JP2013014831A - Composite of metal and resin, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composite of metal and resin in which a metal part and a resin part are rigidly bonded to each other without using an adhesive, and a method for producing the composite.SOLUTION: The method for producing the composite 10 of metal and resin in which the metal part 20 and the resin part 30 are bonded to each other includes: a first plasma process of irradiating a surface of the metal part in an atmosphere with a plasma of a first gas consisting of inert gas or air; a second plasma process of applying a polar functional group 25 deriving from a surface-modification substance by irradiating the surface of the metal part in the atmosphere with a plasma of a second gas consisting of inert gas or air after the first plasma process; and a blending process of preparing a molding material by blending an adhesive surface-modifier having an adhesive functional group 35 interacting with the polar functional group into the resin, wherein, after performing all the processes, the resin part is molded so as to be in contact with the metal part using the molding material to bond the metal part to the resin part.

Description

  The present invention relates to a composite in which a metal part made of metal and a resin part made of resin are bonded, and a method for producing the same.

  As a method for adhering a metal and a resin, there are 1) a method in which the metal surface is made uneven, and an adhesive effect is used, and 2) a method in which an adhesive is used through an adhesive. However, since the adhesion by the anchor effect is weak against a thermal shock, there is a limit to the use site, and there is a concern that the adhesion by the adhesive may increase the number of processes and deteriorate the working environment due to the solvent.

  As a method other than the above, there is a method in which a metal surface is modified and adhered by plasma treatment. For example, a steel sheet that has been subjected to chemical conversion treatment is subjected to plasma treatment at atmospheric pressure using a mixed gas of oxygen gas and argon gas to modify the surface of the steel sheet, and a coating film such as a fluorine resin is applied to the modified surface. (Patent Document 1). Silicone rubber insert molding is performed using a metal reinforcing plate that has been subjected to cleaning and surface modification by atmospheric pressure plasma using compressed air or the like on the joint surface (Patent Document 2). After irradiating the surface of a metal material such as aluminum with plasma using air or the like, a corrosion-resistant layer of an epoxy resin paint is formed (Patent Document 3).

  In addition, there is an example of modifying the wettability of a metal workpiece such as aluminum by plasma-exciting a mixed gas of an inert gas such as argon gas and a reactive gas such as acetone under atmospheric pressure (patent) Reference 4) is not described as a method of adhesion.

JP-A-11-106947 JP 2007-66627 A JP 2005-7710 A JP-A-6-88242

When the present inventors tried to bond a metal treated with plasma using only argon gas or air corresponding to Patent Documents 1 to 3 and a resin, the adhesive force was still weak (Table). 3 comparative examples 3 and 4).
In addition, the present inventors have conceived for the first time that the modification process corresponding to Patent Document 4 is used for adhesion, and specifically, a mixed gas of an inert gas (argon gas) and a reactive gas (allylamine) is used. When the plasma-treated metal used and the resin were bonded, the adhesive strength was still not sufficient (less than 4 MPa) (see Comparative Examples 10 and 11 in Table 3).

  Therefore, the present invention provides a composite of a metal and a resin in which a metal part made of a metal and a resin part made of a resin are firmly bonded without using an adhesive (overlap shear strength of 4 MPa or more), and the metal It aims at providing the manufacturing method of the composite_body | complex of resin and resin.

  Before plasma treatment (modified plasma treatment) for irradiating a metal with an argon gas plasma containing allylamine gas in an air atmosphere, a plasma treatment (air plasma treatment) for irradiating the metal with argon gas plasma in an air atmosphere is performed. And, it was found that the adhesive force between the metal part and the resin part is improved (overlap shear strength is 3 times or more) compared with the case of only the modified plasma treatment (Example 2 in Table 1 and Comparative Example in Table 3). 10).

This is because a hydroxyl group is imparted to the metal surface by irradiating the metal with argon gas plasma in an air atmosphere. This reaction may have the following three aspects. (A) The metal (Me) is activated by the plasma of argon gas, and as shown in FIG. 2a, the activated metal acts with water in the atmosphere or the like to give a hydroxyl group to the metal surface. (B) Water in the atmosphere is activated by the argon gas plasma, and as shown in FIG. 2b, the activated water acts on the metal to give a hydroxyl group to the metal surface. (C) The metal and water in the atmosphere are both activated by the argon gas plasma, and the activated metal and water act to give a hydroxyl group to the metal surface.
Then, after irradiating the metal with an argon gas plasma in an air atmosphere, the activated allylamine is exposed to the metal surface by irradiating the metal with an argon gas plasma containing an allylamine gas in the air atmosphere as shown in FIG. By acting with the hydroxyl group imparted to the metal, allylamine can be firmly and strongly bonded to the metal surface. Therefore, the adhesive force between the metal part and the resin part is improved.

  In order to solve the above problems, a composite of a metal and a resin according to the present invention is a composite of a metal and a resin in which a metal part made of metal and a resin part made of resin are bonded, and the metal part Is provided with a polar functional group on the adhesive surface with the resin part, and the resin is blended with an adhesive modifier having an adhesive functional group that interacts with the polar functional group. The polar functional group irradiates the bonding surface with an inert gas or air plasma containing a surface modification product in an air atmosphere after irradiating the bonding surface with an inert gas or air plasma in an air atmosphere. A functional group derived from the surface modification product imparted to the adhesive surface, and the metal part and the resin part are adhered by the interaction of the polar functional group and the adhesive functional group, and JIS The weight of the adhesion measured according to K 6850 The shear shear strength is 4 MPa or more.

  In order to solve the above problems, the method for producing a composite of a metal and a resin according to the present invention is a method for producing a composite of a metal and a resin in which a metal part made of metal and a resin part made of resin are bonded. A first plasma treatment for irradiating the surface of the metal part with a plasma of a first gas made of an inert gas or air in an air atmosphere; and after the first plasma treatment, an inert gas containing a surface modification product in the air atmosphere. A second plasma treatment for irradiating the surface of the metal part with a plasma of a second gas comprising an active gas or air to impart a polar functional group derived from the surface modification product; and The resin part is molded so as to be in contact with the metal part using the molding material after blending an adhesive modifier having an adhesive functional group that acts to form a molding material. , The metal part and the resin part Characterized in that to wear.

  The aspect of each element of the manufacturing method of the composite_body | complex of the metal and resin of this invention and the composite_body | complex of a metal and resin is illustrated below.

1. Metal part Although it does not specifically limit as an aspect of a metal part, A plate shape, foil shape, a lump shape, etc. can be illustrated, and it may be beforehand formed in predetermined shape with a processing machine etc. according to the use of a composite. However, it may be formed in a predetermined shape after bonding with the resin portion.

  The metal used for the metal part is not particularly limited, but aluminum, copper, iron, magnesium, nickel, titanium, tin, gold, silver, chromium, tungsten, zinc, lead, and the like, and stainless steel that is an alloy thereof, Examples include brass.

2. Inert gas Although it does not specifically limit as an inert gas, Argon gas (Ar), Helium gas (He), Neon gas (Ne) etc. can be illustrated.

3. First Plasma Treatment In the first plasma treatment, hydroxyl groups can be imparted to the surface (adhesion surface) of the metal part by irradiating plasma in an air atmosphere without including water in the first gas. This is because water (water vapor) is contained in the atmosphere.

4). 1st gas Although 1st gas is not specifically limited, Since the adhesive force of a metal part and a resin part improves, it is preferable that the water is included. Although it does not specifically limit as content rate of water, 0.1-30 vol% (volume%) can be illustrated.

5. Second Plasma Treatment The amount of the surface modification product (including the material derived from the surface modification product) applied to the surface of the metal part by the second plasma treatment is not particularly limited, but is 8.9 × 10 ⁻⁶ to An example is 1.0 mg / cm ² . Preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻² mg / cm ² .

6). The second gas The second gas is not particularly limited, but the first plasma treatment and the second plasma treatment can be performed continuously, and workability is good. It is preferable to use gas.

7). Polar functional group Although it does not specifically limit as a polar functional group, An amino group, a carboxyl group, a silanol group, a hydroxyl group etc. can be illustrated, 1 type of these functional groups may be sufficient, and 2 or more types may be sufficient as it.

8). Surface modified product The surface modified product is not particularly limited, but may be a compound having one or two or more polar functional groups, or a derivative thereof. Specific examples include allylamine, acrylic acid, tetraethoxysilane (TEOS), triethyl orthoacetate and the like.
Although the content rate of the surface modification material contained in 2nd gas is not specifically limited, 1-99 vol% can be illustrated.

9. Resin Part The form of the resin part is not particularly limited, and examples thereof include a plate shape, a film shape, and a lump shape. In addition, when the resin part is molded so as to be in contact with the metal part in accordance with the use of the composite, it is preferable to use a predetermined shape in order to reduce the number of processes.

9-1. Resin The resin used for the resin portion is not particularly limited, and examples thereof include engineering plastics such as polyphenylene sulfide (PPS), polyamide (PA), polyester, and fluororesin, and general-purpose plastics such as polyolefin.
Moreover, glass fiber, an inorganic filler, etc. may be mix | blended and resin may not be mix | blended. Mechanical strength etc. improve by mix | blending glass fiber and an inorganic filler.

  The polyphenylene sulfide is not particularly limited, but may be a crosslinked type having a two-dimensional or three-dimensional crosslinked structure through oxygen in the molecule, or the molecule is linear (the structural units are connected in a line). It may be a linear type.

  The polyamide is not particularly limited, but polyamide 6 (PA6), polyamide 11 (PA11), polyamide 12 (PA12), polyamide 66 (PA66), polyamide 6T (PA6T), polyamide 6I (PA6I), polyamide 9T (PA9T) ), And aramid that is an aromatic polyamide.

  The polyester is not particularly limited, and examples thereof include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).

  The polyolefin is not particularly limited, but examples thereof include polyethylene (PE) and polypropylene (PP).

  Although it does not specifically limit as a fluororesin, Tetrafluoroethylene-ethylene copolymer (ETFE), tetrafluoroethylene (PTFE), etc. can be illustrated.

9-2. Adhesive modifier The adhesive modifier added to the resin is not particularly limited, but it is preferable that it can be easily mixed uniformly with the resin. Specifically, a compound obtained by modifying a graft copolymer with polyethylene, polystyrene, polypropylene, etc. as the main chain and a styrene polymer as a side chain, with an adhesive functional group, or polyethylene, polystyrene, polypropylene, etc. with an adhesive functional group. The compound etc. which modified | denatured by can be illustrated. More specifically, a glycidyl methacrylate-modified ethylene-styrene copolymer in which a copolymer of ethylene and styrene is modified with glycidyl methacrylate, a glycidyl methacrylate-modified polyethylene in which polyethylene is modified with glycidyl methacrylate, ethylene and acrylic acid. Examples thereof include a copolymerized ethylene-acrylic acid copolymer, an oxazoline-modified polypropylene in which oxazoline is graft-polymerized on polypropylene, and a maleic anhydride-modified polypropylene.

  The blending ratio of the adhesive modifier varies depending on the type of adhesive modifier (such as the type of adhesive functional group and the amount of adhesive functional group in the adhesive modifier), and is not particularly limited. The total amount of the resin and the adhesive modifier is preferably 1.5 to 50 wt% (wt%). If this value is less than 1.5 wt%, the adhesiveness of the resin part to the metal part is lowered, and if it exceeds 50 wt%, the releasability when molding the resin part is deteriorated. More preferably, it is 10-30 wt%.

The adhesive functional group possessed by the adhesive modifier is not particularly limited, but includes an epoxy group (including an epoxy group in a glycidyl group, the same applies hereinafter), a carboxyl group, a maleic anhydride group, an oxazoline group, an amino group, A hydroxyl group etc. can be illustrated.
When the polar functional group is an amino group, an epoxy group, a carboxyl group, a maleic anhydride group, and an oxazoline group are preferable because adhesion is easy, and an epoxy group is preferable because adhesion is strong.
When the polar functional group is a carboxyl group, a silanol group or a hydroxyl group, it is preferable that the polar functional group is easily adhered or an epoxy group.

  The content of the adhesive functional group in the mixture of resin and adhesive modifier (which is also a molding material) varies depending on the type of adhesive functional group and is not particularly limited, but the resin and adhesive modifier The total amount is preferably 0.05 to 1.5 wt%. If this value is less than 0.05 wt%, the adhesiveness of the resin portion to the metal portion is reduced, and if it exceeds 1.5 wt%, the releasability when molding the resin portion is deteriorated. More preferably, it is 0.3-0.9 wt%.

  The compounding method of blending an adhesive modifier into the resin to form a molding material is not particularly limited, but after melt-kneading at a predetermined temperature using a uniaxial or biaxial extruder, etc., and making it uniform, Examples of the method include a pellet form.

The method of molding the resin part so as to be in contact with the metal part is not particularly limited. However, since the metal part and the resin part can be bonded and the resin part can be molded at a time, the mold in which the metal part is held inside. It is preferable to use insert molding. Although it does not specifically limit as insert molding, Compression molding, injection molding, etc. can be illustrated.
Moreover, shaping | molding may include the annealing process and does not need to include it.

The adhesion between the metal part and the resin part is considered to be due to the interaction between the polar functional group on the surface of the metal part and the adhesive functional group of the resin part.
This interaction is an action in which atoms, electrons, and the like of the polar functional group and the adhesive functional group attract each other at the interface between the metal part and the resin part. Specifically, the primary bond (ion bond, covalent bond, etc.) that involves the transfer and sharing of electrons between the atoms of the polar functional group and the adhesive functional group, and among the polar functional group and the adhesive functional group, the electrons This is a secondary bond (hydrogen bond, van der Waals bond, etc.) in which density uneven distribution occurs and both functional groups attract each other by clonal force.

10. Composite of metal and resin The form of the composite of metal and resin is not particularly limited, and examples thereof include a plate shape, a foil shape, a string shape, a cylindrical shape, a columnar shape, a spherical shape, and a lump shape.
The use of the composite of metal and resin is not particularly limited, but electronic / electrical parts, building civil engineering members, automobile parts, agricultural materials, packing materials, clothing, daily necessities, etc., or materials for manufacturing these, etc. Can be illustrated. Although it does not specifically limit as a motor vehicle part, The sealing member etc. which seal batteries, such as a sealing member which seals engine oil etc., a hybrid vehicle, etc. can be illustrated.

  According to the present invention, there is provided a composite of a metal and a resin in which a metal part made of metal and a resin part made of resin are firmly bonded without using an adhesive (overlapping shear strength is 4 MPa or more). be able to.

It is a cross-sectional schematic diagram of the interface vicinity of the metal part and resin part of the composite_body | complex of the metal of this invention, and resin. It is a schematic diagram of reaction which provides a hydroxyl group to the metal surface by 1st plasma treatment. It is a schematic diagram of reaction which provides an allylamine to a metal surface by 2nd plasma treatment. It is a schematic diagram of the processing apparatus of 1st plasma processing. It is a schematic diagram of the processing apparatus of 2nd plasma processing.

As shown in FIG. 1, the composite 10 of a metal and a resin of the present invention includes an upper surface 21 of a metal part 20 made of a metal and a lower surface 31 of a resin part 30 made of a resin. It is bonded by interaction with the group 35.
The metal part 20 is obtained by adding a polar functional group 25 to the upper surface 21.
The resin of the resin part 30 is blended with an adhesive modifier having an adhesive functional group 35 that interacts with the polar functional group 25.
The polar functional group 25 is applied to the upper surface 21 by irradiating the upper surface 21 with an inert gas or air plasma containing a surface modification product in the air atmosphere after irradiating the upper surface 21 with an inert gas or air plasma in the air atmosphere. It is a functional group derived from the surface modified product.

  A method for producing the composite 10 of metal and resin will be described.

Pretreatment A pretreatment is performed to remove the oil and the like adhering to the upper surface 21 of the metal part 20 and clean the upper surface 21 of the metal part 20.

First plasma treatment After the pretreatment, as shown in FIG. 4, a first gas (process gas) is introduced into the plasma generator to form a plasma, and the plasma is released into the atmosphere. A first plasma process (atmospheric pressure plasma process) is performed by irradiating the upper surface 21 of the metal part 20 with a plasma of gas.

Second Plasma Treatment After the first plasma treatment, as shown in FIG. 5, a second gas composed of a mixed gas containing a surface modified gas in a carrier gas and a process gas is introduced into the plasma generator to generate plasma. The plasma is discharged into the atmosphere, and the second gas treatment (reformed plasma treatment) is performed by irradiating the upper surface 21 of the metal part 20 with the plasma of the second gas in the atmosphere.
The second plasma treatment is performed using the same plasma generator as the first plasma treatment by introducing a mixed gas containing the surface modified gas into the carrier gas into the plasma generator into which the first gas is introduced. May be performed following the first plasma treatment.

-Blending process The adhesive modifier is melt-kneaded with a resin using a kneader to produce a molding material in which the adhesive modifier is blended with the resin.

Molding process After the metal part having the second plasma treatment applied to the upper surface 21 is placed in the mold so that the upper surface 21 faces the inner space of the mold, the molding material is placed in the mold and used as the molding material. Compression molding is performed at a temperature at which the resin being melted.

  Next, the test body of the Example of this invention and a comparative example was produced, the adhesiveness of a metal part and a resin part was measured, and the result is shown to Tables 1-3.

  Each member etc. which were used for the Example and the comparative example are demonstrated.

  The metal part is made of aluminum (aluminum, A1050), copper (C1100), steel (iron), stainless steel (SUS), magnesium, nickel, titanium, or tin (tin), and has a length of 75 mm. A metal plate having a width of 25 mm and a thickness of 2 mm was used.

  As the resin, polyphenylene sulfide (PPS), polyamide 66 (PA66), polybutylene terephthalate (PBT), polypropylene (PP), or tetrafluoroethylene-ethylene copolymer (ETFE) was used.

  As the adhesive modifier, glycidyl methacrylate (GMA) modified polyethylene, ethylene-acrylic acid copolymer, maleic anhydride modified polypropylene or oxazoline modified polypropylene was used.

  Allylamine, acrylic acid, tetraethoxysilane (TEOS) or triethyl orthoacetate was used as the surface modification product.

  Argon gas (Ar), argon gas containing water vapor (Ar / water), or air was used as the process gas for the first plasma treatment.

  Argon gas was used as the process gas and carrier gas for the second plasma treatment.

  Next, conditions for producing each specimen will be described.

-Pretreatment One side of the metal plate is rubbed with sandpaper having a particle size of # 1000 to remove oil and the like adhering to the surface. Then, it wash | cleaned with ethanol and the pre-processing of the metal plate was performed.

First plasma treatment A process gas (first gas, flow rate: 0.5 L / min) is introduced into a plasma generator (plasma generation output: 50 W, frequency: 2 GHz) to form plasma, and this plasma is released into the atmosphere. . Then, a first plasma treatment (atmospheric pressure plasma treatment) was performed by irradiating a pretreated metal plate placed on a three-dimensional stage in an air atmosphere from above for 13 seconds. The metal plate is placed with the pretreated side up.

Second plasma treatment Carrier gas (flow rate: 0.5 L / min) in a liquid surface modification at a predetermined temperature (liquid temperature is 5 ° C. for allylamine and acrylic acid, and liquid temperature is 30 ° C. for TEOS and triethyl orthoacetate) To form a mixed gas containing the surface modified gas in the carrier gas. The mixed gas and the process gas (flow rate: 0.5 L / min) are introduced into a plasma generator (plasma generation output: 50 W, frequency: 2 GHz) to form plasma, and the plasma is released into the atmosphere. Then, a second plasma treatment (modified plasma treatment) was performed by irradiating the metal plate after the first plasma treatment placed on the three-dimensional stage in the air atmosphere from above. The metal plate is placed with the first plasma treated surface up.

・ Blending treatment Adhesive modifier is blended with resin so that the adhesive functional group has a predetermined content, and the resin and adhesive modifier are used using Labo Plast Mill (Toyo Seiki Seisakusho "KF70V2"). Were melt kneaded for 5 minutes at a temperature at which the used resin melted (PPS: 320 ° C., PA 66: 290 ° C., PBT: 260 ° C., PP: 190 ° C., ETFE: 230 ° C.) to obtain a molding material.

Molding process After placing the metal plate in the mold so that the second plasma-treated surface faces the inner space of the mold, the molding material is placed in the mold, and the resin used for the molding material Compression molding was performed at the above temperature at which the melted.

  Next, each specimen will be described.

In Example 1, an aluminum metal plate was used, and after the first plasma treatment using argon gas (Ar) as a process gas, allylamine was used as a surface modification product, and allylamine applied to the surface of the metal plate The second plasma treatment was performed by irradiating with plasma for 0.2 seconds so that the amount was 1.3 × 10 ⁻⁵ mg / cm ² . Moreover, 10 wt% of glycidyl methacrylate (GMA) modified polyethylene was blended with polyphenylene sulfide (PPS) so that the epoxy group content was 0.3 wt%.

In Example 2, except that the second plasma treatment was performed by irradiating plasma for 13 seconds so that the amount of allylamine applied to the metal plate surface was 1.3 × 10 ⁻³ mg / cm ² . Same as Example 1.
In Example 3, except that the second plasma treatment was performed by irradiating the plasma for 65 seconds so that the amount of allylamine applied to the surface of the metal plate was 6.5 × 10 ⁻³ mg / cm ² . The same as in the second embodiment.

  Examples 4 and 5 are the same as Example 2 except that 3 wt% or 30 wt% of glycidyl methacrylate (GMA) modified polyethylene is blended so that the epoxy group content is 0.1 wt% or 0.9 wt%. is there.

  In Examples 6 to 8, except that the ethylene-acrylic acid copolymer was blended in an amount of 3 wt%, 10 wt% or 30 wt% so that the carboxyl group content was 0.1 wt%, 0.3 wt% or 0.9 wt% Is the same as in Example 2.

  Examples 9 and 10 are the same as Example 2 except that argon gas (Ar / water) containing air or water vapor is used as the process gas for the first plasma treatment.

  Examples 11 and 12 were the same as Example 2 except that 10 wt% of maleic anhydride-modified polypropylene or 10 wt% of oxazoline-modified polypropylene was blended so that the maleic anhydride group or oxazoline group content was 0.3 wt%. The same.

  Examples 13 to 16 were the same as Example 2 except that polyamide 66 (PA66), polybutylene terephthalate (PBT), polypropylene (PP), or tetrafluoroethylene-ethylene copolymer (ETFE) was used as the resin. is there.

  Examples 17-22 are the same as Example 2 except having used the metal plate of copper (C1100), steel (iron), stainless steel (SUS), magnesium, nickel, or titanium.

  Example 23 is the same as Example 2 except that polypropylene (PP) is used as the resin and a metal plate made of tin is used.

  Examples 24-26 are the same as Example 2 except that acrylic acid, tetraethoxysilane (TEOS) or triethyl orthoacetate was used as the surface modification product.

Comparative Example 1 differs from Example 2 in that the first and second plasma treatments are not performed and the adhesive modifier is not blended.
Comparative Example 2 is different from Example 2 in that the first and second plasma treatments are not performed.
Comparative Example 3 is different from Example 2 in that the second plasma treatment is not performed and the adhesive modifier is not blended.
Comparative Example 4 is different from Example 2 in that the second plasma treatment is not performed.

  Comparative Examples 5 to 7 differ from Example 2 and the like in that the content of adhesive functional groups (epoxy groups and carboxyl groups) is 0 wt% or 0.03 wt%.

Comparative Examples 8 and 9 differ from Example 2 in that the amount of allylamine applied to the metal plate surface is 8.9 × 10 ⁻⁶ mg / cm ² .

  Comparative Examples 10 and 11 differ from Example 2 in that the first plasma treatment is not performed.

Next, the adhesion test will be described.
Adhesiveness is the overlap shear strength (hereinafter referred to as “adhesive strength”) between the metal part and the resin part in accordance with JIS K 6850 (Adhesive-Tensile Shear Adhesive Tensile Shear Bond Strength Test Method). It was measured.

As mentioned above, the Example of this invention had the adhesive force of 4.1 Mpa or more.
On the other hand, Comparative Examples 1-4, 10, and 11 in which at least one of the first plasma treatment and the second plasma treatment was not performed had an adhesive strength of 3.3 MPa or less.
Moreover, the adhesive force of Comparative Examples 5-7 whose content rate of an epoxy group or a carboxyl group is 0.03 wt% or less was 0.2 MPa or less.
Further, in Comparative Examples 8 and 9 in which the amount of allylamine applied to the surface of the metal plate was 8.9 × 10 ⁻⁶ mg / cm ² , the adhesive force was 0.4 MPa or less.

In Example 2 using argon gas as the process gas for the first plasma treatment, the adhesive force was 12.3 MPa, and the adhesive force was improved over that using air (Example 9).
In Example 10 using argon gas containing water vapor as the process gas for the first plasma treatment, the adhesive force was 13.3 MPa, and the adhesive force was improved over that not containing water vapor (Example 2).

In Example 24 using acrylic acid as the surface modified product, the adhesive force was 10.9 MPa, and the adhesive force was improved compared to that using triethyl orthoacetate (Example 26).
In Example 25 using tetraethoxysilane as the surface modification product, the adhesive force was 11.1 MPa, and the adhesive force was improved compared to that using acrylic acid (Example 24).
In Example 2 using allylamine as the surface modification product, the adhesive force was 12.3 MPa, and the adhesive force was improved from that using tetraethoxysilane (Example 25).

In Examples 2 and ^{3 in which} the amount of allylamine applied to the metal plate surface is 1.3 × 10 ⁻³ mg / cm ² or more, the adhesive strength is 12.3 MPa or more, and the amount of allylamine is 1.3 × 10 6. ^The adhesive strength improved more than twice as much as that of ⁻⁵ mg / cm ² (Example 1).

  In addition, this invention is not limited to the said Example, In the range which does not deviate from the meaning of invention, it can change suitably and can be actualized.

DESCRIPTION OF SYMBOLS 10 Composite of metal and resin 20 Metal part 25 Polar functional group 30 Resin part 35 Adhesive functional group

Claims (11)

A method for producing a composite of a metal and a resin in which a metal part made of metal and a resin part made of resin are bonded,
A first plasma treatment for irradiating the surface of the metal part with a plasma of a first gas comprising an inert gas or air in an air atmosphere;
After the first plasma treatment, the surface of the metal part is irradiated with a plasma of a second gas made of an inert gas or air containing a surface modification product in an air atmosphere to give a polar functional group derived from the surface modification product. A second plasma treatment,
After carrying out a blending treatment to form a molding material by blending an adhesive modifier having an adhesive functional group that interacts with the polar functional group in the resin,
A method for producing a composite of a metal and a resin, wherein the resin part is molded using the molding material so as to be in contact with the metal part, and the metal part and the resin part are bonded.   The method for producing a composite of a metal and a resin according to claim 1, wherein the surface modification product is contained in the first gas to form the second gas.   The method for producing a composite of a metal and a resin according to claim 1 or 2, wherein the surface modification product is allylamine, acrylic acid, tetraethoxysilane, or triethyl orthoacetate.   The method for producing a complex of a metal and a resin according to any one of claims 1 to 3, wherein the adhesive functional group is an epoxy group, a carboxyl group, a maleic anhydride group, or an oxazoline group.   The said resin is polyphenylene sulfide, polyamide, polyester, polyolefin, or a fluororesin, The manufacturing method of the composite_body | complex of the metal and resin as described in any one of Claims 1-4.   The said metal is aluminum, copper, iron, stainless steel, magnesium, nickel, titanium, or tin, The manufacturing method of the composite_body | complex of the metal and resin as described in any one of Claims 1-5. A metal and resin composite in which a metal part made of metal and a resin part made of resin are bonded,
The metal part is provided with a polar functional group on the adhesive surface with the resin part,
The resin is formulated with an adhesive modifier having an adhesive functional group that interacts with the polar functional group,
The polar functional group is formed by irradiating the bonding surface with an inert gas or air plasma in an air atmosphere and then irradiating the bonding surface with an inert gas or air plasma containing a surface modification product in the air atmosphere. A functional group derived from the surface modification product applied to the surface,
The metal part and the resin part are bonded by the interaction between the polar functional group and the adhesive functional group, and the overlap shear strength of the bond measured in accordance with JIS K 6850 is 4 MPa or more. A composite of metal and resin characterized by the above.   The metal / resin composite according to claim 7, wherein the polar functional group is at least one functional group selected from the group consisting of an amino group, a carboxyl group, a silanol group, and a hydroxyl group.   The composite of a metal and a resin according to claim 7 or 8, wherein the adhesive functional group is an epoxy group, a carboxyl group, a maleic anhydride group or an oxazoline group.   The said resin is a polyphenylene sulfide, polyamide, polyester, polyolefin, or a fluororesin, The composite_body | complex of the metal and resin as described in any one of Claims 7-9.   The said metal is aluminum, copper, iron, stainless steel, magnesium, nickel, titanium, or tin, The composite_body | complex of the metal and resin as described in any one of Claims 7-10.

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