Use of glass compositions for achieving an antioxidative effect

Information

  • Patent Grant
  • 9173822
  • Patent Number
    9,173,822
  • Date Filed
    Tuesday, July 13, 2004
    19 years ago
  • Date Issued
    Tuesday, November 3, 2015
    8 years ago
Abstract
Described are the use of glass compositions, for example, in the form of glass powders, glass ceramics, fibers, granules, and spheres for achieving an antioxidative effect. The glass compositions may be used in a versatile manner, such as in cosmetic products, medical products, edibles, paints and lacquers, plasters, cements and concrete, in antifouling products and in polymers. Because of the high photo and temperature stability, the glass antioxidants of the present invention are superior to the organic substances known so far. In addition the glass compositions in contact with human being are non-irritant to skin and even edible. Furthermore, they are toxicologically harmless and environmentally compatible.
Description
CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of German Application No. 10332011.3 filed Jul. 14, 2003, which is incorporated by reference herein.


FIELD OF THE INVENTION

The invention relates to the use of glass compositions in the form of glass powders, fibers, granules, and spheres for achieving an antioxidative effect.


The glass compositions according to the present invention may also be transformed into glass ceramics having a different degree of crystallinity by an annealing step and can be used as antioxidants. Also a complete transformation into a ceramic may be carried out.


With it, the glass composition may be used in a versatile manner, such as in cosmetic products (i.a. “anti-aging” products), medical products, edibles and animal food, paints and lacquers, and in polymers.


In this case on the one hand, the employment of the materials described herein may occur for protecting the product itself, but on the other hand also for achieving an antioxidative effect towards outside (e.g. in food additives).


BACKGROUND OF THE INVENTION

While the use of antimicrobially and/or biocidally acting glasses is known from a plurality of documents, the employment of glass compositions to stop or retard an oxidation reaction has completely been unknown so far.


By the use of antioxidants; oxidation reactions which have a negative effect on various products may be stopped retarded; or respectively.


Thus, for example, the presence of free radicals in the above mentioned products may result in undesired decomposition, discoloration or even in the complete uselessness of the product.


Thus the antioxidants may also have product preservative or even product maintaining properties.


Oxidation effects i.a. are also responsible for the aging of the skin. These oxidations, respectively the formation of radicals are caused i.a. by UV radiation of the sun light also by pollutants in the air, and respectively. These effects are i.a. also responsible for the formation of wrinkles. Items antioxidants are also utilized in cosmetic products which should take precautions against a premature aging of the skin (so-called anti wrinkle agents).


The antioxidants described and known so far are almost exclusively organic compounds. Vitamin C (ascorbic acid) and also vitamin E inter alia are well known to a person skilled in the art. Partly these compounds have the disadvantage not to be photo resistant by itself, i.e. that they may act as a free-radical generator. The known oxidant vitamin C i.a. suffers from this disadvantage, in particular when applied in small concentrations.


Thus there is a need for providing an antioxidant which may be used for the above mentioned applications and which doesn't suffer from the disadvantages of the known antioxidants.


SUMMARY OF THE INVENTION

It was surprisingly now found that glass compositions as defined in the claims may be used for the purpose of avoiding oxidation reactions, i.e. as antioxidant. The glass compositions may be oxidic.


The antioxidative compositions of the present invention have a high photo and temperature stability. Preferably the antioxidative glass compositions have a biocidal effect on bacteria, fungi and viruses or they are biostatic. Further preferably in contact with humans they are non-irritant to skin and even edible, in addition toxicologically harmless and environmentally compatible. Thus the compositions are preferably free of heavy metals, in particular when they are in direct contact with living beings.


The glass compositions used in this case comprise glass ceramics, fibers, granules, spheres and glass powders. A glass powder may be a powder that contains a plurality of glass particles in any form (also fibers), for example glass spheres having a particle size (d50) of smaller than 1 mm up to smaller than 500 μm, more preferably <100 μm and <20 ppm, in particular <10 μm and <5 μm, or glass fibers having a diameter of smaller than 1 mm up to smaller than 500 μm, more preferably <100 μm and <20 μm, in particular <10 μm and <5 μm.


Glass ceramics according to the present invention may be prepared by annealing and may have different degrees of crystallinity.


The antioxidative effect may be based on a reaction of the glass with surrounding substances.


Reactions on the glass surface may also contribute to the antioxidative effect. Presumably the compositions produce the antioxidative effect in different manners, for example by the interception of free radicals, but also by the discontinuation of reaction chains which are responsible for the formation of free radicals and/or oxidation reactions and/or the exertion of an effect of chelation.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 shows the hydroxyl radical inhibiting effect of embodiment 3 in dependence on the concentration; and



FIGS. 2-3 show the measure of the antioxidative effect on the basis of obtained and oxidized proteins.





DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS OF THE INVENTION

According to the following embodiment examples which serve for illustration the invention will be described in more detail:


EXAMPLE 1

Glasses were smelted from the raw materials shown in table 1 which afterwards were formed into ribbons.


By means of dry milling these ribbons were further processed into powder having a particle size of d50=4 μm.









TABLE 1





Compositions (Synthesis Values) [in Percent by Weight] of the Glass Compositions


according to the Present Invention





















Emb. 1
Emb. 2
Emb. 3







SiO2
71.2
45




Al2O3
0.35

6.2



B2O3



P2O5

6
66.3



Li2O



Na2O
14.2
24.5
12.5



K2O
0.05



MgO
4.2



CaO
9.9
24.5
7.5



ZnO


7.5



Fe2O3
0.1
























Emb.
Emb.
Emb.
Emb.
Emb.
Emb.
Emb.
Emb.
Emb.
Emb.
Emb.
Emb.



4
5
6
7
8
9
10
11
12
13
14
15





SiO2



44.00
44.90

63.55
63.40
63.40





Li2O













Na2O
11.90
11.90
14.60
24.50
24.50
14.60
6.57
6.70
5.80


12.50


K2O













CaO


3.30
24.50
24.50
3.30



11.90
11.90
7.50


P2O5
66.90
65.90
33.45
6.00
6.00
33.45



65.90
65.90
66.20


B2O3






29.87
29.80
29.80


Al2O3
6.20
6.20







6.20
6.20
6.20


SO3


15.08


15.08


Ag2O

1.00

1.00
0.10
1.00

0.10
1.00

1.00
0.10


TiO2


ZnO
15.00
15.00
33.56


32.56



16.00
15.00
7.50









The antioxidative efficiency has been detected by means of the so-called “Deoxyribose-Test”


(“The Deoxyribose Method”, Analytical Biochemistry, 165, 215-219, 1987).


The diagram of FIG. 1. shows the hydroxyl radical inhibiting effect of embodiment 3 in dependence on the concentration.



FIG. 1 shows that embodiment 3 produces a clear hydroxyl radical inhibiting effect which increases with rising concentration.


It is possible to show that the antioxidative effect may be based on a discontinuation of the redox reaction chain. In the test method described herein the effect is based on a chelate formation (complexation) of iron which is required for the formation reaction of the free radicals. Thus the Fe(2+)/Fe(3+) redox reaction will be discontinued.


EXAMPLE 2

An alternative test method for detecting the antioxidative effect may be carried out by means of the so-called “Protein-Carbonyl-Assay-Test” which is described in “R. L. Levine et al., Meth. Enzymol. 186, 464-478, 1990”.



FIGS. 2 and 3 show the measure of the antioxidative effect on the basis of obtained and oxidized proteins. The test was carried out, before the irradiation with UV light (−UV) and after the action of UV light (+UV).


The lower the bar in FIG. 3, the higher the antioxidative effect for the composition in each case.


The bar diagram of FIG. 3 shows that with embodiment 2 only few oxidized proteins were obtained, i.e. that the antioxidative effect was high.


Embodiment 3 also shows a clear antioxidative effect after UV irradiation.


EXAMPLE 3

Deoxyribose-Test for the Determination of the Antioxidative Effect of Shampoos which contain Glass Compositions according to the Present Invention.









TABLE 2







Measured Optical Densities and Inhibition calculated thereof












Optical

Optical Density



Sample/
Density at 352 nm,

at 352 nm, 10%


Concentration
1% of the Shampoo
% Inhibition
of the Shampoo
% Inhibition














Shampoo 1
0.3505
Not
0.2922
15.5


with 5%

determinable


glass composition


(emb. 2)


Shampoo 2
0.2426
29.9
0.2477
28.4


with 5%


glass composition


(emb. 3)


Shampoo 3
0.3808
Not
0.3166
 8.5


no

determinable


glass composition


(support)


Catalase
0.0471
86.4
Not
Not


(positive control)


applicable
applicable


Reference
0.3459
Not
Not
Not


(negative control)

applicable
applicable
applicable









From the above table it will be appreciated that the shampoo which contains the glass composition according to embodiment 2 shows a light antioxidative effect when the test concentration of the tested shampoo is 10%.


In the test performed for the shampoo which contains the glass composition according to embodiment 3 a degradation of deoxyribose through hydroxyl radicals in an amount of about 30% can be determined, which corresponds to a distinct antioxidative effect.


The support itself (shampoo 3, without glass composition) shows with an inhibition of 8.5% a light antioxidative effect.


The shampoos 1 to 3 have the following composition (table 3):






















Shampoo 2





Shampoo 1
Shampoo 3
(Support)





[percent by
[percent by
[percent by


No.
Raw Material
INCI*
weight]
weight]
weight]




















1
Texapon NSO
Sodium laureth
50.00
50.00
50.00




sulphate


2
Amphotensid B4
Cocamidopropyl
8.0
8.0
8.0




betain


3
Water,
Water
33.29
38.29
33.29



demineralized


4
Euxyl K4O()
Methyldibromo-
0.1
0.1
0.1




glutaronitril and




phenoxyethanol


5
Edeta BD
Disodium
0.1
0.1
0.1




EDTA


6
Veegum Ultra
Magnesium
2.0
2.0
2.0




aluminium




silicate


7
Propylene
Propylene
0.01
0.01
0.01



carbonate
carbonate


8
Glass composition

5.0





according to emb. 2


9
Glass composition



5.0



according to emb. 3


10
NaCl
Sodium chloride
1.5
1.5
1.5





100.00
100.00
100.00



pH value

10.2
5.7
5.1





*international nomenclature of cosmetic ingredients






EXAMPLE 4

Deoxyribose-Test for the Determination of the Antioxidative Effect of OW Formulations, which contain Glass Compositions according to the Present Invention.









TABLE 4







Measured Optical Densities and Inhibition calculated thereof












Optical Density at

Optical Density at




352 nm, 1%

352 nm, 10%


Sample/
of the OW

of the OW


Concentration
Formulation
% Inhibition
Formulation
% Inhibition





OW formulation 1
0.3986
Not
0.3798
 4.1


with

determinable


glass composition


(emb. 2)


OW formulation 2
0.2505
36.8
0.2039
48.5


with


glass composition


(emb. 3)


Catalase
0.0829
79.1
Not
Not


(positive control)


applicable
applicable


Reference
0.3962
Not
Not
Not


(negative control)

applicable
applicable
applicable









From the above table it will be appreciated that the OW formulation which contains the glass composition according to embodiment 2 shows a light antioxidative effect if the test concentration of the tested formulation is 10%.


In the test performed for the OW formulation which contains the glass composition according to embodiment 3 a degradation of deoxyribose through hydroxyl radicals in amounts of about 37% respectively 49% can be determined, which correspond to a distinct antioxidative effect.


The OW formulations 1 and 2 have the following compositions (table 5):

















OW Formulation 1
OW Formulation 2


No.
Raw Material
[percent by weight]
[percent by weight]


















1
Alacel 165 V
6.65
6.65


2
Cetyl alcohol
0.95
0.95



(Lanette 16)


3
Stearingsaure L2
4.75
4.75



SM (GV S052)


4
Neutral oil vegetab./
22.8
22.8



Crodamol GTCC



(GV N020)


5
Demineralized
59.85
59.85



water


6
Glass composition
5.0




according to emb. 2


7
Glass composition

5.0



according to emb. 3









Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limitative of the remainder of the disclosure in any way whatsoever.


In the foregoing and in the examples, all temperatures are set forth uncorrected in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated.


The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.


From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions

Claims
  • 1. A method for achieving an antioxidative effect in a cosmetic product or deodorizing product for application to the hair or skin, which comprises adding to the product a glass composition which achieves an antioxidative effect in the product, wherein said glass composition comprises the following ingredientsSi02 0-10 percent by weightP205 25-75 percent by weightS03 0-30 percent by weightB203 0-40 percent by weightAl203 0-10 percent by weightLi2O 0-15 percent by weightNa20 0-40 percent by weightK20 0-25 percent by weightCaO 3.3-40 percent by weightMgO 0-15 percent by weightSrO 0-15 percent by weightBa0 0-15 percent by weightZnO 0-40 percent by weightAg20 0-5 percent by weightI 0-10 percent by weight andFe203 0-5 percent by weight; andwherein the glass composition is in the form of fibers, granules, spheres or powders.
  • 2. The method according to claim 1, wherein said glass composition is oxidic.
  • 3. The method according to claim 1, wherein said glass composition has a high photo and temperature stability.
  • 4. The method according to claim 1, wherein in said glass composition the sum of CaO+MgO+SrO+BaO+ZnO is 3.3 to 40 percent by weight.
  • 5. The method according to claim 1, wherein said glass composition is free of alkali.
  • 6. The method according to claim 1, wherein in said glass composition the sum of Li2O+Na20+K20 is 5 to 50 percent by weight.
  • 7. The method according to claim 1 wherein the glass composition is provided in a cosmetic product.
  • 8. The method according to claim 1 wherein the glass composition is provided in a deodorizing product.
  • 9. The method according to claim 1, wherein the glass composition is provided in a cosmetic product for lessening premature aging of the skin.
  • 10. The method of claim 1, wherein the glass composition is provided in the form of a glass ceramic.
  • 11. The method of claim 1, wherein the glass composition is provided in the form of a glass powder or glass spheres having a particle size, d50, of up to 500 μm or glass fibers having a diameter up to 500 μm.
  • 12. The method of claim 7, wherein the glass composition retards the occurrence of oxidation reactions on the hair or skin to which it is applied.
  • 13. The method of claim 1, wherein the glass composition has 0% by weight of Ag20.
  • 14. The method of claim 1, wherein the glass composition has 0% by weight of ZnO.
  • 15. A method for achieving an antioxidative effect in a cosmetic product or deodorizing product for application to the hair or skin, which comprises adding to the product a glass-ceramic composition or a ceramic composition which achieves an antioxidative effect in the product, wherein said glass-ceramic composition or ceramic composition comprises the following ingredientsSi02 0-10 percent by weightP205 25-75 percent by weightS03 0-30 percent by weightB203 0-40 percent by weightAl203 0-10 percent by weightLi2O 0-15 percent by weightNa20 0-40 percent by weightK20 0-25 percent by weightCaO 3.3-40 percent by weightMgO 0-15 percent by weightSrO 0-15 percent by weightBaO 0-15 percent by weightZnO 0-40 percent by weightAg20 0-5 percent by weightI 0-10 percent by weight andFe203 0-5 percent by weight; andwherein the glass-ceramic composition or ceramic composition is in the form of fibers, granules, spheres or powders.
Priority Claims (1)
Number Date Country Kind
103 32 011 Jul 2003 DE national
US Referenced Citations (10)
Number Name Date Kind
4428774 Drake et al. Jan 1984 A
5019293 Burlitch May 1991 A
5196381 Hu et al. Mar 1993 A
5296026 Monroe et al. Mar 1994 A
5614006 Algar Mar 1997 A
5880094 Tam Mar 1999 A
6475631 Yamamoto et al. Nov 2002 B1
6482444 Bellantone et al. Nov 2002 B1
20020086039 Lee et al. Jul 2002 A1
20030008759 Martin et al. Jan 2003 A1
Foreign Referenced Citations (13)
Number Date Country
101 41 230 Mar 2003 DE
10213630 Mar 2003 DE
0 003 903 Dec 1982 EP
1364639 Nov 2003 EP
54-160576 Dec 1979 JP
58-133320 Aug 1983 JP
09-291325 Nov 1997 JP
2001-291770 Oct 2001 JP
WO 0103650 Jan 2001 WO
WO 0172262 Oct 2001 WO
WO 03050052 Jun 2003 WO
WO 03050053 Jun 2003 WO
WO 03059834 Jul 2003 WO
Non-Patent Literature Citations (13)
Entry
Burdock (Encyclopedia of food and color additives 1997, vol. 3, pp. 2596 and 2597) Furia (CRC handbook of food additives 1972, vol. 1; pp. 644, 645, 647 and 649) 4 pages.
Furia (CRC handbook of food additives 1972, vol. 1; pp. 644, 645, 647 and 649) 5 pages.
Ferraz et al. (J. Biomed Mater Res 1999, 45, 376-383).
Materials Protection, Feb. 1996, vol. 29 No. 2, pp. 10-12., Japan.
Abstract of SU Patent #732218.
Abstract of WO Pub #9310058.
Abstract of RU Patent # 2027778.
Abstract of JP 49-119909.
Abstract of CN Patent #1401612.
Abstract: Zhang, Ling et al.; School of Materials Science and Engineering, Anshan Inst. of I. & S. Technology, 11402, (2000), 23(4), pp. 254-256.
English translation of Office Action dated Nov. 4, 2010 for corresponding Japanese Application No. P2004-204195.
Database WPI, XP 002299261.
Patent Abstracts of Japan, Bd. 200, Nr. 10.
Related Publications (1)
Number Date Country
20050013873 A1 Jan 2005 US