JPH0813938B2 - Surface modifiers for inorganic and organic pigments - Google Patents

Description

The present invention relates to the surface of inorganic and organic pigments containing at least one acidic amino acid-ω-long chain amide having an aliphatic alkyl group having 6 to 22 carbon atoms. The present invention relates to a modifier, which is used in the fields of plastics, paints, printing inks, rubbers, stationery, cosmetics and the like.

2. Description of the Related Art In recent years, in various fields such as composite plastics, paints, adhesives, rubbers, inks, etc., strength and rigidity or adhesiveness has been added, heat resistance and weather resistance have been improved, color tone and viscosity characteristics have been improved, and cost reduction has been achieved by increasing the amount. Or, for the purpose of imparting new functions such as conductivity, inorganic pigments such as calcium carbonate, titanium dioxide and talc, inorganic fillers such as silica, ferrite, metal powder, metal fibers and glass fibers, phthalocyanine pigments, Organic pigments or dyes such as quinacdrine pigments, indigo pigments and azo pigments are used. Also in cosmetics, inorganic powders such as titanium dioxide, zinc white, talc, kaolin, and basic magnesium carbonate are known.

However, the surface of the inorganic pigment, the inorganic filler and the inorganic powder is generally poor in lipophilicity because it is covered with a polar group such as a hydroxyl group or an adsorbing component, and the resin, rubber,
It is difficult to disperse it uniformly in an organic medium such as fats and oils, and in the case of organic pigments and dyes, the aggregation of organic pigment particles occurs in a non-aqueous vehicle, and the color unevenness and vividness of the organic pigments and dyes Moreover, the desired composition cannot be obtained, such as loss of gloss.

Therefore, various modifying methods and dispersing methods are actually used for the purpose of improving the wettability or dispersibility of inorganic pigments, inorganic fillers, organic pigments, and inorganic powders.

Various methods have been disclosed as methods for improving the dispersibility of organic pigments. For example, a method in which a powder pigment is previously dispersed in a plasticizer into a paste by a flushing method or a grinding method is used for a long time.
In addition, a method in which a water-containing cake of an organic pigment is suspended in an organic agent using a surfactant, heated, filtered, washed with water, and dried (JP-B-40-1844), the pigment and a large amount of water-soluble anion are used. A method of using a pigment composition obtained by mixing an activator and a water-soluble polymer with water and spray-drying (JP-A-49-788).
7), a method of treating a pigment with an anion activator and a cation activator (JP-A-51-88523), a method of using a thermoplastic resin and a solvent (JP-A-51-54620), a water-soluble thermoplastic resin and a pigment A method of flushing with a water-containing cake (JP-A-54-95638) and the like are disclosed.

Problems to be Solved by the Invention As a method for modifying an inorganic surface using a conventional inorganic surface modifier, for example, a surfactant such as stearate,
It is known that the modification effect is not sufficient with a small amount, and that addition of a large amount causes defects such as blooming during processing of a resin or the like, or deterioration of water repellency and weather resistance of the final product. There is. Further, when the surface is modified with a polymer such as polystyrene, the polymer coating the inorganic surface is swollen and dissolved by the organic solvent serving as the dispersion medium, and desorption from the inorganic surface occurs. In application, the coupling agent molecule reacts with the surface-containing functional group of the inorganic substance containing silicon such as glass and silica,
Since it forms a strong curtain, it has an excellent surface-modifying effect, but it is not expected to have an effect on other inorganic substances such as trihydrated alumina, and it has no effect on calcium carbonate. It has been pointed out as a defect that the target inorganic substance lacks versatility such as not exhibiting it.

On the other hand, in the case of containing an activator as a dispersant for organic pigments, yellowing occurs in the production of laminated paper, and water repellency due to the activator when applied to printing inks, paints, etc.
The deterioration of printing characteristics becomes a problem. Further, the thermoplastic resin composition requires a large amount of resin in order to disperse it uniformly, and as a result, the organic pigment content is lowered, and the coloring power is lowered or it can be applied only to a vehicle which is compatible with the resin used. Such a drawback occurs.

Further, particularly in the case of cosmetic powder, since the surface of titanium dioxide, zinc white, etc. is hydrophilic, the mixing and dispersion with an oily base is poor, and it is difficult to obtain a cosmetic with a uniform and smooth feel, and to the skin. It has the drawback that makeup is easily destroyed by sweat or water due to insufficient adhesion. Further, for example, talc has a remarkably high pH and strong surface activity in comparison with the skin pH of 5 to 6, and thus accelerates the oxidation of the oily base used in cosmetics to generate peroxide. It has the drawback of being severely restricted in terms of safety and stability, such as causing skin irritation and alteration of perfumes.

Therefore, the objects of the present invention are as follows: 1) With a small amount of addition, a high effect of modifying the surfaces of inorganic and organic pigments is exhibited. 2)
The inorganic and organic pigments have strong adsorptive power to the surface and are less likely to be desorbed from the interface after treatment. 3) Surface modification of inorganic and organic pigments that satisfy various properties such as dispersibility, water repellency, solvent resistance, and printability required of modifiers such as adaptability to various inorganic and organic pigments. To provide quality agents.

Means for Solving the Problems In view of such circumstances, the present inventors have proposed a novel surface modifier for inorganic and organic pigments having the properties required for the surface modifier for inorganic and organic pigments as described above. As a result of earnest studies to develop an acidic amino acid, an acidic amino acid obtained by introducing an aliphatic amide group having 6 to 22 carbon atoms into the carboxyl group at the ω-position of an acidic amino acid-ω-excellent surface of inorganic and organic pigments even with a small amount It is an excellent surface modifier for inorganic and organic pigments that exerts a modifying effect, does not desorb from the adsorption surface even in various organic solvents, and has wide applicability for the target inorganic and organic pigments. Found and completed the present invention.

The acidic amino acid-ω-long chain amide obtained by introducing an aliphatic amide group having 6 to 22 carbon atoms into the carboxyl group at the ω-position of the acidic amino acid used in the present invention is an α or ω acidic amino acid such as glutamic acid or aspartic acid. It is easily obtained by introducing a hydrophobic amide group into the position. For example, after protecting the amino groups of these acidic amino acids, they are converted into acid anhydrides, and the carboxyl group at the ω-position is selectively amidated with an alkylamine having 6 to 22 carbon atoms. Is removed, the desired acidic amino acid-ω-long chain amide is obtained. Alternatively, after selectively protecting the ω-position carboxyl group of the acidic amino acid to form a monoester, the amino group is protected, the ester amide exchange reaction is performed with an arbitrary alkylamine, and then the amino group protecting group is replaced. Examples of the acidic amino acid used in the present invention which can be easily obtained by removing the amino acid-ω-long-chain amide include aspartic acid, glutamic acid, α-aminoadipic acid, α-aminopimelic acid and the like. However, these may be optically active or racemic. As the amide group, a saturated or unsaturated aliphatic amine having 6 to 22 carbon atoms is used,
Specific examples thereof include hexylamine, octylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, icosylamine and docosylamine. Further, it may be a mixture of these amide groups. The acidic amino acid-ω-long chain amide obtained by the above-mentioned method is a tabular powder microcrystal and can be used as a surface modifier as it is or by pulverizing to a desired particle size.

The surface modification method of the inorganic or organic pigment using the surface modifier of the present invention includes (1) adding the modifier as it is to the inorganic or organic pigment to be modified and pulverizing with a ball mill, atomizer, colloid mill or the like. Co-grinding using a machine, (2) adding the filler to a suitable organic solvent together with the filler, removing the solvent after stirring and mixing, (3) adding the present modifier to the mixture of the organic medium and the filler However, the method of mixing with a hot roll or the like can be mentioned, but the method of the above (2) is preferable in that a high surface modification effect can be obtained by adding an extremely small amount. It is used in the present invention. The form and particle size of the acidic amino acid-ω-long chain amide are not particularly specified, and they may be used after being appropriately pulverized as necessary.

The surface modifier of the present invention is calcium carbonate, titanium dioxide, kaolin, silica, mica, ferrite, metal powder,
Applicable to inorganic substances such as glass fiber and asbestos, as well as phthalocyanine pigments, dioxane pigments, quinacdrine pigments, anthraquinone pigments, indigo pigments, thioindigo pigments, quinophthalone pigments, azo pigments, perinone pigments. It can also be applied to organic pigments such as pigments and perylene pigments.

Further, the amount of acidic amino acid-ω-long chain amide added to these inorganic and organic pigments varies depending on the addition method.
0.5 to 20% by weight, 0.05 to 20% by weight in the wet method is preferable. If it is less than 0.5 or 0.05% by weight, the surface modification effect is not sufficient, and if it exceeds 20% by weight, the treatment effect does not improve so much. There is no advantage in terms of sex. Further, not only when the surface modifiers of the present invention are used alone or as a mixture, but also within the range not impairing the effect of the acidic amino acid-ω-long chain amide, other conventional agents are used. There is no problem even if a surface modifier is used in combination.

Effects of the Invention Inorganic and organic pigments surface-modified with the modifier of the present invention are resins such as polyurethane resin, vinyl chloride-vinyl acetate copolymer, epoxy resin, phenol resin, acrylic resin, cellulose resin, polyamide resin, urea resin and the like. Kind,
Or, it is very well dispersed in paints containing these resins, natural rubber, rubbers such as styrene-butadiene rubber and urethane rubber, and oils and fats such as squalane, liquid paraffin, beeswax, stearyl alcohol and isopropyl myristate. Elution in organic solvents of surface modifiers often observed when used in paints and the like found in inorganic and organic pigments treated with surface modifiers, aggregation or separation of modified inorganic and organic pigments, It has properties such that it does not cause defects such as graininess, color unevenness, and vividness of the coating film, and is excellent in water repellency, printing characteristics, and further, it is excellent in safety because it is composed of an amino acid that constitutes a living body. Therefore,
The inorganic and organic pigments surface-modified with acidic amino acid-ω-long chain amides are suitable in various fields such as paints, resins, inks, rubbers, stationery, and cosmetics. Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

Examples 1 to 8 Various surface modifiers in 25 ml of the organic solvent shown in the table below.
Add 05g and 0.5g of inorganic filler and shake for 10 minutes with an ultrasonic shaker. Then, it was left standing vertically and the dispersed state of the inorganic filler was visually judged.

As shown in the results of Table-1 to Table-4, the surface modifier of the present invention exerts an excellent dispersing effect even in various organic solvents, and the target inorganic filler has a wide variety of characteristics. Have.

Example 9 100 g of a water-containing cake of Shinka Shared (solid content 25%)
Contains 1 g of glutamic acid-γ-palmitylamide
Neutralize by adding 100 ml of 1N NaOH solution and adding an equivalent amount of 1N HCl solution while stirring vigorously with a homogenizer. After stirring for 1 hour as it is, it is filtered, washed with water, dried and pulverized.

The thus-obtained Shinka Shared is excellent in dispersibility in toluene and spindle oil, and exhibits high water repellency, and thus is suitable as a pigment for paints.

Example 10 Phthalocyanine green water-containing cake (solid content 25%)
100 g is added to 100 ml of a 1 N NaOH solution containing 1 g of aspartic acid-β-laurylamide, and the mixture is neutralized by adding an equivalent amount of a 1 N HCl solution with vigorous stirring with a homogenizer.
After stirring for 1 hour as it is, it is filtered, washed with water, dried and pulverized.

The phthalocyanine green thus obtained has excellent dispersibility in toluene and spindle oil.

Example 11 10 g of the organic pigments obtained in Examples 9 and 10 were mixed with 90 g of various dispersion media in a paint shaker for 10 minutes, and the dispersion stability after standing for 24 hours was visually evaluated, and the results are shown in Table-5. It was
In the comparative example, the water solution cake of the organic pigment was directly dried without adding the alkaline solution of the surface-modifying agent acidic amino acid-ω-long chain amide and the neutralizing agent, and the same method as in Example 9 or 10 was performed. What was crushed was used.

Example 12 Solid foundation A component Yellow iron oxide 0.8 parts by weight Red iron oxide 0.5 〃 Titanium oxide 11.0 〃 Zinc oxide 8.5 〃 Talc 25.0 〃 Kaolin 41.5 〃 B component Glutamic acid-γ-laurylamide (average particle size 2μ) 1.
0〃 glutamic acid-γ-palmitylamide (average particle size 1.5
μ) 2.5 〃 C component Liquid paraffin 6.0 〃 1,3-butylene glycol 3.0 〃 Fragrance 0.2 〃 Component A is mixed with a Hensyl mixer for 10 minutes, then component B is added and stirred for 10 minutes for surface treatment. It was

The component C was added to the surface-treated component A, the mixture was stirred and mixed for 20 minutes, the fragrance was added at 35 ° C. or lower, the mixture was further mixed for 10 minutes, taken out, and press-molded to prepare a solid foundation. Further, as a comparative example, a solid foundation was prepared in the same manner by substituting 14.5 parts by weight of titanium oxide as the component A instead of the component B, and sensory evaluation was conducted by 20 women in their 20s to 40s. Got the result.

From the above results, the solid foundation of the present invention, compared to the solid foundation of Comparative Example, elongation to the skin,
It will be understood that it is an excellent solid foundation that has excellent adhesiveness and also imparts a transparent feeling and a moist feeling.

Claims (1)

[Claims] 1. An acidic amino acid in which an aliphatic amide group having 6 to 22 carbon atoms is introduced into the ω-position carboxyl group of an acidic amino acid
Surface modifiers for inorganic and organic pigments containing at least one ω-long chain amide.