Epoxy resin adhesives for medical devices and their cured products, as well as medical device components and medical devices

Abstract

An epoxy resin adhesive for medical instruments which comprises the following components (A) to (C); a cured object obtained from the epoxy resin adhesive; a medical-instrument member; and a medical instrument.　(A) An epoxy resin (B) A polyamine compound having two or more unsubstituted amino groups (C) A compound having a nonaromatic carbon-carbon double bond and a phenolic hydroxyl group

Description

[Technical Field]

[0001] The present invention relates to an epoxy resin adhesive for medical devices, a cured product thereof, a medical device component, and a medical device. [Background technology]

[0002] Among adhesives, epoxy adhesives are excellent in workability and also have excellent adhesive properties, electrical properties, heat resistance, moisture resistance, etc. of the cured product. For this reason, epoxy adhesives are used in a variety of fields, and their use for fixing components of medical devices is also being considered. Medical devices used to examine or treat the human body require a high level of cleanliness, and must be washed and disinfected with chemicals after each use. In particular, medical devices inserted into or applied to blood vessels, trachea, digestive tract, and other body cavities or tissues require a high level of cleanliness that goes beyond disinfection to prevent bacterial infection. Sterilization using EOG (ethylene oxide gas) is widely used as such a sterilization process, and the application of hydrogen peroxide plasma treatment is also becoming desirable. For example, Patent Document 1 describes an endoscope adhesive containing an epoxy resin containing at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, and phenol novolac epoxy resin, a curing component, and an acid-based curing accelerator. According to the technology described in Patent Document 1, the cured product obtained by the curing reaction of the endoscope adhesive has excellent gas barrier properties against sterilization gas, and is resistant to deterioration even when repeatedly exposed to sterilization gas. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2020 / 175272 Summary of the Invention [Problem to be solved by the invention]

[0004] Some medical devices are used repeatedly over long periods of time, and the state in which the components are fixed by the adhesive must be able to be maintained sufficiently even after the medical device is used repeatedly over long periods of time. In other words, the adhesive must not only have excellent gas barrier properties, but also have durability that allows the fixed state to be maintained sufficiently even when the medical device is repeatedly immersed in a disinfectant solution or subjected to repeated sterilization treatments.

[0005] The present invention aims to provide an epoxy resin adhesive for medical devices that is suitable for fixing components of medical devices, and that has a sufficiently high level of the properties required of ordinary adhesives (work life and shape retention before curing), as well as rapid curing properties and viscosity suitable for the manufacture of medical devices. Another objective of the present invention is to provide an adhesive and a cured product thereof in which the cured product obtained by the curing reaction is resistant to deterioration even when repeatedly immersed in a disinfectant solution and is resistant to loss of adhesive strength even when subjected to repeated sterilization treatments. Another objective of the present invention is to provide a medical device component comprising the cured product, which is suitable as a component of a medical device, and a medical device comprising the medical device component. [Means for solving the problem]

[0006] The above-mentioned problems of the present invention have been solved by the following means. <1> An epoxy resin adhesive for medical devices, comprising the following components (A) to (C): (A) Epoxy resin (B) Polyamine compound having two or more unsubstituted amino groups (C) Compounds having a non-aromatic carbon-carbon double bond group and a phenolic hydroxyl group <2> the non-aromatic carbon-carbon double bond group comprises a vinyl group; <1> Epoxy resin adhesive for medical devices according to claim 1. <3> The component (C) contains a compound having an average polymerization degree of 2 or more. <1> or <2> Epoxy resin adhesive for medical devices according to claim 1. <4> the component (C) contains a compound having a substituent at the ortho position relative to the carbon atom constituting the aromatic hydrocarbon ring to which the phenolic hydroxyl group is bonded; <1> ~ <3> 10. An epoxy resin adhesive for medical devices according to any one of the preceding items. <5> <1> ~ <4> 2. A cured product obtained by curing the epoxy resin adhesive for medical devices according to any one of the preceding items. <6> It has a metal substrate, <5> 10. A medical device component having the cured product according to claim 1 on the metal substrate. <7> The metal substrate is a stainless steel substrate. <6> A medical device component according to claim 1. <8> <5> A medical device having components fixed by the cured product according to claim 1. <9> <6> or <7> A medical device using the medical device member described in 1 as a constituent member. <10> It is an endoscope, <8> or <9> The medical device described in

[0007] In the present invention, the phenolic hydroxyl group means a hydroxyl group bonded to a ring-constituting carbon atom of an aromatic hydrocarbon ring. In the present invention, when there are multiple substituents or linking groups, etc. (hereinafter referred to as substituents, etc.) represented by a specific symbol or formula, or when multiple substituents, etc. are specified simultaneously, unless otherwise specified, the respective substituents, etc. may be the same or different from each other. The same applies to the specification of the number of substituents, etc. Furthermore, when multiple substituents, etc. are adjacent to each other (especially when they are adjacent), they may be linked to each other to form a ring, unless otherwise specified. Furthermore, unless otherwise specified, rings, such as alicyclic rings, aromatic rings, and heterocyclic rings, may be further condensed to form a condensed ring. In the present invention, unless otherwise specified, when double bonds exist in a molecule in the E-type or Z-type, they may be either one or a mixture thereof. In addition, it also means that the structure may be partially modified as long as the effect of the present invention is not impaired. Furthermore, for compounds that are not specified as substituted or unsubstituted, it means that any substituent may be present as long as the effect of the present invention is not impaired. This also applies to substituents and linking groups. Among such optional substituents, preferred substituents in the present invention are those selected from the substituent group T described below. In the present invention, the numerical values ​​before and after the upper limit are used in the sense that they include the lower limit and upper limit. [Effects of the Invention]

[0008] The epoxy resin adhesive for medical devices of the present invention possesses the various properties required of ordinary adhesives (such as pot life and shape retention before curing) at a sufficiently high level, has rapid curing properties and viscosity suitable for the manufacture of medical devices, and the cured product obtained by the curing reaction is resistant to deterioration even when repeatedly immersed in disinfectant solutions and is resistant to loss of adhesive strength even when repeatedly subjected to sterilization treatments. Furthermore, the cured product of the present invention and medical device components of the present invention containing this cured product are resistant to deterioration even when repeatedly immersed in disinfectant solutions and are resistant to loss of adhesive strength even when repeatedly subjected to sterilization treatments, making them suitable as components of medical devices. Therefore, medical devices of the present invention equipped with the above-mentioned medical device components have excellent chemical resistance and sterilization durability and are resistant to loss of performance. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a cross-sectional view showing a schematic diagram of one embodiment of a medical device component of the present invention. [Figure 2] FIG. 2 is a cross-sectional view showing a schematic diagram of a test piece prepared in an example. DETAILED DESCRIPTION OF THE INVENTION

[0010] [Epoxy resin adhesive for medical devices] A preferred embodiment of the epoxy resin adhesive for medical devices of the present invention will be described.

[0011] The epoxy resin adhesive for medical devices of the present invention (hereinafter also referred to as "the adhesive of the present invention") comprises (A) an epoxy resin, (B) a polyamine compound having two or more unsubstituted amino groups, and (C) a compound having a non-aromatic carbon-carbon double bond group and a phenolic hydroxyl group. The epoxy resin (A) (hereinafter referred to simply as "component (A)") is the main component of the adhesive, and the polyamine compound (B) (hereinafter referred to simply as "component (B)") is a curing component that reacts with the epoxy resin to cure the adhesive. The compound (C) having a non-aromatic carbon-carbon double bond group and a phenolic hydroxyl group (hereinafter referred to simply as "component (C)") activates the epoxy groups in the epoxy resin, thereby promoting the curing reaction of the epoxy resin with component (B) and simultaneously forming a self-polymer of the epoxy resin itself. In the adhesive of the present invention, the blend amount of the compound (C) having a non-aromatic carbon-carbon double bond group and a phenolic hydroxyl group is typically less than that of the curing component (B) by mass.

[0012] The adhesive of the present invention is not limited in its form as long as it contains the above-mentioned components. For example, the adhesive of the present invention may be in a form containing a mixture of the above-mentioned components (A) to (C) (one-component type), or may contain the above-mentioned components (A) to (C) in a state where some of the components (A) to (C) are separated from the other components (two-component type). Furthermore, the adhesive of the present invention may contain the components (A) to (C) in a state where each of the components (A) to (C) is separated from each other (three-component type). All of these forms are encompassed by the adhesive of the present invention. When describing the content of each component in an adhesive herein or specifying the content of each component in an adhesive in the present invention, in the case of a two-component or three-component adhesive, this means that, in the case of a two-component or three-component adhesive, components (A) to (C) are mixed at the time of use so that the desired content of each component is achieved in the mixture. That is, in the case of a two-component or three-component adhesive, when the components are separated, the content of each of components (A) to (C) does not need to satisfy the content described herein or the content specified in the present invention. That is, in the case of a two-component or three-component adhesive, this means that the content described herein or the content specified in the present invention is achieved when components (A) to (C) are mixed at the time of use.

[0013] When the adhesive for endoscopes of the present invention is a one-component type, or when it is a two-component type containing components that may react with each other (for example, a mixture of an epoxy resin and a curing component), it is preferable to store the adhesive at a low temperature at which the adhesive does not substantially react, in order to prevent or sufficiently suppress reactions between the components and maintain the stability of each component. For example, it can be stored at -20°C or below, preferably -30°C or below, more preferably -40°C or below, and even more preferably -50°C or below. It can also be stored in a light-shielded condition, if necessary.

[0014] The adhesive of the present invention can contain, for example, solvents, plasticizers, adhesion improvers (silane coupling agents, etc.), surfactants, colorants (pigments, dyes, etc.), weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, brighteners, mold release agents, conductive agents, viscosity adjusters, fillers (silica, calcium carbonate, etc.), thixotropy-imparting agents, diluents, and flame retardants, as long as the effects of the present invention are not impaired.

[0015] The epoxy resin adhesive for medical devices of the present invention has a sufficiently high level of the various properties required of ordinary adhesives (working life and shape retention before hardening), and also has rapid hardening properties and viscosity suitable for the manufacture of medical devices.Furthermore, the hardened product obtained by the hardening reaction is resistant to deterioration even when repeatedly immersed in a disinfectant solution, and is resistant to a decrease in adhesive strength even when subjected to repeated sterilization treatments. The reasons why the epoxy resin adhesive for medical devices of the present invention has rapid curing properties and viscosity suitable for the manufacture of medical devices, and further why the cured product obtained by the curing reaction is resistant to deterioration even when repeatedly immersed in disinfectant solutions and is resistant to a decrease in adhesive strength even when subjected to repeated sterilization treatments are not clear, but are presumed to be as follows. That is, the epoxy resin adhesive for medical devices of the present invention contains a combination of an amine-based curing agent (component (B)) with excellent rapid curing properties and a compound (component (C)) with a phenolic hydroxyl group that has cure-accelerating properties, thereby achieving a high level of rapid curing properties suitable for the manufacture of medical devices. Furthermore, it is presumed that the hydrogen bonding interaction between the amino group and the phenolic hydroxyl group of the amine-based curing agent restricts the movement of molecules, thereby achieving a viscosity suitable for the manufacture of medical devices. Furthermore, the epoxy resin adhesive for medical devices of the present invention has a strong network derived from the hydrogen bonding interaction between the amino group of the amine-based curing agent and the phenolic hydroxyl group, which makes it difficult for the components of the disinfectant to penetrate into the cured product, and it is presumed that the cured product obtained by the curing reaction is unlikely to deteriorate even if repeatedly immersed in the disinfectant (it has excellent chemical resistance). When a cured product of the epoxy-based adhesive of the present invention is subjected to a sterilization treatment such as hydrogen peroxide plasma treatment, alkyl radicals are generated from the cured product, and these alkyl radicals react with oxygen to generate peroxy radicals. Alkyl radicals are highly reactive with oxygen and quickly become peroxy radicals upon generation. In the cured product of the epoxy resin adhesive for medical devices of the present invention, compounds having non-aromatic carbon-carbon double bond groups and phenolic hydroxyl groups are thought to be present in the vicinity of the epoxy resin network due to the interaction between the phenolic hydroxyl groups and amino groups. Therefore, the alkyl radicals and non-aromatic carbon-carbon double bond groups can effectively react to capture the alkyl radicals, and even if peroxy radicals are generated, they can be captured by the phenolic hydroxyl groups. This is presumably one of the reasons why the cured product is able to maintain its adhesive strength even after repeated sterilization treatments, thereby suppressing deterioration (excellent sterilization durability).

[0016] The adhesive of the present invention is primarily used to fasten various components (medical device components) that make up a medical device. That is, the adhesive of the present invention is used to bond a medical device component to another medical device component, thereby fastening the medical device component to another medical device component. The adhesive used to fasten the medical device components becomes a cured product, which forms the adhesive portion of the medical device. There are no particular limitations on the components that can be fixed using the adhesive of the present invention, and preferred examples include metal components, glass components, and resin components. The "fixing" of a medical device component is achieved by adhering the medical device component to another component (supporting member) that constitutes the medical device. The supporting member may be a tube wall or the like of the medical device or a non-movable member fixed to the tube wall or the like, or it may be a member whose relative position within the medical device can move, such as a tube. In the present invention, the term "fixing" is used to mean filling, i.e., sealing, the space between the medical device component and the supporting member into which this component is incorporated with a cured product of the adhesive. Furthermore, the cured product of the adhesive of the present invention can also be used as a medical device component. Each component constituting the adhesive of the present invention will be described below.

[0017] <(A) Epoxy resin> The adhesive of the present invention contains an epoxy resin as component (A), and this epoxy resin preferably contains at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, and phenol novolac epoxy resin. The adhesive of the present invention may contain one or more epoxy resins selected from bisphenol A epoxy resin, bisphenol F epoxy resin, and phenol novolac epoxy resin. The proportion of the total amount of bisphenol A epoxy resin, bisphenol F epoxy resin, and phenol novolac epoxy resin in the total amount of epoxy resins contained in the adhesive of the present invention is preferably 70 mass% or more, more preferably 80 mass% or more, and even more preferably 90 mass% or more. The epoxy resin contained in the adhesive of the present invention is particularly preferably at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, and phenol novolac epoxy resin. The epoxy equivalent of the epoxy resin contained in the adhesive of the present invention is preferably from 10 to 1000, more preferably from 50 to 500, even more preferably from 80 to 400, and particularly preferably from 100 to 300. The epoxy resin contained in the adhesive of the present invention usually has two or more epoxy groups in one molecule. The epoxy equivalent is a value obtained by dividing the molecular weight of an epoxy compound by the number of moles of epoxy groups contained in the epoxy compound.

[0018] The bisphenol A epoxy resin that can be used in the adhesive of the present invention is not particularly limited, and a wide variety of resins commonly used as the base agent for epoxy adhesives can be used. Preferred examples include bisphenol A diglycidyl ether (jER825, jER828, and jER834 (all trade names), manufactured by Mitsubishi Chemical Corporation) and bisphenol A propoxylate diglycidyl ether (manufactured by Sigma-Aldrich).

[0019] The bisphenol F epoxy resin that can be used in the adhesive of the present invention is not particularly limited, and a wide variety of resins commonly used as the base agent for epoxy adhesives can be used. Preferred examples include bisphenol F diglycidyl ether (trade name: EPICLON 830, manufactured by DIC Corporation) and 4,4'-methylenebis(N,N-diglycidylaniline).

[0020] The phenol novolac epoxy resin that can be used in the adhesive of the present invention is not particularly limited, and any resin generally used as a base agent for epoxy adhesives can be used. Such a phenol novolac epoxy resin is commercially available, for example, from Sigma-Aldrich under product number 406775.

[0021] The content of the epoxy resin in the adhesive of the present invention can be 5 to 90 mass %, and more preferably 10 to 75 mass %.

[0022] <(B) Polyamine Compound Having Two or More Unsubstituted Amino Groups> The adhesive of the present invention contains, as component (B), a polyamine compound having two or more unsubstituted amino groups (hereinafter, "a polyamine compound having two or more unsubstituted amino groups" may also be simply referred to as "a polyamine compound.") The adhesive of the present invention may contain one type of component (B) alone, or two or more types in combination. The polyamine compound is more preferably a primary polyamine compound (a polyamine compound in which all of the amino groups are unsubstituted amino groups). The number of amino groups having active hydrogen atoms in one molecule of the polyamine compound is preferably 2 to 10, more preferably 2 to 8, even more preferably 2 to 6, still more preferably 2 to 4, and particularly preferably 2 or 3. Among these, at least one selected from diamine compounds and triamine compounds can be preferably used. The active hydrogen equivalent of the polyamine compound (the equivalent of active hydrogen possessed by the amino group) is preferably 25 to 2,000, more preferably 25 to 550, even more preferably 25 to 200, still more preferably 25 to 100, still more preferably 25 to 85, and particularly preferably 27 to 40. The active hydrogen equivalent is the value obtained by dividing the molecular weight of a polyamine compound by the number of moles of active hydrogen in the amino group of the polyamine compound (meaning the molecular weight per active hydrogen in the amino group of the polyamine compound).

[0023] The molecular weight of the polyamine compound is preferably 100 to 6000, more preferably 100 to 3000, still more preferably 100 to 1000, particularly preferably 100 to 500, and particularly preferably 100 to 300. When the polyamine compound is a polymer (for example, when it has a polyoxyalkylene group described below), the molecular weight is a number average molecular weight.

[0024] The polyamine compound preferably has two or more amino groups bonded via a group selected from an aliphatic hydrocarbon group, a cyclic hydrocarbon group, an aromatic hydrocarbon group, and a heterocyclic group, or a combination thereof. These groups may have a heteroatom (preferably an oxygen atom) such as an oxygen atom, a nitrogen atom, or a sulfur atom between the carbon-carbon bonds.

[0025] In order to make the polyamine compound less susceptible to reaction with radicals generated by hydrogen peroxide plasma treatment, it is preferable that the polyamine compound does not contain an oxygen atom between the carbon-carbon bond, and more preferably does not contain a heteroatom (an atom other than carbon atom) between the carbon-carbon bond. Examples of heteroatoms include oxygen atoms, nitrogen atoms, and sulfur atoms. In the case of the polyamine compound that does not contain a heteroatom between the carbon-carbon bonds, the group that bonds two or more amino groups is preferably a chain-like aliphatic hydrocarbon group, a combination of a chain-like aliphatic hydrocarbon group and an aromatic hydrocarbon group, or a combination of a chain-like aliphatic hydrocarbon group and an alicyclic hydrocarbon group, from the viewpoint of further improving the curability of the adhesive and the chemical resistance and sterilization durability of the cured adhesive, more preferably a chain-like aliphatic hydrocarbon group or a combination of a chain-like aliphatic hydrocarbon group and an aromatic hydrocarbon group, and particularly preferably a chain-like aliphatic hydrocarbon group. The chain aliphatic hydrocarbon group may have a branch, and when the "group bonding an amino group" is a chain aliphatic hydrocarbon group, this chain aliphatic hydrocarbon group preferably has a branched structure. As the "combination of a chain aliphatic hydrocarbon group and an aromatic hydrocarbon group", for example, "a chain aliphatic hydrocarbon group-aromatic hydrocarbon group-chain aliphatic hydrocarbon group" is preferred. Examples of the "combination of a chain aliphatic hydrocarbon group and an alicyclic hydrocarbon group" include "a chain aliphatic hydrocarbon group-alicyclic hydrocarbon group" and "an alicyclic hydrocarbon group-a chain aliphatic hydrocarbon group-alicyclic hydrocarbon group".

[0026] The number of carbon atoms in the chain aliphatic hydrocarbon group is preferably 4 to 50, more preferably 4 to 12, and even more preferably 6 to 12. The chain aliphatic hydrocarbon group is preferably an alkylene group, and specific examples of the alkylene group include methylene, ethylene, hexamethylene, 2,4,4-trimethylhexamethylene, and dodecamethylene. The number of carbon atoms in the alicyclic hydrocarbon group is preferably 4 to 50, more preferably 4 to 12, and even more preferably 6 to 12. The cyclic hydrocarbon group is preferably a cycloalkylene group, and specific examples of the cycloalkylene group include cyclobutylene, cyclopentylene, and cyclohexylene. Examples of aromatic hydrocarbon rings constituting the aromatic hydrocarbon group include a benzene ring and a fused ring of two or more benzene rings, and specific examples of such fused rings include a naphthalene ring, an anthracene ring, a perylene ring, a fluorene ring, and an acenaphthene ring. Among these aromatic hydrocarbon rings, a benzene ring is preferred.

[0027] The polyamine compound may have an oxyalkylene structure, and in this case, it is more preferable that the polyamine compound has a polyoxyalkylene structure. The alkylene group of the oxyalkylene structure may be a linear alkylene group or a branched alkylene group. The alkylene group of the oxyalkylene structure preferably has 1 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms. The above oxyalkylene structure is more preferably an oxyethylene group or an oxypropylene group. When the polyamine compound of component (B) has a polyoxyalkylene structure, the multiple oxyalkylene groups constituting this polyoxyalkylene structure may be the same or different. The average repeat number of the oxyalkylene groups in the polyoxyalkylene structure is preferably 2 to 1,000, more preferably 3 to 500. The average repeat number is also preferably 2 to 100, also preferably 2 to 50, also preferably 2 to 35, and also preferably 2 to 25. The polyamine compound of component (B) may have multiple polyoxyalkylene structures.

[0028] Specific preferred examples of polyamine compounds that can be used in the present invention are shown below: The number in parentheses is the average number of repeating units in the parentheses.

[0029] [ka]

[0030] [ka]

[0031] [ka]

[0032] [ka]

[0033] [ka]

[0034] [ka]

[0035] The polyamine compounds can be synthesized by conventional methods, and commercially available products may also be used.

[0036] The content of component (B) in the adhesive of the present invention is not particularly limited and can be adjusted appropriately depending on the reaction between component (A) and component (B), etc.

[0037] In the adhesive of the present invention, the content of the polyamine compound can be appropriately set taking into consideration the active hydrogen equivalent and the like. For example, the amount may be 5 to 100 parts by mass, more preferably 8 to 75 parts by mass, and even more preferably 10 to 50 parts by mass, per 100 parts by mass of the epoxy resin as component (A).The active hydrogen equivalent of the polyamine compound relative to the epoxy equivalent of the epoxy resin as component (A) (active hydrogen equivalent / epoxy equivalent) is preferably 0.1 to 1.5, more preferably 0.3 to 1.0, and even more preferably 0.5 to 1.0.

[0038] <(C) Compounds Having a Non-Aromatic Carbon-Carbon Double Bond Group and a Phenolic Hydroxyl Group> The adhesive of the present invention contains, as component (C), a compound having a non-aromatic carbon-carbon double bond group and a phenolic hydroxyl group. Hereinafter, the "compound having a non-aromatic carbon-carbon double bond group and a phenolic hydroxyl group" may be simply referred to as a "phenol compound." The adhesive of the present invention may contain one type of component (C) alone, or may contain two or more types in combination.

[0039] The non-aromatic carbon-carbon double bond group is not particularly limited as long as it is a monovalent group containing a non-aromatic carbon-carbon double bond, and the number of carbon atoms therein is preferably 3 to 20, more preferably 3 to 10. The non-aromatic carbon-carbon double bond group is preferably a group having a vinyl group at the terminal. Specific examples of the non-aromatic carbon-carbon double bond group include, for example, an alkenyl group (preferably having 3 to 20 carbon atoms, more preferably having 3 to 10 carbon atoms, and even more preferably having 3 to 5 carbon atoms), an alkenylcarbonyloxy group (preferably having 3 to 20 carbon atoms, more preferably having 3 to 10 carbon atoms, and even more preferably having 3 to 5 carbon atoms), and an alkenyloxy group (preferably having 3 to 20 carbon atoms, and more preferably having 3 to 10 carbon atoms).

[0040] The phenol compound may have a substituent other than a non-aromatic carbon-carbon double bond group, and examples of the substituent include a substituent selected from the below-described substituent group T (excluding substituents containing a non-aromatic carbon-carbon double bond group). The phenol compound generally does not have an epoxy group.

[0041] In the phenolic compound, at least one of the non-aromatic carbon-carbon double bond group and the substituent other than the non-aromatic carbon-carbon double bond group is preferably linked at the ortho position relative to the ring-constituting carbon atom of the aromatic hydrocarbon ring to which the phenolic hydroxyl group is bonded. The presence of the phenolic hydroxyl group in a bulky environment enhances the peroxy radical trapping ability of component (C), thereby improving the sterilization durability of the cured product. Examples of the substituent other than the non-aromatic carbon-carbon double bond group include an alkyl group (preferably having 3 to 20 carbon atoms, more preferably having 3 to 10 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms), an alkoxy group (preferably having 3 to 20 carbon atoms, more preferably having 3 to 10 carbon atoms), an aryloxy group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms), an acyloxy group (preferably having 3 to 20 carbon atoms, more preferably having 3 to 10 carbon atoms), and an alkoxycarbonyloxy group (preferably having 3 to 20 carbon atoms, more preferably having 3 to 10 carbon atoms).

[0042] The phenolic compound may have one type of non-aromatic carbon-carbon double bond group alone or a combination of two or more types. The phenolic compound may have one or two or more phenolic hydroxyl groups. The phenolic compound may be a low-molecular-weight compound or a polymer. Since the phenolic compound is less likely to swim out of the cured product, it is preferably a polymer, and more preferably a polymer with an average degree of polymerization of 2 or more. The average degree of polymerization is preferably 1.05 or more, more preferably 1.5 or more. On the other hand, it is practical for the average degree of polymerization to be 10 or less. The molecular weight of the phenol compound (low molecular weight compound) is not particularly limited, and is preferably from 100 to less than 2000, more preferably from 120 to 1000, and even more preferably from 120 to 500. By setting the molecular weight within the above range, it is possible to suppress the possibility of the phenol compound migrating out of the cured product, and also to obtain sufficient solubility of component (A) in the epoxy resin. The weight average molecular weight of the polymer is not particularly limited and can be, for example, 200 to 2,000, with 200 to 500 being preferred.

[0043] The weight average molecular weight or number average molecular weight of the compounds described herein is determined as follows. The weight average molecular weight or number average molecular weight can be measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (GPC). Specifically, a GPC apparatus HLC-8220 (trade name, manufactured by Tosoh Corporation) is used, tetrahydrofuran is used as the eluent, and a column TSKgel Super AWM-H (trade name, manufactured by Tosoh Corporation) is used, at 23°C, a flow rate of 0.3 to 0.5 mL / min, and UV detection is performed.

[0044] Examples of the phenol compound include compounds represented by the following formula (1) or (2) and polymers having a constituent component represented by the following formula (3), and polymers having the constituent component represented by the following formula (3) as a repeating unit are preferred.

[0045] [ka]

[0046] In the above formula, R 1 , R 2a , R 2b and R 3 represents a substituent. L represents a divalent linking group. X represents a single bond or a divalent linking group. Ring α1, ring α 2a , ring α 2b and ring α3 represent an aromatic hydrocarbon ring. m1 to m3 are integers of 1 or more. n1, n2b, and n3 are integers of 1 or more. n2a is 0 or an integer of 1 or more. The upper limits of m1+n1, m2+n2a, n2b, and m3+n3 are the upper limits of ring α1, ring α 2a , ring α 2b and the upper limit of the number of substituents that ring α3 can have. However, in formula (1), at least one R 1 , in equation (2), R 2a and R 2b and at least one R in formula (3). 3 represents a non-aromatic carbon-carbon double bond group. In formula (1), 1 to 3 R 1 In formula (2), 1 to 3 R 2b and in formula (3), 1 to 3 R 3 represents a non-aromatic carbon-carbon double bond group, and in formula (1), one R 1 , one R in Eq. (2) 2b and one R in equation (3) 3 More preferably, represents a non-aromatic carbon-carbon double bond group.

[0047] R 1 , R 2a , R 2b and R 3 Examples of the substituent that can be adopted as the substituent include a substituent selected from the substituent group T described below, such as an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a cyano group, a nitro group, and —Si(R7 )3 is preferred. 7 represents an alkyl group, an aryl group, an alkoxy group, or an aryloxy group. 7 may be the same or different from each other. R 1 , R 2a , R 2b and R 3 The alkyl group, aryl group, heterocyclic group, alkoxy group, acyl group, alkyloxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group and arylsulfonyl group that can be taken as arylsulfonyl have the same meanings as the corresponding groups in the substituent group T described later, and the preferred groups are also the same. Also, R 1 , R 2a , R 2b and R 3 Each of the above groups that can be taken as R may be an unsubstituted group or a group having a substituent. 1 , R 2a , R 2b and R 3 The substituents that may be possessed by each of the above groups that can be taken as R are not particularly limited. 1 , R 2a , R 2b and R 3 When each of the above groups which can be taken as a group has a substituent, the number of substituents which each group has can be, for example, 4 or less. In addition, when n1, n2a, n2b, and n3 are integers of 2 or more, there are multiple R 1 , R 2a , R 2b and R 3 are adjacent to each other and located at positions where they can be bonded, these substituents may be bonded to each other to form any one of a 5- to 7-membered ring, a spiro ring, or a bicyclo ring. R 7 The alkyl group, aryl group, alkoxy group, and aryloxy group that can be taken as a substituent have the same meanings as the corresponding groups in the substituent group T described later, and the preferred groups are also the same. Also, R 7Each of the above groups that can be taken as R may be an unsubstituted group or a group having a substituent. 7 The substituents that may be possessed by the above groups that can be taken as R are not particularly limited, and are preferably selected from the substituent group T described below. 7 When each of the above groups which can be taken as a substituent has a substituent, the number of the substituent is not particularly limited as long as it is one or more, and can be, for example, four or less. R 1 , R 2a , R 2b and R 3 Examples of the substituent other than the non-aromatic carbon-carbon double bond group that can be taken as the substituent include an alkyl group (preferably having 3 to 20 carbon atoms, more preferably having 3 to 10 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms), an alkoxy group (preferably having 3 to 20 carbon atoms, more preferably having 3 to 10 carbon atoms), an aryloxy group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms), an acyloxy group (preferably having 3 to 20 carbon atoms, more preferably having 3 to 10 carbon atoms), and an alkoxycarbonyloxy group (preferably having 3 to 20 carbon atoms, more preferably having 3 to 10 carbon atoms), and an alkyl group is preferred.

[0048] Preferred examples of the divalent linking group that can be taken as X include an alkylene group, an arylene group, and a heterocyclic group. The alkylene group, arylene group, and heterocyclic group that can be taken as X have the same meaning as the group obtained by further removing one hydrogen atom from an alkyl group, aryl group, and heterocyclic group selected from the substituent group T described later, respectively, and the preferred examples are also the same. Furthermore, each of the above groups that can be taken as X may be an unsubstituted group or a group that has a substituent. The substituent that each of the above groups that can be taken as X may have is not particularly limited and is preferably selected from the substituent group T described below. When each of the above groups that can be taken as X has a substituent, the number of the substituents is not particularly limited as long as it is one or more, and can be, for example, four or less. In particular, when each of the above groups that can be taken as X is assumed to have a linear linking chain in which the number of carbon atoms constituting the linking moiety, i.e., the number of atoms linking the rings α3 between adjacent repeating units, is minimized, the minimum number of carbon atoms in this linking chain is preferably 1 to 50, more preferably 1 to 20, and even more preferably 1 to 6. X is preferably a single bond, an alkylene group, an arylene group or a heterocyclic group, more preferably a single bond or an alkylene group, and even more preferably an alkylene group.

[0049] Ring α1, Ring α 2a , ring α 2b Examples of aromatic hydrocarbon rings that can be used as ring α3 include a benzene ring and a fused ring of two or more benzene rings, and specific examples of such fused rings include a naphthalene ring, an anthracene ring, a perylene ring, a fluorene ring, and an acenaphthene ring. Among these aromatic hydrocarbon rings, a benzene ring is preferred.

[0050] The upper limit values ​​of m1 to m3 and the upper limit values ​​of n1, n2a, n2b, and n3 are set such that the sums (m1+n1, m2+n2a, n2b, and m3+n3) are within the range of ring α1, ring α2, and ring α3, respectively. 2a , ring α 2b and ring α3. Preferably, m1 to m3 are all 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2. Furthermore, n1, n2a, and n3 are each preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 or 2.

[0051] - Substituent group T - In the present invention, preferred substituents include those selected from the following substituent group T. Furthermore, in this specification, when a group is simply described as a substituent, it refers to this group of substituents T, and when only a group, for example, an alkyl group, is described, the corresponding group in this group of substituents T is preferably applied. Furthermore, in this specification, when an alkyl group is described separately from a cyclic (cyclo)alkyl group, the term "alkyl group" is used to encompass both linear and branched alkyl groups. On the other hand, when an alkyl group is not described separately from a cyclic alkyl group, or unless otherwise specified, the term "alkyl group" is used to encompass both linear and branched alkyl groups and cycloalkyl groups. This also applies to groups (alkoxy groups, alkylthio groups, alkenyloxy groups, etc.) containing groups that can form a cyclic structure (alkyl groups, alkenyl groups, alkynyl groups, etc.) and compounds containing groups that can form a cyclic structure. When a group can form a cyclic skeleton, the lower limit of the number of atoms in the group forming the cyclic skeleton is 3 or more, preferably 5 or more, regardless of the lower limit of the number of atoms specifically described below for groups that can form this structure. In the description of the substituent group T below, groups having a linear or branched structure and groups having a cyclic structure are sometimes described separately, for example, alkyl groups and cycloalkyl groups, in order to clarify the groups.

[0052] The groups contained in the substituent group T include the following groups. an alkyl group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, even more preferably having 1 to 12 carbon atoms, even more preferably having 1 to 8 carbon atoms, even more preferably having 1 to 6 carbon atoms, and particularly preferably having 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, even more preferably having 2 to 12 carbon atoms, even more preferably having 2 to 6 carbon atoms, and even more preferably having 2 to 4 carbon atoms), an alkynyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, and even more preferably having a cycloalkyl group (preferably having 3 to 20 carbon atoms), a cycloalkenyl group (preferably having 5 to 20 carbon atoms), an aryl group (which may be a monocyclic group or a fused ring group (preferably a fused ring group of 2 to 6 rings). In the case of a fused ring group, it consists of a 5- to 7-membered ring or the like. The aryl group preferably has 6 to 40 carbon atoms, more preferably has 6 to 30 carbon atoms, still more preferably has 6 to 26 carbon atoms, and particularly preferably has 6 to 10 carbon atoms); Heterocyclic groups (having at least one nitrogen atom, oxygen atom, sulfur atom, phosphorus atom, silicon atom or selenium atom as a ring-constituting atom) may be monocyclic groups or condensed ring groups (preferably condensed ring groups of 2 to 6 rings). In the case of monocyclic groups, the number of ring members is preferably 5 to 7, more preferably 5 or 6. The number of carbon atoms in the heterocyclic group is preferably 2 to 40, more preferably 2 to 20. Heterocyclic groups include aromatic heterocyclic groups (heteroaryl groups) and aliphatic heterocyclic groups (aliphatic heterocyclic groups). ), an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms), an alkenyloxy group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms), an alkynyloxy group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms), a cycloalkyloxy group (preferably having 3 to 20 carbon atoms), an aryloxy group (preferably having 6 to 40 carbon atoms, more preferably having 6 to 26 carbon atoms, even more preferably having 6 to 14 carbon atoms), a heterocyclic oxy group (preferably having 2 to 20 carbon atoms),

[0053] Alkoxycarbonyl groups (preferably having 2 to 20 carbon atoms), cycloalkoxycarbonyl groups (preferably having 4 to 20 carbon atoms), aryloxycarbonyl groups (preferably having 6 to 20 carbon atoms), amino groups (preferably having 0 to 20 carbon atoms, unsubstituted amino groups (-NH), (mono- or di-) alkylamino groups, (mono- or di-) alkenylamino groups, (mono- or di-) alkynylamino groups, (mono- or di-) cycloalkylamino groups, (mono- or di-) cycloalkenylamino groups, and (mono- or di-) arylamino groups. and (mono- or di-)heterocyclic amino groups. The above-mentioned groups substituting the unsubstituted amino group have the same meanings as the corresponding groups in the substituent group T.), a sulfamoyl group (preferably having 0 to 20 carbon atoms, and an alkyl, cycloalkyl, or aryl sulfamoyl group is preferred), an acyl group (preferably having 1 to 20 carbon atoms, more preferably having 2 to 15 carbon atoms), an acyloxy group (preferably having 1 to 20 carbon atoms), a carbamoyl group (preferably having 1 to 20 carbon atoms, and an alkyl, cycloalkyl, or aryl carbamoyl group is preferred),

[0054] an acylamino group (preferably having 1 to 20 carbon atoms), a sulfonamido group (preferably having 0 to 20 carbon atoms, and an alkyl, cycloalkyl, or aryl sulfonamido group is preferred), an alkylthio group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms), a cycloalkylthio group (preferably having 3 to 20 carbon atoms), an arylthio group (preferably having 6 to 40 carbon atoms, more preferably having 6 to 26 carbon atoms, and even more preferably having 6 to 14 carbon atoms), a heterocyclic thio group (preferably having 2 to 20 carbon atoms), an alkyl, cycloalkyl, or arylsulfonyl group (preferably having 1 to 20 carbon atoms),

[0055] Examples of the alkyl group include a silyl group (preferably a silyl group having 1 to 30 carbon atoms, more preferably a silyl group having 1 to 20 carbon atoms, substituted with an alkyl, aryl, alkoxy, or aryloxy), a silyloxy group (preferably a silyloxy group having 1 to 20 carbon atoms, substituted with an alkyl, aryl, alkoxy, or aryloxy), a hydroxy group, a cyano group, a nitro group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), an oxygen atom (specifically, a ring-constituting >CH2 is replaced with >C=O), a carboxy group (-CO2H), a phosphono group [-PO(OH)2], a phosphoryl group [-O-PO(OH)2], a sulfo group (-SO3H), a boric acid group [-B(OH)2], an onio group (including an ammonio group including a cyclic ammonio group, a sulfonio group, or a phosphonio group, preferably having 0 to 30 carbon atoms, more preferably 1 to 20 carbon atoms), a sulfanyl group (-SH), an amino acid residue, or a polyamino acid residue. Further examples include the above alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, aryl groups, heterocyclic groups, alkoxy groups, alkenyloxy groups, alkynyloxy groups, cycloalkyloxy groups, aryloxy groups, heterocyclicoxy groups, alkoxycarbonyl groups, cycloalkoxycarbonyl groups, aryloxycarbonyl groups, amino groups, sulfamoyl groups, acyl groups, acyloxy groups, carbamoyl groups, acylamino groups, sulfonamide groups, alkylthio groups, cycloalkylthio groups, arylthio groups, heterocyclicthio groups, alkyl, cycloalkyl, or arylsulfonyl groups, all of which have a carboxy group, a phosphono group, a sulfo group, an onio group, an amino acid residue, or a polyamino acid residue as a substituent.

[0056] The substituent selected from substituent group T is more preferably an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an amino group, an acylamino group, a cyano group, or a halogen atom, and particularly preferably an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group, or a cyano group.

[0057] Unless otherwise specified, the substituents selected from the substituent group T also include groups formed by combining multiple of the above groups. For example, when a compound or a substituent contains an alkyl group, an alkenyl group, or the like, it may be substituted or unsubstituted. Furthermore, when it contains an aryl group, a heterocyclic group, or the like, it may be a monocyclic or fused ring, and it may be substituted or unsubstituted.

[0058] In a polymer having a constituent component represented by the above formula (3), the content of the constituent component represented by the above formula (3) is not particularly limited, but for example, it is preferably 70 mass% or more, more preferably 80 mass% or more, and even more preferably 90 mass% or more of all the constituent components that make up the polymer. There are no particular limitations on the other constituent components of the polymer other than the above formula (3).

[0059] The phenolic hydroxyl group equivalent of the phenol compound is preferably 100 to 400, more preferably 100 to 300. By setting the phenolic hydroxyl group equivalent within the above range, the polarity does not become too high, sufficient solubility of component (A) in the epoxy resin is obtained, and a sufficient accelerating effect can be obtained. The phenolic hydroxyl group equivalent is a value obtained by dividing the molecular weight of a phenolic compound by the number of moles of phenolic hydroxyl groups contained in the phenolic compound.

[0060] Specific preferred examples of phenol compounds that can be used in the present invention are shown below: The number in parentheses indicates the number of repetitions of the structural unit in the parentheses.

[0061] [ka]

[0062] The above phenolic compounds can be synthesized by conventional methods, and commercially available products may also be used.

[0063] In the adhesive of the present invention, the amount of component (C) blended is preferably 3 to 20 parts by mass, more preferably 5 to 15 parts by mass, and even more preferably 5 to 10 parts by mass, per 100 parts by mass of the epoxy resin. By blending the amount within this range, a sufficient curing-accelerating effect can be obtained without deteriorating the physical properties of the cured product. Furthermore, in the adhesive of the present invention, the blending ratio of component (B) to component (C) is, in parts by mass, preferably component (B):component (C)=30:1 to 1.5:1, more preferably component (B):component (C)=10:1 to 2:1, and even more preferably component (B):component (C)=8:1 to 4:1.

[0064] <(D) Inorganic filler> The adhesive of the present invention may contain an inorganic filler as component (D). Examples of the inorganic filler include so-called inorganic fillers such as alumina (aluminum oxide), magnesia (magnesium oxide), titanium oxide (titanium white), aluminum hydroxide, barium titanate, zinc oxide, silica (including crystalline silica (silicon oxide) and fused silica (silicon oxide)), metal nanoparticles, and glass fibers; layered silicates such as talc, clay, mica, smectite, kaolin minerals, mica clay, and vermiculite; metal powders such as silver powder and copper powder; and nitrides such as aluminum nitride, boron nitride, silicon nitride, and gallium nitride. Silicon carbide, carbon black, graphite, carbon fibers, and carbon nanotubes can also be used. It is also preferable that the inorganic filler is surface-treated. There are no particular limitations on the type of surface treatment. For example, surface treatment with a silane compound is used. In the present invention, the silane compound refers to a compound having a structure in which at least one organic group is bonded to Si. More preferably, it is SiR4 (R4 is an organic group). Preferred silane compounds are silane coupling agents, silazanes, and silicone compounds (polysiloxanes). Such surface treatment methods can be carried out by conventional methods. For example, see paragraphs

[0090] to

[0101] of JP 2018-195964 A.

[0065] The inorganic filler is commercially available. For example, commercially available alumina products include DAM-70, DAM-45, DAM-07, DAM-05, DAW-45, DAW-05, DAW-03, and ASFP-20 (all trade names, manufactured by Denki Kagaku Kogyo Co., Ltd.), AL-43-KT, AL-47-H, AL-47-1, AL-160SG-3, AL-43-BE, AS-30, AS-40, AS-50, AS-400, CB-P02, and CB-P05 (all trade names). , manufactured by Showa Denko K.K.), A31, A31B, A32, A33F, A41A, A43A, MM-22, MM-26, MM-P, MM-23B, LS-110F, LS-130, LS-210, LS-242C, LS-250, and AHP300 (all trade names, manufactured by Nippon Light Metal Co., Ltd.), AA-03, AA-04, AA-05, AA-07, AA-2, AA-5, AA-10, and AA-18 (all trade names, manufactured by Sumitomo Chemical Co., Ltd.), AEROXIDE Alu C, AEROXIDE Alu C805, and AEROXIDE Alu 65 (all trade names, manufactured by Nippon Aerosil Co., Ltd.). Commercially available titanium oxide products include, for example, G-1, G-10, F-2, F-4, and F-6 (all trade names, manufactured by Showa Denko K.K.), TAF-520, TAF-500, TAF-1500, TM-1, TA-100C, and TA-100CT (all trade names, manufactured by Fuji Titanium Kogyo Co., Ltd.), MT-01, MT-10EX, MT-05, MT-100S, MT-100TV, MT-100Z, MT-150EX, MT-100AQ, MT-100WP, MT-100SA, and MT-100HD. , MT-300HD, MT-500SA, MT-600SA, and MT-700HD (all trade names, manufactured by Teika Corporation), TTO-51(A), TTO-51(C), TTO-55(A), TTO-55(B), TTO-55(C), TTO-55(D), TTO-S-1, TTO-S-2, TTO-S-3, TTO-S-4, MPT-136, and TTO-V-3 (all trade names, manufactured by Ishihara Sangyo Kaisha), and Aeroxide NKT90 (trade name, manufactured by Nippon Aerosil Co., Ltd.). Commercially available aluminum hydroxide products include, for example, B-309 and B-309 (all trade names, manufactured by Tomoe Engineering Co., Ltd.), BA173, BA103, B703, B1403, BF013, BE033, BX103, and BX043 (all trade names, manufactured by Nippon Light Metal Co., Ltd.). Commercially available examples of the layered silicates include Nanoace D-1000, Nanoace D-800, Microace SG-95, Microace P-8, and Microace P-6 (all trade names of talc, manufactured by Nippon Talc Co., Ltd.), FH104, FH105, FL108, FG106, MG115, FH104S, and ML112S (all trade names of talc, manufactured by Fuji Talc Co., Ltd.), Y-1800, TM-10, A-11, and SJ-005 (all trade names of mica, manufactured by Yamaguchi Mica Co., Ltd.), and Kunibis-110 (trade name, manufactured by Kunimine Industries Co., Ltd.). Commercially available products of the above barium titanate include, for example, BT-H9DX, HF-9, HF-37N, HF-90D, HF-120D, and HT-F (all trade names, manufactured by Kyoritsu Material Co., Ltd.), BT-100 and HPBT series (all trade names, manufactured by Fuji Titanium Co., Ltd.), BT series (manufactured by Sakai Chemical Industry Co., Ltd.), and Parceram BT (manufactured by Nippon Chemical Industry Co., Ltd.). Commercially available zinc oxide products include, for example, FINEX-30, FINEX-30W-LP2, FINEX-50, FINEX-50S-LP2, and XZ-100F (all trade names, manufactured by Sakai Chemical Industry Co., Ltd.), FZO-50 (manufactured by Ishihara Sangyo Kaisha), MZ-300, MZ-306X, MZY-505S, MZ-506X, and MZ-510HPSX (all trade names, manufactured by Teika Corporation). Commercially available examples of the glass fibers include CS6SK-406, CS13C-897, CS3PC-455, and CS3LCP-256 (all trade names, manufactured by Nitto Boseki Co., Ltd.), ECS03-615, ECS03-650, EFDE50-01, and EFDE50-31 (all trade names, manufactured by Central Glass Co., Ltd.), and ACS6H-103 and ACS6S-750 (all trade names, manufactured by Nippon Electric Glass Co., Ltd.). Commercially available examples of the metal powder include spherical silver powders AG3 and AG4, flake silver powders FA5 and FA2 (all trade names, manufactured by DOWA High-Tech Co., Ltd.), SPQ03R, SPN05N, SPN08S, and Q03R (all trade names of silver powders, manufactured by Mitsui Mining & Smelting Co., Ltd.), AY-6010 and AY-6080 (all trade names of silver powders, manufactured by Tanaka Kikinzoku Co., Ltd.), ASP-100 (trade name of silver powder, manufactured by Aida Chemical Industry Co., Ltd.), Ag-coated powder AG / SP (silver powder are trade names of copper powders, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), MA-O015K, MA-O02K, MA-O025K (all of which are trade names of copper powders, manufactured by Mitsui Mining & Smelting Co., Ltd.), electrolytic copper powders #52-C and #6 (manufactured by JX Nippon Mining & Metals Corporation), 10% Ag coated Cu-HWQ (trade name of copper powders, manufactured by Fukuda Metal Foil & Powder Co., Ltd.), Type-A and Type-B (all of which are trade names of copper powders, manufactured by Dowa Electronics Co., Ltd.), and UCP-030 (trade name of copper powders, manufactured by Sumitomo Metal Mining Co., Ltd.). Commercially available products of the nitrides include, for example, H grade, E grade, and HT grade (all of which are trade names of aluminum nitride, manufactured by Tokuyama Corporation), TOYAL TecFiller TFS-A05P and TOYAL TecFiller TFZ-A02P (all of which are trade names of aluminum nitride, manufactured by Toyo Aluminum Co., Ltd.), ALN020BF, ALN050BF, ALN020AF, ALN050AF, and ALN020SF (all of which are trade names of aluminum nitride, manufactured by Tomoe Engineering Co., Ltd.), FAN-f05 and FAN-f30 (all of which are trade names of aluminum nitride, manufactured by Furukawa Denshi Co., Ltd.), Denka Boron Nitride SGP, Denka Boron Nitride MGP, Denka Boron Nitride Examples of suitable boron nitride include Ido GP, Denka Boron Nitride HGP, Denka Boron Nitride SP-2, and Denka Boron Nitride SGPS (all trade names of boron nitride, manufactured by Denki Kagaku Kogyo Co., Ltd.), UHP-S1, UHP-1K, UHP-2, and UHP-EX (all trade names of boron nitride, manufactured by Showa Denko K.K.), SN-9, SN-9S, SN-9FWS, SN-F1, and SN-F2 (all trade names of silicon nitride, manufactured by Denki Kagaku Kogyo Co., Ltd.). Commercially available examples of the glass fibers include CF0027, CF0093, CF0018, and CF0033 (all trade names, manufactured by Nippon Frit Co., Ltd.). Commercially available silicon carbide products include, for example, GMF-H type, GMF-H2 type, and GMF-LC type (all trade names, manufactured by Pacific Random Corporation), HSC1200, HSC1000, HSC059, HSC059I, and HSC007 (all trade names, manufactured by Tomoe Engineering Co., Ltd.). Commercially available silica products include, for example, Cysilia (manufactured by Fuji Silysia Chemical Ltd.), AEROSIL R972, AEROSIL R104, AEROSIL R202, AEROSIL 805, AEROSIL R812, AEROSIL RX200, AEROSIL R9200, AEROSIL NAX50, AEROSIL 200, and AEROSIL R7200 (all trade names, manufactured by Nippon Aerosil Co., Ltd.), the Leoseal series (manufactured by Tokuyama Corporation), CMC-12, VX-S, and VX-SR (all trade names of crystalline silica, manufactured by Tatsumori Co., Ltd.), FB-3SDC, FB-3SDX, SFP-30M, SFP-20M, SFP-30MHE, SFP-130MC, and UFP-30 (all trade names of fused silica, manufactured by Denki Kagaku Kogyo Co., Ltd.), and the Excelica series (trade name of fused silica, manufactured by Tokuyama Corporation). Commercially available products of the carbon fibers, carbon black, graphite, and carbon nanotubes include, for example, Toray Industries, Inc.'s Torayca Milled Fiber MLD-30 and Torayca Milled Fiber MLD-300 (both trade names of carbon fibers), Nippon Polymer Co., Ltd.'s CFMP-30X and CFMP-150X (both trade names of carbon fibers), Nippon Polymer Co., Ltd.'s #1000 (trade name of carbon black), Mitsubishi Chemical Corporation's XN-100 and HC-600 (trade names of graphite), Nippon Graphite Fiber Co., Ltd.'s SWeNT SG65, SWeNT SGi, IsoNanoTubes-M, IsoNanoTubes-S, PureTubes, Pyrograf PR-25-XT-PS, and PR-25XT-LHT (both trade names of carbon nanotubes, Sigma-Aldrich Chemical).

[0066] The inorganic filler used in the adhesive of the present invention is preferably at least one of silica (preferably fumed silica), titanium oxide, alumina, and layered silicate, with silica being more preferred. Furthermore, from the viewpoint of improving chemical resistance, these are preferably surface-treated to be hydrophobic. More preferred are inorganic fillers in which at least an alkyl group has been introduced onto the surface of the inorganic filler by surface treatment, i.e., alkyl-modified inorganic fillers. Of these, surface-treated silica (preferably alkyl-modified silica particles) is preferred.

[0067] The inorganic filler used in the present invention preferably has a volume average particle diameter (average primary particle diameter) of 1 to 10,000 nm, more preferably 3 to 5,000 nm, even more preferably 5 to 2,000 nm, even more preferably 5 to 1,000 nm, still more preferably 6 to 500 nm, still more preferably 7 to 200 nm, and particularly preferably 8 to 100 nm. In the case of silica, titanium oxide, and alumina, from the viewpoint of chemical resistance of the cured product, the volume average particle diameter is preferably 1 to 500 nm, more preferably 5 to 200 nm, even more preferably 6 to 100 nm, and particularly preferably 7 to 50 nm.

[0068] The inorganic filler was added to methanol to a concentration of 0.5% by mass and dispersed by ultrasonication for 10 minutes. The particle size distribution of the inorganic filler thus treated was measured using a laser diffraction / scattering particle size distribution analyzer (manufactured by Horiba, Ltd., product name: LA950V2), and the volume-based median diameter was determined. The median diameter corresponds to the cumulative 50% when the particle size distribution is expressed as a cumulative distribution.

[0069] In the adhesive of the present invention, the content of component (D) is preferably 4 to 20 mass %, more preferably 4 to 15 mass %, and even more preferably 4 to 12 mass %, from the viewpoint of the viscosity of the adhesive. In the adhesive of the present invention, the content of component (D) can be 1 to 50 parts by mass, and preferably 4 to 20 parts by mass, per 100 parts by mass of the epoxy resin as component (A).

[0070] The inorganic filler of component (D) is preferably in a state where it is uniformly dispersed in the adhesive when components (A) to (C) are mixed (before curing).

[0071] From the perspective of use in the manufacture of medical devices, the adhesive of the present invention preferably has a viscosity of 30 Pa·s or more but less than 2500 Pa·s, more preferably 200 or more but less than 1500 Pa·s, even more preferably 350 to 1350 Pa·s, and particularly preferably 500 to 1100 Pa·s. The viscosity is a value determined by the measurement method described in the Examples below. From the same viewpoint, the adhesive of the present invention preferably has a cure rate described in the examples below of 70% or more, more preferably 80% or more, and even more preferably 90% or more.

[0072] [Cured product] The cured product of the present invention is a cured product produced by curing the adhesive of the present invention. That is, the cured product of the present invention is used as a component constituting the adhesive portion of a medical device or as a component of a medical device. The curing temperature of the adhesive of the present invention is not particularly limited and can be appropriately set depending on the component (B) contained in the adhesive of the present invention. The components can be mixed by conventional methods. This mixing is preferably carried out while removing air bubbles, and therefore is usually carried out under reduced pressure. Specifically, the adhesive of the present invention undergoes an efficient curing reaction even at low temperatures, allowing the cured product of the present invention to be obtained. The curing temperature is, for example, preferably 100°C or lower, more preferably 80°C or lower, even more preferably 60°C or lower, and particularly preferably 50°C or lower. Curing at room temperature (25°C) or lower is also possible and preferred. Furthermore, to ensure sufficient curing reaction, the curing temperature is preferably 15°C or higher, more preferably 20°C or higher. The curing reaction time can be set appropriately depending on the purpose. Typically, the curing reaction is carried out for 1.5 to 200 hours to obtain a cured product. By setting the curing temperature within the above range, the accelerating effect can be fully exerted, and the reaction between component (C) and component (A) can be suppressed. It is preferable that the curing temperature of the adhesive of the present invention be as low as possible, in order to reduce the number of times that the medical device is exposed to high temperatures during the manufacturing process.

[0073] [Medical device components] Hereinafter, a medical device component 10 of the present invention (hereinafter, "medical device component" may also be simply referred to as "component") has a substrate 1 and a cured product 2 (cured product of the present invention) on the substrate. The above symbols correspond to those in FIG.

[0074] <Base material> The base material of the medical device member of the present invention is not particularly limited, and a wide range of materials used in the constituent members of ordinary medical devices can be used. Specifically, the substrate preferably contains, for example, a metal (iron and non-ferrous metal), an inorganic material other than a metal, or an organic material, and more preferably contains a metal (is a metal substrate).

[0075] The iron mentioned above also includes alloys of iron and non-ferrous metals, such as stainless steel, which is preferably used in the present invention.

[0076] Examples of the non-ferrous metal include aluminum, titanium, magnesium, nickel, copper, lead, zinc, tin, chromium, tungsten, cobalt, vanadium, and gold, as well as alloys of at least two of these metals. Aluminum, titanium, magnesium, nickel, copper, lead, zinc, tin, chromium, tungsten, and cobalt, as well as alloys of at least two of these metals, are preferred.

[0077] Examples of inorganic materials other than the above metals include glass and glass ceramics. Examples of the glass include sodium soda glass, Pyrex (registered trademark) glass, quartz glass, and alkali-free glass. Examples of the ceramics include alumina, zirconia, silicon carbide, and silicon nitride.

[0078] Examples of the organic material include thermoplastic resins and thermosetting resins. Examples of the thermoplastic resin include thermoplastic polyimide resin, thermoplastic polyamide resin, polyetherimide resin, polyphenylene ether resin, polycarbonate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polyphenylene sulfide resin, polyether ether ketone resin, polyether sulfone resin, acrylic resin, polyethylene resin, polypropylene resin, polyolefin resin such as polymethylpentene resin, and thermoplastic polycycloolefin such as thermoplastic polynorbornene. Examples of the thermosetting resin include thermosetting polyimide resin, thermosetting polyamide resin, polyamideimide resin, epoxy resin, phenol resin, polystyrene resin, styrene resin such as ABS resin (acrylonitrile-butadiene-styrene copolymer resin) and acrylonitrile-styrene copolymer resin, and thermosetting polycycloolefin such as thermosetting polynorbornene.

[0079] The physical properties of the substrate, such as flexibility and rigidity, can be determined appropriately depending on the medical device to which the member is applied. The same applies to the thickness of the substrate. The thickness of the substrate can be, for example, 0.1 to 50 mm, or may be 0.5 to 10 mm. The shape of the substrate is not particularly limited, and may be either uneven or concave. The adhesive of the present invention has excellent shape retention, so it can be cured while maintaining the shape of a thickly applied layer. Therefore, for example, it can be sealed with high precision regardless of the shape of the concave portion of the substrate. Furthermore, it is also possible to create a desired structure (such as a desired convex shape) by curing the adhesive. In other words, the adhesive of the present invention is also suitable as a resin material or resin composition for obtaining a resin structure (resin molded product).

[0080] The content of at least one of metal, non-metallic inorganic material, and organic material contained in the substrate is not particularly limited, and can be, for example, 80% by mass or more, preferably 90% by mass or more, or may be 100% by mass.

[0081] [Medical devices] Medical devices having components fixed by the cured product of the present invention and medical devices to which the components of the present invention can be applied, i.e., medical devices of the present invention, include, for example, catheters, applicators, X-ray imaging devices, electrosurgical instruments, active treatment instruments, ultrasonic diagnostic devices, and endoscopes.

[0082] [Endoscopy] One embodiment of the endoscope of the present invention has the medical device member of the present invention as a constituent member. In another embodiment of the endoscope of the present invention, components are fixed by the cured product of the present invention. "Components are fixed by the cured product of the present invention" means that at least some of the components constituting the endoscope are fixed to a support member via the cured product of the present invention.

[0083] [Medical device manufacturing method] The medical device of the present invention can be manufactured by a conventional method except for using the adhesive of the present invention, for example, by referring to International Publication No. 2020 / 175272, Japanese Patent Application Laid-Open No. 2009-194934, Japanese Patent Application Laid-Open No. 2014-511191, and Japanese Patent Application Laid-Open No. 2001-128929. [Example]

[0084] The present invention will be described in more detail based on examples. However, the present invention is not to be construed as being limited by the examples except as defined in the present invention.

[0085] <Preparation of epoxy resin adhesive> (Preparation of Epoxy Resin Adhesive 1 (Epoxy Resin Adhesive No. 1 in Table 1 below)) Epoxy resin adhesive 1 was obtained by degassing 10.0 parts by mass of bisphenol A diglycidyl ether (trade name jER828, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 189) (component A-1 in Table 1 below), 1.5 parts by mass of hexamethylenediamine (component B-1 in Table 1 below), 0.6 parts by mass of MEH-8000H (trade name, manufactured by Showa Kasei Co., Ltd.) (component C-5 in Table 1 below), and 1.5 parts by mass of Aerosil NAX50 (trade name, manufactured by Nippon Aerosil Co., Ltd., average primary particle diameter 30 nm) (component D-2 in Table 1 below) using an Awatori Rentaro ARV-310 (trade name, manufactured by Thinky Corporation) at 25°C under a reduced pressure of 1.0 Pa while stirring at 2000 rpm for 5 minutes.

[0086] (Preparation of Epoxy Resin Adhesives 2 to 28 and c1 to c7 (Epoxy Resin Adhesives Nos. 2 to 28 and c1 to c7 in Table 1 below)) Epoxy resin adhesives 2 to 28 and c1 to c7 were prepared in the same manner as epoxy resin adhesive 1, except that the composition of epoxy resin adhesive 1 was changed to the compositions of epoxy resin adhesives 2 to 28 and c1 to c7 listed in Table 1 below.

[0087] [test] Immediately after preparation, the epoxy resin adhesives 1 to 28 and c1 to c7 were subjected to the following tests (Test Examples 1 to 4). The results are summarized in Table 1 (Tables 1-1 to 1-4) below.

[0088] [Test Example 1] Pot life The epoxy resin adhesive was allowed to stand at 25° C. After 25 minutes and 45 minutes of standing, the epoxy resin adhesive was poked with a needle and the pot life was evaluated according to the following evaluation criteria. -Evaluation criteria- S: No stringiness after both 25 and 45 minutes. A: There is no stringiness after 25 minutes, but there is slight stringiness after 45 minutes. It can be used as an adhesive without any problems even 45 minutes after preparation. B: Stringiness occurs after 25 minutes. The adhesive can be used without any problems even 25 minutes after preparation. C: After 25 minutes, stringiness was severe (hardening had progressed). 25 minutes after preparation, the adhesive could not be used.

[0089] [Test Example 2] Curability <Curability> The calorific value (I) of 5 mg of epoxy resin adhesive immediately after preparation and the calorific value (II) of the epoxy resin adhesive heated at 60°C for 2 hours immediately after preparation were measured using a DSC-1 (trade name, manufactured by Mettler Toledo, differential scanning calorimetry), and the cure rate (%) was calculated using the following formula. Cure rate = 100 x {heat generation (I) - heat generation (II)} / heat generation (I) The obtained cure rate was evaluated according to the following evaluation criteria. If the cure rate is insufficient, stickiness occurs when used to assemble medical devices, so a higher cure rate indicates a better adhesive. -Evaluation criteria- S: Curing rate 90% or more A: Cure rate 80% or more but less than 90% B: Cure rate 70% or more but less than 80% C: Less than 70% curing rate

[0090] [Test Example 3] Viscosity The viscosity of the epoxy resin adhesive was measured using a Thermo Fisher Scientific Mars 40 rheometer. The geometry used was a 20 mm diameter aluminum parallel plate. The temperature condition was 25°C. Measurements were performed under rotational conditions at a shear rate of 0.01 / s.

[0091] [Test Example 4] Shape retention The epoxy resin adhesive was molded into a dome shape with a diameter of 5 mm on a stainless steel (SUS) plate measuring 10 mm wide x 40 mm long x 1 mm thick, and left to stand for 10 minutes at 25°C. After 10 minutes, the shape was visually observed and evaluated according to the following evaluation criteria. -Evaluation criteria- S: The shape has not changed. A: The shape has changed very slightly. B: The shape has changed slightly, but it can be restored to its original shape by poking it with a needle. C: The shape is not maintained at all.

[0092] <Preparation of test specimens> Three test pieces shown in FIG. 2 were prepared for each of the Examples and Comparative Examples in the following manner for Test Examples 5 and 6-1. Immediately after preparation, each epoxy resin adhesive was applied to a SUS plate 3 (40 mm long x 5 mm wide x 1 mm thick) to a thickness of 0.08 mm, 5 mm long, and 5 mm wide, and then laminated to another SUS plate 6 and cured at 80°C for 12 hours to obtain a test piece 20 (the area of ​​the overlapping part of the two SUS plates was 5 mm long and 5 mm wide) in which the cured epoxy resin adhesive 4 was sandwiched between the SUS plates 3 and 6. The spacer 5 was a Teflon (registered trademark) sheet with a thickness of 0.08 mm.

[0093] [test] The following tests (Test Examples 5 and 6-1) were carried out on each test piece, and the results are summarized in Table 1 below.

[0094] [Test Example 5] Chemical resistance The test specimen was immersed in Esside disinfectant (product name, manufactured by Fujifilm Medical Co., Ltd., an aqueous solution containing 6% by mass of peracetic acid) for 24 hours at 40° C. After immersion, the test specimen was washed with water, and after wiping off any water droplets, the appearance of the cured epoxy resin adhesive was observed. -Evaluation criteria- S: No change is observed even when observed with a 3x magnifying glass. A: Slight cracks can be seen when observed with a 3x magnifying glass, but no cracks can be seen when observed with the naked eye. B: Slight cracks are visible upon visual inspection. C: Cracks extending into the membrane are visible upon visual inspection.

[0095] [Test Example 6-1] Sterilization durability The test specimens were subjected to hydrogen peroxide plasma sterilization treatment by performing 100 cycles of "Sterilization Cycle: Advanced Cycle" using STERRAD (registered trademark) NX (trade name, manufactured by Johnson & Johnson). The shear bond strength of each test piece was measured before and after sterilization. Specifically, the test piece was pulled toward both sides at a test speed of 2 mm / min and a gripper distance of 50 mm to measure the bond strength. This test was performed at 23°C using a benchtop precision universal testing machine AGS-X (trade name, manufactured by Shimadzu Corporation). The shear bond strength (I) (MPa) of the test piece before sterilization and the shear bond strength (II) (MPa) of the test piece after sterilization were applied to the following formula to calculate the shear bond strength retention rate (%). Shear bond strength retention rate (%) = 100 × (II) / (I) The obtained retention rate (%) of shear adhesive strength was applied to the following evaluation criteria to evaluate sterilization durability. -Evaluation criteria- S: 90% or more A: 80% or more but less than 90% B: 70% or more but less than 80% C: 60% or more but less than 70% D: Less than 60% [Test Example 6-2] Sterilization durability Using epoxy resin adhesive 8 and the substrates shown in Table 2 below, two test pieces having the substrates shown in Table 2 below were prepared for each substrate in the same manner as in <Preparation of test pieces> above. Each test piece was subjected to the same test as in Test Example 6-1. The results are shown in Table 2 below.

[0096] [Table 1-1]

[0097] [Table 1-2]

[0098] [Table 1-3]

[0099] [Table 1-4]

[0100] The blending amounts shown in the table are in parts by mass, except for component (D), whose content in the adhesive (% by mass) is shown below the blending amount. The amount of a component refers to the amount of the component itself, i.e., when the raw material contains a solvent, the amount does not include the solvent.

[0101] [Component (A)] Epoxy resin A-1: Bisphenol A diglycidyl ether (trade name jER828, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 189) A-2: Epoxy novolac resin (product number 406775, manufactured by Aldrich, epoxy equivalent weight 165-175)

[0102] [Component (B)] Amine compound having two or more unsubstituted amino groups B-1: Hexamethylenediamine B-2: 1,12-dodecanediamine B-3: Trimethylhexamethylenediamine B-4: 1,3-Cyclohexanediamine B-5: 1,3-bis(aminomethyl)cyclohexane

[0103] B-6: D-400 (trade name, manufactured by Tomoe Engineering Co., Ltd., compound represented by the following chemical formula, weight-average molecular weight 430) [ka]

[0104] B-7: m-Xylylenediamine B-8: p-menthane-1,8-diamine B-9: Isophoronediamine B-10: 4,4'-methylenebis(cyclohexylamine) B-11: 4,4'-methylenebis(2-methylcyclohexylamine) B-12: m-Phenylenediamine

[0105] [Component (C)] A compound having a non-aromatic carbon-carbon double bond group and a phenolic hydroxyl group C-1: Sumilizer GM (product name, manufactured by Sumitomo Chemical Co., Ltd.) [ka]

[0106] C-2: Sumilizer GS (product name, manufactured by Sumitomo Chemical Co., Ltd.) [ka]

[0107] C-3: Triarylphenol C-4: o-hydroxycinnamic acid C-5:

[0108] MEH-8000H (trade name, manufactured by Showa Kasei Co., Ltd., average degree of polymerization 2, weight average molecular weight 300) [ka]

[0109] C-6: p-Allylphenol

[0110] [Component (P)] Hardener other than component (B) P-1: 2-Octyl succinic anhydride P-2: Bis(3-mercaptopropionic acid) 1,4-butanediol P-3: 1,2-Dimethylimidazole P-4: 1,4-Bis(diphenylphosphino)butane P-5: Cresol novolac (product name: Phenolite KA-1160, manufactured by DIC Corporation)

[0111] P-6: N,N'-Dimethyl-1,6-diaminohexane

[0112] [Component (Q)] A compound that does not have a non-aromatic carbon-carbon double bond group and has a phenolic hydroxyl group Q-1: Nonylphenol

[0113] [Component (D)] Filler D-1: AEROSIL RX200 (product name, manufactured by Nippon Aerosil Co., Ltd., average primary particle size 12 nm) D-2: AEROSIL NAX50 (trade name, manufactured by Nippon Aerosil Co., Ltd., average primary particle size 30 nm) D-3: Fused silica SFP-30M (product name, manufactured by Denka, average primary particle diameter 700 nm) D-4: AEROSIL 200 (trade name, manufactured by Nippon Aerosil Co., Ltd., average primary particle size 12 nm)

[0114] [Table 2]

[0115] Iron SPCC: Standard Test Piece, cold-rolled steel plate Brass: Standard Test Piece, model number C2801 Aluminum: Standard Test Piece, model number A1050 Hot-dip galvanized steel sheet: Standard Test Piece Co., Ltd., hot-dip galvanized steel sheet Polystyrene: Standard Test Piece, polystyrene plate

[0116] The cured products of adhesives Nos. c1 to c6, which used epoxy resin curing agents without unsubstituted amino groups, had poor chemical resistance and sterilization durability. Additionally, adhesives Nos. c1 and c3 to c6 also had poor curing properties. The cured product of adhesive No. c7, which used a compound that did not have a non-aromatic carbon-carbon double bond group but had a phenolic hydroxyl group, had poor chemical resistance and sterilization durability. In contrast, the adhesives of the present invention (Nos. 1 to 28) have the various properties required of ordinary adhesives (working life and shape retention before hardening) at a sufficiently high level, and also have rapid hardening properties and viscosity suitable for the production of medical devices.Furthermore, it can be seen that the hardened products obtained by the hardening reaction have excellent chemical resistance and sterilization durability.

[0117] While the present invention has been described in connection with embodiments thereof, we do not intend to limit our invention to any of the details of the description unless otherwise specified, and believe that the claims should be construed broadly without departing from the spirit and scope of the invention as set forth in the appended claims.

[0118] This application claims priority based on Japanese Patent Application No. 2021-61463, filed on March 31, 2021, the contents of which are incorporated herein by reference as part of the present specification. [Explanation of symbols]

[0119] 1 Base material 2. Hardened epoxy resin adhesive 3 SUS board 4. Cured epoxy resin adhesive 5 spacers 6 SUS board 10 Medical device components 20 test specimens

Claims

1. An epoxy resin adhesive for medical devices comprising the following components (A) to (C): (A) Epoxy resin (B) Polyamine compound having two or more unsubstituted amino groups (C) Compounds having a non-aromatic carbon-carbon double bond group and a phenolic hydroxyl group

2. The epoxy resin adhesive for medical devices according to claim 1, wherein the non-aromatic carbon-carbon double bond group comprises a vinyl group.

3. 3. The epoxy resin adhesive for medical devices according to claim 1, wherein the component (C) comprises a compound having an average degree of polymerization of 2 or more.

4. The epoxy resin adhesive for medical devices according to any one of claims 1 to 3, wherein component (C) comprises a compound having a substituent at the ortho position relative to the ring-constituting carbon atom of the aromatic hydrocarbon ring to which the phenolic hydroxyl group is bonded.

5. A cured product obtained by curing the epoxy resin adhesive for medical devices according to any one of claims 1 to 4.

6. A medical device component having a metal substrate and the cured product according to claim 5 on the metal substrate.

7. The medical device component of claim 6, wherein the metal substrate is a stainless steel substrate.

8. A medical device having components fixed thereto by the cured product according to claim 5.

9. A medical device using the medical device member according to claim 6 or 7 as a constituent member.

10. The medical device according to claim 8 or 9, which is an endoscope.

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