WO2020116273A1 - Procédé de fabrication d'une structure de véhicule et procédé de traitement d'une carrosserie moulée de véhicule - Google Patents

Procédé de fabrication d'une structure de véhicule et procédé de traitement d'une carrosserie moulée de véhicule Download PDF

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Publication number
WO2020116273A1
WO2020116273A1 PCT/JP2019/046340 JP2019046340W WO2020116273A1 WO 2020116273 A1 WO2020116273 A1 WO 2020116273A1 JP 2019046340 W JP2019046340 W JP 2019046340W WO 2020116273 A1 WO2020116273 A1 WO 2020116273A1
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WIPO (PCT)
Prior art keywords
molded body
treatment liquid
adhesive
resin
vehicle
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PCT/JP2019/046340
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English (en)
Japanese (ja)
Inventor
直樹 手嶋
研一 江畑
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Ａｇｃ株式会社
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Priority to JP2020559099A priority Critical patent/JPWO2020116273A1/ja
Publication of WO2020116273A1 publication Critical patent/WO2020116273A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60J—WINDOWS, WINDSCREENS, NON-FIXED ROOFS, DOORS, OR SIMILAR DEVICES FOR VEHICLES; REMOVABLE EXTERNAL PROTECTIVE COVERINGS SPECIALLY ADAPTED FOR VEHICLES
    • B60J1/00—Windows; Windscreens; Accessories therefor
    • B60J1/08—Windows; Windscreens; Accessories therefor arranged at vehicle sides
    • B60J1/12—Windows; Windscreens; Accessories therefor arranged at vehicle sides adjustable
    • B60J1/16—Windows; Windscreens; Accessories therefor arranged at vehicle sides adjustable slidable
    • B60J1/17—Windows; Windscreens; Accessories therefor arranged at vehicle sides adjustable slidable vertically
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/02—Chemical treatment or coating of shaped articles made of macromolecular substances with solvents, e.g. swelling agents

Definitions

  • the present invention relates to a method for manufacturing a vehicle structure and a method for treating a vehicle molded body.
  • resin parts used in vehicles such as automobiles many resin parts or at least parts having resin on the surface are well known. Some of such parts are adhered to a transparent substrate such as glass with an adhesive, and an example thereof is a molded body such as a resin bracket for mounting an in-vehicle device or the like on the inner surface of the windshield. Be done. Such a molded body is often bonded to a transparent substrate via an adhesive.
  • Patent Document 1 In order to improve the adhesiveness of the resin surface of the molded body, it is known to perform plasma irradiation or the like on the molded body to modify the surface of the molded body (for example, Patent Document 1). ).
  • the resin surface of the molded body is treated only by plasma or the like, and The adhesiveness between them may not be sufficient. Therefore, a method for improving the adhesiveness between the molded body and the adhesive is required in the production of a structure in which the molded body and the transparent substrate for a vehicle are bonded together with the adhesive.
  • an object of the present invention is to provide a manufacturing method capable of improving adhesiveness.
  • one embodiment of the present invention is a plasma treatment step of performing plasma treatment on a molded body having a resin surface, and water and a hydrophilic organic solvent on the surface of the molded body after the plasma treatment step.
  • a molecule adsorbing step of adsorbing molecules of a treatment liquid containing at least one of the above, and a step of adhering the molded body after the adsorbing step to a vehicle transparent substrate with an adhesive to obtain a vehicle structure It is a manufacturing method of a structure for vehicles.
  • the adhesiveness between the molded product having a resin surface and the adhesive is improved. It is possible to provide a manufacturing method capable of
  • FIG. 1 is a plan view of a vehicle structure according to an embodiment of the present invention.
  • FIG. 2 is a partial view of a cross section taken along line II of FIG. 1.
  • the plasma treatment step is a step of irradiating the surface of the molded product having a resin surface with plasma.
  • the plasma generating means used in this step is not particularly limited and may be a high frequency plasma generating device or a low frequency plasma generating device.
  • the plasma treatment in the plasma treatment step may be so-called corona treatment that can generate corona. Further, it may be a process using plasma generated by irradiation with laser or microwave.
  • the molded product having a resin surface to be treated in this form may be one that contains a resin on at least the surface. That is, the molded body having a resin surface may be, for example, a molded body made of resin in which the entire molded body is mainly formed of resin, or a part or all of the surface of the molded body made of a material other than resin. May be coated with a resin.
  • the molded product having a resin surface may be referred to as a “resin molded product” or simply “molded product”.
  • the resin material used for the molded product having a resin surface is not particularly limited, but polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polyolefins such as polyethylene (PE) and polypropylene (PP), polycarbonate (PC) Polyamide (PA) such as nylon 6, nylon 6,6, etc., high heat-resistant polyamide based on terephthalic acid or isophthalic acid (PA6T, PA6I, PA6T/6I etc.), polyimide (PI), polyetherimide (PEI), Examples thereof include acrylonitrile-butadiene-styrene (ABS), polyacetal (POM), polyvinyl chloride (PVC) and epoxy (EP).
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PA polyolefins
  • PE polyethylene
  • PP polypropylene
  • PC polycarbonate
  • PA Polyamide
  • PA such as nylon 6, nylon 6,6,
  • the resin material may be used as a homopolymer, or may be used as a copolymer by combining one or more of the above.
  • the resin material is preferably a polymer alloy in which one or more of the above are combined, for example, a polymer alloy of polybutylene terephthalate and styrene acrylonitrile, especially when the molded body is a resin molded body.
  • the resin material may be a resin reinforced with a filler such as fiber or inorganic particles.
  • a filler such as fiber or inorganic particles.
  • the reinforcing fibers glass fibers, carbon fibers and the like are preferable.
  • the fiber reinforced resin glass fiber reinforced polybutylene terephthalate, polyether imide and the like are preferable.
  • the fibers can be contained in an amount of 5 to 70% by mass, preferably about 30 to 50% by mass, based on the whole resin.
  • the molding method is not limited, and the above resin material may be molded by a method such as injection molding, casting, extrusion or blow molding. .. Further, it may be insert-molded using an insert material made of a material (metal or the like) other than resin.
  • the molded body having a resin surface is a molded body made of a material other than resin, in which a part or all of the surface of the molded body is coated with the resin, for example, a base made of metal or the like contains the resin. It may be an electrodeposition coated body that is electrodeposition coated using an electrodeposition coating.
  • the electrodeposition coated body is a film formed by energizing a substrate (base material) in an electrolytic bath to deposit resin coating particles on the surface of a component and heating and curing in a curing furnace.
  • the electrodeposition coating is preferably a cationic electrodeposition coating.
  • the resin contained in the electrodeposition paint can be a thermosetting resin such as an epoxy resin, and preferably contains an epoxy resin modified with amine, ammonium or the like.
  • the base body may be a molded body of metal containing steel, aluminum or the like, particularly a plate-shaped molded body.
  • the electrodeposition coated body include cation electrodeposition coated steel sheet manufactured by Aoki Denki Kogyo (using Electron HG-305E black manufactured by Kansai Paint Co., Ltd. as the electrodeposition coating).
  • the resin surface may be formed by applying a solution or dispersion liquid containing a resin, a resin melt, or the like onto a substrate, or by applying a sheet-shaped resin layer formed in advance, It can also be formed by electrolytic plating or the like.
  • the substrate surface may be covered with the resin layer.
  • at least a part of the surface (bonding surface) to be bonded to the vehicle transparent substrate described later may be covered with the resin layer, and the entire bonding surface may be covered with the resin layer.
  • a molded article having a resin surface as described above can first be chemically surface-modified by a plasma treatment step.
  • hydrophilic functional groups such as hydroxyl group, carbonyl group and carboxyl group can be introduced or formed on the resin surface, and the number of hydrophilic functional groups per unit area can be increased.
  • an adherend such as a transparent substrate by applying an adhesive such as a urethane-based adhesive with the resin surface as an adhesive surface
  • a hydrophilic functional group on the surface is used. It is possible to increase the number of places where the component of the adhesive and the adhesive can interact with each other by a chemical bond or an intermolecular force, and to strengthen the bond (interfacial bond) between the molded body and the adhesive.
  • increasing the number of hydrophilic functional groups per unit area can increase the number of sites where hydrophilic molecules can be adsorbed, and the amount of hydrophilic molecules that can stably exist on the resin surface of the molded body ( Density) can be increased.
  • molecular adhesion is performed in advance on such sites before applying the adhesive, whereby curing of the adhesive at the interface between the molded body and the adhesive is promoted. It was found that the effect can be enhanced.
  • the plasma irradiation conditions can be appropriately adjusted depending on the types of resin and adhesive used in the molded body, the purpose of use of the molded body, and the location of use in a vehicle. Although it cannot be generally stated because it depends on the constituent material of the plasma generator and the molded body, for example, the frequency of the voltage applied to the power source of the plasma generator is 50 Hz to 2.45 GHz, preferably 50 Hz to 25 kHz, and the irradiation distance (electrode And the surface of the molded body) is 50 mm or less, preferably 10 mm to 30 mm.
  • the lower limit of the distance between the nozzle and the work (molded body) facing each other is not particularly limited, but is, for example, 0.5 mm or more.
  • the output power density is 15 W/cm 2 or more, preferably 20 W/cm 2 .
  • the irradiation time is determined by the moving speed of the nozzle.
  • the moving speed of the nozzle can be 0.01 m/min to 50 m/min, preferably 2.5 m/min to 10 m/min, more preferably 2.5 m/min to 4 m/min. If the irradiation distance is 10 mm and the moving speed of the nozzle is in the range of 2.5 m/min to 4 m/min, even plastic that is difficult to modify can be modified.
  • the structure obtained through the subsequent steps is The adhesiveness between the molded body and the adhesive can be further improved.
  • the hot water durability of the obtained vehicle structure (the durability when the molded body and the transparent substrate are bonded by an adhesive and then immersed in hot water for a predetermined time) can be improved.
  • the surface temperature of the molded body before plasma irradiation can be raised to a temperature higher than room temperature (15°C to 25°C), for example, 60°C or higher, preferably 80°C or higher, more preferably 100°C or higher,
  • the temperature can be more preferably 120° C. or higher, further preferably 140° C. or higher.
  • the storage temperature of the molded product before the plasma treatment step when storing a highly hygroscopic material such as polyamide having a saturated water absorption of 1% or more, the storage temperature should be 25°C or lower. Is desirable.
  • the treatment liquid can be adsorbed on the resin surface of the molded body by supplying the treatment liquid to the surface of the molded body after the plasma treatment step.
  • the treatment liquid may contain at least one of water and a hydrophilic organic solvent. That is, the treatment liquid can be water, one containing at least one hydrophilic organic solvent, or a mixture of water and at least one hydrophilic organic solvent.
  • adsorbing a molecule on the surface of a molded article refers to binding a molecule to a functional group existing on the resin surface of the molded article by an intermolecular force, and the molecule is bound to the resin surface of the molded article. It may be said that this means so-called monolayer adsorption.
  • the “surface adsorption molecule” or “adsorption molecule” refers to a molecule directly bonded to a functional group existing on the resin surface of the molded body.
  • a molecule which is not directly bonded to a functional group existing on the resin surface of the molded body may be referred to as a “condensed molecule”.
  • a hydrophilic functional group is introduced or formed on the resin surface of the molded body by the plasma treatment step, and such a hydrophilic functional group is likely to bond water molecules or hydrophilic molecules.
  • a treatment liquid containing at least one of water and a hydrophilic organic solvent to the surface of the molded body, the molecules of water or the hydrophilic organic solvent can be easily adsorbed on the resin surface of the molded body. That is, the water molecule and/or the molecule of the hydrophilic organic solvent can be directly bonded to the hydrophilic functional group existing on the resin surface of the molded body by hydrogen bond, van der Waals force or the like. By such a direct bond, the treatment liquid molecules can be stably present on the resin surface of the molded body.
  • the manufacturing method according to this embodiment further includes a step of adhering an adherend such as a transparent substrate using an adhesive after the molecular adsorption step (adhesion step described later).
  • the former action can be explained by the presence of adsorbed molecules, which improves the wettability between the adhesive and the resin surface and facilitates the interaction between molecules such as electrostatic interaction and van der Waals force.
  • an adhesive contains additives such as a plasticizer in addition to the adhesive component, but when the curing of the adhesive is slow, such an additive component migrates to the interface and the molded product and the coating It may reduce the adhesive strength to the body.
  • the curing of the adhesive is promoted by the treatment liquid molecules existing on the resin surface of the molded body, so that the migration of the additive components to the vicinity of the interface can be prevented, and the additive in the adhesive can be prevented. It is believed that the effects of the components on the adhesiveness at the interface between the molded body and the adhesive can be reduced.
  • the treatment liquid contains at least one of water and a hydrophilic organic solvent.
  • the total amount of water and the hydrophilic organic solvent in the treatment liquid is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more.
  • the treatment liquid is preferably water, a hydrophilic organic solvent, or a mixture thereof.
  • the treatment liquid preferably contains water because it is inexpensive and has high safety and operability. No special additives are required, as can be seen from the use of distilled water as the treatment liquid in the examples.
  • the amount of water in the treatment liquid is preferably 60% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, based on 100% by mass of the processing liquid, and the treatment liquid is water. Is more preferable.
  • the hydrophilic organic solvent contained is an organic solvent which has an affinity for the hydrophilic groups present on the resin surface of the molded body and does not modify the resin material used in the molded body. If it is, there is no particular limitation.
  • Hydrophilic organic solvents used in the treatment liquid include alcohols such as methanol, ethanol, 2-propanol (isopropyl alcohol), 1-propanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; butyl acetate, ethyl acetate, glycol ester. And the like; aliphatic or alicyclic hydrocarbons such as n-hexane and cyclohexane; ethers such as diethyl ether and glycol ether. These organic solvents can be used alone or in combination of two or more. Further, among these organic solvents, it is preferable to use one or more of methanol, ethanol, acetone, methyl ethyl ketone, butyl acetate, and ethyl acetate.
  • organic solvents inevitably contain trace amounts of water. This inevitably contained water is water that cannot be removed at the production stage of the organic solvent, or is mixed in although not actively added at the preparation stage of the treatment liquid.
  • the organic solvent is 5% by mass or less, 1% by mass or less, 0.5% by mass or less, 0.2% by mass or less, and 0.1% by mass or less with respect to 100% by mass of the organic solvent. Inevitably, it may contain water. In the present invention, even an organic solvent containing a trace amount of water and having a low purity is effective.
  • the treatment liquid contains an organic solvent or the treatment liquid consists of an organic solvent
  • the content of unavoidable water contained in the organic solvent before preparation of the treatment liquid is 100% by weight of the treatment liquid.
  • the content of water relative to 100 mass% is 0.001 mass% or more, 0.1 mass% or more, 0.2 mass% or more, 0.4 mass% or more, 0.5 mass% or more, 1 mass% or more, It can be 5 mass% or more.
  • the treatment liquid contains water together with the hydrophilic organic solvent
  • the hydrophilic organic solvent if the hydrophilic organic solvent is volatile, after the treatment liquid is supplied to the surface of the resin molded body, the organic solvent volatilizes first and water molecules are formed. It becomes easier to adsorb on the resin surface. That is, the water molecules are likely to bond with the functional groups present on the resin surface of the molded body.
  • the adsorbed molecules are mainly water molecules as described above, the curing of the adhesive is promoted particularly when a moisture-curable adhesive is used in the adhesion step, and the additive component such as a plasticizer in the adhesive is It is possible to prevent migration and the like.
  • the treatment liquid may contain any additive.
  • additives that can be contained in the treatment liquid include isocyanate, silane coupling agents, and preservatives.
  • the treatment liquid may be substantially free of an organic compound having a sulfo group.
  • the phrase “does not contain a predetermined component” means that the predetermined component is not added as a constituent component when preparing the treatment liquid.
  • the content of the organic compound having a sulfo group in the treatment liquid used in the present embodiment is, for example, less than 0.5% by mass, specifically 0.1% by mass or less, and more specifically 0.01% by mass. % Or less, and more specifically less than 0.001% by mass.
  • the treatment liquid may be substantially free of a strong acid component including an organic compound having a sulfo group, and may be substantially free of an acid component.
  • the acid component include organic compounds having a sulfo group, for example, inorganic acids such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, nitric acid and sulfuric acid, and organic acids such as carboxylic acid and thiol. (Excluding alcohol), and derivatives thereof.
  • ⁇ Corrosion of surrounding metals can be reduced by making the treatment liquid substantially free of organic compounds having sulfo groups, and by making it substantially free of strong acid components.
  • the treatment liquid contains substantially no acid component, a cheaper process can be realized.
  • a functional group can be introduced or formed on the resin surface of the molded body by the plasma treatment step, and the treatment liquid molecule can be adsorbed by the molecule adsorption step.
  • This makes it possible to strengthen the bond between the adhesive to be subsequently applied and the surface of the molded body, accelerates the curing of the adhesive at the interface with the molded body and in the vicinity thereof, and improves the adhesiveness due to the migration of the additive components. It is possible to prevent the decrease.
  • the two steps of the plasma treatment and the molecule adsorption of the present embodiment can improve the adhesiveness between the molded body having the resin surface and the adhesive.
  • the present embodiment it is possible to obtain a structure in which the molded body and the adherend are bonded with high adhesiveness directly through the adhesive without applying a primer or the like on the resin surface of the molded body. ..
  • a primer is used for adhesion, the adhesiveness between the molded product and the primer can be improved.
  • the amount is generally small, and it is difficult to obtain the excellent adhesiveness obtained by the embodiment of the present invention.
  • adsorbed molecules may disappear depending on the treatment conditions. For example, when plasma treatment is performed under a strong condition such as irradiation with high output for a long time, adsorbed molecules may be scattered. Even in such a case, in the present embodiment, since the molecules of the treatment liquid are adsorbed on the resin surface of the molded body after the plasma treatment, the adhesiveness between the molded body and the adhesive is irrespective of the plasma treatment conditions. Can be improved.
  • the supply of the treatment liquid to the surface of the molded body in the molecule adsorption step can be performed as follows.
  • the first form of the molecule adsorption step is to bring the treatment liquid into contact with the molded body using a tool or the like.
  • This contact with the treatment liquid includes allowing the treatment liquid to stand in a state where the treatment liquid is in contact with the treatment liquid, and also includes moving the treatment liquid relative to the treatment liquid while contacting the treatment liquid.
  • the molded body can be immersed in the treatment liquid contained in a container or the like.
  • the immersion includes, in addition to immersing the molded body in the treatment liquid for a predetermined time and then pulling it up, pouring the treatment liquid on the surface of the molded body and rinsing the molded body with the treatment liquid.
  • the treatment liquid can be supplied by spraying the treatment liquid on the surface of the molded body.
  • the spraying of the treatment liquid also includes splashing drops of the treatment liquid, spraying with a spray or the like, and spraying heated steam (steam).
  • the treatment liquid can be applied.
  • the treatment liquid can be applied by immersing the treatment liquid in a cloth or cotton, and stroking the surface of the molded body with the cloth or cotton, or by using a brush or the like.
  • the treatment liquid is dipped in cloth or cotton and the surface of the molded product is rubbed with the cloth or cotton, the fibers and compounds contained in the cloth or cotton remain on the adhesive surface during application, and the adhesion is hindered. I have a concern.
  • a method of immersing the molded body in the treatment liquid contained in a container or spraying the treatment liquid on the surface of the molded body is preferable. If the treatment liquid is supplied by coating, it is preferable that the pressure is not applied to the surface of the molded body or the pressure applied to the surface of the molded body is suppressed to about 0.2 kPa or less. This can reduce the possibility that fibers or compounds will remain on the adhesive surface.
  • a second mode of the molecule adsorption step is to form a space in which the treatment liquid (molecules of the treatment liquid) can exist in a gas state and arrange the molded body so that the resin surface is exposed in the space. Be done. For example, a space in which the vapor pressure of at least one of water and the hydrophilic organic solvent that form the treatment liquid is increased is formed, and the molded body is stored in the space for a predetermined time. As a result, the treatment liquid molecules in a gas state can be adsorbed on the resin surface of the molded body.
  • the molded body is preferably stored for at least a time such that adsorption equilibrium is reached.
  • the molded product can be stored in a high humidity environment.
  • the high humidity environment may be an environment having a humidity exceeding normal humidity (relative humidity 45 to 85% RH).
  • the molecular adsorption by storage in a high humidity environment can be performed in an environment of relative humidity of 60% RH or more, preferably 80% RH or more, more preferably 90% RH or more.
  • the storage temperature is preferably 30° C. or lower.
  • the treatment liquid molecules are adsorbed at least in an amount in equilibrium with the functional groups on the surface of the molded body. ..
  • the surface of the molded body can be cleaned by a known method before the plasma treatment step. That is, the manufacturing method according to the present embodiment may include a cleaning step before the plasma processing step.
  • the cleaning step fine dust or dirt on the surface of the molded body can be physically or chemically removed beforehand. That is, as a specific example of cleaning, removing dust or dirt existing on the surface of the molded body by mechanical force, dissolving the dust or dirt in a solvent, or decomposing the dust or dirt with a solvent , And a combination thereof.
  • the dust or dirt on the surface of the molded body can be sufficiently removed in advance, it is possible to introduce more hydrophilic functional groups into the surface of the molded body in the subsequent plasma treatment, and the hydrophilic functional groups can be bonded to the surface of the molded body. , A more stable bond can be formed. Therefore, it is not necessary to excessively increase the condition of the plasma treatment, and it is possible to reduce the possibility that the resin surface is damaged by the excessive surface treatment.
  • the cleaning method is not particularly limited, but examples include wiping, polishing, and cleaning.
  • wiping the surface of the molded body is wiped with a wiping tool at least within the range where plasma treatment is to be performed.
  • the solvent may be soaked in the wiping material of the wiping tool.
  • the wipe may be provided with, for example, a fiber-containing or porous wipe material capable of absorbing and retaining a solvent.
  • the wiping material may be a sheet-like material such as cloth or non-woven fabric, or a block-like material such as sponge.
  • the solvent can disperse or dissolve dust or dirt that may be present on the surface of the molded article, and is preferably volatile.
  • dirt and stains can be removed by mechanical force from the surface of the molded body while decomposing stains with a solvent or dissolving the stains in the solvent.
  • the wiping may be performed so that no pressure is applied to the surface of the molded body, or may be performed so that a pressure of about 0.2 kPa to 60 kPa is applied to the surface of the molded body.
  • a known surface polishing method using an abrasive and a polishing tool can be used.
  • the material on the surface of the resin molded body is slightly scraped off, so that the dirt on the resin surface can be sufficiently removed.
  • the abrasive for example, mineral particles or a dispersion liquid of mineral particles can be used, but particles of a substance having a sublimation property such as carbon dioxide, that is, a substance that sublimes at room temperature and atmospheric pressure may be used. By using sublimable particles, it is not necessary to remove the abrasive after the polishing process.
  • a known cleaning method for the resin molded body can be used. For example, it can be carried out by immersing the molded body in a cleaning liquid such as a solvent, allowing it to stand for a predetermined time, and then pulling it up. Further, after the molded body is dipped in the cleaning liquid, the cleaning liquid may be made to flow and moved relative to the surface of the molded body. Further, for example, the cleaning liquid may be flowed over the molded body.
  • the solvent can disperse or dissolve dust or dirt that may be present on the surface of the molded article, and is preferably volatile.
  • the manufacturing method according to the present embodiment may have an excess molecule removing step of removing excess processing liquid molecules after the molecule adsorption step.
  • excess molecule removing step at least a part of the condensed molecules of the treatment liquid can be removed.
  • condensed molecules of the treatment liquid can be removed so that the treatment liquid mainly exists as adsorption molecules on the surface of the molded body.
  • the excess molecule removing step it is preferable that the condensed molecules are removed and the adsorbed molecules are not removed. Therefore, the excessive molecule removing step does not include the forcible removal of the processing liquid molecules due to drying such as excessively high temperature heat or gas blowing.
  • the treatment liquid may be allowed to spontaneously evaporate by allowing the molded body after the molecule adsorption step to stand for a predetermined time, or the visible treatment liquid may be absorbed by cloth or cotton. May be.
  • the excess molecule removing step it is preferable to remove the treatment liquid at least on the resin surface of the molded body until the treatment liquid cannot be visually confirmed.
  • Excessive molecules can be removed by the excess molecule removal step, and the existence state of the treatment liquid molecules on the surface of the molded body can be optimized. That is, it is possible to balance the amount (density) of the hydrophilic functional groups present on the surface of the molded body with the amount (density) of the molecules of the treatment liquid. This makes it possible to balance the interfacial bonding between the surface of the molded body and the adhesive and the aggregation within the adhesive when the adhesive is applied.
  • the amount of treatment liquid molecules adsorbed on the surface per unit area is 13 to 15 H 2 O molecules/nm 2 . Certain conditions are preferred. This value is the theoretical maximum density of adsorbed water molecules.
  • the molded body having a resin surface can be adhered to the transparent vehicle substrate by an adhesive.
  • an adhesive can be applied to the resin surface of the molded body that has undergone the plasma treatment and after which the treatment liquid molecules have been adsorbed, and the vehicle transparent substrate can be stacked.
  • the transparent substrate for a vehicle can be coated with an adhesive, and the resin surface of the molded body can be overlaid on the adhesive.
  • a primer for the transparent substrate may be applied to the vehicle transparent substrate side.
  • the adhesive used in the bonding step is preferably a one-component or two-component moisture-curing adhesive, more preferably a urethane adhesive, a modified silicone adhesive, or the like.
  • a moisture-curable adhesive is used, the curing of the adhesive can be promoted by using a treatment liquid containing water.
  • a photo-curing adhesive or a thermosetting adhesive may be used.
  • a photo-curing adhesive or a thermosetting adhesive it is said that the adsorbing molecules improve the adhesiveness by the action of improving the wettability between the resin molding surface and the adhesive after the plasma treatment step. Guessed.
  • the structure obtained by bonding the molded body having a resin surface and the transparent substrate via the adhesive after bonding with the adhesive may be stored in a predetermined environment, that is, cured.
  • Optimum curing conditions vary depending on the materials of the molded body and adhesive, the conditions of the plasma treatment step and the molecular adsorption step, etc., but the curing temperature is preferably 5 to 35°C. Also, the humidity during curing can be set to about 20 to 80% RH. Note that the structure can be cured at a high temperature, for example, by curing the structure at a temperature higher than room temperature. Thereby, the adhesiveness between the adhesive and the molded body can be further enhanced.
  • the vehicle transparent substrate used in this embodiment may be vehicle glass, for example, windshield, rear glass, side glass, or the like.
  • the vehicle glass may be formed from a glass plate such as soda lime silicate glass, aluminosilicate glass, borate glass, lithium aluminosilicate glass, borosilicate glass, or the like.
  • the glass plate may be unstrengthened, or may have been subjected to air-cooling strengthening or chemical strengthening treatment.
  • the unstrengthened glass is formed by shaping molten glass into a plate shape and gradually cooling it.
  • the tempered glass is formed by forming a compressive stress layer on the surface of unstrengthened glass.
  • the tempered glass is a wind-cooled tempered glass
  • the uniformly heated glass plate is rapidly cooled from the temperature near the softening point, and a compressive stress is generated on the glass surface due to the temperature difference between the glass surface and the inside of the glass.
  • the surface may be strengthened.
  • the tempered glass is a chemically tempered glass
  • the glass surface may be strengthened by producing compressive stress on the glass surface by an ion exchange method or the like.
  • a glass plate that absorbs ultraviolet rays or infrared rays may be used as the vehicle glass, and it is preferable that the glass is transparent, but it may be glass that is colored to the extent that transparency is not impaired.
  • Organic glass may be used for vehicle glass. Examples of the organic glass include transparent resins such as polycarbonate.
  • the transparent substrate for vehicles is glass for vehicles
  • gravity forming or press forming is used as the bending forming of the glass plate used.
  • the method for forming the glass plate is not particularly limited, but glass formed by the float method or the like is preferable.
  • the vehicle glass may be a laminated glass including a plurality of the above-mentioned glass plates.
  • An interlayer film of ethylene vinyl acetal, polyvinyl butyral, or the like can be provided between the glass plates forming the laminated glass.
  • the shape of the vehicle transparent substrate is not limited to a rectangular shape or the like, and the vehicle transparent substrate may be processed to have various shapes.
  • the vehicle transparent substrate may be curved, and the curvature is not particularly limited.
  • the vehicle transparent substrate has a shape such that a molded product having a resin surface can be bonded to the surface of the vehicle transparent substrate, and sufficient plasma irradiation can be performed to improve the adhesiveness with the molded product. And has a curvature.
  • the bonding step it is possible to obtain a vehicle structure in which the molded body and the transparent substrate are bonded with an adhesive.
  • vehicle structure include a vehicle bracket such as a resin bracket for mounting vehicle-mounted devices (vehicle-mounted camera, vehicle-mounted sensor, etc.) on a vehicle window glass, for example, a windshield, and a resin temporary fixing pin.
  • the member may be adhered.
  • it may be a structure in which a vehicle member such as a resin door slider or a resin door holder is adhered to the side glass.
  • at least an adhered portion has a plate shape and is flat.
  • FIG. 1 shows a plan view of the vehicle structure 1 in which a resin bracket 20 is bonded to a glass 10 as seen from the inside surface of the vehicle.
  • the structure shown in FIG. 1 is formed by adhering a resin bracket 20 for in-vehicle equipment to the surface of the windshield 10 on the inside of the vehicle.
  • the bracket 20 is configured to support at least the vehicle-mounted camera.
  • FIG. 2 shows a partial view of a cross section taken along the line II of FIG. As shown in FIG. 2, an adhesive layer 30 is arranged between the windshield 10 and the bracket 20.
  • the resin bracket 20 for the in-vehicle device is not limited to the in-vehicle camera.
  • the rain sensor, the infrared sensor, the millimeter wave radar, or the like is not particularly limited as long as it is a device that can support the resin bracket 20 bonded to the glass 10.
  • a shielding layer 15 may be provided on the periphery of the inner surface of the glass 10 on the vehicle interior.
  • the shielding layer 15 may be provided on both the glass plate located outside the vehicle and the glass plate located inside the vehicle, or may be provided on only one of the glass plates. Good.
  • the shielding layer 15 has a function of protecting a urethane sealant or the like that adheres and holds the vehicle transparent substrate 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 a fusible glass frit containing a black pigment and firing the paste.
  • the thickness of the shielding layer 15 is preferably 3 ⁇ m or more and 15 ⁇ m or less.
  • the width of the shielding layer 15 is not particularly limited, but is preferably 20 mm or more and 300 mm or less.
  • the bracket 20 is bonded onto the shielding layer 15 provided on the surface of the glass 10 on the inside of the vehicle, but the bracket 20 may be directly bonded to the surface of the glass 10 on the inside of the vehicle. When viewed from the outside of the vehicle, it is preferable that the bracket 20 is bonded to a position where it is hidden by the shielding layer 15.
  • bracket 20 When the bracket 20 is bonded to a position where it is hidden by the shielding layer 15, not only the bracket 20 and the adhesive layer 30 are less visible from the outside of the vehicle, but also deterioration of the adhesive layer 30 due to ultraviolet rays can be suppressed.
  • the adhesiveness between the molded article having a resin surface and the adhesive is enhanced without using a primer. Therefore, even when a force is applied to the vehicle structure from the outside, peeling at the interface between the molded body and the adhesive is less likely to occur.
  • Resin PBT1 Glass fiber reinforced polybutylene terephthalate ("Plastic Plastics Co., Ltd., “Duranex (registered trademark) 733LD")
  • Resin PBT2 glass fiber reinforced polybutylene terephthalate (manufactured by BASF Japan Ltd., "ULTRADUR (registered trademark) B4300G6")
  • Resin PBT3 glass fiber reinforced polybutylene terephthalate (manufactured by Mitsubishi Engineering Plastics, "Novaduran (registered trademark) 5010G30J”)
  • PA Glass fiber reinforced polyamide (PA6T/6I) ("Grivory (registered trademark) HTV-3H1 9025" manufactured by Emschemy Japan KK)
  • Resin PEI Polyetherimide ("Ultem (registered trademark) 1000" manufactured by SABIC)
  • ⁇ Adhesion evaluation (knife cut test)> The evaluation of the adhesiveness between the molded body and the adhesiveness of the test piece was performed by a hand peeling test by knife cutting.
  • a notch of a certain length is made with a cutter knife between the adhesive layer of the test piece and the plate-shaped molded body (interface between the adhesive and the molded body), and the adhesive layer is molded from the notch. It was done by pulling it off the body. After applying a constant force, a cutter knife was further inserted deeply between the adhesive layer and the plate-shaped molded product to make a notch, and peeling of the adhesive layer was repeated to confirm the peeled state of the adhesive.
  • CF rate the ratio of the area where the adhesive was cohesively destroyed
  • a CF rate of 0% means that the adhesive has not undergone cohesive failure at all and interfacial peeling has occurred
  • a CF rate of 100% means that the adhesive has been cohesively destroyed over the entire surface. It is in a state. It was evaluated that the higher the CF ratio, the greater the proportion of cohesive failure in the adhesive, and the better the adhesiveness between the molded body and the adhesive.
  • Example 1 As a molded body, a plate-shaped molded body (25 mm ⁇ 150 mm ⁇ 5 mm) made of resin PBT1 was prepared. First, the surface of the plate-shaped body was prepared by impregnating the surface of the plate-shaped body with hexane (Sigma Aldrich Japan GK, special grade reagent) and hexane with a non-woven wiper (Bencot (registered trademark) manufactured by Asahi Kasei Corporation). It was cleaned by wiping.
  • hexane Sigma Aldrich Japan GK, special grade reagent
  • a non-woven wiper Billencot (registered trademark) manufactured by Asahi Kasei Corporation
  • an Openair (registered trademark) plasma device using a plasma generator FG5001 and a plasma jet nozzle RD1004, manufactured by Plasma Treat Co., Ltd.
  • an irradiation speed moving of the plasma jet nozzle to the plate-shaped compact.
  • Plasma processing was performed at a speed of 2.5 m/min and an irradiation distance of 10 mm.
  • the frequency of the voltage applied to the power source in the above processing apparatus was 21 kHz.
  • the room temperature during the plasma treatment was 23°C.
  • a urethane-based adhesive (“WS292A” manufactured by Yokohama Rubber Co., Ltd.) is applied to the surface of the plate-shaped molded body after the surface modification using a dedicated coating gun, An adhesive layer having a thickness of 3 mm was formed to obtain a test piece.
  • the test piece was cured at room temperature and normal humidity for 1 day.
  • the test piece after curing was evaluated for adhesiveness by the above-mentioned knife cut test. The results are shown in Table 1.
  • Example 1-2 Plasma treatment and surface treatment were performed under the same conditions as in Example 1-1. However, the subsequent treatment of adsorption of molecules of the treatment liquid is carried out by spraying water (distilled water), which is the treatment liquid, onto the surface of the molded product using a commercially available mist blower, rather than immersing it in water, to modify the surface. The molded body thus obtained was obtained. A test piece was prepared in the same manner as in Example 1-1, and the adhesiveness was evaluated.
  • distilled water distilled water
  • Example 1-3 Plasma treatment and surface treatment were performed under the same conditions as in Example 1-1. However, a surface-modified molded body was obtained without performing the subsequent treatment for adsorption of the treatment liquid molecules. A test piece was prepared and the adhesiveness was evaluated in the same manner as in Example 1-1.
  • Example 1-4 A test piece was prepared in the same manner as in Example 1-1, except that the plasma treatment was not performed, and the adhesiveness was evaluated.
  • Table 1 shows the results of Examples 1-1 to 1-4.
  • Example 2-1 Test pieces were prepared in the same manner as in Example 1-1 to Example 1-3, except that a molded body made of PBT2 was used, and the adhesiveness was evaluated.
  • Table 2 shows the results of Examples 2-1 to 2-3.
  • Examples 3-1 to 3-3 Test pieces were prepared in the same manner as in Example 1-1 to Example 1-3, except that a molded body made of PBT3 was used, and the adhesiveness was evaluated.
  • Table 3 shows the results of Examples 3-1 to 3-3.
  • Example 4-1 to 4-3 Test pieces were prepared in the same manner as in Example 1-1 to Example 1-3 except that a molded article made of PA (PA6T/6I) was used, and the adhesiveness was evaluated.
  • PA PA6T/6I
  • Table 4 shows the results of Examples 4-1 to 4-3.
  • Test pieces were prepared in the same manner as in Example 1-1 and Example 1-3, except that a molded body made of PEI was used, and the adhesiveness was evaluated.
  • Table 5 shows the results of Example 5-1 and Example 5-2.
  • Example 6-1 As in Example 2-1, a molded body made of PBT2 was prepared, plasma treated, and cleaned. After that, instead of using water as a treatment liquid, acetone (Sankyo Chemical Co., Ltd., pure acetone, concentration: 99.5% or more) was impregnated into a nonwoven fabric wiper (Bencot) and wiped to apply it to the surface of the molded body. .. The molded body after surface modification was obtained by visually standing until it was visually confirmed that there was no liquid on the surface. A test piece was prepared in the same manner as in Example 2-1, and the adhesiveness was evaluated.
  • acetone Sudyo Chemical Co., Ltd., pure acetone, concentration: 99.5% or more
  • Example 6-2 Test pieces were prepared in the same manner as in Example 6-1 except that the treatment liquid used was methyl ethyl ketone (MEK) (Gordo Co., Ltd., for business, concentration: 99% or more), and the adhesiveness was evaluated.
  • MEK methyl ethyl ketone
  • Table 6 shows the results of Example 6-1 and Example 6-2.
  • Example 7-1 A molded body of PBT2 was prepared in the same manner as in Example 2-1. Plasma treatment was performed in the same manner as in Example 2-1, except that the irradiation speed was 10 m/min, to perform cleaning. Then, instead of using water as a treatment liquid, ethanol (manufactured by Ganka Chemical Industry Co., Ltd., special grade reagent) was impregnated into a nonwoven fabric wiper (Bencot) and wiped to apply it to the surface of the molded body. The molded body after surface modification was obtained by visually observing until the surface of the molded body was visually confirmed to be free of liquid. A test piece was prepared in the same manner as in Example 2-1 except that the curing time was 4 days, and the adhesiveness was evaluated.
  • ethanol manufactured by Ganka Chemical Industry Co., Ltd., special grade reagent
  • Example 7-2 A test piece was prepared in the same manner as in Example 7-1 except that butyl acetate (manufactured by WAKO, special reagent grade) was used as the treatment liquid, and the adhesiveness was evaluated.
  • butyl acetate manufactured by WAKO, special reagent grade
  • Table 7 shows the results of Example 7-1 and Example 7-2.
  • Example 8-1 a plate-shaped molded product (25 mm ⁇ 150 mm ⁇ 5 mm) made of the resin PBT1 was prepared, and plasma treatment was performed under the same conditions as in Example 1-1 for cleaning. Subsequently, in this example, the molded body after the plasma treatment was placed in a space under an environment of room temperature (23° C.) and a humidity of 50% RH and stored for 24 hours to prepare a test piece. Adhesion was evaluated in the same manner as in Example 1-1.
  • Example 8-2 A test piece was prepared in the same manner as in Example 8-1 except that the test piece was stored in a space under an environment of a humidity of 80% RH for 1 hour, and the adhesiveness was evaluated.
  • Example 8-3 A test piece was prepared in the same manner as in Example 8-1 except that it was stored in a space under an environment of a humidity of 80% RH for 24 hours, and the adhesiveness was evaluated.
  • Example 8-4 A test piece was prepared in the same manner as in Example 8-1 except that the test piece was stored in a space under an environment of a humidity of 90% RH for 1 hour, and the adhesiveness was evaluated.
  • Example 8-5 A test piece was obtained in the same manner as in Example 8-1 except that it was stored in a space under the environment of a humidity of 90% RH for 24 hours, and the adhesiveness was evaluated.
  • Example 9-1 to 9-5 Test pieces were prepared in the same manner as in Example 8-1 to Example 8-5 except that a molded body made of PBT2 was used, and the adhesiveness was evaluated.
  • Example 10-1 to Example 10-5 Test pieces were prepared in the same manner as in Example 8-1 to Example 8-5 except that a molded body made of PBT3 was used, and the adhesiveness was evaluated.
  • Example 10-1 to 10-5 are shown in Table 10 (Example 3-3 is reprinted).
  • Vehicle structure 10 Glass (transparent substrate) 15 Shielding Layer 20 Resin Bracket (Resin Molded Body) 30 adhesive layer

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un procédé comprenant : une étape de traitement au plasma pour effectuer un traitement au plasma sur un corps moulé présentant une surface en résine ; une étape d'adsorption de molécules pour adsorber des molécules d'une solution de traitement, qui contient au moins un élément parmi l'eau et un solvant organique hydrophile, sur la surface du corps moulé après l'étape de traitement au plasma ; et une étape de collage pour coller le corps moulé après l'étape d'adsorption de molécule à un substrat de véhicule transparent au moyen d'un adhésif pour obtenir une structure de véhicule.
PCT/JP2019/046340 2018-12-03 2019-11-27 Procédé de fabrication d'une structure de véhicule et procédé de traitement d'une carrosserie moulée de véhicule WO2020116273A1 (fr)

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JPS59215328A (ja) * 1983-05-24 1984-12-05 Stanley Electric Co Ltd 高分子固体材料表面の親水化方法
JPS62110973A (ja) * 1985-11-06 1987-05-22 平岡織染株式会社 低温プラズマ処理された基材の処理効果保持方法
JPS6386733A (ja) * 1986-09-30 1988-04-18 Sumitomo Bakelite Co Ltd プラズマ処理品の保管方法
JPH0539374A (ja) * 1991-08-06 1993-02-19 Dainippon Printing Co Ltd プラスチツクフイルムの表面濡れ性改良方法
JPH07330930A (ja) * 1994-06-03 1995-12-19 Kanegafuchi Chem Ind Co Ltd 高分子フィルムの表面処理方法
JPH08502767A (ja) * 1992-08-26 1996-03-26 シー・アール・バード・インコーポレーテツド ポリエチレンテレフタレート製品の表面処理方法
JP2001334824A (ja) * 2000-03-24 2001-12-04 Hori Glass Kk 自動車用窓ガラスおよびその製造方法
JP2006282871A (ja) * 2005-03-31 2006-10-19 Univ Nagoya 疎水性高分子基板表面の親水性維持方法
JP2007190511A (ja) * 2006-01-20 2007-08-02 Toppan Printing Co Ltd 基板の表面状態保持方法及び基板
JP2008127428A (ja) * 2006-11-17 2008-06-05 Yokohama Rubber Co Ltd:The 樹脂ホルダー用表面処理剤、表面処理された樹脂ホルダー、表面処理された樹脂ホルダーの製造方法および自動車窓ガラスと樹脂ホルダーとの複合体
JP2013220688A (ja) * 2012-04-13 2013-10-28 Toyota Motor Corp 補給用樹脂ドア部材及び補給用樹脂ドア部材へのドアガラス取付方法

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59215328A (ja) * 1983-05-24 1984-12-05 Stanley Electric Co Ltd 高分子固体材料表面の親水化方法
JPS62110973A (ja) * 1985-11-06 1987-05-22 平岡織染株式会社 低温プラズマ処理された基材の処理効果保持方法
JPS6386733A (ja) * 1986-09-30 1988-04-18 Sumitomo Bakelite Co Ltd プラズマ処理品の保管方法
JPH0539374A (ja) * 1991-08-06 1993-02-19 Dainippon Printing Co Ltd プラスチツクフイルムの表面濡れ性改良方法
JPH08502767A (ja) * 1992-08-26 1996-03-26 シー・アール・バード・インコーポレーテツド ポリエチレンテレフタレート製品の表面処理方法
JPH07330930A (ja) * 1994-06-03 1995-12-19 Kanegafuchi Chem Ind Co Ltd 高分子フィルムの表面処理方法
JP2001334824A (ja) * 2000-03-24 2001-12-04 Hori Glass Kk 自動車用窓ガラスおよびその製造方法
JP2006282871A (ja) * 2005-03-31 2006-10-19 Univ Nagoya 疎水性高分子基板表面の親水性維持方法
JP2007190511A (ja) * 2006-01-20 2007-08-02 Toppan Printing Co Ltd 基板の表面状態保持方法及び基板
JP2008127428A (ja) * 2006-11-17 2008-06-05 Yokohama Rubber Co Ltd:The 樹脂ホルダー用表面処理剤、表面処理された樹脂ホルダー、表面処理された樹脂ホルダーの製造方法および自動車窓ガラスと樹脂ホルダーとの複合体
JP2013220688A (ja) * 2012-04-13 2013-10-28 Toyota Motor Corp 補給用樹脂ドア部材及び補給用樹脂ドア部材へのドアガラス取付方法

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