JP2020152103A - Method for producing composite molded body and composite molded body - Google Patents

Abstract

To provide a composite molded body that has a high bonding strength without using chemicals or the like in a melt bonding of metal and resin.SOLUTION: There is provided a method for producing a composite molded body composed of a thermoplastic elastomer resin composition (X) and a metal (Y), in which in the method for producing the composite molded body, the thermoplastic elastomer resin composition (X) comprises: 66 to 99.98 wt.% of a polyester block-copolymer that has a melting point of less than 210°C and that has the main components of a hard segment (a1) composed of a crystalline aromatic polyester unit and a soft segment (a2) composed of an aliphatic polyether unit and/or an aliphatic polyester unit; 0 to 30 wt.% of a polyvinyl butyral resin (B); 0.01 to 5.0 wt.% of a silane coupling agent (C); and 0.01 to 5.0 wt.% of an antioxidant (D), and the thermoplastic elastomer resin composition (X) is heated and melted to bond with the metal (Y) immersed in water at 80°C or higher for 5 minutes or longer.SELECTED DRAWING: None

Description

The present invention relates to a method for producing a composite molded product and a composite molded product.

Composite molded bodies made of metal and resin are used for various purposes. However, in joining dissimilar materials such as metal and resin, it is required to increase the joining strength. For example, as a method for obtaining a composite molded body of a resin and a metal, a method of joining a resin to a part whose metal part has been surface-treated with an amine compound or the like by injection molding has been proposed (see, for example, Patent Document 1). However, there are concerns that the work becomes complicated by applying a specific surface treatment to the metal parts, the safety of the operator because the chemical solution is used, and the environmental load.
There were issues such as.

On the other hand, it has been proposed to join an elastomer and a metal without using a chemical solution. For example, a method of melting an elastomer using a laser to bond it to a metal (see, for example, Patent Documents 2 and 3), and a method of using an elastomer having a modified molecular end to improve the bonding strength (for example, patent). (See Document 4), has been proposed. However, in this method, the strength of the base material of the elastomer is relatively small, and there is room for improvement in the bonding strength.

In response to the above problems, a method of welding and bonding using a polyester elastomer having a relatively high base material strength among the elastomers (see Patent Document 5) has been proposed.

In addition, the metal-resin bonding force is affected by the metal surface condition before bonding, so the cleaning method is also important. For example, a method of removing stains on a metal surface with an organic solvent or acid is exemplified (see Patent Document 6).

Japanese Unexamined Patent Publication No. 2008-173967 (pages 1 and 2) Japanese Unexamined Patent Publication No. 2008-7584 (pages 1 and 2) Japanese Unexamined Patent Publication No. 2008-173967 (pages 1 and 2) Japanese Unexamined Patent Publication No. 2009-155402 (pages 1 to 3) Patent No. 5610392 Japanese Unexamined Patent Publication No. 8-25409 (page 5)

However, even in the bonding method of Patent Document 5, the bonding strength may not be sufficient, and improvement of the bonding strength has been an issue. Further, also in the cleaning method of Patent Document 6, there are problems that the stain on the metal surface cannot be completely removed depending on the type of the organic solvent, and that the cleaning with an acid dissolves the metal.

The present invention has been achieved as a result of studies for solving the above-mentioned problems of the prior art, and provides a composite molded body having a high bonding force in melt bonding of a metal and a resin without using a chemical or the like. The purpose is to do.

That is, the present invention is a method for producing a composite molded body composed of a thermoplastic elastomer resin composition (X) and a metal (Y), wherein the thermoplastic elastomer resin composition (X) is composed of a crystalline aromatic polyester unit. Polyester block copolymers (A) 66 to 99. A polyester block copolymer (A) having a melting point of less than 210 ° C., mainly composed of a hard segment (a1) and a soft segment (a2) composed of an aliphatic polyether unit and / or an aliphatic polyester unit. 98% by weight, polyvinyl butyral resin (B) 0 to 30% by weight, silane coupling agent (C) 0.01 to 5.0% by weight, antioxidant (D) 0.01 to 5.0% by weight. % And the thermoplastic elastomer resin composition (X) is heated and melted and bonded to the metal (Y) which has been immersed in water at 80 ° C. or higher for 5 minutes or longer. This is a method for manufacturing a molded product.

Further, the present invention is a composite molded body composed of a thermoplastic elastomer resin composition (X) and a metal (Y), wherein the thermoplastic elastomer resin composition (X) is a hard segment composed of a crystalline aromatic polyester unit (a hard segment (X). A polyester block copolymer (A) 66 to 99.98% by weight containing a1) and a soft segment (a2) composed of an aliphatic polyether unit and / or an aliphatic polyester unit as a main component and having a melting point of less than 210 ° C. , Polyvinylbutyral resin (B) 0 to 30% by weight, silane coupling agent (C) and its derivative 0.01 to 5.0% by weight, and antioxidant (D) 0.01 to 5.0% by weight. Is a composite molded body obtained by blending the above and having a bonding strength of the thermoplastic elastomer resin composition (X) and the metal (Y) of 10 MPa or more.

According to the present invention, as described below, in joining a resin and a metal, a composite molded body having a high joining force can be obtained without using a chemical or the like.

Hereinafter, the present invention will be described in detail.

[Thermoplastic Elastomer Resin Composition (X)]
The polyester block copolymer (A) used in the thermoplastic elastomer resin composition (X) of the present invention includes a hard segment (a1) mainly composed of a crystalline aromatic polyester unit, and mainly an aliphatic polyether unit and /. Alternatively, it is a polyester block copolymer mainly composed of a soft segment (a2) composed of an aliphatic polyester unit, and the hard segment (a1) is mainly an aromatic dicarboxylic acid or an ester-forming derivative thereof, and a diol or its ester. A polyester formed from an ester-forming derivative.

Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, anthracenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid. Examples include acids, diphenoxyetanedicarboxylic acids, 4,4'-diphenylether dicarboxylic acids, 5-sulfoisophthalic acid, and sodium 3-sulfoisophthalate. In the present invention, the aromatic dicarboxylic acid is mainly used, and a part of the aromatic dicarboxylic acid is an alicyclic such as 1,4-cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, and 4,4′-dicyclohexyldicarboxylic acid. It may be replaced with a group dicarboxylic acid or an aliphatic dicarboxylic acid such as adipic acid, succinic acid, oxalic acid, sebacic acid, dodecandioic acid, and dimer acid. Further, ester-forming derivatives of dicarboxylic acids such as lower alkyl esters, aryl esters, carbonic acid esters, acid halides and the like can of course be used equally.

In the present invention, it is preferable to use two or more of the above acid components, and examples thereof include combinations of terephthalic acid and isophthalic acid, terephthalic acid and dodecandioic acid, and terephthalic acid and dimer acid. By using two or more kinds of acid components, the crystallinity of the hard segment can be lowered, flexibility can be imparted, and the thermal adhesiveness with other thermoplastic resins is also improved.

Next, specific examples of the diol include diols having a molecular weight of 400 or less, such as 1,4-butanediol, ethylene glycol, trimethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, and decamethylene glycol. Group diols, alicyclic diols such as 1,1-cyclohexanedimethanol, 1,4-dicyclohexanedimethanol, tricyclodecanedimethanol, and xylylene glycol, bis (p-hydroxy) diphenyl, bis (p-hydroxy). ) Diphenyl propane, 2,2'-bis [4- (2-hydroxyethoxy) phenyl] propane, bis [4- (2-hydroxyethoxy) phenyl] sulfone, 1,1-bis [4- (2-hydroxyethoxy) ethoxy] ) Phenyl] Aromatic diols such as cyclohexane, 4,4'-dihydroxy-p-terphenyl, and 4,4'-dihydroxy-p-quarterphenyl are preferred, such diols being ester-forming derivatives such as acetyls. It can also be used in the form of an alkali metal salt or the like. Two or more of these dicarboxylic acids, derivatives thereof, diol components and derivatives thereof may be used in combination.

Preferred examples of such a hard segment (a1) are polybutylene terephthalate units derived from terephthalic acid and / or dimethylterephthalate and 1,4-butanediol, isophthalic acid and / or dimethylisophthalate and 1,4-butanediol. Polybutylene terephthalate units derived from, and copolymers of both are preferably used, and particularly preferably terephthalic acid and / or dimethylterephthalate and isophthalic acid and / or dimethylisophthalate and 1,4-butane. Those consisting of polybutylene terephthalate / isophthalate units derived from diols are used.

The soft segment (a2) of the polyester block copolymer (A) used in the present invention is an aliphatic polyether and / or an aliphatic polyester. Examples of the aliphatic polyether include poly (ethylene oxide) glycol, poly (propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a copolymer of ethylene oxide and propylene oxide, and poly (propylene oxide). Examples thereof include ethylene oxide addition polymers of glycols and copolymer glycols of ethylene oxide and tetrahydrofuran. Examples of the aliphatic polyester include poly (ε-caprolactone), polyenant lactone, polycaprilolactone, polybutylene adipate, and polyethylene adipate. From the elastic properties of the polyester block copolymers obtained among these aliphatic polyethers and / or aliphatic polyesters, poly (tetramethylene oxide) glycol, ethylene oxide adduct of poly (propylene oxide) glycol, ethylene oxide and tetrahydrofuran It is preferable to use the copolymer glycol, poly (ε-caprolactone), polybutylene adipate, polyethylene adipate, etc., among which poly (tetramethylene oxide) glycol, poly (propylene oxide) glycol ethylene oxide adduct, and poly (propylene oxide) glycol are particularly preferable. It is preferable to use a copolymer glycol of ethylene oxide and tetrahydrofuran. The number average molecular weight of these soft segments is preferably about 300 to 6000 in the copolymerized state.

The copolymerization amount of the soft segment (a2) of the polyester block copolymer (A) used in the present invention is usually 20 to 95% by weight, preferably 25 to 90% by weight, and thus (a1) and The copolymerization ratio of (a2) can be set.

The polyester block copolymer (A) used in the present invention can be produced by a known method. Specific examples thereof include, for example, a method in which a lower alcohol diester of a dicarboxylic acid, an excess amount of a low molecular weight glycol and a low melting point polymer segment component are transesterified in the presence of a catalyst, and the obtained reaction product is polycondensed. Any method may be adopted, such as a method in which a dicarboxylic acid, an excess amount of glycol, and a low melting point polymer segment component are transesterified in the presence of a catalyst, and the obtained reaction product is polycondensed.

The blending amount of the polyester block copolymer (A) of the present invention is 66% by weight to 99.98% by weight, particularly preferably 76 to 97% by weight, and less than 66% by weight is obtained as a thermoplastic elastomer resin composition ( X) has low mechanical properties and poor molding processability, and if it exceeds 99.98% by weight, the bonding strength decreases, which is not preferable.

The polyvinyl butyral resin (B) used in the present invention is not particularly limited, and commercially available products can be used. For example, Sflex BL-1, BL-2, BX-L manufactured by Sekisui Chemical Industry Co., Ltd. , BM-S, KS-3, etc., Denka Butyral 3000-1, 3000-2, 3000-4, 4000-2, etc. manufactured by Denki Kagaku Kogyo Co., Ltd., and the present invention is not limited thereto.

The thermoplastic elastomer resin composition (X) of the present invention may contain polyvinyl butyral resin (B) in order to further improve the bonding strength. The blending amount of the polyvinyl butyral resin of the present invention is 0 to 30% by weight, preferably 1 to 30% by weight. By setting it to 1% by weight or more, the effect of improving the joint strength is enhanced. Particularly preferably, it is 3 to 20% by weight. If it exceeds 30% by weight, the mechanical strength of the obtained thermoplastic elastomer resin composition (X) is low and the moldability is also inferior, which is not preferable.

The silane coupling agent (C) used in the present invention is not particularly limited, but preferably has an amino group, an epoxy group, a vinyl group, an allyl group, a methacryl group, a sulfide group or the like in one molecule. Among them, a silane coupling agent having an epoxy group is preferably used. Specific examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminoprocylethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, and 3- (2-aminoethyl) aminopropyl. Methyldimetocisilane, 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyl Methyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, vinyl triacetoxy Silane, Vinyltrimethoxysilane, Vinyltriethoxysilane, Acryltrimethoxysilane, 3-Methacryloxypropyltrimethoxysilane, 3-Methacryloxypropylmethyldimethoxysilane, 3-Mercaptopropyltrimethoxysilane, 3-Mercaptopropylmethyldimethoxy There are silanes and the like, preferably epoxy group-containing compounds, and these can be used alone or in combination of two or more.

The blending amount of the silane coupling agent (C) of the present invention is 0.01 to 5.0% by weight, preferably 0.05 to 3.0% by weight, and more preferably 0.1 to 1.5% by weight. is there. If the blending amount of the silane coupling agent is less than 0.01% by weight, the bonding strength is low, and if it exceeds 5.0% by weight, blooming occurs and the thermal stability is lowered, which is not preferable.

The antioxidant (D) used in the present invention is one selected from the group consisting of aromatic amine-based antioxidants, hindered phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants. , Or two or more kinds, among which aromatic amine-based antioxidants are preferably used.

Specific examples of the aromatic amine-based antioxidant include phenylnaphthylamine, 4,4'-dimethoxydiphenylamine, 4,4'-bis (α, α-dimethylbenzyl) diphenylamine, 4-isopropoxydiphenylamine and the like. However, among these, the use of diphenylamine-based compounds is preferable.

Specific examples of the hindered phenolic antioxidant include 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, and hydroxy. Methyl-2,6-di-t-butylphenol, 2,6-di-t-α-dimethylamino-p-cresol, 2,5-di-t-butyl-4-ethylphenol, 4,4'-bis (2,6-di-t-butylphenol), 2,2'-methylene-bis-4-methyl-6-t-butylphenol, 2,2'-methylene-bis (4-ethyl-6-t-butylphenol) , 4,4'-Methyl-bis (6-t-butyl-o-cresol), 4,4'-methylene-bis (2,6-di-t-butylphenol), 2,2'-methylene-bis ( 4-Methyl-6-cyclohexylphenol), 4,4'-butylidene-bis (3-methyl-6-t-butylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), bis (3-Methyl-4-hydroxy-5-t-butylbenzyl) sulfide, 4,4'-thiobis (6-t-butyl-o-cresol), 2,2'-thiobis (4-methyl-6-t) -Butylphenol), 2,6-bis (2'-hydroxy-3'-t-butyl-5'-methylbenzyl) -4-methylphenol, 3,5-di-t-butyl-4-hydroxybenzenesulfonic acid Diethyl ester, 2,2'-dihydroxy-3,3'-di (α-methylcyclohexyl) -5,5'-dimethyl-diphenylmethane, α-octadecyl-3 (3', 5'-di-t-butyl -4'-Hydroxyphenyl) propionate, 6- (hydroxy-3,5-di-t-butylanilino) -2,4-bis-octyl-thio-1,3,5-triazine, hexamethylene glycol-bis [β] -(3,5-di-t-butyl-4-hydroxyphenol) propionate], N, N'-hexamethylene-bis (3,5-di-t-butyl-4-hydroxyhydrosilicate amide), 2, , 2-thio [diethyl-bis-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate], dioctadecyl ester of 3,5-di-t-butyl-4-hydroxybenzenephosphonic acid, Tetraquis [Methyl-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris ( 3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-4-hydroxy-5-di-t-butylphenyl) butane, tris (3,5-) Examples thereof include di-t-butyl-4-hydroxyphenyl) isocyanurate and tris [β- (3,5-di-t-butyl-4 hydroxyphenyl) propionyl-oxyethyl] isocyanurate. Among these, those having a molecular weight of 500 or more, such as tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, are particularly preferable.

The sulfur-based antioxidant is a compound containing sulfur such as thioether-based, dithioate-based, mercaptobenzimidazole-based, thiocarbanilide-based, and thiodipropion ester-based. Among these, the use of a thiodipropion ester compound is particularly preferable.

The phosphorus-based antioxidant is a compound containing phosphorus such as phosphoric acid, phosphorous acid, hypophosphorous acid derivative, phenylphosphonic acid, polyphosphonate, dialkylpentaerythritol diphosphite, and dialkylbisphenol A diphosphite. Among these, it is preferable to use a compound having a sulfur atom as well as a phosphorus atom in the molecule, or a compound having two or more phosphorus atoms in the molecule.

The total amount of these antioxidants is 0.01 to 5.0% by weight, preferably 0.05 to 3.0% by weight, and more preferably 0.1 to 1.5% by weight.

When the total amount of the antioxidant is less than 0.01% by weight, the degree of the desired improvement effect is small, and at the same time, there is an effect of preventing copper damage when joining with the metal (Y). Further, if it exceeds 5.0% by weight, blooming occurs and the mechanical strength of the thermoplastic elastomer resin composition (X) is lowered, which is not preferable.

Further, various additives can be added to the thermoplastic elastomer resin composition (X) of the present invention as long as the object of the present invention is not impaired. For example, known molding aids such as crystal nucleating agents and lubricants, light-resistant agents such as ultraviolet absorbers and hindered amine compounds, hydrolysis-resistant improving agents, coloring agents such as pigments and dyes, antistatic agents, conductive agents, and flame retardants. Reinforcing agents, fillers, plasticizers, mold release agents and the like can be optionally contained.

The method for producing the thermoplastic elastomer resin composition (X) of the present invention is not particularly limited, but for example, a polyester block copolymer (A), a polyvinyl butyral resin (B), and a silane coupling agent (C). ), The raw material containing the antioxidant (D) can be appropriately adopted, such as a method of supplying the raw material to a screw type extruder and melt-kneading it.

[Metal (Y)]
The metal (Y) of the present invention may be a simple substance of a metal or an alloy of two or more kinds of metals. Specific examples of the metal (Y) include, but are not limited to, iron, steel, lead, aluminum, copper, brass, bronze, nickel, zinc, magnesium, titanium, chromium and the like. The metal (Y) is preferably made of aluminum, iron, titanium, chromium or an alloy thereof. In particular, aluminum is preferable because the metal form is changed by the hot water treatment described later and O (oxygen) atoms are easily added to the metal surface.

[Hot water treatment]
The water used in the present invention is not particularly limited, but it is preferable to use water having low conductivity such as ion-exchanged water, distilled water, and pure water for the purpose of eliminating the influence of complications in water.

By immersing the metal (Y) in high-temperature water, impurities such as organic substances on the metal surface can be reduced. That is, the ratio of C (carbon) elements on the metal surface can be reduced. Further, especially when the metal (Y) is aluminum, the number of O (oxygen) atoms on the metal surface can be increased by changing the metal morphology. The temperature of water is preferably 80 ° C. or higher, but more preferably 90 ° C. or higher.

The immersion time is not particularly limited, but is preferably 5 minutes or longer, more preferably 15 minutes or longer, and even more preferably 30 minutes or longer.

In the method for producing a composite molded product composed of the thermoplastic elastomer resin composition (X) and the metal (Y) of the present invention, the carbon atom ratio on the metal surface of the joint surface is preferably 10% or less. When the carbon atom ratio is 10% or more, the bonding reaction between the elastomer and the metal is inhibited, resulting in a decrease in bonding strength.

In the method for producing a composite molded body composed of the thermoplastic elastomer resin composition (X) and the metal (Y) of the present invention, the silane coupling agent in the thermoplastic elastomer resin composition (X) and the chemical bond on the metal surface are formed. In order to form the resin, the ratio of oxygen atoms on the metal surface of the joint surface is preferably 50% or more.

[Joining method]
The method for joining the composite molded product composed of the thermoplastic elastomer resin composition (X) and the metal (Y) of the present invention is particularly limited as long as it is a method of heating and melting the thermoplastic elastomer resin composition (X) of the present invention. There is nothing to do, for example, a method of irradiating a laser beam, a method of heating with a hot plate, a method of using a high frequency, a method of heating the metal (Y) itself to melt the thermoplastic elastomer resin composition (X), injection. A method of discharging the molten thermoplastic elastomer resin composition (X) from a molding machine or an extrusion molding machine and joining by a method such as two-color molding can be selected.

The composite molded body of the present invention is a composite molded body composed of a thermoplastic elastomer resin composition (X) and a metal (Y), and the thermoplastic elastomer resin composition (X) is made of a crystalline aromatic polyester unit. 66-99 weight of polyester block copolymer (A) having a melting point of less than 210 ° C., mainly composed of a hard segment (a1) and a soft segment (a2) composed of an aliphatic polyether unit and / or an aliphatic polyester unit. %, Polyvinylbutyral resin (B) 1 to 30% by weight, silane coupling agent (C) and its derivative 0.01 to 5.0% by weight, and antioxidant (D) 0.01 to 5.0% by weight. It is made by blending%. The derivative of the silane coupling agent (C) is a reaction product of the silane coupling agent, for example, a polymer of the silane coupling agents or a chemical bond between the resin and the metal via the silane coupling agent. It is an intermediary department, etc.

In the composite molded product of the present invention, the bonding strength between the thermoplastic elastomer resin composition (X) and the metal (Y) is preferably 10 MPa or more, more preferably 13 MPa or more. Since the strength of the base metal of the bonding using an elastomer is relatively small, it has been difficult to develop it in applications requiring bonding strength. If the joint strength is 10 MPa or more, it can be expected to be applied to applications requiring strength such as automobile parts, electrical equipment, and industrial supplies.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
The present invention is not limited to these examples, and can be appropriately modified and carried out within the scope of the gist of the present invention.

[Hot water treatment of metal (Y)]
1 L of distilled water manufactured by Hayashi Junyaku Kogyo Co., Ltd. was added to the beaker, and the beaker was heated using a hot plate. The water temperature was adjusted by adjusting the output of the hot plate.

[Analysis of element ratio on metal surface]
Using JPS-9030 manufactured by JEOL Ltd., the element ratio of the metal surface was measured under the following conditions.
Tilt angle: 0 degrees,
X-ray source: Non-monochromatic MgKα 12kV 25mA
Energy resolution: Ag3d5 / 2 is 1.8 eV (path energy 50 eV)
Aperture diameter: 6 mm
Energy step: 1 ev.

[Metal (Y)]
Aluminum A1050, titanium, SUS304 (alloy of iron, nickel, and chromium) and iron processed into a length of 60 mm, a width of 20 mm, and a wall thickness of 2 mm were used.

[Manufacturing of Thermoplastic Elastomer Resin Composition (X)]
With 443 parts of terephthalic acid and 190 parts of isophthalic acid, which are high melting point crystalline polymer segments (a1) made of crystalline aromatic polyester, and low melting point polymer segments (a2) made of aliphatic polyether units and aliphatic polyester units. 177 parts of poly (tetramethylene oxide) glycol having an average molecular weight of about 1000, 327 parts of 1,4-butanediol, and 1.8 parts of titanium tetrabutoxide were charged into a reaction vessel equipped with a helical ribbon-type stirring blade, and 190- The esterification reaction was carried out by heating at 225 ° C. for 3 hours and distilling the reaction water out of the system. After adding 0.5 part of "Irganox" 1098 (Hindered phenolic antioxidant manufactured by Ciba Geigy) to the reaction mixture, the temperature was raised to 243 ° C., and then the pressure in the system was increased to 0.2 mmHg over 50 minutes. The pressure was reduced and the polymerization was carried out for 2 hours and 45 minutes under the same conditions. The obtained polymer (polyester block copolymer (A)) was discharged into water in a strand form and cut into pellets.

For 854 parts of the obtained polyester block copolymer (A) pellets, 21 parts of a reinforcing agent (Toray Industries, Inc. Trecon 1100S: polybutylene terephthalate resin) and polyvinyl butyral resin (B) (Sekisui Chemical Co., Ltd.) ) Eslek BM-SZ) 100 parts, silane coupling agent (C) (Toray Dow Corning Co., Ltd. OFS-6040) 6 parts, antioxidant (D) (Shiraishi Calcium Co., Ltd. Nowguard 445) ) 40 parts were mixed using a V-blender, melt-kneaded at 250 ° C. using a twin-screw extruder having a diameter of 45 mm and a three-thread screw type screw, and pelletized.

[Joint strength by hot pressing with metal (Y)]
As different materials, various metals (Y) having a length of 60 mm, a width of 20 mm, and a wall thickness of 2 mm are placed under a hot press set at 230 ° C. on both the top and bottom and left for 1 minute. Then, a sheet of polyester elastomer (X) pressed to a length of 10 mm, a width of 20 mm, and a wall thickness of 0.2 mm is placed on the metal (Y), and the same metal (Y) is placed so as to be further overlapped by 10 mm. Then, it is pressed for 30 seconds with a load of 1 MPa to melt the thermoplastic elastomer resin composition (X) and bond it to the metal (Y). Then, the bonded body made of two metals (Y) is pressed for 1 MPa × 30 seconds with a press set at 40 ° C. on the upper side and the lower side to solidify the thermoplastic elastomer resin composition (X). A tensile shear test piece in which ^two metals (Y) were superposed on each other in an area of 20 mm ² was obtained. Then, both ends of the tensile shear test piece were sandwiched between the chucks of the tensile tester, and the force of peeling by tensile shear of the tensile joint surface was measured at a strain rate of 50 mm / min. The value obtained by dividing the peeling force obtained by tensile shearing by the joining area of 20 mm ² was calculated as the joining force.

Table 1 shows the evaluation results of the metal type, sample processing content, bonding strength, and element ratio of Examples and Comparative Examples.

As shown in Table 1, Examples 1 to 4 in which aluminum was used as the metal (Y) and immersed in water at 80 ° C. or higher for 5 minutes or longer showed high bonding strength, and the element ratio of carbon C on the metal surface was high. It was confirmed that it decreased and the element ratios of oxygen O and metal Al increased.

On the other hand, in Comparative Example 1 in which aluminum was used as the metal (Y) and not subjected to hot water treatment, and Comparative Example 2 in which the metal (Y) was immersed in water at 60 ° C., the element ratio of carbon C on the metal surface was an example. It was confirmed that the element ratio of oxygen O was low and the bonding strength was low.

Further, when titanium, SUS304, or iron was used as the metal (Y), Examples 6 to 8 immersed in water at 80 ° C. or higher for 5 minutes or more were more than Comparative Examples 3 to 5 in which no hot water treatment was performed. It was confirmed that it showed high bonding strength.

As described above, the method for producing a composite molded body and the composite molded body of the present invention have sufficient strength as a molded body, excellent molding processability, and high bonding strength with various dissimilar materials. It can be suitably used as a bonding material for bonding with different materials such as equipment and industrial products.

Claims (7)

A method for producing a composite molded body composed of a thermoplastic elastomer resin composition (X) and a metal (Y), wherein the thermoplastic elastomer resin composition (X) is a hard segment (a1) composed of a crystalline aromatic polyester unit. And 66 to 99.98% by weight of the polyester block copolymer (A) having a melting point of less than 210 ° C. and having a soft segment (a2) composed of an aliphatic polyether unit and / or an aliphatic polyester unit as a main component. Polyvinylbutyral resin (B) 0 to 30% by weight, silane coupling agent (C) 0.01 to 5.0% by weight, and antioxidant (D) 0.01 to 5.0% by weight are blended. A method for producing a composite molded body, which comprises heating and melting a thermoplastic elastomer resin composition (X) with respect to a metal (Y) immersed in water at 80 ° C. or higher for 5 minutes or longer. .. The method for producing a composite molded product according to claim 1, which contains 1 to 30% by weight of the polyvinyl butyral resin (B). The method for producing a composite molded body according to claim 1 or 2, wherein the metal (Y) is iron, steel, lead, aluminum, copper, brass, bronze, nickel, zinc, magnesium, titanium, chromium or an alloy thereof. The method for producing a composite molded product according to claim 3, wherein the metal is aluminum, iron, titanium, chromium, or an alloy thereof. The method for producing a composite molded product according to any one of claims 1 to 4, wherein the carbon atom ratio of the metal surface of the joint surface is 10% or less. The method for producing a composite molded product according to any one of claims 1 to 5, wherein the oxygen atom ratio of the metal surface of the joint surface is 50% or more. A composite molded body composed of a thermoplastic elastomer resin composition (X) and a metal (Y), the thermoplastic elastomer resin composition (X) includes a hard segment (a1) made of a crystalline aromatic polyester unit and a fat. A polyester block copolymer (A) 66 to 99.98% by weight containing a soft segment (a2) composed of a group polyether unit and / or an aliphatic polyester unit as a main component and having a melting point of less than 210 ° C., and a polyvinyl butyral resin. (B) 0 to 30% by weight, polyvinyl butyral resin (B) 1 to 30% by weight, silane coupling agent (C) and its derivative 0.01 to 5.0% by weight, and antioxidant (D) 0. A composite molded body obtained by blending 0.01 to 5.0% by weight and having a bonding strength of the thermoplastic elastomer resin composition (X) and the metal (Y) of 10 MPa or more.