JPS61236862A - Stable ultramarine and production thereof - Google Patents

Abstract

PURPOSE:Stable ultramarine, obtained by coating ultramarine particles with a high-molecular weight silicone resin and having improved acid and heat resistance without causing deteriorated odor even in coexistence with a perfume. CONSTITUTION:Stable ultramarine obtained by coating ultramarine particles with a silicone resin prepared by bringing the ultramarine into contact with a cyclic silicone expressed by the formula (R is lower alkyl or aryl; n is 3-7) and polymerizing the cyclic silicone on the surface thereof, expressed by the formula [RSiO3/2]a[RHSiO]b [a and b are 20<=100a/(a+b)<=100] and having >=200,000 molecular weight.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a stable ultramarine blue coated with a specific silicone resin and a method for producing the same. Ultramarine blue is used as a blue colorant in the fields of paints, inks, and cosmetics.

(Background Art and Prior Art) Gunjio is an inorganic pigment that usually exhibits a beautiful blue color with a slight reddish tinge.It was originally made from natural lilystone, but recently it has been made artificially. Manufactured. Ultramarine is sodium aluminum silicate containing sulfur, and is generally represented by the following compositional formula.

NaL8~o) AlaSja 0245 (2-41 ultramarine is a hydrophilic, oleophobic composition, and is heated to about 250°C in air.
It is stable and has ion exchange and catalytic abilities. Some of the sulfur in ultramarine is in the active radical form, and differences in the radical state and oxidation state of this sulfur cause changes in the color tone of ultramarine, and in addition to the reddish blue mentioned above, it also has a purple tinge. There are some that are yellowish and some that are greenish.

Ultramarine blue is used as a blue coloring agent in a wide variety of fields, including building materials, paints, printing inks, paints, paper, textile products, cosmetics, and detergents.Its color is extremely clear and is harmless to humans and animals. It has become important recently.

However, ultramarine blue has serious deficiencies as a colorant. In other words, ultramarine blue is generally stable against alkalis, but extremely weak against acids, and as a result of the reaction between radical sulfuric acid and acid, hydrogen sulfide is generated under acidic conditions and it gradually decomposes and fades, becoming white. Ultramarine blue also generates hydrogen sulfide when subjected to mechanical shearing force such as crushing or heat. The hydrogen sulfide generated in this way causes problems such as secondary deterioration of container materials such as aluminum, and also causes odor changes in products in the field of cosmetics and the like.

In order to overcome these drawbacks, several proposals have been made to improve the stability of ultramarine. Recent methods include, for example, a method of treating ultramarine blue with silicate) and an organic acid to form amorphous silica on the surface (Japanese Patent Application Laid-open No. 54-95632), and a method of forming amorphous silica on the surface of ultramarine blue with acid resistance. There is a method of forming a polymer film (Japanese Patent Publication No. 50-27483). Although these conventional methods improve the acid resistance of ultramarine blue to some extent, they are still not sufficient.

(Structure and Effects of the Invention) In view of the above circumstances, the present inventors have conducted intensive research to develop a stable ultramarine blue having sufficient acid resistance and heat resistance, and as a result, the silicon on the formula % formula % We discovered that resin-coated ultramarine effectively suppresses the generation of hydrogen sulfide under acidic conditions and high temperatures, and that it does not decompose fragrances, etc., and succeeded in developing a stable ultramarine that is suitable for the purpose. did.

That is, the first aspect of the invention satisfies the following relational formula % in the ultramarine particles: shall be taken as a thing. ) It is a stable ultramarine blue coated with silicone resin with a molecular weight of 200,000 or more.

The stable ultramarine blue according to the present invention is stable against acid, heat, and mechanical shearing force, and does not decompose due to these actions and substantially does not generate hydrogen sulfide. Therefore, it can be used, for example, under acidic conditions. It does not alter the quality of container materials such as aluminum, nor does it cause odor to cosmetics.

In addition to these properties, the ultramarine blue according to the present invention has CR8i,
03/2, l a Because it is coated with a silicone resin called CRHS Orb, it exhibits hydrophobicity and not only suppresses "wetting" to acids, but also enters the oil phase in emulsion systems, so it is difficult to use in ultramarine. This restriction has been removed and it has become possible to use it for a wide range of purposes.

In the stable ultramarine blue according to the present invention, the surface of the ultramarine particles is CR8t.
It is coated with a silicone resin called OS/2)a CRH8LO)b, and the reason for its excellent stability is that the sulfur on the ultramarine surface is not in direct contact with the outside air. Sulfur on the surface of ultramarine blue, or surface sulfur, refers to radical sulfur that exists on the surface of the crystal lattice of ultramarine. tend to have various types of activity against substances.

This active surface sulfur decomposes under the action of acid, heat, and mechanical shearing force, generating hydrogen sulfide.

This surface sulfur is coated with silicone resin, which stabilizes the ultramarine and prevents it from decomposing even when exposed to acid or heat, suppressing the generation of hydrogen sulfide. In this case, since the silicone resin is highly transparent, there is no difference in color tone between the stabilized ultramarine and the untreated one.

The stable ultramarine according to the present invention is a powder, and its particle size is not particularly limited, but it is usually 0.1 to 20 μm, preferably 0.3 to 2 μm for blue ones, and has a reddish blue color. For objects, it is 2 to 10μ.

The silicone resin that covers the surface is (R8tOS/2)
It has a structural formula of a[RHstO) b and a molecular weight of 200,000 or more. If the molecular weight is less than 20,000, the coated silicon will be eluted by chloroform or the like, and complete coating cannot be achieved.

In the formula, R is a lower alkyl group such as a methyl group, an ethyl group,
Or it represents an allinyl group such as a phenyl group. Those with methyl group are easily available.

In the formula, the ratio of a and b is 20≦100a/(a+b)≦10
Since the potato seed has a large network structure with a value of tooa/(a+b) in the range of 0, there is a small possibility that it will be liberated if it enters the solvent system. The ratio of a and b can be calculated from the infrared absorption spectral.

The amount of silicone resin present in the stable ultramarine of the present invention is:
It varies depending on the surface area and surface activity of ultramarine, but about 0.1~
20% by weight, preferably 0.2 to 2.0% by weight.

If it is less than 0.11% by weight, effective stability cannot be imparted to the ultramarine blue, and if it exceeds 20% by weight, the ultramarine blue particles tend to bond with each other and cause aggregation, which is disadvantageous.

The stable ultramarine according to the present invention has the above (R
81O3/2) a (RH8jO,) b It only needs to be coated with the silicone resin, so even if it is a plastic or metal oxide whose surface has been treated with ultramarine blue,
A stable ultramarine blue can be obtained by coating with silicone resin.

The second aspect of the present invention is a method for producing the stable ultramarine blue described above, in which ultramarine particles are represented by the following formula (wherein R represents a lower alkyl group or an aryl group, and n is 3 to 7). This is a method in which surface polymerization is carried out by bringing cyclic silicon into contact with each other.

It can be produced by dissolving the cyclic silicon represented by formula (II) in a solvent, dispersing ultramarine blue, and then drying it, or it can also be produced by directly spraying the cyclic silicon dissolved in a solvent and drying it by heating.

In addition to reacting in a liquid phase, the reaction can also be carried out in a solid phase. That is, by treating ultramarine and the cyclic silicon of the formula [■] in a ball mill, it is also possible to produce the stable ultramarine of the present invention through the solid phase reaction.

The method of the present invention in which surface polymerization is carried out using the cyclic silicone of the formula [■] is a simple and effective method that utilizes the polymerization activity of ultramarine blue. This point will be explained in detail below.

When left standing, cyclic silicon is adsorbed in molecular form on the ultramarine surface. Generally, heat or a polymerization catalyst is used to cause polymerization on the surface, but according to the knowledge obtained by the present inventors, the ultramarine surface has &-H groups cross-linked to form st-0-Si. It was found that it has a catalytic effect to generate the bond of .

The cyclic silicone adsorbed on the ultramarine surface is successively crosslinked due to the surface activity of the ultramarine blue, forming a mesh-like silicone resin. When the silicone resin is coated on the ultramarine surface in this way, the surface active sites on the ultramarine surface are blocked, and the subsequent adsorption and crosslinking reactions do not proceed and film formation stops.

After that, degassing removes unreacted cyclic silicon, creating ultramarine blue coated only with silicone resin.

The temperature at which ultramarine blue and cyclic silicon are left at a temperature of 100° C. or less is sufficient, and the conventionally required temperature of 150° C. is not necessary because ultramarine blue has surface activity.

The ultramarine to be treated can be dried in advance, or if it contains some moisture, there is no need to heat it.
If heating is performed at about 0° C., the value of 100 m/(a+b) will only increase and will not exceed the scope of the present invention.

According to this method, stable ultramarine can be produced just by leaving it standing, so even if plastic or metal oxides have been surface-treated with ultramarine, it is easy to process them by processing the plastic and ultramarine in a ball mill to make the surface ultramarine. The present invention can also be applied to composite powder coated with.

The third aspect of the present invention is a manufacturing method for obtaining the stable ultramarine, in which the ultramarine particles are prepared using the following formula:
, -...-CmE (in the formula R
represents a lower alkyl group or an aryl group, and X represents a halogen. ) is a method in which the organohalosilane shown in the formula is brought into contact with each other to cause a hydrolysis/crosslinking reaction.

For example, by dissolving organochlorosilane R54w4 (R: methyl group, ethyl group, phenyl group) in a solvent and dispersing ultramarine, a hydrolysis/crosslinking reaction is caused, and the ultramarine surface is coated with a silicone resin called CR&0372)a (RHStOEb). In this case, the reaction can be controlled by adding calcium carbonate.

Example 1 Ultramarine powder 100? and tetrahydrotetramethylcyclotetrasiloxane 201 were placed in separate containers and left in a sealed relationship at room temperature. After 96 hours, the ultramarine was taken out and its weight was measured, and the treated ultramarine had a weight of 100.78F, and when it was left in a dryer at 50°C for 24 hours, it weighed 100.32.
A final treated ultramarine of F was obtained.

Example 2 50 g of chloroform and 2 g of heptahydrohbutamethylcycloheptasiloxane. After dissolving 10 g of ultramarine blue, the mixture was thoroughly stirred and dried at 80°C. 11.8 with this method
A final treated ultramarine of f was obtained.

Example 3 2 tons of methylhydrodichlorosilane was dissolved in diethyl ether 10F, and ultramarine blue 52 was added while cooling with ice water. After reacting for 2 hours, it was filtered and dried at 80°C. 5.6
A final treated ultramarine of f was obtained.

Example 4 100j of 12 nylon fine powder (spherical, about 5 μm in diameter) was placed in a centrifugal rotary sol mill, ultramarine 20 mm and 2 fmnφ alumina pole 50 o2 were added, and the mixture was stirred at 230 rpm for 5 hours. Thereafter, pentahydroink methylcyclotetrasiloxane 22 was added and stirred for an additional 3 hours to obtain the final treated ultramarine blue.

Example 5 Ultramarine blue powder 10P, tetrahydrotetramethylcyclotetrasiloxane 12, and pentahydropentamethylcyclopentasiloxane 12 were mixed together and a saliva solution was placed in separate containers; they were left in a closed system at 90°C. After 24 hours, the ultramarine was removed and left in a dryer at 90°C for another 24 hours.
A final treated ultramarine of 0.13f was obtained.

Regarding the ultramarine of Example 1, (1) measurement of a, b ratio, (2)
Chloroform elution measurement of silicone resin, (3) hydrogen sulfide measurement using hydrogen sulfide detection method, (4) hydrogen sulfide measurement using silver plate blackening test method, and (5) microreactor Nyorori Naol decomposition measurement were performed.

(1) a, b ratio [crosslinking rate 100 a / (a +
b)) Measurement of silicone resin (R) coated on the ultramarine surface in the present invention.
StO3/2)a (RH,9=O)b 100a/(
a+b) indicates the %-H group crosslinking rate, which can be measured using a Hu IJ conversion infrared spectrophotometer.

Samples 100~ and 900 mg of KBr powder were uniformly mixed, placed in a cell for measuring diffuse reflection spectra, and measured under the following conditions.

Resolution: 1-1 Number of integrations: 100 Wavenumber range: 1,300-1,200 an-"Next, the obtained spectrum was subjected to Kuperkam/refunction conversion using the attached computer software, and then the peaks were determined by the deconstruction method. We did the split.

The spectrum after peak splitting is 126/(1)-1 and 12
The peak was maintained at 72 cm-” and 126/an-”
The peak of (RH81O) b is assigned to the methyl group, and the peak of 1272 sub-1 is assigned to (Rst O3/2
).

The crosslinking rate of the silicone resin can be calculated using the following formula.

■: Peak height of 126/3 ■: Peak height of 127/(1)-1 2) Chloroform elution measurement sample 2 of silicone resin
After dispersing 0f in chloroform 100M and filtering it, P
After concentrating the liquid using an evaporator, the molecular weight was measured using glupermeation chromatography. The device is J
apan Analytical Industry
The solvent for Co, Ltd LC-Q8 was chloroform (1,
07m//mtn), and an RI detector was used. Molecular weight was estimated from a standard polyethylene calibration curve.

The filtered ultramarine blue was dried at 80° C. for 24 hours and tested for water repellency.

(3) Measurement of hydrogen sulfide using the hydrogen sulfide detection method: Attach a 5ON dropping funnel and a simple gas detection tube that can detect hydrogen sulfide to a 200 ml three-necked round-bottomed flask with a magnetic stirrer, connect the detection tube to a water pump, and measure the amount of hydrogen sulfide generated. Hydrogen sulfide gas was always sucked in at a constant pressure. A scale was printed directly on the gas detection tube, and hydrogen sulfide of 0.1 to 2.0% could be directly read.

Measurement was performed using this measuring device in the following manner.

Put ultramarine 0.52 in a three-neck round bottom flask and add 5
It was uniformly dispersed in ion-exchanged water of at. Next, IN hydrochloric acid 5- was added all at once through the funnel.1. Stir with a magnetic stirrer.

The amount (%) of hydrogen sulfide produced by the decomposition of ultramarine blue by acid was read using a detection tube.

(4) Measurement of hydrogen sulfide using silver plate blackening test method Ultramarine blue and silver plates were left at 80°C for 2 days in a sealed container, and the extent to which the silver plates blackened due to the hydrogen sulfide generated during that time was observed with the naked eye. .

(5) Measurement of decomposition of linalool using a microreactor The powder was fixed in a Pyrex glass tube with an inner diameter of 4 mm using quartz wool, and the decomposition of linalool, one of the aroma components, was measured at a reaction temperature of 180'C. . Linalool injection amount is 0.3μ! , carrier gas is nitrogen, flow rate is 50 m
l/min.

The analysis was performed using a bird body GC-7A. Column is 5% FFAP
/ chromosorb w 80/ 1003 m
The column temperature was 80°G (4mln) to 220°C, and the heating rate was 5°C/mln.

(6) Measurement of water repellency 5 ml of ion-exchanged water was placed in a 10+++ sample tube, and 0.12 ml of the sample was added and shaken.

After shaking, it was left to stand for 24 hours and it was determined whether the ultramarine blue was dispersed in the water or floated on the surface.

(Results and evaluation regarding Example 1) (1) From the results of infrared absorption spectrum, 100a/(
It was found that a+b)=44. Therefore (CH3
It can be seen that 44% of the structure of 5i03/2, la C(CH,)H8iO)b is crosslinked with a, forming a fairly network structure.

(2) As a result of the chloroform eluate obtained in the chloroform elution experiment, it was revealed that the silicone resin was not eluted in chloroform. This indicates that the silicone resin on the surface of the ultramarine blue has become a polymer and has become insoluble in chloroform. In a similar glumeation experiment, silicon with a molecular weight of less than 200,000 was eluted into chloroform, so it is thought that the silicone resin polymerized on the ultramarine surface has a molecular weight of 200,000 or more. This result is
In good agreement with the above result of 10oa/(a+b)-44,
This shows that the mesh-structured silicone resin is tightly coated on the ultramarine surface.

(3) According to the results of the hydrogen sulfide detection method, untreated ultramarine rapidly generates hydrogen sulfide, reaching 1.0% or more in 10 minutes, but the ultramarine obtained in Example 1 does not.

(4) In the silver plate blackening test, there was no change in the ultramarine blue obtained in Example 1, but the untreated ultramarine blue was completely blackened. According to these results, it can be seen that the ultramarine blue obtained in Example 1 is extremely excellent in heat resistance.

(5) According to the results of the microreactor Nyorori nalool decomposition measurement, in the untreated ultramarine, linalool decomposes and many decomposition products are produced, but in the ultramarine obtained in Example 1, almost no linalool is decomposed. These results show that the ultramarine blue obtained in Example 1 is resistant to acids and heat, does not release hydrogen sulfide, and has no effect of decomposing fragrance components, and is an excellent product that does not cause odor even when coexisting with fragrances. It is ultramarine.

(6) According to the water repellency measurement results, the untreated ultramarine was well dispersed in water and showed no water repellency at all, whereas the ultramarine of Example 10 exhibited water repellency and floated on water. Furthermore, it was confirmed that the ultramarine blue after chloroform elution also had water repellency. This indicates that the silicone resin on the ultramarine surface was not eluted by chloroform and was coated on the surface, and that the surface condition remained almost unchanged.

(Results and evaluation regarding Examples 2 to 5) It is clear from the results in the table below that the ultramarine blue obtained in Examples 2 to 5 was stable ultramarine, similar to the ultramarine blue obtained in Example 1. .

Table 1 Pickles

Claims (4)

[Claims] (1) For ultramarine particles, use the following formula [RSiO_3_/_2]a [RHSiO]b...
... [I] (In the formula, R represents a lower alkyl group or an aryl group, and a and b satisfy the following relational formula 20≦100a/(a+b)≦100.) A molecular weight of 200,000 or more A stable ultramarine blue coated with silicone resin. (2) The stable ultramarine blue according to claim (1) coated with 0.1 to 20% by weight of silicone resin. (3) Ultramarine particles have the following formula ▲ Numerical formula, chemical formula, table, etc. ▼ ... [II] (In the formula, R represents a lower alkyl group or aryl group, and n is 3 to 7. ) The following formula [RSiO_3_/_2]a[RHSiO]b... is characterized by contacting and surface polymerizing the cyclic silicon represented by
・[I] (In the formula, R represents a lower alkyl group or an aryl group, and a and b satisfy the following relational formula 20≦100a/(a+b)≦100.) With a molecular weight of 200,000 or more Stable ultramarine blue manufacturing method coated with silicone resin. (4) The ultramarine particles are brought into contact with an organohalosilane represented by the following formula RSiHX_2...[III] (wherein R represents a lower alkyl group or aryl group, and X represents a halogen). Hydrolysis·
The following formula [RSiO_3_/_2]a[RHSiO]b is characterized by a crosslinking reaction.
... [I] (In the formula, R represents a lower alkyl group or an aryl group, and a and b satisfy the following relational formula 20≦100a/(a+b)≦100.) A molecular weight of 200,000 or more A stable ultramarine blue coating method coated with silicone resin.