WO2017002592A1 - Procédé de production d'un substrat pourvu d'un film de revêtement, et substrat pourvu d'un film de revêtement - Google Patents

Procédé de production d'un substrat pourvu d'un film de revêtement, et substrat pourvu d'un film de revêtement Download PDF

Info

Publication number
WO2017002592A1
WO2017002592A1 PCT/JP2016/067488 JP2016067488W WO2017002592A1 WO 2017002592 A1 WO2017002592 A1 WO 2017002592A1 JP 2016067488 W JP2016067488 W JP 2016067488W WO 2017002592 A1 WO2017002592 A1 WO 2017002592A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
film
substrate
base material
coating film
Prior art date
Application number
PCT/JP2016/067488
Other languages
English (en)
Japanese (ja)
Inventor
亮太 吉村
武幸 金田
Original Assignee
セントラル硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2015257578A external-priority patent/JP6103032B2/ja
Application filed by セントラル硝子株式会社 filed Critical セントラル硝子株式会社
Priority to US15/741,033 priority Critical patent/US11059743B2/en
Priority to EP16817701.2A priority patent/EP3338901A4/fr
Publication of WO2017002592A1 publication Critical patent/WO2017002592A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C9/00—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important
    • B05C9/06—Apparatus or plant for applying liquid or other fluent material to surfaces by means not covered by any preceding group, or in which the means of applying the liquid or other fluent material is not important for applying two different liquids or other fluent materials, or the same liquid or other fluent material twice, to the same side of the work
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/26—Processes for applying liquids or other fluent materials performed by applying the liquid or other fluent material from an outlet device in contact with, or almost in contact with, the surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/25—Oxides by deposition from the liquid phase

Definitions

  • the present invention relates to a substrate with a coating film, particularly a substrate with a coating film suitable for an automobile window glass, and a method for producing the same.
  • a coating film is provided on the surface of a base material such as a glass plate, particularly an automobile window glass for the purpose of imparting ultraviolet shielding, infrared shielding, water repellency and antifogging properties.
  • a coating film the coating liquid is applied to the substrate by a flow coating method in which the coating liquid is poured out through a nozzle on the upper edge of the plate-like substrate held in the vertical direction, and dried to form the coating film.
  • the method of forming is taken (for example, Patent Documents 1 to 4).
  • the main liquid that discharges the coating liquid for forming the coating film is moved relative to the base material in the horizontal direction or the horizontal direction such as the substantially horizontal direction, and the coating liquid is supplied from the main nozzle to the main surface of the base material.
  • the coating liquid flows from the upper side to the lower side of the substrate, so the film thickness distribution of the coating film is from the upper side to the lower side. The film thickness tends to increase gradually.
  • the film thickness greatly affects the expression of functionality.
  • measures such as providing a coating section where the film thickness is increased more than necessary are required so that a coating section that does not satisfy the required performance does not occur.
  • the film thickness is unlikely to gradually increase in the flow direction of the coating liquid. It is an object of the present invention to provide a substrate with a coating film suitable for a coating method, and thus a window glass for automobiles.
  • the substrate to be coated is tilted or held in a vertical state, and on the upper side of at least one main surface of the substrate, the “coating film” While the main nozzle that discharges a coating liquid for forming a liquid (hereinafter sometimes referred to as a “main coating liquid”) is relatively moved in a substantially horizontal direction, the coating liquid is supplied from the main nozzle to the main body of the substrate.
  • main coating liquid a coating liquid for forming a liquid
  • a step of discharging onto the surface Before discharging the coating liquid onto the main surface of the substrate, a sub nozzle that discharges a “solvent that is dilutable with respect to the main coating liquid (hereinafter sometimes referred to as“ sub coating liquid ”)”
  • a step of discharging the solvent from the sub nozzle onto the main surface of the substrate while relatively moving the sub nozzle in a substantially horizontal direction The step of discharging the coating liquid from the main nozzle onto the main surface of the substrate is performed in a state where a liquid film of the solvent is held on the main surface.
  • the gist of the method for producing a substrate with a coating film of the present invention is based on “a liquid film formed by a sub-coating liquid (hereinafter sometimes referred to as“ underlying liquid film ”)” by applying a sub-coating liquid by a flow coating method.
  • the coating liquid is formed by applying the main coating liquid onto the base liquid film by the flow coating method, and the base liquid film is also gradually formed from the upper side to the lower side where coating is started. Since the base liquid film dilutes the main coating liquid applied thereon, the solid concentration in the coating liquid on the base material is applied after the main coating liquid is applied. Gradually decreases from the upper side to the lower side toward the start of application.
  • the film thickness of the coating film formed after drying and solidifying the coating liquid applied to the base material does not gradually increase from the upper side to the lower side, and is relatively flat.
  • a coating film having a film thickness distribution can be formed. Then, by adjusting the discharge position of the main nozzle, the non-application area of the substrate with the coating film can be adjusted by adjusting the discharge position of the sub nozzle. A region where the film thickness gradually increases toward the lower side) and a portion where the film thickness distribution of the coating film is relatively flat can be arbitrarily set.
  • the base liquid film forming area formed on the substrate is defined as the main coating liquid application area. It can be. For example, when the base liquid film is not formed on the side side on the main surface of the base material, the side side region of the main surface where the base liquid film is not formed can be set as a non-coating region of the coating film. .
  • the substrate with a coating film of the present invention can be produced by the above-described method, and is used as a window glass that can be opened and closed for an automobile door, and the substrate is placed in a storage portion of an upper frame of the door.
  • the area to be stored is in the substrate with a coating film in which the coating film is a non-coating area,
  • the coating film is formed through a step of discharging the coating liquid from the nozzle onto the main surface of the substrate while moving a nozzle for discharging the coating solution for forming the coating film relative to the substrate.
  • the coating film has a film thickness gradually changing portion in which the film thickness gradually decreases toward the non-coating region at the upper side edge of the coating film, and the start position of the film thickness gradually changing portion is a coating In the range of 5 to 200 mm in the vertical direction from the upper edge of the film, the upper edge of the coating film and the start position of the film thickness gradually changing portion are in a substantially parallel relationship, The angle between the main surface of the substrate and the coating film of the gradually changing film thickness is 0.0005 to 0.02 °. In order to exhibit the functionality of the coating film, a certain film thickness is required in most regions of the coating film.
  • the coating film near the non-coating region preferably has a film thickness distribution that can suppress optical distortion. Specifically, it is preferable to have a film thickness gradually changing portion in which the film thickness gradually decreases toward the non-coating region in the peripheral portion on the upper side of the coating film.
  • the start position of the film thickness gradually changing portion is in the vertical direction from the upper edge of the coating film, preferably 5 to 150 mm, more preferably 5 to 50 mm.
  • the start position of the gradual change portion is in a substantially parallel relationship. If it exceeds 200 mm, there is a tendency that the range for securing the performance of the film becomes narrow.
  • the angle formed between the main surface of the base material and the coating film of the gradually changing thickness portion is preferably 0.0005 to 0.002 °, more preferably 0.0015 to 0.015 °. If it is less than 0.0005 °, the film thickness tends to be thin, and the performance tends to decrease.If it exceeds 0.02 °, the film thickness becomes thick, so that the film tends to be caught at the boundary between the film and the glass surface, There is a tendency that film distortion tends to occur.
  • the manufacturing method of the substrate with a coating film of the present invention is that the coating film is formed in the flow-down direction of the coating liquid even if the coating film is formed on the substrate by the flow coat method in which the plate-like substrate is held in the vertical direction.
  • the present invention is effective in providing a substrate with a coating film having a relatively flat film thickness distribution that is unlikely to gradually increase in thickness.
  • the base material with a coating film of the present invention is suitable for automobile window glass. In particular, it is used as a window glass that can be opened and closed for an automobile door, and is suitable for an area in which the base material is stored in a storage part of an upper frame of the door as a non-application area of a coating film. Yes.
  • FIG. 5 schematically illustrates the shape of an XY cross section in FIG. 4.
  • the main coating liquid and the sub coating liquid are discharged while being moved relative to the base material 2 of the main nozzle 50 and the sub nozzle 60.
  • This is a schematic representation of the state to be performed. If the main nozzle 50 and the sub nozzle 60 are moved relative to the base material 2 in the horizontal direction, a mode different from FIG. 6 is schematically shown for the state in which the main coating liquid and the sub coating liquid are discharged. It is. If the main nozzle 50 and the sub nozzle 60 are moved relative to the base material 2 in the horizontal direction, a mode different from FIG. 6 is schematically shown for the state in which the main coating liquid and the sub coating liquid are discharged. It is.
  • region 4 on the side side is typically represented. It is a figure which shows roughly the principal part of a structure when the base material 1 with a coating film is accommodated in the accommodating part of the upper frame of a door. It is a figure which shows schematically the principal part of a structure when the base material 1 with a coating film is accommodated in the accommodating part of the side part frame of a door.
  • the plate-like substrate used in the method for producing a substrate with a coating film of the present invention is a float method used for windows and mirrors for buildings and vehicles, Or, use soda-lime silicate glass manufactured by the roll-out method, soda-lime silicate glass used in display device cover glass and substrate glass, non-alkali glass, etc. it can.
  • the plate glass both colorless and colored ones can be used.
  • the shape of the plate-like substrate is not particularly limited, and a flat plate or a curved plate can be used.
  • the coating film may be formed on the convex surface side.
  • the concave surface side is an indoor side surface, so the coating film is formed. Is preferably a concave side surface.
  • various tempered glasses such as air-cooled tempered glass and chemically tempered glass, netted glass can also be used.
  • various glass substrates such as borosilicate glass, low expansion glass, zero expansion glass, low expansion crystallized glass, zero expansion crystallized glass, TFT glass, PDP glass, and optical filter base glass are used. be able to.
  • a resin plate substrate such as polyethylene terephthalate resin, polycarbonate resin, polycarbonate resin, polyvinyl chloride resin, or polyethylene resin may be used.
  • the main coating solution is a coating film that is formed by drying and solidifying after coating on the substrate, and is limited as long as it has a solid content or a curable compound and a solvent to form the coating film. is not.
  • the main coating liquid for example, an alkoxide compound commonly used in film formation for automobiles is hydrolyzed and polycondensed to form an oligomer-containing coating liquid or a film mainly composed of silicon oxide such as polysilazane. Things are used.
  • the coating liquid which forms films such as an epoxy and urethane, is mentioned.
  • the sub-coating liquid is used for diluting the main coating liquid, is selected according to the type of the main coating liquid, is a solvent that can be diluted without curing or phase-separating the main coating liquid, and the base material.
  • Those having high wettability that is, those having a contact angle of 30 ° or less are preferably used.
  • the said contact angle can be calculated
  • solubility parameter (SP value) between the solvent of the main coating solution and the sub coating solution is, the better, and the difference in SP value of the sub coating solution is less than 1.5 (cal / cm 3 ) 1/2 .
  • the difference in SP value between the main coating solution and the sub-coating solution is 1.5 (cal / cm 3 ) 1/2 or more, the solid content in the main coating solution cannot be dissolved, and precipitation or phase separation occurs.
  • the SP value is a generally known solubility parameter and is an index of solubility and compatibility.
  • a method of calculating from the heat of vaporization of the liquid, a Hansen method, a Hoy method, a Small method, a Fedor estimation method, etc. calculated based on the molecular structure are known.
  • Fedor's estimation method calculated from the molecular structure was used.
  • regulated regarding this invention is a value calculated
  • the sub-coating liquid preferably has high wettability with the substrate.
  • the contact angle with the substrate is preferably 30 ° or less. Furthermore, 20 degrees or less is preferable.
  • the contact angle is large, the liquid film of the sub-coating liquid is liable to break up and a large amount of coating liquid is required, which is not preferable.
  • the sub coating liquid is selected depending on the type of the main coating liquid.
  • the main coating liquid is polysilazane (NP110 manufactured by Merck Performance Materials)
  • xylene SP value: 9.1 (cal / cm 3 ) 1/2
  • the solvent in the main coating liquid As the liquid, xylene having the same SP value (SP value: 9.1 (cal / cm 3 ) 1/2 ), n-hexane (SP value: 7.2 (cal / cm 3 ) 1/2 ), cyclohexanone (SP Value: 9.8 (cal / cm 3 ) 1/2 ), 2-heptane (SP value: 8.5 (cal / cm 3 ) 1/2 ) and the like are preferable.
  • the nozzles used for the main nozzle and the sub nozzle are not particularly limited as long as the main coating liquid and the sub coating liquid can be discharged.
  • a single nozzle, a composite nozzle in which a plurality of nozzles are arranged in parallel, a slit nozzle having a wide slit-like discharge port, or the like is used.
  • the main and sub nozzle diameters are preferably 0.5 mm ⁇ to 5 mm ⁇ , and more preferably 1 mm ⁇ to 2 mm ⁇ .
  • the nozzle diameter of the sub nozzle is preferably larger than that of the main nozzle.
  • FIG. 1 shows the main surface of the base material 2 in the lateral direction with respect to the base material 2 used as a window glass of an automobile having an upper side 2a, a side side 2b, a side side 2c, and a bottom side 2d. If the relative movement is substantially parallel to the inclined upper side 2a, the state in which the main coating liquid and the sub coating liquid are discharged is schematically shown.
  • This figure shows a state in which the main nozzle 50 and the sub nozzle 60 at a position below the main nozzle 50 are relatively moved in the horizontal direction while the base material 2 is held in a vertical direction and left still.
  • the main nozzle 50 and the sub-nozzle 60 are moved relative to the base material 2, they are spaced from the opposing sides (in the case of FIG. 1, the upper side 2 a) and are substantially parallel to the opposing sides.
  • region of a coating film can be formed by making it move relatively with respect to a base material.
  • the base material 2 is a rectangle such as a square or a rectangle
  • the base material is held in the vertical direction with one side as the upper side, and the horizontal direction with respect to the side with the main nozzle 50 and the sub nozzle 60 as the upper side.
  • it is relatively moved in a substantially horizontal direction. This aspect is effective when the substrate with a coating film is used as a substrate for a display device or a building material.
  • FIG. 2 is an observation of the substrate 2 from the side 2b side, and schematically shows the arrangement positions of the nozzles when the main nozzle 50 and the sub nozzle 60 are moved relative to the substrate 2. is there.
  • FIG. 3 is a view of the base material 2 observed from the side 2b side, and schematically shows a state in which the liquid film 52 of the main coating liquid is formed on the base liquid film 62.
  • the sub nozzle 60 is moved with respect to the base material 2.
  • the sub coating liquid is discharged while relatively moving the sub nozzle 60 in the horizontal direction along the uppermost side 61 of the base liquid film 62 (the lowermost side 61 of the film thickness gradually changing portion).
  • the sub coating liquid flows on the glass main surface toward the bottom 2d side of the substrate 2 by gravity.
  • the film thickness of the underlying liquid film generated at this time becomes thicker downward.
  • the uppermost side 61 (shown by a broken line in FIG. 1) of the base liquid film 62 is a position where the film thickness distribution of the coating film is a starting point of a relatively flat portion. 2a is preferably in a substantially parallel relationship.
  • the main nozzle 50 While the base liquid film 62 is held on the base material 2, the main nozzle 50 is moved relative to the base material 2, that is, the uppermost side 51 of the film thickness gradually changing portion (shown by a solid line in FIG. 1). The main coating liquid is discharged while the main nozzle 50 is relatively moved along the horizontal direction.
  • the shape of the uppermost side of the coating film (corresponding to the uppermost side 51 of the film thickness gradually changing portion in the drawing) (also called a parting shape) is a smooth line shape.
  • the appearance of the substrate with a coating film can be improved.
  • the main coating liquid flows through the glass main surface toward the bottom 2d side of the substrate 2 by gravity.
  • the film thickness of the liquid film 52 of the main coating liquid generated at this time becomes thicker as it goes downward. Since the base liquid film 62 and the liquid film 52 of the main coating liquid are mixed with each other, the concentration of solid content in the coating liquid for forming the coating film becomes lower as it goes downward.
  • the film thickness distribution (referred to as “first film thickness distribution”) between the uppermost side 51 of the film thickness gradually changing part and the lowermost side 61 of the film thickness gradually changing part, and the film thickness gradually changing
  • the film thickness distribution (second film thickness distribution) of the film on the base 2d side of the base material is different from the lowest side 61 of the part.
  • each nozzle with respect to the base material 2 and the discharge of each coating liquid may be performed only on the upper side 2a side of the base material, or from the group consisting of the main nozzle 50 and the sub nozzle 60 as shown in FIGS.
  • a method including a step of moving at least one selected relative to the substrate 2 in the longitudinal direction may be adopted. The trajectories of these relative movements are as indicated by the broken and solid arrows shown in FIGS.
  • FIG. 6 shows the main application while moving the main nozzle 50 and the sub-nozzle 60 relative to the base material 2 when forming a non-coating region of the coating film on the side of the main surface of the base material.
  • the state which discharges a liquid and a subcoating liquid is typically represented.
  • the sub coating liquid is discharged while moving the sub nozzle 60 relative to the substrate 2 along the side 2c from the lower side of the substrate 2 at an arbitrary interval from the side 2c. Thereafter, the sub coating liquid is discharged while moving the sub nozzle 60 relative to the base material 2 along the upper side 2a at an arbitrary interval from the upper side 2a side of the base material, and from the side side 2b.
  • the sub-coating liquid is discharged while moving relative to the base material 2 along the side edge 2b from the upper side of the base material 2 to form a base liquid film.
  • the main coating liquid is moved while moving the main nozzle 50 relative to the substrate 2 along the upper side 2a at an arbitrary interval from the upper side 2a of the substrate. Is discharged.
  • region 4 can be formed in the side 2b, 2c side.
  • the main nozzle 50 is moved with respect to the base material 2 in the same locus as the sub nozzle 60 as shown in FIG. It is good also as an aspect to which it moves relatively, and as shown in FIG. 8, each nozzle is moved relative to the base material 2 on the side 2b side and the side 2c side in the vertical direction, and the base sides 2b, 2c. After discharging the liquid to the side, the nozzles may be moved relative to the base 2 in the lateral direction on the upper side 2a side of the base to discharge the liquid onto the base.
  • the main coating liquid applied on the base liquid film spreads and spreads only in the area where the base liquid film is formed, a substrate with a coating film having the non-application area 4 on the sides 2b and 2c is efficiently manufactured.
  • the method shown in FIG. 6 is more preferable.
  • each coating liquid When each coating liquid is discharged, when each nozzle is located at a position close to the side edges 2b and 2c (for example, at a position of 0 to 10 mm in the vertical direction from the side edge), the direction of each nozzle is set to the base material. It is preferable to provide an inclination so that the discharge direction of the liquid from each nozzle becomes the inner direction of the substrate 2 by performing an operation such as directing the inner direction of the substrate 2. By doing so, it becomes easy to prevent the liquid from flowing into the back side of the application target surface of the main coating liquid and the sub coating liquid.
  • the relative movement speed of each nozzle, the discharge angle of each coating liquid with respect to the base material 2, the distance between the base material 2 and the discharge port of each nozzle, the liquid discharge pressure, the viscosity of the liquid to be discharged, and the liquid from each nozzle The amount is appropriately determined in consideration of the discharge amount, the installation angle of the substrate 2, the degree of occurrence of liquid cracking during liquid application, the optical distortion of the formed coating film, the film thickness, and the like.
  • the plate-shaped base material 2 has the side 2c, 2d of the base material 2 in the reference line 7 which shows a horizontal direction. It is preferable to be held in a state of being perpendicular to the surface. By holding in this way, it becomes easy to prevent the coating solution from flowing from the coating surface to the opposite surface.
  • the plate-like substrate 2 is curved, as shown in FIGS. 2 and 3, the upper portions of the sides 2c and 2d of the substrate 2 are perpendicular to the reference line 7 indicating the horizontal direction. It is preferable to hold the substrate in a state. By holding in this way, a smooth flow of the coating liquid occurs, and the coating efficiency increases.
  • 1, 2, 3, 6, 7, and 8 also show an auxiliary line 71 indicating a direction perpendicular to the reference line 7 indicating the horizontal direction.
  • a drying process for evaporating the solvent of the sub-coating liquid, the solvent of the main coating liquid, and a solidification process for forming the coating liquid applied to the substrate 2 as a coating film are performed. Is called.
  • a leveling step for improving the homogeneity of the coating solution applied to the substrate 2 may be provided. In the leveling step, the substrate 2 is held horizontally or tilted for a certain period of time (for example, at room temperature for about 1 to 20 minutes).
  • the drying step may be performed by maintaining the base material 2 at room temperature, heating the coating solution applied to the base material 2, or simultaneously with the solidification step.
  • heating, UV irradiation, application of superheated steam, or the like is appropriately selected according to the type of the solid content.
  • a substrate with a coating film can be suitably used as a window glass capable of opening and closing an automobile door (for example, a window glass slidable up and down installed on a side door of an automobile).
  • a door has a window glass frame, and a storage portion 8 (run channel) for storing the window glass is provided above the door.
  • the coating film is preferably a non-coating region.
  • FIG. 4 is a schematic view when the substrate with a coating film is observed from the main surface side where the coating film is formed.
  • FIG. 5 schematically shows a main part of a cross section when the substrate 1 with a coating film is cut in XY.
  • the portion forming the first film thickness distribution corresponds to the film thickness gradually changing portion 31 in which the film thickness gradually decreases toward the non-coating region 4 at the peripheral edge of the upper side 2 a of the coating film.
  • the starting position of the film thickness gradually changing portion 31 is in the range of 5 to 200 mm in the vertical direction from the peripheral portion on the upper side of the coating film, and is preferably as short as possible.
  • the thickness is less than 0 to 5 mm, the angle formed between the main surface of the base material and the coating film of the film thickness gradually changing portion is large, optical distortion of the film thickness gradually changing portion is likely to occur, and the appearance of the coating film tends to be poor. .
  • the upper peripheral side edge of the coating film and the starting position of the film thickness gradually changing portion are in a substantially parallel relationship, and the angle formed between the main surface of the substrate and the coating film of the film thickness gradually changing portion is 0.0005 to 0.00. Preferably it is at 02 °.
  • the angle formed between the main surface of the base material and the coating film of the film thickness gradually changing portion is determined by using a surface roughness measuring machine (such as Surfcoder ET4000A manufactured by Kosaka Laboratory) at various positions of the film thickness gradually changing portion. And the angle can be obtained from the relationship between the distance from the uppermost side 51 of the film thickness gradually changing portion and the film thickness.
  • a region other than the gradually changing portion of the film thickness that is, a region below the lowermost side 61 of the upper side of the film thickness (a region below the broken line in FIG. 5) is defined as the film main portion 32.
  • the film thickness of the main film portion 32 is preferably 2.5 to 5.5 ⁇ m, more preferably 3.5 to 5.0 ⁇ m. If it is less than 2.5 ⁇ m, it is difficult to obtain desired performance when the function of the coating film is dependent on the film thickness, and if it exceeds 5.5 ⁇ m, optical distortion and cracks are likely to occur in the coating film 3.
  • the standard deviation of the film thickness of the film main portion 32 is preferably 0.5 or less, more preferably 0.3 or less. This is because when the ratio exceeds 0.5, optical distortion tends to occur, and thus there is a tendency that the perspective distortion test and double image test of Japanese Industrial Standard JIS R3211 (1998 revised edition) are not satisfied.
  • the starting position of the film thickness gradual change portion that is, the position of the lowermost side 61 of the film thickness gradual change portion is a distance from the boundary region between the film thickness gradual change portion 31 and the non-application region 4 in the vertical direction.
  • the relationship between the film thickness and the film thickness can be defined as a position where the intercept at the center of the film thickness main portion 32 and the intercept at the film thickness gradually changing portion 31 intersect.
  • the standard deviation of the film thickness can be obtained by measuring the film thickness at any 10 positions (select each arbitrary point not to be too close) in the main film thickness portion 32 and using the standard deviation formula. it can.
  • FIG. 10 is a diagram schematically showing the main part of the structure when the substrate 1 with coating film is housed in the housing part of the upper frame of the door.
  • the run channel 8 has a substantially U-shaped structure in cross section. I have.
  • the end surface of the base material 1 with a coating film shown in FIG. 10 represents a cross section that appears when the base material 1 is cut in the XY shown in FIG.
  • the substrate 1 has a pair of seal lips 81 and an outer lip 82 that are slidably sandwiched from both sides in the thickness direction, and the seal lip 81 is in contact with the non-application region 4.
  • FIG. 10 shows a structure in which the film thickness gradual change portion 31 is not housed in the run channel 8, but a part of the film thickness gradual change portion 31 may be a region housed in the housing portion of the upper frame of the door. Good.
  • the region of the film thickness gradually changing portion 31 that is housed in the upper frame of the door is preferably 0 (extra) to 10 mm, and 0 (extra) to 5 mm from the start position of the thickness gradually changing portion 31. More preferred.
  • the base material 1 with a coating film may be provided with a non-coating region of the coating film also in a region where the base material is stored in a storage part of the side frame of the door.
  • FIG. 9 shows a schematic diagram when the substrate 1 with a coating film is observed from the main surface side where the coating film is formed.
  • the non-coating region 4 on the side 2b, 2c side is stored in a storage portion (run channel) 8 of the side frame of the door. It becomes an area to be.
  • FIG. 9 shows a schematic diagram when the substrate 1 with a coating film is observed from the main surface side where the coating film is formed.
  • FIG. 11 is a diagram schematically showing a main part of the structure when the substrate 1 with a coating film is stored in the storage part of the side frame of the door, and the run channel 8 has a substantially U-shaped cross section. It has. And it has a pair of seal lip 81 and the outer lip 82 which are slidably clamped from both sides in the thickness direction of the substrate 1, and the seal lip 81 is in contact with the non-application area 4.
  • the end surface of the base material 1 with a coating film shown in FIG. 11 represents the cross section which appears when the base material 1 is cut in vw shown in FIG.
  • the side portion of the base material with the coating film has been less concerned by those skilled in the art than the upper side portion. This is because the coating film 3 in the side region of the base material with the coating film in contact with the seal lip 81 is coated as long as the coating film does not peel from the base material 2. This is because even if the portion of the film 3 is damaged, the scratch is not visually recognized by the user of the vehicle.
  • the coating film having the non-coating region 4 on the sides 2b and 2c is required when smooth elevation of the base material 1 with the coating film is required.
  • the attached substrate 1 has a preferable structure.
  • Example 1 Preparation of Base Material Glass used as a curved automobile door glass having a thickness of 3.1 mm, a size of 943 mm ⁇ 512 mm, and a bending rate of 2500 R was used as the base material 2.
  • the sides 2c and 2d of the base material 2 indicate the horizontal direction as shown in FIG.
  • the upper portions of the side edges 2 c and 2 d of the substrate 2 are perpendicular to the reference line 7 indicating the horizontal direction.
  • the sub-nozzle 60 is relatively moved at a speed of 100 mm / second so as to be substantially parallel to the shape of the upper side 2a 15mm below the upper side 2a of the base material in the vertical direction from the upper side 2a of the base material.
  • the sub-application liquid was discharged from the sub-nozzle 60 provided with the discharge port at a flow rate of 5 g / sec, and the sub-application liquid was applied to the substrate.
  • the main nozzle 50 With the sub-coating solution held on the base material 2, the main nozzle 50 is moved 10 mm downward in the vertical direction from the upper side 2a of the base material and relatively moved at a speed of 100 mm / second so as to be substantially parallel to the shape of the upper side 2a.
  • the main coating liquid was discharged from the main nozzle 50 having a discharge port of 2 mm ⁇ at a flow rate of 2 g / second to apply the main coating liquid to the substrate.
  • the substrate is stood and held in a state where the lower side is vertical, and after the leveling for 20 minutes, The substrate surface temperature is preheated to 180 ° C. for 5 minutes.
  • the coating film was cured by exposing the substrate to superheated steam at 180 ° C. for 10 minutes to form a coating film to obtain a coating film-coated substrate.
  • the obtained coated film-coated substrate had a non-coated region 4 formed on the upper side 2a side, and the parting shape (corresponding to the uppermost side 51 of the film thickness gradually changing portion) was smooth and curved and looked good. . Further, while the main nozzle 50 and the sub nozzle 60 were relatively moved, the film thickness gradually changed, and the angle formed between the main surface of the substrate 2 and the coating film of the film thickness gradually changed part was 0.001 °. .
  • the thickness of the other coating film formation region was 3.5 to 4.5 ⁇ m, a relatively flat film shape, and the standard deviation of the film thickness was 0.19. In addition, cracks, distortion, coloration, and white turbidity were difficult to find with the naked eye, and the appearance was good.
  • Comparative Example 1 A substrate with a coating film was obtained by performing the same procedure as in Example 1 except that the sub-coating liquid was not used and the liquid was not applied by the sub-nozzle. In the obtained substrate with a coating film, the coating film gradually increased in thickness toward the lower side 2d.
  • Comparative Example 2 The secondary coating solution is isopropanol (SP value: 11.5 (cal / cm 3 ) 1/2 ) or acetone (SP value: 10.0 (cal / cm 3 ) 1/2 ) which does not dilute the solvent of the main coating solution. The same operation as in Example 1 was performed except that was used. In this comparative example, the difference between the solubility parameter (SP value) of the solvent of the main coating solution and the SP value of the sub-coating solution exceeded 1.5 (cal / cm 3 ) 1/2 .

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne un procédé de production d'un substrat pourvu d'un film de revêtement ayant une distribution d'épaisseur de film relativement plate de façon que l'épaisseur du film ne tende pas à croître progressivement dans la direction aval de la solution de revêtement, même lorsqu'un film de revêtement est formé sur un substrat en forme de plaque par un procédé d'application par aspersion dans lequel le substrat est maintenu dans la direction verticale. Ce substrat pourvu d'un film de revêtement est utilisé en particulier comme verre de fenêtre pouvant être ouverte/fermée pour portières d'automobiles, la région où le substrat est logé à l'intérieur de la partie de logement du cadre supérieur de la portière étant adéquatement une région non revêtue d'un film de revêtement.
PCT/JP2016/067488 2015-06-30 2016-06-13 Procédé de production d'un substrat pourvu d'un film de revêtement, et substrat pourvu d'un film de revêtement WO2017002592A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US15/741,033 US11059743B2 (en) 2015-06-30 2016-06-13 Substrate provided with coating film
EP16817701.2A EP3338901A4 (fr) 2015-06-30 2016-06-13 Procédé de production d'un substrat pourvu d'un film de revêtement, et substrat pourvu d'un film de revêtement

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015-130968 2015-06-30
JP2015130968 2015-06-30
JP2015-257578 2015-12-29
JP2015257578A JP6103032B2 (ja) 2015-06-30 2015-12-29 塗布膜付基材の製法、及び塗布膜付基材

Publications (1)

Publication Number Publication Date
WO2017002592A1 true WO2017002592A1 (fr) 2017-01-05

Family

ID=57608673

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/067488 WO2017002592A1 (fr) 2015-06-30 2016-06-13 Procédé de production d'un substrat pourvu d'un film de revêtement, et substrat pourvu d'un film de revêtement

Country Status (1)

Country Link
WO (1) WO2017002592A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018104218A (ja) * 2016-12-26 2018-07-05 セントラル硝子株式会社 塗布膜付基材の製法、及び塗布膜付基材
JP2018104219A (ja) * 2016-12-26 2018-07-05 セントラル硝子株式会社 塗布膜付基材の製法、及び塗布膜付基材

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03193160A (ja) * 1989-12-21 1991-08-22 Fuji Photo Film Co Ltd 薄層塗膜の連続形成方法
JPH08179101A (ja) * 1994-12-26 1996-07-12 Central Glass Co Ltd 光学薄膜付きガラス及びその製法
JP2001118501A (ja) * 1999-10-15 2001-04-27 Matsushita Electric Ind Co Ltd カラー表示プラズマディスプレイパネルの蛍光体膜形成方法及び装置とそれらにより作製したカラー表示プラズマディスプレイパネル
JP2004039828A (ja) * 2002-07-03 2004-02-05 Tokyo Electron Ltd 塗布膜形成方法およびプリウェット剤
JP2007191322A (ja) * 2006-01-17 2007-08-02 Nippon Sheet Glass Co Ltd 車両用窓ガラス及びその製造方法
JP2011256060A (ja) * 2010-06-07 2011-12-22 Asahi Glass Co Ltd 被膜付き自動車用窓ガラスの製造方法
JP2013129576A (ja) * 2011-12-22 2013-07-04 Asahi Glass Co Ltd 塗膜付き自動車用窓ガラスおよびその製造方法
JP2014200730A (ja) * 2013-04-03 2014-10-27 東京応化工業株式会社 塗布装置及び塗布方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03193160A (ja) * 1989-12-21 1991-08-22 Fuji Photo Film Co Ltd 薄層塗膜の連続形成方法
JPH08179101A (ja) * 1994-12-26 1996-07-12 Central Glass Co Ltd 光学薄膜付きガラス及びその製法
JP2001118501A (ja) * 1999-10-15 2001-04-27 Matsushita Electric Ind Co Ltd カラー表示プラズマディスプレイパネルの蛍光体膜形成方法及び装置とそれらにより作製したカラー表示プラズマディスプレイパネル
JP2004039828A (ja) * 2002-07-03 2004-02-05 Tokyo Electron Ltd 塗布膜形成方法およびプリウェット剤
JP2007191322A (ja) * 2006-01-17 2007-08-02 Nippon Sheet Glass Co Ltd 車両用窓ガラス及びその製造方法
JP2011256060A (ja) * 2010-06-07 2011-12-22 Asahi Glass Co Ltd 被膜付き自動車用窓ガラスの製造方法
JP2013129576A (ja) * 2011-12-22 2013-07-04 Asahi Glass Co Ltd 塗膜付き自動車用窓ガラスおよびその製造方法
JP2014200730A (ja) * 2013-04-03 2014-10-27 東京応化工業株式会社 塗布装置及び塗布方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3338901A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018104218A (ja) * 2016-12-26 2018-07-05 セントラル硝子株式会社 塗布膜付基材の製法、及び塗布膜付基材
JP2018104219A (ja) * 2016-12-26 2018-07-05 セントラル硝子株式会社 塗布膜付基材の製法、及び塗布膜付基材

Similar Documents

Publication Publication Date Title
EP2403817B1 (fr) Procédé d'application d'un revêtement avec une filière en forme de fente
US7905950B2 (en) Coating composition and resin multilayer body
US9561525B2 (en) Process for depositing an anti-reflective layer on a substrate
JP2016117910A (ja) 耐摩耗性コーティング組成物およびコーティングされた物品
JP6986339B2 (ja) 反射防止膜形成用組成物、反射防止膜およびその形成方法
JP6579122B2 (ja) 塗布膜付基材の製法、及び塗布膜付基材
WO2017002592A1 (fr) Procédé de production d'un substrat pourvu d'un film de revêtement, et substrat pourvu d'un film de revêtement
WO2015107904A1 (fr) Verre à vitres pour véhicule, et procédé de fabrication de celui-ci
TW201920993A (zh) 經多層抗反射塗層塗覆之物件
JP2014111453A (ja) 被膜付き自動車用窓ガラス
JP6826285B2 (ja) 塗布膜付基材の製法、及び塗布膜付基材
JP6826286B2 (ja) 塗布膜付基材の製法、及び塗布膜付基材
JP2016084276A (ja) 被膜付き自動車用窓ガラス
JP2021058888A (ja) 塗布膜付基材の製法、及び塗布膜付基材
IL143923A (en) A coating composition containing monomer of silane and items coated with it
US8916328B2 (en) Coated glass substrate with ultraviolet blocking characteristics and including a rheological modifier
JP2004027108A (ja) ハードコート層を有するポリカーボネート樹脂成形体
EP1564192A1 (fr) Procede de formation d'un film fin sur un substrat en verre et substrat en verre revetu d'un film fin
JP2015074588A (ja) 親水化ガラス基板の製造方法
US11117830B2 (en) Glass article with colored coating
JPH0342238A (ja) 結露防止性を付与した耐摩耗性プラスチック積層体
JP2016020204A (ja) 被膜付き自動車用窓ガラス
JP2003131005A (ja) プラスチックレンズ
JP2002022902A (ja) プラスチックレンズの製造方法
EP3587370A1 (fr) Procédé pour la fabrication de verre à glace à revêtement coloré

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16817701

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2016817701

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 15741033

Country of ref document: US