Laminate and medical device

Abstract

The present invention addresses the problem of providing: a laminate which has excellent sterilization durability and is suitable as a constituent member of a medical device; and a medical device including the laminate. The laminate has a substrate, an intermediate layer on the substrate, and a polymer coating layer on the intermediate layer, wherein: the intermediate layer has a porous layer containing a siloxane compound; and the siloxane compound has at least one among a component derived from a compound containing a reactive functional group and a hydrolyzable group, and a component derived from a compound containing a hydrolyzable group having a reactive functional group.

Description

[Technical Field]

[0001] The present invention relates to a laminate and a medical device. [Background technology]

[0002] Siloxane compounds (polysiloxane compounds) have excellent heat resistance and flexibility, and are widely used as functional materials in the food and medical fields. For example, Patent Document 1 describes a laminate having, on a support, a cured film formed by curing a silicone resin composition containing an organopolysiloxane of a specific structure, an organosilicon compound of a specific structure, an inorganic filler having a specific refractive index and band gap, and a phosphoric acid catalyst. According to the technology described in Patent Document 1, the laminate has high UV reflectance, which can enhance the sterilization effect in a sterilization treatment using UV light, and is also said to have high UV resistance. Furthermore, Patent Documents 2 to 4 describe laminates having a siloxane compound-containing layer on a substrate. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2019-151710 [Patent Document 2] JP 2010-149294 A [Patent Document 3] JP 2003-291256 A [Patent Document 4] International Publication No. 2017 / 111121 Summary of the Invention [Problem to be solved by the invention]

[0004] Medical devices used to examine or treat the human body must be highly clean, and must be washed and disinfected with chemicals after each use. In particular, medical devices inserted into or applied to blood vessels, trachea, digestive tract, and other body cavities or tissues require a high level of cleanliness that goes beyond disinfection to prevent bacterial infection. Sterilization using EOG (ethylene oxide gas) is widely used as such a sterilization process, and the application of hydrogen peroxide plasma treatment is also becoming desirable.

[0005] The surfaces of medical devices subjected to such sterilization treatments are often composed of a single-layer or multi-layer polymer coating layer, which is tightly adhered to the underlying substrate. When such laminates are repeatedly subjected to the above-mentioned sterilization treatments, the constituent materials of the laminate deteriorate, resulting in a decrease in adhesion between the polymer layers constituting the laminate or between the polymer layer and the substrate. This decrease in adhesion causes a decrease in the performance of the medical device. Therefore, the components of medical devices are required to have a high level of sterilization durability.

[0006] An object of the present invention is to provide a laminate that has excellent sterilization durability and is suitable as a component of a medical device, and a medical device that includes this laminate. [Means for solving the problem]

[0007] In view of the above-mentioned problems, the present inventors have conducted extensive research into the formation of a polymer coating layer in a laminate. As a result, they have found that the above-mentioned problems can be solved by providing an intermediate layer between a substrate and a polymer coating layer, forming this intermediate layer into a porous layer containing a siloxane compound, and further incorporating into the siloxane compound constituting this porous layer a component derived from a compound having both a reactive functional group and a hydrolyzable group, or a component derived from a compound having a hydrolyzable group with a reactive functional group. Based on these findings, the present invention has been completed through further research.

[0008] The above-mentioned problems of the present invention have been solved by the following means. <1> The present invention relates to a porous film having a substrate, an intermediate layer on the substrate, and a polymer coating layer on the intermediate layer, the intermediate layer having a porous layer containing a siloxane compound, the siloxane compound having at least one of a component derived from a compound having a reactive functional group and a hydrolyzable group and a component derived from a compound having a reactive functional group and a hydrolyzable group. the reactive functional group contains at least one of an amino group, a (meth)acryloyl group, a mercapto group, a phosphorus atom-containing group, and an acyl group, the porous layer has an average pore size of 100 nm to 10 μm, an average layer thickness of 0.1 to 500 μm, and a porosity of 10 to 60%, the substrate contains at least one of iron, a non-ferrous metal, and an inorganic material other than a metal; The polymer coating layer contains at least one of a thermoplastic polymer and a thermosetting polymer. , laminate. < 2 > the intermediate layer is the porous layer, the siloxane compound contained in the porous layer is a dehydration condensate of at least one of an alkoxysilane compound and a hydroxysilane compound with at least one of a silane coupling agent, a titanium alkoxide compound, a zirconium alkoxide compound and an aluminum alkoxide compound, and the silane coupling agent, the titanium alkoxide compound, the zirconium alkoxide compound and the aluminum alkoxide compound have the reactive functional group; 1> The laminate described above. < 3 > the siloxane compound contained in the porous layer is a dehydration condensation product of at least one of an alkoxysilane compound and a hydroxysilane compound with a silane coupling agent, and the silane coupling agent has the reactive functional group; 2 The laminate described in >. < 4 > The non-ferrous metal includes at least one of aluminum, titanium, magnesium, nickel, copper, lead, zinc, tin, chromium, tungsten, cobalt, and an alloy of at least two of these metals; 1>~ <3> One of The laminate according to claim 1. < 5 > The inorganic material other than metal includes at least one of glass and ceramics. 1>~ <3> One of The laminate according to claim 1. < 6 > The intermediate layer has the porous layer and a primer layer on the porous layer. The primer layer has a reactive functional group, and the reactive functional group of the primer layer includes at least one of an amino group, a (meth)acryloyl group, an epoxy group, a mercapto group, an acid anhydride group, a phosphorus atom-containing group, a hydroxy group, a carboxy group, a sulfonyl group, and an acyl group. , <1> ~<5 > The laminate according to any one of the above. < 7 > The primer layer contains at least one of a silane coupling agent, a titanium alkoxide compound, an aluminum alkoxide compound, and a zirconium alkoxide compound. 6> The laminate described above. < 8 > The primer layer contains at least one of a titanium alkoxide compound, an aluminum alkoxide compound, and a zirconium alkoxide compound. 7 The laminate described in >. < 9 > The primer layer contains a titanium alkoxide compound. 8 The laminate described in >. < 10 > The titanium alkoxide compound is a compound represented by general formula (a) or (b): Contains , < 7 >~< 9 > The laminate according to any one of the above. General formula (a): R 1a m1 -Ti-(OR 2a ) 4-m1 General formula (b): O-[Ti-(OR 2a )3]2 R 1a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group, or an unsaturated aliphatic group. R 2a is a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group, or -SO2R S1 Indicates R S1 indicates a substituent. m1 is an integer of 0 to 3. < 11 > The compound represented by the general formula (a) or (b) contains at least one atom of N, P, and S, 10 The laminate described in >. <12 > The aluminum alkoxide compound contains a compound represented by the following general formula (c) or (d): 7 > or < 8 The laminate described in >. General formula (c): R 1b m2 -Al-(OR 2b ) 3-m2 General formula (d): O-[Al-(OR 2b )2]2 R 1b represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group, or an unsaturated aliphatic group. R 2b is a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group, or -SO2R S2 Indicates R S2 indicates a substituent. m2 is an integer of 0 to 2. < 13 > In the above general formulas (c) and (d), OR 2b at least one of which has an acetonato structure or an acetato structure; 12 The laminate described in >. < 14 > The zirconium alkoxide compound is a compound represented by the following general formula (e) or (f): 7 > or < 8 The laminate described in >. General formula (e): R 1c m3 -Zr-(OR 2c ) 4-m3 General formula (f): O-[Zr-(OR 2c )3]2 R 1c represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group, or an unsaturated aliphatic group. R 2c is a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group, or -SO2R S3Indicates R S3 indicates a substituent. m3 is an integer from 0 to 3. < 15 > In the above general formulas (e) and (f), OR 2c At least one of the following has an acetonato structure, an acetato structure, or a lactato structure; 14 The laminate described in >. < 16 > the polymer coating layer comprises a thermoplastic polymer; <1> ~< 15 > The laminate according to any one of the above. < 17 > <1> ~< 16 A medical device using the laminate described in any one of the above as a constituent member.

[0009] In this specification, "metal alkoxide compound (specifically, for example, aluminum alkoxide compound, zirconium alkoxide compound, and titanium alkoxide compound described below)" means a compound having a structure in which at least one alkoxy group is bonded to a metal atom. This alkoxy group may have a substituent. This substituent may be monovalent or divalent (e.g., an alkylidene group). Furthermore, two alkoxy groups bonded to one metal atom may be bonded to each other to form a ring. In this specification, when there are multiple substituents, linking groups, etc. (hereinafter referred to as "substituents, etc.") designated by a specific symbol, or when multiple substituents, etc. are simultaneously or alternatively specified, this means that the respective substituents, etc. may be the same or different from each other. Furthermore, even if not otherwise specified, when multiple substituents, etc. are adjacent, they may be linked to each other or condensed to form a ring. In this specification, a substituent (the same applies to a linking group) that is not specified as substituted or unsubstituted means that the group may have any substituent within the range that produces the desired effect. This also applies to compounds that are not specified as substituted or unsubstituted. In this specification, when the number of carbon atoms of a certain group is specified, this number of carbon atoms means the number of carbon atoms in the entire group. In other words, when this group has a further substituent, this number means the total number of carbon atoms including the substituent. In the present invention, the term "reactive functional group" is used in a broader sense than usual. That is, it includes groups that react with other groups to form covalent bonds, etc., as well as groups that interact with other groups (ionic interactions, hydrogen bonds, etc.). In the present invention, an unsubstituted alkoxy group is not considered to have a structure having a reactive functional group. [Effects of the Invention]

[0010] The laminate of the present invention has excellent sterilization durability and is suitable as a component of a medical device. The medical device of the present invention using this laminate as a component has excellent sterilization durability. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a longitudinal sectional view schematically showing one embodiment of the laminate of the present invention. [Figure 2] FIG. 2 is a longitudinal sectional view schematically showing another embodiment of the laminate of the present invention, which is different from that of FIG. [Figure 3] FIG. 3 is a longitudinal sectional view schematically showing another embodiment of the laminate of the present invention, which is different from those shown in FIGS. [Figure 4] FIG. 4 is a longitudinal sectional view schematically showing another embodiment of the laminate of the present invention, different from those shown in FIGS. DETAILED DESCRIPTION OF THE INVENTION

[0012] [Laminate] The laminate of the present invention will be described below with reference to FIG. The laminate of the present invention has a substrate, an intermediate layer on the substrate, and a polymer coating layer on the intermediate layer, and the intermediate layer has a porous layer containing a siloxane compound having at least one component derived from a compound having a reactive functional group and a hydrolyzable group, and a component derived from a compound having a hydrolyzable group and a reactive functional group. The laminate of the present invention, as shown in Figure 1, has a substrate 1, a porous layer 2 (intermediate layer 2) on the substrate 1 that contains the siloxane compound, and a polymer coating layer 3 on the intermediate layer 2. Hereinafter, a "porous layer containing a siloxane compound having a component derived from a compound having a reactive functional group and a hydrolyzable group, or a component derived from a compound having a hydrolyzable group with a reactive functional group" may also be referred to as a "siloxane compound-containing porous layer."

[0013] The laminate of the present invention has excellent sterilization durability. Although the reason for this is unclear, it is presumed that the interaction between the polymer coating layer 3 and the reactive functional groups contained in the siloxane compound-containing porous layer 2, as well as the anchoring effect of the reactive functional groups penetrating into the pores of the siloxane compound-containing porous layer 2, are factors. Note that the hydrolyzable groups having reactive functional groups are hydrolyzed and separated from the compound during the synthesis of the siloxane compound, and almost all of them are contained in the porous layer in a free state. Even in this form, it is believed that the free compounds derived from the reactive functional groups effectively contribute to the adhesion between the porous layer and the adjacent layer through interactions based on their polarity.

[0014] <Base material> The substrate of the present invention is not particularly limited, and a wide range of materials used as components of ordinary medical devices can be used. Specifically, the substrate is iron, non-ferrous metal, and Non-metallic inorganic materials Fee It is preferable to include at least one type.

[0015] The above-mentioned iron also includes alloys of iron with non-ferrous metals, such as stainless steel.

[0016] Examples of the non-ferrous metal include aluminum, titanium, magnesium, nickel, copper, lead, zinc, tin, chromium, tungsten, cobalt, vanadium, and gold, as well as alloys of at least two of these metals. Aluminum, titanium, magnesium, nickel, copper, lead, zinc, tin, chromium, tungsten, and cobalt, as well as alloys of at least two of these metals, are preferred.

[0017] Examples of inorganic materials other than the above metals include glass and glass ceramics. Examples of the glass include sodium soda glass, Pyrex (registered trademark) glass, quartz glass, and alkali-free glass. Examples of the ceramics include alumina, zirconia, silicon carbide, and silicon nitride.

[0020] The physical properties of the substrate, such as flexibility and rigidity, can be appropriately determined depending on the medical device to which the laminate is to be applied. The same applies to the thickness of the substrate. The thickness of the substrate can be, for example, 0.1 to 50 mm, or may be 0.5 to 10 mm.

[0021] Iron, non-ferrous metals, and Non-metallic inorganic materials Fee The content of at least one kind is not particularly limited, and can be, for example, 80% by mass or more, preferably 90% by mass or more, or may be 100% by mass.

[0022] <Siloxane compound-containing porous layer> The intermediate layer constituting the laminate of the present invention has a siloxane compound-containing porous layer. The siloxane compound-containing porous layer has a large number of pores (voids) in the layer. Examples of the shape of the pores include spherical and ellipsoidal shapes. The pores may be independent pores or continuous pores formed by a series of independent pores.

[0023] The average pore size in the siloxane compound-containing porous layer is not particularly limited, and from the viewpoint of sterilization durability, it is, for example, preferably 50 nm to 100 μm, more preferably 100 nm to 10 μm, more preferably 500 nm to 5 μm, and even more preferably 800 nm to 2.5 μm. In the present specification, the average pore size is a value determined by the method described in the Examples below.

[0024] The porosity of the siloxane compound-containing porous layer is not particularly limited, and is, for example, preferably 10 to 80%, more preferably 20 to 60%, and even more preferably 30 to 50%. In this specification, the term "porosity" refers to the ratio of the volume of pores to the volume of the entire porous layer including pores, and is a value determined by the method described in the Examples below.

[0025] The average thickness of the siloxane compound-containing porous layer is not particularly limited, and is, for example, preferably 0.01 to 1000 μm, more preferably 0.05 to 500 μm, more preferably 0.03 to 100 μm, and even more preferably 0.1 to 50 μm. In this specification, the average layer thickness is a value determined by the method described in the Examples below.

[0026] The siloxane compound contained in the siloxane compound-containing porous layer contains a component derived from a compound having a reactive functional group and a hydrolyzable group, or a component derived from a compound having a hydrolyzable group with a reactive functional group. The reactive functional group is not particularly limited, and from the viewpoint of sterilization durability, it is preferable that the reactive functional group has, for example, a reactive functional group other than a hydroxy group. Examples of the reactive functional group include an amino group, a (meth)acryloyl group, a mercapto group (sulfanyl group), a phosphorus atom-containing group, and an acyl group. From the viewpoint of sterilization durability, the reactive functional group is preferably an amino group, a mercapto group, or a phosphorus atom-containing group.

[0027] The phosphorus atom-containing group refers to a monovalent substituent having at least one phosphorus atom. The number of phosphorus atoms contained in the phosphorus atom-containing group is preferably 2 to 10, more preferably 2 to 5, and even more preferably 2 or 3. The molecular weight of the phosphorus atom-containing group is not particularly limited and is, for example, 100 to 300. The phosphorus atom-containing group also refers to a group having a substituent as part of its structure. An example of the phosphorus atom-containing group is a monovalent substituent having a phosphonic acid group at the terminal. Preferred examples of the phosphorus atom-containing group include monovalent organic groups bonded to a titanium atom via an oxygen atom, such as those contained in TI-2, TI-3, TI-4, and TI-5 described below.

[0028] An acyl group means a monovalent substituent represented by "RC(=O)-". The molecular weight of the acyl group is not particularly limited and is, for example, 40 to 300. Examples of R include alkyl and aryl groups, and an alkyl group is preferred. The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 20, also preferably 1 to 10, and also preferably 1 to 6. Specific examples of the alkyl group include methyl, ethyl, isopropyl, butyl, cyclopentyl, and heptadecyl. The acyl group is also preferably contained as an acyloxy group.

[0029] The total proportion of the components derived from the compound having a reactive functional group and a hydrolyzable group and the components derived from the compound having a hydrolyzable group with a reactive functional group in the total components of the siloxane compound can be, for example, 0.1 to 30 mol %, and preferably 0.5 to 5 mol %.

[0030] The siloxane compound contained in the siloxane compound-containing porous layer is a compound having a siloxane bond (a repeating structure of [-Si-O]). This siloxane compound is, for example, an oligomer or polymer obtained by hydrolysis of at least one of an alkoxysilane compound and a hydroxysilane compound with at least one of a silane coupling agent, a titanium alkoxide compound, a zirconium alkoxide compound, and an aluminum alkoxide compound, followed by polycondensation. These silane coupling agents, titanium alkoxide compounds, zirconium alkoxide compounds, and aluminum alkoxide compounds have the above-mentioned reactive functional groups.

[0031] An alkoxysilane compound (alkyloxysilane compound) is a silane compound having at least one alkoxy group and may have a hydroxy group. A hydroxysilane compound is a silane compound having a hydroxy group and no alkoxy group.

[0032] The alkyl group in the alkoxy group may be linear, branched, or cyclic. The number of carbon atoms in this alkyl group is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 10, and still more preferably 1 or 2. Specific examples of the alkyl group include methyl, ethyl, isopropyl, butyl, and cyclopentyl.

[0033] The alkoxysilane compound and the hydroxysilane compound preferably have no reactive functional groups other than the hydroxy group.

[0034] Examples of the alkoxysilane compound include a tetraalkoxysilane compound, a trialkoxysilane compound, and a dialkoxysilane compound. The tetraalkoxysilane is not particularly limited, and examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetrabutoxysilane. The trialkoxysilane compound is not particularly limited, and examples thereof include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, and phenyltriethoxysilane. The dialkoxysilane compound is not particularly limited, and examples thereof include dimethyldimethoxysilane and dimethyldiethoxysilane.

[0035] The hydroxysilane compound is not particularly limited, and examples thereof include compounds obtained by hydrolyzing the alkoxy group of the above alkoxysilane compound to a hydroxy group.

[0036] The weight average molecular weight of the siloxane compound is not particularly limited, and is, for example, preferably 100 to 2,000, and more preferably 150 to 500.

[0037] The weight average molecular weight or number average molecular weight of the compounds described herein is determined as follows. The weight average molecular weight or number average molecular weight can be measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (GPC). Specifically, a GPC apparatus HLC-8220 (trade name, manufactured by Tosoh Corporation) was used, tetrahydrofuran was used as the eluent, and columns G3000HXL+G2000HXL (both trade names, manufactured by Tosoh Corporation) were used, at 23°C, with a flow rate of 1 mL / min, and detection was possible with RI.

[0038] Examples of siloxane compounds that can be used in the present invention include the compounds used in the examples described below, but the present invention is not limited to these.

[0039] The laminate of the present invention includes a form in which a siloxane compound-containing porous layer reacts with at least one of a substrate and a polymer coating layer. For example, the siloxane compound-containing porous layer may exist by reacting a reactive functional group or its free substance contained in the porous layer with a constituent metal of the substrate or with a group on the surface of the polymer coating layer. Furthermore, when the laminate of the present invention has a primer layer, the reactive functional group or its free substance contained in the porous layer may exist by reacting with a compound contained in the primer layer.

[0040] The content of the siloxane compound in the siloxane compound-containing porous layer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and even more preferably 90% by mass or more, and the siloxane compound-containing layer may be a layer made of a siloxane compound. The siloxane compound-containing layer may contain components other than the siloxane compound as long as the effects of the present invention are not impaired. Examples of such components include metal alkoxides other than the metal alkoxide used to form the siloxane compound, binder resins, and stabilizers (surfactants and antioxidants).

[0041] <Polymer coating layer> The polymer contained in the polymer coating layer is not particularly limited, and examples thereof include thermoplastic polymers and thermosetting polymers, with thermoplastic polymers being preferred.

[0042] Thermoplastic polymers include, for example, thermoplastic elastomers and thermoplastic resins. Examples of thermoplastic elastomers include polyamide elastomers, polyester elastomers, fluorine-containing elastomers, polyurethane elastomers, and polyolefin elastomers. Examples of thermoplastic resins include: Thermoplastic polyimide resin, thermoplastic polyamide resin, polyetherimide resin, polyphenylene ether resin, polycarbonate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polyphenylene sulfide resin, polyether ether ketone resin, polyether sulfone resin, acrylic resin, polyethylene resin, polypropylene resin, polyolefin resin such as polymethylpentene resin, and thermoplastic polycycloolefin such as thermoplastic polynorbornene In addition, acrylic resins and polyamide resins can also be used.

[0043] Thermosetting polymers include, for example, thermosetting elastomers and thermosetting resins. Examples of thermosetting elastomers include silicone elastomers, urethane elastomers, diene rubbers, crosslinked olefin elastomers, and crosslinked fluorine-containing elastomers. Examples of thermosetting resins include: Thermosetting polyimide resin, thermosetting polyamide resin, polyamideimide resin, epoxy resin, phenolic resin, polystyrene resin, styrene resin such as ABS resin (acrylonitrile-butadiene-styrene copolymer resin) and acrylonitrile-styrene copolymer resin, and thermosetting polycycloolefin such as thermosetting polynorbornene In addition, epoxy resins, phenolic resins and unsaturated polyester resins can also be used.

[0044] The polymer coating layer may contain components other than the polymer within the range that does not impair the effects of the present invention. The thickness of the polymer coating layer can be appropriately determined depending on the medical device to which the laminate is applied, and can be, for example, 0.1 to 50 mm, or may be 0.3 to 10 mm.

[0045] <Primer layer> In terms of sterilization durability, the laminate of the present invention preferably has an intermediate layer having a primer layer on the siloxane compound-containing porous layer.

[0046] In the laminate of the present invention, from the viewpoint of sterilization durability, it is preferable that the primer layer contains a compound having a reactive functional group, and it is preferable that the reactive functional group contains at least one of an amino group, a (meth)acryloyl group, an epoxy group, a mercapto group, an acid anhydride group, a phosphorus atom-containing group, a hydroxy group, a carboxy group, a sulfonyl group, and an acyl group. Note that it is also preferable that the reactive functional group in the primer layer is a hydroxy group.

[0047] In the present invention, from the viewpoint of sterilization durability, it is preferable that the primer layer contains at least one of an amino group, a (meth)acryloyl group, an epoxy group, a mercapto group, an acid anhydride group, a phosphorus atom-containing group, a carboxy group, a sulfonyl group, and an acyl group, and a hydroxy group; it is more preferable that the primer layer contains at least one of an amino group, a phosphorus atom-containing group, a carboxy group, a sulfonyl group, and an acyl group, and a hydroxy group; and it is even more preferable that the primer layer contains at least one of an amino group, a phosphorus atom-containing group, and a carboxy group, and a hydroxy group.

[0048] In the present invention, from the viewpoint of sterilization durability, the primer layer preferably contains at least one of a silane coupling agent, a titanium alkoxide compound, an aluminum alkoxide compound, and a zirconium alkoxide compound, more preferably contains at least one of a titanium alkoxide compound, an aluminum alkoxide compound, and a zirconium alkoxide compound, and even more preferably contains a titanium alkoxide compound.

[0049] (Silane coupling agent) As the silane coupling agent used in the present invention, a wide range of ordinary silane coupling agents that can be used as primer layers for components of medical devices can be used. The silane coupling agent preferably does not have a siloxane bond, and preferably has a group other than methyl, ethyl, methoxy, and ethoxy (for example, an amino group, a vinyl group, a propyl group, an acid anhydride group, an epoxy group, or a mercapto group).

[0050] (Titanium alkoxide compounds) As the titanium alkoxide compound (preferably a titanium coupling agent) used in the present invention, a wide range of ordinary titanium alkoxide compounds that can be used as primer layers for components of medical devices can be used.

[0051] The titanium alkoxide compound preferably contains at least one compound represented by the following general formula (a) or (b), and more preferably contains at least one compound represented by the following general formula (a): The total content of the compounds represented by the following general formula (a) or (b) in the titanium alkoxide compound is not particularly limited and can be, for example, 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, or even 100% by mass.

[0052] General formula (a): R 1a m1 -Ti-(OR 2a ) 4-m1 General formula (b): O-[Ti-(OR 2a )3]2

[0053] R 1a represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group, or an unsaturated aliphatic group. Examples of the alkyl group, cycloalkyl group, acyl group, aryl group, and unsaturated aliphatic group include R 1b Examples of the alkyl group, cycloalkyl group, acyl group, aryl group and unsaturated aliphatic group that can be taken as the alkyl group include alkyl, cycloalkyl, acyl, aryl and unsaturated aliphatic groups.

[0054] R 2a is a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group, or -SO2R S1 Indicates R S1 indicates a substituent. Examples of the alkyl group, cycloalkyl group, acyl group, alkenyl group, aryl group, and phosphonate group include R 2b The alkyl group, cycloalkyl group, acyl group, alkenyl group, aryl group, and phosphonate group that can be taken as R can be used. S1 Examples of the substituents that can be adopted as the substituent include R S2 The substituents that can be adopted as the following can be adopted.

[0055] m1 is an integer of 0 to 3.

[0056] The compound represented by the above general formula (a) or (b) preferably contains at least one atom of N, P, and S. When the compound represented by the general formula (a) or (b) contains N, it is preferable that the N is contained as an amino group. When the compound represented by general formula (a) or (b) contains P, it is preferable that this P is contained as a phosphate group (phosphoric acid group) or a phosphonate group (phosphonic acid group). When the compound represented by general formula (a) or (b) has S, it is preferable that this S is present as a sulfonyl group (-SO2-). In addition, the compound represented by the above general formula (a) or (b) may be R 2a The compound has an acyl group as the aryl group, i.e., OR 2a It is also preferred that the alkyl group has an acetate structure as described below.

[0057] Specific examples of the titanium alkoxide compound used in the present invention are listed below, but the present invention is not limited to these. Isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl trioctanoyl titanate, isopropyl tri(dioctyl phosphite) titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tri(dioctyl sulfate) titanate, isopropyl tricumylphenyl titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, isopropyl dimethacrylisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isobutyl trimethyl titanate, diisostearoyl ethylene titanate, diisopropyl bis(dioctyl pyrophosphate) titanate, dioctyl bis(ditridecyl phosphate) titanate, dicumylphenyloxy Acetate titanate, bis(dioctyl pyrophosphate)oxyacetate titanate, bis(dioctyl pyrophosphate)ethylene titanate, bis(dioctyl pyrophosphate)oxyacetate titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraoctyl titanate, tetrastearyl titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(di-tridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl)phosphite titanate, butyl titanate dimer, titanium tetraacetylacetonate, titanium ethyl acetoacetate, titanium octylene glycolate, titanium di-2-ethylhexoxybis(2-ethyl-3-hydroxyhexoxide)

[0058] (aluminum alkoxide compounds) As the aluminum alkoxide compound (preferably an aluminum coupling agent) used in the present invention, a wide range of ordinary aluminum alkoxide compounds that can be used as primer layers for components of medical devices can be used.

[0059] The aluminum alkoxide compound preferably contains at least one compound represented by the following general formula (c) or (d), and more preferably contains at least one compound represented by the following general formula (c): The total content of the compounds represented by the following general formula (c) or (d) in the aluminum alkoxide compound is not particularly limited and can be, for example, 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, or even 100% by mass.

[0060] General formula (c): R 1b m2 -Al-(OR 2b ) 3-m2 General formula (d): O-[Al-(OR 2b )2]2

[0061] R 1b represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group, or an unsaturated aliphatic group. R 1b The alkyl group that can be taken as the alkyl group includes a linear alkyl group, a branched alkyl group, and an aralkyl group. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15, even more preferably 1 to 10, and particularly preferably 1 to 8, and in the case of an aralkyl group, the number of carbon atoms is preferably 7 to 30. Specific preferred examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, tridecyl, octadecyl, benzyl, and phenethyl. R 1b It is also preferable that the alkyl group that can be taken as R has an oxirane ring. 1b The number of ring members of the cycloalkyl group (a cycloalkyl group having a structure in which an oxirane ring is condensed) in the epoxycycloalkylalkyl group that can be taken as above is preferably 4 to 8, more preferably 5 or 6, and even more preferably 6 (i.e., an epoxycyclohexyl group). Also, R 1bThe alkyl group that can be taken as the alkyl group preferably has a group selected from an amino group, an isocyanato group, a mercapto group, an ethylenically unsaturated group, and an acid anhydride group.

[0062] R 1b The cycloalkyl group which can be taken as the group preferably has 3 to 20 carbon atoms, more preferably 3 to 15, still more preferably 3 to 10, and particularly preferably 3 to 8. Specific preferred examples of this cycloalkyl group include cyclopropyl, cyclopentyl, and cyclohexyl.

[0063] R 1b The acyl group which can be taken as the alkyl group preferably has 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, further preferably 2 to 20 carbon atoms, and particularly preferably 2 to 18 carbon atoms.

[0064] R 1b The aryl group which can be taken as the group preferably has a carbon number of 6 to 20, more preferably 6 to 15, even more preferably 6 to 12, and particularly preferably 6 to 10. Specific preferred examples of this aryl group include phenyl and naphthyl, and phenyl is more preferred.

[0065] R 1b The unsaturated aliphatic group which can be taken as above preferably has 1 to 5 carbon-carbon unsaturated bonds, more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 1. The unsaturated aliphatic group may contain a heteroatom and is also preferably a hydrocarbon group. When the unsaturated aliphatic group is a hydrocarbon group, it preferably has 2 to 20 carbon atoms, more preferably 2 to 15, even more preferably 2 to 10, still more preferably 2 to 8, and also preferably 2 to 5. The unsaturated aliphatic group is more preferably an alkenyl group or an alkynyl group.

[0066] R 1b is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, and more preferably an alkyl group or a cycloalkyl group. The compound of general formula (c) is R 1b If there are two or more R 1bmay be linked to each other to form a ring.

[0067] R 2b is a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group (phosphonic acid group), or -SO2R S2 Indicates R S2 indicates a substituent. R 2b The alkyl group, cycloalkyl group, acyl group, and aryl group that can be taken as 1b The alkyl group, cycloalkyl group, acyl group, and aryl group that can be taken as R are the same as those, and the preferred forms of each group are also the same. 2b The alkyl group which can be taken as the alkyl group preferably has an amino group as a substituent.

[0068] R 2b The alkenyl group that can be taken as (R) includes a linear alkenyl group and a branched alkenyl group. The number of carbon atoms in this alkenyl group is preferably 2 to 18, more preferably 2 to 7, and even more preferably 2 to 5. Specific preferred examples of this alkenyl group include vinyl, allyl, butenyl, pentenyl, and hexenyl. The alkenyl group is preferably a substituted alkenyl group.

[0069] R 2b Possible phosphonate groups are -P(=O)(-OR P1 ) OR P2 R is a group represented by P1 and R P2 represents a hydrogen atom or a substituent, and the substituent is preferably an alkyl group or a phosphonate group. P1 and R P2 The alkyl groups that can be used are the above-mentioned R 1b The preferred alkyl groups are also the same as those shown in R P1 and R P2 Possible phosphonate groups are R 2b The meaning and preferred form of the phosphonate group R P1 or R P2When R is a phosphonate group, R constituting this phosphonate group P1 and R P2 is preferably an alkyl group. R 2b Possible phosphonate groups are R P1 and R P2 are both alkyl groups, or R P1 is a hydrogen atom, and R P2 is preferably a phosphonate group. In addition, since a phosphonate group is tautomeric with a phosphite group (phosphorous acid group), the phosphonate group in the present invention is meant to include a phosphite group.

[0070] R 2b -SO2R S2 In the formula, the substituent R S2 is preferably an alkyl group or an aryl group. S2 As preferred forms of the alkyl group and aryl group that can be taken as R 1b Among them, R S2 is preferably a phenyl having an alkyl group as a substituent. A preferred form of this alkyl group is the above-mentioned R 1b The preferred forms of the alkyl group are the same as those of the alkyl group that can be taken as above.

[0071] The compound represented by general formula (c) is R 2b If there are two or more R 2b In the compound represented by general formula (d), two R 2b may be linked to each other to form a ring.

[0072] m2 is an integer of 0 to 2.

[0073] In the above general formulas (c) and (d), OR 2bIt is preferable that at least one of the above has an acetonato structure. This acetonato structure means a structure in which one hydrogen ion is removed from acetone or a compound having a structure in which acetone has a substituent, and the resulting structure is coordinated to Al. The coordinating atom that coordinates to this Al is usually an oxygen atom. This acetonato structure preferably has an acetylacetone structure ("CH3-C(=O)-CH2-C(=O)-CH3") as its basic structure, from which one hydrogen ion is removed, and the oxygen atom is coordinated to Al as the coordinating atom (i.e., an acetylacetonato structure). The above phrase "having an acetylacetone structure as its basic structure" means not only the above acetylacetone structure, but also structures in which the hydrogen atom of the above acetylacetone structure is substituted with a substituent. OR 2b Examples of the compound having an acetonate structure include compounds AL-1 and AL-2 described below. In the above general formulas (c) and (d), OR 2b It is preferable that at least one of the above has an acetate structure. In the present invention, the acetate structure means a structure in which one hydrogen ion is removed from acetic acid or an acetate ester, or a compound having a structure in which these have a substituent (including a form in which the methyl group of acetic acid has an alkyl group as a substituent), and the resulting structure is coordinated to Al. The coordinating atom that coordinates to this Al is usually an oxygen atom. This acetate structure is an alkylacetoacetate structure ("CH3-C(=O)-CH2-C(=O)-OR"). alk " (R alk represents an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, which may be an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms). )) is a basic structure from which one hydrogen ion has been removed, and an oxygen atom is coordinated to Al as a coordinating atom (i.e., an alkylacetoacetate structure). The above phrase "having an alkylacetoacetate structure as a basic structure" means that in addition to the above alkylacetoacetate structure, it also includes structures in which the hydrogen atoms of the above alkylacetoacetate structure have been substituted with substituents. OR 2b Examples of the compound having an acetate structure include compounds AL-2, AL-3, and AL-4 described below.

[0074] Above R 1b or R 2b Each of the groups that can be taken as may have an anionic group (salt-type substituent) having a counter cation as a substituent. An anionic group refers to a group that can form an anion. An example of the anionic group having a counter cation is a carboxylate ion group having an ammonium ion as a counter cation. In this case, the counter cation may be present in the compound represented by the above general formula (c) or (d) so that the overall charge of the compound is 0. This also applies to the compounds represented by the above general formula (a) or (b) and the compounds represented by the below-described general formula (e) or (f).

[0075] Specific examples of the aluminum alkoxide compound used in the present invention are listed below, but the present invention is not limited to these. Aluminum triethylate, aluminum triisopropylate, aluminum tri-sec-butylate, aluminum tris(ethylacetoacetate), ethylacetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bis(ethylacetoacetate), aluminum tris(acetylacetonate), diisopropoxyaluminum-9-octadecenylacetoacetate, aluminum diisopropyloxymonoethylacetoacetate, aluminum trisethylacetoacetate, aluminum trisacetylacetonate, monosec-butoxyaluminum diisopropylate, ethylacetoacetate aluminum diisopropylate, diethylacetoacetate aluminum isopropylate, aluminum bisethylacetoacetate monoacetylacetonate, aluminum octadecylacetoacetate diisopropylate

[0076] (zirconium alkoxide compounds) As the zirconium alkoxide compound (preferably a zirconium coupling agent) used in the present invention, a wide range of ordinary zirconium alkoxide compounds that can be used as primer layers for components of medical devices can be used.

[0077] The zirconium alkoxide compound preferably contains at least one compound represented by the following general formula (e) or (f), and more preferably contains at least one compound represented by the following general formula (e): The total content of the compounds represented by the following general formula (e) or (f) in the zirconium alkoxide compound is not particularly limited and can be, for example, 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, or even 100% by mass.

[0078] General formula (e): R 1c m3 -Zr-(OR 2c ) 4-m3 General formula (f): O-[Zr-(OR 2c )3]2

[0079] R 1c represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group, or an unsaturated aliphatic group. Examples of the alkyl group, cycloalkyl group, acyl group, aryl group, and unsaturated aliphatic group include R 1b Examples of the alkyl group, cycloalkyl group, acyl group, aryl group and unsaturated aliphatic group that can be taken as the alkyl group include alkyl, cycloalkyl, acyl, aryl and unsaturated aliphatic groups.

[0080] R 2c is a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group, or -SO2R S3 Indicates R S3 indicates a substituent. Examples of the alkyl group, cycloalkyl group, acyl group, alkenyl group, aryl group, and phosphonate group include R 2b The alkyl group, cycloalkyl group, acyl group, alkenyl group, aryl group, and phosphonate group that can be taken as R can be used. S2 Examples of the substituents that can be adopted as the substituent include R S2The substituents that can be adopted as the following can be adopted.

[0081] m3 is an integer from 0 to 3.

[0082] In the above general formulas (e) and (f), OR 2c Preferably, at least one of the following has an acetonate structure. This acetonate structure has the same meaning as the acetonate structure described in general formula (c). OR 2c Examples of the compound having an acetonato structure include compounds ZR-1 and ZR-3 described below. In addition, in the above general formula (e), OR 2c Preferably, at least one of the following has an acetato structure. This acetato structure has the same meaning as the acetato structure described in general formula (c). OR 2c An example of a form having an acetate structure is ZR-4, which will be described later. In addition, in the above general formulas (e) and (f), OR 2c It is preferable that at least one of the above has a lactato structure. This lactato structure means a structure in which a lactate ion (lactate) is used as the basic structure, from which one hydrogen ion has been removed and coordinated to Zr. The above phrase "having a lactate ion as the basic structure" means not only the lactate ion but also a structure in which the hydrogen atom of the lactate ion is substituted with a substituent. The coordinating atom coordinated to Zr is usually an oxygen atom. OR 2c An example of a form having a lactato structure is compound ZR-2, which will be described later.

[0083] Specific examples of the zirconium alkoxide compound used in the present invention are listed below, but the present invention is not limited to these. Zirconium tetrapropoxide (also known as zirconium tetra-n-propoxide), zirconium tetrabutoxide (also known as zirconium tetra-n-butoxide), zirconium tetraacetylacetonate, zirconium tributoxymonoacetylacetonate, zirconium dibutoxybis(acetylacetonate), zirconium dibutoxybis(ethylacetoacetate), zirconium tributoxyethylacetoacetate, zirconium monobutoxyacetylacetonate bis(ethylacetoacetate), zirconium tributoxymonostearate (also known as zirconium stearate tri-n-butoxide), zirconium stearate, zirconium lactate ammonium salt, zirconium monoacetylacetonate

[0084] The molecular weight of the silane coupling agent, titanium alkoxide compound, aluminum alkoxide compound and zirconium alkoxide compound used in the present invention is not particularly limited, and is, for example, preferably 100 to 2,000, more preferably 200 to 500. A polymeric silane coupling agent can also be used.

[0085] The content of the compound having a reactive functional group, preferably the silane coupling agent and the metal alkoxide compound, in the primer layer is not particularly limited, and is preferably 90% by mass or more in total, more preferably 95% by mass or more, even more preferably 97% by mass or more, particularly preferably 99% by mass or more, and can be 100% by mass. The silane coupling agent, aluminum alkoxide compound, zirconium alkoxide compound, and titanium alkoxide compound contained in the primer layer may each be one type or two or more types. In addition to the silane coupling agent and the metal alkoxide compound, the primer layer may contain additives such as a surfactant, a thickener, a leveling agent, a stabilizer, and an antifoaming agent, within a range that does not impair the effects of the present invention. The primer layer may be a single layer or multiple layers, and is preferably a single layer.

[0086] In the present invention, the phrase "the primer layer contains at least one of a silane coupling agent, a titanium alkoxide compound, an aluminum alkoxide compound, and a zirconium alkoxide compound" refers to a form in which at least one of a silane coupling agent, a titanium alkoxide compound, an aluminum alkoxide compound, and a zirconium alkoxide compound is contained in a state in which it has reacted with a siloxane compound-containing porous layer or a substrate, and a form in which at least one of a silane coupling agent, a titanium alkoxide compound, an aluminum alkoxide compound, and a zirconium alkoxide compound is contained in a state in which it has reacted with a polymer coating layer. For example, the silane coupling agent, the titanium alkoxide compound, the aluminum alkoxide compound, and the zirconium alkoxide compound are at least partially hydrolyzed to expose hydroxyl groups, which may react with the constituent metals of the siloxane compound-containing porous layer or the substrate, or with groups on the surface of the polymer coating layer.

[0087] The thickness of the primer layer is much thinner than that of a normal adhesive layer, and is preferably, but not limited to, 1 nm to 100 nm, i.e., the primer layer differs from an adhesive layer that requires a certain thickness and softness for adhesion between the substrate and the polymer coating layer. For convenience of explanation, the primer layer is shown in FIG. 2 as a thick layer.

[0088] Medical devices to which the laminate of the present invention can be applied, that is, medical devices of the present invention, include, for example, catheters, applicators, X-ray imaging devices, electrosurgical instruments, active treatment instruments, ultrasonic diagnostic devices, and endoscopes.

[0089] [Method of manufacturing laminate] <Formation of a siloxane compound-containing porous layer> Specific examples of methods for forming a siloxane compound-containing porous layer are shown below, but the present invention is not limited to these.

[0090] The siloxane compound-containing porous layer can be formed on at least one surface of the substrate through the following steps (i) and (ii). (i) A silica composition is prepared by subjecting an alkoxysilane compound to a dehydration condensation reaction with at least one of a silane coupling agent, a titanium alkoxide compound, a zirconium alkoxide compound, and an aluminum alkoxide compound in the presence of a pore-forming agent. (ii) After applying the silica composition to the substrate, the silica composition is dried (or heated) to form a coating film, which is then further heated at a high temperature to decompose and remove the pore-forming agent, thereby forming pores in the coating film.

[0091] In the above step (i), a silica composition is obtained by subjecting an alkoxysilane compound and at least one of a silane coupling agent, a titanium alkoxide compound, a zirconium alkoxide compound, and an aluminum alkoxide compound to a dehydration condensation reaction in a mixed liquid containing at least one of the above-mentioned alkoxysilane compound and hydroxysilane compound, at least one of the above-mentioned silane coupling agent, a titanium alkoxide compound, a zirconium alkoxide compound, and an aluminum alkoxide compound, a pore-forming agent, and a solvent. For example, an alkoxysilane compound is mixed with at least one of a silane coupling agent, a titanium alkoxide compound, a zirconium alkoxide compound, and an aluminum alkoxide compound, a pore-forming agent, and a solvent containing water, and if necessary, a catalyst described below is added. While mixing, the alkoxysilane compound is subjected to a dehydration condensation reaction in the presence of the pore-forming agent, and if necessary, the mixture is concentrated or diluted with a solvent to obtain a silica composition. The reaction conditions (reaction temperature, reaction time) for the dehydration condensation reaction may be those of a conventional method.

[0092] The total silica content in the silica composition (the content of the dehydration condensation reaction product, i.e., the siloxane compound) is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. On the other hand, the total silica content is preferably 70% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and even more preferably 20% by mass or less.

[0093] The pore-forming agent can be one that is encapsulated in silica and can be decomposed and removed by heating. Examples of the pore-forming agent include surfactants. Examples of surfactants that can be used include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. Nonionic surfactants are preferred, and nonionic surfactants with a polymer structure are more preferred. When the surfactant is a polymer, its number average molecular weight is, for example, 300 to 5,000.

[0094] The content of the surfactant in the silica composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 1.2% by mass or more, and even more preferably 1.4% by mass or more, while the content is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

[0095] The solvent is preferably water or a combination of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include alcohol compounds such as monohydric alcohols having 1 to 4 carbon atoms, such as methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-1-propanol, 1-butanol, 2-butanol, t-butanol, and 1-pentanol, dihydric alcohols having 1 to 4 carbon atoms, and polyhydric alcohols, such as glycerin and pentaerythritol; ethers or esters of the above alcohol compounds, such as methyl acetate, ethyl acetate, isobutyl acetate, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, 2-ethoxyethanol, propylene glycol monomethyl ether, and propylene glycol methyl ether acetate; acetone, methyl ethyl ketone, etc. ketone compounds such as those listed above; amide compounds such as formamide, N-methylformamide, N-ethylformamide, N,N-dimethylformamide, N,N-diethylformamide, N-methylacetamide, N-ethylacetamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methylpyrrolidone, N-formylmorpholine, N-acetylmorpholine, N-formylpiperidine, N-acetylpiperidine, N-formylpyrrolidine, N-acetylpyrrolidine, N,N'-diformylpiperazine, N,N'-diformylpiperazine, and N,N'-diacetylpiperazine; lactone compounds such as γ-butyrolactone; ureas such as tetramethylurea and N,N'-dimethylimidazolidine; dimethyl sulfoxide, etc. Among these, alcohols are preferred, and monohydric alcohols are more preferred, in order to perform hydrolysis under conditions that are more stable for the alkoxysilane compound contained therein.

[0096] The silica composition usually contains a catalyst, and any substance that accelerates the hydrolysis and dehydration condensation reaction of the alkoxysilane compound can be used as the catalyst. Examples of such acids include hydrofluoric acid, phosphoric acid, boric acid, hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, maleic acid, methylmalonic acid, stearic acid, linoleic acid, benzoic acid, phthalic acid, citric acid, and succinic acid; amine compounds such as ammonia, butylamine, dibutylamine, and triethylamine; bases such as pyridine; and Lewis acids such as aluminum acetylacetone complexes. Other examples of catalysts include metal chelate compounds, whose metal species include titanium, aluminum, zirconium, tin, and antimony.

[0097] The silica composition may contain components other than at least one of the above-mentioned alkoxysilane compound, silane coupling agent, titanium alkoxide compound, zirconium alkoxide compound, and aluminum alkoxide compound, organic solvent, surfactant, water, and catalyst, as long as the effects of the present invention are not impaired.

[0098] In the step (ii), the substrate is immersed in the silica composition obtained in the step (i), and then the substrate is taken out and dried to form a coating film. Subsequently, the surfactant is decomposed and removed at a high temperature (e.g., 250°C or higher), thereby obtaining a substrate having a siloxane compound-containing porous layer.

[0099] The average pore size and porosity of the siloxane compound-containing porous layer can be controlled by the type of raw materials, the blending ratio of the raw materials, and reaction conditions (for example, drying or heating temperature and heating time).

[0100] In the present invention, within the scope of not impairing the effects of the present invention, a part of the substrate (a part of the surface of the substrate on which the siloxane compound-containing porous layer is formed) may have a part that is not covered with the siloxane compound-containing porous layer (i.e., a part of the porous layer may have voids).

[0101] <Formation of primer layer> In the production of the laminate of the present invention, after forming the siloxane compound-containing porous layer, it is preferable to form a primer layer on this siloxane compound-containing porous layer. The primer layer can be formed by dissolving at least one of the above-mentioned silane coupling agent, titanium alkoxide compound, zirconium alkoxide compound and aluminum alkoxide compound in a solvent to prepare a coating solution, applying or spraying this coating solution on the siloxane compound-containing porous layer, or immersing the substrate in this coating solution to form a coating film on at least one surface of the substrate, and then drying the coating film by a conventional method (for example, drying at a high temperature of about 100 ° C.). The solvent used in the coating solution may be an alcohol solvent such as methanol or ethanol, a ketone solvent such as acetone or methyl ethyl ketone, an ester solvent such as ethyl acetate, a hydrocarbon solvent such as toluene, or a mixture thereof. Furthermore, it is preferable to mix water or an acid catalyst such as acetic acid with these solvents to promote the hydrolysis of the silane coupling agent, titanium alkoxide compound, zirconium alkoxide compound, and aluminum alkoxide compound. The coating solution may be acidic (e.g., pH 1 to 4 at 25°C) or alkaline (e.g., pH 9 to 11 at 25°C). The contents of the silane coupling agent, titanium alkoxide compound, zirconium alkoxide compound, and aluminum alkoxide compound in the coating liquid are not particularly limited, and can be, for example, 0.01 to 2 mass% in total, preferably 0.05 mass% or more and less than 1.5 mass%, and more preferably 0.1 mass% or more and less than 1.0 mass%. The coating liquid may contain at least one of a silane coupling agent, a titanium alkoxide compound, a zirconium alkoxide compound, and an aluminum alkoxide compound, a solvent, a pH adjuster, a surfactant, a catalyst, etc. More preferably, the coating liquid is composed of at least one of a silane coupling agent, a titanium alkoxide compound, a zirconium alkoxide compound, and an aluminum alkoxide compound, and a solvent. In the present invention, within the scope of not impairing the effects of the present invention, there may be a part of the siloxane compound-containing layer that is not covered with the primer layer (i.e., there may be a defect in part of the primer layer).

[0102] <Formation of polymer coating layer> The polymer coating layer can be formed, for example, by heating and pressing the siloxane compound-containing porous layer or primer layer under conditions of a temperature of the polymer melting point +5 to 30°C and a pressure of 1 to 100 MPa. When a polymer coating layer is formed using the thermoplastic polymer used, the polymer coating layer can also be formed on the substrate by extrusion coating. [Example]

[0103] The present invention will be described in more detail below through examples, but the present invention should not be construed as being limited thereto. [Laminate fabrication] A laminate having the structure shown in FIG. 3 or 4 was prepared.

[0104] <Base material> (Stainless steel (SUS304) base material) The metal plate was made of stainless steel (SUS304) and measured 80 mm long, 20 mm wide, and 2 mm thick. A passive layer had been formed on the surface by annealing (heat treatment). After degreasing with acetone, it was immersed in a 1N sodium hydroxide solution at 50°C for 3 minutes and cleaned. It was then rinsed three times with distilled water and dried in an oven heated to 100°C for 10 minutes to prepare the substrate.

[0105] (Substrates other than stainless steel) The dimensions of the substrates other than the stainless steel substrates listed in Table 3 are 80 mm long x 20 mm wide x 2 mm thick. The glass substrate was JIS R3503 (trade name) quartz glass manufactured by Standard Test Piece Co., Ltd., and was pretreated in the same manner as the stainless steel substrate. The ceramic substrate used was AS ONE's stabilized zirconia "PSZ200" (product name). 。

[0106] <Preparation of a substrate having a porous layer (L-1) containing a siloxane compound having a reactive functional group> 40 g (190 mmol) of tetraethoxysilane, 1.0 g (2.8 mmol) of isopropyl tri(N-aminoethyl-aminoethyl) titanate ("Plenact 44" (trade name) manufactured by Ajinomoto Fine-Techno Co., Inc., TI-1 in Table 3 below), 9 g of ethanol, 14 g of water, and 33 g of a 0.3% by mass aqueous hydrochloric acid solution were mixed and stirred in a water bath at 63°C for 30 minutes, and then stirred at room temperature for a further 30 minutes to prepare mixture (A). This mixture (A) was mixed with 15 g of a nonionic surfactant (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock polymer, "PLURONIC (registered trademark) L-31" (trade name) manufactured by BASF, number average molecular weight (Mn) 1,100) and 12 g of ethanol, and the mixture was stirred at room temperature for 60 minutes to prepare mixture (B). This mixture (B) was diluted 25 times with 1-butanol and filtered through a filter with 0.45 μm openings to obtain a silica composition (C) (solid content 1.0%). The washed stainless steel substrate was immersed in silica composition (C) for 5 minutes, then removed and air-dried at 40°C for 30 minutes. The substrate was heated in an oven at 300°C for 5 hours to thermally decompose and remove the nonionic surfactant, producing a substrate having a siloxane compound-containing porous layer (L-1) with a reactive functional group (amino group). The reactive functional group in this porous layer is derived from the raw materials used in the synthesis of the siloxane compound, and includes those present in a liberated state due to hydrolysis.

[0107] <Preparation of a substrate having porous layers (L-2) to (L-5) containing a siloxane compound having a reactive functional group> In preparing the substrate having the porous layer (L-1) containing a siloxane compound having the reactive functional group, the substrate having the porous layer (L-2) to (L-5) containing a siloxane compound having the reactive functional group was prepared in the same manner as the substrate having the porous layer (L-1) containing a siloxane compound having the reactive functional group, except that the nonionic surfactant (PLURONIC L-31) was replaced with the nonionic surfactant shown in Table 1 below.

[0108] <Preparation of a substrate having porous layers (L-6) to (L-12) containing a siloxane compound having a reactive functional group> In preparing the substrate having the porous layer (L-1) containing a siloxane compound having the reactive functional group, the substrate having the porous layer (L-6) to (L-12) containing a siloxane compound having the reactive functional group was prepared in the same manner as the substrate having the porous layer (L-1) containing a siloxane compound having the reactive functional group, except that tetraethoxysilane and the compound described in the "alkoxide" row of Table 3 below were used. The tetraethoxysilane and the compound described in the "alkoxide" row of Table 3 below were used in the same molar amounts as in the preparation of the substrate having the porous layer (L-1) containing a siloxane compound having a reactive functional group.

[0109] <Preparation of a substrate having a siloxane compound-containing layer (R-1) having no reactive functional group> In the preparation of a substrate having a porous layer (L-1) containing a siloxane compound having the above-mentioned reactive functional group, a substrate having a layer (R-1) containing a siloxane compound not having a reactive functional group in the raw material compound was prepared in the same manner as in the preparation of a substrate having a porous layer (L-1) containing a siloxane compound having the above-mentioned reactive functional group, except that TI-1 was not used. The layer (R-1) containing a siloxane compound whose raw material compound did not have a reactive functional group had an average pore size of 1.1 μm, a porosity of 15%, and an average layer thickness of 280 nm.

[0110] <Preparation of a substrate having a siloxane compound-containing layer (R-2) without pores> In the preparation of the substrate that has the siloxane compound-containing porous layer (L-1) with the reactive functional group, except that nonionic surfactant is not used, the substrate that has the siloxane compound-containing porous layer (L-1) with the reactive functional group is prepared in the same manner as the substrate that has the siloxane compound-containing porous layer (L-1), and the substrate that has no pores is prepared with the siloxane compound-containing layer (R-2).No pores are observed in the siloxane compound-containing layer (R-2) that has no pores. The average thickness of the siloxane compound-containing layer (R-2) without voids was 240 nm.

[0111] The average pore size, porosity, and average layer thickness of the siloxane compound-containing porous layer were measured and calculated as follows. The measurement results are shown in Table 1 below. <Average pore diameter, porosity> The substrate having the siloxane compound-containing porous layer was placed in an oven set at 150°C for 4 hours and then left to stand in a desiccator until it reached room temperature, and the substrate was used for measurement. Measurements were performed using a mercury intrusion method using a porosimeter (Micromeritics' "Poresizer 9320" (product number)). The initial pressure was 20 kPa, the measurement pore size was 3 nm to 400 μm, the measurement mode was pressure increase (intrusion), and the measurement cell volume was approximately 6 cm. 3 The mercury contact angle was 130°, and the mercury surface tension was 484 dyn / cm.

[0112] <Average layer thickness> The average thickness of the siloxane compound-containing porous layer was calculated as follows. The laminate prepared above was cut at five random locations, and the cross section of each siloxane compound-containing porous layer was observed at 50,000x magnification using a scanning electron microscope (S-5500 (trade name), manufactured by Hitachi High-Technologies Corporation). The thickness was measured at one point on each cross section of the siloxane compound-containing porous layer (one of two siloxane compound-containing porous layers) formed on one side of the substrate. The average of the five thickness values ​​obtained was taken as the average layer thickness.

[0113] [Table 1]

[0114] <Notes for Table 1> Siloxane compound-containing porous layer: a siloxane compound-containing porous layer having a reactive functional group; L-31: PLURONIC L-31 (product name, manufactured by BASF) L-64: PLURONIC L-64 (product name, manufactured by BASF) L-121: PLURONIC L-121 (product name, manufactured by BASF) L-123: PLURONIC L-123 (product name, manufactured by BASF) F-108: PLURONIC F-108 (product name, manufactured by BASF) Number average molecular weight Mn: Number average molecular weight of nonionic surfactants

[0115] [Table 2]

[0116] <Formation of primer layer (Example 13)> 150 g of ethanol, 350 g of water, and 1.0 g of isopropyl tri(N-aminoethyl-aminoethyl) titanate ("Plenact 44" (trade name) manufactured by Ajinomoto Fine-Techno Co., Ltd., TI-1 in Table 3 below) were mixed at room temperature to prepare a coating liquid for forming a primer layer. The siloxane compound-containing porous layer (L-3) having the reactive functional group was immersed in the primer layer-forming coating solution for 1 minute, then removed from the atmosphere and air-dried for 10 minutes, and then placed in an oven at 150° C. and heated and dried for 10 minutes. In this way, a substrate having a siloxane compound-containing porous layer and a primer layer in this order was prepared. In the same manner, the substrates shown in Table 2, each having a siloxane compound-containing porous layer and a primer layer in this order, were prepared.

[0117] <Formation of polymer coating layer (Examples 1 to 40 and 42 to 60)> A polymer sheet as shown in Table 3 below (Tables 3-1 to 3-4), which had been pre-cut to a length of 60 mm, width of 10 mm, and thickness of 0.4 mm, was heat-pressed onto the siloxane compound-containing porous layer or primer layer (molding temperature: polymer melting point + 10°C, pressure of 10 MPa applied for 20 seconds), to produce a laminate having a polymer coating layer.

[0118] <Formation of polymer coating layer (Example 41)> 6.0 g of bisphenol A type epoxy resin ("jER828" (trade name) manufactured by Mitsubishi Chemical, epoxy equivalent 184 to 194 g / eq.) and 4.0 g of polyamidoamine ("SUNMIDE305" manufactured by Evonik) were added and mixed well to obtain an epoxy resin mixture. This epoxy resin mixture was applied to the primer layer to a thickness of 0.4 mm and cured at room temperature for 1 hour and at 80°C for 2 hours to produce a laminate with the epoxy resin (M-1) as the polymer coating layer.

[0119] The laminates thus produced were subjected to the following tests, and the results are summarized in Table 2 below.

[0120] [Test Example 1] Evaluation of durability against ethylene oxide gas (EOG) sterilization The laminate prepared above was repeatedly subjected to sterilization treatment under the following conditions using an EOG sterilizer (Model EQ-150 (trade name) manufactured by Miura Industries Co., Ltd.). <Sterilization conditions> Ethylene oxide gas:carbon dioxide = 20:80 55℃ 50%RH (relative humidity) Reduced pressure: 71kPa Pressure 69kPa Gas concentration 450mg / L Pretreatment 1 hour Sterilization process: 5 hours Ventilate (55°C) for 12 hours after sterilization

[0121] When peeling or floating of the porous layer containing a siloxane compound from the base material, or peeling or floating of the polymer coating layer from the porous layer containing a siloxane compound occurred, the number of sterilization treatments was evaluated according to the following evaluation criteria. Passing the test requires a rating of "C" or higher. <Evaluation Criteria for EOG Sterilization Resistance> AA: 200 times or more A: 100 times or more and less than 200 times B: 50 times or more and less than 100 times C: 20 times or more and less than 50 times D: Less than 20 times

[0122] [Test Example 2] Evaluation of Hydrogen Peroxide Gas Sterilization Durability The laminate prepared above was repeatedly subjected to low-temperature plasma sterilization treatment in the advanced course of a hydrogen peroxide gas sterilizer ("Stellad (registered trademark) NX" manufactured by ASP). When peeling or floating of the porous layer containing a siloxane compound from the base material, or peeling or floating of the polymer coating layer from the porous layer containing a siloxane compound occurred, the number of treatments was evaluated according to the following evaluation criteria. Passing the test requires a rating of "C" or higher. <Evaluation Criteria> AA: 200 times or more A: 100 times or more and less than 200 times B: 50 times or more and less than 100 times C: 20 times or more and less than 50 times D: Less than 20 times

[0123]

Table 3-1

[0124]

Table 3-2

[0125]

Table 3-3

[0126] [Table 3-4]

[0127] <Notes for Table 3> Actual: Example Comparison: Comparative Example The "reactive functional groups" of the "siloxane compound-containing porous layer" refer to the reactive functional groups of the raw material compounds, while the "reactive functional groups" of the "primer layer" refer to the reactive functional groups of the silane coupling agent, titanium alkoxide compound, aluminum alkoxide compound, and zirconium alkoxide compound, as well as hydroxyl groups formed by partial hydrolysis of hydrolyzable groups.

[0128] The abbreviations listed in the above table are as follows:

[0129] (A-1): Polyamide elastomer (trade name: Pebax 4533, manufactured by Arkema) (E-1): Polyester elastomer (product name: Pelprene P-40B, manufactured by Toyobo Co., Ltd.) (F-1): Fluorine-containing elastomer (product name: Daiel T-530, manufactured by Daikin Industries, Ltd.) (P-1): Polyolefin elastomer (product name: Xelas MC707, manufactured by Mitsubishi Chemical Corporation) (P-2): Polypropylene resin (product name: Novatec PP MA3, manufactured by Japan Polyethylene Corporation) (P-3): Polymethylpentene resin (product name: TPX DX231, manufactured by Mitsui Chemicals, Inc.) (P-4): Acrylonitrile-styrene copolymer resin (copolymerization ratio by mass: acrylonitrile:styrene = 30:70, product name: Stylac AS767, manufactured by Asahi Kasei Chemicals Corporation) (U-1): Polyurethane elastomer (product name: Pandex T-8185, manufactured by DIC Corporation)

[0130] (Titanium alkoxide compounds) (TI-1): Isopropyl tri(N-aminoethyl-aminoethyl) titanate (Ajinomoto Fine-Techno Co., Ltd. "Plenact 44") [ka]

[0131] (TI-2): Dioctylbis(ditridecyl)phosphate titanate (trade name: PLENACT 46B, manufactured by Ajinomoto Fine-Techno Co., Inc.) [ka]

[0132] (TI-3): Diisopropyl bis(dioctyl pyrophosphate) titanate (trade name: PLENACT 38S, manufactured by Ajinomoto Fine-Techno Co., Inc.) [ka]

[0133] (TI-4): Bis(dioctylpyrophosphate)oxyacetate titanate (Ajinomoto Fine-Techno Co., Ltd. "Plenact 138S") [ka]

[0134] (TI-5): Bis(dioctylpyrophosphate)ethylene titanate (Ajinomoto Fine-Techno Co., Ltd. "Plenact 238S") [ka]

[0135] (TI-6): Isopropyl tridodecylbenzenesulfonyl titanate (Ajinomoto Fine-Techno Co., Ltd. "Plenact 9SA") [ka]

[0136] (TI-7): Titanium di-2-ethylhexoxybis(2-ethyl-3-hydroxyhexoxide) ("Orgatix TC-201" manufactured by Matsumoto Fine Chemical Co., Ltd.) [ka]

[0137] (TI-8): Isopropyl triisostearoyl titanate (trade name: PLENACT TTS, manufactured by Ajinomoto Fine-Techno Co., Inc.) [ka]

[0138] (TI-9): Tetra n-butyl titanate (trade name: Orgatix TA-21, manufactured by Matsumoto Fine Chemical Co., Ltd.) [ka]

[0139] (TI-10): n-Butyl titanate dimer (trade name: Orgatix TA-23, manufactured by Matsumoto Fine Chemical Co., Ltd.) [ka]

[0140] (aluminum alkoxide compounds) (AL-1): Aluminum trisacetylacetonate (trade name: Orgatix AL-3100, manufactured by Matsumoto Fine Chemical Co., Ltd.) [ka]

[0141] (AL-2): Aluminum bisethylacetoacetate monoacetylacetonate (trade name: Orgatix AL-3200, manufactured by Matsumoto Fine Chemical Co., Ltd.) [ka]

[0142] (AL-3): Aluminum trisethylacetoacetate (trade name: Orgatix AL-3215, manufactured by Matsumoto Fine Chemical Co., Ltd.) [ka]

[0143] (AL-4): Aluminum octadecyl acetoacetate diisopropylate (product name: PLENACT AL-M, manufactured by Ajinomoto Fine-Techno Co., Inc.) [ka]

[0144] (AL-5): Aluminum sec-butoxide (product name: ASBD, manufactured by Kawaken Fine Chemicals Co., Ltd.) [ka]

[0145] (zirconium alkoxide compounds) (ZR-1): Zirconium tetraacetylacetonate (trade name: Orgatix ZC-150, manufactured by Matsumoto Fine Chemical Co., Ltd.) [ka]

[0146] (ZR-2): Zirconium lactate ammonium salt (trade name: Orgatix ZC-300, manufactured by Matsumoto Fine Chemical Co., Ltd.) [ka]

[0147] (ZR-3): Zirconium tri-n-butoxymonoacetylacetonate ("Orgatics ZC-540" manufactured by Matsumoto Fine Chemical Co., Ltd.) [ka]

[0148] (ZR-4): Zirconium di-n-butoxybis(ethylacetoacetate) ("Orgatics ZC-580" manufactured by Matsumoto Fine Chemical Co., Ltd.) [ka]

[0149] (ZR-5): Zirconium tetra-n-butoxide (trade name: Orgatix ZA-65, manufactured by Matsumoto Fine Chemical Co., Ltd.) [ka]

[0150] (Silane coupling agent) (SI-1): N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (trade name: KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) (SI-2): 3-Aminopropyltrimethoxysilane (trade name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) (SI-3): 3-Trimethoxysilylpropylsuccinic anhydride (trade name: X-12-967C, manufactured by Shin-Etsu Chemical Co., Ltd.) (SI-4): (3-Methacryloxypropyl)trimethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) (SI-5): 3-Glycidoxypropyltrimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) (SI-6): 3-Mercaptopropyltrimethoxysilane (trade name: KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0151] TES: Tetraethoxysilane

[0152] Table 3 reveals the following: The laminate of Comparative Example 1 does not have the siloxane compound-containing porous layer and primer layer defined in the present invention. The laminate of Comparative Example 1 is poor in ethylene oxide gas sterilization durability and hydrogen peroxide gas sterilization durability. The laminate of Comparative Example 2 does not have a siloxane compound-containing porous layer as defined in the present invention, and the laminate of Comparative Example 2 has poor durability to ethylene oxide gas sterilization. The laminate of Comparative Example 3 has a siloxane compound-containing layer on a substrate, but the siloxane compound contained in this layer does not have a reactive functional group. Furthermore, the laminate of Comparative Example 3 does not have a primer layer as defined in the present invention. The laminate of Comparative Example 3 has poor ethylene oxide gas sterilization durability and hydrogen peroxide gas sterilization durability. The laminate of Comparative Example 4 has a siloxane compound-containing layer on a substrate, but the siloxane compound contained in this layer does not have a reactive functional group. The laminate of Comparative Example 4 has a primer layer as defined in the present invention, but its durability to hydrogen peroxide gas sterilization is poor. The laminates of Comparative Examples 6 to 8 have a siloxane compound-containing layer on a substrate, but the siloxane compound contained in this layer does not have a reactive functional group. The laminates of Comparative Examples 6 to 8 have a primer layer as specified in the present invention, but are poor in ethylene oxide gas sterilization durability and hydrogen peroxide gas sterilization durability. The laminates of Comparative Examples 5, 9, and 10 have a siloxane compound-containing layer on a substrate, but this layer is not porous. The laminates of Comparative Examples 5, 9, and 10 have a primer layer as defined in the present invention, but are inferior in ethylene oxide gas sterilization durability and hydrogen peroxide gas sterilization durability. In contrast to this, Examples 1 to 58 It can be seen that the laminate of the present invention is excellent in durability to ethylene oxide gas sterilization and durability to hydrogen peroxide gas sterilization. [Explanation of symbols]

[0153] 1 Base material 2. Siloxane compound-containing porous layer (intermediate layer) 3 Polymer coating layer 4 Primer layer (intermediate layer)

Claims

1. a substrate, an intermediate layer on the substrate, and a polymer coating layer on the intermediate layer; the intermediate layer has a porous layer containing a siloxane compound, the siloxane compound has at least one of a component derived from a compound having a reactive functional group and a hydrolyzable group and a component derived from a compound having a hydrolyzable group with a reactive functional group, the reactive functional group containing at least one of an amino group, a (meth)acryloyl group, a mercapto group, a phosphorus atom-containing group and an acyl group, the porous layer having an average pore size of 100 nm to 10 μm, an average layer thickness of 0.1 to 500 μm and a porosity of 10 to 60%, the substrate contains at least one of iron, a non-ferrous metal, and an inorganic material other than a metal; The laminate, wherein the polymeric coating layer comprises at least one of a thermoplastic polymer and a thermosetting polymer.

2. 2. The laminate according to claim 1, wherein the intermediate layer is the porous layer, the siloxane compound contained in the porous layer is a dehydration condensate of at least one of an alkoxysilane compound and a hydroxysilane compound with at least one of a silane coupling agent, a titanium alkoxide compound, a zirconium alkoxide compound, and an aluminum alkoxide compound, and the silane coupling agent, the titanium alkoxide compound, the zirconium alkoxide compound, and the aluminum alkoxide compound have the reactive functional group.

3. The laminate according to claim 2, wherein the siloxane compound contained in the porous layer is a dehydration condensation product of at least one of an alkoxysilane compound and a hydroxysilane compound with a silane coupling agent, and the silane coupling agent has the reactive functional group.

4. The laminate according to any one of claims 1 to 3, wherein the non-ferrous metal comprises at least one of aluminum, titanium, magnesium, nickel, copper, lead, zinc, tin, chromium, tungsten, cobalt, and an alloy of at least two of these metals.

5. The laminate according to any one of claims 1 to 3, wherein the inorganic material other than metal includes at least one of glass and ceramics.

6. The laminate according to any one of claims 1 to 5, wherein the intermediate layer has the porous layer and a primer layer on the porous layer, the primer layer has a reactive functional group, and the reactive functional group of the primer layer includes at least one of an amino group, a (meth)acryloyl group, an epoxy group, a mercapto group, an acid anhydride group, a phosphorus atom-containing group, a hydroxy group, a carboxy group, a sulfonyl group, and an acyl group.

7. The laminate according to claim 6 , wherein the primer layer contains at least one of a silane coupling agent, a titanium alkoxide compound, an aluminum alkoxide compound, and a zirconium alkoxide compound.

8. The laminate according to claim 7 , wherein the primer layer comprises at least one of a titanium alkoxide compound, an aluminum alkoxide compound, and a zirconium alkoxide compound.

9. The laminate according to claim 8 , wherein the primer layer comprises a titanium alkoxide compound.

10. The laminate according to any one of claims 7 to 9, wherein the titanium alkoxide compound comprises a compound represented by general formula (a) or (b): General form (a): R １ａ ｍ１ -Ti-(OR) ２ａ ) ４－ｍ１ General form (b): O-[Ti-(OR)] ２ａ ) ３ ] ２ R １ａ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group, or an unsaturated aliphatic group. R ２ａ is a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group, or —SO ２ R Ｓ１ Indicates. Ｓ１ indicates a substituent. m1 is an integer of 0 to 3.

11. The laminate according to claim 10 , wherein the compound represented by the general formula (a) or (b) contains at least one atom of N, P, and S.

12. The laminate according to claim 7 or 8, wherein the aluminum alkoxide compound comprises a compound represented by the following general formula (c) or (d): General form (c): R １ｂ ｍ２ -Al-(OR) ２ｂ ) ３－ｍ２ General form (d): O-[Al-(OR)] ２ｂ ) ２ ] ２ R １ｂ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group, or an unsaturated aliphatic group. R ２ｂ is a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group, or —SO ２ R Ｓ２ Indicates. Ｓ２ indicates a substituent. m2 is an integer of 0 to 2.

13. In the general formulas (c) and (d), OR ２ｂ The laminate according to claim 12, wherein at least one of the groups has an acetonato structure or an acetato structure.

14. The laminate according to claim 7 or 8, wherein the zirconium alkoxide compound comprises a compound represented by the following general formula (e) or (f): General form (e): R １ｃ ｍ３ -Zr- (OR) ２ｃ ) ４－ｍ３ General form (f): O-[Zr-(OR)] ２ｃ ) ３ ] ２ R １ｃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an aryl group, or an unsaturated aliphatic group. R ２ｃ is a hydrogen atom, an alkyl group, a cycloalkyl group, an acyl group, an alkenyl group, an aryl group, a phosphonate group, or —SO ２ R Ｓ３ Indicates. Ｓ３ indicates a substituent. m3 is an integer of 0 to 3.

15. In the general formulae (e) and (f), OR ２ｃ The laminate according to claim 14, wherein at least one of the groups has an acetonato structure, an acetate structure, or a lactate structure.

16. The laminate of any one of claims 1 to 15, wherein the polymeric coating layer comprises a thermoplastic polymer.

17. A medical device using the laminate according to any one of claims 1 to 16 as a constituent member.

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