JPS6310661A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. which has excellent moldability, heat resistance, mechanical strengths and slide abrasion and low anisotropy in a coefficient of linear expansion, by blending a polyphenylene sulfide resin with a reinforcing fiber and silicon nitride. CONSTITUTION:A resin compsn. consists of 15-87wt% polyphenylene sulfide resin (a), 3-25wt% reinforcing fiber (b) and 10-82wt% silicon nitride (c). A polyphenylene sulfide resin composed of at least 70mol% of a structure unit of the formula is preferred. When the amount of the unit of the formula is less than 70mol%, no compsn. having excellent characteristics can be obtd. When the amount of the silicon nitride is less than 10wt%, no excellent slide abrasion properties can be obtd. When the reinforcing fiber has a ratio of the fiber diameter D to the fiber length L of not lower than 5, and of inorg., org. and metallic fibers can be used.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a resin composition comprising a polyphenylene resin, a fiber reinforcing material, and silicon nitride, which also has moldability,
The present invention relates to a polyphenylene sulfide resin composition that has excellent heat resistance, mechanical strength, and wear resistance, and has extremely low anisotropy in linear expansion coefficient.

(Conventional technology and problems) Polyphenylene sulfide resin has excellent heat resistance,
In recent years, engineering plastics have attracted attention as having chemical resistance and flammability, but resins alone are brittle and have poor moldability, severely limiting their practicality. For this reason, various properties have been imparted to them by means of compositing, such as adding fibrous reinforcing materials for the purpose of reinforcement, etc., and these have been put into practical use.

In addition, these polyphenylene sulfide resin compositions are
Taking advantage of the characteristics of each, demand is growing rapidly in many fields such as electrical and electronic parts, automobile parts, chemical equipment, aerospace, and leisure goods. The current situation is that as technology becomes more sophisticated, devices become smaller and more precise, and the conditions under which they are used are also becoming stricter.

Against this background, the characteristics required of each component in recent years are as follows:
Materials that have a wide range of heat resistance, formability, mechanical strength, and abrasion characteristics at the same time and also have a small anisotropy of linear expansion coefficient are emerging.

Eight proposals have been made for each of these required characteristics. For example, currently commercially available reinforced polyvinylene sulfide resin compositions containing 40 weight J/jk% of glass fibers have improved mechanical strength and heat resistance; If a molded article made of the composition is used under high temperature conditions, the anisotropy of the resin's coefficient of linear expansion in the flow direction and transverse direction is large. Anisotropy occurs in the lateral direction, resulting in different linear expansion coefficients, and specifically, distortion, warping, etc. occur, which causes practical problems.

In addition, as a means to reduce the anisotropy of the linear expansion coefficient, it is possible to add a filler with relatively small directionality, but although this method improves the anisotropy of the linear expansion coefficient, , resulting in poor mechanical strength and heat resistance.

Furthermore, as a product that satisfies the performance of both of the above requirements,
7-63355 discloses a composition consisting of polyphenylene sulfide/mica/glass fiber, which has good heat resistance, moldability, and mechanical strength, and has anisotropy in linear expansion coefficient. However, it is inferior in terms of abrasion characteristics, and currently there is no material that satisfies all of these required characteristics.

The present inventors have solved these drawbacks (as a result of intensive studies, it has been found that the polyphenylene sulfide resin composition contains a fibrous reinforcing material and (B) silicon nitride, which improves moldability and heat resistance. The inventors have now invented a polyphenylene sulfide resin composition that has excellent mechanical strength and universal abrasion resistance, and has extremely small anisotropy in linear expansion coefficient.

(Means for Solving the Problems) That is, the present invention includes: 1) polyphenylene sulfide resin in an amount of 15 to 871 2) fibrous reinforcement material in an amount of 6 to 25 M; and 3)
, silicon nitride 10 to 82% by weight.

The polyphenylene sulfide resin used in the present invention preferably contains 70 moles or more of the structural unit represented by the general formula ()S-; if the amount is less than 70 moles, it is difficult to obtain a composition with excellent properties. The polymerization method for this polymer is to polymerize p-dichlorobenzene in the presence of sulfur and sodium carbonate, or to sulfurize it in a polar solvent, or to hydroxylate it with sodium hydrogen sulfide or hydrogen sulfide and water. Method of combining in the presence of sodium oxide and p
-Self-condensation of chlorothiophenol is an example, but a method in which sodium sulfide and p-dichlorobenzene are reacted in an amide solvent such as N-methylgyrolidone or dimethylacetamide or a sulfonic solvent such as sulfolane is suitable. be. At this time, in order to control the degree of polymerization, it is preferable to add an alkali hydroxide containing all the alkali metal salts of carboxylic acid or sulfonic acid. Furthermore, as a copolymerization component, if it is less than 30 molar, it indicates a meta bond (8S-), a biphenyl bond (!S-), a substituted phenyl sulfide bond phenyl group, an alkoxy group, a carboxylic acid group, or a metal base of a carboxylic acid group. ) and hexafunctional polymerization properties, but it is preferable that the copolymerization component is 10 molar or less.

Specific methods for producing such polyphenylene sulfide resin include, for example, (1) reaction of a halogen-substituted aromatic compound with an alkali sulfide (U.S. Pat.
(Refer to Publication No. 3368) (2) Condensation reaction of thiophenols with an alkali catalyst or (3) aromatic compounds such as copper salts with sulfur chloride in the coexistence of a Lewis acid catalyst (% Kosho 46-
27255, Belgian Patent No. 29437), etc.

Next, the silicon nitride used in the present invention is in powder form,
The manufacturing methods are (1) directly nitriding metal silicon powder at high temperature, (2) nitriding silica powder while reducing it with carbon powder, and (3) at room temperature. There is a method of synthesizing silicon imide by reacting , and crystallizing it by heating it to a high temperature in a nitrogen or ammonia atmosphere, but any method may be used.

The amount of silicon nitride added is 10 to 8 with respect to the total amount of the composition.
21 weight percent, preferably 20 to 701 weight percent. If it is less than 10 weight percent, excellent sliding wear properties cannot be obtained, and if it exceeds 82 weight percent, moldability is poor. Next, use in the present invention The fibrous reinforcing material may be organic, inorganic, or metal, as long as the ratio of fiber diameter to length L (L/D) in the resin composition is 5 or more.For example, glass fiber may be used as the fibrous reinforcing material. , potassium titanate fiber, carbon fiber m%
Aramid fiber, silica fiber, alumina fiber, silica/alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, stainless steel fiber, aluminum fiber, titanium fiber, copper fiber, brass fiber, magnesium fiber, polyamide fiber, Examples include polyester fiber, polyethylene fiber, polyacrylic fiber, and fluorine tλ fiber. In addition, when using these fibrous reinforcing materials, it may be possible to add a sizing agent or a stabilizer if necessary.

The amount of these fibrous reinforcing materials added is 3 to 253 kfit percent, preferably 5 to 2031 kfit percent, based on the total amount of the composition.
(It is weight percent. If it is less than 31 weight percent, it will not exhibit excellent heat resistance and mechanical strength, and if it exceeds 25 weight percent, anisotropy will occur in the coefficient of linear expansion.

Furthermore, the polyphenylene sulfide resin composition of the present invention may contain various types of organic and/or inorganic fillers, such as asbestos, silicon carbide, silica, barium sulfate, calcium sulfate, kaolin, and clay, within a range that does not reduce the properties of the composition. , pyroferrite, bentonite, sericite, zeolite, curzan, mica, nephelinicinite, talc, atalpulgite, wollastonite, ferrite, calcium silicate, alumina, magnesium carbonate, dolomite, antimony trioxide, oxide It is also possible to add all of zinc, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder, glass balloons, quartz, and quartz glass.

Further, various plasticizers, +*m agents, coupling agents, colorants, lubricants, heat stabilizers, weather stabilizers, foaming agents, rust preventives, flame retardants, flame retardant aids, etc. may be added.

Furthermore, the resin composition of the present invention can be used by mixing the following polymers as necessary. These polymers include
A single combination of monomers such as ethylene, zolopyrene, butylene, pentene, butadiene, isoprene, chlorozolene, styrene, α-methylstyrene, arnyl acetate, vinyl chloride, acrylic ester, methacrylic ester, (meth)acrylonitrile, etc. or comonomer, polyurethane, polyester, polyacetal, polycarbonate, polysulfone, polyallylsulfone, polyethersulfone, polyarylate, polyphenylene oxide, polyetheretherketone, polyimide, polyamideimide, silicone resin, phenoxy resin, fluororesin, Examples include homopolymers, random copolymers, block copolymers, and graft copolymers such as polyallyl ether and polyamide.

The thus obtained boυphenylene sulfide resin composition of the present invention may be prepared by simply tri-blending the components or by melt-mixing them.

In general, the tori is made into a molded article by injection molding, but it is also possible to employ any of transfer molding, calendar molding, extrusion molding, and compression molding.

Furthermore, due to its excellent properties, this polyphenylene sulfide resin composition can be used in various applications such as electrical and electronic parts fields, automobile parts fields, chemical profit and loss fields, and leisure goods fields.

Examples include connectors, coil poggins, capacitor housings, semiconductor encapsulation, trimmer capacitors, relay parts, breaker parts, compact disc player parts, floppy disk drive parts, electronic parts cleaning jigs, dryer grills, hot Parts for melt adhesive guns, microwave oven parts, TV tuner parts, video tape recorder parts, video tape recorder cassette tape guide rolls, motor drums, printer parts, lamp connectors, car radio parts, rice cookers, etc.
Radiator thermostat housing, body pulp, EGR valve, carburetor insulation board, distributor parts, tie rod bearing, chemical pump case, impeller, submersible pump, hot water valve, cleaning tower filling material,
- Electrode holders, hoses, tubes, pipes, irons, wire coatings, optical fiber coatings, gears, cam bearings, bearings, nodding gaskets, O-rings, fasteners, etc., as well as powder coating solution adhesives, Paint sheets, etc.
Can be used as a film.

(Example) This will be explained in detail below using examples.

In the following expressions in Examples, polyphenylene sulfide resin will be abbreviated as pps, silicon nitride tsizlJ4, glass fiber as OF, and carbon fiber as CF.

PPS is manufactured by Philips Petroleum Company under the trade name “R”.
yton P-44f was used.

As Si3N4, Denka Silicon Nitride 5N-BS J manufactured by Denki Kagaku Kogyo Co., Ltd. was used.

The GF used was "Chopped Strand EC8O3T-717Pjk" manufactured by Nippon Electric Glass Co., Ltd. under the trade name.

As the CF, Besphite HTA-C3-8J, manufactured by Toho Rayon Co., Ltd., was used.

The mica used was "Sujirite Mica 400WJ" manufactured by Kuraray Co., Ltd. under the trade name.

Calcium carbonate is manufactured by Shiroishi Calcium Co., Ltd. under the trade name “
I used Whiten S and BJi.

The coupling agent is manufactured by Nippon Unicar Co., Ltd. under the trade name [
NUC silane coupling agent A-1100J was used.

Example 1 After blending 45 weight percent pps, 50 weight percent Si3N, and GFSit amount percent
It was melted into pellets using a co-directional twin-screw extruder.

After drying the above pellets at 130° C. for 3 hours, they were placed in a hopper of a 5-ounce injection molding machine, melted in a plasticizing cylinder, and injected into an injection mold. The temperature conditions of the cylinder were 290-320'C, and the mold temperature was 140°C.

This molded article exhibited the physical properties shown in Table 1, and had good moldability, heat resistance, mechanical surface strength, and surface abrasion resistance, and had small anisotropy in fat expansion coefficient.

Example 2 Si3N450N with 5% pps 35'
Amount percent and G715 weight percent) were molded and evaluated in the same manner as in Example 1.

This molded article exhibited the physical properties shown in Table 1, and had good moldability, heat resistance, mechanical strength, and overall abrasion resistance, as well as small anisotropy in linear expansion coefficient.

Example 3 Molding was evaluated in the same manner as in Example 1 using 30 weight percent pps, 450 weight percent Si3N, and C) F2Q weight percent.

This molded article exhibited the physical properties shown in Table 1, and had good moldability, heat resistance, mechanical strength, and overall abrasion resistance, and had small anisotropy in linear expansion coefficient.

Example 4 PP875 weight percent, 5i3N415 k amount percent, and Gp10 weight percent) f % Molding evaluation was carried out in the same manner as in 1.

This molded article exhibited the physical properties shown in Table 1, and had good moldability, heat resistance, mechanical strength, and overall abrasion resistance, and had small anisotropy in linear expansion coefficient.

Example 5 Molding was evaluated in the same manner as in Example 1 using 40 mji percent pps, 450 weight percent Si3N, and 10 weight percent GF.

This molded article exhibited the physical properties shown in Table 1, and had good moldability, heat resistance, mechanical strength, and overall abrasion resistance, and had small anisotropy in linear expansion coefficient.

Example 6 Molding was evaluated in the same manner as in Example 1 using pps15i amount percent, 75 weight percent, and GF10 weight percent.

This molded article exhibited the physical properties shown in Table 1, and had good moldability, heat resistance, mechanical strength, and overall abrasion resistance, and had small anisotropy in linear expansion coefficient.

Example 7 PP840 weight percent, 8i3N, 50 weight percent and CF10 weight percent. Molding evaluation was carried out in the same manner as in Example 1.

This molded article exhibited the physical properties shown in Table 1, and had good moldability, heat resistance, mechanical strength, and overall abrasion resistance, and had small anisotropy in linear expansion coefficient.

Example 8 PPS 39wt%Si3N, 50wt%, GF103kilt%silane coupling agent A-11001wt%) 11 Example 1
The molding was evaluated in the same manner.

This molded article exhibited the physical properties shown in Table 1, and had good moldability, heat resistance, mechanical strength, and all abrasion resistance, and had small anisotropy in linear expansion coefficient.

Comparative Example 1 PPS 49 weight percent, 81sN450″i amount percent, and GF1tc! percent All molding evaluations were carried out in the same manner as in Example 1.

This molded product had the physical properties shown in Table 2, including good moldability and abrasion resistance, and small anisotropy in linear expansion coefficient, but heat resistance and mechanical strength were not satisfactory. There wasn't.

Comparative Example 2 (pps 20 weight percent, Si3N450 weight percent, GF 30

This molded product had the physical properties shown in Table 2.

Although the mechanical strength, heat resistance and surface abrasion resistance were good, the coefficient of linear expansion was not a satisfactory value due to large anisotropy.

Comparative Example 3 Molding was evaluated in the same manner as in Example 1 using 85 weight percent PPS, 45 weight percent Si3N, and GF104.゛The physical properties of this molded product were as shown in Table 2, and the moldability, mechanical strength, and heat resistance were good, but the anisotropy of the coefficient of linear expansion was large, and the overall mouldability was also satisfactory. It wasn't the value.

Comparative Example 4 PPS 10 weight percent and 813N, 80 weight percent and GF ID weight percent'ft Molding was attempted in the same manner as in Example 1, but the resin composition did not flow into the mold and molding was impossible. .

Comparative Example 5 PPS40] kfIj:%, GF' j Q weight percent, and calcium carbonate 5 oin percent were evaluated for molding in the same manner as in Example 1. This molded product had good moldability, mechanical strength, and heat resistance as shown in Table 2, and had small anisotropy in linear expansion coefficient, but overall abrasion resistance was poor.

Comparative Example 6 PPS 40 weight percent (Float amount percent and Mica 50'N amount percent) 1 Molding evaluation was carried out in the same manner as in Example 1. This molded article had the physical properties shown in Table 2.

The moldability, mechanical strength, and heat resistance were good, and the anisotropy of the coefficient of linear expansion was small, but the overall abrasion resistance was poor.

Comparative Example 7 pps sox amount percent and Si3N450N
The molding evaluation was carried out in the same manner as in Example 1. This molded article had the physical properties shown in Table 2.

The moldability and wear resistance were good, and the anisotropy of the coefficient of linear expansion was small, but the mechanical strength and heat resistance were not satisfactory.

Comparative Example 8 PPS 6031f weight percent and GF 4 Q weight percent Molding was evaluated in the same manner as in Example 1. This molded article had the physical properties of the second garment.

Although moldability, heat resistance, and mechanical strength were good,
The overall abrasion resistance was poor, and the anisotropy of the coefficient of linear expansion was also large.

The physical properties shown in Tables 1 and 2 were measured as follows.

(1) Bending strength/flexural modulus JrS x-7203 compliant method (2) Heating deformation temperature JIS K-7207 compliant method (3) Vessel abrasion/testing machine: Bin-on-disc type manufactured by Tokyo Shikenki Seisakusho Co., Ltd. Abrasion tester O test conditions: Rotation speed 400 rpm, pressurized load 3! L2k
l?・Test method: Create a bottle-shaped sample of 5 mm φ x 60 mm, set it in contact with the opposing material (SUS 304), and perform a break-in operation to make the contact surface uniform.

Then rotate it for 1000 revolutions. The chart shows the degree of wear (length) over time. I read it.

e Evaluation criteria (4) Molding processability Inject the resin melted at a cylinder temperature of 290 to 320°C into a mold for a rod-shaped molded product (date 2 blade m
Those that could be injected at g/α2 and molded without problems were evaluated as good, and those that could not be molded due to resin filling were evaluated as poor.

(5) Coefficient of linear expansion Shimadzu Corporation Thermal analyzer i D T 3 Q (T
All MA units were used and the coefficient of linear expansion was measured in the temperature range from 30°C to 90°C.

(Effects of the Invention) The polyvinylene 7-eyed resin combination acid of the present invention, which is characterized by containing a fibrous reinforcing material and silicon nitride, has good moldability, heat resistance, mechanical strength, and excellent abrasion resistance. It is a highly practical molding material that has good properties and extremely low anisotropy in linear expansion coefficient, and has excellent physical properties as a engineering plastic.

Claims (1)

[Scope of Claims] A polyphenylene sulfide resin comprising 1) 15 to 87% by weight of polyphenylene sulfide resin, 2) 3 to 25% by weight of fibrous reinforcing material, and 3) 10 to 82% by weight of silicon nitride. Composition.