JP2019041872A - Endoscope adhesive, cured material, endoscope, and method for manufacturing endoscope - Google Patents

Abstract

To provide an endoscope adhesive having a substantial pot life, thereafter, capable of implementing quick curing reaction at a low temperature, besides these characteristics, even when it is subject to chemical treatment, with it used for fixing a member, capable of retaining significant adhesive force without causing deterioration, and being suited for fixing the member constituting the endoscope, and a cured material of the endoscope adhesive; and an endoscope using the cured material of the endoscope adhesive, and a manufacturing method thereof.SOLUTION: A two-component endoscope adhesive comprises a main agent and a curing agent, where the main agent includes at least one type of epoxy resin (A) from among a bisphenol-A-type epoxy resin, a bisphenol-F-type epoxy resin, and a phenol novolac-type epoxy resin, and where the curing agent includes a polythiol compound (B) having a specific structure, and a compound (C) for accelerating the curing. The endoscope adhesive, a cured material, an endoscope, and a method for manufacturing the endoscope are provided.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an endoscope adhesive, a cured product, an endoscope, and an endoscope manufacturing method.

  An endoscope for observing the inside of a human body cavity is repeatedly used. Therefore, it is necessary to clean and disinfect the flexible tube constituting the insertion portion of the endoscope every time it is used. Therefore, chemical resistance is required for the insertion portion of the endoscope.

  The insertion portion of the endoscope is inserted into the body cavity through the oral cavity or nasal cavity. In order to reduce the patient's foreign body feeling and pain during insertion, it is desired to further reduce the diameter of the insertion portion of the endoscope. For this reason, an adhesive is mainly used instead of a bulky member such as a screw and a screw for joining members constituting the insertion portion.

Among adhesives, epoxy resins are used in various fields because they are excellent in workability and are excellent in adhesiveness, electrical properties, heat resistance, moisture resistance and the like of cured products.
For example, Patent Document 1 describes that an epoxy adhesive is used for bonding between a tube body and a braid, which is filled in a braided stitch covering a tube body constituting a flexible tube of an endoscope or a catheter. Has been. This adhesive flexible tube has a large allowable curvature, and if the tube body alone is bent to such a degree that it can be flattened and broken, the original cross-sectional shape can be substantially maintained. Patent Document 2 describes a method for producing an adhesive containing an epoxy resin compound and an encapsulated thiol curing agent. This adhesive has a long pot life.

JP 2004-180831 A Japanese Unexamined Patent Publication No. 2016-216072

In the endoscope manufacturing process, if the curing temperature of the epoxy adhesive is high, the endoscope will be exposed to a high temperature several times in the manufacturing process, and therefore the curing temperature needs to be as low as possible.
Also, the endoscope adhesive is applied or injected into a minute member constituting the endoscope. This operation (process) requires a certain time. Therefore, it is necessary for the adhesive for endoscopes to maintain fluidity so as to enable the above operation for a certain period of time. That is, a sufficient pot life is required. That is, the endoscope adhesive is required to have a property of rapidly curing at a low temperature after an application or injection operation while having a desired pot life.

  On the other hand, the parts fixed or adhered with an adhesive are generally easily degraded by degradation of the adhesive cured product due to the above chemical treatment (decrease in adhesive strength, etc.). Causes performance degradation. Therefore, the adhesive agent for endoscopes is required to have high chemical resistance that is not required for other uses with respect to the cured product.

  Since the invention described in Patent Document 1 uses an epoxy resin and a compound that accelerates curing other than polythiol as a curing agent, it is inferior in curability at a low temperature of less than 23 ° C., and the cured product has a disinfectant resistance. Inferior. The adhesive described in Patent Document 2 needs to give a relatively high energy such as ultrasonic irradiation to the curing of the epoxy resin because the curing agent is included in the capsule. When an optical system component such as a lens or a CCD is bonded and fixed by such a process of curing by ultrasonic irradiation in the assembly of an endoscope, there is a risk that the fixed position of the optical system component will deviate from the original position due to the applied ultrasonic vibration. There is. In addition, when curing an adhesive using an encapsulated curing agent with heat, it is necessary to apply a large amount of energy to destroy the capsule shell, and it is necessary to apply a very high temperature. It is not suitable for endoscopic applications that use low parts.

  An object of the present invention is to provide an adhesive for an endoscope that can maintain a sufficient pot life and can also realize a rapid curing reaction at a low temperature. Furthermore, in addition to the above-described characteristics, the present invention can maintain a sufficient adhesive force that does not deteriorate even when subjected to a chemical treatment in a state where the member is fixed, and can fix the member constituting the endoscope. It is an object to provide an endoscope adhesive and a cured product thereof suitable for use. Moreover, this invention makes it a subject to provide the endoscope which has the said hardened | cured material as an immobilization member of the member which comprises an endoscope, and the performance deterioration by a chemical | medical solution process does not produce easily. Moreover, this invention makes it a subject to provide the manufacturing method of the said endoscope using the said adhesive agent for endoscopes.

一般式（１）中、Ｒ^１〜Ｒ^５のうちの１つはスルファニル基を示し、他は各々独立して水素原子、炭素数１〜１０のアルキル基または炭素数６〜１４のアリール基を示し、ｍは０〜２の整数を示す。ｍが２のとき、２つのＲ^１および２つのＲ^５はそれぞれ互いに同じでもよく、異なってもよい。＊はポリチオール化合物（Ｂ）中における結合部を示す。
一般式（２）中、Ｒ^６〜Ｒ^１０のうちの１つはスルファニル基を示し、他は各々独立して水素原子、炭素数１〜１０のアルキル基または炭素数６〜１４のアリール基を示し、ｎは０〜２の整数を示す。ｎが２のとき、２つのＲ^６および２つのＲ^１０はそれぞれ互いに同じでもよく、異なってもよい。＊はポリチオール化合物（Ｂ）中における結合部を示す。 The above problem has been solved by the following means.
<1>
A two-component endoscope adhesive having a main agent and a curing agent,
The main agent contains at least one epoxy resin (A) of bisphenol A type epoxy resin, bisphenol F type epoxy resin and phenol novolac type epoxy resin,
The curing agent includes a polythiol compound (B) and a compound (C) that promotes curing, and the polythiol compound (B) has at least two partial structures represented by the following general formula (1), or An adhesive for an endoscope, which is a compound having at least two partial structures represented by the following general formula (2).

In general formula (1), ^one of R ^{1 to} R ⁵ represents a sulfanyl group, and the other each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 14 carbon atoms. M represents an integer of 0-2. When m is 2, two R ¹ and two R ⁵ may be the same or different from each other. * Represents a bonding part in the polythiol compound (B).
In general formula (2), one of R ^{6 to} R ¹⁰ represents a sulfanyl group, and the other each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 14 carbon atoms. N represents an integer of 0-2. When n is 2, two R ⁶ and two R ¹⁰ may be the same as or different from each other. * Represents a bonding part in the polythiol compound (B).

一般式（３）中、Ｒ^１１およびＲ^１２は、各々独立して水素原子または炭素数１〜１０のアルキル基を示し、ｓは０〜２の整数を示す。＊はポリチオール化合物（Ｂ）中における結合部を示す。 <2>
The adhesive for endoscopes according to <1>, wherein the polythiol compound (B) is a polythiol compound having at least two partial structures represented by the following general formula (3).

In General Formula (3), R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and s represents an integer of 0 to 2. * Represents a bonding part in the polythiol compound (B).

<3>
The adhesive for endoscopes according to <2>, wherein in the general formula (3), R ¹¹ and / or R ¹² represents an alkyl group having 1 to 10 carbon atoms.
<4>
The polythiol compound (B) is 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptopropionate), tetraethylene glycol Bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) and tris [(3-Mercaptopro Oniruokishi) is at least one of ethyl] isocyanurate, endoscopic adhesive according to <1> or <2>.

<5>
The polythiol compound (B) is 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl)- <1> to <4>, which are at least one of 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and trimethylolpropane tris (3-mercaptobutyrate) The endoscope adhesive agent as described in any one of these.
<6>
<1> The polythiol compound (B) is used in an amount of 10 to 120 parts by mass, and the compound (C) that accelerates the curing is used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin (A). >-<5> The endoscope adhesive according to any one of the above.

<7>
Hardened | cured material formed by hardening the adhesive agent for endoscopes as described in any one of <1>-<6>.
<8>
An endoscope in which a resin member, a metal member, and / or a glass member are fixed by the cured product according to <7>.
<9>
The manufacturing method of an endoscope including fixing a resin member, a metal member, and / or a glass member using the adhesive agent for endoscopes as described in any one of <1>-<6>.

  In the description of the present invention, “to” is used in the sense of including the numerical values described before and after it as lower and upper limits.

  In the description of the present invention, when the number of carbon atoms of a certain group is defined, this number of carbons means the total number of carbon atoms of the group. That is, when this group is a form further having a substituent, it means the total number of carbon atoms including this substituent.

  In the present invention, when there are a plurality of substituents, linking groups, etc. (hereinafter referred to as substituents) indicated by a specific symbol, or when a plurality of substituents etc. are defined simultaneously or alternatively, each substitution It means that the groups and the like may be the same or different from each other. Further, even if not specifically stated, when a plurality of substituents and the like are adjacent to each other, it means that they may be connected or condensed to form a ring.

  The endoscope adhesive of the present invention can ensure a sufficient pot life and also realize a rapid curing reaction at a low temperature. In addition, the endoscope adhesive of the present invention can maintain excellent adhesiveness that is hardly deteriorated even when it is subjected to a chemical treatment in a state where it is used for fixing a member. Therefore, the adhesive for endoscopes according to the present invention is suitable for fixing members constituting the endoscope. Moreover, the hardened | cured material of this invention does not deteriorate easily even if it sterilizes. Therefore, the endoscope of the present invention having this cured product as an immobilizing member for the member constituting the endoscope is also less likely to deteriorate in performance due to the chemical treatment. According to the endoscope manufacturing method of the present invention, the endoscope can be obtained.

It is an external view which shows the structure of one Embodiment of the endoscope of this invention. It is a fragmentary sectional view which shows the structure of the insertion part of the endoscope shown in FIG. It is an external appearance perspective view of the front-end | tip part of the said insertion part. It is a partial notch fragmentary sectional view of the said front-end | tip part. The hatching showing the cross section of the lens and prism was omitted.

<Endoscope adhesive>
The endoscope adhesive of the present invention is a two-component adhesive that includes a main agent and a curing agent separately (consisting of a preparation containing the main agent and a preparation containing a curing agent).
The main agent contains at least one epoxy resin (A) of bisphenol A type epoxy resin, bisphenol F type epoxy resin and phenol novolac type epoxy resin. The curing agent contains a polythiol compound (B) and a compound (C) that accelerates curing as a curing component (a component that acts on the epoxy resin to cure or a component that accelerates the curing).
The endoscope adhesive of the present invention is used to fix a resin member (this resin member includes a rubber member), a metal member, and / or a glass member constituting the endoscope. This “fixing” is performed by adhering a resin member, a metal member, and / or a glass member to a support member or the like constituting the endoscope. The support member may be a tube wall or the like of an endoscope or a non-movable member fixed to the tube wall or the like, and a member whose relative position in the endoscope can move like a tube. Also good. In the present invention, the term “fixed” means that the space between the member constituting the endoscope and the support member in which the member is incorporated is filled with an adhesive cured product, that is, sealed. Used to include.
Hereinafter, the “endoscopic adhesive” may be simply referred to as “adhesive”. Moreover, the fixing | fixed part thru | or sealing part formed between the members by the said adhesive hardened | cured material may be called an adhesion part.

While the adhesive of the present invention has a moderately long pot life, it has the property of being rapidly cured even at low temperatures after coating or pouring. In addition, a cured product obtained by curing the adhesive is not easily oxidized and deteriorated even when subjected to a chemical treatment such as an aqueous peracetic acid solution, and exhibits high adhesion to an adherend. That is, it has excellent chemical resistance. Therefore, even if the endoscope manufactured using the adhesive of the present invention is repeatedly subjected to chemical treatment, the performance is not easily deteriorated. The reason for this is not clear yet, but it is thought to be as follows.
It is considered that when the curing agent uses the polythiol compound (B) and the compound (C) that accelerates curing as a curing component, the curing start reaction becomes mild and the pot life of the adhesive can be secured. Further, it is considered that the compound (C) that accelerates curing works catalytically to increase the growth reaction rate of curing, which is one cause of the rapid curing of the adhesive at a low temperature. In addition, by using the polythiol compound (B), the water absorption of the cured product is lowered, the permeation of a chemical solution such as an aqueous solution of peracetic acid into the cured product can be suppressed, and the contact opportunity of peracetic acid to the cured product can be reduced. It is estimated that the resistance against oxidative deterioration caused by chemicals is improved.

(Epoxy resin (A))
The epoxy resin (A) used in the present invention includes a bisphenol A type epoxy resin, a bisphenol F type epoxy resin and / or a phenol novolac type epoxy resin. Each epoxy resin may be used alone or in combination.

  The bisphenol A type epoxy resin used in the present invention is not particularly limited, and those generally used as a main component of an epoxy adhesive can be widely used. Specific examples include bisphenol A diglycidyl ether (for example, “jER825”, “jER828” and “jER834” (all trade names) manufactured by Mitsubishi Chemical Corporation) and bisphenol A propoxylate diglycidyl ether.

  The bisphenol F type epoxy resin used in the present invention is not particularly limited, and those generally used as the main agent of epoxy adhesives can be widely used. Specific examples include bisphenol F diglycidyl ether (for example, “EPICLON830” (trade name) manufactured by DIC) and 4,4′-methylenebis (N, N-diglycidylaniline).

  The phenol novolac type epoxy resin used for the adhesive of the present invention is not particularly limited, and those generally used as the main agent of the epoxy adhesive can be widely used. As a specific example, product number 406775 manufactured by Sigma-Aldrich can be mentioned.

(Polythiol compound (B))
The thiol compound (B) used in the present invention is a compound having at least two partial structures represented by the following general formula (1) or at least two partial structures represented by the following general formula (2). is there. The thiol compound (B) used in the present invention has 3 to 10 (preferably 3 to 6) partial structures represented by the following general formula (1) or the following general formula (2). A structure having 3 to 10 (preferably 3 to 6) partial structures is preferable from the viewpoint of increasing the crosslinking density of the cured product and further improving chemical resistance. On the other hand, the thiol compound (B) used in the present invention has two partial structures represented by the following general formula (1) or two partial structures represented by the following general formula (2). From the viewpoint of exhibiting impact resistance, a relatively soft cured product can be obtained.

In general formula (1), ^one of R ^{1 to} R ⁵ represents a sulfanyl group (thiol group), and the others are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 6 to 14 carbon atoms. M represents an integer of 0 to 2. When m is 2, two R ^{1 s} may be the same as or different from each other, and two R ⁵ may be the same as or different from each other. * Represents a bonding part in the polythiol compound (B).
In general formula (2), one of R ^{6 to} R ¹⁰ represents a sulfanyl group, and the other each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 14 carbon atoms. N represents an integer of 0-2. When n is 2, two R ⁶ may be the same as or different from each other, and two R ¹⁰ may be the same as or different from each other. * Represents a bonding part in the polythiol compound (B).

  The alkyl group having 1 to 10 carbon atoms may be linear or branched. For example, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, hexyl and octyl I can get rid of it. Among these, methyl or ethyl is preferable.

  Specific examples of the aryl group having 6 to 14 carbon atoms include phenyl and naphthyl.

m is preferably 0 or 1.
n is preferably 0 or 1.

一般式（３）中、Ｒ^１１およびＲ^１２は、各々独立して水素原子または炭素数１〜１０のアルキル基を示し、ｓは０〜２の整数を示す。＊はポリチオール化合物（Ｂ）中における結合部を示す。 The partial structure represented by the general formula (1) is preferably a partial structure represented by the following general formula (3).

In General Formula (3), R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and s represents an integer of 0 to 2. * Represents a bonding part in the polythiol compound (B).

R ¹¹ and / or R ¹² preferably represent an alkyl group having 1 to 10 carbon atoms.
An alkyl group having 1 to 10 carbon atoms represented by R ¹¹ and ^{R 12} has the same meaning as the alkyl group which may take as ^{R 1} in the general formula (1), and the preferred range is also the same.

  s is preferably 0 or 1, and more preferably 1.

  The polythiol compound (B) is preferably an ester of a compound represented by the following general formula (4) and a polyfunctional alcohol.

In the general formula ^(4), R 1 to R ⁵ and m are each the ^R 1 to R ⁵ and m in the general formula (1) in the same meaning, and the preferred range is also the same.

  The compound represented by the general formula (4) is preferably a compound represented by the following general formula (5).

In the general formula ^(5), R ^{11, R 12} and s are each and ^{R 11, R 12} and s in the general formula (3) in the same meaning, and the preferred range is also the same.

  Specific examples of the compound represented by the general formula (4) include 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, 2-mercaptoisobutanoic acid, and 3-mercapto-3-phenylpropionic acid. 3-mercaptoisobutyric acid, 2-mercapto-3-methylbutyric acid, 3-mercapto-3-methylbutyric acid, 3-mercaptovaleric acid and 3-mercapto-4-methylvaleric acid.

The polyfunctional alcohol is preferably a 2 to 10 functional alcohol (a polyol having 2 to 10 hydroxy groups), more preferably 2 to 8 functional, and particularly preferably 2 to 6 functional.
Specific examples of the polyfunctional alcohol include alkylene glycol (the alkylene group preferably has 2 to 10 carbon atoms, and the alkylene group may be linear or branched), diethylene glycol, glycerin, dipropylene glycol, trimethylol. Examples include propane, pentaerythritol, dipentaerythritol, and the like.

  Examples of the alkylene glycol include ethylene glycol, trimethylene glycol, 1,2-propane glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, and tetramethylene glycol.

  As the polyfunctional alcohol, alkylene glycol having 2 carbon atoms in the alkylene main chain such as ethylene glycol, 1,2-propane glycol, 1,2-butanediol, and trimethylolpropane and pentaerythritol are preferable.

  Hereinafter, although the specific example of a thiol compound (B) is given, this invention is not limited to these.

  Specific examples include bis (1-mercaptoethyl) phthalate, bis (2-mercaptopropyl) phthalate, bis (3-mercaptobutyl) phthalate, bis (3-mercaptoisobutyl) phthalate, ethylene glycol bis (3 -Mercaptopropionate), ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), tetraethylene glycol bis (3-mercaptopropionate) ), Butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate) , Dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptobutyrate) , Ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol Bis (2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate), dipen Erythritol hexakis (2-mercaptopropionate), ethylene glycol bis (3-mercaptoisobutyrate), propylene glycol bis (3-mercaptoisobutyrate), diethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), octanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptoisobutyrate), dipentaerythritol hexa Kiss (3-mercaptoisobutyrate), ethylene glycol bis (2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis ( 2-mercaptoisobutyrate), dipentaerythritol hexakis (2-mercaptoisobutyrate), ethylene glycol bis (4-mercaptovalerate), propylene glycol bis (4-mercaptoisovalerate), diethylene glycol bis (4- Mercaptovalerate), butanediol bis (4-mercaptovalerate), octanediol bis (4-mercaptovalerate), trimethylolpropane tris (4-mercaptovalerate), pentaerythritol Tetrakis (4-mercaptovalerate), dipentaerythritol hexakis (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), propylene glycol bis (3-mercaptovalerate), diethylene glycol bis (3-mercapto) Valerate), butanediol bis (3-mercaptovalerate), octanediol bis (3-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate), di Pentaerythritol hexakis (3-mercaptovalerate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5- Triazine -2,4,6 (1H, 3H, 5H) - trione, and tris [(3-mercapto propionyloxy) ethyl] isocyanurate.

  The polythiol compound (B) has little odor, has a desired degree of viscosity, good mixing properties with the epoxy resin (A), and handling properties of a mixture obtained by mixing the main agent and the curing agent. ) Is 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5 -Triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptopropionate), tetraethylene glycol bis (3-mercapto Propionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tet Preferably, it is at least one of kiss (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) and tris [(3-mercaptopropionyloxy) ethyl] isocyanurate. , 4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2 , 4, 6 (1H, 3H, 5H) -trione and at least one of trimethylolpropane tris (3-mercaptobutyrate) are preferred.

  The molecular weight of the polythiol compound (B) is not particularly limited, but it is easy to mix with the epoxy resin (A) of the adhesive of the present invention and difficult to re-separate, and the sauce of the mixture obtained by mixing the main agent and the curing agent. From the viewpoint of handleability such that it is difficult to cause unevenness, it is preferably 200 to 1,000, more preferably 300 to 800.

  In the present invention, a commercially available product can be used as the polythiol compound (B). As a specific example, 1,4-bis (3-mercaptobutyryloxy) butane (trade name: Karenz MT BD1, manufactured by Showa Denko KK) , Pentaerythritol tetrakis (3-mercaptobutyrate) (trade name: Karenz MT PE1, manufactured by Showa Denko KK), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2 , 4, 6 (1H, 3H, 5H) -trione (trade name: Karenz MT NR1, manufactured by Showa Denko) and trimethylolpropane tris (3-mercaptobutyrate) (trade name TPMB, manufactured by Showa Denko) It is done.

[Compound (C) that accelerates curing]
The compound (C) for accelerating curing used in the present invention has a reaction activation start temperature at a low temperature of -20 to 23 ° C., and accelerates the curing of the epoxy resin (A).

  Although the compound (C) which accelerates | stimulates hardening used for this invention is not specifically limited, An amine compound, a guanidine compound, an imidazole compound, a phosphonium compound, etc. are mentioned.

  Examples of the amine compound include, but are not limited to, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6, -tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo. And amine compounds such as [5.4.0] -7-undecene (DBU) and 1,5-diazabicyclo [4.3.0] -nonene (DBN).

  The guanidine compound is not particularly limited, but dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, 1,1-dimethylguanidine, 1, 3-diphenylguanidine, 1,2,3-trimethylguanidine, 1,1,3,3-tetramethylguanidine, 1,1,2,3,3-pentamethylguanidine, 1,5,7-triazabicyclo [ 4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1- n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexane Shirubiguanido, 1 Arirubiguanido, 1-phenyl biguanide, 1- (o-tolyl) biguanide, and the like.

  The imidazole compound is not particularly limited, but 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4- Methyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-methylimidazole, 1- (2-cyanoethyl) -2-undecyl Imidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, 1- (2-cyanoethyl) -2-phenylimidazole, 1- (2-cyanoethyl) -2-undecylimidazolium trimellitate, 1- (2-cyanoethyl) -2-phenyl Dazolium trimellitate, 2,4-diamino-6- [2- (2'-methyl-1'-imidazolyl) ethyl] -s-triazine, 2,4-diamino-6- [2- (2'- Undecyl-1′-imidazolyl] ethyl] -s-triazine, 2,4-diamino-6- [2- (2′-ethyl-4′-methyl-1′-imidazolyl) ethyl] -s-triazine, 2, 4-diamino-6- [2- (2'-methyl-1'-imidazolyl) ethyl] -s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 4,5-bis (hydroxymethyl)- 2-phenylimidazole, 5-hydroxymethyl-4-methyl-2-phenylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecy Imidazole compounds such as 2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, 1- (2-hydroxy-3-phenoxy) propyl-2-methylimidazole, and imidazole compounds and epoxy resins Of adducts.

  Although it does not specifically limit as a phosphonium compound, Tetraphenylphosphonium bromide, Tetrabutylphosphonium bromide, Butyltriphenylphosphonium bromide, Tetraphenylphosphonium iodide, Tetrabutylphosphonium iodide, Butyltriphenylphosphonium iodide, Tetraphenylphosphonium tetraphenyl Borate, tetrabutylphosphonium tetraphenylborate, butyltriphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrabutylborate, tetrabutylphosphonium tetrabutylborate, butyltriphenylphosphonium tetrabutylborate, tetraphenylphosphonium acetate, tetrabutylphosphonium acetate, butyl Torife Le phosphonium acetate, tetrabutylphosphonium tetrafluoroborate, tetrabutyl phosphonium hexafluorophosphate, methyl tributyl phosphonium dimethyl phosphate, tetrabutylphosphonium acetate, tetrabutylphosphonium hydroxide, tetrabutylphosphonium chloride, tetraphenylphosphonium chloride, and the like. Among these, from the viewpoint of reactivity and transparency, tetrabutylphosphonium bromide, methyltributylphosphonium dimethyl phosphate, tetrabutylphosphonium chloride, tetrabutylphosphonium iodide, tetrabutylphosphonium tetraphenylborate, tetraphenylphosphonium bromide, tetraphenylphosphonium Chloride, tetraphenylphosphonium iodide and tetraphenylphosphonium tetraphenylborate are preferred, and methyltributylphosphonium dimethylphosphate and tetrabutylphosphonium bromide are more preferred.

  In this invention, the compound (C) which accelerates | stimulates hardening may be used individually by 1 type, and may be used in combination of 2 or more type.

  In the adhesive of the present invention, 10 to 120 parts by mass of the polythiol compound (B) constituting the curing agent and 0% of the compound (C) that promotes curing with respect to 100 parts by mass of the epoxy resin (A) constituting the main agent. 0.1 to 10 parts by mass is preferably used, and 15 to 100 parts by mass of the polythiol compound (B) and 0.2 to 6 parts by mass of the compound (C) that accelerates curing are used. More preferably, the polythiol compound (B) is used in an amount of 20 to 90 parts by mass, and the compound (C) that promotes curing is used in an admixture of 0.5 to 3 parts by mass.

  80 mass% or more is preferable, as for content of the epoxy resin (A) in the said main ingredient, 90 mass% or more is more preferable, and 100 mass% may be sufficient. The above main ingredients are within the range not impairing the effects of the present invention, epoxy resins other than the epoxy resin (A), solvents, plasticizers, adhesion improvers (silane coupling agents, etc.), surfactants, colorants (pigments, dyes) Etc.), weathering agent, antioxidant, heat stabilizer, lubricant, antistatic agent, whitening agent, mold release agent, conductive agent, viscosity modifier, filler (silica, calcium carbonate, etc.), thixotropic agent, Diluents (eg monofunctional epoxy compounds) and / or flame retardants may be included.

  In the present invention, the polythiol compound (B) functions as a curing agent for the epoxy adhesive. The compound (C) that accelerates curing acts as a curing component of the epoxy resin (A) together with the polythiol compound (B). Therefore, the total content of the polythiol compound (B) and the compound (C) that accelerates curing in the curing component in the curing agent is preferably 70% by mass or more, more preferably 80% by mass or more, and 90% A mass% or more is particularly preferred. Moreover, it is also preferable that all the hardening components in the said hardening | curing agent consist of a compound (C) which accelerates | stimulates a polythiol compound (B) and hardening.

  The curing agent may be composed of the above-described curing component, and includes a solvent, a plasticizer, a viscosity modifier, a filler, a colorant, and the like within the range not impairing the effects of the present invention, in addition to the curing component. You may go out. 80 mass% or more is preferable and, as for content of the hardening component in a hardening | curing agent, 90 mass% or more is more preferable.

<Hardened product>
The cured product of the present invention is a cured product generated by curing the adhesive of the present invention. That is, the hardened | cured material of this invention is used as a member which comprises the adhesion part of an endoscope. After mixing the main ingredient of the adhesive of the present invention and the curing agent, for example, the cured product of the present invention can be obtained by curing by heating at -20 to 150 ° C. for 10 minutes to 72 hours. Mixing of the main agent and the curing agent can be performed by a conventional method. This mixing is preferably performed while removing bubbles, and is therefore usually performed under reduced pressure. When the curing temperature is high, the endoscope is exposed to a high temperature several times in the manufacturing process, and therefore it is preferable to make the curing temperature as low as possible. In this respect, the curing temperature is preferably 100 ° C. or lower, and more preferably 80 ° C. or lower. Moreover, in order to fully perform hardening reaction, 0 degreeC or more is preferable and 10 degreeC or more is more preferable.

<Endoscope>
The endoscope of the present invention has an adhesive portion between a resin member, a metal member, or a glass member and a fixed member via the cured product of the present invention.
An example of the endoscope (electronic endoscope) of the present invention will be described. A flexible tube for an endoscope is incorporated in an electronic endoscope (hereinafter, the flexible tube for an endoscope may be simply referred to as “flexible tube”), and is widely used as a medical device. In the example shown in FIG. 1, the electronic endoscope 2 is connected to an insertion unit 3 inserted into a body cavity, a main body operation unit 5 connected to a proximal end portion of the insertion unit 3, a processor device, and a light source device. And a universal cord 6 to be connected. The insertion portion 3 is connected to the flexible tube 3a connected to the main body operation portion 5, the angle portion 3b connected to the flexible tube 3a, and the tip thereof, and is mainly composed of a metal (for example, stainless steel) member. It is comprised from the front-end | tip part 3c. The distal end portion 3c incorporates an imaging device (not shown) for intracorporeal imaging. The flexible tube 3a occupying most of the length of the insertion portion 3 has flexibility over almost the entire length thereof, and in particular, a portion inserted into a body cavity or the like has a more flexible structure.
In FIG. 1, a plurality of channels (not shown) penetrating in the axial direction of the insertion portion 3 are formed from the main body operation portion 5 to the distal end surface of the distal end portion 3c.

As shown in FIG. 2, the flexible tube 3 a in FIG. 1 has a configuration in which the outer peripheral surface of the flexible tube base material 14 is coated with a resin layer 15.
14a is the distal end side (the distal end portion 3c side), and 14b is the proximal end side (the main body operation unit 5 side).
The flexible tube base material 14 is formed by covering a spiral tube 11 formed by spirally winding a metal strip 11a on the innermost side with a cylindrical mesh body 12 formed by braiding metal wires. The bases 13 are respectively fitted at both ends. The resin layer 15 is bonded to the flexible tube base 14 via the adhesive cured material layer 17. Although the cured adhesive layer (adhesive portion) 17 is illustrated as a layer having a uniform thickness for the convenience of illustration, the adhesive cured material layer (adhesive portion) 17 does not necessarily have to be in the form, and the resin layer 15 and the flexible tube base material 14 are not necessarily shaped. May be interposed between the two. Rather, there is almost no thickness, and the resin layer 15 and the flexible tube base material 14 may be bonded in a form of being substantially in contact with each other.
The outer surface of the resin layer 15 is coated with a coating layer 16 containing, for example, fluorine having chemical resistance. The cured adhesive layer 17, the resin layer 15, and the coat layer 16 are drawn thicker than the diameter of the flexible tube base material 14 in order to clearly show the layer structure.

  As shown in FIG. 3, an illumination window 31, an observation window 32, and a forceps port 33 are formed on the distal end surface of the distal end portion 3c. Moreover, in order to wash | clean a front end surface as needed, the nozzle 34 which sends out water and air is formed. The illumination window 31, the observation window 32, the forceps port 33, and the nozzle 34 are connected to the main body operation unit 5 through channels.

  As shown in FIG. 4, the distal end portion 3c includes a distal end portion main body 35 made of metal and a distal end cap 36 made of an electrically insulating member.

  An observation unit 43 that is an optical system device is installed in the observation window 32. In the observation unit 43, an objective optical system composed of the lenses L <b> 1 to L <b> 5 is fixed in a lens holder 37 with adhesive cured products 41 and 42. In this objective optical system, A is an air layer. A prism 38 is bonded and fixed to the end surface of the lens holder 37. By this prism 38, the optical axis of the objective optical system is bent at a right angle. The prism 38 is bonded to the solid-state image sensor 40. The solid-state image sensor 40 is fixed to the substrate 39.

<Endoscope manufacturing method>
The endoscope manufacturing method of the present invention is not particularly limited as long as it includes fixing the resin member, the metal member, and / or the glass member using the adhesive of the present invention, and the resin member, the metal member, and / or About processes other than fixation of a glass member, the normal manufacturing process is employ | adopted and the endoscope of this invention can be manufactured. For example, in the endoscope manufacturing method of the present invention, the main agent of the adhesive of the present invention and the curing agent are mixed under reduced pressure, and then the adhesive of the present invention is injected or applied to the application site, and -20 to 20 is applied. It is preferable to include a step of heating at 150 ° C. (preferably 0 to 100 ° C., more preferably 10 to 80 ° C.) for 10 minutes to 72 hours (preferably 30 minutes to 48 hours, more preferably 1 to 24 hours).

<Use of adhesive>
The adhesive of the present invention is used to fix a resin member, a metal member, and / or a glass member that constitute an insertion portion of an endoscope to another member that constitutes the endoscope. That is, this fixing is performed by bonding a resin member, a metal member, and / or a glass member to a support member (including a resin member, a glass member, and a metal member). The adhesive of the present invention is preferably a resin member fixed to a metal member, a metal member fixed to a resin member, a metal member fixed to another metal member, a glass member fixed to a metal member, a resin member Used for fixing glass members to the surface.
Hereinafter, although the usage example of the adhesive agent of this invention is given and demonstrated with a specific example, this invention is not limited to these.

An example of the resin member is a tube that is inserted into an insertion portion of an endoscope. Examples of the tube include various tubes manufactured using various materials such as fluororesin such as Teflon (registered trademark), resin such as polysulfone, polyester, polyolefin, and silicone, or rubber. The adhesive of the present invention can be used, for example, for bonding a metal member or glass member that constitutes an insertion portion of an endoscope and the tube (fixing of the metal member or glass member to the tube).
It can also be used to form the cured adhesive layer 17 in FIG. Moreover, it can also be used for adhesion between the resin layer 15 and the coat layer 16 in FIG.

The adhesive of the present invention can be used for finishing and fixing the outer surface of the end portion of the flexible outer tube (resin layer 15) (the end portion on the distal end side (angle portion 3b side) of the flexible tube 3a). Specifically, the flexible tube 3a and the angle portion 3b are bonded using the adhesive of the present invention. The vicinity of the bonding portion of the flexible tube 3a, the vicinity of the bonding portion of the angle portion 3b, and the bonding portion are wound with a thread to reinforce the bonding. By forming the outermost layer of the distal end side of the flexible tube 3a and the end portion of the angled portion 3b on the flexible tube 3a side with the adhesive of the present invention, this thread is less likely to fray and the insertion portion is inserted into the body cavity. This is to make it easier. The insertion part thus formed can maintain a glossy appearance even after sterilization.
In addition, the adhesive of the present invention can be used for bonding the tip portion 3 c and the angle portion 3 b and / or bonding the insertion portion 3 and the main body operation unit 5. Specifically, the tip 3c and the angle 3b are bonded using the adhesive of the present invention. The vicinity of the bonding portion of the tip 3c, the vicinity of the bonding portion of the angle portion 3b, and the bonding portion are wound with a thread to reinforce the bonding. Similar to the above, an adhesive is applied to cover the yarn and cured. The same applies to the bonding between the insertion portion 3 and the main body operation portion 5.
Moreover, it is preferable to use for fixing to the front-end | tip part 3c and / or the main body operation part 5 of the various tubes penetrated in the insertion part of an endoscope.

The adhesive of the present invention is preferably used for the tip 3c. Among the forms used for the tip portion 3c, the adhesive of the present invention is also preferably used for sealing the illumination window 31 and the observation window 32 (fixing the glass member to the tip cap 36 (resin member)). This is because the corners on the outer periphery of the lens can be fixed smoothly without any step by thick coating, and the incidence of light from the lateral direction of the lens can be blocked.
Further, the adhesive of the present invention can be used for fixing a metal member and / or a glass member, such as assembling an imaging device built in the distal end portion 3c, adhering components, sealing the solid-state imaging element 40, and the like. The imaging device is a solid system such as an optical system composed of a plurality of optical components such as lenses L1 to L5 and a prism 38, and a CCD (Charge Coupled Device) that photoelectrically converts an optical image formed by this optical system into an imaging signal. An imaging device 40. The adhesive of the present invention is used for bonding lenses L1 to L5 made of a material such as glass and optical components such as prism 38, and bonding of lenses L1 to L5 and / or prism 38 to a substrate 39 made of resin or metal. The glass member can be fixed by this adhesion, and the metal member can be fixed.
Further, the adhesive of the present invention can be used for bonding and fixing the solid-state imaging device 40 and the substrate 39. By this adhesion, the metal member constituting the solid-state imaging device, the substrate, and the like can be fixed.

  Below, based on an Example, it demonstrates still in detail about this invention. The present invention is not construed as being limited thereby. “Room temperature” means 25 ° C.

(Preparation of mixture of main agent and curing agent for endoscope adhesive (Example 1))
Epoxy resin (A-1) (bisphenol A diglycidyl ether ("jER825" (trade name), epoxy equivalent 170, manufactured by Mitsubishi Chemical Corporation) 100 parts by mass as the main agent, thiol compound (B-1) as a curing component in this main agent (Pentaerythritol tetrakis (3-mercaptobutyrate) (trade name “Karenz MT PE1” manufactured by Showa Denko KK) and compound (C-1) (2,4,6-tris (dimethylaminomethyl) phenol ( Nacalai Tesque, trade name “Lebeac DMP-30”)) 2 parts by mass and mixed with “Awatori Netaro ARV-310 (trade name, manufactured by Sinky)” at 1.0 Pa at room temperature. In this state, the mixture was degassed for 3 minutes while stirring at 2000 rpm to prepare a mixture of the main agent and the curing agent for the endoscope adhesive.

(Production of sheet-like cured product (Example 1))
The above mixture was cured at 80 ° C. for 12 hours with a mini test press (manufactured by Toyo Seiki Co., Ltd.) to obtain a sheet-like cured product having a length of 60 mm × width of 60 mm × thickness of 2 mm.

(Preparation of mixture of main agent and curing agent of adhesive for endoscope (Examples 2 to 21 and Comparative Examples 1 to 3))
The main ingredients of the adhesives for endoscopes of Examples 2 to 21 and Comparative Examples 1 to 3 are the same as those of the adhesive for endoscopes of Example 1 except that the composition is changed to the composition described in Table 1 below. A mixture of curing agents was prepared.

(Production of sheet-like cured product (Examples 2 to 21 and Comparative Examples 1 to 3))
Using the prepared mixture, the sheet-like cured products of Examples 2 to 21 and Comparative Examples 1 to 3 were produced in the same manner as the sheet-like cured product of Example 1.

  The following tests were performed on the mixtures of Examples 1-21 and Comparative Examples 1-3. The results are shown in Table 1 below.

[Low temperature curability]
About the mixture prepared above, the exothermic peak (maximum) in 0 degreeC and 23 degreeC was confirmed with the differential scanning calorimeter (DSC), and the sclerosis | hardenability in low temperature was evaluated according to the following evaluation criteria. The results are shown in Table 1. A to C pass this test.
-Evaluation criteria-
A: An exothermic peak was confirmed within 4 hours.
B: Exothermic peak was confirmed within 4 hours over 4 hours.
C: An exothermic peak was confirmed within 12 hours exceeding 8 hours.
D: No exothermic peak was confirmed within 12 hours.
[Indicates that the shorter the time until the exothermic peak is observed, the faster the curing occurs. ]

[Pot life]
About the mixture prepared above, the exothermic start time in 23 degreeC was calculated | required using the differential scanning calorimeter (DSC). The results are shown in Table 1.

  The following tests were performed on the sheet-like cured products of Examples 1-21 and Comparative Examples 1-3. The results are shown in Table 1 below.

[Water absorption test]
The sheet-like cured product produced above was immersed in 23 ° C. water for 24 hours. After immersion, the sheet-like cured product was dried by placing it in an oven at 60 ° C. for 12 hours. The water absorption was calculated from the following equation.

(Water absorption (%)) = [{(mass of sheet-like cured product after dipping and before drying) − (mass of sheet-like cured product after drying)} / (mass of sheet-like cured product after drying)] × 100

[Disinfectant resistance test]
The sheet-like cured product produced above was immersed in a peracetic acid aqueous solution (manufactured by Fuji Film Co., Ltd., trade name: Esside) at 45 ° C. It was immersed for a total of 160 hours while exchanging with a new peracetic acid aqueous solution every 40 hours.
Tensile tests (based on the method of JIS K6251 (2010), dumbbell-shaped test pieces) were performed on the sheet-like cured products before and after the immersion, and each elongation at break was calculated by the following formula.

Elongation at break (%) = {(length of sample at break−length of sample before test) / length of sample before test} × 100

The ratio of the breaking elongation after immersion to the breaking elongation before immersion was calculated and evaluated according to the following evaluation criteria. In this test, an evaluation “G” or higher is a passing level of this test.
-Evaluation criteria-
E (Excellent): 60% or more G (Good): 30% or more and less than 60% P (Poor): Less than 30%

<Notes on the table>
[Epoxy compound (A)]
(A-1) Bisphenol A diglycidyl ether (Mitsubishi Chemical Corporation “jER825” (trade name), epoxy equivalent 170)

(A-2) Bisphenol A diglycidyl ether ("jER828" (trade name), epoxy equivalent 190, manufactured by Mitsubishi Chemical Corporation)

(A-3) Bisphenol A diglycidyl ether (Mitsubishi Chemical Corporation “jER834” (trade name), epoxy equivalent 230)

(A-4) Bisphenol F diglycidyl ether (DIC Corporation "EPICLON 830" (trade name), epoxy equivalent 170)

(A-5) Epoxy novolac resin (manufactured by Sigma-Aldrich, product number 406775, epoxy equivalent 170)

(A-6) Bisphenol A propoxylate diglycidyl ether (manufactured by Sigma-Aldrich, epoxy equivalent 228)

(A-7) 4,4′-methylenebis (N, N-diglycidylaniline) (manufactured by Tokyo Chemical Industry Co., Ltd., epoxy equivalent 106)

[Polythiol compound (B)]
(B-1) Pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko KK, trade name “Karenz MT PE1”)
(B-2) 1,4-bis (3-mercaptobutyryloxy) butane (made by Showa Denko KK, trade name “Karenz MT BD1”)
(B-3) 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (manufactured by Showa Denko KK Product name "Karenz MT NR1")
(B-4) Trimethylolpropane tris (3-mercaptobutyrate) (trade name “TPMB” manufactured by Showa Denko KK)
(B-5) Ethylene glycol bis (3-mercaptopropionate) (Wako Pure Chemical Industries, Ltd. reagent)
(B-6) Tetraethylene glycol bis (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd., trade name “EGMP-4”)
(B-7) Trimethylolpropane tris (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd., trade name “TMTP”)
(B-8) Pentaerythritol tetrakis (3-mercaptopropionate) (product name “PEM” manufactured by Sakai Chemical Industry Co., Ltd.)
(B-9) Dipentaerythritol hexakis (3-mercaptopropionate) (trade name “DPMP” manufactured by Sakai Chemical Industry Co., Ltd.)
(B-10) Tris [(3-mercaptopropionyloxy) ethyl] isocyanurate (manufactured by Sakai Chemical Industry Co., Ltd., trade name “TEMPIC”)

[Compound (C) that accelerates curing]
(C-1) 2,4,6-tris (dimethylaminomethyl) phenol (manufactured by Nacalai Tesque, trade name “RUBEAC DMP-30”)
(C-2) 2-Ethyl-4-methylimidazole (Tokyo Chemical Industry Reagent)
(C-3) Tetraphenylphosphonium bromide (trade name “TPP-PB”, manufactured by Hokuko Chemical Co., Ltd.)

[Other curing agents]
(D-1) Polyamidoamine (manufactured by DIC, trade name “Rakkamide EA-330”)
(D-2) Triethylenetetramine (Reagent manufactured by Tokyo Chemical Industry Co., Ltd.)

Since Comparative Example 1 did not use the compound (C) that promotes curing, the 0 ° C. curability was unacceptable and the disinfectant resistance was poor because of the high water absorption rate. In Comparative Example 2, since the compound (D-2) other than the polythiol compound (B) was used and the compound (C) for promoting curing was not used, the 0 ° C. curability was rejected and the disinfectant resistance was insufficient. Met. In Comparative Example 3, the compound (C) that promotes curing was used, but since the compound (D-2) other than the polythiol compound (B) was used, the 0 ° C. curability was rejected and the disinfectant resistance was not satisfactory. It was enough.
On the other hand, in Examples 1-21, all items were acceptable levels.

2 Electronic endoscope (endoscope)
DESCRIPTION OF SYMBOLS 3 Insertion part 3a Flexible pipe 3b Angle part 3c Tip part 5 Main body operation part 6 Universal cord 11 Spiral pipe 11a Metal strip 12 Cylindrical mesh body 13 Base 14 Flexible pipe base material 14a Tip side 14b Base end side 15 Resin layer DESCRIPTION OF SYMBOLS 16 Coat layer 17 Adhesive hardened | cured material layer 31 Illumination window 32 Observation window 33 Forceps opening 34 Nozzle 35 Tip part main body 36 Tip cap 37 Lens holder 38 Prism 39 Substrate 40 Solid imaging device 41 Adhesive hardened material 42 Adhesive hardened material 43 Observation Unit A Air layer L1-L5 Lens

Claims (9)

A two-component endoscope adhesive having a main agent and a curing agent,
The main agent contains at least one epoxy resin (A) of bisphenol A type epoxy resin, bisphenol F type epoxy resin and phenol novolac type epoxy resin,
The curing agent includes a polythiol compound (B) and a compound (C) that promotes curing, and the polythiol compound (B) has at least two partial structures represented by the following general formula (1), or An adhesive for an endoscope, which is a compound having at least two partial structures represented by the following general formula (2).

In general formula (1), ^one of R ^{1 to} R ⁵ represents a sulfanyl group, and the other each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 14 carbon atoms. M represents an integer of 0-2. When m is 2, two R ¹ and two R ⁵ may be the same or different from each other. * Represents a bonding part in the polythiol compound (B).
In general formula (2), one of R ^{6 to} R ¹⁰ represents a sulfanyl group, and the other each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 14 carbon atoms. N represents an integer of 0-2. When n is 2, two R ⁶ and two R ¹⁰ may be the same as or different from each other. * Represents a bonding part in the polythiol compound (B). The endoscope adhesive according to claim 1, wherein the polythiol compound (B) is a polythiol compound having at least two partial structures represented by the following general formula (3).

In General Formula (3), R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and s represents an integer of 0 to 2. * Represents a bonding part in the polythiol compound (B). The endoscope adhesive according to claim 2, wherein, in the general formula (3), R ¹¹ and / or R ¹² represents an alkyl group having 1 to 10 carbon atoms.   The polythiol compound (B) is 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptopropionate), tetraethylene glycol Bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) and tris [(3-Mercaptopro Oniruokishi) is at least one of ethyl] isocyanurate, endoscopic adhesive according to claim 1 or 2.   The polythiol compound (B) is 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl)- Any one of 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and trimethylolpropane tris (3-mercaptobutyrate) The endoscope adhesive agent according to claim 1.   10 to 120 parts by mass of the polythiol compound (B) and 0.1 to 10 parts by mass of the compound (C) for promoting the curing are used with respect to 100 parts by mass of the epoxy resin (A). The adhesive for endoscopes of any one of 1-5.   Hardened | cured material formed by hardening the adhesive agent for endoscopes of any one of Claims 1-6.   An endoscope in which a resin member, a metal member, and / or a glass member are fixed by the cured product according to claim 7.   The manufacturing method of an endoscope including fixing a resin member, a metal member, and / or a glass member using the adhesive agent for endoscopes of any one of Claims 1-6.

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