JP2019167510A - Compound-adhered aluminum pigment - Google Patents

Abstract

To provide an aluminum pigment that can form a metallic coating film excellent in initial adhesion, excellent in metallic luster, designability and adhesion to a resin and also excellent in base concealing property and has high storage stability.SOLUTION: A compound-adhered aluminum pigment contains: (C) a compound composed of (A) a resin compound being a polymer of a radical polymerizable monomer and/or oligomer having one or more double bonds in the molecule and (B) a zirconium compound; and flaky aluminum powder and has the compound (C) in an amount of 0.1 to 10 pts.mass based on 100 pts.mass of the flaky aluminum powder adhered onto the surface of the flaky aluminum powder.SELECTED DRAWING: None

Description

  The present invention relates to a compound-attached aluminum pigment, and a paint and ink containing the compound-attached aluminum pigment.

Conventionally, aluminum pigments have been used for metallic paints, printing inks, plastics kneading, and the like for the purpose of obtaining a cosmetic effect that emphasizes a metallic feeling.
However, aluminum pigments that have not been subjected to any surface treatment have a high metallic feel and design, while depending on the resin system of the paint or printing ink, the adhesion to the resin in the coating film is low. When the adhesion test is carried out, there is a drawback that a large amount is peeled off.

As a method for improving the adhesion of the aluminum pigment as described above, a method of applying a predetermined surface treatment to the aluminum pigment has been proposed.
For example, Patent Documents 1 and 2 describe metallic coating films that are excellent in adhesion to resins when used as pigments for paints and printing inks while maintaining the excellent metallic luster and design of aluminum pigments. An aluminum pigment capable of providing the same and a method for producing the same are disclosed.

JP 2002-226733 A JP2015-172162 PR

  However, in recent years, the demand for aluminum pigments has further increased. For example, in printing ink applications, it is required to increase the printing speed in order to improve productivity. In order not to occur, improvement of adhesion (initial adhesion) before the ink is completely dried has been a problem. Furthermore, in addition to having excellent design properties, adhesion to resins, and excellent concealment with respect to the base, it is also required to have high storage stability that is hardly affected by outside air temperature.

  Therefore, in the present invention, in view of the above-mentioned problems of the prior art, the metallic coating is excellent in initial adhesion, excellent in metallic luster, design and adhesion with resin, and also in excellent concealment with respect to the base. An object is to provide an aluminum pigment having a high storage stability capable of forming a film.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have (A) a resin compound that is a polymer of a radical polymerizable monomer and / or oligomer having one or more double bonds in the molecule; B) A compound-attached aluminum pigment containing a compound (C) comprising a zirconium compound and flaky aluminum powder, and the compound (C) is attached to the flaky aluminum powder is excellent in the initial stage. The present inventors have found that the adhesiveness, the designability, the excellent adhesiveness with the resin, and the excellent concealing property with respect to the substrate can be exhibited, and that the effect of excellent storage stability can be exhibited, and the present invention has been completed.
That is, the present invention is as follows.

[1]
(A) a resin compound that is a polymer of a radically polymerizable monomer and / or oligomer having one or more double bonds in the molecule;
(C) a compound comprising (B) a zirconium compound;
Flaky aluminum powder,
Containing
0.1 to 10 parts by mass of the (C) compound is attached to the surface of the flaky aluminum powder with respect to 100 parts by mass of the flaky aluminum powder.
Compound-attached aluminum pigment.
[2]
The compound-attached aluminum pigment according to [1], wherein the zirconium compound (B) is zirconium acetate, zirconium propionate, or zirconium phosphate.
[3]
When the compound-attached aluminum pigment is heat-treated at 50 ° C. for 135 days, an average particle diameter difference Δd50 between the compound-attached aluminum pigment subjected to the heat treatment and the compound-attached aluminum pigment not subjected to the heat treatment is 1 The compound-attached aluminum pigment according to [1] or [2], which exhibits a storage stability of less than 0.0 μm.
[4]
A paint containing the compound-attached aluminum pigment according to any one of [1] to [3].
[5]
An ink containing the compound-attached aluminum pigment according to any one of [1] to [3].
[6]
Dispersing the flaky aluminum powder in an organic solvent, and (A) adding a radically polymerizable monomer and / or oligomer having one or more double bonds in the molecule and a polymerization initiator, and addition thereof A method for producing the compound-attached aluminum pigment according to any one of [1] to [3], further comprising (B) a step of further adding a zirconium compound.

  According to the present invention, excellent initial adhesion, excellent metallic luster, design and adhesion to resin, and high storage stability capable of forming a metallic coating film excellent in concealment with respect to the base. A compound-attached aluminum pigment is obtained.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified within the scope of the gist.

[Compound-attached aluminum pigment]
The compound-attached aluminum pigment of this embodiment is
(A) a resin compound that is a polymer of a radically polymerizable monomer and / or oligomer having one or more double bonds in the molecule;
(C) a compound comprising (B) a zirconium compound;
Flaky aluminum powder,
Containing
0.1 to 10 parts by mass of the (C) compound is attached to the surface of the flaky aluminum powder with respect to 100 parts by mass of the flaky aluminum powder.

As described above, the compound-attached aluminum pigment of this embodiment includes (A) a resin compound that is a polymer of a radical polymerizable monomer and / or oligomer having one or more double bonds in the molecule, and (B) zirconium. The (C) compound which consists of a compound, and flaky aluminum powder are contained. And the (C) compound has adhered to the surface of flaky aluminum powder.
The compound (C) adhering to the flaky aluminum powder does not simply mean that the flaky aluminum powder and the compound are mixed, but there is an interaction between the “flaky aluminum powder” and the “compound”. It means a certain state.
Examples of the interaction include a chemical bond, a hydrogen bond, an ionic bond, and a van der Waals force.

(Flake aluminum powder)
As the flaky aluminum powder used for the compound-attached aluminum pigment of the present embodiment, those having surface properties, particle sizes, and shapes required for metallic pigments such as surface gloss, whiteness, and glitter are suitable.
The shape may be various shapes such as a granular shape, a plate shape, a lump shape, and a scaly shape, but a scaly shape is preferable in order to give an excellent metallic feeling and luminance to the coating film.
The flaky aluminum powder has a thickness in the range of 0.001 to 1 μm, and preferably has a length or width in the range of 1 to 100 μm.
The aspect ratio of the flaky aluminum powder is preferably in the range of 10 to 20000.
Here, the aspect ratio is a value obtained by dividing the average major axis of the flaky aluminum powder by the average thickness of the flaky aluminum powder.
In addition, the purity of the flaky aluminum powder is not particularly limited, but it is preferable that the purity of the flaky aluminum powder is 99.5% or more.
The flaky aluminum powder can be obtained by a known method, for example, a production method described in WO99 / 54074, but is usually commercially available in a paste state, and this can also be used.

((A) Resin compound that is a polymer of a radically polymerizable monomer and / or oligomer having one or more double bonds in the molecule)
The resin compound defined in (A) (also referred to as “(A) resin compound” in the present application) is a polymer of a radical polymerizable monomer and / or oligomer having one or more double bonds in the molecule. .
It does not specifically limit as said radically polymerizable monomer and / or oligomer, A conventionally well-known thing can be used.
Examples of the radical polymerizable monomer and / or oligomer include, but are not limited to, for example, (meth) acrylic acid, (meth) acrylic acid ester, aromatic vinyl compound, and vinyl cyanides. Amide group-containing vinyl monomers, hydroxyl group-containing vinyl monomers, epoxy group-containing vinyl monomers, carbonyl group-containing vinyl monomers, anionic vinyl monomers, mono- or diesters of phosphoric acid or phosphonic acid, Examples thereof include vinyl monomers having a silyl group.

  In the present specification, (meth) acrylic is a simple description of methacrylic or acrylic.

Examples of the (meth) acrylic acid ester include, but are not limited to, for example, a (meth) acrylic acid alkyl ester having 1 to 50 carbon atoms in the alkyl part and a number of ethylene oxide groups of 1 to 100. (Poly) oxyethylene di (meth) acrylate etc. are mentioned.
Examples of (meth) acrylic acid alkyl esters include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid. Examples include 2-ethylhexyl, methyl cyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, and the like.
Examples of (poly) oxyethylene di (meth) acrylate include, but are not limited to, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol methoxy (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate.
In addition, trimethylolpropane tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, di-pentaerythritol hexa (meth) acrylate, Examples thereof include di-pentaerythritol penta (meth) acrylate, di-pentaerythritol penta (meth) acrylate monopropionate, and the like.

  The hydroxyl group-containing vinyl monomer is not limited to the following, and examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meta). ) Hydroxyalkyl esters of (meth) acrylic acid such as acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and di-2-hydroxyethyl fumarate , Mono-2-hydroxyethyl monobutyl fumarate, allyl alcohol and (poly) oxyethylene mono (meth) acrylate having 1 to 100 ethylene oxide groups, 1 to 100 (poly) propylene oxide groups Oxypropylene mono (meth) acrylate Furthermore, "PLACCEL FM, FA monomer" (manufactured by Daicel Chemical Industries, Ltd., trade name of caprolactone addition monomer) and other alpha, hydroxyalkyl esters of β- ethylenically unsaturated carboxylic acid and the like.

  Examples of the (poly) oxyethylene mono (meth) acrylate include, but are not limited to, ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, Examples include methoxy (meth) acrylic acid diethylene glycol, (meth) acrylic acid tetraethylene glycol, and methoxy (meth) acrylic acid tetraethylene glycol.

  In addition, the (poly) oxypropylene mono (meth) acrylate is not limited to the following, but, for example, propylene glycol (meth) acrylate, propylene glycol methoxy (meth) acrylate, dimethacrylate (meth) acrylate Examples include propylene glycol, dipropylene glycol methoxy (meth) acrylate, tetrapropylene glycol (meth) acrylate, and tetrapropylene glycol methoxy (meth) acrylate.

  Examples of the epoxy group-containing vinyl monomer include, but are not limited to, glycidyl (meth) acrylate, allyl glycidyl ether, allyl dimethyl glycidyl ether, and the like.

  The mono- or diesters of phosphoric acid or phosphonic acid are not limited to the following, but examples include 2-methacryloyloxyethyl phosphate, di-2-methacryloyloxyethyl phosphate, tri-2- Methacryloyloxyethyl phosphate, 2-acryloyloxyethyl phosphate, di-2-acryloyloxyethyl phosphate, tri-2-acryloyloxyethyl phosphate, diphenyl-2-acryloyloxyethyl phosphate, dibutyl-2-methacryloyl Roxyethyl phosphate, dioctyl-2-acryloyloxyethyl phosphate, 2-methacryloyloxypropyl phosphate, bis (2-chloroethyl) vinylphosphonate, diallyldibutylphosphonosuccinate, 2-methacrylic Gray ethyl phosphate, 2-acryloyl acetoxyphenyl ethyl phosphate.

  Further, the vinyl monomer having a silyl group is not limited to the following, but examples thereof include 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropyltriethoxysilane. 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Examples include allyltrimethoxysilane and 2-trimethoxysilylethyl vinyl ether.

Examples of other (A) resin compounds include, but are not limited to, olefins such as (meth) acrylamide, ethylene, propylene, and isobutylene; dienes such as butadiene; vinyl chloride and vinylidene chloride fluoride Haloolefins such as vinyl, tetrafluoroethylene, chlorotrifluoroethylene; vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl benzoate, vinyl pt-butylbenzoate, vinyl pivalate, 2-ethylhexanoic acid Carboxylic acid vinyl esters such as vinyl, vinyl versatate and vinyl laurate; Carboxylic acid isopropenyl esters such as isopropenyl acetate and isopropenyl propionate; Vinyl vinyl such as ethyl vinyl ether, isobutyl vinyl ether and cyclohexyl vinyl ether Ethers; aromatic vinyl compounds such as styrene and vinyltoluene, allyl esters such as allyl acetate and allyl benzoate; allyl ethers such as allyl ethyl ether and allyl phenyl ether; and 4- (meth) acryloyloxy-2, 2,6,6, -tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6, -pentamethylpiperidine, perfluoromethyl (meth) acrylate, perfluoropropyl (meth) acrylate, Examples thereof include perfluoropropylmethyl (meth) acrylate, vinyl pyrrolidone, allyl (meth) acrylate, and the like.
(A) A resin compound may be used individually by 1 type, and may use 2 or more types together.

((B) zirconium compound)
The zirconium compound defined in (B) (also referred to as “(B) zirconium compound” in the present application) is not particularly limited, and conventionally known compounds can be used.
(B) Examples of zirconium compounds include ammonium zirconium carbonate, zirconium orthosulfate, zirconium nitrate, zirconium sulfate, zirconium acetate, zirconium propionate, basic zirconium carbonate, zirconium zirconium chloride, zirconium oxychloride, zirconium phosphate, phosphoric acid. Examples include sodium zirconium, potassium zirconium carbonate, hydrofluoric zirconate, and ammonium zirconate fluoride.
(B) A zirconium compound may be used individually by 1 type, and may use 2 or more types together.

In the compound-attached aluminum pigment of this embodiment, the compound (C) comprising 0.1 to 10 parts by mass of the (A) resin compound and (B) a zirconium compound with respect to 100 parts by mass of the flaky aluminum powder described above. Containing. And the (C) compound has adhered to the surface of flaky aluminum powder.
(C) Content of a compound shall be 0.1 mass part or more from a viewpoint of adhesiveness etc. (especially adhesiveness), and shall be 10 mass parts or less from a viewpoint of glossiness, designability, etc. (especially glossiness and designability). It is preferable that it is 0.5-6 mass parts with respect to 100 mass parts of flaky aluminum powder from a viewpoint of the more outstanding storage stability.

(Polymerization initiator)
When producing the compound-attached aluminum pigment of this embodiment, it is preferable to use a polymerization initiator.
The method for producing the compound-attached aluminum pigment of this embodiment will be described later.
The polymerization initiator is generally known as a radical generator, and the type thereof is not particularly limited.
Examples of the polymerization initiator include, but are not limited to, peroxides such as benzoyl peroxide, lauroyl peroxide, bis- (4-t-butylcyclohexyl) peroxydicarbonate, and 2,2′-azobis. -Azo compounds such as isobutyronitrile and 2,2'-azobis-2,4-dimethylvaleronitrile.
The amount of the polymerization initiator used is not particularly limited because it is adjusted by the reaction rate of the radically polymerizable monomer and / or oligomer constituting the resin compound (A), but the compound-attached aluminum pigment of this embodiment is not limited. From the viewpoint of manufacturability and the like, it is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the flaky aluminum powder.

(Other ingredients)
As described later, the compound-attached aluminum pigment of the present embodiment is a radical polymerizable monomer and / or oligomer that constitutes the resin compound (A) described above after flaky aluminum powder is dispersed in a predetermined organic solvent. In addition, a chain transfer agent may be added for the purpose of controlling the molecular weight of the reaction product.
Examples of the chain transfer agent include, but are not limited to, alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, and t-dodecyl mercaptan; aromatics such as benzyl mercaptan and dodecyl benzyl mercaptan. Group mercaptans; thiocarboxylic acids such as thiomalic acid or their salts, or alkyl esters thereof, or polythiols, diisopropylxanthogen disulfide, di (methylenetrimethylolpropane) xanthogen disulfide and thioglycol, and α-methylstyrene And allyl compounds such as dimers.
The amount of the chain transfer agent used is preferably 0.001 to 30% by mass, more preferably 0.05 to 10% by mass with respect to (A) the resin compound.

[Method for producing compound-attached aluminum pigment]
The compound-attached aluminum metal pigment of the present embodiment is a radically polymerizable monomer and / or oligomer that constitutes a resin compound while being heated and stirred after dispersing flaky aluminum powder in an organic solvent, Adding a polymerization initiator, reacting (polymerizing) the radical polymerizable monomer and / or oligomer constituting 90% or more of the (A) resin compound, and then adding the (B) zirconium compound and continuing the reaction. Can be manufactured.
The organic solvent may be inert to the flaky aluminum powder, and is not limited to the following, for example, aliphatic hydrocarbons such as hexane, heptane, octane, mineral spirits; benzene, toluene, Aromatic hydrocarbons such as xylene and solvent naphtha; ethers such as tetrahydrofuran and diethyl ether; alcohols such as ethanol, 2-propanol and butanol; esters such as ethyl acetate and butyl acetate; cellosolve such as ethylene glycol monoethyl ether Kind.

The mass concentration of the flaky aluminum powder in the organic solvent is preferably 0.1 to 40% by mass, more preferably 1 to 35% by mass.
0.1 mass% or more is preferable from the viewpoint of reaction rate, and 40 mass% or less is preferable from the viewpoint of dispersibility.

(A) When using a polymerization initiator in the polymerization reaction of the radically polymerizable monomer and / or oligomer constituting the resin compound, the timing of adding the polymerization initiator is not particularly limited. Is preferably added at the same time as the radical polymerizable monomer and / or oligomer, or added later.
The temperature at which the polymerization initiator is added is not particularly limited as long as the polymerization reaction of the radically polymerizable monomer and / or oligomer constituting the resin compound (A) occurs. From the viewpoint of manufacturability of the compound-attached aluminum pigment in the form, 60 ° C. to 150 ° C. is preferable. Moreover, it is preferable to add and react in an inert gas atmosphere such as nitrogen or helium in order to increase the reaction efficiency.

In the reaction of the radically polymerizable monomer and / or oligomer constituting the resin compound (A), a solvent can be added or substituted as necessary.
As the organic solvent, an ester-based solvent is preferable from the viewpoint of environmental load and drying property.
In particular, when propyl acetate is used, the amount of residual solvent is small even when the drying temperature is low, which is preferable from the viewpoint of adhesion and odor.
The particle diameter of the flaky aluminum powder is increased by adhering the compound (C) comprising (A) a resin compound and (B) a zirconium compound. The difference in the average particle size before and after the adhesion is preferably 1.5 μm or less, more preferably 1.0 μm or less, from the viewpoint of concealment of the aluminum pigment of the present embodiment with respect to the base.

[Usage mode of compound-attached aluminum pigment]
The compound-attached aluminum pigment of this embodiment can be used as a pigment for paints and inks. As the paint or ink, either a solvent type or an aqueous type can be used.
When the compound-attached aluminum pigment of this embodiment is used in solvent-type paints and inks, the paint resin or ink resin conventionally used in metallic paints and metallic inks should be used as the paint resin or ink resin. Can do.
The paint or ink resin is not limited to the following, but examples include acrylic resins, alkyd resins, oil-free alkyd resins, vinyl chloride resins, urethane resins, melamine resins, unsaturated polyester resins, urea resins. , Cellulose resin, epoxy resin, fluororesin and the like.
These may be used alone or in combination of two or more.

  When the compound-attached aluminum pigment of the present embodiment is used as a solvent-based paint and ink pigment, the amount of the aluminum pigment used is 0.1 to 300 parts by mass with respect to 100 parts by mass of the resin for paint or ink. Is preferable, and 0.2-200 mass parts is more preferable. 0.1 mass parts or more is preferable from the viewpoint of metallic gloss, and 300 mass parts or less is preferable from the viewpoint of physical properties of the coating film.

Solvent-type paints and ink diluents are not limited to the following, but include, for example, aromatic compounds such as toluene and xylene; aliphatic compounds such as hexane, heptane, and octane; ethanol, butanol, etc. Examples include alcohols; esters such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone; chlorine compounds such as trichloroethylene; and cellosolves such as ethylene glycol monoethyl ether. These diluents may be used alone or in a combination of two or more.
The composition of the diluent may be appropriately determined in consideration of solubility in paint and ink resins, coating film formation characteristics, coating workability, and the like.

  In addition, for paints and inks, pigments, dyes, wetting agents, dispersants, anti-splitting agents, leveling agents, slip agents, anti-skinning agents, anti-gelling agents, antifoaming agents commonly used in the paint industry An additive such as an agent may be further added.

The paint and ink can also be used as a water-based paint by using a water-based paint resin.
However, when an aluminum pigment is used, it may react with water in water-based paints and inks. In such a case, it is necessary to add a reaction inhibitor.
Here, the resin for water-based paints is a water-soluble resin or a water-dispersible resin, and may be used alone or in a mixture of two or more. The type may be appropriately selected depending on the purpose and application, and is not particularly limited, but for paints, water-based paint resins such as acrylic, acrylic-melamine, polyester, and polyurethane are generally used. Of these, acrylic-melamine is most commonly used.

  When used as a water-based paint or ink, the amount of the aluminum pigment used in the present embodiment is preferably 0.1 to 300 parts by weight, and 0.2 parts by weight with respect to 100 parts by weight of the resin for water-based paint. It is more preferable that it is part-200 mass parts. From the viewpoint of obtaining metallic luster, it is preferably 0.1 parts by mass or more, and from the viewpoint of physical properties of the coating film, it is preferably 300 parts by mass or less.

  Examples of various additives include dispersants, thickeners, sagging inhibitors, antifungal agents, ultraviolet absorbers, film forming aids, surfactants, other organic solvents, water, etc. Any of those that can be generally used and that does not impair the effects of the present invention can be used, and it is preferably added in an amount that does not impair the effects of the present invention.

[Painting method]
As a coating method using a paint or ink containing the compound-attached aluminum group pigment of the present embodiment, a known method can be applied.
For example, spraying method, flow coating method, roll coating method, brush coating method, dip coating method, spin coating method, screen printing method, casting method, gravure printing method, flexographic printing method and the like can be mentioned.
Further, after coating, it is possible to carry out heat treatment at 20 to 500 ° C., more preferably 40 to 250 ° C., ultraviolet irradiation or the like, if desired. Moreover, it is also possible to apply | coat a coating material with respect to the base material heated at 40-250 degreeC.

[Use]
The compound-attached aluminum pigment of this embodiment can be used for painting for automobiles, general household appliances, information household appliances represented by mobile phones, or predetermined printing applications.
A base material made of a predetermined material such as a metal such as iron or magnesium alloy or plastic can be painted or printed, and high design properties can be exhibited.

  Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.

In Examples and Comparative Examples, various physical properties were measured by the following methods.
[Method for measuring physical properties]
<1. Average particle diameter>
Manufactured by Shimadzu Corporation; using SALD-2200 (laser diffraction particle size distribution measuring device), a compound-attached aluminum pigment and paste containing flaky aluminum powder (manufactured by Asahi Kasei Corporation, manufactured by Examples and Comparative Examples described later) The average particle size of GX-4100) was measured.

<2. Compound amount>
The amount of the compound (C) relative to 100 parts by mass of the flaky aluminum powder is (A) when the mass (2000 g × 0.74) of the non-volatile content of the aluminum paste used as the flaky aluminum powder component is 100 parts by mass. The mass part which becomes the sum total of a resin compound and (B) zirconium was computed, and it was set as the value.

<3. Initial adhesion>
The metallic ink obtained in each Example and Comparative Example was applied to a PET film with a bar coater so as to have a dry film thickness of 2 μm to obtain a coating film.
A sample obtained by drying the obtained coating film at 50 ° C. for 2 hours was used as an evaluation sample.
Cellotape (registered trademark: manufactured by Nichiban Co., Ltd., width: 18 mm) was closely attached to the coating film, pulled at an angle of 90 °, and the degree of peeling of the aluminum pigment particles was visually observed and evaluated as follows.
◎: No peeling was observed. ○: Almost no peeling was observed. △: Some peeling was observed. ×: Remarkable peeling was observed.

<4. Concealment>
The metallic ink obtained in each Example and Comparative Example was applied to a PET film with a bar coater so as to have a dry film thickness of 2 μm to obtain a coating film.
A sample obtained by drying the obtained coating film at 50 ° C. for 24 hours was used as an evaluation sample.
Using a haze meter HZ-V3 manufactured by Suga Test Instruments Co., Ltd., the total light transmittance (Tt) was evaluated.
The smaller the value, the better the concealment.

<5. Metal gloss>
<3. A coating film produced in the same manner as the dried coating film used for the evaluation of concealment property was subjected to evaluation.
A 60 degree gloss (both incident angle and reflection angle is 60 degrees) is measured using a gloss meter (manufactured by Suga Test Instruments Co., Ltd., digital variable gloss meter UGV-5D). G 'is a measured value of 60 ° gloss of a coated plate using the metal pigment of the present invention, and G is a measured value of 60 ° gloss of a coated plate similarly produced using a metal pigment not coated with a resin. R was determined by the following equation.
R = (G ′ / G) × 100
Depending on the value of the gloss retention rate R, the evaluation was as follows.
The larger the numerical value, the better, and from a practical point of view, a value of 70 or more was judged to be good.
◎ (excellent): 90 or more ○ (good): less than 90 to 80 or more Δ (possible): less than 80 to 70 or more × (impossible): less than 70 <6. Storage stability>
The compound-attached aluminum pigment produced according to Examples and Comparative Examples described later was heat-treated at 50 ° C. The storage stability was evaluated as follows according to the increase degree (aggregation degree) of the average particle diameter before and after heat treatment.
The smaller the Δd50 value was, the better, and from a practical point of view, it was judged to be good if it kept 1.5 or less after 135 days of heat treatment at 50 ° C.
○ (good): 135 days at 50 ° C., Δd50 ≦ 1.0 μm
Δ (possible): 135 days at 50 ° C., 1.0 μm <Δd50 ≦ 1.5 μm
× (Not possible): 135 days at 50 ° C., Δd50> 1.5 μm

[Example 1]
In a 20 L reactor, 2000 g of a commercially available paste containing flaky aluminum powder (manufactured by Asahi Kasei Co., Ltd., GX-4100 “average particle size 10 μm, non-volatile content 74 mass%”) and 8300 g of mineral spirits were charged. And it stirred, introducing nitrogen gas, and raised the temperature in a system to 70 degreeC. Next, 24.0 g of acrylic acid was added and stirring was continued for 30 minutes. Thereafter, a liquid consisting of 3.0 g of 2,2′-azobis-2,4-dimethylvaleronitrile and 1200 g of mineral spirit was added at a rate of about 10 g / min with a metering pump. The mixture was stirred for a total of 6 hours while maintaining the temperature. After completion of the reaction for 6 hours, a mixed liquid consisting of 3.0 g of zirconium phosphate and 12.0 g of isopropanol and 1188.0 g of mineral spirit was then added at a rate of about 10 g / min with a metering pump. The mixture was finally stirred for a total of 12 hours while keeping the temperature at 70 ° C.
After the reaction for 12 hours, the mixture was naturally cooled and the slurry was filtered to obtain a compound-attached aluminum paste (aluminum pigment).
The non-volatile content of the aluminum pigment according to JIS-K-5910 was 50% by mass.
The difference between the average particle size before and after the reaction, that is, the average particle size of the aluminum pigment, and the average particle size of the commercially available paste containing flaky aluminum powder was 0.5 μm.
To 6 g of the obtained aluminum pigment, 10 g of polyurethane resin (Samprene IB-1700D (manufactured by Sanyo Chemical Industries)), 4 g of ethyl acetate, 4 g of methyl ethyl ketone, and 4 g of isopropanol are added, and stirred with a magnetic stirrer for 10 minutes. Got.
The obtained metallic ink was used to evaluate the initial adhesion of the coating film, the concealing property of the coating film, and the metallic gloss, and the storage stability of the compound-attached aluminum pigment obtained in this example was also evaluated. The evaluation results are shown in Table 1 below.

[Examples 2 to 5], [Comparative Examples 1 to 3]
The composition of Example 1 was changed, and the other compound-adhesive aluminum pigments and paints were produced in the same manner. Table 1 also shows compositions of Examples 2 to 5 and Comparative Examples 1 to 3 and evaluation results.

[Table 1]

In Examples 1 to 5, excellent initial adhesion and metallic luster, high concealability, and excellent storage stability can be obtained, and excellent design can be obtained in view of these results. I understood.

  The compound-attached aluminum pigment of the present invention is used for paints and printing inks for information home appliances such as automobiles, general home appliances, and mobile phones, specifically, metals such as iron and magnesium alloys, or plastics. It has industrial applicability in paint and ink applications for such substrates.

Claims (6)

(A) a resin compound that is a polymer of a radically polymerizable monomer and / or oligomer having one or more double bonds in the molecule;
(C) a compound comprising (B) a zirconium compound;
Flaky aluminum powder,
Containing
A compound-attached aluminum pigment, wherein 0.1 to 10 parts by mass of the compound (C) is attached to the surface of the flaky aluminum powder with respect to 100 parts by mass of the flaky aluminum powder.   The compound-attached aluminum pigment according to claim 1, wherein the zirconium compound (B) is at least one selected from zirconium acetate, zirconium propionate, and zirconium phosphate.   When the compound-attached aluminum pigment is heat treated at 50 ° C. for 135 days, the average particle size difference Δd50 between the heat-treated compound-attached aluminum pigment and the compound-attached aluminum pigment not subjected to the heat treatment is 1 The compound-attached aluminum pigment according to claim 1 or 2, which is less than 0.0 µm.   The coating material containing the compound adhesion aluminum pigment as described in any one of Claims 1 thru | or 3.   The ink containing the compound adhesion aluminum pigment as described in any one of Claims 1 thru | or 3.   Dispersing the flaky aluminum powder in an organic solvent, and (A) adding a radically polymerizable monomer and / or oligomer having one or more double bonds in the molecule and a polymerization initiator, and addition thereof The method of manufacturing the compound adhesion aluminum pigment as described in any one of Claims 1 thru | or 3 which includes the process of further adding (B) a zirconium compound later.