JP2001220446A - Molded article and method for cleansing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molded article which scarcely contaminates a contact object. SOLUTION: This molded article has a metal elution rate of <=1 μg/cm2 at the surface of the molded article in water, when immersed in the water for 24 hr, and is obtained by molding an alicyclic structure-containing polymer as a molding material by a method for preventing the contamination of a metal component and then cleansing the molded article.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article made of a polymer having an alicyclic structure, and more particularly, to a molded article suitable for semiconductor processing equipment and the like because the metal content of the surface and the layer near the surface is small. About the body.

[0002]

2. Description of the Related Art An alicyclic structure-containing polymer has a low impurity content and is excellent in low elution, so that it is used for medical applications such as chemical containers and syringes for syringes, chemical solution bottles for semiconductor production, and chemical solution supply piping materials. Is reported to be suitable for semiconductor manufacturing applications.

However, in recent years, the degree of integration of semiconductor components has been remarkably improved, and it is required that chemicals and the like used for the production thereof have higher purity, especially extremely low metal content. As the resin material of the processing equipment for storing and transporting the chemical solution and the like, a material which does not contaminate the chemical solution and has a small metal elution amount is being demanded.

Although an alicyclic structure-containing polymer can be originally produced with a metal content of 1 ppm or less, even if such a material having a low metal content is used, it can be formed into a molded product such as a container or a pipe. In such a case, the environment or the metal components in the molding machine may be mixed as contamination into the surface of the molded body or a layer in the vicinity thereof, and may contaminate a chemical solution or the like during use.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a molded article having low contamination to a contacting object.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that when immersed in water for a certain time, the amount of metal eluted into the water is less than a certain amount. By using the body for a container or the like, it was found that the contents to be stored and the contacting object were less contaminated, and the present invention was completed.

Thus, according to the present invention, an alicyclic structure-containing polymer is formed, and when immersed in water for 24 hours, the amount of metal eluted into the water is 1 μg / cm per unit surface area of the formed body.
There is provided a molded article that is no more than ² . After the alicyclic structure-containing polymer is formed, a method is provided in which the obtained formed body is brought into contact with and / or immersed in water and / or an organic solvent to reduce the metal elution amount of the formed body.

[0008]

Embodiments of the present invention will be described below. Molded article The molded article of the present invention is obtained by molding an alicyclic structure-containing polymer, and the molded article is formed in water (at a temperature of 30 to 40 ° C).
When completely immersed in water for 24 hours, the amount of metal component eluted into water from the molded body is 1 μg per unit surface area of the molded body.
/ Cm ² or less, preferably 0.5 μg / cm ² or less, more preferably 0.1 μg / cm ² or less. As a method of obtaining the molded body,
(1) a method of molding using an alicyclic structure-containing polymer having a low metal content, (2) a method of molding a molded article in an environment having a high degree of cleanliness, (3) a cylinder, a screw, a hopper of a molding machine to be used, A method of using a material such as a metal mold having excellent abrasion resistance with little shaving, (4) contacting and / or immersing the obtained molded body in water and / or an organic solvent before use, A method of reducing the amount of metal eluted from the molded article, and the like are mentioned. In order to obtain a molded article having a smaller amount of metal elution, the method (4) is more preferable, and the method (4) is all other methods. Is most preferably used in combination.

Alicyclic Structure-Containing Polymer The alicyclic structure-containing polymer used in the present invention has a main chain and / or
Alternatively, those having an alicyclic structure in the side chain, and those having an alicyclic structure in the main chain are preferable from the viewpoint of mechanical strength, heat resistance and the like.

Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure, and a cycloalkane structure is preferred from the viewpoint of mechanical strength and heat resistance. The number of carbon atoms that make up the alicyclic structure is
From the viewpoints of heat resistance and moldability, the number is usually 4 to 30, preferably 5 to 20, and more preferably 5 to 15. The proportion of the repeating unit having an alicyclic structure is appropriately selected depending on the purpose of use, and is usually 50% by weight or more.
Preferably 70% by weight or more, more preferably 90% by weight
That is all. It is preferable from the viewpoint of transparency and heat resistance that the proportion of the repeating unit having an alicyclic structure be within this range.

Specific examples of such an alicyclic structure-containing polymer include (1) a norbornene-based polymer, (2) a monocyclic olefin-based polymer, (3) a cyclic conjugated diene-based polymer, and (4) ) Vinyl alicyclic hydrocarbon-based polymers and hydrogenated products thereof. Among these,
A norbornene-based polymer, a cyclic conjugated diene-based polymer and a hydrogenated product thereof are preferable, and a norbornene-based polymer is more preferable in terms of heat resistance and mechanical strength.

(1) Norbornene-based polymer The norbornene-based polymer is disclosed in, for example, JP-A-3-1488.
No. 2, JP-A-3-122137, and the like. Specifically, the polymer is a ring-opened polymer of a norbornene-based monomer, a hydrogenated product thereof, and an addition weight of a norbornene-based monomer. And an addition copolymer of a norbornene-based monomer and a vinyl compound.

Specific examples of the norbornene-based monomer used in the polymerization include bicyclo [2,2,1] -hept-2-
Ene (common name: norbornene), 5-methyl-bicyclo [2,2,1] -hept-2-ene, 5,5-dimethyl-bicyclo [2,2,1] -hept-2-ene, 5- Ethyl-bicyclo [2,2,1] -hept-2-ene, 5
-Butyl-bicyclo [2,2,1] -hept-2-ene, 5-hexyl-bicyclo [2,2,1] -hept-
2-ene, 5-octyl-bicyclo [2,2,1] -hept-2-ene, 5-octadecyl-bicyclo [2,
2,1] -hept-2-ene, 5-ethylidene-bicyclo [2,2,1] -hept-2-ene, 5-methylidene-bicyclo [2,2,1] -hept-2-ene, 5 -Vinyl-bicyclo [2,2,1] -hept-2-ene, 5
-Propenyl-bicyclo [2,2,1] -hept-2-
En,

5-methoxy-carbonyl-bicyclo [2,2,1] -hept-2-ene, 5-cyano-bicyclo [2,2,1] -hept-2-ene, 5-methyl-
5-methoxycarbonyl-bicyclo [2,2,1] -hept-2-ene, 5-methoxycarbonyl-bicyclo [2,2,1] -hept-2-ene, 5-ethoxycarbonyl-bicyclo [2,2 , 1] -Hept-2-ene,
5-methyl-5-ethoxycarbonyl-bicyclo [2,
2,1] -hept-2-ene, bicyclo [2,2,1]
-Hept-5-enyl-2-methylpropionate, bicyclo [2,2,1] -hept-5-enyl-2-methyloctanoate, bicyclo [2,2,1] -hept-2
-Ene-5,6-dicarboxylic anhydride, 5-hydroxymethyl-bicyclo [2,2,1] -hept-2-ene,
5,6-di (hydroxymethyl) -bicyclo [2,2,
1] -hept-2-ene, 5-hydroxy-i-propyl-bicyclo [2,2,1] -hept-2-ene, bicyclo [2,2,1] -hept-2-ene, 5,6 -Dicarboxy-bicyclo [2,2,1] -hept-2-ene, bicyclo [2,2,1] -hept-2-ene-5.
6-dicarboxylic imide, 5-cyclopentyl-bicyclo [2,2,1] -hept-2-ene, 5-cyclohexyl-bicyclo [2,2,1] -hept-2-ene, 5
-Cyclohexenyl-bicyclo [2,2,1] -hept-2-ene, 5-phenyl-bicyclo [2,2,1]-
Hept-2-ene,

Tricyclo [4,3,1^2,5,
0^1,6] -Deca-3,7-diene (common name is dicyclope
Antadiene), tricyclo [4,3,1^2,5, 0
^1,6] -Dec-3-ene, tricyclo [4,4,1
^2,5, 0^1,6] -Undeca-3,7-diene
Is tricyclo [4,4,1^2,5, 0^1,6]-Unde
C-3,8-diene, tricyclo [4,4,1^2,5,
0^1,6] -Undec-3-ene, tetracyclo [7,
4,1^10,13, 0^1,9, 0^2,7] -Trideca-
2,4,6-11-tetraene (1,4-methano-1,
4,4a, 9a-tetrahydrofluorene),
Tetracyclo [8,4,1^11,14, 0^1,10, 0
^3,8] -Tetradeca-3,5,7,12-11-tet
Raen (1,4-methano-1,4,4a, 5,10,1
0a-hexahydroanthracene)
A norbornene monomer having no bornan ring;

Tetracyclo [4,4,1^2,5, 1
^7,10, 0] -dodec-3-ene (simply tetracyclo
Dodecene), 8-methyl-tetracyclo [4,
4,1^{2 , 5}, 1^7,10, 0] -dodec-3-ene,
8-methyl-tetracyclo [4,4,1^2,5, 1
^7,10, 0] -Dodeca-3-ene, 8-ethyl-tet
Lacyclo [4,4,1^2,5, 1^7,10, 0] -dode
Car-3-ene, 8-methylidene-tetracyclo [4,
4,1^2,5, 1^7,10, 0] -dodec-3-ene,
8-ethylidene-tetracyclo [4,4,1^2,5, 1
^7,10, 0] -Dodeca-3-ene, 8-vinyl-tet
Lacyclo [4,4,1^2,5, 1^7,10, 0] -dode
Car-3-ene, 8-propenyl-tetracyclo [4,
4,1^2,5, 1^{7, 10}, 0] -dodec-3-ene,
8-methoxycarbonyl-tetracyclo [4,4,1
^2,5, 1^7,10, 0] -dodec-3-ene, 8-me
Tyl-8-methoxycarbonyl-tetracyclo [4,
4,1^2,5, 1^7,10, 0] -dodec-3-ene,
8-hydroxymethyl-tetracyclo [4,4,1
^2,5, 1^{7,1 0}, 0] -dodeca-3-ene, 8-ca
Ruboxy-tetracyclo [4,4,1^{2, 5}, 1
^7,10, 0] -Dodeca-3-ene, 8-cyclopentene
Le-tetracyclo [4,4,1^2,5, 1^7,10,
0] -dodec-3-ene, 8-cyclohexyl-tetra
Cyclo [4,4,1^2,5, 1^7,10, 0] -dodeca
-3-ene, 8-cyclohexenyl-tetracyclo
[4,4,1^2,5, 1^7,10, 0] -dodeca-3-
Ene, 8-phenyl-tetracyclo [4,4,
1^2,5, 1^{7,1 0}, 0] -dodeka-3-ene, pen
Tacyclo [6,5,1^1,8, 1^3,6, 0 ^2,7, 0
^9,13] -Pentadeca-3,10-diene, pentacyclo
Black [7,4,1^3,6, 1^10,13, 0^1,9, 0
^2,7] -Pentadeca-4,11-diene and other norbo
Norbornene-based monomers having a lunan ring are respectively
No.

The above norbornene monomers can be used alone or in combination of two or more.

In the present invention, in addition to the norbornene-based monomer, copolymerizable monomers include, for example,
Ethylene, propylene, 1-butene, 1-pentene, 1
-Hexene, 3-methyl-1-butene, 3-methyl-1
-Pentene, 3-ethyl-1-pentene, 4-methyl-
1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1- Octene, 1-decene, 1-dodecene, 1-
Tetradecene, 1-hexadecene, 1-octadecene,
Α-olefins having 2 to 20 carbon atoms such as 1-eicosene; cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene; Cycloolefins such as 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene; 1,4-hexadiene, 4-methyl-
Non-conjugated dienes such as 1,4-hexadiene, 5-methyl-1,4-hexadiene and 1,7-octadiene; and the like can be used. These copolymerizable monomers can be used alone or in combination of two or more.

The ring-opening polymer of the above monomer is a catalyst comprising a metal halide such as ruthenium, rhodium, palladium, osmium, iridium, platinum or the like, a nitrate or acetylacetone compound, and a reducing agent as a ring-opening polymerization catalyst. Alternatively, titanium, vanadium, zirconium, tungsten, a metal halide such as molybdenum or an acetylacetone compound, using a catalyst system comprising an organoaluminum compound, in a solvent or without a solvent, usually at -50 ℃ ~ 100 ℃ Polymerization temperature, 0-50k
It can be obtained by ring-opening polymerization at a polymerization pressure of g / cm ² . The hydrogenated norbornene-based polymer can be obtained by adding hydrogen to a ring-opening (co) polymer in the presence of a hydrogenation catalyst according to a conventional method.

The addition copolymer of the norbornene-based monomer and the copolymerizable monomer is, for example, a monomer component comprising a titanium compound, a zirconium compound, or a vanadium compound and an organic aluminum compound in a solvent or without a solvent. In the presence of a catalyst system, usually -50 ° C to 1
It can be obtained by a method of copolymerizing at a polymerization temperature of 00 ° C. and a polymerization pressure of 0 to 50 kg / cm ² .

(2) Monocyclic Cyclic Olefin Polymer Examples of the monocyclic cyclic olefin polymer include monocyclic cycloolefin polymers such as cyclohexene, cycloheptene and cyclooctene disclosed in JP-A-64-66216. Can be used.

(3) Cyclic conjugated diene-based polymer The cyclic conjugated diene-based polymer is described in, for example,
The cyclic conjugated diene-based monomers such as cyclopentadiene and cyclohexadiene disclosed in JP-A-136057 and JP-A-7-258318 are used as 1,2- or 1,2-
4-Polymerized polymers and hydrogenated products thereof can be used.

(4) Vinyl alicyclic hydrocarbon-based polymer Examples of the vinyl alicyclic hydrocarbon-based polymer include vinyl cyclohexene and vinyl cyclohexane disclosed in JP-A-51-59989. Polymers of alicyclic hydrocarbon monomers and hydrogenated products thereof, vinyls such as styrene and α-methylstyrene disclosed in JP-A-63-43910 and JP-A-64-1706. A hydrogenated product of the aromatic ring portion of the polymer of the aromatic monomer can be used. The configuration of these vinyl alicyclic hydrocarbon-based polymers may be any of atactic, isotactic and syndiotactic. For example, any of 0 to 100% in syndiotacticity by dyad display. Can also be used.

The molecular weight of the alicyclic structure-containing polymer used in the present invention is appropriately selected according to the purpose of use, and the gel permeation of a cyclohexane solution (a toluene solution when the polymer is not dissolved) is used. The weight average molecular weight in terms of polyisoprene measured by a chromatographic method is 5,0
00 to 500,000, preferably 8,000 to 20
0000, more preferably 10,000-100,0
When it is in the range of 00, the mechanical strength and the moldability are highly balanced and suitable. The glass transition temperature (Tg) of the alicyclic structure-containing polymer used in the present invention may be appropriately selected according to the purpose of use, but is usually 50 to 300.
° C, preferably 60-200 ° C, more preferably 70-200 ° C.
180 ° C.

Ingredients The alicyclic structure-containing polymer may be added , if desired, to an antioxidant such as a phenolic antioxidant or a phosphorus antioxidant, an ultraviolet absorber such as a benzophenone ultraviolet absorber, or a light stabilizer. Various additives such as antistatic agents, esters of aliphatic alcohols, partial esters of polyhydric alcohols and partial ethers may be blended. In addition, other resins, rubbery polymers and the like can be mixed and used as long as the object of the present invention is not impaired.

Molding Method and Molded Article The method for obtaining the molded article of the present invention using the alicyclic structure-containing polymer includes a method in which the alicyclic structure-containing polymer is heated and melted, and a method in which the solvent is removed from the solution. And a method of molding while being performed. Specifically, methods such as injection molding, injection compression molding, extrusion molding, injection blow molding, direct blow molding, stretch molding, inflation molding, and cast molding can be used. The molded body can be formed into a spherical shape, a rod shape, a cylindrical shape, a disk shape, a sheet shape, a film shape, a shape obtained by combining these, and the like.

When molding a molded article by the above method,
By performing molding in a highly clean environment, that is, by implementing a method of molding a molded body in a highly clean environment, it is possible to reduce the intrusion of foreign substances and the like into the molded product from the environment, The amount of elution can be reduced.

(Clean Environment) In order to increase the cleanness of the molding environment, it is preferable to shut off the molding environment from the external environment to form a closed system to prevent contamination from the external environment. As a specific method for setting the molding environment to a closed system, there is a method of performing molding in a clean room. A clean room is usually set so that the clean gas (mainly oxygen) from which foreign substances causing contamination have been removed by an air filter is sent into the system at a predetermined air volume, and the pressure inside the system is higher than the external pressure. ing. In addition, the degree of cleanliness is classified according to the amount of foreign substances in the clean room. In the present invention, the cleanliness in the clean room in which the molding is performed is preferably class 1000, more preferably class 100, and most preferably class 1. (Cleanness is 30.48 c.
Class 1000 if there are about 1000 microparticles of about 0.5 μm per mx 30.48 cm cubic unit (1 cubic foot), class 100 if there are about 100, and class 10 if there are about 100. It is. Further, a clean booth having a higher degree of cleanness than in the clean room class may be locally installed, or a local exhaust facility may be provided in a place where dust is generated. It is also preferable that a floor of a grating specification is provided so that the air flow of the clean gas is laminar so that contaminants serving as contamination do not stay in the clean room for a long time, and the exhaust port is provided under the floor.

Also, by using a material having excellent abrasion resistance as a material of a molding machine used for molding, in particular, a material of a portion which comes into contact with the polymer having an alicyclic structure, mixing of a metal component into a molded product can be prevented. Can be reduced. More specifically, for example, it is preferable to use a material such as a cylinder, a screw, a hopper, and a mold of an injection molding machine or an extrusion molding machine, which has little wear and is excellent in wear resistance. Specifically, the material is SUS420, SUS440, SMC
440, SNC439 as a base material, TiC, TiN,
A lined TiCN is preferred because of its low abrasion resistance and low resin adhesion.

The molded article of the present invention can be obtained by the above-mentioned method. In order to further reduce the amount of metal eluted from the obtained molded article, the molded article must be treated with water or an organic compound before use. Cleaning with a solvent (hereinafter referred to as a cleaning liquid) is most effective. As a cleaning method, a metal component (including a foreign substance containing a metal component) adhered to the surface of the molded product by contacting or dipping the molded product with a cleaning liquid, and a metal component in a layer near the surface of the molded product. In the cleaning solution. In order to sufficiently transfer the metal component into the cleaning liquid, not only the molded body is simply immersed in or contacted with the cleaning liquid, but also the metal component near the surface of the molded body elutes or contains the metal component on the surface of the molded body. It is preferable that the cleaning liquid is immersed in or brought into contact with the molded body for a time sufficient to dissolve the foreign matter (metallic foreign matter). Also, in order to physically remove metallic foreign matter from the surface of the molded body, the cleaning liquid on the surface of the molded body has a constant flow rate,
Vibration energy can also be given to the cleaning liquid. As described above, as a specific method for further improving the cleaning effect, a method of increasing the temperature of the cleaning liquid (30 ° C. or higher,
(Preferably at least 40 ° C.), a method in which a washing tank to be immersed is sealed and pressurized, a method in which a washing solution is circulated, a method in which a washing layer is ultrasonically vibrated, a method in which a molded body is fixed with a jig and vibrated, and the like. . The cleaning time is 10
It is preferably performed for at least 20 seconds, more preferably for at least 20 seconds.

As the cleaning liquid, either water or an organic solvent may be used, but both water cleaning and organic solvent cleaning may be performed sequentially, or a mixed solution of water and an organic solvent may be used.

At the time of washing, it is preferable to use ultrapure water as water. The organic solvent is not particularly limited as long as it is an organic solvent generally used industrially,
Aromatic hydrocarbons, alicyclic hydrocarbons, alcohols,
It is preferable to use at least one organic solvent selected from the group consisting of ketones. Further, the boiling point (Tb) of the organic solvent and the glass transition temperature (T
g) (Tg-Tb) is 10 ° C. or more, preferably 2
When the temperature is 0 ° C. or higher, the organic solvent is easily removed after washing, and the cleanness of the molded body is improved.

After the washing treatment, the molded article can be dried and used by subjecting it to a heat treatment, a pressure reduction treatment in a container, or a centrifugal treatment. For efficient drying, these methods can be used in combination. Further, by repeating the washing treatment and the drying step, the amount of metal eluted from the molded body can be efficiently reduced.

Method for Measuring the Amount of Metal Elution The amount of metal elution of a molded article having reduced metal components and the like by the above method can be measured by the following method. The surface area of the whole or a part of the molded body is measured, and the molded body is left standing for 24 hours in a state where the whole or a part of the molded body whose surface area is measured is immersed in water. At this time, the amount of water used to immerse the molded body is adjusted from the above measured surface area so as to be a constant amount per unit area of the immersed portion of the molded body. Next, the molded body was taken out of the water, and the metal content was measured by inductively coupled plasma emission spectrometry (ICP-AES) using a certain amount of water in which the molded body was immersed. The amount of extraction is determined by calculation (unit: μg / cm ² ).

[0035] In the applications above, molded metal elution amount is reduced,
Since there is little contamination of the contacting object, storage and transport bottles for chemical liquids for cleaning semiconductor parts, containers for pharmaceutical vials, containers such as resist and insulating varnish, containers for chemical bottles, etc .; cleaning layers for semiconductor parts, etc .; semiconductor parts Piping materials such as ultrapure water piping and chemical supply piping for cleaning; wafer transport containers such as silicon wafer carriers and wafer shippers;
It is suitably used for applications requiring cleanliness, such as jigs for cleaning semiconductor components and liquid crystal components. Further, since it has little contamination to an information recording medium such as a hard disk, it is suitable for a hard disk carrier and the like. Further, when the molded article is used for an optical component, it is preferable that the film is less contaminated even when a reflective film, a protective film, a recording film, or the like is applied and subjected to secondary processing. Specifically, substrates for optical information recording media such as compact disks, write-once optical disks, magneto-optical disks, and phase-change optical disks; substrates for magnetic recording media such as plastic hard disks and magnetic disks; fθ mirrors, polygon mirrors, It can be suitably used as an optical mirror such as a prism mirror; an optical lens such as a pickup lens, a finder lens, and a laser scanning lens.

[0036]

EXAMPLES The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following, “parts” and “%” are based on weight unless otherwise specified. The methods for measuring various physical properties in the following Production Examples, Examples and Comparative Examples are as follows.

Measurement of Physical Properties (1) The weight average molecular weight (Mw) was determined by gel permeation chromatography (GP) using cyclohexane as a solvent.
It was measured as a polyisoprene conversion value by C). (2) The hydrogenation rate (nuclear hydrogenation rate) of the main chain and the aromatic ring is
^It was measured by ¹ H-NMR. (3) The glass transition temperature (Tg) was measured based on JIS-K7121. (4) The surface area of the whole or a part of the molded body is measured, and the molded body is allowed to stand for 24 hours in a water having a known metal content in such a manner that all of the measured surface area of the molded body is immersed. At this time, the amount of water used for immersion is set to be a constant amount per unit area of the portion of the molded body to be immersed.
Next, the molded body was taken out, and a certain amount of water used for immersion was used for ICP-AES (SPS12 manufactured by Seiko Denshi).
00AR), and the amount of extracted metal per surface area of the molded body was calculated from the amount of the sample (water after immersion) used for the measurement (unit: μg / cm ² ). (5) The evaluation of the contamination of the molded article with respect to the object is performed by placing a 3.2-inch silicon wafer on a plate molded by the following method in a class 100 clean bench in a class 1000 clean room. 2 at 60 ° C
After standing for 4 hours, the amount of metal eluted from the silicon wafer was measured by the same method as in (4) above, and the difference from the amount of metal eluted before placing the plate was measured.

Polymer Preparation Example 6-Methyl-1,4: 5,8-dimethano-1,4,4
100 parts of a ring-opened polymer synthesized using a monomer containing 90% of a, 5,6,7,8,8a-octahydronaphthalene (hereinafter referred to as MTD) and 10% of 5-methyl-2-norbornene Was dissolved in 400 parts of cyclohexane, and 5 parts of a nickel-alumina catalyst (manufactured by Nikki Chemical Co., Ltd.) was added as a hydrogenation catalyst, and the mixture was pressurized to 50 kg / cm ² with hydrogen and heated to a temperature of 200 ° C. with stirring. 4
Reaction was carried out for a period of time to synthesize a hydrogenated ring-opening polymer.

The polymer reaction solution containing the hydrogenation catalyst was subjected to pressure filtration (Funda Filter, manufactured by Ishikawajima-Harima Heavy Industries, Ltd.) using Radiolite # 500 as a filtration bed at a pressure of 2.5.
pressure filtration at kg / cm ² to remove the hydrogenation catalyst,
A clear and colorless solution was obtained. After 100 parts of the obtained colorless and transparent solution was further filtered through a metal fiber filter (3 μm in diameter, manufactured by Nichidai Co., Ltd.), it was filtered through a Zetaplus filter 30S (0.5 to 1 μm in diameter, manufactured by Kuno),
In addition, a metal fiber filter (0.2μ aperture)
m, manufactured by Nichidai Co., Ltd.) to remove foreign substances to obtain a solution. From this solution, cyclohexane as a solvent was removed by a cylindrical concentration dryer (manufactured by Hitachi, Ltd.). The operating condition is the first step: temperature 270 ° C, pressure 100To
rr, second step: removed at a temperature of 270 ° C. and a pressure of 5 Torr. In a class 1000 clean room,
The polymer from which the solvent has been removed is brought into a molten state, extruded from a die, cooled with water, and then subjected to a pelletizer (OSP-2,
(Nagada Seisakusho) to obtain 18 parts of pellets. This polymer was filled and stored in a stainless steel closed container having a polished surface. As a result of analyzing a toluene solution containing 10% of the polymer by gas chromatography, the amount of residual cyclohexane was below the measurement limit, and the molecular weight in terms of polyisoprene by GPC analysis was Mn: 27,500 and Mw: 5
6,000, Tg measured by DSC analysis is 140 ° C.
Met. Further, as a deuterated chloroform solution, ¹ H-N
Hydrogenation rate measured by MR spectrum is almost 100
%Met.

Example 1 Using the polymer obtained in the above polymer preparation example, using an injection molding machine (Roboshot α100, manufactured by FANUC), a resin temperature of 300 ° C., a mold temperature of 120 ° C., and a length of 90 were used.
A plate having a thickness of 50 mm, a width of 50 mm and a thickness of 3 mm was formed.
The molding machine is installed in a cleanroom of cleanliness class 1000, and the mold part is further cleaned in cleanliness class 100.
The polymer pellets were heated in a dryer at 100 ° C. for 4 hours and molded within 30 minutes after being taken out of the dryer. SUS420 was used for the cylinder and the screw of the molding machine. The obtained plate was filtered through a 0.1 μm filter 2
It was immersed in 00 ml of ion-exchanged water for 5 hours to extract and wash metal components and the like. Next, the molded product was taken out and dried with hot air at 90 ° C. for 12 hours in a clean oven equipped with a PEPA filter at the air intake. The surface area of the plate was measured, and the metal elution amount was measured by the method described above. The evaluation results are shown in Table 1 (the same applies to Example 9 and Comparative Example).

[0041]

[Table 1]

Example 2 The procedure of Example 1 was repeated except that the drying was performed by spin drying (spin speed: 1800 rpm, rotation time: 30 seconds).

Example 3 When a molded product was immersed in ion-exchanged water, an ultrasonic wave (ultrasonic frequency: 40 KHz, ultrasonic output: 300 KW) was applied, and
The procedure was performed in the same manner as in Example 2 except that the time was changed.

Example 4 The same operation as in Example 3 was carried out except that ultrapure water having a specific resistance of 16 MΩ · cm was used instead of ion-exchanged water.

Example 5 The same procedure as in Example 4 was carried out except that a methanol / ultrapure water mixture in which 1 wt% of methanol filtered with a 0.1 μm filter was mixed with ultrapure water was used.

Example 6 The same procedure as in Example 4 was carried out except that a methanol / ultrapure water mixture obtained by mixing 1% by weight of cyclohexane filtered with a 0.1 μm filter in ultrapure water was used.

Example 7 Example 4 was repeated twice.

Example 8 Example 8 was carried out in the same manner as in Example 1 except that SUS420 was not used as the material of the cylinder and the screw, but nitrided steel was used.

Example 9 In particular, the mold part was not installed in the clean booth,
The procedure was performed in the same manner as in Example 1 except that the injection molding machine including the mold portion was installed in a class 1000 clean room.

Comparative Example The obtained molded body was not washed, and the amount of metal extracted from the molded body was measured and evaluated.

[0051]

According to the present invention, the content of metal components in the surface or in the vicinity of the surface is extremely small. No moldings are provided.

Claims (2)

[Claims] 1. A molded article obtained by molding an alicyclic structure-containing polymer and having a metal elution amount of 1 μg / cm ² or less per unit surface area of the molded article when immersed in water for 24 hours. 2. A method of molding a polymer having an alicyclic structure and then contacting and / or immersing the resulting molded article in water and / or an organic solvent to reduce the amount of metal eluted in the molded article.