Surgical electrode with surface treatment coating

Abstract

The present invention aims to provide a surgical electrode, which is a surgical electrode of an electrosurgical instrument used in the surgery of biological tissues. By having a surface-treated coating with a specific infrared absorption spectrum at the tip of the surgical electrode, carbides such as biological tissues are difficult to adhere to, and the coating exhibits excellent adhesion. It demonstrates good resistance to eschar, especially under conditions with abundant blood or protein and fat. The present invention relates to a surgical electrode, which is a surgical electrode of an electrosurgical instrument used in the surgery of biological tissues. The surgical electrode has a tip capable of releasing high frequencies, and the tip has a surface-treated coating. The surface-treated coating has an infrared absorption spectrum with a specific infrared absorption spectrum at 950 cm⁻¹. ‑1 Up to 1060cm ‑1 The range of peaks (α), at 720 cm⁻¹ ‑1 Up to 830cm ‑1 The range of peaks (β), and at 450 cm⁻¹ ‑1 Up to 495cm ‑1 The range of peaks (γ), and the peak intensity (β) of the aforementioned peak β. A The peak intensity (α) relative to the above peak α A The ratio of (β) A / α A The values ​​range from 0.770 to 1.040.

Description

Technical Field

[0001] The present invention relates to a surgical electrode with a surface-treated coating, which can be used as a medical device and is suitable for use in electrosurgical instruments for surgical procedures in biological tissues. Background Technology

[0002] In surgical procedures, electrosurgical instruments (so-called electrosurgical knives) are indispensable, capable of hemostasis (coagulation) or incision by discharging a high-frequency current generated by the main body from surgical electrodes to biological tissue. As a problem arising from the use of electrosurgical knives, the "eschar" problem, where carbides such as biological tissue adhere to the tip of the electrosurgical knife, is known. To address this problem, a method has been proposed, characterized by a method for mass-producing multiple electrodes, each capable of being connected to a power source suitable for surgical use. This method includes a step of preparing a conductive stock material having a shape and size capable of forming multiple electrode blanks; the method further includes a step of coating at least a portion of the stock material with a non-adhesive layer; and a step of forming the coated multiple electrode blanks (see Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent document 1: Japanese Patent Application Publication No. 2000-333968. Summary of the Invention

[0006] The problem the invention aims to solve

[0007] However, the technology described in Patent Document 1 has the following problem: due to the Joule heating and discharge voltage generated by the high-frequency current released from the tip of the electrosurgical unit, the coated non-adhesive layer is damaged, and the non-adhesive layer peels off or disappears. In particular, depending on the incision site (whether it is high in protein, fat, or blood, etc.), the condition of the eschar is prone to change, which hinders the stable progress of the surgery.

[0008] The present invention aims to solve the problem of providing a surgical electrode, which is a surgical electrode for electrosurgical instruments used in the surgery of biological tissues. This electrode is difficult for carbides such as biological tissues to adhere to and has a film with excellent adhesion. In particular, it exhibits good resistance to eschar under conditions with high blood or high protein and fat content.

[0009] Solution for solving the problem

[0010] The inventors conducted repeated research to solve the above-mentioned problems and discovered that by providing a surface-treated film with a specific infrared absorption spectrum at the tip of the surgical electrode, a surgical electrode with a film that is difficult for carbides such as biological tissues to adhere to even under various conditions and has excellent adhesion can be provided, thus completing the present invention.

[0011] That is, the present invention may include the following.

[0012] <1> A surgical electrode, which is a surgical electrode of an electrosurgical instrument used in the surgery of biological tissues.

[0013] The aforementioned surgical electrode has a tip capable of releasing high frequencies.

[0014] The aforementioned top portion has a surface-treated film.

[0015] The surface-treated film described above exhibits high infrared absorption at 950 cm⁻¹. -1 Up to 1060cm -1 The range of peaks (α), at 720 cm⁻¹ -1 Up to 830cm -1 The range of peaks (β), and at 450 cm⁻¹ -1 Up to 495cm -1 The range of peaks (γ), and the peak intensity (β) of the peak β. A The peak intensity (α) relative to the peak α A The ratio of (β) A / α A The value ranges from 0.770 to 1.040.

[0016] <2> The surgical electrode according to <1>, wherein the surface-treated film comprises silicone resin (A), wherein the silicone resin (A) comprises structural units composed of D units and structural units composed of T units.

[0017] <3> The surgical electrode according to <2>, wherein the surface-treated film comprises a silicon-containing inorganic oxide (B).

[0018] <4> The surgical electrode according to any one of <1> to <3>, wherein the tip portion further comprises a base film formed of a surface treatment agent (Y) containing an amino compound (D).

[0019] Invention Effects

[0020] According to the present invention, a surgical electrode for an electrosurgical instrument used in the operation of biological tissues is provided, which exhibits excellent performance with superior adhesion even under various conditions, as it is difficult for carbides such as biological tissues to adhere to it. Attached Figure Description

[0021] Figure 1 This is a schematic diagram illustrating an example (blade-type electrode) of a surgical electrode (electrosurgical unit).

[0022] Figure 2 This is a schematic diagram showing an example (ring electrode) of a surgical electrode (electrosurgical knife).

[0023] Figure 3 This is a schematic diagram showing an example (spherical electrode) of a surgical electrode (electrosurgical knife).

[0024] Figure 4 This is a schematic diagram showing an example (needle electrode) of a surgical electrode (electrosurgical knife).

[0025] Figure 5 This is a schematic diagram illustrating an example of a surgical electrode (laparoscopy). (a) shows an L-shaped hook type, (b) shows a straight spatula type, (c) shows a J-shaped hook type, and (d) shows a cylindrical type.

[0026] Figure 6 This is a schematic diagram illustrating an example (bipolar) of a surgical electrode (electrosurgical knife).

[0027] Figure 7 This is a schematic diagram illustrating an example of forming a basement membrane on a surgical electrode.

[0028] Figure 8 This is a schematic diagram illustrating an example of forming a basement membrane and a surface-treated coating on a surgical electrode. Detailed Implementation

[0029] The surgical electrode with a surface-treated coating according to embodiments of the present invention is used in surgery on biological tissues. The surgical electrode has a specific surface-treated coating on the surface of its tip. Furthermore, a passivation film or an iron oxide film may be present between the tip of the surgical electrode and the surface-treated coating, but these films may not be present.

[0030] <Surgical Electrodes>

[0031] Surgical electrodes are electrodes detachably attached to the tip of electrosurgical instruments such as electrocautery knives. By releasing high frequencies from the electrode tip into biological tissue, they can achieve hemostasis (coagulation) or incision of biological tissue. Surgical electrodes are made of conductive materials. More specifically, examples include ferrous metals, zinc-based metals, aluminum-based metals, magnesium-based metals, nickel-based metals, titanium-based metals, zirconium-based metals, copper-based metals, tin-based metals, tungsten-based metals, chromium-based metals, manganese-based metals, molybdenum-based metals, and cobalt-based metals, with stainless steel being more preferred. Typical electrosurgical instruments with surgical electrodes include monopolar electrocautery knives, bipolar electrocautery knives, and laparoscopes. A schematic diagram of an example of a surgical electrode is shown below. Figure 1 As shown.

[0032] Figure 1 This is an example of a blade-shaped surgical electrode with a plate-like tip.

[0033] The surgical electrode 10 is a component that can be detachably installed with the main body of an electrosurgical instrument (not shown). The surgical electrode 10 consists of an electrical connection portion 13 that is electrically connected to the main body of the electrosurgical instrument, a tip portion 11 that releases high frequencies when close to biological tissue, and an intermediate portion 12 that connects the electrical connection portion 13 to the tip portion 11.

[0034] <Top section>

[0035] The tip 11 is the site that releases high frequencies when close to biological tissue. The shape of the tip is not particularly limited, except... Figure 1 In addition to the tip 11 of the blade-shaped surgical electrode 10 shown, there is also Figure 2 The tip 21 of the ring-shaped surgical electrode 20 shown Figure 3 The tip 31 of the spherical surgical electrode 30 shown Figure 4 The tip 41 of the needle-type surgical electrode 40 shown is an example of a surgical electrode that can be used as the tip electrode of an electrosurgical unit. In addition, there are... Figure 5 The L-shaped wire hook type (a) shown Figure 5 The straight shovel type (b) shown Figure 5 The J-shaped wire hook type (c) shown Figure 5 The cylindrical (d) type shown is a surgical electrode mounted on a laparoscope. Although the tip shown above is that of a monopolar surgical electrode, it could also be the tip of a bipolar surgical electrode. An example of the tip 61 of the bipolar surgical electrode 60 is shown in... Figure 6 As shown in the image.

[0036] The tip portion 11 can be a component whose surface at least a portion of the conductive material (e.g., the portion forming a surface-treated film) has been roughened, or it can be a component without roughening treatment. Methods for performing roughening treatment include, but are not limited to, sandblasting, etching using a solution (acidic solution, alkaline solution, etc.), polishing, plasma treatment, and corona discharge treatment. These treatments can be performed individually or in combination of two or more. Furthermore, the surface roughness of the tip portion 11 is preferably an arithmetic mean roughness Ra in the range of 0.05 μm or more and 0.39 μm or less, more preferably in the range of 0.08 μm or more and 0.25 μm or less, and particularly preferably in the range of 0.10 μm or more and 0.18 μm or less. Here, "surface roughness" in this specification refers to linear roughness, and the aforementioned Ra is a value measured using a contact surface roughness meter.

[0037] <Electrical Connection>

[0038] The electrical connection portion 13 is the part of the surgical electrode 10 that is electrically connected to the main body of the electrosurgical instrument. The electrical connection portion 13 is detachably mounted to the main body of the electrosurgical instrument, and is usually configured such that the electrical connection portion 13 and the main body of the electrosurgical instrument can be fitted together by a fitting structure or the like. In addition, the electrical connection portion is also made of a conductive material, and the material may be the same as or different from that of the aforementioned tip portion 11.

[0039] <Middle Section>

[0040] The middle part 12 is a component that connects the top part 11 and the electrical connection part 13. In order to conduct electricity to the top part 11, it needs to be made of a conductive material, but its shape, length, etc. are not particularly limited.

[0041] The intermediate portion 12 may have a coating 14. The coating 14 is a cured composition containing an insulating resin. Furthermore, as long as the intermediate portion 12 is in contact with the coating 14, the size, thickness, shape, etc. of the coating 14 are not particularly limited.

[0042] <Surface Treatment Coating>

[0043] The surface-treated film of this embodiment exhibits an absorption maximum (hereinafter referred to as an absorption peak) at a specific wavenumber in the infrared absorption spectrum. The surface-treated film contains: at 950 cm⁻¹ -1 Up to 1060cm -1 The absorption peak α (hereinafter referred to as "peak α") is located in the range of 720 cm⁻¹. -1 Up to 830cm -1 The absorption peak β (hereinafter referred to as "peak β") in the range, and at 450 cm⁻¹ -1 Up to 495cm -1The absorption peak γ (hereinafter referred to as "peak γ") is within the range. Furthermore, the peak intensity (β) of the aforementioned peak β of the surface-treated film... A Peak intensity relative to peak α (α) A The ratio of (β) A / α A Preferably, the value is in the range of 0.770 to 1.040, more preferably in the range of 0.830 to 1.034, and even more preferably in the range of 0.950 to 1.023. This is achieved by adjusting the peak intensity ratio β... A / α A Within the above range, good resistance to eschar and good sealing properties can be obtained.

[0044] Peak α, for example, indicates the presence of stretching vibrations of Si-O. Furthermore, peak β, for example, indicates the presence of stretching vibrations of Si-C. Additionally, peak γ, for example, indicates the presence of inorganic solids containing Si-O bonds.

[0045] In addition, the peak intensity of peak γ (γ A Peak intensity α relative to peak α A The ratio (γ) A / α A The optimal value is within the range of 0.005 to 0.135. Furthermore, the peak intensity (γ) of peak γ is... A Peak intensity β relative to peak β A The ratio (γ) A / β A The preferred value is 0.005 to 0.180.

[0046] There are no particular limitations on the analytical methods for the infrared absorption spectra of surface-treated films; for example, the ATR method, as a type of infrared spectroscopy, can be cited. When performing analysis using the ATR method, an example of an apparatus is the FT-IR (Spectrum Two) manufactured by Perkin Elmer, equipped with an ATR measurement accessory (GladiATR). TM Equipment, etc.

[0047] The surface-treated coating of this embodiment is not limited in method of formation as long as the desired absorption intensity can be obtained at peaks α, β, and γ. For example, it can be formed by contacting the surface-treated agent (X) with the surface of the tip of the surgical electrode. Furthermore, if the tip of the surgical electrode has a base membrane, the surface-treated coating is formed by contacting the surface-treated agent (X) with the surface of the base membrane. Moreover, the contact of the surface-treated agent (X) can be performed on part or all of the tip or the base membrane.

[0048] The surface-treated coating can be formed on the entire surface of the tip or on a portion thereof. In the case of a blade-type surgical electrode, examples of this coating include, for instance, the blade portion of the tip or the planar portion of the tip. Furthermore, in this specification, the planar portion refers to… Figure 7 The largest part of the blade portion at the top 11.

[0049] One more preferred embodiment is that the aforementioned tip portion has a base film formed of a surface treatment agent (Y) containing an amino compound (D).

[0050] In the portion where no surface-treated coating is formed, only a base coat may be formed. For example, in the case of a blade-type surgical electrode, a base coat may be formed on the entire surface of the blade portion, and a surface-treated coating may be formed on a portion thereof. Furthermore, in the tip portion 11, only a base coat may be formed on the entire surface or a portion of the end portion (hereinafter referred to as the "intermediate connection portion") on the side of the intermediate portion 12, or both a base coat and a surface-treated coating may be formed.

[0051] <Surface Treatment Agent (X)>

[0052] From the viewpoint of forming a surface-treated film that satisfies the peak intensity of the infrared absorption spectrum described above, the surface-treated agent (X) of this embodiment preferably contains a silicone resin (A) and a silicon-containing inorganic oxide (B).

[0053] <Silicone Resin (A)>

[0054] As for silicone resin (A), there are no particular restrictions as long as it is a silicone resin with multiple siloxane bonds and an organopolysiloxane structure in which organic groups are bonded on silicon (Si).

[0055] From the viewpoint of ensuring that the surface-treated film meets the peak intensity requirement of the aforementioned infrared absorption spectrum, it is preferable to use a resin comprising the following components: a silicone resin (A2) comprising an organopolysiloxane structure (M unit or D unit) having at least one or two organic groups bonded to Si in one molecule; and a silicone resin (A1) comprising an organopolysiloxane structure (T unit or Q unit) having at least three or four organic groups bonded to Si in one molecule. Among these, it is preferable to use a resin comprising the following components: a rubber-like silicone resin (A2) comprising D units; and a resin-like silicone resin (A1) comprising T units. Furthermore, the position of the organic groups is not particularly limited and can be bonded to the main chain, side chain, or end.

[0056] The silicone resin (A) can be a homopolymer having the aforementioned organopolysiloxane structure, a mixture of a homopolymer having the aforementioned organopolysiloxane structure and a homopolymer having a polysiloxane structure, or a copolymer (block copolymer or graft copolymer) having the aforementioned organopolysiloxane structure and a polysiloxane structure. Furthermore, the silicone resin (A) can be addition-type or condensation-type. Moreover, the silicone resin (A) can be any of the following: thermosetting, room temperature curing (RTV), or UV curing.

[0057] Examples of organic groups bonded to Si in the organopolysiloxane structure include, but are not limited to, saturated hydrocarbon groups, unsaturated hydrocarbon groups, haloalkyl groups, and epoxide cycloalkyl groups. Examples of saturated hydrocarbon groups include, for example, linear or branched alkyl groups and cycloalkyl groups. Examples of unsaturated hydrocarbon groups include, for example, linear or branched alkenyl groups, cycloalkenyl groups, cycloalkenylalkyl groups, and aryl groups. Furthermore, unsaturated hydrocarbon groups are preferably unsaturated hydrocarbon groups, more preferably alkenyl groups, and particularly preferably vinyl or hexenyl groups.

[0058] Examples of haloalkyl groups include chloromethyl, 3-chloropropyl, 1-chloro-2-methylpropyl, and 3,3,3-trifluoropropyl. Examples of epoxycycloalkyl groups include epoxycyclopentyl, epoxycyclohexyl, and epoxycyclooctyl. Examples of linear or branched alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. Examples of cycloalkyl groups include cyclopentyl and cyclohexyl. Examples of linear or branched alkenyl groups include vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, pentenyl, and hexenyl. Examples of cycloalkenyl groups include cyclopentenyl and cyclohexenyl. Examples of cycloalkenyl alkyl groups include cyclopentenylethyl, cyclohexenylethyl, and cyclohexenylpropyl. Examples of aryl groups include phenyl groups.

[0059] As for the polysiloxane structure, there are no particular limitations as long as it differs from the aforementioned organopolysiloxane structures. Examples include polysiloxane structures having at least two hydrogen atoms bonded to Si in one molecule, and polysiloxane structures having at least two alkoxy groups bonded to Si in one molecule. Examples of alkoxy groups include methoxy, ethoxy, propoxy, and butoxy. Furthermore, the alkoxy group can be linear or branched.

[0060] In the preparation of the surface treatment agent (X), one or more of the aforementioned silicone resins (A) may be used. As a preferred embodiment of the silicone resin (A1), a silicone resin containing T units includes a polymer having an organopolysiloxane structure having at least two unsaturated hydrocarbon groups bonded to Si in one molecule, and a mixture of a polymer having a polysiloxane structure having at least two hydrogen atoms bonded to Si in one molecule.

[0061] Examples of polymers having an organopolysiloxane structure having at least two unsaturated hydrocarbon groups bonded to Si in one molecule include: dimethyl polysiloxanes having dimethyl vinyl siloxy groups at both ends of the molecular chain; dimethyl siloxane-methyl phenyl siloxane copolymers having dimethyl vinyl siloxy groups at both ends of the molecular chain; dimethyl siloxane-methyl vinyl siloxane copolymers having dimethyl vinyl siloxy groups at both ends of the molecular chain; dimethyl siloxane-methyl vinyl siloxane copolymers having trimethyl siloxy groups at both ends of the molecular chain; dimethyl siloxane-methyl vinyl siloxane-methyl phenyl siloxane terpolymers having trimethyl siloxy groups at both ends of the molecular chain; dimethyl siloxane-methyl vinyl siloxane copolymers having silanol groups at both ends of the molecular chain; and methyl vinyl polysiloxanes having silanol groups at both ends of the molecular chain. In addition, examples include various homopolymers, copolymers, and terpolymers in which a portion of the methyl group is replaced by an alkyl group other than methyl, such as ethyl or propyl, or a haloalkyl group such as 3,3,3-trifluoropropyl or 3,3,3-trichloropropyl. A mixture of two or more selected from these homopolymers, copolymers, and terpolymers can be used in the preparation of surface treatment agent (X).

[0062] Polymers having a polysiloxane structure having at least two hydrogen atoms bonded to Si in one molecule are not particularly limited, and examples include, for example, SiH groups having at least two hydrogen atoms bonded to Si in one molecule, and organohydrogen polysiloxanes with linear, cyclic, branched, or three-dimensional network structures having repeating diorganosiloxane structures as the main chain and the two ends of the molecular chain being capped by triorganosiloxy groups. More specifically, examples include: methylhydropolysiloxanes with trimethylsiloxy groups at both ends of the molecular chain; dimethylsiloxane-methylhydrosiloxane copolymers with trimethylsiloxy groups at both ends of the molecular chain; methylhydropolysiloxanes with silanol groups at both ends of the molecular chain; dimethylsiloxane-methylhydrosiloxane copolymers with silanol groups at both ends of the molecular chain; dimethylpolysiloxanes with dimethylhydrosiloxy groups at both ends of the molecular chain; and dimethylsiloxane-methylhydrosiloxane copolymers with dimethylhydrosiloxy groups at both ends of the molecular chain. Mixtures of two or more selected from these homopolymers and copolymers can be used in the preparation of the surface treatment agent (X).

[0063] As one of the preferred embodiments of a silicone resin (A2) containing D units, sources of D units for a silicone resin containing D units include dimethyldisilanol, dimethyldimethoxysilane, dimethyldiethoxysilane, tetramethyldisiloxane, dimethylsiloxane oligomers, methacryloyloxypropyldimethoxymethylsilane, methyldimethoxyphenylsilane, diethoxymethylphenylsilane, methylphenyldisilanol, 1,4-bis(methyldimethoxysilyl)benzene, 1,4-bis(methyldiethoxysilyl)benzene, etc. These polymers are examples of silicone resins (A2) containing D units.

[0064] The weight-average molecular weight of silicone resin (A2) is not particularly limited, but is generally in the range of 3,000 to 70,000, preferably in the range of 3,500 to 65,000. Furthermore, the vinyl equivalent of silicone resin (A1) is not particularly limited, but is generally 0.3 to 10 mol of SiH groups per mol of vinyl groups, preferably in the range of 0.5 to 5 mol. The weight-average molecular weight of silicone resin (A1) is not particularly limited, but is generally in the range of 6,000 to 45,000, preferably in the range of 6,500 to 40,000. The weight-average molecular weight is determined by GPC (gel permeation column chromatography) and converted to polystyrene values.

[0065] <Silicon-containing inorganic oxides (B)>

[0066] Silicon-containing inorganic oxides (B) are composed of silicon (Si) and oxygen (O), and are substances other than organic compounds; their types are not limited. Furthermore, silicon dioxide composed of silica is also included, and can be either crystalline or amorphous. Crystalline silica refers to a solid substance with a crystalline structure in which the atoms constituting the crystal are arranged in a three-dimensional, regular, periodic pattern to form a spatial lattice. Examples of crystalline silica include quartz, cristobalite, and tridymite. Amorphous silica refers to a substance in which atoms are not arranged in a regular, periodic pattern and are aggregated without forming a definite crystalline structure. Examples of amorphous silica include glass, silica gel, fumed silica, and diatomaceous earth. Additionally, silicon-containing inorganic oxides (B) can also be compounds containing metallic elements such as sodium, lithium, calcium, magnesium, and zircon as constituent elements; examples include sodium silicate, calcium silicate, magnesium silicate, and zircon.

[0067] The average particle size of silicon-containing inorganic oxides (B) is not particularly limited, but is generally in the range of 1 nm or more and 50 μm or less, preferably in the range of 5 nm or more and 1 μm or less. The average particle size can be determined, for example, by using an electron microscope to measure the average value of 20 or more inorganic oxides (B). Furthermore, in the case of inorganic oxides with a large aspect ratio, the aspect ratio is used to determine the average particle size.

[0068] The manufacturing method of the surface treatment agent (X) in this embodiment is not particularly limited, and it can be manufactured by mixing silicone resin (A), silicon-containing inorganic oxide (B), solvent, curing agent (C), and additives.

[0069] The solvent contained in the surface treatment agent (X) is not particularly limited, but examples include: alcohols, acetonitrile, 2-butoxyethanol, propylene glycol monomethyl ether, benzene, ethylbenzene, toluene, xylene, cyclohexane, methyl acetate, 2-ethoxyethyl acetate, ethyl acetate, butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, and other organic solvents; mixtures of these organic solvents with water, etc.

[0070] <Curing Agent (C)>

[0071] As a curing agent contained in the surface treatment agent (X), there are no particular limitations as long as it can function as a curing agent for the silicone resin (A). For example, substances containing metallic elements selected from titanium, platinum, rhodium, and palladium can be cited. Platinum compounds are particularly preferred. Examples of platinum compounds include: platinum (including platinum black), rhodium, palladium, and other platinum group metals; H2PtCl4·nH2O, H2PtCl6·nH2O, NaHPtCl6·nH2O, KHPtCl6·nH2O, Na2PtCl6·nH2O, K2PtCl4·nH2O, PtCl4·nH2O, PtCl2, Na2HPtCl4·nH2O (wherein, in each formula, n is an integer from 0 to 6). The compounds include: platinum chloride, chloroplatinic acid, or chloroplatinate (preferably 0 or 6); alcohol-modified chloroplatinic acid (the product of the reaction of alcohol and chloroplatinic acid); complexes of chloroplatinic acid and olefins; compounds in which platinum group metals such as platinum black and palladium are supported on supports such as alumina, silica, and carbon; rhodium-olefin complexes; triphenylphosphine rhodium chloride (Wilkinson catalyst); complexes of platinum chloride, chloroplatinic acid, or chloroplatinate with vinylsiloxanes; and compounds in which platinum chloride is supported on polystyrene-polyethylene glycol.

[0072] In addition, one or more of these curing agents can be used in the preparation of surface treatment agent (X).

[0073] <Other Additives>

[0074] The surface treatment agent (X) of this embodiment may contain various additives as needed. Examples of additives include, but are not limited to, solvents, conductive compounds, surfactants, defoamers, leveling agents, thickeners, antibacterial and antifungal agents, colorants, and fluoropolymers. These additives may be added without impairing the effects of the present invention.

[0075] The proportion of each component in the surface treatment agent (X) is not particularly limited as long as the infrared absorption spectrum of the surface treatment film formed by the surface treatment agent (X) is a specified infrared absorption spectrum. As the mass ratio relative to all solid components in the surface treatment agent (X), the silicone resin (A) is preferably in the range of 70.0 to 99.5% by mass, and more preferably in the range of 80.0 to 99.0% by mass.

[0076] As a mass percentage relative to all solid components in the surface treatment agent (X), the silicon-containing inorganic oxide (B) is preferably in the range of 0.3 to 30.0% by mass, more preferably in the range of 0.7 to 20.0% by mass.

[0077] As a mass percentage relative to all solid components in the surface treatment agent (X), the curing agent (C) is preferably in the range of 0.005 to 0.045% by mass, and more preferably in the range of 0.007 to 0.040% by mass.

[0078] Furthermore, when silicone resin (A) comprises silicone resin (A1) and silicone resin (A2), there is no particular limitation on the ratio (by mass) of them, but (A1):(A2) is preferably in the range of 1:5 to 10:1, and more preferably in the range of 1:2 to 5:1.

[0079] <Surface Treatment Agent (Y)>

[0080] The surface treatment agent (Y) of this embodiment contains at least a compound (D) having an amino group. By using the surface treatment agent (Y), it is possible to form a base film that improves the resistance to eschar (especially eschars derived from proteins and fats) and the adhesion of the surface-treated coating disposed on the object material of the surgical electrode.

[0081] The compound (D) containing an amino group is not particularly limited. For example, the amino group can be any one of primary, secondary, and tertiary amino groups, or a substance containing two or more of these amino groups. Specifically, examples include: amine-based curing agents; homopolymers or copolymers containing glycidylamine type epoxy resins, polyethyleneimine resins, melamine resins, aromatic amine resins, etc.; and silane coupling agents containing amino groups. Examples of amine-based curing agents include, but are not limited to, dicyandiamide, diethylenetriamine, N-aminoethylpiperazine, m-phenylenediamine, 2-methylimidazole, and 2-ethyl-4-methylimidazole. Furthermore, when using an amine-based curing agent, it is preferable to use it in combination with an epoxy resin.

[0082] As a silane coupling agent containing an amino group, there is no particular limitation as long as it contains one amino group. Examples include: N-2-(aminoethyl)-3-aminopropyldimethylmethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyldiethylethoxysilane, and N-2-(aminoethyl)-3-aminopropylethyldiethoxysilane. Silanes, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyldimethylmethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyldiethylethoxysilane, 3-aminopropylethyldiethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, etc.

[0083] The solvent contained in the surface treatment agent (Y) is not particularly limited, and examples include: alcohols, acetone, acetonitrile, benzene, cyclohexane, methyl acetate, ethyl acetate, methyl ethyl ketone, and other organic solvents; mixtures of these organic solvents with water, etc. As an organic solvent, alcohols with 5 or fewer carbon atoms are preferred. In addition, in the case of a mixture of organic solvent and water, the mass percentage of water contained is preferably less than 5% by mass, and more preferably substantially anhydrous.

[0084] In addition, the surface treatment agent (Y) may contain conductive compounds that impart conductivity, leveling agents for improving wettability, film-forming aids for improving film-forming properties, organic or inorganic crosslinking agents for forming a strong film, defoamers for inhibiting foaming, thickeners for controlling viscosity, rust inhibitors, and other additives, which may be combined within the scope of not impairing the effects of the present invention.

[0085] The total content of amino-containing compounds (D) in the surface treatment agent (Y) is not particularly limited, but is preferably in the range of 0.1% by mass or more and 10% by mass or less relative to the total amount of the surface treatment agent (Y), and more preferably in the range of 0.5% by mass or more and 5% by mass or less.

[0086] <Surgical electrodes with surface-treated coatings and their manufacturing methods>

[0087] The method for manufacturing a surgical electrode with a surface-treated film according to this embodiment can be exemplified by the following method. First, by performing a contact process that brings a surface-treated agent (Y) into contact with the surface of the shaped surgical electrode (at least part or all of the tip portion) or on the surface, and a drying process that dries the surface-treated agent (Y) in contact with the surface of the surgical electrode, a surgical electrode with a base film can be manufactured.

[0088] Before the process of contacting the surface treatment agent (Y) with the surgical electrode, the metal material may be pretreated to create an uneven surface on the surgical electrode, or to remove oil, dirt, or oxide film adhering to the surface of the surgical electrode. There are no particular limitations on the pretreatment method, and examples include: roughening treatments such as sandblasting, etching using solutions (acidic solutions, alkaline solutions, etc.), polishing, plasma treatment, and corona discharge treatment; cleaning treatments such as hot water washing, solvent cleaning, alkaline degreasing cleaning, and acid pickling; oxide film removal treatments; and water washing. Furthermore, these treatments may be performed individually or in combination of two or more.

[0089] Various contact methods can be used to contact the surface treatment agent (Y), and the optimal method can be appropriately selected according to the shape of the surgical electrode, etc. Specifically, methods such as coating with a coating device, immersion treatment, spray treatment, flow coating, roller coating, and bar coating can be cited, but are not limited to these methods.

[0090] Furthermore, methods for drying the surface treatment agent (Y) include, but are not limited to, drying methods using hot air, induction heaters, infrared rays, near-infrared rays, or vacuum distillation. The drying temperature is not particularly limited, but is preferably in the range of 40–250°C, and more preferably in the range of 60–180°C. Furthermore, the drying time is not particularly limited and can be appropriately varied depending on the type of material used and the amount of surface treatment agent (Y) adhering to the surface of the surgical electrode.

[0091] The method for manufacturing a surgical electrode with a surface-treated film according to this embodiment further includes: a step of contacting a surface-treated agent (X) with the entire surface or a portion of the surface of a base membrane formed on the surgical electrode; and a step of drying the surface-treated agent (X) that has contacted the surgical electrode or the base membrane to form a surface-treated film. By performing these steps, a surface-treated film or a laminated film comprising a base membrane and a surface-treated film can be formed on the surgical electrode.

[0092] Various contact methods can be used for the surface treatment agent (X), and the optimal method can be appropriately selected according to the shape of the surgical electrode being treated. Specifically, examples include: dipping treatment, spraying treatment, flow coating treatment, roller coating, bar coating, and other coating methods; and coating methods using one or more coating devices such as spin coaters, slot coaters, die coaters, doctor blade coaters, and dispensing machines.

[0093] The drying temperature of the surface treatment agent (X) is not particularly limited, but is preferably in the range of 40 to 250°C, and more preferably in the range of 60 to 180°C. The drying method is not particularly limited, and methods such as drying using hot air, induction heaters, infrared radiation, near-infrared radiation, or vacuum distillation are examples. Furthermore, the drying time is not particularly limited and can be appropriately varied depending on the type of material used and the amount of surface treatment agent (X) adhering to the surface of the surgical electrode. For example, it can be 10 minutes or more, 15 minutes or more, or less than 60 minutes or less than 30 minutes.

[0094] Before the process of contacting the surface treatment agent (X) with the surgical electrode, the metal material may be pretreated to create an uneven surface on the surgical electrode, or to remove oil, dirt, or oxide film adhering to the surface of the surgical electrode. There are no particular limitations on the pretreatment method, and examples include: roughening treatments such as sandblasting, etching using solutions (acidic solutions, alkaline solutions, etc.), polishing, plasma treatment, and corona discharge treatment; cleaning treatments such as hot water washing, solvent cleaning, alkaline degreasing cleaning, and acid washing; oxide film removal treatments; and water washing. Furthermore, these treatments may be performed individually or in combination of two or more.

[0095] By treating with surface treatment agents (Y) and (X), a surface-treated membrane comprising a base membrane and a surface-treated membrane can be formed on a surgical electrode. Furthermore, the portion forming the base membrane and the portion forming the surface-treated membrane may be the same region or different regions. However, the base membrane exists beneath the portion forming the surface-treated membrane.

[0096] In one example, the substrate film formed by the surface treatment agent (Y) can be as follows: Figure 7 (a) The shaded line shows the entire surface of the blade portion at the top 11, which can also be as shown in the image. Figure 7 (b) As shown by the shaded line, it is formed on the blade portion at the top end 11 and a part of the intermediate connecting portion, and can also be as follows: Figure 7 (c) shows the portion of the blade portion of the tip portion 11 that is far from the electrical connection portion 13 (not formed on the portion near the middle connection portion).

[0097] Additionally, in one example, the surface treatment film formed by the surface treatment agent (X) can be as follows: Figure 8 (a) The midpoint pattern is formed on the entire surface of the planar portion (the upper and lower surfaces of the blade portion) at the tip, and not on the side surface of the blade portion (surfaces other than the planar portion). However, a surface treatment film may also be formed in the area from the electrical connection portion 13 side to the end 2 mm along the length direction of the blade portion. Additionally, in another example, such as... Figure 8(b) As shown in the midpoint pattern, the surface-treated coating is not formed on the sides, top, and bottom ends of the blade portion. By not forming the surface-treated coating on the sides, top, and bottom ends (parts far from the electrical connection 13), especially at the corners, high frequencies can be sufficiently released from the portion accessible to biological tissue, i.e., the discharge portion (hereinafter referred to as the "discharge portion"), thus ensuring good cutting ability of the surgical electrode instrument. Furthermore, when forming the surface-treated coating on the aforementioned sides, top, and bottom ends, especially at the corners, it is preferable to make the coating thickness thinner (e.g., 10 μm or less, preferably 5 μm or less, more preferably 2 μm or less). Therefore, since high frequencies can be sufficiently released from the discharge portion, which is the portion accessible to biological tissue, a reduction in cutting ability can be prevented.

[0098] The amount of the film composed of the surface-treated agent (Y) at the tip of the surface-treated coating (or the blade portion in the case of a blade-type surgical electrode) is not particularly limited, but is preferably 0.1 mg / m³. 2 Above and 50mg / m 2 Within the following range, more preferably within 1 mg / m³ 2 Above and 40mg / m 2 Within the following range. Furthermore, when the substrate membrane is formed from a silane coupling agent having an amino group, it is preferably within the above range based on the mass equivalent to SiO2.

[0099] Furthermore, the amount of film on the substrate membrane can be determined by measuring the amount of film on a specified area of ​​metallic material. Additionally, when the substrate membrane is formed by a silane coupling agent containing amino groups, it can be analyzed using fluorescence X-ray diffraction, and the mass of SiO2 converted from the intensity of Si can be calculated to determine the amount of film per unit area.

[0100] Furthermore, the combined thickness of the base film (surface treatment agent (Y)) and the surface treatment coating (surface treatment agent (X)) formed at the tip (or blade portion in the case of a blade-type surgical electrode) is preferably in the range of 10 μm or more and 400 μm or less, more preferably in the range of 20 μm or more and 300 μm or less, even more preferably in the range of 30 μm or more and 200 μm or less, and particularly preferably in the range of 50 μm or more and 150 μm or less.

[0101] Example

[0102] The effects of the present invention are illustrated below through specific examples. However, the description of the following examples does not limit the scope of the present invention.

[0103] (1) Preparation of surgical electrodes

[0104] Prepared Figure 1The tip 11 of the surgical electrode shown is a plate-shaped blade-type surgical electrode. The material of the prepared surgical electrode and the dimensions of the blade portion are shown below. The surface roughness (arithmetic mean roughness: Ra) of the blade portion was measured using a three-dimensional surface roughness measuring machine (Surfcom 570A, Tokyo Precision Manufacturing Co., Ltd.). The measurement was performed by scanning 2.0 mm at a speed of 0.3 mm / s.

[0105] (Z1) Material of surgical electrode: SUS304 stainless steel Ra=0.14μm

[0106] Blade dimensions: Plate thickness 0.3mm, length 17.0mm, width 2.5mm.

[0107] (Z2) Material of surgical electrodes: SUS316L stainless steel Ra=0.14μm

[0108] Blade dimensions: Plate thickness 0.3mm, length 17.0mm, width 2.5mm.

[0109] (Z3) Material for surgical electrodes: Tungsten steel Ra=0.14μm

[0110] Blade dimensions: Plate thickness 0.3mm, length 17.0mm, width 2.5mm.

[0111] The blade portion of the surgical electrode was immersed in 2-propanol (manufactured by Pure Chemical Co., Ltd., Grade I) and subjected to ultrasonic treatment for 10 minutes to remove surface oil and dirt. Then, the blade portion was dried at 120°C for 10 minutes to remove the adhering 2-propanol.

[0112] (2) Preparation of surface treatment agent

[0113] The surface treatment agent (X) is prepared by mixing the following: silicone resin (A), silicon-containing inorganic oxide (B), and curing agent (C), with xylene to achieve a solid content concentration of 15-40%, to prepare surface treatment agents X1 to X22. In Table 1, the mass percentages of "silicone resin (A)," "silicone-containing inorganic oxide (B)," and "curing agent (C)" represent the mass ratio of the solid content of each component to their total solid content. Furthermore, the A1:A2 ratio in surface treatment agents X2 to X17 represents the solid content mass ratio.

[0114] [Silicone Resin (A)]

[0115] A1: A mixture of polydimethylsiloxane having dimethylvinylsiloxane at both ends of the molecular chain and methylhydrosiloxane-dimethylsiloxane copolymer having trimethylsilyl at both ends of the molecular chain (T unit)

[0116] A2: Two-component addition-type liquid silicone rubber with vinyl end groups (D unit)

[0117] A3: Single-component curable oligomer (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name = KR-400) (T unit)

[0118] A4: Methyl / phenyl silicone resin (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name = KR-282) (D unit and T unit)

[0119] A5: Methyl / phenyl silicone resin (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name = KR-300) (D unit and T unit)

[0120] [Silicon-containing inorganic oxides (B)]

[0121] B1: Amorphous silica (average particle size 12nm)

[0122] B2: Crystalline silica (average particle size 12nm)

[0123] B3: Sodium silicate (average particle size 50nm)

[0124] B4: Calcium silicate (average particle size 40nm)

[0125] B5: Magnesium silicate (average particle size 30nm)

[0126] B6: Zircon (average grain size 1μm)

[0127] [Curing agent (C)]

[0128] C1: Tetrachloroplatinum(II) acid (manufactured by Shin-Etsu Chemical Industry Co., Ltd., product name = D-168)

[0129] C2: Titanium butoxide (manufactured by Shin-Etsu Silicon Co., Ltd., product name = D-20)

[0130] C3: Titanium acetylacetonate (manufactured by Matsumoto Fine Chemicals Co., Ltd., product name = TC-100)

[0131] C4: Platinum group catalyst (manufactured by Arakawa Chemical Industry Co., Ltd., product name = CATA93B)

[0132] Furthermore, regarding the surface treatment agent (Y), a solution (Y1, Y2) is prepared by mixing D1 or D2, which are compounds (D) containing amino groups, with ethanol in such a way that the mass concentration of the solid component of D1 or D2 reaches 1.0%.

[0133] [Compounds containing amino groups (D)]

[0134] D1: 3-Aminopropyltriethoxysilane

[0135] D2: N-(2-Aminoethyl)-3-aminopropyltrimethoxysilane

[0136] [Table 1]

[0137]

[0138] (3) Manufacturing of the top portion 11 having a surface-treated film

[0139] Using the dispensing machine described below, various surface treatment agents (X) shown in Table 2 were applied to the flat portion (both sides) of the top end 11 and dried at a drying temperature for 30 minutes to obtain surgical electrodes of Examples 1 to 27 and Comparative Examples 1 to 4 with surface treatment films having a specified film thickness (refer to Table 2).

[0140] Dispensing machine (desktop): Manufactured by MUSASHI ENGINEERING, INC., Product names: ML-808GX, SM4000MEGAX-3A-SS

[0141] Furthermore, the same treatment was performed on the planar portion (both sides) of the tip portion 11, which requires a base membrane. Regarding the base membrane, the blade portion, after removing oil and dirt, was immersed in a surface treatment agent (Y). After immersion, the blade portion was dried at 120°C for 10 minutes, thereby obtaining a surgical electrode with a base membrane. Additionally, when using Y1 and Y2 to form the base membrane, analysis was performed using fluorescence X-ray diffraction, and the mass of SiO2 was calculated from the intensity of Si to determine the amount of membrane per unit area.

[0142] [Table 2]

[0143]

[0144] (4) FT-IR measurement (β) A / α A γ A / α A γ A / β A )

[0145] Analysis was performed using the ATR method, a type of infrared spectroscopy. The apparatus used was a Perkin Elmer FT-IR (Spectrum Two) system equipped with an ATR measurement accessory (GladiATR). TMThe equipment was used. Stainless steel samples were treated with a surface treatment agent (X), and the sample surface was pressed onto the measuring section for measurement. After measurement, ATR and baseline corrections were performed, and the result was corrected to 4000 cm. -1 The absorbance was 0. In this measurement, the absorbance of peak β (β) was... A The absorbance relative to the above peak α (α) A The ratio of (β) A / α A The value is the average of three measurements. Furthermore, the peak intensity (γ) of the aforementioned peak γ... A The peak intensity (α) relative to the above peak α A The ratio of γ A / α A The value of ) and the peak intensity of the above peak γ (γ) A The peak intensity (β) relative to the aforementioned peak β A The ratio of γ A / β A The value is also the average of three measurements. The obtained values ​​are shown in Table 3.

[0146] (5) Evaluation test

[0147] (5-1) Eschar resistance A (assuming heavy bleeding)

[0148] Two drops (1 drop: 3 μl) of porcine blood (Tokyo Shibaura Organs Co., Ltd.) were added to a surgical electrode, and the electrode was subjected to three cycles of heating at 350°C for 1 min followed by cooling to room temperature for 1 min in a muffle furnace. After cooling the surgical electrode to room temperature, the blood adhering to the coating was wiped off with Kimwipe paper (two drops of porcine blood were added to the coating again, and the cycle of heating at 350°C for 1 min followed by cooling to room temperature for 1 min was repeated three times). Finally, the surgical electrode was cooled to room temperature and then wiped off with Kimwipe paper. The residual area of ​​eschar adhesion after the final dry wiping was calculated relative to the area of ​​eschar adhesion on the surgical electrode after the second cycle of three sets. The eschar resistance was evaluated according to the following criteria. The results are shown in Table 3.

[0149] S: Residual rate less than 1%

[0150] A: The residue rate is between 1% and less than 15%.

[0151] B: The residue rate is above 15% but less than 30%.

[0152] C: The residue rate is above 30% and less than 45%.

[0153] D: Residual rate of 45% or above or presence of film peeling

[0154] (5-2) Efcale resistance B (assuming a high protein and fat content)

[0155] The surgical electrodes of Examples 1-27 and Comparative Examples 1-4 were electrically connected to the main body of the electrosurgical instrument as shown below. Furthermore, the counter plate, which was electrically connected to the main body of the electrosurgical instrument, was attached to a stainless steel container containing pig liver.

[0156] <Electrosurgical Instrument Body (High-Frequency Device and Control Pen)>

[0157] High-frequency device: EXCALIBUR PLUS PC, Medical Device Approval Number 20700BZY01171

[0158] Control pen: Disposable control pen manufactured by Japan Medicalnext Co., Ltd. Medical Device Approval Number: 20300BZY01003000

[0159] The electrosurgical instrument was operated in pure cutting mode (output power 30W). The blade was inserted vertically at a 45° angle relative to the surface of the pig liver, and a cut was made at a depth of 12 mm, moving parallel to the surface of the pig liver for 60 mm at a speed of 20 mm / s. The surgical electrode, after two repeated cutting operations, was cooled to room temperature. Then, the evaluation site was held by a finger through gauze and wiped once. Afterward, the membrane at the evaluation site was visually observed, and the eschar resistance was evaluated according to the evaluation criteria. The results are shown in Table 3.

[0160] S: The residual eschar is less than 1% relative to the evaluated area.

[0161] A: The residual eschar is more than 1% but less than 5% relative to the evaluated area.

[0162] B: The residual eschar is more than 5% but less than 15% relative to the evaluated area.

[0163] C: The residual eschar is more than 15% relative to the evaluated area.

[0164] (5-3) Fit

[0165] The electrosurgical instrument was operated in pure cutting mode (output power 30W). The blade was inserted vertically at a 45° angle relative to the surface of the pig liver, and a cut was made at a depth of 12 mm, moving parallel to the surface of the pig liver for 60 mm at a speed of 20 mm / s. The surgical electrode, after two repeated cutting operations, was cooled to room temperature. Then, the evaluation site was held by a finger through gauze and wiped once. Afterward, the membrane at the evaluation site was visually observed, and the eschar resistance was evaluated according to the evaluation criteria. The results are shown in Table 3.

[0166] S: The area of ​​film peeling is less than 1% relative to the evaluation object.

[0167] A: The area of ​​film peeling is more than 1% but less than 5% relative to the evaluation object.

[0168] B: The area of ​​film peeling is more than 5% but less than 15% relative to the evaluation object.

[0169] C: The area of ​​film peeling is more than 15% relative to the evaluation object.

[0170] [Table 3]

[0171]

[0172] Furthermore, although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

[0173] Explanation of reference numerals in the attached figures

[0174] 10, 20, 30, 40, 60: Surgical electrodes;

[0175] 11, 21, 31, 41, 61: Top part;

[0176] 12: Middle section;

[0177] 13, 23, 33, 43: Electrical connection parts;

[0178] 14, 24, 34, 44: Covering material.

Claims

1. A surgical electrode, which is a surgical electrode of an electrosurgical instrument used in the surgery of biological tissues. The surgical electrode has a tip capable of releasing high frequencies. The top portion has a surface-treated film. The surface-treated film exhibits a high absorption rate at 950 cm⁻¹ in the infrared spectrum. -1 Up to 1060cm -1 The range of peaks (α), at 720 cm⁻¹ -1 Up to 830cm -1 The range of peaks (β), and at 450 cm⁻¹ -1 Up to 495cm -1 The range of peaks (γ), and the peak intensity (β) of the peak β. A The peak intensity (α) relative to the peak α A The ratio of (β) A / α A It is in the range of 0.770 to 1.

040.

2. The surgical electrode according to claim 1, wherein, The surface-treated film comprises a silicone resin (A), which comprises structural units composed of D units and structural units composed of T units.

3. The surgical electrode according to claim 2, wherein, The surface treatment film comprises a silicon-containing inorganic oxide (B).

4. The surgical electrode according to any one of claims 1 to 3, wherein, The top portion also has a base film formed of a surface treatment agent (Y) containing an amino compound (D).

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