WO2022019107A1 - Pigment composition and coating film - Google Patents

Abstract

The present invention provides a pigment composition which is capable of forming a coating film that has excellent water-resistant adhesion, while exhibiting silky feeling but not exhibiting grain feeling.　A pigment composition which contains a photoluminescent pigment, a basic compound or a salt thereof, a polysaccharide derivative and an organic solvent, wherein: the photoluminescent pigment is a flake-like titanic acid; and the polysaccharide derivative is configured by substituting at least some hydrogen atoms in the hydroxy groups contained in a polysaccharide with organic groups.

Description

Pigment composition and coating film

The present invention relates to a pigment composition containing a brilliant pigment and a coating film using the pigment composition.

Conventionally, bright pigments having a titanium oxide layer on the surface of scaly materials such as mica, scaly alumina, and scaly glass flakes have been used in many fields. Such conventional brilliant pigments have a strong brilliant feeling and a grainy feeling (glossy feeling that seems to shine brilliantly), and are known as pigments that impart a pearly luster to a coating film. .. However, as a design having a higher-class feeling, a design that does not have a grainy feeling and exhibits a silky feeling (smooth shine like silk) is required. Flaky titanium acid is known as a bright pigment exhibiting such a silky feeling.

For example, Patent Document 1 below discloses flake titanic acid in which a titanate having a layered crystal structure is treated with an acid and then an organic basic compound is allowed to act to swell or peel off the layers. The flaky titanium acid has an average major axis of 5 to 30 μm and an average thickness of 0.5 to 300 nm. Patent Document 1 describes that a bright pigment made of flaky titanium acid having such a shape does not have a grainy feeling and exhibits a very excellent silky feeling.

Japanese Unexamined Patent Publication No. 2006-257179

However, the bright pigment made of flaky titanium acid of Patent Document 1 does not have a grainy feeling and exhibits a silky feeling, but has a problem that it is not easy to apply to a solvent-based paint. Further, the bright pigment made of flaky titanium acid of Patent Document 1 has a problem that the water resistance and adhesion when formed into a coating film are not sufficient.

An object of the present invention is to provide a pigment composition and a coating film using the pigment composition, which have no grainy feeling, exhibit a silky feeling, and can form a coating film having excellent water adhesion resistance. ..

The present invention provides the following pigment composition and a coating film using the pigment composition.

Item 1. The bright pigment contains a bright pigment, a basic compound or a salt thereof, a polysaccharide derivative, and an organic solvent. The bright pigment is flaky titanium acid, and the polysaccharide derivative is contained in the polysaccharide. A pigment composition in which at least a part of hydrogen atoms in a hydroxy group is substituted with an organic group.

Item 2. The pigment composition according to Item 1, wherein the polysaccharide is cellulose.

Item 3 The organic group is at least one selected from the group consisting of an alkyl group having a substituent, an alkyl group having no substituent, an acyl group having a substituent, and an acyl group having no substituent. Item 2. The pigment composition according to Item 1 or 2.

Item 4. The pigment composition according to any one of Items 1 to 3, wherein the basic compound or a salt thereof is an amino-modified silicone.

Item 5 The flaky titanium acid is formed by treating the titanate having a layered crystal structure with an acid and then allowing the basic compounds or salts thereof to act on the layers to cause the layers in the layered crystal structure to be swollen and peeled off. , The pigment composition according to any one of Items 1 to 4.

Item 6. The pigment composition according to any one of Items 1 to 5, wherein the average major axis of the flaky titanium acid is 5 μm or more and 30 μm or less.

Item 7. The pigment composition according to any one of Items 1 to 6, wherein the flaky titanium acid has an average thickness of 0.5 nm or more and 300 nm or less.

Item 8. The pigment composition according to any one of Items 1 to 7, wherein the organic solvent is an aprotic organic solvent.

Item 9. The pigment composition according to any one of Items 1 to 8, wherein the content of the brilliant pigment is 5% by mass or more and 50% by mass or less in 100% by mass of the solid content of the pigment composition. thing.

Item 10. The item according to any one of Items 1 to 9, wherein the mass ratio of the brilliant pigment to the polysaccharide derivative (brilliant pigment / polysaccharide derivative) is 5/95 or more and 50/50 or less. Pigment composition.

Item 11 A coating film to which the pigment composition according to any one of Items 1 to 10 is applied.

According to the present invention, it is possible to provide a pigment composition and a coating film using the pigment composition, which have no particle feeling, exhibit a silky feeling, and can form a coating film having excellent water adhesion resistance. ..

FIG. 1 is a schematic diagram for explaining the mechanism of exfoliation in the titanate having a layered crystal structure. FIG. 2 is a cross-sectional photograph showing an example of a coating film formed by the pigment composition of the present invention. FIG. 3 is a cross-sectional photograph showing an example of voids (voids) formed in the coating film.

Hereinafter, an example of a preferred embodiment of the present invention will be described. However, the following embodiments are merely examples. The present invention is not limited to the following embodiments.

[Pigment composition]
The pigment composition of the present invention contains a bright pigment, basic compounds or salts thereof, a polysaccharide derivative, and an organic solvent. The bright pigment is flaky titanium acid. The polysaccharide derivative is composed of at least a part of hydrogen atoms in the hydroxy group contained in the polysaccharide being replaced with an organic group.

Since the pigment composition of the present invention contains a bright pigment which is a flaky titanium acid, a basic compound or a salt thereof, a specific polysaccharide derivative, and an organic solvent, there is no grainy feeling and a silky feeling. At the same time, it is possible to form a coating film having excellent water adhesion resistance.

Conventionally, a bright pigment having a titanium oxide layer on the surface of a scaly material has a grainy feeling and a silky feeling is not sufficient. In addition, flaky titanium acid that swells or peels off the layers of the layered crystal structure titanium salt (hereinafter sometimes referred to as "layered titanium salt") can improve the silky feeling, but when it is formed into a coating film. There was a problem that the water resistance and adhesion were not sufficient.

On the other hand, the present inventors have found that the coating film formed of the conventional flaky titanium acid has many voids (voids) as shown in FIG. Further, since the conventional flaky titanium acid has a high surface hydrophilicity, it is considered that water permeates and is retained in the void as described above, and the water adhesion resistance is lowered.

Then, as a result of diligent studies in consideration of these, the present inventors have made it possible to contain a specific polysaccharide derivative in addition to a bright pigment which is a flaky titanium acid and basic compounds or salts thereof. , It has been found that a coating film having excellent water resistance and adhesion can be formed.

When hydrophobic amine 2 having a long hydrophobic portion is used as the basic compounds or salts thereof, the layers of the layered titanate 1 (titanate having a layered crystal structure) are swollen. It is possible to impart hydrophobicity to the surface of the flaky titanium acid 3 while peeling it off. However, when such basic compounds or salts thereof are used as a release agent, they tend to aggregate in water and then aggregate to form rice cake-like aggregates. On the other hand, the present inventors have found that the dispersibility of the layered titanate 1 can be enhanced even in an organic solvent by containing the specific polysaccharide derivative 4.

Therefore, when the pigment composition of the present invention is used as a coating film, as shown in FIG. 2, the exfoliated flaky titanium acid can be neatly oriented in the coating film, so that the silky feeling can be improved. Further, since the surface of the flaky titanium acid can be imparted with hydrophobicity, the water adhesion resistance can be improved. Furthermore, the dispersibility of flaky titanium acid can be enhanced even in an organic solvent, and it can be applied to a solvent-based paint.

Each component and the like of the pigment composition of the present invention will be described below.

(Glowing pigment)
The flaky titanium acid as a brilliant pigment is, for example, treated with an acid or warm water to obtain a layered titanium acid, and then a basic compound having an interlayer swelling action or a salt thereof is allowed to act on the layered titanium acid. It can be obtained by swelling and peeling off the layers.

Layered Titanate;
The layered titanate as a raw material is obtained by, for example, mixing cesium carbonate and titanium dioxide at a molar ratio of 1: 5.3 and firing at 800 ° C. according to the method disclosed in Japanese Patent No. 2979132. _0.7 Ti _1.83 O ₄ is mentioned.

Further, according to the method disclosed in International Publication No. 99/11574, potassium carbonate, lithium carbonate and titanium dioxide are mixed at K / Li / Ti = 3/1 / 6.5 (molar ratio) and ground. _Examples thereof include _{K 0.8} L _0.27 Ti 1.73 O ₄ obtained by firing at 800 ° C.

Further, according to the method disclosed in Japanese Patent No. 3062497, a mixture in which an alkali metal or a halide or sulfate of an alkali metal is used as a flux and mixed so that the mass ratio of the flux / raw material is 0.1 to 2.0 is prepared. _{General formula A X} M _Y □ _Z Ti _{2- (Y + Z)} O ₄ obtained by firing at 700 ° C to 1200 ° C [In the formula, A and M indicate 1 to trivalent metals different from each other, and □ Indicates the defect site of Ti. X is a positive real number satisfying 0 <X <1.0, and Y and Z are 0 or a positive real number satisfying 0 <Y + Z <1].

Note that A in the above general formula is a metal having a valence of 1 to 3 and is preferably at least one selected from the group consisting of K, Rb, and Cs. M is a metal having a valence of 1 to 3 different from that of the metal A, and is preferably at least one selected from the group consisting of Li, Mg, Zn, Cu, Fe, Al, Ga, Mn, and Ni. Is.

Specific examples include K _0.80 Li _0.27 Ti _1.73 O ₄ , Rb _0.75 Ti _1.75 Li _0.25 O ₄ , and Cs _0.70 Li _0.23 Ti _1.77 O. ₄ , Cs _0.70 □ _0.18 Ti _1.83 O ₄ , Cs _0.70 Mg _0.35 Ti _1.65 O ₄ , K _0.8 Mg _0.4 Ti _1.6 O ₄ , K _{0. 8} Ni _0.4 Ti _1.6 O ₄ , K _0.8 Zn _0.4 Ti _1.6 O ₄ , K _0.8 Cu _0.4 Ti _1.6 O ₄ , K _0.8 Fe _0.8 Ti _1.2 O ₄ , K _0.8 Mn _0.8 Ti _1.2 O ₄ , K _0.76 Li _0.22 Mg _0.05 Ti _1.73 O ₄ , K _0.67 Li _0.2 Al _0.07 Ti _1.73 O _{4 and the} like can be mentioned.

_{Further, K 0.5 to 0.7} L obtained by pickling _{K 0.8} L _0.27 Ti _1.73 O ₄ and then firing according to the method disclosed in International Publication No. 03/0377797. _It may be 0.27 Ti _1.73 O _{3.85 to 3.95.}

Layered titanium acid;
Layered titanic acid can be obtained, for example, by acid-treating the layered titanate and substituting exchangeable metal cations with hydrogen ions or hydronium ions. The acid used for the acid treatment is not particularly limited, and may be a mineral acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, or an organic acid. The type of layered titanium acid, the type and concentration of acid, and the slurry concentration of layered titanium acid affect the exchange rate of metal cations. In general, the lower the acid concentration and the higher the slurry concentration, the larger the residual amount of interlayer metal cations and the more difficult it is to delaminate, so that the thickness of flaky titanium acid after delamination increases.

If it is difficult to remove the metal cation, the acid treatment may be repeated if necessary.

Flaky titanium acid;
The flaky titanium acid can be obtained by treating the layered titanium acid with an acid and then allowing a basic compound or a salt thereof to act to swell and peel off the layers of the layered crystal structure.

The average major axis of flaky titanium acid is preferably 5 μm or more, more preferably 10 μm or more, preferably 30 μm or less, and more preferably 25 μm or less. When the average major axis of flaky titanium acid is at least the above lower limit value, the silky feeling can be further improved. On the other hand, when the average major axis of the flaky titanium acid is not more than the above upper limit value, it can be more uniformly and parallelly dispersed in the coating film.

The average major axis means the particle size in the plane direction perpendicular to the thickness direction of flaky titanium acid. The average major axis can be measured by observation with, for example, a transmission electron microscope (TEM) and a scanning electron microscope (SEM). Specifically, it can be measured by blending flaky titanium acid in the coating film and TEM observing the cross section of the coating film. The average major axis can be, for example, the average of the particle diameters of the 100 flaky titanium acids measured in this way.

The average thickness of flaky titanium acid is preferably 0.5 nm or more, more preferably 10 nm or more, preferably 300 nm or less, and more preferably 100 nm or less. When the average thickness of flaky titanium acid is at least the above lower limit value, it can be produced more easily. On the other hand, when the average thickness of the flaky titanium acid is not more than the above upper limit value, the silky feeling can be further improved.

The average thickness of flaky titanium acid can also be measured by electron microscope observation such as TEM or SEM in the same manner as the above average major axis. The average thickness can be, for example, the average of the thicknesses of the 100 flaky titanium acids measured in this way.

The flaky titanium acid is preferably a single-layer titanium acid nanosheet in which the layered titanium acid is completely peeled off, but may be a laminated body of two to 300 layers of titanium acid nanosheets. The laminate of the titanium acid nanosheets is preferably a laminate of 10 to 300 layers of titanium acid nanosheets. Further, a single-layer titanium acid nanosheet and a laminate of titanium acid nanosheets may be mixed. However, in this case, it is desirable that the average thickness of the flaky titanium acid is mixed so as to be within the above-mentioned range.

The content of the brilliant pigment is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 50% by mass or less, and more preferably 30% by mass or less in the solid content of 100% by mass of the pigment composition. be. When the content of the brilliant pigment is in the above range, the silky feeling can be further improved.

(Basic compounds or salts thereof)
The basic compounds or salts thereof are not particularly limited as long as they have an interlayer swelling action of titanium acid having a layered crystal structure, and are, for example, primary to tertiary organic amines, organic ammonium salts, organic phosphonium salts, and amino modifications. Examples thereof include silicone. Of these, amino-modified silicone is preferable from the viewpoint of further enhancing water resistance. As the basic compounds or salts thereof, one type may be used alone, or a plurality of types may be used in combination.

Examples of primary organic amines include methylamine, ethylamine, n-propylamine, butylamine, pentylamine, hexylamine, octylamine, dodecylamine, 2-ethylhexylamine, 3-methoxypropylamine and 3-ethoxypropylamine. , Octadecylamine or salts thereof and the like.

Examples of the secondary organic amines include diethylamine, dipentylamine, dioctylamine, dibenzylamine, di (2-ethylhexyl) amine, di (3-ethoxypropyl) amine, and salts thereof.

Examples of the tertiary organic amines include triethylamine, trioctylamine, tri (2-ethylhexyl) amine, tri (3-ethoxypropyl) amine, dipolyoxyethylene dodecylamine, dimethyldecylamine, and salts thereof. Be done.

Examples of the quaternary organic ammonium salts include dodecyltrimethylammonium salt, cetyltrimethylammonium salt, stearyltrimethylammonium salt, benzyltrimethylammonium salt, benzyltributylammonium salt, trimethylphenylammonium salt, dimethyldistearylammonium salt and dimethyldidecylammonium. Examples thereof include salts, dimethylstearylbenzylammonium salt, dodecylbis (2-hydroxyethyl) methylammonium salt, trioctylmethylammonium salt, dipolyoxyethylene dodecylmethylammonium salt and the like.

Examples of the organic phosphonium salts include organic phosphonium salts such as tetrabutylphosphonium salt, hexadecyltributylphosphonium salt, dodecyltributylphosphonium salt and dodecyltriphenylphosphonium salt.

The amino-modified silicone has a polysiloxane skeleton composed of repeating (—Si—O—), and a part of the alkyl side chain of the silicon atom is modified by an amino modifying group. The amino modifying group may be bonded to the side chain of silicone, which is the main chain, or may be bonded to the terminal. Examples of the amino modifying group include a primary to tertiary amino group and an organic group having a primary to tertiary amino group. Examples of the organic group having a primary to tertiary amino group include -R ^1- NH ₂ (R ¹ indicates a divalent organic group) and the like. Among these, the compound represented by the following formula (1) is preferable.

(In formula (1), ^{R 2} represents a -NH ₂ or ^-R 1 -NH _2, plural ^{R 2} may being the same or different, n represents an arbitral integer not .R ¹ Indicates a divalent organic group.)

N is preferably an integer of 1 to 2,000.

Examples of the divalent organic group of R ¹ include an alkylene group and an arenediyl group.

As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group and the like.

As the arrangeyl group, an arrangeyl group having 6 to 10 carbon atoms is preferable. Examples of such an arrangeyl group include a phenylene group and the like.

The amino-modified silicone has a kinematic viscosity at 25 ° C., preferably 10 mm ² / s to 2000 mm ² / s. If the kinematic viscosity is ^{smaller than 10 mm 2} / s or ^{larger than 2000 mm 2} / s, it becomes difficult to disperse in an organic solvent. The kinematic viscosity can be measured with a kinematic viscosity measuring device.

The functional group equivalent (amino equivalent) of the amino-modified silicone is preferably 50 g / mol to 100,000 g / mol, more preferably 300 g / mol to 3000 g / mol, and further preferably 400 g / mol to 2000 g / mol. By setting the functional group equivalent within the above range, the degree of peeling can be further increased, and the dispersion stability in an organic solvent can be further improved.

The amino-modified silicone is preferably water-insoluble. Water insoluble means that the amount dissolved in 1 L of water at 25 ° C. is 10 g or less.

Examples of the amino-modified silicone include both-terminal amino-modified silicone represented by the following formula (2). In addition, R in the formula (2) is a methylene group, a phenylene group and the like.

As the amino-modified silicone, one type may be used alone, or a mixture consisting of two or more types may be used.

The content of the basic compounds or salts thereof is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, preferably 50% by mass, based on 100% by mass of the solid content of the pigment composition. It is mass% or less, more preferably 40% by mass or less, still more preferably 30% by mass or less. When the content of the basic compounds or a salt thereof is at least the above lower limit value, the water adhesion resistance can be further improved. When the content of the basic compounds or a salt thereof is not more than the above upper limit value, the silky feeling can be further improved.

In order to allow the basic compounds having an interlayer swelling action or salts thereof to act, the basic compounds or the basic compounds or the basic compounds or the basic compounds or the salt thereof are stirred in a dispersion liquid in which the layered titanic acid after the acid treatment or the hot water treatment is dispersed in an aqueous medium. The salt may be added directly, or a basic compound or a salt thereof diluted with water or an aqueous medium may be added. As the blending amount of the basic compounds or salts thereof, it is preferable to use 0.1 equivalent to 10 equivalents of the basic compounds or salts thereof with respect to the exchangeable ion capacity of the layered titanic acid. Delamination may not be expected if the amount is less than 0.1 equivalent, and if it is larger than 10 equivalent, it is not economically advantageous. The exchangeable ion capacity is a metal ion content replaceable, for example, when the layered titanate is represented by the general formula _{A x M y □ z Ti 2-} (y + z) O 4, the valence of A m , M is a value represented by mx + ny when the valence of M is n. The equivalent of the basic compounds or salts thereof means the amount of cationic groups generated by the reaction between the basic compounds or salts thereof and the hydrogen ions or hydronium ions present in the layered titanic acid. do.

The average major axis of flaky titanium acid can keep the average major axis of the raw material, layered titanate, unless it is stirred with a strong shearing force in the step of delamination by the action of basic compounds or salts thereof. can.

(Polysaccharide derivative)
The polysaccharide derivative has a polysaccharide skeleton in the main skeleton, and is composed of at least a part of hydrogen atoms of the hydroxy group contained in the polysaccharide being replaced with an organic group.

Examples of the organic group include an alkyl group having a substituent, an alkyl group having no substituent, an acyl group having a substituent, and an acyl group having no substituent. These organic groups may be used alone or in combination of two or more.

As the alkyl group, an alkyl group having 1 to 5 carbon atoms is preferable. Examples of such an alkyl group include a methyl group and an ethyl group. Further, examples of the substituent having an alkyl group include a hydroxy group and a carboxy group.

As the acyl group, an acyl group having 2 to 5 carbon atoms is preferable. Examples of such an acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyl group and the like.

Examples of polysaccharides include cellulose and starch. The polysaccharide is preferably cellulose. Cellulose is a linear polymer in which a β-D-glucose molecule (β-D-glucopyranose) represented by the following formula (3) is polymerized by a β-1,4-glycosidic bond. Each glucose unit constituting cellulose has three hydroxy groups (m in the following formula (3) indicates a natural number).

As the polysaccharide derivative, the organic group is introduced into such cellulose by utilizing the hydroxy group. Cellulose is the main component of plants and trees, and is obtained by separating and treating other components such as lignin from plants and trees. In addition to those obtained in this way, cotton (for example, cotton linter) or pulp (for example, wood pulp) having a high cellulose content can be purified or used as it is. As the shape, size, and form of cellulose or its derivative used as a raw material, it is preferable to use a powder form having an appropriate particle size and particle shape from the viewpoint of reactivity, solid-liquid separation, and handleability.

The degree of polymerization of cellulose is preferably in the range of 50 to 5000 as the degree of polymerization of glucose (average degree of polymerization). If the degree of polymerization is too low, the dispersion of the brilliant pigment may not be sufficient. On the contrary, if the degree of polymerization is too high, the compatibility with the organic solvent may be hindered.

The average number of organic groups introduced per glucose unit of cellulose (DS _LO ) (organic group introduction ratio), that is, the average number of hydroxy groups substituted with the organic groups per glucose unit (hydroxyl substitution degree) is. It can be appropriately set according to the physical properties required for the target pigment composition and the efficiency at the time of production, but is preferably 0.1 or more, more preferably 1.8 or more, still more preferably 2.3 or more, preferably 2.3 or more. Is 2.9 or less, more preferably 2.8 or less, still more preferably 2.7 or less.

Examples of polysaccharide derivatives include cellulose esters and cellulose ethers.

Specific examples of cellulose esters include cellulose acetate such as cellulose diacetate (DAC) and cellulose triacetate (TAC); cellulose C _3-5 acylate such as cellulose propionate and cellulose butyrate; cellulose acetate propionate. (CAP), cellulose acetate such as cellulose acetate butyrate (CAB), cellulose acetate such as C _3-5 acylate and the like can be mentioned.

Examples of cellulose ethers include alkyl cellulose, hydroxyalkyl cellulose, hydroxyalkyl alkyl cellulose, carboxyalkyl cellulose, and alkyl-carboxyalkyl cellulose.

Examples of the alkyl cellulose include C _1-4 alkyl cellulose such as methyl cellulose and ethyl cellulose.

_{Examples of the hydroxyalkyl cellulose include hydroxy C 2-4} alkyl cellulose such as hydroxyethyl cellulose (HEC) and hydroxypropyl cellulose (HPC).

Examples of the hydroxyalkylalkyl cellulose include hydroxy C _2-4 alkyl C _1-4 alkyl cellulose such as hydroxypropyl methyl cellulose.

Examples of the carboxyalkyl cellulose include carboxymethyl cellulose (CMC).

Examples of the alkyl-carboxyalkyl cellulose include methyl carboxymethyl cellulose and the like.

Among them, cellulose esters or cellulose ethers are preferable, and ethyl cellulose or cellulose acetate butyrate (CAB) is more preferable.

As for these polysaccharide derivatives, one type may be used alone, or a plurality of types may be used in combination.

The content of the polysaccharide derivative is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 45% by mass or more, preferably 95% by mass or less, based on 100% by mass of the solid content of the pigment composition. It is more preferably 90% by mass or less, still more preferably 85% by mass or less. When the content of the polysaccharide derivative is at least the above lower limit value, the water adhesion resistance can be further improved. When the content of the polysaccharide derivative is not more than the above upper limit value, the silky feeling can be further improved.

The mass ratio of the brilliant pigment to the polysaccharide derivative (brilliant pigment / polysaccharide derivative) is preferably 5/95 or more, more preferably 7/93 or more, still more preferably 9/91 or more, preferably 50/50 or less. , More preferably 40/60 or less, still more preferably 35/65 or less. When the mass ratio (brilliant pigment / polysaccharide derivative) is at least the above lower limit value, the silky feeling can be further improved. When the mass ratio (brilliant pigment / polysaccharide derivative) is not more than the above upper limit value, the water adhesion resistance can be further improved.

(Organic solvent)
The organic solvent is not particularly limited, but for example, aromatic hydrocarbons such as xylene, toluene and ethylbenzene; aliphatic hydrocarbons such as hexane and heptane; esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; tetrachloride. Halogenated hydrocarbons such as carbon; alcohols such as methanol, ethanol, isopropanol, n-butanol, sec-butanol, isobutanol; ethers such as n-butyl ether, dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether; Examples thereof include ketones such as methyl ethyl ketone, methyl isobutyl ketone and diisobutyl ketone. Among them, the organic solvent is preferably an aprotonic organic solvent such as an aromatic hydrocarbon, an ester, a halogenated hydrocarbon, an ether, or a ketone, and more preferably an aromatic hydrocarbon or an ester. .. These organic solvents may be used alone or in combination of two or more.

The content of the organic solvent is not particularly limited and can be adjusted as appropriate. For example, in consideration of the viscosity suitable for coating, it can be 60% by mass or more and 90% by mass or less in 100% by mass of the pigment composition.

(Other additives)
The pigment composition of the present invention contains a curing agent, a binder resin, other bright pigments, pigments other than bright pigments, extender pigments, rust preventive pigments, dyes, matting agents, and ultraviolet absorbers as long as the design is not impaired. Other additives such as agents, light stabilizers, antioxidants, plastics, dispersants, leveling agents, surface preparation agents, sagging agents, thickeners, defoaming agents, lubricants, anti-settling agents, and rhology control agents. It can be contained as appropriate.

Examples of the curing agent include polyisocyanate compounds, amino resins, polycarboxylic acid compounds and the like, and preferably at least one selected from polyisocyanate compounds and amino resins. By containing a curing agent, the water resistance and adhesion of the coating film can be further improved.

Examples of the polyisocyanate compound include aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimerate diisocyanate, and lysine diisocyanate; burette-type adducts and isocyanurate ring adducts of these aliphatic polyisocyanates. Allophanate type adduct, uretdione type adduct; Isophorone diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), methylcyclohexane-2,4- or -2,6-diisocyanate and other alicyclic diisocyanates; these alicyclics Bulet type adduct of group diisocyanate, isocyanurate ring adduct; xylylene diisocyanate, tetramethylxylylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthalenedi isocyanate, 1,4 -Aromatic diisocyanate compounds such as naphthalenediocyanate; burette-type adducts, isocyanurate ring adducts of these aromatic diisocyanates; hydrogenated MDI and derivatives of hydrogenated MDI; ethylene glycol, propylene glycol, 1,4-butylene glycol , Dimethylol propionic acid, polyalkylene glycol, trimethylolpropane, hexanetriol, and other urethanized additives made by reacting a polyisocyanate compound with the hydroxylates of polyols in an excess amount of isocyanate groups; these urethanized additives. The burette type adduct, isocyanurate ring adduct, and the like can be mentioned.

The polyisocyanate compound may be blocked. The blocked polyisocyanate compound is obtained by adding a blocking agent to the isocyanate group of the above-mentioned polyisocyanate compound. The blocked polyisocyanate compound produced by addition is stable at room temperature, but when heated to the baking temperature of the coating film (usually about 80 ° C to about 200 ° C), the blocking agent dissociates and regenerates free isocyanate groups. It is desirable to get something. Examples of the blocking agent satisfying such requirements include phenol-based, lactam-based, alcohol-based, ether-based, oxime-based, active methylene-based, mercaptan-based, acid amide-based, imide-based, amine-based, imidazole-based, and pyrazole-based. Such as a blocking agent. Of these, a blocked polyisocyanate compound containing an active methylene-based or pyrazole-based blocking agent can be preferably used.

When a polyisocyanate compound is used, its content is preferably in the range of 1 part by mass to 300 parts by mass with respect to 100 parts by mass of the total solid content of the polysaccharide derivative.

Examples of the amino resin include methylolated amino resins obtained by reacting aldehydes with amino components such as melamine, urea, benzoguanamine, acetoguanamine, steloganamin, spiroganamin and dicyandiamide. Examples of the aldehyde include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like. Further, a methylolated amino resin etherified with an appropriate alcohol can also be used. Examples of alcohols used for etherification include methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol, 2-ethylbutanol, 2-ethylhexanol and the like. .. As the amino resin, a melamine resin is preferable, and among them, a methylolated melamine resin in which at least a part of a methylol group is alkyl etherified can be preferably used.

When an amino resin is used, its content is preferably in the range of 1 part by mass to 300 parts by mass with respect to 100 parts by mass of the total solid content of the polysaccharide derivative.

Examples of the binder resin include (meth) acrylic resin and polyester resin, and acrylic resin is preferable. In addition, in this specification, "(meth) acrylic" means "at least one of acrylic and methacrylic".

Examples of the (meth) acrylic resin include homopolymers or copolymers obtained by radical polymerization of a radically polymerizable monomer containing (meth) acrylic acid ester as a main component. It is preferable that the molecule of the polymer has a crosslinkable functional group such as a hydroxy group or a carboxy group.

Examples of the (meth) acrylic acid ester include monoesters of (meth) acrylic acid and monovalent alcohol having 1 to 20 carbon atoms, specifically, methyl (meth) acrylate, (meth). Examples thereof include ethyl acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, and lauryl (meth) acrylate.

Examples of the monomer containing the crosslinkable functional group include hydroxyethyl (meth) acrylic acid, hydroxypropyl (meth) acrylic acid, caprolactone hydroxyethyl (meth) acrylic acid, (meth) acrylic acid, and maleic acid. , Or fumaric acid and the like. In addition to the above, other monomers capable of radical copolymerization with the above monomers can be used, for example, (meth) acrylonitrile, styrene, vinyl acetate, vinyl methyl ether, vinyl chloride, vinylidene chloride, ethylene, or. Unsaturated compounds having one or more polymerizable double bonds in one molecule such as propylene can be used.

The acid value of the (meth) acrylic resin is preferably in the range of 3 mgKOH / g to 50 mgKOH / g. If the acid value is too low, the adhesiveness as a coating film may decrease, and conversely, if the acid value is too high, the water resistance may decrease.

The weight average molecular weight (Mw) of the (meth) acrylic resin is preferably in the range of 200,000 to 1,000,000. If the quantity average molecular weight is too low, the effect of the present invention of stably maintaining the orientation of the brilliant pigment in the coating film state before curing may not be sufficiently obtained. If the quantity average molecular weight is too high, the solubility of the coating composition in a solvent may be poor, or the viscosity of the coating composition may be too high, resulting in poor handleability. The quantity average molecular weight can be determined by a gel permeation chromatography (GPC) method using a styrene polymer as a standard. Regarding the ratio of the polysaccharide derivative to the binder resin, the polysaccharide derivative / binder resin is preferably 10/90 or more, more preferably 10/90 or more in terms of solid content mass ratio, from the viewpoint of further enhancing water adhesion, weather resistance and the like. It is 30/70 or more, more preferably 40/60 or more, preferably 90/10 or less, more preferably 70/30 or less, still more preferably 60/40 or less.

Other bright pigments include scaly particles such as mica (artificial mica, synthetic mica, etc.), silica, alumina, or glass flakes, and TIM ₂ , SnO ₂ , ZrO ₂ , Fe ₂ O 3, _{and Fe 2 O 3 on the surface of these particles.} Scale _{particles provided with a multi-layered film made of metal oxides such as ZnO 2} , Cr ₂ O ₃ , or V ₂ O ₅ ; colored aluminum flake pigments; metallic titanium flake pigments; stainless flake pigments; plate-like iron oxide pigments; Examples include hologram pigments.

Examples of the pigment excluding the brilliant pigment include white pigment, black pigment, red pigment, yellow pigment, orange pigment, purple pigment, blue pigment, green pigment and the like, and black pigment or blue pigment is preferable. Pigments other than bright pigments can be used alone or in combination of two or more depending on the hue.

Examples of the white pigment include titanium oxide, zinc white, zinc sulfide and the like.

Black pigments include carbon blacks such as furnace black, channel black, acetylene black, thermal black, lamp black, or bone black; carbon nanotubes; carbon nanofibers; fullerene; graphene; graphene oxide; natural graphite; graphite; aniline black; Perylene-based pigments; lactam-based pigments; titanium black (black particles having titanium atoms such as titanium oxynitride and low-order titanium oxide); metals such as copper, iron, manganese, cobalt, chromium, nickel, zinc, calcium, or silver. Oxides; composite oxides; metal sulfides; metal sulfates; metal carbonates and the like can be mentioned. Among them, the black pigment is preferably carbon black.

Examples of the red pigment include red iron oxide, naphthol AS-based azored, anthrone, anthracinoyl red, perylene maroon, quinacridone-based red pigment, diketopyrrolopyrrole, watching red, and permanent red.

Examples of the yellow pigment include yellow iron oxide, titanium yellow, monoazo yellow, condensed azo yellow, azomethin yellow, bismus vanadate, benzimidazolone, isoindoline, isoindoline, quinophthalone, benzidine yellow, permanent yellow and the like.

Examples of the orange pigment include permanent orange and the like.

Examples of the purple pigment include cobalt purple, quinacridone violet, dioxazine violet and the like.

Examples of blue pigments include metal phthalocyanine pigments such as copper phthalocyanine blue (Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, etc.); Inorganic metal cyanine pigments. Anthraquinone-based pigments (Pigment Blue 60, etc.); Dioxazine-based pigments (Pigment Blue 80, etc.); Cobalt blue and the like. Among them, the blue pigment is preferably a metallic phthalocyanine pigment.

Examples of the green pigment include phthalocyanine green and the like.

Examples of the extender pigment include barita powder, barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, silica, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white, gloss white, mica powder and the like.

Examples of the rust preventive pigment include aluminum dihydrogen tripolyphosphate, aluminum phosphomolybate, and the like.

Examples of the matting agent include fine powder silica (hydrous silicon dioxide), polyethylene powder, resin powder, ceramic beads and the like.

Examples of the ultraviolet absorber include benzotriazole-based absorbers, triazine-based absorbers, salicylic acid derivative-based absorbers, benzophenone-based absorbers, and the like.

[Coating film]
The coating film of the present invention is formed by the above-mentioned pigment composition of the present invention. Therefore, the coating film of the present invention exhibits an excellent silky feeling and is also excellent in water adhesion resistance.

The coating film of the present invention can be produced, for example, as follows.

First, the layered titanate is treated with an acid or warm water to obtain a layered titanic acid, and then a basic compound having an interlayer swelling action or a salt thereof is allowed to act to swell and peel off the layers to form flakes. Obtain titanic acid.

Next, prepare a solution by adding a polysaccharide derivative to the organic solvent. By adding the above-mentioned flaky titanium acid to the obtained solution and stirring the mixture, a pigment composition in which the flaky titanium acid is dispersed in an organic solvent can be obtained. The coating film of the present invention can be obtained by applying the obtained pigment composition on a substrate and drying it. The coating film of the present invention is usually preferably having a cured film thickness of 1 μm to 200 μm.

At the time of application, it is preferable that the solid content concentration of the pigment composition is 10% by mass or more and 40% by mass or less in order to obtain a more excellent silky feeling.

As the material of the base material, for example, a metal material such as steel, aluminum, brass, copper, stainless steel, tin, zinc-plated steel, alloyed zinc (Zn-Al, Zn-Ni, Zn-Fe, etc.) -plated steel; Polyolefin resins typified by polyethylene, polypropylene, etc .; Thermoplastic polyester resins such as polyethylene terephthalate resin, polybutylene terephthalate (PBT) resin, polycarbonate (PC) resin, polycarbonate-polybutylene terephthalate (PC / PBT) resin; acrylonitrile- Styrene resins such as styrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene-acrylate (ASA) resin; other polymethylmethacrylate resin, acrylic resin, vinylidene chloride, polyamide resin, polyphenylene ether resin, polyoxymethylene Plastic materials (synthetic resin molded products) such as resins, polyurethane resins, epoxy resins, hybrid resins thereof, fiber-reinforced plastics (Fiber-Reinforced Plastics), engineering resins, etc.; inorganic materials such as glass cement, concrete; wood; fibers Materials (paper, cloth, etc.) and the like can be mentioned. Depending on these materials, degreasing treatment or surface treatment can be appropriately performed to obtain an object to be coated. Further, an undercoat film or an intermediate coat film formed on the object to be coated can be used as the object to be coated.

The undercoat coating film is formed to conceal the surface of the material and to impart corrosion resistance, rust prevention, etc. to the material, and is formed by applying the undercoat paint, drying, and curing. Obtainable. The undercoat paint is not particularly limited, and examples thereof include electrodeposition paints and solvent-based primers.

The intermediate coating film is formed to conceal the material surface and the undercoat coating film, and to impart adhesiveness, chipping resistance, etc., and is formed on the material surface and the undercoat coating film. It can be obtained by applying an intermediate coating paint, drying and curing. The intermediate coating material is not particularly limited, and for example, an organic solvent-based or water-based intermediate coating material containing a thermosetting resin composition and a coloring material (pigment, dye, etc.) can be preferably used.

The pigment composition can be applied by, for example, spin coating, spray coating, roller coating, dip coating, flow coating, knife coating, electrostatic coating, bar coating, die coating, brush coating, or a method of dropping droplets. can do.

The heating conditions in the method for forming the coating film of the pigment composition are not particularly limited, but can be carried out, for example, by holding at 60 ° C to 200 ° C for 5 to 30 minutes.

The film thickness of the coating film of the present invention is preferably 10 μm or more, more preferably 15 μm or more, still more preferably 20 μm or more, preferably 150 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less. When the film thickness of the coating film is within the above range, there is no grainy feeling and an even more excellent silky feeling can be exhibited.

A paint such as a clear paint may be applied onto the obtained coating film to provide a top coat layer. Examples of the clear paint include solvent-based paints, water-based paints, water-dispersed paints, powder paints and the like. The clear paint may be a colored clear paint. The components contained in the clear paint are not particularly limited, and those containing a coating film-forming thermosetting resin, a curing agent and the like can be used.

Preferred examples of the solvent-type clear paint are a combination of an acrylic resin and / or a polyester resin and an amino resin, or an acrylic resin and / or a polyester having a carboxylic acid / epoxy curing system from the viewpoint of transparency or acid etching resistance. Examples include resin.

Further, as an example of the water-based clear paint, a resin containing a water-based resin obtained by neutralizing the coating film-forming resin contained in the solvent-type clear paint as an example with a base may be mentioned. Can be done. This neutralization can be done by adding tertiary amines such as dimethylaminoethanol and triethylamine before or after polymerization.

On the other hand, as the powder type clear paint, ordinary powder paints such as thermoplastic and thermosetting powder paints can be used. A thermosetting powder coating is preferable because a coating film having good physical properties can be obtained. Specific examples of the thermosetting powder paint include epoxy-based, acrylic-based and polyester-based powder clear paints, and acrylic powder clear paints having good weather resistance are particularly preferable.

The coating film of the present invention exhibits an excellent silky feeling and is also excellent in water resistance. Therefore, for example, the outer panel of an automobile body such as a passenger car, a truck, a motorcycle, a bus; an automobile part; a refrigerator, a washing machine, a smartphone, etc. It can be suitably used for the outer panel of household electric appliances such as audio equipment.

Hereinafter, the present invention will be described in more detail based on specific examples. The present invention is not limited to the following examples, and can be appropriately modified and implemented without changing the gist thereof.

<Synthesis of flaky titanium acid aggregates and flaky titanium acid>
(Synthesis Examples 1 to 5)
A raw material obtained by pulverizing and mixing 67.01 g of titanium oxide, 26.78 g of potassium carbonate, 12.04 g of potassium chloride, and 5.08 g of lithium hydroxide by a dry method was calcined at 1020 ° C. for 4 hours. 7.9 kg of a 10.9% water slurry of the obtained powder was prepared, 470 g of a 10% aqueous sulfuric acid solution was added, and the mixture was stirred for 2 hours to adjust the pH of the slurry to 7.0. The separated and washed products were dried at 110 ° C. and then calcined at 600 ° C. for 12 hours. The obtained white powder had a layered crystal structure of titanium salt K _0.6 Li _0.27 Ti _1.73 O _3.9 and had an average major axis of 15 μm.

22.5 g of 95% sulfuric acid was added while stirring 32.5 g of titanium acid salt having this layered crystal structure dispersed in 474.8 g of deionized water, and the mixture was reacted at room temperature for 1 hour and then separated by suction filtration. , Washed with water. The same step was performed again on the obtained solid content. _{The remaining amount of K 2} O in the obtained layered titanium acid was 2.0%, and the metal ion exchange rate was 94%.

The total amount of the obtained layered titanium acid was added to the deionized water so as to be 2.5 kg in total with the deionized water, and the amino-modified silicone shown in Table 1 below was added while being dispersed and stirred. The mixture was added in an amount and stirred at room temperature for 1 hour. Then, it was separated by suction filtration and washed with water to obtain flaky titanium acid aggregates.

The amino-modified silicones A to D shown in Table 1 are as follows.

Amino-modified silicone A: Double-ended amino-modified silicone (manufactured by Shinetsu Silicone, X-22-161A, side chain: methyl group, kinematic viscosity 25 ° C: 25 mm ² / s, functional group equivalent: 800 g / mol)
Amino-modified silicone B: Double-ended amino-modified silicone (manufactured by Shinetsu Silicone Co., Ltd., KF-8010, side chain: methyl group, kinematic viscosity 25 ° C.: 12 mm ² / s, functional group equivalent: 430 g / mol)
Amino-modified silicone C: Double-ended amino-modified silicone (manufactured by Shinetsu Silicone, X-22-161B, side chain: methyl group, kinematic viscosity 25 ° C: 55 mm ² / s, functional group equivalent: 1500 g / mol)
Amino-modified silicone D: Double-ended amino-modified silicone (manufactured by Shinetsu Silicone Co., Ltd., X-22-9409, side chain: phenyl group, kinematic viscosity 25 ° C.: 105 mm ² / s, functional group equivalent: 670 g / mol)

(Synthesis Example 6)
The total amount of layered titanic acid obtained in the same manner as in Synthesis Example 1 was added to the deionized water so as to be 1.5 kg in total with the deionized water, and while being dispersed and stirred, 52.1 g (1 equivalent) of octadecylamine was added. ) Was dispersed in 1 kg of deionized water, and the mixture was further stirred at 70 ° C. for 1 hour. Then, it was separated by suction filtration and washed with water to obtain flaky titanium acid.

(Synthesis Example 7)
The total amount of layered titanic acid obtained in the same manner as in Synthesis Example 1 was added to the deionized water so as to be 2.5 kg in total with the deionized water, and while being dispersed and stirred, 35.9 g (1) of dimethyldecylamine was added. Equivalent) was added, and the mixture was further stirred at room temperature for 1 hour. Then, it was separated by suction filtration and washed with water to obtain flaky titanium acid.

<Preparation of pigment composition and coating film>
(Example 1)
Ethyl cellulose (hydroxyl substitution degree: 2.54, organic group: ethyl group) 10% by mass solution (solvent:) so that the flaky titanium acid aggregate obtained in Synthesis Example 1 has a PWC (pigment mass concentration) of 10%. After stirring (rotation: 800 rpm, revolution: 2000 rpm) for 10 minutes using xylene) and a defoaming conditioning mixer "Awatori Rentaro AR-250" (manufactured by Shinky Co., Ltd.), defoaming (rotation: 60 rpm, Revolution: 2200 rpm) was carried out for 2 minutes to obtain a pigment composition. The obtained pigment composition did not show sedimentation of solid content even after being allowed to stand for a long time, and had sufficient dispersion stability. The pigment composition was applied twice on a white coating plate with a film applicator having a clearance of 200 μm, and a 10% by mass solution of ethyl cellulose was applied once as a top coat with a film applicator having a clearance of 200 μm. Each time it was applied in the above step, it was dried at room temperature. In the obtained coating film, flaky titanium acid having a thickness of 20 nm to 50 nm and an average major axis of 15 μm is uniformly and parallelly dispersed and oriented in the resin coating film in a very dense state by SEM observation of the cross section of the coating film. It was confirmed that. The film thickness of the obtained coating film was 30 μm for the layer formed from the pigment composition and 50 μm for the top coat layer.

(Examples 2 to 5)
A coating film was prepared in the same manner as in Example 1 using the flaky titanium acid aggregates of Synthesis Examples 2 to 5. In the obtained coating films in Examples 2 to 5, flaky titanium acid having a thickness of 20 nm to 50 nm and an average major axis of 15 μm was contained in the resin coating film in a very dense state by SEM observation of the cross section of the coating film. It was confirmed that the dispersion orientation was uniform and parallel. The film thickness of the obtained coating film was 30 μm for the layer formed from the pigment composition and 50 μm for the top coat layer.

(Example 6)
Ethyl cellulose (hydroxyl substitution degree: 2.54, organic group: ethyl group) 10% by mass solution (solvent: xylene) was applied in the same manner as in Example 1 so that the flaky titanic acid aggregate of Synthesis Example 1 had a PWC of 10%. The mixture was mixed, 1.3% by mass of a polyisocyanate solution (Retan PG80 curing agent manufactured by Kansai Paint Co., Ltd.) was added to the mixed solution, and the mixture was further mixed in the same manner as in Example 1 to obtain a pigment composition. Using the above pigment composition, a coating film was prepared in the same manner as in Example 1. Also in Example 6, the obtained coating film was found to have flaky titanium acid having a thickness of 20 nm to 50 nm and an average major axis of 15 μm uniformly and parallel to the resin coating film in a very dense state by SEM observation of the cross section of the coating film. It was confirmed that the particles were dispersed or oriented. The film thickness of the obtained coating film was 30 μm for the layer formed from the pigment composition and 50 μm for the top coat layer.

(Example 7)
A coating film was prepared in the same manner as in Example 1 by using the flaky titanium acid of Synthesis Example 6 instead of the flaky titanium acid aggregate of Synthesis Example 1. Also in Example 7, the obtained coating film was found to have flaky titanium acid having a thickness of 20 nm to 50 nm and an average major axis of 15 μm uniformly and parallel to the resin coating film in a very dense state by SEM observation of the cross section of the coating film. It was confirmed that the particles were dispersed or oriented. The film thickness of the obtained coating film was 30 μm for the layer formed from the pigment composition and 50 μm for the top coat layer.

(Example 8)
Cellulose acetate butyrate (hydroxyl substitution degree: 2.69, organic group: acetyl group (38%) and butyryl group (62%), number average so that the flaky titanic acid aggregate of Synthesis Example 7 has a PWC of 25%. A 10% by mass solution (solvent: butyl acetate) having a molecular weight of 70,000) was mixed in the same manner as in Example 1, and an acrylic resin (Acrydic WZG-416 manufactured by DIC Co., Ltd.) as a binder resin was mixed with the mixed solution. ), Acid value: 5.8 mgKOH / g) and butylated melamine resin (Amidia J-820-60 manufactured by DIC Co., Ltd.) as a curing agent in a 7: 3 (mass ratio) mixture of flaky titanium. The acid PWC was further added to 10% and mixed in the same manner as in Example 1 to obtain a pigment composition. The pigment composition was applied once on a white coating plate with a film applicator having a clearance of 200 μm, dried at room temperature for 20 minutes, and then baked at 140 ° C. for 20 minutes in a dryer. Further, as a top coat, a 2: 1 (weight ratio) mixture of the main agent and the curing agent of Retan PG Eco HS Clear G (manufactured by Kansai Paint Co., Ltd.) was applied once with a film applicator having a clearance of 200 μm. After drying at room temperature for 20 minutes, it was baked in a dryer at 140 ° C. for 20 minutes. In the obtained coating film, flaky titanium acid having a thickness of 20 nm to 50 nm and an average major axis of 15 μm is uniformly and parallelly dispersed and oriented in the resin coating film in a very dense state by SEM observation of the cross section of the coating film. It was confirmed that. The film thickness of the obtained coating film was 30 μm for the layer formed from the pigment composition and 50 μm for the top coat layer.

(Comparative Example 1)
The total amount of the layered titanic acid obtained in Synthesis Example 1 is added to the deionized water so as to be 800 g together with the deionized water, and 17.3 g (1 equivalent) of dimethylethanolamine is deionized while being dispersed and stirred. A solution dissolved in 182.8 g of water was added, and the mixture was stirred at room temperature for 12 hours to obtain a flaky titanium acid dispersion. The obtained flaky titanium acid dispersion was mixed with an acrylic / melamine cross-linking emulsion paint so as to have a PWC of 10% to prepare a pigment composition. The pigment composition was applied onto a white coated plate with a film applicator so as to have a dry film thickness of 10 μm, and preheated at 80 ° C. for 10 minutes. Acrylic acid / epoxy crosslinked clear paint was applied as a top coat on the surface so as to have a dry film thickness of 35 μm, and baked at 140 ° C. for 25 minutes to prepare a coating film.

<Evaluation of coating film>
The design properties (grainy feeling, silky feeling) of the coating films of Examples 1 to 8 were evaluated by the following test methods. Further, in Examples 5 to 6, Example 8 and Comparative Example 1, the water adhesion resistance was evaluated by the following test method.

[Particle feeling]
The graininess of the coating film was visually evaluated according to the following evaluation criteria.

〇: No grain feeling ×: Particle feeling

[Silky feeling]
With respect to the obtained coating film, a multi-angle spectrophotometer (MA68II, manufactured by X-Rite) was used at an incident angle of 45 ° and a light receiving angle of 15 °, 25 °, 45 °, 75 °, and 110 °. The brightness (L ^* value) was measured and evaluated by the flop index value (FI value) calculated from the lightness (L * value). The higher the FI value, the better the silky feeling.

[Water resistance (cross-cut test)]
According to the "JIS K5400 paint general test method", the coating film coating plate was immersed in warm water at 40 ° C. for 5 hours, and then a tape peeling test was performed by cross-cutting (2 mm square, 100 squares) to evaluate the water adhesion resistance.

<Evaluation result of coating film>
The results are shown in Tables 2 and 3 below.

As can be seen from the evaluation results of the coating film, Examples 1 to 8 have no grainy feeling, excellent silky feeling, and excellent designability. Further, it was confirmed that Examples 5 to 6 and 8 were also excellent in water resistance and adhesion.

1 ... Layered Titanate 2 ... Hydrophobic Amine 3 ... Flake Titanate 4 ... Polysaccharide Derivative

Claims (11)

1. It contains a bright pigment, a basic compound or a salt thereof, a polysaccharide derivative, and an organic solvent.
   The bright pigment is flaky titanium acid,
   A pigment composition in which the polysaccharide derivative is composed of at least a part of hydrogen atoms in the hydroxy group contained in the polysaccharide being replaced with an organic group.
2. The pigment composition according to claim 1, wherein the polysaccharide is cellulose.
3. The organic group is at least one selected from the group consisting of an alkyl group having a substituent, an alkyl group having no substituent, an acyl group having a substituent, and an acyl group having no substituent. The pigment composition according to claim 1 or claim 2.
4. The pigment composition according to any one of claims 1 to 3, wherein the basic compound or a salt thereof is an amino-modified silicone.
5. A claim that the flaky titanium acid is formed by treating the titanate having a layered crystal structure with an acid and then allowing the basic compounds or salts thereof to act on the layers to cause the layers in the layered crystal structure to be swollen and peeled off. The pigment composition according to any one of Items 1 to 4.
6. The pigment composition according to any one of claims 1 to 5, wherein the average major axis of the flaky titanium acid is 5 μm or more and 30 μm or less.
7. The pigment composition according to any one of claims 1 to 6, wherein the flaky titanium acid has an average thickness of 0.5 nm or more and 300 nm or less.
8. The pigment composition according to any one of claims 1 to 7, wherein the organic solvent is an aprotic organic solvent.
9. The pigment composition according to any one of claims 1 to 8, wherein the content of the brilliant pigment is 5% by mass or more and 50% by mass or less in 100% by mass of the solid content of the pigment composition. thing.
10. The invention according to any one of claims 1 to 9, wherein the mass ratio (brilliant pigment / polysaccharide derivative) of the bright pigment to the polysaccharide derivative is 5/95 or more and 50/50 or less. Pigment composition.
11. A coating film to which the pigment composition according to any one of claims 1 to 10 is applied.

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