JPS59199764A - Modification of hydrophobic organic matter - Google Patents

Abstract

PURPOSE:To provide titled matter with hydrophilicity by carrying out a low- temperature oxide gas plasma treatment of said matter such as carbon black to afford it with water-dispersibility without any loss due to ashing. CONSTITUTION:A hydrophobic organic matter such as carbon black, organic pigment, is subjected to low-temperature oxide gas (pref. oxide gas such as CO2, or mixed gas consisting of a little oxygen and suboxide gas such as NO, N2O, CO, SO2) plasma treatment to afford it with water-dispersibility. For low-pressure treatment, said plasma treatment is recommended to be performed at 0.05- 5mm.Hg.

Description

[Detailed Description of the Invention] The invention relates to a method for modifying hydrophobic organic substances such as carbon black and sensitive pigments by subjecting them to low-temperature gas plasma treatment. The aim is to produce the same in a stable manner and in good yield.

Hydrophobic organic substances such as carbon black and organic pigments have low polarity, so they are difficult to wet with water and difficult to maintain a dispersed state in water, making it difficult to maintain a stable dispersion state when used in water-based paints and inks. I can't do it.

Regarding carbon black, the present inventors have discovered that so-called channel-type carbon black, which is manufactured through a process in which it is exposed to air at high temperatures for a long time in its manufacturing process, has a higher level of carbon black than furnace-type carbon black, which does not require such a process. Focusing on the fact that the wettability to water is relatively high, and this is presumed to be due to the particle surface undergoing oxidation (thus forming surface compounds and increasing the amount of volatile matter), we developed furnace-type carbon black. Wet oxidation using an oxidizing agent such as nitric acid or sodium hypochlorite, or oxidation in an electric furnace.
By heating the material to 50°C to 300°C, we succeeded in improving its wettability with water and improving its dispersibility in water.

[Journal of Coloring Materials Association Vol. 45, 637 (1972), Journal of Coloring Materials Association of Japan, Vol. 48, 437 (1975)] However, although the oxidation treatment by these methods was effective to some extent, the yield and effectiveness were Practical treatment effects could not be obtained due to the difficulty in purification through post-treatment.

Next, in order to solve these problems all at once, the present inventors invented a method for producing water-dispersible modified carbon black by low-temperature oxygen plasma treatment.

(Patent Application No. 046057 of 1981) That is, the surface of carbon black particles is oxidized by low-temperature oxygen plasma treatment, and oxygen-containing acidic surface compounds such as carboxyl groups and phenol groups are formed on the particle surfaces, which are resistant to water. It is thought that it contributes to wettability and electrical repulsion, is extremely easy to wet with water, and has excellent dispersibility in water or various aqueous vehicles.

In this case, oxygen is used alone as the oxygen gas,
Alternatively, it was also possible to use air as the oxygen source, or a mixture of oxygen and nitrogen or an inert gas.

However, depending on the low-temperature plasma treatment using oxygen gas or oxygen-containing gas, if the high frequency output is too strong, the carbon black will be significantly ashed (ti: 'r*
This results in extremely poor product yield. Additionally, there is a drawback that the processing effect cannot be fully exhibited and the work is forced to be carried out at a low efficiency.

The present invention improves the drawbacks of the conventional method as described above, and even with C, which has a high high frequency output, ashing hardly occurs, so the product yield is approximately 100%, and high performance products can be stably produced. This work was carried out with the aim of developing a method that could be obtained, and this has now been completed.

Furthermore, the present invention is not limited to the modification of carbon black.
! This work has also been completed to improve the water dispersibility of hydrophobic organic substances such as fins.

Hereinafter, the configuration of the present invention will be explained in detail.

The organic face F1 used in the present invention includes paint,
Organic face M commonly used in ink, plastic T industry, etc.
'+1 is preferred.

For example, the azo pigment Irgazine Red 1-T (manufactured by Ciba 3-), Tuba Palm Yellow H10G (manufactured by Hoechst),
Monolight Red [3R (manufactured by ICI), azo dye
Sudan■, Sudan■, Sudan■, Sudan■ (manufactured by Industria Viemontessedai Colori di Anilina), etc.

Polymerized azo pigments Chromophthal Red A2B (Ciba Rei WA), Monolite Yellow 4G (manufactured by TCT), etc.

Metal Complex Azo Pigment Irgajinero-50
T (manufactured by Ciba), Variotol Yellow 1770 (BA
SF Reisei) etc. Benzimidazolone pigment Hostapalm Elo-83G (manufactured by Hoechst), Hostapalm Orange HL70 (manufactured by Hoechst), Tubapalm Orange I
-IL (manufactured by Hoechst), etc.

Quinacridone pigments Shinkasha Red Y (manufactured by DuPont), Shinkasha Violet (manufactured by DuPont), Hoster Palm Red (manufactured by Hoechst), Paliogen Red (manufactured by BASF), Monolite Violet (manufactured by IC1), etc. . Isoindolinone pigment Irgajinero-2R
LT (manufactured by Ciba) -4=, Pa') l--Lue I:]-2140LI D (1
1A S Fne)'S.

Quinophthalone pigment Variotol Yellow 0960HD (
Perinone-based pigments Hoster Palm Red GR (manufactured by Hoechst), etc. Perylene-based pigments Hoster Palm Red BPT (manufactured by Jibane 1), Tuba Palm Red B
l- (manufactured by Hoechst), Paris Augen Red 3910
(manufactured by 1'3ASF) etc. Dioxazine-based products include Chromophthal Violet (manufactured by Chibane), Hosper Plumby Daiichi Knot RL (manufactured by Hoechst), Dioxazine Violet (IJ, Sumitomo Chemical), etc. Phthalocyanine-based face 1'l Chrome Fuccle Blue 4ON (manufactured by Ciba), Bosta Palm Blue-83G (manufactured by Hoechst), Shinkasha Blue-〇r (manufactured by Decobonne 1), Cromonocle Green G
F (manufactured by Ciba), Hosper Palm Green GG (manufactured by Hoechst), Shinkasha B (manufactured by DuPont), etc. Thioindigo pigment Tubapalm Red Violet MR8 (manufactured by Hekis 1~), Thiofastrette Mv "6606 (
(manufactured by RASF Ne1) etc. Anthraquinone pigment Chromophthal Red △3B (Jivasha 8A), etc. Flavanthron type face + P + Chromophthal Yellow Δ2R (manufactured by Ciba), Monorai 1 to Yellow FR (manufactured by IC1), etc. Indanthrene pigments Chromophthal Blue A3R (manufactured by Ciba), Monolight Blue 3R (manufactured by ICT), Thren Blue 6011
(manufactured by Dainippon Ink Co., Ltd.), etc. Anthrapyrimidine pigment Paliogen Ero-1560 (manufactured by BASF), etc.

Ansu Anthrone pigment Monolight Red 2Y (IC1
), Monolite Red Y (manufactured by ICI), Hostapalm Scarlet Go (manufactured by Hoechst), etc. Bilanthrone series Paris Augen Red 3530 (B A SF
(ceremony made) etc. Various organic pigments such as

The method for modifying the hydrophobic organic substance according to the present invention is carried out by irradiating the hydrophobic organic substance with low-temperature plasma. Power sources for generating such low-temperature plasma include radio frequency, microwave, direct current, alternating current, etc. Types of discharge include glow discharge by inductive load, capacitive load, corona discharge, and boxer charger.

When treating hydrophobic organic substances using such plasma, the degree of vacuum in the treatment tank should be 0.
01~10111m101l1 Preferably 0°05~5
n+n+H (lr exists.

On the other hand, when processing at normal pressure, the processing can be carried out in the atmosphere or by bringing the processing gas into contact with the substance to be processed.

By using an oxide gas such as Co2 as the plasma gas, hydrophobic organic substances are modified into organic substances with good water dispersibility in an extremely high yield while preventing ashing.

Furthermore, low-temperature plasma treatment with suboxide gases such as NO, NzO, Co, and 802 has poor reforming effects, but by mixing a small amount of oxygen gas into these gases, excellent reforming effects can be achieved. It was also successful. Moreover, in this case, the exhaust gas contains NO□, Co
2, SO3, etc., and the processing work is easy.

The invention will be explained below by way of examples.

Example 1 7- Pyrex plasma chamber (inner diameter 7 cm, length approx.
Furnace-type carbon black (
Pyrex sample boats containing Mitsubishi #44>39 were placed one by one, and the inside of the chamber was heated to 1B2 for 1 hour at 0.5mmH++, and then evacuated for 100m (?/mi).
Modified carbon black was produced by maintaining a plasma state for 2 hours at a high frequency output of 2 W while flowing carbon dioxide gas at a rate of n. Unmodified carbon black gets wet with water and has extremely poor dispersibility in water and aqueous vehicles, whereas the modified carbon black produced in this example wets water extremely well and moves in water and in aqueous vehicles. Above all, the dispersibility was excellent, and a uniform and extremely good dispersion state was obtained with short stirring.

In addition, trial 11o was added to water ioomc and boiled for 15 minutes, and after being left for 48 hours, the pl-1 of the suspension was measured, and the unmodified carbon black was 7°2, while the modified carbon black was 7°2. 3.68-, the particle surface was oxidized, and the presence of a considerable amount of acidic oxidation products was observed.

Example 2 Same as in Example 1 - As a result of changing the plasma treatment time (■) to 4 hours under the same rule 1'1, the water dispersion ↑η was the same as in Example 1.
01-( was 3.1 on 14th day with a good score.

Example 3 In Example 1, the high frequency output during the low temperature plasma treatment was set to 5 W, the treatment +1.11 was set to 2 hours and 4 hours, and the modified carbon black was 17.

In each case, the water dispersibility was 1 θf, and 1) 11 was 3.4 and 3.0.

Example 4 The high frequency output was set to 2 W and 5 W using the same strip as in Example 1, and low temperature plasma gas was generated using oxygen scum alone using the same strip as in Example 1. Next, the weight changes for each were measured and the results were as follows.

(Hereinafter ■ζ margin) In other words, the low-temperature plasma treatment using carbon dioxide gas according to the reforming method of the present invention results in much less iodization than the method using oxygen gas, and therefore produces carbon with extremely high yield and excellent water dispersibility. A black product is obtained.

Example 5 Using the same equipment as in Example 1, each of the hydrophobic organic faces F430 (1) to (6) shown below was produced at a high frequency output of 10 W.

Carbon dioxide flow f? After treatment at i100 m+7/min for 2 hours, the mixture was poured into a colorimetric tube containing the same volume of benzene and water mixture, shaken vigorously, and left to stand for 10 minutes. As a result of investigating whether the unmodified organic pigments migrated to the benzene layer or the aqueous layer, almost all of the unmodified organic pigments migrated to the benzene layer, whereas almost all of the modified organic pigments migrated to the aqueous layer, indicating excellent water dispersion. +'t is now 1! -I was happy to see that I had been treated so well.

1) Sudan T (C, 1, 12055) (2)
Sudan T (C, 1, 12140) (3> Sudan m (C, 1, 26100) (/I) Sudan
IV (C, I, 26105) (5) Indigo (6) Lid [-1 Cyanine Blue Example 6 In Example 1, the treatment gas was mixed with carbon monoxide gas and oxygen gas (mixing ratio 2:1). ), the modified carbon black was treated with a high frequency power of 10 W for 211) and 4 hours. Both are water dispersion 1'
1 was good Y, and II 1-1 was 3.2 and 3.0, respectively. Furthermore, it was confirmed that the IJI emission in this case was mostly carbon dioxide gas.

J-state it! As described above, the method for modifying hydrophobic particles according to the present invention provides a product that is extremely compatible with water and has excellent dispersibility in water or in an aqueous vehicle such as an aqueous solution of a water-soluble maleic acid resin. This invention is an extremely efficient manufacturing method that prevents loss due to iodization, and the present invention
This invention has completed a practical manufacturing method for water- or aqueous vehicle-dispersible colorants, etc., which has been desired for industries, printing ink industry, cosmetics industry, eutectic industry, and plastic Ti.

Patent applicant: Educational corporation Kindai University Nippon Paint Co., Ltd. Agent Patent Attorney Kogawa -1

Claims (4)

[Claims] (1) A method for modifying a hydrophobic organic substance, which comprises making the hydrophobic organic substance water-dispersible by treating the hydrophobic organic substance with a low-temperature oxide gas plasma. (2) The method for modifying a hydrophobic organic substance according to claim 1, in which carbon black is used as the hydrophobic organic substance and carbon dioxide gas is used as the oxide gas. (3) A method for modifying a hydrophobic organic substance according to claim 1, in which an organic pigment is used as the hydrophobic organic substance. (4) A method for modifying a hydrophobic organic substance according to claim 1, in which low-temperature plasma treatment is performed by mixing a small amount of oxygen gas into suboxide gas.