Polyarylene sulfide resin composition and its uses

Abstract

To provide a resin composition that strikes a balance between high mechanical properties and high moldability even when containing a polyarylene sulfide resin.SOLUTION: A polyarylene sulfide resin is combined with a fluorene compound represented by the formula (1) to prepare a resin composition. [Ring Z1, ring Z2 each denote a fused polycyclic arene ring or assembled arene rings; X1, X2 each denote an amino group or the like; p1, p2 each denote an integer of 0 or greater; R1, R2 each denote a substituent; m1, m2 each denote an integer of 0 or greater; R3 is a substituent; k is an integer of 0 or greater].SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyarylene sulfide resin composition containing a compound having a 9,9-bis(polycyclic aryl)fluorene skeleton, and uses thereof. [Background technology]

[0002] Polyarylene sulfide resins, such as polyphenylene sulfide (PPS), are crystalline thermoplastic resins that offer excellent heat resistance, mechanical properties such as hardness and strength, low abrasion, flame retardancy, dimensional stability, chemical resistance, and electrical properties. They are widely used as compound products containing various reinforcing materials and fillers. However, while polyarylene sulfide resins have excellent heat resistance, they must be melted at high temperatures for molding. Therefore, when molding polyarylene sulfide resins, it is difficult to improve their fluidity during melting, resulting in poor productivity and ease of handling.

[0003] Japanese Patent Application Laid-Open No. 2016-108531 (Patent Document 1) discloses a reinforced thermoplastic resin composition in which a thermoplastic resin such as PPS is used as a matrix resin and a filler is added to the resin to reinforce the mechanical strength, and in which a fluorene compound is dispersed in the thermoplastic resin in a state in which the fluorene compound is selectively attached to the surface of the filler. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-108531 Summary of the Invention [Problem to be solved by the invention]

[0005] However, Patent Document 1 aims to improve the mechanical strength and heat resistance of a resin composition by efficiently adhering a sizing agent to the surface of a reinforcing material such as carbon fiber, and does not describe improving the moldability of the polyarylene sulfide resin itself.

[0006] Therefore, an object of the present invention is to provide a polyarylene sulfide resin composition which contains a polyarylene sulfide resin and yet is capable of achieving both high mechanical properties and high moldability, and uses thereof. [Means for solving the problem]

[0007] As a result of extensive research to achieve the above object, the present inventors have found that by combining a polyarylene sulfide resin with a 9,9-bis(fused polycyclic or ring-assembly aryl)fluorene compound, it is possible to achieve both high mechanical properties and high moldability even when a PPS resin is contained, and have completed the present invention.

[0008] That is, the polyarylene sulfide resin composition of the present invention contains a polyarylene sulfide resin and a fluorene compound represented by the following formula (1).

[0009] [ka]

[0010] [In the formula, Ring Z 1 and ring Z 2 are the same or different and represent a fused polycyclic arene ring or a ring-assembly arene ring, X 1 and X 2 are the same or different and represent a group -[(OA) n -Y] (In the formula, Y represents a hydroxyl group, a mercapto group, a glycidyloxy group, or a (meth)acryloyloxy group; A's may be the same or different and represent a linear or branched alkylene group; (n is an integer greater than or equal to 0) or an amino group, p1 and p2 are the same or different and represent an integer of 0 or more, R 1 and R 2 are the same or different and represent substituents, m1 and m2 are the same or different and each represent an integer of 0 or more; R 3 represents a substituent, k is an integer equal to or greater than 0.

[0011] In the formula (1), ring Z 1 and ring Z 2 may be the same or different and may be a biphenyl ring or a naphthalene ring, R 1 and R 2 may be the same or different and represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkoxy group; p1 and p2 may be the same or different and represent an integer of 1 or more; m1 and m2 may be the same or different and represent an integer of 0 to 2; R 3 may be an alkyl group, and k may be an integer of 0 to 2.

[0012] The fluorene compound represented by the formula (1) is 9,9-bis(phenyl-hydroxyphenyl)fluorene, 9,9-bis(hydroxynaphthyl)fluorene, and a compound in which 1 to 10 moles of C are used per mole of the hydroxyl group of these compounds. 2-4 It may be at least one selected from the group consisting of alkylene oxide adducts.

[0013] In the formula (1), ring Z 1 and ring Z 2 may be a biphenyl ring.

[0014] The polyarylene sulfide resin may be a polyphenylene sulfide resin.

[0015] The resin composition may further include a fibrous reinforcing material. The resin composition may further include a heat dissipation material. The proportion of the fluorene compound represented by formula (1) may be 0.1 to 10 parts by mass relative to 100 parts by mass of the polyarylene sulfide resin.

[0016] The present invention also includes a molded article formed from the resin composition.

[0017] The present invention also includes a method of improving the melt fluidity of a polyarylene sulfide resin by adding a fluorene compound represented by the formula (1) to the polyarylene sulfide resin.

[0018] In this specification and claims, the number of carbon atoms in a substituent is represented by C1, C6, C 10 For example, "C1 alkyl group" means an alkyl group with 1 carbon atom, and "C 6-10 The term "aryl group" refers to an aryl group having 6 to 10 carbon atoms.

[0019] In the present specification and claims, the term "(meth)acryloyloxy group" is used to mean both an acryloyloxy group and a methacryloyloxy group. [Effects of the Invention]

[0020] In the present invention, a polyarylene sulfide resin and a 9,9-bis(fused polycyclic or ring-assembly aryl)fluorene compound are combined, thereby achieving both high mechanical properties and high moldability (melt fluidity or productivity). In particular, gas generation can be suppressed even when heated to a high temperature for melting, so that the polyarylene sulfide resin composition can be molded with high productivity. DETAILED DESCRIPTION OF THE INVENTION

[0021] [Polyarylene sulfide resin] The polyarylene sulfide resin may be a resin having a repeating unit represented by the following formula (2).

[0022] [ka]

[0023] (In the formula, Z 3 indicates an arene ring, and R 4 represents an alkyl group, and s represents an integer of 0 or more).

[0024] In the formula (2), ring Z 3 Arene rings (or aromatic hydrocarbon rings) represented by the formula (I) are broadly classified into monocyclic aromatic hydrocarbon rings (monocyclic arene rings) such as benzene rings, and polycyclic aromatic hydrocarbon rings (polycyclic arene rings). Examples of polycyclic aromatic hydrocarbon rings include fused polycyclic aromatic hydrocarbon rings (fused polycyclic arene rings) and ring-assembled aromatic hydrocarbon rings (ring-assembled arene rings).

[0025] The fused polycyclic arene ring includes fused bicyclic arene rings, fused tricyclic arene rings, and other fused bicyclic to tetracyclic arene rings. The fused bicyclic arene ring includes fused bicyclic C rings such as naphthalene rings and indene rings. 10-16 Examples of the fused tricyclic arene ring include an acenaphthylene ring, a fluorene ring, a phenalene ring, an anthracene ring, and a phenanthrene ring. Examples of the fused tetracyclic arene ring include a pyrene ring and a naphthacene ring.

[0026] As a ring-assembled arene ring, biC 6-12 Arene rings and other biarene rings, terephthalic acid rings 6-12 Examples include terarene rings such as arene rings. 6-12 Examples of the arene ring include a biphenyl ring, a binaphthyl ring, and a phenylnaphthalene ring such as a 1-phenylnaphthalene ring or a 2-phenylnaphthalene ring. 6-12Examples of the arene ring include a terphenyl ring.

[0027] In this specification and claims, the term "ring assembly arene ring" refers to two or more ring systems (arene ring systems) directly connected by single bonds or double bonds, and the number of bonds directly connecting the rings is one less than the number of ring systems. For example, as described above, phenylnaphthalene rings and binaphthyl rings are classified as ring assembly arene rings even though they have a fused polycyclic arene ring skeleton, and are clearly distinguished from "fused polycyclic arene rings" such as naphthalene rings (non-ring assembly arene rings).

[0028] These arene rings can be used alone or in combination. Among these arene rings, a benzene ring and a biphenyl ring are preferred, and a benzene ring is particularly preferred. Ring Z 3 The phenylene group in which R is a benzene ring may be any of a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group, but preferably contains at least a 1,4-phenylene group, and is particularly preferably a 1,4-phenylene group from the viewpoint of forming a linear polyphenylene sulfide resin and improving the mechanical properties.

[0029] Ring Z 3 is a benzene ring, the proportion of 1,4-phenylene groups (p-phenylene sulfide groups) in the units represented by formula (2) may be 50 mol % or more, preferably 70 mol % or more, more preferably 90 mol % or more, and most preferably 100 mol %.

[0030] R 4 Examples of the alkyl group represented by the formula (I) include a linear or branched C alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, and a t-butyl group. 1-6 These alkyl groups can be used alone or in combination of two or more. Among these, C groups such as methyl groups are preferred. 1-4 Alkyl groups are preferred.

[0031] R 4 The number of substitutions s in the ring Z can be any integer greater than or equal to 0. 3 The number of substitutions s can be appropriately selected depending on the type of group, and may be, for example, an integer of 0 to 8. Preferred substitution numbers s are, in the following stepwise order, integers of 0 to 4, integers of 0 to 3, integers of 0 to 2, 0 or 1, with 0 being the most preferred.

[0032] In the polyarylene sulfide resin, the proportion of the repeating unit represented by the formula (2) may be 50 mol% or more of all structural units, preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably 100 mol%.

[0033] Other units include units containing an arene ring, such as a phenylene ether unit, a phenylene carbonyl unit, and a phenylene sulfonyl unit.

[0034] From the viewpoint of mechanical properties, the polyarylene sulfide resin is preferably a polyphenylene sulfide resin (polyphenylene sulfide resin or polyphenylene thioether resin). Examples of polyphenylene sulfide resins include polyphenylene sulfide (PPS), polyphenylene sulfide ketone (PPSK), polyphenylene sulfide sulfone (PPSS), and polybiphenylene sulfide (PBPS). Among these, PPS is preferred, and linear PPS is particularly preferred.

[0035] The weight-average molecular weight (Mw) of the polyarylene sulfide resin may be 1,000 or more, for example, 1,000 to 500,000, preferably 5,000 to 300,000, further preferably 10,000 to 100,000, even more preferably 15,000 to 80,000, and most preferably 20,000 to 60,000. If the molecular weight is too small, the mechanical properties of the resin composition may be reduced. The range of the weight-average molecular weight may be the range of the weight-average molecular weight of the polyphenylene sulfide resin.

[0036] In this specification and claims, the weight average molecular weight of the polyarylene sulfide resin can be measured using gel permeation chromatography (standard resin: polystyrene).

[0037] The melting point of the polyarylene sulfide resin is, for example, 200 to 350°C, preferably 230 to 320°C, further preferably 250 to 300°C, even more preferably 260 to 290°C, and most preferably 270 to 280°C. If the melting point is too low, heat resistance may be reduced, and conversely, if it is too high, moldability may be reduced. The melting point range may be within the melting point range of the polyphenylene sulfide resin.

[0038] The glass transition temperature of the polyarylene sulfide resin is, for example, 50 to 150°C, preferably 60 to 130°C, further preferably 70 to 120°C, even more preferably 80 to 110°C, and most preferably 90 to 100°C. If the glass transition temperature is too low, there is a risk of reduced heat resistance, and conversely, if it is too high, there is a risk of reduced moldability. The glass transition temperature range may be the same as the glass transition temperature range of the polyphenylene sulfide resin.

[0039] In this specification and claims, the melting point and glass transition temperature of the polyarylene sulfide resin can be measured using a differential scanning calorimeter (DSC).

[0040] The proportion of the polyarylene sulfide resin in the resin composition may be 10% by mass or more, for example, 10 to 99.9% by mass, preferably 30 to 99% by mass, further preferably 50 to 98% by mass, more preferably 60 to 97% by mass, and most preferably 65 to 96% by mass. If the proportion of the polyarylene sulfide resin is too low, there is a risk that the mechanical properties will deteriorate, and conversely, if it is too high, there is a risk that the moldability will deteriorate.

[0041] [Fluorene compounds] The resin composition of the present invention can improve melt flowability without impairing mechanical properties because it contains a polyarylene sulfide resin and a fluorene compound represented by formula (1). In particular, the fluorene compound has a fused polycyclic or ring assembly aryl skeleton at the 9,9-position of the fluorene skeleton, which can suppress gas generation during molding and improve productivity (moldability).

[0042] In the formula (1), ring Z 1 and Z 2 The fused polycyclic arene ring (fused polycyclic aromatic hydrocarbon ring) and the ring-assembled arene ring (ring-assembled aromatic hydrocarbon ring) represented by the formula (2) include ring Z 3 and the fused polycyclic arene rings and ring-assembled arene rings exemplified by:

[0043] Ring Z 1 Types of ring Z 2 Among the fused polycyclic arene rings and ring-assembly arene rings, a biphenyl ring and a naphthalene ring are preferred, and a biphenyl ring is particularly preferred because it can achieve both high mechanical properties and high moldability at a high level.

[0044] The fluorene compound represented by the formula (1) may be a compound having no functional group (or reactive group) [a compound in which p1 and p2 are 0 in the formula (1), for example, a 9,9-bis(polycyclic aryl)fluorene such as 9,9-bis(3-phenylphenyl)fluorene], but is preferably a compound having a functional group (a compound in which p1 and p2 are 1 or more in the formula (1)).

[0045] That is, in the formula (1), the functional group X 1 and X 2 The numbers of substitutions p1 and p2 may be integers of 0 or more, preferably 1 to 3, more preferably 1 to 2, and most preferably 1. The numbers of substitutions p1 and p2 may be different, but are preferably the same. When the numbers of substitutions p1 and p2 are 2 or more, two or more functional groups X1 or functional group X 2 The types of may be different from each other, but are preferably the same.

[0046] Functional group X 1 and X 2 The substitution position of ring Z is not particularly limited. 1 and ring Z 2 For example, ring Z 1 and ring Z 2 When is a biphenyl ring or a naphthalene ring, the following substitution positions may be used:

[0047] Ring Z 1 and ring Z 2 is a biphenyl ring, the functional group X 1 and X 2 The substitution position of may be any of the 2- to 6-positions and the 2'- to 6'-positions of the biphenyl ring, but for example, the 3- or 4-position of the biphenyl ring may be bonded to the 9-position of the fluorene. When the 3-position of the biphenyl ring is bonded to the 9-position of the fluorene, the functional group X 1 and X 2 The substitution position of may be any of the 2-, 4-, 5-, 6-, 2'-, 3'-, and 4'-positions of the biphenyl ring, preferably the 6- or 4'-position, and particularly preferably the 6-position. When the 4-position of the biphenyl ring is bonded to the 9-position of the fluorene, the functional group X 1 and X 2 The substitution position of may be any of the 2-, 3-, 2'-, 3'-, and 4'-positions of the biphenyl ring, preferably at the 2- or 4'-position, and particularly preferably at the 2-position.

[0048] Ring Z 1 and ring Z 2 is a naphthalene ring, the functional group X 1 and X 2The substitution position is often at any one of the 5th to 8th positions of the naphthalene ring bonded at the 1st or 2nd position to the 9th position of the fluorene ring, and the 1st or 2nd position of the naphthalene ring is substituted with the 9th position of the fluorene ring (substitution in a 1-naphthyl or 2-naphthyl relationship), and substitution in a 1,5-position or 2,6-position relationship with respect to this substitution position is preferred, and substitution in a 2,6-position relationship is particularly preferred.

[0049] Functional group X 1 Type and functional group X 2 The types of functional groups X may be different, but are preferably the same. 1 and X 2 Although the group may be an amino group, it is preferable to use the group -[(OA) n -Y] is preferred. Furthermore, the group -[(OA) n -Y] may be a mercapto group, a glycidyloxy group, or a (meth)acryloyloxy group, but is preferably a hydroxyl group from the viewpoints of compatibility with polyarylene sulfide resins, maintenance of mechanical strength, and improvement of flowability.

[0050] In the group X of the formula (1), examples of the linear or branched alkylene group represented by the group A include C alkylene groups such as ethylene, propylene (1,2-propanediyl), trimethylene, 1,2-butanediyl, and tetramethylene. 2-6 Among these, linear or branched C 2-4 Alkylene groups are preferred, and linear or branched C 2-3 An alkylene group is more preferred, and an ethylene group is even more preferred. When n is 2 or more, the alkylene groups may be composed of different alkylene groups, but are preferably composed of the same alkylene group. 1 Group A and ring Z 2 and group A may be different, but are preferably the same.

[0051] The repeat number (number of moles added) n of the oxyalkylene group (OA) may be an integer of 0 or 1 or more, and may be selected from integers in the range of about 0 to 20, for example, an integer of 0 to 15. However, from the viewpoint of heat resistance and compatibility with polyarylene sulfide resins, the repeat number n is preferably in the following stepwise ranges of integers from 1 to 10, 1 to 5, 1 to 3, and 1 to 2, and most preferably 1. If the repeat number n is too large, the mechanical properties of the resin composition may be reduced. Furthermore, when the substitution numbers p1 and p2 are 2 or more, the same ring Z 1 (or ring Z 2 The number of repeats n in the ring Z may be different from each other, but is preferably the same. 1 The repeat number n in the ring Z 2 may be different from the number of repetitions n in (1), but is preferably the same.

[0052] In this specification and claims, the "number of repetitions (number of moles added)" may be an average value (arithmetic mean value, additive mean value) or an average number of moles added, and preferred embodiments are the same as the preferred range of integers.

[0053] In the formula (1), the group R 1 and R 2 Examples of the substituent represented by the formula (I) include a halogen atom, a hydrocarbon group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, a nitro group, and a cyano group.

[0054] Representative examples of these substituents include halogen atoms, hydrocarbon groups such as alkyl groups, cycloalkyl groups, and aralkyl groups, alkoxy groups, acyl groups, nitro groups, cyano groups, and substituted amino groups. 1 and R 2 Examples of the alkyl group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkoxy group. The alkyl group may be a straight-chain or branched C 1-6Examples of the cycloalkyl group include C alkyl groups such as cyclohexyl groups. 5-8 Examples of the aralkyl group include C aryl groups such as benzyl and phenethyl groups. 6-10 Aryl-C 1-4 Examples of the aryl group include C 6-14 The alkoxy group includes a linear or branched C 1-4 Alkoxy groups and the like are examples of the substituent R 1 The type and substituent R 2 The types of the alkyl groups may be different from each other, but are preferably the same. Among these, alkyl groups are preferred, and straight-chain or branched-chain C groups such as methyl groups are preferred. 1-4 Alkyl groups are particularly preferred.

[0055] R 1 and R 2 The numbers of substitutions m1 and m2 may be integers of 0 or more, and the ring Z 1 and ring Z 2 The numbers m1 and m2 can be selected appropriately depending on the type of R and may each be, for example, an integer of 0 to 8. Preferred numbers of substitutions m1 and m2 are, in the following order, integers of 0 to 4, integers of 0 to 3, integers of 0 to 2, 0 or 1, with 0 being the most preferred. The numbers of substitutions m1 and m2 may be different, but are preferably the same. When the numbers of substitutions m1 and m2 are 2 or more, 2 or more R 1 or R 2 The types of R may be different, but are preferably the same. 1 and R 2 The substitution position of ring Z is not particularly limited. 1 and ring Z 2 and functional group X 1 and X 2 The substitution may be made at any position other than the bonding position with the fluorene.

[0056] In the formula (1), R 3Examples of the substituent represented by the formula (I) include a hydrocarbon group, a cyano group, and a halogen atom. Examples of the hydrocarbon group include an alkyl group and an aryl group. Examples of the alkyl group include a linear or branched C alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and a t-butyl group. 1-6 Examples of aryl groups include C alkyl groups such as phenyl groups. 6-10 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, etc. These substituents may be used alone or in combination.

[0057] These groups R 3 Among these, alkyl groups, cyano groups, and halogen atoms are preferred, alkyl groups are more preferred, and linear or branched C groups such as methyl groups are preferred. 1-4 Alkyl groups are more preferred, and C 1-2 Alkyl groups are most preferred.

[0058] base R 3 The number of substitutions k may be an integer of 0 to 8, and preferred ranges are, in the following stepwise order, integers of 0 to 6, integers of 0 to 5, integers of 0 to 4, integers of 0 to 3, integers of 0 to 2, 0 or 1, with 0 being the most preferred. Note that the numbers of substitutions in the two different benzene rings constituting the fluorene ring may be the same or different. In addition, the groups R substituted on the different benzene rings may be the same or different. 3 When k is 2 or more, the two or more groups R substituted on the same or different benzene rings may be different from each other, but are preferably the same. 3 The types of groups R may be the same or different. 3 The substitution position of is not particularly limited, and may be, for example, a substitution position selected from the 2- to 7-positions of the fluorene ring, and is preferably a substitution position selected from the 2-, 3-, and 7-positions.

[0059] Specific fluorene compounds include 9,9-bis(C 6-109,9-bis(hydroxynaphthyl)fluorenes such as 9,9-bis(6-hydroxy-2-naphthyl)fluorene and 9,9-bis(5-hydroxy-1-naphthyl)fluorene; 9,9-bis(C such as 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene 6-10 Aryl-hydroxy(poly)C 2-4 9,9-bis(hydroxy(poly)C) such as 9,9-bis[6-(2-hydroxyethoxy)-2-naphthyl]fluorene; 2-4 alkoxynaphthyl)fluorene; and compounds in which the hydroxyl group in these compounds is substituted with a mercapto group, a glycidyloxy group, or a (meth)acryloyloxy group.

[0060] The fluorene compounds can be used alone or in combination of two or more. Among the fluorene compounds, 9,9-bis(phenyl-hydroxyphenyl)fluorene, 9,9-bis(hydroxynaphthyl)fluorene, and 1 to 10 moles of C per mole of hydroxyl group of these compounds are preferred. 2-4 At least one selected from the group consisting of alkylene oxide adducts is preferred, and 1 to 5 moles of C per mole of hydroxyl group of 9,9-bis(phenyl-hydroxyphenyl)fluorene. 2-4 Adducts with alkylene oxides are particularly preferred.

[0061] The fluorene compound has high heat resistance, and when measured by thermogravimetry-differential thermal analysis (TG-DTA), the mass loss rate at 320°C may be 1.5% by mass or less, with preferred ranges being 1.2% by mass or less, 1% by mass or less, 0.8% by mass or less, and 0.5% by mass or less, in the following stepwise order, for example, 0.1 to 1% by mass, preferably 0.2 to 0.8% by mass. If the mass loss rate is too large, moldability may be reduced.

[0062] The proportion of the fluorene compound can be selected from the range of 0.01 to 50 parts by mass, particularly 0.01 to 30 parts by mass, per 100 parts by mass of the polyarylene sulfide-based resin, for example, 0.05 to 20 parts by mass, preferably 0.1 to 10 parts by mass, more preferably 0.5 to 9 parts by mass, more preferably 2 to 8 parts by mass, and most preferably 3 to 7 parts by mass. When high moldability is required for a resin composition containing a fibrous reinforcing material and / or a heat dissipating material, the proportion of the fluorene compound is, for example, 1 to 50 parts by mass, preferably 5 to 30 parts by mass, more preferably 10 to 25 parts by mass, and more preferably 12 to 20 parts by mass, per 100 parts by mass of the polyarylene sulfide-based resin. If the proportion of the fluorene compound is too low, moldability may be reduced, while if it is too high, mechanical strength may be reduced.

[0063] [Fiber reinforcement] The resin composition of the present invention may further contain a fibrous reinforcing material to improve mechanical strength. Resin compositions containing a fibrous reinforcing material usually have significantly reduced fluidity, but the present invention can improve the mechanical strength of the resin composition without significantly reducing melt fluidity. Therefore, the combination of a polyarylene sulfide resin, the fluorene compound, and a fibrous reinforcing material can achieve both highly excellent mechanical properties and high moldability. Fibrous reinforcing materials can be broadly classified into inorganic fibers and organic fibers.

[0064] Examples of inorganic fibers include glass fibers, carbon fibers, boron fibers, whiskers, wollastonite, etc. Examples of organic fibers include polyester fibers such as polyalkylene asphalt fibers, and polyamide fibers such as aliphatic polyamide fibers and aramid fibers.

[0065] These fibrous reinforcing materials can be used alone or in combination of two or more. Among these, inorganic fibers are preferred, and glass fibers and / or carbon fibers are particularly preferred.

[0066] Examples of glass components that form glass fibers include E-glass (alkali-free electrical insulating glass), S-glass (high-strength glass), C-glass (chemical glass), A-glass (general-use alkali-containing glass), and YM-31-A-glass (high-elasticity glass). Among these, E-glass, C-glass, and S-glass are preferred from the viewpoint of mechanical properties, and E-glass is particularly preferred. Glass fibers formed from these glass components can be used alone or in combination of two or more.

[0067] Examples of carbon fibers include polyacrylonitrile (PAN)-based carbon fibers, pitch-based carbon fibers such as isotropic pitch-based carbon fibers and mesophase pitch-based carbon fibers, and vapor-grown carbon fibers. Of these, PAN-based carbon fibers are preferred from the viewpoint of mechanical strength. These carbon fibers can be used alone or in combination.

[0068] Of these, carbon fiber is most preferred.

[0069] The fibrous reinforcing material may be surface-treated with a sizing agent, a silane coupling agent, or the like.

[0070] The fibrous reinforcing material may be a long fiber, but is preferably a short fiber. The average fiber length of the fibrous reinforcing material is, for example, 0.1 to 20 mm, preferably 0.5 to 15 mm, more preferably 1 to 10 mm, and most preferably 3 to 8 mm. Furthermore, due to the influence of shear forces during mixing (or kneading) of the fibrous reinforcing material with the polyamide resin and the fluorene compound or during molding, the average fiber length of the fibrous reinforcing material in the composition or molded article may be shorter than that before mixing, for example, 0.05 to 10 mm, preferably 0.1 to 8 mm, and more preferably 0.3 to 5 mm.

[0071] The average fiber diameter of the fibrous reinforcing material is not particularly limited, and therefore the fibrous reinforcing material may be a fibrous reinforcing material having an average fiber diameter on the order of nanometers, but from the standpoint of mechanical strength and the like, the average fiber diameter is, for example, 1 to 200 μm, preferably 2 to 100 μm, further preferably 3 to 80 μm, even more preferably 5 to 50 μm, and most preferably 8 to 30 μm.

[0072] In this specification and claims, the average fiber length and average fiber diameter of the fibrous reinforcing material may be calculated by randomly selecting 50 fibers from a scanning electron microscope image and averaging them.

[0073] The fibrous reinforcing material may be in the form of a fabric formed from the inorganic and / or organic fibers.

[0074] The proportion of the fibrous reinforcing material is, for example, 1 to 200 parts by mass, preferably 5 to 150 parts by mass, more preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass, and most preferably 30 to 50 parts by mass, per 100 parts by mass of the polyarylene sulfide resin. The proportion of the fibrous reinforcing material is, for example, 0.1 to 100 parts by mass, preferably 1 to 50 parts by mass, more preferably 2 to 30 parts by mass, more preferably 3 to 20 parts by mass, and most preferably 5 to 10 parts by mass, per 1 part by mass of the fluorene compound. If the proportion of the fibrous reinforcing material is too low, the reinforcing effect may not be exerted, and conversely, if it is too high, moldability may be reduced.

[0075] [Heat dissipation material] The resin composition of the present invention may further contain a heat dissipating material (heat dissipating filler or heat conducting material) to improve thermal conductivity (heat dissipation). A resin composition containing a heat dissipating material usually has a significantly reduced fluidity, but in the present invention, the thermal conductivity of the resin composition can be improved without a significantly reduced melt fluidity. Therefore, by combining a polyarylene sulfide resin, the fluorene compound, and a heat dissipating material, both high thermal conductivity and high moldability can be achieved.

[0076] Examples of heat dissipation materials include metals or alloys such as metallic silicon, iron, copper, magnesium, aluminum, gold, platinum, silver, zinc, manganese, and stainless steel; silicates such as tourmaline and diatomaceous earth; nitrogen compounds (nitrides or metal nitrides) such as boron nitride, aluminum nitride, carbon nitride, and silicon nitride; carbon compounds (carbides or metal carbides) such as silicon carbide, fluorine carbide, boron carbide, and tungsten carbide; carbon materials such as graphite, coke, and diamond; and metal oxides such as silicon oxide, alumina, iron oxide, magnesium oxide, zinc oxide, and beryllium oxide.

[0077] These heat dissipating materials can be used alone or in combination of two or more. Among these, heat dissipating materials formed from nitrogen compounds and metal oxides are preferred.

[0078] The shape of the heat dissipating material may be granular, plate-like (or scale-like), rod-like, fibrous, irregular, etc. Of these shapes, granular and plate-like (or scale-like) shapes are preferred.

[0079] The average particle size of the heat dissipating material is, for example, 0.1 to 100 μm, preferably 1 to 50 μm, and more preferably 5 to 30 μm.

[0080] In this specification and claims, the average particle size of the heat dissipating material may be calculated by randomly selecting 50 particles of heat dissipating material from an image of a scanning electron microscope photograph and averaging the particle sizes.

[0081] The proportion of the heat dissipating material is, for example, 10 to 200 parts by mass, preferably 30 to 150 parts by mass, more preferably 50 to 120 parts by mass, more preferably 60 to 100 parts by mass, and most preferably 70 to 90 parts by mass, per 100 parts by mass of the polyarylene sulfide resin. The proportion of the heat dissipating material is, for example, 1 to 100 parts by mass, preferably 3 to 50 parts by mass, more preferably 5 to 30 parts by mass, more preferably 8 to 20 parts by mass, and most preferably 10 to 15 parts by mass, per 1 part by mass of the fluorene compound. If the proportion of the heat dissipating material is too low, the effect of improving thermal conductivity may not be achieved, and conversely, if it is too high, moldability may be reduced.

[0082] [Other ingredients] The resin composition of the present invention may further contain other thermoplastic resins in addition to the polyarylene sulfide resin.

[0083] Examples of other thermoplastic resins include olefin resins, halogen-containing vinyl resins, acrylic resins, styrene resins, polyester resins, polycarbonate resins, polyacetal resins, polyphenylene ether resins, polysulfone resins, polyether ketone resins, polyamide resins, polyimide resins, liquid crystal polymers, and thermoplastic elastomers. These thermoplastic resins can be used alone or in combination. If necessary, the polyarylene sulfide resin may form a polymer alloy with these thermoplastic resins.

[0084] The proportion of the other thermoplastic resin may be, for example, 100 parts by mass or less, preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 10 parts by mass or less, per 100 parts by mass of the polyarylene sulfide resin, and may be, for example, 1 to 10 parts by mass.

[0085] The resin composition of the present invention may further contain conventional additives as needed. Examples of conventional additives include powdery fillers or reinforcing agents (or reinforcing materials), colorants such as dyes and pigments, conductive agents, flame retardants, flame retardant assistants, plasticizers, lubricants, antioxidants, UV absorbers, heat stabilizers, mold release agents, antistatic agents, dispersants, flow control agents, leveling agents, antifoaming agents, surface modifiers, stress reducers, nucleating agents, and crystallization accelerators. These additives can be used alone or in combination.

[0086] The total proportion of conventional additives may be, for example, 100 parts by mass or less, preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 10 parts by mass or less, for example, 1 to 10 parts by mass, relative to 100 parts by mass of the polyarylene sulfide resin.

[0087] [Resin composition and molded article] The resin composition of the present invention can be prepared by mixing a polyarylene sulfide resin, a fluorene compound represented by the formula (1), and, if necessary, other components (such as a fibrous reinforcing material) by a conventional method such as dry mixing or melt kneading, and the resin composition may be in the form of pellets or the like.

[0088] The resin composition of the present invention has high melt fluidity, and its MFR (melt flow rate or melt flow index (MFI)) measured in accordance with ISO 1133 (temperature: 315°C, load: 2.16 kgf) may be 10 g / 10 min or more, preferably 10 to 200 g / 10 min, and more preferably 30 to 100 g / 10 min. When the resin composition does not contain a fibrous reinforcing material, the MFR of the resin composition is, for example, 20 to 200 g / 10 min, preferably 25 to 100 g / 10 min, and more preferably 30 to 80 g / 10 min. When the resin composition contains a fibrous reinforcing material, the MFR of the resin composition is, for example, 10 to 50 g / 10 min, and preferably 12 to 30 g / 10 min. If the MFR is too low, moldability may be reduced.

[0089] The resin composition of the present invention has good mechanical properties despite containing the fluorene compound having a relatively low molecular weight. The Charpy impact strength of the resin composition measured in accordance with JIS K7111 is 1 kJ / m 2 or more, for example, 1 to 30 kJ / m 2 , preferably 1.5 to 10 kJ / m 2 When a fibrous reinforcing material is contained, it is preferably 3 to 10 kJ / m 2 is.

[0090] The tensile strength measured in accordance with ISO 527 (test speed 5 mm / min) may be 50 MPa or more, for example, 50 to 300 MPa, preferably 80 to 250 MPa, and when a fibrous reinforcing material is contained, preferably 150 to 250 MPa.

[0091] The tensile elongation measured in accordance with ISO 527 (test speed 5 mm / min) may be 1% or more, for example 1 to 10%, preferably 3 to 8%, and when a fibrous reinforcing material is included, preferably 1 to 3%.

[0092] The tensile modulus measured in accordance with ISO 527 (test speed 5 mm / min) may be 1 GPa or more, for example, 1 to 100 GPa, preferably 3 to 30 GPa, and when a fibrous reinforcing material is contained, preferably 10 to 50 GPa.

[0093] The flexural strength measured in accordance with ISO 178 may be 100 MPa or more, for example, 100 to 1000 MPa, preferably 130 to 500 MPa, and when a fibrous reinforcing material is contained, preferably 200 to 500 MPa.

[0094] The flexural modulus measured in accordance with ISO 178 may be 1 GPa or more, for example, 1 to 100 GPa, preferably 3 to 30 GPa, and when a fibrous reinforcing material is contained, preferably 10 to 50 GPa.

[0095] The deflection temperature under load (flexural stress: 1.8 MPa, flatwise) measured in accordance with ISO 75 may be 80°C or higher, for example, 80 to 300°C, preferably 100 to 280°C, and when a fibrous reinforcing material is contained, it is preferably 200 to 300°C, more preferably 250 to 280°C.

[0096] The molded article of the present invention can be produced by molding the resin composition using a conventional molding method. Conventional molding methods include compression molding, injection molding, injection compression molding, extrusion molding, transfer molding, blow molding, pressure molding, and casting molding. In these molding methods, the heating temperature for molding, such as the melt-kneading temperature, may be any temperature equal to or higher than the melting point of the polyarylene sulfide resin, and is preferably 5 to 80°C higher than the melting point, more preferably 10 to 60°C higher than the melting point, and most preferably 20 to 50°C higher than the melting point.

[0097] The shape of the molded article of the present invention is not particularly limited and can be selected depending on the application. Examples of such shapes include one-dimensional structures such as linear or thread-like structures; two-dimensional structures such as film-like, sheet-like, and plate-like structures; and three-dimensional structures such as block-like, rod-like, tubular, and hollow structures. [Example]

[0098] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. The abbreviations and details of the various evaluation methods and raw materials used are also shown below.

[0099] [MFR] In accordance with ISO 1133, measurements were performed under conditions of a holding time of 5 minutes, a temperature of 315°C (320°C in Examples 5 and 6 and Comparative Example 4), and a test load of 2.16 kgf.

[0100] [Charpy impact strength (notched)] Measurement was carried out in accordance with JIS K7111.

[0101] [Izod impact strength (notched)] Measurement was carried out in accordance with JIS K7110.

[0102] [Tensile strength, tensile elongation and tensile modulus] Measurements were made in accordance with ISO 527 at a test speed of 5 mm / min.

[0103] [Flexural strength and flexural modulus] Measured according to ISO 178.

[0104] [Deflection temperature under load] Measurement was carried out in accordance with ISO 75 using the flatwise method at a bending stress of 1.8 MPa.

[0105] [Thermal Conductivity] The resin sample was press-molded at 320°C to prepare a 4 mm thick press sheet. A φ50 mm test piece was cut out from the prepared sheet, and the thermal conductivity was measured in accordance with ASTM E1530 (disk heat flow meter method).

[0106] [Raw materials] (Polyarylene sulfide resin) Polyphenylene sulfide resin (PPS): Toray Industries, Inc. "TORELINA A900" Heat-dissipating polyphenylene sulfide resin (heat-dissipating PPS): DIC Corporation's "DIC.PPS TX-2010-A1", polyphenylene sulfide resin content 30-40% by mass, inorganic filler content 35-45% by mass, glass fiber content 15-25% by mass (fibrous reinforcing material) Carbon fiber (CF): Teijin Limited "TENAX-J HT C702", cut length 6.0 mm (fluorene compounds) 9,9-bis[4-(2-hydroxyethoxy)-3-phenylphenyl]fluorene: "BOPPEF" manufactured by Osaka Gas Chemicals Co., Ltd., mass loss rate at 320°C: 0.4% 9,9-Bis[4-(2-hydroxyethoxy)phenyl]fluorene: "BPEF" manufactured by Osaka Gas Chemicals Co., Ltd., mass loss rate at 320°C: 1.6%

[0107] [Examples 1 to 4 and Comparative Examples 1 to 3] The raw materials were dry-blended in the proportions shown in Table 1. Then, using a twin-screw extruder (Warner & Pfleiderer "ZSK40", L / D: 41.75, screw diameter: 44 mm), the mixture was kneaded at a temperature of 320±10°C, a screw rotation speed of 250 rpm, and a discharge rate of 15 kg / hr to prepare a pellet-shaped resin composition. When CF was added, it was side-fed using a vibrating feeder. The presence or absence of gas generation near the outlet of the kneader was visually confirmed. Test pieces for each evaluation item were prepared by injection molding from the resulting resin compositions that showed no gas generation. The blending proportions and evaluation results are shown in Table 1.

[0108] [Table 1]

[0109] As is clear from the results in Table 1, in comparison with Comparative Example 1, in Examples 1 and 2, despite containing the low molecular weight compound BOPPEF, the MFR was improved by approximately 1.5 to 2.1 times without a significant decrease in mechanical properties.

[0110] In Example 2, which contained BOPPEF at a ratio of 10 mass % relative to the total weight of PPS, a slight decrease in tensile strength was observed compared to Comparative Example 1 and Example 1. The reason for this is unclear, but it is presumed that the relatively high ratio of BOPPEF, a low molecular weight compound, prevented the composition from maintaining its strength.

[0111] Furthermore, for the compositions containing CF, in Examples 3 and 4, despite the inclusion of the low molecular weight compound BOPPEF, the MFR was improved by approximately 1.3 to 1.7 times without a significant decrease in mechanical properties compared to Comparative Example 2. In Example 4, which contained BOPPEF at a ratio of 10 mass% relative to the total weight of PPS, a slight decrease in tensile strength and flexural strength was observed compared to Comparative Example 2 and Example 3. The reason for this is unclear, but it is presumed that the relatively high ratio of BOPPEF, a low molecular weight compound, prevented the composition from maintaining its strength.

[0112] Furthermore, in Comparative Example 3, in which BPEF was added, the generation of gas components was observed near the outlet of the kneader during kneading. This is thought to be because BPEF has a lower thermal weight loss temperature than BOPPEF, and therefore BPEF volatilized or decomposed during kneading with PPS.

[0113] [Examples 5 to 6 and Comparative Example 4] The raw materials were dry-blended in the proportions shown in Table 2. Then, using a twin-screw extruder ("Process 11" manufactured by Thermo Fisher Scientific), the mixture was kneaded at a temperature of 320±10°C, a screw rotation speed of 200 rpm, and a discharge rate of approximately 500 g / hr to prepare a pellet-shaped resin composition. Test pieces for each evaluation item were prepared from the resulting resin composition by injection molding. The blending proportions and evaluation results are shown in Table 2.

[0114] [Table 2]

[0115] As is clear from the results in Table 2, in Examples 5 and 6, despite containing the low molecular weight compound BOPPEF, the MFR was improved by approximately 1.5 to 2.1 times compared to Comparative Example 4 without significantly reducing the mechanical properties and thermal conductivity.

[0116] In Example 6, which contained approximately 13.2 to 17.5 parts by mass of BOPPEF per 100 parts by mass of PPS, a slight decrease in bending strength was observed compared to Comparative Example 4 and Example 5 (which contained approximately 6.2 to 8.1 parts by mass of BOPPEF). The reason for this is unclear, but it is presumed that the relatively high proportion of BOPPEF, a low-molecular-weight compound, prevented the composition from maintaining its strength. [Industrial Applicability]

[0117] The resin composition of the present invention can be effectively used for molded articles requiring higher mechanical strength while taking advantage of the properties of polyarylene sulfide resins, such as toughness and heat resistance. Representative examples include automotive parts such as exhaust gas treatment valves, carburetors, manifolds, distributors, ignition, and terminal connectors; electrical and electronic parts such as connectors, switches, coil bobbins, relays, printed circuit boards, and integrated circuit components; office automation equipment parts such as printer claws, copier bearings, and computer parts; home appliances such as microwave oven parts, iron parts, induction cooker coil bases, and rice cooker valves; and mechanical parts such as gears, piston rings, valves, and pump parts.

Claims

1. A resin composition comprising a polyarylene sulfide resin and a fluorene compound represented by the following formula (1), wherein the proportion of the fluorene compound represented by the formula (1) is 0.01 to 50 parts by mass relative to 100 parts by mass of the polyarylene sulfide resin: 【Chemical 1】 [In the formula, Ring Z １ and ring Z ２ are the same or different and represent a biphenyl ring or a naphthalene ring, X １ and X ２ are the same or different and represent a group -[(OA) ｎ -Y] (In the formula, Y represents a hydroxyl group, a mercapto group, a glycidyloxy group, or a (meth)acryloyloxy group; A's may be the same or different and each represent a linear or branched alkylene group; n represents an integer of 0 or more) or an amino group, p1 and p2 are the same or different and each represent an integer of 0 or more; R １ and R ２ are the same or different and represent an alkyl group, m1 and m2 are the same or different and each represent an integer of 0 or more; R ３ represents an alkyl group, k represents an integer of 0 or more.

2. In the formula (1), p1 and p2 are the same or different and represent an integer of 1 or more, m1 and m2 are the same or different and represent an integer of 0 to 2, and k is an integer of 0 to 2. The resin composition according to claim 1.

3. The fluorene compound represented by the formula (1) is 9,9-bis(phenyl-hydroxyphenyl)fluorene, 9,9-bis(hydroxynaphthyl)fluorene, and 1 to 10 moles of C per mole of hydroxyl group of these compounds. ２－４ 3. The resin composition according to claim 1, wherein the resin is at least one selected from the group consisting of alkylene oxide adducts.

4. In the formula (1), ring Z １ and ring Z ２ The resin composition according to any one of claims 1 to 3, wherein is a biphenyl ring.

5. The resin composition according to any one of claims 1 to 4, wherein the polyarylene sulfide-based resin is a polyphenylene sulfide-based resin.

6. The resin composition according to any one of claims 1 to 5, further comprising a fibrous reinforcing material.

7. The resin composition according to any one of claims 1 to 6, further comprising a heat dissipation material.

8. The resin composition according to any one of claims 1 to 7, wherein the ratio of the fluorene compound represented by the formula (1) is 0.1 to 10 parts by mass relative to 100 parts by mass of the polyarylene sulfide resin.

9. A molded article formed from the resin composition according to any one of claims 1 to 8.

10. A method for improving the melt flowability of a polyarylene sulfide resin, comprising adding a fluorene compound represented by formula (1) according to claim 1 to the polyarylene sulfide resin.

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