KR20210124383A - Composite, manufacturing method thereof, and coated metal plate - Google Patents

Abstract

The composite of the present invention has a coated metal plate and a rubber layer disposed on the primer layer of the coated metal plate. A coating metal plate has a metal plate and the primer layer arrange|positioned on the said metal plate. A primer layer consists of a hardened|cured material of a resin composition containing a curable resin, a hardening|curing agent, and carbon-type particle|grains. The specific surface area of the carbon-based particles is 10 to 1500 m ² /g, the content of the carbon-based particles is 3 to 25 mass% with respect to the curable resin, and the content of the rubber component is 1 mass% or less with respect to the curable resin .

Description

Composite, manufacturing method thereof, and coated metal plate

The present invention relates to a composite, a method for manufacturing the same, and a coated metal plate.

A composite including a metal plate and a rubber layer bonded thereto is widely used, for example, in vibration-proof rubber for automobiles, anti-vibration rubber as a building member, and health care products.

For example, as a composite used in an oil seal, etc., in Patent Document 1, a metal plate, (a) an undercoat adhesive layer containing a phenol resin and an epoxy resin, and (b) a phenol resin, a halogenated polymer and a metal oxide An acrylic rubber-metal composite having an overcoat adhesive layer comprising a, and (c) an acrylic rubber layer in this order is disclosed.

Such a composite is 1) a step of cleaning or surface-treating the surface of a metal plate with a shot blast or the like, 2) a base-coating vulcanizing adhesive on the cleaned or surface-treated metal plate (to ensure adhesion with the metal plate). applying and drying to form an undercoat adhesive layer, 3) applying and drying an overcoating vulcanized adhesive (to ensure adhesion with the rubber layer) on the undercoating vulcanized adhesive layer to form an overcoating adhesive layer, 4) Laminating an unvulcanized rubber composition on the obtained top-coating vulcanized adhesive layer, and thermocompression bonding by hot press, etc., vulcanizing the unvulcanized rubber composition and vulcanization in the undercoating adhesive layer and the overcoating adhesive layer at the same time, It is obtained by bonding a rubber layer.

The vulcanized adhesive used for bonding such a metal plate and a rubber layer usually contains a halogenated rubber such as chlorinated rubber or brominated rubber, and a vulcanizing agent such as sulfur, in order to increase adhesiveness. As such a vulcanizing adhesive, a one-layer type vulcanizing adhesive that bonds a metal plate and a rubber layer with only one layer, a two-layer type vulcanizing adhesive consisting of two layers of an undercoat vulcanizing adhesive applied to the metal plate side and a topcoat vulcanizing adhesive applied to the rubber layer side, etc. have.

Japanese Patent Laid-Open No. 2007-283527

However, in the above method, since many steps are required before finally obtaining the composite, there is a problem that the productivity is low. In particular, it is preferable to abbreviate|omit the process of said 1) (process of washing|cleaning the surface of a metal plate), and the process of said 2) (process of forming an undercoat adhesive bond layer on the surface of a metal plate).

That is, if there is a coated metal plate provided with an undercoat adhesive layer, only the steps of 3) (a step of forming an overcoating adhesive layer) and 4) (a step of laminating and thermocompression bonding a rubber layer on the overcoating adhesive layer) are performed. Thus, a composite in which a metal plate and a rubber layer are adhered can be obtained. As described above, in order to reduce the number of steps and increase productivity, it is preferable to use a coated metal plate provided with an undercoat adhesive layer (ie, pre-coating).

However, in the conventional coated metal sheet having an undercoating vulcanized adhesive layer, for example, during storage by winding in a coil shape, the undercoating adhesive layer of the coated metal plate to be laminated and the backside of the metal plate are adhered, or (the undercoating adhesive layer on both sides of the metal plate) ), there is a problem that the undercoat adhesive layers are adhered or crosslinked, so-called blocking occurs. Therefore, it is calculated|required to obtain the composite_body|complex with favorable adhesiveness between a painted metal plate and a rubber layer, without causing such blocking.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composite having good adhesiveness, a method for producing the same, and a coated metal sheet used therefor that does not cause blocking.

This invention relates to the following composite_body|complex, its manufacturing method, and a coated metal plate.

The composite of the present invention is a composite having a metal plate, a coated metal plate having a primer layer disposed on the metal plate, and a rubber layer disposed on the primer layer of the coated metal plate, wherein the primer layer includes a curable resin, a curing agent and , composed of a cured product of a resin composition containing carbon-based particles, the specific surface area of the carbon-based particles is 10 to 1500 m ² /g, and the content of the carbon-based particles is 3 to 25 mass% with respect to the curable resin and the content of the rubber component is 1% by mass or less with respect to the curable resin.

The method for manufacturing the composite of the present invention includes a metal plate and a primer layer disposed on the metal plate, wherein the primer layer is made of a cured product of a resin composition including a curable resin, a curing agent, and carbon-based particles, The specific surface area of the carbon-based particles is 10 to 1500 m ² /g, the content of the carbon-based particles is 3 to 25% by mass relative to the resin, and the content of the rubber component is 1% by mass or less of the resin. a step of preparing a resin composition for a rubber layer comprising a first rubber-based polymer and a first crosslinking agent on the primer layer of the coated metal plate, followed by crosslinking to obtain a rubber layer disposed on the primer layer.

The coated metal plate of the present invention is a coated metal plate for bonding to a rubber layer, and has a metal plate, a chemical conversion coating film, and a primer layer in this order, wherein the chemical conversion coating film is a chromate coating or a silane coupling agent having an amino group. and an organic resin, wherein the primer layer is disposed on the outermost surface of the coated metal plate, and the primer layer is a cured product of a resin composition including a curable resin, a curing agent, and carbon-based particles. is made, the specific surface area of the carbon-based particles is 10 to 1500 m ² /g, the content of the carbon-based particles is 3 to 25 mass% with respect to the curable resin, and the content of the rubber component is with respect to the curable resin 1 mass % or less.

ADVANTAGE OF THE INVENTION According to this invention, the composite_body|complex which has favorable adhesiveness, its manufacturing method, and the coated metal plate which does not raise|generate blocking used for it can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of the composite_body|complex of this invention.
2 is a schematic cross-sectional view showing another example of the composite of the present invention.

The present inventors have found that, in a coated metal plate having a metal plate and a primer layer, by containing a predetermined amount of carbon-based particles in the primer layer, the rubber layer (or adhesive layer) and the rubber layer (or adhesive layer) can be adhered well without substantially containing a rubber component or the like. found that it can.

The reason is not clear, but it is thought to be as follows. That is, the carbon-based particles contained in the primer layer are easy to chemically adsorb the rubber component contained in the rubber layer (or adhesive layer). Such chemical adsorption is more likely to occur as the average primary particle diameter of the carbon-based particles is small and the specific surface area is large. Thereby, it is thought that the adhesiveness of a primer layer and a rubber layer (or adhesive bond layer) becomes high.

If there is such a coated metal plate, the conventional step 1) (cleaning or surface treatment of the surface of the metal plate) and the step 2) (step of forming an undercoat adhesive layer) can be omitted. That is, a composite can be obtained with a small number of steps. In addition, since the primer layer of the painted metal plate does not contain a rubber component substantially (for obtaining adhesiveness), for example, during the winding state or storage of the painted metal plate, the primer layer of the painted metal plate and the back surface of the metal plate adhere. Alternatively, it is possible to suppress the occurrence of blocking such as adhesion between the primer layers. The present invention has been made based on such knowledge.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

1. Complex

The composite of the present invention has a coated metal plate and a rubber layer disposed on the primer layer of the coated metal plate.

1-1. painted metal plate

A coated metal plate has a metal plate and the primer layer arrange|positioned on this metal plate. It is preferable that the coating metal plate further has a chemical conversion film arrange|positioned between the metal plate and the primer layer from a viewpoint of improving the adhesiveness of a metal plate and a primer layer. Moreover, it is preferable to further have the rust prevention layer (rust prevention layer) arrange|positioned between a chemical conversion film and a primer layer from a viewpoint of suppressing corrosion of a metal plate highly.

[plate]

The kind of metal plate is not specifically limited. Examples of the metal sheet include cold rolled steel sheet, galvanized steel sheet (electrical Zn plating, hot-dip Zn plating), alloyed galvanized steel sheet (hot-dip galvanized steel sheet subjected to alloying treatment after hot-dip Zn plating), zinc alloy plated steel sheet (molten Zn-Mg plating, Hot-dip Zn-Al-Mg plating, hot-dip Zn-Al plating), hot-dip Al-Si coated steel sheet, stainless steel sheet (austenitic, martensitic, ferritic, ferritic/martensitic two-phase), aluminum sheet, aluminum alloy sheet , copper plate, brass plate, titanium plate, and the like.

The metal plate may be subjected to a known pre-treatment such as degreasing treatment or surface cleaning by corona discharge, or roughening by mechanical polishing, acid cleaning, shot blasting, or the like, if necessary.

The thickness of the metal plate can be appropriately set according to the use of the composite, but when used, for example, as a vibration-proof member or the like, it can be, for example, 0.2 to 2.0 mm.

[Chemical treatment film]

A chemical conversion treatment film is arrange|positioned between a metal plate and a primer layer, and improves the adhesiveness between a metal plate and a primer layer. Although the chemical conversion treatment film should just be arrange|positioned in the area|region (joint area|region) joined with a rubber layer at least among the surface of a metal plate, it may be arrange|positioned on the whole surface of a metal plate.

The kind of chemical conversion coating film is not specifically limited, Chromate films, such as a chromate type|system|group and a phosphate chromate type|system|group, may be sufficient, and a chromate-free film may be sufficient. For example, it is preferable that a chemical conversion treatment film is a chromate-free film from a viewpoint of reducing environmental load.

The chromate-free film contains an inorganic compound (which does not contain chromate) and an organic resin.

Examples of the inorganic compound include a silane compound (eg, a silane coupling agent), a titanium compound (eg, Ti-Mo composite material), a fluorine acid compound (eg, hexafluorotitanic acid), and a zirconium compound (eg, hexafluorotitanic acid). fluorozirconic acid). Such an inorganic compound may be used by 1 type, and may be used in combination of 2 or more type. Especially, it is preferable that it is a silane compound, and, as for an inorganic compound, it is more preferable that it is a silane coupling agent at the point which improves the adhesiveness of a metal plate and a primer layer easily.

The silane coupling agent preferably has an amino group, preferably a primary amino group, from the viewpoint of increasing the reactivity with the epoxy resin and curing agent contained in the primer layer to be described later. Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-(2-aminoethyl)aminopropyltrimethoxysilane, N-(2-aminoethyl)aminopropyl Methyldimethoxysilane, N-(2-aminoethyl)aminopropyltriethoxysilane, N-(2-aminoethyl)aminopropylmethyldiethoxysilane, N-(2-aminoethyl)aminopropylmethyldimethoxysilane, etc. This is included.

An organic resin can improve affinity with resin contained in a primer layer, and can improve the adhesiveness of a chemical conversion treatment film and a primer layer. Examples of the organic resin include urethane resin, phenol resin, N-methylglucamine resin, tannic acid and polyacrylic acid. These organic resins may be used by 1 type, and may be used in combination of 2 or more type. Moreover, such an organic resin may be hardened|cured with hardening|curing agents, such as an isocyanate compound and a polycarbodiimide compound.

The amount of adhesion of the chemical conversion coating film is not particularly limited as long as the adhesion between the metal plate and the primer layer can be improved. For example, in the case of a chromate film, what is necessary is just to adjust the adhesion amount so that the ^{total Cr conversion amount may be 5-100 mg/m<2>.} In addition, in the case of a chromate-free film, the adhesion amount is in ^{the range of 10 to 300 mg/m 2} in the film containing the silane compound, and the adhesion amount is in the range of 10 to 500 mg/m ² in the film containing the titanium compound, What is necessary is just to adjust the adhesion amount, respectively, so that it may become the range of 3-100 ^mg/m<2> of the adhesion amount in terms of fluorine or total metal element in a fluorine acid type film.

[Anti-rust layer]

The rust preventive layer is a metal plate, for example, when it is necessary to protect from a corrosive environment such as salt damage, such as a cold rolled steel plate or a plated steel plate, it is arranged in order to improve corrosion resistance.

It is preferable that a rust preventive layer consists of hardened|cured material of the resin composition containing curable resin, a hardening|curing agent, and a rust preventive pigment.

The same thing as what was illustrated as curable resin used for a primer layer is contained in the example of curable resin used for a rust prevention layer. The curable resin used for a rust preventive layer and the curable resin used for a primer layer may be same or different, and the same thing is preferable from the point of being easy to obtain favorable adhesiveness with a primer layer.

Examples of the rust preventive pigment include chromium-based rust preventive pigments such as calcium chromate and strontium chromate; and chromium-free rust preventive pigments such as magnesium phosphate, magnesium hydrogen phosphate, zinc phosphate, aluminum dihydrogen tripolyphosphate, and calcium silicate. One type may be sufficient as these rust preventive pigments, and they may combine 2 or more types.

The thickness of the rust preventive layer should just be a range which can provide sufficient corrosion resistance to a coated metal plate, for example, it is preferable that it is 1-20 micrometers, and it is more preferable that it is 3-10 micrometers.

[Primer layer]

A primer layer is arrange|positioned in the outermost layer of a coating metal plate above a metal plate, and adheres (joins) a metal plate and a rubber layer (or adhesive bond layer). From the viewpoint of increasing the heat resistance of the composite obtained while improving the adhesiveness between the metal plate and the rubber layer (or adhesive layer), the primer layer is composed of a cured product of a resin composition containing a curable resin, a curing agent, and carbon-based particles. desirable.

(curable resin)

Curable resin should just have a functional group (for example, a hydroxyl group, etc.) which reacts with a hardening|curing agent, and has favorable adhesiveness with a chemical conversion coating film, and is not restrict|limited in particular. For example, when the chemical conversion film contains a silane coupling agent having an amino group, the curable resin contained in the primer layer contains a reactive group capable of reacting with an amino group (carboxyl group, ester group, epoxy group, ketone group, halogen group, etc.) It is preferable that it is resin. In addition, when the chemical conversion film contains a silane coupling agent having an epoxy group, the curable resin contained in the primer layer is preferably a resin having a functional group (carboxyl group, amino group, hydroxyl group, etc.) capable of reacting with the epoxy group. Among them, it is easy to obtain good adhesion that does not cause peeling of the coating film during molding processing, or when the chemical conversion film contains a silane coupling agent having an amino group, good adhesion with the chemical conversion film is easily obtained, etc. , It is preferable that curable resin is curable polyester resin or an epoxy resin.

Curable polyester resin is a hydroxyl-group containing polyester resin, for example, It is a polycondensate of a polyhydric carboxylic acid component and a polyhydric alcohol component.

Examples of the polyhydric carboxylic acid component include aromatic polyhydric carboxylic acids and anhydrides thereof, such as terephthalic acid, isophthalic acid, phthalic acid or anhydride thereof, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, trimellitic acid, and and aliphatic polyhydric carboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and butane tricarboxylic acid.

Examples of the polyhydric alcohol component include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, 1,2-propane Diol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-pentanediol, 2,3-pentanediol, 1,4-pentanediol, 1,4-hexane Diol, 2,5-hexanediol, 3-methyl-1,5-pentanediol, 1,2-dodecanediol, 1,2-octadecanediol, 1,4-cyclohexanediol, 1,4-cyclohexane aliphatic polyhydric alcohols such as dimethanol, trimethylol propane (TMP), pentaerythritol (PE), trimethylol ethane (TME), erythritol, dipentaerythritol, sorbitol, and glycerin;

and aromatic polyhydric alcohols such as bisphenol A alkylene oxide adduct and bisphenol S alkylene oxide adduct. The polyhydric alcohol component constituting the hydroxyl group-containing polyester resin preferably contains a trihydric or higher alcohol, and may further contain a dihydric alcohol.

Moreover, epoxy-modified polyester resin is also contained in the example of curable polyester resin. The epoxy-modified polyester resin may be, for example, an esterification reaction of a carboxyl group-containing polyester resin and an epoxy compound.

As described above, the carboxyl group-containing polyester resin as a raw material may be a polycondensate of a polyhydric carboxylic acid component and a polyhydric alcohol component. However, it is preferable that the ratio of the polyhydric carboxylic acid component/polyhydric alcohol component is adjusted so that a carboxyl group may become a predetermined amount, or that a polyhydric carboxylic acid component contains trivalence or more carboxylic acid. Moreover, the carboxyl group-containing polyester resin used as a raw material may make the hydroxyl group-containing polyester resin react with an acid anhydride.

It is preferable that the curable polyester resin has an aromatic skeleton (the polyhydric carboxylic acid component contains an aromatic carboxylic acid component, or the polyhydric alcohol component contains an aromatic polyhydric alcohol) from the viewpoint of improving the heat resistance of the obtained primer layer. .

Although the number average molecular weight of curable polyester resin is not specifically limited, From a viewpoint of the intensity|strength and workability of a coating film, it is several thousands - several thousand, Specifically, it is preferable that they are 3000-15000. Among them, from the viewpoint of increasing the flexibility of the primer layer, making it easier to swell by oil in the rubber layer (or solvent in the adhesive layer), and improving the adhesiveness, the number average molecular weight is preferably higher, 5000 It is more preferable that it is ~15000. The number average molecular weight of curable polyester resin can be measured in polystyrene conversion by the gel permeation chromatography (Gel Permeation Chromatograph) method. Specific measurement conditions can be the same as in Examples described later.

In the example of an epoxy resin, Bisphenol-type epoxy resins, such as a bisphenol A epoxy resin, a bisphenol F-type epoxy resin, a hydrogenated bisphenol A-type epoxy resin, and a brominated bisphenol A-type epoxy resin; novolac-type epoxy resins which are polyglycidyl ethers of phenol or alkylphenol novolac resins, such as phenol novolak-type epoxy resins, orthocresol novolak-type epoxy resins, and bisphenol A novolak-type epoxy resins; Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol tetra alkylene glycol-type epoxy resins that are polyglycidyl ethers of alkylene glycols such as glycidyl ether; Orthophthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid Glycidyl ester type epoxy resins, such as diglycidyl ester, sebacic acid diglycidyl ester, and dimer acid diglycidyl ester; and glycidyl amine type epoxy resins such as triglycidyl isocyanurate and tetraglycidyl diaminodiphenylmethane. Among them, an epoxy resin (aromatic epoxy resin) having an aromatic ring is preferable from the viewpoint of easily obtaining a cured coating film with high strength or heat resistance or easy to obtain adhesion to a metal plate (or chemical conversion film). , more preferably a bisphenol-type epoxy resin, and still more preferably a bisphenol-A epoxy resin.

Although the number average molecular weight of an epoxy resin is not specifically limited, From a viewpoint of the intensity|strength of a coating film, or workability, it is preferable that it is about several thousand. Specifically, it is preferable that the number average molecular weights of an epoxy resin are 400-25000. If the number average molecular weight of the epoxy resin is 400 or more, a coating film of good strength is easily obtained, and corrosion resistance and the like are also easy to be improved. When the number average molecular weight of the epoxy resin is 25000 or less, since the viscosity of the coating liquid does not become too high, the coating workability and workability by a roll coater etc. are hard to fall. Moreover, since the ratio of the solid content to which it occupies in a coating material does not decrease too much, productivity is also hard to fall. Among them, from the viewpoint of increasing the flexibility of the primer layer, making it easy to swell by the oil content in the rubber layer (or the solvent in the adhesive layer), and increasing the adhesiveness, it is preferable that the number average molecular weight is higher, and the number of the epoxy resin is higher. As for average molecular weight, it is more preferable that it is 4000-20000. The number average molecular weight of an epoxy resin can be measured by the method similar to what was mentioned above.

Moreover, the modified epoxy resin (For example, the epoxy resin modified|denatured with alkanolamine etc.) may be sufficient as the epoxy resin which has a functional group which reacts with isocyanate groups, such as an amino group or a hydroxyl group. Especially, from a viewpoint of improving affinity with the component contained in a chemical conversion coating film or a rubber layer, and making it easy to obtain favorable adhesiveness, it is preferable that an epoxy resin is a modified epoxy resin which has a functional group which reacts with an isocyanate group.

It is preferable that content of curable resin is 55-88.5 mass % with respect to solid content of a resin composition. When the content of the curable resin is 55 mass% or more, the resulting primer layer can not only have sufficient film strength, but also have good scratch resistance, corrosion resistance, water resistance, chemical resistance, and the like. Since the viscosity of the resin composition at the time of forming a primer layer does not become high that content of curable resin is 88.5 mass % or less, coating workability and workability are hard to fall. As for content of curable resin, it is more preferable that it is 60-85 mass % with respect to the solid content of a resin composition from the said viewpoint.

(hardener)

The curing agent is not particularly limited as long as it can cure the curable resin. Examples of the curing agent for curing the epoxy resin include an amine compound, an acid anhydride and an imidazole compound. Moreover, an isocyanate compound and a melamine compound are contained in the example of the hardening|curing agent of the modified|denatured epoxy resin and curable polyester resin which has an amino group or a hydroxyl group etc. as mentioned above.

Especially, an isocyanate compound is preferable from a viewpoint of providing flexibility to a primer layer and making it easy to suppress a crack, and also making it easy to improve adhesiveness with a rubber layer (or adhesive bond layer). The primer layer obtained by using an isocyanate compound as a curing agent easily swells appropriately by the solvent in the adhesive layer or oil in the rubber layer (compared to the case of using a melamine-based curing agent), and the reaction point with the carbon-based particles also tends to increase. am.

In the example of an isocyanate compound, Aliphatic isocyanate compounds, such as hexamethylene diisocyanate (HDI), lysine diisocyanate, and dimer acid diisocyanate (DDI); alicyclic isocyanate compounds such as norbornene diisocyanate (NBDI), isophorone diisocyanate (IPDI), cyclohexane diisocyanate, and dicyclohexyl methane diisocyanate; Methylene diphenyl diisocyanate (MDI), tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthylene 1,5-diisocyanate (NDI), tetramethylene xylene diisocyanate (TMXDI), phenylene di Aromatic isocyanate compounds, such as an isocyanate, are contained. Especially, an aliphatic isocyanate compound is preferable from a viewpoint that the primer layer which has favorable adhesiveness can be obtained.

It is preferable that content of a hardening|curing agent is 10-40 mass % with respect to curable resin. Curable resin can fully be hardened as content of a hardening|curing agent is 10 mass % or more. Thereby, it is easy to obtain a primer layer of sufficient film strength, and the adhesiveness (or bonding property) between a primer layer and an adhesive layer is also easy to be obtained. If the content of the curing agent is 40% by mass or less, it is difficult to cause bleed-out.

(carbon-based particles)

The carbon-based particles are preferably carbon-based particles having a nitrogen adsorption specific surface area of 10 to 1500 m ² /g. If the nitrogen adsorption specific surface area of the carbon-based particles is 10 m ² /g or more, since the carbon-based particles are appropriately aggregated, the oil content (or the organic solvent for applying the adhesive composition) for applying the resin composition for rubber layer is easy to trap. Thereby, a primer layer is easy to swell and it is easy to obtain favorable adhesiveness. On the other hand, when the nitrogen adsorption specific surface area of the carbon-based particles is 1500 m ² /g or less, the interaction with the rubber layer (or adhesive layer) with the rubber layer (or adhesive layer) is difficult to decrease because there are suitably many reaction points with the rubber layer (or adhesive layer). . As for the specific surface area of carbon-type particle|grains, it is more preferable that it is ^{30-500 m<2>/g.}

The specific surface area (nitrogen adsorption specific surface area) of carbon-type particle|grains can be measured by the BET method based on JISZ8830:2013.

The type of carbon-based particles is not particularly limited, as long as the nitrogen adsorption specific surface area satisfies the above range. Examples of such carbon-based particles include carbon black, activated carbon, and the like. Among them, the average primary particle diameter is small (it is easy to adjust to the range described later), the crosslinking point with the rubber component contained in the rubber layer (or adhesive layer) is increased, and the adhesion between the primer layer and the rubber layer (or adhesive layer) is increased. Carbon black is preferable from the point of being easy to raise.

It is preferable that the average primary particle diameter of carbon-type particle|grains is 10 nm - 10 micrometers. If the average primary particle diameter is 10 nm or more, it is easy to reduce the cost, and if it is 10 µm or less, it is difficult to expose from the surface of the primer layer, so that it is difficult to cause cracking of the coating film. It is more preferable that it is 10-100 nm, and, as for an average primary particle diameter, it is more preferable that it is 10-50 nm from a viewpoint of remarkably improving adhesiveness with a rubber by small particle hardening.

The average primary particle diameter of carbon-type particle|grains can observe the particle diameter of 20 arbitrary particle|grains with an electron microscope, and can measure them as these arithmetic mean particle diameters. Separation and recovery of carbon-based particles can be carried out, for example, by dissolving the primer layer of the coated metal plate in an organic solvent for dissolving the curable resin constituting the primer layer, and then filtering and drying the separated carbon-based particles. .

The pH of the carbon-based particles is preferably in the range of 6 to 8. If the pH is 6 or more, since the oxygen content of the carbon-based particles is moderately large, the dispersibility becomes good easily, and if it is 8 or less, the storage stability of the obtained coating material is hard to fall. The pH can be measured by a pH meter using a glass electrode.

It is preferable that content of carbon-type particle|grains is 3-25 mass % with respect to curable resin contained in a primer layer. If the content of the carbon-based particles is 3% by mass or more, it is easy to sufficiently increase the adhesion between the primer layer and the rubber layer (or adhesive layer), and it is difficult to partially cause interfacial peeling between the primer layer and the rubber layer (or adhesive layer). have. It is easy to suppress that a primer layer becomes weak that content of a carbon-type particle is 25 mass % or less. Thereby, when processing a coating metal plate, it is easy to suppress generation|occurrence|production of the cohesive failure of a primer layer, and it can suppress that workability falls. It is preferable that content of carbon-type particle|grains is 4-20 mass % with respect to curable resin contained in a primer layer from the said viewpoint.

The carbon-type particle|grains may exist uniformly in a primer layer, and may be unevenly distributed in the thickness direction. From the viewpoint of improving the adhesiveness between the primer layer and the rubber layer (or adhesive layer), the carbon-based particles may be included in at least the surface layer portion on the rubber layer (or adhesive layer) side of the primer layer.

As described above, the primer layer containing carbon-based particles has good adhesion to the rubber layer (or adhesive layer) even if it does not contain a rubber component as in the prior art. Therefore, it is possible for the primer layer to contain substantially no rubber component. Specifically, the content of the rubber component is 1 mass% or less, preferably 0.1 mass% or less, with respect to the curable resin contained in the primer layer.

(other ingredients)

The primer layer is, if necessary, titanium dioxide, iron oxide, various calcined pigments, color pigments such as cyanine blue and cyanine gray, extender pigments such as calcium carbonate, clay, barium sulfate, metal powder such as aluminum powder, bone agent, defoaming agent, leveling agent Agents, surface conditioners, viscosity modifiers, dispersants, waxes, and rust preventive pigments may further contain components other than the above. Moreover, in the example of another component, although a rust preventive pigment may also be contained in addition to the above, when providing a rust preventive layer between a primer layer and a metal plate, it is not required. Especially, it is preferable that a primer layer further contains an aggregate. This is because the dispersibility of the carbon-based particles tends to be higher by the addition of the aggregate.

About aggregate:

An aggregate can improve film hardness and abrasion resistance of a primer layer, or can provide an unevenness|corrugation to the surface of a primer layer, and can improve an external appearance. An inorganic aggregate may be sufficient as an aggregate, and an organic aggregate may be sufficient as it. The shape of the aggregate is not particularly limited, and may be any of scaly, fibrous, granular or lumpy shapes.

Examples of the scaly inorganic aggregate include glass flakes, barium sulfate flakes, graphite flakes, synthetic mica flakes, synthetic alumina flakes, silica flakes, and mica-like iron oxide (MIO). Examples of the fibrous inorganic aggregate include potassium titanate fibers, wollastonite fibers, silicon carbide fibers, alumina fibers, alumina silicate fibers, silica fibers, rock wool, slag wool, glass fibers, carbon fibers. Examples of the organic aggregate include acrylic particles and polyacrylonitrile particles. Glass beads, silica particles, and titania particles are included in examples of the granular or lump-form inorganic aggregate or matting agent.

(Properties)

The thickness of the primer layer is not particularly limited, as long as it can sufficiently adhere the metal plate (or chemical conversion film) and the rubber layer (or adhesive layer).

It is preferable that the thickness of a primer layer is 1-30 micrometers from the said viewpoint. When the thickness of the primer layer is 1 µm or more, good adhesion with the rubber layer (or adhesive layer) is easily obtained. Moreover, it is easy to thin a coating metal plate that the thickness of a primer layer is 30 micrometers or less. It is more preferable that it is 3-20 micrometers from the said viewpoint, and, as for the thickness of a primer layer, it is still more preferable that it is 5-10 micrometers. In addition, when a primer layer is comprised by two or more layers, the thickness of a primer layer says those total thickness.

A primer layer may be comprised by one layer, and may be comprised by two or more layers. For example, when a coating metal plate has a rust prevention layer, it is preferable that a primer layer is comprised by one layer. In addition, when the coated metal plate does not have a rust preventive layer, the primer layer is disposed on the metal plate (or chemical conversion film) side, the first primer layer having a relatively small content of carbon-based particles, and the rubber layer (or adhesive layer) side You may have a 2nd primer layer arrange|positioned at the carbon-type particle|grains with relatively much content. The 1st primer layer may contain a rust preventive pigment from a viewpoint of improving the corrosion resistance of a metal plate.

1-2. rubber layer

The rubber layer is disposed on the primer layer of the painted metal plate. A rubber layer consists of a crosslinked product of the resin composition for rubber layers containing the 1st rubber-type polymer as a raw material, and a 1st crosslinking agent.

(First rubber-based polymer)

The first rubber-based polymer is not particularly limited, and may be a diene-based polymer or a non-diene-based polymer.

Examples of the diene-based polymer include butadiene rubber (BR), isoprene rubber (IR), isobutylene isoprene rubber (IIR), nitrile butadiene rubber (NBR), chloroprene rubber (CR), nitrile isoprene rubber (NIR), natural rubber (NR), vinylpyridine butadiene rubber (PBR), styrene butadiene rubber (SBR), carboxy styrene isoprene rubber (XSBR), carboxy nitrile butadiene rubber (XNBR). Among them, nitrile butadiene rubber (NBR) and styrene butadiene rubber (SBR) are preferable, and natural rubber (NR) and nitrile butadiene rubber (NBR) are more preferable from the viewpoint of adhesiveness and versatility.

Examples of the non-diene-based polymer include ethylene propylene diene rubber (EPDM), chlorosulfonated polyethylene (CSM), acrylic rubber (ACM), urethane rubber (U), silicone rubber (Q), epichlorohydrin rubber (ECO) is included. Among them, ethylene propylene rubber (EPDM) is preferable from the viewpoint of versatility.

(first crosslinking agent)

What is necessary is just to select a 1st crosslinking agent according to the kind of 1st rubber-type polymer as a raw material. Examples of the first crosslinking agent include sulfur (for example, Hooi Chemical Industry Co., Ltd. powder sulfur 200 mesh), an oxime compound (for example, dimethyl glyoxime (DMG), diacetyl monooxime (DAM)), a polyamine compound (for example, For example, N,N'-disinnamylidine 1,6-hexanediamine, hexamethylenediamine monocarbonate, 4,4'-methylenebis(cyclohexylamine) carbamate), organic peroxides (such as dicumyl peroxide, Cumene hydroperoxide, p-methane hydroperoxide, 2,5-dimethyl hexane-2,5-dihydro peroxide, di-t-butyl peroxide, benzoyl peroxide, m-toluyl peroxide, 2,5 -Dimethyl-2,5-di(t-butyl peroxy)hexane), polyol compounds (eg 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl) perfluoropropane, hydroquinone).

The oxime compound can be used as a crosslinking agent for diene polymers such as isobutylene isoprene rubber (IIR), nitrile butadiene rubber (NBR), and styrene butadiene rubber (SBR), for example. The polyamine compound can be used for a rubber-based polymer (CR, ACM, etc.) having a halogen atom serving as a crosslinking point. Organic peroxides can be used as a crosslinking agent for many rubber-based polymers except for a part of IIR and the like. One type may be sufficient as a crosslinking agent, and they may combine two or more types.

It is preferable that content of a 1st crosslinking agent is 3-10 mass % with respect to the 1st rubber-type polymer used as a raw material, for example.

(other ingredients)

The resin composition for rubber layers may further contain components other than the above as needed. Examples of the other component include a heat-resistant rubber polymer, a plasticizer, an anti-aging agent, a crosslinking accelerator, a reinforcing material, and the like.

About heat-resistant rubber polymers:

The resin composition for rubber layers may further contain a polymethylene chain rubber polymer as the heat-resistant rubber polymer. For example, since a diene-based polymer containing many double bonds in a molecule lacks heat resistance, by adding an appropriate amount of a polymethylene chain-based rubber polymer having high heat resistance and not containing a double bond in a molecule, the resin composition for a rubber layer Deterioration due to heat can be further suppressed.

The content of the polymethylene chain rubber polymer is preferably 0 to 60 mass %, more preferably 10 to 50 mass %, still more preferably 15 to 35 mass %, with respect to the first rubber polymer used as a raw material. .

About plasticizers:

Examples of plasticizers include stearic acid. One type may be sufficient as a plasticizer, and they may combine two or more types. Content of a plasticizer may be 0.5-4.0 mass % with respect to the 1st rubber-type polymer used as a raw material, for example.

About antioxidants:

Examples of antioxidants include naphthylamine, diphenylamine, p-phenylenediamine, quinoline, hydroquinone derivative, monophenol, polyphenol, thiobisphenol, hindered phenol, and phosphorous acid ester. do. One type of antioxidant may be sufficient and they may combine 2 or more types. The content of the antioxidant may be, for example, 0.5 to 8.0 mass% with respect to the first rubber-based polymer used as a raw material.

For crosslinking accelerators:

Examples of the crosslinking accelerator include guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, thiourea, thiuram, dithiocarbamate, xanthate, zinc oxide (鉛華)) is included. The number of crosslinking accelerators may be one, and they may combine two or more types. The content of the crosslinking accelerator may be, for example, 1.0 to 8.0 mass% with respect to the first rubber-based polymer used as a raw material.

About the reinforcement:

Examples of the reinforcing material include carbon black, silica, and the like. It is preferable that content of a reinforcing material is 10-60 mass % with respect to a 1st rubber-type polymer. Moreover, it is preferable that the total content of another component is 30 mass % or less with respect to a rubber layer.

(Properties)

The thickness of the rubber layer can be appropriately set depending on the use of the composite, but is preferably 10 µm or more, for example, from the viewpoint of expressing sufficient rubber elasticity. If the thickness of the rubber layer is 10 µm or more, it is easy to express vibration resistance. In addition, if it is a use which has vibration-proof property, it is not necessary to set the thickness of a rubber layer, and 30 mm may be sufficient, for example.

1-3. another floor

The composite of the present invention may further include other layers, such as an adhesive layer, if necessary. For example, when the rubber layer is a rubber layer in which adhesion with a primer layer such as EPDM is difficult to be obtained, an adhesive layer is further disposed between the primer layer and the rubber layer from the viewpoint of further enhancing the adhesion between the primer layer and the rubber layer of the coated metal plate. good to do

[Adhesive layer]

The adhesive layer consists of a crosslinked product of the second rubber-based polymer and the adhesive composition containing the second crosslinking agent.

(Second rubber-based polymer)

Examples of the second rubber-based polymer used for the adhesive layer include those exemplified as the first rubber-based polymer used for the rubber layer. For example, when the first rubber-based polymer included in the rubber layer is a diene-based polymer, the second rubber-based polymer included in the adhesive layer is preferably a halogenated rubber-based polymer.

Examples of the halogenated rubber-based polymer may be a halide of the aforementioned diene-based polymer or a non-diene-based polymer. Examples of such a halogenated rubber polymer include a polymer of dichlorobutadiene, a polymer of brominated dichlorobutadiene, chloroprene rubber (CR), chlorosulfonated polyethylene (CSM), epichlorohydrin rubber (ECO), brominated rubber such as chlorinated polyethylene, or chlorinated polyethylene. rubber is included.

(Second crosslinking agent)

The second crosslinking agent may be sulfur or an organicated oxide.

(other ingredients)

The adhesive composition may further contain other components, such as a metal oxide and a phenol resin, as needed.

The metal oxide may function as a crosslinking aid or filler. Titanium oxide, zinc oxide, magnesium oxide, calcium oxide, etc. are contained in the example of a metal oxide. Among them, a mixture of titanium oxide and an oxide of a divalent metal is preferable.

The phenolic resin may have a function of increasing adhesion between the primer layer and the rubber layer. Examples of the phenol resin include a novolak-type phenol resin and a resol-type phenol resin.

The adhesive composition may be commercially available as a topcoat vulcanization adhesive. Examples of such commercially available products include Chemlock 210, 215, 607, 5150, 6108, 6110, 6125, 6225, XJ150, XJ551, XJ552, and XJ549 from Road Corporation.

(Properties)

The thickness of the adhesive layer is not particularly limited, and may be sufficiently adhered to the primer layer and the rubber layer. The thickness of an adhesive bond layer can be 5-50 micrometers, for example. When the thickness of the adhesive layer is 5 µm or more, good adhesion between the primer layer and the rubber layer is easily obtained. Moreover, it is easy to thin a coating metal plate that the thickness of an adhesive bond layer is 30 micrometers or less. It is more preferable that it is 5-50 micrometers from the said viewpoint, and, as for the thickness of an adhesive bond layer, it is still more preferable that it is 10-30 micrometers.

1-4. layer composition

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of the composite_body|complex of this invention.

As shown in FIG. 1 , the composite 10 includes a coated metal plate 20 , an adhesive layer 30 , and a rubber layer 40 in this order. The coating metal plate 20 has the metal plate 21, the chemical conversion treatment film 22, and the primer layer 23 in this order. The primer layer 23 and the rubber layer 40 of the coated metal plate 20 are favorably adhered (or bonded) via the adhesive layer 30 . In addition, the adhesive bond layer 30 may be abbreviate|omitted.

And, the surface layer part including the adhesive surface with the adhesive layer 30 (in the case of not having an adhesive layer, the rubber layer 40) in the primer layer 23, the solvent in the adhesive layer 30 (or in the rubber layer 40) It is preferable that it is swollen with oil). Thereby, good adhesiveness with the adhesive bond layer 30 (or the rubber layer 40) is easy to be obtained. A swelling part can be confirmed by low-vacuum SEM observation of the cross section of the primer layer 23, for example.

2 is a schematic cross-sectional view showing another example of the composite of the present invention. The composite 10 shown in FIG. 2 is configured in the same manner as in FIG. 1 except that it further has a rust preventive layer 24 disposed between the chemical conversion coating film 22 of the painted metal plate 20 and the primer layer 23, have. Such a composite 10 may have higher corrosion resistance.

2. Method of Preparation of Composite

The method for producing the composite of the present invention includes (1) a step of preparing a coated metal plate, (2) applying a resin composition for a rubber layer on the primer layer of the coated metal plate, crosslinking, and bonding (bonding) a rubber layer with the coated metal plate has a process to obtain Hereinafter, in the example in which a coated metal plate has a chemical conversion treatment film, each process is demonstrated.

About the process of (1)

First, a chemical conversion treatment liquid is applied to the surface of a metal plate, and a chemical conversion treatment film is formed.

As the metal plate, the one described above can be used. The metal plate may be subjected to a known pre-coating treatment such as surface cleaning by degreasing treatment or corona discharge, or roughening by mechanical polishing, acid cleaning, shot blasting, or the like, if necessary.

A chemical conversion liquid is a solution containing the structural component of the chemical conversion treatment film mentioned above. For example, the chromate-free chemical conversion treatment liquid may be an aqueous solution containing the above-described inorganic compound and an organic resin. The chemical conversion treatment liquid may further contain, in addition to water, a small amount of alcohol, a ketone, or a cellosolve-based water-soluble organic solvent as needed.

The chemical conversion liquid may further contain a hardening|curing agent for hardening an organic resin as needed. Examples of the curing agent include isocyanate compounds such as diisocyanate compounds and aliphatic diisocyanate compounds having an aromatic ring, and polycarbodiimide compounds.

It is preferable that the solid content concentration of a chemical conversion treatment liquid is 0.1-40 mass %. If the solid content concentration is 0.1 mass% or more, a chemical conversion coating film having a sufficient thickness is easily obtained. On the other hand, when the solid content concentration is 40% by mass or less, the storage stability of the chemical conversion solution is less likely to decrease. It is preferable that the pH of chemical conversion treatment liquid is adjusted in the range of 3-12.

Then, the chemical conversion solution is applied to the surface of a metal plate subjected to alkali degreasing by a roll coating method, a spray method, a curtain flow method, a spin coating method, a dip coating method, or the like, and dried at room temperature without washing with water. Although it is also possible to form a chemical conversion coating film by drying at room temperature, when continuous operation is considered, it is preferable to shorten the drying time at the temperature of 50 degreeC or more. However, it is preferable that a drying temperature is 200 degrees C or less from a viewpoint of reliably suppressing thermal decomposition of the organic component contained in a chemical conversion treatment film.

Next, on the chemical conversion treatment film of the obtained metal plate, a resin composition (resin composition for a primer layer) containing the above-mentioned curable resin and carbon particles is applied, dried and heat treated to form a primer layer. When the resin composition for a primer layer contains a hardening|curing agent, heat processing is performed under the conditions that the said resin composition hardens. On the other hand, even if the resin composition is completely cured, since a polar group derived from an epoxy resin or the like exists in the surface layer of the primer layer, it is likely to swell by the oil content in the rubber layer (or the solvent in the adhesive layer) or the like.

On the other hand, when the curing agent is an isocyanate compound, it is preferable that the isocyanate compound in the resin composition for the primer layer is blocked from the viewpoint of improving storage stability (the viewpoint of increasing the pot life of the composition for the primer layer). As a blocking agent, well-known epsilon caprolactam, methyl ethyl ketone oxime, etc. can be used, for example.

The resin composition for primer layers may further contain a solvent as needed from a viewpoint of improving application|coating workability, etc. Examples of the solvent include alcohol solvents such as methanol, ethanol, isopropanol and 1-butanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and benzene solvents such as xylene. . One type may be sufficient as such a solvent, and two or more types may be combined.

The coating method of the resin composition for primer layers is not specifically limited, What is necessary is just to select suitably from well-known methods.

The drying method of the resin composition for primer layers is not specifically limited, What is necessary is just to volatilize a solvent. The drying temperature is, for example, when the resin contained in the resin composition for a primer layer has a functional group that reacts with the curing agent, the temperature at which the solvent can be volatilized in a range in which the resin does not completely cure, and the substrate reached during drying It is preferable that temperature is 180-220 degreeC, for example.

About the process of (2)

On the primer layer of the obtained coating metal plate, the resin composition for rubber layers containing the 2nd rubber-type polymer mentioned above and a 2nd crosslinking agent is provided, and the layer which consists of this resin composition for rubber layers is formed. Sheet form may be sufficient as the resin composition for rubber layers, and liquid may be sufficient as it.

The resin composition for rubber layers may further contain a solvent. Examples of the solvent contained in the resin composition for a rubber layer include the same solvent as the solvent contained in the composition for a primer layer.

When the resin composition for a rubber layer is liquid, a method for applying the resin composition for a rubber layer is not particularly limited, and may be, for example, a screen printing method, a roll coating method, a curtain flow method, or a dip coating method.

Next, the resin composition for rubber layers provided on the primer layer of a coating metal plate is crosslinked, and the rubber layer which consists of a crosslinked material of the resin composition for rubber layers is obtained.

It is preferable to perform bridge|crosslinking of the resin composition for rubber layers by heating. The heating method is not particularly limited, but may be, for example, a thermocompression bonding method.

The crosslinking temperature may be a temperature at which the first rubber-based polymer in the resin composition for a rubber layer is crosslinked, depending on the composition of the resin composition for a rubber layer, but can be, for example, 150 to 250°C. The crosslinking time can be, for example, about 2 to 15 minutes.

The pressure at the time of thermocompression bonding should just be a grade which can fully adhere|attach a primer layer and a rubber|gum layer, and can be set as 10-30 MPa, for example.

about other processes

The manufacturing method of the composite_body|complex of this invention may further have another process as needed. For example, between the step (1) and the step (2), (3) the above-described adhesive composition is applied on the primer layer to form a layer made of the adhesive composition.

The adhesive composition may further contain a solvent as needed. Examples of the solvent contained in the adhesive composition include the same solvent as the solvent contained in the composition for a primer layer. Moreover, the provision method in particular of an adhesive composition is not specifically limited, It can be carried out similarly to the provision method of the resin composition for rubber layers mentioned above.

And in the process of said (2), after providing the resin composition for rubber layers on the layer which consists of the adhesive composition obtained in the process of (3), it is made to dry and bridge|crosslink. That is, since many adhesive compositions contain a solvent, it is preferable to bridge|crosslink the resin composition for rubber layers, performing drying and bridge|crosslinking of an adhesive composition.

Drying and crosslinking may be performed simultaneously or may be performed sequentially. From a viewpoint of making it easy to fully adhere|attach a primer layer and a rubber layer through an adhesive bond layer, it is preferable to perform drying and bridge|crosslinking sequentially. That is, after drying the adhesive composition (drying process), it is preferable to crosslink the adhesive composition and the resin composition for rubber layers, respectively (crosslinking process).

The drying temperature should just be a temperature at which the solvent in the adhesive composition can volatilize, and is usually lower than the crosslinking temperature, for example, from room temperature to 80°C. Drying time can be made into about 2 to 15 minutes, for example.

Moreover, in a bridge|crosslinking process, the adhesive composition can also be bridge|crosslinked together with bridge|crosslinking of the resin composition for rubber layers. Thereby, the adhesiveness between a primer layer and an adhesive bond layer can be improved further.

3. Uses of the complex

The composite of the present invention can be used in various applications such as, for example, a vibration-proof rubber for automobiles, a vibration-isolation laminated rubber as a building member, and a health care product.

<Example>

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by these Examples.

1. Preparation of materials

(1) metal plate

Metal plate M1: Zn-6%Al-3%Mg alloy plated steel plate with a thickness of 0.5 mm and a plating adhesion of 90 g/m ^{2 per side}

Metal plate M2: cold-rolled steel plate with a thickness of 2.0 mm

Metal plate M3: Hot-dip Zn-coated steel plate with a thickness of 0.8 mm and a coating weight of 60 g/m ^{2 per side}

Metal plate M4: an alloyed Zn-coated steel plate with a thickness of 1.0 mm and a plating adhesion of 45 g/m ² per side (alloyed hot-dip Zn plated after hot-dip Zn plating)

Metal plate M5: Hot-dip Al-9%Si plated steel plate with a thickness of 0.8 mm and a coating adhesion of 60 g/m ^{2 per side}

Metal plate M6: 0.5 mm thick stainless steel plate

Metal plate M7: aluminum plate 1.5 mm thick

Metal plate M8: aluminum alloy plate with a thickness of 2.0 mm

Metal plate M9: copper plate with a thickness of 1.0 mm

Metal plate M10: brass plate 1.0 mm thick

Metal plate M11: titanium plate 0.5 mm thick

For these metal plates, those obtained by cleaning (hydrophilizing) the surface of the metal plate by hot water washing or water washing after alkali degreasing or acid washing treatment immediately before chemical conversion treatment were used.

(2) chemical conversion solution

<Preparation of chemical conversion treatment liquid C1>

Chemical conversion treatment liquid C1 having a solid content concentration of 3 mass% by adding a mixture of N-(2-aminoethyl)aminopropyltriethoxysilane and a urethane resin (mass ratio 6:4) to water in which 10% by mass of ethanol was dissolved. got

<Preparation of chemical conversion treatment liquid C2>

A coating-type chromate treatment agent (surf coat NRC300, manufactured by Nippon Paint Co., Ltd.) was used.

<Preparation of chemical conversion treatment liquid C3>

Using pure water as a solvent, hexavalent chromium ion: 20 g/l, trivalent chromium ion: 20 g/l, phosphoric acid: 40 g/l, silica: 80 g/l, polymethyl methacrylate: 40 g/l was added to obtain a chemical conversion treatment liquid C3 of a chromium phosphate salt.

<Preparation of chemical conversion treatment liquid C4>

To pure water (solvent), 20 g/L of a Ti compound and 40 g/L of a phenol resin were added to obtain a chromate-free chemical conversion solution C4.

(3) Resin composition for primer layer

<Preparation of resin compositions 1-38 for primer layers>

100 parts by mass of curable polyester 1 (number average molecular weight 12000) and 10 parts by mass of an isocyanate compound (curing agent 1) obtained by blocking hexamethylene diisocyanate (HDI) with ε-caprolactam, and a type shown in Table 1 or Table 2, and A positive additive material, 3 parts by mass of silica particles (average particle diameter 4 μm) as aggregate, mixed solvent (solvent naphtha, coal tar naphtha: 30%, cyclohexanone: 30%, n-butanol: 5%, ethylene glycol monobutyl ether : 5%) to obtain a resin composition for a primer layer.

<Preparation of resin compositions 39-44 for primer layers>

Except having changed the kind of curable resin and hardening|curing agent as shown in Table 2, it carried out similarly to the resin composition 3 for primer layers, and obtained the resin compositions 39-44 for primer layers. Moreover, in the resin compositions 39-43 for primer layers, the isocyanate compound (hardening|curing agent 1) which made hexamethylene diisocyanate (HDI) block with epsilon caprolactam as a main component is used; In the resin composition 44 for primer layers, a melamine-based curing agent (curing agent 2) was used.

The composition of the obtained resin compositions 1-25 for primer layers is shown in Table 1, and the composition of the resin compositions 26-44 for primer layers is shown in Table 2.

In addition, the abbreviation in a table|surface shows the following.

Curable polyester 1: hydroxyl group-containing high molecular weight polyester resin (hydroxyl group-containing aromatic polyester, number average molecular weight: 12000, Tg: 75°C)

Curable polyester 2: hydroxyl group-containing low molecular weight polyester resin (hydroxyl group-containing aromatic polyester, number average molecular weight 3000, Tg: 65°C)

Curable polyester 3: Epoxy-modified polyester resin (epoxy-modified product of aromatic polyester containing carboxyl group, number average molecular weight 4000, Tg: 63°C)

Curable polyester 4: epoxy-modified high molecular weight polyester (epoxy-modified product of aromatic polyester containing carboxyl group, number average molecular weight: 14000, Tg: 70°C)

Epoxy 1: Amine-modified epoxy resin (number average molecular weight: 5000, Tg: 60°C)

Epoxy 2: Amine-modified high molecular weight epoxy resin (number average molecular weight: 20000, Tg: 65°C)

In addition, the number average molecular weight of resin contained in the resin composition for primer layers, and the average primary particle diameter of an additive material were measured by the following method.

(number average molecular weight)

The number average molecular weight of the resin was measured by gel permeation chromatography. Specifically, it measured under the following measurement conditions.

<Measurement conditions>

Eluent: THF

Flow rate: 1.0 ml/min

Temperature: 40℃

Detector: Differential Refractometer

(average primary particle diameter)

The average particle diameter of the additive material was obtained by observing the particle diameters of 20 arbitrary particles with an electron microscope, and obtaining them as the arithmetic average particle diameters.

(specific surface area)

The specific surface area (nitrogen adsorption specific surface area) of the additive material was measured by the BET method in accordance with JIS Z 8830:2013.

(4) adhesive composition

Adhesive composition A1: Chemlac 6125 manufactured by Road Corporation (main ingredient: chlorinated rubber, sub-component: sulfur (vulcanizing agent), zinc oxide (vulcanizing agent) and high boiling point solvent)

Adhesive composition A2: XJ551 manufactured by Road Corporation (main ingredient: chlorinated rubber, sub-component: sulfur (vulcanizing agent) and high boiling point solvent)

(5) Resin composition for rubber layer

<Uncrosslinked rubber sheet R1>

NBR raw rubber: 100 parts by mass

Carbon black (HAF): 50 parts by mass

Naphthenic process oil: 20 parts by mass

Stearic acid: 1 part by mass

Zinc oxide (zinc oxide): 5 parts by mass

Sulfur: 2 parts by mass

Thiazole-based crosslinking accelerator: 2 parts by mass

<Uncrosslinked rubber sheet R2>

EPDM raw rubber: 100 parts by mass

Carbon black (HAF): 50 parts by mass

Naphthenic process oil: 20 parts by mass

Stearic acid: 1 part by mass

Zinc oxide (zinc oxide): 5 parts by mass

Sulfur: 2 parts by mass

Thiazole-based crosslinking accelerator: 2 parts by mass

2. Fabrication and Evaluation of Composites

<Production of Composite 1>

(1) Preparation of painted metal plate

A metal plate M1 (a zinc-6%aluminum-3%magnesium alloy plated steel plate having a thickness of 0.5 mm and a plating adhesion amount of 90 g/m ^{2 per side) was prepared, and the surface was degreased with alkali.} The chemical conversion treatment liquid C1 prepared above was applied on the alkali-degreasing surface of this metal plate by a bar coating method, and then dried to form a chemical conversion treatment film having a ^{film adhesion amount of 100 mg/m 2 .} Next, on the chemical conversion treatment film, the resin composition 1 for a primer layer was applied by a bar coating method, and then dried at a target substrate temperature of 200°C to form a primer layer having a thickness of 5 µm to obtain a coated metal plate.

(2) Preparation of Composite 1

Next, on the primer layer of the obtained coated metal plate, the adhesive composition A1 (Chemrak 6125 manufactured by LOAD) was applied as an adhesive composition by a bar coating method, and then dried at 80° C. for 10 minutes to form an adhesive composition having a thickness of 10 μm. layer was formed. Then, on the layer made of the adhesive composition, an uncrosslinked rubber sheet R1 having a thickness of 3 mm as a resin composition for a rubber layer is placed, and then thermocompressed with a hot press machine at a temperature of 160° C. and a pressure of 200 kgf/cm ² for 15 minutes, The adhesive composition and the uncrosslinked rubber sheet R1 were respectively crosslinked. Thereby, the composite 1 which has a laminated structure of a coated metal plate/adhesive layer/rubber layer was obtained.

<Production of Complexes 2 to 60>

Composites 2 to 60 were obtained in the same manner as in Composite 1 except that the type of the coated metal plate was changed as shown in Tables 3 to 5.

Specifically, the composites 2 to 18 and 32 to 34 are the composite 3 and the composite 3, except that at least one of the average primary particle diameter and content of carbon black contained in the primer layer of the coated metal plate is changed as shown in Table 3 or Table 4. same; Composites 19 to 31 and 35 to 37 were the same as in Composite 3 except that the types and contents of the additive materials contained in the primer layer of the coated metal plate were changed as shown in Table 3 or Table 4; Composite 38 is the same as Composite 3 except that an additive material is not added to the primer layer of the painted metal plate; Composites 39 to 43 are the same as in Composite 3 except that the type of curable resin contained in the primer layer of the coated metal plate was changed as shown in Table 5; Composites 44 to 47 were the same as in Composite 3 except that the thickness of the primer layer of the coated metal plate was changed as shown in Table 5; Composites 48 to 57 were the same as in Composite 3 except that the type of the metal plate of the coated metal plate was changed as shown in Table 5; Composites 58 to 60 are the same as those of Composite 3 except that the type of chemical conversion film on the coated metal sheet is changed as shown in Table 5.

<Production of composite 61>

Composite 61 was obtained in the same manner as in Composite 3 except that the types of the adhesive composition and the uncrosslinked rubber sheet were changed as shown in Table 5.

<Production of composite 62>

(Resin composition for rust prevention layer)

With respect to 100 parts by mass of epoxy 1 (main resin component), aluminum tripolyphosphate, magnesium phosphate, magnesium hydrogen phosphate, and zinc phosphate were blended and mixed with a total of 15 parts by mass to obtain a resin composition for waterproofing layers.

(production of composite)

And after apply|coating the said resin composition for rust prevention layers between a chemical conversion film and a primer layer, it dried and hardened, and it carried out similarly to the coating metal plate 3 except having formed the rust prevention layer with a thickness of 5 micrometers, and obtained the coating metal plate. Composite 62 was obtained in the same manner as in Composite 3 except that this coated metal plate was used.

<Production of Composite 63>

Composite 63 was obtained in the same manner as in Composite 40 except that the kind of curing agent contained in the primer layer was changed as shown in Table 5.

The following method evaluated the blocking resistance of the obtained coated metal plate, and the adhesiveness of a composite_body|complex.

(blocking resistance)

The coated metal plate was cut into a size of 50 mm x 50 mm to obtain two test pieces. These two test pieces were laminated|stacked so that the coating-film surfaces might contact each other, and it hold|maintained for 24 hours in the state which applied temperature: 50 degreeC, and pressure: 2 MPa. Then, the adhesion state (the presence or absence of blocking) of these two test pieces was visually observed, and it evaluated based on the following criteria.

○: No blocking

×: Blocking occurs

If it was ○, it was judged that it was favorable.

(Adhesive)

Adhesion between the primer layer / adhesive layer of the obtained composite was measured by a 90 degree peel test based on JIS K6854-1: 1999 (Adhesive - Peel Adhesive Strength Test Method - Part 1: 90 degree peel). The 90 degree peel test was performed at a tensile speed (moving speed) of 50 mm/min using a test piece having a width of 25 mm and a length of 150 mm. And adhesiveness was evaluated based on the following criteria.

◎◎: The peeling interface is only the cohesive (internal) destruction of the rubber layer, and the adhesion is extremely excellent.

◎: 90% or more and less than 100% of the peeling interface are cohesive (internal) failure of the rubber layer, and the remainder is interfacial failure of the primer layer/adhesive layer, resulting in excellent adhesion

○: 70% or more and less than 90% of the peeling interface are cohesive (internal) failure of the rubber layer, and the remainder is interfacial failure of the primer layer/adhesive layer, resulting in excellent adhesion

Δ: Less than 70% of the peeling interface is cohesive (internal) failure of the rubber layer, and the remainder is interfacial failure of the primer layer/adhesive layer, resulting in poor adhesion

x: All the peeling interfaces are interfacial destruction of the primer layer/adhesive layer, and the adhesiveness is inferior.

○ It was judged that it was favorable if it was more than it.

The evaluation results of the complexes 1 to 25 are shown in Table 3, the evaluation results of the complexes 26 to 38 are shown in Table 4, and the evaluation results of the complexes 39 to 63 are shown in Table 5, respectively.

As shown in Tables 3-5, the coating metal plates other than the coating metal plate 37 did not raise|generate any blocking. Moreover, it turns out that all of the composite_body|complexes of this invention have favorable adhesiveness.

In particular, it can be seen that the use of carbon black as the carbon-based particles increases the adhesiveness (comparison between composites 1 to 4 and 23).

Moreover, it turns out that adhesiveness becomes high by making the average primary particle diameter of carbon black into 50 nm or less (comparison with composites 1-6).

In addition, it turns out that the higher the molecular weight of the resin contained in the primer layer, the higher the adhesiveness (comparison between composites 39 and 3). It is considered that this is because the resin with many molecular weights is easy to swell with the solvent etc. of an adhesive bond layer because the flexibility of the primer layer obtained is high.

Moreover, it turns out that adhesiveness becomes higher by making a hardening|curing agent into an isocyanate compound (contrast with composite 40 and 63). It is thought that this is because the direction of the isocyanate compound has high flexibility of the primer layer obtained, and it is because it is easy to swell with the solvent of an adhesive bond layer, etc.

In addition, even if you change the film thickness of the primer layer (compared to composites 3 and 44 to 47), the type of chemical conversion coating (compared to composites 3 and 58 to 60), or the type of metal plate (compared to composites 3 and 48 to 57) , it turns out that good adhesiveness is obtained. Moreover, it turns out that good adhesiveness is obtained even if the kind of rubber is changed (composite 3 and 61 contrast).

In addition, when the adhesion and corrosion resistance (corrosion resistance in JIS-Z2371 conformance, 35 ° C. 5% NaCl salt water spray test) were evaluated for Composite 62, respectively, while having good adhesion as in Composite 3, corrosion resistance higher than that of Composite 3 confirmed to have

In contrast, as shown in Table 4, it can be seen that neither composite 38 in which the primer layer does not contain carbon-based particles, and composites 35 to 37 in which the primer layer contains a material other than carbon-based particles, cannot obtain sufficient adhesion. can On the other hand, it can be seen that, in place of the carbon-based particles, the composite 37 including the rubber component has relatively good adhesion, but blocking occurs.

Moreover, as shown in Table 4, it turns out that the composite 32 and 33 whose content of carbon-type particle contained in a primer layer exceeds 25 mass % with respect to resin cannot be made into a paint in the first place. On the other hand, it can be seen that the composites 7, 11, and 15 in which the content of carbon-based particles contained in the primer layer is less than 3% by mass relative to the resin cannot obtain sufficient adhesiveness.

This application claims priority based on Japanese Patent Application No. 2019-020812 for which it applied on February 7, 2019. All content described in the said application specification and drawing is integrated in this specification.

<Industrial Applicability>

ADVANTAGE OF THE INVENTION According to this invention, the composite_body|complex which has favorable adhesiveness, its manufacturing method, and the coated metal plate which does not generate|occur|produce the blocking used for it can be provided.

10 complex
20 painted metal plate
30 adhesive layer
40 rubber layer
21 metal plate
22 chemical conversion coating
23 Primer layer
24 Rust layer

Claims (17)

A composite having a metal plate, a coated metal plate having a primer layer disposed on the metal plate, and a rubber layer disposed on the primer layer of the coated metal plate,
The primer layer is made of a cured product of a resin composition comprising a curable resin, a curing agent, and carbon-based particles,
The specific surface area of the carbon-based particles is 10 ~ 1500 m ² /g,
The content of the carbon-based particles is 3 to 25% by mass relative to the curable resin,
The content of the rubber component is 1% by mass or less with respect to the curable resin,
complex. According to claim 1,
The rubber layer is a crosslinked product of a resin composition for a rubber layer comprising a first rubber-based polymer and a first crosslinking agent,
It is disposed between the primer layer and the rubber layer, and further has an adhesive layer comprising a crosslinked product of an adhesive composition comprising a second rubber-based polymer and a second crosslinking agent,
complex. 3. The method of claim 1 or 2,
The painted metal plate further has a chemical conversion film disposed between the metal plate and the primer layer,
complex. 4. The method of claim 3,
The painted metal plate further has a rust preventive layer disposed between the chemical conversion film and the primer layer,
complex. 5. The method according to any one of claims 1 to 4,
The curing agent is an isocyanate compound,
complex. 6. The method of claim 5,
wherein the isocyanate compound is an aliphatic isocyanate;
complex. 7. The method according to any one of claims 1 to 6,
The average primary particle diameter of the carbon-based particles is 10 to 50 nm,
complex. 8. The method of claim 7,
The carbon-based particles are carbon black,
complex. 9. The method according to any one of claims 1 to 8,
The thickness of the primer layer is 3 to 20 μm,
complex. 10. The method according to any one of claims 1 to 9,
The chemical conversion coating is a chromate-based coating or a chromate-free coating comprising a silane coupling agent having an amino group and an organic resin,
complex. 1) having a metal plate and a primer layer disposed on the metal plate,
The primer layer is made of a cured product of a resin composition comprising a curable resin, a curing agent, and carbon-based particles,
The specific surface area of the carbon-based particles is 10 ~ 1500 m ² /g,
The content of the carbon-based particles is 3 to 25% by mass relative to the curable resin,
A step of preparing a coated metal plate in which the content of the rubber component is 1% by mass or less with respect to the curable resin;
2) on the primer layer of the coated metal plate, a resin composition for a rubber layer comprising a first rubber-based polymer and a first crosslinking agent is applied, and then crosslinked to obtain a rubber layer;
Methods of making the complex. 12. The method of claim 11,
3) providing an adhesive composition comprising a second rubber-based polymer and a second crosslinking agent on the primer layer to form a layer comprising the adhesive composition;
In the process of said 2), the said resin composition for rubber layers is provided on the layer which consists of the said adhesive composition,
Methods of making the complex. As a coated metal plate for bonding with a rubber layer,
Having a metal plate, a chemical conversion film, and a primer layer in this order,
The chemical conversion coating is a chromate-based coating or a chromate-free coating comprising a silane coupling agent having an amino group and an organic resin,
The primer layer is disposed on the outermost surface of the painted metal plate,
The primer layer is made of a cured product of a resin composition comprising a curable resin, a curing agent, and carbon-based particles,
The specific surface area of the carbon-based particles is 10 ~ 1500 m ² /g,
The content of the carbon-based particles is 3 to 25% by mass relative to the curable resin,
The content of the rubber component is 1% by mass or less with respect to the curable resin,
painted metal plate. 14. The method of claim 13,
Further having a rust preventive layer disposed between the chemical conversion treatment film and the primer layer,
painted metal plate. 15. The method of claim 13 or 14
The average primary particle diameter of the carbon-based particles is 10 to 50 nm,
painted metal plate. 16. The method of claim 15,
The carbon-based particles are carbon black,
painted metal plate. 17. The method according to any one of claims 13 to 16,
The thickness of the primer layer is 3 to 20 μm,
painted metal plate.

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