JPH04209681A - Manufacture of bonded structure resistant to hot water - Google Patents

Abstract

PURPOSE:To obtain the title structure excellent in resistance to hot water by subjecting the adherends of the constituents of a structure to a specified treatment, putting an adhesive containing a specified compound between the adherends, and polymerizing and curing the adhesive to join the constituents together. CONSTITUTION:After the adherends of the constituents of a structure are treated with a silane coupling agent, an adhesive containing at least one compound selected among the following compounds is put between the adherends and the adhesive is polymerized and cured to join the constituents together, thus forming a bonded structure. The aforementioned compound includes a polyfunctional oligoester acrylate, a trimethylolpropane di(meth)acrylate modified with neopentyl glycol, a trimethylolpropane tri(meth)acrylate, a trimethylolpropane tri(meth)acrylate modified with ethylene oxide, a trimethylolpropane tri(meth)acrylate modified with propylene oxide, a bisphenol A di(meth)acrylate modified with propylene oxide, a pentaerythritol tri(meth) acrylate, a pentaerythritol tetra(meth)acrylate, a ditrimethylolpropane tetra(meth) acrylate, and a dipentaerythritol monohydropenta(meth)acrylate.

Description

[Detailed description of the invention]

[00011

[Industrial Application Field] The present invention relates to a method for manufacturing a heat-resistant adhesive structure, and more particularly, it relates to a method for manufacturing a heat-resistant adhesive structure, and more specifically, even if it is immersed in high-temperature water or treated in an autoclave,
The present invention relates to a method for manufacturing an adhesive structure that maintains a strong adhesive state and has adhesive durability over a long period of time. [0002] [0002] Assembling structures by adhesion has a simpler structure for joining than mechanical assembly using bolts, nuts, or rivets, and can easily join even large-area objects. It is possible to easily join different materials.
It has been widely used in all industrial fields because the joining process is shortened and productivity is high. [0003] Conventionally, bonding of structures assembled by bonding (hereinafter referred to as "bonded structures") involves
In addition to solvent-volatile adhesives such as vinyl chloride adhesives and synthetic rubber adhesives, chemically reactive adhesives such as epoxy resins, epoxy-modified bisphenol A di(meth)acrylates, cyanoacrylates, and urethane-modified di(meth)acrylates. Adhesive is used. [0004] In recent years, the advantages of adhesive bonding have been utilized in the optical field, such as assembly and bonding of lenses, prisms, and optical fibers, and in the electronic and electrical fields, such as manufacturing and assembly of semiconductors, printed circuit boards, and motors. Adhesive technology has been applied to medical fields such as dentistry and surgical treatment, and it is not only possible to simply bond, but also to have more advanced properties such as optical properties, heat resistance, water resistance, electrical properties, and adhesive reliability. Adhesive performance is increasingly required. [0005] As one of the uses of such advanced adhesive technology, there has recently been an increasing desire to manufacture adhesive structures that can be sterilized by boiling or autoclaving in order to sterilize viruses and mold in medical instruments and devices. It's coming. Examples of this include assembly and joining of medical endoscopes, laser fibers for dental oral cavity use, hasid pieces for dental treatment, light irradiators for dental treatment, and the like. [0006] Furthermore, there is a need for adhesive technology that has sufficient adhesive strength and durability even in high-temperature water. An example of this is assembly and joining of industrial products. [0007] In these uses, it is strongly desired that the adhesive has heat resistance and water resistance in addition to adhesive properties. As a bonding method in such a case, conventionally a bonding method using a chemically reactive adhesive having excellent heat resistance and water resistance, such as epoxy resin or epoxy-modified bisphenol A di(meth)acrylate, has been applied. Recently, adhesives that can be sterilized by autoclave and are made of a mixture of urethane-modified oligomers and mono(meth)acrylates that can be polymerized by ultraviolet light have appeared. [0008]

[Problems to be Solved by the Invention] However, with these conventional bonding methods using adhesives, there are cases where immersion in high-temperature water for several minutes or autoclave treatment of about 15 minutes is performed only several times. Although it exhibits good adhesive properties, it has poor durability and shows significant deterioration when immersed in water at around 80°C for several weeks, resulting in a significant decrease in adhesive strength and failure in hot water. Problems such as natural peeling occurred. [00091 Again. When lenses, prisms, etc. are bonded together in a medical endoscope, there is a problem in that after just a few autoclave sterilizations, parts of the bonded area will peel off, causing loss of optical transparency and rendering the product unusable. Was. [00101 Furthermore, in these conventional bonding techniques, when a large area is bonded, deterioration occurs from the surrounding area even when immersed in high-temperature water, so it can be used without reducing the overall adhesive strength. However, when trying to bond small adherends such as small precision parts, there was also a problem regarding the bonding area, such as the fact that it could not be applied because the influence of deterioration in the peripheral area affected the entire area. [0011] The present invention is directed to overcoming such problems with conventional bonding techniques. That is, the object of the present invention is to provide an adhesive having excellent adhesive strength and excellent hot water resistance that maintains good adhesive properties even after being immersed in high-temperature water for a long period of time or undergoing autoclaving many times. An object of the present invention is to provide a method for manufacturing a structure. Furthermore, the present invention has excellent adhesive properties and hot water resistance, as well as good transparency.
Provided is a method for manufacturing a bonded 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 inventors have discovered that after treating the adhesive surface of an adherend constituting an adhesive structure with a silane coupling agent, Excellent adhesion can be achieved by interposing an adhesive containing at least one compound selected from Group A below between the adherends and polymerizing and curing the adhesive to bond the adherends together. The inventors have now invented a method for producing an adhesive structure that has excellent characteristics and excellent hot water resistance, as well as good transparency. [0013] Group A polyfunctional oligoester (meth)acrylate, bis(
4-(meth)acryloxymethyl)tricyclo(5゜2
．． 1,026) Decane, neopentyl glycol modified trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethylene oxide modified trimethylolpropane di(meth)acrylate
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 monohydropenta(meth)acrylate. [0014] That is, the present invention treats the adhesive surface of an adherend constituting an adhesive structure with a silane coupling agent, and then performs adhesive bonding using an adhesive containing a polyfunctional monomer represented by Group A as a component. By doing so, the above objective was achieved. [00151 Next, the present invention will be explained in more detail. [00161 In the present invention, the adhesive surface of the adherend to be bonded is first treated with a silane coupling agent, but this silane treatment is a surface modification method using a silane coupling agent that is used in normal bonding operations. means. Specifically, a silane treatment solution is prepared by dissolving conventionally used silane coupling agents such as γ-(meth)acryloxypropyltrimethoxysilane, trichlorovinylsilane, and triethoxyvinylsilane in an appropriate solvent such as ethyl alcohol and water. A method is used in which the adhesive is applied to the surface of the adherend and then dried. Alternatively, after exposing the adherend to the vapor of the silane coupling agent, the surface of the adherend may be dried. [00171 Next, the compounds represented by Group A will be explained. Among the compounds used in the present invention, the polyfunctional oligoester (meth)acrylate is represented by the general formula (1),
It is preferable to use a compound represented by (2) or (3) with 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. [00201 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. [00211 In any general formula, n is approximately 1
Represents an integer from ~4. [0022] These polyfunctional oligoesters (meth)
As a specific example of acrylate, for example, oligoester acrylate M-8030 manufactured by Toagosei Chemical Industry Co., Ltd.
and M-9050. [0023] Further, among the compounds represented by Group A, neopentyl glycol-modified trimethylolpropane di(meth)acrylate includes a compound represented by the following structural formula (4). [0024] However, in the formula, R+ is hydrogen or a methyl group. [0025] 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]

embedded image [0027] However, in the formula, R2 and R3 are hydrogen or a methyl group. [0028] Also, among the compounds shown in Group A, ethylene oxide modified trimethylolpropanetri(meth)
Examples of acrylate and propylene oxide-modified trimethylolpropane tri(meth)acrylate include a compound represented by the following structural formula (6). [0029]

embedded image [00301 However, in the formula, R4 and R5 are hydrogen or a methyl group. [00311 All of these Group A compounds shown in the present invention are characterized in that they are polyfunctional monomers that are highly crosslinked during fusion curing to provide extremely hard cured products. [00321 Furthermore, one remarkable feature of the compounds represented by Group A used in the present invention is that all of the compounds are basically hydrophobic compounds that contain almost no polar groups such as hydroxyl groups or carboxyl groups. At the point. [o o 33] The adhesive used in the present invention can be obtained by adding a small amount of a commonly used polymerization initiator to at least one compound of Group A. [00341 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. I can do it. [0035] When these polymerization initiators are added,
Heat treatment is performed when polymerizing and curing the adhesive. [0036] Further, in the present invention, a photopolymerization initiator may be used as a polymerization initiator, such as 1-hydroxycyclohexyl phenyl ketone, benzophenone, benzoin ethers, acetophenones, benzyl, camphorquinone, benzyl methyl ketal. and thioxanthone. [0037] When these photoinitiators are used,
By irradiating the adhesive with light such as ultraviolet rays or visible light, the adhesive is polymerized and cured, and when at least one of the adherends transmits light, the adhesion time can be significantly shortened. [0038] When using such a photopolymerization initiator, N, N-dimethyl-p-toluidine, N
, a tertiary amine such as N-dimethylaminoethyl (meth)acrylate, or the above-mentioned organic peroxide may be added as a reaction accelerator, thereby making it possible to further increase the reaction rate of photopolymerization. [0039] In the present invention, the above-mentioned A
It is preferable to use an adhesive in which at least one type of compound shown in the group is further added with one type of monofunctional monomer selected from the following group B. [00401 Group B 4-(meth)acryloxytricyclo(5,2,1,0
26) Decane, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)
Acrylate, phenyl (meth)acrylate, adamantyl (meth)acrylate, 4-tert, -butyl (meth)acrylate, dicyclopentenyl (meth)acrylate. [00411 These compounds represented by Group B are monofunctional monomers that have low water absorption and excellent heat resistance. [0042] In the present invention, the compound represented by Group B is A
The addition ratio is preferably 80% by weight or less based on the compounds represented by the group. If the amount added exceeds the above range, a problem arises in that the hot water resistance of the adhesive is impaired. [00431] Examples of the adherend used in the present invention include adhesives, glass, metals, adhesive composite materials filled with inorganic fillers, and it is particularly preferable to use glass, metals, and ceramics. The reason for this is that when glass, metal, or ceramics are used as the adherend, the adherend itself does not have substantial water absorbency, so it is even more superior than when adhesives are used as the adherend. This is because hot water resistance and adhesive strength are exhibited. [0044] In the present invention, the surface of the adherend may be made grainy in advance using sandblasting or the like in order to further improve the adhesive strength of the resulting adhesive structure. In particular, when metal is used as the adherend, sandblasting not only increases adhesive strength but also significantly increases hot water resistance. [0045] Examples of the sand used for sandblasting include alumina and glass peas. The grain size of the sand is preferably from several microns to several hundred microns. [00461] Next, a method for manufacturing a bonded structure having excellent hot water resistance according to the present invention will be specifically described. [00471 The surface of the adherend used in the present invention is preferably cleaned prior to the adhesive operation, as is done in conventional adhesive operations. The surface of the adherend is cleaned by applying normal cleaning operations such as wiping with fingers, ultrasonic cleaning, heating, and drying using a cleaning liquid such as a detergent, an organic solvent, an acid, an alkali, or purified water. Further, when sandblasting is performed, it is applied in advance before this cleaning operation. [00481 Next, the surface of the adherend is subjected to silane treatment. As a specific method for silane treatment, an alcohol solution containing several weight percent of a silane coupling agent and several weight percent of pure water is prepared, and the adherend is immersed in this alcohol solution for several minutes.
10 to 12 hours in a constant temperature bath at 60℃ to 200℃
A method of heat drying for about 0 minutes is used. Further, as another method of silane treatment, the above-mentioned alcohol solution may be applied to the surface of the adherend and then heated and dried in the same temperature bath under the above-mentioned conditions. Furthermore, it is also possible to heat and dry the adherend after exposing it to the vapor of the silane coupling agent. [00493] Next, a polymerization initiator is added to the compound of Group A to prepare an adhesive suitable for a desired polymerization method such as a heating polymerization method or a photopolymerization method. When a thermal polymerization method is employed, 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 a compound of group A. Furthermore, by adding a thermal polymerization initiator such as an organic peroxide together with a photopolymerization initiator to the compound of Group A, it is also possible to create an adhesive that combines both photopolymerization method and heat polymerization method. be. [00501 The heat polymerization type adhesive is preferably used for adhering adherends with poor light transmittance, such as when adhering metals together. [00511 Hikarihongo type adhesive is suitably used for adherends with good light transmittance such as glass. [0052] When using both photopolymerization and heat polymerization type adhesives, a part of the adhesive is polymerized and cured in a short time by light irradiation to bond and fix the adherend, and then heated. Since the adhesive can be completely polymerized and cured, adhesive fixation can be performed with a simple operation regardless of whether the adherend is transparent or not, or how difficult it is to position and hold the adherend. [0053] Furthermore, the adhesive used in the present invention can be prepared by dividing the adhesive into two liquids, and adding an organic peroxide to one liquid and a tertiary amine to the other liquid, if desired. It is also possible to adopt a so-called redox polymerization method in which the adhesives are polymerized when mixed together, or to use an anaerobic curable or primer curable adhesive. [0054] The polymerization initiator is used in the adhesive in a range of about 0.01% to 10% by weight, but preferably 0.01% to 10% by weight.
．． It is used in a range of 1% to 3% by weight. [0055] The thus prepared adhesive is applied to the silane-treated adherend, and 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 light irradiation depending on the polymerization method. [0056] The heating conditions when using the heating polymerization method are 6
A temperature range of 0°C to 180°C for several tens of minutes to several hours is suitable. [0057] When using the photopolymerization method, it is preferable to irradiate light with an irradiance of several milliwatts to several hundred milliwatts for several seconds to several tens of minutes. [0058] During polymerization and curing, heating and light irradiation are performed in an atmosphere of an inert gas such as nitrogen or argon, so that the polymerization and curing can be more complete and the adhesive strength can be further increased. Moreover, even the excess adhesive that protrudes from the adherend can be polymerized and cured without being inhibited by oxygen in the air. [0059] The adherend that has been adhesively fixed in this manner exhibits strong adhesive properties, and maintains its adhesive state even when immersed in high-temperature water or subjected to multiple autoclave treatments, and has excellent heat resistance. Shows water-based. [00601

[Function] The structure of the present invention has been described above, and now the function of the present invention will be explained. [0061] An essential requirement of the present invention is to bond between silane-treated adherends using an adhesive containing a compound shown in Group A. This is caused by the bonding force between the silane coupling agent applied to the surface of the adherend and the compound of group A. For example, when the silane coupling agent is trichlorovinylsilane, the adhesive strength depends on the chemical bond formed by the addition reaction between the vinyl group of the silane coupling agent and the (meth)acryloxy group of the compound of group A. [0062] Furthermore, the Group A compound disclosed in the present invention itself mainly functions to protect the adhesive effect thus obtained from deterioration caused by high-temperature water and water vapor, and also functions to maintain airtightness between adherends. doing. [0063] In this respect, the present invention is significantly different from conventional bonding methods. In other words, in general adhesive methods, strong adhesive strength is developed through intermolecular forces such as hydrogen bonds and van der Waals forces between the adhesive's polar groups such as hydroxyl and carboxyl groups and the surface of the adherend. Therefore, when exposed to water vapor or high-temperature hot water, these polar groups deteriorate when exposed to moisture, resulting in a significant decrease in adhesive properties. [0064] On the other hand, the compounds of Group A used in the present invention are basically hydrophobic compounds having almost no hydroxyl or carboxyl groups, and are polymerized and cured to form an adhesive with a highly crosslinked three-dimensional network structure. Because of the provision of a chemical agent, it is possible to avoid deterioration due to water absorption as in the prior art, and also to have excellent heat resistance. [00651 Next, a preferred application example of the present invention will be described. [0066] The present invention can be applied to adhesion of adherends such as adhesives, glass, metal ceramics, etc. to produce a bonded structure having excellent adhesive strength and hot water resistance. Therefore, it is suitably used for assembling electrical and mechanical parts that are exposed to high-temperature water or steam, and for joining or sealing piping in hot water or steam circuits. The present invention can also be applied to the assembly of medical and sanitary instruments and instruments that require autoclave sterilization, boiling sterilization, and the like. Furthermore, since the adhesive obtained by polymerization and curing in the present invention has excellent transparency, it can be suitably used for joining optical parts that require hot water resistance. [0067] Preferred application examples in the general field of the present invention include piping parts, water supply and drainage parts used in water heaters, humidifiers, rice cookers, pressure cookers, boiling sterilizers, bath appliances, steam boiler equipment, etc. , internal monitoring windows, various sensors, and various electrical and mechanical parts, etc., joining, sealing and assembly. It can also be applied to the assembly of bathroom lighting fixtures, bathroom mirrors, kitchen lighting fixtures, bathroom fixtures such as dishwashers, and kitchen fixtures. Furthermore, the present invention may be applied to construction of bathrooms, sinks, washrooms, etc. [0068] Preferred application examples of the present invention in the medical and hygiene fields include dental treatment handpieces, dental treatment light irradiators, dental intraoral laser treatment devices, dental intraoral irrigators, and dental intraoral irrigators. We assemble various treatment and diagnostic equipment such as optical probes for observation, tooth surface cleaners, ultrasonic scaler-1 medical endoscopes, and high-frequency electric scalpels. [0069] Further, as an application example of the present invention in the field of optics and optronics, there is the joining of communication equipment, measuring equipment, and measuring equipment using optical fibers, lenses, prisms, etc. used in special environments such as hot water and steam. Examples include assembly. [00701] [Example] The present invention will be explained in more detail below using Examples. [00711 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 prepare a silane treatment liquid. Made of soda glass, width 25mm, length 80mm, thickness 1. A 5 mm clean glass plate was immersed in the silane treatment solution for 3 minutes, and then heat treated in a constant temperature bath at 100° C. to perform silane treatment. (0072) Bis(4-acryloxymethyl)tricyclo(5,2,L,O2.6)decane (hereinafter abbreviated as rD CP AJ) was selected as the compound of Group A, and 100 parts by weight of DCPA and camphorquinone were added. An adhesive was prepared by mixing 1 part by weight and 1 part by weight of dibenzoyl peroxide and thoroughly stirring the mixture. [0073] The adhesive was thinly applied to two glass plates treated with the silane, and Two glass plates are brought together,
This was irradiated with visible light for 5 minutes using a halogen lamp to polymerize and harden the adhesive. The visible light irradiance of the halogen lamp was 10 mW/cm2 at a wavelength of 420 nm. [0074] The glass plates bonded in this manner had very strong adhesion and were colorless and transparent. [00751] Next, the bonded glass plates were immersed in 80°C hot water to examine the durability of the adhesive, and the result was that it did not peel off even after 120 days, and it showed excellent hot water resistance with no decrease in transparency. had. [0076] In addition, in order to examine the adhesive strength of the adhesive structure obtained in this example, a soda glass glass with a diameter of 20 mm,
A round bar with a length of 20 mm and a disk with a diameter of 10 mm and a thickness of 5M were prepared. The surface of the adherend is coated with #6 waterproof abrasive paper.
Polished to No. 00, hexane, acetone, alcohol,
After washing thoroughly using pure water, the above-mentioned silane treatment was performed. [00771 Next, a cellophane tape having a window with a diameter of 4 InIII was pasted on the end face of the round bar to limit the adhesive area, and then one drop of the adhesive of the present invention was added to the adhesive surface and polymerized in the same manner as in the case of the glass plate. After curing, a bonded structure was obtained. [0078] The compressive shear adhesive strength of the joint surface of the adhesive structure thus obtained was measured and found to be 260 kgf/co
It was +2. Further, when this adhesive structure was immersed in hot water at 80° C. for two weeks, the compressive shear adhesive strength was measured, and it was 254 kgf/cI112, indicating excellent hot water resistance. [0079] Furthermore, instead of immersion in 80°C warm water, 13
Autoclave treatment was performed 20 times for 15 minutes at 2°C, and the compressive shear adhesive strength of the joint surface was measured, and it was 262 kgf.
/C1112. [00801 From the above results, it was found that the adhesive structure of this example had excellent hot water resistance. [00811 Compressive shear adhesive strength was measured by applying a compressive shear load to the bonded bonded surfaces in a direction parallel to the bonded surfaces using a universal testing machine manufactured by Instron, and measuring the load at which the bonded surfaces would break. It was calculated by dividing by the area of the joint surface. [0082] Example 2 A clean Pyrex glass plate of the same size as in Example 1 was used as an adherend, and bonding was performed by the bonding method of the present invention. [0083] Polyfunctional oligoester acrylate (Toagosei Chemical Industry Co., Ltd., Aronix M
8030) 100 parts by weight, camphorquinone and N,
1 part by weight of each of N-dimethyl-p-toluidine was mixed and stirred to prepare an adhesive. [0084] After the adherend was subjected to silane treatment in the same manner as in Example 1, the glass plates thus joined had good transparency and were firmly adhered. When this adhesive was immersed in 80° C. hot water in the same manner as in Example 1, there was no change in appearance even after 60 days or more, and the bonded surfaces were firmly adhered. [00851 Next, in order to examine the adhesive strength of this example, a Pyrex glass round bar and disk were prepared according to the method of Example 1, and a bonded structure was produced. [0086] The adhesive structure thus obtained was firmly adhered, and the compressive shear adhesive strength of the joint surface was measured to be 270 kgf/cm2 ◇ [0087] This adhesive structure was placed in hot water at 80°C. After being immersed in water for two weeks, the compressive shear adhesive strength of the bonded surfaces was measured to be 261 kgf/cm2, indicating excellent hot water resistance with almost no deterioration. [0088] Furthermore, the adhesive structure obtained in this example was subjected to autoclave treatment in the same manner as in Example 1. The bonded surface of the adhesive structure of this example had a compressive shear adhesive strength of 240 kgf/cm2 or more even after autoclave treatment, and had excellent durability with no change in appearance. . [00891 Example 3 A clean stainless steel (SUS) plate and a Pyrex glass plate of the same size as in Example 1 were used as adherends, and bonding was performed by the bonding method of the present invention. [00901] After washing the adherend in the same manner as in Example 1, silane treatment was performed in the same manner as in Example 1 except that the heating temperature was 130°C. [00911 Next, 60 parts by weight of the polyfunctional oligoester acrylate used in Example 1, 4-methacryloxytricyclo(5,2°1,O2.6)decane, which is a compound of group B disclosed in the present invention, and 40 parts by weight of the polyfunctional oligoester acrylate used in Example 1. parts by weight and 3 parts by weight of 1-hydroxycyclohexylphenyl ketone were mixed and sufficiently stirred to prepare an adhesive. [0092] Subsequently, the adhesive was applied to adherends, the adherends were stacked, and ultraviolet rays were irradiated from the Pyrex glass plate side for 10 minutes to polymerize and harden the adhesive. The irradiance of this ultraviolet ray is 10 mW/at a wavelength of 360 nm.
It was cm2. [0093] The adhesive structure thus obtained was firmly adhered. [00941 Next, in order to examine this adhesive strength, Example 1
According to the method of 20 mm in diameter of stainless steel,
A round rod with a length of 20 mm and a diameter of 10 mm made of Pyrex glass.
After preparing a disk with a diameter of 5 mm and a thickness of 5 mm, an adhesive structure was produced by the method of this example. [0095] The bonded structure thus obtained had a compressive shear adhesive strength of 283 kgf/cm2 at the joint surface. Furthermore, after immersing this bonded structure in hot water at 80°C for two weeks, the compressive shear adhesive strength of the bonded surface was measured and found to be 70k.
gf/cm2, which was lower than the initial strength, but maintained sufficient adhesion for practical use. [0096] Furthermore, after performing autoclave treatment 20 times, the compressive shear adhesive strength of the joint surface was measured. 2
00 kgf/cm2 and had excellent durability. [0097] Example 4 A clean stainless steel plate of the same size as in Example 1 was used as the adherend, and silane treatment was performed in the same manner as in Example 3. [00981] Next, 80 parts by weight of tolmethylolpropane triacrylate, which is a compound of group A, 20 parts by weight of isobonyl methacrylate, which is a compound of group B, 1 part by weight of camphorquinone, and 1 part by weight of dibenzoyl peroxide were mixed sufficiently. An adhesive was prepared by stirring. [0099] The adhesive was applied to a silane-treated adherend, the adherends were overlapped, and the adhesive was polymerized and cured by heating in a constant temperature bath at 70° C. in which nitrogen gas was flowed for 4 hours. [01001 The adhesive structure thus obtained was firmly adhered and did not peel off even after being immersed in hot water at 80° C. for 30 days. [01013 In order to examine the adhesive strength of this example, round bars and disks for compression shear tests were prepared according to Example 3,
An adhesive structure was produced by the method of this example. [0102] The bonded structure thus obtained had a compressive shear adhesive strength of 320 kgf/cm2 at the joint surface, indicating strong adhesiveness. Furthermore, after immersing this adhesive structure in hot water at 80°C for 2 weeks, the compressive shear adhesive strength of the joint surface was 12
4 kgf/cm2, and the compressive shear adhesive strength after 20 autoclave treatments was 180 kgf/cm2. [0103] Examples 5 to 8 Table 1 shows the results of manufacturing bonded structures by bonding various adherends with various adhesives according to the methods of Examples 1 to 4. [0104] As shown in the results in Table 1, the adhesive structures of Examples 5 to 8 had excellent adhesive strength and excellent hot water resistance. [0105] [Table 1] [01061 Explanation of Table 1 The term silane treatment in Table 1 indicates that the following treatment is performed. [0107] Sl The adherend is immersed in a silane treatment solution 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 100° C. for 30 minutes. [0108] S2 The adherend is immersed in a silane treatment solution 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 30 minutes. [0109] S3 After exposing the adherend to vinyltrichlorosilane vapor for 20 minutes, it is heated at 100° C. for 30 minutes. [01101S4 The adherend is immersed in a silane treatment solution 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. [0111] The abbreviations listed in the adhesive composition in Table 1 indicate the following compounds. [0112] TCDA: Bis(4-acryloxymethyl)tricyclo(5,2,1,O2.6)decane PEA: Polyfunctional oligoester acrylate (
Aronix M-803 manufactured by Toagosei Chemical Industry Co., Ltd.
0) TCM: 4-methacryloxytricyclo(5
, 2゜1, 026) Decane TMPTA Nitrimethylolpropane triacrylate IBM: Isobornyl methacrylate TCA
:4-acryloxytricyclo(5,2゜1.O2.
6) Decane BPEM: Ethylene oxide modified bisphenol A
Dimethacrylate PETA: Pentaerythritol tetraacrylate CQ: Camphorquinone BPO: Dibenzoyl peroxide DMPT: N,N-dimethyl-p-toluidine Ir
g184: 1-hydroxycyclohexylphenyl ketone. [0113] Example 9 In the production of a bonded structure in which the adherends are stainless steel and glass, the surface of one of the adherends, stainless steel, was subjected to sandblasting once using alumina having an average particle size of 50 μm. It was applied for a minute. [0114] Subsequently, a bonded structure was produced in the same manner as in Example 3. [0115] The compressive shear adhesive strength of the joint surface of this adhesive structure was determined in the same manner as in Example 3, and was found to be 382 kgf.
/cm2. [0116] Next, when this adhesive structure was immersed in 80° C. hot water, it exhibited adhesive durability of 60 days or more, and the compressive shear adhesive strength at this time was 440 kgf/cnx2. [0117] Furthermore, the bonded structure was subjected to autoclave treatment 20 times, and the compressive shear adhesive strength of the bonded surface was determined to be 410 kgf/cm2. [01181 From this example, sandblasting not only improves the adhesive strength of the adhesive structure, but also
It was also shown that hot water resistance was significantly improved. [0119] Example 10 Diameter 10 m obtained by curing 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.
One adherend was a composite resin having a diameter of 20 mm and a thickness of 5 mm, and the other was a round bar made of Pyrex glass with a diameter of 20 mm and a length of 10, and bonding was performed by the method for manufacturing an adhesive structure of the present invention. [01201 The adhesion surfaces of both adherends were previously sandblasted in the same manner as in Example 9, and then silane treated in the same manner as in Example 3. (01211 Next, 20 parts by weight of ethylene oxide-modified bisphenol A dimethacrylate, 50 parts by weight of bis(4-methacryloxymethyl)tricyclo(5,2,1,O2.6)decane, 4-acryloxytricyclo(5,2
゜1, 026) 30 parts by weight of decane and 1 part by weight of dibenzoyl peroxide were mixed and stirred to prepare an adhesive. [0122] Subsequently, 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 a bonded structure. [0123] The compressive shear adhesive strength of the adhesive structure thus obtained was 235 kgf/cm2. [0124] Furthermore, the compressive shear adhesive strength after immersion in 80°C hot water was 128 kgf/cm2,
After 20 autoclave treatments at 132° C. for 30 minutes, the compressive shear adhesive strength was 148 kgf/cm 2 . In this example, the adhesion strength was slightly decreased because the hot water resistance of the composite resin adherend itself was low, but even after the above-mentioned hot water resistance test, it had practically sufficient hot water resistance. [0125] Comparative Example 1 An attempt was made to bond soda glass in the same manner as in Example 1 except that no silane treatment was performed, but the adherend peeled off after the adhesive was polymerized and cured, and no adhesiveness was exhibited. [0126] Comparative Example 2 Epoxy-modified bisphenol A dimethacrylate 100
parts 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. [0127] Using the adhesive, a bonded structure was produced in the same manner as in Example 1, using silane-treated soda glass as an adherend. [0128] This adhesive structure was firmly adhered, and its compressive shear adhesive strength was 240 kgf/cm2, and it had excellent adhesive strength in a dry state. [0129] When the adhesive structure of 'L' was immersed in warm water at 80° C., on the third day, the area around the bonded surface began to peel off and became cloudy. Moreover, when autoclave treatment was performed 20 times, most of the adhesive surface was beginning to peel off, and practical hot water resistance was not exhibited. [01301 Comparative Example 3 Polyfunctional oligoester acrylate in adhesive composition
Stainless steel and Pyrex glass were bonded in the same manner as in Example 3, except that urethane-modified diacrylate was used instead of urethane. [0131] The compressive shear adhesive strength of the joint surface of this adhesive structure was 117 kgf/cm2, which was relatively low. [0132] Furthermore, when this adhesive structure was immersed in warm water at 80°C, it spontaneously peeled off on the second day. Furthermore, wrinkles appeared on the bonded surface after just one autoclave treatment, making it completely unusable. [0133] Comparative Example 4 Example 4 was prepared by heating at 130° C. for 30 minutes using a silane treatment solution consisting of 3 parts by weight of 3-glycidoxypropyltrimethoxysilane, 1 part by weight of pure water, and 100 parts by weight of ethanol. Stainless steel was treated with silane similar to that used in [0134] Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd. as a bisphenol A type epoxy adhesive
1 using diaminodiphenylsulfone as a curing agent.
Stainless steel was joined as in Example 4 by heating at 20° C. for 12 hours. [0135] The compressive shear adhesive strength of the bonded structure in the dry state was 273 kgf/cm2, which was good, but after being immersed in warm water at 80°C for two weeks, it was only a few kgf.
/cm2, and it peeled off easily by pressing lightly with fingers. Furthermore, even when the autoclave treatment was performed 20 times, a significant decrease in adhesive strength was observed as in the case of immersion in 80° C. hot water, and practical hot water resistance was not exhibited. [0136] Comparative Example 5 100 parts by weight of 4-methacryloxytricyclo(5,2,1,026)decane, which is a compound of Group B of the present invention, 1 part by weight of camphor quinone, and 1 part by weight of dibenzoyl peroxide were added to the adhesive. A soda glass bonded structure was produced in the same manner as in Example 1, except that a mixture of the following parts was used. [0137] The compressive shear adhesive strength of this adhesive structure in the dry state was 173 kgf/cm2, which was relatively good, but when it was immersed in water at 80°C, it naturally peeled off in 5 days, indicating good hot water resistance. did not show. [0138]

[Effects of the Invention] As explained above, by using the method for manufacturing a bonded 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. [0139] In the method for manufacturing a bonded structure of the present invention, the adhesive used for the bonding surface also has excellent transparency, so it can also be applied to bonding optical components. It has the advantage of being able to [01401 The excellent adhesive properties and hot water resistance of the adhesive structure of the present invention are achieved by bonding silane-treated adherends by polymerizing and curing an adhesive containing a group A compound. This is an effect unique to the present invention that can only be obtained when the method of the invention is used.

Claims (4)

[Claims] Claim 1: After treating the adhesive surface of the adherends constituting the adhesive structure with a silane coupling agent, at least one compound selected from the following group A is contained between the adherends. A method for producing a hot water-resistant adhesive structure, which comprises adhering the adherends together by interposing an adhesive and polymerizing and curing the 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 acrylate,
Pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol monohydropenta(meth)acrylate. 2. The method for producing a hot water-resistant adhesive structure according to claim 1, wherein the adhesive further contains at least one compound selected from the following group B: ) 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 (
Meta) acrylate. 3. The method for producing a hot water-resistant bonded structure according to claim 1, wherein the adherend is glass, metal, or ceramic. 4. Claims 1 to 3, wherein the adhesive surface of the adherend is subjected to sandblasting treatment in advance.
A method for producing a hot water-resistant adhesive structure according to any one of the above.