TW201226510A - Manufacturing method for junction structure and junction structure - Google Patents

Abstract

The present invention is a manufacturing method for a junction structure, which is a manufacturing method for a junction structure made by joining two junction materials, and which is characterized in containing a junction intermediate layer formation step and a junction step. The junction intermediate layer formation step is to form a junction intermediate layer constituted by at least one selected from the group consisting of free hydrogen, water vapor gas, alcohol gas, hydrogen peroxide gas, organic metal compound, and silane coupling agent on at least one junction surface of two junction materials; the junction step is to carry out heating and/or irradiation of the electromagnetic wave towards the two junction materials and the junction intermediate layer through the state in which the junction intermediate layer overlaps the two junction materials.

Description

201226510 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a method of manufacturing a joined structure in which two joining materials are joined, and a joined structure. Ο [Previous 彳 术 】 [0002] In recent years, flat panel displays and solar panels represented by liquid crystals and organic ELs have been strongly requested to be transferred from the viewpoint of energy saving and environmental protection. Glass and tantalum inorganic material substrates, thinner and lighter flexible film substrates. :. . -,.+ .. ... ;''... . 2:: The LCD panel is encased in 2 pieces of glass substrate seals > LCD, Japanese, Bu, multi-layered with light manipulation It is composed of many functional membranes. Such a functional film includes a polarizing film, a phase difference 臈, an antireflection film, a light control film, a protective film, and the like. [0003] [0004] [0004] The liquid crystal display panel manufacturing process described above frequently performs bonding between different materials of different materials and bonding of glass and film. However, in general, compared with the inorganic material substrate, the heat resistance of the film is low in the manufacturing process, and the thermal program is widely used in the manufacturing process to several hundred degrees. Therefore, the system is governed by the method of rectifying the hot age of the company. [0005] Nothing, as a technique for using a pick-up agent between the film and the film, it is not a technique that will apply a corona discharge: 'heart to dance* plastic saturated decene resin, through polyester plural The alcohol-based film is bonded to a polarizer made of polyethylene glycol to form a protective film for a polarizing plate (Patent Document 1). /... 099144806 Form No. A0101 Page 3 / Total 5i Page 1003055875-0 201226510 [0006] [0007] [0009] And 'Ί场' (4) - a technique that is attached to a polarizer (polarizing film), In the surface of the adhesive layer, a hydrocarbon resin film is laminated, and a cellulose acetate resin film is laminated on the other surface to form a polarizing plate (see Patent Document 2). On the other hand, there are also proposals to prevent the protective film layer from being bonded to the polarized light without passing through the adhesive. For example, a technique disclosed in which a protective film is formed by using two resin films having different softening points, and a polarizing plate is attached to the side of the low-softening point layer, and a polarizing plate is obtained by thermocompression bonding (see Patent Document 3 to 5) and disclose a method of manufacturing a polarizing plate by heat-treating a protective film and a polarizer at a temperature lower than a softening point of a protective film and irradiating electromagnetic waves (see Patent Document 6). [Patent Document 1] [Patent Document 1] JP-A-2000-241627 (Patent Document 2) JP-A-2006-053725/A. 〇 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2002 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 2008 When the bonding is performed using an adhesive, 'there is a case where the adhesive adversely affects the characteristics of the film. For example, when an adhesive is used in the production of a polarizing plate, there are problems such as optical characteristics of the adhesive and influence of the composition on the polarization of the polarizer. 099144806 Form No. A0101 Page 4 of 51 1003055875-0 201226510 [0011] [0012] Further, when an adhesive is used, there is also a problem that it takes time to increase in the drying step and the like. . For example, when a cycloolefin-based resin film having a small photoelastic modulus which has been gradually used in the past is used as a protective film and is bonded to a polarizing mirror using a water-based adhesive, as shown in the above Patent Document 2, in order to sufficiently follow The force appears to be necessary after the lamination-drying, and then matures at a temperature slightly higher than room temperature for several days, resulting in a longer production time. Further, in the method described in the above-mentioned Patent Documents 3 to 5, in order to bond the protective film and the polarizer by heating and bonding, it is necessary to use a resin film having a low softening point on at least the side of the polarizer. limit. In addition, since the heat treatment temperature is required to be equal to or higher than the softening point of the resin film to which the polarizer is bonded, the performance change of the polarizing plate such as deterioration of the polarizer is also worried, although Patent Document 6 uses a softening point than the protective film. Bonding is performed at a low temperature, but sufficient joint strength cannot be obtained. As described above, the film produced by the conventional bonding method has problems in that the use of an adhesive and heating at a softening point or higher of the resin film causes deterioration of optical characteristics, and sufficient bonding strength cannot be obtained. The present invention has been made in view of the above problems. It is an object of the invention to provide a method for producing a bonded structure capable of obtaining sufficient joint strength while suppressing deterioration of optical properties, and a joint structure. [Means for Solving the Problems] In order to solve the above problems, the present invention provides a method of manufacturing a bonded structure, which is a method for producing a bonded structure in which two bonding materials are joined, and characterized in that a bonding dielectric layer is formed. Step and bonding step 099144806 Form No. A0101 Page 5 / Total 51 page 1003055875-0 [0015] 201226510, the bonding dielectric layer forming step is formed on the bonding surface of at least one of the two bonding materials, and is formed from hydrogen gas and water vapor. a bonding medium layer composed of one or more of a group consisting of a gas, an alcohol gas, a hydrogen peroxide gas, an organometallic compound, and a decane coupling agent; and the bonding step is performed on the two bonding materials and the bonding dielectric layer The bonding medium layer heats and/or illuminates electromagnetic waves in a state in which the two bonding materials are overlapped. [0016] In the method for producing such a bonded structure, hydrogen gas, steam gas, alcohol gas, hydrogen peroxide gas, an organometallic compound, or a decane coupling agent formed on the joint surface in the step of forming the dielectric layer is bonded. The step and the two bonding materials each form a new joint. Thereby, it is possible to manufacture a joined structure in which the two joining materials are strongly joined. [0017] In the bonded structure produced by the above-described manufacturing method, since the adhesive is not used, deterioration of optical characteristics due to the adhesive does not occur. Further, since the heat treatment applies a relatively low temperature for bonding the material of the bonding medium layer, it is possible to suppress deterioration of optical properties of the bonding material due to heating at a high temperature, and the bonding material is not softened for bonding at a low temperature. Low resin is limited. According to the above-described production method, it is possible to produce a bonded structure in which sufficient bonding strength can be obtained while suppressing deterioration of optical characteristics. [0019] Further, the above-described steam gas system means that a water film as a bonding medium layer is formed on the joint surface of the two bonding materials, and the vapor which is vaporized by water and the minute water droplets scattered in the gas, or Such mixtures and the like. In order to make the water film well formed into the bonding medium layer (as a very thin water film) ' 099144806 Form No. A0101 Page 6 / Total 51 Page 1003055875-0 201226510 [0020] ο [0022] The above tiny water droplets It is better to use 10G as the water droplets. It can be considered to use a bubbler that can form tiny water droplets, a super-theta wave trap, etc., in a (four) tank and a high-humidity warehouse. Finance (four). The above-mentioned organometallic compound is formed by combining Si and Ti with an organic site. The method of applying the organometallic compound to the substrate can be carried out by a method of adsorbing it after gasification, a method of diluting it with a solvent such as water or alcohol, and a method of dipping or rubbing, or a coating method such as a crucible (four) cloth. A variety of methods. In addition, the method of adsorbing it after the tempering, even if S1 and τ 1 are combined with the singularity of the singularity of the lyophilized solution, the coating is applied to the surface of the substrate and coated by a very thin organic body of about 2 nm. The metal film can exert a higher bonding force. As the organometallic compound, a compound cerium coupling agent, tetraethoxy oxet (TEOS), and the like are known. According to a second aspect of the invention, in the method of manufacturing the bonded structure of the first aspect, the two-bonding material is a ring-dough-type resin and a glass, and the bonding (4), the money coupling, and the bonding step It is a step of heating. In the method for producing such a bonded structure, the reactive group (methoxy, ethoxy, etc.) chemically bonded to the inorganic material by the Wei coupling agent can be combined with the glass, and the reactive group of the carbon-bonding bond ( A vinyl group, an epoxy group, an anthranyl propyl group, a thiol group, or the like is bonded to a cyclazone resin to form a bonded structure in which a glass and a cycloolefin resin are combined. 099144806 Form No. A0101 The present invention is directed to the method of manufacturing a bonded structure according to the second aspect of the present invention, characterized in that the bonding medium layer is exposed to a vapor of a decane coupling agent. The bonding material is formed. [0024] In the method for producing such a bonded structure, an extremely thin bonding medium layer can be formed by a decane coupling agent, and a high bonding force can be obtained. According to a fourth aspect of the invention, in the method of manufacturing the bonded structure of the first aspect, the two bonding materials are each an organic compound, and the bonding medium layer is made of steam gas or organic The metal compound is composed of the metal compound, and the bonding step is a step of heating. In the manufacturing method of the bonded structure, the bonding surface of the two bonding materials can be formed by heat-treating the two bonding materials in a state of being superposed by the bonding medium layer (the vapor gas or the organometallic compound adsorption layer). Engage between. This is considered to be because the Si-type covalent bond (O-Si-O) and hydrogen can be formed between the contact faces of the organic compound, that is, the bonding material, by heating the bonding medium layer formed of the organometallic compound and the water vapor gas. The reason for the key (HC). According to a fifth aspect of the invention, in the method of producing a bonded structure according to the fourth aspect, the two joining materials are a cycloolefin resin and a polyvinyl alcohol resin. [0028] In the method of producing the joined structure, the joining of the cycloolefin resin and the polyvinyl alcohol resin can be achieved. According to a sixth aspect of the invention, in the method of manufacturing the bonded structure of the first aspect, the two bonding materials are selected from the group consisting of a cycloolefin resin, a polyvinyl alcohol resin, and a glass. 1 or 2, the above is connected to 099144806 Form No. A0101 Page 8 / Total 51 Page 1003055875-0 201226510 The dielectric layer is heated by steaming. The gas gas is composed of the gas and the bonding step is [0030] when the method of preparing the bonded body selected from the group consisting of cycloolefin glass, or the like, It is said that the alcohol resin is bonded. [0031] The method of producing the present invention of the seventh aspect, wherein the temperature is from ° C to 130 ° C. The joining structure of any of the first to sixth aspects is characterized in that the heating temperature of the joining step is 8〇

[0032] ===: When manufacturing the ' method, the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ In the production of the joined structure of the first aspect, the second joining material is an organic compound. The joining medium layer is composed of an organometallic compound, and the front joining step is performed. The step of illuminating electromagnetic waves.

[0034] In the method of manufacturing such a bonded structure, the bonding is performed by transmitting the dielectric layer. The electromagnetic wave is irradiated in the state of the material weight 4, and the sigma planes of the two bonding materials can be joined. This is considered to be because a covalent bond can be formed between the contact faces of the bonding material by irradiating the bonding medium layer formed of the organic metal compound with electromagnetic waves. [0035] 099144806 A specific example is a bonding medium layer composed of an organometallic compound containing Si such as tetraethoxysilane or the like, which is subjected to decomposition reaction by irradiation of electromagnetic waves to form a Ο-Si-O- bond. And the bonding medium layer composed of the organometallic compound containing Ti is decomposed by irradiation of electromagnetic waves, and the reaction is carried out to form a 0-Ti-Ο-bond. According to a ninth aspect of the invention, in the method of manufacturing the bonded structure of the first aspect, the two bonding materials are an organic compound and glass, and the bonding medium layer is composed of steam gas or alcohol gas. And the aforementioned joining step is a step of heating. In the method of manufacturing the joined structure, the bonding between the bonding surfaces of the two bonding materials can be performed by heat-treating the glass and the organic compound layer in a state of being superposed on the bonding medium layer. This is considered to be because the -C-H-0-chain can be formed between the contact surface of the glass and the organic compound by heating the bonding medium layer formed of the steam gas. According to a tenth aspect of the invention, in the method of manufacturing the bonded structure of the first aspect, the two bonding materials are an organic compound and glass, and the bonding dielectric layer is composed of an organic metal compound, and The bonding step is a step of irradiating electromagnetic waves. In the method of manufacturing the bonded structure, the electromagnetic waves are irradiated in a state in which the glass and the organic compound layer are superposed on each other by the transmission bonding medium layer, and the bonding surfaces of the two bonding materials can be joined to each other. This is considered to be because a covalent bond can be formed between the contact faces of the bonding material by irradiating the bonding medium layer formed of the organometallic compound with electromagnetic waves. [0040] As a specific example, a bonding medium layer composed of an organometallic compound containing Si such as tetraethoxysilane or the like is subjected to decomposition reaction by irradiation of electromagnetic waves to form a -O-Si-Ο-bond; The bonding medium layer composed of the organometallic compound containing Ti is subjected to decomposition reaction by irradiation of electromagnetic waves to form a -0_Ti-0- bond. 099144806 Form No. A0101 Page 10/51 Page 1003055875-0 201226510 [0043] [0043] [The first aspect of the 11th aspect of the system is in the first to eighth aspects of the joint structure The surface treatment is included in the step of forming the bonding layer, and the surface treatment step is a surface treatment for performing wettability on at least one of the surfaces before the lifting. This bonding constituting a* ▲ material between the faces: 4 squares' because the layer f and the bonding form the bonding strength. The addition of A ' can promote the bonding at the bonding step and the method of the twelfth aspect, and (4) the fabrication of the bonded structure in the U-th aspect, the surface treatment step is subjected to corona treatment, electric discharge . Oxygen treatment, irradiation of electrical wave pains - the above steps [0044] ΞΗ:=::::=二电 [0045]

[0047] The method of the invention relates to the production of the joined structure according to the first aspect of the invention, wherein the surface treatment step is performed by corona treatment, and the heating is performed for 35 minutes or more. step. In the method of producing the joined structure, the thermal stress in the case where heat is applied to the joined structure can prevent the peeling of the two joining materials. The present invention is in the first to thirteenth aspects. In the method of manufacturing the bonded structure, the ruthenium/dan is to be formed after the bonding medium layer forming step, and the nip step is to overlap the two bonding materials through the bonding medium layer. (4) Carrying out pinching. In the manufacturing method of the bonded structure, since the contact surface of the bonding material can be brought close by the nip step, the bonding at the bonding step can be promoted. Improve joint strength. [0049] Moreover, the specific method of the pinching step is not particularly limited. For example, it is conceivable to use a pressurization such as a press or a press using a press machine, and the pressure to be pinched is a pressure which does not impair the characteristics of the bonding material. Further, the nip step may be performed before the above-described joining step, or may be carried out simultaneously with the joining step. According to a ninth aspect of the invention, in the method of manufacturing the joined structure according to the aspect of the invention, the step of heating is performed while squeezing the two joining materials. In the method of manufacturing such a bonded structure, the bonding of the contact faces can be promoted by the thermocompression bonding at the nip step. [0053] The invention according to claim 16 is a bonded structure in which two bonding materials are joined, wherein the two bonding materials are bonded by hydrogen bonding between surfaces or by covalent bonding of metal molecules. . [0054] Since such a joint construction system does not use an adhesive, deterioration of optical characteristics caused by an adhesive does not occur. Further, since the heat treatment applies a relatively low temperature for the joining of the steam gas and the organometallic compound, it is possible to suppress deterioration of the optical properties of the bonding material due to heating at a high temperature, and the bonding material is not softened for bonding at a low temperature. Low resin limit. Therefore, as long as it is the above-described bonded structure, it is possible to suppress the optical characteristics of 099144806. Form No. A0101 Page 12 / Total 51 Page 1003055875-0 201226510 [0056] [0058] [0059] [0060] Deterioration, while obtaining sufficient joint strength. [Embodiment] Hereinafter, embodiments of the present invention will be described. <Joining of Polyvinyl Alcohol (PVA) Film and Cyclic Olefin Polymer Film> The PVA film used in the present invention is obtained by forming a polyvinyl alcohol-based resin. The method of molding the polyvinyl alcohol-based resin is not particularly limited, and a film can be formed by a known method. Further, the method for producing the polyvinyl alcohol-based resin is not particularly limited. The polyethylene glycol-based resin can be obtained by saponification of a release-polymerized vinyl acetate. The polyvinyl acetate-based crepe is a copolymer of vinyl acetate and another monomer copolymerizable therewith, in addition to polyvinyl acetate, which is a homopolymer of vinyl acetate. Examples of the other monomer copolymerizable with the vinyl acetate include an unsaturated carboxylic acid, an unsaturated sulfonic acid, an olefin, a vinyl alcohol, and an acrylamide having an ammonium group. The degree of saponification of the polyvinyl alcohol-based resin is usually about 85 to 1 mol%, preferably 98 or more. The polyvinyl alcohol-based resin may be further modified, for example, by using a modified polyethylene group and a polyethylene group, etc., or a polymerization degree system of the H-polyvinyl alcohol resin. Usually 1, 〇〇〇 ~ 10, 〇〇〇 around, with 15 〇〇 ~ 5,000 or so is better. Further, the film thickness of the PVA film is not particularly limited. When a polarizer is used to form a polarizing plate, it is a function of a polarizer as long as it is about 10 cents to about ^^. The cycloaliphatic polymer film used in the present invention is composed of a ring-based resin 099144806, Form No. A0101, Page 13 of 51, 1003055875-0 201226510. The cycloolefin-based resin is, for example, a thermoplastic resin having a unit derived from a monomer composed of a cyclic olefin (cycloolefin) of a reduced lanthanum and a polycyclic norbornene-based monomer. The cycloolefin resin may be a hydrogenated product using a ring-opening polymer of the above cyclic olefin and a ring-opening polymer of two or more kinds of cyclic olefins, or may be an aromatic having a cyclic olefin and a chain olefin and a vinyl group. An addition copolymer of a compound. Further, a polar group can also be introduced. [0062] As a commercially available thermoplastic resin cycloolefin-based resin, there is a "polycyclic olefin (ZEQNOR)" manufactured by Japan Reion Co., Ltd., and sold by Ticona, Germany. What are the “ART0N” and Japanese ΖΕΟΝ(shares) sold by Topas” and JSR(shares)? ZE0NEX,, "APEL" sold by Mitsui Chemicals Co., Ltd. (any one is a trade name). This cycloolefin oxime resin is formed into a film. The film formation can be suitably carried out by a well-known method such as a solvent casting method or a melt extrusion method. There are also sold olefin-based resin molds, for example:::::' - : . If there is a "S-SINA" and "'SCA40" by Sekisui Chemical Industry Co., Ltd., "ZE0N0RFILM" or the like (any of which is a trade name) sold by the PTES (shares). In the present invention, since the surface treatment system described later is remarkably exhibited, a film composed of a cycloolefin-based resin can be used, but it can also be used. For example, when a film made of a resin having excellent transparency is selected, a protective film as a polarizing plate can be used. Specific examples thereof include polyethylene terephthalate and polyethylene naphthalate. Diester polyester, polyethylene and polypropylene olefin, cellulose diacetate and cellulose triacetate, cellulose ester resin of cellulose propionate propionate, polyvinylidene gas, poly 4 carbon acid 099144806 Form number A0101 Page 14 of 51 1003055875-0 201226510 [0063] [0066] [0066] Ester, cycloolefin resin, polymethylpentene, polyether ketone, polyether base, Polyfluorene resin, polyether ketone imine, polyamine, acrylic resin [Embodiment 1] In the present embodiment, as an example of the bonded structure, a polarizing plate widely used for a liquid crystal display element is manufactured. Specifically, as a polarizing plate, a polarizing plate is selected as a polyvinyl alcohol. Membrane (POVALFILM, manufactured by KURARAY Co., Ltd., 100 / zm thick, hereinafter referred to as PVA film), and as a protective film, a cycloolefin polymer film (COP), that is, polycycloolefin (ZE0N0R) is selected. In addition, a manufacturing sample of a bonded structure having a plurality of different bonding conditions is produced, and the relationship between the bonding condition and the bonding strength is examined. (1) Surface treatment step Here, plasma treatment is performed. The surface treatment of the bonding material is carried out. The plasma treatment is a treatment in which the surface of the resin is irradiated with a plasma such as an inert gas or oxygen generated under reduced pressure or atmospheric pressure to be surface-activated. Gas species and input electric power, the hydrophilicity of the treated surface (introduction of hydrophilic groups, hydrophobic groups), coarseness (concavity and convexity), and chemical activity change significantly. Before the step, a test for selecting the discharge gas to be used is performed. As the discharge gas to be used, one of oxygen, nitrogen, and argon is selected, and the hydrophilicity of the selected gas is investigated for each gas species. As a result of the chemical state, it was found that although hydrophilization can be achieved by plasma treatment using nitrogen gas or argon gas, the hydrophilicity using oxygen is optimal. Therefore, 099144806 Form No. 1010101 Page 15 / Total 51 Page 1003055875-0 201226510 [0073] [0073] 099144806 'This step uses oxygen to perform surface treatment. As the electropolymerization treatment apparatus, a SAMc® dry cleaning machine (Piasma Dry Cleaner) M〇dei pc_3〇〇 was used. (1.1) Surface Hydrophilization Treatment of Polycycloolefin (ZE0N0R) A polycycloolefin (ze〇n〇r) ′ composed of a cyclic smoky polymer is a polymer mainly composed of a C-H bond. The surface energy of the C-fluorenyl group is 20 to 4 Å mN/m, and the contact angle with respect to water is about 90 degrees. In order to hydrophilize the polycycloolefin (ZE〇N〇R), an oxygen plasma is applied; and the hydrophilic group is introduced to the surface of the polyene olefin (ZEONOR). In Fig. 1, the change in contact angle by oxygen plasma treatment on the surface of polycycloolefin CZEONOR) is shown. Further, Fig. 2 shows the results of X-ray photoelectron analysis (XPS) of the state of the surface C of the polycycloolefin (ZEONOR) which was changed by the oxygen plasma treatment. In Fig. 2, the thick line shows the unprocessed state; the other line shows the results of the surface treatment after changing the voltage and processing time. From Fig. 1, it is found that the contact angle of the surface of the polycycloolefin (ZEONOR) is reduced by the oxygen plasma treatment, and the hydrophilicity is improved. Further, from the second drawing, it is known that, by the surface treatment, in addition to the hydrophobic groups, i.e., the C-C and C-H bonds, the new hydrophilic groups -OH, =C0, -C00H, and the like appear. (12) Surface treatment of polyvinyl alcohol-based film Since the PVA film is structurally having a 〇H group in the main body, it has been rendered hydrophilic on the surface untreated state. Therefore, the surface treatment of the PVA film is carried out by removing particulate grease and contamination adhering to the surface of the film as an incidental purpose. Form bat number A0101 Page 16 of 51 page 1〇〇 (201226510 [0074] In Fig. 3, the X-ray photoelectron analysis (XPS) result of the state of the surface C of the pv A film which is changed due to the treatment of the sputum is displayed. In the same manner as in Fig. 2, it was found that a new hydrophilic group = CO, -COOH, etc. [0075] (1. 3) Measurement of surface roughness and mass after oxygen plasma treatment The above polycycloolefin was determined. (ZEONOR) and surface roughness Ra after surface treatment of PVA film. Surface roughness Ra was measured by KEYENCE VN-8010 atomic force microscope (AFM), and the surface was scanned to measure the unevenness and calculate the average Ra value. The surface roughness Ra of olefin (ZEONOR) is all

The sample to be produced was about 1 nm, and the surface roughness Ra of the PVA film was varied from 5 to 20: n: m. Further, the total mass after the surface treatment of the polycycloolefin (ZEONOR) and the PVA film group constituting the bonded structure was measured for each manufactured sample. (2) a bonding medium layer forming step of forming a bonding medium layer (a water vapor gas adsorption layer, a polycycloolefin (ZEONOR) and a surface of a PVA film which are hydrophilized by the surface treatment to adsorb a water vapor gas, A film of water, hereinafter also referred to as a water film). [0078] The formation of the bonding medium layer can use a mist atomizer or an ultrasonic humidifier or the like, but in the present embodiment, an ultrasonic humidifier (TUH-A10) is used. ) to spray the steam gas. Since the joint surface has been hydrophilized, the atomized water vapor gas can be made thin and uniformly adsorbed on the surface. Further, in the present embodiment, the amount of the water vapor gas adsorbed on the surface is varied in a variety of ways for each sample to be produced. [0080] (3) Clamping step 099144806 Form No. A0101 Page 17 of 51 1003055875-0 201226510 [0083] [0083] 099144806 After the above-described bonding dielectric layer forming step, in order to uniformly cover with a water film The surface of the PVA film and the polycycloolefin (ZEONOR) are brought close to each other by the surface tension of the water film when they are superimposed, and the PVA film and the polycycloolefin are made by further rolling with a roll. (ZEONOR) The surface is closer. In the present embodiment, the hand roller was processed by ARUART Co., Ltd. and the PVA film and the polycycloolefin (ZE0N0IO were pinched at a pressure of 10 Kg/cm2. Further, the mass after the pinch was measured (polyoxene (ZEONOR)) The mass of the PVA film and the water film was compared with the mass measured after the surface treatment step, and the mass of the water film present between the joint surface of the PVA film and the polycycloolefin (ZEONOR) was calculated from the amount of increase in mass. Since the thickness of the bonding dielectric layer is proportional to the mass thereof, the thickness can be measured by measuring the mass. Further, the number and time of using the hand roller described above are changed to adjust the water content S of the average unit area of the bonding surface to 〇. .1 g/cm2, ο ι〗 g/cm2, 0. 14 g/cm2. -·:-- . . . . . , .:. ....* (4) Joining step by In the above-described nip step, the PVA film and the polycycloolefin (ZEONOR) which are passed through the extremely thin water film are joined by a low-temperature heat treatment. Here, the manufactured sample is allowed to stand in a thermostat adjusted to a predetermined temperature. The temperature of the heat treatment is 50., 8 (rc, 1 〇 (either rc, χ, during heat treatment) The bonding was performed for any of 1 minute, 5 minutes, and 1 minute. [Performance Evaluation (Example 1)] The bonding strength of the bonded structure produced was measured using a peeling measuring device. The bonding conditions and the bonding strength evaluation results are shown in Table 1. The bonding strength evaluation was carried out in four stages in accordance with the peeling force of the PVA film 'polycycloolefin form number A0101 page 18/51 page 1003055875-0 201226510 (ZEONOR) interface. In addition, the bonding strength was also evaluated at the same time as the surface treatment step (marked as untreated) and the bonding medium layer forming step (labeled as natural adsorption) was not performed. [0084] In the table, the thickness of the bonding dielectric layer was evaluated. Set the water content S[mg/Cm2] of the average unit area of the joint surface as the reference, and set it as "medium" when S=0. g/cm2 is set to "small" and 'S=0.12/Cm2. When S = 0.14 g/cm2, it is set to be "large." Further, the evaluation criteria of the joint strength are "4" (&lt;〇.〇〇1 Kg/mm2), and "3" (0.001 to 〇.〇1 Kg/nun2) ), "2" (〇〇ι ~〇·1 Kg/mm2), "l" (〇.i Kg/mm2~). The numerical value of the strength evaluation is as small as possible. In the case of "1", the joint strength is the highest, and the order of high joint strength is [2], [3], [0085] [Table 1] Treat plasma treatment conditions to treat 〇A: polycycloolefin (ZEONOR)

B : PVA 100 W 5 pure 100 W 10 minutes bonding medium layer thickness natural adsorption small small natural small medium large natural adsorption small medium large

[0086] As shown in Table 1, '80 is performed in the joining step. When (: or l〇〇°c is heated, high joint strength can be obtained. Especially in the case where the thickness of the joint dielectric layer is small or medium, high joint strength can be obtained by a short-time low-temperature heat treatment. 099144806 Form No. A0101 Page 19 of 51 1003055875-0 201226510 [0087] Further, the surface treatment of the oxygen plasma is not able to obtain high joint strength regardless of the bonding conditions. This is considered to be because of the untreated polycycloolefin (ZE0N0R). The surface is hydrophobic and a sufficient bonding area cannot be obtained. [Example 2] In the present example, the above polycycloolefin (ZEONOR) and the above pva film were used as a bonding material, and were produced in accordance with the following procedures. (1) Surface treatment step Here, the same treatment as the surface treatment step of Example 1 was carried out. The plasma treatment conditions were 100 W for 10 minutes. [0090] (2) Bonding medium Layer forming step Here, the surface-treated polycycloolefin (ZEONOR) and PVA film were allowed to stand in a constant temperature and humidity chamber at 3 ° C and a humidity of 80% for 1 hour. [0091] (3) Clamping step; [.:::] This is the same as the cooling step of the embodiment 1. [0092] (4) Joining step): , i:: Here, the bonding with the embodiment 1 is performed. The procedure was carried out in the same manner, and the polycycloolefin (ZE〇N〇R) and the pVA film which were brought close by the above-mentioned nip step were heat-treated at 40 ° C for 30 minutes to be joined. 099144806 [Comparative Example 1] In the present comparative example, the above-mentioned polycycloolefin (ZE〇N〇R) and the above PVA film were used as a bonding material. Basically, the same procedure as in Example 2 was used to produce a joint structure. However, the temperature of the constant temperature and humidity chamber in which the dielectric layer was formed was set to 30 ° C and the humidity was set to 3 %. Form No. A0101 Page 20/51 Page 1〇〇201226510 [Performance Evaluation (Example 2 and Comparative Example 1)] The bonding strength of the polycycloolefin (ZE0N0R) and the PVA film of Example 2 was "1". (0. 1 Kg/mm2~). On the other hand, the ZEONOR and PVA film of Comparative Example 1 could not be joined. [Jointing of a hydrocarbon polymer film, polyethylene terephthalate, and glass] [Example 3]

In the present embodiment, a cycloolefin polymer film (polycycloolefin (N R N 0 R)) and a polyethylene terephthalate tablet (manufactured by Toray Co., Ltd., hereinafter also referred to as PET sheet) are used as the film. The bonding material is joined to form a bonded structure. Further, in the following embodiment, the term "PET sheet" means the PET sheet. In the production of the joined structure, the same manufacturing method as in the above-described first embodiment is basically employed. The electropolymerization treatment in the surface treatment step was 1 〇〇W, 10 minutes' and the heat treatment temperature in the joining step was 80 ° C, and the heat treatment time was 10 minutes. Further, the surface roughness Ra after the surface treatment was 1 nm for the polycycloolefin (ZE0N0R) and 1 nm for the PET sheet. :.

[_] [Example 4] In this example, a bonded structure was formed using a polycycloolefin (ZEONOR) and glass as a bonding material ′ and using the same manufacturing method as in the above-described Example 3. The glass system was EAGLE2000 GLASS manufactured by Furuchi Chemical. Moreover, in the following examples, the term "glass" refers to the glass. 5纳米。 [0099] The surface roughness of the surface of the polycyclic olefin (ZEONOR) was 1 nm, the glass was 0. 5 nm. [Example 5] 099144806 S single number A0101 page 21/51 page 1003055875-0 201226510 In this example, two sheets of polycycloolefin (ZE0N0R) were used as a bonding material, and the same as in the above-described Example 3 was used. Manufacturing Method to Form Joint Structure 〇 [0101] Further, the surface roughness Ra of each of the surface-treated polycycloolefins (ZE0N0R) was 1 nm. [Embodiment 6] In this embodiment, a PET sheet and glass were used as a bonding material to form a joined structure. [0103] The manufacturing method of the joined structure basically uses the same manufacturing method as that of the above-described first embodiment. The plasma treatment strip in the surface treatment step was 50 W for 10 minutes, and the heat treatment temperature in the joining step was 80 ° C, and the heat treatment time was 10 minutes. Further, the surface roughness of the surface-treated Ra-based PET sheet was 1 nm, and the glass was 0.5 nm. [Example 7] This example was a PET sheet and a polycycloolefin (ZE0N0R). The bonded structure was joined and the joint structure was formed using the same manufacturing method as in the above-described Example 6. Further, the surface roughness Ra after the surface treatment was 1 nm for the PET sheet, and the polycycloolefin (ZE0N0R) was 1 nra. [Embodiment 8] In this embodiment, two sheets of PET sheets were used as a bonding material, and a bonding structure was formed using the same manufacturing method as in the above-described Example 6. 099144806 Form No. A0101 Page 22 of 51 1003055875-0 201226510 [0108] Further, the surface roughness Ra of each of the PET sheets after the surface treatment was 1 nm. [Example 9] In this example, a bonded structure was formed using glass and polycycloolefin (ZEONOR) as a bonding material. The manufacturing method of the joined structure basically uses the same manufacturing method as that of the above-described first embodiment. The plasma treatment strip in the surface treatment step was 300 W for 2 minutes, and the heat treatment temperature in the joining step was 80 ° C, and the heat treatment time was 10 minutes. Further, the surface roughness Ra-based glass after the surface treatment was 0.5 nm, and the polyene olefin (ZEONOR) was 0.5 nm. [Example 10] In this example, a glass and a PET sheet were used as a bonding material, and a bonding structure was formed using the same manufacturing method as in the above-described Example 9. 5微米。 The surface of the surface of the film is 0. 5 nm. [Example 11] In this example, two sheets of glass were used as a bonding material, and a bonding structure was formed using the same manufacturing method as in the above-described Example 9. 5纳米。 The surface roughness of the surface roughness Ra is 0. 5 nm. [Performance Evaluation (Examples 3 to 11)] The bonding conditions and the bonding strength evaluation results of the bonded structures produced in Examples 3 to 11 are shown in Table 2. 099144806 In the table, the thickness of the joined structure is the table number of the average unit area of the joint surface A0101 page 23 / 51 page 1003055875-0 [0117] 201226510 The water content S [mg / cin2] is used as the base ' s = 〇. When 1 g/cm2 is set to "small" 'S = 0. 12/cm2 is set to "medium", and when s = 14 g/cm2 is set to "large". In addition, the evaluation criteria of the joint strength are r 4 (<0.001 Kg/mm2), "3" (0.〇〇1 to 〇〇iKg/mni2), "2" (0.01 to 0.1 Kg/mm2), "l (〇.iKg/_2~). [Table 2] Example A/B-based plasma treatment conditions Bonded dielectric layer thickness Bonding conditions Bonding strength AB Power CW) Time (minutes) Temperature CC) Time 贲 Example 3 Polycyclic smoke (ZEONOR) PET sheet 100 10 contends 80 10 2 Example 4 螭 100 100 10 80 10 2 Example 5 ZEONOR 100 10 80 10 3 Example 6 PET rupture 50 10 Medium ~ Large 80 10 1 Example 7 Polycycloolefin (ZEONOR) 50 10 Medium ~ Large 80 10 2 Implementation 刿 8 PET sheet 50 10 medium ~ large 80 10 1 Example 9 瑀ON olefin (ZEONOR) 300 2 small 80 10 2 Example Ϊ0 PET sheet 300 2 small 80 10 1 Example 11 Breaking 300 2 Small 80 10 3 [0119] As shown in Table 2, all the bonding systems of Examples 3 to 1 can be realized; ::: : Bonding. In particular, a polycycloolefin (ZEOfiOR)-PET sheet, a polycycloolefin (ZE0N0R)-glass, a PET sheet-glass, a PET sheet-PET sheet, etc., can be manufactured to have a strength of 0.01 Kg/mm2 or more. Joint structure of joint strength. [Example 12] In this example, the above-mentioned polycycloolefin (ZENOS) and the above-mentioned glass were used as a bonding material, and the bonded structure was produced in accordance with the following procedure. (1) Surface treatment step The surface of the polycycloolefin (ZE0N0R) was subjected to atmospheric corona discharge treatment (300 W/V, 10 to 20 seconds). Surface Roughness of Polycycloolefin (ZE0N0R) Ra 099144806 Form No. A0101 Page 24 of 51 1003055875-0 201226510 By the surface treatment, the % is again 1 nm to 1 〇 nm. 5 minutes). Glass and oxygen on the glass surface ♦

Ding Wei plasma treatment (100 wW

[0122] The surface roughness Ra of the glass is 〇5, and the total mass after the surface treatment of each of the touch test (four) (ΖΕ_) and the glass group (2) the bonding medium layer forming step is here/ The bonding medium layer forming step of Example 1 was carried out in the same manner. (3) Pinching Step Here, the same treatment as the nip step of Example 1 was carried out. Further, the mass after the nip (polycycloolefin (z_〇R), the mass of the glass and the water film) was measured and compared with the mass measured after the above surface treatment step, and the bonding medium was measured from the amount of increase in mass. Thickness of layer (average water content per unit area) (4) Joining step Here, the same treatment as that of the bonding step of Example 1 is performed, and the poly ring which is close by the above-described nip step is used. The thin smoke (ZE0N0R) and the glass were bonded at 10 (TC for 5 minutes for heat treatment. [Performance evaluation (Example 12)] The bonding strength of the polycycloolefin (ZEONOR) to the glass was 0.1 g of the thickness of the bonding medium layer. /cm2, 0.12 g/cm2 is "1" (〇.1 Kg/mm2~), 0.14§/(^2 is "2" (〇.01~0.11^/咖2~). Also, when bonding When the thickness of the dielectric layer is 0.14 g/cin2, the bonding strength is [1] when the bonding treatment (heat treatment) is performed for 30 minutes. 099144806 Form No. A0101 25 Buy/Total 51 Page 1003055875-0 201226510 [0126] Further, the bonded structures were immersed in 6 (the warm water of TC for 4 hours, and the thickness of the bonding medium layer was 0.1 g/cm. 2, 〇12 g/cm2, the thickness of the bonding medium layer is 0.14 g/cm2, and the heat treatment which is carried out for 3 〇 minutes is difficult to peel off and the stable bonding can be maintained. [0127] Further, the atmosphere is not carried out. In the corona discharge treatment, the polyoxyalkylene (ZEONOR) and the ruthenium which were subjected to the usual oxygen plasma treatment were joined, and the joint strength was changed to "1" when the joint method was used in the same manner as in Example 12. When the system was impregnated with warm water at 60 ° C for 30 minutes, the joint strength was lowered. [0128] After the atmospheric corona discharge treatment was performed to increase the surface roughness, the peeling resistance to the thermal stress was changed by the long-time heat treatment. [Example 13] In the present example, a cycloolefin polymer film (COP), that is, a polycycloolefin (ZE0N0R) (manufactured by Nippon Co., Ltd.) was selected as an example of a bonded structure, and the glass was bonded to the glass. [_] (1) Surface treatment step Here, the surface treatment of the bonding material is performed by corona plasma (electrication per treatment), specifically at atmospheric pressure to the metal electrode and the dielectric body. Apply high pressure and will The corona plasma generated by the irradiation is irradiated onto the surface of the resin and the surface to be broken, and the surface is activated. [0131] The corona plasma treatment member under atmospheric pressure is as follows. Corona treatment machine: spring 曰Large linear corona treatment experimental device for motor. Processing conditions: output power 150 W, scanning speed 〇.5 m/min, electrode 'substrate distance 1 mm and 'plasma irradiation power (discharge energy [KJ/m2] system output Power and sweep 099144806 Form No. A0101 Page 26 of 51 1003055875-0 201226510 [0132] [0133] [0135] [0136] The speed is calculated. (1. 1) Surface hydrophilization treatment of polycycloolefin (ZEONOR) A polycycloolefin (ZEONOR) composed of a cycloolefin polymer is a polymer mainly composed of a C-H bond. The surface energy of the c-H bond is 20 to 40 mN/m, and the contact angle with water is hydrophobic to exhibit about 9 degrees. In order to make the polycycloolefin (ZEONOR) hydrophilic, an atmospheric piezoelectric corona treatment is carried out to introduce a hydrophilic group to the surface of a polycycloolefin (ZEONOR). Fig. 4 shows the relationship between the contact angle of the surface and the discharge energy of the corona plasma treatment. Further, in Fig. 5, the change of the C functional group component on the surface of the polycycloolefin (ZE0N0R) which is changed by the atmospheric piezoelectric corona treatment is shown. The functional group component of C was determined in the same manner as in Example 1 (Fig. 2) from X-ray photoelectron analysis (xps). w From Fig. 4, it is found that the contact angle of the surface of the polycycloolefin (ZE0N0R) is reduced and the hydrophilicity is improved by corona plasma treatment. When the discharge energy to be irradiated exceeds a certain value, the contact angle of the polycycloolefin becomes constant near 40°. Further, from Fig. 5, it is known that by surface treatment, in addition to the CC and C-Η bonds of the hydrophobic group, the new hydrophilic groups 〇H, C=0, -(:〇3, etc. appear. The corona plasma was irradiated with a discharge energy of 15 kJ/m 2 , and the contact angle of the polycycloolefin (ZE0N0R) was set to about 40° ^ (1.2) The hydrophilicity change of the glass surface to the water contact angle of the glass surface The relationship with the corona plasma treatment discharge energy is shown in Fig. 6. It is found that as the treatment energy increases, the contact angle of the glass surface decreases sharply, and becomes the contact angle 5. The super-hydrophilic 099144806 form number A0101 Page 27 of 51 1003055875-0 201226510 State [0138] [0140] [0140] This κ example uses a discharge energy of 15 kj/m2 to illuminate the corona plasma, and the glass is The contact angle was set to about 5. (1. 3) The surface roughness of the surface of the atmospheric corona plasma treatment surface was measured. The surface roughness of the surface of the above polycycloolefin (ZEONOR) and glass after surface treatment was measured. The Ra system uses a KEYENCE VN-8010 atomic force microscope (AFM) to scan the surface and measure the unevenness and calculate The average "value. As a result, the surface roughness of the polycycloolefin (ZE0N0R) was about 1 run for all the manufactured samples, and the surface roughness Ra of the glass was 〇.1 nm. (2) Bonding dielectric layer forming step The surface of the polycycloolefin (ZEONOR) and the glass which have been hydrophilized by the above surface treatment is coated with an organometallic compound as a bonding medium layer. In this embodiment, a decane coupling agent is used as the organometallic compound. The decane coupling agent is composed of an organic substance and a compound composed of ruthenium and having a reactive bond with an inorganic material (glass, ceramic, genus, etc.) in a molecular structure, and an organic material (ethylene, epoxy, methacrylic acid) , a hydrogenthio group, an olefin group, etc.) two or more different reactive groups which are chemically bonded to a reactive group. Therefore, a bonding agent which is a combination of an organic material and an inorganic material is widely used, and the organic material is usually combined with an inorganic material. It is difficult to use. The used sulphur coupling agent is 3-aminopropyltrimethoxy sulphate (KBM903, manufactured by Shin-Etsu Chemical Co., Ltd.) and 3-glycidoxypropyltrimethoxy Alkane (KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.) The detailed molecular structure of these decane coupling agents is shown in Table 3. 099144806 Form nickname A0101 Page 28/51 Page 1003055875-0 201226510 [0141] [Table 3] KB surface 3 (信信化*工黧 KBM«3t信越化摩工|制制) 3-ammonium propyl trimethyl sulfonate: 3-glycidoxypropyltrimethyl decane (CH30) 3SiC3HeNH2 /〇\ (CH3 〇) 3SiC3H6OCH2CH CK2 [0143] 〇 [0144] The decane coupling agent-OCHQ, -0 (: 9 Ης, -OCOCH, etc., the hydrolyzable 〇L b 3 group is hydrolyzed to become a stanol (Si- OH) and partial condensation to form a decane oligomer, and hydrogen-bonded to the surface of the inorganic substrate, and a strong O-Si-Ο covalent bond is formed by a subsequent dehydration condensation reaction. On the other hand, the reaction and interaction with the organic substrate have a reaction with a side chain or a terminal functional group (amine group, epoxy group, mercaptopropenyl group, vinyl group, hydrogenthio group, etc.) of the organic material, and A mechanism for linking a branch polymerization reaction, a co-reaction, a mutual dissolution of an organic material, and mutual penetration. The decane coupling coating treatment of the glass-treated and polycycloolefin (ZE0N0R) surface which was hydrophilized in the above surface treatment step was carried out in accordance with the following procedure. The hydrophilized glass substrate was exposed to fog; the decane coupling agent (KBM903) after evaporation was vaporized for 30 minutes. Specifically, a dissocial coupling agent (liquid) is added to the bottom of the sealed glass container, and the glass substrate is placed on a mesh plate and sealed. Further, the surface-treated polycycloolefin (ZE0N0R) film was exposed to a decane coupling agent (KBM403) vapor for 30 minutes using the same method. It is considered that the film thickness of the organic decane coupling film adsorbed on the glass and the polycycloolefin (ZE0N0R) by the exposure is 2 nra or less (A. Hozumi, K, Uchiyaraa, H. Sugimura and 0. Takai, Langmuir 15, 7600 (1999)). 099144806 Form No. A0101 Page 29/51 Page 1003055875-0 201226510 [3] Pinching step (hot press bonding step) This embodiment is previously subjected to heat treatment in the joining step described later, and the manufacturing sample is prepared. The pinch pressure is simultaneously subjected to heat treatment (heating and pressure bonding). The glass and the polycycloolefin (ZEONOR) coated with the decane coupling agent were subjected to pressure-bonding using an electric heating press by the above-mentioned bonding medium layer forming step. The joining conditions were a temperature of 130 ° C, a pressure of 6 MPa, and a time of 5 minutes. [0147] Further, it is considered that the corona plasma treatment surface of glass and polyoxane (ZEONOR) adsorbs water vapor in the atmosphere, and by the water vapor, the decane coupling agent is hydrolyzed and the formation of stanol is slowly formed. The β is considered to be a covalent bond by the dehydration condensation reaction of the bonding medium layer forming step [0148] and the water vapor adsorption in the corona plasma treatment surface is in addition to the natural adsorption from the gas phase. It is possible to use a mist atomizer, an ultrasonic humidifier, etc. [0149] (4) Joining step (heating step) bonding of the glass and polycycloolefin (ZE〇N〇R) subjected to the above-mentioned thermocompression bonding stepping The body is further heat treated to form a more reliable bonding state. Here, the production sample of the glass and the polycycloolefin (ZE〇N〇R) (the joint structure before the completion of all the steps, in the same manner as in the other examples) was allowed to stand at a temperature of 13 预先 in advance. 〇c in the thermostatic bath for 5 minutes. [0150] By the above steps, a bonded structure composed of glass and polycycloolefin (ZEONOR) was produced. [Embodiment 14] This embodiment is a step of forming a bonding dielectric layer, which is only covered with glass 099144806 1003055875-0 Form No. A0101 Page 30 / 51 pages [0151] 201226510 ΚΒΜ 903, and no polycycloolefin (ZEONOR) is carried out. The bonded structure was produced basically using the same bonding material and procedure as in Example 13 except that the coating agent was coated. [Example 15] In this example, a bonded structure composed of glass and polycycloolefin (ZEONOR) was produced. (1) Surface treatment step Polycycloolefin (ZEONOR) was subjected to surface treatment using the same atmospheric piezoelectric halo plasma treatment as in Example 13, and the surface contact angle was set to about 40. 〇 ..... a ... [0154] The glass is treated with an atmospheric pressure photo-plasma treatment for surface treatment. The plasma treatment conditions are as follows. Plasma processor: SAMCO Plasma Dry Cleaner Model PC-300. Processing conditions: discharge gas N2220 L / min, power 150 kw, conveying speed 1. 5 m / min x 2, electrode-substrate spacing 2 mm.使用 [0155] The contact angle of the glass is about 5 使用 using the atmospheric pressure glow plasma treatment described above. (2) Bonding dielectric layer forming step In the present embodiment, the surface is treated in the same manner as in the embodiment 13. The glass substrate was exposed to vaporized decane coupling agent (KBM903) for 15 minutes. Again, the surface treated polycycloolefin (ZEONOR) film was exposed to a decane coupling agent (KBM403) vapor for 15 minutes. [0157] (3) Clamping step 099144806 Table Cui number A0101 Page 31 of 51 1003055875-0 201226510 Dust and polycycloolefin (ZE0N0R) formed by coating the decane coupling agent by the above-mentioned bonding dielectric layer forming step Under a reduced pressure atmosphere (about 500 T rr) and at room temperature (25 ° C), a hand roller manufactured by ALUART Processing Co., Ltd. was used and crimped at a pressure of 10 Kg/cm 2 . (4) Joining step (heating step) The joined body of the glass and the polycycloolefin (ZEONOR) subjected to the above-described nip step is further subjected to heat treatment to form a more reliable bonding state. Here, a sample of the glass and a polycycloolefin (ZEONOR) was allowed to stand in a thermostat previously adjusted to a temperature of 130 ° C for 3 minutes. C〇159] A bonded structure composed of glass and polycycloolefin (ZEONOR) was produced by the above procedure. [Embodiment 16] This embodiment is a step of forming a bonding dielectric layer, and is basically used and implemented only in the case where the glass is coated with KBM903' and the point where the polycycloolefin (ZEONOR) is coated with the decane coupling agent is not used. The joining material was produced in the same bonding material and procedure as in Example 15. [Example 17] This example is in the step of joining the medium (4), except that the glass is coated with KBM4〇3, and the point where the EOONOR is coated with the decane coupling agent is not used. The bonding material and the procedure of Example 15 were used to produce a bonded structure. [Example 18] In this example, a joint structure composed of smear n &amp; ming and polycycloolefin (ZEONOR) was produced. 099144806 Form No. A0101 Page 32 of 51 1003055875-0 201226510 [0164] 016 [0167] (1) Surface treatment step Polycyclic olefin (ZEONOR) and glass system use and implementation Example 13 The same atmospheric piezoelectric corona treatment was used for surface treatment, and the contact angle of the polycycloolefin (ZENOS) was set to about 40 and the contact angle of the glass was set to about 5. . (2) Bonding Dielectric Layer Forming Step In the present example, the surface-treated glass substrate was exposed to vaporized decane coupling agent (KBM903) vapor for 15 minutes in the same manner as in Example 13, and the surface-treated The polycycloolefin (ZEONOR) membrane was exposed to a vapor of decane coupling agent (KBM403) for 15 minutes. (3) The nip process is a glass and a polycycloolefin (ZEONOR) obtained by coating a decane coupling agent by the above-mentioned bonding medium layer forming step, at atmospheric pressure (about 760 Torr), and at room temperature (25 ° C). The hand roller was manufactured by ALUART Processing Co., Ltd. and was brought to the house at a pressure of 10 kg/cm2. Is: ^ - I %:. -:5:: ¢: %: I (4) Joining step (heating step) Heat the bonded body of glass and polycycloolefin (ZEONOR) subjected to the above nip step To form a more realistic state of bonding. Here, a sample of the glass and a polycycloolefin (ZEONOR) was allowed to stand in a thermostat previously adjusted to a temperature of 130 ° C for 10 minutes. By the above steps, a bonded structure composed of glass and polycycloolefin (ZEONOR) was produced. [Embodiment 19] This embodiment is a step of forming a bonding dielectric layer, which is only covered with glass 099144806 Form No. A0101 Page 33 / Total 51 Page 1003055875-0 [0168] 201226510 KBM903 'and no polycycloolefin (ZE0N0R) The joint structure was produced by basically using the same bonding material and procedure as in Example 18 except that the decane coupling agent was coated. [01δ9] [Example 20] This example is basically the same bonding material as that of Example 18 except that the glass and the polycycloolefin (ZEONOR) were coated with the decane coupling agent in the step of forming the bonding medium layer. And a step to produce a joined structure [Example 17] [Example 21] In this example, a joined structure composed of glass and polycycloolefin (ΖΕ 0Ν0 R) was produced. (1) Surface treatment step Glass and polycycloolefin (ZEONOR) were subjected to surface treatment using a reduced pressure photovoltaic slurry treatment. The plasma treatment conditions are as follows. Plasma processor: SAMC0 plasma dry cleaner Model PC-300 Discharge gas: N2 '220 L/min Output power (glass): 300W, containing #^ Output power (polycycloolefin (ZE0N0R)): 100 W The pressure-reducing photovoltaic slurry treatment was carried out for 10 minutes, and the contact angle of the surface of the polycycloolefin (ZE〇N〇R) was 40. And the contact angle of the glass surface was set to about 5. . (2) Bonding dielectric layer forming step The hydrophilized polycycloolefin (ZE〇N〇R) and the glass surface are adsorbed with a vapor gas by the surface treatment to form a bonded structure. Further, the adsorption of the vapor gas is naturally adsorbed at room temperature of 25 ° C and a humidity of 50%. Form No. A0101 Page 34 / Total 51 Page 1003055875-0 201226510 [0173] [0174] ❹ [0175] [0176] 实现 30 minutes to achieve. That is, this embodiment does not expose the decane coupling agent. (3) The nip step is to use a glass and a polycycloolefin (ZEONOR) obtained by adsorbing a vapor gas by the above-described bonding medium layer forming step, and is used in an atmosphere (about 760 Torr) at room temperature. ALUART Processing Co., Ltd. made a hand roller and clamped it with a force of 10 Kg/cm2. (4) Joining step (heating step) The joined body which has passed through the above-described nip step and is subjected to heat treatment to form a more reliable bonding state. Here, the production sample of glass and polycycloolefin (ZEONOR) was allowed to stand in a thermostatic chamber adjusted to a temperature of 80 ° C for 1 minute in advance. By the above steps, glass and polycyclic hydrocarbon were produced. (ZEONOR) The joint structure formed by (ZEONOR). [Embodiment 22] This embodiment was produced by using the same bonding material and procedure as in Example 2 except that the heat treatment was not performed in the joining step and the temperature was allowed to stand at room temperature for 30 minutes. 099144806 [Performance evaluation (Examples 13 to 22)] The joint strength of the joined structures produced in the above Examples 13 to 22 was measured using a peeling tester. The bonding conditions and bonding strength evaluation results are shown in Table 4. The joint strength was measured by both the person who did not perform the moisture resistance test and the one who performed the moisture resistance test. The Wet and Wet Test is allowed to stand in an environment with a temperature of 60T: and a humidity of 90%. Form No. A0101 Page 35 of 51 1003055875-0 [0178] 201226510 4 7 0 hours. The test for the moisture resistance test was allowed to stand for 470 hours in an environment of a temperature of 25 ° C and a humidity of 50%. . The evaluation criteria of the joint strength are "4" (&lt;0.001 Kg/mm2)' "3" (0.001 to 〇.〇1 Kg/mm2), "2" (0.01 to 0.1 Kg/mm2), and "1" (〇) . [Kg/mm2~). [Table 4] Example joint surface treatment 矽 偶 coupling agent exposure condition bonding method (pressure loss step field 〇 heat treatment (joining step) joint strength glass poly. cycloolefin (ZEONOR) carbene polycycloolefin (2EONOR1 251) , 50% 60t, 90% Example 13 Atmospheric Piezoelectric Plasma Treatment of Atmospheric Electroacoustic Electric Oscillator « KBM903 KBM403 Atmospheric Thermal Power Fit 1 Grab, 5 Minutes 1 1 Example 14 Atmosphere "Electrical Plasma Treatment of Atmosphere* Corona "Processing KB\©03 No atmospheric thermoelectric bonding 130*t, 5 minutes 镔 1 1 Example 15 Atmospheric glow plasma treatment atmosphere * Electricity most t «Processing KBM903 KBM403 Decompression mixing 130X:, 3 cents 1 1 贲 Example 16 Atmospheric pressure glow paste treatment too pressure corona plasma treatment KBM903 no decompression fit 13 (TC, 3 minutes 锸 1 4 Example 17 atmospheric pressure glow paste treatment atmosphere 魇 electricity _ slurry treatment KBM403 no decompression Lamination 130 ° C, 10 minutes 铕 1 4 Example 18 Atmospheric Piezoelectric 荤 Plasma Treatment Atmosphere * Electric 翚 Plasma Treatment KBM9Q3 KBM403 Atmospheric Fit 130 Ϊ;, 10 DM 1 2 Example 19 Atmosphere * Electric * * Atmospheric piezoelectric翚 electric paddle treatment KBM903 no atmosphere fit i3tyc, ίο cents 1 2 Example 20 Atmospheric helium corona plasma treatment atmosphere * electric 翚 plasma treatment without air atmosphere 130 ° c ' 10 cents 1 4 Example 21 Reduction of Yinghui Photoelectric Pulp Treatment, Depressurization, Photoelectric Pulp Treatment, No Atmosphere Bonding, 80 °C, 10 Minutes, 1 4 Example 22 Laihui Photoelectric Pulp Treatment Subtracted “Glow Photoelectric Pulp Treatment Without Air Fit No 1~2 4 [ 0180] As shown in Table 4, the conditions of any of Examples 13 to 22 were able to bond a polycycloolefin (ZEONOR) to glass, and further, after 470 hours at a temperature of 25 ° C and a humidity of 50%. Further, the bonding strength was also shown. [0181] Further, from the evaluation results of Example 13 '14, it was found that a decane coupling agent was applied to both or one of glass or polycycloolefin (ZEONOR) and thermoelectric bonding was carried out. 099144806 Form No. A0101 36 pages/total 51 pages 1003055875-0 201226510 [0184] [0185] [0185] The joined structure is a joint strength of "1" and sufficient resistance even after the moisture resistance test. Wet. Further, it was found from the evaluation results of Example 15 that it was found that the glass coating agent (KBM903) was coated with a decane coupling agent (KBM403) in a polycycloolefin (ZEONOR) and the pressure was applied under reduced pressure. In addition, even after the moisture resistance test, the joint strength was "1" and the moisture resistance was sufficient. Further, from the evaluation results of Examples 17 and 18, it was found that when both of the glass and the ZEONOR were coated with the sulphur coupling agent and bonded at atmospheric pressure, the heat treatment was performed at 130 ° C. The joint structure formed in 1 minute is a joint strength of "2" after the dampness test, and has sufficient richness. ...Κ.. „ 1 Boxing-si ψ τ In addition, it is known that in the surface treatment step, the fatigue of any of the atmospheric piezoelectric corona plasma, the atmospheric pressure glow plasma paste, and the reduced pressure photovoltaic paste can be obtained. It is advantageous to be able to operate at atmospheric pressure when cooperating with the industry, and it is not necessary to form a decompression environment. Also, when thermoelectric bonding is carried out in the pinch step (pressure bonding using an electrothermal pressurizer) Further, in the case of Comparative Example 15 and Example 16 '17, it was found that the bonding strength was improved when the decane coupling agent was applied to both of the bonding materials. From these cases, the above Examples 13 to 22 were improved. In terms of joint strength and moisture resistance, the production conditions of Example 13 were optimized. That is, the bonding material was hydrophilized by using an atmospheric piezoelectric corona slurry and coated with KBM903 in a glass and in a polycycloolefin (ZEONOR). Coating KBM403, and clamping while maintaining the treated surface at 130 °C (hot pressing 099144806 Form No. A0101 Page 37/51 pages 1003055875-0 [0186] 201226510 Adhesive bonding), followed by heat treatment at 130 ° C , can [Effect of the Invention] According to the production method of the present invention, it is possible to join the various types of joints with high joint strength without using an adhesive. Further, since no adhesive is used. Therefore, deterioration of optical characteristics caused by the adhesive is not generated, and since bonding using heating of 130 ° C or less can be achieved, the bonding material for achieving bonding is not limited to a low softening point at low temperature softening, or It is a case where the optical properties of the bonding material are deteriorated by using a high temperature of more than 130 ° C. [0188] When a bonding medium layer is formed using a water vapor gas (water film), even when various thin film layers are multilayered, it is possible to borrow It is formed by optimizing the thickness of the bonding medium layer (water vapor gas adsorbing layer) suitable for each bonding system, and forming a bonding system by an interfacial reaction caused by low-temperature heat treatment of 100 ° C or lower. Further, the method of the present invention There is a degree of freedom in optimizing the thickness of the bonding dielectric layer in accordance with the state of the bonding surface. [0189] Moreover, the bonding step remains. The reaction product and the gas at the joint interface are small in amount when the dielectric layer is thin, and can be scattered to the outside of the bonding system in a short time after the bonding step. The adhesive coating method which is currently widely used because its thickness is 10 private m~50 μηι, it takes 10 hours to 20 hours to scatter a large amount of solvent and water contained in the adhesive agent to the outside of the bonding system, but consider the bonding medium layer (water vapor gas adsorption layer, water) of the present invention. When the film is 5 μm or less, the usefulness of the present invention and its effects can be clearly understood. 099144806 Form No. A0101 Page 38 of 51 1003055875-0 201226510 [0190] Further, the smaller the thickness of the bonding medium layer, the productivity The more you improve. On the other hand, the greater the thickness of the bonding dielectric layer, the stronger the thermal stress. Further, when the bonding medium layer is formed using a decane coupling agent, it is also possible to perform an appropriate bonding treatment such as heating and pressure bonding, applying a decane coupling agent to both of the bonding materials, and heat-treating at 130 ° C for 10 minutes or more. Make it highly rich in moisture. [Other Embodiments] In the above-described respective embodiments, the surface treatment step is exemplified by the configuration of the oxygen plasma treatment or the atmospheric corona discharge treatment, but a plasma other than oxygen may be used. Treatment, ozone treatment, irradiation electromagnetic wave treatment, and the like. Further, in the above-described bonding medium layer forming steps of the first to the twelfth embodiments, the bonding medium layer is formed on both surfaces of the two bonding materials. However, the bonding medium layer may be formed only on one surface. Further, in the above-described bonding medium layer forming steps of Examples 1 to 22, a configuration in which a bonding medium layer is formed using a steam gas or a decane coupling agent is exemplified, but it is also considered to be selected from hydrogen gas and alcohol gas. One or more types of hydrogen peroxide gas or a group of organometallic compounds are used instead of a vapor gas or a decane coupling agent to form a bonding medium layer. At this time, in the joining step, at the same time as or in place of the heat treatment, the joining of the respective joining materials can be realized by performing the electromagnetic wave (ultraviolet) treatment. In addition, when any of hydrogen gas, steam gas, alcohol gas, hydrogen peroxide gas, and decane coupling agent is used, when electromagnetic waves are irradiated, bonding can be favorably performed, and when an organic metal compound is used, electromagnetic waves are irradiated. At the time, the joining can be achieved well. Here, 099144806, Form No. A0101, Page 39 of 51, 1003055875-0 201226510, an organometallic compound is equivalent to an organometallic compound gas which is widely used when a film is formed by a chemical vapor deposition (CVD, Chemical Vapor Deposition). [0195] However, in Examples 1 to 12, the thickness of the above-mentioned bonding medium layer is important in forming the joint structure system of the present invention. In particular, the time required for the reaction in the bonding step and the time during which the unreacted gas, the gas generated by the reaction, and the like are excluded from the bonded structure to the outside of the system are remarkably the productivity of the left and right bonding processes, and it is necessary to control The full thickness is preferred. Further, the thickness of the joined structure is also preferably in consideration of the surface roughness of the joint surface. Further, the joined structure also has a function of absorbing the stress generated at the interface with the joining. Therefore, the thickness of the joined structure is preferably determined in consideration of the unevenness of the joint surface, the gentle absorption of the joint stress, and the productivity. Further, in Examples 1 to 12 and 15 to 22, the configuration in which the bonding material is sandwiched at a pressure of 10 Kg/cm 2 in the nip step is exemplified, but the pressure range is from 0.1 Kg/cm 2 to 100 Kg/cm 2 . Good results can be obtained. When the dielectric layer is a water film, the thickness can be adjusted by the pinching time and the number of times of pinching. Further, in each of the above-described embodiments, the surface treatment step is performed by an oxygen plasma treatment, an atmospheric corona discharge treatment, or the like. However, when the joint structure of the present invention is used, the joint material is used. In the case where the required properties (wetness, cleanliness, presence of a predetermined functional group, etc.) are required in advance, the bonding medium layer forming step can be carried out without performing the surface treatment step. 099144806 Form No. A0101 Page 40/51 Page 1003055875-0 201226510 [0198] Further, when the step of joining can be performed without the pinching step, or when the step of bringing the two joining materials by another method is performed, It is also possible not to perform the crimping step. In the case where the bonding state of the two bonding materials is high-sealing property (sealing property), it is possible to manufacture the bonding of the water vapor or the like which can be suppressed when the electronic component or the like is disposed between the two bonding materials. Construct. Further, in each of the above embodiments, the bonding material is heated (or not heated) in the bonding step and the nip step in the range of 50 ° C to 130 ° C, and the heating temperature may be 130 ° C or lower. The heating temperature at this time may be set to a temperature lower than the glass transition point of the resin material of the bonding material. For example, when a cycloolefin resin having a glass transition point of 160 ° C is used as the bonding material, it is preferably heated at 160 ° C or lower. BRIEF DESCRIPTION OF THE DRAWINGS [0201] Fig. 1 is a graph showing a change in contact angle by oxygen plasma treatment on a surface of a polycycloolefin (ZEONOR). Fig. 2 is a graph showing the results of X-ray photoelectron analysis (XPS) of the state of the polycyclic olefin q (ZEONOR) surface C which was changed by oxygen plasma treatment. Fig. 3 is a graph showing the results of X-ray photoelectron analysis (XPS) of the state of the surface C of the PVA which was changed by the oxygen plasma treatment. Figure 4 is a graph showing the relationship between the discharge energy of atmospheric piezoelectric corona treatment and the contact angle of a polycycloolefin (ZEONOR) surface. Fig. 5 is a graph showing the results of X-ray photoelectron analysis (XPS) of the state of the surface C of a polycycloolefin (ZEONOR) which was changed by atmospheric piezoelectric corona treatment. Figure 6 is a graph showing the relationship between the discharge energy of atmospheric piezoelectric corona treatment and the water contact angle of the glass surface. 099144806 Form No. A0101 Page 41 of 51 1003055875-0 201226510 [Description of main component symbols] [0202] None 099144806 Form No. A0101 Page 42 of 51 1003055875-0

Claims (1)

201226510 VII, Ο Patent application scope: • 2::: The manufacturing method of the creator's system--the two-joining material is joined and *weighed: the connection method = the manufacturing method' wherein the ～ 介 介 layer formation ==: step one At least one-way hydrogen of the bonding material: hydrogen, water vapor gas, alcohol gas, peroxometalloide compound, decane coupling _ above-bonding dielectric layer; and one of the group = 3 = The second material and the bonding medium layer transmit electromagnetic waves through the irradiation. I bonding material _, heating and / or = = =: 1 joint structure Zhao manufacturing method, which is composed of ten of the τ agent, and the joining step is in accordance with the second paragraph of the patent scope The manufacturer of the joined structure = the dielectric layer is exposed to the bonding material by the machine coupling vapor: as claimed in the patent scope! In the manufacturing method of the joint structure ship, the two joints (four) are all organic compounds, and the transition medium layer is composed of steam gas or an organometallic compound, and is heated (4). The transfer step is a method for producing a bonded structure according to item 4 of the patent application. The bonding material is a cycloolefin resin and a polyethylol alcohol tree. The method of manufacturing the joined structure of claim 1, wherein the two joining materials are selected from the group consisting of a cyclic olefin resin, poly, = 5 , such as 6. For example, 099144806, Form No. A0101, page 43 / 51 Page 1003055875-0 201226510 One or two types of groups of glass, the bonding medium layer is composed of steam gas, and the bonding step is a step of heating. The method of producing a joined structure according to any one of claims 1 to 6, wherein the heating temperature in the joining step is from 80 ° C to 130 ° C. 8. The method of manufacturing a joined structure according to claim 1, wherein the two joining materials are each an organic compound, and the joining medium layer is composed of an organometallic compound, and the joining step is performed. The step of illuminating electromagnetic waves. 9. The method of manufacturing a bonded structure according to claim 1, wherein the two bonding materials are an organic compound and glass, and the bonding medium layer is composed of steam gas or alcohol gas, and the bonding step is performed. The step of heating. 10. The method of manufacturing a bonded structure according to claim 1, wherein the two bonding materials are an organic compound and glass, and the bonding dielectric layer is composed of an organometallic compound, and the bonding step is performed by irradiating electromagnetic waves. step. The method of manufacturing a joined structure according to any one of claims 1 to 10, wherein a surface treatment step is provided prior to the step of forming the bonded dielectric layer, the surface treating step being performed to lift the two bonding materials A surface treatment of the wettability of at least one of the surfaces. The method of manufacturing a bonded structure according to claim 11, wherein the surface treating step is a step of performing any one of corona treatment, plasma treatment, ozone treatment, and irradiation electromagnetic wave treatment. 13. The method of producing a joined structure according to claim 11, wherein the surface treating step is a corona treatment, and the joining step is a step of heating for more than 35 minutes. The manufacturing method of the joined structure according to any one of the above claims, wherein the bonding medium layer forming step is provided with a clip after the bonding medium layer forming step, the method of manufacturing the bonded structure according to any one of claims 1 to 13 In the pressing step, the nip step is performed by sandwiching the two bonding materials in a state of being superposed by the bonding medium layer. The method of manufacturing a joined structure according to claim 14, wherein the clamping step is a step of heating while sandwiching the two joining materials. An engaging structure which is a joined structure obtained by joining one or two joining materials, wherein the two joining materials are joined by hydrogen bonding between surfaces or by covalent bonds of metal molecules. ❹ 099144806 Form number A0101 Page 45 of 51 1003055875-0