WO2020066630A1 - Method for manufacturing laminate, and laminate - Google Patents

Method for manufacturing laminate, and laminate Download PDF

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Publication number
WO2020066630A1
WO2020066630A1 PCT/JP2019/035728 JP2019035728W WO2020066630A1 WO 2020066630 A1 WO2020066630 A1 WO 2020066630A1 JP 2019035728 W JP2019035728 W JP 2019035728W WO 2020066630 A1 WO2020066630 A1 WO 2020066630A1
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group
formula
compound represented
functional layer
forming
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PCT/JP2019/035728
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French (fr)
Japanese (ja)
Inventor
悠太 滋野井
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富士フイルム株式会社
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Publication of WO2020066630A1 publication Critical patent/WO2020066630A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/34—Macromolecular materials
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers

Definitions

  • the present invention relates to a method for producing a laminate and a laminate.
  • adhesion of the pathogenic yeast Candida albicans to the denture base is one of the causes of denture stomatitis, and particularly in the elderly, the bacteria grown in the oral cavity migrate to the lungs. It has been pointed out that it may cause fatal pneumonia.
  • medical devices such as cannulas, catheters, stents, and implants that are placed or implanted in the body can cause bacteremia and even sepsis due to the attachment and growth of pathogenic yeast or pathogenic bacteria.
  • cannulas, catheters, stents, and implants that are placed or implanted in the body can cause bacteremia and even sepsis due to the attachment and growth of pathogenic yeast or pathogenic bacteria.
  • Patent Literature 1 discloses a phospholipid-like structure comprising a structural unit based on a phosphorylcholine group-containing (meth) acrylate, a hydrophobic group-containing (meth) acrylate and a hydroxy group-containing (meth) acrylate. Prepolymers having the same and polyurethanes using the same are described (claims). It is described that this polyurethane has an antithrombotic property because it has a phospholipid-like structure (paragraph [0019]).
  • Patent Literature 1 the laminate obtained by coating the substrate with the polyurethane described in Patent Literature 1 was insufficient in the ability to inhibit bacterial adhesion (refers to the property of less bacterial adhesion).
  • an object of the present invention is to provide a method for producing a laminate and a laminate which are excellent in inhibiting bacterial adhesion.
  • the inventor of the present invention has made intensive studies to solve the above-described problems, and as a result of the method for manufacturing a laminate including a predetermined process, has learned that a laminate excellent in bacterial adhesion inhibition can be obtained.
  • the present invention has been completed.
  • the present invention includes the following [1] to [7].
  • [1] a pretreatment step of disposing an intermediate layer having a substituent that reacts with a polymerizable group on at least a part of the surface of the substrate;
  • a functional layer-forming composition containing a monomer having a polymerizable group a coating layer forming step of forming a coating layer that covers at least a part of the intermediate layer, Curing step of curing the coating layer to form a functional layer,
  • the monomer having a polymerizable group A compound represented by the formula (IV) described later, a compound represented by the formula (V) described later, a compound represented by the formula (VI) described later, a compound represented by the formula (VII) described later, At least one selected from the group consisting of a compound represented by formula (I), a compound represented by formula (II) described below, and a compound represented by formula (VIII) described below;
  • a method for manufacturing a laminate A method for manufacturing a laminate.
  • the monomer having a polymerizable group is a compound represented by the following formula (E), a compound represented by the following formula (F), or a compound represented by the following formula (A)
  • a laminate having: The functional layer is a layer obtained by curing a functional layer-forming composition containing a monomer having a polymerizable group, The intermediate layer and the functional layer are bonded by a covalent bond, The monomer having a polymerizable group, A compound represented by the formula (IV) described later, a compound represented by the formula (V) described later, a compound represented by the formula (VI) described later, a compound represented by the formula (VII) described later, At least one selected from the group consisting of a compound represented by formula (I), a compound represented by formula (II) described below, and a compound represented by formula (VIII) described below; Laminate. [7] The laminate according to the above [6], wherein the intermediate layer and the base material are bonded by a covalent bond.
  • a range represented by using “to” includes both ends of “to”.
  • the range expressed as “AB” includes “A” and “B”.
  • the “bacterial adhesion inhibitory property” means a property that bacterial adhesion is small.
  • the method for producing a laminate of the present invention includes a pretreatment step, a coating layer forming step, and a curing step.
  • the pretreatment step is a step of disposing an intermediate layer having a substituent that reacts with a polymerizable group on at least a part of the surface of the substrate.
  • the substrate is not particularly limited, and examples thereof include a glass substrate and a resin substrate.
  • the resin substrate include a polyester resin substrate, a polyimide resin substrate, an epoxy resin substrate, a polyether resin substrate, and a polystyrene resin substrate.
  • the glass substrate is preferably a substrate made of a substance that is in a glass state containing silicate as a main component (here, “main component” refers to a component occupying 75% by mass or more). For example, any one selected from the group consisting of soda glass (also referred to as “soda lime glass”), borosilicate glass, and quartz glass is more preferable.
  • the surface of the glass substrate may be coated or uncoated, but is preferably not coated.
  • the polyester resin base material means a base material containing 75% by mass or more of the polyester resin based on the total mass of the base material.
  • the polyimide resin substrate means a substrate containing 75% by mass or more of a polyimide resin based on the total mass of the substrate.
  • the epoxy resin substrate means a substrate containing 75% by mass or more of an epoxy resin based on the total mass of the substrate.
  • the polyether-based resin substrate means a substrate containing 75% by mass or more of a polyether resin based on the total mass of the substrate.
  • the polystyrene resin substrate means a substrate containing 75% by mass or more of a polystyrene resin based on the total mass of the substrate.
  • the substrate may have been subjected to a surface treatment. That is, the substrate may be a surface-treated substrate (surface-treated substrate).
  • the surface treatment method is not particularly limited, and examples thereof include a corona treatment, a plasma treatment, a flame treatment, and a UV (Ultra Violet) treatment, and a plasma treatment or a UV treatment is preferable.
  • the substrate By subjecting the substrate to the above surface treatment, a group capable of forming a covalent bond with an intermediate layer described later can be introduced into the surface of the substrate. That is, the substrate may be a substrate having on its surface a substituent capable of covalently bonding to the intermediate layer.
  • the type of the substituent that can be covalently bonded to the intermediate layer is not particularly limited, and examples include a hydroxyl group.
  • the substituent that can be covalently bonded to the intermediate layer can be confirmed by measuring an infrared light reflection spectrum.
  • the measurement of the infrared light reflection spectrum is preferably performed by a total reflection measurement method (ATR: Attenuated Total Reflection) of Fourier Transform Infrared Spectroscopy (FT-IR).
  • the intermediate layer is a layer having a substituent that reacts with the polymerizable group.
  • the method for forming the intermediate layer is not particularly limited as long as it can form a layer having a substituent that reacts with a polymerizable group.
  • a chemical vapor deposition method, a physical vapor deposition method, and a polymerizable There is a method in which a compound having a substituent that reacts with a group is provided on a substrate.
  • the type of the substituent contained in the compound having a substituent that reacts with the polymerizable group is not particularly limited, for example, amino group, thiol group, vinyl group, hydroxy group, carbonyl group, formyl group, carboxyl group, ether group and An ester group is mentioned, and among these, at least one selected from the group consisting of an amino group, a thiol group and a vinyl group is preferable.
  • the type of the compound having a substituent that reacts with the polymerizable group is not particularly limited, but, for example, a silane coupling agent having a substituent that reacts with the polymerizable group is preferable because reactivity with a substrate is more excellent. More specifically, a silane coupling agent having a vinyl group, a silane coupling agent having an amino group, a silane coupling agent having a mercapto group, and a silane coupling agent having a styryl group are exemplified. Examples of the silane coupling agent having a vinyl group include vinyltrimethoxysilane and vinyltriethoxysilane.
  • silane coupling agent having an amino group examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N- (vinyl (Benzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride.
  • silane coupling agent having a mercapto group examples include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.
  • silane coupling agent having a styryl group examples include p-styryltrimethoxysilane.
  • the density of the substituent that reacts with the polymerizable group in the intermediate layer is not particularly limited, but is preferably 0.1 moles / nm 2 or more, and more preferably 0.1 moles / nm 2 to 10 moles / nm 2. More preferably, it is 1 moles / nm 2 to 10 moles / nm 2 .
  • the density of the substituent which reacts with the polymerizable group in the intermediate layer is determined by Sumimura et al. (Molecular packing density of a self-assembled monolayer formed from N- (2-aminopropyl) acrylonitrile propylamorphous chromosome. , 47: 8841-8843).
  • An example using 3-aminopropyltrimethoxysilane will be described below as an example.
  • 3-aminopropyltrimethoxysilane is further evaporated to produce a glass substrate having a silane coupling agent layer.
  • the prepared glass substrate having a silane coupling agent layer was treated with 2,4,6-trinitrobenzenesulfonic acid (TNBS), and the wavelength was 420 nm using an ultraviolet-visible spectrophotometer (V-550, manufactured by JASCO Corporation). The absorbance is measured, and the density of the TNBS molecule is calculated. Further, the peak area ratio of the N1s spectrum derived from the TNBS and the N1s spectrum derived from the unreacted substituent is measured using an X-ray photoelectron spectrometer (XPS), and the density of the substituent (molecules / nm 2 ) is calculated.
  • XPS X-ray photoelectron spectrometer
  • the coating layer forming step is a step of forming a coating layer by coating at least a part of the intermediate layer using a functional layer forming composition containing a monomer having a polymerizable group.
  • Method of forming coating layer The method of coating at least a part of the intermediate layer using the composition for forming a functional layer is not particularly limited, and examples thereof include methods such as dipping, spray coating, spraying, and coating with a bar coater.
  • the composition for forming a functional layer is a composition containing a monomer having a polymerizable group.
  • the content of the monomer having a polymerizable group in the composition for forming a functional layer is preferably 50% by mass or more based on the total mass of the solid content in the composition.
  • the upper limit is not particularly limited, but may be 100% by mass, and is often 99% by mass or less.
  • the said solid content intends the component contained in the composition except the solvent, and it calculates as a solid content even if the property is liquid.
  • the monomer having a polymerizable group includes the compound represented by the formula (IV), the compound represented by the formula (V), the compound represented by the formula (VI), the compound represented by the formula (VII), It is at least one selected from the group consisting of a compound represented by I), a compound represented by formula (II), and a compound represented by formula (VIII).
  • R 41 represents a methyl group, an ethyl group, a propyl group, or a propan-2-yl group, and a plurality of R 41 may be the same or different.
  • R 41 is preferably a methyl group or an ethyl group, and more preferably a methyl group.
  • R 42 represents a hydrogen atom or a methyl group, and is preferably a methyl group.
  • R 43 represents —NH— or —O—, and is preferably —NH—.
  • n4 represents an integer of 1 to 4, preferably 2 or 3, and more preferably 2.
  • 14 represents an integer of 1 to 4, and 14 is preferably 3 or 4, and more preferably 4.
  • M 4 represents SO 3 ⁇ or COO ⁇ , and is preferably SO 3 ⁇ .
  • R 51 represents a methyl group, an ethyl group, a propyl group, or a propan-2-yl group, and a plurality of R 51 may be the same or different.
  • R 51 is preferably a methyl group or an ethyl group, more preferably a methyl group.
  • R 52 represents a hydrogen atom or a methyl group, and is preferably a methyl group.
  • n5 represents an integer of 1 to 4, preferably 2 or 3, and more preferably 2.
  • L 51 represents a linear or branched alkylene group having 3 or 4 carbon atoms, preferably a propane-1,3-diyl group or a butane-1,4-diyl group, and butane-1,4. And more preferably a diyl group.
  • M 5 represents SO 3 ⁇ or COO ⁇ , and is preferably SO 3 ⁇ .
  • R 61 represents a hydrogen atom or a methyl group.
  • R 71 and R 72 each independently represent a hydrogen atom or a methyl group.
  • n represents an integer of 1 to 100, preferably an integer of 1 to 50, and more preferably an integer of 1 to 15.
  • R represents a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different.
  • R is preferably a hydrogen atom.
  • L represents —O—, a linear or branched alkylene group having 2 to 4 carbon atoms, and any one of divalent linking groups selected from the group consisting of a combination of two or more thereof. , A plurality of Ls may be the same or different.
  • -O- may be arranged in the middle of a linear or branched alkylene group having 2 to 4 carbon atoms.
  • L is preferably-(CH 2 ) m -O- (CH 2 ) n- .
  • m and n are each independently an integer of 1 to 4 (preferably an integer of 1 to 3), and preferably an integer of 1 to 3 (preferably 1).
  • R 1 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
  • R 2 and R 4 are each independently any one selected from the group consisting of —O—, a linear or branched alkylene group having 1 to 4 carbon atoms, and a combination of two or more thereof. Represents a species of divalent linking group.
  • R 2 is preferably an ethyleneoxy group (—C 2 H 4 O—) or an ethylene group.
  • R 4 is preferably an oxyethylene group (—OC 2 H 4 —) or an ethylene group.
  • R 3 is —O—, a linear or branched alkylene group having 1 to 4 carbon atoms, a group represented by the formula (III), and any one selected from the group consisting of a combination of two or more thereof. Or one kind of divalent linking group.
  • R 3 is preferably an ethyleneoxyethylene group (—C 2 H 4 —OC 2 H 4 —) or an ethylene group.
  • L 1 and L 2 each independently represent a single bond or a group represented by the formula (III). It is preferable that both L 1 and L 2 are a single bond or a group represented by the formula (III).
  • R 31 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
  • * Represents a bonding site to another atom.
  • R 81 and R 82 each independently represent a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
  • n represents an integer of 1 to 10, preferably an integer of 2 to 8, and more preferably an integer of 3 to 5.
  • the monomer having a polymerizable group is a compound represented by the formula (E), a compound represented by the formula (F), or a compound represented by the formula (A) and a compound represented by the formula (C). Combinations are preferred.
  • the proportion of the monomer having a polymerizable group in the solid content is preferably 50% by mass or more, more preferably 70% by mass or more, and preferably 80% by mass or more. It is more preferably 90% by mass or more, particularly preferably 95% by mass or more. The upper limit is 100% by mass.
  • the composition for forming a functional layer may further include a polymerization initiator.
  • the polymerization initiator is not particularly limited, for example, a photo-radical polymerization initiator, a photo-polymerization initiator such as a photo-cationic polymerization initiator and a photo-anionic polymerization initiator, and a heat-radical polymerization initiator and a thermo-cationic polymerization initiator such as Thermal polymerization initiators are exemplified.
  • the ratio of the polymerization initiator in the solid content is not particularly limited, but is preferably 0.1% by mass to 10% by mass, and is preferably 0.5% by mass to 5% by mass. Is more preferred.
  • the composition for forming a functional layer may further include a solvent.
  • the solvent is not particularly limited as long as it can dissolve or disperse the above-mentioned monomer having a polymerizable group, but is preferably a solvent which can be easily removed from the composition for forming a functional layer.
  • alcohol is preferable, alcohol that is liquid at 25 ° C. and 1013 hPa is more preferable, and alcohol having 3 or less carbon atoms is further preferable.
  • As the alcohol having 3 or less carbon atoms methanol, ethanol, propanol or 2-propanol is preferable, and methanol is more preferable.
  • the proportion of the solvent in the composition for forming a functional layer is not particularly limited, but is 10% by mass to 95% by mass relative to the total mass of the composition for forming a functional layer. It is preferably 30% by mass to 90% by mass, and more preferably 50% by mass to 80% by mass.
  • the curing step is a step of curing the coating layer to form a functional layer.
  • the curing of the coating layer is performed by polymerizing a monomer having a polymerizable group. At this time, not only the monomer is polymerized, but also a covalent bond is formed between the intermediate layer and the functional layer by a reaction between the ⁇ substituent which reacts with the polymerizable group '' of the intermediate layer and the polymerizable group of the monomer. Is also good.
  • the curing method is not particularly limited, and includes light irradiation and / or heating.
  • the composition for forming a functional layer contains a polymerization initiator, it is preferable to use a curing method corresponding to the polymerization initiator.
  • the laminate of the present invention has a substrate, an intermediate layer disposed on at least a part of the surface of the substrate, and a functional layer disposed on at least a part of a surface of the intermediate layer opposite to the substrate. And a laminate having:
  • the substrate is as described in the method for producing a laminate of the present invention.
  • the intermediate layer is a layer that is covalently bonded to the functional layer.
  • the method for forming the intermediate layer is as described in the method for producing a laminate of the present invention.
  • the intermediate layer is a layer formed using a compound having a substituent that reacts with a polymerizable group.
  • the intermediate layer may be bonded to the surface of the substrate via a covalent bond or may be bonded via a non-covalent bond.
  • a non-covalent bond is intended to mean a bond other than a covalent bond such as a Van der Waals force, a hydrogen bond, an electromagnetic force including a dipole interaction or an ionic interaction.
  • the functional layer is a layer obtained by curing a composition for forming a functional layer containing a monomer having a polymerizable group.
  • composition for forming functional layer >> This is described in the method for manufacturing a laminate of the present invention.
  • the functional layer can be formed by curing the functional layer forming composition covering at least a part of the intermediate layer. The details are as described in the method for producing a laminate of the present invention.
  • the laminate of the present invention is excellent in inhibiting the adhesion of bacteria, it can be suitably used for instruments or devices that require a reduction in the attachment of bacteria, particularly medical instruments or medical devices.
  • composition for forming functional layer Compound 1 (95.0 parts by mass) represented by the formula (A), water-soluble azo polymerization initiator (VA-046B, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (5.0 parts by mass), and methanol
  • the composition for forming a functional layer (hereinafter sometimes referred to as “functional layer forming composition 1”) is mixed so that the solid content of the compound 1 and the water-soluble azo polymerization initiator is 20% by mass. .) was prepared.
  • the column of the composition for forming a functional layer in Table 1 shows the composition of the composition for forming a functional layer. In the column of the composition for forming a functional layer in Table 1, "-" indicates that the component was not used.
  • the glass substrate with an intermediate layer and the sample for evaluation are each placed in a sterile petri dish, and Candida albicans (Candida albicans JCM2085; “JCM” is a yeast of “Japan Collection of Microsomi” or “Mic”) in a Yeast Extract Peptone Dextrose (YPD) medium.
  • JCM Candida albicans
  • YPD Yeast Extract Peptone Dextrose
  • the bacterial cells were inoculated and a bacterial solution adjusted to be 1000 cfu / mL was added. Next, the cells were cultured under aerobic conditions at 37 ° C. for 3 hours, and the cultured samples were washed with a PBS (Phosphate buffered saline) buffer.
  • PBS Phosphate buffered saline
  • the number of bacteria was determined by a colorimetric method (XTT method; “XTT” is an abbreviation of “2,3-bis- (2-methoxy-4-nitro-5-sulfophenyl) -2H-tetrazolium-5-carboxanilide”). Quantified. Based on the absorbance of the glass substrate with the intermediate layer as a reference, the difference in absorbance (decrease in absorbance) of the evaluation sample was determined and evaluated according to the following criteria.
  • ⁇ Substituent density on the surface of the glass substrate with an intermediate layer The density of the substituent on the surface of the glass substrate with an intermediate layer was measured by the method described above. Details are as follows. The glass substrate with the intermediate layer was treated with 2,4,6-trinitrobenzenesulfonic acid (TNBS), and the absorbance was measured at a wavelength of 420 nm using an ultraviolet-visible spectrophotometer (V-550 manufactured by JASCO Corporation). The density of the TNBS molecule was calculated. Further, the peak area ratio of the N1s spectrum derived from TNBS and the N1s spectrum derived from the unreacted substituent was measured using X-ray photoelectron spectroscopy (XPS) to calculate the density of the substituent. As a result, in Examples 1 to 8, a substituent density of 1.5 molecules / nm 2 was obtained.
  • XPS X-ray photoelectron spectroscopy
  • composition 2 A composition for forming a functional layer (hereinafter referred to as “functional layer-forming composition 2”) was prepared in the same manner as in Example 1 except that compound 2 represented by formula (B) was used instead of compound 1. ) was prepared.
  • the column of the composition for forming a functional layer in Table 1 shows the composition of the composition for forming a functional layer. In the column of the composition for forming a functional layer in Table 1, "-" indicates that the component was not used.
  • composition 3 for forming a functional layer A composition for forming a functional layer (hereinafter referred to as “composition 3 for forming a functional layer”) was prepared in the same manner as in Example 1 except that the compound 3 represented by the formula (C) was used instead of the compound 1. ) was prepared.
  • the column of the composition for forming a functional layer in Table 1 shows the composition of the composition for forming a functional layer. In the column of the composition for forming a functional layer in Table 1, "-" indicates that the component was not used.
  • composition 4 A composition for forming a functional layer (hereinafter referred to as “functional layer-forming composition 4”) was prepared in the same manner as in Example 1 except that the compound 4 represented by the formula (D) was used instead of the compound 1. ) was prepared.
  • the column of the composition for forming a functional layer in Table 1 shows the composition of the composition for forming a functional layer. In the column of the composition for forming a functional layer in Table 1, "-" indicates that the component was not used.
  • composition 5 A composition for forming a functional layer (hereinafter referred to as “functional layer-forming composition 5”) was prepared in the same manner as in Example 1 except that compound 5 represented by formula (E) was used instead of compound 1. ) was prepared.
  • the column of the composition for forming a functional layer in Table 1 shows the composition of the composition for forming a functional layer. In the column of the composition for forming a functional layer in Table 1, "-" indicates that the component was not used.
  • composition 6 A composition for forming a functional layer (hereinafter referred to as “functional layer-forming composition 6”) was prepared in the same manner as in Example 1 except that compound 6 represented by formula (F) was used instead of compound 1. ) was prepared.
  • the column of the composition for forming a functional layer in Table 1 shows the composition of the composition for forming a functional layer. In the column of the composition for forming a functional layer in Table 1, "-" indicates that the component was not used.
  • composition 7 for forming a functional layer A composition for forming a functional layer (hereinafter referred to as “composition 7 for forming a functional layer”) was prepared in the same manner as in Example 1 except that the compound 7 represented by the formula (G) was used instead of the compound 1. ) was prepared.
  • the column of the composition for forming a functional layer in Table 1 shows the composition of the composition for forming a functional layer. In the column of the composition for forming a functional layer in Table 1, "-" indicates that the component was not used.
  • Example 8 ⁇ Preparation of composition for forming functional layer> Compound 1 (25.0 parts by mass), Compound 3 (70.0 parts by mass), water-soluble azo polymerization initiator (VA-046B, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (5.0 parts by mass), Methanol is mixed, and the composition for forming a functional layer (hereinafter referred to as the “composition for forming a functional layer”) is mixed so that the solid content of the compound 1, the compound 3, and the water-soluble azo polymerization initiator is 20% by mass. 8 ").
  • the column of the composition for forming a functional layer in Table 1 shows the composition of the composition for forming a functional layer. In the column of the composition for forming a functional layer in Table 1, "-" indicates that the component was not used.
  • Example 9 ⁇ Preparation of composition for forming functional layer>
  • a composition 1 for forming a functional layer was prepared.
  • the column of the composition for forming a functional layer in Table 1 shows the composition of the composition for forming a functional layer.
  • "-" indicates that the component was not used.
  • Examples 1 to 9 were excellent in inhibiting bacterial adhesion.
  • Examples 5 and 6 in which the composition for forming a functional layer contains Compound 5 and Example 6 in which Compound 6 contains Compound 6, and Examples 8 in which the composition for forming a functional layer contains Compound 3 and Compound 1 show the ability to inhibit bacterial adhesion. And the storage stability at high humidity were both excellent.

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Abstract

The present invention provides a method for manufacturing a laminate that is exceptional in terms of prevention of bacterial adhesion, and a laminate. This method for manufacturing a laminate includes: a pre-processing step in which an intermediate layer having a substituent group that reacts with a polymerizing group is arranged on at least part of the surface of a substrate; a coating layer formation step in which at least part of the intermediate layer is coated using a functional-layer-forming composition, which has as a main component a monomer having a polymerizing group, to form a coating layer; and a curing step in which the coating layer is cured to form a functional layer. The monomer having a polymerizing group is at least one from among a set of specific compounds.

Description

積層体の製造方法および積層体Laminated body manufacturing method and laminated body
　本発明は、積層体の製造方法および積層体に関する。 The present invention relates to a method for producing a laminate and a laminate.
　基材の表面への菌の付着は、菌の増殖の原因となることから、基材の表面に対する菌の付着を減少させることが求められている。 菌 Because bacteria adhere to the surface of the substrate, which causes the growth of bacteria, it is required to reduce the adherence of bacteria to the surface of the substrate.
　例えば、義歯床に対する病原性酵母カンジダ・アルビカンス（Ｃａｎｄｉｄａ　ａｌｂｉｃａｎｓ）の付着は、義歯性口内炎の原因の一つとなっており、特に高齢者においては、口腔内で増殖した菌が肺に移行することにより、致命的な肺炎を引き起こす可能性が指摘されている。また、カニューレ、カテーテル、ステントおよびインプラントなどの体内に留置したり、埋め込んだりする医療器具は、病原性酵母または病原性細菌が付着し、増殖することにより、菌血症、さらには敗血症の原因となるおそれがある。 For example, adhesion of the pathogenic yeast Candida albicans to the denture base is one of the causes of denture stomatitis, and particularly in the elderly, the bacteria grown in the oral cavity migrate to the lungs. It has been pointed out that it may cause fatal pneumonia. In addition, medical devices such as cannulas, catheters, stents, and implants that are placed or implanted in the body can cause bacteremia and even sepsis due to the attachment and growth of pathogenic yeast or pathogenic bacteria. Could be.
　このような事情から、基材、特に医療器具に用いられる基材、の表面の菌付着をより少なくすることが求められている。 か ら Under such circumstances, it is required to further reduce bacterial adhesion on the surface of a substrate, particularly a substrate used for a medical device.
　特許文献１には、ホスホリルコリン基含有の（メタ）アクリル酸エステル、疎水性基含有の（メタ）アクリル酸エステルおよびヒドロキシ基含有の（メタ）アクリル酸エステルに基づく構成単位からなるリン脂質類似構造を有するプレポリマーおよびそれを用いたポリウレタンが記載されている（特許請求の範囲）。このポリウレタンは、リン脂質類似構造を有しているため抗血栓性があることが記載されている（段落［００１９］）。 Patent Literature 1 discloses a phospholipid-like structure comprising a structural unit based on a phosphorylcholine group-containing (meth) acrylate, a hydrophobic group-containing (meth) acrylate and a hydroxy group-containing (meth) acrylate. Prepolymers having the same and polyurethanes using the same are described (claims). It is described that this polyurethane has an antithrombotic property because it has a phospholipid-like structure (paragraph [0019]).
特開平９－２４１３３０号公報JP-A-9-241330
　しかし、特許文献１に記載されたポリウレタンを基材にコーティングして得られる積層体は、菌付着抑制性（菌の付着が少ない特性をいう）が不十分であった。 However, the laminate obtained by coating the substrate with the polyurethane described in Patent Literature 1 was insufficient in the ability to inhibit bacterial adhesion (refers to the property of less bacterial adhesion).
　そこで、本発明は、菌付着抑制性に優れる積層体の製造方法および積層体を提供することを課題とする。 Therefore, an object of the present invention is to provide a method for producing a laminate and a laminate which are excellent in inhibiting bacterial adhesion.
　本発明者は、上記課題を解決すべく鋭意検討を重ねた結果、所定の工程を含む積層体の製造方法によれば、菌付着抑制性に優れた積層体を得られることを知得し、本発明を完成させた。 The inventor of the present invention has made intensive studies to solve the above-described problems, and as a result of the method for manufacturing a laminate including a predetermined process, has learned that a laminate excellent in bacterial adhesion inhibition can be obtained. The present invention has been completed.
　すなわち、本発明は、以下の［１］～［７］である。
　［１］　基材の表面の少なくとも一部に、重合性基と反応する置換基を有する中間層を配置する前処理工程と、
　重合性基を有するモノマーを含む機能層形成用組成物を用いて、上記中間層の少なくとも一部を被覆する被覆層を形成する被覆層形成工程と、
　上記被覆層を硬化させて機能層を形成する硬化工程と
を含み、
　上記重合性基を有するモノマーが、
　後述する式（ＩＶ）で表される化合物、後述する式（Ｖ）で表される化合物、後述する式（ＶＩ）で表される化合物、後述する式（ＶＩＩ）で表される化合物、後述する式（Ｉ）で表される化合物、後述する式（ＩＩ）で表される化合物、および、後述する式（ＶＩＩＩ）で表される化合物からなる群から選択される少なくとも１種である、
積層体の製造方法。
　［２］　上記重合性基と反応する置換基が、アミノ基、チオール基およびビニル基からなる群から選択される少なくとも１種を有する、上記［１］に記載の積層体の製造方法。
　［３］　上記基材が、上記中間層と共有結合し得る置換基をその表面に有する、上記［１］または［２］に記載の積層体の製造方法。
　［４］　上記重合性基と反応する置換基の密度が、０．１ｍｏｌｅｃｕｌｅｓ／ｎｍ２以上である、上記［１］～［３］のいずれか１つに記載の積層体の製造方法。
　［５］　上記重合性基を有するモノマーが、後述する式（Ｅ）で表される化合物、後述する式（Ｆ）で表わされる化合物、または、後述する式（Ａ）で表される化合物と後述する式（Ｃ）で表される化合物との組合せである、上記［１］～［４］のいずれか１つに記載の積層体の製造方法。
　［６］　基材と、上記基材の表面の少なくとも一部に配置された中間層と、上記中間層の上記基材の側とは反対側の面の少なくとも一部に配置された機能層とを有する積層体であって、
　上記機能層は、重合性基を有するモノマーを含む機能層形成用組成物を硬化させた層であり、
　上記中間層と上記機能層とは共有結合で結合しており、
　上記重合性基を有するモノマーが、
　後述する式（ＩＶ）で表される化合物、後述する式（Ｖ）で表される化合物、後述する式（ＶＩ）で表される化合物、後述する式（ＶＩＩ）で表される化合物、後述する式（Ｉ）で表される化合物、後述する式（ＩＩ）で表される化合物、および、後述する式（ＶＩＩＩ）で表される化合物からなる群から選択される少なくとも１種である、
積層体。
　［７］　上記中間層と上記基材とが共有結合により結合している、上記［６］に記載の積層体。 That is, the present invention includes the following [1] to [7].
[1] a pretreatment step of disposing an intermediate layer having a substituent that reacts with a polymerizable group on at least a part of the surface of the substrate;
Using a functional layer-forming composition containing a monomer having a polymerizable group, a coating layer forming step of forming a coating layer that covers at least a part of the intermediate layer,
Curing step of curing the coating layer to form a functional layer,
The monomer having a polymerizable group,
A compound represented by the formula (IV) described later, a compound represented by the formula (V) described later, a compound represented by the formula (VI) described later, a compound represented by the formula (VII) described later, At least one selected from the group consisting of a compound represented by formula (I), a compound represented by formula (II) described below, and a compound represented by formula (VIII) described below;
A method for manufacturing a laminate.
[2] The method for producing a laminate according to [1], wherein the substituent that reacts with the polymerizable group has at least one selected from the group consisting of an amino group, a thiol group, and a vinyl group.
[3] The method for producing a laminate according to the above [1] or [2], wherein the base material has on its surface a substituent capable of covalently bonding to the intermediate layer.
[4] The method for producing a laminate according to any one of [1] to [3], wherein the density of the substituent that reacts with the polymerizable group is 0.1 molecules / nm 2 or more.
[5] When the monomer having a polymerizable group is a compound represented by the following formula (E), a compound represented by the following formula (F), or a compound represented by the following formula (A), The method for producing a laminate according to any one of the above [1] to [4], which is a combination with a compound represented by the formula (C):
[6] a substrate, an intermediate layer disposed on at least a part of the surface of the substrate, and a functional layer disposed on at least a part of a surface of the intermediate layer on a side opposite to the side of the substrate. A laminate having:
The functional layer is a layer obtained by curing a functional layer-forming composition containing a monomer having a polymerizable group,
The intermediate layer and the functional layer are bonded by a covalent bond,
The monomer having a polymerizable group,
A compound represented by the formula (IV) described later, a compound represented by the formula (V) described later, a compound represented by the formula (VI) described later, a compound represented by the formula (VII) described later, At least one selected from the group consisting of a compound represented by formula (I), a compound represented by formula (II) described below, and a compound represented by formula (VIII) described below;
Laminate.
[7] The laminate according to the above [6], wherein the intermediate layer and the base material are bonded by a covalent bond.
　本発明によれば、菌付着抑制性に優れる積層体の製造方法および積層体を提供できる。 According to the present invention, it is possible to provide a method for producing a laminate excellent in bacterial adhesion control and a laminate.
　本発明において「～」を用いて表される範囲は、「～」の両端を含むものとする。例えば、「Ａ～Ｂ」と表現される範囲には、「Ａ」および「Ｂ」を含む。
　本発明において「菌付着抑制性」は、菌の付着が少ない特性を意味する。
　以下では、本発明をより詳細に説明する。 In the present invention, a range represented by using “to” includes both ends of “to”. For example, the range expressed as “AB” includes “A” and “B”.
In the present invention, the “bacterial adhesion inhibitory property” means a property that bacterial adhesion is small.
Hereinafter, the present invention will be described in more detail.
［積層体の製造方法］
　本発明の積層体の製造方法は、前処理工程と、被覆層形成工程と、硬化工程とを含む。 [Production method of laminate]
The method for producing a laminate of the present invention includes a pretreatment step, a coating layer forming step, and a curing step.
　各工程について詳細に説明する。 Each step will be described in detail.
〈前処理工程〉
　前処理工程は、基材の表面の少なくとも一部に、重合性基と反応する置換基を有する中間層を配置する工程である。 <Pretreatment step>
The pretreatment step is a step of disposing an intermediate layer having a substituent that reacts with a polymerizable group on at least a part of the surface of the substrate.
《基材》
　基材は、特に限定されないが、例えば、ガラス基材、および、樹脂基材が挙げられる。
　樹脂基材としては、ポリエステル系樹脂基材、ポリイミド系樹脂基材、エポキシ系樹脂基材、ポリエーテル系樹脂基材、およびポリスチレン系樹脂基材が挙げられる。
　ガラス基材は、ケイ酸塩を主成分（ここで、「主成分」は「７５質量％以上の含有量を占める成分」をいう。）とするガラス状態となる物質からなる基材が好ましく、例えば、ソーダガラス（「ソーダ石灰ガラス」ともいう）、ホウケイ酸ガラスおよび石英ガラスからなる群から選択されるいずれか１種がより好ましい。
　ガラス基材の表面はコーティングがされていてもよいし、コーティングがされていなくてもよいが、コーティングがされていないことが好ましい。 "Base material"
The substrate is not particularly limited, and examples thereof include a glass substrate and a resin substrate.
Examples of the resin substrate include a polyester resin substrate, a polyimide resin substrate, an epoxy resin substrate, a polyether resin substrate, and a polystyrene resin substrate.
The glass substrate is preferably a substrate made of a substance that is in a glass state containing silicate as a main component (here, “main component” refers to a component occupying 75% by mass or more). For example, any one selected from the group consisting of soda glass (also referred to as “soda lime glass”), borosilicate glass, and quartz glass is more preferable.
The surface of the glass substrate may be coated or uncoated, but is preferably not coated.
　なお、ポリエステル系樹脂基材とは、基材の全質量に対して、ポリエステル樹脂を７５質量％以上含む基材を意味する。
　ポリイミド系樹脂基材とは、基材の全質量に対して、ポリイミド樹脂を７５質量％以上含む基材を意味する。
　エポキシ系樹脂基材とは、基材の全質量に対して、エポキシ樹脂を７５質量％以上含む基材を意味する。
　ポリエーテル系樹脂基材とは、基材の全質量に対して、ポリエーテル樹脂を７５質量％以上含む基材を意味する。
　ポリスチレン系樹脂基材とは、基材の全質量に対して、ポリスチレン樹脂を７５質量％以上含む基材を意味する。 In addition, the polyester resin base material means a base material containing 75% by mass or more of the polyester resin based on the total mass of the base material.
The polyimide resin substrate means a substrate containing 75% by mass or more of a polyimide resin based on the total mass of the substrate.
The epoxy resin substrate means a substrate containing 75% by mass or more of an epoxy resin based on the total mass of the substrate.
The polyether-based resin substrate means a substrate containing 75% by mass or more of a polyether resin based on the total mass of the substrate.
The polystyrene resin substrate means a substrate containing 75% by mass or more of a polystyrene resin based on the total mass of the substrate.
　基材には、表面処理が施されていていてもよい。つまり、基材は、表面処理が施された基材（表面処理済み基材）であってもよい。
　表面処理の方法は特に限定されないが、例えば、コロナ処理、プラズマ処理、フレーム処理、およびＵＶ（Ｕｌｔｒａ　Ｖｉｏｌｅｔ；紫外線）処理が挙げられ、プラズマ処理またはＵＶ処理が好ましい。 The substrate may have been subjected to a surface treatment. That is, the substrate may be a surface-treated substrate (surface-treated substrate).
The surface treatment method is not particularly limited, and examples thereof include a corona treatment, a plasma treatment, a flame treatment, and a UV (Ultra Violet) treatment, and a plasma treatment or a UV treatment is preferable.
　基材に対して上記表面処理が施されることにより、基材の表面に後述する中間層と共有結合を形成し得る基を導入できる。つまり、基材は、中間層と共有結合し得る置換基をその表面に有する基材であってもよい。
　中間層と共有結合し得る置換基の種類は特に限定されないが、例えば、水酸基が挙げられる。 By subjecting the substrate to the above surface treatment, a group capable of forming a covalent bond with an intermediate layer described later can be introduced into the surface of the substrate. That is, the substrate may be a substrate having on its surface a substituent capable of covalently bonding to the intermediate layer.
The type of the substituent that can be covalently bonded to the intermediate layer is not particularly limited, and examples include a hydroxyl group.
　中間層と共有結合し得る置換基は、赤外光反射スペクトルを測定することで確認できる。赤外光反射スペクトルの測定は、フーリエ変換赤外分光法（ＦＴ－ＩＲ：Fourier Transform Infrared Spectroscopy）の全反射測定法（ＡＴＲ：Attenuated Total Reflection）で行うことが好ましい。 置換 The substituent that can be covalently bonded to the intermediate layer can be confirmed by measuring an infrared light reflection spectrum. The measurement of the infrared light reflection spectrum is preferably performed by a total reflection measurement method (ATR: Attenuated Total Reflection) of Fourier Transform Infrared Spectroscopy (FT-IR).
《中間層》
　中間層は、重合性基と反応する置換基を有する層である。
　中間層の形成方法は、重合性基と反応する置換基を有する層を形成できるものであれば特に限定されないが、例えば、化学蒸着法、物理蒸着法、および、スパッタ法など用いて、重合性基と反応する置換基を有する化合物を基材上に付与する方法が挙げられる。 《Intermediate layer》
The intermediate layer is a layer having a substituent that reacts with the polymerizable group.
The method for forming the intermediate layer is not particularly limited as long as it can form a layer having a substituent that reacts with a polymerizable group.For example, a chemical vapor deposition method, a physical vapor deposition method, and a polymerizable There is a method in which a compound having a substituent that reacts with a group is provided on a substrate.
　重合性基と反応する置換基を有する化合物に含まれる置換基の種類は特に限定されないが、例えば、アミノ基、チオール基、ビニル基、ヒドロキシ基、カルボニル基、ホルミル基、カルボキシル基、エーテル基およびエステル基が挙げられ、これらのうちでも、アミノ基、チオール基およびビニル基からなる群から選択される少なくとも１種が好ましい。 The type of the substituent contained in the compound having a substituent that reacts with the polymerizable group is not particularly limited, for example, amino group, thiol group, vinyl group, hydroxy group, carbonyl group, formyl group, carboxyl group, ether group and An ester group is mentioned, and among these, at least one selected from the group consisting of an amino group, a thiol group and a vinyl group is preferable.
　重合性基と反応する置換基を有する化合物の種類は特に限定されないが、例えば、基材との反応性がより優れる点で、重合性基と反応する置換基を有するシランカップリング剤が好ましい。より具体的には、ビニル基を有するシランカップリング剤、アミノ基を有するシランカップリング剤、メルカプト基を有するシランカップリング剤、およびスチリル基を有するシランカップリング剤が挙げられる。
　ビニル基を有するシランカップリング剤としては、例えば、ビニルトリメトキシシランおよびビニルトリエトキシシランが挙げられる。
　アミノ基を有するシランカップリング剤としては、例えば、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルジメトキシシラン、Ｎ－２－（アミノエチル）－３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリメトキシシラン、３－アミノプロピルトリエトキシシラン、３－トリエトキシシリル－Ｎ－（１，３－ジメチル－ブチリデン）プロピルアミン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、およびＮ－（ビニルベンジル）－２－アミノエチル－３－アミノプロピルトリメトキシシランの塩酸塩が挙げられる。
　メルカプト基を有するシランカップリング剤としては、例えば、３－メルカプトプロピルメチルジメトキシシラン、および３－メルカプトプロピルトリメトキシシランが挙げられる。
　スチリル基を有するシランカップリング剤としては、例えば、ｐ－スチリルトリメトキシシランが挙げられる。 The type of the compound having a substituent that reacts with the polymerizable group is not particularly limited, but, for example, a silane coupling agent having a substituent that reacts with the polymerizable group is preferable because reactivity with a substrate is more excellent. More specifically, a silane coupling agent having a vinyl group, a silane coupling agent having an amino group, a silane coupling agent having a mercapto group, and a silane coupling agent having a styryl group are exemplified.
Examples of the silane coupling agent having a vinyl group include vinyltrimethoxysilane and vinyltriethoxysilane.
Examples of the silane coupling agent having an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N- (vinyl (Benzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride.
Examples of the silane coupling agent having a mercapto group include 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane.
Examples of the silane coupling agent having a styryl group include p-styryltrimethoxysilane.
（重合性基と反応する置換基の密度）
　中間層における重合性基と反応する置換基の密度は、特に限定されないが、０．１ｍｏｌｅｃｕｌｅｓ／ｎｍ２以上であることが好ましく、０．１ｍｏｌｅｃｕｌｅｓ／ｎｍ２～１０ｍｏｌｅｃｕｌｅｓ／ｎｍ２であることがより好ましく、１ｍｏｌｅｃｕｌｅｓ／ｎｍ２～１０ｍｏｌｅｃｕｌｅｓ／ｎｍ２であることがさらに好ましい。 (Density of substituents that react with polymerizable groups)
The density of the substituent that reacts with the polymerizable group in the intermediate layer is not particularly limited, but is preferably 0.1 moles / nm 2 or more, and more preferably 0.1 moles / nm 2 to 10 moles / nm 2. More preferably, it is 1 moles / nm 2 to 10 moles / nm 2 .
　中間層における重合性基と反応する置換基の密度は、Ｓｕｇｉｍｕｒａら（Ｍｏｌｅｃｕｌａｒ　ｐａｃｋｉｎｇ　ｄｅｎｓｉｔｙ　ｏｆ　ａ　ｓｅｌｆ－ａｓｓｅｍｂｌｅｄ　ｍｏｎｏｌａｙｅｒ　ｆｏｒｍｅｄ　ｆｒｏｍ　Ｎ－（２－ａｍｉｎｏｒｔｈｙｌ）－３－ａｍｉｎｏｐｒｏｐｙｌｔｒｉｅｔｈｏｘｙｓｉｌａｎｅ　ｂｙ　ａ　ｖａｐｏｒ　ｐｈａｓｅ　ｐｒｏｃｅｓｓ，　Ｃｈｅｍｉｃａｌ　Ｃｏｍｍｕｎｉｃａｔｉｏｎｓ，　２０１１，　４７：　８８４１－８８４３）に記載された方法により計測したものである。
　以下に一例として、３－アミノプロピルトリメトキシシランを用いた例を示す。
　ガラス基板（テンパックス）を、酸素プラズマ処理した後、さらに、３－アミノプロピルトリメトキシシランを蒸着してシランカップリング剤層を有するガラス基板を作製する。
　作製したシランカップリング剤層を有するガラス基板を２，４，６－トリニトロベンゼンスルホン酸（ＴＮＢＳ）で処理し、紫外可視分光光度計（Ｖ－５５０，日本分光社製）を用いて波長４２０ｎｍで吸光度の測定を行い、ＴＮＢＳ分子の密度を算出する。
　さらに、Ｘ線光電子分光装置（ＸＰＳ）を用いてＴＮＢＳ由来および未反応の置換基由来のＮ１ｓスペクトルのピーク面積比の測定を行い、置換基の密度（ｍｏｌｅｃｕｌｅｓ／ｎｍ２）を算出する。 The density of the substituent which reacts with the polymerizable group in the intermediate layer is determined by Sumimura et al. (Molecular packing density of a self-assembled monolayer formed from N- (2-aminopropyl) acrylonitrile propylamorphous chromosome. , 47: 8841-8843).
An example using 3-aminopropyltrimethoxysilane will be described below as an example.
After the glass substrate (Tempax) is subjected to oxygen plasma treatment, 3-aminopropyltrimethoxysilane is further evaporated to produce a glass substrate having a silane coupling agent layer.
The prepared glass substrate having a silane coupling agent layer was treated with 2,4,6-trinitrobenzenesulfonic acid (TNBS), and the wavelength was 420 nm using an ultraviolet-visible spectrophotometer (V-550, manufactured by JASCO Corporation). The absorbance is measured, and the density of the TNBS molecule is calculated.
Further, the peak area ratio of the N1s spectrum derived from the TNBS and the N1s spectrum derived from the unreacted substituent is measured using an X-ray photoelectron spectrometer (XPS), and the density of the substituent (molecules / nm 2 ) is calculated.
〈被覆層形成工程〉
　被覆層形成工程は、重合性基を有するモノマーを含む機能層形成用組成物を用いて上記中間層の少なくとも一部を被覆して被覆層を形成する工程である。 <Coating layer forming step>
The coating layer forming step is a step of forming a coating layer by coating at least a part of the intermediate layer using a functional layer forming composition containing a monomer having a polymerizable group.
《被覆層の形成方法》
　機能層形成用組成物を用いて上記中間層の少なくとも一部を被覆する方法は、特に限定されないが、ディッピング、スプレー塗布、吹き付け、および、バーコーターによる塗布などの方法が挙げられる。 << Method of forming coating layer >>
The method of coating at least a part of the intermediate layer using the composition for forming a functional layer is not particularly limited, and examples thereof include methods such as dipping, spray coating, spraying, and coating with a bar coater.
《機能層形成用組成物》
　機能層形成用組成物は、重合性基を有するモノマーを含む組成物である。
　なお、機能層形成用組成物中における重合性基を有するモノマーの含有量は、組成物中の固形分全質量に対して、５０質量％以上が好ましい。上限は特に制限されないが、１００質量％が挙げられ、９９質量％以下の場合が多い。
　なお、上記固形分とは、溶媒を除いた組成物に含まれる成分を意図し、その性状が液状であっても固形分として計算する。 << Composition for forming functional layer >>
The composition for forming a functional layer is a composition containing a monomer having a polymerizable group.
The content of the monomer having a polymerizable group in the composition for forming a functional layer is preferably 50% by mass or more based on the total mass of the solid content in the composition. The upper limit is not particularly limited, but may be 100% by mass, and is often 99% by mass or less.
In addition, the said solid content intends the component contained in the composition except the solvent, and it calculates as a solid content even if the property is liquid.
（重合性基を有するモノマー）
　重合性基を有するモノマーは、式（ＩＶ）で表される化合物、式（Ｖ）で表される化合物、式（ＶＩ）で表される化合物、式（ＶＩＩ）で表される化合物、式（Ｉ）で表される化合物、式（ＩＩ）で表される化合物、および、式（ＶＩＩＩ）で表される化合物からなる群から選択される少なくとも１種である。 (Monomer having a polymerizable group)
The monomer having a polymerizable group includes the compound represented by the formula (IV), the compound represented by the formula (V), the compound represented by the formula (VI), the compound represented by the formula (VII), It is at least one selected from the group consisting of a compound represented by I), a compound represented by formula (II), and a compound represented by formula (VIII).
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　式（ＩＶ）中、各記号の意味は以下のとおりである。
　Ｒ４１はメチル基、エチル基、プロピル基またはプロパン－２－イル基を表し、複数のＲ４１は互いに同じであってもよいし異なっていてもよい。Ｒ４１はメチル基またはエチル基であることが好ましく、メチル基であることがより好ましい。
　Ｒ４２は水素原子またはメチル基を表し、メチル基であることが好ましい。
　Ｒ４３は－ＮＨ－または－Ｏ－を表し、－ＮＨ－であることが好ましい。
　ｎ４は１～４の整数を表し、２または３であることが好ましく、２であることがより好ましい。
　ｌ４は１～４の整数を表し、ｌ４は３または４であることが好ましく、４であることがより好ましい。
　Ｍ４はＳＯ３ －またはＣＯＯ－を表し、ＳＯ３ －であることが好ましい。 In the formula (IV), the meaning of each symbol is as follows.
R 41 represents a methyl group, an ethyl group, a propyl group, or a propan-2-yl group, and a plurality of R 41 may be the same or different. R 41 is preferably a methyl group or an ethyl group, and more preferably a methyl group.
R 42 represents a hydrogen atom or a methyl group, and is preferably a methyl group.
R 43 represents —NH— or —O—, and is preferably —NH—.
n4 represents an integer of 1 to 4, preferably 2 or 3, and more preferably 2.
14 represents an integer of 1 to 4, and 14 is preferably 3 or 4, and more preferably 4.
M 4 represents SO 3 − or COO −, and is preferably SO 3 − .
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　式（Ｖ）中、各記号の意味は以下のとおりである。
　Ｒ５１はメチル基、エチル基、プロピル基またはプロパン－２－イル基を表し、複数のＲ５１は互いに同じであってもよいし異なっていてもよい。Ｒ５１はメチル基またはエチル基であることが好ましく、メチル基であることがより好ましい。
　Ｒ５２は水素原子またはメチル基を表し、メチル基であることが好ましい。
　ｎ５は１～４の整数を表し、２または３であることが好ましく、２であることがより好ましい。
　Ｌ５１は炭素数３または４の直鎖状または分岐鎖状のアルキレン基を表し、プロパン－１，３－ジイル基またはブタン－１，４－ジイル基であることが好ましく、ブタン－１，４－ジイル基であることがより好ましい。
　Ｍ５はＳＯ３ －またはＣＯＯ－を表し、ＳＯ３ －であることが好ましい。 In the formula (V), the meaning of each symbol is as follows.
R 51 represents a methyl group, an ethyl group, a propyl group, or a propan-2-yl group, and a plurality of R 51 may be the same or different. R 51 is preferably a methyl group or an ethyl group, more preferably a methyl group.
R 52 represents a hydrogen atom or a methyl group, and is preferably a methyl group.
n5 represents an integer of 1 to 4, preferably 2 or 3, and more preferably 2.
L 51 represents a linear or branched alkylene group having 3 or 4 carbon atoms, preferably a propane-1,3-diyl group or a butane-1,4-diyl group, and butane-1,4. And more preferably a diyl group.
M 5 represents SO 3 − or COO −, and is preferably SO 3 − .
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　式（ＶＩ）中、記号の意味は以下のとおりである。
　Ｒ６１は水素原子またはメチル基を表す。
Figure JPOXMLDOC01-appb-C000024
 In the formula (VI), the meanings of the symbols are as follows.
R 61 represents a hydrogen atom or a methyl group.
Figure JPOXMLDOC01-appb-C000024
　式（ＶＩＩ）中、各記号の意味は以下のとおりである。
　Ｒ７１およびＲ７２は、それぞれ独立に、水素原子またはメチル基を表す。
　ｎは１～１００の整数を表し、１～５０の整数が好ましく、１～１５の整数がより好ましい。 In the formula (VII), the meaning of each symbol is as follows.
R 71 and R 72 each independently represent a hydrogen atom or a methyl group.
n represents an integer of 1 to 100, preferably an integer of 1 to 50, and more preferably an integer of 1 to 15.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　式（Ｉ）中、各記号の意味は以下のとおりである。
　Ｒは水素原子またはメチル基を表し、複数のＲは互いに同じであってもよいし異なっていてもよい。Ｒは水素原子であることが好ましい。
　Ｌは－Ｏ－、炭素数２～４の直鎖状または分岐鎖状のアルキレン基およびこれらのうち２種以上の組合せからなる群から選択されるいずれか１種の２価の連結基を表し、複数のＬは互いに同じであってもよいし異なっていてもよい。上記組み合わせにおいて、－Ｏ－は、炭素数２～４の直鎖状または分岐鎖状のアルキレン基の途中に配置されていてもよい。
　Ｌは－（ＣＨ２）ｍ－Ｏ－（ＣＨ２）ｎ－であることが好ましい。ここで、ｍおよびｎは、それぞれ独立に、１～４の整数（好ましくは、１～３の整数）であり、１～３の整数（好ましくは、１）であることが好ましい。 In the formula (I), the meaning of each symbol is as follows.
R represents a hydrogen atom or a methyl group, and a plurality of Rs may be the same or different. R is preferably a hydrogen atom.
L represents —O—, a linear or branched alkylene group having 2 to 4 carbon atoms, and any one of divalent linking groups selected from the group consisting of a combination of two or more thereof. , A plurality of Ls may be the same or different. In the above combination, -O- may be arranged in the middle of a linear or branched alkylene group having 2 to 4 carbon atoms.
L is preferably-(CH 2 ) m -O- (CH 2 ) n- . Here, m and n are each independently an integer of 1 to 4 (preferably an integer of 1 to 3), and preferably an integer of 1 to 3 (preferably 1).
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　式（ＩＩ）中、各記号の意味は以下のとおりである。
　Ｒ１は水素原子またはメチル基を表し、水素原子であることが好ましい。
　Ｒ２およびＲ４は、それぞれ独立に、－Ｏ－、炭素数１～４の直鎖状または分岐鎖状のアルキレン基およびこれらのうち２種以上の組合せからなる群から選択されるいずれか１種の２価の連結基を表す。Ｒ２はエチレンオキシ基（－Ｃ２Ｈ４Ｏ－）であるか、またはエチレン基であることが好ましい。Ｒ４はオキシエチレン基（－ＯＣ２Ｈ４－）であるか、またはエチレン基であることが好ましい。
　Ｒ３は－Ｏ－、炭素数１～４の直鎖状または分岐鎖状のアルキレン基、式（ＩＩＩ）で表される基およびこれらのうち２種以上の組合せからなる群から選択されるいずれか１種の２価の連結基を表す。Ｒ３はエチレンオキシエチレン基（－Ｃ２Ｈ４－Ｏ－Ｃ２Ｈ４－）であるか、またはエチレン基であることが好ましい。
　Ｌ１およびＬ２は、それぞれ独立に、単結合または式（ＩＩＩ）で表される基を表す。Ｌ１およびＬ２はいずれも単結合であるか、または式（ＩＩＩ）で表される基であることが好ましい。 In the formula (II), the meaning of each symbol is as follows.
R 1 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
R 2 and R 4 are each independently any one selected from the group consisting of —O—, a linear or branched alkylene group having 1 to 4 carbon atoms, and a combination of two or more thereof. Represents a species of divalent linking group. R 2 is preferably an ethyleneoxy group (—C 2 H 4 O—) or an ethylene group. R 4 is preferably an oxyethylene group (—OC 2 H 4 —) or an ethylene group.
R 3 is —O—, a linear or branched alkylene group having 1 to 4 carbon atoms, a group represented by the formula (III), and any one selected from the group consisting of a combination of two or more thereof. Or one kind of divalent linking group. R 3 is preferably an ethyleneoxyethylene group (—C 2 H 4 —OC 2 H 4 —) or an ethylene group.
L 1 and L 2 each independently represent a single bond or a group represented by the formula (III). It is preferable that both L 1 and L 2 are a single bond or a group represented by the formula (III).
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　式（ＩＩＩ）中、各記号の意味は以下のとおりである。
　Ｒ３１は水素原子またはメチル基を表し、水素原子であることが好ましい。
　＊は他の原子との結合箇所を表す。 In the formula (III), the meaning of each symbol is as follows.
R 31 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
* Represents a bonding site to another atom.
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
　式（ＶＩＩＩ）中、各記号の意味は以下のとおりである。
　Ｒ８１およびＲ８２は、それぞれ独立に、水素原子またはメチル基を表し、水素原子であることが好ましい。
　ｎは１～１０の整数を表し、２～８の整数であることが好ましく、３～５の整数であることがより好ましい。 In the formula (VIII), the meaning of each symbol is as follows.
R 81 and R 82 each independently represent a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
n represents an integer of 1 to 10, preferably an integer of 2 to 8, and more preferably an integer of 3 to 5.
　重合性基を有するモノマーは、式（Ｅ）で表される化合物、式（Ｆ）で表わされる化合物、または、式（Ａ）で表される化合物と式（Ｃ）で表される化合物との組合せが好ましい。 The monomer having a polymerizable group is a compound represented by the formula (E), a compound represented by the formula (F), or a compound represented by the formula (A) and a compound represented by the formula (C). Combinations are preferred.
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
（固形分中の重合性基を有するモノマーの割合）
　機能層形成用組成物において、固形分中の重合性基を有するモノマーの割合は５０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、８０質量％以上であることがさらに好ましく、９０質量％以上であることが特に好ましく、９５質量％以上であることが最も好ましい。上限は１００質量％である。 (Ratio of monomer having polymerizable group in solid content)
In the composition for forming a functional layer, the proportion of the monomer having a polymerizable group in the solid content is preferably 50% by mass or more, more preferably 70% by mass or more, and preferably 80% by mass or more. It is more preferably 90% by mass or more, particularly preferably 95% by mass or more. The upper limit is 100% by mass.
（重合開始剤）
　機能層形成用組成物は、さらに、重合開始剤を含んでもよい。
　重合開始剤は特に限定されないが、例えば、光ラジカル重合開始剤、光カチオン重合開始剤および光アニオン重合開始剤などの光重合開始剤、ならびに、熱ラジカル重合開始剤および熱カチオン重合開始剤などの熱重合開始剤が挙げられる。 (Polymerization initiator)
The composition for forming a functional layer may further include a polymerization initiator.
The polymerization initiator is not particularly limited, for example, a photo-radical polymerization initiator, a photo-polymerization initiator such as a photo-cationic polymerization initiator and a photo-anionic polymerization initiator, and a heat-radical polymerization initiator and a thermo-cationic polymerization initiator such as Thermal polymerization initiators are exemplified.
　機能層形成用組成物において、固形分中の重合開始剤の割合は特に限定されないが、０．１質量％～１０質量％であることが好ましく、０．５質量％～５質量％であることがより好ましい。 In the composition for forming a functional layer, the ratio of the polymerization initiator in the solid content is not particularly limited, but is preferably 0.1% by mass to 10% by mass, and is preferably 0.5% by mass to 5% by mass. Is more preferred.
（溶媒）
　機能層形成用組成物は、さらに、溶媒を含んでもよい。
　溶媒は、上述した重合性基を有するモノマーを溶解または分散することができるものであれば特に限定されないが、機能層形成用組成物から除去することが容易であるものが好ましい。具体的には、アルコールが好ましく、２５℃、１０１３ｈＰａにおいて液体であるアルコールがより好ましく、炭素数３以下のアルコールがさらに好ましい。炭素数が３以下のアルコールとしては、メタノール、エタノール、プロパノールまたは２－プロパノールが好ましく、メタノールがより好ましい。 (solvent)
The composition for forming a functional layer may further include a solvent.
The solvent is not particularly limited as long as it can dissolve or disperse the above-mentioned monomer having a polymerizable group, but is preferably a solvent which can be easily removed from the composition for forming a functional layer. Specifically, alcohol is preferable, alcohol that is liquid at 25 ° C. and 1013 hPa is more preferable, and alcohol having 3 or less carbon atoms is further preferable. As the alcohol having 3 or less carbon atoms, methanol, ethanol, propanol or 2-propanol is preferable, and methanol is more preferable.
　機能層形成用組成物が溶媒を含む場合の機能層形成用組成物中の溶媒の割合は特に限定されないが、機能層形成用組成物全質量に対して、１０質量％～９５質量％であることが好ましく、３０質量％～９０質量％であることがより好ましく、５０質量％～８０質量％であることがさらに好ましい。 When the composition for forming a functional layer contains a solvent, the proportion of the solvent in the composition for forming a functional layer is not particularly limited, but is 10% by mass to 95% by mass relative to the total mass of the composition for forming a functional layer. It is preferably 30% by mass to 90% by mass, and more preferably 50% by mass to 80% by mass.
〈硬化工程〉
　硬化工程は、被覆層を硬化させて機能層を形成する工程である。
　被覆層の硬化は、重合性基を有するモノマーを重合させることにより行う。この際、モノマーが重合するだけではなく、中間層の「重合性基と反応する置換基」とモノマーの重合性基との反応により、中間層と機能層との間に共有結合が形成されてもよい。 <Curing process>
The curing step is a step of curing the coating layer to form a functional layer.
The curing of the coating layer is performed by polymerizing a monomer having a polymerizable group. At this time, not only the monomer is polymerized, but also a covalent bond is formed between the intermediate layer and the functional layer by a reaction between the `` substituent which reacts with the polymerizable group '' of the intermediate layer and the polymerizable group of the monomer. Is also good.
　硬化の方法は特に限定されず、光照射および／または加熱が挙げられる。機能層形成用組成物が重合開始剤を含むときは、その重合開始剤に対応した硬化方法を用いることが好ましい。 The curing method is not particularly limited, and includes light irradiation and / or heating. When the composition for forming a functional layer contains a polymerization initiator, it is preferable to use a curing method corresponding to the polymerization initiator.
［積層体］
　本発明の積層体は、基材と、基材の表面の少なくとも一部に配置された中間層と、中間層の基材の側とは反対側の面の少なくとも一部に配置された機能層とを有する積層体である。 [Laminate]
The laminate of the present invention has a substrate, an intermediate layer disposed on at least a part of the surface of the substrate, and a functional layer disposed on at least a part of a surface of the intermediate layer opposite to the substrate. And a laminate having:
〈基材〉
　基材は、本発明の積層体の製造方法において説明したとおりである。 <Base material>
The substrate is as described in the method for producing a laminate of the present invention.
〈中間層〉
　中間層は、機能層とは共有結合で結合している層である。
　中間層を形成する方法は、本発明の積層体の製造方法において説明したとおりである。例えば、中間層は、重合性基と反応する置換基を有する化合物を用いて形成された層である。 <Intermediate layer>
The intermediate layer is a layer that is covalently bonded to the functional layer.
The method for forming the intermediate layer is as described in the method for producing a laminate of the present invention. For example, the intermediate layer is a layer formed using a compound having a substituent that reacts with a polymerizable group.
　中間層は、基材の表面と共有結合を介して結合していてもよいし、非共有結合を介して結合していてもよい。非共有結合とは、ファンデルワールス力、水素結合、双極子相互作用またはイオン間相互作用を含む電磁気学的な力など、共有結合以外の結合を意図する。 The intermediate layer may be bonded to the surface of the substrate via a covalent bond or may be bonded via a non-covalent bond. A non-covalent bond is intended to mean a bond other than a covalent bond such as a Van der Waals force, a hydrogen bond, an electromagnetic force including a dipole interaction or an ionic interaction.
〈機能層〉
　機能層は、重合性基を有するモノマーを含む機能層形成用組成物を硬化させた層である。 <Functional layer>
The functional layer is a layer obtained by curing a composition for forming a functional layer containing a monomer having a polymerizable group.
《機能層形成用組成物》
　本発明の積層体の製造方法において説明したものである。 << Composition for forming functional layer >>
This is described in the method for manufacturing a laminate of the present invention.
《機能層の形成方法》
　機能層は、中間層の少なくとも一部を被覆した機能層形成用組成物を硬化させることにより形成できる。
　詳細には、本発明の積層体の製造方法において説明したとおりである。 《Method of forming functional layer》
The functional layer can be formed by curing the functional layer forming composition covering at least a part of the intermediate layer.
The details are as described in the method for producing a laminate of the present invention.
　本発明の積層体は、菌付着抑制性に優れることから、菌の付着を少なくすることが求められる器具または器材、特に医療器具または医療器材、に好適に用いることができる。 積 層 Since the laminate of the present invention is excellent in inhibiting the adhesion of bacteria, it can be suitably used for instruments or devices that require a reduction in the attachment of bacteria, particularly medical instruments or medical devices.
　以下では、実施例によって本発明をより具体的に説明するが、本発明はこれらの実施例に制限されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
［実施例１］
〈機能層形成用組成物の調製〉
　式（Ａ）で表される化合物１（９５．０質量部）と、水溶性アゾ重合開始剤（ＶＡ－０４６Ｂ，富士フイルム和光純薬社製）（５．０質量部）と、メタノールとを混合し、化合物１と水溶性アゾ重合開始剤とをあわせた固形分の含有量が２０質量％となるように機能層形成用組成物（以下「機能層形成用組成物１」という場合がある。）を調製した。
　表１の機能層形成用組成物の欄に、機能層形成用組成物の組成を示す。なお、表１の機能層形成用組成物の欄中、「－」はその成分を用いなかったことを表す。 [Example 1]
<Preparation of composition for forming functional layer>
Compound 1 (95.0 parts by mass) represented by the formula (A), water-soluble azo polymerization initiator (VA-046B, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (5.0 parts by mass), and methanol The composition for forming a functional layer (hereinafter sometimes referred to as “functional layer forming composition 1”) is mixed so that the solid content of the compound 1 and the water-soluble azo polymerization initiator is 20% by mass. .) Was prepared.
The column of the composition for forming a functional layer in Table 1 shows the composition of the composition for forming a functional layer. In the column of the composition for forming a functional layer in Table 1, "-" indicates that the component was not used.
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
〈各種評価〉
《ガラス基板の表面処理》
　ガラス基板（テンパックス）を、プラズマクリーニング装置（ＥＸＡＭ，神港精機社製）を用いて、酸素プラズマ処理した。その後、さらに、３－アミノプロピルトリメトキシシラン（ＴＣＩ社製；以下「ＡＰＴＭ」という場合がある。）を密閉式気相法により蒸着処理をして、エタノールで洗浄し乾燥させ、中間層（シランカップリング剤層）を有するガラス基板（以下「中間層付きガラス基板」という場合がある。）を得た。中間層は、アミノ基を有していた。 <Various evaluations>
《Surface treatment of glass substrate》
The glass substrate (Tempax) was subjected to oxygen plasma treatment using a plasma cleaning device (EXAM, manufactured by Shinko Seiki Co., Ltd.). Thereafter, 3-aminopropyltrimethoxysilane (manufactured by TCI; hereinafter, sometimes referred to as “APTM”) is subjected to a vapor deposition treatment by a closed gas phase method, washed with ethanol and dried, and dried to form an intermediate layer (silane). A glass substrate having a coupling agent layer (hereinafter sometimes referred to as a “glass substrate with an intermediate layer”) was obtained. The intermediate layer had an amino group.
《評価用サンプルの作製》
　中間層付きガラス基板の表面に、機能層形成用組成物をスピンコートした後、８０℃で１時間加熱して評価用サンプルを作製した。 << Preparation of evaluation sample >>
The composition for forming a functional layer was spin-coated on the surface of the glass substrate with an intermediate layer, and then heated at 80 ° C. for 1 hour to prepare a sample for evaluation.
《菌付着抑制性の評価》
　中間層付きガラス基板および評価用サンプルをそれぞれ滅菌シャーレに入れて、ＹＰＤ（ｙｅａｓｔ　ｅｘｔｒａｃｔ　ｐｅｐｔｏｎｅ　ｄｅｘｔｒｏｓｅ）培地にカンジダ・アルビカンス（Ｃａｎｄｉｄａ　ａｌｂｉｃａｎｓ　ＪＣＭ２０８５；「ＪＣＭ」は「Ｊａｐａｎ　Ｃｏｌｌｅｃｔｉｏｎ　ｏｆ　Ｍｉｃｒｏｏｒｇａｎｉｓｍｓ」の略称）の酵母型菌体を接種して、１０００ｃｆｕ／ｍＬとなるように調整した菌液を加えた。
　次に、好気的条件、３７℃で３時間培養し、培養後の試料をＰＢＳ（Ｐｈｏｓｐｈａｔｅ　ｂｕｆｆｅｒｅｄ　ｓａｌｉｎｅ）緩衝液で洗浄した後に、中間層付きガラス基板および評価用サンプルのそれぞれに付着した菌の菌数を、比色定量法（ＸＴＴ法；「ＸＴＴ」は「２，３－ビス－（２－メトキシ－４－ニトロ－５－スルホフェニル）－２Ｈ－テトラゾリウム－５－カルボキサニリド」の略称）によって定量した。中間層付きガラス基板の吸光度を基準とし、評価用サンプルの吸光度の差（吸光度の減少率）を求め、以下の基準により評価した。
　Ａ：基準との差が５０％以上
　Ｂ：基準との差が３０％以上、５０％未満
　Ｃ：基準との差が１０％以上、３０％未満
　Ｄ：基準との差が１０％未満
　表１の「評価」の欄に、菌付着抑制性の評価を示す（「菌付着抑制性」欄）。菌付着抑制性は基準との差が大きいほど菌の付着が少なくて、菌付着抑制性が優れる。 << Evaluation of bacterial adhesion inhibition >>
The glass substrate with an intermediate layer and the sample for evaluation are each placed in a sterile petri dish, and Candida albicans (Candida albicans JCM2085; “JCM” is a yeast of “Japan Collection of Microsomi” or “Mic”) in a Yeast Extract Peptone Dextrose (YPD) medium. The bacterial cells were inoculated and a bacterial solution adjusted to be 1000 cfu / mL was added.
Next, the cells were cultured under aerobic conditions at 37 ° C. for 3 hours, and the cultured samples were washed with a PBS (Phosphate buffered saline) buffer. The number of bacteria was determined by a colorimetric method (XTT method; “XTT” is an abbreviation of “2,3-bis- (2-methoxy-4-nitro-5-sulfophenyl) -2H-tetrazolium-5-carboxanilide”). Quantified. Based on the absorbance of the glass substrate with the intermediate layer as a reference, the difference in absorbance (decrease in absorbance) of the evaluation sample was determined and evaluated according to the following criteria.
A: Difference from reference 50% or more B: Difference from reference 30% or more, less than 50% C: Difference from reference 10% or more, less than 30% D: Difference from reference less than 10% Table 1 In the column of "Evaluation", the evaluation of the bacterial adhesion inhibitory property is shown ("Bacterial adhesive inhibitory" column). The greater the difference between the standard and the standard, the smaller the adhesion of bacteria and the better the inhibition of bacterial adhesion.
《高湿保存安定性の評価》
　中間層付きガラス基板および評価用サンプルを、４０℃、湿度７５％の条件に４８時間暴露した。その後、上述した菌付着抑制性の評価を行い、以下の基準により高湿保存安定性を評価した。
　Ａ：基準との差が５０％以上
　Ｂ：基準との差が３０％以上、５０％未満
　Ｃ：基準との差が１０％以上、３０％未満
　Ｄ：基準との差が１０％未満
　表１の「評価」の欄に、高湿保存安定性の評価を示す（「高湿保存安定性」欄）。高湿保存安定性は基準との差が大きいほど菌の付着量が少なくて、高湿保存安定性に優れる。 << Evaluation of high humidity storage stability >>
The glass substrate with the intermediate layer and the sample for evaluation were exposed to a condition of 40 ° C. and a humidity of 75% for 48 hours. Then, the above-mentioned bacteria adhesion inhibitory property was evaluated, and the high humidity storage stability was evaluated according to the following criteria.
A: Difference from reference 50% or more B: Difference from reference 30% or more, less than 50% C: Difference from reference 10% or more, less than 30% D: Difference from reference less than 10% Table 1 The column of “Evaluation” shows the evaluation of high humidity storage stability (“High humidity storage stability” column). The higher the storage stability under high humidity, the greater the difference from the standard, the smaller the amount of bacteria attached, and the higher the storage stability under high humidity.
〈中間層付きガラス基板の表面の置換基の密度〉
　中間層付きガラス基板の表面の置換基の密度は、上述した方法により測定した。
　詳細には以下のとおりである。
　中間層付きガラス基板を、２，４，６－トリニトロベンゼンスルホン酸（ＴＮＢＳ）で処理し、紫外可視分光光度計（日本分光社製　Ｖ－５５０）を用いて波長４２０ｎｍで吸光度の測定を行い、ＴＮＢＳ分子の密度を算出した。さらに、Ｘ線光電子分光（ＸＰＳ）を用いてＴＮＢＳ由来および未反応の置換基由来のＮ１ｓスペクトルのピーク面積比の測定を行い、置換基の密度を算出した。
　その結果、実施例１～８では、置換基密度１．５ｍｏｌｅｃｕｌｅｓ／ｎｍ２が得られた。 <Substituent density on the surface of the glass substrate with an intermediate layer>
The density of the substituent on the surface of the glass substrate with an intermediate layer was measured by the method described above.
Details are as follows.
The glass substrate with the intermediate layer was treated with 2,4,6-trinitrobenzenesulfonic acid (TNBS), and the absorbance was measured at a wavelength of 420 nm using an ultraviolet-visible spectrophotometer (V-550 manufactured by JASCO Corporation). The density of the TNBS molecule was calculated. Further, the peak area ratio of the N1s spectrum derived from TNBS and the N1s spectrum derived from the unreacted substituent was measured using X-ray photoelectron spectroscopy (XPS) to calculate the density of the substituent.
As a result, in Examples 1 to 8, a substituent density of 1.5 molecules / nm 2 was obtained.
［実施例２］
〈機能層形成用組成物の調製〉
　化合物１に代えて式（Ｂ）で表される化合物２を用いた点を除いて、実施例１と同様にして機能層形成用組成物（以下「機能層形成用組成物２」という場合がある。）を調製した。表１の機能層形成用組成物の欄に、機能層形成用組成物の組成を示す。なお、表１の機能層形成用組成物の欄中、「－」はその成分を用いなかったことを表す。 [Example 2]
<Preparation of composition for forming functional layer>
A composition for forming a functional layer (hereinafter referred to as “functional layer-forming composition 2”) was prepared in the same manner as in Example 1 except that compound 2 represented by formula (B) was used instead of compound 1. ) Was prepared. The column of the composition for forming a functional layer in Table 1 shows the composition of the composition for forming a functional layer. In the column of the composition for forming a functional layer in Table 1, "-" indicates that the component was not used.
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
〈各種評価〉
　機能層形成用組成物１に代えて機能層形成用組成物２を用いた点を除いて、実施例１と同様にして各種評価を実施した。結果を表１の「評価」欄に示す。 <Various evaluations>
Various evaluations were performed in the same manner as in Example 1 except that the composition 2 for forming a functional layer was used instead of the composition 1 for forming a functional layer. The results are shown in the "Evaluation" column of Table 1.
［実施例３］
〈機能層形成用組成物の調製〉
　化合物１に代えて式（Ｃ）で表される化合物３を用いた点を除いて、実施例１と同様にして機能層形成用組成物（以下「機能層形成用組成物３」という場合がある。）を調製した。表１の機能層形成用組成物の欄に、機能層形成用組成物の組成を示す。なお、表１の機能層形成用組成物の欄中、「－」はその成分を用いなかったことを表す。 [Example 3]
<Preparation of composition for forming functional layer>
A composition for forming a functional layer (hereinafter referred to as “composition 3 for forming a functional layer”) was prepared in the same manner as in Example 1 except that the compound 3 represented by the formula (C) was used instead of the compound 1. ) Was prepared. The column of the composition for forming a functional layer in Table 1 shows the composition of the composition for forming a functional layer. In the column of the composition for forming a functional layer in Table 1, "-" indicates that the component was not used.
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
〈各種評価〉
　機能層形成用組成物１に代えて機能層形成用組成物３を用いた点を除いて、実施例１と同様にして各種評価を実施した。結果を表１の「評価」欄に示す。 <Various evaluations>
Various evaluations were performed in the same manner as in Example 1 except that the composition 3 for forming a functional layer was used instead of the composition 1 for forming a functional layer. The results are shown in the "Evaluation" column of Table 1.
［実施例４］
〈機能層形成用組成物の調製〉
　化合物１に代えて式（Ｄ）で表される化合物４を用いた点を除いて、実施例１と同様にして機能層形成用組成物（以下「機能層形成用組成物４」という場合がある。）を調製した。表１の機能層形成用組成物の欄に、機能層形成用組成物の組成を示す。なお、表１の機能層形成用組成物の欄中、「－」はその成分を用いなかったことを表す。 [Example 4]
<Preparation of composition for forming functional layer>
A composition for forming a functional layer (hereinafter referred to as “functional layer-forming composition 4”) was prepared in the same manner as in Example 1 except that the compound 4 represented by the formula (D) was used instead of the compound 1. ) Was prepared. The column of the composition for forming a functional layer in Table 1 shows the composition of the composition for forming a functional layer. In the column of the composition for forming a functional layer in Table 1, "-" indicates that the component was not used.
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
〈各種評価〉
　機能層形成用組成物１に代えて機能層形成用組成物４を用いた点を除いて、実施例１と同様にして各種評価を実施した。結果を表１の「評価」欄に示す。 <Various evaluations>
Various evaluations were performed in the same manner as in Example 1 except that the composition 4 for forming a functional layer was used instead of the composition 1 for forming a functional layer. The results are shown in the "Evaluation" column of Table 1.
［実施例５］
〈機能層形成用組成物の調製〉
　化合物１に代えて式（Ｅ）で表される化合物５を用いた点を除いて、実施例１と同様にして機能層形成用組成物（以下「機能層形成用組成物５」という場合がある。）を調製した。表１の機能層形成用組成物の欄に、機能層形成用組成物の組成を示す。なお、表１の機能層形成用組成物の欄中、「－」はその成分を用いなかったことを表す。 [Example 5]
<Preparation of composition for forming functional layer>
A composition for forming a functional layer (hereinafter referred to as “functional layer-forming composition 5”) was prepared in the same manner as in Example 1 except that compound 5 represented by formula (E) was used instead of compound 1. ) Was prepared. The column of the composition for forming a functional layer in Table 1 shows the composition of the composition for forming a functional layer. In the column of the composition for forming a functional layer in Table 1, "-" indicates that the component was not used.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
〈各種評価〉
　機能層形成用組成物１に代えて機能層形成用組成物５を用いた点を除いて、実施例１と同様にして各種評価を実施した。結果を表１の「評価」欄に示す。 <Various evaluations>
Various evaluations were carried out in the same manner as in Example 1 except that the composition 5 for forming a functional layer was used instead of the composition 1 for forming a functional layer. The results are shown in the "Evaluation" column of Table 1.
［実施例６］
〈機能層形成用組成物の調製〉
　化合物１に代えて式（Ｆ）で表される化合物６を用いた点を除いて、実施例１と同様にして機能層形成用組成物（以下「機能層形成用組成物６」という場合がある。）を調製した。表１の機能層形成用組成物の欄に、機能層形成用組成物の組成を示す。なお、表１の機能層形成用組成物の欄中、「－」はその成分を用いなかったことを表す。 [Example 6]
<Preparation of composition for forming functional layer>
A composition for forming a functional layer (hereinafter referred to as “functional layer-forming composition 6”) was prepared in the same manner as in Example 1 except that compound 6 represented by formula (F) was used instead of compound 1. ) Was prepared. The column of the composition for forming a functional layer in Table 1 shows the composition of the composition for forming a functional layer. In the column of the composition for forming a functional layer in Table 1, "-" indicates that the component was not used.
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
〈各種評価〉
　機能層形成用組成物１に代えて機能層形成用組成物６を用いた点を除いて、実施例１と同様にして各種評価を実施した。結果を表１の「評価」欄に示す。 <Various evaluations>
Various evaluations were performed in the same manner as in Example 1 except that the composition 6 for forming a functional layer was used instead of the composition 1 for forming a functional layer. The results are shown in the "Evaluation" column of Table 1.
［実施例７］
〈機能層形成用組成物の調製〉
　化合物１に代えて式（Ｇ）で表される化合物７を用いた点を除いて、実施例１と同様にして機能層形成用組成物（以下「機能層形成用組成物７」という場合がある。）を調製した。表１の機能層形成用組成物の欄に、機能層形成用組成物の組成を示す。なお、表１の機能層形成用組成物の欄中、「－」はその成分を用いなかったことを表す。 [Example 7]
<Preparation of composition for forming functional layer>
A composition for forming a functional layer (hereinafter referred to as “composition 7 for forming a functional layer”) was prepared in the same manner as in Example 1 except that the compound 7 represented by the formula (G) was used instead of the compound 1. ) Was prepared. The column of the composition for forming a functional layer in Table 1 shows the composition of the composition for forming a functional layer. In the column of the composition for forming a functional layer in Table 1, "-" indicates that the component was not used.
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
〈各種評価〉
　機能層形成用組成物１に代えて機能層形成用組成物７を用いた点を除いて、実施例１と同様にして各種評価を実施した。結果を表１の「評価」欄に示す。 <Various evaluations>
Various evaluations were performed in the same manner as in Example 1, except that the composition 7 for forming a functional layer was used instead of the composition 1 for forming a functional layer. The results are shown in the "Evaluation" column of Table 1.
［実施例８］
〈機能層形成用組成物の調製〉
　化合物１（２５．０質量部）と、化合物３（７０．０質量部）と、水溶性アゾ重合開始剤（ＶＡ－０４６Ｂ，富士フイルム和光純薬社製）（５．０質量部）と、メタノールとを混合し、化合物１と化合物３と水溶性アゾ重合開始剤とをあわせた固形分の含有量が２０質量％となるように機能層形成用組成物（以下「機能層形成用組成物８」という場合がある。）を調製した。表１の機能層形成用組成物の欄に、機能層形成用組成物の組成を示す。なお、表１の機能層形成用組成物の欄中、「－」はその成分を用いなかったことを表す。 Example 8
<Preparation of composition for forming functional layer>
Compound 1 (25.0 parts by mass), Compound 3 (70.0 parts by mass), water-soluble azo polymerization initiator (VA-046B, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (5.0 parts by mass), Methanol is mixed, and the composition for forming a functional layer (hereinafter referred to as the “composition for forming a functional layer”) is mixed so that the solid content of the compound 1, the compound 3, and the water-soluble azo polymerization initiator is 20% by mass. 8 "). The column of the composition for forming a functional layer in Table 1 shows the composition of the composition for forming a functional layer. In the column of the composition for forming a functional layer in Table 1, "-" indicates that the component was not used.
〈各種評価〉
　機能層形成用組成物１に代えて機能層形成用組成物８を用いた点を除いて、実施例１と同様にして各種評価を実施した。結果を表１の「評価」欄に示す。 <Various evaluations>
Various evaluations were performed in the same manner as in Example 1 except that the composition 8 for forming a functional layer was used instead of the composition 1 for forming a functional layer. The results are shown in the "Evaluation" column of Table 1.
［実施例９］
〈機能層形成用組成物の調製〉
　実施例１と同様にして、機能層形成用組成物１を調製した。表１の機能層形成用組成物の欄に、機能層形成用組成物の組成を示す。なお、表１の機能層形成用組成物の欄中、「－」はその成分を用いなかったことを表す。 [Example 9]
<Preparation of composition for forming functional layer>
In the same manner as in Example 1, a composition 1 for forming a functional layer was prepared. The column of the composition for forming a functional layer in Table 1 shows the composition of the composition for forming a functional layer. In the column of the composition for forming a functional layer in Table 1, "-" indicates that the component was not used.
〈各種評価〉
　ＡＰＴＭに代えて、３－メルカプトプロピルトリメトキシシラン（ＴＣＩ社製；以下「ＭＰＴＭ」という場合がある。）を用いた点を除いて、実施例１と同様にして各種評価を実施した。結果を表１の「評価」欄に示す。 <Various evaluations>
Various evaluations were performed in the same manner as in Example 1 except that 3-mercaptopropyltrimethoxysilane (manufactured by TCI; hereinafter, sometimes referred to as “MPTM”) was used instead of APTM. The results are shown in the "Evaluation" column of Table 1.
［比較例１］
〈各種評価〉
　ガラス基板（テンパックス）上に中間層を形成せず、さらに、機能層も形成しなかった点を除いて、実施例１と同様にして各種評価を実施した。結果を表１の「評価」欄に示す。 [Comparative Example 1]
<Various evaluations>
Various evaluations were performed in the same manner as in Example 1 except that no intermediate layer was formed on the glass substrate (Tempax) and no functional layer was formed. The results are shown in the "Evaluation" column of Table 1.
［比較例２］
〈各種評価〉
　ガラス基板（テンパックス）上に中間層を形成しなかった点を除いて、実施例１と同様にして各種評価を実施した。結果を表１の「評価」欄に示す。 [Comparative Example 2]
<Various evaluations>
Various evaluations were performed in the same manner as in Example 1 except that the intermediate layer was not formed on the glass substrate (Tempax). The results are shown in the "Evaluation" column of Table 1.
Figure JPOXMLDOC01-appb-T000040
Figure JPOXMLDOC01-appb-T000040
　実施例１～９の積層体は、菌付着抑制性に優れていた。
　実施例１～９のうちでも、機能層形成用組成物が化合物５を含む実施例５および化合物６を含む実施例６、ならびに、化合物３および化合物１を含む実施例８は、菌付着抑制性および高湿保存安定性のいずれもが優れていた。 The laminates of Examples 1 to 9 were excellent in inhibiting bacterial adhesion.
Among Examples 1 to 9, Examples 5 and 6 in which the composition for forming a functional layer contains Compound 5 and Example 6 in which Compound 6 contains Compound 6, and Examples 8 in which the composition for forming a functional layer contains Compound 3 and Compound 1 show the ability to inhibit bacterial adhesion. And the storage stability at high humidity were both excellent.

Claims (7)

  1. 　基材の表面の少なくとも一部に、重合性基と反応する置換基を有する中間層を配置する前処理工程と、
    　重合性基を有するモノマーを含む機能層形成用組成物を用いて、前記中間層の少なくとも一部を被覆する被覆層を形成する被覆層形成工程と、
    　前記被覆層を硬化させて機能層を形成する硬化工程と
    を含み、
    　前記重合性基を有するモノマーが、
    　式（ＩＶ）で表される化合物、式（Ｖ）で表される化合物、式（ＶＩ）で表される化合物、式（ＶＩＩ）で表される化合物、式（Ｉ）で表される化合物、式（ＩＩ）で表される化合物、および、式（ＶＩＩＩ）で表される化合物からなる群から選択される少なくとも１種である、
    積層体の製造方法。
    Figure JPOXMLDOC01-appb-C000001
     　式（ＩＶ）中、Ｒ４１はメチル基、エチル基、プロピル基またはプロパン－２－イル基を表し、複数のＲ４１は互いに同じであってもよいし異なっていてもよく、Ｒ４２は水素原子またはメチル基を表し、Ｒ４３は－ＮＨ－または－Ｏ－を表し、ｎ４は１～４の整数を表し、ｌ４は１～４の整数を表し、Ｍ４はＳＯ３ －またはＣＯＯ－を表す。
    Figure JPOXMLDOC01-appb-C000002
     　式（Ｖ）中、Ｒ５１はメチル基、エチル基、プロピル基またはプロパン－２－イル基を表し、複数のＲ５１は互いに同じであってもよいし異なっていてもよく、Ｒ５２は水素原子またはメチル基を表し、ｎ５は１～４の整数を表し、Ｌ５１は炭素数３または４の直鎖状または分岐鎖状のアルキレン基を表し、Ｍ５はＳＯ３ －またはＣＯＯ－を表す。
    Figure JPOXMLDOC01-appb-C000003
     　式（ＶＩ）中、Ｒ６１は水素原子またはメチル基を表す。
    Figure JPOXMLDOC01-appb-C000004
     　式（ＶＩＩ）中、Ｒ７１およびＲ７２は、それぞれ独立に、水素原子またはメチル基を表し、ｎは１～１００の整数を表す。
    Figure JPOXMLDOC01-appb-C000005
     　式（Ｉ）中、Ｒは水素原子またはメチル基を表し、複数のＲは互いに同じであってもよいし異なっていてもよく、Ｌは－Ｏ－、炭素数２～４の直鎖状または分岐鎖状のアルキレン基およびこれらのうち２種以上の組合せからなる群から選択されるいずれか１種の２価の連結基を表し、複数のＬは互いに同じであってもよいし異なっていてもよい。
    Figure JPOXMLDOC01-appb-C000006
     　式（ＩＩ）中、Ｒ１は水素原子またはメチル基を表し、Ｒ２およびＲ４は、それぞれ独立に、－Ｏ－、炭素数１～４の直鎖状または分岐鎖状のアルキレン基およびこれらのうち２種以上の組合せからなる群から選択されるいずれか１種の２価の連結基を表し、Ｒ３は－Ｏ－、炭素数１～４の直鎖状または分岐鎖状のアルキレン基、式（ＩＩＩ）で表される基およびこれらのうち２種以上の組合せからなる群から選択されるいずれか１種の２価の連結基を表し、Ｌ１およびＬ２は、それぞれ独立に、単結合または式（ＩＩＩ）で表される基を表す。
    Figure JPOXMLDOC01-appb-C000007
     　式（ＩＩＩ）中、Ｒ３１は水素原子またはメチル基を表し、＊は他の原子との結合箇所を表す。
    Figure JPOXMLDOC01-appb-C000008
     　式（ＶＩＩＩ）中、Ｒ８１およびＲ８２は、それぞれ独立に、水素原子またはメチル基を表し、ｎは１～１０の整数を表す。     Pretreatment step of arranging an intermediate layer having a substituent that reacts with a polymerizable group on at least a part of the surface of the substrate,
    Using a composition for forming a functional layer containing a monomer having a polymerizable group, a coating layer forming step of forming a coating layer that covers at least a part of the intermediate layer,
    Curing step of curing the coating layer to form a functional layer,
    The monomer having a polymerizable group,
    A compound represented by the formula (IV), a compound represented by the formula (V), a compound represented by the formula (VI), a compound represented by the formula (VII), a compound represented by the formula (I), At least one selected from the group consisting of a compound represented by the formula (II) and a compound represented by the formula (VIII),
    A method for manufacturing a laminate.
    Figure JPOXMLDOC01-appb-C000001
     In the formula (IV), R 41 represents a methyl group, an ethyl group, a propyl group or a propan-2-yl group, a plurality of R 41 may be the same or different, and R 42 is hydrogen Represents an atom or a methyl group, R 43 represents —NH— or —O—, n4 represents an integer of 1 to 4, 14 represents an integer of 1 to 4, and M 4 represents SO 3 — or COO − . Represent.
    Figure JPOXMLDOC01-appb-C000002
     In the formula (V), R 51 represents a methyl group, an ethyl group, a propyl group or a propan-2-yl group, a plurality of R 51 may be the same or different, and R 52 is hydrogen. Represents an atom or a methyl group, n5 represents an integer of 1 to 4, L 51 represents a linear or branched alkylene group having 3 or 4 carbon atoms, and M 5 represents SO 3 — or COO − . .
    Figure JPOXMLDOC01-appb-C000003
     In the formula (VI), R 61 represents a hydrogen atom or a methyl group.
    Figure JPOXMLDOC01-appb-C000004
     In the formula (VII), R 71 and R 72 each independently represent a hydrogen atom or a methyl group, and n represents an integer of 1 to 100.
    Figure JPOXMLDOC01-appb-C000005
     In the formula (I), R represents a hydrogen atom or a methyl group, a plurality of Rs may be the same or different, L is —O—, a linear group having 2 to 4 carbon atoms or Represents one type of divalent linking group selected from the group consisting of a branched alkylene group and a combination of two or more types thereof, and a plurality of Ls may be the same or different; Is also good.
    Figure JPOXMLDOC01-appb-C000006
     In the formula (II), R 1 represents a hydrogen atom or a methyl group, and R 2 and R 4 each independently represent —O—, a linear or branched alkylene group having 1 to 4 carbon atoms, Represents any one of divalent linking groups selected from the group consisting of two or more of the following, and R 3 is —O—, a linear or branched alkylene group having 1 to 4 carbon atoms. , And any one of divalent linking groups selected from the group consisting of a group represented by the formula (III) and a combination of two or more of them; L 1 and L 2 each independently represent Represents a single bond or a group represented by the formula (III).
    Figure JPOXMLDOC01-appb-C000007
     In the formula (III), R 31 represents a hydrogen atom or a methyl group, and * represents a bonding position to another atom.
    Figure JPOXMLDOC01-appb-C000008
     In the formula (VIII), R 81 and R 82 each independently represent a hydrogen atom or a methyl group, and n represents an integer of 1 to 10.
  2. 　前記重合性基と反応する置換基が、アミノ基、チオール基およびビニル基からなる群から選択される少なくとも１種を有する、請求項１に記載の積層体の製造方法。 The method according to claim 1, wherein the substituent that reacts with the polymerizable group has at least one selected from the group consisting of an amino group, a thiol group, and a vinyl group.
  3. 　前記基材が、前記中間層と共有結合し得る置換基をその表面に有する、請求項１または２に記載の積層体の製造方法。 方法 The method for producing a laminate according to claim 1 or 2, wherein the base material has on its surface a substituent capable of covalently bonding to the intermediate layer.
  4. 　前記重合性基と反応する置換基の密度が、０．１ｍｏｌｅｃｕｌｅｓ／ｎｍ２以上である、請求項１～３のいずれか１項に記載の積層体の製造方法。 4. The method for producing a laminate according to claim 1, wherein the density of the substituent that reacts with the polymerizable group is 0.1 molecules / nm 2 or more.
  5. 　前記重合性基を有するモノマーが、式（Ｅ）で表される化合物、式（Ｆ）で表わされる化合物、または、式（Ａ）で表される化合物と式（Ｃ）で表される化合物との組合せである、請求項１～４のいずれか１項に記載の積層体の製造方法。
    Figure JPOXMLDOC01-appb-C000009
    Figure JPOXMLDOC01-appb-C000010
    Figure JPOXMLDOC01-appb-C000011
    Figure JPOXMLDOC01-appb-C000012
         The monomer having a polymerizable group is a compound represented by the formula (E), a compound represented by the formula (F), or a compound represented by the formula (A) and a compound represented by the formula (C). The method for producing a laminate according to any one of claims 1 to 4, which is a combination of the following.
    Figure JPOXMLDOC01-appb-C000009
    Figure JPOXMLDOC01-appb-C000010
    Figure JPOXMLDOC01-appb-C000011
    Figure JPOXMLDOC01-appb-C000012
  6. 　基材と、前記基材の表面の少なくとも一部に配置された中間層と、前記中間層の前記基材の側とは反対側の面の少なくとも一部に配置された機能層とを有する積層体であって、
    　前記機能層は、重合性基を有するモノマーを含む機能層形成用組成物を硬化させた層であり、
    　前記中間層と前記機能層とは共有結合で結合しており、
    　前記重合性基を有するモノマーが、
    　式（ＩＶ）で表される化合物、式（Ｖ）で表される化合物、式（ＶＩ）で表される化合物、式（ＶＩＩ）で表される化合物、式（Ｉ）で表される化合物、（ＩＩ）で表される化合物、および、式（ＶＩＩＩ）で表される化合物からなる群から選択される少なくとも１種である、
    積層体。
    Figure JPOXMLDOC01-appb-C000013
     　式（ＩＶ）中、Ｒ４１はメチル基、エチル基、プロピル基またはプロパン－２－イル基を表し、複数のＲ４１は互いに同じであってもよいし異なっていてもよく、Ｒ４２は水素原子またはメチル基を表し、ｎ４は１～４の整数を表し、ｌ４は１～４の整数を表し、Ｍ４はＳＯ３ －またはＣＯＯ－を表す。
    Figure JPOXMLDOC01-appb-C000014
     　式（Ｖ）中、Ｒ５１はメチル基、エチル基、プロピル基またはプロパン－２－イル基を表し、複数のＲ５１は互いに同じであってもよいし異なっていてもよく、Ｒ５２は水素原子またはメチル基を表し、ｎ５は１～４の整数を表し、Ｌ５１は炭素数３または４の直鎖状または分岐鎖状のアルキレン基を表し、Ｍ５はＳＯ３ －またはＣＯＯ－を表す。
    Figure JPOXMLDOC01-appb-C000015
     　式（ＶＩ）中、Ｒ６１は水素原子またはメチル基を表す。
    Figure JPOXMLDOC01-appb-C000016
     　式（ＶＩＩ）中、Ｒ７１およびＲ７２は、それぞれ独立に、水素原子またはメチル基を表し、ｎは１～１００の整数を表す。
    Figure JPOXMLDOC01-appb-C000017
     　式（Ｉ）中、Ｒは水素原子またはメチル基を表し、複数のＲは互いに同じであってもよいし異なっていてもよく、Ｌは－Ｏ－、炭素数２～４の直鎖状または分岐鎖状のアルキレン基およびこれらのうち２種以上の組合せからなる群から選択されるいずれか１種の２価の連結基を表す。
    Figure JPOXMLDOC01-appb-C000018
     　式（ＩＩ）中、Ｒ１は水素原子またはメチル基を表し、Ｒ２およびＲ４は、それぞれ独立に、－Ｏ－、炭素数１～４の直鎖状または分岐鎖状のアルキレン基およびこれらのうち２種以上の組合せからなる群から選択されるいずれか１種の２価の連結基を表し、Ｒ３は－Ｏ－、炭素数１～４の直鎖状または分岐鎖状のアルキレン基、式（ＩＩＩ）で表される基およびこれらのうち２種以上の組合せからなる群から選択されるいずれか１種の２価の連結基を表し、Ｌ１およびＬ２は、それぞれ独立に、単結合または式（ＩＩＩ）で表される基を表す。
    Figure JPOXMLDOC01-appb-C000019
     　式（ＩＩＩ）中、Ｒ３１は水素原子またはメチル基を表し、＊は他の原子との結合箇所を表す。
    Figure JPOXMLDOC01-appb-C000020
     　式（ＶＩＩＩ）中、Ｒ８１およびＲ８２は、それぞれ独立に、水素原子またはメチル基を表し、ｎは１～１０の整数を表す。     A laminate having a substrate, an intermediate layer disposed on at least a part of the surface of the substrate, and a functional layer disposed on at least a part of a surface of the intermediate layer opposite to the substrate. Body
    The functional layer is a layer obtained by curing a composition for forming a functional layer containing a monomer having a polymerizable group,
    The intermediate layer and the functional layer are covalently bonded,
    The monomer having a polymerizable group,
    A compound represented by the formula (IV), a compound represented by the formula (V), a compound represented by the formula (VI), a compound represented by the formula (VII), a compound represented by the formula (I), At least one selected from the group consisting of a compound represented by (II) and a compound represented by formula (VIII):
    Laminate.
    Figure JPOXMLDOC01-appb-C000013
     In the formula (IV), R 41 represents a methyl group, an ethyl group, a propyl group or a propan-2-yl group, a plurality of R 41 may be the same or different, and R 42 is hydrogen represents an atom or a methyl group, n4 is an integer of 1 ~ 4, l4 represents an integer of 1 ~ 4, M 4 is SO 3 - represents an - or COO.
    Figure JPOXMLDOC01-appb-C000014
     In the formula (V), R 51 represents a methyl group, an ethyl group, a propyl group or a propan-2-yl group, a plurality of R 51 may be the same or different, and R 52 is hydrogen. Represents an atom or a methyl group, n5 represents an integer of 1 to 4, L 51 represents a linear or branched alkylene group having 3 or 4 carbon atoms, and M 5 represents SO 3 — or COO − . .
    Figure JPOXMLDOC01-appb-C000015
     In the formula (VI), R 61 represents a hydrogen atom or a methyl group.
    Figure JPOXMLDOC01-appb-C000016
     In the formula (VII), R 71 and R 72 each independently represent a hydrogen atom or a methyl group, and n represents an integer of 1 to 100.
    Figure JPOXMLDOC01-appb-C000017
     In the formula (I), R represents a hydrogen atom or a methyl group, a plurality of Rs may be the same or different, L is —O—, a linear group having 2 to 4 carbon atoms or It represents any one type of divalent linking group selected from the group consisting of a branched alkylene group and a combination of two or more of these.
    Figure JPOXMLDOC01-appb-C000018
     In the formula (II), R 1 represents a hydrogen atom or a methyl group, and R 2 and R 4 each independently represent —O—, a linear or branched alkylene group having 1 to 4 carbon atoms, Represents any one of divalent linking groups selected from the group consisting of two or more of the following, and R 3 is —O—, a linear or branched alkylene group having 1 to 4 carbon atoms. , And any one of divalent linking groups selected from the group consisting of a group represented by the formula (III) and a combination of two or more of them; L 1 and L 2 each independently represent Represents a single bond or a group represented by the formula (III).
    Figure JPOXMLDOC01-appb-C000019
     In the formula (III), R 31 represents a hydrogen atom or a methyl group, and * represents a bonding position to another atom.
    Figure JPOXMLDOC01-appb-C000020
     In the formula (VIII), R 81 and R 82 each independently represent a hydrogen atom or a methyl group, and n represents an integer of 1 to 10.
  7. 　前記中間層と前記基材とが共有結合により結合している、請求項６に記載の積層体。 The laminate according to claim 6, wherein the intermediate layer and the base material are bonded by a covalent bond.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022209922A1 (en) * 2021-03-31 2022-10-06 富士フイルム株式会社 Curable composition, hardcoat film, and product, image display device, and flexible display including hardcoat film

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02152915A (en) * 1988-12-01 1990-06-12 Sankin Kogyo Kk Dental adhesive composition and adhesion method
WO2014041940A1 (en) * 2012-09-14 2014-03-20 富士フイルム株式会社 Curable composition and image-forming method
JP2014055115A (en) * 2012-09-11 2014-03-27 Sun Medical Co Ltd Dental composition
WO2017135186A1 (en) * 2016-02-01 2017-08-10 富士フイルム株式会社 Root canal treatment material and kit for root canal treatment
WO2018038270A1 (en) * 2016-08-26 2018-03-01 三井化学株式会社 Antifog laminate
WO2018143051A1 (en) * 2017-01-31 2018-08-09 富士フイルム株式会社 Denture base coating composition, coating film-bearing denture base, plate denture, and method for producing coating film-bearing denture base
WO2018155578A1 (en) * 2017-02-27 2018-08-30 リンテック株式会社 Hydrophilic composition and hydrophilic structure
WO2018212061A1 (en) * 2017-05-16 2018-11-22 富士フイルム株式会社 Laminate, kit, and method for producing laminate

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02152915A (en) * 1988-12-01 1990-06-12 Sankin Kogyo Kk Dental adhesive composition and adhesion method
JP2014055115A (en) * 2012-09-11 2014-03-27 Sun Medical Co Ltd Dental composition
WO2014041940A1 (en) * 2012-09-14 2014-03-20 富士フイルム株式会社 Curable composition and image-forming method
WO2017135186A1 (en) * 2016-02-01 2017-08-10 富士フイルム株式会社 Root canal treatment material and kit for root canal treatment
WO2018038270A1 (en) * 2016-08-26 2018-03-01 三井化学株式会社 Antifog laminate
WO2018143051A1 (en) * 2017-01-31 2018-08-09 富士フイルム株式会社 Denture base coating composition, coating film-bearing denture base, plate denture, and method for producing coating film-bearing denture base
WO2018155578A1 (en) * 2017-02-27 2018-08-30 リンテック株式会社 Hydrophilic composition and hydrophilic structure
WO2018212061A1 (en) * 2017-05-16 2018-11-22 富士フイルム株式会社 Laminate, kit, and method for producing laminate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ANONYMOUS: "Colcoat N-103X, Colcoat PX", COLCOAT, April 2018 (2018-04-01), XP055700130, Retrieved from the Internet <URL:https://www.colcoat.co.jp/wp/wp-content/uploads/2018/04/kinousei_01.pdf> [retrieved on 20191105] *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022209922A1 (en) * 2021-03-31 2022-10-06 富士フイルム株式会社 Curable composition, hardcoat film, and product, image display device, and flexible display including hardcoat film

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