DE2159342A1 - White pigment - with resistance to fire and corrosion consisting of a phosphate of silicon,titanium or zirconium - Google Patents

Abstract

White pigment consists of a phosphate of formula (I) contg. at least 0.1% of a water soluble cpd. M'O2. xY. (0.1 is approx. 1.5 + mx/2) P2O5 (I) M2On/2 (II) (where M' is Si, Ti and Zr; Y is a nitrogen base or the oxide of formula (II); M2 is an alkali (ne earth) metal, Al, Pb or Zn; n is the valence of M2; x is a 1-6; and m is 1 when Y is a nitrogen base, or is n when Y is (II). The pigment is cheap and combines a high degree of whiteness with an excellent fire and corrosion resistance. Used in flame-retarding paints and rust-resisting paints. A soln. of TiCl4 and a soln. of orthophosphoric acid were supplied to a reactor to form a white gel. of Ti phosphate, the molar ratio of TiO2:P2O5 being 1:1. The pdt. was calcined for 1 hr. at 400 degrees C, and ground in a ball mill. The pigment consisted essentially of TiP2O7.

Description

New white pigment The invention relates to a new white pigment with excellent flame and corrosion resistance as well as rust preventive Paint containing this pigment and a method of preventing rust of metals using this rust preventive paint composition. In particular the invention deals with a white pigment, which consists of a specific silicon phosphate, Titanium phosphate or zirconium phosphate is built up, and with color masses that this Contain pigment.

While colloidal silica, the so-called white carbon, known as a filler, which has excellent abrasion resistance in rubber or synthetic Resins such as vinyl polymer He for such purposes as white pigment or @@@ breaking gloss of shaped Resin objects, such as fibers, are not entirely suitable as the finely divided silica usually has a transparency. Farther are special operations in the manufacture of the above silica filler required in order to obtain an extremely fine particle size. That's why the The disadvantage that the manufacturing costs also inevitably increased.

On the other hand, titanium dioxide is known as a white pigment, its opacity is very excellent, but j is its degree of whiteness, especially the reflection in the ultraviolet range, not sufficiently high and it still has the disadvantage that its price is also relatively high.

In view of the foregoing reasons, in the field of Pigments a considerable need for a cheap white pigment of excellent quality Wisdom.

Corrosion-resistant pigments are also red lead, lead powder, Zinc dust, aluminum powder, zinc chromate, barium chromate, glycyanamide and basic Known chromate. The corrosion-resistant pigments dissolved in a carrier are used as rust preventive paints, primers or washing primers. However, these rust preventive paints are still not entirely satisfactory, if the point of view is that these paints adhere perfectly to the metal substrate and the prevention of penetration or penetration of water, moisture or corrode either sewn between the metal substrate and the paintwork or between these coats and the coating finally applied over them is being considered.

On the other hand, corrosion-resistant pigments show how Zinc chromate, in general, a tendency to damage the carrier or the binding substance and are unsatisfactory in that they are used to form a solid rust preventive Coating can be used on a metal.

Of the above corrosion-resistant pigments, those are with a great resistance to corrosion in all cases either from lead or of the chromic acid type. These corrosion-resistant pigments give the surface of the metal eir, e pronounced coloring and therefore tz-itt thereby the disadvantage, that a paint film of sufficient strength over this rust preventive paint film must be applied to cover up its color. Since continue the above Corrosion resistant belts contain lead and chromates that are common to humans are harmful, there arises a serious problem that the workers who do these rust preventive Handle paints exposed to very serious damage to health.

Furthermore, it is in the case of flame retardant paints or of molded articles coated with flame retardant resins known, a flame retardant, which consists of various phosphates.

The property required for such flame retardants consists in the formation of a non-combustible foam upon exposure to the above Coating masses on the flame and in the carbonization of the coating mass.

Although the usual flame retardants; those from ammonium phosphates are built up, form foams on exposure to the flame and by release of the free phosphate carbonization of the combustible substances are effective on the other hand, these compounds are completely water-soluble and have the disadvantage that them Not only is there a lack of durability, it is also lacking Dispersibility. as they show a tendency to aggregate. To this one To improve the disadvantage, the proposal has already been made to use amnonium polyphosphate to be used as a flame retardant, but there is a disadvantage of ammonium polyphosphate in that it has no special properties, it is suitable for use as a filler or make pigment valuable. For example, it arises in the case of ammonium polyphosphate easily induces secondary aggregation and therefore it is difficult in a paint composition to disperse to a particle size in which the pigments are commonly used will. The properties of one using a coating compound, the ammonium polyphosphate containing, obtained coating films are generally poor.

It has now been found that a white powder made of silicon phosphate, Titanium phosphate or zirconium phosphate, and a water-soluble component within a specific quantitative range contains both an excellent Whiteness and in particular- good reflectance in the ultraviolet range as well a marked superiority in terms of flame resistance and corrosion prevention property shows.

A main object of the invention is therefore a new white Pigment which, although white in color as such, is both excellent Flame resistance as well as excellent corrosion resistance as well as in paints that contain this white pigment.

Another object of the invention is a rust preventive pigment, that is not of the lead or chromic acid type, that is white in color and continues to be excellent Has properties for preventing rusting of metals, as well as in rust preventive Paints containing this rust preventive pigment.

Another function is a white pigment which, though it has the water-soluble g'ieitseffects necessary for rust prevention and lamb resistance Contains constituents, has no tendency to aggregate, so that it easily turns into carriers or resins can be dispersed.

The invention thus results in a white pigment of excellent flame resistance and. Corrosion resistance, this being white Pigment from a phosphate with a composition of the following formula M1O2 # xY # (0.1 # 1.5 + ##) P2O5 (I) is constructed in which silicon, titanium or zirconium, Y is a nitrogen-containing Base or an oxide of the formula M20n 2 in which M2 is an alkali metal, an alkaline earth metal, Aluminum, lead or zinc and n represent the valence of the metal M2, x is a positive number up to 6, including 0, and m has the value 1 if Y is a nitrogenous one Is base and the value in the event Y is the group N2On, mean, where the phosphate contains at least 0.1% of a water-soluble component.

Composition and properties of the pigment The invention White pigment can be made from either silicon phosphate, titanium phosphate or zirconium phosphate consist alone or can consist of a combination of some of these phosphates or consist of a complex of these phosphates with other phosphorus compounds.

According to one embodiment of the invention, a white pigment is used obtained from excellent flame resistance and corrosion resistance, which is composed of a phosphate of the formula SiO2 # xY # (0.1 # 1.5 + ##) P2O5 (I-1), in which Y is a nitrogenous base or an oxide of the formula N2On 2 in which N2 is an alkali metal, LYdalkali metal, aluminum, lead or zinc and n the valence of the metal N2 represent, x is a positive number up to 6, including 0, and m the value 1 if Y is a nitrogenous gas, and the value n. If Y is a group M2On.

2 is mean.

The silicon phosphates according to the invention usually consist of one of the silicon phosphates 2SiO2 # P2O5, 3SiO2 # 2P2O5 or SiO2 # P2O5 or mixtures such compounds or mixtures of such silicon phosphates with silicic acid anhydride, silicon salts and / or other phosphates. Although the-foregoing Silicon phosphate compounds are substances that are known per se so far nothing at all is known about the properties that these compounds possess, or whether they are useful or valuable substances.

Since silicic acid compounds such as egg silicic acid, lead silicate, Calcium silicate or aluminum silicate are usually transparent and as a result for these silicic acid compounds it is possible to serve as a filler that the If the document shows transparency, there is no indication that these connections can serve as a white pigment, due to the non-transparency for the documents is achieved. Surprisingly, it has now been found that of the various Silicic acid compounds the present silicon phosphates or mixtures that predominantly consist of silicon phosphates, in that they are unique in that they are non-transparent and have excellent whiteness and especially reflectance in the near ultraviolet and ultraviolet range, making them a white pigment result, which has new properties compared to the usual white pigments.

The values obtained are given in Table I below, when the white pigment according to the invention made of silicon phosphate (2SiO2 # P2O5) and a Commercial titanium dioxide of the 7tutil type and white carbon (finely divided Silica) were compared with regard to their whiteness. is it turns out da-ss the wisdom and especially the reflectance in the near ultraviolet and clearly superior in the ultraviolet range for the pigment of the present invention is.

Table I pigment whiteness * (% reflectance at different Wavelengths) 320 mµ 350mµ 400mµ 450mµ 500mµ 550mµ 600mµ 37.5 80.7 98.2 100.8 101.8 to 8 101.9 102.0 phat white pigment rutile type titanium dioxide 2.9 7.7 42.8 92.8 93.7 95.7 96.0 Finely divided silica 16.8 30.9 73.0 79.2 83.1 84.6 86.8 anhydride * The degree of whiteness was determined by the reflectance measurement method determined by the powder method using a spectrophotometer. A sheet of aluminum oxide (Al @ O @) was used as a standard and on the base of the aluminum oxide sheet as 100 was the% reflectance at each wavelength specified.

When in the silicon phosphate pigment according to the invention in which SiO2 indicates the silica component and P2O5 indicates the phosphoric acid component, the molar ratio of P2O5 with respect to one mole of SiO2 is less than 0.1, the desired degree of whiteness can be achieved and the one you want Non-transparency cannot be obtained. on the other hand there is neither flame resistance nor corrosion resistance when the molar ratio from P2O5 to SiO2 is greater than 1.5, with no further increase in whiteness, the flame resistance and the corrosion resistance can be achieved more. Much more the chemical stability of the pigment itself decreases. With regard to wisdom and non-transparency of the pigment to be obtained therefore becomes a molar ratio of SiO2 P2O5 in the range from 1: 0.2 to 0.8 is particularly preferred in the context of the invention.

Alkali metals such as sodium or potassium, alkaline earth metals such as calcium or magnesium, or metals such as aluminum, lead or zinc, can be used in the invention Silicon phosphate pigments in the form of phosphates or silicates or as double salts are present. From the facial puff of the whiteness and nontransparency of the figures These metals, specified as oxides in a molar ratio of MOn / 2, are allowed to SiO2 of no greater than 6 and preferably no greater than 3 may be present.

If these metal components are present in the pigment, the phosphoric acid component can be used (P2O5) in an amount greater than that specified above, up to an amount of not greater than n / 2 moles per mole of MOn / 2 must be present.

It was also found that of the pigments corresponding to the above formula (I-1) a solid ammonium phosphate silicate, as required Ingredients a silica component, a phosphoric acid component and a Ammonia nitrogen component and wherein is the molar ratio of the silica component (SiO2) to the phosphoric acid component in the range of 0.2 to 5 and the melar ratio the ammonia nitrogen component (NH3) to the phosphoric acid component (P2O5) is in the range of 1 to 6, particularly superior in terms of flame resistance is.

It is not entirely clear whether these flame retardant pigments are in accordance with of the invention consist of a single substance or a so-called mixture. In view of the fact that the flame-resistant pigments according to the invention generally an X-ray diffraction pattern characteristic of ammonium phosphate, show and flame retardant pigments made using either triammonium phosphate or diammonium phosphate and mixing with silica, an X-ray diffraction pattern, which is characteristic of diammonium phosphates or monoammoni umpho sphate, show it is believed that the flame-resistant pigment according to the invention consists of a intimate mixture of ammonium phosphate and either ammonium silicate or a silicate with adsorbed ammonia.

Particularly suitable flame-resistant pigments according to the invention are those obtained from a solid powder ml t have the following X-ray diffraction values consist: A. Those with the following X-ray diffraction pattern: d (Å) I / Io 5.04 100 3.36 3.06 55 5.30 50 3.17 45 3.75 40 .B. Such with the following X-ray diffraction pattern: d (Å) I / Io 3.06 100 5.34 90 3.76 80 2.00 55 2.66 30 2.7s7 17 C. Those with the following X-ray diffraction pattern: d (Å) I / Io 6.02 100 5.43 70 3.23 65 3.81 55 3.49 50 3.98 40 If a differential thermal analysis of the inventive flame-resistant ammonium phosphate silicate pigments shows this an endothermic peak accompanying the separation of ammonia at a temperature from usually 120 to 260 ° C and has the foaming property that is required in the case of a heat-resistant coating compound. It also sets this Compound phosphoric acid concurrently with the separation of ammonia free. These Phosphoric acid is effective for carbonizing combustible substances.

D @@ Am @@@@ umphospl @ tsilikat thus makes the combustible @ ateriali @@ of the coating compound flame retardant. Simultaneously reacts the released Phosphoric acid with the silica at even higher temperatures, so that completely the heat of combustion is discharged; the endothermic reaction of free phosphoric acid and the silica shows up as striking in differential thermal analysis endothermic peak at the temperature from 360 to 5000 C.

The excellent self-extinguishing properties of the invention Ammonium phosphate silicates can be explained in this way.

In another embodiment of the invention there is a white, rust-preventing pigment, which consists of a titanium phosphate of the formula TiO2 # (0.2 # 1.5) P2O5 (I-2), this titanium oxide being at least 0.1% by weight of a water-soluble Ingredient it contains and has a pH of no more than 3.5 when it is too a 10% aqueous suspension is processed.

In a further embodiment of the invention, a white pigment, which is made from a zirconium phosphate of the formula ZrGr (0ç4 ~ 1, 0) P2O5 (1-3) consists, the zirconium phosphate at least 0.1% of a water-soluble component contains.

The atomic ratio of zirconium or titanium to phosphorus in the zirconium phosphate or titanium phosphate can be within a wide range. General is However, it is favorable if the zirconium or titanium component in the phosphate by NO2, where N is either zirconium or titanium, and the phosphoric acid component by P205 it is indicated that the P205 is at least 0.1 mole and preferably at least 0.4 mol, per mol of NO2 and furthermore not more than 1.5 mol and preferably not more is than 1 mole per mole of MO2. With an amount of the phosphoric acid component below Namely, 0.1 mol cannot have a marked rust preventive and flame retardant effect be achieved. -Furthermore, even if the phosphoric acid component can be in amounts greater than 1.5 mol, no noticeable increase in rust prevention and Flame resistance effects can be achieved as a limit to the improvement that can be achieved is present. In addition, the chemical stability of the rust prevention pigment suffers itself. Titanium phosphate or zirconium phosphate, the most favorable- to achieve the Objects of the invention are those in which the molar ratio MO2: P2O5 has a value of about 1: 1.

It is most important from the point of view of preventing rust and the resistance to flames, that in the white ones according to the invention Phosphate pigments the water-soluble component in an amount of at least 0.1 % is contained and that in the case of titanium phosphate the pH value of a 10% aqueous Suspension of the same is not more than 3.5. A phosphate pigment which neither one or both of these conditions does not have the excellent rust prevention properties, as shown by the phosphate pigments according to the invention.

Titanium phosphate itself is a well-known white pigment of excellent Whiteness and especially has a reflectance in the ultraviolet range (for example British patent specification 994 669). However, the well-known white pigments were the consist of titanium phosphate, in all cases practically completely by calcining made insoluble in order to increase their chemical stability, - so that the titanium phosphate no water-soluble component in amounts of at least 0.1% by weight as in the case contains the titanium phosphate to be used according to the invention. On the other hand, it is possible according to the invention, as will be explained below, the content of water-soluble constituents to at least 0.1% through a suitable choice of drying and regulate calcining conditions of phosphates such as titanium phosphate. Consequently can have excellent rust prevention properties and flame resistance can be obtained from the phosphates.

However, a water-soluble component content of more than 24% is not favorable, since this causes a decrease in the properties of the phosphate pigment will.

On the other hand, when the acidity of the titanium phosphate, i.e. h the pH value an aqueous suspension thereof becomes smaller than 1, this is likewise unfavorable because this tends to damage the carrier material.

In the following Tables II and ITI are the relationships between the calcining temperature, the amount of the water-soluble component and the acidity in relation to the rust prevention property shown when the calcining temperatures of titanium phosphate and silicon phosphate can be varied.

The evaluation of the rust preventive property was made by means of following simple test procedure: water was converted into finely divided titanium phosphate or silicon phosphate added in a weight ratio of 1: 1, followed by thoroughly mixed, whereupon a white fast was obtained.

A commercially available iron sheet with a Protective film from one. Vinyl chloride resin used on both surfaces after: the resin film had been peeled off. The inner surface of this iron sheet (thickness 0.32 mm), from which the resin film had been freshly stripped, was then with a Coating of the white paste obtained above in a thickness of 60 to 40 microns coated so that a film coating was formed on an iron sheet.

For comparison, test panels were applied in a similar manner of calcium phosphate and zinc phosphate as phosphates, basic lead silica and White carbon as silicates, and red lead as commercially available rust-preventing pigments on the inner surface of the iron sheets, so that a film coating on it the iron sheets was formed. The rust preventive effect of these film coatings became with that of the film coating from the above white paste of titanium phosphate and silicon phosphate compared.

After the film coatings on the test iron sheets in the above Were formed in the way 1 the metal sheets were placed in a closed chamber of 400 C and a relative humidity of 100 96 and left there for 100 hours. After 100 hours, the test panels were removed from the closed chamber and the surface of the iron sheets coated with the film became in terms of the states the rust formation assessed. Ratings A, X, C, D and E were given accordingly the states of rust formation are given in the following manner.

A: no bost ever detected; there was no change compared to when the coating was applied.

B: Rust visible in the size of pinholes.

C: Rust noted on parts of the arch, and cracks and bulges found in parts of the film coating.

D: Rust formation found in the greater part of the sheet and peeling of a larger part of the film coating.

E: Crack in the film coating and rust formation over the entire surface of the substrate.

The other values given in Tables II and III were obtained in the following manner: (1) Water-soluble ingredient.

20 g of the pigment powder was placed in a 100 ml volumetric flask and then added about 70 ml of water and heated for 5 minutes. To to cool the mixture, water was added up to the calibration mark and the mixture shaken well and then left to stand for 1 hour. Then the content Filtered the flask through a dry filter paper. The first part of 20 m was discarded and the next 50 ml amount of the clear liquid was in. a weighing bottle was taken for evaporation drying purposes and evaporated to dryness. After drying for 1 hour at 105 to 1-100 C, the evaporation became obtained residue weighed, whereupon the percentage of water-soluble component was calculated from the amount of the residue thus obtained.

(2) pH of a 10% aqueous suspension.

A 10% aqueous dispersion was thoroughly shake well dispersed. This suspension was left to stand for 1 hour and then the pH determined with a pH meter.

(3) Degree of whiteness.

A spectrophotometer was used and the reflectance (%) was the individual wavelengths determined using the powder method. An alumina bow was used as the standard arch and the one based on the aluminum arch of 100 numerical values obtained are used to indicate whiteness.

(4) Opacity.

The opacity was determined according to the method (a) the opacity determined according to the Pigment Testing Method 6 in accordance with JIS K-5101-1964. Three ml of boiling flaxseed oil was added to 3 g of the sample and the mixture a kneading cycle of 25 revolutions with a Hoover-type grinder four times subjected and thereby processed to a paste-like state. The opacity was then determined with a cryptometer using the sample treated in this way. The graduation (mm) at which the border line is visible on the indicator of the cryptometer is the value given as opacity.

The smaller this value, the greater the opacity.

Table II Properties of the various titanium phosphates Example Conditions of preparation water pH whiteness deck rating no. Des Titanium phosphate soluble 10%, (% reflectance) by virtue of the rust molar treatment Ingredient aqueous wave length (mm) prevent retention time part suspension (mµ) rungsnis (n) temperature (hrs.) (wt.%) 350 400 500 intrinsic TiO2 # ture shank (° C) nP2O5 1 2 450 4 17.20 0.5 85.0 103.0 105.0 30 A 2 2 600 4 6.55 1.4 90.2 103.0 105.0 25 A 3 2 800 3 1.91 1.9 90.5 103.0 105.0 19 A 4 2 1000 2 0.56 2.4 91.0 103.0 105.0 17 B 5 1 200 4 2.90 0.8 39.2 93.2 101.0 37 A 6 1 400 4 2.55 1.2 60.0 101.0 101.0 25 A 7 1,600 3 0.75 1.9 65.32 102.0 102.0 20 A 8 1,850 3 0.07 3.7 80.7 102.0 105.0 18 C 9 1 1000 3 0.05 4.2 87.2 102.0 105.0 16 C 10 0.5 150 3 1.05 2.2 22.5 87.0 100.0 40 A 11 0.5 350 3 0.68 2.3 24.3 87.4 100.0 25 A 12 0.5 600 2 0.58 2.6 28.5 90.2 101.0 20 B 13 0.5 850 2 0.05 3.9 46.0 90.5 101.2 18 C 14 0.5 1000 2 0.04 4.5 50.3 90.2 100.5 16 C 15 0.3 100 1 0.20 2.4 21.0 90.0 100.0 30 ß 16 0.3 400 1 0.13 2.9 37.5 91.0 100.5 20 ß Table II (continued) Example Conditions of manufacture water pH a degree of whiteness deck rating No. of the titanium phosphate more soluble 10%, (% reflectance) by virtue of d. Rust-Molar- Treat- Treat- Stock- aqueous wave length (mm) prevention time of partial suspension (mµ) rungsnis (n) temperature (hrs.) (wt.%) 350 400 500 property (° C) nP2O5 17 0.25 100 1 0.17 2.5 20.5 90.2 100.0 25 B 18 0.25 400 1 0.11 3.0 39.0 91.5 101.0 18 B Control 1 calcium phosphate [Ca3 (PO4) 2] 0.0025 12.59 92.1 102.2 102.0 100 < E comparison 2 zinc phosphate [Zn3 (PO4) 2] insoluble 7.59 27.3 89.8 92.7 100 <D Tabel III Properties of the various silicon phosphates Example conditions of manufacture Water pH of a degree of whiteness deck rating No. of the titanium phosphate more soluble 10% igen, (% reflectance) by virtue of d. Rust-Molar- Treat- Treat- Ingredient- aqueous Wavelength (mm) reduction time partial suspension (mµ) change (n) temperature (hrs.) (wt.%) 350 400 500 intrinsic SiO2 # tures (° C) nP2O5 1 1 300 2 11.04 1.6 58.0 76.3 84.2 65 A 2 1 500 2 8.31 1.9 83.3 92.8 95.5 60 A 3 1 800 2 7.70 2.2 76.7 92.6 95.8 55 A 4 1 1000 2 5.74 2.7 68.0 94.0 95.5 45 A 5 0.5 300 2 4.69 2.6 55.0 70.1 81.6 70 A 6 0.5 500 2 3.00 2.7 74.3 87.2 91.7 60 A 7 0.5 800 2 2.64 2.8 67.6 91.2 94.5 55 A 8 0.5 1000 2 2.16 2.9 66.0 93.4 96.1 47 A 9 0.3 200 2 1.85 2.7 62.4 74.5 87.2 62 A 10 0.3 500 "1.22 2.9 64.3 77.8 91.5 57 B 11 0.2 200 2 1.03 2.8 59.2 71.6 85.0 60 B 12 0.2 500 2 0.95 3.0 60.3 72.1 86.7 55 B 13 0.2 800 2 0.41 4.1 61.8 72.9 88.2 55 C comparison 3 basic lead silicate (1.6 PbO # SiO2) 0.07 6.8 - - - 100 <C comparison 4 welsser coals @@@ ff (mostly finely divided SiO2) 0.002 6.9 - - - 100 <E Comparison 5 red lead (Pb3O4) - - - - - - B. It results from the above Tables II and III, -that by choosing the in the- Titanium phosphate and silicon phosphate contained close to water-soluble component and the acidity such that they are within the ranges given above excellent rust preventive properties can be obtained which not only far superior to those of calcium phosphate, zinc phosphate, basic lead silicate and white carbon are chosen for comparison but are also superior to those of red lead which are commercially available as a rust preventive pigment. The inventive phosphate pigments of the above Formula (I) most preferably contain the water-soluble ingredient in one Amount from 0.6 to 20%.

The inventive phosphate pigments of the formula I are usually than particles smaller than 20 in diameter, and preferably less used as 10. A surprising fact is that the inventive Phosphate pigments show no tendency to aggregate, even if they are too finely divided Particles with sizes less than 5X are crushed - As stated above, contain the inventive phosphate pigments at least 0.1% and preferably 0.6 to 20% by weight of the water-soluble component. Usually it is difficult a solid substance containing such water-soluble components, for example shred to a size of less than 10 and even if possible, the tendency towards aggregation is excessive. However, in the case of the invention Phosphate pigments this tendency to aggregate surprisingly small, although they contain a water-soluble ingredient that helps to achieve the resistance is favorable to flames and corrosion.

The tendency of a finely divided substance to aggregate leaves Determine yourself in the following way: A finely divided substance that passes through a sieve with an exemplary mesh size is given during a For a period of time in air of given humidity. This finely divided Substance is then sieved with the same sieve and the amount of particles that passes through the sieve is obtained. The phosphate pigments according to the invention are those whose degree of aggregation is less than 50% and in particular less than 10%, calculated according to the following equation: Q = A-A 'x 100, (II) where A is the Weight of powder passing through a sieve with a given mesh size 'A' the weight of this through the same sieve after standing at room temperature for 24 hours powder passing through in air at 90% relative humidity and Q mean the degree of aggregation in%.

Preparation of the pigment The white phosphate pigments according to the invention of formula (I) above can be obtained by a number of methods: The inventive white pigment of the formula (is produced by intimately mixing amorphous silica, silicates or earth minerals, which are predominantly made up of these materials consist, either with oxyacids of phosphorus, anhydrides of oxyacids of phosphorus or salts of oxyacids of phosphorus and subsequent calcination of the obtained Mixture produced.

As a starting material for the silica component according to the invention is amorphous silica, colorless silicate or earth minerals, which are predominantly - consist of these components, used. As amorphous silicas according to of the invention are hydrosols of silica, hydrogels of silica, zerogels of silica and amorphous, calcined products of silica are useful. With the term "amorphous" as used herein becomes that for aiesen in crystallography Purpose used as a result of the X-ray diffraction analysis.

On the other hand, alkali, alkaline earth or aluminum salts can also be used the silica can be used. These are in the process according to the invention in Can be used in the form of aqueous solutions, sols, gels, as powders or crystals.

Of the above silicates, sodium silicate, potassium silicate, Magnesium silicate, calcium silicate, barium silicate and aluminum silicate are preferred.

Various mixtures of the above derivatives or the naturally occurring colorless clay-like minerals, consisting predominantly of amorphous Silicic acid and / or silicate can also be used according to the invention will. For example, mixtures containing silica and aluminum silicate are different Contain proportions as the starting material for the silica component according to suitable for the invention.

Furthermore, the starting material for the silica component can be used contain some impurities to such an extent that the whiteness of the material is not influenced. For example, it can contain small amounts of metal components of Al, Lig and Ca, for example in the case of the acid-treated acids Clays obtained by treating acidic clays with an acid will, or diatomaceous earth obtained by treating naturally occurring diatomaceous earth were obtained in pure white form. Furthermore, the colorless earth minerals, for example the naturally formed zeolites, fliatome earths and high grade Kaolins can also be used favorably in the invention. The one used here The term "earth minerals" denotes the phyllosilicate materials bound in a stratiform manner (clay-like minerals), the sterically reticularly bound tectosilicate materials and the natural non-crystalline silicates. Therefore all silicas can or silicates, which are by-products of inorganic chemical or ceramic Industry or as an intermediate or end product in these industries arise as starting materials for the silica material according to the invention can be used.

Furthermore, all oxyacids can be used as starting materials Phosphorus, for example orthophosphoric acid (H3PO4), metaphosphoric acid (HPO3), Pyrophosphoric acid (H4P2O7), hexametaphosphoric acid [(HPO3) 6], tripolyphosphoric acid (H5P3O10), phosphorous acid (H3PO3) and typophosphoric acid (R3PO?) Can be used. Furthermore, these oxyacids serving as starting material can of course be used of phosphorus also in the anhydride form, for example as phosphorus pentoxide (P205) be used.

As examples of colorless, usable oxy acid salts of phosphorus be the alkali salts, ammonium salts, alkaline earth salts, zinc salts, lead salts or Called aluminum salts of the oxyacids of phosphorus.

According to the invention, the above starting materials for the silica component and the phosphoroxy acid component intimately mixed and crushed. In all of this there can be mixing and grinding the both materials by both a dry and a wet process are executed.

For example, the starting silica component can be in sol form or hydrogel form can be used, including the phosphoroxy acid component as an aqueous Added to solution or in slurry form to form an intimate mixture or the phosphoroxy acid can be added to the dried gel or as a liquid Powder of the starting silica component can be added. Furthermore you can the two starting materials are mixed by dry grinding, if a salt of phosphorusoxy acid is used, but a more intimate mixture can using either water or some other liquid medium.

Even if the ratio, with which the starting silicic acid component and the starting phosphorus oxide ingredient are mixed considerably in depends on the classes of the starting materials used this has no effect, provided the finished composition is within the above specified range.

Next, according to the invention, the intimate mixture of the starting silica component and calcining the starting phosphoroxy acid component. Even if the calcining temperatures vary considerably depending on the classes of the two starting materials, Temperatures in the range from 200 to 10,000 ° C. are generally preferred. From the point of view the whiteness of the pigment to be obtained should preferably be a temperature above 4000 C can be used when calcining the above mixtures. From the point of view both the whiteness and the stability of the pigment obtained it becomes general preferred if the calcination of the above.

Mixtures at temperatures above 400 ° C is carried out. The calcining conditions must be selected in a suitable manner so that the requirements given above are met and there becomes a temperature above 2000 and preferably between 400 and 10000 C and a period of 1 to 4 hours chosen.

If the calcination of the starting silicic acid component and the starting phosphoroxy acid constituent existing mixture with addition an inorganic halogen-containing compound, for example a chloride, Bromides or iodides of an alkali metal such as lithium, sodium or potassium, one Chlorides, bromides or iodides of an alkaline earth metal such as magnesium, calcium or barium, or a chloride, bromide or iodide of metals such as zinc, Aluminum and tin running, the amount of contaminating can be staining Ingredients contained in the above mixture to a noticeable extent -be reduced. The whiteness of the pigment can be improved considerably, when the inorganic halogen-containing compound is in an amount of 0.01 to 0.3 Mol, in particular 0.05 to 0.02 mol, is used per mole of SiO2.

On the other hand, the above flame-resistant white pigment can be used of the ammonium phosphate silicate type, for example, by intimately mixing a combination the following materials can be produced: (a) a combination of reactive Silica, phosphoric acid and an ammonia-nitrogen compound; (b) a combination of reactive silica, ammonia adsorbed silica and ammonium phosphate; or (c) a combination of silicon phosphate and an ammonia-nitrogen compound, the ratio of SiO2 / P2O5 being in the range from 0.2 to 5 and preferably 0.5 to 3 and the molar ratio of NH3 / P2O5 is in the range of 1 to 6.

As starting silica materials and starting phosphoric acid materials those listed above can be used.

Examples of ammoniacal nitrogen compounds are urea, Ammonium carbamate, guanylurea, aminourea and biureth or biurea in addition usable with ammonia.

Instead of the separate use of phosphoric acid and the ammonia nitrogen f-compound, ammonium phosphate can be used as a starting material. As. Ammonium phosphates can use the mono-, di- and tri-ammonium orthophosphates, ammonium metaphosphates as well the ammonium salts of phosphorusoxy acids and also ammonium phosphoric acids of the P-O-P type can also be used instead of the separate use of silica and phosphoric acid silicon phosphates, for example those of the formula xSiO2 # yP2O5 where x / y = 1 to 5, are used as starting materials.

The above starting materials are in intimate contact with Temperatures in the range of room temperature up to 200 ° C Q brought. The conditions, under which this contact occurs vary depending on the classes of the used raw materials.

For example, after mixing.

Silicic acid, phosphoric acid and the ammonia-nitrogen compound the constituents advantageously usually to a temperature above 800.degree reacted under conditions sufficient to volatilize the moisture. On the other hand will. when mixing silica or adsorbed with ammonia Silicic acid with ammonium phosphate, although also mixing in the solid phase is possible, mixing is preferably carried out at the temperature indicated above carried out using a small amount of water as a medium.

Furthermore, in the reaction of silicon phosphate with an ammonia-nitrogen compound the reaction can be carried out by passing ammonia gas through the solid silicon phosphate is performed or the solid silicon phosphate can with an aqueous solution of the Ammonia-nitrogen compound are mixed, after which the mixture is dried, to get the product you want.

Furthermore, if necessary, ammonia can be adsorbed the solid powder obtained can be carried out to produce the desired product, which the phosphoric acid, silica and ammonia components in the desired areas contains, to receive.

The titanium phosphate to be used as rust prevention pigment obtained according to the invention by processes known per se, but with a sufficient content of the water-soluble component and an acidity within of the range listed above is ensured. The material can for example after those of British Patent 1,161,141 and U.S. Patent 3,471 252 can be produced. For example, the titanium phosphate easy by reacting either an inorganic or organic acidic solution of a Titanium compound, a titanium salt as such or an amorphous titanium oxide with an oxyacid of phosphorus or a phosphorusoxyacid derivative containing the phosphorusoxyacid component can release under the reaction conditions and subsequent calcining of the obtained phosphoroxy acid salt of titanium in the desired manner will.

For the production of the titanium phosphate for use according to the invention is first an inorganic or organic acid solution of a titanium compound, either a titanium salt as such or an amorphous titanium oxide in the presence of water with a phosphoroxy acid or a phosphoroxy acid derivative the one phosphoroxy acid residue can form under the reaction conditions to form a titanium phosphate gel implemented, its composition within the range given above lies. Then this titanium phosphate gel is either dried or calcined in the way that the water-soluble ingredient in the product obtained in a Amount of at least 0.1 Yo and preferably 0.6 to 20% is included and the pH of a 10% aqueous suspension of the product obtained is no longer than 3.5 and preferably 1 to 2.5. Although the Grocknungs- or Calcini er conditions considerably depending on the composition of the titanium phosphate can vary, usually a temperature of 100 to 10,000 C and preferably 250 to 8000 C and a period of 30 minutes to 3 hours can be selected, so that the requirements specified above are met.

The zirconium phosphate, which according to the invention as a flame-resistant and corrosion-resistant white pigment is used can be prepared in the following manner will. The zirconium material used as the starting material consists of either (1) one Acid solution obtained by melting a concentrate of zirconium minerals such as Zirconia (ZrO2 # SiO2) and baddeleyite (ZrO2) with an alkali, if necessary, for vitrification of the zirconium mineral and subsequent dissolution of the same in one Nineral acid, such as sulfuric acid, hydrochloric acid, or nitric acid, (2) a zirconium chloride, which in an intermediate stage of the so-called Kroll process was obtained, wherein a zirconium mineral in the presence of carbon, be @ for example Eoks, is heated and then chlorine is passed through it, (3) a zirconium hydroxide, which by hydrolysis into a zirconium mineral, usually an acid extract was obtained. These starting zirconium materials are either treated with a phosphorusoxy acid or a reactive derivative thereof, followed by the zirconium phosphate obtained is calcined. The starting amounts of the zirconium material and the phosphorusoxy acid or the reactive derivative thereof are chosen so that the conditions the above formula e: are met. When calcining the zirconium phosphate suitable conditions are a temperature in the range of 100 to 9000 C and a period of 30 minutes to 3 hours is selected to ensure that that the water-soluble component is at least 0.1%.

This creates new pigments of a composition corresponding to the obtained above general formula (I) according to the invention. Of course If necessary, the pigments obtained can be washed with an acid and / or washed with water and by either the dry method or the wet method crushed and become a product in the form of a slurry, paste or powder are processed. Furthermore, the dispersibility of the inventive White pigments are improved if a coating is made of metal oxides or organic Substances are formed on their surface in the usual way. According to the invention the pigment is preferably comminuted so that the conditions of -above given formula (II) are met, preventing aggregation of the particles will. In order to achieve this goal, those obtained by the above methods must be obtained Pigments - in an organic solvent, which is the water-soluble component of the above phosphates does not dissolve, for example alcohol, such as methanol or Ethanol, ethers such as diethyl ether and tetrahydrofuran, ketones such as acetone and methyl ethyl ketone, Hydrocarbon solvents such as n-hexane, kerosene, benzene, toluene and xylene and halogenated hydrocarbon solvents such as chloroform, methylene chloride or tetrachlorethylene, using a grinder such as a Ball mill or tube mill. If in this case a low boiling point Solvent is used, the pigment can be finely divided without aggregation the pigment particles are recovered. If a resin, for example colophony or natural resins, alkyd resins or petroleum resins or higher fatty acids, such as stearic acid, or metallic soaps such as calcium or barium stearate previously in the above Solvents are dissolved and the comminution of the pigment in this solvent takes place, the surfaces can after the evaporation of the solvent the pigment particles are coated with these substances. Furthermore, the pigment, that in the The solvent was crushed, its intended end use in the condition in which e.s was obtained (condition of Slurry or state of a cake). On the other hand, it can Pigment can be comminuted in a paint carrier specified below and put to its intended end use in this condition. RJm furthermore the drying of the applied film with the prevention of interaction with the hardener contained in the carrier, it is effective to accelerate the Particles of titanium phosphate or silicon phosphate with 0.5 to 5 wt.%, Based on Titanium or silicon phosphate, an oxide of an alkaline earth metal, for example Magnesium or calcium oxide, aluminum oxide or silica gel to coat uses The white phosphate pigments according to the invention not only show excellent But possess reflectance in the ultraviolet range and near ultraviolet range also ~ new properties, d. H. excellent flame resistance and rust prevention properties, which are not shown by the usual white pigments.

When the inventive white phosphate pigments in a resin incorporated or dispersed in a carrier and placed on a support can be applied, a pronounced flame resistance of the resinous molded article, t'berzuges or the base can be obtained. Even if a known white pigment, such as titanium dioxide, is dispersed in a carrier and then applied to paper the self-burning property of the paper cannot be prevented; if however, a coating containing the white pigment according to the invention on paper is applied, the self-burning ability of paper practically be prevented.

The white pigments according to the invention are thus valuable as pigments for paints, as pigments for use in paper making, as gloss breaking agents for textiles and as pigments for use with the various molding resins. They can also be incorporated into known pigments to improve their whiteness or they can be used as white pigments to achieve fire resistance or flame retardant properties as well as to achieve corrosion resistance can be used for different classes of molded articles.

The inventive phosphate pigments can, for example, in Paint carriers or molding resins in quantities of 1 to 300 parts by weight, preferably 5 to 100 parts by weight for 100 parts by weight of the carrier base or the resin will.

According to one embodiment: the invention provides a rust preventive paint for netal surfaces, which consists of (a) a carrier, which is a coating film Contains forming base material, which is preferably selected from the group consisting of alkyd resins, epoxy resins, air-drying oils, phenolic resins, polyvinyl acetals, vinyl chloride resins or polyvinyl acetates and (b) a rust preventive pigment which is composed of a phosphate a composition according to the formula M1O2 # xY # (0.1 # 1.5 + mx / 2) P2O5, wherein 111 is silicon, titanium or zirconium, Y is a nitrogenous, base or an oxide the formula M20n 2 where M2 is an alkali metal, alkaline earth metal aluminum, Lead or zinc and n represent the valence of the metal M2, x a positive one Number up to 6 including 0, and m the value 1 if Y is a nitrogenous base is, and the value n, if Y has the meaning M20n, mean, where d.as phosphate contains at least G% 2 of a water-soluble component, is built up and continues to do so the phosphate in an amount of 1 to 300 parts by weight per 100 parts by weight of the den Coating film forming base material is present.

The above rust preventive paints according to the invention can easily be applied as an undercoat on a metal base by the consumer and show excellent adhesion between the paint and the metal substrate as well as the finally applied coating. In addition, it has the rust preventive effect for a long period of time.

As a base material for the formation of the cover film of the carrier material for rust preventive paint, for example, alkyd resins, epoxy resins, air-drying ones Oils, phenolic resins, polyvinyl acetals, vinyl chloride resins and polyvinyl acetates can be used, which can be used singly or in combination of 2 or more kinds thereof. These base materials used to form the coating film are in the form of either a solution in an organic solvent or as an aqueous emulsion.

As alkyd resins, either the condensation products are polybasic Acid, such as phthalic anhydride, terephthalic acid, succinic acid, adipic acid, sebacic acid, Fumaric acid, Itaconic acid or cyclopentadiene maleic anhydride adducts with a polyvalent one Alcohol, such as ethylene glycol, propylene glycol, glycerine, trimethylolpropane, pentaerythritol, Mannitol or: r sorbitol or modified alkyd resins, which are produced by condensation of the the above polybasic acids and polyhydric alcohols with oils or fats and higher fatty acids such as soybean oil, linseed oil, dunk oil, coconut oil, stearic acid, Oleic acid, linoleic acid and linolenic acid and modifiers such as natural resins, such as rosin, copal or shellac or synthetic resins such as phenolic resins, Urea resins and nelamine resins were obtained.

These alkyd resins can be in solution form, dissolved in an aromatic Hydrocarbons, such as toluene or xylene, or in the form of an aqueous emulsion by emulsification with a known emulsifier such as non-ionic surfactants Oils, cationic surfactants, or siloxaneoxyalkylene copolymers be used. Of course, the carrier material can be equipped with a dryer be, for example cobalt naphthenate or manganese naphthenate, as is the case with such Approaches is common.

As epoxy resins, bisepoxy compounds obtained from a condensation product can be used of epichlorohydrin and a polyhydric phenol, for example a bisphenol or resole, and combinations with a hardener, such as phenolic resins, urea resins, Polyamide resins and organic acids can be used. On the other hand, reaction products of the above bisepoxy compounds with oils and fats or fatty acids as well be used. These epoxy resins are diluted with a mineral oil and used as a carrier used.

As drying oils, linseed oil, perilla oil, tung oil, boiled linseed oil, Maleic oil, styrenated oil and epoxidized oil along with hardeners such as cobalt naphthenate and manganese naphthenate are used.

As phenolic resins, besides the usual phenolic resin paints, are from Resole type those usable that consist of a fatty acid or a resin acid modified with subsequent addition of a drying oil and heat treatment Phenolic resins consist or those phenolic resins that consist of condensation products of an alkylphenol, for example p-tert-butylphenol and formaldehyde followed by Adding a drying oil and heat treatment can be used. These phenolic resins are used diluted with a ketone or an aromatic hydrocarbon -As polyvinyl acetals, polyvinyl butyral and copolymers with vinyl alcohol units can be used and vinyl butyral units can be used.

The copolymers of Vinyl chloride with a low close to vinyl acetate and the ternary copolymers of vinyl chloride, a small amount of vinyl acetate and a small amount of Vinyl alcohol or maleic acid used. These come in the form of a solution all in one Ketone and / or an aromatic hydrocarbon as a solvent together with a small amount of a plasticizer is used.

On the other hand, the vinyl chloride resins can also use surface-active Agents are emulsified and dispersed and used in the form of an aqueous emulsion will.

A1S polyvinyl acetates are polyvinyl acetate or aqueous emulsions a vinyl acetate resin containing a small amount of vinyl alcohol units or a little Amount of vinyl alcohol and vinyl butyral units contains, usable.

The above carriers for the rust-preventive paints are known in the art. If necessary, you can add to these coating substrates Plasticizers such as dibutyl phthalate, tricresyl phosphate, dioctyl phthalate and n-hydroxymethyl phthalamide, Dryers such as cobalt naphthenate, manganese naphthenate, cobalt linolate, lead naphthenate and zirconium naphthenate, hardeners such as benzoyl peroxide and methyl ethyl ketone peroxide, dispersants, such as aluminum stearate, lecithin and polyethylene glycol alkyl ethers, enulsion stabilizers, such as polyvinyl alcohol and methyl cellutose, emulsifiers such as triethanolamine and surfactants Agents, thickeners or extenders, such as kaolin, magnesium silicate, calcium silicate and silica gel or other rust preventive pigments can be added.

Although the rust preventive paints according to the invention are particularly are effective in preventing iron substrates from rusting, they are also effective about the rusting of various other metals, such as copper, nickel, with chromic acid treated iron, galvanized iron and nagnesium alloys. For applying the rust prevention paints according to the invention to iron substrates can depending on the different methods of applying paints on the amount of pigment used in the paint. If for example If the pigment content is high, it can be applied using an island, spatula - or Roller take place while, if the content of @igment is low, the application by spraying or dipping, or by electrostatic or electrophoretic Procedure can be done. In any of the above cases one Use water, thinner, or other thinners to reduce the viscosity of the paint. The rust preventive according to the invention Paints can be applied directly to the surface of the iron base or can be applied to the surface of iron substrates that have a phosphoric acid treatment received, must be applied.

The rust prevention paints used as a pigment according to the invention sen silicon phosphates or titanium phosphates not only show superior results Rust prevention properties compared to the usual rust prevention paints, but also show no tendency to damage the carrier material. Also sticking the rust prevention paints according to the invention after application as an undercoat on a metal surface very excellent on the metal surface and retained the rust preventive effect for very long periods of time even if during exposed to corrosive conditions for long periods of time.

Furthermore, the rust prevention paints according to the invention a white color and therefore no tendency to discolour the metal base with a specific color. Therefore they bring with them the characteristic that a pure retention of the color of the final coating becomes possible, even when the coating film of the final coating is relatively thin. The inventive Rust preventive paints are also superior in the point that they are not are toxic because they do not contain lead. Therefore, the rust preventive paint compositions of the present invention can used for various purposes as a white rust preventive coating and the various common rust prevention paints, zinc chromate Primers and replace primers and wash primers.

As an example: a number of approaches are given below.

Recipe 1 white rust prevention paint based on linseed oil.

Parts of titanium phosphate according to Example 2 220 titanium dioxide of the rutile type 110 Nagnesiumsiikat 250 Raw linseed oil 210, heavy-bodied linseed oil 110 6% cobalt naphthenate 2 6% manganese naphthenate 10 Mineral-Spirit 88 Recipe 2 White rust prevention paint based on alkyd.

Parts of titanium phosphate according to Example 2 100 silicon phosphate according to Example 1 60 Titanium dioxide of the rutile type 100 Calcium carbonate 210 Modified with soybean oil Alkyd resin (50% solution in mineral spirit, acid number 10) 280 Linseed oil 3 24% lead naphthenate 1 6% cobalt naphthenate 1 mineral spirit 245 Recipe 3 phenolic resin primer.

Parts of silicon phosphate according to Example 1 14 titanium dioxide of the rutile type 10 calcium silicate 20 dehydrated castor oil phenol ether ester resin 18 xylene 20 Mineralspirit 18 Recipe 4 Rust prevention and flame prevention paint on Epoxy base.

eil'e Titanpllosphat according to Example 2 100 silicon phosphate according to Example 1 50 Rutile-type titanium dioxide 100 Alkyd resin modified with dehydrated castor oil (50% solution in mineral spirit) 400 aluminum stearate 100 soybean lecithin 5 6 % Cobalt naphthenate 2 6% zirconium catalyst 10 xylene 120 naphtha 113 vinyl chloride resin primer.

Parts of titanium phosphate according to Example 2 22 Parts vinyl chloride resin * 15 tricresyl phosphate 3 methyl ethyl ketone / toluene (1: 1) 60 * ternary copolymer with 90 vinyl chloride, 3% vinyl acetate and 6% vinyl alcohol.

20 ° C (#) Cyclohexane = 0.57 Recipe 6 White rust prevention and Flame retardant pigment based on polyvinyl acetate.

Parts of titanium phosphate according to Example 2 130 silicon phosphate according to Example 1 40 titanium dioxide of the rutile type 140 polyvinyl acetate emulsion (55% solids), 270 Dibutyl phthalate 20 propylene glycol 45 methocel (2% aqueous solution) 200 water 155 Recipe 7 Flame-resistant and rust-preventing oil paint.

Parts boiled linseed oil 100 polyamide resin (50% solution) 50 titanium dioxide 50 titanium phosphate according to example 2 50 Parts ammonium phosphate silicate according to example 9 30 zinc borate 30 melamine resin 20 starch 5 chlorinated paraffin 10 Recipe 8 Emulsion-type flame retardant paint.

Parts of water 100 polyvinyl acetate emulsion (55 solids) 50 titanium dioxide of the rutile type 50 dibutyl phthalate 5 ammonium phosphate silicate according to Example 9 20 dicyandiamide 20 Pentaerythritol 50 Chlorinated paraffin 5 Recipe 9 Formmase made from unsaturated polyester Parts Unsaturated polyester resin 100 peroxide 0.2 to 3 naphthenate 0.2 to 2 ammonium phosphate silicate from example 9 5 to 80 chlorinated paraffin 5 to 20 pigment 0 to 50 recipe 10 polyvinyl butyral mesh primer.

Parts of silicon phosphate according to Example 1 10 finely divided polyvinyl butyral 8 Silicic acid 2 Isopropanol (99%) 60 Butanol Water 4 The following examples serve to further explain the invention.

Example 1 A white silicon phosphate pigment was used made of a xerogeis of silicic acid and of orthophosphoric acid. That. production method and, the properties of the white pigment obtained are shown below.

The silicon phosphate was produced in the following way: One technical Available sodium silicate solution was mixed with sulfuric acid to gel the silica neutralized, whereupon this gel thoroughly under formation of small, purified aggregates the hydrogel of the silica was washed and then dried. The resulting silica xerogel was then mixed with the phosphoric acid component by adding a technical orthophosphoric acid (first JIS quality 85% H3PO4, specific weight 1.690) impregnated.

The composition of the silica component and the phosphoric acid component adjusted so that that the molar ratio of SiO2: P2O5 had the value of 1: 0.5. After drying this impregnated Product it was calcined for 2 hours at 8000 C in an electric furnace, then for 3 hours in a pot mill filled with balls using crushed wet by methyl alcohol as a grinding medium. After that as a grinding medium methyl alcohol had been separated and recovered, the product became dried. A finely divided white silicon phosphate pigment was obtained.

Then an identification was carried out by means of X-ray diffraction analysis of the fine, white silicon phosphate pigment obtained and the determination of the Properties such as whiteness, especially reflectance in the ultraviolet range, are more water-soluble Constituent, pH value of a 10% aqueous suspension, particle size and extent of secondary aggregation. The results are summarized in Table IV.

The degree of whiteness was determined in the following way: The determinations were made by the powder method using a spectrophotometer. An alumina sheet was used as the standard white sheet and the reflectance at different wavelengths in% based on the alumina arc as 100 indicated as degree of whiteness.

The water-soluble content was determined in the following manner determined: 20 g of the pigment powder were placed in a 100 ml volumetric flask. After adding about 70 ml of water, the mixture was heated for 5 minutes and then cooled, whereupon Water was added up to the calibration mark. The contents were shaken well in the gut and then left to stand for 1 hour. The content of the Flask with a dry Filter paper filtered. The first 20 ml of filtrate were discarded, whereupon the next 50 ml of the clear liquid in a weighing bottle for use in evaporative drying and evaporated to dryness. Then after drying the residue The vessel was weighed at 105 to 1100 ° C. for 1 hour. The amount of water soluble Ingredient contained in the sample, in percent by weight, was then eliminated the weight of the residue obtained after evaporation of the liquid. calculated.

The pH of the 10% aqueous suspension was as follows Way determined: an aqueous suspension with a concentration of 10% was Shaken well and dispersed at room temperature (23 + 20 C). This suspension was left to stand for 1 hour and the pH was determined with a pH meter.

The particle size was determined by determining the size of the lignent particles determined when examined with a microscope.

The extent of aggregation (Q) was determined in the following way: The pigment powder, dried at 90 to 1100 C, was first passed through a sieve of 74 microns (100 mesh), whereupon the powder in a desiccator for 24 hours, adjusted to a relative humidity of 90% with a sulfuric acid solution was left to stand so that the moisture is fully adsorbed by the powder became. The powder sample was then sieved again, taking it up for 10 minutes a 74 micron (100 mesh) sieve using a self shaker (product the Maruto-Seisakujo, Japan) was shaken. The one on the sieve at this point the remaining sample part was given in% and this value as the degree of aggregation (%) stated.

The general test method was used as the rust resistance test applied to paints according to JIS K5400 and the evaluations of rust resistance effects were carried out by means of the weathering test and the salt water spray test of film coatings, which were applied to a soft steel plate. When performing this ses Rust resistance tests were carried out at the same time as tests with commercially available rust prevention pigments, such as red lead, lead cyanamide, zinc chromate, zinc white, and calcium phosphate and comparative evaluations against the case of using the silicon phosphate made according to the invention.

The results are given in Table IV.

To produce the paints with these pigments, 10 Parts by weight of the individual pigments with 100 parts by weight of a commercially available alkyd resin as a carrier (Beckosol P-470, product of Dainippon Ink & Chemical Company) blended and mixed and dispersed in the carrier in a ball mill. The one with it Receiving paints were used and the rust resistance test carried out in the following manner.

As a soft steel test plate according to JIS K5400, a cold-rolled steel plate (JI'cJ G3141, Regulation B) was used. This plate, whose Thoroughly and evenly cover the entire surface with a waterproof sandpaper No. 280 had been polished until it showed a metallic sheen is for use suitable in the above test.

The obtained steel plate was used and the train was followed of JIS K5400 to a film thickness of 40 to 50 µ with the spray method applied, after which it dried by itself at room temperature and normal humidity became.

The weathering test was carried out according to JIS conditions K5400 in the following manner: The coated surface of the test plate was exposed outdoors exposed to air. After a period of 2 years the coated surface became of the individual plates observed in comparison and the condition of the coated The surface of the rust that has occurred is compared and assessed. The evaluation method used consisted of a classification of the state of rust on the plate surface in five classes with the ratings A, B, 0, D and E in the following way: A: None Rust noted, so practically no change since the time of painting the residual disk occurred; B: rust on the order of pinholes found; C: Rust from parts of the remainder plate and cracks and bulges from parts of the film coating established; D: Larger part of the remaining plate is rusted and the greater part of the film coating peeled off; E: Breakage of the film coating and rust occurred over the entire substrate.

The salt water spray test was carried out according to the conditions JIS K5400 in the following manner: The coated surface of the test plate was spraying with salt water at 600 C in a water spray chamber exposed for a period of 300 hours. The coated surface of the The exposed test plates were then observed for comparison and the condition of the ftoctes rated and divided into five grades A, B, C, D and E as in the case of the preceding Weathering test.

The results of the above tests to determine: Rust resistance the pigments are summarized in Table IV.

Furthermore, the flame resistance test was carried out in the following manner carried out: After the pigment has been processed into a paint with a binder became a test sheet by coating a sheet of paper with this paint manufactured. The fire resistance effect was then determined by using a flame was directed against the test sheet, This test was also carried out with usual technical white pigments, for example titanium dioxide of the rutile type, white Carbon and ammonium phosphate and the flame resistance of these pigments and with that of the silicon phosphate obtained in the present example compared.

When processing these pigments into paints, a commercially available one was used Latex (Dow Chemical Product 402) used as a binder and 3 parts by weight thereof were together with 10 parts by weight of a commercially available melamine resin powder (technical Reagent from Wako Junyaku Co., Japan) and 10 parts of water and 10 parts by weight der.einzelllen pigments mixed and through thorough mixing a homogeneous Paste received. Each flame retardant paint obtained was applied to both sides a drawing paper applied to a thickness of 1 to 0.8 mm and dried. Small pieces of the arches produced were used as test pieces.

The flame resistance of the test pieces was first determined, by directing a flame against them and determining whether there was any spread the flame took place. If the flame spread, the test piece possesses no flame resistance and was from further investigation locked out. The test pieces that were found to be flame resistant were given to one Tested for a paper given a fire resistance treatment has, d. H. the test according to ASTM D77-46. The length in mm of the Charring, if a flame was applied to the test piece for 12 seconds, was determined and the degree of flame resistance based on the length of char estimated. The shorter the charring distance, the better the elam resistance.

The results of the above flaw resistance tests are also included in Table IV.

Table IV Identification by means of X-ray diffraction analysis Si2P2O9 degree of whiteness (, b reflectance): Wavelength (mZu) 350 67.6 400 91.2 500 94.5 Water-soluble component (% by weight) 26.9 pH of a 10% aqueous suspension 2.8 Particle size (µ) below 5 degree of aggregation (Q) ( %) 5 Rust resistance test: weathering salt water test spray test pigment of the present example AA red lead (Pb3O4) BB weathering salt water test spray test lead cyanamide (PbCN2) BB zinc chromate (K20-4ZnO-4CrO.3H20) BB zinc wise (ZnO) Ca3 calcium phosphate [ZnO) CD calcium phosphate (PO4) 2] EE flame resistance test (mm / 12 sec.): Pigment of the present example 8-rutile type titanium dioxide (TiO2) no flame resistance white carbon (SiO2) no flame resistance ammonium phosphate [(NH3) 2HPO4] 20 It is evident from the above Values that the silicon phosphate pigment produced according to the present example is a white pigment which shows very satisfactory results in terms of rust resistance and flame resistance.

Example 2 A white pigment composed of titanium phosphate became made from titanium tetrachloride and orthophosphoric acid. That in the production The process used in this white figment and its properties are as follows specified.

Titanium phosphate was produced in the following way: One Solution of technical titanium tetrachloride and technical orthophosphoric acid placed in a high speed stir mixer and slowly to form a white titanium phosphate gels implemented.

After weighing this gel at a temperature of -60 to 700 C. It was washed thoroughly first with aqueous hydrochloric acid and then with water. The preparation of d, e, s pigment was carried out so that the composition the titanium and phosphoric acid components were adjusted to have a molar ratio of T, iO2; P205 of 1: 1 was obtained at this time.

After drying this washed titanium phosphate gel, it became during Calcined in an electric furnace at 400 ° C. for 1 hour, then during 3 hours in a ball-filled pot mill using methyl alcohol crushed wet as a grinding medium.

After the separation and recovery of the methyl alcohol as an abrasive the product was dried and a finely divided white titanium phosphate pigment obtain.

The identification of the finely divided white titanium phosphate pigment obtained by means of X-ray diffraction analysis and determination of the properties with regard to the degree of whiteness, in particular reflectance in the ultraviolet range, content of water-soluble constituents, pH of a 10% aqueous suspension, particle size and degree of aggregation were performed. Both the sun resistance and the flame resistance were examined and evaluated in the same manner as in Example 1, The results ~ are summarized in Table V.

Table V Identification by means of X-ray diffraction analysis predominantly non-crystalline TiP2O7 degree of whiteness (% reflectance) wavelengths (mµ) 350 60.0 400 105.0 500 105.0 Water-soluble component (% by weight) 2.55 pH of a 10% aqueous Suspension 1.2 particle size (/ a) below 2 degree of aggregation (Q) (%) 5 rust resistance test: Weathering method A Salt water spray method A Flame resistance test (mm / 6 Sec.) 10 s shows that the titanium phosphate pigment produced according to this example is a white pigment, which gives very satisfactory results in terms of Shows rust resistance and flame resistance.

Example 3 A white pigment composed of zirconium phosphate became made from zirconium nitrate and orthophosphoric acid.

Ground the manufacturing process and the properties of the product given below.

The zirconium phosphate was made by using a technical grade zirconium nitrate solution and a technical grade orthophosphoric acid in a high speed mixer mixer were added, wherein the ingredients were mixed and formed to form a white Zirkon.phospha-tgels were unset, which was washed thoroughly, namely first in aqueous hydrochloric acid and then in water. The composition of the zirconium and phosphoric acid components were adjusted so that at that time the The ratio of ZrO2: P205 was 1: 1. After drying the washed zirconium phosphate gel it was calcined in an electric furnace at 2000 C for 1 hour, whereupon N, ae size reduction of the product as in Example 1 using methyl alcohol was executed. The comminuted product was then dried and concentrated finely divided white zirconium phosphate pigment obtained.

The identification of the finely divided white zirconium phosphate pigment obtained was carried out by means of X-ray diffraction analysis and determination of the properties, such as degree of whiteness, Content of water-soluble component, pH of a 10% aqueous suspension, particle size and extent of aggregation. The tests on rust resistance and flame resistance were carried out and evaluated as in Example 1. The results obtained are summarized in Table VI.

Table -VI identification by means of X-ray diffraction analysis ZrP2O7 Degree of whiteness (% reflectance) Wavelength (mµ) 350 117 400 115 500 115 Soluble in water Constituent (% by weight) 11.5 pH of a 10% aqueous suspension 2.45 particle size (µ) below 5 degree of aggregation (Q) (%) 1 rust resistance test: weathering method A Salt water spray method A Flame resistance test 12 EG results from the above values that the zirconium phosphate pigment produced according to this example is a white pigment, which gives very satisfactory results in terms of Shows rust resistance and flame resistance.

Example 5 This example explains the case where various Silicon phosphate, titanium phosphate and zirconium phosphate pigments as rust preventive pigments can be used.

15 classes of finely divided, white silicon phosphate pigments became according to the procedure given in Example 1 in the following manner. manufactured: Those made from a xerogel of silica and orthophosphoric acid in the way Silicon phosphates that the molar ratios of SiO2: P2O (indicated by the Number n in SiO2 # nP @ O5) as shown in Table VII were obtained then treated at the temperatures and periods of time listed in Table VII. The products obtained were as in Example 1 using methyl alcohol Crushed wet and then dried to obtain the desired pigments.

14 classes of finely divided, white Titanphos-Phat pigments were made prepared according to the procedure of Example 2 in the following manner: Die titanium phosphates produced in this way from titanium etra chloride and orthophosphoric acid, that the molar ratios of TiO2: P2O5 (indicated by the number n for TiO2 # nP2O5) had the value shown in Table VII, were then used in those in Table VII specified te'np-eratures and periods. The products obtained in the process were then crushed as in Example 1 using methyl alcohol and then dried to the desired pigments.

Six leave from finely divided white zirconium phosphate pigments were prepared according to the procedure of Example 3 in the following manner: The zirconium phosphates produced from zirconium nitrate and orthophosphoric acid in this way, that the molar ratio of ZrO2 # P2O5 (given as number n of ZrO2 # nP2O5) the The value given in Table VII was then used for the 'in Table VII specified temperatures and periods. The product obtained in the process became as in example 1 using methyl alcohol wet crushed and then dried to obtain the desired pigments.

The properties, such as pH of the aqueous suspension, content of water-soluble component and degree of aggregation of the above, n5 types of finely divided white pigments were determined. The results are shown in the table VII summarized. The rust-proofing effect was as in Example 1 through rated the weathering and salt water spray tests and also these ratings are given in Table VII.

It can be seen from the values in the table, that very satisfactory Results on rust resistance were obtained in cases where the Content of water-soluble components at least 0.1 9 'and preferably at least 0.6% and were still obtained when the pII-IJert of the aqueous Suspension was not greater than 3.5.

Table VII Sample of silicon, conditions of phosphate properties the phosphate rust resistance no. Titanium manufacturing pigments rating or molar Treat- Treat- pH of the water- Aggre- Bewitte- Salt-Zircon- dissolution water ratio tempe- rature time of Suscher (%) experiment spray test (n) rature (hrs.) pension stock-MO2 # nP2O5 (° C) part (wt.%) 1 silicon 0.1 150 2 3.5 0.28 2 B C 2 also 0.2 150 2 2.8 1.17 2 B B 3 also 0.2 500 2 3.0 0.56 1 B C 4 as well 0.3 300 2 2.8 1.57 1 A B 5 as well 0.3 600 2 2.9 1.03 1 B B 6 as well 0.5 300 2 2.6 4.69 2 A A 7 as well as 0.5 500 2 2.7 3.00 2 A A 8 as well as 0.5 800 2 2.8 2.64 2 A A 9 also 0.7 500 2 2.6 5.73 5 A A 10 also 0.7 700 2 2.7 4.22 5 A A 11 as well 0.7 900 2 2.8 3.17 5 A A 12 as well 1.0 400 2 1.8 9.75 5 A A 13 as well 1.0 1000 2 2.7 5.75 5 A A 14 as well as 1.5 400 2 1.7 9.87 10 A A 15 as well as 1.5 1000 2 2.5 5.98 5 A A 16 titanium 0.2 250 1 2.8 0.15 1 B C 17 also 0.3 110 3 2.4 0.20 1 B B 18 also 0.3 250 2 2.6 0.14 1 B B 19 also 0.3 500 2 2.9 0.12 1 B C Tabel VII (continued) sample silicon, conditions of the phosphate properties of the phosphate Rust resistance no. Titanium Manufacture Pigments Assessment Or Molar Treat- Treat- pH of the water- Aggre- Bewitte- Salt-Zircon- gation water ratio tempe- time gen Suscher (%) test spray test (s) rature (hrs.) pension stock-MO2 # nP2O5 (° C) part.

(% By weight) 20 titanium 0.5 250 2 2.2 0.69 2 A A 21 as well as 0.5 500 2 2.5 0.52 2 B B 22 also 0.7 250 2 1.6 1.23 2 A A 23 also 0.7 500 2 1.9 0.89 2 A A 24 as well 0.7 800 2 2.7 0.25 1 B B 25 as well 1.0 400 3 1.2 2.55 5 A A 26 as well 1.0 600 3 1.9 0.75 5 A A 27 also 1.0 850 3 3.7 0.07 3 C C 28 also 2.0 500 2 0.7 12.20 5 A A 29 also 2.0 800 2 1.9 2.04 3 A A 30 zirconia 0.5 150 1 2.5 33.8 2 A A 31 as well as 0.5 300 1 2.5 15.5 1 B B 32 as well as 0.5 900 1 3.7 0.8 1 B C 33 as well 1.0 150 1 2.3 14.2 2 A A 34 also 1.0 400 1 2.9 6.7 1 B B 35 also 1.0 700 1 3.8 0.1 1 B C Example 5 This example shows the different Silicon phosphate, titanium phosphate and zirconium phosphate pigments as flame-resistant Pigments used.

As the phosphate pigments, ten kinds of those shown in Table VII were used finely divided, white phosphate pigments of samples 4, 8, 12, 14, 17, 21, 23, 25, 30 and 33 are used and the flame resistance test according to the procedure carried out according to example 1.

The ratings obtained are: summarized in Table VIII.

It is found from the values that there is a satisfactory flame retardant effect of the finely divided white phosphate pigments examined in this example shown.

Table VIII Sample of silicon, production conditions of the flame retardant no. Titanium phosphate test or molar treatment (mm / 6 sec.) Zirconium relationship temperature (s) rature (hrs.) MO2 # nP2O5 (° C) 4, silicon 0.3 300 2 13 8 as well as 0.5 800 2 -10 12 as well as 1.0 400 2 8 14 as well as 1.5 400 2 8 17 titanium 0.3 250 2 15 21 as well as 0.5 500 2 '14 23 as well as 0.7 500 2 13 25 as well as 1.0 400 3 10 30 Zirconia 0.5 150 1 15 32 as well as 1.0 150 1 10 Example 6 According to this example white phosphate pigments are made using various amorphous silicas manufactured.

As amorphous silicas, four types have been used: a) Acid-treated acid clay (composition 94.28 X SiO2, 1.49% A1203, 0.39% Fe203, loss on ignition 3.36%), which by removing the acid-soluble basic components from a Acid montmorillonite clay obtained by thorough treatment with sulfuric acid b) one obtainable from a silica gel by roasting at 2500 C ' Naterial, the gel being commercially available Use as a drying and adsorbent is available, wherein the roasted product obtained decomposes nert was, c) a by treating an ice, ensand slag with dilute sulfuric acid to form a silica sol containing impurities, -wherein the impurities removed after the silica has gelled, obtained silica hydrogel and d) a commercially available powdered silica gel product for reagent use.

Technical orthophosphoric acid was added to each of these silica materials (first quality according to JIS, 85.0% H3PO4, specific weight 1.69) in such Amount added so that the molar ratio of SiO2: P2O5 was 1: 0.5, the two ingredients then in a mortar for thorough and intimate contact were mixed.

After drying the individual mixtures, this was for 2 hours Calcined at 8000 C and then as in Example 1 using methyl a3 alcohol Crushed wet, after which it was dried and the individual finely divided white Pigments were obtained.

The properties of the individual finely divided pieces obtained in this way white pigments, such as degree of whiteness, content of water-soluble components, pH a 10% aqueous suspension, particle size and degree of aggregation certainly. Furthermore, the rust resistance test was carried out using the salt water spray method and the flame resistance test from S. The results are in the table IX included.

Table IX Initial whiteness water pH of the particle aggregate Rust, flame, silica (% reflectance) soluble 10% size gation resistant gel (Wave length mµ) cher aqueous (%) fluidity understanding suspension test such 350 400 450 500 550 part (%) a) White carbon, 78.5 94.0 94.5 95.2 95.5 2.0 2.9 below 2A 10 made from acid clay b) silica gel as reagent for 83.3 93.2 96.7 98.1 99.2 2.5 2.8 below 2A 10 drying 5 and adsorption c) Silica hydrogel, 76.5 90.4 92.1 92.8 93.4 2.8 below 2A 10 produced 5 au from iron sand slag d) silica gel reagent 75.8 95.4 99.0 100.0 100.0 2.5 2.8 below 2 A 10 5 -It follows that the received Pigments are very satisfactory white phosphate pigments, even if different amorphous silicas can be used as starting materials.

Example 7 This example uses various white phosphate pigments described using various silicates and earth minerals were manufactured.

Four bottles of silicate were used: aluminum silicate (Al2O3 # SiO2), calcium silicate (CaO # SiO2), magnesium silicate and sodium silicate (0.3 Na2O # SiO2).

Four types of natural earth minerals were used: As stratified The acidic clays of kaolin became bound material of phyllosilicic acid salts and @ontmorillonit were chosen, while a zeolite was chosen for the non-natural silicates was chosen and for the natural non-crystalline silica salts diatomaceous earth was chosen. The various earth minerals were either preserved in the natural State or after a 'calcination at 8000 C used.

Commercial orthophosphoric acid was added to the individual silicates (first quality according to JIS, 85.0% H3PO4, specific gravity 1.69) in the table X specified amounts were added and orthophosphoric acid was added to the earth minerals in a molar ratio of the silica component to the phosphoric acid component of 1: 0.5 was added, followed by mixing the two starting materials through thorough and intimate contact of the constituents was effected in a mortar.

After drying these individual mixtures, they were Calcined for hours at 8000 ° C., then as in Example 1 with prior use of ethyl alcohol Chopped wet and then dried and - the individual, finely divided white pigments are preserved -.

The properties of the finely divided particles obtained in this way. white. Pigments were determined as in Example 6 and the rust resistance test was also carried out by means of a salt water spray process and the flame resistance test with these pigments carried out; the results are given in Table X.

Table X II a, 60 1 P o a co MK \ MP CUN O 0 ddPm cd: drlk -lcua, Fi7 cn # 3 4D R @ ° l amount of whiteness water pH parts aggre ¢ ra: fjrlk and -er-ineral admixture- - reflectance soluble- a, constantly- constantly- WmW3 I component õ try try i.e., n (U KA (N n (U 400 500 h0bv ¢ bo silicate 25 98.2 103.0 102.3 1.2 3.5 half I 2, A 13 Lead 78 87.2 98.0 100.2 1.3 3.0 h 1 3 A 13 rldro (up rl a): ot 43 H ~ ~ Calcium E 59 94.5 101.1 102.7 1.2 3.0 2 A 13 (CaO.5102) 98 86.8 95.0 97.4 1.4 2.9 3 A 13 W rn no nn Pi rc \ CU lfU .CU CU l rl O a) ht P) 68 87.1 99.2 4 -1-, 3 2.8 "'a ° 88.6 97.6 99.3 1.5 2.2 1? 5 e cn rl k dV rlMa) <U : oS4 z 1 \ Tatrium 4.9 ml / 75.8 95.4 100, 1 ,? 2.6 2 A 10 K> (U L'4 100 ml E (0.3iNa20.5i02) o cMo cMS oO o ç NaOH 34.97 Q oo 11.6 ml / 77.0 97.0 99.5 1.9 oO o O cr ea dd N to R «) oovo 71 tD 4 O w 4) R 4) so NtX v lt ON o N H tH o oO oO OO OO fKi HOQ rv tO ¢ i H (oo cs oo O rl a) o P ve sæ.3 u \ æ 9 L <n N 3 \ <Nt O0 O0 o30 NL h SI a) w e ce AX e UI O 2 OH O tA OO Ov O wv (\ JC ~ U> \ C) <t0 0 rol rl hO a) hN (\ [1 S) F3 0 rd rO O ov 0 z tq p A, t0 vxw Ct .dD HO 4D rd ro O X to N rl C.Uz X [4 IO n I n U2 Od wr IG} E3 rl (M f rwl a CQ IO Ci OIO d Q rl rl rl 4) @ FA 4) rl rl 4) rl E waan uX X u) U2 gb rl, O rd rl X> t10 h FR trl (MO rl OR rt O h rl n ° ° g (9 g mI rl rd rl EtOr-l a0 @ «1 e sa rl i'J | ^ rl rl c U rJ V ld rl t CN | O to U2 llo <UW au U! / . <2 zeX.llTS Table X (continued) cu cu cu cu MN; cu rt - - - - - - «¢ 79.35, How- <77.5 81.6 1.3 2 ,? half past five 2 A 12 HAl 17.64, hold I ZI: track, ~~~~~ 90 ~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~ ~~~~~~~~~~~~~~~~ 0.38, - Ng0 0.26, calci- G1ür: r- nated 69.2 92.5 94.8 1.3 2.8 2 A 12 lust WWW aì W u cu cu 510 78.65, as Al 6 13.12, hold 90 43.5 59.8 72.3 1, -2 2.8 1: 2 A 12 11Ca 3 1.13, calci- dro 0.57, NgO 3.5, ned 63 ,? 89.7 92 ',? 1.2 2.8 2 A '12 product Scx oo oo o- F tov Ct WW (M nn How- ore hold N .60 ,? (t1,3 3,0 2 13 Fe07 0.40, Ca 2.03 ', calci- v 0.04, r? 3, O 0.04, product 87.0 87.8 1, -3 3.0 2 A 13 2.07, u, ccr n Cx n T. WO = Jm rnn v 4 ct cm in c0? 9.56, how- usa hold lrs 34, '2. 1.1, 2.7 2 A 12, 2o3 -3.03.90 rx W Ca, lc, - co, ô rw - :: X- o NO t OD ned Oh v. W LrX N product t9 O i - n 8.36 tO tD 4 tQ 4 rS X ar uX o oo [k (h OO o] 4) l) l ep l X 4) h <IX h UIOX hd I @ X sn IOA: .ID- O rl 4) M a) G1 srl 4> a ZD r 1 43 aa) fi} rl -1 D- 4) c) h ^ d 4> c) Fß rd p cD h rd 4> C) 'h U rd rl a) Q rQ rl tD o (1) rwl rd o aD rl rol tD o zrl X tderl h rl to Usrl h wrS liJ: Mrl h erl td ri h : 3S v S SS v nS> S () m> SOS 0 F F. us h (DS 4 uz t ^ ux coOO n to1resr @ n AN ns ^ oro v O o4-nJ 4Ng oKw07T n vC ~ PS g -v otg e I * Fo F0 0 0 0 0 I rs F vn> I e (> r cn OO h ra (rD vov rs [t trx t O ^ Lt- OW trio x cx a) N @ t, o N Cs ~ ba rmn P rGrG,>rN>hAG> -Ct 0. ß '»OL3 0 .q 4) C4D 0 æ .q -13 æ o, oc \ lso N ommo -NQ o Wev c) o X cO approx rl rQ rA t: Dd a rl rd a) (\ l tO.wl 2 r1 re rl a; cwl .2 rl rl (D; t oi a UX I lEq VS Ct IW t) rS Of 2, 1h V s Ct r- | U} rD 2 "1 alloe. IIO ;; IEIZtdS M4'F Lt) 0Z apaolra. moW tl ~~~ lelaulwPt tS ~ It can be seen from the above results that excellent results are obtained when the various silicates and the various earth minerals are used in the production of the white pigments and when the amount of phosphoric acid added is varied within the range according to the invention. - Example 8 In this example, white phosphate pigments are described which are made using the various phosphoroxy acids and. various salts of phosphorus oxy acids were produced.

Five types of phosphorusoxyacids have been used: Phosphoric anhydride (P2O5), metaphosphoric acid, pyrophosphoric acid, phosphorous acid and hypophosphorous acid.

Twelve kinds of salts of phosphorus oxy acids were chosen: ammonium orthophosphate, Disodium orthophosphate, sodium pyrophosphate, - sodium hexametaphosphate, sodium metaphosphate, Sodium tripolyphosphate, potassium phosphate, tricalcium phosphate, aluminum phosphate, Zinc phosphate, sodium phosphite and sodium hypophosphate.

That used in Example 1 was used as the starting silica component finely divided 'silica material (xerogel) is used.

The two starting materials were thoroughly and intimately into one Mortars mixed in such proportions that the molar ratio of SiO2: P2O5 Was 1: 0.5.

The ingredients are mixed with the addition of water as Mixed medium. This mixture was then dried and at 800 ° for 2 hours C calcined.

If phosphorous acid is a component of phosphoric acid in this package was used. stepped towards ae others Try the difference on that she burned. The obtained calcined product was then used crushed wet by methyl alcohol and then dried and the various finely divided obtained white pigments.

As in Example 6, the properties obtained were various finely divided white pigments and also the rust resistance test by means of the salt water spray method and the flame resistance test with the Pigments carried out, the results reported in Table XI were obtained Tabel XI Type of phosphorus whiteness water pH particles Aggre- Rostbe- Flammbeoxy-acid or of the phosphorus (% reflectance) soluble gation permanent- permanent phosphoroxy acid salt (Wavelength mµ) notch (µ) (%) stiffness test 350 400 450 500 part (%) phosphoric anhydride below (P2O5) 85.8 92.7 92.9 93.6 2.6 2.2 5 2 A 10 metaphosphoric acid (HPO3) 80.1 91.2 93.3 94.3 2.7 2.4 "2 A 10 pyrophosphoric acid (H4P2O7) 87.5 100.5 102.0 103.1 2.7 2.6 "2 A 10 Phosphorous acid (H3PO3) 78.6 101.1 100.9 101.6 2.5 2.4 "2 A 10 Hypophosphorous Acid (H3PO2) 40.8 80.6 83.5 85.8 2.5 2.4 "2 A 10 ammonium orthophosphate ((NH4) 2HPO4) 86.0 97.3 98.6 99.9 2.6 2.4 "2 A 11 Disodium Orthophosphate (Na2HPO4) 94.0 104.6 104.1 105.1 1.7 3.0" 2 A 12 Sodium Pyrophosphate (Na4P2O7) 90.0 103.7 103.8 104.3 1.9 2.8 "2 A 12 Sodium Hexametaphosphate ((NaPO3) 6) 65.3 85.3 88.4 90.6 1.8 2.8 "2A 12 Sodium Metaphosphate (NaPO3) 72.9 88.0 95.3 99.8 1.5 3.0 "2 A 12 sodium tripolyphosphate (Na5P3O10) 90.6 100.7 100.9 101.9 2.3 2.8 "2 A 12 Table XI (continued) Type of phosphorus Degree of whiteness water- pH particle-aggregate- Rostbe- Flammbeoxy-acid or the Phos- (% Reflectance) soluble gation permanent- permanent phosphoroxy acid salt (Weller length mµ) notch (µ) (%) skill test attempt 350 400 450 500 part (%) Monopotassium phosphate below (KH2PO4) 69.0 95.9 98.3 99.4 2.2 2.8 5 2 A 12 tricalcium phosphate (Ca3 (PO4) 2) 88.7 97.4 99.3 100.5 1.3 3.2 "2 A 12 aluminum phosphate (AlPO4) 76.9 93.8 96.2 97.9 1.2 3.0 "2 A 12 zinc phosphate (Zn3 (PO4) 2) 48.9 96.1 92.6 97.3 1.2 3.0 "2 A 12 Sodium Phosphite (Na2HPO3) 85.3 101.8 102.8 103.8 2.2 2.8" 2 A 11 Sodium Hypophosphite (NaH2PO2) 61.0 90.4 96.3 98.3 2.4 2.8 "2 A 11 From the above Values show that excellent results are obtained both when the white phosphate pigment using the phosphoroxy acids as well as if that Pigment using the salts of phosphorus oxy acids.

Example 9 In this example, white pigments are of the silicic acid-phosphoric acid-ammonia type described using a xerogel of silica, phosphoric acid and ammonia was produced as raw materials.

The silica xerogel prepared according to Example 1 was used as the starting silica Silica xerogel used with small aggregates.

A commercial orthophosphoric acid (JIS first quality, 85% PO specific gravity 1.69) was used as the starting phosphoric acid.

Ammonia water (25 to 29%) as an industrial chemical.

was used as the starting ammonia.

First, the ammonia water was thoroughly attached to the silica xerogel absorbed at room temperature. In this procedure, 11.5% by weight was calculated as NH4OH, ammonia absorbed by the silica xerogel.

Even if the temperature- this silica gel with ammonia absorption was raised to the counter of 600 ° C under a dry atmosphere, no deposition was made of ammonia and the differential thermal analysis also showed none endothermic peak within this temperature range.

Phosphoric acid was added to this silica gel with ammonia absorption in an amount corresponding to 1 mole of P2O5 per mole of SiO2 added. Furthermore was ammonia water admitted and the mixture is intimately mixed, so that a slurry A mixture was obtained, the pH of which was about 9 to 9.5. This mixture was dried and dehydrated at about 80 ° and further at 800 for about 1 hour C heated. This was followed by wet comminution of the product as in the example 1 using methyl alcohol, whereupon the ground product is dried became. A finely divided white pigment was obtained.

The X-ray diffraction analysis, differential thermal analysis and analysis the composition of the finely divided white pigment obtained were also determined like the determination of the pH value of a 10% aqueous suspension, the content of the water-soluble component, the degree of aggregation and the particle size distribution performed. The flame resistance test was also carried out with this pigment.

For comparison purposes, (A) ammonium polyphosphate, a commercially available Flame retardant, and (B) diammonium phosphate [(NH4) 2HPO4] as the reagent chosen and their properties and flame retardancy in that given above Way investigated.

The results are summarized in Table XII. Tabel XII sample Röntgenbeu- thermal analysis of the pH of a content Aggre- part flame exposure analysis Differential Composition of 10% concentration chemical analysis (formula of Mo- suspen- water- (%) size- (0-600 ° C) lar ratio) sion soluble sen- experiment (endothermic stock distribution (mm / mer peak division 12 sec.) ° C) (µ) product X-ray diffraction pattern A-1 193 SiO2 # P2O5 # 6 7.5 23.8 0.5 4-0.5 8 according to this the example description NH3 # 3H2O comparison A (Ammo- (NH4) 2.7H1.3P2O7 224.229 (NH4) 2.7H1.3P2O7 4.4 14.7 45.5 100-10 10 nium polyphosphate) Comparison B (Diam- (NH4) 2HPO4 210 (NH4) 2HPO4 8.2 63.9 100 100-10 15 monium phosphate) It is evident from the foregoing Values that the finely-divided, white manufactured according to this example Pigment not just compared to similar white powders that are for comparison purposes have been investigated, is superior in terms of the flame retardancy effect, but rather also differs completely in terms of the various properties. Besides that it has superior pigment properties, especially with regard to the degree of aggregation, a property that is particularly required for a pigment. It follows from this that this white 1-pigment is extremely suitable for use as a flame-resistant pigment is satisfactory.

Example 10 In this example, the flame retardancy effects obtained, when the white pigment of the silicic acid-phosphoric acid-ammonia type produced according to Example 9 with different. Resins is mixed, described.

It was a commercial polyester resin and alkyd, melamine and Polyamide resins commonly used as paint resins for coating purposes are elected.

It became the polyester resin, "Polymal," polyester from Takeda Chemical Company, used.

70, 50 and 30 parts by weight of the white, powdery Pi gLientes of the Ki esel acid-phosphoric acid-ammonia type, which according to the method of Example 11 were each made to 100 parts by weight of the above polyester resin added, whereupon 10 parts by weight of chlorinated paraffin (CP 70), 0.6 parts by weight of cobalt naphthenate, 1.0 part by weight of a peroxide and 0.1 part by weight of dimethylaniline were added to each mixture became. They began by mixing the individual mixtures with thorough stirring in about 5 to 7 minutes to harden while the mixtures are still in the flowable state found, they were eaten in sheets 3 mm thick and left to harden.

The arches obtained were. then on-the flame retardancy effect examined after the ignition test according to ASTN D-635.

A commercially available alkyd resin that dries at room temperature was used as the alkyd resin Alkyd resin paint used. For every 100 parts of this material, 50 Parts by weight of the white, powdery pigment prepared according to Example 9 are mixed in.

A solution in butanol was used as the melamine resin. a butylated melamine used as a precondensation product of the melamine resin. To this solution were 50 parts by weight of the white powdery pigment prepared according to Example 11 mixed in.

As an application type polyamide resin solution with isano oil, linseed oil and Polyamide resin as the basis was a paint made of 100 parts by weight of a polyamide resin solution, 100 parts by weight of isano oil, 100 parts by weight of linseed oil, 40 parts by weight of chlorinated paraffin (70% Cl) and 0.5 parts by weight of cobalt naphthenate plus lead naphthenate are used. 150 Parts by weight of the white, powdery produced by the method of Example 11 Pigment were mixed with the above paint.

These pigment-added resin paints were put on pieces of a Drawing paper is applied and dried by leaving it for 24 hours at room temperature in the case of the alkyd resin were left to stand for 1 hour at 110 ° C i @ Fall of the melamine resin were dried and for 24 hours at room temperature in Case of the polyamide resin. Film covers each with the This made resins mixed with pigments on the pieces of paper obtain.

The pieces of paper with the various film covers on their surfaces 1 were subjected to the flame resistance test according to Example 1 The results of this experiment are summarized in Table XIII.

Table e XIII Polyester Resin Added amount of time to self-extinguishing white pigment of fire (parts) (minute, second) 70 3 sec.

50 7 sec.

30 1 min., 50 sec.

Paint type resins Type of resin Flame resistance test (mm / 12 sec.) alkyd resin 17 melamine resin 4 polyamide resin 6 From the above values it turns out that there are satisfactory flame retardancy effects also in the case can be obtained where the white pigments obtainable according to the invention in different Resins are incorporated and mixed with the white pigments according to the invention Resins can either be made into a base or applied as a coating will.

Claims (8)

Claims 1. White pigment with excellent flame resistance and corrosion resistance, consisting of a phosphate with a composition of the formula M1O2 # xY. (0.1 # 1.5 + mx / 2) P2O5, in which M1 is one of the atoms silicon, titanium or zirconium Y is nitrogen-containing Base or an oxide of the formula M2On 2 in which N2 is an alkali metal, alkaline earth metal, Aluminum, lead or zinc, and n represent the valence of this metal N2, x a positive number up to 6, including 0, and m is 1 if Y is one represents nitrogenous base, and the value n, if Y has the meaning N2On, mean, 2 where the phosphate is at least 0.1% of a water-soluble component contains. 2. White pigment according to claim 1, characterized in that the phosphate contains 0.6 to 20% of the water soluble component. 3. White pigment according to claim 1 or 2, characterized in that that the phosphate has an aggregation rate of not more than 50%, accordingly the following formula = ### x 100, where A is the weight of the Powder passing through a sieve of a given mesh size, A 'the weight this through the same sieve after standing for 24 hours at room temperature in air with a relative humidity of 90% powder and Q the degree of aggregation mean in percent. 4. White pigment with excellent flame resistance and corrosion resistance, consisting of a phosphate of the formula SiO2 # xY # (0.1 # 1.5 + mx / 2) P2O5 where Y is a nitrogenous base or an oxide of the formula M20n in which M2 is an alkali metal, Alkaline earth metal, aluminum, lead or zinc, and n the valence of the metal M2 represent, x a positive number up to e including 0, and m the value 1 if Y is a nitrogenous base, and the value n if Y is the group N2On is mean. 5. White rust-preventing pigment, consisting of a titanium phosphate of the formula TiO2. (0.2 # 1.5) P2O5, where the titanium phosphate is at least 0.1% of a water-soluble Contains constituent and a 10%, aqueous Suspension of the Titanium phosphate has a pH of no more than 3.5. 6. White pigment, consisting of a zirconium phosphate of the formula ZrO. (0.4 # 1.0) P2O5, where the zirconium phosphate is at least 0.1% of a water-soluble Component contains. 7. Coating compound to prevent rusting of metal surfaces, consisting of (a) a carrier material containing a film-forming coating material, wherein the carrier material is preferably made of alkyd resins, epoxy resins, air-drying Oils, phenolic resins, polyvinyl acetals, vinyl chloride resins or polyvinyl acetates and (b) a rust preventive pigment composed of a phosphate of a composition of the formula M1O2 # xY # (0.1 # 1.5 + mx / 2) P2O5, where M1 is one of the atoms silicon, Titanium or zirconium, Y a nitrogenous base or an oxide of the formula M2On, 2 wherein M2 is an alkali metal, alkaline earth metal, aluminum, lead or zinc and n die Represent the valence of the petall M2, x a positive number up to 6 including by O tind m is 1 if Y is a nitrogenous base, and the value n, if Y is the group N2On, is 2, where the phosphate is at least 0.1 só of a water-soluble component and the phosphate in an amount from 1 to 50 parts by weight per 100 parts by weight of the base material constituting the coating film is present. 8. A method for preventing rusting of nets, characterized in that that on the surface of the metals as an undercoat layer a paint is applied which (a) a carrier which is a coating film forming Base material: has, the carrier material preferably made of alkyd resins, epoxy resins, air-drying oils, phenolic resins, polyvinyl acetals, vinyl chloride resins or polyvinyl acetate consists, and - (b) a white, rust-preventing pigment, which consists of a phosphate having a composition of the formula M1O2 # xY # (0.1 # 1.5 + mx / 2) P2O5, wherein M1 one of the atoms silicon, titanium or zirconium, Y a nitrogenous base or an oxide of the formula M2On / 2, where M2 is an alkali metal, alkaline earth metal, aluminum, Lead or zinc and n represent the valence of the metal M2, x a positive number up to 6 including 0, and m is 1 if -y is one nitrogenous base isti and the value n, if Y is a group M2On, is 2, wherein the phosphate contains at least 0.1% of a water-soluble component and the phosphate in an amount of 1 to 50 parts by weight per 100 parts by weight of the coating film forming base material is present.