Manufacturing method for automotive window glass structure and evaluation method for dry processing

Abstract

To make it possible to evaluate dry processing of a resin surface of a component in a non-contact manner, in the production of an automotive window glass structure obtained by bonding the component having the resin surface to an automotive window glass.SOLUTION: In a method for producing an automotive window glass structure obtained by bonding a component having a resin surface to an automotive window glass, a fluorescent substance is attached to a bonding face of the component having the resin surface, the bonding face is subjected to dry processing, the dry processing is evaluated by observing the fluorescence emitted from the bonding face, and the component is bonded to the automotive window glass through an adhesive applied to the bonding face.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The present invention relates to a method for manufacturing an automotive window glass structure and a method for evaluating dry processing. [Background technology]

[0002] Structures are known in which a resin part, such as a bracket, is bonded to an automobile window glass via an adhesive. In the manufacture of such structures, it is also known to modify the bonding surface of the resin part by subjecting the bonding surface to a dry treatment, such as plasma treatment, in order to improve the adhesion between the resin part and the adhesive. For example, Patent Document 1 describes a surface treatment method for a component containing a crystalline thermoplastic resin, in which the surface state before and after the dry treatment satisfies a predetermined relationship based on the contact angle and the surface free energy of the surface. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-127428 Summary of the Invention [Problem to be solved by the invention]

[0004] In the technology described in Patent Document 1, dry treatments applied to component surfaces are evaluated by measuring the contact angle and surface tension of a specific liquid. However, since contact angle measurements involve dropping a liquid onto a surface, the surface condition of the component may change depending on the material that makes up the component and the type of liquid used for the measurement. Therefore, there is a need for a method that can appropriately evaluate dry treatments applied to bonding surfaces without contact.

[0005] In view of the above, one aspect of the present invention aims to provide a method for non-contact evaluation of the dry treatment of the resin surface of a part in the manufacture of an automotive window glass structure in which a part having a resin surface is bonded to an automotive window glass. [Means for solving the problem]

[0006] In order to solve the above problems, there is provided a method for manufacturing an automobile window glass structure in which a component having a resin surface is bonded to an automobile window glass, the method comprising: attaching a fluorescent substance to the bonding surface of the component having the resin surface; performing a dry treatment on the bonding surface; evaluating the dry treatment by observing the fluorescence emitted from the bonding surface; and bonding the component to the automobile window glass via the adhesive applied to the bonding surface. [Effects of the Invention]

[0007] According to one aspect of the present invention, in the production of an automobile window glass structure in which a component having a resin surface is bonded to an automobile window glass, the dry treatment of the resin surface of the component can be evaluated in a non-contact manner. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a plan view of an automotive glazing structure according to one embodiment of the present invention; [Figure 2] FIG. 2 is a partial cross-sectional view taken along line II in FIG. [Figure 3] FIG. 1 is a flow diagram of an evaluation method or a manufacturing method according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, embodiments for carrying out the present invention will be described, but the present invention is not limited to the following embodiments.

[0010] <Automotive window glass structure> In this specification, the term "automotive window glass structure" refers to a structure in which a component having a resin surface is bonded to a main surface of an automotive window glass with an adhesive. More specifically, the automotive window glass may be a windshield, rear glass, side glass, etc.

[0011] Glass sheets used for automotive window glass may be inorganic glass sheets such as soda-lime silicate glass, aluminosilicate glass, borate glass, lithium aluminosilicate glass, or borosilicate glass. The glass sheets may be untempered or may have been subjected to air-cooling or chemical strengthening treatment. Untempered glass is produced by forming molten glass into a plate shape and slowly cooling it. Tempered glass is produced by forming a compressive stress layer on the surface of untempered glass. When the tempered glass is air-cooled tempered glass, the glass surface may be strengthened by rapidly cooling a uniformly heated glass sheet from a temperature near its softening point, thereby generating compressive stress on the glass surface due to the temperature difference between the glass surface and the interior of the glass. On the other hand, when the tempered glass is chemically strengthened glass, the glass surface may be strengthened by generating compressive stress on the glass surface using an ion exchange method or the like. Furthermore, glass sheets that absorb ultraviolet or infrared rays may be used for vehicle glass. Furthermore, transparent glass is preferable, but colored glass may also be used to the extent that transparency is not impaired. Organic glass may also be used for vehicle glass. The organic glass may be a transparent resin such as polycarbonate.

[0012] The window glass for an automobile may be a laminated glass comprising a plurality of the above-mentioned glass plates, for example, a laminated glass comprising two glass plates bonded together via an interlayer film. Examples of the interlayer film disposed between the glass plates include ethylene vinyl acetal and polyvinyl butyral.

[0013] The planar shape of the automotive window glass is not limited to a rectangle, and it may be processed to have various shapes. Furthermore, the automotive window glass may be curved, and its curvature is not particularly limited. The curvature can be obtained by bending the glass sheet to be used by gravity forming, press forming, or the like. The shape and curvature of the automotive window glass are set so that components can be bonded to its main surface and sufficient dry processing can be performed on the bonding surface.

[0014] Specific examples of the structure in which a part having a resin surface is adhered to the above-mentioned automotive window glass include a structure in which a part such as a resin bracket or base for mounting on-board equipment (on-board camera, on-board sensor, mirror, etc.), or a resin temporary fixing pin, is adhered to the surface facing the interior of the vehicle when the windshield is installed in the vehicle. Also, the structure may be a structure in which a part such as a resin door slider or a resin door holder is adhered to the side glass. In this way, it is preferable that the part to be adhered to the automotive window glass has at least a plate-like portion to be adhered, and that the adhesive surface is formed to correspond to the shape of the adhesive surface of the main surface of the automotive window glass.

[0015] When the part having a resin surface is a part for mounting an on-vehicle device, the on-vehicle device that can be mounted may be an on-vehicle camera, a rain sensor, a defrost sensor, an infrared sensor, a millimeter-wave radar, etc. It may also be a resin base for mounting an interior mirror. The automotive window glass structure manufactured according to this embodiment is also suitable for use in automobiles equipped with a Driving Safety Support System (DSSS) or an Advanced Driver-Assistance System (ADAS).

[0016] The component to be attached to the automobile window glass may have a resin surface, i.e., at least the surface is formed from resin, or may be formed primarily from resin. Furthermore, the component may have a resin surface at least on the surface to be bonded to the automobile window glass. Therefore, a component having a resin surface may be a molded body formed entirely from resin or primarily from resin, or a molded body made from a material other than resin, the surface of which is partially or entirely coated with a resin layer. The phrase "mainly formed from resin" refers to a component containing resin in a proportion that maintains the inherent properties of the resin, e.g., a component containing 50% by weight or more of resin. In this specification, a component having a resin surface may also be referred to as a "resin component" or a "resin part."

[0017] Resin materials used for parts with resin surfaces are not particularly limited, but include polyesters such as polybutylene terephthalate (PBT) and polyethylene terephthalate (PET), polyolefins such as polyethylene (PE) and polypropylene (PP), polycarbonate (PC), polyamides (PA) such as nylon 6 and nylon 6,6, high-heat-resistant polyamides based on terephthalic acid or isophthalic acid (e.g., PA6T, PA6I, PA6T / 6I), polyimide (PI), polyetherimide (PEI), acrylonitrile-butadiene-styrene (ABS), polyacetal (POM), polyvinyl chloride (PVC), and epoxy (EP). These resin materials may be used as homopolymers or as copolymers formed by combining one or more of the above. Furthermore, the resin material may be a polymer alloy formed by combining one or more of the above, such as a polymer alloy of polybutylene terephthalate and styrene-acrylonitrile.

[0018] The resin material may also contain components other than the resin component, such as fillers, pigments, and resin modifiers. For example, the resin material may be a reinforced resin reinforced with fillers such as fibers and inorganic particles. Examples of reinforcing fibers include glass fiber and carbon fiber. Preferred fiber-reinforced resins are polybutylene terephthalate and polyetherimide reinforced with glass fiber. When the resin contains reinforcing fibers, the fibers may be contained in an amount of 5% by weight to 70% by weight, preferably 30% by weight to 50% by weight, based on the total weight of the resin.

[0019] When a part having a resin surface is a molded body molded entirely or mainly from resin, the molding method is not limited, and the above-mentioned resin material may be molded by a method such as injection molding, casting, extrusion, blow molding, etc. Also, it may be insert molded using an insert material made of a material other than resin (such as metal).

[0020] Furthermore, when the part having a resin surface is a molded body made of a material other than resin, the surface of which is partially or entirely coated with resin, it may be, for example, an electrodeposition-coated body obtained by electrodeposition-coating a substrate made of metal or the like with an electrodeposition paint containing a resin. The electrodeposition-coated body is formed by passing an electric current through an electrolytic bath to deposit resin paint particles on the surface of the part, and then heating and curing the resulting film in a curing oven. When the resin surface is formed by electrodeposition coating, the electrodeposition paint is preferably a cationic electrodeposition paint. Furthermore, the resin contained in the electrodeposition paint may be a thermosetting resin such as an epoxy resin, and preferably contains an epoxy resin modified with an amine, ammonium, or the like. Meanwhile, the substrate may be a metal molded body, particularly a plate-shaped molded body, made of steel, aluminum, or the like. An example of an electrodeposition-coated body is a cationic electrodeposition-coated steel plate manufactured by Aoki Electric Industrial Co., Ltd. (using Elecron HG-305E Black manufactured by Kansai Paint Co., Ltd. as the electrodeposition paint). The resin surface can also be formed by applying a solution or dispersion containing a resin, or a molten resin liquid, etc., onto the substrate, or by depositing a pre-formed sheet-like resin layer, or by electroless plating, etc. In the case of such a part whose surface is partially or entirely coated with resin, it is sufficient that at least a part of the surface to be bonded to the automotive window glass (bonding surface) is covered with the resin layer, and it is preferable that the entire bonding surface is covered with the resin layer.

[0021] FIG. 1 shows an example of an automobile window glass structure 1 formed by bonding an automobile window glass to a component having a resin surface. In the structure shown in FIG. 1, a resin bracket 20 for in-vehicle equipment is bonded to the interior surface of the windshield 10. The bracket 20 is configured to support, for example, an in-vehicle camera. FIG. 2 also shows a partial cross section taken along line II in FIG. 1. As shown in FIG. 2, the windshield 10 and the bracket 20 are bonded via an adhesive layer 30.

[0022] As shown in FIGS. 1 and 2 , a shielding layer 15 may be provided on the periphery of the interior surface of the glass 10. When the glass 10 is a laminated glass, the shielding layer 15 may be provided on both the glass sheet located on the exterior side of the vehicle and the glass sheet located on the interior side of the vehicle, or on only one of them. The shielding layer 15 functions to protect urethane sealants and other materials that adhere and hold the vehicle transparent substrate to the vehicle body from deterioration due to ultraviolet rays. The shielding layer 15 is formed, for example, by applying and firing a ceramic color paste containing a fusible glass frit containing a black pigment. The thickness of the shielding layer 15 is preferably 3 μm to 15 μm. The width of the shielding layer 15 is not particularly limited, but is preferably 20 mm to 300 mm. In the illustrated example, the bracket 20 is bonded to the shielding layer 15 provided on the interior surface of the glass 10. However, the bracket 20 may also be bonded directly to the interior surface of the glass 10. When viewed from outside the vehicle, it is preferable that bracket 20 be adhered in a position that is hidden by shielding layer 15. When bracket 20 is adhered in a position that is hidden by shielding layer 15, not only does it become difficult for bracket 20 and adhesive layer 30 to be seen from outside the vehicle, but it also makes it possible to suppress deterioration of adhesive layer 30 due to ultraviolet rays.

[0023] <Method for manufacturing an automobile window glass structure> One embodiment of the present invention is a method for manufacturing the above-mentioned automotive window glass structure. Fig. 3 shows an example of a flow of the manufacturing method according to this embodiment. As shown in Fig. 3, the manufacturing method according to this embodiment includes evaluating a dry treatment applied to a surface (adhesion surface) of a part having a resin surface that will be bonded to the automotive window glass (S10), and bonding the adhesion surface of the part to the automotive window glass via an adhesive (S20).

[0024] Dry treatments such as plasma treatment modify the surface of components, thereby increasing their adhesive affinity (as described in detail below). This allows for the elimination of the need to apply a primer to the component surface during the manufacture of automotive window glass structures. Conventionally, determining whether dry treatment has been performed properly involves measuring the contact angle and surface tension of a component by dripping a specific liquid onto the surface. However, this method of dripping liquid involves contact with the component surface, which can potentially alter the surface condition of the component depending on the component material, the type of liquid, and other factors. In contrast, the present method uses the emission of fluorescent substances to evaluate dry treatment of the component surface in a non-contact manner, thereby minimizing changes in the component surface quality due to the evaluation process and achieving higher adhesion quality. Furthermore, while conventional methods using contact angles and other factors only evaluate a very limited area of ​​the resin surface, the present method allows for a comprehensive evaluation of the entire adhesive surface. Therefore, it is possible to determine, for example, whether there is any incomplete treatment in areas that require dry treatment. Therefore, according to this embodiment, dry processing can be evaluated with higher reliability than conventional methods, and an automotive window glass structure can be obtained with higher reliability.

[0025] The evaluation of the dry treatment (S10) includes attaching a fluorescent substance to the bonding surface of the component (S11), performing the dry treatment (S12), and evaluating the dry treatment by observing the fluorescence emitted from the bonding surface (S13).

[0026] Each step in the manufacturing method according to this embodiment will be described below.

[0027] (Attachment of fluorescent material (S11)) In this method, a fluorescent material is applied to the bonding surfaces of the components before the dry treatment of the bonding surfaces. The fluorescent material may be applied directly to the bonding surfaces of the components, or may be dissolved in a solvent to prepare a solution, which is then applied to the bonding surfaces. Applying the fluorescent material in solution form is preferable because it allows the fluorescent material to be evenly applied to the desired area and the amount of fluorescent material used can be kept small.

[0028] The solvent used to prepare the phosphor solution is not particularly limited and can be appropriately selected depending on the solubility of the phosphor used and the type of resin material on the resin surface. The solvent may be, for example, an organic solvent, water, etc. Among these, an organic solvent is preferred because it volatilizes easily after application. Furthermore, the organic solvent is preferably a solvent with a high degreasing effect that can be suitably used as a cleaning solution for cleaning or washing resin surfaces. The organic solvent may be one or a mixture of two or more alkanes and alcohols that are liquid at room temperature (15 to 25°C). Specific examples include n-hexane, ethanol, 1-propanol, and 2-propanol. The solvent may be a single component or a combination of two or more components. It may also be a mixture of lower alcohols primarily containing ethanol (e.g., a mixture of ethanol, 1-propanol, and 2-propanol), known as mixed ethanol.

[0029] The fluorescent substance is not particularly limited as long as its fluorescence can be observed visually or by some means, such as a fluorescence detection device, when observing the resin surface of a component to which the fluorescent substance is attached. It is sufficient that the difference between the area where the fluorescent substance is present and the area where it is not present can be recognized during observation. Furthermore, fluorescent substances whose fluorescence can be visually confirmed, i.e., substances that emit light in the visible range, are preferred because they facilitate observation. A suitable fluorescent substance in this embodiment is at least one of 2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene (hereinafter also referred to as BBOT) and methylene blue (also referred to as 3,7-bis(dimethylamino)phenothiazinium chloride or MeB). These fluorescent substances are preferred because they have high quantum yields and low toxicity. They also dissolve well in organic solvents such as n-hexane, ethanol, 1-propanol, and 2-propanol.

[0030] When using a phosphor solution, the phosphor can be applied by, for example, soaking a wipe in the solution and then rubbing or wiping the adhesive surface of the component with the wipe. The wipe may be a fibrous or porous material capable of absorbing and retaining the solvent, such as a sheet-like material such as cloth or nonwoven fabric, or a bulk material such as a sponge. The phosphor solution can also be applied to the component surface by spraying the solution onto the adhesive surface, or by contacting or immersing at least the adhesive surface of the component in the phosphor solution.

[0031] The concentration of the phosphor solution is preferably 1×10 -6 mol / L or more 1×10 -2 mol / L or less, more preferably 1×10 -5 mol / L or more 1×10 -3 mol / L or less, more preferably 1×10 -5 mol / L or more 1×10 -4In particular, when 2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene is used as the fluorescent substance, the concentration of the solution may be 1×10 -5 mol / L or more 1×10 -4 mol / L or less. By using a solution with a concentration in the above range, sufficient fluorescence for observation can be obtained, and the influence on the adhesion between the bonding surfaces of the parts and the adhesive can be suppressed. For example, by using a solution with a concentration in the above range, when an adhesive is applied and tested, it is possible to obtain adhesive quality such that the cohesive failure rate (adhesive adhesion area rate) is preferably 30% or more, more preferably 40% or more, and even more preferably 60% or more.

[0032] When a fluorescent material is attached to a resin surface using a fluorescent material solution, a cleaning liquid for cleaning the component surface can be used as a solvent for dissolving the fluorescent material. By using a liquid suitable for use as a cleaning liquid for cleaning component surfaces as the solvent for the fluorescent material solution, cleaning of the bonding surface of the component with the fluorescent material solution can also be performed during the fluorescent material attachment process. In this case, dust or dirt that may be present on the component surface can be dispersed or dissolved in the solution or solvent during the fluorescent material attachment process and removed from the component surface. Alternatively, the dust or dirt can be decomposed by the solution, and the substances resulting from this decomposition can be dispersed or dissolved in the solution or solvent and removed from the component surface.

[0033] In other words, in this embodiment, by adding a fluorescent substance to the cleaning solution used in the surface cleaning process, the fluorescent substance can be attached to the surface of the component simultaneously during the surface cleaning process. Therefore, the fluorescent substance can be applied to the bonding surface during cleaning without significantly changing the cleaning or washing process performed before the dry processing.

[0034] When wiping a component surface with a wiper impregnated with a fluorescent solution, the wiper may be wiped without applying pressure to the component surface, or with a pressure of 0.2 kPa to 60 kPa. Wiping with pressure ensures reliable removal of dirt from the component surface. Dust and dirt can be mechanically removed from the resin surface by breaking down or dissolving the dirt in the solvent.

[0035] Furthermore, it is preferable that the phosphor material be attached over a wider area than the area to be dry-processed in the subsequent dry process (S12) (the area that is preset to be dry-processed). For example, it is preferable that the area to which the phosphor material is attached be formed over an area that extends beyond the periphery of the area to be dry-processed.

[0036] (Dry processing (S12)) The dry treatment is performed on the bonding surface after the step (S11) of attaching the fluorescent material to the bonding surface of the component as described above. The dry treatment is performed on at least the area of ​​the bonding surface that is to be dry treated, more specifically, on the area that includes the area to be coated with adhesive in the subsequent step (S20) of coating with adhesive.

[0037] Specific examples of dry treatments include plasma treatment, corona treatment, flame treatment, itro treatment, ultraviolet irradiation treatment, and excimer treatment, among which at least one of plasma treatment and corona treatment is preferred. When the dry treatment is plasma treatment, the means for generating plasma is not particularly limited and may be a high-frequency plasma generator or a low-frequency plasma generator. Furthermore, plasma generated by irradiation with laser, microwave, or the like may also be used.

[0038] Dry treatment can introduce or form hydrophilic functional groups, such as hydroxyl, carbonyl, and carboxyl groups, on the resin surface, thereby increasing the number of hydrophilic functional groups per unit area. This increases the number of sites where the hydrophilic functional groups on the surface can interact with the adhesive components through chemical bonds or intermolecular forces, strengthening the bond (interfacial bond) between the component and the adhesive when the resin surface of the component is used as the bonding surface and bonded to an automotive window glass via an adhesive. Dry treatment can also decompose and remove substances on the component surface that may interfere with adhesion (contaminants that were not completely removed by the above-mentioned cleaning). Therefore, dry treatment (S12) can also be considered a dry cleaning or washing process. In this case, if cleaning is performed in conjunction with the fluorescent substance deposition process (S11), this embodiment can also be considered a two-stage cleaning process.

[0039] Since the dry treatment can increase the adhesion between the part and the adhesive, an automotive window glass structure can be manufactured without applying a primer to the part surface, but the part and the automotive window glass may be bonded by applying a primer after the dry treatment and then applying an adhesive to the primer. In this case, the adhesion between the dry-treated surface and the primer can be increased, thereby increasing the adhesion between the part and the automotive window glass.

[0040] The conditions for dry processing can be adjusted as appropriate depending on the type of resin and adhesive used on the surface of the part, the purpose of use of the part and its location in the automobile, the desired adhesive strength, etc. Specific conditions for dry processing cannot be generalized because they depend on the type of device used for dry processing and the configuration of the part, but when the dry processing is plasma processing, for example, the frequency of the applied voltage of the power supply for the plasma generation means may be 50 GHz or higher and 2.45 GHz or lower, preferably 50 Hz or higher and 25 kHz or lower, and the irradiation distance (the distance between the electrode and the surface of the molded body) may be 50 mm or lower, preferably 10 mm or higher and 30 mm or lower. There is no particular restriction on the lower limit of the distance between the opposing nozzle and the workpiece (molded body), but it may be, for example, 0.5 mm or higher. The output power density is 15 W / cm 2 More than 20W / cm, preferably 20W / cm 2 The irradiation time is determined by the nozzle movement speed, which may be 0.01 m / min or more and 50 m / min or less, preferably 2.5 m / min or more and 10 m / min or less.

[0041] When performing plasma treatment, if the surface temperature of the part having a resin surface is increased by, for example, heating the molded body with a heater before plasma irradiation, the adhesion between the part and the adhesive in the structure obtained through the subsequent steps can be further improved. The surface temperature of the part before plasma irradiation can be set to, for example, a temperature above room temperature, and may be set to, for example, 60°C or higher.

[0042] (Evaluation of dry processing (S13)) After the dry treatment is performed on the surface to which the fluorescent substance is attached as described above (S12), the dry treatment is evaluated by observing the fluorescence emitted from the bonding surface of the parts (S13). This observation may be performed on the entire bonding surface, but it can also be performed on at least the area of ​​the bonding surface to be dry treated (the area including the area where the adhesive is actually scheduled to be applied).

[0043] It is believed that if an appropriate dry treatment is performed on the area where the fluorescent substance was attached, the fluorescent substance will decompose and lose its fluorescent ability. Therefore, in the evaluation step (S13), by measuring the fluorescence intensity of the adhesive surface, it can be determined whether the adhesive surface has been appropriately dry-treated. For example, if the fluorescence intensity detected during observation after the dry treatment is zero or is below a predetermined value, it can be determined that the dry treatment has been appropriately performed.

[0044] Here, appropriate dry processing may mean that the component has been subjected to dry processing, or that the area to be dry-processed (the area previously designated as being dry-processed) has been subjected to dry processing. Furthermore, appropriate dry processing may mean that the degree of dry processing actually performed in the area to be dry-processed is appropriate and / or that the range of dry processing is appropriate. Therefore, users of the method according to this embodiment can appropriately set the standard for the intensity of fluorescent light and / or the standard for the range of detected fluorescent light intensity for determining appropriate dry processing, depending on the desired degree of dry processing. Therefore, depending on the configuration, dry processing may be determined to be appropriate even if fluorescent material remains in the area to be dry-processed. Here, appropriate dry processing may be processing that results in adhesive quality such that, when tested with an adhesive, the cohesive failure rate (adhesive adhesion area rate) is preferably 30% or more, more preferably 40% or more, and even more preferably 60% or more.

[0045] When measuring fluorescence intensity, it is preferable to provide a control area on the bonding surface for comparison. For example, a region adjacent to the region to be dry-processed can be provided where the fluorescent substance is applied under the same conditions as the region to be dry-processed but where no dry processing is performed. Such a control area where no dry processing is performed can be formed, for example, by covering the region with a mask during dry processing. If the component itself is not subjected to the dry processing process due to a malfunction of the dry processing equipment, or if a surface other than the bonding surface of the component is dry-processed, no fluorescent substance will be applied to any region of the bonding surface. Therefore, observing the fluorescence in the control area allows accurate judgment even in such cases. When a control area is provided, the ratio of the fluorescence intensity in the region to be dry-processed to the fluorescence intensity in the control area can be calculated, and the dry processing, i.e., whether or not the dry processing was performed appropriately, can be evaluated based on this ratio. In addition, if the area to which the fluorescent substance is to be applied in the fluorescent substance application step (S11) is formed so that it extends beyond the periphery of the area to be dry-processed, the contrast area can be made to surround the area to be dry-processed, which is preferable because it makes the contrast area easier to identify.

[0046] In the fluorescent substance application step (S11), if a fluorescent substance solution using a cleaning solution as a solvent is used to clean the resin surface and apply the fluorescent substance, it is possible to determine whether the dry treatment was properly performed and also whether cleaning was performed. For example, if the fluorescent substance solution is applied to areas other than the area to be dry treated, such as the control area, it is possible to determine whether cleaning was performed by observing the fluorescence in those areas.

[0047] The fluorescence observation in the dry processing evaluation step (S13) may be performed, for example, visually. Direct visual observation is preferable and practical from the viewpoints of simplicity and low cost, since it does not require large-scale equipment. When visually observing, a light irradiation device may be placed nearby to irradiate light. For example, ultraviolet light can be irradiated onto the adhesive surface using a UV-LED light generator, and the fluorescence can be visually observed. When BBOT is used as the fluorescent substance, visual observation can be easily achieved by irradiating ultraviolet light.

[0048] Fluorescence observation may also be performed using a device capable of detecting fluorescence, such as a fluorescence microscope or a fluorescent filter. Observation through such a device allows detection of fluorescence even at low fluorescence intensity, which is preferable from the viewpoint of potentially reducing the amount of fluorescent substance used in the fluorescent substance application step (S11). When using a device such as a fluorescence microscope, the fluorescence intensity may be visually confirmed through an eyepiece, or the adhesion surface may be imaged using a camera or the like, and the image data may be imported into a personal computer or the like and displayed on a display device to confirm the fluorescence intensity. Furthermore, image processing may be performed using the imported image data, thereby enabling more accurate measurement of fluorescence intensity. Furthermore, when using a device, the determination of whether or not the drying process was performed appropriately may be automated.

[0049] In this evaluation step (S13), the dry treatment performed in the previous step (S12) can be evaluated by visually or instrumentally observing the fluorescent emission state. Therefore, one embodiment of the present invention may be a method for evaluating dry treatment, including attaching a fluorescent substance to the bonding surface of a component having a resin surface (S11), performing dry treatment (S12), and evaluating the dry treatment by observing the fluorescent emission state of the dry-treated bonding surface (S13). The evaluation method according to this embodiment is non-contact, meaning that no object is brought into contact with the bonding surface after dry treatment. Therefore, the component can be subjected to the subsequent bonding step (S20) without changing the state of the dry treatment. Furthermore, since the entire area to be dry-treated can be easily observed, any remaining processing can be detected, enabling a more reliable evaluation than conventional methods that only allow localized evaluation.

[0050] (Adhesion to automobile window glass (S20)) If it is determined through the evaluation (S10) including the above-mentioned steps S11 to S13 that the area to be dry-treated has actually been properly dry-treated (dry-treated area), an adhesive can be applied to the dry-treated area of ​​the bonding surface and bonded to the automotive window glass (S20). During bonding, a primer can also be applied to the bonding surface of the automotive window glass.

[0051] If the evaluation (S10) determines that the dry treatment was not performed appropriately, for example, if the dry treatment was not performed to a sufficient degree or if there is undesired incomplete treatment in an area that should have been dry treated, the dry treatment (S12) may be performed again. The newly performed dry treatment is then evaluated (S13), and if it is confirmed that the dry treatment was appropriate, the process can proceed to the bonding step (S20).

[0052] The adhesive used in the bonding step (S20) is preferably a one-component or two-component moisture-curing adhesive, and more preferably a urethane-based adhesive, a modified silicone-based adhesive, etc. In addition to moisture-curing adhesives, photo-curing adhesives and heat-curing adhesives can also be used.

[0053] After bonding the automotive window glass and the component having a resin surface with the adhesive, the glass may be stored in a predetermined environment, i.e., cured. This curing can also enhance the adhesion between the automotive window glass and the component. For example, curing can be performed by storing the glass for a predetermined period of time under a temperature and humidity appropriate for the type of adhesive. [Example]

[0054] Hereinafter, the embodiments of the present invention will be described in more detail based on examples. In these examples, the surface of a resin molded body was cleaned using a solution of a fluorescent substance, followed by dry treatment. The dry treatment was evaluated by observing the fluorescence of the surface after the dry treatment. An adhesive was applied to the surface of the resin molded body, and the adhesion between the resin molded body and the adhesive was evaluated. Examples 1 to 6 are examples, and Example 7 is a comparative example.

[0055] (Example 1) A plate-shaped molded body (25 mm × 150 mm × 5 mm) made of glass fiber reinforced polybutylene terephthalate (PBT GF-30) (Polyplastics Co., Ltd., 733LD) containing 30% glass fiber was used as the resin molded body. 2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene (BBOT) was dissolved in n-hexane (Wako Pure Chemical Industries, Ltd., special grade) to a concentration of 1 × 10 -4 A solution of 0.0065 mol / L (wt%) was prepared. The resin molded body was cleaned by wiping almost the entire surface with a nonwoven wiper (Bencott (registered trademark), manufactured by Asahi Kasei Corporation) soaked in the solution. After visually confirming that the solution had evaporated, one half of the cleaned area was plasma-treated (dry treatment) using an atmospheric pressure plasma treatment device (PS-601SW, manufactured by Wedge Corporation). The distance between the head and the component surface during the plasma treatment was 10 mm, and the irradiation time was 4 seconds. The plasma treatment was evaluated using the method described below, and then an adhesive was applied to the plasma-treated area, and the adhesion was evaluated using the method described below.

[0056] (Example 2) The concentration of the solution is 1 x 10 -5 The resin molded body was cleaned and plasma-treated in the same manner as in Example 1, except that the concentration was set to 0.00065% by weight. The plasma treatment and the adhesiveness were evaluated.

[0057] (Example 3) BBOT was dissolved in mixed ethanol (Yamaichi Chemical Industry Co., Ltd., Mixed Ethanol NP) to obtain a concentration of 1 × 10 -4 The resin molded body was cleaned and plasma-treated in the same manner as in Example 1, except that a solution of 0.0065 mol / L (0.0065 wt %) was used, and the plasma treatment and adhesion were evaluated.

[0058] (Example 4) The concentration of the solution is 1 x 10 -5 The resin molded body was cleaned and plasma-treated in the same manner as in Example 3, except that the concentration was set to 0.00065% by weight. The plasma treatment and the adhesiveness were evaluated.

[0059] (Example 5) The concentration of the solution is 1 x 10 -3 The resin molded body was cleaned and plasma-treated in the same manner as in Example 1, except that the concentration was set to 0.065 wt %. The plasma treatment and the adhesiveness were evaluated.

[0060] (Example 6) Methylene blue (MeB) was dissolved in mixed ethanol (Yamaichi Chemical Industry Co., Ltd., Mixed Ethanol NP) at a concentration of 1 × 10 -5 The resin molded body was cleaned in the same manner as in Example 1, except that a solution of 0.00065% by weight of 1.25 mol / L was used. Thereafter, the body was subjected to a plasma treatment and evaluated.

[0061] (Example 7) In this example, n-hexane (solute concentration 0 wt%) was used instead of the solution, and plasma treatment was not performed. Other than that, cleaning was performed in the same manner as in Example 1. Then, plasma treatment was performed, and adhesion was evaluated.

[0062] <Evaluation of plasma treatment (dry treatment)> In Examples 1 to 5, in which BBOT was used as the fluorescent material, and Example 7, in which no fluorescent material was used, the dry-treated surface of the resin molded body was irradiated with UV-LED light at a wavelength of 365 nm using an LED light (Optocode, LED-UV365P), and the fluorescence intensity in the plasma-treated area was confirmed visually. In these examples, if the fluorescence intensity in the plasma-treated area was determined to be zero by visual inspection, it was considered that no fluorescence was detected, and it was determined that the plasma treatment had actually been performed appropriately. In addition, when making the determination, the light emission state of the plasma-treated area was compared with the light emission state of the adjacent area that was not plasma-treated.

[0063] In Example 6, in which methylene blue was used as the fluorescent substance, the dry-treated surface of the resin molded article was observed using a fluorescence microscope, and the images obtained through the fluorescence microscope were analyzed. Based on the image analysis, the fluorescence intensity in the plasma-treated area was measured. In this example, if the fluorescence intensity in the plasma-treated area was zero, it was determined that no fluorescence was detected, and that the plasma treatment had actually been performed appropriately. In making this determination, the luminescence state of the plasma-treated area was compared with the luminescence state of the adjacent area that was not subjected to plasma treatment, as described above.

[0064] <Evaluation of Adhesion> A urethane adhesive (WS292, manufactured by Yokohama Rubber Co., Ltd.) was applied to the plasma-treated area, and evaluation was performed based on the adhesive adhesion area ratio (the ratio of the area where adhesive remained, or the cohesive failure rate) after knife cutting using a method in accordance with JASO M338-89 standard 9.11 pot life test. Note that an adhesive adhesion area ratio of 0% indicates that the adhesive has not undergone cohesive failure at all and interfacial peeling has occurred, while a ratio of 100% indicates that cohesive failure has occurred over the entire surface where the adhesive has been applied. The higher the adhesive adhesion area ratio, the greater the proportion of cohesive failure that has occurred in the adhesive, and the better the adhesion between the resin molded product and the adhesive can be evaluated.

[0065] Table 1 shows the conditions and evaluation results for each example.

[0066] [Table 1]

[0067] As shown in Table 1, in all of Examples 1 to 6, by cleaning with a solution of a fluorescent substance before the dry treatment, it was possible to evaluate the dry treatment (determine whether or not plasma treatment was performed) and the adhesion between the test piece and the glass plate was also ensured. In addition, when the concentration of the fluorescent substance in the solution used for cleaning was 1 × 10 -4 In the cases where the concentration was mol / L or less (Examples 1 to 4 and Example 6), the adhesive adhesion area ratio exceeded 40%, and it was found that particularly good adhesiveness was obtained. [Explanation of symbols]

[0068] 1. Automotive window glass structure 10. Glass 15 Shielding layer 20 Resin parts (brackets) 30 Adhesive layer

Claims

1. A method for manufacturing an automobile window glass structure in which a component having a resin surface is bonded to an automobile window glass, comprising: A fluorescent substance is attached to the adhesive surface of the component having the resin surface; performing a dry treatment on the adhesive surface to which the fluorescent material is attached; evaluating the dry treatment by observing fluorescence emitted from the adhesive surface; The component is bonded to an automobile window glass via an adhesive applied to the bonding surface.

2. The manufacturing method according to claim 1 , wherein the fluorescent material is attached using a solution of the fluorescent material.

3. The manufacturing method according to claim 2 , wherein the attachment of the fluorescent substance is carried out simultaneously with cleaning of the adhesive surface.

4. The method of claim 3 , wherein the cleaning step comprises wiping the adhesive surface with a wipe material saturated with the solution.

5. The manufacturing method according to claim 2 , wherein the solution is a solution obtained by dissolving the fluorescent substance in an organic solvent.

6. The concentration of the fluorescent substance in the solution is 1×10 －６ mol / L or more 1×10 －２ The method according to any one of claims 2 to 5, wherein the concentration is 1000 ppm or less.

7. 7. The method according to claim 1, wherein the fluorescent substance is at least one of 2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene and methylene blue.

8. The method according to claim 1 , wherein the dry treatment is at least one of a plasma treatment and a corona treatment.

9. The method according to claim 1 , wherein the observation of the fluorescence comprises direct visual observation under irradiation with UV light.

10. The manufacturing method according to claim 1 , wherein the observing of the fluorescence comprises observing with a fluorescence microscope.

11. A manufacturing method described in any one of claims 1 to 10, wherein the deposition of the fluorescent substance is carried out over an area wider than the area to be dry-treated by the subsequent dry treatment, and the area to which the fluorescent substance is deposited is formed in an area that extends beyond the periphery of the area to be dry-treated.

12. The adhesive surface is provided with a control area for evaluating the dry treatment by measuring fluorescence intensity; The manufacturing method according to claim 11 , wherein the control region is provided adjacent to the region to be dry-processed and surrounds the region to be dry-processed.

13. 1. A method for evaluating a dry treatment applied to a part having a resin surface to be bonded to an automobile window glass, comprising: A fluorescent substance is attached to the adhesive surface of the component having the resin surface; performing a dry treatment on the adhesive surface to which the fluorescent material is attached; The dry treatment is evaluated by observing the fluorescence emitted from the adhesive surface.

Images