JP3092978B2 - Polyarylene sulfide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene sulfide resin having high elongation, high toughness, and improved sliding characteristics while substantially maintaining the inherent strength and rigidity inherent to polyarylene sulfide resin. The present invention relates to a polyarylene sulfide resin composition. The polyarylene sulfide resin of the present invention has the above-mentioned properties, and therefore can be used in a wide range of fields as a sliding member.

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter referred to as "P
Polyarylene sulfide resin represented by resin (PS) is known as a high-performance engineering plastic having excellent mechanical properties, heat resistance, chemical resistance and electrical insulation. One of the typical applications is sliding parts (friction and wear parts) used under high loads utilizing high rigidity.
It is used in the form of a composition comprising PPS and a reinforcing fiber such as glass fiber, carbon fiber or aramid fiber or a composition comprising PPS and such a reinforcing fiber and a fluororesin represented by polytetrafluoroethylene.

[0003] The sliding material comprising the PPS resin composition as described above causes the material to soften or seize due to frictional heat storage under high-speed sliding. Is limited to use in As an attempt to further improve the slidability of the sliding parts of such a PPS resin composition, a potassium titanate whisker, graphite, silica, aluminum silicate, titanium dioxide or a thermosetting resin is added to these PPS resin compositions. It has been proposed to incorporate a small amount of However, there is a problem that a sufficient effect of improving the slidability is not achieved or one of the excellent characteristics inherent in the PPS resin composition is impaired. In addition, it has not been possible to use it under high-speed sliding.

[0004] Under the circumstances described above, it is required that a sliding material comprising a PPS resin composition suppress heat generation, enable use under high-speed sliding, and improve rigidity at high temperatures. Have been.

[0005] On the other hand, PPS resin has excellent mechanical properties and rigidity, but also has a disadvantage that it is brittle. In order to solve this problem, it is known to blend a thermoplastic elastomer with a PPS resin, whereby the brittleness is improved but the rigidity is reduced. If this difficulty is solved, it is expected that the use of the sliding material composed of the PPS resin composition will be further expanded.

[0006]

An object of the present invention is to provide a polyarylene sulfide (hereinafter abbreviated as "PAS").
The resin composition inherently has good mechanical properties, while substantially retaining rigidity, exhibits high elongation, is highly tough, and has a reduced friction coefficient and its fluctuation under high-speed sliding,
An object of the present invention is to provide a PAS resin composition useful as a sliding material in which heat generation is significantly suppressed.

[0007]

The object of the present invention is to provide (A) P
100 to 100 parts by weight of a resin mixture composed of 50 to 99% by weight of an AS resin and (B) 50 to 1% by weight of a thermoplastic elastomer;
(C) 0.1 to 10 parts by weight of at least one compound selected from aromatic maleimide compounds represented by the following general formulas (1) and (2), and (F) reinforcing fiber 5 as an optional component ~ 100 parts by weight and / or inorganic filler 5
80 parts by weight, and 0.05 to 30 parts by weight of molybdenum disulfide (based on a total of 100 parts by weight of the above components (A), (B), (C) and (F)) as essential components and (E) A) a PAS comprising 0.05 to 25 parts by weight of a silicone compound having a functional group on at least one terminal (based on a total of 100 parts by weight of the components (A), (B), (C) and (F)). This is achieved by a resin composition.

[0008]

Embedded image In the formula (1), R ₁ is a divalent organic group containing a phenylene group or a phenylene group having a substituent.

[0009]

Embedded image In the formula (2), R ₂ is a divalent hydrocarbon group, and n is 0.1, or 2.

Conventionally, the addition of molybdenum disulfide or a silicone compound to a PPS resin has not been able to greatly improve its slidability.
By adding molybdenum disulfide and a specific silicone compound to a resin composition comprising S resin, (B) a thermoplastic elastomer, and (C) an aromatic maleimide compound,
It was surprising that the slidability was significantly improved without impairing the properties of the unadded resin composition, particularly the compatibility and toughness. In addition, many silicone compounds have the property of transferring to the molded product surface when added to thermoplastics,
The specific silicone compound used in the present invention is (A) PAS
When added to a resin composition comprising a resin, (B) a thermoplastic elastomer, and (C) an aromatic maleimide, no migration to the surface of a molded article is unexpectedly observed, which contributes to the achievement of the above object. It is thought to be.

The PAS resin used in the present invention is a polymer substantially consisting of repeating units -RS- (R: arylene group). Preferably, the following formula (3)

Embedded image And a random copolymer and a block copolymer containing the repeating unit in an amount of 70 mol% or more, more preferably 90 mol% or more. Examples of the small-quantity copolymerization component in the copolymer include an arylene sulfide unit represented by the following formula.

[0012]

Embedded image

[0013] PAS resins generally include Japanese Patent Publication No. 45-3
No. 368, a polymer having a relatively low molecular weight obtained by a production method is heated under an oxygen atmosphere after polymerization, or heated by adding a crosslinking agent such as a peroxide to form a polymer having a high molecular weight. So-called thermally crosslinked PAS resin, and JP-B-52-12240,
JP-B-54-8719 and linear-high-molecular-weight polymers obtained by the production methods represented by JP-A-61-7332, so-called linear PAS resins, etc. Either can be used.

The melt viscosity of the PAS resin used in the present invention is not particularly limited as long as a molded product can be obtained by a usual method such as injection molding or extrusion molding.
A resin having an apparent melt viscosity of about 100 poise to about 30,000 poise at a temperature of 10 ° C. and a shear rate of 10 ¹ to 10 ⁴ sec ⁻¹ is preferable from the viewpoint of resin properties and moldability.

Examples of the thermoplastic elastomer used in the present invention include diene elastomers, polyurethane elastomers, polyamide elastomers, polyester elastomers, and polyolefin elastomers, and those having high reactivity with an aromatic maleimide compound are preferred. .

Examples of the diene elastomer include polybutadiene elastomers and vinyl aromatic hydrocarbons represented by styrene / butadiene / styrene block copolymer elastomers and styrene / isoprene / styrene block copolymer elastomers and conjugated dienes. Block copolymer elastomers. Polybutadiene elastomer is obtained by polymerizing 1,3-butadiene using a polymerization catalyst comprising a transition metal component such as titanium, cobalt, nickel, and vanadium and an organoaluminum compound component, and a polymerization initiator comprising butyllithium and other alkyllithium. Is an elastomer obtained by Examples of the commercially available product include JSR-BR820 manufactured by Nippon Synthetic Rubber Co., Ltd.

The block copolymer elastomer comprising a vinyl aromatic hydrocarbon and a conjugated diene includes (a)
Styrene / butadiene / styrene type block copolymer elastomer having a styrene content of 10 to 50% by weight (hereinafter referred to as "SBS elastomer"); (b) Styrene obtained by selectively hydrogenating these block copolymers
Ethylene / butylene / styrene / block copolymer (S
EBS elastomers), and (C) these (a),
Modified block copolymers obtained by adding a small amount of unsaturated dicarboxylic acid or a derivative thereof to the block copolymer (b) are exemplified.

The unsaturated dicarboxylic acid or derivative thereof contained in the modified block copolymer may be a known one, such as maleic acid, fumaric acid, chloromaleic acid, itaconic acid, cis-4-cyclohexane- 1,2
-Dicarboxylic acids, and acid anhydrides, esters, amides, imides and the like of these dicarboxylic acids. Among them, maleic acid, fumaric acid and maleic anhydride are more preferred.

The SBS-based elastomer, SEBS-based elastomer and their modified block copolymers can be obtained from commercial products. For example, as a SBS elastomer, Asahiprene T430 (manufactured by Asahi Kasei Corporation),
As a SEBS elastomer, Tuftec H1041
(Asahi Kasei Kogyo Co., Ltd.), Clayton G1652 (Shell Chemical Co., Ltd.), and as acid-modified block copolymer of SBS elastomer, Tufpren 912 (Asahi Kasei Kogyo), SEBS
Examples of acid-modified block copolymers based on elastomers include Tuftec M-1913 (manufactured by Asahi Kasei Corporation) and Clayton FG
-1901X (manufactured by Shell Chemical).

The polyurethane elastomer is a rubber-like elastic body having a urethane bond —NHCO—O— in the main chain, and is obtained by reacting a polyester polyol with a diisocyanate compound. Representative examples of polyester-based polyols include esters of 1,4-butanediol and adipic acid that have a hydroxyl group at the terminal. Specific examples of the diisocyanate compound include MDI (4,4'-diphenylmethane diisocyanate), TDI (tolylene diisocyanate),
1,5-naphthalenediisocyanate and the like can be mentioned.
Examples of commercially available polyurethane elastomers include Urethane E3095A manufactured by Toyobo Co., Ltd. and Desmopan 590 manufactured by Bayer Japan K.K.

As the polyamide-based elastomer, a block copolymer comprising a hard segment of a polyamide component such as polyundecaneamide (nylon 11) and polydodecaneamide (nylon 12) and a soft segment of a polyether component or an aliphatic polyester component is used. Coalesced elastomers. Specific examples of the polyether soft segment component include polyethers represented by-(OR) _n- (R is an alkylene group having 2 to 12 carbon atoms). Specific examples of the aliphatic polyester segment component include polycaprolactone and Alkylene glycol HO-R'-OH (R 'is an alkylene group having 2 to 12 carbon atoms) and di- or tricarboxylic acid (R〃)-(COO
H) _2-3 (R〃 is an alkylene group having 2 to 12 carbon atoms). Commercially available polyamide elastomers include Glylamid ELY-2742.
(Manufactured by EMS CHEMIE), Pebax 6333-
SN00 (manufactured by Toray).

Examples of the polyester elastomer include a block copolymer elastomer comprising a hard segment of polyalkylene terephthalate such as polyethylene terephthalate and polybutylene terephthalate and a soft segment of the same polyether component or aliphatic polyester component as described above. No. Ethylene-propylene copolymer as a polyolefin-based elastomer,
Examples include an ethylene-butene copolymer and an ethylene-propylene-diene copolymer.

In the resin composition of the present invention, the mixing ratio of the PAS resin to the thermoplastic elastomer is 50 to 50%.
50-1% by weight of thermoplastic elastomer to 99% by weight
And preferably 70 to 95% by weight of the PAS resin.
In the range of 30 to 5% by weight of the thermoplastic elastomer. When the amount of the thermoplastic elastomer is less than 1% by weight, the effect of improving the impact resistance, elongation and flexibility of the resin is small, and when the amount of the thermoplastic elastomer exceeds 50% by weight, the strength, heat resistance and rigidity of the PAS resin itself are significantly impaired. It is.

The aromatic maleimide compound used in the present invention is roughly classified into a compound represented by the general formula (1) and a compound represented by the general formula (2). In the general formula (1), R ₁ is a divalent organic group containing a phenylene group or a phenylene group having a substituent. Examples of such an organic group include a divalent organic group represented by the following formula.

[0025]

Embedded image X in the organic group is a direct bond or a divalent group represented by the following formula.

[0026]

Embedded image Further, Y ₁ to Y ₈ in the organic group are an alkyl group having 1 to ₈ carbon atoms or hydrogen, and at least one of Y ₁ to Y ₈ in each radical corresponding to R ₁ is an alkyl group. is there.

In the aromatic maleimide compound represented by the general formula (2), R ₂ is a divalent hydrocarbon group, preferably an alkylene group having 1 to 8 carbon atoms, and n is 0,
1 or 2. Specific examples of the aromatic maleimide compound represented by the general formula (1) include p-phenylenebismaleimide, m-phenylenebismaleimide, (2-methyl) m-phenylenebismaleimide, and 4,4′-diphenyletherbismaleimide. 4,4'-diphenylsulfide bismaleimide, 4,4'-diphenylsulfonebismaleimide, 4,4'-diphenylmethanebismaleimide, 3,3'-diphenylether bismaleimide, 3,3'-diphenylsulfidebismaleimide, , 3'-diphenylsulfonebismaleimide,
3,3'-diphenylmethane bismaleimide, 4,4 '
-(2-dimethyl) diphenylmethane bismaleimide,
4,4 '-(2-dimethyl) diphenyl ether bismaleimide, 4,4'-biphenylene bismaleimide,
4,4'-diphenylisopropylidenebismaleimide, 3,4'-diphenylisopropylidenebismaleimide, 1,4-bis (maleimide-4'-phenoxy)
Phenylene, 1,3-bis (maleimido-4 "-phenoxy) phenylene, 4,4'-diphenoxydiphenylsulfone-4" -bismaleimide, 4,4'-bis (maleimide-4 "-phenoxy) diphenylsulfone As a specific example of the aromatic maleimide compound represented by the general formula (2), R ₂ in the general formula (2) is-
CH ₂ — and —C ₂ H ₄ —. These may be used alone or in combination of two or more.

The aromatic maleimide compound has an effect of remarkably improving the compatibility between the PAS resin and the thermoplastic elastomer. In order to achieve this effect, the mixing ratio of the aromatic maleimide to the resin mixture of the PAS resin and the thermoplastic elastomer is 0.1 to 100 parts by weight of the resin mixture.
It is 1 to 10 parts by weight, preferably 0.5 to 5 parts by weight.
If the amount of the aromatic maleimide is less than 0.1 part by weight, the effect of improving the compatibility is small, and if the amount of the aromatic maleimide exceeds 10 parts by weight, the resin composition thickens and the moldability deteriorates.

In the PAS resin composition of the present invention, in order to improve strength, heat resistance, rigidity and dimensional stability,
Reinforcing fibers and / or inorganic fillers can be included. Examples of the reinforcing fibers include glass fibers, carbon fibers such as polyacrylonitrile and pitch, inorganic fibers such as graphite fibers, potassium titanate fibers, silicon carbide fibers, asbestos fibers, ceramic fibers, and stainless steel fibers, and aromatic polyamides (aramids). And organic fibers such as fibers. As inorganic fillers, kaolin, clay, bentonite, zeolite, mica, mica, talc, wollastonite, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, molybdenum dioxide, graphite, gypsum, glass , Beads, glass balloons and the like. If necessary, the surface of these reinforcing fibers and the inorganic filler can be pretreated with a silane-based, titanate-based or aluminate-based coupling agent before use.

The compounding amount of the reinforcing fiber and the inorganic filler is P
Based on 100 parts by weight of the resin mixture composed of the AS resin and the thermoplastic elastomer, 5 to 100 parts by weight and 5 to 80 parts by weight are preferred, respectively.

The main feature of the resin composition of the present invention is that it contains molybdenum disulfide (MoS ₂ ) and a silicone compound having a functional group at one or both terminals.
By adding molybdenum disulfide and such a silicone compound, elongation is imparted, the toughness is increased, and the sliding characteristics are remarkable, without substantially impairing the strength and rigidity of the unadded PPS resin composition. To be improved. The molybdenum disulfide used has an average particle size of 0.1 in view of its sliding characteristics.
~ 5.0 µm is preferred. The amount of molybdenum disulfide is 0.05 to 30 parts by weight based on 100 parts by weight of the total weight of the mixture of the PAS resin and the thermoplastic elastomer, the aromatic maleimide compound and the optional reinforcing fiber and / or inorganic filler. Parts, preferably 0.5-2
0 parts by weight.

A preferred silicone compound is represented by the following formula (4).

Embedded image In the formula (4), the terminal R is hydrogen, a methyl group, a vinyl group (—CH ＝ CH ₂ ), an aminopropyl group (—CH ₂ CH).
₂ CH ₂ NH ₂ ), other amino group-containing hydrocarbon groups,-
Hydroxyl-terminated hydrocarbon groups such as C ₃ H ₆ OC ₂ H ₄ OH,

Embedded image And a glycidyl group-terminated hydrocarbon group. Here, at least one of R must have a group other than hydrogen and a methyl group, that is, a group having a functional group.
The silicone compound used in the present invention has a molecular weight of 500 to
50,000 (in the above formula (4), n = 4 to 7)
00), desirably 5,000 to 20,000 (also n = 60 to 270). These silicone compounds may be used alone or in combination of two or more, and a silicone compound having no functional group at a terminal may be used in combination.

Commercial products of the silicone compound used in the present invention include Thylaprene FM3325, (both terminal amino groups, modified silicone oil) and Thylaprene F
M5526 (both terminal epoxy group-modified silicone oil) (all manufactured by Chisso). Examples of the silicone compound having no functional group at the terminal that may be used in combination include L-40 manufactured by Nippon Unicar.

The amount of the silicone compound is from 0.05 to 100 parts by weight based on the total weight of the mixture of the PAS resin and the thermoplastic elastomer, the aromatic maleimide compound and the optional reinforcing fiber and / or inorganic filler. 2
It is 5 parts by weight, preferably 0.5 to 15 parts by weight. If the amount of the silicone compound is less than 0.1 part by weight, the object of the present invention cannot be achieved, and if it exceeds 25 parts by weight, the inherent rigidity of the PAS is impaired.

The resin composition of the present invention contains a heat stabilizer, an ultraviolet absorber, a foaming agent, a flame retardant, a colorant, a mold release agent, a gas adsorbent and the like as long as the object of the present invention is not hindered. I can do it.

The resin composition of the present invention is generally in the form of pellets, and is mainly used as a raw material for injection molding and extrusion molding. The means for producing the pellets is not particularly limited. A typical method is to melt-knead the mixture in a single-screw or twin-screw extruder at a temperature equal to or higher than the melting point of the PAS resin, and then extrude and cut into pellets. The melting and kneading temperature in this case is PAS
A temperature equal to or higher than the melting point of the resin, ie, 285 ° C. to 380
° C, preferably 290-340 ° C. The timing at which the aromatic maleimide compound, molybdenum disulfide, silicone compound, inorganic filler and reinforcing fiber are added is not limited to the above-mentioned method, and is added to either one of the PAS resin and the thermoplastic elastomer before mixing. Alternatively, a method of adding the mixture to the resin mixture after the preliminary mixing and mixing again can be employed. The reinforcing fibers are preferably mixed into the resin composition during the kneading process from the middle of the extruder in order to prevent the breakage of the reinforcing fibers.

[0037]

The resin composition of the present invention has favorable properties inherent in PAS resin, namely, mechanical properties, rigidity,
It has good impact resistance, elongation and flexibility without substantially impairing heat resistance, chemical resistance and electric insulation, and compatibility of resin components provided by an aromatic maleimide compound. Molybdenum disulfide and the silicone compound exhibit excellent sliding characteristics and flexibility without impairment. In particular, the resin composition of the present invention has a small coefficient of friction and its fluctuation under high-speed sliding, and heat generation is largely suppressed. Accordingly, the resin composition of the present invention has sliding members such as bearings, shaft seals and cams, for example, sliding members for OA equipment and home appliances, sliding members for automobiles requiring heat resistance, and chemical resistance. It is useful as a required sliding member for chemical plants.

[0038]

EXAMPLES Hereinafter, the resin composition of the present invention will be specifically described with reference to examples. As the PAS resin, a polyparaphenylene sulfide resin powder / toprene “T-4” powder (manufactured by Toprene, melt viscosity 900 poise) was used. T-4 powder, thermoplastic elastomer, aromatic maleimide compound (N, N'-m-phenylenebismaleimide ("Barnock, PM" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.))
A resin composition was prepared by mixing molybdenum disulfide (A powder made by Nichimori), a silicone compound, and a glass fiber chopped strand (03MA404 made by Asahi Glass) in the ratio shown in Table 1. As a thermoplastic elastomer, styrene-butadiene-styrene block copolymer (SBS)
(Asahiprene T430 manufactured by Asahi Kasei Kogyo), hydrogenated product of SBS (SEBS) (Tuftec H104 manufactured by Asahi Kasei Kogyo)
1) and an acid-modified product of SEBS (SEBS-M) (ToughTech M1913 manufactured by Asahi Kasei Kogyo).

As the silicone compound, a silicone oil modified with amino groups at both terminals (Silaprene FM3325, manufactured by Chisso) was used. Upon mixing, each component was melt-kneaded at 300 ° C. using a twin-screw extruder after pelletization to form pellets. The glass fibers were added to the kneaded resin composition in the middle of the extruder.

Each resin composition was prepared at 300 ° C. and a mold temperature of 110
A test piece for evaluating physical properties was prepared by injection molding at ° C., and the physical properties were evaluated according to the following criteria. The results are shown in Table 1. Tensile strength: JIS K-7113 (test speed 5 mm /
Miner) Taber index: JIS K-7204 (Wear wheel: Taber CS-17, displayed as abrasion amount (mg) per 1,000 rotations) Limit PV value: JIS K-7218, A method (V: 80c)
m / sec, P: arbitrary, friction distance: 1500 m, contact area:
2cm ² )

[0041]

[Table 1]

Embedded image

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ identification symbol FI // (C08L 81/02 101: 00 83:04) (58) Investigated field (Int.Cl. ⁷ , DB name) C08L 81 / 00-81/02 C08L 83/00-83/04 C08L 53/00-53/02 C08L 9/00 C08L 101/00 C08K 5/34-5/3415 C08K 3/30

Claims (2)

(57) [Claims] (A) polyarylene sulfide resin 5
0-99% by weight, (B) thermoplastic elastomer 50-1
(C) at least one compound selected from the group consisting of aromatic maleimide compounds represented by the following formulas (1) and (2):
0 parts by weight, (D) molybdenum disulfide ((A),
(Based on a total of 100 parts by weight of the three components (B) and (C))
0.05 to 30 parts by weight, and (E) a silicone compound having a functional group on at least one terminal (the above (A),
(Based on a total of 100 parts by weight of the three components (B) and (C))
A polyarylene sulfide resin composition comprising 0.05 to 25 parts by weight. Embedded image In the formula (1), R ₁ is a divalent organic group containing a phenylene group or a phenylene group having a substituent. Embedded image In the formula (2), R ₂ is a divalent hydrocarbon group, and n is 0, 1 or 2. 2. (A) Polyarylene sulfide resin 5
0-99% by weight, (B) thermoplastic elastomer 50-1
(C) at least one compound selected from the group consisting of aromatic maleimide compounds represented by the following formulas (1) and (2):
0 parts by weight, (F) 5 to 100 parts by weight of reinforcing fibers and / or 5 to 80 parts by weight of an inorganic filler, (D) molybdenum disulfide (the above components (A), (B), (C), and (F) A total of 1
0.05 to 30 parts by weight) and (E) a silicone compound having a functional group on at least one terminal (total of components (A), (B), (C) and (F) (Based on 100 parts by weight). A polyarylene sulfide resin composition comprising 0.05 to 25 parts by weight. Embedded image In the formula (1), R ₁ is a divalent organic group containing a phenylene group or a phenylene group having a substituent. Embedded image In the formula (2), R ₂ is a divalent hydrocarbon group, and n is 0, 1 or 2.