Joined body for semiconductor manufacturing-related device, method for manufacturing joined body for semiconductor manufacturing-related device, and semiconductor manufacturing-related device

Abstract

The present disclosure provides a joined body for a semiconductor manufacturing-related device in which the joining in the joined body is strong, a method for manufacturing the joined body for a semiconductor manufacturing-related device, and a semiconductor manufacturing-related device using the joined body for a semiconductor manufacturing-related device. The present disclosure relates to a joined body for a semiconductor manufacturing-related device, the joined body comprising an olefin resin and having a tensile strength of 5 MPa or more.

Description

Assembly for semiconductor manufacturing equipment, method for manufacturing assembly for semiconductor manufacturing equipment, and semiconductor manufacturing equipment

[0001] This disclosure relates to a bond for semiconductor manufacturing equipment, a method for manufacturing a bond for semiconductor manufacturing equipment, and semiconductor manufacturing equipment.

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

[0003] Japanese Patent Application Publication No. 10-17729

[0004] This disclosure aims to provide a joint for semiconductor manufacturing equipment having a strong bond at the joint, a method for manufacturing the joint for semiconductor manufacturing equipment, and semiconductor manufacturing equipment using the joint for semiconductor manufacturing equipment.

[0005] (1) of this disclosure is a bonded body for semiconductor manufacturing equipment, comprising an olefin resin and having a tensile strength of 5 MPa or more.

[0006] Disclosure (2) is a bonded body for semiconductor manufacturing equipment according to Disclosure (1), wherein the tensile strength is 5 to 15 MPa.

[0007] Disclosure (3) is a semiconductor manufacturing equipment assembly according to Disclosure (1) or (2), wherein the olefin 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 bonded body for semiconductor manufacturing equipment in any combination of any of Disclosures (1) to (3), wherein the olefin resin is at least one selected from the group consisting of polyethylene resin, polypropylene resin, amorphous cycloolefin resin, and polymethylpentene resin.

[0009] Disclosure (5) is a bonded body for semiconductor manufacturing equipment in any combination of any of Disclosures (1) to (4) having a thickness of 1 to 40 mm.

[0010] Disclosure (6) is a semiconductor manufacturing equipment assembly in any combination of Disclosure (1) to (5) that comes into contact with corrosive substances.

[0011] The present disclosure (7) is a semiconductor manufacturing equipment assembly according to the present disclosure (6), wherein the corrosive substance is at least one selected from the group consisting of acidic substances, basic substances, oxidizing substances, organic solvents, and brine.

[0012] Disclosure (8) is a semiconductor manufacturing equipment-related bond in any combination of any of Disclosures (1) to (7), wherein the total metal content of 17 elements (Li, Na, Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Ba, Pb) when the bond is ashed is 200 ppm or less.

[0013] Disclosure (9) is a semiconductor manufacturing equipment-related bond, any combination of Disclosure (1) to (8), wherein the total amount of metal leaching of 16 elements (Li, Na, Mg, Al, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Ag, Cd, Pb) when the bond is immersed in 3.6 mass% hydrochloric acid at 23°C for one week is 65 ppb or less.

[0014] The present disclosure (10) is a semiconductor manufacturing equipment-related bond, which is any combination of the present disclosure (1) to (9) and the bond, wherein the surface roughness Sa of the bonded portion of the bond is 5 to 100 μm.

[0015] The present disclosure (11) is a semiconductor manufacturing equipment-related bond, which is any combination of the present disclosure (1) to (10) and the bond portion of the bond, wherein the surface roughness Sa of the bond is 20 to 30 μm.

[0016] The present disclosure (12) is a joint for semiconductor manufacturing-related equipment in any combination with any of the present disclosures (1) to (11), wherein the joint portion of the joint is joined by ultrasonic welding.

[0017] The present disclosure (13) is a joint for semiconductor manufacturing-related equipment in any combination with any of the present disclosures (1) to (11), wherein the joint portion of the joint is joined by hot plate welding.

[0018] The present disclosure (14) is a semiconductor manufacturing equipment assembly in any combination with any of the present disclosures (1) to (13), which is at least one semiconductor manufacturing equipment component selected from the group consisting of pipes, nozzles, tubes, fittings, tanks, housings and containers.

[0019] The present disclosure (15) is a method for manufacturing a bonded body for semiconductor manufacturing-related equipment, in any combination of the present disclosures (1) to (12) and (14), which includes a step of ultrasonically welding the objects to be joined under the conditions of an amplitude of 0.01 to 3 mm, a friction pressure of 0.05 to 10 MPa, and a pressurizing time of 0.2 to 10 seconds.

[0020] The present disclosure (16) is a manufacturing method according to the present disclosure (15), which includes a step of ultrasonically welding objects to be joined under the conditions of an amplitude of 0.03 to 0.05 mm, a friction pressure of 0.5 to 1 MPa, and a pressurizing time of 0.2 to 2 seconds.

[0021] (17) of this disclosure is a method for manufacturing a bonded body for semiconductor manufacturing-related equipment, which includes a step of welding the object to be joined to the hot plate using a hot plate with a surface temperature of 400 to 800°C, with a clearance of 0.1 to 2 mm between the object to be joined and the hot plate and a heating time of 0.1 to 5 seconds, in any combination with any of (1) to (11), (13), or (14) of this disclosure.

[0022] The present disclosure (18) is a manufacturing method according to the present disclosure (17), which includes a step of welding the objects to be joined to a hot plate using a hot plate with a surface temperature of 550 to 650°C, with a clearance of 0.5 to 0.8 mm between the objects to be joined and the hot plate, and a heating time of 2 to 3.5 seconds.

[0023] Disclosure (19) is a semiconductor manufacturing apparatus equipped with a semiconductor manufacturing apparatus assembly in any combination of Disclosure (1) to (14).

[0024] Disclosure (20) is a semiconductor manufacturing-related apparatus according to Disclosure (19), which is at least one selected from the group consisting of semiconductor manufacturing apparatus and semiconductor manufacturing apparatus-related apparatus.

[0025] The present disclosure (21) is a semiconductor manufacturing-related apparatus according to the present disclosure (20), wherein 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, and the semiconductor manufacturing-related 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-related apparatus.

[0026] The present disclosure (22) states that the photolithography process 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 / drying apparatus is at least one selected from the group consisting of a vacuum deposition apparatus, a cleaning apparatus, a drying apparatus, and a scrub cleaning apparatus; the inspection and evaluation apparatus / manufacturing apparatus is a defect correction apparatus; 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 cleaning / drying apparatus is at least one selected from the group consisting of a wet cleaning apparatus, a scrub cleaning apparatus, and a drying apparatus; and the CVD apparatus is at least one selected from the group consisting of a high-pressure CVD apparatus, SACVD, reduced-pressure CVD, plasma CVD apparatus, metal CVD apparatus, mist CVD apparatus, and ALD apparatus. The thin film forming 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 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 apparatus is a life testing apparatus; the pure water / chemical solution apparatus is at least one selected from the group consisting of a chemical supply apparatus, a slurry supply apparatus, a chemical purification apparatus, and a waste liquid treatment apparatus; the gas apparatus is at least one selected from the group consisting of a gas generator, a gas purification apparatus, a gas mixing apparatus, a gas detection apparatus, and an exhaust gas treatment apparatus; and the cleanroom apparatus is at least one selected from the group consisting of a thermal chamber and an environmental testing apparatus. The semiconductor manufacturing equipment described in (21) of this disclosure is at least one selected from the group consisting of a jig cleaning and drying device, a flow rate control device, a packaging device, and a liquid / gas measuring device.

[0027] According to this disclosure, it is possible to provide a joint for semiconductor manufacturing equipment having a strong bond at the joint portion, a method for manufacturing the joint for semiconductor manufacturing equipment, and a semiconductor manufacturing equipment using the joint for semiconductor manufacturing equipment.

[0028] The following provides a detailed explanation of this disclosure.

[0029] This disclosure relates to a joint for semiconductor manufacturing equipment (hereinafter also referred to as "the joint of this disclosure") that contains an olefin resin and has a tensile strength of 5 MPa or more. Because the joint of this disclosure has the above configuration, the joint is strong. For this reason, breakage and delamination are less likely to occur during use, and the joint can be maintained. The joint of this disclosure also has excellent corrosion resistance (particularly chemical resistance).

[0030] The composite material of this disclosure includes an olefin resin (polyolefin resin). The olefin resin preferably has a fluorine content of 1% by mass or less, more preferably 0.1% by mass or less, and even more preferably 0.01% by mass or less. The lower limit is not particularly limited and may be 0% by mass. The fluorine content of the olefin resin is determined by burning 10 mg of the resin sample by the oxygen flask combustion method, absorbing the decomposition gas in 20 ml of deionized water, and measuring the fluorine ion concentration in the absorption solution by the fluorine selective electrode method (fluorine ion meter, Model 901, Orion Corporation).

[0031] Examples of the olefin resins mentioned above include polyethylene resin, polypropylene resin, ethylene-propylene copolymer resin, amorphous cycloolefin resin, crystalline cycloolefin resin, polymethylpentene resin, amorphous polystyrene resin, crystalline polystyrene resin, and polybutylene resin, and one or more of these can be used. In particular, from the viewpoint of making the joints even stronger and 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 at least one selected from the group consisting of polyethylene resin, polypropylene resin, amorphous cycloolefin resin, and polymethylpentene resin is more preferred.

[0032] 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.

[0033] Examples of the above 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.

[0034] 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.

[0035] 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.

[0036] 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 is 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.

[0037] 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.

[0038] 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.

[0039] The above MFR is measured at 190°C under a 2.16 kg load in accordance with JIS K6922-2:1997.

[0040] The MFR of the above polyethylene resin can be adjusted by the ethylene polymerization temperature, the use of a chain transfer agent, or the like. For example, increasing the polymerization temperature of ethylene and an α-olefin decreases the molecular weight and consequently increases the MFR, while decreasing the polymerization temperature increases the molecular weight and consequently decreases the MFR. In the copolymerization reaction of ethylene and an α-olefin, increasing the amount of coexisting hydrogen (amount of chain transfer agent) decreases the molecular weight and consequently increases the MFR, while decreasing the amount of coexisting hydrogen (amount of chain transfer agent) increases the molecular weight and consequently decreases the MFR.

[0041] The polyethylene resin has a density of 0.900 to 0.980 g / cm ３ , which is preferable. More preferably, it is 0.910 g / cm ３ or more, still more preferably 0.920 g / cm ３ or more, even more preferably 0.930 g / cm ３ or more, particularly preferably 0.932 g / cm ３ or more, and more preferably 0.970 g / cm ３ or less, still more preferably 0.960 g / cm ３ or less, even more preferably 0.950 g / cm ３ or less, particularly preferably 0.948 g / cm ３ or less. The above density is measured in accordance with JIS K6922-1, 2:1997. The density can be adjusted, for example, by changing the type or amount of the α-olefin copolymerized with ethylene.

[0042] The polyethylene resin can be produced by a known method, and the production catalyst, process, and the like are not limited. Further, the raw material monomer may be derived from a petroleum raw material, may be derived from a biomass raw material, or may be derived from both of them.

[0043] 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.

[0044] Polymerization methods include high-pressure methods, solution methods, slurry methods, and gas-phase methods. The high-pressure method uses a radical source such as oxygen or peroxide, or a catalyst consisting of a metal complex, as an initiator, and polymerizes ethylene, comonomers, and the initiator by introducing them into a reaction vessel under high temperature and high pressure conditions. 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 melting point of the polymer. The slurry method is a polymerization method in which a hydrocarbon compound is used as the solvent, and the resulting polyethylene exists in the solvent as a slurry. Depending on the shape of the reaction vessel, it can be broadly divided into the autoclave method and the loop-pipe method. Preferably, 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 used as the solvent. The gas-phase method is a polymerization method in which ethylene and α-olefin as a comonomer and hydrogen as a chain transfer agent are fed in gaseous form from the bottom of a vertical reaction vessel, and a polymerization catalyst is introduced thereto.

[0045] The polyethylene resin described above may contain polar groups. Examples of polyethylene resins containing polar groups include polymers obtained by graft-modifying ethylene homopolymers and / or copolymers of ethylene and α-olefins with polar groups. Preferred α-olefins and their copolymerization ratios are as described above. The polar groups refer to electrically polar substituents, and are preferably carboxyl groups and / or carboxylic acid anhydride groups. Polyethylene resins containing polar groups can be produced by reacting ethylene homopolymers and / or copolymers of ethylene and α-olefins with a compound containing polar groups. Examples of compounds containing polar groups include α,β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, and itaconic acid, or their anhydrides, and 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.

[0046] The amount of polar groups contained in the polyethylene resin containing polar groups is 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).

[0047] Polyethylene resins containing polar groups can be produced by methods such as graft modification of polyethylene with polar group-containing monomers, and known methods can be used as appropriate. Specifically, known methods include a melt 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, etc., 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 melt method is more suitably selected in terms of production cost and environmental impact. The melt kneading equipment used to carry out graft modification is not limited, but single-screw extruders, twin-screw extruders, kneaders, Banbury mixers, Brabenders, and reciprocating kneaders (Buss Kneaders) are commonly used, and among these, single-screw extruders and twin-screw extruders are more suitably used in terms of productivity. Examples of reaction initiators used for graft modification include radical initiators that decompose by heating, etc., and generate radicals. Examples of radical initiators include organic peroxides, dihydroaromatic compounds, and dicumyl compounds. The graft modification temperature is appropriately selected considering 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.

[0048] 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.

[0049] 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.

[0050] The high-density polyethylene mentioned above has a density of 0.940 g / cm³. 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 / cm³. ３ Preferably, it is 0.965 g / cm³. ３ The following is more preferable: The density of polyethylene is measured in accordance with JIS K7112.

[0051] 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.

[0052] Molecular weight fractionation is performed by the following method: A glass bead-packed column (diameter: 21 mm, length: 60 cm) is used as the column, and the column temperature is set to 130°C. A solution of 1 g of sample dissolved in 30 mL of xylene is injected. Next, a xylene / 2-ethoxyethanol mixture in a 5 / 5 ratio is used as the developing solvent, and the distillate is removed. Then, xylene is used as the developing solvent, and the components remaining in the column are distilled off to obtain a polymer solution. Five times the amount of methanol is added to the obtained polymer solution to precipitate the polymer, and the solution is filtered and dried to recover components with a Mn of 100,000 or more.

[0053] The number of long-chain branchings is measured by the following method: Using a JNM-GSX400 nuclear magnetic resonance spectrometer manufactured by JEOL Ltd. １３The number of hexyl or greater branches is measured by 13C-NMR. The solvent is benzene-d6 / orthodichlorobenzene (volume ratio 30 / 70). The number of hexyl or greater 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-carbons (34.6 ppm) and β-carbons (27.3 ppm).

[0054] 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.

[0055] 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-norbornenic acid anhydride being particularly preferred.

[0056] 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.

[0057] 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 mixture is dissolved in a suitable solvent, a slurry method in which the mixture is suspended in a suitable solvent, or the so-called gas-phase graft method. The processing temperature is appropriately selected considering the degradation of the high-density polyethylene, the decomposition of the unsaturated carboxylic acid and its derivatives, and the decomposition temperature of the peroxide used. Taking the above-mentioned melt-kneading method as an example, the temperature is usually 190 to 350°C, and 200 to 300°C is particularly preferred.

[0058] 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 an epoxy compound or a polyfunctional compound containing an amino group or a hydroxyl group 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. The graft amount of at least one monomer selected from the group consisting of the above-mentioned unsaturated carboxylic acids and their derivatives is desirable to be as high as possible, but is generally in the range of 0.001 to 10% by mass.

[0059] The above ultra-high molecular weight polyethylene has a weight-average molecular weight of 1.0 × 10⁻⁶. ６ Preferably, it is 1.2 × 10 ６ It is more preferable that the above is true, and also 7.0 × 10 ７Preferably, 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.

[0060] 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.

[0061] 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 excellent 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.

[0062] 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.

[0063] 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.).

[0064] 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 that has 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 in 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.

[0065] The above-mentioned 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-mentioned polypropylene resin.

[0066] Other monomers copolymerized with propylene include α-olefins and non-conjugated dienes, which can be used individually or in combination of two or more.

[0067] 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.

[0068] The non-conjugated diene mentioned above is given by the following formula (A): CH ２ =CR １Ａ - (CH ２ ) ｎ -CR ２Ａ =CR ３Ａ R ４Ａ (In the formula, R １Ａ , R ２Ａ , R ３Ａ , and R ４Ａ Examples of compounds represented by ) are, where each is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is an integer from 1 to 20.

[0069] R １Ａ , R ２Ａ , R ３Ａ , and R ４Ａ The 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.

[0070] When the above-mentioned polypropylene resin is a copolymer, it may be either a random copolymer or a block copolymer. The content of propylene-derived skeletons in the random copolymer is usually 90 to 99 mol%, preferably 92 to 98 mol%. The content of propylene-derived skeletons in the block copolymer is usually 70 to 99 mol%, preferably 75 to 98 mol%.

[0071] The above-mentioned polypropylene resin is preferably a crystalline polypropylene resin.

[0072] 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.

[0073] The above polypropylene resin is suitable in terms of flexural modulus and heat resistance. １３ The 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.

[0074] Here, the isotactic pentad fraction (mmmm fraction) is the method described by A. Zambelli et al. in Macromolecules, Vol. 6, 925 (1973), i.e. １３This is the isotactic fraction of a pentad unit in a polypropylene molecular chain, measured by 13C-NMR (nuclear magnetic resonance), and represents the fraction of a propylene monomer unit in which five propylene units are isotactically linked.

[0075] １３ The assignment of peaks in the 1C-NMR spectrum is based on the description in Macromolecules, Vol. 8, 687 (1975). １３ ¹³C-NMR can be measured using a Fourier transform NMR [500 MHz (for hydrogen nucleus measurement)] instrument, with the signal detection limit improved to 0.001 by performing 20,000 integrated measurements at a frequency of 125 MHz.

[0076] The above polypropylene resin may have a long-chain branched structure. Having a long-chain branched structure improves 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 the degree of 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.

[0077] The above polypropylene resin has a weight-average molecular weight of 5.0 × 10 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 the polypropylene resin is measured by gel permeation chromatography (GPC, column temperature: 140°C, eluent: 1,2,4-trichlorobenzene) on a polystyrene basis.

[0078] The melt flow rate (MFR) of the above polypropylene resin is not particularly limited, but 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.

[0079] 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, more preferably 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.

[0080] 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.

[0081] The MFR of the above-mentioned 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] The amorphous cycloolefin resin and crystalline cycloolefin resin described above may be a homopolymer (COP) of cycloolefin, or a cycloolefin copolymer (COC) which is a copolymer of cycloolefin and an acyclic olefin such as ethylene.

[0086] 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 ５The following is more preferable: The molecular weight of the amorphous cycloolefin resin is measured by gel permeation chromatography (GPC, column temperature: 40°C, eluent: methylcyclohexane) on a polyisobutylene basis.

[0087] The glass transition temperature of the amorphous cycloolefin resin is typically 70°C or higher, preferably 80°C or higher, more preferably 90°C or higher, even more preferably 100°C or higher, even more preferably 120°C or higher, even more preferably 130°C or higher, and particularly preferably 150°C or higher. It is also typically 200°C or lower, preferably 180°C or lower, and more preferably 160°C or lower. The glass transition temperature can be determined using a DSC (Differential Scanning Calorimeter: DSC7000 manufactured by Hitachi High-Tech Science Corporation) by raising the temperature in the range of 30°C to 200°C at a rate of 10°C / min (first run) - cooling - raising the temperature (second run), and taking the midpoint of the endothermic curve in the second run.

[0088] 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, etc. These may have hydrocarbon groups or polar groups as substituents. Examples of 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, aryloxycarbonyl 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, etc. 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 above norbornene monomers may have 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 preferably 4.

[0089] 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; norbornene compounds with three rings, such as 5-cyclohexyl-2-norbornene, 5-cyclopentyl-2-norbornene, 5-cyclohexenyl-2-norbornene, and 5-phenyl-2-norbornene; and 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);

[0090] 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 having four rings, such as dodeca-4-ene; 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 ２，７ dodeca-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 having 5 rings, such as dodeca-4-ene;

[0091] dicyclopentadiene, methyldicyclopentadiene, dihydrodicyclopentadiene (tricyclo[5.2.1.0 ２，６ also called deca-8-ene.) dicyclopentadienes having 3 rings, such as the above;

[0092] 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 heptadeca-4-ene, and other norbornene-based monomers having 5 or more rings, other than norbornenes, tetracyclododecenes and dicyclopentadienes; and the like.

[0093] Examples of norbornene-based monomers containing a polar group include 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 ２，７ Examples 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-carbonitrile, 2-acetyl-5-norbornene, 7-oxa-2-norbornene, etc. The above norbornene monomers may be used individually or in combination of two or more.

[0094] 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.

[0095] 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.

[0096] The other cycloolefin monomers mentioned above are preferably cyclooctene, cycloheptene, and their derivatives, more preferably cyclooctene and its derivatives, and even more preferably cyclooctene.

[0097] 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.

[0098] 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.

[0099] 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.

[0100] Examples of the reinforcing materials mentioned above include glass fibers, glass cloth, paper substrates, and glass nonwoven fabrics.

[0101] 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.

[0102] Examples of the antioxidant include various antioxidants for plastics and rubbers such as hindered phenol-based, phosphorus-based, and amine-based antioxidants. These antioxidants may be used alone, but it is preferable to use two or more of them in combination.

[0103] Examples of the flame retardant 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. The flame retardant may be used alone, but it is preferable to use two or more of them in combination.

[0104] The crystalline cycloolefin resin has a number average molecular weight of 5.0×10 ３ or more, preferably 1.0×10 ４ or more, more preferably, and 1.0×10 ６ or less, preferably 5.0×10 ５ or less, more preferably. The molecular weight of the crystalline cycloolefin resin is １ calculated based on 1H-NMR measurement, on the basis of the ratio between the number of hydrogen atoms present at polymer chain ends and the number of hydrogen atoms present in polymer chains other than the ends.

[0105] Examples of the cycloolefin monomer used for the crystalline cycloolefin resin include those exemplified as cycloolefin monomers used for amorphous cycloolefin resins. The crystalline cycloolefin resin may be a hydrogenated crystalline norbornene-based ring-opened polymer or a hydrogenated crystalline dicyclopentadiene ring-opened polymer, and a hydrogenated crystalline dicyclopentadiene ring-opened polymer is preferable from the viewpoint of heat resistance.

[0106] The hydrogenated crystalline norbornene-based ring-opened polymer is represented by the following formula (2-1): having the repeating unit represented thereby.

[0107] Here, m is 1 or 2. R ａ , R ｂEach 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.

[0108] 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.

[0109] 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 dyads with respect to the repeating units of the norbornene monomer is preferably 20% or less, and more preferably 10% or less. The proportion of racemo dyads in a crystalline norbornene-based ring-opening polymer hydride is determined using orthodichlorobenzene-d4 as a solvent at 150°C. １３ This can be calculated by performing C-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.

[0110] 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.

[0111] Furthermore, the norbornene monomer described above can be used in combination with other cycloolefin monomers. However, from the viewpoint of providing particularly good heat resistance to 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.

[0112] The above-mentioned crystalline norbornene-based ring-opening polymer hydrides having isotactic regularity are, for example, obtained by dividing the above-mentioned norbornene-based monomer into the following formula: (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, R ２ ~R ９ These 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.

[0113] 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%.

[0114] 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 C-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 13C-NMR spectroscopy (of the non-backchain methine carbon atoms of the five-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.

[0115] Examples of norbornene monomers used in the above-mentioned crystalline norbornene-based ring-opening polymer hydrides having syndiotactic stereoregularity include those listed above.

[0116] 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.

[0117] 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: (In the formula, M １１ R represents an atom selected from the transition metal atoms of Group 6 of the periodic table.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 L 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. １２ , L １３ Each independently comprises a substituted or unsubstituted conjugated heterocyclic ring group having 5 to 15 ring members, each having at least one nitrogen atom, or O-R １３ It is a group represented by R １３ L is a group selected from substituted or unsubstituted C1-C12 alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, and substituted or unsubstituted C6-C30 aryl groups. １４ It can be produced by ring-opening polymerization using a polymerization catalyst that uses a Group 6 transition metal compound of the periodic table represented by (), and then hydrogenating the resulting norbornene-based ring-opening polymer.

[0118] The above crystalline dicyclopentadiene ring-opening polymer hydride is given by the following formula (2-2): It has repeating units represented by .

[0119] 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 has syndiotactic stereoregularity from the viewpoint of high melting point and processability, and it is preferable that the polymer 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) of more than 90%. 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%.

[0120] 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 １３ It can be calculated by analyzing the C-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), orthodichlorobenzene-d ４ / In a mixed solvent of trichlorobenzene [mixing ratio (by weight) 1 / 2] at 200°C １３ By performing C-NMR spectral 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.

[0121] The above crystalline dicyclopentadiene ring-opening polymer hydride is given by the following formula (3-2): It has repeating units derived from dicyclopentadiene, represented by [formula].

[0122] 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.

[0123] 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.

[0124] 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.

[0125] 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.

[0126] 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: (In the formula, W represents a tungsten atom, and 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 L 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. ２２ L 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. ２３ O-R ２３ R represents the alkoxy group shown, ２３ L represents a group selected from alkyl groups having 1 to 12 carbon atoms that may have substituents, and aryl groups having 6 to 30 carbon atoms that may have substituents. ２４ This can be produced by ring-opening polymerization using a polymerization catalyst containing a tungsten compound represented by (), which has at least two nitrogen atoms and a ring membership of 12 to 24, and the conjugated heterocyclic ligand may have substituents. The obtained dicyclopentadiene ring-opening polymer can be produced by hydrogenation.

[0127] The amorphous cycloolefin resin and the crystalline cycloolefin resin described above are also preferably cycloolefin copolymers (COCs).

[0128] 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.

[0129] The cycloolefin monomer in the above-described cycloolefin copolymer is not particularly limited as long as it does not hinder the purpose of this disclosure. Typically, norbornene, 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 preferably used as cycloolefin monomers. Among the cycloolefin monomers, norbornene, TCD, and dicyclopentadiene are particularly preferred, with norbornene being particularly preferred, in terms of a good balance of cost, polymerizability, and the physical properties of the resulting cycloolefin copolymer. The cycloolefin monomers can be used individually or in combination of two or more.

[0130] 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 the following formula (I): (In the formula, R ａ１ ~R ａ１２ These may be the same or different atoms or groups selected from the group consisting of hydrogen atoms, halogen atoms, and hydrocarbon groups. ａ９ and R ａ１０ , R ａ１１ and R ａ１２ These may integrate to form a divalent hydrocarbon group. 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 can be the same or different within each repeating unit. However, if n is 0, R ａ１ ~R ａ４ and R ａ９ ~R ａ１２ Examples of compounds represented by ) include those in which at least one of the atoms is not a hydrogen atom.

[0131] R ａ１ ~R ａ８Specific 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.

[0132] 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.

[0133] 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.

[0134] R ａ９ or R ａ１０ And, R ａ１１ or R ａ１２ When these elements bond to each other to form a ring, the formed ring may be monocyclic or polycyclic. The formed ring may be polycyclic with bridges. The formed ring may have double bonds. The formed ring may have substituents such as methyl groups.

[0135] 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-ene; tricyclo[4.4.0.1 ２，５ ]Undeca-3,7-diene or tricyclo[4.4.0.1 ２，５ ] Tricyclo[4.4.0.1] which is undeca-3,8-diene or a partially hydrogenated version thereof (or an adduct of cyclopentadiene and cyclohexene) ２，５ ]undeca-3-ene; 5-cyclopentyl-bicyclo[2.2.1]hepta-2-ene, 5-cyclohexyl-bicyclo[2.2.1]hepta-2-ene, 5-cyclohexenyl-bicyclo[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 1. ７，１０ ] 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 ２，５1. 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 1. ３，６ 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.

[0136] 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.

[0137] 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.

[0138] 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.

[0139] 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.

[0140] 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 usually 400 g / 10 min or less, preferably 200 g / 10 min or less, more preferably 100 g / 10 min or less. The above MFR is a value measured in accordance with ASTM 1238 (260°C, 2.16 kg).

[0141] 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.

[0142] The above-mentioned polymethylpentene resin (PMP) may be a homopolymer of 4-methyl-1-pentene, or a copolymer of 4-methyl-1-pentene and another monomer.

[0143] 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 ease of availability and copolymerization characteristics, preferred examples of the other monomers are 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, 4,4-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, and α-olefins other than methyl-1-pentene having 6 to 20 carbon atoms, such as 1-hexene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-octadecene are more preferred, and 1-hexene, 1-decene, 1-hexadecene, and 1-octadecene are even more preferred.

[0144] 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, and 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 C-NMR.

[0145] 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.

[0146] 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.

[0147] 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.

[0148] The melt flow rate (MFR) of the above-mentioned polymethylpentene resin, measured according to 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, it is usually 1 g / 10 min or more, preferably 8 g / 10 min or more, more preferably 15 g / 10 min or more, and also usually in the range of 200 g / 10 min or less, preferably 100 g / 10 min or less, and more preferably 30 g / 10 min or less.

[0149] The melting point of the above-mentioned polymethylpentene resin is not particularly limited, but is usually 200°C or higher, preferably 210°C or higher, and usually 240°C or lower.

[0150] 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 is also usually 100% or less.

[0151] The polymethylpentene resin described above preferably has a weight-average molecular weight of 30,000 or more, more preferably 100,000 or more, more preferably 1,000,000 or less, and more preferably 600,000 or less. The molecular weight of the polymethylpentene resin is measured by polystyrene equivalent using gel permeation chromatography (GPC, column temperature: 140°C, eluent: 1,2,4-trichlorobenzene).

[0152] 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.

[0153] Depending on its application, the polymethylpentene resin may optionally contain at least one polymer other than 4-methyl-1-pentene polymer and resin additives, to the extent that they do not impair the effects of the present disclosure.

[0154] As the other polymers mentioned above, a wide range of thermoplastic resins different from 4-methyl-1-pentene polymer can be used. The content of the other polymer is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, relative to the content of 4-methyl-1-pentene polymer.

[0155] The thermoplastic resin is not particularly limited as long as it is different from 4-methyl-1-pentene polymer, but includes: Thermoplastic polyolefin resins: for example, polyethylene such as low-density, medium-density, and high-density polyethylene, high-pressure low-density polyethylene, polypropylene such as isotactic polypropylene and syndiotactic polypropylene, 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, amorphous 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, amorphous polystyrene, crystalline polystyrene, ABS resin, AS resin, styrene 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 resins; polycarbonate; polyacetal; polyphenylene oxide; polyphenylene sulfide polyimide; polyarylate; polysulfone; polyethersulfone; rosin-based resins; terpene-based resins and petroleum resins;Copolymer rubbers include, 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, etc.

[0156] 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.

[0157] 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 elastomer, vinyl acetate copolymer, ethylene-methacrylate copolymer, ionomer, fluororesin-based resin, rosin-based resin, terpene-based resin, and petroleum resin. More preferably, in terms of improved heat resistance, improved low-temperature resistance, and flexibility, are polyethylene, isotactic polypropylene, syndiotactic polypropylene, amorphous cyclic olefin polymer, crystalline cyclic olefin polymer, cyclic olefin copolymer, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, 1-butene-α-olefin copolymer, vinyl acetate copolymer, styrene-based elastomer, rosin-based resin, terpene-based resin, and petroleum resin.

[0158] 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.

[0159] The joints 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 impact-improving elastomers.

[0160] Examples of the above-mentioned 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. It is preferable to use a primary antioxidant and a secondary antioxidant in combination, and a combination of a phenol-based antioxidant and a phosphorus-based antioxidant is particularly preferred.

[0161] 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 olefin resin. A content exceeding 5 parts by mass is undesirable because it causes bleeding.

[0162] 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 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less, per 100 parts by mass of the olefin resin, and may also be 0.01 parts by mass or more.

[0163] In the joint of the present disclosure, the content of the olefin resin is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more. It is also preferable that the content of the olefin resin is 100% by mass, i.e., that the joint consists only of olefin resin.

[0164] The joints of the present disclosure typically have a structure in which two or more parts are joined, and have at least one joint. The parts to be joined may be different members (e.g., a tube and a tank, a tube and a fitting) or different parts of the same member (e.g., a part of a tank and another part of the same tank, a tube and a tube).

[0165] The joint of this disclosure is preferably one in which parts containing an olefin resin are joined. Multiple parts containing an olefin resin may be joined, or parts containing an olefin resin may be joined to parts containing other materials, but it is preferable that multiple parts containing an olefin resin are joined, and more preferably that only multiple parts containing an olefin resin are joined. When multiple parts containing an olefin resin are joined, the olefin resin contained in each part may be the same or different, but it is preferable that they be of the same type of olefin resin. The parts containing the other materials may be parts that do not contain an olefin resin. Examples of the other materials include resins other than olefin resin, rubber, metals, ceramics, etc. The shape of the parts to be joined is not limited, and they just need to have a shape that allows them to be joined together.

[0166] The bonded body of this disclosure may be a laminate in which two or more layers are bonded (laminated). One preferred embodiment is that the bonded body of this disclosure is a laminate having a layer containing an olefin resin. In this case, there may be multiple layers containing the olefin resin, or a layer containing an olefin resin and a layer containing other materials, but it is preferable to have multiple layers containing the olefin resin, and it is more preferable to consist only of multiple layers containing the olefin resin. The layer containing the other material may be a layer that does not contain the olefin resin. Examples of the other material include those described above.

[0167] The joints of this disclosure have a tensile strength of 5 MPa or more, but it is preferable that they be 7 MPa or more, more preferably 9 MPa or more, even more preferably 10 MPa or more, and may also be 20 MPa or less, or 15 MPa or less, in that the joint is even stronger. The above tensile strength is determined by performing a tensile test at a tensile speed of 100 mm / min using a Shimadzu Corporation tensile testing machine "AG-3000kNX plus" and measuring the strength at the breaking point. In the case of joints obtained by ultrasonic welding, both ends of the sample (10 mm × 90 mm × 5 mm, 10 mm × 90 mm × 1.5 mm, 10 mm × 90 mm × 2 mm, or 10 mm × 90 mm × 3 mm) are clamped with a jig, and the strength at the breaking point is measured with a clamping distance of 40 mm. In the case of a joint obtained by hot plate welding, the sample (20 mm x 200 mm x 5 mm) is clamped at both ends with a jig, and the breaking strength is measured at a distance of 150 mm between the clamps. The above tensile strength may be the tensile strength of the joint. Joints with a tensile strength within the above range can be manufactured by the manufacturing method described later.

[0168] The bonded body (preferably a laminate) of the present disclosure is preferably 1 mm or more in thickness, more preferably 1.5 mm or more, even more preferably 2 mm or more, even more preferably 3 mm or more, even more preferably 4 mm or more, particularly preferably 5 mm or more, and also preferably 40 mm or less, more preferably 30 mm or less, even more preferably 25 mm or less, even more preferably 20 mm or less, even more preferably 15 mm or less, and particularly preferably 10 mm or less.

[0169] If the bonded body of this disclosure has a portion (layer) containing the other material, it is preferable that the thickness of the portion (layer) excluding the portion (layer) containing the other material, i.e., the thickness of the portion (layer) containing the olefin resin, is within the range described above.

[0170] In the joint of the present disclosure, the surface roughness Sa (arithmetic mean height) of the joint is preferably 5 μm or more, more preferably 8 μm or more, even more preferably 10 μm or more, even more preferably 15 μm or more, particularly preferably 20 μm or more, and also preferably 100 μm or less, more preferably 70 μm or less, even more preferably 50 μm or less, even more preferably 40 μm or less, and particularly preferably 30 μm or less, in order to further strengthen the joint of the joint. The above surface roughness Sa is measured using a shape analysis laser microscope VK-X1000 / 1100 manufactured by Keyence Corporation. Note that the above surface roughness Sa is the surface roughness of the joint surface of the part to be joined before joining.

[0171] The above surface roughness Sa can be adjusted by grinding, honing, electrical discharge machining, filing, polishing cloth and paper, lapping, sandblasting, buffing, tumbling, barrel polishing, chemical polishing, electrolytic polishing, etc.

[0172] The joints of the joints of the joints of this disclosure are preferably joined by ultrasonic welding, and also preferably by hot plate welding, as this results in a stronger joint. Ultrasonic welding and hot plate welding will be described later.

[0173] The joint of the present disclosure is preferably in contact with a corrosive substance. Part of the joint may be in contact with the corrosive substance, or the entire joint may be in contact with the corrosive substance. The joint of the present disclosure preferably contains an olefin resin in at least a portion of the part in contact with the corrosive substance, more preferably contains an olefin resin in all of the part in contact with the corrosive substance, and even more preferably consists solely of an olefin resin in all of the part in contact with the corrosive substance.

[0174] The corrosive substance mentioned above may be any substance that is corrosive, and may be a substance that is corrosive to rubber, resin, metal, etc. Furthermore, the corrosive substance may be a liquid, solid, or gas. In terms of exhibiting the effects of this disclosure more significantly, it is preferable that it be a fluid, and more preferably a liquid.

[0175] Furthermore, it is preferable that the corrosive substance is one that has been used in the treatment of objects to be treated with the corrosive substance. Examples of such corrosive substances include chemical solutions used in chemical treatment, which may be chemical solutions recovered after treatment, or they may be waste liquids.

[0176] 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.

[0177] Examples of the corrosive substances mentioned above include acidic substances, basic substances, oxidizing substances, organic solvents, and saltwater.

[0178] 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, examples 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). Among these, at least one selected from the group consisting of sulfuric acid, hydrofluoric acid, nitric acid, phosphoric acid, hydrochloric acid, mixed acids of hydrofluoric acid and nitric acid, mixed chemical solutions of hydrogen peroxide solution and hydrochloric acid, and mixed chemical solutions of hydrogen peroxide solution and sulfuric acid is preferred, and at least one selected from the group consisting of hydrofluoric acid, nitric acid, phosphoric acid, hydrochloric acid, mixed acids of hydrofluoric acid and nitric acid, mixed chemical solutions of hydrogen peroxide solution and hydrochloric acid, and mixed chemical solutions of hydrogen peroxide solution and sulfuric acid is more preferred.

[0179] Examples of the basic substance mentioned above include chemical solutions with a pH of 8 or higher, preferably 9 or higher, and more preferably 10 or higher. Specifically, TMAH([(CH ３ ) ４ N] ＋ [OH] － Examples include bases such as sodium hydroxide aqueous solution and ammonia; mixtures of these bases; and mixtures of these bases with other substances (such as hydrogen peroxide). In particular, TMAH ([(CH ３ ) ４ N] ＋ [OH] － Preferably, at least one selected from the group consisting of ), ammonia water, and a mixed chemical solution of hydrogen peroxide water and ammonia water.

[0180] 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([(CH ３ ) ４ N] ＋ [OH] － Examples include basic substances such as sodium hydroxide aqueous solution, ammonia water, hydroxylamine, hydrazine, hydrogen water, and sodium sulfite; and mixtures of these basic substances with other substances. In particular, TMAH ([(CH ３ ) ４ N] ＋ [OH] － Preferably, at least one selected from the group consisting of ), ammonia water, and a mixed chemical solution of hydrogen peroxide water and ammonia water.

[0181] Examples of the above-mentioned oxidizing substances 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, examples include sulfuric acid, nitric acid, hydrochloric acid, hydrogen peroxide; and mixtures of these oxidizing substances with other substances (such as hydrofluoric acid). Among these, at least one selected from the group consisting of sulfuric acid, nitric acid, hydrochloric acid, hydrogen peroxide, 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 nitric 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.

[0182] Examples of the above 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.

[0183] 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.

[0184] 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, 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, aqueous sodium hydroxide solution, aqueous ammonia, a 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, 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, a mixed chemical solution of hydrogen peroxide and aqueous ammonia, and isopropyl alcohol is preferred. Even more preferably, at least one selected from the group consisting of hydrofluoric acid, hydrochloric acid, a mixed acid of hydrofluoric acid and nitric acid, a mixed chemical solution of hydrogen peroxide and sulfuric acid, and TMAH is preferred.

[0185] The joint of this disclosure may have only a portion (layer) containing an olefin resin, or it may have a portion (layer) containing an olefin resin and a portion (layer) other than an olefin resin. From the viewpoint of ensuring corrosion resistance, it is preferable that at least a portion of the surface that comes into contact with corrosive substances is composed of a portion (layer) containing an olefin resin, and it is more preferable that the entire surface that comes into contact with corrosive substances is composed of a portion (layer) containing an olefin resin.

[0186] The joint of the present disclosure is preferably at least one selected from the group consisting of pipes, nozzles, tubes, fittings, tanks, housings and containers, more preferably at least one selected from the group consisting of pipes, tubes and fittings, and even more preferably at least one selected from the group consisting of tubes and fittings, given the requirement for strength of the joint.

[0187] The piping is not particularly limited, but examples include robust pipe types, flexible hoses that can be incorporated according to the installation space, and bellows pipes that can be bent despite their large diameter. Furthermore, the inside of the piping is made of a material that is clean (less contamination of the chemical solution by extracted ions) and chemical resistant, and may be polished to a high degree that does not generate dust and does not disturb the liquid flow or gas flow. Depending on the chemical solution to be flowed, such as organic solvents, antistatic properties may be required to prevent static electricity buildup, and conductive fillers (carbon black, carbon nanotubes, etc.) may be incorporated to provide antistatic properties within a range that does not worsen cleanliness. The inner diameter of the piping is preferably 2 mm or more, more preferably 5 mm or more, and preferably 1000 mm or less, more preferably 500 mm or less. The length is preferably 1 m or more, more preferably 2 m or more, and preferably 100 m or less, more preferably 50 m or less. The burst pressure of the piping at 23°C is preferably 0.2 MPa or more, more preferably 1.0 MPa or more, and preferably 15 MPa or less, more preferably 12 MPa or less. The flow velocity of the corrosive substance (preferably a fluid, more preferably a liquid) circulating in the piping is preferably 0.1 m / min or more, more preferably 1 m / min or more, and also preferably 500 m / min or less, more preferably 100 m / min or less.

[0188] 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.

[0189] The tube is not particularly limited, but a material having stress crack resistance, chemical resistance, excellent mechanical strength, and cleanliness (less contamination of the chemical solution by extracted ions) is used. 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. The inner diameter of the tube is preferably 1 mm or more, more preferably 2 mm or more, and preferably 400 mm or less, more preferably 40 mm or less. The length is preferably 1 m or more, more preferably 10 m or more, and preferably 500 m or less, more preferably 200 m or less. The 23°C burst pressure of the tube is preferably 0.2 MPa or more, more preferably 1 MPa or more, and preferably 15 MPa or less, more preferably 12 MPa or less. The flow velocity of the corrosive substance (preferably a fluid, more preferably a liquid) circulating through the tube is preferably 0.1 m / min or more, more preferably 1 m / min or more, and also preferably 500 m / min or less, more preferably 100 m / min or less.

[0190] The fittings 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 Φ3.2 mm to 40 mm.

[0191] While there are no particular limitations on the housing, liquid-repellent properties are sometimes required to suppress the adhesion of splashed chemicals during rotary dispensing.

[0192] The tanks and containers are not particularly limited, but they may be subjected to precision cleaning (water washing, acetic acid immersion, wiping, pure water washing, etc.) to remove dirt and residue. Packaging after cleaning may be carried out in a cleanroom or clean booth environment.

[0193] The assemblies of this disclosure are used in semiconductor manufacturing equipment. In this specification, semiconductor manufacturing equipment means semiconductor manufacturing equipment and related equipment. Related equipment for semiconductor manufacturing equipment includes equipment used in semiconductor manufacturing but not mounted on the semiconductor manufacturing equipment.

[0194] The above semiconductor manufacturing-related equipment includes photolithography equipment (coating equipment, resist stripping equipment, developing equipment (developer), baking equipment, discam equipment), thin film formation / etching / cleaning and drying equipment (vacuum deposition equipment, sputtering equipment, CVD equipment, cleaning equipment, etching equipment, drying equipment, scrub cleaning equipment), inspection and evaluation equipment and 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 (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 deposition equipment, CVD equipment (high-pressure CVD equipment, SACVD, reduced-pressure CVD, plasma CVD equipment, metal CVD equipment, mist CVD equipment, ALD equipment), sputtering equipment, other thin film deposition equipment (vacuum deposition equipment, silicon epitaxial growth equipment, compound semiconductor epitaxial growth equipment (MO) CVD 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, tape application machine for back grinder, back grinder, tape peeling machine for back grinder), dicing equipment (dicing equipment, wafer mounting equipment), bonding equipment (die bonding equipment, hybrid bonding equipment, wire bonding equipment, inner lead bonding equipment, outer lead bonding equipment, f Lip-tip bonding equipment, packaging equipment (molding equipment, deburring equipment, soldering equipment), other testing equipment (electron beam testing equipment, laser beam testing equipment), probing equipment (probers), handlers, aging equipment (aging equipment, burn-in equipment, IC insertion equipment, IC extraction equipment), other inspection equipment (cold and heat testing equipment, temperature and humidity testing equipment, pressure cooker equipment, laser processing systems, various life testing equipment), various transport equipment (in-process wafer transport equipment, inter-process wafer transport equipment, stockers),Examples include pure water and chemical solution equipment (pure water production equipment, ultrafiltration equipment, reverse osmosis equipment, sterilization equipment, chemical supply equipment, slurry supply equipment, chemical purification equipment, wastewater treatment equipment), various gas equipment (gas generators, gas purification equipment, gas mixing equipment, gas detection equipment, exhaust gas treatment equipment), 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 equipment, flow control equipment, various taping equipment, various packaging equipment, measuring instruments for liquids and various gases), etc.

[0195] As described above, the bonded body of this disclosure can be suitably used as a component for semiconductor manufacturing equipment (semiconductor manufacturing equipment and related equipment), and due to its excellent chemical resistance, it is particularly suitable as a component constituting semiconductor manufacturing equipment in which chemicals are used, and especially as a component that comes into contact with chemicals.

[0196] Semiconductor manufacturing equipment that uses corrosive substances within the apparatus is not particularly limited, but from the perspective of taking advantage of 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 and 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), cleaning and drying equipment ( Preferred equipment includes wet cleaning equipment, scrub cleaning equipment, drying equipment), CVD equipment (high-pressure CVD equipment, SACVD, reduced-pressure CVD, plasma CVD equipment, metal CVD equipment, mist 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, CMP cleaning equipment), 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). 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 systems), and other manufacturing-related equipment (various jig cleaning and drying systems, flow control equipment, various packaging systems, measuring instruments for liquids and various gases).

[0197] Semiconductor manufacturing equipment that uses corrosive substances within the apparatus is not particularly limited, but from the perspective of taking advantage of the high tensile strength properties, photolithography equipment (coating equipment, resist stripping equipment, developing equipment (developer), discam equipment), thin film formation / etching / cleaning and drying equipment (cleaning equipment, etching equipment, drying equipment, scrub cleaning equipment), resist processing equipment (coating equipment, developing equipment, resist stripping equipment), etching equipment (dry etching equipment, wet etching equipment), cleaning and drying equipment (wet cleaning equipment, scrub cleaning equipment, drying equipment), and other thin film formation equipment (silicon epitaxial growth equipment, compound semiconductor epitaxial equipment (MOCVD equipment, MBE equipment)) are also available. Examples include plating equipment, inspection and evaluation equipment (Auger electron spectrometer), CMP equipment (CMP equipment, CMP cleaning equipment), other processing equipment (bump plating equipment), bonding equipment (hybrid bonding equipment, wire bonding equipment, deburring equipment, soldering equipment), pure water and chemical equipment (pure water production equipment, ultrafiltration equipment, reverse osmosis equipment, sterilization equipment, chemical supply equipment, slurry supply equipment, chemical purification equipment, wastewater treatment equipment), various gas equipment (gas generators, gas purification equipment, gas mixing equipment, gas detection equipment, exhaust gas treatment equipment), cleanroom equipment (environmental testing equipment, air showers), and other manufacturing-related equipment (various jig cleaning and drying equipment, measuring instruments for liquids and various gases).

[0198] 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.

[0199] Specifically, the above-mentioned chemical is TMAH([(CH ３ ) ４ N] ＋ [OH] － ), sodium hydroxide aqueous solution, sulfuric acid, isopropyl alcohol, hydrofluoric acid, hydrofluoric acid and nitric acid mixture, SPM (Sulfuric Acid Hydrogen Peroxide Mixture), SC1 (NH ４ OH, H ２ O ２ and H ２ (O mixture), SC2 (HCl, H ２ O ２ and H２ Examples include at least one selected from the group consisting of a mixture of O, 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, SPM, and hydrochloric acid are more preferred.

[0200] 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 and halogenated 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.

[0201] Examples of silicon-based gases include monosilane, dichlorosilane, trichloride silane, silicon tetrachloride, silicon tetrafluoride, and disilane. Examples of arsenic-based gases include arsine, arsenic(III) fluoride, arsenic(V) fluoride, arsenic(III) chloride, and arsenic(V) chloride. Examples of phosphorus-based gases include phosphine, phosphorus(III) fluoride, phosphorus(V) fluoride, phosphorus(III) chloride, phosphorus(V) chloride, and phosphorus oxychloride. Examples of boron-based gases include diborane, boron trifluoride, boron trichloride, and boron tribromide. Examples of metal hydride gases include hydrogen selenide, monogermane, hydrogen telluride, stivin, and tin hydride. Examples of 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 halogenated 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 above-mentioned nitrogen oxide gases include nitric oxide, nitrogen dioxide, and dinitrogen monoxide. Among these, ammonia gas, nitrogen trifluoride, dinitrogen monoxide, monosilane, and cyclobutane octafluoride are preferred, and ammonia gas, nitrogen trifluoride, and dinitrogen monoxide are more preferred.

[0202] The composite material of the present disclosure preferably has a total metal content of 17 elements (Li, Na, Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Ba, Pb) of 200 ppm or less when the composite material is ashed. The total metal content is preferably 195 ppm or less, more preferably 190 ppm or less, even more preferably 180 ppm or less, even more preferably 170 ppm or less, even more preferably 150 ppm or less, even more preferably 100 ppm or less, even more preferably 70 ppm or less, and may also be 1 ppm or more, 2 ppm or more, 3 ppm or more, or 10 ppm or more. The metal content can be determined by the method described in the examples.

[0203] The joint of the present disclosure is preferably such that the standard deviation of the relative mass after immersion is calculated by immersing the joint in each of the 10 chemical solutions (1) to (10) described later for one week, with the mass before immersion set to 100, is 1.5 or less. Members that satisfy this requirement have excellent corrosion resistance. The standard deviation of the above relative value is more preferably 1.1 or less, even more preferably 1.0 or less, even more preferably 0.9 or less, and may be 0 or more, or 0.4 or more. Ideally (most preferably) it is 0.

[0204] The chemical solution used for immersing the above test specimens is as follows: (1) 25% by mass TMAH ([(CH ３ ) ４ N] ＋ [OH] －(1) 98% by mass sulfuric acid (90°C) (2) 100% by mass isopropyl alcohol (80°C) (4) 49% by mass hydrofluoric acid (70°C) (5) Mixed acid of hydrofluoric acid and nitric acid (a mixture of 49% by mass hydrofluoric acid and 69-71% by mass nitric acid in a volume ratio of 1:5) (20°C) (6) Mixed acid of hydrofluoric acid and nitric acid (a mixture of 49% by mass hydrofluoric acid and 69-71% by mass nitric acid in a volume ratio of 1:100) (20°C) (7) SPM (a mixture of 98% by mass sulfuric acid and 30-36% by mass hydrogen peroxide in a volume ratio of 2:1) (80°C) (8) SC1 (a mixture of 25-28% by mass ammonia water, 30-36% by mass hydrogen peroxide, and deionized water in a volume ratio of 1:1:5) (70°C) (9) SC2 (a mixture of 35-37% by mass hydrochloric acid, 30-36% by mass hydrogen peroxide solution, and deionized water in a volume ratio of 1:1:4) (70°C) (10) 85% by mass phosphoric acid (80°C)

[0205] The bonded body of the present disclosure is preferably such that the total amount of metals leached from 16 elements (Li, Na, Mg, Al, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Ag, Cd, Pb) when the bonded body is immersed in 3.6% by mass hydrochloric acid at 23°C for one week is 65 ppb or less. A member that satisfies this requirement has excellent cleanliness. The total amount of metals leached is preferably 50 ppb or less, more preferably 45 ppb or less, even more preferably 30 ppb or less, even more preferably 20 ppb or less, and may be 0.5 ppb or more, 1 ppb or more, 3 ppb or more, 5 ppb or more, or 15 ppb or more. The amount of metals leached can be determined by the method described in the examples.

[0206] The composite material of this disclosure has a total organic carbon (TOC) elution amount of 40,000 μg / m³ leached from its surface into ultrapure water. ２ Preferably, it is 20,000 μg / m³ ２ It is more preferable that the following conditions are met: 10,000 μg / m³ ２ It is even more preferable that the following conditions apply: 5000 μg / m ２ It is even more preferable that the following conditions are met, and also 100 μg / m³ ２ It may be greater than or equal to 1000 μg / m². ２The above amounts may also be used. The amount of total organic carbon (TOC) eluted is determined in accordance with SEMI F57 "Specifications for polymer materials and components used in ultrapure water and chemical supply systems," by placing the component in a PFA container, fully immersing it in ultrapure water, and storing it at 85±3°C for 7 days (168 hours). The eluate is then measured for TOC concentration using a TOC meter.

[0207] The number of particles per 1 mL of ultrapure water released from the member of this disclosure is preferably within the following ranges for each particle size: For particles with a diameter of 0.5 μm or more, the number of particles is preferably 10 or less, more preferably 7 or less, even more preferably 5 or less, even more preferably 3 or less, and even more preferably 1 or less. For particles with a diameter of 0.3 μm or more, the number of particles is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, even more preferably 10 or less, and even more preferably 5 or less. For particles with a diameter of 0.2 μm or more, the number of particles is preferably 70 or less, more preferably 50 or less, even more preferably 30 or less, even more preferably 20 or less, and even more preferably 10 or less. For particles with a diameter of 0.1 μm or more, the number of particles is preferably 500 or less, more preferably 300 or less, even more preferably 200 or less, even more preferably 100 or less, and even more preferably 50 or less. It may also be 0 or 1 or more. The above particle count is determined by completely immersing the material in ultrapure water (resistivity: ≥ 18.0 MΩ·cm), storing it for 24 hours, and then analyzing the immersion solution using a particle counter.

[0208] The joints of this disclosure can be suitably used not only for semiconductor manufacturing equipment applications but also for medical applications, for example, the following: Piping materials such as medical infusion tubes, blood collection tubes, drain tubes, catheters, catheter connectors, stents, pipes, fittings, tube connectors, valves, and filters; liquid, powder, or solid drug containers such as packaging packages, 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 testing, blood collection tubes, test cells, and specimen containers; etc. Among these, the joints are particularly suitable for medical infusion tubes, blood collection tubes, drain tubes, catheters, pipes, fittings, tube connectors, valves, bottles, bottle caps, vials, ampoules, pre-filled syringes, infusion bags, urine collection bags, test tubes for blood testing, blood collection tubes, test cells, and specimen containers, where the strength of the joint is required.

[0209] The joints of this disclosure can be suitably manufactured, for example, by the following manufacturing methods. This disclosure also relates to these manufacturing methods. A method for manufacturing joints for semiconductor manufacturing equipment (hereinafter also referred to as manufacturing method (1) of this disclosure) includes a step of ultrasonically welding the objects to be joined under the conditions of an amplitude of 0.01 to 3 mm, a friction pressure of 0.05 to 10 MPa, and a pressurizing time of 0.2 to 10 seconds. A method for manufacturing joints for semiconductor manufacturing equipment (hereinafter also referred to as manufacturing method (2) of this disclosure) includes a step of using a hot plate with a surface temperature of 400 to 800°C, welding the objects to be joined to the hot plate under the conditions of a clearance of 0.1 to 2 mm between the objects to be joined and the hot plate, and a heating time of 0.1 to 5 seconds. According to these manufacturing methods, a joint with a strong bond at the joint can be obtained under relatively mild conditions. Furthermore, even thick members can be strongly joined.

[0210] In the manufacturing method (1) of this disclosure, the objects to be joined (the parts to be joined in order to form the desired joint) are ultrasonically welded under specific conditions. The ultrasonic welding can be performed using a known ultrasonic welding machine.

[0211] The amplitude of ultrasonic welding in the manufacturing method (1) of the present disclosure is 0.01 to 3 mm, but it is preferably 0.02 mm or more, more preferably 0.03 mm or more, preferably 1 mm or less, more preferably 0.5 mm or less, even more preferably 0.1 mm or less, even more preferably 0.08 mm or less, and particularly preferably 0.05 mm or less, in terms of making the joint of the joint even stronger.

[0212] The friction pressure in ultrasonic welding of the manufacturing method (1) of the present disclosure is 0.05 to 10 MPa, but it is preferably 0.1 MPa or more, more preferably 0.3 MPa or more, even more preferably 0.5 MPa or more, and also preferably 5 MPa or less, more preferably 3 MPa or less, and even more preferably 1 MPa or less, in that the joint of the joint becomes even stronger.

[0213] The pressurizing time in ultrasonic welding of the manufacturing method (1) of the present disclosure is 0.2 to 10 seconds, but it is preferably 0.3 seconds or more, more preferably 0.4 seconds or more, even more preferably 0.5 seconds or more, and also preferably 5 seconds or less, more preferably 3 seconds or less, even more preferably 2 seconds or less, and even more preferably 1 second or less.

[0214] In the ultrasonic welding method (1) of the present disclosure, it is preferable to perform the welding with a surface roughness Sa (arithmetic mean height) of 5 to 100 μm on the joining surface of the objects to be joined, in that the joint becomes even stronger. The surface roughness Sa is more preferably 8 μm or more, even more preferably 10 μm or more, even more preferably 15 μm or more, particularly preferably 20 μm or more, and also preferably 100 μm or less, more preferably 70 μm or less, even more preferably 50 μm or less, even more preferably 40 μm or less, and particularly preferably 30 μm or less.

[0215] In the manufacturing method (2) of this disclosure, the objects to be joined (the parts to be joined in order to form the desired joint) are hot plate welded under specific conditions. The hot plate welding can be performed using a known hot plate welding machine.

[0216] In the hot plate welding of the manufacturing method (2) of the present disclosure, the surface temperature of the hot plate is 400 to 800°C, but it is preferable that it be 450°C or higher, more preferably 500°C or higher, even more preferably 550°C or higher, and also preferable that it be 750°C or lower, more preferably 700°C or lower, and even more preferably 650°C or lower, in order to make the joint of the joint even stronger.

[0217] In the hot plate welding of the manufacturing method (2) of the present disclosure, the clearance between the objects to be joined and the hot plate is 0.1 to 2 mm, but it is preferable that it be 0.2 mm or more, more preferably 0.3 mm or more, even more preferably 0.5 mm or more, and also preferable that it be 1.5 mm or less, more preferably 1 mm or less, and even more preferably 0.8 mm or less, in order to make the joint of the joint even stronger.

[0218] In the hot plate welding of the manufacturing method (2) of the present disclosure, the heating time is 0.1 to 5 seconds, but it is preferable to be 0.5 seconds or more, more preferably 1 second or more, even more preferably 1.5 seconds or more, even more preferably 2 seconds or more, and also preferable to be 4.5 seconds or less, more preferably 4 seconds or less, and even more preferably 3.5 seconds or less, in that the joint of the joint becomes even stronger.

[0219] The bonded body obtained by the manufacturing method of this disclosure may be subjected to precision cleaning (water washing, acetic acid immersion, wiping cleaning, pure water washing, etc.) to reduce the amount of particles and metal elution and to remove dirt and residue. The packaged body after cleaning may be carried out in a cleanroom or clean booth environment.

[0220] This disclosure also relates to semiconductor manufacturing equipment to which the bonded assembly of this disclosure described above is attached. The use of the bonded assembly of this disclosure can provide the equipment with excellent strength and corrosion resistance.

[0221] The semiconductor manufacturing equipment described herein is preferably at least one selected from the group consisting of semiconductor manufacturing equipment and related equipment for semiconductor manufacturing equipment. Examples of semiconductor manufacturing equipment and related equipment for semiconductor manufacturing equipment include those described above.

[0222] Among those described above, it is preferable that the semiconductor manufacturing apparatus is at least one selected from the group consisting of photolithography apparatus, thin film formation / etching / cleaning and drying apparatus, inspection and evaluation apparatus / manufacturing apparatus, resist processing apparatus, etching apparatus, cleaning and drying apparatus, CVD apparatus, thin film formation apparatus, CMP apparatus, processing apparatus, aging apparatus, and inspection apparatus, and that the semiconductor manufacturing apparatus-related apparatus is at least one selected from the group consisting of pure water / chemical solution apparatus, gas apparatus, cleanroom apparatus, and manufacturing-related apparatus.

[0223] Furthermore, the above photolithography process 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 thin film formation / etching / cleaning / drying apparatus is at least one selected from the group consisting of a vacuum deposition apparatus, a cleaning apparatus, a drying apparatus, and a scrub cleaning apparatus; the above inspection and evaluation apparatus / manufacturing apparatus is a defect correction apparatus; the above 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 above etching apparatus is at least one selected from the group consisting of a dry etching apparatus and a wet etching apparatus; the above cleaning / drying apparatus is at least one selected from the group consisting of a wet cleaning apparatus, a scrub cleaning apparatus, and a drying apparatus; the above CVD apparatus is at least one selected from the group consisting of a high-pressure CVD apparatus, SACVD, reduced-pressure CVD, plasma CVD apparatus, metal CVD apparatus, mist 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 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 apparatus is a life testing apparatus; the pure water / chemical solution apparatus is at least one selected from the group consisting of a chemical supply apparatus, a slurry supply apparatus, a chemical purification apparatus, and a waste liquid treatment apparatus; the gas apparatus is at least one selected from the group consisting of a gas generator, a gas purification apparatus, a gas mixing apparatus, a gas detection apparatus, and an exhaust gas treatment apparatus; and the cleanroom apparatus is at least one selected from the group consisting of a thermal chamber and an environmental testing apparatus. It is also preferable that the above-mentioned manufacturing-related equipment is 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.

[0224] 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.

[0225] The present disclosure will now be further described with reference to examples, but the present disclosure is not limited to these examples.

[0226] Various physical properties were measured using the following method.

[0227] <Surface Roughness Sa> Surface roughness was measured by observing the surface using a "Shape Analysis Laser Microscope VK-X1000 / 1100" manufactured by Keyence Corporation.

[0228] <Tensile Strength> Tensile tests were performed at a tensile speed of 100 mm / min using a Shimadzu Corporation AG-3000kNX plus tensile testing machine, and the breaking point strength was measured and defined as the tensile strength. In the case of joints obtained by ultrasonic welding, the breaking point strength was measured by clamping both ends of the sample (10 mm × 90 mm × 5 mm (Examples 1-3, Comparative Examples 1 and 2), 10 mm × 90 mm × 1.5 mm (Examples 8, 11, Comparative Example 6), 10 mm × 90 mm × 2 mm (Example 9, Comparative Example 7), 10 mm × 90 mm × 3 mm (Example 10, Comparative Example 8)) with a jig, and the breaking point strength was measured with a clamping distance of 40 mm. In the case of joints obtained by hot plate welding, the breaking point strength was measured by clamping both ends of the sample (20 mm × 200 mm × 5 mm) with a jig, and the breaking point strength was measured with a clamping distance of 150 mm.

[0229] <Welding Evaluation> Based on tensile strength, the following criteria were used for evaluation: ○: Tensile strength of 5 MPa or more △: Tensile strength of 0.1 MPa or more and less than 5 MPa ×: Tensile strength less than 0.1 MPa, or no welding occurred

[0230] <Chemical Resistance (Corrosion Resistance) Test> The test specimens were dried at 60°C for 2 hours. After drying, the mass of the test specimens was measured under room temperature (20°C) conditions before immersion. The measured test specimens were then completely immersed in each of the chemical solutions (1) to (10) below and held for 1 week (168 hours). After holding, the test specimens were washed with pure water, the surface water droplets were wiped off, and they were dried at 60°C for 12 hours. The mass of the test specimens after immersion was 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. In addition, the standard deviation of the post-immersion mass (relative value) for the 10 types (1) to (10) was determined. (Chemical Solutions) (1) 25% by mass TMAH ([(CH ３ ) ４ N] ＋ [OH] － (2) 98% by mass sulfuric acid (90°C) Oxidation-reduction potential (vs NHE): 1.1V (3) 100% by mass isopropyl alcohol (80°C) (4) 49% by mass hydrofluoric acid (70°C) (5) Mixed acid of hydrofluoric acid and nitric acid (mixture of 49% by mass hydrofluoric acid and 69-71% by mass nitric acid in a volume ratio of 1:5) (20°C) (6) Mixed acid of hydrofluoric acid and nitric acid (mixture of 49% by mass hydrofluoric acid and 69-71% by mass nitric acid in a volume ratio of 1:100) (20°C) (7) SPM (mixture of 98% by mass sulfuric acid and 30-36% by mass hydrogen peroxide in a volume ratio of 2:1) (80°C) Oxidation-reduction potential (vs NHE): 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 (vs NHE): 1.2V (9) SC2 (a mixture of 35-37% by mass hydrochloric acid, 30-36% by mass aqueous hydrogen peroxide, and deionized water in a volume ratio of 1:1:4) (70°C) Redox potential (vs NHE): 1.6V (10) 85% by mass phosphoric acid (80°C)

[0231] <Metal Leaching Test> As a preliminary cleaning, the test specimens were immersed in 3.6% hydrochloric acid for 1 hour, and then rinsed with pure water. After that, the test specimens were immersed in 100 mL of 3.6% 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.

[0232] <Metal Content> A 0.5 g test specimen was washed with 10 mL of ultrapure water and ashed using a muffle furnace (FUW222PB, Advantec Toyo Co., Ltd.) at 600°C for 5 hours. The ashed sample was dissolved in 10 mL of 5% by mass nitric acid, and the metal concentrations of 17 elements (Li, Na, Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Ba, Pb) were measured using ICP-MSI (Agilent 5900, Agilent Technologies) to determine the metal content.

[0233] The materials used in each example are listed below. (Resins) PE: HDPE (high-density polyethylene), melting point 134°C PP: melting point 166°C COP: amorphous cycloolefin resin, glass transition temperature 154°C COC: amorphous cycloolefin resin, glass transition temperature 158°C PMP: polymethylpentene resin, melting point 232°C Crystalline COP: crystalline cycloolefin resin, melting point 264°C

[0234] Examples 1-3, 8-11 and Comparative Examples 1, 2, 6-8 were welded using a SONOPET JII400 / JII900 series ultrasonic welding machine with oscillator unit press [S type] (manufactured by Seidensha Electronics Industry Co., Ltd.) under the conditions shown in Tables 1 and 2. Specifically, two test pieces were prepared: 10 × 50 × 5 mm (Examples 1-3, Comparative Examples 1 and 2), 10 × 50 × 1.5 mm (Example 8, Example 11, Comparative Example 6), 10 × 50 × 2 mm (Example 9, Comparative Example 7), and 10 × 50 × 3 mm (Example 10, Comparative Example 8). The ends of each test piece were overlapped by 10 × 10 mm in the longitudinal direction and fixed. The machine was vibrated under the conditions shown in Tables 1 and 2, and the frictional heat generated during the vibration melted the contact area of ​​both test pieces, thereby welding them together to create a laminate (joint). The tensile strength of the obtained laminate was measured. The results are shown in Tables 1 and 2. In Comparative Examples 1 and 2, and 6-8, the resins did not weld together, and a laminate could not be obtained.

[0235]

[0236]

[0237] Examples 4 and Comparative Examples 3-5: Welding was performed using a high-frequency induction heating device (non-contact hot plate welding machine, servo press type) (manufactured by Seidensha Electronics Industry Co., Ltd.) under the conditions shown in Table 3. Two 20 × 100 × 5 mm test pieces were prepared, and each was fixed so that its cross-section (5 × 20 mm) was opposite. The contact portion of both test pieces was melted under the conditions shown in Table 3, and a laminate (joint) was fabricated by welding. The tensile strength was measured using the obtained laminate. The results are shown in Table 3. In Comparative Examples 3 and 4, the resins did not weld to each other, and no laminate was obtained.

[0238]

[0239] Example 5 <Chemical Resistance (Corrosion Resistance) Test> Laminates (joints) of PE from Example 4, PP from Example 2, COP from Example 8, COC from Example 9, PMP from Example 10, and crystalline COP from Example 11 were prepared as test specimens, and chemical resistance (corrosion resistance) tests were performed using the method described above. The results are shown in Table 4.

[0240]

[0241] In Example 6, a metal elution test was performed using the method described above with test specimens of the PE laminate (joint) from Example 4, the PP laminate (joint) from Example 2, the COP laminate (joint) from Example 8, the COC laminate (joint) from Example 9, the PMP laminate (joint) from Example 10, and the crystalline COP laminate (joint) from Example 11. The results are shown in Table 5.

[0242]

[0243] In Example 7, the PE laminate (joint) from Example 4, the PP laminate (joint) from Example 2, the COP laminate (joint) from Example 8, the COC laminate (joint) from Example 9, and the PMP laminate (joint) from Example 10 were used as test specimens, and the metal content was determined using the method described above. The results are shown in Table 6.

[0244]

[0245] The assembled body of the embodiment was suitable for use as a component (part) in semiconductor manufacturing equipment where chemicals are used.

Claims

1. A joint for semiconductor manufacturing equipment, containing an olefin resin and having a tensile strength of 5 MPa or more.

2. The joint for semiconductor manufacturing equipment according to claim 1, wherein the tensile strength is 5 to 15 MPa.

3. The semiconductor manufacturing equipment-related joint according to claim 1 or 2, wherein the olefin resin is at least one selected from the group consisting of polyethylene resin, polypropylene resin, amorphous cycloolefin resin, crystalline cycloolefin resin, and polymethylpentene resin.

4. The semiconductor manufacturing equipment assembly according to any one of claims 1 to 3, wherein the olefin resin is at least one selected from the group consisting of polyethylene resin, polypropylene resin, amorphous cycloolefin resin, and polymethylpentene resin.

5. A bonding body for semiconductor manufacturing-related equipment according to any one of claims 1 to 4, wherein the thickness is 1 to 40 mm.

6. A joint for semiconductor manufacturing equipment according to any one of claims 1 to 5, which comes into contact with corrosive substances.

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

8. The semiconductor manufacturing equipment-related joint according to any one of claims 1 to 7, wherein the total metal content of the 17 elements (Li, Na, Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Ba, Pb) when the joint is ashed is 200 ppm or less.

9. The semiconductor manufacturing equipment-related joint according to any one of claims 1 to 8, wherein the total amount of metal leaching of 16 elements (Li, Na, Mg, Al, K, Ca, Ti, Cr, Mn, Fe, Ni, Cu, Zn, Ag, Cd, Pb) when the joint is immersed in 3.6 mass% hydrochloric acid at 23°C for one week is 65 ppb or less.

10. The semiconductor manufacturing equipment-related joint according to any one of claims 1 to 9, wherein the surface roughness Sa of the joint portion of the joint is 5 to 100 μm.

11. The semiconductor manufacturing equipment-related joint according to any one of claims 1 to 10, wherein the surface roughness Sa of the joint portion of the joint is 20 to 30 μm.

12. The joint portion of the joint is joined by ultrasonic welding, as described in any one of claims 1 to 11, for use in semiconductor manufacturing equipment.

13. The joint portion of the joint is joined by hot plate welding, according to any one of claims 1 to 11, for use in semiconductor manufacturing equipment.

14. The semiconductor manufacturing equipment assembly according to any one of claims 1 to 13, which is at least one semiconductor manufacturing equipment component selected from the group consisting of pipes, nozzles, tubes, fittings, tanks, housings and containers.

15. A method for manufacturing a joint for semiconductor manufacturing equipment according to any one of claims 1 to 12 or 14, comprising the step of ultrasonically welding the objects to be joined under the conditions of an amplitude of 0.01 to 3 mm, a friction pressure of 0.05 to 10 MPa, and a pressurizing time of 0.2 to 10 seconds.

16. The manufacturing method according to claim 15, comprising the step of ultrasonically welding objects to be joined under the conditions of an amplitude of 0.03 to 0.05 mm, a friction pressure of 0.5 to 1 MPa, and a pressurizing time of 0.2 to 2 seconds.

17. A method for manufacturing a bonded body for semiconductor manufacturing equipment according to any one of claims 1 to 11, 13, or 14, comprising the step of welding the object to be joined to the hot plate using a hot plate with a surface temperature of 400 to 800°C, with a clearance of 0.1 to 2 mm between the object to be joined and the hot plate, and a heating time of 0.1 to 5 seconds.

18. The manufacturing method according to claim 17, comprising the step of welding the objects to be joined to a hot plate using a hot plate with a surface temperature of 550 to 650°C, with a clearance of 0.5 to 0.8 mm between the objects to be joined and the hot plate, and a heating time of 2 to 3.5 seconds.

19. A semiconductor manufacturing apparatus equipped with a semiconductor manufacturing apparatus assembly according to any one of claims 1 to 14.

20. The semiconductor manufacturing-related apparatus according to claim 19, which is at least one selected from the group consisting of semiconductor manufacturing equipment and related equipment for semiconductor manufacturing equipment.

21. The semiconductor manufacturing apparatus according to claim 20, wherein the semiconductor manufacturing apparatus is at least one selected from the group consisting of a photolithography apparatus, a thin film formation / etching / cleaning and drying apparatus, an inspection and evaluation apparatus / manufacturing apparatus, a resist processing apparatus, an etching apparatus, a cleaning and drying apparatus, a CVD apparatus, a thin film formation apparatus, a CMP apparatus, a processing apparatus, an aging apparatus, and an inspection apparatus, and the semiconductor manufacturing apparatus-related 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-related apparatus.

22. The photolithography process 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 / drying apparatus is at least one selected from the group consisting of a vacuum deposition apparatus, a cleaning apparatus, a drying apparatus, and a scrub cleaning apparatus; the inspection and evaluation apparatus / manufacturing apparatus is a defect correction apparatus; 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 cleaning / drying apparatus is at least one selected from the group consisting of a wet cleaning apparatus, a scrub cleaning apparatus, and a drying apparatus; the CVD apparatus is at least one selected from the group consisting of a high-pressure CVD apparatus, SACVD, reduced-pressure CVD, plasma CVD apparatus, metal CVD apparatus, mist CVD apparatus, and ALD apparatus. The thin film forming 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 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 apparatus is a life testing apparatus; the pure water / chemical solution apparatus is at least one selected from the group consisting of a chemical supply apparatus, a slurry supply apparatus, a chemical purification apparatus, and a waste liquid treatment apparatus; the gas apparatus is at least one selected from the group consisting of a gas generator, a gas purification apparatus, a gas mixing apparatus, a gas detection apparatus, and an exhaust gas treatment apparatus; and 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 21, 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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