JP6801296B2 - Composite structure and its manufacturing method - Google Patents

Description

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

The present invention relates to a composite structure composed of a metal or an alloy thereof and a resin composition used for electronic devices, home electric appliances, automobile parts, structural parts, mechanical parts and the like. More specifically, metal and resin compositions produced by machining such as cutting, cutting, bending, drawing, that is, machining such as sawing, milling, electric discharge machining, drilling, pressing, grinding, and polishing. It is a structure integrated with a molded body made of an electric discharge machine and a manufacturing method thereof. Various electronic devices, home appliances, medical devices, structural parts for vehicles, vehicle mounting supplies, building materials, other structural parts, exterior parts, etc. The present invention relates to a composite structure of a metal and resin composition used in.

Polyphenylene sulfide resin (hereinafter sometimes abbreviated as PPS resin) has excellent heat resistance, chemical resistance, electrical insulation, moisture and heat resistance, and other properties suitable for engineering plastics. It is used in a wide range of fields, mainly, and is already widely used in composite structures of metal and resin compositions.

As a means for compounding a metal and a resin composition, a method of embedding a part of metal in a resin molded product, a method of forming a hole in the metal and embedding a part of the resin molded product, and a method of fixing with rivets or bolts are known. However, there are many restrictions on the shape of the composite structure, and there are problems such as a decrease in strength due to the occurrence of stress concentration.

For this reason, in applications and shapes in which the bonding strength between the metal and the resin composition affects the strength of the entire structure, the bonding strength on the surface where the metal and the resin composition are in direct contact with each other is required. For example, in automobile applications, a composite structure of a metal and a resin composition is often used for weight reduction, but there is a strong demand for expansion of the applicable range for further weight reduction. However, there 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, complicated processes such as cleaning of the adhesive surface, application of the adhesive, and curing are one of the problems in mass production.

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

For example, Patent Document 1 describes a composite in which a resin composition composed of a polyphenylene sulfide resin and a specific polyolefin resin is injection-molded on a metal whose surface is covered with recesses having a number average inner diameter of 10 nm to 80 nm by immersion treatment in a chemical solution. Body suggestions have been made.

On the other hand, a resin composition containing a core-shell type rubber and glass fiber in a polyphenylene resin is disclosed in Patent Document 2 and the like, but a method for obtaining high bonding strength on a surface in which a metal and a resin composition are in direct contact with each other. Is not disclosed at all.

The present inventors have discovered that a uniquely high bonding strength is exhibited by melting and bonding a surface-treated metal and a specific polyphenylene sulfide resin composition.

JP-A-2007-50630 Japanese Unexamined Patent Publication No. 2011-6555

As described above, the composite structure of the metal and the resin composition is required to have the bonding strength on the surface where the metal and the resin composition are in direct contact with each other, but the technique described in Patent Document 1 is insufficient in the metal bonding property. there were.

An object of the present invention is to obtain a high bonding strength on a surface in direct contact between a metal and a polyphenylene sulfide resin composition, and the molten resin composition is solidified in a state of being in contact with the metal to solidify the metal and polyphenylene. A method of joining the sulfide resin composition, or in a state where the molded product made of the resin composition is in contact with the metal, energy is applied to the resin composition to make it in a molten state, and then it is cooled and solidified to form the metal and the resin composition. An object of the present invention is to obtain a composite molded body having high bonding strength by a bonding method.

That is, the present invention provides the following.
(1) A composite structure of a molded product composed of a metal and a polyphenylene sulfide resin composition.
The surface of the metal is roughened, and the roughening treatment is a physical and / or chemical roughening treatment, and the roughness Ra of the physically roughened metal surface is It is 1 μm to 50 μm, and is characterized in that the chemically roughened metal surface is covered with recesses having a number average inner diameter of 10 to 80 nm.
The polyphenylene sulfide resin composition contains a core made of a rubbery polymer obtained by polymerizing (B) an acrylic monomer with respect to 100 parts by weight of (A) polyphenylene sulfide resin, and a glycidyl group, and is an acrylic simple substance. A composite structure characterized by being a polyphenylene sulfide resin composition comprising 1 to 15 parts by weight of a core-shell type rubber containing a polymerized outermost layer and 10 to 150 parts by weight of (C) glass fiber.
(2) The composite structure according to (1), wherein the chemical roughening treatment is a chemical etching treatment and / or anodizing treatment.
(3) The composite structure of the metal and the polyphenylene sulfide resin composition according to (1) or (2), wherein the metal is aluminum, copper, iron, nickel, chromium, magnesium, molybdenum, or an alloy thereof. body.
(4) The polyphenylene sulfide resin composition is characterized in that 0.1 to 5 parts by weight of the (D) alkoxysilane compound is further blended with respect to 100 parts by weight of the (A) polyphenylene sulfide resin (1). ) The composite structure according to any one of (3) .
(5) The polyphenylene sulfide resin composition is characterized in that (1 ) to 15 parts by weight of (E) epoxy resin is further blended with respect to 100 parts by weight of (A) polyphenylene sulfide resin. 4) Neu composite structure as set forth in any shift.
(6) The major axis of the (C) glass fiber contained in the polyphenylene sulfide resin composition having a cross-sectional area of 2 × 10 ^-5 to 8 × 10 ^-3 mm ² and a cross section perpendicular to the length direction (6). It is characterized by being a glass fiber having a flat cross-sectional shape in which the ratio of the longest straight line distance of the cross section to the short diameter (the longest straight line distance in the direction perpendicular to the long diameter) is between 1.3 to 10. 1) The composite structure according to any one of (5 ) to (5) .
(7) The composite structure according to any one of (1) to (6) joined by injection welding.
(8) The roughened metal contains a core made of a rubbery polymer obtained by polymerizing (B) an acrylic monomer with respect to 100 parts by weight of (A) polyphenylene sulfide resin, and a glycidyl group. A polyphenylene sulfide resin composition containing 1 to 15 parts by weight of a core-shell type rubber containing an outermost layer polymerized with an acrylic monomer and 10 to 150 parts by weight of a glass fiber (C) is melted and brought into contact with a metal. A method for producing a composite structure of a molded product made of a polyphenylene sulfide resin composition .
The roughening treatment was a physical and / or chemical roughening treatment, and the roughness Ra of the physically roughened metal surface was 1 μm to 50 μm, and the chemical roughening treatment was performed. A method for producing a composite structure of a molded body composed of a metal and a polyphenylene sulfide resin composition, wherein the metal surface is covered with recesses having a number average inner diameter of 10 to 80 nm.

According to the present invention, it is possible to obtain a composite structure in which a metal and a molded product made of a polyarylene sulfide resin composition are bonded with high bonding strength.

[Resin composition]
The polyphenylene sulfide resin composition of the present invention contains at least a core made of a rubbery polymer obtained by polymerizing (B) an acrylic monomer with respect to 100 parts by weight of (A) polyphenylene sulfide resin, and a glycidyl group. A polyphenylene sulfide resin composition comprising 1 to 15 parts by weight of a core-shell type rubber containing an outermost layer polymerized with an acrylic monomer and 10 to 150 parts by weight of (C) glass fiber.

(1) Polyphenylene sulfide resin The (A) 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 the polymer containing the repeating unit represented by the above structural formula is preferable. Further, less than 30 mol% of the repeating unit of the PPS resin may be composed of a repeating unit having the following structure or the like.

The smaller the amount of chloroform extracted from the PPS resin, the smaller the oligomer component and the lower the chlorine content. Therefore, the PPS resin used in the present invention has a chloroform extraction amount of 0.5% by weight or less. It is preferable to obtain a low-salt resin composition, and more preferably 0.4% by weight or less.

When the amount of chloroform extracted from the PPS resin exceeds 0.5% by weight, the amount of chloroform extracted from the resin composition using the PPS resin becomes excessive, which is not preferable. In the present invention, as a method for reducing the amount of chloroform extracted, a method of combining a polymerization step and a post-treatment step described later is preferably used. The amount of chloroform extracted from the (A) PPS resin in the present invention was obtained by freezing and crushing the PPS resin using a Soxhlet extractor and extracting for 5 hours using 32 mesh passes, 2.0 g of 42 mesh-on particles, and 200 ml of chloroform. The extract was dried at 50 ° C., the obtained residue was divided by the amount of the charged PPS resin sample, and multiplied by 100 to express a percentage.

The melt viscosity of the (A) PPS resin used in the present invention ranges from 5 to 50 Pa · s (310 ° C., shear rate 1,216 / s) from the viewpoint of obtaining a resin composition having excellent melt fluidity. Preferably, the range of 10 to 45 Pa · s is more preferable, and the range of 10 to 40 Pa · s is further preferable. Further, two or more kinds of polyphenylene sulfide resins having different melt viscosities may be used in combination. The melt viscosity of the (A) PPS resin in the present invention is a value measured using a capillograph manufactured by Toyo Seiki Co., Ltd. under the conditions of 310 ° C. and a shear rate of 1,216 / s.

The method for producing the (A) PPS resin used in the present invention will be described below, but the method is not limited to the following method as long as a PPS resin having the above structure and characteristics can be obtained. However, a method in which dichlorobenzene and a sulfur source are the main monomers (90 mol% or more) and polymerization is carried out in the presence of an aprotic polar solvent is most preferable in terms of production stability.

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

[Polyhalogenated aromatic compounds]
The polyhalogenated aromatic compound used in the present invention 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, and hexa. Polyhalogenated fragrances such as chlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, 1-methoxy-2,5-dichlorobenzene Group compounds are mentioned, preferably p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5- Polychlorobenzene such as tetrachlorobenzene is preferably used, and p-dichlorobenzene is particularly preferably used. It is also possible to combine two or more different polyhalogenated aromatic compounds to form a copolymer, but the p-dihalogenated aromatic compound typified by p-dichlorobenzene can be used as a main component. preferable.

The amount of the polyhalogenated aromatic compound used is 0.8 to 1.023 mol, preferably 0.8 to 1 mol, per mol of the sulfidizing agent, from the viewpoint of obtaining a PPS resin having a viscosity suitable for processing and a low oligomer elution. The range of 1.020 mol, and 0.9 to 1.015 mol is useful from the viewpoint of achieving both the degree of polymerization and low oligomerism useful in the present invention. In the case of the above range, a PPS resin in which the above-mentioned chloroform extraction amount is in a preferable range can be obtained.

[Sulfide agent]
Examples of the sulfidizing agent used in the present invention include alkali metal sulfide, alkali metal hydrosulfide, 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 sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and a mixture of two or more of these, among which sodium hydrosulfide is used. It is preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures, or in the form of anhydrides.

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

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

In the present invention, the amount of the charged sulfidating agent means the residual amount obtained by subtracting the lost amount from the actual charged amount when a partial loss of the sulfidizing agent occurs before the start of the polymerization reaction due to a dehydration operation or the like. It shall be.

It is also possible to use an alkali metal hydroxide and / or an alkaline earth metal hydroxide in combination with the sulfide agent. Specific examples of the alkali metal hydroxide include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide and a mixture of two or more of these, and alkaline earth. Specific examples of the metal hydroxide include calcium hydroxide, strontium hydroxide, barium hydroxide and the like, and sodium hydroxide is preferably used.

When alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use alkali metal hydroxide at the same time, but the amount used is 0.90 to 1. per 1 mol of alkali metal hydrosulfide. An example is in the range of 10 mol, preferably 0.90 to 1.05 mol, more preferably 0.95 to 1.02 mol.

[Polymerization solvent]
In the present invention, an organic polar solvent is 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-imidazolidi. Examples thereof include aprotic organic solvents typified by non-, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphate triamide, dimethylsulfone, tetramethylene sulfoxide, and mixtures thereof, and all of them are used. It is preferably used because of its high reaction stability. Among these, N-methyl-2-pyrrolidone (hereinafter, may be abbreviated as NMP) is particularly preferably used.

The amount of the organic protic 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]
In the present invention, a monohalogen compound (not necessarily an aromatic compound) is used as the polyhalogenated aromatic in order to form the end of the PPS resin to be produced, or to adjust the polymerization reaction or molecular weight. Can be used in combination with compounds. Examples of the monohalogenated compound include monohalogenated benzene, monohalogenated naphthalene, monohalogenated anthracene, a monohalogenated compound containing two or more benzene rings, and a monohalogenated heterocyclic compound. Of these, benzene monohalogenated is preferable from the viewpoint of economy. Specifically, 2-chlorobenzoic acid, 3-chlorobenzoic acid, 4-chlorobenzoic acid, sodium hydrogen 4-chlorophthalate, 2-amino-4-chlorobenzoic acid, 4-chloro-3-nitrobenzoic acid, Examples thereof include 4'-chlorobenzophenone-2-carboxylic acid. 3-Chlorobenzoic acid, 4-chlorobenzoic acid, and sodium hydrogen 4-chlorophthalate are preferable from the viewpoint of reactivity during polymerization and versatility. The monohalogenated compound can also be used for the purpose of adjusting the molecular weight of the PPS resin or for the purpose of reducing the chlorine content of the PPS resin. When the carboxyl group-containing monohalogenated compound is used, the PPS resin It contributes not only to the increase of the carboxyl group content in the medium but also to the decrease of the chlorine content.

[Polymerization aid]
In the present invention, it is also one of the preferable embodiments to use a polymerization aid for adjusting the degree of polymerization. Here, the polymerization aid 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 soils. Examples include metal phosphates. These can be used alone or in combination of two or more. Of these, organic carboxylates, water, and alkali metal chlorides are preferred, and sodium, lithium carboxylates and / or water are particularly preferred.

The alkali metal carboxylate is a general formula R (COOM) n (in the formula, R is an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group having 1 to 20 carbon atoms. M is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium. 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 lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluic acid, and mixtures thereof. Can be mentioned.

The alkali metal carboxylate is a reaction 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 added in approximately equal chemical equivalents and reacted. It may be formed by. Among the above alkali metal carboxylates, the lithium salt is highly soluble in the reaction system and has a large auxiliary effect, but is expensive, and the potassium, rubidium and cesium salts are insufficiently soluble in the reaction system. Therefore, sodium acetate, which is inexpensive and has an appropriate solubility in a polymerization system, is most preferably used.

When these alkali metal carboxylates are used as polymerization aids, the amount used is usually 0.01 mol per 1 mol of the charged sulfidizing agent from the viewpoint of obtaining a PPS resin having a viscosity suitable for processing and low oligomer elution. It is in the range of ~ 2 mol, and is preferably in the range of 0.010 to 0.088 mol from the viewpoint of achieving both the degree of polymerization useful for the present invention and low oligomerism. In the case of the above range, a PPS resin having the above-mentioned melt viscosity in a preferable range can be obtained.

When water is used as a polymerization aid, the amount added is usually in the range of 0.3 mol to 15 mol with respect to 1 mol of the charged sulfidizing agent, and is 0.6 to 10 in the sense of obtaining a higher degree of polymerization. The molar range is preferred, and the range of 1-5 moles is more preferred. Of course, two or more of these polymerization aids can be used in combination. For example, when an alkali metal carboxylate and water are used in combination, it is possible to increase the molecular weight in a smaller amount of each.

The timing of addition of these polymerization aids is not particularly specified, and may be added at any time of the pre-process, the start of polymerization, and the middle of polymerization, which will be described later, or may be added in a plurality of times. When an alkali metal carboxylate is used as the polymerization aid, it is more preferable to add it at the same time as the start of the previous step or the start of polymerization because it is easy to add. When water is used as a polymerization aid, it is effective to add the polyhalogenated aromatic compound in the middle of the polymerization reaction after charging it.

[Polymerization stabilizer]
In the present invention, a polymerization stabilizer can also be used in order to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to the stabilization of the polymerization reaction system and suppresses unwanted side reactions. One guideline for the side reaction is the production of thiophenol, and the production of thiophenol can be suppressed by adding a polymerization stabilizer. 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 them, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferable. Since the above-mentioned alkali metal carboxylate also acts as a polymerization stabilizer, it is one of the polymerization stabilizers used in the present invention. Further, when an alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use the alkali metal hydroxide at the same time, but here, the alkali metal water which is excessive with respect to the sulfidizing agent. Oxides can also be polymerization stabilizers.

These polymerization stabilizers can be used alone or in combination of two or more. The polymerization stabilizer is usually 0.02 to 0.2 mol, preferably 0.03 to 0.1 mol, more preferably 0.04 to 0.09 mol, based on 1 mol of the charged sulfide agent. It is preferable to use it. If this ratio is small, the stabilizing effect is insufficient, and if it is too large, it tends to be economically disadvantageous or the polymer yield tends to decrease.

The timing of addition of the polymerization stabilizer is not particularly specified, and it may be added at any time of the pre-process, the start of polymerization, and the middle of polymerization, which will be described later, or it may be added in a plurality of times. It is more preferable to add them at the same time at the start of the process or at the start of polymerization because the addition is easy.

Next, the method for producing the (A) PPS resin used in the present invention will be specifically described step by step in the pre-step, polymerization reaction step, recovery step, and post-treatment step.

[pre-process]
In the method for producing the (A) PPS resin used in the present invention, the sulfidizing agent is usually used in the form of a hydrate, but before adding the polyhalogenated aromatic compound, an organic polar solvent and a sulfidizing agent are added. It is preferable to heat the temperature of the containing mixture to remove an excess amount of water from the system.

Further, as described above, as the sulfidizing agent, a sulfidizing agent prepared from alkali metal hydrosulfide and alkali metal hydroxide in situ in the reaction system or in a tank separate from the polymerization tank is also used. Can be done. Although this method is not particularly limited, it is desirable to use alkali metal hydrosulfide and alkali metal hydroxide as an organic polar solvent in a temperature range of room temperature to 150 ° C., preferably room temperature to 100 ° C. in an inert gas atmosphere. In addition, there is a method in which the temperature is raised to at least 150 ° C. or higher, preferably 180 to 260 ° C. under normal pressure or reduced pressure to distill off water. A polymerization aid may be added at this stage. Further, in order to promote the distilling of water, toluene or the like may be added to carry out the reaction.

The amount of water in the polymerization system in the polymerization reaction is preferably 0.3 to 10.0 mol per 1 mol of the charged sulfidizing agent. Here, the amount of water in the polymerization system is the amount obtained by subtracting the amount of water removed from the polymerization system from the amount of water charged in the polymerization system. Further, the water to be charged may be in any form such as water, an aqueous solution, and water of crystallization.

[Polymerization reaction step]
In the present invention, 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 mixed in a temperature range of preferably room temperature to 240 ° C., preferably 100 to 230 ° C. in an inert gas atmosphere. .. A polymerization aid may be added at this stage. The order in which these raw materials are charged may be random or simultaneous.

Such a mixture is usually heated to the range of 200 ° C to 290 ° C. The rate of temperature rise is not particularly limited, but a rate of 0.01 to 5 ° C./min is usually selected, and a range of 0.1 to 3 ° C./min is more preferable. In general, the temperature is finally raised to a temperature of 250 to 290 ° C., and the reaction is carried out at that temperature for usually 0.25 to 50 hours, preferably 0.5 to 20 hours. A method of reacting at 200 ° C. to 260 ° C. for a certain period of time before reaching the final temperature and then raising the temperature to 270 to 290 ° C. is effective in obtaining a higher degree of polymerization. At this time, the reaction time at 200 ° C. to 260 ° C. is usually selected in the range of 0.25 hours to 20 hours, preferably in the range of 0.25 to 10 hours.

In addition, in order to obtain a polymer having a higher degree of polymerization, it may be effective to carry out the polymerization in a plurality of steps. When the polymerization is carried out in a plurality of steps, it is effective that the conversion rate 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 (abbreviated as PHA here) is a value calculated by the following formula. The residual amount of PHA can usually be determined by gas chromatography.
(A) When the polyhalogenated aromatic compound is excessively added to the alkali metal sulfide in a molar ratio, conversion rate = [PHA charge amount (mol) -PHA residual amount (mol)] / [PHA charge amount (mol)) -PHA excess (mol)]
(B) In cases other than the above (a) Conversion rate = [PHA charge amount (mol) -PHA residual amount (mol)] / [PHA charge amount (mol)]

[Recovery process]
In the method for producing the (A) PPS resin used in the present invention, a solid substance is recovered from a polymerization reaction product containing a polymer, a solvent and the like after the completion of polymerization. As the PPS resin used in the present invention, any known recovery method may be adopted.

For example, a method of slowly cooling after the completion of the polymerization reaction to recover the particulate polymer may be used. The slow cooling rate at this time is not particularly limited, but is usually about 0.1 ° C./min to 3 ° C./min. It is not necessary to slowly cool at the same rate in the entire process of the slow cooling process, and a method of slowly cooling at a rate of 0.1 to 1 ° C./min until the polymer particles crystallize and precipitate, and then at a rate of 1 ° C./min or more is used. You may adopt it. When the above recovery method is used, a PPS resin in which the above-mentioned chloroform extraction amount is in a preferable range can be obtained.

Further, it is also preferable to carry out the above recovery under quenching conditions, and a flash method is mentioned as a preferable method of this recovery method. The flash method is a method in which a polymerization reaction product is flushed from a state of high temperature and high pressure (usually 250 ° C. or higher, 8 kg / cm2 or higher) into an atmosphere of normal pressure or reduced pressure, and the polymer is recovered in powder form at the same time as solvent recovery. The term "flash" as used herein means that the polymerization reaction product is ejected from the nozzle. Specific examples of the flashing atmosphere include nitrogen or water vapor under normal pressure, and the temperature is usually selected in the range of 150 ° C. to 250 ° C.

Among them, in order to exhibit more excellent low oligomeric properties, a method of slowly cooling after completion of the polymerization reaction to recover the particulate polymer is preferably used in order to enhance the cleaning effect with an organic solvent described later.

[Post-treatment process]
The PPS resin (A) used in the present invention 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 performing acid treatment, it is as follows. The acid used for the acid treatment of the PPS resin in the present invention 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. Of these, acetic acid and hydrochloric acid are more preferably used, but those that decompose and deteriorate PPS resins such as nitric acid are not preferable.

The acid treatment method includes a method of immersing the PPS resin in an acid or an aqueous solution of an acid, and it is also 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 solution of pH 4 heated to 80 to 200 ° C. and stirring for 30 minutes. The pH after the treatment may be 4 or more, for example, pH 4 to 8. The acid-treated PPS resin is preferably washed with water or warm water several times 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 preferable chemical modification of the PPS resin by acid treatment is not impaired.

When hot water treatment is performed, it is as follows. When treating the PPS resin used in the present invention with hot water, the temperature of the hot water is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, still more preferably 150 ° C. or higher, and particularly preferably 170 ° C. or higher. If the temperature is lower 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 exhibit the preferable chemical modification effect of the PPS resin by the hot water washing of the present invention. The operation of the hot water treatment is not particularly limited, and is carried out by a method of putting a predetermined amount of PPS resin into a predetermined amount of water, heating and stirring in a pressure vessel, a method of continuously performing hot water treatment, and the like. The ratio of the PPS resin to water is preferably more than that of water, but usually, a bath ratio of 200 g or less of PPS resin is selected with respect to 1 liter of water.

In addition, the treatment atmosphere is preferably an inert atmosphere in order to avoid decomposition of the terminal groups. Further, the PPS resin that has been subjected to this hot water treatment operation is preferably washed with warm water several times in order to remove residual components.

When cleaning with an organic solvent, it is as follows. The organic solvent used for cleaning the PPS resin in the present invention 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 − Nitrogen-containing polar solvents such as dimethylimidazolidinone, hexamethylphosphorasamide and piperazinones, sulfoxide-sulfone solvents such as dimethylsulfoxide, dimethylsulfone and sulfolane, ketone solvents such as acetone, methylethylketone, diethylketone and acetophenone, Ether-based solvents such as dimethyl ether, dipropyl ether, dioxane, tetrahydrofuran, halogen-based solvents such as chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, tetrachloroethane, perchlorethane, and chlorobenzene. , Methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol and other alcohol / phenol solvents and benzene, toluene, xylene and other aromatic hydrocarbon solvents. Can be mentioned. Among these organic solvents, the use of N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform and the like is preferable, and the use of N-methyl-2-pyrrolidone is particularly preferable in the sense of obtaining a particularly excellent oligomer removing effect. preferable. Moreover, these organic solvents are used in one kind or a mixture of two or more kinds.

As a method of cleaning with an organic solvent, there is a method such as immersing the PPS resin in the organic solvent, and it is also possible to appropriately stir or heat as necessary. The cleaning temperature when cleaning the PPS resin with an organic solvent is not particularly limited, and any temperature of about room temperature to 300 ° C. can be selected. The higher the cleaning temperature, the higher the cleaning efficiency tends to be, but usually, a sufficient effect can be 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 higher than the boiling point of the organic solvent. In addition, there is no particular limitation on the cleaning time. Although it depends on the cleaning conditions, in the case of batch-type cleaning, a sufficient effect is usually obtained by cleaning for 5 minutes or more. It is also possible to wash continuously. Cleaning with such an organic solvent is a process suitable for producing the (A) PPS resin used in the present invention because a high oligomer removing effect can be obtained.

In the present invention, the polyphenylene sulfide resin obtained as described above may be treated by washing with water containing an alkaline earth metal salt. The following method can be exemplified as a specific method for washing the polyphenylene sulfide resin with water containing an alkaline earth metal salt. The type of alkaline earth metal salt is not particularly limited, but alkaline earth metal salts of water-soluble organic carboxylic acids such as calcium acetate and magnesium acetate, and alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide. Is mentioned as a preferable example, and an alkaline earth metal salt of a water-soluble organic carboxylic acid such as calcium acetate or magnesium acetate is particularly preferable. The temperature of the water is preferably room temperature to 200 ° C., more preferably 50 to 90 ° C. The amount of the alkaline earth metal salt used in the water is preferably 0.1 g to 50 g, more preferably 0.5 g to 30 g, based on 1 kg of the dried polyphenylene sulfide resin. The washing time is preferably 0.5 hours or more, more preferably 1.0 hours or more. The preferable washing bath ratio (weight of hot water containing alkaline earth metal salt per unit weight of dry polyphenylene sulfide resin) depends on the washing time and temperature, but hot water containing the above alkaline earth metal is used per 1 kg of dry polyphenylene sulfide. It is preferable to wash with 5 kg or more, and more preferably with 10 kg or more. The upper limit is not particularly limited and may be high, but it is preferably 100 kg or less from the viewpoint of the amount used and the effect obtained. Such hot water washing may be performed a plurality of times.

The PPS resin (A) used in the present invention can also be used after the polymerization is completed by heating in an oxygen atmosphere and by performing thermal oxidative cross-linking treatment by adding a cross-linking agent such as a peroxide to increase the molecular weight. ..

In the case of dry heat treatment for the purpose of increasing the molecular weight by thermal oxidative crosslinking, the temperature is preferably 160 to 260 ° C, more preferably 170 to 250 ° C. Further, it is desirable that the oxygen concentration is 5% by volume or more, more preferably 8% by volume or more. The upper limit of the oxygen concentration is not particularly limited, but is limited to about 50% by volume. The treatment time is preferably 0.5 to 100 hours, more preferably 1 to 50 hours, still more preferably 2 to 25 hours. The heat treatment device may be a normal hot air dryer or a rotary type or a heating device with a stirring blade, but for efficient and more uniform processing, a heating device with a rotary type or a stirring blade is used. It is more preferable to use it.

However, from the viewpoint of achieving both low oligomer elution and excellent melt fluidity, introduction of a crosslinked structure is not so preferable, and linear PPS is preferable.

In addition, it is possible to perform a dry heat treatment for the purpose of suppressing thermal oxidation cross-linking and removing volatile components. The temperature is preferably 130 to 250 ° C, more preferably 160 to 250 ° C. Further, the oxygen concentration in this case is preferably less than 5% by volume, more preferably less than 2% by volume.

The treatment time is preferably 0.5 to 50 hours, more preferably 1 to 20 hours, still more preferably 1 to 10 hours. The heat treatment device may be a normal hot air dryer or a rotary type or a heating device with a stirring blade, but for efficient and more uniform processing, a heating device with a rotary type or a stirring blade is used. It is more preferable to use it.

In the present invention, using a PPS resin in which the ash content of the PPS resin is reduced to 0.2% by weight or less by deionization or the like makes the resin composition containing the PPS resin more excellent toughness and molding process. It is preferable in terms of obtaining sex. Specific examples of such deionization treatment include acid aqueous solution cleaning treatment, hot water cleaning treatment, organic solvent cleaning treatment, and the like, and these treatments may be used in combination of two or more methods. Here, the following method can be mentioned for measuring the ash content. About 5 g of the dry PPS raw powder is weighed in a platinum crucible and fired on an electric stove until it becomes a black mass. Next, firing is continued in an electric furnace set at 550 ° C. until the carbides are completely calcined. After cooling in a desiccator, the weight can be measured and the ash content can be calculated by comparing with the initial weight. The lower limit of the ash content of the PPS resin is ideally 0, but a PPS resin having an ash content of 0.1% by weight or more can be preferably used.

For example, by adopting the above-mentioned production method, it is possible to obtain an (A) PPS resin having excellent oligomer low elution and melt fluidity, and the present invention uses the (A) PPS resin. It is preferable to use it.

(2) Core-shell type rubber The polyphenylene sulfide resin composition of the present invention comprises a core composed of (A) a rubbery polymer obtained by polymerizing at least an acrylic monomer with respect to 100 parts by weight of the polyphenylene sulfide resin. , 0.5 to 15 parts by weight of a core-shell type rubber containing an outermost layer containing a glycidyl group and polymerizing an acrylic monomer.

The core-shell type rubber (B) used in the present invention is composed of a core layer (innermost layer) and one or more layers (shell layers) covering the core layer, and adjacent layers are composed of different kinds of polymers. It is a polymer having such a structure. The number of layers constituting the core-shell type rubber is not particularly limited, and may be two or more layers, and may be three or more layers or four or more layers. The core-shell type rubber is a core-shell type rubber containing a rubbery polymer obtained by polymerizing an acrylic monomer as a core and an outermost layer containing a glycidyl group and polymerizing an acrylic monomer. It may have different layers.

In the present invention, in order to obtain high bonding strength on the surface in direct contact with the resin composition, which is the effect of the present invention, a core made of a rubbery polymer polymerized with an acrylic monomer and a glycidyl group. It is necessary to add a core-shell type rubber containing an outermost layer in which an acrylic monomer is polymerized.

The type of the rubber layer of the (B) core-shell type rubber used in the present invention is not particularly limited as long as it is a rubber polymer obtained by polymerizing an acrylic monomer, and two or more types can be combined with a silicone component or the like. A rubber composed of a copolymer is also preferable. For example, a combination of a rubber composed of a polymerized component of an acrylic component such as an ethyl acrylate unit or a butyl acrylate unit and a rubber composed of a polymerized component of a silicone component such as a dimethylsiloxane unit or a phenylmethylsiloxane unit. That is, a rubber composed of an acrylic component such as an ethyl acrylate unit or a butyl acrylate unit and a component obtained by copolymerizing a silicone component such as a dimethylsiloxane unit or a phenylmethylsiloxane unit is also preferable. The type of the outermost layer of the core-shell type rubber (B) used in the present invention is not particularly limited as long as the outermost layer contains a glycidyl group and is a polymer of an acrylic monomer. Examples of the glycidyl group-containing compound contained in the above include polymers of glycidyl group-containing vinyl-based units. Specific examples of the glycidyl group-containing vinyl-based unit include glycidyl (meth) acrylate, glycidyl itaconic acid, diglycidyl itaconic acid, allyl glycidyl ether, styrene-4-glycidyl ether, and 4-glycidyl styrene. In the present invention, glycidyl (meth) acrylate is most preferably used in order to obtain high bonding strength on the surface in direct contact with the resin composition, which is the effect of the present invention. These units may be used alone or in combination of two or more.

As a preferable specific example of the core-shell type rubber (B) used in the present invention, the core layer is a butyl acrylate polymer, the outermost layer is a methyl methacrylate / glycidyl methacrylate copolymer, and the core layer is a dimethylsiloxane / butyl acrylate copolymer. Examples of the polymer include a methyl methacrylate / glycidyl methacrylate copolymer as the outermost layer, and among these, most preferably, high bonding strength can be obtained on the surface in direct contact with the resin composition. The core layer is a butyl acrylate polymer and the outermost layer is a methyl methacrylate / glycidyl methacrylate copolymer.

The particle size of the core-shell type rubber (B) used in the present invention is not particularly limited, but the primary particle size is preferably 0.05 to 1 μm, preferably 0.1 to 0.8 μm. Is more preferable, and most preferably 0.2 to 0.6 μm.

In the core-shell type rubber (B) used in the present invention, the weight ratio of the core to the shell is not particularly limited, but the core layer is preferably 50 to 95 parts by weight with respect to the entire core-shell type rubber. It is more preferably 55 to 93 parts by weight, and most preferably 60 to 90 parts by weight.

As a commercially available variety of (B) core-shell type rubber used in the present invention, for example, Pararoid (registered trademark) EXL2314 can be obtained from Rohm and Haas.

The blending amount of the (B) core-shell type rubber used in the present invention is 1 to 15 parts by weight with respect to 100 parts by weight of the (A) polyphenylene sulfide resin. If the blending amount of the core-shell type rubber (B) is less than 1 part by weight with respect to 100 parts by weight of the (A) polyphenylene sulfide resin, the bonding strength of the surface in direct contact with the resin composition decreases. 3 parts by weight or more is preferable. Even if the blending amount of the (B) core-shell type rubber exceeds 15 parts by weight with respect to 100 parts by weight of the (A) polyphenylene sulfide resin, the bonding strength of the surface in direct contact with the resin composition decreases. It is preferably 10 parts by weight or less.

(3) Glass Fiber The polyphenylene sulfide resin composition of the present invention comprises at least 10 to 150 parts by weight of (C) glass fiber blended with 100 parts by weight of (A) polyphenylene sulfide resin.

The cross-sectional shape of the (C) glass fiber used in the present invention is not limited, but is flat, eyebrows, oval, elliptical, semicircular or arcuate, rectangular, or in that the warp of the molded product is improved. These similar cross-sectional shapes are preferable, and a flat cross-sectional shape is more preferable.

The fiber diameter of the glass fiber (C) of the present invention having a round cross-sectional shape (hereinafter, may be abbreviated as round glass fiber) is preferably 4 μm or more and 25 μm or less, more preferably 6 μm or more and 20 μm. It is as follows.

Further, in the present invention, the round glass fiber (C) is preferably opened in the polyphenylene sulfide resin composition. Here, the open fiber state means a state in which the round glass fiber (C) in the polyphenylene sulfide resin composition is opened to a single fiber, and specifically, the observed reinforcing fiber. It means that the number of reinforcing fibers bundled in 10 or more is 40% or less of the total number of reinforcing fibers.

The round glass fiber (C) used in the present invention is preferably treated with a converging agent or a surface treatment agent. Examples of the convergent or surface treatment agent include functional compounds such as epoxy compounds, isocyanate compounds, silane compounds and titanate compounds, and epoxy compounds having a high epoxy content are used from the viewpoint of improving the moist heat resistance of reinforcing fibers. Is particularly preferable.

The glass fiber (C) of the present invention having a round cross-sectional shape can be obtained from, for example, Nippon Electric Glass Co., Ltd. under the trade name T-760H.

The glass fiber (C) of the present invention having a flat cross-sectional shape (hereinafter, may be abbreviated as flat glass fiber) has a major axis (the longest cross section) in a cross section perpendicular to the length direction. The ratio of the minor axis (the longest linear distance in the direction perpendicular to the major axis) is 1.3 to 10, preferably 1.5 to 5, and more preferably 1.5 to 4.

It is preferable to use a glass fiber having a major axis to minor axis ratio of 1.3 or more because the bonding strength with a metal can be further increased. Further, if the ratio exceeds 10, the production itself is difficult. Further, as the glass fiber, a hollow fiber can be used for the purpose of reducing the specific gravity.

(C) As the cross-sectional area of the flat glass fiber increases, a sufficient reinforcing effect cannot be obtained, and if it is too small, it becomes difficult to manufacture the flat glass fiber itself, and there is a problem in handling. Therefore, the cross-sectional area of the (C) flat glass fiber in the present invention is 2 × 10 ^-5 to 8 × 10 ^-3 mm ² , preferably 8 × 10 ^-5 to 8 × 10 ^-3 mm ² , and particularly preferably 8 ×. It is ^10-5 to 8 × 10 ^-4 mm ² .

(C) The length of the flat glass fiber is arbitrary, but due to the balance between the mechanical properties of the molded product and the deformation, a shorter length is preferable in order to reduce the amount of deformation of the molded product, but in terms of mechanical strength. Therefore, it is preferable that the average fiber length is at least 30 μm or more and is long, and it is appropriately selected according to the required performance. Usually, 50 to 1000 μm is preferable.
(C) The ratio, cross-sectional area, and length of the major axis to the minor axis of the flat glass fiber can be obtained from the observation image by observing the cross section of the glass fiber with a scanning electron microscope (SEM).

When using these (C) flat glass fibers, it is desirable to use a converging agent or a surface treatment agent if necessary. To show this example, it is a functional compound such as an epoxy compound, an isocyanate compound, a silane compound, and a titanate compound. These compounds may be used after being surface-treated or converged in advance, or may be added at the same time as the material preparation.

(C) The flat glass fiber is prepared by spinning using a nozzle having an appropriate hole shape such as an oval shape, an elliptical shape, a rectangular shape, or a slit shape as a bushing used for discharging molten glass. Further, it is prepared by spinning molten glass from a plurality of nozzles provided in close proximity having various cross-sectional shapes (including a circular cross section) and joining the spun molten glass to each other to form a single filament. it can.

(C) As a commercially available flat glass fiber, for example, CSG3PA-830 (registered trademark) can be obtained from Nitto Boseki Co., Ltd.

The blending amount of the (C) glass fiber used in the present invention is 10 to 150 weight by weight with respect to 100 parts by weight of the (A) polyphenylene sulfide resin. If the blending amount of the glass fiber (C) is less than 10 parts by weight with respect to 100 parts by weight of the (A) polyphenylene sulfide resin, the bonding strength of the surface in direct contact with the resin composition decreases. It is preferably 30 parts by weight or more. Even if the blending amount of the glass fiber (C) exceeds 150 parts by weight with respect to 100 parts by weight of the (A) polyphenylene sulfide resin, the bonding strength of the surface in direct contact with the resin composition decreases. It is preferably 70 parts by weight or less.

(4) Alkoxysilane compound The polyphenylene sulfide resin composition of the present invention preferably contains 0.1 to 5 parts by weight of the (D) alkoxysilane compound with respect to 100 parts by weight of the (A) polyphenylene sulfide resin. ..

By using the (D) alkoxysilane compound of the present invention, it is possible to obtain the effect of improving the bonding strength of the surface in direct contact with the resin composition in combination with other essential components.

Examples of the (D) alkoxysilane compound used in the present invention include an epoxy group-containing alkoxysilane compound, an amino group-containing alkoxysilane compound, a ureido group-containing alkoxysilane compound, an isocyanato group-containing alkoxysilane compound, a mercapto group-containing alkoxy compound, and a hydroxyl group-containing alkoxy. Examples include silane compounds.

In the present invention, the (D) alkoxysilane compound can be used alone or in combination of two or more.

Specific examples include epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysisilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ. Amino group-containing alkoxysilane compounds such as-(2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane , Γ-Ureidopropyltrimethoxycisilane, ureido group-containing alkoxysilane compounds such as γ- (2-ureidoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, Contains isocyanato groups such as γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane A mercapto group-containing alkoxysilane compound such as an alkoxysilane compound, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, and a hydroxyl group-containing alkoxysilane such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane. Examples include compounds.

Preferred are epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and amino group-containing compounds such as γ-aminopropyltrimethoxysilane. Examples thereof include isocyanato group-containing alkoxysilane compounds such as alkoxysilane compounds and γ-isocyanatopropyltriethoxysilane.

Examples of commercially available products of the alkoxysilane compound (D) include KBM303 (registered trademark), KBE9007 (registered trademark), KBE903 (registered trademark) from Shin-Etsu Silicone Co., Ltd., and SH6040 (registered trademark) from Toray Dow Corning Co., Ltd. Registered trademark) is available.

The blending amount of the (D) alkoxysilane compound used in the present invention is 0.1 to 5% by weight with respect to 100 parts by weight of the above (A) polyphenylene sulfide resin. If the amount of the (D) alkoxysilane compound is less than 0.1 part by weight with respect to 100 parts by weight of the (A) polyphenylene sulfide resin, the bonding strength of the surface in direct contact with the resin composition decreases. Even if the blending amount of the (D) alkoxysilane compound exceeds 5 parts by weight with respect to 100 parts by weight of the (A) polyphenylene sulfide resin, the bonding strength of the surface in direct contact with the resin composition decreases. It is preferably 3 parts by weight or less.

(5) Epoxy Resin The polyphenylene sulfide resin composition of the present invention is preferably prepared by blending 0.5 to 15 parts by weight of (E) epoxy resin with respect to 100 parts by weight of (A) polyphenylene sulfide resin.

By using the epoxy resin (E) of the present invention, it is possible to obtain the effect of improving the bonding strength of the surface in direct contact with the resin composition in combination with other essential components.

As the epoxy resin (E) used in the present invention, a liquid or solid resin containing two or more epoxy groups can be used.

In the present invention, the epoxy resin (E) can be used alone or in combination of two or more.

Specific examples include 2,2-bis (4'-hydroxyphenyl) propane (bisphenol A), bis (2-hydroxyphenyl) methane (bisphenol F), 4,4'-dihydroxydiphenyl sulfone (bisphenol S), 4 , 4'-dihydroxybiphenyl, resorcin, saligenin, trihydroxydiphenyldimethylmethane, tetraphenylol ethane, these halogen and alkyl group substituents, butanediol, ethylene glycol, erythritol, novolak, glycerin, polyoxyalkylene, etc. Glycidyl ether type synthesized from epichlorohydrin and other compounds containing two or more hydroxyl groups in the molecule, glycidyl ester type such as phthalic acid glycidyl ester, aniline, diaminodiphenylmethane, metaxylene diamine, 1,3-bisaminomethyl Epoxy resins containing glycidyl groups such as glycidylamines synthesized from primary or secondary amines such as cyclohexane and epichlorohydrin, etc., epoxidized soybean oil, epoxidized polyolefins, vinylcyclohexendioxides, dicyclopentadiene Epoxy resins that do not contain glycidyl groups such as oxides can be mentioned.

Preferred examples include glycidyl ether of bisphenols such as bisphenol A, bisphenol F and bisphenol S, and bisphenol type epoxy resin such as glycidyl ester. Particularly preferable is a bisphenol A type epoxy resin.

As a commercially available epoxy resin (E), for example, JER1009 (registered trademark) can be obtained from Mitsubishi Chemical Corporation.

The blending amount of the (E) epoxy resin used in the present invention is 0.5 to 15 parts by weight with respect to 100 parts by weight of the above (A) polyphenylene sulfide resin. If the blending amount of the epoxy resin (E) is less than 0.5 parts by weight with respect to 100 parts by weight of the polyphenylene sulfide resin (A), the bonding strength of the surface in direct contact with the resin composition decreases. Even if the blending amount of the epoxy resin (E) exceeds 15 parts by weight with respect to 100 parts by weight of the polyphenylene sulfide resin (A), the bonding strength of the surface in direct contact with the resin composition decreases. It is preferably 10 parts by weight or less.

The polyphenylene sulfide resin composition in the present invention includes other components such as heat-resistant stabilizers (hindered phenol-based, hydroquinone-based, phosphite-based and substitutes thereof, etc.) and antistatic agents within the range not impairing the effects of the present invention. (Resolsinol type, salicylate type, benzotriazole type, benzophenone type, hinderedamine type, etc.), mold release agent and antistatic agent (montanoic acid and its metal salt, its ester, its half ester, stearyl alcohol, stearamide, various bisamides, bisurea and Polyethylene wax, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black for coloring, etc.), dyes (niglosin, etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agents (alkylsulfate, etc.) Type anionic antistatic agent, quaternary ammonium salt type cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monoesterate, betaine type amphoteric antistatic agent, etc., flame retardant (for example, red) Hydroxide such as phosphorus, phosphoric acid ester, melamine cyanurate, magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin or brominated flame retardants thereof And other polymers (eg, amorphous resins such as polyamideimide, polyarylate, polyether sulfone, polysulfone, polyphenylene ether, etc.) can be added.

In the polyphenylene sulfide resin composition of the present invention, it is preferable that the above (A) to (E) and other components blended as necessary are uniformly dispersed.

As a method for producing the polyphenylene sulfide resin composition of the present invention, for example, a method of melt-kneading each component using a known melt-kneader such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader or a mixing roll. Can be mentioned. Each component may be mixed in advance and then melt-kneaded. Further, as a method of charging each component into the melt-kneader, for example, a single-screw or twin-screw extruder is used, and the screw root is used. The components (A), (B), (D), and (E) are supplied from the main inlet installed on the side, and (C) glass is supplied from the sub inlet installed between the main inlet and the tip of the extruder. Examples thereof include a method of supplying fibers and melting and mixing them.

The melt-kneading temperature is preferably 220 ° C. or higher, more preferably 280 ° C. or higher, in terms of excellent fluidity and mechanical properties. Further, 400 ° C. or lower is preferable, and 360 ° C. or lower is more preferable. Here, the melt-kneading temperature refers to the set temperature of the melt-kneading machine, for example, in the case of a twin-screw extruder, it refers to the cylinder temperature.

〔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 containing these as main components are preferably used. Among them, aluminum, copper, iron, nickel, chromium, magnesium, molybdenum, and alloys thereof are particularly preferably used.

The shape and processing method of the metal used in the present invention are not particularly limited, but usually cutting, cutting, bending, drawing, etc., that is, sawing, milling, electric discharge machining, drilling, pressing, grinding, etc. It is processed into a desired shape and structure by machining such as polishing. By these machining, a metal part having a shape and structure required as a part can be obtained. When the composite structure of the present invention is obtained by metal insert molding, this metal part becomes an insert product by injection molding.

It is preferable that the metal portion processed into the required shape and structure does not have an oxide film, a hydroxide film, or the like having a thick surface to be adhered. It is preferable to remove stains other than rust, that is, an oil layer on the surface attached in the metal processing process, finger oil attached by carrying, and the like in the degreasing step described below.

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

In addition, an acidic aqueous solution such as a hydrochloric acid aqueous solution, a nitric acid aqueous solution, or a hydrogen difluorinated ammonium aqueous solution having a concentration of several percent is prepared in another tank at about 40 ° C., and the acid solution used differs depending on the type of metal. Different alloys can be used by preparing several kinds of solutions. The alloy-shaped material that has been immersed in an aqueous solution of caustic soda and washed with water is immersed in these acid solutions and further washed with water to complete the pretreatment step.

[Metal roughening treatment]
The roughening treatment method for the metal constituting the present invention is not particularly limited, and can be performed by using a known technique according to the material and shape of the metal and the required performance. Specifically, for example, blasting, laser processing, chemical etching, anodizing, etc. can be used as the physical roughening treatment, and one or more of them may be used. .. The chemical etching and anodizing methods are preferable because they can stably form fine pores of a dozen nm to several tens of nm.

Specifically, for example, TRI (Toa Denka Co., Ltd. registered trademark) that forms an adhesive layer on a metal surface using an adhesive containing a specific triazine compound and an organic compound capable of chemically reacting with the specific triazine compound. ) NMT (Taisei Brass) that forms fine irregularities on the metal surface by sequentially performing post-treatment such as degreasing treatment with alkaline solution, neutralization treatment with acidic solution, immersion treatment with hydrazine-based special solution, washing with water and drying on the metal surface. Surface treatment can also be promoted by a surface treatment technology called Amalfa (registered trademark of MEC Co., Ltd.) that treats the metal surface in a special etching solution.

[Physical roughening process]
The physical roughening defined in the present invention means that fine solid particles or a sand-like jig are brought into contact with or collide with a metal surface, or high-energy electromagnetic rays (ultraviolet rays, plasma, electron beams, lasers, etc.) are applied. It refers to roughening the metal surface by physical means such as irradiation or sputtering.

There are various methods of physically roughening that can be used industrially, but in consideration of industrial productivity and processing cost, sandblasting and grinder treatment 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., and the particle size is also various, but these Is used properly according to the purpose and purpose of processing.

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

In the present invention, the roughness Ra of the physically roughened metal surface is preferably 1 μm to 50 μm, and more preferably 1 μm to 10 μm.

The roughness Ra of the metal surface is the center line average roughness defined by JIS B 0601: 2013.

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

-Immersion treatment of water-soluble amine-based compound in aqueous solution After degreasing and washing with water using a commercially available metal degreasing agent to remove machining oil and fats and oils, metal parts are subjected to an aqueous solution of water-soluble amine-based compound. Immerse in. In this dipping treatment, the surface of the aluminum alloy component is etched in order to form ultrafine irregularities by immersing it 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 be weakly basic with a pH of 9 to 10, and the surface of the metal soaked for an appropriate time is etched into ultrafine irregularities, and when observed with an electron microscope, it is covered with an uneven portion having a diameter of 5 to 100 nm. It will be a broken situation. When an aqueous solution of water-soluble amine or hydrazine is used, it can be used as an aqueous solution having a concentration of 1% to 30% for 0.5 minutes to a dozen minutes at room temperature to 70 ° C. When ammonia water is used, it can be used at a concentration of about 20% at room temperature for a dozen to several tens of minutes of immersion time. After soaking, wash with water and dry with warm air.

・ Anodization treatment After degreasing with a commercially available metal degreasing agent and washing with water to remove machining oil and fats and oils, the surface is cleaned by pretreatment such as alkaline etching and chemical polishing, and electrolysis is performed in an acidic aqueous solution. This is a method of forming an aluminum oxide layer having innumerable fine pores on the surface. The standard alkaline etching method is a method in which a caustic soda aqueous solution having a concentration of 10 to 20% is set at 50 to 90 ° C. and immersed in the caustic soda aqueous solution for 10 to several tens of seconds to dissolve the alloy surface. It is usually 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, or sulfuric acid is set at 80 to 100 ° C. and immersed therein for several seconds to ten and several seconds.

The metal surface is scraped by several μm or more in both steps. Next is anodization, but it is well known that the metal is used as an anode and is energized in a sulfuric acid aqueous solution at 10 to 20 ° C. at a concentration of about 10% to oxidize the metal, and the surface is made into a tough and hard oxide layer. It is a method of covering with. If the metal surface is covered with a non-conducting oxide layer, electricity will not pass and oxidation should end there, but in reality, electricity continues to be applied, and the thickness of the oxide layer reaches more than 20 μm. This is because innumerable pores having a diameter of a dozen to several tens of nm are opened on the surface of the oxide layer, and electricity is continuously applied through the pores. This can be seen from the fact that when a metal anodized oxide with innumerable pores is immersed in an aqueous solution dissolved in a dye, the dye enters the pores and is dyed. Dyeing alumite is made of aluminum, which is further treated to seal the holes so that the dye does not escape. Although the recessed or perforated portion itself is not a metal, the present invention is naturally effective in principle as long as it is a metal oxide that is stronger and harder than the metal. That is, in the present invention, dyeing and sealing are not performed. Also, when the anodizing is completed and the product washed with water is dried, it is performed at a low temperature. If the temperature during drying is raised too much, the metal oxide in the opening may react with water to form a hydroxide, which may deform the opening and close the hole. The drying temperature is preferably 60 to 70 ° C.

-Surface treatment with triazine thiols The triazine thiols used for surface treatment of metal parts are represented by the following formula (1).

(In the formula, R ¹ represents -SR2-OR2 or -NHR2, R2 represents a hydrogen atom, an alkyl group, a phenyl group or an alkenyl group. M ¹ and M ² may be the same or different. It is represented by a hydrogen atom, an alkali metal, or 1/2 (alkaline earth metal). In the triazine thiols represented by the above general formula (1), when R ¹ and R 2 are alkyl groups, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and t-butyl. Group etc. can be mentioned. In the case of an alkenyl group, for example, a vinyl group, a 1-propenyl group, a 2-butenyl group, a 2-pentenyl group, a 1,3-butanjienyl group and the like can be mentioned.

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

Specific examples of the above 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, Examples thereof include 3,5-triazine. The surface treatment of the metal part is performed by immersing the metal part in the aqueous solution of the triazine thiols (1) or a solution of an organic solvent, or by applying the solution to the metal. When the metal part is immersed in an aqueous solution of triazinethiols (1) or a solution of an organic solvent, the temperature and immersion time of the aqueous solution or solution are not particularly limited, but the liquid temperature is usually set to 10 to 40 ° C. It is preferable to set the immersion time to 1 to 30 minutes, preferably 5 to 10 minutes.

The organic solvent is also not particularly limited, and examples thereof include alcohols such as methanol and ethanol; ketones such as methyl ethyl ketone; and 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. For the roughening treatment of the metal surface, for example, a method of performing microetching with an etching solution such as an aqueous solution of permanganate having a strong oxidizing power, a so-called blackening treatment of forming an oxide film on the surface with an oxidizing agent, or the like is preferable. is there. In particular, when copper is used as a metal part, the so-called ME Ceth Bond method (Yoshiro Maki et al., Electronic materials) in which etching is performed in combination with chelating action and air oxidation in order to avoid the problem of pink ring caused by blackening treatment. , 26-30, October 1995 issue) is preferred.

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

The number average inner diameter means that the surface of the metal after drying is observed with a scanning electron microscope "S-4800 (manufactured by Hitachi, Ltd.)" at a magnification of 100,000 times, and a square having a side of 200 nm is observed therein. Was partitioned on an electron micrograph of the metal surface, all the diameters of the concave objects observed therein were measured on the photograph, and the total was divided by the number of the measured recesses.

Taking the example of A5052 (JIS standard), which is the most obvious aluminum alloy, when a water-soluble 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 immediately 20 to 40 nm. The recesses are generated, and the depth of the recesses reaches the same level as the inner diameter in about 1 minute. Then, as the immersion is continued, the depth of the recess is corroded and becomes deeper. This corrosion also corrodes the edge portion which is the outer circumference forming the recess, and the inner diameter of the recess is further increased on average.

[Method of joining a polyphenylene sulfide resin composition and a metal in producing a composite molded product]
The composite molded product of the present invention is produced by joining a metal with the polyphenylene sulfide resin composition obtained by the above method. As a joining method, a molding method such as blow molding, extrusion molding, or injection molding is applied to the polyphenylene sulfide resin composition obtained by the above method to form a fibrous one-dimensional molded product, a film sheet, or the like. A vibration welding method or an ultrasonic welding method in which a dimensional molded body or a three-dimensional molded body is obtained in advance, and the resin composition molded body is joined to a metal by melting the resin with frictional energy such as (1) vibration energy. , Spin welding method, (2) Laser welding method using the absorbed energy of the laser beam and its radiant energy, (3) The resin molded product 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 composition and heat-bonded. First, the method can be illustrated. (4) A metal is placed in a mold in advance, and the polyphenylene sulfide resin composition of the present invention is melted by various moldings such as injection molding, extrusion molding, blow molding, and transfer molding, and is brought into contact with the metal at the same time. The method can be exemplified.

In the present invention, a method in which the metal is pre-installed in the mold and the polyphenylene sulfide resin composition of the present invention is directly bonded to the metal by injection molding can be mentioned as a particularly preferable method. Specifically, an injection molding die is prepared, the movable die is opened, the metal of the present invention is inserted into one of them, the movable die is closed, the polyphenylene sulfide resin composition of the present invention is injected, and the movable die is injected. This is a method of opening and releasing the mold.

In this method, when injection molding is performed, the mold temperature and the injection temperature may be set higher than usual to obtain higher bonding strength.

Examples are shown below, and the present invention will be described in more detail, but the present invention is not limited to the description of these examples.

[Measuring method]
(1) Chloroform extraction amount of PPS resin Using a Soxhlet extractor, PPS sample amount of about 10 g and chloroform of 200 ml were used for extraction for 5 hours, the extract was dried at 50 ° C., and the obtained residue was charged with the amount of PPS sample. It is divided and multiplied by 100 to express a percentage.

(2) Melt flow rate (MFR) of PPS resin
The measurement temperature was 315.5 ° C. and a load of 5000 g, and the measurement was performed by a method according to ASTM-D1238-70.

(3) Metal joint strength Using an injection molding machine (SE-50D) manufactured by Sumitomo Heavy Industries, the cylinder temperature is 320 degrees, the mold temperature is 140 ° C, and the injection pressure = molding lower limit pressure + 10 MPa conforms to ISO19095-2 Type A. The test piece (composite structure) was molded. The obtained composite structure was subjected to a tensile test under a tensile speed of 2 mm / min to measure the metal bonding strength. It can be said that it is good if the metal bonding strength is 33 MPa or more. 40 MPa or more is desirable.

[Ingredients used]
[Reference Example 1] Polymerization of PPS (A1)
8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2957.21 g (70.97 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP) in a 70 liter autoclave with a stirrer. ) 11434.50 g (115.50 mol), 1722.00 g (21.00 mol) of sodium acetate, and 10500 g of ion-exchanged water were charged and gradually heated to 245 ° C. over about 3 hours while passing nitrogen under normal pressure. After distilling 14780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The amount of residual water 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 1 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 are added, the reaction vessel is sealed under nitrogen gas, and the reaction vessel is stirred at 240 rpm at 0.6 ° C./. The temperature was raised to 238 ° C. at a rate of 1 minute. After the reaction was carried out at 238 ° C. for 95 minutes, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min. After the reaction was carried out at 270 ° C. for 100 minutes, 1260 g (70 mol) of water was press-fitted over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./min. Then, it was cooled to 200 ° C. at a rate of 1.0 ° C./min and then rapidly cooled to near room temperature.

The contents were taken out, diluted with 26300 g of NMP, the solvent and the solid matter were filtered off by a sieve (80 mesh), and the obtained particles were washed with 31900 g of NMP and filtered off. This was washed with 56,000 g of ion-exchanged water several times and filtered off, and then washed with 70000 g of a 0.05 wt% acetic acid aqueous solution and filtered off. After washing with 70,000 g of ion-exchanged water and filtering, the obtained hydrous PPS particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C. The obtained PPS was linear, the ash content was 0.18%, and the MFR was 600 g / 10 minutes.

B1: Core shell type rubber: Core: Butyl acrylate rubber, Shell: Methyl methacrylate / glycidyl methacrylate copolymer (Paraloid 2314 (trade name) manufactured by Roam & Haas)

C1: Circular glass fiber (T-760H (trade name) manufactured by Nippon Electric Glass Co., Ltd., 3 mm long, average fiber diameter 10.5 μm).

C2: Flat glass fiber (CSG 3PA-830 (trade name) manufactured by Nitto Boseki Co., Ltd.) The ratio of the major axis to the minor axis of the cross section is 2, and the cross-sectional area is 2 × 10 ^-4 mm ² )

D1: γ-isocyanatopropyltriethoxysilane (KBE9007 manufactured by Shinetsu Silicone Co., Ltd.)

E1: Bisphenol A type epoxy resin (JER1009 (trade name) manufactured by Mitsubishi Chemical Corporation)

[Metal used]
(Physically roughened metal)
The aluminum A5052 (JIS standard) plate was blasted using shot blasting to obtain the following metals-1 and metal-2.
Metal-1: Aluminum A5052 (JIS standard), Ra = 30 μm
Metal-2: Aluminum A5052 (JIS standard), Ra = 2 μm

(Chemically roughened metal)
The following metals-3 and metal-4 were obtained from the aluminum A5052 (JIS standard) plate and the copper C1100 (JIS standard) plate by the TRI (Toa Denka, Ltd. registered trademark) system.
Metal-3: Aluminum A5052 (JIS standard), average number of recesses 50 nm
Metal-4: Copper C1100 (JIS standard), average number of recesses 50 nm
The following metal-5 was obtained from the aluminum plate A5052 (JIS standard) by NMT (registered trademark of Taisei Plus Corporation).
Metal-5: Aluminum A5052 (JIS standard), average number of recesses 50 nm

[Examples 1 to 14]
As shown in Table 1, the composition of the resin composition was changed, and the components (A), (B), (D), and (E) were supplied from the main inlet of the twin-screw extruder, and the component (C) was added. , It was supplied from a secondary inlet installed between the main inlet and the tip of the extruder, melt-kneaded with a twin-screw extruder having a screw diameter of 44 mmφ set at a cylinder temperature of 320 ° C., and pelletized with a strand cutter. Molding and evaluation were carried out using pellets dried at 120 ° C. overnight.

[Comparative Examples 1 to 5]
As shown in Table 2, the composition of the resin composition is changed, the components (A) and (B) are supplied from the main inlet of the twin-screw extruder, and the component (C) is supplied to the main inlet and the tip of the extruder. It was supplied from an auxiliary inlet installed between the two, melt-kneaded with a twin-screw extruder having a screw diameter of 44 mmφ set at a cylinder temperature of 320 ° C., and pelletized with a strand cutter. Molding and evaluation were carried out using pellets dried at 120 ° C. overnight. In each case, the metal bonding strength was inferior.

By utilizing the present invention, the polyphenylene sulfide resin composition and the metal shape can be firmly injection-bonded, and the obtained integrated product will not be easily peeled off. Therefore, it is possible to manufacture housings, parts, structures, and the like of various devices having a high degree of freedom in terms of shape, structure, and mechanical strength. The housing, parts, and structures manufactured by the present invention are useful for weight reduction and simplification of the equipment manufacturing process.

Claims (8)

A composite structure of a molded product composed of a metal and a polyphenylene sulfide resin composition.
The surface of the metal is roughened, and the roughening treatment is a physical and / or chemical roughening treatment, and the roughness Ra of the physically roughened metal surface is It is 1 μm to 50 μm, and is characterized in that the chemically roughened metal surface is covered with recesses having a number average inner diameter of 10 to 80 nm.
The polyphenylene sulfide resin composition contains a core made of a rubbery polymer obtained by polymerizing (B) an acrylic monomer with respect to 100 parts by weight of (A) polyphenylene sulfide resin, and a glycidyl group, and is an acrylic single amount. A composite structure characterized by being a polyphenylene sulfide resin composition comprising 1 to 15 parts by weight of a core-shell type rubber containing a polymerized outermost layer and 10 to 150 parts by weight of (C) glass fiber. The composite structure according to claim 1, wherein the chemical roughening treatment is a chemical etching treatment and / or an anodizing treatment. The composite structure according to claim 1 or 2, wherein the metal is one selected from aluminum, copper, iron, nickel, chromium, magnesium, molybdenum, and alloys thereof. The claim is characterized in that the polyphenylene sulfide resin composition is a composition obtained by further blending 0.1 to 5 parts by weight of the (D) alkoxysilane compound with 100 parts by weight of the (A) polyphenylene sulfide resin. Item 3. The composite structure according to any one of Items 1 to 3 . Claims 1 to 1 characterized in that the polyphenylene sulfide resin composition is a composition obtained by further blending 1 to 15 parts by weight of (E) epoxy resin with respect to 100 parts by weight of (A) polyphenylene sulfide resin. 4. The composite structure according to any one of 4. The cross-sectional area of the glass fiber (C) contained in the polyphenylene sulfide resin composition is 2 × 10 ^-5 to 8 × 10 ^-3 mm ² , and the major axis of the cross section perpendicular to the length direction (the longest cross section). 1 to 5, wherein the glass fiber has a flat cross-sectional shape in which the ratio of the minor axis (the longest linear distance in the direction perpendicular to the major axis) is between 1.3 to 10. The composite structure described in any of the above. The composite structure according to any one of claims 1 to 6, which is joined by injection welding. The roughened metal contains a core made of a rubbery polymer obtained by polymerizing (B) an acrylic monomer with respect to 100 parts by weight of (A) polyphenylene sulfide resin, and a glycidyl group. A polyphenylene sulfide resin composition containing 1 to 15 parts by weight of a core-shell type rubber containing a polymerized outermost layer and 10 to 150 parts by weight of (C) glass fiber is melted and brought into contact with a metal and polyphenylene sulfide. A method for producing a composite structure of a molded product made of a resin composition .
The roughening treatment was a physical and / or chemical roughening treatment, and the roughness Ra of the physically roughened metal surface was 1 μm to 50 μm, and the chemical roughening treatment was performed. A method for producing a composite structure of a molded body composed of a metal and a polyphenylene sulfide resin composition, wherein the metal surface is covered with recesses having a number average inner diameter of 10 to 80 nm.