Medical device, treatment liquid, and method for manufacturing medical device

Abstract

Provided are: a medical instrument provided with a sliding part, which has excellent sliding properties and in which peeling of a coating film provided on the sliding part is suppressed; a chemical solution suitable for use in the production of the medical instrument; and a method for producing a medical instrument including forming a coating film using the chemical solution. In the medical instrument provided with a sliding part, a coating film composed of a cured product of a composition containing a silicone resin having a hydroxyl group and a silane coupling agent is formed on the surface of the sliding part, and the composition contains an aminosilane having a specific structure as the silane coupling agent or an amine compound not belonging to the aminosilane. And a haloalkylsilane having a specific structure.

Description

Technical Field

[0001] This invention relates to medical devices, treatment solutions, and methods for manufacturing medical devices. Background Technology

[0002] Many medical devices, such as syringe barrels, plungers, injection needles, and vials, require sliding properties. One known method for imparting sliding properties to medical devices is to apply a lubricant to the sliding parts of the device. Specifically, a method has been proposed to apply a small amount of silicone compound to a laminated film covering a stop (gasket) at the tip of the plunger constituting a pre-filled syringe (see Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2020-182677 Summary of the Invention

[0006] The problem the invention aims to solve

[0007] When medical devices are coated with certain pharmaceutical agents, it is desirable that the coating is not easily peeled off to prevent adverse effects on the medication or the human body. In the pre-filled syringe described in Patent Document 1, since a small amount of silicone compound is coated on the surface of the stop, the silicone compound itself peels off less from the surface of the stop. However, since only a small amount of silicone compound is coated, the pre-filled syringe described in Patent Document 1 has room for improvement in terms of abrasiveness.

[0008] The present invention was made in view of the above-mentioned problems, and its object is to provide a medical device having a sliding part with excellent sliding properties and suppressing peeling of the coating disposed on the sliding part, a pharmaceutical solution suitable for manufacturing the medical device, and a manufacturing method comprising forming a coating using the pharmaceutical solution.

[0009] Solution for solving the problem

[0010] The inventors discovered that, in medical devices having sliding parts, by forming a coating on the surface of the sliding part consisting of a cured product of a composition comprising a silicone resin having hydroxyl groups and a silane coupling agent, such that the composition contains an aminosilane with a specific structure as a silane coupling agent or an amine compound not belonging to aminosilanes, and contains a haloalkylsilane with a specific structure, the above-mentioned problems can be solved, thereby completing the present invention.

[0011] Invention Effects

[0012] According to the present invention, a medical device having a sliding portion that has excellent sliding properties and inhibits peeling of a coating disposed at the sliding portion is provided; a pharmaceutical solution suitable for manufacturing the medical device; and a manufacturing method comprising forming a coating using the pharmaceutical solution. Detailed Implementation

[0013] Medical Equipment

[0014] The medical device has a sliding part. The sliding part is covered by a coating. The coating is composed of a cured product containing a composition of a silicone resin having hydroxyl groups and a silane coupling agent.

[0015] The above-described compositions contain an aminosilane as a silane coupling agent, or contain an amine compound that is not an aminosilane.

[0016] Moreover, the above-mentioned composition contains a haloalkylsilane.

[0017] Halogenated alkylsilanes are compounds represented by the following formula (1).

[0018] R 1 Si(OR 2 )3···(1)

[0019] In equation (1), R 1 It is a haloalkyl group with 1 or more but less than 6 carbon atoms. R 2 It is an alkyl group having 1 or more but less than 6 carbon atoms.

[0020] Specific examples of medical devices include injection needles with a film on the outer surface, bottle needles with a film on the outer surface, infusion tubing with a film on the outer surface, catheters with a film on the outer surface, guide wires with a film on the outer surface, syringe barrels with a film on the outer or inner surface, and syringe plungers with a film on the outer surface of the gasket.

[0021] The coating formed by the cured film of the above composition bonds well with various materials and is not easily peeled off.

[0022] Silane coupling agents form covalent bonds with functional groups containing active hydrogen atoms, such as hydroxyl and amino groups, present on the surface of various materials. Additionally, silane coupling agents can also bond with silicone resins containing hydroxyl groups to form a mesh-like network.

[0023] Based on the reasons stated above, the coating formed by the cured film of the above composition has the lubricity of silicone resin and is firmly bonded to various materials.

[0024] There are no particular restrictions on the material used for the sliding parts. The sliding parts can be made of polymer materials, metals, or glass.

[0025] Examples of polymer materials include polyolefins, (meth)acrylic resins, polyesters, and polyamides.

[0026] Specific examples of polyolefins include low-density polyethylene, high-density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, poly-1-butene, and poly-4-methyl-1-pentene.

[0027] Specific examples of (meth)acrylate resins include polymers of one or more (meth)acrylate monomers selected from (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate.

[0028] Examples of polyesters include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), and polylactic acid (PLA).

[0029] Examples of polyamides include nylon 6, nylon 6,6, nylon 12, nylon 6,12, and MXD nylon.

[0030] In addition, cyclic olefin polymers (COPs), which are polymers of cyclic olefins such as norbornene, and cyclic olefin copolymers (COCs), which are copolymers of cyclic olefins and olefins such as ethylene, are also preferred as polymer materials.

[0031] Furthermore, various elastic materials are preferred as polymer materials. Specific examples of elastic materials include natural rubber, isoprene rubber, butyl rubber, styrene-butadiene rubber, chloroprene rubber, silicone rubber, styrene-based elastomers, polyurethane-based elastomers, polyvinyl chloride-based elastomers, and polyolefin-based elastomers.

[0032] Specific examples of metals include various stainless steels, aluminum, aluminum alloys, titanium, and titanium alloys.

[0033] To ensure a stronger bond between the cured film of the above composition and the sliding portion, hydroxyl groups can be introduced onto the surface of the sliding portion before the coating is formed, using methods such as steam plasma treatment. Increasing the amount of hydroxyl groups on the surface of the sliding portion increases the amount of covalent bonds formed between the coating and the surface of the sliding portion. As a result, the coating bonds more firmly to the sliding portion.

[0034] The composition used to form the coating will be described below.

[0035] <Composition>

[0036] As previously stated, the composition comprises a silicone resin having hydroxyl groups and a silane coupling agent.

[0037] In addition, the composition contains an aminosilane as a silane coupling agent, or contains an amine compound that is not an aminosilane.

[0038] Furthermore, the composition contains a haloalkylsilane.

[0039] The composition may contain only one type of silicone resin with hydroxyl groups, or it may contain a combination of two or more types of silicone resins with hydroxyl groups.

[0040] The composition may contain only one aminosilane or a combination of two or more aminosilanes.

[0041] The composition may contain only one amine compound that is not an aminosilane, or it may contain a combination of two or more amine compounds that are not aminosilanes.

[0042] The composition may contain only one haloalkylsilane or a combination of two or more haloalkylsilanes.

[0043] A coating is formed by applying the composition to the sliding parts of a medical device. Therefore, the composition typically contains an organic solvent.

[0044] Aminosilanes and amine compounds catalyze the condensation reaction of silane coupling agents with each other or with hydroxyl-containing silicone resins. Therefore, by including aminosilanes or amine compounds in the composition, the composition cures well, forming a coating that is not easily peeled off from the surface of the sliding parts.

[0045] The following describes the essential or optional components contained in the composition.

[0046] [Silicone resins containing hydroxyl groups]

[0047] The composition comprises a silicone resin having hydroxyl groups. The silicone resin having hydroxyl groups imparts lubricity to the coating formed using the composition and, through reaction with the silane coupling agent described later, provides a coating having a mesh-like network and being firmly bonded to sliding parts.

[0048] The molecular structure of silicone resin is not particularly limited. The molecular structure of silicone resin can be linear or branched, with linear being preferred.

[0049] The molecular chain structure of silicone resin is a polyorganosiloxane structure, preferably a polydimethylsiloxane structure.

[0050] The position of the hydroxyl groups in silicone resins is not particularly limited, but the ends of the molecular chains are preferred.

[0051] Silicone resins may have hydroxyl groups (silanol groups) bonded to the silicon atoms of the molecular chain constituting the silicone resin, or they may have organic groups containing hydroxyl groups. As organic groups containing hydroxyl groups, hydroxyalkyl groups are preferred, hydroxyalkyl groups with 1 or more and 4 or fewer carbon atoms are more preferred, hydroxyethyl and hydroxymethyl groups are even more preferred, and hydroxymethyl groups are particularly preferred.

[0052] As a silicone resin containing hydroxyl groups, a bifunctional silicone resin in which hydroxyl groups are bonded to the silicon atoms at both ends of the linear molecule is preferred, and a modified polydimethylsiloxane in which hydroxyl groups are bonded to the silicon atoms at both ends of the linear molecule is more preferred.

[0053] [Silane coupling agent]

[0054] The composition contains a silane coupling agent. Additionally, the composition contains an aminosilane as a silane coupling agent, or an amine compound that is not an aminosilane. Furthermore, the composition contains a haloalkylsilane.

[0055] In other words, the composition contains a combination of aminosilane and haloalkylsilane, or a combination of an amine compound that is not an aminosilane and haloalkylsilane.

[0056] In addition, the composition may also contain a combination of aminosilanes, haloalkylsilanes, and amine compounds that are not aminosilanes.

[0057] Additionally, the composition may also contain a silane coupling agent that is not an aminosilane or a haloalkylsilane, to the extent that it does not impair the desired effect.

[0058] (Aminosilane)

[0059] Aminosilanes are any silane coupling agents containing an amino group; there are no particular limitations. The amino group in an aminosilane can be a primary, secondary, or tertiary amino group.

[0060] In addition, aminosilanes can also have more than two amino groups. When an aminosilane has more than two amino groups, these two or more amino groups can be the same or different.

[0061] As an aminosilane, a compound represented by the following formula (2) is preferred.

[0062] (R 5 -(R 3 -NR 7 ) a -R 4 )-Si(OR 6)3···(2)

[0063] In equation (2), R 3 It is an alkylene group with 1 or more but less than 4 carbon atoms. R 4 It is an alkylene group having 1 or more but less than 6 carbon atoms. R 5 It is a hydrogen atom or an amino group. As R 5 The amino group can be a primary amino group, a secondary amino group, or a tertiary amino group. R 6 It is an alkyl group having 1 or more but less than 6 carbon atoms. R 7 It is a hydrogen atom or an alkyl group having 1 or more but less than 6 carbon atoms. a is 0 or 1. When a is 0, R 5 It is an amino group.

[0064] Regarding R 3 Specific examples of alkylene groups include methylene, ethane-1,2-diyl (ethylene), ethane-1,1-diyl, propane-1,3-diyl, propane-1,2-diyl, and butane-1,4-diyl.

[0065] Regarding R 4 Specific examples of alkylene groups include methylene, ethane-1,2-diyl (ethylene), ethane-1,1-diyl, propane-1,3-diyl, propane-1,2-diyl, butane-1,4-diyl, pentane-1,5-diyl, and hexane-1,6-diyl.

[0066] As R 5 When the amino group is a primary amino group, R 5 It is an amino group (-NH2).

[0067] As R 5 When the amino group is a secondary amino group, R is preferred. 5 It is a monoalkylamino group. Preferably, the alkyl group comprising the monoalkylamino group is an alkyl group having 1 or more and 4 or fewer carbon atoms. Suitable specific examples of monoalkylamino groups include methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, sec-butylamino, and tert-butylamino.

[0068] As R 5 When the amino group is a tertiary amino group, R is preferred. 5 It is a dialkylamino group. Preferably, the alkyl group contained in the dialkylamino group is an alkyl group having 1 or more and 4 or fewer carbon atoms. Suitable specific examples of dialkylamino groups include dimethylamino, diethylamino, di-n-propylamino, diisopropylamino, di-n-butylamino, diisobutylamino, di-sec-butylamino, di-tert-butylamino, methyl(ethyl)amino, methyl(n-propyl)amino, and ethyl(n-propylamino).

[0069] Regarding R 6 Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl.

[0070] Regarding R 7 Specific examples of alkyl groups are those that are R 6 Specific examples of alkyl groups are the same.

[0071] a can be 0 or 1, with 1 being the preferred value.

[0072] As a suitable specific example of a compound represented by equation (2), the following can be cited:

[0073] 2-Aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, and 2-aminoethyltri-n-propoxysilane, etc., are 2-aminoethyltrialkoxysilanes.

[0074] 3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-aminopropyltri-n-propoxysilane, etc., are 3-aminopropyltrialkoxysilanes.

[0075] 4-Aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, and 4-aminobutyltri-n-propoxysilane, etc., are 4-aminobutyltrialkoxysilanes.

[0076] N-methyl-2-aminoethyltrimethoxysilane, N-methyl-2-aminoethyltriethoxysilane, and N-methyl-2-aminoethyltri-n-propoxysilane are all examples of N-methyl-2-aminoethyltrialkoxysilanes.

[0077] N-methyl-3-aminopropyltrimethoxysilane, N-methyl-3-aminopropyltriethoxysilane, and N-methyl-3-aminopropyltrin-propoxysilane are examples of N-methyl-3-aminopropyltrialkoxysilanes.

[0078] N-methyl-4-aminobutyltrimethoxysilane, N-methyl-4-aminobutyltriethoxysilane, and N-methyl-4-aminobutyltri-n-propoxysilane are examples of N-methyl-4-aminobutyltrialkoxysilanes.

[0079] N-ethyl-2-aminoethyltrimethoxysilane, N-ethyl-2-aminoethyltriethoxysilane, and N-ethyl-2-aminoethyltri-n-propoxysilane are examples of N-ethyl-2-aminoethyltrialkoxysilanes.

[0080] N-ethyl-3-aminopropyltrimethoxysilane, N-ethyl-3-aminopropyltriethoxysilane, and N-ethyl-3-aminopropyltrin-propoxysilane are examples of N-ethyl-3-aminopropyltrialkoxysilanes.

[0081] N-ethyl-4-aminobutyltrimethoxysilane, N-ethyl-4-aminobutyltriethoxysilane, and N-ethyl-4-aminobutyltri-n-propoxysilane are examples of N-ethyl-4-aminobutyltrialkoxysilanes.

[0082] N,N-Dimethyl-2-aminoethyltrimethoxysilane, N,N-Dimethyl-2-aminoethyltriethoxysilane, and N,N-Dimethyl-2-aminoethyltri-n-propoxysilane are examples of N,N-dimethyl-2-aminoethyltrialkoxysilanes.

[0083] N,N-Dimethyl-3-aminopropyltrimethoxysilane, N,N-Dimethyl-3-aminopropyltriethoxysilane, and N,N-Dimethyl-3-aminopropyltrin-propoxysilane are examples of N,N-dimethyl-3-aminopropyltrialkoxysilanes.

[0084] N,N-Dimethyl-4-aminobutyltrimethoxysilane, N,N-Dimethyl-4-aminobutyltriethoxysilane, and N,N-Dimethyl-4-aminobutyltri-n-propoxysilane are examples of N,N-dimethyl-4-aminobutyltrialkoxysilanes.

[0085] N,N-Diethyl-2-aminoethyltrimethoxysilane, N,N-Diethyl-2-aminoethyltriethoxysilane, and N,N-Diethyl-2-aminoethyltri-n-propoxysilane are examples of N,N-diethyl-2-aminoethyltrialkoxysilanes.

[0086] N,N-Diethyl-3-aminopropyltrimethoxysilane, N,N-Diethyl-3-aminopropyltriethoxysilane, and N,N-Diethyl-3-aminopropyltrin-propoxysilane are examples of N,N-diethyl-3-aminopropyltrialkoxysilanes.

[0087] N,N-Diethyl-4-aminobutyltrimethoxysilane, N,N-Diethyl-4-aminobutyltriethoxysilane, and N,N-Diethyl-4-aminobutyltri-n-propoxysilane are examples of N,N-diethyl-4-aminobutyltrialkoxysilanes.

[0088] N-(2-aminoethyl)-2-aminoethyltrimethoxysilane, N-(2-aminoethyl)-2-aminoethyltriethoxysilane, and N-(2-aminoethyl)-2-aminoethyltri-n-propoxysilane, etc.

[0089] N-(3-aminopropyl)-2-aminoethyltrimethoxysilane, N-(3-aminopropyl)-2-aminoethyltriethoxysilane, and N-(3-aminopropyl)-2-aminoethyltri-n-propoxysilane, etc.

[0090] N-(4-aminobutyl)-2-aminoethyltrimethoxysilane, N-(4-aminobutyl)-2-aminoethyltriethoxysilane, and N-(4-aminobutyl)-2-aminoethyltri-n-propoxysilane, etc.

[0091] N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrin-propoxysilane, etc., are N-(2-aminoethyl)-3-aminopropyltrialkoxysilanes.

[0092] N-(3-aminopropyl)-3-aminopropyltrimethoxysilane, N-(3-aminopropyl)-3-aminopropyltriethoxysilane, and N-(3-aminopropyl)-3-aminopropyltrin-propoxysilane are examples of N-(3-aminopropyl)-3-aminopropyltrialkoxysilanes.

[0093] N-(4-aminobutyl)-3-aminopropyltrimethoxysilane, N-(4-aminobutyl)-3-aminopropyltriethoxysilane, and N-(4-aminobutyl)-3-aminopropyltrin-propoxysilane, etc., are N-(4-aminobutyl)-3-aminopropyltrialkoxysilanes.

[0094] N-(2-aminoethyl)-4-aminobutyltrimethoxysilane, N-(2-aminoethyl)-4-aminobutyltriethoxysilane, and N-(2-aminoethyl)-4-aminobutyltri-n-propoxysilane, etc.

[0095] N-(3-aminopropyl)-4-aminobutyltrimethoxysilane, N-(3-aminopropyl)-4-aminobutyltriethoxysilane, and N-(3-aminopropyl)-4-aminobutyltrin-propoxysilane, etc., are N-(3-aminopropyl)-4-aminobutyltrialkoxysilanes.

[0096] N-(4-aminobutyl)-4-aminobutyltrimethoxysilane, N-(4-aminobutyl)-4-aminobutyltriethoxysilane, and N-(4-aminobutyl)-4-aminobutyltri-n-propoxysilane are all examples of N-(4-aminobutyl)-4-aminobutyltrialkoxysilanes.

[0097] (haloalkylsilane)

[0098] Halogenated alkylsilanes are compounds represented by the following formula (1).

[0099] R 1 Si(OR 2 )3···(1)

[0100] In equation (1), R 1 It is a haloalkyl group with 1 or more but less than 6 carbon atoms. R 2 It is an alkyl group having 1 or more but less than 6 carbon atoms.

[0101] Regarding R 1 The halogen atom contained in the haloalkyl group can be fluorine, chlorine, bromine, or iodine, with fluorine, chlorine, or bromine being preferred. As R 1 The alkyl halogroup can contain only one type of halogen atom or a combination of two or more types of halogen atoms.

[0102] Regarding R 1 Specific examples of haloalkyl groups can be given as follows:

[0103] Monohalomethyl groups such as chloromethyl, bromomethyl, and fluoromethyl;

[0104] Dichloromethyl, dibromomethyl, and difluoromethyl, etc., are dihalomethyl groups;

[0105] Trichloromethyl, tribromomethyl, and trifluoromethyl, etc.

[0106] 2-Hydroethyl compounds such as 2-chloroethyl, 2-bromoethyl, and 2-fluoroethyl;

[0107] 1-Haloethyls such as 1-chloroethyl, 1-bromoethyl, and 1-fluoroethyl;

[0108] 2,2-Dichloroethyl, 2,2-dibromoethyl, and 2,2-difluoroethyl, etc., are 2,2-dihaloethyl compounds;

[0109] 1,2-Dichloroethyl, 1,2-dibromoethyl, and 1,2-difluoroethyl, etc., are 1,2-dihaloethyl compounds.

[0110] 2,2,2-Trichloroethyl, 2,2,2-Tribromoethyl, and 2,2,2-Trifluoroethyl, etc., are 2,2,2-trihaloethyl compounds.

[0111] 3-Chloropropyl, 3-bromopropyl, and 3-fluoropropyl, etc., are 3-halopropyl groups;

[0112] 2-Chloropropyl, 2-bromopropyl, and 2-fluoropropyl, etc., are 2-halopropyl groups;

[0113] 2,3-Dichloropropyl, 2,3-Dibromopropyl, and 2,3-Difluoropropyl, etc., are 2,3-dihalopropyl groups.

[0114] 3,3,3-trichloropropyl, 3,3,3-tribromopropyl, and 3,3,3-trifluoropropyl, etc., are 3,3,3-trihalopropyl groups;

[0115] 2,2,3,3-Tetrachloropropyl, 2,2,3,3-Tetrabromopropyl, and 2,2,3,3-Tetrafluoropropyl, etc., are 2,2,3,3-tetrahalopropyl groups.

[0116] 2,2,3,3,3-pentachloropropyl, 2,2,3,3,3-pentabromopropyl, and 2,2,3,3,3-pentafluoropropyl, etc., are 2,2,3,3,3-pentahalopropyl groups;

[0117] 1-Hydro-1-methylethyl, 1-bromo-1-methylethyl, and 1-fluoro-1-methylethyl are examples of 1-halo-1-methylethyl.

[0118] 2-Hydro-1-methylethyl, 2-bromo-1-methylethyl, and 2-fluoro-1-methylethyl are examples of 2-halo-1-methylethyl.

[0119] 4-Chlorobutyl, 4-bromobutyl, and 4-fluorobutyl, etc., are 4-halobutyl groups;

[0120] 5-Chloropentyl, 5-bromopentyl, and 5-fluoropentyl, etc., are 5-halopentyl groups;

[0121] 6-Hydrohexyl groups, such as 6-chlorohexyl, 6-bromohexyl, and 6-fluorohexyl.

[0122] Because haloalkylsilanes have small molecular weights, they are easy to form coatings with high crosslinking density or to form more covalent bonds between the coating and the sliding site. Furthermore, haloalkylsilanes are readily available. For these reasons, regarding R... 1 The alkyl halogroup is preferably a chloroalkyl group having 1 or more and 3 or fewer carbon atoms. Alternatively, a chloroalkyl group having 1 or more and 3 or fewer carbon atoms may also contain 2 or more chlorine atoms.

[0123] Regarding R 6 Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, and n-hexyl.

[0124] As a specific example of a haloalkylsilane represented by formula (1), the following can be cited:

[0125] Monohalomethyltrialkoxysilanes such as chloromethyltrimethoxysilane, bromomethyltrimethoxysilane, fluoromethyltrimethoxysilane, chloromethyltriethoxysilane, bromomethyltriethoxysilane, fluoromethyltriethoxysilane, chloromethyltri-n-propoxysilane, bromomethyltri-n-propoxysilane, and fluoromethyltri-n-propoxysilane.

[0126] Dichloromethyltrimethoxysilane, dibromomethyltrimethoxysilane, difluoromethyltrimethoxysilane, dichloromethyltriethoxysilane, dibromomethyltriethoxysilane, difluoromethyltriethoxysilane, dichloromethyltri-n-propoxysilane, dibromomethyltri-n-propoxysilane, and difluoromethyltri-n-propoxysilane, etc., are dihalomethyltrialkoxysilanes.

[0127] Trichloromethyltrimethoxysilane, tribromomethyltrimethoxysilane, trifluoromethyltrimethoxysilane, trichloromethyltriethoxysilane, tribromomethyltriethoxysilane, and trifluoromethyltriethoxysilane, trichloromethyltri-n-propoxysilane, tribromomethyltri-n-propoxysilane, and trifluoromethyltri-n-propoxysilane, etc., are trihalomethyltrialkoxysilanes;

[0128] 2-chloroethyltrimethoxysilane, 2-bromoethyltrimethoxysilane, 2-fluoroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, 2-bromoethyltriethoxysilane, 2-fluoroethyltriethoxysilane, 2-chloroethyltri-n-propoxysilane, 2-bromoethyltri-n-propoxysilane, and 2-fluoroethyltri-n-propoxysilane, etc., are 2-haloethyltrialkoxysilanes;

[0129] 1-Chloroethyltrimethoxysilane, 1-bromoethyltrimethoxysilane, 1-fluoroethyltrimethoxysilane, 1-chloroethyltriethoxysilane, 1-bromoethyltriethoxysilane, 1-fluoroethyltriethoxysilane, 1-chloroethyltri-n-propoxysilane, 1-bromoethyltri-n-propoxysilane, and 1-fluoroethyltri-n-propoxysilane, etc., are 1-haloethyltrialkoxysilanes;

[0130] 2,2-Dichloroethyltrimethoxysilane, 2,2-dibromoethyltrimethoxysilane, 2,2-difluoroethyltrimethoxysilane, 2,2-dichloroethyltriethoxysilane, 2,2-dibromoethyltriethoxysilane, 2,2-difluoroethyltriethoxysilane, 2,2-dichloroethyltri-n-propoxysilane, 2,2-dibromoethyltri-n-propoxysilane, and 2,2-difluoroethyltri-n-propoxysilane, etc., are 2,2-dihaloethyltrialkoxysilanes.

[0131] 1,2-Dichloroethyltrimethoxysilane, 1,2-dibromoethyltrimethoxysilane, 1,2-difluoroethyltrimethoxysilane, 1,2-dichloroethyltriethoxysilane, 1,2-dibromoethyltriethoxysilane, 1,2-difluoroethyltriethoxysilane, 1,2-dichloroethyltri-n-propoxysilane, 1,2-dibromoethyltri-n-propoxysilane, and 1,2-difluoroethyltri-n-propoxysilane, etc., are 1,2-dihaloethyltrialkoxysilanes.

[0132] 2,2,2-trichloroethyltrimethoxysilane, 2,2,2-tribromoethyltrimethoxysilane, 2,2,2-trifluoroethyltrimethoxysilane, 2,2,2-trichloroethyltriethoxysilane, 2,2,2-tribromoethyltriethoxysilane, 2,2,2-trifluoroethyltriethoxysilane, 2,2,2-trichloroethyltri-n-propoxysilane, 2,2,2-tribromoethyltri-n-propoxysilane, and 2,2,2-trifluoroethyltri-n-propoxysilane, etc., are 2,2,2-trihaloethyltrialkoxysilanes;

[0133] 3-Chloropropyltrimethoxysilane, 3-bromopropyltrimethoxysilane, 3-fluoropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3-bromopropyltriethoxysilane, 3-fluoropropyltriethoxysilane, 3-chloropropyltri-n-propoxysilane, 3-bromopropyltri-n-propoxysilane, and 3-fluoropropyltri-n-propoxysilane, etc., are 3-halopropyltrialkoxysilanes;

[0134] 2-Chloropropyltrimethoxysilane, 2-bromopropyltrimethoxysilane, 2-fluoropropyltrimethoxysilane, 2-chloropropyltriethoxysilane, 2-bromopropyltriethoxysilane, 2-fluoropropyltriethoxysilane, 2-chloropropyltri-n-propoxysilane, 2-bromopropyltri-n-propoxysilane, and 2-fluoropropyltri-n-propoxysilane, etc., are 3-halopropyltrialkoxysilanes;

[0135] 2,3-Dichloropropyltrimethoxysilane, 2,3-dibromopropyltrimethoxysilane, 2,3-difluoropropyltrimethoxysilane, 2,3-dichloropropyltriethoxysilane, 2,3-dibromopropyltriethoxysilane, 2,3-difluoropropyltriethoxysilane, 2,3-dichloropropyltri-n-propoxysilane, 2,3-dibromopropyltri-n-propoxysilane, and 2,3-difluoropropyltri-n-propoxysilane, etc., are 2,3-dihalopropyltrialkoxysilanes.

[0136] 3,3,3-trichloropropyltrimethoxysilane, 3,3,3-tribromopropyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trichloropropyltriethoxysilane, 3,3,3-tribromopropyltriethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3,3,3-trichloropropyltrin-propoxysilane, 3,3,3-tribromopropyltrin-propoxysilane, and 3,3,3-trifluoropropyltrin-propoxysilane, etc., are 3,3,3-trihalopropyltrialkoxysilanes.

[0137] 2,2,3,3-Tetrachloropropyltrimethoxysilane, 2,2,3,3-Tetrabromopropyltrimethoxysilane, 2,2,3,3-Tetrafluoropropyltrimethoxysilane, 2,2,3,3-Tetrachloropropyltriethoxysilane, 2,2,3,3-Tetrabromopropyltriethoxysilane, 2,2,3,3-Tetrafluoropropyltriethoxysilane, 2,2,3,3-Tetrachloropropyltriethoxysilane Silanes, 2,2,3,3-tetrabromopropyltriethoxysilane, 2,2,3,3-tetrafluoropropyltriethoxysilane, 2,2,3,3,3-pentachloropropyltrinoxysilane, 2,2,3,3,3-pentabromopropyltrinoxysilane, and 2,2,3,3,3-pentafluoropropyltrinoxysilane, etc., are 2,2,3,3,3-pentahalopropyltrialkoxysilanes;

[0138] 1-Chloro-1-methylethyltrimethoxysilane, 1-bromo-1-methylethyltrimethoxysilane, 1-fluoro-1-methylethyltrimethoxysilane, 1-chloro-1-methylethyltriethoxysilane, 1-bromo-1-methylethyltriethoxysilane, 1-fluoro-1-methylethyltriethoxysilane, 1-chloro-1-methylethyltri-n-propoxysilane, 1-bromo-1-methylethyltri-n-propoxysilane, and 1-fluoro-1-methylethyltri-n-propoxysilane, etc., are 1-halo-1-methylethyltrialkoxysilanes;

[0139] 2-chloro-1-methylethyltrimethoxysilane, 2-bromo-1-methylethyltrimethoxysilane, 2-fluoro-1-methylethyltrimethoxysilane, 2-chloro-1-methylethyltriethoxysilane, 2-bromo-1-methylethyltriethoxysilane, 2-fluoro-1-methylethyltriethoxysilane, 2-chloro-1-methylethyltri-n-propoxysilane, 2-bromo-1-methylethyltri-n-propoxysilane, and 2-fluoro-1-methylethyltri-n-propoxysilane, etc., are 2-halo-1-methylethyltrialkoxysilanes;

[0140] 4-Chlorobutyltrimethoxysilane, 4-bromobutyltrimethoxysilane, 4-fluorobutyltrimethoxysilane, 4-chlorobutyltriethoxysilane, 4-bromobutyltriethoxysilane, 4-fluorobutyltriethoxysilane, 4-chlorobutyltri-n-propoxysilane, 4-bromobutyltri-n-propoxysilane, and 4-fluorobutyltri-n-propoxysilane, etc., are 4-halobutyltrialkoxysilanes;

[0141] 5-chloropentyltrimethoxysilane, 5-bromopentyltrimethoxysilane, 5-fluoropentyltrimethoxysilane, 5-chloropentyltriethoxysilane, 5-bromopentyltriethoxysilane, 5-fluoropentyltriethoxysilane, 5-chloropentyltri-n-propoxysilane, 5-bromopentyltri-n-propoxysilane, and 5-fluoropentyltri-n-propoxysilane, etc., are 5-halopentyltrialkoxysilanes;

[0142] 6-Chlorohexyltrimethoxysilane, 6-bromohexyltrimethoxysilane, and 6-fluorohexyltrimethoxysilane, 6-chlorohexyltriethoxysilane, 6-bromohexyltriethoxysilane, 6-fluorohexyltriethoxysilane, 6-chlorohexyltri-n-propoxysilane, 6-bromohexyltri-n-propoxysilane, and 6-fluorohexyltri-n-propoxysilane, etc., are 6-halohexyltrialkoxysilanes.

[0143] (Other silane coupling agents)

[0144] Silane coupling agents may also include other silane coupling agents besides aminosilanes and haloalkylsilanes, to the extent that the desired effect is not compromised.

[0145] The ratio of the mass of other silane coupling agents to the mass of the silane coupling agent is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, particularly preferably 1% by mass or less, and most preferably 0% by mass.

[0146] Other specific examples of silane coupling agents include n-propyltrimethoxysilane, n-propyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-dodecyltrimethoxysilane, n-dodecyltriethoxysilane, n-hexadecyltrimethoxysilane, n-hexadecyltriethoxysilane, n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, n-phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, and 1-hexenyltrimethoxysilane. 1-Hexenyltriethoxysilane, 1-Octenyltrimethoxysilane, 1-Octenyltriethoxysilane, 3-Mercaptopropyltrimethoxysilane, 3-Mercaptopropyltriethoxysilane, 3-Acryloyloxypropyltrimethoxysilane, 3-Acryloylpropyltriethoxysilane, 3-Methacryloxypropyltrimethoxysilane, 3-Methacryloxypropyltriethoxysilane, 3-Isocyanate-propyltrimethoxysilane, 3-Isocyanate-propyltriethoxysilane, 3-Glycidyletheroxypropyltrimethoxysilane, and 3-Glycidyletheroxypropyltriethoxysilane, etc.

[0147] Preferably, the coating formed by the composition comprises a condensate formed by condensing a hydroxyl-containing silicone resin with a silane coupling agent comprising 11 to 150 parts by weight of a hydroxyl-containing silicone resin relative to 100 parts by weight.

[0148] The amount of silane coupling agent used is preferably 18 parts by mass or more and 100 parts by mass or less relative to 100 parts by mass of hydroxyl-containing silicone resin, more preferably 25 parts by mass or more and 43 parts by mass or less.

[0149] By condensing hydroxyl-containing silicone resins with silane coupling agents at such a ratio, it is easy to form a coating with high crosslinking density and strong adhesion to the sliding parts.

[0150] When the silane coupling agent comprises aminosilane and haloalkylsilane, the ratio of the mass of haloalkylsilane to the total mass of haloalkylsilane and aminosilane is preferably 20% by mass or more and 85% by mass or less, more preferably 25% by mass or more and 80% by mass or less, and even more preferably 30% by mass or more and 75% by mass or less.

[0151] [Amine compounds]

[0152] As amine compounds, amine compounds that have been used as catalysts in the condensation reactions of silane compounds having hydrolyzable groups such as alkoxy groups can be used without particular limitation.

[0153] Examples of amine compounds include: aliphatic primary amines, aliphatic secondary amines, aliphatic tertiary amines, aromatic amines, nitrogen-containing heterocyclic compounds; compounds with amidine structures, compounds with guanidine structures, compounds with biguanide structures, and other amines that do not belong to these categories.

[0154] Specific examples of amine compounds include:

[0155] Methamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, n-pentylamine, n-hexylamine, n-octylamine, 2-ethylhexylamine, n-nonylamine, n-decylamine, laurylamine, n-pentadecanamine, hexadecylamine, stearylamine, cyclohexylamine, oleylamine monoethanolamine, 3-hydroxypropylamine, ethylenediamine, propylenediamine, hexamethylenediamine, and aliphatic primary amines such as 3-methoxypropylamine;

[0156] Dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-pentylamine, di-n-hexylamine, di-n-octylamine, di(2-ethylhexyl)amine, di-n-decylamine, dilaurylamine, dihexadecylamine, distearate, methylstearylamine, ethylstearylamine, butylstearylamine, diethanolamine, and aliphatic secondary amines such as N,N′-dimethyl-1,3-propanediamine;

[0157] Triethylamine, diisopropylethylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-octylamine, triallylamine, and triethanolamine and other aliphatic tertiary amines;

[0158] Aromatic amines such as aniline, lauryl aniline, stearyl aniline, and triphenylamine;

[0159] Pyridine, 2-aminopyridine, 2-(dimethylamino)pyridine, 4-(dimethylaminopyridine), 2-hydroxypyridine, imidazole, 2-ethyl-4-methylimidazolium, morpholine, N-methylmorpholine, piperidine, 2-piperidinemethanol, 2-(2-piperidinyl)ethanol, piperidinone, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,4-diazabicyclo[2,2,2]octane (DABCO), and nitrogen-containing heterocyclic compounds such as aziridine;

[0160] Compounds with amidine structures, such as 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU), 6-(dibutylamino)-1,8-diazabicyclo[5,4,0]undec-7-ene (DBA-DBU), 6-(2-hydroxypropyl)-1,8-diazabicyclo[5,4,0]undec-7-ene (OH-DBU), and 1,5-diazabicyclo[4,3,0]non-5-ene (DBN);

[0161] Compounds with guanidine structures, such as guanidine, phenylguanidine, and diphenylguanidine;

[0162] Compounds with biguanide structures, such as butylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide.

[0163] There is no particular limitation on the amount of amine compounds used, provided that the desired effect is not impaired.

[0164] The amount of amine compound used relative to 100 parts by mass of silane coupling agent is preferably 6 parts by mass or more and 30 parts by mass or less, more preferably 10 parts by mass or more and 20 parts by mass or less.

[0165] [Organic solvents]

[0166] Regarding the applicability to medical devices, the composition preferably contains an organic solvent. The type of organic solvent is not particularly limited, provided that the components of the organic solvent described above dissolve well.

[0167] Regarding the solubility of silicone resins containing hydroxyl groups, hydrochlorofluoroolefins (HCFOs) can be cited as organic solvents. Examples of HCFOs include AMOLEA (registered trademark) AS-300 ((E)-1-chloro-2,3,3-trifluoropropene / (Z)-1-chloro-2,3,3-trifluoropropene, manufactured by AGC Corporation) and CELEFIN (registered trademark) 1233Z (manufactured by Honmachi Chemical Industry Co., Ltd.).

[0168] In addition, chlorinated hydrocarbon solvents that are not hydrochlorofluoroolefins, such as dichloromethane, chloroform, 1,2-dichloroethane, 1,1-dichloroethane, and carbon tetrachloride, are preferred in terms of the solubility of silicone resins with hydroxyl groups.

[0169] Furthermore, regarding the solubility of silane coupling agents, alkanols are preferred. Examples of alkanols include methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, and n-hexanol.

[0170] The preferred composition is prepared by mixing a solution of a hydroxyl-containing silicone resin dissolved in a hydrochlorofluoroolefin or a chlorinated hydrocarbon solvent that is not a hydrochlorofluoroolefin with a solution of a silane coupling agent dissolved in an alkanol.

[0171] Amine compounds can be added to solutions of silicone resins containing hydroxyl groups, or to solutions of silane coupling agents. Alternatively, amine compounds can be added to solutions formed by mixing solutions of silicone resins containing hydroxyl groups and solutions of silane coupling agents.

[0172] The amount of organic solvent in the composition is not particularly limited, and should be appropriately determined considering factors such as the thickness of the film formed by using the composition. The higher the content of hydroxyl-containing silicone resin and silane coupling agent in the composition, the easier it is to form a thicker film.

[0173] 〔water〕

[0174] The composition can be cured by moisture in the air. Therefore, the composition may not contain water. However, it is preferable to add water to the composition for rapid curing.

[0175] The water content in the composition is preferably 10 parts by mass and 50 parts by mass and less than 100 parts by mass of silane coupling agent, more preferably 20 parts by mass and 35 parts by mass and less.

[0176] <Methods for forming a coating>

[0177] The composition described above is applied to the surface of the sliding part of a medical device to form a coating. There are no particular limitations on the application method. Examples of application methods include dip coating, spray coating, inkjet printing, screen printing, and roller coating. Among these methods, dip coating is preferred because it is easy to apply the composition to the surface of medical devices with complex shapes. Alternatively, spray coating, which does not involve the evaporation of organic solvents and therefore does not cause changes in the concentration of the composition, is preferred.

[0178] There are no particular limitations on the method for curing the composition coated on the medical device. The composition can also be cured at room temperature. Alternatively, to accelerate curing, the composition can be cured by heating. The heating temperature is not particularly limited, as long as the material constituting the medical device does not undergo thermal degradation or deformation, and the components contained in the coating do not decompose or thermally degrade. The heating temperature is preferably, for example, 50°C or higher and 200°C or lower, more preferably 60°C or higher and 190°C or lower, and particularly preferably 80°C or higher and 180°C or lower.

[0179] The heating time is appropriately determined taking into account factors such as heating temperature. Typically, the heating time is preferably 5 minutes or more and 6 hours or less, more preferably 10 minutes or more and 5 hours or less, and even more preferably 30 minutes or more and 2 hours or less.

[0180] Medical devices manufactured in this manner exhibit excellent sliding properties at their sliding parts. Furthermore, in medical devices manufactured in this manner, the coating formed at the sliding parts is not easily peeled off, thus maintaining the sliding properties of the medical device for a long time, and minimizing the adverse effects of peeling coating on medications or organisms.

[0181] "syringe"

[0182] A syringe consists of a barrel and a plunger.

[0183] The cylinder typically has a Luer connector at one end for allowing liquid to flow into or out of the cylinder, and an opening at the other end. The Luer connector has an opening for allowing liquid to flow.

[0184] The plunger consists of a plunger rod and a gasket. The plunger is inserted into the cylinder through an opening on the side opposite to the Luer joint of the cylinder. The gasket seals the interior space of the cylinder by sealing it against the inner surface of the cylinder. By pressing the plunger rod into or pulling it out of the cylinder, the gasket moves within the cylinder while simultaneously sealing the interior space.

[0185] In terms of ease of forming a well-sealed coating, lightweight, and resistance to breakage, the preferred material for the gaskets of the cylinder and plunger is a polymer. Specific examples of polymer materials are as described above.

[0186] In the aforementioned syringe, the aforementioned coating is formed on at least one of the inner surface of the barrel and the outer surface of the liner. Therefore, in the aforementioned syringe, the plunger can be moved smoothly with a small force.

[0187] Furthermore, the aforementioned syringes typically contain various liquid medications, liquid biological samples, etc., within their barrels. However, in the aforementioned syringes, because the coating is prevented from peeling off from the inner surface of the barrel and the outer surface of the liner, there are fewer adverse effects on the liquid medications, liquid biological samples, etc., contained within the barrel.

[0188] Pre-filled Injector

[0189] A prefilled syringe comprises a syringe barrel, a syringe plunger, a closure, and a reagent. The reagent is filled into the syringe barrel. The plunger has a gasket. One opening of the syringe barrel is closed by the gasket. The other opening of the syringe barrel is closed by the closure.

[0190] The syringe has a Luer connector at one end for allowing liquid to flow into or out of the syringe, and an opening at the other end. The Luer connector has an opening for liquid flow. In a pre-filled syringe, the opening of the Luer connector is sealed with a sealing agent.

[0191] Regarding the plunger, as previously stated.

[0192] The medication filled into the cylinder is a liquid. Examples of such medications include physiological saline, heparinized saline, contrast agents, hyaluronic acid preparations, insulin preparations, rheumatoid arthritis treatments, and anticancer agents.

[0193] In the pre-charge injector, the aforementioned coating is formed on at least one of the inner surface of the barrel and the outer surface of the gasket. Therefore, in the pre-charge injector described above, the plunger can be moved smoothly with minimal force.

[0194] Furthermore, in the aforementioned pre-filled syringe, peeling of the coating from the inner surface of the barrel and the outer surface of the liner is suppressed. Therefore, there are fewer adverse effects on the medication contained within the barrel.

[0195] Example

[0196] [Example 1]

[0197] A solution of a hydroxyl-containing silicone resin was obtained by dissolving 40 parts by mass of a modified dimethyl polysiloxane having hydroxyl groups at both ends of a linear molecular chain in 783 parts by mass of AMOLEA (registered trademark) AS-300 (manufactured by AGC).

[0198] A solution of a silane coupling agent was obtained by dissolving 30 parts by mass of chloromethyltrimethoxysilane and 30 parts by mass of N-(2-aminoethyl)-2-aminoethyltrimethoxysilane in 783 parts by mass of isopropanol.

[0199] While stirring the solution of hydroxyl-containing silicone resin with a magnetic stirrer, a solution of silane coupling agent is dripped into the solution of hydroxyl-containing silicone resin.

[0200] After the silane coupling agent solution is dripped, 17 parts by mass of water are added to the mixture of the hydroxyl-containing silicone resin solution and the silane coupling agent solution to obtain a composition for coating formation.

[0201] The liner of a plunger for a 2.25 mL syringe was immersed in the resulting composition for 5 seconds, forming a coating film on the surface of the liner.

[0202] After the pad coated with the composition was air-dried at room temperature, the pad was heated at 145°C for 120 minutes to form a film.

[0203] [Examples 2-16 and Comparative Examples 1-7]

[0204] The composition was obtained in the same manner as in Example 1, except that the amounts of hydroxyl-containing silicone resin and the types and amounts of silane coupling agents listed in Table 1 were used.

[0205] Using the compositions of the various examples and comparative examples obtained, a coating consisting of the cured composition was formed on the surface of the liner of a plunger for a 2.25 mL syringe, similar to that in Example 1.

[0206] [Example 17]

[0207] The composition was obtained in the same manner as in Example 1, except that the amount of hydroxyl-containing silicone resin listed in Table 1, the type and amount of silane coupling agent listed in Table 1, and 11 parts by weight of triethylamine were added to the composition as an amine compound.

[0208] Using the obtained composition, a coating consisting of the cured composition was formed on the surface of the liner of a plunger for a 2.25 mL syringe, similar to that in Example 1.

[0209] The types of silane coupling agents listed in Table 1 are shown below.

[0210] (Haloalkylsilane coupling agents)

[0211] A: Chloromethyltrimethoxysilane

[0212] B: 3-Chloropropyltrimethoxysilane

[0213] C: 3-Trifluoropropyltrimethoxysilane

[0214] D: 3-Bromopropyltrimethoxysilane

[0215] (Aminosilane coupling agent)

[0216] a: N-(2-aminoethyl)-2-aminoethyltrimethoxysilane

[0217] b: 3-Aminopropyltrimethoxysilane

[0218] c: N-Methyl-3-aminopropyltrimethoxysilane

[0219] d: N,N-Dimethyl-3-aminopropyltrimethoxysilane

[0220] (Other silane coupling agents)

[0221] I: 3-Glycidyl etheroxypropyltrimethoxysilane

[0222] II: Methyltrimethoxysilane

[0223] Using the syringes with a liner having a film on its surface obtained in the various embodiments, the sliding properties of the liner inside the barrel were evaluated by the following method.

[0224] In addition, the amount of coating peeled off from the liner was evaluated using the liner with a coating on its surface obtained in each embodiment and each embodiment. The evaluation results are recorded in Table 2.

[0225] <Evaluation of the sliding properties of the pad>

[0226] Insert the liner into the 2.25 mL COP syringe. Then, align the liner with the nominal capacity of the syringe.

[0227] Water is injected into the syringe through the Luer connector to fill the inside of the syringe. A rubber cap is then fitted onto the Luer connector, and a plunger rod is fitted onto the gasket, thus assembling the syringe. The assembled syringe filled with water is then left to stand at 20–30°C for 24 hours.

[0228] Then, using an Autograph (AG-X plus, manufactured by Shimadzu Corporation) equipped with a load sensor (SLBL-500N, Shimadzu Corporation), the plunger was pressed in at a speed of 300 mm / min until the gasket had moved 5 mm from the top of the barrel. The load applied by the plunger's insertion was measured, and a load-stroke graph was obtained. Furthermore, the rubber cap was removed from the syringe during the measurement using the load sensor.

[0229] The initial slip value (N) and maximum slip value (N) were read from the obtained load-stroke diagram. In the load-stroke diagram, a peak appears at the start of piston insertion, where the load is extremely high. The maximum load at this peak is the initial slip value (N). The maximum load within a range of insertion amounts exceeding the range corresponding to the aforementioned peak is the maximum slip value (N).

[0230] Furthermore, when a person manually presses the plunger into a syringe, the initial slip value has a greater impact on the perceived ease of pressing the plunger in than the maximum slip value. This is because once the plunger begins to move after being pressed in, it will continue to move even if the maximum slip value is somewhat large.

[0231] Based on the initial and maximum sliding values, the sliding properties of the gasket were determined according to the following criteria. The determination results are recorded in Table 2.

[0232] (Initial sliding value)

[0233] ◎: The initial sliding value is less than 6N.

[0234] ○: The initial sliding value is below 8N.

[0235] ×: The initial sliding value is 8N.

[0236] (Maximum sliding value)

[0237] ◎: The maximum sliding value is less than 10N.

[0238] ○: The maximum sliding value is below 15N.

[0239] ×: The maximum sliding value exceeds 15N.

[0240] <Determination of Coating Peel-off Amount>

[0241] Four coated pads were placed into 50 mL volumetric flasks with caps, and the flasks were then capped. The pads were shaken for 3 hours at 40 rpm using a shaker (R2200, manufactured by Argos Technologies, Inc.). After removing the pads from the flasks, 2 mL of methyl isobutyl ketone (Methyl isobutyl ketone) was added to the flasks to dissolve the peeled-off coating.

[0242] Using methyl isobutyl ketone added to a volumetric flask as a sample, ICP-ELISA analysis was performed to quantify the amount of silicon atoms from the coating peeled off the gaskets. Based on the quantified amount of silicon atoms and the calculated silicon atom content per unit mass of the cured compositions constituting the coatings in each example and comparative example, the amount of coating peeled off from four gaskets was calculated. The calculated amount of coating peeled off from four gaskets was divided by 4 to calculate the amount of coating peeled off from one gasket (average). The amount of coating peeled off from one gasket (average) ...

[0243] Based on the calculated peeling amount of the coating (μg / liner (1 piece)), the difficulty of coating peeling was determined according to the following criteria. The determination results are recorded in Table 2.

[0244] ◎: The amount of silicon atoms from the coating peeled off from the pad is less than 20 μg per pad.

[0245] ○: The amount of silicon atoms from the coating peeled off from the pad is less than 45 μg per pad.

[0246] ×: The amount of silicon atoms from the coating peeled off from the pads is more than 45 μg per pad.

[0247] Table 1

[0248]

[0249] Table 2

[0250]

[0251] As can be seen from Tables 1 and 2, the syringe with a liner having a coating formed using a composition that meets the aforementioned conditions not only has excellent liner slippage, but also the coating is not easily peeled off.

[0252] On the other hand, the syringe with a liner of a comparative example having a coating formed using a composition that does not meet the aforementioned conditions is poor in at least one aspect of the liner's slippage and the coating's peel resistance.

Claims

1. A medical device comprising a sliding portion covered by a film, characterized in that, The coating is composed of a cured product comprising a composition of a silicone resin having hydroxyl groups and a silane coupling agent. The composition comprises an aminosilane as the silane coupling agent, or comprises an amine compound that is not an aminosilane. The silane coupling agent comprises a haloalkylsilane represented by the following formula (1): R 1 Si(OR 2 )3···(1) (In equation (1), R) 1 It is a haloalkyl group with 1 or more but less than 6 carbon atoms, R 2 It is an alkyl group having 1 or more but less than 6 carbon atoms.

2. The medical device according to claim 1, wherein, The composition contains the aminosilane. The aminosilane comprises a silane compound represented by the following formula (2): (R 5 -(R 3 -NR 7 ) a -R 4 )-Si(OR 6 )3···(2) (In equation (2), R) 3 It is an alkylene group with 1 or more but less than 4 carbon atoms, R 4 It is an alkylene group with 1 or more but less than 6 carbon atoms, R 5 It is a hydrogen atom or an amino group, as R 5 The amino group can be a primary amino group, a secondary amino group, or a tertiary amino group, R 6 It is an alkyl group with 1 or more but less than 6 carbon atoms, R 7 It is an alkyl group with 1 or more but less than 6 carbon atoms, where a is 0 or 1. When a is 0, R 5 It is an amino group.

3. The medical device according to claim 1 or 2, wherein, The medical device is an injection needle with the coating on its outer surface, a vial needle with the coating on its outer surface, an infusion tube with the coating on its outer surface, a catheter with the coating on its outer surface, a guidewire with the coating on its outer surface, a syringe barrel with the coating on its outer or inner surface, or a syringe plunger with the coating on the outer surface of a liner.

4. The medical device according to claim 1 or 2, wherein, The coating comprises the condensate formed by condensing the silicone resin with a silane coupling agent comprising 11 to 150 parts by weight relative to 100 parts by weight of the silicone resin.

5. The medical device according to claim 1 or 2, wherein, The ratio of the mass of the haloalkylsilane to the total mass of the haloalkylsilane and the aminosilane is 20% by mass or more and 85% by mass or less.

6. The medical device according to claim 1 or 2, wherein, The R 1 It is a chloroalkyl group with 1 or more but less than 3 carbon atoms.

7. The medical device according to claim 1 or 2, wherein, The value of 'a' is 1.

8. A syringe comprising a barrel and a plunger, characterized in that, The cylinder is the syringe cylinder as described in claim 3 as the medical device, or the plunger is the syringe plunger as described in claim 3 as the medical device.

9. The syringe according to claim 8, wherein, The gaskets of the syringe barrel and the syringe plunger are made of polymer material.

10. A pre-filled syringe comprising a syringe barrel, a syringe plunger, a closure element, and a pharmaceutical agent, characterized in that, The medicine is filled into the cylinder. The syringe plunger has a liner. One opening of the syringe barrel is sealed by the gasket. The other opening of the syringe barrel is closed by the closure. At least one of the inner surface of the syringe barrel and the surface of the liner is covered by a film. The coating is composed of a cured product comprising a composition of a silicone resin having hydroxyl groups and a silane coupling agent. The composition comprises an aminosilane as the silane coupling agent, or comprises an amine compound that is not an aminosilane. The silane coupling agent comprises a haloalkylsilane represented by the following formula (1): R 1 Si(OR 2 )3···(1) (In equation (1), R) 1 It is a haloalkyl group with 1 or more but less than 6 carbon atoms, R 2 It is an alkyl group having 1 or more but less than 6 carbon atoms.

11. The pre-filled syringe according to claim 10, wherein, The composition contains the aminosilane. The aminosilane comprises a silane compound represented by the following formula (2): (R 5 -(R 3 -NR 7 ) a -R 4 )-Si(OR 6 )3···(2) (In equation (2), R) 3 It is an alkylene group with 1 or more but less than 4 carbon atoms, R 4 It is an alkylene group with 1 or more but less than 6 carbon atoms, R 5 It is a hydrogen atom or an amino group, as R 5 The amino group can be a primary amino group, a secondary amino group, or a tertiary amino group, R 6 It is an alkyl group with 1 or more but less than 6 carbon atoms, R 7 It is an alkyl group with 1 or more but less than 6 carbon atoms, where a is 0 or 1. When a is 0, R 5 It is an amino group.

12. A treatment solution used in a medical device having a sliding part for forming a film on the rubbing part, characterized in that, The treatment solution comprises: a silicone resin with hydroxyl groups and a silane coupling agent. The treatment liquid contains an aminosilane as the silane coupling agent, or contains an amine compound that is not an aminosilane. The silane coupling agent comprises a haloalkylsilane represented by the following formula (1): R 1 Si(OR 2 )3···(1) (In equation (1), R) 1 It is a haloalkyl group with 1 or more but less than 6 carbon atoms, R 2 It is an alkyl group having 1 or more but less than 6 carbon atoms.

13. The treatment liquid according to claim 12, wherein, The treatment solution contains the aminosilane. The aminosilane comprises a silane compound represented by the following formula (2): (R 5 -(R 3 -NR 7 ) a -R 4 )-Si(OR 6 )3···(2) (In equation (1), R) 3 It is an alkylene group with 1 or more but less than 4 carbon atoms, R 4 It is an alkylene group with 1 or more but less than 6 carbon atoms, R 5 It is a hydrogen atom or an amino group, as R 5 The amino group can be a primary amino group, a secondary amino group, or a tertiary amino group, R 6 It is an alkyl group with 1 or more but less than 6 carbon atoms, R 7 It is an alkyl group with 1 or more but less than 6 carbon atoms, where a is 0 or 1. When a is 0, R 5 It is an amino group.

14. A method for manufacturing a medical device, comprising a sliding part, characterized in that, It includes: applying the processing liquid of claim 12 or 13 to the sliding portion of the device to form a coating.

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