JP2002038009A - Polyphenylenee sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyphenylene sulfide resin composition having a small size change by heat and high rigidity, and to provide an injection-molding product. SOLUTION: A polyphenylene sulfide resin composition comprises comprising (B) 0.1-100 pts.wt. of a swelling lamellar silicate and (C) 10-400 pts.wt. of a non-fibrous filler to (A) 100 pts.wt. of a polyphenylene sulfide resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene sulfide resin composition having a small dimensional change due to heat and high rigidity, and more particularly to a resin composition suitable for optical parts and an injection-molded product thereof.

[0002]

2. Description of the Related Art Polyphenylene sulfide resin (hereinafter referred to as P
Abbreviated as PS resin. ) Is suitable for engineering plastics, such as excellent heat resistance, flame retardancy, chemical resistance, dimensional stability, rigidity, and electrical insulation. parts,
Used for applications such as machine parts and automobile parts.

In such applications, in place of conventionally used metal materials, resin products obtained by injection and extrusion molding of engineering plastics are widely used as a measure to reduce the weight and cost of metal working. Performance levels are increasing.

When a metal material is replaced with a PPS resin, dimensional stability, especially suppression of dimensional change due to heat, and high rigidity are often important, especially for precision parts. PPS resin can provide a relatively excellent resin composition in this regard, but the demand for ultra-precision has increased, and the demand has been increasing. That is the current situation.

[0005]

SUMMARY OF THE INVENTION In view of the above situation, an object of the present invention is to obtain a material having higher dimensional stability and higher rigidity than the level achieved by the prior art and having high rigidity, and an injection molded product thereof. I do.

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, the swelling phyllosilicate, especially the swelling cation obtained by exchanging exchangeable cations existing between layers with organic onium ions, was added to the PPS resin. Achieved the present invention by finding that by adding a specific amount of a layered silicate, a non-fibrous filler, and if necessary, a fibrous filler, a material excellent in both dimensional stability and rigidity and an injection molded product thereof can be obtained. did.

[0007] A composition in which a layered silicate is mixed with a PPS resin is disclosed in, for example, JP-A-5-194851 or JP-A-10-60277.

[0008] Japanese Patent Application Laid-Open No. Hei 5-194851 discloses that a layered silicate is added to PPS for the purpose of improving heat resistance and rigidity. No mention is made of the fact that a material which is better in both aspects of rigidity and rigidity can be obtained.

Japanese Patent Application Laid-Open No. 10-60277 discloses that a specific PPS and a layered silicate are blended, but when used together with a non-fibrous filler, both dimensional stability and rigidity are improved. No mention is made of the availability of such materials.

[0010]

That is, the present invention provides the following resin composition and molded article. 1. (A)
For 100 parts by weight of polyphenylene sulfide resin,
(B) 0.1-100 parts by weight of a swellable layered silicate, (C)
A polyphenylene sulfide resin composition comprising 10 to 400 parts by weight of a non-fibrous filler. 2. (B) The polyphenylene sulfide resin composition according to (1), wherein the swellable layered silicate is a swellable layered silicate in which exchangeable cations existing between layers have been exchanged with organic onium ions. 3. (B) The polyphenylene sulfide resin composition according to the above item 2, wherein the organic onium ion is a quaternary ammonium ion. 4. (B) 0.1 to 100 parts by weight of swellable layered silicate, (C) non-fibrous filler 10 per 100 parts by weight of polyphenylene sulfide resin
To 400 parts by weight, and (D) fibrous filler 5 to 150 parts
4. The polyphenylene sulfide resin composition according to any one of the above items 1 to 3, which is blended by weight. 5. (B) 0.1 to 100 parts by weight of swellable layered silicate, (C) 10 to 400 parts by weight of non-fibrous filler, (D) fibrous filler 5 based on 100 parts by weight of polyphenylene sulfide resin
5. The polyphenylene sulfide resin composition, wherein the amount of the non-fibrous filler (C) is greater than the amount of the fibrous filler (D). Polyphenylene sulfide resin composition. 6. Further, (E) 5 to 200 parts by weight of an amorphous resin having a glass transition temperature of 100 ° C. or higher is added to 100 parts by weight of the polyphenylene sulfide resin (A). Polyphenylene sulfide resin composition. 7. Further, (F) an epoxy group,
An alkoxysilane compound having a functional group selected from an amino group, a ureide group, and an isocyanate group is added to 0.1 part by weight of (A) 100 parts by weight of the polyphenylene sulfide resin.
7. The polyphenylene sulfide resin composition according to any one of the above items 1 to 6, which is added in an amount of 5 to 5 parts by weight. 8.
A molded article obtained by injection molding the polyphenylene sulfide resin composition according to any one of the above 1 to 7. 9. 1 to 7 above
An optical component obtained by injection molding the polyphenylene sulfide resin composition according to any one of the above items.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The polyphenylene sulfide resin used in the present invention is a polymer containing a repeating unit represented by the following structural formula,

[0012]

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From the viewpoint of heat resistance, a polymer containing 70 mol% or more, particularly 90 mol% or more of the repeating unit represented by the above structural formula is preferable. In the PPS resin, 30 mol% or less of the repeating unit can be constituted by a repeating unit having the following structural formula.

[0014]

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The PPS resin used in the present invention can be prepared by a generally known method, that is, a method of obtaining a polymer having a relatively small molecular weight described in JP-B No. 45-3368 or JP-B No. 52-3368.
It can be produced by a method for obtaining a polymer having a relatively large molecular weight described in JP-A-12240 or JP-A-61-7332. In the present invention, the PPS resin obtained as described above is crosslinked / polymerized by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or under reduced pressure,
Washing with organic solvent, hot water, aqueous acid solution, acid anhydride,
Various treatments such as activation with a functional group-containing compound such as an amine, an isocyanate, and a functional group-containing disulfide compound can be used before use, and it is of course possible to carry out two or more of these treatments. is there.
In addition, it is of course possible to use the PPS resin subjected to these treatments in a mixture of two or more types. As a specific method of using the PPS resin in a mixture of two or more types, a PPS resin cross-linked by heating in air is used. PPS without heat treatment
, A mixture of PPS washed with an aqueous acid solution and PPS washed with an organic solvent, a mixture of PPS washed with an organic solvent and PPS not washed with an organic solvent, and the like.

The melt viscosity of the PPS resin used in the present invention is not particularly limited as long as melt kneading is possible.
Up to 10,000 poise (5 to 1,000 Pa · s) (32
0 ° C. and a shear rate of 1000 sec ⁻¹ ) are used, and among them, 100 to 5,000 poise (10 to 500 Pa)
-Those of s) are preferred. In addition, 2 having different viscosity levels
It is also possible to use a mixture of two or more PPS resins.

As a specific method for crosslinking / high molecular weight of the PPS resin by heating, the method may be carried out in an atmosphere of an oxidizing gas such as air or oxygen, or a mixed gas of the oxidizing gas and an inert gas such as nitrogen or argon. A method in which heating is performed under a given atmosphere at a predetermined temperature until a desired melt viscosity is obtained can be exemplified. The heat treatment temperature is usually 170 to 28
0 ° C is selected, preferably between 200 and 270 ° C,
The time is generally selected from 0.5 to 100 hours, and preferably from 2 to 50 hours. The target viscosity level can be obtained by appropriately controlling the heat treatment temperature and time. The heating device may be a normal hot air dryer with a reduced pressure specification or a high sealing property, or may be a rotary type or a heating device with stirring blades. Alternatively, it is more preferable to use a heating device with a stirring blade.

When the PPS resin is heat-treated in an inert gas atmosphere such as nitrogen or under reduced pressure, a specific method is as follows.
Heat treatment temperature 150 to 280 ° C, preferably 200 to 2
70 ° C., heating time is 0.5 to 100 hours, preferably 2 hours
A method of performing heat treatment for up to 50 hours can be exemplified. The heating device may be a stationary heating device or a rotary heating device or a heating device with stirring blades. For efficient and more uniform treatment, a heating device with a rotating or stirring blade is used. Is more preferred.

The following method can be exemplified as a specific method for washing the PPS resin with an organic solvent. That is,
The organic solvent used for washing is not particularly limited as long as it does not have a function of decomposing the PPS resin. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide, dimethylsulfoxide, dimethyl Sulfoxide and sulfone solvents such as sulfone, acetone, methyl ethyl ketone, diethyl ketone, ketone solvents such as acetophenone, dimethyl ether, dipropyl ether, ether solvents such as tetrahydrofuran, chloroform, methylene chloride,
Halogen solvents such as trichloroethylene, dichlorinated ethylene, dichloroethane, tetrachloroethane, and chlorobenzene; alcohol and phenol solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, and polyethylene glycol And aromatic hydrocarbon solvents such as benzene, toluene and xylene. Among these organic solvents, use of N-methylpyrrolidone, acetone, dimethylformamide, chloroform or the like is preferred. These organic solvents can be used alone or in combination of two or more. As a method for washing with an organic solvent, there is a method such as immersing a PPS resin in an organic solvent, and it is also possible to appropriately stir or heat as necessary. The washing temperature when washing the PPS resin with an organic solvent is not particularly limited, and an arbitrary temperature from ordinary temperature to about 300 ° C. can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect can usually be obtained at a cleaning temperature of normal temperature to 150 ° C.

Further, the PPS resin which has been subjected to the organic solvent washing is preferably washed several times with water or hot water in order to remove the remaining organic solvent.

The following method can be exemplified as a specific method for treating the PPS resin with hot water. That is, the water used is preferably distilled water or deionized water in order to exhibit a favorable effect of chemical modification of the PPS resin by washing with hot water. The operation of the hot water treatment is usually performed by charging a predetermined amount of PPS resin into a predetermined amount of water, and heating and stirring the mixture at normal pressure or in a pressure vessel. The proportion of PPS resin to water is preferably as high as possible, but a bath ratio of 200 g or less of PPS resin to 1 liter of water is usually selected.

The following method can be exemplified as a specific method for treating the PPS resin with an acid.

That is, there is a method of immersing the PPS resin in an acid or an aqueous solution of an acid, or the like, and if necessary, stirring or heating can be performed. The acid used is P
There is no particular limitation as long as it does not have the action of decomposing PS, and aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, chloroacetic acid, and halo-substituted aliphatic saturated carboxylic acids such as dichloroacetic acid, acrylic Acids, aliphatic unsaturated monocarboxylic acids such as crotonic acid, aromatic carboxylic acids such as benzoic acid and salicylic acid, dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, phthalic acid and fumaric acid, sulfuric acid, phosphoric acid, and hydrochloric acid And inorganic acidic compounds such as carbonic acid and silicic acid. Among them, acetic acid and hydrochloric acid are more preferably used. The PPS resin subjected to the acid treatment is preferably washed several times with water or hot water in order to remove the remaining acid or salt. Further, the water used for washing is preferably distilled water or deionized water in the sense that the effect of the preferred chemical modification of the PPS resin by the acid treatment is not impaired.

The swellable layered silicate used as the component (B) in the present invention includes aluminum, magnesium,
The octahedral sheet containing a metal such as lithium has a 2: 1 type structure in which a tetrahedral silicate sheet is superimposed on top and bottom to form one plate-like crystal layer. Have exchangeable cations between the layers.

The size of the single plate-shaped crystal is usually 0.05 to 0.5 μm in width and 6 to 15 Å in thickness. Further, the cation exchange capacity of the exchangeable cation is 0.2 to 3 meq / g, and preferably the cation exchange capacity is 0.8 to 1.5 meq / g.

Specific examples of the layered silicate include montmorillonite, bentonite, beidellite, nontronite,
Smectite clay minerals such as saponite, hectorite, sauconite, vermiculite, halloysite,
Various clay minerals such as kanemite, keniyaite, zirconium phosphate, and titanium phosphate, swelling mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluoromica, Li-type tetrasilicon fluoromica, and the like are exemplified. It may be a composite or a composite. Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable mica such as Na-type tetrasilicon fluorine mica and Li-type fluorine teniolite are preferable, and montmorillonite is particularly preferable.

In the present invention, it is preferable to use a layered silicate in which exchangeable cations existing between layers have been exchanged with organic onium ions.

Examples of the organic onium ion include an ammonium ion, a phosphonium ion, and a sulfonium ion. Among these, ammonium ions and phosphonium ions are preferable, and ammonium ions are particularly preferably used. As ammonium ions,
Any of primary ammonium, secondary ammonium, tertiary ammonium and quaternary ammonium may be used.

The primary ammonium ion includes decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, benzyl ammonium and the like.

Examples of the secondary ammonium ion include methyl dodecyl ammonium, methyl octadecyl ammonium and the like.

Examples of the tertiary ammonium ion include dimethyldodecylammonium and dimethyloctadecylammonium.

The quaternary ammonium ion includes benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium and benzyldimethyloctadecylammonium, trimethyloctylammonium, trimethyldodecylammonium, trimethyloctadecylammonium and the like. Alkyltrimethylammonium ion, dimethyldialkylammonium ion such as dimethyldioctylammonium, dimethyldidodecylammonium and dimethyldioctadecylammonium, and trialkylmethylammonium ion such as trioctylmethylammonium and tridodecylmethylammonium.

Besides these, aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine,
-Aminocaproic acid, 11-aminoundecanoic acid, 12
-Ammonium ions derived from aminododecanoic acid and the like.

Of these ammonium ions, 4
A quaternary ammonium ion is preferable, and specifically, trioctylmethylammonium, trimethyloctadecylammonium, and benzyldimethyloctadecylammonium are preferable, and in particular, trioctylmethylammonium,
Benzyldimethyloctadecyl ammonium is most preferred.

In the present invention, as the organic onium ion, a carboxyl group, a nitro group, a vinyl group, an epoxy group, or the like described in JP-A-5-194851 can be used.
An organic onium ion having a functional group such as a thiol group, a halogen group, a disulfide group, or an azo group can be used, but an organic onium ion having such a functional group is not preferable in terms of economical efficiency. Since the intended effect of the present invention can be sufficiently obtained by using an organic onium ion having no functional group, it is more preferable in the present invention to use an organic onium ion having no functional group.

In the present invention, the layered silicate in which the exchangeable cation existing between the layers has been exchanged with an organic onium ion is:
It can be produced by reacting a layered silicate having an exchangeable cation between layers with an organic onium ion by a known method. Specific examples include a method based on an ion exchange reaction in a polar solvent such as water, methanol and ethanol, and a method based on directly reacting a liquid or molten ammonium salt with a layered silicate.

In the present invention, the amount of the organic onium ion with respect to the layered silicate is determined by considering the dispersibility of the layered silicate, the thermal stability during melting, the gas during molding, and the suppression of generation of odor. Typically 0.4 for cation exchange capacity
The range is from 2.0 to 2.0 equivalents, but preferably from 0.8 to 1.2 equivalents.

It is preferable to use these layered silicates by pre-treating them with a coupling agent having a reactive functional group, in addition to the above-mentioned organic onium salts, in order to obtain more excellent mechanical strength. Examples of such a coupling agent include an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound.

Particularly preferred is (F) an alkoxysilane compound having a functional group selected from an epoxy group, an amino group, a ureido group and an isocyanate group. Specific examples thereof include γ-glycidoxypropyltrimethoxysilane. Epoxy-containing alkoxysilane compounds such as γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-ureidopropyltriethoxysilane,
γ-ureidopropyltrimethoxysilane, γ- (2
-Ureidoethyl) aminopropyltrimethoxysilane and other ureido group-containing alkoxysilane compounds, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyl Isocyanato group-containing alkoxysilane compounds such as methyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) aminopropyl Amino group-containing alkoxysilane compounds such as methyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane. . In particular, an alkoxysilane compound containing an epoxy group, an amino group, a ureide group, and an isocyanate group is preferably used.

Epoxy compounds, in particular, (G) polyfunctional epoxy compounds having two or more epoxy groups in one molecule can also be exemplified as preferred compounds. Specific examples thereof include bisphenol A, bisphenol F, bisphenol S, bisphenol AF, bisphenol AD,
4,4'-dihydroxybiphenyl, resorcin, saligenin, trihydroxydiphenyldimethylmethane, tetraphenylolethane, their halogen-substituted and alkyl-substituted products, butanediol, ethylene glycol, erythrit, novolak, glycerin, polyoxyalkylene Glycidyl ethers such as glycidyl ethers synthesized from compounds containing two or more hydroxyl groups in the molecule and epichlorohydrin, glycidyl esters such as glycidyl phthalate, aniline, diaminodiphenylmethane, metaxylenediamine, 1,3-bis Glycidylamines synthesized from primary or secondary amines such as aminimethylcyclohexane and epichlorohydrin,
Non-glycidyl epoxy resins such as glycidyl epoxy resin, epoxidized soybean oil, vinylcyclohexenedionoxide, dicyclopentadienedionoxide and the like, among which the polyfunctional phenol type epoxy resin shown below is preferable, and among them orthocresol Novolak glycidyl ether is particularly preferred.

[0041]

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[0042]

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The treatment of the layered silicate with these coupling agents can be performed in an organic solvent such as water, methanol or ethanol.
Alternatively, a method of adsorbing the coupling agent to the layered silicate in these mixed solvents or a method of dropping and adsorbing the coupling agent solution while stirring the layered silicate in a high-speed stirring mixer such as a Henschel mixer, Further, any method may be used in which a liquid coupling agent is added to the layered silicate and mixed and adsorbed in a mortar or the like. When the layered silicate is treated with a silane coupling agent, a method of simultaneously mixing water, acidic water, alkaline water and the like in order to promote the hydrolysis of the alkoxy group of the coupling agent can be exemplified. Further, in order to enhance the reaction efficiency of the coupling agent, water such as methanol or ethanol and an organic solvent which dissolves both the coupling agent may be mixed in addition to water. The reaction can be further promoted by heat-treating the layered silicate treated with such a coupling agent. When the composition of the present invention is produced by melt-kneading a layered silicate and a polyphenylene sulfide resin, the layered silicate and the polyphenylene sulfide resin are melt-kneaded without performing a treatment with a layered silicate coupling agent in advance. In this case, it is also possible to use a method of adding these coupling agents.

The order of the treatment of the layered silicate with the organic onium ion and the treatment with the coupling agent is not particularly limited. However, it is preferable that the treatment is performed first with the organic onium ion and then with the coupling agent.

In the present invention, the content of (B) the swellable phyllosilicate is 0.1 to 100 as an inorganic ash content based on 100 parts by weight of the polyphenylene sulfide resin (A) of the present invention.
Parts by weight, preferably 0.1 to 50 parts by weight, particularly preferably 1 to 20 parts by weight. (B) If the amount of the swellable layered silicate is too small, the effect of suppressing dimensional change due to heat is small, and if it is too large, strength and fluidity may decrease.
The weight of the swellable layered silicate treated with an organic onium ion, a coupling agent, or the like changes depending on the treatment amount with the organic onium ion, the coupling agent, or the like. Therefore, the content of the (B) swellable layered silicate in the present invention is:
Based on the inorganic ash content of the swellable layered silicate. Here, the inorganic ash content of the swellable phyllosilicate refers to the swellable phyllosilicate (sample amount: about 0.1 g) treated with an organic onium ion, a coupling agent, etc., fired in an electric furnace at 600 ° C. for 3 hours. Indicates the amount of ash obtained by volatilizing the organic component.

In the polyphenylene sulfide resin composition of the present invention, the layered silicate is uniformly dispersed at a single layer level in the polyphenylene sulfide resin (or a mixture of the polyphenylene sulfide resin and an amorphous resin described later) as a matrix. Is preferred. The state in which the layered silicate is uniformly dispersed at the level of a single layer means that the layered silicate is dispersed in the entire matrix resin without secondary aggregation in a state of about 10 to 10 layers. This state can be confirmed by cutting a section from the polyphenylene sulfide resin composition and observing the section with an electron microscope.

In the present invention, the use of the non-fibrous filler (C) is indispensable for economically obtaining a composition having excellent mechanical strength while exhibiting the effect of suppressing dimensional change due to heat and high rigidity. is there.

The non-fibrous filler (C) used in the present invention refers to a filler having various shapes such as a true sphere, a substantially true sphere, a cube, a substantially cube, and a plate. If the composition is fibrous but the aspect ratio in the composition is less than 5, the composition is classified as a non-fibrous filler. However, the swellable layered silicate is excluded. Here, the aspect ratio indicates a ratio (l / d) between the average diameter (d) and the weight average length (l).

Examples of the non-fibrous filler include powdery silicates such as zeolite, sericite, kaolin, pyrophyllite, talc, alumina silicate, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, and the like. Metal compounds such as iron oxide; carbonates such as calcium carbonate, magnesium carbonate and dolomite; sulfates such as calcium sulfate and barium sulfate; hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide; glass beads; and ceramics beads,
Examples thereof include boron nitride, potassium whisker and silicon carbide, and talc, calcium carbonate, calcium sulfate, and glass fine particles are particularly preferably used.

These may be hollow, and it is also possible to use two or more of these fillers in combination.
Pretreatment of these fillers with a coupling agent such as an isocyanate-based compound, an organic silane-based compound, an organic titanate-based compound, an organic borane-based compound, or an epoxy compound means that more excellent mechanical strength is obtained. Is preferred.

In the present invention, it is preferable to incorporate a fibrous filler (D) from the viewpoint of obtaining superior strength and rigidity. The (D) fibrous filler refers to a filler having a fibrous shape and having an aspect ratio of at least 5 in the composition. Examples of such a fibrous filler include glass fiber, carbon fiber, metal fiber, metal oxide fiber, aramid fiber, and the like, and a method of using these alone or in combination of two or more.

Pretreatment of these fibrous fillers with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, an epoxy compound, etc., results in a more excellent mechanical strength. Is preferred in the sense of obtaining

The amount of the non-fibrous filler (C) used in the present invention is usually 10 to 10 parts by weight of the PPS resin.
A range of 400 parts by weight is selected, with a range of 50-300 parts by weight being more preferred. If the amount is too small, sufficient dimensional stabilizing effect and high rigidity effect cannot be obtained even when (B) swellable layered silicate is added, and if too large, the melt fluidity of the PPS composition is impaired. It is not preferable because injection moldability is impaired.

In the present invention, when (D) the fibrous filler is compounded, the compounding amount is 5 parts per 100 parts by weight of the PPS resin.
A range of １５０150 parts by weight is selected, with a range of 20-100 parts by weight being more preferred. If the amount is too large, the melt fluidity of the PPS composition is impaired, and the dimensional change is anisotropic, that is, the difference between the dimensional change in the fiber orientation direction and the dimensional change in the direction perpendicular to the fiber orientation is undesirably large.

In particular, when the degree of dimensional change due to heat, that is, the anisotropy of the coefficient of thermal expansion occurs, it is not preferable because the molded product is twisted. To suppress this,
More preferably, (C) the non-fibrous filler is in excess of (D) the fibrous filler.

In the present invention, it is preferable to use (E) an amorphous resin having a glass transition temperature of 100 ° C. or higher in order to obtain a more excellent dimensional stabilizing effect.

Specific examples of the (E) amorphous resin having a glass transition temperature of 100 ° C. or higher include polycarbonate resins, polyphenylene ether resins, polysulfone resins, polyethersulfone resins, polyarylate resins, Examples thereof include a polyetherimide resin and a polyamideimide resin. Among them, a polyphenylene ether resin, a polysulfone resin, a polyethersulfone resin, and a polyamideimide resin are particularly preferable.

When the (E) amorphous resin having a glass transition temperature of 100 ° C. or more is used, the compounding amount is as follows.
5 to 200 parts by weight, especially 10 to 100 parts by weight
A range of 100 parts by weight is more preferred.

In the PPS resin composition of the present invention, plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, and organic phosphorus compounds, talc, kaolin, organic compounds, etc., as long as the effects of the present invention are not impaired. Crystal nucleating agents such as phosphorus compounds and polyetheretherketone, release agents such as polyolefin compounds, silicone compounds, long-chain aliphatic ester compounds and long-chain aliphatic amide compounds, zinc carbonate, manganese carbonate, and magnesium carbonate , Calcium carbonate, particulate zinc oxide,
Hydrotalcite (Mg _0.7・ Al _0.3 (OH) ₂・ CO ₃・ 0.55H ₂
O), metal solid solution (Mg _0.4・ Zn _0.3・ Al (OH) ₂ (CO ₃ ) _0.15・ 0.5
_{5H 2 O, Mg 0.5 · Pb} 0.22 · Al 0.28 (OH) 2 · I 0 .28 · 0.16H 2 O)
Mold additives such as mold corrosion inhibitors, coloring inhibitors, antioxidants, heat stabilizers, lubricants such as lithium stearate and aluminum stearate, UV additives, coloring agents, flame retardants, and foaming agents. Can be added.

The PPS resin composition of the present invention may be any polyester, polyamide, polytetrafluoroethylene, polyetherketone, polythioetherketone, polyetheretherketone, epoxy resin, phenolic resin as long as the effects of the present invention are not impaired. And resins such as polyethylene, polystyrene, polypropylene, ABS resin, polyamide elastomer, polyester elastomer, polyalkylene oxide, and olefin-based copolymer containing a carboxyl group or the like.

In the present invention, the PPS
The method for preparing the resin composition is not particularly limited, and the mixture of the raw materials is supplied to a generally known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader and a mixing roll, and the mixture is heated to 280 to 380 ° C. A typical example is a method of melt-kneading at a temperature. There is no particular limitation on the mixing order of the raw materials, and a method in which all the raw materials are blended and then melt-kneaded according to the above method, a part of the raw materials are mixed, and this mixture and the remaining raw materials are blended, and then melt-kneaded according to the above method A method in which some raw materials are blended and then melt-kneaded according to the above method, and the remaining raw materials are blended and melt-kneaded. Alternatively, some raw materials are blended and then melt-kneaded by a single- or twin-screw extruder. Any method such as a method of mixing the remaining raw materials using a side feeder may be used. Further, as for the small amount of the additive component, it is of course possible to knead the other component by the above-mentioned method and the like to form a pellet, and then add it before molding to provide for molding.

The PPS resin composition obtained according to the present invention has better dimensional stability and higher rigidity without significantly impairing the inherent thermal stability, electrical properties, mechanical properties, etc. of the PPS resin composition. It is a PPS resin composition.

The PPS resin composition thus obtained is particularly suitable for use in injection molding, and in particular, it is important to suppress dimensional changes due to heat and to increase the elastic modulus.
It can be particularly suitably used for optical system components such as optical pickup components (lens holder, slide base) used for ROM, DVD and the like.

Further, the resin composition of the present invention also has a characteristic that it does not easily lose its shape at a high temperature.
Furthermore, it is also useful for applications exposed to a high temperature of 300 ° C. or higher. In particular, in recent years, lead-free soldering has been progressing in the electronic and electrical industry due to environmental problems, and higher solder heat resistance than ever before has been required. The above-mentioned feature that the shape collapse hardly occurs at high temperatures is also useful from such a viewpoint,
That is, the resin composition of the present invention is also useful as a material for electronic-electric parts compatible with lead-free solder.

The molded article of the PPS resin composition of the present invention can be used in addition to the above-mentioned optical parts, sensors, LED lamps, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, variable condenser cases, oscillators, Terminal board, transformer, plug, printed circuit board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder, parabolic antenna, computer related parts, etc. In addition to being suitable for electronic component applications represented by, generators, motors, transformers, current transformers, voltage regulators, rectifiers,
Inverters, relays, power contacts, switches, circuit breakers,
Applications for electrical equipment parts such as knife switches, other pole rods, electrical parts cabinets, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, audio parts, audio and laser disk (registered trademark), etc. Home and office electrical product parts such as equipment parts, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc .; office computer related parts, telephone related parts, facsimile related parts, copier related parts, washing Jigs, motor parts,
Machine-related parts such as lighters and typewriters: optical equipment such as microscopes, binoculars, cameras, watches, etc., precision machine-related parts; alternator terminals,
Alternator connector, IC regulator, potentiometer base for light deer, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint,
Carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, air conditioner thermostat base, heating hot air Flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dust distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve Coil, fuse connector, horn terminal, electrical component insulation plate, Flop motor rotor, lamp socket, lamp reflector, lamp housing,
It can be applied to various applications such as automobile / vehicle related parts such as a brake piston, a solenoid bobbin, an engine oil filter, and an ignition device case.

[0066]

The present invention will be described in more detail with reference to the following examples.

Experimental Method (1) Method of Measuring Linear Expansion Coefficient PPS resin pellets were injection molded by Sumitomo-Nestal Co., Ltd. under the conditions of cylinder temperature 280 (bottom of hopper) to 320 ° C. (nozzle side) and mold temperature 140 ° C. Machine (SG-75HIPRO MI
Injection molding was performed using II) to obtain an ASTM No. 1 test piece. This was annealed at 120 ° C. for 1 hour to remove residual strain.

From the vicinity of the center of the test piece, a sample was cut out in the flow direction of the resin (hereinafter abbreviated as MD) and the direction perpendicular to the flow direction (hereinafter abbreviated as TD). The sample was a prism having a length of about 10 mm and a width of about 3 mm.

For the measurement, TMA100 manufactured by Seiko Instruments Inc. was used, and the coefficient of linear expansion was measured in the range of 30 to 90 ° C.

(2) Flexural strength and modulus of elasticity PPS resin pellets were injected at a cylinder temperature of 280 (bottom side of hopper) to 320 ° C. (nozzle side) and a mold temperature of 140 ° C. using an injection molding machine (SG) manufactured by Sumitomo-Nestal Company. -75HIPRO MI
Injection molding using II), 127 mm x 12.7 m
A rectangular parallelepiped specimen of mx 6.35 mm was obtained. Using this test piece, in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, using an Orientec Tensilon RTA-1T tester,
The test piece was placed in a direction in which the 12.7 mm × 127 mm surface was in contact with the fulcrum, the distance between the fulcrum was 100 mm, and the crosshead was 3 m
The relationship between the amount of strain and the stress was determined by performing a bending test at m, and the elastic modulus was calculated.

(3) Evaluation of Shape Distortion Approximately 10 g of resin composition pellets were measured in an aluminum cup, preliminarily dried at 130 ° C. for 3 hours, treated at 320 ° C. for 2 hours, and visually observed for the shape of the pellets. did.

：: The pellet shape is kept almost as it is.

Δ: A part of the pellet was melted and the shape was broken.

×: The whole was melted, and the pellet hardly kept its original shape.

Raw Materials (A) PPS resin PPS-1: M2888, manufactured by Toray Industries, Inc. (B) Swellable layered silicate Reference Example 1 (Production of organically modified layered silicate) B-1: Na-type montmorillonite ( Kunimine industry: Kunipia F, cation exchange capacity 120 meq / 100 g) 1
Of benzyldimethyloctadecyl ammonium chloride in an amount of 51 g.
(Equivalent to the cation exchange capacity) in 2 L of warm water dissolved therein and stirred for 1 hour. The resulting precipitate was separated by filtration and washed with warm water. This washing and filtration operations were performed three times, and the obtained solid was vacuum-dried at 80 ° C. to obtain a dried organically modified layered silicate (B-1). The obtained organically modified layered silicate had an inorganic ash content of 68% by weight. In addition,
The inorganic ash content is a value obtained by incineration of 0.1 g of the organically modified layered silicate in an electric furnace at 600 ° C. for 3 hours.

Reference Example 2 (Production of Organized Layered Silicate) B-2: 50 g of the above-mentioned organically modified layered silicate (B-1) was weighed, and β- (3,4-epoxycyclohexyl) was added thereto.
1.7 g of ethyltrimethoxysilane was added dropwise and mixed in a mortar for 15 minutes to obtain an organized layered silicate (B-2).
The obtained organically modified layered silicate was found to have an inorganic ash content of 66% by weight.

(C) Non-fibrous filler C-1: calcium carbonate (KSS-10, manufactured by Konpei Mining Co., Ltd.)
00, amorphous filler) C-2: glass beads (Toshiba Barodini, EGB)
(731B, spherical filler) (D) Fibrous filler D-1: Glass fiber E glass chopped strand having a length of 3 mm and a diameter of 10 µm. Asahi Fiberglass C
S03JAFT523 (E) Amorphous resin E-1: Polyphenylene ether resin (YPX-100L manufactured by Mitsubishi Gas Chemical Company) E-2: Polyamideimide resin (TI manufactured by Toray Industries, Inc.)
-5013) Examples 1 to 5 (A) PPS resin, (B) organically modified layered silicate and other fillers were dry blended in the proportions shown in Table 1 and preliminarily mixed in a tumbler for 2 minutes. 2
The mixture was melt-kneaded with a twin-screw extruder set at 80 ° C (lower side of hopper) to 320 ° C (discharge port side), pelletized by a strand cutter, and dried at 120 ° C overnight. The linear expansion coefficient, flexural strength and flexural modulus were measured using the pellets. Table 1 shows the results.

[0078]

[Table 1]

Examples 6 and 7 (A) PPS resin, (B) organically modified layered silicate and other components were dry blended in the proportions shown in Table 1 and preliminarily mixed in a tumbler for 2 minutes.
The mixture was melt-kneaded with a twin-screw extruder set at 0 ° C (lower side of hopper) to 350 ° C (discharge port side), pelletized by a strand cutter, and dried at 120 ° C overnight. The linear expansion coefficient, flexural strength and flexural modulus were measured using the pellets. Table 1 shows the results.

Comparative Examples 1 to 3 (B) Dry blending was carried out in the proportions shown in Table 1 in the same manner as in Examples 1, 4 and 7 except that the organically modified layered silicate was not added. After mixing, the mixture was melt-kneaded with a twin-screw extruder, pelletized with a strand cutter, and dried at 120 ° C. overnight. The linear expansion coefficient and the flexural modulus were measured using such pellets. Table 1 shows the results.

[0081]

Industrial Applicability The PPS resin composition of the present invention relates to a polyphenylene sulfide resin composition having a small dimensional change due to heat and high rigidity, and particularly provides a resin composition suitable for optical parts and an injection-molded product thereof. I do.

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Claims (9)

[Claims] 1. A polyphenylene sulfide resin (A)
(B) 0.1 to 1 parts by weight of the swellable layered silicate with respect to 0 parts by weight.
A polyphenylene sulfide resin composition comprising 00 parts by weight and (C) 10 to 400 parts by weight of a non-fibrous filler. 2. The polyphenylene sulfide according to claim 1, wherein the swellable phyllosilicate (B) is a swellable phyllosilicate obtained by exchanging exchangeable cations existing between layers with organic onium ions. Resin composition. 3. The polyphenylene sulfide resin composition according to claim 2, wherein the organic onium ion is a quaternary ammonium ion. 4. A polyphenylene sulfide resin (A)
(B) 0.1 to 1 parts by weight of the swellable layered silicate with respect to 0 parts by weight.
The polyphenylene sulfide resin composition according to any one of claims 1 to 3, wherein the polyphenylene sulfide resin composition is obtained by mixing 00 parts by weight, (C) 10 to 400 parts by weight of the non-fibrous filler, and (D) 5 to 150 parts by weight of the fibrous filler. 5. A polyphenylene sulfide resin (A)
(B) 0.1 to 1 parts by weight of the swellable layered silicate with respect to 0 parts by weight.
(C) 10 to 400 parts by weight of the non-fibrous filler, (D) 5 to 150 parts by weight of the fibrous filler, and (C) the non-fibrous filler. The polyphenylene sulfide resin composition according to claim 4, wherein the compounding amount of (F) is larger than the compounding amount of the fibrous filler (D). 6. A polyphenylene sulfide resin comprising: (E) an amorphous resin having a glass transition temperature of 100 ° C. or higher;
The polyphenylene sulfide resin composition according to any one of claims 1 to 5, wherein the polyphenylene sulfide resin composition is blended in an amount of 5 to 200 parts by weight based on 00 parts by weight. 7. An alkoxysilane compound having a functional group selected from the group consisting of (F) an epoxy group, an amino group, a ureide group and an isocyanate group is added in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin (A). The polyphenylene sulfide resin composition according to any one of claims 1 to 6, wherein the polyphenylene sulfide resin composition is blended in parts. 8. A molded article obtained by injection molding the polyphenylene sulfide resin composition according to claim 1. 9. An optical component obtained by injection molding the polyphenylene sulfide resin composition according to claim 1.