Classifications

• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • 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
  • 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
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • 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
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
• • 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
  • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
  • B32B2379/08—Polyimides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2379/00—Characterised by the use 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 C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present invention relates to polyimide resin compositions and molded articles.
• Polyimide resins are useful engineering plastics with high thermal stability, high strength, and high solvent resistance due to the rigidity of the molecular chain, resonance stabilization, and strong chemical bonding, and are applied in a wide range of fields.
• polyimide resins have high heat resistance, they do not exhibit thermoplasticity and have a problem of low moldability.
• polyimide resins having thermoplasticity have also 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 cannot be used.
• thermoplasticity to polyimide resins As one of the molecular designs for imparting thermoplasticity to polyimide resins, a method of incorporating a flexible structure such as an aliphatic structure into the main chain is generally known.
• the aliphatic structure has the merits of being able to impart thermoplasticity to polyimide relatively easily, and being easy to exhibit low dielectric properties due to its bulkiness.
• thermoplastic polyimide resins there is a problem that it is inferior to the aromatic structure in oxidation resistance, and as a result, the high flame retardancy inherent in polyimide is lowered.
• Patent Document 1 describes that a polyimide resin composition containing a polyimide resin having a specific structure and a metal phosphinate flame retardant is excellent in moldability and can achieve both high flame retardancy and good appearance. is disclosed.
• polyimide resins semi-aromatic polyimide resins, wholly aliphatic polyimide resins, or polyimide resins having bulky substituents such as fluorine, in addition to the high heat resistance and dimensional stability inherent in polyimide resins, As a resin material, it can achieve extremely low dielectric properties (low dielectric constant and low dielectric loss tangent). Therefore, polyimide resin is attracting attention for its application to 5th generation mobile communication system (5G)-related members (flexible printed circuit boards, antennas, etc.), which require low dielectric properties, and other electrical and electronic members.
• 5G 5th generation mobile communication system
• An object of the present invention is to provide a polyimide resin composition capable of producing a molded article having both high flame retardancy and good appearance even when the thickness is thin (for example, 500 ⁇ m or less).
• the present inventors have found that a polyimide resin composition containing a polyimide resin obtained by combining specific different polyimide structural units at a specific ratio and an organic flame retardant having a specific structure can solve the above problems. That is, the present invention relates to the following. [1] A repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2) are included, and the sum of the repeating structural unit of the formula (1) and the repeating structural unit of the formula (2) A polyimide resin composition containing a polyimide resin (A) having a content ratio of the repeating structural unit of the formula (1) of 20 to 70 mol% and a compound (B) represented by the following formula (5).
• R 1 is a C 6-22 divalent 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 group having 6 to 22 carbon atoms containing at least one aromatic ring.
• R 51 is an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms
• R 52 to R 53 and R 61 to R 66 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms
• p 51 is an integer of 0 to 6
• p 52 and p 53 are each independently an integer of 0 to 4
• p 63 and p 66 are each independently an integer of 0 to 3 an integer, when p 51 to p 53 , p 63 or p 66 is 2 or more, a plurality of R 51 to R 53 , R 63 or R
• the polyimide resin composition of the present invention it is possible to produce a molded article that achieves both high flame retardancy and good appearance even when the thickness is thin (for example, 500 ⁇ m or less). Furthermore, the polyimide resin composition and molded articles containing the same have high heat resistance (high glass transition temperature) and low dielectric properties.
• the polyimide resin composition and molded article of the present invention are used for applications requiring high flame retardancy, low dielectric constant and low dielectric loss tangent, for example, 5G, or 70G to 300GHz frequency band 6th generation Mobile communication system (6G) related parts, various antennas, various antenna substrates, wire coating materials, bonding sheets, insulating films, raw materials for carbon fiber reinforced plastics (CFRP), high frequency circuit boards, printed wiring boards, chip-on-films (COF) Flexible substrates, multilayer laminates, LED mounting substrates, industrial robot substrates, home robot communication substrates, semiconductor element materials, high frequency device wafers, Wi-fi chips, wireless communication devices, transmission lines, bearing coatings, heat insulation Shafts, trays, various belts, heat-resistant low-dielectric tape, heat-resistant low-dielectric tubes, various sensors, various radars, radomes (radomes), optical communication modules (TOSA/ROSA), 8k-TV cable mobile terminals or digital home appliances, bases Stations, drones, surveillance cameras, indoor or outdoor
• the polyimide resin composition of the present invention comprises a repeating structural unit represented by the following formula (1) and a repeating structural unit represented by the following formula (2), wherein the repeating structural unit of the formula (1) and the formula (2) contains a polyimide resin (A) having a content ratio of 20 to 70 mol % of repeating structural units of the formula (1) with respect to the total repeating structural units of and a compound (B) represented by the following formula (5).
• R 1 is a C 6-22 divalent 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 group having 6 to 22 carbon atoms containing at least one aromatic ring.
• R 51 is an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms
• R 52 to R 53 and R 61 to R 66 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms
• p 51 is an integer of 0 to 6
• p 52 and p 53 are each independently an integer of 0 to 4
• p 63 and p 66 are each independently an integer of 0 to 3 an integer, when p 51 to p 53 , p 63 or p 66 is 2 or more, a plurality of R 51 to R 53 , R 63 or R 66 may be the same or different
• n is 1; is an integer of ⁇ 10.
• the polyimide resin composition of the present invention expresses thermoplasticity by containing a polyimide resin (A) obtained by combining specific different polyimide structural units in the above specific ratio, and a resin composition having excellent moldability. Become.
• a molded article that can achieve both high flame retardancy and good appearance even when the thickness is thin (for example, 500 ⁇ m or less) can be obtained. can be made.
• Compound (B) has high heat resistance among aromatic condensed phosphate flame retardants.
• the polyimide resin (A) since it is an organic flame retardant with a melting point, it is compatible with the polyimide resin (A) during thermoforming, unlike a granular flame retardant that does not have a melting point such as a metal phosphinate flame retardant. It is considered relatively high. Therefore, according to the polyimide resin composition of the present invention, even when a molded article having a small thickness is produced, high flame retardancy can be exhibited, and the compound (B) precipitates, thermally decomposes, and bleeds out in the molded article. etc. are unlikely to occur, and it is thought that a good appearance can be maintained.
• the polyimide resin (A) is a highly crystalline thermoplastic resin, and when a granular flame retardant having no melting point such as a metal phosphinate flame retardant is added thereto, the flame retardant acts as a crystal nucleating agent. It tends to promote crystallization. In general, if the crystallization of the crystalline thermoplastic resin is too rapid, solidification proceeds as the crystallization progresses, and the extrudability during melt-kneading and cooling may decrease. However, the compound (B) has the effect of delaying the crystallization of the polyimide resin (A), that is, reducing the solidification speed, and also has the effect of improving the extrudability of the resulting polyimide resin composition. Furthermore, since the polyimide resin composition containing the compound (B) can maintain or improve the low dielectric properties derived from the polyimide resin (A), it can achieve extremely low dielectric constant and dielectric loss tangent as a resin material.
• the polyimide resin (A) used in the present invention 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 formula (
• the content ratio of the repeating structural units of formula (1) to the total repeating structural units of 2) is 20 to 70 mol %.
• R 1 is a C 6-22 divalent 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 group having 6 to 22 carbon atoms containing at least one aromatic ring.
• the polyimide resin (A) used in the present invention is a thermoplastic resin, and its form is preferably 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
• R 1 is a C 6-22 divalent 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;
• 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 may be can be any value.
• X 1 is a tetravalent group having 6 to 22 carbon atoms 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.
• 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 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 within the range of 10 to 22. Similarly, L 11 , R 14 , R 15 , p 14 and p 15 in formula (X-3) are in the range of 12 to 22 carbon atoms in the tetravalent group represented by formula (X-3).
• L 12 , L 13 , R 16 , R 17 , R 18 , p 16 , p 17 and p 18 in formula (X-4) are selected to contain tetravalent is selected so that the number of carbon atoms in the group is in the range of 18-22.
• 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, 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 an octamethylene group and a decamethylene group, and more preferably an 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.
• the content ratio is less than 20 mol %, moldability is deteriorated, and when it exceeds 70 mol %, crystallinity is deteriorated, resulting in deterioration of 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 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 (A) is high, and a resin composition 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 (A) 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 (A) 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.
• Polyimide resin (A) 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 (A) 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 thereof 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 (A) 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 (A) is 100 in total of all repeating structural units constituting the polyimide resin (A). 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 %.
• the content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (A) is It is preferably 10 mol % or less, more preferably 6 mol % or less, still more preferably 3.5 mol % or less, based on a total of 100 mol % of all repeating structural units.
• the content of the chain aliphatic group having 5 to 14 carbon atoms in the polyimide resin (A) can be obtained by depolymerizing the polyimide resin (A).
• Polyimide resin (A) 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 more preferably 280° C. or higher, 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 expressing high moldability. 335° C. or lower, more preferably 335° C. or lower.
• the glass transition temperature of the polyimide resin (A) 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. Below, more preferably 230° C.
• both the melting point and glass transition temperature of the polyimide resin (A) can be measured with a differential scanning calorimeter.
• the polyimide resin (A) 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 melting point, glass transition temperature and heat of crystallization of the polyimide resin (A) can be measured by the methods described in Examples.
• Logarithmic viscosity at 30 ° C. of 0.5 mass% concentrated sulfuric acid solution of polyimide resin (A) 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 formed into a molded product, 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 (A) 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. If the weight-average molecular weight Mw of the polyimide resin (A) is 10,000 or more, the mechanical strength of the molded article obtained is good, and if it is 40,000 or more, the stability of the mechanical strength is good. ,000 or less, the moldability is improved.
• the weight average molecular weight Mw of the polyimide resin (A) can be measured by gel permeation chromatography (GPC) using polymethyl methacrylate (PMMA) as a standard sample.
• Polyimide resin (A) can be produced by reacting a tetracarboxylic acid component and a diamine component.
• the tetracarboxylic acid component contains a tetracarboxylic acid and/or derivative thereof containing at least one aromatic ring
• the diamine component contains a diamine containing at least one alicyclic hydrocarbon structure and a linear 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.
• the tetracarboxylic acid preferably has 6 to 26 carbon atoms.
• Examples of the tetracarboxylic acid include pyromellitic acid, 2,3,5,6-toluenetetracarboxylic acid, 3,3′,4,4′-benzophenonetetracarboxylic acid, and 3,3′,4,4′-biphenyl. Tetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid and the like are preferred. Among these, pyromellitic acid is more preferable.
• Derivatives of tetracarboxylic acids containing at least one aromatic ring include anhydrides or alkyl esters of tetracarboxylic acids containing at least one aromatic ring.
• the tetracarboxylic acid derivative preferably has 6 to 38 carbon atoms.
• Anhydrides of tetracarboxylic acids 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, 8-naphthalenetetracarboxylic dianhydride and the like are included.
• alkyl esters of tetracarboxylic acids include dimethyl pyromellitic acid, diethyl pyromellitic acid, dipropyl pyromellitic acid, diisopropyl pyromellitic acid, dimethyl 2,3,5,6-toluenetetracarboxylate, 3,3′,4 ,4′-diphenylsulfonetetracarboxylate dimethyl, 3,3′,4,4′-benzophenonetetracarboxylate dimethyl, 3,3′,4,4′-biphenyltetracarboxylate dimethyl, 1,4,5,8 -Naphthalenetetracarboxylate dimethyl 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) , carvonediamine, 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. 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 molar amount of the diamine charged containing at least one alicyclic hydrocarbon structure with respect to the total amount of the diamine containing at least one alicyclic hydrocarbon structure and the chain aliphatic diamine The ratio is preferably 20-70 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.
• 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 molar ratio of the charged amount of the diamine containing at least one aromatic ring to the total amount of the diamine containing at least one alicyclic hydrocarbon structure and the chain aliphatic diamine is 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, and more preferably 20 mol % or less. Preferably, it is 15 mol % or less.
• 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 charged amount 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.
• a terminal blocking agent may be mixed in addition to the tetracarboxylic acid component and the diamine component.
• the terminal blocking agent at least one selected from the group consisting of monoamines and dicarboxylic acids is preferable.
• the amount of the terminal blocking agent used may be an amount that can introduce a desired amount of terminal groups into the polyimide resin (A), 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 (A). , 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.
• polymerization method for producing the polyimide resin (A) As a polymerization method for producing the polyimide resin (A), a known polymerization method can be applied, and the method described in International Publication No. 2016/147996 can be used.
• the polyimide resin composition of the present invention contains a polyimide resin (A) and a compound (B) represented by the following formula (5).
• the compound (B) represented by the formula (5) as a flame retardant for the polyimide resin (A) having the specific structure, the molded article obtained has a high flame retardancy even when the thickness is thin. Flammability and good appearance are obtained.
• the extrudability of the polyimide resin composition can be improved, and furthermore, extremely low dielectric constant and dielectric loss tangent can be achieved as a resin material.
• R 51 is an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms;
• R 52 to R 53 and R 61 to R 66 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms,
• p 51 is an integer of 0 to 6
• p 52 and p 53 are each independently an integer of 0 to 4
• p 63 and p 66 are each independently an integer of 0 to 3 an integer, when p 51 to p 53 , p 63 or p 66 is 2 or more, a plurality of R 51 to R 53 , R 63 or R 66 may be the same or different
• n is 1; is an integer of ⁇ 10.
• R 51 is an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. It is an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms.
• the alkyl group having 1 to 10 carbon atoms may be either linear or branched, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert- Butyl group, n-pentyl group, isopentyl group, 2-methylbutyl group, 1-methylbutyl group, 1,2-dimethylpropyl group, neopentyl group (2,2-dimethylpropyl group), tert-pentyl group (1,1- dimethylpropyl group), n-hexyl group, isohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group, 1 , 2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbut
• the alkoxy group having 1 to 10 carbon atoms may be either linear or branched, and examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert -butoxy group, n-pentyloxy group, isopentyloxy group, 2-methylbutoxy group, 1-methylbutoxy group, 1,2-dimethylpropoxy group, neopentyloxy group (2,2-dimethylpropoxy group), tert -pentyloxy group (1,1-dimethylpropoxy group), n-hexyloxy group, isohexyloxy group, 1-methylpentyloxy group, 2-methylpentyloxy group, 3-methylpentyloxy group, 1-ethylbutoxy group, 2-ethylbutoxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2,2-dimethylbutoxy group, 2,3-dimethyl
• R 52 to R 53 and R 61 to R 66 are each independently an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, more preferably It is an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms.
• the alkyl group having 1 to 4 carbon atoms may be either linear or branched, and examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, or tert -Butyl group.
• a methyl group, an ethyl group, an n-propyl group or an isopropyl group is preferred, a methyl group or an ethyl group is more preferred, and a methyl group is even more preferred.
• the alkoxy group having 1 to 4 carbon atoms may be either linear or branched, and examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, or A tert-butoxy group can be mentioned.
• methoxy, ethoxy, n-propoxy and isopropoxy are preferred, and methoxy and ethoxy are more preferred.
• p51 is an integer of 0-6, preferably 0-5, more preferably 0-3.
• p52 and p53 are each independently an integer of 0-4, preferably 0-2, more preferably 0;
• p 63 and p 66 are each independently an integer of 0-3, preferably 0-1, more preferably 0;
• n is an integer of 1 to 10, preferably 1 to 5, more preferably 1 to 3, still more preferably 1;
• the compound (B) consists of compounds represented by the following structural formulas (B1) to (B3) from the viewpoint of achieving both high flame retardancy and good appearance even in a thin molded article having a thickness of, for example, 500 ⁇ m or less. It is preferably at least one selected from the group. More preferably, compound (B) is a compound represented by the following structural formula (B3).
• the content of the compound (B) in the polyimide resin composition is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 30 parts by mass, more preferably 100 parts by mass of the polyimide resin (A). 1 to 30 parts by mass, more preferably 2 to 30 parts by mass, even more preferably 4 to 25 parts by mass, even more preferably 5 to 25 parts by mass, even more preferably 5 to 20 parts by mass, even more preferably 5 to 15 parts by mass. If the content of the compound (B) is 0.1 parts by mass or more with respect to 100 parts by mass of the polyimide resin (A), it is easy to impart a flame retardant improvement effect and low dielectric properties, and if it is 30 parts by mass or less, a good Appearance and heat resistance can be maintained.
• Component (C) At least one selected from the group consisting of metal phosphinate (C1) and fluororesin (C2)>
• the polyimide resin composition of the present invention has at least one selected from the group consisting of metal phosphinate (C1) and fluororesin (C2) for the purpose of improving anti-drip effect and further enhancing flame retardancy. of component (C).
• the metal phosphinate (C1) is a salt of at least one metal selected from the group consisting of Mg, Ca, Al, Zn, Ti, Sn, Zr, and Fe from the viewpoint of improving the anti-drip effect. preferable.
• the metal is more preferably at least one selected from the group consisting of Mg, Ca, and Al, and more preferably Al.
• the metal phosphinate (C1) is preferably a compound represented by the following formula (i) from the viewpoint of improving the anti-drip effect and obtaining a good appearance.
• R′ and R′′ are each independently a hydrocarbon group having 1 to 12 carbon atoms, M is a metal atom, and p is the valence of the metal atom represented by M.
• R′ and R′′ each independently represent a hydrocarbon group having 1 to 12 carbon atoms.
• the hydrocarbon group include an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, An aralkyl group and the like can be mentioned.
• alkyl group examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n -decyl group, n-undecyl group, lauryl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isopentyl group, neopentyl group, 2-methylpentyl group, 2-methylhexyl group, 2-ethylpentyl 3-ethylpentyl group, isooctyl group, 2-ethylhexyl group, 3-ethylhexyl group, isononyl group, 2-ethyloctyl group, isodecyl group and isododecyl group.
• Examples of the cycloalkyl group include cycloalkyl groups having 5 to 12 carbon atoms such as cyclopentyl group, cyclohexyl group, cyclooctyl group and cyclodecanyl group.
• Examples of the alkenyl group include vinyl group, allyl group, butenyl group, 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, and other alkenyl groups having 2 to 12 carbon atoms.
• aryl group examples include aryl groups having 6 to 12 carbon atoms such as phenyl group, toluyl group, biphenyl group and naphthyl group.
• aralkyl group examples include aralkyl groups having 7 to 12 carbon atoms such as aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group.
• R′ and R′′ are preferably alkyl groups.
• the number of carbon atoms in the alkyl group is preferably 1-8, more preferably 1-6, and still more preferably 1-3.
• R' and R'' may be the same or different, but are preferably the same.
• M is a metal atom, preferably at least one selected from the group consisting of Mg, Ca, Al, Zn, Ti, Sn, Zr, and Fe. M is more preferably at least one selected from the group consisting of Mg, Ca and Al, more preferably Al.
• the metal phosphinate (C1) is preferably a compound (dialkylaluminum phosphinate) in which R′ and R′′ are alkyl groups having 1 to 12 carbon atoms and M is Al in the above formula (i). In this case, p in the above formula (i) is 3. More preferred embodiments of R' and R'' are the same as above. More preferably, the metal phosphinate (C1) is a compound (aluminum diethylphosphinate) in which R′ and R′′ are ethyl groups and M is Al in the formula (i). Aluminum diethylphosphinate is is a compound represented by the following structural formula (ii).
• the metal phosphinate (C1) is a metal phosphinate, it is usually a solid compound, and is preferably powdery from the viewpoint of dispersibility in the polyimide resin (A). In addition, from the viewpoint of improving the anti-drip effect and maintaining a good appearance, it is preferable that the metal phosphinate (C1) has a small particle size. From the above viewpoint, the particle diameter (D50) of the metal phosphinate (C1) is preferably 40 ⁇ m or less, more preferably 30 ⁇ m or less, still more preferably 20 ⁇ m or less, even more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less. be.
• the particle diameter (D50) of the metal phosphinate (C1) is 40 ⁇ m or less, particularly 10 ⁇ m or less, the obtained polyimide resin composition and molded article have higher flame retardancy and good appearance.
• the particle diameter (D50) of the metal phosphinate (C1) is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, and still more preferably 1 ⁇ m or more.
• the particle size (D50) of the metal phosphinate (C1) can be measured with a laser diffraction particle size distribution meter.
• the phosphorus content of the metal phosphinate (C1) is preferably 0.5% by mass or more, more preferably 1% by mass or more, from the viewpoint of improving the anti-drip effect. From the viewpoint of expression, it is preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more. Moreover, from the viewpoint of improving the dispersibility in the polyimide resin (A) and maintaining a good appearance, the phosphorus content of the metal phosphinate (C1) is preferably 40% by mass or less.
• the phosphinate metal salt (C1) can be produced by a known method.
• a commercially available metal phosphinate flame retardant can also be used as the metal phosphinate (C1).
• Examples of commercially available metal phosphinate flame retardants include "EXOLIT OP1230", “EXOLIT OP1240", “EXOLIT OP1400", “EXOLIT OP930", “EXOLIT OP935" and “EXOLIT OP945" manufactured by Clariant Chemicals Co., Ltd. , "EXOLIT OP945TP” and the like.
• fluororesin (C2) examples include polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), a copolymer of tetrafluoroethylene and hexafluoropropylene (FEP), A copolymer of tetrafluoroethylene and perfluoroalkyl vinyl ether (PFA), a copolymer of tetrafluoroethylene and ethylene (ETFE), a copolymer of tetrafluoroethylene and perfluoroalkoxyethylene, etc. 1 type, or 2 or more types can be used among these.
• polytetrafluoroethylene is preferable from the viewpoint of improving the anti-drip effect and maintaining good appearance and heat resistance.
• the fluororesin (C2) used in the present invention is preferably powdery from the viewpoint of dispersibility in the polyimide resin (A) and handleability.
• its average particle size (D50) is not particularly limited, but from the viewpoint of dispersibility and handleability in the polyimide resin (A), preferably 1 to 50 ⁇ m, more preferably 2 to 40 ⁇ m, more preferably 3 to 30 ⁇ m, even more preferably 5 to 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.
• the component (C) may be used alone or in combination of two or more, and the metal phosphinate (C1) and the fluororesin (C2) may be used in combination.
• a metal phosphinate (C1) is preferred as the component (C) from the viewpoints of improving the anti-drip effect, maintaining good appearance and heat resistance, and adhesion to metals such as copper and steel plates.
• the content of the component (C) in the polyimide resin composition is preferably 0.01 to 5 parts by mass, more preferably 0.05, per 100 parts by mass of the polyimide resin (A). to 3 parts by mass, more preferably 0.1 to 2 parts by mass, and even more preferably 0.2 to 2 parts by mass. If the content of the component (C) in the polyimide resin composition is 0.01 parts by mass or more with respect to 100 parts by mass of the polyimide resin (A), it is easy to impart a drip prevention effect, and if it is 5 parts by mass or less, it is good. Appearance and heat resistance can be maintained.
• the mass ratio of the component (B) to the component (C) in the polyimide resin composition [(B) / (C)] is the anti-drip effect, flame retardancy, good appearance And from the viewpoint of obtaining heat resistance, it is preferably 1.0 to 40, more preferably 5.0 to 30, still more preferably 10 to 20.
• polyimide The smaller the content of component (C) in the resin composition, the better.
• the content of the component (C) in the polyimide resin composition is more preferably 1 per 100 parts by mass of the polyimide resin (A). 0.5 parts by mass or less, more preferably 1 part by mass or less, even more preferably 0.5 parts by mass or less, and even more preferably 0.1 parts by mass or less.
• the polyimide resin composition of the present invention contains fillers, reinforcing fibers, delustering agents, plasticizers, antistatic agents, anti-coloring agents, anti-gelling agents, coloring agents, slidability improvers, antioxidants, and conductive agents.
• Additives other than component (C), such as agents and resin modifiers, can be blended as needed.
• inorganic fillers such as mica and talc, especially when micro- to submicron-sized or nano-sized powders (solid particles) are added, the resulting molded body (especially Film) This is preferable because it can provide the effect of lowering the CTE (coefficient of linear expansion) of the filler while ensuring the appearance.
• the particle diameter (D50) of the solid particles and hollow materials is preferably 40 ⁇ m or less, more preferably 30 ⁇ m or less. , more preferably 20 ⁇ m or less, still more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
• the thickness is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, and still more preferably 1 ⁇ m or more.
• D50 can be measured with a laser diffraction particle size distribution meter.
• the amount thereof is not particularly limited, but from the viewpoint of expressing the effect of the additive while maintaining the physical properties derived from the polyimide resin (A), usually 50 mass in the polyimide resin composition % or less, preferably 0.0001 to 30% by mass, more preferably 0.001 to 15% by mass, still more preferably 0.01 to 10% by mass.
• the polyimide resin composition of the present invention may contain other resins than the polyimide resin (A) as long as the properties thereof are not impaired.
• a highly heat-resistant thermoplastic resin is preferable, and examples thereof include polyamide resins, polyester resins, polyimide resins other than the polyimide resin (A), polycarbonate resins, polyetherimide resins, polyamideimide resins, and polyphenylene etherimide. Resin, polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polyarylate resin, liquid crystal polymer, polyetheretherketone resin, polyetherketone resin, polyetherketoneketone resin, polyetheretherketoneketone resin, polybenzimidazole resin, etc.
• polyetherimide resins one or more selected from the group consisting of polyetherimide resins, polyphenylene sulfide resins, and polyether ether ketone resins is preferable from the viewpoint of heat resistance, molding processability, strength and solvent resistance, and has low water absorption.
• a liquid crystal polymer is preferred, and from the viewpoint of obtaining high flame retardancy, a polyphenylene sulfide resin is preferred.
• the polyimide resin (A) is used in combination with another resin, there is no particular limitation on the blending ratio as long as the properties of the polyimide resin composition are not impaired.
• the total content of the polyimide resin (A) and the compound (B) in the polyimide resin composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, from the viewpoint of obtaining the effects of the present invention. , More preferably 50% by mass or more, still more preferably 70% by mass or more, still 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 It is below.
• the polyimide resin composition of the present invention can take any form, pellets are preferred. Since the polyimide resin composition of the present invention and the polyimide resin (A) used therein have thermoplasticity, for example, the polyimide resin (A), the compound (B), and optionally various optional components are added and dry blended. After that, or after feeding the compound (B) and optional components from a place different from the feeding of the polyimide resin (A) to the extruder, the strands are extruded by melt-kneading in the extruder, and the strands are cut. It can be pelletized by Further, by introducing the pellets into various molding machines and thermoforming them by the method described below, a molded body having a desired shape can be easily produced.
• the polyimide resin composition of the present invention does not contain a solvent from the viewpoint of forming pellets.
• the solvent content in the polyimide resin composition is preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.1% by mass or less.
• the present invention provides a molded article containing the polyimide resin composition.
• the shape of the molded body is not particularly limited, but from the viewpoint of effectively exhibiting the effect of the present invention that high flame retardancy and good appearance can be obtained even with a thin molded body, the thickness is 500 ⁇ m. It is preferably 200 ⁇ m or less, more preferably less than 100 ⁇ m, still more preferably 80 ⁇ m or less, and even more preferably 60 ⁇ m or less in film shape.
• the lower limit of the thickness is usually 5 ⁇ m or more, preferably 10 ⁇ m or more.
• the term "thickness of the film-shaped molded article" means the average value of the thickness of the film-shaped molded article.
• the film-shaped molded body includes the form of a resin layer constituting a multilayer laminate, the form of a coating layer, and the like, in addition to the form of a resin film.
• the shape of the molded article of the present invention is not limited to a film shape having a thickness of 500 ⁇ m or less.
• the effect of the present invention can be obtained even with a flat plate-shaped compact having a thickness exceeding 500 ⁇ m.
• thermoforming Since the polyimide resin composition of the present invention has thermoplasticity, the molded article of the present invention can be easily produced by thermoforming.
• thermoforming methods include injection molding, extrusion molding, inflation molding, blow molding, hot press molding, vacuum molding, pressure molding, laser molding, welding, and welding. Molding is also possible by the method. Extrusion molding is preferred when producing a film-shaped molding having a thickness of 500 ⁇ m or less. Injection molding or the like can be used to manufacture a flat molded article having a thickness of more than 500 ⁇ m. Thermoforming is preferred because molding can be performed without setting the molding temperature to a high temperature exceeding, for example, 400°C.
• injection molding is preferable because molding can be performed without setting the molding temperature and the mold temperature at the time of molding to a high temperature.
• the molding temperature is preferably 400° C. or lower, more preferably 360° C. or lower
• the mold temperature is preferably 260° C. or lower, more preferably 220° C. or lower.
• the polyimide resin (A) used in the present invention has a very fast crystallization rate compared to general crystalline resins, so even at a mold temperature that is much lower than the glass transition temperature (for example, Tg-50 ° C.) , it is possible to proceed with crystallization.
• a method for producing a molded product preferably includes a step of thermoforming a polyimide resin composition at 290 to 360°C.
• Thermoforming at temperatures above 360° C. to 390° C. is also possible, but from the viewpoint of suppressing deterioration of the polyimide resin (A) and other resin components, thermoforming at a temperature of 360° C. or less is preferred.
• Specific procedures include, for example, the following method. First, the polyimide resin (A), compound (B) and optionally various optional components are added and dry blended, and then introduced into an extruder, preferably melted at 290 to 360 ° C. and extruded. Melt-knead and extrude in the machine to produce pellets.
• the polyimide resin (A) is introduced into the extruder, preferably melted at 290 to 360 ° C., and the compound (B) and various optional components are introduced here, and the polyimide resin (A ) and extruded to produce the aforementioned pellets. After the pellets are dried, they are introduced into various molding machines and thermoformed preferably at 290 to 360° C. to produce a molded article having a desired shape. Since the polyimide resin composition of the present invention can be subjected to thermoforming such as extrusion molding at a relatively low temperature of 290 to 360 ° C., it has excellent moldability and can easily produce a molded product having a desired shape. can do. The temperature during thermoforming is preferably 310-360°C.
• the polyimide resin composition and molded article of the present invention exhibit high flame retardancy even when formed into a thin molded article having a thickness of 500 ⁇ m or less.
• the flame retardancy can be evaluated by a method conforming to the UL94 VTM test (thin material vertical burning test; ASTM D4804), specifically based on the method described in Examples.
• the polyimide resin composition and molded article of the present invention have low dielectric properties, and can achieve, for example, a dielectric constant of 3.0 or less and a dielectric loss tangent of 0.005 or less at a measurement frequency of 10 GHz.
• the dielectric constant is preferably 2.90 or less, more preferably 2.85 or less
• the dielectric loss tangent is preferably 0.004 or less, more preferably 0.003 or less.
• the dielectric constant and dielectric loss tangent can be specifically measured by the methods described in Examples.
• the polyimide resin composition of the present invention a molded article having both high flame retardancy and good appearance can be produced even when the thickness is thin (for example, 500 ⁇ m or less). Furthermore, the polyimide resin composition and the molded article containing it have high heat resistance (high glass transition temperature) and low dielectric properties, so that high flame retardancy, low dielectric constant and low dielectric loss tangent are required.
• 5G or 6th generation mobile communication system 6G related parts using the frequency band of 70G to 300GHz (smartphones, flexible printed circuit boards, metal foil laminates such as copper clad laminates, antennas, antenna substrates, etc.),
• various antennas microwave antennas, millimeter wave antennas, waveguide slot antennas, horn antennas, lens antennas, printed antennas, triplate antennas, microstrip antennas, patch antennas, etc.
• various antenna substrates (77 GHz) Automotive millimeter wave radar antenna substrate, terahertz wave radar antenna substrate, aircraft radar antenna substrate, caterpillar type special vehicle antenna substrate, WiGig antenna substrate, etc.), wire coating materials (low dielectric wire coating materials, etc.), bonding Sheets, insulating films, raw materials for carbon fiber reinforced plastics (CFRP), high-frequency circuit boards, printed wiring boards, chip-on-film (COF) flexible boards, multi-layer laminates, LED mounting boards, industrial robot boards, communications for home robots substrates, semiconductor element materials, high-
• the present invention provides a metal foil laminate having a layer made of a molded body containing the polyimide resin composition and a layer made of a metal foil.
• the metal foil laminate mainly includes a copper-clad laminate, and the copper-clad laminate is a layer (hereinafter also simply referred to as "resin film layer") made of a film-shaped molded body containing the polyimide resin composition. and at least one copper foil layer.
• a laminate having a configuration in which a copper foil is laminated on at least one surface, preferably both surfaces of a resin film containing the polyimide resin composition can be mentioned.
• the resin film used for manufacturing the copper-clad laminate can be manufactured by the same method as the method for manufacturing the molded product.
• the thickness of the resin film and the resin film layer in the copper-clad laminate is preferably 5 to 500 ⁇ m from the viewpoint of ensuring the strength of the copper-clad laminate and improving the adhesion between the resin film layer and the copper foil layer. , more preferably 10 to 300 ⁇ m, still more preferably 12.5 to 200 ⁇ m.
• the copper foil used for producing the copper-clad laminate is not particularly limited, and commercially available rolled copper foil, electrolytic copper foil, etc. can be used, but rolled copper foil is preferable from the viewpoint of flexibility.
• the thickness of the copper foil layer and the copper foil used for its formation is preferably 2 to 50 ⁇ m, more preferably 3 to 30 ⁇ m, from the viewpoint of ensuring sufficient conductivity and improving adhesion with the resin film layer. More preferably, it is 5 to 20 ⁇ m.
• the thickness is the thickness per copper foil layer or per copper foil.
• the surface roughness of the copper foil used in the production of the copper-clad laminate is not particularly limited, but the surface roughness of the copper foil is directly linked to the electrical properties of the laminate itself obtained after laminating the resin film, and generally In theory, the lower the roughness, the better the dielectric properties of the laminate. Therefore, the maximum height Rz of the copper foil surface is preferably in the range of 0.1 to 1 ⁇ m, more preferably in the range of 0.2 to 0.8 ⁇ m. The maximum height Rz of the copper foil surface can be measured, for example, with a surface roughness meter.
• the thickness of the copper-clad laminate is preferably 15-600 ⁇ m, more preferably 25-500 ⁇ m, still more preferably 50-300 ⁇ m, from the viewpoint of improving the strength and conductivity of the copper-clad laminate.
• the copper-clad laminate may have any layer other than the resin film layer and the copper foil layer as long as the effects of the present invention are not impaired.
• the method for producing the copper-clad laminate is not particularly limited, and known methods can be used. For example, there is a method of stacking the resin film and the copper foil on top of each other, and then laminating them under heating and pressurizing conditions. Since the resin film contains the thermoplastic polyimide resin (A), it can be bonded to the copper foil by pressure bonding with the surface melted by heat.
• the apparatus used for manufacturing the copper-clad laminate may be any apparatus as long as it can bond the resin film and the copper foil together under heat and pressure conditions. Examples include a roll laminator, flat plate laminator, vacuum press apparatus, A double belt press device and the like can be mentioned.
• a double belt press device is equipped with endless belts arranged in a pair of upper and lower parts, and between the belts, film-shaped materials (resin film and copper foil) forming each layer are continuously fed and heated through the endless belts. It is an apparatus capable of producing a laminate by heating and pressurizing the above materials using a pressurizing mechanism.
• the double belt press device include the device described in JP-A-2010-221694 and the double belt press device manufactured by DIMCO Co., Ltd.
• the heating temperature for producing a copper-clad laminate by the above method is not particularly limited as long as it is a temperature at which the resin film can be softened or melted. It is in the range of 250-400°C, more preferably 280-350°C.
• the pressure conditions for producing the copper-clad laminate are preferably from 0.1 to 0.1, from the viewpoint of improving the adhesion between the resin film and the copper foil, and from the viewpoint of reducing the burden on the apparatus and manufacturing. 20 MPa, more preferably 0.15 to 15 MPa, still more preferably 0.2 to 12 MPa.
• the pressurization time is preferably in the range of 1 to 600 seconds, more preferably 5 to 400 seconds, and even more preferably 10 to 300 seconds.
• the resin film is characterized in that it can be heat-sealed, but it is also possible to bond the resin film and the copper foil together using an adhesive in the production of the copper-clad laminate.
• an adhesive a varnish-like adhesive, a sheet-like adhesive, a powder-like adhesive, or the like can be arbitrarily selected.
• the adhesive also have low dielectric properties. Examples of adhesives with low dielectric properties include the "PIAD" series of polyimide adhesives manufactured by Arakawa Chemical Industries, Ltd.
• IR measurement ⁇ Infrared spectroscopic analysis (IR measurement)>
• the IR measurement of the polyimide resin was performed using "JIR-WINSPEC50" manufactured by JEOL Ltd.
• the melting point Tm, glass transition temperature Tg, crystallization temperature Tc, and crystallization heat value ⁇ Hm of the polyimide resin or polyimide resin composition were measured using a differential scanning calorimeter ("DSC-6220" manufactured by SII Nanotechnology Co., Ltd.). was measured using In a nitrogen atmosphere, the polyimide resin or polyimide resin composition was subjected to thermal history under the following conditions.
• 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.
• the semi-crystallization time of the polyimide resin was measured using a differential scanning calorimeter ("DSC-6220" manufactured by SII Nanotechnology Co., Ltd.).
• the measurement conditions for the polyimide resin having a semi-crystallization time of 20 seconds or less were held at 420° C. for 10 minutes in a nitrogen atmosphere to melt the polyimide resin completely, and then perform a rapid cooling operation at a cooling rate of 70° C./min. Second, the time taken from the appearance of the observed crystallization peak to the peak top was calculated and determined.
• the film was wound in a cylindrical shape, attached vertically to a clamp, and subjected to two 3-second indirect flames with a 20 mm flame using methane gas, and the flame retardancy was evaluated from the combustion behavior.
• a flat plate-like molded body of 80 mm ⁇ 10 mm ⁇ 4 mm in thickness was produced by the method described later, and the flat plate was heated at 23 ⁇ 2° C. and 50 ⁇ 5% RI. H. after conditioning for 48 hours at 25 ⁇ 10° C., 75% R.I. H. It was used for the UL94V test (20 mm vertical burn test; ASTM D3801) under the following test environment. Specifically, the flat plate was vertically attached to a clamp, and 20-mm flame using methane gas was applied twice for 10 seconds, and the flame retardancy was evaluated from the combustion behavior.
• V-0 if it has flame retardancy equivalent to V-0 according to the criteria of UL94V
• V-1 if it has flame retardancy equivalent to V-1
• V-2 flame retardancy equivalent to V-2 If it has, it is written as "V-2”.
• the flame retardance is higher in the order of V-0>1>2, and when the flame retardance equivalent to V-2 is not achieved, it is judged as "V unsuitable”.
• ⁇ Dielectric constant and dielectric loss tangent> Using the polyimide resin or the polyimide resin composition obtained in each example, a film-shaped molded body is produced by extrusion molding by the method described later, and then cut to 62 mm ⁇ 75 mm ⁇ thickness 0.05 ⁇ A 0.01 mm evaluation film was obtained. After drying the film in a hot air dryer at 100°C for 24 hours, it was dried at 23 ⁇ 2°C and 50 ⁇ 5% RH. H. was conditioned for 48 hours at . After that, it was immediately used for measurement. As a measuring device, "P5008A Keysight Streamline USB Vector Network Analyzer, 53 GHz" manufactured by Keysight Technologies, Inc.
• a molded body of 200 mm ⁇ 50 mm ⁇ thickness 0.05 ⁇ 0.01 mm is produced by the method described later, and the appearance is visually observed and evaluated according to the following criteria. and shown in Table 4.
• ⁇ Strand extrudability> The strand extrudability of the polyimide resin or polyimide resin composition was evaluated according to the following criteria and shown in Table 4.
• AA Maintains a constant strand diameter and can be continuously extruded without breaking. Also, after extrusion, it takes 3 seconds or longer for the strands to become opaque.
• A Maintains a constant strand diameter and can be continuously extruded without breaking. Also, after extrusion, the strands become opaque within 3 seconds.
• C Strand breakage, strong smoke emission, and vent-up occurred, making it difficult to continuously extrude.
• Production Example 1 (Production of Polyimide Resin 1)
• a 2 L separable flask equipped with a Dean-Stark apparatus, a Liebig condenser, a thermocouple, and four paddle blades 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.
• 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. The mixed diamine solution was added slowly 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.
• 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 are values calculated from the amount of each component charged during the production of the polyimide resin.
• Examples 1 to 8, Comparative Examples 1 to 3 manufactured and evaluation of polyimide resin composition and molded article (resin film)
• the polyimide resin 1 obtained in Production Example 1, the compounds shown in Tables 2 to 4, and other components were thoroughly mixed by dry blending.
• the resulting mixed powder was extruded in a co-rotating twin-screw kneading extruder (“HK-25D-41D” manufactured by Parker Corporation) at a barrel temperature of 350° C. and a screw rotation speed of 120 rpm to form strands having a diameter of 2 to 3 mm. pushed out.
• the strand extrudability at this time was evaluated according to the above criteria.
• pelletizer Fluorescence FC-Mini-4/N manufactured by Hoshi Plastics Co., Ltd.
• the obtained pellets were dried at 190° C. for 10 hours and then used for extrusion molding.
• the pellets were put into a ⁇ 20 mm single-screw extruder equipped with a T-die with a width of 150 mm, melt-kneaded at a resin temperature of 340 to 360° C., and continuously extruded through the T-die of the single-screw extruder.
• EXOLIT OP945 Metal phosphinate flame retardant (aluminum diethylphosphinate) represented by the following structural formula (ii), manufactured by Clariant Chemicals Co., Ltd., particle size (D50): 1.3 ⁇ m, phosphorus content: 23% by mass (C2)
• KTL-450 Polytetrafluoroethylene (PTFE), manufactured by Kitamura Co., Ltd.
• Tables 2 and 3 show the evaluation results of flame retardancy.
• Table 2 shows that the molded articles containing the polyimide resin composition of the present invention have a shorter burning time and better flame retardancy than the molded articles of the comparative examples. Also, from Table 3, in particular, in Examples 2 to 8, despite the very thin molded body with a thickness of 0.05 mm ⁇ 0.01 mm, it has flame retardancy equivalent to VTM-0 according to the UL94 VTM criteria. I was able to achieve it.
• Table 4 shows evaluation results of thermophysical properties, dielectric properties, appearance, and strand extrudability. From Table 4, all the molded articles containing the polyimide resin composition of the present invention have good appearance. Regarding the strand extrudability, the polyimide resin compositions of Examples 1 to 5 containing only the compound (B) as the flame retardant showed particularly good results. This is probably because, unlike other flame retardants (component (C1)), the compound (B) does not act as a crystal nucleating agent and has the effect of delaying the crystallization of the polyimide resin (A).
• the molded article containing the polyimide resin composition of the present invention had a dielectric constant of 3 or less and a dielectric loss tangent of 0.005 or less, showing extremely low dielectric constant and dielectric loss tangent as a resin molded article.
• Example 9 (manufacture and evaluation of polyimide resin composition and molded article (4 mm thick flat plate)) Pellets of the polyimide resin composition were produced in the same manner as in Example 2. The pellets were dried at 190° C. for 10 hours and then used for injection molding. Using an injection molding machine (“ROBOSHOT ⁇ -S30iA” manufactured by FANUC CORPORATION), injection molding is performed with a barrel temperature of 350 ° C, a mold temperature of 200 ° C, and a molding cycle of 50 seconds. A type 1A test piece was prepared. After processing the obtained type 1A test piece into a flat plate of 80 mm ⁇ 10 mm ⁇ 4 mm in thickness, flame retardancy was evaluated by the method described above. Table 5 shows the results. The evaluation results other than flame retardancy are the same as in Example 2.
• ROBOSHOT ⁇ -S30iA manufactured by FANUC CORPORATION
• the molded article containing the polyimide resin composition of the present invention exhibited good flame retardancy even when the thickness exceeded 500 ⁇ m.
• the polyimide resin composition of the present invention it is possible to produce a molded article that achieves both high flame retardancy and good appearance even when the thickness is thin (for example, 500 ⁇ m or less). Furthermore, the polyimide resin composition and molded articles containing the same have high heat resistance (high glass transition temperature) and low dielectric properties.
• the polyimide resin composition and molded article of the present invention are used for applications requiring high flame retardancy, low dielectric constant and low dielectric loss tangent, for example, 5G, or 70G to 300GHz frequency band 6th generation Mobile communication system (6G) related parts, various antennas, various antenna substrates, wire coating materials, bonding sheets, insulating films, raw materials for carbon fiber reinforced plastics (CFRP), high frequency circuit boards, printed wiring boards, chip-on-films (COF) Flexible substrates, multilayer laminates, LED mounting substrates, industrial robot substrates, home robot communication substrates, semiconductor element materials, high frequency device wafers, Wi-fi chips, wireless communication devices, transmission lines, bearing coatings, heat insulation Shafts, trays, various belts, heat-resistant low-dielectric tape, heat-resistant low-dielectric tubes, various sensors, various radars, radomes (radomes), optical communication modules (TOSA/ROSA), 8k-TV cable mobile terminals or digital home appliances, bases Stations, drones, surveillance cameras, indoor or outdoor

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