JPS581761A - Coating composition - Google Patents

Abstract

PURPOSE:To provide a coating compsn. which prevents fogging due to aggregation of organic pigment particles and imparts high gloss, prepared by simultaneous dispersion of pigment dispersing resin, organic pigment and specified inorganic pigment in superfine particles. CONSTITUTION:At least one organic pigment (B) selected from (condensed) azo, perylene, quinacridone, vat dye, thioindigo, isoindolinone and quinophthalone type pigments and superfine inorganic pigment (C) having a speccific surface area of 45m<2>/g or smaller (by BET method) and an average particle size of 0.06mu or less. with 90% of the particles being less than 0.1mu (e.g. precipitated barium sulfate) are added to a vehicle (A) contg. 100pts.wt. pigment dispersing resin (e.g. alkyd resin with an oil length of less than 40) in 0.1-50pts.wt. and in 5- 200pts.wt. per 100pts.wt. (B), respectively, followed by dispersion in a sand grinding mill.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention #i relates to a coating composition containing a resin and an organic pigment.

In recent years, high-grade organic pigments have come to be used as the weather resistance of automobile eardrums has been demanded to be improved.Also, in Japan, the use of lead-based pigments has been restricted from the perspective of pollution prevention. S-Do.

Yellow-based MS materials have been used. However, most of these organic pigments are difficult to disperse, and even when dispersed, it is often difficult to obtain sufficient gloss. Conventionally, methods used in such cases include:
The above-mentioned problems could not be solved by using a special dispersion method such as hot roll dispersion or roll fk dispersion, or by dispersion using a general sand grind mill or the like. hot roll, o
- The dispersion method according to the method of Luro et al. has low productivity and requires a lot of man-hours, so it has poor adaptability to mass production on an industrial scale.

Recently, there has been a demand for improved weather resistance of alkyd melamine resins in the field of resins for automobile sleds and collars, and products with extremely short oil lengths have been considered.
In some cases, oil-free products are also being considered.

However, these trees W! However, in general, there are problems in that they have poor wetting with pigments, poor dispersibility of pigments, and difficulty in obtaining sufficient gloss.

As resins for pigment dispersion, alkyd resins with an oil length of 40 or less, oil-free polyester resins, acrylic resins, etc. are generally used, but alkyd resins (with an oil length of 40 or more),
Examples include melamine resin and Nixie resin, but it is particularly difficult to disperse organic pigments in alkali resins, oil-free polyester resins, and acrylic resins with an oil length of 40 or less.

On the other hand, organic pigments include azo and perylene.

One or more pigments selected from quinacridone series, architectural dye series, condensed azo series, thioindi-f series, isoindolinone series, quinophthalone series, and phthalocyanine series are used. It is difficult to obtain the desired dispersion coating performance.

Conventionally, the above-mentioned problems regarding dispersion of organic pigments and resins have been individually addressed by devising dispersion methods.

The present invention provides Il! containing a pigment dispersion resin and an organic pigment that have a dispersion state that allows a sufficient gloss to be obtained without changing the conventional dispersion means, that is, using a dispersing machine such as a sand grandon. The purpose is to release the composition in one shot, and this purpose is compared using the BIT method! ! The IWjJ product is 45wI/l or less, the average particle size is 0.06μ or less, and 901 of all particles is 0.
This was achieved by simultaneously dispersing ultrafine inorganic particles of 1 micron or less in size with a pigment dispersion resin and an organic pigment. When these ultrafine particle-free pigments are simultaneously dispersed, they exist between the organic pigment particles to prevent 1 capri 1 due to agglomeration, etc., and to improve the glossiness.

As mentioned above, the ultrafine inorganic pigment used in the present invention has a ratio of 1
1 area is 45wn/I or less by the method, the average particle size is 0.06μ or less, and the 90- of all particles is 0.1μ or less. 9. Ratio of ultrafine inorganic Jll material by BET method If the surface area exceeds 45*/7, the amount of oil absorbed increases, which tends to lower the glossiness, which is not desirable. Specific surface area (BET method), which is difficult for ultrafine inorganic pigments to adhere to, IIi, 3
Less than 0 turbidity/l.

Further, the ultrafine inorganic jIIi material must have an average particle diameter of 0.06 tones or less, and 90% of all particles must be 0.1 μ or less.

If the particle size exceeds these values, the dispersion effect will be significantly reduced, and no effect will be found in preventing agglomeration or the like.

Nine generations of ultrafine particles suitable for use in the present invention
IIIlts materials include barium sulfate treated with alkali, such as commercially available BF-1, 8F-10 (both Onahama Sakai Chemical! #), precipitated barium sulfate 100 (# Chemical (all), ultrafine silicic acid, etc.) MIZUK-A8I
By using 5 to 200 parts by weight, preferably 10 to 100 parts by weight of L (manufactured by Mizusawa Kagaku (A), etc.) for 100 parts by weight of the sn-dispersible pigment, the glossiness of the coating film can be improved. If the amount of the ultrafine inorganic pigment is less than 5 parts by weight, the desired effect of improving the dispersibility will be small, and if it exceeds 200 parts by weight, the problem will be fading and the negative effect of the sunken WI cape. This is not preferable because it deteriorates weather resistance.

Using the commercially available BF-1 and BF-1n described above, excess Bus and H2S04 are reacted according to the reaction formula below, and excess la and S are treated with FiNaOH. That is, Ba8 +
H,5o4-+ Ba1iO4+ H! II-
・(1) 1mg +2NaO)I −+ l1a(
OH) 2 → 12s... (2) Commercial product BP-1 has some S content remaining, while IF-10 has almost no S content remaining. When it is, it is easy to form complex salts with rich functional groups in the resin such as carboxylic acid group (COOH), and it becomes 7v1,9, increasing the chatrobiity by 4. Therefore, it is preferable to use BF-10 for materials with many C0OH groups and OH groups, such as I-reesters and acrylic resins.

Furthermore, recently, discoloration of warp and color has become a problem, and as a countermeasure, methods are sometimes taken to lower the pigment concentration, but in this case, in addition to the problem of decreasing the hiding power of the paint, it is also possible to This may be accompanied by a decrease in strength or hardness.The paint containing the ultrafine inorganic pigment used in the present invention can prevent such a decrease in the physical properties of the paint film.As mentioned above, The organic dispersion pigment is difficult to disperse below the primary particles as a pigment, and it is easy to cause secondary aggregation in the dispersion system at the same time as dispersion, so in the present invention, as described above,
By blending the ultrafine particle-free 1aIIA material, the ultrafine inorganic pigment intervenes between the 11i materials that are being dispersed during the dispersion process, providing a dispersion auxiliary effect and preventing secondary agglomeration of the dispersed bales, thereby eliminating the above drawbacks. It is intended to prevent

Here, "simultaneous dispersion" refers to adding and blending an organic pigment into a vehicle and dispersing it simultaneously with an ultrafine inorganic pigment.

When performing dispersion, it is most preferable to add the ultrafine inorganic pigment to the vehicle at the stage of premixing the pigment and resin before dispersion using a sand grind mill, but if it is convenient, the pigment can be dispersed in the resin. An ultrafine inorganic pigment dispersed in a solvent or/and a resin varnish may be added to the pigment, and in this case, the only effect is to prevent secondary aggregation of the pigment.

There is no particular restriction on the Fi distribution ratio of the poorly dispersible resin and the organic poorly dispersible JIli material in the coating composition of the present invention, but generally 0.1 to 50 parts of the organic dispersible pigment per 100 parts by weight of the poorly dispersible Fi resin. Add parts by weight.

The present invention will be described in detail below, but it goes without saying that the technical scope of the present invention is not limited to these Examples. In J, "part" means "part by weight"
shows.

Example 1 Short oil alkyl, resin A (oil length 20, hydroxyl value 80°, acid value 8
1 molecular weight M1! +2000. An alkyd resin paint containing coconut oil and neopentyl glycol as the main ingredients was developed.

As melamine, suit arm, Cain G-821-
60 (Dainippon Ink Chemical #) was used in an amount with an alkyl, to/melon ratio of 7/3 (weight ratio), and Shinka Shared Y (De & In If) was used as the organic pigment.
Pre-mixed and mixed dispersion pace)'t? The mixture was dispersed in a conventional method in a dry blind oil, and a sample was prepared by dissolving Sue/Peccamin G-821-60 (18 parts) therein.

Shinkasha Red Y 20 parts BP - 120 parts Alkyd resin 60 parts Doluol 30 parts (total 130 parts) Ratio 111JI Example 1 except that the ultrafine inorganic pigment IP-1 was not blended in the formulation of Example 1 above. An alkylene resin topcoat was prepared in the same manner as above.

IM! Example 2 An acrylic resin paste coat containing acrylic resin Almatex NT-U-448 (manufactured by Mitsui Toatsu Chemical Co., Ltd.) as a main component was prepared in the following quantity. Knee pants 208 as melamine
F (manufactured by Mitsui Toatsu Chemical), acrylic/melamine ratio: 8
Used at a ratio of /2 (weight ratio), there is II! As the 4th ingredient, use Shanin Green 8 (manufactured by Dainippon Ink Chemical Co., Ltd.), and disperse the pre-mixed dispersion paste with the following composition in a Sanddarind (ru) in the usual manner, and add Kneepan 208K (15 parts) to this. ) and Almatex NT-U-4
48 (36 parts) was dissolved to prepare a sample.

Shanin Green 8 Part 10 Almachi,
NT-44836 parts IP-IQ 5 parts xylene 9 parts butanol
3 parts (total 63 parts) Comparative Example 2 In the formulation of Example 2, ultrafine inorganic ljA material BF-1O
An acrylic resin paste coat was prepared in the same manner as in Example 2 except that Fi was not blended.

Example 3 An alkyl-deresin IIITo material containing Kid resin Phthalkid 133-60 (manufactured by Hitachi Chemical) as a main component was prepared as follows. Mother 5 (suit mother)
Petsuka f G-821-60 was used in alcohol at a de/melane ratio of 75/25 (weight ratio), and Nogapalm Orange HL-70 (manufactured by Hechust) was used as the organic pigment. The mixed dispersion paste with the following composition was dispersed using a sandblasting oil in the usual manner, and a sample was prepared by dissolving Suit Minna-Petskain G-821-60 (20 parts) into the sample.
Part BF-129゜Phthalkyd 133-60 60 parts A 111111 material was prepared on IpI resin.

Test Example 1 A coating test was carried out on the paint samples of Examples 1 to 3 and Comparative Examples 1 to 3 prepared above under the following conditions, and the gloss of the paint film (20° gloss, 600 gloss) and the presence or absence of capri (visual observation) were carried out under the following conditions. Kaashii) was evaluated. The results are shown in Table 1.

(1) Is the compounded paint on each side of fiLm/triene/? Dilute the diluted paint as shown in the table below with a diluting thinner of 30/40/30 (Siren/Serotsuru 1 acetate) and apply the diluted paint to 100m/m x 200m/
Pour enough water onto a 0.3 m/m tin plate, stand the plate vertically, set it indoors for 10 minutes, and then bake at 140℃ for 30 minutes. Do the test and rate it I! ! I had it as a meal. The thickness of the obtained film is as shown below.

The E material prepared on each side was spray-painted using a paint sprayer (Iwata Painter side) at 61 degrees of pressure so that the dry film thickness shown in the table was obtained, and baked at 140C for 30 minutes.

The object to be coated is (JIS-G3141) 8PCC.
-8D iron plate was chemically treated by immersing it in zinc phosphate treatment solution (Japan (India@) "Granodine 16NJ"),
Washed with water, then electrodeposited using cationic electrodeposition paint (Nippon Paint @ Tsutaward, 7'U-30), washed with water, baked at 1180℃ for 20 minutes, and electrodeposited with a dry spread thickness of 20#IO. M film was formed. On top of this, Ol f8-52E Miller (manufactured by Nippon Paint Co., Ltd.) was spray-painted as a medium-m paint according to the specified coating specifications, and the temperature was 140°C.
Bake for 20 minutes at 25. An intermediate coated board having a dry film thickness of gm was obtained and used as a coating object for a wrinkled coated board system.

Table 1 * I JIS-54006, 7: 60 degree Tablet surface reflectance measurement method, angle of incidence and reflection measured at 20 degrees.

Book 2 JI8-54006, 7:601ij In the III constant plane of specular reflectance, the angle of incidence and angle of reflection are fixed at 60 degrees.

Umbrella 3 Visual judgment: Painted MI! Test Example 2 The paints of Example 2 and Comparative Example 2 were applied to the above-mentioned 3i! The ridge was spray-painted using the above method, and after 5 minutes of setting, a clear resin 17!1 (Nippon Paint Co., Ltd. Suit Arm 2, Coo 0-35 Clear) was applied to the beating membrane according to the standard specifications. After spray painting at 100° C., setting for about 10 minutes, and baking at 140° C. for 30 minutes, a test coated plate was obtained. The results were as shown in the table below.

See footnotes in Table 1 of this book. patent applicant Japan (India Co., Ltd. patent application agent Patent attorney Akira Aoki Patent attorney Kazuyuki Nishidate Patent Attorney Ishi 1) Takashi Patent attorney Akira Yamaguchi

Claims (1)

[Scope of Claims] 1. The resin for feed dispersion and the organic pigment have a specific surface area of 45 J711 or less, an average particle size of 0.06 μ or less, and a total particle size of 90 of less than 0.1 μ. A paint composition made by simultaneously dispersing an inorganic pigment. 2. The composition according to claim 1, wherein the ultrafine non-threaded noodle material is an alkali-treated fine powder of palitum sulfate. 3. The composition according to claim 1 or 2J, wherein the amount of the fine inorganic pigment is 5 to 200 parts by weight per 100 parts by weight of the organic pigment. Alkyd resin of 40 or less, oil-free ester resin or ac I))L
5. The composition according to claim 1 using tM fat, as an organic pigment, azo type, perylene type, quinacridone type, architectural dye type, condensed azo type, thioindigo type, isoindolinone type, kino7 type. pn system. The composition according to claim 1, which uses one or more pigments selected from the phthalocyanine family.