JP2006096032A - Regenerated resin molded body, molding method of regenerated resin molded body and method of obtaining regenerated resin stamper - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a regenerated resin molded body obtained by re-molding a resin material obtained by pulverizing a resin molded body such as a used resin stamper or the like, a molding method of the regenerated resin molded body, and a method of obtaining the regenerated resin stamper. <P>SOLUTION: The regenerated resin molded body obtained by molding the resin material obtained by pulverizing the resin molded body of an alicyclic structure-containing thermoplastic resin is characterized in that the number of foreign substances having a longer diameter of not less than 30 μm in the molded body is not more than 100/10 g. The manufacturing method of the regenerated resin molded body comprises pulverizing the resin molded body of the alicyclic structure-containing thermoplastic resin under a surrounding environment of class 6 or more according to air cleanliness classification; air-transporting the obtained pulverized material through a metallic transporting tube 5 having surface roughness Rmax of the inner side of not more than 1.8μm to a molding machine in the plasticizing portion of which an inert gas is injected; and molding the air-transported pulverized material using the molding machine. The regenerated resin stamper containing not more than 100/10 g of the foreign substances having a longer diameter of not less than 30 μm is obtained by the method. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a recycled resin molded body obtained by remolding a used alicyclic structure-containing thermoplastic resin molded body, a method for molding a recycled resin molded body, and a method for obtaining a recycled resin stamper.

  Conventionally, a resin molded body such as a resin stamper (also referred to as a transparent stamper) is formed by laminating an uncured photocurable resin layer and a resin molded body made of an alicyclic structure-containing thermoplastic resin on a substrate in this order. Used in a method for manufacturing an optical component or the like, which includes a step of curing the uncured photocurable resin with light transmitted through the resin molded body, and peeling (removing) the resin molded body (Patent Literature). 1, 2). In addition, the alicyclic structure-containing thermoplastic resin is excellent in heat distortion resistance and moisture absorption deformation resistance, etc., and has excellent releasability from curable resin, and can transfer uneven surface shapes with high surface accuracy. It is used as a material for

  However, in a resin molded body made of an alicyclic structure-containing thermoplastic resin, when a recycled resin molded body obtained by re-molding using a resin material obtained by pulverizing a used resin molded body is used. In the process of peeling the recycled resin molded body, cracks occurred in the recycled resin molded body, which could not be used again as a molded body.

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

  The present invention has been made in view of such problems of the prior art, and a recycled resin molded body obtained by remolding a resin material obtained by pulverizing a resin molded body such as a used resin stamper, It is an object of the present invention to provide a method for forming a recycled resin molded body and a method for obtaining a recycled resin stamper.

  In order to solve the above problems, the present inventors measured the number of foreign matters in the resin molded body and the toughness of the resin molded body. As a result, the number of foreign matters having a major axis of 30 μm or more in the molded body was 100 or less in 10 g. If it exists, even if it was a resin molding repeatedly remolded, the knowledge that it functions as a resin molding was acquired.

  As a result of various studies on methods for reducing the amount of foreign matter, the resin molded body is pulverized in an ambient environment where the classification of air cleanliness is Class 6 or higher, and the pulverizer is changed to an injection molding machine. For air transportation, the inner surface roughness Rmax of the transport tube is 1.8 μm or less, preferably an austenitic stainless steel is used, and the plastic of an injection molding machine for molding a resin molded body is used. It was found that a resin molded body having a number of foreign matters having a major axis of 30 μm or more of 100 pieces / 10 g can be obtained by injecting nitrogen gas into the forming portion, and the present invention has been completed.

  Thus, according to the first aspect of the present invention, there is provided a recycled resin molded article obtained by molding a resin material obtained by pulverizing a resin molded article comprising an alicyclic structure-containing thermoplastic resin, the recycled resin molded article. There is provided a recycled resin molded product characterized in that the number of foreign matters having a major axis of 30 μm or more is 100/10 g or less.

In the recycled resin molded article of the present invention, the resin molded article made of the alicyclic structure-containing thermoplastic resin is preferably a resin mold.
The recycled resin molding of the present invention is preferably a recycled resin mold, and more preferably a recycled resin stamper.

According to the second aspect of the present invention, a resin molded body made of an alicyclic structure-containing thermoplastic resin was obtained in an ambient environment with a classification of air cleanliness of class 6 or higher. The pulverized product was transported through a transport pipe using a metal material and having an inner surface roughness Rmax of 1.8 μm or less, and then transported to a molding machine in which an inert gas was injected into the plasticizing part. There is provided a method for molding a recycled resin molded article, wherein a pulverized product is molded using the molding machine.
In the forming method of the present invention, the metal material is preferably made of austenitic stainless steel.

According to the third aspect of the present invention,
(I) A resin stamper made of an alicyclic structure-containing thermoplastic resin is pulverized in an ambient environment where the classification of air cleanliness is Class 6 or higher,
(Ii) The obtained resin material is passed through a transport pipe having an inner surface roughness Rmax of 1.8 μm or less using a metal material, and is empty in a molding machine in which an inert gas is injected into the plasticizing portion. After carrying
(Iii) Molding the pulverized material in the molding machine,
There is provided a method for obtaining a recycled resin stamper in which the number of foreign matters having a major axis of 30 μm or more is 100/10 g or less.

Since the recycled resin molded body of the present invention has a small amount of foreign matter and hardly deteriorates the molded body toughness, it can be reused repeatedly as a resin molded body.
According to the method for molding a resin molded body of the present invention, the recycled resin molded body of the present invention can be efficiently produced.
According to the molding method of the present invention, a recycled resin molded body that can be used repeatedly two or more times is provided with little decrease in the toughness of the molded body due to a small amount of foreign matter.
According to the molding method of the present invention, the recycled resin molded body of the present invention can be regenerated repeatedly, which is economical.
According to the method for obtaining the recycled resin stamper of the present invention, the recycled resin stamper can be efficiently produced.

Hereinafter, the present invention will be described in detail.
1) Recycled resin molded body The recycled resin molded body of the present invention is a recycled resin molded body obtained by molding a resin material obtained by pulverizing a resin molded body comprising an alicyclic structure-containing thermoplastic resin, The number of foreign matters having a major axis of 30 μm or more in the recycled resin molding is 100/10 g or less.

(1) Resin molded body The resin molded body used for this invention consists of an alicyclic structure containing thermoplastic resin.
In the present invention, the alicyclic structure-containing thermoplastic resin is a polymer containing a repeating unit having an alicyclic structure, and a polymer resin having an alicyclic structure in the main chain and an alicyclic ring in the side chain. Any polymer resin having the formula structure is included.

  A resin molded body made of a thermoplastic resin containing an alicyclic structure is capable of molding a fine structure with high precision, has excellent durability (heat resistance, moisture absorption resistance deformation, can be used repeatedly, etc.), and has a cured molded body. It has excellent properties for releasability.

  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) norbornene polymer, (ii) monocyclic olefin polymer, (iii) cyclic conjugated diene polymer, (iv) 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.

Specific examples of norbornene polymers include ring-opening polymers of norbornene monomers, ring-opening copolymers of norbornene monomers and other monomers capable of ring-opening copolymerization, and hydrogens thereof. And addition polymers of norbornene monomers, addition copolymers with other monomers copolymerizable with norbornene monomers, and the like. 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-benzotricyclo [4.3.0.1 ^2,5 ] dec-3-ene (common name: methanotetrahydrofluorene), 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.

  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.

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.

  The vinyl alicyclic hydrocarbon polymer is a polymer having a repeating unit derived from vinylcycloalkane or vinylcycloalkene. 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.

The vinyl alicyclic hydrocarbon polymer is a random copolymer of a vinyl alicyclic hydrocarbon compound or a vinyl aromatic hydrocarbon compound and another monomer copolymerizable with these monomers, 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 and molecular weight distribution of the alicyclic structure-containing thermoplastic resin are appropriately selected according to the purpose of use.
The molecular weight of the alicyclic structure-containing thermoplastic resin is converted to monodisperse polyisoprene measured by gel permeation chromatography (GPC) using cyclohexane (or toluene) as a solvent (when the solvent is toluene, converted to monodisperse polystyrene) The weight average molecular weight (Mw) measured by (1) is usually in the range of 1,000 to 1,000,000, preferably 5,000 to 500,000, more preferably 10,000 to 200,000. When the weight average molecular weight (Mw) of the alicyclic structure-containing thermoplastic resin is within this range, it is preferable that the balance between mechanical strength and moldability is maintained.

  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 molding processability of the resin molded body 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 molded body are highly balanced and suitable.

  The melt mass 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 range is 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 molded body having a fine shape becomes optimum. preferable.

  The resin molded body comprising the alicyclic structure-containing thermoplastic resin used in the present invention is prepared by preparing a composition comprising the alicyclic structure-containing thermoplastic resin and molding the resin composition by a known molding method. Can be manufactured.

  In the resin composition, as long as the effect of the present invention is not substantially inhibited, a lubricant such as a hydroxyl group-containing fatty acid ester compound, an anti-aging agent such as a phenolic or phosphoric acid, a benzophenone or benzotriazole Various additives such as an amine-based antistatic agent, a hindered amine-based weathering stabilizer, and the like may be added.

  As a method for preparing the resin composition, for example, an additive is optionally added to the solution of the alicyclic structure-containing thermoplastic resin and then dried to remove the solvent, or the alicyclic structure-containing heat is used. Examples thereof include a method in which a predetermined amount of each of a plastic resin and, if desired, an additive is mixed and mechanically stirred using a roll, a brabender, an extruder, or the like.

  The glass transition temperature (Tg) of the obtained resin composition is not particularly limited, but is preferably 90 to 110 ° C, preferably 95 to 105 ° C, and the melt mass flow rate (MFR) is 50 to 70 g / 10 minutes. By using a composition that is preferably 60 to 70 g / 10 min, it is possible to obtain a resin mold that is excellent in releasability from a cured resin and transferability of a fine uneven shape.

  The glass transition temperature (Tg) of the resin composition can be measured based on JIS K7121, and the melt mass flow rate (MFR) can be measured at 280 ° C. under a 2.16 kg load based on JIS K7210. .

  Examples of the molding method include molding methods such as injection molding, press molding, extrusion blow molding, injection blow molding, multilayer blow molding, connection blow molding, double wall blow molding, stretch blow molding, vacuum molding, and rotational molding. It is done. Among these, 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 a sheet or film produced by a melt extrusion method in an uneven mold to be molded.

  The molding conditions vary depending on the molding method and the type of the alicyclic structure-containing thermoplastic resin used, but the resin temperature is usually 100 to 400 ° C, preferably 200 to 380 ° C, more preferably 200 to 350 ° C. The pressure is usually 0.1 to 100 MPa, preferably 0.5 to 50 MPa, and the heating time is usually several seconds to several tens of minutes.

(2) Recycled resin molding The recycled resin molding of the present invention is obtained by molding a resin material obtained by pulverizing the resin molding.

  The means for pulverizing the resin molded body is not particularly limited, and normal pulverizing means for plastic plates can be employed. For example, a method using a cutting type or hammer type pulverizer can be mentioned. Among these pulverizing means, since a small amount of fine powder is generated, a method using a cutting-type pulverizer is preferable, and a pulverizer having a rotating rotary blade and a fixed blade and having a circular screen at the bottom is used. The method of doing is more preferable. By using such a cutting type pulverizer, it is possible to obtain only a small piece of a resin molded body that can pass through a screen with less fine powder from the resin molded body.

  The fine pieces of the pulverized resin molded body may be uniform in shape and size, or may be random. The size is suitably such that it substantially passes through a 15 mm diameter circular hole and 90% by weight does not pass through a 2 mm diameter circular hole.

  The fine pieces of the resin molded body can be used as a resin material as they are, but can also be formed into pellets. The pellets can be obtained by melting and kneading the pulverized resin molded product pieces, extruding them into strands or rods through a strand die, and then cutting them with a cutter or the like.

  In addition, when melt-kneading the pulverized pieces of the resin molded body, if desired, an unused alicyclic structure-containing thermoplastic resin, a lubricant such as a hydroxyl group-containing fatty acid ester compound, a phenolic or phosphorus-based compound Add various additives such as anti-aging agents such as phenol, thermal degradation inhibitors such as phenols, UV stabilizers such as benzophenone and benzotriazole; antistatic agents such as amines, and weathering stabilizers such as hindered amines. Also good.

  The recycled resin molded product of the present invention can be produced by molding the resin material by a known molding method. Examples of the molding method include the same molding methods used for the production of the resin molded body described above.

  Although the molding conditions vary depending on the molding method and the type of the alicyclic structure-containing thermoplastic resin used, the resin temperature is usually 100 to 400 ° C, preferably 200 to 380 ° C, more preferably 200 to 350 ° C, The pressure is usually 0.1 to 100 MPa, preferably 0.5 to 50 MPa, and the heating time is usually several seconds to several tens of minutes.

  The recycled resin molded product of the present invention is characterized in that the number of foreign matters having a major axis of 30 μm or more in the molded product is 100/10 g or less, preferably 50/10 g or less.

Since the recycled resin molded product of the present invention has a small number of foreign matters having a major axis of 30 μm or more in the molded product, the molded product is excellent in toughness.
For example, in the case of manufacturing an optical component having a high surface accuracy uneven shape on the surface, the resin molded body is a resin stamper, and after being laminated on the curable resin layer and curing the curable resin layer, the resin stamper In the case of peeling (removing), no cracks are generated, so that high-quality optical components can be efficiently manufactured.

  The number of foreign matters in the molded body is 10 g of resin molded body dissolved in 1200 g of tetralin, suction filtered using a filter paper having a reserved particle diameter of 20 to 25 μm, and the number of foreign matters remaining on the filter paper with a major axis of 30 μm or more is measured with an optical microscope. Can be observed and requested. Here, the foreign matter means dust mixed in the molding and pulverization process of the molded body, or a resin oxide, a resin decomposition product, a carbide or the like derived from a raw material resin.

  The recycled resin molded body of the present invention is not particularly limited in shape and size as long as it can be recycled. Since the recycled resin molded body of the present invention contains almost no foreign matter, it has excellent molded body toughness and optical characteristics, electrical characteristics, and surface characteristics.

  The recycled resin molded body of the present invention includes an optical disk molded body, an optical fiber, a camera lens, an overhead projector lens, an LBP Fθ lens, a prism, a liquid crystal display element (LCD), a light diffusion plate, a light guide plate, a polarizing film, a phase difference Optical molded products such as films, brightness enhancement films, condensing films; various clean containers such as liquid chemical containers, ampoules, infusion bags, eye drops containers, semiconductor wafer storage containers; medical equipment such as syringes and medical infusion tubes And these resin molds are suitable. Among these, it is more suitable as a resin mold that requires toughness.

  Resin molds are roughly classified into two types: a type (resin stamper) that forms an internal space with a mold and a base, and a type that forms an internal space with a mold. More specifically, in the first type, a curable resin is applied on a substrate, the recycled resin molded body of the present invention is overlaid on the obtained coating film, and the curable resin is cured. This is a type (resin stamper) in which a resin mold is peeled and removed from a composite made of a cured resin. By using this type of resin mold, a molded body having a cured resin layer having a concavo-convex shape on the surface of the substrate can be produced.

  The second type is a type in which the resin mold is removed from the cured resin after filling the internal space formed by the resin mold with the curable resin and curing the curable resin. By using the second type of resin mold, a resin molded body having an uneven shape on the surface can be produced. The second type of resin mold is not particularly limited as long as the resin mold is removed after filling the internal space formed by the resin mold with the curable resin and curing the curable resin. For example, one that is integrally molded and has an internal space filled with a curable resin, one that is formed so as to be separable and combined to form an internal space filled with a curable resin, and a resin mold Examples include a combination of a mold and an internal space.

  Among these, it is particularly suitable as a resin mold for manufacturing an optical component such as an optical disk forming body that is required to mold a concavo-convex shape with high surface accuracy, and is most preferable as a resin stamper for manufacturing an optical disk.

3) Molding method of recycled resin molding The molding method of the recycled resin molding according to the present invention is based on (a) class [Classification of Air Cleanliness]. The same shall apply hereinafter.) In an ambient environment of 6 or more, pulverize a resin molded body made of an alicyclic structure-containing thermoplastic resin, and (b) Pass through a transport pipe having a thickness Rmax of 1.8 μm or less, and carry it to a molding machine in which an inert gas is injected into the plasticizing part. (C) Form the crushed material using the molding machine. It is characterized by doing.
The molding method of the recycled resin molding of the present invention is suitable as a method for producing the above-mentioned recycled resin molding of the present invention.
Hereinafter, the molding method of the recycled resin molding of the present invention will be described in detail.

(a) First, a resin material made of an alicyclic structure-containing thermoplastic resin material is pulverized in a surrounding environment of class 6 or higher to obtain a resin material.
The means for pulverizing the resin molded body is not particularly limited, but the same methods as those listed in the section of the recycled resin molded body of the present invention can be used.

  The pulverized product can be used as a resin material as it is, but it can also be formed into pellets. The pellets can be obtained by melting and kneading the pulverized resin molded product pieces, extruding them into strands or rods through a strand die, and then cutting them with a cutter or the like. At this time, in addition to pellets obtained from the resin molded body, resin pellets obtained by newly polymerizing can also be mixed.

  In the present invention, the resin molded body is preferably pulverized and molded in a clean environment with an air cleanliness classification of class 6 or higher, more preferably class 5 or higher. By crushing and molding a used resin molded body in a clean environment of class 6 or higher, it is possible to prevent foreign matters from being mixed during crushing and molding.

Here, class 6 or higher means class 6, 5, 4, 3, 2, or 1. Class 6 or higher is defined by ISO 14644-1 as a class of air cleanliness that is not more than 1,000,000 particles per m ³ , and Class 5 or higher is defined by ISO 14644-1. The air cleanliness classification means that there are 100,000 or less particles of 0.1 μm or more per 1 m ³ .

(b) Next, a molding machine in which the obtained resin material is passed through a transport pipe using a metal material and having an inner surface roughness Rmax of 1.8 μm or less, and an inert gas is injected into the plasticized portion. Carry in the air.
The resin material obtained above is transported to the molding machine by a pneumatic transportation system by suction or pressure feeding. In the case of pressure feeding, 1 to 7 kg / cm ² , and in the case of suction, it is pneumatically transported at a flow rate of 3 to 20 m / sec through a transport pipe made of a metal material at a pressure of −500 mmAq to −1000 mmAq. Normally, a corrosion-resistant metal pipe whose inner surface is finished by mechanical polishing is used for the pneumatic transport pipe.

Generally, in mechanical polishing, polishing is performed using a mineral abrasive according to the finishing accuracy, and the surface finish is mirror-finished in terms of visual appearance, but microscopically fine polishing streaks are in front of the polishing surface. Exists on the surface. The concave portion of the polishing streak is in a state where the metal component of the abrasive is wedged. When the resin material having the above flow velocity collides with the polished surface, mineral fine particles are mixed into the resin material.
In the present invention, by using a metal pipe having an inner surface roughness Rmax of 1.8 μm or less, it is possible to prevent mineral fine particles from being mixed into the resin material as much as possible due to the collision of the resin material.

  Here, Rmax on the inner surface of the transport pipe means the maximum roughness measured according to JIS B0601. A transport pipe having an inner surface roughness Rmax of 1.8 μm or less can be obtained, for example, by buffing or electrolytic polishing the inside of the pipe. In buffing, buff # 150 to # 500, preferably # 400 is usually used. For example, the Rmax of the inner surface of the container when SUS is buffed is in the range of 1 to 5 μm, and the surface roughness Rmax inside the transport pipe when electrolytically polished is in the range of 0.01 to 1 μm.

In the present invention, it is particularly preferable to use a metal pipe made of austenitic stainless steel from the viewpoint of preventing foreign matter contamination.
As the austenitic stainless steel, alloys 1 to 4 having components shown in Table 1 below are preferable.

  In the present invention, the resin material is preferably transported to a molding machine in which an inert gas is injected into the plasticizing portion. By injecting an inert gas into the plasticized part, it is possible to prevent resin burnt due to air mixing and carbides called black spots from being mixed into the recycled resin molded body.

(c) Finally, the air-pulverized pulverized product is formed using a molding machine.
As the molding method of the resin material, the same methods and molding conditions as those listed in the section of the method for producing a recycled resin molded product of the present invention can be employed.

  The recycled resin molded body of the present invention can be manufactured using, for example, a resin molding apparatus (molding machine) shown in FIG. The resin molding apparatus shown in FIG. 1 includes an airborne resin transfer apparatus (not shown), a resin storage cylinder 6, a blister valve 7, an inert gas injection apparatus 2, and a plasticizing apparatus 15. In this apparatus, the bottom of the transport gas / resin separation unit 13 of the airborne resin transport device and the top of the resin storage cylinder are connected, the blister valve 7 is connected to the top of the resin storage cylinder, and the plasticizer is connected to the bottom of the resin storage cylinder The raw material supply port 15 is connected, the inert gas injection device 2 is installed in the vicinity of the raw material supply port of the plasticizing device 15, and the gland packing 10 in which vacuum grease is applied between the screw bearing 9 part and the screw 12. It has.

  The airborne resin transport device is a device that transports a resin material from a drying hopper or the like to a resin storage cylinder through an air current transport pipe (duct, pipe, etc.). More specifically, the resin material is transported to a transport gas / resin material separation unit such as a cyclone connected to the top of the resin storage cylinder using gas as a mobile phase, and the resin material and the gas are separated by the separation unit. The material is dropped into the resin storage cylinder, and the gas is discharged from the exhaust port.

  In the resin transport apparatus of the resin molding apparatus shown in FIG. 1, the apparatus in contact with the pellets and the equipment through which the transport gas passes are all made of austenitic stainless steel except for the filter.

  As the transport method of the airborne resin transport device, (1) a pressurization method in which the transport gas / resin material is pressurized and transported to the transport gas / resin material separation unit, and (2) the exhaust of the transport gas / resin material separation unit. Examples include a suction method for sucking and transporting the carrier gas / resin material by reducing the mouth, and (3) a combination method of these.

  The top of the resin storage cylinder is connected to the bottom of the transport gas / resin separation section 13 of the airborne resin transport device, and the bottom of the resin storage cylinder is connected to the raw material supply port of the screw type injection molding machine (plasticizer) 15. Has been.

  The blister valve 7 is installed on the upper part of the resin storage cylinder 6, and when the pellet / conveying gas separation unit 13 becomes a negative pressure with respect to the atmospheric pressure, a gas is introduced from the outside, and the raw material of the plasticizer 15 The increase in oxygen concentration in the vicinity of the supply port is prevented.

  The blister valve 7 is a valve having a function of keeping the pressure in the resin storage cylinder 6 constant. For example, when the pressure in the resin storage cylinder is lower than a certain pressure such as atmospheric pressure, the valve is opened and gas is introduced into the resin storage cylinder. When the pressure is greater than a certain pressure such as atmospheric pressure, the valve is opened and the gas is stored in the resin. Examples include those that discharge to the outside of the cylinder, and filters that have the above-mentioned functions by having a specific resistance are also included.

  The void portion of the pellet accumulated in the resin storage cylinder 6 is replaced with nitrogen by an inert gas introduced from the inert gas injection device 2 installed at the lower part of the resin storage cylinder.

  The inert gas injection device 2 is a device for injecting an inert gas in order to prevent contact with oxygen when the resin material is plasticized, and its installation position is in the vicinity of the raw material supply port of the plasticizer 15. If there is no particular limitation. Specifically, the resin storage cylinder lower part, the raw material supply port of the plasticizing apparatus 15, etc. are mentioned.

  Examples of the inert gas include nitrogen, helium, and argon, but high purity is preferable. From the viewpoint of production cost, it is preferable to use nitrogen gas.

  The inert gas injection amount is not particularly limited, but is preferably in the range of 1 to 50 liters / minute and more preferably in the range of 3 to 20 liters / minute with respect to 10 mL of the pellet space of the resin storage cylinder 6. A range of 5 to 10 liter / min is particularly preferable. When the inert gas injection amount is in this range, the effect of preventing the resin from burning is high, which is preferable in terms of the cost of the inert gas.

  When the amount of pellets falls below the level meter 14 installed in the resin storage cylinder 6, the airborne resin transport device is activated, and the pellets and transport gas are introduced into the pellet / transport gas separation unit 13 through the transport pipe 5. . The pellet and the carrier gas are separated into pellets and gas in the separation unit 13, the carrier gas is discharged from the carrier gas exhaust pipe 4 through the filter 3, and the pellet falls and accumulates in the resin storage cylinder 6.

  As the carrier gas, a gas inert to the resin such as air or nitrogen is used. The carrier gas is preferably one that has been dedusted and dehumidified. For example, air removed from a cyclone, a filter or the like is passed through a cooling device to condense moisture, then passed through a filter to remove condensed water, and further, heating, cooling and dehumidification are repeated 1 to 3 times before use.

  Although it does not specifically limit as the plasticizing apparatus 15, An injection molding machine; Extruder; Blow molding machine; A vacuum molding machine etc. are mentioned. Among these, a screw type plasticizing device is preferable, and a gland packing is preferably provided between the screw bearing portion of the screw holder and the screw. It is preferable that the gland packing is provided because oxygen mixing between the screw bearing portion and the screw and leakage of the filling nitrogen are prevented.

  The gland packing 10 is an O-ring provided between the screw bearing 9 portion of the screw holder 1 and the screw 1, and the O-ring is lubricated with vacuum grease or the like in order to reduce friction and increase airtightness. It is preferable to apply an agent. Moreover, although it does not specifically limit as a screw, It is preferable that the surface of the screw 1 is titanium nitride aluminum. When the surface of the screw 1 is titanium nitride aluminum, the effect of preventing resin burn can be enhanced.

3) Method of Obtaining Recycled Resin Stamper The third aspect of the present invention is that (i) a resin stamper made of an alicyclic structure-containing thermoplastic resin is used one or more times, and the classification of air cleanliness (Classification of air cleanliness) (Ii) The obtained resin material is passed through a transport pipe having an inner surface roughness Rmax of 1.8 μm or less using a metal material, and pulverized in a plastic environment. (Iii) A method of obtaining a recycled resin stamper in which the number of foreign matters having a major axis of 30 μm or more is 100/10 g or less after being transported to a molding machine into which inert gas has been injected. .

  Each step of the method for obtaining the recycled resin stamper of the present invention can be performed in the same manner as the steps (a) to (c) described in the method for molding a recycled resin molded body of the present invention.

According to the present invention, since the number of foreign matters is small, a recycled resin stamper that can be reused repeatedly three times or more with almost no decrease in toughness of the molded product is supplied.
Further, according to the present invention, the recycled resin stamper of the present invention can be regenerated repeatedly, which is economical.

Hereinafter, the present invention will be described more specifically with reference to reference examples, examples and comparative examples.
However, the present invention is not limited to these examples. In the following, unless otherwise specified, parts and% are based on weight, and pressure is gauge pressure.

The measuring methods of various physical properties in the following examples and comparative examples are as follows.
(1) Hydrogenation rate The hydrogenation rate to the unsaturated bond of the alicyclic structure-containing thermoplastic resin was measured by ¹ H-NMR.
(2) Glass transition temperature (Tg)
Tg of the alicyclic structure-containing thermoplastic resin was measured by a differential scanning calorimeter based on JIS K7121 at a temperature increase rate of 10 ° C./min.
(3) Molecular Weight The molecular weight of the alicyclic structure-containing thermoplastic resin was measured by gel permeation chromatography (GPC) at 40 ° C. using cyclohexane as a solvent, and the number average molecular weight (Mn) in terms of monodispersed polyisoprene and The weight average molecular weight (Mw) was determined.
(4) Amount of foreign matter in the molded body The amount of foreign matter in the molded body is determined by dissolving 10 g of the molded body in 1200 g of tetralin and suction filtering using a filter paper having a reserved particle diameter of 20 to 25 μm. The number of foreign matters of 30 μm or more was determined by observing with an optical microscope. Here, the foreign matter means dust or carbide of raw material resin mixed in the molding and pulverization processes of the molded body.
(5) Molded body toughness The molded body toughness was measured using a universal compression tester 20 (TCM500CR, manufactured by Minebea) shown in FIG. That is, a compression test was performed in which a rod 22 having a conical tip with a diameter of 25 mm was pushed into the center of a 0.6 mm thick resin stamper 21 from above to give a deflection of 7 mm. The test was performed on 1000 molded bodies, and the number of ruptures at that time was determined to evaluate the toughness of the molded body as a rupture rate. If the rupture rate is 5% or less, it is judged that there is toughness that can be used as a molded body.

[Reference Example 1: Production of alicyclic structure-containing thermoplastic resin]
6-methyl-1,4: 5,8-dimethano-1,4,4a, 5,6,7,8,8a-octahydronaphthalene (hereinafter referred to as MTD) 90% and 5-methyl-2- 100 parts of a ring-opening copolymer obtained by polymerizing a monomer mixture consisting of 10% norbornene (hereinafter referred to as MNB) using a ring-opening polymerization catalyst is dissolved in 400 parts of cyclohexane, and a hydrogenation catalyst is obtained. As a catalyst, 5 parts of nickel-alumina catalyst (manufactured by JGC Chemical Co., Ltd.) is added, the gauge pressure is increased to 5 MPaG with hydrogen, the mixture is heated to 200 ° C. with stirring, and then reacted for 4 hours. A combined hydrogenated product was obtained. The reaction solution after hydrogenation was diluted with cyclohexane so that the content of hydrogenated MTD-MNB ring-opening copolymer was 20%, diatomaceous earth (Radiolite # 500) was used as a filter bed, and a pressure filter (funda Using a filter (manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd.), pressure filtration was performed at a pressure of 0.25 MPa to obtain a colorless and transparent MTD-MNB ring-opening copolymer hydrogenated solution I.

  100 parts of MTD-MNB ring-opening copolymer hydrogenated solution I was further filtered through a metal fiber filter (caliber 3 μm, manufactured by Nichidai), and then zeta plus filter 10H (caliber 0.5-1 μm, Cuno). The product is then filtered through a metal fiber filter (caliber 0.2 μm, manufactured by Nichidai Co., Ltd.) to remove foreign matter, and the resulting filtrate is respectively dissolved in cyclohexane with an antioxidant (Irganox 1010). , Manufactured by Ciba Specialty Chemicals Co., Ltd.) and a rubbery polymer (Tuftec H1052, manufactured by Asahi Kasei Co., Ltd.), so that both are 0.2 parts with respect to 100 parts of MTD-MNB ring-opening copolymer hydrogenated product, Added in solution. Then, cyclohexane was removed as a first step (temperature 270 ° C., pressure 13.3 kPa) and a second step (temperature 270 ° C., pressure 667 Pa) using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.). . The resulting resin composition was extruded from a die in a molten state in a class 1000 clean room, extruded from a die, cooled with water, passed through a pelletizer (OSP-2, manufactured by Nagata Seisakusho) into a 3 mm diameter strand, and a strand cutter. It cut | disconnected to length 3mm each, and obtained 18 parts of MTD-MNB ring-opening copolymer hydrogenated pellets. The pellets were stored in a sealed stainless steel container whose surface was polished. As a result of analyzing a 10% by weight pellet solution in toluene by gas chromatography, the amount of residual cyclohexane was below the measurement limit. The hydrogenated MTD-MNB ring-opening copolymer was colorless and transparent, Mw 42,000, Mn 18,000, Tg 140 ° C., and the hydrogenation rate was almost 100%.

[Example 1]
Using the pellet obtained in Reference Example 1 as a resin material, a disk-shaped resin stamper was molded using the resin molding apparatus shown in FIG. An injection molding machine (SD40ER, manufactured by Sumitomo Heavy Industries, Ltd.) was used as the plasticizing apparatus.
As molding conditions, the resin molding equipment is installed in a clean room whose air cleanliness class is Class 6, the resin temperature (barrel set maximum temperature) is 330 ° C, and the mold temperature is 80 ° C on both the fixed and movable sides. It was.
The pellets were heat-treated at 100 ° C. for 4 hours in a dryer until just before molding.
As the inert gas, nitrogen having a purity of 99.99% was used and introduced at a supply rate of 10 liters / minute.

  The resin stamper molded as described above was used once for the production of an optical disk, and pulverized by a pulverizer to obtain a pulverized stamper having a maximum particle size of 5 mm. The pulverized product was transported to the resin supply unit of the resin molding apparatus shown in FIG. 1, and a resin stamper having the same shape as that before pulverization was produced using only the recycled product. The above use, pulverization, air transportation, and production steps were repeated twice more.

As the pulverizer, a cutting pulverizer (MGL-100, manufactured by Matsui Seisakusho) was used.
Molding and pulverization are operations in a clean environment of class 6, and the surface roughness Rmax inside the transport pipe when transported is 0.5 μm. During molding, nitrogen gas was injected into the plasticizing part of the injection molding machine. .
In the resin stamper obtained in Example 1, the amount of foreign matter having a major axis of 30 μm or more (foreign matter amount), classification of air cleanliness during molding and pulverization, presence or absence of nitrogen injection during molding, and toughness of the resin stamper (Stamper toughness) is shown in Table 2.

[Example 2]
A resin stamper was produced in the same procedure as in Example 1 except that the surface roughness Rmax inside the transport pipe was 1.8 μm.
In the resin stamper obtained in Example 2, the amount of foreign matter having a major axis of 30 μm or more (foreign matter amount), molding, classification of air cleanliness during pulverization, presence or absence of nitrogen injection during molding, and toughness of the resin stamper (Stamper toughness) is shown in Table 2.

[Comparative Example 1]
A resin stamper was produced in the same procedure as in Example 2 except that nitrogen injection was not performed during molding.
In the resin stamper obtained in Comparative Example 1, the amount of foreign matter having a major axis of 30 μm or more (foreign matter amount), classification of air cleanliness during molding and pulverization, presence or absence of nitrogen injection during molding, and toughness of the resin stamper (Stamper toughness) is shown in Table 2.

[Comparative Example 2]
A stamper was produced in the same procedure as in Example 2 except that the surface roughness Rmax inside the transport tube was 10.0 μm.
In the resin stamper obtained in Comparative Example 2, the amount of foreign matter having a major axis of 30 μm or more (foreign matter amount), molding, classification of air cleanliness during pulverization, presence or absence of nitrogen injection during molding, and toughness of the molded body (Stamper toughness) is shown in Table 2.

[Comparative Example 3]
A stamper was produced in the same procedure as in Example 2 except that the ambient environment during molding and pulverization was class 8.
In the resin stamper obtained in Comparative Example 3, the amount of foreign matter having a major axis of 30 μm or more (foreign matter amount), classification of air cleanliness during molding and pulverization, presence or absence of nitrogen injection during molding, and toughness of the resin stamper (Stamper toughness) is shown in Table 2.

Table 2 shows the following.
If the air cleanliness classification of the molding and pulverization environment is class 6 or higher, the surface roughness Rmax inside the transport pipe is 1.8 μm or less, and if nitrogen gas is injected into the plasticized part at the time of molding, A resin stamper having an amount of foreign matter of 100 or less is obtained, and the toughness of the resin stamper is 10% or less at breakage, and has a toughness that can be used as a stamper.
On the other hand, even if the air cleanliness classification is class 6 and the surface roughness Rmax inside the transport pipe is 1.8 μm or less, the amount of foreign matter in the resin stamper must be injected unless nitrogen gas is injected into the plasticizing part during molding. More than 100 resin stampers are obtained, and the toughness of the resin stampers is 20% at breakage and cannot be reused as a resin stamper due to insufficient toughness (Comparative Example 1).

In addition, even if the air cleanliness classification is class 6, even if nitrogen gas is injected into the plasticizing part during molding, the amount of foreign matter in the resin stamper is 10 μm when the surface roughness Rmax inside the transport pipe is 10.0 μm. More than 100 resin stampers are obtained, and the toughness of the resin stampers is 50% at breakage and cannot be reused as a resin stamper due to insufficient toughness (Comparative Example 2).
Furthermore, if the surface roughness Rmax inside the transport pipe is 1.8 μm and nitrogen gas is injected into the plasticized part at the time of molding, if the air cleanliness classification is class 8, the amount of foreign matter in the resin stamper is More than 100 resin stampers were obtained, and the toughness of the resin stampers was 100% (all resin stampers were broken), and because of insufficient toughness, they could not be reused as resin stampers (Comparative Example 3).

It is the schematic which shows an example of the resin molding apparatus for enforcing the method which remolds the resin stamper of this invention. It is a schematic diagram of the universal compression tester which measures a molded object toughness.

Explanation of symbols

P ... resin material, 1 ... screw holder, 2 ... inert gas injection device, 3 ... filter, 4 ... carrier gas exhaust pipe, 5 ... transport pipe, 6 ... resin storage cylinder, 7 ... blister valve, 8 ... oxygen concentration meter DESCRIPTION OF SYMBOLS 9 ... Screw bearing, 10 ... Gland packing, 11 ... Drive device, 12 ... Screw, 13 ... Carrier gas / resin separation part, 14 ... Level meter, 15 ... Plasticizer, 20 ... Universal compression tester, 21 ... Resin Stamper, 22 ... Rod

Claims (7)

  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, wherein the number of foreign matters having a major axis of 30 μm or more in the recycled resin molded article is 100. Recycled resin molded body characterized in that the number is 10/10 g or less.   The recycled resin molded body according to claim 1, wherein the resin molded body made of the alicyclic structure-containing thermoplastic resin is a resin mold.   The recycled resin molded article according to claim 1 or 2, which is a recycled resin mold.   It is a recycled resin stamper, The recycled resin molding in any one of Claims 1-3.   In a surrounding environment where the classification of air cleanliness is Class 6 or higher, a resin molded body made of an alicyclic structure-containing thermoplastic resin was pulverized, and the obtained pulverized product was made of a metal material. The inner surface roughness Rmax is 1.8 μm or less, and is transported to a molding machine in which an inert gas is injected into the plasticizing part. A method for molding a recycled resin molded product, characterized by: molding.   The forming method according to claim 5, wherein the metal material is made of austenitic stainless steel. (I) A resin stamper made of an alicyclic structure-containing thermoplastic resin is pulverized in an ambient environment where the classification of air cleanliness is Class 6 or higher,
(Ii) The obtained resin material was passed through a transport pipe having an inner surface roughness Rmax of 1.8 μm or less using a metal material, and was transported to a molding machine in which an inert gas was injected into the plasticizing part. rear,
(Iii) Molding the pulverized material in the molding machine,
A method for obtaining a recycled resin stamper in which the number of foreign matters having a major axis of 30 μm or more is 100/10 g or less.

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