Components and semiconductor manufacturing-related equipment

Abstract

To provide a member having excellent corrosion resistance and a semiconductor manufacturing-related device using the same.SOLUTION: Provided is a member that includes at least one thermoplastic resin selected from the group consisting of polyolefin resins and chlorine-based resins, where the member is at least one member selected from the group consisting of building material members, mobility members, aerospace members, semiconductor members and information communication members, and where the member comes into contact with a corrosive substance.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to components and semiconductor manufacturing-related equipment. [Background technology]

[0002] It has been proposed to use polyethylene that meets certain requirements for high-purity chemical containers (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 10-17729 [Overview of the project] [Problems that the invention aims to solve]

[0004] This disclosure aims to provide a component with excellent corrosion resistance and semiconductor manufacturing-related equipment using the same. [Means for solving the problem]

[0005] (1) This disclosure relates to a component comprising at least one thermoplastic resin selected from the group consisting of polyolefin resins and chlorine-based resins, The aforementioned member is at least one selected from the group consisting of building materials, mobility components, aerospace components, semiconductor components, and information and communication components. It is a component that comes into contact with corrosive substances.

[0006] Disclosure (2) is the component according to Disclosure (1) wherein the thermoplastic resin is crystalline.

[0007] Disclosure (3) is a component according to Disclosure (1) or (2), wherein the polyolefin resin is at least one selected from the group consisting of polyethylene resin, polypropylene resin, amorphous cycloolefin resin, crystalline cycloolefin resin, and polymethylpentene resin.

[0008] Disclosure (4) is a component in any combination of any of Disclosures (1) to (3), wherein the chlorine-based resin is at least one selected from the group consisting of vinyl chloride resin, chlorinated vinyl chloride resin, and chlorinated polyethylene resin.

[0009] Disclosure (5) is a component in any combination of any of Disclosures (1) to (4), wherein the thermoplastic resin is at least one selected from the group consisting of polyethylene resin, polypropylene resin, amorphous cycloolefin resin, crystalline cycloolefin resin, polymethylpentene resin, and vinyl chloride resin.

[0010] Disclosure (6) is a component in any combination of any of Disclosures (1) to (4), wherein the thermoplastic resin is at least one selected from the group consisting of polypropylene resin, amorphous cycloolefin resin, crystalline cycloolefin resin, and polymethylpentene resin.

[0011] The present disclosure (7) is a component in any combination of any of the present disclosures (1) to (6), wherein the component is at least one selected from the group consisting of containers, pipes, nozzles, tubes, tanks, fittings, valves, pumps, spin chucks, O-rings, packings, gaskets, washers, and sealing materials.

[0012] Disclosure (8) is a component in any combination of any of Disclosures (1) to (7), wherein the thermoplastic resin is at least one selected from the group consisting of polypropylene resin, amorphous cycloolefin resin, crystalline cycloolefin resin and polymethylpentene resin, and the component is at least one selected from the group consisting of container, piping, nozzle, tube, tank, fitting, valve, pump, spin chuck, O-ring, packing, gasket, washer, and sealing material.

[0013] Disclosure (9) is a component in any combination of any of Disclosures (1) to (8) wherein the pH of the corrosive substance is 6 or less or 8 or more.

[0014] Disclosure (10) is a component in any combination of any of Disclosures (1) to (9) wherein the oxidation-reduction potential (vsNHE) of the corrosive substance is -2.0 to 3.0 V.

[0015] Disclosure (11) is a component in any combination of any of Disclosures (1) to (10), wherein the corrosive substance is at least one selected from the group consisting of acidic substances, basic substances, oxidizing substances, organic solvents and brine.

[0016] The present disclosure (12) is a component according to the present disclosure (11), wherein the acidic substance is at least one selected from the group consisting of sulfuric acid, hydrofluoric acid, nitric acid, phosphoric acid, hydrochloric acid, a mixed acid of hydrofluoric acid and nitric acid, a mixed chemical solution of hydrogen peroxide and hydrochloric acid, and a mixed chemical solution of hydrogen peroxide and sulfuric acid.

[0017] This disclosure (13) states that the basic substance is TMAH([(CH3)4N] + [OH] - The component is the one described in (11) or (12) of this disclosure, which is at least one selected from the group consisting of an aqueous solution of sodium hydroxide, aqueous ammonia, and a mixed chemical solution of hydrogen peroxide and aqueous ammonia.

[0018] This disclosure (14) states that the corrosive substance is sulfuric acid, hydrofluoric acid, nitric acid, phosphoric acid, hydrochloric acid, a mixed acid of hydrofluoric acid and nitric acid, a mixed chemical solution of hydrogen peroxide and hydrochloric acid, a mixed chemical solution of hydrogen peroxide and sulfuric acid, TMAH([(CH3)4N] + [OH] - The component is any combination of any of (1) to (13) of the present disclosure, which is at least one selected from the group consisting of sodium hydroxide aqueous solution, a mixed chemical solution of hydrogen peroxide and ammonia water, and isopropyl alcohol.

[0019] The present disclosure (15) is a component in any combination with any of the present disclosures (1) to (14), the component being a component for semiconductor manufacturing equipment.

[0020] This disclosure (16) is a component of this disclosure (15) in which the semiconductor manufacturing-related equipment is an equipment in which chemicals are used within the equipment.

[0021] Disclosure (17) is a component in any combination of any of Disclosures (1) to (16) in which a test piece of the component (size: 10 mm × 50 mm × 2 mm) is immersed in each of the following three chemical solutions for one week, and the relative value of the mass after immersion, with the mass before immersion set to 100, is 95 or more and 105 or less in all cases. (Medicinal solution) 25% by mass TMAH([(CH3)4N] + [OH] - )(80℃), Mixed acid of hydrofluoric acid and nitric acid (a mixture of 49% hydrofluoric acid and 69-71% nitric acid by mass in a volume ratio of 1:100) (20℃) SPM (a mixture of 98% sulfuric acid by mass and 30-36% hydrogen peroxide by mass in a volume ratio of 2:1) (80°C)

[0022] Disclosure (18) is a member in any combination of any of Disclosures (1) to (17) in which a test piece of the member (size: 10 mm × 50 mm × 2 mm) is immersed in each of the following 10 chemical solutions for one week, and the relative value of the mass after immersion, with the mass before immersion set to 100, is determined, and the average of the relative values ​​for the 10 chemical solutions is 95 or more and 105 or less, with a standard deviation of 20 or less. (Medicinal solution) 25% by mass TMAH([(CH3)4N] + [OH] - (80℃) 98% by mass sulfuric acid (90℃) 100% by mass isopropyl alcohol (80℃) 49% by mass hydrofluoric acid (70℃) Mixed acid of hydrofluoric acid and nitric acid (a mixture of 49% hydrofluoric acid and 69-71% nitric acid in a volume ratio of 1:5) (20℃) Mixed acid of hydrofluoric acid and nitric acid (a mixture of 49% hydrofluoric acid and 69-71% nitric acid by mass in a volume ratio of 1:100) (20℃) SPM (a mixture of 98% sulfuric acid by mass and 30-36% hydrogen peroxide by mass in a volume ratio of 2:1) (80°C) SC1 (a mixture of 25-28% by mass of aqueous ammonia, 30-36% by mass of aqueous hydrogen peroxide, and deionized water in a volume ratio of 1:1:5) (70°C) SC2 (a mixture of 35-37% hydrochloric acid, 30-36% hydrogen peroxide, and deionized water in a volume ratio of 1:1:4) (70°C) 85% by mass phosphoric acid (80℃)

[0023] The present disclosure (19) is a member in any combination with any of the present disclosures (1) to (18), wherein the load deflection temperature at a load of 1.82 MPa is 50°C or higher.

[0024] Disclosure (20) is a component in any combination of any of Disclosures (1) to (19) in which the amount of metal leaching of 16 elements (Li, Na, Mg, Al, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Ag, Cd, Pb) is 20 ppb or less when a test piece of the component (size: 10 mm × 50 mm × 2 mm) is immersed in 3.6 mass% hydrochloric acid at 23°C for one week.

[0025] Disclosure (21) is a semiconductor manufacturing-related apparatus equipped with any combination of components from Disclosures (1) to (20).

[0026] Disclosure (22) is a semiconductor manufacturing-related apparatus of Disclosure (21), which is at least one selected from the group consisting of semiconductor manufacturing apparatus and semiconductor manufacturing apparatus-related apparatus.

[0027] This disclosure (23) states that the semiconductor manufacturing apparatus is at least one selected from the group consisting of photolithography apparatus, thin film formation / etching / cleaning / drying apparatus, inspection / evaluation apparatus / manufacturing apparatus, resist processing apparatus, etching apparatus, cleaning / drying apparatus, CVD apparatus, thin film formation apparatus, CMP apparatus, processing apparatus, aging apparatus, and inspection apparatus. The semiconductor manufacturing equipment according to the present disclosure (22) is a semiconductor manufacturing equipment in which the semiconductor manufacturing equipment is at least one selected from the group consisting of a pure water / chemical equipment, a gas equipment, a cleanroom equipment, and manufacturing equipment.

[0028] This disclosure (24) states that the photolithography apparatus is at least one selected from the group consisting of a coating apparatus, a resist stripping apparatus, a developing apparatus (developer), and a discam apparatus. The thin film formation, etching, cleaning, and drying apparatus is at least one selected from the group consisting of a vacuum deposition apparatus, a cleaning apparatus, a drying apparatus, and a scrubbing cleaning apparatus. The aforementioned inspection and evaluation device / manufacturing device is a defect correction device, The resist processing apparatus is at least one selected from the group consisting of a coating apparatus, a developing apparatus, a resist stripping apparatus, and an ashing apparatus. The etching apparatus is at least one selected from the group consisting of a dry etching apparatus and a wet etching apparatus. The washing and drying apparatus is at least one selected from the group consisting of a wet washing apparatus, a scrubbing washing apparatus, and a drying apparatus. The CVD apparatus is at least one selected from the group consisting of high-pressure CVD apparatus, SACVD, reduced-pressure CVD, plasma CVD apparatus, metal CVD apparatus, and ALD apparatus. The thin film formation apparatus is at least one selected from the group consisting of a vacuum deposition apparatus, a silicon epitaxial growth apparatus, a compound semiconductor epitaxial apparatus (MOCVD apparatus, MBE apparatus), and a plating apparatus. The CMP device is at least one selected from the group consisting of a CMP device and a CMP cleaning device. The aforementioned processing apparatus is a bump plating apparatus, The aging apparatus is at least one selected from the group consisting of an aging apparatus, a burn-in apparatus, an IC insertion apparatus, and an IC extraction apparatus. The inspection device is a life test device, The aforementioned pure water / chemical solution system is at least one selected from the group consisting of a chemical supply system, a slurry supply system, a chemical purification system, and a waste liquid treatment system. The gas apparatus is at least one selected from the group consisting of a gas generator, a gas purification device, a gas mixing device, a gas detection device, and an exhaust gas treatment device. The cleanroom equipment is at least one selected from the group consisting of a thermal chamber and an environmental testing apparatus. The semiconductor manufacturing equipment of this disclosure (23) is at least one selected from the group consisting of a jig cleaning and drying device, a flow control device, a packaging device, and a liquid / gas measuring device. [Effects of the Invention]

[0029] According to this disclosure, it is possible to provide a component with excellent corrosion resistance and semiconductor manufacturing-related equipment using the same. [Modes for carrying out the invention]

[0030] The following provides a detailed explanation of this disclosure.

[0031] This disclosure relates to a component comprising at least one thermoplastic resin selected from the group consisting of polyolefin resins and chlorine-based resins, wherein the component is at least one selected from the group consisting of building materials, mobility components, aerospace components, semiconductor components, and information and communication components, and is a component that comes into contact with corrosive substances. The components of this disclosure have excellent corrosion resistance (particularly chemical resistance).

[0032] The components of this disclosure also have excellent heat resistance and can suppress metal leaching.

[0033] The components of this disclosure include at least one thermoplastic resin selected from the group consisting of polyolefin resins and chlorine-based resins. In terms of heat resistance, the inclusion of a polyolefin resin is preferable.

[0034] The thermoplastic resin described above may be crystalline or amorphous, but it is preferable that it be crystalline in terms of corrosion resistance and heat resistance.

[0035] In the case of crystalline resins, the above thermoplastic resin preferably has a melting point of 100°C or higher, more preferably 120°C or higher, even more preferably 150°C or higher, and particularly preferably 180°C or higher, as this further improves corrosion resistance and heat resistance. It is also preferably 350°C or lower, and more preferably 320°C or lower. The melting point of a thermoplastic resin is the temperature corresponding to the maximum value in the heat of fusion curve when the temperature is increased at a rate of 10°C / min using a differential scanning calorimetry (DSC) device.

[0036] In the case of crystalline resins, the above thermoplastic resin preferably has a glass transition temperature of -130°C or higher, more preferably -10°C or higher, even more preferably 5°C or higher, and also preferably 300°C or lower, more preferably 250°C or lower, even more preferably 200°C or lower, and even more preferably 100°C or lower, in terms of further improving corrosion resistance and heat resistance.

[0037] In the case of an amorphous resin, the above thermoplastic resin preferably has a glass transition temperature of 60°C or higher, more preferably 100°C or higher, still more preferably 120°C or higher, and preferably 300°C or lower, more preferably 250°C or lower, still more preferably 200°C or lower, in terms of further improving corrosion resistance and heat resistance.

[0038] The glass transition temperature of the thermoplastic resin is measured under the condition of a heating rate of 10°C / min using a differential scanning calorimetry (DSC) apparatus in accordance with JIS K7121.

[0039] In terms of further improving corrosion resistance and heat resistance, the above thermoplastic resin preferably has a heat of fusion of 1 J / g or more, more preferably 5 J / g or more, still more preferably 10 J / g or more, still more preferably 30 J / g or more, particularly preferably 40 J / g or more, and preferably 300 J / g or less, more preferably 150 J / g or less, still more preferably 120 J / g or less, still more preferably 100 J / g or less, particularly preferably 90 J / g or less. The heat of fusion of the thermoplastic resin is measured under the condition of a heating rate of 10°C / min using a differential scanning calorimetry (DSC) apparatus.

[0040] In terms of corrosion resistance, the above thermoplastic resin preferably has a density of 1.50 g / m 3 or less, more preferably 1.10 g / m 3 or less, and preferably 0.80 g / m 3 or more. The density of the thermoplastic resin is measured in accordance with JIS K7112.

[0041] Examples of the above-mentioned polyolefin resins include polyethylene resin, polypropylene resin, ethylene-propylene copolymer resin, amorphous cycloolefin resin, crystalline cycloolefin resin, polymethylpentene resin, amorphous polystyrene resin, crystalline polystyrene resin, polybutylene resin, etc., and one or more of these can be used. In particular, from the viewpoint of corrosion resistance, at least one selected from the group consisting of polyethylene resin, polypropylene resin, amorphous cycloolefin resin, crystalline cycloolefin resin, and polymethylpentene resin is preferred, and from the viewpoint of heat resistance, at least one selected from the group consisting of polypropylene resin, amorphous cycloolefin resin, crystalline cycloolefin resin, and polymethylpentene resin is more preferred, and at least one selected from the group consisting of amorphous cycloolefin resin, crystalline cycloolefin resin, and polymethylpentene resin is even more preferred.

[0042] The polyethylene resin described above may be a homopolymer of ethylene and / or a copolymer of ethylene and α-olefin. In the case of a copolymer of ethylene and α-olefin, α-olefins having 3 to 20 carbon atoms are preferred, α-olefins having 3 to 18 carbon atoms are more preferred, and α-olefins having 3 to 12 carbon atoms are even more preferred.

[0043] Examples of the above-mentioned α-olefins include propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, etc., and one or more of these can be used. Among these, 1-butene and 1-hexene are preferred.

[0044] As the polyethylene resin mentioned above, copolymers of ethylene and diene can also be used. Examples of diene compounds used in this case include butadiene, 1,4-hexadiene, ethylidene norbornene, dicyclopentadiene, etc., and one or more of these can be used.

[0045] The proportion of copolymer monomers such as α-olefins and dienes is preferably 40 mol% or less, more preferably 30 mol% or less, even more preferably 20 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5.0 mol% or less. It may also be 0 mol% or more, or 0.001 mol% or more.

[0046] The melt flow rate (MFR) of the above polyethylene resin (excluding the ultra-high molecular weight polyethylene described later) is not particularly limited, but in terms of the appearance of the resulting molded article, for example when used in blow molding, it is preferable that the MFR measured at 190°C and a load of 2.16 kg be 0.03 g / 10 min or more, more preferably 0.1 g / 10 min or more, even more preferably 0.2 g / 10 min or more, and also preferably 3 g / 10 min or less, more preferably 2 g / 10 min or less, even more preferably 1.5 g / 10 min or less, even more preferably 1 g / 10 min or less, and particularly preferably 0.5 g / 10 min or less.

[0047] When the above polyethylene resin (excluding the ultra-high molecular weight polyethylene described later) is used in extrusion molding, it is preferable that the MFR is 0.01 g / 10 min or more, more preferably 0.1 g / 10 min or more, and also preferable that it is 5 g / 10 min or less, more preferably 4.5 g / 10 min or less, and even more preferably 4 g / 10 min or less.

[0048] When the above polyethylene resin (excluding the ultra-high molecular weight polyethylene described later) is used in injection molding, it is preferable that the MFR is 1 g / 10 min or more, more preferably 3 g / 10 min or more, even more preferably 5 g / 10 min or more, even more preferably 10 g / 10 min or more, particularly preferably 20 g / 10 min or more, and also preferably 300 g / 10 min or less, more preferably 200 g / 10 min or less, even more preferably 100 g / 10 min or less, even more preferably 90 g / 10 min or less, and particularly preferably 80 g / 10 min or less.

[0049] The above MFR is measured in accordance with JIS K6922-2:1997 at 190°C and under a load of 2.16 kg.

[0050] The molecular weight-bearing capacity (MFR) of the polyethylene resin described above can be adjusted by controlling the ethylene polymerization temperature and the use of chain transfer agents. For example, increasing the polymerization temperature between ethylene and α-olefin can lower the molecular weight and thus increase the MFR, while lowering the polymerization temperature can increase the molecular weight and thus decrease the MFR. Furthermore, in the copolymerization reaction between ethylene and α-olefin, increasing the amount of coexisting hydrogen (amount of chain transfer agent) can lower the molecular weight and thus increase the MFR, while decreasing the amount of coexisting hydrogen (amount of chain transfer agent) can increase the molecular weight and thus decrease the MFR.

[0051] The polyethylene resin mentioned above has a density of 0.900 to 0.980 g / cm³. 3 Preferably, it is 0.910 g / cm³. More preferably, it is 0.910 g / cm³. 3 More preferably 0.920 g / cm³ 3 More preferably, 0.930 g / cm³ 3 In particular, 0.932 g / cm³ is preferred. 3 More preferably, 0.970 g / cm³ 3 More preferably, 0.960 g / cm³ 3Even more preferably, 0.950 g / cm³ 3 The following is particularly preferred: 0.948 g / cm³ 3 The following applies: The above densities are measured in accordance with JIS-K6922-1,2:1997. The above density can be adjusted, for example, by changing the type and amount of α-olefin copolymerized with ethylene.

[0052] The polyethylene resin described above can be manufactured by known methods, and the manufacturing catalyst, process, etc., are not limited. Furthermore, the monomer used as a raw material may be derived from petroleum raw materials, biomass raw materials, or both.

[0053] Conventional known catalysts such as Ziegler-Natta catalysts, Phillips catalysts, and metal catalysts such as metallocene catalysts can be used as polymerization catalysts. Generally, these catalysts are complexes composed of organometallic compounds supported on a carrier such as silica or a magnesium compound.

[0054] Polymerization methods include high-pressure methods, solution methods, slurry methods, and gas-phase methods. The high-pressure method is a method in which polymerization is carried out under high temperature and high pressure by introducing ethylene, comonomers, and the catalyst into a reaction vessel, using a radical generating source such as oxygen or peroxides, or a catalyst consisting of a metal complex, as the initiator. Depending on the shape of the reaction vessel, it can be further divided into the tubular method and the autoclave method. The solution method is a polymerization method in which the polymer is dissolved in a hydrocarbon solvent at a temperature above the polymer's melting point. The slurry method is a polymerization method in which a hydrocarbon compound is used as a solvent, and the resulting polyethylene exists as a slurry in the solvent. Depending on the shape of the reaction vessel, it is broadly classified into two types: the autoclave method and the loop pipe method. As the solvent, an inert hydrocarbon solvent selected from aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene, and xylene, and alicyclic hydrocarbons such as cyclohexane and methylcyclohexane is preferably used. The gas-phase method is a polymerization method in which ethylene and α-olefin as a comonomer, along with hydrogen as a chain transfer agent, are fed in gaseous form from the bottom of a vertical reaction vessel, and a polymerization catalyst is then added.

[0055] The polyethylene resin described above may contain polar groups. Examples of polyethylene resins containing polar groups include ethylene homopolymers and / or copolymers of ethylene and α-olefins in which polar groups have been graft-modified. Preferred α-olefins and their copolymerization ratios are as described above. The above polar group refers to a substituent that has electrical polarity, and is preferably a carboxyl group and / or a carboxylic acid anhydride group. Polyethylene resins containing polar groups can be produced by reacting a homopolymer of ethylene and / or a copolymer of ethylene and α-olefin with a compound containing polar groups. Examples of compounds containing the above polar group include α,β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, and itaconic acid, or their anhydrides, as well as unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, vinylacetic acid, and pentenoic acid, among which maleic anhydride, acrylic acid, and methacrylic acid are preferred.

[0056] The polar groups contained in the polyethylene resin containing polar groups are preferably 0.05% by mass or more, more preferably 0.10% by mass or more, and preferably 2.0% by mass or less, and more preferably 1.0% by mass or less, relative to the polyethylene resin containing polar groups. The amount of polar groups can be measured by infrared spectroscopy (IR).

[0057] Polyethylene resins containing polar groups can be produced by methods such as grafting a polar group-containing monomer onto polyethylene, and known methods can be used as appropriate. Specifically, known methods include a melting method in which a polar group-containing monomer is reacted with a reaction initiator to a polyethylene resin that has been brought to a molten state by an extruder or the like, and a solution method in which the polyethylene resin is dissolved in a solvent and the polar group-containing monomer is reacted with a reaction initiator. Both can be suitably used, but the melting method is more suitably selected in terms of production cost and environmental impact. While there are no limitations on the melt kneading equipment used for graft modification, single-screw extruders, twin-screw extruders, kneaders, Banbury mixers, Brabenders, and reciprocating kneaders (Buss Kneaders) are commonly used, with single-screw and twin-screw extruders being more preferable in terms of productivity. Reaction initiators used in graft modification include radical initiators that decompose upon heating or other means to generate radicals. Examples of radical initiators include organic peroxides, dihydroaromatic compounds, and dicumyl compounds. The graft modification temperature is appropriately selected considering factors such as the degradation of the polyethylene resin, the decomposition of polar group-containing monomers, and the decomposition temperature of the peroxide used. However, taking the aforementioned melt kneading method as an example, the temperature is usually 190 to 350°C, with 200 to 300°C being particularly preferable.

[0058] The polyethylene resin described above may contain additives commonly used in polyolefins, such as antioxidants, weather stabilizers, antistatic agents, lubricants, antiblocking agents, and organic and inorganic pigments, as needed. The method of mixing the above additives into the resin is not particularly limited, but examples include adding them directly during the granulation process of the pellets after polymerization, or preparing a high-concentration masterbatch in advance and dry-blending it during molding.

[0059] Examples of the polyethylene resin (PE) mentioned above include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), very low-density polyethylene (VLDPE), ultra-high molecular weight polyethylene (UHPE), and cross-linked polyethylene (PEX). Among these, from the viewpoint of corrosion resistance, at least one selected from the group consisting of high-density polyethylene and ultra-high molecular weight polyethylene is preferred, and ultra-high molecular weight polyethylene is more preferred.

[0060] The high-density polyethylene mentioned above has a density of 0.940 g / m³. 3 Preferably, it is 0.945 g / cm³ or more. 3 It is more preferable that the amount be greater than or equal to 0.970 g / m². 3 Preferably, it is 0.965 g / m 3 The following is more preferable: The density of polyethylene is measured in accordance with JIS K7112.

[0061] The high-density polyethylene described above preferably has a linear structure, and preferably the number of long-chain branches in the fraction with a molecular weight of 100,000 or more Mn per 1,000 carbon atoms of the main chain is 0.10 or less, and may be 0.01 or more.

[0062] Molecular weight fractionation is performed by the following method. A glass bead-packed column (diameter: 21 mm, length: 60 cm) was used, and the column temperature was set to 130°C. A solution of 1 g of sample dissolved in 30 mL of xylene was injected. Next, a xylene / 2-ethoxyethanol mixture in a 5 / 5 ratio was used as the developing solvent, and the distillate was removed. Then, xylene was used as the developing solvent, and the components remaining in the column were distilled to obtain a polymer solution. Five times the volume of methanol was added to the obtained polymer solution to precipitate the polymer, and the solution was filtered and dried to recover components with a manganese content of 100,000 or more.

[0063] The number of long-chain branches is measured by the following method. Using the JNM-GSX400 nuclear magnetic resonance spectrometer manufactured by JEOL Ltd., 13 The number of branches with hexyl or more groups is measured by 13C-NMR. The solvent is benzene-d6 / orthodichlorobenzene (volume ratio 30 / 70). The number of branches per 1,000 methylene carbons in the main chain (chemical shift: 30 ppm) is determined from the average value of the peaks for α-carbon (34.6 ppm) and β-carbon (27.3 ppm).

[0064] The above-mentioned high-density polyethylene may be modified high-density polyethylene. The above-mentioned modified high-density polyethylene is a resin obtained by grafting at least one monomer selected from the group consisting of unsaturated carboxylic acids and their derivatives onto unmodified high-density polyethylene in the presence of a radical generator.

[0065] Unsaturated carboxylic acids and their derivatives used in the production of the above-mentioned modified high-density polyethylene include monobasic unsaturated carboxylic acids and dibasic unsaturated carboxylic acids, as well as their metal salts, amides, imides, esters, and anhydrides. Of these, monobasic unsaturated carboxylic acids generally have at most 20 carbon atoms, preferably 15 or fewer. The number of carbon atoms in their derivatives is usually at most 20 or fewer, preferably 15 or fewer. Furthermore, dibasic unsaturated carboxylic acids generally have 30 carbon atoms or fewer, preferably 25 or fewer. The number of carbon atoms in their derivatives is usually 30 or fewer, preferably 25 or fewer. Among these unsaturated carboxylic acids and their derivatives, acrylic acid, methacrylic acid, maleic acid and its anhydride, 5-norbornene-2,3-dicarboxylic acid and its anhydride, and glycidyl methacrylate are preferred, with maleic anhydride and 5-norbornene anhydride being particularly preferred.

[0066] The radical generating agent used in the production of the above-mentioned modified high-density polyethylene is not particularly limited, but organic peroxides are preferred. Suitable organic peroxides have a half-life decomposition temperature of 100°C or higher. Suitable organic peroxides include dicumyl peroxide, benzoyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-di-(t-butylperoxy)hexane, 2,5-dimethyl-2,5-(t-butylperoxy)hexane-3, lauroyl peroxide, and t-butylperoxybenzoate.

[0067] The above-mentioned modified high-density polyethylene is produced by uniformly mixing and processing unmodified high-density polyethylene resin, an unsaturated carboxylic acid and / or its derivatives, and a radical generator. Specifically, this can be done by a melt-kneading method using an extruder, Banbury mixer, kneader, etc., a solution method in which the material is dissolved in a suitable solvent, a slurry method in which the material is suspended in a suitable solvent, or the so-called gas-phase graft method. The processing temperature is appropriately selected considering factors such as the degradation of high-density polyethylene, the decomposition of unsaturated carboxylic acids and their derivatives, and the decomposition temperature of the peroxides used. However, taking the above-mentioned melt kneading method as an example, the temperature is usually 190 to 350°C, with 200 to 300°C being particularly preferable.

[0068] In producing the above-mentioned modified high-density polyethylene, in order to improve its performance, known methods can be employed, such as those described in Japanese Patent Publication No. 62-010107, including treatment with epoxy compounds or polyfunctional compounds containing amino groups or hydroxyl groups during or after graft modification, and further methods to remove unreacted monomers (unsaturated carboxylic acids and their derivatives) and by-products by heating or washing. While a higher graft amount of at least one monomer selected from the group consisting of the above-mentioned unsaturated carboxylic acids and their derivatives is desirable, it is generally in the range of 0.001 to 10% by mass.

[0069] The above ultra-high molecular weight polyethylene has a weight-average molecular weight of 1.0 × 10⁻⁶. 6Preferably, it is 1.2 × 10 6 It is more preferable that the above is true, and also 7.0 × 10 7 Preferably, it is 7.0 × 10 6 The following is more preferable: The molecular weight of polyethylene is measured by converting it to polystyrene equivalent using gel permeation chromatography (GPC), and the molecular weight of ultra-high molecular weight polyethylene is measured by converting it from its intrinsic viscosity using the viscosity method.

[0070] Examples of the above-mentioned ultra-high molecular weight polyethylene include ultra-high molecular weight ethylene homopolymers; ultra-high molecular weight ethylene-α-olefin copolymers such as ultra-high molecular weight ethylene-propylene copolymers, ultra-high molecular weight ethylene-1-butene copolymers, ultra-high molecular weight ethylene-1-hexene copolymers, and ultra-high molecular weight ethylene-1-octene copolymers; and the like.

[0071] The above-mentioned ultra-high molecular weight polyethylene may be in any form, such as particulate, pelletized, sheeted, or lumpy. Among these forms, particulate polyethylene with an average particle size of 1 to 1000 μm is preferred because it offers excellent productivity during processing and the resulting material has superior physical properties and moldability. The above average particle size can be measured by methods such as the sieving test method using a standard sieve specified in JIS Z8801.

[0072] The above-mentioned ultra-high molecular weight polyethylene preferably has an intrinsic viscosity ([η]) of 10 dl / g or more, more preferably 15 dl / g or more, even more preferably 20 dl / g or more, and also preferably 80 dl / g or less, more preferably 60 dl / g or less, and even more preferably 50 dl / g or less, from the viewpoint of mechanical strength and heat resistance. The above-mentioned intrinsic viscosity can be measured, for example, using an Ubbelohde viscometer with a polymer concentration of 0.0005 to 0.01% in a solution with decahydronaphthalene as the solvent, at 135°C.

[0073] The above-mentioned ultra-high molecular weight polyethylene may be obtained as a commercially available product. Examples of commercially available products (product names) include GUR4113, GUR4120, GUR4130 (all manufactured by Celanese), Sunfine UH900, Sunfine UH950 (both manufactured by Asahi Kasei Chemicals Corporation), Hyzex Million 240M, Hyzex Million 340M (both manufactured by Mitsui Chemicals, Inc.).

[0074] Any method may be used to produce the ultra-high molecular weight polyethylene described above. For example, a method can be used to perform homopolymerization of ethylene or copolymerization of ethylene with other olefins using a polyethylene production catalyst. Examples of α-olefins in this case include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, and 1-octene. As for the polymerization method, examples include solution polymerization, bulk polymerization, gas-phase polymerization, and slurry polymerization. Among these, slurry polymerization is particularly preferred because it enables the production of ultra-high molecular weight polyethylene with uniform particle shape, and allows for the efficient and stable production of ultra-high molecular weight polyethylene compositions that have a high melting point, high crystallinity, and excellent mechanical strength, heat resistance, and abrasion resistance. Furthermore, any commonly used organic solvent can be used as the solvent for the slurry polymerization method, such as benzene, toluene, xylene, pentane, hexane, and heptane. Liquefied gases such as isobutane and propane, and olefins such as propylene, 1-butene, 1-octene, and 1-hexene can also be used as solvents.

[0075] The above polypropylene resin (PP) may be a propylene homopolymer, a copolymer of propylene and another monomer, or a hydrogenated product of the above polymer. Two or more propylene resins (for example, a propylene homopolymer and a propylene copolymer) may be used in combination as the above polypropylene resin.

[0076] Other monomers copolymerized with propylene include α-olefins and non-conjugated dienes, which can be used individually or in combination of two or more.

[0077] Examples of the above-mentioned α-olefins include α-olefins having 2 or 4 to 20 carbon atoms. More specifically, examples include ethylene, 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, etc.

[0078] The above non-conjugated diene is given by the following formula (A): CH2=CR 1A -(CH2) n -CR 2A =CR 3A R 4A (In the formula, R 1A , R 2A , R 3A , and R 4A Each of these is independently either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer from 1 to 20. Examples of compounds represented by [the formula shown] are given.

[0079] R 1A , R 2A , R 3A , and R 4AThe alkyl group having 1 to 6 carbon atoms may be linear or branched. Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, t-pentyl, neopentyl, n-hexyl, and isohexyl groups.

[0080] If the polypropylene resin is a copolymer, it may be either a random copolymer or a block copolymer. The content of propylene-derived skeletons in random copolymers is typically 90-99 mol%, preferably 92-98 mol%. The content of propylene-derived skeletons in block copolymers is typically 70-99 mol%, preferably 75-98 mol%.

[0081] The above-mentioned polypropylene resin is preferably a crystalline polypropylene resin.

[0082] The above polypropylene resin may also be a propylene-based block copolymer containing a crystalline propylene polymer portion and a propylene-ethylene random copolymer portion. Such a propylene-based block copolymer is a reaction mixture of a crystalline propylene polymer portion and a propylene-ethylene random copolymer portion, and is obtained by a manufacturing process consisting of polymerization of the crystalline propylene polymer portion, which is a propylene homopolymer portion (first stage), followed by polymerization of the propylene-ethylene random copolymer portion (second stage). The above crystalline propylene polymer is produced in one or more polymerization steps (the reaction conditions for each step are the same or different), and the propylene-ethylene random copolymer portion is also produced in one or more polymerization steps (the reaction conditions for each step are the same or different). Therefore, the entire manufacturing process of the above propylene-based block copolymer consists of at least two sequential multi-stage polymerization steps.

[0083] The above polypropylene resin is suitable in terms of flexural modulus and heat resistance. 13The isotactic pentad fraction (mmmm fraction) of the propylene homopolymer, as measured by 13C-NMR, is preferably 96.0% or higher, more preferably 96.5% or higher, and even more preferably 97.0% or higher.

[0084] Here, the isotactic pentad fraction (mmmm fraction) is the method described by A. Zambelli et al. in Macromolecules, Vol. 6, 925 (1973), i.e. 13 This is the isotactic fraction of pentad units in a polypropylene molecular chain, measured by 13C-NMR (nuclear magnetic resonance spectroscopy), and represents the fraction of propylene monomer units in which five propylene units are isotactically linked.

[0085] 13 The assignment of peaks in the 1C-NMR spectrum is based on the description in Macromolecules, Vol. 8, 687 (1975). 13 ¹¹C-NMR can be measured using a Fourier transform NMR [500 MHz (for hydrogen nucleus measurement)] instrument, with a frequency of 125 MHz and 20,000 integrated measurements, thereby improving the signal detection limit to 0.001.

[0086] The above polypropylene resin may have a long-chain branched structure. Having a long-chain branched structure improves the melt properties. The above long-chain branched structure can be evaluated, for example, by the degree of strain hardening (λmax) in the measurement of extensional viscosity, and the greater the amount of branching and the longer the length of the branching, the greater the degree of strain hardening. The above degree of strain hardening is preferably 6.0 or higher, more preferably 7.0 or higher, even more preferably 8.0 or higher, and even more preferably 9.0 or higher. Regarding the method for measuring strain hardening, any method that can measure uniaxial extensional viscosity will, in principle, yield the same value. For example, the measurement method and measuring equipment described in Polymer 42 (2001) 8663 can be used.

[0087] The above polypropylene resin has a weight-average molecular weight of 5.0 × 104 Preferably, it is 1.0 × 10 5 It is more preferable that the above is true, and also 1.0 × 10 6 Preferably, it is 7.0 × 10 5 The following is more preferable: The molecular weight of polypropylene resin is measured by gel permeation chromatography (GPC, column temperature: 140°C, eluent: 1,2,4-trichlorobenzene) in polystyrene equivalent.

[0088] While there are no particular restrictions on the melt flow rate (MFR) of the above-mentioned polypropylene resin, in terms of the appearance of the resulting molded article, when used in blow molding, the MFR is preferably 0.03 g / 10 min or more, more preferably 0.1 g / 10 min or more, even more preferably 0.2 g / 10 min or more, and also preferably 3 g / 10 min or less, more preferably 2 g / 10 min or less, even more preferably 1.5 g / 10 min or less, even more preferably 1 g / 10 min or less, and particularly preferably 0.5 g / 10 min or less.

[0089] When the above polypropylene resin is used in extrusion molding, it is preferable that the MFR is 0.01 g / 10 min or more, more preferably 0.1 g / 10 min or more, and also preferable that it is 5 g / 10 min or less, more preferably 4.5 g / 10 min or less, and even more preferably 4 g / 10 min or less.

[0090] When the above polypropylene resin is used in injection molding, it is preferable that the MFR is 1 g / 10 min or more, more preferably 3 g / 10 min or more, even more preferably 5 g / 10 min or more, particularly preferably 10 g / 10 min or more, and also preferably 300 g / 10 min or less, more preferably 200 g / 10 min or less, even more preferably 100 g / 10 min or less, even more preferably 90 g / 10 min or less, and particularly preferably 80 g / 10 min or less.

[0091] The MFR of the above polypropylene resin is measured in accordance with JIS K7210 at 230°C and under a load of 21.18 N (2.16 kg). The above-mentioned polypropylene resin may be a mixture of two or more polypropylene resins with different MFRs.

[0092] The above-mentioned polypropylene resin may contain reinforcing fibers. Examples of the reinforcing fibers include glass fibers, carbon fibers, carbon nanotubes, basic magnesium sulfate fibers (magnesium oxysulfate fibers), potassium titanate fibers, aluminum borate fibers, calcium silicate fibers, calcium carbonate fibers, silicon carbide fibers, wollastonite, xonotlite, metal fibers, natural fibers (cotton, cellulose, silk, wool, and hemp, etc.), regenerated fibers (rayon and cupro, etc.), semi-synthetic fibers (acetate and promix, etc.), synthetic fibers (polyester, polyacrylonitrile, polyamide, aramid, and polyolefin, etc.), and modified fibers obtained by chemically modifying the surface and ends thereof. Among these, glass fibers are preferred.

[0093] Chopped strands are preferred as the form of the reinforcing fibers. Chopped strands typically have a length of 1 to 10 mm and a fiber diameter of 5 to 20 μm, preferably 1.5 to 6 mm in length and 8 to 14 μm in fiber diameter. As another form, continuous fiber bundles can also be used. Continuous fiber bundles are commercially available, for example, as rovings. Their fiber diameter is typically 5 to 30 μm, preferably 13 to 20 μm.

[0094] The content of the reinforcing fibers is preferably 10 to 50 parts by mass, more preferably 20 to 40 parts by mass, based on 100 parts by mass of the total of the propylene polymer and reinforcing fibers.

[0095] The amorphous cycloolefin resin and crystalline cycloolefin resin described above may be a cycloolefin homopolymer (COP), or a cycloolefin copolymer (COC), which is a copolymer of cycloolefin and an acyclic olefin such as ethylene.

[0096] The above amorphous cycloolefin resin has a weight-average molecular weight of 1.0 × 10⁻⁶. 4 Preferably, it is 2.0 × 10 4 It is more preferable that the above is true, and also 1.0 × 10 6 Preferably, it is 7.0 × 10 5 The following is more preferable: The molecular weight of amorphous cycloolefin resins is measured by gel permeation chromatography (GPC, column temperature: 40°C, eluent: methylcyclohexane) and converted to polyisobutylene equivalent.

[0097] Norbornene monomers are preferred as cycloolefin monomers used in the above amorphous cycloolefin resin. Norbornene monomers are monomers containing a norbornene ring, and specifically include norbornenes, tetracyclododecenes, dicyclopentadienes, and the like. These may have hydrocarbon groups or polar groups as substituents. Examples of the above hydrocarbon groups include alkyl groups, alkenyl groups, alkylidene groups, and aryl groups. Examples of polar groups include hydroxyl groups, alkoxy groups having 1 to 10 carbon atoms, alkoxycarbonyl groups, allyloxycarbonyl groups, cyano groups, amide groups, imide ring-containing groups, triorganosiloxy groups, triorganosilyl groups, amino groups, acyl groups, alkoxysilyl groups, sulfonyl-containing groups, carboxyl groups, acid anhydride groups, halogens, and the like. More specifically, examples of the above alkoxy groups include methoxy groups and ethoxy groups; examples of alkoxycarbonyl groups include methoxycarbonyl groups and ethoxycarbonyl groups; examples of allyloxycarbonyl groups include phenoxycarbonyl groups, naphthyloxycarbonyl groups, fluorenyloxycarbonyl groups, and biphenylyloxycarbonyl groups; examples of triorganosiloxy groups include trimethylsiloxy groups and triethylsiloxy groups; examples of triorganosilyl groups include trimethylsilyl groups and triethylsilyl groups; examples of amino groups include primary amino groups, and examples of alkoxysilyl groups include trimethoxysilyl groups and triethoxysilyl groups. Furthermore, the norbornene monomer described above may have additional double bonds in addition to the double bond of the norbornene ring. Among these, norbornene monomers that do not contain polar groups, i.e., those composed only of carbon and hydrogen atoms, are preferred. The number of rings constituting the norbornene monomer is preferably 3 to 6, more preferably 3 or 4, and particularly preferred to be 4.

[0098] Examples of norbornene monomers that do not contain polar groups include norbornene compounds with two rings, such as 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-decyl-2-norbornene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, and 5-propenyl-2-norbornene; Norbornenes, such as 5-cyclohexyl-2-norbornene, 5-cyclopentyl-2-norbornene, 5-cyclohexenyl-2-norbornene, 5-cyclopentenyl-2-norbornene, and 5-phenyl-2-norbornene, which have three rings; Tetracyclo[9.2.1.0 2,10 .0 3,8 Tetradeca-3,5,7,12-tetraene (also known as 1,4-methano-1,4,4a,9a-tetrahydro-9H-fluorene), tetracyclo[10.2.1.0 2,11 .0 4,9 Norbornenes with four rings, such as pentadeca-4,6,8,13-tetraene (also known as 1,4-methano-1,4,4a,9,9a,10-hexahydroanthracene);

[0099] Tetracyclo[6.2.1.1 3,6 .0 2,7 ] Dodeca-4-ene, 9-methyltetracyclo[6.2.1.1 3,6 .0 2,7 ] Dodeca-4-ene, 9-ethyltetracyclo[6.2.1.1 3,6 .0 2,7 ] Dodeca-4-ene, 9-methylenetetracyclo[6.2.1.1 3,6 .0 2,7 ] Dodeca-4-ene, 9-ethylidenetetracyclo[6.2.1.1 3,6 .0 2,7 ] Dodeca-4-ene, 9-vinyltetracyclo[6.2.1.1 3,6 .0 2,7 ] Dodeca-4-ene, 9-propenyltetracyclo[6.2.1.1 3,6 .0 2,7 Tetracyclododecenes, such as dodeca-4-ene, which have four rings; 9-Cyclohexyltetracyclo[6.2.1.1 3,6 .0 2,7 ] Dodeca-4-ene, 9-cyclopentyltetracyclo[6.2.1.1 3,6 .0 2,7 ] Dodeca-4-ene, 9-cyclohexenyltetracyclo[6.2.1.1 3,6 .0 2,7Dodeca-4-ene, 9-cyclopentenyltetracyclo[6.2.1.1 3,6 .0 2,7 Dodeca-4-ene, 9-phenyltetracyclo[6.2.1.1 3,6 .0 2,7 Tetracyclododecenes with 5 rings such as dodeca-4-ene;

[0100] Dicyclopentadiene, methyldicyclopentadiene, dihydrodicyclopentadiene (tricyclo[5.2.1.0 2,6 Deca-8-ene (also called).) Dicyclopentadienes with 3 rings such as;

[0101] Pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 Pentadeca-4,10-diene, pentacyclo[9.2.1.1 4,7 .0 2,10 .0 3,8 Pentadeca-5,12-diene, hexacyclo[6.6.1.1 3,6 .1 10,13 .0 2,7 .0 9,14 Norbornenes with 5 or more rings such as heptadeca-4-ene, norbornene-based monomers other than tetracyclododecenes and dicyclopentadienes; etc. are included.

[0102] As norbornene-based monomers containing a polar group, tetracyclo[6.2.1.1 3,6 .0 2,7 Methyl dodeca-9-ene-4-carboxylate, tetracyclo[6.2.1.1 3,6 .0 2,7 Dodeca-9-ene-4-methanol, tetracyclo[6.2.1.1 3,6 .0 2,7 Dodeca-9-ene-4-carboxylic acid, tetracyclo[6.2.1.1 3,6 .0 2,7 Dodeca-9-ene-4,5-dicarboxylic acid, tetracyclo[6.2.1.1 3,6 .0 2,7Examples include dodeca-9-en-4,5-dicarboxylic acid anhydride, methyl 5-norbornene-2-carboxylate, methyl 2-methyl-5-norbornene-2-carboxylate, 5-norbornene-2-yl acetate, 5-norbornene-2-methanol, 5-norbornene-2-ol, 5-norbornene-2-carbonitride, 2-acetyl-5-norbornene, and 7-oxa-2-norbornene. Furthermore, the norbornene monomers mentioned above may be used individually or in combination of two or more.

[0103] Other cycloolefin monomers other than norbornene monomers may be used in combination as the above cycloolefin monomer. Examples of other cycloolefin monomers include cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, cycloheptadiene, cyclooctene, cyclooctadiene, cyclodecene, cyclododecene, and tricyclo[6.2.1.0 2,7 Examples include undeca-4-ene (tricycloundecene) and derivatives thereof. Here, "derivative" means one having substituents on the ring (olefin ring). Examples of such substituents include alkyl groups, alkylene groups, vinyl groups, alkoxycarbonyl groups, and alkylidene groups. The ring of the "derivative" may have one of these substituents or two or more. The above other cycloolefin monomers may be used individually or in combination of two or more.

[0104] The number of carbon atoms constituting the ring (olefin ring) of the above-mentioned other cycloolefin monomers is preferably 4 or more, more preferably 5 or more, even more preferably 6 or more, preferably 20 or less, more preferably 15 or less, even more preferably 12 or less, and particularly preferably 8 or less.

[0105] The other cycloolefin monomers mentioned above are preferably cyclooctene, cycloheptene, and their derivatives, more preferably cyclooctene and its derivatives, and even more preferably cyclooctene.

[0106] The content of the above-mentioned other structural units derived from cycloolefin monomers is preferably 10 mol% or more, more preferably 30 mol% or more, even more preferably 40 mol% or more, and preferably 50 mol% or less.

[0107] The melt flow rate (MFR) of the above amorphous cycloolefin resin, measured according to JIS-K-6719 at 280°C and a load of 2.16 kg, can be appropriately selected depending on the intended use, but is usually 0.1 g / 10 min or more, preferably 1 g / 10 min or more, more preferably 5 g / 10 min or more, and is usually in the range of 200 g / 10 min or less, preferably 150 g / 10 min or less, and more preferably 100 g / 10 min or less. When the MFR is within the above range, moldability and the yield rate of good molded products are improved.

[0108] The amorphous cycloolefin resin described above may contain various additives, such as polymerization reaction retardants, radical crosslinking retardants, reinforcing agents, modifiers, antioxidants, flame retardants, fillers, colorants, and light stabilizers.

[0109] Examples of the reinforcing materials mentioned above include glass fibers, glass cloth, paper substrates, and glass nonwoven fabrics.

[0110] Examples of the above-mentioned modifiers include natural rubber, butadiene rubber (BR), isoprene rubber (IR), cyclopentene rubber (CPR), styrene-butadiene copolymer (SBR), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), ethylene-propylene-diene polymer (EPDM), ethylene-vinyl acetate copolymer (EVA), and elastomers such as their hydrides.

[0111] Examples of the above-mentioned antioxidants include various plastic and rubber antioxidants such as hindered phenol-based, phosphorus-based, and amine-based antioxidants. These antioxidants may be used individually, but it is preferable to use two or more in combination.

[0112] Examples of the above-mentioned flame retardants include phosphorus-based flame retardants, nitrogen-based flame retardants, halogen-based flame retardants, metal hydroxide-based flame retardants such as aluminum hydroxide, and antimony compounds such as antimony trioxide. Flame retardants may be used individually, but it is preferable to use two or more in combination.

[0113] The above crystalline cycloolefin resin has a number-average molecular weight of 5.0 × 10⁻⁶. 3 Preferably, it is 1.0 × 10 4 It is more preferable that the above is true, and also 1.0 × 10 6 Preferably, it is 5.0 × 10 5 The following is more preferable: The molecular weight of crystalline cycloolefin resin is 1 Based on 1H-NMR measurements, the number of hydrogen atoms is calculated based on the ratio of the number of hydrogen atoms present at the ends of the polymer chain to the number of hydrogen atoms present in the rest of the polymer chain.

[0114] Examples of cycloolefin monomers used in the above-mentioned crystalline cycloolefin resin include those exemplified as cycloolefin monomers used in amorphous cycloolefin resins. The above-mentioned crystalline cycloolefin resin may be a crystalline norbornene-based ring-opening polymer hydride or a crystalline dicyclopentadiene ring-opening polymer hydride, with crystalline dicyclopentadiene ring-opening polymer hydride being preferred from the viewpoint of heat resistance.

[0115] The above crystalline norbornene-based ring-opening polymer hydride is given by the following formula (2-1): [ka] It has repetitions represented by [the symbol].

[0116] Here, m is either 1 or 2. R a , R b Each of these independently represents a hydrogen atom, or a group selected from substituted or unsubstituted C1-C12 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, and substituted or unsubstituted C6-C12 aryl groups.

[0117] The crystalline norbornene ring-opening polymer hydride containing the repeating unit represented by formula (2-1) exhibits stereoregularity because the carbon atom represented by (*) in formula (2-1) is an asymmetric carbon atom.

[0118] The presence or absence of stereoregularity in the above-mentioned crystalline norbornene-based ring-opening polymer hydrides is not particularly limited as long as the polymer is crystalline (i.e., has a melting point), but a crystalline norbornene-based ring-opening polymer hydride having isotactic or syndiotactic regularity is one preferred embodiment. In a crystalline norbornene-based ring-opening polymer hydride having isotactic regularity, the proportion of racemo diads (racemo dyads) to the repeating units of the norbornene monomer is preferably 20% or less, and more preferably 10% or less. The racemo-dyad ratio of crystalline norbornene-based ring-opening polymer hydrides was determined using orthodichlorobenzene-d4 as the solvent at 150°C. 13 This can be calculated by performing 1C-NMR measurements and basing the calculation on the intensity ratio of the 43.35 ppm signal from the meso-dyad and the 43.43 ppm signal from the racemo-dyad.

[0119] From the viewpoint of providing particularly good heat resistance and a fast crystallization rate for the crystalline norbornene-based ring-opening polymer hydride having the above-mentioned isotactic regularity, it is preferable to use a norbornene-based monomer that contains dicyclopentadiene. The proportion of dicyclopentadiene in the norbornene-based monomer is not particularly limited, but it is preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more.

[0120] Furthermore, the norbornene monomer described above can be used in combination with other cycloolefin monomers. However, from the viewpoint of particularly good heat resistance of the norbornene-based ring-opening polymer hydride and a fast crystallization rate, the amount of other cycloolefin monomers used is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less, relative to the total amount of monomers.

[0121] The above-mentioned crystalline norbornene-based ring-opening polymer hydrides having isotactic regularity are, for example, obtained by using the above-mentioned norbornene-based monomers in the following formula: [ka] (In the formula, M represents an atom selected from the transition metal atoms of Group 6 of the periodic table, and R 1 R represents a group selected from alkyl groups having 1 to 12 carbon atoms and aryl groups having 6 to 12 carbon atoms, which may have substituents. 2 ~R 9 Each of these independently represents a hydrogen atom, a C1-C12 alkyl group which may have substituents, and a C6-C12 aryl group which may have substituents, and R 2 ~R 9These atoms may bond to each other to form a ring structure. Also, X represents an atom independently selected from halogen atoms, n is 1 or 2, and m is 0 or 2. It can be produced by ring-opening polymerization using a polymerization catalyst with a Group 6 transition metal compound of the periodic table represented by ( ), and then hydrogenating the resulting norbornene-based ring-opening polymer.

[0122] The above-mentioned crystalline norbornene-based ring-opening polymer hydride is also preferably a syndiotactic-norbornene-based ring-opening polymer hydride having a racemo dyad ratio higher than 90% and high syndiotactic stereoregularity, from the viewpoint of solvent resistance. The racemo dyad ratio is preferably higher than 90%, more preferably higher than 95%, and particularly preferably higher than 99%.

[0123] Syndiotacticity can be calculated using the formula [(racemo diad) / (meso diad + racemo diad) × 100]. The proportion of racemo diads (racemo dyads) is determined by the norbornene-based ring-opening polymer hydride. 13 This can be calculated by analyzing the 1C-NMR spectrum. For example, using chloroform-d as the solvent, at 60°C, the norbornene-based ring-opening polymer hydride 13 ¹³C-NMR spectral analysis can be performed to quantitatively determine the spectrum of the methylene carbon atoms in the five-membered ring. Specifically, the ratio of racemo-dyads to meso-dyads can be determined based on the intensity ratio of the 31.787 ppm signal attributed to the meso-dyad and the 31.799 ppm signal attributed to the racemo-dyad. For example, a tetracyclododecene ring-opening polymer hydride can be analyzed using a mixed solvent of orthodichlorobenzene-d4 / trichlorobenzene (1 / 2 weight ratio) at 200°C. 13 By performing 1C-NMR spectroscopy (of the non-backchain methine carbon atoms of the 5-membered ring), the ratio of racemo-dyads to meso-dyads can be determined based on the intensity ratio of the 51.63 ppm signal attributed to meso-dyads and the 51.72 ppm signal attributed to racemo-dyads.

[0124] Examples of norbornene monomers used in the above-mentioned crystalline norbornene-based ring-opening polymer hydrides having syndiotactic stereoregularity include those listed above.

[0125] The above-mentioned crystalline norbornene-based ring-opening polymer hydrides having syndiotactic stereoregularity may also be produced by combining a norbornene-based monomer with the other cycloolefin monomers mentioned above, provided that the resulting norbornene-based ring-opening polymer hydrides are solvent-resistant.

[0126] The above syndiotactic stereoregularity-having crystalline norbornene-based ring-opening polymer hydrides are, for example, obtained by dividing the above-mentioned norbornene-based monomer into the following formula: [ka] (In the formula, M 11 This represents an atom selected from the transition metal atoms of Group 6 of the periodic table. R 11 , R 12 Each of these independently represents a hydrogen atom, or a group selected from substituted or unsubstituted C1-C12 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, and substituted or unsubstituted C6-C12 aryl groups. L 11 This represents an oxygen atom, or a nitrogen atom substituted with a substituent selected from substituted or unsubstituted C1-C12 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, and substituted or unsubstituted C6-C12 aryl groups, or an unsubstituted nitrogen atom. L 12 , L 13 Each independently comprises a substituted or unsubstituted conjugated heterocyclic ring group with 5 to 15 members, each having at least one nitrogen atom, or OR 13 It is a base represented by, R 13This group is selected from substituted or unsubstituted C1-C12 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, and substituted or unsubstituted C6-C30 aryl groups. L 14 These are phosphorus-containing compounds, oxygen-containing compounds, or nitrogen-containing compounds. n is 0 or 1. It can be produced by ring-opening polymerization using a polymerization catalyst that utilizes a Group 6 transition metal compound of the periodic table (represented by ), and then hydrogenating the resulting norbornene-based ring-opening polymer.

[0127] The above crystalline dicyclopentadiene ring-opening polymer hydride is given by the following formula (2-2): [ka] It has repeating units represented by .

[0128] In the above-mentioned crystalline dicyclopentadiene ring-opening polymer hydride, the carbon atoms represented by (1,4) in formula (2-2) are chiral carbons (indicated by *), and therefore stereoregularity (tacticity) exists. The above-mentioned crystalline dicyclopentadiene ring-opening polymer hydride is preferably a polymer with syndiotactic stereoregularity in terms of high melting point and processability, and preferably has a syndiotacticity, that is, a high proportion of racemo diads in the total of meso diads and racemo diads in its stereoconfiguration (hereinafter sometimes simply referred to as the proportion of racemo diads). In the above-mentioned crystalline dicyclopentadiene ring-opening polymer hydride, the proportion of racemo diads is preferably higher than 91%, and more preferably higher than 92%.

[0129] Syndiotacticity can be specifically calculated using formula I: [(racemo diplex) / (meso diplex + racemo diplex) × 100 (%)]. The proportion of racemo diplex is the proportion of crystalline dicyclopentadiene ring-opening polymer hydride. 13It can be calculated by analyzing the 1C-NMR spectrum. Specifically, it can be determined by quantifying the spectrum of the carbon atoms represented by (5,9) in formula (2-2) of the above crystalline dicyclopentadiene ring-opening polymer hydride. That is, for the carbon atoms of (5,9) in the repeating unit represented by formula (2-2) above, in an orthodichlorobenzene-d4 / trichlorobenzene [mixing ratio (by weight) 1 / 2] mixed solvent at 200°C 13 By performing 13C-NMR spectroscopy measurements and substituting the peak area value of the 43.35 ppm signal originating from the mesoscale double and the peak area value of the 43.43 ppm signal originating from the racemoscale double into the aforementioned equation I, the proportion of racemoscale doubles can be determined.

[0130] The above crystalline dicyclopentadiene ring-opening polymer hydride is given by the following formula (3-2): [ka] It has repeating units derived from dicyclopentadiene, represented by [formula].

[0131] The above-mentioned crystalline dicyclopentadiene ring-opening polymer hydride is preferably one that contains a large amount of repeating units derived from dicyclopentadiene, from the viewpoint of having particularly good heat resistance and a fast crystallization rate. The proportion of repeating units derived from dicyclopentadiene among the total repeating units in the above-mentioned crystalline dicyclopentadiene ring-opening polymer hydride is not particularly limited, but is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 97% by mass or more.

[0132] Dicyclopentadiene has endo and exo stereoisomers, both of which can be used as monomers. One isomer may be used alone, or an isomer mixture containing the endo and exo isomers in any proportion may be used. From the viewpoint of improving the crystallinity of crystalline dicyclopentadiene ring-opening polymer hydrides and particularly improving their heat resistance, it is preferable to increase the proportion of one stereoisomer. The dicyclopentadiene used preferably contains 90% or more of the endo or exo isomer, more preferably 95% or more, and particularly preferably 99% or more. From the viewpoint of ease of synthesis, the stereoisomer whose proportion is increased is preferably the endo isomer.

[0133] Dicyclopentadiene can also be used in combination with other cyclic olefin monomers. The amount of other cyclic olefin monomers used is usually less than 10% by mass, preferably less than 3% by mass, and more preferably less than 1% by mass, relative to the total amount of dicyclopentadiene and the other cyclic olefin monomers.

[0134] Other cyclic olefin monomers that can be used in combination with dicyclopentadiene include the norbornene monomers mentioned above (excluding dicyclopentadiene), and other cycloolefin monomers mentioned above.

[0135] The above-mentioned crystalline dicyclopentadiene ring-opening polymer hydride is, for example, the above-mentioned dicyclopentadiene, or a monomer mixture containing dicyclopentadiene and other cyclic olefin monomers, as shown in the following formula: [ka] (In the formula, W represents a tungsten atom, R 21 and R 22 Each of these independently represents a group selected from a hydrogen atom, a C1-C12 alkyl group, an optionally substituted C6-C12 aryl group, and an optionally substituted C3-C20 cycloalkyl group. L 21 This represents a nitrogen atom which may have substituents selected from alkyl groups having 1 to 12 carbon atoms, aryl groups having 6 to 12 carbon atoms which may have substituents, and cycloalkyl groups having 3 to 20 carbon atoms which may have substituents. L 22 This represents a conjugated heterocyclic group having 5 to 15 members and having at least one nitrogen atom, and the conjugated heterocyclic group may have substituents. L 23 is OR 23 R represents the alkoxy group shown, 23 This represents a group selected from C1-C12 alkyl groups which may have substituents, and C6-C30 aryl groups which may have substituents. L 24 This can be produced by ring-opening polymerization using a polymerization catalyst containing a tungsten compound represented by (), and then hydrogenating the resulting dicyclopentadiene ring-opening polymer.

[0136] The amorphous cycloolefin resin and the crystalline cycloolefin resin described above are also preferably cycloolefin copolymers (COCs).

[0137] The above-mentioned cycloolefin copolymer may be a copolymer of ethylene or α-olefin with a cycloolefin monomer, a ring-opened copolymer of a cycloolefin monomer, a hydride of a ring-opened copolymer of a cycloolefin monomer, or a graft-modified product thereof.

[0138] The cycloolefin monomers in the above-described cycloolefin copolymers are not particularly limited as long as they do not hinder the purpose of this disclosure. Typically, norbornene and substituted norbornene, dicyclopentadiene, 1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene (TCD), and 1,4,4a,9a-tetrahydro-1,4-methanofluorene (MTF) are preferred as cycloolefin monomers. Among the cycloolefin monomers, norbornene, TCD, and dicyclopentadiene are particularly preferred in terms of a good balance of cost, polymerizability, and the physical properties of the resulting cycloolefin copolymers. Cycloolefin monomers can be used individually or in combination of two or more.

[0139] The above-mentioned substituted norbornene is not particularly limited. Examples of substituents on substituted norbornene include halogen atoms and monovalent or divalent hydrocarbon groups. A specific example of substituted norbornene is shown in formula (I) below: [ka] (In the formula, R a1 ~R a12 These atoms or groups may be the same or different, and are selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups. R a9 and R a10 , R a11 and R a12 These may integrate to form a divalent hydrocarbon group. R a9 or R a10 And, R a11 or R a12 These elements may be joined together to form a ring. n is 0 or a positive integer. If n is 2 or greater, R a5 ~R a8 These elements may be identical or different within each repeating unit. However, if n is 0, R a1 ~R a4 and Ra9 ~R a12 At least one of them is not a hydrogen atom. Examples of compounds represented by [the formula shown] are given.

[0140] R a1 ~R a8 Specific examples include, for instance, hydrogen atoms; halogen atoms such as fluorine, chlorine, and bromine; and alkyl groups having 1 to 20 carbon atoms. a1 ~R a8 It may consist entirely of different atoms or groups. a1 ~R a8 Some or all of these may be the same atom or group.

[0141] R a9 ~R a12 Specific examples include, for instance, hydrogen atoms; halogen atoms such as fluorine, chlorine, and bromine; alkyl groups having 1 to 20 carbon atoms; cycloalkyl groups such as cyclohexyl groups; substituted or unsubstituted aromatic hydrocarbon groups such as phenyl, tolyl, ethylphenyl, isopropylphenyl, naphthyl, and anthryl groups; and aralkyl groups such as benzyl and phenethyl groups. a9 ~R a12 It may consist entirely of different atoms or groups. a9 ~R a12 Some or all of these may be the same atom or group.

[0142] R a9 and R a10 , or R a11 and R a12 Specific examples of divalent hydrocarbon groups that can be formed by the integration of these include alkylidene groups such as ethylidene, propyridene, and isopropylidene.

[0143] R a9 or R a10 And, R a11 or R a12When these elements bond to each other to form a ring, the resulting ring may be monocyclic or polycyclic. The resulting ring may be polycyclic with bridges. The resulting ring may have double bonds. The resulting ring may have substituents such as methyl groups.

[0144] Specific examples of substituted norbornenes represented by formula (I) include 5-methyl-bicyclo[2.2.1]hepta-2-ene, 5,5-dimethyl-bicyclo[2.2.1]hepta-2-ene, 5-ethyl-bicyclo[2.2.1]hepta-2-ene, 5-butyl-bicyclo[2.2.1]hepta-2-ene, 5-ethylidene-bicyclo[2.2.1]hepta-2-ene, and 5-hexyl-bi Bicyclic cycloolefins such as cyclo[2.2.1]hepta-2-ene, 5-octyl-bicyclo[2.2.1]hepta-2-ene, 5-octadecyl-bicyclo[2.2.1]hepta-2-ene, 5-methylidene-bicyclo[2.2.1]hepta-2-ene, 5-vinyl-bicyclo[2.2.1]hepta-2-ene, and 5-propenyl-bicyclo[2.2.1]hepta-2-ene; Tricyclo[4.3.0.1 2,5 Deca-3,7-diene (common name: dicyclopentadiene), tricyclo[4.3.0.1 2,5 Deca-3-en; Tricyclo[4.4.0.1 2,5 ]Undeca-3,7-diene or tricyclo[4.4.0.1 2,5 ] Tricyclo[4.4.0.1 2,5 ]undeca-3-ene; 5-cyclopentyl-bicyclo[2.2.1]hepta-2-ene, 5-cyclohexyl-bicyclo[2.2.1]hepta-2-ene, 5-cyclohexenylbicyclo[2.2.1]hepta-2-ene, 5-phenyl-bicyclo[2.2.1]hepta-2-ene, and other tricyclic cycloolefins; Tetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene (also simply called tetracyclododecene), 8-methyltetracyclo[4.4.0.1 2,5 .17,10 ] Dodeca-3-ene, 8-ethyltetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene, 8-methylidenetetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene, 8-vinyltetracyclo[4,4.0.1 2,5 .1 7,10 ] Dodeca-3-ene, 8-propenyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene and other four-ring cycloolefins; 8-Cyclopentyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene, 8-cyclohexyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene, 8-cyclohexenyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene, 8-phenyl-cyclopentyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene; Tetracyclo[7.4.1 3,6 .0 1,9 .0 2,7 ]Tetradeca-4,9,11,13-tetraene (also known as 1,4-methano-1,4,4a,9a-tetrahydrofluorene), tetracyclo[8.4.1 4,7 .0 1,10 .0 3,8 ]Pentadeca-5,10,12,14-tetraene (also known as 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene); pentacyclo[6.6.1.1 3,6 .0 2,7 .0 9,14 ]-4-Hexadecene, pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 ]-4-pentadecene, pentacyclo[7.4.0.0 2,7 .13,6 .1 10,13 ]-4-pentadecene; heptacyclo[8.7.0.1 2,9 .1 4,7 .1 11,17 .0 3,8 .0 12,16 ]-5-eicosene, heptacyclo[8.7.0.1 2,9 .0 3,8 .1 4,7 .0 12,17 .1 13,l6 Examples include polycyclic cycloolefins such as tetramers of ]-14-eicosene and cyclopentadiene.

[0145] Among these, alkyl-substituted norbornene such as bicyclo[2.2.1]hepta-2-ene substituted with one or more alkyl groups, and alkylidene-substituted norbornene such as bicyclo[2.2.1]hepta-2-ene substituted with one or more alkylidene groups are preferred. 5-Ethylidene-bicyclo[2.2.1]hepta-2-ene (common name: 5-ethylidene-2-norbornene, or simply ethylidene norbornene) is particularly preferred.

[0146] The ethylene and α-olefins mentioned above are preferably α-olefins having 2 to 20 carbon atoms, and ethylene is particularly preferred. As such α-olefins, not only unsubstituted α-olefins but also substituted α-olefins having substituents such as halogen atoms can be used. The number of carbon atoms in the α-olefin is 3 to 20, preferably 4 to 12, and more preferably 6 to 10.

[0147] Specific examples of α-olefins having 3 to 12 carbon atoms include 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, and 1-dodecene. Among these, 1-hexene, 1-octene, and 1-decene are preferred.

[0148] The molecular weight of the above cycloolefin copolymer is not particularly limited. The weight-average molecular weight (Mw) of the above cycloolefin copolymer is preferably 5,000 to 200,000, and more preferably 10,000 to 100,000, as measured by gel permeation chromatography (GPC) in terms of polystyrene. The number-average molecular weight (Mn) of the above cycloolefin copolymer is preferably 5,000 to 200,000, and more preferably 10,000 to 100,000, as measured by gel permeation chromatography (GPC) in terms of polystyrene. The dispersion ratio (Mw / Mn) is preferably 1.2 or higher, and more preferably 1.3 or higher.

[0149] The melt flow rate (MFR) of the above cycloolefin copolymer is not particularly limited, but from the viewpoint of the appearance of the resulting molded article, it is usually 1 g / 10 min or more, preferably 2 g / 10 min or more, more preferably 5 g / 10 min or more, and is usually in the range of 400 g / 10 min or less, preferably 200 g / 10 min or less, and more preferably 100 g / 10 min or less. The above MFR values ​​were measured according to ASTM1238 (260°C, 2.16 kg).

[0150] The above-mentioned cycloolefin copolymer can be mixed with various additives as needed, and then molded into, for example, films, sheets, etc., and widely used in various applications. Additives that can be added to the cycloolefin copolymer include antioxidants, weather stabilizers, UV absorbers, antibacterial agents, flame retardants, and colorants. These additives are added to the cycloolefin copolymer in amounts that take into account the typical usage amounts for each type of additive.

[0151] The polymethylpentene resin (PMP) described above may be a homopolymer of 4-methyl-1-pentene, or a copolymer of 4-methyl-1-pentene and another monomer.

[0152] The other monomers (comonomers) in the polymethylpentene resin described above are not particularly limited as long as they are monomers that can copolymerize with 4-methyl-1-pentene. From the viewpoint of availability and copolymerization characteristics, preferred examples of the other monomers include α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, and 3-ethyl-1-hexene. The other monomers may be used individually or in combination of two or more. Among these, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene are preferred, α-olefins other than methyl-1-pentene with 6 to 20 carbon atoms are more preferred, such as 1-hexene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene, and 1-hexene, 1-decene, 1-hexadecene, and 1-octadecene are even more preferred.

[0153] In the above polymethylpentene resin, the content of structural units derived from 4-methyl-1-pentene is usually 85 mol% or more, preferably 90 mol% or more, and more preferably 95% or more. The content of structural units derived from other monomers is usually 15 mol% or less, preferably 10 mol% or less, and more preferably 5 mol% or less. The monomer composition is IR or 13 It can be measured by 13C-NMR.

[0154] The polymethylpentene resin described above may also be a graft-modified polymer obtained by graft-modifying a 4-methyl-1-pentene polymer with a polar monomer.

[0155] Examples of polar monomers used for graft modification include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, epoxy group-containing ethylenically unsaturated compounds, aromatic vinyl compounds, unsaturated carboxylic acids or their derivatives, vinyl ester compounds, vinyl chloride, and carbodiimide compounds. Unsaturated carboxylic acids or their derivatives are particularly preferred. Examples of unsaturated carboxylic acids or their derivatives include unsaturated compounds having one or more carboxylic acid groups, esters of compounds having carboxylic acid groups with alkyl alcohols, and unsaturated compounds having one or more anhydride carboxylic acid groups. Examples of unsaturated groups include vinyl groups, vinylene groups, and unsaturated cyclic hydrocarbon groups.

[0156] Specifically, the polar monomers mentioned above include unsaturated carboxylic acids such as acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and nadic acid (endosis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid), and derivatives of unsaturated carboxylic acids, such as acid halides, amides, imides, anhydrides, and esters. Specific examples of such derivatives include malenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate.

[0157] Depending on its use, the above-mentioned polymethylpentene resin can optionally contain at least one selected from other polymers different from the 4-methyl-1-pentene polymer and resin additives, as long as it does not inhibit the effects of the present disclosure.

[0158] As the above-mentioned other polymers, thermoplastic resins different from the 4-methyl-1-pentene polymer can be widely used. The content of the other polymer is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less, based on the content of the 4-methyl-1-pentene polymer.

[0159] The thermoplastic resin is not particularly limited as long as it is different from the 4-methyl-1-pentene polymer. Thermoplastic polyolefin resins: For example, polyethylene such as low-density, medium-density, high-density polyethylene, high-pressure low-density polyethylene, etc., polypropylene such as isotactic polypropylene, syndiotactic polypropylene, etc., poly-1-butene, poly-4-methyl-1-pentene, poly-3-methyl-1-pentene, poly-3-methyl-1-butene, ethylene·α-olefin copolymer, propylene·α-olefin copolymer, 1-butene·α-olefin copolymer, 4-methyl-1-pentene·α-olefin copolymer, cyclic olefin polymer, crystalline cyclic olefin polymer, cyclic olefin copolymer, chlorinated polyolefin, and modified polyolefin resins obtained by modifying these olefin resins; Thermoplastic polyamide resins: For example, aliphatic polyamides (nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 612); Thermoplastic polyester resins: For example, polyethylene terephthalate, polybutylene terephthalate, polyester elastomers; Thermoplastic vinyl aromatic resins: for example, polystyrene, crystalline polystyrene, ABS resin, AS resin, styrene-based elastomers (styrene-butadiene-styrene block polymer, styrene-isoprene-styrene block polymer, styrene-isobutylene-styrene block polymer, and their hydrogenated versions); Thermoplastic polyurethane; vinyl chloride resin; vinylidene chloride resin; acrylic resin; vinyl acetate copolymers such as ethylene-vinyl acetate copolymer; ethylene-methacrylate copolymer; ionomer; ethylene-vinyl alcohol copolymer; polyvinyl alcohol; fluorine-based resin; polycarbonate; polyacetal; polyphenylene oxide; polyphenylene sulfide polyimide; polyarylate; polysulfone; polyethersulfone; rosin-based resin; terpene-based resin and petroleum resin; Copolymer rubbers: For example, ethylene-α-olefin-diene copolymer, propylene-α-olefin-diene copolymer, 1-butene-α-olefin-diene copolymer, polybutadiene rubber, polyisoprene rubber, cyclopentene rubber, neoprene rubber, nitrile rubber, butyl rubber, polyisobutylene rubber, natural rubber, silicone rubber; Examples include the following.

[0160] Among the thermoplastic polyolefin resins mentioned above, polyethylene and polypropylene can be used as crystal nucleating agents, and in that case, the preferred content is 0.001 to 5% by mass relative to the content of 4-methyl-1-pentene polymer.

[0161] Among thermoplastic resins, preferred are low-density, medium-density, and high-density polyethylene, high-pressure low-density polyethylene, isotactic polypropylene, syndiotactic polypropylene, amorphous cyclic olefin polymers, crystalline cyclic olefin polymers, cyclic olefin copolymers, poly-1-butene, poly-3-methyl-1-pentene, poly-3-methyl-1-butene, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, 1-butene-α-olefin copolymer, styrene-based elastomers, vinyl acetate copolymers, ethylene-methacrylate copolymers, ionomers, fluororesins, rosin-based resins, terpene-based resins, and petroleum resins. More preferably, in terms of improved heat resistance, improved low-temperature resistance, and flexibility, are polyethylene, isotactic polypropylene, syndiotactic polypropylene, cyclic olefin copolymers, ethylene-α-olefin copolymers, propylene-α-olefin copolymers, 1-butene-α-olefin copolymers, vinyl acetate copolymers, styrene-based elastomers, rosin-based resins, terpene-based resins, and petroleum resins.

[0162] Some or all of the other polymers mentioned above may be graft-modified polymers obtained by graft-modifying the polymer with polar monomers. Graft modification is as described above.

[0163] Examples of the above-mentioned additives for resins include nucleating agents, antiblocking agents, pigments, dyes, fillers, lubricants, plasticizers, mold release agents, antioxidants, flame retardants, UV absorbers, antibacterial agents, surfactants, antistatic agents, weather stabilizers, heat stabilizers, anti-slip agents, foaming agents, crystallization aids, anti-fogging agents, anti-aging agents, hydrochloric acid absorbers, impact modifiers, crosslinking agents, co-crosslinking agents, crosslinking aids, adhesives, softeners, and processing aids.

[0164] The above resin additives may be used individually or in combination of two or more. The content of the above-mentioned resin additives is not particularly limited, depending on the application, as long as it does not impair the purpose of this disclosure, but it is preferably 0.001 to 30% by mass of each additive relative to the content of the 4-methyl-1-pentene polymer.

[0165] As nucleating agents, known nucleating agents can be used to further improve the moldability of the resin, that is, to raise the crystallization temperature and accelerate the crystallization rate. Specifically, examples include dibenzylidenesorbitol-based nucleating agents, phosphate ester salt-based nucleating agents, rosin-based nucleating agents, metal benzoate salt-based nucleating agents, fluorinated polyethylene, sodium 2,2-methylenebis(4,6-di-t-butylphenyl)phosphate, pimelic acid and its salts, 2,6-naphthalene dicarboxylic acid dicyclohexylamide, and ethylenebisstearate amide.

[0166] The amount of nucleating agent is not particularly limited, but is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of 4-methyl-1-pentene polymer and other polymers. The nucleating agent can be added as appropriate during polymerization, after polymerization, or during molding.

[0167] Known antiblocking agents can be used. Specifically, these include finely powdered silica, finely powdered aluminum oxide, finely powdered clay, powdered or liquid silicone resin, tetrafluoroethylene resin, finely powdered crosslinked resin, such as crosslinked acrylic or methacrylic resin powder, and amide-based lubricants. Of these, finely powdered silica and crosslinked acrylic or methacrylic resin powder are preferred.

[0168] Examples of pigments include inorganic pigments (titanium dioxide, iron oxide, chromium oxide, cadmium sulfide, etc.) and organic pigments (azo lake type, thioindigo type, phthalocyanine type, anthraquinone type). Examples of dyes include azo type, anthraquinone type, triphenylmethane type, etc. The amount of these pigments and dyes added is not particularly limited, but the total amount is usually 5% by mass or less, preferably 0.1 to 3% by mass, relative to the content of 4-methyl-1-pentene polymer.

[0169] Examples of fillers include glass fibers, carbon fibers, silica fibers, metal (stainless steel, aluminum, titanium, copper, etc.) fibers, carbon black, silica, glass beads, silicates. Examples include calcium silicate, talc, clay, etc., metal oxides (iron oxide, titanium oxide, alumina, etc.), metal carbonates (calcium sulfate, barium sulfate), and powders of various metals (magnesium, silicon, aluminum, titanium, copper, etc.), mica, and glass flakes.

[0170] Examples of lubricants include waxes (such as carnauba wax), higher fatty acids (such as stearic acid), higher alcohols (such as stearyl alcohol), and higher fatty acid amides (such as stearic acid amide).

[0171] Examples of plasticizers include aromatic carboxylic acid esters (such as dibutyl phthalate), aliphatic carboxylic acid esters (such as methylacetyl ricinolate), aliphatic dicarboxylic acid esters (such as adipic acid-propylene glycol polyesters), aliphatic tricarboxylic acid esters (such as triethyl citrate), phosphate triesters (such as triphenyl phosphate), epoxy fatty acid esters (such as epoxybutyl stearate), and petroleum resins.

[0172] Examples of release agents include lower (C1-C4) alcohol esters of higher fatty acids (such as butyl stearate), polyhydric alcohol esters of fatty acids (C4-C30) (such as hydrogenated castor oil), glycol esters of fatty acids, and liquid paraffin.

[0173] Known antioxidants can be used as antioxidants. Specifically, these include phenolic antioxidants (such as 2,6-di-t-butyl-4-methylphenol), polycyclic phenolic antioxidants (such as 2,2'-methylenebis(4-methyl-6-t-butylphenol)), phosphorus-based antioxidants (such as tri(2,4-di-t-butylphenyl)phosphate and tetrakis(2,4-di-t-butylphenyl)-4,4-biphenylenediphosphonate), sulfur-based antioxidants (such as dilauryl thiodipropionate), amine-based antioxidants (such as N,N-diisopropyl-p-phenylenediamine), and lactone-based antioxidants.

[0174] Examples of the flame retardant include organic flame retardants (nitrogen-containing, sulfur-containing, silicon-containing, phosphorus-containing, etc.), inorganic flame retardants (antimony trioxide, magnesium hydroxide, zinc borate, red phosphorus, etc.).

[0175] Examples of the ultraviolet absorber include benzotriazole-based, benzophenone-based, salicylic acid-based, and acrylate-based ultraviolet absorbers. Examples of the antibacterial agent include quaternary ammonium salts, pyridine-based compounds, organic acids, organic acid esters, halogenated phenols, and organic iodine.

[0176] Examples of the surfactant include nonionic, anionic, cationic, or amphoteric surfactants. Examples of the nonionic surfactant include polyethylene glycol type nonionic surfactants such as higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, and polypropylene glycol ethylene oxide adducts, and polyhydric alcohol type nonionic surfactants such as polyethylene oxide, fatty acid esters of glycerin, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol or sorbitan, alkyl ethers of polyhydric alcohols, and aliphatic amides of alkanolamines. Examples of the anionic surfactant include sulfate esters such as alkali metal salts of higher fatty acids, sulfonates such as alkylbenzene sulfonates, alkyl sulfonates, and paraffin sulfonates, and phosphate esters such as higher alcohol phosphate esters. Examples of the cationic surfactant include quaternary ammonium salts such as alkyltrimethylammonium salts. Examples of the amphoteric surfactant include amino acid type amphoteric surfactants such as higher alkylaminopropionates, and betaine type amphoteric surfactants such as higher alkyldimethylbetaines and higher alkylhydroxyethylbetaines.

[0177] Examples of antistatic agents include the surfactants, fatty acid esters, and polymeric antistatic agents mentioned above. Examples of fatty acid esters include esters of stearic acid and oleic acid, and examples of polymeric antistatic agents include polyether ester amides.

[0178] Examples of heat-resistant stabilizers include conventionally known stabilizers such as amine-based stabilizers, phenol-based stabilizers, and sulfur-based stabilizers. Specifically, examples include aromatic secondary amine stabilizers such as phenylbutylamine and N,N'-di-2-naphthyl-p-phenylenediamine; phenolic stabilizers such as dibutylhydroxytoluene and tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]methane and octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate; thioether stabilizers such as bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide; dithiocarbamate stabilizers such as dibutyldithiocarbamate nickel; 2-mercaptobenzoylimidazole and zinc salts of 2-mercaptobenzoylimidazole; and sulfur-based stabilizers such as dilaurylthiodipropionate and distearylthiodipropionate. These stabilizers may be used individually or in combination of two or more.

[0179] For example, organic peroxides are used as crosslinking agents. Examples of organic peroxides include dicumyl organic peroxide, di-tert-butyl organic peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexine-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate, benzoyl organic peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl organic peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl carbonate, diacetyl organic peroxide, lauroyl organic peroxide, and tert-butylcumyl organic peroxide.

[0180] The organic peroxide is used in a ratio of preferably 0.05 to 10 parts by mass per 100 parts by mass of the total amount of the 4-methyl-1-pentene polymer and the other polymers.

[0181] In crosslinking treatment with organic peroxides, peroxy crosslinking aids such as sulfur, p-quinone dioxime, p,p'-dibenzoylquinone dioxime, N-methyl-N-4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, and trimethylolpropane-N,N'-m-phenylenedimaleimide can be incorporated, or polyfunctional methacrylate monomers such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate, or polyfunctional vinyl monomers such as vinyl butyrate and vinyl stearate can be incorporated.

[0182] By using the above-mentioned compounds, a uniform and mild crosslinking reaction can be expected. Divinylbenzene is particularly suitable. Divinylbenzene is easy to handle, has good compatibility with polymers, and has the effect of solubilizing organic peroxides, acting as a dispersant for organic peroxides. As a result, a homogeneous crosslinking effect can be obtained, and a dynamically heat-treated product with a good balance of fluidity and physical properties can be obtained.

[0183] The above-mentioned crosslinking aid is used in a ratio of preferably 0.05 to 10 parts by mass per 100 parts by mass of the total amount of the 4-methyl-1-pentene polymer and the other polymers.

[0184] The melt flow rate (MFR) of the above-mentioned polymethylpentene resin, measured in accordance with ASTM D1238 under conditions of a load of 5 kg and a temperature of 260°C, is not particularly limited, but from the viewpoint of the appearance of the resulting molded article, is usually 1 g / 10 min or more, preferably 2 g / 10 min or more, more preferably 5 g / 10 min or more, and is usually in the range of 400 g / 10 min or less, preferably 200 g / 10 min or less, and more preferably 100 g / 10 min or less.

[0185] The melting point of the polymethylpentene resin described above is not particularly limited, but is usually 100°C or higher, preferably 150°C or higher, and usually 240°C or lower.

[0186] The mesodiad isotacticity (mesodiad fraction) of the above polymethylpentene resin is not particularly limited, but is usually 85% or more, preferably 90% or more, more preferably 95% or more, and usually 100% or less.

[0187] The above polymethylpentene resin has a weight-average molecular weight of 5.0 × 10⁻⁶. 4 Preferably, it is 1.0 × 10 5 It is more preferable that the above is true, and also 1.0 × 10 6 Preferably, it is 7.0 × 10 5 The following is more preferable: The molecular weight of polymethylpentene resin is measured by gel permeation chromatography (GPC, column temperature: 140°C, eluent: 1,2,4-trichlorobenzene) in polystyrene equivalent.

[0188] The above polymethylpentene resin can be produced by conventionally known methods, for example, by the method disclosed in Comparative Example 9 of International Publication No. 2006 / 054613.

[0189] Examples of the chlorine-based resins mentioned above include vinyl chloride resin, chlorinated vinyl chloride resin, chlorinated polyethylene resin, and polyvinylidene chloride, and one or more of these can be used. In particular, polyvinyl chloride resin and chlorinated polyvinyl chloride resin are preferred from the viewpoint of corrosion resistance.

[0190] The vinyl chloride resin described above may be a homopolymer of vinyl chloride, or a copolymer of vinyl chloride and other monomers.

[0191] Other monomers that copolymerize with vinyl chloride include vinyl monomers. Specifically, examples include α-olefins such as ethylene, propylene, and butylene; vinyl esters such as vinyl acetate, vinyl capronate, vinyl laurate, and vinyl stearate; alkyl vinyl ethers such as 2-ethylhexyl vinyl ether, butyl vinyl ether, octyl vinyl ether, dodecyl vinyl ether, and phenyl vinyl ether; esters of acrylic acid or methacrylic acid such as ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate; aromatic vinyls such as styrene and α-methylstyrene; halogenated olefins such as vinylidene chloride, vinyl fluoride, vinyl bromide, and propylene chloride; N-substituted maleimides such as Nt-butyl maleimide, N-phenyl maleimide, and N-cyclohexyl maleimide; and acrylic derivatives such as acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, and itaconic anhydride. These are used individually or in combination of two or more.

[0192] The average degree of polymerization of the vinyl chloride resin is preferably 500 to 3000, and particularly preferably 700 to 1300. When the average degree of polymerization is within the range of 500 to 3000, the melt viscosity does not become too high, making it easy to mold into the desired shape, and the resulting molded product tends to have sufficient impact strength, easily satisfying the required properties. In this specification, the average degree of polymerization of the vinyl chloride resin is measured by the method of JIS K 7367-2.

[0193] The vinyl chloride resin described above preferably has a chlorine content of 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or less.

[0194] In this specification, the chlorine content of chlorine-based resins is measured by heating and burning the sample in a glass tube with a gas burner flame to dehydrochlorinate it, absorbing the resulting hydrochloric acid gas into distilled water, and then neutralizing and titrating it with a 0.1 mol / L sodium hydroxide normal solution.

[0195] To improve injection moldability, a methyl methacrylate copolymer may be added to the vinyl chloride resin. The methyl methacrylate copolymer is a copolymer of methyl methacrylate and an acrylic acid ester. Examples of acrylic acid esters used here include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and 2-ethylhexyl methacrylate, and these are used individually or in combination of two or more. These methyl methacrylate copolymers are used in an amount of 0.1 to 5 parts by mass, preferably 0.5 to 2 parts by mass, per 100 parts by mass of the vinyl chloride resin.

[0196] The vinyl chloride resin composition may, as needed, contain stabilizers, plasticizers, modifiers, fillers, colorants, lubricants, processing aids, antioxidants, UV absorbers, heat resistance improvers, smoke suppressants, and the like, which are commonly used in vinyl chloride resins, to the extent that they do not impair the purpose of this disclosure.

[0197] Examples of stabilizers include lead-based stabilizers such as tribasic lead sulfate, dibasic lead phosphate, basic lead sulfite, dibasic lead phthalate, lead white, lead laurate or stearate; and tin compounds such as butyltin maleate, octyltin maleate, di-n-alkyltin mercaptide, di-n-alkyltin dilaurate, dibutyltin dimalate, dibutyltin lauryl mercaptide, dioctyltin-S,S'-bis(isooctyl mercaptoacetate), dibutyltin bisisooctyl thioglycolate, di-n-octyltin maleate polymer, and dibutyltin mercaptopropionate. Examples of stabilizers include: organometallic salt stabilizers such as laurate or stearate of calcium, cadmium, barium, or zinc, and metal soap stabilizers; antimony stabilizers such as antimony mercaptocarboxylate or ester salts; phosphate stabilizers; epoxidized oil stabilizers such as epoxidized soybean oil and epoxidized linseed oil; hindered phenols such as bisphenol dimerized with BHT, sulfur, or methylene groups; salicylic acid esters; benzophenone and benzotriazole; and these are used individually or in combination of two or more.

[0198] Examples of plasticizers include phthalate esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di-n-octyl phthalate (hereinafter referred to as DOP), diisodecyl phthalate, and butylbenzyl phthalate; aliphatic dibasic acid esters such as dibutyl adipate, di-n-hexyl adipate, and dibutyl sebacate; phosphate esters such as tributyl phosphate, tri-2-n-ethylhexyl phosphate, tricresyl phosphate, and triphenyl phosphate; trimellitate-tri-2-ethylhexyl, trimellitate Examples include trimellitic acid esters such as tributyl triate; glycol esters such as pentaerythritol ester and diethylene glycol benzoate; epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; citrate esters such as acetyl tributyl citrate, acetyl trioctyl citrate, and tri-n-butyl citrate; tetra-n-octyl pyromelitate, polypropylene adipate, and other polyester-based plasticizers, which are used individually or in combination of two or more.

[0199] Examples of modifiers include impact modifiers such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, chlorinated polyethylene, methyl methacrylate-butadiene-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, and acrylic rubber; heat modifiers such as acrylonitrile-butadiene-α-methylstyrene copolymer, methyl methacrylate-acrylic acid ester copolymer, and other copolymers using maleimide; flame retardants such as antimony trioxide, aluminum hydroxide, sodium antimonate, phosphate esters and phosphate compounds, chlorinated paraffin, chlorinated olefin, and hexabromobenzene; elasticity modifiers such as partially crosslinked NBR, acrylic rubber, and polyurethane; and further, foaming agents, antistatic agents, surfactants, conductivity modifiers, etc., which can be arbitrarily selected and used individually or in combination of two or more.

[0200] Examples of fillers include carbonates such as heavy calcium carbonate, light calcium carbonate, precipitated calcium carbonate, magnesium carbonate, and dawsonite; oxides such as silica, diatomaceous earth, and titanium dioxide; hydroxides such as aluminum hydroxide and magnesium hydroxide; (sulfite) salts such as calcium sulfate and barium sulfate; silicates such as talc, clay, mica, and calcium silicate; carbons such as carbon black and graphite; inorganic fibers such as hollow or solid glass beads, glass short fibers, metal fibers, carbon short fibers, and carbon fibers; metal powders such as iron powder and copper powder; and heat-resistant resins such as polyimide and silicone. These are used individually or in combination of two or more types.

[0201] Colorants can be selected from those conventionally used for coloring plastics. Examples of such colorants include inorganic pigments such as metal powders like aluminum powder and bronze powder, carbon salts like carbon black, oxides like titanium dioxide, zinc oxide, and red iron oxide, sulfates like precipitated barium sulfate, carbonates like calcium carbonate and basic magnesium carbonate, silicates like clay and ultramarine, chromates like yellow lead, aluminates like cobalt blue, and ferrocyanate compounds like Prussian blue; azo pigments like toluidine red, permanent carmine FB, disazo yellow AAA, and lake red C; polycyclic pigments like phthalocyanine blue, indanthron blue, and quinacridone red; dye lakes like Victoria pure blue BO lake and alkaline blue toner; azine pigments; fluorescent pigments; and dyes such as basic dyes, acid dyes, oil-soluble dyes, and disperse dyes. These can be used individually or in combination of two or more.

[0202] Examples of lubricants include aliphatic hydrocarbon lubricants such as low molecular weight waxes, polyethylene waxes, paraffin waxes, and liquid paraffin; higher aliphatic alcohol lubricants such as stearyl alcohol; aliphatic amide lubricants such as stearamide, palmitamide, and methylenebisstearate; fatty acid ester lubricants such as glyceryl monostearate, ethyl diaminostearate, and butyl stearate; or metal soaps and silicone oils, which are used individually or in combination of two or more.

[0203] The above-mentioned polyvinyl chloride resin and other components can be mixed using the same process as with conventional polyvinyl chloride resins. Specifically, it is preferable to dry blend the resin at a temperature of 100-120°C using a mixer such as a Henschel mixer or ribbon blender. In particular, it is preferable to put the mixture consisting of polyvinyl chloride resin and other components into the mixer at room temperature and mix it, then remove it when the resin temperature rises to the range of 100-120°C. The temperature of the mixer may be adjusted at that time. The above-mentioned mixture can be kneaded and granulated using a Banbury mixer, mixing roll, single-screw or twin-screw extruder, etc., in the same way as with conventional polyvinyl chloride resins. Alternatively, the mixture can be molded using an injection molding machine to obtain molded products without granulation.

[0204] The above-mentioned chlorinated polyvinyl chloride resin is typically produced by using polyvinyl chloride resin as a raw material, supplying chlorine to the polyvinyl chloride resin dispersed in an aqueous medium, and then chlorinating it in an aqueous medium by irradiating it with a mercury lamp, heating it for chlorination, or chlorinating it in the presence of a catalyst, or by chlorinating the polyvinyl chloride resin in a gas phase under irradiation with a mercury lamp.

[0205] Examples of vinyl chloride resins used as raw materials before chlorination include, but are not limited to, homopolymers of vinyl chloride and copolymers of vinyl chloride with other copolymerizable monomers (e.g., ethylene, propylene, vinyl acetate, allyl chloride, allyl glycidyl ether, acrylic acid ester, vinyl ether, etc.).

[0206] The average degree of polymerization of the vinyl chloride resin before chlorination may be 600 to 1500, preferably 600 to 1300, and more preferably 600 to 1200.

[0207] The degree of chlorination of the above-mentioned chlorinated polyvinyl chloride resin may be 62 to 70% by mass, preferably 63 to 70% by mass, and more preferably 64 to 70% by mass.

[0208] From the viewpoint of impact resistance at low temperatures, MBS (a copolymer of methyl methacrylate, butadiene, and styrene) may be added to the above-mentioned chlorinated polyvinyl chloride resin. The butadiene content of the above-mentioned MBS is preferably greater than 60% by mass. Examples of such MBS include B56 manufactured by Kaneka Corporation or BTAIIINX manufactured by Kureha Corporation. The above-mentioned MBS is preferably blended in an amount of 1 to 9 parts by mass per 100 parts by mass of the above-mentioned chlorinated vinyl chloride resin.

[0209] The above-mentioned chlorinated polyvinyl chloride resin may also be to which processing aids, stabilizers, lubricants, fillers, pigments, etc., commonly used in chlorinated polyvinyl chloride resins, can be added to the extent that the purpose of this disclosure can be achieved.

[0210] The above-mentioned chlorinated polyethylene resin is obtained by chlorinating polyethylene. Various methods for chlorinating polyethylene are generally classified into three types: solution chlorination, suspension chlorination, and mass chlorination. Chlorination in aqueous suspension or inert liquid is described, for example, in U.S. Patents 2,592,763 and 3,454,544. Mass chlorination, or chlorination in the absence of a liquid suspension or solvent, is described, for example, in U.S. Patents 2,890,213 and 4,425,206 and British Patent No. 834,905.

[0211] The above-mentioned chlorinated polyethylene resin preferably has a chlorine content of 5 to 25% by mass, more preferably 10% by mass or more, and even more preferably 20% by mass or less. The above-mentioned chlorinated polyethylene resin preferably has a chlorine content of 50 to 85% by mass, more preferably 60% by mass or more, and more preferably 75% by mass or less.

[0212] The above chlorinated polyethylene resin may contain a plasticizer as needed. For example, the following formula may be used for the plasticizer: [ka] Examples of compounds represented by the formula (wherein R represents a 2-propylheptyl group or a mixture of a 2-propylheptyl group and a 4-methyl-2-propylhexyl group) include those with heat resistance and bleedability, R must have 10 carbon atoms, and in the case of a mixture, it is preferable that the 4-methyl-2-propylhexyl group content is 30% by mass or less.

[0213] To further improve flame retardancy, the above-mentioned chlorinated polyethylene resin may be blended with metal oxides such as antimony trioxide and antimony pentoxide, bromine-based and chlorine-based organic substances such as tetrabromobisphenol A, hexabromobenzene, and chlorinated paraffin, or well-known heat stabilizers such as tribasic lead sulfate, dibasic lead stearate, dibasic lead phosphite, and basic lead sulfite. Alternatively, vinyl chloride resin may be blended into the resin component. Furthermore, various well-known additives may be added as needed, such as phenolic antioxidants like 1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenyl)butane and tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, crosslinking agents like di-t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane and 2,5-dimethyl-2,5-di(t-butylperoxy)hexine-3, crosslinking aids like trimethylolpropane triacrylate, lubricants, UV absorbers, fillers, colorants, etc. In addition, the resin components may be crosslinked by, for example, irradiation with ionizing radiation or addition of peroxides.

[0214] The above-mentioned chlorinated polyethylene resin can be molded using molding machines that mold general thermoplastic resins, such as single-screw extruders, twin-screw extruders, injection molding machines, and compression molding machines.

[0215] When using the above-mentioned additives, for example, the chlorinated polyethylene resin and the additives can be mixed in predetermined proportions, uniformly dispersed using a ribbon blender, cake mixer, high-speed mixer, etc., and then kneaded at a temperature of 110-180°C using a mill roll, Banbury mixer, pressure kneader, single-screw extruder, twin-screw compounding extruder, plastifier, con-kneader, injection molding machine, compression molding machine, etc., before being pelletized and molded into the desired shape.

[0216] As the vinylidene chloride resin mentioned above, a copolymer of vinylidene chloride and a monomer copolymerizable with vinylidene chloride (vinylidene chloride copolymer) is preferred. In terms of stability and barrier properties against gases, the amount of vinylidene chloride in the heated melt extrusion is preferably 50% by mass or more of the total monomers in the vinylidene chloride resin, more preferably 70% by mass or more, even more preferably 80% by mass or more, and preferably 98% by mass or less, more preferably 97% by mass or less, and even more preferably 95% by mass or less.

[0217] Examples of monomers copolymerizable with vinylidene chloride include vinyl halides such as vinyl chloride; alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, and lauryl acrylate; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; acrylic acid, methacrylic acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride, alkyl maleate, alkyl itaconic acid, acrylonitrile, vinyl acetate, ethylene, propylene, isobutylene, and butadiene. These can be used individually or in combination of two or more.

[0218] The weight-average molecular weight (Mw) of the vinylidene chloride resin is not particularly limited, but in terms of strength and thermal stability during melt molding, it is preferably 50,000 or more, more preferably 60,000 or more, preferably 150,000 or less, more preferably 130,000 or less, and even more preferably 120,000 or less. In this specification, the weight-average molecular weight (Mw) of vinylidene chloride resin is defined as the value obtained by gel permeation chromatography (GPC) using polystyrene as the standard.

[0219] The polymerization method for the vinylidene chloride resin is not particularly limited, and any known method such as suspension polymerization, emulsion polymerization, or solution polymerization can be used. Among these, suspension polymerization is preferred. Examples of suspension polymerization include the direct suspension method, in which monomers are added to water in which a suspension agent is dissolved, and the suspension method described in Japanese Patent Publication No. 62-280207, in which water in which a suspension agent is dissolved is added to the monomer to form a dispersion in which the monomer is discontinuous and water is continuous, via a dispersion in which the monomer is continuous and water is discontinuous.

[0220] The vinylidene chloride resin described above may contain various known additives as needed. Examples of additives include plasticizers, heat stabilizers, light stabilizers, organic lubricants, inorganic powders, and colorants.

[0221] Furthermore, the vinylidene chloride resin may be mixed with at least one thermoplastic resin selected from the group consisting of polyolefin resins and diene polyurethane resins, if necessary.

[0222] The polyolefin resin used in the above-mentioned mixing with vinylidene chloride resin refers to a homopolymer of olefin monomers (ethylene, propylene, butylene, etc.), a copolymer of two or more olefin monomers, or a copolymer of an olefin monomer and a non-olefin monomer. Specifically, examples include high-density polyethylene, low-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene using a Ziegler multi-site catalyst, ethylene-α-olefin copolymer using a single-site catalyst, as well as polypropylene, polybutylene, ethylene-propylene copolymer, ethylene-butylene copolymer, ethylene-propylene-butylene copolymer, and ethylene-propylene-butylene copolymer. Furthermore, polyolefin copolymers modified by copolymerization or graft polymerization of unsaturated carboxylic acids such as maleic acid, fumaric acid, and acrylic acid, or their acid anhydrides, can be used.

[0223] The diene-based polyurethane resin used in the mixing with the vinylidene chloride resin mentioned above refers to a thermoplastic polyurethane resin having a polydiene skeleton (or diene skeleton). Typically, thermoplastic polyurethane resins are polyurethane resins having a soft segment (e.g., derived from a polyol such as polymeric glycol) and a hard segment (e.g., derived from a polyisocyanate such as diisocyanate). Chain extenders and / or crosslinking agents may be used during the reaction between the polyol and polyisocyanate. Multiple types of polyols, polyisocyanates, chain extenders, and crosslinking agents may be used. By using such a diene-based polyurethane resin, the low-temperature properties of the vinylidene chloride resin can be improved while maintaining its barrier properties.

[0224] In the above-mentioned diene-based polyurethane resin, it is preferable that at least one of the raw materials, the polyol and the polyisocyanate, has a polydiene skeleton (or diene skeleton), and it is more preferable that the polyol has a polydiene skeleton (or diene skeleton). As for the diene-based polyurethane resin, it is preferable that at least one of the raw materials, the polyol and the polyisocyanate, has a butadiene skeleton or an isoprene skeleton, and it is more preferable that the butadiene-based polyurethane resin has a butadiene skeleton.

[0225] As the polyisocyanate used as a raw material for the above diene-based polyurethane resin, for example, compounds such as methylene diisocyanate (HDI), tolylene diisocyanate (TDI), diphenylmethane diisocyanate, naphthalene diisocyanate, isophorone diisocyanate (IPDI), xylylene diisocyanate, and phenylene diisocyanate, as well as modified versions, derivatives, mixtures, and polymer compounds thereof, can be used. In addition, as chain extenders and / or crosslinking agents, for example, ethylene glycol, butanediol, propanediol, etc., can be used.

[0226] The thermoplastic resin is preferably at least one selected from the group consisting of polyethylene resin, polypropylene resin, amorphous cycloolefin resin, crystalline cycloolefin resin, polymethylpentene resin, and vinyl chloride resin; more preferably at least one selected from the group consisting of high-density polyethylene, ultra-high molecular weight polyethylene, polypropylene resin, amorphous cycloolefin resin, crystalline cycloolefin resin, polymethylpentene resin, and vinyl chloride resin; even more preferably at least one selected from the group consisting of ultra-high molecular weight polyethylene, polypropylene resin, amorphous cycloolefin resin, crystalline cycloolefin resin, polymethylpentene resin, and vinyl chloride resin; even more preferably at least one selected from the group consisting of polypropylene resin, amorphous cycloolefin resin, crystalline cycloolefin resin, polymethylpentene resin, and vinyl chloride resin; and particularly preferably at least one selected from the group consisting of amorphous cycloolefin resin, crystalline cycloolefin resin, and polymethylpentene resin.

[0227] The components of this disclosure may contain other components as needed. These components include various known additives such as antioxidants, stabilizers, antistatic agents, lubricants, mold release agents, ultraviolet absorbers, dyes and pigments, reinforcing materials (e.g., glass fiber fillers, carbon fiber fillers), drip inhibitors, fillers, flame retardants, and elastomers for improving impact resistance.

[0228] Using antioxidants as other components is one preferred embodiment. Examples of antioxidants include amine-based antioxidants and phenol-based antioxidants as primary antioxidants, and one or more of these can be used. Examples of secondary antioxidants include sulfur-based antioxidants and phosphorus-based antioxidants. The use of primary and secondary antioxidants in combination is preferred, and a combination of phenol-based and phosphorus-based antioxidants is particularly preferred.

[0229] The antioxidant content is preferably 0 parts by mass or more, more preferably 0.1 parts by mass or more, particularly preferably 0.2 parts by mass or more, and preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less, per 100 parts by mass of the thermoplastic resin. A content exceeding 5 parts by mass is undesirable because it causes bleeding.

[0230] The other components mentioned above can be added insofar as they do not impair the effects of the present disclosure. The content of the other components is preferably 20% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 3% by mass or less, relative to the thermoplastic resin, and may also be 0.01% by mass or more.

[0231] The components of this disclosure come into contact with corrosive substances. Part of the component may come into contact with the corrosive substance, or the entire component may come into contact with the corrosive substance.

[0232] The above-mentioned corrosive substance may be any substance that is corrosive, and may be a substance that is corrosive to rubber, resin, metal, etc. Furthermore, the above-mentioned corrosive substance may be a liquid, solid, or gas. It is preferable that it be a liquid in which the effects of this disclosure are more pronounced.

[0233] The above-mentioned corrosive substance has an oxidation-reduction potential (vsNHE) of preferably -2.0V or higher, more preferably -1.0V or higher, even more preferably -0.5V or higher, and also preferably 3.0V or lower, more preferably 2.5V or lower, and even more preferably 2.1V or lower.

[0234] Examples of the corrosive substances mentioned above include acidic substances, basic substances, oxidizing substances, organic solvents, and saltwater.

[0235] Examples of the above-mentioned acidic substances include chemical solutions with a pH of 6 or less, preferably 5 or less, and more preferably 4 or less. Specifically, these include acids such as sulfuric acid, hydrofluoric acid, nitric acid, phosphoric acid, and hydrochloric acid; mixtures of these acids; and mixtures of these acids with other substances (such as hydrogen peroxide). In particular, at least one selected from the group consisting of sulfuric acid, hydrofluoric acid, nitric acid, phosphoric acid, hydrochloric acid, a mixed acid of hydrofluoric acid and nitric acid, a mixed chemical solution of hydrogen peroxide and hydrochloric acid, and a mixed chemical solution of hydrogen peroxide and sulfuric acid is preferred, and at least one selected from the group consisting of hydrofluoric acid, nitric acid, phosphoric acid, hydrochloric acid, a mixed acid of hydrofluoric acid and nitric acid, a mixed chemical solution of hydrogen peroxide and hydrochloric acid, and a mixed chemical solution of hydrogen peroxide and sulfuric acid is more preferred.

[0236] Examples of the above basic substances include chemical solutions with a pH of 8 or higher, preferably 9 or higher, and more preferably 10 or higher. Specifically, TMAH([(CH3)4N] + [OH] - Examples include sodium hydroxide aqueous solution, ammonia and other bases; mixtures of these bases; and mixtures of these bases with other substances (such as hydrogen peroxide). In particular, TMAH([(CH3)4N] + [OH] - Preferably, at least one selected from the group consisting of aqueous sodium hydroxide solution, aqueous ammonia solution, and a mixed chemical solution of hydrogen peroxide solution and aqueous ammonia solution.

[0237] Examples of basic substances include chemical solutions with an oxidation-reduction potential (vsNHE) of -2.0 to 0V, preferably -1.0 to 0V, and more preferably -0.5 to 0V. Specifically, TMAH([(CH3)4N] + [OH] - Examples include basic substances such as aqueous sodium hydroxide solution, aqueous ammonia, hydroxylamine, hydrazine, hydrogen water, and sodium sulfite; and mixtures of these basic substances with other substances. In particular, TMAH([(CH3)4N] + [OH] - Preferably, at least one selected from the group consisting of aqueous sodium hydroxide solution, aqueous ammonia solution, and a mixed chemical solution of hydrogen peroxide solution and aqueous ammonia solution.

[0238] Examples of the oxidizing substances mentioned above include chemical solutions with an oxidation-reduction potential (vsNHE) of 0 to 3.0 V, preferably 0.5 to 2.5 V, and more preferably 1.0 to 2.1 V. Specifically, these include sulfuric acid, nitric acid, hydrochloric acid, hydrogen peroxide, and mixtures of these oxidizing substances with other substances (such as hydrofluoric acid). In particular, at least one selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, hydrogen peroxide solution, a mixed acid of hydrofluoric acid and nitric acid, a mixed chemical solution of hydrogen peroxide solution and hydrochloric acid, and a mixed chemical solution of hydrogen peroxide solution and sulfuric acid is preferred, and at least one selected from the group consisting of nitric acid, hydrochloric acid, a mixed acid of hydrofluoric acid and nitric acid, a mixed chemical solution of hydrogen peroxide solution and hydrochloric acid, and a mixed chemical solution of hydrogen peroxide solution and sulfuric acid is more preferred.

[0239] Examples of the above-mentioned organic solvents include esters such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, and tert-butyl acetate; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aliphatic hydrocarbons such as hexane, cyclohexane, octane, nonane, decane, undecane, dodecane, and mineral spirits; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, and solvent naphtha; alcohols such as methanol, ethanol, isopropyl alcohol, tert-butanol, and ethylene glycol monoalkyl ethers; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; nitriles such as acetonitrile and propionitrile; amides such as dimethyl sulfoxide, N,N-dimethylformamide, and N,N-dimethylacetamide; halogenated hydrocarbons such as dichloromethane, dichloroethane, and chloroform, and mixtures thereof. Among these, alcohols are preferred, and isopropyl alcohol is more preferred.

[0240] The corrosive substance is preferably at least one selected from the group consisting of acidic substances, basic substances, oxidizing substances, organic solvents, and brine; more preferably at least one selected from the group consisting of acidic substances, basic substances, oxidizing substances, and organic solvents; and even more preferably at least one selected from the group consisting of acidic substances and basic substances.

[0241] The corrosive substance mentioned above is preferably at least one selected from the group consisting of sulfuric acid, hydrofluoric acid, nitric acid, phosphoric acid, hydrochloric acid, mixed acid of hydrofluoric acid and nitric acid, mixed chemical solution of hydrogen peroxide and hydrochloric acid, mixed chemical solution of hydrogen peroxide and sulfuric acid, TMAH, aqueous sodium hydroxide solution, aqueous ammonia, mixed chemical solution of hydrogen peroxide and aqueous ammonia, isopropyl alcohol, and saline solution. More preferably, at least one selected from the group consisting of hydrofluoric acid, nitric acid, phosphoric acid, hydrochloric acid, mixed acid of hydrofluoric acid and nitric acid, mixed chemical solution of hydrogen peroxide and hydrochloric acid, mixed chemical solution of hydrogen peroxide and sulfuric acid, TMAH, aqueous sodium hydroxide solution, mixed chemical solution of hydrogen peroxide and aqueous ammonia, and isopropyl alcohol. Even more preferably, at least one selected from the group consisting of hydrofluoric acid, hydrochloric acid, mixed acid of hydrofluoric acid and nitric acid, mixed chemical solution of hydrogen peroxide and sulfuric acid, and TMAH.

[0242] The member of this disclosure may have only a portion (layer) containing the thermoplastic resin, or it may have a portion (layer) containing the thermoplastic resin and other portions (layers). From the viewpoint of ensuring corrosion resistance, it is preferable that at least a part of the surface that comes into contact with the corrosive substance is composed of a portion (layer) containing the thermoplastic resin, and it is more preferable that the entire surface that comes into contact with the corrosive substance is composed of a portion (layer) containing the thermoplastic resin.

[0243] The components of this disclosure are used as at least one component selected from the group consisting of components for building materials, components for mobility, components for aerospace, components for medical use, components for semiconductors, and components for information and communication. Among the above components, semiconductor components are preferred due to their excellent corrosion resistance and low metal leaching, and components for semiconductor manufacturing-related equipment (articles for semiconductor manufacturing-related equipment) are more preferred.

[0244] When the component of this disclosure includes polypropylene resin, it is used as at least one component selected from the group consisting of components for building materials, components for mobility, components for aerospace, components for medical use, components for semiconductors, and components for information and communication. As the above component, components for semiconductors are preferred due to their excellent corrosion resistance and low metal leaching, and components for semiconductor manufacturing-related equipment (articles for semiconductor manufacturing-related equipment) are more preferred.

[0245] When the component of this disclosure contains an amorphous cycloolefin resin, it is used as at least one component selected from the group consisting of components for building materials, components for mobility, components for aerospace, components for medical use, components for semiconductors, and components for information and communication. As the above component, components for semiconductors are preferred due to their excellent corrosion resistance and low metal leaching, and components for semiconductor manufacturing-related equipment (articles for semiconductor manufacturing-related equipment) are more preferred.

[0246] When the component of this disclosure contains a crystalline cycloolefin resin, it is used as at least one component selected from the group consisting of components for building materials, components for mobility, components for aerospace, components for medical use, components for semiconductors, and components for information and communication. As the above component, components for semiconductors are preferred due to their excellent corrosion resistance and low metal leaching, and components for semiconductor manufacturing-related equipment (articles for semiconductor manufacturing-related equipment) are more preferred.

[0247] When the component of this disclosure contains polymethylpentene resin, it is used as at least one component selected from the group consisting of components for building materials, components for mobility, components for aerospace, components for medical use, components for semiconductors, and components for information and communication. As the above component, components for semiconductors are preferred due to their excellent corrosion resistance and low metal leaching, and components for semiconductor manufacturing-related equipment (articles for semiconductor manufacturing-related equipment) are more preferred.

[0248] Examples of building materials (construction materials) components include interior building materials such as baseboards, ceiling materials, and plumbing materials, as well as exterior building materials such as waterproofing sheets, water-stopping materials, exterior wall materials, and roofing materials. Examples of mobility components mentioned above include parts used in ferries, railways, automobiles, motorcycles, drones, robots, and the like. Examples of the above-mentioned aerospace components include exterior and interior materials for aircraft and rockets, wire insulation materials, cable protection materials, jet engines, cabin interior materials, and their components. Examples of the above-mentioned medical components include piping materials, chemical containers, sterilization containers, medical devices, laboratory and analytical instruments, and packaging materials. Examples of semiconductor materials mentioned above include process materials used in semiconductor manufacturing and components for semiconductor manufacturing-related equipment. Examples of the above-mentioned information and communication components include parts for devices such as wireless LAN transmission and reception circuits, circuit boards, and parts for devices such as optical communications.

[0249] Examples of components of this disclosure include containers, piping, nozzles, tubes, tanks, fittings, valves, pumps, housings, spin chucks, O-rings, packings, gaskets, washers, sealing materials, nuts, bolts, films, bottles, wire insulation, hoses, pipes, sheets, rollers, cocks, connectors, filter housings, filter cages, flow meters, wafer carriers, wafer boxes, and the like.

[0250] The components of this disclosure are suitably applicable to at least one selected from the group consisting of containers, piping, nozzles, tubes, tanks, fittings, valves, pumps, spin chucks, O-rings, packings, gaskets, washers, and sealing materials, given that corrosion resistance is required. In one preferred embodiment, the thermoplastic resin is at least one selected from the group consisting of polypropylene resin, amorphous cycloolefin resin, crystalline cycloolefin resin, and polymethylpentene resin, and the component is at least one selected from the group consisting of container, piping, nozzle, tube, tank, fitting, valve, pump, spin chuck, O-ring, packing, gasket, washer, and sealing material. Furthermore, another preferred embodiment is that the thermoplastic resin is a polyethylene resin with a melting point of 120°C or higher, and the component is at least one selected from the group consisting of piping (excluding piping for transporting ultrapure water), nozzles, tubes, fittings, valves, pumps, spin chucks, O-rings, packings, gaskets, washers, and sealing materials.

[0251] The components of this disclosure can be suitably applied to at least one selected from the group consisting of containers, pipes, nozzles, tubes, tanks, fittings, valves, pumps, and spin chucks, and are particularly suitably applied to containers, pipes, nozzles, tubes, tanks, fittings, and valves. Furthermore, it can be suitably used in the above-mentioned containers, piping, nozzles, tubes, tanks, fittings, valves, pumps, spin chucks, O-rings, packings, gaskets, and sealing materials (preferably containers, piping, nozzles, tubes, tanks, fittings, valves, more preferably containers, piping, nozzles, tubes, tanks, fittings) within semiconductor manufacturing-related equipment.

[0252] The components of this disclosure, when containing polypropylene resin, can be suitably applied to at least one selected from the group consisting of containers, pipes, nozzles, tubes, tanks, fittings, valves, pumps, and spin chucks, and are particularly suitably applied to containers, pipes, nozzles, tubes, tanks, fittings, and valves. Furthermore, it can be suitably used in the above-mentioned containers, piping, nozzles, tubes, tanks, fittings, valves, pumps, spin chucks, O-rings, packings, gaskets, and sealing materials (preferably containers, piping, nozzles, tubes, tanks, fittings, valves, more preferably containers, piping, nozzles, tubes, tanks, fittings) within semiconductor manufacturing-related equipment.

[0253] The components of this disclosure, when containing a crystalline cycloolefin resin, can be suitably applied to at least one selected from the group consisting of containers, piping, nozzles, tubes, tanks, fittings, valves, pumps, and spin chucks, and are particularly suitably applied to containers, piping, nozzles, tubes, tanks, fittings, and valves. Furthermore, it can be suitably used in the above-mentioned containers, piping, nozzles, tubes, tanks, fittings, valves, pumps, spin chucks, O-rings, packings, gaskets, and sealing materials (preferably containers, piping, nozzles, tubes, tanks, fittings, valves, more preferably containers, piping, nozzles, tubes, tanks, fittings) within semiconductor manufacturing-related equipment.

[0254] The components of this disclosure, when containing amorphous cycloolefin resin, can be suitably applied to at least one selected from the group consisting of containers, piping, nozzles, tubes, tanks, fittings, valves, pumps, and spin chucks, and are particularly suitably applied to containers, piping, nozzles, tubes, tanks, fittings, and valves. Furthermore, it can be suitably used in the above-mentioned containers, piping, nozzles, tubes, tanks, fittings, valves, pumps, spin chucks, O-rings, packings, gaskets, and sealing materials (preferably containers, piping, nozzles, tubes, tanks, fittings, valves, more preferably containers, piping, nozzles, tubes, tanks, fittings) within semiconductor manufacturing-related equipment.

[0255] The components of this disclosure, when containing polymethylpentene resin, can be suitably applied to at least one selected from the group consisting of containers, piping, nozzles, tubes, tanks, fittings, valves, pumps, and spin chucks, and are particularly suitably applied to containers, piping, nozzles, tubes, tanks, fittings, and valves. Furthermore, it can be suitably used in the above-mentioned containers, piping, nozzles, tubes, tanks, fittings, valves, pumps, spin chucks, O-rings, packings, gaskets, and sealing materials (preferably containers, piping, nozzles, tubes, tanks, fittings, valves, more preferably containers, piping, nozzles, tubes, tanks, fittings) within semiconductor manufacturing-related equipment.

[0256] The piping is not particularly limited, but in terms of shape, an inner diameter of 2 mm to 400 mm is preferred, 2 mm to 100 mm is more preferred, and 2 mm to 25 mm is particularly preferred. Examples include robust pipe types, flexible hoses that can be incorporated according to the installation space, and bellows pipes that can be bent despite having a large diameter. Furthermore, the inside of the piping may be made of a material that is clean (less contamination of the chemical solution by extracted ions) and chemical resistant, and may be subjected to high-precision polishing that does not generate dust and does not disturb the liquid flow or gas flow. Depending on the type of chemical being used, such as organic solvents, antistatic properties may be required to prevent static electricity buildup. In such cases, conductive fillers (carbon black, carbon nanotubes, etc.) may be added to provide antistatic properties, provided that cleanliness is not compromised.

[0257] While there are no particular limitations on the nozzle itself, the tip may be precisely machined to match the size and shape of the part. In addition, since it comes into contact with the part, it can be made of a highly hard and durable material that is resistant to friction and bending.

[0258] The tube is not particularly limited, but the tube diameter is preferably 2 mm to 400 mm, more preferably 2 mm to 100 mm, and especially preferably 2 to 25 mm. A material with stress crack resistance, chemical resistance, excellent mechanical strength, and cleanliness (less contamination of the chemical solution by extracted ions) is used. In addition, depending on the chemical solution to be flowed, such as organic solvents, antistatic properties may be required to prevent electrostatic charge buildup, and conductive fillers (carbon black, carbon nanotubes, etc.) may be added to provide antistatic properties within a range that does not worsen cleanliness.

[0259] The containers and tanks are not particularly limited, but they may be subjected to precision cleaning (water washing, acetic acid immersion, hydrochloric acid immersion, nitric acid immersion, wiping cleaning, pure water washing, etc.) to remove dirt and residue. Packaging after cleaning may be carried out in a cleanroom or clean booth environment.

[0260] The fittings and valves are not particularly limited, but they are required to be oil-free, particle-free, dead space-free, and externally leak-free, and their size is preferably in the range of Φ3.2mm to 40mm, and more preferably in the range of Φ3.2 to 12.7mm.

[0261] While not particularly limited, a pump may sometimes require retractability.

[0262] While not particularly limited, spin chucks may require hardness, corrosion resistance, and dimensional stability, and conductivity may be added.

[0263] While there are no particular limitations on the O-ring and sealing material, the material properties that are required include excellent elasticity, good compression set, high wear resistance, excellent heat resistance, resistance to the liquids and gases to which it is applied, and a long lifespan. In particular, O-rings used in semiconductor manufacturing equipment are used in harsh chemical environments, such as being exposed to various plasmas, and therefore high heat resistance, chemical resistance, and plasma resistance are required. The compression set is preferably 25% or less at 100°C for 72 hours, more preferably 20% or less, even more preferably 15% or less, and even more preferably 10% or less.

[0264] While there are no particular limitations on packings and gaskets, they are often required to have good compression set, a low coefficient of friction, and excellent wear resistance. To prevent leaks, heat resistance, cold resistance, pressure resistance, and chemical resistance are also sometimes required. The compression set is preferably 25% or less at 100°C for 72 hours, more preferably 20% or less, even more preferably 15% or less, and even more preferably 10% or less.

[0265] While washers are not particularly limited, they are often intended for use in cleanrooms and similar environments, requiring durability, corrosion resistance, and rust prevention.

[0266] The components of this disclosure can be used, for example, for the following purposes: <Building materials> Exterior materials for furniture, interior building materials for walls, ceilings, floors, etc. Exterior building materials such as siding, fences, roofs, gates, and gable boards; Window frames, doors, handrails, thresholds, lintels, etc. - decorative surface materials; Membrane materials (roofing materials, ceiling materials, exterior wall materials, interior wall materials, covering materials, etc.) for membrane structures (sports facilities, horticultural facilities, atriums, etc.); Outdoor-use lumber (soundproof walls, windbreak fences, wave overhang fences, garage canopies, shopping malls, walkway walls, roofing materials); Building materials such as tent materials for tent warehouses, sunshade membranes, partial roofing materials for letting in light, window materials to replace glass, fire-resistant partition membranes, curtains, exterior wall reinforcement, waterproof membranes, smoke barriers, non-combustible transparent partitions, and road reinforcement; Agricultural films, weather-resistant covers for various roofing materials and side walls; Covering materials for glass products such as non-combustible fire-resistant safety glass; etc. Among these, given the requirement for corrosion resistance, it is particularly suitable for use in membrane materials for membrane structures, outdoor paneling, tent materials for tent warehouses, sunshade membranes, partial roofing materials for letting in light, window materials as an alternative to glass, fire-resistant partition membranes, curtains, exterior wall reinforcement, waterproof membranes, smoke-proof membranes, non-combustible transparent partitions, road reinforcement and other building materials, agricultural films, and weather-resistant covers for various roofing materials and side walls. When using the components of this disclosure for the above applications, from the viewpoint of corrosion resistance, weather resistance, and economic efficiency, at least one thermoplastic resin selected from the group consisting of polyethylene resin, polypropylene resin, amorphous cycloolefin resin, crystalline cycloolefin resin, and polymethylpentene resin is preferred.

[0267] <Mobility> O-rings, tubes, gaskets, valve cores, hoses, seals, and diaphragms used in the fuel systems and peripheral equipment of automobiles (for example, injector O-rings, injector gaskets, fuel pump O-rings, diaphragms, fuel hoses, filler hoses, and evaporator hoses) (these may be for sour gasoline, alcohol fuel, or fuels containing gasoline additives such as methyl tert-butyl ether and amines). Hoses and sealing materials used in automatic transmission (AT) systems of automobiles (e.g., ATF hoses); Gaskets, shaft seals, valve stem seals, sealing materials, and hoses used in automobile engines and peripheral equipment (e.g., carburetor flange gaskets, engine head gaskets, metal gaskets, crankshaft seals, camshaft seals, valve stem seals, manifold packings, oil hoses); Oxygen sensor for automotive engines; Automotive components such as brake hoses, air conditioning hoses, radiator hoses, radiator tanks, chemical tanks, bellows, spacers, rollers, gasoline tanks, bumpers, door trims, instrument panels, wire insulation materials, and other automotive parts; O-rings, tubes, gaskets, valve cores, hoses, seals, and diaphragms used in the fuel systems and peripheral equipment of ships; Corrosion-preventive tapes for pipes, such as tapes used to wrap around pipes on ship decks; etc. Among these, due to the requirement of corrosion resistance, it can be particularly suitably used in tubes, valve cores, hoses, and diaphragms used in the fuel systems and peripheral equipment of automobiles; other automotive components such as brake hoses, air conditioning hoses, radiator hoses, radiator tanks, chemical tanks, bellows, spacers, rollers, gasoline tanks, bumpers, door trims, instrument panels, and wire insulation materials; hoses used in the automatic transmission systems of automobiles; and tubes, valve cores, hoses, and diaphragms used in the fuel systems and peripheral equipment of ships. When using the components of this disclosure for the above applications, from the viewpoint of corrosion resistance and oil resistance, at least one thermoplastic resin selected from the group consisting of polyethylene resin, polypropylene resin, amorphous cycloolefin resin, crystalline cycloolefin resin, and polymethylpentene resin is preferred.

[0268] <Aerospace> O-rings, tubes, packings, valve cores, hoses, seals, and diaphragms used in the fuel systems and peripheral equipment of aircraft and rockets; etc. Among these, due to the requirement of corrosion resistance, it can be particularly suitable for use in tubes, valve cores, hoses, and diaphragms used in the fuel systems and peripheral equipment of aircraft and rockets. When using the components of this disclosure for the above applications, from the viewpoint of corrosion resistance and heat resistance, at least one thermoplastic resin selected from the group consisting of amorphous cycloolefin resin, crystalline cycloolefin resin, and polymethylpentene resin is preferred.

[0269] <Medical> Medical infusion tubes, blood collection tubes, drainage tubes, catheters, catheter connectors, stents, pipes, fittings, tube connectors, valves, filters, and other piping materials; Liquid, powder, or solid drug containers such as packaging, bottles, bottle caps, vials, ampoules, pre-filled syringes, infusion bags, infusion bag connectors, sealed drug bags, press-through packages, and eye drop containers; Sample containers such as urine collection bags, test tubes for blood sampling, blood collection tubes, test cells, and specimen containers; Sterilization containers for medical instruments such as scalpels, forceps, gauze, and contact lenses; Housings for electronic devices such as medical sensors, cardiac devices, and pacemakers; Medical devices such as inhalation masks, syringes, syringe rods, injection needles, surgical trays, protective plugs, rubber stoppers, and endoscopes; Laboratory and analytical equipment such as beakers, petri dishes, flasks, test tubes, and centrifuge tubes; Medical optical components such as plastic lenses for medical examinations; Artificial organs and their components, such as denture bases, dentures, artificial hearts, artificial tooth roots, artificial bones, and artificial joints; etc. Among these, from the viewpoint of chemical resistance and heat resistance, it can be used particularly suitably for medical infusion tubes, blood collection tubes, drain tubes, catheters, piping, fittings, tube connectors, valves, bottles, bottle caps, vials, ampoules, pre-filled syringes, infusion bags, urine collection bags, test tubes for blood sampling, blood collection tubes, test cells, specimen containers, sterile containers, syringes, syringe rods, surgical trays, and protective stoppers. When using the components of this disclosure for the above applications, at least one thermoplastic resin selected from the group consisting of polyethylene resin, polypropylene resin, amorphous cycloolefin resin, crystalline cycloolefin resin, and polymethylpentene resin is preferred.

[0270] <Information and Communication> Insulating boards for high-frequency circuits, insulating materials for connecting components, printed circuit boards; Bases and antenna covers for high-frequency vacuum tubes; Wire insulation material for coaxial cables, LAN cables, etc. Optical fiber coating material; LCD displays and other types of displays; Components for mobile phones; etc. Among these, due to the requirement of corrosion resistance, it can be particularly suitable for use in insulating boards for high-frequency circuits, insulating materials for connecting components, printed circuit boards, bases and antenna covers for high-frequency vacuum tubes, wire coverings for coaxial cables and LAN cables, and optical fiber coverings. When using the components of this disclosure for the above applications, at least one thermoplastic resin selected from the group consisting of polyethylene resin, polypropylene resin, amorphous cycloolefin resin, crystalline cycloolefin resin, and polymethylpentene resin is preferred.

[0271] <Semiconductors> Chemical transfer components for semiconductor factories and semiconductor manufacturing-related equipment, including chemical tanks, containers, housings, piping, O-rings, tubes, packings, valve cores, hoses, seals, rolls, gaskets, washers, diaphragms, nozzles, fittings, coatings, and inner linings for pipes; Drug stoppers and packaging films; Wastewater transport components such as tanks, containers, piping, tubes, hoses, fittings, and nozzles; Containers, tubes, hoses, and other components for transporting high-temperature liquids; Steam piping components such as tubes and hoses for steam piping; etc. Among these, from the viewpoint of chemical resistance and heat resistance, it can be suitably used for chemical transfer components such as chemical tanks, containers, housings, piping, O-rings, tubes, packings, valve cores, hoses, sealing materials, gaskets, washers, diaphragms, nozzles, and fittings for semiconductor manufacturing-related equipment, as well as waste liquid transport components such as containers, piping, tubes, and hoses for waste liquid transport. When using the components of this disclosure for the above applications, from the viewpoint of chemical resistance and heat resistance, at least one thermoplastic resin selected from the group consisting of polypropylene resin, amorphous cycloolefin resin, crystalline cycloolefin resin, polymethylpentene resin, and vinyl chloride resin is preferred, at least one selected from the group consisting of polypropylene resin, amorphous cycloolefin resin, crystalline cycloolefin resin, and polymethylpentene resin is more preferred, and at least one selected from the group consisting of amorphous cycloolefin resin, crystalline cycloolefin resin, and polymethylpentene resin is particularly preferred.

[0272] The semiconductor manufacturing equipment mentioned above includes photolithography equipment (coating equipment, resist stripping equipment, developing equipment (developer), baking equipment, discam equipment), thin film formation / etching / cleaning / drying equipment (vacuum deposition equipment, sputtering equipment, CVD equipment, cleaning equipment, etching equipment, drying equipment, scrub cleaning equipment), inspection and evaluation equipment / other manufacturing equipment (defect correction equipment), wafer processing equipment (wafer marking equipment), resist processing equipment (coating equipment, developing equipment, resist stripping equipment, ashing equipment, baking equipment), etching equipment. Etching equipment (dry etching equipment, wet etching equipment), cleaning and drying equipment (dry cleaning equipment, wet cleaning equipment, scrub cleaning equipment, drying equipment), heat treatment equipment (oxidation equipment, diffusion equipment, annealing equipment), ion implantation equipment (high-current ion implantation equipment, medium-current ion implantation equipment, high-energy ion implantation equipment), thin film formation equipment, CVD equipment (high-pressure CVD equipment, SACVD, reduced-pressure CVD, plasma CVD equipment, metal CVD equipment, ALD equipment), sputtering equipment, and other thin film formation equipment (vacuum deposition equipment, silicon epitaxial growth equipment, compound semiconductor semiconductor equipment). Conductor epitaxial equipment (MOCVD equipment, MBE equipment), plating equipment), inspection and evaluation equipment (Auger electron spectrometer), CMP equipment (CMP equipment, CMP cleaning equipment), other processing equipment (wafer marking equipment, back grinding machine, bump plating equipment, back grinder tape application machine, back grinder, back grinder tape removal machine), dicing equipment (dicing equipment, wafer mounting equipment), bonding equipment (die bonding equipment, hybrid bonding equipment, wire bonding equipment, inner lead bonding equipment) Examples include molding equipment, outer lead bonding equipment, flip-chip bonding equipment, packaging equipment (molding equipment, deburring equipment, soldering equipment), other testing equipment (electron beam testing equipment, laser beam testing equipment), probing equipment (proppers), handlers, aging equipment (aging equipment, burn-in equipment, IC insertion equipment, IC extraction equipment), and other inspection equipment (cold and heat testing equipment, temperature and humidity testing equipment, pressure cooker equipment, laser processing systems, various life testing equipment). Related equipment for semiconductor manufacturing includes various transport devices (in-process wafer transport devices, inter-process wafer transport devices, stockers), pure water and chemical solution equipment (pure water production devices, ultrafiltration devices, reverse osmosis devices, sterilization devices, chemical supply devices, slurry supply devices, chemical purification devices, wastewater treatment devices), various gas equipment (gas generators, gas purification devices, gas mixing devices, gas detection devices, exhaust gas treatment devices), cleanroom equipment (clean benches, clean tunnels, thermal chambers, environmental testing equipment, air showers, pass boxes), and other manufacturing-related equipment (various jig cleaning and drying devices, flow control equipment, various taping devices, various packaging devices, measuring instruments for liquids and various gases).

[0273] Among these, semiconductor manufacturing equipment that uses corrosive substances within the device is not particularly limited, but from the perspective of utilizing the chemical resistance properties, photolithography process equipment (coating equipment, resist stripping equipment, developing equipment (developer), discam equipment), thin film formation / etching / cleaning and drying equipment (vacuum deposition equipment, CVD equipment, cleaning equipment, etching equipment, drying equipment, scrub cleaning equipment), inspection and evaluation equipment / other manufacturing equipment (defect correction equipment), resist processing equipment (coating equipment, developing equipment, resist stripping equipment, ashing equipment), etching equipment (dry etching equipment, wet etching equipment), washing Cleaning and drying equipment (wet cleaning equipment, scrub cleaning equipment, drying equipment), CVD equipment (high-pressure CVD equipment, SACVD, reduced-pressure CVD, plasma CVD equipment, metal CVD equipment, ALD equipment), other thin-film deposition equipment (vacuum deposition equipment, silicon epitaxial growth equipment, compound semiconductor epitaxial equipment (MOCVD equipment, MBE equipment), plating equipment), CMP equipment (CMP equipment, cleaning equipment for CMP), other processing equipment (bump plating equipment), aging equipment (aging equipment, burn-in equipment, IC insertion equipment, IC extraction equipment), and other inspection equipment (various life testing equipment) are preferred. As related equipment for semiconductor manufacturing equipment, the following are preferred: pure water and chemical solution systems (chemical supply systems, slurry supply systems, chemical purification systems, wastewater treatment systems), various gas systems (gas generators, gas purification systems, gas mixing systems, gas detection systems, exhaust gas treatment systems), cleanroom systems (thermal chambers, environmental testing equipment), and other manufacturing-related equipment (various jig cleaning and drying systems, flow control equipment, various packaging systems, measuring instruments for liquids and various gases).

[0274] As described above, the components of this disclosure can be suitably used as components (articles for semiconductor manufacturing equipment) and, due to their excellent chemical resistance, are particularly suitable as components constituting semiconductor manufacturing equipment in which chemicals are used, and especially as components that come into contact with chemicals.

[0275] The above-mentioned chemicals are not particularly limited, but examples include chemicals used in semiconductor manufacturing equipment. These chemicals can be used individually or in combination of two or more.

[0276] Specifically, the above-mentioned chemical is TMAH([(CH3)4N] + [OH] - Examples include at least one selected from the group consisting of sodium hydroxide aqueous solution, sulfuric acid, isopropyl alcohol, hydrofluoric acid, a mixed acid of hydrofluoric acid and nitric acid, SPM (Sulfuric Acid Hydrogen Peroxide Mixture), SC1 (a mixture of NH4OH, H2O2, and H2O), SC2 (a mixture of HCl, H2O2, and H2O), phosphoric acid, and hydrochloric acid. Among these, TMAH, isopropyl alcohol, hydrofluoric acid, a mixed acid of hydrofluoric acid and nitric acid, SPM, SC1, SC2, phosphoric acid, and hydrochloric acid are preferred, and TMAH, hydrofluoric acid, a mixed acid of hydrofluoric acid and nitric acid, and SPM are more preferred.

[0277] Other examples of the above-mentioned chemicals include at least one selected from the group consisting of silicon-based gases, arsenic-based gases, phosphorus-based gases, boron-based gases, metal hydride gases, metal alkyl gases, halogenated hydrocarbon gases, halogen / halogen gases, nitrogen oxide gases, hydrogen sulfide gases, ammonia gas, trimethylamine gas, propane gas, trimethylaluminum gas, hydrogen gas, helium gas, nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas.

[0278] Examples of the silicon-based gases mentioned above include monosilane, dichlorosilane, trichloride silane, silicon tetrachloride, silicon tetrafluoride, and disilane. Examples of the above-mentioned arsenic gases include arsine, arsenic(III) fluoride, arsenic(V) fluoride, arsenic(III) chloride, and arsenic(V) chloride. Examples of the phosphorus-based gases mentioned above include phosphine, phosphorus(III) fluoride, phosphorus(V) fluoride, phosphorus(III) chloride, phosphorus(V) chloride, and phosphorus oxychloride. Examples of the boron-based gases mentioned above include diborane, boron trifluoride, boron trichloride, and boron tribromide. Examples of the above-mentioned metal hydride gases include hydrogen selenide, monogermane, hydrogen telluride, styvin, and tin hydride. Examples of the above-mentioned metal alkyl gases include trialkylgallium and trialkylindium. Examples of the above-mentioned halogenated hydrocarbon gases include methane tetrafluoride, methane trifluoride, methane difluoride, propane hexafluoride, propane octafluoride, and cyclobutane octafluoride. Examples of the above-mentioned halogen and halide gases include fluorine, hydrogen fluoride, chlorine, hydrogen chloride, carbon tetrachloride, hydrogen bromide, sulfur hexafluoride, nitrogen trifluoride, sulfur tetrafluoride, tungsten(VI) fluoride, molybdenum(VI) fluoride, germanium tetrachloride, tin(IV) chloride, antimony(V) chloride, tungsten(VI) chloride, and molybdenum hexachloride. Examples of the nitrogen oxide gases mentioned above include nitric oxide, nitrogen dioxide, and dinitrogen monoxide. Among these, ammonia gas, nitrogen trifluoride, nitrous oxide, monosilane, and cyclobutane octafluoride are preferred, and ammonia gas, nitrogen trifluoride, and nitrous oxide are more preferred.

[0279] The above-mentioned semiconductor manufacturing equipment component (semiconductor manufacturing equipment article) may have only a portion (layer) containing the thermoplastic resin, or it may have a portion (layer) containing the thermoplastic resin and other portions (layers). From the viewpoint of ensuring chemical resistance, it is preferable that at least a part of the surface that comes into contact with the chemical is composed of a portion (layer) containing the thermoplastic resin, and it is more preferable that the entire surface that comes into contact with the chemical is composed of a portion (layer) containing the thermoplastic resin.

[0280] The components of this disclosure are preferably such that, when a test specimen (size: 10 mm × 50 mm × 2 mm) of the component is immersed for one week in each of the three chemical solutions described in (1), (6), and (7) below, the relative mass after immersion, with the mass before immersion set to 100, is between 95 and 105. Components that satisfy this requirement have excellent corrosion resistance. The above relative value is more preferably 97 or higher, even more preferably 98 or higher, even more preferably 99 or higher, and more preferably 103 or lower, even more preferably 102 or lower, and even more preferably 101 or lower. Ideally (most preferably) it is 100.

[0281] It is more preferable that, when a test specimen of the component (size: 10 mm × 50 mm × 2 mm) is immersed in each of the 10 chemical solutions (1) to (10) described later for one week, the relative mass after immersion, with the mass before immersion set to 100, falls within the range described above.

[0282] Preferably, the member of this disclosure is such that when a test specimen (size: 10 mm x 50 mm x 2 mm) of the member is immersed in each of the 10 chemical solutions (1) to (10) described below for one week, and the relative mass after immersion is calculated with the mass before immersion set to 100, the average of the relative values ​​for the 10 chemical solutions is 95 or more and 105 or less, and the standard deviation is 20 or less. Members that satisfy this requirement have excellent corrosion resistance. The average of the above relative values ​​is more preferably 97 or higher, even more preferably 98 or higher, even more preferably 99 or higher, and more preferably 103 or lower, even more preferably 102 or lower, and even more preferably 101 or lower. Ideally (most preferably) it is 100. The standard deviation of the above relative values ​​is more preferably 10 or less, even more preferably 5 or less, even more preferably 3 or less, even more preferably 2 or less, particularly preferably 1 or less, and may be 0 or greater. Ideally (most preferably) it is 0.

[0283] The chemical solution used for immersing the above test specimens is as follows: (1)25% by mass TMAH([(CH3)4N] + [OH] - (80℃) (2) 98% by mass sulfuric acid (90℃), (3) 100% by mass isopropyl alcohol (80°C) (4) 49% by mass hydrofluoric acid (70℃) (5) Mixed acid of hydrofluoric acid and nitric acid (a mixture of 49% hydrofluoric acid and 69-71% nitric acid in a volume ratio of 1:5) (20℃) (6) Mixed acid of hydrofluoric acid and nitric acid (a mixture of 49% hydrofluoric acid and 69-71% nitric acid by mass in a volume ratio of 1:100) (20℃) (7) SPM (a mixture of 98% sulfuric acid by mass and 30-36% hydrogen peroxide by mass in a volume ratio of 2:1) (80°C) (8) SC1 (a mixture of 25-28% by mass of aqueous ammonia, 30-36% by mass of aqueous hydrogen peroxide, and deionized water in a volume ratio of 1:1:5) (70°C) (9) SC2 (a mixture of 35-37% hydrochloric acid, 30-36% hydrogen peroxide, and deionized water in a volume ratio of 1:1:4) (70°C) (10)85% by mass phosphoric acid (80℃)

[0284] The material disclosed herein preferably has a metal leaching amount (by mass) of 16 elements (Li, Na, Mg, Al, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Ag, Cd, Pb) of 20 ppb or less, more preferably 10 ppb or less, even more preferably 6 ppb or less, even more preferably 3 ppb or less, even more preferably 2 ppb or less, even more preferably 1.6 ppb or less, and particularly preferably 1 ppb or less when a test specimen (size: 10 mm × 50 mm × 2 mm) of the material is immersed in 3.6 mass% hydrochloric acid at 23°C for one week.

[0285] The component of this disclosure is obtained by immersing a test piece of the component (size: 10 mm × 50 mm × 2 mm) in each of the 10 chemical solutions (1) to (10) described above for one week, and confirming the change in color before and after immersion by the degree of yellowing (ΔYI). Preferably, the number of chemical solutions in which ΔYI changed by 3 or more is 4 or less, more preferably 3 or less, even more preferably 2 or less, and may also be 0 or more, or 1 or more.

[0286] In terms of heat resistance, the member of this disclosure preferably has a load deflection temperature of 50°C or higher at a load of 1.82 MPa, more preferably 60°C or higher, even more preferably 70°C or higher, even more preferably 85°C or higher, particularly preferably 120°C or higher, and may also be 200°C or lower, or 150°C or lower. The above load deflection temperature is measured at a load of 1.82 MPa in accordance with ASTM D648.

[0287] The components of this disclosure can be manufactured, for example, by molding a material containing the thermoplastic resin and, if necessary, other components described above. The molding method is not particularly limited, and known methods such as extrusion molding, injection molding, transfer molding, blow molding, inflation molding, and compression molding can be employed.

[0288] This disclosure also relates to semiconductor manufacturing equipment equipped with the components of this disclosure described above. The use of these components provides the equipment with excellent corrosion resistance.

[0289] The semiconductor manufacturing equipment described in this disclosure is preferably the semiconductor manufacturing equipment and related equipment described above. Furthermore, the semiconductor manufacturing equipment described in this disclosure is preferably at least one selected from the group consisting of semiconductor manufacturing equipment and related equipment for semiconductor manufacturing equipment.

[0290] The above semiconductor manufacturing equipment is at least one selected from the group consisting of photolithography equipment, thin film formation / etching / cleaning / drying equipment, inspection / evaluation equipment / manufacturing equipment, resist processing equipment, etching equipment, cleaning / drying equipment, CVD equipment, thin film formation equipment, CMP equipment, processing equipment, aging equipment, and inspection equipment. The above-mentioned semiconductor manufacturing equipment-related equipment is preferably at least one selected from the group consisting of pure water / chemical solution equipment, gas equipment, cleanroom equipment, and manufacturing-related equipment.

[0291] The above-mentioned photolithography apparatus is at least one selected from the group consisting of a coating apparatus, a resist stripping apparatus, a developing apparatus (developer), and a discam apparatus. The above-mentioned thin-film formation, etching, cleaning, and drying apparatus is at least one selected from the group consisting of a vacuum deposition apparatus, a cleaning apparatus, a drying apparatus, and a scrubbing cleaning apparatus. The above inspection and evaluation equipment and manufacturing equipment are defect correction devices. The above-mentioned resist processing apparatus is at least one selected from the group consisting of a coating apparatus, a developing apparatus, a resist stripping apparatus, and an ashing apparatus. The etching apparatus described above is at least one selected from the group consisting of a dry etching apparatus and a wet etching apparatus. The above-mentioned washing and drying apparatus is at least one selected from the group consisting of a wet washing apparatus, a scrubbing washing apparatus, and a drying apparatus. The above-mentioned CVD apparatus is at least one selected from the group consisting of high-pressure CVD apparatus, SACVD, reduced-pressure CVD, plasma CVD apparatus, metal CVD apparatus, and ALD apparatus. The thin-film formation apparatus described above is at least one selected from the group consisting of a vacuum deposition apparatus, a silicon epitaxial growth apparatus, a compound semiconductor epitaxial apparatus (MOCVD apparatus, MBE apparatus), and a plating apparatus. The above-mentioned CMP equipment is at least one selected from the group consisting of a CMP device and a CMP cleaning device. The above-mentioned processing apparatus is a bump plating apparatus, The above-mentioned aging apparatus is at least one selected from the group consisting of an aging apparatus, a burn-in apparatus, an IC insertion apparatus, and an IC extraction apparatus. The above inspection device is a life test device. The above-mentioned pure water / chemical solution system is at least one selected from the group consisting of a chemical supply system, a slurry supply system, a chemical purification system, and a waste liquid treatment system. The above-mentioned gas apparatus is at least one selected from the group consisting of a gas generator, a gas purification device, a gas mixing device, a gas detection device, and an exhaust gas treatment device. The above-mentioned cleanroom equipment is at least one selected from the group consisting of a thermal chamber and an environmental testing apparatus. The above-mentioned manufacturing-related equipment is preferably at least one selected from the group consisting of jig cleaning and drying equipment, flow rate control equipment, packaging equipment, and liquid and gas measuring equipment.

[0292] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Examples]

[0293] The present disclosure will now be further described with reference to examples, but the present disclosure is not limited to these examples.

[0294] Various physical properties were measured using the following method.

[0295] <Chemical resistance (corrosion resistance) test> The resin sheets obtained in the examples and comparative examples were cut to a size of 10 mm × 50 mm × 2 mm to be used as test specimens. The test specimens were dried at 60°C for 2 hours. After drying, the mass of the test specimen was measured under room temperature (20°C) conditions before immersion. After measurement, the test specimens were completely immersed in each of the following chemical solutions (1) to (10) and kept there for one week (168 hours). After holding, the test specimens were washed with pure water, surface water droplets were wiped off, and they were dried at 60°C for 12 hours. The mass of the immersed test specimens was then measured under room temperature (20°C) conditions. From the measured masses before and after immersion, the relative value of the mass after immersion was calculated, with the mass before immersion set to 100. Furthermore, the mean and standard deviation of the immersion mass (relative value) for the 10 types (1) to (10) were calculated. (Medicinal solution) (1)25% by mass TMAH([(CH3)4N] + [OH] - (80℃) (2) 98% by mass sulfuric acid (90°C) Oxidation-reduction potential (vsNHE): 1.1V (3) 100% by mass isopropyl alcohol (80°C) (4) 49% by mass hydrofluoric acid (70℃) (5) Mixed acid of hydrofluoric acid and nitric acid (a mixture of 49% hydrofluoric acid and 69-71% nitric acid in a volume ratio of 1:5) (20℃) (6) Mixed acid of hydrofluoric acid and nitric acid (a mixture of 49% hydrofluoric acid and 69-71% nitric acid by mass in a volume ratio of 1:100) (20℃) (7) SPM (a mixture of 98% sulfuric acid by mass and 30-36% hydrogen peroxide by mass in a volume ratio of 2:1) (80°C) Redox potential (vsNHE): 1.8V (8) SC1 (a mixture of 25-28% by mass aqueous ammonia, 30-36% by mass aqueous hydrogen peroxide, and deionized water in a volume ratio of 1:1:5) (70°C) Redox potential (vsNHE): 1.2V (9) SC2 (a mixture of 35-37% hydrochloric acid, 30-36% hydrogen peroxide, and deionized water in a volume ratio of 1:1:4) (70°C) Redox potential (vsNHE): 1.6V (10)85% by mass phosphoric acid (80℃)

[0296] <Changes in appearance> The color change of the test specimens before and after immersion in the chemical solution was confirmed by the degree of yellowing (ΔYI), and the evaluation was based on the number of chemical solutions in which the ΔYI changed by 3 or more. The degree of yellowing was determined in accordance with JIS K 7373.

[0297] <Temperature of deflection under load> Measurements were taken at a load of 1.82 MPa in accordance with ASTM D648.

[0298] <Metal elution test> The resin sheets obtained in the examples and comparative examples were cut to a size of 10 mm × 50 mm × 2 mm to be used as test specimens. As a pre-cleaning step, the test specimens were immersed in 3.6% by mass hydrochloric acid for 1 hour, followed by rinsing with pure water. Then, the test specimens were immersed in 100 mL of 3.6% by mass hydrochloric acid at 23°C. One week (168 hours) after the start of immersion, a portion of each immersion solution was withdrawn, and the metal concentrations of 16 elements (Li, Na, Mg, Al, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Ag, Cd, Pb) were measured using ICP-MSI (Agilent 8900, Agilent Technologies) to determine the amount of metal leached.

[0299] The materials used in the examples and comparative examples are shown below. (resin) LDPE: Novatec LD LJ802, manufactured by Nippon Polyethylene Co., Ltd., melting point: 106℃, heat of fusion: 100 J / g, density: 0.921 g / m³ 3 HDPE: Novatec HD HJ360 manufactured by Nippon Polyethylene Co., Ltd., melting point: 130℃, heat of fusion: 180 J / g, density: 0.951 g / m³ 3 Ultra-high molecular weight PE: "Lubmer L4000" manufactured by Mitsui Chemicals, Inc., melting point: 138°C, heat of fusion: 127 J / g, density: 0.967 g / m³ 3 PP: Novatec PP MA3 manufactured by Nippon Polypropylene Co., Ltd., melting point: 163℃, heat of fusion: 84 J / g, density: 0.90 g / m³ 3 PMP: Mitsui Chemicals, Ltd. "TPX RT31", melting point: 232℃, heat of fusion: 42 J / g, density: 0.83 g / m³ 3 Amorphous COP: ZEONEX T62R, manufactured by Zeon Corporation; glass transition temperature: 154°C; density: 1.01 g / m³ 3 Crystalline COP: A crystalline ring-opening polymer hydride (syndiotactic crystalline dicyclopentadiene ring-opening polymer hydride) synthesized as described in Synthesis Example 1 below was used. PVC: Mitsubishi Chemical Corporation "Vinica D7653", glass transition temperature: 72℃, density: 1.35g / m³ 3 Chlorine content: 57% by mass PEEK: VICTREX PEEK 450G manufactured by Victrex, melting point: 338°C, heat of fusion: 51 J / g, density: 1.30 g / m³ 3 PPS: DIC Corporation "FZ-2100", melting point: 277℃, heat of fusion: 33 J / g, density: 1.34 g / m³ 3 PEI: Duratron U1000PEI manufactured by Mitsubishi Chemical Advanced Materials, Glass transition temperature: 217℃, Density: 1.27g / m³ 3

[0300] Synthesis Example 1 (Synthesis of Crystalline COP) <Catalytic Synthesis> (Synthesis of bis{3,3'-di(t-butyl)-5,5',6,6'-tetramethyl-2,2'-biphenoxy}phenylimidotungsten(VI)) 5.80 g of tungstenphenylimide tetrachloride diethyl ether complex (W(=NPh)Cl4(Et2O)) and 60 ml of diethyl ether were added to a glass reactor with a stirrer, and the mixture was cooled to -78°C. Then, 8.38 g of 3,3'-di(t-butyl)-5,5',6,6'-tetramethyl-2,2'-biphenoxylithium dissolved in 60 ml of diethyl ether was added. The mixture was gradually returned to room temperature and reacted for 20 hours. After the reaction, the diethyl ether was removed from the reaction mixture by distillation, and the mixture was dissolved in a toluene / hexane mixed solvent in a weight ratio of 1 / 3. The white precipitate was filtered off using Celite, and the solvent was completely removed from the solution by distillation to obtain a red solid in 94% yield. This was cooled to -30°C, allowed to stand, and recrystallized to obtain a red needle-shaped microcrystalline solid. The yield of the obtained solid was 8.96 g (76% yield). This solid was, 1 H-NMR, 13 ¹¹C-NMR and elemental analysis identified it as bis{3,3'-di(t-butyl)-5,5',6,6'-tetramethyl-2,2'-biphenoxy}phenylimidotungsten(VI).

[0301] <Polymerization> In a glass reactor equipped with a stirrer, 0.1112 g of bis{3,3'-di(t-butyl)-5,5',6,6'-tetramethyl-2,2'-biphenoxy}phenylimidotungsten(VI) obtained in the synthesis example and 8 ml of toluene were added and the mixture was cooled to -78°C. Then, 0.01452 g of n-butyllithium dissolved in 2 ml of hexane was added, the mixture was allowed to return to room temperature, and the reaction was carried out for 20 minutes. Next, 15.0 g of dicyclopentadiene, 54 g of cyclohexane, and 0.64 g of 1-hexene were added to the resulting reaction mixture, and the polymerization reaction was carried out at 80°C. A white precipitate rapidly formed after the start of the polymerization reaction. After reacting for 2 hours, a large amount of acetone was poured into the polymerization reaction solution to agglomerate the precipitate, and after filtering and washing, the mixture was dried under reduced pressure at 40°C for 24 hours. The yield of the resulting ring-opening polymer was 14.8 g, and the number-average molecular weight was 18,000. Next, 6.0 g of the obtained ring-opening polymer and 95 g of cyclohexane were added to an autoclave equipped with a stirrer. Then, 40.00314 g of RuHCl(CO)(PPh3) dispersed in 20 ml of cyclohexane was added, and the hydrogenation reaction was carried out at a hydrogen pressure of 4.0 MPa and 160°C for 12 hours. The hydrogenation reaction solution was poured into a large amount of acetone to completely precipitate the resulting ring-opening polymer hydride, and after filtration and washing, it was dried under reduced pressure at 40°C for 24 hours. The hydrogenation rate of the obtained ring-opening polymer hydride was 99% or more, and the racemo-dyad ratio was 5% or less. Furthermore, the melting point measured using the vacuum-dried ring-opening polymer hydride as a sample was 290°C. Then, the vacuum-dried ring-opening polymer hydride was heated at 300°C for 10 minutes to completely melt it, and then cooled to room temperature at 10°C / min to allow it to crystallize completely. The melting point measured using this sample was 289°C. The analysis was performed using the following methods (1) to (4). (1) Number average molecular weight of ring-opening polymers 1 Based on 1H-NMR measurements, the ratio of hydrogen atoms present at the polymer chain ends to the number of hydrogen atoms present in the rest of the polymer chain was determined, and the number-average molecular weight of the ring-opening polymer was calculated based on this ratio. (2) Hydrogenation rate in the hydrogenation reaction of ring-opening polymers 1 This was determined based on H-NMR measurements. (3) Melting point of crystalline ring-opening polymer hydrides Measurements were taken using a differential scanning calorimeter, with the temperature increased at 10°C / min. (4) Ratio of racemo-dyad of crystalline ring-opening polymer hydrides Using orthodichlorobenzene-d4 as the solvent, at 150°C 13 13C-NMR measurements were performed, and the determination was made based on the intensity ratio of the 43.35 ppm signal from the meso-dyad and the 43.43 ppm signal from the racemo-dyad.

[0302] Examples 1-4 The resin pellets shown in Table 1 were heated and melted at 220°C for 10 minutes using a heat press to form a shape of 10 mm × 500 mm × 2 mm, and then cooled to room temperature at 10°C / min to produce a resin sheet (component). The obtained resin sheets were used for chemical resistance testing and evaluation of changes in appearance. Load deflection temperature measurements and metal leaching tests were also performed. The results are shown in Table 1.

[0303] Example 5 The resin pellets shown in Table 1 were heated and melted at 280°C for 10 minutes using a heating press to form a shape of 10 mm × 500 mm × 2 mm. The resin sheets (components) were then cooled at 10°C / min to room temperature. Chemical resistance tests and evaluation of appearance changes were performed on the obtained resin sheets in the same manner as in Examples 1-4. Load deflection temperature measurements and metal leaching tests were also conducted. The results are shown in Table 1.

[0304] Example 6 The resin pellets shown in Table 1 were heated and melted at 230°C for 10 minutes using a heating press to form a shape of 10 mm × 500 mm × 2 mm. The resin sheets (components) were then cooled at 10°C / min to room temperature. Chemical resistance tests and evaluation of appearance changes were performed on the obtained resin sheets in the same manner as in Examples 1-4. Load deflection temperature measurements and metal leaching tests were also conducted. The results are shown in Table 1.

[0305] Example 7 The crystalline COP obtained in Synthesis Example 1 was heated and melted at 320°C for 10 minutes to form a 10mm × 500mm × 2mm shape, and then cooled to room temperature at 10°C / min to produce a resin sheet (component). Using the obtained resin sheet, chemical resistance tests, evaluation of appearance changes, measurement of load deflection temperature, and metal leaching tests were performed in the same manner as in Examples 1 to 4. The results are shown in Table 1.

[0306] Example 8 The resin pellets shown in Table 1 were heated and melted at 180°C for 10 minutes using a heating press to form a shape of 10 mm × 500 mm × 2 mm. The resin sheets (components) were then cooled at 10°C / min to room temperature. The obtained resin sheets were used for chemical resistance testing, evaluation of appearance changes, and measurement of load deflection temperature, similar to Examples 1-4. The results are shown in Table 1.

[0307] Comparative Examples 1 and 3 The resin pellets shown in Table 1 were heated and melted at 350°C for 10 minutes using a heat press to form a shape of 10 mm × 500 mm × 2 mm. Then, the temperature was lowered at 10°C / min to room temperature to produce a resin sheet (component). Chemical resistance tests and evaluation of appearance changes were performed on the obtained resin sheet in the same manner as in Examples 1 to 4. The results are shown in Table 1.

[0308] Comparative Example 2 The resin pellets shown in Table 1 were heated and melted at 300°C for 10 minutes using a heat press to form a shape of 10 mm × 500 mm × 2 mm. Then, the temperature was lowered at 10°C / min to room temperature to produce a resin sheet (component). Chemical resistance tests and evaluation of appearance changes were performed on the obtained resin sheet in the same manner as in Examples 1 to 4. The results are shown in Table 1.

[0309] [Table 1]

[0310] The components of the embodiment were suitable for use as components (parts) in semiconductor manufacturing equipment where chemicals are used.

Claims

1. A semiconductor manufacturing apparatus comprising a thermoplastic resin selected from the group consisting of polypropylene resin, amorphous cycloolefin resin, crystalline cycloolefin resin, and polymethylpentene resin, and equipped with a component that comes into contact with a corrosive substance.

2. The semiconductor manufacturing apparatus according to claim 1, wherein the thermoplastic resin is crystalline.

3. The semiconductor manufacturing apparatus according to claim 1 or 2, wherein the member is at least one selected from the group consisting of a container, piping, nozzle, tube, tank, fittings, valve, pump, spin chuck, O-ring, packing, gasket, washer, and sealing material.

4. The semiconductor manufacturing apparatus according to claim 1 or 2, wherein the pH of the corrosive substance is 6 or less or 8 or more.

5. The semiconductor manufacturing apparatus according to claim 1 or 2, wherein the oxidation-reduction potential (vsNHE) of the corrosive substance is -2.0 to 3.0 V.

6. The semiconductor manufacturing apparatus according to claim 1 or 2, wherein the corrosive substance is at least one selected from the group consisting of acidic substances, basic substances, oxidizing substances, organic solvents, and brine.

7. The semiconductor manufacturing apparatus according to claim 6, wherein the acidic substance is at least one selected from the group consisting of sulfuric acid, hydrofluoric acid, nitric acid, phosphoric acid, hydrochloric acid, a mixed acid of hydrofluoric acid and nitric acid, a mixed chemical solution of hydrogen peroxide and hydrochloric acid, and a mixed chemical solution of hydrogen peroxide and sulfuric acid.

8. The basic substance is TMAH([(CH ３ ) ４ N] ＋ [OH] － The semiconductor manufacturing apparatus according to claim 6, wherein the chemical is selected from the group consisting of sodium hydroxide aqueous solution, ammonia water, and a mixed chemical solution of hydrogen peroxide water and ammonia water.

9. The corrosive substance is sulfuric acid, hydrofluoric acid, nitric acid, phosphoric acid, hydrochloric acid, a mixed acid of hydrofluoric acid and nitric acid, a mixed chemical solution of hydrogen peroxide and hydrochloric acid, a mixed chemical solution of hydrogen peroxide and sulfuric acid, TMAH([(CH ３ ) ４ N] ＋ [OH] － The semiconductor manufacturing apparatus according to claim 1 or 2, wherein the liquid is at least one selected from the group consisting of sodium hydroxide aqueous solution, a mixed chemical solution of hydrogen peroxide and ammonia water, and isopropyl alcohol.

10. The semiconductor manufacturing-related apparatus according to claim 1 or 2, wherein a chemical is used within the apparatus.

11. The semiconductor manufacturing apparatus according to claim 1 or 2, wherein a test piece of the aforementioned member (size: 10 mm x 50 mm x 2 mm) is immersed in each of the following three chemical solutions for one week, and the relative value of the mass after immersion, with the mass before immersion set to 100, is 95 or more and 105 or less in each case. (Medicinal solution) 25% by mass TMAH ([(CH ３ ) ４ N] ＋ [OH] － (80℃) Mixed acid of hydrofluoric acid and nitric acid (a mixture of 49% hydrofluoric acid by mass and 69-71% nitric acid by mass in a volume ratio of 1:100) (20°C) SPM (a mixture of 98% sulfuric acid by mass and 30-36% hydrogen peroxide by mass in a volume ratio of 2:1) (80°C)

12. The semiconductor manufacturing apparatus according to claim 1 or 2, wherein a test piece of the aforementioned member (size: 10 mm x 50 mm x 2 mm) is immersed in each of the following 10 chemical solutions for one week, and the relative mass after immersion is calculated with the mass before immersion set to 100, and the average of the relative values ​​for the 10 chemical solutions is 95 or more and 105 or less, with a standard deviation of 20 or less. (Medicinal solution) 25% by mass TMAH ([(CH ３ ) ４ N] ＋ [OH] － (80℃) 98% by mass sulfuric acid (90°C) 100% by mass isopropyl alcohol (80°C) 49% by mass hydrofluoric acid (70°C) Mixed acid of hydrofluoric acid and nitric acid (a mixture of 49% hydrofluoric acid and 69-71% nitric acid in a volume ratio of 1:5) (20°C) Mixed acid of hydrofluoric acid and nitric acid (a mixture of 49% hydrofluoric acid by mass and 69-71% nitric acid by mass in a volume ratio of 1:100) (20°C) SPM (a mixture of 98% sulfuric acid by mass and 30-36% hydrogen peroxide by mass in a volume ratio of 2:1) (80°C) SC1 (a mixture of 25-28% by mass of aqueous ammonia, 30-36% by mass of aqueous hydrogen peroxide, and deionized water in a volume ratio of 1:1:5) (70°C) SC2 (a mixture of 35-37% hydrochloric acid, 30-36% hydrogen peroxide solution, and deionized water in a volume ratio of 1:1:4) (70°C) 85% by mass phosphoric acid (80°C)

13. The semiconductor manufacturing apparatus according to claim 1 or 2, wherein the member has a load deflection temperature of 50°C or higher at a load of 1.82 MPa.

14. The semiconductor manufacturing apparatus according to claim 1 or 2, wherein the amount of metal leaching of 16 elements (Li, Na, Mg, Al, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Ag, Cd, Pb) is 20 ppb or less when a test piece (size: 10 mm x 50 mm x 2 mm) of the aforementioned member is immersed in 3.6 mass% hydrochloric acid at 23°C for one week.

15. The semiconductor manufacturing-related apparatus according to claim 1 or 2, which is at least one selected from the group consisting of semiconductor manufacturing equipment and semiconductor manufacturing equipment-related apparatus.

16. The semiconductor manufacturing apparatus is at least one selected from the group consisting of a photolithography apparatus, a thin film formation / etching / cleaning / drying apparatus, an inspection / evaluation apparatus / manufacturing apparatus, a resist processing apparatus, an etching apparatus, a cleaning / drying apparatus, a CVD apparatus, a thin film formation apparatus, a CMP apparatus, a processing apparatus, an aging apparatus, and an inspection apparatus. The semiconductor manufacturing apparatus according to claim 15, wherein the semiconductor manufacturing apparatus is at least one selected from the group consisting of a pure water / chemical solution apparatus, a gas apparatus, a cleanroom apparatus, and a manufacturing apparatus.

17. The photolithography apparatus is at least one selected from the group consisting of a coating apparatus, a resist stripping apparatus, a developing apparatus (developer), and a discam apparatus. The thin film formation, etching, cleaning, and drying apparatus is at least one selected from the group consisting of a vacuum deposition apparatus, a cleaning apparatus, a drying apparatus, and a scrubbing cleaning apparatus. The aforementioned inspection and evaluation device / manufacturing device is a defect correction device, The resist processing apparatus is at least one selected from the group consisting of a coating apparatus, a developing apparatus, a resist stripping apparatus, and an ashing apparatus. The etching apparatus is at least one selected from the group consisting of a dry etching apparatus and a wet etching apparatus. The washing and drying apparatus is at least one selected from the group consisting of a wet washing apparatus, a scrubbing washing apparatus, and a drying apparatus. The CVD apparatus is at least one selected from the group consisting of high-pressure CVD apparatus, SACVD, reduced-pressure CVD, plasma CVD apparatus, metal CVD apparatus, and ALD apparatus. The thin film formation apparatus is at least one selected from the group consisting of a vacuum deposition apparatus, a silicon epitaxial growth apparatus, a compound semiconductor epitaxial apparatus (MOCVD apparatus, MBE apparatus), and a plating apparatus. The CMP apparatus is at least one selected from the group consisting of a CMP apparatus and a CMP cleaning apparatus. The aforementioned processing apparatus is a bump plating apparatus, The aging apparatus is at least one selected from the group consisting of an aging apparatus, a burn-in apparatus, an IC insertion apparatus, and an IC extraction apparatus. The inspection device is a life test device, The aforementioned pure water / chemical solution system is at least one selected from the group consisting of a chemical supply device, a slurry supply device, a chemical purification device, and a waste liquid treatment device. The gas apparatus is at least one selected from the group consisting of a gas generator, a gas purification device, a gas mixing device, a gas detection device, and an exhaust gas treatment device. The cleanroom apparatus is at least one selected from the group consisting of a thermal chamber and an environmental testing apparatus. The semiconductor manufacturing apparatus according to claim 16, wherein the manufacturing apparatus is at least one selected from the group consisting of a jig cleaning and drying apparatus, a flow rate control apparatus, a packaging apparatus, and liquid and gas measuring instruments.

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