JP3425490B2 - Aluminum pigment - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aluminum pigment used in organic solvent type paints and organic solvent type inks.

[0002]

2. Description of the Related Art Organic solvent-based metallic paints containing aluminum pigments have already been widely used for coating automobile exterior panels. The aluminium pigment is usually produced by wet-milling aluminum in the presence of a lubricant such as saturated or unsaturated fatty acid such as stearic acid or oleic acid. The surface of the aluminum pigment thus treated is inactivated, but if anthraquinone-based, pyranthrone-based, quinacridone-based, and perylene-based organic pigments coexist in the system, these organic pigments discolor in the paint. (Bleaching) may occur.

In order to prevent such discoloration, it has been considered to treat the aluminum pigment after pulverization with an aliphatic amine, but there was little effect. Further, after treating with the above fatty acid, further treating with water dispersed in isopropyl alcohol (Japanese Patent Publication No. 63-25634).
Or acid phosphate compound treatment (Japanese Patent Publication No. 2-
31751), but it was difficult to solve the discoloration prevention.

Further, in the organic solvent type metallic paint, it is necessary to add 8 phr or more of aluminum pigment (8 parts by weight of aluminum flakes per 100 parts by weight of resin solid content) in order to finish it in silver or light color. If this amount of aluminum pigment treated with is blended to this extent, the adhesion to the vehicle component in the coating film is not sufficient,
As a result, it has a defect of causing cohesive failure in the metallic coating film.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic solvent type aluminum pigment that solves the above problems (discoloration of organic pigment and cohesive failure in metallic coating film).

[0006]

[Means for Solving the Problems] As a result of study to solve the above-mentioned problems, it was found that P on the aluminum flakes was 0.0 in terms of P with respect to the aluminum flakes.
1% by weight or more of a phosphoric acid ester (A) produced by an esterification reaction of a polyfunctional epoxy compound and a phosphorus compound, or a phosphoric acid ester amine salt (B) obtained by neutralizing the phosphoric acid ester (A) with an amine compound or an amide compound. ) [Hereinafter, the components (A) and (B) are collectively referred to as a "treatment agent"), thereby adsorbing an organic solvent type aluminum pigment excellent in discoloration resistance and cohesive failure resistance in a coating film. Found that can be provided.

The aluminum flakes used for preparing the aluminum pigment of the present invention are produced by crushing and grinding aluminum in a ball mill or attritor mill in the presence of a grinding medium with a grinding aid. It is a flake. From the viewpoint of color tone, the average particle diameter (D ₅₀ ) is 1 to 5
It is preferably about 0 μm, particularly preferably about 5 to 40 μm.
As the grinding aid, higher fatty acids such as oleic acid, stearic acid, isostearic acid, lauric acid, palmitic acid and myristic acid, as well as aliphatic amines and aliphatic amides,
Aliphatic alcohols are used. Aliphatic hydrocarbons such as mineral spirits are used as the grinding medium.

It is effective to replace the aluminum flakes with an organic solvent capable of dissolving the treating agent in advance. As the organic solvent, an aromatic hydrocarbon solvent such as toluene, xylene, solvent naphtha, Solvesso 100 (manufactured by Esso Oil Co., Ltd.) is desirable.

The polyfunctional epoxy compound used for preparing the treating agent is a compound having two or more epoxy groups in one molecule, and more specifically, it is an alicyclic hydrocarbon (having 4 to 4 carbon atoms). (Preferably seven), an alicyclic epoxy compound having two or more alicyclic epoxy groups in which an epoxy group is directly bonded to a carbon atom constituting a ring, and two or more hydroxyl groups contained in an aliphatic polyhydric alcohol. Examples thereof include aliphatic epoxy compounds formed by glycidyl etherification.

Examples of the alicyclic epoxy compound include 2
It is preferable that one or more alicyclic epoxy groups are bound by a lactone chain or the like. Specific examples include trade names of "Celoxide 2081" and "Celoxide 2085" manufactured by Daicel Chemical Industries, Ltd., and their chemical structural formulas are as follows.

Structural formula of "Celoxide 2081":

[0012]

[Chemical 1]

Structural formula of "Celoxide 2085":

[0014]

[Chemical 2]

The alicyclic epoxy compound has a molecular weight of about 30.
0 to about 1000, especially about 700 to about 1000, and epoxy equivalents in the range of about 150 to about 500, especially about 350 to about 500 are preferred.

The aliphatic epoxy compound is formed by glycidyl etherification of two or more hydroxyl groups contained in the aliphatic polyhydric alcohol. The aliphatic polyhydric alcohol is a compound having two or more hydroxyl groups in one molecule, and specific examples thereof include neopentyl glycol, hexanediol and propylene glycol. An aliphatic epoxy compound can be obtained by converting all the hydroxyl groups of these aliphatic polyhydric alcohols into glycidyl ethers by a known method. The molecular weight of the aliphatic epoxy compound is about 150 to about 1000, especially about 180 to about 400, and the epoxy equivalent is about 100 to about 600, especially about 120 to about 250.
The range of is preferable.

The phosphorus compound used in the preparation of the treating agent has the formula O
The compound represented by P (OH) ₃ is preferred.

The treating agent used in the present invention is obtained by subjecting the polyfunctional epoxy compound and the phosphorus compound to an esterification reaction, and this reaction is carried out by opening the epoxy group of the polyfunctional epoxy compound and the hydroxyl group of the phosphorus compound. It is carried out by a ring reaction, and the reaction conditions can be carried out according to a usual ring opening reaction. The reaction ratio between the epoxy group of the polyfunctional epoxy compound and the hydroxyl group of the phosphorus compound is most preferably 1: 1.

Specific examples of the phosphate ester (A) (treatment agent) thus obtained are as follows.

Example using "Celoxide 2081" (Structural Formula 1):

[0021]

[Chemical 3]

Example using "Celoxide 2085" (Structural Formula 2):

[0023]

[Chemical 4]

Example using an aliphatic diol:

[0025]

[Chemical 5]

[In the formula, n ₁ is an integer of 0 to 9, and X is —CH ₂ —CHR ₁ R ₂ —CH ₂ —O— (where R ₁ ,
R ₂ is hydrogen or —CH ₃ or —CH ₂ —CH ₃ or —C
H ₂ represented by any of OH) or - (CH _2)
n2 -O- (where n ₂ is a is an integer from 1 to 6) is represented by, Y ² is the formula (i) or formula (ii):

[0027]

[Chemical 6]

It is represented by The treatment agent used in the present invention also includes a phosphoric acid ester amine salt (B) obtained by neutralizing the phosphoric acid ester (A) by reacting it with an amine compound or an amide compound. As the amine compound used for neutralization, for example, ammonia: benzylamine, monoethanolamine, neopentanolamine, 2-aminopropanol, 3-
Primary amines such as aminopropanol and linear or branched aliphatic amines having 1 to 18 carbon atoms: diethanolamine, dipropanolamine and 1 to 1 carbon atoms
Secondary amines such as linear or branched aliphatic amines of 8: dimethylethanolamine, trimethylamine,
Tertiary amines such as triethylamine, triisopropylamine, methyldietalamine, dimethylaminoethanol, etc.
Primary monoamines: polyethylenes such as diethylenetriamine, hydroxyethylaminoethylamine, ethylaminoethylamine, methylaminopropylamine and the like. Examples of the amide compound used for neutralization is preferably a compound having an amide amino group represented by -CH-C (O) -NH ₂ at its molecular end, for example, lauramide, having 6 to 18 carbon atoms such as stearyl amide Aliphatic amide compounds can be mentioned.

The treating agent used in the treatment of the present invention can be used as it is, but it is previously aromatic hydrocarbon solvent such as toluene, xylene, solvent naphtha, Solvesso 100 (manufactured by Esso Oil Co., Ltd.) or It may be diluted with a glycol ether solvent.

The treatment of the surface of the aluminum flakes with the treating agent is carried out by mixing with a mixer such as a ribbon type mixer or a kneader type kneader. The amount of the treating agent is 0.01% by weight or more, preferably 0.1 to 5% by weight, more preferably 0.1 to 1.5% by weight, in terms of P element, based on the aluminum flakes. If it is less than 0.01% by weight, it is insufficient to improve the discoloration resistance and the cohesive failure resistance in the coating film. Further, even if the treatment is performed in an amount exceeding 5% by weight, no further effect can be obtained.

The surface of the aluminum flakes is P as a treating agent.
The adsorption of the —OH group prevents the organic pigment from being discolored by being coated with the treatment agent and resulting from the active aluminum surface. Furthermore, the strong cohesive force of the polyfunctional epoxy compound as the treating agent improves the adhesion between the aluminum pigment and the vehicle component in the paint. In particular, even if the content of the aluminum pigment increases, cohesive failure does not occur in the coating film.

[0032]

EFFECT OF THE INVENTION Since the metallic coating film using the aluminum pigment not subjected to the treatment of the present invention is coated with the fatty acid, increasing the blending ratio of the aluminum pigment causes cohesive failure in the metallic coating film. Membrane adhesion is impaired. However, in the metallic coating film using the aluminum pigment treated according to the present invention, even if the mixing ratio of the aluminum pigment is increased, cohesive failure does not occur in the metallic coating film, and the coating film adhesion can be significantly improved.
Further, in a paint obtained by mixing an untreated aluminum pigment with an organic pigment such as anthraquinone-based, pyranthrone-based, quinacridone-based, and perylene-based which is used as a coloring metallic, the organic pigment is discolored during storage. However, the aluminum pigment treated according to the present invention has an excellent paint stability effect without causing discoloration of the organic pigment.

[0033]

【Example】

<Replacement of solvent contained in aluminum pigment> 1 kg of aluminum pigment [trade name, manufactured by Toyo Aluminum Co., Ltd.,
Alpaste (registered trademark) 7670NS] was used as a substituted aluminum paste obtained by solvent substitution with 1 liter of Solvesso 100 (manufactured by Esso Oil Co., Ltd.) on a pan filter (substituted aluminum paste).

Example 1 An additive (Structural Formula 1) (treatment agent) of celoxide 2081 (manufactured by Daicel Chemical Industries, Ltd.) and a phosphorus compound was added to 100 parts of aluminum metal of the above substituted aluminum paste to contain P element. Blended so that the ratio is 0.25%,
The aluminum pigment was surface-treated by mixing for 30 minutes with a kneader mixer.

Example 2 An additive (Structural Formula 2) (treatment agent) of celoxide 2085 (manufactured by Daicel Chemical Industries, Ltd.) and a phosphorus compound was added to the above-mentioned substituted aluminum paste containing P element for 100 parts of aluminum metal. Blended so that the ratio is 0.25%,
The aluminum pigment was surface-treated by mixing for 30 minutes with a kneader mixer.

Example 3 Adduct 1 of celoxide 2085 of the above 2 and a phosphorus compound
1 mol of dilaurylamine was reacted with 1 mol to neutralize a part of the phosphoric acid groups, and the P element content was 0.1% with respect to 100 parts of the aluminum metal of the above substituted aluminum paste.
The mixture was blended so as to be 25%, and the aluminum pigment was surface-treated by mixing for 30 minutes with a kneader mixer.

Example 4 An addition product (treatment agent) of neopentyl glycol diglycidyl diether [manufactured by Daicel Chemical Industries, Ltd.] and a phosphorus compound was contained in P element with respect to 100 parts of aluminum metal of the substituted aluminum paste. The mixture was mixed so that the ratio would be 0.25%, and mixed with a kneader mixer for 30 minutes to perform surface treatment of the alnium pigment.

Comparative Example 1 Commercially available organic solvent type aluminum pigment, Alpaste (registered trademark) 7670NS (manufactured by Toyo Aluminum Co., Ltd.).

Comparative Example 2 The above substituted aluminum paste which was solvent-substituted with Solvesso 100 (manufactured by Esso Oil Co., Ltd.).

Comparative Example 3 Organic solvent type aluminum pigment, Alpaste (registered trademark) 1109MA (manufactured by Toyo Aluminum Co., Ltd.) 100
To 1 part, deionized water 0.7 parts isopropyl alcohol 1
Dissolve in 0 parts and add and mix at a temperature of 50 ° C for 30
Aluminum pigment stored for a day.

Paints and coatings were prepared from the aluminum pigments of the above Examples and Comparative Examples according to the following specifications, and the discoloration resistance and the cohesive failure resistance in the coating were evaluated.

[0042]Test Example 1 (evaluation of cohesive fracture resistance in the coating film
Price) Preparation of organic solvent type metallic paint The following formulation: Acridic A-322 (manufactured by Dainippon Ink and Chemicals, Inc.)                                                 80 parts by weight Super Beckamine L-117-60 (manufactured by Dainippon Ink and Chemicals, Inc.)                                                 16.65 parts by weight Aluminum pigment (Al content 65%) 7.69 parts by weight                                             (Equivalent to 10 phr)                                           Or                                                 11.53 parts by weight                                             (Equivalent to 15 phr) Thinner 100 parts by weight Depending on 10 phr or 15 phr aluminum pigment
Dispersed in thermosetting acrylic melamine resin liquid,
A metallic paint was prepared.

Preparation of Coated Plate A test piece was coated with the above metallic paint, and the following formulation was added on it: Acridic A-345 (manufactured by Dainippon Ink and Chemicals, Inc.) 140 parts by weight Super Beckamine L-117-60 (Manufactured by Dainippon Ink and Chemicals, Inc.) 55 parts by weight Solvesso 100 (manufactured by Esso Oil Co., Ltd.) 50 parts by weight of the top clear prepared by coating is overcoated at 140 ° C. for 3 days.
Bake for 0 minutes. The dry film thickness is 13-for the metallic layer.
The top clear layer has a thickness of 15 to 40 μm.

Evaluation method For the cohesive failure resistance, the obtained two-coated coating film was cut with a knife so as to reach the substrate, 100 pieces of 1 mm × 1 mm goggles were made, and an adhesive cellophane tape was attached to the surface. The number of coating films on the remaining burrs after being worn and rapidly peeled off was examined.

Test Example 2 (Discoloration resistance) Preparation of organic solvent type metallic paint Primary color paint 1 Acridic A-322 (manufactured by Dainippon Ink and Chemicals, Inc.) 160 parts by weight Super Beckamine L-117-60 (large) 33.3 parts by weight, manufactured by Nippon Ink Chemical Co., Ltd. 20.0 parts by weight of anthraquinone pigment (Chiba Geigy, trade name Chromophtal Blue A3R).

[0046] Silver metallic base paint 2   Acridic A-322 (manufactured by Dainippon Ink and Chemicals, Inc.)                                                       80 parts by weight   Super Beckamine L-117-60 (manufactured by Dainippon Ink and Chemicals, Inc.)                                                       16.65 parts by weight   Aluminum pigment (Al content 65%) 10 parts by weight.

The primary color paint 1 and the silver metaclick base paint 2 were mixed at a ratio of 1 to 5 (weight ratio) to prepare a colored metallic paint.

Storage test and preparation of coated plate The above organic solvent type metallic paint was stored at 50 ° C. for 2 weeks. Paint the test piece before and after storage on the test piece, and then add the following composition: Acridic A-345 (manufactured by Dainippon Ink and Chemicals, Inc.) 140 parts by weight Super Beckamine L-117-60 (Dainippon Ink and Chemicals) Industrial Co., Ltd. 55 parts by weight Solvesso 100 (manufactured by Esso Oil Co., Ltd.)
Bake for 0 minutes. The dry film thickness is 13-for the metallic layer.
The top clear layer has a thickness of 15 to 40 μm.

Evaluation method The test piece prepared above was subjected to color measurement with an SM color computer (manufactured by Suga Test Instruments Co., Ltd.) to determine the color difference before and after storage.

The test results are shown in the table below.

[0051]

[Table 1]

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitsugu Endo 4-17-1, Higashi-Hachiman, Hiratsuka City, Kanagawa Kansai Paint Co., Ltd. (56) Reference JP-A-7-70468 (JP, A) JP-A-7- -133440 (JP, A) JP-A-2-120368 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C09C 1/64 C09C 3/08

Claims (2)

(57) [Claims] 1. A phosphoric acid ester (A) produced by an esterification reaction of a polyfunctional epoxy compound and a phosphorus compound in an amount of 0.01% by weight or more in terms of P element relative to aluminum flakes, or a phosphoric acid ester (A) thereof. An organic solvent type aluminum pigment treated with a phosphoric acid ester amine salt (B) obtained by neutralizing (4) with an amine compound or an amide compound. 2. An alicyclic epoxy compound or fat in which the polyfunctional epoxy compound has two or more alicyclic epoxy groups in which an epoxy group is directly bonded to carbon atoms constituting a ring of an alicyclic hydrocarbon. 2 epoxy groups formed by glycidyl etherification of two or more hydroxyl groups contained in a group polyhydric alcohol
It is an aliphatic epoxy compound which has one or more pieces, The aluminum pigment of Claim 1 characterized by the above-mentioned.