JP2005152461A - Endoscope apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an endoscope whose parts are jointed and fixed with a durable adhesive free from softening degradation, hardening degradation, brittle fracture, a lowering of bonding strength, and the like caused by oxidative degradation, hydrolysis and heat even by various disinfecting methods. <P>SOLUTION: The parts constituting the endoscope are jointed with a three component reactive adhesive comprising a main agent in which 5-15 wt.% of a rubber and/or a plastic is added to an epoxy resin, an amine curing agent mixed with a mix ratio of 10:1-10:4 to the main agent, and 0.1-1% pts.wt. thermal cationic curing initiator. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an endoscope apparatus, and more particularly, to joining with an adhesive such as parts constituting an endoscope.

  Since an endoscope is a device that is inserted into a body cavity or the like, it is necessary to make the diameter of the insertion portion as thin as possible. On the other hand, various contents are inserted into the insertion portion in order to diversify the functions of the endoscope. Has been.

  For example, in the insertion portion of the endoscope, for the purpose of improving the endoscopic treatment by the endoscope, a forceps tube for passing a larger treatment tool, and a body cavity to reduce the burden on the patient Tubes for supplying air, tubes for cleaning the lens surface incorporated in the hard end of the insertion portion, and cleaning filth in the body cavity are inserted, and these tubes are usually made of resin such as Teflon, polyolefin, silicone or the like. Rubber material is used.

  An adhesive is used to fix the mouth portion of these tubes to the distal end of the insertion portion of the endoscope or the operation portion.

  In addition, a cover lens and its lens group, an illumination cover lens from the light guide, and its lens group are arranged as an optical system for observing the inside of the body cavity at the distal end hard portion of the insertion portion.

  An adhesive is used to fix these lens groups to the lens frame of the insertion portion and the hard end portion.

  Further, a light guide that transmits light to the distal end portion and an image guide that transmits video to the eyepiece portion are inserted through the insertion portion. In these light guides and image guides, fiber bundles in which a large number of fiber strands are bundled are used. An adhesive is used to fix the fiber bundle to the lens frame or the hard tip portion of the insertion portion.

  Furthermore, in the case of an electronic endoscope, in addition to the tubes and fiber bundles, a cable or the like for transmitting an electrical signal from a CCD or the like built in the hard end of the insertion portion to the connector portion is inserted. Yes. An adhesive is used to protect and fix these CCDs.

  In addition to joining the parts constituting the endoscope as described above, after securing the end of the flexible outer tube with a thread from the outside and fixing it to the inner member, securing the insertability and the thread In order to prevent fraying, an adhesive is applied from the outside to finish the outer surface and fix the yarn.

  In this way, the endoscope has a diameter of the insertion portion as thin as possible, and various contents are inserted through the insertion portion to diversify the endoscope function.・ Because it cannot be fixed with screws, it is done with an adhesive. In general, an epoxy-based adhesive is frequently used as the adhesive (see, for example, Patent Document 1).

  By the way, since a medical endoscope is inserted into a body cavity of a patient, it must be completely sterilized and sterilized. Conventionally, as an antiseptic, an aldehyde-based disinfectant represented by glutaraldehyde has been used. Acetic acid, strongly acidic water, alcohol, benzalkonium chloride (ammonium), chlorhexidine gluconate (biguanato), alkyldiaminoethylglycine hydrochloride (amphoteric surfactant), phenol, iodine, sodium hypochlorite (Chlorine) is used.

  Endoscope disinfection is performed by immersing the endoscope in the chemical solution of the disinfectant after filth removal by rinsing or wiping the surface of the endoscope with gauze containing the disinfectant. In recent years, disinfection by exposing to a plasma gas of formalin gas, ethylene oxide gas, and hydrogen peroxide having a high disinfection effect has been adopted.

  In addition, boil sterilization and autoclave sterilization with saturated steam at 135 ° C. × 2.3 atm are also employed.

  Among these, hydrogen peroxide plasma gas sterilization, boiling sterilization and autoclave sterilization do not require ventilation equipment as in the case of using formalin gas and ethylene oxide gas, and thus are widely adopted. ing.

  However, due to the diversification of sterilization and disinfection methods and the accompanying increase in the number of chemical solutions, conventional epoxy adhesives used for joining endoscope parts are not capable of reacting with the active oxygen of peracetic acid or the acidity of strongly acidic water. Substances and hydrogen peroxide plasma gas, boiling disinfection and autoclave sterilized hot water or hot steam, etc., will reduce the adhesive strength, so it may not be compatible with some sterilization / disinfection methods and will be used for a long time In this case, there is a problem that it is difficult to maintain the performance as an endoscope.

  The cause of this was thought to be oxidation degradation, heat softening, curing aging, and hydrolysis of the adhesive, so that the chemical resistance was maintained at the current level, while maintaining these oxidation degradation resistance, heat aging resistance, and hydrolysis resistance. An improved adhesive was required.

Therefore, there is a demand for an endoscope having improved resistance to oxidation deterioration, heat aging resistance and hydrolysis resistance of an adhesive and having excellent resistance to all sterilization / disinfection methods.
JP 2003-126023 A

  By the way, since the temperature of the hot water vapor for autoclave sterilization is around 135 ° C., it is necessary to use a part having the same heat resistance as that of the endoscope. Further, the heat resistance of the adhesive for bonding endoscope parts needs to be the same. An epoxy adhesive becomes a cured product by curing a main agent made of an epoxy resin with a curing agent made of an acid anhydride or amine.

  That is, when assembling and producing the endoscope, it is preferable to bond the parts by curing the adhesive in the lowest possible temperature and in the shortest possible time. Moreover, since the material of a component is a metal, a plastic, rubber | gum, etc., it is preferable that there is fixed adhesive force from a hard thing to a soft thing. Therefore, it is desirable that the adhesive is cured at 60 to 80 ° C. and has a heat resistance of 135 ° C.

  In order to increase the chemical resistance and heat resistance of the adhesive, it is necessary to increase the curing density and to set the glass transition point of the cured epoxy resin to 100 ° C. or higher so as to be very hard.

  However, as described above, the component needs to have a high adhesive force from a hard object to a soft object. Especially in the case of joining soft parts, the curing density is increased or the glass transition point is set to 100 ° C. or higher. With a hard cured epoxy resin, high adhesive strength cannot be obtained.

  That is, since the adhesive is required to improve not only the shear strength but also the peel strength, an adhesive having conflicting properties of being hard and soft is necessary.

  It is an object of the present invention to use various durable disinfecting methods, in particular, a component using a durable adhesive that does not decrease the adhesive strength even when treated in a hydrogen peroxide solution environment or a hydrogen peroxide plasma environment. It is an object of the present invention to provide an endoscope capable of maintaining performance over a long period of time by bonding and fixing.

In order to achieve the above object, the present invention firstly,
A main agent obtained by adding 5 to 15% by weight of rubber and / or plastic to an epoxy resin, an amine-based curing agent having a compounding ratio of 10: 1 to 10: 4 with respect to the main agent, and a thermal / cationic curing initiator 0.1 to Provided is an endoscope apparatus in which a member constituting an endoscope is joined with a three-component reactive adhesive containing 1% by weight.

  In addition, the present invention secondly relates to a main agent obtained by adding 5 to 15% by weight of rubber and / or plastic to an epoxy resin, an amine curing agent having a compounding ratio of 10: 1 to 10: 4 with respect to the main agent, Provided is an endoscope apparatus in which an imaging device of an endoscope is sealed with a three-component reactive adhesive containing 0.1 to 1% by weight of a cationic curing initiator.

  Thirdly, according to the present invention, after securing the end of the flexible outer tube of the insertion portion of the endoscope with a thread from the outside and fixing it to the inner member thereof, securing the insertability and preventing fraying of the thread Therefore, an endoscope apparatus in which an adhesive is applied to the thread to finish and fix the outer surface, and the adhesive is a main agent obtained by adding 5 to 15% by weight of rubber and / or plastic to an epoxy resin And a three-component reactive adhesive containing an amine curing agent with a compounding ratio of 10: 1 to 10: 4 with respect to the main agent and 0.1 to 1% by weight of a thermal / cationic curing initiator. An endoscope apparatus characterized by the above is provided.

  Fourthly, the present invention relates to a main agent obtained by adding 5 to 15% by weight of rubber and / or plastic to an epoxy resin, an amine curing agent having a compounding ratio of 10: 1 to 10: 4 with respect to the main agent, a heat / cation A three-component reactive adhesive containing 0.1 to 1% by weight of a system curing initiator, and by forming an adhesive layer around the observation lens or illumination lens of the endoscope, Provided is an endoscope apparatus characterized in that corners on the outer periphery of the lens are smoothed.

  As described above, the present invention uses a three-component reactive epoxy adhesive comprising a main agent containing rubber and / or plastic-modified epoxy resin, an amine curing agent, and a thermal / cationic curing initiator. When mirror parts are joined, the joint will not be deteriorated by sterilization using an oxidizing chemical solution or autoclave. Therefore, any sterilization / disinfection method, especially in a hydrogen peroxide environment or in a hydrogen peroxide plasma environment. An endoscope having excellent resistance to processing can be obtained, and the sterilization level of the endoscope after various disinfection and sterilization can be improved.

  In the endoscope apparatus of the present invention, as an epoxy adhesive for bonding parts or the like, a main agent obtained by adding 5 to 15% by weight of rubber and / or plastic to an epoxy resin, and a mixing ratio with respect to the main agent is 10: 1 to A three-component reactive adhesive containing a 10: 4 amine curing agent and 0.1 to 1% by weight of a heat / cationic curing initiator is used.

  An essential component of the main component of the three-component reaction heating type adhesive is an epoxy resin obtained by adding rubber and / or plastic to an epoxy resin.

  In the present invention, examples of the epoxy resin used as the main agent include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, brominated epoxy resin, alicyclic type epoxy resin, and polyfunctional type epoxy resin. The at least 1 sort (s) chosen from the group which consists of can be mentioned. Moreover, in this invention, the epoxy resin which comprises a main ingredient can use a glycidyl type reactive diluent individually or as a mixture with the epoxy resin illustrated above.

  Addition of rubber or plastic to epoxy resin can be done by blending rubber or plastic with epoxy resin to modify the epoxy resin to increase both adhesive shear strength and adhesive peel strength, and from soft metal parts to soft rubber parts It is performed in order to enable bonding to each other. For this purpose, it is necessary to add 5-15% by weight of rubber or plastic to the epoxy resin.

  Examples of the rubber and / or plastic used in the present invention include rubbers such as acrylic rubber, nitrile rubber, chlorinated polyethylene, polyolefin-based elastomer, polystyrene-based elastomer, silicone rubber, and fluorine rubber; acrylic resin , Urethane resins, polysulfone resins, polyethersulfone resins, and plastics such as fluorine resins; and mixtures thereof.

  As described above, by adding rubber or plastic to the epoxy resin, it is possible to improve the adhesive shear strength and particularly the adhesive peel strength of the bonded portion bonded with the epoxy adhesive.

  The amount of rubber or plastic added to the epoxy resin is 5 to 15% by weight, preferably 15% by weight. When the concentration of rubber and / or plastic is within the above range, an adhesive layer having excellent water resistance and strong oxidation resistance can be obtained. Further, when a rubber / plastic fine powder is dispersed in an epoxy resin in a weight ratio of 5 to 15%, the shear adhesive strength and particularly the peel adhesive strength can be improved. It has been experimentally found that if it is 5% by weight or less, there is no effect of giving elasticity, and if it exceeds 15% by weight, the water resistance is extremely lowered. Moreover, when the addition amount of the rubber / plastic fine powder is out of the above range, the autoclave resistance and the chemical resistance may be lowered.

  In the present invention, the rubber and / or plastic is preferably dispersed in an epoxy resin in the form of fine powder having an average particle size of 300 nm or less, more preferably 10 nm, and then mixed with a main agent, a curing agent, a curing initiator, and the like. Can do. An adhesive mainly composed of a mixture of an epoxy resin and rubber and / or plastic forms a sea-island structure in which rubber and / or plastic is distributed in islands in the epoxy resin by heating for the curing reaction. Various characteristics are developed based on the sea-island structure. However, this sea-island structure strongly depends on the mixing / curing conditions and the like when rubber and / or plastic is added in a liquid state, and desired adhesive properties can be obtained only under extremely limited conditions. On the other hand, when rubber and / or plastic is dispersed in advance in the epoxy resin in the form of fine powder, the sea-island structure hardly depends on the mixing / curing conditions and can be easily controlled. Accordingly, it is possible to increase the degree of freedom such as bonding work and curing conditions. An epoxy resin in which 5 to 15% by weight of this rubber / plastic fine powder is dispersed can adhere from hard metal parts to soft rubber parts.

  Furthermore, in this invention, while using an amine-type hardening | curing agent as a hardening | curing agent, the weight ratio of a main ingredient and an amine-type hardening | curing agent shall be 10: 1-10: 4. Preferably, it is 10: 4. In the epoxy resin, the molecular weight per functional group is referred to as epoxy equivalent, and the amine equivalent of the amine curing agent is also referred to as active hydrogen equivalent. The above blending ratio is set based on the theoretical blending ratio calculated from the epoxy equivalent and the amine equivalent and various properties such as adhesive strength.

  That is, when the weight ratio of the amine curing agent to the main agent is less than 0.1, sufficient adhesive strength cannot be obtained, and active oxygen in peracetic acid, acidic substances in strongly acidic water, plasma of hydrogen peroxide When exposed to gas, hot water in boiling disinfection, or hot water vapor in autoclave sterilization, it may cause oxidative deterioration of the adhesive layer, softening deterioration due to heat, hardening aging, hydrolysis, brittle fracture, and decrease in adhesive strength. is there. In addition, in this case, the unreacted epoxy resin becomes excessive and desired characteristics cannot be obtained. In addition, when the weight ratio of the amine curing agent to the main agent exceeds 0.7, unreacted amine becomes excessive and free amine remains, reducing water resistance, active oxygen in peracetic acid, Acidic substances in strongly acidic water, plasma gas of hydrogen peroxide, hot water in boiling disinfection, thermal oxidation in autoclave sterilization, adhesive layer deterioration due to heat, softening deterioration due to heat, hardening aging, hydrolysis, It may cause brittle fracture and reduced adhesive strength.

  In the present invention, as the amine, for example, at least one selected from the group consisting of aliphatic amines, alicyclic amines, aromatic amines, and polyamide amines can be used.

  As aliphatic amine curing agents, diethylenetriamine, ethylenediamine, and triethylenetetramine are used, and as polyamideamine curing agents, a condensate of 36-carbon dimer acid and DETA obtained by thermal polymerization of linoleic acid or oleic acid is used as an aromatic amine. Examples of the curing agent include diaminodiphenylmethane and diaminodiphenyl sulfone, examples of the cyclic amine curing agent include isophoronediamine and xylylenediamine, and examples of the aliphatic aromatic amine curing agent include m-xylenediamine.

Examples of the thermal / cationic curing initiator include aromatic iodonium compounds represented by the following structural formula (1), and aromatic sulfonium compounds represented by the following structural formulas (2) to (4). it can.

(Wherein R ¹ and R ² are C ₁₂ H ₂₅ , or R ¹ is C ₁₈ H ₁₇ O and R ² is H)

(Wherein R ¹ and R ² are alkyl groups)

Wherein R ¹ and R ² are selected from CH ₃ and C ₂ H ₅
Specific product names include CI-2624 (manufactured by Nippon Soda Co., Ltd.), CI-2855 (manufactured by Nippon Soda Co., Ltd.), Sun-Aid SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.), Sun-Aid SI-80L (Sanshin Chemical Industry Co., Ltd.) Sanadeid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.), Adeka Opton CP-66 (manufactured by Asahi Denka Kogyo Co., Ltd.), and Adeka Opton CP-77 (manufactured by Asahi Denka Kogyo Co., Ltd.). .

  According to the present invention, in addition to an epoxy resin in which a fine powder of rubber / plastic is dispersed at a weight ratio of 5 to 15% and an amine curing agent, a heat / cation curing initiator is blended, and these blending ratios, particularly By joining the endoscope parts with an adhesive that optimizes the mixing ratio of amine-based curing agent and heat / cationic curing initiator, better heat resistance, chemical resistance, and strong oxidation chemical resistance can be achieved. The endoscope apparatus which has is obtained. In particular, according to the present invention, a conventional two-component reactive adhesive containing an epoxy resin in which a fine powder of rubber / plastic is dispersed at a weight ratio of 5 to 15% and an amine curing agent cannot be realized. It is possible to markedly improve the strong oxidation chemical resistance in a hydrogen oxide water environment, a hydrogen peroxide plasma environment, and the like, and an endoscope apparatus having better strength can be obtained.

  Among amine-based curing agents, polyamine-based curing agents tend to be weak against heat resistance, chemical resistance, and particularly strong oxidation chemical resistance. This is because the active oxygen in the strong oxidizing chemical solution attacks the amine bond and causes deterioration of the adhesive. On the other hand, an acid anhydride type or phenol type curing agent instead of a polyamine type requires a curing temperature of 120 to 150 ° C. and is slightly inferior in low-temperature curability. Moreover, if the adhesive strength is taken, the polyamine curing by the polyamine curing agent is the maximum. According to the present invention, by adding a heat / cationic curing initiator, the weak point can be reinforced while taking advantage of the strength of curing with an amine curing agent, preferably a polyamine curing agent, and the hydrogen peroxide resistance can be enhanced.

  Theoretically, the amount of amine-based curing agent is reduced by adding a new curing initiator. The heat and cationic curing initiator is added in an amount of 0.1 to 1% by weight with respect to the main agent. Preferably, the amine-based curing agent is 80 to 120% of the theoretical blending amount, and high adhesive strength can be obtained by adding 0.2 to 0.4% by weight of a heat / cationic curing initiator.

  More preferably, as an essential component of the main component, an epoxy resin in which a fine powder of rubber / plastic having an average particle size of 300 nm or less is dispersed in a weight ratio of 5 to 15% in a bisphenol-based epoxy resin is used to further improve heat resistance. Therefore, 10-40% of phenol novolac epoxy resin can be added to the above-mentioned components. Furthermore, a bisphenol-based epoxy resin can be added. As the curing agent, at least one of a modified aromatic polyamine and a metaxylylenediamine-based curing agent can be added to the thermal / cationic curing initiator in an optimum blending ratio.

  In the present invention, the three-component reactive adhesive includes a catalyst, an adhesion-imparting agent, a solvent, a plasticizer, a filler, an antioxidant, a polymerization inhibitor, an interface in addition to the above-mentioned main agent, curing agent, and curing initiator. Additives such as activators, fungicides, and colorants can be further included. In order to mix the adhesive of the present invention, various devices for producing a normal adhesive may be used. These additives may be added to the main agent or may be added to a mixture of the main agent and the curing agent. For example, the three-component reactive adhesive may further contain 0.1 to 3 parts by weight of epoxy silane with respect to 100 parts by weight of the main agent as an adhesiveness imparting agent. The three-component reactive adhesive further contains, as a filler, 40 to 50 parts by weight of fused silica spherical powder and 10 to 20 parts by weight of ultrafine powdered spherical silica with respect to 100 parts by weight of the main agent. May be.

  Using the three-component reaction heating type adhesive described above, for example, the parts of the endoscope are bonded to each other as follows.

  That is, first, the A liquid containing the main agent and the B liquid containing the curing agent are mixed at a predetermined ratio. Next, this mixture is applied to the surface of a predetermined endoscopic part to be applied with a brush or the like, the two are joined, fixed, and heated at a predetermined heating temperature for a predetermined heating time. The mirror parts are firmly bonded together.

  Similarly, sealing the imaging device of the endoscope, finishing and fixing the outer surface of the end portion of the flexible outer tube, and raising the adhesive layer around the observation lens or the illumination lens. Can do.

  The heating temperature is preferably 60 ° C. to 135 ° C., although it varies depending on the type and blending ratio of the main agent and the curing agent of the adhesive. The heating time is preferably about 0.5 to 3 hours. If the heating temperature is less than 60 ° C., the curing reaction proceeds slowly and takes too much time for curing. On the other hand, if it exceeds 135 ° C., endoscope parts with low heat resistance may cause thermal deterioration, which is not preferable. .

  In the present invention, the members to be joined using the three-component reactive adhesive are not particularly limited as long as they are constituent members of the endoscope apparatus. For example, using the above-mentioned three-component reactive adhesive, the mouth portion of various tubes inserted into the insertion portion of the endoscope apparatus is fixed to the distal end of the insertion portion or the operation portion, and is disposed at the distal end hard portion of the insertion portion. Fixing the lens group etc. to the lens frame or the hard tip part, fixing the fiber bundle inserted through the insertion part to the lens frame or the hard tip part, and the CCD of the imaging device incorporated in the hard tip part, etc. Can be protected, fixed, sealed, and the like.

  In addition, after the end of the flexible outer tube of the insertion portion of the endoscope apparatus is fastened with a thread from the outside and fixed to the inner member, the above three-component reactive adhesive is applied to the thread. Also good. When such an adhesive application is performed, it is possible to simultaneously ensure the insertability by finishing the outer surface and prevent the yarn from fraying.

  As described above, in the present invention, as an adhesive, a main agent obtained by adding a predetermined amount of rubber and / or plastic to an epoxy resin, a curing agent composed of a predetermined amine, and a heat / cationic curing agent are used. Using a three-component reactive adhesive obtained by mixing at a compounding ratio, the parts of the endoscope are joined to each other, the outer surface finish and the thread are fixed to the end of the flexible outer tube of the insertion part of the endoscope. Since the image sensor of the endoscope is sealed or the adhesive is raised around the observation lens or illumination lens of the endoscope to smooth the corners of the lens outer periphery, various disinfection methods are used. However, it is possible to obtain an end appearance of the flexible outer tube that has excellent adhesive strength and is not different from the initial appearance.

[Example]
Hereinafter, the present invention will be specifically described with reference to examples.

Example 1
As the main component, 60 parts by weight of bisphenol A type epoxy resin BPA328 (manufactured by Nippon Shokubai) in which 20 parts by weight of acrylic rubber having an average particle size of 300 nm is dispersed, 30 parts by weight of phenol novolac type epoxy resin Epicoat 152, and bisphenol A 10 parts by weight of type epoxy resin are prepared, and 40 parts by weight of aliphatic aromatic amine curing agent (Fuji Kasei) and thermal / cationic curing initiator CI-2624 (manufactured by Nippon Soda) 2 parts by weight were added, and 0.1 part by weight of an epoxy silane coupling agent was mixed as an adhesion promoter to prepare an adhesive. It apply | coated to the endoscope components and the curing reaction was carried out at 80 degreeC for 2 hours in the state which bonded these components together.

  Further, the end portion of the flexible outer tube of the insertion portion was fastened with a thread from the outside and fixed to the inner member, and the outer surface was finished by applying the adhesive to the thread. The imaging device of the endoscope was sealed with this adhesive. Furthermore, by using this adhesive to form an adhesive layer around the observation lens and illumination lens of the endoscope, the corners of the outer periphery of the observation lens and illumination lens were smoothed. . The endoscope apparatus was assembled as described above.

Example 2
As main ingredients, 60 parts by weight of bisphenol A type epoxy resin BPA328 (manufactured by Nippon Shokubai) in which 20 parts by weight of acrylic rubber having an average particle size of 300 nm is dispersed, 30 parts by weight of phenol novolac type epoxy resin Epicoat 152, and bisphenol A Prepare 10 parts by weight of type epoxy resin, and add 40 parts by weight of alicyclic amine curing agent and 6 parts by weight of thermal / cationic curing initiator CI-2855 (manufactured by Nippon Soda) as components on the curing agent side. Then, 0.14 parts by weight of an epoxysilane coupling agent was mixed as an adhesiveness imparting agent to prepare an adhesive. An endoscope was assembled in the same manner as in Example 1 using the obtained adhesive.

Example 3
As the main component, 75 parts by weight of bisphenol A type epoxy resin BPA328 (manufactured by Nippon Shokubai Co., Ltd.) in which 20 parts by weight of acrylic rubber having an average particle size of 300 nm is dispersed and 25 parts by weight of bisphenol A type epoxy resin are prepared. 40 parts by weight of aliphatic aromatic amine curing agent and 2 parts by weight of thermal / cationic curing initiator CI-2624 are added as side components, and 0.3 weight of epoxy silane coupling agent is added as an adhesion-imparting agent. Parts were mixed to prepare an adhesive. An endoscope was assembled in the same manner as in Example 1 using the obtained adhesive.

Comparative Example 1
An adhesive was prepared in the same manner as in Example 1 except that the heat / cationic curing initiator CI-2624 was not added. An endoscope was assembled in the same manner as in Example 1 using the obtained adhesive.

Comparative Example 2
An adhesive was prepared in the same manner as in Example 1 except that 40 parts by weight of a heat / cationic curing initiator C1 2624 (manufactured by Nippon Shokubai Co., Ltd.) was mixed without adding an epoxysilane coupling agent. An endoscope was assembled in the same manner as in Example 1 using the obtained adhesive.

Comparative Example 3
Instead of bisphenol A type epoxy resin BPA328, 75 parts by weight of bisphenol F type epoxy resin BPF307 (manufactured by Nippon Shokubai Co., Ltd.) in which 20 parts by weight of acrylic rubber having an average particle size of 300 nm is dispersed, and bisphenol instead of bisphenol A type epoxy resin Implemented except that 25 parts by weight of F-type epoxy resin was used, no phenol novolac-type epoxy resin Epicoat 152 was used, and the addition amount of the thermal / cationic curing initiator CI-2855 was increased to 6 parts by weight. An adhesive was prepared in the same manner as in Example 1. An endoscope was assembled in the same manner as in Example 1 using the obtained adhesive.

  Table 1 shows the component prescriptions of the above Examples and Comparative Examples.

In addition, Table 1 shows the results of the initial adhesion strength between stainless steels of each of these examples (SUS + SUS), stainless steel and engineering plastics, the oxidation chemical solution test (peracetic acid / hydrogen peroxide solution immersion), and the test strength after the autoclave test. Show. The oxidation chemical solution test and autoclave test were performed after the samples were bonded and cured at 80 ° C. for 2 hours.

  Here, the bond strength test conforms to JIS K 6850 ° “Test method for tensile shear bond strength of adhesive”, and the test pieces are made of stainless steel 304 (SUS + SUS), stainless steel 304 and engineering plastic. And measured.

  The peracetic acid environment test and the hydrogen peroxide solution environment test were in accordance with JIS K 6858 “Adhesive chemical resistance test”. In the peracetic acid environment test, the above-mentioned test piece was heated to 53 ° C. in a 4% peracetic acid aqueous solution, taken out after being immersed for 24 hours, and then subjected to a tensile shear bond strength test after drying at room temperature. Further, in the hydrogen peroxide aqueous environment test, the sample was taken out after being immersed in a 30% aqueous peroxide solution for 100 hours, and the tensile shear bond strength test was measured after drying at room temperature for 24 hours.

  In the autoclave test, 600 test pieces were sterilized and removed by a steam sterilization apparatus using steam at 135 ° C., and the tensile shear bond strength test was measured after drying at room temperature for 24 hours. The unit of adhesive strength is MPa.

  As is clear from these test results, Examples 1 to 3 were significantly improved in a hydrogen peroxide environment as compared with Comparative Examples 1 to 3. Thus, it has been found that when the present invention is used, the endoscope parts are not deteriorated by the oxidizing chemical solution or the autoclave, and the adhesive strength of the endoscope apparatus is improved.

  The present invention is not limited to the above embodiments, and various modifications can be made without departing from the spirit of the present invention.

(Appendix)
Appendix 1. A main agent obtained by adding 5 to 15% by weight of rubber and / or plastic to an epoxy resin, an amine curing agent having a compounding ratio of 10: 1 to 10: 4 with respect to the main agent, and a thermal / cationic curing initiator 0.1 An endoscope apparatus, wherein members constituting an endoscope are joined with a three-component reactive adhesive containing 1% by weight.

  Appendix 2. A main agent obtained by adding 5 to 15% by weight of rubber and / or plastic to an epoxy resin, an amine-based curing agent having a compounding ratio of 10: 1 to 10: 4 with respect to the main agent, and a thermal / cationic curing initiator 0.1 to An endoscope apparatus, wherein an endoscope imaging device is sealed with a three-component reactive adhesive containing 1% by weight.

  Appendix 3. After fixing the end of the flexible outer tube of the insertion part of the endoscope with a thread from the outside and fixing it to the inner member, an adhesive is applied to the thread to ensure insertion and prevent fraying of the thread. Is an endoscope apparatus in which the outer surface is finished and fixed, and the adhesive includes an epoxy resin containing 5 to 15% by weight of rubber and / or plastic, an aliphatic amine, and a polyamidoamine A curing agent having a compounding ratio of 10: 1 to 10: 4 with respect to the main agent, and a heat / cation, comprising at least one amine selected from the group consisting of aromatic amines, cyclic amines, and aliphatic aromatic amines An endoscope apparatus comprising a three-component reactive adhesive containing 0.1 to 1% by weight of a system curing initiator.

  Appendix 4. A main agent obtained by adding 5 to 15% by weight of rubber and / or plastic to an epoxy resin, an amine-based curing agent having a compounding ratio of 10: 1 to 10: 4 with respect to the main agent, and a thermal / cationic curing initiator 0.1 to A three-component reactive adhesive containing 1% by weight of an adhesive layer is formed on the periphery of an observation lens or an illumination lens of an endoscope to form a smooth corner portion on the outer periphery of the lens. An endoscope apparatus characterized by comprising:

  Appendix 5. The epoxy resin is a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolac type epoxy resin, a brominated epoxy resin, an alicyclic type epoxy resin, a polyfunctional type epoxy resin, or a mixture of two or more of these. The endoscope apparatus according to any one of 1 to 4.

  Appendix 6. The endoscope apparatus according to any one of appendices 1 to 5, wherein the rubber added to the epoxy resin is acrylic rubber or liquid nitrile rubber, and the plastic added to the epoxy resin is acrylic resin or urethane resin. .

  Appendix 7. The endoscope apparatus according to any one of appendices 1 to 6, wherein the amine curing agent is an aliphatic amine, a polyamide amine, an aromatic amine, a cyclic amine, an aliphatic aromatic amine, or a mixture of two or more thereof. .

Appendix 8. The thermal / cationic curing agent is one of the following structural formulas (1) to (5)

(Wherein R ¹ and R ² are C ₁₂ H ₂₅ , or R ¹ is C ₁₈ H ₁₇ O and R ² is H)

(Wherein R ¹ and R ² are alkyl groups)

Wherein R ¹ and R ² are selected from CH ₃ and C ₂ H ₅
Alternatively, the endoscope apparatus according to any one of appendices 1 to 7, which is a mixture of two or more of these.

  Appendix 9 Additional notes 1 to 8 in which a catalyst, an adhesion-imparting agent, a solvent, a plasticizer, a filler, and others (an antioxidant, a polymerization inhibitor, a surfactant, a fungicide, and a colorant) are added to the adhesive. The endoscope apparatus according to any one of the above.

  Appendix 10. The endoscope apparatus according to any one of appendices 1 to 9, wherein the heating temperature after applying the adhesive is 60 to 135 ° C, and the heating time is 0.5 to 3 hours.

  Appendix 11. When the parts of the endoscope are joined by an adhesive, the mouth portion of the tubes inserted into the insertion portion of the endoscope is fixed to the distal end of the insertion portion of the endoscope or the operation portion. In order to fix the lens group arranged in the hard tip portion to the lens frame or hard tip portion of the insertion portion, to fix the fiber bundle inserted through the insertion portion to the lens frame or hard tip portion of the insertion portion, or to the insertion portion The endoscope apparatus according to any one of appendices 1 to 10, which is for protecting and fixing a CCD incorporated in the hard end portion of the endoscope.

Claims (7)

  A main agent obtained by adding 5 to 15% by weight of rubber and / or plastic to an epoxy resin, an amine-based curing agent having a compounding ratio of 10: 1 to 10: 4 with respect to the main agent, and a thermal / cationic curing initiator 0.1 to An endoscope apparatus characterized in that a member constituting the endoscope is joined with a three-component reactive adhesive containing 1% by weight.   A main agent obtained by adding 5 to 15% by weight of rubber and / or plastic to an epoxy resin, an amine-based curing agent having a compounding ratio of 10: 1 to 10: 4 with respect to the main agent, and a thermal / cationic curing initiator 0.1 to An endoscope apparatus, wherein an endoscope imaging device is sealed with a three-component reactive adhesive containing 1% by weight.   After fixing the end of the flexible outer tube of the insertion part of the endoscope with a thread from the outside and fixing it to the inner member, an adhesive is applied to the thread to ensure insertion and prevent fraying of the thread. Is an endoscope apparatus in which the outer surface is finished and fixed, and the adhesive comprises a main agent obtained by adding 5 to 15% by weight of rubber and / or plastic to an epoxy resin, and a mixing ratio with respect to the main agent. An endoscopic device comprising a three-component reactive adhesive containing an amine-based curing agent of 10: 1 to 10: 4 and 0.1 to 1% by weight of a thermal / cationic curing initiator. .   A main agent obtained by adding 5 to 15% by weight of rubber and / or plastic to an epoxy resin, an amine-based curing agent having a compounding ratio of 10: 1 to 10: 4 with respect to the main agent, and a thermal / cationic curing initiator 0.1 to A three-component reactive adhesive containing 1% by weight of an adhesive layer is formed on the periphery of an observation lens or an illumination lens of an endoscope to form a smooth corner portion on the outer periphery of the lens. An endoscope apparatus characterized by comprising:   The epoxy resin is at least one selected from the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, brominated epoxy resin, alicyclic type epoxy resin, and polyfunctional type epoxy resin. The endoscope apparatus according to any one of claims 1 to 4, wherein the endoscope apparatus is substantially made of an epoxy resin.   The amine-based curing agent substantially comprises at least one amine selected from the group consisting of aliphatic amines, polyamide amines, aromatic amines, cyclic amines, and aliphatic aromatic amines. The endoscope apparatus according to any one of 1 to 5. The heat / cationic curing agent is at least one selected from the group consisting of an aromatic iodonium compound represented by the following structural formula (1) and an aromatic sulfonium compound represented by the following structural formulas (2) to (5). The endoscope apparatus according to any one of claims 1 to 6, wherein the endoscope apparatus substantially comprises a seed.

(Wherein R ¹ and R ² are C ₁₂ H ₂₅ , or R ¹ is C ₁₈ H ₁₇ O and R ² is H)

(Wherein R ¹ and R ² are alkyl groups)

Wherein R ¹ and R ² are selected from CH ₃ and C ₂ H ₅