Thin wall molding composed of polyphenylene sulfide resin composition

Abstract

To obtain a thin wall molding using a polyphenylene sulfide resin composition provided with excellent fluidity, and toughness, and having high productivity, and reliability based on low warpage, and dimension stability.SOLUTION: A thin wall molding having a thickness of a most-thinnest portion of 1 mm or less, is composed of, (a) with respect to 100 pts.wt. of polyolefin sulfide resin, (b) 0.1-0.5 pt.wt. of a silane coupling agent, (c) 1-5 pts.wt. of carboxylic acid amide wax obtained by reacting a higher aliphatic monocarboxylic acid with a polybasic acid and diamine, and (d) a polyphenylene sulfide resin composition obtained by blending 0.5 pt.wt. or less of a thermoplastic elastomer, and has tensile breaking elongation of a test piece obtained by extrusion molding the polyphenylene sulfide resin composition (measured according to ISO527-1,2 (2012) of 5% or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a thin-walled molded article that uses a polyphenylene sulfide resin composition that combines excellent fluidity and toughness, and that has high productivity and reliability due to low warpage and dimensional stability. [Background technology]

[0002] As awareness of protecting the global environment grows, electric vehicles that reduce CO2 emissions while driving and secondary batteries for home use that efficiently utilize surplus electricity at night are becoming more widespread, and there is a demand for further efficiency improvements in the secondary batteries used in vehicles and stationary batteries for homes.

[0003] Thin-walled molded products made of resin materials have traditionally been used for battery insulating materials, but the use of polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin, which has excellent heat resistance and chemical resistance, is being considered as a material that can withstand the heat generated by the battery itself and the thermal effects of the surrounding environment.While PPS resin has these excellent properties, it has the disadvantage of low toughness, and improvements to its toughness, such as tensile breaking elongation, are being considered in order to prevent damage to battery insulating materials during the crimping and fitting processes during battery manufacturing.

[0004] For example, in Patent Document 1, it was found that a PPS resin composition containing a PPS resin and an organosilane compound has excellent resistance to hydrofluoric acid and caulking, and the PPS resin composition is applied to an insulating member for a battery.

[0005] Patent Document 2 discloses a gasket for lithium ion batteries made of a PPS resin composition containing a thermoplastic elastomer having a reactive functional group. The PPS resin composition contains a thermoplastic elastomer, which is a flexible material compared to PPS resin, and thus has excellent toughness such as elongation and impact resistance. This gives the gasket excellent sealing properties, and is therefore used for gaskets for lithium ion batteries. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent Publication No. 2022-36538 [Patent Document 2] Patent Publication No. 2022-165484 Summary of the Invention [Problem to be solved by the invention]

[0007] In recent years, further increases in the capacity of secondary batteries such as lithium-ion batteries used in vehicles and stationary batteries for residential use have been considered. In particular, for secondary batteries for vehicles, higher battery capacity is required to extend the driving range required for the spread of electric vehicles, and battery insulating materials tend to become larger. As the batteries become larger, warping of battery insulating materials becomes a new issue because the materials are thin-walled molded products. To address this issue, there is a demand for improvement in the suppression of warping (low warpage) of insulating materials, which leads to improved reliability of the materials and ultimately the reliability of the batteries. In addition, a rapid increase in demand for electric vehicles is expected, and high productivity is required for battery insulating materials, so they are also expected to have small warpage variations and excellent dimensional stability.

[0008] However, Patent Documents 1 and 2 are silent about suppressing warpage or reducing the variation, and these problems are not addressed. Furthermore, the present inventors evaluated the warpage of molded products made of the resin composition of PPS resin and an organosilane compound described in Patent Document 1, and found that the amount of warpage and its variation were large. [Means for solving the problem]

[0009] The present inventors conducted research to solve the above problems, and found that a polyphenylene sulfide resin composition containing (a) a polyphenylene sulfide resin, (b) a silane coupling agent, and (c) a carboxylic acid amide wax obtained by reacting a higher aliphatic monocarboxylic acid with a polybasic acid and a diamine in a specific composition, and (d) a thermoplastic elastomer in an amount of 0.5 parts by weight or less and substantially no thermoplastic elastomer, the polyphenylene sulfide resin composition having a tensile elongation at break of 5% or more when the resin composition is injection molded, has excellent fluidity and toughness, and a thin-walled molded product made of the polyphenylene sulfide resin composition has excellent low warpage and dimensional stability, and thus has high productivity and reliability. That is, the present invention has been made to solve at least a part of the above problems, and can be carried out in the following forms. (1) A thin-walled molded product having a thickness of 1 mm or less at its thinnest part, comprising a polyphenylene sulfide resin composition obtained by blending, with respect to (a) 100 parts by weight of polyphenylene sulfide resin, (b) 0.1 to 0.5 parts by weight of a silane coupling agent, (c) 1 to 5 parts by weight of a carboxylic acid amide wax obtained by reacting a higher aliphatic monocarboxylic acid with a polybasic acid and a diamine, and (d) 0.5 parts by weight or less of a thermoplastic elastomer, wherein a test piece obtained by injection molding the polyphenylene sulfide resin composition has a tensile elongation at break (measured in accordance with ISO527-1, 2 (2012)) of 5% or more. (2) The thin-walled molded product according to (1), having a thickness of 1 mm or less at its thinnest portion, wherein the content of a product of a higher aliphatic monocarboxylic acid and a diamine, which is not containing a structure derived from a polybasic acid, in the (c) carboxylic acid amide wax obtained by reacting a higher aliphatic monocarboxylic acid with a polybasic acid and a diamine, is 5 to 65% by weight. (3) The thin-walled molded product according to (1) or (2), wherein the deflection temperature under load (measured in accordance with ISO75-1,2 (2013), load of 0.45 MPa) of a test piece obtained by injection molding the polyphenylene sulfide resin composition is 180°C or higher, and the thin-walled molded product has a thickness of 1 mm or less at its thinnest part. (4) The thin-walled molded product having a thickness of 1 mm or less at its thinnest part according to any one of (1) to (3), wherein the polyphenylene sulfide resin composition is injection molded at a cylinder temperature of 320°C and a mold temperature of 150°C to obtain a square plate (W: 80 mm × D: 80 mm × H: 1 mm) having a warpage of 1.8 mm or less. (5) A thin-walled molded product for use as an insulating member for a battery according to any one of (1) to (4), the thinnest part of which has a thickness of 1 mm or less. (6) A thin-walled molded product for use as an insulating member for an in-vehicle lithium-ion battery according to any one of (1) to (5), the thinnest part of which has a thickness of 1 mm or less. Effect of the Invention

[0010] According to the present invention, by using a polyphenylene sulfide resin composition having both excellent fluidity and toughness, it is possible to obtain a thin-walled molded product having high productivity and reliability due to low warpage and dimensional stability. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, an embodiment of the present invention will be described in detail.

[0012] (1)(a) Polyphenylene sulfide resin The polyphenylene sulfide resin (a) used in the present invention is a polymer having a repeating unit represented by the following structural formula:

[0013] [ka]

[0014] From the viewpoint of heat resistance, it is preferable for the polymer to contain 70 mol % or more, and more preferably 90 mol % or more, of the repeating unit represented by the above structural formula. In addition, about 30 mol % or less of the repeating units of the (a) PPS resin may be composed of repeating units having the following structure.

[0015] [ka]

[0016] A PPS copolymer partially having such a structure has a melting point lower than the general melting point of PPS, 280° C., and therefore such a resin composition is advantageous in terms of moldability.

[0017] There is no particular restriction on the weight-average molecular weight of the (a) PPS resin used in the present invention, but from the viewpoint of obtaining a good balance between excellent mechanical properties represented by tensile elongation at break and high fluidity required in molding thin-walled molded products, the weight-average molecular weight is preferably 40,000 to 90,000, more preferably 40,000 to 80,000, and particularly preferably 50,000 to 70,000. If the weight-average molecular weight is small, the mechanical properties of the PPS resin itself will decrease, and damage to components will occur during crimping and fitting processes during battery manufacturing, so a weight-average molecular weight of 40,000 or more is preferable. On the other hand, if the weight-average molecular weight exceeds 90,000, the melt viscosity will be significantly increased, which tends to be undesirable in molding thin-walled molded products. In addition, in the present invention, a mixture of multiple (a) PPS resins having different weight-average molecular weights may be used.

[0018] The weight average molecular weight in the present invention is a value calculated in terms of polystyrene using a gel permeation chromatography (GPC) manufactured by Senshu Scientific.

[0019] A method for producing the (a) PPS resin used in the present invention will be described below, but the method is not limited to the method described below as long as the (a) PPS resin having the above-mentioned properties can be obtained.

[0020] First, the polyhalogenated aromatic compound, sulfidizing agent, polymerization solvent, molecular weight regulator, polymerization aid and polymerization stabilizer used in the production method will be described.

[0021] [Polyhalogenated aromatic compounds] Polyhalogenated aromatic compounds refer to compounds having two or more halogen atoms in one molecule.Specific examples of polyhalogenated aromatic compounds include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene, hexachlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, and 1-methoxy-2,5-dichlorobenzene, and preferably p-dichlorobenzene. In addition, for the purpose of introducing a carboxyl group, a carboxyl group-containing dihalogenated aromatic compound such as 2,4-dichlorobenzoic acid, 2,5-dichlorobenzoic acid, 2,6-dichlorobenzoic acid, or 3,5-dichlorobenzoic acid, or a mixture thereof, can be used as a copolymerization monomer in one preferred embodiment. Although it is also possible to combine two or more different polyhalogenated aromatic compounds to form a copolymer, it is preferable to use a p-dihalogenated aromatic compound as the main component.

[0022] The amount of the polyhalogenated aromatic compound used, in order to obtain a PPS resin (a) having a viscosity suitable for processing, can be, for example, in the range of 0.9 to 2.0 mol, preferably 0.95 to 1.5 mol, and more preferably 1.005 to 1.2 mol, per mol of the sulfidizing agent.

[0023] [Sulfidizing agent] The sulfidizing agent includes alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.

[0024] 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 preferred. These alkali metal sulfides can be used as hydrates or aqueous mixtures, or in the anhydrous form.

[0025] Specific examples of the alkali metal hydrosulfide include sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and mixtures of two or more of these, with sodium hydrosulfide being preferred. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures, or in the anhydrous form.

[0026] In addition, an alkali metal sulfide prepared in situ in the reaction system from an alkali metal hydrosulfide and an alkali metal hydroxide can also be used.Alkali metal sulfide can also be prepared from an alkali metal hydrosulfide and an alkali metal hydroxide, and then transferred to a polymerization tank for use.

[0027] Alternatively, an alkali metal sulfide prepared in situ in the reaction system from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide can be used.Alkaline metal sulfides can also be prepared from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide, and then transferred to a polymerization tank for use.

[0028] When a part of the sulfidizing agent is lost before the start of the polymerization reaction due to a dehydration operation or the like, the amount of the charged sulfidizing agent means the remaining amount obtained by subtracting the lost amount from the actual charged amount.

[0029] It is also possible to use an alkali metal hydroxide and / or an alkaline earth metal hydroxide together with the sulfidizing agent.Specific examples of the alkali metal hydroxide include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and mixtures of two or more of these.Specific examples of the alkaline earth metal hydroxide include, for example, calcium hydroxide, strontium hydroxide, barium hydroxide, etc., and among these, sodium hydroxide is preferably used.

[0030] When an alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use an alkali metal hydroxide simultaneously. The amount of the alkali metal hydroxide used is, for example, in the range of 0.95 to 1.20 mol, preferably 1.00 to 1.15 mol, and more preferably 1.005 to 1.100 mol, per mol of the alkali metal hydrosulfide.

[0031] [Polymerization solvent] As the polymerization solvent, it is preferable to use an organic polar solvent. Specific examples include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, caprolactams such as N-methyl-ε-caprolactam, aprotic organic solvents such as 1,3-dimethyl-2-imidazolidinone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, dimethylsulfone, and tetramethylene sulfoxide, and mixtures thereof, all of which are preferably used because of their high reaction stability. Among these, N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) is particularly preferably used.

[0032] The amount of the organic polar solvent used is selected from the range of 2.0 to 10 moles, preferably 2.25 to 6.0 moles, and more preferably 2.5 to 5.5 moles, per mole of the sulfidizing agent.

[0033] [Molecular weight regulator] A monohalogen compound (which does not necessarily have to be an aromatic compound) can be used in combination with the polyhalogenated aromatic compound in order to form terminals in the resulting (a) PPS resin or to adjust the polymerization reaction or molecular weight.

[0034] [Polymerization aid] In order to obtain a (a) PPS resin having a relatively high degree of polymerization in a short time, it is also a preferred embodiment to use a polymerization aid. Here, the polymerization aid means a substance that has the effect of increasing the viscosity of the (a) PPS resin obtained. Specific examples of such polymerization aids include organic carboxylates, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates, and alkaline earth metal phosphates. These can be used alone or in combination of two or more. Among them, organic carboxylates, water, and alkali metal chlorides are preferred, and alkali metal carboxylates are more preferred as organic carboxylates, and lithium chloride is more preferred as alkali metal chlorides.

[0035] The above alkali metal carboxylate has the general formula R(COOM) n (wherein R is an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group, or an arylalkyl group having 1 to 20 carbon atoms; M is an alkali metal selected from lithium, sodium, potassium, rubidium, and cesium; and n is an integer of 1 to 3). The alkali metal carboxylate can also be used as a hydrate, anhydride, or an aqueous solution. Specific examples of the alkali metal carboxylate include lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluate, and mixtures thereof.

[0036] The alkali metal carboxylate may be formed by adding and reacting an organic acid with one or more compounds selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, and alkali metal bicarbonates in approximately equal chemical equivalents. Among the above alkali metal carboxylates, lithium salts have high solubility in the reaction system and have a large auxiliary effect, but are expensive, while potassium, rubidium, and cesium salts are thought to have insufficient solubility in the reaction system, so sodium acetate, which is inexpensive and has moderate solubility in the polymerization system, is most preferably used.

[0037] When these alkali metal carboxylates are used as polymerization aids, the amount used is usually in the range of 0.01 mol to 2 mol per mol of the charged alkali metal sulfide. In terms of obtaining a higher degree of polymerization, the amount used is preferably in the range of 0.1 mol to 0.6 mol, and more preferably in the range of 0.2 mol to 0.5 mol.

[0038] When water is used as a polymerization aid, the amount added is usually in the range of 0.3 mol to 15 mol per mol of the charged alkali metal sulfide, and in terms of obtaining a higher degree of polymerization, the range of 0.6 mol to 10 mol is preferable, and the range of 1 mol to 5 mol is more preferable.

[0039] Of course, two or more of these polymerization aids can be used in combination. For example, when an alkali metal carboxylate and water are used in combination, a higher molecular weight can be achieved with a smaller amount of each.

[0040] The timing of addition of these polymerization aids is not particularly specified, and they may be added at any time during the pre-step, at the start of polymerization, or during the polymerization, as described below, or may be added in several portions, but when an alkali metal carboxylate is used as the polymerization aid, it is more preferable to add it at the start of the pre-step or at the start of polymerization, because it is easy to add it. When water is used as the polymerization aid, it is effective to add it during the polymerization reaction after the polyhalogenated aromatic compound is charged.

[0041] [Polymerization stabilizer] A polymerization stabilizer can be used to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to the stabilization of the polymerization reaction system and suppresses undesirable side reactions. One of the indicators of side reactions is the generation of thiophenol, and the addition of a polymerization stabilizer can suppress the generation of thiophenol. 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 them, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferred. The above-mentioned alkali metal carboxylates also act as polymerization stabilizers. In addition, when an alkali metal hydrosulfide is used as a sulfidizing agent, it is particularly preferable to use an alkali metal hydroxide at the same time, as mentioned above, but an alkali metal hydroxide that is in excess of the sulfidizing agent can also serve as a polymerization stabilizer.

[0042] These polymerization stabilizers can be used alone or in combination of two or more. The polymerization stabilizer is preferably used in a ratio of usually 0.02 to 0.2 mol, preferably 0.03 to 0.1 mol, more preferably 0.04 to 0.09 mol, per mol of the charged alkali metal sulfide. If this ratio is too small, the stabilizing effect is insufficient, and conversely, if it is too large, it is economically disadvantageous and the polymer yield tends to decrease.

[0043] The timing of adding the polymerization stabilizer is not particularly specified, and it may be added at any time during the pre-step described below, at the start of polymerization, or during the polymerization, or may be added in several divided portions. However, it is more preferable to add it simultaneously at the start of the pre-step or at the start of polymerization from the viewpoint of ease.

[0044] Next, a preferred method for producing the PPS resin (a) used in the present invention will be specifically described in order, including a pre-process, a polymerization reaction process, a recovery process, and a post-treatment process, although the method is not limited to this method.

[0045] [Pre-process] (a) In the production process for PPS resin, the sulfidizing agent is usually used in the form of a hydrate. It is preferable to heat a mixture containing an organic polar solvent and a sulfidizing agent and remove excess water from the system before adding a polyhalogenated aromatic compound.

[0046] As described above, the sulfidizing agent may be prepared in situ in the reaction system from an alkali metal hydrosulfide and an alkali metal hydroxide, or in a tank separate from the polymerization tank. There is no particular restriction on this method, but a preferable method is to add an alkali metal hydrosulfide and an alkali metal hydroxide to an organic polar solvent in an inert gas atmosphere at room temperature to 150°C, preferably from room temperature to 100°C, and then heat the mixture to at least 150°C or higher, preferably 180 to 260°C, under normal pressure or reduced pressure, to distill off water. A polymerization aid may be added at this stage. Toluene or the like may be added to promote the distillation of water.

[0047] In the polymerization reaction, the amount of water in the polymerization system is preferably 0.3 mol to 10.0 mol per 1 mol of the charged sulfidizing agent. Here, the amount of water in the polymerization system is the amount of water charged to the polymerization system minus the amount of water removed from the polymerization system. The charged water may be in any form such as water, an aqueous solution, or crystal water.

[0048] [Polymerization reaction process] (a) PPS resin is produced by reacting a sulfidizing agent with a polyhalogenated aromatic compound in an organic polar solvent at a temperature range of 200° C. or higher and lower than 290° C.

[0049] When starting the polymerization reaction process, the organic polar solvent, the sulfidizing agent, and the polyhalogenated aromatic compound are mixed, desirably in an inert gas atmosphere, at a temperature range of room temperature to 240° C., preferably 100° C. to 230° C. A polymerization aid may be added at this stage. The order of charging these raw materials may be random, or they may be charged simultaneously.

[0050] The mixture is usually heated to a temperature in the range of 200° C. to less than 290° C. There are no particular limitations on the heating rate, but 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.

[0051] In general, the temperature is finally raised to 250 to less than 290° C., and the reaction is carried out at that temperature for usually 0.25 to 50 hours, preferably 0.5 to 20 hours.

[0052] In order to obtain a higher degree of polymerization, it is effective to react at 200° C. to 260° C. for a certain period of time before the final temperature is reached, and then to raise the temperature to 270° C. to less than 290° C. In this case, the reaction time at 200° C. to 260° C. is usually selected within the range of 0.25 hours to 20 hours, and preferably 0.25 hours to 10 hours.

[0053] In order to obtain a polymer with a higher degree of polymerization, it may be effective to carry out the polymerization in multiple stages. When carrying out the polymerization in multiple stages, it is effective to carry out the polymerization when the conversion rate of the polyhalogenated aromatic compound in the system at 245°C reaches 40 mol% or more, preferably 60 mol%.

[0054] The conversion rate of polyhalogenated aromatic compounds (abbreviated as PHA here) is a value calculated by the following formula: The amount of remaining PHA can usually be determined by gas chromatography.

[0055] (A) When a polyhalogenated aromatic compound is added in excess of an alkali metal sulfide in terms of molar ratio Conversion rate=[charged amount of PHA (mol)−remaining amount of PHA (mol)] / [charged amount of PHA (mol)−excess amount of PHA (mol)].

[0056] (B) Cases other than (A) above Conversion rate=[charged amount of PHA (mol)−remaining amount of PHA (mol)] / [charged amount of PHA (mol)].

[0057] [Recovery process] In the (a) PPS resin manufacturing method, after the polymerization is completed, solid matter is recovered from the polymerization reaction product containing the polymer, the solvent, etc. As for the recovery method, it is essential to adopt a method of recovering the particulate polymer by slowly cooling after the polymerization reaction is completed. The cooling speed is not particularly limited, but is usually about 0.1°C / min to 3°C / min. It is not necessary to slowly cool at the same speed throughout the entire cooling process, and a method of slowly cooling at a speed of 0.1 to 1°C / min until the polymer particles crystallize and precipitate, and then at a speed of 1°C / min or more may be adopted.

[0058] [Post-processing process] The (a) PPS resin may be produced through the above-mentioned polymerization and recovery steps, and then may be subjected to acid treatment, hot water treatment, washing with an organic solvent, or treatment with an alkali metal or alkaline earth metal.

[0059] The acid treatment is carried out as follows: There are no particular limitations on the acid used in the acid treatment of the (a) PPS resin so long as it does not have the effect of decomposing the (a) PPS resin, and examples of the acid include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propylic acid, and among these, acetic acid and hydrochloric acid are more preferably used, but acids such as nitric acid that decompose and deteriorate the (a) PPS resin are undesirable.

[0060] The acid treatment may be carried out by immersing the PPS resin (a) in an acid or an aqueous solution of an acid, and may be carried out with appropriate stirring or heating, if necessary. For example, when acetic acid is used, a sufficient effect can be obtained by immersing the PPS resin powder in an aqueous solution of pH 4 heated to 80 to 200°C and stirring for 30 minutes. The pH after the treatment may be 4 or higher, for example, about pH 4 to 8. The PPS resin (a) that has been subjected to the acid treatment is preferably washed several times with water or warm water to remove the remaining acid or salt. The water used for washing is preferably distilled water or deionized water, so as not to impair the effect of the preferable chemical modification of the PPS resin (a) by the acid treatment.

[0061] The hot water treatment is carried out as follows: When the (a) PPS resin is subjected to hot water treatment, the temperature of the hot water is preferably 100° C. or higher, more preferably 120° C. or higher, still more preferably 150° C. or higher, and particularly preferably 170° C. or higher. If the temperature is less than 100° C., the desired chemical modification effect of the (a) PPS resin is small, which is not preferred.

[0062] In order to achieve the desired chemical modification effect of the (a) PPS resin by hot water washing, it is preferable that the water used is distilled water or deionized water. There are no particular limitations on the procedure for the hot water treatment, and it can be carried out by adding a specified amount of (a) PPS resin to a specified amount of water, heating and stirring in a pressure vessel, or by continuously carrying out hot water treatment. The ratio of (a) PPS resin to water is preferably higher, but a bath ratio of 200 g or less of (a) PPS resin to 1 liter of water is usually selected.

[0063] In addition, since decomposition of the terminal groups is undesirable, it is desirable to carry out the treatment in an inert atmosphere to avoid this. Furthermore, after the hot water treatment, the (a) PPS resin is preferably washed several times with warm water to remove any remaining components.

[0064] When washing with an organic solvent, the procedure is as follows. The organic solvent used for washing the (a) PPS resin is not particularly limited as long as it does not have the action of decomposing the (a) PPS resin, and examples thereof include nitrogen-containing polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, 1,3-dimethylimidazolidinone, hexamethylphosphoramide, and piperazinones, sulfoxide-sulfone solvents such as dimethylsulfoxide, dimethylsulfone, and sulfolane, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, and acetophenone, dimethyl ether, dipropyl ether, dioxane, and tetrahydrofuran. Examples of the organic solvent include ether solvents such as hydrofuran, halogen-based solvents such as chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchloroethylene, monochloroethane, dichloroethane, tetrachloroethane, perchloroethane, and chlorobenzene, alcohol-phenol solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, and polypropylene glycol, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene. Among these organic solvents, N-methyl-2-pyrrolidone, acetone, dimethylformamide, and chloroform are particularly preferred. These organic solvents are used alone or in combination of two or more.

[0065] The method of washing with an organic solvent includes immersing the (a) PPS resin in the organic solvent, and stirring or heating can be performed as necessary. There is no particular restriction on the washing temperature when washing the (a) PPS resin with an organic solvent, and any temperature between room temperature and about 300°C can be selected. The higher the washing temperature, the higher the washing efficiency tends to be, but usually a washing temperature between room temperature and 150°C is sufficient to obtain the desired effect. Washing can also be performed under pressure in a pressure vessel at a temperature above the boiling point of the organic solvent. There is also no particular restriction on the washing time. Although it depends on the washing conditions, in the case of batch washing, washing for 5 minutes or more usually obtains the desired effect. Continuous washing is also possible.

[0066] Examples of the method of alkali metal or alkaline earth metal treatment include a method of adding an alkali metal salt or alkaline earth metal salt before, during, or after the previous step, a method of adding an alkali metal salt or alkaline earth metal salt into a polymerization vessel before, during, or after the polymerization step, or a method of adding an alkali metal salt or alkaline earth metal salt at the beginning, middle, or end of the washing step. The easiest method among them is a method of adding an alkali metal salt or alkaline earth metal salt after removing residual oligomers and residual salts by washing with an organic solvent or washing with warm or hot water. The alkali metal or alkaline earth metal is preferably introduced into PPS in the form of an alkali metal ion or alkaline earth metal ion such as an acetate, hydroxide, or carbonate. It is also preferable to remove excess alkali metal salt or alkaline earth metal salt by washing with warm water or the like. The concentration of the alkali metal ion or alkaline earth metal ion when introducing the alkali metal or alkaline earth metal is preferably 0.001 mmol or more per 1 g of PPS, and more preferably 0.01 mmol or more. The temperature is preferably 50° C. or higher, more preferably 75° C. or higher, and particularly preferably 90° C. or higher. There is no particular upper limit to the temperature, but from the viewpoint of operability, it is usually preferably 280° C. or lower. The bath ratio (weight of cleaning solution relative to the weight of dry PPS) is preferably 0.5 or higher, more preferably 3 or higher, and even more preferably 5 or higher.

[0067] In the present invention, from the viewpoint of obtaining a polyphenylene sulfide resin composition excellent in retention stability, a method in which residual oligomers and residual salts are removed by repeatedly washing with an organic solvent and with warm water of about 80° C. or the above-mentioned hot water several times, and then the method in which the resin is treated with an acid, an alkali metal salt, or an alkaline earth metal salt is treated is preferred, and in particular a method in which the resin is treated with an alkali metal salt or an alkaline earth metal salt is more preferred.

[0068] In addition, the (a) PPS resin can also be used after being polymerized by a thermal oxidative crosslinking treatment in which heating is performed in an oxygen atmosphere after polymerization or by heating with the addition of a crosslinking agent such as a peroxide, thereby increasing the molecular weight.

[0069] When dry heat treatment is performed for the purpose of increasing the molecular weight by thermal oxidation crosslinking, the temperature is preferably 160 to 260°C, more preferably 170 to 250°C. The oxygen concentration is desirably 5% by volume or more, more desirably 8% by volume or more. There is no particular upper limit to the oxygen concentration, but the limit is about 50% by volume. The treatment time is preferably 0.5 to 100 hours, more preferably 1 to 50 hours, and even more preferably 2 to 25 hours. The heat treatment device may be a normal hot air dryer, or a rotary or stirring blade-equipped heating device, but in the case of efficient and more uniform treatment, it is more preferable to use a rotary or stirring blade-equipped heating device.

[0070] Dry heat treatment can also be performed to suppress thermal oxidative crosslinking and remove volatiles. The temperature is preferably 130 to 250°C, more preferably 160 to 250°C. In this case, the oxygen concentration is preferably less than 5% by volume, and even less than 2% by volume. The treatment time is preferably 0.5 to 50 hours, more preferably 1 to 20 hours, and even more preferably 1 to 10 hours. The heat treatment device may be a normal hot air dryer, or a rotary or stirring blade-equipped heating device, but in the case of efficient and more uniform treatment, it is more preferable to use a rotary or stirring blade-equipped heating device.

[0071] In the (a) PPS resin of the present invention, functional groups such as carboxyl groups and amino groups may be introduced into the PPS resin terminals or side chains from the viewpoint of improving the reaction efficiency with the (b) silane coupling agent. A preferred embodiment has a functional group amount of 25 to 400 μmol / g, more preferably 25 to 250 μmol / g, more preferably 30 to 150 μmol / g, and even more preferably 30 to 80 μmol / g. By setting the functional group amount to 25 μmol / g or more, reactivity with the (b) silane coupling agent and other additives can be obtained, which is preferable. On the other hand, by setting the functional group amount of the PPS resin to 400 μmol / g or less, a decrease in processability and a decrease in flame retardancy and chemical resistance due to an increase in the amount of volatile components can be suppressed, which is preferable.

[0072] Examples of methods for introducing functional groups such as carboxyl groups and amino groups into the (a) PPS resin include a method of copolymerizing a polyhalogenated aromatic compound containing a carboxyl group or an amino group with a sulfidizing agent, and a method of adding a compound containing a carboxyl group or an amino group, such as maleic anhydride or sorbic acid, and reacting it with the (a) PPS resin while melt-kneading. The type of functional group is preferably a carboxyl group or an amino group.

[0073] (2)(b) Silane coupling agent In order to obtain a thin-walled molded article having excellent productivity and reliability, it is essential to blend 0.1 to 0.5 parts by weight of (b) a silane coupling agent per 100 parts by weight of PPS resin in the PPS resin composition constituting the thin-walled molded article of the embodiment of the present invention.

[0074] The blending amount of the (b) silane coupling agent used in the present invention must be 0.1 to 0.5 parts by weight relative to 100 parts by weight of the PPS resin, and is preferably 0.3 to 0.5 parts by weight. If the blending amount of the (b) silane coupling agent is less than 0.1 parts by weight, the tensile breaking elongation of the PPS resin composition is low, so that the thin-walled molded product is easily damaged in the crimping or fitting process, and the productivity is reduced. In addition, the reliability of the thin-walled molded product during actual use is also reduced. On the other hand, if the blending amount of the (b) silane coupling agent exceeds 0.5 parts by weight, the shrinkage anisotropy of the molded product increases, making it easier for warping to occur, and the reliability of the thin-walled molded product is reduced. In addition, the flowability of the PPS resin composition is reduced, making it difficult to perform injection molding of the thin-walled molded product.

[0075] Specific examples of the (b) silane coupling agent are preferably silane coupling agents having at least one functional group selected from an isocyanate group, an epoxy group, an amino group, a hydroxyl group, a mercapto group, a ureido group, and an alkoxy group.Specific examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N-phenylaminomethyltrimethoxysilane, N-phenylaminopropyl Preferred examples of such silane include γ-ureidopropyltrimethoxysilane, dimethoxymethyl-3-piperazinopropylsilane, 3-piperazinopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylethyldimethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptomethyldimethoxysilane, and γ-ureidopropyltrimethoxysilane.

[0076] Among the above-mentioned (b) silane coupling agents, from the viewpoints of reactivity and ease of handling, 3-isocyanatopropyltriethoxysilane, 3-aminopropyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane are preferred, and 3-isocyanatopropyltriethoxysilane is particularly preferred.

[0077] These (b) silane coupling agents can be used alone or in the form of a mixture of two or more kinds.

[0078] (3)(c) Carboxylic acid amide wax obtained by reacting higher aliphatic monocarboxylic acid with polybasic acid and diamine In order to obtain a thin-walled molded article having excellent productivity and reliability, it is essential to blend 1 to 5 parts by weight of (c) a carboxylic acid amide wax obtained by reacting a higher aliphatic monocarboxylic acid with a polybasic acid and a diamine (hereinafter sometimes abbreviated as carboxylic acid amide wax) with respect to 100 parts by weight of PPS resin in the PPS resin composition constituting the thin-walled molded article of the embodiment of the present invention. Conventionally, it has been known that blending (c) carboxylic acid amide wax with about 0.1 to 1 part by weight with respect to 100 parts by weight of PPS resin exerts an effect as a mold release agent. On the other hand, in the present invention, it has been newly found that by blending a higher amount, the shrinkage anisotropy of a molded article made of a PPS resin composition is reduced, and the effect of suppressing warpage and reducing warpage variation is exerted, making it suitable for thin-walled molded articles. In addition, it is suitable for thin-walled molded articles in terms of improved fluidity and small decrease in high-temperature rigidity, as represented by deflection temperature under load (hereinafter sometimes abbreviated as DTUL).

[0079] The amount of the (c) carboxylic acid amide wax used in the present invention must be 1 part by weight or more and 5 parts by weight or less per 100 parts by weight of PPS resin, preferably more than 1 part by weight and 5 parts by weight or less, more preferably 1.5 parts by weight or more and 5 parts by weight or less, and particularly preferably 3 parts by weight or more and 5 parts by weight or less. If the amount of the (c) carboxylic acid amide wax is less than 1 part by weight, the effect of suppressing warpage and reducing warpage variation is not sufficiently obtained, and the productivity and reliability of the thin-walled molded product are reduced. On the other hand, if the amount of the (c) carboxylic acid amide wax is more than 5 parts by weight, the amount of gas derived from the (c) carboxylic acid amide wax increases and the fluidity also increases excessively, making it difficult to perform injection molding of the thin-walled molded product.

[0080] The (c) carboxylic acid amide wax used in the present invention is a carboxylic acid amide wax obtained by reacting a higher aliphatic monocarboxylic acid with a polybasic acid and a diamine. The higher aliphatic monocarboxylic acid is preferably an aliphatic monocarboxylic acid having 10 or more carbon atoms and a hydroxycarboxylic acid. Specific examples include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, behenic acid, montanic acid, and 12-hydroxystearic acid. Among them, a saturated aliphatic monocarboxylic acid having 16 or more carbon atoms, such as palmitic acid, stearic acid, behenic acid, montanic acid, and 12-hydroxystearic acid, and a hydroxycarboxylic acid are preferred. Two or more of these higher aliphatic monocarboxylic acids may be used in combination.

[0081] The polybasic acid is a carboxylic acid having a dibasic acid or more. Specific examples include aliphatic dicarboxylic acids such as malonic acid, succinic acid, adipic acid, sebacic acid, pimelic acid, and azelaic acid, aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, and isophthalic acid, and alicyclic dicarboxylic acids such as cyclohexyl dicarboxylic acid and cyclohexyl succinic acid. Two or more of these may be used in combination, and among them, succinic acid, adipic acid, sebacic acid, and pimelic acid are preferred.

[0082] Specific examples of the diamine include ethylenediamine, 1,3-diaminopropane, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylylenediamine, paraxylylenediamine, tolylenediamine, phenylenediamine, and isophoronediamine. These may be used in combination of two or more. Among these, ethylenediamine is preferred.

[0083] The mixing ratio of the higher aliphatic monocarboxylic acid and the polybasic acid is preferably 0.18 mol or more, more preferably 0.2 mol or more, of the polybasic acid per 2 mol of the higher aliphatic monocarboxylic acid. The amount of the polybasic acid is preferably 1.0 mol or less. The mixing ratio of the higher aliphatic monocarboxylic acid and the diamine is preferably 1.0 mol or more, more preferably 1.2 mol or more, of the diamine per 2 mol of the higher aliphatic monocarboxylic acid. The amount of the diamine is preferably 2.2 mol or less, more preferably 2.0 mol or less.

[0084] The carboxylic acid amide wax used in the embodiment of the present invention is obtained by a dehydration condensation reaction by heating a higher aliphatic monocarboxylic acid, a polybasic acid, and a diamine, and the product obtained by such a dehydration condensation reaction is often a mixture of a product of the reaction of a higher aliphatic monocarboxylic acid, a polybasic acid, and a diamine, and a product of the reaction of a higher aliphatic monocarboxylic acid and a diamine that does not contain a structure derived from a polybasic acid. The product ratio varies depending on the synthesis conditions, such as the molar ratio of each component charged during synthesis. In the embodiment of the present invention, the ratio of the product of the reaction of a higher aliphatic monocarboxylic acid and a diamine that does not contain a polybasic acid to the total carboxylic acid amide wax is preferably 5 to 65% by weight, more preferably 15 to 65% by weight, even more preferably 20 to 65% by weight, and particularly preferably 30 to 65% by weight, based on the total carboxylic acid amide wax, from the viewpoints of toughness, warpage suppression, and flowability.

[0085] The weight percent of the product of the reaction of higher aliphatic monocarboxylic acid with diamine and not containing polybasic acid is determined by using a differential scanning calorimeter. Specifically, it can be determined by comparing the heat of fusion of the peak corresponding to the product of the reaction of higher aliphatic monocarboxylic acid with diamine and not containing polybasic acid, which appears during the second scan (when the temperature is raised, lowered, and then raised again) using a carboxylic acid amide wax as a sample, with the heat of fusion of a sample of a separately available pure compound product of the reaction of higher aliphatic monocarboxylic acid with diamine and not containing polybasic acid, which is similarly determined.

[0086] The carboxylic acid amide wax (c) used in the present invention may contain an antioxidant. By adding an antioxidant, it is possible to reduce gas generation and mold staining caused by the carboxylic acid amide wax (c). As the antioxidant, for example, a phosphorus-based antioxidant, a hindered phenol-based antioxidant, a sulfur-based antioxidant, and an amine-based antioxidant are used. Two or more of these antioxidants may be used in combination. More preferably, a phosphorus-based antioxidant and / or a hindered phenol-based antioxidant is used. The amount of the antioxidant is preferably 0.01 to 5 parts by weight, more preferably 0.01 to 3 parts by weight, based on 100 parts by weight of the carboxylic acid amide wax (c).

[0087] (4)(d) Thermoplastic elastomer In the PPS resin composition constituting the thin molded article according to the embodiment of the present invention, the blending amount of the thermoplastic elastomer (d) is essentially 0.5 parts by weight or less per 100 parts by weight of the PPS resin. The blending amount of the thermoplastic elastomer (d) is more preferably 0.3 parts by weight or less, and even more preferably 0.1 parts by weight or less. Most preferably, the blending amount does not contain the thermoplastic elastomer (d), i.e., 0 parts by weight.

[0088] Thermoplastic elastomers are materials that plasticize at high temperatures and exhibit rubber-like elasticity at room temperature. When a thermoplastic elastomer is blended into a PPS resin composition, the thermoplastic elastomer becomes plasticized and exhibits rubber elasticity, resulting in a decrease in the mechanical properties of thin-walled molded products and a decrease in dimensional stability due to a decrease in high-temperature rigidity, as represented by DTUL. In other words, the reliability and productivity of thin-walled molded products decrease. In addition, the blending of a thermoplastic elastomer reduces the fluidity, resulting in a decrease in the productivity of thin-walled molded products. For the above reasons, in the present invention, it is essential that the blending amount of (d) thermoplastic elastomer is 0.5 parts by weight or less.

[0089] Specific examples of the thermoplastic elastomer include olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and styrene-based thermoplastic elastomers. Examples of the olefin-based thermoplastic elastomers include ethylene-butene copolymers, ethylene-propylene copolymers, ethylene-hexene copolymers, ethylene-octene copolymers, ethylene-vinyl acetate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-glycidyl methacrylate copolymers, ethylene-butyl acrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-styrene copolymers, ethylene-methyl acrylate-glycidyl methacrylate copolymers, ethylene-ethyl acrylate-glycidyl methacrylate copolymers, and ethylene-vinyl acetate-glycidyl methacrylate copolymers.

[0090] (5)(e) Other additives Resins other than (a) PPS resin and (d) thermoplastic elastomer may be added to the PPS resin composition of the embodiment of the present invention, as long as the effects of the present invention are not impaired. Specific examples of such resins include polyamide, polybutylene terephthalate, polyethylene terephthalate, polyetherimide, polyetherimide-siloxane copolymer, polyketone, liquid crystal polymer, polyether ketone, polyether ether ketone, fluororesin (polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluoro(alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene-hexafluoropropylene copolymer, polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE)), and silicone elastomer, but are not limited thereto. The amount of such resin added is preferably less than 10 parts by weight, more preferably less than 5 parts by weight, and more preferably less than 3 parts by weight, relative to 100 parts by weight of PPS resin. The lower limit is preferably such that these resins are not included, that is, 0 parts by weight.

[0091] The PPS resin composition according to the embodiment of the present invention may contain the following compounds for the purpose of modification. Plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, and organic phosphorus compounds, crystal nucleating agents such as organic phosphorus compounds and polyether ether ketones, metal soaps such as montanic acid waxes, lithium stearate, and aluminum stearate, mold release agents such as silicone compounds, water, lubricants, UV inhibitors, coloring inhibitors, colorants, foaming agents, phosphorus-based flame retardants, halogen-based flame retardants, and inorganic flame retardants may be blended. If the amount of any of the above compounds exceeds 10 parts by weight per 100 parts by weight of the total PPS resin composition, the inherent properties of the PPS resin composition of the present invention are impaired, and it is not preferable to add 5 parts by weight or less, more preferably 1 part by weight or less.

[0092] In the present invention, an epoxy resin can be added to the PPS resin composition for the purpose of increasing the toughness of the composition.

[0093] Specific examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, brominated epoxy resins, special skeleton bifunctional epoxy resins having a biphenyl skeleton or a naphthalene skeleton, glycidyl ether type epoxy resins such as multifunctional epoxy resins such as cresol novolac type, trisphenol methane type, and dicyclopentadiene type, glycidyl amine type epoxy resins such as aromatic amine type and aminophenol type, and glycidyl ester type epoxy resins such as hydrophthalic acid type and dimer acid type. The amount of such epoxy resins to be added is preferably 0.1 to 5 parts by weight, particularly preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the total PPS resin composition.

[0094] Although not essential, inorganic fillers can be used in the PPS resin composition according to the embodiment of the present invention as long as they do not impair the effects of the present invention. Specific examples of such inorganic fillers include fullerene, talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, silicates such as alumina silicate, metal compounds such as silicon oxide, magnesium oxide, alumina, zirconium oxide, titanium oxide, and iron oxide, carbonates such as calcium carbonate, magnesium carbonate, and dolomite, sulfates such as calcium sulfate and barium sulfate, non-fibrous fillers such as glass beads, glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black, and graphite, among which mica, calcium carbonate, and carbon black are preferred. Mica is particularly preferred from the viewpoint of reducing the anisotropy of mold shrinkage and suppressing warpage, and calcium carbonate and carbon black are particularly preferred from the viewpoint of corrosion prevention and lubricant effects. In addition, these inorganic fillers may be hollow, and two or more types may be used in combination. Furthermore, these inorganic fillers may be 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 before use.

[0095] The amount of the inorganic filler is selected to be less than 10 parts by weight, preferably less than 5 parts by weight, more preferably less than 3 parts by weight, and even more preferably 1 part by weight or less, relative to 100 parts by weight of the total PPS resin composition. There is no particular lower limit, but 0.0001 parts by weight or more is preferred. While the incorporation of an inorganic filler is effective in improving the strength of the material, an incorporation of more than 10 parts by weight is not preferred because it reduces toughness.

[0096] In the present invention, the incorporation of fibrous fillers such as glass fibers and carbon fibers is not preferred because it not only reduces toughness like other inorganic fillers, but also increases the anisotropy of molding shrinkage due to the orientation of the fibrous fillers, making warping more likely to occur. The amount of fibrous filler to be incorporated is preferably 0.5 parts by weight or less, more preferably 0.1 parts by weight or less, and most preferably is not substantially contained, i.e., 0 parts by weight, relative to 100 parts by weight of the PPS resin.

[0097] (6) Method for producing resin composition The method for producing the PPS resin composition according to the embodiment of the present invention includes production in a molten state and production in a solution state, but from the viewpoint of simplicity, production in a molten state is preferably used. For production in a molten state, melt kneading using an extruder or melt kneading using a kneader can be used, but from the viewpoint of productivity, melt kneading using an extruder that can be continuously produced is preferably used. For melt kneading using an extruder, at least one extruder such as a single screw extruder, a twin screw extruder, a multi-screw extruder such as a four-screw extruder, or a twin-screw single screw composite extruder can be used, but from the viewpoint of kneading property, reactivity, and productivity improvement, a multi-screw extruder such as a twin screw extruder or a four-screw extruder can be preferably used, and melt kneading using a twin screw extruder is most preferable.

[0098] A more specific method of melt kneading is not necessarily limited to this, but it is preferable to use a twin-screw extruder having an L / D (L: screw length, D: screw diameter) of 10 or more, preferably 20 or more, and having two or more kneading sections, preferably three or more. There is no particular upper limit to L / D, but 60 or less is preferable from the viewpoint of economic efficiency. There is also no particular upper limit to the number of kneading sections, but 10 or less is preferable from the viewpoint of productivity. The ratio of the kneading sections to the entire screw length is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more, from the viewpoint of dispersibility of (e) other resins in the PPS resin. On the other hand, the upper limit of the ratio of the kneading sections to the entire screw length is preferably 40% or less, from the viewpoint of preventing deterioration of the resin due to the generation of excessive shear heat during kneading.

[0099] The screw rotation speed is preferably 150 to 1000 rpm, more preferably 300 to 1000 rpm, and even more preferably 350 to 800 rpm. When the screw rotation speed exceeds 150 rpm, the kneading force is sufficient, so that when (e) other additives are added, their aggregation is suppressed, leading to the development of the desired toughness. When the screw rotation speed exceeds 1000 rpm, deterioration of the resin and additives occurs due to excessive shear heat generation during kneading, leading to a decrease in toughness, a decrease in mold fouling, the generation of burrs due to a decrease in melt viscosity, and a decrease in the productivity and reliability of thin-walled molded products due to decomposition products, which is not preferable.

[0100] Specifically, the preferred range of the cylinder temperature (°C) is 280 to 400°C, more preferably 280 to 360°C, and even more preferably 280 to 330°C.

[0101] The order of mixing the raw materials when melt-kneading is not particularly limited, and any of the following methods may be used: a method in which all the raw materials are mixed and then melt-kneaded by the above-mentioned method; a method in which a portion of the raw materials are mixed and then melt-kneaded by the above-mentioned method, and then the remaining raw materials are mixed and melt-kneaded; or a method in which a portion of the raw materials are mixed and then the remaining raw materials are mixed using a side feeder while being melt-kneaded by a twin-screw extruder.

[0102] (7) PPS resin composition The PPS resin composition constituting the thin-walled molded product of the embodiment of the present invention must have a tensile breaking elongation, which is one of the physical properties indicating the toughness of a material (dumbbell test piece (ISO527-2-1A), tensile speed of 50 mm / min, 23°C, conforming to ISO527-1,2 (2012)), of 5% or more. 10% or more is more preferable, and 12% or more is even more preferable. From the viewpoint of preventing damage during the crimping and fitting process of the thin-walled molded product and during actual use, it is desirable for the tensile breaking elongation of the resin composition to be 5% or more. From the viewpoint of productivity and reliability by preventing damage to components, a higher tensile breaking elongation is preferable, and although there is no particular upper limit, it can be exemplified as being substantially 500% or less. The method for obtaining a PPS resin composition having such properties is not particularly limited, but examples thereof include (a) setting the amount of (b) silane coupling agent to 0.1 to 0.5 parts by weight relative to 100 parts by weight of PPS resin, (c) setting the amount of carboxylic acid amide wax to 1 to 5 parts by weight, and (c) ensuring that the content of the reaction product of higher aliphatic monocarboxylic acid and diamine (excluding polybasic acid) contained in the carboxylic acid amide wax is 5 to 65% by weight.

[0103] From the viewpoint of the reliability of the thin-walled molded product, the PPS resin composition constituting the thin-walled molded product of the embodiment of the present invention has a warpage of 1.8 mm or less in a square plate (W (width): 80 mm × D (depth): 80 mm × H (height): 1 mm) obtained by injection molding the PPS resin composition, more preferably 1.7 mm or less, even more preferably 1.6 mm or less, and most preferably 1.4 mm or less. If the warpage is 1.8 mm or less, the warpage is small when the PPS resin composition is made into a thin-walled molded product, and the originally expected member function is fully exhibited during actual use of the thin-walled molded product, which is preferable, and thus the reliability is high. From the viewpoint of the reliability of the thin-walled molded product, the warpage is most preferably 0 mm, and although there is no particular lower limit, it can be exemplified as being substantially 0.1 mm or more. In addition, the standard deviation of the warpage is preferably 0.3 mm or less, more preferably 0.25 mm or less, and particularly preferably 0.2 mm or less. A standard deviation of 0.3 mm or less in the amount of warpage means that the variation in the amount of warpage is small and the dimensional stability is excellent, and the rate of obtaining good products in thin-walled molded products is improved, resulting in excellent productivity, and the thin-walled molded products can achieve stable functional expression during actual use, resulting in excellent reliability. From the viewpoint of productivity and reliability of thin-walled molded products, it is most preferable that the standard deviation of the amount of warpage is 0 mm, and although there is no particular lower limit, it can be exemplified as being substantially 0.05 mm or more.

[0104] The amount of warpage and its standard deviation can be evaluated as follows. The PPS resin composition constituting the thin-walled molded product is injection molded at a cylinder temperature of 320°C and a mold temperature of 150°C to obtain a square plate (W: 80 mm x D: 80 mm x H: 1 mm), which is then left to stand at room temperature for 24 hours or more. A 20g weight is placed in the center of the square plate placed on a reference stand, and the height of the reference stand is set to 0 mm. The height of the corner that has been warped the most is taken as the amount of warpage and measured with a height gauge. Similar measurements are made using five square plates, and the average value and standard deviation are adopted.

[0105] The amount of warpage and its standard deviation of a molded article made of a PPS resin composition can be reduced by reducing the mold shrinkage anisotropy of the molded article, or by maintaining high high-temperature rigidity, such as DTUL, and suppressing deformation during release from the mold in injection molding. There are no particular limitations on the method for obtaining a PPS resin composition having such characteristics, but examples of the method include (a) setting the amount of (b) silane coupling agent to 0.1 to 0.5 parts by weight relative to 100 parts by weight of PPS resin, (c) setting the amount of carboxylic acid amide wax to 1 to 5 parts by weight, (c) setting the content of the reaction product of higher aliphatic monocarboxylic acid and diamine (excluding polybasic acid) contained in the carboxylic acid amide wax to 5 to 65% by weight, and (d) setting the amount of thermoplastic elastomer to 0.5 parts by weight or less.

[0106] The mold shrinkage anisotropy of the molded product can be evaluated by the mold shrinkage ratio. Specifically, the PPS resin composition constituting the thin-walled molded product is injection molded at a cylinder temperature of 320°C and a mold temperature of 150°C to obtain a square plate (W: 80 mm x D: 80 mm x H: 1 mm), which is left at room temperature for 24 hours or more. Then, the square plate dimensions in the MD direction are measured using a caliper. Measurements are performed at three points, the center of the square plate and positions 10 mm from both ends, and the difference between the mold dimension in the MD direction and the square plate dimension at each position is calculated, and the average value of the difference divided by the mold dimension is calculated as the mold shrinkage ratio in the MD direction. The mold shrinkage ratio is also calculated in the TD direction in the same manner, and the mold shrinkage ratio in the MD direction is divided by the mold shrinkage ratio in the TD direction to calculate the mold shrinkage ratio. The closer the mold shrinkage ratio is to 1, the smaller the mold shrinkage anisotropy is, which means that warping is less likely to occur. The mold shrinkage ratio is preferably 0.6 or more, more preferably 0.63 or more, and particularly preferably 0.65 or more. The molding shrinkage ratio is most preferably 1, and although there is no particular upper limit, it can be, for example, substantially 0.95 or less.

[0107] The PPS resin composition constituting the thin-walled molded product of the embodiment of the present invention preferably has a DTUL of 180° C. or more, measured under a load of 0.45 MPa in accordance with ISO 75-1, 2 (2013). A DTUL of 180° C. or more is expected to suppress deformation when the thin-walled molded product is released from the mold in injection molding, and also suppress deformation during actual use of the thin-walled molded product in a high-temperature environment, which is preferable because it provides excellent productivity and reliability of the thin-walled molded product.

[0108] There are no particular limitations on the method for obtaining a PPS resin composition having such properties. For example, the amount of (d) thermoplastic elastomer blended per 100 parts by weight of (a) PPS resin may be 0.5 parts by weight or less.

[0109] The PPS resin composition constituting the thin-walled molded article of the embodiment of the present invention preferably has a fluidity of 300 Pa·s or less, more preferably 200 Pa·s or less, even more preferably 160 Pa·s or less, and particularly preferably 120 Pa·s or less, as measured by melt viscosity. A fluidity of 300 Pa·s or less is preferable because it can suppress insufficient filling during injection molding of the thin-walled molded article, thereby improving productivity. Furthermore, the fluidity measured by melt viscosity is preferably 30 Pa·s or more, more preferably 50 Pa·s or more, and particularly preferably 70 Pa·s or more. A fluidity of 30 Pa·s or more is preferable because it can suppress nasal dripping during injection molding and suppress burrs on the molded article. The method for obtaining a PPS resin composition having such properties is not particularly limited, but examples thereof include (a) setting the amount of (b) silane coupling agent to 0.1 to 0.5 parts by weight relative to 100 parts by weight of PPS resin, (c) setting the amount of carboxylic acid amide wax to 1 to 5 parts by weight, (c) setting the content of reaction product of higher aliphatic monocarboxylic acid and diamine (excluding polybasic acid) contained in the carboxylic acid amide wax to 5 to 65% by weight, and (d) setting the amount of thermoplastic elastomer to 0.5 parts by weight or less.

[0110] The fluidity can be evaluated by the following method. The shear rate was 1216 s when measured using a capillograph under the conditions of 320°C, orifice length L (mm) / orifice diameter D (mm) = 10. -1 The melt viscosity of the PPS resin composition is measured at this temperature and used as an index of fluidity.

[0111] (8)Thin-walled molded products The thin-walled molded product according to the embodiment of the present invention suppresses warping and its variation that occurs when the thickness of the thinnest part of the thin-walled molded product is 1 mm or less, and has excellent productivity and reliability. Even if the thickness of the thinnest part of the thin-walled molded product is thinner, the warping suppression effect is exhibited, so the thickness of the thinnest part of the thin-walled molded product is preferably 0.8 mm or less, and more preferably 0.6 mm or less. There is no particular lower limit, but from the viewpoint of maintaining the shape and function of the thin-walled molded product, a preferable range is 0.1 mm or more.

[0112] The thin-walled molded article of the present invention can be molded by various molding techniques such as injection molding, extrusion molding, compression molding, blow molding, and injection compression molding, among which injection molding is preferred from the viewpoint of productivity. Even in molding techniques such as injection molding, in which orientation occurs in the molded article and molding shrinkage anisotropy increases, which tends to cause warpage, the warpage and its variation can be suppressed, and the productivity and reliability of the thin-walled molded article are excellent.

[0113] The thin-walled molded product according to the embodiment of the present invention can be particularly preferably used as a battery insulating member. The battery insulating member refers to an insulating member for a primary or secondary battery, and is used to prevent an internal short circuit and an external short circuit in the primary or secondary battery.

[0114] Examples of primary or secondary batteries include primary batteries such as alkaline manganese dry batteries, galvanic batteries, nickel-based primary batteries, lithium batteries, manganese dry batteries, mercury batteries, and all-solid-state batteries, as well as secondary batteries such as lead-acid batteries, lithium-air batteries, lithium ion secondary batteries, lithium ion polymer secondary batteries, lithium iron phosphate batteries, lithium-sulfur batteries, nickel-cadmium storage batteries, nickel-hydrogen rechargeable batteries, nickel-lithium batteries, nickel-zinc batteries, and all-solid-state batteries.

[0115] Examples of battery insulating members include insulating plates, gaskets, terminal holders, cases, insulating rings, insulating tubes, wire coatings, bus bar coatings, etc. Battery insulating members made of the PPS resin composition of the present invention have excellent toughness, which can reduce the risk of breakage during the crimping process, and are also highly reliable, so that they are preferably applied to insulating plates, gaskets, terminal holders, and cases, which are important safety members of batteries.

[0116] The thin-walled molded product for battery insulating members of the present invention can be molded into a thin wall due to the high fluidity of the PPS resin composition constituting the molded product, and the high toughness prevents damage during the crimping and fitting process of the thin-walled molded product for battery insulating members. In addition, the suppression of warpage variation results in a high rate of obtaining good products for the thin-walled molded product for battery insulating members. These effects result in excellent productivity. Furthermore, the high toughness prevents damage during actual use, and the suppression of warpage and its variation is expected to stably exhibit the short-circuit prevention function of the battery, so that it is highly reliable. In recent years, with the background of increasing awareness of environmental protection, a rapid increase in demand for electric vehicles is predicted. By using the product as an insulating material for on-board lithium-ion batteries to be installed in these vehicles, it is possible to achieve a particularly suitable use, as it has productivity that can meet the demand, while also becoming a highly reliable battery that also contributes to ensuring the safety of passengers. EXAMPLES

[0117] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto.

[0118] In the examples and comparative examples, the following were used as (a) PPS resin, (b) silane coupling agent, (c) carboxylic acid amide wax, (d) thermoplastic elastomer, and (e) other additives.

[0119] [(a) PPS resin (a-1, a-2)] [Reference example 1 PPS resin (a-1)] In an autoclave equipped with a stirrer, 8267.37g (70.00 mol) of 47.5% sodium hydrosulfide, 2923.88g (70.17 mol) of 96% sodium hydroxide, 11434.50g (115.50 mol) of N-methyl-2-pyrrolidone (NMP), 1894.20g (23.10 mol) of sodium acetate, and 10500g of ion-exchanged water were charged, and the mixture was gradually heated to 230°C over about 3 hours while passing nitrogen through it at normal pressure. After distilling out 14780.1g of water and 280g 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 1.06 mol, including the water consumed in the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.017 mol per mole of charged alkali metal sulfide.

[0120] Next, 10420g (70.89 mol) of p-dichlorobenzene and 9078.30g (91.70 mol) of NMP were added, and the reaction vessel was sealed under nitrogen gas. While stirring at 240 rpm, the temperature was raised to 240°C at a rate of 0.6°C / min, and after reacting at 240°C for 40 minutes, the temperature was raised to 275°C at a rate of 0.8°C / min. Then, 2394g (133 mol) of ion-exchanged water was pressed into the autoclave while cooling to 250°C at a rate of 1.3°C / min. Then, it was cooled to 200°C at a rate of 1.0°C / min, and then quenched to near room temperature.

[0121] The contents were taken out and diluted with 26,300 g of NMP, after which the solvent and solids were filtered off using a sieve (80 mesh), and the resulting particles were washed with 31,900 g of NMP and filtered off. These were washed and filtered off several times with 56,000 g of ion-exchanged water, and then washed and filtered off with 70,000 g of 0.05 wt% acetic acid aqueous solution. After washing and filtering with 70,000 g of ion-exchanged water, the resulting hydrous PPS particles were dried with hot air at 80°C and dried under reduced pressure at 120°C. The resulting PPS resin (a-1) had a weight average molecular weight of 73,000, a melting point of 280°C, a carboxyl group amount of 35 μmol / g, and a melt viscosity of 177 Pa·s. The melt viscosity was measured using a capillograph under the conditions of 320°C, orifice length L (mm) / orifice diameter D (mm) = 10, and a shear rate of 1216 s -1 The value at .

[0122] [Reference example 2 PPS resin (a-2)] PPS resin (a-2) was obtained under the same conditions as in Reference Example 1, except that the amount of p-dichlorobenzene added was 10,458.90 g (71.15 mol). The obtained PPS resin (a-2) had a weight average molecular weight of 54,000, a melting point of 280°C, a carboxyl group amount of 42 μmol / g, and a melt viscosity of 57 Pa s. The melt viscosity was measured in the same manner as in Reference Example 1.

[0123] [(b) Silane coupling agent (b-1)] b-1: 3-isocyanatopropyltriethoxysilane ("KBE9007N" manufactured by Shin-Etsu Silicone Co., Ltd.)

[0124] [(c) Carboxylic acid amide wax (c-1, c-2)] [Reference Example 1 Carboxylic acid amide wax (c-1)] 2 moles of stearic acid and 1 mole of sebacic acid were charged in a reactor, and after heating and dissolving, 2 moles of ethylenediamine were added, and a dehydration reaction was started at 160°C in a nitrogen stream, and the reaction was continued until the amine value was 5 or less at 250-260°C, and a carboxylic acid amide wax (c-1) was obtained. This wax was used as a sample and measured with a differential scanning calorimeter under the conditions of a heating rate and a cooling rate of 20°C / min, a scanning range of 50-170°C, and a sample amount of about 4 mg. When the second melting peak value was measured by scanning twice consecutively, an endothermic peak was observed at 144°C, and the heat value was 40 J / g. On the other hand, when ethylene bisstearylamide (corresponding to a product of a higher aliphatic monocarboxylic acid and a diamine when the above raw material is used and does not contain a polybasic acid) was used as a sample and measured in the same manner with a differential scanning calorimeter, an endothermic peak was observed at 145°C, and the heat value was 125 J / g. Since the endothermic peaks almost coincide with each other, it is considered that the endothermic peak at 144°C of the carboxylic acid amide wax (c-1) corresponds to ethylene bisstearylamide, and from the calorific value ratio, it was derived that the amount of ethylene bisstearylamide in the carboxylic acid amide wax (c-1) was approximately 32% by weight.

[0125] [Reference Example 2 Carboxylic acid amide wax (c-2)] A reactor was charged with 1.97 moles of stearic acid and 0.32 moles of sebacic acid, which were then heated to dissolve, and 1.37 moles of ethylenediamine were gradually added. The dehydration reaction was initiated at 160°C in a nitrogen stream, and the reaction continued until the amine value reached 5 or less at 250°C, yielding a carboxylic acid amide wax (c-2). When measured using a differential scanning calorimeter in the same manner as above, an endothermic peak was observed at 145°C, with a calorific value of 75 J / g. From the calorific value ratio, it was derived that the ethylenebisstearylamide in the carboxylic acid amide wax (c-2) was approximately 60% by weight.

[0126] [(d) Thermoplastic elastomer (d-1)] d-1: Ethylene-glycidyl methacrylate copolymer (olefin resin manufactured by Sumitomo Chemical Co., Ltd., Bondfast BF-E, melting point 105°C, MFR: 3g / 10min (190°C, 21.2N load), reactive functional group content: 12% by weight)

[0127] [(e) Other additives (e-1)] e-1: Glass fiber (Nippon Electric Glass Co., Ltd., T760H) In the following examples, material properties were evaluated by the following methods.

[0128] [Tensile test] The PPS resin composition pellets obtained in the examples and comparative examples were dried at 120°C for 3 hours using a hot air dryer, then fed to a Sumitomo Heavy Industries injection molding machine (SE-75DUZ) set at a cylinder temperature of 310°C and a mold temperature of 145°C, and injection molding was performed using a mold with a type A1 test piece shape specified in ISO 20753 (2008) under conditions where the average speed of the molten resin passing through the cross-sectional area of ​​the central parallel part was 400±50 mm / s to obtain a test piece. The test piece was conditioned for 16 hours under conditions of 23°C and 50% relative humidity, and then the tensile elongation (and strain) at break was measured according to the ISO 527-1,2 (2012) method under conditions of a chuck distance of 114 mm and a test speed of 50 mm / min.

[0129] [DTUL] A type B2 test specimen was obtained by cutting out the central parallel portion of a type A1 test specimen molded under the same conditions as the test specimen used for the tensile test. Using this test specimen, the DTUL was measured under a load of 0.45 MPa in accordance with ISO75-1,2 (2013).

[0130] [Warpage amount and its standard deviation] The PPS resin compositions obtained in the examples and comparative examples were dried at 120°C for 3 hours using a hot air dryer, and then fed to a Sumitomo Heavy Industries injection molding machine (SE-75DUZ) with a cylinder temperature of 320°C and a mold temperature of 150°C, and a molded product was obtained using a square plate mold (W: 80mm x D: 80mm x H: 1mm). The square plate was left at room temperature for 24 hours or more. A 20g weight was placed in the center of the square plate placed on a reference table, and the height of the reference table was set to 0mm. The height of the corner that was most highly warped was measured as the amount of warpage using a height gauge. Similar measurements were performed using five square plates, and the average value and standard deviation were adopted, respectively.

[0131] [Molding shrinkage ratio] A square plate (W: 80mm x D: 80mm x H: 1mm) molded under the same conditions as the test specimen used to measure the amount of warpage was left at room temperature for more than 24 hours. After that, the dimensions of the square plate in the MD direction were measured using a caliper. Measurements were performed at three points, the center of the square plate and 10mm from both ends, and the difference between the mold dimensions in the MD direction and the square plate dimensions at each point was calculated. The average value of the difference divided by the mold dimensions was calculated as the molding shrinkage ratio in the MD direction. The molding shrinkage ratio in the TD direction was also calculated in the same way, and the molding shrinkage ratio in the MD direction was divided by the molding shrinkage ratio in the TD direction to calculate the molding shrinkage ratio.

[0132] [Liquidity] The shear rate was 1216 s when measured using a capillograph at 320°C and under the conditions of orifice length L (mm) / orifice diameter D (mm) = 10. -1 The melt viscosity of the PPS resin composition was measured at 100° C. and used as an index of fluidity.

[0133] [Examples 1 to 6, Comparative Examples 1 to 6] PPS resin, silane coupling agent, carboxylic acid amide wax, thermoplastic elastomer, and other additives were dry blended according to the composition shown in Table 1, and then fed into a Japan Steel Works TEX30α twin-screw extruder (L / D=30, two kneading sections) and melt-kneaded. Kneading was performed at a temperature of 300°C and a rotation speed of 300 rpm. After pelletizing with a strand cutter, the pellets were dried at 120°C for 3 hours and then subjected to injection molding. The evaluation results are shown in Table 1.

[0134] [Table 1]

[0135] The results of the above-mentioned Examples and Comparative Examples will be compared and explained.

[0136] In Examples 1 to 6, (a) PPS resin, (b) silane coupling agent, and (c) carboxylic acid amide wax are blended in a specific composition, and (d) a PPS resin composition is obtained without blending a thermoplastic elastomer. The composition has excellent toughness and fluidity, as represented by tensile elongation at break, while having a large molding shrinkage ratio, i.e., small anisotropy, which reduces the amount of warpage and suppresses its variation. The decrease in DTUL is also suppressed. These characteristics make the composition suitable for thin-walled molded products.

[0137] On the other hand, in Comparative Example 1, the composition not containing (c) carboxylic acid amide wax and consisting only of (a) PPS resin and (b) silane coupling agent has a small molding shrinkage ratio, i.e., a large anisotropy, resulting in a large amount of warpage and its variation. The same result was obtained in Comparative Example 2, in which the amount of (c) carboxylic acid amide wax was small. In Comparative Example 4, in which the amount of (c) carboxylic acid amide wax was excessive, gas generation originating from (c) carboxylic acid amide wax and excessive increase in fluidity caused runny nose during injection molding, making it impossible to evaluate the characteristics.

[0138] In Comparative Example 3, the molding shrinkage ratio is small because of the large amount of (b) silane coupling agent, that is, the anisotropy is large, and the amount of warpage and its variation are large. From the comparison with Example 1, it is presumed that the anisotropy of the molding shrinkage ratio is caused by the reaction of the silane coupling agent.

[0139] In Comparative Example 5, the blended amount of (d) thermoplastic elastomer was large, and the DTUL and fluidity were reduced.

[0140] Comparative Example 6 has low toughness due to the inclusion of glass fiber as a fibrous filler, and also has a significantly small molding shrinkage ratio due to the orientation of the glass fiber, resulting in a large amount of warpage.

Claims

1. A polyphenylene sulfide resin composition comprising (a) 100 parts by weight of polyphenylene sulfide resin, (b) 0.1 to 0.5 parts by weight of a silane coupling agent, and (c) 1 to 5 parts by weight of a carboxylic acid amide wax obtained by reacting a higher aliphatic monocarboxylic acid with a polybasic acid and a diamine, and (d) a thermoplastic elastomer in an amount of 0.5 parts by weight or less, wherein the polyphenylene sulfide resin composition is injection molded to obtain a test piece having a tensile elongation at break (measured in accordance with ISO 527-1, 2 (2012)) of 5% or more, and the polyphenylene sulfide resin composition is injection molded to obtain a square plate (W: 80 mm × D: 80 mm × H: 1 mm) having a warpage of 1.8 mm or less, and the thinnest part of the thinnest part has a thickness of 1 mm or less.

2. 2. The thin-walled molded product according to claim 1, wherein the (c) carboxylic acid amide wax obtained by reacting a higher aliphatic monocarboxylic acid with a polybasic acid and a diamine contains 5 to 65% by weight of a product of a higher aliphatic monocarboxylic acid and a diamine, the product not containing a structure derived from a polybasic acid.

3. 2. The thin-walled molded product according to claim 1, wherein a test piece obtained by injection molding the polyphenylene sulfide resin composition has a deflection temperature under load (measured in accordance with ISO 75-1, 2 (2013), 0.45 MPa load) of 180°C or higher.

4. 2. The thin-walled molded product for battery insulating members according to claim 1, wherein the thickness of the thinnest part is 1 mm or less.

5. The thin-walled molded product for an insulating member of an in-vehicle lithium-ion battery according to claim 1, having a thickness of 1 mm or less at its thinnest portion.