JP6859024B2 - Method for producing polyphenylene sulfide resin composition - Google Patents

Description

The present invention relates to a polyphenylene sulfide resin composition and a molded product thereof.

Polyphenylene sulfide resin has a good balance of rigidity, heat resistance, heat resistance, water resistance, chemical resistance, and dimensional stability, and is therefore widely used in various applications. In recent years, for the purpose of improving the fuel efficiency of automobiles, it has been studied to replace metal parts in the engine room of automobiles with resin parts to reduce the weight. As described above, the polyphenylene sulfide resin is used as a cooling system component or an engine peripheral component because it has properties suitable for substituting for metal components.

Cooling parts and engine peripheral parts not only have rigidity (for example, tensile strength) and heat resistance to withstand use under high temperature conditions, but also vibration resistance during vehicle running (for example, weld strength, tensile elongation, impact strength). Is required to have. In order to increase the vibration resistance of resin parts, it is necessary to increase the toughness of the resin used. However, polyphenylene sulfide resins generally tend to be inferior in toughness to other engineering plastics. Therefore, it has been studied to increase the toughness of the polyphenylene sulfide resin.

On the other hand, a resin composition in which various elastomers are blended with a polyphenylene sulfide resin has been proposed. For example, a resin composition containing a polyphenylene sulfide resin and an ethylene / α-olefin elastomer has been proposed (see, for example, Patent Document 1). By blending an ethylene / α-olefin elastomer with the polyphenylene sulfide resin, the toughness can be increased, but on the other hand, there is a problem that the molding processability is lowered. On the other hand, a resin composition containing a polyphenylene sulfide resin, an ethylene / α-olefin elastomer, and a carboxylic acid amide wax has been proposed (for example, Patent Document 2).

In addition to resinification of cooling parts and intake parts around the engine, resinification of hollow parts such as metal pipes and pipes is also being studied. Moreover, not only the use of resin for metal parts, but also the compactification of engine rooms and the resulting miniaturization of parts are rapidly progressing. Along with this, the resins used for these parts are required to have higher toughness than ever before.

Japanese Unexamined Patent Publication No. 2000-198923 Japanese Patent No. 5218706

However, since the resin compositions of Patent Documents 1 and 2 do not have sufficient toughness in a high temperature environment, the molded product does not have sufficient vibration resistance (for example, weld strength, tensile elongation, impact strength). There wasn't.

Further, in order to obtain a hollow part, it is required to have excellent extrusion moldability and blow moldability. Specifically, since the hollow part is required to have little fluctuation in wall thickness, it is required to have an appropriately high viscosity at the time of melting. However, since the resin compositions of Patent Documents 1 and 2 have low viscosities at the time of melting, wall thickness fluctuation (drawdown) is likely to occur, and extrusion moldability and blow moldability are low.

Further, in the resin compositions of Patent Documents 1 and 2, there is a concern that gas due to thermal decomposition of the ethylene / α-olefin elastomer is generated, resulting in deterioration of moldability and deterioration of the appearance of the molded product.

The present invention has been made in view of the above circumstances, and is a polyphenylene sulfide resin composition that imparts a molded product having high strength and heat resistance to withstand use under high temperature conditions and high vibration resistance. The purpose is to provide.

[1] Polyphenylene sulfide resin (A) 10 to 94% by mass,
6 to 20% by mass of the functional group-containing olefin polymer (B) containing at least one functional group selected from the group consisting of an epoxy group and a carbodiimide group.
A polyphenylene sulfide resin composition containing 0 to 70% by mass of the fibrous filler (C) (provided that the total of the components (A), (B) and (C) is 100% by mass).
[2] The polyphenylene sulfide resin composition according to [1], wherein the functional group is a carbodiimide group.
[3] The method according to [1] or [2], wherein the fibrous filler (C) is contained in an amount of 20 to 60% by mass based on the total of the components (A), (B) and (C). Polyphenylene sulfide resin composition.
[4] The content of the functional group of the functional group-containing olefin polymer (B) is 0.1 to 6.0% by mass with respect to the total mass of the functional group-containing olefin polymer (B). 1] The polyphenylene sulfide resin composition according to any one of [3].
[5] The content of the functional group-containing olefin polymer (B) is any of [1] to [4], which is 11 to 40% by mass with respect to the total mass of the polyphenylene sulfide resin (A). The polyphenylene sulfide resin composition according to the above.
[6] A molded product obtained by molding the polyphenylene sulfide resin composition according to any one of [1] to [5].
[7] A molded product having a hollow portion obtained by molding the polyphenylene sulfide resin composition according to any one of [1] to [5].

According to the present invention, it is possible to provide a polyphenylene sulfide resin composition which has high strength and heat resistance to withstand use under high temperature conditions and imparts a molded product having high vibration resistance.

1. 1. Polyphenylene sulfide resin composition The polyphenylene sulfide resin composition of the present invention contains at least a polyphenylene sulfide resin (A) and a functional group-containing olefin polymer (B).

1-1. Polyphenylene sulfide resin (A)
The polyphenylene sulfide resin (A) is a polymer containing a structural unit represented by the following formula (1).

The structural unit represented by the formula (1) is derived from a polycondensate of p-dichlorobenzene and a sulfide agent (for example, alkali metal sulfide or alkali metal hydrosulfide).

From the viewpoint of strength and heat resistance, the content ratio of the structural unit represented by the formula (1) is preferably 70 mol% or more, preferably 90 mol% or more, based on the total of the structural units constituting the polymer. Is more preferable.

The polyphenylene sulfide resin (A) may further contain structural units other than the structural units represented by the formula (1), if necessary.

Other structural units are derived from polycondensates of other polyhalogenated aromatic compounds other than p-dichlorobenzene and sulfidating agents. Examples of other polyhalogenated aromatic compounds include m-dichlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5-tetra. Includes chlorobenzene, hexachlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1-methoxy-2,5-dichlorobenzene and the like. Examples of other structural units include those of the following equations. Polymers containing these other structural units may not have too high a melting point and may have high moldability.

The content ratio of the other structural units is preferably 30 mol% or less, more preferably 10 mol% or less, based on the total of the structural units constituting the polymer, from the viewpoint of not impairing the heat resistance. ..

The polyphenylene sulfide resin (A) is produced by any method. For example, the polyphenylene sulfide resin (A) can be produced by reacting a polyhalogenated aromatic compound with a sulfidizing agent in an organic polar solvent. The specific manufacturing method is the same as, for example, Japanese Patent No. 5218706.

The amount of chloroform extracted from the polyphenylene sulfide resin (A) is preferably 1.8% by mass or less, more preferably 1.0% by mass or less.

The polyphenylene sulfide resin (A) having a chloroform extraction amount of 1.8% by mass or less tends to have a high weld strength. In order to reduce the amount of chloroform extracted to 1.8% by mass or less, for example, in the step of polymerizing a polyhalogenated aromatic compound and a sulfidizing agent and then post-treating the obtained solid, the solid is solidified with an organic solvent. It is preferable to wash things.

The amount of chloroform extracted is determined by extracting 10 g of a polyphenylene sulfide resin sample with 200 ml of chloroform for 5 hours using a Soxhlet extractor and drying the extract at 50 ° C. The ratio (percentage) of the weight of the residue obtained after drying to the weight of the sample before extraction is defined as the amount of chloroform extracted.

The melt viscosity of the polyphenylene sulfide resin (A) may be 5 to 2000 Pa · s from the viewpoint of reducing wall thickness fluctuation without impairing the fluidity of the molten resin during extrusion molding or blow molding. It is preferably 20 to 1300 Pa · s, and more preferably 20 to 1300 Pa · s. The melt viscosity can be measured using a capillograph manufactured by Toyo Seiki Co., Ltd. under the conditions of 320 ° C. and a shear rate of 1000 / s.

The melt flow rate (MFR) of the polyphenylene sulfide resin (A) according to ISO 1133 at 190 ° C. and a load of 5 kg has less fluctuation in wall thickness without impairing the fluidity of the molten resin during extrusion molding or blow molding. From the viewpoint of the above, it is preferably 10 to 1000 g / 10 minutes, and more preferably 50 to 800 g / 10 minutes.

The content of the polyphenylene sulfide resin (A) is preferably 10 to 94% by mass, preferably 30 to 72% by mass, based on the total mass of the components (A), (B) and (C). Is more preferable, and 40 to 66% by mass is further preferable. When the content of the polyphenylene sulfide resin (A) with respect to the total mass of the components (A), (B) and (C) is 10% by mass or more, the molded product of the resin composition is provided with high strength and heat resistance. It is easy to apply, and when it is 94% by mass or less, the vibration resistance of the molded product is not easily impaired.

1-2. Functional group-containing olefin polymer (B)
The functional group-containing olefin polymer (B) is an olefin polymer containing one or more functional groups selected from the group consisting of an epoxy group and a carbodiimide group. A carbodiimide group is a group containing one or more carbodiimide units (-N = C = N-R-, R: divalent organic group).

In the polyphenylene sulfide resin composition containing the functional group-containing olefin polymer (B), the functional group of the functional group-containing olefin polymer (B) reacts with or interacts with the molecular end of the polyphenylene sulfide resin (A). .. As a result, the functional group-containing olefin polymer (B) is more likely to be uniformly dispersed in the polyphenylene sulfide resin composition than a simple mixture of the polyphenylene sulfide resin (A) and the carbodiimide compound. Molded articles of such polyphenylene sulfide resin compositions have high impact resistance in addition to high rigidity and heat resistance.

The functional group-containing olefin polymer (B) is a polymer obtained by graft-modifying a modified olefin polymer (b1) with a carbodiimide group-containing compound (b2) or an epoxy group-containing compound (b3).

The modified olefin polymer (b1) can be obtained by graft-modifying the olefin polymer with a compound having a reactive functional group.

The olefin polymer is preferably an ethylene (co) polymer, a propylene (co) polymer, or a butene (co) polymer, and more preferably an ethylene (co) polymer.

The ethylene (co) polymer is an ethylene homopolymer or an ethylene / α-olefin copolymer. The ethylene / α-olefin copolymer is a copolymer of ethylene and an α-olefin having 3 to 12 carbon atoms, and is preferably a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms. Examples of α-olefins include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and the like. Examples of ethylene / α-olefin copolymers include ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene / 1-hexene copolymers, ethylene / 1-octene copolymers and ethylene / 4 -Methyl-1-pentene copolymer and the like are included. Among these, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer and ethylene / 1-octene copolymer are preferable.

The content ratio of the structural unit derived from ethylene in the ethylene / α-olefin copolymer is preferably 70 to 99.5 mol%, more preferably 80 to 99 mol%. On the other hand, the content ratio of the structural unit derived from α-olefin is preferably 0.5 to 30 mol%, more preferably 1 to 20 mol%.

The melt flow rate (MFR) of the olefin polymer by ASTM D1238 at 190 ° C. and a load of 2.16 kg is 0.01 to 20 g / 10 minutes from the viewpoint of increasing the fluidity of the polyphenylene sulfide resin composition during molding. It is preferably 0.05 to 20 g / 10 minutes, and more preferably 0.05 to 20 g / 10 minutes.

The compound having a reactive functional group is preferably an unsaturated carboxylic acid or a derivative thereof. Examples of unsaturated carboxylic acids or derivatives thereof include acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid and endocis-bicyclo [2]. , 2,1] Unsaturated carboxylic acids or unsaturated dicarboxylic acids such as hept-5-ene-2,3-dicarboxylic acid (nadic acid®), and their acid halides, amides, imides, acid anhydrides. And derivatives such as esters are included. Among these, unsaturated dicarboxylic acids and their acid anhydrides are preferable, maleic acid, nadic acid (registered trademark) and their acid anhydrides are more preferable, and maleic anhydride is particularly preferable.

While maleic anhydride has high reactivity with the olefin polymer, the reaction between maleic anhydride is unlikely to occur. Therefore, maleic anhydride can stably react with the olefin polymer.

The graft modification of the olefin polymer with a compound having a reactive functional group may be carried out in the presence of a radical initiator (for example, a peroxide such as an organic peroxide) from the viewpoint of reaction efficiency and the like.

The carbodiimide group-containing compound (b2) is a polycarbodiimide compound having two or more structural units represented by the following formula (2).

R in the formula (2) represents a divalent organic group. Examples of divalent organic groups include alkylene groups, cycloalkylene groups, and arylene groups. The number of structural units represented by the formula (2) can be 2-32.

Examples of carbodiimide group-containing compounds (b2) include poly (4,4'-diphenylmethanecarbodiimide), poly (4,4'-dicyclohexylmethanecarbodiimide), poly (1,3,5-triisopropylbenzene) polycarbodiimide, Poly (1,3,5-triisopropylbenzene, 1,5-diisopropylbenzene) polycarbodiimide and the like are included.

The number average molecular weight (Mn) of the carbodiimide group-containing compound (b2) is usually preferably 400 to 500,000, more preferably 1000 to 10000, and even more preferably 2000 to 4000. When the number average molecular weight (Mn) is in this range, the impact resistance of the molded product of the polyphenylene sulfide resin composition tends to increase. The number average molecular weight (Mn) is measured by gel permeation chromatography (GPC) in terms of polystyrene.

The carbodiimide group-containing compound (b2) may be a commercially available product. Examples of commercially available products include Carbodilite HMV-8CA and LA1 manufactured by Nisshinbo Holdings.

The epoxy group-containing compound (b3) is preferably glycidyl (meth) acrylate. Examples of glycidyl (meth) acrylate include (meth) acrylic acid glycidyl ester and the like.

The graft modification of the modified olefin polymer (b1) with the carbodiimide group-containing compound (b2) or the epoxy group-containing compound (b3) can be carried out by a known method. For example, the modified olefin polymer (b1) and the carbodiimide group-containing compound (b2) or the epoxy group-containing compound (b3) can be melt-kneaded to obtain a functional group-containing olefin polymer (B). The reaction temperature can be, for example, equal to or higher than the melting point of the modified olefin polymer (b11), specifically 100 to 350 ° C. The reaction time can usually be 0.5-10 minutes.

The olefin polymer containing an epoxy group can also be obtained by radical copolymerizing an olefin monomer and an epoxy group-containing compound (b3) in addition to the above-mentioned method. In that case, other copolymerization components may be copolymerized as needed. Examples of other copolymerization components include α, β-unsaturated glycidyl ethers such as allyl glycidyl ether and 2-methylallyl glycidyl ether; styrene, α-methylstyrene, 4-methylstyrene, 4-methoxystyrene, chlorostyrene. , 2,4-Dimethylstyrene and other aromatic vinyl compounds; and unsaturated vinyl esters such as vinyl acetate and vinyl propionate are included.

The functional group of the functional group-containing olefin polymer (B) is preferably a carbodiimide group. Since the functional group-containing olefin polymer (B) has high reactivity with the molecular terminal group of the polyphenylene sulfide resin (A) having a carbodiimide group, it is easily compatible with the polyphenylene sulfide resin (A) and can be contained in the resin composition. Easy to disperse evenly. As a result, high impact resistance can be easily obtained without impairing the strength.

The content of the functional group in the functional group-containing olefin polymer (B) is preferably 0.1 to 6.0% by mass with respect to the total mass of the functional group-containing olefin polymer (B). When the content of the functional group is 0.1% by mass or more, it is easy to increase the vibration resistance of the molded product of the polyphenylene sulfide resin composition. When the content of the functional group is 6.0% by mass or less, the reaction or interaction between the functional group-containing olefin polymer (B) and the polyphenylene sulfide resin (A) becomes excessive, resulting in excessive melt fluidity. It is easy to suppress the increase. When the functional group is a carbodiimide group, not only the carbodiimide unit at the terminal portion of the carbodiimide group but also the carbodiimide unit at the main chain portion can contribute to the reaction or interaction with the polyphenylene sulfide resin (A). The content of the functional group in the functional group-containing olefin polymer (B) is preferably 0.5 to 5.0% by mass, preferably 1.5 to 5.0% by mass, based on the total mass of the functional group-containing olefin polymer (B). More preferably, it is ~ 5.0% by mass. The number of functional groups contained in the unit mass of the functional group-containing olefin polymer (B) is preferably 1.5 to 20 mmol / 100 g per 100 g of the functional group-containing olefin polymer (B). More preferably, it is ~ 20 mmol / 100 g.

The functional group content of the functional group-containing olefin polymer (B) can be measured by ^{13 C-NMR.}

^{13 For} C-NMR measurement, an ECP500 type nuclear magnetic resonance device manufactured by JEOL Ltd. is used as a measuring device, and the solvent is an orthodichlorobenzene / heavy benzene (80/20% by volume) mixed solvent. In addition, the measurement temperature is 120 ° C, the observation nucleus is ¹³ C (125 MHz), single pulse proton decoupling, 45 ° pulse, repetition time is 5.5 seconds, the number of integrations is 10,000 times or more, and 27.50 ppm is a chemical shift. Use as a reference value. The assignment of various signals can be performed based on a conventional method, and can be quantified based on the integrated value of signal intensity.

Peak attributable to carbodiimide ^groups, the 13 C-NMR 130~142ppm, peak attributable to the epoxy group ^are observed at 43~69ppm the 13 C-NMR. From these peaks, the content of carbodiimide groups and epoxy groups can be specified.

The ultimate viscosity [η] of the functional group-containing olefin polymer (B) measured in a 135 ° C. decalin solution is preferably 0.2 to 3.0 dl / g. When the ultimate viscosity of the functional group-containing olefin polymer (B) is 0.2 dl / g or more, good impact resistance is easily obtained, and when it is 3.0 dl / g or less, excellent fluidity is easily obtained. .. The ultimate viscosity [η] of the functional group-containing olefin polymer (B) measured in a 135 ° C. decalin solution is more preferably 0.2 to 2.0 dl / g.

The ultimate viscosity [η] of the functional group-containing olefin polymer (B) measured in a 135 ° C. decalin solution is measured as follows based on a conventional method. 20 mg of the sample is dissolved in 15 ml of decalin, and the specific viscosity (ηsp) is measured in an atmosphere of 135 ° C. using an Ubbelohde viscometer. Further, 5 ml of decalin is added to this decalin solution to dilute it, and then the same specific viscosity measurement is performed. Based on the measurement result of repeating this dilution operation and the viscosity measurement twice more, the "ηsp / C" value when the concentration (C) is extrapolated to zero is defined as the ultimate viscosity [η].

The melt flow rate of the functional group-containing olefin polymer (B) measured at 190 ° C. and a load of 2160 g according to ASTM-D1238 is preferably 0.3 to 50 g / min. When the melt flow rate of the functional group-containing olefin polymer (B) is 0.3 g / min or more, the fluidity of the polyphenylene sulfide resin composition at the time of melting can be appropriately increased, so that the moldability is not easily impaired. When the melt flow rate of the functional group-containing olefin polymer (B) is 50 g / min or less, not only the strength of the molded product of the polyphenylene sulfide resin composition is not significantly impaired, but also the fluidity during molding is moderately low. Therefore, for example, it is easy to suppress drawdown when performing extrusion molding or blow molding.

The content of the functional group-containing olefin polymer (B) is preferably 6 to 20% by mass with respect to the total mass of the component (A), the component (B) and the component (C). When the content of the functional group-containing olefin polymer (B) with respect to the total mass of the components (A), (B) and (C) is 6% by mass or more, the toughness (particularly impact strength) of the polyphenylene sulfide resin composition ) Is easy to increase, so it is easy to obtain a molded product with high vibration resistance. When the content of the functional group-containing olefin polymer (B) with respect to the total mass of the components (A), (B) and (C) is 20% by mass or less, it is excessive during molding of the polyphenylene sulfide resin composition. Not only is it less likely to cause an increase in viscosity, but it is also possible to suppress insufficient dispersion, so that a decrease in strength can be highly suppressed, and heat resistance is not easily impaired. The content of the functional group-containing olefin polymer (B) is more preferably 8 to 18% by mass, more preferably 9 to 16% by mass, based on the total mass of the component (A), the component (B) and the component (C). It is more preferably%.

The content of the functional group-containing olefin polymer (B) is preferably 11 to 40% by mass, more preferably 15 to 35% by mass, based on the total mass of the component (A). When the content of the functional group-containing olefin polymer (B) with respect to the total mass of the component (A) is 11% by mass or more, the toughness of the polyphenylene sulfide resin composition can be easily increased, and when it is 40% by mass or less, the polyphenylene sulfide The strength and heat resistance of the resin composition are not easily impaired.

1-3. Fibrous filler (C)
The polyphenylene sulfide resin composition of the present invention preferably further contains a fibrous filler (C) from the viewpoint of facilitating the increase in strength (rigidity) of the molded product.

The fibrous filler (C) can impart high strength (rigidity) to the molded product. Examples of the fibrous filler (C) include fibrous inorganics such as glass fiber, wallastnite, potassium titanate whiskers, calcium carbonate whiskers, aluminum borate whiskers, magnesium sulfate whiskers, sepiolite, zonotrite, and zinc oxide whiskers. Includes filler. Among these, glass fiber, wallastnite and carbon fiber are preferable because the strength (rigidity) and heat resistance of the molded product can be easily increased. The fibrous filler (C) may contain only one type, or may contain two or more types.

The average fiber length of the fibrous filler (C) is preferably 1 μm to 20 mm, more preferably 5 μm to 10 mm, from the viewpoint of obtaining a molded product having sufficient strength without impairing moldability. It is more preferably 10 μm to 7 mm. The aspect ratio of the fibrous filler (C) is preferably 5 to 2000, more preferably 30 to 1000.

The average fiber length and average fiber diameter of the fibrous filler (C) can be measured by the following methods.
1) The polyphenylene sulfide resin composition or a molded product thereof is dissolved in a hexafluoroisopropanol / chloroform solution (0.1 / 0.9% by volume), and then the filtered product obtained by filtration is collected.
2) The filter obtained in 1) above is dispersed in water, and the fiber length (Li) and fiber diameter (Di) of each of 300 arbitrary fibers are measured with an optical microscope (magnification: 50 times). Let qi be the number of fibers having a fiber length of Li, calculate the weight average length (Lw) based on the following equation, and use this as the average fiber length of the fibrous filler (C).
Weight average length (Lw) = (Σqi × Li ² ) / (Σqi × Li)
Similarly, let ri be the number of fibers having a fiber diameter of Di, calculate the weight average diameter (Dw) based on the following equation, and use this as the average fiber diameter of the fibrous filler (C).
Weight average diameter (Dw) = (Σri × Di ² ) / (Σri × Di)

The average fiber length and average fiber diameter of the fibrous fibrous filler (C) in the polyphenylene sulfide resin composition and its molded product are usually the average fiber length of the fibrous fibrous filler (C) before melt-kneading. Is almost the same as the average fiber diameter.

The content of the fibrous filler (C) is, for example, 0 to 70% by mass and 20 to 60% by mass with respect to the total mass of the component (A), the component (B) and the component (C). preferable. When the content of the fibrous filler (C) with respect to the total mass of the components (A), (B) and (C) is 20% by mass or more, the polyphenylene sulfide resin composition has high strength ( Rigidity) is easily imparted, and when it is 70% by mass or less, an excessive increase in viscosity during molding of the polyphenylene sulfide resin composition and impact resistance and weld strength of the molded product are unlikely to be impaired. The content of the fibrous filler (C) is more preferably 25 to 50% by mass with respect to the total mass of the component (A), the component (B) and the component (C).

The content of the fibrous filler (C) is preferably 70 to 95% by mass, more preferably 75 to 93% by mass, based on the total mass of the component (A). When the content of the component (A) of the fibrous filler (C) is 70% by mass or more, the toughness of the polyphenylene sulfide resin composition can be easily increased, and when it is 95% by mass or less, the polyphenylene sulfide resin composition The strength and heat resistance of objects are not easily impaired.

1-4-1. Heat-resistant stabilizer (D)
The heat-resistant stabilizer (D) preferably contains at least one of a copper-based stabilizer (D1) and an organic heat stabilizer (D2).

Copper-based stabilizers (D1) are composed of (i) salts of halogens and Group 1 or Group 2 metal elements of the Periodic Table of the Elements (halogen metal salts), (ii) copper compounds, and (iii) higher fatty acid metal salts. Contains the mixture.

(I) Examples of halide metal salts include potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride. Of these, potassium iodide and potassium bromide are preferable. Only one type of halogen metal salt may be contained, or two or more types may be contained.

(Ii) Examples of copper compounds include copper halides; copper sulfates, acetates, propionates, benzoates, adipates, terephthalates, sulfates, nicotinates, stearate. Includes copper chelate compounds (compounds of copper with ethylenediamine, ethylenediamine tetraacetic acid, etc.). Of these, copper iodide, cuprous bromide, cupric bromide, cupric chloride, and copper acetate are preferred. Only one type of copper compound may be contained, or two or more types may be contained.

The mass ratio of (i) halogen metal salt and (ii) copper compound is the molar ratio of halogen and copper from the viewpoint of facilitating improvement of heat resistance and corrosiveness during production of the molded product of the polyphenylene sulfide resin composition. The ratio can be adjusted to be 0.1 / 1 to 200/1, preferably 0.5 / 1 to 100/1, more preferably 2/1 to 40/1.

(Iii) Examples of higher fatty acid metal salts include higher saturated fatty acid metal salts and higher unsaturated fatty acid metal salts.

（式（３）中、金属元素（Ｍ１）は、元素周期律表の１、２、３族元素、亜鉛又はアルミニウムであり、ｎは、８〜３０でありうる） The higher saturated fatty acid metal salt is preferably a metal salt of a saturated fatty acid having 6 to 22 carbon atoms and a metal element (M1) such as group 1, 2 and 3 elements of the Periodic Table of the Elements, zinc, and aluminum. .. Such a higher saturated fatty acid metal salt is represented by the following formula (3).

(In the formula (3), the metal element (M1) is a Group 1, 2 or 3 element, zinc or aluminum in the Periodic Table of the Elements, and n can be 8 to 30).

Examples of higher saturated fatty acid metal salts include capric acid, uradecic acid, lauric acid, tridecylic acid, myristic acid, pentadecic acid, palmitic acid, heptadecic acid, stearic acid, nonadecanic acid, araquinic acid, bechenic acid, lignoseric acid, cellotin. Acids, heptacosanoic acid, montanic acid, melicic acid, laxelic acid, undecylene acid, oleic acid, ellagic acid, setreic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, stearolic acid, 2- Includes hexadecenoic acid, 7-hexadecenoic acid, 9-hexadecenoic acid, gadrainic acid, gadoelaidic acid, lithium salt of 11-eicosenoic acid, sodium salt, magnesium salt, calcium salt, zinc salt and aluminum salt. Of these, stearic acid, behenic acid, lithium salt of montanic acid, sodium salt, magnesium salt, calcium salt, zinc salt and aluminum salt are preferable.

The organic heat stabilizer (D2) is preferably at least one selected from hindered phenol compounds, hindered amine compounds, phosphites, organic phosphorus compounds, and bisphenol type epoxy resins.

Examples of hindered phenolic compounds include N, N'-hexamethylenebis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, bis (3,3-bis (4'-). Hydroxy-3'-tert-butylphenyl) butanoic acid) glycol ester 2,1'-thioethylbis-(3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4'-butylidenebis (3-Methyl-6-tert-butylphenol), triethylene glycol-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate and the like are included.

Examples of hindered amine compounds include phenylenediamine acetone adduct (Naugard A), phenylenediamine linolene adduct, Naugard 445, N, N'-dinaphthyl-p-phenylenediamine, N-phenyl-N'-cyclohexyl-p. -Phenylenediamine and Nylostab S-EED [N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,3-benzenedicarboxamide] manufactured by Clariant Co., Ltd. are included.

Examples of phosphite and organophosphorus compounds include triphenylphosphite, diphenylalkylphosphite, phenyldialkylphosphite, tris (nonylphenyl) phosphite, trilaurylphosphite, trioctadecylphosphite, distearylpentaerythritoldi. Phosphite, Tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6) -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris (tert-butylphenyl)) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite , 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz- [d, g] -1,3,2-dioxaphosphocin, 6-fluoro-2,4 8,10-Tetra-tert-butyl-12-methyldibenz [d, g] -1,3,2-dioxaphosphocin, bis (2,4-di-tert-butyl-6-methylphenyl) methylphosphite And bis (2,4-di-tert-butyl-6-methylphenyl) ethylphosphite and the like, preferably tris [2-tert-butyl-4-thio- (2'-methyl-4'-hydroxy). -5'-tert-butyl) phenyl-5-methyl] phenyl phosphite and tris (2,4-di-tert-butylphenyl) phosphite (Basel, Clariant's commercial product, Hostanox® PAR 24) is there.

Examples of the bisphenol type epoxy resin include EPIKOTE manufactured by Yuka Shell Epoxy Co., Ltd.

As described above, the organic heat stabilizer (D2) may be a mixture of two or more selected from a hindered phenol compound, a hindered amine compound, phosphites, an organic phosphorus compound, and a bisphenol type epoxy resin. Examples of such mixtures include BASF's Irgatec NC66 and the like.

The content of the heat-resistant stabilizer (D) is preferably 0.05 to 3.0% by mass with respect to the total mass of the component (A), the component (B) and the component (C). When the content of the heat-resistant stabilizer (D) with respect to the total mass of the components (A), (B) and (C) is 0.05% by mass or more, it is easy to impart high heat resistance to the molded product. When it is 3.0% by mass or less, the strength (rigidity) of the molded product is not easily impaired. The content of the heat-resistant stabilizer (D) is more preferably 0.1 to 1.0% by mass with respect to the total mass of the component (A), the component (B) and the component (C).

The content mass ratio of the copper-based stabilizer (D1) and the organic heat stabilizer (D2) is, for example, 10/90 to 100/0, preferably 50/50 to 90/10. When the ratio of copper-based stabilizer (D1) is high, good heat aging resistance is likely to be exhibited in the temperature range over 150 ° C; when the ratio of organic heat stabilizer (D2) is high, in the temperature range of 100 to 150 ° C. It tends to show good heat aging resistance.

1-5. Other Ingredients The polyphenylene sulfide resin composition of the present invention may further contain other ingredients as long as the effects of the present invention are not impaired. Examples of other components include antioxidants (phenols, amines, sulfurs, phosphorus, etc.), non-fibrous inorganic fillers (clay, silica, alumina, talc, kaolin, quartz, mica, graphite, etc.). ), Light stabilizers (benzotriazoles, triazines, benzophenones, benzoates, hindered amines and ogizanilides, etc.), other polymers (polyformates, ethylene / propylene copolymers, ethylene / 1-butene copolymers) Olefin copolymers such as, olefin copolymers such as propylene / 1-butene copolymers, polystyrene, polyamide, polycarbonate, polyacetal, polysulphon, polyphenylene oxide, fluororesin, silicone resin, LCP, etc.), flame retardant (bromine) System, chlorine type, phosphorus type, antimony type, inorganic type, etc.), mold release agent, fluidity improver, hydrolysis inhibitor, fluorescent whitening agent, plasticizer, thickener, antistatic agent, pigment, crystal nuclei Includes agents and the like. Among them, non-fibrous inorganic fillers, fluidity improvers, hydrolysis inhibitors and the like are preferable.

The fluidity improver may be added for the purpose of increasing the fluidity of the resin composition during molding. In particular, the polyphenylene sulfide resin composition may contain a relatively large amount of the fibrous filler (C) in order to increase the rigidity and heat resistance of the molded product. Even in such a case, an excessive increase in viscosity of the polyphenylene sulfide resin composition during molding can be suppressed, and a decrease in moldability and releasability can be suppressed. Examples of such fluidity improvers include aliphatic metal salts.

The fatty acid metal salt may be a known compound. Examples of fatty acids constituting the fatty acid metal salt include montanic acid, behenic acid, stearic acid and the like. Examples of metal salts constituting the fatty acid metal salt include lithium salt, calcium salt, barium salt, zinc salt, aluminum salt and the like. Preferred examples of the fatty acid metal salt include, and more preferably, montanic acid, a lithium salt, a calcium salt, a barium salt, a zinc salt, and an aluminum salt of montanic acid or behenic acid from the viewpoint of increasing fluidity during molding. Contains calcium.

2. Method for producing polyphenylene sulfide resin composition The polyphenylene sulfide resin composition of the present invention is heat-stable with at least a polyphenylene sulfide resin (A), a functional group-containing olefin polymer (B), and preferably an inorganic filler (C). The agent (D) is mixed by a known method, for example, a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, or the like, or after mixing, the agent (D) is further melt-kneaded by a uniaxial extruder, a multiaxial extruder, a kneader, a Banbury mixer, or the like. After that, it can be produced by a method of granulating or crushing.

3. 3. Applications The polyphenylene sulfide resin composition of the present invention has high toughness in addition to high strength and heat resistance, so that the molded product has high rigidity, high heat resistance, and high vibration resistance. Therefore, the polyphenylene sulfide resin composition of the present invention can be widely used in applications requiring these properties.

Examples of such applications include automobile and vehicle related parts. Examples of automobile / vehicle-related parts include fuel-related / exhaust / intake system pipes, engine support members (for example, engine mounts, engine mount brackets, oil pan uppers, engine torque rods, etc.), cooling system parts, and lighting equipment. Parts (eg, aiming nuts) and the like are included.

Among these, the polyphenylene sulfide resin composition of the present invention is preferably used for molded products having a hollow portion (for example, fuel-related, exhaust system, various intake system pipes, etc.).

A molded product having a hollow portion is manufactured by blow molding or extrusion molding of a resin composition. In blow molding or extrusion molding, if the viscosity of the resin composition at the time of melting is too low, drawdown is likely to occur. On the other hand, the polyphenylene sulfide resin composition of the present invention has an appropriately high viscosity when melted, so that drawdown during extrusion molding or blow molding can be suppressed.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to these Examples.

1. 1. Material (1) Polyphenylene sulfide resin (A)
<Synthesis of polyphenylene sulfide resin (A-1)>
8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.94 kg (70.63 mol) of 96% sodium hydroxide, N-methyl-2 in a 70 liter autoclave with a stirrer and bottom plug valve. -Pyrrolidone (NMP) 11.45 kg (115.50 mol), sodium acetate 0.513 kg (6.25 mol), and ion-exchanged water 3.82 kg were charged, and it took about 3 hours to reach 245 ° C while passing nitrogen under normal pressure. After gradually heating and distilling 8.09 kg of water and 0.28 kg of NMP, the inside of the autoclave was cooled to 200 ° C. The amount of residual water in the system per 1 mol 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.
After cooling the inside of the autoclave to 200 ° C., 10.34 kg (70.32 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added, the autoclave 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 0.6 ° C./min, and the reaction was carried out at 270 ° C. for 140 minutes. Then, 2.67 kg (148.4 mol) of water was press-fitted while cooling from 270 ° C. to 250 ° C. over 15 minutes. Then, after gradually cooling from 250 ° C. to 220 ° C. over 75 minutes, the mixture was rapidly cooled to near room temperature, and the contents were taken out.
The contents were diluted with about 35 liters of NMP to form a slurry, stirred at 85 ° C. for 30 minutes, and filtered through an 80 mesh wire mesh (opening 0.175 mm) to obtain a solid substance. The obtained solid was similarly washed and filtered with about 35 liters of NMP. The operation of diluting the obtained solid with 70 liters of ion-exchanged water, stirring at 70 ° C. for 30 minutes, and then filtering with an 80-mesh wire mesh to recover the solid was repeated a total of 3 times. The obtained solid matter and 32 g of acetic acid are diluted with 70 liters of ion-exchanged water, stirred at 70 ° C. for 30 minutes, filtered through an 80-mesh wire mesh, and the obtained solid matter is further diluted with 70 liters of ion-exchanged water. Then, after stirring at 70 ° C. for 30 minutes, the solid matter was recovered by filtering with an 80 mesh wire mesh.
The obtained solid was dried at 120 ° C. under a nitrogen stream to obtain a polyphenylene sulfide resin (A-1). When the MFR, melt viscosity and chloroform extraction amount of the polyphenylene sulfide resin (A-1) were measured by the above methods, the MFR was 600 g / 10 minutes and the melt viscosity was 100 Pa · s (320 ° C., shear rate 1000 / s). The amount of chloroform extracted was 1.4% by mass.

<Synthesis of polyphenylene sulfide resin (A-2)>
8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.96 kg (70.97 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP) in a 70 liter autoclave with a stirrer. ) 11.45 kg (115.50 mol), 2.58 kg (31.50 mol) of sodium acetate, and 10.5 kg of ion-exchanged water are charged and gradually heated to 245 ° C. over about 3 hours while passing nitrogen under normal pressure. Then, 14.78 kg of water and 0.28 kg of NMP were distilled off, and then the inside of the autoclave was cooled to 160 ° C. The amount of residual water in the system per 1 mol 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 autoclave was sealed under nitrogen gas, and the autoclave was stirred at 240 rpm at 0.6 ° C./min. The temperature was raised to 238 ° C. at the same rate as above. After the reaction was carried out 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 press-fitted over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./min. Then, it was cooled to 200 ° C. at a rate of 1.0 ° C./min and rapidly cooled to near room temperature.
The contents were taken out, diluted with 26.3 kg of NMP, the solvent and solids were filtered off by sieving (80 mesh), and the obtained particles were washed with 31.9 kg of NMP and filtered off. This was washed with 56.0 kg of ion-exchanged water several times and filtered off, and then washed with 70.0 kg of a 0.05 mass% acetic acid aqueous solution and filtered off.
Further, after washing and filtering with 70.0 kg of ion-exchanged water, the obtained hydrophenylene sulfide resin particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C. to obtain the polyphenylene sulfide resin (A-2). Obtained. When the MFR, melt viscosity and chloroform extraction amount of the obtained polyphenylene sulfide resin (A-2) were measured by the above-mentioned methods, the MFR was 100 g / 10 minutes, the melt viscosity was 180 Pa · s (320 ° C., shear rate 1000). / S), the amount of chloroform extracted was 1.2% by mass.

(2) Functional group-containing olefin polymer (B)
<Synthesis of carbodiimide group-containing olefin polymer (B-1)>
1) Synthesis of olefin polymer PO1 Linear low-density polyethylene (ethylene content: 98.0 mol%, density: 0.925 g / cm ³ , MFR: 2 g / 10 minutes) with respect to 100 parts by mass of maleic anhydride (maleic anhydride) MAH (abbreviated as MAH) 0.5 parts by mass, as peroxide 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexin-3 (trade name: perhexin 25B, manufactured by Nippon Yushi) 0.03 parts by mass Was mixed, and graft modification was performed using a 30 mmφ twin-screw extruder set at a cylinder temperature of 250 ° C. As a result, a maleic anhydride-modified ethylene polymer (olefin polymer PO1) having a charged mass ratio of maleic anhydride and a polyethylene chain of 0.5 was obtained.

2) Synthesis of carbodiimide group-containing olefin polymer (B-1) Carbodiimide group-containing compound (polycarbodiimide manufactured by Nisshin Spinning Co., Ltd.) with respect to 100 parts by mass of the obtained maleic anhydride-modified ethylene polymer (olefin polymer PO1). , Trade name: carbodilite HMV-8CA) 6.54 parts by mass (number of moles of polycarbodiimide chain when calculated assuming that the molecular weight of the carbodiimide group-containing compound is 2500: in maleic anhydride-modified ethylene polymer (olefin polymer PO1) The number of moles of maleic anhydride = 1: 2 ) was melt-kneaded in a 30 mmφ twin-screw extruder set at a cylinder temperature of 250 ° C. to obtain a carbodiimide group-containing ethylene polymer (carbodiimide group-containing olefin polymer (B-1)). Obtained. The obtained carbodiimide group-containing ethylene polymer was a pale yellow translucent pellet.

The carbodiimide group content of the obtained carbodiimide group-containing ethylene polymer ^{was measured by 13} C-NMR in the same manner as described above and found to be 17 mmol / 100 g (4.73% by mass). ¹³ The measurement conditions for C-NMR were as follows.
[ ¹³ C-NMR measurement conditions]
Measuring device: An ECP500 type nuclear magnetic resonance device manufactured by JEOL Ltd. was used, and the solvent was an orthodichlorobenzene / heavy benzene (80/20% by volume) mixed solvent. In addition, the measurement temperature is 120 ° C, the observation nucleus is ¹³ C (125 MHz), single pulse proton decoupling, 45 ° pulse, repetition time is 5.5 seconds, the number of integrations is 10,000 times or more, and 27.50 ppm is a chemical shift. It was used as a reference value.
The content of the carbodiimide group and the epoxy group was specified from the peak derived from the carbodiimide group observed in the range of 130 to 142 ppm and the peak derived from the epoxy group observed in the range of 43 to 69 ppm.

Further, when the MFR and the ultimate viscosity of the carbodiimide group-containing ethylene polymer were measured by the above-mentioned methods, the MFR (190 ° C., 2.16 kg load) was 3.1 g / 10 minutes, respectively, in a 135 ° C. decalin solution. The measured ultimate viscosity [η] was 1.58 g / dl. Moreover, since the maleic acid peak disappeared by IR analysis, the reaction rate was 100%.

<Synthesis of carbodiimide group-containing olefin polymer (B-2)>
1) Synthesis of olefin polymer PO2 0.63 mg of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride was placed in a glass flask fully substituted with nitrogen, and a toluene solution of methylaminoxane (Al; 0.13) was added. 1.57 ml (mmol / liter) and 2.43 ml of toluene were further added to obtain a catalytic solution.
Next, 912 ml of hexane and 320 ml of 1-butene were put into a stainless steel autoclave having an internal volume of 2 liters sufficiently substituted with nitrogen, and the temperature in the system was raised to 80 ° C. Subsequently, 0.9 mmol of triisobutylaluminum and 2.0 ml (0.0005 mmol as Zr) of the catalyst solution prepared above were press-fitted into the system together with ethylene to start the polymerization reaction. Ethylene was continuously supplied to maintain the total pressure at 8.0 kg / cm ^2- G, and polymerization was carried out at 80 ° C. for 30 minutes.
After putting a small amount of ethanol into the system to stop the polymerization, unreacted ethylene was purged. The resulting solution was poured into a large excess of methanol to precipitate a white solid. The obtained white solid was collected by filtration and dried under reduced pressure overnight to obtain a white solid (ethylene 1-butene copolymer).
The density of the obtained ethylene / 1-butene copolymer was 0.865 g / cm ³ , the MFR (ASTM D1238 standard, 190 ° C.: 2160 g load) was 0.5 g / 10 minutes, and the 1-butene structural unit content was It was 4 mol%.

To 100 parts by mass of the obtained ethylene / 1-butene copolymer, 2.3 parts by mass of maleic anhydride and 0.04 parts by mass of peroxide [perhexin 25B, manufactured by Nippon Oil & Fats Co., Ltd.] are mixed. did. The obtained mixture was melt-grafted with a uniaxial extruder set at 230 ° C. to obtain a maleic anhydride-modified ethylene / 1-butene copolymer (olefin polymer PO2). The amount of maleic anhydride graft modification of the maleic anhydride-modified ethylene / 1-butene copolymer is 22.4 mmol / 100 g (2.2% by mass), and the MFR (190 ° C., 2.16 kg load) is 0. It was 5 g / 10 minutes, and the ultimate viscosity [η] measured in a 135 ° C. decalin solution was 1.98 dl / g.

2) Synthesis of carbodiimide group-containing olefin polymer (B-2) The obtained maleic anhydride-modified ethylene / 1-butene copolymer (olefin polymer PO2) was used, and the amount of the carbodiimide group-containing compound added was 3. Carbodiimide group-containing ethylene / 1-butene copolymer (carbodiimide group-containing olefin polymer (B-2)) in the same manner as in the method for synthesizing carbodiimide group-containing polyolefin (B-1) except that it was changed to 28 parts by mass. Got The obtained carbodiimide group-containing ethylene / 1-butene copolymer was a pale yellow translucent pellet.

The carbodiimide group content of the obtained carbodiimide group-containing ethylene / 1-butene copolymer was measured in the same manner as described above and found to be 6 mmol / 100 g (1.67% by mass). Further, when the MFR and the ultimate viscosity of the carbodiimide group-containing ethylene / 1-butene copolymer were measured by the above-mentioned methods, the MFR (190 ° C., 2.16 kg load) was 1.1 g / 10 minutes, which was 135. The ultimate viscosity [η] measured in the ° C. decalin solution was 1.81 g / dl. Moreover, since the maleic acid peak disappeared by IR analysis, the reaction rate was 100%.

<Synthesis of Epoxy Group-Containing Polyolefin (B-3)>
After thoroughly mixing 100 parts by weight of maleic anhydride-modified ethylene-butene copolymer (olefin polymer PO2), 5 parts by weight of glycidyl methacrylate, and 0.1 parts by weight of dicumylperoxide with a super mixer, a twin-screw extruder (TEM-50: trade name manufactured by Toshiba Machine Co., Ltd.) was melt-kneaded at 230 ° C. As a result, a glycidyl group-containing ethylene-butene copolymer (glycidyl group-containing polyolefin (B-3)) was obtained.
When the glycidyl methacrylate content of the obtained glycidyl group-containing ethylene-butene copolymer (glycidyl group-containing polyolefin (B-3)) was measured in the same manner as described above, 14.8 mmol / 100 g (2.1% by mass) was measured. )Met. Further, when the MFR and the ultimate viscosity of the glycidyl group-containing ethylene-butene copolymer were measured by the above-mentioned methods, the MFR (190 ° C., 2.16 kg load) was 0.4 g / 10 minutes, which was 135 ° C. The ultimate viscosity [η] measured in the decalin solution was 2.22 g / dl. Moreover, since the maleic acid peak disappeared by IR analysis, the reaction rate was 100%.

<Maleic anhydride group-containing polyolefin (R-1)>
The maleic anhydride-modified ethylene-butene copolymer (olefin polymer PO2) was designated as a maleic anhydride group-containing polyolefin (R-1).

Table 1 shows the physical characteristics of the obtained polymers (B-1) to (B-3) and (R-1).

(3) Inorganic filler (C)
Inorganic filler (C-1): FT756D manufactured by Owens Corning, glass fiber, average fiber length: 3 mm, aspect ratio: 300

(4) Heat-resistant stabilizer (D)
Heat-resistant stabilizer (D-1): A mixture of a copper-based stabilizer (14.3% by mass of copper (I) iodide) and 85.7% by mass of potassium iodide / calcium distearate (98/2 mass ratio). )

(5) Other components Talc: Average particle size 1.6 μm (other inorganic fillers)
Calcium montanate: mold release improver / fluidity improver

<Example 1>
89 parts by mass of polyphenylene sulfide resin (A-1), 10 parts by mass of functional group-containing olefin polymer (B-1), 0.25 parts by mass of heat-resistant stabilizer (D-1), 0.5 parts by mass of talc. Parts and calcium montanate were mixed in an amount of 0.25 parts by mass using a tumbler blender, and the raw materials were melt-kneaded at a cylinder temperature of 320 ° C. using a twin-screw extruder (TEX30α manufactured by Japan Steel Works, Ltd.). Then, the melt-kneaded product was extruded into a strand shape and cooled in a water tank. Then, the strand was taken up with a pelletizer and cut to obtain a pellet-shaped resin composition.

<Examples 2 to 5, Reference Example 1 , Comparative Examples 1 to 4>
A pellet-shaped resin composition was obtained in the same manner as in Example 1 except that the composition was changed to that shown in Table 2 or 3.

Of the obtained resin composition, the tensile strength and tensile elongation, weld flexural strength, Izod impact strength (23 ℃, - 40 ℃) a well blow moldability was evaluated by the following method.

(Tensile strength / tensile elongation)
Each resin composition adjusted by the above method was prepared by using the following injection molding machine, and a test piece of ASTM-1 (dumbbell piece) having a thickness of 3.2 mm adjusted under the following molding conditions was prepared according to ASTM D638 and the temperature. It was left at 23 ° C. in a nitrogen atmosphere for 24 hours. Next, a tensile test was performed in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, and the tensile strength and the elongation rate (%) were measured.
Molding machine: Sodick Plastic Co., Ltd., Tupearl TR40S3A
Molding machine cylinder temperature: 320 ° C,
Mold temperature: 130 ° C

(Bending strength of weld)
Using the following injection molding machine, a test piece having a thickness of 3.2 mm having an ATM No. 1 welded portion was produced under the following molding conditions.
Molding machine: Sodick Plastic Co., Ltd., Tupearl TR40S3A
Molding machine cylinder temperature: 320 ° C,
Mold temperature: 130 ° C
Then, the obtained test piece was left at a temperature of 23 ° C. and in a nitrogen atmosphere for 24 hours. Next, a bending test was performed under the conditions of a bending tester AB5 manufactured by INTESCO, a span of 51 mm, and a bending speed of 12.7 mm / min in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, and the elastic modulus (MPa) was measured.

(Izod impact strength)
Using the following injection molding machine, a test piece with a notch and a thickness of 3.2 mm was prepared under the following molding conditions. The IZOD impact strength of this test piece was measured in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50%, and an atmosphere of a temperature of -40 ° C. and a relative humidity of 50%, respectively, in accordance with ASTMD256.
Molding machine: SE50DU manufactured by Sumitomo Heavy Industries, Ltd.
Molding machine cylinder temperature: 320 ℃
Mold temperature: 130 ° C

(Blow moldability)
Using a large blow molding machine (direct blow molding machine manufactured by Bekm Co., Ltd.), a cylindrical (pipe-shaped) parison was extruded in a continuous manner with a die of φ70 mm and a mandrel of φ60 mm without using an accumulator. The extrusion conditions were a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C. The air was blown immediately after the mold was fastened with a blowing time of 10 hours.
Then, the shapeability (solidification, elongation state) and drawdown state of the parison were evaluated according to the following criteria.
A: The shape of the parison is stable and the molded product can be obtained without drawdown. B: The shape of the parison is possible, but the drawdown is severe, and the molded product has remarkable thickness unevenness. C: The shape of the parison is stable. It draws down without doing so, and there are significant molding defects (perforations, tears).

The evaluation results of Examples 1 to 5 and Reference Example 1 are shown in Table 2, and the evaluation results of Comparative Examples 1 to 4 are shown in Table 3.

As shown in Table 2, the olefin polymer containing epoxy groups or carbodiimide groups (B) an including real施例1-5 and the resin composition of Reference Example 1 has a high tensile strength and high tensile It can be seen that it has elongation, weld bending strength, and Izod impact strength. That is, it can be seen that the resin compositions of Examples 1 to 5 and Reference Example 1 can achieve both high strength and toughness. Further, it can be seen that the resin compositions of Examples 1 to 5 and Reference Example 1 also have good blow moldability.

Above all, from the comparison of Examples 3 and 5 and Reference Example 1 , an olefin polymer containing a carbodiimide group (
The resin compositions of Examples 3 and 5 containing B-1) or (B-2) are stronger (tensile strength) than the resin composition of Reference Example 1 containing an olefin polymer (B-3) containing an epoxy group. ) And toughness (tensile elongation, weld bending strength, Izod impact strength) are higher.

On the other hand, as shown in Table 3, it can be seen that the resin compositions of Comparative Examples 1 to 4 cannot achieve both high strength and toughness (particularly impact strength). Specifically, since the resin composition of Comparative Example 1 does not contain the olefin polymer (B) containing an epoxy group or a carbodiimide group, it can be seen that the Izod impact strength is low and the blow moldability is also low. The resin composition of Comparative Example 2 has an excessively high content of the olefin polymer (B) containing an epoxy group or a carbodiimide group, resulting in insufficient dispersion and a non-uniform dispersion state, resulting in a decrease in strength. I understand. Further, it can be seen that the resin composition of Comparative Example 4 has an excessively small content of the olefin polymer (B) containing an epoxy group or a carbodiimide group, making it difficult to obtain an effect of improving the impact strength, and the Izod impact strength is low. Since the resin composition of Comparative Example 3 contains an olefin polymer (R-1) containing a maleic anhydride group, it interacts with a polyphenylene sulfide resin as compared with an olefin polymer (B) containing an epoxy group or a carbodiimide group. Is unlikely to occur. As a result, the dispersion of the olefin polymer (R-1) becomes insufficient and the dispersed state becomes non-uniform. Therefore, the strength (tensile strength) and toughness (tensile elongation, weld bending strength, Izod impact strength) will be either It turns out that is also low.

Claims (1)

A modified olefin polymer (b1) obtained by graft-modifying an olefin polymer with an unsaturated dicarboxylic acid or an acid anhydride thereof, and a carbodiimide compound (b2) having two or more structural units represented by the formula (2). A step of melt-kneading to obtain a functional group-containing olefin polymer (B) which is a carbodiimide group-containing olefin polymer graft-modified with the carbodiimide compound (b2) .
Equation (2):-(N = C = N-R)-
(R in formula (2) represents a divalent organic group)
6 to 20% by mass of the functional group-containing olefin polymer (B), 10 to 94% by mass of the polyphenylene sulfide resin (A), and 0 to 70% by mass of the fibrous filler (C) (however, the component (A), The total of the component (B) and the component (C) is 100% by mass), which includes a step of melt-kneading.
A method for producing a polyphenylene sulfide resin composition.