JP2010076437A - Manufacturing method for composite of molding comprising thermoplastic resin composition and metal - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite capable of firmly joining different kinds of materials, a metal and a molding comprising thermoplastic resin composition, to each other using a laser beam as a heat source, and having high shape flexibility and high reliability, even the molding comprising thermoplastic resin composition does not transmits the laser beam. <P>SOLUTION: The manufacturing method for the composite of the molding comprising the thermoplastic resin composition and the metal overlaps (A) the molding 12 comprising the thermoplastic resin composition and (B) the metal 11, and joins those by irradiation of the laser beam 9 from a (B) metal side, and by softening and/or fusing at least one part of the molding comprising thermoplastic resin composition. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a composite, characterized in that a molded body made of a thermoplastic resin composition and a metal are joined (also referred to as welding) using laser light (also referred to as laser or laser light). .

  Thermoplastic resin compositions are widely used in automobiles, electrical electronics, and general industrial applications because they have excellent molding processability and a large degree of freedom in shape, and have high designability. Among them, polyphenylene sulfide (hereinafter abbreviated as PPS) resin, polyamide resin (hereinafter abbreviated as PA), and polybutylene terephthalate (hereinafter abbreviated as PBT) are further superior in heat resistance, barrier property, chemical resistance, electrical insulation, machine It has properties suitable for engineering plastics such as mechanical strength and elastic modulus, and is used for various automobile parts, electrical / electronic parts, mechanical parts, etc. mainly for injection molding and extrusion molding.

  In recent years, with the advancement of industry, various physical properties required for PPS resin, PA resin, and PBT resin are further improved and diversified.

  There has been a great demand for integration and compounding by bonding a molded body made of a thermoplastic resin composition and metal, and in recent years, compounding by bonding using laser light has become known.

For example, Patent Document 1 describes a method for joining two different members using laser light as a heating source. In this method, a resin member that transmits laser light and the other member are overlapped, the laser light is irradiated from the laser light transmitting resin side, and unevenness is provided on one of the bonding surfaces to absorb the laser light. This is a technique for joining one or both members by melting or softening them.

  Patent Documents 2 and 3 are methods for joining a thermoplastic resin member and a metal member, in which a foam having a communication hole in the thickness direction, a fine wire sintered body, and a metal member having a through hole and a resin member are overlapped. , A method of joining by irradiating laser light from the resin side that transmits laser light, melting the resin by heat generation of the metal and blackening of the resin side mating surface, impregnating the molten resin into the communication hole, and extruding from the through hole It is.

  Patent Document 4 describes a method in which two types of resin materials are overlapped and laser light is irradiated from one side as a heating source to melt and bond the resin on the adhesive surface.

JP 2006-15405 A (Claims) JP 2005-297288 A (Claims) JP-A-61-258730 (Claims) Japanese Patent Laying-Open No. 2005-329669 (Claims)

  However, each of the above Patent Documents 1 to 4 is a joining method using a laser beam as a heating source, but the method overlaps a resin member that transmits the laser beam and another member that absorbs the laser beam, Laser light is irradiated from the side of the resin member that transmits the laser light, and the laser light is absorbed by the joining surface to generate heat, and the resin is softened and melted by this heat to join. Therefore, the bonding member needs to be a combination of a member having a property of transmitting laser light and a member that absorbs laser light.

  As described above, the conventional technique using laser light as a heating source is a technique in which laser light is irradiated from the side of a molded body made of a thermoplastic resin composition that transmits laser light. When attempting to join a molded article made of a resin composition to a metal, the molded article made of the thermoplastic resin composition has insufficient laser transmittance, or molded from the thermoplastic resin composition depending on the shape of the composite. When laser light cannot be irradiated from the body side, there are problems such as inability to join or insufficient strength of joining.

  Therefore, the present inventors have studied to solve the above problems in a method for producing a composite of a molded article composed of a thermoplastic resin composition and a metal, and as a result, the molded article composed of the thermoplastic resin composition and the metal are overlapped. In addition, laser light transmission of the molded body made of the thermoplastic resin composition is achieved by softening and / or melting at least part of the molded body made of the thermoplastic resin composition by irradiating from the metal side with a laser beam as a heat source. The present inventors have found that both can be firmly joined without being affected by the property, and have reached the present invention.

That is, the present invention is as follows.
(1) (A) A molded body made of a thermoplastic resin composition and (B) a metal are overlaid, and (B) at least part of a molded body made of a thermoplastic resin composition is irradiated with laser light from the metal side. A method of producing a composite of a molded body and a metal comprising a thermoplastic resin composition, wherein the composite is bonded by softening and / or melting.
(2) The heat according to (1), wherein the linear expansion coefficient of the molded body made of the thermoplastic resin composition (A) is 2.0 to 4.5 × 10 ⁻⁵ / ° C. in a temperature range of 23 to 80 ° C. A method for producing a composite of a molded body comprising a plastic resin composition and a metal.
(3) The (A) thermoplastic resin composition is a composition obtained by blending 17.6 to 100 parts by weight of (C) an inorganic filler with respect to 100 parts by weight of the thermoplastic resin (1) or ( The manufacturing method of the composite of the molded object which consists of a thermoplastic resin composition as described in 2), and a metal.
(4) The (A) thermoplastic resin composition is a composition obtained by blending at least one selected from (A1) polyphenylene sulfide resin, (A2) polyamide resin, and (A3) polybutylene terephthalate resin ( The manufacturing method of the composite_body | complex of the molded object which consists of a thermoplastic resin composition in any one of 1)-(3), and a metal.
(5) The metal surface reflectance when the laser beam with a wavelength of 800 to 1100 nm is irradiated on the surface on the laser irradiation side of the metal (B) is 80% or less. The manufacturing method of the composite_body | complex of the molded object which consists of a thermoplastic resin composition, and a metal.
(6) The heat according to any one of (1) to (5), wherein a surface of the metal (B) to be combined with a molded body made of a thermoplastic resin composition is surface-treated. A method for producing a composite of a molded body comprising a plastic resin composition and a metal.
(7) Production of a composite of a molded body and a metal comprising the thermoplastic resin composition according to (6), wherein the surface of the metal (B) is surface-treated with a triazine thiol derivative. Method.
(8) The thermoplastic resin according to (6), wherein the surface of the metal (B) has been surface-treated with at least one compound selected from ammonia, hydrazine and a water-soluble amine compound. A method for producing a composite of a molded body and a metal comprising the composition.
(9) The method for producing a composite of a molded body and a metal comprising the thermoplastic resin composition according to (6), wherein the surface of the metal (B) is anodized.

  As described above, the bonding between the molded body made of the thermoplastic resin composition of the present invention and the metal exhibits a strong bonding strength without being affected by the laser beam transmittance of the molded body made of the thermoplastic resin composition. Therefore, it is useful for the production of a composite comprising a molded body made of a thermoplastic resin composition and a metal in automobile parts, electrical / electronic parts, general industrial equipment parts, and the like.

It is a figure which shows the shape of the test piece before cutting of a linear expansion coefficient measurement sample, a laser beam transmittance measurement sample, and a laser welding resin sample. It is a figure which shows MD and TD cutting position of a linear expansion coefficient. It is a figure which shows the shape of a linear expansion coefficient measurement test piece. It is a figure which shows the shape of a laser beam transmittance measuring test piece (resin), a laser beam reflectance measuring test piece (metal), and a laser welding test piece (resin, metal). It is a figure which shows the laser welding method. It is a figure which shows the shape of the test piece for laser welding strength measurement.

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

  In the present invention, “weight” means “mass”.

  In the present invention, it is important to superimpose a molded body made of a thermoplastic resin composition on a metal and irradiate laser light from the metal side. The metal surface is heated by irradiating a laser beam from the metal side as a heating source, and the thermoplastic resin composition at the bonding interface is softened and / or melted by this heat, whereby the resin molded body and the metal are bonded. Therefore, it is possible to obtain a composite in which both are firmly bonded without being affected by the laser light transmittance of the molded body made of the thermoplastic resin composition.

The molded body made of the thermoplastic resin composition (A) used in the present invention preferably has a linear expansion coefficient of 2.0 to 4.5 × 10 ⁻⁵ / ° C. in a temperature range of 23 to 80 ° C. Further, (B) the metal is preferably subjected to a specific surface treatment.

  The linear expansion coefficient of the molded body made of the thermoplastic resin composition is a value measured by the following method. From a molded body made of a thermoplastic resin composition, the width W is 5 mm and the length L is 10 mm in the resin flow direction (hereinafter abbreviated as MD) and the direction perpendicular to the resin flow direction (hereinafter abbreviated as TD) during molding. , Using a test piece prepared by cutting a molded body having a thickness D of 3 mm, using a TMA-100 manufactured by Seiko Electronics Industry Co., Ltd., a load range of 2 g, a temperature range of −40 ° C. to 80 ° C. is 5 ° C. / The temperature is increased at a rate of minutes, and the value of (MD linear expansion coefficient + TD linear expansion coefficient) / 2 in the temperature range of 23 to 80 ° C. is defined as the linear expansion coefficient.

  In the present invention, the thermoplastic resin contained in the thermoplastic resin composition constituting the resin molded body is not limited with respect to laser beam transmission, and may not transmit laser beam at all. As the thermoplastic resin, a known thermoplastic resin such as a PPS resin, a polyamide resin, a polyester resin, or a polycarbonate resin can be used. In particular, the present invention is effective when a metal body and a molded body made of a thermoplastic resin composition containing a PPS resin or the like that does not sufficiently transmit laser light are joined.

  Here, there is no restriction | limiting in the thermoplastic resin contained in the thermoplastic resin composition which comprises a molded article, Especially at least 1 sort (s) chosen from PPS resin, PA resin, and PBT resin is used preferably. These resins are preferable in that chemical resistance, heat resistance, mechanical strength, electrical insulation, and barrier properties are well balanced as engineering plastics, and that processability is also good. These PPS resins, PA resins, and PBT resins may be used alone or in combination with PPS and PPS copolymers, PA and PA copolymers, and PBT and PBT copolymers.

(A1) PPS resin (A1) PPS resin used in the present invention is a polymer having a repeating unit represented by the following structural formula (I),

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. Moreover, about 30 mol% or less of the repeating unit of the PPS resin may be composed of a repeating unit having the following structure.

  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 melt viscosity of PPS resin used by this invention, From the meaning which obtains more excellent mechanical strength, for example, 5 Pa * s (310 degreeC, shear rate 1000 / s) or more is preferable, and 10 Pa * s or more is preferable. Is more preferable. The upper limit is preferably 600 Pa · s or less from the viewpoint of maintaining melt fluidity.

  In addition, the melt viscosity in this invention is the value measured using the Toyo Seiki Co., Ltd. capilograph on the conditions of 310 degreeC and the shear rate of 1000 / s.

  Although the manufacturing method of PPS resin used for this invention is demonstrated below, if the 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. 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 amount of the polyhalogenated aromatic compound used is 0.9 to 2.0 mol, preferably 0.95 to 1.5 mol, per mol of the sulfidizing agent, from the viewpoint of obtaining a PPS 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 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 monohalogen compound (not necessarily an aromatic compound) is used in combination with the polyhalogenated aromatic compound in order to form a terminal of the produced PPS resin or to adjust a polymerization reaction or a molecular weight. Can do.

[Polymerization aid]
In order to obtain a PPS resin 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 assistant means a substance having an action of increasing the viscosity of the obtained PPS resin. 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, as the organic carboxylates, alkali metal carboxylates are preferable, and as the alkali metal chlorides, lithium chloride is preferable.

  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, and in the sense of obtaining a higher degree of polymerization, 0.6 to 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. 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 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 to add at the start of the process or at the start of the polymerization from the viewpoint of easy addition.

  Next, the production method of the PPS resin used in the present invention will be described in detail in order of the pre-process, the polymerization reaction process, the recovery process, and the post-treatment process.

[pre-process]
In the method for producing a PPS resin, the sulfiding agent is usually used in the form of a hydrate. 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 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, conversion rate = [PHA charge amount (mol) −PHA remaining amount (mol)] / [PHA charge amount (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 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 recovery method may be employed for the PPS resin.

  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. There is no need for slow cooling at the same rate in the entire process of the slow cooling step, and a method of slow cooling at a rate of 0.1 to 1 ° C./minute until the polymer particles crystallize and then 1 ° C./minute or more is used. 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 PPS resin may be produced through the above polymerization and recovery steps and then subjected to acid treatment, hot water treatment or washing with an organic solvent.

  When acid treatment is performed, it is as follows. The acid used for the acid treatment of the PPS resin is not particularly limited as long as it does not have an action of decomposing the PPS resin, 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 deteriorate the PPS resin such as nitric acid are not preferable.

  As the acid treatment method, there is a method of immersing 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 PPS resin is preferably washed several times with water or warm water in order to remove residual acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that the effect of the preferred chemical modification of the PPS resin by the acid treatment is not impaired.

  When performing hot water treatment, it is as follows. 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, still more preferably 150 ° C. or higher, and particularly preferably 170 ° C. or higher. If it is less than 100 ° C., the effect of preferable chemical modification of the PPS resin is small, which is not preferable.

  The water used is preferably distilled water or deionized water in order to develop a preferable chemical modification effect of the PPS resin by hot water washing. There is no particular limitation on the operation of the hot water treatment, and a predetermined amount of PPS resin is put into a predetermined amount of water and heated and stirred in a pressure vessel, or a continuous hot water treatment is performed. The ratio of the PPS resin to water is preferably higher, but usually a bath ratio of 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 preferably an inert atmosphere in order to avoid this. Further, the PPS resin after the hot water 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 the PPS resin is not particularly limited as long as it does not have an action of decomposing the PPS resin. For example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, 1,3-dimethylimidazo Nitrogen-containing polar solvents such as lysinone, hexamethylphosphoramide, piperazinones, sulfoxide and 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, dichloroethane, tetrachloro Halogen solvents such as tan, perchlorethane, chlorobenzene, alcohol / phenol solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol, and benzene, Examples thereof include aromatic hydrocarbon solvents such as 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 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 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.

  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.

  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.

  PPS resins that can be used in the present invention include Toray Industries, Inc. M2588, M2888, M2088, M3088, T1881, L2120, L2480, L2520, L4230, M2100, M2900, M3910, E2280, E2180, E2080, manufactured by Kureha Corporation. W203A, W205A, and the like can be mentioned, and among these, M2588, M2888, M2088, M3088, T1881, L2480, L4230, M2100, M3910, E2280, E2180, E2080, W203A, W205A, and the like are preferably used.

(Compounding agent blended in thermoplastic resin composition)
In the present invention, the compounding agent is preferably blended into the thermoplastic resin composition in order to impart excellent bonding strength with metal and the strength, moldability, toughness, heat resistance, and the like of the resin molded body.

(Elastomer)
In the thermoplastic resin composition containing the (A1) PPS resin of the present invention, an olefin copolymer having an epoxy group can be blended in the sense of imparting toughness. Examples of the olefin copolymer having an epoxy group (epoxy group-containing olefin copolymer) include an olefin copolymer obtained by introducing a monomer component having an epoxy group into an olefinic (co) polymer. . Moreover, the copolymer which epoxidized the double bond part of the olefin polymer which has a double bond in a principal chain can also be used.

  Examples of functional group-containing components for introducing a monomer component having an epoxy group into an olefinic (co) polymer include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, etc. And a monomer containing an epoxy group.

  The method for introducing these epoxy group-containing components is not particularly limited, and methods such as copolymerization with α-olefin and the like, or graft introduction to an olefin (co) polymer using a radical initiator can be used.

  The introduction amount of the monomer component containing an epoxy group is 0.001 to 40 mol%, preferably 0.01 to 35 mol% with respect to the whole monomer as a raw material of the epoxy group-containing olefin copolymer. It is appropriate to be within the range.

  As the epoxy group-containing olefin copolymer particularly useful in the present invention, an olefin copolymer having an α-olefin and a glycidyl ester of α, β-unsaturated carboxylic acid as a copolymerization component is preferably exemplified. As said alpha olefin, ethylene is mentioned preferably. These copolymers further include α, β-unsaturated carboxylic acids such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like. It is also possible to copolymerize the alkyl ester, styrene, acrylonitrile and the like.

  Such an olefin copolymer may be any random, alternating, block, or graft copolymerization mode.

  An olefin copolymer obtained by copolymerizing an glycidyl ester of an α-olefin and an α, β-unsaturated carboxylic acid is, among others, a glycidyl ester 1 of 60 to 99% by weight of an α-olefin and an α, β-unsaturated carboxylic acid. An olefin copolymer obtained by copolymerizing ˜40% by weight is particularly preferable.

  Specific examples of the glycidyl ester of α, β-unsaturated carboxylic acid include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Among them, glycidyl methacrylate is preferably used.

  As a specific example of an olefin copolymer having an α-olefin and a glycidyl ester of α, β-unsaturated carboxylic acid as an essential copolymerization component, an ethylene / propylene-g-glycidyl methacrylate copolymer ("g" Representing graft, the same shall apply hereinafter), ethylene / butene-1-g-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate copolymer-g-polystyrene, ethylene-glycidyl methacrylate copolymer-g-acrylonitrile-styrene copolymer Polymer, ethylene-glycidyl methacrylate copolymer-g-PMMA, ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / Glycidi methacrylate Copolymers thereof.

  An elastomer that does not contain an epoxy group can also be used. Examples of such an elastomer include an ethylene / propylene copolymer, an ethylene / butene copolymer, an ethylene / hexene copolymer, and an ethylene / octene copolymer. When using the elastomer which does not contain this epoxy group, it is preferable to use together with the olefin copolymer which has an epoxy group.

The blending amount of the olefin copolymer having an epoxy group and the elastomer not containing an epoxy group depends on the required characteristics of the target item, but is usually 3 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin. A range is preferred.

  Furthermore, as other compounding agents, other thermoplastic resins may be blended with the PPS resin composition in addition to the resin as the main component such as the PPS resin, as long as the effects of the present invention are not impaired. Specific examples thereof include polyetherimide resin, polyether sulfone resin, polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, modified polyphenylene ether resin, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyarylate resin, liquid crystal Examples include polymers, polyetherketone resins, polythioetherketone resins, polyetheretherketone resins, polyimide resins, polyamideimide resins, polytetrafluoroethylene resins, and polyethylene.

(Antioxidant)
Moreover, in this invention, in order to suppress the color tone change by oxidation coloring of the resin molding, it is possible to mix | blend antioxidant with a PPS resin composition. Specific examples of the antioxidant include calcium hypophosphite, 2,6-di-t-butyl-4-methylphenol, tetrakis (methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate) phenolic compounds such as methane, tris (3,5-di-t-butyl-4-hydroxybenzidine) isocyanurate, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipro Sulfur compounds such as pionate, phosphorus compounds such as trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite and the like can be mentioned, among which calcium hypophosphite is preferable. The compounding quantity of antioxidant is 0.01-5 weight part normally with respect to 100 weight part of thermoplastic resins, Preferably it is 0.05-3 weight part, More preferably, it is 0.1-1 weight part.

  Moreover, in order to suppress the color tone change by oxidation coloring, the said antioxidant can also be used in combination of 2 or more types.

  Further, as a compounding agent, the following compounds can be added for the purpose of modifying the PPS fat composition. 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 Normal additives such as metal soaps such as ethylenediamine / stearic acid / sebacic acid polycondensate, mold release agents such as silicone compounds, water, lubricants, UV inhibitors, colorants, foaming agents, etc. . If any of the above compounds exceeds 20% by weight of the total composition, the inherent properties of the thermoplastic resin are impaired, and therefore it is not preferred, and 10% by weight or less, more preferably 1% by weight or less is added.

  In addition, the thermoplastic resin composition containing the (A1) PPS resin of the present invention has an epoxy group, an amino group, an isocyanate group for the purpose of improving mechanical strength, toughness and the like within a range not impairing the effects of the present invention. An alkoxysilane having at least one functional group selected from a group, a hydroxyl group, a mercapto group, and a ureido group may be added. Specific examples of such compounds include epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Compounds, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) ) Ureido group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, Isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2- Amino group-containing alkoxysilane compounds such as aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and γ-hydroxypropyltrimethoxysilane, γ- Examples thereof include a hydroxyl group-containing alkoxysilane compound such as hydroxypropyltriethoxysilane.

  A suitable addition amount of the silane compound is selected in a range of 0.05 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin.

(A2) PA resin The (A2) PA resin used in the present invention is a resin mainly composed of amino acids, lactams or diamines and dicarboxylic acids. Representative examples of the raw materials include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, tetramethylenediamine, hexa Methylenediamine, nonamethylenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, (2,2,4- or 2,4,4-) trimethylhexamethylenediamine, 5-methylnonamethylenediamine, Metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, Bis (4-aminosi Chlohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, aliphatic, alicyclic, aromatic Diamines, and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid Examples thereof include aliphatic, alicyclic and aromatic dicarboxylic acids such as acid, hexahydroterephthalic acid and hexahydroisophthalic acid. In the present invention, polyamide homopolymers or copolymers derived from these raw materials are used alone or It can be used in the form of a mixture.

  In the present invention, the (A1) polyamide resin that is particularly preferably used is a polyamide resin having a melting point of 200 ° C. or higher and excellent in heat resistance and strength. Specific examples include polycaproamide (nylon 6), poly Hexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyhexamethylene terephthalamide (nylon 6T) ), Polynonamethylene terephthalamide (nylon 9T), polyhexamethylene isophthalamide (nylon 6I), polyxylylene adipamide (nylon XD6), polycaproamide / polyhexamethylene adipamide copolymer (nylon 6/66) , Polyhexamethylenete Phthalamide / polycaproamide copolymer (nylon 6T / 6), polyhexamethylene terephthalamide / polydodecanamide copolymer (nylon 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), Polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide copolymer (nylon 66 / 6I / 6), polyhexamethylene azide Pamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyhexamethylene terephthalamide / polyhexamethylene iso Talamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / poly (2-methylpentamethylene) terephthalamide copolymer (nylon 6T / M5T), polyhexamethylene terephthalamide / polyhexamethylene sebacamide / polycaproamide Copolymer (nylon 6T / 610/6), polyhexamethylene terephthalamide / polydodecanamide / polyhexamethylene adipamide copolymer (nylon 6T / 12/66), polyhexamethylene terephthalamide / polydodecanamide / polyhexamethylene isophthal Examples thereof include amide copolymers (nylon 6T / 12 / 6I) and mixtures or copolymers thereof.

  Particularly preferred are nylon 6, nylon 66, nylon 610, nylon 6/66 copolymer and nylon 66 / 6I / 6 copolymer, and nylon 6T / 66 copolymer, nylon 6T / 6I copolymer, nylon 6T / 6 copolymer, nylon 6T. / 12 copolymer, nylon 6T / 12/66 copolymer, nylon 6T / 12 / 6I copolymer, and at least one polyamide selected from copolymers having hexamethine terephthalamide units. These polyamide resins are also practically suitable for use as a mixture depending on required properties such as moldability, heat resistance, toughness, and surface properties. The degree of polymerization of the polyamide used here is not particularly limited, but a polyamide having a relative viscosity (ηr) of 1.9 to 4.0 measured at 25 ° C. in 98% sulfuric acid concentration 1% according to JIS-K6920. A range of 2.0 to 3.5 is particularly preferable. When the relative viscosity is within this range, the moldability and mechanical properties are excellent, which is suitable for the present invention.

(A3) PBT resin (A3) PBT resin (hereinafter also referred to as component (A3)) used as a thermoplastic resin in the present invention is terephthalic acid (or its ester-forming derivative such as dimethyl terephthalate) and 1,4-butanediol. (Or an ester-forming derivative thereof) as a main raw material and a polymer obtained by polycondensation reaction.

  PBT copolymers that can be used in combination with the PBT include terephthalic acid (or an ester-forming derivative such as dimethyl terephthalate), 1,4-butanediol (or an ester-forming derivative thereof), and these And other dicarboxylic acids copolymerizable with (or ester-forming derivatives thereof) or other diols (or ester-forming derivatives thereof).

  Examples of other dicarboxylic acids (or ester-forming derivatives thereof) include isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, and anthracene dicarboxylic acid. 4,4′-diphenyl ether dicarboxylic acid, aromatic dicarboxylic acid such as 5-sodium sulfoisophthalic acid, aromatic dicarboxylic acid such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, And alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid.

  The component (A3) is selected from (D) polycarbonate resin, acrylonitrile / styrene copolymer, polyphenylene oxide, styrene resin, acrylic resin, polyethersulfone, polyarylate, and polyethylene terephthalate resin (hereinafter also referred to as component D). It is also practically preferable to use at least one selected from the above as a mixture because of necessary properties such as moldability, toughness, and low warpage of the molded product.

  When only the PBT copolymer is used as the component (A3), the addition of at least one selected from polycarbonate resin, styrenic resin and polyethylene terephthalate resin may undesirably deteriorate moldability.

  The viscosity of the component (A3) is not particularly limited as long as it can be melt-kneaded. However, it is usually preferable that the intrinsic viscosity when an o-chlorophenol solution is measured at 25 ° C. is 0.36 to 1.60. . When the component (A3) is composed of polybutylene terephthalate and polybutylene terephthalate copolymer, the physical or molten mixture is dissolved in o-chlorophenol after pulverization or in the form of pellets, and o-chloro The result of adjusting the phenol solution and measuring the viscosity only has to be within the viscosity condition.

  In the present invention, impact resistance and cold resistance can be imparted to the component (A3) by further blending an elastomer. The elastomer can be blended even if it is an elastomer that blocks the transmission of laser light. Examples of such an elastomer include ethylene and styrene. Here, the heat resistance refers to the resistance to cracking in a low temperature and high temperature repeated environment in a resin molded body formed by insert molding of a metal or the like, which is greatly different from a polybutylene terephthalate resin or the like. .

  The amount added when the elastomer is blended is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the component (A3) in view of moldability such as fluidity and releasability. The elastomer may be used alone or in combination of two or more.

(A) Thermoplastic resin composition The (A) thermoplastic resin composition used in the present invention further comprises a group consisting of a higher fatty acid having 12 or more carbon atoms, an alkali metal salt, an alkaline earth metal salt, an ester, and an amide compound. At least one selected from can be blended.

  Alkali metal salts, alkaline earth metal salts, esters, amide compounds composed of higher fatty acids having 12 or more carbon atoms, acidic compounds and aluminum, barium, calcium, etc. are hydrochloric acid, sulfuric acid, nitric acid, perchloric acid, sulfurous acid, nitrous acid. , Phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, benzenesulfonic acid, p-toluenesulfonic acid, acetic acid, propionic acid, butyric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, isostearic acid Benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, succinic acid, malonic acid, succinic acid, adipic acid, sebacic acid, montanic acid, etc., (A1) PPS resin, (A2) PA resin, (A3) Affinity and mechanical properties with PBT resin, especially lauric acid, myristic acid, Michin acid, stearic acid, oleic acid, behenic acid, fatty acids such as montanic acid are preferred. These fatty acids may be a single compound or a mixture of two or more.

  The blended amounts of higher fatty acids having 12 or more carbon atoms and alkali metal salts, alkaline earth metal salts, esters and amide compounds used in the present invention are (A1) PPS resin, (A2) PA resin, (A3) PBT resin. The amount is 0.005 to 1 part by weight, preferably 0.05 to 0.5 part by weight per 100 parts by weight of the thermoplastic resin. It is preferable to add 0.005 parts by weight or more, since an effect of improving the releasability is obtained, and setting the amount to 2 parts by weight or less can prevent deterioration of physical properties and mold contamination due to generated gas.

  Furthermore, the thermoplastic resin composition (A) of the present invention contains other components, for example, weathering agents (resorcinol-based, salicylate-based, benzotriazole-based, benzophenone-based, hindered amine-based, etc.) within the range not impairing the object of the present invention. , Lubricants (montanic acid and metal salts thereof, esters thereof, half esters thereof, stearyl alcohol, stearamide, various bisamides, bisureas and polyethylene waxes), pigments (cadmium sulfide, phthalocyanine, rylene, perylene, naphthacocyanin, quinacridone, Carbon black, titanium oxide, iron oxide, azo, monoazo, metal complex salts, etc.), dyes (azine, azo, perylene, anthraquinone, etc.), crystal nucleating agents (talc, polyether ether ketone, etc.), plastic Agent (octyl p-oxybenzoate, N-butylbenzene) Zensulfonamide, etc.), antistatic agents (alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric Antistatic agents, etc.), flame retardants (eg red phosphorus, melamine cyanurate, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resins or their brominated flame retardants and antimony trioxide) And the like), coloring inhibitors (hypophosphite, etc.), foaming agents, other polymers, and the like.

The addition of the crystal nucleating agent increases the crystallization rate (solidification rate) and shortens the molding cycle. Further, the addition of pigments and dyes can improve the design of the molded product.
These additives may interfere with the transmission of laser light. Moreover, since a synergistic effect may be acquired by combining two or more types, you may use together.

(Inorganic filler)
In the (A) thermoplastic resin composition used in the present invention, one or more kinds of (C) inorganic fillers are preferably blended as a compounding agent in order to develop strong bonding strength with metal. As such an inorganic filler component, fibrous, granular, plate-like, hollow and the like can be used. Specific examples 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, silicon carbide fiber, ceramic fiber, Fibrous fillers such as asbestos fiber, stone fiber, metal fiber, basalt fiber, milled glass 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, iron oxide, calcium carbonate, magnesium carbonate, dolomite Acid salts, sulfates such as calcium sulfate, barium sulfate, hydroxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, glass beads, glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black In addition, non-fibrous fillers such as silica and graphite are used, and glass fiber, carbon fiber, milled glass fiber, glass bead, and glass flake are preferable in terms of mechanical strength and molded product low warpage, and glass fiber. Carbon fiber is particularly preferable from the viewpoint of reducing linear expansion.

  These (C) inorganic fillers can be used in combination of two or more. Further, these inorganic fillers may be used after being pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound.

  In the present invention, an inorganic filler that blocks the transmission of laser light can also be used, and an inorganic filler necessary to satisfy the performance required for the resin molding can be blended.

  The blending amount of the inorganic filler is preferably in the range of 17.6 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin such as (A1) PPS resin, (A2) PA resin, (A3) PBT resin, and the like. The range of .6 to 66.7 parts by weight is preferable from the viewpoint of strength, rigidity and moldability. The content of the inorganic filler can be appropriately changed depending on the application from the balance of strength, rigidity, and other characteristics.

The molded body made of the thermoplastic resin composition used in the present invention preferably has a linear expansion coefficient of 2.0 to 4.5 × 10 ⁻⁵ / ° C. in a temperature range of 23 to 80 ° C., and has a linear expansion coefficient of In order to make this range, it is preferable to blend an inorganic filler.

(Kneading method)
The thermoplastic resin composition constituting the resin molded body of the present invention can be obtained by melt-kneading each of the above compounding agents by a known method. The melt kneader is supplied to a generally known melt kneader such as a single-screw, twin-screw extruder, Banbury mixer, kneader, and mixing roll at a melting temperature of the thermoplastic resin at a processing temperature of 5 to 100 ° C. A typical example is a kneading method. At this time, the mixing order of the raw materials is not particularly limited, and a method in which all raw materials are blended and then melt-kneaded by the above method, a part of the raw materials are blended and then melt-kneaded by the above method, and the remaining raw materials are blended. Any method such as a method of melt kneading or a method of mixing a part of raw materials and mixing the remaining raw materials using a side feeder during melt kneading by a single-screw or biaxial extruder may be used. As for the small amount additive component, other components can be kneaded by the above-mentioned method and pelletized, then added before molding and used for molding.

  As a molding method of a molded article to be bonded to a metal in the present invention, it can be applied to any molded product obtained by any of extrusion molding, extrusion molding such as injection molding, film, sheet, fiber, blow molding, tube / pipe molding, In particular, a molded product obtained by injection molding is preferably used.

  When (A1) PPS resin, (A2) PA resin, (A3) PBT resin are used as the thermoplastic resin composition, the mold temperature during injection molding is usually set to obtain a crystallized resin injection molded body. PPS resin is 130-180 ° C. Moreover, PA resin and PBT resin shall be 60-100 degreeC. From the dimensional stability and molding cycle, the PPS resin is more preferably 130-150 ° C. The PA resin and PBT resin preferably have a mold temperature of 60 to 80 ° C.

(metal)
The (B) metal of the present invention is preferably surface-treated on the surface to be combined with the molded body made of the thermoplastic resin composition and / or the laser light irradiation surface.
By surface-treating the joint surface with the molded body made of the resin composition, an improvement in adhesive strength can be expected. Moreover, the effect which reduces the laser beam reflectance of a metal surface can be anticipated by surface-treating a laser beam irradiation surface.

  (B) Examples of metals include iron, copper, nickel, gold, silver, platinum, palladium, cobalt, zinc, lead, tin, titanium, chromium, aluminum, magnesium, manganese, and alloys thereof (stainless steel, brass, phosphor bronze, etc.) ) And the like. In addition, metal coatings (metal plating, vapor deposition films, coating films, etc.) are also targeted. Of these, aluminum, aluminum alloy, copper, and copper alloy are particularly suitable.

  The (B) metal in the present invention is preferable in terms of obtaining a higher welding strength by removing the surface oxide layer and performing surface roughening on the surface to be bonded to the resin molded body by sandblasting or sanding.

  Further, (B) the surface to be bonded to the metal resin molded body is a surface treatment with a triazine thiol derivative, or at least one compound selected from ammonia, hydrazine, and a water-soluble amine compound, an anodizing treatment, boehmite treatment, Chromate treatment is preferable for obtaining excellent welding strength.

  The surface treatment with such a triazine thiol derivative is to prepare an electrolytic solution using water, an organic solvent or a mixture thereof of a polyfunctional triazine dithiol derivative as a solvent, and using this electrolytic solution by an electrochemical method (B And (B) a method for producing a polyfunctional triazine dithiol derivative coating on the surface of the metal.

As the multifunctional triazine dithiol derivative used in the present invention,
General formula

(In the above formula, R is —OR ₁ , —OOR ₁ , —SmR ₁ , —NR ₁ (R ₂ ); R ₁ , R ₂ is H, hydroxyl group, carbonyl group, ether group, ester group, amide group, amino group; Group, phenyl group, cycloalkyl group, alkyl group, or a substituent containing an unsaturated group such as alkyne or alkene, m is an integer of 1 to 8, and M is H or Na, Li, K, Ba, Ca, alkalis such as ammonium salts) are preferable.

(Metal electrochemical treatment method)
In this method, water or an organic solvent of a polyfunctional triazinedithiol derivative containing an electrolyte substance as necessary is treated as an electrolyte, and (B) a metal as an anode, and platinum, titanium, carbon, aluminum or stainless steel plate As the cathode, the polyfunctional triazinedithiol derivative is primarily bonded in the molecular orientation state by electrochemical surface treatment methods such as cyclic method, constant current method, constant potential method, pulse constant potential method, pulse constant current method, etc. A film having high adhesion reactivity is generated on the surface of a conductive object such as metal.

The electrolyte material may be dissolved in a solvent, exhibit electrical conductivity and be stable, and is generally NaOH, Na ₂ CO ₃ , Na ₂ SO ₄ , K ₂ SO ₃ , Na ₂ SO ₃ , K ₂ CO ₃ , NaNO. ₂ , KNO ₂ , NaNO ₃ , NaClO ₄ , CH ₃ COONa, Na ₂ B ₂ O ₇ , NaBO ₃ , NaH ₂ PO ₂ , (NaPO ₃ ) ₆ , Na ₂ MnO ₄ , Na ₃ SiO _{3 and the} like and mixtures thereof Can be mentioned. These concentrations are generally in the range of 0.001N to saturation concentration, desirably 0.01 to 0.1N. Solvents that dissolve electrolyte substances and polyfunctional triazinedithiol derivatives at the same time are desirable, and the combinations are not limited and cannot be specified. For example, water, methanol, ethanol, carbitol, cellosolve, dimethylformamide, methylpyrrolidone, acrylonitrile, ethylene Examples thereof include carbonates and mixed solvents thereof.

  Since the concentration of the polyfunctional triazine dithiol derivative is related to the resin molded body to be combined, it cannot be uniquely identified. For example, 0.000001 to 10 mol / L, preferably 0.00001 to 1 mol / L is preferable. The temperature of the electrolytic solution cannot be uniquely specified because it is related to the freezing point or boiling point of the solvent. For example, when an aqueous solution is used as the electrolytic solution, it is 1 to 99 ° C, preferably 20 to 80 ° C.

  The counter electrode (cathode) material may be any material that does not react with the electrolytic solution or have extremely low conductivity. Generally, platinum, titanium, carbon, aluminum, stainless steel plate, etc. are used. The potential width of the cyclic method is within a range where the solvent is not decomposed. This range cannot be uniquely identified because it is affected by the type of solvent and electrolyte substance. The scanning speed is 0.001 to 100 mV / sec, preferably 0.01 to 50 mV / sec. If it is 0.001 mV / sec or less, the treatment takes too much time, and metal alteration occurs. Moreover, it is too fast at 100 mV / sec or more, and it is not possible to obtain an alignment film in which polyfunctional triazine dithiol derivative molecules are arranged. The potential of the constant potential method is 0.01 to 100 V, preferably in the range of natural potential to oxidation potential. Below the natural potential, the film does not grow at all, and above the oxidation potential, the solvent is decomposed and the film is destroyed.

The current density of the constant current method 0.00005~50mA / cm ^2, and preferably is 0.001~10mA / cm ² suitable. When the value is less than 0.001 mA / cm ² , the film growth is slow, and metal alteration occurs. On the other hand, if it is larger than 10 mA / cm ² , cracks grow in the coating or metal elution occurs, which is not preferable. The electrolytic potential and electrolytic current density in the pulse method are as described above, but the time width is 0.01 to 10 minutes, preferably 0.1 to 2 minutes. If it is shorter than 0.1 minute, a film is not formed and the effect of the pulse method cannot be obtained. In the pretreatment of metal, if foreign matter such as organic matter is adhered, it must be removed. A metal oxide or the like causes the surface conductivity to be remarkably lowered or the weldability to be lowered. Therefore, it is desirable to perform pretreatment until the metal surface is exposed. Each of the above ranges is a guideline, and changes as the condition factors and combinations thereof change.

  In addition, it is also useful to obtain excellent welding strength when (B) the surface of the metal is aluminum or aluminum alloy which has been surface-treated with at least one compound selected from ammonia, hydrazine, and a water-soluble amine compound. Is the method.

Such treatment methods are formation of an aluminum alloy shaped article, pretreatment, main treatment, and posttreatment.
Details of each of these steps will be described below.

[Formation of aluminum alloy shape]
Aluminum alloys are those of Japanese Industrial Standard 1000-7000 series, and die casting aluminum alloys AC1-9, ADC1-12, and the like. Aluminum alloy is processed by sawing, milling, electrical discharge machining, drilling, forging, pressing, grinding, polishing, etc., from materials, cutting, drilling, cutting, compression, bending, drawing, polishing, etc. , Finished in the required shape. Finally, it may be processed into a surface state required by sandblasting or the like. The aluminum alloy shape processed into the required shape needs to have no dirt on its surface and no thick oxidized or hydroxylated film.

  Even if it is a finished aluminum alloy shaped product, it is necessary to polish and remove the one that seems to have rust on the surface when left for a long period of time. In addition, in the case of using a casting alloy such as ADC12 and shaped by casting, the composition of the surface layer is different from the internal composition, and the composition of the surface layer is not uniform. Therefore, it is necessary to remove the surface layer by polishing or the like. In any case, finally, surface oxide, adhered dirt, and the like are removed, and surface polishing is performed by sandblasting, cutting, or the like so as not to hinder the subsequent process.

[Pretreatment process (degreasing and cleaning)]
In this step, after surface processing such as sand blasting and cutting, degreasing and washing are performed as pretreatment to remove processing oil, finger grease, and chips remaining on the surface of the aluminum alloy.
This degreasing and cleaning step is not a necessary condition, and is not necessary if machine oil, finger oil, and other dirt are not attached. The aluminum alloy shaped article is not welded immediately after formation, and may be left for a long time in a bad environment such as storage and transportation. When the adhesion amount of the oil agent is large, it is preferable to treat the degreasing process in two stages.

  A method of degreasing twice by washing with an aqueous solution using a commercially available degreasing agent for an aluminum alloy may be used. When using a commercially available degreasing agent for an aluminum alloy, it is dissolved in water, and the aluminum alloy shaped product is immersed in the degreasing agent aqueous solution for this aluminum alloy at a specified temperature and time, that is, at about 60 to 80 ° C. for about 5 minutes. Further, in order to obtain a clean surface by chemically scraping the aluminum surface, it is immersed in an aqueous solution of basic, acidic, or both. As the basic liquid, it is preferable to use an alkali metal hydroxide aqueous solution having a concentration of 0.5 to 3.0%, particularly an aqueous sodium hydroxide solution at a temperature of 35 to 40 ° C. As the acidic liquid, 0.5 to 5.0% concentration of hydrohalic acid, hydrofluoric acid derivative, and nitric acid can be used, and in particular, an aqueous solution of hydrochloric acid, nitric acid, or 1 hydrogen difluoride ammonium at 35 to 40 ° C. It is preferable to control the temperature. The proper use of these depends on the composition of the small amount of metal contained in the various alloys, so each solution is actually tested to select an aqueous solution with optimal conditions. If ultrasonic waves are used during immersion, reproducibility may be improved. In any case, the purpose of degreasing and cleaning is to immerse in a basic solution or an acidic solution for several minutes and roughly etch to chemically remove the surface layer film so that it is suitable for the subsequent main treatment. Wash with water and send the aluminum alloy shape to the next process.

[Main processing]
The pre-treated aluminum alloy shaped article is immersed in an aqueous solution of ammonia, hydrazine, or a water-soluble amine compound. This is the main processing referred to in the present invention. The purpose of this step is to finely etch the surface of the aluminum alloy shaped product obtained in the previous step and simultaneously adsorb these amine compounds. The broad meaning of amine compounds is ammonia, hydrazine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, ethanolamine, allylamine, ethanolamine, diethanolamine, triethanolamine, aniline, and other Amines are included.

Of these, hydrazine is particularly preferable. The reason is that the odor is small, effective at a low concentration, inexpensive, and the like. Immersion is performed at 40 to 80 ° C., particularly preferably 50 to 70 ° C., and the concentration varies depending on the compound used, but in the case of hydrazine, 2 to 10% as hydrated hydrazine (N ₂ H ₄ .H ₂ O) An aqueous solution having a concentration of 3 to 5% is particularly preferable, and the immersion time is preferably 30 to 90 seconds. After this immersion, it is washed with water and dried with hot air at 40 to 90 ° C.

  In addition, (B) using an aluminum alloy whose surface has been surface-treated by an anodic oxidation method is a useful method for obtaining excellent welding strength.

  Such an anodizing method of an aluminum alloy is a mature technique having a history of nearly 80 years, and a known method is used.

  That is, the surface oxide is formed by the same treatment as the formation, surface polishing, degreasing, and washing of the aluminum alloy shaped article described in the surface treatment method using at least one compound selected from the above-mentioned ammonia, hydrazine, and a water-soluble amine compound. After removing the machining oil and the fats and oils, the anodizing treatment which is the main treatment is performed.

In this anodizing method, an aluminum alloy shaped article is immersed in an electrolytic bath of phosphoric acid or sodium hydroxide, and fine etching is performed on the aluminum alloy surface by direct current electrolysis and an aluminum oxide layer is formed. When phosphoric acid is used for the electrolytic bath, the temperature of the solution is 10 to 30 ° C., the concentration of the phosphoric acid aqueous solution is 15 to 40%, the aluminum alloy shape is an anode, the cathode is an aluminum plate or a lead plate, the voltage is 20 to 100 V, and the current density is 0.5 to It is preferable to perform direct current electrolysis at 2 A / dm ² for 5 to 25 minutes. When sodium hydroxide is used for the electrolytic bath, the aluminum alloy shaped article is used as an anode and the cathode is used as an aluminum plate or a bath comprising a 0.05 to 0.3 mol sodium hydroxide aqueous solution at a liquid temperature of 10 to 30 ° C. It is preferable to perform direct current electrolysis at a voltage of 15 to 45 V and a current density of 0.5 to 3 A / dm ² for 5 to 25 minutes using a lead plate.

  In addition, it is a useful method for obtaining excellent welding strength to use an aluminum alloy that has been boehmized by leaving the aluminum alloy in pure water boiling water for 1 to 3 hours.

(Laser reflectance of metal surface)
The (B) metal used in the present invention is preferable because the reflectance of the laser incident side surface is 80% or less, so that the reflection of the laser beam on the metal surface is suppressed and the amount of heat generated on the metal surface increases.

  Here, for the laser reflectance, an ultraviolet / visible / near infrared spectrophotometer (UV-3150) manufactured by Shimadzu Corporation and a φ60 integrating sphere (ISR-3100) manufactured by Shimadzu Corporation are used. In a test piece cut to a width of 25 mm, a length of 65 mm, and a thickness of 1.0 mm, the laser beam incident angle is 8 degrees, the laser beam reflectivity is expressed as a percentage of the reflected light amount and the incident light amount, and the near infrared ray is 800 to 1100 nm. The wavelength region was measured every 50 nm. It is preferable that both the minimum value and the maximum value are 80% or less.

(Manufacture of complex)
In the present invention, the molded body made of the thermoplastic resin composition (A) and the metal (B) are overlapped, and (B) the laser beam is irradiated from the metal side to soften and / or melt at least a part of the molded body. By doing so, the resin molded body and the metal are joined. The method of the present invention is also effective when the laser transmission of a molded article made of a thermoplastic resin composition is insufficient, or when the laser cannot be irradiated from the resin molded article side due to the shape of the molded article. .

  The laser used in the method of the present invention can be a laser having a wavelength of 800 to 1200 nm, and a preferred laser type is a YAG or a diode laser.

  The composite body obtained by joining the molded article of the thermoplastic resin composition of the present invention and metal obtained in this way is used as a specific application, for example, sensor, LED lamp, connector, socket, resistor, relay case, switch. , Coil bobbin, condenser, variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, plug, printed circuit board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage Electric / electronic parts such as FDD chassis, motor brush holder, parabolic antenna, lithium battery electrolyte injection sealing port, lithium battery electrode seal, computer related parts. VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts Household electrical appliance parts represented by Machine-related parts such as office computer-related parts, telephone equipment-related parts, facsimile-related parts, copier-related parts, cleaning jigs, motor parts, lighters, typewriters, bicycle wheels, etc. Optical equipment such as microscopes, binoculars, cameras, and watches, and precision machine related parts. Watering parts such as water faucet tops, mixing faucets, pump parts, pipe joints, water volume control valves, relief valves, hot water temperature sensors, water volume sensors, and water meter housings. Valves, alternator terminals, alternator connectors, IC regulators, light meter potentiometer bases, various valves such as exhaust gas valves, various fuel / exhaust / intake pipes, air intake pipes, intake manifolds, intercooler tanks, fuel Pump, engine coolant joint, radiator tank, LLC reserve tank, throttle body, throttle butterfly valve, variable intake bar, lub, exhaust gas sensor, coolant sensor, oil temperature sensor, throttle position sensor, cylinder head cover, crankshaft position sensor , Air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve, radiator Brush holder for motor, water pump impeller housing, 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 related electromagnetic valve, Fuse connector, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, vehicle speed sensor, cable liner, engine control unit case, Engine driver unit case, condenser case, electromagnetic valve, motor insulation material, hive Ddoka of control system component case, the accelerator pedal, parking brake pedal, front-end modules, door modules, cockpit modules, seat frames, automotive and vehicle-related parts, such as Hostelling members. Other various uses can be exemplified.

  The present invention will be described more specifically with reference to the following examples. The present invention is not limited to the following examples as long as the gist thereof is not exceeded. Moreover, all the additive formulations shown in Examples and Comparative Examples are parts by weight. Each evaluation was measured according to the method described below.

(1) General mechanical properties and moldability Measured according to the following standard method. In addition, the test piece in the following tensile test, a bending test, etc. was produced with the Nissei Resin Co., Ltd. injection molding machine NEX-1000-9E. (Cylinder temperature: 320 ° C (PPS), 280 ° C (PA66), 260 ° C (PA6, PA66 / PA6I / PA6 copolymerization, PBT)), mold temperature 130 ° C (PPS), 80 ° C (PA6, PA66, PA66) / PA6I / PA6 copolymerization, PBT), the injection pressure was the molding lower limit pressure + 12.8 MPa, the injection time was 15 sec, and the cooling time was 15 sec.

-Moldability test piece When the resin test piece is filled with the above temperature, pressure, injection time, and cooling time, and then cooled, the resin test piece is greatly deformed when the resin test piece is ejected from the mold by the ejection pin. Or “x” indicates that the protruding portion is greatly buckled, and “◯” indicates that there is no deformation.

-Tensile strength It was performed according to ASTM D638. Using a No. 1 dumbbell-shaped test piece (test piece thickness: 1/8 inch (3.2 mm)), the test was conducted at 23 ° C. at a test speed of 10 mm / min.

-Flexural modulus It carried out based on ASTM D790. The test was performed at 23 ° C. at a test speed of 3 mm / min using a bending test piece (test piece thickness: 1/4 inch (6.4 mm)).

-Izod impact strength It carried out based on ASTM D256. The test was performed at 23 ° C. using an impact test piece (test piece thickness: 1/8 inch (3.2 mm), cut notch).

-Deflection temperature under load It was performed according to ASTM D648. A load deflection test piece (test piece thickness: 1/4 inch (6.4 mm)) was used, and the load stress was 1.82 MPa.

(2) Linear expansion coefficient The linear expansion coefficient of the thermoplastic resin composition was evaluated by measuring the test piece 4 having a square L of 80 mm and a thickness D of 3 mm shown in FIG. 1 from the position shown in FIG. (Hereinafter abbreviated as MD) 5 and a direction perpendicular to the resin flow direction (hereinafter abbreviated as TD) 6 shown in FIG. 3 by cutting a molded body having a width W of 5 mm, a length L of 10 mm, and a thickness D of 3 mm. The produced test pieces 5 and 6 were used. The injection molding was carried out using an injection molding machine NEX-1000-9E manufactured by Nissei Plastic Industry Co., Ltd., cylinder temperature: 320 ° C. (PPS), 280 ° C. (PA 66), 260 ° C. (PA6, PA66 / PA6I / PA6 copolymerization, PBT), mold temperature 130 ° C. (PPS), 80 ° C. (PA6, PA66, PA66 / PA6I / PA6 copolymerization, PBT), injection pressure: molding lower limit pressure + 12.8 MPa, injection time: 15 sec, cooling time: 15 sec. It was produced by injection molding under conditions.

  Fig.1 (a) is a top view of the flat plate for cutting of the said linear expansion test piece, (b) is a side view of the test piece. The flat plate 4 for cutting the linear expansion test piece includes a sprue 1, a runner 2, and a gate 3, and is manufactured by cutting into the shape shown in FIG. 3 from the position shown in FIG. 2. FIG. 3A is a plan view of a linear expansion test piece, and FIG. 3B is a side view.

  The linear expansion coefficient was TMA-100 manufactured by Seiko Denshi Kogyo Co., Ltd., and the temperature was raised at a rate of 5 ° C./min at a load range of 2 g and a temperature range of −40 ° C. to 80 ° C. It was expressed by a numerical value of (MD linear expansion coefficient + TD linear expansion coefficient) / 2 in the range.

(3) Laser transmittance The test piece 4 for evaluating the laser transmittance of the thermoplastic resin was a square having an L of 80 mm and a thickness D of 1 mm shown in FIG. The injection molding conditions were created under the same conditions as the above linear expansion coefficient test piece, the gate 3 was cut, and a laser beam transmittance evaluation test piece was obtained.

  The laser beam transmittance was measured using an ultraviolet / visible / near infrared spectrophotometer (UV-3150) manufactured by Shimadzu Corporation and a φ60 integrating sphere (ISR-3100) manufactured by Shimadzu Corporation. . The laser beam incident angle is 0 degree. The laser beam transmittance represents the ratio between the transmitted light amount and the incident light amount as a percentage.

  For the laser beam transmittance, a wavelength region of near infrared rays of 800 to 1100 nm was measured every 50 nm using a sample having a thickness of 1 mm, and the minimum value and the maximum value were described in the table.

(4) Laser reflectivity The metal laser reflectivity evaluation test piece used was a test piece 7 having a width W of 25 mm, a length L of 65 mm, and a thickness D of 1 mm shown in FIG. FIG. 4A is a plan view and FIG. 4B is a side view.

  For laser beam reflectivity measurement, Shimadzu Corporation UV / visible / near infrared spectrophotometer (UV-3150) and Shimadzu Corporation φ60 integrating sphere (ISR-3100) are used. It was. The laser beam incident angle is 8 degrees. The laser beam reflectivity represents the ratio between the amount of reflected light and the amount of incident light as a percentage.

  For the laser beam reflectance, a wavelength region of near infrared rays of 800 to 1100 nm was measured every 50 nm using a sample having a thickness of 1 mm, and the minimum value and the maximum value were described in the table.

(5) Laser Weldability The thermoplastic resin test piece is molded under the same conditions as the linear expansion coefficient test piece, and has the same shape as the laser beam transmittance evaluation test piece 4 in FIG. Is a laser welding test piece 7 obtained by cutting a molded product having a length of 25 mm, a length L of 65 mm, and a thickness D of 1 mm. As the metal test piece, a test piece 7 having a width W of 25 mm, a length L of 65 mm, and a thickness D of 1 mm shown in FIG. 4 was used. FIG. 4A is a plan view of the test piece after cutting, and FIG. 4B is a side view thereof.

  As the laser welding machine, LDL-80 manufactured by Laser Line Co. was used. This welding machine is a device using a semiconductor laser, the wavelength of the laser light is near infrared of 940 nm, and the maximum output is 1000 W.

FIG. 5 is a schematic view showing a laser welding method.
As shown in FIG. 5, the laser welding method is such that a metal test piece 11 for welding is placed on the upper side, a thermoplastic resin test piece 12 for welding is placed on the lower side, the two test pieces are overlapped, and a laser beam 9 is placed from the upper part of the metal. Irradiate. The laser beam irradiation is performed along the laser welding trajectory 10, and the laser welding conditions are performed under the condition that the best welding strength is obtained in the range of output 500 to 800 W and the laser scanning speed of 5 to 50 mm / sec. It was.

  FIG. 6A is a plan view of a laser welding strength measurement test piece laser-welded by the above method, and FIG. 6B is a side view of the test piece. The test piece 13 for measuring the laser welding strength was obtained by superimposing the metal test piece 11 and the thermoplastic resin test piece 12 which are laser welding test pieces shown in FIG. The welding distance Y is 20 mm, and the welded portion 14 of the overlapped metal test piece and thermoplastic resin test piece is laser welded.

  A general tensile tester (AG-500B manufactured by Shimadzu Corporation) is used to measure the welding strength, and both ends of the test piece are fixed with a chuck, and a tensile test is performed so that a tensile shear stress is generated at the welded portion. Went. The welding strength was the stress when the welded site was broken. The strength measurement conditions were a tensile speed of 1 mm / min and a span of 40 mm.

  The laser welding test piece was evaluated for laser welding using a surface-treated metal and a thermoplastic resin.

(6) [Reference Example 1] Polymerization of PPS resin In a 70 liter autoclave equipped with a stirrer, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide and 2957.21 g (70.97 g) of 96% sodium hydroxide were added. Mol), 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 while flowing nitrogen at normal pressure, 245 After gradually heating up to about 3 hours and distilling out 14780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The residual water content in the system per 1 mol 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 had a melt viscosity of 60 Pa · s (310 ° C., shear rate of 1000 / s).

(7) [Reference Example 2] PA resin / PA66 resin (also referred to as PA-1) Relative viscosity (ηr) 2.75
PA6 resin (also referred to as PA-2) Relative viscosity (ηr) 2.75
PA66 / PA6I / PA6 copolymer (also referred to as PA-3) Relative viscosity (ηr) 2.00
Composition PA66 / PA6I / PA6: 77/17/6 wt%

(8) [Reference Example 3] PBT resin Intrinsic viscosity (measured at 25 ° C using an orthochlorophenol solution) 0.85

(9) [Reference Example 4] Treatment with triazine dithiol derivative A monosodium salt of a polyfunctional triazine dithiol derivative is dissolved at a concentration of 5 × 10 ⁻³ mol / L, and Na ₂ CO ₃ is dissolved in 1N distilled water. Make a solution. This was put in an electrolytic cell, a platinum plate was used for the cathode, various laser welding metals with a thickness of 1 mm were used for the anode, current was applied at a current density of 0.1 mA / cm ² at 60 ° C. for 10 minutes, A functional triazine dithiol derivative coating was prepared and then washed with methanol to remove adhering impurities and dried. It processed with this polyfunctional triazine dithiol derivative, and it was set as the metal test piece 11 for laser welding.

(10) [Reference Example 5] Surface treatment of hydrazine A commercially available A5052 aluminum alloy plate having a thickness of 1 mm was purchased and cut into rectangular pieces of 25 mm × 65 mm to obtain aluminum alloy shapes. A commercially available aluminum alloy degreasing agent “NE-6 (manufactured by Meltex Co., Ltd.)” was dissolved in water at a concentration of 15% to 75 ° C. It was immersed in a degreasing bath containing this aqueous solution for 5 minutes and washed with water. Subsequently, it was immersed in a bath containing a 1% hydrochloric acid aqueous solution at 40 ° C. for 1 minute and washed with water. Subsequently, it was immersed in a bath containing 1% aqueous sodium hydroxide solution at 40 ° C. for 2 minutes and washed with water.

Next, it was immersed in a bath containing 1% aqueous hydrochloric acid at 40 ° C. for 1 minute and washed with water. Subsequently 60 ° C. of 3.5% concentration of 1 aqueous solution of hydrazine hydrate _{(N 2 H 4 · H 2} O) was immersed for 1 minute in a first processing bath containing, 40 ° C. 1 water at a 0.5% concentration of It was immersed in a second treatment tank containing a hydrazine aqueous solution (N ₂ H ₄ .H ₂ O) for 0.5 minutes and washed with water. This was dried in warm air for 15 minutes at 40 ° C. and for 5 minutes at 60 ° C. and stored in dry air to obtain an aluminum alloy specimen 11 for laser welding.

(11) [Reference Example 6] Anodizing treatment A commercially available A5052 aluminum alloy plate having a thickness of 1 mm was purchased and cut into rectangular pieces of 25 mm × 65 mm to obtain aluminum alloy shapes. A commercially available aluminum alloy degreasing agent “NE-6 (manufactured by Meltex Co., Ltd.)” was dissolved in water at a concentration of 15% to 75 ° C. It was immersed in a degreasing tank containing this aqueous solution for 1 minute and washed with water. Then, it was immersed in a tank containing a 60% nitric acid aqueous solution at 90 ° C. for 15 seconds and washed with water. Subsequently, a tank containing a 5% sulfuric acid aqueous solution at 20 ° C. was prepared, and an anode of a DC power supply “ASR3SD-150-500” manufactured by Chuo Seisakusho was connected to the aluminum alloy and placed in the tank. The cathode was connected to a lead plate and placed in the same tank. This was anodized by constant current control with a current density of 5 A / dm ² to obtain a laser welded aluminum alloy test piece 11.

(12) [Reference Example 7] Glass fiber Glass fiber: PPS resin T-717 (fibrous filler, E glass manufactured by NEC Glass, single fiber diameter 13 μm, refractive index (n _D ) 1.55), PA Resin T-289 (fibrous filler, E glass manufactured by Nippon Electric Glass Co., Ltd., single fiber diameter 13 μm, refractive index (n _D ) 1.55), PBT resin T-187 ((fibrous filler, Nippon Electric Glass ( Co., Ltd. E glass, single fiber diameter 13 μm, refractive index (n _D ) 1.55).

(13) [Reference Example 8] Carbon black Carbon black: # 30 (carbon black for coloring, manufactured by Mitsubishi Chemical Corporation) was used.

Examples 1-13, Comparative Examples 1-4
The manufacturing method of the resin material described in Examples 1-13 and Comparative Examples 1-4 is as follows. That is, using a twin screw extruder TEX30α type (Screw L / D = 45.5) manufactured by Nippon Steel Co., Ltd., the PPS resin of Reference Example 1, the additive, and the carbon black of Reference Example 8 were supplied from the original filling portion. In addition, the glass fiber of Reference Example 7 is supplied from the side feeder, the screw speed is 300 rpm, the cylinder temperature is set so that the resin temperature discharged from the die is 330 ° C., melt kneaded, and discharged from the die. The strands were cooled in a cooling bath and pelletized with a strand cutter.

  Each of the obtained materials was dried for 3 hours with a 130 ° C. hot air dryer, and then molded and evaluated using the evaluation method described above.

  Tables 1 and 2 show the resin formulation and characteristics of Examples 1 to 13 and Comparative Examples 1 to 4, and metal types, surface treatment methods and characteristics, and welding characteristics.

  The glass fiber reinforced PPS resin obtained in the present invention of Examples 1 to 13, triazine thiol derivative, hydrazine, copper treated with anodization, aluminum, and aluminum alloy were combined, and a laser beam was used as a heating source from the metal side. When irradiated, the PPS resin at the contact interface where the metal and the PPS resin are overlapped is softened and / or melted, so that the tensile shear strength of the joint portion is 17 to 25 MPa. Even in the case of a molded body made of a resin that does not contain glass fiber, the tensile shear strength of the joint is 3 to 8 MPa by irradiating laser light from the metal side.

  On the other hand, in all of Comparative Examples 1 to 4, the joint tensile shear strength was 0 MPa, and the surface of the PPS resin on the laser beam irradiation side burned and could not be joined.

Examples 14-26, Comparative Examples 5-8
The manufacturing method of the resin material described in Examples 14-26 and Comparative Examples 5-8 is as follows. That is, using a twin screw extruder TEX30α type (Screw L / D = 45.5) manufactured by Nippon Steel, Ltd., the PA resin of Reference Example 2 and the additive were fed from the original filling portion to the glass fiber of Reference Example 7. The cylinder temperature is set so that the resin temperature supplied from the side feeder is 300 rpm and the resin temperature discharged from the die is 310 ° C. (PA66 resin) and 280 ° C. (PA6, PA66 / 6I / PA6 copolymer resin). Then, after melt-kneading, the strand discharged from the die was cooled in a cooling bath, and then pelletized by a strand cutter.
Each obtained material was dried for 24 hours with a vacuum dryer at 80 ° C., and then molded and evaluated using the evaluation method described above.

  Tables 3 and 4 show the resin formulation and characteristics of Examples 14 to 26 and Comparative Examples 5 to 8, and metal types, surface treatment methods and characteristics, and bonding characteristics.

  The glass fiber reinforced PA resin obtained in the present invention of Examples 14 to 26, triazine thiol derivative, hydrazine, copper treated with anodization, aluminum, and aluminum alloy were combined, and a laser beam was used as a heating source from the metal side. When the PA resin at the contact interface where the metal and the PA resin are overlapped with each other is softened and / or melted, the tensile shear strength of the joint portion is 15 to 25 MPa. Even in the case of a molded body made of a resin that does not contain glass fiber, the tensile shear strength of the bonded portion is expressed by 3 to 8 by irradiating laser light from the metal side.

  On the other hand, in all of Comparative Examples 5 to 8, the joint tensile shear strength was 0 MPa, and the surface of the PA resin on the laser beam irradiation side burned and could not be joined.

Examples 27-38, Comparative Examples 9-12
The manufacturing method of the resin material described in Examples 27-38 and Comparative Examples 9-12 is as follows. That is, using a twin screw extruder TEX30α type (Screw L / D = 45.5) manufactured by Nippon Steel, Ltd., the PBT resin of Reference Example 3 and the additive were supplied from the original filling portion, and the glass fiber of Reference Example 7 Is supplied from the side feeder, the screw rotation speed is 300 rpm, the cylinder temperature is set so that the resin temperature discharged from the die is 290 ° C., melt kneading, and the strand discharged from the die is cooled in the cooling bath And then pelletized with a strand cutter.
Each of the obtained materials was dried for 3 hours with a 130 ° C. hot air dryer, and then molded and evaluated using the evaluation method described above.

  Tables 5 and 6 show the resin formulation and characteristics of Examples 27 to 38 and Comparative Examples 9 to 12, and metal types, surface treatment methods and characteristics, and bonding characteristics.

  The glass fiber reinforced PBT resin obtained in the present invention of Examples 27 to 38, triazine thiol derivative, hydrazine, copper, aluminum, and aluminum alloy subjected to surface treatment by anodization were combined, and a laser beam was used as a heating source from the metal side. Irradiation causes the PBT resin at the contact interface where the metal and the PBT resin are overlapped to soften and / or melt, whereby the tensile shear strength of the joint is 13 to 21 MPa. Also in the case of a molded body made of a resin not containing glass fiber, the tensile shear strength of the bonded portion is expressed as 3 to 6 by irradiating laser light from the metal side.

  On the other hand, in all of Comparative Examples 9 to 12, the joint tensile shear strength was 0 MPa, and the surface of the PBT resin on the laser beam irradiation side burned and could not be joined.

1 Sprue 2 Runner 3 Gate 4 Linear expansion coefficient measurement sample, laser transmittance measurement sample, shape of test piece before cutting of laser welding resin sample 5 Linear expansion coefficient test piece (MD)
6 Linear expansion coefficient test piece (TD)
7 Laser beam reflectance measurement test piece (metal), laser beam transmittance measurement test piece (resin), laser welding test piece (resin test piece, metal test piece) Shape 8 Laser beam irradiation part 9 Laser beam 10 Laser beam trajectory DESCRIPTION OF SYMBOLS 11 Laser welding metal test piece 12 Laser welding thermoplastic resin test piece 13 Laser welding strength measurement test piece 14 Laser welding part

Claims (9)

(A) A molded body made of a thermoplastic resin composition and (B) a metal are overlapped, and (B) the laser beam is irradiated from the metal side, and at least a part of the molded body made of the thermoplastic resin composition is softened and A method for producing a composite of a molded body and a metal comprising a thermoplastic resin composition, characterized by joining by melting. (A) The thermoplastic resin composition according to claim 1, wherein a linear expansion coefficient of the molded body made of the thermoplastic resin composition is 2.0 to 4.5 × 10 ⁻⁵ / ° C. in a temperature range of 23 to 80 ° C. A method for producing a composite of a molded article made of a product and a metal. The said (A) thermoplastic resin composition is a composition formed by mix | blending 17.6-100 weight part of (C) inorganic filler with respect to 100 weight part of thermoplastic resins. A method for producing a composite of a molded body and a metal comprising a thermoplastic resin composition. The (A) thermoplastic resin composition is a composition comprising at least one selected from (A1) polyphenylene sulfide resin, (A2) polyamide resin, and (A3) polybutylene terephthalate resin. A method for producing a composite of a molded body and a metal comprising the thermoplastic resin composition according to any one of 3 above. 5. The thermoplastic resin according to claim 1, wherein the metal surface has a reflectance of 80% or less when laser light having a wavelength of 800 to 1100 nm is irradiated on the surface of the metal on the laser irradiation side. A method for producing a composite of a molded body and a metal comprising the composition. From the thermoplastic resin composition according to any one of claims 1 to 5, wherein a surface of the metal (B) to be combined with a molded body made of the thermoplastic resin composition is surface-treated. A method for producing a composite of a molded body and a metal. The method for producing a composite of a molded body and a metal comprising the thermoplastic resin composition according to claim 6, wherein the surface of the metal (B) is surface-treated with a triazine thiol derivative. From the thermoplastic resin composition according to claim 6, wherein the surface of the metal (B) is surface-treated with at least one compound selected from ammonia, hydrazine and a water-soluble amine compound. A method for producing a composite of a molded body and a metal. The method for producing a composite of a molded body and a metal comprising the thermoplastic resin composition according to claim 6, wherein the surface of the metal (B) is anodized.

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