A product obtained by treating surface-modified, pyrogenically produced titanium dioxide with at least one ammonium-functional silane, such as by spraying the pyrogenically produced titanium dioxide with the at least one silane, alone or in ethanol solution, and tempering, and useful in the field of cosmetics in sunblocks, in toner powders, in paints and varnishes, in silicone rubber, as abrasives and polishes, for example, in the field of CMP.

Description

5 parts

›BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to a surface-modified, pyrogenically produced titanium dioxide, a process for its production as well as its use.

2. Description of the Background

It is known that highly-disperse pyrogenic titanium dioxide (for example, titanium dioxide P 25 S from Degussa-Hüls AG), on account of its low average primary particle size (21 nm) and of the structure of the aggregates and agglomerates resulting from the pyrogenic production process, has advantageous properties as a UV-A and UV-B blocker in cosmetic sunblock preparations. In addition, it is known that an increasing degree of dispersion of the titanium dioxide has a favourable effect on the UV-blocking action.

The hydrophilic surface of the pyrogenically produced titanium dioxide necessitates the use of high shear forces in order to achieve a high degree of dispersion, above all in oleophilic preparations. Consequently, pyrogenically produced titanium dioxides already surface-modified with alkylsilyl groups are known (titanium dioxide T 805 from Degussa-Hüls Aktiengesellschaft) which, in addition to the improved dispersibility in oleophilic preparations even at low shear energies, also bring about an improved UV-blocking and a decreased photochemical activity in the pyrogenic titanium dioxide. (Technical Information TI 1176 “Highly dispersed Titanium Dioxide for sunblock preparations”).

A disadvantage of the known surface-modified pyrogenic titanium dioxides is the low interaction with hydrophilic constituents of the cosmetic sunblock preparations, which is due to the exclusively oleophilic character of the surface.

The object of the invention is the development of a pyrogenically produced titanium dioxide, the surface modification of which imparts to it an oleophilic as well as a hydrophilic character, and which exhibits a good dispersibility in hydrophilic and in oleophilic media.

›SUMMARY OF THE INVENTION

The invention provides surface-modified, pyrogenically produced titanium dioxide, which is characterized in that it is treated with at least one ammonium-functional silane.

›BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows UV transmission of highly disperse titanium oxide as a function of wavelength for two examples of the present invention and a comparative material.

›DETAILED DESCRIPTION OF THE INVENTION

In one embodiment of the invention, the invention is a pyrogenically produced titanium dioxide surface-modified with an ammonium-functional silane and having the following physicochemical data:

Another embodiment of the invention is a pyrogenically produced titanium dioxide surface-modified with:

an ammonium-functional silane corresponding to the general formula

(RO) 4−n+m SiR 1 n {(CH 2 ) y (NR 2 R 3 R 4 ) + X − } m

n=0-3; m=1-3 with n+m<4; y=1-5; X=F, Cl, Br, or I

R=alkyl (C1-C5); R 1 =alkyl (C1-C1 8), aryl; R 2 and R 3 independently=H, alkyl, aryl, or benzyl;

R 4 =H, alkyl, aryl, or —C 2 H 4 NR 5 2 with R 5 =alkyl; or an ammonium-functional silane listed below:

(RO) 3 SiC 3 H 6 (N 4 C 6 H 12 ) + X −

R=alkyl (C1-C5); X=Cl, Br, or I

(RO) 3 SiC 3 H 6 (pyridinyl) + X −

R=alkyl (C1-C5); X=Cl, Br, or I

(RO) 3 SiC 3 H 6 OCH 2 CH(OH)CH 2 N + (CH 3 ) 3 X −

R=alkyl (C1-l-C5); X=Cl, Br, or I; or

an ammonium-functional silane listed below:

Examples of ammonium-functional silanes which can be used are:

X − (CH 3 ) 3 N + —C 3 H 6 —Si(OC 2 H 5 ) 3 wherein X=Cl, Br, or I

X − (C 18 H 37 )(CH 3 ) 2 N + —C 3 H 6 —Si(OC 2 H 5 ) 3 wherein X=Cl, Br, or I

A mixture of two or more of the above-described silanes can be used for the surface modification.

The invention also provides a process for the production of the surface-modified, pyrogenically produced titanium dioxide, which is characterised in that the pyrogenically produced titanium dioxide, in a mixing unit with intensive mixing, optionally in the presence of water or dilute acid, is sprayed with the at least one ammonium-functional silane, or with a solution of the at least one ammonium-functional silane in ethanol, and then further stirred for approximately 10 to 30 minutes and subsequently tempered for between 0.5 and 6 hours at a temperature of 100 to 400° C. The tempering can be carried out in an atmosphere of protective gas, for example, N 2 .

The pyrogenically produced titanium dioxide used can be a titanium dioxide of the type described in Ullmanns Enzyklopädie der technischen Chemie, 4th Edition, Volume 21 (1982) pages 464-465.

The surface-modified, pyrogenically produced titanium dioxide according to the invention can be used in the field of cosmetics, in particular as a sunblock, also in toner powders, paints and varnishes, in silicone rubber, as abrasives and polishes, for example, in the field of CMP.

In the field of cosmetics, in particular in sunblock preparations, the surface-modified pyrogenically produced titanium dioxide according to the invention exhibits the following IV advantages:

improved absorption of radiation in the range of 300-500 nm

good dispersibility in oleophilic and hydrophilic preparations.

›EXAMPLES

The titanium dioxide used was the pyrogenically produced titanium dioxide P 25 . Titanium dioxide P 25 is known from the series of publications Pigmente No. 56 “Hochdisperse Metalloxide nach dem Aerosilverfahren”, 4th Edition, February 1989, Degussa AG.

The physicochemical data for titanium dioxide P 25 is as follows:

Preparation - general procedure

In the Examples below, TiO 2 P 25 is placed in a mixer and sprayed with the silane, dissolved in ethanol, with mixing. On conclusion of the spraying, mixing is continued for a further 10 to 30 minutes, followed by tempering for a period of 0.5 to 6 hours at a temperature of 100 to 400° C. The spraying and/or the tempering can be carried out in an atmosphere of protective gas, for example, under nitrogen. Materials and process parameters are described in the table below.

Silanes used

Si 270/75=C1 − (CH 3 ) 3 N + —C 3 H 6 —Si(OC 2 H 5 ) 3 (75% solution in ethanol)

Si 275/75=C1 − (C 18 H 37 )(CH 3 ) 2 N + —C 3 H 6 —Si(OC 2 H 5 ) 3 (75% solution in ethanol)

Physicochemical data are described in the table below.

Results of the tests of applicability

The measured UV/VIS spectra of prepared sunblock pastes exhibited good adsorptions in the UV-A and UV-B region.

FIG. 1 compares UV transmission as a function of wavelength of surface-modified, pyrogenically produced titanium dioxide treated with an ammonium-functional silane of the above-described Examples 2 and 5 with a known product T 805 . The product T 805 is a pyrogenically produced titanium dioxide which has been treated with a trialkoxyoctylsilane.

These results show that the titanium dioxides according to the invention can be used very effectively in sunblock preparations.

Thus a better absorption of the radiation is achieved primarily in the 300 to 500 nm range.

Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein.

The disclosure of German priority application No. 19929845.9 filed Jun. 29, 1999, is hereby incorporated by reference.

›Tables in the description — 6

BET surface area:	15 to 100 m 2 /g
Bulk density:	150 to 700 g/l
pH value:	2.5 to 8.5
Loss on drying:	0.1 to 2.0 wt. %
Loss on ignition:	0.3 to 13.0 wt. %
Carbon content:	0.3 to 12.0 wt. %
Methanol wettability:	0 to 50 wt. %

2 Cl −	C 6 H 12 N 4 2+ (—C 3 H 6 —Si(OC 2 H 5 ) 3 ) 2
3 Cl −	C 6 H 12 N 4 3+ (—C 3 H 6 —Si(OC 2 H 5 ) 3 ) 3
Cl	(CH 3 ) 2 N—C 2 H 4 —N + —(CH 3 ) 2 C 3 H 6 —Si(OC 2 H 5 ) 3
2 Br −	CH 2 (— + N(CH 3 ) 2 —C 3 H 6 —Si(OC 2 H 5 ) 3 ) 2
2 I −	(—CH 2 + NH(CH 3 )—C 3 H 6 —Si(OC 2 H 5 ) 3 ) 2 .

Cl −	(CH 3 ) 3 + N—C 3 H 6 —Si(OC 2 H 5 ) 3
I −	(C 6 H 5 )(CH 3 ) 2 + N—C 3 H 6 —Si(OC 2 H 5 ) 3
Br −	(C 6 H 5 —CH 2 )(CH 3 ) 2 + N—C 3 H 6 —Si(OC 2 H 5 ) 3
Cl −	(C 12 H 25 )(CH 3 ) 2 + N—C 3 H 6 —Si(OC 2 H 5 ) 3
Br −	(C 12 H 25 )(CH 3 ) 2 + N—C 3 H 6 —Si(OC 2 H 5 ) 3
I −	(C 12 H 25 )(CH 3 ) 2 + N—C 3 H 6 —Si(OC 2 H 5 ) 3
Cl −	(C 16 H 33 )(CH 3 ) 2 + N—C 3 H 6 —Si(OC 2 H 5 ) 3
Cl −	(C 2 H 5 ) 3 + N—C 3 H 6 —Si(OC 2 H 5 ) 3
I −	(C 2 H 5 ) 3 + N—C 2 H 4 —Si(OC 2 H 5 ) 3
I −	(C 2 H 5 ) 3 + N—C 3 H 6 —Si(OC 2 H 5 ) 3
Cl −	(C 4 H 9 ) 3 + N—C 3 H 6 —Si(OC 2 H 5 ) 3
Br −	(C 4 H 9 ) 3 + N—C 3 H 6 —Si(OC 2 H 5 ) 3

Titanium dioxide P 25

CAS Reg. Number	13463-67-7
Behaviour towards water	hydrophilic
Appearance	loose white powder
BET surface area 1)	50 ± 15 m 2 /g
Average size of primary particles	21 nm
Tamped density 2)	ca. 100 g/ml
Specific weight 10)	ca. 3.7 g/ml
Loss on drying 3) on leaving the supplier's premises	<1.5 wt. %
(2 hours at 105° C.)
Loss on ignition 4)7) (2 hours at 1000° C.)	<2 wt. %
pH value 5) (in 4% aqueous dispersion)	3-4 wt. %
SiO 2 8)	<0.2 wt. %
Al 2 O 3 8)	<0.3 wt. %
Fe 2 O 3 8)	<0.01 wt. %
TiO 2 8)	>99.5 wt. %
ZrO 2 8)
HfO 2 8)
HCl 8)9)	<0.3 wt. %
Screen oversize 6) (after Mocker, 45 μm)	<0.05 wt. %
1) in accordance with DIN 66131
2) in accordance with DIN ISO 787/XI, JIS K 5101/18 (not screened)
3) in accordance with DIN ISO 787/II, ASTM D 280, JIS K 5101/21
4) in accordance with DIN 55921, ASTM D 1208, JIS K 5101/23
5) in accordance with DIN ISO 787/IX; ASTM D 1208, JIS K 5101/24
6) in accordance with DIN ISO 787/XVIII; JIS K 5101/20
7) based on the substance dried for 2 hours at 105° C.
8) based on the substance calcined for 2 hours at 1000° C.
9) HCl content is a constituent of the loss on ignition
10) determined by means of a pycnometer with reference to air

Tem-

Ex-		Quantity of	Quantity of	per-	Temper-
am-		silane	ethanol	ing	ature
ple	Silane	(g/100 g P25)	(g/100 g P25)	time (h)	(° C.)
1	Si 270/75	5	10	2	120
2	Si 270/75	7.5	0	2	120
3	Si 270/75	10	20	2	120
4	Si 275/75	5	10	2	120
5	Si 275/75	7.5	0	2	120
6	Si 275/75	10	20	2	120

1. Physicochemical data The products exhibit a hydrophilic and oleophilic character and can be used with advantage in cosmetic preprations.

			Carbon		Loss on	Loss on	CH 3 OH
		Tamped	content	pH	drying	ignition	wettability
Example	Silane	density (g/l)	(wt. %)	value	(wt. %)	(wt. %)	wt. %
1	Si 270/75	225	1.3	3.7	0.5	2.9	0%
2	Si 270/75	282	1.6	3.5	0.8	3.6	0%
3	Si 270/75	397	2.1	3.6	0.4	4.6	0%
4	Si 275/75	215	2.1	3.6	0.8	3.4	0%
5	Si 275/75	368	3.2	3.3	1.0	4.9	20%
6	Si 275/75	384	3.5	3.3	0.8	5.2	10%

Claims as granted

22 claims

Classifications

24 codes

IPC · International Patent Classification

Section A — Human necessities

A61Q17/04
A61K8/29
A61K8/00

Section C — Chemistry; metallurgy

C09D7/62
C09C1/36
C08K9/06
C09D201/00
C01G23/047
C09K3/14
C09G1/02
C08L83/04
C09G1/00
C09C3/12

Section G — Physics

G03G9/097

USPC · US Patent Classification

424/59424/60424/400106/448106/437424/401106/820106/436106/447424/490

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