Stacked body and medical device

Abstract

To provide a laminate excellent in sterilization durability and suitable as a constituent member of a medical instrument, and a medical instrument provided with the laminate. The laminate has a substrate, an intermediate layer on the substrate, and a polymer cover layer on the intermediate layer, the intermediate layer having a porous layer containing a siloxane compound having at least one of a constituent component from a compound provided with a reactive functional group and a hydrolyzable group and a constituent component from a compound provided with a hydrolyzable group having a reactive functional group.

Description

Technical Field

[0001] This invention relates to a laminate and a medical device. Background Technology

[0002] Siloxane compounds (polysiloxane compounds) possess 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 with a cured film on a support. The cured film is formed by curing an organosilicon resin composition containing an organopolysiloxane with a specific structure, an organosilicon compound with a specific structure, an inorganic filler with a specific refractive index and band gap, and a phosphoric acid catalyst. According to the technology described in Patent Document 1, the laminate exhibits high UV reflectivity during ultraviolet sterilization, improving the sterilization effect, and also demonstrates high UV durability.

[0003] In addition, patent documents 2 to 4 describe laminates having a siloxane compound layer on a substrate.

[0004] Previous technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2019-151710

[0007] Patent Document 2: Japanese Patent Application Publication No. 2010-149294

[0008] Patent Document 3: Japanese Patent Application Publication No. 2003-291256

[0009] Patent Document 4: International Publication No. 2017 / 111121 Summary of the Invention

[0010] The technical problem to be solved by the invention

[0011] Medical devices used for diagnosis or treatment of the human body require a high degree of cleanliness and need to be cleaned and disinfected with chemicals each time they are used.

[0012] In particular, for medical devices inserted into or applied to blood vessels, trachea, digestive tract, and other body cavities or tissues, a high level of cleanliness beyond sterilization is required to prevent bacterial contamination. As such sterilization processes, EOG (ethylene oxide gas)-based sterilization is widely used, and the application of hydrogen peroxide plasma treatment is also desirable.

[0013] The surfaces of medical devices subjected to this sterilization process are often composed of single-layer or multi-layer polymer coatings, which are applied in a tightly sealed manner to the underlying substrate. If such laminates are repeatedly subjected to the sterilization process described above, the constituent materials of the laminate will deteriorate, leading to a decrease in the adhesion between the polymer layers or between the polymer layers and the substrate. This decrease in adhesion will cause a reduction in the performance of the medical device. Therefore, high sterilization durability is required for the components of medical devices.

[0014] The objective of this invention is to provide a laminate with excellent sterilization durability and suitable as a component of a medical device, and a medical device having the laminate.

[0015] means for solving technical problems

[0016] In view of the above-mentioned problems, the inventors have repeatedly studied the formation of the polymer capping layer in the laminate. They discovered that by providing an intermediate layer between the substrate and the polymer capping layer, and by forming this intermediate layer into a porous layer (porous layer) containing a siloxane compound, and by assembling constituent components from compounds that independently possess both reactive and hydrolyzable functional groups, or from compounds possessing hydrolyzable functional groups, into the siloxane compound constituting this porous layer, the above-mentioned problems can be solved. The present invention was made based on these insights and further repeated studies.

[0017] The above-mentioned problems of the present invention are solved by the following solution.

[0018] <1>

[0019] A laminate having a substrate, an intermediate layer on the substrate, and a polymer capping layer on the intermediate layer, the intermediate layer having a porous layer comprising a siloxane compound having at least one of components derived from compounds having reactive functional groups and hydrolyzable groups, and components derived from compounds having reactive functional groups and hydrolyzable groups.

[0020] <2>

[0021] according to <1> The aforementioned laminate, wherein,

[0022] The average pore size of the above porous layer is 50 nm to 100 μm.

[0023] <3>

[0024] according to <2> The aforementioned laminate, wherein,

[0025] The average pore size of the above porous layer is 100 nm to 10 μm.

[0026] <4>

[0027] according to <1> ~ <3> The laminated body described in any one of the following statements, wherein,

[0028] The aforementioned reactive functional groups include at least one of amino, (meth)acryloyl, mercapto, phosphorus-containing groups, and acyl groups.

[0029] <5>

[0030] according to <1> ~ <4> The laminated body described in any one of the following statements, wherein,

[0031] The aforementioned intermediate layer is the aforementioned porous layer, and the aforementioned siloxane compound contained in the aforementioned porous layer is a dehydration condensate of at least one of alkoxysilane compound and hydroxysilane compound with at least one of silane coupling agent, alkanolate titanium compound, alkanolate zirconium compound and alkanolate aluminum compound, wherein the aforementioned silane coupling agent, alkanolate titanium compound, alkanolate zirconium compound and alkanolate aluminum compound have the aforementioned reactive functional groups.

[0032] <6>

[0033] according to <5> The aforementioned laminate, wherein,

[0034] The siloxane compound contained in the porous layer is a dehydration condensate of at least one of alkoxysilane compound and hydroxysilane compound with a silane coupling agent, and the silane coupling agent has the above-mentioned reactive functional groups.

[0035] <7>

[0036] according to <1> ~ <6> The laminated body described in any one of the following statements, wherein,

[0037] The aforementioned substrate includes at least one of iron, non-ferrous metals, inorganic materials other than metals, and organic materials.

[0038] <8>

[0039] according to <7> The aforementioned laminate, wherein,

[0040] The aforementioned non-ferrous metals include at least one of aluminum, titanium, magnesium, nickel, copper, lead, zinc, tin, chromium, tungsten, cobalt, and alloys of at least two of these.

[0041] <9>

[0042] according to <7> The aforementioned laminate, wherein,

[0043] The aforementioned inorganic materials other than metals include at least one of glass and ceramics.

[0044] <10>

[0045] according to <7> The aforementioned laminate, wherein,

[0046] The aforementioned organic materials include at least one of thermoplastic resins and thermosetting resins.

[0047] <11>

[0048] according to <1> ~ <10> The laminated body described in any one of the following statements, wherein,

[0049] The aforementioned intermediate layer has the aforementioned porous layer and a primer layer on the aforementioned porous layer.

[0050] <12>

[0051] according to <11> The aforementioned laminate, wherein,

[0052] The aforementioned primer layer has reactive functional groups.

[0053] <13>

[0054] according to <12> The aforementioned laminate, wherein,

[0055] The reactive functional groups of the above-mentioned primer layer include at least one of amino, (meth)acryloyl, epoxy, mercapto, acid anhydride, phosphorus-containing group, hydroxyl, carboxyl, sulfonyl and acyl groups.

[0056] <14>

[0057] according to <11> ~ <13> The laminated body described in any one of the following statements, wherein,

[0058] The aforementioned primer layer contains at least one of silane coupling agent, alkanolate titanium compound, alkanolate aluminum compound, and alkanolate zirconium compound.

[0059] <15>

[0060] according to <14> The aforementioned laminate, wherein,

[0061] The aforementioned primer layer contains at least one of alkanolate titanium compound, alkanolate aluminum compound, and alkanolate zirconium compound.

[0062] <16>

[0063] according to <15> The aforementioned laminate, wherein,

[0064] The aforementioned primer layer contains alkanolate titanium compounds.

[0065] <17>

[0066] according to <14> ~ <16> The laminated body described in any one of the following statements, wherein,

[0067] The above-mentioned alkanolide titanium compounds are those represented by general formula (a) or (b).

[0068] General formula (a): R 1a m1 -Ti-(OR 2a ) 4-m1

[0069] General formula (b): O-[Ti-(OR 2a )3]2

[0070] R 1a It represents a hydrogen atom, alkyl, cycloalkyl, acyl, aryl, or unsaturated aliphatic group;

[0071] R 2a Represents hydrogen atom, alkyl, cycloalkyl, acyl, alkenyl, aryl, phosphonate group or -SO2R S1 ;R S1 Indicates substituents;

[0072] m1 is an integer from 0 to 3.

[0073] <18>

[0074] according to <17> The aforementioned laminate, wherein,

[0075] The compounds represented by the above general formula (a) or (b) contain at least one atom of N, P and S.

[0076] <19>

[0077] according to <14> or <15> The aforementioned laminate, wherein,

[0078] The above-mentioned aluminum alkoxide compounds include compounds represented by the following general formula (c) or (d).

[0079] General formula (c): R 1b m2 -Al-(OR 2b ) 3-m2

[0080] General formula (d): O-[Al-(OR) 2b )2]2

[0081] R 1b It represents a hydrogen atom, alkyl, cycloalkyl, acyl, aryl, or unsaturated aliphatic group;

[0082] R 2b Represents hydrogen atom, alkyl, cycloalkyl, acyl, alkenyl, aryl, phosphonate group or -SO2R S2 ;R S2 Indicates substituents;

[0083] m2 is an integer from 0 to 2.

[0084] <20>

[0085] according to <19> The aforementioned laminate, wherein,

[0086] In the above general formulas (c) and (d), OR 2b At least one of them has an acetone ligand structure or an acetate ligand structure.

[0087] <21>

[0088] according to <14> or <15> The aforementioned laminate, wherein,

[0089] The aforementioned zirconium alkoxide compounds are those represented by the following general formula (e) or (f).

[0090] General formula (e): R 1c m3 -Zr-(OR 2c ) 4-m3

[0091] General formula (f): O-[Zr-(OR) 2c )3]2

[0092] R 1c It represents a hydrogen atom, alkyl, cycloalkyl, acyl, aryl, or unsaturated aliphatic group;

[0093] R 2c Represents hydrogen atom, alkyl, cycloalkyl, acyl, alkenyl, aryl, phosphonate group or -SO2R S3 ;R S3 Indicates substituents;

[0094] m3 is an integer from 0 to 3.

[0095] <22>

[0096] according to <21> The aforementioned laminate, wherein,

[0097] In the above general formulas (e) and (f), OR 2c At least one of them has an acetone ligand structure, an acetate ligand structure, or a lactate ligand structure.

[0098] <23>

[0099] according to <1> ~ <22> The laminated body described in any one of the following statements, wherein,

[0100] The aforementioned polymer coating layer comprises at least one of thermoplastic polymers and thermosetting polymers.

[0101] <24>

[0102] according to <1> ~ <23> The laminated body described in any one of the following statements, wherein,

[0103] The aforementioned polymer coating layer comprises a thermoplastic polymer.

[0104] <25>

[0105] A medical device, which is used <1> ~ <24> The laminated body described in any one of the above is used as a constituent component.

[0106] In this specification, "alkanol metal compounds (specifically, for example, aluminum alkoxides, zirconium alkoxides, and titanium alkoxides described later)" refers to a compound having a structure in which at least one alkoxy group is bonded to a metal atom. This alkoxy group may also have substituents. These substituents may be monovalent or divalent (e.g., alkylene groups). Furthermore, the two alkoxy groups bonded to a single metal atom may bond together to form a ring.

[0107] In this specification, when there are multiple substituents and linking groups (hereinafter referred to as substituents, etc.) represented by specific symbols, or when multiple substituents, etc. are specified simultaneously or alternatively, it means that the substituents, etc., may be the same or different from each other. In addition, unless otherwise specified, when multiple substituents, etc., are adjacent, it means that they may be linked together or cyclically formed into a ring.

[0108] In this specification, for substituents that are not explicitly substituted or unsubstituted (the same applies to linking groups), it is indicated that any substituent may be present on the group to the extent that the desired effect is achieved. This also applies to compounds that are not explicitly substituted or unsubstituted.

[0109] In this specification, when the number of carbon atoms of a certain group is specified, that number of carbon atoms represents the total number of carbon atoms of the group. That is, when the group is in the form of further having substituents, it represents the total number of carbon atoms including the substituents.

[0110] In this invention, the term "reactive functional group" is used in a broader sense than is usually understood. That is, it includes groups that react with other groups to form covalent bonds, etc., in addition to groups that react with other groups to form covalent bonds, etc. Furthermore, in this invention, unsubstituted alkoxy groups are not structures having reactive functional groups.

[0111] Invention Effects

[0112] The laminate of the present invention exhibits excellent sterilization durability and is suitable as a component of a medical device. Medical devices of the present invention using this laminate as a component exhibit excellent sterilization durability. Attached Figure Description

[0113] Figure 1This is a longitudinal sectional view schematically illustrating one embodiment of the laminate of the present invention.

[0114] Figure 2 It is an illustrative representation of... Figure 1 A longitudinal sectional view of one embodiment of the laminate of the present invention.

[0115] Figure 3 It is an illustrative representation of... Figure 1 and 2 A longitudinal sectional view of one embodiment of the laminate of the present invention.

[0116] Figure 4 It is an illustrative representation of... Figures 1-3 A longitudinal sectional view of one embodiment of the laminate of the present invention. Detailed Implementation

[0117] [Layered Body]

[0118] The following is for reference Figure 1 The laminate of the present invention will be described.

[0119] The laminate of the present invention has a substrate, an intermediate layer on the substrate, and a polymer capping layer on the intermediate layer. The intermediate layer has a porous layer comprising a siloxane compound having at least one of the components of a compound having reactive functional groups and hydrolyzable groups, and components of a compound having reactive functional groups and hydrolyzable groups. Figure 1 The laminate of the present invention, as shown, has a substrate 1, a porous layer 2 (intermediate layer 2) on the substrate 1 containing the aforementioned siloxane compound, and a polymer capping layer 3 on the intermediate layer 2.

[0120] Hereinafter, "porous layer containing siloxane compound" will also be referred to as "porous layer containing siloxane compound", wherein the siloxane compound has components derived from compounds having reactive functional groups and hydrolyzable groups or components derived from compounds having reactive functional groups and hydrolyzable groups.

[0121] The laminate of the present invention exhibits excellent sterilization durability. The reasons for this are not yet clear, but it can be speculated that, in addition to the interaction with the aforementioned reactive functional groups contained in the polymer capping layer 3 and the porous layer 2 containing the siloxane compound, the anchoring effect within the pores of the porous layer 2 containing the siloxane compound is also a contributing factor. Furthermore, it is generally believed that hydrolyzable groups with reactive functional groups are hydrolyzed during the synthesis of the siloxane compound and separated from the compound. These hydrolyzable groups are almost entirely contained in the porous layer in a free state. Even in this form, the free compounds from the reactive functional groups effectively contribute to the adhesion between the porous layer and its adjacent layers through interactions based on their polarity.

[0122] <Substrate>

[0123] The substrate of this invention is not particularly limited and can be widely used in the components of common medical devices.

[0124] Specifically, the substrate preferably includes at least one of iron, non-ferrous metals, inorganic materials other than metals, and organic materials.

[0125] The aforementioned iron also includes alloys of iron and non-ferrous metals. Stainless steel is an example of such an alloy.

[0126] Examples of non-ferrous metals 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, with aluminum, titanium, magnesium, nickel, copper, lead, zinc, tin, chromium, tungsten, and cobalt, as well as alloys of at least two of these metals, being preferred.

[0127] Examples of inorganic materials other than metals include glass and glass ceramics.

[0128] Examples of the aforementioned types of glass include: sodium-alkali glass, PYREX (registered trademark) glass, quartz glass, and alkali-free glass.

[0129] Examples of ceramics mentioned above include: alumina, zirconium oxide, silicon carbide, and silicon nitride.

[0130] Examples of the aforementioned organic materials include thermoplastic resins and thermosetting resins.

[0131] Examples of the aforementioned thermoplastic resins include: thermoplastic polyimide resins, thermoplastic polyamide resins, polyetherimide resins, polyphenylene ether resins, polycarbonate resins, polyethylene terephthalate resins, polyethylene naphthalate resins, polyphenylene sulfide resins, polyether ether ketone resins, polyether sulfone resins, acrylic resins, polyethylene resins and polypropylene resins, polymethylpentene resins, and other polyolefin resins, as well as thermoplastic polycyclic olefins such as thermoplastic polynorbornene.

[0132] Examples of the aforementioned thermosetting resins include: thermosetting polyimide resins, thermosetting polyamide resins, polyamide-imide resins, epoxy resins, phenolic resins, polystyrene resins, and styrene resins such as ABS resin (acrylonitrile-butadiene-styrene copolymer resin) and acrylonitrile-styrene copolymer resin, as well as thermosetting polycyclic olefins such as thermosetting polynorbornene.

[0133] Alternatively, the thermosetting polymers and thermoplastic polymers contained in the polymer coating layer described later can also be used as the aforementioned organic materials. That is, the laminate of the present invention can also utilize the same polymers to form the substrate and the polymer coating layer.

[0134] The physical properties of the substrate, such as flexibility and rigidity, can be appropriately determined according to the medical device using the laminate. The thickness of the substrate is also the same. The thickness of the substrate can be set, for example, 0.1–50 mm, or 0.5–10 mm.

[0135] The content of at least one of iron, non-ferrous metals, inorganic materials other than metals, and organic materials in the substrate is not particularly limited. For example, it can be set to 80% by mass or more, preferably 90% by mass or more, or 100% by mass.

[0136] <Porous layers containing siloxane compounds>

[0137] The intermediate layer constituting the laminate of the present invention has a porous layer (porous layer) containing siloxane compounds. The porous layer containing siloxane compounds has a large number of pores (pores) in the layer. Examples of pore shapes include spheres and ellipsoids. The pores can be individual pores or continuous pores formed by connecting individual pores.

[0138] The average pore size in the porous layer containing siloxane compounds is not particularly limited, but from the perspective of sterilization durability, for example, 50 nm to 100 μm is preferred, more preferably 100 nm to 10 μm, even more preferably 500 nm to 5 μm, and even more preferably 800 nm to 2.5 μm. In the specification of this application, the average pore size is a value determined by the method described in the examples below.

[0139] The porosity of the siloxane compound porous layer is not particularly limited, but is preferably 10-80%, more preferably 20-60%, and even more preferably 30-50%. In this specification, "porosity" is the proportion of the volume of the pores in the total volume of the porous layer containing the pores, and is a value determined by the method described in the examples below.

[0140] The average thickness of the porous layer containing the siloxane compound is not particularly limited, but is preferably 0.01 to 1000 μm, more preferably 0.05 to 500 μm, even 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.

[0141] The siloxane compound contained in the porous layer of siloxane compound has components derived from compounds possessing reactive functional groups and hydrolyzable groups, or components derived from compounds possessing reactive functional groups and hydrolyzable groups. The aforementioned reactive functional groups are not particularly limited, but from the perspective of sterilization durability, for example, reactive functional groups other than hydroxyl groups are preferred. Examples of such reactive functional groups include: amino, (meth)acryloyl, mercapto (thioalkyl), phosphorus-containing groups, and acyl groups. From the perspective of sterilization durability, amino, mercapto, and phosphorus-containing groups are preferred as the aforementioned reactive functional groups.

[0142] A phosphorus-containing group refers to a monovalent substituent having at least one phosphorus atom. The phosphorus-containing group preferably contains 2 to 10 phosphorus atoms, more preferably 2 to 5, and even more preferably 2 or 3. The molecular weight of the phosphorus-containing group is not particularly limited, for example, 100 to 300. A phosphorus-containing group refers to a form that includes a portion of its structure having substituents.

[0143] Examples of phosphorus-containing groups include monovalent substituents with a terminal phosphonic acid group.

[0144] Preferred examples of phosphorus-containing groups include, for example, the monovalent organic groups of TI-2, TI-3, TI-4 and TI-5 described below, which are bonded to titanium atoms by oxygen atoms.

[0145] An acyl group refers to a monovalent substituent represented by "RC(=O)-". The molecular weight of the acyl group is not particularly limited, for example, it is 40 to 300. As R, examples include alkyl or aryl groups, with alkyl groups being preferred.

[0146] The alkyl group can be straight-chain, branched, or cyclic. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, also preferably 1 to 10, and even more preferably 1 to 6. Specific examples of alkyl groups include methyl, ethyl, isopropyl, butyl, cyclopentyl, and heptadecanyl.

[0147] The acyl group is preferably contained in the form of an acyloxy group.

[0148] The proportion of the constituent components of compounds having reactive functional groups and hydrolyzable groups, and the constituent components of compounds having reactive functional groups and hydrolyzable groups, in the total constituent components of the siloxane compound can be set to, for example, 0.1 to 30 mol, preferably 0.5 to 5 mol.

[0149] The siloxane compound contained in the porous layer is a compound having a repeating siloxane bond ([-Si-O] structure). This siloxane compound is, for example, an oligomer or polymer obtained by hydrolyzing at least one of an alkoxysilane compound and a hydroxysilane compound with at least one of a silane coupling agent, a titanium alkanol compound, a zirconium alkanol compound, and an aluminum alkanol compound, followed by polycondensation. These silane coupling agents, titanium alkanol compounds, zirconium alkanol compounds, and aluminum alkanol compounds possess the aforementioned reactive functional groups.

[0150] Alkoxysilane compounds (alkyloxysilane compounds) are silane compounds having at least one alkoxy group, and may also have a hydroxyl group. Hydroxylsilane compounds are silane compounds having a hydroxyl group but no alkoxy group.

[0151] The alkyl group in the alkoxy group can be straight-chain, branched, or cyclic. The alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, even more preferably 1 to 10, and even more preferably 1 or 2. Specific examples of alkyl groups include methyl, ethyl, isopropyl, butyl, and cyclopentyl.

[0152] Alkoxysilane compounds and hydroxysilane compounds preferably do not have reactive functional groups other than hydroxyl groups.

[0153] Examples of alkoxysilane compounds include tetraalkoxysilane compounds, trialkoxysilane compounds, and dialkoxysilane compounds.

[0154] The aforementioned tetraalkoxysilanes are not particularly limited, and examples include: tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, etc.

[0155] Trialkoxysilane compounds are not particularly limited, and examples include: methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, etc.

[0156] Dialkoxysilane compounds are not particularly limited, and examples include: dimethyldimethoxysilane, dimethyldiethoxysilane, etc.

[0157] Hydroxysilane compounds are not particularly limited, and examples include compounds obtained by hydrolyzing the alkoxy group of the above-mentioned alkoxysilane compounds into a hydroxyl group.

[0158] The weight-average molecular weight of the siloxane compound is not particularly limited, but is preferably 100 to 2000, more preferably 150 to 500.

[0159] The weight-average molecular weight or number-average molecular weight of the compounds described in this application specification is determined as follows.

[0160] Weight-average molecular weight or number-average molecular weight can be measured as the molecular weight of polystyrene by gel permeation chromatography (GPC).

[0161] Specifically, the GPC device HLC-8220 (trade name, manufactured by Tosoh Corporation) can be used, with tetrahydrofuran as the eluent, and the chromatographic column used is G3000HXL+G2000HXL (both trade names, manufactured by Tosoh Corporation), at a flow rate of 1 mL / min at 23°C, and detection is performed by RI.

[0162] Examples of siloxane compounds that can be used in the present invention include those used in the following examples, but the invention is not limited thereto.

[0163] The laminate of the present invention represents a form in which a porous layer containing a siloxane compound reacts with at least one of a substrate and a polymer capping layer. For example, the porous layer containing a siloxane compound is a layer in which reactive functional groups or their free forms contained in the porous layer can react with the constituent metal of the substrate or with groups on the surface of the polymer capping layer. Furthermore, when the laminate of the present invention has a primer layer, the reactive functional groups or their free forms contained in the porous layer can also react with compounds contained in the primer layer.

[0164] The content of siloxane compounds in the porous layer containing siloxane compounds 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. The siloxane compound layer can be a layer composed of siloxane compounds.

[0165] Provided that the effect of the present invention is not impaired, the siloxane compound layer may contain components other than siloxane compounds. Examples of such components include: alkoxide metals other than alkoxide metals used in the formation of the siloxane compounds, adhesive resins, and stabilizers (surfactants and antioxidants).

[0166] <Polymer Covering Layer>

[0167] The polymer contained in the polymer coating is not particularly limited, and examples include thermoplastic polymers and thermosetting polymers, with thermoplastic polymers being preferred.

[0168] Examples of thermoplastic polymers include thermoplastic elastomers and thermoplastic resins.

[0169] Examples of thermoplastic elastomers include: polyamide elastomers, polyester elastomers, fluorinated elastomers, polyurethane elastomers, and polyolefin elastomers.

[0170] Examples of thermoplastic resins include those contained in the "substrate" mentioned above. Acrylic resins and polyamide resins may also be used.

[0171] Examples of thermosetting polymers include thermosetting elastomers and thermosetting resins.

[0172] Examples of thermosetting elastomers include: silicone elastomers, urethane elastomers, diene rubbers, cross-linked olefin elastomers, and cross-linked fluorinated elastomers.

[0173] Examples of thermosetting resins include the thermosetting resins contained in the "substrate" mentioned above. Epoxy resins, phenolic resins, and unsaturated polyester resins may also be used.

[0174] The polymer coating may also contain components other than polymers, to the extent that the effects of the invention are not impaired.

[0175] The thickness of the polymer coating can be appropriately determined according to the medical device using the laminate, for example, it can be set to 0.1-50 mm or 0.3-10 mm.

[0176] <Primer layer>

[0177] In the laminate of the present invention, from the perspective of sterilization durability, the intermediate layer preferably has a primer layer on the above-mentioned porous layer containing siloxane compound.

[0178] In the laminate of the present invention, from the perspective of sterilization durability, it is preferable that the primer layer contains a compound having a reactive functional group, and preferably the reactive functional group includes at least one selected from amino, (meth)acryloyl, epoxy, mercapto, acid anhydride, phosphorus-containing group, hydroxyl, carboxyl, sulfonyl, and acyl groups. Furthermore, in the primer layer, it is also preferable that the reactive functional group is in the form of a hydroxyl group.

[0179] In this invention, from the perspective of sterilization durability, it is preferred that the primer layer contains at least one of amino, (meth)acryloyl, epoxy, mercapto, acid anhydride, phosphorus-containing group, carboxyl, sulfonyl and acyl and hydroxyl; more preferably, the primer layer contains at least one of amino, phosphorus-containing group, carboxyl, sulfonyl and acyl and hydroxyl; and even more preferably, the primer layer contains at least one of amino, phosphorus-containing group and carboxyl and hydroxyl.

[0180] In this invention, from the perspective 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, it contains at least one of a titanium alkoxide compound, an aluminum alkoxide compound, and a zirconium alkoxide compound; and even more preferably, it contains a titanium alkoxide compound.

[0181] (Silane coupling agent)

[0182] As the silane coupling agent used in this invention, common silane coupling agents that can be used as primer layers for components of medical devices can be widely adopted.

[0183] The silane coupling agent preferably does not have siloxane bonds, and in addition, it is preferred to have groups other than methyl, ethyl, methoxy and ethoxy (e.g., amino, vinyl, propyl, acid anhydride, epoxy, mercapto).

[0184] (Alkyl Titanium Compounds)

[0185] As the alkanolate titanium compound (preferably a titanium coupling agent) used in the present invention, common alkanolate titanium compounds that can be used as primer layers for components of medical devices can be widely adopted.

[0186] The alkanolate titanium compound preferably contains at least one of the compounds represented by general formula (a) or (b) below, more preferably at least one of the compounds represented by general formula (a) below. The total percentage of the compounds represented by general formula (a) or (b) in the above-mentioned alkanolate titanium compound is not particularly limited, but may be, for example, 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, or even 100% by mass.

[0187] General formula (a): R 1a n1 -Ti-(OR 2a ) 4-m1

[0188] General formula (b): O-[Ti-(OR 2a )3]2

[0189] R 1a It represents a hydrogen atom, alkyl, cycloalkyl, acyl, aryl, or unsaturated aliphatic group.

[0190] As alkyl, cycloalkyl, acyl, aryl, and unsaturated aliphatic groups, R can be used, for example, as a general formula (c) described later. 1b Alkyl, cycloalkyl, acyl, aryl, and unsaturated aliphatic groups.

[0191] R 2a Represents hydrogen atom, alkyl, cycloalkyl, acyl, alkenyl, aryl, phosphonate group or -SO2R s1 R S1 Indicates a substituent.

[0192] As alkyl, cycloalkyl, acyl, alkenyl, aryl, and phosphonate groups, R can be used, for example, as a general formula (c) described later. 2b Alkyl, cycloalkyl, acyl, alkenyl, aryl, and phosphonate groups. Additionally, as a group that can be used as R...S1 The substituents can be, for example, R that can be used as the general formula (c) described later. S2 Substituents.

[0193] ml is an integer from 0 to 3.

[0194] The compounds represented by general formula (a) or (b) above preferably contain at least one atom selected from N, P, and S. When the compound represented by general formula (a) or (b) contains N, it is preferable that the N is an amino group.

[0195] When the compound represented by general formula (a) or (b) has P, it is preferable that the P is a phosphate ester group (phosphate group) or a phosphonate group (phosphonic acid group).

[0196] In the case where the compound represented by general formula (a) or (b) has S, it is preferable that the S is a sulfonyl group (-SO2-).

[0197] Furthermore, compounds represented by the above general formula (a) or (b) preferably have an acyl group as R. 2a That is, having the acetate oxy-structure described later as an OR 2a .

[0198] The following are specific examples of alkanolate titanium compounds used in the present invention, but the present invention is not limited thereto.

[0199] Isopropyl triisostearoyl titanate, isopropyl tri-dodecylbenzenesulfonyl titanate, isopropyl trioctyl titanate, isopropyl tris(dioctyl phosphite) titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tris(dioctyl sulfate) titanate, isopropyl tricumylphenyl titanate, isopropyl tris(N-aminoethyl-aminoethyl) titanate, isopropyl dimethacryloyl isostearyl titanate, isopropyl isostearyl diacrylate titanate, isobutyltrimethyl titanate, diisostearoyl vinyl titanate, diisopropyl bis(dioctyl pyrophosphate) titanate, dioctyl bis(di-tridecyl phosphate) titanate, dicumylphenyloxy Acetate titanate, bis(dioctyl pyrophosphate)oxy acetate titanate, bis(dioctyl pyrophosphate)vinyl titanate, bis(dioctyl pyrophosphate)oxy acetate titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraoctyl titanate, tetrastearyl titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(di-tetrazyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(di-tetrazyl)phosphite titanate, butyl titanate dimer, titanium tetraacetylacetone, ethyl acetoacetate titanium, titanium octyl glycolate, titanium di-2-ethylhexyloxybis(2-ethyl-3-hydroxyhexyloxy)

[0200] (Aluminum alkoxides)

[0201] As the aluminum alkoxide compound (preferably an aluminum coupling agent) used in the present invention, common aluminum alkoxide compounds that can be used as primer layers for components of medical devices can be widely adopted.

[0202] The aluminum alkoxide compound preferably comprises at least one of the compounds represented by general formula (c) or (d) below, more preferably at least one of the compounds represented by general formula (c) below. The total percentage of the compounds represented by general formula (c) or (d) in the above-mentioned aluminum alkoxide compound is not particularly limited, but may be, for example, 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, or even 100% by mass.

[0203] General formula (c): R 1b m2 -Al-(OR 2b ) 3-m2

[0204] General formula (d): O-[Al-(OR) 2b )2]2

[0205] R 1b It represents a hydrogen atom, alkyl, cycloalkyl, acyl, aryl, or unsaturated aliphatic group.

[0206] Can be used as R 1b The alkyl group includes straight-chain alkyl groups, branched alkyl groups, and aralkyl groups. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15, even more preferably 1 to 10, particularly preferably 1 to 8, and in the case of aralkyl groups, preferably 7 to 30. Preferred examples of this alkyl group include: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, decyl, tridecyl, octadecyl, benzyl, and phenethyl.

[0207] Can be used as R 1b The alkyl group preferably also has an ethylene oxide ring. It can be used as R... 1b The number of ring units in the cycloalkyl group (cycloalkyl group with a structure condensed with an ethylene oxide ring) is preferably 4 to 8, more preferably 5 or 6, and even more preferably 6 (i.e., cyclohexyl epoxide).

[0208] Additionally, it can be used as R 1b The alkyl group preferably has a group selected from amino, isocyanate group, mercapto group, olefinic unsaturated group and acid anhydride group.

[0209] Can be used as R 1bThe cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15, even more preferably 3 to 10, and particularly preferably 3 to 8. Examples of preferred cycloalkyl groups include cyclopropyl, cyclopentyl, and cyclohexyl.

[0210] Can be used as R 1b The number of carbon atoms in the acyl group is preferably 2 to 40, more preferably 2 to 30, even more preferably 2 to 20, and particularly preferably 2 to 18.

[0211] Can be used as R 1b The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15, even more preferably 6 to 12, and particularly preferably 6 to 10. Examples of preferred aryl groups include phenyl and naphthyl groups, with phenyl being even more preferred.

[0212] Can be used as R 1b The number of carbon-carbon unsaturated bonds in the unsaturated aliphatic group is preferably 1 to 5, more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 1. The unsaturated aliphatic group may contain heteroatoms, and is also preferably a hydrocarbon group. When the unsaturated aliphatic group is a hydrocarbon group, the number of carbon atoms is preferably 2 to 20, more preferably 2 to 15, even more preferably 2 to 10, even more preferably 2 to 8, and also preferably 2 to 5. The unsaturated aliphatic group is more preferably an alkenyl or alkynyl group.

[0213] R 1b Hydrogen atoms, alkyl, cycloalkyl or aryl groups are preferred, and alkyl or cycloalkyl groups are more preferred.

[0214] Compounds of general formula (c) have more than two R... 1b In the case of two Rs 1b They can be connected to form a ring.

[0215] R 2b Represents hydrogen atom, alkyl, cycloalkyl, acyl, alkenyl, aryl, phosphonate (phosphonic acid) group, or -SO2R S2 R S2 Indicates a substituent.

[0216] Can be used as R 2b The alkyl, cycloalkyl, acyl, and aryl groups are respectively used as R 1b The terms alkyl, cycloalkyl, acyl, and aryl have the same meaning, and the preferred forms of each group are also the same. Additionally, it can be used as R. 2b The alkyl group also preferably has an amino group as a substituent.

[0217] Can be used as R 2bThe alkenyl group comprises straight-chain alkenyl and branched alkenyl. The alkenyl group preferably has 2 to 18 carbon atoms, more preferably 2 to 7, and even more preferably 2 to 5. Preferred examples of this alkenyl group include vinyl, propenyl, butenyl, pentenyl, and hexenyl. The alkenyl group is preferably substituted.

[0218] Can be used as R 2b The phosphonate group is -P(=O)(-OR) P1 OR P2 The group represented. R P1 and R P2 This represents a hydrogen atom or a substituent, preferably an alkyl or phosphonate group. It can be used as R. P1 and R P2 alkyl groups and those that can be used as the above R 1b The meaning of alkyl is the same, and the preferred forms of alkyl are also the same. It can be used as R. P1 and R P2 Phosphate groups and those that can be used as R 2b The phosphonate group has the same meaning, and the preferred form is also the same. In R P1 or R P2 In the case of a phosphonate group, the R that constitutes the phosphonate group P1 and R P2 Alkyl groups are preferred.

[0219] In which it can be used as R 2b Of the phosphonate groups, R is preferred. P1 and R P2 All are alkyl groups, or R P1 For hydrogen atoms, R P2 It is a phosphonate group.

[0220] Furthermore, since the phosphonate group and the phosphite group (phosphite group) are tautomers, in this invention, the phosphonate group indicates that it contains a phosphite group.

[0221] In which it can be used as R 2b -SO2R S2 In, as a substituent R S2 Alkyl or aryl groups are preferred. As can be used as R... S2 Preferred forms of alkyl and aryl groups, respectively, can be listed as those that can be used as the above-mentioned R. 1b Preferred forms of alkyl and aryl groups. Wherein, R S2 Preferably, it has an alkyl group as a substituent. The preferred form of this alkyl group is the one that can be used as R in the above description. 1b The preferred forms of the alkyl groups are the same.

[0222] The compounds represented by general formula (c) have two or more R... 2b In the case of two Rs 2bThey can link together to form a ring. In the compound represented by general formula (d), the two Rs... 2b They can be connected to form a ring.

[0223] m2 is an integer from 0 to 2.

[0224] In the above general formulas (c) and (d), OR is preferred. 2b At least one of them has an acetone coordination group structure. This acetone coordination group structure represents a structure in which a hydrogen ion is removed from acetone or a compound having a substituent in acetone and coordinates with Al. The coordinating atom coordinating with Al is typically an oxygen atom. Preferably, the acetone coordination group structure is based on an acetylacetone coordination group structure (“CH3-C(=O)-CH2-C(=O)-CH3”), and a hydrogen ion is removed from this basic structure, with an oxygen atom as the coordinating atom coordinating with Al (i.e., an acetylacetone coordination group structure). The phrase “based on an acetylacetone coordination group structure” indicates, in addition to the aforementioned acetylacetone coordination group structure, a structure in which the hydrogen atoms of the aforementioned acetylacetone coordination group structure are replaced by substituents. As OR 2b Examples of compounds with acetone ligand structures include, for example, compounds AL-1 and AL-2, which will be described later.

[0225] In the above general formulas (c) and (d), OR is preferred. 2b At least one of them has an acetate ester structure. In this invention, the acetate ester structure represents a structure in which a hydrogen ion is removed from acetic acid or an acetate ester or a compound having a substituent (including a methyl group of acetic acid having an alkyl group as a substituent) and coordinated with Al. The coordinating atom coordinated with Al is usually an oxygen atom. As this acetate ester structure, an alkyl acetoacetate structure is preferred ("CH3-C(=O)-CH2-C(=O)-OR..."). alk (R) alk This indicates a structure with an alkyl group (preferably an alkyl group with 1 to 20 carbon atoms, but may be an alkyl group with 1 to 10 carbon atoms, more preferably an alkyl group with 1 to 4 carbon atoms) as the basic structure, from which one hydrogen ion is removed and an oxygen atom is coordinated with Al (i.e., an alkyl acetoacetate complex structure). The phrase "based on an alkyl acetoacetate structure" above indicates structures other than the aforementioned alkyl acetoacetate structure, where the hydrogen atoms of the aforementioned alkyl acetoacetate structure are replaced by substituents. As an OR 2b Examples of compounds with an acetate alkylation structure include, for example, compounds AL-2, AL-3, and AL-4, which will be described later.

[0226] Can be used as the above R 1b or R 2bEach group may have anionic substituents (salt-type substituents) that counteract cations. Anionic groups refer to groups capable of forming anions. Examples of anionic groups having the aforementioned counteract cations include carboxylic acid ions with ammonium ions as counteracting cations. In this case, the counteracting cation is present in such a way that the overall charge of the compound reaches 0 in the compound represented by the above general formula (c) or (d). This also applies to the compounds represented by the aforementioned general formula (a) or (b) and the compounds represented by the following general formula (e) or (f).

[0227] The following are specific examples of aluminum alkoxide compounds used in the present invention, but the present invention is not limited thereto.

[0228] Aluminum triethanolamine, aluminum triisopropoxide, aluminum trisec-butoxide, aluminum tri(ethyl acetoacetate), aluminum diisopropoxide of ethyl acetoacetate, aluminum bis(ethyl acetoacetate) monoacetylacetonate, aluminum tri(acetylacetonate), aluminum diisopropoxy-9-octadecenyl acetoacetate, aluminum diisopropoxy-monoethyl acetoacetate, aluminum triethyl acetoacetate, aluminum triacetylacetonate, aluminum diisopropoxy-monosec-butoxy, aluminum diisopropoxy-monoethyl acetoacetate, aluminum diethyl acetoacetate-isopropoxide, aluminum diacetoacetate-monoacetylacetonate, aluminum octadecyl acetoacetate-monoethyl acetylacetonate, aluminum diisopropoxide of octadecyl acetoacetate.

[0229] (Alkyl zirconium compounds)

[0230] As the alkanozirconium compound (preferably a zirconium coupling agent) used in the present invention, common alkanozirconium compounds that can be used as primer layers for components of medical devices can be widely adopted.

[0231] The zirconium alkanoate compound preferably comprises at least one of the compounds represented by general formula (e) or (f) below, more preferably at least one of the compounds represented by general formula (e) below. The total percentage of the compounds represented by general formula (e) or (f) in the above-mentioned zirconium alkanoate compound is not particularly limited, but may be, for example, 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, or even 100% by mass.

[0232] General formula (e): R 1c m3 -Zr-(OR 2c ) 4-m3

[0233] General formula (f): O-[Zr-(OR) 2c )3]2

[0234] R 1c It represents a hydrogen atom, alkyl, cycloalkyl, acyl, aryl, or unsaturated aliphatic group.

[0235] As alkyl, cycloalkyl, acyl, aryl, and unsaturated aliphatic groups, R can be used, for example, as a group that can be used in the above general formula (c). 1b Alkyl, cycloalkyl, acyl, aryl, and unsaturated aliphatic groups.

[0236] R 2c Represents hydrogen atom, alkyl, cycloalkyl, acyl, alkenyl, aryl, phosphonate group or -SO2R S3 R S3 Indicates a substituent.

[0237] As alkyl, cycloalkyl, acyl, alkenyl, aryl, and phosphonate groups, R can be used, for example, as a group that can be used in the above general formula (c). 2b Alkyl, cycloalkyl, acyl, alkenyl, aryl, and phosphonate groups. Additionally, as a group that can be used as R... S3 The substituents can be, for example, R that can be used as the general formula (c) above. S2 Substituents.

[0238] m3 is an integer from 0 to 3.

[0239] In the above general formulas (e) and (f), OR is preferred. 2c At least one of them has an acetone coordination group structure. This acetone coordination group structure has the same meaning as the acetone coordination group structure described in general formula (c). As OR 2c Examples of compounds with acetone ligand structures include, for example, compounds ZR-1 and ZR-3, which will be described later.

[0240] Furthermore, in the above general formula (e), OR is preferred. 2c At least one of them is an acetate alkylation structure. This acetate alkylation structure has the same meaning as the acetate alkylation structure described in general formula (c). As OR 2c Forms with an acetate alkylation structure, such as ZR-4 described later, can be cited as examples.

[0241] Furthermore, in the above general formulas (e) and (f), OR is preferred. 2c At least one of them has a lactate chelate structure. This lactate chelate structure represents a structure with a lactate ion (lactate ester) as the basic structure, from which a hydrogen ion is removed and coordinated with Zr. The phrase "with a lactate ion as the basic structure" indicates that, in addition to the lactate ion itself, the hydrogen atom of the lactate ion is replaced by a substituent. The coordinating atom with Zr is typically an oxygen atom. As an OR 2c Examples of compounds with lactate alkylation structures include, for instance, the compound ZR-2, which will be described later.

[0242] The following are specific examples of zirconium alkanoates used in the present invention, but the present invention is not limited thereto.

[0243] Tetrapropoxyzirconium (also known as tetra-n-propoxyzirconium), tetrabutoxyzirconium (also known as tetra-n-butanolzirconium), tetraacetylacetonezirconium, monoacetylacetone tributoxyzirconium, dibutoxybis(acetylacetone)zirconium, dibutoxybis(ethyl acetoacetate)zirconium, tributoxyethyl acetoacetatezirconium, monobutoxyacetylacetone bis(ethyl acetoacetate)zirconium, tributoxyzirconium monostearate (also known as tri-n-butanol stearate), zirconium stearate, zirconium lactate ammonium salt, monoacetylacetonezirconium

[0244] The molecular weights of the silane coupling agents, alkanolate titanium compounds, alkanolate aluminum compounds and alkanolate zirconium compounds used in this invention are not particularly limited, for example, preferably 100 to 2000, more preferably 200 to 500.

[0245] Alternatively, polymeric silane coupling agents can also be used.

[0246] The content of the compounds with reactive functional groups, preferably silane coupling agents and alkanolate metal compounds in the primer layer is not particularly limited, but preferably the total is 90% by mass or more, more preferably 95% by mass or more, even more preferably 97% by mass or more, particularly preferably 99% by mass or more, and may also be set to 100% by mass.

[0247] The primer layer may contain one or more of the following: silane coupling agent, aluminum alkoxide compound, zirconium alkoxide compound, and titanium alkoxide compound.

[0248] In addition to silane coupling agents and alkanoyl metal compounds, the primer layer may also contain additives such as surfactants, tackifiers, leveling agents, stabilizers and defoamers, within a range that does not impair the effects of the present invention.

[0249] In addition, the primer layer can be a single layer or multiple layers, preferably a single layer.

[0250] In this invention, "the primer layer comprises at least one of a silane coupling agent, a titanium alkoxide compound, an aluminum alkoxide compound, and a zirconium alkoxide compound" means that it includes: the form in which at least one of the silane coupling agent, titanium alkoxide compound, aluminum alkoxide compound, and zirconium alkoxide compound is contained after reacting with a porous layer or substrate containing a siloxane compound, and the form in which at least one of the silane coupling agent, titanium alkoxide compound, aluminum alkoxide compound, and zirconium alkoxide compound is contained after reacting with a polymer capping layer. For example, the silane coupling agent, titanium alkoxide compound, aluminum alkoxide compound, and zirconium alkoxide compound are in a state where at least a portion is hydrolyzed to expose hydroxyl groups, and can be present by reacting with the constituent metal of the porous layer or substrate containing a siloxane compound or by reacting with the groups on the surface of the polymer capping layer.

[0251] The thickness of the primer layer is much thinner than that of a conventional adhesive layer, and is not limited, but is preferably 1 nm to 100 nm. That is, the primer layer is different from the adhesive layer, which requires a certain thickness and flexibility to bond the substrate and the polymer cover layer.

[0252] exist Figure 2 For ease of explanation, the primer layer is shown as a layer with thickness.

[0253] Examples of medical devices that can utilize the laminate of the present invention, i.e., medical devices of the present invention, include catheters, dressings, X-ray imaging devices, electric surgical instruments, treatment devices, ultrasound diagnostic devices, and endoscopes.

[0254] [Manufacturing method of laminated bodies]

[0255] <Formation of porous layers containing siloxane compounds>

[0256] The following are specific examples of methods for forming porous layers containing siloxane compounds, but the present invention is not limited thereto.

[0257] A porous layer containing siloxane compounds can be formed on at least one side of a substrate through the processes described in (i) and (ii).

[0258] (i) A silica composition is prepared by dehydration condensation reaction of an alkoxysilane compound with at least one of a silane coupling agent, a titanium alkanol compound, a zirconium alkanol compound, and an aluminum alkanol compound in the presence of a pore-forming agent.

[0259] (ii) After coating a substrate with a silica composition, the silica composition is dried (or heated) to form a coating film, and then heated at a high temperature to decompose and remove the pore-forming agent, thereby forming pores in the coating film.

[0260] In step (i) above, the alkoxysilane compound is subjected to a dehydration condensation reaction with at least one of the alkoxysilane compound and hydroxysilane compound, at least one of the silane coupling agent, alkanolate titanium compound, alkanolate zirconium compound and alkanolate aluminum compound, pore-forming agent and solvent in a mixture to obtain a silica composition.

[0261] For example, at least one of an alkoxysilane compound, 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 are mixed, and a catalyst (described later) is added as needed. While mixing, the alkoxysilane compound undergoes a dehydration condensation reaction in the presence of the pore-forming agent, and the mixture is concentrated or diluted with a solvent as needed to obtain a silica composition. The reaction conditions (reaction temperature, reaction time) for the dehydration condensation reaction can be carried out according to conventional methods.

[0262] The total silica content (including the content of the dehydration condensation reaction product, i.e., the siloxane compound) in the silica composition 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.

[0263] As a pore-forming agent, a substance contained within silica and removable by heating can be used. Examples of pore-forming agents include surfactants. Nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used; nonionic surfactants are preferred, and polymeric nonionic surfactants are more preferred. When the surfactant is a polymer, its number-average molecular weight is, for example, 300 to 5000.

[0264] The surfactant content 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. On the other hand, the above-mentioned content is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less.

[0265] As a solvent, water or a combination of water and a water-soluble organic solvent is preferred. Examples of water-soluble organic solvents include: monohydric alcohols with 1 to 4 carbon atoms such as methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-1-propanol, 1-butanol, 2-butanol, tert-butanol, and 1-pentanol; dihydric alcohols with 1 to 4 carbon atoms, polyhydric alcohols such as glycerol and pentaerythritol; ethers or esters of the above alcohols 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; ketones such as acetone and methyl ethyl ketone; and formamide and N-methylformamide. The compounds include amides such as 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'-diacetylpiperazine, etc.; lactones such as γ-butyrolactone; ureas such as tetramethylurea and N,N'-dimethylimidazoline; and dimethyl sulfoxide. Among these, alcohols are preferred, and monohydric alcohols are more preferred, for hydrolysis of the contained alkoxysilane compounds under more stable conditions.

[0266] Silica compositions typically contain a catalyst. The catalyst can be any substance that promotes the hydrolysis and dehydration condensation reactions of alkoxysilane compounds.

[0267] Examples include: acids such as hydrofluoric acid, phosphoric acid, boric acid, hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, maleic acid, methylmalonic acid, stearic acid, linolenic 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.

[0268] Furthermore, metal chelate compounds can also be cited as examples of catalysts. Examples of metals that can be used in such chelate compounds include titanium, aluminum, zirconium, tin, and antimony.

[0269] The silica composition may also contain, without impairing the effects of the present invention, at least one of the above-mentioned alkoxysilane compounds, silane coupling agents, alkanolate titanium compounds, alkanolate zirconium compounds and alkanolate aluminum compounds, organic solvents, surfactants, water and catalysts.

[0270] In step (ii) above, the substrate is immersed in the silica composition obtained in step (i) above, and then the substrate is removed and dried to form a coating film. Next, the surfactant is decomposed and removed at a high temperature (e.g., above 250°C) to obtain a substrate having a porous layer containing a siloxane compound.

[0271] The average pore size and porosity of porous layers containing siloxane compounds can be controlled by the type of raw materials, the proportion of raw materials, and reaction conditions (e.g., drying or heating temperature and heating time).

[0272] In this invention, without impairing the effects of the invention, a portion of the substrate (a portion of the side of the substrate on which the porous layer containing the siloxane compound is formed) may have a portion not covered by the porous layer containing the siloxane compound (i.e., a portion of the porous layer may have voids).

[0273] <Formation of the primer layer>

[0274] In manufacturing the laminate of the present invention, it is preferable to form a primer layer on the porous layer containing a siloxane compound after forming the porous layer containing the siloxane compound. 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 liquid, coating or spraying the coating liquid onto the porous layer containing the siloxane compound, or immersing the substrate in the coating liquid, forming a coating film on at least one side of the substrate, and then drying the coating film by conventional methods (e.g., high-temperature drying at around 100°C).

[0275] As solvents for the coating solution, alcohol solvents such as methanol and ethanol, ketone solvents such as acetone and methyl ethyl ketone, ester solvents such as ethyl acetate, hydrocarbon solvents such as toluene, or mixtures thereof can be used. Furthermore, to promote the hydrolysis of silane coupling agents, alkanolate titanium compounds, alkanolate zirconium compounds, and alkanolate aluminum compounds, it is preferable to further mix water, acetic acid, or other acid catalysts into these solvents. Additionally, the coating solution can be prepared as acidic (e.g., pH 1–4 at 25°C) or alkaline (e.g., pH 9–11 at 25°C).

[0276] The content of silane coupling agent, alkanolate titanium compound, alkanolate zirconium compound and alkanolate aluminum compound in the coating solution is not particularly limited. For example, the total content can be set to 0.01 to 2% by mass, preferably 0.05% by mass or more and less than 1.5% by mass, and more preferably 0.1% by mass or more and less than 1.0% by mass.

[0277] The coating solution may contain surfactants, catalysts, etc., in addition to at least one of silane coupling agents, titanium alkoxide compounds, zirconium alkoxide compounds, and aluminum alkoxide compounds, solvents, and pH adjusters. More preferably, the coating solution consists of at least one of silane coupling agents, titanium alkoxide compounds, zirconium alkoxide compounds, and aluminum alkoxide compounds, and a solvent.

[0278] In this invention, without impairing the effects of the invention, a portion of the siloxane compound layer may have a portion not covered by the primer layer (i.e., a defect may occur in a portion of the primer layer).

[0279] <Formation of Polymer Coating>

[0280] The polymer capping layer can be formed, for example, by heating and pressing on a porous layer or primer layer containing a siloxane compound. For example, the polymer capping layer can be formed at a temperature of +5 to 30°C and 1 to 100 MPa, where the polymer's melting point is within the range of 1 to 30°C.

[0281] Alternatively, when using the thermoplastic polymer to form the polymer coating, the polymer coating can also be formed by extrusion onto the substrate.

[0282] [Example]

[0283] The present invention will be described in more detail below through embodiments, but the content of the present invention is not limited to these interpretations.

[0284] [Creating Layered Objects]

[0285] Production Figure 3 Or a stacked structure as shown in Figure 4.

[0286] <Substrate>

[0287] (Stainless steel (SUS304) substrate)

[0288] The substrate is a stainless steel (SUS304) sheet measuring 80mm in length, 20mm in width, and 2mm in thickness, with a passivation layer formed on the surface through annealing (heat treatment). After degreasing with acetone, it is immersed in a 1N sodium hydroxide aqueous solution at 50°C for 3 minutes and then rinsed. Next, it is rinsed three times with distilled water and dried in an oven heated to 100°C for 10 minutes to prepare the substrate.

[0289] (Substrates other than stainless steel)

[0290] The dimensions of the substrates other than stainless steel substrates listed in Table 3 are 80mm long × 20mm wide × 2mm thick.

[0291] The glass substrate used is JIS R3503 (trade name) quartz glass manufactured by Standard Test Piece, and it is pretreated in the same way as the stainless steel substrate mentioned above.

[0292] The ceramic substrate uses stabilized zirconium oxide "PSZ200" (trade name) manufactured by ASONE.

[0293] The ABS resin substrate is made from a sheet of "130" (trade name) manufactured by Techno-UMG through injection molding, and the surface is cleaned with ethanol.

[0294] The epoxy resin substrate used was an epoxy resin sheet manufactured by Standard Test Piece, and the surface was cleaned with ethanol.

[0295] Fabrication of a substrate containing a porous layer (L-1) of a siloxane compound with reactive functional groups.

[0296] Mix 40 g (190 mmol) of tetraethoxysilane, 1.0 g (2.8 mmol) of isopropyltris(N-aminoethyl-aminoethyl)titanate (PLENACT44 manufactured by Ajinomoto Fine-Techno Co., Inc., or TI-1 listed in Table 3 below), 9 g of ethanol, 14 g of water, and 33 g of 0.3% hydrochloric acid aqueous solution. Stir in a water bath at 63°C for 30 minutes, and then stir at room temperature for 30 minutes to prepare mixture (A).

[0297] Mix 15g of a nonionic surfactant (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock polymer, BASF's "PLURONIC (registered trademark) L-31" (trade name), number average molecular weight (Mn) 1, 100) and 12g of ethanol into mixture (A), and stir at room temperature for 60 minutes to prepare mixture (B).

[0298] The mixture (B) was diluted 25 times with 1-butanol and filtered through a filter with a sieve aperture of 0.45 μm to obtain a silica composition (C) (1.0% solids).

[0299] The cleaned stainless steel substrate was immersed in the silica composition (C) for 5 minutes, then removed and air-dried at 40°C for 30 minutes. The substrate was then heated in an oven at 300°C for 5 hours to thermally decompose and remove the nonionic surfactant, thereby producing a substrate having a porous layer (L-1) containing a siloxane compound with reactive functional groups (amino groups). Furthermore, the reactive functional groups in this porous layer originate from the raw materials used to synthesize the siloxane compound, indicating that they include groups present in a free state formed through hydrolysis.

[0300] <Fabrication of a substrate containing porous siloxane compound layers (L-2) to (L-5) with reactive functional groups>

[0301] In the fabrication of a substrate having a porous layer (L-1) of a siloxane compound with the aforementioned reactive functional groups, a nonionic surfactant (PLURONIC L-31) as described in Table 1 below is used instead of the nonionic surfactant. Otherwise, the same procedure is followed as for the substrate having a porous layer (L-1) of a siloxane compound with the aforementioned reactive functional groups to prepare substrates having porous layers (L-2) to (L-5) of a siloxane compound with reactive functional groups.

[0302] <Fabrication of a substrate with porous siloxane compound layers (L-6) to (L-12) containing reactive functional groups>

[0303] In the fabrication of a substrate having a porous layer (L-1) of a siloxane compound having the aforementioned reactive functional groups, tetraethoxysilane and the compounds described in the "alkoxide" row of Table 3 below are used. Otherwise, the same procedure is followed as for the substrate having a porous layer (L-1) of a siloxane compound having the aforementioned reactive functional groups to fabricate a substrate having a porous layer (L-6) to (L-12) of a siloxane compound having reactive functional groups.

[0304] Furthermore, the tetraethoxysilane and the compounds described in the "alkoxide" row of Table 3 below were prepared using the same molar method as the substrate having a porous layer (L-1) of a siloxane compound having the aforementioned reactive functional groups.

[0305] Fabrication of a substrate containing a siloxane compound layer (R-1) with non-reactive functional groups.

[0306] In the fabrication of a substrate having a porous layer (L-1) of a siloxane compound having the aforementioned reactive functional groups, TI-1 is not used. Otherwise, the same procedure is followed as for the substrate having a porous layer (L-1) of a siloxane compound having the aforementioned reactive functional groups to prepare a substrate having a siloxane compound layer (R-1) that does not have reactive functional groups in the raw material compound.

[0307] The average pore size of the siloxane compound layer (R-1) without reactive functional groups in the raw material compound is 1.1 μm, the porosity is 15%, and the average layer thickness is 280 nm.

[0308] Fabrication of a substrate with a non-porous siloxane compound layer (R-2)

[0309] In the fabrication of the substrate having a porous siloxane compound layer (L-1) with the aforementioned reactive functional groups, no nonionic surfactants are used. Otherwise, the same procedures are followed as for the substrate having the porous siloxane compound layer (L-1) with the aforementioned reactive functional groups to fabricate a substrate having a non-porous siloxane compound layer (R-2). No pores were observed in the non-porous siloxane compound layer (R-2).

[0310] The average thickness of the non-porous siloxane compound layer (R-2) is 240 nm.

[0311] The average pore size, porosity, and average layer thickness of the porous layer containing siloxane compounds were determined and calculated as follows. The results are shown in Table 1 below.

[0312] <Average pore size, porosity>

[0313] The substrate with a porous layer containing siloxane compounds was placed in an oven set to 150°C for 4 hours and then allowed to stand in a desiccator to room temperature for testing.

[0314] The porosity was determined using mercury intrusion porosimetry with a Micromeritics Pore Sizer 9320 (trade name). The initial pressure was set to 20 kPa, the pore size to be measured was 3 nm–400 μm, the measurement mode was pressurization (injection), and the cell volume was approximately 6 cm³. 3 Mercury contact angle 130°, mercury surface tension 484 dyn / cm.

[0315] <Average layer thickness>

[0316] Calculate the average layer thickness of the porous layer containing siloxane compounds as described below.

[0317] The laminate fabricated above was randomly cut at five points, and the cross-sections of each siloxane-containing porous layer were observed at 50,000x magnification using a scanning electron microscope (S-5500 (trade name), manufactured by Hitachi High Technology Co., Ltd.). The thickness was obtained at each point on each cross-section of the siloxane-containing porous layer formed on one side of the substrate (one of the two siloxane-containing porous layers). The average of the five thickness values ​​was taken as the average layer thickness.

[0318] [Table 1]

[0319]

[0320] <Notes to Table 1>

[0321] Porous layers containing siloxane compounds: Porous layers containing siloxane compounds with reactive functional groups.

[0322] L-31: PLURONIC L-31 (trade name, manufactured by BASF)

[0323] L-64: PLURONIC L-64 (trade name, manufactured by BASF)

[0324] L-121: PLURONIC L-121 (trade name, manufactured by BASF)

[0325] L-123: PLURONIC L-123 (trade name, manufactured by BASF)

[0326] F-108: PLURONIC F-108 (trade name, manufactured by BASF)

[0327] Number-average molecular weight Mn: The number-average molecular weight of nonionic surfactants

[0328] [Table 2]

[0329]

[0330] Formation of the primer layer (Example 13)

[0331] Mix 150g of ethanol, 350g of water, and 1.0g of isopropyl tris(N-aminoethyl-aminoethyl)titanate (PLENACT44 manufactured by Ajinomoto Fine-Techno Co., Inc., and TI-1 listed in Table 3 below) at room temperature to prepare a coating solution for primer layer formation.

[0332] The substrate having a porous siloxane compound layer (L-3) with the aforementioned reactive functional groups is immersed in a primer coating solution for 1 minute, lifted out to air, air-dried for 10 minutes, and then placed in an oven at 150°C for 10 minutes to dry. A substrate having a porous siloxane compound layer and a primer layer is prepared sequentially according to the above procedure.

[0333] The same procedure was followed to produce the substrates listed in Table 3, which sequentially have a porous layer containing a siloxane compound and a primer layer.

[0334] <Formation of Polymer Coating (Examples 1-40 and 42-60)>

[0335] By hot pressing, polymer sheets pre-cut to 60 mm long × 10 mm wide × 0.4 mm thick, as described in Table 3 (Tables 3-1 to 3-4) below, are pressed onto a porous layer or primer layer containing siloxane compounds to create a laminate with a polymer overlay.

[0336] <Formation of Polymer Coating (Example 41)>

[0337] Add 6.0 g of bisphenol A type epoxy resin (Mitsubishi Chemical "jER828" (trade name), epoxy equivalent 184-194 g / eq.) and 4.0 g of polyaminoamide (Evonik "SUNMIDE305") and mix thoroughly to obtain an epoxy resin mixture.

[0338] The epoxy resin mixture is applied to the primer layer to achieve a thickness of 0.4 mm, cured at room temperature for 1 hour, and then cured at 80°C for 2 hours to produce a laminate with epoxy resin (M-1) as the polymer coating layer.

[0339] The following tests were conducted on the fabricated laminates. The results are summarized in Table 3 below.

[0340] [Experimental Example 1] Evaluation of the sterilization durability of ethylene oxide gas (EOG)

[0341] The above-prepared laminate was repeatedly sterilized under the following conditions using an EOG sterilization apparatus (Mitsu Kogyo Co., Ltd. "EQ-150" (trade name)).

[0342] <Sterilization conditions>

[0343] Ethylene oxide gas: carbon dioxide = 20:80

[0344] 55℃

[0345] 50% RH (relative humidity)

[0346] 71 kPa decompression

[0347] Pressurize to 69 kPa

[0348] Gas concentration: 450 mg / L

[0349] Pretreatment for 1 hour

[0350] Sterilization treatment for 5 hours

[0351] Ventilation after sterilization (55 °C) for 12 hours

[0352] The number of sterilization treatments when the porous layer containing the siloxane compound peels off or floats up from the substrate, or the polymer coating peels off or floats up from the porous layer containing the siloxane compound, is evaluated according to the following evaluation criteria. "C" or above is considered qualified for this test.

[0353] <EOG Sterilization Resistance Evaluation Criteria>

[0354] AA: 200 times or more

[0355] A: More than 100 times and less than 200 times

[0356] B: More than 50 times and less than 100 times

[0357] C: More than 20 times and less than 50 times

[0358] D: Less than 20 times

[0359] [Test Example 2] Evaluation of Hydrogen Peroxide Gas Sterilization Durability

[0360] The laminate produced above is repeatedly subjected to low-temperature plasma sterilization treatment through the advanced program of a hydrogen peroxide gas sterilizer ("STERRAD (registered trademark) NX" manufactured by ASP). The number of treatments when the porous layer containing the siloxane compound peels off or floats up from the substrate, or the polymer coating peels off or floats up from the porous layer containing the siloxane compound, is evaluated according to the following evaluation criteria. "C" or above is considered qualified for this test.

[0361] <Evaluation Criteria>

[0362] AA: 200 times or more

[0363] A: More than 100 times and less than 200 times

[0364] B: More than 50 times and less than 100 times

[0365] C: More than 20 times and less than 50 times

[0366] D: Less than 20 times

[0367] [Table 3-1]

[0368]

[0369] [Table 3-2]

[0370]

[0371] [Table 3-3]

[0372]

[0373] [Table 3-4]

[0374]

[0375] <Notes to Table 3>

[0376] Example: Implementation

[0377] Comparison: Example

[0378] The "reactive functional groups" of the "porous layer containing siloxane compounds" describe the reactive functional groups possessed by the raw material compounds. On the other hand, the "reactive functional groups" of the "primer layer" describe the reactive functional groups possessed by silane coupling agents, alkanolate titanium compounds, alkanolate aluminum compounds, alkanolate zirconium compounds, and hydroxyl groups formed by partial hydrolysis of hydrolyzable groups.

[0379] The abbreviations recorded in the table above are as follows.

[0380] (A-1):

[0381] Polyamide elastomer (trade name: PEBAX 4533, manufactured by ARKEMA)

[0382] (E-1):

[0383] Polyester elastomer (trade name: PELPRENE P-40B, manufactured by Toyobo Co., Ltd.) (F-1):

[0384] Fluorinated elastomer (trade name: DAI-EL T-530, manufactured by Daikin Industries, Ltd.) (P-1):

[0385] Polyolefin elastomer (trade name: ZELAS MC707, manufactured by Mitsubishi Chemical Corporation) (P-2):

[0386] Polypropylene resin (trade name: NOVATEC PP MA3, manufactured by Japan Polyethylene Co., Ltd.)

[0387] (P-3):

[0388] Polymethylpentene resin (trade name: TPX DX231, manufactured by Mitsui Chemicals Co., Ltd.)

[0389] (P-4):

[0390] Acrylonitrile-styrene copolymer resin (copolymer ratio by mass: acrylonitrile:styrene = 30:70, trade name: STYLAC AS767, manufactured by Asahi Kasei Chemicals Co., Ltd.)

[0391] (U-1):

[0392] Polyurethane elastomer (trade name: PANDEX T-8185, manufactured by DIC)

[0393] (Alkyl Titanium Compounds)

[0394] (TI-1):

[0395] Isopropyl tris(N-aminoethyl-aminoethyl) titanate (manufactured by Ajinomoto Fine-Techno Co., Inc., "PLENACT44")

[0396] [Chemical Formula 1]

[0397]

[0398] (TI-2):

[0399] Dioctyl bis(di-tridecyl) phosphate titanate (trade name: PLENACT46B, manufactured by Ajinomoto Fine-Techno Co., Inc.)

[0400] [Chemical Formula 2]

[0401]

[0402] (TI-3):

[0403] Diisopropyl bis(dioctyl pyrophosphate) titanate (trade name: PLENACT38S, manufactured by Ajinomoto Fine-Techno Co., Inc.)

[0404] [Chemical Formula 3]

[0405]

[0406] (TI-4):

[0407] bis(dioctyl pyrophosphate)oxyacetate titanate (manufactured by Ajinomoto Fine-Techno Co., Inc., "PLENACT 138S")

[0408] [Chemical Formula 4]

[0409]

[0410] (TI-5):

[0411] bis(dioctyl pyrophosphate) vinyl titanate (manufactured by Ajinomoto Fine-Techno Co., Inc., "PLENACT238S")

[0412] [Chemical Formula 5]

[0413]

[0414] (TI-6):

[0415] Isopropyl tri-dodecylbenzenesulfonyl titanate (manufactured by Ajinomoto Fine-Techno Co., Inc., "PLENACT 9SA")

[0416] [Chemical Formula 6]

[0417]

[0418] (TI-7):

[0419] Titanium di-2-ethylhexyloxybis(2-ethyl-3-hydroxyhexyloxy) (Matsumoto Fine Chemicals Co., Ltd. "ORGATICSTC-201")

[0420] [Chemical Formula 7]

[0421]

[0422] (TI-8):

[0423] Isopropyl triisostearoyl titanate (trade name: PLENACT TTS, manufactured by Ajinomoto Fine-Techno Co., Inc.)

[0424] [Chemical Formula 8]

[0425]

[0426] (TI-9):

[0427] Tetrabutyl titanate (trade name: ORGATICS TA-21, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0428] [Chemical Formula 9]

[0429]

[0430] (TI-10):

[0431] Tetrabutyl titanate dimer (trade name: ORGATICS TA-23, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0432] [Chemical Formula 10]

[0433]

[0434] (Aluminum alkoxides)

[0435] (AL-1):

[0436] Aluminum triacetylacetonate (trade name: ORGATICS AL-3100, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0437] [Chemical Formula 11]

[0438]

[0439] (AL-2):

[0440] Ethyl diacetate, aluminum monoacetylacetonate (trade name: ORGATICS AL-3200, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0441] [Chemical Formula 12]

[0442]

[0443] (AL-3):

[0444] Aluminum triethylacetoacetate (trade name: ORGATICS AL-3215, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0445] [Chemical Formula 13]

[0446]

[0447] (AL-4):

[0448] Aluminum diisopropoxide of octadecyl acetoacetate (trade name: PLENACT AL-M, manufactured by Ajinomoto Fine-TechnoCo., Inc.)

[0449] [Chemical Formula 14]

[0450]

[0451] (AL-5):

[0452] Aluminum sec-butoxide (trade name: ASBD, manufactured by Sichuan Research Institute of Fine Chemicals Co., Ltd.)

[0453] [Chemical Formula 15]

[0454]

[0455] (Alkyl zirconium compounds)

[0456] (ZR-1):

[0457] Zirconium tetraacetylacetonate (trade name: ORGATICS ZC-150, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0458] [Chemical Formula 16]

[0459]

[0460] (ZR-2):

[0461] Zirconium lactate (trade name: ORGATICS ZC-300, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0462] [Chemical Formula 17]

[0463]

[0464] (ZR-3):

[0465] Monoacetylacetone tri-n-butoxyzirconium (Matsumoto Fine Chemicals Co., Ltd. "ORGATICS ZC-540")

[0466] [Chemical Formula 18]

[0467]

[0468] (ZR-4):

[0469] Di-n-butoxybis(ethyl acetoacetate)zirconium (Matsumoto Fine Chemicals Co., Ltd. "ORGATICS ZC-580")

[0470] [Chemical Formula 19]

[0471]

[0472] (ZR-5):

[0473] Zirconium tetrabutoxide (trade name: ORGATICS ZA-65, manufactured by Matsumoto Fine Chemicals Co., Ltd.)

[0474] [Chemical Formula 20]

[0475]

[0476] (Silane coupling agent)

[0477] (SI-1):

[0478] N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (trade name: KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0479] (SI-2):

[0480] 3-Aminopropyltrimethoxysilane (trade name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0481] (SI-3):

[0482] 3-Trimethoxysilylpropylsuccinic anhydride (trade name: X-12-967C, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0483] (SI-4):

[0484] (3-Methacryloxypropyl)trimethoxysilane (trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0485] (SI-5):

[0486] 3-Epoxypropoxypropyltrimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0487] (SI-6):

[0488] 3-Mercaptopropyltrimethoxysilane (trade name: KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.)

[0489] TES: Tetraethoxysilane

[0490] The following conclusions can be drawn from Table 3.

[0491] The laminate of Comparative Example 1 does not have the porous layer containing siloxane compounds and the primer layer specified in this invention. The laminate of Comparative Example 1 has poor durability under ethylene oxide gas sterilization and hydrogen peroxide gas sterilization.

[0492] The laminate of Comparative Example 2 does not have the porous layer containing siloxane compounds specified in this invention. The laminate of Comparative Example 2 exhibits poor durability under ethylene oxide gas sterilization.

[0493] Although the laminate of Comparative Example 3 has a siloxane compound layer on the substrate, the siloxane compound contained in this layer does not have reactive functional groups. Furthermore, the laminate of Comparative Example 3 does not have the primer layer specified in this invention. The laminate of Comparative Example 3 exhibits poor durability under ethylene oxide gas sterilization and hydrogen peroxide gas sterilization.

[0494] Although the laminate of Comparative Example 4 has a siloxane compound layer on the substrate, the siloxane compound contained in this layer does not have reactive functional groups. Although the laminate of Comparative Example 4 has the primer layer specified in this invention, its hydrogen peroxide gas sterilization durability is poor.

[0495] Although the laminates of Comparative Examples 6-8 have a siloxane compound layer on the substrate, the siloxane compound contained in this layer does not have reactive functional groups. Although the laminates of Comparative Examples 6-8 have the primer layer specified in this invention, their sterilization durability with ethylene oxide gas and hydrogen peroxide gas is poor.

[0496] Although the laminates of Comparative Examples 5, 9, and 10 have a siloxane compound layer on the substrate, this layer is not a porous material. Although the laminates of Comparative Examples 5, 9, and 10 have the primer layer specified in this invention, their sterilization durability with ethylene oxide gas and hydrogen peroxide gas is poor.

[0497] In contrast, it can be seen that the laminates of the present invention in Examples 1 to 60 exhibit excellent durability under ethylene oxide gas sterilization and hydrogen peroxide gas sterilization.

[0498] Symbol Explanation

[0499] 1 Substrate

[0500] 2. Porous layer (intermediate layer) containing siloxane compounds

[0501] 3 Polymer Covering Layer

[0502] 4. Primer layer (intermediate layer)

Claims

1. A laminate comprising a substrate, an intermediate layer on the substrate, and a polymer capping layer on the intermediate layer, the intermediate layer having a porous layer comprising a siloxane compound, the siloxane compound having at least one component selected from compounds having reactive functional groups and hydrolyzable groups, and components selected from compounds having reactive functional groups and hydrolyzable groups, the porous layer having an average pore size of 100 nm to 10 μm, a porosity of 10% to 60%, and an average layer thickness of 0.1 μm to 500 μm. The reactive functional group includes at least one selected from amino, (meth)acryloyl, mercapto, and phosphorus-containing groups. The substrate comprises at least one of iron, non-ferrous metals, inorganic materials other than metals, and organic materials. The polymer coating layer comprises at least one of a thermoplastic polymer and a thermosetting polymer.

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

3. The laminated body according to claim 2, wherein, The porous layer contains a siloxane compound that is a dehydration condensate of at least one of alkoxysilane compounds and hydroxysilane compounds with a silane coupling agent, wherein the silane coupling agent has the reactive functional group.

4. The laminated body according to claim 1, wherein, The non-ferrous metals include at least one of aluminum, titanium, magnesium, nickel, copper, lead, zinc, tin, chromium, tungsten, cobalt, and alloys of at least two of these.

5. The laminated body according to claim 1, wherein, The inorganic material other than metal includes at least one of glass and ceramics.

6. The laminate according to claim 1, wherein, The organic material includes at least one of thermoplastic resin and thermosetting resin.

7. The laminate according to claim 1 or 2, wherein, The intermediate layer has the porous layer and a primer layer on the porous layer.

8. The laminate according to claim 7, wherein, The primer layer has reactive functional groups.

9. The laminate according to claim 8, wherein, The reactive functional groups of the primer layer include at least one of amino, (meth)acryloyl, epoxy, mercapto, acid anhydride, phosphorus-containing group, hydroxyl, carboxyl, sulfonyl and acyl groups.

10. The laminate according to claim 7, 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.

11. The laminate according to claim 10, wherein, The primer layer contains at least one of alkanolate titanium compound, alkanolate aluminum compound, and alkanolate zirconium compound.

12. The laminate according to claim 11, wherein, The primer layer contains an alkanol titanium compound.

13. The laminate according to claim 10, wherein, The alkanolate titanium compounds include compounds represented by general formula (a) or (b). General formula (a): R 1a m1 -Ti-(OR 2a ) 4-m1 General formula (b): O-[Ti-(OR 2a )3]2 R 1a It represents a hydrogen atom, alkyl, cycloalkyl, acyl, aryl, or unsaturated aliphatic group; R 2a Represents hydrogen atom, alkyl, cycloalkyl, acyl, alkenyl, aryl, phosphonate group or -SO2R S1 ;R S1 Indicates substituents; m1 is an integer from 0 to 3.

14. The laminate according to claim 13, wherein, The compound represented by the general formula (a) or (b) contains at least one atom of N, P and S.

15. The laminate according to claim 10, wherein, The aluminum alkanolate compounds include those represented by the following general formula (c) or (d). General formula (c): R 1b m2 -Al-(OR) 2b ) 3-m2 General formula (d): O-[Al-(OR) 2b )2]2 R 1b It represents a hydrogen atom, alkyl, cycloalkyl, acyl, aryl, or unsaturated aliphatic group; R 2b Represents hydrogen atom, alkyl, cycloalkyl, acyl, alkenyl, aryl, phosphonate group or -SO2R S2 ;R S2 Indicates substituents; m2 is an integer from 0 to 2.

16. The laminate according to claim 15, wherein, In the general formulas (c) and (d), OR 2b At least one of them has an acetone ligand structure or an acetate ligand structure.

17. The laminate according to claim 10, wherein, The zirconium alkanolate compounds comprise compounds represented by the following general formula (e) or (f), General formula (e): R 1c m3 -Zr-(OR 2c ) 4-m3 General formula (f): O-[Zr-(OR)] 2c )3]2 R 1c It represents a hydrogen atom, alkyl, cycloalkyl, acyl, aryl, or unsaturated aliphatic group; R 2c Represents hydrogen atom, alkyl, cycloalkyl, acyl, alkenyl, aryl, phosphonate group or -SO2R S3 ;R S3 Indicates substituents; m3 is an integer from 0 to 3.

18. The laminate according to claim 17, wherein, In the general formulas (e) and (f), OR 2c At least one of them has an acetone ligand structure, an acetate ligand structure, or a lactate ligand structure.

19. The laminate according to claim 1 or 2, wherein, The polymer coating layer comprises a thermoplastic polymer.

20. A medical device that uses the laminate as a constituent component as described in any one of claims 1 to 19.

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