JP2003088489A - Index composition of endoscope - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an index composition with which an insertion portion of an endoscope is coated or printed and cured and which obviates the occurrence of yellowing, cracking, deteriorating by curing and peeling and makes the insertion of the insertion portion of the endoscope into a celom possible. SOLUTION: This index composition includes coloring pigments, a binder consisting of a fluorine-contained copolymer, a liquid plasticizer, a solvent for preparing a chief material of ink by being mixed together with the pigments, the binder and the plasticizer and an isocyanate hardener of a non-yellowing type which can cure the chief material of the ink by a two-part reaction.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an index composition for an endoscope.

[0002]

2. Description of the Related Art Generally, an endoscope is a device that is inserted into a body cavity of a human body to observe, inspect, diagnose, and treat the body cavity of the human body. The insertion portion of the endoscope is provided with an index such as a distance scale by printing or marking so that the operator can determine the length to be inserted into the body cavity or the like.

As a method of attaching an index to the insertion portion of such an endoscope, a method using photocurable ink (Japanese Patent Application No. 61-
No. 241184), a method of using a marking liquid in which fluororubber before vulcanization is used as a solvent for the outer coat of fluororubber (Japanese Patent Application No. 63-277031).

In general, the white ink for the index of the insertion portion of the endoscope uses urethane type two-component curable ink, but the insertion portion is inserted along a curved path in the body cavity. Therefore, it is preferable to use an ink composition that is as flexible and stretchable as possible. However, at present, there is almost no ink composition that is flexible and stretchable.

The endoscope is generally sterilized using a glutaraldehyde-based sterilizing solution, a sterilizing solution containing peracetic acid, and a sterilizing solution containing hydrogen peroxide, or a sterilizing method using both hydrogen peroxide and low temperature plasma. Sterilized by the autoclave sterilization method. However, according to these sterilization methods, the urethane-based two-component curable ink used as the index of the insertion portion turns yellow,
The phenomenon of discoloration occurs.

In addition, such a two-component curing type ink undergoes thermal curing deterioration or thermal softening deterioration due to oxidation or hydrolysis, and becomes hard and cracks, or becomes soft or liquid and becomes an insertion portion. The ink used for the index may be separated from the outer resin of the insertion part.

For this reason, it becomes difficult to measure the insertion depth when the endoscope is inserted into the body cavity, and when inserting the endoscope, the mucous membrane in the body cavity is damaged and slippage occurs. There is also a problem in that it may worsen and the burden on the patient may increase.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and is applied or printed on an insertion portion of an endoscope and cured, and yellowing, cracking, deterioration of curing, and peeling. It is an object of the present invention to provide an index composition that can be inserted into a body cavity of an endoscope insertion part without causing any trouble.

[0009]

In order to solve the above problems, the present invention provides a coloring pigment, a binder comprising a fluorocopolymer, a liquid plasticizer, the pigment, the binder, and the plasticizer. A solvent for mixing to prepare an ink base and a non-yellowing type isocyanate-based curing agent capable of curing the ink base by a two-component reaction, which is inserted into a body cavity. The present invention provides an endoscope index composition for applying or printing on the insertion portion of the endoscope.

In the indicator composition of the present invention, the color pigment may be a white pigment. As the white pigment, it is desirable to use titanium white containing ultrafine particle titanium oxide capable of shielding ultraviolet rays. Further, the indicator composition of the present invention can further contain a curing catalyst composed of dibutyltin dilaurate or amine. .

In the indicator composition of the present invention, as the plasticizer, liquid polyisoprene, liquid polybutadiene, liquid acrylonitrile-butadiene rubber, liquid polychloroprene, liquid polyoxypropylene, liquid polyoxytetramethylene glycol, liquid polyolefin glycol, liquid It is preferable to use at least one liquid chemical substance selected from the group consisting of poly-ε-caprolactone, liquid silicone rubber, liquid polysulfide rubber, liquid fluororubber, and liquid polyisobutylene.

This liquid chemical substance imparts flexibility, flexibility, elongation and adhesion to the indicator composition film by reacting with or without reacting with the non-yellowing type isocyanate curing agent.

In the indicator composition of the present invention, it is desirable to use a polyfluoroolefin-vinyl ether copolymer or a polyfluoroolefin-vinyl ester copolymer as the fluorine-containing copolymer.

The index composition for an endoscope of the present invention will be described in more detail below. The index composition of the present invention uses a binder made of a fluorinated copolymer, to which a color pigment, a liquid plasticizer, and a solvent are added to prepare an ink base, and the ink base is mixed with the ink by a two-liquid reaction. The present invention is characterized in that a non-yellowing type isocyanate-based curing agent capable of curing is combined.

In the indicator composition of the present invention, the composition of each component is not particularly limited, but usually, the ink main component 10
In 0% by weight, the fluorine-containing copolymer is 10 to 60% by weight, the color pigment is 10 to 60% by weight, the liquid plasticizer is 1 to 30% by weight, and the solvent is 10 to 60% by weight.
It is preferable that the non-yellowing type isocyanate curing agent is 3 to 30 parts by weight with respect to 00 parts by weight.

By coating or printing such an indicator composition on the insertion portion of an endoscope and curing it by heating, the indicator composition is free from yellowing, cracking, deterioration of curing, and peeling, and is kept in a body cavity. It is possible to obtain an endoscope having an insertion portion with an index, which does not hinder the insertion into the endoscope.

On the other hand, as a method for sterilizing an endoscope, there is a sterilization method using both hydrogen peroxide and low temperature plasma. According to this sterilization method, ultraviolet rays are generated. In addition, it may be sterilized using an ultraviolet ray generator. In these cases, ultraviolet rays pass through the index composition and reach the adhesion interface between the index composition and the outer skin of the endoscope insertion portion, resulting in interface deterioration.

In such a case, by using titanium white containing ultrafine titanium oxide capable of shielding ultraviolet rays as the pigment, ultraviolet rays can be shielded and the above interface deterioration can be prevented. Titanium white (titanium oxide), which is a general white pigment, usually has a particle size of 20 to 50 μm, and has a UV shielding property of 0.01 to
By blending ultrafine titanium oxide particles (titanium white for UV shielding) with a particle size of 0.05 μm, the UV rays are effectively shielded and the UV rays pass through the indicator composition and the endoscope composition and the endoscope insertion part. It is possible to prevent the occurrence of interface deterioration due to reaching the adhesion interface with the outer skin.

Yellowing of the indicator composition is caused by a certain type of isocyanate contained in the curing agent. In general, when an aromatic isocyanate such as tolylene diisocyanate is used as a curing agent, ultraviolet rays, heat, due to molecular cleavage and deterioration reaction due to oxidation, including deterioration over time, an index composition Turn yellow or turn brown.

In the present invention, since the non-yellowing type isocyanate curing agent is used as the curing agent, such discoloration of the indicator composition does not occur.

In the indicator composition of the present invention, the liquid plasticizer is added to impart flexibility, flexibility, elongation and adhesion to the indicator composition. That is, when the liquid plasticizer is not added, a binder composed of a fluorine-containing copolymer is used, a color pigment and a solvent are added to the binder to prepare an ink base, and the ink base can be cured by a two-liquid reaction. Even if a non-yellowing type isocyanate-based curing agent is blended and cured, the fluorine-containing copolymer is originally hard and does not stretch, so the coating itself of the indicator composition when the insertion part of the endoscope is bent Cracks and cracks occur.

On the other hand, when the liquid plasticizer is added, flexibility, flexibility, elongation and adhesion are imparted to the indicator composition, and the film itself does not crack and cracks occur.

Further, in the indicator composition of the present invention, the binder composed of the fluorine-containing copolymer is very excellent in chemical resistance, heat resistance and wet heat resistance, so that it has been used conventionally. , Used in place of urethane, which is inferior in heat resistance and wet heat resistance. Yellowing or discoloration due to long-term storage or various sterilization, thermosetting deterioration due to oxidation or hydrolysis at high temperature of 135 ° C or high heat and humidity, or thermal softening deterioration causes the indicator composition to harden and break, or become soft or liquid. Therefore, in order to prevent the peeling between the indicator composition and the outer coat resin of the insertion portion from occurring, it is essential to use a binder made of a fluorine-containing copolymer having excellent chemical resistance, heat resistance, and wet heat resistance. is there.

Specific examples of the fluorine-containing copolymer used as the binder in the indicator composition of the present invention include alternating copolymers of chlorotrifluoroethylene and vinyl ether or random copolymers of chlorotrifluoroethylene and vinyl ester. Can be mentioned. This copolymer is commercially available, for example, as Lumiflon (trade name: manufactured by Asahi Glass Co., Ltd.) or Cefral Coat (trade name: manufactured by Central Glass Co., Ltd.). Lumiflon is a copolymer in which fluoroethylene units and vinyl ether units are regularly arranged alternately, and Cefraralcoat is a copolymer in which fluoroethylene units and vinyl ester units are randomly arranged. Is stable,
It has excellent weather resistance and has the unique property of being soluble in various solvents despite being a fluororesin.

Among the fluoroethylene units and vinyl ether units or vinyl ester units constituting the Lumiflon or Cefraral coat, the fluoroethylene units fulfill the functions of weather resistance and durability, and the alkyl groups of the vinyl ether units or vinyl ester units are solvent-soluble and transparent. The hydroxyl group and the carboxyl group fulfill the functions of adhesion to the base material, respectively, and the gloss, hardness, and flexibility.

The index composition of the present invention requires the use of a solvent because it is applied or printed on the outer resin of the insertion portion of the endoscope. As the solvent, various types can be used, and for example, aromatic hydrocarbons such as xylene and toluene, ketones such as methyl ethyl ketone, and high boiling point ester solvents can be mixed and used.

From the viewpoint of printing performance, it is preferable to use a curing catalyst in the index composition of the present invention. As the curing catalyst, dibutyltin dilaurate or amine can be used, and printing workability (material to be printed, index composition viscosity, index composition solvent evaporation rate, index composition dry curing rate, index composition It is desirable to make an appropriate selection in consideration of overall flexibility of the product).

In general, the pigment is often a white pigment from the viewpoint of visibility.
The indicator composition may be colored by adding pigments such as yellow, green and blue.

Regarding the curing catalyst, however, tin-containing organic substances such as dibutyltin dilaurate should be used as much as possible from the viewpoint of environmental hormones, or the white pigment titanium white (titanium oxide) should act as a catalyst. It is preferable not to use it or use an amine type.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, various examples will be shown as embodiments of the present invention. Example 1 Alternate copolymer of chlorotrifluoroethylene and vinyl ether or random copolymer of chlorotrifluoroethylene and vinyl ester (hereinafter referred to as compound A, Lumiflon LF200F: trade name, manufactured by Asahi Glass Co., Ltd., or Sepural coat A402B: trade name , Made by Central Glass Co., Ltd.) and polytetramethylene ether glycol (PTMG: trade name, 20% by weight (solid content)).
10% by weight of a plasticizer consisting of Mitsubishi Chemical Co., Ltd., 35% by weight of titanium white as a white pigment, 15% by weight of aromatic hydrocarbon (xylene), 10% by weight of a ketone system (methyl ethyl ketone), and a high boiling point. A mixed solvent composed of 10% by weight of an ester solvent (isobutyl acetate) was blended to prepare an ink base material.

Hexamethylene diisocyanate (Coronate EH: trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.) as a curing agent is added to the main component of the ink in an amount of 1 per 100 parts by weight of the main component.
0 part by weight was added and mixed to obtain an index composition according to this example.

A white line was printed on the outer peripheral portion of the flexible tube of the endoscope using a printing apparatus such as screen printing or tampo printing, and the index composition was heat-cured to mark the index.

Comparative Example 30% by weight (solid content) of a binder consisting of an alternating copolymer of chlorotrifluoroethylene and vinyl ether or a random copolymer of chlorotrifluoroethylene and vinyl ester (compound A), and titanium as a white pigment. 30% by weight of white and 0.
Ultra fine particle titanium oxide (TT-TT) with a particle size of 01 to 0.05 μm
O-D2: trade name, manufactured by Ishihara Sangyo Kaisha, Ltd.) 5% by weight, further aromatic hydrocarbon (toluene) 15% by weight, ketone type (methyl ethyl ketone) 10% by weight, and high boiling point ester solvent (isobutyl acetate) 10% by weight. The main solvent of the ink was prepared by blending the mixed solvent of.

Hexamethylene diisocyanate (Duranate TSE-10) as a curing agent was added to this ink base material.
0: trade name, manufactured by Asahi Kasei Co., Ltd.) was added to 20 parts by weight with respect to 100 parts by weight of the main ingredient and mixed to obtain an index composition according to this example.

A white line was printed on the outer peripheral portion of the flexible tube of the endoscope using a printing device such as screen printing or tampo printing, and the index composition was heat-cured to mark the index.

Example 2 Liquid polyolefin glycol was added to 25% by weight (solid content) of a binder consisting of an alternating copolymer of chlorotrifluoroethylene and vinyl ether or a random copolymer of chlorotrifluoroethylene and vinyl ester (Compound A). (Polyether HA: trade name, manufactured by Mitsubishi Chemical)
10% by weight of a plasticizer consisting of 30% by weight of titanium white as a white pigment, and a UV-shielding effect of 0.1.
Ultra fine particle titanium oxide (TT-TT) with a particle size of 01 to 0.05 μm
O-D2: trade name, manufactured by Ishihara Sangyo Kaisha, Ltd.) 5% by weight, aromatic hydrocarbon (toluene) 10% by weight, ketone solvent (methyl ethyl ketone) 10% by weight, and high boiling point ester solvent (isobutyl acetate) 10% by weight. %, A mixed solvent of 100% was mixed to prepare an ink main component.

A non-yellowing type isocyanate (LTI: trade name, manufactured by Kyowa Hakko Kogyo Co., Ltd.) as a curing agent is added to the main component of the ink.
5 parts by weight was added to 100 parts by weight of the ink base material and mixed to obtain an index composition according to this example.

A white line was printed on the outer peripheral portion of the flexible tube of the endoscope using a printing device such as screen printing or tampo printing, and the index composition was heat-cured to mark the index.

Example 3 Liquid fluororubber (G-101) was added to 20% by weight of a binder composed of an alternating copolymer of chlorotrifluoroethylene and vinyl ether or a random copolymer of chlorotrifluoroethylene and vinyl ester (Compound A). : 10% by weight of a plasticizer composed of trade name, Daikin), 30% by weight of titanium white as a white pigment, and ultrafine titanium oxide particles having a particle size of 0.01 to 0.05 μm and exhibiting an ultraviolet shielding property (TTO-D2: product Name, manufactured by Ishihara Sangyo Kaisha, Ltd.) 5% by weight, further aromatic mixed hydrocarbon (toluene) 15% by weight,
10% by weight of ketone solvent (methyl ethyl ketone) and 10% by weight of high boiling ester solvent (isobutyl acetate)
An ink base material was prepared by blending a mixed solvent consisting of

A non-yellowing type xylylene diisocyanate (Takenate 500:
5) based on 100 parts by weight of the main agent
Parts by weight were added and mixed to obtain an index composition according to this example.

A white line was printed on the outer peripheral portion of the flexible tube of the endoscope using a printing device such as screen printing or tampo printing, and the ink composition was heated and cured to mark the index.

Conventional example: 20% by weight of urethane resin as a binder, 35% by weight of titanium white as a white pigment, 20% by weight of aromatic mixed hydrocarbon (toluene), 15% by weight of ketone solvent (methyl ethyl ketone), and high boiling point. An ink base was prepared by blending with a mixed solvent consisting of 10% by weight of an ester solvent (isobutyl acetate).

A non-yellowing type xylylene diisocyanate (Takenate 500:
5) based on 100 parts by weight of the main agent
A weight part was added and mixed to obtain an index composition.

A white line was printed on the outer peripheral portion of the flexible tube of the endoscope using a printing apparatus such as screen printing or tampo printing, and the index composition was heat-cured to mark the index.

Table 1 below shows the component compositions of the index compositions according to each of the above Examples, Comparative Examples and Conventional Examples. The characteristic test was performed after printing on the outer peripheral portion of the flexible tube of the endoscope, followed by drying at 80 ° C. for 1 hour and conditioning at room temperature for one day.

[0046]

[Table 1]

* 1: The printability was evaluated by evaluating the print workability when printing on the flexible tube of the endoscope insertion portion and the adhesion by bending. * 2: The index composition according to the example, the comparative example and the conventional example is printed on the outer resin sheet of the flexible tube of the endoscope insertion part, and the elongation of the index composition is investigated by stretching the sheet and the elongation is 150% or more. If it is not peeled off, it is OK, and if it is peeled off,
G. * 3: The color tone after 600 cases of autoclave sterilization was visually inspected. * 4: The state of peeling of the index of the endoscope insertion portion after 600 autoclave sterilization cases was visually inspected. * 5: The overall evaluation was determined by the printability, elongation, color tone after autoclave sterilization, and peeling state of the index after autoclave, and the overall evaluation was performed according to the following criteria. ⊚: excellent, ◯: good, Δ: acceptable, ×: not acceptable.

From Table 1 above, all of the index compositions within the scope of the present invention (Examples 1 to 3) show excellent properties, while the compositions according to the comparative example using no liquid plasticizer. As for the product, the elongation of the index composition was inferior, and peeling occurred in the autoclave sterilization, and the overall evaluation was acceptable. Further, the composition according to the conventional example using a urethane resin as a binder,
Discoloration and peeling occurred after autoclave sterilization, and comprehensive evaluation was impossible.

[0049]

As described above in detail, according to the present invention, a fluorine-containing copolymer as a binder is mixed with a white pigment and a plasticizer as a main component, and a non-yellowing type isocyanate curing agent is added to the mixture. Since the agent is blended, by using this index composition to mark the index of the flexible tube in the insertion part of the endoscope, the composition yellows or peels off due to oxidation or heat deterioration. It is prevented from occurring.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4C061 FF21 JJ03 JJ06 JJ17                 4J038 CA022 CA072 CA082 CB122                       CD091 CD092 CE051 CF011                       CR072 DD022 DF012 DG191                       DG27 DL032 GA13 HA216                       JA05 JA32 JB01 JC41 KA04                       KA06 KA08 KA10 NA03 NA12                       PB01                 4J039 AD01 AD04 AD06 AD08 AD11                       AD15 AE04 AE06 AE07 AE10                       AE11 BA13 BA35 BC03 BC16                       BE01 BE12 CA07 EA18 EA34                       EA43 FA02 GA10

Claims (7)

[Claims] 1. A coloring pigment, a binder composed of a fluorine-containing copolymer, a liquid plasticizer, a solvent for mixing with the pigment, the binder, and the plasticizer to prepare an ink main component, and A non-yellowing type isocyanate curing agent capable of curing an ink main component by a two-component reaction, which is used for applying or printing to an insertion portion of an endoscope to be inserted into a body cavity. Index composition for endoscopes. 2. The index composition according to claim 1, wherein the color pigment is a white pigment. 3. The index composition according to claim 2, wherein the white pigment is titanium white containing ultrafine particles of titanium oxide capable of blocking ultraviolet rays. 4. The indicator composition according to claim 1, further comprising a curing catalyst composed of dibutyltin dilaurate or amine. 5. The plasticizer is liquid polyisoprene, liquid polybutadiene, liquid acrylonitrile-butadiene rubber, liquid polychloroprene, liquid polyoxypropylene, liquid polyoxytetramethylene glycol, liquid polyolefin glycol, liquid poly-ε-caprolactone, The index composition for an endoscope according to claim 1, which is at least one liquid chemical substance selected from the group consisting of liquid silicone rubber, liquid polysulfide rubber, liquid fluororubber, and liquid polyisobutylene. . 6. The liquid chemical substance imparts flexibility, flexibility, elongation and adhesion to the ink film by reacting with or without reacting with a non-yellowing type isocyanate curing agent. The index composition for an endoscope according to claim 5. 7. The index composition for an endoscope according to claim 1, wherein the fluorine-containing copolymer is a polyfluoroolefin-vinyl ether copolymer or a polyfluoroolefin-vinyl ester copolymer. object.