JP2011173353A - Composite structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a composite comprising a metal and polyarylene sulfide resin or resin composition and having a high joining strength. <P>SOLUTION: In a composite structure of metal and polyarylene sulfide resin or resin composition, the surface of metal is roughened physically and/or chemically, and the polyarylene sulfide resin or the polyarylene sulfide component composing the resin composition contains a copolymer comprising at least a para-arylene sulfide repeating unit, and contains 2-20 mol% of meta-arylene sulfide repeating units in the polyarylene sulfide component. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a composite structure of a molded body made of a resin or a resin composition and a metal, and in particular, by cooling and solidifying the molten resin or resin composition in contact with the metal, the resin or resin The present invention relates to a composite structure in which a molded body made of a composition and a metal are directly bonded.

  The present invention relates to a composite structure in which a molded article made of a metal or an alloy thereof and a resin or a resin composition is used for electronic devices, home appliances, automobile parts, structural parts, mechanical parts, and the like. More specifically, metal and resin or resin produced by machining such as cutting, cutting, bending, drawing, that is, machining such as sawing, milling, electrical discharge machining, drilling, pressing, grinding, polishing, etc. A structure in which a molded body made of a composition is integrated and a method for producing the same, and various electronic devices, home appliances, medical devices, vehicle structural parts, vehicle-mounted products, building materials, other structural parts and exteriors The present invention relates to a composite structure of a molded body made of a metal and a resin or a resin composition used for parts and the like.

  Polyarylene sulfide resins or resin compositions have excellent properties as engineering plastics such as excellent heat resistance, chemical resistance, electrical insulation, and heat and humidity resistance, so they can be used in a wide range of fields, mainly in the electric and automotive fields. It has already been widely used in a composite structure of a molded body made of a metal and a resin or a resin composition.

  As a means for compounding a molded body made of a metal and a resin or a resin composition, a method of embedding a part of the metal in a resin molded product, a method of embedding a part of the resin molded product by providing a hole in the metal, a rivet or a bolt However, there are significant restrictions on the shape of the composite structure, and there are problems such as strength reduction due to the occurrence of stress concentration.

  Therefore, in applications and shapes where the bonding strength between the metal and the molded body made of the resin or resin composition affects the strength of the entire structure, the molded body made of the metal and the resin or resin composition is in direct contact. There is a demand for bonding strength on the surface. For example, in automobile applications, a composite structure of a molded body made of a metal and a resin or a resin composition is often used for weight reduction, but there is a strong demand for expansion of the application range for further weight reduction. ing. However, it is a big problem in adapting to structural parts and exterior parts that require strength.

  On the other hand, a method using an adhesive has been proposed. When an adhesive is used, complication of processes such as cleaning of the adhesive surface, application and curing of the adhesive is one of the problems in mass production.

  On the other hand, when a method for modifying a metal surface is used, a method of directly welding a resin or a resin composition to a metal by a method such as injection molding has been proposed.

  For example, Patent Document 1 discloses a method in which a metal surface is treated in advance with an aqueous hydrazine solution, and a resin or resin composition containing polyarylene sulfide is injected and integrated on the surface-treated metal surface. However, this method may cause problems such as a long surface treatment time.

  On the other hand, a resin or resin composition containing a polyarylene sulfide copolymer containing a paraarylene sulfide unit (hereinafter referred to as p-arylene sulfide unit) and a metaarylene sulfide unit (hereinafter referred to as m-arylene sulfide unit). Is disclosed in Patent Document 2, etc., and there is a description that it can be used for insert molding, etc., but a method for obtaining high bonding strength on a surface where a metal and a resin or a resin composition are in direct contact with each other. Is not disclosed at all.

  The present inventors have discovered that a specially high bonding strength is exhibited by melting and bonding a surface-treated metal and a specific polyarylene sulfide copolymer.

JP 2009-6721 A JP 2004-59835 A

  An object of the present invention is to obtain a high bonding strength at a surface in direct contact with a metal and a polyarylene sulfide resin or resin composition, and solidify the molten resin or resin composition in contact with the metal. In a state where the metal and the polyarylene sulfide resin or the resin composition are joined, or in a state where the metal and the molded article made of the resin or the resin composition are in contact with each other, energy is applied to the resin or the resin composition to be in a molten state. It is an object of the present invention to obtain a composite molded body having a high bonding strength by a method of cooling and solidifying thereafter and bonding a metal and a resin or a resin composition.

That is, the present invention provides the following.
(1) A composite structure of a molded body comprising a metal and a polyarylene sulfide resin or a resin composition, wherein the surface of the metal is physically and / or chemically roughened, and the polyarylene sulfide resin Or the polyarylene sulfide resin contained in the resin composition contains a copolymer containing at least paraarylene sulfide repeating units and 2 to 20 mol% of metaarylene sulfide repeating units based on all repeating units. .
(2) The roughness Ra of the physically roughened metal surface is 1 μm to 300 μm. The composite structure according to (1).
(3) The composite structure according to (1), wherein the chemically roughened metal surface is covered with a recess having a number average inner diameter of 10 to 80 nm.
(4) The composite structure according to (1) or (3), wherein the chemical roughening treatment is chemical etching treatment or anodizing treatment.
(5) The metal is at least one selected from aluminum, copper, iron, nickel, chromium, magnesium, molybdenum, and alloys thereof, and any one of (1) to (4) Composite structure.
(6) The polyarylene sulfide resin contained in the polyarylene sulfide resin or the resin composition is a polyarylene sulfide (co) polymer not containing a metaarylene sulfide repeating unit and a polyarylene sulfide copolymer containing a metaarylene sulfide repeating unit. Any one of (1) to (5), wherein the polyarylene sulfide resin is a mixture with a polymer, and the metaarylene sulfide repeating unit is 2 to 20 mol% with respect to all repeating units of the polyarylene sulfide resin. The composite structure according to claim 1.
(7) The composite structure according to any one of (1) to (6), wherein the composite structure is joined by injection welding.
(8) The composite structure according to any one of (1) to (6), wherein the molded body is in the form of a film or a sheet and is melt-bonded to a metal.

  ADVANTAGE OF THE INVENTION According to this invention, the composite structure which joined the molded object which consists of a metal and a polyarylene sulfide resin or a resin composition with high joint strength can be obtained.

1 is a cross-sectional view of an injection mold for producing a composite molded body of an aluminum alloy part and a part made of a polyarylene sulfide resin or a resin composition. It is an external view which shows an example of the composite molding of the aluminum alloy component and the component which consists of a polyarylene sulfide resin or a resin composition.

  The composite structure of the present invention can be obtained by joining a surface-treated metal and a molded body made of a specific polyarylene sulfide resin or resin composition.

[Polyarylene sulfide]
The polyarylene sulfide resin or the polyarylene sulfide resin contained in the resin composition used in the present invention is mainly composed of a homopolymer or copolymer having a repeating unit of-(Ar-S)-. Ar includes structural units represented by the following formulas (A) to (K).

(R1 and R2 are substituents selected from hydrogen, an alkyl group, an alkoxy group, and a halogen group, and R1 and R2 may be the same or different.)

  Specific examples include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, random copolymers, block copolymers, and mixtures thereof. Particularly preferred polyarylene sulfide is preferably polyphenylene sulfide (PPS) from the viewpoint of heat resistance and economy, and is represented by the following structural formula as the main structural unit of the polymer.

(Here, X represents an alkylene, CO, or SO ₂ unit.)

(Here, R represents an alkyl, nitro, phenylene, or alkoxy group.)

  It is important for the polyarylene sulfide resin or resin composition of the present invention to contain a polyarylene sulfide resin containing a metaarylene sulfide repeating unit, and preferably a polyarylene sulfide copolymer containing an m-phenylene sulfide unit as an essential unit. Includes coalescence.

  The content of the metaarylene sulfide repeating unit in the polyarylene sulfide resin needs to be 2 mol% or more and 20 mol% or less, more preferably 5 mol% or more and 20 mol% or less with respect to all the repeating units. When such a metaarylene sulfide unit is less than 2 mol%, sufficient bonding strength cannot be obtained in a composite structure of a metal and a resin or a resin composition, and when the metaarylene sulfide unit exceeds 20 mol%, polymer crystals Property, glass transition temperature, etc. are low, and heat resistance, electrical characteristics, chemical resistance, liquid chemical resistance, etc., which are the characteristics of PPS, may be impaired. As a copolymerization mode, any of random copolymerization, block copolymerization, and graft copolymerization may be used. In the present invention, as the polyarylene sulfide resin, it is also possible to use a mixture of a polyarylene sulfide (co) polymer not containing a metaarylene sulfide repeating unit and a polyarylene sulfide polymer containing a metaarylene sulfide repeating unit. In this case, the polyarylene sulfide resin may be mixed so that the metaarylene sulfide repeating unit is 2 to 20 mol% with respect to all the repeating units of the polyarylene sulfide resin.

  Such a polyarylene sulfide copolymer can be preferably produced by the following method.

  That is, it is a method in which an alkali metal sulfide, a p-dihaloaromatic compound, and an m-dihaloaromatic compound are reacted in an aprotic polar solvent. Although there is no restriction | limiting in particular in the injection | throwing-in order of a p-dihalo aromatic compound and a m-dihalo aromatic compound, First, p-dihalo aromatic compound is prepared to the reaction system, The reaction rate of p-dihalo aromatic compound is 0-50. A method in which the m-dihaloaromatic compound is added to the reaction system with respect to the total amount of the charged dihaloaromatic compound at a time of less than% and the polymerization is carried out at an elevated temperature is preferred.

  Hereinafter, for the polymerization method of the present invention, alkali metal sulfide, dihaloaromatic compound, molecular weight regulator, branching / crosslinking agent, polymerization solvent, polymerization aid, polymerization stabilizer, polymerization reaction, post-treatment and product polyarylene sulfide. Further details will be described in order, and the kneading method for the polyarylene sulfide resin composition will be described in detail.

-Alkali metal sulfides As the alkali metal sulfides used in the present invention, lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and a mixture of two or more thereof can be mentioned as preferable examples. Particularly preferred is sodium sulfide. These alkali metal sulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides. Further, an alkali metal sulfide prepared in situ from an alkali metal hydrosulfide and an alkali metal hydroxide in a reaction system or in a separate reactor can also be used. Alternatively, alkali metal sulfide prepared in situ in a reaction system or in a separate reactor from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide can also be used.

  In the present invention, the amount of charged alkali metal sulfide means the remaining amount obtained by subtracting the loss from the actual charged amount when a partial loss of alkali metal sulfide occurs before the start of the reaction due to dehydration operation or the like. It shall be.

Dihaloaromatic compound As the paradihaloaromatic compound used in the present invention, dihalogenated benzene such as p-dichlorobenzene, p-dibromobenzene, 1-chloro-4-bromobenzene, or 2,5-dichlorotoluene, 2,5-dichloroxylene, 1-ethyl-2,5-dibromobenzene, 1-ethyl-2,5-dichlorobenzene, 1-ethyl-2-bromo-5-chlorobenzene, 1,3,4,6-tetra Methyl-2,5-dichlorobenzene, 1-cyclohexyl-2,5-dichlorobenzene, 1-phenyl-2,5-dichlorobenzene, 1-benzyl-2,5-dichlorobenzene, 1-phenyl-2,5- Dibromobenzene, 1-p-toluyl-2,5-dichlorobenzene, 1-p-toluyl-2,5-dibromobenzene, 1-he Examples thereof include substituted dihalogenated benzene such as xyl-2,5-dichlorobenzene. Of these, dihalogenated benzene is preferred, and p-dichlorobenzene is particularly preferred. These compounds can be used alone or as a mixture.

  Examples of the metadihaloaromatic compound include dihalogenated benzene such as m-dichlorobenzene, m-dibromobenzene, and 1-chloro-3-bromobenzene, or 2,4-dichlorotoluene, 2,4-dichloroxylene, and 1-ethyl. -2,4-dibromobenzene, 1-ethyl-2,4-dichlorobenzene, 1-ethyl-2-bromo-4-chlorobenzene, 1,2,4,6-tetramethyl-3,5-dichlorobenzene, 1 -Cyclohexyl-2,4-dichlorobenzene, 1-phenyl-2,4-dichlorobenzene, 1-benzyl-2,4-dichlorobenzene, 1-phenyl-2,4-dibromobenzene, 1-p-toluyl-2 , 4-dichlorobenzene, 1-p-toluyl-2,4-dibromobenzene, 1-hexyl-2,4-dichlorobenzene It includes substituted dihalogenated benzene and the like. Of these, dihalogenated benzene is preferred, and m-dichlorobenzene is particularly preferred. These compounds can be used alone or as a mixture.

-Molecular weight regulator, branching / crosslinking agent In the present invention, a monohalo compound (not necessarily an aromatic compound) is used to form a terminal of the resulting polyarylene sulfide copolymer, or to regulate a polymerization reaction or molecular weight. Or may be used in combination. Moreover, in order to form a branched or crosslinked polymer, it is also possible to use a trihalo or higher polyhalo compound in combination. Specific examples thereof include 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-tribromobenzene, 1,2,4-tribromobenzene, and the like. It does not have to be an aromatic compound. Further, an active hydrogen-containing halogen aromatic compound and a halogen aromatic nitro compound can be used in combination.

-Polymerization solvent In this invention, an organic amide solvent is normally used as a polymerization solvent. Examples of the organic amide solvent include N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP), N-alkylpyrrolidone such as N-ethyl-2-pyrrolidone, and caprolactams such as N-methyl-ε-caprolactam. Aprotic organic amide solvents represented by 1,3-dialkyl-2-imidazolidinone, tetraalkylurea, hexaalkylphosphoric triamide, and mixtures thereof are preferably used because of their high reaction stability. . Among these, use of N-methyl-2-pyrrolidone is particularly preferable. The amount of the polymerization solvent used in the present invention is preferably in the range of 0.2 to 10 mol, more preferably in the range of 2 to 5 mol, per mol of the charged alkali metal sulfide.

-Polymerization aid In this invention, in order to obtain polyarylene sulfide with a high degree of polymerization in a shorter time, it is one of the preferable methods to use a polymerization aid. In particular, when applied to applications requiring high toughness, polyarylene sulfide having a high degree of polymerization using a polymerization aid is preferably used. Specific examples of polymerization aids include alkali metal carboxylates, lithium halides, water, etc., which are generally known as polymerization aids for polyarylene sulfides, but lithium halides are expensive. Particularly preferred are alkali metal carboxylates, water, or a combination of both because of their drawbacks.

  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. , Lithium, sodium, potassium, rubidium and cesium, and n is an integer of 1 to 3). The alkali metal carboxylate can also be used as a hydrate or an aqueous solution. 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. However, since lithium salts and the like are expensive, sodium acetate, potassium acetate, and sodium benzoate are preferable, and sodium acetate is particularly preferable.

  Alkali metal carboxylate is an organic amide solvent in which an organic acid and one or more compounds selected from the group consisting of alkali metal hydroxide, alkali metal carbonate and alkali metal bicarbonate are mixed at approximately equal chemical equivalents. You may form by adding and making it react.

  When the alkali metal carboxylate is used as the polymerization aid, the amount of these polymerization aids used is preferably in the range of 0.2 mol to 0.7 mol with respect to 1 mol of the charged alkali metal sulfide. The range of 0.6 mol is more preferable, and the range of 0.3 to 0.55 mol is more preferable. If it is less than the above range, the effect of increasing the degree of polymerization is insufficient, and if it exceeds the above range, not only the effect of increasing the degree of polymerization beyond that can be obtained, but also an adverse effect depending on the polymerization time.

  Moreover, when using water as a polymerization aid, the range of 0.2 mol-10 mol is preferable with respect to 1 mol of preparation alkali metal sulfide, The range of 0.3-5.0 mol is more preferable, 0.5- A range of 3.0 moles is more preferred. If it is less than the above range, the effect of increasing the degree of polymerization is insufficient, and if it exceeds the above range, not only the effect of increasing the degree of polymerization beyond that can be obtained, but also an adverse effect depending on the polymerization time.

  These polymerization aids may be added before the start of polymerization, during polymerization, or a combination thereof.

-Polymerization stabilizer In this invention, in order to stabilize a polymerization reaction system and to prevent a side reaction, a polymerization stabilizer can also be used. 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 and potassium hydroxide are preferable. Since the alkali metal carboxylate described above also acts as a polymerization stabilizer, it is one of the polymerization stabilizers used in the present invention.

  These polymerization stabilizers can be used alone or in combination of two or more. The polymerization stabilizer is usually 0.01 to 0.2 mol, preferably 0.03 to 0.1 mol, more preferably 0.03 to 0.09 mol, relative to 1 mol of the charged alkali metal sulfide. Used in. If this ratio is small, the stabilizing effect is insufficient. Conversely, if it is too much, it is economically disadvantageous and the polymer yield tends to decrease. The timing for adding the polymerization stabilizer may be before the start of polymerization or during the polymerization.

  In addition, when a part of alkali metal sulfide decomposes | disassembles at the time of spin-drying | dehydration operation and hydrogen sulfide generate | occur | produces, the alkali metal hydroxide produced | generated as a result can also become a polymerization stabilizer.

-Polymerization reaction In the present invention, the alkali metal sulfide and the dihaloaromatic compound in an organic amide solvent, preferably in the presence of a polymerization aid, are preferably within a temperature range of 200 ° C. or higher and lower than 290 ° C. React for 5-20 hours. More preferably, polyarylene sulfide is produced by reacting at a temperature of 245 ° C. to 280 ° C. for 1 to 10 hours.

  Two or more temperature profiles may be used to obtain a higher degree of polymer. In this case, the first stage is 195 ° C. to 240 ° C. for 1 to 10 hours, and the second stage is 240 ° C. to 290 ° C. for 1 to 10 hours.

  When starting the reaction step, the alkali metal sulfide and the dihaloaromatic compound are added to the organic amide solvent in an inert gas atmosphere at a temperature ranging from room temperature to 220 ° C, preferably 100 to 220 ° 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.

  Alkali metal sulfides are usually used in the form of hydrates, but if the water content is less than 0.5 moles per mole of alkali metal sulfide charged, the required amount may be added and replenished. Good. On the other hand, if the alkali metal sulfide contains too much water, before adding the dihaloaromatic compound, the mixture containing the organic amide solvent and the alkali metal compound is heated to remove excess water out of the system. May be. In addition, when water is removed excessively by this operation, a deficient amount of water may be added and replenished.

  As the alkali metal sulfide, an alkali metal sulfide prepared in situ from an alkali metal hydrosulfide and an alkali metal hydroxide in a reaction system or in a separate reactor can also be used. Although there is no particular limitation on this method, desirably an alkali metal hydrosulfide and an alkali metal hydroxide are added to the organic amide solvent in an inert gas atmosphere at room temperature to 150 ° C., preferably in the temperature range of room temperature to 100 ° C. In addition, a method in which the temperature is raised to at least 150 ° C. or more, preferably 180 to 240 ° 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.

-Post-treatment In the present invention, post-treatment after completion of the polymerization reaction can be carried out by a conventional method. For example, after the polymerization reaction is completed, the polyarylene sulfide can be obtained by filtering the cooled product slurry as it is or after diluting with water or the like, filtering it with water and drying it. In addition, after completion of the reaction, the contents are released from the high-temperature reaction system to normal pressure to volatilize and remove the polymerization solvent to recover the polymer, and then heated to volatilize and remove the polymerization solvent, and then washed with water to remove the polymer. A method of recovery is also possible. Further, the polymer may be sieved while the product slurry is kept at a high temperature. In addition, after the above filtration, collection and sieving, the polyarylene sulfide may be washed with the same organic amide solvent as the polymerization solvent, ketones such as acetone, organic solvents such as alcohols, and high-temperature water. The polyarylene sulfide can be treated with an acid such as acetic acid or hydrochloric acid or a salt such as ammonium chloride, calcium acetate or zinc acetate.

[Polyarylene sulfide resin composition]
The polyarylene sulfide resin composition of the present invention can be used in combination with the above polyarylene sulfide (co) polymer in a range that does not impair the effects of the present invention. Addition is preferably used.

  Specific examples of such fillers include glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, Fibrous fillers such as stone kou fiber, metal fibers, or silicates such as talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, silicon oxide, magnesium oxide , Metal compounds such as alumina, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, calcium hydroxide, magnesium hydroxide, water Non-fibrous fillers such as hydroxides such as aluminum fluoride, glass beads, glass flakes, glass powders, ceramic beads, boron nitride, silicon carbide, carbon black and silica, and graphite are used. It is also possible to use two or more kinds of these fillers in combination.

  These fillers may be used after pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound. The organosilane compound is blended in an amount of 0.1 to 3% by weight, preferably 0.5 to 2.5% by weight, based on 100 parts by weight of the polyarylene sulfide resin.

  The polyarylene sulfide resin composition of the present invention may be used by blending other resins together with the polyarylene sulfide (co) polymer as long as the effects of the present invention are not impaired. The blendable resin is not particularly limited, and specific examples thereof include cyclic olefin copolymer, nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, aromatic nylon, and other polyamides, polyethylene terephthalate, poly Polyester resins such as butylene terephthalate, polycyclohexyldimethylene terephthalate, polynaphthalene terephthalate, polyethylene, ethylene butene copolymer, ethylene hexene copolymer, ethylene octene copolymer, polypropylene, polytetrafluoroethylene, carboxyl group, carboxylic acid ester group and acid anhydride group And olefin copolymers having functional groups such as epoxy groups, polyolefin elastomers, polyetherester elastomers, polyethers Amide elastomers, polyamide-imide, polyacetal, polycarbonate resins, polyphenylene ether resins, polysulfone resins, polyethersulfone resins, polyarylate resins, polyether imide resins and polyimides. The above compounds are preferably added in an amount of 10% by weight or less.

  The polyarylene sulfide resin or resin composition of the present invention, together with the above polyarylene sulfide (co) polymer, is a plastic such as a thioether compound, an ester compound, or an organic phosphorus compound within a range that does not impair the effects of the present invention. Agents, crystal nucleating agents such as talc, kaolin, organophosphorus compounds, antioxidants such as hindered phenolic compounds, hindered amine compounds, mold release agents, heat stabilizers, lubricants, strength improvers such as polyfunctional epoxy compounds, Conventional additives such as ultraviolet light inhibitors, colorants, flame retardants and foaming agents can be added.

[Method for producing polyarylene sulfide resin composition]
When the polyarylene sulfide resin composition of the present invention is produced by mixing two or more kinds of polymers and the above compounding agents / additives, a melt kneading method is used as a method for producing the polyarylene sulfide resin composition of the present invention. Preferably mentioned.

  As the production method, it is supplied to a commonly known melt kneader such as a single-screw or twin-screw extruder, a bumper mixer, a kneader, or a mixing roll, and the melting peak temperature of the polyarylene sulfide (co) polymer +5 to 100 A representative example is a method of kneading at a processing temperature of 230 ° C. (230 to 360 ° C.). Specifically, a method of kneading using a twin screw extruder so that the resin temperature during mixing is the melting peak temperature of the polyarylene sulfide (co) polymer +10 to 20 ° C. can be preferably used. .

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

〔metal〕
The metal used in the present invention is not particularly limited, but aluminum, copper, iron, nickel, chromium, magnesium, molybdenum, gold, silver, zinc, tin and alloys based on these are preferably used. Of these, aluminum, copper, iron, nickel, chromium, magnesium, molybdenum, and alloys thereof are particularly preferably used.

  There are no particular restrictions on the metal shape and processing method used in the present invention, but usually cutting, cutting, bending, drawing, etc., that is, sawing, milling, electrical discharge machining, drilling, pressing, grinding, etc. Then, it is processed into a desired shape and structure by machining such as polishing. By these machining processes, a metal part having a shape and structure necessary as a part can be obtained. When the composite of the present invention is obtained by metal insert molding, this metal part becomes an insert product in injection molding.

  It is preferable that the metal part processed into a necessary shape and structure is not formed with an oxide film, a hydroxide film or the like having a thick surface to be bonded. It is preferable to remove dirt other than rust, that is, an oil layer on the surface attached in the metal processing step, finger grease attached on carrying, etc. in the degreasing step described below.

  It is preferable to perform degreasing and cleaning because the surface of the metal is attached with processing oil, finger oil, chips, etc., and fine oil droplets and dirt are attached even after processing by sandblasting or the like. . Usually, the processed alloy part is put into a solvent degreasing machine for degreasing and processed. Or when adhesion | attachment of an oil agent is light, it is preferable to perform the degreasing process which first immerses in the aqueous solution which melt | dissolved the commercially available degreasing agent which is a usual method for several minutes, and is washed with water. Furthermore, it is preferable to prepare a thin caustic soda aqueous solution tank having a concentration of several percent at about 40 ° C. and immerse the alloy parts in the caustic soda aqueous solution tank in order to chemically scrape the surface to give a clean surface. This step is not included in the chemical roughening treatment.

  In addition, acid aqueous solutions such as hydrochloric acid solution, nitric acid solution, 1 hydrogen ammonium difluoride aqueous solution of several percent concentration are prepared in a separate tank at about 40 ° C., and the acid solution used varies depending on the type of metal. If several kinds of solutions are prepared, different alloys can be handled. The alloy-shaped product immersed in an aqueous caustic soda solution and washed with water is immersed in these acid solutions and further washed with water to finish the pretreatment step.

[Physical roughening treatment]
The physical roughening defined in the present invention refers to the contact or collision of fine solid particles or a file-like jig on the metal surface, or irradiation with high-energy electromagnetic rays (ultraviolet rays, plasma, electron beams, etc.). Or roughening the metal surface by physical means such as sputtering.

  There are various methods for industrially available physical roughening. In consideration of industrial productivity and processing cost, sandblasting and grinder processing are particularly preferably used in the present invention. There are various types of abrasives such as sand, steel grid, steel shot, cut wire, alumina, silicon carbide, metal slag, glass beads, plastic beads, etc. Can be selected according to the purpose and application of processing.

  In the present invention, when the insert part is a part of an electric circuit, such as an electric terminal, copper, copper alloy, stainless steel, aluminum or the like is preferably used as the insert metal. At that time, the surface of the metal insert part may be partially or entirely coated by plating or the like before or after physical roughening to the extent that physical surface roughening is not hindered.

  In the present invention, the roughness Ra of the metal surface subjected to the physical roughening treatment is preferably 1 μm to 300 μm, and more preferably in the range.

  The roughness Ra of the metal surface is a center line average roughness defined in JIS B 0601.

[Chemical roughening treatment]
The chemical surface treatment defined in the present invention is a method of chemically roughening a metal surface using a chemical or the like. Below, the method of chemically roughening the metal surface is illustrated.

・ Immersion treatment of aluminum alloy / water-soluble amine compound in aqueous solution Degreased using a commercially available aluminum degreasing agent, washed with water to remove machining oils and fats, and then the aluminum alloy parts Immerse in an aqueous solution of a compound. In this immersion treatment, the surface of the aluminum alloy component is etched to form ultra-fine irregularities by being immersed in one or more aqueous solutions selected from ammonia, hydrazine, and a water-soluble amine compound. Examples of the water-soluble amine compound include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, ethanolamine, allylamine, ethanolamine, diethanolamine, triethanolamine, and aniline.

  These aqueous solutions are preferably adjusted to a weakly basic pH of 9 to 10, and the aluminum alloy immersed for an appropriate period of time is etched into ultra-fine irregularities and covered with irregularities with a diameter of 5 to 100 nm when observed with an electron microscope. It will be a situation. In the case of using an aqueous solution of a water-soluble amine or hydrazine, the aqueous solution having a concentration of 1% to 30% can be used at normal temperature to 70 ° C. for 0.5 minutes to tens of minutes. When ammonia water is used, it can be used at a concentration of about 20% and a dipping time of ten to several tens of minutes at room temperature. After immersion, wash with water and dry with warm air.

・ Aluminum alloy / anodizing treatment Degreased using a commercially available aluminum degreasing agent, washed with water to remove machining oils and oils and fats, cleaned with a pretreatment such as alkali etching and chemical polishing, and then in an acidic aqueous solution. This is a method of forming an aluminum oxide layer having countless fine pores on the surface by electrolysis. The standard alkali etching method is a method in which a 10 to 20% strength aqueous caustic soda solution is brought to 50 to 90 ° C. and immersed in this for 10 seconds to several tens of seconds to dissolve the alloy surface. Usually, it is washed with water and then chemically polished. Chemical polishing is a method in which a high-concentration aqueous solution of an acid such as nitric acid, phosphoric acid, sulfuric acid or the like is set at 80 to 100 ° C. and is immersed therein for several seconds to tens of seconds.

  The surface of the aluminum alloy is shaved by several μm or more in both steps. Subsequently, anodic oxidation is well known, and aluminum is oxidized by applying an electric current in an aqueous solution of sulfuric acid having a concentration of about 10% with an aluminum alloy as an anode at 10 to 20 ° C., and the surface is strong and hard. This is a method of covering with an aluminum layer. If the surface is covered with non-conducting aluminum oxide, electricity will not pass and the oxidation should end there, but in reality, the energization continues and the thickness of the aluminum oxide layer reaches 20 μm. This is because innumerable holes having a diameter of 10 to several tens of nm are opened on the surface of the aluminum oxide layer, and current is continuously passed through the holes. This can also be explained by the fact that when the anodic oxide of aluminum or aluminum alloy having innumerable pores is immersed in an aqueous solution in which the dye is dissolved, the dye enters the pores and is dyed.

  This is further processed and sealed to prevent the dye from escaping, which is dyed alumite. The portion where the recess and the hole are opened is not a metal, but the present invention is naturally effective from the viewpoint of the principle as long as the metal oxide is stronger and harder than the metal. That is, in the present invention, dyeing and sealing are not performed. Also, when the anodic oxidation is completed and the washed water is dried, it is performed at a low temperature. If the temperature at the time of drying is raised too much, aluminum oxide in the opening may react with water to form a hydroxide, deforming the opening and sealing the hole. The drying temperature is preferably 60 to 70 ° C.

・ Surface treatment with copper alloy / triazine thiols Triazine thiols used for surface treatment of metal parts

(In the formula, R ¹ represents —SR ² —OR ² or —NHR ² , and R ² represents a hydrogen atom, an alkyl group, a phenyl group or an alkenyl group. M ¹ and M ² are the same or different. , Hydrogen atom, alkali metal, or 1/2 (alkaline earth metal). In the triazine thiols represented by the general formula (1), as the alkyl group among the groups R ^{2 in} the group: —SR ² , the group: —OR ² or the group: —NHR ² represented by the group R ¹ Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl and the like. Examples of the alkenyl group include vinyl, 1-propenyl, 2-butenyl, 2-pentenyl, 1,3-butanedienyl and the like.

Examples of the alkali metal represented by the groups M ¹ and M ² include sodium and potassium. Examples of the alkaline earth metal include magnesium and calcium.

  Specific examples of the triazine thiols include, for example, 2-octylamino-4,6-dithiol-1,3,5-triazine, 2-anilino-4,6-dithiol-1,3,5-triazine, 2 , 4,6-trithiol-1,3,5-triazine, 2,4-dimercapto-6-sodium mercaptide-1,3,5-triazine, 2-mercapto-4,6-bispotassium mercaptide-1, 3,5-triazine and the like can be mentioned. The surface treatment on the metal part is performed by immersing the metal part in an aqueous solution of the triazine thiols (1) or a solution of an organic solvent, or by applying the solution to the metal. In the case of immersing a metal part in an aqueous solution of triazine thiols (1) or an organic solvent solution, the temperature or immersion time of the aqueous solution or solution is not particularly limited, but the liquid temperature is usually 10 to 40 ° C. It is suitable that the immersion time is set to 1 to 30 minutes, preferably 5 to 10 minutes.

  The organic solvent is not particularly limited, and examples thereof include alcohols such as methanol and ethanol; ketones such as methyl ethyl ketone; esters such as ethyl acetate.

  When surface treatment with triazine thiols is performed, it is preferable to roughen the metal surface in advance by chemical and / or physical treatment. As the roughening treatment of the metal surface, for example, a method of micro-etching with an etching solution such as a strong permanganic acid aqueous solution or a so-called blackening treatment in which an oxide film is formed on the surface with an oxidizing agent is suitable. is there. In particular, when copper is used as a metal part, in order to avoid the pink ring problem caused by the blackening treatment, the so-called MECeth Bond method (Makiyoshiro et al., Electronic materials, 26-30 pages, October 1995 issue) is preferably employed.

  In the present invention, it is preferable that the chemically roughened metal surface is covered with a recess having a number average inner diameter of 10 to 80 nm.

  The number average inner diameter means that the dried metal surface is observed with a field emission scanning electron microscope “JSM-6701F (manufactured by JEOL Ltd.)” at a magnification of 200,000 times, in which one side is 200 nm. Are squared on an electron micrograph of the metal surface, the diameters of the recesses observed therein are all measured on the photograph, and the total is divided by the number of the measured recesses.

  In the case of A5052 (JIS standard) of the aluminum alloy with the clearest phenomenon, when the aqueous amine aqueous solution is adjusted to a weak basicity of about PH10 and immersed at a temperature of about 50 ° C., the inner diameter is 20 to 40 nm immediately. And the depth of the recess becomes the same level as the inner diameter in about 1 minute. When the immersion is further continued, the depth of the concave portion is corroded and deepened, and the edge portion which is the outer periphery forming the concave portion is also corroded by this corrosion, and the inner diameter of the concave portion is further increased on average.

[Method of joining a molded body comprising a polyarylene sulfide resin or a resin composition to a metal when producing a composite molded body]
The composite molded body of the present invention is produced by joining a molded body made of the polyarylene sulfide resin or the resin composition obtained by the above method and a metal. As a bonding method, a polyarylene sulfide resin or resin composition obtained by the above method is applied to a molding method such as blow molding, extrusion molding, injection molding, etc. A two-dimensional molded body or a three-dimensional molded body is obtained in advance, and (1) a vibration welding method or an ultrasonic welding method in which the molded body is bonded to a metal by melting a resin with frictional energy such as vibration energy. , Spin welding method, (2) laser welding method using absorption energy and radiation energy of laser beam, (3) resin molded body is brought close to or brought into contact with a metal plate having a temperature equal to or higher than the melting point of the resin or resin composition The method of crimping can be exemplified first. (4) A metal is placed in the mold in advance, and the polyarylene sulfide resin or resin composition of the present invention is melted by various moldings such as injection molding, extrusion molding, blow molding, transfer molding, and the metal The method of contacting with can be illustrated.

  In the present invention, a method in which a metal is previously placed in a mold and the polyphenylene sulfide resin or resin composition of the present invention is directly bonded to the metal by injection molding is particularly preferable. Specifically, an injection mold is prepared, the movable mold is opened, the metal of the present invention is inserted into one of the molds, the movable mold is closed, and the polyarylene sulfide resin or resin composition of the present invention is injected. In this method, the movable mold is opened and released.

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

(Adjustment of PPS-1)
In a 1 liter autoclave equipped with a stirrer, 118 g (1.00 mol) of 47% sodium hydrosulfide, 42.4 g (1.02 mol) of 96% sodium hydroxide, 163 g (1) of N-methyl-2-pyrrolidone (NMP) .65 mol), 32.0 g (0.39 mol) of sodium acetate, and 150 g of ion-exchanged water, gradually heated to 225 ° C. over about 3 hours while flowing nitrogen at normal pressure, and 210 g of water and 4 g of NMP were distilled. After dispensing, the reaction vessel was cooled to 150 ° C. The amount of hydrogen sulfide scattered was 1.8 mol%. Next, 130.8 g (0.89 mol) of p-dichlorobenzene (p-DCB), 16.2 g (0.11 mol) of m-dichlorobenzene (m-DCB), and 131 g (1.31 mol) of NMP were added. The reaction vessel was sealed under nitrogen gas, heated at a rate of 0.8 ° C./min to 227 ° C. while stirring at 400 rpm, and then heated at a rate of 0.6 ° C./min to 270 ° C. Hold at 170 ° C. for 170 minutes. Meanwhile, 14.4 g (0.8 mol) of water was added over 10 minutes after 30 minutes had passed after reaching 270 ° C. Thereafter, it was cooled to 180 ° C. at a rate of 0.4 ° C./min, and then rapidly cooled to near room temperature. Take out the contents, dilute with 0.5 liters of NMP, filter off the solvent and solids with a sieve (80 mesh), wash the resulting particles several times with 1 liter of warm water, filter and remove the PPS polymer particles Got. This was dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C.

(Adjustment of PPS-2)
PPS except that the addition amount of p-dichlorobenzene (p-DCB) was 117.6 g (0.75 mol) and the addition amount of m-dichlorobenzene (m-DCB) was 29.4 g (0.25 mol). Polymerization, washing, and recovery were performed in the same manner as in -1.

(Adjustment of PPS-3)
Production of PPS-1 copolymerized polyphenylene sulfide resin, except that 1.0 mole of p-dichlorobenzene is used as the main component monomer, and no secondary component monomer is used as the PPS resin mainly containing p-phenylene sulfide units. In the same manner as described above, a PPS resin was produced.

(Adjustment of PPS-1 + 3)
After PPS-1 and PPS-3 were dry blended at a ratio of 1: 1, the cylinder temperature was adjusted to the melting peak temperature of the PPS (co) polymer + 20 ° C. (230 to 230 ° C.) using a TEX30 twin screw extruder manufactured by Nippon Steel Works. 300 ° C.), melt-kneaded with a screw rotation of 200 rpm, and pelletized with a strand cutter.

(Metal degreasing treatment)
A predetermined metal plate was cut into a large number of 18 mm × 45 mm rectangular pieces to obtain metal insert parts. A tank containing 15% of the degreasing material “NE-6 (manufactured by Meltex Co., Ltd.)” was prepared, and the liquid temperature was 75 ° C. It was immersed in this degreasing material aqueous solution for 5 minutes and washed with water. Subsequently, a 1% hydrochloric acid aqueous solution was prepared in another tank, and the liquid temperature was set to 40 ° C. The previous metal plate was immersed here for 1 minute and washed with water. Subsequently, a 1% sodium hydroxide aqueous solution was prepared in another tank, and the liquid temperature was set to 40 ° C. The previous metal plate was immersed here for 1 minute and washed with water. Subsequently, a 1% hydrochloric acid aqueous solution was prepared in another tank, and the liquid temperature was set to 40 ° C. The previous metal plate was immersed here for 1 minute and washed with water.

(Physical surface treatment of metals)
Then, the metal plate which performed the degreasing process was blasted using shot blasting. By this treatment, a metal plate having the following surface roughness (centerline average roughness, JIS B0601) was obtained.
Metal-1: Aluminum, Ra = 600 μm
Metal-2: Copper, Ra = 100 μm
Metal-3: SUS, Ra = 100 μm
Metal-8: Aluminum, Ra = 0.1 μm
Metal-9: Aluminum, Ra = 600 μm.

(Chemical surface treatment of metals)
(Treatment with aluminum / amine compound aqueous solution)
A 1% sodium hydroxide aqueous solution was prepared, and the liquid temperature was 40 ° C. The degreased aluminum alloy piece was immersed for 1 minute and washed with water. Subsequently, a 1% hydrochloric acid aqueous solution was prepared in another tank, and the liquid temperature was set to 40 ° C. The above alloy piece was dipped for 1 minute and recommended. Subsequently, the alloy piece was immersed in a 3.5% monohydric hydrazine aqueous solution at 60 ° C. for 1 minute, washed with water, and dried with a hot air dryer at 60 ° C. for 20 minutes. The aluminum alloy piece was removed from the copper wire and wrapped with aluminum foil, which was then sealed in a polyethylene bag. The next day, a field emission scanning electron microscope “JSM-6701F (manufactured by JEOL Ltd.)” was observed at a magnification of 200,000 times to obtain a metal plate whose entire surface was covered with a recess having the following number average inner diameter. It was.
Metal-4: Aluminum, number of recesses average inner diameter 50 nm
Metal-7: SUS, number of recesses average inner diameter 50 nm
Metal-10: Aluminum, number of recesses average inner diameter 5 nm
Metal-11: Aluminum, number of recesses average inner diameter 500 nm.

(Aluminum / anodizing)
A hole is made in the end of the aluminum alloy plate, and a copper wire coated with vinyl chloride is passed to dozens, and the copper wire is bent and processed so that the aluminum alloy plates do not overlap each other, so that all can be hung at the same time I made it. After putting 7.5% of commercially available degreasing agent “NE-6 (Meltex Co., Ltd.)” for aluminum alloy into water in a tank, heat and dissolve it at 75 ° C., soak the aluminum alloy plate for 5 minutes, Washed with water.

Subsequently, a 10% aqueous solution of caustic soda at 50 ° C. was prepared in another tank, and the aluminum alloy plate was immersed in this for 0.5 minutes and washed with water. Subsequently, a 60% nitric acid solution having a temperature of 90 ° C. was prepared in another tank, which was immersed for 15 seconds and washed with water. Subsequently, a 5% sulfuric acid aqueous solution at 20 ° C. was prepared in another tank, and the anode of the DC power supply device “ASR3SD-150-500 (manufactured by Chuo Seisakusho)” was connected to the hole of the aluminum alloy. The lead plate was connected to a lead plate and anodized by constant current control to obtain a current density of 5 A / dm ² . It was anodized for 40 minutes, washed with water, and placed in a hot air drier at 60 ° C. for 1 hour for drying. One day later, one of them was observed with an electron microscope to obtain Metal-5 having a fine pore opening with a number average inner diameter of 50 nm covering the surface.

(Surface treatment with copper / triazine thiols)
The copper plate was immersed in a 1% methanol solution of triazine thiols (trade name “Disnet F” manufactured by Sankyo Kasei Co., Ltd.) for 5 minutes, and the metal terminal was surface-treated, then washed with water, at room temperature. Drying gave metal-6.

(Injection welding)
Metal plates shown in Tables 1 and 2 were inserted into an injection mold. The structure of the injection mold is shown in FIG. 1. In the figure, 1 is a metal plate, 2 is a movable side plate, 3 is a fixed side plate, 4 is a cavity part where resin is injected, 5 is A pinpoint gate, 6 indicates a bonding surface. When injection joining is performed, an integrated product shown in FIG. 2 is obtained. In FIG. 2, 1 is a metal plate (1.6 mm × 45.0 mm × 18.0 mm), 4 is a resin part (3 mm × 50 mm × 10 mm), 5 is a pinpoint gate, and 6 is a joint surface (5 mm × 10 mm). . The area of the joint surface was 0.5 cm ² . The mold was closed and the resins or resin compositions shown in Tables 1 and 2 were injected to evaluate whether the composite structure shown in FIG. 2 could be obtained. At the time of injection molding, the injection temperature was 270 ° C. to 290 ° C., and the mold temperature was 120 ° C. Further, the obtained composite structure was subjected to a tensile test. The tensile test was performed three times under the condition of a tensile speed of 2 mm / min, and the average shear breaking force of the three times was defined as the shear stress.

  By using the present invention, a molded body made of polyphenylene sulfide resin or a resin composition and a metal shape can be firmly bonded by injection bonding or the like, and the resulting composite structure is not easily peeled off. Therefore, it is possible to make housings, parts, structures, and the like of various devices with many degrees of freedom in terms of shape, structure, and mechanical strength. The housing, parts, and structures manufactured by the present invention are useful for reducing the weight and simplifying the device manufacturing process.

DESCRIPTION OF SYMBOLS 1 Aluminum alloy component 2 Movable side template 3 Fixed side template 4 Component 5 which consists of polyarylene sulfide resin or resin composition 5 Pinpoint gate 6 Joint surface 7 Composite structure

Claims (8)

  A composite structure of a molded body comprising a metal and a polyarylene sulfide resin or resin composition, wherein the metal surface is physically and / or chemically roughened, and the polyarylene sulfide resin or resin composition A polyarylene sulfide resin contained in a product contains a copolymer containing at least a paraarylene sulfide repeating unit and 2 to 20 mol% of a metaarylene sulfide repeating unit based on all repeating units.   2. The composite structure according to claim 1, wherein the roughness Ra of the physically roughened metal surface is 1 μm to 300 μm.   2. The composite structure according to claim 1, wherein the chemically roughened metal surface is covered with a recess having a number average inner diameter of 10 to 80 nm.   4. The composite structure according to claim 1, wherein the chemical roughening treatment is chemical etching treatment or anodizing treatment.   5. The composite structure according to claim 1, wherein the metal is at least one selected from aluminum, copper, iron, nickel, chromium, magnesium, molybdenum, and alloys thereof.   The polyarylene sulfide resin contained in the polyarylene sulfide resin or the resin composition is a polyarylene sulfide (co) polymer not containing a metaarylene sulfide repeating unit, and a polyarylene sulfide copolymer containing a metaarylene sulfide repeating unit; 6. The polyarylene sulfide resin according to claim 1, wherein the polyarylene sulfide resin is 2 to 20 mol% of the metaarylene sulfide repeating unit with respect to all the repeating units of the polyarylene sulfide resin. Composite structure.   The composite structure according to any one of claims 1 to 6, wherein the composite structure is joined by injection welding.   The composite structure according to any one of claims 1 to 6, wherein the molded body is in the form of a film or a sheet and is melt-bonded to a metal.

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