JP7424181B2 - Polyphenylene sulfide resin composition and molded article - Google Patents

Description

The present invention provides a PPS resin composition that maintains high mechanical strength and rigidity, has excellent heat cycle resistance, and has excellent adhesion to an epoxy sealant, and a molded article obtained by injection molding the same. A composite molded article is provided.

Polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) has a good balance of rigidity, heat resistance, hot water resistance, chemical resistance, and moldability, so it is widely used in electrical and electronic parts, plumbing parts, automobile parts, etc. It is used. Among these, PPS resins containing elastomers are used in inverter parts for automobiles such as hybrid cars and electric cars, which require heat resistance, water vapor permeability, and heat cycle resistance.

For example, Patent Documents 1 and 3 disclose PPS resin compositions reinforced with glass fibers and blended with inorganic fillers, elastomers, bisphenol-type epoxy resins, and the like. Further, Patent Document 2 discloses a PPS resin composition reinforced with glass fiber and blended with a phenoxy resin. Further, Patent Document 4 discloses a PPS resin composition reinforced with glass fiber and blended with an elastomer and a bisphenol A type epoxy resin. Further, Patent Document 5 discloses a PPS resin composition containing an elastomer and having a defined flexural modulus.

International Publication No. 2013/141363 Japanese Patent Application Publication No. 06-329906 Japanese Patent Application Publication No. 2018-35229 Japanese Patent Application Publication No. 2017-149797 Japanese Patent Application Publication No. 2008-211000

In recent years, as the number of components installed in automobiles has increased, there has been a strong need to save space in the inverter room. For this reason, each component is becoming smaller, and the development of modules that combine multiple components instead of a single component and integrate multiple functions is progressing. As a result, each component has become thinner and more complex in shape, requiring high mechanical strength and dimensional stability.

In particular, for capacitor parts, a method is used to suppress the permeation of water vapor by placing a film capacitor inside the capacitor case, injecting a sealant such as epoxy resin into it, and curing it. In addition to the above, high adhesion with sealants such as epoxy resins is required.

Therefore, there is a need for a PPS resin composition that has excellent heat cycle resistance while maintaining high mechanical strength and rigidity, and also has excellent adhesiveness with an epoxy sealant.

However, although Patent Document 1 describes mechanical strength, epoxy adhesion, and heat cycle resistance, the effect of heat cycle resistance is not satisfactory. Although Patent Document 2 describes mechanical strength and epoxy adhesion, no specific study on heat cycle resistance was conducted, and the desired effect of heat cycle resistance was not satisfied. . Furthermore, although Patent Document 3 describes epoxy adhesive properties and heat cycle resistance, no specific studies regarding epoxy resins have been carried out, and the desired effects of epoxy adhesive properties are not satisfied. . Furthermore, although Patent Document 4 describes mechanical strength and fluidity, no specific studies have been conducted regarding epoxy adhesion or heat cycle resistance, and it does not satisfy epoxy adhesion. Ta. Furthermore, the level of glass fiber blending did not satisfy heat cycle resistance and dimensional stability. Further, in Patent Document 5, no specific studies regarding epoxy adhesiveness and heat cycle resistance were conducted, and the epoxy adhesiveness and heat cycle resistance were not satisfied.

The present invention provides a PPS resin composition that maintains high mechanical strength and rigidity, has excellent heat cycle resistance, and has excellent adhesion to an epoxy sealant, and a method of injection molding the PPS resin composition. The present invention provides a molded article and a composite molded article.

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, they have arrived at the present invention. That is, the present invention provides the following.
(1) (A-1) Linear type polyphenylene sulfide resin and (A-2) Cross-linked type polyphenylene sulfide resin (B) Bisphenol type having an epoxy equivalent of 800 to 3,500 based on 100 parts by weight of the total (A) 0.5 to 15 parts by weight of an epoxy resin, (C) 50 to 200 parts by weight of glass fiber, (D) 10 to 100 parts by weight of calcium carbonate, and (E-1) an olefin system containing no glycidyl group (common). A polyphenylene sulfide resin composition comprising a total of 5 to 15 parts by weight of (E-2) a polymer containing a glycidyl group and an olefin copolymer containing a glycidyl group.
(2) (A-1) The linear polyphenylene sulfide resin has a non-Newtonian index of 1.05 or less, (A-2) the crosslinked polyphenylene sulfide resin has a non-Newtonian index of 1.30 or more, and ( The blending ratio of A-1) linear type polyphenylene sulfide resin and (A-2) crosslinked type polyphenylene sulfide resin is (A-1):(A-2) = 50:50 to 70:30 (weight ratio ), the polyphenylene sulfide resin composition according to (1).
(3) The polyphenylene sulfide resin composition according to (1) or (2), which is for use in a molded article that is at least partially in contact with an epoxy resin for sealing.
(4) A molded article obtained by injection molding the polyphenylene sulfide resin composition according to any one of (1) to (3).
(5) A composite molded product in which the molded product according to (4) and an epoxy resin for sealing are at least partially in contact with each other.

The present invention uses a linear type polyphenylene sulfide resin and a crosslinked type polyphenylene sulfide resin in combination, and produces a bisphenol type epoxy resin with an epoxy equivalent of 800 to 3,500, glass fiber, calcium carbonate, and an olefin copolymer that does not contain glycidyl groups. , and a polyphenylene sulfide resin composition containing an olefin copolymer containing a glycidyl group has excellent heat cycle resistance while maintaining high mechanical strength and rigidity, and is highly compatible with epoxy sealants. They discovered an unknown property: excellent adhesiveness. Due to these properties, the resin composition of the present invention is useful for automobile inverter parts, and is particularly useful for capacitor parts sealed with epoxy resin.

FIG. 1(a) is a top view of a test piece whose dimensional stability was evaluated, and FIG. 1(b) is a side view thereof. FIG. 2(a) is a top view of a metal insert test piece whose heat cycle resistance was evaluated, and FIG. 2(b) is a side view thereof.

Embodiments of the present invention will be described below. In the present invention, "weight" means "mass".

Since the resin composition of the present invention requires heat resistance, it is a composition containing polyphenylene sulfide resin (hereinafter referred to as PPS resin).

(A) PPS resin used in the present invention is a polymer having a repeating unit represented by the following structural formula,

From the viewpoint of heat resistance, a polymer containing 70 mol% or more, more preferably 90 mol% or more of a polymer containing a repeating unit represented by the above structural formula is preferable. In addition, less than 30 mol% of the repeating units in the PPS resin may be composed of repeating units having the following structure.

Below, the contents of the polyhalogenated aromatic compound, sulfidating agent, polymerization solvent, molecular weight regulator, polymerization aid, and polymerization stabilizer used in the production method of the present invention will be explained.

[Polyhalogenated aromatic compound]
The polyhalogenated aromatic compound refers to a compound having two or more halogen atoms in one molecule. Specific examples include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, and hexachlorobenzene. Polyhalogenated aromatics such as chlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, 1-methoxy-2,5-dichlorobenzene Among them, p-dichlorobenzene is preferably used. It is also possible to form a copolymer by combining two or more different types of polyhalogenated aromatic compounds, but it is preferable to use a p-dihalogenated aromatic compound as the main component.

The amount of the polyhalogenated aromatic compound to be used is 0.9 to 2.0 mol, preferably 0.95 to 1.5 mol, per 1 mol of the sulfidating agent, in order to obtain a PPS resin with a viscosity suitable for processing. A more preferable range is 1.005 to 1.2 moles.

[Sulfiding agent]
Sulfidating agents include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.

Specific examples of alkali metal sulfides include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and mixtures of two or more of these, with sodium sulfide being preferably used. These alkali metal sulfides can be used as hydrates or aqueous mixtures or in anhydrous form.

Specific examples of alkali metal bisulfides include sodium bisulfide, potassium bisulfide, lithium bisulfide, rubidium bisulfide, cesium bisulfide, and mixtures of two or more of these. Among them, sodium bisulfide is preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures or in anhydrous form.

Furthermore, a sulfidating agent prepared in situ in the reaction system from an alkali metal hydrosulfide and an alkali metal hydroxide can also be used. Alternatively, a sulfidating agent can be prepared from an alkali metal hydrosulfide and an alkali metal hydroxide, and this can be transferred to a polymerization tank for use.

Alternatively, a sulfidating agent prepared in situ in a reaction system from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide can also be used. Alternatively, a sulfidating agent may be prepared from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide, and this may be transferred to a polymerization tank for use.

The amount of sulfidating agent charged means the amount remaining after subtracting the loss from the actual amount of sulfidating agent, if a portion of the sulfidating agent is lost before the start of the polymerization reaction due to dehydration or the like.

In addition, it is also possible to use an alkali metal hydroxide and/or an alkaline earth metal hydroxide together with the sulfidating agent. Preferred examples of alkali metal hydroxides include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and mixtures of two or more of these. Specific examples of metal hydroxides include calcium hydroxide, magnesium hydroxide, strontium hydroxide, barium hydroxide, etc. Among them, sodium hydroxide is preferably used.

When an alkali metal hydrosulfide is used as a sulfidating agent, it is particularly preferable to use an alkali metal hydroxide at the same time, and the amount used is 0.95 to 1. For example, the amount is 20 mol, preferably 1.00 to 1.15 mol, and more preferably 1.005 to 1.100 mol.

[Polymerization solvent]
It is preferable to use an organic polar solvent 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, and 1,3-dimethyl-2-imidazolidone. Examples include aprotic organic solvents such as non-, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, dimethylsulfone, tetramethylene sulfoxide, and mixtures thereof. It is preferably used because of its high reaction stability. Among these, N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) is particularly preferably used.

The amount of the organic polar solvent used is selected in the range of 2.0 to 10 moles, preferably 2.25 to 6.0 moles, more preferably 2.5 to 5.5 moles per mole of the sulfidating agent. .

[Molecular weight regulator]
A monohalogenated compound (not necessarily an aromatic compound) is used in combination with the above-mentioned polyhalogenated aromatic compound in order to form the ends of the PPS resin to be produced or to adjust the polymerization reaction and molecular weight. be able to.

[Polymerization aid]
It is also one of the preferred embodiments to use a polymerization aid in order to obtain a PPS resin with a relatively high degree of polymerization in a shorter time. The term "polymerization aid" as used herein means a substance that has the effect of increasing the viscosity of the resulting PPS resin. Specific examples of such polymerization aids include organic carboxylic acid metal salts, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates, and Examples include alkaline earth metal phosphates. These may be used alone or in combination of two or more. Among these, organic carboxylic acid metal salts and/or water are preferably used.

The organic carboxylic acid metal salt has the general formula R(COOM) _n (wherein R is an alkyl group, cycloalkyl group, aryl group, alkylaryl group, or arylalkyl group having 1 to 20 carbon atoms. M is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium; n is an integer from 1 to 3). The organic carboxylic acid metal salt can also be used as a hydrate, anhydride or an aqueous solution. Specific examples of organic carboxylic acid metal salts include lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluate, and mixtures thereof. can be mentioned.

Organic carboxylic acid metal salts are prepared by adding approximately equal chemical equivalents of an organic acid and one or more compounds selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, and alkali metal bicarbonates and reacting them. It may be formed by. Among the organic carboxylic acid metal salts mentioned above, lithium salts have high solubility in the reaction system and have a large auxiliary effect, but are expensive, while potassium, rubidium, and cesium salts have insufficient solubility in the reaction system. Therefore, sodium acetate, which is inexpensive and has appropriate solubility in the polymerization system, is most preferably used.

When using these polymerization aids, the amount used is usually in the range of 0.01 mol to 0.7 mol per 1 mol of the charged alkali metal sulfide, and in the sense of obtaining a higher degree of polymerization, the amount used is 0.1 to 0.7 mol. A range of 0.6 mol is preferred, and a range of 0.2 to 0.5 mol is more preferred.

Furthermore, using water as a polymerization aid is one of the effective means for obtaining a resin composition with a highly balanced fluidity and high toughness. In that case, the amount added is usually in the range of 0.5 to 15 moles per mole of the charged alkali metal sulfide, and preferably in the range of 0.6 to 10 moles in order to obtain a higher degree of polymerization. The range of 1 to 5 moles is more preferable.

There is no particular specification regarding the timing of addition of these polymerization aids, and they may be added at any time during the pre-process described below, at the start of polymerization, or during polymerization, or may be added in multiple portions. When an organic carboxylic acid metal salt is used as a polymerization aid, it is more preferable to add it simultaneously at the start of the previous step or at the start of the polymerization because addition is easy. When water is used as a polymerization aid, it is effective to add it during the polymerization reaction after charging the polyhalogenated aromatic compound.

[Polymerization stabilizer]
A polymerization stabilizer can also be used to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to stabilizing the polymerization reaction system and suppresses undesirable side reactions. One measure of side reactions is the production of thiophenol, and the production of thiophenol can be suppressed by adding a polymerization stabilizer. Specific examples of polymerization stabilizers include compounds such as alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, and alkaline earth metal carbonates. Among these, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferred. The above-mentioned organic carboxylic acid metal salts also act as polymerization stabilizers and are therefore included in the polymerization stabilizers used in the present invention. Furthermore, when using an alkali metal hydrosulfide as a sulfidating agent, it is particularly preferable to use an alkali metal hydroxide at the same time. Oxides can also serve as polymerization stabilizers.

These polymerization stabilizers can be used alone or in combination of two or more. The polymerization stabilizer is used in a proportion of usually 0.02 to 0.2 mol, preferably 0.03 to 0.1 mol, more preferably 0.04 to 0.09 mol, per 1 mol of the charged alkali metal sulfide. It is preferable to use it in If this proportion is too small, the stabilizing effect will be insufficient, and if it is too large, it will be economically disadvantageous, and the polymer yield will tend to decrease.

There is no particular specification as to when to add the polymerization stabilizer; it may be added at any time during the pre-process, at the start of polymerization, or during polymerization, which will be described later.Also, it may be added in multiple parts, but It is more preferable to add it simultaneously at the start of the process or at the start of polymerization because it is easy to add.

[pre-process]
The sulfidating agent is usually used in the form of a hydrate, but before adding the polyhalogenated aromatic compound, the mixture containing the organic polar solvent and the sulfidating agent is heated to remove excess water from the system. It is preferable to remove it immediately. In addition, if too much water is removed by this operation, it is preferable to replenish the shortage by adding water.

Furthermore, as mentioned above, an alkali metal sulfide prepared from an alkali metal hydrosulfide and an alkali metal hydroxide in situ in the reaction system or in a tank different from the polymerization tank is also used as the sulfidating agent. be able to. Although there are no particular limitations on this method, it is preferable to add an alkali metal hydrosulfide and an alkali metal hydroxide to an organic polar solvent under an inert gas atmosphere at a temperature ranging from room temperature to 150°C, preferably from room temperature to 100°C. In addition, there is a method in which the temperature is raised to at least 150°C, preferably 180 to 260°C, under normal pressure or reduced pressure, and water is distilled off. A polymerization aid may be added at this stage. Further, in order to promote distillation of water, toluene or the like may be added to carry out the reaction.

In the polymerization reaction, the amount of water in the polymerization system is preferably 0.5 to 10.0 moles per mole of the charged sulfidating agent. Here, the amount of water within the polymerization system is the amount obtained by subtracting the amount of water removed from the polymerization system from the amount of water charged into the polymerization system. Further, the water to be charged may be in any form such as water, an aqueous solution, or crystal water.

[Polymerization reaction process]
Preferably, the PPS resin is produced by reacting a sulfidating agent and a polyhalogenated aromatic compound in an organic polar solvent within a temperature range of 200 to 290°C.

When starting the polymerization reaction step, the sulfidating agent and the polyhalogenated aromatic compound are added to the organic polar solvent, desirably under an inert gas atmosphere at a temperature range of room temperature to 220°C, preferably 100 to 220°C. A polymerization aid may be added at this stage. There is no particular restriction on the order in which these raw materials are added, and they may be added at the same time.

The temperature of such a mixture is generally raised to a range of 200°C to 290°C. Although there is no particular restriction on the heating rate, a rate of 0.01 to 5°C/min is usually selected, and a range of 0.1 to 3°C/min is more preferable.

Generally, the temperature is finally raised to 250 to 290°C, and the reaction is carried out at that temperature for usually 0.25 to 50 hours, preferably 0.5 to 20 hours.

Before reaching the final temperature, for example, a method of reacting at 200° C. to 260° C. for a certain period of time and then raising the temperature to 270° C. to 290° C. is effective in obtaining a higher degree of polymerization. At this time, the reaction time at 200° C. to 260° C. is usually selected in the range of 0.25 to 20 hours, preferably in the range of 0.25 to 10 hours.

In addition, in order to obtain a polymer with a higher degree of polymerization, it is effective to perform the polymerization in multiple stages. When performing polymerization in multiple stages, it is effective to proceed to the next stage when the conversion rate of the polyhalogenated aromatic compound in the system at 245 ° C reaches 40 mol% or more, preferably 60 mol%. It is.

[Collection process]
After the polymerization is completed, solid matter is recovered from the polymerization reaction product including the polymer, solvent, and the like.

A preferable recovery method for PPS resin is to perform it under quenching conditions, and one preferable recovery method is a flash method. The flash method involves flashing the polymerization reaction product from a high temperature and high pressure state (usually above 250°C, above 8 kg/ ^cm2 ) into an atmosphere of normal pressure or reduced pressure, and simultaneously recovering the solvent and converting the polymer into powder. This is a recovery method, and the term "flash" here means spouting out the polymerization reaction product from a nozzle. Specific examples of the flashing atmosphere include, for example, nitrogen or water vapor at normal pressure, and the temperature is usually selected within the range of 150°C to 250°C.

The flash method is an economically efficient recovery method because solid matter can be recovered simultaneously with solvent recovery and the recovery time can be relatively short. In this recovery method, ionic compounds typified by Na and organic low-polymerization products (oligomers) tend to be incorporated into the polymer during the solidification process.

However, the method for recovering the PPS resin used in the production method of the present invention is not limited to the flash method, but any method that satisfies the requirements of the present invention may include slow cooling to recover particulate polymer. (quench method) may also be used. However, in view of economic efficiency, it is more preferable to use PPS resin recovered by the flash method.

[Post-treatment process (acid treatment)]
In the present invention, as the PPS resin, for example, it is preferable to acid-treat the PPS resin obtained through the above polymerization reaction step and recovery step.

The acid used in the acid treatment in the present invention is not particularly limited as long as it does not have the effect of decomposing the PPS resin, and examples include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propylic acid, among others. Acetic acid and hydrochloric acid are more preferably used, but those that decompose and deteriorate the PPS resin, such as nitric acid, are not preferred.

When using an aqueous acid solution, the water is preferably distilled water or deionized water. The pH of the acid aqueous solution is preferably 1 to 7, more preferably 2 to 4. If the pH is higher than 7, the metal content of the PPS resin will increase, which is undesirable, and if the pH is lower than 1, the volatile components of the PPS resin will increase, which is not preferred.

As for the acid treatment method, it is preferable to immerse the PPS resin in an acid or an aqueous solution of an acid, and it is also possible to stir and heat the resin as necessary. The heating temperature is preferably 80 to 250°C, more preferably 120 to 200°C, even more preferably 150 to 200°C. If it is less than 80°C, the acid treatment effect will be small and the metal content will increase, and if it exceeds 250°C, the pressure will become too high, which is not preferable from a safety standpoint. Further, when the PPS resin is immersed in an aqueous acid solution, the pH thereof is preferably less than 8, more preferably 2 to 8. If the pH is higher than 8, the metal content of the resulting PPS resin will increase, which is not preferable.

The acid treatment time is preferably a time when the reaction between the PPS resin and the acid is sufficiently equilibrated, and when the treatment is performed at 80°C, it is preferably 2 to 24 hours, and when the treatment is performed at 200°C, it is 0.01 to 5 hours. preferable.

Regarding the ratio of PPS resin and acid or acid aqueous solution in the acid treatment, it is preferable to perform the treatment while the PPS resin is sufficiently immersed in the acid or acid aqueous solution. The aqueous solution is preferably 0.5 to 500 L, more preferably 1 to 100 L, even more preferably 2.5 to 20 L. If the amount of acid or acid aqueous solution is less than 0.5 L per 500 g of PPS resin, the PPS resin will not be sufficiently immersed in the aqueous solution, resulting in poor cleaning, and the metal content of the PPS resin will increase, which is not preferable. Furthermore, if the amount of the acid or aqueous acid solution exceeds 500 L per 500 g of PPS resin, the amount of solution relative to the PPS resin will be greatly excessive, which will significantly reduce production efficiency, which is not preferable.

These acid treatments are performed by adding a predetermined amount of PPS resin to a predetermined amount of water and acid, and heating and stirring the resin in a pressure vessel, or by continuously performing acid treatment. A simple method for separating the aqueous solution and PPS resin from the treated solution after acid treatment is filtration using a sieve or filter, and examples include methods such as natural filtration, pressure filtration, vacuum filtration, and centrifugal filtration. In order to remove residual acids and impurities on the surface of the PPS resin separated from the treatment liquid, it is preferable to wash the resin several times with water or hot water. Examples of cleaning methods include filtering while pouring water onto the PPS resin on the filtration device, and separating the aqueous solution and PPS resin by adding the separated PPS resin to pre-prepared water and filtering it again. can. The water used for washing is preferably distilled water or deionized water. It is thought that the terminal structure of PPS resin treated with acid changes in this way, but it is difficult to express the structure of PPS resin obtained by acid treatment with a general formula, and it is also difficult to specify it by characteristics. Therefore, it can only be identified through the process (acid treatment) used to obtain PPS resin.

[Post-treatment process (hot water treatment)]
In the present invention, it is preferable to perform hot water treatment before the acid treatment step, and the method is as follows. The water used for the hydrothermal treatment in the present invention is preferably distilled water or deionized water. The hot water treatment temperature is preferably 80 to 250°C, more preferably 120 to 200°C, even more preferably 150 to 200°C. If the temperature is less than 80°C, the effect of hot water treatment will be small and the amount of volatilized gas will increase, and if it exceeds 250°C, the pressure will become too high, which is not preferable from a safety standpoint.

The time for hot water treatment is preferably a time that allows sufficient extraction treatment with PPS resin and hot water, preferably 2 to 24 hours when processing at 80°C, and 0.01 to 5 hours when processing at 200°C. is preferred.

The ratio of PPS resin and water in the hot water treatment is preferably 0.5 to 500 L of water, preferably 1 to 100 L of water per 500 g of PPS resin. is more preferable, and 2.5 to 20 L is even more preferable. If the amount of water is less than 0.5 L per 500 g of PPS resin, the PPS resin will not be sufficiently immersed in water, resulting in poor cleaning, and the amount of evaporated gas will increase, which is not preferable. Furthermore, if the amount of water exceeds 500 L relative to 500 g of PPS resin, the amount of water relative to the PPS resin will be excessive and the production efficiency will drop significantly, which is not preferable.

There are no particular restrictions on these hot water treatment operations, and methods include adding a predetermined amount of PPS resin to a predetermined amount of water and heating and stirring it in a pressure vessel, or continuously performing hot water treatment. . There are no particular restrictions on the method for separating the aqueous solution and PPS resin from the treated solution after hot water treatment, but filtration using a sieve or filter is simple, and methods such as natural filtration, pressure filtration, vacuum filtration, centrifugal filtration, etc. can be exemplified. In order to remove impurities remaining on the surface of the PPS resin separated from the treatment liquid, it is preferable to wash the resin several times with water or warm water. There are no particular restrictions on the cleaning method, but the aqueous solution and PPS resin can be washed by filtering while pouring water over the PPS resin on the filtration device, or by pouring the separated PPS resin into pre-prepared water and filtering it again. An example of a method for separating the The water used for washing is preferably distilled water or deionized water.

Further, since it is undesirable that the PPS terminal groups are decomposed during these acid treatments and hot water treatments, it is desirable to carry out the acid treatments and hot water treatments under an inert atmosphere. Examples of the inert atmosphere include nitrogen, helium, argon, etc., and a nitrogen atmosphere is preferable from the viewpoint of economy.

[Post-treatment process (cleaning with organic solvent)]
The present invention may include a step of washing the PPS resin with an organic solvent before the step of treating the PPS resin with an acid or hot water, and the method thereof is as follows. The organic solvent used for cleaning the PPS resin in the present invention is not particularly limited as long as it does not have the effect of decomposing the PPS resin. For example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, 1,3 - Nitrogen-containing polar solvents such as dimethylimidazolidinone, hexamethylphosphorusamide, and piperazinone; sulfoxide/sulfone solvents such as dimethyl sulfoxide, dimethyl sulfone, and sulfolane; ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, and acetophenone; Ether solvents such as dimethyl ether, dipropyl ether, dioxane, and tetrahydrofuran; halogen solvents such as chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, tetrachloroethane, perchloroethane, and chlorobenzene. , alcohol/phenolic solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene. Can be mentioned. Among these organic solvents, N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform, and the like are particularly preferred. Further, these organic solvents may be used alone or in combination of two or more.

As a method for washing with an organic solvent, there is a method such as immersing the PPS resin in an organic solvent, and it is also possible to stir or heat the resin as needed. There are no particular restrictions on the cleaning temperature when cleaning PPS resin with an organic solvent, and any temperature from room temperature to about 300°C can be selected. Although the higher the cleaning temperature, the higher the cleaning efficiency tends to be, usually a cleaning temperature of room temperature to 150° C. can be sufficiently effective. It is also possible to wash under pressure in a pressure vessel at a temperature above the boiling point of the organic solvent. Furthermore, there is no particular restriction on the cleaning time. Although it depends on the cleaning conditions, in the case of batch cleaning, sufficient effects can usually be obtained by cleaning for 5 minutes or more. It is also possible to wash continuously.

These acid treatment, hot water treatment, or washing with an organic solvent can also be performed in an appropriate combination.

[Heat treatment process]
In the present invention, by further heat-treating the PPS resin after the above post-treatment process, the molecular chains are crosslinked with each other, and a PPS resin with high mechanical strength and excellent dimensional stability can be obtained. . The PPS resin that has undergone such a heat treatment process corresponds to (A-2) crosslinked PPS resin in the present invention. The heat treatment process will be specifically explained below.

In the present invention, heat treatment can be performed in order to obtain a PPS resin with high mechanical strength. However, excessive heat treatment may cause a decrease in melt fluidity and an increase in gelled substances in the resin, resulting in non-filling during molding. This is not desirable as it may cause However, if the heat treatment is too light, the effect of reducing volatile components will be small, the strength of the resin will decrease, and the antifreeze resistance will also tend to decrease. According to the heat treatment of the present invention, it is possible to obtain a PPS resin with improved mechanical strength while suppressing the generation of gelled substances without impairing melt fluidity.

The heat treatment may be performed in an atmosphere with a high oxygen concentration or an atmosphere with a low oxygen concentration, as long as the heat treatment temperature and heat treatment time are set within a specific range.

The conditions for the high oxygen concentration atmosphere are preferably such that the oxygen concentration exceeds 2% by volume, the heat treatment temperature is preferably 160 to 270° C., and the heat treatment time is preferably 0.1 to 17 hours. However, although the rate of reduction of volatile components is rapid under conditions of high oxygen concentration, oxidative crosslinking also proceeds rapidly, making it easier to generate gelled products. Therefore, it is generally preferable to perform the heat treatment at a low temperature for a long time or at a high temperature for a short time. Specific conditions for heat treatment at low temperature and for a long time are preferably 1 hour or more and 17 hours or less at 160° C. or more and 210° C. or less, and more preferably 1 hour or more and 10 hours or less at 170° C. or more and 200° C. or less. Even if heat treatment is performed at a temperature lower than 160° C., the effect of reducing volatile components is small and the effect of improving mechanical strength is small. Furthermore, even at low temperatures, under conditions where the oxygen concentration exceeds 2% by volume, if the heat treatment time exceeds 17 hours, oxidative crosslinking progresses and gelled products are likely to occur. Specific conditions for heat treatment at high temperature and short time are preferably 0.1 hour or more and less than 1 hour at more than 210 ° C. and 270 ° C. or less, more preferably 0.2 to 0.8 hours at 220 ° C. or more and 260 ° C. or less. . When the heat treatment temperature exceeds 270°C, oxidative crosslinking rapidly progresses and gelled products are likely to occur. Furthermore, even at high temperatures, if the heat treatment time is less than 0.1 hour, the effect of reducing volatile components is small and the effect of improving mechanical strength is small.

The conditions for the low oxygen concentration atmosphere are preferably such that the oxygen concentration is 2% by volume or less, the heat treatment temperature is preferably 210 to 270° C., and the heat treatment time is preferably 0.2 to 50 hours. If the oxygen concentration is low, the effect of reducing volatile components tends to be small, so it is generally preferable to perform the heat treatment at a high temperature and for a long time, and it is preferable to perform the heat treatment at a heat treatment temperature of 220 ° C to 260 ° C for 2 to 20 hours. More preferred. If the heat treatment time is less than 210°C, the volatile components will not be reduced and the effect of improving mechanical strength will be small, and if the heat treatment time is more than 50 hours, productivity will decrease.

The heating device for the heat treatment of the present invention may be a normal hot air dryer, a rotating type or a heating device with stirring blades, but for efficient and more uniform treatment, a rotating It is more preferable to use a heating device with a type or stirring blade, and examples include a paddle dryer, a fluidized bed dryer, a KID dryer, a steam tube dryer, an inclined disk dryer, a hopper dryer, a vertical stirring dryer, etc. . Among these, paddle dryers, fluidized bed dryers, and KID dryers are preferred for uniform and efficient heating. In order to adjust the oxygen concentration during heat treatment, there is no problem in mixing an oxidizing gas such as oxygen, air, or ozone with a non-oxidizing inert gas such as nitrogen, argon, helium, or water vapor. As long as the heat treatment can be performed within the heating device, there is no particular restriction on introducing the oxidizing gas or inert gas from the top, bottom, or side of the heating device, but a simpler method is to One example is introducing gas from the top. Additionally, the oxidizing gas and inert gas may be mixed before introducing the heating device and then introduced into the device, or the oxidizing gas and inert gas may be mixed separately from different locations in the heating device. .

Although it is thought that the structure of PPS resin changes through the heat treatment process, the PPS resin obtained through heat treatment has a complex and diverse structure. There are circumstances that make it impractical to specify the structure of By going through the heat treatment step, volatile matter and moisture contained in the PPS resin can be removed, and a PPS resin that has excellent mechanical strength, weld strength, and dimensional stability can be obtained.

The melt flow rate (hereinafter sometimes abbreviated as MFR) of the PPS resin obtained through the above polymerization reaction step, recovery step, preferably post-treatment step, and heat treatment step may be 1000 g/10 minutes or less. It is preferably 700 g/10 minutes or less, more preferably 500 g/10 minutes or less. When the MFR exceeds 1000 g/10 minutes, the degree of polymerization is too low, resulting in a decrease in mechanical strength. The lower limit is preferably greater than 80 g/10 minutes from the viewpoint of moldability, and preferably 100 g/10 minutes or more. Here, MFR is a value measured according to ASTM-D1238-70 at a measurement temperature of 315.5° C. and a load of 5000 g.

The PPS resin used in the present invention needs to be a combination of (A-1) a linear type PPS resin and (A-2) a crosslinked type PPS resin. (A-1) By using a linear type PPS resin, epoxy adhesion can be improved, and (A-2) By using a crosslinked type PPS resin, dimensional stability can be improved. be able to. In particular, by blending (A-1) linear type PPS resin and (A-2) crosslinked type PPS resin in a weight ratio of 50:50 to 70:30, epoxy adhesion and size can be improved. It becomes possible to achieve both stability and stability.

The non-Newtonian index is determined by measuring the shear rate and shear stress using a capillograph at 300°C, with the length of the orifice as "L" and the diameter as "D", and L/D = 40, and is calculated using the following formula (1). It can be calculated using
SR=K・SS ^N (1)
(Here, N is a non-Newtonian index, SR is shear rate (sec ^-1 ), SS is shear stress (dyne/cm ² ), and K is a constant)

The non-Newtonian index of PPS resin is an index indicating the viscoelastic properties of a fluid that does not correspond to a Newtonian fluid. The higher the molecular weight of the polymer obtained by the above-mentioned polymerization method, the larger the polymer tends to be. The method of heating in a heating container at a predetermined temperature under a mixed gas atmosphere of an inert gas until the desired viscosity is obtained, that is, the so-called oxidative crosslinking method, increases the size and takes a long time for oxidative crosslinking. It tends to become larger when the temperature is high.

In the present invention, it is preferable that the non-Newtonian index of the linear PPS resin (A-1) is 1.05 or less. By setting it as this range, excellent epoxy adhesiveness can be obtained. The lower limit is preferably 0.95 or more from the viewpoint of mechanical strength. Further, the non-Newtonian index of the crosslinked PPS resin (A-2) is preferably 1.30 or more. By setting it as this range, excellent dimensional stability can be obtained. Preferably it is 1.35 or more, more preferably 1.40 or more. The upper limit is preferably 1.70 or less from the viewpoint of fluidity. Methods for bringing the non-Newtonian index of the PPS resin into the preferred range described above are not limited as long as such a PPS resin can be obtained, but include, for example, an atmosphere of an oxidizing gas or mixed gas after polymerization, as described above. Examples include a method of heating under the

The PPS resin composition of the present invention contains (B) a bisphenol type epoxy resin having an epoxy equivalent of 800 to 3,500.

The blending amount of (B) bisphenol type epoxy resin having an epoxy equivalent of 800 to 3500 in the PPS resin composition of the present invention is as follows: (A-1) linear type PPS resin and (A-2) crosslinked type PPS resin. For a total of 100 parts by weight (hereinafter sometimes abbreviated as (A) PPS resin 100 parts by weight), (B) a bisphenol type epoxy resin having an epoxy equivalent of 800 to 3,500 is 0.5 to 15 parts by weight. The above blending amount is necessary in order to obtain excellent epoxy adhesive strength.

If the amount of (B) bisphenol type epoxy resin having an epoxy equivalent of 800 to 3,500 is less than 0.5 parts per 100 parts by weight of (A) PPS resin, it is not preferable because sufficient epoxy adhesive strength cannot be obtained. (B) If the bisphenol type epoxy resin with an epoxy equivalent of 800 to 3,500 exceeds 15 parts by weight, the melt fluidity of the composition will increase, appropriate moldability will not be obtained, and the amount of gas generated will increase. This is undesirable because it causes an increase in mold contamination.

Examples of the bisphenol type epoxy resin (B) having an epoxy equivalent of 800 to 3500 include bisphenol A, bisphenol F, bisphenol S, bisphenol AF, and bisphenol AD type epoxy resins, and among them, bisphenol A type epoxy resin. is more preferable.

Further, the epoxy equivalent of such an epoxy resin is preferably 800 to 3,500, more preferably 2,000 to 3,500. If it is less than 800, it is not preferable because the viscosity increases during molding or the amount of gas generated increases. Moreover, if it exceeds 3500, the epoxy adhesiveness deteriorates, which is not preferable. The lower limit of the epoxy equivalent is preferably 1,500 or more, more preferably 2,000 or more from the viewpoint of achieving both moldability and adhesiveness. Further, the upper limit is preferably 3,400 or less, more preferably 3,300 or less.

The PPS resin composition of the present invention contains (C) glass fiber.

The blending amount of (C) glass fiber in the PPS resin composition of the present invention is 50 to 200 parts by weight based on 100 parts by weight of (A) PPS resin. The above blending amount is necessary in order to obtain excellent mechanical strength, weld strength, and dimensional accuracy.

If the amount of (C) glass fiber is less than 50 parts by weight based on 100 parts by weight of (A) PPS resin, it is not preferable because appropriate strength as a composition cannot be obtained. (C) If the number of glass fibers exceeds 200, it is not preferable because the melt flowability of the composition decreases, appropriate moldability cannot be obtained, and mechanical strength cannot be obtained.

Specific examples of such glass fiber (C) include glass fiber, glass flat fiber, irregular cross-section glass fiber, glass cut fiber, flat glass fiber, etc., and two or more types of these can also be used in combination. be. Among them, glass fiber is preferred. Furthermore, by pre-treating these glass fibers with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, or an epoxy compound, better mechanical strength can be obtained. It is preferable in this sense, and it is particularly preferable to treat with a sizing agent containing an epoxy group.

The PPS resin composition of the present invention contains (D) calcium carbonate.

The blending amount of (D) calcium carbonate in the PPS resin composition of the present invention is 10 to 100 parts by weight of (D) calcium carbonate per 100 parts by weight of (A) PPS resin. The above blending amount is necessary in order to obtain excellent dimensional accuracy.

If (D) calcium carbonate is less than 10 parts by weight with respect to 100 parts by weight of (A) PPS resin, it is not preferable because appropriate dimensional accuracy as a composition cannot be obtained. (D) If calcium carbonate exceeds 100, it is not preferable because the melt flowability of the composition decreases, appropriate moldability cannot be obtained, and mechanical strength cannot be obtained.

The PPS resin composition of the present invention contains (E) an olefin copolymer.

First, (E-1) olefin-based (co)polymers that do not contain glycidyl groups are α-olefins such as ethylene, propylene, butene-1, pentene-1, octene-1, 4-methylpentene-1, isobutylene, etc. Alternatively, examples include polymers or copolymers obtained by polymerizing two or more types, and compounds that do not contain glycidyl groups.

(E-1) The blending amount of the olefin-based (co)polymer containing no functional group is preferably 2 to 9 parts by weight, particularly preferably 3 to 8 parts by weight, based on 100 parts by weight of (A) PPS resin. . When 2 parts by weight or more is blended, heat cycle resistance is dramatically improved compared to when the amount is not blended. Moreover, when it is added in an amount exceeding 9 parts by weight, heat cycle resistance is improved, but mold fouling resistance is significantly deteriorated.

Next, (E-2) an olefin copolymer containing a glycidyl group can be obtained by introducing a monomer component having a glycidyl group (functional group-containing component) into an olefin (co)polymer; Examples of the functional group-containing component include monomers containing glycidyl groups such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, and glycidyl citraconate. Types of olefin-based (co)polymers include α-olefins such as ethylene, propylene, butene-1, pentene-1, octene-1, 4-methylpentene-1, isobutylene, and other α-olefins or polymers of two or more. The resulting (co)polymers contain α,β-unsaturations such as α-olefins and acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc. There are copolymers with acids and their alkyl esters, and specific examples include ethylene/propylene copolymers (“/” represents copolymerization, the same applies hereinafter), ethylene/butene-1 copolymers, and ethylene/propylene copolymers. Hexene-1, ethylene/octene-1, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/butyl acrylate copolymer, ethylene/methyl methacrylate copolymer, ethylene/methacrylic acid Examples include ethyl copolymer and ethylene/butyl methacrylate copolymer.

There are no particular restrictions on the method of introducing functional group-containing components into these olefin (co)polymers, and when copolymerizing the same olefin (co)polymer as used as the olefin (co)polymer, Methods such as copolymerization with an olefin copolymer or graft introduction using a radical initiator into an olefin copolymer can be used. The amount of the functional group-containing component introduced is suitably within the range of 0.001 to 40 mol%, preferably 0.01 to 35 mol%, based on the total monomers constituting the modified olefin copolymer. be. A specific example of an olefin copolymer obtained by introducing a monomer component having a glycidyl group into a particularly useful olefin donor polymer is ethylene/propylene-g-glycidyl methacrylate copolymer ("g" is a grafted polymer). ), ethylene/butene-1-g-glycidyl methacrylate copolymer, ethylene/glycidyl acrylate copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/methyl acrylate/glycidyl methacrylate copolymer Examples include polymers, ethylene/methyl methacrylate/glycidyl methacrylate copolymers, and the like.

(E-2) The functional group-containing olefin copolymer is preferably 2 to 9 parts by weight, particularly preferably 3 to 8 parts by weight, based on 100 parts by weight of the (A) PPS resin. When the amount is 2 parts by weight or more, it is possible to suppress the occurrence of cracks during heat cycling, and when it is 9 parts by weight or less, it is possible to suppress the deposits that adhere to the mold during injection molding, and the generation of gas due to decomposition is suppressed, thereby improving the quality of the product. A good appearance can be maintained.

The (E-1) olefin-based (co)polymer not containing a glycidyl group and (E-2) the olefin-based copolymer containing a glycidyl group are blended in the above-mentioned amounts, but (A) The total amount of components (E-1) and (E-2) relative to 100 parts by weight of the PPS resin needs to be 5 to 15 parts by weight. With such a blending amount, a composition that can achieve both heat cycle resistance and dimensional stability can be obtained.

The PPS resin composition of the present invention includes (F) at least one functional group selected from epoxy groups, amino groups, isocyanate groups, hydroxyl groups, mercapto groups, and ureido groups, within a range that does not impair the effects of the present invention. An alkoxysilane compound having the following (hereinafter sometimes referred to as (F) silane compound) may be blended.

The amount of the silane compound (F) blended in the PPS resin composition of the present invention is preferably 0.1 to 3 parts by weight based on 100 parts by weight of the PPS resin (A). With such a blending amount, excellent fluidity and weld strength can be achieved at the same time.

If the amount of the silane compound (F) is 0.1 part by weight or more with respect to 100 parts by weight of the PPS resin (A), it is not preferable because appropriate strength as a composition cannot be obtained. When the amount of the silane compound (F) is 3 parts by weight or less, it is preferable because the melt fluidity of the composition can be maintained and appropriate moldability can be obtained.

Specifically, the silane compound (F) includes γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. Epoxy group-containing alkoxysilane compounds, γ-mercaptopropyltrimethoxysilane, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-( ureido group-containing alkoxysilane compounds such as 2-ureidoethyl)aminopropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, γ-isocyanatepropylmethyldiethoxy Silane, isocyanate group-containing alkoxysilane compounds such as γ-isocyanatepropylethyldimethoxysilane, γ-isocyanatepropylethyldiethoxysilane, γ-isocyanatepropyltrichlorosilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ- Amino group-containing alkoxysilane compounds such as (2-aminoethyl)aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-hydroxypropyltrimethoxysilane, γ-hydroxypropyltrimethoxysilane, etc. Examples include hydroxyl group-containing alkoxysilane compounds such as ethoxysilane. Among these, alkoxysilanes having an epoxy group, an amino group, an isocyanate group, or a hydroxyl group are suitable for obtaining excellent weld strength.

Furthermore, the PPS resin composition of the present invention may contain other resins other than (A) PPS resin, (B) bisphenol A epoxy resin, and (E) olefin copolymer within a range that does not impair the effects of the present invention. You may also use a blend of these. Such blendable resins are not particularly limited, but specific examples include polyamide resins such as nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, aromatic nylon, polyethylene terephthalate, polybutylene terephthalate, Polyester resins such as polycyclohexyl dimethylene terephthalate and polynaphthalene terephthalate, polyamideimide, polyacetal, polyimide, polyetherimide, polyethersulfone, modified polyphenylene ether resin, polysulfone resin, polyallylsulfone resin, polyketone resin, polyarylate resin, Examples include liquid crystal polymer, polyetherketone resin, polythioetherketone resin, polyetheretherketone resin, polytetrafluoride polyethylene resin, and the like.

The PPS resin composition of the present invention may contain other components such as antioxidants and heat stabilizers (hindered phenol type, hydroquinone type, phosphorus type, phosphite type, amine type) to the extent that the effects of the present invention are not impaired. weathering agents (resorcinol-based, salicylate-based, benzotriazole-based, benzophenone-based, hindered amine-based, etc.), mold release agents and lubricants (montanic acid and its metal salts, its esters, its (half ester, stearyl alcohol, stearamide, stearate, bisurea, polyethylene wax, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black for coloring, etc.), dyes (nigrosine, etc.), crystal nucleating agents (talc, silica, kaolin, clay) (inorganic crystal nucleating agents or organic crystal nucleating agents such as cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agents, etc.), flame retardants (e.g. red phosphorus, phosphoric acid esters, melamine cyanurate, hydroxylated magnesium, hydroxides such as aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin, or combinations of these brominated flame retardants with antimony trioxide, etc.), heat. Usual additives such as stabilizers, lubricants such as calcium stearate, aluminum stearate, lithium stearate, strength enhancers such as novolac phenolic epoxy resins, cresol novolak epoxy resins, UV inhibitors, colorants, flame retardants and blowing agents. Additives can be added. Among these, polyethylene as a mold release agent is preferred from the viewpoint of antifreeze resistance, and amide compounds are particularly preferred from the viewpoint of suppressing mold deposits in addition to antifreeze resistance. The type of crystal nucleating agent is not particularly limited, but examples include inorganic crystal nucleating agents and organic crystal nucleating agents, with organic crystal nucleating agents being particularly preferred from the viewpoint of antifreeze resistance and weld strength. Organic crystal nucleating agents used in the present invention include sorbitol compounds and their metal salts; phosphate ester metal salts; rosin compounds; oleic acid amide, acryl amide, stearic acid amide, decanedicarboxylic acid dibenzoyl hydrazide, hexanedicarboxylic acid dibenzoyl Benzoyl hydrazide, 1,4-cyclohexanedicarboxylic acid dicyclohexylamide, trimesic acid amide, anilide compound, 2,6-naphthalenedicarboxylic acid dicyclohexylamide, N,N'-dibenzoyl-1,4-diaminocyclohexane, N,N'-di Cyclohexanecarbonyl-1,5-diaminonaphthalene, amide compounds such as octanedicarboxylic acid dibenzoylhydrazide, ethylenediamine/stearic acid/sebacic acid polycondensate, montanic acid waxes, aliphatic carboxylic acid metal salts, aromatic carboxylic acid metal salts, Aromatic phosphonic acids and metal salts, aromatic phosphoric acid metal salts, metal salts of aromatic sulfonic acids, metal salts of β-diketones, metal salts of carboxyl groups, organic phosphorus compounds, polyethylene, polypropylene, polybutadiene, polystyrene, AS Resin, ABS resin, poly(acrylic acid), poly(acrylic ester), poly(methacrylic acid), poly(methacrylic ester), polyamide 6, polyamide 46, polyamide 66, polyamide 6T, polyamide 9T, polyamide 10T, poly Examples include organic compounds and polymer compounds such as ether ether ketone and polyether ketone, among which polymer compounds having a carbonyl group are preferred, and polyether ether ketone is more preferred. The amount of the organic crystal nucleating agent blended is preferably 0.06 to 0.19 parts by weight based on 100 parts by weight of the PPS resin (A).

The PPS resin composition of the present invention may further contain inorganic fillers other than (C) glass fiber and (D) calcium carbonate, as long as the effects of the present invention are not impaired. There are no particular restrictions on the inorganic fillers that can be added, but specific examples of fibrous fillers as inorganic fillers include stainless steel fibers, aluminum fibers, brass fibers, rock wool, PAN-based and pitch-based carbon fibers, Carbon nanotubes, carbon nanofibers, calcium carbonate whiskers, wollastenite whiskers, potassium titanate whiskers, barium titanate whiskers, aluminum borate whiskers, silicon nitride whiskers, aramid fibers, alumina fibers, silicon carbide fibers, asbestos fibers, gypsum fibers, ceramics Examples include fibers, zirconia fibers, silica fibers, titanium oxide fibers, silicon carbide fibers, etc., and two or more types of these can also be used in combination. In addition, pre-treatment of these fibrous fillers with coupling agents such as isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, and epoxy compounds provides superior mechanical strength. It is preferable in the sense that it obtains the following.

Specific examples of non-fibrous fillers as inorganic fillers include talc, wollastenite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, and hydrotalcite. Silicates, silicon oxide, magnesium oxide, aluminum oxide (alumina), silica (crushed/spherical), quartz, glass beads, glass flakes, crushed/irregularly shaped glass, glass microballoons, molybdenum disulfide, aluminum oxide (crushed) ), translucent alumina (fiber-like, plate-like, scale-like, granular, irregular-shaped, crushed product), titanium oxide (crushed), zinc oxide (fibrous-like, plate-like, scale-like, granular, irregular-shaped, oxides such as crushed products), carbonates such as magnesium carbonate and zinc carbonate, sulfates such as calcium sulfate and barium sulfate, hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide, silicon carbide, and carbon black. and silica, graphite, aluminum nitride, translucent aluminum nitride (fiber-like, plate-like, scale-like, granular, irregularly shaped, crushed products), calcium polyphosphate, graphite, metal powder, metal flakes, metal ribbons, metal oxides, etc. Examples of the metal species of the metal powder, metal flakes, and metal ribbon include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin. Further, carbon powder, graphite, carbon flakes, scaly carbon, fullerene, graphene, etc. may be mentioned, and these may be hollow, and it is also possible to use two or more types of these fillers in combination. Further, these inorganic fillers may be used after being pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, or an epoxy compound. Among them, carbon powder and graphite are preferred.

There are no particular limitations on the method for preparing the PPS resin composition of the present invention, but each raw material is fed to a commonly known melt mixer such as a single- or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll. A typical example is a method of kneading at a temperature of 380°C. There is no particular restriction on the order of mixing the raw materials, either by blending all the raw materials and then melt-kneading them by the above method, or by blending some of the raw materials and then melt-kneading them by the above method, and then blending the remaining raw materials and melt-kneading them. Either method may be used, such as a method of blending a part of the raw materials, or a method of mixing the remaining raw materials using a side feeder during melt-kneading using a single-screw or twin-screw extruder. Further, as for a small amount of additive components, it is of course possible to knead and pelletize other components by the above-mentioned method or the like, and then add them before molding and use them for molding.

The PPS resin composition of the present invention obtained in this manner can be subjected to various molding processes such as injection molding, extrusion molding, blow molding, and transfer molding, and is particularly suitable for injection molding.

As described above, the PPS resin composition of the present invention has excellent heat cycle resistance while maintaining high mechanical strength and rigidity, and also has excellent adhesiveness with epoxy sealants, so it is suitable for inverter parts. It is useful, especially for capacitor parts.

Other uses to which the PPS resin composition of the present invention can be applied include, for example, sensors, LED lamps, consumer connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, resonators, and various terminals. Typical products include boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, and computer-related parts. Electrical/electronic parts: VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, audio parts, audio equipment parts such as audio/laser discs (registered trademark)/compact discs, lighting parts, refrigerator parts, It can also be applied to household and office appliance parts, such as air conditioner parts, typewriter parts, and word processor parts. Other machinery-related parts include office computer-related parts, telephone-related parts, facsimile-related parts, copying machine-related parts, cleaning jigs, motor parts, lighters, typewriters, etc.; microscopes, binoculars, cameras, watches, etc. Optical equipment and precision machinery related parts; water-related parts such as water faucet frames, mixer faucets, pump parts, pipe joints, water flow control valves, relief valves, hot water temperature sensors, water flow sensors, water meter housings; valves; Alternator terminals, alternator connectors, IC regulators, potentiometer bases for light dimmers, various valves such as exhaust gas valves, various fuel-related/exhaust system/intake system pipes, air intake nozzles snorkels, intake manifolds, fuel pumps, engine cooling water joints. , carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, air conditioner thermostat base, heating hot air flow control valve, Brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dust distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, fuel-related electromagnetic valve coil, fuse Automobile/vehicle related parts such as connectors, horn terminals, electrical component insulating plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition cases, vehicle speed sensors, cable liners, etc. Examples of various uses include:

EXAMPLES The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to the description of these Examples.

[Measurement method for PPS resin]
(1) Melt flow rate (MFR)
The measurement temperature was 315.5°C, the load was 5000g, and the measurement was carried out in accordance with ASTM-D1278-70.

(2) Non-Newtonian exponent Using a capillograph, the shear rate and shear stress were measured at 300°C, with the orifice length as "L" and the diameter as "D", and L/D = 40, and the shear rate and shear stress were measured using the above formula ( 1) was used to calculate the non-Newtonian index.

[Reference Example 1] Polymerization of PPS (PPS-1)
In an autoclave equipped with a stirrer and a valve at the bottom, 8267.4 g (70.0 mol) of 47.5% sodium bisulfide, 2925.0 g (70.2 mol) of 96% sodium hydroxide, and N-methyl-2- Pyrrolidone (NMP) 13,860.0g (140.0 mol), sodium acetate 1,894.2g (23.1 mol), and ion-exchanged water 10,500.0g were charged, and the mixture was heated to 240°C for about 3 hours while passing nitrogen under normal pressure. After gradually heating and distilling 14,772.1 g of water and 280.0 g of NMP, the reaction vessel was cooled to 160°C. The amount of water remaining in the system per mole of charged alkali metal sulfide was 1.08 moles, including the water consumed for hydrolysis of NMP. Further, the amount of hydrogen sulfide scattered was 0.023 mol per 1 mol of the charged alkali metal sulfide.

Next, 10646.7 g (72.4 mol) of p-dichlorobenzene (p-DCB) and 6444.9 g (65.1 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and while stirring at 240 rpm, The temperature was raised from 200°C to 270°C at a rate of 0.6°C/min and held at 270°C for 70 minutes. The extraction valve at the bottom of the autoclave was opened, and the contents were flushed over 15 minutes into a stirred vessel while pressurized with nitrogen, and stirred for a while at 250°C to remove most of the NMP.

The obtained solid substance and 53 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 70°C for 30 minutes, and then suction filtered through a glass filter with a pore size of 10 to 16 μm. Next, 60 liters of ion-exchanged water heated to 70° C. was poured into a glass filter with a pore size of 10 to 16 μm and filtered by suction to obtain 18,000 g of PPS resin cake (including 7,550 g of PPS resin).

18,000 g of the PPS resin cake, 40 liters of ion-exchanged water, and 43 g of acetic acid were charged into an autoclave equipped with a stirrer, and after purging the inside of the autoclave with nitrogen, the temperature was raised to 192° C. and held for 30 minutes to perform acid treatment. The pH during acid treatment was 7. After cooling the autoclave, the contents were filtered through a glass filter with a pore size of 10-16 μm. Next, 60 liters of ion-exchanged water heated to 70°C was poured into a glass filter and filtered with suction to obtain a cake. The resulting cake was dried at 120° C. for 4 hours under a nitrogen stream to obtain an acid-treated linear type PPS-1. The obtained polymer had an MFR of 6300 g/10 minutes and a non-Newtonian index of 1.05.

[Reference Example 2] Polymerization of PPS (PPS-2)
PPS-1 was placed in a heating device with a volume of 100 liters and equipped with a stirrer, and thermal oxidation treatment was performed at 220° C. and an oxygen concentration of 2% for 2 hours to obtain crosslinked PPS-1. The obtained polymer had an MFR of 5000 g/10 minutes and a non-Newtonian index of 1.07.

[Reference Example 3] Polymerization of PPS (PPS-3)...Equivalent to L2120 In a 70 liter autoclave equipped with a stirrer and a bottom plug valve, 8.27 kg (70.00 mol) of 47.5% sodium bisulfide, 96% 2.91 kg (69.80 mol) of sodium hydroxide, 11.45 kg (115.50 mol) of N-methyl-2-pyrrolidone (NMP), and 10.5 kg of ion-exchanged water were charged, and 245 ml of The reaction vessel was gradually heated to 200° C. over about 3 hours to distill off 14.78 kg of water and 0.28 kg of NMP, and then cooled to 200° C. The amount of water remaining in the system per mole of alkali metal sulfide charged was 1.06 moles, including the water consumed for hydrolysis of NMP. Further, the amount of hydrogen sulfide scattered was 0.02 mol per mol of the alkali metal sulfide charged.

Thereafter, it was cooled to 200°C, 10.48 kg (71.27 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and while stirring at 240 rpm. The temperature was raised from 200°C to 270°C at a rate of 6°C/min. After reacting at 270°C for 100 minutes, the bottom valve of the autoclave was opened, and the contents were flushed into a container with a stirrer for 15 minutes while pressurized with nitrogen, and most of the NMP was removed by stirring at 250°C for a while. .

The obtained solid matter and 76 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 70°C for 30 minutes, and then suction-filtered through a glass filter. Next, 76 liters of ion-exchanged water heated to 70°C was poured into a glass filter and filtered with suction to obtain a cake.

The resulting cake and 90 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, and acetic acid was added to adjust the pH to 7. After purging the inside of the autoclave with nitrogen, the temperature was raised to 192°C and held for 30 minutes. Thereafter, the autoclave was cooled and the contents were taken out.

After the contents were suction-filtered through a glass filter, 76 liters of ion-exchanged water at 70°C was poured thereinto and suction-filtered to obtain a cake. Dry PPS was obtained by drying the obtained cake at 120° C. under a nitrogen stream. This was heat-treated at 220° C. with an oxygen concentration of 12% until the MFR value became 150 g/10 minutes to obtain crosslinked PPS-3. The obtained polymer had an MFR of 130 g/10 min and a non-Newtonian index of 1.40.

[Blends used in Examples and Comparative Examples]
The formulations used in the present examples and comparative examples are as follows.

(A) PPS resin PPS-1: Linear PPS resin polymerized by the method described in Reference Example 1 PPS-2: Crosslinked PPS resin polymerized by the method described in Reference Example 2 PPS-3: Described in Reference Example 3 Cross-linked PPS resin polymerized by the method of

(B) Epoxy resin B-1: Bisphenol A epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER1009 (trade name), epoxy equivalent weight 2,400 to 3,300)
B-2: Bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation jER1004AF (trade name) epoxy equivalent 875-975)
B-3: Bisphenol A type phenoxy resin (manufactured by Mitsubishi Chemical Corporation jER1256 (trade name) epoxy equivalent 7,500 to 8,500)

(C) Glass fiber C: chopped strand (manufactured by Nippon Electric Glass Co., Ltd., T-760H, 3 mm length, average fiber diameter 10.5 μm)

(D) Calcium carbonate D: Heavy calcium carbonate (Sankyo Seifun Co., Ltd. Escalon #800 50% average particle diameter 3.5 μm)

(E) Olefin copolymer E-1: Ethylene/1-octene copolymer (manufactured by Dow Chemical Co., Ltd. Engage 8842)
E-2: Ethylene glycidyl methacrylate copolymer (“Bond First” BF-E manufactured by Sumitomo Chemical Co., Ltd.)

(F) Silane compound F: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.).

[Measurement evaluation method]
The measurement and evaluation methods in the present examples and comparative examples are as follows.

(1) Tensile strength Measurement was performed in accordance with ISO 527-1, 2 (2012). Specifically, measurements were performed as follows. After drying the PPS resin composition pellets at 130°C for 3 hours using a hot air dryer, an injection molding machine manufactured by Sumitomo Heavy Industries, Ltd. (SE- 50D) and using a mold with a type A1 test piece shape (4 mm thickness) specified in ISO 20753 (2008), the average speed of the molten resin passing through the cross-sectional area of the central parallel part was 400 ± 50 mm/ Injection molding was performed under the conditions of s to obtain a test piece. This test piece was conditioned for 16 hours at 23°C and 50% relative humidity, and then under conditions of 23°C and 50% relative humidity, distance between grips: 115 mm, and test speed: 5 mm/min. The tensile strength was measured in accordance with ISO 527-1, -2 (2012). If it is 185 MPa or more, it can be said that it is at a product level with no practical problems, but the higher this value is, the better the mechanical strength is, which is preferable.

(2) Weld strength An ASTM No. 4 dumbbell piece (1.6 mm) with gates at both ends and a weld line near the center of the test piece was molded using an injection molding machine at a cylinder temperature of 320°C and a mold temperature of 135°C. Molded under the following conditions. Ten samples for measurement were obtained, and the tensile strength was measured at a test speed of 10 mm/min and a distance between grips of 64 mm. If it is 50 MPa or more, it can be said that it is at a product level with no practical problems, but the higher this value is, the better the mechanical strength is, which is preferable.

(3) Fluidity Molding was performed using a 1 mm thick spiral flow mold under the following conditions: cylinder temperature 320°C, mold temperature 140°C, injection speed 230mm/sec, injection pressure 98MPa, injection time 5sec, cooling time 15sec, Flow length was measured (injection molding machine used: "SE-30D" manufactured by Sumitomo Heavy Industries). The larger this value is, the better the fluidity is.

(4) Dimensional accuracy The molded product shown in FIG. 1 was molded using an injection molding machine (SE-100DU) manufactured by Sumitomo Heavy Industries. The molding conditions were a cylinder temperature of 320°C, a mold temperature of 130°C, and other general molding conditions. The dimensions of the molded article in the MD direction were measured at three points, and the average value was calculated. The dimensional accuracy was determined by subtracting the measured average value from the actual size of the mold and dividing it by the actual size of the mold. The measurement was performed using a three-dimensional dimension measuring machine manufactured by Mitutoyo in accordance with JIS B0621. If it is less than 0.15%, it can be said that the product level has no practical problems, but the smaller this value is, the better the dimensional accuracy is, which is preferable. Those smaller than 0.15% were rated ○, and those 0.15% or more were rated ×.

(5) Heat cycle resistance A metal insert molded product shown in FIG. 2, in which a metal block was insert molded under conditions of a cylinder temperature of 320°C and a mold temperature of 140°C, was used. After treatment at 130° C. for 1 hour and then at -40° C. for 1 hour, thermal shock treatment was performed, and the presence or absence of cracks was visually checked every 5 times. The number of thermal shock treatments at which cracking was observed was defined as the thermal shock resistance. If cracks do not occur 25 times or more, it can be said that the product is at a level with no practical problems, but the greater the number of treatments until cracks occur, the better the thermal shock resistance is, which is preferable.

(6) Epoxy adhesiveness Resin pellets were supplied to a Sumitomo-Nestal injection molding machine (SG75-HIPRO/MIII) set at a cylinder temperature of 320°C, and the mold temperature was adjusted to 130°C for ASTM No. 1 dumbbell piece molding. Injection molding was performed using a mold to obtain an ASTM No. 1 dumbbell piece. The obtained ASTM No. 1 dumbbell piece was divided into two equal parts from the center, and a spacer (thickness: 1.8 to ^2.2 mm, opening: 5 mm x 10 mm) was created so that the contact area with the epoxy adhesive was 50 mm 2. ) is sandwiched between two ASTM No. 1 dumbbell pieces that have been divided into two halves, and fixed using clips, and then the opening is filled with epoxy resin (2-component epoxy resin manufactured by Nagase ChemteX Co., Ltd., base material: XNR5002, curing agent). :XNH5002 (mixing ratio: base resin: curing agent = 100:90) was injected and heated in a hot air dryer set at 105° C. for 3 hours to cure and adhere. After cooling at 23°C for one day, the spacer was removed, and the tensile breaking strength was measured using an Instron tensile tester at 23°C at a strain rate of 1 mm/min and a distance between supports of 80 mm. The value divided by the adhesive area was determined as the epoxy adhesive strength.

[Manufacture of PPS resin composition] (Example 3, Comparative Example 15)
(A), (B), ( Components D) and (E) were added from the raw material supply port in the weight ratio shown in Table 1 to form a molten state, and (C) glass fiber was fed from the intermediate addition port in the weight ratio shown in Table 1, with a discharge amount of 30 kg. / hour to obtain pellets. Each of the above characteristics was evaluated using this pellet. The results are shown in Table 1.

The PPS resin composition obtained in this way has unknown properties such as excellent heat cycle resistance while maintaining high mechanical strength and rigidity, and excellent adhesion with epoxy sealants, so it is suitable for inverter parts. It is particularly useful for capacitor parts.

1. Molded product for dimensional accuracy evaluation 2. Gate 3. Insert metal 4. Gate 5. metal insert molded products

Claims (5)

(B) A bisphenol type epoxy resin having an epoxy equivalent of 800 to 3500 to 100 parts by weight of the total (A) of (A-1) linear type polyphenylene sulfide resin and (A-2) crosslinked type polyphenylene sulfide resin. 0.5 to 15 parts by weight, (C) 50 to 200 parts by weight of glass fiber, (D) 10 to 100 parts by weight of calcium carbonate, and (E-1) an olefin-based (co)polymer containing no glycidyl group. and (E-2) a glycidyl group-containing olefin copolymer in a total of 5 to 15 parts by weight. (A-1) The linear polyphenylene sulfide resin has a non-Newtonian index of 1.05 or less, (A-2) the crosslinked polyphenylene sulfide resin has a non-Newtonian index of 1.30 or more, and (A-1 ) The blending ratio of linear type polyphenylene sulfide resin and (A-2) crosslinked type polyphenylene sulfide resin is (A-1):(A-2) = 50:50 to 70:30 (weight ratio) , the polyphenylene sulfide resin composition according to claim 1. The polyphenylene sulfide resin composition according to claim 1 or 2, the polyphenylene sulfide resin composition for a molded article that is at least partially in contact with an epoxy resin for sealing. A molded article obtained by injection molding the polyphenylene sulfide resin composition according to any one of claims 1 to 3. A composite molded product comprising the molded product according to claim 4 and an epoxy resin for sealing at least in part.