JPWO2020137497A1 - Method of manufacturing a laminate - Google Patents

Abstract

An object of the present invention is to provide a laminate having excellent initial adhesive strength between a metal base material and a resin coating layer. The method for producing a laminate of the present invention includes an intermediate layer forming step of forming an intermediate layer containing a silicon oxide on the surface of a metal base material, a resin coating step of coating the surface of the intermediate layer with a resin coating layer, and a resin coating step. The resin coating layer is composed of a polymer block [A] containing an aromatic vinyl monomer unit as a main component and a polymer block [B] containing a chain conjugated diene monomer unit as a main component. It is characterized by containing a modified block copolymer hydride [E] obtained by introducing an alkoxysilyl group into the block copolymer hydride [D] obtained by hydrogenating the block copolymer [C].

Description

The present invention relates to a method for producing a laminate.

Laminates formed by forming a resin coating layer on the surface of a metal substrate include packaging materials for pharmaceuticals, packaging materials for foods, packaging materials for electronic parts, back surface protective sheets for solar cell modules, water pipes, gas transport pipes, etc. It is used in various applications such as fuel transport pipes and cable protection pipes. Further, as a specific example of such a laminate, a laminate formed by forming a resin coating layer as a sealing material on the surface of a metal base material such as an LED element, an organic EL element, and an electronic substrate wiring. It can also be mentioned.

For example, in Patent Document 1, a composite multilayer sheet obtained by laminating a sheet made of a predetermined modified block copolymer hydride having an alkoxysilyl group introduced and a metal foil has moisture resistance, oxygen barrier property, light shielding property, and heat resistance. It has been reported that it is useful for packaging of pharmaceuticals and foods, back surface protective sheets for solar cell modules, sealing of organic EL elements, packaging of electronic parts, etc. because of its excellent properties and hydrolysis resistance.

Further, in Patent Document 2, a predetermined polyethylene-coated steel pipe coated with a silane coupling agent-treated layer, an epoxy primer layer, an adhesive polyethylene layer, and a polyethylene layer on the surface of the steel pipe in this order from the surface side of the steel pipe is coated at a high temperature. It is disclosed that the layer has excellent adhesive durability and can be suitably used as a line pipe for transporting oil, natural gas, city gas, water and the like.

International Publication No. 2015/137376 JP-A-2018-69592

However, in the above-mentioned laminate of the prior art, there is room for improvement in the adhesive strength between the metal base material and the resin coating layer. In particular, the adhesive strength between the metal base material and the resin coating layer (hereinafter, may be referred to as "initial adhesive strength") immediately after the laminate was manufactured was not sufficient.

Therefore, an object of the present invention is to provide a laminate having excellent initial adhesive strength between a metal base material and a resin coating layer.

The present inventor has conducted diligent studies for the purpose of solving the above problems. Then, the present inventor forms an intermediate layer containing a silicon oxide on the surface of a metal base material, and then coats the surface of the intermediate layer with a resin coating layer containing a predetermined modified block copolymer hydride. The present invention has been completed by finding that the laminated body is excellent in the initial adhesive strength between the metal base material and the resin coating layer.

That is, the present invention aims to advantageously solve the above problems, and the method for producing a laminate of the present invention is an intermediate layer in which an intermediate layer containing a silicon oxide is formed on the surface of a metal substrate. A layer forming step and a resin coating step of coating the surface of the intermediate layer with a resin coating layer are included, and the resin coating layer comprises a polymer block [A] containing an aromatic vinyl monomer unit as a main component. , A block obtained by hydrogenating a block copolymer [C] composed of a polymer block [B] containing a chain-conjugated diene monomer unit (linear conjugated diene, branched chain-conjugated diene) as a main component. It is characterized by containing a modified block copolymer hydride [E] in which an alkoxysilyl group is introduced into the copolymer hydride [D]. As described above, after forming the intermediate layer containing silicon oxide on the surface of the metal base material, the surface of the intermediate layer is coated with the resin coating layer containing the above-mentioned predetermined modified block copolymer hydride. The laminate is excellent in the initial adhesive strength between the metal base material and the resin coating layer.
In the present specification, the "polymer block [A] containing an aromatic vinyl monomer unit as a main component" is a "polymer block [A] containing more than 50% by mass of an aromatic vinyl monomer unit". ] ”, And“ polymer block [B] containing a chain-conjugated diene monomer unit as a main component ”is a“ polymer block [B] containing more than 50% by mass of a chain-conjugated diene monomer unit. ] ”Mean. Further, "containing a monomer unit" means that "a structural unit derived from a monomer is contained in a polymer obtained by using the monomer".

Here, in the method for producing a laminate of the present invention, it is preferable to directly form the intermediate layer on the surface of the metal base material. By forming the intermediate layer directly on the surface of the metal base material in this way, the adhesive strength between the metal base material and the resin coating layer after the laminate has been used for a long period of time (hereinafter, simply "long-term adhesive strength"). It may be referred to as), and the moisture resistance of the laminate can be enhanced.

Further, in the method for producing a laminate of the present invention, the silicon ratio on the surface of the intermediate layer is preferably 2.0 atom% or more and 30.0 atom% or less. As described above, when the ratio of silicon on the surface of the intermediate layer is within the above-mentioned predetermined range, the initial adhesive strength between the metal base material and the resin coating layer can be further increased, and the long-term adhesive strength between the metal base material and the resin coating layer can be further increased. And the moisture resistance of the laminate can be improved.
In the present invention, the silicon ratio on the surface of the intermediate layer can be measured by the method described in the examples of the present specification.

Further, in the method for producing a laminate of the present invention, it is preferable to form the intermediate layer by an itro treatment and / or an atmospheric pressure plasma coating treatment. In this way, if the intermediate layer is formed by the itro treatment and / or the atmospheric pressure plasma coating treatment, the initial adhesive strength between the metal base material and the resin coating layer can be further increased.

Further, in the method for producing a laminate of the present invention, the dissolution curve measured by gel permeation chromatography (GPC) of a sample containing the modified block copolymer hydride [E] has a co-weight of at least two modified blocks. A modified block copolymer hydride [E] having a peak derived from the coalesced hydride [E] and showing the peak top with the highest detection sensitivity among the peaks derived from the at least two modified block copolymer hydride [E]. When the derived peak is set as the first peak and the peak derived from the modified block copolymer hydride [E] showing the peak top having the earliest elution time next to the elution time of the peak top of the first peak is set as the second peak, The ratio of the standard polystyrene-equivalent molecular weight (first peak molecular weight) based on the elution time of the first peak to the standard polystyrene-equivalent molecular weight (second peak molecular weight) based on the elution time of the second peak (first peak molecular weight / second peak). The molecular weight) is preferably 1.50 or more. As described above, the dissolution curve measured by GPC of the sample containing the modified block copolymer hydride [E] has at least the above-mentioned predetermined first peak and second peak, and is based on the dissolution time of the second peak. The ratio (first peak molecular weight / second peak molecular weight) of the standard polystyrene-equivalent molecular weight (first peak molecular weight) based on the elution time of the first peak to the standard polystyrene-equivalent molecular weight (second peak molecular weight) should be equal to or higher than the above-mentioned predetermined value. For example, the initial adhesive strength between the metal base material and the resin coating layer can be further increased.

According to the present invention, it is possible to provide a laminate having excellent initial adhesive strength between a metal base material and a resin coating layer.

It is a figure for demonstrating an example of the elution curve measured by gel permeation chromatography (GPC) of the sample containing block copolymer hydride [D]. The vertical axis of FIG. 1 indicates the polystyrene-equivalent molecular weight (left vertical axis) or the sensitivity (mV) (right vertical axis), and the horizontal axis of FIG. 1 indicates the elution time (minutes).

Hereinafter, embodiments of the present invention will be described in detail.
Here, the method for producing a laminate of the present invention can be used when producing a laminate having excellent initial adhesive strength between a metal base material and a resin coating layer.

(Manufacturing method of laminated body)
The method for producing a laminate of the present invention includes an intermediate layer forming step of forming an intermediate layer containing a silicon oxide on the surface of a metal base material, and a resin coating layer containing a predetermined modified block copolymer hydride [E]. Includes a resin coating step of coating the surface of the intermediate layer.

Here, the laminate produced by the method for producing a laminate of the present invention is a resin coating layer containing a metal base material, an intermediate layer containing a silicon oxide, and a predetermined modified block copolymer hydride [E]. An intermediate layer is interposed between the surface of the metal base material and the resin coating layer.

The laminate produced by the method for producing a laminate of the present invention is excellent in the initial adhesive strength between the metal base material and the resin coating layer.

The method for producing the laminate of the present invention may include other steps other than the intermediate layer forming step and the resin coating step described above.

<Intermediate layer forming process>
In the intermediate layer forming step, an intermediate layer containing a silicon oxide is formed on the surface of the metal base material.

<< Metallic base material >>
The metal base material is a base material made of a metal material.
The metal material constituting the metal base material is not particularly limited, and is, for example, a transition metal such as iron (Fe), silver (Ag), copper (Cu), nickel (Ni), chromium (Cr); aluminum (Al). ); Lead (Pb); Zinc (Zn); Tin (Sn); Alloys containing these as main components; and the like can be used. Of these, copper (Cu), nickel (Ni), iron (Fe), aluminum (Al), stainless steel, and carbon steel are preferably used. As the stainless steel, SUS304, SUS316, SUS410, SUS430 and the like can be used. Further, as the carbon steel, S55C, S15C, S65C and the like can be used.

The shape, thickness, size, etc. of the metal base material can be appropriately selected according to the use of the laminate.

Examples of the shape of the metal base material include sheet shape, tubular shape, and columnar shape.

In the present specification, the "surface of the metal base material" is not particularly limited as long as it is the surface of the metal base material.
For example, when the metal base material is in the form of a sheet, the "surface of the metal base material" may be the main surface of either one of the sheet-shaped metal base materials, or both of the sheet-shaped metal base materials. It may be the main surface.
When the metal base material is tubular, the "surface of the metal base material" may be the outer surface (outer surface) of the tubular metal base material or the inner surface of the tubular metal base material (the outer surface). (Inner surface) may be used.

Further, the surface of the metal base material may be a flat surface or a curved surface.

Further, from the viewpoint of increasing the long-term adhesive strength between the metal base material and the resin coating layer in the laminated body, the surface of the metal base material on the side where the intermediate layer and the resin coating layer are formed is subjected to a rust removing method such as blasting. It may be rust-removed.

<< Method of forming the intermediate layer >>
The method for forming the intermediate layer containing the silicon oxide is not particularly limited, and for example, surface treatment such as itro treatment, atmospheric pressure plasma coating treatment, and reduced pressure plasma coating treatment can be used. Above all, from the viewpoint of further increasing the initial adhesive strength between the metal base material and the resin coating layer, the intermediate layer is preferably formed by an itro treatment and / or an atmospheric pressure plasma coating treatment.

Then, by performing the above-mentioned surface treatment on the metal base material, an intermediate layer containing a silicon oxide can be formed on the surface of the metal base material.

After forming a layer other than the intermediate layer and the resin coating layer (for example, an organic adhesive layer described later) on the surface of the metal base material in advance, the metal base material is indirectly connected to the metal base material via the other layers. By specifically performing the surface treatment, the other layer may be interposed between the surface of the metal base material and the intermediate layer to be formed, but the initial adhesive strength between the metal base material and the resin coating layer and From the viewpoint of enhancing the moisture resistance of the laminate, it is preferable to directly form an intermediate layer on the surface of the metal base material by directly performing the surface treatment on the metal base material.

Further, in the intermediate layer forming step, the intermediate layer may be formed on at least a part of the surface (resin coating layer forming surface) on the side where the resin coating layer of the metal base material is formed, but the metal base material and the resin coating may be formed. From the viewpoint of further increasing the initial adhesive strength with the layer, it is preferable to form an intermediate layer on the entire resin coating layer forming surface.
For example, when one main surface of a sheet-shaped metal base material is used as a resin coating layer forming surface and an intermediate layer is formed on the main surface, from the viewpoint of further increasing the initial adhesive strength between the metal base material and the resin coating layer. , It is preferable to form an intermediate layer on the entire main surface.
Further, for example, when the outer surface (or inner surface) of the tubular metal base material is used as the resin coating layer forming surface and the intermediate layer is formed on the outer surface (or inner surface), the metal base material and the resin coating layer are used. From the viewpoint of further increasing the initial adhesive strength of the above, it is preferable to form an intermediate layer on the entire outer surface (or inner surface).

Further, when the resin coating layer is formed at a plurality of places of the metal base material, the same intermediate layer may be formed or different intermediate layers may be formed on the surface of the plurality of places of the metal base material. And.
For example, when forming intermediate layers on both main surfaces of a sheet-like base material, the same intermediate layer may be formed on one main surface and the other main surface, or different intermediate layers may be formed. It may be formed.
Further, for example, when an intermediate layer is formed on both the outer surface and the inner surface of a tubular metal base material, the same intermediate layer may be formed on the outer surface and the inner surface, or different intermediate layers may be formed. May be formed.

When an intermediate layer is formed on a region that is at least a part of the resin coating layer forming surface of the metal base material, components such as silicon oxide constituting the intermediate layer should be present on the region without gaps. The area may be completely covered with, or the area may be partially covered by being scattered on the area.

Hereinafter, the itro treatment, the atmospheric pressure plasma coating treatment, and the reduced pressure plasma coating treatment, which are surface treatments that can be used as a method for forming the intermediate layer, will be described in detail.

[Itro processing]
In the itro treatment, a flame released by igniting a mixture of a flammable gas, a gas obtained by evaporating a silane compound as a silicon supply source in a vapor-liquid equilibrium state, and air is applied to the surface of a metal substrate. It is applied (sprayed) to form an intermediate layer containing silicon oxide.

Here, as the flammable gas, for example, propane gas or LPG (liquefied petroleum gas other than propane gas alone) can be used. Examples of LPG include butane (normal butane, isobutane), butane / propane mixed gas, ethane, pentane (normal pentane, isopentane, cyclopentane) and the like.

The silane compound as a silicon supply source is not particularly limited as long as it contains a silicon atom and can form a layer containing a silicon oxide by an itro treatment, and examples thereof include an organosilicon compound.
Examples of the organic silicon compound include hexamethyldisiloxane; hexamethyldisilazane; tetramethylsilane, tetraethylsilane, dimethyldichlorosilane, dimethyldiphenylsilane, diethyldichlorosilane, diethyldiphenylsilane, methyltrichlorosilane, methyltriphenylsilane, and the like. Alkylsilanes such as dimethyldiethylsilane; tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, dichlorodimethoxysilane, dichlorodiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trichloromethoxy Silane, trichloroethoxysilane, triphenylmethoxysilane, triphenylethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, Alkoxysilanes such as trifluoropropyltrichlorosilane and trifluoropropyltrimethoxysilane; and the like can be used.

The Itro treatment includes, for example, a burner that ignites the above-mentioned mixture of a flammable gas, a silane compound, and air to emit a flame, and a table for transporting a metal base material to be treated. It can be carried out by using an apparatus such as "Itro processing apparatus" manufactured by Japan.
In the itro treatment using the above apparatus, various conditions such as the distance between the burner nozzle and the metal base material, the flow rate of the silicon supply source, the air flow rate, the combustible gas flow rate, and the number of treatments are desired by the present invention. It can be set as appropriate within the range where the effect can be obtained.

[Atmospheric pressure plasma coating treatment]
In the atmospheric pressure plasma coating treatment, a silane compound, which is a silicon supply source, is applied to the surface of a metal substrate together with plasma generated under atmospheric pressure to form an intermediate layer containing a silicon oxide.

As the silane compound as the silicon supply source, the silane compound described above in the section of "Itro treatment" can be used. Above all, it is preferable to use hexamethyldisilane from the viewpoint of further increasing the initial adhesive strength between the metal base material and the resin coating layer.
Examples of the gas required for generating plasma under atmospheric pressure include oxygen, nitrogen, argon, and a mixed gas thereof.
The atmospheric pressure plasma coating treatment can be performed using, for example, an apparatus such as "UL-Coat" manufactured by AcXys Technologies.

Various conditions in the atmospheric pressure plasma coating treatment can be appropriately adjusted within a range in which the desired effect of the present invention can be obtained.

[Decompression plasma coating treatment]
In the reduced pressure plasma coating treatment, a silane compound, which is a silicon supply source, is applied to the surface of a metal substrate together with plasma generated under reduced pressure to form an intermediate layer containing a silicon oxide.

As the silane compound as the silicon supply source, the silane compound described above in the section of "Itro treatment" can be used.
Further, examples of the gas required for generating plasma under reduced pressure include oxygen and argon.
For the reduced pressure plasma coating treatment, for example, an apparatus such as "CME-200E" manufactured by ULVAC can be used.
Various conditions in the reduced pressure plasma coating treatment can be appropriately adjusted within a range in which the desired effect of the present invention can be obtained.

[Middle class]
The intermediate layer formed in the intermediate layer forming step described above contains a silicon oxide, and optionally contains other components other than the silicon oxide. Then, the intermediate layer is interposed between the surface of the metal base material described above and the resin coating layer used in the resin coating step described later.

The laminated body to be produced is interposed between the surface of the metal base material and the resin coating layer, and has an intermediate layer containing a silicon oxide, thereby increasing the initial adhesive strength between the metal base material and the resin coating layer. be able to.

Examples of the silicon oxide contained in the intermediate layer include silicon dioxide, silicon monoxide, and a mixture thereof. In addition, examples of other components other than the silicon oxide contained in the intermediate layer include carbon derived from the organosilicon compound used in the surface treatment at the time of forming the intermediate layer, which will be described later, and carbon-containing compounds.

The ratio of silicon on the surface of the intermediate layer is not particularly limited, but is preferably 2.0 atm% or more, more preferably 5.0 atm% or more, still more preferably 6.7 atom% or more. It is more preferably 0 atom% or more, further preferably 14.1 atom% or more, more preferably 30.0 atom% or less, and even more preferably 25.0 atom% or less. When the silicon ratio on the surface of the intermediate layer is within the above-mentioned predetermined range, the initial adhesive strength between the metal base material and the resin coating layer can be further increased, the long-term adhesive strength between the metal base material and the resin coating layer, and the moisture resistance of the laminate. You can improve your sex.

The silicon ratio on the surface of the intermediate layer can be adjusted, for example, by changing various conditions such as the table speed of the itro treatment and the number of treatments in the method for forming the intermediate layer described above.

<Resin coating process>
In the resin coating step, the surface of the intermediate layer is coated with a resin coating layer containing a predetermined modified block copolymer hydride [E]. That is, the surface of the intermediate layer formed on the surface of the metal base material is coated with the resin coating layer containing the predetermined modified block copolymer hydride [E]. Therefore, the resin coating layer is formed on the side opposite to the side adjacent to the metal base material of the intermediate layer. As a result, it has a metal base material, an intermediate layer containing silicon oxide, and a resin coating layer containing a predetermined modified block copolymer hydride [E], and the intermediate layer is the surface of the metal base material and the resin. A laminated body is obtained which is interposed and arranged between the coating layer and the coating layer.

Here, the resin coating layer in the resin coating step coats the intermediate layer formed on the surface of the metal base material. That is, the resin coating layer covers the surface of the metal base material on the side where the intermediate layer is arranged. Therefore, the resin coating layer also covers the surface of the metal base material via the intermediate layer. As described above, by coating the surface of the metal base material with the resin coating layer via the intermediate layer, it is possible to satisfactorily prevent the metal base material from being corroded in the manufactured laminate.

When the surface of the intermediate layer is coated with the resin coating layer, a layer other than the intermediate layer and the resin coating layer may be interposed between the intermediate layer and the resin coating layer, but a metal base material is used. From the viewpoint of increasing the long-term adhesive strength between the resin coating layer and the resin coating layer, it is preferable to directly bond the intermediate layer and the resin coating layer.

Further, in the resin coating step, at least a part of the surface of the intermediate layer may be coated with the resin coating layer, but from the viewpoint of improving the corrosion resistance of the laminate, the entire surface of the intermediate layer is coated with the resin coating layer. It is preferable to do so.

Further, when the surfaces of the plurality of intermediate layers formed on the plurality of surfaces of the metal base material are coated with the resin coating layer, the surfaces of the plurality of intermediate layers may be coated with the same resin coating layer. , It may be coated with a different resin coating layer.
For example, when an intermediate layer is formed on the surfaces of both main surfaces of a sheet-like base material, the surface of the intermediate layer formed on the surface of one main surface and the surface of the other main surface are formed. The surface of the formed intermediate layer may be coated with the same resin coating layer, or may be coated with a different resin coating layer.
Further, for example, when the intermediate layer is formed on both the outer surface and the inner surface of the tubular metal base material, the surface of the intermediate layer formed on the outer surface and the intermediate layer formed on the inner surface are formed. The surface of the layer may be coated with the same resin coating layer or different resin coating layers.

<< Resin coating layer >>
The resin coating layer has a block co-weight consisting of a polymer block [A] containing an aromatic vinyl monomer unit as a main component and a polymer block [B] containing a chain conjugated diene monomer unit as a main component. The block copolymer hydride [D] obtained by hydrogenating the coalescence [C] contains a modified block copolymer hydride [E] in which an alkoxysilyl group is introduced, and optionally, a modified block such as an additive. It is a layer containing a component other than the copolymer hydride [E].

-Modified block copolymer hydride [E]-
The modified block copolymer hydride [E] is a polymer in which an alkoxysilyl group is introduced into the block copolymer hydride [D] which is a precursor.

Here, the content ratio of the modified block copolymer hydride [E] in the resin coating layer is preferably 65% by mass or more, preferably 70% by mass, from the viewpoint of initial adhesive strength, long-term adhesive strength, and moisture resistance. The above is more preferable, 75% by mass or more is further preferable, and 100% by mass or less is preferable.

--Block Copolymer Hydride [D]-
The block copolymer hydride [D] is a polymer obtained by hydrogenating the block copolymer [C] which is a precursor, and more specifically, a polymer containing an aromatic vinyl monomer unit as a main component. It is a polymer obtained by hydrogenating a block copolymer [C], which is a polymer having a block [A] and a polymer block [B] containing a chain conjugated diene monomer unit as a main component.

Here, the block copolymer hydride [D] selectively hydrogens only the carbon-carbon unsaturated bonds of the main chain and the side chains derived from the chain-conjugated diene monomer of the block polymer [C]. It may be a polymer, or it may be derived from a carbon-carbon unsaturated bond in the main chain and side chains derived from the chain-conjugated diene monomer of the block copolymer [C], and an aromatic vinyl monomer. It may be a polymer obtained by hydrogenating the carbon-carbon unsaturated bond of the aromatic ring, or it may be a mixture thereof.
When only the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain-conjugated diene monomer of the block copolymer [C] are selectively hydrogenated, the carbon-carbon unsaturated bonds of the main chain and side chains are used. The hydrogenation rate of the saturated bond is usually 95% or more, preferably 97% or more, more preferably 99% or more, and the hydrogenation rate of the carbon-carbon unsaturated bond of the aromatic ring derived from the aromatic vinyl monomer is Is usually 10% or less, preferably 5% or less, and more preferably 3% or less.
Here, "hydrogenating the carbon-carbon unsaturated bond of the main chain and the side chain" means "hydrogenating the double bond derived from the chain-conjugated diene monomer in the block copolymer". Meaning, "hydrogenating the carbon-carbon unsaturated bond of the aromatic ring" means "hydrogenating the double bond derived from the aromatic ring in the block copolymer".
Main chain and side chain carbon-carbon unsaturated bonds derived from the chain conjugated diene monomer of the block copolymer [C], and carbon-carbon unsaturated bonds of the aromatic ring derived from the aromatic vinyl monomer. When the bond is hydrogenated, the hydrogenation rate is usually 90% or more, preferably 95% or more, more preferably 99% or more of the total carbon-carbon unsaturated bond. The higher the hydrogenation rate, which indicates the degree of hydrogenation, the better the light resistance and heat resistance of the resin coating layer.

In the present invention, "hydrogenation of carbon-carbon unsaturated bond in main chain and side chain" means "hydrogenation of double bond derived from chain conjugated diene monomer in block copolymer [C]". "Hydrogenation of carbon-carbon unsaturated bonds in the aromatic ring" means "hydrogenation of double bonds derived from the aromatic ring in the block copolymer [C]". Further, in the present invention, the hydrogenation rate of the block copolymer hydride [D] is determined by a method of measuring ^{1 H-NMR of the block copolymer [C] and the block copolymer hydride [D].} be able to.

The method for hydrogenating the carbon-carbon unsaturated bond, the reaction form, and the like are not particularly limited, and may be carried out according to a known method.

As a method for selectively hydrogenating the carbon-carbon unsaturated bond of the main chain and the side chain derived from the chain-conjugated diene compound of the block copolymer [C], for example, Japanese Patent Application Laid-Open No. 2015-78090 can be used. The described methods can be mentioned.

In addition, carbon-carbon unsaturated bonds in the main chain and side chains derived from the chain-conjugated diene monomer of block copolymer [C] and carbon-carbon unsaturated bonds in the aromatic ring derived from the aromatic vinyl monomer. Examples of the method for hydrogenating the bond include the methods described in International Publication No. 2011/0963889, International Publication No. 2012/043708, and the like.
After completion of the hydrogenation reaction, the hydrogenation catalyst and / or the polymerization catalyst can be removed from the reaction solution, and then the block copolymer hydride [D] can be recovered from the obtained solution. The form of the recovered block copolymer hydride [D] is not particularly limited, but it is preferable to form pellets and subject them to the subsequent introduction reaction of the alkoxysilyl group.

The molecular weight of the block copolymer hydride [D] is not particularly limited, but from the viewpoint of improving the heat resistance and mechanical strength of the resin coating layer, gel permeation chromatography (GPC) using THF as a solvent ), The polystyrene-equivalent weight average molecular weight (Mw) is preferably 35,000 or more, more preferably 38,000 or more, further preferably 40,000 or more, and 200, It is preferably 000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less.
The molecular weight distribution (Mw / Mn) of the block copolymer hydride [D] is not particularly limited, but is preferably 3 or less from the viewpoint of improving the heat resistance and mechanical strength of the resin coating layer. It is more preferably 2 or less, and further preferably 1.7 or less.

[Elution curve measured by gel permeation chromatography (GPC)]
The number of peaks derived from block copolymer hydride [D] in the elution curve measured by gel permeation chromatography (GPC) of a sample containing block copolymer hydride [D] is not particularly limited, but the resin. From the viewpoint of enhancing the shape followability of the coating layer and further enhancing the initial adhesive strength between the metal base material and the resin coating layer, the number is preferably two or more, preferably four or less, and three or less. It is more preferable, and it is particularly preferable that there are two.
Here, the elution curve may be any as long as the peak derived from the block copolymer hydride [D] can be detected, and only the elution curve obtained by GPC measurement of only the block copolymer hydride [D]. Instead, it may be an elution curve obtained from a composition containing the block copolymer hydride [D] (for example, a composition containing an antioxidant and the block copolymer hydride [D]).
In the present specification, the "peak" means "a portion protruding from the baseline", and the "peak top" is the apex having the highest detection sensitivity (mV) of the differential refractometer (RI). Means.
Here, when the number of peaks derived from block copolymer hydride [D] in the dissolution curve measured by GPC is two or more, the most detected peak among at least two peaks derived from block copolymer hydride [D]. The peak derived from the block copolymer hydride [D] showing a highly sensitive peak top is set as the first peak, and the block copolymer hydrogen showing the peak top having the fastest elution time next to the elution time of the peak top of the first peak. The peak derived from the compound [D] is set as the second peak. For example, in FIG. 1, F is the first peak, G is the second peak, and H detected at an elution time of about 16 minutes was used to produce the block copolymer hydride [D]. The peak is derived from a solvent (for example, cyclohexane), and the two peaks detected on the negative side after 16.5 minutes are the peaks derived from tetrahydrofuran (THF) as the solvent used in the GPC measurement. I is the peak derived from the anti-aging agent.
Further, in FIG. 1, J is a plot (calibration curve) of the molecular weight of standard polystyrene measured by GPC, and as shown in FIG. 1, this calibration curve and the block copolymer hydride measured by GPC. From the elution time of [D], "standard polystyrene-equivalent molecular weight based on the elution time with the highest sensitivity of the first peak (first peak molecular weight)" and "standard polystyrene-equivalent molecular weight based on the elution time with the highest sensitivity of the second peak" (Second peak molecular weight) ”is calculated.
In the elution curve of FIG. 1, the peak derived from the anti-aging agent of I is not due to the block copolymer hydride [D].

[[First peak]]
The standard polystyrene-equivalent molecular weight (first peak molecular weight) based on the elution time of the first peak is not particularly limited, but is preferably 15,000 or more, more preferably 20,000 or more, and further preferably 25,000 or more. It is preferably 200,000 or less, more preferably 170,000 or less, and even more preferably 140,000 or less. If the standard polystyrene-equivalent molecular weight (first peak molecular weight) based on the elution time of the first peak is 15,000 or more, the impact strength of the resin coating layer can be secured, and if it is 200,000 or less, the resin coating layer can be secured. The shape followability of the metal substrate can be further enhanced, and the initial adhesive strength between the metal base material and the resin coating layer can be further enhanced.

[[Second peak]]
The standard polystyrene-equivalent molecular weight (second peak molecular weight) based on the elution time of the second peak is not particularly limited, but is preferably 1000 or more, more preferably 1200 or more, and further preferably 1500 or more. It is preferably 1800 or more, more preferably 153800 or less, more preferably 100,000 or less, and even more preferably 50,000 or less. If the standard polystyrene-equivalent molecular weight (second peak molecular weight) based on the elution time of the second peak is 1000 or more and 153,800 or less, the shape followability of the resin coating layer is further enhanced, and the metal substrate and the resin coating are further enhanced. The initial adhesive strength with the layer can be further increased.

The ratio of the standard polystyrene-equivalent molecular weight (first peak molecular weight) based on the elution time of the first peak to the standard polystyrene-equivalent molecular weight (second peak molecular weight) based on the elution time of the second peak (first peak molecular weight / second peak molecular weight) Is not particularly limited, but is preferably 1.50 or more, more preferably 2.0 or more, further preferably 4.0 or more, preferably 200 or less, and 150 or less. Is more preferable, and 100 or less is further preferable. When the ratio of the first peak molecular weight to the second peak molecular weight is 1.50 or more and 200 or less, the shape followability of the resin coating layer is further enhanced, and the initial adhesion between the metal base material and the resin coating layer is further enhanced. The strength can be further increased.

The detection sensitivity of the differential refractometer (RI) indicated by the peak top of the first peak (first peak top) with respect to the detection sensitivity (second peak top sensitivity) (mV) of the differential refractometer (RI) indicated by the peak top of the second peak. The ratio of sensitivity) (mV) (first peak top sensitivity (mV) / second peak top sensitivity (mV)) is not particularly limited, but is preferably 1.0 or more, and is preferably 1.5 or more. More preferably, it is more preferably 2.0 or more, further preferably 99 or less, further preferably 70 or less, and further preferably 50 or less. When the ratio of the first peak top sensitivity (mV) to the second peak top sensitivity (mV) is 1.0 or more, the shape followability of the resin coating layer is further enhanced, and the initial stage between the metal base material and the resin coating layer is improved. The adhesive strength can be further increased, and if it is 99 or less, the uneven film thickness of the resin coating layer can be further improved.

The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the block copolymer [C] to be subjected to the hydrogenation reaction (hydrogenation reaction), the hydrogenation temperature (hydrogenation temperature), and the hydrogenation reaction time. By appropriately adjusting the (hydrogenation reaction time) and the hydrogen supply stop time in the hydrogenation reaction (hydrogenation reaction), a predetermined first peak and a predetermined peak are defined in the dissolution curve measured by gel permeation chromatography (GPC). A block copolymer hydrogenated product [D] having a second peak of is obtained.

[Block copolymer [C]]
The block copolymer [C] contains one or more polymer blocks [A] containing an aromatic vinyl monomer unit as a main component and a polymer block [A] containing a chain conjugated diene monomer unit as a main component [ Although the polymer has one or more B], it is preferably a polymer composed of two or more polymer blocks [A] and one or more polymer blocks [B].
Here, the number of polymer blocks [A] in the block copolymer [C] is preferably 3 or less, and more preferably 2.
The number of polymer blocks [B] in the block copolymer [C] is preferably 2 or less, and more preferably 1.
A block copolymer obtained by using the block copolymer [C] by setting the numbers of the polymer blocks [A] and the polymer blocks [B] in the block copolymer [C] within the above ranges, respectively. In a resin composition containing a modified block copolymer hydride [E] obtained by introducing an alkoxysilyl group into the hydride [D], a hydride polymer block derived from the polymer block [A] (hereinafter, "hydrogenation"). It is sometimes referred to as "polymer block [A _h ]".) By preventing the phase separation between the polymer block [B] -derived hydride polymer block from becoming unclear, the hydride polymer block [A] is prevented. _It is possible to prevent the glass transition temperature on the high temperature side based on [h] from decreasing, and thus prevent the heat resistance of the resin coating layer from decreasing.

The form of the block copolymer [C] is not particularly limited and may be a chain type block or a radial type block, but from the viewpoint of improving the mechanical strength of the resin coating layer, it may be a chain type block or a radial type block. It is preferably a chain block. Here, a particularly preferable form of the block copolymer [C] is a triblock copolymer ([A]-[B]-[A] in which a polymer block [A] is bonded to both ends of the polymer block [B]. ]). It is preferable that the copolymer, which is a block copolymer, is not terminal-modified at the stage after block polymerization and before hydrogenation.
The block copolymer was composed of two polymer blocks [A] (first polymer block [A1], second polymer block [A2]) and one polymer block [B]. In the case of a triblock copolymer ([A1]-[B]-[A2]), the mass of the aromatic vinyl monomer unit derived from the first polymer block [A1] in the entire block polymer. Of the fraction and the mass fraction of the aromatic vinyl monomer unit derived from the second polymer block [A2] in the entire block polymer, one is St1 and the other is St2 (however, St1 ≦). When it is set to St2), the ratio of St1 to St2 (St1 / St2) is preferably 20/80 or more, and preferably 50/50 or less.

The mass fraction of the total aromatic vinyl monomer unit in the block copolymer [C] to the entire block copolymer [C] is wA, and the full-chain conjugated diene simple substance in the block copolymer [C] is defined as wA. When the mass fraction of the block copolymer [C] in which the polymer unit occupies the entire block copolymer [C] is wB, wA is preferably 60% or less, more preferably 55% or less, and more preferably 50% or less. It is more preferably 20% or more, more preferably 30% or more, further preferably 40% or more, and wB is preferably 80% or less, preferably 70% or less. More preferably, it is more preferably 60% or less, further preferably 40% or more, further preferably 45% or more, further preferably 50% or more.
Adhesion of the resin coating layer obtained by reducing the mass fraction (wA) of the total aromatic vinyl monomer unit in the block copolymer [C] to the entire block copolymer [C] to 60% or less. Sex can be ensured. On the other hand, the heat resistance of the resin coating layer is increased by setting the mass fraction (wA) of the total aromatic vinyl monomer unit in the block copolymer [C] to the entire block copolymer [C] to 20% or more. Sex can be ensured.

The molecular weight of the block copolymer [C] is not particularly limited, but from the viewpoint of improving the heat resistance and mechanical strength of the resin coating layer, it is a polystyrene-equivalent weight measured by GPC using tetrahydrofuran (THF) as a solvent. The average molecular weight (Mw) is preferably 35,000 or more, more preferably 38,000 or more, further preferably 40,000 or more, preferably 200,000 or less, and 150. It is more preferably 000 or less, and further preferably 100,000 or less.
The molecular weight distribution (Mw / Mn) of the block copolymer [C] is not particularly limited, but is preferably 3 or less from the viewpoint of improving the heat resistance and mechanical strength of the resin coating layer. It is more preferably less than or equal to 1.7 or less.

The method for producing the block copolymer [C] is not particularly limited, and for example, the methods described in International Publication No. 2003/018656, International Publication No. 2011/096389, and the like can be adopted.

[[Polymer block [A]]]
The polymer block [A] is a polymer block containing an aromatic vinyl monomer unit as a main component. The content ratio of the aromatic vinyl monomer unit in the polymer block [A] needs to be more than 50% by mass, assuming that all the structural units constituting the polymer block [A] are 100% by mass. It is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 99% by mass or more. The upper limit of the content ratio of the aromatic vinyl monomer unit in the polymer block [A] is not particularly limited and may be 100% by mass or less.
When the content ratio of the aromatic vinyl monomer unit in the polymer block [A] is more than 50% by mass, the heat resistance of the resin coating layer can be ensured.

The polymer block [A] may contain a monomer unit (other monomer unit) other than the aromatic vinyl monomer unit.

Examples of other monomer units that can be contained in the polymer block [A] include chain-conjugated diene monomer units and / or other vinyl monomer units, which will be described later. The total content of the chain-conjugated diene monomer unit and other vinyl monomer units in the polymer block [A] is 100% by mass with all the monomer units constituting the polymer block [A] as 100% by mass. It is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less. When the total content of the chain-conjugated diene monomer unit and the other vinyl monomer unit in the polymer block [A] is 10% by mass or less, the heat resistance of the resin coating layer can be ensured. ..

When the polymer block [A] contains a chain-conjugated diene monomer unit and / or other vinyl monomer unit, the polymer block [A] is usually an aromatic vinyl monomer unit. It is preferable to have a portion in which a chain-conjugated diene monomer unit and other vinyl monomer units are irregularly repeated.

Further, when the block copolymer [C] has a plurality of polymer blocks [A], the polymer blocks [A] may be the same as each other or may be different from each other.

Examples of the aromatic vinyl monomer capable of forming an aromatic vinyl monomer unit include styrene; α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, and 2,4-diisopropylstyrene. , 2,4-Dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, and other styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent; 4-methoxystyrene, etc. Styrenes having an alkoxy group having 1 to 6 carbon atoms as a substituent; styrenes having an aryl group as a substituent such as 4-phenylstyrene; vinylnaphthalene such as 1-vinylnaphthalene and 2-vinylnaphthalene. Kind; These may be used individually by 1 type or in combination of 2 or more type.
Among these, aromatic vinyl monomers that do not contain polar groups, such as styrene and styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, from the viewpoint of reducing the hygroscopicity of the resin coating layer. Is preferable, and styrene is more preferable because of its easy availability in the industry.

Other vinyl monomers that can form other vinyl monomer units include vinyl compounds other than aromatic vinyl monomers and chain-conjugated diene monomers, such as chain vinyl compounds and cyclic vinyl compounds. Examples thereof include unsaturated cyclic acid anhydrides and unsaturated imide compounds. These compounds may have a substituent such as a nitrile group, an alkoxycarbonyl group, a hydroxycarbonyl group, or a halogen atom. In addition, these compounds may be used alone or in combination of two or more. Among these, from the viewpoint of reducing the hygroscopicity of the resin coating layer, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-norbornene, 1-decene, 1 Chain vinyl compounds (chain olefins) with 2 to 20 carbon atoms such as −dodecene, 1-eicosene, 4-methyl-1-pentene, 4,6-dimethyl-1-heptene; vinylcyclohexane, norbornene, etc. Cyclic vinyl compounds (cyclic olefins) having 5 to 20 carbon atoms; cyclic diene compounds such as 1,3-cyclohexadiene and norbornene; and the like; which do not contain polar groups are preferable.

[[Polymer block [B]]]
The polymer block [B] is a polymer block containing a chain conjugated diene monomer unit as a main component. The content ratio of the chain-conjugated diene monomer unit in the polymer block [B] needs to be more than 50% by mass, assuming that all the structural units constituting the polymer block [B] are 100% by mass. , 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more. The upper limit of the content ratio of the chain conjugated diene monomer unit in the polymer block [B] is not particularly limited and may be 100% by mass or less.
When the content ratio of the chain-conjugated diene monomer unit in the polymer block [B] is more than 50% by mass, the flexibility of the resin coating layer is increased, and for example, the resin coating layer undergoes a rapid temperature change in the environment. It is also preferable because it is unlikely to cause problems such as cracking.

The polymer block [B] may contain a monomer unit (other monomer unit) other than the chain conjugated diene monomer unit. Examples of other monomer units that can be contained in the polymer block [B] include the above-mentioned aromatic vinyl monomer unit and / or the above-mentioned other vinyl monomer unit. The total content of the aromatic vinyl monomer unit and the other vinyl monomer unit in the polymer block [B] is 30% by mass, assuming that all the structural units constituting the polymer block [B] are 100% by mass. % Or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less. When the total content of the aromatic vinyl monomer unit and other monomer units in the polymer block [B] is 30% by mass or less, the flexibility of the resin coating layer is increased, for example, the resin coating layer. However, it is preferable because problems such as cracking are unlikely to occur due to a sudden temperature change in the environment.

When the polymer block [B] contains an aromatic vinyl monomer unit and / or other vinyl monomer unit, the polymer block [B] is usually a chain conjugated diene monomer unit, It is preferable to have a portion in which the aromatic vinyl monomer unit and other vinyl monomer units are irregularly repeated.

Further, when the block copolymer [C] has a plurality of polymer blocks [B], the polymer blocks [B] may be the same as each other or may be different from each other.

Here, the polymer block [B] is a structural unit (1,2- and 3, in which a part of the chain-conjugated diene monomer unit is polymerized by 1,2-bond and / or 3,4-bond. It has a structural unit derived from 4-addition polymerization), and the rest of the chain-conjugated diene monomer unit has a structural unit polymerized by 1,4-bond (structural unit derived from 1,4-addition polymerization). May be. In the chain-conjugated diene moiety composed of the chain-conjugated diene monomer unit in the polymer block [B], "1,2-bond (3,4-bond)" and "1,4-bond" The ratio of "1,4-bond" to the total of is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more.

The polymer block [B] containing a structural unit derived from a chain-conjugated diene monomer polymerized by 1,2-bond and / or 3,4-bond is a chain-conjugated diene monomer, if necessary. It can be obtained by polymerizing an aromatic vinyl monomer or other vinyl monomer as a randomizing agent in the presence of a specific compound having an electron donating atom. The content of the structural unit derived from the chain-conjugated diene monomer polymerized by 1,2-bond and / or 3,4-bond can be controlled by the amount of the randomizing agent added.

Examples of the compound having an electron donating atom (for example, oxygen (O) and nitrogen (N)) include an ether compound, an amine compound, and a phosphine compound. Among these, an ether compound is preferable from the viewpoint that the molecular weight distribution of the random copolymer block can be reduced and the hydrogenation reaction is less likely to be inhibited.

Specific examples of the compound having an electron donating atom include diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol diisopropyl ether, ethylene glycol dibutyl ether, and ethylene glycol methyl phenyl ether. Examples thereof include propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol diisopropyl ether, propylene glycol dibutyl ether, di (2-tetrahydrofuryl) methane, diethylene glycol dibutyl ether, dipropylene glycol dibutyl ether and tetramethylethylenediamine. These may be used individually by 1 type or in combination of 2 or more type. The content of the compound having these electron donating atoms is preferably 0.001 part by mass or more, and more preferably 0.01 part by mass or more, based on 100 parts by mass of the chain conjugated diene monomer. It is preferably 10 parts by mass or less, and more preferably 1 part by mass or less.

Examples of the chain conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and chloroprene. These may be used individually by 1 type or in combination of 2 or more type. Among these, a chain-conjugated diene monomer containing no polar group is preferable from the viewpoint of reducing the hygroscopicity of the resin coating layer, and 1,3-butadiene, isoprene is also preferable from the viewpoint of industrial availability. Is more preferable.

--Introduction of alkoxysilyl group to block copolymer hydride [D]-
Examples of the alkoxysilyl group to be introduced into the above-mentioned block copolymer hydride [D] include a tri (1 to 6 alkoxy) silyl group such as a trimethoxysilyl group and a triethoxysilyl group; a methyldimethoxysilyl group. , (Methyldiethoxysilyl group, ethyldimethoxysilyl group, ethyldiethoxysilyl group, propyldimethoxysilyl group, propyldiethoxysilyl group, etc., (1 to 20 alkyl carbon number) di (1 to 6 alkoxy carbon number) silyl group Examples thereof include (aryl) di (alkoxy of 1 to 6 carbon atoms) silyl group such as phenyldimethoxysilyl group and phenyldiethoxysilyl group.
The alkoxysilyl group is a block copolymer hydride [D] via a divalent organic group such as an alkylene group having 1 to 20 carbon atoms and an alkyleneoxycarbonylalkylene group having 2 to 20 carbon atoms. May be combined.

[Introduction amount of alkoxysilyl group]
The amount of the alkoxysilyl group introduced with respect to 100 parts by mass of the block copolymer hydride [D] is not particularly limited, and is preferably 0.5 parts by mass or more, preferably 5 parts by mass or less, and 3 parts by mass. More preferably, it is less than or equal to parts by mass.
When the amount of the alkoxysilyl group introduced is 5 parts by mass or less, cross-linking between the alkoxysilyl groups decomposed by a trace amount of water or the like is suppressed before forming the obtained modified block copolymer hydride [E]. , It is possible to prevent gelation or deterioration of fluidity at the time of melting and deterioration of moldability. On the other hand, when the amount of the alkoxysilyl group introduced is 0.5 parts by mass or more, the adhesiveness of the resin coating layer is improved, and for example, the initial adhesive strength between the metal base material and the resin coating layer can be further increased.
The introduction of the alkoxysilyl group can be confirmed by the IR spectrum of the modified block copolymer hydride [E] into which the alkoxysilyl group has been introduced. ^{Further, the amount to be introduced can be calculated from the 1} H-NMR spectrum of the modified block copolymer hydride [E] into which the alkoxysilyl group has been introduced.

[Method of introducing alkoxysilyl group]
The method for introducing an alkoxysilyl group into the block copolymer hydride [D] is not particularly limited. For example, the block copolymer hydride [D] is not ethylenic in the presence of an organic peroxide. A method for introducing an alkoxysilyl group by reacting a saturated silane compound (grafting reaction), more specifically, it comprises a block copolymer hydride [D], an ethylenically unsaturated silane compound and an organic peroxide. Examples thereof include a method of kneading the mixture in a molten state with a twin-screw kneader, a twin-screw extruder, or the like for a desired time.

The ethylenically unsaturated silane compound used in the above-mentioned introduction method may be one in which an alkoxysilyl group can be introduced into the block copolymer hydride [D] by grafting reaction with the block copolymer hydride [D]. For example, there are no particular restrictions, for example, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, 3-acryloxylpropyl. Trimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-Acryloxypropyltrimethoxysilane, etc. are preferably mentioned. These may be used alone or in combination of two or more.

The organic peroxide used in the grafting reaction is not particularly limited, but one having a one-minute half-life temperature of 170 ° C. or higher and 190 ° C. or lower is preferable. Di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butyl peroxide, 1,4-bis (2-t-butylperoxyisopropyl) ) Benzene, etc. are preferably mentioned. These may be used alone or in combination of two or more.

For example, the kneading temperature by the twin-screw extruder is not particularly limited, but is preferably 180 ° C. or higher, more preferably 185 ° C. or higher, further preferably 190 ° C. or higher, and 220 ° C. or lower. It is preferably 210 ° C. or lower, more preferably 200 ° C. or lower.
The heat-kneading time is not particularly limited, but is preferably 0.1 minutes or longer, more preferably 0.2 minutes or longer, still more preferably 0.3 minutes or longer, and 10 minutes. It is preferably less than or equal to 5 minutes, more preferably less than or equal to 5 minutes, and even more preferably less than or equal to 2 minutes.
By keeping the heat kneading temperature and the heat kneading time (residence time) within the above preferable ranges, continuous kneading and extrusion can be efficiently performed.

The form of the obtained modified block copolymer hydride [E] is not particularly limited, but it is usually preferable to form pellets and to use them for subsequent molding and blending of additives.

--Characteristics of modified block copolymer hydride [E]--
As for the molecular weight of the modified block copolymer hydride [E], since the molecular weight of the alkoxysilyl group to be introduced is usually small, it is substantially the same as the molecular weight of the block copolymer hydride [D] used as a raw material. does not change. However, since the ethylenically unsaturated silane compound is reacted (grafted reaction) with the block copolymer hydride [D] in the presence of an organic peroxide, the cross-linking reaction and the cleavage reaction of the polymer occur together. The value of the molecular weight distribution of the modified block copolymer hydride [E] becomes large.

The molecular weight of the modified block copolymer hydride [E] is not particularly limited, but is converted to polystyrene as measured by GPC using THF as a solvent from the viewpoint of improving the heat resistance and mechanical strength of the resin coating layer. The weight average molecular weight (Mw) is preferably 20,000 or more, more preferably 25,000 or more, further preferably 30,000 or more, and preferably 200,000 or less. It is more preferably 150,000 or less, and even more preferably 100,000 or less.
The molecular weight distribution (Mw / Mn) of the modified block copolymer hydride [E] is not particularly limited, but is 3.5 or less from the viewpoint of improving the heat resistance and mechanical strength of the resin coating layer. It is preferably 3.0 or less, more preferably 2.5 or less.

[Elution curve measured by gel permeation chromatography (GPC)]
The number of peaks derived from the modified block copolymer hydride [E] in the dissolution curve measured by gel permeation chromatography (GPC) of the sample containing the modified block copolymer hydride [E] is not particularly limited. From the viewpoint of enhancing the shape followability of the resin coating layer and further enhancing the initial adhesive strength between the metal substrate and the resin coating layer, the number is preferably two or more, preferably four or less, and three or less. Is more preferable, and two are particularly preferable.
Here, the elution curve may be any one as long as the peak derived from the modified block copolymer hydride [E] can be detected, and the elution obtained by GPC measurement of only the modified block copolymer hydride [E]. Not only the curve, but also the dissolution curve obtained from the composition containing the modified block copolymer hydride [E] (for example, the composition containing the antiaging agent and the modified block copolymer hydride [E]). You may.
In the present specification, the "peak" means "a portion protruding from the baseline", and the "peak top" is the apex having the highest detection sensitivity (mV) of the differential refractometer (RI). Means.
Here, when the number of peaks derived from the modified block copolymer hydride [E] in the dissolution curve measured by GPC is two or more, among at least two peaks derived from the modified block copolymer hydride [E], among the peaks derived from the modified block copolymer hydride [E], Modified block showing the peak top with the highest detection sensitivity The modified block showing the peak top derived from the polymer hydride [E] as the first peak, and the peak top showing the fastest elution time next to the elution time of the peak top of the first peak. The peak derived from the copolymer hydride [E] is set as the second peak.

[[First peak]]
The standard polystyrene-equivalent molecular weight (first peak molecular weight) based on the elution time of the first peak is not particularly limited, but is preferably 15,000 or more, more preferably 20,000 or more, and further preferably 25,000 or more. It is preferably 200,000 or less, more preferably 170,000 or less, and even more preferably 140,000 or less. If the standard polystyrene-equivalent molecular weight (first peak molecular weight) based on the elution time of the first peak is 15,000 or more, the impact strength of the resin coating layer can be secured, and if it is 200,000 or less, the resin coating layer can be secured. The shape followability of the metal substrate can be further enhanced, and the initial adhesive strength between the metal base material and the resin coating layer can be further enhanced.

[[Second peak]]
The standard polystyrene-equivalent molecular weight (second peak molecular weight) based on the elution time of the second peak is not particularly limited, but is preferably 1000 or more, more preferably 1200 or more, and further preferably 1500 or more. It is preferably 1800 or more, more preferably 153800 or less, more preferably 100,000 or less, and even more preferably 50,000 or less. If the standard polystyrene-equivalent molecular weight (second peak molecular weight) based on the elution time of the second peak is 1000 or more and 153,800 or less, the shape followability of the resin coating layer is further enhanced, and the metal substrate and the resin coating are further enhanced. The initial adhesive strength with the layer can be further increased.

The ratio of the standard polystyrene-equivalent molecular weight (first peak molecular weight) based on the elution time of the first peak to the standard polystyrene-equivalent molecular weight (second peak molecular weight) based on the elution time of the second peak (first peak molecular weight / second peak molecular weight) Is not particularly limited, but is preferably 1.50 or more, more preferably 2.0 or more, further preferably 4.0 or more, preferably 200 or less, and 150 or less. Is more preferable, and 100 or less is further preferable. When the ratio of the first peak molecular weight to the second peak molecular weight is 1.50 or more and 200 or less, the shape followability of the resin coating layer is further enhanced, and the initial adhesion between the metal base material and the resin coating layer is further enhanced. The strength can be further increased.

The detection sensitivity of the differential refractometer (RI) indicated by the peak top of the first peak (first peak top) with respect to the detection sensitivity (second peak top sensitivity) (mV) of the differential refractometer (RI) indicated by the peak top of the second peak. The ratio of sensitivity) (mV) (first peak top sensitivity (mV) / second peak top sensitivity (mV)) is not particularly limited, but is preferably 1.0 or more, and is preferably 1.5 or more. More preferably, it is more preferably 2.0 or more, further preferably 99 or less, further preferably 70 or less, and further preferably 50 or less. When the ratio of the first peak top sensitivity (mV) to the second peak top sensitivity (mV) is 1.0 or more, the shape followability of the resin coating layer is further enhanced, and the initial stage between the metal base material and the resin coating layer is improved. The adhesive strength can be further increased, and if it is 99 or less, the uneven film thickness of the resin coating layer can be improved.

The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the block copolymer [C] to be subjected to the hydrogenation reaction (hydrogenation reaction), the hydrogenation temperature (hydrogenation temperature), and the hydrogenation reaction time. By appropriately adjusting the (hydrogenation reaction time) and the hydrogen supply stop time in the hydrogenation reaction (hydrogenation reaction), a predetermined first peak and a predetermined peak are defined in the dissolution curve measured by gel permeation chromatography (GPC). A modified block copolymer hydrogenated product [E] having a second peak of is obtained.

-Additive-
Examples of the additive that the resin coating layer can optionally contain include an antioxidant, an antioxidant, a light stabilizer, and a processing aid. These may be used alone or in combination of two or more. Further, the content ratio of each of the above additives in the resin coating layer can be appropriately adjusted within a range in which the desired effect of the present invention can be obtained.

-Antioxidant-
By blending an antioxidant, the processability of the resin coating layer can be improved.
Specific examples of the antioxidant include phosphorus-based antioxidants, phenol-based antioxidants, sulfur-based antioxidants, and the like.

-Anti-blocking agent-
By blending an anti-blocking agent, it is possible to prevent blocking of pellets containing a thermoplastic resin as a main component.
Specific examples of the blocking inhibitor include lithium stearate, sodium stearate, potassium stearate, magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, barium stearate, calcium laurate, zinc laurate, barium laurate. , Zinc myristate, calcium ricinolate, zinc ricinolate, barium ricinolate, zinc behenate, sodium montanate, magnesium 12-hydroxystearate, calcium 12-hydroxystearate, zinc 12-hydroxystearate, and the like.

-Light stabilizer-
By blending a light stabilizer, the durability of the resin coating layer can be enhanced.
Specific examples of the light stabilizer include a hindered amine-based light stabilizer.

-Processing aid-
The processing aid is preferably one that can be uniformly dissolved or dispersed in the modified block copolymer hydride [E], and more preferably a hydrocarbon-based polymer having a number average molecular weight of 300 or more and 5,000 or less.

Specific examples of the hydrocarbon polymer include polyisobutylene, polybutene, poly-4-methylpentene, poly-1-octene, polyisoprene, ethylene / α-olefin copolymer, polyisoprene-butadiene copolymer and the like. Low-molecular-weight compounds and their hydrides; and the like. One of these may be used alone, or two or more of them may be used in combination at any ratio.
Among these, low molecular weight (number average molecular weight is preferably 500 or more and 3,000 or less, more preferably 500 or more and 2,500 or less) in that transparency and light resistance are maintained and the softening effect is excellent. Polyisobutylene hydrides and low molecular weight polybutene hydrides (with a number average molecular weight of preferably 500 or more and 3,000 or less, more preferably 500 or more and 2,500 or less) are preferable.

The blending amount of the low molecular weight hydrocarbon polymer is usually 40 parts by mass or less, preferably 30 parts by mass or less, and more preferably 20 parts by mass or less with respect to 100 parts by mass of the copolymer hydride. When the blending amount of the low molecular weight hydrocarbon polymer is increased, the heat resistance tends to decrease and the eluate tends to increase when the interlayer film for laminated glass is used.

<< Coating method with resin coating layer >>
As a method of coating the surface of the intermediate layer formed on the surface of the metal base material with the resin coating layer containing the above-mentioned modified block copolymer hydride [E], for example,
(I) The resin coating layer is formed while molding the resin composition containing the modified block copolymer hydride [E] into a shape that covers the surface of the intermediate layer formed on the surface of the metal base material. The method (ie, the method of molding and coating the resin composition at the same time), and
(Ii) A resin composition containing the modified block copolymer hydride [E] is preliminarily molded into a sheet to obtain a resin coating layer, and then the sheet-like resin coating layer is arbitrarily deformed while being deformed. A method of attaching to the surface of an intermediate layer formed on the surface of a metal substrate (that is, a method of coating after molding a resin composition).
Any of the above may be adopted.

When the resin composition used in the above methods (i) and (ii) contains an additive other than the modified block copolymer hydride [E], the additive is added to the modified block copolymer hydride [E]. As a method for blending, a commonly used known method can be applied. For example, (a) pellets and additives of the modified block copolymer hydride [E] are mixed with a mixer such as a tumbler, a ribbon blender, or a Henschel type mixer. After mixing evenly using ] Is melt-kneaded and extruded by a twin-screw extruder equipped with a side feeder while continuously adding various additives from the side feeder to form pellets. By these methods, a resin composition in which the additive is uniformly dispersed in the modified block copolymer hydride [E] can be produced.

The method for molding the resin composition containing the modified block copolymer hydride [E] into a desired shape in the methods (i) and (ii) is not particularly limited, and is, for example, melt extrusion. Examples thereof include a molding method, an inflation molding method, a calendar molding method, and the like.

For example, when the resin coating layer is molded by a melt extrusion molding method, the temperature of the resin composition is preferably 170 ° C. or higher, more preferably 180 ° C. or higher, and even more preferably 190 ° C. or higher. , 250 ° C. or lower, more preferably 240 ° C. or lower, and even more preferably 230 ° C. or lower. By setting the temperature of the resin composition to 170 ° C. or higher, it is possible to prevent deterioration of fluidity, prevent defects such as shavings and die lines on the surface of the resin coating layer, and increase the extrusion speed. Therefore, it can be molded industrially advantageously. On the other hand, by setting the temperature of the resin composition to 250 ° C. or lower, it is possible to prevent the fluidity of the resin composition from becoming too high and to form a resin coating layer having an uniform thickness.

In the method (i) above, the "shape that covers the surface of the intermediate layer formed on the surface of the metal base material" means, for example, when a tubular metal base material is used, the intermediate layer is used. It refers to the shape of a tube that covers the outer or inner surface of a tubular metal base material, or the shape that corresponds to a part of the tube.

Further, in the method (ii) above, as a method of attaching the sheet-shaped resin coating layer to the surface of the intermediate layer formed on the surface of the metal base material while arbitrarily deforming, for example, a flat plate press or a roll. A press, a method using a vacuum laminator device, a method using a vacuum bag, a method using a vacuum ring, a method of pressurizing with an autoclave after temporary crimping, a TOM method (Three-dimension Over-ray Method), and the like can be used.

For example, in the method of pressurizing with an autoclave after temporary crimping, a laminate obtained by superimposing a sheet-like resin coating layer on the surface of an intermediate layer formed on the surface of a metal base material is placed in a heat-resistant bag and degassed. After the temporary crimping, the resin coating layer can be melted by heating and pressurizing with an autoclave, and the resin coating layer can be attached to the surface of the intermediate layer.
The depressurizing condition when degassing using the heat-resistant bag, the heating temperature in the autoclave, and the pressurizing condition can be appropriately set within a range in which the desired effect of the present invention can be obtained.

The thickness of the resin coating layer obtained as described above is not particularly limited, and can be appropriately set according to the use of the laminate.

<Other processes>
The method for producing a laminate of the present invention may include other steps other than the intermediate layer forming step and the resin coating step described above.

The method for producing a laminate of the present invention is produced by, for example, including a step of forming an intermediate layer and a layer other than the resin coating layer on the surface of the resin coating layer after the resin coating step. The other layer may be arranged on the outside of the resin coating layer (that is, the side opposite to the side adjacent to the intermediate layer).

Further, the method for producing a laminate of the present invention includes, for example, a step of forming an intermediate layer and a layer other than the resin coating layer on the surface of the intermediate layer between the intermediate layer forming step and the resin coating step. As a result, in the manufactured laminate, the other layer may be interposed between the intermediate layer and the resin coating layer.

Further, the method for producing a laminate of the present invention includes, for example, a step of forming a layer other than the intermediate layer and the resin coating layer on the surface of the metal base material before the intermediate layer forming step. In the laminated body to be formed, the other layer may be interposed between the surface of the metal base material and the intermediate layer.

More specifically, the method for producing a laminate of the present invention includes an organic adhesive layer forming step of forming an organic adhesive layer on the surface of a metal base material before the intermediate layer forming step. In the body, an organic adhesive layer may be interposed between the surface of the metal base material and the intermediate layer.
Further, the method for producing a laminate of the present invention is produced by including an organic adhesive layer forming step of forming an organic adhesive layer on the surface of the intermediate layer between the intermediate layer forming step and the resin coating step. In the laminated body, an organic adhesive layer may be interposed between the intermediate layer and the resin coating layer.

<< Organic adhesive layer forming process >>
In the organic adhesive layer forming step, an organic adhesive layer is formed on the surface of the metal substrate before the intermediate layer forming step described above, and / or on the surface of the intermediate layer between the intermediate layer forming step and the resin coating step. An organic adhesive layer is formed on the surface.
Here, the component composition of the organic adhesive layer formed in the organic adhesive layer forming step is different from any of the component compositions of the intermediate layer and the resin coating layer described above.
The organic adhesive layer is not particularly limited, and includes, for example, an organosilicon compound such as 3-acryloxypropyltrimethoxysilane.
Then, in the organic adhesive layer forming step, for example, an aqueous solution or an aqueous dispersion containing the above-mentioned organic silicon compound is prepared as a treatment liquid, and is placed on the surface of the metal base material or the intermediate layer by a known method such as dipping and coating. A film of the treatment liquid is formed, and after heating the formed film, treatments such as washing, reheating, and drying are appropriately performed to remove water, whereby an organic adhesive layer is formed on the surface of the metal substrate. Can be formed.

From the viewpoint of enhancing the long-term adhesive strength between the metal base material and the resin coating layer and the moisture resistance of the laminate, it is preferable to directly form the intermediate layer on the surface of the metal base material. It is preferable not to form an organic adhesive layer. That is, it is preferable that the method for producing a laminate of the present invention does not include the above-mentioned organic adhesive layer forming step before the intermediate layer forming step.

<Laminated body>
The laminate produced by the method for producing a laminate of the present invention includes a metal base material, an intermediate layer containing a silicon oxide, and a resin coating layer containing the above-mentioned predetermined modified block copolymer hydride [E]. , And the intermediate layer is an intervening arrangement between the surface of the metal base material and the resin coating layer.
As described above, it has a metal base material, an intermediate layer containing silicon oxide, and a resin coating layer containing a predetermined modified block copolymer hydride [E], and the intermediate layer is a surface of the metal base material. A laminate formed by interposing and arranging between the resin coating layer has excellent initial adhesive strength between the metal base material and the resin coating layer.

The laminate produced by the method for producing a laminate of the present invention is a packaging material for pharmaceuticals, a packaging material for food, a packaging material for electronic parts, a back surface protective sheet for a solar cell module, a water pipe, a gas transport pipe, and a fuel. It can be suitably used as a transport pipe, a cable protection pipe, and the like. Further, the laminate produced by the method for producing a laminate of the present invention has a metal base material such as an LED element, an organic EL element, and an electronic substrate wiring, an intermediate layer containing a silicon oxide, and a sealing material. It may be a laminate having a resin coating layer and an intermediate layer interposed between the surface of the metal base material and the resin coating layer (sealing material).

The laminate produced by the method for producing a laminate of the present invention may optionally further have other members other than the above-mentioned metal base material, intermediate layer, and resin coating layer.

For example, the laminate produced by the method for producing a laminate of the present invention may further have an organic adhesive layer interposed between the surface of the metal base material and the intermediate layer as another member. ..

Here, the organic adhesive layer can be formed, for example, by the method for forming the organic adhesive layer described above.

From the viewpoint of enhancing the long-term adhesive strength between the metal base material and the resin coating layer and the moisture resistance of the laminate, it is preferable that the surface of the metal base material is directly adhered to the intermediate layer. It is preferable that no organic adhesive layer is interposed between the intermediate layer and the intermediate layer. That is, it is preferable that the manufactured laminate does not have an organic adhesive layer interposed between the surface of the metal base material and the intermediate layer.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following examples and comparative examples, "parts" and "%" are based on mass unless otherwise specified.
In a polymer prepared by copolymerizing a plurality of types of monomers, the mass fraction of a certain monomer unit in the entire polymer is usually prepared unless otherwise specified. It coincides with the ratio (preparation ratio) of the mass of the certain monomer to the total mass of all the monomers that sometimes polymerize.
The measurement and evaluation in this example were carried out according to the following method.

<Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)>
The weight average molecular weight (Mw) of the block copolymer [C], the block copolymer hydride [D], and the modified block copolymer hydride [E] is determined by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent. ) As a standard polystyrene-equivalent value, measured at a rate of 0.6 cc / min at 40 ° C. Tosoh's "HLC8320GPC" is used as the measuring device, and Tosoh's "TSKgel SuperH G5000HLX", Tosoh's "G4000HLX", and Tosoh's "G2000HLX" are used in series. bottom. The amount of polymer was adjusted to a concentration of 4 mg / 1 cc.
Further, after measuring the number average molecular weight (Mn) in the same manner as above, the molecular weight distribution of the block copolymer [C], the block copolymer hydride [D], and the modified block copolymer hydride [E]. (Mw / Mn) was calculated.

<Hydrogenation rate>
The hydrogenation rate (mol%) of the block copolymer hydride [D] disappeared from all unsaturated bonds present in the copolymer by performing ¹ H-NMR measurement (measurement solvent: CDCl _3). It was derived by calculating the percentage of unsaturated bonds.

<Ratio of silicon on the surface of the intermediate layer>
The intermediate layer formed in each Example and Comparative Example was subjected to elemental analysis of the surface using XPS (“PHI5000 VersaProbeII” manufactured by ULVAC-PHI) with an X-ray irradiation diameter of 100 μm. The silicon ratio on the layer surface was measured. The elements to be analyzed were nine elements: silicon, oxygen, carbon, nitrogen, iron, chromium, nickel, copper, and aluminum.

<Initial adhesive strength>
Using a cutter knife, a cutter knife was used to completely penetrate the resin coating layer on the surface of the evaluation test piece (width 100 mm × length 150 mm × thickness 7 mm) produced in each Example and Comparative Example. In addition, two notches were made at intervals of 10 mm in parallel with the length direction of the evaluation test piece. Next, the resin coating layer and the metal piece were partially peeled off on one end side of the band-shaped portion formed between the two cuts. The evaluation test piece subjected to the above treatment was fixed to a tensile tester (“AGS-10KNX” manufactured by Shimadzu Corporation) so that only the resin coating layer could be pulled, and at 23 ° C. according to JIS G3477-1. A 180 ° peel strength test was carried out, and the obtained value was evaluated as the initial adhesive strength between the metal base material and the resin coating layer according to the following criteria. The higher the value of the initial adhesive strength, the better the initial adhesive strength between the metal base material and the resin coating layer.
A: Initial adhesive strength is 100N / 10mm or more B: Initial adhesive strength is 50N / 10mm or more and less than 100N / 10mm C: Initial adhesive strength is 30N / 10mm or more and less than 50N / 10mm D: Initial adhesive strength is less than 30N / 10mm

<Adhesive strength after temperature cycle test>
The evaluation test pieces prepared in each Example and Comparative Example were stored at −50 ° C. for 12 hours, and then stored at 60 ° C. for 12 hours, and the temperature cycle test was repeated for 30 cycles. Then, after each evaluation test piece was further stored at 23 ° C. for 24 hours, a 180 ° peel strength test was performed by the same treatment and operation as the above-mentioned initial adhesive strength, and the obtained value was obtained by coating the metal substrate and the resin. The adhesive strength after the temperature cycle test with the layer was used. The higher the value of the adhesive strength after the temperature cycle test, the better the long-term adhesive strength between the metal base material and the resin coating layer.
A: Adhesive strength after temperature cycle test is 100N / 10mm or more B: Adhesive strength after temperature cycle test is 50N / 10mm or more and less than 100N / 10mm C: Adhesive strength after temperature cycle test is 30N / 10mm or more and less than 50N / 10mm D: Adhesive strength after temperature cycle test is less than 30N / 10mm

<Moisture resistance>
Using the prepared test piece for evaluation, it was stored in a constant temperature bath at 85 ° C. and 85% RH for 1000 hours and then taken out. A peel strength test was conducted, and the moisture resistance was evaluated from the obtained values.
A: Adhesive strength after storage is 100N / 10mm or more B: Adhesive strength after storage is 50N / 10mm or more and less than 100N / 10mm C: Adhesive strength after storage is 30N / 10mm or more and less than 50N / 10mm D: Adhesion after storage Strength is less than 30N / 10mm

(Manufacturing Example 1)
<Synthesis of block copolymer [C] -1>
In a reactor equipped with a stirrer and the inside of which is sufficiently nitrogen-substituted, 550 parts of dehydrated cyclohexane, 25.0 parts of dehydrated styrene, and 0.475 parts of n-dibutyl ether are placed, and n-butyllithium is stirred at 60 ° C. 2.93 parts (15% n-hexane solution) was added to initiate polymerization, and the polymerization reaction was carried out at 65 ° C. for 60 minutes. When the reaction solution was analyzed by gas chromatography (GC), the polymerization conversion rate at this point was 99.9%.
Next, 50.0 parts of dehydrated isoprene was added to the reaction solution, and stirring was continued for 40 minutes as it was. When the reaction solution was analyzed by GC, the polymerization conversion rate was 99.6% at this point.
Then, 25.0 parts of dehydrated styrene was further added, and the reaction was carried out for 60 minutes. When the reaction solution was analyzed by GC, the polymerization conversion rate at this point was almost 100%. Here, 2.0 parts of methanol was added to terminate the reaction. The weight average molecular weight (Mw) of the obtained block copolymer [C] -1 was 42,900, and the molecular weight distribution (Mw / Mn) was 1.03.
In the obtained block copolymer [C] -1, the polymer block [A] composed of styrene monomer units and the polymer block [B] composed of isoprene monomer units are [A]-[. It was a triblock copolymer arranged in the order of B]-[A].

<Synthesis of block copolymer hydride [D] -1>
Next, the solution of the block copolymer [C] -1 obtained above is transferred to a pressure resistant reactor equipped with a stirrer, and a silica-alumina-supported nickel catalyst (Clariant catalyst Co., Ltd.) as a hydrogenation catalyst is transferred. ) 4.0 parts of "T-8400RL") and 100 parts of dehydrated cyclohexane were added and mixed. At room temperature, the inside of the reactor was replaced with hydrogen gas, and the inside of the reactor was pressurized to 2.0 MPa with a gauge pressure, and the temperature was raised to 180 ° C. When the internal temperature of the pressure resistant reactor reached 180 ° C., the temperature was maintained at 180 ° C. for 60 minutes without supplying hydrogen. After 60 minutes, the hydrogen pressure was increased to 4.5 MPa, and the hydrogenation reaction was carried out for 6 hours. The weight average molecular weight (Mw) of the block copolymer hydride [D] -1 contained in the reaction solution obtained by the hydrogenation reaction was 43,900, and the molecular weight distribution (Mw / Mn) was 1.45. Further, in the GPC elution curve of block copolymer hydride [D] -1, the standard polystyrene-equivalent molecular weight (first peak molecular weight) based on the elution time of the first peak is 45,000, and the elution time of the second peak. The standard polystyrene-equivalent molecular weight (second peak molecular weight) based on the above was 9,200. Further, the first peak molecular weight / second peak molecular weight is 4.89, and the detection sensitivity (first peak top sensitivity) (mV) / second peak of the differential refractometer (RI) indicated by the peak top of the first peak. The detection sensitivity (second peak top sensitivity) (mV) of the differential refractometer (RI) indicated by the peak top was 10.18.
The hydrogenation rate of the block copolymer hydride [D] -1 was 99.9%.

After completion of the hydrogenation reaction, the reaction solution was filtered to remove the hydrogenation catalyst, and then the obtained solution was subjected to pentaerythrityl tetrakis [3- (3,5-di-t-), which is a phenolic antioxidant. Butyl-4-hydroxyphenyl) propionate] (“Songnox 1010” manufactured by Matsubara Sangyo Co., Ltd.) was dissolved by adding 2.0 parts of a xylene solution in which 0.1 part was dissolved.
Next, using a cylindrical concentrating dryer (“Contro” manufactured by Hitachi, Ltd.), the solvents cyclohexane, xylene and other volatile components were removed from the above solution at a temperature of 260 ° C. and a pressure of 0.001 MPa or less. It was extruded into a strand in a molten state from a die directly connected to a concentration dryer, cooled, and then cut with a pelletizer to obtain pellets composed of block copolymer hydride [D] -1.

<Preparation of modified block copolymer hydride [E] -1>
For 100 parts of the obtained block copolymer hydride [D] -1 pellet, 3.0 parts of vinyltrimethoxysilane as an ethylenically unsaturated silane compound and 2,5 parts as an organic peroxide. 0.1 part of −dimethyl-2,5-di (t-butylperoxy) hexane (“Perhexa® 25B” manufactured by Nichiyu Co., Ltd.) was added. This mixture was kneaded using a twin-screw extruder at a resin temperature of 200 ° C. and a residence time of 60 to 70 seconds. The obtained kneaded product was extruded into a strand shape, air-cooled, and then cut with a pelletizer to obtain pellets of a modified block copolymer hydride [E] -1 having an alkoxysilyl group.

After dissolving 10 parts of the obtained block copolymer hydride [E] -1 pellet in 100 parts of cyclohexane, the obtained solution was poured into 400 parts of dehydrated methanol to modify the block copolymer hydride [E]. E] -1 was coagulated. The obtained coagulated product was vacuum dried at 25 ° C. to isolate 9.0 parts of crumb of the modified block copolymer hydride [E] -1.

The resulting modified block copolymer hydrides [E] using the crumb -1, was measured for FT-IR spectra, Si-OCH ₃ group in 1090 cm ^-1, the 825Cm ^-1 and 739cm ^-1 Si- New absorption bands derived from ₂ CH groups are observed at different positions _{from the 3} Si-OCH groups of vinyltrimethoxysilane and the absorption bands derived from Si-CH groups (1075 cm ^-1 , 808 cm ^-1 and 766 cm ^-1). Was done.
^{Further, when the 1} H-NMR spectrum (in deuterated chloroform) of the modified block copolymer hydride [E] -1 was measured, a peak based on the proton of the methoxy group was observed at 3.6 ppm. From the peak area ratio, it was confirmed that 2.6 parts of vinyltrimethoxysilane was bonded to 100 parts of the block copolymer hydride [D] -1.

The weight average molecular weight (Mw) of the modified block copolymer hydride [E] -1 was 40,000, and the molecular weight distribution (Mw / Mn) was 2.38. Further, in the GPC elution curve of the modified block copolymer hydride [E] -1, the standard polystyrene-equivalent molecular weight (first peak molecular weight) based on the elution time of the first peak is 45,000, and the elution of the second peak. The standard polystyrene-equivalent molecular weight (second peak molecular weight) based on time was 9,200. Further, the first peak molecular weight / second peak molecular weight is 4.89, and the detection sensitivity (first peak top sensitivity) (mV) / second peak of the differential refractometer (RI) indicated by the peak top of the first peak. The detection sensitivity (second peak top sensitivity) (mV) of the differential refractometer (RI) indicated by the peak top was 11.35.

(Manufacturing Example 2)
<Synthesis of block copolymer hydride [D] -2>
The solution of the block copolymer [C] -1 obtained in Production Example 1 is transferred to a pressure-resistant reaction vessel equipped with a stirrer, and a silica-alumina-supported nickel catalyst as a hydrogenation catalyst (product name: T-). 8400RL, 4 parts of Clarian Catalyst Co., Ltd.) and 100 parts of dehydrated cyclohexane were added and mixed. The temperature was raised to 170 ° C. in a state where the inside of the reaction was replaced with hydrogen gas at room temperature and pressurized by 2 MPa with a gauge pressure. When the internal temperature of the pressure-resistant reaction vessel reached 170 ° C., hydrogen was not supplied for 20 minutes, and the temperature at 170 ° C. was kept constant. After 20 minutes, the hydrogen pressure was increased to 4.5 MPa and the hydrogenation reaction was carried out for 7 hours. The weight average molecular weight (Mw) of the block copolymer hydride [D] -2 obtained after the hydrogenation reaction was 39,500, and the molecular weight distribution (Mw / Mn) was 1.76. Further, in the GPC elution curve of block copolymer hydride [D] -2, the standard polystyrene-equivalent molecular weight (first peak molecular weight) based on the elution time of the first peak is 45,000, and the elution time of the second peak. The standard polystyrene-equivalent molecular weight (second peak molecular weight) based on the above was 31,200. Further, the first peak molecular weight / second peak molecular weight is 1.44, and the detection sensitivity (first peak top sensitivity) (mV) / second peak of the differential refractometer (RI) indicated by the peak top of the first peak. The detection sensitivity (second peak top sensitivity) (mV) of the differential refractometer (RI) indicated by the peak top was 2.36.
The hydrogenation rate of the block copolymer hydride [D] -2 was 99.8%.

After completion of the hydrogenation reaction, the reaction solution was filtered to remove the hydrogenation catalyst, and then the obtained solution was subjected to pentaerythrityl tetrakis [3- (3,5-di-t-), which is a phenolic antioxidant. Butyl-4-hydroxyphenyl) propionate] (“Songnox 1010” manufactured by Matsubara Sangyo Co., Ltd.) was dissolved by adding 2.0 parts of a xylene solution in which 0.1 part was dissolved.
Next, using a cylindrical concentrating dryer (“Contro” manufactured by Hitachi, Ltd.), the solvents cyclohexane, xylene and other volatile components were removed from the above solution at a temperature of 260 ° C. and a pressure of 0.001 MPa or less. It was extruded into a strand in a molten state from a die directly connected to a concentration dryer, cooled, and then cut with a pelletizer to obtain pellets composed of block copolymer hydride [D] -2.

<Preparation of modified block copolymer hydride [E] -2>
For 100 parts of the obtained block copolymer hydride [D] -2 pellets, 3.0 parts of vinyltrimethoxysilane as an ethylenically unsaturated silane compound and 2,5 parts as an organic peroxide. 0.1 part of −dimethyl-2,5-di (t-butylperoxy) hexane (“Perhexa® 25B” manufactured by Nichiyu Co., Ltd.) was added. This mixture was kneaded using a twin-screw extruder at a resin temperature of 200 ° C. and a residence time of 60 to 70 seconds. The obtained kneaded product was extruded into a strand shape, air-cooled, and then cut with a pelletizer to obtain pellets of a modified block copolymer hydride [E] -2 having an alkoxysilyl group.

After dissolving 10 parts of the obtained block copolymer hydride [E] -2 pellet in 100 parts of cyclohexane, the obtained solution was poured into 400 parts of dehydrated methanol to modify the block copolymer hydride [E]. E] -2 was coagulated. The obtained coagulated product was vacuum dried at 25 ° C. to isolate 9.0 parts of crumb of the modified block copolymer hydride [E] -2.

The resulting modified block copolymer hydrides [E] using the -2 crumb was measured with FT-IR spectra, Si-OCH ₃ group in 1090 cm ^-1, to 825cm ^-1 and 739cm ^-1 Si- New absorption bands derived from ₂ CH groups are observed at different positions _{from the 3} Si-OCH groups of vinyltrimethoxysilane and the absorption bands derived from Si-CH groups (1075 cm ^-1 , 808 cm ^-1 and 766 cm ^-1). Was done.
^{Moreover, when the 1} H-NMR spectrum (in deuterated chloroform) of the modified block copolymer hydride [E] -2 was measured, a peak based on the proton of the methoxy group was observed at 3.6 ppm. From the peak area ratio, it was confirmed that 2.6 parts of vinyltrimethoxysilane was bonded to 100 parts of the block copolymer hydride [D].

The weight average molecular weight (Mw) of the modified block copolymer hydride [E] -2 was 35,900, and the molecular weight distribution (Mw / Mn) was 2.79. Further, in the GPC elution curve of the modified block copolymer hydride [E] -2, the standard polystyrene-equivalent molecular weight (first peak molecular weight) based on the elution time of the first peak is 45,000, and the elution of the second peak. The standard polystyrene-equivalent molecular weight (second peak molecular weight) based on time was 31,200. Further, the first peak molecular weight / second peak molecular weight is 1.44, and the detection sensitivity (first peak top sensitivity) (mV) / second peak of the differential refractometer (RI) indicated by the peak top of the first peak. The detection sensitivity (second peak top sensitivity) (mV) of the differential refractometer (RI) indicated by the peak top was 5.14.

(Example 1)
<Intermediate layer forming process>
As a metal base material, a metal piece (material: copper (Cu), width 100 mm × length 150 mm × thickness 5 mm) that had been rust-removed by blasting was prepared. After the metal piece is washed with acetone and dried, an intermediate layer containing a silicon oxide is formed on one surface of the metal piece by an itro treatment (hereinafter, may be referred to as "itro treatment (1)"). Formed. The itro treatment (1) was performed with the following equipment and conditions. Then, the ratio of silicon on the surface of the formed intermediate layer was measured. The results are shown in Table 1.
<< Equipment and conditions used in Itro processing (1) >>
Equipment: "Itro processing equipment" manufactured by Itro
Distance between burner nozzle and metal piece: 5 mm
Silicon supply source (Itro's "Itro treatment agent <A>") Flow rate: 1.2NL / min
Air flow rate: 150NL / min
Combustible gas (LPG) flow rate: 8NL / min
Table speed: 750 mm / sec
Number of processes: 1 round trip

<Resin coating process>
<< Preparation of sheet-shaped resin coating layer >>
The modified block copolymer hydride [E] -1 obtained in Production Example 1 is cast by a T-die film melt extrusion molding machine (T-die width 400 mm) having a twin-screw kneader equipped with a screw having a diameter of 37 mm. Using an extrusion sheet molding machine equipped with a roll, a rubber nip roll, and a sheet take-up device, extrusion molding is performed under the conditions of a molten resin temperature of 200 ° C., a T-die temperature of 200 ° C., and a cast roll temperature of 90 ° C. A sheet-shaped resin coating layer (width: 330 mm, thickness: 0.5 mm) containing the polymer hydride [E] -1 was obtained. The obtained sheet-shaped resin coating layer was wound on a roll and recovered.
<< Coating with resin coating layer >>
Next, the sheet-shaped resin coating layer (thickness: 0.5 mm) produced above was cut out to a width of 100 mm and a length of 150 mm, and four sheets were laminated on the surface of the intermediate layer formed on one surface of the metal piece. rice field. The obtained laminate was placed in a heat-resistant bag made of NY (nylon) / PP (polypropylene) with a thickness of 75 μm, and after heat-sealing both sides with a heat sealer, leaving a width of 200 mm at the center of the opening of the heat-resistant bag. Using a sealed packer (“BH-951” manufactured by Panasonic Corporation), the opening was heat-sealed while degassing the inside of the heat-resistant bag, and the laminate was temporarily crimped by sealing and packaging. Then, the hermetically sealed laminate is placed in an autoclave and heated and pressurized at a temperature of 125 ° C. for 30 minutes at a pressure of 0.8 MPa to provide a metal piece, an intermediate layer, and a resin coating layer, and the intermediate layer is formed. An evaluation test piece (laminated in the order of metal piece / intermediate layer / resin coating layer, width 100 mm × length 150 mm × thickness 7 mm), which is a laminate formed between the surface of the metal piece and the resin coating layer, is placed. Obtained.
The initial adhesive strength, long-term adhesive strength, and moisture resistance were evaluated using the obtained evaluation test pieces. The results are shown in Table 1.

(Example 2)
In the intermediate layer forming step of Example 1, the material of the metal piece as the metal base material was changed from copper (Cu) to aluminum (Al), and the silicon supply source flow rate was set to 1 under the conditions of the itro treatment (1). The intermediate layer was formed by the itro treatment (2) changed from 2 NL / min to 0.6 NL / min, and was obtained in Production Example 1 in the production of the sheet-shaped resin coating layer in the resin coating step of Example 1. The same as in Example 1 except that the modified block copolymer hydride [E] -2 obtained in Production Example 2 was used instead of the modified block copolymer hydride [E] -1. , An evaluation test piece was prepared. Then, the evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 3)
In the intermediate layer forming step of Example 1, the evaluation test piece was prepared in the same manner as in Example 1 except that the material of the metal piece as the metal base material was changed from copper (Cu) to carbon steel (S55C). Made. Then, the evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 4)
In the intermediate layer forming step of Example 1, the following organic adhesive layer forming step is carried out before forming the intermediate layer to form the organic adhesive layer on one surface of the metal piece and to form the intermediate layer. Instead of the itro treatment (1), a silicon oxide is applied to the surface of the organic adhesive layer formed on one surface of the metal piece by the atmospheric pressure plasma coating treatment under the following equipment and conditions. The evaluation test piece is the same as in Example 1 except that the evaluation test piece in which the metal piece / organic adhesive layer / intermediate layer / resin coating layer is laminated in this order is produced by forming the intermediate layer containing the metal piece. Was produced. Then, the evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
<Organic adhesive layer forming process>
A 1% by mass aqueous solution of 3-acryloxypropyltrimethoxysilane (“KBM-5103” manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared. Next, the metal piece was immersed in the aqueous dispersion for 5 minutes in an environment of 23 ° C. The metal pieces were then removed from the diluent and held in an oven at 40 ° C. for 5 minutes. The metal pieces were taken out of the oven and immersed in pure water for 5 minutes in an environment of 23 ° C. The metal piece taken out from pure water was held in an oven at 40 ° C. for 120 minutes to evaporate water as a solvent to form an organic adhesive layer on the surface of the metal piece.
<Devices and conditions used in atmospheric pressure plasma coating treatment>
Equipment: Atmospheric pressure plasma processing equipment ("UL-Coat" manufactured by AcXys Technologies)
Output: 0.2kW
Distance between nozzle and metal piece: 15 mm
Air flow rate: 5NL / min
Silicon source (hexamethyldisilane) flow rate: 120 μL / min
Table speed: 320 mm / min

(Comparative Example 1)
In Example 1, the itro treatment (1) was not performed in the intermediate layer forming step, and in the resin coating step, an intermediate layer was formed on the surface instead of the metal piece having the intermediate layer formed on one surface. By directly superimposing a sheet-like resin coating layer on one surface of a metal piece, an evaluation test piece (metal piece /) in which an intermediate layer is not interposed between the surface of the metal piece and the resin coating layer. An evaluation test piece was prepared in the same manner as in Example 1 except that the resin-coated layers were laminated in this order). Then, the evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
In the production of the sheet-shaped resin coating layer in the resin coating step of Example 1, a block in which an alkoxysilyl group is not introduced is used in place of the modified block copolymer hydride [E] -1 obtained in Production Example 1. An evaluation test piece was prepared in the same manner as in Example 1 except that the copolymer hydride [D] -1 was used. Then, the evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

From Table 1, in the intermediate layer forming step of forming an intermediate layer containing a silicon oxide on the surface of a metal substrate, and the resin coating layer containing a predetermined modified block copolymer hydride in which an alkoxysilyl group is introduced. According to the method for producing a laminate of Examples 1 to 4 including the resin coating step of coating the surface of the intermediate layer, it is possible to produce a laminate having excellent initial adhesive strength between the metal base material and the resin coating layer. Recognize.

On the other hand, the laminate produced by the method for producing the laminate of Comparative Example 1 in which the intermediate layer containing silicon oxide was not formed on the surface of the metal substrate has the initial adhesive strength between the metal substrate and the resin coating layer. It turns out that it is inferior to.

Further, instead of the predetermined modified block copolymer hydride having an alkoxysilyl group introduced, the surface of the intermediate layer was coated with a resin coating layer containing a block copolymer hydride having no alkoxysilyl group introduced. It can be seen that the laminate produced by the method for producing the laminate of Comparative Example 2 is also inferior in the initial adhesive strength between the metal base material and the resin coating layer.

According to the present invention, it is possible to provide a laminate having excellent initial adhesive strength between a metal base material and a resin coating layer.

Claims (5)

An intermediate layer forming step of forming an intermediate layer containing a silicon oxide on the surface of a metal base material,
A resin coating step of coating the surface of the intermediate layer with a resin coating layer is included.
The resin coating layer is a block composed of a polymer block [A] containing an aromatic vinyl monomer unit as a main component and a polymer block [B] containing a chain conjugated diene monomer unit as a main component. A method for producing a laminate, which comprises a modified block copolymer hydride [E] in which an alkoxysilyl group is introduced into a block copolymer hydride [D] obtained by hydrogenating the polymer [C]. The method for producing a laminate according to claim 1, wherein the intermediate layer is directly formed on the surface of the metal base material. The method for producing a laminate according to claim 1 or 2, wherein the silicon ratio on the surface of the intermediate layer is 2.0 atom% or more and 30.0 atom% or less. The method for producing a laminate according to any one of claims 1 to 3, wherein the intermediate layer is formed by an itro treatment and / or an atmospheric pressure plasma coating treatment. The dissolution curve measured by gel permeation chromatography (GPC) of the sample containing the modified block copolymer hydride [E] has at least two peaks derived from the modified block copolymer hydride [E]. Of the at least two modified block copolymer hydride [E] -derived peaks, the modified block copolymer hydride [E] -derived peak showing the peak with the highest detection sensitivity is set as the first peak, and the first peak is defined as the first peak. When the peak derived from the modified block copolymer hydride [E] showing the peak top having the earliest elution time next to the elution time of the peak top is set as the second peak, the standard polystyrene conversion based on the elution time of the second peak is used. Claimed that the ratio (first peak molecular weight / second peak molecular weight) of the standard polystyrene-equivalent molecular weight (first peak molecular weight) based on the elution time of the first peak to the molecular weight (second peak molecular weight) is 1.50 or more. Item 8. The method for producing a laminate according to any one of Items 1 to 4.

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