JPH0737593B2 - Method for manufacturing hot water resistant adhesive structure - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a heat-resistant adhesive structure, and more particularly, to a method for immersing in heat-resistant water or treatment with an autoclave.
The present invention relates to a method for producing an adhesive structure that maintains a strong adhesive state and has adhesive durability for a long period of time.

[0002]

2. Description of the Related Art Assembling a structure by adhesion has a simpler structure for joining as compared with mechanical assembling such as a bolt, a nut or a rivet, and even a large area can be easily joined. It is easy to join materials.
It has been widely used in all industrial fields because of the shortened joining process and high productivity.

Conventionally, a structure assembled by these bondings (hereinafter referred to as "bonded structure") has been conventionally bonded.
Solvent volatilizing adhesives such as vinyl chloride adhesives and synthetic rubber adhesives, as well as chemical reaction types such as epoxy resin, epoxy modified bisphenol A di (meth) acrylate, cyanoacrylate and urethane modified di (meth) acrylate Adhesive is used.

In addition, in recent years, in addition to the fields of optics such as assembling and bonding of lenses, prisms, optical fibers, etc., electronic and electrical fields such as manufacturing and assembling of semiconductors, printed boards, motors, etc. Adhesive technology has been applied to medical fields such as dental and surgical treatments, and not only simple adhesion but also more advanced optical characteristics, heat resistance, water resistance, electrical characteristics, adhesion reliability, etc. Adhesive performance is required.

As one of the applications of such high-level adhesive technology, recently, there is an increasing demand for manufacturing an adhesive structure that can be subjected to boiling sterilization and autoclave treatment for sterilization of viruses and molds in medical instruments and devices. Is coming. Examples of this include assembling and joining of medical endoscopes, dental intraoral laser fibers, dental treatment handpieces, dental treatment light irradiators, and the like.

There is also a demand for an adhesive technique having sufficient adhesive strength and durability even in high-temperature water, and examples of such an adhesive technique include household water heaters, humidifiers, rice cookers, steam boilers and the like. Assembling and joining industrial products.

In these applications, it is strongly desired to have heat resistance and water resistance in addition to the adhesive property. As a bonding method in such a case, a bonding method using a chemically reactive adhesive having excellent heat resistance and water resistance such as epoxy resin and epoxy-modified bisphenol A di (meth) acrylate has been conventionally applied. Recently, as an adhesive that can be sterilized by autoclave, a mixture of a UV-polymerizable urethane-modified oligomer and a mono (meth) acrylate has been introduced.

[0008]

However, in the bonding method using these conventional adhesives, when it is immersed in high temperature water for several minutes, or when the autoclave treatment of about 15 minutes is performed only several times. Shows good adhesive properties, but has poor durability, and shows remarkable deterioration when immersed in water at about 80 ° C for several weeks, resulting in a marked decrease in adhesive strength or in hot water. There was a problem such as spontaneous peeling.

Further, when a lens or prism is joined to a medical endoscope, it is used only by autoclave sterilization only a few times to cause partial peeling at the bonding site and lose optical transparency. It had the defect of disappearing.

Further, in these conventional adhesion techniques, when a large area is adhered, even if it is immersed in high temperature water, deterioration occurs from the periphery, so that the adhesive strength as a whole is not lowered and it can be used. However, when attempting to adhere a small adherend such as a small precision component, there is a problem regarding the adhesion area such that it cannot be applied because the influence of the deterioration of the peripheral portion affects the whole.

The present invention is to eliminate the problems of the conventional bonding technique. That is, the object of the present invention is to provide an adhesive having excellent adhesive strength and having excellent hot water resistance that maintains good adhesive properties even if it is immersed in high temperature water for a long period of time or subjected to a number of autoclave treatments. It is to provide a method for manufacturing a structure. The present invention also has good adhesive properties and hot water resistance and good transparency,
Provided is a method of manufacturing an adhesive structure that can be applied to special optical applications.

[0012]

Means for Solving the Problems As a result of intensive research to solve the above-mentioned problems, the present inventor has treated an adhesive surface of an adherend constituting an adhesive structure with a silane coupling agent, and An excellent adhesion is obtained by interposing an adhesive containing at least one compound selected from the following Group A between the adherends and polymerizing and curing the adhesive to adhere the adherends to each other. The inventors have invented a method for producing an adhesive structure having properties and excellent hot water resistance, and also having good transparency.

Group A Polyfunctional oligoester (meth) acrylate, bis (4- (meth) acryloxymethyl) tricyclo (5,
2,1, O ^2,6 decane, neopentyl glycol modified trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane Tri (meth) acrylate, bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol mono Doropenta (meth) acrylate.

That is, according to the present invention, after the adhesive surface of the adherend constituting the adhesive structure is treated with a silane coupling agent, it is adhered using an adhesive containing a polyfunctional monomer represented by Group A as a component. By doing so, the above object is achieved.

Next, the present invention will be described in more detail.

In the present invention, the adhesive surface of the adherend to be adhered is first treated with a silane coupling agent. This silane treatment is a surface modification with a silane coupling agent used in ordinary adhesion operations. It means quality. Specifically, a silane treatment solution prepared by dissolving a conventionally used silane coupling agent such as γ- (meth) acryloxypropyltrimethoxysilane, trichlorovinylsilane, and triethoxyvinylsilane in a suitable solvent such as ethyl alcohol and water is used. A method of coating the surface of an adherend and then drying it is used. The surface of the adherend may be dried after exposing the adherend to the vapor of the silane coupling agent.

Next, the compounds represented by Group A will be described. Among the compounds used in the present invention, the polyfunctional oligoester (meth) acrylate has the general formula (1),
It is preferable to use the compound represented by (2) or (3) and having a molecular weight of 1000 or less.

[0018] However, in the formula, A represents a (meth) acryloxy group, X represents a polyhydric alcohol, and Y represents a polybasic acid.

[0019] However, in the formula, A represents a (meth) acryloxy group, X represents a polyhydric alcohol, Y represents a polybasic acid, and M represents a dihydric alcohol.

[0020] However, in the formula, A represents a (meth) acryloxy group, X represents a polyhydric alcohol, Y represents a polybasic acid, and M represents a dihydric alcohol.

In any general formula, n is about 1
Represents an integer of ~ 4.

These polyfunctional oligoesters (meth)
Specific examples of the acrylate include oligoester acrylates M-8030 and M manufactured by Toagosei Kagaku Kogyo Co., Ltd.
Examples include −9050.

Among the compounds represented by Group A, examples of neopentyl glycol-modified trimethylolpropane di (meth) acrylate include compounds represented by the following structural formula (4).

[0024] However, in the formula, R ₁ is hydrogen or a methyl group.

Among the compounds represented by Group A, bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate and propylene oxide modified bisphenol A di (meth) acrylate are represented by the following structural formula (5). Mention may be made of the compounds shown.

[0026]

[Chemical 1]

However, in the formula, R ₂ and R ₃ are hydrogen or a methyl group.

Among the compounds represented by Group A, examples of ethylene oxide-modified trimethylolpropane tri (meth) acrylate and propylene oxide-modified trimethylolpropane tri (meth) acrylate include compounds represented by the following structural formula (6). .

[0029]

[Chemical 2]

However, in the formula, R ₄ and R ₅ are hydrogen or a methyl group.

All of the compounds of the group A shown in the present invention are characterized by being polyfunctional monomers which are highly crosslinked during polymerization and curing to give an extremely hard cured product.

One remarkable feature of the compounds of Group A used in the present invention is that each compound is basically a hydrophobic compound containing almost no polar groups such as hydroxyl group and carboxyl group. There is a point.

The adhesive used in the present invention can be obtained by adding a small amount of a polymerization initiator usually used to at least one compound of the group A.

Specific examples of the polymerization initiator include organic peroxides such as dibenzoyl peroxide, lauroyl peroxide and cumene hydroperoxide, and azo compounds such as azobisisobutyronitrile and azobisdimethylvaleronitrile. be able to.

When these polymerization initiators are added,
Heat treatment is performed when the adhesive is polymerized and cured.

In the present invention, a photopolymerization initiator may be used as the polymerization initiator, and examples thereof include 1-hydroxycyclohexyl phenyl ketone, benzophenone, benzoisoethers, acetophenones, benzyl, camphorquinone, benzylmethyl ketal and Examples thereof include thioxanthones.

When these photopolymerization initiators are used,
The adhesive is polymerized and cured by irradiating it with light such as ultraviolet rays and visible light, and when at least one adherend transmits light, the adhesion time can be significantly shortened.

When such a photopolymerization initiator is used, if desired, N, N-dimethyl-p-toluidine,
Tertiary amines such as N, N-dimethylaminoethyl (meth) acrylate and the above organic peroxides may be added as a reaction accelerator, which makes it possible to further increase the reaction rate of photopolymerization. .

In the present invention, for the purpose of further improving the adhesiveness and hot water resistance and adjusting the viscosity of the adhesive to make the bonding work more suitable, the above-mentioned A
It is preferable to use an adhesive in which at least one compound represented by the group is further added with one monofunctional monomer selected from the following group B.

Group B 4- (meth) acryloxytricyclo (5,2,1,0
^2,6 ) Decane, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth)
Acrylate, phenyl (meth) acrylate, adamantyl (meth) acrylate, 4-tert. -Butyl (meth) acrylate, dicyclopentenyl (meth) acrylate.

The compounds shown in Group B are monofunctional monomers having low water absorption and excellent heat resistance.

In the present invention, the compounds represented by Group B are A
It is preferable that the addition ratio is 80% by weight or less based on the compounds shown in the group. If the amount added exceeds the above range, there arises a problem that the hot water resistance of adhesion is impaired.

Examples of the adherend used in the present invention include adhesives, glass, metals, and adhesive composite materials filled with an inorganic filler, and glass, metal and ceramics are particularly preferable. The reason for this is that when glass, metal or ceramics is used as the adherend, the adherend itself does not have substantial water absorption, so it is more excellent than when the adhesive is used as the adherend. This is because hot water resistance and adhesive strength are exhibited.

Further, in the present invention, the surface of the adherend may be preliminarily grained by sandblasting or the like for the purpose of further improving the adhesive strength of the obtained adhesive structure. In particular, when a metal is used for the adherend, the sandblast treatment not only increases the adhesive strength but also significantly increases the hot water resistance.

Examples of the sand used in the sandblasting treatment include alumina and glass beads. Further, the particle size of sand is preferably several microns to several hundreds of microns.

Next, a method for producing an adhesive structure having excellent hot water resistance according to the present invention will be specifically described.

The surface of the adherend used in the present invention is preferably cleaned before the bonding operation, as in the ordinary bonding operation. The surface of the adherend is cleaned by applying a normal cleaning operation such as wiping with a finger using a cleaning liquid such as a detergent, an organic solvent, an acid, an alkali, and purified water, ultrasonic cleaning, heating, and drying. Also, when sandblasting is performed, it is performed before this cleaning operation.

Next, the surface of the adherend is treated with silane. As a specific method of silane treatment, a silane coupling agent of several wt%, an alcohol solution containing pure water of several wt% is prepared, and an adherend is immersed in this alcohol solution for several minutes,
10 to 12 in a constant temperature bath at 60 ℃ to 200 ℃
A method of heating and drying for about 0 minutes is used. As another method of the silane treatment, the alcohol solution may be applied to the surface of the adherend and then dried by heating in a constant temperature bath under the above conditions. Furthermore, it is also possible to heat and dry the adherend after exposing the adherend to the vapor of the silane coupling agent.

Next, a polymerization initiator is added to the compound of group A to prepare an adhesive suitable for a desired polymerization system such as a heat polymerization system or a photopolymerization system. When the heating polymerization method is adopted, a thermal polymerization initiator such as dibenzoyl peroxide or azobisisobutyronitrile is added to the compound of group A. Also,
The adhesive used in the photopolymerization method is obtained by adding a photopolymerization initiator such as benzophenone or camphorquinone to the compound of group A. Furthermore, by adding a thermal polymerization initiator such as an organic peroxide to the compound of group A together with a photopolymerization initiator, it is possible to obtain an adhesive having both a polymerization system of a photopolymerization system and a heating polymerization system. is there.

The heat-polymerization type adhesive is preferably used in the case of adhering adherends having poor optical transparency such as in case of adhering metals.

The photopolymerization type adhesive is preferably used for an adherend having a good light transmission property such as glass.

When an adhesive of both photopolymerization and heating polymerization is used, a part of the adhesive is polymerized and cured by light irradiation in a short time to bond and fix the adherend, and then by heating. Since the adhesive can be completely polymerized and cured, the adhesive can be bonded and fixed by a simple operation regardless of the presence or absence of light transmissivity of the adherend and the difficulty of positioning and holding the adherend.

If desired, the adhesive used in the present invention is divided into two liquids. One liquid is added with an organic peroxide, and the other liquid is added with a tertiary amine. It is also possible to adopt a so-called redox polymerization method in which the above are polymerized when mixed with each other, or to use an anaerobic curable or primer curable adhesive.

The polymerization initiator is used in the range of 0.01 to 10% by weight in the adhesive, preferably 0.1 to 3% by weight.

The adhesive thus prepared is applied to the silane-treated adherends, and then the adherends are brought into close contact with each other, so that the adhesive is interposed between the adherends. The adhesive is polymerized and cured by heating or irradiating light according to the polymerization method.

When the heating polymerization method is used, the heating condition is 6
A range of several tens of minutes to several hours at a temperature of 0 ° C to 180 ° C is preferable.

The light irradiation conditions in the case of using the photopolymerization method are preferably irradiation with light having an irradiance of several milliwatts to several hundred milliwatts for several seconds to several tens minutes.

It should be noted that upon polymerization and curing, heating and light irradiation are carried out in an atmosphere of an inert gas such as nitrogen or argon, whereby the polymerization and curing become more complete and the adhesive strength can be further increased. Further, the surplus adhesive protruding from the adherend can be polymerized and cured without being obstructed by the oxygen in the air.

The adherend adhered and fixed in this manner exhibits strong adhesiveness and maintains its adhered state even when immersed in hot water of high temperature or subjected to a number of autoclave treatments, and has excellent heat resistance. Shows aqueous.

[0060]

The structure of the present invention has been described above. Next, the function of the present invention will be described.

In the present invention, it is essential that the silane-treated adherends are adhered using an adhesive containing a compound represented by Group A, but in the present invention, the adherends are adhered. It is due to the binding force between the silane coupling agent applied to the surface of the adherend and the group A compound. For example, when the silane coupling agent is trichlorovinylsilane, the adhesive strength depends on a chemical bond by an addition reaction between the vinyl group of the silane coupling agent and the (meth) acryloxy group of the compound of group A.

Further, the group A compound itself disclosed in the present invention mainly serves to protect the adhesive effect thus obtained from the deteriorating effect due to high temperature hot water or steam, and also to maintain the airtightness between adherends. Are doing

In this respect, the present invention is significantly different from the conventional bonding method. That is, in a general adhesive method, a strong adhesive force is expressed by hydrogen bonds between polar groups such as a hydroxyl group or a carboxyl group of the adhesive itself and the surface of the adherend or intermolecular force such as Van der Waals force. Therefore, in the case of steam or high-temperature hot water, these polar groups handle water and deteriorate, resulting in a marked decrease in adhesiveness.

On the other hand, the compound of group A used in the present invention is basically a hydrophobic compound having almost no hydroxyl group or carboxyl group, and has a highly crosslinked three-dimensional network structure obtained by polymerization and curing. Since the agent is added, it is possible to obtain the one which does not have water absorption deterioration as in the above-mentioned prior art and has excellent heat resistance.

Next, a preferred application example of the present invention will be described.

The present invention can be applied to the adhesion of adherends such as adhesives, glass and metal ceramics to produce an adhesive structure having excellent adhesive strength and hot water resistance. Therefore, it is suitably used for electricity exposed to high-temperature hot water, steam, etc., assembly of mechanical parts, joining or sealing of hot water or steam circuit pipes, and the like. Further, the present invention can be applied to the assembly of medical and sanitary instruments and instruments that require autoclave sterilization, boiling disinfection, and the like. Further, since the adhesive obtained by polymerization and curing in the present invention has excellent transparency, it can be suitably used for joining optical parts which require hot water resistance.

Suitable application examples of the present invention in general fields include water heaters, humidifiers, rice cookers, pressure cookers, boiling sterilizers, bath equipment, and steam / boiler equipment, etc. , Internal monitoring windows, various sensors, and various electrical and mechanical parts such as joining, sealing and assembling. It can also be applied to the assembly of bathroom auxiliary equipment such as bathroom lighting equipment, bathroom mirrors, kitchen lighting equipment and dishwashers, and kitchen auxiliary equipment. Furthermore, the present invention may be applied to the construction of bathrooms, sinks and washrooms.

Further, preferred examples of application of the present invention in the medical and hygiene fields include a dental treatment handpiece, a dental treatment light irradiator, a dental intraoral laser treatment device, a dental oral cavity cleaning device, and a dental oral cavity. Assembling various therapeutic or diagnostic devices such as an optical probe for observation, a tooth surface cleaner, an ultrasonic scaler, a medical endoscope, and a high-frequency electric scalpel.

Further, as an example of application of the present invention in the field of optics and optronics, joining of communication equipment, measuring equipment and measuring equipment using optical fibers, lenses, prisms, etc. used in special environments such as hot water or steam. Or assembling.

[0070]

EXAMPLES The present invention will be described in more detail with reference to the following examples.

Example 1 3 parts by weight of γ-methacryloxypropyltrimethoxysilane, 1 part by weight of pure water and 100 parts by weight of ethyl alcohol were mixed and sufficiently stirred to obtain a silane treatment liquid. A clean glass plate made of soda glass and having a width of 25 mm, a length of 80 mm, and a thickness of 1.5 mm was dipped in the silane treatment solution for 3 minutes, and then 100
Silane treatment was performed by heat treatment in a constant temperature bath at ℃.

Bis (4-acryloxymethyl) tricyclo (5,2,1,0 ^2,6 ) decane (hereinafter abbreviated as "DCPA") is selected as the compound of group A, and DCP is selected.
An adhesive was prepared by mixing 100 parts by weight of A, 1 part by weight of camphorquinone, and 1 part by weight of dibenzoyl peroxide and thoroughly stirring.

The adhesive was thinly applied to the two silane-treated glass plates to bring the two glass plates into close contact,
This was irradiated with visible light for 5 minutes using a halogen lamp to polymerize and cure the adhesive. The irradiance of visible light of the halogen lamp was 10 mW / cm ² at a wavelength of 420 nm.

The glass plates thus joined were very strongly bonded and were colorless and transparent.

Next, the adhered glass plate was dipped in warm water at 80 ° C. and the durability of the adhered product was examined. As a result, no peeling occurred even after 120 days, and there was no decrease in transparency. Had.

Further, in order to investigate the adhesive strength of the adhesive structure obtained in this example, a round bar made of soda glass having a diameter of 20 mm and a length of 20 mm and a disk having a diameter of 10 mm and a thickness of 5 mm were prepared. The surface of the adherend was polished up to # 600 with a water-resistant abrasive paper, washed cleanly with hexane, acetone, alcohol, and pure water in this order, and then subjected to the above-mentioned silane treatment.

Then, a cellophane tape having a window with a diameter of 4 mm was applied to the end surface of the round bar to limit the adhesive area, and then one drop of the adhesive of the present invention was dropped on the adhesive surface, as in the case of the above glass plate. It was polymerized and cured to obtain an adhesive structure.

The compression shear adhesive strength of the joint surface of the thus obtained adhesive structure was measured and found to be 260 kgf / cm ² . Moreover, when this adhesive structure was immersed in warm water of 80 ° C. for 2 weeks and then the compression shear adhesive strength was measured, it was 25.
It was 4 kgf / cm ² and showed excellent hot water resistance.

Further, instead of immersion in warm water at 80 ° C., 13
Autoclave treatment was carried out 20 times at 2 ° C for 15 minutes, and the compression shear adhesive strength of the joint surface was measured to be 262 kgf /
It was cm ² .

From the above results, it was found that the adhesive structure of this example has excellent hot water resistance.

The compression shear bond strength was measured by using a universal testing machine manufactured by Instron Co., Ltd., and a compressive shear load was applied to the bonded joint surfaces in a direction parallel to the joint surfaces, and the load at which the joint surfaces were broken was measured. Then, it was calculated by dividing by the area of the joint surface.

Example 2 As the adherend, a glass plate made of clean Pyrex glass having the same size as that in Example 1 was used and joined by the bonding method of the present invention.

Polyfunctional oligoester acrylate (Aronix M manufactured by Toagosei Kagaku Kogyo Co., Ltd.) as a compound of group A
-8030) 100 parts by weight, and 1 part by weight each of camphorquinone and N, N-dimethyl-p-toluidine were mixed and stirred to prepare an adhesive.

After subjecting the adherend to silane treatment in the same manner as in Example 1, the glass plate thus bonded had good transparency and was firmly bonded. When this adhesive was immersed in warm water at 80 ° C. as in Example 1, there was no change in appearance even after 60 days, and the bonding surface was firmly bonded.

Next, in order to investigate the adhesive strength of this example, a round bar and a disc made of Pyrex glass were prepared according to the method of Example 1 to prepare an adhesive structure.

The adhesive structure thus obtained was firmly adhered, and the compression shear adhesive strength of the joint surface was measured and found to be 270 kgf / cm ² .

This adhesive structure was dipped in warm water at 80 ° C. for 2 weeks, and the compression shear adhesive strength of the joint surface was measured to give 261 kgf / cm ² , showing excellent hot water resistance with almost no deterioration. .

Further, the adhesive structure obtained in this example was autoclaved in the same manner as in Example 1. The joint surface of the adhesive structure of this example has a compressive shear adhesive strength of 240 kgf / cm ² or more even after the autoclave treatment, and has no change in appearance and has excellent durability. It was

Example 3 Using a clean stainless steel (SUS) plate having the same size as in Example 1 and a Pyrex glass plate, the adherends were bonded to the adherend by the bonding method of the present invention.

After washing the adherend in the same manner as in Example 1, silane treatment was carried out in the same manner as in Example 1 except that the heating temperature was 130 ° C.

Next, 60 parts by weight of the polyfunctional oligoester acrylate used in Example 1 and 4-methacryloxytricyclo (5,2,2), which is the compound of Group B disclosed in the present invention, were used.
40 parts by weight of 1,0 ^2,6 ) decane and 3 parts by weight of 1-hydroxycyclohexyl phenyl ketone were mixed and sufficiently stirred to prepare an adhesive.

Subsequently, the adhesive was applied to an adherend, the adherends were superposed, and ultraviolet rays were irradiated for 10 minutes from the glass plate side of Pyrex glass to polymerize and cure the adhesive. The irradiance of this ultraviolet ray was 10 mW / cm ² at a wavelength of 360 nm.

The bonded structure thus obtained was firmly bonded.

Next, in order to examine this adhesive strength, Example 1 was used.
20mm diameter, 20mm long round bar and Pyrex glass 10mm diameter
After preparing a disk having a thickness of 5 mm, an adhesive structure was produced by the method of this example.

The compressive shear adhesive strength of the joint surface of the thus obtained adhesive structure was 283 kgf / cm ² . After immersing this bonded structure in warm water at 80 ° C for 2 weeks, the compression shear bonding strength of the joint surface was measured and found to be 70 kgf / cm ²
Although the strength was lower than the initial strength, practically sufficient adhesiveness was maintained.

Further, after the autoclave treatment was performed 20 times, the compression shear adhesive strength of the joint surface was measured and found to be 2
It exhibited 00 kgf / cm ² and had excellent durability.

Example 4 Silane treatment was carried out in the same manner as in Example 3 using a clean stainless steel plate having the same size as in Example 1 for the adherend.

Next, 80 parts by weight of trimethylolpropane triacrylate which is a compound of group A, 20 parts by weight of isobornyl methacrylate which is a compound of group B, 1 part by weight of camphorquinone and 1 part by weight of dibenzoyl peroxide are mixed and mixed sufficiently. The adhesive was prepared by stirring.

The adhesive was applied to a silane-treated adherend, and the adherends were superposed on each other and heated in a constant temperature bath of nitrogen gas at 70 ° C. for 4 hours for polymerization and curing.

The bonded structure thus obtained was firmly bonded and did not peel off even when immersed in warm water of 80 ° C. for 30 days.

In order to examine the adhesive strength of this example, a round bar and a disk for compression shear test were prepared according to Example 3,
An adhesive structure was produced by the method of this example.

The compressive-shear adhesive strength of the joint surface of the thus obtained adhesive structure was 320 kgf / cm ² , showing a strong adhesive property. Moreover, the compression shear adhesive strength of the joint surface after immersing this adhesive structure in warm water of 80 ° C. for 2 weeks is 124 kgf.
/ Cm ² and the compressive shear adhesive strength after autoclaving 20 times was 180 kgf / cm ² .

Examples 5 to 8 Table 1 shows the results of producing bonded structures by bonding various adherends with various adhesives according to the methods of Examples 1 to 4.

The adhesive structures of Examples 5 to 8 had excellent adhesive strength and excellent hot water resistance as shown in the results in Table 1.

[0105]

[Table 1]

Description of Table 1 The silane treatment item in Table 1 indicates that the following treatment is performed.

The adherend is dipped in a silane treatment liquid consisting of 3 parts by weight of S1 γ-methacryloxypropyltrimethoxysilane, 1 part by weight of pure water and 100 parts by weight of ethyl alcohol, and then heated at 100 ° C. for 30 minutes.

The adherend is dipped in a silane treatment liquid consisting of 3 parts by weight of S2 γ-methacryloxypropyltrimethoxysilane, 1 part by weight of pure water and 100 parts by weight of ethyl alcohol, and then heated at 130 ° C. for 30 minutes.

After exposing the adherend to the vapor of S3 vinyltrichlorosilane for 20 minutes, it is heated at 100 ° C. for 30 minutes.

The adherend was immersed in a silane treatment liquid consisting of 3 parts by weight of γ-methacryloxypropyltrimethoxysilane, 1 part by weight of pure water, and 100 parts by weight of ethyl alcohol, and then heated at 130 ° C. for 10 minutes.

Abbreviations described in the adhesive composition in Table 1 indicate the following compounds.

TCDA: bis (4-acryloxymethyl) tricyclo (5,2,1,0 ^2,6 ) decane PEA: polyfunctional oligoester acrylate (Aronix M-8030 manufactured by Toagosei Kagaku Kogyo Co., Ltd.) TCM : 4-methacryloxytricyclo (5,2,1,
0 ^2,6 decane TMPTA: trimethylolpropane triacrylate IBM: isobornyl methacrylate TCA: 4-acryloxytricyclo (5,2,1,0
^2,6 ) Decane BPEM: Ethylene oxide modified bisphenol A dimethacrylate PETA: Pentaerythritol tetraacrylate CQ: Camphorquinone BPO: Dibenzoyl peroxide DMPT: N, N-Dimethyl-p-toluidine Irg184: 1-hydroxycyclohexyl phenyl ketone.

Example 9 In the production of a bonded structure in which adherends are stainless steel and glass, a sandblast treatment was performed on the surface of one of the adherends, stainless steel, using alumina having an average particle size of 50 μm. I gave it for a minute.

Subsequently, an adhesive structure was produced in the same manner as in Example 3.

The compression shear adhesive strength of the joint surface of this adhesive structure was determined in the same manner as in Example 3 and found to be 382 kgf /
It was cm ² .

Next, when this adhesive structure was immersed in warm water at 80 ° C., it showed an adhesive durability of 60 days or longer, and the compression shear adhesive strength at this time was 440 kgf / cm ² .

Further, the adhesive structure was subjected to autoclave treatment 20 times, and the compression shear adhesive strength of the joint surface was determined to be 410 kgf / cm ² .

According to this embodiment, the sandblast treatment not only improves the adhesive strength of the adhesive structure,
It was shown that the hot water resistance was also significantly improved.

Example 10 60 parts by weight of ethylene oxide-modified bisphenol A dimethacrylate, 30 parts by weight of methyl methacrylate, and 10 parts by weight of fumed silica were polymerized and cured to obtain a diameter of 10 m.
The composite resin of m and thickness of 5 mm was used as one adherend, and the other was used as a round bar made of Pyrex glass having a diameter of 20 mm and a thickness of 10 mm, and joined by the method for producing an adhesive structure of the present invention.

The adhered surfaces of both adherends were previously sandblasted in the same manner as in Example 9, and then treated with silane in the same manner as in Example 3.

Next, 20 parts by weight of ethylene oxide-modified bisphenol A dimethacrylate, 50 parts by weight of bis (4-methacryloxymethyl) tricyclo (5,2,1,0 ^2,6 ) decane, and 4-acryloxytricyclo (5,5). Two
1,0 ^2,6 ) Decane 30 parts by weight, dibenzoyl peroxide 1
An adhesive was prepared by mixing and stirring the parts by weight.

Then, after applying the adhesive to the adherend,
According to the method of Example 6, the adhesive was polymerized and cured by heating at 70 ° C. for 6 hours under a nitrogen stream to obtain an adhesive structure.

The compression-shear adhesive strength of the adhesive structure thus obtained was 235 kgf / cm ² .

The compressive shear adhesive strength after immersion in 80 ° C. hot water was 128 kgf / cm ² , and 132 ° C., 3
The compression-shear adhesive strength after 20-minute autoclave treatments was 148 kgf / cm ² . In this example, although the adherend consisting of the composite resin itself had a small hot water resistance, the adhesive strength was slightly lowered, but the hot water resistance was practically sufficient even after the hot water resistance test.

Comparative Example 1 An attempt was made to bond soda glass in the same manner as in Example 1 except that the silane treatment was not carried out. However, after the adhesive was polymerized and cured, the adherend peeled off and showed no adhesiveness.

Comparative Example 2 Epoxy-modified bisphenol A dimethacrylate 100
By weight, 1 part by weight of camphorquinone and 1 part by weight of dibenzoyl peroxide were mixed and sufficiently stirred to prepare an adhesive.

An adhesive structure was prepared by using silane-treated soda glass as an adherend in the same manner as in Example 1 using the adhesive.

This adhesive structure was firmly adhered, its compression shear adhesive strength was 240 kgf / cm ² , and had excellent adhesive strength in the dry state.

However, when this bonded structure was dipped in warm water of 80 ° C., the periphery of the joint surface began to peel off and became cloudy on the third day. When the autoclave treatment was carried out 20 times, most of the adhesive surface was peeling off, and practical hot water resistance was not exhibited.

Comparative Example 3 Stainless steel and Pyrex glass were joined in the same manner as in Example 3 except that urethane-modified diacrylate was used instead of the polyfunctional oligoester acrylate in the adhesive composition.

The compressive shear adhesive strength of the joint surface of this adhesive structure was 117 kgf / cm ² , and the adhesive strength was relatively low.

When this bonded structure was dipped in warm water at 80 ° C., it spontaneously peeled off on the second day. Moreover, wrinkling occurred on the joint surface even after performing only one autoclave treatment, which was not practical at all.

Comparative Example 4 A silane treatment liquid consisting of 3 parts by weight of 3-glycidoxypropyltrimethoxysilane, 1 part by weight of pure water, and 100 parts by weight of ethanol was heated at 130 ° C. for 30 minutes to obtain Example 4. Silane treatment of stainless steel equivalent to that used was performed.

Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd. as a bisphenol A type epoxy adhesive
Using diaminodiphenyl sulfone as a curing agent
Stainless steel was joined as in Example 4 by heating at 20 ° C. for 12 hours.

The compression-shear adhesive strength of the adhesive structure in the dry state was 273 kgf / cm ² , which was good, but 80
When it was soaked in warm water at ℃ for 2 weeks, it dropped to only a few kgf / cm ² and peeled off easily with a light pressing with fingers. Also, when the autoclave treatment was carried out 20 times, the adhesive strength was remarkably reduced as in the immersion in warm water at 80 ° C., and practical hot water resistance was not exhibited.

Comparative Example 5 100 parts by weight of 4-methacryloxytricyclo (5,2,1,0 ^2,6 ) decane, which is a compound of Group B of the present invention, 1 part by weight of camphoraquinone, and peroxide were used as an adhesive agent. An adhesive structure of soda glass was produced in the same manner as in Example 1 except that a mixture of 1 part by weight of dibenzoyl was used.

The compression-shear adhesive strength of this adhesive structure in the dry state was 173 kgf / cm ² , which was relatively good. It did not show aqueous.

[0138]

As described above, by using the method for manufacturing an adhesive structure according to the present invention, it has excellent adhesive strength and excellent hot water resistance even when immersed in high temperature water or subjected to autoclave treatment. A bonded structure is obtained.

In addition, the adhesive structure manufacturing method of the present invention has a feature that the adhesive used for the bonding surface is also excellent in transparency, and therefore can be applied to the bonding of optical components. It has the advantages of

The excellent adhesive properties and hot water resistance of the adhesive structure of the present invention are characterized in that a silane-treated adherend is joined by polymerizing and curing an adhesive containing a compound of group A. This is the first effect obtained when the method of the present invention is used, and is an effect unique to the present invention.

Claims (4)

[Claims] 1. An adhesive surface of an adherend constituting an adhesive structure is treated with a silane coupling agent, and at least one compound selected from the following group A is contained between the adherends. A method for producing a heat resistant water-resistant adhesive structure, which comprises adhering the adherends by polymerizing and curing the adhesive through an adhesive: Group A polyfunctional oligoester (meth) acrylate, bis (4 -(Meth) acryloxymethyl) tricyclo (5,
2,1, O ^2,6 decane, neopentyl glycol modified trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane Tri (meth) acrylate, bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol mono Doropenta (meth) acrylate. 2. The method for producing a heat resistant water-resistant adhesive structure according to claim 1, wherein the adhesive further contains at least one compound selected from the following Group B: Group B 4- (meta ) Acryloxytricyclo (5,2,1, O
^2,6 ) Decane, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth)
Acrylate, phenyl (meth) acrylate, adamantyl (meth) acrylate, 4-tert. -Butyl (meth) acrylate, dicyclopentenyl (meth) acrylate. 3. The method for manufacturing a heat resistant water-resistant adhesive structure according to claim 1, wherein the adherend is glass, metal, or ceramics. 4. An adhesive surface of the adherend is sandblasted in advance.
The method for producing a hot water resistant adhesive structure according to any one of 1.