JP2005239944A - Adhesive, method for bonding article and bonded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an adhesive comprising an organic/inorganic hybrid glassy material as the main component, to provide a method for bonding articles using the adhesive and to provide a bonded article. <P>SOLUTION: The adhesive uses the organic/inorganic hybrid glassy material having melt properties as an adhesive component. The adhesive has a softening temperature of not less than 40°C to not more than 400°C wherein the softening temperature rises every time heat treatment is conducted, and has an average visible light transmittance at a wavelength of 300-800 nm of not less than 80 % in 100 μm thickness. The method for bonding articles using the adhesive comprises sandwiching the adhesive between at least two articles and melt bonding by heat treatment wherein the heat treatment for bonding is conducted at 40-600°C and at least one of two articles is made of glass. The article bonded by the above method has adhesive strength of 5 MPa or more. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an adhesive mainly composed of an organic-inorganic hybrid glassy substance, an adhesion method for an article using the adhesive, and an adhered article.

  Adhering articles to each other is an important technique and has been done in many places. However, adhesion is a technique with difficult aspects, in which, if the processing temperature, use temperature, material, etc. are different, the adhesive must often be changed. Furthermore, there still exist problems relating to adhesion that have been considered difficult in the past, such as when other required performance such as adhesion while ensuring transparency, or when the shape of the adhesion surface is complicated. In particular, the demand for these problems has become apparent in relation to the bonding processing temperature and the use temperature.

  For example, in the case of bonding while ensuring transparency, glass-to-glass bonding is often used, and as an example, for example, it is possible to make a transparent material while improving safety against brittle fracture, which is a drawback of glass it can. A typical so-called laminated glass that is bonded using polyvinyl butyral (hereinafter referred to as PVB) is representative, and has the characteristics that even when broken, the glass is less likely to scatter and fall off and has the characteristics of PVB that absorbs ultraviolet rays. Therefore, it is used in many places such as places where safety and crime prevention are required, or places where you want to prevent ultraviolet rays. Use cases include windshields for automobiles, doors and window glass for buildings and railway vehicles, show windows, water tanks, pool viewing windows, and fences on verandas. The use of laminated glass has been increasing in recent years. . For example, in order to further enhance the safety of automobile windshields, partially tempered glass that has been used until now is prohibited, and only laminated glass can be used.

  For example, PVB and EVA (hereinafter referred to as EVA) are bonded to each other, but PVB and EVA are typical organic substances, and thus cannot withstand temperatures of 300 ° C. or higher. Also, when the temperature exceeds 100 ° C., for example, many problems occur such as changing from the characteristics of laminated glass to the characteristics of laminated glass. For this reason, the adhesive agent which can respond also in a higher temperature state is anticipated.

Further, even when the surface shape is complicated, the adhesion becomes difficult. For example, when bonding IC ceramic packages, diesel exhaust gas filters, incinerator walls, structural members of various furnace gaskets, and the like, it is difficult to bond on complicated shapes. In general, in such a case, since the bonding processing temperature is often high, so-called low melting glass of 500 to 600 ° C. has been used. However, even when bonding such materials, it goes without saying that it is desirable that the temperature of the bonding process be lower. This is because the work of confirming the bonding status is often important because the bonding surface is complex. Generally, the temperature of the bonding process should be low, preferably 400 ° C or lower, particularly 300 ° C or lower. May be around 600 ° C. In addition, when the adhesion treatment is performed at 300 ° C. or lower, adhesion retention at 300 ° C. or higher is required. Considering the above, it is desirable to use an adhesive having a softening temperature of 400 ° C. or lower and an adhesive retention of more than 300 ° C. On the other hand, it is also necessary to be able to process at around 600 ° C. However, it has been very difficult to obtain an adhesive having such useful adhesion. When the glass had adhesiveness at a softening temperature of less than 400 ° C., no low melting glass was suitable. In addition, while there is a strong demand for glass that does not contain lead due to global environmental problems, it is more difficult to develop a low-melting-point glass that is adhesive with lead-free glass.

  As a general method for producing a low melting glass, a melting method and a low temperature synthesis method are known. The melting method is a method in which a glass raw material is directly heated to be melted and vitrified. Many glasses are produced by this method, and low-melting glass is also produced by this method. However, in the case of a low-melting glass, there are many restrictions on the glass composition that can be constructed, such as the need to contain lead, alkali, bismuth, etc. in order to lower the melting point.

  On the other hand, as a low-temperature synthesis method of amorphous bulk, a sol-gel method, a liquid phase reaction method, and an acid anhydride base reaction method are considered. In the sol-gel method, a bulk body can be obtained by hydrolysis-polycondensation of metal alkoxide and the like, and heat treatment at a temperature exceeding 500 ° C., usually 700 to 1600 ° C. However, the bulk body produced by the sol-gel method does not have properties as an adhesive material. In addition, it is often porous due to the decomposition and combustion of organic substances such as alcohol introduced during the preparation of the meltable raw material solution, or evaporation and release in the process of heating organic decomposition gas or water. There was also a problem with the strength.

  In addition, the liquid phase reaction method has a low yield, resulting in low productivity, the use of hydrofluoric acid in the reaction system and the limited synthesis of thin films. It is almost impossible to synthesize. That is, a practical low-melting glass by the liquid phase reaction method has not been developed yet.

  As described above, many low-melting-point glasses have been produced not by a low-temperature synthesis method but by a melting method, but the glass composition is limited for the purpose of melting a glass raw material. Further, when producing glass having adhesiveness, it is very difficult to make the softening point 400 ° C. or lower even if lead is used. Furthermore, it has not been developed in the world when it becomes a practical low-melting glass that does not use lead, is transparent, and has adhesiveness at 400 ° C. or lower.

  To further describe the demand for this adhesive, the adhesive is colorless and transparent in order to make use of the transparency of the glass, that it has an adhesive treatment property than PVB and EVA, and that the thickness of the adhesive can be controlled. In addition, it will ultimately be desirable for the adhesion to persist to high temperatures.

Looking at publicly known literatures, the main component is PbO—B ₂ O ₃ which is often used for sealing of laminated ceramic glass (see, for example, Patent Document 1), which is a combination of a PVB film and a sound insulation film, and IC ceramic packages. Solder glass materials (for example, see Patent Document 2) for bonding ceramic materials to be bonded, sealing materials made of a crystalline glass composition (for example, see Patent Document 3), and the like are disclosed.

  Under such circumstances, organic-inorganic hybrid glass is attracting attention as a low-melting-point material replacing lead glass (for example, see Non-Patent Document 1, Patent Documents 4 and 5). The organic-inorganic hybrid glass has received attention as a functional film material (for example, Patent Document 6), but other applications have not been studied much. For this reason, organic-inorganic hybrid glass has been limited to some uses such as outer wall coating materials. Research on the use of organic-inorganic hybrid glass as a so-called bulk body rather than a functional film or coating material has just started, and its properties are often unknown. In particular, the basic matters regarding the adhesive action are almost unknown, and it cannot be said that the manufacturing method and the thickness control method have been completed.

JP-A-9-165235 JP 7-330374 A JP-A-9-255360 JP 2003-313300 A JP 2003-313048 A JP-A-2-137737 Masahide Takahashi, Haruki Niida, Toshinobu Yokoo, New Glass, 8-14, 17 (2002).

  For example, an article bonded using PVB or EVA has an advantage that the bonding process can be performed at 300 ° C. or lower, but cannot withstand a temperature of 300 ° C. or higher, and also exceeds, for example, 100 ° C. during use. And, there was a problem that the adhesiveness deteriorated remarkably.

  In addition, since the production of adhesives using many low softening point materials, particularly conventional low melting point glass adhesives, has been performed by a melting method, the glass composition has many limitations and has a heat resistance of 300 ° C. or higher. There was no adhesive that simultaneously satisfied the adhesion and workability of adhesion at 400 ° C. or lower. In particular, there was no glass that satisfies the above conditions while having transparency.

  On the other hand, when trying to produce a low-melting glass by a sol-gel method of a low-temperature synthesis method, a temperature treatment of 500 ° C. or higher is required for densification, but if it is treated at that temperature, it does not become a low-melting glass. As a result, it was not a transparent glass adhesive having heat resistance of 300 ° C. or higher and adhesion workability at 400 ° C. or lower.

The method disclosed in Japanese Patent Laid-Open No. 9-165235 is useful in that it shows the possibility of glass bonding using two types of films having different properties, PVB film and sound insulation film, but the atmosphere is 300 ° C. or higher. Cannot be used below. The material disclosed in Japanese Patent Application Laid-Open No. 7-330374 has an adhesive action, but has PbO—B ₂ O ₃ as a main component and has a problem from the viewpoint of the global environment. Further, the material disclosed in Japanese Patent Laid-Open No. 9-255360 cannot be used as an adhesive having an adhesion treatment temperature of 400 ° C. or lower. Further, JP-A-2003-313300, JP-A-2003-313048, or JP-A-2-137737 does not describe anything related to adhesiveness.

  Thus, for example, conventional adhesive films such as PVB, low-melting glass not containing lead, and other adhesives simultaneously satisfy heat resistance of 300 ° C. or more and adhesion processability of 400 ° C. or less. I couldn't. In particular, there was no adhesive that simultaneously satisfies the adhesion processability at 300 ° C. or lower, the heat resistance at 300 ° C. or higher, and the transparency.

  The present invention is an adhesive using an organic-inorganic hybrid glassy material having meltability as an adhesive component.

  Moreover, it is said adhesive agent whose softening temperature is 40 degreeC or more and 400 degrees C or less.

  Moreover, it is said adhesive agent whose softening temperature rises whenever it heat-processes.

  Further, the adhesive has an average visible light transmittance at 300 to 800 nm of 3 mm thickness and 80% or more.

  Furthermore, it is the adhesion | attachment method of the articles | goods using said adhesive agent.

  Further, in the above-described bonding method, an adhesive is sandwiched between at least two articles and fused by heat treatment.

  In addition, in the method for adhering an article described above, the heat treatment for adhering is performed at 40 to 600 ° C.

  Further, it is the method for adhering an article as described above, wherein at least one of the articles is glass.

  Furthermore, it is an article bonded by the above method.

  Moreover, it is the above-mentioned bonded article having an adhesive strength of 5 MPa or more.

  According to the present invention, the heat resistance of 300 ° C. or higher and the adhesion processability of 400 ° C. or lower, which have not been conventionally achieved, can be satisfied at the same time. In addition, it has become possible to bond to an article having a complicated surface shape or to be adhered to various parts with a narrow interval, or a flexible electronic material.

  The present invention is an adhesive that uses a meltable organic-inorganic hybrid glassy material as a main component when bonding articles. Here, the meltability literally refers to the property of melting, that is, the property of greatly reducing the viscosity by heating and becoming a so-called molten state.

  Since conventional organic-inorganic hybrid glass is manufactured by a conventional sol-gel method, it does not have meltability, and it has been considered that there is not much change in physical properties even when heated. Although some sol-gel materials were known to soften, they were only at the level of softening and not in a molten state. Moreover, it tends to color when heated strongly. For these reasons, organic-inorganic hybrid glass has so far been focused mainly as a thin film-like functional film material having a thickness of several μm or less, and its industrial use has been limited to film-like or coating materials. However, in the case of an organic-inorganic hybrid glassy material exhibiting meltability, it can be used as an adhesive. This is because by having the meltability, it is possible to enter between complex shapes and to bond them.

  The reason why the content of the organic-inorganic hybrid glassy substance is used as a main component is that the adhesive can be used in many different applications and usage conditions, so that many choices can be made regarding its content. For example, when the use temperature is low, a large amount of organic adhesive can be mixed, whereas when the use temperature is high, a large amount of inorganic adhesive is mixed. Further, depending on how much transparency is required, the mixing of subcomponents varies. Thus, although the selection is wide, it is preferable that the organic-inorganic hybrid glassy substance as the main component is mixed by 30% or more by weight%, and more preferably 50% or more. If it is less than 30%, the limitation of the bonding temperature and holding temperature increases, and the problem of transparency also arises. Naturally, the upper limit is 100%. Further, the concept regarding the inclusion of the main component is the same in the following.

  In addition, it is preferable to use an adhesive whose main component is an organic-inorganic hybrid glassy material having a softening temperature of 40 ° C. or higher and 400 ° C. or lower. Below 40 ° C., the effect of heat treatment is extremely small, and at 400 ° C. and above, stable adhesion often does not occur, and there are cases where coloring occurs. More preferably, it is 60-360 degreeC, More preferably, it is 100-350 degreeC. This heat treatment is not performed once, but may be divided into two or more times, or the temperature condition may be changed. In general, it is preferable to change the heating temperature in the increasing direction. In addition, the softening temperature of the organic-inorganic hybrid glassy substance was judged from TMA measurement which was heated at 10 ° C./min. That is, the shrinkage was measured under the above conditions, and the change start temperature of the shrinkage was defined as the softening temperature.

  In addition, it is preferable to use an adhesive whose main component is an organic-inorganic hybrid glassy material whose softening temperature increases each time heat treatment is performed. An organic-inorganic hybrid glassy material having meltability often has a characteristic that the softening point changes. By using an organic-inorganic hybrid glassy substance whose softening temperature rises, it is desirable to obtain a predetermined adhesive property by initially processing at a low temperature to form a layer, and then heating to raise the softening temperature. In the case of an organic-inorganic hybrid glassy material whose softening temperature is lowered or an organic-inorganic hybrid glassy material whose softening temperature is lowered as a result of various treatments, it is difficult to obtain a predetermined adhesive strength.

  Further, it is preferable to use an adhesive mainly composed of an organic-inorganic hybrid glassy material having an average visible light transmittance of 3 mm and a thickness of 80% or more at 300 to 800 nm. By using an adhesive whose main component is an organic-inorganic hybrid glassy material having such characteristics, a highly transparent glass article can be obtained. In particular, when both of the articles are made of glass, by having a transmittance comparable to that of a general float glass, an article having high transparency can be manufactured as a result. Moreover, even when one is glass, the article | item which can utilize the permeability | transmittance effectively can be manufactured.

  Further, it is preferable to use a method for adhering an article using the above adhesive. By using such an adhesive, it becomes possible to simultaneously satisfy the heat resistance of 300 ° C. or higher and the adhesive processability of 400 ° C. or lower, which has not been conventionally achieved, and have various complex surface shapes or narrow intervals. This is because it is possible to adhere to an article adhered to a part or the like, or a flexible electronic material.

  In addition, it is preferable that the adhesive is sandwiched between at least two articles and fused by heat treatment. The article may be a structural member of an IC ceramic package, a diesel exhaust gas filter, an incinerator wall, various furnace gaskets, or glass. A so-called solid material can be an object to be bonded. In addition, in order to give adhesiveness, it is necessary to heat-process. This heating is performed after sandwiching a predetermined organic-inorganic hybrid material.

  The organic-inorganic hybrid glassy substance used as an adhesive is preferably bonded in a layered form, a powdery form or a paste form. It is more preferable to bond using a layered organic-inorganic hybrid glassy material. In this case, it is common to apply a powdery organic-inorganic hybrid glassy substance to the surface of the substance to be bonded, heat to fluidize it into a layer, and then heat to bond, but once cooled May be reheated. Of course, the powdery organic-inorganic hybrid glassy material may be subjected to heat treatment as it is. Further, a paste may be used, and in this case, a paste dissolved in an organic solvent is preferable. If conditions such as adhesiveness allow, so-called film-like organic-inorganic hybrid glassy materials may be used. However, adhesion in a layered or powdery form is more stable and secures adhesion. Is done. The thickness of the bonded portion is preferably 30 μm or more, more preferably 100 μm or more, and further preferably 500 μm or more, from the viewpoint of strength. Moreover, although the upper limit of the thickness of an adhesion part changes greatly with each conditions, since organic-inorganic hybrid glass also has a large coefficient of thermal expansion, it is generally several millimeters.

  Moreover, it is preferable that the heat processing temperature for adhesion | attachment is an adhesion method performed at 40-600 degreeC. Below 40 ° C, the effect of heat treatment is extremely small, and at 600 ° C and above, stable adhesion is often not achieved. When coloring is a problem, the temperature is preferably 400 ° C. or lower, and when coloring is not a problem, it can be up to 600 ° C. Even when the temperature exceeds 400 ° C., the coloration is often small when the treatment time is short. Considering the above, the range of 60 to 400 ° C is more preferable, and the range of 100 to 350 ° C is more preferable. This heat treatment is not performed once, but may be divided into two or more times, or the temperature condition may be changed. In that case, it is preferable to change the heating temperature in the direction of increasing.

  Moreover, it is preferable that at least one of the articles is glass. By using at least one of the articles as glass, the transparency can be utilized. Furthermore, since glass is chemically stable, the adhesion effect tends to be sustained. Typical examples of the glass include commercially available soda-lime glass, aluminosilicate glass, borosilicate glass, and other architectural glass, automotive glass, and electronic material glass. There is no big problem.

  It is preferable to use an organic-inorganic hybrid glassy material having a visible light transmittance of, for example, 3 mm and a thickness of 80% or more and a glass of, for example, a thickness of 5 mm and 80% or more. In this case, the visible light transmittance is an average visible light transmittance at a wavelength of 300 to 800 nm. By combining an organic-inorganic hybrid glassy material having such characteristics with a highly transparent glass article, a highly transparent article can be produced. Moreover, even when one side is not glass, the article | item which can utilize effectively the permeability | transmittance of a glass part can be manufactured.

  In addition, there exists a tendency for adhesive force to become large when the surface of an article | item is hydrophilically processed and for adhesiveness to become small when water-repellent treatment is carried out. In order to obtain a larger adhesive force, it is desirable to hydrophilically treat the surface of the article.

  Further, the article is bonded by the above method. This article has the characteristics of simultaneously satisfying heat resistance of 300 ° C. or higher and adhesion processability of 400 ° C. or lower, which has not been achieved conventionally. It is also useful when high transparency is required.

  Furthermore, an article having an adhesive strength of 5 MPa or more is preferable. The adhesive strength is a shear strength, and can be determined by a test method according to JIS K6850 “Testing method for tensile shear bond strength of adhesive-rigid adhesive”. The reason why the adhesive strength is 5 MPa or more is that if the adhesive strength is less than 5 MPa, a predetermined strength cannot be obtained and sufficient adhesiveness cannot be obtained.

  In the present invention, an organic-inorganic hybrid glassy material produced as follows is preferably used as an adhesive. That is, the starting raw material is a metal alkoxide, and an organic-inorganic hybrid glassy substance produced through a heating reaction step, a melting step and an aging step after a mixing step using the metal alkoxide as a raw material and water, an acid catalyst and an alcohol is provided. preferable. The organic-inorganic hybrid glassy material obtained by this method has high stability and can be produced at low cost while maintaining good quality. Next, a method having at least three steps of a gel body production process by a sol-gel method, a melting process by heating, and an aging process is preferable. Although this method can also obtain an organic-inorganic hybrid glassy material, there is a problem in that productivity is lowered because the gelation process takes 1 to 3 days. Here, what is important is that it is meltable and cannot be produced by a conventional sol-gel method having no meltability.

  The metal alkoxide used as a raw material is an alkoxysilane substituted with an organic substituent. The organic substituent is a phenyl group, a methyl group, an ethyl group, a propyl group (n-, i-), a butyl group (n-, i-, t-), pentyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, mercaptomethyl group, mercaptopropyl group, 3,3,3-trifluoropropyl group, 3-trifluoroacetoxypropyl group, vinyl It is preferably selected from metal alkoxides consisting of methoxy, ethoxy, propoxy (n-, i-), etc. as alkoxyl groups from the group, benzyl group, styryl group and the like. These are extremely useful raw materials for producing an organic-inorganic hybrid glassy material, particularly a transparent material that is softened at room temperature or lower. Metal alkoxides other than those described above may be used. Further, metal acetylacetonate, metal carboxylate, metal nitrate, metal hydroxide, metal halide and the like used in the sol-gel method can be produced.

  Typical alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 1.1-dimethyl-1-ethanol and the like. However, it is not limited to these.

It is preferable to have a heating reaction step before entering the melting step, that is, between the starting material mixing step and the melting step by heating. This heating reaction step is preferably performed at a temperature of 40 ° C. or higher and 100 ° C. or lower. Outside this temperature range, a metal unit having an organic functional group R in its structure, for example, a silicon unit represented by (R _n SiO _{(4-n) / 2} ) (selected from n = 1, 2, 3), Further, in detail, a phenyl group metal unit (Ph _n SiO _{(4-n) / 2} ), a methyl group metal unit (Me _n SiO _{(4-n) / 2} ), an ethyl group metal unit (Et _n SiO _{(4-n) / 2} ), butyl group metal units (Bt _n SiO _{(4-n) / 2} ) (n = 1 to 3) and the like cannot be appropriately contained, so that the glass can be melted organic Obtaining an inorganic hybrid glassy material becomes extremely difficult.

  The organic functional group R is typically an alkyl group or an aryl group. The alkyl group may be linear, branched or cyclic. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group (n-, i-), a butyl group (n-, i-, t-), a pentyl group, a hexyl group (carbon number: 1 to 20). Particularly preferred are methyl and ethyl groups. Furthermore, examples of the aryl group include a phenyl group, a pyridyl group, a tolyl group, and a xylyl group, and a phenyl group is particularly preferable. Of course, the organic functional group is not limited to the above-described alkyl group or aryl group.

  The melting step by heating is preferably performed at a temperature of 40 ° C. or higher and 500 ° C. or lower. At temperatures lower than 40 ° C., it cannot be melted substantially. Further, when the temperature exceeds 500 ° C., the organic group bonded to the metal element forming the network burns, so that a desired organic-inorganic hybrid glassy material cannot be obtained, and it becomes opaque due to crushing or generation of bubbles. Or Desirably, it is 100 degreeC or more and 300 degrees C or less.

  In the aging step, the treatment is performed at a temperature of 30 ° C. or higher and 400 ° C. or lower. At a temperature lower than 30 ° C., it cannot be aged substantially. When it exceeds 400 ° C., it may be thermally decomposed, and it becomes difficult to obtain a stable glassy substance. The effect of the aging temperature becomes extremely small at a temperature lower than the melting lower limit temperature. Generally, the lower limit of melting temperature to the lower limit of melting temperature (+ 150 ° C.) is desirable. Furthermore, the time required for aging is 5 minutes or more. The aging time varies depending on the processing amount, processing temperature, and allowable residual amount of reactive hydroxyl group (—OH), but generally it is extremely difficult to reach a satisfactory level in less than 5 minutes. Moreover, since productivity falls in a long time, it is 10 minutes or more and less than 1 week desirably. In the case of aging, it is divided into two steps of a first aging performed at a temperature of 40 ° C. to 230 ° C. and a pressure of 0.1 Torr or less and a second aging performed at 70 ° C. to 350 ° C. under atmospheric pressure. Is also effective.

  A stable organic-inorganic hybrid glassy material can be obtained through the melting step and the aging step. Since the conventional sol-gel method does not have the melting step, it naturally has no subsequent aging step, but also has a characteristic of passing through a gel body. Thus, it has different properties from the conventional organic-inorganic hybrid glassy material.

  The upper limit temperature of the heating reaction step is 100 ° C. or lower when an alcohol having a boiling point exceeding 100 ° C., for example, 1-butanol having a boiling point of 118 ° C. is used, but it is desirable to consider the boiling point of alcohol having a boiling point of 100 ° C. or lower. For example, when ethanol is used, the boiling point tends to be better at 80 ° C. or lower. This is presumably because when the boiling point is exceeded, the alcohol rapidly evaporates, so that it is difficult to achieve a uniform reaction from the amount of alcohol and changes in state. In addition, after a heating reaction process, you may enter into a melting process immediately, and after cooling once, you may enter into a melting process.

As described above, a method of melting and aging after producing a gel body over time may be used. However, since it takes 1 to 3 days for gelation, productivity is considerably lowered as compared to obtaining a desired organic-inorganic hybrid glassy material in about 30 minutes to 5 hours.
Hereinafter, description will be made based on examples.

  Two float glass plates having a thickness of 40 mm × 40 mm and a thickness of 5 mm were prepared. After placing the powdered organic-inorganic hybrid glassy substance on this glass plate, each glass was heated at 150 ° C. for 5 minutes, then cooled to room temperature, and two sheets of organic-inorganic hybrid glassy substance adhered in layers I got a plate. The two glass plates were heated at 170 ° C. for 5 minutes with the layered organic-inorganic hybrid glassy material facing each other, and then cooled to room temperature to obtain a pair of bonded glass articles. . The thickness of the adhesive layer of this glass article was about 100 μm.

The organic-inorganic hybrid glassy material used was manufactured as follows. That is, a metal alkoxide phenyltriethoxysilane (PhSi (OEt) ₃ ) was used as a starting material. As a mixing step, about 40 ml of water, about 30 ml of ethanol, and about 0.30 ml of acetic acid as a catalyst were added to 10 ml of phenyltriethoxysilane at room temperature. After heating at 60 ° C. for 3 hours as a heating reaction step, the temperature was increased to 150 ° C. 4 Melted for hours. Furthermore, after aging for 5 minutes in an atmosphere of about 80 ° C. and about 0.05 Torr, the mixture was aged for 2 hours at 120 ° C. and then cooled to room temperature. Furthermore, the obtained organic-inorganic hybrid glassy material was pulverized to a size of 5 to 20 μm. In addition, although the softening temperature of this organic-inorganic hybrid glassy substance was 130 degreeC at the beginning, when heat-processing on the same conditions as adhesion | attachment, it has confirmed changing to 145 degreeC.

  When the transmittance curve in each wavelength region in the bonded part of the glass article was measured using a Hitachi U-3500 type self-recording spectrophotometer, there was no significant coloration, especially absorption in the blue region, which was observed in the past, and visible light transmission was achieved. The rate was 86.6%. From this value, it was estimated that the average transmittance of visible light at a wavelength of 300 to 800 nm of the organic-inorganic hybrid glassy substance was about 90% in terms of 3 mm thickness.

  The glass article was placed in a heating test furnace capable of strength test and held at 350 ° C. for 1 hour, and then an adhesive strength test was performed. The adhesion test was a shear test, and was determined by a test method according to JIS K6850 “Testing method for tensile shear bond strength of adhesive-rigid adhesive”. That is, a shear stress was applied to the bonded glass article, and the shear strength was determined from the amount of load when shear failure occurred. At this time, the shear strength was about 16 MPa. Moreover, after cooling to room temperature, the glass article was taken out and the state of destruction of the organic-inorganic hybrid glassy material used as an adhesive was observed. As a result, since it was destroyed from the interface between the glass article and the organic-inorganic hybrid glassy substance, it was confirmed that the adhesive strength of the organic-inorganic hybrid glassy substance was larger than the above-mentioned value. Moreover, the organic-inorganic hybrid glassy substance remained colorless and transparent.

  Two aluminum plates having a thickness of 40 mm × 40 mm and a thickness of 5 mm were prepared. After placing the powdered organic-inorganic hybrid glassy material on this aluminum plate, heating at 150 ° C. for 5 minutes, cooling to room temperature, and two layers of aluminum with the organic-inorganic hybrid glassy material attached in layers I got a plate. The two aluminum plates were heated at 170 ° C. for 5 minutes with the layered organic-inorganic hybrid glassy material facing each other, and then cooled to room temperature to obtain a pair of bonded aluminum articles. . The thickness of the adhesive layer of this aluminum article was about 100 μm.

The organic-inorganic hybrid glassy material used was manufactured as follows. That is, metal alkoxides phenyltriethoxysilane (PhSi (OEt) ₃ ) and diethoxydiphenylsilane (Ph ₂ (OEt) ₂ ) were used as starting materials. As a mixing step, about 40 ml of water, about 25 ml of ethanol, and about 0.30 ml of acetic acid as a catalyst were added to 10 ml of phenyltriethoxysilane at room temperature. After heating at 60 ° C. for 1 hour as a heating reaction step, 2.5 ml of Ethoxydiphenylsilane and about 5 ml of ethanol were added dropwise, and the mixture was further stirred at 60 ° C. for 2 hours, then heated to 150 ° C. and melted for 4 hours. Furthermore, after aging for 5 minutes in an atmosphere of about 80 ° C. and about 0.05 Torr, the mixture was aged for 2 hours at 120 ° C. and then cooled to room temperature. Furthermore, the obtained organic-inorganic hybrid glassy material was pulverized to a size of 5 to 20 μm. In addition, although the softening temperature of this organic-inorganic hybrid glassy substance was 100 degreeC at the beginning, when it processed on the same conditions as adhesion | attachment, it has confirmed changing to 120 degreeC.

  This article was subjected to the same adhesive strength test as in Example 1 (retaining conditions were 500 ° C. for 1 hour). As a result, the shear strength was about 7 MPa.

  Two aluminum plates having a thickness of 40 mm × 40 mm and a thickness of 5 mm were prepared. After placing the powdered organic-inorganic hybrid glassy substance between the aluminum plates, the mixture was heated at 160 ° C. for 10 minutes, cooled to room temperature, and a set of bonded aluminum articles was obtained. The thickness of the adhesive layer of this aluminum article was about 100 μm.

The organic-inorganic hybrid glassy material used was manufactured as follows. That is, metal alkoxides phenyltriethoxysilane (PhSi (OEt) ₃ ) and diethoxydiethylsilane (Et ₂ (OEt) ₂ ) were used as starting materials. As a mixing step, about 40 ml of water, about 25 ml of ethanol, and about 0.30 ml of acetic acid as a catalyst were added to 10 ml of phenyltriethoxysilane at room temperature. After heating at 60 ° C. for 1 hour as a heating reaction step, 1.0 ml of Ethoxydiethylsilane and about 5 ml of ethanol were added dropwise, and the mixture was further stirred at 60 ° C. for 2 hours, then heated to 150 ° C. and melted for 4 hours. Furthermore, after aging for 5 minutes in an atmosphere of about 80 ° C. and about 0.05 Torr, the mixture was aged for 2 hours at 120 ° C. and then cooled to room temperature. Furthermore, the obtained organic-inorganic hybrid glassy material was pulverized to a size of 5 to 20 μm. In addition, although the softening temperature of this organic-inorganic hybrid glassy substance was 105 degreeC at the beginning, when it processed on the same conditions as adhesion | attachment, it has confirmed changing to 135 degreeC.
The adhesive strength test similar to Example 1 was done about this article. As a result, the shear strength was about 9 MPa.

(Comparative Example 1)
PVB was used as the adhesive, and a glass article having the same shape as in Example 1 was produced. The thickness of PVB was about 0.38 mm (15 mil), and the adhesion treatment could be performed at about 230 ° C. under vacuum conditions. However, although it tried to heat to 350 degreeC, foaming started from the temperature range over 100 degreeC, and also there was a flow phenomenon of PVB, and since the glass article was stood and heated, PVB between glasses flowed out in large quantities. For this reason, since the meaning of adhesion was lost, it was stopped when the temperature was raised to about 250 ° C.
This article was subjected to the same adhesive strength test as in Example 1 (retaining conditions were 500 ° C. for 1 hour). As a result, the shear strength was less than 0.1 MPa, which was extremely close to zero.

(Comparative Example 2)
As the adhesive, SiO ₂ —B ₂ O ₃ —ZnO—Na ₂ O-based glass called low-melting glass was used, and production of a glass article having the same shape as in Example 1 was attempted. That is, using glass in which all are by weight, SiO ₂ is about 15%, B ₂ O ₃ is about 27%, ZnO is about 40%, Na ₂ O is about 16%, and K ₂ O is about 2%. , Tried to glue. However, even if it is a low melting glass, the softening point may have exceeded 450 ° C., and as a result, it could not be bonded at less than 300 ° C.

  Materials for sealing and covering display components such as PDP, optical information communication device materials such as optical switches and optical couplers, optical equipment materials such as LED chips, optical functional (non-linear) optical materials, It can be used in fields where low-melting glass is used, such as adhesive materials, and fields where organic materials such as epoxy are used.

Claims (10)

An adhesive comprising an organic-inorganic hybrid glassy material having meltability as an adhesive component. The adhesive according to claim 1, wherein the softening temperature is 40 ° C or higher and 400 ° C or lower. The adhesive according to claim 1 or 2, wherein the softening temperature rises every time heat treatment is performed. The adhesive according to any one of claims 1 to 3, wherein an average visible light transmittance at 300 to 800 nm is 80% or more at a thickness of 3 mm. A method for adhering an article, wherein the adhesive according to any one of claims 1 to 4 is used. 6. The method for adhering an article according to claim 5, wherein an adhesive is sandwiched between at least two articles and fused by heat treatment. The method for bonding an article according to claim 6, wherein the heat treatment for bonding is performed at 40 to 600 ° C. The method for adhering an article according to any one of claims 5 to 7, wherein at least one of the articles is glass. An article bonded by the method according to claim 5. The article according to claim 9, which has an adhesive strength of 5 MPa or more.