JP2013227366A - Thermoplastic resin composition and its molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition having high adhesive strength to a metal and heat resistance, and a molding comprising the same.SOLUTION: There is disclosed a thermoplastic resin composition formulated of 40-90 wt.% of polyphenylene sulfide (A), 5-50 wt.% of a liquid crystalline polyester (B), and 1-20 wt.% of an elastomer (C) with a melt flow rate of 10-400 g/10 min (measured pursuant to ISO1133, temperature 190°C, load 2,160 g).

Description

  The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a thermoplastic resin composition obtained by blending polyphenylene sulfide, liquid crystalline polyester, and an elastomer having a specific melt flow rate, and a molded product obtained therefrom.

  Polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) has excellent heat resistance, chemical resistance, and electrical insulation, and is used for various electric / electronic parts, mechanical parts, automobile parts and the like. In addition, liquid crystalline polyesters are excellent in heat resistance, fluidity, and dimensional stability due to their liquid crystal structure, and the demand is growing mainly for small electric and electronic parts that require them. Therefore, for the purpose of solving problems such as anisotropy of liquid crystalline polyester by applying PPS, polyphenylene sulfide and liquid crystalline polyester are blended, and examination of improvement of toughness by controlling the alloy structure is performed. Studies have been made on improving the weld strength by reducing the directivity (for example, Patent Documents 1 and 2). Moreover, about those, the examination which improves the toughness of a thermoplastic resin composition by further mix | blending an appropriate elastomer, respectively is also performed.

  By the way, for electrical / electronic parts such as connectors and switches, and automobile parts, parts are being designed with composite materials of resin and metal parts for miniaturization and precision. Resin and metal composite materials are required to have high adhesion between the resin and the metal in order to obtain waterproofness and sealing properties. However, the resin and metal adhere to each other due to the difference in coefficient of linear expansion due to temperature changes. Is known to decrease. Therefore, as a study for improving the adhesion between polyphenylene sulfide and / or liquid crystalline polyester and metal, studies are being made on mold temperature control during insert molding and surface modification of resin molded products by plasma treatment (for example, Patent Documents 3 and 4). In addition, since patent document 1 makes toughness and flexibility a subject, and patent document 2 makes impact resistance a subject, all are about the adhesive improvement between resin and a metal, It is not described at all.

JP 2007-146123 A JP-A-5-156135 JP 2009-190294 A JP 2003-268241 A

  However, in the conventional technology, in order to improve the adhesion between the resin and the metal, it is necessary to introduce a special mold and process the molded product, and it is difficult to apply to various shaped parts and simplify the process. In addition, in the case where the above treatment is not performed, the adhesion is not sufficiently satisfied. Furthermore, if the heat resistance of the thermoplastic resin composition is not sufficient due to the high temperature during reflow treatment of lead-free solder surface mounting in recent electrical and electronic component applications, the resin-metal warping or blistering may cause Adhesion decreases, and weld position variation occurs due to fluctuations in fluidity between the thin and thick portions of the resin flow path of the molded product during insert molding of composite molded products with metal parts. There was a problem such as.

  The present invention provides a thermoplastic resin composition having excellent adhesive strength between a resin and a metal, having high metal adhesion even after high-temperature treatment, and further having a small dependence on flow thickness, and a molded product thereof. It is intended to do.

  As a result of intensive studies to solve the above problems, the present inventors have formulated a thermoplastic resin composition comprising polyphenylene sulfide and liquid crystalline polyester, and further blended with an elastomer having a specific melt flow rate. The present inventors have found that it has a high adhesive strength between a resin and a metal, maintains high metal adhesion even after high-temperature treatment, and further has a small thickness dependency of fluidity.

That is, the present invention has been made to solve the above-described problems, and embodiments of the present invention can include at least a part of the following configurations.
(1) The total of (A), (B) and (C) is 100% by weight, the polyphenylene sulfide (A) is 40 to 90% by weight, the liquid crystalline polyester (B) is 5 to 50% by weight, and the melt flow A thermoplastic resin composition comprising 1 to 20% by weight of an elastomer (C) having a rate (according to ISO 1133, measured at a temperature of 190 ° C. and a load of 2160 g) of 10 to 400 g / 10 minutes.
(2) The thermoplastic resin composition as described in (1), wherein the elastomer (C) is an elastomer having a structural unit derived from acrylic acid.
(3) The thermoplastic resin composition according to (1) or (2), wherein the elastomer (C) is a copolymerized elastomer having a content of structural units derived from acrylic acid of 20 to 50% by weight. .
(4) Any of (1) to (3), wherein the liquid crystalline polyester (B) is composed of the following structural units (I), (II), (III), (IV) and (V) The thermoplastic resin composition according to claim 1.

(5) Any one of (1) to (4), further comprising 10 to 200 parts by weight of filler (D) with respect to 100 parts by weight of the total of (A), (B) and (C). The thermoplastic resin composition described in 1.
(6) A molded product obtained by melt-molding the thermoplastic resin composition according to any one of (1) to (5).
(7) The molded article according to (6), which is in contact with a metal.
(8) The molded article according to (6) or (7), wherein the molded article is a connector or a breaker.

  According to the present invention, a thermoplastic resin composition having high metal adhesive strength can be obtained. Moreover, the molded article excellent in the metal adhesiveness after a high temperature process can be provided using the thermoplastic resin composition of this invention. In particular, it can be suitably used for applications such as connectors and breakers that require high metal adhesion strength.

  Hereinafter, the present invention will be described in detail.

[Polyphenylene sulfide]
The polyphenylene sulfide (A) as an embodiment of 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 preferred. In addition, polyphenylene sulfide may be composed of one or more repeating units having the following structure, with less than about 30 mol% of the repeating units.

  Since polyphenylene sulfide having such a structure has a low melting point, such polyphenylene sulfide is advantageous in terms of moldability. Two or more of these polyphenylene sulfides may be used in combination.

  Although there is no restriction | limiting in the melt viscosity of the polyphenylene sulfide of embodiment of this invention, From a viewpoint of improving the adhesiveness to the metal component surface, it is preferable that it is 200 Pa * s (300 degreeC, shear rate 1000 / s) or less, 100 Pa · S or less is more preferable, and 50 Pa · s or less is more preferable. The lower limit is preferably 1 Pa · s or more from the viewpoint of melt molding processability and gas generation amount. A mixture of a plurality of polyphenylene sulfides having different melt viscosities may be used as long as they fall within the above melt viscosity range. In addition, the melt viscosity of polyphenylene sulfide in the present invention is a value measured using a capillograph manufactured by Toyo Seiki Co., Ltd. under conditions of 300 ° C. and a shear rate of 1000 / s.

  Although the manufacturing method of the polyphenylene sulfide of embodiment of this invention is demonstrated below, if the polyphenylene sulfide of the said structure is obtained, it will not be limited to the following method.

  First, the contents of the polyhalogen aromatic compound, sulfidizing agent, polymerization solvent, molecular weight regulator, polymerization aid and polymerization stabilizer used in the production method will be described.

[Polyhalogenated aromatic compounds]
A 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, hexa Polyhalogenated aroma such as chlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, 1-methoxy-2,5-dichlorobenzene Group compounds, and preferably p-dichlorobenzene is used. Further, it is possible to combine two or more different polyhalogenated aromatic compounds into a copolymer, but it is preferable to use a p-dihalogenated aromatic compound as a main component.

  The polyhalogenated aromatic compound is used in an amount of 0.9 to 2.0 mol, preferably 0.95 to 1.5 mol per mol of sulfidizing agent, from the viewpoint of obtaining a polyphenylene sulfide resin having a viscosity suitable for processing. More preferably, the range of 1.005 to 1.2 mol can be exemplified.

[Sulfiding agent]
Examples of the sulfiding agent include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.

  Specific examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and a mixture of two or more of these, and sodium sulfide is preferably used. These alkali metal sulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.

  Specific examples of the alkali metal hydrosulfide include, for example, sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide and a mixture of two or more of these. Preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.

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

  Alternatively, an alkali metal sulfide 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. Moreover, an alkali metal sulfide can be prepared from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide, and transferred to a polymerization tank for use.

  The amount of the sulfidizing agent charged means a residual amount obtained by subtracting the loss from the actual charged amount when a partial loss of the sulfiding agent occurs before the start of the polymerization reaction due to dehydration operation or the like.

  An alkali metal hydroxide and / or an alkaline earth metal hydroxide can be used in combination with the sulfidizing agent. Specific examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and a mixture of two or more thereof. Specific examples of the metal hydroxide include, for example, calcium hydroxide, strontium hydroxide, barium hydroxide, and sodium hydroxide is preferably used.

  When an alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use an alkali metal hydroxide at the same time, but the amount used is 0.95-1. A range of 20 mol, preferably 1.00 to 1.15 mol, more preferably 1.005 to 1.100 mol can be exemplified.

[Polymerization solvent]
An organic polar solvent is preferably used as the polymerization solvent. Specific examples include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, caprolactams such as N-methyl-ε-caprolactam, and 1,3-dimethyl-2-imidazolide. Non-, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric acid triamide, dimethyl sulfone, tetramethylene sulfoxide and the like, and mixtures thereof, and the like are all included. It is preferably used because of its high reaction stability. Of 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 mol to 10 mol, preferably 2.25 to 6.0 mol, more preferably 2.5 to 5.5 mol, per mol of the sulfidizing agent.

[Molecular weight regulator]
Monohalogen compounds (not necessarily aromatic compounds) are used in combination with the above polyhalogenated aromatic compounds in order to form the ends of the generated polyphenylene sulfide or to adjust the polymerization reaction or molecular weight. Can do. Examples of the monohalogenated compound include monohalogenated benzene, monohalogenated naphthalene, monohalogenated anthracene, monohalogenated compounds containing two or more benzene rings, and monohalogenated heterocyclic compounds. Of these, monohalogenated benzene is preferable from the viewpoint of economy. It is also possible to use a combination of two or more different monohalogenated compounds.

[Polymerization aid]
In order to obtain a polyphenylene sulfide having a relatively high degree of polymerization in a shorter time, it is also one of preferred embodiments to use a polymerization aid. Here, the polymerization aid means a substance having an action of increasing the viscosity of the obtained polyphenylene sulfide. Specific examples of such polymerization aids include, for example, organic carboxylates, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates and alkaline earths. Metal phosphates and the like. These may be used alone or in combination of two or more. Of these, organic carboxylates, water, and alkali metal chlorides are preferable. Further, alkali metal carboxylates are preferable as organic carboxylates, and lithium chloride is preferable as alkali metal chlorides.

  The alkali metal carboxylate is a general formula R (COOM) n (wherein R is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group, or an arylalkyl group). M is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium, and n is an integer of 1 to 3). Alkali metal carboxylates can also be used as hydrates, anhydrides or aqueous solutions. Specific examples of the alkali metal carboxylate include, for example, lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluate, and mixtures thereof. Can be mentioned.

  The alkali metal carboxylate is 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 are allowed to react by adding approximately equal chemical equivalents. You may form by. Among the alkali metal carboxylates, lithium salts are highly soluble in the reaction system and have a large auxiliary effect, but are expensive, and potassium, rubidium and cesium salts are insufficiently soluble in the reaction system. Therefore, sodium acetate, which is inexpensive and has an appropriate solubility in the polymerization system, is most preferably used.

  When these alkali metal carboxylates are used as polymerization aids, the amount used is usually in the range of 0.01 to 2 moles with respect to 1 mole of the sulfidizing agent. The range of 1-0.6 mol is preferable, and the range of 0.2-0.5 mol is more preferable.

  In addition, when water is used as a polymerization aid, the addition amount is usually in the range of 0.3 to 15 mol with respect to 1 mol of the charged sulfidizing agent, and 0.6 to 10 in the sense of obtaining a higher degree of polymerization. The molar range is preferable, and the range of 1 to 5 mol is more preferable.

  Of course, two or more kinds 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 obtained in a smaller amount.

  There is no particular designation as to the timing of addition of these polymerization aids, which may be added at any time during the previous step, polymerization start, polymerization in the middle to be described later, or may be added in multiple times. When using an alkali metal carboxylate as a polymerization aid, it is more preferable to add it at the start of the previous step or at the start of the polymerization from the viewpoint of easy addition. When water is used as a polymerization aid, it is effective to add the polyhalogenated aromatic compound during the polymerization reaction after charging.

[Polymerization stabilizer]
A polymerization stabilizer can also be used to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to stabilization of the polymerization reaction system and suppresses undesirable side reactions. One measure of the side reaction is the generation of thiophenol, and the addition of a polymerization stabilizer can suppress the generation of thiophenol. Specific examples of the polymerization stabilizer include compounds such as alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides, and alkaline earth metal carbonates. Among these, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferable. Since the alkali metal carboxylate described above also acts as a polymerization stabilizer, it is one of the polymerization stabilizers. In addition, when an alkali metal hydrosulfide is used as a sulfidizing agent, it has been described above that it is particularly preferable to use an alkali metal hydroxide at the same time. Oxides can also be polymerization stabilizers.

  These polymerization stabilizers can be used alone or in combination of two or more. The polymerization stabilizer is 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 sulfidizing agent. It is preferable to use it. If this ratio is small, the stabilizing effect is insufficient, or conversely, if it is too much, it tends to be economically disadvantageous or the polymer yield tends to decrease.

  The addition timing of the polymerization stabilizer is not particularly specified, and may be added at any time during the previous step, at the start of polymerization, or during the polymerization described later, or may be added in multiple times. It is more preferable because it is easy to add at the start of the process or at the start of the polymerization.

  Next, a preferred method for producing polyphenylene sulfide according to an embodiment of the present invention will be described in detail in order of a pre-process, a polymerization reaction process, a recovery process, and a post-treatment process, but of course, it is limited to this method. It is not a thing.

[pre-process]
In the method for producing polyphenylene sulfide, the sulfiding agent is usually used in the form of a hydrate, but before adding the polyhalogenated aromatic compound, the temperature of the mixture containing the organic polar solvent and the sulfiding agent is increased, It is preferable to remove an excessive amount of water out of the system.

  As described above, a sulfidizing agent 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 sulfidizing agent. Can do. Although there is no particular limitation on this method, desirably an alkali metal hydrosulfide and an alkali metal hydroxide are added to the organic polar solvent in 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. or more, 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. Moreover, in order to accelerate | stimulate distillation of a water | moisture content, you may react by adding toluene etc.

  The amount of water in the polymerization system in the polymerization reaction is preferably 0.3 to 10.0 moles per mole of the charged sulfidizing agent. Here, the amount of water in the polymerization system is an amount obtained by subtracting the amount of water removed from the polymerization system from the amount of water charged in the polymerization system. In addition, the water to be charged may be in any form such as water, an aqueous solution, and crystal water.

[Polymerization reaction step]
A polyphenylene sulfide is produced by reacting a sulfidizing agent and a polyhalogenated aromatic compound in an organic polar solvent within a temperature range of 200 ° C. or higher and lower than 290 ° C.

  When starting the polymerization reaction step, the organic polar solvent, the sulfidizing agent, and the polyhalogenated aromatic compound are desirably mixed in an inert gas atmosphere at room temperature to 240 ° C., preferably 100 to 230 ° C. . A polymerization aid may be added at this stage. The order in which these raw materials are charged may be out of order or may be simultaneous.

  The mixture is usually heated to a temperature in the range of 200 ° C to 290 ° C. Although there is no restriction | limiting in particular in a temperature increase rate, Usually, the speed of 0.01-5 degreeC / min is selected, and the range of 0.1-3 degreeC / min is more preferable.

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

  In the stage before reaching the final temperature, for example, a method of reacting at 200 to 260 ° C. for a certain time and then raising the temperature to 270 to 290 ° C. is effective in obtaining a higher degree of polymerization. Under the present circumstances, as reaction time in 200 to 260 degreeC, the range of 0.25 to 20 hours is selected normally, Preferably the range of 0.25 to 10 hours is selected.

  In order to obtain a polymer having a higher degree of polymerization, it may be effective to perform polymerization in multiple stages. When the polymerization is performed in a plurality of stages, it is effective that the conversion of the polyhalogenated aromatic compound in the system at 245 ° C. reaches 40 mol% or more, preferably 60 mol%.

The conversion rate of the polyhalogenated aromatic compound (herein abbreviated as PHA) is a value calculated by the following formula. The residual amount of PHA can usually be determined by gas chromatography.
(A) When polyhalogenated aromatic compound is added excessively in a molar ratio with respect to the alkali metal sulfide, the conversion rate = [PHA charge (mol) −PHA remaining amount (mol)] / [PHA charge (mol) -PHA excess (mole)]
(B) In cases other than (A) above, conversion rate = [PHA charge (mol) −PHA remaining amount (mol)] / [PHA charge (mol)]

[Recovery process]
In the method for producing polyphenylene sulfide, after the polymerization is completed, a solid is recovered from a polymerization reaction product containing a polymer, a solvent, and the like. Any known method may be adopted as the recovery method.

  For example, after completion of the polymerization reaction, a method of slowly cooling and recovering the particulate polymer may be used. Although there is no restriction | limiting in particular in the slow cooling rate in this case, Usually, it is about 0.1 degree-C / min-about 3 degree-C / min. It is not necessary to perform slow cooling at the same rate in the entire process of the slow cooling step, such as a method of gradually cooling at a rate of 0.1 to 1 ° C / min until the polymer particles are crystallized and precipitated, and then at a rate of 1 ° C / min or more. It may be adopted.

Moreover, it is also one of the preferable methods to perform said collection | recovery on quenching conditions, As a preferable method of this collection method, the flash method is mentioned. In the flash method, the polymerization reaction product is flushed from a high temperature and high pressure (usually 250 ° C. or more, 8 kg / cm ² or more) into an atmosphere of normal pressure or reduced pressure, and the polymer is recovered in the form of powder simultaneously with the solvent recovery. This is a method, and the term “flash” here means that a polymerization reaction product is ejected from a nozzle. Specific examples of the atmosphere to be flushed include nitrogen or water vapor at normal pressure, and the temperature is usually in the range of 150 ° C to 250 ° C.

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

  When acid treatment is performed, it is as follows. The acid used for acid treatment of polyphenylene sulfide is not particularly limited as long as it does not have an action of decomposing polyphenylene sulfide, and examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propyl acid. Acetic acid and hydrochloric acid are more preferably used, but those that decompose and degrade polyphenylene sulfide such as nitric acid are not preferred.

  As the acid treatment method, there is a method of immersing polyphenylene sulfide in an acid or an acid aqueous solution, and it is possible to appropriately stir or heat as necessary. For example, when acetic acid is used, a sufficient effect can be obtained by immersing the polyphenylene sulfide powder in an aqueous pH 4 solution heated to 80 to 200 ° C. and stirring for 30 minutes. The pH after the treatment may be 4 or more, for example, about pH 4-8. The polyphenylene sulfide subjected to the acid treatment is preferably washed several times with water or warm water in order to remove the remaining acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that it does not impair the preferable chemical modification effect of polyphenylene sulfide by acid treatment.

  When performing hot water treatment, it is as follows. In the hydrothermal treatment of polyphenylene sulfide, 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. A temperature lower than 100 ° C. is not preferable because the effect of preferable chemical modification of polyphenylene sulfide is small.

  The water used is preferably distilled water or deionized water in order to develop a preferable chemical modification effect of polyphenylene sulfide by hot water washing. There is no particular limitation on the operation of the hot water treatment, and a predetermined amount of polyphenylene sulfide resin is charged into a predetermined amount of water and heated and stirred in a pressure vessel, or a method of continuously performing hot water treatment. The ratio of polyphenylene sulfide to water is preferably as much as possible, but usually a bath ratio of 200 g or less of polyphenylene sulfide per 1 liter of water is selected.

  Further, since the decomposition of the terminal group is not preferable, the treatment atmosphere is desirably an inert atmosphere in order to avoid this. Further, the polyphenylene sulfide after the hydrothermal treatment operation is preferably washed several times with warm water in order to remove remaining components.

  When washing with an organic solvent, it is as follows. The organic solvent used for washing polyphenylene sulfide is not particularly limited as long as it does not have an action of decomposing polyphenylene sulfide. For example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, 1,3-dimethylimidazo Nitrogen-containing polar solvents such as lysinone, hexamethylphosphoramide, piperazinones, sulfoxide-sulfone solvents such as dimethyl sulfoxide, dimethyl sulfone, sulfolane, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, dimethyl ether, di Ether solvents such as propyl ether, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, Halogen solvents such as chloroethane, tetrachloroethane, perchlorethane, chlorobenzene, alcohols and phenols such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, and polypropylene glycol Examples of the solvent include aromatic hydrocarbon solvents such as benzene, toluene, and xylene. Among these organic solvents, use of N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform and the like is particularly preferable. These organic solvents are used alone or in combination of two or more.

  As a method of washing with an organic solvent, there is a method of immersing polyphenylene sulfide in an organic solvent, and it is possible to appropriately stir or heat as necessary. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning polyphenylene sulfide with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect is usually obtained at a cleaning temperature of room temperature to 150 ° C. It is also possible to wash under pressure in a pressure vessel at a temperature above the boiling point of the organic solvent. There is no particular limitation on the cleaning time. Depending on the cleaning conditions, in the case of batch-type cleaning, a sufficient effect can be obtained usually by cleaning for 5 minutes or more. It is also possible to wash in a continuous manner.

  As a method of treating alkali metal or alkaline earth metal, before the previous step, during the previous step, after the previous step, a method of adding an alkali metal salt or alkaline earth metal salt, before the polymerization step, during the polymerization step, during the polymerization step Examples include a method of adding an alkali metal salt or an alkaline earth metal salt into the polymerization vessel later, or a method of adding an alkali metal salt or an alkaline earth metal salt at the first, middle or last stage of the washing step. Among them, the easiest method includes a method of adding an alkali metal salt or an alkaline earth metal salt after removing residual oligomers or residual salts by washing with an organic solvent or washing with warm water or hot water. Alkali metals and alkaline earth metals are preferably introduced into PPS in the form of alkali metal ions such as acetates, hydroxides and carbonates, and alkaline earth metal ions. It is preferable to remove excess alkali metal salt and alkaline earth metal salt by washing with warm water. The concentration of alkali metal ions and alkaline earth metal ions at the time of introduction of the alkali metal and alkaline earth metal is preferably 0.001 mmol or more, more preferably 0.01 mmol or more with respect to 1 g of polyphenylene sulfide. As temperature, 50 degreeC or more is preferable, 75 degreeC or more is more preferable, and 90 degreeC or more is especially preferable. Although there is no upper limit temperature, it is usually preferably 280 ° C. or lower from the viewpoint of operability. The bath ratio (the weight of the cleaning solution with respect to the dry PPS weight) is preferably 0.5 or more, more preferably 3 or more, and still more preferably 5 or more.

  In addition, polyphenylene sulfide can be used after having been polymerized to have a high molecular weight by heating in an oxygen atmosphere and thermal oxidative crosslinking treatment by heating with addition of a crosslinking agent such as peroxide.

  When the 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 preferably 5% by volume or more, more preferably 8% by volume or more. Although there is no restriction | limiting in particular in the upper limit of oxygen concentration, About 50 volume% is a limit. The treatment time is preferably 0.5 to 100 hours, more preferably 1 to 50 hours, and further preferably 2 to 25 hours. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary type or a stirring blade. However, for efficient and more uniform processing, a heating apparatus with a rotary type or a stirring blade is used. More preferably it is used.

  In addition, it is possible to carry out dry heat treatment for the purpose of suppressing thermal oxidative crosslinking and removing volatile matter. The temperature is preferably 130 to 250 ° C, and more preferably 160 to 250 ° C. In this case, the oxygen concentration is preferably less than 5% by volume, and more preferably less than 2% by volume. The treatment time is preferably 0.5 to 50 hours, more preferably 1 to 20 hours, and further preferably 1 to 10 hours. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary type or a stirring blade. However, for efficient and more uniform processing, a heating apparatus with a rotary type or a stirring blade is used. More preferably it is used.

  However, from the viewpoint of improving mechanical properties such as impact strength, the polyphenylene sulfide is preferably a substantially linear PPS that does not undergo high molecular weight by thermal oxidation crosslinking treatment.

[Liquid crystal polyester]
The liquid crystalline polyester (B) according to an embodiment of the present invention is a polyester called a thermotropic liquid crystal polymer that exhibits optical anisotropy when melted. For example, an aromatic oxycarbonyl unit, an aromatic and / or an aliphatic dioxy unit, A liquid crystalline polyester comprising a structural unit selected from aromatic and / or aliphatic dicarbonyl units and forming an anisotropic melt phase.

  Examples of the aromatic oxycarbonyl unit include structural units generated from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and the like, and p-hydroxybenzoic acid is preferable. Examples of the aromatic and / or aliphatic dioxy unit include 4,4′-dihydroxybiphenyl, hydroquinone, 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxybiphenyl, t-butylhydroquinone, Phenylhydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,2-bis (4-hydroxyphenyl) propane and 4,4′-dihydroxydiphenyl ether, ethylene glycol, 1,3-propylene glycol, 1, Examples include structural units generated from 4-butanediol, and 4,4′-dihydroxybiphenyl and hydroquinone are preferred. Examples of the aromatic and / or aliphatic dicarbonyl units include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-4, Examples include structural units formed from 4′-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4′-dicarboxylic acid and 4,4′-diphenyl ether dicarboxylic acid, adipic acid, sebacic acid and the like. Terephthalic acid and isophthalic acid are preferred.

  Specific examples of the liquid crystalline polyester include a liquid crystalline polyester composed of a structural unit generated from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, a structural unit generated from p-hydroxybenzoic acid, and 6-hydroxy-2. A structural unit produced from naphthoic acid, a liquid crystalline polyester comprising a structural unit produced from an aromatic dihydroxy compound, an aromatic dicarboxylic acid and / or an aliphatic dicarboxylic acid, a structural unit produced from p-hydroxybenzoic acid, 4, 4 A liquid crystalline polyester comprising a structural unit produced from a structural unit produced from '-dihydroxybiphenyl, an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid and / or an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, p-hydroxybenzoic acid Structural units generated from acids, 4,4 ' Liquid crystalline polyester comprising structural units generated from dihydroxybiphenyl, structural units generated from hydroquinone, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid and / or structural units generated from aliphatic dicarboxylic acids such as adipic acid and sebacic acid , Structural units generated from p-hydroxybenzoic acid, structural units generated from 4,4′-dihydroxybiphenyl, structural units generated from hydroquinone, and structural units generated from aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid Polyesters, structural units generated from p-hydroxybenzoic acid, structural units generated from ethylene glycol, liquid crystalline polyesters consisting of structural units generated from terephthalic acid and / or isophthalic acid, generated from p-hydroxybenzoic acid Liquid crystalline polyester comprising structural units produced from ethylene glycol, structural units produced from 4,4′-dihydroxybiphenyl, structural units produced from aliphatic dicarboxylics such as terephthalic acid and / or adipic acid and sebacic acid From structural units generated from p-hydroxybenzoic acid, structural units generated from ethylene glycol, structural units generated from aromatic dihydroxy compounds, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid Liquid crystalline polyester composed of the generated structural unit, structural unit generated from 6-hydroxy-2-naphthoic acid, structural unit generated from 4,4′-dihydroxybiphenyl, structural unit generated from 2,6-naphthalenedicarboxylic acid Is a liquid crystalline polyester And so on.

  Particularly preferred are structural units generated from p-hydroxybenzoic acid, structural units generated from 4,4′-dihydroxybiphenyl, structural units generated from hydroquinone, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid. It is a liquid crystalline polyester of a structural unit, and is a liquid crystalline polyester composed of the following structural units (I), (II), (III), (IV) and (V).

  The structural unit (I) was generated from p-hydroxybenzoic acid, the structural unit (II) was generated from 4,4′-dihydroxybiphenyl, and the structural unit (III) was generated from hydroquinone. The structural unit, the structural unit (IV) represents a structural unit produced from terephthalic acid, and the structural unit (V) represents a structural unit produced from isophthalic acid.

  The liquid crystalline polyester of the present invention is preferably composed of the above structural units because the balance between heat resistance and workability is excellent.

  The structural unit (I) is 68 to 80 mol% based on the total of the structural units (I), (II) and (III), and the structural unit (II) is the total of the structural units (II) and (III). The structural unit (IV) is 50 to 95 mol% based on the total of the structural units (IV) and (V), and the total of the structural units (II) and (III). It is particularly preferred that the sum of (IV) and (V) is substantially equimolar.

  The structural unit (I) is preferably 68 to 80 mol% with respect to the total of the structural units (I), (II) and (III). 70 mol% or more is more preferable, and 73 mol% or more is especially preferable. On the other hand, 78 mol% or less is more preferable.

  Moreover, it is preferable that structural unit (II) is 55-75 mol% with respect to the sum total of structural unit (II) and (III). 58 mol% or more is more preferable. On the other hand, 70 mol% or less is more preferable, and 65 mol% or less is particularly preferable.

  Moreover, it is preferable that structural unit (IV) is 50-95 mol% with respect to the sum total of structural unit (IV) and (V). 55 mol% or more is more preferable, and 60 mol% or more is particularly preferable. On the other hand, 90 mol% or less is more preferable, and 85 mol% or less is particularly preferable.

  Further, the sum of the structural units (II) and (III) and the sum of (IV) and (V) are substantially equimolar. Here, “substantially equimolar” means that the structural unit constituting the polymer main chain excluding the terminal is equimolar. For this reason, the aspect which does not necessarily become equimolar when it includes even the structural unit which comprises the terminal can satisfy the requirement of “substantially equimolar”.

In the embodiment of the present invention, the content of each structural unit is determined by measuring the liquid crystalline polyester in an NMR (nuclear magnetic resonance) test tube and dissolving the liquid crystalline polyester in a solvent (for example, pentafluorophenol / heavy tetrachloroethane- d ₂ mixed solvent), ¹ H-NMR spectrum measurement is performed, and the peak area ratio derived from each structural unit can be calculated.

  By making content of said structural unit (I)-(V) into the said range, since liquid crystalline polyester excellent in heat resistance, mechanical characteristics, and low gas property is obtained easily, it is preferable. In addition, a thermoplastic resin composition comprising the same is preferable because it has excellent metal adhesion after high-temperature treatment without a decrease in metal adhesion strength.

  The melting point (Tm) of the liquid crystalline polyester of the embodiment of the present invention is preferably 220 to 350 ° C., more preferably 270 to 345 ° C., further preferably 300 to 340, from the viewpoint of the balance between processability and heat resistance. ° C.

Here, the melting point (Tm) is the difference between Tm1 + 20 ° C. after observing the endothermic peak temperature (Tm1) observed when the polymer having been polymerized is measured under the temperature rising condition from room temperature to 20 ° C./min in differential calorimetry. This is the endothermic peak temperature (Tm2) observed when the temperature is held for 5 minutes, then cooled to room temperature under a temperature drop condition of 20 ° C./minute, and measured again under a temperature rise condition of 20 ° C./minute.
The number average molecular weight of the liquid crystalline polyester of the embodiment of the present invention is preferably 3,000 to 50,000, more preferably 8,000 to 30,000, and still more preferably 8,000 to 20,000. .

  The number average molecular weight can be measured by GPC-LS (gel permeation chromatography-light scattering) method using a solvent in which the liquid crystalline polyester is soluble as an eluent. Examples of the solvent in which the liquid crystalline polyester is soluble include halogenated phenols and a mixed solvent of a halogenated phenol and a general organic solvent. Preferable are pentafluorophenol and a mixed solvent of pentafluorophenol and chloroform. Among them, a pentafluorophenol / chloroform mixed solvent is preferable from the viewpoint of handleability.

The melt viscosity of the liquid crystalline polyester of the embodiment of the present invention is preferably 1 to 200 Pa · s, more preferably 10 to 100 Pa · s, and still more preferably 20 to 50 Pa · s. The melt viscosity of the liquid crystalline polyester in the present invention is a value measured by a Koka flow tester under the condition of the melting point of the liquid crystalline polyester + 10 ° C. and the shear rate of 1,000 / sec.

The method for producing the liquid crystalline polyester of the embodiment of the present invention is not particularly limited, and can be produced according to a known polyester polycondensation method. Examples of known polyester polycondensation methods include the following production methods.
(1) A method for producing a liquid crystalline polyester from p-acetoxybenzoic acid and 4,4′-diacetoxybiphenyl, diacetoxybenzene, terephthalic acid and isophthalic acid by a deacetic acid condensation polymerization reaction.
(2) Liquid crystalline polyester by reacting p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl and hydroquinone with terephthalic acid and isophthalic acid with acetic anhydride to acetylate the phenolic hydroxyl group, followed by deacetic acid polymerization How to manufacture.
(3) A method for producing a liquid crystalline polyester from phenyl p-hydroxybenzoate and 4,4′-dihydroxybiphenyl, hydroquinone, diphenyl terephthalate and diphenyl isophthalate by a dephenol polycondensation reaction.
(4) A predetermined amount of diphenyl carbonate is reacted with p-hydroxybenzoic acid and aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid to form phenyl esters, respectively, and then aromatics such as 4,4′-dihydroxybiphenyl and hydroquinone. A method for producing a liquid crystalline polyester by adding a group dihydroxy compound and dephenol polycondensation reaction.

  Among them, (2) p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, and isophthalic acid are reacted with acetic anhydride to acetylate the phenolic hydroxyl group, and then liquid crystal is obtained by deacetic acid polycondensation reaction. A method for producing a reactive polyester is preferably used from the viewpoint of polymerization reaction control.

  The amount of acetic anhydride to be used is preferably 1.00 to 1.15 molar equivalent of the total of the phenolic hydroxyl groups of p-hydroxybenzoic acid, 4,4′-dihydroxybiphenyl and hydroquinone, 1.03-1. 12 molar equivalents are more preferred, and 1.05-1.12 molar equivalents are even more preferred. By making the usage-amount of acetic anhydride into the said range, the acetylation rate of hydroquinone with a small acetylation reaction rate can be controlled easily. By controlling the terminal structure of the liquid crystalline polyester, a liquid crystalline polyester composition with less gas generation can be obtained, which is preferable.

  When the liquid crystalline polyester of the embodiment of the present invention is produced by a deacetic acid polycondensation reaction, a melt polymerization method in which the polycondensation reaction is completed by reacting under reduced pressure at a temperature at which the liquid crystalline polyester melts is preferable. The melt polymerization method is an advantageous method for producing a uniform polymer, and is preferable because a polymer with less gas generation can be obtained.

  For example, in a reaction vessel equipped with a predetermined amount of p-hydroxybenzoic acid and 4,4′-dihydroxybiphenyl, hydroquinone, terephthalic acid, isophthalic acid, acetic anhydride, a stirring blade, a distillation pipe, and a discharge port at the bottom. There is a method in which the reaction is completed after charging and heating under stirring in a nitrogen gas atmosphere to acetylate the hydroxyl group, raising the temperature to the melting temperature of the liquid crystalline polyester, and performing polycondensation under reduced pressure. The conditions for the acetylation are usually 130 to 300 ° C., preferably 135 to 200 ° C. for 1 to 6 hours, more preferably 140 to 180 ° C. for 2 to 4 hours. The polycondensation temperature is a melting temperature of the liquid crystalline polyester, for example, in the range of 250 to 365 ° C., and preferably a melting point of the liquid crystalline polyester + 10 ° C. or higher. The degree of vacuum during polycondensation is usually 0.1 mmHg (13.3 Pa) to 20 mmHg (2660 Pa), preferably 10 mmHg (1330 Pa) or less, more preferably 5 mmHg (665 Pa) or less. In addition, although acetylation and polycondensation may be performed continuously in the same reaction vessel, acetylation and polycondensation may be performed in different reaction vessels.

  After the polymerization, the obtained polymer is taken out from the reaction vessel by pressurizing the inside of the reaction vessel at a temperature at which the polymer melts, discharging the polymer from the discharge port provided in the reaction vessel, and cooling the discharged polymer. The method of cooling in water can be mentioned. The pressurization in the reaction vessel may be 0.02 to 0.5 MPa, for example. The discharge port may be provided at the lower part of the reaction vessel. Moreover, what is necessary is just to discharge a polymer in a strand form from a discharge outlet. Resin pellets can be obtained by cutting the polymer cooled in the cooling liquid into pellets.

  When the liquid crystalline polyester of the embodiment of the present invention is produced, the polycondensation reaction can be completed by a solid phase polymerization method. For example, the liquid crystalline polyester polymer or oligomer of the embodiment of the present invention is pulverized with a pulverizer, heated in a nitrogen stream or under reduced pressure, and polycondensed to a desired degree of polymerization to complete the reaction. It is done. What is necessary is just to perform the said heating for 1 to 50 hours in the range of melting | fusing point-5 degreeC-melting point-50 degreeC (for example, 200-300 degreeC) of liquid crystalline polyester.

  Although the polycondensation reaction of the liquid crystalline polyester as an embodiment of the present invention proceeds even without a catalyst, a metal compound such as stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, and magnesium metal is used as a catalyst. It can also be used.

[Elastomer]
The elastomer (C) of the embodiment of the present invention is an elastomer characterized by having a melt flow rate (hereinafter sometimes abbreviated as MFR) of 10 to 400 g / 10 minutes. In addition, MFR is calculated | required by 190 degreeC and a 2160g load based on ISO1133. The MFR of the elastomer as an embodiment of the present invention is 10 to 400 g / 10 minutes, preferably 15 g / 10 minutes or more, and more preferably 20 g / 10 minutes or more. On the other hand, 200 g / 10 min or less is preferable, and 100 g / 10 min or less is more preferable. When the MRF is less than 10 g / 10 minutes, the fluidity is not sufficient, the adhesion to the fine irregularities on the surface of the metal part is small, and the metal adhesion strength is inferior. On the other hand, when the MFR exceeds 400 g / 10 min, heat resistance and mechanical properties are deteriorated.

  Examples of the elastomer include, for example, a polyamide-based elastomer formed by a rubber component such as a polyol and a polyamide, a polyurethane-based elastomer generated by a rubber component such as a polyol and an isocyanate compound, a polyester component generated by a rubber component such as a polyol and a polyester. A rubber component composed of a block copolymer composed of one or more of elastomer, ethylene, propylene and butylene, a polystyrene elastomer composed of polystyrene, a polyolefin polymer obtained by polymerizing an α-olefin, and an α-olefin Examples thereof include polyolefin elastomers composed of a copolymer with an α, β-unsaturated acid and an alkyl ester thereof. These elastomers may be modified products having functional groups such as a carboxyl group, a carboxylic ester group, an acid anhydride group, and an epoxy group. These elastomers may be used alone or in combination of two or more. As the elastomer, a polyolefin-based elastomer is preferable because it is easy to introduce a structure having high metal adhesion.

  As a polymer obtained by polymerizing α-olefin in a polyolefin elastomer, a polymer obtained by polymerizing ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, isobutylene, etc., [( Copolymer of ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester)], [(ethylene and / or propylene) and (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) And a polymer obtained by subjecting at least a part of the carboxyl group of the copolymer to a metal salt], a single polymer or a copolymer may be used. As the α-olefin in the copolymer of the α-olefin and the α, β-unsaturated acid and its alkyl ester, the α-olefin described above can be used, and the α, β-unsaturated acid is an acrylic. Examples include acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, and butyl methacrylate. One or two or more α-olefins and α, β-unsaturated acids may be used.

  More preferably, polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / methyl acrylate copolymer, ethylene / Ethyl acrylate copolymer, ethylene / butyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / butyl methacrylate copolymer, and the like.

  In particular, it is preferable that the elastomer of the embodiment of the present invention is an elastomer having a structural unit derived from acrylic acid because the effects of the present invention remarkably appear.

  As components having structural units derived from acrylic acid, α, β-unsaturated acids such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like The alkyl ester is mentioned.

  The proportion of the component having an acrylic acid-derived structure of the elastomeric copolymer component of the embodiment of the present invention is preferably 20% by weight or more, and more preferably 30% by weight or more. On the other hand, it is preferably 50% by weight or less, and more preferably 45% by weight or less. When the proportion of the component having a structure derived from acrylic acid is 20% by weight or more, the polar group having the acrylic acid structure is excellent in affinity with the metal part, and high adhesiveness is obtained. Moreover, the heat resistant fall by there being few olefin components is suppressed as the ratio of the component which has a structure derived from acrylic acid is 50 weight% or less. The component having a structure derived from acrylic acid as a copolymerization component of the elastomer is obtained from the peak area of FTIR.

  In addition, the elastomer of the embodiment of the present invention may use two or more kinds of elastomers in combination. In that case, MFR of all the elastomers in a thermoplastic resin composition can be calculated | required from MFR and each compounding ratio of each elastomer. As the elastomer of the present invention, for example, Rotoril 35BA40, Bondine HX8210 (both manufactured by Arkema) and the like are commercially available.

  The blending amounts of the polyphenylene sulfide (A), the liquid crystalline polyester (B) and the elastomer (C) are 40 to 90% by weight of the polyphenylene sulfide (A), 5 to 50% by weight of the liquid crystalline polyester (B) and the elastomer (C). 1 to 20% by weight is blended so that the total of (A), (B) and (C) is 100% by weight. More preferably, it is in the range of 65 to 85% by weight of polyphenylene sulfide (A), 7 to 30% by weight of liquid crystalline polyester (B) and 4 to 15% by weight of elastomer (C).

  When the amount of polyphenylene sulfide (A) is less than 40% by weight, the affinity with the surface of the metal part is inferior, the metal adhesion strength and the metal adhesion at the time of high temperature treatment are not sufficient, and the fluctuation of the fluidity with respect to the thickness of the molded article increases. On the other hand, if it is more than 90% by weight, the heat resistance is not sufficient and the metal adhesion is lowered during high temperature treatment. When the amount of the liquid crystalline polyester (B) component is less than 5% by weight, the heat resistance and fluidity are inferior, the metal adhesion strength and the metal adhesion during high-temperature treatment are lowered, and the fluidity varies with the thickness of the molded product. On the other hand, when the amount is more than 50% by weight, the affinity with the surface of the metal part is inferior and the metal bonding strength is not sufficient, and the fluctuation of the fluidity with respect to the thickness of the molded product becomes large. When the elastomer (C) is less than 1% by weight, the affinity with the surface of the metal part is inferior, the metal adhesion strength and the metal adhesion at the time of high temperature treatment are not sufficient, and the fluctuation of fluidity with respect to the thickness of the molded product becomes large. On the other hand, if it is more than 20% by weight, the heat resistance is lowered, the metal adhesion strength and the metal adhesion during high-temperature treatment are lowered, and the fluctuation of the fluidity with respect to the thickness of the molded product is increased.

  In the thermoplastic resin composition of the embodiment of the present invention, the occurrence of burrs during molding derived from polyphenylene sulfide and the shear rate dependence of the fluidity derived from liquid crystalline polyester are alleviated, and the thickness dependence of the flow length during molding is reduced. And the fluidity of the molded product including the thin-walled portion and the thick-walled portion is stabilized. The reason for this is not clear, but by blending polyphenylene sulfide, liquid crystalline polyester, and the elastomer of the embodiment of the present invention within the scope of the present invention, the flow characteristics of the thermoplastic resin composition are highly enhanced. It is thought that it was balanced. As a result, even when the thickness of the molded product varies due to the inclusion of a metal part, it exhibits uniform fluidity and suppresses a shift of the weld part and a decrease in strength due thereto.

  In the thermoplastic resin composition of the embodiment of the present invention, it is preferable from the viewpoint of metal adhesive strength and mechanical strength that the filler (D) is further blended within a range not impairing the effects of the present invention. Examples of the filler (D) include fillers such as fibers, plates, powders, and granules. Specifically, glass fibers, PAN and pitch carbon fibers, stainless fibers, metal fibers such as aluminum fibers and brass fibers, organic fibers such as aromatic polyamide fibers and liquid crystalline polyester fibers, gypsum fibers, ceramic fibers, Asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, acicular titanium oxide, etc. Or whisker-like filler, mica, talc, kaolin, silica, glass beads, glass flakes, clay, molybdenum disulfide, wollastonite, titanium oxide, zinc oxide, calcium polyphosphate and graphite, etc. Materials . The surface of the filler used in the present invention may be treated with a known coupling agent (for example, a silane coupling agent or a titanate coupling agent) or other surface treatment agent.

  Among these fillers, glass fiber is particularly preferable from the viewpoint of metal adhesive strength and mechanical strength, and the type of glass fiber is not particularly limited as long as it is generally used for resin reinforcement. For example, long fiber type or A short fiber type chopped strand or milled fiber can be selected and used. The glass fiber used in the embodiment of the present invention is preferably weakly alkaline in terms of mechanical strength. In particular, glass fibers having a silicon oxide content of 50 to 80% by weight are preferably used, and more preferably glass fibers having a silicon oxide content of 65 to 77% by weight. The glass fiber is preferably treated with an epoxy-based, urethane-based, acrylic-based coating or sizing agent, and epoxy-based is particularly preferable. Further, it is preferably treated with a silane-based or titanate-based coupling agent or other surface treatment agent, and an epoxysilane or aminosilane-based coupling agent is particularly preferable. The glass fiber may be coated or bundled with a thermoplastic resin such as ethylene / vinyl acetate copolymer or a thermosetting resin such as epoxy resin. Two or more fillers may be used in combination.

  The blending amount of the filler (D) is preferably 10 to 200 parts by weight based on 100 parts by weight of the total of the polyphenylene sulfide (A), the liquid crystalline polyester (B) and the elastomer (C). The blending amount of the filler is more preferably 20 parts by weight or more, and particularly preferably 25 parts by weight or more. Moreover, 150 weight part or less is more preferable, and 100 weight part or less is especially preferable.

  When the blending amount of the filler is larger than 10 parts by weight, the difference in the coefficient of linear expansion between the thermoplastic resin composition and the metal part is small during the high temperature treatment, and the decrease in metal adhesion due to blistering and warping is suppressed during the high temperature treatment. preferable. Moreover, since it has high fluidity | liquidity, it is preferable if the compounding quantity of a filler is smaller than 200 weight part.

  In the thermoplastic resin composition of the embodiment of the present invention, the polyphenylene sulfide (A) and the liquid crystalline polyester (B), and / or the thermoplastic resin composition and the filler (D) are within the range not impairing the effects of the present invention. For the purpose of improving the compatibility with (A), a compatibilizer can be further added.

  Specific examples of the compatibilizer include organic silane compounds such as alkoxysilanes having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, and a ureido group. A functional epoxy compound etc. are mentioned, These can also be used simultaneously 2 or more types. Here, the polyfunctional epoxy compound contains two or more epoxy groups in the molecule, and a liquid or solid one can be used. For example, a copolymer of an α-olefin such as ethylene, propylene, and 1-butene and an α, β-unsaturated glycidyl ester such as glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate, having an unsaturated double bond Epoxy group-containing polymer compound obtained by epoxidizing the double bond part of the polymer, bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-diphenyl Bisphenol-glycidyl ether type epoxy compounds such as dimethylmethane, 4,4′-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol, 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, phthalate Glycidyl ester type epoxy compounds such as glycidyl esters, N- glycidyl amine-based epoxy compound glycidyl aniline, novolac type phenolic resin novolak type epoxy resins obtained by reacting epichlorohydrin and the like. Preferably, a copolymer of an α-olefin and an α, β-unsaturated carboxylic acid glycidyl ester, a glycidyl ester type epoxy resin, an organic silane compound having an epoxy group or an isocyanate group, or a bisphenol-glycidyl ether type epoxy compound is used. Of these, the use of a glycidyl ester type epoxy resin is preferred because of excellent compatibility.

  The compounding amount of the compatibilizer is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight as a total of the polyphenylene sulfide (A), the liquid crystalline polyester (B) and the elastomer (C).

  The thermoplastic resin composition according to the embodiment of the present invention further includes an antioxidant and a heat stabilizer (for example, hindered phenol, hydroquinone, phosphites, and substituted products thereof) as long as the effects of the present invention are not impaired. , UV absorbers (eg, resorcinol, salicylate), anti-coloring agents such as phosphites and hypophosphites, lubricants and mold release agents (montanic acid and its metal salts, its esters, their half esters, stearyl alcohol) , Stearamide and polyethylene wax), colorants containing dyes or pigments, carbon black, crystal nucleating agents, plasticizers, flame retardants (bromine flame retardants, phosphorus flame retardants, red phosphorus, silicones) as conductive agents or colorants Conventional additives selected from flame retardants, flame retardant aids, and antistatic agents can be blended. Alternatively, a polymer other than liquid crystalline polyester and / or polyphenylene sulfide can be blended to further impart predetermined characteristics.

  The method of blending fillers and additives into the thermoplastic resin composition of the embodiment of the present invention is not particularly limited, and dry blending, solution blending method, addition during polymerization of the thermoplastic resin composition Melt kneading can be used, and melt kneading is particularly preferable. A known method can be used for melt kneading. For example, using a Banbury mixer, rubber roll machine, kneader, single-screw or twin-screw extruder, etc., the thermoplastic resin composition is melted and kneaded at a melting point of + 50 ° C. or higher that is higher than the melting point of the thermoplastic resin composition. Can do. Of these, a twin screw extruder is preferable.

  As a kneading method, 1) a method in which polyphenylene sulfide (A), liquid crystalline polyester (B) and elastomer (C), fillers, and other additives are added all at once from the original feeder and kneaded (collective kneading method) ), 2) Polyphenylene sulfide (A), liquid crystalline polyester (B), elastomer (C) and other additives are added from the original feeder and kneaded, and then the filler and, if necessary, other additives are added. Method of adding from the side feeder and kneading (side feed method), 3) Producing a master pellet containing polyphenylene sulfide (A), liquid crystalline polyester (B) and elastomer (C) and other additives at a high concentration, The master pellet is then polyphenylene sulfide (A) and liquid crystalline polyester so that the specified concentration is achieved. Etc. B) and elastomer (C) a method of kneading a filler (master pellet method), may be used any method. The thermoplastic resin composition of the embodiment of the present invention has an excellent surface appearance (color tone) by performing known melt molding such as injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, and spinning. ) And a molded article having mechanical properties, heat resistance and flame retardancy. Examples of the molded product include injection molded products, extrusion molded products, press molded products, sheets, pipes, unstretched films, uniaxially stretched films, various films such as biaxially stretched films, unstretched yarns, and superstretched yarns. Examples include various fibers. In particular, the effect of the present invention can be remarkably obtained when injection molding is used.

  Molded articles made of the thermoplastic resin composition thus obtained include, for example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relay cases, relay bases, relay spools, switches, coil bobbins , Capacitors, variable capacitor cases, optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystal display components , FDD carriages, FDD chassis, HDD parts, motor brush holders, parabolic antennas, thermal protectors, breakers, computer-related parts and other electrical / electronic parts, VTR parts, TV parts, eye , Hair dryer, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser disc (registered trademark) / compact disc, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Representative home / office electrical product parts, office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, oilless bearings, stern bearings, submersible bearings, motor parts, Machine-related parts such as lighters and typewriters, optical equipment such as microscopes, binoculars, cameras and watches, precision machine-related parts, alternator terminals, alternator connectors, IC regulators, light dimmer potentiometer bases, exhaust Various valves such as exhaust valves, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature Sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, thermostat base for air conditioner, motor insulator for air conditioner, automotive motor insulator such as power window, heating hot air flow control valve, brush for radiator motor Holder, water pump impeller, turbine vane, wiper motor related parts, distributor, starter Switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, coil for fuel solenoid valve, fuse connector, horn terminal, electrical component insulation plate, step motor rotor, lamp bezel, lamp socket, lamp reflector , Lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases and other automobile / vehicle-related parts.

  The molded product made of the thermoplastic resin composition according to the embodiment of the present invention may be a molded product in contact with a metal. Since the molded article made of the thermoplastic resin composition of the above-described embodiment of the present invention is excellent in metal adhesion strength, the thermoplastic resin composition of the embodiment of the present invention is bonded to a metal part by insert molding or the like to form a composite material High sealing properties and waterproofness can be obtained. Examples of the metal herein include aluminum, copper, iron, tin, nickel, and zinc, and may be an aluminum alloy or an alloy such as stainless steel. Moreover, even if the surface is plated with aluminum, tin, nickel, gold, silver or the like can be preferably used. Of these, aluminum and aluminum alloys are preferable.

  Among the various uses described above, the molded article of the present invention is useful for parts that come into contact with metals such as electrical / electronic parts and automobile parts, particularly connectors or breakers, taking advantage of the excellent metal adhesive strength.

  Hereinafter, although an example explains the present invention still in detail, the gist of the present invention is not limited only to the following example.

  The polyphenylene sulfide resin (A) used in each example and comparative example is shown below.

Production Example 1 Polyphenylene sulfide resin (A-1)
In a 20 liter autoclave with a stirrer and a valve at the bottom, 2383 g (20.0 mol) of 47% sodium hydrosulfide (Sankyo Kasei), 831 g (19.9 mol) of 96% sodium hydroxide, N-methyl-2 -3960 g (40.0 mol) of pyrrolidone (NMP) and 3000 g of ion-exchanged water were charged, gradually heated to 225 ° C over about 3 hours while flowing nitrogen at normal pressure, and after distilling 4200 g of water and 80 g of NMP, The reaction vessel was cooled to 160 ° C. The residual water content in the system per mole of the alkali metal sulfide charged was 0.17 mole. The amount of hydrogen sulfide scattered per mole of the alkali metal sulfide charged was 0.021 mol. Next, 2942 g (20.0 mol) of p-dichlorobenzene (Sigma Aldrich) and 1515 g (15.3 mol) of NMP were added, and the reaction vessel was sealed under nitrogen gas. Then, while stirring at 400 rpm, the temperature was raised from 200 ° C. to 227 ° C. at a rate of 0.8 ° C./min, then the temperature was raised to 274 ° C. at a rate of 0.6 ° C./min and held at 274 ° C. for 50 minutes. Then, the temperature was raised to 282 ° C. Open the extraction valve at the bottom of the autoclave, pressurize with nitrogen, flush the contents into a vessel with a stirrer over 15 minutes, stir at 250 ° C for a while to remove most of the NMP, polyphenylene sulfide (PPS) and Solids containing salts were collected.

  The obtained solid and 15120 g of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 70 ° C. for 30 minutes, and suction filtered through a glass filter. Next, 17280 g of ion-exchanged water heated to 70 ° C. was poured into a glass filter, and suction filtered to obtain a cake.

  The obtained cake and 11880 g of ion-exchanged water were charged into an autoclave equipped with a stirrer, and the inside of the autoclave was replaced with nitrogen, and then the temperature was raised to 192 ° C. and held for 30 minutes. Thereafter, the autoclave was cooled and the contents were taken out.

  The contents were subjected to suction filtration with a glass filter, and then 17280 g of ion-exchanged water at 70 ° C. was poured into the contents, followed by suction filtration to obtain a cake. The obtained cake was dried with hot air at 80 ° C. and further vacuum-dried at 120 ° C. for 24 hours to obtain dry PPS (A-1). The melt viscosity of the obtained PPS was measured using a capillograph (manufactured by Toyo Seiki Co., Ltd.) under conditions of a die length of 10 mm, a die hole diameter of 0.5 mm, 300 ° C., and a shear rate of 1000 / sec. s.

Production Example 2 Polyphenylene sulfide resin (A-2)
In a 70 liter autoclave equipped with a stirrer, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2957.21 g (70.97 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP ) 11434.50 g (115.50 mol), sodium acetate 861.00 g (10.5 mol), and ion-exchanged water 10500 g, and gradually heated to 245 ° C. over about 3 hours while passing nitrogen at normal pressure, After distilling out 14780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The amount of water remaining in the system per mole of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

  Next, 10235.46 g (69.63 mol) of p-dichlorobenzene and 900.00 g (91.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm while stirring at 0.6 ° C. / The temperature was raised to 238 ° C. at a rate of minutes. After reacting at 238 ° C. for 95 minutes, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min. After performing the reaction at 270 ° C. for 100 minutes, 1260 g (70 mol) of water was injected over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./minute. Then, after cooling to 200 ° C. at a rate of 1.0 ° C./min, it was rapidly cooled to near room temperature.

  The contents were taken out, diluted with 26300 g of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the resulting particles were washed with 31900 g of NMP and filtered off. This was washed several times with 56000 g of ion-exchanged water and filtered, then washed with 70000 g of 0.05 wt% aqueous acetic acid and filtered. After washing with 70000 g of ion-exchanged water and filtering, the resulting hydrous PPS particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C. The obtained PPS resin (A-2) had a melt viscosity of 60 Pa · s (310 ° C., shear rate of 1000 / s).

Production Example 3 Liquid crystalline polyester resin (B-1)
In a 5 L reaction vessel equipped with a stirring blade and a distillation pipe, 870 parts by weight of p-hydroxybenzoic acid, 292 parts by weight of 4,4′-dihydroxybiphenyl, 125 parts by weight of hydroquinone, 292 parts by weight of terephthalic acid, 157 parts by weight of isophthalic acid And 1302 parts by weight of acetic anhydride (1.09 equivalents of total phenolic hydroxyl groups) were allowed to react at 145 ° C. for 1 hour with stirring under a nitrogen gas atmosphere, and the jacket temperature was changed from 145 ° C. to 330 ° C. for 4 hours. The temperature was raised at. Thereafter, the polymerization temperature was maintained at 330 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm ² (0.1 MPa), the polymer is discharged onto a strand through a die having a circular discharge port having a diameter of 10 mm, and pelletized by a cutter. A liquid crystal polyester (B-1) was obtained.

  As a result of composition analysis of the liquid crystal polyester (B-1), the ratio of the structural unit (I) to the total of the structural unit (I), the structural unit (II), and the structural unit (III) was 70 mol%. It was. The ratio of the structural unit (II) to the total of the structural unit (II) and the structural unit (III) was 58 mol%. The ratio of the structural unit (IV) to the total of the structural unit (IV) and the structural unit (V) was 65 mol%. The total of the structural unit (II) and the structural unit (III) and the total of the structural unit (IV) and the structural unit (V) were substantially equimolar. Moreover, Tm was 310 degreeC and melt viscosity was 30 Pa.s.

Production Example 4 Liquid crystalline polyester resin (B-2)
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 994 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4′-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, and an intrinsic viscosity of about 0.6 dl / g 216 parts by weight of polyethylene terephthalate and 960 parts by weight of acetic anhydride (1.10 equivalents of total phenolic hydroxyl groups) were charged and reacted at 145 ° C. for 1 hour with stirring under a nitrogen gas atmosphere. The temperature was raised in 4 hours. Thereafter, the polymerization temperature was maintained at 320 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), the polymer was discharged to a strand-like material via a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

  The composition analysis of this liquid crystalline polyester (B-2) revealed that the structural unit (I) was 66.7 mol%, the structural unit (II) was 6.3 mol%, and the ethylenedioxy unit derived from polyethylene terephthalate was The content was 10.4 mol% and the structural unit (IV) was 16.6 mol%. Moreover, Tm was 313 degreeC and melt viscosity was 13 Pa.s.

Production Example 5 Liquid crystalline polyester resin (B-3)
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 25 parts by weight of p-hydroxybenzoic acid, 813 parts by weight of 6-hydroxy-2-naphthoic acid, 419 parts by weight of 4,4′-dihydroxybiphenyl, 374 terephthalic acid 1 part by weight and 965 parts by weight of acetic anhydride (1.05 equivalents of total phenolic hydroxyl groups) were allowed to react at 145 ° C. for 1 hour with stirring in a nitrogen gas atmosphere, and then from 145 ° C. to 360 ° C. over 4 hours. The temperature was raised. Thereafter, the polymerization temperature was maintained at 360 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), the polymer was discharged to a strand-like material via a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

  Composition analysis of this liquid crystalline polyester (B-3) revealed that the structural unit (I) was 2 mol%, the 6-oxy-2-naphthalate unit was 48 mol%, the structural unit (II) was 25 mol%, and the structure The unit (IV) was 25 mol%. The Tm was 350 ° C. and the melt viscosity was 25 Pa · s.

The elastomer (C) used in each example and comparative example is shown below.
(C-1): Arkema Rotoryl 35BA40 (MFR = 40 g / 10 min, content of structural unit derived from acrylic acid = 35 wt%)
(C-2): Arkema Bondine HX8210 (MFR = 200 g / 10 min, content of structural unit derived from acrylic acid = 9 wt%)
(C-3): Toray DuPont Hytrel 3046 (MFR = 10 g / 10 min, content of structural unit derived from acrylic acid = 0 wt%)
(C-4): Sumitomo Chemical Bond First 7M (MFR = 7 g / 10 min, content of structural unit derived from acrylic acid = 33 wt%)

The filler (D) used in each example and comparative example is shown below.
(D-1): Nippon Electric Glass Chopped Strand (T-747H)

The additive (E) used in each example and comparative example is shown below.
(E-1): Japan Epoxy Resin Epicoat 191P (cyclodicarboxylic acid type epoxy resin)

Examples 1-10, Comparative Examples 1-7
In a TEM35B type twin screw extruder manufactured by Toshiba Machine equipped with a side feeder, polyphenylene sulfide resins (A-1, A-2), liquid crystalline polyester resins (B-1 to B-3) obtained in the respective production examples, and Elastomers (C-1 to C-4) were blended in a blending amount shown in Table 1 so that the total amount was 100% by weight, and an additive (E-1) was added from a hopper in a blending amount shown in Table 1, The filler (D-1) was added from the side in the amount shown in Table 1, the cylinder temperature was set to 300 ° C. (only Comparative Example 1 was 330 ° C.), and melt-kneaded to obtain pellets. The pellets of the obtained thermoplastic resin composition were dried with hot air, and the following (1) to (3) were evaluated. The results are shown in Table 1.

(1) Metal adhesion strength evaluation The thermoplastic resin composition was subjected to a FANUC α30C injection molding machine (FANUC screw diameter 28 mm), the cylinder temperature was 330 ° C, and the mold temperature was 130 ° C (only Comparative Example 1 was 90 ° C). A test piece having a length of 15 × 15 × 30 mm was formed so as to cover an end of an aluminum prism having a length of 5 × 5 × 50 mm held in the mold with a thickness of 5 mm and a length of 5 mm. The obtained metal adhesion test piece was pulled with Orientec Tensilon at a strain rate of 10 mm / min, and the strength at which the resin / metal adhesion surface was peeled off was determined. The strength necessary for peeling off the resin / metal bonding surface was defined as the metal bonding strength, and the higher the strength, the higher the metal bonding property of the thermoplastic resin composition.

(2) Metal adhesion evaluation at the time of reflow 75 metal adhesion test pieces obtained in the same manner as in (1) were heated to 200 ° C. at 1.6 ° C./second by a reflow simulator core 9030c (manufactured by Cores Co., Ltd.). The sample was preheated for 2 minutes, reflowed at a maximum surface temperature of 260 ° C. for 30 seconds, and then cooled to room temperature for reflow treatment. After the reflow treatment, the metal adhesion test piece was dipped in red ink, washed with water, dried, and then subjected to a penetrating deep wound method to check for cracks with a stereomicroscope, and ink oozed out from the resin / metal adhesion site. The number was examined. The smaller the number of ink oozing out, the better the adhesion.

(3) Thickness dependence evaluation of flow length The thermoplastic resin composition was subjected to a FANUC α30C injection molding machine (FANUC screw diameter 28 mm), the cylinder temperature was 330 ° C, and the mold temperature was 130 ° C (Comparative Example 2 only 90 ° C). ) As a rod-shaped molded product having two types of thickness (width 12.7 mm, thickness 0.5 mm and 0.3 mm, side gate 0.5 mm × 5.0 mm), and 0.5 mm-thick molded product has a length of 100 mm. Under the conditions, the average value of the difference between the maximum value and the minimum value of the flow length of 0.3 mm thickness when 100 shots of 0.5 mm thickness and 0.3 mm thickness were simultaneously formed was examined. It was evaluated that the smaller the value, the smaller the dependency of the flow length on the thickness, and the smaller the change in flowability with respect to the thickness of the molded product

  From the results of Table 1, it can be seen that the thermoplastic resin composition of the embodiment of the present invention has excellent metal adhesion strength and retains high metal adhesion even after high temperature treatment. In addition, the thickness dependency of the flow length is small, and the change in the flowability with respect to the thickness of the molded product is small. Therefore, it can be seen that heat resistance is required and it is suitable for a molded product such as a part in contact with a metal.

  The thermoplastic resin composition of the present invention has characteristics such as high metal adhesion strength, metal adhesion after high-temperature treatment, and small thickness dependence of flow length, and thus is useful for parts that come into contact with metal.

Claims (8)

The total of (A), (B) and (C) is 100% by weight, the polyphenylene sulfide (A) is 40 to 90% by weight, the liquid crystalline polyester (B) is 5 to 50% by weight, and the melt flow rate (ISO 1133). A thermoplastic resin composition obtained by blending 1 to 20% by weight of an elastomer (C) having a temperature of 190 ° C. and a load of 2160 g (10 to 400 g / 10 min). The thermoplastic resin composition according to claim 1, wherein the elastomer (C) is an elastomer having a structural unit derived from acrylic acid. The thermoplastic resin composition according to claim 1 or 2, wherein the elastomer (C) is a copolymerized elastomer having a content of structural units derived from acrylic acid of 20 to 50% by weight. The heat according to any one of claims 1 to 3, wherein the liquid crystalline polyester (B) is composed of the following structural units (I), (II), (III), (IV) and (V). Plastic resin composition.

The thermoplastic resin according to any one of claims 1 to 4, wherein the filler (D) is further blended in an amount of 10 to 200 parts by weight with respect to a total of 100 parts by weight of the (A), (B) and (C). Resin composition. A molded product obtained by melt-molding the thermoplastic resin composition according to claim 1. The molded article according to claim 6, which is in contact with a metal. The molded article according to claim 6 or 7, wherein the molded article is a connector or a breaker.