WO2022014394A1 - Coating composition for application with roller, roll, brush, or spatula - Google Patents

Coating composition for application with roller, roll, brush, or spatula Download PDF

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Publication number
WO2022014394A1
WO2022014394A1 PCT/JP2021/025372 JP2021025372W WO2022014394A1 WO 2022014394 A1 WO2022014394 A1 WO 2022014394A1 JP 2021025372 W JP2021025372 W JP 2021025372W WO 2022014394 A1 WO2022014394 A1 WO 2022014394A1
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WO
WIPO (PCT)
Prior art keywords
coating
viscosity
paint
coating composition
mass
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PCT/JP2021/025372
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French (fr)
Japanese (ja)
Inventor
聡 石田
晋也 川上
Original Assignee
日本ペイントホールディングス株式会社
日本ペイント株式会社
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Application filed by 日本ペイントホールディングス株式会社, 日本ペイント株式会社 filed Critical 日本ペイントホールディングス株式会社
Publication of WO2022014394A1 publication Critical patent/WO2022014394A1/en

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    • 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
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/43—Thickening agents

Definitions

  • the present invention relates to a coating composition for roller coating, roll coating, brush coating or spatula coating.
  • paint tool holding the paint and the object to be coated come into contact with each other, and the paint tool or the object to be coated is applied to the other. Painting is done by moving.
  • Patent Document 1 a coating composition having excellent coating workability and a good coating feeling.
  • paint streaks the paint moves downward until the paint film dries
  • local abnormalities in film thickness also deteriorate the appearance of the coating film, it is necessary to suppress the sagging of the paint.
  • an object of the present invention is to provide a coating composition capable of suppressing paint streaks and sagging and forming a coating film having an excellent appearance.
  • the coating composition according to the present invention is A paint composition for roller coating, roll coating, brush coating, or spatula coating.
  • the viscosity ⁇ 1 when shear deformation at a shear rate of 0.01 s -1 is applied for 5 seconds is 40 Pa ⁇ s or less.
  • the storage elastic modulus of the coating composition at 23 ° C. is 50 Pa or more
  • the constant value ⁇ 2 of the viscosity of the coating composition in the steady flow measurement of shear deformation at 23 ° C. and a shear rate of 0.01 s -1 is 50 Pa ⁇ s or more.
  • a coating composition for roller coating, roll coating, brush coating, or spatula coating As a result, it is possible to suppress paint streaks and sagging and obtain a coating film having an excellent appearance.
  • the steady-state value ⁇ 2 of the viscosity is 50 to 500 Pa ⁇ s.
  • the viscosity ⁇ 1 is 3 to 40 Pa ⁇ s.
  • the storage elastic modulus is 50 to 400 Pa.
  • the coating composition for roller coating, roll coating, brush coating or spatula coating contains a resin component and a viscosity modifier.
  • the viscosity adjuster is one or more selected from the group consisting of an alkaline swelling type viscosity adjuster, a urethane association type viscosity adjuster, and a cellulosic viscosity adjuster.
  • the present invention it is possible to provide a coating composition capable of suppressing paint streaks and sagging and forming a coating film having an excellent appearance.
  • FIG. 1 is a diagram showing the appearance of the coating film of Example 5.
  • FIG. 2 is a diagram showing the appearance of the coating film of Comparative Example 2.
  • FIG. 3 is a schematic diagram showing a process of forming paint streaks during roller coating using a conventional paint.
  • the paint and the paint composition can be used interchangeably.
  • the numerical range is intended to include the upper limit value and the lower limit value of the range unless otherwise specified.
  • 50 to 500 Pa ⁇ s means 50 Pa ⁇ s or more and 500 Pa ⁇ s or less.
  • the viscosity ⁇ 1 when the coating composition is subjected to a shear deformation of a shear rate of 1000 s -1 at 23 ° C. for 30 seconds and then a shear deformation of a shear rate of 0.01 s -1 for 5 seconds is used as an example. Obtained by the method described.
  • the storage elastic modulus of the coating composition at 23 ° C. is determined by the method described in Examples.
  • the constant value ⁇ 2 of the viscosity of the coating composition in the steady flow measurement of shear deformation at 23 ° C. and a shear rate of 0.01 s- 1 is obtained by the method described in Examples.
  • the coating composition according to the present invention is A paint composition for roller coating, roll coating, brush coating, or spatula coating.
  • the viscosity ⁇ 1 when shear deformation at a shear rate of 0.01 s -1 is applied for 5 seconds is 40 Pa ⁇ s or less.
  • the storage elastic modulus of the coating composition at 23 ° C. is 50 Pa or more
  • the constant value ⁇ 2 of the viscosity of the coating composition in the steady flow measurement of shear deformation at 23 ° C. and a shear rate of 0.01 s -1 is 50 Pa ⁇ s or more.
  • a coating composition for roller coating, roll coating, brush coating, or spatula coating is 50 Pa ⁇ s or more.
  • the present inventors investigated the relationship between the paint streaks and the appearance of the paint film by painting with a roller or the like. As a result, the lower the height of the paint streaks, the less visible the paint streaks were to the observer of the paint film. It was found that the observer of the coating film evaluated the appearance of the coating film as good.
  • FIG. 3 is a schematic diagram showing the process of forming paint streaks during roller painting using a conventional paint. Further examination of the paint streaks by the present inventors revealed that the paint streaks were formed as shown in FIGS. 3A to 3E.
  • a liquid film 3 of the paint is generated at a portion where the roller 2 and the surface 1 are becoming separated (A in FIG. 3). ..
  • a part of the liquid film 3 is broken to form a void 4 (B in FIG. 3).
  • the void 4 becomes larger and becomes a thread-like paint thread 5 (C in FIG. 3).
  • the paint thread 5 breaks (D in FIG. 3). Then, the broken paint thread 5 remains on the coating film 6 and the paint streaks 7 are formed (E in FIG. 3).
  • the present inventors initially performed a steady flow of shear deformation at a shear rate of 0.01 s-1 , which corresponds to the viscosity of the coating composition forming the coating film and the coating streaks before drying. It was considered that the height of the paint streaks could be lowered and the appearance of the paint film could be improved by lowering the viscosity in the measurement and promoting the leveling of the paint streaks. However, it has been found that when the viscosity in the steady flow measurement is lowered, the height of the paint streaks is lowered, but the paint composition sags before the paint film dries, and the appearance of the paint film is deteriorated.
  • the present inventors then describe the following (1) and (2) to lower the height of the paint streaks, and the following (3) to suppress the sagging of the paint composition. I speculated that it would be effective for: (1) The viscosity of the paint streaks is lowered to promote the leveling of the paint streaks. (2) By shortening the length of the paint streaks and increasing the surface area (surface free energy) of the paint streaks, the leveling of the paint streaks is promoted. (3) Increase the viscosity of the paint composition forming the paint film and the paint streaks before drying, not the viscosity of the paint streaks.
  • the paint streaks in a short time immediately after painting are constant by the rollers (painting tools) as shown in C to E of FIG. 3, unlike the paint before painting. It is considered that the microstructure is broken (Fig. 3E) such that the entanglement of the molecular chains of the paint is reduced by the above shear rate. Therefore, assuming the viscosity of the paint streaks in this state, the present inventors applied the paint composition to a shear deformation at a shear rate of 1000 s -1 at 23 ° C. for 30 seconds, and immediately after that, the shear rate was 0.01 s -1 .
  • the viscosity ⁇ 1 (hereinafter, may be simply referred to as “viscosity ⁇ 1”) when shear deformation is applied for 5 seconds is set.
  • Shear deformation of the paint at a shear rate of 1000 s -1 for 30 seconds results in a state of paint thread (eg, D in FIG. 3) broken by painting with a paint tool, and immediately after this 30 seconds further into the paint composition.
  • a shear deformation with a shear rate of 0.01 s -1 for 5 seconds the shear deformation with a shear rate of 0.01 s -1 starts after the lapse of 30 seconds
  • the state of the paint streaks can be reproduced or approximated.
  • the leveling of the paint streaks is promoted.
  • the liquid film and paint thread of the paint (B to D in FIG. 3) at the time of painting can be considered as a viscoelastic body having an elastic component and a viscous component, and when the elastic component (storage elasticity) is increased.
  • the present inventors set the viscosity ⁇ 1 of the coating composition to 40 Pa ⁇ s or less, and the storage elastic modulus of the coating composition at 23 ° C. (hereinafter, “storage elastic modulus” is not specified unless otherwise specified. It was found that the height of the paint streaks can be lowered by setting (pointing to the value at 23 ° C.) to 50 Pa or more.
  • the height of the paint streaks is evaluated by the visual visibility of the paint streaks in the coating film. be able to.
  • the present inventors also examined quantifying the height of the paint streaks.
  • the paint film having the paint film is placed horizontally on the desk; then, the paint film surface is irradiated with light from the side of the paint film, and the paint film surface is photographed from the front of the paint film with a digital camera; Next, the brightness of the coating film surface of the obtained image is quantified (the brightness is high in the place where the height of the paint streaks is high, and the brightness is low in the place where there is no paint streaks and the place where the paint film surface is flat); Then, from the obtained numerical values, a value corresponding to the height of the paint streaks is calculated. Even with this quantified method, it was found that the appearance of the coating film was inferior when the value corresponding to the height of the paint streaks was high.
  • the sagging of the paint composition is a downward movement of the paint composition after painting and before the coating film is dried, it is not the viscosity of the paint streaks in a short time immediately after formation, but after painting. It is considered that sagging of the coating composition can be suppressed by increasing the viscosity of the coating composition forming the coating film and the coating streaks, which are stable but not dried with almost no shear deformation. ..
  • the present inventors express the viscosity of the stable but undried coating composition after coating as the viscosity when the viscosity reaches a steady value after a lapse of more time than the viscosity ⁇ 1.
  • the coating composition can be sagging. It was found that it can be suppressed.
  • the viscosity ⁇ 1 of the coating composition of the present invention is 40 Pa ⁇ s or less. If the viscosity ⁇ 1 is higher than 40 Pa ⁇ s, the height of the paint streaks cannot be sufficiently lowered, and a coating film having an excellent appearance cannot be obtained.
  • the viscosity ⁇ 1 of the coating composition of the present invention is, for example, 1 to 40 Pa ⁇ s. In one embodiment of the coating composition of the present invention, the viscosity ⁇ 1 is 40 Pa ⁇ s or less, 35 Pa ⁇ s or less, 30 Pa ⁇ s or less, 25 Pa ⁇ s or less, 20 Pa ⁇ s or less, 15 Pa ⁇ s or less, 10 Pa ⁇ s or less.
  • the viscosity ⁇ 1 is 1 Pa ⁇ s or more, 3 Pa ⁇ s or more, 5 Pa ⁇ s or more, 7 Pa ⁇ s or more, 10 Pa ⁇ s or more, 15 Pa ⁇ s or more, 20 Pa ⁇ s.
  • the above is 25 Pa ⁇ s or more, 30 Pa ⁇ s or more, or 35 Pa ⁇ s or more.
  • the viscosity ⁇ 1 is 5-40 Pa ⁇ s.
  • the viscosity ⁇ 1 is 3 to 40 Pa ⁇ s.
  • a method of using a viscosity adjusting agent having a small molecular weight which will be described later, can be mentioned.
  • the viscosity adjusting agent having a small molecular weight include UH series such as UH-140S, UH-752, UH-420, and UH-472 manufactured by ADEKA; and urethane association type viscosity adjusting agents such as SN Thickener 612 manufactured by San Nopco Ltd. And so on.
  • the storage elastic modulus of the coating composition of the present invention is 50 Pa or more. If the storage elastic modulus is less than 50 Pa, the height of the paint streaks cannot be sufficiently lowered, and a coating film having an excellent appearance cannot be obtained.
  • the storage elastic modulus of the coating composition of the present invention is, for example, 50 to 700 Pa. In one embodiment of the coating composition of the present invention, the storage elastic modulus is 50 Pa or more, 60 Pa or more, 70 Pa or more, 80 Pa or more, 90 Pa or more, 100 Pa or more, 130 Pa or more, 150 Pa or more, 170 Pa or more, 200 Pa or more, 230 Pa or more.
  • the storage elastic modulus is 700 Pa or less, 650 Pa or less, 600 Pa or less, 550 Pa or less, 500 Pa or less, 450 Pa or less, 400 Pa or less, 350 Pa or less, 300 Pa or less, 250 Pa or less, 230 Pa or less. , 200 Pa or less, 170 Pa or less, 150 Pa or less, 130 Pa or less, 100 Pa or less, 90 Pa or less, 80 Pa or less, 70 Pa or less, or 60 Pa or less.
  • the storage modulus is 70-500 Pa.
  • the storage elastic modulus is 50 to 400 Pa.
  • a method of using a viscosity adjusting agent having a large molecular weight or having a hard structure which will be described later, can be mentioned.
  • viscosity adjusting agents include SN thickeners 630 and 636 manufactured by San Nopco; Banstar S100A manufactured by Chubu Saiden; primal ASE-60 thickener manufactured by Dow Chemical Co., Ltd. and other alkaline swelling type viscosity adjusting agents; Cellulose-based viscosity modifiers such as cellosize QP4400 and 52000H manufactured by Dow Chemical Co., Ltd. can be mentioned.
  • the cellulosic viscosity adjuster tends to have a higher storage elastic modulus than the alkaline swelling type viscosity modifier.
  • the steady-state value ⁇ 2 of the viscosity of the coating composition of the present invention is 50 Pa ⁇ s or more. If the steady-state value ⁇ 2 of the viscosity is less than 50 Pa ⁇ s, sagging of the coating composition cannot be sufficiently suppressed, and a coating film having an excellent appearance cannot be obtained.
  • the steady-state value ⁇ 2 of the viscosity of the coating composition of the present invention is, for example, 50 to 1000 Pa ⁇ s.
  • the constant value ⁇ 2 of viscosity is 50 Pa ⁇ s or more, 60 Pa ⁇ s or more, 70 Pa ⁇ s or more, 80 Pa ⁇ s or more, 90 Pa ⁇ s or more, 100 Pa ⁇ s or more, 150 Pa.
  • -S or more 200 Pa ⁇ s or more, 250 Pa ⁇ s or more, 300 Pa ⁇ s or more, 350 Pa ⁇ s or more, 400 Pa ⁇ s or more, 450 Pa ⁇ s or more, 500 Pa ⁇ s or more, 550 Pa ⁇ s or more, 600 Pa ⁇ s or more, 650 Pa -S or more, 700 Pa ⁇ s or more, 750 Pa ⁇ s or more, 800 Pa ⁇ s or more, 850 Pa ⁇ s or more, 900 Pa ⁇ s or more, 950 Pa ⁇ s or more, or 1000 Pa ⁇ s or more.
  • the constant value ⁇ 2 of viscosity is 1000 Pa ⁇ s or less, 950 Pa ⁇ s or less, 900 Pa ⁇ s or less, 850 Pa ⁇ s or less, 800 Pa ⁇ s or less, 750 Pa ⁇ s or less, 700 Pa ⁇ s or less, 650 Pa ⁇ s or less, 600 Pa ⁇ s or less, 550 Pa ⁇ s or less, 500 Pa ⁇ s or less, 450 Pa ⁇ s or less, 400 Pa ⁇ s or less, 350 Pa ⁇ s or less, 300 Pa ⁇ s or less, 250 Pa ⁇ s or less, 200 Pa ⁇ s or less, 150 Pa ⁇ s or less, 100 Pa ⁇ s or less, 90 Pa ⁇ s or less, 80 Pa ⁇ s or less, 70 Pa ⁇ s or less, or 60 Pa ⁇ s or less.
  • the steady-state value ⁇ 2 of the viscosity is 50 to 500 Pa ⁇ s.
  • a method of using a viscosity adjusting agent having a large molecular weight which will be described later, can be mentioned.
  • the viscosity adjusting agent having a large molecular weight include SN thickener 630 and 636 manufactured by San Nopco; Banstar S100A manufactured by Chubu Saiden; and alkaline swelling type viscosity adjusting agent such as Dow Chemical's Primal ASE-60 thickener; Cellulose-based viscosity modifiers such as cellosize QP4400 and 52000H manufactured by Dow Chemical Co., Ltd. can be mentioned.
  • the viscosity ⁇ 1 is 0.1 to 10 Pa ⁇ s
  • the storage elastic modulus is 200 to 500 Pa
  • the steady-state value ⁇ 2 of the viscosity is 200 to 200. It is 400 Pa ⁇ s.
  • the viscosity ⁇ 1 is 5 to 40 Pa ⁇ s
  • the storage elastic modulus is 70 to 500 Pa
  • the steady-state viscosity ⁇ 2 is 80 to 400 Pa. ⁇ S.
  • the coating composition of the present invention typically comprises a resin component, a viscosity modifier, a pigment, and water and / or a solvent.
  • the coating composition may contain a cross-linking agent and other components.
  • the resin component has a function as a coating film forming element.
  • a resin component of a conventionally known coating composition can be used.
  • the resin component include acrylic resin, polyester resin, alkyd resin, fluororesin, epoxy resin, polyurethane resin, and polyether resin.
  • a polymer compound containing or composed of an inorganic component such as a silicone resin or an alkoxysilane condensate can also be used.
  • the resin component may be used alone or in combination of two or more.
  • the resin component may be an organic solvent type, an aqueous type (water-soluble, water-dispersible or emulsion), or a non-water-dispersed type.
  • the coating composition using the resin component may be, for example, a one-component type, a two-component mixed type composed of a main agent and a curing agent, or a multi-component mixed type consisting of a three-component mixed type or more.
  • the resin component can proceed with the curing reaction by heating or at room temperature.
  • the content of the resin component is not particularly limited and may be appropriately adjusted.
  • the solid content of the resin component is 10 to 90 parts by mass or 10 to 60 parts by mass with respect to a total of 100 parts by mass of the solid content of the resin component and the solid content of the pigment.
  • a known viscosity adjusting agent may be used to adjust the viscosity ⁇ 1 of the coating composition, the storage elastic modulus and the constant value ⁇ 2 of the viscosity.
  • the viscosity adjusting agent include an alkali swelling type viscosity adjusting agent, a urethane associated type viscosity adjusting agent, a cellulose-based viscosity adjusting agent, an amide-based viscosity adjusting agent, an inorganic layered compound-based viscosity adjusting agent, and an aminoplast-based viscosity adjusting agent. Can be mentioned.
  • alkali swelling type viscosity regulator examples include a polycarboxylic acid-based viscosity regulator, a polysulfonic acid-based viscosity regulator, and a polyphosphate-based viscosity regulator.
  • alkaline swelling type viscosity modifiers include, for example, SN thickener series such as SN thickener 615, 630, 636, 640 manufactured by San Nopco; primal series such as Primal ASE-60 thickener manufactured by Dow Chemical Co., Ltd .; Chubu Saiden. Banstar S100A manufactured by the company can be mentioned.
  • the alkali swelling type viscosity modifier is one or more selected from the group consisting of SN thickeners 630 and 636, Banster S100A and primal ASE-60 thickeners.
  • urethane-associating type viscosity adjusting agent examples include urethane-modified polyether type viscosity adjusting agents.
  • urethane-associated viscosity modifiers examples include ADEKA's Adecanol (registered trademark) UH-140S, 420, 450, 472, 526, 540, 550, 752 and other Adecanol (registered trademark) UH series; Examples include SN thickeners 612 and 665T manufactured by San Nopco Ltd.
  • the urethane associated viscosity modifier is one or more selected from the group consisting of Adecanol® UH-140S, 420, 472, 752 and SN Thickener 612.
  • cellulosic viscosity adjusting agent examples include cellulose-based viscosity adjusting agents such as crystalline cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.
  • cellulosic viscosity modifiers examples include the Theoras (registered trademark) series such as Asahi Kasei's Theoras (registered trademark) RC series; and the cellosize series such as Dow Chemical's cellosize QP 4400 and 52000H. Be done.
  • the cellulosic viscosity modifier is one or more selected from the group consisting of cellosize QP 4400 and cellosize QP 52000H.
  • amide-based viscosity modifier examples include fatty acid amide, polyamide, acrylic amide, long-chain polyaminoamide, aminoamide and salts thereof (for example, phosphate).
  • inorganic layered compound-based viscosity modifier examples include layered compounds such as montmorillonite, bentonite, and clay.
  • aminoplast-based viscosity modifier examples include hydrophobically modified ethoxylate aminoplast-based viscosity modifiers.
  • the viscosity modifier may be used alone or in combination of two or more.
  • the viscosity adjusting agent is one or more selected from the group consisting of an alkaline swelling type viscosity adjusting agent, a urethane association type viscosity adjusting agent, and a cellulosic viscosity adjusting agent.
  • the coating composition for roller coating, roll coating, brush coating or spatula coating contains a resin component and a viscosity modifier.
  • the viscosity adjuster is one or more selected from the group consisting of an alkaline swelling type viscosity adjuster, a urethane association type viscosity adjuster, and a cellulosic viscosity adjuster.
  • the content of the viscosity adjusting agent in the coating composition of the present invention is not particularly limited and may be appropriately adjusted.
  • the solid content of the viscosity modifier in the coating composition of the present invention is, for example, 0.1 to 3.0 parts by mass or 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the coating composition.
  • the solid content of the viscosity modifier is 0.1 part by mass or more, 0.3 part by mass or more, and 0.5 part by mass or more with respect to 100 parts by mass of the coating composition.
  • the solid content of the viscosity modifier is 3.0 parts by mass or less, 2.8 parts by mass or less, and 2.6 parts by mass with respect to 100 parts by mass of the coating composition.
  • 2.4 parts by mass or less 2.2 parts by mass or less, 2.0 parts by mass or less, 1.8 parts by mass or less, 1.6 parts by mass or less, 1.4 parts by mass or less, 1.2 parts by mass or less.
  • 1.0 part by mass or less, 0.9 part by mass or less, 0.8 part by mass or less, 0.7 part by mass or less, 0.6 part by mass or less, 0.5 part by mass or less or 0.3 part by mass or less be.
  • “100 parts by mass of the coating composition” is the whole coating composition containing water and / or a solvent in addition to the solid content in the resin component, the pigment component, the viscosity modifier and the like. It means 100 parts by mass.
  • the coating composition may contain a crosslinking agent.
  • the cross-linking agent can be selected according to the curable functional group of the resin component.
  • examples of the cross-linking agent include carbodiimide compounds, hydrazine compounds, amino resins, (blocking) polyisocyanate compounds, amine compounds, polyamide compounds and polyvalent carboxylic acid compounds.
  • the cross-linking agent may be used alone or in combination of two or more.
  • the pigments are not particularly limited, and known paint pigments can be used.
  • the pigment include colored pigments such as titanium dioxide, carbon black, petals, and phthalocyanine blue; extender pigments such as calcium carbonate, talc, and mica; and rust preventive pigments.
  • the pigment may be used alone or in combination of two or more.
  • the coating composition of the present invention may be either a water-based coating composition or a solvent-based coating composition.
  • the coating composition of the present invention is a water-based coating composition.
  • it is a coating composition satisfying the provisions of JIS A 6909.
  • the dispersion medium having the highest content in the coating composition is water, which is referred to as an aqueous coating composition.
  • a solvent-based coating composition is one in which the dispersion medium having the highest content in the coating composition is a solvent.
  • the total amount of paint solids in the paint composition of the present invention may be appropriately adjusted and is not particularly limited.
  • the total amount of the paint solid content is 20 to 80 parts by mass with respect to 100 parts by mass of the paint composition.
  • the total amount of the coating solid content is 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, and 50 parts by mass or more with respect to 100 parts by mass of the coating composition. 60 parts by mass or more, 70 parts by mass or more, or 80 parts by mass or more.
  • the total amount of the coating solid content is 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, and 50 parts by mass or less with respect to 100 parts by mass of the coating composition. , 40 parts by mass or less, 30 parts by mass or less, or 20 parts by mass or less.
  • water When water is used, conventionally known water can be appropriately selected and used. Examples of water include tap water, distilled water, deionized water, purified water and the like.
  • the water content of the paint composition may be adjusted as appropriate.
  • the water content of the coating composition is, for example, 20 to 80 parts by mass with respect to 100 parts by mass of the coating composition. In one embodiment of the coating composition of the present invention, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, 60 parts by mass or more, 70 parts by mass with respect to 100 parts by mass of the coating composition. Or more or 80 parts by mass or more. In one embodiment of the coating composition of the present invention, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, and 30 parts by mass with respect to 100 parts by mass of the coating composition. It is less than or equal to 20 parts by mass or less.
  • a solvent of a conventionally known coating composition can be appropriately selected and used.
  • the solvent include alcohols such as methanol, ethanol, 2-propanol and 1-butanol; ethyl acetate, butyl acetate, isobutyl acetate, ethyl propionate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol mono.
  • Ethers such as ethyl ether acetate; ethers such as diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dioxane, tetrahydrofuran (THF); ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, Glycols such as 1,3-butylene glycol, pentamethylene glycol, 1,3-octylene glycol; formamide, N-methylformamide, dimethylformamide (DMF), dimethylacetamide, dimethylsulfoxide (DMSO), N-methyl Amidos such as pyrrolidone (NMP); ketones such as acetone, methyl ethyl ketone (MEK), methyl propyl ketone, methyl isobutyl ketone, acetyl acetone, cyclohexanone; aliphatic hydrocarbons such as mineral spirit,
  • the coating composition of the present invention may be a room temperature drying type or a heat drying type. In one embodiment, the coating composition of the present invention is a room temperature dry type.
  • the coating composition of the present invention may be a one-component type or a two-component type.
  • the content of the solvent may be appropriately adjusted.
  • it is 0 to 15 parts by mass, preferably 0 to 10 parts by mass with respect to 100 parts by mass of the coating composition.
  • the solvent in this case for example, alcohols can be used.
  • the coating composition of the present invention contains a dispersant, a film-forming auxiliary, an antifreeze agent, a cross-linking accelerator, a curing agent, a leveling agent, a surface conditioner, an antifoaming agent, and a plasticizer.
  • a dispersant e.g., a sulfate, a sulfate, a sulfate, a sulfate, a curing agent, a leveling agent, a surface conditioner, an antifoaming agent, and a plasticizer.
  • Preservatives, fungicides, UV stabilizers and other other ingredients may be included. These other components may be used alone or in combination of two or more.
  • the coating composition according to the present invention is a coating composition for roller coating, roll coating, brush coating, or spatula coating.
  • the roller coating is not particularly limited, and may be a known roller coating such as coating using a hand-held roller.
  • the roll coating is not particularly limited, and may be a known roll coating such as a roll coating.
  • the number of rolls for roll coating is not limited, and may be 1, 2, 3, or 4.
  • the brush coating is not particularly limited, and may be a known brush coating using a brush, a round brush, a flat brush, a bracing brush, a brush, or the like.
  • the brush includes a brush.
  • the spatula coating is not particularly limited, and may be a known spatula coating such as a steel spatula, a wooden spatula, a plastic spatula, or a knife.
  • the method for preparing the coating composition is not particularly limited as long as the viscosity ⁇ 1, the storage elastic modulus and the constant value ⁇ 2 of the viscosity are within the predetermined ranges, and the above-mentioned resin component, pigment and viscosity adjusting agent are not particularly limited. Etc. can be mixed and prepared by a conventionally known method. Further, the coating composition of the present invention may be obtained by adding a viscosity adjusting agent or the like to a commercially available paint containing a resin component and a pigment to adjust the viscosity ⁇ 1, the storage elastic modulus and the constant value ⁇ 2 of the viscosity within predetermined ranges. ..
  • a conventionally known roller coating, roll coating, brush coating or spatula coating method can be used as a method for producing a coating film.
  • the drying temperature after applying the coating composition may be appropriately adjusted depending on the solvent and the like. For example, when drying in a short time such as 10 seconds to 30 minutes is required, the temperature can be 60 to 200 ° C, preferably 80 to 160 ° C. If it is not necessary to dry in a short time, it may be dried at room temperature, for example.
  • the object for forming a coating film using the coating composition of the present invention is not particularly limited and can be appropriately selected.
  • the objects include the body of a vehicle such as an automobile or a railroad vehicle, the body of an aircraft, the body and superstructure (furnishing) of a ship, the interior and exterior; the interior, exterior and roof of a building; furniture, fittings.
  • examples of the article having a coating film formed by using the coating composition of the present invention include vehicles such as automobiles and railroad vehicles, aircraft, ships, buildings, furniture, fittings, windowpanes, and transparent bodies (cases). , Including containers, resin plates and films), electrical appliances and the like.
  • the viscosity ⁇ 1 of the coating composition is a 50 mm cone plate, a gap of 0.1 mm, a measurement temperature of 23 ° C., and a shear deformation of a shear rate of 1000 s -1 using a stress-controlled rheometer "MCR302" manufactured by Anton Pearl. Was applied for 30 seconds, and immediately after that, the viscosity obtained by performing a steady flow measurement in which a shear deformation with a shear rate of 0.01 -1 was applied for 5 seconds was used.
  • a stress-controlled rheometer "MCR302" manufactured by Anton Pearl Co., Ltd. was used, a cone plate of 50 mm, a gap of 0.1 mm, a measurement temperature of 23 ° C., a strain: linear strain, and an angular frequency.
  • the storage elastic modulus obtained by measuring under the condition of 100s -1 was used.
  • the steady value ⁇ 2 of the coating composition was set to a 50 mm cone plate, a gap of 0.1 mm, a measurement temperature of 23 ° C., and a shear rate of 0.01 -1 using a stress-controlled rheometer “MCR302” manufactured by Anton Pearl.
  • the steady value of the viscosity in the steady flow measurement of the shear deformation in was used.
  • Viscosity Adjuster 1 (Urethane Association Type Viscosity Adjuster): Product name "ADEKA NOL (registered trademark) UH-140S” manufactured by ADEKA (solid content: 30%, indicated as UH140S in Table 1).
  • Viscosity Adjuster 2 (Urethane Association Type Viscosity Adjuster): Product name "ADEKA NOL (registered trademark) UH-752” manufactured by ADEKA (solid content: 30%, indicated as UH752 in Table 1).
  • Viscosity Adjuster 3 (Urethane Association Type Viscosity Adjuster): Product name "ADEKA NOL (registered trademark) UH-420” manufactured by ADEKA (solid content: 30%, indicated as UH420 in Table 1).
  • Viscosity Adjuster 4 (Urethane Association Type Viscosity Adjuster): Product name "ADEKA NOL (registered trademark) UH-472” manufactured by ADEKA (solid content: 30%, indicated as UH472 in Table 1).
  • Viscosity Adjuster 5 (Urethane Association Type Viscosity Adjuster): Product name "SN Thickener 612" manufactured by San Nopco Ltd.
  • Viscosity adjuster 6 Alkaline swelling type viscosity adjuster: Product name "SN Thickener 630" manufactured by San Nopco Ltd. (solid content: 30%, indicated as SN630 in Table 1)
  • Viscosity adjuster 7 Alkaline swelling type viscosity adjuster: Product name "Banster S100A” manufactured by Chubu Saiden Co., Ltd. (solid content: 28%, indicated as S100A in Table 1)
  • Viscosity adjuster 8 Alkaline swelling type viscosity adjuster: Product name "SN Thickener 636” manufactured by San Nopco Ltd.
  • Viscosity adjuster 9 Alkaline swelling type viscosity adjuster: Product name "Primal ASE-60 Thickener” manufactured by Dow Chemical Co., Ltd. (solid content: 28%, indicated as ASE60 in Table 1)
  • Viscosity Adjuster 10 Cellulose Viscosity Adjuster: Product name "Cellosize QP 4400” manufactured by Dow Chemical Co., Ltd. (solid content: 100%, indicated as QP 4400 in Table 1)
  • Viscosity Adjuster 11 Cellulose Viscosity Adjuster: Product name "Cellosize QP 52000H” manufactured by Dow Chemical Co., Ltd. (solid content: 100%, indicated as QP 52000H in Table 1)
  • the slate plate a trade name “slate plate” (length 90 cm, width 45 cm) manufactured by TP Giken Co., Ltd. was used.
  • the undercoat paint the product name "Nippe Aqueous Transparent Sealer” manufactured by Nippon Paint Co., Ltd. was used.
  • Example 1 Each component was mixed in the formulation (part by mass) shown in Table 1 to prepare a coating composition.
  • the viscosity ⁇ 1, the storage elastic modulus and the steady-state value ⁇ 2 of the viscosity were measured. The results are shown in Table 1.
  • the present invention it is possible to provide a coating composition capable of suppressing paint streaks and sagging and forming a coating film having an excellent appearance.

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Abstract

Provided is a coating composition which is inhibited from streaking or sagging and can form coating films having an excellent appearance. This coating composition is for application with a roller, roll, brush, or spatula and, after having undergone a shear deformation at a shear rate of 1,000 s-1 at 23°C for 30 seconds and, immediately thereafter, a shear deformation at a shear rate of 0.01 s-1 for five seconds, has a viscosity ƞ1 of 40 Pa·s or less. The coating composition has a storage modulus at 23°C of 50 Pa or greater. In a steady-flow measurement with a shear deformation at 23°C and a shear rate of 0.01 s-1, the coating composition has a steady-flow viscosity ƞ2 of 50 Pa·s or greater.

Description

ローラー塗装用、ロール塗装用、刷毛塗装用またはヘラ塗装用の塗料組成物Paint composition for roller coating, roll coating, brush coating or spatula coating 関連出願の相互参照Cross-reference of related applications
　本願は、２０２０年７月１３日に出願の日本国特許出願第２０２０－１２００５２号の優先権の利益を主張するものであり、その内容は、参照により本願に組み込まれる。 This application claims the priority benefit of Japanese Patent Application No. 2020-120052 filed on July 13, 2020, the contents of which are incorporated herein by reference.
　本発明は、ローラー塗装用、ロール塗装用、刷毛塗装用またはヘラ塗装用の塗料組成物に関する。 The present invention relates to a coating composition for roller coating, roll coating, brush coating or spatula coating.
　ローラー、ロール、刷毛、ヘラなどの塗装具を用いる塗装では、スプレーを用いるスプレー塗装と異なり、塗料を保持した塗装具と被塗物とが接触し、塗装具または被塗物が他方に対して移動することによって、塗装が行われる。 In painting using a paint tool such as a roller, roll, brush, or spatula, unlike spray painting using a spray, the paint tool holding the paint and the object to be coated come into contact with each other, and the paint tool or the object to be coated is applied to the other. Painting is done by moving.
　本発明者らは、特許文献１で塗装作業性に優れ、かつ塗料の塗り感が良好な塗料組成物を開示している。 The present inventors disclose in Patent Document 1 a coating composition having excellent coating workability and a good coating feeling.
国際公開第２０１８／０７９２１２号International Publication No. 2018/079212
　本発明者らが特許文献１の塗料組成物をさらに検討したところ、被塗物と接触するローラーなどの塗装具を用いる塗装では、例えば、図２に示すように、得られた塗膜に塗料の筋（ローラーによる塗料の筋の場合はローラーマークともいう）が生じ、塗膜の外観に劣る場合があることがわかった。 As a result of further study of the coating composition of Patent Document 1, the present inventors have found that in coating using a coating tool such as a roller that comes into contact with an object to be coated, for example, as shown in FIG. 2, a coating film is applied to the obtained coating film. It was found that the appearance of the paint film may be inferior due to the occurrence of streaks (also called roller marks in the case of paint streaks by rollers).
　また、垂直または傾斜した面に塗装した塗膜では、塗料の筋（以下、「塗料筋」という）だけでなく、塗料のタレ（塗膜の乾燥までの間に塗料が下方に移動して起こる局所的な膜厚の異常）も塗膜の外観を低下させるため、塗料のタレも抑制する必要がある。 In addition, in a coating film applied to a vertical or inclined surface, not only the paint streaks (hereinafter referred to as "paint streaks") but also the paint sagging (the paint moves downward until the paint film dries) occurs. Since local abnormalities in film thickness) also deteriorate the appearance of the coating film, it is necessary to suppress the sagging of the paint.
　そこで、本発明は、塗料筋およびタレを抑制し、外観に優れた塗膜を形成可能な、塗料組成物を提供することを目的とする。 Therefore, an object of the present invention is to provide a coating composition capable of suppressing paint streaks and sagging and forming a coating film having an excellent appearance.
　本発明に係る塗料組成物は、
　ローラー塗装用、ロール塗装用、刷毛塗装用またはヘラ塗装用の塗料組成物であって、
　前記塗料組成物に２３℃でせん断速度１０００ｓ-1のせん断変形を３０秒間かけた直後、せん断速度０．０１ｓ-1のせん断変形を５秒間かけたときの粘度η１が、４０Ｐａ・ｓ以下であり、
　前記塗料組成物の２３℃での貯蔵弾性率が、５０Ｐａ以上であり、かつ、
　前記塗料組成物の２３℃、せん断速度０．０１ｓ-1でのせん断変形の定常流測定での粘度の定常値η２が、５０Ｐａ・ｓ以上である、
　ローラー塗装用、ロール塗装用、刷毛塗装用またはヘラ塗装用の塗料組成物である。これにより、塗料筋およびタレを抑制し、外観に優れた塗膜を得ることができる。 The coating composition according to the present invention is
A paint composition for roller coating, roll coating, brush coating, or spatula coating.
Immediately after the coating composition is subjected to shear deformation at a shear rate of 1000 s -1 at 23 ° C. for 30 seconds, the viscosity η 1 when shear deformation at a shear rate of 0.01 s -1 is applied for 5 seconds is 40 Pa · s or less. ,
The storage elastic modulus of the coating composition at 23 ° C. is 50 Pa or more, and
The constant value η2 of the viscosity of the coating composition in the steady flow measurement of shear deformation at 23 ° C. and a shear rate of 0.01 s -1 is 50 Pa · s or more.
A coating composition for roller coating, roll coating, brush coating, or spatula coating. As a result, it is possible to suppress paint streaks and sagging and obtain a coating film having an excellent appearance.
　本発明に係る塗料組成物の一実施形態では、前記粘度の定常値η２が、５０～５００Ｐａ・ｓである。 In one embodiment of the coating composition according to the present invention, the steady-state value η2 of the viscosity is 50 to 500 Pa · s.
　本発明に係る塗料組成物の一実施形態では、前記粘度η１が、３～４０Ｐａ・ｓである。 In one embodiment of the coating composition according to the present invention, the viscosity η1 is 3 to 40 Pa · s.
　本発明に係る塗料組成物の一実施形態では、前記貯蔵弾性率が、５０～４００Ｐａである。 In one embodiment of the coating composition according to the present invention, the storage elastic modulus is 50 to 400 Pa.
　本発明に係る塗料組成物の一実施形態では、ローラー塗装用、ロール塗装用、刷毛塗装用またはヘラ塗装用の塗料組成物は、樹脂成分と粘性調整剤とを含み、
　前記粘性調整剤が、アルカリ膨潤型粘性調整剤、ウレタン会合型粘性調整剤およびセルロース系粘性調整剤からなる群より選択される１種以上である。 In one embodiment of the coating composition according to the present invention, the coating composition for roller coating, roll coating, brush coating or spatula coating contains a resin component and a viscosity modifier.
The viscosity adjuster is one or more selected from the group consisting of an alkaline swelling type viscosity adjuster, a urethane association type viscosity adjuster, and a cellulosic viscosity adjuster.
　本発明によれば、塗料筋およびタレを抑制し、外観に優れた塗膜を形成可能な、塗料組成物を提供することができる。 According to the present invention, it is possible to provide a coating composition capable of suppressing paint streaks and sagging and forming a coating film having an excellent appearance.
図１は、実施例５の塗膜の外観を示した図である。FIG. 1 is a diagram showing the appearance of the coating film of Example 5. 図２は、比較例２の塗膜の外観を示した図である。FIG. 2 is a diagram showing the appearance of the coating film of Comparative Example 2. 図３は、従来の塗料を用いたローラー塗装時の塗料筋の形成過程を示した模式図である。FIG. 3 is a schematic diagram showing a process of forming paint streaks during roller coating using a conventional paint.
　以下、本発明の実施形態について説明する。これらの記載は、本発明の例示を目的とするものであり、本発明を何ら限定するものではない。 Hereinafter, embodiments of the present invention will be described. These descriptions are for the purpose of exemplifying the present invention and do not limit the present invention in any way.
　本発明において、２以上の実施形態を任意に組み合わせることができる。 In the present invention, two or more embodiments can be arbitrarily combined.
　本発明において、塗料と塗料組成物は相互互換的に用いることができる。 In the present invention, the paint and the paint composition can be used interchangeably.
　本明細書において、数値範囲は、別段の記載がない限り、その範囲の上限値および下限値を含むことを意図している。例えば、５０～５００Ｐａ・ｓは、５０Ｐａ・ｓ以上５００Ｐａ・ｓ以下を意味する。 In the present specification, the numerical range is intended to include the upper limit value and the lower limit value of the range unless otherwise specified. For example, 50 to 500 Pa · s means 50 Pa · s or more and 500 Pa · s or less.
　本発明において、塗料組成物に２３℃でせん断速度１０００ｓ-1のせん断変形を３０秒間かけた直後、せん断速度０．０１ｓ-1のせん断変形を５秒間かけたときの粘度η１は、実施例に記載の方法により求める。 In the present invention, the viscosity η1 when the coating composition is subjected to a shear deformation of a shear rate of 1000 s -1 at 23 ° C. for 30 seconds and then a shear deformation of a shear rate of 0.01 s -1 for 5 seconds is used as an example. Obtained by the method described.
　本発明において、塗料組成物の２３℃での貯蔵弾性率は、実施例に記載の方法により求める。 In the present invention, the storage elastic modulus of the coating composition at 23 ° C. is determined by the method described in Examples.
　本発明において、塗料組成物の２３℃、せん断速度０．０１ｓ-1でのせん断変形の定常流測定での粘度の定常値η２は、実施例に記載の方法により求める。 In the present invention, the constant value η2 of the viscosity of the coating composition in the steady flow measurement of shear deformation at 23 ° C. and a shear rate of 0.01 s- 1 is obtained by the method described in Examples.
　（塗料組成物）
　本発明に係る塗料組成物は、
　ローラー塗装用、ロール塗装用、刷毛塗装用またはヘラ塗装用の塗料組成物であって、
　前記塗料組成物に２３℃でせん断速度１０００ｓ-1のせん断変形を３０秒間かけた直後、せん断速度０．０１ｓ-1のせん断変形を５秒間かけたときの粘度η１が、４０Ｐａ・ｓ以下であり、
　前記塗料組成物の２３℃での貯蔵弾性率が、５０Ｐａ以上であり、かつ、
　前記塗料組成物の２３℃、せん断速度０．０１ｓ-1でのせん断変形の定常流測定での粘度の定常値η２が、５０Ｐａ・ｓ以上である、
　ローラー塗装用、ロール塗装用、刷毛塗装用またはヘラ塗装用の塗料組成物である。 (Paint composition)
The coating composition according to the present invention is
A paint composition for roller coating, roll coating, brush coating, or spatula coating.
Immediately after the coating composition is subjected to shear deformation at a shear rate of 1000 s -1 at 23 ° C. for 30 seconds, the viscosity η 1 when shear deformation at a shear rate of 0.01 s -1 is applied for 5 seconds is 40 Pa · s or less. ,
The storage elastic modulus of the coating composition at 23 ° C. is 50 Pa or more, and
The constant value η2 of the viscosity of the coating composition in the steady flow measurement of shear deformation at 23 ° C. and a shear rate of 0.01 s -1 is 50 Pa · s or more.
A coating composition for roller coating, roll coating, brush coating, or spatula coating.
　本発明者らは、ローラーなどを用いた塗装による塗料筋と塗膜の外観との関係について調べたところ、塗料筋の高さが低いほど、塗料筋が塗膜の観察者に視認されにくく、塗膜の観察者は塗膜の外観が良いと評価することがわかった。 The present inventors investigated the relationship between the paint streaks and the appearance of the paint film by painting with a roller or the like. As a result, the lower the height of the paint streaks, the less visible the paint streaks were to the observer of the paint film. It was found that the observer of the coating film evaluated the appearance of the coating film as good.
　図３は、従来の塗料を用いたローラー塗装時の塗料筋の形成過程を示した模式図である。本発明者らが塗料筋をさらに調べたところ、塗料筋は図３のＡ～Ｅのように形成されることがわかった。まず、垂直方向の面１に対してローラー２を下側に引いて塗装を行う場合、ローラー２と面１とが離れつつある部分では、塗料の液膜３が発生する（図３のＡ）。ローラー２が下方に移動すると、その液膜３の一部が破れて空隙４が生ずる（図３のＢ）。さらにローラー２が移動すると、空隙４が大きくなり、糸状の塗料糸５になる（図３のＣ）。さらにローラー２が移動すると、塗料糸５が破断する（図３のＤ）。そして、破断した塗料糸５が塗膜６上に残り、塗料筋７が形成される（図３のＥ）。 FIG. 3 is a schematic diagram showing the process of forming paint streaks during roller painting using a conventional paint. Further examination of the paint streaks by the present inventors revealed that the paint streaks were formed as shown in FIGS. 3A to 3E. First, when the roller 2 is pulled downward with respect to the surface 1 in the vertical direction for painting, a liquid film 3 of the paint is generated at a portion where the roller 2 and the surface 1 are becoming separated (A in FIG. 3). .. When the roller 2 moves downward, a part of the liquid film 3 is broken to form a void 4 (B in FIG. 3). When the roller 2 further moves, the void 4 becomes larger and becomes a thread-like paint thread 5 (C in FIG. 3). When the roller 2 further moves, the paint thread 5 breaks (D in FIG. 3). Then, the broken paint thread 5 remains on the coating film 6 and the paint streaks 7 are formed (E in FIG. 3).
　この観察結果から、本発明者らは、当初、乾燥前の塗膜と塗料筋とを形成している塗料組成物の粘度に相当する、せん断速度０．０１ｓ-1でのせん断変形の定常流測定での粘度を低くして、塗料筋のレベリングを促進することで塗料筋の高さを低くし、塗膜の外観を向上することができると考えた。しかし、上記定常流測定での粘度を低くすると、塗料筋の高さは低くなるが、塗膜が乾燥する前に塗料組成物がタレてしまい、塗膜の外観を低下させることがわかった。 From this observation result, the present inventors initially performed a steady flow of shear deformation at a shear rate of 0.01 s-1 , which corresponds to the viscosity of the coating composition forming the coating film and the coating streaks before drying. It was considered that the height of the paint streaks could be lowered and the appearance of the paint film could be improved by lowering the viscosity in the measurement and promoting the leveling of the paint streaks. However, it has been found that when the viscosity in the steady flow measurement is lowered, the height of the paint streaks is lowered, but the paint composition sags before the paint film dries, and the appearance of the paint film is deteriorated.
　これらの結果に基づき、次に本発明者らは、以下の（１）および（２）が、塗料筋の高さを低くし、そして以下の（３）が塗料組成物のタレを抑制するのに有効であろうと推測した：
（１）塗料筋の粘度を低くして、塗料筋のレベリングを促進する。
（２）塗料筋の長さを短くして、塗料筋の表面積（表面自由エネルギー）を大きくすることで、塗料筋のレベリングを促進する。
（３）塗料筋の粘度ではなく、乾燥前の塗膜と塗料筋とを形成している塗料組成物の粘度を高くする。 Based on these results, the present inventors then describe the following (1) and (2) to lower the height of the paint streaks, and the following (3) to suppress the sagging of the paint composition. I speculated that it would be effective for:
(1) The viscosity of the paint streaks is lowered to promote the leveling of the paint streaks.
(2) By shortening the length of the paint streaks and increasing the surface area (surface free energy) of the paint streaks, the leveling of the paint streaks is promoted.
(3) Increase the viscosity of the paint composition forming the paint film and the paint streaks before drying, not the viscosity of the paint streaks.
　上記（１）について、塗装直後の短い時間（例えば、約５秒）における塗料筋は、塗装前の塗料とは異なり、図３のＣ～Ｅに示したように、ローラー（塗装具）による一定以上のせん断速度によって塗料の分子鎖の絡み合いが少なくなるなどミクロな構造が壊れた状態（図３Ｅ）であると考えられる。そのため、この状態における塗料筋の粘度を想定して、本発明者らは、塗料組成物に２３℃でせん断速度１０００ｓ-1のせん断変形を３０秒間かけた直後、せん断速度０．０１ｓ-1のせん断変形を５秒間かけたときの粘度η１（以下、単に「粘度η１」ということがある）を設定した。塗料にせん断速度１０００ｓ-1のせん断変形を３０秒間かけることで、塗装具による塗装で破断した塗料糸（例えば、図３のＤ）の状態となり、そしてこの３０秒間の直後に塗料組成物にさらにせん断速度０．０１ｓ-1のせん断変形を５秒間かける（前記３０秒経過した時点で０．０１ｓ-1のせん断速度のせん断変形を開始する）ことで、図３のＥに示した、形成直後の塗料筋の状態を再現ないし近似することができると考えられる。そして、この形成直後の塗料筋の粘度を想定した粘度η１を低くすることで、塗料筋のレベリングを促進する。 Regarding (1) above, the paint streaks in a short time immediately after painting (for example, about 5 seconds) are constant by the rollers (painting tools) as shown in C to E of FIG. 3, unlike the paint before painting. It is considered that the microstructure is broken (Fig. 3E) such that the entanglement of the molecular chains of the paint is reduced by the above shear rate. Therefore, assuming the viscosity of the paint streaks in this state, the present inventors applied the paint composition to a shear deformation at a shear rate of 1000 s -1 at 23 ° C. for 30 seconds, and immediately after that, the shear rate was 0.01 s -1 . The viscosity η1 (hereinafter, may be simply referred to as “viscosity η1”) when shear deformation is applied for 5 seconds is set. Shear deformation of the paint at a shear rate of 1000 s -1 for 30 seconds results in a state of paint thread (eg, D in FIG. 3) broken by painting with a paint tool, and immediately after this 30 seconds further into the paint composition. By applying a shear deformation with a shear rate of 0.01 s -1 for 5 seconds (the shear deformation with a shear rate of 0.01 s -1 starts after the lapse of 30 seconds), immediately after the formation shown in E of FIG. It is considered that the state of the paint streaks can be reproduced or approximated. Then, by lowering the viscosity η1 assuming the viscosity of the paint streaks immediately after the formation, the leveling of the paint streaks is promoted.
　上記（２）について、１個当たりの塗料筋の長さを短くすると、１個当たりの塗料筋の長さが長い場合よりも、その塗料筋の表面積は大きくなる。塗料筋の表面積が大きいと、塗料筋の表面自由エネルギーも大きくなるが、このとき、表面積を小さくして表面自由エネルギーを小さくしようとする力が塗料筋に働き、塗料筋のレベリングが促進されると考えられる。そこで、本発明者らは、塗料組成物の貯蔵弾性率に着目した。塗装時の塗料の液膜および塗料糸（図３のＢ～図３のＤ）は、弾性成分と粘性成分とを有する粘弾性体と考えることができ、弾性成分（貯蔵弾性率）を大きくすると、液膜および塗料糸の伸びが小さくなり、塗料糸とその塗料糸から生ずる塗料筋も短くなると考えられる。そして、この塗料組成物の貯蔵弾性率を高くすることで、塗料筋のレベリングを促進する。 Regarding (2) above, if the length of the paint streaks per piece is shortened, the surface area of the paint streaks becomes larger than when the length of the paint streaks per piece is long. When the surface area of the paint streaks is large, the surface free energy of the paint streaks also increases. At this time, the force to reduce the surface area and the surface free energy acts on the paint streaks, and the leveling of the paint streaks is promoted. it is conceivable that. Therefore, the present inventors focused on the storage elastic modulus of the coating composition. The liquid film and paint thread of the paint (B to D in FIG. 3) at the time of painting can be considered as a viscoelastic body having an elastic component and a viscous component, and when the elastic component (storage elasticity) is increased. It is considered that the elongation of the liquid film and the paint thread is reduced, and the paint thread and the paint streaks generated from the paint thread are also shortened. Then, by increasing the storage elastic modulus of this paint composition, the leveling of the paint streaks is promoted.
　そして、本発明者らは、塗料組成物の粘度η１を４０Ｐａ・ｓ以下とすること、および塗料組成物の２３℃での貯蔵弾性率（以下、「貯蔵弾性率」は、特に断らない限り、２３℃での値を指す）を５０Ｐａ以上とすることで、塗料筋の高さを低くすることができることを見出した。 Then, the present inventors set the viscosity η1 of the coating composition to 40 Pa · s or less, and the storage elastic modulus of the coating composition at 23 ° C. (hereinafter, “storage elastic modulus” is not specified unless otherwise specified. It was found that the height of the paint streaks can be lowered by setting (pointing to the value at 23 ° C.) to 50 Pa or more.
　上述したように、塗料筋の高さが低くなるほど、塗料筋が塗膜の観察者に視認されにくくなることから、塗膜における塗料筋の目視での視認性によって塗料筋の高さを評価することができる。また、本発明者らは、塗料筋の高さを定量化することについても検討した。まず、塗膜を有する塗装板を机上に水平に置く；次に、塗膜表面に塗装板の真横から光を照射し、塗膜に対して正面方向からデジタルカメラで塗膜表面を撮影する；次に、得られた画像の塗膜表面の輝度を数値化する（塗料筋の高さが高い場所では輝度が高く、塗料筋がない場所および塗膜表面が平坦な場所では輝度が低い）；そして、得られた数値から、塗料筋の高さに相当する値を算出する。この定量化した方法によっても、塗料筋の高さに相当する値が高い場合は、塗膜の外観に劣ることがわかった。また、塗膜を目視で観察した場合と、塗料筋の高さを定量化した場合で、塗料筋についての塗膜の外観の評価結果はほぼ同じであることもわかった。そのため、目視での塗膜の観察は、塗料筋の高さの定量化に比べて非常に簡便ながら、十分な塗料筋の高さの評価が可能であることもわかった。 As described above, the lower the height of the paint streaks, the less visible the paint streaks are to the observer of the coating film. Therefore, the height of the paint streaks is evaluated by the visual visibility of the paint streaks in the coating film. be able to. The present inventors also examined quantifying the height of the paint streaks. First, the paint film having the paint film is placed horizontally on the desk; then, the paint film surface is irradiated with light from the side of the paint film, and the paint film surface is photographed from the front of the paint film with a digital camera; Next, the brightness of the coating film surface of the obtained image is quantified (the brightness is high in the place where the height of the paint streaks is high, and the brightness is low in the place where there is no paint streaks and the place where the paint film surface is flat); Then, from the obtained numerical values, a value corresponding to the height of the paint streaks is calculated. Even with this quantified method, it was found that the appearance of the coating film was inferior when the value corresponding to the height of the paint streaks was high. It was also found that the evaluation results of the appearance of the paint film with respect to the paint streaks were almost the same when the paint film was visually observed and when the height of the paint streaks was quantified. Therefore, it was also found that visual observation of the coating film is much easier than quantifying the height of the paint streaks, but it is possible to sufficiently evaluate the height of the paint streaks.
　上記（３）について、塗料組成物のタレは、塗装後かつ塗膜の乾燥前の塗料組成物の下方への移動であるため、形成直後の短い時間における塗料筋の粘度ではなく、塗装後のせん断変形がほとんどなく安定しているが乾燥していない塗膜と塗料筋とを形成している塗料組成物の粘度を高くすることで、塗料組成物のタレを抑制することができると考えられる。本発明者らは、この塗装後の安定しているが乾燥していない塗料組成物の粘度は、上記粘度η１よりもさらに時間が経過し、粘度が定常値となったときの粘度で表すことができること、および、塗料組成物の２３℃、せん断速度０．０１ｓ-1でのせん断変形の定常流測定での粘度の定常値η２を５０Ｐａ・ｓ以上とすることで、塗料組成物のタレを抑制することができることを見出した。 Regarding (3) above, since the sagging of the paint composition is a downward movement of the paint composition after painting and before the coating film is dried, it is not the viscosity of the paint streaks in a short time immediately after formation, but after painting. It is considered that sagging of the coating composition can be suppressed by increasing the viscosity of the coating composition forming the coating film and the coating streaks, which are stable but not dried with almost no shear deformation. .. The present inventors express the viscosity of the stable but undried coating composition after coating as the viscosity when the viscosity reaches a steady value after a lapse of more time than the viscosity η1. By setting the constant value η2 of the viscosity of the coating composition in the steady flow measurement of shear deformation at 23 ° C. and a shear rate of 0.01s -1 to 50 Pa · s or more, the coating composition can be sagging. It was found that it can be suppressed.
　本発明の塗料組成物の粘度η１は、４０Ｐａ・ｓ以下である。粘度η１が４０Ｐａ・ｓより高いと、塗料筋の高さを十分に低くすることができず、外観に優れた塗膜を得られない。本発明の塗料組成物の粘度η１は、例えば、１～４０Ｐａ・ｓである。本発明の塗料組成物の一実施形態では、粘度η１は、４０Ｐａ・ｓ以下、３５Ｐａ・ｓ以下、３０Ｐａ・ｓ以下、２５Ｐａ・ｓ以下、２０Ｐａ・ｓ以下、１５Ｐａ・ｓ以下、１０Ｐａ・ｓ以下、７Ｐａ・ｓ以下、５Ｐａ・ｓ以下または３Ｐａ・ｓ以下である。本発明の塗料組成物の別の実施形態では、粘度η１は、１Ｐａ・ｓ以上、３Ｐａ・ｓ以上、５Ｐａ・ｓ以上、７Ｐａ・ｓ以上、１０Ｐａ・ｓ以上、１５Ｐａ・ｓ以上、２０Ｐａ・ｓ以上、２５Ｐａ・ｓ以上、３０Ｐａ・ｓ以上または３５Ｐａ・ｓ以上である。本発明の塗料組成物のさらに別の実施形態では、粘度η１は、５～４０Ｐａ・ｓである。 The viscosity η1 of the coating composition of the present invention is 40 Pa · s or less. If the viscosity η1 is higher than 40 Pa · s, the height of the paint streaks cannot be sufficiently lowered, and a coating film having an excellent appearance cannot be obtained. The viscosity η1 of the coating composition of the present invention is, for example, 1 to 40 Pa · s. In one embodiment of the coating composition of the present invention, the viscosity η1 is 40 Pa · s or less, 35 Pa · s or less, 30 Pa · s or less, 25 Pa · s or less, 20 Pa · s or less, 15 Pa · s or less, 10 Pa · s or less. , 7 Pa · s or less, 5 Pa · s or less, or 3 Pa · s or less. In another embodiment of the coating composition of the present invention, the viscosity η1 is 1 Pa · s or more, 3 Pa · s or more, 5 Pa · s or more, 7 Pa · s or more, 10 Pa · s or more, 15 Pa · s or more, 20 Pa · s. The above is 25 Pa · s or more, 30 Pa · s or more, or 35 Pa · s or more. In yet another embodiment of the coating composition of the present invention, the viscosity η1 is 5-40 Pa · s.
　本発明に係る塗料組成物の一実施形態では、前記粘度η１が、３～４０Ｐａ・ｓである。 In one embodiment of the coating composition according to the present invention, the viscosity η1 is 3 to 40 Pa · s.
　本発明の塗料組成物の粘度η１を低くするためには、例えば、後述する粘性調整剤として、分子量の小さいものを用いる方法が挙げられる。分子量の小さい粘性調整剤としては、例えば、ＡＤＥＫＡ社製のＵＨ－１４０Ｓ、ＵＨ－７５２、ＵＨ－４２０、ＵＨ－４７２などのＵＨシリーズ；サンノプコ社製のＳＮ　シックナー　６１２などのウレタン会合型粘性調整剤などが挙げられる。 In order to reduce the viscosity η1 of the coating composition of the present invention, for example, a method of using a viscosity adjusting agent having a small molecular weight, which will be described later, can be mentioned. Examples of the viscosity adjusting agent having a small molecular weight include UH series such as UH-140S, UH-752, UH-420, and UH-472 manufactured by ADEKA; and urethane association type viscosity adjusting agents such as SN Thickener 612 manufactured by San Nopco Ltd. And so on.
　本発明の塗料組成物の貯蔵弾性率は、５０Ｐａ以上である。貯蔵弾性率が５０Ｐａ未満では、塗料筋の高さを十分に低くすることができず、外観に優れた塗膜を得られない。本発明の塗料組成物の貯蔵弾性率は、例えば、５０～７００Ｐａである。本発明の塗料組成物の一実施形態では、貯蔵弾性率は、５０Ｐａ以上、６０Ｐａ以上、７０Ｐａ以上、８０Ｐａ以上、９０Ｐａ以上、１００Ｐａ以上、１３０Ｐａ以上、１５０Ｐａ以上、１７０Ｐａ以上、２００Ｐａ以上、２３０Ｐａ以上、２５０Ｐａ以上、３００Ｐａ以上、３５０Ｐａ以上、４００Ｐａ以上、４５０Ｐａ以上、５００Ｐａ以上、５５０Ｐａ以上、６００Ｐａ以上、６５０Ｐａ以上または７００Ｐａ以上である。本発明の塗料組成物の別の実施形態では、貯蔵弾性率は、７００Ｐａ以下、６５０Ｐａ以下、６００Ｐａ以下、５５０Ｐａ以下、５００Ｐａ以下、４５０Ｐａ以下、４００Ｐａ以下、３５０Ｐａ以下、３００Ｐａ以下、２５０Ｐａ以下、２３０Ｐａ以下、２００Ｐａ以下、１７０Ｐａ以下、１５０Ｐａ以下、１３０Ｐａ以下、１００Ｐａ以下、９０Ｐａ以下、８０Ｐａ以下、７０Ｐａ以下または６０Ｐａ以下である。本発明の塗料組成物のさらに別の実施形態では、貯蔵弾性率は、７０～５００Ｐａである。 The storage elastic modulus of the coating composition of the present invention is 50 Pa or more. If the storage elastic modulus is less than 50 Pa, the height of the paint streaks cannot be sufficiently lowered, and a coating film having an excellent appearance cannot be obtained. The storage elastic modulus of the coating composition of the present invention is, for example, 50 to 700 Pa. In one embodiment of the coating composition of the present invention, the storage elastic modulus is 50 Pa or more, 60 Pa or more, 70 Pa or more, 80 Pa or more, 90 Pa or more, 100 Pa or more, 130 Pa or more, 150 Pa or more, 170 Pa or more, 200 Pa or more, 230 Pa or more. 250 Pa or more, 300 Pa or more, 350 Pa or more, 400 Pa or more, 450 Pa or more, 500 Pa or more, 550 Pa or more, 600 Pa or more, 650 Pa or more, or 700 Pa or more. In another embodiment of the coating composition of the present invention, the storage elastic modulus is 700 Pa or less, 650 Pa or less, 600 Pa or less, 550 Pa or less, 500 Pa or less, 450 Pa or less, 400 Pa or less, 350 Pa or less, 300 Pa or less, 250 Pa or less, 230 Pa or less. , 200 Pa or less, 170 Pa or less, 150 Pa or less, 130 Pa or less, 100 Pa or less, 90 Pa or less, 80 Pa or less, 70 Pa or less, or 60 Pa or less. In yet another embodiment of the coating composition of the present invention, the storage modulus is 70-500 Pa.
　本発明に係る塗料組成物の一実施形態では、前記貯蔵弾性率が、５０～４００Ｐａである。 In one embodiment of the coating composition according to the present invention, the storage elastic modulus is 50 to 400 Pa.
　本発明の塗料組成物の貯蔵弾性率を高くするためには、例えば、後述する粘性調整剤として、分子量の大きいものまたは硬い構造を有するものを用いる方法が挙げられる。このような粘性調整剤としては、例えば、サンノプコ社製のＳＮ　シックナー　６３０、６３６；中部サイデン社製のバンスター　Ｓ１００Ａ；ダウケミカル社製のプライマル　ＡＳＥ－６０　シックナーなどのアルカリ膨潤型粘性調整剤；およびダウケミカル社製のセロサイズ　ＱＰ４４００、５２０００Ｈなどのセルロース系粘性調整剤などが挙げられる。貯蔵弾性率を高くする場合、アルカリ膨潤型粘性調整剤よりもセルロース系粘性調整剤の方が、貯蔵弾性率を高くしやすい。 In order to increase the storage elastic modulus of the coating composition of the present invention, for example, a method of using a viscosity adjusting agent having a large molecular weight or having a hard structure, which will be described later, can be mentioned. Examples of such viscosity adjusting agents include SN thickeners 630 and 636 manufactured by San Nopco; Banstar S100A manufactured by Chubu Saiden; primal ASE-60 thickener manufactured by Dow Chemical Co., Ltd. and other alkaline swelling type viscosity adjusting agents; Cellulose-based viscosity modifiers such as cellosize QP4400 and 52000H manufactured by Dow Chemical Co., Ltd. can be mentioned. When increasing the storage elastic modulus, the cellulosic viscosity adjuster tends to have a higher storage elastic modulus than the alkaline swelling type viscosity modifier.
　本発明の塗料組成物の粘度の定常値η２は、５０Ｐａ・ｓ以上である。粘度の定常値η２が５０Ｐａ・ｓ未満では、塗料組成物のタレを十分に抑制できず、外観に優れた塗膜を得られない。本発明の塗料組成物の粘度の定常値η２は、例えば、５０～１０００Ｐａ・ｓである。本発明の塗料組成物の一実施形態では、粘度の定常値η２は、５０Ｐａ・ｓ以上、６０Ｐａ・ｓ以上、７０Ｐａ・ｓ以上、８０Ｐａ・ｓ以上、９０Ｐａ・ｓ以上、１００Ｐａ・ｓ以上、１５０Ｐａ・ｓ以上、２００Ｐａ・ｓ以上、２５０Ｐａ・ｓ以上、３００Ｐａ・ｓ以上、３５０Ｐａ・ｓ以上、４００Ｐａ・ｓ以上、４５０Ｐａ・ｓ以上、５００Ｐａ・ｓ以上、５５０Ｐａ・ｓ以上、６００Ｐａ・ｓ以上、６５０Ｐａ・ｓ以上、７００Ｐａ・ｓ以上、７５０Ｐａ・ｓ以上、８００Ｐａ・ｓ以上、８５０Ｐａ・ｓ以上、９００Ｐａ・ｓ以上、９５０Ｐａ・ｓ以上または１０００Ｐａ・ｓ以上である。本発明の塗料組成物の別の実施形態では、粘度の定常値η２は、１０００Ｐａ・ｓ以下、９５０Ｐａ・ｓ以下、９００Ｐａ・ｓ以下、８５０Ｐａ・ｓ以下、８００Ｐａ・ｓ以下、７５０Ｐａ・ｓ以下、７００Ｐａ・ｓ以下、６５０Ｐａ・ｓ以下、６００Ｐａ・ｓ以下、５５０Ｐａ・ｓ以下、５００Ｐａ・ｓ以下、４５０Ｐａ・ｓ以下、４００Ｐａ・ｓ以下、３５０Ｐａ・ｓ以下、３００Ｐａ・ｓ以下、２５０Ｐａ・ｓ以下、２００Ｐａ・ｓ以下、１５０Ｐａ・ｓ以下、１００Ｐａ・ｓ以下、９０Ｐａ・ｓ以下、８０Ｐａ・ｓ以下、７０Ｐａ・ｓ以下または６０Ｐａ・ｓ以下である。本発明の塗料組成物のさらに別の実施形態では、粘度の定常値η２は、８０～４００Ｐａ・ｓである。 The steady-state value η2 of the viscosity of the coating composition of the present invention is 50 Pa · s or more. If the steady-state value η2 of the viscosity is less than 50 Pa · s, sagging of the coating composition cannot be sufficiently suppressed, and a coating film having an excellent appearance cannot be obtained. The steady-state value η2 of the viscosity of the coating composition of the present invention is, for example, 50 to 1000 Pa · s. In one embodiment of the coating composition of the present invention, the constant value η2 of viscosity is 50 Pa · s or more, 60 Pa · s or more, 70 Pa · s or more, 80 Pa · s or more, 90 Pa · s or more, 100 Pa · s or more, 150 Pa. -S or more, 200 Pa · s or more, 250 Pa · s or more, 300 Pa · s or more, 350 Pa · s or more, 400 Pa · s or more, 450 Pa · s or more, 500 Pa · s or more, 550 Pa · s or more, 600 Pa · s or more, 650 Pa -S or more, 700 Pa · s or more, 750 Pa · s or more, 800 Pa · s or more, 850 Pa · s or more, 900 Pa · s or more, 950 Pa · s or more, or 1000 Pa · s or more. In another embodiment of the coating composition of the present invention, the constant value η2 of viscosity is 1000 Pa · s or less, 950 Pa · s or less, 900 Pa · s or less, 850 Pa · s or less, 800 Pa · s or less, 750 Pa · s or less, 700 Pa · s or less, 650 Pa · s or less, 600 Pa · s or less, 550 Pa · s or less, 500 Pa · s or less, 450 Pa · s or less, 400 Pa · s or less, 350 Pa · s or less, 300 Pa · s or less, 250 Pa · s or less, 200 Pa · s or less, 150 Pa · s or less, 100 Pa · s or less, 90 Pa · s or less, 80 Pa · s or less, 70 Pa · s or less, or 60 Pa · s or less. In yet another embodiment of the coating composition of the present invention, the steady-state value η2 of viscosity is 80 to 400 Pa · s.
　本発明に係る塗料組成物の一実施形態では、前記粘度の定常値η２が、５０～５００Ｐａ・ｓである。 In one embodiment of the coating composition according to the present invention, the steady-state value η2 of the viscosity is 50 to 500 Pa · s.
　本発明の塗料組成物の粘度の定常値η２を高くするためには、例えば、後述する粘性調整剤として、分子量の大きいものを用いる方法が挙げられる。分子量の大きい粘性調整剤としては、例えば、サンノプコ社製のＳＮ　シックナー　６３０、６３６；中部サイデン社製のバンスター　Ｓ１００Ａ；ダウケミカル社製のプライマル　ＡＳＥ－６０　シックナーなどのアルカリ膨潤型粘性調整剤；およびダウケミカル社製のセロサイズ　ＱＰ４４００、５２０００Ｈなどのセルロース系粘性調整剤などが挙げられる。 In order to increase the steady-state value η2 of the viscosity of the coating composition of the present invention, for example, a method of using a viscosity adjusting agent having a large molecular weight, which will be described later, can be mentioned. Examples of the viscosity adjusting agent having a large molecular weight include SN thickener 630 and 636 manufactured by San Nopco; Banstar S100A manufactured by Chubu Saiden; and alkaline swelling type viscosity adjusting agent such as Dow Chemical's Primal ASE-60 thickener; Cellulose-based viscosity modifiers such as cellosize QP4400 and 52000H manufactured by Dow Chemical Co., Ltd. can be mentioned.
　本発明の塗料組成物の好適な一実施形態では、粘度η１が、０．１～１０Ｐａ・ｓであり、貯蔵弾性率が、２００～５００Ｐａであり、かつ、粘度の定常値η２が、２００～４００Ｐａ・ｓである。本発明の塗料組成物の好適な別の実施形態では、粘度η１が、５～４０Ｐａ・ｓであり、貯蔵弾性率が、７０～５００Ｐａであり、かつ、粘度の定常値η２が、８０～４００Ｐａ・ｓである。 In a preferred embodiment of the coating composition of the present invention, the viscosity η1 is 0.1 to 10 Pa · s, the storage elastic modulus is 200 to 500 Pa, and the steady-state value η2 of the viscosity is 200 to 200. It is 400 Pa · s. In another preferred embodiment of the coating composition of the present invention, the viscosity η1 is 5 to 40 Pa · s, the storage elastic modulus is 70 to 500 Pa, and the steady-state viscosity η 2 is 80 to 400 Pa.・ S.
　本発明の塗料組成物は、典型的には、樹脂成分、粘性調整剤、顔料、ならびに水および／または溶剤を含む。塗料組成物は、架橋剤、その他の成分を含んでいてもよい。 The coating composition of the present invention typically comprises a resin component, a viscosity modifier, a pigment, and water and / or a solvent. The coating composition may contain a cross-linking agent and other components.
　・樹脂成分
　樹脂成分は塗膜形成要素としての働きを有する。樹脂成分としては、従来公知の塗料組成物の樹脂成分を用いることができる。樹脂成分としては、例えば、アクリル樹脂、ポリエステル樹脂、アルキド樹脂、フッ素樹脂、エポキシ樹脂、ポリウレタン樹脂、ポリエーテル樹脂などを挙げることができる。また、樹脂成分として、例えば、シリコーン樹脂、アルコキシシラン縮合物などの、無機成分を含む、または、無機成分からなる高分子化合物を用いることもできる。樹脂成分は、１種単独でまたは２種以上を組み合わせて用いてもよい。 -Resin component The resin component has a function as a coating film forming element. As the resin component, a resin component of a conventionally known coating composition can be used. Examples of the resin component include acrylic resin, polyester resin, alkyd resin, fluororesin, epoxy resin, polyurethane resin, and polyether resin. Further, as the resin component, a polymer compound containing or composed of an inorganic component such as a silicone resin or an alkoxysilane condensate can also be used. The resin component may be used alone or in combination of two or more.
　樹脂成分は、有機溶剤形、水性形（水溶性、水分散性もしくはエマルション）、または非水分散形のいずれでもよい。 The resin component may be an organic solvent type, an aqueous type (water-soluble, water-dispersible or emulsion), or a non-water-dispersed type.
　樹脂成分を用いた塗料組成物は、例えば、一液形でもよいし、主剤および硬化剤から構成される二液混合形でもよく、三液混合形以上の多成分混合形であってもよい。 The coating composition using the resin component may be, for example, a one-component type, a two-component mixed type composed of a main agent and a curing agent, or a multi-component mixed type consisting of a three-component mixed type or more.
　樹脂成分は、加熱により、または常温で硬化反応を進行させることができる。 The resin component can proceed with the curing reaction by heating or at room temperature.
　樹脂成分の含有量は、特に限定されず、適宜調節すればよい。一実施形態では、樹脂成分の固形分と顔料の固形分との合計１００質量部に対して、樹脂成分の固形分が１０～９０質量部または１０～６０質量部である。 The content of the resin component is not particularly limited and may be appropriately adjusted. In one embodiment, the solid content of the resin component is 10 to 90 parts by mass or 10 to 60 parts by mass with respect to a total of 100 parts by mass of the solid content of the resin component and the solid content of the pigment.
　・粘性調整剤
　本発明では、塗料組成物の粘度η１、貯蔵弾性率および粘度の定常値η２を調節するために公知の粘性調整剤を用いてもよい。粘性調整剤としては、例えば、アルカリ膨潤型粘性調整剤、ウレタン会合型粘性調整剤、セルロース系粘性調整剤、アマイド系粘性調整剤、無機層状化合物系粘性調整剤およびアミノプラスト系粘性調整剤などが挙げられる。 -Viscosity Adjusting Agent In the present invention, a known viscosity adjusting agent may be used to adjust the viscosity η1 of the coating composition, the storage elastic modulus and the constant value η2 of the viscosity. Examples of the viscosity adjusting agent include an alkali swelling type viscosity adjusting agent, a urethane associated type viscosity adjusting agent, a cellulose-based viscosity adjusting agent, an amide-based viscosity adjusting agent, an inorganic layered compound-based viscosity adjusting agent, and an aminoplast-based viscosity adjusting agent. Can be mentioned.
　アルカリ膨潤型粘性調整剤としては、例えば、ポリカルボン酸系粘性調整剤、ポリスルホン酸系粘性調整剤、ポリリン酸系粘性調整剤などが挙げられる。 Examples of the alkali swelling type viscosity regulator include a polycarboxylic acid-based viscosity regulator, a polysulfonic acid-based viscosity regulator, and a polyphosphate-based viscosity regulator.
　アルカリ膨潤型粘性調整剤の市販品としては、例えば、サンノプコ社製のＳＮ　シックナー　６１５、６３０、６３６、６４０などのＳＮ　シックナーシリーズ；ダウケミカル社製のプライマル　ＡＳＥ－６０　シックナーなどのプライマルシリーズ；中部サイデン社製のバンスター　Ｓ１００Ａなどが挙げられる。一実施形態では、アルカリ膨潤型粘性調整剤は、ＳＮ　シックナー　６３０、６３６、バンスター　Ｓ１００Ａおよびプライマル　ＡＳＥ－６０　シックナーからなる群より選択される１種以上である。 Commercially available products of alkaline swelling type viscosity modifiers include, for example, SN thickener series such as SN thickener 615, 630, 636, 640 manufactured by San Nopco; primal series such as Primal ASE-60 thickener manufactured by Dow Chemical Co., Ltd .; Chubu Saiden. Banstar S100A manufactured by the company can be mentioned. In one embodiment, the alkali swelling type viscosity modifier is one or more selected from the group consisting of SN thickeners 630 and 636, Banster S100A and primal ASE-60 thickeners.
　ウレタン会合型粘性調整剤としては、例えば、ウレタン変性ポリエーテル型粘性調整剤などが挙げられる。 Examples of the urethane-associating type viscosity adjusting agent include urethane-modified polyether type viscosity adjusting agents.
　ウレタン会合型粘性調整剤の市販品としては、例えば、ＡＤＥＫＡ社製のアデカノール（登録商標）　ＵＨ－１４０Ｓ、４２０、４５０、４７２、５２６、５４０、５５０、７５２などのアデカノール（登録商標）　ＵＨシリーズ；サンノプコ社製のＳＮ　シックナー　６１２、６６５Ｔなどが挙げられる。一実施形態では、ウレタン会合型粘性調整剤は、アデカノール（登録商標）　ＵＨ－１４０Ｓ、４２０、４７２、７５２およびＳＮ　シックナー　６１２からなる群より選択される１種以上である。 Examples of commercially available urethane-associated viscosity modifiers include ADEKA's Adecanol (registered trademark) UH-140S, 420, 450, 472, 526, 540, 550, 752 and other Adecanol (registered trademark) UH series; Examples include SN thickeners 612 and 665T manufactured by San Nopco Ltd. In one embodiment, the urethane associated viscosity modifier is one or more selected from the group consisting of Adecanol® UH-140S, 420, 472, 752 and SN Thickener 612.
　セルロース系粘性調整剤としては、例えば、結晶セルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロースなどのセルロース系粘性調整剤などが挙げられる。 Examples of the cellulosic viscosity adjusting agent include cellulose-based viscosity adjusting agents such as crystalline cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.
　セルロース系粘性調整剤の市販品としては、例えば、旭化成社製のセオラス（登録商標）ＲＣシリーズなどのセオラス（登録商標）シリーズ；ダウケミカル社製のセロサイズ　ＱＰ　４４００、５２０００Ｈなどのセロサイズシリーズが挙げられる。一実施形態では、セルロース系粘性調整剤は、セロサイズ　ＱＰ　４４００およびセロサイズ　ＱＰ　５２０００Ｈからなる群より選択される１種以上である。 Examples of commercially available cellulosic viscosity modifiers include the Theoras (registered trademark) series such as Asahi Kasei's Theoras (registered trademark) RC series; and the cellosize series such as Dow Chemical's cellosize QP 4400 and 52000H. Be done. In one embodiment, the cellulosic viscosity modifier is one or more selected from the group consisting of cellosize QP 4400 and cellosize QP 52000H.
　アマイド系粘性調整剤としては、例えば、脂肪酸アマイド、ポリアマイド、アクリルアマイド、長鎖ポリアミノアマイド、アミノアマイドおよびこれらの塩（例えばリン酸塩）などが挙げられる。 Examples of the amide-based viscosity modifier include fatty acid amide, polyamide, acrylic amide, long-chain polyaminoamide, aminoamide and salts thereof (for example, phosphate).
　無機層状化合物系粘性調整剤として、例えば、モンモリロナイト、ベントナイト、クレーなどの層状化合物が挙げられる。 Examples of the inorganic layered compound-based viscosity modifier include layered compounds such as montmorillonite, bentonite, and clay.
　アミノプラスト系粘性調整剤としては、例えば、疎水変性エトキシレートアミノプラスト系会合型粘性調整剤などが挙げられる。 Examples of the aminoplast-based viscosity modifier include hydrophobically modified ethoxylate aminoplast-based viscosity modifiers.
　粘性調整剤は、１種単独でまたは２種以上を組み合わせて用いてもよい。 The viscosity modifier may be used alone or in combination of two or more.
　本発明に係る塗料組成物の一実施形態では、粘性調整剤が、アルカリ膨潤型粘性調整剤、ウレタン会合型粘性調整剤およびセルロース系粘性調整剤からなる群より選択される１種以上である。 In one embodiment of the coating composition according to the present invention, the viscosity adjusting agent is one or more selected from the group consisting of an alkaline swelling type viscosity adjusting agent, a urethane association type viscosity adjusting agent, and a cellulosic viscosity adjusting agent.
　本発明に係る塗料組成物の一実施形態では、ローラー塗装用、ロール塗装用、刷毛塗装用またはヘラ塗装用の塗料組成物は、樹脂成分と粘性調整剤とを含み、
　前記粘性調整剤が、アルカリ膨潤型粘性調整剤、ウレタン会合型粘性調整剤およびセルロース系粘性調整剤からなる群より選択される１種以上である。 In one embodiment of the coating composition according to the present invention, the coating composition for roller coating, roll coating, brush coating or spatula coating contains a resin component and a viscosity modifier.
The viscosity adjuster is one or more selected from the group consisting of an alkaline swelling type viscosity adjuster, a urethane association type viscosity adjuster, and a cellulosic viscosity adjuster.
　本発明の塗料組成物における粘性調整剤の含有量は、特に限定されず、適宜調節すればよい。 The content of the viscosity adjusting agent in the coating composition of the present invention is not particularly limited and may be appropriately adjusted.
　本発明の塗料組成物における粘性調整剤の固形分量は、例えば、塗料組成物１００質量部に対して、０．１～３．０質量部または０．５～２．０質量部である。本発明の塗料組成物の一実施形態では、粘性調整剤の固形分量は、塗料組成物１００質量部に対して、０．１質量部以上、０．３質量部以上、０．５質量部以上、０．６質量部以上、０．７質量部以上、０．８質量部以上、０．９質量部以上、１．０質量部以上、１．２質量部以上、１．４質量部以上、１．６質量部以上、１．８質量部以上、２．０質量部以上、２．２質量部以上、２．４質量部以上、２．６質量部以上、２．８質量部以上または３．０質量部以上である。本発明の塗料組成物の別の実施形態では、粘性調整剤の固形分量は、塗料組成物１００質量部に対して、３．０質量部以下、２．８質量部以下、２．６質量部以下、２．４質量部以下、２．２質量部以下、２．０質量部以下、１．８質量部以下、１．６質量部以下、１．４質量部以下、１．２質量部以下、１．０質量部以下、０．９質量部以下、０．８質量部以下、０．７質量部以下、０．６質量部以下、０．５質量部以下または０．３質量部以下である。なお、本発明では、「塗料組成物１００質量部」は、樹脂成分、顔料成分、粘性調整剤などにおける固形分に加えて、これらの分散媒；水および／または溶剤を含む塗料組成物全体の１００質量部を意味する。 The solid content of the viscosity modifier in the coating composition of the present invention is, for example, 0.1 to 3.0 parts by mass or 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the coating composition. In one embodiment of the coating composition of the present invention, the solid content of the viscosity modifier is 0.1 part by mass or more, 0.3 part by mass or more, and 0.5 part by mass or more with respect to 100 parts by mass of the coating composition. , 0.6 parts by mass or more, 0.7 parts by mass or more, 0.8 parts by mass or more, 0.9 parts by mass or more, 1.0 part by mass or more, 1.2 parts by mass or more, 1.4 parts by mass or more, 1.6 parts by mass or more, 1.8 parts by mass or more, 2.0 parts by mass or more, 2.2 parts by mass or more, 2.4 parts by mass or more, 2.6 parts by mass or more, 2.8 parts by mass or more or 3 It is more than 0.0 parts by mass. In another embodiment of the coating composition of the present invention, the solid content of the viscosity modifier is 3.0 parts by mass or less, 2.8 parts by mass or less, and 2.6 parts by mass with respect to 100 parts by mass of the coating composition. Below, 2.4 parts by mass or less, 2.2 parts by mass or less, 2.0 parts by mass or less, 1.8 parts by mass or less, 1.6 parts by mass or less, 1.4 parts by mass or less, 1.2 parts by mass or less. , 1.0 part by mass or less, 0.9 part by mass or less, 0.8 part by mass or less, 0.7 part by mass or less, 0.6 part by mass or less, 0.5 part by mass or less or 0.3 part by mass or less be. In the present invention, "100 parts by mass of the coating composition" is the whole coating composition containing water and / or a solvent in addition to the solid content in the resin component, the pigment component, the viscosity modifier and the like. It means 100 parts by mass.
　・架橋剤
　塗料組成物は架橋剤を含むことができる。架橋剤は、上記樹脂成分の有する硬化性官能基に応じて選択することができる。例えば、架橋剤としては、カルボジイミド化合物、ヒドラジン化合物、アミノ樹脂、（ブロック）ポリイソシアネート化合物、アミン系化合物、ポリアミド系化合物および多価カルボン酸化合物などが挙げられる。架橋剤は、１種単独でまたは２種以上を組み合わせて用いてもよい。 -Crosslinking agent The coating composition may contain a crosslinking agent. The cross-linking agent can be selected according to the curable functional group of the resin component. For example, examples of the cross-linking agent include carbodiimide compounds, hydrazine compounds, amino resins, (blocking) polyisocyanate compounds, amine compounds, polyamide compounds and polyvalent carboxylic acid compounds. The cross-linking agent may be used alone or in combination of two or more.
　・顔料
　顔料は、特に限定されず、公知の塗料用顔料を用いることができる。顔料としては、例えば、二酸化チタン、カーボンブラック、弁柄、フタロシアニンブルーなどの着色顔料；炭酸カルシウム、タルク、マイカなどの体質顔料；防錆顔料などが挙げられる。顔料は、１種単独でまたは２種以上を組み合わせて用いてもよい。 -Pigments The pigments are not particularly limited, and known paint pigments can be used. Examples of the pigment include colored pigments such as titanium dioxide, carbon black, petals, and phthalocyanine blue; extender pigments such as calcium carbonate, talc, and mica; and rust preventive pigments. The pigment may be used alone or in combination of two or more.
　本発明の塗料組成物は、水性塗料組成物または溶剤系塗料組成物のいずれでもよい。一実施形態では、本発明の塗料組成物は、水性塗料組成物である。別の実施形態として、ＪＩＳ　Ａ　６９０９の規定を満たす塗料組成物である。 The coating composition of the present invention may be either a water-based coating composition or a solvent-based coating composition. In one embodiment, the coating composition of the present invention is a water-based coating composition. As another embodiment, it is a coating composition satisfying the provisions of JIS A 6909.
　本発明では、塗料組成物中の含有量が最も多い分散媒が、水であるものを水性塗料組成物という。本発明では、塗料組成物中の含有量が最も多い分散媒が、溶剤であるものを溶剤系塗料組成物という。 In the present invention, the dispersion medium having the highest content in the coating composition is water, which is referred to as an aqueous coating composition. In the present invention, a solvent-based coating composition is one in which the dispersion medium having the highest content in the coating composition is a solvent.
　本発明の塗料組成物における塗料固形分の合計量としては、適宜調節すればよく、特に限定されない。例えば、塗料固形分の合計量は、塗料組成物１００質量部に対して、２０～８０質量部である。本発明の塗料組成物の一実施形態では、塗料固形分の合計量は、塗料組成物１００質量部に対して、２０質量部以上、３０質量部以上、４０質量部以上、５０質量部以上、６０質量部以上、７０質量部以上または８０質量部以上である。本発明の塗料組成物の別の実施形態では、塗料固形分の合計量は、塗料組成物１００質量部に対して、８０質量部以下、７０質量部以下、６０質量部以下、５０質量部以下、４０質量部以下、３０質量部以下または２０質量部以下である。 The total amount of paint solids in the paint composition of the present invention may be appropriately adjusted and is not particularly limited. For example, the total amount of the paint solid content is 20 to 80 parts by mass with respect to 100 parts by mass of the paint composition. In one embodiment of the coating composition of the present invention, the total amount of the coating solid content is 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, and 50 parts by mass or more with respect to 100 parts by mass of the coating composition. 60 parts by mass or more, 70 parts by mass or more, or 80 parts by mass or more. In another embodiment of the coating composition of the present invention, the total amount of the coating solid content is 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, and 50 parts by mass or less with respect to 100 parts by mass of the coating composition. , 40 parts by mass or less, 30 parts by mass or less, or 20 parts by mass or less.
　・水
　水を用いる場合、従来公知の水を適宜選択して用いることができる。水としては、例えば、水道水、蒸留水、脱イオン水、精製水などが挙げられる。 -Water When water is used, conventionally known water can be appropriately selected and used. Examples of water include tap water, distilled water, deionized water, purified water and the like.
　水を用いる場合、塗料組成物の水の含有量は、適宜調節すればよい。塗料組成物の水の含有量は、例えば、塗料組成物１００質量部に対して、２０～８０質量部である。本発明の塗料組成物の一実施形態では、塗料組成物１００質量部に対して、２０質量部以上、３０質量部以上、４０質量部以上、５０質量部以上、６０質量部以上、７０質量部以上または８０質量部以上である。本発明の塗料組成物の一実施形態では、塗料組成物１００質量部に対して、８０質量部以下、７０質量部以下、６０質量部以下、５０質量部以下、４０質量部以下、３０質量部以下または２０質量部以下である。 When water is used, the water content of the paint composition may be adjusted as appropriate. The water content of the coating composition is, for example, 20 to 80 parts by mass with respect to 100 parts by mass of the coating composition. In one embodiment of the coating composition of the present invention, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, 60 parts by mass or more, 70 parts by mass with respect to 100 parts by mass of the coating composition. Or more or 80 parts by mass or more. In one embodiment of the coating composition of the present invention, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, and 30 parts by mass with respect to 100 parts by mass of the coating composition. It is less than or equal to 20 parts by mass or less.
　・溶剤
　溶剤を用いる場合、従来公知の塗料組成物の溶剤を適宜選択して用いることができる。溶剤としては、例えば、メタノール、エタノール、２－プロパノール、１－ブタノールなどのアルコール類；酢酸エチル、酢酸ブチル、酢酸イソブチル、プロピオン酸エチル、エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテートなどのエステル類；ジエチルエーテル、プロピレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジオキサン、テトラヒドロフラン（ＴＨＦ）などのエーテル類；エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、１、３－ブチレングリコール、ペンタメチレングリコール、１、３－オクチレングリコールなどのグリコール類；ホルムアミド、Ｎ－メチルホルムアミド、ジメチルホルムアミド（ＤＭＦ）、ジメチルアセトアミド、ジメチルスルフォキシド（ＤＭＳＯ）、Ｎ－メチルピロリドン（ＮＭＰ）などのアミド類；アセトン、メチルエチルケトン（ＭＥＫ）、メチルプロピルケトン、メチルイソブチルケトン、アセチルアセトン、シクロヘキサノンなどのケトン類；ミネラルスピリット、灯油などの脂肪族炭化水素；トルエン、キシレン、メシチレン、ドデシルベンゼンなどの芳香族炭化水素；クロロホルム、ジクロロメチレンなどのハロゲン系溶媒などが挙げられる。溶剤は、１種単独でまたは２種以上を組み合わせて用いてもよい。 -Solvent When a solvent is used, a solvent of a conventionally known coating composition can be appropriately selected and used. Examples of the solvent include alcohols such as methanol, ethanol, 2-propanol and 1-butanol; ethyl acetate, butyl acetate, isobutyl acetate, ethyl propionate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol mono. Ethers such as ethyl ether acetate; ethers such as diethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dioxane, tetrahydrofuran (THF); ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, Glycols such as 1,3-butylene glycol, pentamethylene glycol, 1,3-octylene glycol; formamide, N-methylformamide, dimethylformamide (DMF), dimethylacetamide, dimethylsulfoxide (DMSO), N-methyl Amidos such as pyrrolidone (NMP); ketones such as acetone, methyl ethyl ketone (MEK), methyl propyl ketone, methyl isobutyl ketone, acetyl acetone, cyclohexanone; aliphatic hydrocarbons such as mineral spirit, kerosene; toluene, xylene, mesitylene, dodecyl Aromatic hydrocarbons such as benzene; halogen-based solvents such as chloroform and dichloromethylene can be mentioned. The solvent may be used alone or in combination of two or more.
　本発明の塗料組成物は、常温乾燥型でもよいし、加熱乾燥型でもよい。一実施形態では、本発明の塗料組成物は、常温乾燥型である。 The coating composition of the present invention may be a room temperature drying type or a heat drying type. In one embodiment, the coating composition of the present invention is a room temperature dry type.
　本発明の塗料組成物は、１液型でもよいし、２液型でもよい。 The coating composition of the present invention may be a one-component type or a two-component type.
　塗料組成物が、水性塗料組成物である場合、溶剤の含有量は、適宜調節すればよい。例えば、塗料組成物１００質量部に対して、０～１５質量部、好ましくは０～１０質量部である。また、この場合の溶剤としては、例えば、アルコール類を用いることができる。 When the coating composition is a water-based coating composition, the content of the solvent may be appropriately adjusted. For example, it is 0 to 15 parts by mass, preferably 0 to 10 parts by mass with respect to 100 parts by mass of the coating composition. Further, as the solvent in this case, for example, alcohols can be used.
　・その他の成分
　本発明の塗料組成物は、上述した成分以外に、分散剤、造膜助剤、凍結防止剤、架橋促進剤、硬化剤、レベリング剤、表面調整剤、消泡剤、可塑剤、防腐剤、防カビ剤、紫外線安定剤などのその他の成分を含んでいてもよい。これらその他の成分はそれぞれ、１種単独でまたは２種以上を組み合わせて用いてもよい。 -Other components In addition to the above-mentioned components, the coating composition of the present invention contains a dispersant, a film-forming auxiliary, an antifreeze agent, a cross-linking accelerator, a curing agent, a leveling agent, a surface conditioner, an antifoaming agent, and a plasticizer. , Preservatives, fungicides, UV stabilizers and other other ingredients may be included. These other components may be used alone or in combination of two or more.
　本発明に係る塗料組成物は、ローラー塗装用、ロール塗装用、刷毛塗装用またはヘラ塗装用の塗料組成物である。ローラー塗装は、特に限定されず、手持ちローラーを用いた塗装など公知のローラー塗装であってもよい。ロール塗装は、特に限定されず、ロールコーティングなど公知のロール塗装であってもよい。ロール塗装のロールの本数は、限定されず、１本、２本、３本または４本でもよい。刷毛塗装は、特に限定されず、ずんどうばけ、丸はけ、平はけ、すじかいばけ、ブラシなどを用いた、公知の刷毛塗装であってもよい。本発明では、刷毛は、ブラシを含むものとする。ヘラ塗装は、特に限定されず、鋼べら、木べら、プラスチックへら、ナイフなど公知のヘラ塗装であってもよい。 The coating composition according to the present invention is a coating composition for roller coating, roll coating, brush coating, or spatula coating. The roller coating is not particularly limited, and may be a known roller coating such as coating using a hand-held roller. The roll coating is not particularly limited, and may be a known roll coating such as a roll coating. The number of rolls for roll coating is not limited, and may be 1, 2, 3, or 4. The brush coating is not particularly limited, and may be a known brush coating using a brush, a round brush, a flat brush, a bracing brush, a brush, or the like. In the present invention, the brush includes a brush. The spatula coating is not particularly limited, and may be a known spatula coating such as a steel spatula, a wooden spatula, a plastic spatula, or a knife.
・塗料組成物の調製方法
　塗料組成物の調製方法は、粘度η１、貯蔵弾性率および粘度の定常値η２が所定範囲内であれば、特に限定されず、上述した樹脂成分、顔料、粘性調整剤などを従来公知の方法で混合して調製することができる。また、樹脂成分と顔料を含む市販の塗料に粘性調整剤などを添加して粘度η１、貯蔵弾性率および粘度の定常値η２を所定範囲内に調節して、本発明の塗料組成物としてもよい。 -Method for preparing the coating composition The method for preparing the coating composition is not particularly limited as long as the viscosity η1, the storage elastic modulus and the constant value η2 of the viscosity are within the predetermined ranges, and the above-mentioned resin component, pigment and viscosity adjusting agent are not particularly limited. Etc. can be mixed and prepared by a conventionally known method. Further, the coating composition of the present invention may be obtained by adding a viscosity adjusting agent or the like to a commercially available paint containing a resin component and a pigment to adjust the viscosity η1, the storage elastic modulus and the constant value η2 of the viscosity within predetermined ranges. ..
・塗膜の作製方法
　塗膜の作製方法は、従来公知のローラー塗装、ロール塗装、刷毛塗装またはヘラ塗装法を用いることができる。塗料組成物を塗布した後の乾燥温度は、溶剤などに応じて適宜調節すればよい。例えば、１０秒～３０分などの短時間での乾燥が必要な場合には、６０～２００℃とすることができ、８０～１６０℃が好ましい。また、短時間での乾燥が必要でない場合には、例えば、室温などで乾燥してもよい。 -Method for producing a coating film As a method for producing a coating film, a conventionally known roller coating, roll coating, brush coating or spatula coating method can be used. The drying temperature after applying the coating composition may be appropriately adjusted depending on the solvent and the like. For example, when drying in a short time such as 10 seconds to 30 minutes is required, the temperature can be 60 to 200 ° C, preferably 80 to 160 ° C. If it is not necessary to dry in a short time, it may be dried at room temperature, for example.
　本発明の塗料組成物を用いて塗膜を形成する対象物としては、特に限定されず、適宜選択することができる。例えば、対象物としては、自動車、鉄道車両などの車両の車体、航空機の機体、船舶の船体および上部構造物（艤装）、の内装および外装；建築物の内装、外装および屋根部；家具、建具；車両、航空機、船舶、建築物などの窓ガラス；ケース、容器、樹脂板、フィルム；ディスプレイ、モニター、冷蔵庫などの電化製品の筺体およびガラス部材；これらに塗装した塗膜；各種セメント、窯業建材、軽量発泡コンクリート、モルタル、スレート板、屋根、瓦、ＡＬＣなどの無機建材；木材；各種ガラス類；鋼板、アルミニウム、ステンレススチールなどの金属基材；などが挙げられる。 The object for forming a coating film using the coating composition of the present invention is not particularly limited and can be appropriately selected. For example, the objects include the body of a vehicle such as an automobile or a railroad vehicle, the body of an aircraft, the body and superstructure (furnishing) of a ship, the interior and exterior; the interior, exterior and roof of a building; furniture, fittings. Window glass for vehicles, aircraft, ships, buildings, etc .; Cases, containers, resin plates, films; Housings and glass members for electrical appliances such as displays, monitors, refrigerators; Coatings applied to these; Various cements, ceramic building materials , Lightweight foam concrete, mortar, slate board, roof, tile, inorganic building materials such as ALC; wood; various glasses; metal base materials such as steel plate, aluminum, stainless steel; and the like.
　したがって、本発明の塗料組成物を用いて形成された塗膜を有する物品としては、例えば、自動車、鉄道車両などの車両、航空機、船舶、建築物、家具、建具、窓ガラス、透明体（ケース、容器、樹脂板およびフィルムを含む）、電化製品などが挙げられる。 Therefore, examples of the article having a coating film formed by using the coating composition of the present invention include vehicles such as automobiles and railroad vehicles, aircraft, ships, buildings, furniture, fittings, windowpanes, and transparent bodies (cases). , Including containers, resin plates and films), electrical appliances and the like.
　以下、実施例を挙げて本発明をさらに詳しく説明するが、これらの実施例は、本発明の例示を目的とするものであり、本発明を何ら限定するものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for the purpose of exemplifying the present invention and do not limit the present invention in any way.
　塗料組成物の粘度η１は、アントンパール社製の応力制御型レオメーター「ＭＣＲ３０２」を用いて、５０ｍｍのコーンプレート、ギャップ：０．１ｍｍ、測定温度：２３℃、せん断速度１０００ｓ-1のせん断変形を３０秒間かけ、その直後、せん断速度＝０．０１-1のせん断変形を５秒間かける定常流測定を行ったときの粘度を用いた。 The viscosity η1 of the coating composition is a 50 mm cone plate, a gap of 0.1 mm, a measurement temperature of 23 ° C., and a shear deformation of a shear rate of 1000 s -1 using a stress-controlled rheometer "MCR302" manufactured by Anton Pearl. Was applied for 30 seconds, and immediately after that, the viscosity obtained by performing a steady flow measurement in which a shear deformation with a shear rate of 0.01 -1 was applied for 5 seconds was used.
　塗料組成物の貯蔵弾性率は、アントンパール社製の応力制御型レオメーター「ＭＣＲ３０２」を用いて、５０ｍｍのコーンプレート、ギャップ：０．１ｍｍ、測定温度：２３℃、ひずみ：線形ひずみ、角周波数：１００ｓ-1の条件で測定して得られた貯蔵弾性率を用いた。 For the storage elastic modulus of the coating composition, a stress-controlled rheometer "MCR302" manufactured by Anton Pearl Co., Ltd. was used, a cone plate of 50 mm, a gap of 0.1 mm, a measurement temperature of 23 ° C., a strain: linear strain, and an angular frequency. : The storage elastic modulus obtained by measuring under the condition of 100s -1 was used.
　塗料組成物の定常値η２は、アントンパール社製の応力制御型レオメーター「ＭＣＲ３０２」を用いて、５０ｍｍのコーンプレート、ギャップ：０．１ｍｍ、測定温度：２３℃、せん断速度０．０１-1でのせん断変形の定常流測定での粘度の定常値を用いた。 The steady value η2 of the coating composition was set to a 50 mm cone plate, a gap of 0.1 mm, a measurement temperature of 23 ° C., and a shear rate of 0.01 -1 using a stress-controlled rheometer “MCR302” manufactured by Anton Pearl. The steady value of the viscosity in the steady flow measurement of the shear deformation in was used.
　実施例で用いた塗料組成物の各成分の詳細は以下のとおりである。
水：水道水
樹脂成分：後述する調製例で調製したアクリルエマルション
白色顔料：二酸化チタン（固形分量：１００％）
体質顔料：炭酸カルシウム（固形分量：１００％）
添加剤：分散剤（ビックケミージャパン社製の商品名「ＤＩＳＰＥＲＢＹＫ－１９０」）、消泡剤（共栄社化学社製の商品名「アクアレン８０２０」）、造膜助剤（ＪＮＣ社製の商品名「ＣＳ－１２」）および表面調整剤（共栄社化学社製の商品名「ポリフローＫＬ－１００」）。表１では、分散剤、消泡剤、造膜助剤および表面調整剤をまとめて添加剤と表記する。添加剤の固形分量は、５０％である。
粘性調整剤１（ウレタン会合型粘性調整剤）：ＡＤＥＫＡ社製の商品名「アデカノール（登録商標）ＵＨ－１４０Ｓ」（固形分量：３０％、表１ではＵＨ１４０Ｓと表記）
粘性調整剤２（ウレタン会合型粘性調整剤）：ＡＤＥＫＡ社製の商品名「アデカノール（登録商標）ＵＨ－７５２」（固形分量：３０％、表１ではＵＨ７５２と表記）
粘性調整剤３（ウレタン会合型粘性調整剤）：ＡＤＥＫＡ社製の商品名「アデカノール（登録商標）ＵＨ－４２０」（固形分量：３０％、表１ではＵＨ４２０と表記）
粘性調整剤４（ウレタン会合型粘性調整剤）：ＡＤＥＫＡ社製の商品名「アデカノール（登録商標）ＵＨ－４７２」（固形分量：３０％、表１ではＵＨ４７２と表記）
粘性調整剤５（ウレタン会合型粘性調整剤）：サンノプコ社製の商品名「ＳＮ　シックナー　６１２」（固形分量：４０％、表１ではＳＮ６１２と表記）
粘性調整剤６（アルカリ膨潤型粘性調整剤）：サンノプコ社製の商品名「ＳＮ　シックナー　６３０」（固形分量：３０％、表１ではＳＮ６３０と表記）
粘性調整剤７（アルカリ膨潤型粘性調整剤）：中部サイデン社製の商品名「バンスター　Ｓ１００Ａ」（固形分量：２８％、表１ではＳ１００Ａと表記）
粘性調整剤８（アルカリ膨潤型粘性調整剤）：サンノプコ社製の商品名「ＳＮ　シックナー　６３６」（固形分量：３０％、表１ではＳＮ６３６と表記）
粘性調整剤９（アルカリ膨潤型粘性調整剤）：ダウケミカル社製の商品名「プライマル　ＡＳＥ－６０　シックナー」（固形分量：２８％、表１ではＡＳＥ６０と表記）
粘性調整剤１０（セルロース系粘性調整剤）：ダウケミカル社製の商品名「セロサイズ　ＱＰ　４４００」（固形分量：１００％、表１ではＱＰ　４４００と表記）
粘性調整剤１１（セルロース系粘性調整剤）：ダウケミカル社製の商品名「セロサイズ　ＱＰ　５２０００Ｈ」（固形分量：１００％、表１ではＱＰ　５２０００Ｈと表記） The details of each component of the coating composition used in the examples are as follows.
Water: Tap water Resin component: Acrylic emulsion prepared in the preparation example described later White pigment: Titanium dioxide (solid content: 100%)
Constituent pigment: Calcium carbonate (solid content: 100%)
Additives: Dispersant (trade name "DISPERBYK-190" manufactured by Big Chemie Japan), defoamer (trade name "Aqualen 8020" manufactured by Kyoeisha Chemical Co., Ltd.), film-forming aid (trade name "JNC" CS-12 ") and surface conditioner (trade name" Polyflow KL-100 "manufactured by Kyoeisha Chemical Co., Ltd.). In Table 1, dispersants, defoamers, film-forming aids and surface conditioners are collectively referred to as additives. The solid content of the additive is 50%.
Viscosity Adjuster 1 (Urethane Association Type Viscosity Adjuster): Product name "ADEKA NOL (registered trademark) UH-140S" manufactured by ADEKA (solid content: 30%, indicated as UH140S in Table 1).
Viscosity Adjuster 2 (Urethane Association Type Viscosity Adjuster): Product name "ADEKA NOL (registered trademark) UH-752" manufactured by ADEKA (solid content: 30%, indicated as UH752 in Table 1).
Viscosity Adjuster 3 (Urethane Association Type Viscosity Adjuster): Product name "ADEKA NOL (registered trademark) UH-420" manufactured by ADEKA (solid content: 30%, indicated as UH420 in Table 1).
Viscosity Adjuster 4 (Urethane Association Type Viscosity Adjuster): Product name "ADEKA NOL (registered trademark) UH-472" manufactured by ADEKA (solid content: 30%, indicated as UH472 in Table 1).
Viscosity Adjuster 5 (Urethane Association Type Viscosity Adjuster): Product name "SN Thickener 612" manufactured by San Nopco Ltd. (solid content: 40%, indicated as SN612 in Table 1)
Viscosity adjuster 6 (Alkaline swelling type viscosity adjuster): Product name "SN Thickener 630" manufactured by San Nopco Ltd. (solid content: 30%, indicated as SN630 in Table 1)
Viscosity adjuster 7 (Alkaline swelling type viscosity adjuster): Product name "Banster S100A" manufactured by Chubu Saiden Co., Ltd. (solid content: 28%, indicated as S100A in Table 1)
Viscosity adjuster 8 (Alkaline swelling type viscosity adjuster): Product name "SN Thickener 636" manufactured by San Nopco Ltd. (solid content: 30%, indicated as SN636 in Table 1)
Viscosity adjuster 9 (Alkaline swelling type viscosity adjuster): Product name "Primal ASE-60 Thickener" manufactured by Dow Chemical Co., Ltd. (solid content: 28%, indicated as ASE60 in Table 1)
Viscosity Adjuster 10 (Cellulose Viscosity Adjuster): Product name "Cellosize QP 4400" manufactured by Dow Chemical Co., Ltd. (solid content: 100%, indicated as QP 4400 in Table 1)
Viscosity Adjuster 11 (Cellulose Viscosity Adjuster): Product name "Cellosize QP 52000H" manufactured by Dow Chemical Co., Ltd. (solid content: 100%, indicated as QP 52000H in Table 1)
　ローラーは、大塚刷毛製造社製の商品名「ウーローラーＢ　レギュラー　４Ｂ」を用いた。スレート板は、ＴＰ技研社製の商品名「スレート板」（長さ９０ｃｍ、幅４５ｃｍ）を用いた。下塗り塗料として、日本ペイント社製の商品名「ニッペ水性透明シーラー」を用いた。 For the roller, the product name "Wool Roller B Regular 4B" manufactured by Otsuka Brush Manufacturing Co., Ltd. was used. As the slate plate, a trade name "slate plate" (length 90 cm, width 45 cm) manufactured by TP Giken Co., Ltd. was used. As the undercoat paint, the product name "Nippe Aqueous Transparent Sealer" manufactured by Nippon Paint Co., Ltd. was used.
　（アクリルエマルションの調製例）
　撹拌機、還流冷却管、温度計および窒素導入管を備えた反応器に、脱イオン水６８．５質量部、およびポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム（花王社製の商品名「レベノールＷＺ」）１質量部を仕込んだ。次いで、その溶液を８０℃まで昇温して保持した。次いで、その溶液に、１０％濃度の過硫酸アンモニウム水溶液１質量部を添加した。次いで、その溶液に、スチレン６６．０質量部、２－エチルヘキシルアクリレート２８．５質量部、アクリル酸３．５質量部、２－ヒドロキシエチルメタクリレート２．０質量部、アセトアセトキシエチルメタクリレート８．５質量部、ｎ－ドデシルメルカプタン０．８５質量部、ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム（「レベノールＷＺ」）８質量部および脱イオン水４９．４質量部からなるモノマー混合物と、２％濃度の過硫酸アンモニウム水溶液１０質量部とを並行して３時間かけて滴下した。その反応容器内を８０℃に保持したまま５時間撹拌を続けた。次いで、その反応容器を室温まで冷却した。次いで、その反応容器内に、２５％アンモニア水２質量部およびジエチレングリコールモノブチルエーテルアセテート１７質量部を添加して撹拌した。生成物として、固形分４９質量％、体積平均粒子径０．１２μｍのエマルション樹脂を得た。表１ではＡｃＥｍと表記する。 (Preparation example of acrylic emulsion)
A reactor equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube, 68.5 parts by mass of deionized water, and sodium polyoxyethylene nonylphenyl ether sulfate (trade name "Revenol WZ" manufactured by Kao Corporation). 1 part by mass was charged. The solution was then heated to 80 ° C. and held. Then, 1 part by mass of a 10% concentrated ammonium persulfate aqueous solution was added to the solution. Then, 66.0 parts by mass of styrene, 28.5 parts by mass of 2-ethylhexyl acrylate, 3.5 parts by mass of acrylic acid, 2.0 parts by mass of 2-hydroxyethyl methacrylate and 8.5 parts by mass of acetoacetoxyethyl methacrylate were added to the solution. A monomer mixture consisting of 0.85 parts by mass of n-dodecyl mercaptan, 8 parts by mass of polyoxyethylene nonylphenyl ether sodium sulfate (“Revenol WZ”) and 49.4 parts by mass of deionized water, and 2% concentration ammonium persulfate. 10 parts by mass of the aqueous solution was added dropwise in parallel over 3 hours. Stirring was continued for 5 hours while keeping the inside of the reaction vessel at 80 ° C. The reaction vessel was then cooled to room temperature. Next, 2 parts by mass of 25% aqueous ammonia and 17 parts by mass of diethylene glycol monobutyl ether acetate were added to the reaction vessel and stirred. As a product, an emulsion resin having a solid content of 49% by mass and a volume average particle diameter of 0.12 μm was obtained. In Table 1, it is expressed as AcEm.
（実施例１～７および比較例１～３）
　表１に示す配合（質量部）で、各成分を混合して塗料組成物を調製した。その塗料組成物について、粘度η１、貯蔵弾性率および粘度の定常値η２を測定した。その結果を表１に合わせて示す。 (Examples 1 to 7 and Comparative Examples 1 to 3)
Each component was mixed in the formulation (part by mass) shown in Table 1 to prepare a coating composition. For the coating composition, the viscosity η1, the storage elastic modulus and the steady-state value η2 of the viscosity were measured. The results are shown in Table 1.
（塗装板の調製）
　地面に対してスレート板を垂直に立て、下塗り塗料をローラーでスレート板に塗装した。次いで、約３０μｍの乾燥膜厚となるように、各実施例および比較例の塗料組成物をローラーでスレート板に塗装した。そのスレート板を室温で２時間静置した。次いで、再度、約３０μｍの乾燥膜厚となるように、各実施例および比較例の塗料組成物をローラーでスレート板に塗装した。そのスレート板を室温で１日静置して、塗膜を有するスレート板を調製した。実施例５と比較例２の塗膜の外観をそれぞれ、図１，図２に示す。 (Preparation of painted plate)
The slate plate was erected perpendicular to the ground, and the undercoat paint was applied to the slate plate with a roller. Then, the coating compositions of each Example and Comparative Example were coated on the slate plate with a roller so as to have a dry film thickness of about 30 μm. The slate plate was allowed to stand at room temperature for 2 hours. Then, the coating compositions of each Example and Comparative Example were again coated on the slate plate with a roller so as to have a dry film thickness of about 30 μm. The slate plate was allowed to stand at room temperature for 1 day to prepare a slate plate having a coating film. The appearances of the coating films of Example 5 and Comparative Example 2 are shown in FIGS. 1 and 2, respectively.
（塗膜の外観の評価）
　得られた塗膜の外観について、以下に述べる方法で塗料筋の視認性と、塗料組成物のタレを評価した。 (Evaluation of the appearance of the coating film)
Regarding the appearance of the obtained coating film, the visibility of the paint streaks and the sagging of the paint composition were evaluated by the method described below.
・塗料筋の視認性
　以下に示す基準で、塗料筋の目視での視認性を５人で評価し、評価の中央値を求めた。その結果を表１に合わせて示す。評点３～５が合格である。
評点５：全塗装面積における占める長さ２ｃｍ以上の塗料筋の割合が、５％未満
評点４：塗料筋の割合が、５％以上～１０％未満
評点３：塗料筋の割合が、１０％以上～２０％未満
評点２：塗料筋の割合が、２０％以上～３０％未満
評点１：塗料筋の割合が、３０％以上 -Visibility of paint streaks The visual visibility of paint streaks was evaluated by 5 people based on the following criteria, and the median evaluation was calculated. The results are shown in Table 1. Scores 3 to 5 are acceptable.
Score 5: The proportion of paint streaks with a length of 2 cm or more in the total painted area is less than 5% Score 4: The proportion of paint streaks is 5% or more and less than 10% Score 3: The proportion of paint streaks is 10% or more ~ 20% or less Score 2: The ratio of paint streaks is 20% or more and less than 30% Score 1: The ratio of paint streaks is 30% or more
・塗料組成物のタレ
　以下に示す基準で、塗料組成物のタレを５人で評価し、過半数の評価結果を採用した。結果を表１に合わせて示す。
合格：塗料組成物がタレていない
不合格：塗料組成物がタレている -Paint composition sagging Based on the criteria shown below, the paint composition sagging was evaluated by five people, and the evaluation results of the majority were adopted. The results are shown in Table 1.
Pass: The paint composition is not sagging Fail: The paint composition is sagging
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、本発明によれば、塗料筋およびタレを抑制し、外観に優れた塗膜を形成可能な、塗料組成物を提供することができた。 As shown in Table 1, according to the present invention, it was possible to provide a coating composition capable of suppressing paint streaks and sagging and forming a coating film having an excellent appearance.
　本発明によれば、塗料筋およびタレを抑制し、外観に優れた塗膜を形成可能な、塗料組成物を提供することができる。 According to the present invention, it is possible to provide a coating composition capable of suppressing paint streaks and sagging and forming a coating film having an excellent appearance.
１：面
２：ローラー
３：液膜
４：空隙
５：塗料糸
６：塗膜
７：塗料筋 1: Surface 2: Roller 3: Liquid film 4: Void 5: Paint thread 6: Paint film 7: Paint streaks

Claims (5)

  1. 　ローラー塗装用、ロール塗装用、刷毛塗装用またはヘラ塗装用の塗料組成物であって、
    　前記塗料組成物に２３℃でせん断速度１０００ｓ-1のせん断変形を３０秒間かけた直後、せん断速度０．０１ｓ-1のせん断変形を５秒間かけたときの粘度η１が、４０Ｐａ・ｓ以下であり、
    　前記塗料組成物の２３℃での貯蔵弾性率が、５０Ｐａ以上であり、かつ、
    　前記塗料組成物の２３℃、せん断速度０．０１ｓ-1でのせん断変形の定常流測定での粘度の定常値η２が、５０Ｐａ・ｓ以上である、
    　ローラー塗装用、ロール塗装用、刷毛塗装用またはヘラ塗装用の塗料組成物。     A paint composition for roller coating, roll coating, brush coating, or spatula coating.
    Immediately after the coating composition is subjected to shear deformation at a shear rate of 1000 s -1 at 23 ° C. for 30 seconds, the viscosity η 1 when shear deformation at a shear rate of 0.01 s -1 is applied for 5 seconds is 40 Pa · s or less. ,
    The storage elastic modulus of the coating composition at 23 ° C. is 50 Pa or more, and
    The constant value η2 of the viscosity of the coating composition in the steady flow measurement of shear deformation at 23 ° C. and a shear rate of 0.01 s -1 is 50 Pa · s or more.
    A paint composition for roller coating, roll coating, brush coating or spatula coating.
  2. 　前記粘度の定常値η２が、５０～５００Ｐａ・ｓである、請求項１に記載のローラー塗装用、ロール塗装用、刷毛塗装用またはヘラ塗装用の塗料組成物。 The coating composition for roller coating, roll coating, brush coating or spatula coating according to claim 1, wherein the steady value η2 of the viscosity is 50 to 500 Pa · s.
  3. 　前記粘度η１が、３～４０Ｐａ・ｓである、請求項１または２に記載のローラー塗装用、ロール塗装用、刷毛塗装用またはヘラ塗装用の塗料組成物。 The coating composition for roller coating, roll coating, brush coating or spatula coating according to claim 1 or 2, wherein the viscosity η1 is 3 to 40 Pa · s.
  4. 　前記貯蔵弾性率が、５０～４００Ｐａである、請求項１～３のいずれか一項に記載のローラー塗装用、ロール塗装用、刷毛塗装用またはヘラ塗装用の塗料組成物。 The coating composition for roller coating, roll coating, brush coating or spatula coating according to any one of claims 1 to 3, wherein the storage elastic modulus is 50 to 400 Pa.
  5. 　樹脂成分と粘性調整剤とを含み、
    　前記粘性調整剤が、アルカリ膨潤型粘性調整剤、ウレタン会合型粘性調整剤およびセルロース系粘性調整剤からなる群より選択される１種以上である、請求項１～４のいずれか一項に記載のローラー塗装用、ロール塗装用、刷毛塗装用またはヘラ塗装用の塗料組成物。     Contains resin components and viscosity regulators,
    The invention according to any one of claims 1 to 4, wherein the viscosity adjusting agent is at least one selected from the group consisting of an alkali swelling type viscosity adjusting agent, a urethane association type viscosity adjusting agent, and a cellulose-based viscosity adjusting agent. A paint composition for roller coating, roll coating, brush coating or spatula coating.
PCT/JP2021/025372 2020-07-13 2021-07-05 Coating composition for application with roller, roll, brush, or spatula WO2022014394A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04370161A (en) * 1991-06-17 1992-12-22 Dainippon Ink & Chem Inc Emulsion paint for interior or exterior of building
JP2002047450A (en) * 2000-07-31 2002-02-12 Nippon Paint Co Ltd Water-based coating composition
JP2011225657A (en) * 2010-04-16 2011-11-10 Kansai Paint Co Ltd Emulsion resin-based coating

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04370161A (en) * 1991-06-17 1992-12-22 Dainippon Ink & Chem Inc Emulsion paint for interior or exterior of building
JP2002047450A (en) * 2000-07-31 2002-02-12 Nippon Paint Co Ltd Water-based coating composition
JP2011225657A (en) * 2010-04-16 2011-11-10 Kansai Paint Co Ltd Emulsion resin-based coating

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