WO2020137497A1 - Procédé de production d'un stratifié - Google Patents

Procédé de production d'un stratifié Download PDF

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Publication number
WO2020137497A1
WO2020137497A1 PCT/JP2019/048151 JP2019048151W WO2020137497A1 WO 2020137497 A1 WO2020137497 A1 WO 2020137497A1 JP 2019048151 W JP2019048151 W JP 2019048151W WO 2020137497 A1 WO2020137497 A1 WO 2020137497A1
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Prior art keywords
block copolymer
peak
resin coating
intermediate layer
coating layer
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PCT/JP2019/048151
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English (en)
Japanese (ja)
Inventor
大道 千葉
荒井　邦仁
春樹 上村
小原　禎二
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日本ゼオン株式会社
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Priority to JP2020563028A priority Critical patent/JP7380593B2/ja
Publication of WO2020137497A1 publication Critical patent/WO2020137497A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • the above-mentioned conventional laminated body had room for improvement in the adhesive strength between the metal base material and the resin coating layer.
  • the adhesive strength hereinafter sometimes referred to as “initial adhesive strength”
  • 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.
  • 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 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.
  • containing a monomer unit means "a structural unit derived from a monomer is contained in a polymer obtained by using the monomer”.
  • the intermediate layer 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.
  • the silicon ratio on the surface of the intermediate layer is preferably 2.0 atom% or more and 30.0 atom% or less.
  • the silicon ratio on the surface of the intermediate layer can be measured by the method described in Examples of this specification.
  • the intermediate layer is formed by itro treatment and/or atmospheric pressure plasma coating treatment.
  • the initial adhesive strength between the metal base material and the resin coating layer can be further increased.
  • 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.
  • the molecular weight) is preferably 1.50 or more.
  • 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.
  • the initial adhesive strength between the metal base material and the resin coating layer can be further increased.
  • FIG. 1 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).
  • 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.
  • 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.
  • 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 an intermediate layer containing silicon oxide is formed on the surface of the metal base material.
  • 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.
  • the “surface of the metal base material” is not particularly limited as long as it is a surface of the metal base material.
  • 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.
  • 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).
  • the surface of the metal base material may be flat or curved.
  • 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.
  • 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.
  • an intermediate layer containing silicon oxide can be formed on the surface of the metal substrate.
  • 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.
  • 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.
  • an intermediate layer is preferably formed on the entire outer surface (or inner surface).
  • 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.
  • 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.
  • 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.
  • 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.
  • combustible gas for example, propane gas or LPG (liquefied petroleum gas other than propane gas alone) can be used.
  • LPG liquefied petroleum gas other than propane gas alone
  • 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.
  • 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, dichlorodieth
  • 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”.
  • 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.
  • 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.
  • the silane compound which is the silicon supply source the silane compound described above in the section “ITRO treatment” can be used.
  • hexamethyldisilane is preferably used from the viewpoint of further increasing the initial adhesive strength between the metal base material and the resin coating layer.
  • the gas required for generating plasma under atmospheric pressure include oxygen, nitrogen, argon, and a mixed gas thereof.
  • the atmospheric pressure plasma coating treatment can be performed using, for example, an apparatus such as "UL-Coat" manufactured by AcXys Technologies.
  • various conditions in the atmospheric pressure plasma coating treatment can be appropriately adjusted within a range in which a desired effect of the present invention can be obtained.
  • 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.
  • the silane compound which is the silicon supply source the silane compound described above in the section “ITRO treatment” can be used.
  • the gas necessary for generating plasma under reduced pressure include oxygen and argon.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the intermediate layer formed on the outer surface and the intermediate layer formed on the inner surface may be covered with the same resin coating layer or different resin coating layers.
  • 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].
  • the modified block copolymer hydride [E] is a polymer in which an alkoxysilyl group is introduced into the precursor block copolymer hydride [D].
  • 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.
  • 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.
  • 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.
  • 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.
  • “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”.
  • hydrogenating a carbon-carbon unsaturated bond of an aromatic ring means “hydrogenating a double bond derived from an aromatic ring in a block copolymer”.
  • 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.
  • “hydrogenation of carbon-carbon unsaturated bond in main chain and side chain” means “hydrogenation of double bond derived from chain conjugated diene monomer in block copolymer [C]”.
  • “hydrogenation of carbon-carbon unsaturated bond in aromatic ring” means “hydrogenation of double bond derived from aromatic ring in block copolymer [C]”.
  • 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.
  • 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.
  • 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.
  • 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]).
  • peak means "a portion protruding from the baseline”
  • peak top is a peak at which the differential refractometer (RI) has the highest detection sensitivity (mV). Means.
  • the most detected peak is obtained from at least two block copolymer hydride [D] derived peaks.
  • the peak derived from compound [D] is designated as the second peak. For example, in FIG.
  • F is the first peak
  • G is the second peak
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 ratio of (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.
  • 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.
  • hydrogenation reaction time hydrogenation reaction time
  • hydrogenation temperature hydrogenation temperature
  • hydrogenation reaction time hydrogenation reaction time
  • hydrogen supply stop time hydrogenation reaction time
  • a predetermined first peak and a predetermined peak are obtained in the elution curve measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • 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.
  • 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].
  • the number of polymer blocks [A] in the block copolymer [C] is preferably 3 or less, and more preferably 2.
  • the number of polymer blocks [B] in the block copolymer [C] is preferably 2 or less, and more preferably 1.
  • a 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.
  • 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].
  • 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
  • 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.
  • 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.
  • 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.
  • 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. ..
  • 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.
  • 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.
  • aromatic vinyl monomer capable of forming the aromatic vinyl monomer unit examples include styrene; ⁇ -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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the flexibility of the resin coating layer increases, and for example, the resin coating layer
  • 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.
  • the polymer blocks [B] may be the same or different from each other.
  • 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
  • “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 include ether compounds, amine compounds, phosphine compounds, and the like.
  • 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.
  • 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.
  • 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.
  • chain conjugated diene monomer examples 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.
  • alkoxysilyl group into hydride block copolymer [D]--
  • 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
  • (aryl)di(C 1-6 alkoxy)silyl groups such as phenyldimethoxysilyl group and phenyldiethoxysilyl group
  • 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.
  • 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.
  • 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.
  • 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.
  • 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].
  • an alkoxysilyl group into the block copolymer hydride [D] through a graft reaction with the block copolymer hydride [D].
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • peak means "a portion protruding from the baseline”
  • peak top is a peak at which the differential refractometer (RI) has the highest detection sensitivity (mV). Means.
  • 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 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.
  • 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.
  • 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.
  • 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 ratio of (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.
  • 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.
  • hydrogenation reaction time hydrogenation reaction time
  • hydrogenation temperature hydrogenation temperature
  • hydrogenation reaction time hydrogenation reaction time
  • hydrogen supply stop time hydrogenation reaction time
  • a predetermined first peak and a predetermined peak are obtained in the elution curve measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • 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.
  • the processability of the resin coating layer can be improved.
  • the antioxidant include phosphorus-based antioxidants, phenol-based antioxidants, sulfur-based antioxidants and the like.
  • the anti-blocking agent By blending the anti-blocking agent, it is possible to prevent the pellet containing the thermoplastic resin as a main component from blocking.
  • 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.
  • the durability of the resin coating layer can be increased.
  • the light stabilizer include hindered amine light stabilizers.
  • 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.
  • hydrocarbon-based polymer examples include polyisobutylene, polybutene, poly-4-methylpentene, poly-1-octene, polyisoprene, ethylene/ ⁇ -olefin copolymer, polyisoprene-butadiene copolymer and the like.
  • 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.
  • the heat resistance tends to decrease and the eluate tends to increase easily when the interlayer film for laminated glass is used.
  • 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
  • (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.
  • the additive is added to the modified block copolymer hydride [E].
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • the other layer may be interposed between the intermediate layer and the resin coating layer in the manufactured laminate.
  • 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.
  • 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.
  • an organic adhesive layer may be disposed between the surface of the metal base material and the intermediate layer.
  • 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.
  • an organic adhesive layer may be interposed between the intermediate layer and the resin coating layer.
  • Organic Adhesive Layer Forming Step an organic adhesive layer is formed on the surface of the metal substrate before the intermediate layer forming step described above, and/or on the surface of the intermediate layer between the intermediate layer forming step and the resin coating step. An organic adhesive layer is formed on.
  • the 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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. ..
  • the organic adhesive layer can be formed, for example, by the method for forming the organic adhesive layer described above.
  • 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.
  • 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.
  • Mn number average molecular weight
  • 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 ⁇ m.
  • 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.
  • 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.
  • 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.
  • 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
  • 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
  • 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
  • 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].
  • 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.
  • 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.
  • 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%.
  • 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.
  • 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.
  • 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.
  • the first peak molecular weight/second peak molecular weight is 4.89
  • the detection sensitivity (first peak top sensitivity) (mV)/second peak of the differential refractometer (RI) indicated by the peak top of the first peak was 11.35.
  • 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.
  • Mw weight average molecular weight
  • Mw/Mn molecular weight distribution
  • the standard polystyrene-equivalent molecular weight (first peak molecular weight) based on the elution time of the first peak was 45,000
  • the elution time of the second peak was Based on the standard polystyrene equivalent molecular weight (second peak molecular weight) was 31,200.
  • the first peak molecular weight/second peak molecular weight is 1.44
  • the detection sensitivity (first peak top sensitivity) (mV)/second peak of the differential refractometer (RI) indicated by the peak top of the first peak was 2.36
  • the hydrogenation rate of the block copolymer hydride [D]-2 was 99.8%.
  • 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.
  • 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.
  • 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.
  • the first peak molecular weight/second peak molecular weight is 1.44
  • the detection sensitivity (first peak top sensitivity) (mV)/second peak of the differential refractometer (RI) indicated by the peak top of the first peak was 5.14.
  • Example 1 ⁇ Intermediate layer forming step>
  • a metal piece material: copper (Cu), width 100 mm x length 150 mm x thickness 5 mm
  • 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)”).
  • 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.
  • 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.
  • the obtained laminate was put in a heat-resistant bag made of NY (nylon)/PP (polypropylene) having a thickness of 75 ⁇ m, 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.
  • 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.
  • the hermetically-sealed laminate is put into an autoclave and heated and pressurized at a temperature of 125° C.
  • 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.
  • 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.
  • 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.
  • KBM-5103 3-acryloxypropyltrimethoxysilane
  • Example 1 (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.
  • 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.
  • 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.
  • 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.

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  • Laminated Bodies (AREA)
  • Graft Or Block Polymers (AREA)
  • Chemical Vapour Deposition (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'un stratifié ayant une excellente force de liaison initiale entre un matériau de base métallique et une couche de revêtement de résine. Un procédé de production d'un stratifié selon la présente invention est caractérisé en ce qu'il comprend une étape de formation de couche intermédiaire consistant à former une couche intermédiaire contenant un oxyde de silicium sur la surface d'un matériau de base métallique et une étape de revêtement de résine consistant à revêtir la surface de la couche intermédiaire avec une couche de revêtement de résine, la couche de revêtement de résine contenant un produit hydrogéné de copolymère bloc modifié [E] qui est produit par l'introduction d'un groupe alcoxysilyle dans un produit hydrogéné de copolymère bloc [D] produit par hydrogénation d'un copolymère bloc [C] composé d'un bloc polymère [A] contenant une unité monomère vinylique aromatique en tant que composant principal et un bloc polymère [B] contenant une unité monomère diène conjugué linéaire en tant que composant principal.
PCT/JP2019/048151 2018-12-28 2019-12-09 Procédé de production d'un stratifié WO2020137497A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS557194B2 (fr) * 1975-04-26 1980-02-22
JP2001260275A (ja) * 2000-03-14 2001-09-25 Mitsubishi Chemicals Corp 積層体
JP2009078434A (ja) * 2007-09-26 2009-04-16 Toyoda Gosei Co Ltd 金属−樹脂複合成形品及びその製造方法
JP4408879B2 (ja) * 2006-08-22 2010-02-03 株式会社イトロ 固体物質の表面改質装置およびそれを用いた表面改質方法
JP2010189732A (ja) * 2009-02-19 2010-09-02 Dental Frontier:Kk 金属の表面改質方法
WO2012043708A1 (fr) * 2010-09-29 2012-04-05 日本ゼオン株式会社 Copolymère bloc hydrogéné comprenant un groupe alcoxysilyle et son utilisation
WO2015137376A1 (fr) * 2014-03-13 2015-09-17 日本ゼオン株式会社 Feuille multicouches composite

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3557194B2 (ja) * 2002-02-13 2004-08-25 泰浩 森 固体物質の表面改質方法、表面改質された固体物質および固体物質の表面改質装置

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS557194B2 (fr) * 1975-04-26 1980-02-22
JP2001260275A (ja) * 2000-03-14 2001-09-25 Mitsubishi Chemicals Corp 積層体
JP4408879B2 (ja) * 2006-08-22 2010-02-03 株式会社イトロ 固体物質の表面改質装置およびそれを用いた表面改質方法
JP2009078434A (ja) * 2007-09-26 2009-04-16 Toyoda Gosei Co Ltd 金属−樹脂複合成形品及びその製造方法
JP2010189732A (ja) * 2009-02-19 2010-09-02 Dental Frontier:Kk 金属の表面改質方法
WO2012043708A1 (fr) * 2010-09-29 2012-04-05 日本ゼオン株式会社 Copolymère bloc hydrogéné comprenant un groupe alcoxysilyle et son utilisation
WO2015137376A1 (fr) * 2014-03-13 2015-09-17 日本ゼオン株式会社 Feuille multicouches composite

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