CA2004112C - Dispersions - Google Patents
DispersionsInfo
- Publication number
- CA2004112C CA2004112C CA002004112A CA2004112A CA2004112C CA 2004112 C CA2004112 C CA 2004112C CA 002004112 A CA002004112 A CA 002004112A CA 2004112 A CA2004112 A CA 2004112A CA 2004112 C CA2004112 C CA 2004112C
- Authority
- CA
- Canada
- Prior art keywords
- titanium dioxide
- aqueous dispersion
- weight
- dispersion according
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/0241—Containing particulates characterized by their shape and/or structure
- A61K8/0245—Specific shapes or structures not provided for by any of the groups of A61K8/0241
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
- A61K8/04—Dispersions; Emulsions
- A61K8/044—Suspensions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
- A61K8/29—Titanium; Compounds thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3615—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C1/3623—Grinding
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/007—Metal oxide
- C09D17/008—Titanium dioxide
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
- A61K2800/26—Optical properties
- A61K2800/262—Transparent; Translucent
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/413—Nanosized, i.e. having sizes below 100 nm
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
Abstract
An aqueous dispersion of acicular fine particle size titanium dioxide containing from 20 to 60% by weight solids content and a polycarboxylic dispersant is of outstanding use in the preparation of sun screens. The dispersions are transparent to visible light and absorbant to UV light of broad spectrum. Usually the titanium dioxide has a largest dimension within the range 0.01 to 0.15 micron.
The dispersions are produced by milling, preferably in a high speed mill, until the required UV absorbancy is attained.
The dispersions are produced by milling, preferably in a high speed mill, until the required UV absorbancy is attained.
Description
-2- 20G~41l2 This invention relates to dispersions and particularly to aqueous dispersions of titanium dioxide suitable for use in the m~mlf~cture of absorbers for UV radiation.
Various aspects of the invention are a~ follows:
An aqueous dispersion oftitanium dioxide comprising water, particles of titanium dioxide having an acicular shape and having a ratio of the longest dimension to the shortest dimension within the range 8:1 to 2:1 and wherein the longest dimension is within the range 0.01 to 0.15 microns and a dispersing agent being a polymer or a copolymer of an acrylic acid or a substituted acrylic acid or a salt thereof and said titanium dioxide being present in an amount to produce a solids content for the dispersion of from 20 to 60 per cent by weight and said dispersion being substantially transparent to visible light and having a maximum extinction coefficient (E(max)) in the ultra-violet range of wavelengths of at least 30 litres per gm per cm.
A method for the m~nllf~ctllre of an aqueous dispersion comprising milling in the preser~ce of particulate grinding medium particulate titanium dioxide in water in the presence of a dispersing agent being a polymer or a copolymer of an acrylic acid or a substituted acrylic acid or a salt thereof, said tit~ni. Im dioxide having an acicular shape and having a ratio of the longest dimension to the shortest dimension within the range 8: I to 2: 1 and wherein the longest dimension is within the range 0.01 to 0.15 microns and the titanium dioxide is present in an amount sufficient to produce a solids content of from 20 to 60 per cent by weight until the titanium dioxide is dispersed in said water to produce a product having a maximum extinction coefficient (E(max)) in the ultra-violet wavelengths of at least 30 litres per gm per cm and being substantially transparent to visible light.
4 ~ 1 2 The aqueous dispersions of the present invention contain a high proportion of the specified particulate titanium dioxide and as described there is sufficient present to confer on the dispersion or solids content of at least 20 per cent by weight. The dispersion can have a solids content of up to 60~o per cent by weight but preferably sufficient particulate titanium dioxide is present for the aqueous dispersion to have a solids content of from 25 to 50 per cent by weight. The ~tt~inment of such high solids contents with the specified particulate titanium dioxide enables the aqueous dispersion to be of beneficial and convenient use in the m~nl-f~cture of compositions or mixtures to be used to absorb UV
radiations. In some cases the aqueous dispersion may be in the form of a light gel which can be mixed easily and reliquefied. This gelling has no adverse effects on the absorption of UV light.
The particulate titanium dioxide is of a specified form. The material is acicular in shape and preferably the particles have a ratio of the largest dimension to the shortest dimension within the range 8:1 to 2:1.
Usually the particles of titanium dioxide have a largest dimension within the range 0.01 to 0.15 micron and preferably 0.02 to 0.1 micron.
Preferably the particulate material has a narrow size range with at least .~, 20041~Z
80% by weight falling within the range of largest dimensions of 0.01 to 0.15 micron.
The particles of titanium dioxide forming the aqueous dispersions of the invention can be anatase, rutile or amorphous titanium dioxide S and each particle can be composed of aggregated smaller particles or crystals but preferably each particle is a single particle of the desired size.
The particles of titanium dioxide can be uncoated or coated with one or more hydrous oxides of a metal such as aluminium, zirconium, zinc or titanium and of silicon. Preferably however when the particles 10 are coated then the coating includes a hydrous oxide of aluminium and of silicon, e.g in a weight ratio of Al203:SiO2 of at least 1.5 and not greater than 4.5. Preferably the weight ratio Al203:SiO2 in the coating is from 2.0 to 3.5.
Usually the actual amount of the coating is such that the amount of hydrous oxide when expressed as the oxide, e.g. A1203, iS from 1.0 to 30.0 weight percent based on weight of titanium dioxide and preferably from 5.0 to 20.0 weight per cent oxide, e.g A1203, on weight of titanium dioxide. When the particles are coated with a hydrous oxide of alnminillm and of silicon then the amount of hydrous oxide of silicon will be that necessary to m~int~in the ratio of the amounts of coating hydrous oxides, A1203 and SiO2, within the specified range and generally speaking the weight of the hydrous oxide of silicon will be within the range 0.2 to 20.0 weight percent as SiO2 based on titanium dioxide and preferably from 1.5 to 7.0 weight percent.
The particulate material of the present invention may be formed by any suitable process for m~king acicular products. Typical processes -may involve hydrolysis of an appropriate titanium compound such as titanium tetrachloride or an organic or inorganic titanate or oxidation of an oxidisable titanium compound for example in the vapour state.
A typical process involves the preparation of a solution of a 5 soluble titanium salt which is then hydrolysed to form hydrous titanium oxide. The solution can be that obtained in the so-called "sulphate"
process for the m:~mlf~ctllre of titanium dioxide pigment in which a titaniferous ore is digested with concentrated sulphuric acid and the digestion cake dissolved in water or dilute acid to produce a solution of 10 titanyl sulphate. During the process additional process stages of classification and reduction are usually employed. Hydrolysis of the titanyl sulphate solution produces the precipitate of hydrous titania which is sometimes called "pulp". Soluble iron compounds remain in solution and after neutralisation and washing to an appropriate degree of 15 impurity level the precipitated pulp of hydrous titania is treated with, say sodium hydroxide and subsequently hydrochloric acid to produce the acicular titanium dioxide.
Usually prior to coating of the acicular titanium dioxide product it is preferred to mill the product to an appropriate particle size falling 20 within that speciffed hereinbefore. Milling conveniently can be effected in a wet milling process employing a grinding medium such as sand which can be separated easily and effectively from the milled pulp. Milling, preferably, as carried out in the presence of a dispersing agent which may be an alkali metal silicate, e.g. sodium silicate, which provides at least 25 some of the source of the coating hydrous silica when this is to be deposited subsequently. Should another dispersant be used for example, 200AllZ
an organic dispersant, then the source of coating hydrous silica is added subsequently if to be present.
If desired the milled product is then treated to deposit the coating of the hydrous oxide(s) in the specified amounts. To an aqueous 5 dispersion of the particulate product containing a hydrolysable salt or salts of the desired metal and/or of silicon there is added a reagent which effects hydrolysis of the salt to form the chosen hydrous oxide(s).
Typically aluminium sulphate can be a source of ~lnmin~ or an alkaline ~lnmin~te can be employed or if desired both an acidic aluminium salt 10 and an alkaline solution of an alnmin~te can be added either together or sequentially. Other metal salts and silicates can be used depending on the particular desired coating.
Depending on the pH of the dispersion of the product, hydrolysis and precipitation may require the addition of an alkali or an acid as the 15 reagent. The preferred coating is obtained by adding to an acid reacting dispersion of the particles of titanium dioxide cont~inin~ an alkali metal silicate an amount of ahlminillm sulphate followed by an amount of an alkali metal alllmin~te prior to the addition of a mineral acid such as sulphuric acid to effect formation and precipitation of hydrous alumina 20 and adjustment of the pH of the dispersion to a value in the range 6 to 8, preferably pH 6.8 to 7.5 The product can be separated from the aqueous dispersion, wa~hed and then dried at an elevated temperature of say 70C to 110C
or even higher. In contrast to the usual "sulphate" process for the 25 production of pigmentary titanium dioxide no calcination of hydrous titania is carried out prior to coating. Consequently it may be that some . -2()~4112 of the titania in the product of the invention, if prepared from pulp, is present in a hydrous form even after drying.
Alternatively the particles of titania according to the present invention can be prepared by decomposition or hydrolysis of suitable 5 titanium compounds e.g. titanium tetrachloride. Typically high temperature hydrolysis of an organic titanium compound such as a titanium alkoxide can be used to produce a fine particle sized titania pulp to be converted to acicular form. Oxidation or hydrolysis in the vapour state of titanium halides under appropriate conditions can be also used to 10 prepare the titania to be coated.
The products of the present invention have the property of absorbing UV light and transmitting visible light. This means that the products can find use in a wide variety of applications wherein it is important to m~int~in transparency of visible light while substantially 15 preventing tr:~n~mi~ion of UV light to a surface. Cosmetics, in any form such as lotions, creams, milks, pastes, sticks, face powders, sun screens and hair care products are a number of applications for the products of the invention.
The dispersions of the present invention are prepared by milling 20 the particulate titanium dioxide into water in the presence of a specified organuc dlspersing agent.
The mill which is employed to effect the grinding of the titanium dioxide product in the water is one which uses a particulate grinding medium to grind the product. Such mills are the various types of mills 25 equipped with one or more agitators and using sand or glass beads or ceramic beads or other particles as the particulate grinding medium.
200~112 -Particularly useful are those mills which operate at a high speed and depending on the size of mill a speed of the order of 2500 rev. per minute (r.p.m) is not unusual. For instance mills operating at a speed of from 500 r.p.m to 6000 r.p.m are suitable. Agitator mills in which the tip speed 5 of the agitator is up to and can exceed 10 metres/sec are of use. If desired the mill can be cooled. Also the dispersions can be pre-mixed using a high speed stirrer or the water can be added to the mill initially and then the titanium dioxide and the organic dispersant co-added to the water subsequently. After milling has been carried out for the required 10 time the dispersion is separated from the grinding medium.
The dispersing agent which is present in the aqueous dispersion of the present invention is a polycarboxylic acid or a salt thereof. Partially or fully neutralized salts are usable e.g. the alkali metal salts and ammonium salts. Examples of dispersing agents are polyacrylic acids, 15 substituted acrylic acid polymers, acrylic copolymers, sodium and/or ammonium salts of polyacrylic acids and sodium and/or ammonium salts of acrylic copolymers. Such dispersing agents are typified by polyacrylic acid itself and sodium or ammonium salts thereof as well as copolymers of an acrylic acid with other suitable monomers such as a sulphonic acid 20 derivative such as 2-acrylamido 2-methyl propane sulphonic acid.
Comonomers polymerisable with the acrylic or a substituted acrylic acid can also be one cont~ining a carboxyl grouping. Usually the dispersing agents have a molecular weight of from 1000 to 10,000 and are substantially linear molecules.
`- 2004112 g The amount of the dispersion agent used is usually within the range 5 to 35 per cent by weight of the titanium dioxide in the dispersion and preferably 10 to 25 per cent by weight.
The preferred dispersions of the present invention have a 5 m~ximllm extinction coefficient of at least 30 litres per gram per cm at a wavelength of 308nm. More preferably the dispersion has a m~ximllm extinction coefficient of at least 40 litres per gram per cm at a wavelength of 308nm. The products of the invention are substantially transparent to visible light.
In the past an ideal sunscreen was considered as being one which absorbs or filters out UVB radiation (290-320nm), as it is this which causes erythema. More recently, however, there has been growing concern about the effect that UVA radiation (320-400nm) has on the shn.
It is now widely accepted that the definition of the ideal sunscreen is one which can provide photoprotection from both UVB and UVA
radiation. This ideal sunscreen must therefore contain agents which can absorb or filter out radiation in the range 290-400nm.
The spectra of the acicular ultra-fine titanium dioxide dispersions 20 40% solid content of the invention indicate that there should be protection provided in both the UVB and UVA regions, and values of extinction coefficients covering the range 290-400nm are given as shown below.
-NO. DIOXIDE PIGMENT
E (300nm) 47.8 56.9 57.2 49.6 18.9 E (320nm) 37.2 39.2 44.2 41.6 19.2 E (340nm) 26.1 27.5 29.2 29.0 20.1 E(360nm) 18.3 21.0 18.7 19.5 21.3 E (380nm) 13.9 15.7 13.1 13.8 21.9 E(400nm) 10.6 12.7 9.3 10.2 22.3 For comparison, extinction coefficients are given for similar dispersions of anatase titanium dioxide pigment (uncoated) of solids contents of 40~o by weight. It can be seen that extinction coefficients in the UVB region (290-320nm) are much lower for pigmentary TiO2 than for the products of the invention.
In the UVA region, again extinction is higher for the acicular ultra-fine grade between 320-340nm. From 360nm to 400nm the pigmentary TiO2 has a higher extinction coefficient, but this level of extinction is m~int~ined into the visible region for the pigmentary grade.
This means that the pigment dispersion looks white when applied to the skin.
The ultra-fine TiO2 extinction is very low in the visible region (above 400nm) which means that the dispersion is more transparent and aesthetically acceptable than the pigment dispersion, while still m~int~ining good UVB and UVA extinction coefficients.
The invention is illustrated in the following Examples.
20041~Z
Example 1 Ilmenite was digested with concentrated sulphuric acid. The digestion cake obtained was dissolved in water to form a crude liquor cont~ining iron and titanium sulphates and some suspended insoluble 5 matter. Any iron present in the ferric form was reduced chemically prior to filtering insoluble matter. The liquor after any necessary cryst~ tion and filtration was concentrated by vacuum treatment and then hydrolysed to precipitate hydrous titanium dioxide by boiling and addition of any necessary reaction agent. The product on filtering was a 10 pulp of uncoated hydrous TiO2.
In the subsequent process any water added or used was taken to be demineralised water.
The pulp of the uncoated hydrous TiO2 obtained was diluted to a concentration of 280 grams per litre TiO2 and a sample amount of 2.5 15 litres taken and heated to 60C. Aqueous sodium hydroxide solution cont~ining 700 grams per litre NaOH in an amount of 1.5 litres was heated to 90C and then transferred to a reaction flask having a volume of 5 litres fitted with a condenser. The hot diluted pulp was added over a period of 30 minutes to the reaction flask whilst agitating the contents 20 vigorously and the mixture temperature was held at 117C whilst agitating for a period of 2 hours after the addition had been completed.
Cold water was added to quench the solution in the flask to 90C and to decrease the concentration of titanium dioxide to 140 grams per litre.
The amount of water added was approxim~tely 20~o of the total volume 25 achieved. The contents were agitated for a further 15 minutes at this temperature of 90C prior to cooling to a temperature of 50 to 55C by - 2004~12 -the addition of a further amount of cold water which reduced the concentration of titanium dioxide to about 80 to 90 grams per litre. The dispersion was filtered and the filter cake washed with warm water at a temperature of 50C to 60C so that the filtrate contained less than 1500 5 ppm Na2O. The washed filter cake was then reslurried in water to a concentration of 200 grams per litre TiO2 and at this stage the product was sodium titanate.
Two litres of the washed sodium titanate was added to a reaction flask having a volume of 6 litres and fitted with a condenser. The pH of 10 the dispersion in the flask was reduced to a value within the range 2.8 to 3.1 by the addition of aqueous hydrochloric acid (30% w/w) and the mixture then heated to a temperature of 60C at the rate of 1C per minute. The pH of the mixture was rechecked and adjusted, if necessary, to a value within the range 2.8 to 3.1 by a further addition of the aqueous 15 hydrochloric acid. The dispersion was held at this temperature for 30 minlltes whilst agitated. A further quantity of hydrochloric acid was then added such that the volume added was 0.754 litres of 30~ HCI acid per kilogram of TiO2 in the dispersion such that the ratio of HCl/TiO2 equalled 0.26. The slurry was then heated to the boiling point over a 20 period of 40 minutes and held at the boiling point for a period of 90 minlltes whilst being agitated. The treated product was then quenched by addition of two litres of water and the dispersion had a pH value of 0.4.
Sodium hydroxide solution at a concentration of 400 grams per litres NaOH was then added to neutralise the dispersion to a pH of 7.5 and 25 appr-~xim:~tely 460 ml of the aqueous sodium hydroxide was required.
The dispersion was filtered and the filter cake washed with two litres of 20041~
water. The washed filter cake was then redispersed with a further quantity of two litres of water and filtered again to produce a filter cake having a solids content of 34% by weight.
The filter cake is then dried in an oven at 110C overnight. The 5 product was acicular rutile titanium dioxide having an average size of 0.02 x 0.1 microns.
276g of the dried TiO2 product was added to 414g of water and 33.1g of sodium polyacrylate obtainable under the name Antiprex A. This mixture was milled in a sandmill for 1 hour using 800ml of glass beads, 10 known as Ballotini (Grade 4), as grinding media to disperse the product in water and to separate any aggregated particles. The glass beads were removed from the milled dispersion at the end of the milling period by filtration.
The millbase, which contained 38.2% solids was diluted with 15 demineralised water in the proportion O.lg millbase in lOOml water, and then lml of this diluted millbase in 20ml water. The mill base was then exposed in a spectrometer (Beckman DU-50) with a 1 cm pathlength and the absorbance of UV and visible light measured.
Extinction coefficients at two wavelengths and at the m~ximllm 20 wavelength were then calc~ ted from the equation A = E.c.l where A
= absorbance, E = Extinction coefficient in litres per gram per cm, c =
concentration in grams per litre and 1 = pathlength in cm. W =
wavelength (nm) - 2~0~1~Z
Results were:
E (524nm) 5.1 E (308nm) 60.8 E (max) 65.5 W(max) 293 Example 2 As Example 1 except that milling was carried out on a high speed bead mill (Eiger M750-SSE-EXD) using 400ml glass Ballotini as grinding media. 385g TiO2 was mixed with 658g of water and 46.4g of the sodium 10 polyacrylate used in Example 1. The dispersion was milled for 30 mins and the solids content of the dispersion was 35.4~o.
After separation from the grinding aid a O.lg portion was diluted as previously with water and this diluted sample was exposed in a spectrometer (Beckman DU-50). Extinction coefficients were calculated 15 as previously.
E (524nm) 5.5 E (308nm) 45.5 E (max) 50.7 W (max) 279 20 Example 3 The procedure of Example 1 was repeated to obtain a washed filter cake of 34% by weight solids content of uncoated titanium dioxide.
882 grams of the filter cake (300 grams TiO2) was diluted to a concentration of 100 grams per litre TiO2 with demineralised water and 25 mixed with sodium silicate in an amount equivalent to 5% by weight SiO2 on weight of TiO2 and milled in a sand mill for 2 hours after adjusting the - 20041~2 pH of the dispersion to 10.0 to 11.5 with aqueous sodium hydroxide. The grinding medium was Ottowa sand and was removed from the milled dispersion at the end of the milling period by filtration.
The aqueous dispersion after removal of the sand had a pH of 9.1 and was heated to 60C and m~int~ined at this during the coating operation.
To the stirred dispersion aqueous ~ minium sulphate solution (68 grams per litre Al2O3 equivalent) was added dropwise in an amount sufficient to introduce ahlminillm sulphate in an amount equivalent to 5% Al2O3 on weight of TiO2 over a period of 60 minutes. Approximately 219 mls of the solution were added. After the addition has been completed the dispersion had a pH of 2.4 and was allowed to age for 30 mimltes at 60C whilst stirring was m~int~ined.
An ~lk~line solution of sodium ahlmin~te (80 grams per litre A1203) was then added over a period of 60 minutes to the stirred dispersion in an amount sufficient to introduce the equivalent of 10% by weight A1203 on weight of TiO2. Approxim~tely 375 mls of the solution was found to have been added. The dispersion which had a pH of 11.8 was stirred at 60C for 45 minutes.
Sulphuric acid (10%) was added to the aqueous dispersion to reduce the pH to 7.5. The neutralised dispersion was aged for 15 minutes whilst being stirred. The dispersion was filtered to produce a filter cake of the coated product which was then washed with 1 litre of demineralised water. The cake was redispersed in 1 litre of demineralised water, re-filtered and then washed again with demineralised water.
- 20041~2 The product was dried at 110C overnight. The product was acicular rutile titanium dioxide having an average size of 0.02 x 0.10 microns with a coating of hydrous silica in an amount equivalent to 4.8%
by weight SiO2 on TiO2 and hydrous alumina in an amount of 11.2% by S weight A1203 on TiO2 as determined by analysis of the product.
50g of the dried coated TiO2 product was added to 70ml of water and 5.03g of the sodium polyacrylate used in Example 1. This mixture was milled in a high speed bead mill (Eiger M-50-VSE) for 2 hours using 35ml of glass beads. The millbase, which contained 40% solids was 10 diluted as in previous examples and exposed in a spectrometer.
Extinction coefficients are listed below:
E (524nm) 4.2 E (308nm) 44.5 E (max) 50.0 W(max) 287nm Example 4 276g of the dried coated TiO2 product of Example 3 was added to 414g of water and 33.1g of the sodium polyacrylate used in Example 1.
The mixture was milled in a sandmill for 1 hour using 800g of glass 20 beads. The millbase, which contained 38~o solids, was diluted as previously and a spectrum was recorded E (525nm) 5.6 E (308nm) 49.7 E (max) 53.1 W (max) 288 `- 20041~2 Example 5 A solution of titanium tetrachloride in hydrochloric acid having an acid /titanium ratio (weight ratio) of 1.77 was prepared containing 200 grams per litre TiO2 equivalent. An aqueous solution of sodium 5 hydroxide (110 grams per litre) was prepared from carbonate free ingredients.
To a 3 litre glass flask fitted with a stirrer there was added 1203ml of the aqueous sodium hydroxide solution and 400 ml of water (demineralised). To the stirred solution there was then added 400 mls of 10 the titanium tetrachloride solution over a period of 15 minutes and during this period the stirrer speed was controlled at 100 rev. per minute.
After the addition had been completed the temperature was raised from its initial value of 40-45C to 82C at a rate of 1C per minute and the mixture was held at this temperature for a further 120 minutes whilst 15 stirring continued. During the heating to the temperature of 82C the solution was observed to clear partially, normally at about 60-70C as the titanium dioxide peptises and then re-precipitates.
After holding at 82C for 120 minutes the mixture was added to 2.5 litres of cold distilled water to quench the mixture then a further 5 20 litres of the water at 60C is added to the quenched mixture. Sodium hydroxide solution (110 grams per litre) is then added to the mixture to neutralise the ~ u~e to a pH value of 7.5. The neutralised and flocculated mixture was allowed to settle, filtered and the cake washed with 2.5 litres of water by stirring prior to refiltering. The cake was 25 washed again by re-slurrying with 2.5 litres of water and filtered to produce a cake having a solids content of 22% by weight.
- 200~112 The titanium dioxide in the cake was acicular and rutile having an average size of 0.01 to 0.05 microns.
The acicular titanium dioxide product obtained was coated in accordance with Example 3 with hydrous silica (5~o by weight on weight S of TiO2) and hydrous alumina (l5~o by weight).
276g of the TiO2 product was added to 414g of water and 33.1g of the sodium polyacrylate used in Example 1. This mixture was milled in a sandmill for 1 hour using 800g of glass beads. The millbase, which contained 41~o solids, after milling, was diluted as previously and a 10 ,spectrum was recorded.
E (524nm) 4.9 E (308nm) 35.7 E (max) 42.7 W (max) 276nm Example 6 Ilmenite was digested with concentrated sulphuric acid. The digestion cake obtained was dissolved in water to form a crude liquor cont~ining iron and titanium sulphate and some suspended insoluble matter. Any iron present in the ferric form was reduced chemically prior to filtering insoluble matter. The liquor after any necessary cryst~ ation and filtration was concentrated by vacuum treatment and then hydrolysed to precipitate hydrous titanium dioxide by boiling and addition of any necessary reaction agent. The product on filtering was a pulp of uncoated hydrous TiO2.
Four kilograms of the pulp so obtained was mixed with 5 litres of demineralised water. The pH of the diluted pulp was 1.9 and 375 ml of - 20041~2 an aqueous solution of sodium hydroxide (cont~ining 400 grams per litre NaOH) added to increase the pH to a value within the range 7.5 to 7.8.
The dispersed pulp was filtered and the cake washed with 6.5 litres of demineralised water. The washed filter cake was then redispersed in 3 5 litres of demineralised water and the pH measured at a value of 8.4.
Sulphuric acid (10%) (118ml) was added to reduce the pH of the dispersion to 7.5 prior to filtering again. After washing the filter cake with 6.0 litres of demineralised water the solids content of the cake was 44.3% by weight.
The filter cake was dried in an oven at 110C overnight. 50g of the product was added to 70g of water and 8.78g of the sodium polyacrylate used in Example A. The mixture was milled (Eiger M-50-VSE) for 2 hours using 35ml glass beads.
The millbase which contained 38.8% solids was diluted and a 15 spectrum was recorded.
E (524nm) 5.6 E (308nm) 40.4 E (max) 54.1 W (max) 257nm 20 Example 7 276g of the dried TiO2 product of Example 1 was added to 257g of water and 33.1g of the sodium polyacrylate used in Example 1. This rnixture was rnilled in a sand mill for 1 hour using 800ml of glass beads.
The millbase, which contained 48.7% solids was diluted as before and a 25 spectrum was recorded.
2~1 12 E (524nm) 6.9 E (308nm) 44.3 E (max) 47.6 W (max) 293 S Example 8 35g of the dried coated TiO2 product of Example 3 was added to 61.5g of water and 3.5g of a dispersant which is a sodium salt of an acrylic copolymer (35% solution) obtainable under the name Bevaloid 226/35.
The mixture was milled in a sand mill for 1 hour using SOg of glass beads.
10 The millbase, which contained 35~o solids was diluted as previously and a spectrum was recorded.
E (524nm) 3.3 E (308nm) 43.1 E (max) 45.1 W (max) 296 Example 9 35g of the same dried coated TiO2 product used in Example 8 was added to 61.5g of water and 3.5g of a sodium salt of an acrylic acid (50%
solution) obtainable under the name BevaloidTM 6770. The ~ u~e was 20 milled in a sand mill for 1 hour using SOg of glass beads. The millbase, which contained 35~o solids, was diluted as previously and a spectrum was recorded.
E (524nm) 4.9 E (308nm) 46.4 E(max) 49.0 W (max) 296nm Z0041~Z
Example 10 35g of the same dried coated TiO2 product used in Example 8 was added to 61.5g of water and 3.5g of a polyacrylic acid of molecular weight 2100 and obtainable under the name Carbopol 420.. The mixture was 5 milled as in Example 9. Millbase was 3so~o solids.
E (524nm) 6.6 E (308nm) 41.6 E (max) 42.9 W (max) 296 10 Example 11 35g of the same dried coated TiO2 product used in Example 8 was added to 61.5g of water and 3.5g of a polyacrylic acid having a molecular weight of 5100 and obtainable under the name Carbopol 430. Mixture milled as in Example 9. The millbase which contained 3so~c solids was 15 diluted as before.
E (524 nm) 4.9 E (308nm) 46.5 E (max) 48.2 W (max) 296 20 Example 12 328g of the same dried coated TiO2 product used in Example 8 was added to 369.2g of water and 32.8g of a fully neutralised sodium salt of a polycarboxylic acid obtainable under the name DP6. The sample was milled in a s~n(lmill for 1 hour using 800g of glass beads. The millbase, 25 which contained 42.8,~o solids after milling, was diluted as before.
- 2~4i~2 E (524nm) 4.8 E (308nm) 51.4 E (max) 57.1 W (max) 293 5 Example 13 385g of the acicular titanium dioxide product produced by the method of Example 5 was used, except that it was uncoated. This product was mixed with 658g of water and 46.4g of the sodium salt used in Example 12 obtainable under the name DP6, and was milled for 30 10 minutes on a high speed be~-lmill (Eiger M750-SSE-EXD). The solids content of the dispersion was 35.4% and this was diluted as previously and a spectrum was recorded (Perkin Elmer Lambda 2 UV/Vis Spectrometer).
E (524nm) 2.5 E (308nm) 28.4 E (max) 35.8 W (max) 279nm Example 14 50g of the acicular titanium dioxide product in Example 1 was added to 58.8g of water and 4.31g of an ammonium salt of an acrylic acid obtainable under the name Dispex A40. The product was milled (Eiger M50VSE) for 2 hours using 35ml of glass beads. The millbase, which had a solids content of 44.2% was diluted as before and a spectrum was recorded E (524nm) 5.0 E (308nm) 44.6 E (max) 46.7 W (max) 294nm 5 Example 15 50g of the acicular product produced in Example 1 was added to 58.8g of water and 3.01g of the fully neutralized sodium salt used in Example 12. The sample was milled as in Example 14. The millbase, which had a solids content of 44.7~o was diluted as before and a spectrum 10 was recorded.
E (524nm) 3.2 E (308nm) 55.5 E (max) 61.4 W (max) 290nm 15 Example 16 50g of the acicular titanium dioxide product of Example 8 was added to 58.8g of water and 5.84 g of a sodium salt of a polymethacrylic acid having a molecular weight of 12000 and obtainable under the name Orotan 850.. The sample was milled as in Example 14. The millbase, 20 which had a solids content of 43.6~o was diluted as before.
E (524nm) 7.3 E (308nm) 45.4 E (max) 46.4 W (max) 298 nm 20041~X
Example 17 50g of the acicular titanium dioxide product of Example 8 was added to 58.8g of water and 6.5g of the ammonium salt of an acrylic acid as used in Example 14. The sample was milled as in Example 14. The 5 millbase, which contained 43.4~o solids, was diluted as before.
E (524nm) 6.1 E (308nm) 50.5 E (max) 52.7 W (max) 294nm 10 Example 18 385g of the acicular titanium dioxide product of Example 5 was mixed with 658g water and 45.3g of the sodium salt used in Example 16..
This mixture was milled for 45 minutes (Eiger M750-SSE-EXD). The solids content of the dispersion was 35.4% and this was diluted as before.
E (524nm) 3.6 E (308nm) 30.1 E (max) 37.2 W (max) 278nm Example 19 The titanium dioxide product was as Example 3, except that the product was not dried at 110C overnight - instead the TiO2 filtercake was used after washing. The % solids in this filtercake was 23.6%. 600g of this pulp was additioned with 14.2g of the sodium polyacrylate used in Example 3 and this mixture was milled for 1 hour on a s~n~lmill. The millbase, which contained 23.1% solids was diluted as previously.
~004~2 E (524nm) 3.4 E (308nm) 47.3 E (max) 50.0 W (max) 293nm 5 Example 20 The 40% TiO2 aqueous dispersion from Example 3 was incorporated into the oil in water sunscreen formulation given below, and a range of sunscreens containing 0, 2.5, 5.0, 7.5% TiO2 were prepared by adding varying amounts of the TiO2 dispersion. The sunscreens were 10 made by heating phase A to 75C. Heat phase B to 75C and add to phase A, mixing with a Silverson stirrer. Phase C is then added. The batch is cooled to 40C and then phases D and E are added.
The sunscreen formulations are as follows:
PHASE INGREDIENI % BY WEIGHT OF INGREDIENTS
0% TiO22.5% TiO2 5.0% TiO2 A Deionised water 62.95 56.70 50.45 TM
A Thickener (Carbopol 940) 15.00 15.00 15.00 (2% Solution) A Tetrasodium EDTA 0.10 0.10 0.10 A Propylene Glycol 2.00 2.00 2.00 B Mineral oil 65/75 7.50 7.50 7.50 B Isopropyl myristate 5.00 5.00 5.00 B Stearic Acid XXX 3.00 3.00 3.00 TM
B Emulsifier (Promulgen D) 1.50 1.50 1.50 B Silicone oil (SF96-100) 2.00 2.00 2.00 C Triethanolamine 99~o 0.75 0.75 0.75 TM
D Preservative (Glydant) 0.20 0.20 0.20 E TiO2Dispersion(40%) 0.00 6.25 12.50 Similarly, for the 7.5% TiO2 sunscreen, 44.20% deionised water was used and 18.75% of the 40% TiO2 aqueous dispersion.
(EDTA = ethylenediamine tetra acetic acid).
These sunscreens were tested for monochromatic protection factors 20 and the Sun Protection Factors (SPF) of the sunscreens were calculated using the in vitro method described by Dr. B.L. Diffey and J. Robson in the Journal of the Society of Cosmetic Chemists, 40, 1989.
This method involves obtaining monochromatic protection factors every Snm over a range of wavelengths from 290-400mn, and from these the 25 sun protection factor can be calculated. The suncreams were applied at 2ul/cm2 (ul = microlitres).
.~- .
j ~,, `~ Z~O~lZ
The monochromatic protection factors can assist in predicting if the product will be efficient as a UVB absorber, a UVA absorber or indeed as both a UVB and UVA absorber. The following results were obtained.
~ 2()04~12 EX~MPLE 20, 0% TiO2 EX~MPLE 20, 2.5% TiO2 Wavelength Monochromatic Wavelength Monochromatic r~n Protection Factor nm Protection Factor 290 1.5 +- .1 290 5.0 +- .9 295 1.4 +- .1 295 4.8 +- .8 300 1.4 +- .2 300 4.7 +- .7 305 1.4 +- .1 305 4.6 +- .7 310 1.4 +- .1 310 4.5 +- .6 315 1.4 +- .1 315 4.2 +- .6 320 1.4 +- .1 320 4.0 +- .5 325 1.4 +- .1 325 3.7 +- .4 330 1.4 +- .1 330 3.5 +- .4 335 1.3 +- .1 335 3.2 +- .3 340 1.3 +- .1 340 2.9 +- .3 345 1.3 +- .1 345 2.7 +- .2 350 1.2 +- .1 350 2.4 +- .2 355 1.2 +- .1 355 2.3 +- .1 360 1.2 +- .1 360 2.1 +- .1 365 1.2 +- .1 365 2.0 +- .1 370 1.2 +- .1 370 1.9 +- .1 375 1.2 +- .1 375 1.9 +- .1 380 1.2 +- .1 380 1.8 +- .1 385 1.2 +- .1 385 1.7 +- .1 390 1.2 +- .1 390 1.6 +- .1 395 1.2 +- .1 395 1.6 +- .1 400 1.2 +- .1 400 1.6 +- .1 ~- 200~1~2 EXAMPLE 20, 5~o TiO2 EXAMPLE 20, 7.5% TiO2 Wavelength Monochromatic Wavelength Monochromatic nm Protection Factor nm Protection Factor 290 7.8 +- 1.7 290 11.5 +- 1.8 S 295 7.7 +- 1.6 295 11.3 +- 1.8 300 7.6 +- 1.5 300 11.3 +- 1.9 305 7.6 +- 1.4 305 11.2 +- 1.8 310 7.4 +- 1.3 310 11.1 +- 1.8 315 7.1 +- 1.1 315 10.6 +- 1.7 320 6.8 +- 1.0 320 10.2 +- 1.6 325 6.4 +- .8 325 9.8 +- 1.5 330 5.9 +- .7 330 9.1 +- 1.5 335 5.4 +- .6 335 8.4 +- 1.4 340 5.0 +- .6 340 7.7 +- 1.4 345 4.5 +- .5 345 7.1 +- 1.3 350 4.1 +- .5 350 6.4 +- 1.2 355 3.8 +- .4 355 5.8 +- 1.1 360 3.5 +- .4 360 5.3 +- 1.0 365 3.2 +- .4 365 4.8 +- .9 370 3.0 +- .4 370 4.4 +- .8 375 2.8 +- .3 375 3.9 +- .7 380 2.6 +- .3 380 3.6 +- .6 385 2.4 +- .3 385 3.2 +- .5 390 2.3 +- .3 390 3.0 +- .4 395 2.2 +- .2 395 2.8 +- .4 400 2.2 +- .2 400 2.6 +- .4 200~Z
The overall SPF values obtained were as follows:
% TiO2 SPF
0.0 1.4 +- 0.1 2.5 4.1 +- 0.2 5.0 6.7 +- 0.5 7.5 10.0 +- 0.6 These overall SPF values in this Example and those following are obtained from CIE (1987) action spectrum and solar spectrum at 40 degrees N and solar altitude of 20 degrees.
The results for the monochromatic protection factors show that there is protection provided throughout the UVB and UVA region.
Example 21 The 40% TiO2 aqueous dispersion from example 3 was incorporated into the water in oil sunscreen formulation given below and two sunscreens were formulated, cont~ining 2.55'o and 10~o TiO2.
The suncreams were made as follows:
Add items 3 and 4 to water with mixing Slowly add TiO2 dispersion and heat with agitation to 75C. Add phase A to phase B at 75C with vigorous agitation. Cool with mixing to room temperature.
The suncream formulations are:
- 200~1Z
No. PHASE INGREDIENT % BY WEIGHT OF INGREDIENT
2.5% TiO2 10.0% TiO~
A TiO2 Dispersion (40~o) 6.25 25.00 2 A Deionised water 54.45 35.70 3 A Propylene glycol 3.00 3.00 4 A Preservative (Glydant) 0.20 0.20 B Octyl palmitate 11.00 11.00 6 B Mineral oil65/75 7.50 7.50 7 B F.m~ ifier (Elfacos E 200)5.00 5.00 8 B Stabiliser (Elfacos ST 9) 8.60 8.60 9 B Emollient (Elfacos C 26) 4.00 4.00 These suncreams were tested for monochromatic protection factors and SPF using the method above and the following results were obtained - 200~112 EX~MPLE 21, 10% TiO2 EXAMPLE 21, 2.S~o TiO2 Wavelength Monochromatic Wavelength Monochromatic nrn Protection Factor nm Protection Factor 290 25.0 +- 5.6 290 9.5 +- 1.7 295 25.7 +- 5.7 295 9.5 +- 1.8 300 25.8 +- 5.8 300 9.4 +- 1.8 305 25.8 +- 6.1 305 9.3 +- 1.8 310 25.4 +- 6.0 310 8.9 +- 1.8 315 24.5 +- 5.8 315 8.3 +- 1.6 320 22.9 +- 5.3 320 7.5 +- 1.5 325 21.4 +- 4.9 325 6.6 +- 1.3 330 19.5 +- 4.4 330 5.9 +- 1.1 335 17.3 +- 3.7 335 5.1 +- .9 340 15.1 +- 3.1 340 4.5 +- .7 345 13.0 +- 2.6 345 3.9+- .6 350 11.1 +- 2.1 350 3.4 +- .4 355 9.5 +- 1.7 355 3.1 +- .4 360 8.2 +- 1.4 360 2.8 +- .4 365 7.0 +- 1.1 365 2.5 +- .2 370 6.1 +- .8 370 2.3 +- .2 375 5.3 + .7 375 2.1 +- .2 380 4.6 +- .5 380 2.0 +- .1 385 4.0 +- .4 385 1.9 +- .1 390 3.6 +- .3 390 1.8 +- .1 395 3.3 +- .2 395 1.7 +- .1 400 3.1 +- .2 400 1.6 +- .1 200~1~LZ
The overall SPF values were as follows:
% TiO2 SPF
2.5 7.4 + - 0.5 10.0 21.0 +- 1.7 5 Again the results for the monochromatic protection factors show that there is some protection provided throughout the UVB and UVA region.
Example 22 The 40% TiO2 aqueous dispersion from example 3 was incorporated into an oil in water suncream formulation containing 10% TiO2. The cream 10 was made by heating phase A to 75C and heating phase B to 75C. Phase B
is added to phase A, then phase C is added. Cool to 40C and add phases D
and E.
- ~o~
PHASE INGREDIENT % BY VVEIGHT OF INGREDIENT
A Deionised water 35.95 A Thickener (Carbopol 940) 15.00 (2% Solution) A Tetrasodium EDTA 0.10 A Propylene glycol 2.00 A Fmlllsifier (Mon~m~te CPA-40) 2.00 B Mineral oil 65/75 7.50 B Isopropyl Myristate 5.00 B Stearic acid XXX 3.00 B Solvent (Promulgen D) 1.50 B Silicone oil (SF96-100) 2.00 C Triethanolamine 99% 0.75 D Preservative (Glydant) 0.20 E TiO2 Dispersion (40~o) 25.00 This cream was tested for monochromatic protection factors and SPF as previously.
`- 20(~41~2 EXAMPLE 22, 10% TiO2 Wavelength Monochromatic nm Protection Factor 290 9.6 +- 1.1 295 9.4 +- 1.3 300 9.4 +- 1.2 305 9.3 +- 1.1 310 9.1 +- 1.1 315 8.3 +- 1.1 320 8.5 +- 1.0 325 8.0 +- .9 330 7.6 +- .8 335 7.1 +- .8 340 6.6 +- .7 345 6.1 +- .6 350 5.6 +- .5 355 5.1 +- .4 360 4.7 +- .4 365 4.3 +- .3 370 4.0 +- .2 375 3.6 +- .2 380 3.3 +- .2 385 3.0 + - .1 390 2.8 +- .1 395 2.6 +- .1 400 2.5 +- .1 ~ 200~1~2 ,_ The overall SPF value obtained was 8.4 +- 0.4 and again there is protection throughout the UVB and UVA regions.
Various aspects of the invention are a~ follows:
An aqueous dispersion oftitanium dioxide comprising water, particles of titanium dioxide having an acicular shape and having a ratio of the longest dimension to the shortest dimension within the range 8:1 to 2:1 and wherein the longest dimension is within the range 0.01 to 0.15 microns and a dispersing agent being a polymer or a copolymer of an acrylic acid or a substituted acrylic acid or a salt thereof and said titanium dioxide being present in an amount to produce a solids content for the dispersion of from 20 to 60 per cent by weight and said dispersion being substantially transparent to visible light and having a maximum extinction coefficient (E(max)) in the ultra-violet range of wavelengths of at least 30 litres per gm per cm.
A method for the m~nllf~ctllre of an aqueous dispersion comprising milling in the preser~ce of particulate grinding medium particulate titanium dioxide in water in the presence of a dispersing agent being a polymer or a copolymer of an acrylic acid or a substituted acrylic acid or a salt thereof, said tit~ni. Im dioxide having an acicular shape and having a ratio of the longest dimension to the shortest dimension within the range 8: I to 2: 1 and wherein the longest dimension is within the range 0.01 to 0.15 microns and the titanium dioxide is present in an amount sufficient to produce a solids content of from 20 to 60 per cent by weight until the titanium dioxide is dispersed in said water to produce a product having a maximum extinction coefficient (E(max)) in the ultra-violet wavelengths of at least 30 litres per gm per cm and being substantially transparent to visible light.
4 ~ 1 2 The aqueous dispersions of the present invention contain a high proportion of the specified particulate titanium dioxide and as described there is sufficient present to confer on the dispersion or solids content of at least 20 per cent by weight. The dispersion can have a solids content of up to 60~o per cent by weight but preferably sufficient particulate titanium dioxide is present for the aqueous dispersion to have a solids content of from 25 to 50 per cent by weight. The ~tt~inment of such high solids contents with the specified particulate titanium dioxide enables the aqueous dispersion to be of beneficial and convenient use in the m~nl-f~cture of compositions or mixtures to be used to absorb UV
radiations. In some cases the aqueous dispersion may be in the form of a light gel which can be mixed easily and reliquefied. This gelling has no adverse effects on the absorption of UV light.
The particulate titanium dioxide is of a specified form. The material is acicular in shape and preferably the particles have a ratio of the largest dimension to the shortest dimension within the range 8:1 to 2:1.
Usually the particles of titanium dioxide have a largest dimension within the range 0.01 to 0.15 micron and preferably 0.02 to 0.1 micron.
Preferably the particulate material has a narrow size range with at least .~, 20041~Z
80% by weight falling within the range of largest dimensions of 0.01 to 0.15 micron.
The particles of titanium dioxide forming the aqueous dispersions of the invention can be anatase, rutile or amorphous titanium dioxide S and each particle can be composed of aggregated smaller particles or crystals but preferably each particle is a single particle of the desired size.
The particles of titanium dioxide can be uncoated or coated with one or more hydrous oxides of a metal such as aluminium, zirconium, zinc or titanium and of silicon. Preferably however when the particles 10 are coated then the coating includes a hydrous oxide of aluminium and of silicon, e.g in a weight ratio of Al203:SiO2 of at least 1.5 and not greater than 4.5. Preferably the weight ratio Al203:SiO2 in the coating is from 2.0 to 3.5.
Usually the actual amount of the coating is such that the amount of hydrous oxide when expressed as the oxide, e.g. A1203, iS from 1.0 to 30.0 weight percent based on weight of titanium dioxide and preferably from 5.0 to 20.0 weight per cent oxide, e.g A1203, on weight of titanium dioxide. When the particles are coated with a hydrous oxide of alnminillm and of silicon then the amount of hydrous oxide of silicon will be that necessary to m~int~in the ratio of the amounts of coating hydrous oxides, A1203 and SiO2, within the specified range and generally speaking the weight of the hydrous oxide of silicon will be within the range 0.2 to 20.0 weight percent as SiO2 based on titanium dioxide and preferably from 1.5 to 7.0 weight percent.
The particulate material of the present invention may be formed by any suitable process for m~king acicular products. Typical processes -may involve hydrolysis of an appropriate titanium compound such as titanium tetrachloride or an organic or inorganic titanate or oxidation of an oxidisable titanium compound for example in the vapour state.
A typical process involves the preparation of a solution of a 5 soluble titanium salt which is then hydrolysed to form hydrous titanium oxide. The solution can be that obtained in the so-called "sulphate"
process for the m:~mlf~ctllre of titanium dioxide pigment in which a titaniferous ore is digested with concentrated sulphuric acid and the digestion cake dissolved in water or dilute acid to produce a solution of 10 titanyl sulphate. During the process additional process stages of classification and reduction are usually employed. Hydrolysis of the titanyl sulphate solution produces the precipitate of hydrous titania which is sometimes called "pulp". Soluble iron compounds remain in solution and after neutralisation and washing to an appropriate degree of 15 impurity level the precipitated pulp of hydrous titania is treated with, say sodium hydroxide and subsequently hydrochloric acid to produce the acicular titanium dioxide.
Usually prior to coating of the acicular titanium dioxide product it is preferred to mill the product to an appropriate particle size falling 20 within that speciffed hereinbefore. Milling conveniently can be effected in a wet milling process employing a grinding medium such as sand which can be separated easily and effectively from the milled pulp. Milling, preferably, as carried out in the presence of a dispersing agent which may be an alkali metal silicate, e.g. sodium silicate, which provides at least 25 some of the source of the coating hydrous silica when this is to be deposited subsequently. Should another dispersant be used for example, 200AllZ
an organic dispersant, then the source of coating hydrous silica is added subsequently if to be present.
If desired the milled product is then treated to deposit the coating of the hydrous oxide(s) in the specified amounts. To an aqueous 5 dispersion of the particulate product containing a hydrolysable salt or salts of the desired metal and/or of silicon there is added a reagent which effects hydrolysis of the salt to form the chosen hydrous oxide(s).
Typically aluminium sulphate can be a source of ~lnmin~ or an alkaline ~lnmin~te can be employed or if desired both an acidic aluminium salt 10 and an alkaline solution of an alnmin~te can be added either together or sequentially. Other metal salts and silicates can be used depending on the particular desired coating.
Depending on the pH of the dispersion of the product, hydrolysis and precipitation may require the addition of an alkali or an acid as the 15 reagent. The preferred coating is obtained by adding to an acid reacting dispersion of the particles of titanium dioxide cont~inin~ an alkali metal silicate an amount of ahlminillm sulphate followed by an amount of an alkali metal alllmin~te prior to the addition of a mineral acid such as sulphuric acid to effect formation and precipitation of hydrous alumina 20 and adjustment of the pH of the dispersion to a value in the range 6 to 8, preferably pH 6.8 to 7.5 The product can be separated from the aqueous dispersion, wa~hed and then dried at an elevated temperature of say 70C to 110C
or even higher. In contrast to the usual "sulphate" process for the 25 production of pigmentary titanium dioxide no calcination of hydrous titania is carried out prior to coating. Consequently it may be that some . -2()~4112 of the titania in the product of the invention, if prepared from pulp, is present in a hydrous form even after drying.
Alternatively the particles of titania according to the present invention can be prepared by decomposition or hydrolysis of suitable 5 titanium compounds e.g. titanium tetrachloride. Typically high temperature hydrolysis of an organic titanium compound such as a titanium alkoxide can be used to produce a fine particle sized titania pulp to be converted to acicular form. Oxidation or hydrolysis in the vapour state of titanium halides under appropriate conditions can be also used to 10 prepare the titania to be coated.
The products of the present invention have the property of absorbing UV light and transmitting visible light. This means that the products can find use in a wide variety of applications wherein it is important to m~int~in transparency of visible light while substantially 15 preventing tr:~n~mi~ion of UV light to a surface. Cosmetics, in any form such as lotions, creams, milks, pastes, sticks, face powders, sun screens and hair care products are a number of applications for the products of the invention.
The dispersions of the present invention are prepared by milling 20 the particulate titanium dioxide into water in the presence of a specified organuc dlspersing agent.
The mill which is employed to effect the grinding of the titanium dioxide product in the water is one which uses a particulate grinding medium to grind the product. Such mills are the various types of mills 25 equipped with one or more agitators and using sand or glass beads or ceramic beads or other particles as the particulate grinding medium.
200~112 -Particularly useful are those mills which operate at a high speed and depending on the size of mill a speed of the order of 2500 rev. per minute (r.p.m) is not unusual. For instance mills operating at a speed of from 500 r.p.m to 6000 r.p.m are suitable. Agitator mills in which the tip speed 5 of the agitator is up to and can exceed 10 metres/sec are of use. If desired the mill can be cooled. Also the dispersions can be pre-mixed using a high speed stirrer or the water can be added to the mill initially and then the titanium dioxide and the organic dispersant co-added to the water subsequently. After milling has been carried out for the required 10 time the dispersion is separated from the grinding medium.
The dispersing agent which is present in the aqueous dispersion of the present invention is a polycarboxylic acid or a salt thereof. Partially or fully neutralized salts are usable e.g. the alkali metal salts and ammonium salts. Examples of dispersing agents are polyacrylic acids, 15 substituted acrylic acid polymers, acrylic copolymers, sodium and/or ammonium salts of polyacrylic acids and sodium and/or ammonium salts of acrylic copolymers. Such dispersing agents are typified by polyacrylic acid itself and sodium or ammonium salts thereof as well as copolymers of an acrylic acid with other suitable monomers such as a sulphonic acid 20 derivative such as 2-acrylamido 2-methyl propane sulphonic acid.
Comonomers polymerisable with the acrylic or a substituted acrylic acid can also be one cont~ining a carboxyl grouping. Usually the dispersing agents have a molecular weight of from 1000 to 10,000 and are substantially linear molecules.
`- 2004112 g The amount of the dispersion agent used is usually within the range 5 to 35 per cent by weight of the titanium dioxide in the dispersion and preferably 10 to 25 per cent by weight.
The preferred dispersions of the present invention have a 5 m~ximllm extinction coefficient of at least 30 litres per gram per cm at a wavelength of 308nm. More preferably the dispersion has a m~ximllm extinction coefficient of at least 40 litres per gram per cm at a wavelength of 308nm. The products of the invention are substantially transparent to visible light.
In the past an ideal sunscreen was considered as being one which absorbs or filters out UVB radiation (290-320nm), as it is this which causes erythema. More recently, however, there has been growing concern about the effect that UVA radiation (320-400nm) has on the shn.
It is now widely accepted that the definition of the ideal sunscreen is one which can provide photoprotection from both UVB and UVA
radiation. This ideal sunscreen must therefore contain agents which can absorb or filter out radiation in the range 290-400nm.
The spectra of the acicular ultra-fine titanium dioxide dispersions 20 40% solid content of the invention indicate that there should be protection provided in both the UVB and UVA regions, and values of extinction coefficients covering the range 290-400nm are given as shown below.
-NO. DIOXIDE PIGMENT
E (300nm) 47.8 56.9 57.2 49.6 18.9 E (320nm) 37.2 39.2 44.2 41.6 19.2 E (340nm) 26.1 27.5 29.2 29.0 20.1 E(360nm) 18.3 21.0 18.7 19.5 21.3 E (380nm) 13.9 15.7 13.1 13.8 21.9 E(400nm) 10.6 12.7 9.3 10.2 22.3 For comparison, extinction coefficients are given for similar dispersions of anatase titanium dioxide pigment (uncoated) of solids contents of 40~o by weight. It can be seen that extinction coefficients in the UVB region (290-320nm) are much lower for pigmentary TiO2 than for the products of the invention.
In the UVA region, again extinction is higher for the acicular ultra-fine grade between 320-340nm. From 360nm to 400nm the pigmentary TiO2 has a higher extinction coefficient, but this level of extinction is m~int~ined into the visible region for the pigmentary grade.
This means that the pigment dispersion looks white when applied to the skin.
The ultra-fine TiO2 extinction is very low in the visible region (above 400nm) which means that the dispersion is more transparent and aesthetically acceptable than the pigment dispersion, while still m~int~ining good UVB and UVA extinction coefficients.
The invention is illustrated in the following Examples.
20041~Z
Example 1 Ilmenite was digested with concentrated sulphuric acid. The digestion cake obtained was dissolved in water to form a crude liquor cont~ining iron and titanium sulphates and some suspended insoluble 5 matter. Any iron present in the ferric form was reduced chemically prior to filtering insoluble matter. The liquor after any necessary cryst~ tion and filtration was concentrated by vacuum treatment and then hydrolysed to precipitate hydrous titanium dioxide by boiling and addition of any necessary reaction agent. The product on filtering was a 10 pulp of uncoated hydrous TiO2.
In the subsequent process any water added or used was taken to be demineralised water.
The pulp of the uncoated hydrous TiO2 obtained was diluted to a concentration of 280 grams per litre TiO2 and a sample amount of 2.5 15 litres taken and heated to 60C. Aqueous sodium hydroxide solution cont~ining 700 grams per litre NaOH in an amount of 1.5 litres was heated to 90C and then transferred to a reaction flask having a volume of 5 litres fitted with a condenser. The hot diluted pulp was added over a period of 30 minutes to the reaction flask whilst agitating the contents 20 vigorously and the mixture temperature was held at 117C whilst agitating for a period of 2 hours after the addition had been completed.
Cold water was added to quench the solution in the flask to 90C and to decrease the concentration of titanium dioxide to 140 grams per litre.
The amount of water added was approxim~tely 20~o of the total volume 25 achieved. The contents were agitated for a further 15 minutes at this temperature of 90C prior to cooling to a temperature of 50 to 55C by - 2004~12 -the addition of a further amount of cold water which reduced the concentration of titanium dioxide to about 80 to 90 grams per litre. The dispersion was filtered and the filter cake washed with warm water at a temperature of 50C to 60C so that the filtrate contained less than 1500 5 ppm Na2O. The washed filter cake was then reslurried in water to a concentration of 200 grams per litre TiO2 and at this stage the product was sodium titanate.
Two litres of the washed sodium titanate was added to a reaction flask having a volume of 6 litres and fitted with a condenser. The pH of 10 the dispersion in the flask was reduced to a value within the range 2.8 to 3.1 by the addition of aqueous hydrochloric acid (30% w/w) and the mixture then heated to a temperature of 60C at the rate of 1C per minute. The pH of the mixture was rechecked and adjusted, if necessary, to a value within the range 2.8 to 3.1 by a further addition of the aqueous 15 hydrochloric acid. The dispersion was held at this temperature for 30 minlltes whilst agitated. A further quantity of hydrochloric acid was then added such that the volume added was 0.754 litres of 30~ HCI acid per kilogram of TiO2 in the dispersion such that the ratio of HCl/TiO2 equalled 0.26. The slurry was then heated to the boiling point over a 20 period of 40 minutes and held at the boiling point for a period of 90 minlltes whilst being agitated. The treated product was then quenched by addition of two litres of water and the dispersion had a pH value of 0.4.
Sodium hydroxide solution at a concentration of 400 grams per litres NaOH was then added to neutralise the dispersion to a pH of 7.5 and 25 appr-~xim:~tely 460 ml of the aqueous sodium hydroxide was required.
The dispersion was filtered and the filter cake washed with two litres of 20041~
water. The washed filter cake was then redispersed with a further quantity of two litres of water and filtered again to produce a filter cake having a solids content of 34% by weight.
The filter cake is then dried in an oven at 110C overnight. The 5 product was acicular rutile titanium dioxide having an average size of 0.02 x 0.1 microns.
276g of the dried TiO2 product was added to 414g of water and 33.1g of sodium polyacrylate obtainable under the name Antiprex A. This mixture was milled in a sandmill for 1 hour using 800ml of glass beads, 10 known as Ballotini (Grade 4), as grinding media to disperse the product in water and to separate any aggregated particles. The glass beads were removed from the milled dispersion at the end of the milling period by filtration.
The millbase, which contained 38.2% solids was diluted with 15 demineralised water in the proportion O.lg millbase in lOOml water, and then lml of this diluted millbase in 20ml water. The mill base was then exposed in a spectrometer (Beckman DU-50) with a 1 cm pathlength and the absorbance of UV and visible light measured.
Extinction coefficients at two wavelengths and at the m~ximllm 20 wavelength were then calc~ ted from the equation A = E.c.l where A
= absorbance, E = Extinction coefficient in litres per gram per cm, c =
concentration in grams per litre and 1 = pathlength in cm. W =
wavelength (nm) - 2~0~1~Z
Results were:
E (524nm) 5.1 E (308nm) 60.8 E (max) 65.5 W(max) 293 Example 2 As Example 1 except that milling was carried out on a high speed bead mill (Eiger M750-SSE-EXD) using 400ml glass Ballotini as grinding media. 385g TiO2 was mixed with 658g of water and 46.4g of the sodium 10 polyacrylate used in Example 1. The dispersion was milled for 30 mins and the solids content of the dispersion was 35.4~o.
After separation from the grinding aid a O.lg portion was diluted as previously with water and this diluted sample was exposed in a spectrometer (Beckman DU-50). Extinction coefficients were calculated 15 as previously.
E (524nm) 5.5 E (308nm) 45.5 E (max) 50.7 W (max) 279 20 Example 3 The procedure of Example 1 was repeated to obtain a washed filter cake of 34% by weight solids content of uncoated titanium dioxide.
882 grams of the filter cake (300 grams TiO2) was diluted to a concentration of 100 grams per litre TiO2 with demineralised water and 25 mixed with sodium silicate in an amount equivalent to 5% by weight SiO2 on weight of TiO2 and milled in a sand mill for 2 hours after adjusting the - 20041~2 pH of the dispersion to 10.0 to 11.5 with aqueous sodium hydroxide. The grinding medium was Ottowa sand and was removed from the milled dispersion at the end of the milling period by filtration.
The aqueous dispersion after removal of the sand had a pH of 9.1 and was heated to 60C and m~int~ined at this during the coating operation.
To the stirred dispersion aqueous ~ minium sulphate solution (68 grams per litre Al2O3 equivalent) was added dropwise in an amount sufficient to introduce ahlminillm sulphate in an amount equivalent to 5% Al2O3 on weight of TiO2 over a period of 60 minutes. Approximately 219 mls of the solution were added. After the addition has been completed the dispersion had a pH of 2.4 and was allowed to age for 30 mimltes at 60C whilst stirring was m~int~ined.
An ~lk~line solution of sodium ahlmin~te (80 grams per litre A1203) was then added over a period of 60 minutes to the stirred dispersion in an amount sufficient to introduce the equivalent of 10% by weight A1203 on weight of TiO2. Approxim~tely 375 mls of the solution was found to have been added. The dispersion which had a pH of 11.8 was stirred at 60C for 45 minutes.
Sulphuric acid (10%) was added to the aqueous dispersion to reduce the pH to 7.5. The neutralised dispersion was aged for 15 minutes whilst being stirred. The dispersion was filtered to produce a filter cake of the coated product which was then washed with 1 litre of demineralised water. The cake was redispersed in 1 litre of demineralised water, re-filtered and then washed again with demineralised water.
- 20041~2 The product was dried at 110C overnight. The product was acicular rutile titanium dioxide having an average size of 0.02 x 0.10 microns with a coating of hydrous silica in an amount equivalent to 4.8%
by weight SiO2 on TiO2 and hydrous alumina in an amount of 11.2% by S weight A1203 on TiO2 as determined by analysis of the product.
50g of the dried coated TiO2 product was added to 70ml of water and 5.03g of the sodium polyacrylate used in Example 1. This mixture was milled in a high speed bead mill (Eiger M-50-VSE) for 2 hours using 35ml of glass beads. The millbase, which contained 40% solids was 10 diluted as in previous examples and exposed in a spectrometer.
Extinction coefficients are listed below:
E (524nm) 4.2 E (308nm) 44.5 E (max) 50.0 W(max) 287nm Example 4 276g of the dried coated TiO2 product of Example 3 was added to 414g of water and 33.1g of the sodium polyacrylate used in Example 1.
The mixture was milled in a sandmill for 1 hour using 800g of glass 20 beads. The millbase, which contained 38~o solids, was diluted as previously and a spectrum was recorded E (525nm) 5.6 E (308nm) 49.7 E (max) 53.1 W (max) 288 `- 20041~2 Example 5 A solution of titanium tetrachloride in hydrochloric acid having an acid /titanium ratio (weight ratio) of 1.77 was prepared containing 200 grams per litre TiO2 equivalent. An aqueous solution of sodium 5 hydroxide (110 grams per litre) was prepared from carbonate free ingredients.
To a 3 litre glass flask fitted with a stirrer there was added 1203ml of the aqueous sodium hydroxide solution and 400 ml of water (demineralised). To the stirred solution there was then added 400 mls of 10 the titanium tetrachloride solution over a period of 15 minutes and during this period the stirrer speed was controlled at 100 rev. per minute.
After the addition had been completed the temperature was raised from its initial value of 40-45C to 82C at a rate of 1C per minute and the mixture was held at this temperature for a further 120 minutes whilst 15 stirring continued. During the heating to the temperature of 82C the solution was observed to clear partially, normally at about 60-70C as the titanium dioxide peptises and then re-precipitates.
After holding at 82C for 120 minutes the mixture was added to 2.5 litres of cold distilled water to quench the mixture then a further 5 20 litres of the water at 60C is added to the quenched mixture. Sodium hydroxide solution (110 grams per litre) is then added to the mixture to neutralise the ~ u~e to a pH value of 7.5. The neutralised and flocculated mixture was allowed to settle, filtered and the cake washed with 2.5 litres of water by stirring prior to refiltering. The cake was 25 washed again by re-slurrying with 2.5 litres of water and filtered to produce a cake having a solids content of 22% by weight.
- 200~112 The titanium dioxide in the cake was acicular and rutile having an average size of 0.01 to 0.05 microns.
The acicular titanium dioxide product obtained was coated in accordance with Example 3 with hydrous silica (5~o by weight on weight S of TiO2) and hydrous alumina (l5~o by weight).
276g of the TiO2 product was added to 414g of water and 33.1g of the sodium polyacrylate used in Example 1. This mixture was milled in a sandmill for 1 hour using 800g of glass beads. The millbase, which contained 41~o solids, after milling, was diluted as previously and a 10 ,spectrum was recorded.
E (524nm) 4.9 E (308nm) 35.7 E (max) 42.7 W (max) 276nm Example 6 Ilmenite was digested with concentrated sulphuric acid. The digestion cake obtained was dissolved in water to form a crude liquor cont~ining iron and titanium sulphate and some suspended insoluble matter. Any iron present in the ferric form was reduced chemically prior to filtering insoluble matter. The liquor after any necessary cryst~ ation and filtration was concentrated by vacuum treatment and then hydrolysed to precipitate hydrous titanium dioxide by boiling and addition of any necessary reaction agent. The product on filtering was a pulp of uncoated hydrous TiO2.
Four kilograms of the pulp so obtained was mixed with 5 litres of demineralised water. The pH of the diluted pulp was 1.9 and 375 ml of - 20041~2 an aqueous solution of sodium hydroxide (cont~ining 400 grams per litre NaOH) added to increase the pH to a value within the range 7.5 to 7.8.
The dispersed pulp was filtered and the cake washed with 6.5 litres of demineralised water. The washed filter cake was then redispersed in 3 5 litres of demineralised water and the pH measured at a value of 8.4.
Sulphuric acid (10%) (118ml) was added to reduce the pH of the dispersion to 7.5 prior to filtering again. After washing the filter cake with 6.0 litres of demineralised water the solids content of the cake was 44.3% by weight.
The filter cake was dried in an oven at 110C overnight. 50g of the product was added to 70g of water and 8.78g of the sodium polyacrylate used in Example A. The mixture was milled (Eiger M-50-VSE) for 2 hours using 35ml glass beads.
The millbase which contained 38.8% solids was diluted and a 15 spectrum was recorded.
E (524nm) 5.6 E (308nm) 40.4 E (max) 54.1 W (max) 257nm 20 Example 7 276g of the dried TiO2 product of Example 1 was added to 257g of water and 33.1g of the sodium polyacrylate used in Example 1. This rnixture was rnilled in a sand mill for 1 hour using 800ml of glass beads.
The millbase, which contained 48.7% solids was diluted as before and a 25 spectrum was recorded.
2~1 12 E (524nm) 6.9 E (308nm) 44.3 E (max) 47.6 W (max) 293 S Example 8 35g of the dried coated TiO2 product of Example 3 was added to 61.5g of water and 3.5g of a dispersant which is a sodium salt of an acrylic copolymer (35% solution) obtainable under the name Bevaloid 226/35.
The mixture was milled in a sand mill for 1 hour using SOg of glass beads.
10 The millbase, which contained 35~o solids was diluted as previously and a spectrum was recorded.
E (524nm) 3.3 E (308nm) 43.1 E (max) 45.1 W (max) 296 Example 9 35g of the same dried coated TiO2 product used in Example 8 was added to 61.5g of water and 3.5g of a sodium salt of an acrylic acid (50%
solution) obtainable under the name BevaloidTM 6770. The ~ u~e was 20 milled in a sand mill for 1 hour using SOg of glass beads. The millbase, which contained 35~o solids, was diluted as previously and a spectrum was recorded.
E (524nm) 4.9 E (308nm) 46.4 E(max) 49.0 W (max) 296nm Z0041~Z
Example 10 35g of the same dried coated TiO2 product used in Example 8 was added to 61.5g of water and 3.5g of a polyacrylic acid of molecular weight 2100 and obtainable under the name Carbopol 420.. The mixture was 5 milled as in Example 9. Millbase was 3so~o solids.
E (524nm) 6.6 E (308nm) 41.6 E (max) 42.9 W (max) 296 10 Example 11 35g of the same dried coated TiO2 product used in Example 8 was added to 61.5g of water and 3.5g of a polyacrylic acid having a molecular weight of 5100 and obtainable under the name Carbopol 430. Mixture milled as in Example 9. The millbase which contained 3so~c solids was 15 diluted as before.
E (524 nm) 4.9 E (308nm) 46.5 E (max) 48.2 W (max) 296 20 Example 12 328g of the same dried coated TiO2 product used in Example 8 was added to 369.2g of water and 32.8g of a fully neutralised sodium salt of a polycarboxylic acid obtainable under the name DP6. The sample was milled in a s~n(lmill for 1 hour using 800g of glass beads. The millbase, 25 which contained 42.8,~o solids after milling, was diluted as before.
- 2~4i~2 E (524nm) 4.8 E (308nm) 51.4 E (max) 57.1 W (max) 293 5 Example 13 385g of the acicular titanium dioxide product produced by the method of Example 5 was used, except that it was uncoated. This product was mixed with 658g of water and 46.4g of the sodium salt used in Example 12 obtainable under the name DP6, and was milled for 30 10 minutes on a high speed be~-lmill (Eiger M750-SSE-EXD). The solids content of the dispersion was 35.4% and this was diluted as previously and a spectrum was recorded (Perkin Elmer Lambda 2 UV/Vis Spectrometer).
E (524nm) 2.5 E (308nm) 28.4 E (max) 35.8 W (max) 279nm Example 14 50g of the acicular titanium dioxide product in Example 1 was added to 58.8g of water and 4.31g of an ammonium salt of an acrylic acid obtainable under the name Dispex A40. The product was milled (Eiger M50VSE) for 2 hours using 35ml of glass beads. The millbase, which had a solids content of 44.2% was diluted as before and a spectrum was recorded E (524nm) 5.0 E (308nm) 44.6 E (max) 46.7 W (max) 294nm 5 Example 15 50g of the acicular product produced in Example 1 was added to 58.8g of water and 3.01g of the fully neutralized sodium salt used in Example 12. The sample was milled as in Example 14. The millbase, which had a solids content of 44.7~o was diluted as before and a spectrum 10 was recorded.
E (524nm) 3.2 E (308nm) 55.5 E (max) 61.4 W (max) 290nm 15 Example 16 50g of the acicular titanium dioxide product of Example 8 was added to 58.8g of water and 5.84 g of a sodium salt of a polymethacrylic acid having a molecular weight of 12000 and obtainable under the name Orotan 850.. The sample was milled as in Example 14. The millbase, 20 which had a solids content of 43.6~o was diluted as before.
E (524nm) 7.3 E (308nm) 45.4 E (max) 46.4 W (max) 298 nm 20041~X
Example 17 50g of the acicular titanium dioxide product of Example 8 was added to 58.8g of water and 6.5g of the ammonium salt of an acrylic acid as used in Example 14. The sample was milled as in Example 14. The 5 millbase, which contained 43.4~o solids, was diluted as before.
E (524nm) 6.1 E (308nm) 50.5 E (max) 52.7 W (max) 294nm 10 Example 18 385g of the acicular titanium dioxide product of Example 5 was mixed with 658g water and 45.3g of the sodium salt used in Example 16..
This mixture was milled for 45 minutes (Eiger M750-SSE-EXD). The solids content of the dispersion was 35.4% and this was diluted as before.
E (524nm) 3.6 E (308nm) 30.1 E (max) 37.2 W (max) 278nm Example 19 The titanium dioxide product was as Example 3, except that the product was not dried at 110C overnight - instead the TiO2 filtercake was used after washing. The % solids in this filtercake was 23.6%. 600g of this pulp was additioned with 14.2g of the sodium polyacrylate used in Example 3 and this mixture was milled for 1 hour on a s~n~lmill. The millbase, which contained 23.1% solids was diluted as previously.
~004~2 E (524nm) 3.4 E (308nm) 47.3 E (max) 50.0 W (max) 293nm 5 Example 20 The 40% TiO2 aqueous dispersion from Example 3 was incorporated into the oil in water sunscreen formulation given below, and a range of sunscreens containing 0, 2.5, 5.0, 7.5% TiO2 were prepared by adding varying amounts of the TiO2 dispersion. The sunscreens were 10 made by heating phase A to 75C. Heat phase B to 75C and add to phase A, mixing with a Silverson stirrer. Phase C is then added. The batch is cooled to 40C and then phases D and E are added.
The sunscreen formulations are as follows:
PHASE INGREDIENI % BY WEIGHT OF INGREDIENTS
0% TiO22.5% TiO2 5.0% TiO2 A Deionised water 62.95 56.70 50.45 TM
A Thickener (Carbopol 940) 15.00 15.00 15.00 (2% Solution) A Tetrasodium EDTA 0.10 0.10 0.10 A Propylene Glycol 2.00 2.00 2.00 B Mineral oil 65/75 7.50 7.50 7.50 B Isopropyl myristate 5.00 5.00 5.00 B Stearic Acid XXX 3.00 3.00 3.00 TM
B Emulsifier (Promulgen D) 1.50 1.50 1.50 B Silicone oil (SF96-100) 2.00 2.00 2.00 C Triethanolamine 99~o 0.75 0.75 0.75 TM
D Preservative (Glydant) 0.20 0.20 0.20 E TiO2Dispersion(40%) 0.00 6.25 12.50 Similarly, for the 7.5% TiO2 sunscreen, 44.20% deionised water was used and 18.75% of the 40% TiO2 aqueous dispersion.
(EDTA = ethylenediamine tetra acetic acid).
These sunscreens were tested for monochromatic protection factors 20 and the Sun Protection Factors (SPF) of the sunscreens were calculated using the in vitro method described by Dr. B.L. Diffey and J. Robson in the Journal of the Society of Cosmetic Chemists, 40, 1989.
This method involves obtaining monochromatic protection factors every Snm over a range of wavelengths from 290-400mn, and from these the 25 sun protection factor can be calculated. The suncreams were applied at 2ul/cm2 (ul = microlitres).
.~- .
j ~,, `~ Z~O~lZ
The monochromatic protection factors can assist in predicting if the product will be efficient as a UVB absorber, a UVA absorber or indeed as both a UVB and UVA absorber. The following results were obtained.
~ 2()04~12 EX~MPLE 20, 0% TiO2 EX~MPLE 20, 2.5% TiO2 Wavelength Monochromatic Wavelength Monochromatic r~n Protection Factor nm Protection Factor 290 1.5 +- .1 290 5.0 +- .9 295 1.4 +- .1 295 4.8 +- .8 300 1.4 +- .2 300 4.7 +- .7 305 1.4 +- .1 305 4.6 +- .7 310 1.4 +- .1 310 4.5 +- .6 315 1.4 +- .1 315 4.2 +- .6 320 1.4 +- .1 320 4.0 +- .5 325 1.4 +- .1 325 3.7 +- .4 330 1.4 +- .1 330 3.5 +- .4 335 1.3 +- .1 335 3.2 +- .3 340 1.3 +- .1 340 2.9 +- .3 345 1.3 +- .1 345 2.7 +- .2 350 1.2 +- .1 350 2.4 +- .2 355 1.2 +- .1 355 2.3 +- .1 360 1.2 +- .1 360 2.1 +- .1 365 1.2 +- .1 365 2.0 +- .1 370 1.2 +- .1 370 1.9 +- .1 375 1.2 +- .1 375 1.9 +- .1 380 1.2 +- .1 380 1.8 +- .1 385 1.2 +- .1 385 1.7 +- .1 390 1.2 +- .1 390 1.6 +- .1 395 1.2 +- .1 395 1.6 +- .1 400 1.2 +- .1 400 1.6 +- .1 ~- 200~1~2 EXAMPLE 20, 5~o TiO2 EXAMPLE 20, 7.5% TiO2 Wavelength Monochromatic Wavelength Monochromatic nm Protection Factor nm Protection Factor 290 7.8 +- 1.7 290 11.5 +- 1.8 S 295 7.7 +- 1.6 295 11.3 +- 1.8 300 7.6 +- 1.5 300 11.3 +- 1.9 305 7.6 +- 1.4 305 11.2 +- 1.8 310 7.4 +- 1.3 310 11.1 +- 1.8 315 7.1 +- 1.1 315 10.6 +- 1.7 320 6.8 +- 1.0 320 10.2 +- 1.6 325 6.4 +- .8 325 9.8 +- 1.5 330 5.9 +- .7 330 9.1 +- 1.5 335 5.4 +- .6 335 8.4 +- 1.4 340 5.0 +- .6 340 7.7 +- 1.4 345 4.5 +- .5 345 7.1 +- 1.3 350 4.1 +- .5 350 6.4 +- 1.2 355 3.8 +- .4 355 5.8 +- 1.1 360 3.5 +- .4 360 5.3 +- 1.0 365 3.2 +- .4 365 4.8 +- .9 370 3.0 +- .4 370 4.4 +- .8 375 2.8 +- .3 375 3.9 +- .7 380 2.6 +- .3 380 3.6 +- .6 385 2.4 +- .3 385 3.2 +- .5 390 2.3 +- .3 390 3.0 +- .4 395 2.2 +- .2 395 2.8 +- .4 400 2.2 +- .2 400 2.6 +- .4 200~Z
The overall SPF values obtained were as follows:
% TiO2 SPF
0.0 1.4 +- 0.1 2.5 4.1 +- 0.2 5.0 6.7 +- 0.5 7.5 10.0 +- 0.6 These overall SPF values in this Example and those following are obtained from CIE (1987) action spectrum and solar spectrum at 40 degrees N and solar altitude of 20 degrees.
The results for the monochromatic protection factors show that there is protection provided throughout the UVB and UVA region.
Example 21 The 40% TiO2 aqueous dispersion from example 3 was incorporated into the water in oil sunscreen formulation given below and two sunscreens were formulated, cont~ining 2.55'o and 10~o TiO2.
The suncreams were made as follows:
Add items 3 and 4 to water with mixing Slowly add TiO2 dispersion and heat with agitation to 75C. Add phase A to phase B at 75C with vigorous agitation. Cool with mixing to room temperature.
The suncream formulations are:
- 200~1Z
No. PHASE INGREDIENT % BY WEIGHT OF INGREDIENT
2.5% TiO2 10.0% TiO~
A TiO2 Dispersion (40~o) 6.25 25.00 2 A Deionised water 54.45 35.70 3 A Propylene glycol 3.00 3.00 4 A Preservative (Glydant) 0.20 0.20 B Octyl palmitate 11.00 11.00 6 B Mineral oil65/75 7.50 7.50 7 B F.m~ ifier (Elfacos E 200)5.00 5.00 8 B Stabiliser (Elfacos ST 9) 8.60 8.60 9 B Emollient (Elfacos C 26) 4.00 4.00 These suncreams were tested for monochromatic protection factors and SPF using the method above and the following results were obtained - 200~112 EX~MPLE 21, 10% TiO2 EXAMPLE 21, 2.S~o TiO2 Wavelength Monochromatic Wavelength Monochromatic nrn Protection Factor nm Protection Factor 290 25.0 +- 5.6 290 9.5 +- 1.7 295 25.7 +- 5.7 295 9.5 +- 1.8 300 25.8 +- 5.8 300 9.4 +- 1.8 305 25.8 +- 6.1 305 9.3 +- 1.8 310 25.4 +- 6.0 310 8.9 +- 1.8 315 24.5 +- 5.8 315 8.3 +- 1.6 320 22.9 +- 5.3 320 7.5 +- 1.5 325 21.4 +- 4.9 325 6.6 +- 1.3 330 19.5 +- 4.4 330 5.9 +- 1.1 335 17.3 +- 3.7 335 5.1 +- .9 340 15.1 +- 3.1 340 4.5 +- .7 345 13.0 +- 2.6 345 3.9+- .6 350 11.1 +- 2.1 350 3.4 +- .4 355 9.5 +- 1.7 355 3.1 +- .4 360 8.2 +- 1.4 360 2.8 +- .4 365 7.0 +- 1.1 365 2.5 +- .2 370 6.1 +- .8 370 2.3 +- .2 375 5.3 + .7 375 2.1 +- .2 380 4.6 +- .5 380 2.0 +- .1 385 4.0 +- .4 385 1.9 +- .1 390 3.6 +- .3 390 1.8 +- .1 395 3.3 +- .2 395 1.7 +- .1 400 3.1 +- .2 400 1.6 +- .1 200~1~LZ
The overall SPF values were as follows:
% TiO2 SPF
2.5 7.4 + - 0.5 10.0 21.0 +- 1.7 5 Again the results for the monochromatic protection factors show that there is some protection provided throughout the UVB and UVA region.
Example 22 The 40% TiO2 aqueous dispersion from example 3 was incorporated into an oil in water suncream formulation containing 10% TiO2. The cream 10 was made by heating phase A to 75C and heating phase B to 75C. Phase B
is added to phase A, then phase C is added. Cool to 40C and add phases D
and E.
- ~o~
PHASE INGREDIENT % BY VVEIGHT OF INGREDIENT
A Deionised water 35.95 A Thickener (Carbopol 940) 15.00 (2% Solution) A Tetrasodium EDTA 0.10 A Propylene glycol 2.00 A Fmlllsifier (Mon~m~te CPA-40) 2.00 B Mineral oil 65/75 7.50 B Isopropyl Myristate 5.00 B Stearic acid XXX 3.00 B Solvent (Promulgen D) 1.50 B Silicone oil (SF96-100) 2.00 C Triethanolamine 99% 0.75 D Preservative (Glydant) 0.20 E TiO2 Dispersion (40~o) 25.00 This cream was tested for monochromatic protection factors and SPF as previously.
`- 20(~41~2 EXAMPLE 22, 10% TiO2 Wavelength Monochromatic nm Protection Factor 290 9.6 +- 1.1 295 9.4 +- 1.3 300 9.4 +- 1.2 305 9.3 +- 1.1 310 9.1 +- 1.1 315 8.3 +- 1.1 320 8.5 +- 1.0 325 8.0 +- .9 330 7.6 +- .8 335 7.1 +- .8 340 6.6 +- .7 345 6.1 +- .6 350 5.6 +- .5 355 5.1 +- .4 360 4.7 +- .4 365 4.3 +- .3 370 4.0 +- .2 375 3.6 +- .2 380 3.3 +- .2 385 3.0 + - .1 390 2.8 +- .1 395 2.6 +- .1 400 2.5 +- .1 ~ 200~1~2 ,_ The overall SPF value obtained was 8.4 +- 0.4 and again there is protection throughout the UVB and UVA regions.
Claims (19)
1 . An aqueous dispersion of titanium dioxide comprising water, particles of titanium dioxide having an acicular shape and having a ratio of the longest dimension to the shortest dimension within the range 8:1 to 2:1 and wherein the longest dimension is within the range 0.01 to 0.15 microns and a dispersing agent being a polymer or a copolymer of an acrylic acid or a substituted acrylic acid or a salt thereof and said titanium dioxide being present in an amount to produce a solids content for the dispersion of from 20 to 60 per cent by weight and said dispersion being substantially transparent to visible light and having a maximum extinction coefficient (E(max)) in the ultra-violet range of wavelengths of at least 30 litres per gm per cm.
2. An aqueous dispersion according to claim I in which the maximum extinction coefficient at a wavelength of 308 nm is 40 litres per gram per cm.
3. An aqueous dispersion according to claim 1 in which the longest dimension is 0.02 to 0.1 micron.
4. An aqueous dispersion according to claim 1 in which the solids content is from 25 to 50 per cent by weight.
5. An aqueous dispersion according to claim 1 in which at least 80% by weight of the particles of said titanium dioxide have a longest dimension within the range 0.01 to 0.15 micron.
6. An aqueous dispersion according to claim 1 in which the particles of titanium dioxide are coated with one or more hydrous oxides of a metal or of silicon.
7. An aqueous dispersion according to claim 6 in which the hydrous oxide is of aluminium, zirconium, zinc or titanium.
8. An aqueous dispersion according to claim 6 in which the particles of titanium dioxide are coated with an amount of hydrous oxide when expressed as oxide of from 1.0 to 30.0 weight per cent based on weight of titanium dioxide.
9. An aqueous dispersion according to claim 8 in which the amount of hydrous oxide is from 5.0 to 20.0 weight per cent as oxide on weight of titanium dioxide.
10. An aqueous dispersion according to claim 6 in which the particles of titanium dioxide are coated with a hydrous oxide of aluminium and of silicon in a weight ratio of Al2O3:SiO7 of at least 1. 5 and not greater than 4.5.
11. An aqueous dispersion according to claim 10 in which the weight ratio Al2O3: SiO7 is from 2.0 to 3.5.
12. An aqueous dispersion according to claim 1 in which the dispersing agent is an alkali metal salt or ammonium salt of said polymer or copolymer of an acrylic acid or a substituted acrylic acid.
13. An aqueous dispersion according to claim 1 in which the copolymer is a copolymer of an acrylic acid and a sulphonic acid derivative.
14. An aqueous dispersion according to claim 1 in which the dispersing agent is a substantially linear molecule having a molecular weight of from 1000 to 10000.
15. An aqueous dispersion according to claim 1 in which the amount of the dispersing agent is from 5 to 35 per cent by weight of the titanium dioxide in the dispersion.
16. An aqueous dispersion according to claim 15 in which the amount is from 10 to 25 per cent by weight.
17. A method for the manufacture of an aqueous dispersion comprising milling in the presence of particulate grinding medium particulate titanium dioxide in water in the presence of a dispersing agent being a polymer or a copolymer of an acrylic acid or a substituted acrylic acid or a salt thereof, said titanium dioxide having an acicular shape and having a ratio of the longest dimension to the shortest dimension within the range 8: 1 to 2: 1 and wherein the longest dimension is within the range 0.01 to 0.15 microns and the titanium dioxide is present in an amount sufficient to produce a solids content of from 20 to 60 per cent by weight until the titanium dioxide is dispersed in said water to produce a product having a maximum extinction coefficient (E(max)) in the ultra-violet wavelengths of at least 30 litres per gm per cm and being substantially transparent to visible light.
18. A method according to claim 17 in which the milling is effected in a mill having one or more agitators operating at a speed of from 500 r.p.m. to 6000 r.p.m.
19. A method according to claim 17 in which milling is effected with an agitator mill having an agitator operating at a tip speed of the agitator of up to 10 metres/sec.
~q
~q
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8829402.0 | 1988-12-16 | ||
| GB888829402A GB8829402D0 (en) | 1988-12-16 | 1988-12-16 | Dispersion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2004112A1 CA2004112A1 (en) | 1990-06-16 |
| CA2004112C true CA2004112C (en) | 1995-08-08 |
Family
ID=10648618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002004112A Expired - Lifetime CA2004112C (en) | 1988-12-16 | 1989-11-29 | Dispersions |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US5068056A (en) |
| JP (1) | JP2781433B2 (en) |
| AU (1) | AU620473B2 (en) |
| BE (1) | BE1004166A5 (en) |
| CA (1) | CA2004112C (en) |
| DE (1) | DE3941543B4 (en) |
| ES (1) | ES2029152A6 (en) |
| FR (1) | FR2640635B1 (en) |
| GB (2) | GB8829402D0 (en) |
| IT (1) | IT1238010B (en) |
| MY (1) | MY105755A (en) |
| NL (1) | NL8903014A (en) |
| ZA (1) | ZA899319B (en) |
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-
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- 1988-12-16 GB GB888829402A patent/GB8829402D0/en active Pending
-
1989
- 1989-11-24 GB GB8926575A patent/GB2226018B/en not_active Expired - Lifetime
- 1989-11-28 AU AU45640/89A patent/AU620473B2/en not_active Expired
- 1989-11-29 CA CA002004112A patent/CA2004112C/en not_active Expired - Lifetime
- 1989-12-01 US US07/444,811 patent/US5068056A/en not_active Expired - Lifetime
- 1989-12-06 ZA ZA899319A patent/ZA899319B/en unknown
- 1989-12-07 NL NL8903014A patent/NL8903014A/en active Search and Examination
- 1989-12-13 IT IT04865789A patent/IT1238010B/en active IP Right Grant
- 1989-12-15 DE DE3941543A patent/DE3941543B4/en not_active Expired - Lifetime
- 1989-12-15 ES ES8904229A patent/ES2029152A6/en not_active Expired - Fee Related
- 1989-12-15 FR FR8916667A patent/FR2640635B1/en not_active Expired - Lifetime
- 1989-12-15 BE BE8901340A patent/BE1004166A5/en not_active IP Right Cessation
- 1989-12-15 JP JP1325734A patent/JP2781433B2/en not_active Expired - Lifetime
- 1989-12-16 MY MYPI89001793A patent/MY105755A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ES2029152A6 (en) | 1992-07-16 |
| BE1004166A5 (en) | 1992-10-06 |
| GB8829402D0 (en) | 1989-02-01 |
| AU620473B2 (en) | 1992-02-20 |
| GB8926575D0 (en) | 1990-01-17 |
| AU4564089A (en) | 1990-06-21 |
| DE3941543A1 (en) | 1990-06-28 |
| CA2004112A1 (en) | 1990-06-16 |
| ZA899319B (en) | 1990-09-26 |
| NL8903014A (en) | 1990-07-16 |
| JPH02212315A (en) | 1990-08-23 |
| MY105755A (en) | 1995-01-30 |
| FR2640635B1 (en) | 1994-08-26 |
| JP2781433B2 (en) | 1998-07-30 |
| IT1238010B (en) | 1993-06-21 |
| DE3941543B4 (en) | 2005-11-03 |
| FR2640635A1 (en) | 1990-06-22 |
| GB2226018A (en) | 1990-06-20 |
| US5068056A (en) | 1991-11-26 |
| IT8948657A0 (en) | 1989-12-13 |
| IT8948657A1 (en) | 1991-06-13 |
| GB2226018B (en) | 1992-08-05 |
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