WO2024004602A1 - 熱可塑性樹脂組成物、成形体、及び、検査用ｉｃソケットの構成部材 - Google Patents

熱可塑性樹脂組成物、成形体、及び、検査用ｉｃソケットの構成部材 Download PDF

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WO2024004602A1
WO2024004602A1 PCT/JP2023/021667 JP2023021667W WO2024004602A1 WO 2024004602 A1 WO2024004602 A1 WO 2024004602A1 JP 2023021667 W JP2023021667 W JP 2023021667W WO 2024004602 A1 WO2024004602 A1 WO 2024004602A1
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Prior art keywords
component
thermoplastic resin
group
resin composition
mass
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PCT/JP2023/021667
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English (en)
French (fr)
Japanese (ja)
Inventor
勇希 佐藤
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Priority to EP23831051.0A priority Critical patent/EP4549517A4/en
Priority to US18/878,150 priority patent/US20250388735A1/en
Priority to CN202380048223.2A priority patent/CN119403887A/zh
Priority to JP2024530642A priority patent/JPWO2024004602A1/ja
Priority to KR1020247042675A priority patent/KR20250027668A/ko
Publication of WO2024004602A1 publication Critical patent/WO2024004602A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R1/00—Details of instruments or arrangements of the types included in groups G01R5/00 - G01R13/00 and G01R31/00
    • G01R1/02—General constructional details
    • G01R1/04—Housings; Supporting members; Arrangements of terminals
    • G01R1/0408—Test fixtures or contact fields; Connectors or connecting adaptors; Test clips; Test sockets
    • G01R1/0433—Sockets for IC's or transistors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02—Contact members
    • H01R13/22—Contacts for co-operating by abutting
    • H01R13/24—Contacts for co-operating by abutting resilient; resiliently-mounted
    • H01R13/2407—Contacts for co-operating by abutting resilient; resiliently-mounted characterized by the resilient means
    • H01R13/2421—Contacts for co-operating by abutting resilient; resiliently-mounted characterized by the resilient means using coil springs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C08K2003/282—Binary compounds of nitrogen with aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/14—Carbides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R1/00—Details of instruments or arrangements of the types included in groups G01R5/00 - G01R13/00 and G01R31/00
    • G01R1/02—General constructional details
    • G01R1/04—Housings; Supporting members; Arrangements of terminals
    • G01R1/0408—Test fixtures or contact fields; Connectors or connecting adaptors; Test clips; Test sockets
    • G01R1/0433—Sockets for IC's or transistors
    • G01R1/0441—Details
    • G01R1/0466—Details concerning contact pieces or mechanical details, e.g. hinges or cams; Shielding
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
    • G01R31/28—Testing of electronic circuits, e.g. by signal tracer
    • G01R31/2851—Testing of integrated circuits [IC]
    • G01R31/2855—Environmental, reliability or burn-in testing
    • G01R31/286—External aspects, e.g. related to chambers, contacting devices or handlers
    • G01R31/2863—Contacting devices, e.g. sockets, burn-in boards or mounting fixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R2201/00—Connectors or connections adapted for particular applications
    • H01R2201/20—Connectors or connections adapted for particular applications for testing or measuring purposes

Definitions

  • the present invention relates to a thermoplastic resin composition, a molded article, and a component of an IC socket for testing.
  • thermoplastic resins that have excellent properties such as moldability, heat resistance, and strength, and are used in a wide range of fields such as automobile parts, mechanical parts, and electrical and electronic parts.
  • Thermoplastic resin compositions in which engineering plastics contain functional fillers are also known.
  • a thermoplastic resin component containing a crystalline thermoplastic resin and an amorphous thermoplastic resin, a carbon precursor, and a conductive filler are formed from a resin composition containing predetermined amounts of each. It is described that a low-contamination injection molded article can have a surface resistivity that can be strictly controlled to a desired value within a semiconductive region, and that the amount of foreign particles generated is extremely small.
  • Patent Document 2 discloses that a flame-retardant polyimide molding material containing a semi-aromatic polyimide resin and a predetermined amount of graphite, carbon fiber, etc. has excellent moldability and can exhibit high flame retardancy. There is.
  • Patent Document 3 discloses that the ball guide film 180 constituting the test socket can be composed of a polyimide film that is thin and has excellent wear resistance.
  • the flame-retardant polyimide molding material described in Patent Document 2 can be applied to IC sockets for testing.
  • the testing IC socket include an IC socket for product testing (test socket), an IC socket for burn-in testing (burn-in socket), and the like.
  • test socket IC socket for product testing
  • burn-in socket burn-in testing
  • a method for producing the member using a molded body containing a thermoplastic resin and an inorganic filler, such as the flame-retardant polyimide molding material includes, for example, cutting the molded body to produce a flat plate; An example of this method is to make a fine through hole in a flat plate into which the measuring device is fitted.
  • an example of this method is to make a fine through hole in a flat plate into which the measuring device is fitted.
  • the machinability of a molded body there is room for further improvement in the machinability of the molded body and the fine machinability in manufacturing components of IC sockets for testing using the flat plate obtained by cutting.
  • the machinability of a molded body there is a problem that when a molded body manufactured by injection molding or the like is cut, if the resulting flat plate surface has large irregularities, it is not suitable for micromachining.
  • microfabrication when making a large number of through holes at a narrow pitch in the obtained flat plate, if the hole diameter distribution increases, pattern
  • An object of the present invention is to provide a thermoplastic resin composition from which a molded article with excellent cutting workability and fine workability can be produced.
  • thermoplastic resin composition containing a specific thermoplastic resin and a specific inorganic filler can solve the above problems. That is, the present invention relates to the following.
  • Component (A) at least one member selected from the group consisting of a crystalline thermoplastic resin (a1) with a melting point of 270°C or higher and an amorphous thermoplastic resin (a2) with a glass transition temperature of 200°C or higher.
  • the component (A) is a polyimide resin, a polyetherimide resin, a polyetherimide sulfone resin, a polyphenylene sulfide resin, a polyetheretherketone resin, a polyetherketoneketone resin, a liquid crystal polymer, and a wholly aromatic resin other than a liquid crystal polymer.
  • thermoplastic resin composition which is at least one selected from the group consisting of polyester resins.
  • the component (A) contains a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), and the repeating structural unit of the formula (1) and the repeating structural unit of the formula (2) )
  • Resin composition. (R 1 is a divalent group having 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure.
  • R 2 is a divalent chain aliphatic group having 5 to 16 carbon atoms.
  • X 1 and X 2 are each independently a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.
  • D50 volume median particle size
  • the component (B) further contains an inorganic filler (b2) other than the component (b1), and the component (b2) is talc, mica, silica, alumina, silicon nitride, aluminum nitride, boron nitride. , silicon carbide, boron carbide, calcium carbonate, and titanium oxide, the thermoplastic resin composition according to any one of [1] to [5] above.
  • a molded article comprising the thermoplastic resin composition according to any one of [1] to [7] above.
  • a component of an IC socket for testing obtained by processing the molded article described in [8] above.
  • thermoplastic resin composition of the present invention a molded article having excellent cutting workability and fine workability can be produced.
  • the molded body is suitable for producing components of IC sockets for inspection, etc.
  • FIG. 2 is a schematic plan view showing an embodiment of a component 100 of an IC socket for inspection.
  • a molded object having excellent machinability means that a molded object obtained by thermoforming a thermoplastic resin composition is cut into a flat plate-like molded object (hereinafter also simply referred to as a "flat plate”). ) means that a flat plate with low surface roughness on the cut surface can be obtained. Surface roughness can be evaluated by arithmetic mean roughness (Ra). Furthermore, when the flat plate obtained by cutting has little warpage, it is judged that the molded body has better cutting workability.
  • through-hole means a fine through-hole having a diameter of, for example, 200 ⁇ m or less, preferably 100 ⁇ m or less, more preferably less than 100 ⁇ m, and the pitch is, for example, in the range of 1 to 5 times the diameter of the through-hole.
  • the machinability and micromachinability can be specifically evaluated by the methods described in Examples.
  • the content of the component (b1) is 2 to 40 parts by mass, and the content of the component (B) is 2 to 60 parts by mass relative to 100 parts by mass of the component (A).
  • the thermoplastic resin composition of the present invention has excellent machinability and machinability by using a thermoplastic resin (A) having predetermined thermophysical properties and a predetermined amount of an inorganic filler (B) containing zirconium oxide (b1).
  • a molded body with excellent microprocessability can be produced.
  • the volume median particle size (D50) of the zirconium oxide (b1) is preferably 1 ⁇ m or less.
  • the wall surfaces of the fine through-holes are also kept smooth, which increases the accuracy of hole formation and is thought to suppress an increase in the pore size distribution and pattern collapse. It is also presumed that by incorporating a predetermined amount of the highly hard component (b1) into the thermoplastic resin (A), the material becomes appropriately brittle and the occurrence of burrs can be suppressed.
  • thermoplastic resin (A) (hereinafter also simply referred to as “component (A)” or “thermoplastic resin (A)”) used in the present invention includes a crystalline thermoplastic resin (a1) with a melting point of 270°C or higher and glass. At least one type selected from the group consisting of amorphous thermoplastic resins (a2) having a transition temperature of 200° C. or higher.
  • a crystalline thermoplastic resin refers to a resin that has a melting point and a glass transition temperature
  • an amorphous thermoplastic resin refers to a resin that has a glass transition temperature but no melting point. Note that resins that have essentially crystallinity but have an extremely slow crystallization rate and that can only be processed in an amorphous state by various molding methods are classified as amorphous thermoplastic resins.
  • the crystalline thermoplastic resin (a1) used as component (A) (hereinafter also simply referred to as "component (a1)”) has a melting point of 270 from the viewpoint of producing a molded product with excellent cutting workability and fine workability. It is a crystalline thermoplastic resin with a temperature of °C or higher.
  • the melting point of component (a1) is preferably 280°C or higher, more preferably 290°C or higher, and even more preferably 300°C or higher, from the viewpoint of improving the machinability and microprocessability of the molded product obtained.
  • the temperature is preferably 400°C or lower, more preferably 380°C or lower, and even more preferably 350°C or lower.
  • the melting point of component (a1) can be measured using a differential scanning calorimeter, specifically by the method described in the Examples.
  • the glass transition temperature (Tg) of component (a1) is not particularly limited, but from the viewpoint of improving the machinability and fine machinability of the resulting molded product, it is preferably 130°C or higher, more preferably 140°C or higher, and even more preferably The temperature is 150°C or higher, and from the viewpoint of ease of molding, the temperature is preferably 250°C or lower, more preferably 230°C or lower, and still more preferably 200°C or lower.
  • the glass transition temperature of component (a1) can be measured using a differential scanning calorimeter, specifically by the method described in the Examples.
  • the amorphous thermoplastic resin (a2) used as component (A) has a glass transition property from the viewpoint of producing a molded product with excellent cutting workability and fine workability. It is an amorphous thermoplastic resin with a temperature of 200°C or higher.
  • the glass transition temperature (Tg) of component (a2) is preferably 210°C or higher, more preferably 230°C or higher, and even more preferably 250°C or higher, from the viewpoint of improving the machinability and microprocessability of the obtained molded product. be.
  • the temperature is preferably 400°C or lower, more preferably 350°C or lower, and even more preferably 300°C or lower.
  • the glass transition temperature of component (a2) can be measured by the same method as described above.
  • Component (A) includes, for example, polyimide resin, polyamide resin, polyetherimide resin, polyetherimide sulfone resin, polyphenylene sulfide resin, polyetheretherketone resin, polyetherketoneketone resin, polycarbonate resin, polyamideimide resin, polysulfone.
  • component (A) is preferably polyimide resin, polyetherimide resin, polyetherimide sulfone resin, polyphenylene sulfide resin, polyether ether, from the viewpoint of producing a molded product with excellent cutting workability and fine workability.
  • component (A) is more preferably a polyimide resin, among which polyimide resins having an aliphatic structure (other than wholly aromatic) or polyimides having a bulky structure such as halogen. It is resin.
  • component (A) As component (A), component (a1), component (a2), or a mixture of component (a1) and component (a2) can be used. From the viewpoint of improving the machinability and fine machinability of the obtained molded body, it is preferable that component (A) contains component (a1) which is a crystalline thermoplastic resin.
  • component (a1) in component (A) is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably The content is 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more and 100% by mass or less.
  • component (A) contains component (a1)
  • the component ( a1) is more preferably a polyimide resin, more preferably contains a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), and the repeating structural unit of the formula (1) and
  • the polyimide resin (a1-1) has a content ratio of repeating structural units of the formula (1) to the total repeating structural units of the formula (2) from 20 to 70 mol%.
  • R 1 is a divalent group having 6 to 22 carbon atoms containing at least one alicyclic hydrocarbon structure.
  • R 2 is a divalent chain aliphatic group having 5 to 16 carbon atoms.
  • X 1 and X 2 are each independently a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.
  • the polyimide resin (a1-1) is a crystalline thermoplastic resin, and its form is preferably powder or pellets.
  • the polyimide resin is, for example, a polyimide resin that does not have a glass transition temperature (Tg), which is formed by molding a polyimide precursor such as polyamic acid, and then closing the imide ring, or a polyimide resin that is formed at a temperature lower than the glass transition temperature. It is distinguished from polyimide resin, which decomposes.
  • R 1 is a divalent group having 6 to 22 carbon atoms and containing at least one alicyclic hydrocarbon structure.
  • the alicyclic hydrocarbon structure means a ring derived from an alicyclic hydrocarbon compound, and the alicyclic hydrocarbon compound may be saturated or unsaturated, and the alicyclic hydrocarbon structure may be saturated or unsaturated. It may be a ring or a polycyclic ring.
  • alicyclic hydrocarbon structure examples include, but are not limited to, cycloalkane rings such as cyclohexane rings, cycloalkene rings such as cyclohexene, bicycloalkane rings such as norbornane rings, and bicycloalkene rings such as norbornene. Do not mean. Among these, preferred is a cycloalkane ring, more preferred is a cycloalkane ring having 4 to 7 carbon atoms, and even more preferred is a cyclohexane ring.
  • the number of carbon atoms in R 1 is 6 to 22, preferably 8 to 17.
  • R 1 contains at least one alicyclic hydrocarbon structure, preferably 1 to 3 alicyclic hydrocarbon structures.
  • R 1 is preferably a divalent group represented by the following formula (R1-1) or (R1-2).
  • (m 11 and m 12 are each independently an integer of 0 to 2, preferably 0 or 1.
  • m 13 to m 15 are each independently an integer of 0 to 2, preferably 0 or 1)
  • R 1 is particularly preferably a divalent group represented by the following formula (R1-3).
  • R1-3 the positional relationship of the two methylene groups with respect to the cyclohexane ring may be cis or trans, and the ratio of cis to trans is Any value is acceptable.
  • X 1 is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.
  • the aromatic ring may be a single ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring, but are not limited thereto. Among these, benzene rings and naphthalene rings are preferred, and benzene rings are more preferred.
  • the number of carbon atoms in X 1 is 6 to 22, preferably 6 to 18.
  • X 1 contains at least one aromatic ring, preferably 1 to 3 aromatic rings.
  • X 1 is preferably a tetravalent group represented by any of the following formulas (X-1) to (X-4).
  • R 11 to R 18 are each independently an alkyl group having 1 to 4 carbon atoms.
  • p 11 to p 13 are each independently an integer of 0 to 2, preferably 0.
  • p 14 , p 15 , p 16 and p 18 are each independently an integer of 0 to 3, preferably 0.
  • p 17 is an integer of 0 to 4, preferably 0.
  • Each of 13 is independently a single bond, an ether group, a carbonyl group, or an alkylene group having 1 to 4 carbon atoms.
  • X 1 is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring
  • R 12 , R 13 , p 12 and p 13 in formula (X-2) are represented by formula (X-
  • the number of carbon atoms in the tetravalent group represented by 2) is selected to be within the range of 10 to 22.
  • L 11 , R 14 , R 15 , p 14 and p 15 in formula (X-3) are such that the number of carbon atoms in the tetravalent group represented by formula (X-3) is in the range of 12 to 22.
  • L 12 , L 13 , R 16 , R 17 , R 18 , p 16 , p 17 and p 18 in formula (X-4) are tetravalent groups represented by formula (X-4). is selected such that the number of carbon atoms in the group falls within the range of 18 to 22.
  • X 1 is particularly preferably a tetravalent group represented by the following formula (X-5) or (X-6).
  • R 2 is a divalent chain aliphatic group having 5 to 16 carbon atoms, preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and even more preferably 8 to 10 carbon atoms.
  • the chain aliphatic group means a group derived from a chain aliphatic compound, and the chain aliphatic compound may be saturated or unsaturated, and the chain aliphatic group may be saturated or unsaturated. It may be branched or branched, and may contain a heteroatom such as an oxygen atom.
  • R 2 is preferably an alkylene group having 5 to 16 carbon atoms, more preferably an alkylene group having 6 to 14 carbon atoms, even more preferably 7 to 12 carbon atoms, and especially preferably an alkylene group having 8 to 10 carbon atoms. It is an alkylene group.
  • the alkylene group may be a straight chain alkylene group or a branched alkylene group, but is preferably a straight chain alkylene group.
  • R 2 is preferably at least one selected from the group consisting of an octamethylene group and a decamethylene group, particularly preferably an octamethylene group.
  • R 2 is a divalent chain aliphatic group having 5 to 16 carbon atoms and containing an ether group.
  • the number of carbon atoms is preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, and still more preferably 8 to 10 carbon atoms.
  • divalent groups represented by the following formula (R2-1) or (R2-2) are preferred.
  • (m 21 and m 22 are each independently an integer of 1 to 15, preferably 1 to 13, more preferably 1 to 11, even more preferably 1 to 9.
  • m 23 to m 25 are each (Independently, it is an integer from 1 to 14, preferably from 1 to 12, more preferably from 1 to 10, and even more preferably from 1 to 8.)
  • R 2 is a divalent chain aliphatic group having 5 to 16 carbon atoms (preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, even more preferably 8 to 10 carbon atoms)
  • m 21 and m 22 in formula (R2-1) are divalent groups represented by formula (R2-1) having 5 to 16 carbon atoms (preferably 6 to 14 carbon atoms, more preferably 7 carbon atoms). to 12 carbon atoms, more preferably 8 to 10 carbon atoms.
  • m 21 +m 22 is 5 to 16 (preferably 6 to 14, more preferably 7 to 12, still more preferably 8 to 10).
  • m 23 to m 25 in formula (R2-2) is a divalent group represented by formula (R2-2) having 5 to 16 carbon atoms (preferably 6 to 14 carbon atoms, more preferably The number of carbon atoms is selected to fall within the range of 7 to 12 carbon atoms, more preferably 8 to 10 carbon atoms. That is, m 23 +m 24 +m 25 is 5 to 16 (preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, still more preferably 8 to 10 carbon atoms).
  • X 2 is defined in the same manner as X 1 in formula (1), and preferred embodiments are also the same.
  • the content ratio of the repeating structural unit of formula (1) to the total of the repeating structural unit of formula (1) and the repeating structural unit of formula (2) is 20 to 70 mol%.
  • the content ratio of the repeating structural unit of formula (1) is within the above range, it becomes possible to sufficiently crystallize the polyimide resin (a1-1) even in a general injection molding cycle. If the content ratio is less than 20 mol%, thermoformability will decrease, and if it exceeds 70 mol%, crystallinity will decrease, resulting in a decrease in heat resistance.
  • the content ratio of the repeating structural unit of formula (1) to the total of the repeating structural unit of formula (1) and the repeating structural unit of formula (2) is preferably 65 mol% or less, More preferably it is 60 mol% or less, and still more preferably 50 mol% or less.
  • the content ratio of the repeating structural unit of formula (1) to the total of the repeating structural unit of formula (1) and the repeating structural unit of formula (2) is preferably 20 mol% or more and less than 40 mol%.
  • the crystallinity of the polyimide resin (a1-1) will be high, and a resin composition with better heat resistance can be obtained.
  • the above content ratio is preferably 25 mol% or more, more preferably 30 mol% or more, even more preferably 32 mol% or more, and even more preferably from the viewpoint of developing high crystallinity. is 35 mol% or less.
  • the total content ratio of the repeating constituent units of formula (1) and repeating constituent units of formula (2) to all repeating constituent units constituting the polyimide resin (a1-1) is preferably 50 to 100 mol%, more preferably is 75 to 100 mol%, more preferably 80 to 100 mol%, even more preferably 85 to 100 mol%.
  • the polyimide resin (a1-1) may further contain a repeating structural unit of the following formula (3).
  • the content ratio of the repeating structural unit of formula (3) to the total of the repeating structural unit of formula (1) and the repeating structural unit of formula (2) is preferably 25 mol % or less.
  • the lower limit is not particularly limited as long as it exceeds 0 mol%.
  • the content ratio is preferably 5 mol% or more, more preferably 10 mol% or more, while from the viewpoint of maintaining crystallinity, it is preferably 20 mol% or less, more Preferably it is 15 mol% or less.
  • R 3 is a divalent group having 6 to 22 carbon atoms containing at least one aromatic ring.
  • X 3 is a tetravalent group having 6 to 22 carbon atoms containing at least one aromatic ring.
  • R 3 is a divalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.
  • the aromatic ring may be a single ring or a condensed ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a tetracene ring, but are not limited thereto. Among these, benzene rings and naphthalene rings are preferred, and benzene rings are more preferred.
  • the number of carbon atoms in R 3 is 6 to 22, preferably 6 to 18.
  • R 3 contains at least one aromatic ring, preferably 1 to 3 aromatic rings. Further, a monovalent or divalent electron-withdrawing group may be bonded to the aromatic ring.
  • Examples of monovalent electron-withdrawing groups include nitro group, cyano group, p-toluenesulfonyl group, halogen, halogenated alkyl group, phenyl group, and acyl group.
  • Examples of divalent electron-withdrawing groups include fluorinated alkylene groups (for example, -C(CF 3 ) 2 -, -(CF 2 ) p - (where p is an integer from 1 to 10)).
  • examples include -CO-, -SO 2 -, -SO-, -CONH-, -COO-, and the like.
  • R 3 is preferably a divalent group represented by the following formula (R3-1) or (R3-2).
  • (m 31 and m 32 are each independently an integer of 0 to 2, preferably 0 or 1.
  • m 33 and m 34 are each independently an integer of 0 to 2, preferably 0 or 1.
  • R 21 , R 22 and R 23 are each independently an alkyl group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, or an alkynyl group having 2 to 4 carbon atoms.
  • p 21 , p 22 and p 23 are integers of 0 to 4, preferably 0.
  • L 21 is a single bond, an ether group, a carbonyl group, or an alkylene group having 1 to 4 carbon atoms.
  • R 3 is a divalent group having 6 to 22 carbon atoms and containing at least one aromatic ring
  • m 31 , m 32 , R 21 and p 21 in formula (R3-1) are represented by formula (R3-1).
  • the number of carbon atoms in the divalent group represented by 1) is selected to be within the range of 6 to 22.
  • L 21 , m 33 , m 34 , R 22 , R 23 , p 22 and p 23 in formula (R3-2) have the number of carbon atoms in the divalent group represented by formula (R3-2). It is selected to fall within the range of 12 to 22.
  • X 3 is defined in the same manner as X 1 in formula (1), and preferred embodiments are also the same.
  • the polyimide resin (a1-1) may further contain a repeating structural unit represented by the following formula (4).
  • R 4 is a divalent group containing -SO 2 - or -Si(R x ) (R y ) O-, and R x and R y are each independently a chain aliphatic group having 1 to 3 carbon atoms. group or phenyl group.
  • X 4 is a tetravalent group having 6 to 22 carbon atoms and containing at least one aromatic ring.
  • X 4 is defined in the same manner as X 1 in formula (1), and preferred embodiments are also the same.
  • the polyimide resin (a1-1) has a chain aliphatic group having 5 to 14 carbon atoms at the terminal.
  • the chain aliphatic group may be saturated or unsaturated, and may be linear or branched.
  • Examples of the saturated chain aliphatic group having 5 to 14 carbon atoms include n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, Lauryl group, n-tridecyl group, n-tetradecyl group, isopentyl group, neopentyl group, 2-methylpentyl group, 2-methylhexyl group, 2-ethylpentyl group, 3-ethylpentyl group, isooctyl group, 2-ethylhexyl group , 3-ethylhexyl group, isononyl group, 2-ethyloctyl group, isodecyl group, isododecyl group, isotridecyl group, isotetradecyl group, and the like.
  • Examples of unsaturated chain aliphatic groups having 5 to 14 carbon atoms include 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group, 1-heptenyl group, 2-heptenyl group, 1-octenyl group. , 2-octenyl group, nonenyl group, decenyl group, dodecenyl group, tridecenyl group, tetradecenyl group and the like.
  • the chain aliphatic group is preferably a saturated chain aliphatic group, more preferably a saturated straight chain aliphatic group.
  • the chain aliphatic group preferably has 6 or more carbon atoms, more preferably 7 or more carbon atoms, even more preferably 8 or more carbon atoms, and preferably 12 or less carbon atoms, more preferably has 10 or less carbon atoms, more preferably 9 or less carbon atoms.
  • the number of the above-mentioned chain aliphatic groups may be one, or two or more.
  • the chain aliphatic group is particularly preferably at least one selected from the group consisting of n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, n-decyl group, and isodecyl group. More preferably at least one selected from the group consisting of n-octyl group, isooctyl group, 2-ethylhexyl group, n-nonyl group, and isononyl group, most preferably n-octyl group, isooctyl group, and At least one type selected from the group consisting of 2-ethylhexyl group.
  • the polyimide resin (a1-1) preferably has only a chain aliphatic group having 5 to 14 carbon atoms at the end in addition to the terminal amino group and the terminal carboxy group.
  • the terminal group has a group other than the above, its content is preferably 10 mol % or less, more preferably 5 mol % or less, based on the chain aliphatic group having 5 to 14 carbon atoms.
  • the content of the above-mentioned chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (a1-1) is determined based on the total repeating structure constituting the polyimide resin (a1-1) from the viewpoint of exhibiting excellent heat aging resistance. It is preferably 0.01 mol% or more, more preferably 0.1 mol% or more, and even more preferably 0.2 mol% or more, based on the total 100 mol% of units.
  • the content of the above-mentioned chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (a1-1) must be It is preferably 10 mol% or less, more preferably 6 mol% or less, and still more preferably 3.5 mol% or less, based on the total 100 mol% of all repeating structural units constituting 1).
  • the content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (a1-1) can be determined by depolymerizing the polyimide resin (a1-1).
  • the polyimide resin (a1-1) preferably has a melting point of 360°C or lower and a glass transition temperature of 150°C or higher.
  • the melting point of the polyimide resin is preferably 280°C or higher, still more preferably 290°C or higher, from the viewpoint of heat resistance, and preferably 345°C or lower, more preferably 340°C from the viewpoint of achieving high moldability.
  • the temperature below is more preferably 335°C or below.
  • the glass transition temperature of the polyimide resin (a1-1) is more preferably 160°C or higher, more preferably 170°C or higher from the viewpoint of heat resistance, and from the viewpoint of achieving high moldability, it is preferably The temperature is 250°C or lower, more preferably 230°C or lower, even more preferably 200°C or lower.
  • the melting point and glass transition temperature of the polyimide resin (a1-1) can both be measured with a differential scanning calorimeter.
  • the polyimide resin (a1-1) was determined to have a cooling rate of 20°C/min after melting the polyimide resin by differential scanning calorimeter measurement.
  • the amount of heat of the crystallization exothermic peak observed when cooling is preferably 5.0 mJ/mg or more, and preferably 10.0 mJ/mg or more. is more preferable, and even more preferably 17.0 mJ/mg or more.
  • the upper limit of the crystallization calorific value is not particularly limited, but is usually 45.0 mJ/mg or less.
  • the melting point, glass transition temperature, and crystallization heat value of the polyimide resin (a1-1) can be specifically measured by the methods described in Examples.
  • the logarithmic viscosity of the 0.5% by mass concentrated sulfuric acid solution of the polyimide resin (a1-1) at 30°C is preferably in the range of 0.2 to 2.0 dL/g, more preferably in the range of 0.3 to 1.8 dL/g. It is. If the logarithmic viscosity is 0.2 dL/g or more, sufficient mechanical strength will be obtained when the obtained polyimide resin composition is made into a molded product, and if it is 2.0 dL/g or less, moldability and handling will be improved. Improves sex.
  • the logarithmic viscosity ⁇ is determined by measuring the flow times of concentrated sulfuric acid and the polyimide resin solution at 30° C.
  • the weight average molecular weight Mw of the polyimide resin (a1-1) is preferably 10,000 to 150,000, more preferably 15,000 to 100,000, still more preferably 20,000 to 80,000, even more preferably The range is from 30,000 to 70,000, more preferably from 35,000 to 65,000. If the weight average molecular weight Mw of the polyimide resin (a1-1) is 10,000 or more, the resulting molded product will have good mechanical strength, and if it is 40,000 or more, the mechanical strength will have good stability. , 150,000 or less, the thermoformability will be good.
  • the weight average molecular weight Mw of the polyimide resin (a1-1) can be measured by gel filtration chromatography (GPC) using polymethyl methacrylate (PMMA) as a standard sample.
  • the polyimide resin (a1-1) can be produced by reacting a tetracarboxylic acid component and a diamine component.
  • the tetracarboxylic acid component contains a tetracarboxylic acid containing at least one aromatic ring and/or a derivative thereof
  • the diamine component contains a diamine containing at least one alicyclic hydrocarbon structure and a chain aliphatic diamine. .
  • the tetracarboxylic acid containing at least one aromatic ring is preferably a compound in which four carboxy groups are directly bonded to the aromatic ring, and may contain an alkyl group in its structure. Further, the tetracarboxylic acid preferably has 6 to 26 carbon atoms.
  • the tetracarboxylic acid include pyromellitic acid, 2,3,5,6-toluenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-biphenyl Tetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid and the like are preferred. Among these, pyromellitic acid is more preferred.
  • Examples of the derivative of tetracarboxylic acid containing at least one aromatic ring include anhydrides or alkyl esters of tetracarboxylic acid containing at least one aromatic ring.
  • the tetracarboxylic acid derivative preferably has 6 to 38 carbon atoms.
  • tetracarboxylic acid anhydrides include pyromellitic monoanhydride, pyromellitic dianhydride, 2,3,5,6-toluenetetracarboxylic dianhydride, 3,3',4,4'-diphenyl Sulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,4,5, Examples include 8-naphthalenetetracarboxylic dianhydride.
  • alkyl esters of tetracarboxylic acids include dimethyl pyromellitate, diethyl pyromellitate, dipropyl pyromellitate, diisopropyl pyromellitate, dimethyl 2,3,5,6-toluenetetracarboxylate, 3,3',4 , dimethyl 4'-diphenylsulfonetetracarboxylate, dimethyl 3,3',4,4'-benzophenonetetracarboxylate, dimethyl 3,3',4,4'-biphenyltetracarboxylate, 1,4,5,8 -Dimethyl naphthalenetetracarboxylate and the like.
  • the alkyl group preferably has 1 to 3 carbon atoms.
  • At least one compound selected from the above may be used alone, or two or more compounds may be used in combination.
  • the diamine containing at least one alicyclic hydrocarbon structure preferably has 6 to 22 carbon atoms, such as 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4- Bis(aminomethyl)cyclohexane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-diaminodicyclohexylmethane, 4,4'-methylenebis(2-methylcyclohexylamine) , carbondiamine, limonenediamine, isophoronediamine, norbornanediamine, bis(aminomethyl)tricyclo[5.2.1.0 2,6 ]decane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylpropane and the like are preferred.
  • diamines containing an alicyclic hydrocarbon structure generally have structural isomers, but the ratio of cis/trans isomers is not limited.
  • the chain aliphatic diamine may be linear or branched, and preferably has 5 to 16 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 7 to 12 carbon atoms. Further, as long as the chain portion has 5 to 16 carbon atoms, an ether bond may be included therebetween.
  • chain aliphatic diamines examples include 1,5-pentamethylene diamine, 2-methylpentane-1,5-diamine, 3-methylpentane-1,5-diamine, 1,6-hexamethylene diamine, 1,7-hepta Methylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-trideca Preferred are methylene diamine, 1,14-tetradecamethylene diamine, 1,16-hexadecamethylene diamine, 2,2'-(ethylenedioxy)bis(ethyleneamine), and the like.
  • Chain aliphatic diamines may be used alone or in combination. Among these, chain aliphatic diamines having 8 to 10 carbon atoms can be preferably used, and at least one selected from the group consisting of 1,8-octamethylene diamine and 1,10-decamethylene diamine is particularly preferred. Can be used.
  • the amount of diamine containing at least one alicyclic hydrocarbon structure charged relative to the total amount of diamine containing at least one alicyclic hydrocarbon structure and chain aliphatic diamine The molar ratio of is preferably 20 to 70 mol%.
  • the molar amount is preferably 25 mol% or more, more preferably 30 mol% or more, even more preferably 32 mol% or more, and from the viewpoint of expressing high crystallinity, preferably 60 mol% or less, more preferably 50 mol% or more. It is less than mol %, more preferably less than 40 mol %, even more preferably less than 35 mol %.
  • the diamine component may contain a diamine containing at least one aromatic ring.
  • the diamine containing at least one aromatic ring preferably has 6 to 22 carbon atoms, such as orthoxylylene diamine, metaxylylene diamine, paraxylylene diamine, 1,2-diethynylbenzenediamine, 1,3-diethynyl Benzenediamine, 1,4-diethynylbenzenediamine, 1,2-diaminobenzene, 1,3-diaminobenzene, 1,4-diaminobenzene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4 , 4'-diaminodiphenylmethane, ⁇ , ⁇ '-bis(4-aminophenyl)1,4-diisopropylbenzene, ⁇ , ⁇ '-bis(3-aminophenyl)-1,4-diisoprop
  • the molar ratio of the charged amount of diamine containing at least one aromatic ring to the total amount of diamine containing at least one alicyclic hydrocarbon structure and chain aliphatic diamine may be 25 mol% or less.
  • the lower limit is not particularly limited as long as it exceeds 0 mol%.
  • the molar ratio is preferably 5 mol% or more, more preferably 10 mol% or more, while from the viewpoint of maintaining crystallinity, it is preferably 20 mol% or less, more Preferably it is 15 mol% or less.
  • the molar ratio is preferably 12 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less, and even more preferably 0 mol%. .
  • the charging ratio of the tetracarboxylic acid component to the diamine component is 0.9 to 1.1 mol of the diamine component per 1 mol of the tetracarboxylic acid component. is preferred.
  • a terminal capping agent may be mixed in addition to the tetracarboxylic acid component and the diamine component.
  • the terminal capping agent is preferably at least one selected from the group consisting of monoamines and dicarboxylic acids.
  • the amount of the terminal capping agent to be used may be any amount that can introduce a desired amount of terminal groups into the polyimide resin (a1-1), and is from 0.0001 to 1 mole of the tetracarboxylic acid and/or its derivative. It is preferably 0.1 mol, more preferably 0.001 to 0.06 mol, and even more preferably 0.002 to 0.035 mol.
  • monoamine end-capping agents are preferred as the terminal-capping agent, and the above-mentioned chain aliphatic group having 5 to 14 carbon atoms is introduced to the end of the polyimide resin (a1-1) to improve heat aging resistance.
  • monoamines having a linear aliphatic group having 5 to 14 carbon atoms are more preferred, and monoamines having a saturated linear aliphatic group having 5 to 14 carbon atoms are even more preferred.
  • the terminal capping agent is particularly preferably at least one selected from the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, isononylamine, n-decylamine, and isodecylamine. , more preferably at least one selected from the group consisting of n-octylamine, isooctylamine, 2-ethylhexylamine, n-nonylamine, and isononylamine, and most preferably n-octylamine, isooctylamine, and 2-ethylhexylamine.
  • polymerization method for producing the polyimide resin (a1-1) As a polymerization method for producing the polyimide resin (a1-1), a known polymerization method can be applied, and the method described in International Publication No. 2016/147996 can be used.
  • the content of the polyimide resin (a1-1) in component (A) is determined from the viewpoints of improving the machinability and microprocessability of the resulting molded product, ease of thermoforming, and obtaining low dielectric properties. , preferably 30% by mass or more, more preferably 50% by mass or more, still 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 100% by mass or less.
  • the content of component (A) in the thermoplastic resin composition is preferably 40% by mass or more, more preferably 50% by mass or more, from the viewpoint of thermoformability and improvement of cutting workability and microprocessability of the obtained molded product. It is at least 60% by mass, even more preferably at least 65% by mass, even more preferably at least 70% by mass. In addition, from the viewpoint of improving the machinability and fine machinability of the obtained molded body, preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, even more preferably 80% by mass or less. It is.
  • thermoplastic resin composition of the present invention contains an inorganic filler containing zirconium oxide (b1) as component (B).
  • the shape of the zirconium oxide (b1) used in the present invention is not particularly limited, and examples thereof include spherical, plate-like, scale-like, columnar, and fibrous shapes. Among these, spherical or plate-shaped particles are preferable, and spherical particles are more preferable, from the viewpoint of improving the machinability and micro-processability of the obtained molded body. The smaller the particle size of zirconium oxide (b1), the better from the viewpoint of improving the machinability and microfabrication properties of the obtained molded body, and from the viewpoint of availability.
  • the volume median particle size (D50) of component (b1) is preferably 1 ⁇ m or less, more preferably 0.80 ⁇ m or less, even more preferably is 0.60 ⁇ m or less, more preferably 0.50 ⁇ m or less, even more preferably 0.40 ⁇ m or less.
  • the thickness is usually 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, and even more preferably It is 0.05 ⁇ m or more. D50 of component (b1) can be measured using a laser diffraction light scattering particle size distribution analyzer.
  • zirconium oxide particles used as component (b1) include, for example, the KZ series manufactured by Kyoritsu Materials Co., Ltd., the TZ series manufactured by Tosoh Corporation, the UEP series manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd. etc. Among these, KZ series high purity zirconia "KZ-0Y-LSF" manufactured by Kyoritsu Materials Co., Ltd. can be suitably selected.
  • the content of component (b1) in component (B) is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more, even more preferably 40% by mass or more, even more preferably 50% by mass or more, even more preferably 60% by mass or more, and 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or more. It is not more than 70% by mass, more preferably not more than 70% by mass.
  • the content of component (b1) with respect to 100 parts by mass of component (A) in the thermoplastic resin composition is 2 to 40 parts by mass, from the viewpoint of thermoformability and from the viewpoint of improving the machinability and microprocessability of the obtained molded product. It is preferably 5 to 35 parts by weight, more preferably 5 to 30 parts by weight, even more preferably 10 to 30 parts by weight, even more preferably 20 to 30 parts by weight.
  • Component (b2) Inorganic filler other than component (b1)
  • Component (B) may be an inorganic filler consisting only of component (b1), or may further contain an inorganic filler (b2) other than component (b1).
  • Ingredients (b2) include talc, mica, silica, alumina, wollastonite, silicon nitride, aluminum nitride, boron nitride, silicon carbide, boron carbide, calcium carbonate, titanium oxide, zinc oxide, calcium oxide, magnesium carbonate, carbonate.
  • Examples include barium, magnesium sulfate, barium sulfate, antimony trisulfide, tin sulfide, copper sulfide, iron sulfide, bismuth sulfide, zinc sulfide, and one or more of these can be used.
  • the component (b2) is preferably talc, mica, silica, alumina, silicon nitride, aluminum nitride, boron nitride, silicon carbide, At least one selected from the group consisting of boron carbide, calcium carbonate, and titanium oxide, more preferably at least one selected from the group consisting of talc, mica, silica, and titanium oxide, still more preferably talc and It is at least one selected from the group consisting of silica, and more preferably talc.
  • a hollow inorganic filler such as hollow silica or hollow alumina.
  • the shape of component (b2) is also not particularly limited, and examples include spherical, plate-like, scale-like, columnar, and fibrous shapes. Among these, spherical or plate-shaped particles are preferable from the viewpoint of improving the machinability and fine machinability of the obtained molded body, and from the viewpoint of availability.
  • the volume median particle size (D50) of component (b2) is preferably 3 ⁇ m or less, more preferably 2 ⁇ m or less, from the viewpoint of improving the machinability and micromachinability of the obtained molded product, and from the viewpoint of availability. , more preferably 1.5 ⁇ m or less, even more preferably 1.2 ⁇ m or less, even more preferably 1 ⁇ m or less.
  • the thickness is usually 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, and even more preferably It is 0.1 ⁇ m or more. D50 of component (b2) can be measured in the same manner as component (b1).
  • the content of component (b2) in component (B) is preferably 80 mass from the viewpoint of thermoformability and improvement of machinability and micromachinability of the resulting molded product.
  • % or less more preferably 70% by mass or less, still more preferably 65% by mass or less, even more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably 40% by mass or less, and Preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more. be.
  • the content of component (b2) with respect to 100 parts by mass of component (A) in the thermoplastic resin composition is preferably from the viewpoint of improving the machinability and microprocessability of the molded product obtained. is 1 to 40 parts by weight, more preferably 2 to 30 parts by weight, even more preferably 5 to 30 parts by weight, even more preferably 10 to 20 parts by weight.
  • the content of component (B) with respect to 100 parts by mass of component (A) in the thermoplastic resin composition is 2 to 60 parts from the viewpoint of thermoformability and from the viewpoint of improving the cutting workability and microprocessability of the obtained molded product. parts by weight, preferably 5 to 50 parts by weight, more preferably 10 to 45 parts by weight, even more preferably 15 to 45 parts by weight, even more preferably 20 to 45 parts by weight, even more preferably 25 to 45 parts by weight. , and even more preferably 30 to 45 parts by mass.
  • the thermoplastic resin composition of the present invention includes reinforcing fibers, a matting agent, a plasticizer, an antistatic agent, an anticoloring agent, an antigelation agent, a coloring agent, a sliding property improver, an antioxidant, a conductive agent, Additives other than component (B), such as a resin modifier, may be blended as necessary.
  • Additives other than component (B), such as a resin modifier may be blended as necessary.
  • component (B) such as a resin modifier
  • a resin modifier such as a resin modifier
  • the blending amount it is usually 50% by mass or less in the thermoplastic resin composition, preferably 0.0001 ⁇
  • the amount is 30% by weight, more preferably 0.001 to 15% by weight, even more preferably 0.01 to 10% by weight.
  • thermoplastic resin (A) can be blended into the thermoplastic resin composition of the present invention as long as the properties thereof are not impaired.
  • thermoplastic resin (A) and a resin other than the thermoplastic resin (A) are used together, there is no particular restriction on the blending ratio as long as the properties of the thermoplastic resin composition are not impaired.
  • the total content of component (A) and component (B) in the thermoplastic resin composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more. , more preferably 50% 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 100% by mass or less.
  • thermoplastic resin composition of the present invention can take any form, it is preferably in the form of pellets.
  • the thermoplastic resin composition of the present invention can be prepared, for example, after dry-blending the thermoplastic resin (A), an inorganic filler (B), and various optional components as necessary, or After feeding the inorganic filler (B) and any optional ingredients separately from the feed to the extruder, melt-knead them in the extruder to extrude the strands, and cut the strands to pelletize them. can. Further, by introducing the pellets into various molding machines and thermoforming them by the method described below, a molded article having a desired shape can be easily produced. On the other hand, it is also possible to obtain a molded body without going through the pellet form.
  • thermoplastic resin composition of the present invention preferably does not contain a solvent from the viewpoint of forming it into pellet form and compression molding it.
  • the content of the solvent in the thermoplastic resin composition is preferably 5% by mass or less, more preferably 1% by mass or less, and still more preferably 0.1% by mass or less.
  • the present invention provides a molded article containing the thermoplastic resin composition.
  • the molded article of the present invention can be produced by thermoforming the thermoplastic resin composition.
  • Thermoforming methods include injection molding, extrusion molding, inflation molding, blow molding, hot press molding (compression molding), vacuum forming, pressure forming, laser molding, welding, welding, etc. Molding is possible using any method.
  • Injection molding or extrusion molding is preferable from the viewpoint of performing thermoforming using the pellets described above and cutting the obtained molded product. Particularly, injection molding is preferred from the viewpoint of production efficiency, and extrusion molding is preferred from the viewpoint of higher dimensional stability.
  • the method for producing the molded article varies depending on the melting point or glass transition temperature of the thermoplastic resin (A), but when the thermoplastic resin (A) contains the polyimide resin (a1-1), the thermoplastic resin It is preferable to include a step of thermoforming the composition at 290 to 380°C. Thermoforming at temperatures above 380° C. to 400° C. is also possible, but from the viewpoint of suppressing deterioration of the thermoplastic resin (A) and other components, thermoforming at a temperature of 380° C. or lower is preferable. Specific procedures include, for example, the following method.
  • an inorganic filler (B) and various optional components as needed are added to the thermoplastic resin (A) and dry blended, and then introduced into an extruder and melted preferably at 290 to 380°C. The mixture is then melt-kneaded and extruded in an extruder to produce pellets.
  • the thermoplastic resin (A) is introduced into an extruder and melted preferably at 290 to 380°C, and the inorganic filler (B) and various optional components are introduced therein and heated in the extruder.
  • the above-mentioned pellets may be produced by melt-kneading with the plastic resin (A) and extruding it. After the pellets are dried, they are introduced into various molding machines and thermoformed, preferably at 290 to 380° C., to produce molded bodies having a desired shape.
  • the molded body obtained by the above thermoforming may be further subjected to cutting or the like to give it a desired shape.
  • an injection molded article can be produced using the thermoplastic resin composition, and then cutting can be performed to obtain a molded article having a desired shape.
  • the molded body obtained by the above-mentioned thermoforming is preferably further subjected to an annealing treatment from the viewpoint of further improving machinability and fine machinability.
  • a molded body obtained by further performing an annealing treatment after thermoforming a thermoplastic resin composition can be cut into a flat plate with low surface roughness on the cut surface and less warpage. Further, using the flat plate, finer through holes can be formed.
  • the annealing temperature can be set depending on the type of thermoplastic resin (A) used.
  • the annealing treatment temperature is a temperature lower than the melting point of the crystalline thermoplastic resin (a1) from the viewpoint of avoiding deformation of the molded product, and cutting From the viewpoint of further improving processability and microprocessability, and from the viewpoint of avoiding deformation of the molded article, when the melting point of the crystalline thermoplastic resin (a1) is Tm (°C), preferably Tm - 100°C to Tm It is in the range of -20°C.
  • the annealing treatment temperature is a temperature lower than the glass transition temperature of the amorphous thermoplastic resin (a2) from the viewpoint of avoiding deformation of the molded product.
  • the glass transition temperature of the amorphous thermoplastic resin (a2) is Tg (°C). is in the range of Tg-100°C to Tg-20°C.
  • the annealing treatment temperature include, when the thermoplastic resin (A) contains the polyimide resin (a1-1), from the viewpoint of further improving cutting workability and fine workability, and avoiding deformation of the molded body. From this point of view, the temperature is preferably in the range of 200 to 360°C, more preferably 220 to 340°C, even more preferably 240 to 330°C, even more preferably 250 to 320°C.
  • the annealing treatment time is not particularly limited, but is preferably in the range of 1 to 120 minutes, more preferably 5 to 60 minutes, from the viewpoint of further improving the machinability and micromachinability of the compact, and from the viewpoint of improving manufacturing efficiency. be.
  • the molded body can be annealed using a known heating device. After the annealing treatment, from the viewpoint of suppressing the occurrence of warping of the molded body due to residual stress, slow cooling is preferably performed to a temperature of 100° C. or lower.
  • the present invention further provides a component of an IC socket for testing (hereinafter also simply referred to as "member of the present invention” or “member”) obtained by processing the molded body.
  • a component of an IC socket for testing hereinafter also simply referred to as "member of the present invention” or “member” obtained by processing the molded body.
  • the test IC socket in this specification include an IC socket for product testing (test socket), an IC socket for burn-in test (burn-in socket), and the like.
  • the member of the present invention may be any member that constitutes at least a portion of an IC socket for testing, and includes, for example, a substantially flat member used in a region where a device to be tested is mounted. The substantially flat member has a fine through hole into which the device is fitted.
  • the member of the present invention can be produced, for example, by the following method.
  • thermoforming preferably injection molding
  • the thermoplastic resin composition to produce a molded body.
  • the molded body is cut using an electric drill or the like to obtain a cut plate.
  • This cut plate is micro-machined using an electric drill, a laser, etc. to form a plurality of through holes, thereby obtaining a member having a desired shape.
  • FIG. 1 is a schematic plan view showing an embodiment of a component 100 of an IC socket for testing.
  • 10 is a cutting plate
  • 20 is a through hole forming area.
  • the machined plate 10 used for producing the member 100 preferably has a machined surface with low surface roughness from the viewpoint of improving microfabrication properties.
  • the arithmetic mean roughness (Ra) of the cut surface of the cut plate 10 is preferably 1 ⁇ m or less, more preferably 0.8 ⁇ m or less, still more preferably 0.6 ⁇ m or less, even more preferably 0.3 ⁇ m or less.
  • the arithmetic mean roughness can be specifically measured by the method described in Examples.
  • a plurality of through-holes are regularly arranged at a narrow pitch.
  • the diameter of the through holes is usually selected in the range of ⁇ 0.01 to 0.20 mm, and the pitch is selected in the range of 0.02 to 0.40 mm.
  • the hole diameter is 0.1 mm or more, it is suitable because various probes such as wire probes or spring probes can be used. If the hole diameter is less than 0.1 mm, a wire probe with a smaller diameter can be used for more detailed inspection. This is suitable because it can be adapted.
  • the surface roughness of the cut surface is low, resulting in good cutting workability.
  • the hole diameter distribution does not increase, pattern collapse, or burrs do not easily occur, and the microprocessability is also good.
  • the molded product manufactured by injection molding or the like using the thermoplastic resin composition of the present invention has excellent cutting workability as described above, so it can be used not only for IC socket members but also for gears, bearings, wristwatch housings, etc. It is also highly adaptable to applications that require precision cutting.
  • IR measurement of the polyimide resin was performed using "JIR-WINSPEC50" manufactured by JEOL Ltd.
  • ⁇ Logarithmic viscosity ⁇ > After drying the polyimide resin at 190 to 200°C for 2 hours, a polyimide resin solution prepared by dissolving 0.100 g of the polyimide resin in 20 mL of concentrated sulfuric acid (96%, manufactured by Kanto Kagaku Co., Ltd.) was used as a measurement sample, and the Cannon-Fenske viscosity was measured. Measurements were made at 30°C using a meter.
  • ⁇ Melting point, glass transition temperature, crystallization temperature, crystallization heat value> The melting point Tm, glass transition temperature Tg, crystallization temperature Tc, and crystallization calorific value ⁇ Hm of the polyimide resin were measured using a differential scanning calorimeter device (“DSC-6220” manufactured by SII Nanotechnology Co., Ltd.). .
  • a polyimide resin was subjected to a thermal history under the following conditions in a nitrogen atmosphere. The thermal history conditions were as follows: first temperature increase (temperature increase rate: 10°C/min), then cooling (temperature decrease rate: 20°C/min), and then second temperature increase (temperature increase rate: 10°C/min).
  • the melting point Tm was determined by reading the peak top value of the endothermic peak observed at the second temperature rise.
  • the glass transition temperature Tg was determined by reading the value observed at the second temperature rise.
  • the crystallization temperature Tc was determined by reading the peak top value of the exothermic peak observed during cooling. Further, the crystallization calorific value ⁇ Hm (mJ/mg) was calculated from the area of the exothermic peak observed during cooling.
  • the half-crystallization time of the polyimide resin was measured using a differential scanning calorimeter device (“DSC-6220” manufactured by SII Nano Technology Co., Ltd.).
  • the measurement conditions for polyimide resins with a half-crystalization time of 20 seconds or less are to hold the temperature at 420°C for 10 minutes in a nitrogen atmosphere, completely melt the polyimide resin, and then perform a rapid cooling operation at a cooling rate of 70°C/min.
  • the time taken from the appearance of the observed crystallization peak to the peak top was calculated and determined.
  • Production example 1 (manufacture of polyimide resin 1) 500 g of 2-(2-methoxyethoxy) ethanol (manufactured by Nippon Nyukazai Co., Ltd.) and pyromellitic dianhydride ( 218.12 g (1.00 mol) of Mitsubishi Gas Chemical Co., Ltd. was introduced, and after nitrogen flow, the mixture was stirred at 150 rpm to form a uniform suspension solution.
  • 1,8- A mixed diamine solution was prepared by dissolving 93.77 g (0.65 mol) of octamethylene diamine (manufactured by Kanto Kagaku Co., Ltd.) in 250 g of 2-(2-methoxyethoxy)ethanol.
  • the mixed diamine solution was added slowly using a plunger pump. Although heat generation occurred during dropping, the internal temperature was adjusted to within 40 to 80°C.
  • Logarithmic viscosity is 1.30 dL/g
  • Tm is 323°C
  • Tg is 184°C
  • Tc is 266°C
  • crystallization calorific value is 21.0 mJ/mg
  • half crystallization time is less than 20 seconds
  • Mw is 55,000. there were.
  • Table 1 shows the composition and evaluation results of the polyimide resin in Production Example 1.
  • the mol% of the tetracarboxylic acid component and the diamine component in Table 1 is a value calculated from the amount of each component charged at the time of producing the polyimide resin.
  • thermoplastic resin compositions and molded bodies (1) Component (A) and component (B) shown in Table 2 were thoroughly mixed by dry blending.
  • the obtained mixed powder was mixed with a co-rotating twin-screw kneading extruder ("HK-25D-41D” manufactured by Parker Corporation, screw diameter: 25 mm) at a barrel temperature of 360°C and a screw rotation speed of 120 rpm. ⁇ 3mm strands were extruded. At this time, the discharge amount and dischargeability of the strands were observed, and the manufacturing stability of the resin composition during twin-screw extrusion was evaluated according to the following criteria.
  • ⁇ Manufacturing stability during twin screw extrusion> The discharge rate (kg/h) and extrusion properties of the strands extruded from the twin-screw kneading extruder in the above method were observed, and the production stability of the resin composition during twin-screw extrusion was evaluated according to the following criteria.
  • C The discharge amount was less than 3 kg/h.
  • the strand extruded from the extruder was air-cooled and then pelletized using a pelletizer ("Fan Cutter FC-Mini-4/N” manufactured by Hoshi Plastics Co., Ltd.).
  • the obtained pellets (thermoplastic resin composition) were dried at 150° C. for 10 hours and then used for injection molding.
  • Injection molding was performed using an injection molding machine (“Roboshot ⁇ -S30iA” manufactured by Fanuc Corporation) at a barrel temperature of 375°C, a mold temperature of 200°C, and a molding cycle of 60 seconds to form a 70 mm x 70 mm x 4 mm thick product.
  • a flat plate-shaped injection molded body was produced. The injection moldability at this time was evaluated by the following method.
  • thermoplastic resin composition examples 6, 10 to 12 (Production and evaluation of thermoplastic resin composition and molded object (2)) Component (A) and component (B) shown in Table 3 were thoroughly mixed by dry blending.
  • the obtained mixed powder was mixed with a co-rotating twin-screw extruder ("HK-25D-41D” manufactured by Parker Corporation, screw diameter: 25 mm) at a barrel temperature of 360°C and a screw rotation speed of 120 rpm. ⁇ 3mm strands were extruded.
  • the strand extruded from the extruder was air-cooled and then pelletized using a pelletizer ("Fan Cutter FC-Mini-4/N" manufactured by Hoshi Plastics Co., Ltd.).
  • the obtained pellets (thermoplastic resin composition) were dried at 150° C.
  • Injection molding was performed using an injection molding machine (“Roboshot ⁇ -S30iA” manufactured by Fanuc Corporation) at a barrel temperature of 375°C, a mold temperature of 200°C, and a molding cycle of 60 seconds to form a 70 mm x 70 mm x 4 mm thick product.
  • a flat plate-shaped injection molded body was produced.
  • the injection molded product was annealed for 60 minutes at the temperature listed in Table 3 using a constant air temperature incubator (“DN610H” manufactured by Yamato Scientific Co., Ltd.), slowly cooled to room temperature, and the injection molded product was collected. After that, evaluation was performed using the following method.
  • the injection molded article obtained by the above method was cut to produce a flat plate measuring 50 mm x 50 mm x 3 mm thick.
  • the arithmetic mean roughness (Ra) of a continuous area of 20 mm in length was measured in the direction orthogonal to the cutting direction using a 3D shape measuring device (Keyence Corporation's "VR"). -6000''), and the surface roughness was evaluated according to the following criteria.
  • Arithmetic mean roughness is 0.3 ⁇ m or less
  • LM series high-precision image dimension measuring device
  • A The diameter of all through holes is between ⁇ 0.047 and 0.053 mm.
  • C Some of the through holes have diameters exceeding the range of ⁇ 0.047 to 0.053 mm. In Table 3, those for which microfabrication itself was difficult are marked with a "-".
  • thermoplastic resin composition of the present invention a molded article having excellent cutting workability and fine workability can be produced.
  • the molded body is suitable for producing components of IC sockets for inspection, etc.

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PCT/JP2023/021667 2022-06-28 2023-06-12 熱可塑性樹脂組成物、成形体、及び、検査用ｉｃソケットの構成部材 Ceased WO2024004602A1 (ja)

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EP23831051.0A EP4549517A4 (en) 2022-06-28 2023-06-12 THERMOPLASTIC RESIN COMPOSITION, MOLDED BODY AND CONSTITUENT ELEMENT OF AN IC SOCKET FOR INSPECTION
US18/878,150 US20250388735A1 (en) 2022-06-28 2023-06-12 Thermoplastic resin composition, molded body, and constituting member of ic socket for inspection
CN202380048223.2A CN119403887A (zh) 2022-06-28 2023-06-12 热塑性树脂组合物、成型体以及检查用ic插座的构成构件
JP2024530642A JPWO2024004602A1 (https=) 2022-06-28 2023-06-12
KR1020247042675A KR20250027668A (ko) 2022-06-28 2023-06-12 열가소성 수지 조성물, 성형체, 및, 검사용 ic소켓의 구성부재

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