WO2020137497A1

WO2020137497A1 - Method for producing laminate

Info

Publication number: WO2020137497A1
Application number: PCT/JP2019/048151
Authority: WO
Inventors: 大道千葉; 荒井　邦仁; 春樹上村; 小原　禎二
Original assignee: 日本ゼオン株式会社
Priority date: 2018-12-28
Filing date: 2019-12-09
Publication date: 2020-07-02
Also published as: JP7380593B2; JPWO2020137497A1

Abstract

The present invention addresses the problem of providing a laminate having excellent initial bonding strength between a metallic base material and a resin coating layer. A method for producing a laminate according to the present invention is characterized by comprising an intermediate layer formation step of forming an intermediate layer containing a silicon oxide on the surface of a metallic base material and a resin coating step of coating the surface of the intermediate layer with a resin coating layer, wherein the resin coating layer contains a modified block copolymer hydrogenated product [E] which is produced by introducing an alkoxysilyl group into a block copolymer hydrogenated product [D] produced by hydrogenating a block copolymer [C] composed of a polymer block [A] containing an aromatic vinyl monomer unit as the main component and a polymer block [B] containing a linear conjugated diene monomer unit as the main component.

Description

Method for manufacturing laminated body

The present invention relates to a method for manufacturing a laminated body.

A laminate formed by forming a resin coating layer on the surface of a metal substrate is a packaging material for pharmaceuticals, a packaging material for foods, a packaging material for electronic parts, a back protective sheet for solar cell modules, a water pipe, a gas transportation pipe, It is used in various applications such as fuel transportation pipes and cable protection pipes. Further, as a specific example of such a laminated body, a laminated body 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. You can also list them.

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 a moisture-proof property, an oxygen barrier property, a light-shielding property, and a heat resistance. It has been reported that it is useful for applications such as packaging of pharmaceuticals and foods, back surface protection sheet for solar cell modules, encapsulation of organic EL elements, and packaging of electronic parts due to 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 steel pipe surface in order from the surface side of the steel pipe is coated at high temperature. It is disclosed that the layer has excellent adhesion durability and can be suitably used as a line pipe for carrying oil, natural gas, city gas, water and the like.

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

However, the above-mentioned conventional laminated body had room for improvement in the adhesive strength between the metal base material and the resin coating layer. In particular, the adhesive strength (hereinafter sometimes referred to as “initial adhesive strength”) between the metal base material and the resin coating layer 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 earnest studies for the purpose of solving the above problems. Then, the present inventor produced by forming an intermediate layer containing a silicon oxide on the surface of a metal substrate, and then coating 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 such a laminated body is excellent in the initial adhesive strength between the metal base material and the resin coating layer.

That is, the present invention has an object to advantageously solve the above problems, and a method for producing a laminate of the present invention is an intermediate step of forming an intermediate layer containing a silicon oxide 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, wherein 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] consisting of a polymer block [B] containing a chain conjugated diene monomer unit (linear conjugated diene, branched conjugated diene) as a main component It is characterized in that it contains a modified block copolymer hydride [E] in which an alkoxysilyl group is introduced into the copolymer hydride [D]. Thus, after the intermediate layer containing silicon oxide is formed on the surface of the metal substrate, the surface of the intermediate layer is produced by coating the surface of the intermediate layer with the resin coating layer containing the predetermined modified block copolymer hydride. The laminate has excellent initial adhesive strength between the metal base material and the resin coating layer.
In the present specification, "a polymer block [A] containing an aromatic vinyl monomer unit as a main component" means "a polymer block containing an aromatic vinyl monomer unit in an amount of more than 50% by mass [A]. ], "a polymer block [B] containing a chain conjugated diene monomer unit as a main component" means a polymer block [B containing more than 50% by mass of the chain conjugated diene monomer unit. ]] is meant. In addition, "containing a monomer unit" means "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. Thus, if the intermediate layer is directly formed on the surface of the metal base material, the adhesive strength between the metal base material and the resin coating layer after the laminate is used for a long time (hereinafter, simply “long-term adhesive strength”) , And the moisture resistance of the laminate can be improved.

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. Thus, if the silicon ratio of the intermediate layer surface is within the above predetermined range, it is possible to further increase the initial adhesive strength between the metal base material and the resin coating layer, and the long-term adhesive strength between the metal base material and the resin coating layer, And the moisture resistance of a laminated body 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 Examples of this specification.

Further, in the method for producing a laminate of the present invention, it is preferable that the intermediate layer is formed by itro treatment and/or atmospheric pressure plasma coating treatment. As described above, when 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.

Furthermore, according to the method for producing a laminate of the present invention, the elution curve of the sample containing the modified block copolymer hydride [E] measured by gel permeation chromatography (GPC) has at least two modified block copolymers. A modified block copolymer hydride [E] having a peak derived from the above-mentioned at least two modified block copolymer hydrides [E], which has a peak with the highest detection sensitivity. When the derived peak is the first peak, and the modified block copolymer hydride [E]-derived peak showing the peak top with the shortest elution time next to the elution time of the peak top of the first peak is the second peak, Ratio of standard polystyrene reduced molecular weight (first peak molecular weight) based on elution time of the first peak to standard polystyrene reduced molecular weight (second peak molecular weight) based on 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 elution curve of the sample containing the modified block copolymer hydride [E] measured by GPC has at least the predetermined first peak and the second peak, and is based on the elution time of the second peak. The ratio of the standard polystyrene reduced molecular weight (first peak molecular weight) based on the elution time of the first peak to the standard polystyrene reduced molecular weight (second peak molecular weight) (first peak molecular weight/second peak molecular weight) is not less than the above 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 the metal base material and the resin coating layer.

It is a figure for demonstrating an example of the elution curve measured by the gel permeation chromatography (GPC) of the sample containing a block copolymer hydride [D]. The vertical axis of FIG. 1 represents the polystyrene reduced molecular weight (left vertical axis) or the sensitivity (mV) (right vertical axis), and the horizontal axis of FIG. 1 represents 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 the metal substrate and the resin coating layer.

(Method for manufacturing laminated body)
The method for producing a laminate of the present invention comprises an intermediate layer forming step of forming an intermediate layer containing silicon oxide on the surface of a metal substrate, and a resin coating layer containing a predetermined modified block copolymer hydride [E]. And a resin coating step of coating the surface of the intermediate layer with.

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

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

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

<< metal substrate >>
The metal base material is a base material made of a metal material.
The metal material forming the metal substrate is not particularly limited, but examples thereof include transition metals such as iron (Fe), silver (Ag), copper (Cu), nickel (Ni), and chromium (Cr); aluminum (Al ); lead (Pb); zinc (Zn); tin (Sn); alloys containing these as the main components; and the like. Above all, it is preferable to use copper (Cu), nickel (Ni), iron (Fe), aluminum (Al), stainless steel, and carbon steel. As stainless steel, SUS304, SUS316, SUS410, SUS430, etc. can be used. Moreover, S55C, S15C, S65C etc. can be used as carbon steel.

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

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

In addition, in this specification, the “surface of the metal base material” is not particularly limited as long as it is a 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 either one of the main surfaces of the metal base material in the form of a sheet, or both surfaces of the metal base material in the form of a sheet. 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 ( Inner surface).

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

Furthermore, from the viewpoint of increasing the long-term adhesive strength between the metal base material and the resin coating layer in the laminate, the surface of the metal base material on which the intermediate layer and the resin coating layer are formed is rust-removing such as blast treatment. It may be derusted.

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

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

In addition, after forming a layer other than the intermediate layer and the resin coating layer in advance on the surface of the metal base material (for example, an organic adhesive layer described later), the metal base material is indirectly bonded to the metal base material via the other layer. The other layer may be interposed between the surface of the metal base material and the intermediate layer to be formed by subjecting the metal base material to the surface treatment, 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 the intermediate layer on the surface of the metal base material by directly performing the surface treatment on the metal base material.

In the intermediate layer forming step, the intermediate layer may be formed on at least a part of the surface of the metal base material on which the resin coating layer is formed (resin coating layer forming surface). From the viewpoint of further increasing the initial adhesive strength with the layer, it is preferable to form the intermediate layer on the entire surface on which the resin coating layer is formed.
For example, when one main surface of the sheet-shaped metal base material is the resin coating layer forming surface and the 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 the 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 From the viewpoint of further increasing the initial adhesive strength of, an intermediate layer is preferably formed on the entire outer surface (or inner surface).

Further, when the resin coating layer is formed at a plurality of locations on the metal base material, the same intermediate layer may be formed on the surface of the plurality of locations on the metal base material, or different intermediate layers may be formed. And
For example, when the intermediate layer is formed on both main surfaces of the sheet-shaped substrate, 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 the intermediate layer is formed on both the outer surface and the inner surface of the tubular metal substrate, 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 the intermediate layer is formed on at least a part of the surface of the metal base material on which the resin coating layer is formed, the components such as silicon oxide forming the intermediate layer must be present on the area without any gap. The area may be completely covered, or the area may be partially covered by being scattered on the area.

The following is a detailed description of itro treatment, atmospheric pressure plasma coating treatment, and reduced pressure plasma coating treatment, which are surface treatments that can be used as a method for forming the intermediate layer.

[ITRO processing]
In the itro treatment, a flame that is emitted by igniting a mixture of flammable gas, a gas obtained by evaporating a silane compound that is a silicon source under a gas-liquid equilibrium state, and air is emitted to the surface of the metal substrate. Apply (spray) to form an intermediate layer containing silicon oxide.

Here, as the combustible 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 and 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 the intro treatment, and examples thereof include an organic silicon compound.
Examples of the organic silicon compound include hexamethyldisiloxane; hexamethyldisilazane; tetramethylsilane, tetraethylsilane, dimethyldichlorosilane, dimethyldiphenylsilane, diethyldichlorosilane, diethyldiphenylsilane, methyltrichlorosilane, methyltriphenylsilane, Alkylsilane 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.

In addition, itro treatment includes, for example, a burner that ignites a mixture of the above-described combustible gas, a silane compound, and air to release a flame, and a table that conveys a metal base material that is a target object. It can be carried out using a device such as a product “ITRO processing device”.
In the itro treatment using the above apparatus, various conditions such as the distance between the nozzle of the burner and the metal substrate, the flow rate of the silicon supply source, the air flow rate, the combustible gas flow rate, the number of treatments, etc. are set according to the desired conditions of the present invention. It can be appropriately set within the range in which the effect is obtained.

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

As the silane compound which is the silicon supply source, the silane compound described above in the section “ITRO treatment” can be used. Among them, hexamethyldisilane is preferably used from the viewpoint of further increasing the initial adhesive strength between the metal base material and the resin coating layer.
In addition, 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.

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

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

As the silane compound which is the silicon supply source, the silane compound described above in the section “ITRO treatment” can be used.
In addition, examples of the gas necessary for generating plasma under reduced pressure include oxygen and argon.
For the low pressure plasma coating treatment, for example, an apparatus such as "CME-200E" manufactured by ULVAC Co. can be used.
Various conditions in the low pressure plasma coating treatment can be appropriately adjusted within a range where the desired effects of the present invention can be obtained.

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

The laminate to be produced is interposed between the surface of the metal base material and the resin coating layer, and has an intermediate layer containing 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 the 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 proportion of silicon on the surface of the intermediate layer is not particularly limited, but is preferably 2.0 atom% or more, more preferably 5.0 atom% or more, further preferably 6.7 atom% or more. It is more preferably 0 atom% or more, still more preferably 14.1 atom% or more, further preferably 30.0 atom% or less, and more preferably 25.0 atom% or less. When the silicon ratio on the surface of the intermediate layer is within the above 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 and the moisture resistance of the laminate can be improved. You can improve your sex.

The ratio of silicon on the surface of the intermediate layer can be adjusted, for example, by changing various conditions such as the table speed of the itro process and the number of times of the process in the method of 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 substrate is covered with a resin coating layer containing a predetermined modified block copolymer hydride [E]. Therefore, the resin coating layer is formed on the side of the intermediate layer opposite to the side adjacent to the metal base material. Thereby, 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 has a surface of the metal base material and a resin. A laminate is obtained that is interposed between the coating layer and the coating layer.

Here, the resin coating layer in the resin coating step covers the intermediate layer formed on the surface of the metal base material. That is, the resin coating layer covers the surface of the metal substrate on the side where the intermediate layer is arranged. Therefore, the resin coating layer also covers the surface of the metal substrate through the intermediate layer. In this way, the resin coating layer covers the surface of the metal base material via the intermediate layer, whereby corrosion of the metal base material in the manufactured laminate can be favorably suppressed.

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. 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.

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 enhancing the corrosion resistance of the laminate, the entire surface of the intermediate layer is coated with the resin coating layer. Preferably.

Furthermore, 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 the intermediate layer is formed on the surface of both main surfaces of the sheet-shaped substrate, the surface of the intermediate layer formed on the surface of one main surface and the surface of the other main surface The surface of the formed intermediate layer may be covered with the same resin coating layer or different resin coating layers.
Further, for example, when the intermediate layer is formed on both the outer surface and the inner surface of the tubular metal substrate, the intermediate layer formed on the outer surface and the intermediate layer formed on the inner surface The surface of the layer may be covered with the same resin coating layer or different resin coating layers.

<<Resin coating layer>>
The resin coating layer is a block copolymer 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 modified block copolymer hydride [E] obtained by introducing an alkoxysilyl group into a block copolymer hydride [D] obtained by hydrogenating a polymer [C], and optionally a modified block such as an additive It is a layer containing components 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 precursor block copolymer hydride [D].

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

--Block copolymer hydride [D]--
The block copolymer hydride [D] is a polymer obtained by hydrogenating a 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 hydrogenates only carbon-carbon unsaturated bonds in the main chain and side chains derived from the chain conjugated diene monomer of the block copolymer [C]. It may be a polymerized polymer, or may be derived from the main chain and side chain carbon-carbon unsaturated bonds derived from the chain conjugated diene monomer of the block copolymer [C] and from the aromatic vinyl monomer. The polymer may be a polymer in which the carbon-carbon unsaturated bond of the aromatic ring is hydrogenated, or a mixture thereof.
In the case of selectively hydrogenating 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], the main chain and side chain carbon-carbon unsaturated bonds 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 usually 10% or less, preferably 5% or less, more preferably 3% or less.
Here, “hydrogenating carbon-carbon unsaturated bonds in the main chain and side chains” means “hydrogenating a double bond derived from a chain conjugated diene monomer in a block copolymer”. Meaning, "hydrogenating a carbon-carbon unsaturated bond of an aromatic ring" means "hydrogenating a double bond derived from an aromatic ring in a block copolymer".
Carbon-carbon unsaturated bonds of main chain and side chain derived from chain conjugated diene monomer of block copolymer [C], and carbon-carbon unsaturated of aromatic ring derived from aromatic vinyl monomer When the bonds are hydrogenated, the hydrogenation rate is usually 90% or more, preferably 95% or more, more preferably 99% or more of the total carbon-carbon unsaturated bonds. The higher the hydrogenation rate indicating 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]”. And "hydrogenation of carbon-carbon unsaturated bond in aromatic ring" means "hydrogenation of double bond derived from aromatic ring in block copolymer [C]". Further, in the present invention, the hydrogenation rate of the block copolymer hydride [D] is obtained by a method of measuring ¹ H-NMR of the block copolymer [C] and the block copolymer hydride [D]. be able to.

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

A method for selectively hydrogenating carbon-carbon unsaturated bonds in the main chain and side chains derived from the chain conjugated diene compound of the block copolymer [C] is described in, for example, JP-A-2015-78090. Mention may be made of the methods described.

In addition, carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain conjugated diene monomer of the block copolymer [C] and carbon-carbon unsaturated of 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. 2011/096389 and International Publication No. 2012/043708.
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. There are no particular restrictions on the form of the recovered block copolymer hydride [D], but it is preferable to use it in the form of pellets for subsequent introduction reaction of an 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, still more preferably 40,000 or more, 200, It is preferably 000 or less, more preferably 150,000 or less, still 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, still more preferably 1.7 or less.

[Elution curve measured by gel permeation chromatography (GPC)]
The number of peaks derived from the block copolymer hydride [D] in the elution curve measured by gel permeation chromatography (GPC) of the sample containing the block copolymer hydride [D] is not particularly limited. From the viewpoint of enhancing the shape following property of the coating layer and further enhancing the initial adhesive strength between the metal base material and the resin coating layer, it is preferably 2 or more, preferably 4 or less, and 3 or less. It is more preferable, and it is particularly preferable that the number is two.
Here, the elution curve may be any that can detect the peak derived from the block copolymer hydride [D], and only the elution curve obtained by GPC measurement of the block copolymer hydride [D] alone Instead, it may be an elution curve obtained from a composition containing a block copolymer hydride [D] (for example, a composition containing an antioxidant and a block copolymer hydride [D]).
In the present specification, "peak" means "a portion protruding from the baseline", and "peak top" is a peak at which the differential refractometer (RI) has the highest detection sensitivity (mV). Means.
Here, when the number of peaks derived from the block copolymer hydride [D] in the elution curve measured by GPC is 2 or more, the most detected peak is obtained from at least two block copolymer hydride [D] derived peaks. A block copolymer hydrogen having a peak with a high sensitivity and a peak derived from the block copolymer hydride [D] having the first peak as the first peak, and having the shortest elution time after the elution time of the peak top of the first peak. The peak derived from compound [D] is designated 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 in the production of the block copolymer hydride [D]. It is a peak derived from a solvent (for example, cyclohexane), and two peaks detected on the minus side after 16.5 minutes are peaks derived from tetrahydrofuran (THF) as a solvent used in the GPC measurement. I is a peak derived from the antiaging agent.
Further, in FIG. 1, J is a plot (calibration curve) of the molecular weight of standard polystyrene measured by GPC. As shown in FIG. 1, this calibration curve and the hydride of the block copolymer measured by GPC are shown. From the elution time of [D], “standard polystyrene-equivalent molecular weight based on elution time with highest sensitivity of first peak (first peak molecular weight)” and “standard polystyrene-equivalent molecular weight based on elution time with highest sensitivity of second peak” (Second peak molecular weight)" is calculated.
In the elution curve of FIG. 1, the peak derived from the antioxidant 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 170000 or less, still more preferably 140000 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. It is possible to further improve the shape following property and to further increase the initial adhesive strength between the metal base material and the resin coating layer.

[[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 100000 or less, and further preferably 50000 or less. When the standard polystyrene-equivalent molecular weight (second peak molecular weight) based on the elution time of the second peak is 1000 or more and 153800 or less, the shape-following property of the resin coating layer is further enhanced, and the metal base material and the resin coating The initial adhesive strength with the layer can be further increased.

Ratio of standard polystyrene reduced molecular weight (first peak molecular weight) based on elution time of first peak to standard polystyrene reduced molecular weight (second peak molecular weight) based on elution time of 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 following property of the resin coating layer is further enhanced, and the initial adhesion between the metal base material and the resin coating layer is performed. The strength can be further increased.

The detection sensitivity of the differential refractometer (RI) indicated by the peak top of the second peak (second peak top sensitivity) (mV) to the detection sensitivity of the differential refractometer (RI) indicated by the peak top of the first peak (first peak top) 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 1.5 or more. More preferably, it is more preferably 2.0 or more, further preferably 99 or less, more preferably 70 or less, and further preferably 50 or less. If the ratio of the first peak top sensitivity (mV) to the second peak top sensitivity (mV) is 1.0 or more, the shape following property of the resin coating layer is further enhanced, and the initial stage of the metal base material and the resin coating layer. The adhesive strength can be further increased, and when it is 99 or less, the unevenness of the 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 hydrogenation reaction (hydrogenation reaction), hydrogenation temperature (hydrogenation temperature), and 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 obtained in the elution curve measured by gel permeation chromatography (GPC). A block copolymer hydride [D] having a second peak of

[Block copolymer [C]]
The block copolymer [C] includes at least one polymer block [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 it is a polymer having 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.
Further, 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 adjusting the numbers of the polymer block [A] and the polymer block [B] in the block copolymer [C] to the above ranges, respectively. In a resin composition containing a modified block copolymer hydride [E] obtained by introducing an alkoxysilyl group into a hydride [D], a hydrogenated polymer block derived from the polymer block [A] (hereinafter referred to as "hydrogenation The polymer block [A _h ]") and the hydrogenated polymer block derived from the polymer block [B] are prevented from becoming unclear, and the hydrogenated polymer block [A _h ] _It is possible to prevent the glass transition temperature on the high temperature side based on [ _h ] from lowering, and thus to prevent the heat resistance of the resin coating layer from lowering.

The block form of the block copolymer [C] is not particularly limited and may be a chain block or a radial block, but from the viewpoint of improving the mechanical strength of the resin coating layer, 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 the polymer blocks [A] are bonded to both ends of the polymer block [B]. ]). The block copolymer is preferably not subjected to terminal modification at the stage after block polymerization and before hydrogenation.
The block copolymer is 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 copolymer Of the mass fraction and the mass fraction of the aromatic vinyl monomer unit derived from the second polymer block [A2] in the entire block copolymer, one is St1 and the other is St2 (where St1≦ When it is St2), the ratio (St1/St2) of St1 and St2 is preferably 20/80 or more, and preferably 50/50 or less.

The mass fraction of all aromatic vinyl monomer units in the block copolymer [C] in the entire block copolymer [C] is wA, and the whole chain conjugated diene monomer in the block copolymer [C] is When the mass fraction of the monomer unit in the entire block copolymer [C] is wB, wA is preferably 60% or less, more preferably 55% or less, and 50% or less. More preferably, it is preferably 20% or more, more preferably 30% or more, further preferably 40% or more, wB is preferably 80% or less, and 70% or less. More preferably, it is more preferably 60% or less, further preferably 40% or more, more preferably 45% or more, still more preferably 50% or more.
Adhesion of the resin coating layer obtained by setting the mass fraction (wA) of all the aromatic vinyl monomer units in the block copolymer [C] in the entire block copolymer [C] to 60% or less. It is possible to secure the sex. On the other hand, by setting the mass fraction (wA) of all aromatic vinyl monomer units in the block copolymer [C] in the entire block copolymer [C] to be 20% or more, the heat resistance of the resin coating layer can be improved. It is possible to secure the sex.

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, the 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, and preferably 200,000 or less, 150 It is more preferably 2,000 or less, still more 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 not more than 1.7, still more preferably not more than 1.7.

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 based on 100% by mass of all structural units constituting the polymer block [A], It is preferably 90% by mass or more, more preferably 95% by mass or more, still more 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 can 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 secured.

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 a chain conjugated diene monomer unit described below and/or other vinyl monomer units. The total content of the chain conjugated diene monomer units and the other vinyl monomer units in the polymer block [A] is 100% by mass based on all the monomer units constituting the polymer block [A]. It is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less. When the total content ratio 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 secured. ..

When the polymer block [A] contains a chain conjugated diene monomer unit and/or another 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 or different from each other.

Examples of the aromatic vinyl monomer capable of forming the aromatic vinyl monomer unit include styrene; α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene. Styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, such as 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene; 4-methoxystyrene, etc. A styrene having an alkoxy group having 1 to 6 carbon atoms as a substituent; a styrene having an aryl group as a substituent such as 4-phenylstyrene; a vinylnaphthalene such as 1-vinylnaphthalene or 2-vinylnaphthalene And the like; You may use these individually by 1 type or in combination of 2 or more type.
Among these, aromatic vinyl monomers containing no polar group, 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 preferred, and styrene is more preferred because of its industrial availability.

Other vinyl monomers capable of forming other vinyl monomer units include vinyl compounds other than aromatic vinyl monomers and chain conjugated diene monomers, for example, chain vinyl compounds, 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 and a halogen atom. 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-nonene, 1-decene, 1 -Chain vinyl compounds having 2 to 20 carbon atoms (chain olefins) such as dodecene, 1-eicosene, 4-methyl-1-pentene, 4,6-dimethyl-1-heptene; vinylcyclohexane, norbornene, etc. A cyclic vinyl compound having 5 to 20 carbon atoms (cyclic olefin); a cyclic diene compound such as 1,3-cyclohexadiene or norbornadiene; and the like, which does not contain a polar group, 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 based on 100% by mass of all structural units constituting the polymer block [B]. , 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more. The upper limit of the content of the chain conjugated diene monomer unit in the polymer block [B] is not particularly limited and can 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 has a sharp temperature change in the environment. However, it is difficult to cause defects such as cracks, which is preferable.

The polymer block [B] may contain a monomer unit (other monomer unit) other than the chain conjugated diene monomer unit. Examples of the other monomer unit 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 units and the other vinyl monomer units in the polymer block [B] is 30% by mass based on 100% by mass of all the structural units constituting the polymer block [B]. % Or less, more preferably 20% by mass or less, still more preferably 10% by mass or less. When the total content ratio of the aromatic vinyl monomer unit and the other monomer unit in the polymer block [B] is 30% by mass or less, the flexibility of the resin coating layer increases, and for example, the resin coating layer However, it is difficult to cause a defect such as cracking due to a rapid temperature change in the environment, which is preferable.

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

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

Here, the polymer block [B] is a structural unit (1,2- and 3, in which a part of a chain conjugated diene monomer unit is polymerized with 1,2-bond and/or 3,4-bond). 4-addition polymerization-derived structural units), and the rest of the chain conjugated diene monomer units have structural units polymerized with 1,4-bonds (1,4-addition polymerization-derived structural units) May be In the chain conjugated diene portion composed of the chain conjugated diene monomer units 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 the above 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. Then, the aromatic vinyl monomer and other vinyl monomers are polymerized in the presence of a specific compound having an electron donating atom as a randomizing agent. 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 addition amount of the randomizing agent.

Examples of the compound having an electron donating atom (for example, oxygen (O) and nitrogen (N)) include ether compounds, amine compounds, phosphine compounds, and the like. Among these, ether compounds are preferable from the viewpoints that the molecular weight distribution of the random copolymer block can be made small and the hydrogenation reaction is difficult to be inhibited.

Specific examples of the compound having an electron donating atom include, for example, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol diisopropyl ether, ethylene glycol dibutyl ether, ethylene glycol methylphenyl 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 tetramethylethylene diamine. You may use these 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, relative to 100 parts by mass of the chain conjugated diene monomer. It is preferably 10 parts by mass or less, 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, chloroprene and the like. You may use these individually by 1 type or in combination of 2 or more type. Among these, from the viewpoint of reducing the hygroscopicity of the resin coating layer, a chain conjugated diene monomer containing no polar group is preferable, and further, 1,3-butadiene and isoprene are preferred because of their industrial availability. Is more preferable.

--Introduction of alkoxysilyl group into hydride block copolymer [D]--
Examples of the alkoxysilyl group to be introduced into the above hydrogenated block copolymer [D] include, for example, trimethoxysilyl group, triethoxysilyl group and the like, tri(C 1-6 alkoxy)silyl group; methyldimethoxysilyl group. (C1-C20 alkyl)di(C1-C6 alkoxy)silyl groups such as, methyldiethoxysilyl group, ethyldimethoxysilyl group, ethyldiethoxysilyl group, propyldimethoxysilyl group and propyldiethoxysilyl group And (aryl)di(C 1-6 alkoxy)silyl groups such as phenyldimethoxysilyl group and phenyldiethoxysilyl group;
In addition, the alkoxysilyl group is bonded to the block copolymer hydride [D] through a divalent organic group such as an alkylene group having 1 to 20 carbon atoms or an alkyleneoxycarbonylalkylene group having 2 to 20 carbon atoms. May be combined with each other.

[Introduction amount of alkoxysilyl group]
The introduction amount of the alkoxysilyl group 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, and preferably 5 parts by mass or less. It is more preferably less than or equal to parts by mass.
When the introduced amount of the alkoxysilyl group is 5 parts by mass or less, the crosslinking of the alkoxysilyl groups decomposed with a small amount of water or the like is suppressed before molding the obtained modified block copolymer hydride [E]. It is possible to prevent gelation and deterioration of moldability due to deterioration of fluidity during melting. On the other hand, when the introduction amount of the alkoxysilyl group 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] having the alkoxysilyl group introduced. The amount of introduction can be calculated from the ¹ H-NMR spectrum of the modified block copolymer hydride [E] having an alkoxysilyl group introduced.

[Method for introducing alkoxysilyl group]
The method for introducing an alkoxysilyl group into the block copolymer hydride [D] is not particularly limited, and for example, the block copolymer hydride [D] may be added with an ethylenic monomer in the presence of an organic peroxide. A method of introducing an alkoxysilyl group by reacting (grafting reaction) with a saturated silane compound, more specifically, 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 for a desired time with a twin-screw kneader, a twin-screw extruder, or the like.

The ethylenically unsaturated silane compound used in the above-described introduction method may be one that is capable of introducing an alkoxysilyl group into the block copolymer hydride [D] through a graft reaction with the block copolymer hydride [D]. If there is no particular limitation, for example, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, 3-acryloxypropyl. Trimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, Preferable is 3-acryloxypropyltrimethoxysilane. 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, and examples thereof include t-butyl cumyl peroxide, dicumyl peroxide, Di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-t-butyl peroxide, 1,4-bis(2-t-butylperoxyisopropyl) ) Benzene and the like are preferable. 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. Is preferable, 210° C. or lower is more preferable, and 200° C. or lower is further preferable.
The heating and 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. It is preferably not more than minutes, more preferably not more than 5 minutes, further preferably not more than 2 minutes.
By setting the heating and kneading temperature and the heating and 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 make it into a pellet shape and then use it for the subsequent molding processing and compounding of additives.

--Properties of modified block copolymer hydride [E]--
Regarding the molecular weight of the modified block copolymer hydride [E], since the molecular weight of the introduced alkoxysilyl group 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, in order to react the ethylenically unsaturated silane compound with the block copolymer hydride [D] in the presence of an organic peroxide (grafting reaction), a crosslinking reaction and a cleavage reaction of the polymer occur simultaneously, The value of the molecular weight distribution of the modified block copolymer hydride [E] becomes large.

The molecular weight of the hydride of the modified block copolymer [E] is not particularly limited, but from the viewpoint of improving the heat resistance and mechanical strength of the resin coating layer, it can be converted into polystyrene by GPC using THF as a solvent. 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, still 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. Preferably, it is 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 elution curve measured by gel permeation chromatography (GPC) of the sample containing the modified block copolymer hydride [E] is not particularly limited. From the viewpoints of improving the shape conformability of the resin coating layer and further increasing the initial adhesive strength between the metal substrate and the resin coating layer, it is preferably 2 or more, preferably 4 or less, and 3 or less. Is more preferable, and it is particularly preferable that it is two.
Here, the elution curve may be any as long as the peak derived from the modified block copolymer hydride [E] can be detected, and the elution curve obtained by GPC measurement of only the modified block copolymer hydride [E]. Not only the curve but also the elution curve obtained from the composition containing the modified block copolymer hydride [E] (for example, the composition containing the antioxidant and the modified block copolymer hydride [E]). May be.
In the present specification, "peak" means "a portion protruding from the baseline", and "peak top" is a peak at which the differential refractometer (RI) has the highest detection sensitivity (mV). Means.
Here, when the number of modified block copolymer hydride [E]-derived peaks in the elution curve measured by GPC is two or more, among at least two modified block copolymer hydride [E]-derived peaks, A modified block copolymer hydride [E]-derived peak exhibiting the highest peak of detection sensitivity is defined as the first peak, and a modified block exhibiting a peak top with the shortest elution time after the elution time of the peak top of the first peak. The peak derived from the copolymer hydride [E] is designated as the second peak.

The detection sensitivity of the differential refractometer (RI) indicated by the peak top of the second peak (second peak top sensitivity) (mV) to the detection sensitivity of the differential refractometer (RI) indicated by the peak top of the first peak (first peak top) 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 1.5 or more. More preferably, it is more preferably 2.0 or more, further preferably 99 or less, more preferably 70 or less, and further preferably 50 or less. If the ratio of the first peak top sensitivity (mV) to the second peak top sensitivity (mV) is 1.0 or more, the shape following property of the resin coating layer is further enhanced, and the initial stage of the metal base material and the resin coating layer. The adhesive strength can be further increased, and if it is 99 or less, the unevenness of the 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 hydrogenation reaction (hydrogenation reaction), hydrogenation temperature (hydrogenation temperature), and 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 obtained in the elution curve measured by gel permeation chromatography (GPC). A modified block copolymer hydride [E] having a second peak of

-Additive-
Examples of additives that the resin coating layer may optionally include include antioxidants, antiblocking agents, light stabilizers, and processing aids. These may be used alone or in combination of two or more. Further, the content ratio of each of the above-mentioned additives in the resin coating layer can be appropriately adjusted within a range in which the desired effects 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.

-Antiblocking agent-
By blending the anti-blocking agent, it is possible to prevent the pellet containing the thermoplastic resin as a main component from blocking.
Specific examples of the antiblocking agent 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 ricinoleate, zinc ricinoleate, barium ricinoleate, zinc behenate, sodium montanate, magnesium 12-hydroxystearate, calcium 12-hydroxystearate, zinc 12-hydroxystearate, and the like.

-Light stabilizer-
By incorporating a light stabilizer, the durability of the resin coating layer can be increased.
Specific examples of the light stabilizer include hindered amine light stabilizers.

-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 polymer having a number average molecular weight of 300 or more and 5,000 or less.

Specific examples of the hydrocarbon-based polymer include polyisobutylene, polybutene, poly-4-methylpentene, poly-1-octene, polyisoprene, ethylene/α-olefin copolymer, polyisoprene-butadiene copolymer and the like. Low molecular weight substances and hydrides thereof; and the like. These may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.
Among these, transparency, light resistance are maintained, and in terms of excellent softening effect, a 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). Polyisobutylene hydride and 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) polybutene hydride.

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 easily when the interlayer film for laminated glass is used.

<<Coating method with resin coating layer>>
Examples of the method for coating the surface of the intermediate layer formed on the surface of the metal substrate with the resin coating layer containing the modified block copolymer hydride [E] described above include:
(I) A 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 substrate. A method (that is, a method of simultaneously molding and coating a resin composition), and
(Ii) A resin composition containing the modified block copolymer hydride [E] is preformed into a sheet to obtain a resin coating layer, and the sheet resin coating layer is optionally deformed, Method of sticking to the surface of the intermediate layer formed on the surface of the metal substrate (that is, method of coating after molding the resin composition)
Either of these 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 of blending, a generally used known method can be applied. For example, (a) pellets of the modified block copolymer hydride [E] and additives are mixed with a mixer such as a tumbler, a ribbon blender or a Henschel type mixer. And then uniformly mixing, and then melt-mixing with a continuous melt-kneader such as a twin-screw extruder and extruding to form pellets, or (b) modified block copolymer hydride [E] ] Is melt-kneaded and extruded while continuously adding various additives from the side feeder with a twin-screw extruder equipped with a side feeder, thereby forming a pellet. 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 above methods (i) and (ii) is not particularly limited, and examples thereof include melt extrusion. Examples of the molding method include a molding method, an inflation molding method, a calender molding method, and the like.

For example, when the resin coating layer is molded by the melt extrusion molding method, the temperature of the resin composition is preferably 170° C. or higher, more preferably 180° C. or higher, and further preferably 190° C. or higher. The temperature is preferably 250° C. or lower, more preferably 240° C. or lower, still more preferably 230° C. or lower. By setting the temperature of the resin composition to 170° C. or higher, it is possible to prevent the fluidity from deteriorating and prevent the surface of the resin coating layer from causing defects such as orange peel and die lines, while increasing the extrusion speed. Thus, it can be molded industrially advantageously. On the other hand, by setting the temperature of the resin composition to 250° C. or less, it is possible to suppress the fluidity of the resin composition from becoming too high and form a resin coating layer having a uniform thickness.

In the above method (i), the “shape of covering the surface of the intermediate layer formed on the surface of the metal substrate” means, for example, when a tubular metal substrate is used, It refers to the shape of a tube covering the outer surface or the inner surface of a tubular metal substrate, or the shape corresponding to a part of the tube.

In the method (ii), a method of attaching the sheet-shaped resin coating layer to the surface of the intermediate layer formed on the surface of the metal substrate while arbitrarily deforming the resin coating layer is, for example, flat plate press or roll. A method using a press, 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 pressure bonding, a TOM method (Three-dimension Over-lay Method), etc. can be used.

For example, in the method of pressurizing with an autoclave after temporary pressure bonding, a laminate obtained by stacking a sheet-shaped resin coating layer on the surface of an intermediate layer formed on the surface of a metal substrate is placed in a heat-resistant bag and degassed. By doing so, after temporary pressure bonding, the resin coating layer can be melted by heating and pressurizing in an autoclave, and the resin coating layer can be attached to the surface of the intermediate layer.
The depressurizing condition when degassing using a heat resistant bag and the heating temperature and pressurizing condition in the autoclave can be appropriately set within the range where 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 application of the laminate.

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

A laminate produced by the method for producing a laminate of the present invention including, for example, 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. In, the other layer may be arranged outside the resin coating layer (that is, on 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, the other layer may be interposed between the intermediate layer and the resin coating layer in the manufactured laminate.

Furthermore, the manufacturing method of the laminate of the present invention, for example, by including a step of forming an intermediate layer and a layer other than the resin coating layer on the surface of the metal substrate before the intermediate layer forming step, In the laminated body, 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 comprises a laminate produced by including an organic adhesive layer forming step of forming an organic adhesive layer on the surface of the metal substrate before the intermediate layer forming step. In the body, an organic adhesive layer may be disposed 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 laminate, an organic adhesive layer may be interposed between the intermediate layer and the resin coating layer.

<< Organic Adhesive Layer Forming Step >>
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.
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 includes, but is not particularly limited to, 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 organosilicon compound is prepared as a treatment liquid, and by a known method such as dipping and coating, on the surface of the metal substrate or the intermediate layer. After forming a coating film of the treatment liquid and heating the formed coating film, appropriate treatments such as washing, reheating and drying are performed to remove water to form an organic adhesive layer 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, and thus the surface of the metal base material is not formed. It is preferable not to form the 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.

<Laminate>
A laminate produced by the method for producing a laminate of the present invention comprises a metal substrate, an intermediate layer containing silicon oxide, and a resin coating layer containing the above-mentioned predetermined modified block copolymer hydride [E]. And the intermediate layer is disposed between the surface of the metal base material and the resin coating layer.
Thus, 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. A laminate having an interposition between the resin coating layer and 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 foods, a packaging material for electronic parts, a solar cell module rear surface protection sheet, a water pipe, a gas transportation pipe, a fuel. It can be suitably used as a transportation 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 silicon oxide, and a sealing material. And a resin coating layer, and the intermediate layer may be a laminate in which the intermediate layer is 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 include other members other than the above-mentioned metal base material, intermediate layer, and resin coating layer.

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

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 increasing 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 produced 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 more specifically 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.
Incidentally, in a polymer prepared by copolymerizing a plurality of types of monomers, the mass fraction of the whole polymer of a certain monomer unit is usually the preparation of the polymer unless otherwise specified. It coincides with the ratio (charge ratio) of the mass of a certain monomer to the total mass of all the monomers that are sometimes polymerized.
The measurement and evaluation in this example were performed according to the following methods.

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

<Hydrogenation rate>
Regarding the hydrogenation rate (mol %) of the block copolymer hydride [D], ¹ H-NMR measurement (measurement solvent: CDCl ₃ ) was carried out, and all the unsaturated bonds existing in the copolymer disappeared. It was derived by calculating the ratio of unsaturated bonds.

<Silicon ratio on intermediate layer surface>
The intermediate layer formed in each of the Examples and Comparative Examples was subjected to elemental analysis of the surface by using XPS (“PHI5000 VersaProbe II” manufactured by ULVAC-PHI, Inc.) with the irradiation diameter of X-ray being 100 μm. The silicon ratio on the layer surface was measured. The elements to be analyzed were 9 elements of silicon, oxygen, carbon, nitrogen, iron, chromium, nickel, copper and aluminum.

<Initial adhesive strength>
Using a cutter knife on the resin coating layer side surface of the test piece for evaluation (width 100 mm x length 150 mm x thickness 7 mm) produced in each example and comparative example, so as to completely penetrate the resin coating layer, In addition, two cuts 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 strip-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 performed, and the obtained value was evaluated as the initial adhesive strength between the metal substrate and the resin coating layer according to the following criteria. The higher the initial adhesive strength value, the better the initial adhesive strength between the metal base material and the resin coating layer.
A: Initial adhesive strength of 100 N/10 mm or more B: Initial adhesive strength of 50 N/10 mm or more and less than 100 N/10 mm C: Initial adhesive strength of 30 N/10 mm or more and less than 50 N/10 mm D: Initial adhesive strength of less than 30 N/10 mm

<Adhesive strength after temperature cycle test>
With respect to the test pieces for evaluation produced in each of the examples and the comparative examples, a temperature cycle test in which one cycle of storing at −50° C. for 12 hours and then at 60° C. for 12 hours was repeated 30 times. Then, after each test piece for evaluation 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 used as the metal base material and the resin coating. It was taken as the adhesive strength after the temperature cycle test with the layer. The higher the value of the adhesive strength after the temperature cycle test, the better the long-term adhesive strength between the metal substrate and the resin coating layer.
A: Adhesive strength after the temperature cycle test is 100 N/10 mm or more B: Adhesive strength after the temperature cycle test is 50 N/10 mm or more and less than 100 N/10 mm C: Adhesive strength after the temperature cycle test is 30 N/10 mm or more and less than 50 N/10 mm D: Adhesive strength after the temperature cycle test is less than 30 N/10 mm

<Moisture resistance>
Using the produced test piece for evaluation, it was stored in a thermostatic chamber at 85° C. and 85% RH for 1000 hours, then taken out and stored at 23° C. for 24 hours, and then subjected to the same treatment and operation as the above-mentioned initial adhesive strength to 180°. A peel strength test was conducted, and moisture resistance was evaluated from the obtained values.
A: Adhesive strength after storage is 100 N/10 mm or more B: Adhesive strength after storage is 50 N/10 mm or more and less than 100 N/10 mm C: Adhesive strength after storage is 30 N/10 mm or more and less than 50 N/10 mm D: Adhesion after storage Strength is less than 30N/10mm

(Production Example 1)
<Synthesis of Block Copolymer [C]-1>
In a reactor equipped with a stirrer and whose inside was sufficiently replaced with nitrogen, 550 parts of dehydrated cyclohexane, 25.0 parts of dehydrated styrene and 0.475 part of n-dibutyl ether were charged, and n-butyllithium was stirred at 60°C. (15% n-hexane solution) (2.93 parts) was added to initiate polymerization, and a polymerization reaction was carried out at 65°C for 60 minutes. When the reaction liquid was analyzed by gas chromatography (GC), the polymerization conversion rate at this time 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 liquid was analyzed by GC, the polymerization conversion ratio was 99.6% at this point.
After that, 25.0 parts of dehydrated styrene was further added and reacted 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 stop 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.
The obtained block copolymer [C]-1 had a polymer block [A] composed of styrene monomer units and a polymer block [B] composed of isoprene monomer units [A]-[ It was a triblock copolymer which was 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 was transferred to a pressure resistant reactor equipped with a stirrer, and a silica-alumina-supported nickel catalyst (Clariant catalyst (stock) ) "T-8400RL") and 4.0 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 heated to 180° C. with the gauge pressure increased to 2.0 MPa. When the internal temperature of the pressure-resistant reactor reached 180°C, the temperature was kept 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 performed for 6 hours. The block copolymer hydride [D]-1 contained in the reaction solution obtained by the hydrogenation reaction had a weight average molecular weight (Mw) of 43,900 and a molecular weight distribution (Mw/Mn) of 1.45. In the GPC elution curve of the block copolymer hydride [D]-1, the standard polystyrene-equivalent molecular weight (first peak molecular weight) based on the elution time of the first peak was 45,000, and the elution time of the second peak was The standard polystyrene-equivalent molecular weight (second peak molecular weight) based on the above was 9,200. Furthermore, 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 the resulting solution was mixed with pentaerythrityl tetrakis[3-(3,5-di-t- Butyl-4-hydroxyphenyl)propionate] (“Songnox 1010” manufactured by Matsubara Sangyo Co., Ltd.) was dissolved in 2.0 parts of xylene solution.
Then, using a cylindrical concentrating dryer (“Contro” manufactured by Hitachi, Ltd.), at a temperature of 260° C. and a pressure of 0.001 MPa or less, the solvents cyclohexane, xylene and other volatile components are removed from the solution, A die directly connected to the concentrating dryer was extruded in a molten state into a strand, cooled, and cut with a pelletizer to obtain pellets of the block copolymer hydride [D]-1.

<Preparation of modified block copolymer hydride [E]-1>
To 100 parts of the obtained pellets of the block copolymer hydride [D]-1, 3.0 parts of vinyltrimethoxysilane as an ethylenically unsaturated silane compound and 2,5 as an organic peroxide. 0.1 part of dimethyl-2,5-di(t-butylperoxy)hexane (“Perhexa® 25B” manufactured by NOF CORPORATION) 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 in 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 pellets of the obtained block copolymer hydride [E]-1 in 100 parts of cyclohexane, the obtained solution was poured into 400 parts of dehydrated methanol to obtain a modified block copolymer hydride [[ E]-1 solidified. 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 FT-IR spectrum of the obtained modified block copolymer hydride [E]-1 crumb was measured. Si-OCH ₃ group was found at 1090 cm ^-1 , Si-OCH ₃ was found at 825 cm ^-1 and 739 cm ^-1 . A new absorption band derived from the CH ₂ group is observed at a position different from the absorption bands (1075 cm ^-1 , 808 cm ^-1 and 766 cm ^-1 ) derived from the Si-OCH ₃ group and Si-CH group of vinyltrimethoxysilane. Was done.
Further, the ¹ H-NMR spectrum (in deuterated chloroform) of the hydrogenated modified block copolymer [E]-1 was measured, and 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 bound to 100 parts of the block copolymer hydride [D]-1.

The modified block copolymer hydride [E]-1 had a weight average molecular weight (Mw) of 40,000 and a molecular weight distribution (Mw/Mn) of 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 was 45,000, and the second peak was eluted. The standard polystyrene-equivalent molecular weight (second peak molecular weight) based on time was 9,200. Furthermore, 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.

(Production Example 2)
<Synthesis of block copolymer hydride [D]-2>
The solution of the block copolymer [C]-1 obtained in Production Example 1 was transferred to a pressure-resistant reaction vessel equipped with a stirrer, and a silica-alumina-supported nickel catalyst (product name: T- 8400RL, 4 parts of Clariant Catalyst Co., Ltd.) and 100 parts of dehydrated cyclohexane were added and mixed. At room temperature, the inside of the reaction was replaced with hydrogen gas, and the pressure was raised to 170° C. with a gauge pressure of 2 MPa. When the internal temperature of the pressure resistant reactor reached 170°C, hydrogen was not supplied for 20 minutes and the temperature of 170°C was kept constant. After 20 minutes, the hydrogen pressure was increased to 4.5 MPa to carry out a hydrogenation reaction for 7 hours. The block copolymer hydride [D]-2 obtained after the hydrogenation reaction had a weight average molecular weight (Mw) of 39,500 and a molecular weight distribution (Mw/Mn) of 1.76. In the GPC elution curve of the block copolymer hydride [D]-2, the standard polystyrene-equivalent molecular weight (first peak molecular weight) based on the elution time of the first peak was 45,000, and the elution time of the second peak was Based on the standard polystyrene equivalent molecular weight (second peak molecular weight) 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 the resulting solution was mixed with pentaerythrityl tetrakis[3-(3,5-di-t- Butyl-4-hydroxyphenyl)propionate] (“Songnox 1010” manufactured by Matsubara Sangyo Co., Ltd.) was dissolved in 2.0 parts of xylene solution.
Then, using a cylindrical concentrating dryer (“Contro” manufactured by Hitachi, Ltd.), at a temperature of 260° C. and a pressure of 0.001 MPa or less, the solvents cyclohexane, xylene and other volatile components are removed from the solution, A die directly connected to the concentrating dryer was extruded in a molten state into a strand, cooled, and cut with a pelletizer to obtain pellets of the block copolymer hydride [D]-2.

<Preparation of modified block copolymer hydride [E]-2>
To 100 parts of the obtained pellets of the block copolymer hydride [D]-2, 3.0 parts of vinyltrimethoxysilane as an ethylenically unsaturated silane compound and 2,5 as an organic peroxide. 0.1 part of dimethyl-2,5-di(t-butylperoxy)hexane (“Perhexa® 25B” manufactured by NOF CORPORATION) 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 pellet of the obtained block copolymer hydride [E]-2 in 100 parts of cyclohexane, the obtained solution was poured into 400 parts of dehydrated methanol to obtain a modified block copolymer hydride [[ E]-2 solidified. 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 FT-IR spectrum of the obtained modified block copolymer hydride [E]-2 crumb was measured. Si-OCH ₃ group was found at 1090 cm ^-1 and Si-at 825 cm ^-1 and 739 cm ^-1 . A new absorption band derived from the CH ₂ group is observed at a position different from the absorption bands (1075 cm ^-1 , 808 cm ^-1 and 766 cm ^-1 ) derived from the Si-OCH ₃ group and Si-CH group of vinyltrimethoxysilane. Was done.
Further, the ¹ H-NMR spectrum (in deuterated chloroform) of the hydride of the modified block copolymer [E]-2 was measured, and 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 modified block copolymer hydride [E]-2 had a weight average molecular weight (Mw) of 35,900 and a molecular weight distribution (Mw/Mn) of 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 was 45,000, and the second peak was eluted. 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 step>
As the metal base material, a metal piece (material: copper (Cu), width 100 mm x length 150 mm x thickness 5 mm) that was removed by blast treatment was prepared. After washing the metal piece with acetone and drying it, an intermediate layer containing silicon oxide is formed on one surface of the metal piece by the itro treatment (hereinafter, may be referred to as “itro treatment (1)”). Formed. The itro process (1) was performed using the following apparatus and conditions. Then, the silicon ratio on the surface of the formed intermediate layer was measured. The results are shown in Table 1.
<<Devices and Conditions Used in Itro Process (1)>>
Device: "ITRO processing device" manufactured by Itro
Distance between burner nozzle and metal piece: 5 mm
Silicon supply source (“ITRO treatment agent <A>” manufactured by Itro) Flow rate: 1.2 NL/min
Air flow rate: 150 NL/min
Flammable gas (LPG) flow rate: 8 NL/min
Table speed: 750 mm/sec
Number of processing times: 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 was cast using a T-die type film melt extrusion molding machine (T-die width 400 mm) having a biaxial 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 collected.
<<Coating with resin coating layer>>
Next, the sheet-shaped resin coating layer (thickness: 0.5 mm) produced above is cut into a width of 100 mm and a length of 150 mm, and four sheets are stacked on the surface of the intermediate layer formed on one surface of the metal piece. It was The obtained laminate was put in a heat-resistant bag made of NY (nylon)/PP (polypropylene) having a thickness of 75 μm, and the both sides of the heat-resistant bag were heat-sealed with a heat sealer while leaving the center of the opening of the heat-resistant bag at a width of 200 mm. Using a sealed pack device (“BH-951” manufactured by Panasonic Corporation), the opening was heat-sealed while the inside of the heat-resistant bag was deaerated, and the laminate was hermetically sealed for temporary pressure bonding. Then, the hermetically-sealed laminate is put into 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. A test piece for evaluation (a metal piece/intermediate layer/resin coating layer, laminated in this order, width 100 mm×length 150 mm×thickness 7 mm), which is a laminate formed by being interposed between the surface of the metal piece and the resin coating layer, Obtained.
Using the obtained test pieces for evaluation, initial adhesive strength, long-term adhesive strength, and moisture resistance were evaluated. 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 source flow rate was set to 1 in the condition of the itro treatment (1). The intermediate layer was formed by the itro treatment (2) in which the pressure was changed from 2 NL/min to 0.6 NL/min, and the sheet-shaped resin coating layer was obtained in Production Example 1 in the resin coating step of Example 1. In the same manner as in Example 1 except that the modified block copolymer hydride [E]-1 obtained in Production Example 2 was used in place of the modified block copolymer hydride [E]-1. A test piece for evaluation was prepared. Then, 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, an 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). It was made. Then, 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, before forming the intermediate layer, the following organic adhesive layer forming step is performed to form the organic adhesive layer on one surface of the metal piece and to form the intermediate layer. In doing so, instead of itro treatment (1), silicon oxide was formed on the surface of the organic adhesive layer formed on one surface of the metal piece by atmospheric pressure plasma coating treatment under the following apparatus and conditions. An evaluation test piece was prepared in the same manner as in Example 1 except that an evaluation test piece in which metal pieces/organic adhesive layer/intermediate layer/resin coating layer were laminated in this order was formed by forming an intermediate layer containing the same. Was produced. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
<Organic adhesive layer forming step>
A 1 mass% aqueous solution of 3-acryloxypropyltrimethoxysilane (“KBM-5103” manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared. Then, the metal piece was immersed in the aqueous dispersion for 5 minutes in an environment of 23°C. Then, the metal piece was taken out from the diluent and kept in an oven at 40° C. for 5 minutes. The metal piece was 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 the pure water was kept 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.
<Apparatus and conditions used in atmospheric plasma coating>
Equipment: Atmospheric pressure plasma processing equipment ("UL-Coat" manufactured by AcXys Technologies)
Output: 0.2kW
Distance between nozzle and metal piece: 15mm
Air flow rate: 5NL/min
Flow rate of silicon supply source (hexamethyldisilane): 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, the intermediate layer was formed on the surface instead of the metal piece having the intermediate layer formed on one surface. By directly laying a sheet-shaped resin coating layer on one surface of the metal piece that does not exist, an intermediate test piece is not placed between the surface of the metal piece and the resin coating layer. A test piece for evaluation was prepared in the same manner as in Example 1 except that the resin coating layer was laminated in this order). Then, 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 a sheet-shaped resin coating layer in the resin coating step of Example 1, a block in which an alkoxysilyl group is not introduced is substituted for the modified block copolymer hydride [E]-1 obtained in Production Example 1. A test piece for evaluation was prepared in the same manner as in Example 1 except that the copolymer hydride [D]-1 was used. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.

From Table 1, an intermediate layer forming step of forming an intermediate layer containing a silicon oxide on the surface of a metal substrate, and a 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 step of coating the surface of the intermediate layer with a resin, it is possible to produce a laminate having excellent initial adhesion strength between the metal substrate and the resin coating layer. Recognize.

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

Further, the surface of the intermediate layer was coated with a resin coating layer containing a block copolymer hydride in which an alkoxysilyl group was not introduced, instead of a predetermined modified block copolymer hydride in which an alkoxysilyl group was introduced. It can be seen that the laminate produced by the method for producing a laminate of Comparative Example 2 is also inferior in the initial adhesive strength between the metal base material and the resin coating layer.

Claims

An intermediate layer forming step of forming an intermediate layer containing silicon oxide on the surface of the metal substrate,
A resin coating step of coating the surface of the intermediate layer with a resin coating layer,
The resin coating layer is a block copolymer 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 process for producing a laminate, comprising a modified block copolymer hydride [E] obtained by introducing an alkoxysilyl group into a block copolymer hydride [D] obtained by hydrogenating a polymer [C].
The method for manufacturing 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 itro treatment and/or atmospheric pressure plasma coating treatment.
The elution curve of the sample containing the modified block copolymer hydride [E] measured by gel permeation chromatography (GPC) has at least two peaks derived from the modified block copolymer hydride [E], Among the at least two modified block copolymer hydride [E]-derived peaks, the modified block copolymer hydride [E]-derived peak exhibiting the highest peak detection sensitivity is defined as the first peak, and the first peak When the peak derived from the modified block copolymer hydride [E] showing a peak top with the next shortest elution time after the elution time of the second peak is defined as the second peak, the standard polystyrene conversion based on the elution time of the second peak is performed. The ratio 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) (first peak molecular weight/second peak molecular weight) is 1.50 or more. Item 5. A method for producing a laminate according to any one of Items 1 to 4.