WO2012132429A1 - Polyphenylene sulfide resin composition and moldings thereof - Google Patents

Abstract

A polyphenylene sulfide resin composition obtained by blending (A) 100 parts by weight of a polyphenylene sulfide resin with (B) 0.1 to 30 parts by weight of hydrotalcite particles which each comprise an Mg-Al hydrotalcite core particle and an Mg-M-Al hydrotalcite layer provided on the surface of the core particle, M being a divalent metal.

Description

Polyphenylene sulfide resin composition and molded article comprising the same

The present invention relates to a polyphenylene sulfide resin composition having a small amount of gas generated in a region below the melting point of a polyphenylene sulfide resin near 200 ° C. and a molded article thereof without impairing fluidity and mechanical strength. The molded article made of the polyphenylene sulfide resin composition of the present invention is particularly suitable for optical parts having lenses and reflecting surfaces.

Polyphenylene sulfide resin (hereinafter sometimes abbreviated as PPS resin) belongs to high heat-resistant super engineering plastics and has excellent mechanical strength, rigidity, flame resistance, chemical resistance, electrical properties and dimensional stability, etc. ing. Therefore, it is widely used for various electric / electronic parts, home appliance parts, automobile parts, machine parts, etc., mainly for injection molding.

In recent years, taking advantage of the high heat resistance of polyphenylene sulfide resin, the composition has been applied to lamp case parts such as projectors, parts around lamps such as lens holder parts, and chassis parts. However, with the miniaturization of the projector itself and the increase in the output of the light source, the temperature environment inside the projector becomes more severe, and parts made of a polyphenylene sulfide resin composition are used in a temperature environment near 200 ° C. It was. In this temperature region, since gas is generated from the polyphenylene sulfide resin composition, it has become a problem that the lens adheres to the lens or mirror and fogging occurs.

As a polyphenylene sulfide resin composition, for example, Patent Documents 1 and 2 disclose a polyphenylene sulfide resin composition containing hydrotalcite. According to the method for producing a resin composition described in Patent Document 1, a polyphenylene sulfide resin composition in which the content of free electrolyte impurities is reduced is obtained. Moreover, according to the manufacturing method of the resin composition of patent document 2, the polyphenylene sulfide resin composition by which generation | occurrence | production of the corrosive gas at the time of shaping | molding was suppressed is obtained. The hydrotalcite used in these documents is Mg—Al hydrotalcite. On the other hand, Patent Document 3 describes that a highly transparent resin composition is obtained by blending Mg—Zn—Al hydrotalcite with vinyl chloride or the like.

In addition, as a resin composition with improved workability such as high crystallization in low temperature mold molding and insert molding by improving the crystallization speed, polyphenylene sulfide resin is blended with Mg-Al hydrotalcite. A polyphenylene sulfide resin composition has been proposed (see, for example, Patent Document 4). Further, as a resin composition in which metal corrosion during molding and mold contamination are suppressed, a polyphenylene sulfide resin composition obtained by blending magnesium aluminum hydroxyperchlorate hydrotalcite with polyphenylene sulfide resin has been proposed (for example, , See Patent Document 5).

On the other hand, hydrotalcite is blended with synthetic resin as a synthetic resin composition for agricultural films, etc. for preventing whitening of agricultural films, preventing blooming, preventing electrical resistance, and coloring (yellowing). A synthetic resin composition has been proposed (see, for example, Patent Document 6). Further, as a synthetic resin composition having improved heat deterioration resistance, non-aggregability, molding suitability, and impact strength, a synthetic resin obtained by blending hydrotalcite particles with a thermoplastic synthetic resin has been proposed (for example, Patent Document 7). The hydrotalcite particles used in Patent Documents 6 to 7 are composed entirely of hydrotalcite particles having the same composition.

However, the resin compositions described in Patent Documents 4 to 7 have insufficient fluidity and mechanical strength, and the molded product obtained from the resin composition has insufficient effect of suppressing defects such as clouding. There was a problem that there was.

Moreover, the polyphenylene sulfide resin composition which can prevent fogging of a lens etc. by using specific polyphenylene sulfide resin is disclosed (for example, refer patent document 8). Alternatively, it is disclosed that decomposition of a resin by an acid can be suppressed by blending a hydrotalcite-type powder having a core-shell structure (corresponding to a core-surface layer structure in the present application) with an ethylene-vinyl acetate copolymer. (For example, refer to Patent Document 9) However, the compositions specifically disclosed in Patent Documents 8 and 9 are insufficient for reducing the fogging of lenses and the like near 200 ° C.

Japanese Patent Laid-Open No. 61-120856 JP-A-6-322271 JP 2004-299931 A Japanese Patent Laid-Open No. 4-103665 Japanese Patent Publication No.4-221831 WO2006 / 043352 Publication JP 2004-225052 A JP 2009-275197 A JP 2011-105573 A

The present invention has been achieved as a result of diligent investigations aimed at solving the above-described problems in the prior art. That is, the present invention provides a polyphenylene sulfide resin composition and a molded product thereof with a small amount of gas generated in a region below the melting point of the polyphenylene sulfide resin near 200 ° C. without impairing fluidity and mechanical strength.

The inventors of the present invention provide a hydrotalcite particle comprising Mg-Al hydrotalcite as a core particle in polyphenylene sulfide resin, and Mg-M-Al hydrotalcite layer having M as a divalent metal on the particle surface of the core particle. The polyphenylene sulfide resin composition which can suppress the generated gas in the vicinity of 200 ° C. without impairing the fluidity and mechanical strength was found by blending.

That is, the present invention has been made to solve at least a part of the above-described problems, and embodiments of the present invention can include at least a part of the following configurations.

(1) (A) Mg-M-Al hydrotalcite with (B) Mg-Al hydrotalcite as core particles and M as a divalent metal on the particle surface of 100 parts by weight of (A) polyphenylene sulfide resin A polyphenylene sulfide resin composition comprising 0.1 to 30 parts by weight of hydrotalcite particles having a site layer.

(2) The polyphenylene sulfide resin composition according to (1), wherein the divalent metal M contains Mg and / or Zn.

(3) The polyphenylene sulfide resin composition according to (1) or (2), wherein the average plate surface diameter of the hydrotalcite particles is 0.1 to 1 μm.

However, in the polyphenylene sulfide resin composition described in (1) or (2) above, the average plate surface diameter of the hydrotalcite particles may be less than 0.1 μm. Further, in the polyphenylene sulfide resin composition described in (1) or (2) above, the average plate surface diameter of the hydrotalcite particles may exceed 1 μm.

(4) The polyphenylene according to any one of (1) to (3), wherein (A) 5 to 300 parts by weight of an inorganic filler other than hydrotalcite is blended with 100 parts by weight of the polyphenylene sulfide resin A sulfide resin composition.

However, in the polyphenylene sulfide resin composition according to any one of the above (1) to (3), (A) the inorganic filler other than hydrotalcite (C) blended in 100 parts by weight of the polyphenylene sulfide resin is 5 parts by weight. It may be less. In the polyphenylene sulfide resin composition according to any one of the above (1) to (3), (A) the inorganic filler other than (C) hydrotalcite to be added to 100 parts by weight of the polyphenylene sulfide resin is 300 parts by weight. It is good as exceeding.

(5) Any one of (1) to (4), wherein the haze value of the glass plate after a fogging test is performed at 200 ° C. for 168 hours on a pellet made of the polyphenylene sulfide resin composition is 10% or less A polyphenylene sulfide resin composition.

However, in the polyphenylene sulfide resin composition according to any one of the above (1) to (4), the haze value of the glass plate after a fogging test of a pellet made of the polyphenylene sulfide resin composition at 200 ° C. for 168 hours is 10 It is good as exceeding%.

(6) A molded article comprising the polyphenylene sulfide resin composition according to any one of (1) to (5).

(7) The molded body according to (6), wherein the molded body is an optical component.

However, the molded body described in (6) may be other than optical parts.

According to an embodiment of the present invention, polyphenylene which can prevent fogging of a lens or the like with less generated gas in a region below the melting point of a polyphenylene sulfide resin near 200 ° C. without impairing fluidity and mechanical strength. It is possible to obtain a sulfide resin composition and a molded body thereof. The polyphenylene sulfide resin composition of the embodiment of the present invention can prevent fogging of a lens or the like, and is suitable for applications such as various electric / electronic parts, automobile parts and mechanical parts. In particular, it is suitable as a material for an optical component (structural member for a light projecting device) such as a projector component that is used under severely used heat conditions and avoids the occurrence of fogging such as a lens.

((A) polyphenylene sulfide resin)
The polyphenylene sulfide resin (A) (hereinafter sometimes abbreviated as PPS) used in the embodiment of the present invention is a repeating unit represented by the following structural formula.

Is a polymer containing 70 mol% or more, preferably 90 mol% or more. When the repeating unit is less than 70 mol%, the heat resistance tends to be impaired.

In addition, the polyphenylene sulfide resin used in the embodiment of the present invention can comprise 30 mol% or less of the repeating unit with a repeating unit having the following structural formula.

Such a polyphenylene sulfide resin can be obtained by a generally known method, for example, a method described in Japanese Patent Publication No. 45-3368, or a method described in Japanese Patent Publication No. 52-12240 or Japanese Patent Publication No. 61-7332. Can be manufactured. The method described in Japanese Patent Publication No. 45-3368 is a method for obtaining a polymer having a relatively small molecular weight. The methods described in Japanese Patent Publication Nos. 52-12240 and 61-7332 are methods for obtaining a polymer having a relatively large molecular weight.

In the embodiment of the present invention, the polyphenylene sulfide resin obtained as described above is washed with an acid aqueous solution (acid washing), treatment with an organic solvent or hot water, washing with water containing an alkaline earth metal salt, Various treatments such as activation with functional group-containing compounds such as acid anhydrides, amines, isocyanates, functional group-containing disulfide compounds, crosslinking / high molecular weight by heating in air, under inert gas atmosphere such as nitrogen or under reduced pressure It can be used after being subjected to a treatment selected from the above heat treatment. Of course, it is possible to repeat these processes a plurality of times or to combine different processes. In particular, the use of the polyphenylene sulfide resin after acid cleaning is particularly effective for achieving the effects of the embodiment of the present invention more remarkably.

The following method can be exemplified as a specific method in the case of acid cleaning the polyphenylene sulfide resin. That is, it is a method of immersing a polyphenylene sulfide resin in an acid or an aqueous solution of an acid, and it is possible to appropriately stir or heat as necessary. The acid used is not particularly limited as long as it does not have the action of decomposing polyphenylene sulfide resin, and is saturated with aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, and halo-substituted fatty acids such as chloroacetic acid and dichloroacetic acid. Aliphatic unsaturated monocarboxylic acid such as aromatic saturated carboxylic acid, acrylic acid, crotonic acid, aromatic carboxylic acid such as benzoic acid, salicylic acid, dicarboxylic acid such as oxalic acid, malonic acid, succinic acid, phthalic acid, fumaric acid, And inorganic acidic compounds such as sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid and silicic acid. Of these acids, acetic acid and hydrochloric acid are particularly preferably used. The pH of the acid or acid aqueous solution used for the acid cleaning of the polyphenylene sulfide resin is preferably 2.5 to 5.5. The amount of the acid or acid aqueous solution used for the acid cleaning is preferably 2 to 100 kg, more preferably 4 to 50 kg, and more preferably 5 to 15 kg with respect to 1 kg of the dried polyphenylene sulfide resin. Further preferred. There is no particular limitation on the washing temperature, and it can usually be carried out at room temperature. When heating, it can be carried out at 50 to 90 ° C. The washing time is usually preferably 30 minutes or longer, and more preferably 45 minutes or longer. The upper limit is not particularly limited, but is preferably about 90 minutes from the viewpoint of cleaning efficiency. For example, when acetic acid is used, it is preferable to immerse the polyphenylene sulfide resin powder in a pH 4 aqueous solution kept at room temperature and stir for 45 to 90 minutes. The acid-treated polyphenylene sulfide resin is preferably washed several times with water or warm water in order to remove residual acid or salt. The water washing temperature is preferably 50 to 100 ° C, more preferably 60 to 95 ° C. The water used for washing is preferably distilled water or deionized water in the sense that it does not impair the preferable chemical modification effect of the polyphenylene sulfide resin by acid washing.

The following method can be illustrated as a specific method when the polyphenylene sulfide resin is washed with an organic solvent. That is, the organic solvent used for washing is not particularly limited as long as it does not have the action of decomposing polyphenylene sulfide resin. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, etc. , Sulfoxide / sulfone solvents such as dimethylsulfone, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, ether solvents such as dimethyl ether, dipropyl ether, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene chloride, dichloroethane , Halogen solvents such as tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol Propylene glycol, phenol, cresol, alcohol phenol based solvents such as polyethylene glycol, and benzene, toluene, and aromatic hydrocarbon solvents such as xylene. Among these organic solvents, use of N-methylpyrrolidone, acetone, dimethylformamide, chloroform and the like is particularly preferable. These organic solvents are used alone or in combination of two or more. As a method of washing with an organic solvent, there is a method of immersing a polyphenylene sulfide resin in an organic solvent, and if necessary, stirring or heating can be appropriately performed. There is no particular limitation on the washing temperature when washing the polyphenylene sulfide resin with an organic solvent, and an arbitrary temperature of about room temperature to about 300 ° C. can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect is usually obtained at a cleaning temperature of room temperature to 150 ° C. The polyphenylene sulfide resin that has been washed with an organic solvent is preferably washed several times with water or warm water in order to remove the remaining organic solvent.

The following method can be illustrated as a specific method when the polyphenylene sulfide resin is treated with hot water. That is, in order to express the preferable chemical modification effect of the polyphenylene sulfide resin by hot water washing, the water used is preferably distilled water or deionized water. The operation of the hot water treatment is usually performed by charging a predetermined amount of polyphenylene sulfide resin into a predetermined amount of water, and heating and stirring at normal pressure or in a pressure vessel. The ratio of the polyphenylene sulfide resin to water is preferably larger, but usually a bath ratio of 200 g or less of polyphenylene sulfide resin is selected per 1 liter of water.

The following method can be exemplified as a specific method when the polyphenylene sulfide resin is washed with water containing an alkaline earth metal salt. There are no particular restrictions on the type of alkaline earth metal salt, but alkaline earth metal salts of water-soluble organic carboxylic acids such as calcium acetate and magnesium acetate, and alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide. Is a preferred example. In particular, alkaline earth metal salts of water-soluble organic carboxylic acids such as calcium acetate and magnesium acetate are preferred. The temperature of water is preferably room temperature to 200 ° C., more preferably 50 to 90 ° C. The amount of the alkaline earth metal salt used in the water is preferably 0.1 to 50 g, more preferably 0.5 to 30 g, based on 1 kg of the dried polyphenylene sulfide resin. The cleaning time is preferably 0.5 hours or longer, and more preferably 1.0 hour or longer. The washing bath ratio (weight of hot water containing alkaline earth metal salt per unit weight of dry polyphenylene sulfide resin) depends on the washing time and temperature, but hot water containing the above alkaline earth metal per kg of dry polyphenylene sulfide. Is preferably washed with 5 kg or more, more preferably 10 kg or more. The upper limit of the washing bath ratio is not particularly limited and may be high, but it is preferably 100 kg or less from the viewpoint of the amount used and the effect obtained. Such warm water cleaning may be performed a plurality of times.

Specific methods for crosslinking / high molecular weight polyphenylene sulfide resin by heating include 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 of heating in an atmosphere can be exemplified. In the case of crosslinking / high molecular weight by heating, heating may be performed until a desired melt viscosity is obtained at a predetermined temperature in a heating container. As the heat treatment temperature, a range of 150 to 280 ° C. is usually selected, and preferably 200 to 270 ° C. The heat treatment time is usually selected in the range of 0.5 to 100 hours, preferably 2 to 50 hours. By controlling the heat treatment temperature and the heat treatment time, a target viscosity level can be obtained. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary blade or a stirring blade. However, for efficient and more uniform treatment, a heating device with a rotary blade or a stirring blade is used. Is more preferable. When a polyphenylene sulfide resin that has been crosslinked / polymerized by heating is used as the (A) polyphenylene sulfide resin of the embodiment of the present invention, the amount of generated gas is more significantly reduced.

A specific method for heat-treating the polyphenylene sulfide resin under an inert gas atmosphere such as nitrogen or under reduced pressure is a heat treatment temperature of 150 to 280 ° C., preferably 200, under an inert gas atmosphere such as nitrogen or under reduced pressure. A method of heat treatment under conditions of ˜270 ° C. can be exemplified. As the heating time, conditions of 0.5 to 100 hours, preferably 2 to 50 hours can be selected. The heat treatment apparatus may be a normal hot air drier or a heating apparatus with a rotary or stirring blade. However, for efficient and more uniform treatment, a heating apparatus with a rotary or stirring blade may be used. More preferably it is used.

The melt viscosity of the polyphenylene sulfide resin used in the embodiment of the present invention is not particularly limited as long as it has a range of 1 to 1500 Pa · s. However, from the viewpoint of easily obtaining a thin injection molded body, it is preferably 300 Pa · s or less, and more preferably 200 Pa · s or less. Regarding the lower limit, if the melt viscosity is 1 Pa · s or less, melt molding processability is inferior, and it may be difficult to increase the amount of gas generated. Therefore, it is preferably 1 Pa · s or more, and preferably 5 Pa · s or more. More preferably.

In addition, the melt viscosity in the embodiment of the present invention is a value measured using a capillograph manufactured by Toyo Seiki Co., Ltd. under conditions of 300 ° C. and a shear rate of 1000 / s.

In the embodiment of the present invention, a plurality of types of polyphenylene sulfide resins having different melt viscosities may be mixed and used.

((B) Mg-M-Al hydrotalcite particles)
Next, (B) Mg—Al hydrotalcite used in the embodiment of the present invention is used as a core particle, and a Mg—M—Al hydrotalcite layer is provided on the particle surface of the core particle with M as a divalent metal. The hydrotalcite particles (hereinafter referred to as Mg-M-Al based hydrotalcite particles) will be described.

In the embodiment of the present invention, by blending 0.1 to 30 parts by weight of (B) Mg-M-Al hydrotalcite particles with respect to 100 parts by weight of the polyphenylene sulfide resin, the fluidity and mechanical strength are impaired. Thus, a polyphenylene sulfide resin composition with less generated gas near 200 ° C. is obtained. Furthermore, when the polyphenylene sulfide resin composition of the embodiment of the present invention is molded, it is possible to obtain a molded body that can prevent fogging of lenses, mirrors and the like.

The (B) Mg-M-Al hydrotalcite particles used in the embodiment of the present invention have Mg-Al hydrotalcite as core particles, and Mg-M with M as a divalent metal on the particle surface of the core particles. -Hydrotalcite particles having an Al-based hydrotalcite layer, preferably having an average plate surface diameter of 0.1 to 1 µm, more preferably 0.15 to 0.8 µm.
The (B) Mg-M-Al hydrotalcite particles used in the embodiment are specifically hydrotalcite-type particle powders disclosed in JP-A No. 2004-299931 or JP-A No. 2011-105573. Can be used.

Here, the average plate surface diameter of the Mg-M-Al-based hydrotalcite particles is a value obtained by observing the particle size of 100 particles with an electron micrograph, measuring the particle size of 100 particles, and taking the number average. The particle diameter of each particle is a value obtained by adding the longest diameter and the shortest diameter on the surface shown in the photograph and dividing by two.

When the average plate surface diameter of the Mg-M-Al hydrotalcite particles is 0.1 μm or more, the dispersibility when blended with the PPS resin is improved. Also, industrial production is practical when the average plate surface diameter of the Mg-M-Al hydrotalcite particles is 1 μm or less.

The BET specific surface area of the (B) Mg-M-Al hydrotalcite particles used in the embodiment of the present invention is preferably 5 to 150 m ² / g, more preferably 5 to 60 m ² / g, and still more preferably. Is 7 to 30 m ² / g. The BET specific surface area was measured using B.I. E. T.A. It is a value measured by the method. Since the hydrotalcite particles having a BET specific surface area of 5 m ² / g or more do not have a specific surface area that is too small, it is possible to obtain sufficient gas adsorbability. When the BET specific surface area is 150 m ² / g or less, the particles hardly aggregate and can be uniformly dispersed in the resin.

The Mg—M—Al hydrotalcite particles are preferably those represented by the following composition formula as a whole. The molar ratio of the total number of moles of Mg, divalent metal M and Al in the outer layer formed on the particle surface of the core particles to the total number of moles of Mg and Al of the core particles is preferably 0.50 or less, 0.35 The following is more preferable.

<Composition of Mg-M-Al hydrotalcite particles>
_{(Mg 1-y M y)} 1-x · Al x · (OH) 2 · An n- p · mH 2 O
0.2 ≦ x ≦ 0.5,
0.003 ≦ y ≦ 0.6,
0 <m ≦ 1,
p = x / n,
An: n-valent anion

Here, the value of m is a value indicating the water content of the Mg-M-Al-based hydrotalcite particles, and is preferably 0.8 to 1.0.

The values of x and y in the above composition formula can be obtained by dissolving Mg-M-Al hydrotalcite particles with an acid and analyzing them with a plasma emission spectrometer SPS4000 (Seiko Electronics Co., Ltd.). it can.

The ratio x of the Al content of the Mg-M-Al hydrotalcite particles of the embodiment of the present invention is preferably 0.2 to 0.5. When x is less than 0.2 and more than 0.5, it is difficult to obtain a single layer of hydrotalcite particles. The single layer means that each component of the core particle and the outer layer on the surface of the core particle is uniform. More preferably, it is 0.2 to 0.4. By using the hydrotalcite particles in which x is in this range, the effect of suppressing the generated gas when blended with the PPS resin can be expressed. The proportion y of the divalent metal M content is preferably 0.003 to 0.6. By using the hydrotalcite particles having y in this range, the effect of suppressing the generated gas when blended with the PPS resin can be expressed. A preferred range of y is 0.003 to 0.4.

The content of the divalent metal M present on the surface of the Mg-M-Al hydrotalcite particle used in the embodiment of the present invention is the magnesium in the outer layer provided on the surface of the core particle relative to the number of moles of magnesium in the core particle. The molar ratio (Mg + M) / Mg of the total number of moles of metal and divalent metal M is preferably 0.05 to 0.6, more preferably 0.2 to 0.4, and even more preferably 0.2 to 0.3. . When the molar ratio is in the range of 0.05 to 0.6, the effect of suppressing the amount of gas generated when blended with the PPS resin can be exhibited. The number of moles of Mg contained in the core particle and the number of moles of the divalent metal M on the surface are estimated to coincide with the charged amount when producing the hydrotalcite particles.

The type of anion (An ⁿ⁻ ) contained in the Mg—M—Al-based hydrotalcite particles of the embodiment of the present invention is not particularly limited. For example, hydroxide ion, carbonate ion, sulfate ion , Phosphate ions, silicate ions, organic carboxylate ions, organic sulfonate ions, and organic phosphate ions.

Examples of the divalent metal represented by M include one or more selected from Mg, Zn, Ca, Fe, Ni, Cu, Co, Mn, and the like. If necessary, two or more kinds of divalent metals can be contained. As the divalent metal represented by M, Mg and / or Zn are preferable in terms of productivity and economy. The Mg-M-Al hydrotalcite particles according to the embodiment of the present invention are, for example, Mg-Al hydrotalcite as core particles and an Mg-M-Al hydrotalcite layer grown on the core particle surface. Obtained by. In the embodiment of the present invention, heat-treated particles may be used as Mg-M-Al-based hydrotalcite particles.

In the Mg-M-Al hydrotalcite particles of the embodiment of the present invention, the particle surface is made of a higher fatty acid, an anionic surfactant, a higher fatty acid phosphate ester, a coupling agent, and a polyhydric alcohol ester, if necessary. It may be coated with at least one selected surface treatment agent. By covering with the surface coating, the dispersibility of the Mg-M-Al hydrotalcite particles in the PPS resin can be improved, and further the function and stability of the PPS resin composition can be improved.

Examples of higher fatty acids include lauric acid, stearic acid, palmitic acid, oleic acid, linoleic acid and the like. Examples of higher fatty acid phosphates include stearyl ether phosphate, oleyl ether phosphate, lauryl ether phosphate, and the like. Examples of the polyhydric alcohol ester include sorbitan monooleate, sorbitan monolaurate, and stearic acid monoglyceride.

Examples of the anionic surfactant include salts such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium stearate, potassium oleate, and potassium castor oil.

Examples of coupling agents include silane-based, aluminum-based, titanium-based, and zirconium-based coupling agents.

((B) Method for producing Mg-M-Al hydrotalcite particles)
Next, a method for producing Mg-M-Al hydrotalcite particles used in the embodiment of the present invention will be described.

An alkaline aqueous solution containing an anion, a magnesium salt aqueous solution, and an aluminum salt aqueous solution are mixed to obtain a mixed solution having a pH value in the range of 10 to 14. Thereafter, the mixed solution is treated at a temperature range of 40 to 105 ° C., preferably 80 to 105 ° C., to form core particles of Mg—Al hydrotalcite-type particles (primary reaction). Next, the total number of moles is 0.50 or less, preferably 0.35 or less, based on the total number of moles of the magnesium and the aluminum added to the aqueous suspension containing the core particles when the core particles are formed. A magnesium salt aqueous solution containing magnesium, divalent metal M and aluminum, a divalent metal M salt aqueous solution and an aluminum salt aqueous solution are added in such a ratio as follows. Thereafter, Mg-M-Al-based hydrotalcite particles are obtained by treatment (secondary reaction) at a pH value of 8 to 11 and a temperature of 45 to 105 ° C., preferably 65 to 105 ° C. Can do.

Here, the alkaline aqueous solution containing anions is preferably a mixed alkaline aqueous solution of an aqueous solution containing anions and an aqueous alkali hydroxide solution.

As the aqueous solution containing anions, aqueous solutions such as sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, sodium sulfate, organic carboxylate, organic sulfonate, and organic phosphate are preferable.

As the alkali hydroxide aqueous solution, sodium hydroxide, potassium hydroxide, ammonia, urea aqueous solution and the like are preferable.

As the magnesium salt aqueous solution, a magnesium sulfate aqueous solution, a magnesium chloride aqueous solution, a magnesium nitrate aqueous solution and the like can be used, and a magnesium sulfate aqueous solution and a magnesium chloride aqueous solution are preferable. A slurry of magnesium oxide powder or magnesium hydroxide powder may be substituted.

As the aluminum salt aqueous solution, an aluminum sulfate aqueous solution, an aluminum chloride aqueous solution, an aluminum nitrate aqueous solution or the like can be used, and preferably an aluminum sulfate aqueous solution or an aluminum chloride aqueous solution. A slurry of aluminum oxide powder or aluminum hydroxide powder may be substituted.

In the primary reaction, the mixing order of the alkaline aqueous solution containing anions, magnesium and aluminum is not particularly limited, and each aqueous solution or slurry may be mixed simultaneously. Preferably, an aqueous solution or slurry in which magnesium and aluminum are mixed in advance is added to an aqueous alkaline solution containing anions.

In addition, when each aqueous solution is added, the aqueous solution may be added at one time or continuously dropped.

The concentration of the alkaline aqueous solution containing anions in the primary reaction, and the reaction solution in which magnesium and aluminum are mixed is preferably 0.1 to 1.5 mol / l for magnesium, more preferably 0.1 to 1.2 mol / l. Aluminum is preferably 0.03 to 1.0 mol / l, more preferably 0.04 to 0.8 mol / l, and an anion is preferably 0.05 to 1.4 mol / l, more preferably 0.06. The amount is preferably 1.2 to 1.2 mol / l, and the alkali is preferably 0.5 to 8 mol / l, more preferably 0.8 to 6 mol / l. The molar ratio of magnesium to aluminum to be added (Mg / Al) is preferably 0.8 to 5.0, more preferably 0.9 to 4.5.

The temperature during the primary reaction is 40 to 105 ° C, preferably 45 to 105 ° C, more preferably 80 to 105 ° C, and still more preferably 85 to 105 ° C. Even when the temperature is lower than 40 ° C., core particles are produced, but it is difficult to obtain core particles having a large particle size. When the temperature exceeds 105 ° C., a pressure vessel such as an autoclave is required, which is not economical.

The pH value during the primary reaction is 10 to 14, preferably 11 to 14. When the pH value is less than 10, core particles having a large particle size are difficult to obtain.

The reaction time for performing the primary reaction is preferably 2 to 24 hours. When the reaction time is less than 2 hours, it is difficult to obtain core particles having a large particle size. Reaction times exceeding 24 hours are not economical.

At the end of the primary reaction, magnesium and aluminum do not remain in the reaction suspension, and all contribute to the formation of core particles. Therefore, the composition of the core particles is estimated to be the same as the charged composition.

The average plate surface diameter of the core particles obtained by the primary reaction is preferably 0.1 to 0.9 μm. The BET specific surface area of the core particles obtained by the primary reaction is preferably 5 to 150 m ² / g, more preferably 5 to 80 m ² / g. Here, the average plate surface diameter and the BET specific surface area are values measured by the methods described in the paragraphs [0041] and [0043] described above.

In the secondary reaction, the total number of moles of magnesium, divalent metal M and aluminum added is preferably 0.50 or less, more preferably the total number of moles of magnesium and aluminum added in the primary reaction. 0.45 or less, more preferably 0.35 or less. When the total number of moles of the primary reaction exceeds 0.50, the growth reaction does not occur and a large amount of fine particles are deposited outside the core particles, and a uniform core-surface layer structure cannot be obtained. It may be insufficient. The molar ratio of the total number of moles of magnesium and divalent metal M in the outer layer provided on the surface of the core particles to the number of moles of magnesium of the core particles is preferably 0.05 to 0.6, 0.2 Is more preferably 0.4, and still more preferably 0.2 to 0.3. By using the hydrotalcite particles in this range, the effect of suppressing the generated gas when blended with the PPS resin can be expressed.

In the secondary reaction, the order of addition of magnesium, divalent metal M and aluminum is not particularly limited, and each aqueous solution or slurry may be added simultaneously. Preferably, an aqueous solution or slurry in which magnesium, divalent metal M and aluminum are mixed in advance is added.

In addition, when each aqueous solution is added, the aqueous solution may be added at one time or continuously dropped.

The total metal concentration in the mixed solution in which magnesium, divalent metal M and aluminum are mixed in the secondary reaction is preferably 0.1 to 1.5 mol / l, more preferably 0.1 to 1.2 mol / l. is there. When the total metal concentration in the mixed solution is less than 0.1 mol / l, the effect of suppressing the generated gas when blended with the PPS resin may be insufficient. When the total metal concentration in the mixed solution exceeds 1.5 mol / l, a uniform growth reaction does not occur and fine particles exist outside the core particles, and dispersibility in the PPS resin may be deteriorated.

The temperature at the time of performing the secondary reaction is 45 to 105 ° C, more preferably 65 to 105 ° C. Even when the temperature is lower than 45 ° C., Mg—M—Al hydrotalcite particles are produced, but Mg—M—Al hydrotalcite particles having a large average plate surface diameter cannot be obtained. In order to obtain desired particles thereafter, it is effective to perform the aging by extending the reaction time or raising the temperature to 105 ° C. or higher. The aging temperature range is 105 ° C. to 200 ° C., but if it exceeds 105 ° C., a pressure vessel such as an autoclave is required, which is not economical.

The pH value at the time of performing the secondary reaction is 8 to 11, preferably 8 to 10. When the pH value is less than 8, it is difficult to obtain Mg—M—Al hydrotalcite particles having a large average plate surface diameter. If the pH exceeds 11, a part of the added divalent metal M does not precipitate and remains in the aqueous solution, so it is neither economical nor industrial.

The reaction time for performing the secondary reaction is preferably 2 to 24 hours. When the reaction time is less than 2 hours, it is difficult to obtain Mg—M—Al hydrotalcite particles having a large average plate surface diameter. Reaction times exceeding 24 hours are not economical.

At the end of the secondary reaction, magnesium, divalent metal M and aluminum do not remain in the reaction suspension, and all contribute to the production of hydrotalcite-type particle powder. Therefore, the composition of the hydrotalcite layer coated on the surface of the core particle is estimated to be the same as the charged composition in the growth reaction.

After completion of the reaction, if filtered, washed with water and dried by a conventional method, Mg—M—Al hydrotalcite is used as a core particle, and a Mg—M—Al hydrotalcite layer is provided on the particle surface of the core particle. -Al hydrotalcite particles are obtained.

(Heat treatment of Mg-M-Al hydrotalcite particles)
The Mg—M—Al hydrotalcite particles obtained by the above method can be used after heat treatment. The heat treatment is performed on the Mg—M—Al-based hydrotalcite particles in a temperature range of 80 to 500 ° C., preferably 80 to 350 ° C., more preferably 180 to 320 ° C. The heat treatment time may be adjusted depending on the heat treatment temperature. The atmosphere during the heat treatment may be either an oxidizing atmosphere or a non-oxidizing atmosphere, but a gas having a strong reducing action such as hydrogen is not preferable.

(Surface treatment of Mg-M-Al hydrotalcite particles)
The Mg—M—Al hydrotalcite particles obtained by the above method can be used after being coated with a surface treatment agent.

Coating with the surface treatment agent can be performed by either dry surface treatment or wet surface treatment. When performing dry surface treatment, put Mg-M-Al hydrotalcite particles in a Henschel mixer, sand mill, edge runner, Taninaka grinder, rakai mill, etc., add a surface treatment agent, dry blend and grind To do.

When wet surface treatment is performed, an aqueous suspension such as a higher fatty acid salt is added to an aqueous suspension obtained by dispersing Mg-M-Al hydrotalcite particles, and the water temperature is adjusted to 20 to 95 ° C. The particle surfaces of the Mg-M-Al hydrotalcite particles are coated by mixing and stirring, or if necessary, adjusting the pH value after mixing and stirring. Then, it is filtered, washed with water, dried and pulverized. In the case of further heat treatment, an arbitrary surface treatment agent that does not decompose at the heat treatment temperature is selected.

When the surface treatment agent is decomposed at a desired heat treatment temperature, a dry surface treatment using a Henschel mixer or the like may be performed after the heat treatment. When performing the dry surface treatment, the Mg-M-Al hydrotalcite particles and the surface treatment agent may be heated from the outside if necessary while being pulverized and mixed.

As the surface treatment agent, those described above can be used.

(PPS resin composition)
In the embodiment of the present invention, it is important to blend the Mg-M-Al hydrotalcite particles described above, and the blending amount is 0.1 to 30 parts by weight with respect to 100 parts by weight of the (A) polyphenylene sulfide resin. It is. The blending amount is preferably 0.5 parts by weight or more, and more preferably 1.0 part by weight or more. The blending amount is preferably 25 parts by weight or less, more preferably 20 parts by weight or less. If the amount is less than 0.1 parts by weight, the fogging property (the effect of preventing fogging of the glass due to the generated gas) is insufficient. If the amount exceeds 30 parts by weight, the fluidity and mechanical strength are insufficient, It becomes difficult to obtain a resin composition having excellent fogging properties.

In the embodiment of the present invention, it is preferable to further blend 5 to 300 parts by weight of an inorganic filler other than (C) hydrotalcite. As the inorganic filler, either a fibrous filler or a non-fibrous filler can be used.

((C) inorganic filler)
The PPS resin composition of the embodiment of the present invention can further contain an inorganic filler other than hydrotalcite, and can impart necessary mechanical properties, dimensional stability, and the like. As the inorganic filler, a fibrous filler or a non-fibrous filler can be used.

Specific examples of the fibrous filler include glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber. , Asbestos fibers, stone-gypsum fibers, metal fibers, and the like are used, and two or more of these may be used in combination. In addition, it is better to use these fibrous fillers after pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound and an epoxy compound. It is preferable in the meaning which obtains. Of these, glass fiber and carbon fiber are more preferably used.

Specific examples of non-fibrous fillers include silicates such as talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, silicon oxide, magnesium oxide, alumina, Metal compounds such as zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, hydroxylation such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide Products, glass beads, glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black and silica, graphite and the like. These non-fibrous fillers may be hollow, and two or more of these fillers may be used in combination. These non-fibrous fillers may be used after pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound. Of these, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, and silicates such as kaolin, clay and talc are particularly preferable.

The blending amount of the (C) inorganic filler used in the embodiment of the present invention is preferably 5 parts by weight or more, more preferably 50 parts by weight or more with respect to 100 parts by weight of the (A) polyphenylene sulfide resin. preferable. Further, the blending amount of the (C) inorganic filler is preferably 300 parts by weight or less, more preferably 225 parts by weight or less, and 180 parts by weight or less with respect to 100 parts by weight of the (A) polyphenylene sulfide resin. It is particularly preferable that By setting the blending amount of the inorganic filler to 5 parts by weight or more, strength, rigidity, and dimensional stability can be improved, and when it is 300 parts by weight or less, fluidity during molding can be maintained.

(Other additives, etc.)
In the polyphenylene sulfide resin composition of the embodiment of the present invention, a silane compound can be further blended in order to further improve the low burr property and high toughness within the range not impairing the effects of the embodiment of the present invention. is there. Examples of the silane compound include an alkoxysilane compound having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, and a ureido group. Specific examples thereof include epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) amino Ureido group-containing alkoxysilane compounds such as propyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanate Isocyanato group-containing alkoxysilane compounds such as natopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) Amino group-containing alkoxysilane compounds such as aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-hydroxypropyltrimethoxysilane, γ-hydroxypropyltriethoxy Examples include hydroxyl group-containing alkoxysilane compounds such as silane, among which γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxy Chlohexyl) Epoxy group-containing alkoxysilane compounds such as ethyltrimethoxysilane, ureido groups such as γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane Alkoxysilane compounds, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, Isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropylethyldiethoxysilane and γ-isocyanatopropyltrichlorosilane are preferred. Particularly preferred are epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. .

The content of the silane compound is preferably 0.05 parts by weight or more with respect to 100 parts by weight of the (A) polyphenylene sulfide resin, from the viewpoint of obtaining more excellent low burr and high toughness, More preferably, it is more than part. Further, it is preferably 3 parts by weight or less, and more preferably 1.5 parts by weight or less. By blending 0.05 part by weight or more, the effect of improving low burr and high toughness by adding the silane compound can be exhibited. By setting the blending amount to 3 parts by weight or less, the amount of gas generated from the polyphenylene sulfide resin composition is not increased.

The polyphenylene sulfide resin composition of the embodiment of the present invention may further be blended with other resins within a range not impairing the effects of the embodiment of the present invention. The blendable resin is not particularly limited, and specific examples thereof include amorphous resins such as polystyrene, polyphenylene ether, polyarylate, polysulfone, polyethersulfone, and polyetherimide, nylon 6, nylon 66, Polyamide such as nylon 610, nylon 11, nylon 12, nylon 46, aromatic nylon, polyethylene terephthalate, polybutylene terephthalate, polycyclohexyldimethylene terephthalate, polynaphthalene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene, Olefin copolymers, polyolefin elastomers, and polyethers having functional groups such as carboxyl groups, carboxylate ester groups, acid anhydride groups, and epoxy groups Ester elastomers, polyetheramide elastomers, polyamide-imide, and the like polyacetals, and polyimides.

In addition, the polyphenylene sulfide resin composition of the embodiment of the present invention includes a plasticizer such as a thioether compound, an ester compound, and an organic phosphorus compound, an organic phosphorus compound, and the like as long as the effects of the embodiment of the present invention are not impaired. Crystal nucleating agents, polyolefin compounds, silicone compounds, long-chain aliphatic ester compounds, release agents such as long-chain aliphatic amide compounds, antioxidants such as hindered phenolic compounds and hindered amine compounds, thermal stability Conventional additives such as lubricants, lubricants such as calcium stearate, aluminum stearate, lithium stearate, UV inhibitors, colorants, flame retardants and foaming agents can be added.

(Method for producing PPS resin composition)
Although there is no restriction | limiting in particular in the manufacturing method of the polyphenylene sulfide resin composition of embodiment of this invention, Each raw material is supplied to normally well-known melt mixers, such as a single screw or a twin screw extruder, a Banbury mixer, a kneader, and a mixing roll. Examples of the method include kneading at a temperature of 280 to 380 ° C. There are no particular restrictions on the mixing order of the raw materials, a method in which all raw materials are blended and melt kneaded by the above method, a part of the raw materials are melted and kneaded by the above method, and the remaining raw materials are further blended and melt kneaded. Any method may be used, such as a method of mixing a part of raw materials or a method of mixing the remaining raw materials using a side feeder during melt kneading by a single-screw or twin-screw extruder after compounding. As for the small amount additive component, other components may be kneaded and pelletized by the above-described method and then added before molding and used for molding.

The polyphenylene sulfide resin composition of the embodiment of the present invention thus obtained can be used for various moldings such as injection molding, extrusion molding, blow molding, transfer molding, and is particularly suitable for injection molding applications. .

(Characteristics of PPS resin composition)
The PPS resin composition of the embodiment of the present invention generates less gas in the region below the melting point of polyphenylene sulfide near 200 ° C. In addition, when the polyphenylene sulfide resin composition of the embodiment of the present invention is molded, a molded body that can prevent fogging of a lens or the like can be obtained.

Specifically, it is possible to obtain a glass plate having a haze value of 10% or less, which is an index of fogging of a glass plate after performing a fogging test by the following method.

Examples of fogging tests are given below.

After pellets made of PPS resin composition were pre-dried at 130 ° C. for 3 hours in a hot air dryer, 100 g of this was weighed in a 500 ml glass bottle, a slide glass was placed on it, and the dish was capped. Place in a hot air circulating oven and heat at 200 ° C. for 168 hours. The gas generated at this time was adhered onto the slide glass, and the haze value of the slide glass was measured with a direct reading haze meter manufactured by Toyo Seiki Co., Ltd. The smaller the haze value, the less the generated gas and the less fogging of the glass. Therefore, the haze value is preferably 10% or less, and more preferably 7% or less.

(Use of PPS resin composition)
As described above, the polyphenylene sulfide resin composition of the embodiment of the present invention generates less gas in the region below the melting point of polyphenylene sulfide near 200 ° C. and can prevent fogging of the lens, etc. It is suitably used for optical parts such as holders and cases, particularly projector parts.

Other applicable applications of the polyphenylene sulfide resin composition of the embodiment of the present invention include, for example, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, oscillators, various terminals. Board, transformer, plug, printed circuit board, tuner, speaker, microphone, headphones, small motor, magnetic head base, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder, parabolic antenna, computer related parts Audio / video such as electric / electronic parts, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / compact discs / DVD / Blu-ray discs Vessel parts, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, home typified word processor parts, various and office electrical product parts can be exemplified. Further, various examples include machine computer-related parts such as office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, lighters, typewriters, and the like. Moreover, various types such as optical equipment represented by a microscope, binoculars, a camera, a watch, and precision machine related parts can be exemplified. Further, various examples such as water faucet tops, mixing faucets, pump parts, pipe joints, water volume control valves, relief valves, hot water temperature sensors, water volume sensors, water meter parts such as water meter housings can be exemplified. Valve alternator terminals, alternator connectors, IC regulators, light meter potentiometer bases, various valves such as exhaust gas valves, various fuel / exhaust / intake pipes, 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, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air Flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper Starter related parts, distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve, fuse connector, horn terminal, electrical component insulation plate, step motor rotor Examples include various uses such as lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, vehicle speed sensors, and cable liners.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of these examples.

<Melt viscosity measurement>
The melt viscosity of the PPS resin was measured using a Capillograph manufactured by Toyo Seiki Co., Ltd. under the conditions of 300 ° C. and a shear rate of 1000 / s.

<Ash content measurement>
The PPS resin was heated in a furnace at 540 ° C. for 6 hours, and the weight fraction of the residue after heating was measured and calculated.

[Raw materials used]
(A-1) PPS resin-1:
An autoclave equipped with a stirrer was charged with 2.98 kg (25 mol) of a 47% aqueous sodium hydrosulfide solution, 2.17 kg (26 mol) of 48% sodium hydroxide and 5 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP). The temperature was raised to 205 ° C., and 2.8 liters of extracted water containing 2.7 kg of water was removed. To the residual mixture, 3.75 kg (25.5 mol) of 1,4-dichlorobenzene and 2.5 kg of NMP were added and heated at 270 ° C. for 1 hour. This was filtered, poured into 25 liters of a pH 4 acetic acid aqueous solution, stirred for about 1 hour at 192 ° C. in a sealed autoclave, filtered, and ionized at about 90 ° C. until the pH of the filtrate reached 7. After washing with exchanged water, the polymer was dried under reduced pressure at 120 ° C. for 24 hours to obtain PPS resin-1 having an ER85 (g / 10 min) (melt viscosity of 10 Pa · s). The obtained PPS resin-1 had an ash content of 0.21% by weight.

(A-2) PPS resin-2:
In a 70 liter autoclave with a stirrer and bottom plug valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.91 kg (69.80 mol) of 96% sodium hydroxide, N-methyl-2 -Pyrrolidone (NMP) 11.45 kg (115.50 mol), sodium acetate 1.89 kg (23.10 mol), and 10.5 kg of ion-exchanged water were charged to 245 ° C over about 3 hours while passing nitrogen at normal pressure. After gradually heating and distilling out 14.78 kg of water and 0.28 kg of NMP, the reaction vessel was cooled to 200 ° C. The amount of water remaining in the system per mole of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide. Thereafter, the mixture was cooled to 200 ° C., 10.45 kg (71.07 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and the mixture was stirred at 240 rpm. The temperature was raised from 200 ° C. to 270 ° C. at a rate of 6 ° C./min. After reacting at 270 ° C. for 100 minutes, the bottom valve of the autoclave was opened, the contents were flushed into a vessel equipped with a stirrer while being pressurized with nitrogen, and stirred for a while at 250 ° C. to remove most of NMP. . The obtained solid and 76 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 70 ° C. for 30 minutes, and then suction filtered through a glass filter. Next, 76 liters of ion-exchanged water heated to 70 ° C. was poured into a glass filter, and suction filtered to obtain a cake. The obtained cake and 90 liters of ion-exchanged water were charged into an autoclave equipped with a stirrer, and acetic acid was added so that the pH was 7. After replacing the inside of the autoclave with nitrogen, the temperature was raised to 192 ° C. and held for 30 minutes. Thereafter, the autoclave was cooled and the contents were taken out. The contents were subjected to suction filtration with a glass filter, and then 76 liters of ion-exchanged water at 70 ° C. was poured into the contents to perform suction filtration to obtain a cake. The obtained cake was heat-treated at 200 ° C. under an oxygen stream to obtain dry PPS resin-2. The obtained PPS resin-2 had a melt viscosity of 150 Pa · s and an ash content of 0.16% by weight.

(A-3) PPS resin-3:
In a 70 liter autoclave equipped with a stirrer, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 3.0 kg (70.97 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP ) 11.43 kg (115.50 mol), sodium acetate 0.86 kg (10.5 mol), and ion-exchanged water 10.50 kg were charged and gradually heated to 245 ° C. over about 3 hours while passing nitrogen at normal pressure. After distilling 14.78 kg of water and 0.28 kg of NMP, the reaction vessel was cooled to 160 ° C. The amount of water remaining in the system per mole of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide. Next, 10.24 kg (69.63 mol) of p-dichlorobenzene and 9.01 kg (91.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm while stirring at 0.6 ° C. / The temperature was raised to 238 ° C. at a rate of minutes. After reacting at 238 ° C. for 95 minutes, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min. After reacting at 270 ° C. for 100 minutes, 1.26 kg (70 mol) of water was injected over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./minute. Then, after cooling to 200 ° C. at a rate of 1.0 ° C./min, it was rapidly cooled to near room temperature. The contents were taken out, diluted with 26.30 kg of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the resulting particles were washed with 31.90 kg of NMP and filtered off. This was washed several times with 56.00 kg of ion-exchanged water and filtered, then washed with 70.00 kg of 0.05% by weight acetic acid aqueous solution and filtered. After washing with 70.00 kg of ion-exchanged water and filtering, the obtained hydrous PPS particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C. to obtain dry PPS resin-3. The obtained PPS resin-3 had a melt viscosity of 60 Pa · s and an ash content of 0.04% by weight.

(A-4) PPS resin-4: In a 70 liter autoclave equipped with a stirrer and a bottom plug valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.91 kg of 96% sodium hydroxide (69 .80 mol), 11.45 kg (115.50 mol) of N-methyl-2-pyrrolidone (NMP), and 10.5 kg of ion-exchanged water, and gradually increase to 245 ° C. over about 3 hours while passing nitrogen at normal pressure. Then, 14.78 kg of water and 0.28 kg of NMP were distilled off, and then the reaction vessel was cooled to 200 ° C. The amount of water remaining in the system per mole of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide. Thereafter, the mixture was cooled to 200 ° C., 10.48 kg (71.27 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and the mixture was stirred at 240 rpm. The temperature was raised from 200 ° C. to 270 ° C. at a rate of 6 ° C./min. After reacting at 270 ° C. for 100 minutes, the bottom valve of the autoclave was opened, the contents were flushed into a vessel equipped with a stirrer while being pressurized with nitrogen, and stirred for a while at 250 ° C. to remove most of NMP. . The obtained solid and 76 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 70 ° C. for 30 minutes, and then suction filtered through a glass filter. Next, 76 liters of ion-exchanged water heated to 70 ° C. was poured into a glass filter, and suction filtered to obtain a cake. The obtained cake and 90 liters of ion-exchanged water were charged into an autoclave equipped with a stirrer, and the interior of the autoclave was replaced with nitrogen, and then the temperature was raised to 192 ° C. and held for 30 minutes. Thereafter, the autoclave was cooled and the contents were taken out. The contents were subjected to suction filtration with a glass filter, and then 76 liters of ion-exchanged water at 70 ° C. was poured into the contents, followed by suction filtration to obtain a cake. The obtained cake was dried at 120 ° C. under a nitrogen stream to obtain dry PPS resin-4. The obtained PPS resin-4 had a melt viscosity of 130 Pa · s and an ash content of 0.6% by weight.

(B-1) Mg-M-Al-based (M = Mg) hydrotalcite particles:
Hydrotalcite “NAOX-91N” manufactured by Toda Kogyo Co., Ltd. The average plate surface diameter is 0.15 μm (core particles: Mg—Al, outer layer: Mg—Mg—Al, the total number of Mg and divalent metal M in the outer layer relative to the number of moles of Mg in the core particles (Mg ₁ ). Number (Mg ₂ + M), molar ratio (Mg ₂ + M) / Mg ₁ is 0.2 to 0.3).

(B-2) Mg-M-Al-based (M = Zn) hydrotalcite particles:
Hydrotalcite “N-57D” manufactured by Toda Kogyo Co., Ltd. The average plate surface diameter is 0.20 μm (core particles: Mg—Al, outer layer: Mg—Zn—Al, the total number of Mg and divalent metal M in the outer layer relative to the number of moles of Mg in the core particles (Mg ₁ ). Number (Mg ₂ + M), molar ratio (Mg ₂ + M) / Mg ₁ is 0.2 to 0.4.

(B-3) Mg-Al hydrotalcite:
Hydrotalcite “KW-2100” manufactured by Kyowa Chemical Industry Co., Ltd. (Core particles, outer layer have a uniform composition; Mg—Al).

(C-1) Fibrous filler:
Glass fiber. Glass chopped strand “ECS 03 T-747H” manufactured by Nippon Electric Glass Co., Ltd.

(C-2) Non-fibrous filler:
Calcium carbonate. Heavy calcium carbonate “KSS-1000” manufactured by Dowa Calfine.

[Method for adjusting resin or resin composition pellet]
Each of the above materials was dry blended in advance at the ratio shown in Table 1, and a screw type twin screw extruder (TEX-44 manufactured by Nippon Steel Works) was set at a cylinder temperature of 280 ° C. (lower hopper) to 310 ° C. (discharge port side). ) Was melt kneaded and pelletized to obtain pellets. Using these pellets, mechanical properties were measured by the following means. In each test, preliminary drying was performed for 3 hours in a hot air dryer in which the temperature of the pellet was adjusted to 130 ° C. before molding.

[Haze value after fogging test]
Pellets made of polyphenylene sulfide resin or polyphenylene sulfide resin composition were pre-dried at 130 ° C. for 3 hours in a hot air dryer. Thereafter, 100 g of this was weighed in a 500 ml glass bottle, a slide glass was placed thereon, covered with a petri dish, and the glass bottle was placed in a hot air circulation oven and heated at 200 ° C. for 168 hours. The gas generated at this time was adhered onto the slide glass, and the haze value of the slide glass was measured with a direct reading haze meter manufactured by Toyo Seiki Co., Ltd. The smaller the haze value, the less generated gas and the less haze.

[Bending strength]
Measurements were performed according to ISO D178. Specifically, the measurement was performed as follows. The pellets obtained by the above method are supplied to an injection molding machine “SE100DU” manufactured by Sumitomo Heavy Industries, Ltd. set to a cylinder temperature of 320 ° C., mold temperature 140 ° C., injection pressure = lower filling pressure + 10 MPa, injection speed 100 mm / Injection molding was performed in sec to obtain a test piece of length 80 mm × width 10 mm × thickness 4 mm. Using this test piece, measurement was performed under the conditions of a span of 64 mm and a test speed of 2 mm / min in an atmosphere of 23 ° C. and a relative humidity of 50%.

[Flow length]
Using a spiral flow mold having a thickness of 1 mm, molding was performed under conditions of a cylinder temperature of 320 ° C., a mold temperature of 140 ° C., an injection speed of 230 mm / sec, an injection pressure of 98 MPa, an injection time of 5 sec, and a cooling time of 15 sec. Used molding machine: injection molding machine “SE-30D” manufactured by Sumitomo Heavy Industries, Ltd.). It can be said that the larger the value of the flow length, the better the melt fluidity.

[Mold shrinkage]
Using a square plate mold of 80 mm × 80 mm × 3 mm thickness (film gate), cylinder temperature 320 ° C., mold temperature 130 ° C., injection speed 100 mm / sec, injection pressure = filling lower limit pressure + 10 MPa, injection time 10 sec, cooling time 15 sec. Molding was performed under the conditions, and the dimensions of the square plate in the flow direction / perpendicular direction were measured (molding machine used: injection molding machine “SE100DU” manufactured by Sumitomo Heavy Industries, Ltd.). It can be said that the smaller the molding shrinkage value and the smaller the difference between the flow direction and the perpendicular direction, the better the dimensional accuracy.

[Examples 1 to 10]
Table 1 shows examples. Examples 1 to 4 are compositions in which Mg-M-Al hydrotalcite particles are blended with PPS. This indicates that the more Mg—M—Al hydrotalcite particles, the smaller the haze value and the less generated gas.

In Examples 5 to 7, PPS is further mixed with glass fibers in addition to Mg-M-Al hydrotalcite particles. This indicates that the more Mg—M—Al hydrotalcite particles, the smaller the haze value and the less generated gas. Moreover, the molding shrinkage ratio was reduced by the blending of the glass fibers.

Examples 8 to 10 are obtained by blending glass fiber and calcium carbonate in addition to Mg-M-Al hydrotalcite particles in PPS. This indicates that the more Mg—M—Al hydrotalcite particles, the smaller the haze value and the less generated gas. The molding shrinkage was the same as in Examples 5 to 7 containing only glass fibers.

[Comparative Examples 1 to 8]
Table 2 shows a comparative example. Comparative Example 1 is only PPS, indicating a high haze value and a large amount of generated gas. In Comparative Example 2, 45 parts by weight of Mg-M-Al-based hydrotalcite particles were blended with Comparative Example 1, and although the haze value was small, the bending strength and fluidity were lowered. Comparative Examples 3 to 5 are those in which an inorganic filler is blended with Comparative Example 1, and Comparative Examples 6 to 8 are those in which an Mg-Al hydrotalcite different from the hydrotalcite of the present invention is blended. It can be seen that the amount of gas generated is smaller when the Mg-M-Al hydrotalcite particles are blended.

[Examples 11 to 27]
Table 3 shows examples when two types of PPS resins are mixed. The melt viscosity of 40 parts by weight of (A-1) PPS resin-1 and 60 parts by weight of (A-2) PPS resin-2 was 90 Pa · s. Examples 11 to 14 are compositions in which Mg-M-Al hydrotalcite particles (M = Mg) are blended with PPS resin. It shows that the haze value decreases as the compounding amount of Mg-M-Al hydrotalcite particles increases, and the generated gas decreases.

Examples 15 to 17 are obtained by further blending glass fibers with a composition in which Mg-M-Al hydrotalcite particles (M = Mg) are blended with PPS resin. This indicates that the more Mg—M—Al hydrotalcite particles, the smaller the haze value and the less generated gas. Further, the blending of the glass fibers improved the bending strength and reduced the molding shrinkage rate.

Examples 18 to 22, 26, and 27 are compositions in which glass fiber and calcium carbonate are further blended with a composition in which PPS resin is blended with Mg-M-Al hydrotalcite particles (M = Mg). It shows that the haze value decreases as the compounding amount of Mg-M-Al hydrotalcite particles increases, and the generated gas decreases. By blending glass fiber and calcium carbonate, the bending strength was improved, the molding shrinkage ratio was reduced, and the difference between the flow direction and the perpendicular direction was also reduced.

In Example 23, Mg-M-Al hydrotalcite particles (M = Mg) used in Example 18 were replaced with Mg-M-Al hydrotalcite particles (M = Zn). The raw materials and blending amounts are the same as in Example 18. In Example 23, the haze value was larger than that in Example 18, but the amount of generated gas and fogging of the glass are considered to be sufficiently reduced. Therefore, even when hydrotalcite particles of M = Zn are used, the effect of the present invention is considered to be sufficiently exerted.

In Examples 24 and 25, a resin having a viscosity different from the melt viscosity of the PPS resin used in Examples 1 to 23, 26 and 27 was added to Mg-M-Al hydrotalcite particles (M = Mg). Glass fiber and calcium carbonate are blended. It can be seen that the Mg-M-Al hydrotalcite particles of the present invention have the effect of reducing the amount of generated gas even for resins having various melt viscosities.

[Comparative Examples 9 to 20]
Table 4 shows a comparative example when two types of PPS resins are mixed. Comparative Example 9 has only two types of PPS resins, and has a high haze value and a large amount of generated gas. In Comparative Example 10, 45 parts by weight of Mg—M—Al-based hydrotalcite particles were blended with Comparative Example 1, and although the haze value was small, the bending strength and fluidity were lowered. Comparative Examples 11 to 13 are those in which an inorganic filler is added to Comparative Example 9, and Comparative Examples 14 to 18 are those in which Mg-Al hydrotalcite, which is different from the hydrotalcite of the present invention, is added. By comparing Comparative Examples 11 to 18 with Examples, when the Mg-M-Al hydrotalcite particles of the present invention were blended, the amount of generated gas was small without impairing fluidity and mechanical strength. It can be seen that this is an excellent effect.

Comparative Examples 19 and 20 are obtained by replacing the hydrotalcite particles described in Examples 24 and 25 with a hydrotalcite different from that of the present invention. Compared with Comparative Examples 19 and 20, by blending the Mg-M-Al hydrotalcite particles of the present invention, the excellent effect of generating less gas without impairing fluidity and mechanical strength is obtained. I understand that I play.

The present invention relates to a polyphenylene sulfide resin composition having a small amount of gas generated in a region below the melting point of polyphenylene sulfide near 200 ° C. and a molded article thereof without impairing fluidity and mechanical strength. The molded article made of the polyphenylene sulfide resin composition of the present invention is particularly suitable for optical parts having lenses and reflecting surfaces.

Claims (7)

1. (A) For 100 parts by weight of polyphenylene sulfide resin, (B) Mg—Al hydrotalcite is used as the core particle, and Mg—M—Al hydrotalcite layer is formed on the particle surface of the core particle using M as a divalent metal. A polyphenylene sulfide resin composition comprising 0.1 to 30 parts by weight of hydrotalcite particles provided.
2. The polyphenylene sulfide resin composition according to claim 1, wherein the divalent metal M contains Mg and / or Zn.
3. 3. The polyphenylene sulfide resin composition according to claim 1, wherein the average plate surface diameter of the hydrotalcite particles is 0.1 to 1 μm.
4. 4. The polyphenylene sulfide resin composition according to claim 1, wherein 5 to 300 parts by weight of an inorganic filler other than (C) hydrotalcite is blended with 100 parts by weight of (A) polyphenylene sulfide resin.
5. 5. The polyphenylene sulfide resin composition according to claim 1, wherein the glass plate has a haze value of 10% or less after a fogging test is carried out at 200 ° C. for 168 hours on a pellet made of the polyphenylene sulfide resin composition. object.
6. A molded article comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 5.
7. The molded body according to claim 6, wherein the molded body is an optical component.