JPS63165461A - Surface-treated powder - Google Patents

Abstract

PURPOSE:To obtain the titled powder having high hydrophobic property, water- repellency and stability and useful for cosmetics, pharmaceuticals, resin compositions, paints, inks, colors, etc., by irradiating powder with low- temperature plasma in the presence of a specific organosiloxane. CONSTITUTION:The objective powder can be produced by irradiating (A) powder (e.g. talc, kaolin, gamma-iron oxide, etc.) with low-temperature plasma (preferably in vacuum or in the presence of N2, O2, H2, Ar, He or air) in the presence of (B) an organosiloxane of formula [R1-R5 are H, halogen, OH, mercapto, acyloxy, alkoxy, amino, nitro, carboxyl, sulfone, 1-30C (substituted)hydrocarbon group, aromatic group, heterocyclic group, alicyclic group, spiro compound residue or terpene compound residue; excluding the case that 2H atoms are bonded to the same Si atom; m is 1-250; n is 0 or 2]. The amount of the component B is preferably 0.1-20wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a powder surface-treated with organosiloxane. More specifically, the present invention relates to a surface-treated powder in which the powder is treated with an organosiloxane using low-temperature plasma irradiation to improve the color separation, blocking of active sites, and dispersibility of the powder, and to provide various functions.

Such surface-treated powders can be used in cosmetics, pharmaceuticals, resin compositions, paints, inks, paints, ornaments, fragrances, magnetic materials, chromatographic carriers, and the like.

[Prior Art] In most conventional sulganosiloxane treatments, a surface reaction is carried out in a solvent while adding a catalyst, and this method involves complicated steps. Furthermore, when drying the surface-treated powder, problems such as agglomeration of the powder and residual catalyst occur.

In particular, residual catalyst is undesirable because it causes deterioration of the coated organosiloxane and decomposition and deterioration of cosmetic ingredients such as fragrances.

Also, JP-A-56-16404, JP-A-55-1
No. 36213 and JP-A-56-29512 disclose that organosiloxane and oil are added to powder,
A technique for baking the powder surface is disclosed. However, these methods have the fatal drawback of impairing the color tone of powders such as yellow iron oxide and deep blue among heat-sensitive organic and inorganic powders.

Furthermore, JP-A-56-16404 describes a method for treating sulganosiloxane powder using a mechanochemical reaction. Since this method does not require a baking treatment, it can also be applied to powders with poor temperature stability. However, since this mechanochemical method inevitably involves crushing force, it has the disadvantage that it may destroy some powder shapes (particularly powders characterized by plate-like or spherical shapes).

Furthermore, in the treatment of organosiloxane oil, methylhydrogen polysiloxane is often used, and the treatment effect is enhanced by the reactivity of its 5i-H group, but the 5i-H group becomes unstable over time, and water or ethanol When it comes into contact with other substances, hydrogen gas is generated, which impairs the stability of the product.

In addition, silane coupling agents are used to bond functional groups with various functions to powders, but although silane coupling agents can treat silica well, they are not satisfactory for other substances. It was not something I could enjoy.

[Problems to be Solved by the Invention] In view of these circumstances, the present inventors have developed an effective sulganosiloxane that has a simple process, no agglomeration of powder, no residual catalyst, and no deterioration of powder due to heat. As a result of intensive research into whether there is a surface treatment method, the present invention was completed.

[Means for Solving the Problems] That is, the present invention is a surface-treated powder obtained by irradiating a powder with low-temperature plasma together with one or more organosiloxanes represented by (a) below.

The present invention will be explained in more detail below.

The organosiloxane used in the present invention has the following formula (
(hereinafter referred to as silicone) (a).

(a) (RIR2Sio)m(1't3R4R5Si0□, 5
) n ′ (wherein R1, R2, R3, R4 and R
5 is a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, an acyloxy group, an alkoxy group, an amino group,
Nitro group, carboxyl group, sulfone group or substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms [e.g. aliphatic group (e.g. alkyl group, alkenyl group, alkynyl group), aromatic group (e.g. phenyl group, naphthyl group) ), heterocyclic groups (e.g. those containing one or more nitrogen atoms, oxygen atoms or sulfur atoms as heteroatoms), alicyclic groups (e.g. cycloalkyl groups, cycloalkenyl groups, cycloalkynyl groups), spiro compound residues or terpene compound residue]. However, the hydrogen atom is 2 times the same silicon atom.
They do not exist in combination. m is an integer from 1 to 250, and n is O or 2.

More specifically, it is a linear organosiloxane represented by (b) in the following formula or a cyclic organosiloxane represented by (C).

In the formula, R6, R7 and R8 are each a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, an acyloxy group, an alkoxy group, an amino group, a nitro group, a carboxyl group, a sulfone group, or a substituted or unsubstituted group having 1 to 30 carbon atoms. Hydrocarbon groups [e.g. aliphatic groups (e.g. alkyl, alkenyl, alkynyl), aromatic groups (e.g. phenyl, naphthyl), heterocyclic groups (e.g. a nitrogen atom as a petro atom, an acid g atom or an acid atom) alicyclic group (e.g., cycloalkyl group, cycloalkenyl group, cycloalkynyl group), spiro compound residue, or terpene compound residue]. However, two hydrogen atoms cannot exist bonded to the same silicon atom. X represents an integer of 1 to 250, and y represents a numerical value of 3 to 250. The smaller the number of X in formula (b) and the number of y in formula (c), the lower the boiling point and the larger the amount of adsorption of the powder due to its lower boiling point, so it is preferable. It is most preferred because it is easy to polymerize due to its properties. However, even those with a high boiling point can be added and processed in liquid form.

In the present invention, any one or a combination of two or more of these may be selected and applied. The amount of silicone used is generally preferably 0.1 to 20% by weight based on the powder. If it is less than 0.1% by weight, it is insufficient to produce a treatment effect, and if it exceeds 20% by weight, it is undesirable because it is excessive and tends to cause the powder to aggregate.

The powder used in the present invention is not particularly limited, and includes, for example, talc, kaolin, sericite, muscovite, synthetic mica, phlogopite, red mica, biotite, lithium mica, vermiculite, magnesium carbonate, calcium carbonate, diatomaceous earth, Inorganic powders such as magnesium silicate, calcium silicate, aluminum silicate, barium silicate, barium sulfate, strontium silicate, metal tungstate, silica, hydroxyapatite, zeolite, boron nitride, ceramic powder, nylon powder, polyethylene powder , benzoguanamine powder, tetrafluoroethylene powder, distyrene benzene vinyl polymer powder,
Organic powders such as microcrystalline cellulose, inorganic white pigments such as titanium oxide and zinc oxide, inorganic red pigments such as iron oxide (red iron oxide) and iron titanate, inorganic brown pigments such as γ-iron oxide, yellow iron oxide, and ocher. Inorganic yellow pigments such as black saponified iron, inorganic black pigments such as carbon black, mango violet,
Inorganic purple pigments such as cobalt violet, chromium oxide,
Inorganic edge color pigments such as chromium hydroxide and cobalt titanate, inorganic blue pigments such as ultramarine and navy blue, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, bismuth oxychloride, titanium oxide coated talc, fish scale foil, colored titanium oxide Pearl pigments such as Courtrad mica, metal powder pigments such as aluminum powder and copper powder, Red No. 201, Red No. 202, Red No. 204, Red 205
Organic pigments such as Red No. 220, Red No. 226, Red No. 228, Red No. 405, Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401 and Blue No. 404, Red No. 3
No., Red No. 104, Red No. 106, Red No. 227, Red No. 203, Red No. 401, Red No. 505, Orange No. 205, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203,
Organic pigments such as green No. 3 and blue No. 1 zirconium, barium or aluminum lake, chlorophyll, β
-Natural pigments such as carotene are used, but are not limited thereto.Next, in the present invention, the mixture of silicone and powder is irradiated with low-temperature plasma, and the plasma used at this time is: It can be generated by corona discharge, glow discharge, etc. in low frequency and high frequency regions. This low-temperature plasma irradiation makes it possible to create stable skin FfA even with dimethyl-type silicone, which could hardly be treated in the past.
Not only does it show better water repellency than conventional methyl hydrogen type treatment, it also makes it possible to produce a powder that is surprisingly stable against water and methanol. The irradiation atmosphere is
It may be carried out under vacuum or in the presence of nitrogen, oxygen, hydrogen, argon, helium, or air. The processing time changes the hue of the powder,
It is preferable to carry out the treatment within a range that does not adversely affect weather resistance, etc., and an appropriate treatment time can be selected depending on the type of gas used, the output of plasma, the type of powder to be treated, etc., but preferably 20 seconds to 60 seconds. It's a minute.

Specifically, low-temperature plasma irradiation may be performed using, for example, Practical Line (manufactured by Sankyo Dengyo ■). Practical lines can be processed either directly in the atmosphere or with specific gases in contact with the powder. It is particularly suitable for processing on an industrial scale.

The molecular weight of the silicone resin formed on the powder surface using the above low-temperature plasma irradiation is 150,000 or more. There is no way to confirm that the molecular weight is 150,000 or more. In other words, in the case of silicone, as it becomes polymerized through polymerization, it becomes less soluble in water and organic solvents, making it impossible to extract the resin and measure its molecular weight, and the state in which it is coated on the powder surface becomes difficult to dissolve in water and organic solvents. It is impossible to measure the molecular weight of the resin at

Therefore, in order to estimate the molecular weight indirectly, we extracted with chloroform without sufficient polymerization, and the extract was
When analyzed by PC (gel permeation chromatography) and the molecular weight of the extracted resin was determined in terms of polystyrene, the maximum was 150,000. therefore,
It can be said that the molecular weight of the resin that has been sufficiently polymerized to eight states that are not extracted by chloroform is 150,000 or more.

[Example] Next, the present invention will be explained in more detail by giving examples. However, the present invention is not limited thereto.

Example 1 10 g of yellow iron oxide and cyclic silicone [in formula (c) R6=CH3, R7=CH2CH2CF3 and y=3
] Ig was mixed uniformly, and using a practical line (manufactured by Sankyo Dengyo ■), nitrogen was added at 200 m1/m.
Low-temperature plasma irradiation was performed for 20 minutes under conditions of low frequency (5 kHz) and output of 30 W while flowing in.

-Infrared absorption spectrum- The results were measured using a powder reflection method using an infrared absorption spectrum measuring device, Orimai Tsuta, manufactured by DigiLab.

Figure 1 is an infrared absorption spectrum of the cyclic silicone used in Example 1. Figure 2 (A) is an infrared absorption spectrum of untreated yellow iron oxide.

FIG. 2(B) is an infrared absorption spectrum of the treated powder of Example 1.

Figure 2 (B) is compared with Figure 2 (A) (A) 1025
5l-0-Si group in cm, (b) 5i in 1265cm
-CH3 group, (c) C-F group at 1308cm, (d)
5i-CH3 group at 1425cm, (e) 1440c
Peaks suggesting CH2 groups appear at a+. Although these peaks are weaker in intensity, they are the same as peaks 1 to 5 in Figure 1, indicating that silicone covers the yellow iron oxide surface. Figure 2 (C) is an example. It can be seen that the same peak as in Figure 0-2 (B), which is an infrared absorption spectrum of the treated powder of No. 1, which was soaked in chloroform for 12 hours, filtered, and dried, was obtained.

As mentioned above, it does not elute even in chloroform etc.
It is clear that the silicone covers the yellow iron oxide surface quite firmly.

Comparative Example 1 Cyclic silicone [formula (c
) in R6=Cl-13, rt7=c H2CH2
CF3 and y=3] Hexane solution 2 containing Ig
After adding 5 g and stirring well, the mixture was evaporated and transposed. Thereafter, baking was performed at 250°C.

Comparative Example 2 10 g of yellow iron oxide and cyclic silicone [in formula (C), Rθ=CH3, R7=CH2CH2CF3 and y=3
11 g of the sample was placed in a ball mill and mixed and ground for 30 minutes. Regarding each of Example 1, Comparative Example 1, Comparative Example 2, and untreated yellow iron oxide, hydrophobicity, water repellency,
Activity against color change and fragrance was determined.

- Hydrophobic - Put 5 ml of ion-exchanged water into a 10 ml sample tube, add 0.1 g of sample, and shake.

The criteria for determining hydrophobicity are as follows.

×... Dispersed in water.

Δ: Hydrophobic, but partially dispersed in water.

0...It was hydrophobic and the entire amount floated on top of water.

The results are shown in Table-1.

The untreated yellow iron oxide was dispersed in water, but in Example 1 and Comparative Example 2, it was hydrophobic and floated on water, and in Comparative Example 1, the treatment was not complete and a portion was dispersed in water.

One ice-repellent sample (0.5 g) was molded into a pellet using a tablet molding machine, and 50 μl of distilled water was dropped onto the pellet. The measurement was performed twice, immediately after dropping and once 30 minutes later, by determining the contact angle using a microscope. It was shown that the larger the contact angle, the higher the water repellency.

Fill a sample with one color change degree into a cell for powder measurement, and fill it with Hitachi Color Analyzer 60? 380nm to 780n in mold
It was measured in a range of m. Measurement results are displayed on the beam, a, b,
Table 1 also shows the color difference ΔE before and after the treatment.

It can be seen that the color difference ΔB in Example 1 is significantly smaller than that in the comparative example.

Decomposition of a fragrance - 20 mg of powder was fixed with quartz wool in a Pyrex glass tube with an inner diameter of 4 mm, and linalool, one of the fragrance components, was passed through the tube at 185°C to measure its decomposition behavior. Linalool injection amount: 0.3μ, carrier gas: nitrogen, flow rate;
50m1/m1n0 analysis was performed using Shimadzu GC-7A, column PEG-20M, 0.31mm x 25m,
The column temperature was 80°C (4 ml) → 220°C, and the heating rate was 5°C/min. The indications in the table are as follows.

Untreated yellow iron oxide Δ Decomposition is more rapid than untreated yellow iron oxide X Decomposition is less than untreated yellow iron oxide In untreated yellow iron oxide receptor, part of linalool decomposed and five decomposition products appeared: myrcene, limonene, cis-ocimene, trans-ocimene, and turbinolene. In Example 1, no decomposition products appear and only the peak of linalool appears, indicating that the linalool decomposition activity is absent compared to the untreated product. In Comparative Example 1, linalool was completely decomposed and eight decomposition products appeared: myrcene, α-terpinene, limonene, cis-ocimene, trans-ocimene, para-cymene, cis-alloocimene, and trans-alloocimene. In other words, the decomposition activity of the powder of Comparative Example 1 was increased compared to the untreated powder, indicating that the fragrance stability was worsened. In Comparative Example 2, a portion of linalool was decomposed and six decomposition products appeared: myrcene, α-terpinene, limonene, cis-ocimene, trans-ocimene, and para-cymene. The activity was weaker than in Comparative Example 1, and unreacted glue remained, but
It is clear that the activity is stronger than that of the untreated one.

As described above, Comparative Examples 1 and 2 have stronger linalool decomposition activity and worse flavor stability than the untreated sample. On the other hand, in Example 1, the linalool decomposition activity was weakened and the fragrance stability was improved.

Judging from Table 1 comprehensively, it can be seen that Example 1 maintains almost the same color as the untreated sample and has hydrophobicity and water repellency. Furthermore, the stability of fragrances has been improved, and it is considered to be an extremely excellent treated powder when blended into cosmetics and the like.

Example 2 5g of ultramarine blue and linear silicone [R6= in formula (b)
CH3, R7=CH3, R6=CH3 and X=3-2
0] were mixed uniformly, and using a practical line (manufactured by Sankyo Dengyo ■), 200ml/nitrogen was added.
Output 20W by applying low frequency (5KHz) through min.
A treated powder was obtained by irradiating the powder with low temperature plasma for 15 minutes under the following conditions. The resulting treated powder had good hydrophobicity and water repellency.

Example 3 5 g of navy blue and linear silicone [formula (b) Re”CH3,
R7=CH3, R8=CH2CH2CF3 and X=3
- 10 pieces] were mixed uniformly, and using a practical line (manufactured by Sankyo Dengyo ■), low frequency (5 kHz) was applied in the atmosphere, and the output was 30 W.
A treated powder was obtained by irradiating the powder with low-temperature plasma for a minute. The obtained treated powder had good hydrophobicity and water repellency.

Example 4 5 g of Red No. 202 and 1 g of cyclic silicone [of formula (c) with Ra''CH3, R7''0CH2CH3 and y=5] were mixed uniformly and mixed to form Practic Line (manufactured by Sankyo Dengyo ■). Argon 200m1/m using
Low frequency (5kHz) through the in! -30W
A treated powder was obtained by irradiating low-temperature plasma for 10 minutes under the following conditions. The resulting treated powder had good hydrophobicity and water repellency.

Example 5 5 g of kaolin and linear silicone [R in formula (b)
6=CH3, R7=CH3,1(e=CH2CH2Ce
0.7 g of F13 and
High frequency (
13.56 MHz) and 20 W output for 10 minutes to obtain a treated powder. This treated powder had good hydrophobicity and water repellency.

[Effects of the present invention] As is clear from the above explanation, the silicone coating on the powder surface is strong, dense, and homogeneous, so the treated powder has high hydrophobicity and water repellency, and has good stability with active sites blocked. was gotten.

Such treated powders can be used in cosmetics, pharmaceuticals, resin compositions, paints, inks, paints, ornaments, fragrances, magnetic materials, chromatographic carriers, and the like.

In addition, Red No. 202 has two crystal systems, α-type and β-type, and the β-type changes to the α-type in the presence of water, changing its color. Since the surface of such an organic pigment is completely covered by the silicone coating according to the present invention, it does not change to the α type even in the presence of water, resulting in a stable treated powder.

Ultramarine blue decomposes with acid and releases hydrogen sulfide, but the coating of the present invention eliminates this problem.

[Brief explanation of the drawing]

Figures 1 and 2 (A) to (C) show the results of measuring infrared absorption spectra. Figure-1: Cyclic silicone used in Example 1 Figure-2 (A
) : Untreated yellow iron oxide diagram - 2 (B) : Treated powder diagram of Example 1 - 2CC) : The treated powder of Example 1 was immersed in chloroform, filtered and then dried.

Claims (4)

[Claims] (1) A surface-treated powder obtained by irradiating a powder with low-temperature plasma along with one or more organosiloxanes represented by (a) below. (a) (R_1R_2SiO)_m(R_3R_4R_5Si
O_0_. _5)_n (wherein, R_1, R_2, R_3, R_4 and R_5
are hydrogen atoms, halogen atoms, hydroxyl groups, mercapto groups, acyloxy groups, alkoxy groups, amino groups, nitro groups, carboxyl groups, sulfone groups, or substituted or unsubstituted hydrocarbon groups having 1 to 30 carbon atoms [e.g. aliphatic groups (e.g. alkyl groups, alkenyl groups, alkynyl groups), aromatic groups (e.g. phenyl groups, naphthyl groups), heterocyclic groups (e.g. those containing one or more nitrogen atoms, oxygen atoms or sulfur atoms as heteroatoms), represents an alicyclic group (e.g. cycloalkyl group, cycloalkenyl group, cycloalkynyl group), spiro compound residue or terpene compound residue], provided that two hydrogen atoms may not exist bonded to the same silicon atom. No, m is an integer from 1 to 250,
n is 0 or 2. ) (2) The surface-treated powder according to claim (1), wherein the low-temperature plasma irradiation is a low-temperature plasma irradiation generated by corona discharge or glow discharge in a low frequency or high frequency region. (3) Low-temperature plasma irradiation under vacuum, nitrogen, oxygen, hydrogen,
The surface-treated powder according to any one of claims (1) to (2), which is carried out in an atmosphere of argon, helium, or air. (4) Any one of claims (1) to (3), wherein the total treatment amount of the organosiloxane represented by (a) is 0.1 to 20% by weight based on the powder. The surface treatment powder described in .