JP6798130B2 - Polyarylene sulfide resin composition - Google Patents

Description

The present invention relates to a polyarylene sulfide resin composition having excellent durability even under long-term harsh conditions while maintaining the original high melting point of polyarylene sulfide.

Polyphenylene sulfide (hereinafter abbreviated as PPS) represented by polyphenylene sulfide (hereinafter abbreviated as PPS) is suitable as an engineering plastic due to its excellent heat resistance, barrier property, moldability, chemical resistance, electrical insulation, and moisture heat resistance. It has properties and is used for various electric / electronic parts, mechanical parts, automobile parts, films, fibers, etc., mainly for injection molding and extrusion molding.

In recent years, advanced management by electronic control in various applications has progressed, and the usage environment has become harsher due to high temperature and high humidity. On the other hand, as quality requirements are increasing, PAS is also required to have stricter quality than before, such as durability under long-term harsh conditions and high dimensional accuracy.

The main clavicle of PPS, which is a representative of PAS, has a benzene ring and sulfur as main components and has a structure that can withstand harsh conditions, so that it has extremely high durability. However, the mechanical properties of the resin alone are low, and it is common to add a different material such as a filler or another resin in order to develop various properties such as high strength and improvement of electrical properties. However, since PAS does not have a sufficient functional group, has poor adhesion to different materials, and has a limit in improving physical properties, introduction of a functional group into PAS has been conventionally attempted. For example, Patent Document 1 discloses a PAS having a specific amount of carboxyl groups. Further, Patent Document 2 in which an acid anhydride group is introduced as a functional group of PAS, Patent Document 3 in which a resin composition of PAS and polyamide in which an acid anhydride group is introduced, and PAS and polyamideimide in which an acid anhydride group is introduced Patent Document 4, which is a resin composition, is disclosed.

JP 2001-279097 (Claims) JP-A-04-18422 (Claims) Japanese Patent Application Laid-Open No. 06-9872 (Claims) Japanese Unexamined Patent Publication No. 2000-160009 (Claims)

However, in Patent Document 1, the functional group of PAS is a carboxyl group, and an epoxy-based coupling agent is used as a coupling agent having reactivity with the carboxyl group. The bonding group produced by the reaction between the two is an ester, which has low durability under harsh conditions such as high temperature, high humidity, and solvent environment.

In Patent Document 2, an acid anhydride group is introduced as a functional group, but it is obtained by reacting a prepared side chain amino group-introduced PAS with a carboxylic acid halide. That is, since a bulky acid anhydride group is introduced into the side chain of PAS, the melting point is low, which impairs the high heat resistance inherent in PAS.

Patent Document 3 is a resin composition of PAS and polyamide in which an acid anhydride group is introduced. The imide group produced by the reaction between the two has high durability, but polyamide has low resistance to acid, so that the resin is used. When the molded product of the composition is subjected to long-term acid treatment, there is a problem that the mechanical properties are significantly deteriorated.

In Patent Document 4, the resin composition of PAS and polyamide-imide having an acid anhydride group introduced therein is used. However, like the polyamide of Patent Document 3, polyamide-imide is a polymer having low resistance to acid, and therefore, when treated with a long-term acid, There was a problem that the mechanical properties deteriorated. Patent Document 4 also discloses that a filler is used, but the amount of amino groups or isocyanate groups contained in the filler is very small, and there is a problem in durability in a long-term harsh test.

The present invention has been achieved as a result of studying an object of obtaining a polyarylene sulfide resin composition having excellent durability even under long-term harsh conditions while maintaining the original high melting point of polyarylene sulfide.

As a result of diligent studies to solve this problem, in the PAS resin composition, an acid anhydride group-containing PAS having a high melting point inherent in PAS, an amino group exceeding 5 μmol / g and less than 1000 μmol / g, and / or We have found that the inclusion of a filler having an isocyanate group is excellent in durability even under long-term harsh conditions while maintaining the high melting point inherent in PAS, leading to the present invention. That is, the present invention is as follows.
(A) An acid anhydride group-containing polyarylene sulfide having a melting point of more than 270 ° C. and less than 300 ° C. and (B) a filler having an amino group and / or an isocyanate group of more than 5 μmol / g and less than 1000 μmol / g are blended. (A) The acid anhydride group of the acid anhydride group-containing polyarylene sulfide having a melting point of more than 270 ° C. and less than 300 ° C. exceeds 10 μmol / g and 700 μmol / g. A polyarylene sulfide resin composition that is less than .

According to the present invention, it is possible to obtain a polyarylene sulfide resin composition having excellent durability even under long-term harsh conditions while maintaining the original high melting point of polyarylene sulfide.

The PAS resin composition of the present invention requires a PAS containing an acid anhydride group. The acid anhydride group may be introduced into the arylene sulfide unit constituting the main skeleton of PAS, or may be introduced into the aryl sulfide unit constituting the terminal. Further, even if the acid anhydride group has a structure directly bonded to an arylene sulfide unit or an aryl sulfide unit, the arylene sulfide unit or the aryl sulfide unit has an amino group, an amide group, an ester group, an imide group, an alkyl group, or an alkoxy group. , The structure may be indirectly bonded via a phenylene group or the like. However, if the arylene sulfide unit of PAS has a structure in which an acid anhydride group is indirectly bonded via an amino group, an amide group, an ester group, an imide group, an alkyl group, an alkoxy group, a phenylene group, etc., the main PAS is A bulky component is introduced as a side chain with respect to the chain, which leads to a decrease in melting point and a decrease in mechanical properties. Therefore, it is a structure in which an acid anhydride group is directly bonded to an arylene sulfide unit constituting the main chain of PAS, or a structure in which an acid anhydride group is directly or indirectly bonded to an aryl sulfide unit constituting the terminal of PAS. Is preferable. Among the arylene sulfide units to which the acid anhydride group is directly bonded, the fact that the p-phenylene sulfide unit is formed like the p-phthalic anhydride sulfide unit is from the viewpoint of high melting point and excellent mechanical properties. More preferred.

The PAS resin composition of the present invention requires a filler having an amino group and / or an isocyanate group of more than 5 μmol / g and less than 1000 μmol / g, preferably more than 10 μmol / g and less than 750 μmol / g, preferably 20 μmol / g. More preferably, it exceeds g and is less than 500 μmol / g.

The (A) PAS, (B) filler, (C) and other additives used in the PAS resin composition of the present invention will be described below.

(A) PAS
The PAS in the present invention is a homopolymer or a copolymer having a repeating unit of the formula, − (Ar—S) − as a main constituent unit. The main structural unit here means that the repeating unit is contained in an amount of 80 mol% or more among all the structural units constituting PAS. As the Ar, any unit represented by the following formulas (A) to (K) is exemplified, and among them, the unit represented by the formula (A) is particularly preferable.

R1 and R2 are substituents selected from hydrogen, alkyl group, alkoxy group, halogen group and acid anhydride group, and R1 and R2 may be the same or different.

As long as this repeating unit is used as the main constituent unit, a small amount of branching units or cross-linking units represented by the following formulas (L) to (N) can be included. The copolymerization amount of these branching units or cross-linking units is preferably in the range of 0 to 1 mol% with respect to 1 mol of the- (Ar-S)-unit.

Further, the PAS in the present invention may be any of a random copolymer containing the above repeating unit, a block copolymer and a mixture thereof.

As the repeating unit of PAS, the p-allylen sulfide unit of the formula (A) is preferably contained in an amount of 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more. It is preferable for maintaining a high melting point. If the p-allylen sulfide unit is less than 90 mol%, that is, if the o-allylen sulfide unit or the m-allylen sulfide unit is large, the high melting point inherent in PAS tends to decrease and the mechanical properties tend to decrease, which is not preferable.

Typical examples of these PASs include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ether, polyphenylene sulfide ketone, random copolymers thereof, block copolymers, and mixtures thereof. Particularly preferred PAS is the p-phenylene sulfide unit as the main building block of the polymer.

90 mol% or more, preferably 95 mol% or more, and more preferably 98 mol% or more of polyphenylene sulfide.

The PAS used in the polyarylene sulfide resin composition of the present invention is a PAS having an acid anhydride group in the molecule. A PAS having an acid anhydride group can be obtained by heating and dehydrating a PAS having two or more carboxyl groups on adjacent carbon atoms. PAS can be prepared by a polymerization reaction, and hereinafter, a sulfide agent, an organic polar solvent, a dihalogenated aromatic compound, a monohalogenated compound, a polymerization aid, a branching / cross-linking agent, and a molecular weight adjustment used for the polymerization of PAS. The agent, the polymerization stabilizer, the dehydration step, the polymerization step, the polymer recovery, and the produced PAS will be described in this order.

(A-1) Sulfidating Agent Examples of the sulfidizing agent include alkali metal sulfide, alkali metal hydrosulfide, and hydrogen sulfide. Alkali metal sulfides, alkali metal hydrosulfides, and mixtures thereof are preferably used because of their handleability and versatility. Sulfidating agents can be used as hydrates or aqueous mixtures, or in the form of anhydrides. A sulfidizing agent prepared in situ in the reaction system from alkali metal hydrosulfide and alkali metal hydroxide can also be used.

Preferred sulfurizing agents include sodium sulfide and sodium hydrosulfide, which are preferably used in the form of an aqueous mixture from the viewpoint of handleability.

In the following description, the amount of the sulfidizing agent means the residual amount obtained by subtracting the loss from the charged amount when a partial loss of the sulfidizing agent occurs before the start of the polymerization reaction due to the dehydration operation described later or the like. It shall be.

When alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use alkali metal hydroxide at the same time. The amount of the alkali metal hydroxide used is preferably in the range of 90 mol or more and less than 120 mol, more preferably 95 mol or more and less than 115 mol, and further preferably 95 mol or more and less than 110 mol with respect to 100 mol of the alkali metal hydroxide. It can be illustrated. By setting the amount used in this range, PAS with a small amount of polymerization by-biomass can be obtained without causing decomposition.

(A-2) Organic polar solvent An organic polar solvent is used as the polymerization solvent. Specific examples include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone; caprolactams such as N-methyl-ε-caprolactam; 1,3-dimethyl-2-imidazolidis. Approtic organic solvents such as non-, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphate triamide, dimethylsulfone, tetramethylenesulfocide; and mixtures thereof have high reaction stability. It is preferably used in. Of these, N-methyl-2-pyrrolidone (NMP) is particularly preferably used.

The amount of the organic protic solvent used as the polymerization solvent for PAS is not particularly limited, but from the viewpoint of stable reactivity and economy, it is preferably 250 mol or more and less than 550 mol, more preferably 250 mol or more, per 100 mol of the sulfide agent. The range of 250 mol or more and less than 500 mol, more preferably 250 mol or more and less than 450 mol is exemplified.

(A-3) Dihalogenated Aromatic Compound When producing PAS, a dihalogenated aromatic compound is used as a raw material. Since the benzene ring and sulfur form the main skeleton of the polymer when producing PPS, which is a representative of PAS, the dihalogenated aromatic compounds used are p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, and p-. Examples thereof include dihalogenated benzene such as dibromobenzene. In addition, for the purpose of introducing an acid anhydride group, two or more carboxyl groups may be formed on adjacent carbon atoms such as 3,6-dichlorophthalic acid, 4,5-dichlorophthalic acid, and 4,6-dichlorophthalic acid. It is also one of the preferable embodiments to use a dihalogenated aromatic compound (adjacent carboxyl group-containing dihalogenated aromatic compound), an anhydride or an alkali metal salt thereof, and a mixture thereof as a copolymerization monomer. Further, as long as the effects of the present invention are not impaired, 2,4-dichlorobenzoic acid, 2,5-dichlorobenzoic acid, 2,6-dichlorobenzoic acid, 3,5-dichlorobenzoic acid, 2,4-dichloroaniline, 2,5-Dichloroaniline, 2,6-dichloroaniline, 3,5-dichloroaniline, 2,4-dichlorophenol, 2,5-dichlorophenol, 2,6-dichlorophenol, 3,5-dichlorophenol, 1 It is also possible to use dihalogenated aromatic compounds such as −methoxy-2,5-dichlorobenzene, 4,4′-dichlorophenyl ether, 4,4′-dichlorodiphenylsulfoxide, and 4,4′-dichlorophenylketone. Of these, it is preferable that the main component is p-dihalogenated benzene represented by p-dichlorobenzene. Further, it is also one of the preferable embodiments to partially use an adjacent carboxyl group-containing aromatic compound typified by 3,6-dichlorophthalic acid as a copolymerization component.

The amount of the dihalogenated aromatic compound used is preferably 80 mol or more and less than 150 mol, more preferably 90 mol, per 100 mol of the sulfidizing agent from the viewpoint of suppressing decomposition and efficiently obtaining PAS having a viscosity suitable for processing. The range of more than 110 mol, more preferably 95 mol or more and less than 105 mol can be exemplified. If the amount of the dihalogenated aromatic compound is less than 80 mol per 100 mol of the sulfidizing agent, the obtained PAS tends to be decomposed. When the amount of the dihalogenated aromatic compound is 150 mol or more per 100 mol of the sulfidizing agent, the molecular weight of the obtained PAS tends to decrease, and the mechanical properties and chemical resistance tend to decrease. When an adjacent carboxyl group-containing dihalogenated aromatic compound is used as the copolymerization component, the amount of the adjacent carboxyl group-containing dihalogenated aromatic compound used out of the total amount of the dihalogenated aromatic compound is 100 mol of the sulfidizing agent. A range of preferably 0.1 mol or more and less than 20 mol, more preferably 1 mol or more and less than 15 mol, and further preferably 2 mol or more and less than 10 mol can be exemplified. When the amount of the adjacent carboxyl group-containing dihalogenated aromatic compound is less than 0.1 mol per 100 mol of the sulfidizing agent, the amount of the acid anhydride group of the obtained PAS is small. When the amount of the adjacent carboxyl group-containing dihalogenated aromatic compound is 20 mol or more per 100 mol of the sulfidizing agent, the molecular weight of the obtained PAS tends to decrease and the mechanical properties tend to decrease.

When an adjacent carboxyl group-containing dihalogenated aromatic compound is used, the timing of its addition is not particularly limited, and it may be added at any time during the dehydration step, the start of polymerization, or the middle of polymerization, which will be described later, and may be added a plurality of times. It may be added separately. When added during the dehydration step, a reflux device is required so that the adjacent carboxyl group-containing dihalogenated aromatic compound does not volatilize during the dehydration step. In addition, a press-fitting device is required to add the mixture during the polymerization (pressurized state), and the adjacent carboxyl group-containing dihalogenated aromatic compound reacts during the polymerization, so that the adjacent carboxyl group is contained at the end of the polymerization. Since the consumption of the dihalogenated aromatic compound is not completed, it remains in the polymerization system, and the amount of the acid anhydride group introduced into the PAS is small, it tends to be difficult to develop excellent moist heat resistance and chemical resistance. .. Therefore, the timing of adding the adjacent carboxyl group-containing dihalogenated aromatic compound is preferably when the conversion rate of the dihalogenated aromatic compound is less than 80%, more preferably when it is less than 70%, from the completion of the dehydration step to the start of polymerization. It is more preferable to add it at the start of polymerization, that is, at the same time as the dihalogenated aromatic compound.

(A-4) Monohalogenated Compound When producing PAS, it is also a preferable embodiment to add an adjacent carboxyl group-containing monohalogenated compound for the purpose of obtaining PAS having a high acid anhydride group content. As the adjacent carboxyl group-containing monohalogenated compound, an adjacent carboxyl group-containing monohalogenated aromatic compound can be mentioned as a preferable example. Specifically, 3-chlorophthalic acid, sodium hydrogen 3-chlorophthalate, 3-chlorophthalic anhydride, 4-chlorophthalic acid, sodium hydrogen 4-chlorophthalate, 4-chlorophthalic anhydride, 4-amino-5-chlorophthalate. Acids, 4-chloro-5-nitrophthalic acid and the like can be mentioned. 3-Chlorophthalic acid, 4-chlorophthalic acid, sodium hydrogen 4-chlorophthalate, and 4-chlorophthalic anhydride are preferable monohalogenated compounds from the viewpoint of reactivity and versatility during polymerization. 2-Chlorobenzoic acid, 3-chlorobenzoic acid, 4-chlorobenzoic acid, chlorobenzene, 1-chloronaphthalene, 2-chloroaniline, 3-chloroaniline, 4-chloroaniline, as long as the effects of the present invention are not impaired. , 2-Chlorophenol, 3-chlorophenol, 4-chlorophenol, 4-chlorobenzamide, 4-chlorobenzeneacetamide, 4-chlorobenzenesulfonamide, 4-chlorobenzenesulfonic acid, 4-chlorobenzenethiol, 2-amino-5-chloro It is also possible to use monohalogenated compounds such as benzophenone, 2-amino-4-chlorophenol, 2-chloronitrobenzene, 3-chloronitrobenzene, 4-chloronitrobenzene, and mixtures thereof.

When a monohalogenated compound is used, the amount used is preferably 0.01 mol or more and less than 20 mol, more preferably 0.1 mol or more and less than 15 mol, and further preferably 1.0 mol per 100 mol of the sulfide agent. It is in the range of 10 mol or more, particularly preferably 2.0 mol or more and less than 8 mol. If the amount of the monohalogenated compound is less than 0.01 mol per 100 mol of the sulfidizing agent, the amount of carboxyl groups of the obtained PAS is small. When the amount of the monohalogenated compound is 20 mol or more per 100 mol of the sulfidizing agent, the molecular weight of the obtained PAS tends to decrease and the mechanical properties tend to decrease.

Further, it is preferable that the total amount of halogenated compounds such as dihalogenated aromatic compounds and monohalogenated compounds is within a specific range. The total amount of the halogenated compound is preferably 98 mol or more and less than 110 mol, more preferably 100 mol or more and less than 108 mol, and further preferably 103 mol or more and less than 107 mol with respect to 100 mol of the sulfidizing agent. If the total amount of the halogenated compound is less than 98 mol with respect to 100 mol of the sulfidizing agent, the obtained PAS tends to be decomposed. When the total amount of the halogenated compound is 110 mol or more with respect to 100 mol of the sulfidizing agent, the molecular weight of the obtained PAS tends to decrease, and the mechanical properties and chemical resistance tend to decrease. The halogenated compound also includes a polyhalogenated compound having a trihalogenation or higher used in a branching / cross-linking agent described later.

The timing of addition of the monohalogenated compound is not particularly limited, and the monohalogenated compound may be added at any of the dehydration step, the start of polymerization, and the middle of polymerization, which will be described later, or may be added in a plurality of times. A reflux device is required in which the monohalogenated compound does not volatilize during the dehydration step when added during the dehydration step. In addition, a press-fitting device is required to add the compound during the polymerization (pressurized state), and the monohalogenated compound reacts during the polymerization, so that the consumption of the monohalogenated compound is completed at the end of the polymerization. It does not remain in the polymerization system. Therefore, the timing of adding the monohalogenated compound is preferably when the conversion rate of the dihalogenated aromatic compound is less than 80%, more preferably when it is less than 70%, and even more preferably between the completion of the dehydration step and the start of polymerization. Most preferably, it is added at the start of polymerization, that is, at the same time as the dihalogenated aromatic compound.

(A-5) Polymerization Aid It is also one of the preferable embodiments to use a polymerization aid when producing PAS. The purpose of using the polymerization aid is to adjust the resulting PAS to the desired melt viscosity. Specific examples of the polymerization aid include organic carboxylic acid metal salts, water, alkali metal chlorides (excluding sodium chloride), organic sulfonic acid metal salts, alkali metal sulfates, alkaline earth metal oxides, and alkalis. Examples include metal phosphates and alkaline earth metal phosphates. These can be used alone or two or more at the same time. Of these, organic carboxylic acid metal salts and / or water are preferably used.

The organic carboxylic acid metal salt can also be used as a hydrate, an anhydride or an aqueous solution. Specific examples include lithium acetate, sodium acetate, potassium acetate, magnesium acetate, calcium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, and mixtures thereof. Sodium acetate, which is inexpensive and has appropriate solubility in a reaction system, is preferably used.

(A-6) Molecular Weight Adjusting Agent When producing PAS, a branched or crosslinked polymer is formed, and in order to adjust the obtained PAS to a desired melt viscosity, branching / crosslinking of a polyhalogen compound having a trihalogenation or higher is performed. It is also possible to use the agent in combination. The polyhalogen compound is preferably a polyhalogenated aromatic compound, and specific examples thereof include 1,3,5-trichlorobenzene and 1,2,4-trichlorobenzene.

(A-7) Polymerization Stabilizer When producing PAS, it is also possible to use a polymerization stabilizer in order to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to the stabilization of the polymerization reaction system and suppresses undesired side reactions such as the production of thiophenol. Specific examples of the polymerization stabilizer include compounds such as alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, and alkaline earth metal carbonates. Of these, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferred. The above-mentioned organic carboxylic acid metal salt also acts as a polymerization stabilizer. Further, when an alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use the alkali metal hydroxide at the same time, but here, the alkali metal water which is excessive with respect to the sulfidizing agent. Oxides can also be polymerization stabilizers.

These polymerization stabilizers can be used alone or in combination of two or more. The polymerization stabilizer is preferably used in a ratio of 1 to 20 mol, more preferably 3 to 10 mol, based on 100 mol of the sulfidizing agent in the reaction system before the start of the polymerization reaction. If this ratio is too large, it tends to be economically disadvantageous and the polymer yield tends to decrease. If a part of the alkali metal sulfide is decomposed during the reaction to generate hydrogen sulfide, the resulting alkali metal hydroxide can also be a polymerization stabilizer.

The timing of addition of the polymerization stabilizer is not particularly limited, and the polymerization stabilizer may be added at any of the dehydration step, the start of polymerization, and the middle of polymerization, which will be described later, or may be added in a plurality of times.

(A-8) Dehydration Step When producing PAS, the sulfidizing agent is usually used in the form of a hydrate. Before adding the dihalogenated aromatic compound or the monohalogenated compound, it is preferable to heat the mixture containing the organic polar solvent and the sulfidizing agent to remove an excess amount of water from the system. This process is called a dehydration process. Although this method is not particularly limited, it is desirable to use alkali metal hydrosulfide and alkali metal hydroxide as an organic polar solvent in a temperature range of normal temperature to 150 ° C., preferably normal temperature to 100 ° C. in an inert gas atmosphere. In addition, there is a method in which the temperature is raised to at least 150 ° C. or higher, preferably 180 ° C. to 260 ° C. under normal pressure or reduced pressure to distill off water.

The amount of water in the system at the stage when the dehydration step is completed is preferably 90 to 110 mol per 100 mol of the charged sulfidizing agent. Here, the amount of water in the system is the amount obtained by subtracting the amount of water removed from the system from the amount of water charged in the dehydration step.

(A-9) Polymerization Step When producing PAS, a polymerization step is carried out in which the reaction product prepared in the dehydration step is brought into contact with a dihalogenated aromatic compound or a monohalogenated compound in an organic polar solvent to carry out a polymerization reaction. .. At the start of the polymerization step, a dihalogenated aromatic compound or a monohalogenated compound is added in a temperature range of 100 to 220 ° C., preferably 130 to 200 ° C., preferably under an inert gas atmosphere. The order in which these raw materials are charged may be random or simultaneous.

The polymerization step is preferably carried out in a temperature range of 200 ° C. or higher and lower than 280 ° C., but the polymerization conditions are not limited as long as the effects of the present invention can be obtained. For example, a method in which the temperature is raised at a constant rate and then the reaction is continued for a certain period of time in a temperature range of 245 ° C. or higher and lower than 280 ° C., or 245 ° C. after the reaction is carried out at a constant temperature in a temperature range of 200 ° C. or higher and lower than 245 ° C. The reaction was carried out at a constant temperature for a certain period of time in a temperature range of 200 ° C. or higher and lower than 245 ° C., particularly in a temperature range of 230 ° C. or higher and lower than 245 ° C. After that, a method of raising the temperature to a temperature range of 245 ° C. or higher and lower than 280 ° C. to complete the reaction in a short time can be mentioned. Among them, sulfide in an organic polar solvent is a preferable polymerization condition for obtaining PAS having a high acid anhydride group amount required for obtaining the PAS resin composition of the present invention and having a small amount of reaction by-products. When the agent is reacted with a predetermined amount of a dihalogenated aromatic compound or a monohalogenated compound in a temperature range of 200 ° C. or higher and lower than 280 ° C. to obtain PAS.
<Step 1> In the temperature range of 230 ° C. or higher and lower than 245 ° C., the polymerization time (T1a) including the elevating temperature time is 30 minutes or more and less than 3.5 hours, and the dihalogenated aromatic compound at the end of the step A step of reacting so that the conversion rate becomes 70 to 98 mol% to form a PAS prepolymer, and <step 2> in the temperature range of 245 ° C. or higher and lower than 280 ° C., the polymerization time including the elevating temperature time (step 2). A step of reacting the prepolymer of PAS in T2) for 5 minutes or more and less than 1 hour to obtain PAS.
The polymerization conditions that go through the above can be mentioned.

Hereinafter, steps 1 and 2 will be described in detail.

<Step 1> In order to obtain PAS having a high amount of acid anhydride and a small amount of volatile components, step 2 is performed after sufficiently increasing the conversion rate of the dihalogenated aromatic compound or monohalogenated compound at a low temperature. Is preferable. However, in a reaction with a polymerization temperature of less than 230 ° C., the reaction rate is slow, so that the conversion rate of the dihalogenated aromatic compound or the monohalogenated compound is difficult to increase, the melt viscosity of the obtained PAS is low, and the melt flow suitable for injection molding. It tends to be difficult to obtain sex. Further, it takes a long time to increase the conversion rate of the dihalogenated aromatic compound by the reaction only at less than 230 ° C., which is not preferable in terms of production efficiency. Therefore, in step 1, in a temperature range of 230 ° C. or higher and lower than 245 ° C., which has a relatively high reaction rate, 30 minutes or more and less than 3.5 hours, preferably 40 minutes or more and less than 3.5 hours, more preferably 1 hour or more and 3 hours. It is preferable to carry out the reaction for less than an hour, more preferably 1.5 hours or more and less than 3 hours. In order to increase the conversion rate of the dihalogenated aromatic compound in the temperature range of 230 ° C. or higher and lower than 245 ° C., it is preferable to shorten the polymerization time in the temperature range of lower than 230 ° C. in terms of production efficiency. The polymerization time in the temperature range of 200 ° C. or higher and lower than 230 ° C. is preferably 2 hours or less, and more preferably 1 hour or less. Further, the polymerization time (T1) including the elevating temperature time in the temperature range of 200 ° C. or higher and lower than 245 ° C. including step 1 is preferably 1.5 hours or more and less than 4 hours, and 1.5 hours or more and 3 hours. . Less than 5 hours is more preferable, and 2 hours or more and 3.5 hours or less is further preferable. When T1 is less than 1.5 hours, the conversion rate of the sulfidizing agent becomes low, which tends to cause a side reaction in step 2. Further, if T1 exceeds 4 hours, the production efficiency is lowered.

It is desirable that the average heating rate within such a polymerization temperature range is 0.1 ° C./min or more. The average temperature rise rate is the time m required to raise the temperature in the temperature interval (where t2 <t1) from a certain constant temperature t2 (° C.) to a certain constant temperature t1 (° C.). From (minutes), the following formula average temperature rise rate (° C / min) = [t1 (° C) -t2 (° C)] / m (minute)
Is the average speed calculated by. Therefore, as long as it is within the range of the above-mentioned average temperature rise rate, the rate does not necessarily have to be constant, there may be a constant temperature section, and there is no problem even if the temperature is raised in multiple stages, and the temperature rises temporarily negatively. There may be a section where the temperature is high.

The average heating rate is more preferably 2.0 ° C./min or less, and even more preferably 1.5 ° C./min or less. If the average heating rate is too high, it may be difficult to control the reaction, and more energy tends to be required to increase the temperature. When a violent reaction occurs at the initial stage of the reaction, it tends to be preferable to carry out the reaction at 240 ° C. or lower to some extent and then raise the temperature to over 240 ° C.

It is preferable to react so that the conversion rate of the sulfidizing agent at the end of step 1 is 70 to 98 mol% to produce a PAS prepolymer, more preferably 75 mol% or more, still more preferably 80 mol% or more. More preferably, the reaction is carried out so as to be 90 mol% or more. If the process proceeds to step 2 in a state where the conversion rate is low, a side reaction tends to occur. Further, if the reaction is carried out until the conversion rate in step 1 exceeds 98 mol%, a long polymerization time is required, which leads to a decrease in production efficiency.

<Step 2> The final temperature of step 2 is preferably 275 ° C. or lower, more preferably 270 ° C. or lower. When the polymerization is completed only in step 1 without going through step 2, or when the polymerization time in step 2 is extremely short, the melt viscosity of the obtained PAS tends to decrease, and the strength of the molded product tends to decrease. On the other hand, if the polymerization in step 2 is carried out for a long time, a side reaction proceeds and the acid anhydride group tends to be unable to be efficiently introduced into PAS. When the final temperature of step 2 reaches 280 ° C. or higher, the melt viscosity of the obtained PAS becomes too high and the internal pressure of the reactor tends to increase significantly, so that a reactor having high withstand voltage performance is required. Therefore, it is not preferable in terms of economy and safety.

The polymerization time (T2) of the step 2 is preferably 5 minutes or more and less than 1 hour, more preferably 10 minutes or more and less than 40 minutes, and even more preferably 10 minutes or more and less than 30 minutes. By controlling within this range, the acid anhydride group can be efficiently introduced into PAS while suppressing side reactions.

The reaction in step 2 may be a one-step reaction performed at a constant temperature, a multi-step reaction in which the temperature is raised stepwise, or a reaction in which the temperature is continuously changed.

Further, it is preferable that the ratio (T1a / T2) of the polymerization time (T1a) of the step 1 to the polymerization time (T2) of the step 2 is 0.5 or more. The higher the ratio, the more sufficient the polymerization time in step 1 can be secured and the conversion rate of the dihalogenated aromatic compound or monohalogenated compound can be increased, and at the same time, the polymerization time in step 2 can be suppressed to a short time. .. Further, the acid anhydride group can be efficiently introduced into PAS while suppressing the side reaction by suppressing the reaction at a high temperature as in step 2 in a short time. Therefore, T1a / T2 is more preferably 1 or more, further preferably 2 or more, and even more preferably 5 or more. The upper limit of T1a / T2 is not particularly limited, but is preferably 25 or less, more preferably 20 or less, in order to obtain PAS having preferable melt fluidity.

Further, it is preferable that the ratio (T1 / T2) of the polymerization time (T1) in the temperature range of 200 ° C. or higher and lower than 245 ° C. including step 1 to the polymerization time (T2) of step 2 is 1.2 or more. The higher the ratio, the more sufficient the polymerization time at a low temperature can be secured and the conversion rate of the sulfidizing agent can be increased, and at the same time, the polymerization time in the step 2 can be suppressed to a short time. Therefore, T1 / T2 is more preferably 3 or more, and even more preferably 5 or more. The upper limit of T1 / T2 is not particularly limited, but is preferably 30 or less, more preferably 25 or less, in order to obtain PAS having preferable melt fluidity.

Further, the total reaction time (T1 + T2) from the start of step 1 to the end of step 2 is preferably less than 5 hours, more preferably less than 4 hours, and even more preferably less than 3.5 hours. Prolonged polymerization time leads to a decrease in production efficiency and tends to increase side reactions.

The atmosphere at the time of polymerization is preferably a non-oxidizing atmosphere, and preferably an atmosphere of an inert gas such as nitrogen, helium, or argon. In particular, nitrogen is preferable from the viewpoint of economy and ease of handling. The reaction pressure is not particularly limited because it cannot be unconditionally specified depending on the type and amount of the raw material and solvent used, the reaction temperature, and the like.

(A-10) Polymer Recovery When producing PAS, after the completion of the polymerization step, PAS is recovered from the polymerization reaction product containing the PAS component and the solvent obtained in the polymerization step. As a recovery method, for example, a flash method, that is, the polymerization reaction product is flushed from a high temperature and high pressure (usually 250 ° C. or higher, 0.8 MPa or higher) state into an atmosphere of normal pressure or reduced pressure, and the polymer is powdered and granulated at the same time as solvent recovery. The method of recovering the polymer or the quenching method, that is, the polymerization reaction product is gradually cooled from a high temperature and high pressure state to precipitate PAS components in the reaction system, and filtered at 70 ° C. or higher, preferably 100 ° C. or higher. Examples thereof include a method of recovering a solid containing a PAS component.

The recovery method is not limited to either the quench method or the flush method, but the flash method is capable of recovering solids at the same time as solvent recovery, has a relatively short recovery time, and is compared with the quench method. Because it is an economically excellent recovery method, such as a large amount of recovered material obtained, and the PAS obtained by the flash method contains a large amount of oligomer components such as chloroform extract components, it is quenched. The flash method is a preferable recovery method because it is easy to easily obtain PAS having high melt fluidity as compared with PAS obtained by the method.

Since the PAS obtained by such a flash method contains ionic impurities such as alkali metal halides and alkali metal organic substances which are polymerization by-products, it is preferable to perform cleaning. The cleaning conditions are not particularly limited as long as they are sufficient to remove such ionic impurities. Examples of the cleaning liquid include a method of cleaning with water or an organic solvent. Cleaning with water can be exemplified as a preferable method in that it is simple and inexpensive, and that the PAS contains an oligomer component to provide high melt fluidity. It is preferable to perform the treatment of immersing the PAS in a liquid of water, an acid or an aqueous solution of an acid, an aqueous solution of an alkali metal salt or an aqueous solution of an alkaline earth metal salt at least once, and a polymer and a cleaning liquid are mixed between each cleaning treatment. It is more preferable to go through a separation filtration step.

When the PAS is immersed in an acid or an aqueous solution of an acid, the pH of the cleaning solution after the treatment is preferably 2 to 8. The acid or an aqueous solution of an acid is an organic acid, an inorganic acid, or water added with an organic acid, an inorganic acid, or the like to make it acidic. Examples of the organic acid and the inorganic acid to be used include acetic acid, propionic acid, hydrochloric acid, sulfuric acid, phosphoric acid and formic acid. Acetic acid or hydrochloric acid is preferred.

When PAS is immersed in an aqueous solution of an alkali metal salt or an alkaline earth metal salt, examples of the alkali metal salt and the alkaline earth metal salt to be used include the calcium salt, potassium salt, sodium salt, magnesium salt and the like of the above organic acids. It can, but is not limited to these.

The temperature at which the PAS is washed with the cleaning liquid is preferably 80 ° C. or higher and 220 ° C. or lower, more preferably 150 ° C. or higher and 200 ° C. or lower, and further preferably 180 ° C. or higher and 200 ° C. or lower in terms of obtaining PAS with less ionic impurities. ..

Any cleaning solution may be used, but treatment with an acid provides higher melt fluidity, and thus can be exemplified as a suitable method.

The PAS thus obtained is dried under normal pressure and / or reduced pressure. The drying temperature is preferably in the range of 120 to 280 ° C. in order to dry the PAS and dehydrate the adjacent carboxyl groups to form an acid anhydride. The dry atmosphere may be any of an inert atmosphere such as nitrogen, helium and under reduced pressure, an oxidizing atmosphere such as oxygen and air, and a mixed atmosphere of air and nitrogen, but the inert atmosphere is preferable because of the melt viscosity. The drying time is preferably 0.5 to 50 hours.

It is also possible to treat the obtained PAS in an oxygen-containing atmosphere at a temperature of 130 to 260 ° C. for 0.1 to 20 hours for the purpose of removing volatile components and increasing the cross-linked high molecular weight.

(A-11) Generated PAS
The melting point of the PAS thus obtained needs to be 270 ° C. or higher and lower than 300 ° C. When a large amount of acid anhydride group is introduced into the side chain of PAS, the melting point tends to decrease, and the high heat resistance inherent in PAS tends to be impaired. Therefore, it is preferable to introduce an acid anhydride at the PAS terminal having a small influence on the melting point, and the melting point is more preferably 270 ° C. or higher and lower than 285 ° C.

Further, the acid anhydride group contained in PAS preferably exceeds 10 μmol / g and is less than 700 μmol / g. From the viewpoint of high melting point and excellent mechanical properties, the structure in which the acid anhydride group is directly bonded to the arylene sulfide unit or aryl sulfide unit of PAS among the total acid anhydride groups is more than 50 μmol / g and less than 600 μmol / g. It is preferably more than 100 μmol / g and less than 400 μmol / g.

In the present invention, the weight average molecular weight of PAS is preferably 10,000 or more and less than 100,000. When the molecular weight of PAS is low, the mechanical properties of PAS itself are significantly lowered. Therefore, even if the content of the acid anhydride group is high, the mechanical properties of the molded product using the resin composition tend to be lowered. On the other hand, if the molecular weight of PAS is too high, the viscosity at the time of melting increases significantly, and the resin composition tends not to enter the mold at the time of injection molding, so that a molded product cannot be obtained. The weight average molecular weight of PAS is preferably 15,000 or more, more preferably 16,000 or more, and even more preferably 17,000 or more. The weight average molecular weight of PAS is preferably less than 80,000, more preferably less than 60,000, and even more preferably less than 40,000.

When a monohalogenated compound containing an adjacent carboxyl group is added at the time of polymerization when obtaining PAS, a part of the terminal chlorine of PAS is replaced with an adjacent carboxyl group or an acid anhydride group, so that the chlorine content of PAS tends to decrease. is there. In the field of electrical and electronic parts, the movement toward lower halogenation is becoming active as an environmental initiative, and PAS with a low chlorine content also has an effect as a material for reducing environmental load. The chlorine content of PAS in the present invention is preferably 3500 ppm or less, more preferably 3000 ppm or less, still more preferably 2500 ppm or less.

As the PAS used in the PAS resin composition, two or more types of PAS can be used in combination.

(B) Filler The PAS resin composition of the present invention needs to contain a filler having an amino group and / or an isocyanate group of more than 5 μmol / g and less than 1000 μmol / g in the above PAS, and it is necessary to add 10 μmol. It is preferably more than / g and less than 750 μmol / g, and more preferably more than 20 μmol / g and less than 500 μmol / g. In the present invention, when the PAS resin composition is prepared, the acid anhydride group of PAS reacts with the amino group and the isocyanate group of the filler to form a highly durable imide group, and high durability is exhibited even in a long-term harsh test. If the number of amino groups or isocyanate groups is too small, the formation of imide groups is too small, and the durability of the obtained PAS resin composition tends to be low. On the other hand, if the amount is too large, the amount of volatile components increases during melting, which causes voids and deterioration of mechanical properties during injection molding, and also tends to cause problems such as mold stains. Here, the content of the amino group and / or the isocyanate group contained in the filler is a value calculated by a method such as titration using an appropriate indicator.
Examples of the filler include an inorganic filler and an organic filler.

Inorganic fillers include glass fiber, glass milled fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, warastenite whisker, aluminum borate whisker, alumina fiber, silicon carbide fiber, ceramic fiber, and stone shaving fiber. , Metal fiber, fibrous inorganic filler such as basalt fiber; talc, wallastenite, zeolite, sericite, mica, kaolin, clay, mica, ferrite, pyrophyllite, bentonite, alumina silicate, silicon oxide, magnesium oxide, alumina , Zirconium oxide, titanium oxide, iron oxide, magnesium oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, glass beads, glass flakes, glass powder, ceramic beads , Non-fibrous inorganic fillers such as boron nitride, silicon nitride, silicon carbide, aluminum silicate, calcium silicate, silica, graphite, carbon black and graphite.

Organic fillers include polyethylene fibers, polypropylene fibers, polyester fibers, polyamide fibers, polyaramid fibers, fluororesin fibers, thermosetting resin fibers, epoxy resin fibers, polyvinylidene chloride fibers, polyvinylidene fluoride fibers, cellulose fibers, etc. Fibrous organic fillers; non-fibrous organic fillers such as ebonyite powder, cork powder, wood powder and the like.

These inorganic fillers and organic fillers may be hollow. It is also possible to use two or more of these fillers together. Further, these fillers may be pretreated with an isocyanate-based compound, an organic silane-based compound, an organic titanate-based compound, an organic borane-based compound, an epoxy compound, or the like before use.

The fibrous filler is not limited in fiber shape, and short fibers or long fibers can be used. The short fiber generally refers to a fibrous filler having an average fiber length of 1 mm or more and less than 10 mm before compounding. Further, the long fiber generally refers to a fibrous filler in which the average fiber length before compounding is in the range of 10 mm or more and less than 50 mm. Generally, it is prepared by cutting or crushing strand-shaped fibers. Here, the average fiber length refers to the average fiber length calculated from the following formula in consideration of the contribution of the fiber length.
Average fiber length (Lw) = Σ (Wi x Li) / ΣWi
= Σ (πri ² × Li × ρ × ni × Li) / Σ (πri ² × Li × ρ × ni)
When the fiber diameter ri and the density ρ are constant, the above equation is simplified and becomes the following equation.
Average fiber length (Lw) = Σ (Li ² x ni) / Σ (Li x ni)
Li: Fiber length of fibrous filler ni: Number of fibrous fillers with fibrous length Li Wi: Weight of fibrous filler ri: Fiber diameter of fibrous filler ρ: Density of fibrous filler.

In the present invention, the type of the filler is not specified, but a fibrous inorganic filler such as glass fiber or carbon fiber is preferable in consideration of the reinforcing effect of the filler as the resin composition. Carbon fiber has not only the effect of improving mechanical properties but also the effect of reducing the weight of molded products. Further, when the filler is carbon fiber, the effect of improving the mechanical properties of the PAS resin composition is more exhibited. Among the PAN-based, pitch-based, and rayon-based carbon fibers, the PAN-based carbon fiber is preferable from the viewpoint of the balance between the strength and elastic modulus of the molded product.

The method of imparting an amino group and / or an isocyanate group to the filler is not specified, but a method of forming an amino group and / or an isocyanate group by surface treatment of the filler, an amino group and / or an isocyanate group is used. Examples thereof include a method of applying the sizing agent to the filler. Examples of the sizing agent include urethane resin, amino resin, and alkoxysilane compound. These may be used alone or in combination of two or more. Of these, a method of applying a sizing agent containing a primary amine or isocyanate to the filler is preferable. Further, if necessary, an epoxy resin, polyethylene glycol, polyester, an emulsifier, a surfactant and the like may be used in combination.

Examples of the amino resin include urea resin, melamine resin, benzoguanamine resin, glycoluril resin and the like, and those having an amino group, a methylol group or an alkoxymethyl group and further having an imino group can also be used. These can be used alone or in combination of two or more, and are preferably used in an aqueous dispersion such as an emulsion or dispersion, and a water-soluble amino resin that is easily dissolved in water is preferably used.

Examples of the alkoxysilane compound containing an amino group include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and N-2- (amino). Ethyl) -3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl)- 2-Aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 4-aminobutyltriethoxysilane, p-aminophenyltrimethoxysilane, m-aminophenyltrimethoxysilane, 3-aminopropyltris (methoxyethoxy) silane, 11-Aminoundecyltriethoxysilane, 3- (m-aminophenoxy) propyltrimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyldiisopropylethoxysilane, 3-aminopropyldimethylethoxysilane, N-( 2-Aminoethyl) -3-aminopropyltriethoxysilane, N- (6-aminoethyl) aminomethyltriethoxysilane, N- (6-aminohexyl) aminopropyltrimethoxysilane, N- (2-aminoethyl) -11-Aminoundecyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminoisobutylmethyldimethoxysilane, (aminoethylamino)- Examples include 3-isobutyldimethylmethoxysilane, (3-trimethoxysilylpropyl) diethylenetriamine, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxycisilane, 3- (2-ureidoethyl) aminopropyltrimethoxysilane, etc. Be done.

Examples of the alkoxysilane compound having an isocyanate group include 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropylmethyldimethoxysilane, 3-isocyanatepropylmethyldiethoxysilane, and 3-isocyanatepropylethyldimethoxysilane. , 3-Isocyanatepropylethyldiethoxysilane, 3-Isocyanatepropyltrichlorosilane (isocyanatemethyl) methyldimethoxysilane and the like.

Among the above alkoxysilane compounds, an alkoxysilane compound having a primary amine or an isocyanate group is preferable.

The amount of the sizing agent adhered is preferably 0.05 to 20% by mass, more preferably 0.05 to 10% by mass, still more preferably 0.1 to 5% by mass, based on the filler. If the amount of the sizing agent adhered is less than 0.05% by mass, the effect of improving the mechanical properties of the PAS resin composition is unlikely to appear, and at the same time, problems such as fluff and thread breakage tend to occur. If the amount of adhesion exceeds 20% by mass, the sizing agent volatilizes when the PAS resin composition is melted, and the working environment tends to deteriorate due to gas generation.

(C) Other Additives In the PAS resin composition of the present invention, in addition to (A) an acid anhydride group-containing PAS, (B) a filler having a specific amount of amino groups and / or isocyanate groups, the effects of the present invention can be obtained. If necessary, an alkoxysilane compound, a resin other than PAS, or the like may be added as long as it is not impaired.

As the alkoxysilane compound, 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 may be used. Of these, alkoxysilanes having a primary amine or an isocyanate group are preferable in order to enhance durability such as moisture and heat resistance. If the amount added is too small, the effect of improving physical properties is small, and if the amount added is too large, the melt viscosity increases and injection molding becomes difficult. Therefore, (A) 0.05 to 0.05 to 100 parts by mass of the PAS. Addition of 5 parts by mass is desirable.

Resins other than PAS include polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, modified polyphenylene ether resin, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyetherimide resin, polyarylate resin, liquid crystal polymer, and polyether. Examples thereof include sulfone resin, polyether ketone resin, polythioether ketone resin, polyether ether ketone resin, polyimide resin, polyamideimide resin, tetrafluoride polyethylene resin, polytetrafluoroethane, ethylene-tetrafluoroethylene and the like. Although flexibility and impact resistance can be improved by adding these resins, long-term acid treatment is performed by using a large amount of resins with low acid resistance such as polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, and polyamideimide resin. At that time, the mechanical properties tend to be significantly reduced, and the effect of the present invention tends to be impaired. Therefore, the amount is preferably less than 30 parts by mass, more preferably 25 parts by mass or less, based on 100 parts by mass of the PAS resin composition. It is also possible to add an olefin copolymer to improve toughness. Although the presence or absence of a functional group is not limited in the olefin-based copolymer, at least one functional group selected from the group consisting of an epoxy group, a carboxyl group, an acid anhydride group, an amino group, an isocyanate group, a hydroxyl group and a mercapto group can be used. The olefin-based copolymer having is preferable. Among them, in order to exhibit high durability under long-term harsh conditions, an olefin copolymer having an acid anhydride group, an amino group and an isocyanate group is more preferable, and (A) 1 to 30 parts by mass with respect to 100 parts by mass of PAS. The part can be exemplified as a preferable range.

Further, the following compounds can be added for the purpose of modification. Halogen-based and phosphorus-based flame retardants; phenol-based and phosphorus-based antioxidants; isocyanate-based compounds, organic titanate-based compounds, organic borane-based compounds, polyalkylene oxide oligoma-based compounds, thioether-based compounds, ester-based compounds, organic phosphorus Plasticizers such as system compounds; Crystal nucleating agents such as talc, kaolin, organophosphorus compounds, polyether ether ketones; Metal soaps such as waxes montanate, lithium stearate, aluminum stearate; ethylenediamine, stearic acid, sebacic acid weight Release agents such as condensates and silicone compounds; anticolorants such as hypophosphates; and additives such as lubricants, UV inhibitors, colorants and foaming agents.

The PAS resin composition thus obtained preferably contains (A) 30 to 90 parts by mass of PAS and (B) 10 to 70 parts by mass of a filler with respect to 100 parts by mass of the PAS resin composition, and (B) filling. The material is more preferably in the range of 20 to 60 parts by mass, further preferably in the range of 20 to 50 parts by mass, and even more preferably in the range of 30 to 50 parts by mass. (B) When the blending amount of the filler exceeds 70 parts by mass, the melt fluidity of the PAS resin composition decreases. If the blending amount of the filler is less than 10 parts by mass, the reinforcing effect as the filler is small, so that it tends to be difficult to develop excellent mechanical properties.

The PAS resin composition of the present invention can be obtained by melt-kneading the above-mentioned (A) PAS and (B) filler, and if necessary, (C) other additives. In melt-kneading, the raw material is supplied to a known melt-kneader such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll, at a processing temperature of + 5 to 100 ° C. A typical example is a kneading method.

The mixing order of the raw materials is not particularly limited, and all the raw materials are blended and then melt-kneaded by the above method, some raw materials are blended and then melt-kneaded by the above method, and the remaining raw materials are blended and melt-kneaded. Any method may be used, such as a method, or a method in which a part of the raw materials is mixed and then the remaining raw materials are mixed by using a side feeder during melt-kneading by a single-screw or twin-screw extruder. Further, as for the small amount additive component, it is of course possible to knead other components by the above method or the like to pelletize them, and then add them before molding and use them for molding.

The molded product obtained from the PAS resin composition of the present invention has excellent durability even under long-term harsh conditions while maintaining the high heat resistance inherent in PAS. The PAS resin composition of the present invention can be used not only for injection molding, injection compression molding, blow molding, etc., but also for molding into extrusion-molded products such as sheets, films, fibers and pipes by extrusion molding. it can.

Applications of the PAS resin composition of the present invention include, for example, sensors, LED lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable power storage cases, optical pickups, oscillators, various terminal boards, and transformers. , Plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystal, motor brush holders, parabolic antennas, computer-related parts, and other electrical and electronic parts; recorder parts , TV parts, irons, hair dryers, rice cooker parts, microwave parts, acoustic parts, audio equipment parts such as CD / DVD / Blu-ray discs, lighting parts, refrigerator parts, air conditioner parts, etc. Parts: Office computer-related parts, telephone-related parts, facsimile-related parts, copying machine-related parts, cleaning jigs, motor parts, lighters, and other machine-related parts: microscopes, binoculars, cameras, watches, etc. Optical equipment, precision machinery related parts; water faucet tops, mixing faucets, pump parts, pipe joints, water volume control valves, relief valves, hot water temperature sensors, water volume sensors, water meter housings and other water-related parts; valve alternator terminals, alternators Connector, IC regulator, Potency meter base for light dimmer, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body , Carburettor 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 for radiator motor Holder, water pump impeller, turbine vane, wiper motor related parts, dustributor, starter switch, starter relay, wire harness for transmission, window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, fuse connector, horn Terminals, electrical component insulation plates, step motor rotors, lamp sockets, lamp reflectors Examples include automobile / vehicle-related parts such as tars, lamp housings, brake pistons, solenoid bobbins, engine oil filters, fuel tanks, ignition device cases, vehicle speed sensors, and cable liners, and various other uses.

Hereinafter, the method of the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. The method for measuring physical properties is as follows.

[Acid anhydride group content]
The acid anhydride group content of PAS was calculated using a Fourier transform infrared spectroscope (hereinafter abbreviated as FT-IR).

First, phthalic anhydride was measured by FT-IR as a standard substance, and the absorption intensity (b1) of the peak of 3066 cm-1, which is the absorption of the CH bond of the benzene ring, and the absorption of the acid anhydride group, 1850 cm-. The absorption intensity (c1) of the peak of 1 was read, and the amount of carboxyl groups (U1) and (U1) = (c1) / [(b1) / 5] with respect to 1 unit of the benzene ring were determined. Next, PAS was melt-pressed at 320 ° C. for 1 minute and then rapidly cooled to perform FT-IR measurement of the obtained amorphous film. Read the absorption intensity (b2) of 3066 cm-1 and the absorption intensity (c2) of 1850 cm-1, and determine the amount of carboxyl groups (U2) and (U2) = (c2) / [(b2) / 4] for one unit of the benzene ring. I asked. When the PAS was PPS, it was composed of phenylene sulfide units, so the carboxyl group content with respect to 1 g of PPS was calculated from the following formula. Acid anhydride group content of PPS (μmol / g) = (U2) / (U1) /108.161 × 1000000

When the PPS contained a metaphenylene sulfide unit, absorption was observed at 780 cm-1, but the absorption was not observed in the following PPS-1 to 9.

[Carboxylic acid group content]
First, benzoic acid was measured by FT-IR as a standard substance, and the absorption intensity (b1) of the peak of 3066 cm-1, which is the absorption of the CH bond of the benzene ring, and the peak of 1704 cm-1, which is the absorption of the carboxyl group, were measured. The absorption intensity (c1) of the above was read, and the amount of carboxyl groups (U1) and (U1) = (c1) / [(b1) / 5] with respect to one unit of the benzene ring were determined. Next, PAS was melt-pressed at 320 ° C. for 1 minute and then rapidly cooled to perform FT-IR measurement of the obtained amorphous film. Read the absorption intensity (b2) of 3066 cm-1 and the absorption intensity (c2) of 1704 cm-1, and determine the amount of carboxyl groups (U2) and (U2) = (c2) / [(b2) / 4] for one unit of the benzene ring. I asked. When the PAS was PPS, it was composed of phenylene sulfide units, so the carboxyl group content with respect to 1 g of PPS was calculated from the following formula. Carboxylic group content of PPS (μmol / g) = (U2) / (U1) /108.161 × 1000000.

[Melting point]
Using DSC7 manufactured by PerkinElmer, about 5 mg of the sample was prepared in a nitrogen atmosphere at a temperature raising / lowering rate of 20 ° C./min.
(1) After raising the temperature from 50 ° C to 340 ° C, hold at 340 ° C for 1 minute;
(2) Temperature down to 100 ° C;
(3) After raising the temperature to 340 ° C again, hold at 340 ° C for 1 minute;
(4) Lower the temperature to 100 ° C again;
The melting peak temperature observed in the step (3) was defined as the melting point (Tm).

[(A) Synthesis of PAS]
PPS-1 to 4 were synthesized in the following synthesis examples 1 to 4. Table 1 shows various physical properties of the synthesized PPS.

[Synthesis Example 1 (Synthesis of PPS-1)]
8.26 kg (70.00 mol) of 47.5% sodium hydrosulfide, 3.04 kg (73.72 mol) of 97% 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) and 5.50 kg of ion-exchanged water are charged, and the reaction vessel is gradually heated to 225 ° C. for about 3 hours while passing nitrogen under normal pressure to perform a dehydration step. Was done. When 9.82 kg of water and 0.28 kg of NMP were distilled off, heating was finished and cooling was started. The amount of residual water in the system per mol of the charged alkali metal hydrosulfide at this time was 1.01 mol including the water consumed for the hydrolysis of NMP. Moreover, since the amount of hydrogen sulfide scattered was 1.4 mol, the amount of the sulfidizing agent in the system after this dehydration step was 68.6 mol. Along with the scattering of hydrogen sulfide, 1.4 mol of sodium hydroxide was newly generated in the system.

After that, the reaction vessel was cooled to 200 ° C., 10.08 kg (68.60 mol) of p-dichlorobenzene (p-DCB), 0.376 kg (2.06 mol) of 4-chlorophthalic anhydride and 9.37 kg of NMP (NMP). After adding 94.50 mol), the reaction vessel was sealed under nitrogen gas, and the polymerization step was carried out under the following reaction conditions while stirring at 240 rpm.

The temperature was raised from 200 ° C. to 230 ° C. at 0.8 ° C./min over 38 minutes.

<Step 1> The temperature was raised from 230 ° C. to 238 ° C. at 0.6 ° C./min over 13 minutes. After the reaction was carried out at a constant temperature of 238 ° C. for 128 minutes, the temperature was raised from 238 ° C. to 245 ° C. at 0.8 ° C./min over 9 minutes. T1 was 188 minutes and T1a was 150 minutes. The conversion rate of the sulfidizing agent was 94.5%.

<Step 2> Continuing from step 1, the temperature was raised from 245 ° C. to 255 ° C. at 0.8 ° C./min over 12 minutes. The polymerization time (T2) in step 2 was 12 minutes.

Immediately after the end of step 2, the bottom valve of the autoclave was opened, the contents were flushed to a device with a stirrer, and in the device with a stirrer at 230 ° C. until 95% or more of the NMP used during polymerization was volatilized and removed. After drying for 1.5 hours, a solid containing PPS and salts was recovered. The obtained recovered product and 74 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 75 ° C. for 15 minutes, and then filtered through a filter to obtain a cake. After washing the obtained cake with ion-exchanged water at 75 ° C. for 15 minutes and filtering it three times, put the cake, 74 liters of ion-exchanged water and 0.4 kg of acetic acid into an autoclave with a stirrer, and put nitrogen inside the autoclave. After the replacement, the temperature was raised to 195 ° C. After that, the autoclave was cooled and the contents were taken out. The contents were filtered through a filter to obtain a cake. The obtained cake was dried at 120 ° C. under a nitrogen stream to obtain a dried PPS.

[Synthesis Example 2 (Synthesis of PPS-2)]
The amount of 97% sodium hydroxide charged was 3.15 kg (76.46 mol), p-DCB was 9.98 kg (67.91 mol), and 4-chlorophthalic anhydride was 0.626 kg (3.43 mol). The same operation as in Synthesis Example 1 was performed except for the above.

[Synthesis Example 3 (Synthesis of PPS-3)]
Synthesis Example 1 except that the amount of 97% sodium hydroxide charged was 2.87 kg (69.60 mol) and the p-DCB was 10.39 kg (70.66 mol), and 4-chlorophthalic anhydride was not used. The same operation as was performed.

[Synthesis Example 4 (Synthesis of PPS-4)]
The amount of 97% sodium hydroxide charged was 2.96 kg (71.66 mol), the p-DCB was 10.08 kg (68.60 mol), and p-chlorobenzoic acid was 0 instead of 4-chlorophthalic anhydride. The same operation as in Synthesis Example 1 was carried out except that 322 kg (2.06 mol) was used.

[(B) Filler having amino group and / or isocyanate group]
[Filler-1]
A sizing agent was applied to a glass fiber monofilament (filament diameter 10.5 μm) of E glass using a roller type applicator to obtain 2000 glass fiber strands to be focused. At this time, the blending amount of the sizing agent was adjusted so that the applied sizing agent was 4.5 parts by mass with respect to 100 parts by mass of the glass fiber and the amino group content contained in the obtained glass fiber was 250 μmol / g. .. As the sizing agent, an aqueous solution containing a urethane resin (HUX-290H manufactured by ADEKA), a melamine resin (MS-78-2 manufactured by Shin-Nakamura Chemical Co., Ltd.), and 3-aminopropyltriethoxysilane was used. The glass fiber strands were cut with a rotary cutter so that the average fiber length was 3 mm and dried to obtain chopped strands.

The amino group content contained in the glass fiber was calculated from hydrochloric acid titration using thymol blue as an indicator.

[Filler-2]
The same operation as for filler-1 was carried out except that the amount of the applied sizing agent was adjusted to 8.0 parts by mass and the content of amino groups contained in the glass fiber was adjusted to 450 μmol / g.

[Filler-3]
The same operation as for the filler-1 was carried out except that the applied sizing agent was adjusted to 22 parts by mass and the amino group content contained in the glass fiber was adjusted to 1200 μmol / g.

[Filler-4]
The same operation as for the filler-1 was performed except that the applied sizing agent was adjusted to 0.04 parts by mass and the amino group content contained in the glass fiber was adjusted to 2 μmol / g.

[(C) Other additives]
Alkoxysilane compound: 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM903)

[Examples 1 to 4, Comparative Examples 1 to 4]
A material other than the filler (B) was dry-blended in advance with respect to 100 parts by mass of the PAS resin composition at the ratio shown in Table 2, and then the TEX30α twin-screw extruder (L / D = 30) manufactured by Japan Steel Works, Ltd. I put it in the original part. On the other hand, the filler (B) was charged from the side feeder of the twin-screw extruder at the ratio shown in Table 2. The melt kneading was carried out under the conditions of a temperature of 320 ° C. and a rotation speed of 200 rpm. After melt-kneading, the resin composition discharged from the twin-screw extruder was pelletized with a strand cutter and then dried with hot air at 120 ° C. overnight to obtain pellets of the resin composition.

The tensile test was performed under the following conditions. Using an injection molding machine (SE75DUZ-C250) manufactured by Sumitomo Heavy Industries, Ltd., an ASTM No. 1 dumbbell test piece for a tensile test was molded at a resin temperature of 310 ° C. and a mold temperature of 130 ° C. Using the obtained test piece, the tensile strength was measured according to ASTM D638 under the conditions of a distance between fulcrums of 114 mm, a tensile speed of 10 mm / min, a temperature of 23 ° C. and a relative humidity of 50%. Further, as a long-term harsh test, a dumbbell test piece for a tensile test was immersed in 37% by mass hydrochloric acid, and the tensile strength after treatment at 23 ° C. for 1000 hours was measured under the same conditions to maintain the strength with respect to the tensile strength before immersion. The rate was measured.

The measurement results are shown in Table 2.

In Example 1 using (A) PAS having an acid anhydride group and (B) a filler having a specific amount of amino group and / or isocyanate group, high mechanical properties are maintained even after a long-term severe test. On the other hand, in Comparative Example 3 using PAS having a carboxyl group, the mechanical properties before the acid treatment are similar to those in Example 1, but the mechanical properties are significantly reduced in the long-term severe test.

Claims (6)

(A) An acid anhydride group-containing polyarylene sulfide having a melting point of more than 270 ° C. and less than 300 ° C. and (B) a filler having an amino group and / or an isocyanate group of more than 5 μmol / g and less than 1000 μmol / g are blended. (A) The acid anhydride group of the acid anhydride group-containing polyarylene sulfide having a melting point of more than 270 ° C. and less than 300 ° C. exceeds 10 μmol / g and 700 μmol / g. A polyarylene sulfide resin composition that is less than. The polyarylene sulfide resin composition according to claim 1, wherein the acid anhydride group is a polyarylene sulfide having a phthalic anhydride group. With respect to 100 parts by mass of the polyarylene sulfide resin composition, 30 to 90 parts by mass of (A) acid anhydride group-containing polyarylene sulfide and 10 to 70 parts by mass of a filler having (B) amino group and / or isocyanate group are added. The polyarylene sulfide resin composition according to claim 1 or 2, which comprises. The polyarylene sulfide resin composition according to any one of claims 1 to 3 , wherein a sizing agent is applied to the filler. The polyarylene sulfide resin composition according to claim 4, wherein the sizing agent applied to the filler is a sizing agent having an amino group and / or an isocyanate group. A molded product comprising the polyarylene sulfide resin composition according to any one of claims 1 to 5 .