WO2022049775A1

WO2022049775A1 - Coating material composition

Info

Publication number: WO2022049775A1
Application number: PCT/JP2020/033805
Authority: WO
Inventors: 聡石田; 晋也川上; 聡宏久保
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
Priority date: 2020-09-07
Filing date: 2020-09-07
Publication date: 2022-03-10

Abstract

Provided is a coating material composition that reduces or prevents scattering of a coating material not only in a horizontal direction but also in the vertical direction. This coating material composition exhibits a first normal line stress difference of 10 Pa or more and a loss tangent (Tanδ) of 1.00 or less, and coating material threads obtained therefrom have a constriction occurrence suppression (CON) value of 0.45 or less.

Description

Paint composition

The present invention relates to a coating composition.

The paint is required not only to have excellent paint film performance after painting, but also to have excellent painting workability. For example, even if the quality of the paint film after painting is excellent, if the painting workability of the paint is low, such as requiring a lot of man-hours for painting or being difficult to paint, the value of the paint will be greatly reduced. ..

One of the important items of painting workability is that there is little paint scattering (also called spatter). In painting using a roller or the like, the time required for curing to prevent the surrounding stains due to paint scattering may occupy about 1/3 of the entire painting process. Further, if the paint is scattered a lot, the work efficiency of the painter is lowered, and the painting process may be delayed. Therefore, suppressing or reducing the scattering of the paint leads to a significant shortening of the process and makes it possible to increase the value of the paint.

The present inventor discloses in Patent Document 1 a coating composition having excellent coating workability and a good coating feeling.

International Publication No. 2018/079212

However, although Patent Document 1 discloses that the scattering of the paint in the horizontal painting is suppressed as shown in FIGS. 1 and 6 of the Patent Document 1, the scattering of the paint in the vertical painting is suppressed. There is no disclosure about the method of reduction.

In the case of horizontal painting, even if the paint is scattered, the surroundings will not be soiled if the scattered paint adheres to the object surface to be painted, but in the case of vertical painting, the surroundings will be soiled if the paint is scattered and dropped. Therefore, vertical coating is required to control the scattering of paint to a higher degree than horizontal coating.

Therefore, an object of the present invention is to provide a coating composition that suppresses or reduces the scattering of the coating material not only in the horizontal direction but also in the vertical direction.

The coating composition according to the present invention is
The first normal stress difference is 10 Pa or more,
The loss tangent (Tanδ) is 1.00 or less, and the constriction generation suppression (CON) value of the paint yarn is 0.45 or less.
It is a paint composition. When the first normal stress difference, Tan δ and CON values are in the above ranges, it is possible to suppress or reduce the scattering of the paint not only in the horizontal direction but also in the vertical direction.

In one embodiment of the coating composition according to the present invention, the first normal stress difference is 10 to 200 Pa.

In one embodiment of the coating composition according to the present invention, the Tan δ is 0.5 to 1.0.

In one embodiment of the coating composition according to the present invention, the CON value is 0.20 to 0.45.

In one embodiment of the coating composition according to the present invention, a resin component and a viscosity adjusting agent are included.
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.

In one embodiment of the coating composition according to the present invention, the viscosity is 0.1 to 2.0 Pa · s.

The paint composition according to the present invention is for interior use in one embodiment.

According to the present invention, it is possible to provide a coating composition that suppresses or reduces scattering of a coating material not only in the horizontal direction but also in the vertical direction.

FIG. 1A is a schematic diagram of observation results of roller coating in the vertical direction using a high-speed camera. FIG. 1B is a schematic diagram of observation results of roller coating in the vertical direction using a high-speed camera. FIG. 1C is a schematic diagram of the observation result of roller coating in the vertical direction using a high-speed camera. FIG. 1D is a schematic diagram of the observation result of roller coating in the vertical direction using a high-speed camera. FIG. 1E is a schematic diagram of the observation result of roller coating in the vertical direction using a high-speed camera. FIG. 1F is a schematic diagram of observation results of roller coating in the vertical direction using a high-speed camera. FIG. 2 is a schematic diagram showing a method of measuring the amount of paint scattered in the examples.

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.

In the present invention, two or more embodiments can be arbitrarily combined.

In the present invention, the paint and the paint composition can be used interchangeably.

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, 10 to 200 Pa means 10 Pa or more and 200 Pa or less.

(Paint composition)
The coating composition according to the present invention is
The first normal stress difference is 10 Pa or more,
The loss tangent (Tanδ) is 1.00 or less, and the constriction generation suppression (CON) value of the paint yarn is 0.45 or less.
It is a paint composition.

The present inventors observed the state of roller painting using a high-speed camera in order to investigate the process of paint scattering during vertical painting by a roller or the like. 1A to 1F are schematic views of a series of observation results of roller coating in the vertical direction using a high-speed camera. 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 (FIG. 1A). As the roller 2 moves downward, the liquid film 3 grows (FIG. 1B). When the roller 2 is further moved, the liquid film 3 is cut off to form a thread-like paint thread 4 (FIG. 1C). Further, when the roller 2 moves, a plurality of thin portions (constrictions) 5 are formed in the paint thread 4 (FIG. 1D). When the roller 2 further moves, the paint thread 4 breaks at the constriction 5 (FIG. 1E). Then, the broken paint thread 4 is further broken to become fine droplets 6 and scatter (FIG. 1F).

From this observation result, the present inventors speculated that the following (1) to (3) would be effective in suppressing the scattering of the paint.
(1) Prevent the liquid films of FIGS. 1A and 1B and the paint thread of FIG. 1C from stretching.
(2) To suppress the occurrence of constriction in the paint thread of FIG. 1D.
(3) In FIG. 1E, the broken paint thread is immediately returned to the roller direction or the painted surface direction, in other words, the first normal stress difference of the paint is increased.

Regarding (1) above, the liquid film and the paint thread can be considered as a viscoelastic body having an elastic component and a viscous component, and it is considered that the paint thread stretches when the viscous component is larger than the elastic component. The loss tangent (Tanδ) is expressed as a loss elastic modulus (viscous component) / storage elastic modulus (elastic component). Therefore, in order to prevent the liquid film and the paint thread from stretching, the elastic component may be increased with respect to the viscous component, that is, Tan δ may be lowered.

In the present invention, the loss tangent (Tanδ) is a 50 mm parallel plate, gap: 0.5 mm, strain: linear strain, angular frequency: 100s ^-1 , using the stress control type leometer "MCR302" manufactured by Anton Pearl. Measurement temperature: Data of dynamic viscoelasticity measured under the condition of 23 ° C. is used.

Regarding (2) above, when the present inventors observed the constriction of the paint thread in FIG. 1D, the constriction did not occur in the central portion of the paint thread, that is, the intermediate portion between the liquid film and the roller, but the paint thread. It was found that the paint thread broke due to random constriction. From this, the present inventors have found that in the microstructure in the paint thread, a portion where the microstructure is broken and a portion where the microstructure is not broken are mixed, and the viscosity is lowered and the constriction is formed in the broken portion. Estimated to occur. Here, a non-Newtonian fluid such as a paint usually has a property that as the shear rate increases in a certain shear rate range, the microstructure is broken and the viscosity decreases, such as less entanglement of molecular chains. Therefore, in order to suppress the occurrence of constriction in the paint yarn, the amount of change in viscosity when the shear rate changes may be reduced, that is, the dependence of the viscosity of the paint on the shear rate may be reduced. In the present invention, the value of the viscosity depending on the shear rate is set to the CON value from the control of the Occurrence of a Neck.

In the present invention, the method for measuring the CON value is as follows. Shear velocity (dγ / dt) = 10s ^-1 , ^100s- under the conditions of 50mm parallel plate, gap: 0.5mm, measurement temperature: 23 ° C. using stress control type leometer "MCR302" manufactured by Anton Pearl Co., Ltd. Steady flow measurement is performed at ¹ and 1000s ^-1 , and the viscosities 30 seconds after the start of measurement are η (10), η (100), and η (1000), respectively. Generally, the shear rate corresponding to the rate at which the paint thread is stretched during painting with a roller or the like is about 100s ^-1 , so the shear rates of 10s ^-1 and 1000s ^-1 before and after that are used. Then, from the three sets of data, a graph with log ₁₀ (dγ / dt) on the horizontal axis and log ₁₀ (η) on the vertical axis is created, and a linear approximation formula is calculated from the three points by the least squares method. Let the absolute value of the slope of the straight line be the CON value.

With respect to the above (3), the normal stress is the stress generated in the direction orthogonal to the direction in which the shear is applied when the measurement object made of the viscoelastic fluid is subjected to rotational deformation. The normal stress is not grasped by itself, but is grasped by the difference from the shear stress. The first normal stress difference N ₁ is the first normal stress difference N ₁ = σ _xx − using the component of the stress tensor σ in a steady shear flow state where the flow velocity direction is x and the velocity gradient direction is y. Defined as σ _yy .

In the present invention, the first normal stress difference is a 50 mm parallel plate, a gap: 0.5 mm, a shear rate: 100s ^-1 , and a measurement temperature: 23, using a stress control type reometer "MCR302" manufactured by Anton Pearl. Steady flow measurement is performed under the condition of ° C, and it is obtained from the measurement data 30 seconds after the start of measurement.

The present inventors have determined that the first normal stress difference obtained from these is 10 Pa or more, Tan δ is 1.00 or less, and the CON value is 0.45 or less, so that only in the horizontal direction. Instead, it was found that the scattering of the paint can be suppressed or reduced even in the vertical direction.

When the first normal stress difference is less than 10 Pa, the force of the paint thread generated during painting with a roller or the like to return to the painting surface direction or the direction of the painting tool such as a roller is weak, so that paint scattering is sufficiently suppressed in vertical painting. Or cannot be reduced.

In one embodiment, the first normal stress difference is 10 Pa or more, 20 Pa or more, 30 Pa or more, 40 Pa or more, 50 Pa or more, 60 Pa or more, 70 Pa or more, 80 Pa or more, 90 Pa or more, 100 Pa or more, 110 Pa or more, 120 Pa or more, 130 Pa. These are 140 Pa or more, 150 Pa or more, 160 Pa or more, 170 Pa or more, 180 Pa or more, 190 Pa or more, or 200 Pa or more. In one embodiment, the first normal stress difference is 1000 Pa or less, 900 Pa or less, 800 Pa or less, 700 Pa or less, 600 Pa or less, 500 Pa or less, 400 Pa or less, 300 Pa or less, 200 Pa or less, 190 Pa or less, 180 Pa or less, 170 Pa or less, 160 Pa. Below, 150 Pa or less, 140 Pa or less, 130 Pa or less, 120 Pa or less, 110 Pa or less, 100 Pa or less, 90 Pa or less, 80 Pa or less, 70 Pa or less, 60 Pa or less, 50 Pa or less, 40 Pa or less, 30 Pa or less or 20 Pa or less. The first normal stress difference is 10 to 200 Pa in another embodiment. The first normal stress difference is 10 to 190 Pa in yet another embodiment.

When Tan δ is larger than 1.00, the elongation of the liquid film and the paint thread becomes large, and the paint scattering cannot be sufficiently suppressed or reduced in the vertical painting.

In one embodiment, Tan δ is 1.00 or less, 0.95 or less, 0.90 or less, 0.85 or less, 0.80 or less, 0.75 or less, 0.70 or less, 0.65 or less, 0. 60 or less, 0.55 or less, 0.50 or less, 0.45 or less, 0.40 or less, 0.35 or less, 0.30 or less, 0.25 or less, 0.20 or less, 0.15 or less or 0. It is 10 or less. In one embodiment, Tanδ has 0.05 or more, 0.10 or more, 0.15 or more, 0.20 or more, 0.25 or more, 0.30 or more, 0.35 or more, 0.40 or more, 0. 45 or more, 0.50 or more, 0.55 or more, 0.60 or more, 0.65 or more, 0.70 or more, 0.75 or more, 0.80 or more, 0.85 or more, 0.90 or more or 0. It is 95 or more. Tan δ is 0.50 to 1.00 in another embodiment. Tan δ is 0.70 to 1.00 in still another embodiment.

If the CON value is larger than 0.45, the paint thread is likely to be constricted, leading to breakage of the paint thread, and it is not possible to sufficiently suppress or reduce paint scattering in vertical painting.

In one embodiment, the CON value is 0.45 or less, 0.40 or less, 0.35 or less, 0.30 or less, 0.25 or less, 0.20 or less, 0.15 or less, or 0.10 or less. .. In one embodiment, the CON value is 0.05 or more, 0.10 or more, 0.15 or more, 0.20 or more, 0.25 or more, 0.30 or more, 0.35 or more, or 0.40 or more. .. The CON value is 0.30 to 0.45 in another embodiment. In yet another embodiment, the CON value is 0.30 to 0.40.

The viscosity of the coating composition is not particularly limited and may be adjusted as appropriate. As shown in Examples described later, there is no correlation between the viscosity and the amount of paint scattered. Therefore, the viscosity is not a key factor for controlling the amount of scattering of the paint, but from the viewpoint of maintaining or enhancing the coating feeling of the paint, the viscosity of the paint composition is, for example, 0.1 to 2.0 Pa. s is preferable, and 0.1 to 1.5 Pa · s is more preferable.

On the other hand, the topcoat film is required to have a uniform coating film in order to improve the appearance of the coating film as compared with the undercoat film, so that a coating film having a thin film thickness is often formed. With a relatively high viscosity paint, the amount of paint applied to the target surface tends to be large, and it is suitable for forming a coating film with a thick film thickness, but it forms a homogeneous coating film with a thin film thickness. That is difficult. On the other hand, a paint having a relatively low viscosity tends to reduce the amount of paint applied to the target surface, and is suitable for forming a homogeneous coating film having a thin film thickness. Therefore, from the viewpoint of forming a coating film having a thin film thickness, the viscosity of the coating composition is preferably 0.1 to 2.0 Pa · s, more preferably 0.1 to 1.5 Pa · s, for example.

In one embodiment of the coating composition according to the present invention, the viscosity is 0.1 to 2.0 Pa · s. This makes it easy to form a coating film with a thin film thickness, and is suitable for forming topcoat coating films for interior and exterior coatings.

In the present invention, the viscosity (Pa · s) of the coating composition is a stress control type reometer “MCR302” manufactured by Anton Pearl Co., Ltd., 50 mm parallel plate, gap: 0.5 mm, shear rate: 1000s ^-1 , measurement temperature: A steady flow measurement is performed under the condition of 23 ° C., and the viscosity 30 seconds after the start of measurement is used.

The paint composition usually contains a resin component, a cross-linking agent, a pigment, and water and / or a solvent. The coating composition may contain other components.

<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.

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 above 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. 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.

<Crosslinking agent>
The coating composition can include a cross-linking 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.

<Pigment>
The pigment is 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.

<Viscosity adjuster>
In the present invention, known viscosity modifiers may be used to adjust the first normal stress difference, Tan δ and CON values of the coating composition. 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.

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.

Commercially available products of the alkaline swelling type viscosity modifier include, for example, SN thickener series such as SN thickener 615, 630, 636, 640 manufactured by San Nopco; and primal (registered trademark) ASE-60 manufactured by Dow Chemical Co., Ltd. Registered trademark) series and the like.

Examples of the urethane-associating type viscosity adjusting agent include urethane-modified polyether type viscosity adjusting agents.

Commercially available urethane-associated viscosity modifiers include, for example, ADEKA's Adecanol (registered trademark) UH-140S, 420, 450, 526, 540, 550 and other Adecanol (registered trademark) UH series; manufactured by San Nopco Ltd. SN Thickener 665T and the like can be mentioned.

Examples of the cellulosic viscosity adjusting agent include cellulose-based viscosity adjusting agents such as crystalline cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

Commercially available products of cellulosic viscosity modifiers include, for example, Theoras (registered trademark) series such as Asahi Kasei's Theoras (registered trademark) RC series; Dow Chemical's cellosize QP 4400, 52000H and other cellosize (registered trademark). The series can be mentioned.

Examples of the amide-based viscosity modifier include fatty acid amide, polyamide, acrylic amide, long-chain polyamino amide, amino amide and salts thereof (for example, phosphate).

Examples of the inorganic layered compound-based viscosity modifier include layered compounds such as montmorillonite, bentonite, and clay.

Examples of the aminoplast-based viscosity modifier include hydrophobically modified ethoxylate aminoplast-based viscosity modifiers.

The following are examples of guidelines for adjusting the first normal stress difference, Tanδ and CON values of the paint composition.

In order to increase the first normal stress difference, a viscosity modifier having a large molecular weight may be used. Examples of such a viscosity adjuster include SN thickener series such as SN thickener 615, 630, 636, 640, which is an alkaline swelling type viscosity adjuster; and primal such as Dow Chemical's primal (registered trademark) ASE-60. (Registered trademark) series and the like.

In order to lower Tan δ, a viscosity modifier having a hard structure may be used. Examples of such a viscosity adjusting agent include Theoras (registered trademark) series such as Asahi Kasei's Theoras (registered trademark) RC series, which is a cellulosic viscosity adjusting agent; and Dow Chemical's cellosize QP 4400, 52000H. The cellosize (registered trademark) series can be mentioned.

In order to reduce the CON value, a viscosity modifier with a small interaction may be used. Examples of such a viscosity adjusting agent include Adecanol (registered trademark) UH-140S, 420, 450, 526, 540, 550 and the like, which is a urethane-associated viscosity adjusting agent manufactured by ADEKA. Can be mentioned.

The viscosity modifier may be used alone or in combination of two or more.

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. 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.

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.

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.

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, preferably 50 to 80 parts by mass with respect to 100 parts by mass of the paint composition.

<Solvent>
When a solvent is used, a solvent of a conventionally known coating composition can be appropriately selected and used. For example, 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, propylene glycol monoethyl ether acetate and the like. Ethers; 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, 1,3- Glycols such as butylene glycol, pentamethylene glycol, 1,3-octylene glycol; formamide, N-methylformamide, dimethylformamide (DMF), dimethylacetamide, dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP) Amids such as: acetone, methyl ethyl ketone (MEK), methyl propyl ketone, methyl isobutyl ketone, acetyl acetone, cyclohexanone and other ketones; mineral spirit, kerosene and other aliphatic hydrocarbons; toluene, xylene, mesitylene, dodecylbenzene and other aromatics. Group hydrocarbons; examples include halogen-based solvents such as chloroform and dichloromethylene. The solvent may be used alone or in combination of two or more.

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.

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.

<Other ingredients>
In addition to the above-mentioned components, the coating composition of the present invention includes 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, a plasticizer, and a preservative. It may contain other components such as antifungal agents and UV stabilizers. These other components may be used alone or in combination of two or more.

The coating composition according to the present invention is, in one embodiment, a coating composition for a roller or a brush. The coating composition according to the present invention is, in another embodiment, a coating composition for rollers.

The paint composition according to the present invention is for interior use in one embodiment. Further, when the viscosity of the coating composition is 0.1 to 2.0 Pa · s, it is easy to form a coating film having a thin film thickness, which is suitable for forming a topcoat coating film for an interior.

<Preparation method of paint composition>
The method for preparing the coating composition is not particularly limited as long as the first normal stress difference, Tanδ and CON values are within the predetermined ranges, and the above-mentioned resin components, pigments, viscosity modifiers and the like are mixed by a conventionally known method. Can be prepared. Further, the coating composition of the present invention may be obtained by adding a viscosity adjusting agent or the like to a commercially available coating material containing a resin component and a pigment to adjust the first normal stress difference, Tan δ and CON values within a predetermined range.

<How to make a coating film>
The method for producing the coating film is not particularly limited, and a conventionally known coating method can be used. For example, it can be painted using a roller, a brush, or the like. 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. For example, 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.

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). , Containers, resin plates and films), electrical appliances and the like.

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.

The first normal stress difference, Tanδ, CON value and viscosity of the coating composition were determined by the above method.

In measuring the amount of paint scattered, the roller uses the product name "Wool Roller B Regular 4B" manufactured by Otsuka Brush Manufacturing Co., Ltd., and the slate plate uses the product name "Slate Plate" manufactured by TP Giken Co., Ltd. (length 600 mm, width). 210 mm) was used.

For the measurement of the amount of paint scattered, image analysis software (trade name "A image-kun" (registered trademark)) manufactured by Asahi Kasei Engineering Co., Ltd. was used as the image analysis software.

The details of each component of the coating composition used in the examples are as follows.
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.), surface conditioner (trade name "Aqualen 8020" manufactured by Kyoeisha Chemical Co., Ltd.) Polyflow KL-100 ")
Viscosity Adjuster 1 (Cellulose Viscosity Adjuster): Product name "Theoras (registered trademark) RC-591" manufactured by Asahi Kasei Corporation (solid content: 100%, indicated as RC-591 in Table 1).
Viscosity Adjuster 2 (Cellulose Viscosity Adjuster): Product name "Cellosize QP 52000H" manufactured by Dow Chemical Co., Ltd. (solid content: 100%, indicated as QP 52000H in Table 1)
Viscosity Adjuster 3 (Urethane Association Type Viscosity Adjuster): Product name "ADEKA NOL (registered trademark) UH-540" manufactured by ADEKA (solid content: 30%, indicated as UH-540 in Table 1).
Viscosity Adjuster 4 (Urethane Association Type Viscosity Adjuster): Product name "ADEKA NOL (registered trademark) UH-140S" manufactured by ADEKA (solid content: 30%, indicated as UH-140S in Table 1).
Viscosity Adjuster 5 (Urethane Association Type Viscosity Adjuster): Product name "ADEKA NOL (registered trademark) UH-420" manufactured by ADEKA (solid content: 30%, indicated as UH-420 in Table 1).
Viscosity Adjuster 6 (Urethane Association Type Viscosity Adjuster): Product name "ADEKA NOL (registered trademark) UH-450" manufactured by ADEKA (solid content: 30%, indicated as UH-450 in Table 1).
Viscosity adjuster 7 (polycarboxylic acid-based viscosity adjuster): Product name "SN Thickener 640" manufactured by San Nopco Ltd. (solid content: 30%, indicated as SN 640 in Table 1)
Viscosity Adjuster 8 (Alkaline Swelling Viscosity Adjuster): Product name "Primal (registered trademark) ASE-60" manufactured by Dow Chemical Co., Ltd. (solid content: 28%, indicated as ASE-60 in Table 1)
Viscosity adjuster 9 (alkaline swelling type viscosity adjuster): Product name "SN Thickener 630" manufactured by San Nopco Ltd. (solid content: 30%, indicated as SN 630 in Table 1)

(Preparation example of acrylic emulsion)
68.5 parts by mass of deionized water and sodium polyoxyethylene nonylphenyl ether sulfate (trade name "Revenol WZ" manufactured by Kao Co., Ltd.) in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube. 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.

(Examples 1 to 15 and Comparative Examples 1 to 7)
Each component was mixed in the formulation (part by mass) shown in Table 1 to prepare a coating composition. The first normal stress difference, Tanδ, CON value and viscosity were measured for the coating composition. The results are shown in Table 1.

(Evaluation of painting workability)
The amount of paint scattered was evaluated by the method described below.

<Measurement method of paint scattering amount>
For Examples 1 to 14 and Comparative Examples 1 to 7, the amount of paint scattered in the vertical coating was measured. FIG. 2 is a schematic diagram showing a method of measuring the amount of paint scattered in the vertical coating of the embodiment. As shown in FIG. 2, the slate plate 7 was erected vertically. Next, a sheet of A3 size black paper 8 was placed so that its short side was in contact with the short side of the slate plate 7. Using the roller 2 soaked with the paint, the slate plate 7 was started from the lower end, folded back at the upper end, and painted again to the lower end in about 1 second, and this was repeated 6 times. Then, the area of the paint scattered on the black paper 8 was obtained by image analysis. The amount of scattering in each Example and Comparative Example was indexed, with the amount of scattering in Comparative Example 1 being 100. The values are shown in Table 1. The smaller the value, the smaller the amount of paint scattered. An index value of 60 or less for paint scattering is acceptable.

For Example 15, the amount of paint scattered in the horizontal coating was measured (not shown). As the coating composition of Example 15, the same coating composition as that of Example 1 was used. Further, as in Example 1, a slate plate and black paper (two sheets) were used. First, the slate plate was placed horizontally. Next, one sheet of A3 size black paper was placed so that the short sides of the paper were in contact with each short side of the slate plate. Using a roller soaked in paint, the slate plate was started from one end, folded back at the other end, and painted again to the one end in about 1 second, and this was repeated 6 times. Then, the area of the paint scattered on the black paper was obtained by image analysis. The amount of scattering in Example 15 was indexed, with the amount of scattering in Comparative Example 1 being 100. The values are shown in Table 1. The smaller the value, the smaller the amount of paint scattered. An index value of 60 or less for paint scattering is acceptable.

* 1: The value in parentheses indicates the amount of solid content. * 2: The values in parentheses represent the solid content of each viscosity adjusting agent or the total solid content of the viscosity adjusting agent with respect to 100 parts by mass of the coating composition. * 3: Example 15 is an example of horizontal coating.

As shown in Table 1, according to the present invention, it was possible to suppress or reduce the scattering of the paint not only in the horizontal direction but also in the vertical direction. Further, from the comparison between Examples 9 and 13, it can be seen that even if the paint compositions have the same viscosity, the paint scattering differs depending on the physical property values. From this, it can be seen that the paint scattering cannot be suppressed simply by the viscosity.

1: Surface 2: Roller 3: Liquid film 4: Paint thread 5: Constriction 6: Droplet 7: Slate plate 8: Black paper

Claims

The first normal stress difference is 10 Pa or more,
The loss tangent (Tanδ) is 1.00 or less, and the constriction generation suppression (CON) value of the paint yarn is 0.45 or less.
Paint composition.
The coating composition according to claim 1, wherein the first normal stress difference is 10 to 200 Pa.
The coating composition according to claim 1 or 2, wherein the Tan δ is 0.5 to 1.0.
The coating composition according to any one of claims 1 to 3, wherein the CON value is 0.20 to 0.45.
Contains resin components and viscosity modifiers,
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 alkaline swelling type viscosity adjusting agent, a urethane associated viscosity adjusting agent, and a cellulosic viscosity adjusting agent. Paint composition.
The coating composition according to any one of claims 1 to 5, which has a viscosity of 0.1 to 2.0 Pa · s.
The paint composition according to any one of claims 1 to 6, which is for interior use.