JP2019006884A - Plastic fastener comprising polyphenylene sulfide resin composition - Google Patents

Abstract

To obtain a plastic fastener comprising a polyphenylene sulfide resin composition, which combines excellent toughness (tensile elongation), long-term high-temperature durability, chemical resistance, and surface appearance.SOLUTION: The plastic fastener comprises a PPS resin composition containing (a) a PPS resin and (b) a thermoplastic resin having a melting point or a glass transition temperature of 150°C or higher. In the morphology (phase structure) of the plastic fastener, the PPS resin forms a continuous phase (sea phase), and the thermoplastic resin having a melting point or a glass transition temperature of 150°C or higher forms a dispersed phase (island phase) dispersed with a number average dispersed particle diameter of 500 nm or less.SELECTED DRAWING: None

Description

  The present invention relates to a plastic fastener comprising a polyphenylene sulfide resin composition having excellent toughness, high temperature long-term durability, chemical resistance and surface appearance.

  Plastic fasteners such as clips, clamps, hook-and-loop fasteners, cable ties, cable ties, bands, point fasteners, and wire fasteners are subjected to a tensile test from the viewpoint of preventing damage to deformed parts, hinge parts, and bonded parts during use. Resins with excellent toughness, typically represented by the elongation, are used, and conventionally polyamide resins and polypropylene resins have been widely used.

  However, in recent years, the usage environment of plastic fasteners used in automobiles and electrical / electronic applications has changed to environments exposed to high temperatures and new lubricating oils and refrigerants. With conventional polyamide resins and polypropylene resins, Satisfying toughness, high-temperature long-term durability, etc. has become difficult. Therefore, creation of a new resin material that can withstand these use environments is required.

  On the other hand, polyphenylene sulfide (hereinafter abbreviated as “PPS”) resin is an engineering plastic excellent in heat resistance, flame retardancy, chemical resistance and mechanical properties. Various resins can be used by various molding methods such as injection molding and extrusion molding. Since it can be molded into molded articles, fibers, films, etc., it is put to practical use in a wide range of fields such as electric / electronic parts, mechanical parts, and automobile parts.

  Therefore, taking advantage of the characteristics of these PPS resins, Patent Document 1 describes a base fabric and a hook-like engagement element from the viewpoint of heat resistance, flame resistance, hook shape maintenance, and hook engagement element pull-out resistance. A hook-and-loop fastener using fibers made of polyphenylene sulfide resin in the part is described.

  In addition, Patent Document 2 discloses injection molding that exhibits excellent impact strength and impact strength retention after 1000 hours of treatment at 165 ° C. by adding a crosslinking impact resistance improver (olefin elastomer, etc.) to the PPS resin. Parts and fasteners are described.

  On the other hand, Patent Document 3 describes an attempt to improve the high-temperature and long-term durability of a PPS resin by adding an alkali metal or alkaline earth metal hydroxide to the PPS resin.

International Publication No. 2008-59958 Special table 2017-500404 gazette JP 2013-28761 A

  However, although Patent Document 1 is derived from the features of PPS resin, high heat resistance and flame resistance can be obtained, but since the toughness, which is an essential problem of PPS resin, has not been improved, deformation of the resin occurs during repeated use. This causes a decrease in engagement force.

  Moreover, although patent document 2 can obtain the outstanding impact strength by adding bridge | crosslinking impact modifiers (olefin type elastomer etc.) to PPS resin, it is a plastic fastener from the lack of heat resistance of a bridge | crosslinking impact modifier. It is difficult to achieve the required excellent toughness (tensile elongation) after high-temperature long-term durability treatment.

  In Patent Document 3, although an excellent tensile elongation can be obtained after high-temperature and long-term durability treatment by adding an alkali metal or alkaline earth metal hydroxide to a PPS resin, the composition exhibits strong alkalinity and has a composition. Since a high concentration of alkali metal salt or alkaline earth metal salt is present as an impurity in the product, it is difficult to apply to practical use.

  Then, this invention makes it a subject to obtain the plastic fastener which consists of a polyphenylene sulfide resin composition which has the outstanding toughness (tensile elongation), high temperature long-term durability, chemical resistance, and surface appearance.

  The present invention is a plastic fastener comprising a PPS resin composition comprising a PPS resin and a thermoplastic resin having a melting point of 150 ° C. or higher or a glass transition temperature as a result of intensive studies to solve such problems. In the morphologies (phase structures), a dispersed phase (island) in which a PPS resin forms a continuous phase (sea phase) and a thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher is dispersed with a number average dispersed particle diameter of 500 nm or less. By controlling the phase separation structure forming the phase), a plastic fastener having excellent toughness (tensile elongation), high-temperature long-term durability, chemical resistance, and surface appearance is obtained.

That is, the present invention has been made to solve at least a part of the problems described above, and can be implemented as the following forms.
(1) A plastic fastener comprising a polyphenylene sulfide resin composition comprising (a) a polyphenylene sulfide resin and (b) a thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher, and the morphology of the plastic fastener (phase structure) (A) A plastic fastener in which a polyphenylene sulfide resin forms a continuous phase (sea phase), and (b) a thermoplastic resin dispersed in a number average dispersed particle diameter of 500 nm or less (dispersed phase (island phase)).
(2) ASTM No. 4 dumbbell obtained by injection molding the polyphenylene sulfide resin composition was treated in the atmosphere at 165 ° C. for 1000 hours, and then in accordance with ASTM-D638 under the conditions of a tensile speed of 10 mm / min and an ambient temperature of 23 ° C. The plastic fastener according to (1), wherein the measured tensile breaking elongation is 10% or more.
(3) ASTM No. 4 dumbbell obtained by injection molding the polyphenylene sulfide resin composition was treated in ATF at 150 ° C. for 1000 hours, and then in accordance with ASTM-D638 under conditions of a tensile speed of 10 mm / min and an ambient temperature of 23 ° C. The plastic fastener according to (1) or (2), wherein the measured tensile breaking elongation is 10% or more.
(4) The (b) thermoplastic resin is at least one selected from a polyetherimide resin, a poly (etherimide-siloxane) copolymer, a polyamide resin, and a fluororesin (1) to (3) A plastic fastener according to any one of the above.
(5) The polyphenylene sulfide resin composition further comprises (c) 0.01 to 5 parts by weight of an oxo acid metal salt of phosphorus per 100 parts by weight of the (a) polyphenylene sulfide resin. ) The plastic fastener according to any one of
(6) The plastic fastener according to any one of (1) to (5), wherein the plastic fastener is selected from a clip, a clamp, a hook-and-loop fastener, a binding band, a cable tie, and a band.

  According to the present invention, in the plastic fastener morphology (phase structure), the PPS resin forms a continuous phase (sea phase), and the thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher has a number average dispersed particle size of 500 nm. Polyphenylene sulfide resin that combines excellent toughness (tensile elongation), high temperature long-term durability, chemical resistance, and surface appearance by controlling the phase separation structure to form the dispersed phase (island phase) dispersed below. A plastic fastener made of the composition can be obtained.

It is a schematic diagram of the plastic fastener used for product evaluation in the Example.

  The present invention relates to a plastic fastener made of a PPS resin composition comprising a PPS resin and a thermoplastic resin having a melting point of 150 ° C. or higher or a glass transition temperature. In the plastic fastener morphology (phase structure), the PPS resin is a continuous phase. This is a plastic fastener forming a (sea phase) and forming a dispersed phase (island phase) in which a thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher is dispersed with a number average dispersed particle diameter of 500 nm or less. In the present invention, the plastic fastener refers to a fastener using a resin as a material of an element. Plastic fasteners are used in a wide range of general and industrial fields such as those used for clothing, those that hold substrates in equipment, and those that bind or fix cables. Details of the plastic fastener will be described later.

  Hereinafter, embodiments of the present invention will be described in detail.

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

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

  Since the PPS copolymer having a part of such a structure has a low melting point, such a resin composition is advantageous in terms of moldability.

  Although there is no restriction | limiting in particular in the weight average molecular weight of (a) PPS resin used by this invention, 30000-150,000 are preferable, and 40000-130,000 are more preferable from the meaning which acquires the more outstanding mechanical physical property, 45000-110000. Is more preferable, and 50000-90000 is more preferable. When the weight average molecular weight is small, the mechanical properties of the PPS resin itself are lowered. On the other hand, when the weight average molecular weight exceeds 150,000, the melt viscosity is remarkably increased, which is not preferable in the molding process.

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

  Although the manufacturing method of (a) PPS resin used for this invention is demonstrated below, if (a) PPS resin 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 aromatics 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. For the purpose of introducing a carboxyl group, carboxyl group-containing dihalogenated aromatics such as 2,4-dichlorobenzoic acid, 2,5-dichlorobenzoic acid, 2,6-dichlorobenzoic acid, and 3,5-dichlorobenzoic acid It is also one of preferred embodiments to use a compound and a mixture thereof as a copolymerization monomer, and it is also possible to combine two or more different polyhalogenated aromatic compounds into a copolymer. 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. mol per mol of sulfidizing agent, from the viewpoint of obtaining a (a) PPS resin having a viscosity suitable for processing. A range of 5 moles, more preferably 1.005 to 1.2 moles 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 sulfiding agent, it is particularly preferable to use an alkali metal hydroxide at the same time, but the amount used is 0.95 to 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 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]
(A) A monohalogen compound (not necessarily an aromatic compound) is combined with the polyhalogenated aromatic compound for the purpose of forming a terminal of the PPS resin or adjusting the polymerization reaction or the molecular weight. Can be used together.

[Polymerization aid]
In order to obtain a relatively high degree of polymerization (a) PPS resin in a shorter time, it is also one of preferred embodiments to use a polymerization aid. Here, the polymerization assistant means (a) a substance having an action of increasing the viscosity of the PPS resin to be obtained. 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 using these alkali metal carboxylates as polymerization aids, the amount used is usually in the range of 0.01 to 2 moles per mole of charged alkali metal sulfide, and in the sense of obtaining a higher degree of polymerization. The range of 0.1-0.6 mol is preferable, and the range of 0.2-0.5 mol is more preferable.

  Moreover, the addition amount in the case of using water as a polymerization aid is usually in the range of 0.3 mol to 15 mol with respect to 1 mol of the charged alkali metal sulfide. The range of 10 mol 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. The alkali metal carboxylate described above also acts as a polymerization stabilizer. 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 in a proportion of 0.02 to 0.2 mol, preferably 0.03 to 0.1 mol, more preferably 0.04 to 0.09 mol, relative to 1 mol of the charged alkali metal sulfide. Is preferably used. If this ratio is small, the stabilizing effect is insufficient. Conversely, if the ratio is too large, it is 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 the (a) PPS resin used in the present invention will be described in detail in the order of a pre-process, a polymerization reaction process, a recovery process, and a post-treatment process. Of course, the process is limited to this process. It is not something.

[pre-process]
(A) In the production method of PPS resin, the sulfiding agent is usually used in the form of a hydrate, but before adding the polyhalogenated aromatic compound, the mixture containing the organic polar solvent and the sulfiding agent is increased. It is preferable to warm and remove excess 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) A PPS resin 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 normally selected, 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]
(A) In the method for producing a PPS resin, 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]
(A) The PPS resin 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. (A) The acid used for the acid treatment of the PPS resin is not particularly limited as long as it does not have the function of decomposing the (a) PPS resin, such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propyl acid. Among them, acetic acid and hydrochloric acid are more preferably used, but (a) those that decompose and deteriorate the PPS resin such as nitric acid are not preferable.

  As the acid treatment method, there is a method of immersing (a) the PPS resin 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 PPS resin powder in an aqueous PH4 solution heated to 80 to 200 ° C. and stirring for 30 minutes. The PH after processing may be 4 or more, for example, about PH 4-8. The acid-treated (a) PPS resin 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 effect of the preferred chemical modification of the (a) PPS resin by acid treatment.

  When performing hot water treatment, it is as follows. (A) In the hot water treatment of the PPS resin, the temperature of the hot water is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 150 ° C. or higher, and particularly preferably 170 ° C. or higher. If it is less than 100 degreeC, since the effect of the preferable chemical modification | denaturation of (a) PPS resin is small, it is not preferable.

  The water used is preferably distilled water or deionized water in order to exhibit the effect of preferable chemical modification of the (a) PPS resin by hot water washing. There is no particular restriction on the operation of the hot water treatment, and a predetermined amount of (a) PPS resin is put into a predetermined amount of water and heated and stirred in a pressure vessel, or a method of continuous hot water treatment is performed. Is called. The ratio of (a) PPS resin to water is preferably larger, but usually a bath ratio of (a) 200 g or less of PPS resin is selected for 1 liter of water.

  Further, since the decomposition of the terminal group is not preferable, the treatment atmosphere is desirably an inert atmosphere in order to avoid this. Furthermore, it is preferable that the (a) PPS resin that has finished this hot water treatment operation is washed several times with warm water in order to remove the remaining components.

  When washing with an organic solvent, it is as follows. (A) The organic solvent used for washing the PPS resin is not particularly limited as long as it does not have the action of decomposing (a) the PPS resin. For example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, Nitrogen-containing polar solvents such as 1,3-dimethylimidazolidinone, hexamethylphosphoramide, piperazinones, sulfoxide / sulfon solvents such as dimethyl sulfoxide, dimethyl sulfone, sulfolane, ketones such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone Solvents, ether solvents such as dimethyl ether, dipropyl ether, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, Halogen solvents such as trachlorethane, perchlorethane, chlorobenzene, alcohol / phenol solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol and the like Aromatic hydrocarbon solvents such as benzene, toluene, xylene and the like can be mentioned. 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 such as (a) immersing a PPS resin in an organic solvent, and if necessary, stirring or heating can be appropriately performed. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning (a) PPS resin 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, after adding the 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 is 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 alkali metal ion and alkaline earth metal ion concentration 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 PPS. 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 the present invention, from the viewpoint of obtaining a polyphenylene sulfide resin composition having excellent residence stability, residual oligomers and residual salts were removed by repeating organic solvent washing and warm water of about 80 ° C. or hot water washing several times. Thereafter, an acid treatment or a method of treating with an alkali metal salt or an alkaline earth metal salt is preferred, and a method of treating with an alkali metal salt or an alkaline earth metal salt is particularly preferred.

  In addition, (a) the PPS resin can be used after having been polymerized to have a high molecular weight by heating in an oxygen atmosphere and thermal oxidation 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.

  Moreover, it is also possible to perform 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, the (a) PPS resin of the present invention is a substantially linear PPS resin that is not subjected to high molecular weight by thermal oxidation cross-linking treatment from the viewpoint of expressing excellent toughness, or is mildly oxidized cross-linking treatment The semi-crosslinked PPS resin is preferable. On the other hand, the PPS resin subjected to the thermal oxidative cross-linking treatment is suitable from the viewpoint of suppressing the creep distortion, and can be used by appropriately mixing with the linear PPS resin. In the present invention, a plurality of (a) PPS resins having different melt viscosities may be mixed and used.

  The (a) PPS resin of the present invention preferably includes 25 to 400 μmol / g of a carboxyl group from the viewpoint of improving compatibility with (b) a thermoplastic resin having a melting point of 150 ° C. or higher or a glass transition temperature. Can be mentioned. The carboxyl group content is more preferably 25 to 250 μmol / g, further preferably 30 to 150 μmol / g, and further preferably 30 to 80 μmol / g. When the amount of carboxyl groups in the PPS resin is less than 25 μmol / g, the interaction with (b) the thermoplastic resin and (d) the organic silane compound tends to decrease, such being undesirable. On the other hand, when the carboxyl group content of the PPS resin exceeds 400 μmol / g, the volatile content in the processing step increases, which is not preferable.

  (A) As a method of introducing a carboxyl group into a PPS resin, a method of copolymerizing a polyhalogenated aromatic compound containing a carboxyl group or a compound containing a carboxyl group, such as maleic anhydride or sorbic acid, is added. Then, (a) a method of introducing by reacting with PPS resin while melt-kneading can be exemplified.

(2) (b) Thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher The PPS resin composition constituting the plastic fastener of the present invention contains a thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher. Formulation is essential. By finely dispersing a thermoplastic resin having a melting point of 150 ° C. or higher or a glass transition temperature in the PPS resin, it is possible to improve the toughness (tensile elongation), which is an essential problem of the PPS resin, and to achieve a high temperature long-term durability treatment. It becomes possible to show excellent toughness later. On the other hand, when a thermoplastic resin having a melting point or glass transition temperature lower than 150 ° C. is used, excellent toughness (tensile elongation) cannot be expressed after high-temperature long-term durability treatment. Specifically, olefin elastomers that have been generally used as modifiers for PPS resins cannot satisfy high temperature long-term durability.

  Examples of the thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher used in the present invention include polyamide resins (PA6, PA66, PA610, PA46, MXD6, PA6T / 66, PA9T, PA10T, PA11, PA12, etc.), poly Butylene terephthalate resin, polyethylene terephthalate resin, modified polyphenylene ether resin, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyetherketone resin, polythioetherketone resin, polyetherimide resin, poly (ether) (Imido-siloxane) copolymer, polyetheretherketone resin, polyimide resin, polyamideimide resin, fluororesin (polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene) Oroethylene copolymer (ETFE), tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene-hexafluoropyrene copolymer Specific examples thereof include, but are not limited to, coalescence, polyvinylidene fluoride (PVDF), and polychlorotrifluoroethylene (PCTFE).

  Among them, polyamide resin, polyetherimide resin, poly (etherimide-siloxane) copolymer, modified polyphenylene ether resin, polysulfone resin, polyallyl sulfone resin, polyether ether ketone resin, polyimide resin, polyamideimide resin, fluorine resin Polyamide resin, polyetherimide resin, poly (etherimide-siloxane) copolymer, and fluorine resin are particularly preferable.

  The thermoplastic resin (b) having a melting point or glass transition temperature of 150 ° C. or higher used in the present invention may contain a reactive functional group from the viewpoint of forming an intermolecular bond with the PPS resin or the organosilane compound. It is mentioned as a preferred embodiment.

  The reactive functional group is not particularly limited, and specifically, vinyl group, epoxy group, carboxyl group, acid anhydride group, ester group, aldehyde group, carbonyldioxy group, haloformyl group, alkoxycarbonyl group, amino group. Groups, hydroxyl groups, styryl groups, methacryl groups, acrylic groups, ureido groups, mercapto groups, sulfide groups, isocyanate groups, hydrolyzable silyl groups, etc., among which epoxy groups, carboxyl groups, acid anhydride groups, amino groups A hydroxyl group is preferred, and two or more of these reactive functional groups may be contained.

  As a method for introducing a reactive functional group into a thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher, it is compatible with a thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher and contains the functional group In the method of blending a compound or resin to be polymerized, or when polymerizing a thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher, a polymerizable monomer containing the functional group or a functional group convertible to the functional group A method of copolymerizing with a polymerizable monomer contained, an initiator containing the functional group or a functional group convertible to the functional group when polymerizing a thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher. A method using a contained initiator, a thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher, a polymerizable monomer containing the functional group, A method of reacting a polymerizable monomer containing a functional group that can be converted into a functional group in the presence of a radical generator, a method of oxidizing, thermally decomposing a thermoplastic resin having a melting point of 150 ° C. or higher or a glass transition temperature Among them, a method of introducing a functional group into a main chain or a side chain by copolymerization, a thermoplastic resin having a melting point of 150 ° C. or higher or a glass transition temperature and a polymerizable monomer containing the functional group Is preferable from the viewpoint of quality, cost, and control of the amount introduced.

  The polymerizable monomer containing the functional group is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, crotonic acid, highmic acid, acid anhydrides thereof, and acrylic acid. Examples thereof include glycidyl, glycidyl methacrylate, glycidyl ethyl acrylate, glycidyl itaconate, vinyl acetate, vinyl propionate, vinyl trimethoxysilane, vinyl triethoxysilane, and γ-methacryloxypropyltrimethoxysilane.

  The amount of the functional group contained in the thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher is a thermoplastic having a melting point or glass transition temperature of 150 ° C. or higher from the viewpoint of sufficient reaction with the PPS resin. 0.01 mol% or more is preferable with respect to 1 mol of resin, 0.05 mol% or more is more preferable, and it is still more preferable that it is 0.1 mol% or more. The upper limit of the functional group amount is not particularly limited as long as the original properties of the thermoplastic resin having a melting point of 150 ° C. or higher or a glass transition temperature are not impaired. The following are preferable, and 3 mol% or less can be illustrated as a more preferable range.

  The blending amount of the thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher in the embodiment of the present invention is not particularly limited, but (b) 150 ° C. with respect to 100 parts by weight of (a) PPS resin. The range of 5 to 100 parts by weight of the thermoplastic resin having the above melting point or glass transition temperature is preferably selected, more preferably 5 to 70 parts by weight, and still more preferably 5 to 50 parts by weight. By setting the thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher to 100 parts by weight or less, it becomes possible to control the dispersion diameter of the island phase formed by (b) the thermoplastic resin to 500 nm or less. The excellent toughness characteristic of the plastic fastener made of the resin composition is exhibited. Moreover, the thermoplastic resin which has 150 degreeC or more melting | fusing point or glass transition temperature shall be 5 weight part or more, and there exists an expression effect of the desired toughness. Two or more thermoplastic resins having a melting point or glass transition temperature of 150 ° C. or higher can be used in combination.

(3) (c) Phosphorus Oxo Acid Metal Salt In the present invention, it is preferable to blend a phosphorus oxo acid metal salt. As a result of promoting the reaction between (a) the PPS resin and (b) the thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher and other additives, the initial toughness and the high temperature long-term durability The effect of improving toughness after processing can be expected.

  As the oxo acid metal salt of phosphorus, metal salts of hypophosphorous acid, phosphorous acid, phosphoric acid, phosphinic acid, phosphonic acid, diphosphoric acid and triphosphoric acid are preferable, and metal salts of hypophosphorous acid and phosphinic acid are preferred. More preferred. Specifically, potassium hypophosphite, sodium hypophosphite, calcium hypophosphite, potassium phosphinate, sodium phosphinate, calcium phosphinate, aluminum phosphinate, aluminum diethylphosphinate, zinc phosphinate, magnesium phosphinate, etc. Can be mentioned. Among these, phosphinic acid metal salts are preferable from the viewpoint of phosphorus concentration and handling, and sodium phosphinate is more preferable.

  Each of these phosphorus oxo acid metal salts can be used alone or in the form of a mixture of two or more.

  The amount of phosphorus oxoacid metal salt used in the present invention is preferably 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the PPS resin. More preferably, it is 0.1 to 1 part by weight. It is preferable that the amount of phosphorus oxoacid metal salt is 5 parts by weight or less, because gas generation during dry heat treatment is suppressed and microvoids are hardly formed. If the amount of phosphorus oxoacid metal salt is 0.01 parts by weight or more, the reaction between the PPS resin and the thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher and other additives sufficiently proceeds. preferable.

(4) (d) Organosilane compound Addition of an organosilane compound to the PPS resin composition constituting the plastic fastener of the present invention is the dispersibility of a thermoplastic resin having a melting point of 150 ° C or higher or a glass transition temperature with respect to the PPS resin. It is useful for increasing the strength and is effective for improving toughness.

  Specific examples of such organic silane compounds include epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Mercapto group-containing alkoxysilane compounds such as alkoxysilane compounds, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2- Ureido group-containing alkoxysilane compounds such as ureidoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldi Isocyanate group-containing alkoxysilane compounds such as methoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2-amino And organic silane compounds such as amino group-containing alkoxysilane compounds such as ethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane. A group-containing alkoxysilane compound is particularly preferred from the viewpoint of reactivity.

  The amount of the organosilane compound added is preferably 0.1 to 5 parts by weight, particularly preferably 0.2 to 3 parts by weight with respect to 100 parts by weight of the PPS resin.

(5) (e) Inorganic filler The PPS resin composition constituting the plastic fastener of the present invention is not an essential component but should be used by blending (e) an inorganic filler within a range not impairing the effects of the present invention. Is also possible. Specific examples of the inorganic filler (e) include glass fiber, carbon fiber, carbon nanotube, carbon nanohorn, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, Fibrous fillers such as silicon carbide fiber, ceramic fiber, asbestos fiber, stone-kow fiber, metal fiber, or fullerene, talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, silica, bentonite, Silicates such as asbestos and 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, hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide, glass beads, glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black and silica, Non-fibrous fillers such as graphite are used, among which glass fiber, silica, and calcium carbonate are preferable, and calcium carbonate and silica are particularly preferable from the viewpoint of the effects of the anticorrosive material and the lubricant. Further, these (e) inorganic fillers may be hollow, and two or more kinds may be used in combination. These (e) inorganic fillers may be used after pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound. Of these, calcium carbonate, silica, and carbon black are preferable from the viewpoint of the anticorrosive material, the lubricant, and the effect of imparting conductivity.

  The blending amount of the inorganic filler is selected within a range of 10 parts by weight or less with respect to a total of 100 parts by weight of (a) polyphenylene sulfide resin and (b) a thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher. A range of less than 5 parts by weight is preferred, a range of less than 1 part by weight is more preferred, and a range of 0.8 parts by weight or less is even more preferred. There is no particular lower limit, but 0.0001 parts by weight or more is preferable. The blending of the inorganic filler is effective for improving the elastic modulus of the material, but a large amount of blending exceeding 10 parts by weight is not preferable because the toughness is greatly lowered. The content of the inorganic filler can be appropriately changed depending on the application from the balance between toughness and rigidity.

(6) (f) Other additives Furthermore, in the PPS resin composition constituting the plastic fastener of the present invention, the following compounds are added for the purpose of modification within the range not impairing the effects of the present invention. Is possible. Plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, organophosphorus compounds, crystal nucleating agents such as organophosphorus compounds, polyetheretherketone, montanic acid waxes, lithium stearate, aluminum stearate Metal additives such as ethylenediamine / stearic acid / sebacic acid polycondensate, release agents such as silicone compounds, anti-coloring agents, and other normal additives such as water, lubricants, anti-UV agents, coloring agents, foaming agents, etc. Can be blended. If any of the above compounds exceeds 10% by weight of the total composition, the original properties of the PPS resin composition of the present invention are impaired, and therefore it is not preferred, and 5% by weight or less, more preferably 1% by weight or less is added.

(7) Manufacturing method of resin composition As a method of manufacturing the PPS resin composition constituting the plastic fastener of the present invention, manufacturing in a molten state or manufacturing in a solution state can be used. Manufacturing in a molten state is preferably used. For production in a molten state, melt kneading with an extruder, melt kneading with a kneader, or the like can be used. From the viewpoint of productivity, melt kneading with an extruder that can be continuously produced is preferably used. For melt kneading by an extruder, one or more extruders such as a single screw extruder, a twin screw extruder, a multi screw extruder such as a four screw extruder, and a twin screw single screw compound extruder can be used. From the viewpoint of improvement in productivity, reactivity, and productivity, a multi-screw extruder such as a twin-screw extruder or a four-screw extruder can be preferably used, and melt kneading with a twin-screw extruder is most preferable.

  A more specific method of melt kneading is not necessarily limited to this, but L / D (L: screw length, D: screw diameter) is 10 or more, preferably 20 or more. It is preferable to use a twin screw extruder having two or more parts, preferably three or more parts. The upper limit of L / D is not particularly limited, but 60 or less is preferable from the viewpoint of economy. The upper limit of the kneading portion is not particularly limited, but is preferably 10 or less from the viewpoint of productivity. The ratio of the kneading part with respect to the total length of the screw is preferably 15% or more, more preferably 20% or more, and further preferably 30% or more. When the ratio of the kneading part with respect to the total length of the screw is less than 15%, the kneading force is inferior, so that the number average dispersion diameter of the (b) thermoplastic resin becomes coarse and the desired physical properties are hardly exhibited. On the other hand, the upper limit of the ratio of the kneading portion relative to the total length of the screw is preferably 70% or less from the viewpoint of preventing the resin from being deteriorated due to the generation of excessive shearing heat during kneading.

  Regarding the screw rotation speed, a method of kneading under conditions of 150 to 1000 rotations / minute, preferably 300 to 1000 rotations / minute is preferable.

  The preferable range of the cylinder temperature (° C.) is desirably a temperature range exceeding (a) the melting point of the PPS resin and (b) the melting point of the thermoplastic resin or the glass transition temperature, specifically a range of 280 to 400 ° C. The range of 280 to 360 ° C is more preferable, and the range of 280 to 330 ° C is still more preferable.

  The order of mixing the raw materials at the time of melt kneading is not particularly limited, but a method of melt kneading by the above method after blending all raw materials, a melt kneading by the above method after blending some raw materials, Any method, such as a method of blending this and the remaining raw materials and melt-kneading, or a method of mixing a part of the raw materials and mixing the remaining raw materials using a side feeder during melt-kneading with a twin-screw extruder May be used.

  In addition, when (c) the phosphorus oxo acid metal salt is blended, after (a) the PPS resin and (c) the phosphorus oxo acid metal salt are previously melt-kneaded, (b) a melting point of 150 ° C. or higher or A method of melt-kneading with a thermoplastic resin having a glass transition temperature, or (b) a melt-kneading of a thermoplastic resin having a melting point of 150 ° C. or higher or a glass transition temperature and (c) a metal salt of oxo acid of phosphorus in advance, (A) The method of melt kneading with the PPS resin can be exemplified as a preferred method.

  In addition, about a small amount additive component, after kneading | mixing and pelletizing another component by said method etc., it is of course possible to add before shaping | molding and to use for shaping | molding.

(8) PPS resin composition The PPS resin composition constituting the plastic fastener according to the embodiment of the present invention has a tensile elongation (ASTM 4 dumbbell test piece, tensile speed of 10 mm / min), which is one of physical property values indicating material strength. , 23 ° C., measured according to ASTM-D638 (2010)) is preferably 10% or more, more preferably 25% or more, and even more preferably 40% or more. A tensile elongation of 10% or more means that the toughness of the PPS resin composition is excellent, and a plastic fastener shape is preferable because it can suppress cracking during fitting or deformation. The upper limit of the tensile elongation is preferably as high as possible and is not particularly limited, but the upper limit is substantially about 300%.

  (A) In the PPS resin, (b) a thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher is dispersed with a number average dispersion diameter of 500 nm or less, whereby the tensile elongation of the PPS resin composition is 10%. Expresses the above.

  Regarding the toughness of the PPS resin composition constituting the plastic fastener of the embodiment of the present invention, the tensile elongation after heat treatment, which is an index of high-temperature long-term durability, is preferably in the following range. The tensile elongation after heat treatment at 165 ° C. in air for 1000 hours is preferably 10% or more, more preferably 15% or more, and further preferably 20% or more (ASTM 4 dumbbell test piece) , Tensile speed 10 mm / min, 23 ° C., measured according to ASTM-D638 (2010)).

  The upper limit of the tensile elongation after the heat treatment is preferably as high as possible but is not particularly limited, but the upper limit is substantially about 300%. The tensile elongation after heat treatment being in the above range means that the PPS resin composition has good high-temperature and long-term durability, and is similarly preferable even when it is formed into a plastic fastener shape. The tensile elongation before and after heat treatment of the PPS resin composition is greatly influenced by the dispersion state of the thermoplastic resin having a melting point of 150 ° C. or higher or a glass transition temperature. In the phase separation structure, a thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher is coarsely dispersed, and when the phase separation structure desired by the present invention is not formed, the tensile elongation is lowered.

  Since the PPS resin composition constituting the plastic fastener of the embodiment of the present invention has a high tensile elongation after heat treatment, it is considered that the plastic fastener also exhibits high durability in continuous use under a high temperature environment even when it is used as a plastic fastener. It is done.

  The tensile elongation after the ATF (automatic transmission fluid) immersion treatment of the PPS resin composition, which is an index of chemical resistance of the thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher of the present invention, is in the following range. Preferably there is. The tensile elongation after treatment in ATF at 150 ° C. for 1000 hours is preferably 10% or more, more preferably 15% or more, and further preferably 20% or more (ASTM 4 dumbbell test piece) , Tensile speed 10 mm / min, 23 ° C., measured according to ASTM-D638 (2010)). ATF is a fluid used in automobile automatic transmissions, transmissions, etc., and there are no particular restrictions on the type of ATF, but the ingredients are antioxidants, viscosity index improvers, friction modifiers, detergent dispersants, pour point depressants. Agents, extreme pressure agents, antifoaming agents, rust inhibitors, corrosion inhibitors, oiliness agents, colorants, and the like. Specifically, “ATF + 4” manufactured by Mobile, “Mercon” manufactured by Ford, “Dexron” manufactured by GM, “ATF-F1” manufactured by Honda, “ATF-DW-1” manufactured by Honda, and “Made by Mitsubishi” "SP-III", Daihatsu "ATF-D3-SP", Nissan "Matic Fluid", Mazda "ATF-MV", Subaru "ECVT Fluid", Toyota "T-IV" “Toyota Corporation“ ATF-WS ”.

  The upper limit of the tensile elongation after the ATF immersion treatment is preferably as high as possible, but is not particularly limited, but the upper limit is substantially about 300%. That the tensile elongation after the ATF immersion treatment is in the above range means that the chemical resistance of the PPS resin composition is good. The tensile elongation before and after the ATF dipping treatment of the PPS resin composition is greatly affected by the dispersion state of the thermoplastic resin having a melting point of 150 ° C. or higher or a glass transition temperature. In the phase separation structure, a thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher is coarsely dispersed, and when the phase separation structure desired by the present invention is not formed, the tensile elongation is lowered.

  Since the PPS resin composition of the embodiment of the present invention has a high tensile elongation after the ATF immersion treatment, it exhibits high chemical resistance in continuous use in an environment exposed to oil, refrigerant, etc. including ATF. it is conceivable that.

  In the PPS resin composition of the embodiment of the present invention, the center line average roughness (Ra), which is an index of surface smoothness, is preferably 1.00 μm or less, more preferably 0.50 μm or less, and further 0.30 μm or less. It is preferably 0.20 μm or less. When plastic fasteners are used to bind wiring cables, cords, tubes, and hoses, inferior surface smoothness may cause looseness during use, and may damage the bound object. Yes, not preferred.

  For surface smoothness, an injection molding machine (SE75DUZ-C250) manufactured by Sumitomo Heavy Industries, Ltd. was used. Cylinder temperature: PPS resin and melting point or glass transition temperature of thermoplastic resin having a melting point of 150 ° C. or higher or glass transition temperature + 20 ˜40 ° C., mold temperature: 150 ° C. by injection molding to form a square plate of 80 mm × 80 mm × (thickness) 1 mm, and the obtained square plate has a surface roughness made by Mitutoyo Corporation Using a measuring instrument, scan the measurement terminal 2 cm in the resin flow direction (gate part → filling end part), measure the centerline average roughness Ra specified in JIS B0601, and adopt the average value of n = 3 did. It can be said that the smaller this value is, the better the surface smoothness is.

  Further, the plastic fastener has a shape having a thin portion, and the PPS resin composition is preferably excellent in fluidity due to its characteristics. Specifically, the melt viscosity of the PPS resin composition is preferably 600 Pa · s or less, more preferably 400 Pa · s, and even more preferably 250 Pa · s. The lower limit is preferably 10 Pa · s or more from the viewpoint of mechanical properties.

  The melt viscosity in the present invention is a value measured using a Toyo Seiki Capillograph under conditions of 310 ° C. and a shear rate of 1000 / s.

(9) Plastic Fastener The plastic fastener according to the embodiment of the present invention has excellent initial toughness and toughness after high-temperature long-term durability treatment, as well as excellent heat resistance and chemical resistance inherent in the PPS resin. In order to express such characteristics, in a plastic fastener made of a PPS resin composition, the resin phase separation structure observed with an electron microscope is as follows: (a) the PPS resin forms a continuous phase (sea phase or matrix); b) It is necessary to form a dispersed phase (island phase) in which a thermoplastic resin having a melting point of 150 ° C. or higher or a glass transition temperature is dispersed with a number average dispersed particle diameter of 500 nm or less.

  By forming the above-mentioned resin phase separation structure, it exhibits excellent initial toughness, toughness after high-temperature and long-term durability treatment, and surface appearance without impairing the excellent heat resistance and chemical resistance of the PPS resin. Can be applied to plastic fasteners.

  The number average dispersed particle size of the island phase of the thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher is required to be 500 nm or less, more preferably 400 nm or less, and even more preferably 300 nm or less.

  (B) The number average dispersed particle size of the thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher is within the above range. (A) PPS resin and (b) melting point or glass transition temperature of 150 ° C. or higher. This means that the compatibility with the thermoplastic resin is good, leading to the development of excellent toughness and surface appearance.

  In addition, (b) when the number average dispersed particle diameter of the thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher exceeds 500 nm, the adhesiveness at the resin interface is inferior, so the surface smoothness of the molded product is insufficient. It was difficult to apply to thin plastic fasteners, but it was found for the first time that the surface appearance was excellent by controlling the dispersion structure of 500 nm or less, and could be applied to this application. became. In addition, although the lower limit of the number average dispersed particle diameter of the thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher is not particularly limited, it is preferably about 1 nm. When the number average dispersion diameter is smaller than 1 nm, (a) a PPS resin and (b) a thermoplastic resin having a melting point of 150 ° C. or higher or a glass transition temperature are close to being in a completely compatible state. The expression is not certain.

  In the plastic fastener, (b) the number average dispersed particle size of the island phase of the thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher is calculated by the following method. The plastic fastener shown in FIG. 1 (W1: 15 mm, W2: 20 mm, W3: 5.) at the molding temperature of the melting point or glass transition temperature of the PPS resin and a thermoplastic resin having a melting point of 150 ° C. or higher or glass transition temperature + 20-40 ° C. 0 mm, H1: 2 mm, H2: 8.5 mm), and the inner spring portion is cut in the cross-sectional area direction (vertical direction) with respect to the resin flow direction to cut out a thin piece of 0.1 μm or less, and a transmission electron microscope The camera is photographed at a magnification of about 1000 to 5000 times. From the photograph, for any 100 dispersed phases, first, the maximum diameter and the minimum diameter of each dispersed phase are measured to determine the average value of the diameters of the respective dispersed phases, and then the average value of those diameters is determined. The number average value.

  In order to make the plastic fastener of the present invention have the above structure, it is possible to obtain a PPS resin composition by the following melt-kneading method. Specifically, when (a) a PPS resin and (b) a thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher are melt-kneaded, L / D (L: screw length, D: screw diameter) Is 10 or more, preferably 20 or more, and it is preferable to use a twin screw extruder having two or more kneading portions, preferably three or more. Moreover, the ratio of the kneading part with respect to the screw full length is preferably 15% or more, more preferably 20% or more, and further preferably 30% or more. Regarding the screw rotation speed, a method of kneading under conditions of 150 to 1000 rotations / minute, preferably 300 to 1000 rotations / minute is preferable. The preferable range of the cylinder temperature (° C.) is desirably a temperature range exceeding (a) the melting point of the PPS resin and (b) the melting point of the thermoplastic resin or the glass transition temperature, specifically a range of 280 to 400 ° C., The range of 280 to 360 ° C is more preferable, and the range of 280 to 330 ° C is still more preferable.

  The plastic fastener of the present invention can be molded by various molding methods such as injection molding, extrusion molding, compression molding, blow molding, injection compression molding, etc., in order to make the dispersion state of the plastic fastener the above structure. Of these, injection molding and extrusion molding are useful. The range of the processing temperature at that time is desirably a temperature range exceeding (a) the melting point of the PPS resin and (b) the melting point of the thermoplastic resin or the glass transition temperature, specifically, a range of 280 to 400 ° C. The range of -360 degreeC is more preferable, and the range of 280-330 degreeC is still more preferable.

  Regarding the plastic fastener of the present invention, the composition for making the dispersion state of the plastic fastener have the above structure essentially comprises (a) a PPS resin and (b) a thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher, It is preferable to use a metal salt of phosphorus oxo acid or an organic silane compound in combination.

  The plastic fastener made of the polyphenylene sulfide resin composition according to the embodiment of the present invention is utilized for various applications such as automobile parts, electrical / electronic parts, building members, various containers, daily necessities, household goods and sanitary goods, taking advantage of its excellent characteristics. can do. The plastic fastener made of the polyphenylene sulfide resin composition of the embodiment of the present invention is particularly excellent in toughness (tensile elongation), high temperature long-term durability, chemical resistance, and surface appearance. Suitable for

  In the present invention, the plastic fastener refers to a fastener using a resin as a material of an element. Plastic fasteners are, for example, point fasteners such as buttons and rivets, line fasteners such as zippers, clips, clamps, hook-and-loop fasteners, cable ties, cable ties, and bands, especially wiring cables, cords, Clips that bundle tubes and hoses, clamps, hook-and-loop fasteners, cable ties, cable ties, and bands. Moreover, the plastic fastener of a shape which has a fitting part is preferable.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto.

In Examples and Comparative Examples, (a) PPS resin, (b) thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher, (c) phosphorus oxo acid metal salt, (d) organosilane compound, etc. The following were used.
[(A) PPS resin (a-1 to 2)]
a-1: Linear PPS resin Weight average molecular weight: 60000
a-2: Linear PPS resin Weight average molecular weight: 95000, Na content: 300 ppm
[(B) Thermoplastic resin (b-1 to 4) having a melting point or glass transition temperature of 150 ° C. or higher]
b-1: Polyetherimide resin (Sabic, Ultem 1010) Glass transition temperature: 217 ° C.
b-2: Poly (ether imide-siloxane) copolymer (Sabic, Siltem 1500), glass transition temperature: 165 ° C.
b-3: ethylene-tetrafluoroethylene copolymer (AH-2000, manufactured by Asahi Glass Co., Ltd.), melting point: 240 ° C.
b-4: polyamide 610 resin (manufactured by Toray Industries, Inc., CM2001), melting point: 225 ° C.
[(C) Metal salt of phosphorus oxo acid]
c: Sodium phosphinate monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.)
[(D) Organosilane compound]
d: 3-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Silicone, KBE9007)
[Others]
Other-1: Olefin elastomer: ethylene-glycidyl methacrylate copolymer (manufactured by Arkema, LOTADAR AX8840), melting point: 109 ° C
Other-2: Calcium hydroxide Other-3: Terephthalic acid.

  In the following examples, material characteristics were evaluated by the following methods.

[Number average dispersion diameter of island phase]
Using an injection molding machine (SE75DUZ-C250) manufactured by Sumitomo Heavy Industries, Ltd., cylinder temperature: PPS resin and melting point or glass transition temperature of thermoplastic resin having a melting point of 150 ° C. or higher or glass transition temperature + 20 to 40 ° C., mold temperature : The plastic fastener shown in FIG. 1 (W1: 15 mm, W2: 20 mm, W3: 5.0 mm, H1: 2 mm, H2: 8.5 mm) was molded by injection molding under the conditions of 150 ° C. and FIG. The inner spring portion shown in A) was cut in the cross-sectional area direction (vertical direction) with respect to the resin flow direction, and a piece having a thickness of 0.1 μm or less was cut out and photographed with a transmission electron microscope at a magnification of about 1000 to 5000 times. From the photograph, for any 100 dispersed phases, first, the maximum diameter and the minimum diameter of each dispersed phase were measured to obtain an average value, and then the number average value obtained from the average value of the dispersed phases was calculated as the island phase. Was the number average dispersion diameter.

[Tensile test]
Using an injection molding machine (SE75DUZ-C250) manufactured by Sumitomo Heavy Industries, Ltd., cylinder temperature: PPS resin and melting point or glass transition temperature of thermoplastic resin having a melting point of 150 ° C. or higher or glass transition temperature + 20 to 40 ° C., mold temperature : ASTM No. 4 dumbbell specimen was molded by injection molding at 150 ° C. About the obtained test piece, tensile elongation was measured according to ASTM D638 (2010) under the conditions of a distance between fulcrums of 64 mm, a tensile speed of 10 mm / min, a temperature of 23 ° C. and a relative humidity of 50%.

[Tensile elongation after treatment at 165 ° C. × 1000 hours]
A dumbbell test piece obtained by the same method as above was treated in an atmosphere at 165 ° C. for 1000 hours, and then ASTM-D638 (under a distance between fulcrums of 64 mm, a tensile speed of 10 mm / min, a temperature of 23 ° C. and a relative humidity of 50%. 2010), a tensile test was performed, and the elongation at break of the test piece was measured.

[Tensile rupture elongation after chemical immersion treatment]
A dumbbell specimen obtained by the same method as described above was treated for 1000 hours in an atmosphere of 150 ° C. immersed in ATF (ATF WS manufactured by Toyota), a distance between fulcrums of 64 mm, a tensile speed of 10 mm / min, a temperature of 23 ° C. × relative humidity. Under a 50% condition, a tensile test was performed under the condition based on ASTM-D638 (2010), and the elongation at break of the test piece was measured.

[Surface smoothness test]
Using an injection molding machine (SE75DUZ-C250) manufactured by Sumitomo Heavy Industries, Ltd., cylinder temperature: PPS resin and melting point or glass transition temperature of thermoplastic resin having a melting point of 150 ° C. or higher or glass transition temperature + 20 to 40 ° C., mold temperature : A square plate of 80 mm × 80 mm × (thickness) 1 mm was formed by injection molding under the condition of 150 ° C. About the obtained square plate, using a surface roughness measuring instrument manufactured by Mitutoyo Corporation, the measurement terminal was scanned 2 cm in the resin flow direction (gate portion → filled end portion), and the center line average defined in JIS B0601 The roughness Ra was measured, and an average value of n = 3 was adopted.

[Characteristic evaluation of plastic fasteners]
[Evaluation of cracks during wiring attachment (initial toughness)]
The pellets obtained in each Example and Comparative Example were dried at 130 ° C. for 8 hours, using an injection molding machine (SE75DUZ-C250) manufactured by Sumitomo Heavy Industries, Ltd., cylinder temperature: PPS resin, melting point of 150 ° C. or higher, or glass transition. A plastic fastener shown in FIG. 1 (W1: 15 mm, W2: 20 mm, W3: 5) is formed by injection molding under the conditions of a melting point or glass transition temperature of a thermoplastic resin having a temperature +20 to 40 ° C. and a mold temperature: 150 ° C. 0.0 mm, H1: 2 mm, H2: 8.5 mm) 30 molded products were obtained. Next, a cable having a diameter of 4.5 mm was fixed using the obtained plastic fastener molded product, and the presence or absence of a crack (fitting portion and / or inner spring) at the time of attachment fitting was evaluated. Of the 30 molded products, the ratio of the number of cracks observed at the time of mounting and fitting was used as an index of initial toughness as the cracking rate (%) at the time of mounting and fitting. It can be said that the lower the cracking ratio, the better the initial toughness.

[High-temperature long-term durability evaluation at the time of wiring fitting]
For plastic fasteners that were not cracked during fitting in the previous section, they were treated at 165 ° C for 1000 hours (high-temperature and long-term durability treatment), and the plastic fasteners after the treatment were fitted and / or inside The presence or absence of spring cracks was evaluated. Of the number of plastic fastener molded products in which cracking was not recognized at the time of mounting and fitting in the previous section, the ratio of the number of cracks recognized after high-temperature long-term durability treatment was the crack rate after treatment at 165 ° C. × 1000 h (%) It was used as an index of long-term durability at high temperatures. It can be said that the lower the crack rate, the better the long-term durability at high temperatures.

[Examples 1 to 8, Comparative Examples 1 and 3]
After dry blending each raw material in the proportions shown in Table 1, using a TEX30α twin screw extruder (L / D = 45) manufactured by Nippon Steel Works equipped with a vacuum vent, kneading for three kneading parts and the total screw length The proportion of the part was 45%, and the temperature of the cylinder was set to 320 ° C., and melt kneading was performed. This kneading method is referred to as Method A. Then, it pelletized with the strand cutter. The obtained pellets are dried at 130 ° C. for 8 hours and then subjected to injection molding. The obtained molded product is subjected to morphological observation, tensile test, high-temperature long-term durability test, chemical resistance test, and surface smoothness test. It was.

[Comparative Example 2]
After dry blending each raw material in the proportions shown in Table 1, using a TEX30α twin screw extruder (L / D = 45) manufactured by Nippon Steel Works equipped with a vacuum vent, kneading for one kneading part and the total screw length The ratio of the parts was 10%, and the temperature of the cylinder was set to 320 ° C., and melt kneading was performed. This kneading method will be referred to as Method B. Thereafter, evaluation was performed in the same manner as in the previous section.

  The results of the above examples and comparative examples will be described.

  In Examples 1 to 8, in the plastic fastener, (b) the number average dispersed particle diameter of the island phase formed by the thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher is controlled to 500 nm or less. Excellent toughness, toughness after high-temperature and long-term durability treatment, chemical resistance, surface appearance, and suppression of cracks when mounting and fitting in the initial state of plastic fasteners, and suppression of cracking after high-temperature and long-term durability treatment Yes.

  On the other hand, in Comparative Example 1 using an olefin elastomer having a melting point of 109 ° C., although the olefin elastomer forms an island phase of 500 nm or less and has an effect of improving a certain initial elongation, high temperature long-term durability treatment and chemical treatment The later tensile elongation is inferior, and a PPS resin composition having excellent toughness cannot be obtained. Therefore, even after the plastic fastener shape, the crack after the high temperature long-term durability treatment is remarkable.

  On the other hand, compared with other examples and comparative examples, Comparative Example 2 in which the kneading ratio with respect to the kneading location and the screw full length was reduced by melt kneading, the number average dispersed particle size of the polyetherimide resin was as large as 2300 nm, Inferior tensile elongation after initial, high-temperature, long-term durability treatment and chemical treatment. Moreover, it originated in being inferior to the dispersion state of polyetherimide resin, was inferior to surface smoothness, and the appearance defect occurred. Even in the plastic fastener shape, cracks are remarkable both in the initial stage and after the high-temperature long-term durability treatment.

  Comparative Example 3 simulating the high-temperature long-term durability improvement formulation described in Patent Document 3 is inferior in tensile elongation after the initial high-temperature long-term durability treatment and chemical treatment, and even in the plastic fastener shape, after the initial high-temperature long-term durability treatment Both cracks are prominent.

1. 1. Inner spring part 2. Fitting part Wiring (cable)

Claims (6)

A plastic fastener comprising a polyphenylene sulfide resin composition comprising (a) a polyphenylene sulfide resin and (b) a thermoplastic resin having a melting point or glass transition temperature of 150 ° C. or higher, and in the morphology (phase structure) of the plastic fastener, ( a) A plastic fastener in which a polyphenylene sulfide resin forms a continuous phase (sea phase), and (b) a dispersed phase (island phase) in which the thermoplastic resin is dispersed with a number average dispersed particle diameter of 500 nm or less. ASTM No. 4 dumbbell obtained by injection molding the polyphenylene sulfide resin composition was treated in accordance with ASTM-D638 under conditions of a tensile speed of 10 mm / min and an ambient temperature of 23 ° C. after 1000 hours of treatment at 165 ° C. in the atmosphere. The plastic fastener according to claim 1, wherein the elongation at break is 10% or more. The ASTM No. 4 dumbbell obtained by injection molding the polyphenylene sulfide resin composition was treated in accordance with ASTM-D638 under conditions of a tensile speed of 10 mm / min and an ambient temperature of 23 ° C. after being treated in ATF at 150 ° C. for 1000 hours. The plastic fastener according to claim 1 or 2, wherein the elongation at break is 10% or more. The said (b) thermoplastic resin is at least 1 sort (s) selected from polyether imide resin, a poly (ether imide- siloxane) copolymer, a polyamide resin, and a fluororesin. Plastic fasteners. The said polyphenylene sulfide resin composition mix | blends 0.01-5 weight part of (c) phosphorus oxo acid metal salt with respect to (a) 100 weight part of polyphenylene sulfide resin further. The described plastic fastener. The plastic fastener according to any one of claims 1 to 5, wherein the plastic fastener is any one selected from a clip, a clamp, a hook-and-loop fastener, a binding band, a cable tie, and a band.