants, ultraviolet absorbers, light stabilizers. And compounding agents such as near infrared absorbers, colorants such as dyes and pigments, lubricants, plasticizers, antistatic agents, and fluorescent brighteners.

  Antiaging agents include the above-mentioned phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, etc. Among them, phenolic antioxidants are preferable, and alkyl-substituted phenolic antioxidants. Agents are particularly preferred.

  These antioxidants can be used alone or in combination of two or more. The blending amount of the antioxidant is appropriately selected depending on the purpose of reuse, but is usually 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the polymer component.

  The method for mixing the compounding agent and the like is not particularly limited. When the foreign matter is removed by the melting method, following the removal of the foreign matter, or by re-melting the pellet after the removal of the foreign matter and kneading, the necessary compounding agent can be added or added as a solution. The solvent may be dried as necessary.

  When foreign matter is removed by the solution method, the solvent may be dried as needed after adding and mixing the necessary compounding agents, etc., or melting after drying the solvent to remove it. It may be added after kneading.

  As a method of melt kneading, for example, there is a method of kneading a resin in a molten state with a mixer, a biaxial kneader or the like, and a melt kneading method is preferable because a homogeneous material can be obtained.

  In the case of melt-kneading, it is appropriate that the resin temperature is set to 330 ° C. or less, more preferably 300 ° C. or less, and particularly preferably 280 ° C. or less from (temperature higher by 70 ° C. than the glass transition temperature of the resin). Yes, a sufficiently uniform mixed state can be obtained by applying sufficient shear. The kneading conditions such as the screw shape are appropriately selected depending on the type and shape of the kneader. After melt-kneading, it is usually extruded in a rod shape in the molten state, cut into an appropriate length with a strand cutter, and formed into pellets.

<Molding method>
The method for molding the recycled resin of the present invention is not particularly limited and is appropriately selected depending on the purpose. For example, injection molding, press molding, extrusion blow molding, injection blow molding, multilayer blow molding, connection blow molding, double wall Examples include blow molding, stretch blow molding, vacuum molding, and rotational molding. When the reclaimed resin of the present invention is molded into a resin stamper for producing an optical recording medium, the injection molding method and the press molding method are preferable because they can reduce the in-plane variation of the uneven shape. Examples of the press molding method include a method of heating and pressurizing in an uneven mold for molding a sheet or film produced by a melt extrusion method.

  Although molding conditions are set as appropriate, the resin temperature is usually 100 to 400 ° C, preferably 200 to 380 ° C, more preferably 200 to 370 ° C. The injection pressure is usually 0.1 to 100 MPa, preferably 0.5 to 50 MPa.

  The shape of the resin stamper in the case of reusing as a resin stamper is appropriately selected depending on the shape of the laminate to be manufactured, but has a convex portion on the surface in contact with the curable resin, and the height of the convex portion is 10 nm to It is preferable that the pitch of the convex portions is 200 nm and 0.2 μm to 2.0 μm.

  The thickness of the resin stamper is not particularly limited, but is preferably in the range of 0.3 to 2 mm, more preferably in the range of 0.3 to 1.5 mm, and particularly in the range of 0.5 to 1.0 mm. preferable.

  If the thickness of the resin stamper is within this range, the resin stamper has appropriate flexibility, so that when the resin stamper is peeled off from the curable resin layer, the resin stamper can be peeled off while being deformed. Peeling is easy and it is difficult to damage the surface of the laminate.

<Characteristics of recycled resin>
The recycled resin of the present invention is excellent in transparency, releasability, and transferability because there are few foreign substances such as curable resin components.

  The number of foreign substances of 5 μm or more measured with a particle counter (manufactured by HACH ULTRA ANALYTICS, HIAC ROYCO 8000A) using a 1 wt% tetralin solution of the recycled resin of the present invention is 100 / g, preferably 50 / g, The number is preferably 30 / g or less, particularly preferably 10 / g or less.

  It can be confirmed that the recycled resin of the present invention is excellent in transparency by, for example, making the recycled resin a cyclohexane solution having a concentration of 10% by weight and measuring light transmittance measured at a wavelength of 365 nm and an optical path length of 10 mm. Usually, it is 85% or more, preferably 87% or more, and more preferably 90% or more. Within this range, when the recycled resin is used as a resin stamper for manufacturing an optical recording medium, the active energy rays are well transmitted through the resin stamper, so that the curing time of the curable resin is short and sufficiently cured. Can do.

  The fact that the reclaimed resin of the present invention is excellent in releasability is, for example, that the reclaimed resin is a resin stamper for an optical recording medium, and the load applied when the resin stamper is peeled from the curable resin layer is measured with a peel test device (STP, It is normally 15N or less, preferably 13N or less, more preferably 10N or less. Within this range, the resin stamper can be easily peeled off from the curable resin layer, and the resin stamper is repeatedly used because it is difficult for the curable resin to adhere to the fine uneven surface of the resin stamper or to deform the uneven surface. be able to.

  The reproduction resin of the present invention is excellent in transferability. For example, a DVD + R produced from the reproduction resin using a resin stamper for an optical recording medium is recorded with a commercially available recording drive, and SA-300 manufactured by Audio Development, Inc. The PI error is usually 280 or less, preferably 200 or less, more preferably 150 or less, still more preferably 120 or less, and particularly preferably 100 or less.

Hereinafter, the present invention will be described with reference to examples.
Measurement and evaluation of physical properties in Examples and Comparative Examples were performed by the following methods.

(1) Weight average molecular weight (Mw), number average molecular weight (Mn)
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured as standard polyisoprene conversion values by gel permeation chromatography (GPC) using cyclohexane as an eluent.

(2) Hydrogenation rate The hydrogenation rate was measured by ¹ H-NMR using deuterated chloroform as a solvent.

(3) Glass transition temperature (Tg)
The glass transition temperature (Tg) was measured according to JIS-K7121 using a differential scanning calorimeter (DSC6220, manufactured by SII Nanotechnology) under the condition of a heating rate of 10 ° C./min.

(4) Melt flow rate (MFR)
The melt flow rate (MFR) was measured at 280 ° C. and a 2.16 kg load based on JIS-K7210.

(5) Light transmittance The light transmittance is obtained by dissolving a pellet in cyclohexane at a concentration of 10% by weight to make a solution, placing it in a quartz cell with a 10 mm optical path, and a light transmittance at a wavelength of 365 nm (spectrophotometer: Japan). Spectroscopic V-570) was measured.

(6) Number of foreign matters The number of foreign matters was determined by using a particle counter (HIAC ROYCO 8000A, manufactured by HACH ULTRA ANALYTICS), a solution obtained by dissolving pellets in tetralin obtained by filtering a pellet through a cartridge filter having a pore size of 0.2 μm. Measured.

(7) Peel strength Peel strength was evaluated using a peel test apparatus STP [manufactured by Origin Electric Co., Ltd.] for the load applied when the resin stamper was peeled.

(8) PI error The PI error was recorded on each DVD + R produced by a commercially available recording drive, and the PI error was measured by SA-300 manufactured by Audio Development.

[Production Example 1]
(Production method of resin)
In a reactor at room temperature and in a nitrogen atmosphere, 250 parts of dehydrated cyclohexane was added, and 0.84 part of 1-hexene, 0.06 part of dibutyl ether and 0.11 part of triisobutylaluminum were added and mixed. 85 parts of tricyclo [4.3.0.1 ^2,5 ] dec-3-ene (hereinafter sometimes abbreviated as “DCP”), 8-ethyl-tetracyclo [4.4.0.1 ^{2, 5} . 1 ^7,10 ] dodec-3-ene (hereinafter abbreviated as “ETD”) and 15 parts of 0.7% toluene solution of tungsten hexachloride were continuously added over 2 hours for polymerization. . The polymerization conversion rate was 100%.

  The obtained polymerization reaction liquid was transferred to a pressure resistant hydrogenation reactor, and 5 parts of a diatomaceous earth-supported nickel catalyst (manufactured by Nissan Gardler; G-96D, nickel support rate of 58%) and 100 parts of cyclohexane were added, and 150 ° C. The reaction was carried out at a hydrogen pressure of 4.4 MPa for 8 hours. The reaction solution was subjected to pressure filtration (Hunda filter, manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd.) at a pressure of 0.25 MPa using Radiolite # 500 as a filter bed to remove the hydrogenation catalyst, and a colorless and transparent solution was obtained. Subsequently, 0.5 parts of antioxidant per 100 parts of the hydrogenated product: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 1010, manufactured by Ciba Geigy) (Hereinafter may be abbreviated as “antioxidant (A)”) was added to the obtained solution and dissolved. Next, it is sequentially filtered through a Zeta Plus filter 30H (pore size 0.5 to 1 μm, manufactured by Cuno filter), and further filtered through another metal fiber filter (pore size 0.4 μm, manufactured by Nichidai Corp.). Minutes removed.

  Next, using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.), the solvent is cyclohexane and other volatile components are removed from the solution at a temperature of 270 ° C. and a pressure of 1 kPa or less, and specified in ISO 14644-1. In a clean booth of clean class 6 or less, the melt was extruded from a die directly connected to a concentrator into a strand, cooled and pelletized to obtain a ring-opening copolymer resin hydride pellet (A).

  The pelletized ring-opening copolymer resin hydride has a weight average molecular weight (Mw) of 30,000, a number average molecular weight (Mn) of 10,000, a hydrogenation rate of 99.5%, and a glass transition point of 105. C and MFR were 60.5 g / 10 min.

[Production Example 2]
(Resin stamper molding)
Using the pellet (A) obtained in Production Example 1 as a resin material, injection molding was performed under the following conditions in a clean booth of clean class 6 or less defined in ISO 14644-1, and the inner diameter was 15 mm, the outer diameter was 120 mm, and the thickness was A disc-shaped resin stamper (A) having a thickness of 0.6 mm was obtained.
The pellets were heat-treated at 100 ° C. for 4 hours in a dryer until just before molding.

  The plasticizing apparatus used for injection molding is a mold having a cavity depth of 0.580 mm to which a Ni + stamper for DVD + R having a concentric uneven pattern with a width of 0.16 μm, an arrangement pitch of 0.32 μm, and a depth of 180 nm is attached. A mounted injection molding machine (SD40ER, manufactured by Sumitomo Heavy Industries, Ltd.) was used.

  A transfer pipe having a surface roughness Rmax of 1.8 μm inside the transfer pipe was used for transfer to the resin supply part of the pellet forming apparatus.

As molding conditions, the resin temperature (barrel set maximum temperature) was 360 ° C., the mold temperature was 90 ° C. on the mold fixing side, and 88 ° C. on the mold movable side. The maximum compression force of the mold is 35 tons, the initial opening width of the mold (initial mold opening amount) is set to 0.4 mm by the mold opening amount control, and the maximum compression force is 0.12 seconds after the start of injection. Closed the mold.
The amount of filled resin was 6.4 g, and the maximum injection speed was 180 mm / s.

  At the time of molding, nitrogen gas having a purity of 99.99% was introduced into the plasticizing part of the injection molding machine at a flow rate of 10 liters / minute.

[Production Example 3]
(Creation of polycarbonate substrate)
The substrate made of polycarbonate (Panlite AD5503 manufactured by Teijin Chemicals Ltd.) has the same shape as the resin stamper (A), and the same injection molding machine and Ni stamper were used. The polycarbonate pellets were heat-treated at 120 ° C. for 4 hours in a dryer until immediately before molding. As molding conditions, the resin temperature (barrel set maximum temperature) was 385 ° C., and the mold temperature was 124 ° C. on both the mold fixing side and the mold movable side. The maximum compression force of the mold is 38 tons, the initial opening width of the mold (initial mold opening amount) is set to 0.6 mm by controlling the opening amount of the mold, and the maximum compressive force is 0.10 seconds after the start of injection. Closed the mold.
The amount of filled resin was 6.4 g, and the maximum injection speed was 180 mm / s.

[Production Example 4]
(Create used stamper)
An ultraviolet curable resin (Nippon Kayaku Co., Ltd. DVD-595) was dropped onto the signal surface side of each of the resin stamper (A) and the polycarbonate substrate obtained as described above, and then rotated to remove excess. The ultraviolet curable resin was removed, and both were bonded together with a vacuum bonding apparatus (Cielo-RB manufactured by Shibaura Mechatronics).

  Thereafter, ultraviolet rays were irradiated through the resin stamper (A) to cure the ultraviolet curable resin, and then the resin stamper was peeled off to obtain a used resin stamper (B).

[Example 1]
(Recycle used stamper)
100 parts by weight of the used resin stamper (B) obtained in Production Example 4 was pulverized to about 5 mm square by a pulverizer in a clean booth of clean class 6 or less as defined in ISO 14644-1.

The pulverized product of the used resin stamper was dissolved in 400 parts of cyclohexane in a closed tank. 10 parts of activated alumina (manufactured by JGC Chemical Co., E1Q1) was added and stirred at 40 ° C. for 4 hours. After diatomaceous earth (Showa Chemical Co., Ltd., Radiolite # 500) was used as a filter aid, the alumina was removed by filtration at a pressure of 2.5 kg / cm ² with a pressure filter (Hunda filter, manufactured by Ishikawajima-Harima Heavy Industries). Furthermore, it filtered with the filter made from a metallic fiber (caliber 5 micrometers, Nichidai make). Next, after adding 0.1 part by weight of the antioxidant (A) per 100 parts by weight of the solution, cyclohexane, which is a volatile component, was added to the first operating condition using a cylindrical thin film concentration dryer (manufactured by Hitachi, Ltd., Contro). Step: temperature 270 ° C., pressure 100 Torr, second step: temperature 270 ° C., pressure 5 Torr. In the melted state, it was melt extruded from a die into a strand in a clean booth of clean class 6 or less defined in ISO 14644-1, and cut with a pelletizer to obtain 93 parts by weight of pellets (B).

(Creation of recycled resin stamper)
Thereafter, in Production Example 2, a recycled resin stamper (C) was obtained in the same manner as in Production Example 2 except that the pellet (B) was used instead of the pellet (A) obtained in Production Example 1.

(Create optical disc)
A polycarbonate resin (Panlite AD5503 manufactured by Teijin Chemicals Ltd.) is injection-molded to provide a guide groove for tracking laser light called a recording track (groove) having an inner diameter of 15 mm, an outer diameter of 120 mm, and a thickness of 0.1 mm. A 6 mm substrate was produced. Next, a tetrafluorolopentanol solution (concentration 2% by weight) of a metal-containing azo dye was prepared, and then a dye recording layer was formed by spin coating on the surface on the recording track side. Further thereon, a semi-transparent light reflecting layer was formed by sputtering a silver alloy to produce a first recording layer.

  Next, an ultraviolet curable resin [DVD-595 manufactured by Nippon Kayaku Co., Ltd.] is applied on the translucent light reflecting layer of the produced substrate and bonded to the resin stamper (C). The ultraviolet curable resin was cured by irradiating ultraviolet rays from the stamper side. Thereafter, the resin stamper was peeled off to form a curable resin layer having a film thickness of about 40 μm onto which the recording track (groove) was transferred. Subsequently, a tetrafluorolopentanol solution (concentration of 2% by weight) of a metal-containing azo dye is prepared on the surface of the curable resin layer of the optical disk substrate having the recording track (groove), and the dye is then spin-coated. A recording layer was formed. Further, a second recording layer was produced by sputtering a silver alloy to form a light reflecting layer.

  Next, a polycarbonate resin [Panlite AD5503 manufactured by Teijin Kasei Co., Ltd.] was injection molded to produce a substrate having an inner diameter of 15 mm, an outer diameter of 120 mm, and a thickness of 0.6 mm without a recording layer. UV curable resin Dicure Clear SD-694 (manufactured by Dainippon Ink & Chemicals, Incorporated) is applied to the surface of the light reflecting layer of the substrate having the two recording layers obtained as described above and pasted. In addition, ultraviolet light was irradiated from the surface of the substrate of the bonded disk to cure the ultraviolet curable adhesive, and an adhesive layer was formed to produce an optical disk (A).

[Example 2]
A polymer provided with a stainless sintered filter having a pore size of 5 μm in a clean booth of clean class 6 or less as defined in ISO 14644-1 with a pulverized product of a used resin stamper (B) obtained in the same manner as in Example 1. While supplying nitrogen to the hopper at 500 cc / min at a cylinder temperature of 250 ° C. and a polymer filter temperature of 250 ° C. by a single screw extruder (manufactured by Tanabe Plastic Machinery Co., Ltd., VS-40) connected with a filter (manufactured by Fuji Filter) The pulverized product was melt-extruded from a die into a strand shape and cut with a pelletizer to obtain 95 parts of regenerated pellet (C).

  In Example 1, a recycled resin stamper (C) and an optical disk (B) were obtained in the same manner as in Example 1 except that the pellet (C) was used instead of the pellet (B).

[Example 3]
In Example 1, a recycled resin stamper (D) and an optical disc (C) were obtained in the same manner as in Example 1 except that the outer peripheral portion was removed so that the diameter of the used resin stamper (B) was 100 mm.

[Comparative Example 1]
In Example 2, the used stamper (E) and the optical disk (D) were obtained in the same manner as in Example 2 except that the resin stamper (B) was pulverized as it was to obtain a pulverized product and the polymer filter was not used. It was.

  The number of foreign matters of 5 μm or more contained in the recycled pellets obtained in Examples 1 to 3 and Comparative Example 1, the light transmittance of the solution, and the peel strength of the resin stamper obtained using the recycled pellets, creation Table 1 summarizes the measurement results of the PI error of the optical disc.

[Consideration] As shown in Table 1, when a recycled pellet having a foreign matter number of 5 μm or more within the definition of the present invention is used, it has a high light transmittance for sufficiently curing the curable resin layer, and a resin stamper. The peel strength from the curable resin layer was small, and no adhesion of the curable resin was observed on the uneven surface of the resin stamper after peeling, and the resin stamper could be used repeatedly. Further, the obtained optical disk had a PI error within a practical range (Examples 1 to 3).

  On the other hand, if the number of foreign matters of 5 μm or more is outside the limits of the present invention, the light transmittance is reduced, the peel strength from the curable resin layer of the resin stamper is increased, and the uneven surface of the resin stamper is cured after peeling. The resin stamper could not be used repeatedly. The obtained optical disk had a large PI error and did not reach a practical level. (Comparative Example 1)

  The recycled resin of the present invention is excellent in transparency, releasability, and transferability because there are few foreign substances such as curable resin components. The use of the recycled resin of the present invention is a molded article for optical use such as a lens, a prism, a deflection film, a light guide plate, a light diffusing plate, an optical disk substrate, or a resin stamper for producing an optical recording medium; press-through package, disposable syringe, chemical solution Molded articles for medical use such as vials and infusion bags; Molded articles for electric or electronic materials such as electric wire coverings, wafer shippers, and hard disk substrates; Building materials such as carports and glazings; Automobiles such as room mirrors, inner lenses, and lamp reflectors Components: Wrapping films, stretch films, shrink films, packaging films such as blister packs, and stationery such as ballpoint pen cores.

  Among these, the resin stamper for manufacturing an optical recording medium is preferable because the resin stamper can be repeatedly used because of its low peel strength, and the obtained optical recording medium has a low PI error.

Claims (4)

  Recycled resin of curable resin molding resin mold, wherein the resin mold is formed from a resin material containing an alicyclic structure-containing thermoplastic resin, and is 5 μm or more contained in the recycled resin A recycled resin of a resin mold for curable resin molding, characterized in that the number of foreign matters is 100 / g or less.   The recycled resin according to claim 1, wherein the light transmittance at a wavelength of 365 nm measured with an optical path length of 10 mm of a cyclohexane solution having a recycled resin concentration of 10% by weight is 85% or more.   The molded object formed from the resin material containing the reproduction | regeneration resin of Claim 1 or 2.   The molded article according to claim 3, which is a resin stamper for producing an optical recording medium.