TW202026150A - Pre-coated metal material, composite manufacturing method and composite - Google Patents

Abstract

An object of the invention is to provide a pre-coated metal material which is a metal material previously given bondability to a rubber by pre-coating, and does not demonstrate adhesiveness affecting these during storage and transfer, but on the other hand, has sufficient bondability to a vulcanized rubber when bonded to a rubber. The invention for achieving the above purpose is related to a pre-coated metal material which has a metal material, an inorganic-organic composite layer configured on the metal material, and a rubber layer configured to contact with a surface of the inorganic-organic composite layer. The rubber layer contains a halogen rubber and a vulcanizing agent of the halogen rubber.

Description

Method for manufacturing pre-coated metal material, composite material and composite material

The invention relates to a pre-coated metal material, a manufacturing method of a composite material, and a composite material.

The so-called "metal material" is a metal plate or its press-formed product that is shaped to metal by heat or pressure, or a metal part formed by casting, forging, cutting, powder metallurgy, etc., and resin The composite material in which the formed material of the composition is joined to the "metal material" is known. A composite material joined by a molded material of a metal material and a resin composition is lighter than a part made of only metal, and has higher strength than a part made of only a resin, so it is used in portable phones. Or various electronic devices such as personal computers.

On the other hand, when trying to bond rubber to the surface of a metal material, conventionally, an adhesive has been used to bond the metal material and rubber. For example, Patent Document 1 describes the use of a synthetic resin adhesive to join a specific chromate treated product and a chlorinated vulcanized rubber to the surface of a metal that has been electrogalvanized, and the manufacture of rubber and metal bonding composites method. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 9-221552

[The problem to be solved by the invention]

According to Patent Document 1, the vulcanized rubber can be joined to the metal by the above-mentioned method, and since it is not necessary to vulcanize the rubber at the time of joining, the rubber and metal adhesive composite material can be manufactured simply and inexpensively.

However, in the method of bonding the vulcanized rubber to the metal material using an adhesive, the bonding (adhesion) is required immediately after the adhesive is applied. Therefore, when the shape of any one of the metal material and the rubber to be joined is complicated or the joining area is large, it is difficult to adjust the time for the process of applying the adhesive to the joining surface and the subsequent joining process. In addition, when a two-component adhesive is used, the pot life after mixing the main agent and the hardening agent, and the adjustment of the hardening time to sufficiently increase the bonding strength, are likely to be a burden on the manufacturing process.

On the other hand, if the metal material is prepared first and the metal material is processed with a metal that has been pre-coated with an adhesive for rubber on a large area in advance, and the adhesiveness to rubber has been given in advance, it can be used for Since the metal material and rubber are joined at a desired time, it is also considered that the burden of the application of the adhesive on the manufacturing process is also reduced. However, in this method, since it is necessary to use an adhesive that does not have restrictions on the usable time, etc., an adhesive that is bonded by a primary bond such as a covalent bond as described in Patent Document 1 is not practical. Adhesives bonded by secondary bonds such as hydrogen bonds and intermolecular forces can be used. Furthermore, since the adhesive adhered by the secondary bond exhibits adhesiveness at the time of application, the metal material that has been coated with the adhesive adhered by the secondary bond makes it difficult to load or coil into a coil for storage and transportation. .

The present invention was completed in view of the related points, and its purpose is to provide: pre-coated metal material, which is a metal material that has been given pre-coating and adhesiveness with rubber, and does not exert such effects during storage and movement. On the other hand, it has sufficient adhesion to rubber that has been vulcanized when it is bonded with rubber; a method for manufacturing composite materials, which uses this pre-coated metal material to manufacture metal and rubber bonded composite materials ; And composite materials, which are manufactured from pre-coated metal materials. [Means to solve the problem]

The pre-coated metal material of one embodiment of the present invention to solve the above-mentioned problems includes: a metal material; an inorganic-organic composite layer arranged on the above-mentioned metal material; and a rubber layer arranged on top of the above-mentioned inorganic-organic composite layer Surface contact; wherein the rubber layer contains halogen rubber and a vulcanizing agent for the halogen rubber.

In addition, a method for manufacturing a composite material according to one embodiment of the present invention to solve the above-mentioned problems includes: arranging a rubber molding material containing a vulcanized rubber composition on the surface of the pre-coated metal material in contact with the rubber layer And a step of heating the rubber layer in contact with the rubber molding material to join the precoated metal material and the rubber molding material.

In addition, a composite material related to an embodiment of the present invention to solve the above-mentioned problems has: a metal material; an inorganic-organic composite layer arranged on the metal material; and a rubber layer arranged on the surface of the inorganic-organic composite layer It is in contact with and includes vulcanized halogen rubber; and a rubber molding material, which is placed in contact with the surface of the rubber layer, and includes a vulcanized rubber composition. [Invention Effect]

According to the present invention, the following is provided: a pre-coated metal material, which is a metal material that has been given adhesion to rubber due to the pre-coating, and does not exert such adhesion as it affects these during storage and movement. On the other hand, It has sufficient adhesion to rubber that has been vulcanized when it is joined with rubber; a method for manufacturing a composite material, which uses this pre-coated metal material to produce a composite material in which metal and rubber have been joined; and a composite material, thereby Manufactured with pre-coated metal materials.

1. Pre-coated metal material One embodiment of the present invention relates to a pre-coated metal material, which has: a metal material; an inorganic organic composite layer disposed on the metal material; and a rubber layer disposed in contact with the surface of the inorganic organic composite layer. In the pre-coated metal material, the rubber layer includes a halogen rubber and a vulcanizing agent for the halogen rubber. Since the pre-coated metal material has adhesiveness with the rubber molding material and the rubber molding material contains a rubber composition that has been vulcanized, in order to manufacture the metal material and the composite material in which the rubber molding material is joined (hereinafter, also referred to as It is a "composite material".) And the above-mentioned pre-coated metal materials can be used.

In the present embodiment, the rubber layer is partially vulcanized when the halogen rubber is formed, so it does not have adhesiveness to such an extent that it affects storage and movement. On the other hand, since the above-mentioned rubber layer is partially unvulcanized, the above-mentioned halogen rubber can be bonded to the rubber molding material well by heating and pressure bonding. Furthermore, in this embodiment, the inorganic-organic composite layer has a function of improving the bonding strength to the rubber layer of the metal material.

1-1. Metal materials The metal material is a so-called metal, which can be shaped by applying forces such as forming. Specifically, the metal material is a metal plate, a press-formed product thereof, or a metal part formed by casting, forging, cutting, powder metallurgy, or the like. The type of metal material is not particularly limited. In the example of metal materials, metal plates, press-worked products of metal plates, metal parts, and the like are included. In the example of the above metal plate, zinc-plated steel plate, Zn-Al alloy plated steel plate, Zn-Al-Mg alloy plated steel plate, Zn-Al-Mg-Si alloy plated steel plate, aluminum plated steel plate, stainless steel plate (including Austin System, Matian powder system, fertilizer granule system, and two-phase system of fertilizer granule and Matian powder), aluminum plate, aluminum alloy plate, and copper plate are included. The metal plate may be a rolled steel plate such as a cold rolled steel plate. Among the above-mentioned metal parts, various metal parts formed by casting, forging, cutting, powder metallurgy, etc., including aluminum die-casting and zinc die-casting, are included. Metal materials may be subjected to conventional coating pretreatments such as degreasing and pickling as needed.

1-2. Inorganic organic composite layer The inorganic-organic composite layer is arranged on the surface of the metal material in contact with the surface of the metal material or via another layer such as the plating layer between the surface of the metal material.

The above-mentioned inorganic-organic composite layer is a layer containing an inorganic compound and an organic compound.

The above-mentioned inorganic compound may be a compound capable of binding with the above-mentioned organic compound or forming a chelate compound. From the viewpoint of forming more bonding sites or chelate complexes with the organic compound to make the inorganic-organic composite layer denser and stronger, the above-mentioned inorganic compound preferably contains a metal that forms a polyvalent ion, more preferably from the four An oxide, hydroxide or fluoride of a metal selected from the group consisting of a group metal, a group five metal or a group six metal. However, from the viewpoint of dechromating the aforementioned precoated metal material, the aforementioned metal is preferably a metal other than chromium, and Ti, Zr, Hf, V, Nb, Ta, Mo, or W is preferable.

These metals and metal ions that have been eluted from the surface of the metal material (for example, when the metal material is a stainless steel sheet, it is composed of metal ions such as Cr, Ni, Mo, Fe, and when the metal material has a coating layer, it is composed of Zn, Mg, Al, etc. The ions of the plated metal) react to form a poorly soluble conversion coating with excellent corrosion resistance. In addition, these metals react with an organic compound to crosslink the organic compound, etc., to form a poorly soluble inorganic-organic composite compound in which the inorganic compound and the organic compound are composited. The inorganic-organic composite layer having a dense skeleton made of the inorganic-organic composite compound formed in this way has high adhesion to the metal material and can also improve the corrosion resistance of the metal material.

In addition, these metals also function as a vulcanizing agent for the halogen rubber contained in the rubber layer. Therefore, when the rubber molding material is thermocompression-bonded to the above-mentioned precoated metal material, these metals are combined with the halogen rubber in the rubber layer to further increase the bonding strength between the inorganic-organic composite layer and the rubber layer, thereby improving the bonding The bonding strength of the rubber molding material to the metal material in the rubber layer.

For example, when it contains an inorganic compound containing Ti (hereinafter also referred to as "titanium compound"), the above-mentioned inorganic-organic composite layer preferably contains a Ti (titanium atom) conversion amount of 1 mg/m ² or more and 100 mg /m ² or less titanium compound. In addition, when it contains an inorganic compound containing Zr (hereinafter also referred to as a "zirconium compound"), the inorganic-organic composite layer preferably contains an adhesion amount of 0.1 mg/m ² or more in terms of Zr (zirconium atom) and 30 mg /m ² or less zirconium compound.

On the other hand, the inorganic-organic composite layer may be a so-called chromate-free conversion treatment film that does not substantially contain chromium as the metal. Therefore, the pre-coated metal material having the inorganic-organic composite layer can be chromate-free.

Here, "chromate-free" means that the pre-coated metal material does not substantially contain hexavalent chromium. "Chromate-free" means, for example, by cutting out four test pieces of 50 mm x 50 mm from the above-mentioned pre-coated metal material, and immersing them in 100 mL of boiling pure water for 10 minutes. JIS H8625 (1993) appendix 2.4.1 "Diphenylaminourea colorimetric method" concentration analysis method to quantify the hexavalent chromium dissolved in this pure water, the detection value is below the detection limit, and Able to confirm.

It is considered that the above-mentioned metal mainly becomes an amorphous oxide or hydroxide in the above-mentioned inorganic-organic composite layer to constitute the above-mentioned dense framework. Alternatively, the metal may be present in the inorganic-organic composite layer as a poorly soluble fluoride. The above-mentioned fluoride is eluted into the moisture in the atmosphere, and then becomes a poorly soluble oxide or hydroxide on the surface of the metal material exposed from the defect part and then precipitates again, and can play a so-called self-repairing function of filling the defect part. , So it is better.

In the example of the above-mentioned organic compound, an organic acid and an organic resin are included. Among these, the organic compound is preferably an organic acid from the viewpoint of forming a dense inorganic-organic composite layer excellent in adhesion and corrosion resistance to the metal material by allowing the chelate compound to be easily formed with the metal.

The above-mentioned organic compounds have a high effect of forming intermolecular forces and hydrogen bonds. Therefore, the above-mentioned organic compound forms an interaction with the halogen rubber constituting the rubber layer to improve the adhesion to the rubber layer of the inorganic-organic composite layer, thereby improving the resistance to metal of the rubber molding material bonded to the rubber layer. The bonding strength of the material.

In addition, it is also considered that the above-mentioned organic compound functions as a binder for the rubber layer to improve the adhesion to the rubber layer of the inorganic-organic composite layer. Thereby, the organic compound suppresses the adhesion of the rubber layer of the pre-coated metal material and the rubber layer of other pre-coated metal materials in an unheated state during movement and storage. Hereinafter, the rubber layer of the pre-coated metal material is also unintentionally adhered to other surfaces when it is not heated, and easily becomes inseparable, which is called "blocking".).

In particular, when an inorganic-organic composite treatment solution is applied to a metal material and heated and dried to form an inorganic-organic composite layer, the organic acid is removed and the treatment solution is concentrated, so the pH of the treatment solution is locally lowered. Due to this local pH drop, the surface in contact with the inorganic-organic composite layer on the metal material side is finely etched. Therefore, the organic acid increases the contact area between the surface of the metal material side and the inorganic-organic composite layer by the etching, and can also increase the bonding strength of the inorganic-organic composite layer to the metal material.

In addition, the organic acid elutes metal salts and oxides from the metal material into the inorganic-organic composite layer during the etching. The eluted metal salts and oxides, etc., also function as vulcanizing materials for halogen rubber, so the inorganic-organic composite layer (metal salts and oxides) is formed by heating when the rubber molding materials are joined. The combination with the rubber layer (halogen rubber) can also improve the bonding strength of the inorganic-organic composite layer to the metal material after the rubber molding material is bonded.

The above-mentioned organic acid may be an organic compound having a hydroxyl group in the molecule, and is preferably an organic compound having a carboxyl group in the molecule. Furthermore, the above-mentioned organic acid is preferably a multivalent organic acid having two or more hydroxyl groups or carboxyl groups in the molecule. In examples of such organic acids, tartaric acid, tannic acid, citric acid, oxalic acid, malonic acid, lactic acid, and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC), etc. are included .

Among these, polyvalent phenols such as tannic acid and organic phosphonic acids such as PBTC are easy to form stable inorganic-organic composite compounds, and they also have the function of supplementing the self-repairing effect caused by the fluorides of the above-mentioned metals. Therefore, the adhesion of the inorganic-organic composite layer can be further improved. In addition, since the above-mentioned polyvalent phenols and organic phosphonic acids are soluble even in strong acidity, when the inorganic-organic composite layer is formed in the treatment solution, it can reach the surface on the metal material side more significantly. The effect of improving the bonding strength caused by the etching.

In addition, the above-mentioned organic acids may also form salts with Mg, Al, Fe, Ni, Zn, Mo and the like.

In the example of the above-mentioned organic resin, phenol resin, acrylic resin, acrylic olefin resin, urethane resin, etc. are contained.

In addition, the above-mentioned inorganic-organic composite layer may further contain other components in addition to the aforementioned components. In the example of this other component, a rust preventive component, wax, and an inorganic lubricant are included. In the example of the anti-rust component described above, porous silica, metal phosphates, and complex phosphates are included. In the example of the above wax, various organic waxes of fluorine, polyethylene, and styrene are included. In the examples of the above-mentioned inorganic lubricants, silicon dioxide, molybdenum disulfide, and talc are included.

The composition of the above-mentioned inorganic-organic composite layer, for example, can be confirmed by a Fourier transform infrared spectrophotometer if it is an organic component, and can be confirmed by a fluorescent X-ray analyzer if it is an inorganic component.

The adhesion amount of the inorganic-organic composite layer is preferably 10 mg/m ² or more and 300 mg/m ² or less, more preferably 30 mg/m ² or more and 200 mg/m ² or less.

The above-mentioned inorganic-organic composite layer can be formed by applying an aqueous inorganic-organic composite treatment solution (dispersion or solution) containing the above-mentioned inorganic compound, organic compound, and other components optionally added on a metal material, and heating To make it dry.

The aforementioned inorganic-organic composite treatment liquid, for example, when forming an inorganic-organic composite layer containing a titanium compound as the aforementioned inorganic compound, if it contains K _n TiF ₆ (K: alkali metal or alkaline earth metal, n: 1 or 2), K ₂ [TiO(COO) ₂ ], (NH ₄ ) ₂ TiF ₆ , H ₂ TiF ₆ , TiCl ₄ , TiOSO ₄ , Ti(SO ₄ ) ₂ , Ti(OH) ₄ , (NH ₄ ) ₂ TiF ₆ , H ₂ TiF ₆ , KnTiF _6, etc., but when forming an inorganic-organic composite layer containing a zirconium compound as the above-mentioned inorganic compound, if it contains zirconate such as zirconium oxide and sodium zirconate, or fluorinated zirconic acid and A fluorinated zirconate such as sodium fluoride zirconate may be used.

In addition, the inorganic-organic composite treatment liquid may contain the organic acid or its salt, or the organic resin as the organic compound.

The coating method of the inorganic-organic composite treatment liquid is not particularly limited, and it may be appropriately selected from a conventional method including a roll coating method, a curtain flow method, a spin coating method, a spray method, and a dip pulling method.

The conditions for heating and drying the inorganic-organic composite treatment liquid may be appropriately set according to the composition and amount of the inorganic-organic composite treatment liquid. For example, by putting the metal material coated with the inorganic-organic composite treatment liquid into the drying oven, and drying the metal material with a hot air dryer so that the surface temperature of the metal material is in the range of 110~200℃, The surface of the metal material forms a uniform inorganic-organic composite layer.

1-3. Rubber layer The rubber layer is a layer containing halogen rubber as a main component and a vulcanizing agent for the halogen rubber. In addition, as the main component, it means that 50% by mass or more of the organic resin contained in the rubber layer is halogen rubber.

The above-mentioned halogen rubber has high adhesion to both the inorganic-organic composite layer and the rubber molded material, and therefore can improve the bonding strength to the rubber molded material of the metal material.

Among the above examples of halogen rubber, fluorine-containing rubber such as vinylidene fluoride rubber, fluorine-containing vinyl ether rubber, and fluorine-containing phosphazene rubber, including 2-chloroprene rubber, chlorosulfonated polyethylene rubber, and epoxy Chlorinated rubber, such as chloropropane rubber, chlorinated butyl rubber, chlorinated polyethylene rubber, butenedioic acid modified chlorinated polyethylene rubber, and chlorinated rubber made from chlorinated natural rubber, and Bromine-containing rubber such as base rubber and the like are included.

Among these halogen rubbers, from the viewpoint of further improving the adhesion to the inorganic-organic composite layer and the rubber molding material, the chloro-containing rubber is preferred, and 2-chloroprene rubber, chlorosulfonated polyethylene rubber, And chlorinated rubber.

The vulcanizing agent may be a compound capable of vulcanizing the halogen rubber. In the above-mentioned examples of the vulcanizing agent, metal oxides, metal salts of unsaturated fatty acids, organic peroxides, and thiourea compounds are included.

In the example of the metal oxide as the above-mentioned vulcanizing agent, magnesium oxide, zinc oxide, and the like are included.

In the example of the metal salt of the unsaturated fatty acid as the vulcanizing agent, the zinc salt and the magnesium salt of the unsaturated fatty acid having a carbon number of 3 or more and 8 or less are included.

Examples of organic peroxides as the above-mentioned vulcanizing agent include bis-isophenylpropyl peroxide, bis(tertiary butyl) peroxide, 2,5-dimethyl-2,5-bis(tertiary) Butperoxy)-3-hexyne, 2,5-dimethyl-2,5-bis(tertiary butperoxy)hexane, and 1,3-bis(tertiary butperoxycumyl)benzene, etc. Dialkyl peroxides, dialkyl peroxides containing benzyl peroxide and isobutyryl peroxide, and dialkyl peroxides containing 2,5-dimethyl-2,5-bis(benzyl peroxide) Peroxy esters such as hexamethylene peroxy)hexane and tributylperoxy isopropyl carbonate are included.

In the example of the thiourea compound as the above-mentioned vulcanizing agent, ethylthiourea, diethylthiourea, dibutylthiourea, trimethylthiourea, and the like are included.

In addition, the above-mentioned inorganic-organic composite layer may also contain aldehyde-ammonia, aldehyde-amine, imidazoline, thiourea, guanidine, thiazole, sulfenamide, and thioblue (Tetramethylthiuram) in addition to the aforementioned components. Disulfide) series, dithiocarbamate series, xanthate series and other vulcanization accelerators.

When the rubber layer is heated when forming the rubber layer, the halogen rubber is partially vulcanized by the vulcanizing agent, and the reactivity and fluidity of the halogen rubber decrease. Therefore, the adhesiveness to other rubber layers and the like is not so high in the unheated state during movement and storage.

On the other hand, since the above-mentioned rubber layer is partially unvulcanized, the halogen rubber is heated to generate fluidity. Therefore, when the rubber molding material is brought into contact with the above-mentioned rubber layer and heated and compressed, the molecules of the halogen rubber that has developed fluidity penetrate into the outermost layer of the rubber molding material and become entangled with the molecules constituting the rubber molding material. When heating is continued in this state, the halogen rubber is vulcanized by the vulcanizing agent in a state of being entangled with the molecules constituting the rubber molding material and hardened. Therefore, the rubber layer can increase the bonding strength to the rubber molded material of the metal material.

In addition, it can be confirmed by a conventional method that it is partially vulcanized (or partially unvulcanized as it is).

From the viewpoint of achieving the predetermined vulcanization state during the formation of the rubber layer, relative to the total mass of the halogen rubber, the rubber layer preferably contains a vulcanizing agent in an amount of 1% by mass to 50% by mass, and more preferably Contained in an amount of 10% by mass or more and 30% by mass or less.

The adhesion thickness of the rubber layer is preferably 1 μm or more and 200 μm or less, more preferably 5 μm or more and 60 μm or less.

The rubber layer is preferably capable of being coated with a pre-coating film liquid on the surface of the inorganic-organic composite layer, and the pre-coating film liquid is the halogen rubber that has been unvulcanized, a vulcanizing agent, and other components optionally added It is formed by a method of dispersing or dissolving in an organic solvent pre-coating film liquid, and heating and drying it.

The coating method of the pre-coating film liquid is not particularly limited, and may be appropriately selected from conventional methods including roll coating, curtain flow, spin coating, spraying, dipping and pulling.

The conditions for heating and drying the pre-coating film liquid may be appropriately set according to the composition and application amount of the pre-coating film liquid, etc., but it is preferably performed to the extent that the rubber layer is partially vulcanized. For example, by putting the metal material that has been coated with the pre-coated film liquid into the drying oven, and making the surface temperature of the metal material within the range of 120~200℃, drying it with a hot air dryer for 10 seconds to 3 minutes The above-mentioned halogen rubber can form the above-mentioned rubber layer which has been partially vulcanized. In addition, the above-mentioned halogen rubber is not completely vulcanized under heating conditions of this level, but remains in a partially vulcanized state.

1-4. Rubber molding materials The above-mentioned rubber molding material is a molding material containing a vulcanized rubber composition having a desired shape.

The rubber composition may be a rubber composition having adhesion with the halogen rubber contained in the rubber layer, but it is particularly preferably natural rubber, 2-chloroprene rubber, nitrile butadiene rubber, etc. A diene rubber having an unsaturated bond in the main chain.

The above-mentioned rubber composition is a vulcanized rubber composition. Furthermore, the aforementioned precoated metal material has sufficient bonding properties with the rubber composition that has been vulcanized. Therefore, the rubber molding material does not need to be vulcanized during joining, and it does not require a device for vulcanization and preparation beforehand, making it possible to produce a composite material simply and inexpensively.

The above-mentioned rubber molding material may have a shape corresponding to the application. From the viewpoint of improving the bondability to the pre-coated metal material, it is preferable that the surface of the molding material that contacts the rubber layer has approximately the same shape as the surface of the rubber layer that contacts the molding material. .

2. Manufacturing method of composite material Another embodiment of the present invention relates to a method of manufacturing the above-mentioned composite material. The composite material can be manufactured by a method having the following steps: on the surface of the pre-coated metal material, a step of arranging a rubber molding material containing a vulcanized rubber composition in contact with the rubber layer; and heating and molding the rubber The step of joining the pre-coated metal material and the rubber molded material to the rubber layer in contact with the material.

2-1. Process of placing rubber molding material on the surface of pre-coated metal material In this step, the above-mentioned pre-coated metal material is prepared, and the above-mentioned rubber molding material is arranged in contact with the rubber layer on its surface.

If the above-mentioned pre-coated metal material is coated with the above-mentioned inorganic-organic composite treatment liquid on the metal material, heated and dried to form an inorganic-organic composite layer, the surface of the above-mentioned inorganic-organic composite layer is then coated The coating liquid is heated and dried, and what has been prepared is enough.

The rubber molded material is arranged in contact with the rubber layer with respect to the precoated metal material.

For example, in order that the part to be joined of the rubber molded material and the part to be joined of the precoated metal material are in contact with the rubber layer, the rubber molded material is arranged at least with respect to the precoated metal material. In addition, in this step, the portion to be joined of the rubber molding material and the portion to be joined of the precoated metal material may be in contact with the rubber layer at least at the time when the heating step described later is performed. At this time, the rubber molded material and the precoated metal material are pressed against each other by a fixing jig or the like to adhere, and it is preferable from the viewpoint of preventing positional deviation or the like.

2-2. Process of heating the rubber layer In this step, the contact portion between the rubber layer of the pre-coated metal material and the rubber molding material is heated to heat the rubber layer and the rubber molding material to bond the rubber molding material to the metal material. At this time, at the same time, the halogen rubber contained in the rubber layer is further vulcanized, so that the rubber molded material and the metal material can be joined more firmly.

The heating may be performed on at least a part of the surface in contact with the rubber layer and the rubber molding material, but from the viewpoint of further improving the adhesion, it is preferably performed on the entire surface of the surface in contact.

The heating method is not particularly limited, as long as it is appropriately selected from a conventional method. In examples of such heating methods, heating by hot pressing, heating by heating rollers, electromagnetic induction heating, direct energization heating, heating by resistance heating, heating by ultrasonic waves, lightning Jet heating, heating by a hot-air heating furnace, heating by a heater wafer, etc. are included.

From the viewpoint that the molecules of the halogen rubber contained in the rubber layer are sufficiently entangled with the molecules constituting the rubber molding material, and the bonding strength between the rubber molding material and the metal material is improved, it is preferable that the heating In order for the rubber molded material and the precoated metal material to face each other and be urged, either or both of these are pressurized.

The conditions such as the temperature and pressure during heating may be sufficient if the halogen rubber is fully vulcanized.

For example, the surface temperature of the metal material is within the range of 150 to 300°C, and the halogen rubber is sufficiently vulcanized by heating for about 10 to 30 minutes, and the rubber molding material can be bonded to the metal material with sufficient strength. .

In addition, at this time, between the rubber molded material and the precoated metal material, a pressure of 0.5 MPa or more may be applied, and a pressure of 2 MPa or more is preferably applied. Although the upper limit of the said pressure is not specifically limited, for example, it can be 100 MPa or less.

3. Composite Another embodiment of the present invention relates to the composite material manufactured by the above-mentioned manufacturing method. The composite material includes: a metal material; an inorganic-organic composite layer disposed on the metal material; a rubber layer disposed in contact with the surface of the inorganic-organic composite layer and containing vulcanized halogen rubber; and a rubber molding material , Is placed in contact with the surface of the above-mentioned rubber layer, and contains a vulcanized rubber composition.

The aforementioned metal material and the inorganic-organic composite layer have substantially the same components as the aforementioned metal material and the inorganic-organic composite layer for the pre-coated metal material.

The above-mentioned vulcanized rubber layer is a layer derived from the above-mentioned rubber layer for the pre-coated metal material. However, the halogen rubber contained in the above-mentioned rubber layer is vulcanized in this embodiment.

The rubber molding material is a rubber molding material joined to the aforementioned precoated metal material. A clear boundary may not be formed between the rubber molded material and the vulcanized rubber layer, but an interface region where the rubbers of the two are mixed in the thickness direction.

Hereinafter, although the present invention is described in detail with reference to embodiments, the present invention is not limited by these embodiments. [Example]

1. Production of pre-coated metal materials 1-1. Preparation of inorganic-organic composite treatment liquid As the organic acid, tannic acid which is a polyvalent phenol and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) which is an organic phosphonic acid were prepared.

The combination of organic compounds (organic acids) and inorganic compounds (compounds containing metals that form polyvalent ions) as described in Table 1 are dissolved in ion-exchange water so that the content of both is 2% by mass to prepare inorganic organic Composite treatment solution 1~Inorganic-organic composite treatment solution 8 (hereinafter referred to as "treatment solution 1" ~ "treatment solution 8").

[Table 1] Treatment fluid No. Organic compound Inorganic compound 1 Tannin Ammonium Vanadate 2 Tannin Ammonium zirconium carbonate 3 Tannin Ammonium molybdate 4 Tannin Titanium fluoride 5 Tannin Zirconium fluoride 6 PBTC Ammonium Vanadate 7 PBTC Ammonium zirconium carbonate 8 PBTC Ammonium molybdate

Ion exchange water to which neither organic compound nor inorganic compound was added was used as the comparative treatment liquid 1. In addition, the organic compound or inorganic compound described in Table 2 was dissolved in ion-exchanged water so that the content was 2% by mass, and comparative treatment liquid 2 to comparative treatment liquid 6 were prepared.

[Table 2] Comparative treatment fluid No. Organic compound Inorganic compound 2 Tannin - 3 PBTC - 4 - Ammonium Vanadate 5 - Ammonium zirconium carbonate 6 - Ammonium molybdate

1-2. Preparation of pre-coating liquid Chlorosulfonated polyethylene rubber (15 parts by mass) as a halogen rubber was dissolved in toluene (85 parts by mass). Furthermore, zinc oxide (5 parts by mass) as a vulcanizing agent was added to this solution and uniformly stirred to prepare a pre-coating film solution 1 (hereinafter, the "pre-coating film solution" is referred to as "film solution").

Except that the halogen rubber was changed to 2-chlorobutadiene, the same procedure as the coating liquid 1 was performed, and the coating liquid 2 was prepared.

A comparative film liquid 1 performed in the same manner as the film liquid 1 except that the vulcanizing agent was not added, and a comparative film liquid 2 that was performed in the same manner as the film liquid 1 except that a vulcanizing agent was added in a trace amount to 100% of the total amount of the halogen rubber were prepared.

1-3. Preparation of pre-coated metal materials Prepare a 1.6 mm thick hot-dip galvanized steel sheet, solvent-degreased and dried with ethanol. The surface of the plating layer of this steel sheet was coated with an inorganic-organic composite treatment liquid 1 by a bar coater in order to have a coating thickness of 4 μm (adhesion amount during drying: 65 mg/m ² ). Thereafter, the steel sheet is placed in an electric hot-air oven, and the inorganic-organic composite treatment liquid 1 is dried at an ambient temperature of 300°C for 5-10 seconds to form an inorganic-organic composite layer so that the surface temperature of the steel sheet becomes 150°C. The temperature of the steel plate is measured by attaching a thermocouple directly to the molten zinc-plated steel plate of the base material.

Thereafter, on the surface of the inorganic-organic composite layer, the pre-coating film liquid 1 was applied by a bar coater in order to have a coating thickness of 50 μm and a thickness of 20 μm after drying. After that, the steel plate is placed in an electric hot-air oven, and the pre-coating film solution 1 is dried at an ambient temperature of 300°C so that the surface temperature of the steel plate becomes 160°C to form a partially vulcanized rubber layer and obtain a pre-coating Metal material 1.

The combination of the inorganic-organic composite treatment liquid and the precoating film liquid was changed to the combination described in Table 3, and the precoating metal material 2 to the precoating metal material 10 were obtained.

Instead of the inorganic-organic composite treatment liquid 1, use any one of the comparative treatment liquid 1 to the comparative treatment liquid 6, or use the comparative pre-coating film liquid 1 instead of the pre-coating film liquid 1, to obtain the pre-coated metal materials described in Table 3 11~Pre-coated metal material 18.

In place of the coating liquid 1, the comparative coating liquid 2 in which the amount of the vulcanizing agent is excessive is used or the temperature at the time of forming the rubber layer is increased to obtain the precoated metal material 19 to the precoated metal material 22 in which the rubber layer is completely vulcanized.

Except that the rubber layer was not formed, the same procedure as the pre-coated metal material 1 or the pre-coated metal material 6 was performed, and the pre-coated metal material 23 and the pre-coated metal material 24 described in Table 3 were obtained.

[table 3] Pre-coated metal material Treatment liquid / comparison treatment liquid Coating liquid / comparative coating liquid Surface temperature of steel sheet when coating liquid is dried [℃] 1 Treatment liquid 1 Film 1 160 2 Treatment liquid 2 Film 1 160 3 Treatment liquid 3 Film 1 160 4 Treatment solution 4 Film 1 160 5 Treatment solution 5 Film 1 160 6 Treatment solution 6 Film 1 160 7 Treatment liquid 7 Film 1 160 8 Treatment solution 8 Film 1 160 9 Treatment liquid 1 Coating liquid 2 160 10 Treatment solution 6 Coating liquid 2 160 11 Comparative treatment solution 1 Film 1 160 12 Comparative treatment liquid 2 Film 1 160 13 Comparative treatment solution 3 Film 1 160 14 Comparative treatment solution 4 Film 1 160 15 Comparative treatment solution 5 Film 1 160 16 Comparative treatment solution 6 Film 1 160 17 Treatment liquid 1 Comparative film 1 160 18 Treatment solution 6 Comparative film 1 160 19 Treatment liquid 1 Comparative film 2 160 20 Treatment solution 6 Comparative film 2 160 twenty one Treatment liquid 1 Film 1 300 twenty two Treatment liquid 1 Film 1 300 twenty three Treatment liquid 1 - 160 twenty four Treatment solution 6 - 160

2. Evaluation 2-1. Adhesion resistance Cut the pre-coated metal material 1 to pre-coated metal material 20 into 50 mm squares, and superimpose the rubber layers of the cut pre-coated metal materials, and press them at 23°C and 2 MPa for 24 hours. After that, the pre-coated metal material was peeled off, the area where the rubber layer was transferred and peeled from the overlapped steel plate was measured, and the blocking resistance was evaluated based on the following criteria. ○ The transferred and peeled area is less than 5% × The transferred and peeled area is more than 5%

2-2. Bonding strength of vulcanized rubber Cut out the pre-coated metal material 1 ~ pre-coated metal material 20 into 25 mm wide x 60 mm long, so that the rubber layer surface is exposed in a 25 mm square area, and the cut out is sealed with a 17.5 mm heat-resistant fluorine tape Both ends of the pre-coated metal material in the longitudinal direction. Arrange the vulcanized nitrile rubber that has been cut into 25 mm wide x 125 mm long and 6 mm thick with a hardness of 60 degrees, and align it with the end face on the long side of the cut pre-coated metal material. It is in contact with the exposed rubber layer. Thereafter, the pre-coated metal material and the vulcanized nitrile rubber were thermocompression-bonded at 170°C and 98 MPa for 15 minutes, and the two were joined to obtain a composite material.

Fix the obtained composite material in the test jig described in Figure 1 of JIS K6256-2, grasp the end surface that is not in contact with the precoated metal material of the vulcanized nitrile rubber with a width of 50 mm, and use a tensile testing machine (Shimadzu Manufactured by the Mfg. Co., Ltd., with the device name "AUTOGRAPH AG-IS") and peeled at 90 degrees at a speed of 50 mm/min. The peel force due to the cohesive failure of the vulcanized nitrile rubber was measured, and the vulcanized rubber was evaluated based on the following criteria The bonding strength. ○ Cohesive failure occurs when the maximum peel force is 4 N/mm or more △ Cohesive failure occurs when the maximum peel force is 2 N/mm or more but less than 4 N/mm × Cohesive failure occurs when the maximum peel force is less than 2 N/mm

Table 4 shows the evaluation results. In addition, in the remarks of Table 4, the production conditions of individual pre-coated metal materials (the presence or absence of addition of inorganic compounds, organic compounds, halogen rubbers, and vulcanizing agents are indicated as follows: "○" means that the above components have been Add, "×" means that the above components are not added.).

[Table 4] Pre-coated metal material Evaluation Remarks Adhesion resistance Joint strength of vulcanized rubber Inorganic organic composite membrane Rubber layer Surface temperature of steel plate during pre-coating Inorganic compound Organic compound Halogen rubber Vulcanizing agent 1 ○ ○ ○ ○ ○ ○ 160 2 ○ ○ ○ ○ ○ ○ 160 3 ○ ○ ○ ○ ○ ○ 160 4 ○ ○ ○ ○ ○ ○ 160 5 ○ ○ ○ ○ ○ ○ 160 6 ○ ○ ○ ○ ○ ○ 160 7 ○ ○ ○ ○ ○ ○ 160 8 ○ ○ ○ ○ ○ ○ 160 9 ○ ○ ○ ○ ○ ○ 160 10 ○ ○ ○ ○ ○ ○ 160 11 × × × × ○ ○ 160 12 ○ △ × ○ ○ ○ 160 13 ○ △ × ○ ○ ○ 160 14 × △ ○ × ○ ○ 160 15 × △ ○ × ○ ○ 160 16 × △ ○ × ○ ○ 160 17 × △ ○ ○ ○ × 160 18 × △ ○ ○ ○ × 160 19 ○ × ○ ○ ○ excess 160 20 ○ × ○ ○ ○ excess 160 twenty one ○ × ○ ○ ○ ○ 300 twenty two ○ × ○ ○ ○ ○ 300 twenty three ○ × ○ ○ × × 160 twenty four ○ × ○ ○ × × 160

Pre-coated metal material 1 to pre-coated metal material 10 with a metal material, an inorganic-organic composite layer arranged on the above-mentioned metal material, and a rubber layer arranged in contact with the surface of the above-mentioned inorganic-organic composite layer, and adhesion is difficult to occur And the bonding strength of the vulcanized rubber is also high.

On the other hand, the pre-coated metal material 11 in which the inorganic-organic composite layer is not formed is prone to blocking, and the bonding strength of the vulcanized rubber is low. This is considered to be due to the fact that there is no inorganic-organic composite layer, so the adhesion to the rubber layer of the inorganic-organic composite layer is low, and the vulcanization reaction between the rubber layer and the surface of the metal material is incomplete, so the rubber layer and Joining of metal materials.

In addition, the pre-coated metal material 12 and the pre-coated metal material 13 to which the inorganic compound is not added to the inorganic-organic composite layer make it difficult to increase the bonding strength of the vulcanized rubber. This is considered to be because a hard coating that is easily broken by cohesion, which is caused by salts of metals derived from metal materials and organic acids, is formed.

In addition, the pre-coated metal material 14 to the pre-coated metal material 16 to which an organic compound is not added to the inorganic-organic composite layer tends to cause blocking, and it is difficult to increase the bonding strength of the vulcanized rubber. This is considered to be because the interaction between the organic acid and the halogen rubber did not occur, and the metal salts and oxides eluted from the metal material by the organic acid etching the metal material, and the bonding between the halogen rubber Nor did it happen.

In addition, the pre-coated metal material 17 and the pre-coated metal material 18 to which the vulcanizing agent is not added to the rubber layer are likely to cause blocking, and it is difficult to increase the joint strength of the vulcanized rubber. This is considered to be because the rubber layer was partially unvulcanized during the preparation of the pre-coated metal material, so the adhesion to other rubber layers did not decrease, and because the halogen rubber was also used during thermocompression bonding with the rubber molding material. It is not vulcanized, so the halogen rubber is not sufficiently hardened.

In addition, the precoated metal material 19 to the precoated metal material 22 in which the rubber layer has been completely vulcanized have difficulty in improving the bonding strength of the vulcanized rubber. This is considered to be because it is difficult for the molecules of the halogen rubber that has developed fluidity by heating to penetrate the outermost layer of the rubber molding material, and it is difficult to entangle with the molecules constituting the rubber molding material.

In addition, since the pre-coated metal material 23 and the pre-coated metal material 24 without a rubber layer have no rubber layer, although adhesion is difficult to occur, it is difficult to increase the joint strength of the vulcanized rubber.

This application is an application claiming priority based on the Japanese application No. 2018-247246 filed on December 28, 2018, and the patent scope of the application and the content described in the specification are used in this application. [Industrial use possibility]

The pre-coated metal material of the present invention is difficult to produce adhesion during storage and movement, and has good adhesion to the vulcanized rubber molding material. The composite material formed by joining the pre-coated metal material and rubber molding material of the present invention is preferably used in various electronic equipment, household electrical appliances, medical equipment, automobile bodies, vehicle mounting products, building materials, and the like.

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Claims (10)

A pre-coated metal material with: A metal material; An inorganic-organic composite layer disposed on the metal material; and A rubber layer configured to be in contact with the surface of the inorganic organic composite layer; wherein The rubber layer contains a halogen rubber and a vulcanizing agent for the halogen rubber. The pre-coated metal material as described in claim 1, wherein the inorganic organic composite layer comprises: An oxide, hydroxide or fluoride of a metal selected from the group consisting of Group IV metals, Group V metals and Group VI metals; and An organic acid. The pre-coated metal material as described in claim 2, wherein the metal selected from the group consisting of Group IV metals, Group V metals or Group VI metals is selected from Ti, Zr, Hf, V, Nb, A metal selected from the group consisting of Ta, Mo, and W. The pre-coated metal material as described in claim 1 or 2, wherein the inorganic-organic composite layer comprises: one selected from the group consisting of organic phosphonic acid and its salts, and polyvalent phenol and its salts Organic acid. The pre-coated metal material as described in claim 1 or 2, wherein the adhesion amount of the inorganic-organic composite layer is 10 mg/m ² or more and 200 mg/m ² or less. The pre-coated metal material as described in claim 1 or 2, wherein the halogen rubber is a halogen rubber selected from the group consisting of 2-chloroprene, chlorosulfonated polyethylene, and chlorinated rubber. The pre-coated metal material as described in claim 1 or 2, wherein the vulcanizing agent is selected from the group consisting of metal oxides, metal salts of unsaturated fatty acids, organic peroxides, and thiourea compounds Vulcanizing agent. The pre-coated metal material as described in claim 1 or 2, wherein the rubber layer is partially vulcanized by the halogen rubber. A method for manufacturing composite materials, including: On the surface of a pre-coated metal material as described in claim 1 or 2, a process in which a rubber molded material containing a rubber composition that has been vulcanized is placed in contact with the rubber layer; and A process of heating the rubber layer in contact with the rubber molding material to join the precoated metal material and the rubber molding material. A composite material with: A metal material; An inorganic-organic composite layer is disposed on the metal material; A rubber layer configured to be in contact with the surface of the inorganic-organic composite layer and containing a halogen rubber that has been vulcanized; and A rubber molding material is placed in contact with the surface of the rubber layer and contains a rubber composition that has been vulcanized.