JP2023069900A - Method for producing automotive window glass structure, and method for evaluating dry processing - Google Patents

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 The present invention relates to a method for manufacturing an automobile window glass structure and a method for evaluating dry processing.

2. Description of the Related Art A structural body is known in which a resin component such as a bracket is adhered to an automobile window glass via an adhesive. In the manufacture of such a structure, in order to improve the adhesiveness between the resin parts and the adhesive, it is also possible to modify the surface by subjecting the bonding surfaces of the resin parts to dry treatment such as plasma treatment. Are known. For example, Patent Literature 1 discloses a surface treatment method for a member in which the surface of a member containing a crystalline thermoplastic resin is treated by dry treatment. Ensuring that a given relationship based on energy is satisfied is described.

JP-A-2008-127428

In the technique described in Patent Document 1, the dry treatment applied to the member surface is evaluated by measuring the contact angle and surface tension of a predetermined liquid. However, in measuring the contact angle, liquid is dropped on the surface, so the surface state of the part may change depending on the material forming the part and the type of liquid used for measurement. Therefore, there is a need for a non-contact method for appropriately evaluating the dry treatment applied to the adhesive surface.

In view of the above points, one aspect of the present invention provides a non-contact dry treatment of the resin surface of the component in the manufacture of an automotive window glass structure in which a component having a resin surface is adhered to the automotive window glass. An object is to provide a method that can be evaluated.

In order to solve the above problems, there is provided a method for manufacturing an automobile window glass structure in which a part having a resin surface is adhered to an automobile window glass, wherein a fluorescent material is adhered to the bonding surface of the part having the resin surface. Then, the adhesive surface is subjected to a dry treatment, the dry treatment is evaluated by observing the fluorescence emitted from the adhesive surface, and the part is attached to an automobile window glass via the adhesive applied to the adhesive surface. to adhere to.

ADVANTAGE OF THE INVENTION According to one aspect of the present invention, dry treatment of a resin surface of a part can be evaluated in a non-contact manner in manufacturing an automobile window glass structure in which a part having a resin surface is adhered to the automobile window glass.

1 is a plan view of an automotive glazing structure according to one embodiment of the present invention; FIG. FIG. 2 is a partial view of a section taken along the line II of FIG. 1; 1 is a flow diagram of an evaluation method or manufacturing method according to one embodiment of the present invention; FIG.

EMBODIMENT OF THE INVENTION Hereinafter, although the form for implementing this invention is demonstrated, this invention is not limited to the following form.

<Automotive Window Glass Structure>
In this specification, the automobile window glass structure refers to a structure in which a part having a resin surface is adhered to the main surface of the automobile window glass with an adhesive. Automotive window glass may more specifically be a windshield, a rear window, a side window, or the like.

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, and borosilicate glass. The glass plate may be unstrengthened, or may be subjected to air-cooling tempering or chemical strengthening treatment. Untempered glass is obtained by shaping molten glass into a plate and slowly cooling it. Tempered glass is obtained by forming a compressive stress layer on the surface of untempered glass. When the tempered glass is air-cooled tempered glass, the uniformly heated glass plate is rapidly cooled from a temperature near the softening point, and the temperature difference between the glass surface and the inside of the glass causes a compressive stress on the glass surface, thereby reducing the temperature of the glass. The surface may be strengthened. On the other hand, when the tempered glass is chemically tempered glass, the glass surface may be strengthened by applying compressive stress to the glass surface by an ion exchange method or the like. Further, a glass plate that absorbs ultraviolet rays or infrared rays may be used for the vehicle glass, and it is preferable that the glass plate is transparent. Organic glass may be used for the vehicle glass. Examples of organic glass include transparent resins such as polycarbonate.

The window glass for automobiles may be a laminated glass including a plurality of the glass plates described above, for example, a laminated glass obtained by laminating two glass plates with an intermediate film interposed therebetween. Examples of the intermediate film placed between the glass plates include ethylene vinyl acetal, polyvinyl butyral and the like.

The plane view shape of the window glass for automobiles is not limited to a rectangle, and may be processed to have various shapes. Further, the automobile window glass may be curved, and the curvature is not particularly limited. The curvature can be obtained by bending the glass plate used, such as gravity molding or press molding. The shape and curvature of the automotive glazing are designed to allow parts to be glued to its major surfaces and to allow sufficient dry treatment of the glued surfaces.

As a specific example of the structure in which parts having a resin surface are adhered to the above-mentioned automobile window glass, a resin bracket or base for mounting in-vehicle equipment (vehicle camera, in-vehicle sensor, mirror, etc.), or a resin A structural body in which a part such as a temporary fixing pin made by the manufacturer is adhered to the surface facing the inside of the vehicle when the windshield is attached to the vehicle. Alternatively, the structure may be a structure in which parts such as a resin door slider and a resin door holder are adhered to the side glass. In this way, the part to be bonded to the window glass for an automobile has at least a plate-like portion to be bonded, and an adhesive surface corresponding to the shape of the bonding surface of the main surface of the window glass for an automobile is formed. things are preferred.

When the part having a resin surface is a part for mounting an on-vehicle device, the on-vehicle device that can be attached may be a rain sensor, a defrost sensor, an infrared sensor, a millimeter wave radar, etc., in addition to an on-vehicle camera. It may also be a resin base for mounting an interior mirror. In addition, the automobile window glass structure manufactured according to the present embodiment is suitably used in automobiles equipped with a Driving Safety Support System (DSSS) or an Advanced Driver-Assistance System (ADAS). be done.

A part to be attached to a window glass for an automobile may have a resin surface, that is, at least the surface is formed of resin, or formed mainly of resin. Further, the component may have a resin surface at least on the surface to be adhered to the automobile window glass. Therefore, the part having a resin surface may be a molded article entirely or mainly made of resin, or a molded article made of a material other than resin whose surface is partly or wholly made of resin. It may be coated with a layer. Note that "mainly made of resin" means that the resin is contained in a proportion that maintains the inherent properties of the resin, for example, the resin is contained in an amount of 50% by weight or more. Further, in this specification, a part having a resin surface may be referred to as a "resin part" or a "resin part".

The resin material used for parts having a resin surface is not particularly limited, but polyesters such as polybutylene terephthalate (PBT) and polyethylene terephthalate (PET), polyolefins such as polyethylene (PE) and polypropylene (PP), polycarbonate (PC), Polyamide (PA) such as nylon 6, nylon 6,6, high heat resistant polyamide (PA6T, PA6I, PA6T/6I, etc.) based on terephthalic acid or isophthalic acid, polyimide (PI), polyetherimide (PEI), acrylonitrile -butadiene-styrene (ABS), polyacetal (POM), polyvinyl chloride (PVC), epoxy (EP), and the like. These resin materials may be used as homopolymers, or may be used as copolymers by combining one or more of the above. The resin material may also be a polymer alloy combining one or more of the above, such as a polymer alloy of polybutylene terephthalate and styrene acrylonitrile.

In addition, components other than resin components, such as fillers, pigments, and resin modifiers, may be added to the resin material. 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 fibers and carbon fibers. As the fiber-reinforced resin, glass fiber-reinforced polybutylene terephthalate, polyetherimide, and the like are preferable. When the resin contains reinforcing fibers, the fibers can be contained in an amount of 5% by weight or more and 70% by weight or less, preferably 30% by weight or more and 50% by weight or less, based on the total weight of the resin.

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

In addition, in the case where the part having a resin surface is a molded body made of a material other than resin, the surface of which is partly or wholly coated with resin, for example, a base made of metal or the like is coated with an electrode containing resin. It may be an electrodeposition-coated body that has been electrodeposition-coated using a coating material. The electrodeposition coating is produced by energizing a substrate (basis) in an electrolytic bath, depositing resin coating particles on the surface of the component, and heating and curing the coating in a curing furnace to form a film. When the resin surface is formed by electrodeposition coating, the electrodeposition coating is preferably a cationic electrodeposition coating. Also, the resin contained in the electrodeposition coating can be a thermosetting resin such as an epoxy resin, and preferably contains an epoxy resin modified with amine, ammonium or the like. On the other hand, the substrate can be a molded body of metal containing steel, aluminum, etc., especially a plate-shaped molded body. Examples of the electrodeposition coated body include cationic electrodeposition coated steel sheets manufactured by Aoki Electric Industry Co., Ltd. (Elecron HG-305E black manufactured by Kansai Paint Co., Ltd. is used as the electrodeposition paint). The surface of the resin may be formed by applying a resin-containing solution or dispersion, or a resin melt, or the like, by coating a pre-formed sheet-like resin layer, or by coating the substrate with a resin surface. It can also be formed by electrolytic plating or the like. In the case of such a part whose surface is partly or wholly coated with resin, at least part of the surface (adhesive surface) to be adhered to the automobile window glass should be covered with a resin layer, and the entire adhesive surface is preferably covered with a resin layer.

FIG. 1 shows an example of an automobile window glass structure 1 formed by bonding an automobile window glass and a part having a resin surface. In the structure shown in FIG. 1, a resin bracket 20 for in-vehicle equipment is adhered to the surface of the windshield 10 on the inside of the vehicle. The bracket 20 is configured to support an onboard camera, for example. Further, FIG. 2 partially shows a cross section taken along the line II of FIG. As shown in FIG. 2 , the windshield 10 and the bracket 20 are adhered via an adhesive layer 30 .

As shown in FIGS. 1 and 2, a shielding layer 15 may be provided on the periphery of the surface of the glass 10 on the vehicle interior side. When the glass 10 is laminated glass, the shielding layer 15 may be provided on both the glass plate positioned on the outside of the vehicle and the glass plate positioned on the inside of the vehicle, or may be provided on only one of them. good. The shielding layer 15 has a function of protecting a urethane sealant or the like that adheres and holds the transparent substrate for a vehicle to the vehicle body from deterioration due to ultraviolet rays. The shielding layer 15 is formed, for example, by applying a ceramic color paste containing fusible glass frit containing a black pigment and baking it. The thickness of the shielding layer 15 is preferably 3 μm or more and 15 μm or less. Although the width of the shielding layer 15 is not particularly limited, it is preferably 20 mm or more and 300 mm or less. In the illustrated example, the bracket 20 is adhered onto the shielding layer 15 provided on the vehicle-interior surface of the glass 10 , but the bracket 20 may be directly adhered to the vehicle-interior surface of the glass 10 . It is preferable that the bracket 20 is adhered to a position that is hidden by the shielding layer 15 when viewed from the outside of the vehicle. When the bracket 20 is adhered to the position hidden by the shielding layer 15, not only the bracket 20 and the adhesive layer 30 are hardly visible from the outside of the vehicle, but also the deterioration of the adhesive layer 30 by ultraviolet rays can be suppressed.

<Manufacturing Method for Automobile Window Glass Structure>
One embodiment of the present invention is a method of manufacturing the automotive glazing structure described above. FIG. 3 shows an example of the flow of the manufacturing method according to this embodiment. As shown in FIG. 3, the manufacturing method according to the present embodiment evaluates the dry treatment applied to the surface (adhesive surface) of a part having a resin surface that is to be adhered to an automobile window glass (S10). Adhering (S20) the surface to the automobile window glass via an adhesive.

Dry treatment such as plasma treatment has the effect of modifying the surface of the part, which can increase the affinity for the adhesive (detailed later). Application of a primer to the part surface can be omitted. Here, in order to determine or confirm whether the dry treatment is properly performed, conventionally, a predetermined liquid is dropped on the surface to measure the contact angle and surface tension, and the measured value is calculated. It was done by using However, in this method of dripping the liquid, the liquid comes into contact with the surface of the part, so depending on the material of the part, the type of liquid, etc., the surface condition of the part where the liquid comes into contact may change. There was a possibility of it getting lost. On the other hand, in this embodiment, since the dry treatment of the surface of the component is evaluated without contact using the light emission of the fluorescent substance, it is possible to suppress the change in the surface quality of the component due to the work for evaluation, resulting in higher adhesion. You can get quality. In addition, in the conventional method using the contact angle, etc., only a very limited area of the resin surface is actually evaluated, but according to the present embodiment, the entire adhesive surface can be evaluated evenly. It becomes possible. Therefore, for example, it is possible to determine whether or not there is any unprocessed area in the area to be dry processed. Therefore, according to the present embodiment, it is possible to evaluate the dry treatment with higher reliability than the conventional method, and thus to obtain an automotive window glass structure with higher reliability.

Evaluation of the dry process (S10) involves attaching a fluorescent substance to the adhesive surface of the part (S11), performing dry process (S12), and evaluating the dry process by observing the fluorescence emitted from the adhesive surface. (S13) is included.

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

(Adhesion of fluorescent substance (S11))
In the method according to this embodiment, a fluorescent material is attached to the bonding surface of the component before the bonding surface of the component is subjected to the dry treatment. The fluorescent substance may be applied directly to the bonding surface of the component, or may be dissolved in a solvent to prepare a solution, and the solution may be applied to the bonding surface. When the fluorescent substance is applied in the form of a solution, the fluorescent substance can be uniformly adhered to the desired region, and the amount of the fluorescent substance used can be suppressed to a small amount, which is preferable.

The solvent used in preparing the above fluorescent substance solution is not particularly limited, and can be appropriately selected according to the solubility of the fluorescent substance used and the type of resin material on the resin surface. The solvent may be, for example, an organic solvent, water, or the like. Among these, it is preferable to contain an organic solvent because it is easily volatilized after coating. Furthermore, the organic solvent is preferably a solvent having a high degreasing action that can be suitably used for cleaning the resin surface or as a cleaning liquid for washing. The organic solvent may be one or a mixture of two or more of alkanes and alcohols that are liquid at room temperature (15 to 25° C.). Specific examples include n-hexane, ethanol, 1-propanol, 2-propanol and the like. The solvent may be one component or a combination of two or more. A lower alcohol mixture containing ethanol as the main component (eg, a mixture of ethanol, 1-propanol, and 2-propanol), called mixed ethanol, may also be used.

The fluorescent substance is not particularly limited as long as fluorescence can be observed visually or through some means such as a fluorescence detection device when observing the resin surface of the component to which the fluorescent substance is adhered. During observation, it is sufficient if the difference can be recognized by comparing the area where the fluorescent substance exists and the area where it does not exist. In addition, it is preferable to use a fluorescent substance whose fluorescence emission can be visually confirmed, that is, a substance that can emit light in the visible region, because it is easy to observe. Preferred fluorescent substances in this embodiment are 2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene (hereinafter also referred to as BBOT) and methylene blue (3,7-bis(dimethylamino)phenothiazinium chloride, or MeB). These fluorophores are preferred because they have high quantum yields and are less toxic. Also, it can dissolve well in organic solvents such as n-hexane, ethanol, 1-propanol and 2-propanol.

When a fluorescent substance solution is used, the fluorescent substance can be adhered by, for example, a technique in which a wipe material is impregnated with the fluorescent substance solution and the wipe material is stroked or wiped over the bonding surface of the component. The wipe material may be a fiber-containing or porous material capable of absorbing and retaining a solvent, for example, a cloth, a sheet-like material such as a non-woven fabric, or a lump-like material such as a sponge. good. Further, the application of the fluorescent substance solution to the surface of the component can be carried out by spraying the fluorescent substance solution onto the bonding surface of the component, or by contacting or immersing at least the bonding surface of the component in the fluorescent substance solution. be able to.

The concentration of the fluorescent substance solution is preferably 1×10 ⁻⁶ mol/L or more and 1×10 ⁻² mol/L or less, more preferably 1×10 ⁻⁵ mol/L or more, relative to the total volume of the fluorescent substance solution. It may be 1×10 ⁻³ mol/L or less, more preferably 1×10 ⁻⁵ mol/L or more and 1×10 ⁻⁴ mol/L or less. In particular, when 2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene is used as the fluorescent substance, the concentration of the solution is 1×10 ⁻⁵ mol/L or more and 1×10 ⁻⁴ mol/L. It is preferable to: By using a solution with a concentration within the above range, sufficient fluorescence emission for observation can be obtained, and the influence on the adhesiveness between the bonding surface of the component and the adhesive can be suppressed. For example, by using a solution with a concentration in the above range, the cohesive failure rate (adhesive adhesion area ratio) is preferably 30% or more, more preferably 40% or more when an adhesive is applied and tested. More preferably, an adhesive quality of 60% or more can be obtained.

When a fluorescent substance solution is used to adhere the fluorescent substance to the resin surface, a cleaning liquid for cleaning the component surface can be used as a solvent for dissolving the fluorescent substance. By using the liquid that is preferably used as a cleaning liquid for cleaning the surface of the component as described above as a solvent for the fluorescent substance solution, the adhesion surface of the component can be cleaned with the fluorescent substance solution in the step of attaching the fluorescent substance. can also be performed together. In this case, dust or dirt that may be present on the component surface may be dispersed or dissolved in the solution or solvent during the deposition process of the fluorescent material and removed from the component surface. Alternatively, dust or dirt can be decomposed by a solution and the resulting material dispersed or dissolved in the solution or solvent and removed from the component surface.

In other words, in this embodiment, by adding the fluorescent substance to the cleaning liquid used in the step of cleaning the surface of the component, the fluorescent substance can be attached simultaneously in the step of cleaning the surface of the component. Therefore, the fluorescent material can be applied to the adhesive surface during cleaning without significantly changing the cleaning or washing process performed before the dry treatment from the conventional one.

When wiping the surface of the component with a wiping material impregnated with the fluorescent substance solution, the surface of the component may be wiped without applying pressure, or a pressure of 0.2 kPa or more and 60 kPa or less may be applied to the surface of the component. You can go to Dirt on the surface of the component can be reliably removed by performing the wiping operation under pressure. Dirt and dirt can be mechanically removed from the resin surface while the solvent decomposes the dirt or dissolves the dirt in the solvent.

In addition, it is preferable to attach the fluorescent substance in a wider range than the area to be dry-processed (the area preset to be dry-processed) in the subsequent dry process (S12). For example, it is preferable that the area to which the fluorescent material is adhered is formed in a range protruding from the periphery of the area to be dry-processed.

(Dry process (S12))
The dry treatment is performed on the bonding surface after the step (S11) of attaching the fluorescent substance to the bonding surface of the component as described above. The dry treatment is applied to at least the area to be dry treated on the bonding surface, more specifically, to the area including the area to be coated with the adhesive in the subsequent step of applying the adhesive (S20).

Specific examples of dry treatment include plasma treatment, corona treatment, flame treatment, itro treatment, ultraviolet irradiation treatment, excimer treatment, etc. Among them, at least one of plasma treatment and corona treatment is preferred. When the dry treatment is plasma treatment, the generating means is not particularly limited, and may be a high-frequency plasma generator or a low-frequency plasma generator. Further, plasma generated by irradiation with laser, microwave, or the like may be used.

Dry treatment can introduce or form hydrophilic functional groups such as hydroxyl groups, carbonyl groups, and carboxyl groups on the resin surface, and can increase the number of hydrophilic functional groups per unit area. As a result, when the resin surface of the part is used as the adhesive surface and is adhered to the window glass of an automobile via an adhesive, the hydrophilic functional groups on the surface and the components of the adhesive can interact with each other through chemical bonds or intermolecular forces. can be increased and the bond (interfacial bond) between the part and the adhesive can be strengthened. In addition, the dry treatment can decompose and remove substances that may interfere with adhesion existing on the surface of the parts (dirty substances that could not be removed even by the above-described cleaning). Therefore, the dry process (S12) can also be said to be a process of dry cleaning or washing. Further, in that case, when cleaning is performed together with the step of attaching the fluorescent substance (S11), it can be said that cleaning is performed in two stages in this embodiment.

Since the adhesion between the part and the adhesive can be enhanced by performing the dry treatment, the automobile window glass structure can be manufactured without applying the primer to the surface of the part, but the dry treatment was performed. A primer may be applied later and an adhesive may be applied to the primer to bond the part to the automotive glazing. In that case, the adhesiveness between the dry-treated surface and the primer can be enhanced, so that the adhesiveness between the part and the automobile window glass can be enhanced.

The dry treatment conditions can be appropriately adjusted according to the type of resin and adhesive used on the surface of the part, the purpose of use of the part, the place of use in the automobile, the desired adhesive strength, and the like. The specific conditions for the dry process cannot be generalized because they depend on the type of the apparatus for the dry process and the configuration of parts. The frequency of the voltage may be 50 GHz or more and 2.45 GHz or less, preferably 50 Hz or more and 25 kHz or less, and the irradiation distance (the distance between the electrode and the molded body surface) may be 50 mm or less, preferably 10 mm or more and 30 mm or less. The lower limit of the distance between the opposing nozzle and the workpiece (molding) is not particularly limited, but may be, for example, 0.5 mm or more. The output power density may be 15 W/cm ² or higher, preferably 20 W/cm ² or higher. The irradiation time is determined by the moving speed of the nozzle. The moving speed of the nozzle 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.

When plasma treatment is performed, if the surface temperature of the part having a resin surface is increased by heating the molded body with a heater or the like in advance before plasma irradiation, the part in the structure obtained through the subsequent steps will be heated. Adhesion between adhesives can be further improved. The surface temperature of the component before plasma irradiation can be set to a temperature exceeding room temperature, for example, and may be set to 60° C. or higher, for example.

(Evaluation of dry processing (S13))
After dry processing is applied to the surface to which the fluorescent substance is adhered as described above (S12), the dry processing is evaluated by observing the fluorescence emitted from the bonding surface of the component (S13). Although this observation may be performed on the entire bonding surface, it can be performed on at least the area to be dry-processed (the area including the area to be actually coated with the adhesive) of the bonding surface. .

It is believed that when the area where the fluorescent material adheres is subjected to an appropriate dry treatment, the fluorescent material decomposes and loses its ability to emit fluorescence. Therefore, in the evaluation step (S13), by measuring the fluorescence intensity of the bonding surface, it is possible to determine whether or not the bonding surface has been appropriately dry-processed. For example, when the observation after the dry treatment shows that the detected fluorescence intensity is zero or the fluorescence intensity is equal to or less than a predetermined value, it can be determined that an appropriate dry treatment has been performed.

Appropriate dry processing means that the part has been subjected to the dry processing step, or that the area to be dry processed (the region preset to be dry processed) has been subjected to the dry processing step. It may be what is being done. Additionally, proper dry processing may be the proper degree of dry processing actually performed in the area to be dry processed and/or the proper extent of dry processing. Therefore, the user of the method according to the present embodiment, depending on the degree of dry processing desired, the intensity of fluorescence intensity criteria and / or fluorescence intensity for determining that the dry processing is appropriate Range criteria can be set as appropriate. Therefore, depending on the configuration, it may be determined that the dry process has been properly performed even if the fluorescent material remains in the area to be dry processed. Here, an appropriate dry treatment is such that when an adhesive is applied and tested, the cohesive failure rate (adhesive adhesion area ratio) is preferably 30% or more, more preferably 40% or more, and still more preferably 60%. It is possible to perform a treatment that provides the adhesion quality described above.

When measuring the fluorescence intensity, it is preferable to have a control area on the adhesive surface for comparison. For example, adjacent to the area to be dry-processed, an area to which the fluorescent substance is deposited under the same conditions as the area to be dry-processed, but which is not dry-processed, is provided. Such non-dry processed control areas can be formed during the dry process by, for example, covering the areas with a mask. If the part itself is not subjected to the dry treatment process due to a malfunction of the dry treatment equipment, etc., or if the surface other than the adhesion surface of the part is dry treated, the fluorescent material will not adhere to any area of the adhesion surface. Therefore, by observing the fluorescence in the control area, it is possible to make a correct judgment even if the above case occurs. When a control area is provided, the ratio of the fluorescence intensity in the area to be dry-processed to the fluorescence intensity in the control area is obtained, and the dry process is evaluated based on the ratio, that is, the determination of whether or not the appropriate dry process has been performed. may be performed. The control area may be an area surrounding the area to be dry-processed when the area to which the fluorescent material is to be adhered is formed so as to protrude from the periphery of the area to be dry-processed in the step of attaching the fluorescent material (S11). It is preferred because it allows for easier recognition of control regions.

In addition, in the step of attaching the fluorescent substance (S11), when both the cleaning of the resin surface and the adhesion of the fluorescent substance are performed using a fluorescent substance solution using a cleaning liquid for cleaning as a solvent, Along with determining whether the dry treatment was properly applied, it is also possible to determine whether cleaning has taken place. For example, if a fluorescent substance solution is applied to an area other than the area to be dry-processed, such as the above-mentioned control area, whether or not the cleaning is being performed can be determined by observing the fluorescence in that area. I can judge.

Observation of fluorescence in the evaluation step (S13) of the dry treatment may be performed visually, for example. Direct visual observation is preferable and practical from the viewpoint of simplicity and low cost because it does not require a large-scale apparatus. For visual observation, a light irradiation device may be brought close to irradiate light for observation. For example, a UV-LED light generator can be used to irradiate the bonding surface with ultraviolet light, and fluorescence can be visually observed. When BBOT is used as the fluorescent material, it can be easily observed visually by irradiating it with ultraviolet rays.

Fluorescence observation may be performed using a device capable of detecting fluorescence, such as a fluorescence microscope or a fluorescence filter. When observing through an instrument in this way, it is possible to detect fluorescence even if the fluorescence intensity is low. preferable from this point of view. When using a device such as a fluorescence microscope, the fluorescence intensity may be confirmed with the human eye through an eyepiece, or the adhesive surface may be imaged with a camera or the like, and the image data may be captured by a personal computer or the like and displayed on a display device. You may confirm fluorescence intensity by displaying. Additionally, the captured image data can be used for image processing, which allows for more accurate measurements of fluorescence intensity. Also, if equipment is used, the determination of whether proper dry processing has been performed may be automated.

As described above, in the main evaluation step (S13), the dry treatment (S12) performed in the previous step can be evaluated by observing the fluorescence emission state visually or through an instrument. Therefore, in one embodiment of the present invention, a fluorescent substance is attached to the bonding surface of a component having a resin surface (S11), dry treatment is performed (S12), and the fluorescence emission state of the dry-treated bonding surface is observed. It may be a dry process evaluation method including evaluating the dry process (S13). Evaluation according to this embodiment is a non-contact type, and since no object is brought into contact with the adhesive surface after dry processing, the parts are subjected to the subsequent bonding step (S20) without changing the state of dry processing. be able to. In addition, since it is possible to easily observe the entire area to be dry-processed, it is possible to detect unprocessed areas and the like. High evaluation is possible.

(Adhesion with automotive window glass (S20))
Through the evaluation (S10) including the above steps S11 to S13, when it is determined that the area to be dry-processed is actually an appropriately dry-processed area (dry-processed area), the dry-processed adhesive surface An adhesive can be applied to the region to adhere it to the automobile window glass (S20). At the time of adhesion, a primer can also be applied to the adhesion surface of the automobile window glass.

If it is determined by the evaluation (S10) that the appropriate dry treatment is not performed, for example, if the degree of dry treatment is weak or there is an undesired untreated area in the area to be dry treated, The dry process (S12) may be performed again. Then, the newly performed dry process is evaluated (S13), and if it is confirmed that it is an appropriate dry process, it is possible to proceed to the bonding step (S20).

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

Note that after bonding the automobile window glass and the part having the resin surface with an adhesive, they may be stored in a predetermined environment, that is, cured. This curing can also improve adhesion between the automotive glazing and the part. For example, curing can be performed by storing for a predetermined period of time under temperature and humidity depending on the type of adhesive.

Hereinafter, embodiments of the present invention will be described in further detail based on examples. In this example, the surface of the resin molded body was cleaned with a solution of a fluorescent substance and then subjected to dry treatment, and the dry treatment was evaluated by observing the fluorescence of the surface after the dry treatment. Adhesive was applied to the resin molding and the adhesion between the resin molding and the adhesive was evaluated. Examples 1 to 6 are working examples, and example 7 is a comparative example.

(Example 1)
As the resin molded body, a plate-shaped molded body (25 mm × 150 mm × 5 mm) made of glass fiber reinforced polybutylene terephthalate (PBT GF-30) (manufactured by Polyplastics Co., Ltd., 733LD) containing 30% glass fiber was used. . On the other hand, 2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene (BBOT) was dissolved in n-hexane (manufactured by Wako Pure Chemical Industries, Ltd., special grade) to give a concentration of 1×10 ⁻⁴ mol/L ( 0.0065% by weight) was prepared. Almost the entire surface of the resin molding was wiped with a non-woven cloth wiper (BENCOT (registered trademark) manufactured by Asahi Kasei Corp.) soaked with the solution to clean it. After visually confirming that the solution had evaporated, one half of the cleaned region was subjected to plasma treatment (dry treatment) using an atmospheric pressure plasma treatment apparatus (PS-601SW manufactured by Wedge Co., Ltd.). The distance between the head and the component surface in the plasma treatment was 10 mm, and the irradiation time was 4 seconds. The plasma treatment was evaluated by the method described later, and then an adhesive was applied to the plasma-treated region, and the adhesiveness was evaluated by the method described later.

(Example 2)
The resin molded body was cleaned and plasma-treated in the same manner as in Example 1, except that the concentration of the solution was 1 × 10 ^-5 mol / L (0.00065% by weight), and evaluation of plasma treatment and adhesiveness was performed. made an evaluation.

(Example 3)
Example 1 except that a solution with a concentration of 1×10 ⁻⁴ mol/L (0.0065% by weight) obtained by dissolving BBOT in mixed ethanol (manufactured by Yamaichi Chemical Industry Co., Ltd., mixed ethanol NP) was used. Similarly, the resin molding was cleaned, plasma-treated, and evaluated for plasma treatment and adhesiveness.

(Example 4)
The resin molded body was cleaned and plasma-treated in the same manner as in Example 3, except that the concentration of the solution was 1 × 10 ^-5 mol / L (0.00065% by weight), and evaluation of plasma treatment and adhesiveness was performed. made an evaluation.

(Example 5)
The resin molded body was cleaned and plasma-treated in the same manner as in Example 1, except that the concentration of the solution was 1 × 10 ^-3 mol / L (0.065% by weight), and evaluation of plasma treatment and adhesiveness was performed. made an evaluation.

(Example 6)
Except for using a solution with a concentration of 1×10 ⁻⁵ mol/L (0.00065% by weight) obtained by dissolving methylene blue (MeB) in mixed ethanol (manufactured by Yamaichi Chemical Co., Ltd., mixed ethanol NP), The resin molding was cleaned in the same manner as in Example 1. After that, it was plasma-treated and evaluated.

(Example 7)
In this example, n-hexane (with a solute concentration of 0% by weight) was used instead of the solution, and plasma treatment was not performed. Otherwise, cleaning was carried out in the same manner as in Example 1. After that, plasma treatment was performed, and adhesion was evaluated.

<Evaluation of plasma treatment (dry treatment)>
In Examples 1 to 5 using BBOT as a fluorescent substance and Example 7 in which no fluorescent substance was used, an LED light (LED-UV365P, manufactured by Optocode Co., Ltd.) was applied to the dry-processed surface of the resin molding. A UV-LED light with a wavelength of 365 nm was irradiated using a laser, and the fluorescence intensity in the plasma-treated region was visually confirmed. In these examples, when the fluorescence intensity was visually judged to be zero in the plasma-treated region, no fluorescence was detected, and it was judged that the plasma treatment was actually properly performed. In making the judgment, the light emission state of the plasma-treated region was compared with the light emission state of the region adjacent to the plasma-treated region on the other side, which was not subjected to the plasma treatment.

In Example 6, in which methylene blue was used as the fluorescent substance, the dry-treated surface of the resin molding was observed with a fluorescence microscope, and the image obtained through the fluorescence microscope was analyzed. Then, based on the image analysis, fluorescence intensity was measured in the plasma-treated region. In this example, when the fluorescence intensity was zero in the plasma-treated region, no fluorescence was detected, and it was determined that the plasma treatment was actually properly performed. At the time of judgment, similarly to the above, the light emission state of the plasma-treated region was compared with the light emission state of the region adjacent to the plasma-treated region on the other side, which was not subjected to the plasma treatment.

<Evaluation of adhesiveness>
A urethane-based adhesive (WS292, manufactured by Yokohama Rubber Co., Ltd.) is applied to the plasma-treated area, and the adhesive adhesion area after knife cutting is performed by a method that conforms to the 9.11 pot life test of JASO M338-89 standards. It was evaluated based on the rate (percentage of the area where the adhesive remained or the rate of cohesive failure). When the adhesive adhesion area ratio is 0%, the adhesive does not undergo cohesive failure at all, and interfacial peeling occurs. It is in a state of destruction. The higher the adhesion area ratio of the adhesive, the higher the rate of cohesive failure in the adhesive, and the adhesiveness between the resin molding and the adhesive can be evaluated as good.

Table 1 shows the conditions and evaluation results of each example.

As shown in Table 1, in any of Examples 1-6, evaluation of dry processing (determining whether or not plasma processing was performed) was performed by cleaning with a solution of fluorescent material prior to dry processing. It was found that it is possible and the adhesion between the test piece and the glass plate is also ensured. In addition, when the concentration of the fluorescent substance in the solution used for cleaning is 1×10 ⁻⁴ mol/L or less (Examples 1 to 4 and Example 6), the adhesive adhesion area ratio exceeds 40%. It was found that particularly good adhesion was obtained.

1 Automobile Window Glass Structure 10 Glass 15 Shielding Layer 20 Resin Part (Bracket)
30 adhesive layer

Claims (11)

A method for manufacturing an automobile window glass structure in which a part having a resin surface is adhered to an automobile window glass,
Adhering a fluorescent substance to the bonding surface of the part having the resin surface,
Performing a dry treatment on the adhesive surface,
evaluating the dry treatment by observing fluorescence emitted from the adhesive surface;
A method of manufacturing an automobile window glass structure, wherein the component is adhered to the automobile window glass via an adhesive applied to the adhesion surface. 2. The manufacturing method according to claim 1, wherein said fluorescent material is attached using a solution of said fluorescent material. 3. The manufacturing method according to claim 2, wherein the adhesion of the fluorescent substance is performed while cleaning the bonding surface. 4. The manufacturing method of claim 3, wherein said cleaning includes wiping said adhesive surface with a wiping material soaked with said solution. 5. The manufacturing method according to any one of claims 2 to 4, wherein the solution is a solution obtained by dissolving the fluorescent material in an organic solvent. 6. The production method according to any one of claims 2 to 5, wherein the concentration of the fluorescent substance in the solution is 1 x 10 ^-6 mol/L or more and 1 x 10 ^-2 mol/L or less. 7. The production method according to any one of claims 1 to 6, wherein the fluorescent substance is at least one of 2,5-bis(5-tert-butyl-2-benzoxazolyl)thiophene and methylene blue. 8. The manufacturing method according to any one of claims 1 to 7, wherein the dry treatment is at least one of plasma treatment and corona treatment. 9. The manufacturing method according to any one of claims 1 to 8, wherein the observation of fluorescence includes irradiating UV light and directly observing visually. 10. The manufacturing method according to any one of claims 1 to 9, wherein observing the fluorescence includes observing with a fluorescence microscope. A method for evaluating a dry treatment applied to a part having a resin surface that is adhered to an automobile window glass,
Adhering a fluorescent substance to the bonding surface of the part having the resin surface,
Performing a dry treatment on the adhesive surface,
An evaluation method, wherein the dry treatment is evaluated by observing fluorescence emitted from the adhesive surface.

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