Classifications

• • 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
• • 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
  • 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
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
  • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
  • C08G73/1017—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)amine
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
  • C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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  • 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
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/10—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
• • 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
  • C08K3/34—Silicon-containing compounds
  • C08K2003/343—Peroxyhydrates, peroxyacids or salts thereof
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
• • 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
  • C08K3/02—Elements
  • C08K3/04—Carbon
• • 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
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/06—Elements
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/30—Applications used for thermoforming

Definitions

• the present invention relates to thermoplastic polyimide resin compositions and molded articles.
• polyimide resin Due to the rigidity of the molecular chain, resonance stabilization, and strong chemical bonding, polyimide resin is a useful engineering plastic with high thermal stability, high strength, and high solvent resistance, and is applied in a wide range of fields. Polyimide resins having crystallinity can further improve their heat resistance, strength and chemical resistance, and thus are expected to be used as metal substitutes. However, although the polyimide resin has high heat resistance, it does not show thermoplasticity and has a problem of low moldability.
• Patent Document 1 As polyimide molding materials, highly heat-resistant resin Vespel (registered trademark) and the like are known (Patent Document 1). Since it is necessary to perform molding, it is also disadvantageous in terms of cost. On the other hand, a resin such as a crystalline resin that has a melting point and is fluid at high temperatures can be molded easily and inexpensively.
• thermoplastic polyimide resins have been reported.
• Thermoplastic polyimide resins are excellent in moldability in addition to the inherent heat resistance of polyimide resins. Therefore, thermoplastic polyimide resins can also be applied to moldings used in harsh environments where general-purpose thermoplastic resins such as nylon and polyester could not be applied.
• Patent Document 2 a predetermined A thermoplastic polyimide resin is disclosed that contains a repeating unit of
• Patent Document 3 a flame-retardant polyimide containing a semi-aromatic polyimide resin and a predetermined amount of either graphite or a combination of two or more selected from the group consisting of graphite, fluororesin, and carbon fiber A molding material is disclosed. Further, in Patent Document 4, a polyimide resin composition containing a thermoplastic polyimide resin containing a predetermined repeating unit and a fluororesin that satisfies predetermined requirements is easy to mold, has high slidability and good appearance. It is disclosed that it is possible to produce a compacted product.
• the polyimide resin composition described in Patent Document 4 further contains at least one selected from the group consisting of carbon fiber and graphite for the purpose of improving various properties such as slidability, mechanical strength, and flame retardancy. It is stated that it can contain However, when the polyimide resin composition contains carbon fiber or graphite, the specific wear tends to increase, and there is room for further improvement in this respect. In particular, in the prior art, it was difficult to reduce the specific wear amount while keeping the coefficient of dynamic friction at a low level among the indices of slidability.
• the subject of the present invention is a thermoplastic polyimide resin composition capable of producing a highly slidable molded article having a high rigidity, a low coefficient of dynamic friction and a small amount of specific wear, and molding containing the thermoplastic polyimide resin composition It is about providing goods.
• thermoplastic polyimide resin A resin composition containing predetermined amounts of thermoplastic polyimide resin, carbon fiber, fluororesin, and inorganic filler can solve the above problems. That is, the present invention relates to the following.
• Thermoplastic polyimide resin A 30 to 60% by mass, carbon fiber (B) 5 to 50% by mass, fluororesin (C) 5 to 20% by mass, and inorganic filler (D) 1 to 40% by mass
• a thermoplastic polyimide resin composition containing % A molded article containing the thermoplastic polyimide resin composition described in [1] above.
• thermoplastic polyimide resin composition of the present invention it is possible to produce a highly slidable molded product with high rigidity, a low coefficient of dynamic friction, and a small amount of specific wear.
• the resin composition and molded article are suitable for applications requiring excellent rigidity and sliding properties, such as bearings for automobiles, bearings for copiers, etc., gears, bearings, bushes, mechanical seals, and transmission seals. etc. is suitably used.
• thermoplastic polyimide resin composition of the present invention is a thermoplastic polyimide resin (A) 30 to 60% by mass, carbon fiber (B) 5 to 50% by mass, fluorine It contains 5 to 20% by mass of resin (C) and 1 to 40% by mass of inorganic filler (D).
• thermoplastic polyimide resin composition of the present invention a highly slidable molded article having high rigidity, a low coefficient of dynamic friction and a small amount of specific wear can be produced.
• the flexural modulus is used as an index for "rigidity”
• the flexural strength is used as an index for "mechanical strength” or “strength”.
• the slidability is indexed by the coefficient of dynamic friction and the amount of specific wear, and the lower the coefficient of dynamic friction and the amount of specific wear, the higher the slidability.
• thermoplastic polyimide resin composition of the present invention achieves the above effect.
• the composition of the present invention has thermoplasticity and relatively high heat resistance and slidability as a thermoplastic resin composition.
• the carbon fiber (B) contributes to rigidity
• the fluororesin (C) contributes to improvement of slidability.
• predetermined amounts of these in the composition of the present invention high rigidity and slidability can be imparted.
• the molded article made of the resin composition containing the carbon fiber (B) has improved rigidity, the specific wear amount tends to increase even if the molded article contains the fluororesin (C).
• the composition of the present invention further contains a predetermined amount of the inorganic filler (D), thereby improving the hardness of the resulting molded article, thereby suppressing an increase in the specific wear loss.
• thermoplastic polyimide resin (A) (hereinafter also simply referred to as "component (A)") used in the present invention is thermoplastic, and preferably in the form of powder or pellets.
• the thermoplastic polyimide resin is formed by closing the imide ring after molding in the state of a polyimide precursor such as polyamic acid, for example, a polyimide resin having no glass transition temperature (Tg), or a temperature lower than the glass transition temperature It is distinguished from polyimide resin that decomposes at
• component (A) examples include wholly aromatic thermoplastic polyimide resins, semi-aromatic thermoplastic polyimide resins, and aliphatic thermoplastic polyimide resins.
• wholly aromatic thermoplastic polyimide resins include thermoplastic polyimide resins mainly containing repeating structural units derived from an aromatic tetracarboxylic acid component and an aromatic diamine component.
• An aromatic tetracarboxylic acid or its derivative can be used as the aromatic tetracarboxylic acid component.
• Commercially available wholly aromatic thermoplastic polyimide resins include, for example, "AURUM” manufactured by Mitsui Chemicals, Inc.
• thermoplastic polyimide resin a thermoplastic polyimide resin mainly containing repeating structural units derived from an aromatic tetracarboxylic acid component and an aliphatic diamine component, and derived from an aliphatic tetracarboxylic acid component and an aromatic diamine component and a thermoplastic polyimide resin mainly containing repeating structural units.
• the aliphatic diamine component may be either a chain aliphatic diamine or an aliphatic diamine containing a cyclic structure.
• aliphatic tetracarboxylic acid component a chain aliphatic tetracarboxylic acid, an aliphatic tetracarboxylic acid containing a cyclic structure, and derivatives thereof (anhydrides or alkyl esters) can be used.
• thermoplastic polyimide resins examples include thermoplastic polyimide resins that mainly contain repeating structural units derived from an aliphatic tetracarboxylic acid component and an aliphatic diamine component.
• the aliphatic tetracarboxylic acid component and the aliphatic diamine component are the same as above.
• mainly containing refers to the total of repeating structural units derived from the tetracarboxylic acid component and the diamine component, which constitute the main chain of the polyimide resin, preferably 50 to 100 mol%, more preferably 75 to 100 mol %, more preferably 80 to 100 mol %, still more preferably 85 to 100 mol %, and may contain other structural units as necessary.
• a semi-aromatic thermoplastic polyimide resin is preferable, and a repeating structural unit derived from an aromatic tetracarboxylic acid component and an aliphatic diamine component.
• 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) ) is a polyimide resin (A1) in which the content ratio of the repeating structural unit of the formula (1) is 20 to 70 mol % with respect to the total repeating structural units of (A1).
• R 1 is a C 6-22 divalent aliphatic group containing at least one alicyclic hydrocarbon structure.
• R 2 is a C 5-16 divalent chain aliphatic group.
• X 1 and X 2 are each independently a tetravalent aromatic group having 6 to 22 carbon atoms.
• the polyimide resin will be simply referred to as “polyimide resin (A1)", and details will be described with the polyimide resin (A1) as an example.
• R 1 is a C 6-22 divalent aliphatic group 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 It may be cyclic or polycyclic.
• Examples of the alicyclic hydrocarbon structure include, but are not limited to, cycloalkane rings such as cyclohexane ring, cycloalkene rings such as cyclohexene, bicycloalkane rings such as norbornane ring, and bicycloalkene rings such as norbornene. Do not mean.
• a cycloalkane ring is preferred, a cycloalkane ring having 4 to 7 carbon atoms is more preferred, and a cyclohexane ring is even more preferred.
• R 1 has 6 to 22 carbon atoms, preferably 8 to 17 carbon atoms.
• R 1 contains at least one, 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, more preferably 1;
• m 13 to m 15 are each independently an integer of 0 to 2; Yes, 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 may be can be any value.
• X 1 is a tetravalent aromatic group having 6 to 22 carbon atoms.
• the aromatic ring in the aromatic group may be a single ring or a condensed ring, and examples include, but are not limited to, benzene ring, naphthalene ring, anthracene ring, and tetracene ring. Among these, benzene ring and naphthalene ring are preferred, and benzene ring is more preferred.
• X 1 has 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms.
• X 1 contains at least one, preferably 1 to 3, aromatic rings.
• X 1 is preferably a tetravalent group represented by any one of formulas (X-1) to (X-4) below.
• 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.
• L 11 to L 13 are each independently a single bond, an ether group, a carbonyl group or an alkylene group having 1 to 4 carbon atoms.) Since X 1 is a tetravalent aromatic group having 6 to 22 carbon atoms, R 12 , R 13 , p 12 and p 13 in formula (X-2) are represented by formula (X-2). is selected so that the number of carbon atoms in the tetravalent aromatic group is within the range of 10 to 22. Similarly, L 11 , R 14 , R 15 , p 14 and p 15 in formula (X-3) are tetravalent aromatic groups having 12 to 22 carbon atoms.
• 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, still more preferably 8 to 10 carbon atoms.
• the chain aliphatic group means a group derived from a chain aliphatic compound, the chain aliphatic compound may be saturated or unsaturated, straight-chain It may be single 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, still more preferably an alkylene group having 7 to 12 carbon atoms, and most 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 octamethylene group and decamethylene group, and particularly preferably octamethylene group.
• R 2 is a divalent chain aliphatic group having 5 to 16 carbon atoms containing an ether group.
• the number of carbon atoms is preferably 6 to 14 carbon atoms, more preferably 7 to 12 carbon atoms, still more preferably 8 to 10 carbon atoms.
• a divalent group represented by the following formula (R2-1) or (R2-2) is preferred.
• (m 21 and m 22 are each independently an integer of 1 to 15, preferably 1 to 13, more preferably 1 to 11, still more preferably 1 to 9.
• m 23 to m 25 are each independently an integer of 1 to 14, preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 8.) Since 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, still 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, more preferably 8 to 10 carbon atoms). That is, 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) are divalent groups represented by formula (R2-2) having 5 to 16 carbon atoms (preferably 6 to 14 carbon atoms, more preferably It 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).
• X2 is defined in the same manner as X1 in Formula ( 1 ), and the 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, the polyimide resin can be sufficiently crystallized even in a general injection molding cycle. If the content ratio is 20 mol % or more, the moldability is good, and if it is 70 mol % or less, the crystallinity is high and the heat resistance is excellent.
• 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, from the viewpoint of expressing high crystallinity.
• 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 %. Within this range, the crystallinity of the polyimide resin (A1) is high, and a molded article having more excellent heat resistance can be obtained.
• the content ratio is preferably 25 mol% or more, more preferably 30 mol% or more, and still more preferably 32 mol% or more from the viewpoint of moldability, and is even more preferable from the viewpoint of expressing high crystallinity. is 35 mol % or less.
• the total content ratio of the repeating structural units of the formula (1) and the repeating structural units of the formula (2) with respect to all repeating structural units constituting the polyimide resin (A1) is preferably 50 to 100 mol%, more preferably 75 ⁇ 100 mol%, more preferably 80 to 100 mol%, still more preferably 85 to 100 mol%.
• Polyimide resin (A1) 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 sum of the repeating structural units of formula (1) and the repeating structural units 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, from the viewpoint of improving heat resistance, and is preferably 20 mol % or less, more preferably 20 mol % or less, from the viewpoint of maintaining crystallinity. Preferably, it is 15 mol % or less.
• R 3 is a C 6-22 divalent group containing at least one aromatic ring.
• X 3 is a C 6-22 tetravalent group containing at least one aromatic ring.
• R 3 is a C 6-22 divalent group containing at least one aromatic ring.
• the aromatic ring may be a single ring or a condensed ring, and examples include, but are not limited to, benzene ring, naphthalene ring, anthracene ring, and tetracene ring. Among these, benzene ring and naphthalene ring are preferred, and benzene ring is more preferred.
• R 3 has 6 to 22 carbon atoms, preferably 6 to 18 carbon atoms.
• R 3 contains at least one, preferably 1 to 3, aromatic rings. 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 (e.g., -C(CF 3 ) 2 -, -(CF 2 ) p - (where p is an integer of 1 to 10)). -CO-, -SO 2 -, -SO-, -CONH-, -COO-, etc., in addition to halogenated alkylene groups.
• 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.) Since 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- It is selected so that the number of carbon atoms of the divalent group represented by 1) falls within the range of 6-22. Similarly, L 21 , m 33 , m 34 , R 22 , R 23 , p 22 and p 23 in formula (R3-2) have It is chosen to fall within the range of 12-22.
• X3 is defined in the same manner as X1 in Formula ( 1 ), and the preferred embodiments are also the same.
• the polyimide resin (A1) 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 each independently represent a chain aliphatic group having 1 to 3 carbon atoms or a phenyl group, and 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 the preferred embodiments are also the same.
• the terminal structure of the polyimide resin (A1) is not particularly limited, it preferably has a chain aliphatic group having 5 to 14 carbon atoms at its terminal.
• the chain aliphatic group may be saturated or unsaturated, linear or branched.
• saturated chain aliphatic groups 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 and 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, and 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, still more preferably 8 or more carbon atoms, and preferably 12 or less carbon atoms, more preferably 12 or less carbon atoms. has 10 or less carbon atoms, more preferably 9 or less carbon atoms. Only one type of chain aliphatic group may be used, or two or more types may be used.
• 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 It is at least one selected from the group consisting of 2-ethylhexyl groups.
• the polyimide resin (A1) preferably has only chain aliphatic groups having 5 to 14 carbon atoms at its terminals in addition to terminal amino groups and terminal carboxy groups.
• the content thereof is preferably 10 mol % or less, more preferably 5 mol % or less, relative to the chain aliphatic group having 5 to 14 carbon atoms.
• the content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (A1) is 100 in total for all repeating structural units constituting the polyimide resin (A1). It is preferably 0.01 mol % or more, more preferably 0.1 mol % or more, and still more preferably 0.2 mol % or more based on mol %. Further, in order to secure a sufficient molecular weight and obtain good mechanical strength, the content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (A1) constitutes the polyimide resin (A1).
• the content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (A1) can be determined by depolymerizing the polyimide resin (A1).
• the polyimide resin (A1) 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 (A1) is preferably 280° C. or higher, more preferably 290° C. or higher, from the viewpoint of heat resistance, and is preferably 345° C. or lower, more preferably 345° C. or lower, from the viewpoint of achieving high moldability. is 340° C. or less, more preferably 335° C. or less.
• the glass transition temperature of the polyimide resin (A1) is more preferably 160° C. or higher, more preferably 170° C. or higher from the viewpoint of heat resistance, and preferably 250° C. from the viewpoint of expressing high moldability.
• both the melting point and the glass transition temperature of the polyimide resin (A1) can be measured by a differential scanning calorimeter, and specifically can be measured by the method described in Examples.
• the polyimide resin (A1) is measured by a differential scanning calorimeter, and after melting the polyimide resin, it is cooled at a cooling rate of 20 ° C./min.
• the heat quantity at the crystallization exothermic peak (hereinafter also simply referred to as “crystallization exothermic value”) observed when the It is preferably 17.0 mJ/mg or more, and more preferably 17.0 mJ/mg or more.
• the upper limit of the crystallization heat value is not particularly limited, it is usually 45.0 mJ/mg or less.
• the crystallization heat value of the polyimide resin (A1) can be measured by the method described in Examples.
• Logarithmic viscosity at 30 ° C. of a 0.5% by mass concentrated sulfuric acid solution of the polyimide resin (A1) is preferably in the range of 0.2 to 2.0 dL / g, more preferably 0.3 to 1.8 dL / g . If the logarithmic viscosity is 0.2 dL / g or more, sufficient mechanical strength is obtained when the resulting polyimide resin composition is molded, and if it is 2.0 dL / g or less, moldability and handling becomes better.
• the weight average molecular weight Mw of the polyimide resin (A1) is preferably 10,000 to 150,000, more preferably 15,000 to 100,000, still more preferably 20,000 to 80,000, still more preferably 30, 000 to 70,000, more preferably 35,000 to 65,000.
• the weight average molecular weight Mw of the polyimide resin (A1) can be measured by gel permeation chromatography (GPC) using polymethyl methacrylate (PMMA) as a standard sample.
• thermoplastic polyimide resin (A) can be produced by reacting a tetracarboxylic acid component and a diamine component.
• a method for producing the polyimide resin (A1) will be described below as an example.
• the tetracarboxylic acid component contains an aromatic tetracarboxylic acid and/or a derivative thereof
• the diamine component comprises an aliphatic diamine containing at least one alicyclic hydrocarbon structure and a chain containing aliphatic diamines.
• Aromatic tetracarboxylic acids are compounds in which four carboxy groups are directly bonded to an aromatic ring, and may contain alkyl groups in the structure. Further, the aromatic tetracarboxylic acid preferably has 6 to 26 carbon atoms. Examples of aromatic tetracarboxylic acids include pyromellitic acid, 2,3,5,6-toluenetetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, 3,3′,4,4′- Biphenyltetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid and the like are preferred. Among these, pyromellitic acid is more preferable.
• Derivatives of aromatic tetracarboxylic acids include anhydrides and alkyl esters of aromatic tetracarboxylic acids.
• the tetracarboxylic acid derivative preferably has 6 to 38 carbon atoms.
• Anhydrides of aromatic tetracarboxylic acids include pyromellitic monoanhydride, pyromellitic dianhydride, 2,3,5,6-toluenetetracarboxylic dianhydride, 3,3',4,4' -diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 1,4, 5,8-naphthalenetetracarboxylic dianhydride and the like.
• Alkyl esters of aromatic tetracarboxylic acids include dimethyl pyromellitic acid, diethyl pyromellitic acid, dipropyl pyromellitic acid, diisopropyl pyromellitic acid, dimethyl 2,3,5,6-toluenetetracarboxylate, and 3,3′. , dimethyl 4,4′-diphenylsulfonetetracarboxylate, dimethyl 3,3′,4,4′-benzophenonetetracarboxylate, dimethyl 3,3′,4,4′-biphenyltetracarboxylate, 1,4,5 , 8-naphthalenetetracarboxylic acid dimethyl.
• the alkyl group preferably has 1 to 3 carbon atoms.
• aromatic tetracarboxylic acid and/or its derivative at least one compound selected from the above may be used alone, or two or more compounds may be used in combination.
• the aliphatic 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-methylcyclohexyl amine), carvonediamine, limonenediamine, isophoronediamine, norbornanediamine, bis(aminomethyl)tricyclo[5.2.1.0 2,6 ]decane, 3,3′-dimethyl-4,4′-diaminodicyclohexyl Methane, 4,4'-diaminodicyclohexylpropane and the like are preferred.
• Aliphatic 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. In addition, if the chain portion has 5 to 16 carbon atoms, an ether bond may be included therebetween.
• Chain aliphatic diamines such as 1,5-pentamethylenediamine, 2-methylpentane-1,5-diamine, 3-methylpentane-1,5-diamine, 1,6-hexamethylenediamine, 1,7-hepta methylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 1,10-decamethylenediamine, 1,11-undecamethylenediamine, 1,12-dodecamethylenediamine, 1,13-trideca Methylenediamine, 1,14-tetradecamethylenediamine, 1,16-hexadecamethylenediamine, 2,2'-(ethylenedioxy)bis(ethyleneamine) and the like are preferred.
• Chain aliphatic diamines may be used singly 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-octamethylenediamine and 1,10-decamethylenediamine is particularly preferable. Available.
• the total amount of the aliphatic diamine and the chain aliphatic diamine containing at least one alicyclic hydrocarbon structure the aliphatic diamine containing at least one alicyclic hydrocarbon structure
• the molar ratio of charged amount is preferably 20 to 70 mol %.
• the molar amount is preferably 25 mol% or more, more preferably 30 mol% or more, still 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.
• mol % or less more preferably less than 40 mol %, more preferably 35 mol % or less.
• 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 orthoxylylenediamine, metaxylylenediamine, paraxylylenediamine, 1,2-diethynylbenzenediamine, 1,3-diethynyl.
• the lower limit of the molar ratio is not particularly limited as long as it exceeds 0 mol %. From the viewpoint of improving heat resistance, it is preferably 5 mol % or more, more preferably 10 mol % or more. Further, the molar ratio is preferably 25 mol % or less, preferably 20 mol % or less, more preferably 15 mol % or less from the viewpoint of maintaining crystallinity.
• the molar ratio is preferably 12 mol% or less, more preferably 10 mol% or less, even more preferably 5 mol% or less, and even more preferably 0 mol%. .
• the charging ratio of the tetracarboxylic acid component and the diamine component is preferably 0.9 to 1.1 mol of the diamine component with respect to 1 mol of the tetracarboxylic acid component.
• the polyimide resin (A1) it is preferable to mix a terminal blocking agent in addition to the tetracarboxylic acid component and the diamine component.
• a terminal blocking agent at least one selected from the group consisting of monoamines and dicarboxylic acids is preferable.
• the amount of the terminal blocker to be used may be an amount that can introduce a desired amount of terminal groups into the polyimide resin (A1), and is 0.0001 to 0.001 to 0.001 to 1 mol of the tetracarboxylic acid and/or derivative thereof. 1 mol is preferred, 0.001 to 0.06 mol is more preferred, and 0.002 to 0.035 mol is even more preferred.
• a monoamine terminal blocking agent is preferable as the terminal blocking agent, and from the viewpoint of improving heat aging resistance by introducing the chain aliphatic group having 5 to 14 carbon atoms described above at the end of the polyimide resin (A1). , monoamines having a chain aliphatic group of 5 to 14 carbon atoms are more preferred, and monoamines having a saturated linear aliphatic group of 5 to 14 carbon atoms are even more preferred.
• the terminal blocking 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, most preferably n-octylamine, isooctylamine, and 2-ethylhexylamine.
• thermoplastic polyimide resin (A) A known polymerization method can be applied as the polymerization method for producing the thermoplastic polyimide resin (A).
• a method for producing the polyimide resin (A1) the method described in International Publication No. 2016/147996 can be used.
• the thermoplastic polyimide resin composition of the present invention contains carbon fiber as component (B) from the viewpoint of improving rigidity.
• component (B) used in the composition of the present invention include polyacrylonitrile-based carbon fibers and pitch-based carbon fibers.
• the form of the carbon fiber is not particularly limited, and depending on the form of the resulting thermoplastic polyimide resin composition and molded article, either continuous fiber or staple fiber can be used, or both can be used in combination.
• the component (B) is short fibers having an average fiber length of less than 10 mm from the viewpoint of extrusion moldability. preferable.
• the average fiber length of the component (B), which is short fibers, is more preferably 0.5 to 8 mm, more preferably 2 to 8 mm.
• the average fiber diameter of component (B) is preferably 1 to 100 ⁇ m, more preferably 3 to 50 ⁇ m, still more preferably 4 to 20 ⁇ m. When the average fiber diameter of the component (B) is within this range, processing is easy, and the resulting molded article has excellent rigidity.
• the average fiber length (in the case of short fibers) and average fiber diameter of component (B) are observed and measured by randomly selecting 50 or more fibers with a scanning electron microscope (SEM) or the like, and the number average is calculated. It is obtained by calculating
• the number of filaments of component (B) is usually in the range of 500-100,000, preferably 5,000-80,000, more preferably 10,000-70,000.
• the component (B) is preferably surface-treated with a surface treatment agent.
• the surface treatment agent is a concept including a sizing agent and a sizing agent.
• Examples of surface treatment agents include epoxy-based materials, urethane-based materials, acrylic materials, polyamide-based materials, polyester-based materials, vinyl ester-based materials, polyolefin-based materials, and polyether-based materials.
• a species or a combination of two or more species can be used. At least one selected from the group consisting of epoxy-based materials and urethane-based materials is preferable as the surface treatment agent from the viewpoint of obtaining higher rigidity.
• the amount of treatment with the component (B) surface treatment agent can be appropriately selected depending on the type of surface treatment agent, the form of the carbon fiber, and the like.
• the amount of the sizing agent attached is preferably is in the range of 1.5 to 10% by weight, more preferably 2 to 5% by weight.
• a commercially available product can also be used as the component (B).
• Examples of commercially available carbon fibers include chopped fibers “CFUW”, “CFEPP”, “CFEPU”, “CFA4", "FX1", “EX1”, and “BF-WS” manufactured by Nippon Polymer Sangyo Co., Ltd. , "CF-N” series, Mitsubishi Chemical's “Pyrofil Chopped Fiber” series, and Teijin Limited's "Tenax Chopped Fiber” series.
• thermoplastic polyimide resin composition of the present invention contains a fluororesin as component (C) from the viewpoint of improving slidability.
• the component (C) used in the composition of the present invention includes, for example, polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), a co-polymer of tetrafluoroethylene and hexafluoropropylene.
• FEP Polymer
• PFA copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether
• ETFE copolymer of tetrafluoroethylene and ethylene
• polytetrafluoroethylene is preferable from the viewpoint of improving slidability and heat resistance.
• Component (C) used in the present invention is preferably in the form of powder from the viewpoint of dispersibility in component (A) and handleability.
• its average particle size (D50) is not particularly limited, but from the viewpoint of dispersibility in component (A) and handleability, it is preferably 1 to 50 ⁇ m, more preferably 2 to 50 ⁇ m. 40 ⁇ m, more preferably 3-30 ⁇ m, even more preferably 5-20 ⁇ m.
• the average particle diameter (D50) can be measured with a laser diffraction light scattering particle size distribution analyzer.
• polytetrafluoroethylene includes, for example, Kitamura Co., Ltd. "KT-300M”, “KT-400M”, “KT-600M”, “KTL-450A”, “KTL-450”, “KTL-610", “KTL-610A”, “KTL-620", “KTL-20N”, “KTL-10N”, “KTL-10S”, “KTL-9N”, “KTL-9S”, “KTL” -8N", “KTL-4N", "KTL-2N”, “KTL-1N”, “KTL-8F”, “KTL-8FH”, “KTL-500F", 3M Dynion PTFE manufactured by 3M Japan Ltd.
• Examples include micropowder "TF9201Z”, “TF9205", “TF9207”, “Polyflon PTFE-M” series, “Polyflon PTFE-F” series and “Polyflon PTFE Rubron” series manufactured by Daikin Industries, Ltd.
• the thermoplastic polyimide resin composition of the present invention contains an inorganic filler as component (D) from the viewpoint of reducing the specific wear loss of the resulting molded article.
• component (D) in the present invention does not include fillers consisting only of carbon atoms, such as graphite and graphite.
• the shape of component (D) used in the composition of the present invention is not particularly limited, and examples thereof include spherical, plate-like and fibrous shapes.
• Component (D) includes, for example, silica, alumina, kaolinite, wollastonite (calcium silicate), mica, talc, clay, sericite, magnesium carbonate, calcium carbonate, magnesium sulfate, calcium oxide, titanium oxide, carbonization Silicon, antimony trisulfide, tin sulfide, copper sulfide, iron sulfide, bismuth sulfide, zinc sulfide, metal powder, glass powder, glass flakes, glass beads, glass balloon, metal fiber, silica fiber, silica-alumina fiber, alumina fiber, Zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, potassium titanate whisker, aluminum borate whisker, magnesium-based whisker, silicon-based whisker, etc., and one or more of these can be used. .
• the component (D) is preferably an inorganic filler containing calcium element, more preferably a group consisting of calcium carbonate and wollastonite, from the viewpoint of further reducing the specific wear amount of the resulting molded article.
• Inorganic fillers containing calcium elements have a moderately high Mohs hardness, which increases the hardness of the molded product obtained, and increases the amount of wear due to the abrasion powder generated by abrasion of the molded product acting as an abrasive. can be suppressed, it is thought that the specific wear amount can be further reduced.
• the size of component (D) also varies depending on the shape of the inorganic filler.
• the average particle diameter is preferably from 0.01 to 0.01 from the viewpoint of improving mechanical strength, reducing specific wear loss, and improving dispersibility in component (A). 50 ⁇ m, more preferably 0.1 to 30 ⁇ m, still more preferably 0.2 to 20 ⁇ m, still more preferably 0.2 to 15 ⁇ m, still more preferably 0.2 to 10 ⁇ m, still more preferably 0.5 to 5 ⁇ m be.
• the average particle size can be measured by the same method as for component (C).
• the average fiber length is preferably 5 to 300 ⁇ m, from the viewpoint of improving mechanical strength, reducing specific wear loss, and improving dispersibility in component (A) It is preferably 10 to 180 ⁇ m, and the average fiber diameter is preferably 0.1 to 100 ⁇ m, more preferably 0.2 to 50 ⁇ m, still more preferably 0.2 to 20 ⁇ m.
• the average fiber length and average fiber diameter of the fibrous inorganic filler can be measured in the same manner as for component (B).
• thermoplastic polyimide resin composition of the present invention is high in rigidity, and from the viewpoint of obtaining a highly slidable molded article with a low coefficient of dynamic friction and a small amount of specific wear. , preferably in the following range.
• the content of component (A) in the thermoplastic polyimide resin composition is 30-60% by mass, preferably 35-60% by mass, more preferably 40-55% by mass. If the content of component (A) in the thermoplastic polyimide resin composition is 30% by mass or more, molding processability is good, and if it is 60% by mass or less, rigidity and slidability are good.
• the content of component (B) in the thermoplastic polyimide resin composition is 5 to 50% by mass, preferably 5 to 40% by mass, more preferably 10 to 35% by mass, still more preferably 10 to 30% by mass. is. If the content of the component (B) in the thermoplastic polyimide resin composition is 5% by mass or more, the effect of improving rigidity is obtained, and if it is 50% by mass or less, molding processability is reduced, specific wear amount and dynamic friction coefficient are reduced. You can control the increase.
• the content of component (C) in the thermoplastic polyimide resin composition is 5-20% by mass, preferably 5-15% by mass. If the content of the component (C) in the thermoplastic polyimide resin composition is 5% by mass or more, the effect of improving slidability can be obtained, and if it is 20% by mass or less, the rigidity can be maintained.
• the content of component (D) in the thermoplastic polyimide resin composition is 1 to 40% by mass, preferably 5 to 40% by mass, more preferably 5 to 30% by mass, still more preferably 10 to 30% by mass. is. If the content of component (D) in the thermoplastic polyimide resin composition is 1% by mass or more, the specific wear amount can be reduced, and if it is 40% by mass or less, moldability can be maintained.
• the total content of components (A) to (D) in the thermoplastic polyimide resin composition is preferably 50% by mass or more, more preferably 65% by mass or more, and still more preferably 70% by mass, from the viewpoint of obtaining the effects of the present invention. % by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and 100% by mass or less.
• the thermoplastic polyimide resin composition of the present invention may further contain graphite as component (E) from the viewpoint of imparting various properties such as blackness and flame retardancy.
• Graphite used as component (E) may be either natural graphite or artificial graphite, for example, flake graphite, flaky graphite (vein graphite, also referred to as massive graphite), earthy graphite, spherical graphite, etc. natural graphite, expanded graphite obtained by chemically treating flake graphite with concentrated sulfuric acid or the like and then heating it, expanded graphite obtained by heat-treating expanded graphite at a high temperature, and artificial graphite.
• natural graphite is preferable as the graphite used for the component (E), and at least one selected from the group consisting of flake graphite and flake graphite is more preferable.
• Component (E) may be surface-treated with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or the like, as long as the effects of the present invention are not impaired.
• the average particle size of component (E) is not particularly limited, but from the viewpoint of improving various properties such as blackness and flame retardancy, and from the viewpoint of dispersibility in component (A) and handleability, it is preferably 1 to 50 ⁇ m, More preferably 2 to 40 ⁇ m, still more preferably 3 to 30 ⁇ m, still more preferably 5 to 20 ⁇ m.
• the average particle size can be measured by the same method as for component (C).
• a commercially available product can also be used as the component (E) graphite.
• Examples of commercially available graphite include flake graphite "BF-3AK”, “BF-15AK”, “FBF”, “CBR”, “CPB-6S”, and “CPB-3” manufactured by Chuetsu Graphite Co., Ltd. , "96L”, “96L-3”, “K-3”, scale graphite “BF-10AK”, “HLP”, spherical graphite "WF-15C”, scale graphite powder CP series manufactured by Nippon Graphite Industry Co., Ltd.
• the content of component (E) in the thermoplastic polyimide resin composition is preferably 0.1 to 15 mass%, more preferably 1 to 15 mass. %, more preferably 5 to 15 mass %, even more preferably 5 to 10 mass %. If the content of the component (E) in the thermoplastic polyimide resin composition is 0.1% by mass or more, the effect of imparting various properties such as blackness and flame retardancy is easily obtained, and if it is 15% by mass or less, molding A decrease in workability can be suppressed. When emphasizing the mechanical strength and slidability improvement of the resulting molded article, the content of component (E) in the thermoplastic polyimide resin composition is preferably less than 10% by mass, more preferably It is 5% by mass or less.
• the thermoplastic polyimide resin composition of the present invention contains a matting agent, a nucleating agent, a plasticizer, an antistatic agent, an anti-coloring agent, an anti-gelling agent, a coloring agent, an antioxidant, a conductive agent, a resin modifier, Additives such as flame retardants can be incorporated as required.
• the amount of the above additive is not particularly limited, but from the viewpoint of expressing the effect of the additive without impairing the effect of the present invention, it is usually 50% by mass or less, preferably 35% by mass, in the thermoplastic polyimide resin composition. % by mass or less, more preferably 0.0001 to 30% by mass, still more preferably 0.001 to 15% by mass, even more preferably 0.01 to 10% by mass, still more preferably 0.01 to 5% by mass %.
• thermoplastic polyimide resin composition of the present invention may contain resins other than the component (A) as long as the properties thereof are not impaired.
• resins include polyamide resins, polyester resins, polycarbonate resins, polyetherimide resins, polyamideimide resins, polyphenylene etherimide resins, polyphenylene sulfide resins, polysulfone resins, polyethersulfone resins, polyarylate resins, liquid crystal polymers, and polyetherimide resins.
• thermoplastic polyimide resin composition of the present invention can take any form, but from the viewpoint of extrusion molding to produce a molded product, it is preferably powder or pellets, more preferably pellets. .
• a pellet made of a thermoplastic polyimide resin composition can be produced, for example, as follows. First, component (C), component (D), component (E) used as necessary, and various other optional components are added and dry-blended. Next, the dry blend and component (B) are side-fed to component (A) melted in advance in an extruder, melt-kneaded, extruded into strands, and cut into strands.
• a molded article having a desired shape can be easily produced by introducing the pellets into various molding machines and thermoforming them by the method described below.
• the present invention provides a molded article containing the thermoplastic polyimide resin composition. Since the thermoplastic polyimide resin composition of the present invention has thermoplasticity derived from the component (A), the molded article of the present invention can be easily produced by thermoforming. For example, after drying the pellets of the thermoplastic polyimide resin composition obtained by the above method, the pellets can be introduced into various molding machines and thermoformed to produce a molded article having a desired shape. Examples of thermoforming methods include injection molding, extrusion molding, sheet extrusion molding, blow molding, hot press molding, vacuum molding, pressure molding, laser molding, insert molding, welding, and welding. Molding is possible by any method. Among them, injection molding is preferable because molding can be performed without setting the molding temperature to a high temperature exceeding, for example, 400°C.
• thermoplastic polyimide resin composition of the present invention is excellent in moldability, and can be used to produce molded articles with high rigidity, low dynamic friction coefficient, low specific wear, and high slidability.
• the molded product can be applied to applications that require excellent rigidity and sliding properties, such as bearings for automobiles, bearings for copiers, etc., gears, bearings, bushes, mechanical seals, transmission seals, etc. .
• thermoplastic polyimide resin was prepared using "JIR-WINSPEC50" manufactured by JEOL Ltd.
• thermoplastic polyimide resin The melting point Tm, glass transition temperature Tg, crystallization temperature Tc, and crystallization heat value ⁇ Hm of the thermoplastic polyimide resin were measured using a differential scanning calorimeter ("DSC-6220" manufactured by SII Nanotechnology Co., Ltd.). It was measured.
• a thermoplastic polyimide resin was subjected to a thermal history under the following conditions in a nitrogen atmosphere. The thermal history conditions were a first temperature increase (temperature increase rate of 10° C./min), then cooling (temperature decrease rate of 20° C./min), and then a second temperature increase (temperature increase rate of 10° C./min).
• the melting point Tm was determined by reading the peak top value of the endothermic peak observed the second time the temperature was raised.
• the glass transition temperature Tg was determined by reading the value observed at the second heating.
• the crystallization temperature Tc was determined by reading the peak top value of the exothermic peak observed during cooling.
• the crystallization heat value ⁇ Hm (mJ/mg) was calculated from the area of the exothermic peak observed during cooling.
• thermoplastic polyimide resin was measured using a differential scanning calorimeter ("DSC-6220" manufactured by SII Nanotechnology Co., Ltd.). After holding at 420 ° C. for 10 minutes in a nitrogen atmosphere to completely melt the thermoplastic polyimide resin, when performing a rapid cooling operation at a cooling rate of 70 ° C./min, the peak from the appearance of the crystallization peak observed Calculate the time it took to reach the top. In addition, in Table 1, when the semi-crystallization time was 20 seconds or less, it was described as " ⁇ 20".
• the cutting test piece After cutting the ISO multi-purpose test piece to a thickness of 80 mm ⁇ 10 mm ⁇ 4 mm, the cutting test piece was used to measure bending strength (unit: MPa) and bending elastic modulus (unit: GPa) at a temperature of 23 ° C. in accordance with ISO 178. It was measured.
• thermoplastic polyimide resin 1 2-(2-methoxyethoxy) ethanol (Nippon Emulsifier Co., Ltd. )) and 218.12 g (1.00 mol) of pyromellitic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.) were introduced, and after nitrogen flow, the mixture was stirred at 150 rpm to form a uniform suspension. .
• 1,8- A mixed diamine solution was prepared by dissolving 93.77 g (0.65 mol) of octamethylenediamine (manufactured by Kanto Chemical Co., Ltd.) in 250 g of 2-(2-methoxyethoxy)ethanol. This mixed diamine solution was slowly added into the flask using a plunger pump. Heat was generated by the dropwise addition, but the internal temperature was adjusted to be within the range of 40 to 80°C.
• thermoplastic polyimide resin 1 powder was washed with 300 g of 2-(2-methoxyethoxy)ethanol and 300 g of methanol, filtered, and dried in a dryer at 180° C. for 10 hours to obtain 317 g of thermoplastic polyimide resin 1 powder. got When the IR spectrum of thermoplastic polyimide resin 1 was measured, characteristic absorption of the imide ring was observed at ⁇ (C ⁇ O) 1768, 1697 (cm ⁇ 1 ).
• Table 1 shows the composition and physical property measurement results of thermoplastic polyimide resin 1 in Production Example 1.
• the mol % of the tetracarboxylic acid component and the diamine component in Table 1 are values calculated from the amount of each component charged during the production of the polyimide resin.
• thermoplastic polyimide resin composition Each component was weighed so as to obtain the composition shown in Table 2, which will be described later.
• the fluororesin, inorganic filler, and graphite were blended in a tumbler.
• the temperature setting of the extruder was 340° C., and the screw rotation speed was 150 rpm.
• Comparative Example 3 is a thermoplastic polyimide resin A pellet consisting of 1) was produced. Using the obtained pellets, test pieces were prepared as described above, and various evaluations were performed. Table 2 shows the results.
• the molded articles made of the thermoplastic polyimide resin of this example had a specific wear amount of 12.0 (10 ⁇ 4 mm 3 /N ⁇ km) or less, which was obtained in Comparative Examples 1 to 4. Compared with the molded product, the specific wear amount was small and the dynamic friction coefficient was able to achieve 0.600 or less. In addition, the molded article of this example also had good mechanical properties, and in particular showed a higher value than those of Comparative Examples 1, 3 and 4 in flexural modulus. From the comparison between Example 4 and Comparative Example 2, it can be seen that the slidability is inferior when graphite is used instead of the component (D).
• thermoplastic polyimide resin composition of the present invention it is possible to produce a highly slidable molded product with high rigidity, a low coefficient of dynamic friction, and a small amount of specific wear.
• the resin composition and molded article are suitable for applications requiring excellent rigidity and sliding properties, such as bearings for automobiles, bearings for copiers, etc., gears, bearings, bushes, mechanical seals, and transmission seals. etc. is suitably used.

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• 2022
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  • 2022-03-17 WO PCT/JP2022/012143 patent/WO2022220007A1/ja not_active Ceased
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