DE2159342C2 - New white pigment - Google Patents

Description

On the other hand, titanium dioxide is known as a white pigment, the covering power of which is excellent. However is his Whiteness, especially the reflection in the ultraviolet range, is not sufficiently high and it also has ^ There is also a considerable need for pigments in the field of pigments

Corrosion-resistant pigments are red lead, lead powder, zinc dust, aluminum powder, zinc chromate, barium chromate, lead cyanamide and basic chroma! known. The pigments, which are corrosion-resistant in a carrier solution, are used as rust-preventive paints, primers or washing primers. However, these rust prevention coatings are still not fully satisfied-end when the Haftungrfieser A nstriche on the metal surface and the prevention of penetration or penetration of Waswr, moisture or corrosive gases, either between the Metallunterfage and coating compounds or r 'een the Anslrichmassen and here on applied coatings should be considered. In addition, corrosion-resistant pigments such as zinc chromate show. quite generally a tendency to deterioration of the carrier or the binding substance and are therefore not satisfied if they are used to form a solid preventive coating on a metal surface ^{A n} d ^{n d} s v ⁸ ors ⁰ td ^ ndcn corrosion-resistant pigments, those having a large Korp -. "Onsbeständidkeit always either the Bleilyp or by chromic acid type. These corrosion-resistant pigments impart a pronounced color to the SM surface and therefore the disadvantage arises that a color coating of sufficient thickness must be applied over this anti-corrosion system. to hide its color, furthermore, since the above corrosion-resistant pigments contain lead and chromates which are harmful to health, there arises a serious problem that workers handling these rust-modifying paints are exposed to very serious damage to health. .

Further, in the case of flame retardant paints or molded articles coated with flame retardant resins, it is known a flame retardant composed of various phosphates. ein'uveSen The door such a flame retardant property required consists m the formation of a non-combustible foam when the above coating compounds are exposed to the flame and in the carbonization of the coating mass. Although the usual flame retardants those made of Ammo-SumphScn, form foams on exposure to the flame and by the release of the If free phosphates cause carbonization of the combustible SUTs, these compounds of other SS are completely soluble in water and have the disadvantage that they not only lack durability, but they also have no dispersibility, since they show a tendency to aggregate, / ur elimination of this The disadvantage was that ammonium polyphosphate was used as a flame retardant agent. However, one thing about ammonium polyphosphate is that it has no special properties that make it useful as a filler or pigment. For example, it arises in the case of ammonium polyphosphate easily induces secondary aggregation and, therefore, it is difficult to disperse in an aggregate in a particle size which is commonly used in pigments. The properties of a coating film obtained by using a coating composition containing ammonium polyphosphate are general

^In DrI-AS 12 23 349, a process for the production of a titanium phosphate suitable as a pigment by reacting titanium tetrahalogen with phosphoric acid or a phosphate is described. The thereby obtained

Titanium phosphate pigment, however, is extremely soluble in water and its aggregate behavior

satisfactory. u τ ττ \ ο η ι u η rw

The US-PS 18 76 065 describes the production of titanium compounds such. ti. I \ i {) _: r _; U <S «: ^υ · ^υιε

Titanium compounds obtained in this way are, however, not yet permitted, especially when used as a white pigment.

developing.

Fern-r describes the GB-PS 9 16 550 the production of zirconium phosphate, which however also not yet have the desired properties for satisfactory white pigments _

Finally, DE-AS 11 37 721 describes a process for the production of K.eselphosphorsaure wherein Products are obtained which in terms of water solubility and the extent of aggregation are still not

lASU is therefore the creation of a new white pigment that has both excellent resistance to corrosion and excellent resistance to corrosion, as a rustproofing agent that is not of the lead or chromium acid type and that although it has the water-soluble components necessary for rustproofing contains, no inclination; to ^ aggreg ^ tion so that it can be easily dispersed in carriers or resins. Furthermore, the invention aims to produce paint compositions to prevent roasting

^M D? E ^{n n} ser solution ^C, the object is achieved according to the Erfindung'durch creating a white pigment on Phosphatbäsfs which is characterized in that it consists of a phosphate having a composition of the formula is

M ¹ O ₂ · .χ-Υ

consists in what

M ¹ one of the atoms silicon, titanium or zirconium,
Y a nitrogenous base or an oxide of the form!

M ² O ,.

wherein M ^{2 is} an alkali metal. Alkaline earth metal. Aluminum, lead or zinc,

and π represent the valence of this metal M ^:
λ is a positive number up to 6 including 0, and

the value 1 if Y is a nitrogenous base, and the value n if Y is the meaning

m
M ² O _n

has, mean,

the phosphate pigment having a water solubility between 0.1 and 20% by weight after wet comminution and an amount of aggregation of not more than 50% according to the following formula

Q = x 100

possesses wherein A is the weight of the sieved through a mesh size of 74 ηι continuous powder A ', the weight this- by the same sieve after standing for 24 hours at room temperature in luit a relative humidity of 90% solid powder and Q _μ the aggregation degree ι mean ηpercent. The phosphate-based white pigment according to the present invention has excellent whiteness, and particularly, good reflectance in the ultraviolet range, as well as superior flame resistance and corrosion preventive property.

Composition and properties of the pigment

The white pigment according to the invention can be made from either silicon phosphate, titanium phosphate or zirconium phosphate consist alone or can consist of a combination of individual ones of these phosphates or a complex of these Phospha'.e exist with other phosphorus compounds.

M) According to one embodiment of the invention, a white pigment has excellent flame resistance and corrosion resistance obtained, soft from a phosphate of the formula

_h <CiO: -vY (ol ~ 1-5 + -γ-) P; O < ^(M)

is built up in which

Y cine nitrogenous bunny or an oxide of the formula

wherein M 'is an alkali metal, alkaline earth metal, aluminum. Lead oiler / ink and η the valence of the metal

M ² represent.

.v is a positive number up to / ud, including O, and m the value 1 if Y is a nitrogenous rabbit, and the value n if Y is a group in

is.

The initial silicon phosphates usually consist of one of the silicon phosphates 2 SiO _2, P ₂ O _S , 3 SiO; 2 PiPs or SiO ₃ PjO, or mixtures of such compounds or further mixtures: o see such silicon phosphates with silicic acid anhydride, silicon salts and / or other phosphates according to claim I. Although the above silicon phosphate compounds are substances which are known per se, So far, nothing at all is known about the properties that these compounds have, or whether they are useful or valuable substances. Furthermore, since silicic acid compounds such as silicic acid, blcisilicate, calcium sulfite or aluminum silicate are usually transparent and consequently it is possible for these silicic acid compounds to serve as a filler that gives the substrate transparency, there is no indication that these compounds are white pigment can serve, through 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, which consist predominantly of silicon phosphates, are unique in that they are non-transparent and have an excellent degree of whiteness and, in particular, have a reflectance in the near ultraviolet and ultraviolet range, so that they have a White pigment result, which has new properties compared to the usual white pigments.

Table I below shows the values obtained when the white pigment _{according to the invention composed of silicon phosphate (2 SiO, P 2} OO and a commercial titanium dioxide of the rutile type and white carbon dioxide (finely divided silica) were compared with regard to their degree of whiteness that the whiteness and especially the reflectance in the near ultraviolet and in the ultraviolet range is clearly superior to the pigment according to the invention.

Table I. Pigment Weilinrad ') (7th Relleklan / at different wavelengths)

32 () ιιι _μ 350 nvi 4 (XIm _1. 450 ma 500 nw 550 nw 600 nvi

. _4i

According to the invention 37.5 80.7 98.2 100.8 101.8 101.9 102.0 Silicon phosphate white pigment Rutile type titanium dioxide Finely divided silica anhydride

*) The degree of viscosity was determined by the reactance measurement method by means of the powder method using a spectrophotometer. F. in sheet made of aluminum oxide (Al ₂ Oj) was used as the standard and on the basis of the aluminum oxide sheet as 100, the luminance was given in% at the individual wavelengths,

When in the silicon phosphate pigment according to the invention, wherein SiO. If the silica component and P ₃ O ₅ indicates the phosphoric acid component, the molar ratio of P ₂ O with respect to one mole of SiO _{2 is} less than 0.1, the desired whiteness and non-transparency cannot be obtained. On the other hand, if the molar ratio of P ₂ O ₅ to SiO _{2 is} greater than 1.5, neither ramming resistance wedge nor corrosion resistance results, and no further increase in whiteness, ramming resistance and corrosion resistance can be achieved. Rather, the chemical stability of the pigment itself decreases. With regard to the whiteness and non-transparency of the pigment to be obtained, a molar ratio of SiO ₂ : P ₂ O ₅ in the range from 1: OJ to 0.8 is therefore particularly preferred in the context of the invention. Alkali metals (like sodium or potassium), alkaline earth metals (like calcium or magnesium) or aluminum. Lead or zinc can be present in the silicon phosphate pigments according to the invention in the form of phosphates or silicates or also as double salts. From the point of view of the whiteness and non-transparency of the pigments, these metals, indicated as oxides, in a molar ratio of MO «to SiO ₂ of not

2.9 7.7 42.8 92.8 93.7 95.7 96.0 16.8 30.9 73.0 79.2 83.1 84.6 86.8

greater than 6 and preferably not greater than 3 presence. Iams present these Metallbestandleile in the pigment, the Phosphorsiiurebestandteil (P ()) is greater than indicated above in an amount up to a m

Extent of not greater than - moles per mole of MC) _{n be} present.

2 j

It was also found that, among the pigments represented by the above formula (1-1), a test ammonium phosphine silicate. which contains as necessary constituents a silica constituent, a phosphoric acid region and an ammonia nitrogen constituent and in which the molar ratio of the silica constituent (SiO;) to the phosphoric acid region is in the range from 0.2 to 5 and the molar ratio of _{the phosphoric acid constituent (NH 1} ) to the phosphoric acid constituent < P _: O <) is in the range from 1 to (>,

ι «is particularly superior with regard to the flame retardant wedge.

It is not entirely clear whether these flame-resistant pigments according to the invention are made from 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 which is characteristic of ammonium phosphate, show and flame retardant pigments made either using triammonium phosphate or

Diammonium phosphate and mixing with silica were prepared using an X-ray diffractometer. the

for diammonium phosphate or monoammonium phosphate is characteristic, show, it is assumed

that the flame-resistant pigment according to the invention consists of an intimate mixture of ammonium phosphai and either ammonium silicate or a silicate with adsorbed ammonia.

Particularly suitable lamb-resistant pigments according to the invention are those consisting of a solid

> (i powders with the following X-ray diffraction values exist:

A. Those with the following X-ray diffraction pattern:

5.04 100

3.36 75

3.06 55

5.30 50

3.17 45

3.75 40

B. Those with the following diffraction pattern:

3.06 100

5.3-1 90

3.76 80

2.00 55

2.66 30

2.37 Π

C. Those with the following X-ray diffraction pattern:

St. _n

6.02 HK)

5.43 70

3.23 65

3.81 55

3.49 50

3.98 40

If a thermal differential analysis of the flame-resistant ammonium phosphate silicate pigments according to the invention is carried out, this shows an endothermic peak, which accompanies the separation of the ammonia, at a temperature of usually 120 to 260 ^° C. and has the foaming properties which is required for a heat-resistant coating composition. In addition, this compound releases phosphoric acid simultaneously with the separation of ammonia. This phosphoric acid is effective for carbonizing the combustible substances. The ammonium phosphate silicate thus makes the combustible materials of the

Coating compound llammvcrz. ^ Rnd. (ilcich / ciiig the released phosphoric acid reacts with the silicic acid even higher temperatures, so that the heat of combustion is completely discharged; the endo hcrme Reactmr "of free phosphoric acid and silicic acid show, he, the thermal Dillereni.alanalysc as distinctive endothermic peak at temperatures from 360 to 500 ° C.

The excellent self-extinguishing properties of the ammonium phosphate silicates according to the invention _? lissen see explain in this way.

With a different design cylinder there is a wciUes. Rose-preventing P.gment. which from a titanium phosphate of the formula

TiO., - ((). 2 ~ i.5) PA ⁽¹ " ^{2) U1}

consists wherein this titanium oxide contains at least 0.1% by weight of a water-soluble component and one Has a pH of no more than 3.5 if it is apt. aqueous suspension is processed.

A further embodiment of the curvature results in a white peeling. that from a zirconium phos- ^ ^ phal of the formula

ZrO (0.4 ~ 1, O) PP ₅ ⁽¹ ' ³⁾

where the zirconium phosphate contains at least one water-soluble reading material.

The AuZerhältnis of zirconium or titanium to phosphorus in the, or Zirkonphosphal T.lanphosphat _2u can be within a wide range. In general, however, it is favorable if the zirconium or titanium constituent in the phosphate is indicated by MO, in which M is either zirconium or itane, and the phosphoric acid constituent is indicated by PA, that the PA is at least 0.1 mol and preferably at least 4MoI ie MoI M0, and furthermore not more than 1.5 moles and preferably not more than 1 mole per mole MO, with an amount of the phosphoric acid constituent less than 1 mole, no distinctive rust:> preventing and flaming wedge effect can be achieved will. Furthermore, even if the phosphoric acid component is present in amounts larger than 1.5 moles, the rust preventive properties cannot be remarkably increased

Flame resistance effects can be achieved because there is a limit to the improvement that can be achieved the chemical stability of the rust prevention pigment itself suffers. Titanium phosphate or zirconium phosphate, those that are most favorable for achieving the objects of discovery are those in which the molar behavior

nis MO ₂ : P, O, a value of about I: 1 hai. , _, "· ■, ·, · κ ei _m

It is most important from the viewpoint of rust prevention and flame resistance that in the white phosphate pigments according to the invention the water-soluble component in an amount of at least 0 1% is included and that in the case of titanium phosphate the pH value is 10%. aqueous Suspension of the same is not more than 3.5. A phosphate pigment, which neither one nor both the .u Satisfied with these conditions, it does not have the excellent rust-preventing properties as found in the Pnosnian DiRmenia Throw like the invention shown. ...

Titanium phosphate itself is a well-known white pigment of an excellent degree of whiteness and has one in particular Ultraviolet reactance (e.g. British patent specification 9 94 669) However, the known ones have become White pigments which consist of titanium phosphai, in all cases practically completely by calcining made insoluble in order to increase their chemical stability, so that the titanium phosphate does not dissolve in water Constituent in amounts of at least 0.1% by weight as in the case of those to be used according to the invention Contains titanium phosphates. On the other hand, it is possible according to the invention, as will be explained below the content of water-soluble constituents is reduced to at least 0.1% by suitable choice of drying and Calcination conditions of phosphates such as tilane phosphate. to regulate. As a result, out-denoted Rust prevention properties as well as flame retardant wedge can be obtained in the phosphates A content of water-soluble constituents of more than 24% is not favorable, however, as it is caused by a waste the properties of the phosphate pigment is caused. On the other hand, when the acidity of the titanium phosphate is st d. H. the pH value of a 10% aqueous suspension is evident. becomes smaller than 1, this is also unfavorable since this tends to damage the carrier material. ? "

In the following tables II and III are the relationship between the calcinic temperature. the amount of water-soluble ingredient and acidity in relation to rust preventive property, if the calcining temperatures of titanium phosphate and silicon phosphate can be varied. The evaluation of the anti-rust properties was carried out by means of the following simple test procedure

^r ° Was.ser was added to the finely-zcrtcilten titanium phosphate and silicon phosphate in a Gcwichisverhälinis of I · I then mixed thoroughly, was obtained whereupon a white paste.

A commercially available iron sheet with a protective film made of a vinyl chloride resin was used as the test sheet used on both surfaces after peeling off the resin film. The inner surface of this Sheet iron (thickness 0 32 mm), from which the resin film had been freshly stripped, was then given an over- n> Zug of the white paste obtained above in a thickness of 60 to 40 μ coated, so that a film coating was formed on the iron sheet.

For comparison, test panels were made in a similar manner by applying calcium phosphate and Zinc phosphate as phosphates, basic lead silicate and white carbon as silicates, and red lead as commercially available Rust prevention pigment is made on the inner surface of the iron sheets so that em FUmf >> coating was formed on the iron sheets. The rust preventive effect of these film coatings was with that of the film coating of the above white paste of titanium phosphate and silicon phosphate visualize.

δι jy

After the film over / .iiye tolerate Vcrsuehseisenbleehen in the above manner had been formed, the sheets into a closed chamber of 40 ⁰ C and a relative humidity rin 100 hours, of 100 "hung /" and d .-. Left. After 100 hours When the text sheets were taken out of the closed chamber, and the film-coated surface of the sheet metal was evaluated for the degree of rust formation, ratings Λ, B, C. D and Π were given according to the states of rust formation in the following manner.

A: No rust at all. Found: there was practically no change from the point in time where

the coating had been applied.
ιυ B: rust on the order of pinholes visible.

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

D: Rust formation found in the larger part of the sheet and peeling off of a larger part of the film coating found.
\> E: Crack in the film coating and rust formation over the entire surface of the liner.

The other values given in Tables 11 and III were obtained in the following way:

IJ) Wa ««: pr! Ös! I. Cr Ks

: n 20 b of the pigment powder were placed in a 100 ml measuring flask and then about 70 ml

Added water and heated for 5 minutes. After cooling the mixture, water became up added to the calibration mark and the mixture shaken well and then left to stand for 1 hour. The contents of the flask were then filtered through a dry filter paper. The first portion of 20 ml was discarded and the next 50 ml amount of the clear liquid was placed in a weighing bottle for

. '<Taken for evaporation drying purposes and evaporated to dryness. After drying for 1 hour at 105 to 110 ^° C., the residue obtained on evaporation was weighed, whereupon the percentage of water-soluble constituent was calculated from the amount of the residue thus obtained.

(2) pH of a 10% aqueous suspension.

.-o A 10% aqueous dispersion was well dispersed by shaking thoroughly. This suspension

was left to stand for 1 hour and then the pI-Wcrt was determined with a pH meter.

(3) Whiteness.

A spectrophotometer was used and the reflectance (%) at each wavelength was mil determined by the powder method. An alumina bogeii was used as a Slandard bow and the used on the basis of the aluminum sheet of 100 numerical values obtained to indicate the degree of whiteness.

(4) Opacity.

The hiding power was determined according to the method (a) for determining the hiding power according to the pigment Testing Method 6 determined in accordance with JIS K-5101-1964. Three ml of boiling flaxseed oil became 3 g of the Sample added and the mixture a Knctarbeitsgang with 25 revolutions with a grinder from Subjected to the Hoover type four times and thereby processed to the pasolous state. The ücckkraft was then determined with a cryptometer using the Pro'oe thus treated. The graduation (mm) at which the boundary line became visible on the Cryplomctcr's indicator is the value that is specified as opacity. The smaller this value is, the greater the opacity.

Table II

Properties of the various titanium phosphates

Example no. Conditions of manufacture
of the Titunphosphals
Molar hand
reverberation
nis (n) temperature time ( ⁰ C) (Hours.) water
more soluble
Duration
part pH one
107. own.
aqueous
Suspen
sion Degree of whiteness
(% Rellcklan /)
Wavelength (m> i) 400 500 Deck-
force valuation
d. Rust-
prevent
in-house
shaft 5 · ■■!
ΐ \
;. ■■ ( TiO,
nPjÖ, 450 4th (wt .-%) 350 103.0 105.0 (mm) 10 1 2 600 4th 173 0.5 85.0 103.0 105.0 30th A. I. 2 2 800 3 6.55 1.4 90.2 103.0 105.0 25th A. 15th S. 3 2 1000 2 1.9! 1.9 90.5 103.0 105.0 19th A. 1 4th 2 200 4th 0.56 2.4 91.0 93.2 101.0 17th B. ; i 5 1 400 4th 2.90 0.8 39.2 101.0 101.0 37 A. 6th 1 600 3 2.55 1.2 60.0 ιΰϊ, υ 102.0 25th A. 2U 7th 1 850 3 0.75 1.9 65.3 102.0 105.0 20th A. 8th 1 1000 3 0.0 " 3.7 80.7 102.0 105.0 18th C. 9 1 150 3 0.05 4.2 87.2 87.0 100.0 16 C. 10 0.5 350 3 1.05 2.2 22.5 87.4 100.0 40 A. 11th 0.5 600 2 0.68 2.3 24.3 9Q.2 101.0 25th A. 12th 0.5 850 2 0.58 2.6 28.5 90.5 101.2 20th B. 13th 0.5 1000 2 0.05 3.9 46.0 90.2 100.5 18th C. 14th 0.5 100 1 0.04 4.5 50.3 90.0 100.0 16 C. 30th 15th 0.3 400 1 0.20 2.4 21.0 91.0 100.5 30th B. 16 0.3 100 1 0.13 2.9 37.5 90.2 100.0 20th B. 17th 0.25 400 1 0.17 2.5 20.5 91.5 101.0 25th B. 18th 0.25 Calcium phosphate
(Caj (PO ₄ ) ₂ ] 0.11 3.0 39.0 102.2 102.0 18th B. 35 Control 1 Zinc phosphate
| Zn, (PO ₄ ) ₂ l 0.0025 12.59 92.1 89.8 92.7 100 < E. Comparison 2 insoluble 7.59 27.3 100 < D. 40

Table IH

Properties of the various silicon spheres

Example no. Conditions of manufacture Treatment Treatment water pH one WciUgrad 4 (X) I. deck valuation of the titanium phosphate neck liings- lung more soluble 10%. C /. Kcliektan /) crane d. Rosi- Molar lcnipcmlui ■ / express Duration aqueous Wavelength (m> i 76.3 prevent reverberating ( ^u f) (Std.I part Suspen 92.8 MM) in-house nis (μ) sion 92.6 > ch « SiO ₂ 300 2 Kiev. · "/«) .150 94.0 84.2 (mm) n PjO, 500 2 70.1 95.5 I. 1 800 2 04/11 1.6 58.0 87.2 95.8 65 A. 2 1 1000 2 8.31 1.9 83.3 91.2 95.5 60 A. 3 1 300 2 7.70 2.2 76.7 93.4 81.6 55 A. 4th 1 500 2 5.74 2.7 68.0 74.5 91.7 45 A. 5 0.5 800 2 4.69 2.6 55.0 77.8 94.5 70 A. 6th 0.5 1000 2 3.00 2.7 74.3 96.1 60 Λ 7th 0.5 200 2 2.64 2.8 (»7.6 X7.2 55 Λ 8th 0.5 500 2 2.16 2.9 66.1) 91.5 47 Λ 9 0.3 1.85 2.7 62.4 62 A. H) 0.3 1.22 2.9 64.3 57 B.

45

M)

continuation

Example no. Conditions of manufacture Treatment water pi I one Whiteness deck valuation of the tilane phosphate lung more soluble IO% igen. (% Rcllcktan /) crane d. Rust- Molar treatment '/ CIt Duration wälirigen Wavelength (mn) prevent- decay (Sld.) part Suspen- qualification
■ ichafl nis (n) temperature SiO: CO (Ciew.%) 350 400 500 (mm)

U 12th 13th

Comparison 3 Comparison 4 Comparison 5

0.2 0.2 0.2

200 500 800

basic blcisilical (1.6 PbO SiOj)

White carbon consists mainly of crushed SiO

Red lead (Pb ₁ O ₁ )

1.03 2.8 59.2 71.6 85.0 60 B. 0.95 3.0 60.3 72.1 86.7 55 B. 0.41 4.1 61.8 72.9 88.2 55 C.

0.07 6.8

0.002 6.9

1 (XK C

KKK F.

It can be seen from Tables 11 and IH above. that by selecting the amount of the water-soluble ingredient contained in the titanium phosphate and silicon phosphate and the acidity to be within the above-mentioned ranges, excellent anti-rust properties are obtained

Which are not only far superior to those of calcium phosphate, zinc phosphate, basic lead silicate and white carbon. which were chosen for comparison, but also considered to those of red lead, which is commercially available as a rust preventive pigment. The phosphate pigments of the above formula (I) according to the invention most preferably contain the water-soluble one Ingredient in an amount of 0.6 to 20%.

ί> The phosphhalpigmenle of the formula I according to the invention are usually used as particles with a diameter smaller than 20 μ and preferably less than 10 μ. A surprising fact consists in the fact that the phosphate pigments according to the invention show no tendency to aggregate, even when they are crushed into finely divided particles with sizes less than 5μ. As stated above, contain the phosphalpigmenia according to the invention at least 0.1% and preferably 0.6 to 20% by weight

«Ι water-soluble component. Usually, it is difficult to crush such a water-soluble component-containing solid substance to a size of less than 10 µ, for example, and even if so is possible. the tendency for aggregation is excessive. However, in the case of the phosphor pigments according to the invention, this tendency to aggregate is surprisingly unduly small, although they contain a water-soluble component which is used to achieve resistance to flames and corrosion

4? is cheap.

The tendency of a finely divided substance to aggregate can be determined in the following way: A Finely divided substance passed through a sieve having an exemplary mesh size is allowed to stand in air of given moisture for a given period of time. This finely divided substance is then sieved with the same sieve, and the amount of particles which pass through the sieve is crhal-

> o th. The inventive phosphate pigments are those whose degree of aggregation is less than 50% and in particular is less than 10%. calculated according to the following equation:

Q =

A- A "

* 100.

where A is the weight of the powder passing through a sieve of a given mesh size, A 'is the weight this through the same sieve after standing for 24 hours at room temperature in air with a relative humidity of 90% powder passing through and Q denotes the degree of aggregation in%.

Manufacture of the pigment

The inventive white Phosphaipigmcntc of the above formula (I) can according to a number obtained from procedures;

The white pigment of the formula (I-1) according to the invention is produced by intimate mixing of amorphous silica, silicates or earth minerals. which consist predominantly of these materials, either with oxyacids of phosphorus. Anhydrides of oxyacids of phosphorus or salts of oxyacids of phosphorus and subsequent calcination of the mixture obtained.

IO

The starting material used for the silica component according to the invention is amorphous silica, colorless silicate or earth minerals, which mainly consist of these components. As amorphous Silicic acid according to the invention are hydrosols of silicic acid, hydrogels of silicic acid, xerogels of Silicic acid and amorphous, calcined products of silicic acid are useful. With the expression used here The term used in crystallography for this purpose as a result of X-ray diffraction analysis becomes "amorphous" designated.

On the other hand, alkali, alkaline earth or aluminum salts of silicic acid can also be used. These can be used in the process according to the invention 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 particularly preferred.

Various mixtures of the above derivatives or the naturally occurring colorless clay-like minerals consisting predominantly of amorphous silica and / or silicate can also be used in accordance with the invention. For example, mixtures containing silica and aluminum silicate in different ratios are suitable as starting materials for the silica land part according to the invention. Furthermore, the starting material for the silica component may contain some impurities to such an extent that the whiteness of the material is not affected. For example, small amounts of metal components of Al, Mg and Ca may be contained therein, for example in the case of acidic clays treated with acid, which are obtained by treating acidic clays with an acid, or diatomaceous earth ^! c, which were obtained in a pure white form by treating the naturally occurring dialome earth. Furthermore, the colorless earth minerals, for example the naturally formed zeolites, diatomaceous earths and high-grade kaolins can likewise be used advantageously in the invention. The term "Erdmincralicn" used here denotes the phyllosilicate materials (clay-like minerals) bound in stratiform, the sterically reticularly bound tectosilicate materials and the natural non-crystalline silicates. Therefore, all silicas or silicates which are obtained as by-products in the inorganic chemical or ceramic industries or which arise as intermediate or end products in these industries can be used as starting materials for the silica material according to the invention.

Furthermore, all oxyacids of phosphorus, for example orthophosphoric acid (H ₁ PO ₄ ), mctaphosphoric acid (HPOj), pyrophosphoric acid (H ₄ P ₂ O ₇ ), hexametaphosphoric acid [(HPOj) ₆ ), triphosphoric acid (H, PjO | ₀ ), phosphorous acid (H ₁ POj) and hypophosphorous acid (HjPOi) can be used. Furthermore, these can of course be used as the starting material! Serving oxyacids of phosphorus can also be used in the anhydride, for example as phosphorus pentoxide (P2O5). Examples of colorless oxyacid salts of phosphorus that can be used are the alkali metal salts, ammonium salts, alkaline earth metal salts, zinc salts, lead salts or aluminum salts of 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 this case, the mixing and crushing of the two materials can be carried out by either a dry or a wet method will. For example, the starting silica component can be used in sol form or hydrogel are added, for which the phosphoroxy acid region is added as an aqueous solution or in slurry form to form an intimate mixture, or the phosphoroxy acid can be added as a liquid wedge to the dried gel or powder of the starting silica region. But the two of them can Starting materials can be mixed by dry milling when a salt of phosphoric acid is used, but a more intimate mixture can be made using either water or another liquid medium.

Although the proportions with which the starting skic acid component and the starting phophoroxy acid component are mixed varies considerably depending on the classes of the starting materials used, this has no effect as long as the final composition is within the range given above.

Next, according to the invention, the intimate mixture of the starting silicic acid component and the starting phosphoroxy acid component is calcined. Even if the calcining temperature. vary considerably depending on the classes of the two starting materials, temperatures in the range from 200 to 1000 ^° C. are generally preferred. From the point of view of the whiteness of the pigment to be obtained, a temperature above 400 ^° C. should preferably be used when calcining the above mixtures. From the viewpoint of both the whiteness and the stability of the pigment obtained, it is generally preferred if the Calcinicrung the above mixtures is carried out at temperatures above 400 ^0C. The Calcinierbcdingungen must be suitably selected so that the above-angegebcncn Anfordernisse be met and it is chosen a temperature above 200 ⁰ C and preferably 400 to ¹ OOO ⁰ C and a period of I to 4 hours.

If the calcination of the mixture consisting of the starting silica component and the starting phosphoroxy acid component with the addition of an inorganic halogen-containing compound, for example a chloride, bromide or iodide of an alkali metal such as lithium, sodium or potassium, is a Chloride, bromide or iodide of an alkaline earth metal such as magnesium, calcium or barium, or one Chlorides, Bromides or Jodides of metals like zinc. Aluminum and tin can run, the Amount of contaminating coloring constituents contained in the above mixture in a noticeable 6> chcm extent can be reduced. The whiteness of the pigment can be improved considerably if the inorganic halogen-containing compound in an amount of 0.01 to (U mol. In particular 0.05 to 0.02 mol Mol SiOi is applied.

On the other hand, the above flame-retardant ammonium phosphate silicate type white pigment may, for example by intimately mixing a combination of the following materials:

a combination of reactive silicic acid, phosphoric acid and an ammonia-nitrogen compound,

a combination of reactive silica, ammonia adsorbed silica and ammonium phosphate; or

a combination of silicon phosphate and an ammonia-nitrogen compound, the ratio being of SiO ^ / PiOj in the range from 0.2 to 5 and preferably 0.5 to 3 and the molar ratio of N H., / HjO, ranges from 1 to 6.

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

Examples of ammoniacal nitrogen compounds are urea. Ammonium carbamate, guanylurea, Aminourea and biurea or biurea can be used in addition to ammonia.

Instead of using phosphoric acid and the ammonia-nitrogen compound separately Ammonium phosphate can be used as a starting material. As ammonium phosphates, the mono-, Di- and tri-ammonium orthophosphates, ammonium metaphosphates and the ammonium salts of Phosphoroxy acids and also ammonium phosphoric acids from P-O-P-TVp can be used. Furthermore you can instead of using silica and phosphoric acid separately, silicon phosphates, for example those of the formula

.tSiO, · VP ₂ O ₅ ,

where .v / v = 1 to 5 are used as starting materials.

The above starting materials are brought into intimate contact, at temperatures ranging from room temperature to 200 ⁰ C. The conditions under which this contact occurs will vary depending on the classes of starting materials used.

For example, after the mixing of silicic acid, phosphoric acid and the ammonia SlickstofT compound the components günstigerweisc usually to a temperature above 8O ⁰ C under such conditions sufficient to volatilize the moisture implemented. On the other hand, when silica or ammonia adsorbed silica is mixed with ammonium phosphate, although mixing in the solid phase is also possible, mixing is preferably carried out at the above temperature using a small amount of water as a medium. Furthermore, when silicon phosphate is reacted with an ammonia-nitrogen compound, the reaction can be carried out by passing ammonia gas directly through the solid silicon phosphate, or the solid silicon phosphate can be mixed with an aqueous solution of the ammonia-nitrogen compound, and the mixture is dried to get the product you want.

Further, if necessary, adsorption of ammonia can be carried out on the obtained solid powder to obtain the desired product which contains the phosphoric acid, silica and ammonia ingredients in the desired areas contains / u received.

The tilane phosphate to be used as rust preventive pigment is according to the invention according to per se known method obtained, but with a sufficient content of the water-soluble component and acidity within the above range is ensured. The material can for example according to the procedures set out in British Patent 1161 141 and US Patent 3,471,252 getting produced. For example, the titanium phosphate can easily by reacting either an inorganic or organic acidic solution of a titanium compound, a titanium salt or a amorphous titanium oxide with an oxyacid of phosphorus or a phosphorusoxyacid derivative which contains the phosphorusoxyacid component can release under the Rcaklionsbedingungen and then calcining the phosphoroxy acid salt of titanium obtained in the desired manner.

To prepare the titanium phosphate for use according to the invention, an inorganic or organic acid solution of a titanium compound, a titanium salt as such or an amorphous titanium oxide in the presence of water either with a phosphoroxy acid or a phosphoroxy acid derivative which can form a phosphoroxy acid residue under the reaction conditions implemented to form a Titanphosphaigeles, the composition of which is within the range specified above. Then this Titanphobphatgel is either dried or calcined in such a way that the water-soluble constituent in the product obtained is contained in an amount of at least 0.1% and before / .ugsvcise 0.6 to 20% and the pH value is 10% igen, aqueous suspension of the product obtained is not more than 3.5 and preferably 1 to 2.5. Although the drying or calcining conditions vary considerably depending on the composition of Titunphosphais, usually, a temperature of 100 to 1000 ⁰ C and preferably 250 to 800 ⁰ C and a period of time selected from 30 minutes to 3 hours, so that the above-mentioned Requirements 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. The zirconium material used as a starting point consists either (1) of an acid solution, which by melting a concentration of zirconium minerals, such as zirconium / (ZrO? · SiO;) and Baddclcyil (ZrOj) with an alkali, if necessary, for Vitrification of the zirconium mineral and subsequent dissolution of the same in a mineral acid such as sulfuric acid, Sal / siiirc or nitric acid was obtained, (2) a zirconium chloride, which in an intermediate stage of the so-called Kroll method, whereby one zirconium mineral in the presence of carbon, two

for example coke, is saved and then chlorine is passed through. (3) a zirconium hydroxide. which was obtained by hydrolysis in the usual way of an acid extract of a zirconium mineral. These starting zirconium materials are reacted with either a phosphorus oxy acid or a reactive derivative thereof, whereupon the obtained zirconium phosphate is treated. The starting amounts of the zirconium material and the phosphorusoxy acid or the reactive derivative thereof are chosen so that the ^; Conditions of the above formula (1-3) are satisfied. Upon calcination of the / irkonphosphats suitable conditions are a temperature in the range of KH) to 900 ⁰ C and a period of .M) dug minutes to 3 hours, so that it is ensured that the water-soluble component cheating at least 0.1%.

As a result, new pigments are of a composition corresponding to the above general formula mcl (I) obtained according to the invention. Of course, the pigments obtained can be used if necessary washed with an acid and / or washed with water and either by the dry method or crushed by the wet process and into a product in the form of a slurry, paste or a Powder can be processed. Furthermore, according to the dispersion capacity of the white pigments according to the invention can be improved if a coating of metal oxides or organic substances on their upper surface surface is formed in the usual way.

According to the invention, the pigment is preferably comminuted in such a way that the conditions of the above formula (II) are met, whereby aggregation of the particles is prevented. To achieve this goal, the pigments obtained by the voisichenucn process must be in an organic solvent which does not dissolve the water-soluble constituent of the above phosphates, 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-llexane. Kerosene, benzene, toluene and xylene and halogenated hydrocarbon solvents such as chloroform, methyl chloride or tetrachlorethylene are comminuted using a grinding device, for example a ball mill or tube mill. If a low-boiling solvent is used in this case, the pigment can be obtained in a finely divided form without aggregation of the pigment particles. If a resin such as rosin or natural resins, alkyl resins or ^E: .rdölharze or higher fatty acids such as stearic acid, or metal soaps, such as calcium or barium stearate can be previously dissolved in the above solvents, and is carried out the size reduction of the pigment in this solvent, can then When the solvent evaporates, the surfaces of the pigment particles are coated with these substances. Further, the pigment pulverized in the above solvents can be supplied to its intended end-use in the state as it was obtained (state of slurry or state of cake). On the other hand, the pigment can be comminuted in a paint vehicle specified below and passed on to its intended end use in this state. In order to further accelerate the drying of the applied film while preventing interaction with the hardener contained in the carrier, it is effective to add 0.5 to 5% by weight to the particles of titanium phosphate or silicon phosphate, based on titanium or silicon phosphate, of an oxide of an alkaline earth metal , for example Magncsium or calcium oxide, aluminum oxide or silica gel to be coated.

Uses

The white phosphate pigments according to the invention not only show excellent reflectance Ultraviolet and near ultraviolet, but also have new properties, i. H. excellent Flame resistance and rust preventive properties that of the usual white pigments not be shown. - »5

When the white phosphate pigments of the present invention are incorporated in a resin or in a carrier can be dispersed and applied to a surface, a pronounced flame resistance of the Resin-like molded article, coating or the substrate will be reverberated. Even if a familiar one White pigment, such as titanium dioxide, is dispersed in a carrier and then applied to paper the self-burning property of the paper is not prevented; However, if a coating that is inventive so If the appropriate white pigment is applied to paper, the self-burning properties of the paper can come in handy be prevented.

The white pigments according to the invention are thus valuable as pigments for paints, as pigments for Used in papermaking, as gloss breakers for textiles and as pigments for use with the various molding resins. They can also be used in known pigments to improve their Whiteness can be incorporated or they can be used as white pigments to achieve a fire resistant wedge or Flame retardant properties as well as to achieve corrosion resistance for different classes be used by molded articles.

The phosphate pigments according to the invention can be used, for example, in paint carriers or molding resins Amounts from 1 to 300 parts by weight, preferably 5 to IOC parts by weight per 100 parts by weight of the carrier base or m> of the resin are mixed in.

According to one embodiment of the invention, a rust-preventive paint for metal surfaces results, that of (a) a support containing a base material forming a coating film, preferably from the group of alkyd resins, epoxy resins, air-drying oils, phenolic resins, polyvinyl acetates, vinyl chloride resins or polyvinyl acetates is selected, and (b) a rust-preventive pigment which is composed of a Phosphate of a composition corresponding to the formula

M ¹ C). · ΛΥ (ο. \ 1.5 + - \ Ρ.Ο <

consists, άο'.ίιι

M ¹ silicon. Titanium or zircon. Y is a nitrogenous base or an oxide of the formula

MO ₁ ,

wherein M 'is an alkali metal, alkaline earth metal. Aluminum. Lead or zinc and «the value of the metal

M '' represent

ν is a positive number up to 6 including C), and m is 1. Calls Y is a nitrogenous base. and the value / i if Y is the meaning

Has.

mean, where the phosphate contains at least 0.1 "/» of a water-soluble component, is built up and furthermore, the phosphate is present in an amount of 1 to 300 parts by weight per 100 parts by weight of the base material constituting the coating film.

The above rust preventive paints according to the invention can easily be used as an undercoat on a Metal backing applied by the consumer and show excellent adhesion between the

Paint and the metal base as well as the finally applied coating. In addition, the rust preventive effect is maintained for a long period of time.

Alkyd resins, epoxy resins, air-drying oils, phenolic resins, polyvinyl acetate, vinyl chloride resins and polyvinyl acetate, which are used individually or in combination of 2 or more kinds, are suitable as the base material for the formation of the coating film of the carrier material. del can be. These base materials used to form the coating film are used in the form of either a solution in an organic solvent or an aqueous emulsion.

The alkyd resins are either the condensation products of a 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 polyhydric alcohol, such as ethylene glycol, propylene glycol, glycol cerin, trimelhylolpropane, pentaerythritol, mannitol or sorbitol or modified alkyd resins, which by condensation of 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 marzes such as rosin, copal or shellac or synthetic resins such as phenolic resins, urea resins and melamine resins! were obtained.

These alkyd resins can be in solution form, dissolved in an aromatic hydrocarbon such as toluene or Xylene, or in the form of an aqueous emulsion by emulsification with a known emulsifier such as nonionic surfactants, kaiionic surfactants or siloxaneoxyalkylene copolymers. Of course, the carrier material can be equipped with a dryer, for example cobalt naphthenate or manganese naphthenate. as is common with such approaches.

As epoxy resins, bisepoxy compounds obtained from a condensation product of epichlorohydrin can be used and a polyhydric phenol such as a bisphenol or resole, and combinations with a hardener such as phenol 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 can be used or fatty acids can also be used. These epoxy resins are diluted with a mineral oil and used as

Carrier used.

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

As the phenolic resins, in addition to the usual resol type phenolic resin paints, those consisting of one with fatty acids or a resin acid with subsequent addition of a drying oil and heat action modified phenolic resins or those phenolic resins that are formed from condensation products of a

Alkylphenol, for example p-tert-butylphenol and formaldehyde with subsequent addition of a dry

Knendes oil and heat treatment exist, usable. These phenolic resins are diluted with a

Ketone or an aromatic hydrocarbon is used. Polyvinyl butyral and copolymers with vinyl alcohol units and vinyl butyral can be used as polyvinyl acetate Units are used.

Favorably, as vinyl chloride resins, the copolymers of vinyl chloride with a small amount of Vinyl acetate and the ternary copolymers of vinyl chloride, a small amount of vinyl acetate and one 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 hydrochloric acid solvent as a solvent with a small amount of a Pluslifi / iurcr einsel / .i. On the other hand, the vinyl chloride resins can also be produced by means of surface-active agents emulsifiable and dispersible and used in the form of an aqueous emulsion.

As polyvinyl acetate, polyvinyl acetate or aqueous emulsions of a Vinylaecla'har / cs, which a small amount of vinyl alcohol unit or a small amount of vinyl alcohol and vinyl butyral F.in- ^; heal contains, usable.

The above vehicles for the anti-release paints are known in the art. To this Paint strikers can, if necessary, pla. Dioetyl phthalate and n-llydroxymelhyl phthalamide. Dryer, such as cobalt naphthenate, manganese naphthenate, Cobalt linoleum, lead naphthenate and zirconium phthalate, hardeners such as benzyl peroxide and methyl ethyl ketone peroxide oxide, dispersants such as aluminum slearai, lecithin and polyethylene glycol alkyl ethers. Emulsion stabilizers, such as polyvinyl alcohol and methylcellulose, emulsifiers such as triethanolamine and surface-active agents, Thickeners or extenders, such as kaolin, magnesium silicate. Calcium silicate and Silicagcl or other rust preventive Pigments are added.

Although the rust prevention paints according to the invention are particularly effective for preventing the ι> Are also effective in preventing rusting of various other metals, such as copper, nickel, chromic acid treated iron, galvanized iron, and magnesium alloys impede. To apply the rust preventive paints according to the invention to ice substrates the different methods of applying paints depending on the grain of the srrs paintwork contained pigment are applied. For example, if the content of pigment is large, the order can: o Apply by means of a brush, spatula or roller, while, if the pigment content is low, the application be done by spraying or dipping or by electrostatic or electrophorelic processes can. In any of the foregoing cases, use of water, diluent, or others Thinners to reduce the viscosity of the paint. The rust preventive agents according to the invention Paints can be applied directly to the surface of the iron backing or can be applied to the J * Surface of iron substrates that have received a phosphoric acid treatment can be applied.

The rust prevention paints which contain the silicon phosphate or titanium phosphate according to the invention as pigment contain, not only show superior rust prevention properties over the usual rust prevention paints, but also show no tendency to damage the carrier material. aside from that the anti-rust paints according to the invention adhere to a> υ after application as an undercoat Metal surface quite excellent on the metal surface and keep the rust preventing effect during very long periods of time, even when exposed to corrosive conditions for long periods of time will.

Furthermore, the rust preventive paints according to the invention are white in color and therefore have no color Tendency to discolour the metal substrates with a specific color. Therefore they bring the Merkjs sometimes with it that a pure retention of the color of the final coating is possible, even if the coating on the auschiäcikrsdcri (Jbsr / agös is relatively thin. The rust prevention paints according to the invention are also superior in that they are non-toxic since they do not contain lead. Therefore, the anti-rusting paints of the present invention can be used for various purposes as white rust preventive paints are used and the various common rust preventive paints, Replace zinc chromate primers and primers and wash primers. As examples, a number of approaches are given below.

Recipe I.

White anti-rust paint based on linseed oil

Parts

Tilanphosphhal according to Example 2 220

Rutile Type Titanium Dioxide 110

Magnesium silicate 250

Raw linseed oil 210

Heavy bodied linseed oil 110

6% cobaline naphthenate 2

h% manganese naphthenate 10

Mineral Spirit 88

i.ezcpi 2

White alkyd-based rust preventive paint

Titanium phosphate according to Example 2 H) O

Silicon phosphate according to Example 1 M)

Ruliliyp titanium dioxide! 00

Calcium carbonate 210

With soybean oil niodili / ieries Alkydhar / (50% solution in Mincralspirit, 280 Surer number 10)

Linseed oil 3

24% Bleinaphlhen.it I

ti'- cobalt naphlhenate I.

Mineral spirit 245

Phcnt har / primer

: 5 silicon phosphate according to Example I 14

Rutile-type titanium dioxide 10

Potassium silicate 20

Dehydrated oil phenol ether ester resin 18

Xylene 20

: -ύ Mineral spirit 18

Recipe 4

Rust prevention and lamb prevention paint based on epoxy

Parts of titanium phosphate according to Example 2 100

Rutile-type titanium dioxide 100

Alkydhar modified with dehydrated castor oil / (50% solution in 4 (M)

Mineral spirit)

Aluminum stearal 100

Soybean lecithin .T

6% cobalt naphthenate 2

6% zirconium catalyst 10

Xylene 120

Naphtha 113

Recipe 5

Vinyl chloride resin primer
Parts

Tilane phosphate according to Example 2 22

Vinyl chloride resin *) 15

Tricresyl phosphate 3

«Ο methyl ethyl ketone / toluene (1: 1) 60

*) Ternary's copolymer with 91% vinyl chloride, 3% vinyl acetate and 6% vinyl alcohol. (.,); T ... h,., "= 0.57

Recipe 6

White rust prevention and flame retardant pigment based on polyvinyl acetate

Parts

Titanphosphhal according to Example 2 130 Silicon phosphate according to Example 1 40 Rutile-type titanium dioxide 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 Polyamidhar / (50% solution) 50 Titanium dioxide 50 Titanphosphhal according to Example 2 50 Ammonium imphosphate silical according to Example 9 30

Zinc borate 30

Melamine har / 20

Strength 5

Chlorinated paraffin 10

Recipe 8 Ju

Emulsion type flame retardant paint

Parts

Water 100 .'5

Polyvinyl acetate emulsion (55% solids) 50 Rutile-type titanium dioxide 50 Dibutyl phthalate 5 Ammonium phosphate silicate according to Example 9 20 Dicyandiamide 20 Pentaerythritol 50 Chlorinated Purutil η 5

Recipe 9

45 moldings made of unsaturated polyester

Parts

Unsaturated polyester resin 100 Peroxide 0.2 to 3 Naphthenate 0.2 to Ammonium phosphate silicate from Example 9 5 bis Chlorinated Paratlin 5 üis Pigment 0 his

Recipe 10

Polyvinyl butyral mesh primer

Parts

Silicon phosphate according to Example 1 10 Polyvinyl butyral 8 Fcin-zcrlcillc silica 2 Isopropunol (99%) Wl

Butnnol 16 to

Water 4

The following examples serve to explain the winding further. example 1

A white pigment of silicon phosphate was made using a xerogel of the silica and of Orthophosphoric acid produced. The manufacturing method and properties of the obtained white pigment are shown below.

The silicon phosphate was prepared in the following manner: A commercially available sodium silicate solution was neutralized with sulfuric acid to gel the silica, whereupon this gel was washed thoroughly to form small, purified aggregates of the hydrogel of the silica and was then dried. The resulting silica xerogel was then impregnated with a mild phosphoric acid component ίο by adding a technical grade orthophosphoric acid (first JIS quality, 85% HjPO ₄ , specific weight 1.690). The composition of the silicic acid component and the phosphoric acid component was adjusted so that the molar ratio of SiO .: PjO _{5 was} 1: 0.5. After drying this impregnated product was calcined for 2 hours at 800 ⁰ C in an electric furnace, subsequently comminuted wet for 3 hours in a chamber filled with balls pot mill using methyl alcohol as a grinding medium. After the methyl alcohol serving as the grinding medium was separated and recovered, the product was dried. A finely divided white silicon phosphate pigment was obtained.

The resulting fine, white silicon phosphate pigment was then identified by means of an X-ray diffraction analysis and the properties such as whiteness, in particular reflectance in the ultraviolet range, water-soluble constituent, pH of an aqueous suspension, particle size and pH value were determined Extent of secondary aggregation. The results are summarized in Table IV.

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

The content of water-soluble constituents was determined in the following way: 20 g of the pigment powder

were placed in a 100 ml volumetric flask. About 70 ml of water were added and the mixture was heated for 5 minutes and then cooled, after which water was added up to the calibration mark. The content then turned out to be good shaken and then left to stand for 1 hour. Thereupon the contents of the flask were with

.ίο filtered through a dry filter paper. The first 20 ml of filtrate was discarded, followed by 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 for 1 hour at 105 to 110 ⁰ C the vessel was weighed. The amount of water-soluble component contained in the sample was, in percent by weight, was then calculated from the weight of that obtained after evaporation of the liquid

Arrears calculated.

The pH of the 10% aqueous suspension was determined in the following way: An aqueous suspension with a concentration of 10% was shaken well and dispersed ^{at room temperature (23 ± 2 ° C.).} This suspension was left to stand for 1 hour and the pH was then determined with a pH meter. The particle size was determined by determining the size of the pigment particles when examined with a microscope.

The extent of aggregation (Q) was determined as follows: The ^{pigment powder, dried at 90 to 110 °} C., was first passed through a 74 micron (100 mesh) sieve, whereupon the powder was placed in a desiccate, r. which was adjusted to a relative humidity of 90% with a sulfuric acid solution. was allowed to stand so that the moisture was fully adsorbed by the powder. The powder sample was then sieved again, shaking for 10 minutes on a 74 micron (100 mesh) sieve using a Sicb shaker (product of Maruto-Scisakujo. Japan). The sample part remaining on the sieve at this point in time was given in% and this value was given as the degree of aggregation (%).

As a rust resistance test, the general procedure for painting in accordance with JIS K 5400 was used, and the rust resistance tests were evaluated by means of the weather test and the Salt water spray testing of film coatings applied to a soft steel plate. When this rust resistance test was carried out, tests were carried out at the same time with commercially available rust-preventing pigments such as red lead, lead cyanamide and zinc chromal. ZinkY.eiß, and Calciumphosphal executed and comparative evaluations against the case of using the silicon phosphate according to the invention performed.

The results are given in Table IV. To produce the coating compositions with these pigments, 100 parts by weight of the individual pigments were used

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 powder in a ball mill. the N) The resulting paints were used and the rust resistance test was carried out in the following manner

executed.

A cold-rolled steel plate (JIS G 3141, regulation B) was used as the soft steel test plate in accordance with JIS K 5400. This plate, the entire surface of which had been polished thoroughly and evenly with a No. 280 waterproof sandpaper. until it showed a Mclullglan / is for use with the protruding> suitable for the upcoming test

The obtained steel plate was used and the coating was made into one according to JIS K 5400 procedure Film thickness of 40 to 50 μ applied with the spray method, after which by itself at room temperature and normal humidity.

The weathering test was carried out according to the conditions according to JLS K 5400 in the following manner: The coated surface of the Tesl plate was exposed to air in the open air. After a period of 2 years it was the coated surface of the individual panels was observed in comparison and the condition of the external coated surface was compared and assessed. The applied evaluation procedure passed in a classification of the state of the rust of the plate surface in five classes with the ratings A, B, C, D and E in the following way:

A: No rust found, so there is practically no change from the time the test plate was painted

occurred;

B: Rust of the order of pinholes found;

C: Rust of parts of the test plate and cracks and bulges of parts of the film coating found; D: Larger part of the test plate rusted and the greater part of the film coating peeled off; E: Breakage of the film cover and rust occurred over the entire substrate.

The salt water-Sprühtesl carried out according to the conditions according to JIS K 5400 in the following manner: The coated surface was exposed to the Versuchsplalte scr-Besprühungskammer over a period of 300 hours of salt spray water at 6O ⁰ C in a salt-water ■. The coated surface of the exposed tiles was then observed in comparison and the condition of the rust was evaluated and classified into five classes, A, B, C, D and E, as in the case of the above weathering test.

The results of the above experiments to determine the rust resistance of the pigments are in Table! V zussnunengefaüi.

Furthermore, the flame resistance kit test was carried out in the following way: After the pigment closed a paint was processed with a binder, a test sheet was made by coating a Paper sheet made with this coating. The FcuerbesistentkitselTckl was then determined by a Flame was directed against the prospect sheet. This experiment was also carried out with common technical white pigments, for example titanium dioxide of the rutile type, white carbon and ammonium phosphate and the flame resistance of these pigments was rated and matched that of the n * h of the present example silicon phosphate obtained compared.

When processing these pigments into paints, a commercially available latex (Dow Chemical Product 402) was used as a binder and 3 parts by weight of this were used together with 10 parts by weight of a han- the usual Mr. laminate resin powder (technical reagent from Wako Junyaku Co., Japan) and 10 parts of water as well as mixed with 10 parts by weight of the individual pigments and a homogeneous one by thorough mixing Paste received. Each obtained film was applied to both ropes of drawing paper to a thickness of 1 to 8 mm and dried. Small pieces of the arches were made used as test pieces.

The flame resistance of the test pieces was first determined by directing a flame against them and determining whether the flame spread. In case of flame spread took place, the test piece has no flame resistance and was locked out from further investigation. The test pieces which were found to be lambskin were subjected to a test for an animal which had received fire-retardant treatment; H. the test according to ASTM D 77-46. The - »o Length in mm of the charred found on the surface if a flame was applied to the test gap for 12 seconds was applied was determined and the degree of flammability based on the length of the char estimated. The shorter the charring length, the better the flame resistance.

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

2 SiO _: PA identification by means of X-ray diffraction analysis Si.p, O,

Whiteness (% reflectance): Wavelength (πΐμ)

350 67.6

400 91.2

500 94.5 ■ *>

I- Water-soluble component (% by weight) 26.9

t'5 pH of a lOVnigcn, aqueous suspension 2.8

Particle size (μ) below 5 I: aggregation waste (Q) (%) 5 ^ml

Weathering test salt water spray test

Pigment of the present example red lead (PbjO.,) Lead cyanamide (PbCN _:) zinc chromate (K _: O 4 ZnO - 4 CrO ₁ ■ 3 H _: 0) zinc white (ZnO) calcium phosphate [Ca ₁ (PO ₄ ).]

Flame resistance test (mm / 12 sec.): Pigment of the present example rutile titanium dioxide (TiOi) white carbon (SiO;) ammonium phosphate [(NH,): HPO ₄ '|

A. A. B. B. B. B. B. B. C. D. F. E. 8th no Flame resistance no Flame resistance 20th

It can be seen from the above values that the silicon phosphate pigment prepared according to the present example a white pigment which gives very satisfactory results in terms of rust resistance and shows flame resistance.

Example 2

A white pigment consisting of tilane phosphate was made from titanium tetrachloride and orthophosphoric acid manufactured. The process used to make this white pigment and its properties are given below.

The titanium phosphate was prepared in the following manner: A solution of technical grade titanium tetrachloride and technical grade orthophosphoric acid was placed in a high speed mixer and slowly reacted to form a white titanium phosphate glass. After Algerung this gel at a temperature of 60 to 70 ⁰ C, it was thoroughly washed first with aqueous hydrochloric acid and then with water. The pigment was prepared in such a way that the composition of the titanium and phosphoric acid constituents were adjusted so that a molar ratio of TiO.: P ₂ O <1: 1 was obtained at this point. After drying of this washed Titanphosphatgels was calcinierl for 1 hour at 400 ⁰ C in an electric furnace, subsequently comminuted wet for 3 hours in a chamber filled with balls pot mill using methyl alcohol as a grinding medium. After separating and recovering the methyl alcohol as an abrasive, the product was dried, and a pure-divided white titanium phosphate pigment was obtained.

The identification of the single-crinkled 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 im Ullravioletl range, content of water-soluble constituents, pH of a 10% aqueous suspension, particle size and extent of aggregation were made. Both the rust resistance and the flame resistance were examined and evaluated in the same manner as in Example I. The results are in Table V summarized.

Table V

Identification by means of X-ray diffraction analysis Whiteness (% reflectance) Wavelengths Imu)

predominantly non-crystalline T1P1O7

350 400 500

Water-soluble constituent (% by weight) pH of a 107-strong aqueous suspension Particle size (ti) Aggregation factor (Q) (%)

Rosi resistance test: weathering method SaI water spray method

Flammability test (mm / 6 sec.)

60.0 105.0 105.0 2.55 1.2 and a half 2

Λ
A.

It turns out that the titanium phosphate pigment produced according to this example is a white pigment which shows very interesting results in terms of comfort and convenience.

20th

Example 3

liin white pigment, which consisted of zirconium phosphate, was made from zirconium nitrate and orthophosphoric acid. The manufacturing process and the properties of the product are given below.

The zirconium phosphate was prepared by adding a technical grade zirconium nitrate solution and a technical grade orthophosphoric acid to a high-speed stirring mixer, in which the ingredients were mixed and reacted to form a white zirconium phosphate, followed by thorough washing, first in aqueous hydrochloric acid and then in water. The composition of the zirconium and phosphoric acid components were adjusted so that the molar ratio of ZrO ₂ : P ₂ O _{5 was} 1: 1 at that time. After the washed zirconium phosphate gel had been dried, it was ^{calcined for 1 hour at 20O 0} C in an electric furnace, whereupon a wet reduction of the product was carried out as in Example 1 using methyl alcohol. The comminuted product was then dried and a finely divided white zirconium phosphate pigment was obtained.

The identification of the finely-torn, white zirconium phosphorous pigmentation obtained was carried out by means of X-ray diffraction analysis and determination of the properties, such as whiteness, content of water-soluble constituents, pH of an aqueous suspension, particle size and degree of aggregation carried out. The trials on Rust resistance and flame resistance were carried out and evaluated as in Example I. The received Results are summarized in Table VI.

Table Vl: n Identification using X-ray diffraction analysis ZrP-O- Whiteness (% reflectance) Wavelength (πΐμ)

350 117 2 *

400 115

500 115

Water-soluble component (% by weight) 11.5

pH of a 10% ipen, aqueous suspension 2.45

Particle size (α) below 5 Amount of aggregation (Q) (%)!> Rust resistance test: Weathering procedure A _{; 5} Salt water spray method A. Flame resistance test 12

It can be seen from the above values that the zirconium phosphate pigment prepared according to this example is a white pigment, which gives very satisfactory results in terms of rust resistance and Shows flame resistance.

Example 4

This example explains the case where various silicon phosphate, titanium phosphate and zirconium phosphate pigments are used as rust preventive pigments.

15 classes of finely divided, white silicon phosphate pigments were produced according to the procedure given in Example 1 in the following way: The silicon phosphate produced from a xerogel of silica and orthophosphoric acid in such a way that the molar ratio of SiO ₂ : P ₂ O (indicated by the number nbei SiOj · / 7P ₂ OO, as given in Table VII, were then treated at the temperatures and periods of time listed in Table VII. The products obtained were wet-crushed as in Example 1 using methyl alcohol and then dried and obtained pigments.

14 classes of finely divided, white titanium phosphate pigments were prepared according to the method of Example 2 in the following manner: The titanium phosphates prepared from titanium tetrachloride and orthophosphoric acid in such a way that the molar ratios of TiO ₂ : P ₂ O ₅ (indicated by the number π at TiO ₃ · / IPiO ₅ ) had the value shown in Table VI, were then treated at the temperatures and periods of time given in Table VI. The products obtained in this way were then comminuted as in Example 1 using methyl alcohol and then dried to give the desired pigments.

Six classes of finely divided white zirconium phosphate pigments were produced according to the procedure of Example 3 in the following way: The zirconium phosphates produced from zirconium nitrate and orthophosphoric acid in such a way that the molar ratio of ZrO ₂ P ₁ Oj (given as a number η of ZrOj · / JP ₂ O ₅ ) had the value given in Table VI, were then treated at the temperatures and periods of time given in Table VI. The product obtained was wet comminuted as in Example 1 using methyl alcohol and then dried and the desired pigments 6! obtain.

The properties, such as the pH value of the aqueous suspension, include the water-soluble constituent and the extent of aggregation of the above 35 kinds of fcin-divided white pigments were determined. The results are summarized in Table VI. The rust resistance select was as in Example I by the Weathering and salt water spray tests are rated and these ratings are also given in Table VII.

The values in the table show that very satisfactory results in terms of rust resistance have been obtained in cases where the content of water-soluble components is at least 0.1% and was preferably at least 0.6% and were further obtained when the pH of the aqueous ■ .Suspension was not greater than 3.5.

Table VU

^J robe no. Silicon.
Titanium or conditions
Manufacturing the phosphate Hand-held
lung
Time liigenscharten of the phosphal-
pigmentc water
more soluble
Duration
part Aggre
gation Rust resistance
valuation 1
i Zircon Molar
condemnation
in)
M (J ₁ Treatment
lung
tcnipe-
ralur (Hours.) pll the
angry
Suspen
sion (Ciew .-%) (%) Bewitte- SaI /.-
water
try spray test 1 "P, 0" CC)

1 2 3 4 5 6 7 8 9 10 Il 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

60 31 32 33 34

65 35

Silicon

as well

as well

as well

as well

as well

as well

as well

as well

as well

as well

as well

as well

as well

as well

titanium

as well

as well

as well

titanium

as well

as well

as well

as well

as well

as well

as well

as well

as well

Zircon

as well

as well

as well

as well

as well

0.1

0.2

0.2

0.3

0.3

0.5

0.5

0.5

0.7

0.7

0.7

0.2

0.3

0.3

0.3

0.5

0.5

0.7

150 150 500 300 600 300 500 800 500 700 900 400 1000 400 1000 250 110 250 500 250 500 250 500 800 400 600 850 500 800 150 300 900 150 400 700

2 2 2 2 2 2 2 2 2 2 2 2

2 I 3 2 2 2 2 2 2 2 3 3 3 2 2 1 1 1 1 I 1

3.5

2.8

3.0

2.8

2.9

2.6

2.7

2.8

2.6

2.7

2.8

1.8

2.7

1.7

2.5

2.8

2.4

2.6

2.9

2.2

2.5

1.6

1.9

2.7

1.2

1.9

3.7

0.7

1.9

2.3

2.5

3.7

2.3

2.9

3.8

0.28 1.17 0.56 1.57 1.03 4.69 3.00 2.64 5.73 4.22 3.17 9.75 5.75 9.87 5.98 0.15 0.20 0.14 0.12 0.69 0.52 1.23 0.89 0.25 2.55 0.75 0.07 12.20 2.04 33.8 15.5 0.8 14.2 6.7 0.1

2 2 2 2 1 5 5 3 5 3 2 1 I.

Example 5

In this example, the various silicon phosphate, titanium phosphate and zirconium phosphate pigments are used as lamb-resistant pigments.

As the phosphate pigments, ten kinds of fcin shown in Table VU were divided. white phosphate pigment from samples 4, 8, 12, 14,17,21, 23, 25, 3ü and 33 used and the flame ignition test carried out according to the procedure of Example I. The ratings obtained are shown in Table VIII summarized.

Ks results from the values that a satisfactory flame resistance is shown by the single-colored white phosphate pigments examined in this example.

Table VIII

l'robe no.

Silicon, titanium or zirconium

Conditions for the formation of phosphate

Moliirvriiltnis treatment- processing part

MOj ΙΙ \ 'Λ),

temperature

(SnI)

r lamb resistance test 15

(mm / 6 sec.)

is 4th
8th 12th 14th H 17th 21 23 25th I.
I. 30th
32 1

Silicon 0.3 JOU 2 13

also 0.5 800 2 10

also 1.0 400 2 8

also 1.5 400 2 8

Titanium 0.3 250 2 15

also 0.5 500 2 14

also 0.7 500 2 13

also 1.0 400 3 10

ZirkorT 0.5 150 1 15

also 1.0 150 1 10

Example 6

According to this example, white phosphate pigments are made using various amorphous silicas. Four types have been used as amorphous silicas:

a) acid-treated acid clay (composition 94.28% _SiO;, 1.49% AUO _1, 0.39% to Fc, 0 ,, ignition loss 3.36%) obtained by removal of the acid-soluble basic components of an acidic Montmc "MIonitton through. thorough treatment with sulfuric acid had been obtained,

b) a material obtainable from a silica gel by roasting at 250 ° C., the gel being commercially available for Application as drying and adsorbent is available. the roasted product obtained was crushed,

c) by treating an iron sand slag with dilute sulfuric acid to form a silica brine which contained impurities, the impurities after the gelation of the silica were removed, obtained silicic acid hydrochloride and

d) a commercially available powdered silica gel product for reagent use.

For each of these silica materials (quality first, according to JIS 85.0% H PO _{4 1} specific gravity 1.69.) Was added to technical orthophosphoric acid in an amount such that the molar ratio of _{SiO: P;} O <had the value of 1: 0.5, the two ingredients then being mixed in a mortar for thorough and intimate contact.

After drying the individual mixtures, they were ^{calcined for 2 hours at 800 °} C. and then wet comminuted as in Example 1 using methyl alcohol, whereupon drying was carried out and the individual finely divided white pigments were obtained.

The properties of the individual finely divided white pigments obtained, such as whiteness, content of water-soluble component, pH of a 10% aqueous suspension, particle size and degree of aggregation were set. Furthermore, the rust resistance test was carried out using the salt water spray method and of the flame resistance test. The results are shown in Table IX.

23

Table IX

Exit pebbles aurally

WeiUgr.ui (Ki-Ilckiun / ". (Wavelength niii)

350 400 4S (|

500

Water- pH of the particles- Aggre- Rust- Flame

Come on-

IO "/ nigen big

licher wiiUn-Bcsl.mdgen
lcil suspen-

55Ü (%)

Galion resists national wedge test attempt

'"a) White coal 78.5 94.0 94.5 95.2 95.5 2.0 fabric, made

from sour clay

b) silica gel as 83.3 93.2 96.7 98.1 99.2 2.5

15 reagents / for

Drying u.

adsorption

O silica 76.5 90.4 <> 2.1 92.8 93.4 2.8

hydrogel,

: n made from

Eisensandschiacke
d) Silicagelreugen / 75.8 95.4 94.0 100.0 100.0 2.5

2.9 under- 2
half past five

2.8 under- 2

half past five

2.8 under- 2

half past five

2 8 under- 2
half past five

K)

10

10

10

It follows that the pigments obtained are very satisfactory white phosphate pigments, even if various amorphous silicas are used as starting materials.

Example 7

This example describes various white phosphate pigments made using various silicates and earth minerals were produced.

Four classes of silicates were used: aluminum silicate (Al ₂ Oi · SiOi), calcium silicate (CaO · SiOi), magnesium silicate and sodium silicate (0.3 Na _; 0 · SiOi).

Four types of natural earth minerals were used: The acidic clays of kaolin and M.on mori lonite were chosen as the stralified bound material of phyüGkieselsüuresäUsn, while for the unnatural silicates a zeolite was chosen and for the natural non-crystalline silica salts diatomaceous earth became. The various Erdmineralicn were either used in the obtained natural state or after calcination at 800 ⁰ C.

Commercial orthophosphoric acid (first grade according to JIS, 85.0% H ₁ PO ₄ , specific weight 1.69) was added to the individual silicates in the amounts given in Table X, and the orthophosphoric acid was added to the earth minerals in a molar ratio of the silicic acid component to the Phosphoric acid constituent of 1: 0.5 was added, after which the mixing of the two starting materials was effected by thorough and intimate contact of the constituents in a mortar.

After drying these individual mixtures, they were then calcined at 800 ° C. for 2 hours as in Example 1 using methyl alcohol wet crushed and then dried! and the individual finely-divided white pigments obtained.

The properties of the finely divided white pigments obtained were determined as in Example 6 and further, the rust resistance test by a salt water spray method and the flame resistance test executed with these pigments; the results are given in Table X.

Amount of Whiteness 21 400 500 59 342 ?H Part- Aggre Rostbe Flame retardant 5 Table X admixed (% Rcfleklan /} small gation constant- constant- Starting point th phos- 103.0 102.3 water coarse wedge wedge and earth mineral boric acid 98.0 100.2 more soluble attempt attempt 10 (m! / IOOg) (Wavelength π \ μ) Duration (μ) <%) 101.1 102.7 part 25th 350 95.0 97.4 (%) 3.5 under 2 A. 13th silicate 78 99.2 100.7 3.0 half past five 3 A. 13th aluminum 98.2 97.6 99.3 1.2 15th silicate 59 87.2 1.3 3.0 under 2 A. 13th (AI ₂ Oj - SiO ₇ ) 98 95.4 100.0 2.9 half past five 3 A. 13th Calcium silicate 68 94.5 1.2 2.8 under 2 A. 12th (CaO ■ SiO ₂ ) 204 86.8 1.4 2.2 half past five 5 A. 12th 20th magnesium 87.1 97.0 99.5 1.3 silicate 4.9 ml / 88.6 1.5 2.6 under 2 A. 10 (MgO SiO ₂ ) 100 ml half past five Sodium silicate 75.8 1.7 (0.3 Na, 0 11.6 ml / 2.0 under 4th A. 10 25th • SiO ₂ ) 100 ml half past five NaOH 77.0 77.5 81.6 1.9 34.97 g / l SiO ₂ 30th 84.45 g / l 92.5 94.8 Earth minera! Like him 2.7 under 2 A. 12th kaolin hold 90 half past five SiO ₂ 79.35, 66.1 1.3 AI ₂ O, 17.64, Calci- 2.8 under 2 A. 12th 35 Fe, O ₃ trace, nierles half past five CaO 0.38, Product 90 69.2 1.3 MgO 0.26, Annealing lust 3.34

Sour tone

SiO ₂ 78.65. Al ₂ O., 13.12, Fe ₂ O ₁ 0.57, CaO 1.13, MgO 3.5, loss on ignition 3.15

Zeolite

SiO ₂ 66.08, Al ₂ O, 11.92, FCjO, 0.40, CaO 2.03, MgO 0.04, TiO ₂ 0.04, Na ₂ O 2.07, K; O 2.05, Loss on ignition 15.86

Diatomccncrdc

SiO ₂ 79.56, ΛΙ, Ο, 6.37, Fe ₇ O, 3.03, CaO Π. 16, MgO 1.13, loss on ignition 8.36

How received 43.5 59.8 72.3 1.2 hold

CaId- 63.7 89.7 92.7 1.2

nicrles

product

How received 49.2 60.7 72.3 1.3 keep

Calci- 73.0 87.0 87.8 1.3

ned

product

2.8 2.8

3.0 3.0

under- 2 half past five

under- 2 half past five

under- 2 half past five

under- 2 half past five

How received

Cnlcined product

21.3 34.2 49.2 l.i

56.6 90.8 95.9 1.1

2.7 2.8

under- 2 Λ

half past five

under- 2 Λ

half past five

12 12

13 13

12th

12th

It can be seen from the above results that when the various silicates and the various earth minerals are used in the production of the wet pigments and when the amount of the mixed phosphoric acid in the range according to the invention excellent results can be obtained.

Example 8

This example describes white phosphate pigments made using the various Phosphorusoxyacids and various salts of phosphorusoxyacids were produced.

Five types of phosphorusoxyacids have been used: phosphoric anhydride (P ₂ O ₅ ). Meiaphosphoric acid, pyrophosphoric acid, phosphorous acid and hypophosphorous acid.

Twelve types of salts of phosphorusoxyacids were chosen: ammonium orthophosphate, disodium orthophosphate, sodium pyrophosphate, sodium hexametaphosphate, sodium metaphosphate, sodium tripolyphosphate, monopotassium phosphate, tricalcium phosphate, aluminum phosphate, zinc phosphate, sodium phosphite and Sodium hypophosphate.

The finely divided silica material used in Example 1 was used as the starting silica component (Xerogel) used.

The two starting materials were mixed thoroughly and intimately in a mortar in such proportions that the molar ratio of SiO ₃ : P ₂ O _{5 was} 1: 0.5. The components are mixed with the addition of water as a mixing medium. This mixture was then dried and calcined for 2 hours at 20 800 ⁰ C. If phosphorous acid was used as the phosphoric acid component in this case, there was a difference from the other experiments that it burned. The resulting caicirated product was then crushed using methyl alcohol and then dried and the various finely dividedF. obtained white pigments.

As in Example 6, the properties of the various finely divided white pigments obtained 25 and the test of independence by means of the salt water spray method and the test of flame resistance with the pigments were also carried out, the results given in Table XI being obtained became.

Table Xl

Type of phosphoroxy acid or des Phosphoroxy acid salt

Whiteness

(% Return)

(Wavelength mu)

350 400 450

500

Water-pll soluble component

CA)

Particle size

(μ)

Aggregation

Rust resistance test

Flammable wedge test

Phosphoric anhydride (P _: OO Mctaphosphoric acid

(HPO,)

Pyrophosphoric acid

(H ₄ P _: O0

Phosphorous acid

(H ₁ PO ₁ )

Hydrophosphoric acid

(H ₁ PO,)

Ammonium orthophosphate

((NH ₄ I ₂ HPO ₄ )

Disodium orlphosphate (NaJlPO ₄ )

Sodium ^pyro-?> Phosphate (Na ₄ P ^ O ₇ ) sodium hexametaphosphate ((NaPO ₁ ) ,,)

Sodium metaphosphate (NaPO,)

Sodium tripolyphosphate (Na, 1 ', O ₁₁₁ ) monopotassium phosphate (KIUO ₄ ) tricalium phosphate; u (Ca ₁ (K) ₄ ) O

85.8 92.7 92.9 93.6 2.6

80.1 91.2 93.3 94.3 2.7

87.5 100.5 102.0 103.1 2.7

78.6 101.1 100.9 101.6 2.5

40.8 80.6 83.5 85.8 2.5 86.0 97.3 98.6 99.9 2.6

94.0 104.6 104.1 105.1 1.7

90.0 103.7 103.8 104.3 1.9

65.3 85.3 88.4 90.6 1.8

72.9 88.0 95.3 99.8 1.5

90.6 100.7 100.9 101.9 2.3 69.0 95.9 ofj.3 99.4 2.2

88.7 97.4 99.3 100.5 1.3

2.2 below 5

2.4 below 5

2.6 below 5

2.4 below 5

2.4 below 5

2.4 below 5

3.0 below 5

2.8 below 5

2.8 below 5

3.0 below 5

2.8 below 5 2.8 unlcr-

3.2 below 5

2 2 2 2 2 2

2 2 2 2 2 2 2

A A A A A A

Λ A A Λ Λ A A

IO 10 10 10 10 11

12 12 12 12 12 12 12

26th

continuation

Type of phosphoroxy acid or / or Phusphoroxysäuresal / es

White ingredient

(% Reactance)

(Wavelength nifxj

350 400 450 500

Water pH Particle Aggre Rust Flame Resistant

soluble size gation constantly- constantly-

Constituency- kcils-

part try try

Aluminum phosphate 76.9 93.8 96.2 97.9 1.2 3.0 under- 2 A 12

(AlPO ₄ ) half past five

Zinc phosphate 48.9 96.1 92.6 97.3 1.2 3.0 under- 2 A 12

(Zn ₃ (PO ₄ J ₂ ) half past 5

Sodium phosphite 85.3 101.8 102.8 103.8 2.2 2.8 under- 2 A 11

(Na ₂ HPO ₃ ) half past five

Sodium hypo- 61.0 90.4 96.3 98.3 2.4 2.8 our- 2 A 11

phosphite (NaH ₂ PO ₂ ) halfway through 5th

From the above values, it can be seen that excellent results are obtained, sewoh! if that white phosphate pigment using phosphorus oxy acids as well as when the pigment is produced using salts of phosphorus oxy acids.

Example 9

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

Silica xerogel with small aggregates produced in Example 1 was used as the starting silica exerogel used.

A commercially available orthophosphoric acid (JIS first quality, 85% KiPO ₄ , specific weight 1.69) was used as the starting phosphoric acid.

Ammonia water (25 to Z9%) as industrial chemical was used as the starting ammonia.

First, the ammonia water was thoroughly absorbed on the silica xerogel at room temperature. In this procedure, 11.5% by weight, calculated as NH ₄ OH, of ammonia was absorbed by the silica xerogel. Even if the temperature of this silica was increased ammonia absorption in the region of 600 ⁰ C in a dry atmosphere without removal of ammonia was noted and the thermal DifTcrentialanaiyse showed no endothermic peak within this temper '' ifbereichcs.

Phosphoric acid was added to this silica gel with ammonia absorption in an amount corresponding to 1 mol of P ₂ O <per mol of SiO ₂ . Furthermore, ammonia water was added and the mixture was mixed intimately, so that a slurried mixture was obtained, the pH of which was about 9 to 9.5. This mixture was ^{dried and dehydrated at about 80 °} C. and further heated ^{at 80 °} C. for about 1 hour. This was followed by wet grinding of the product as in Example 1 using methyl alcohol, after which the ground product was dried. A finely divided white pigment was obtained.

The X-ray diffraction analysis, differential thermal analysis and analysis of the composition of the finely divided white pigment obtained, as well as the determination of the pH value of a 10%. aqueous suspension, the content of water-soluble constituents, the extent of aggregation and the particle size distribution. 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 [(NHi) ₂ HPO ₄ ) were chosen as the reagent and their properties and flame resistance were investigated in the manner indicated above.

The results are summarized in Table XII.

Table XII X-ray diffraction Thermi Analysis of the pH salary Aggre Part- Flame sample analysis sch Together one at gation small persistent Differ- settlement IO% igen water size dignity tialanalysc (Formula of Suspen sol distribute attempt (0-600 ⁰ C) Molarver sion lichem lung (endother
mer summit
"C) ratio) Duration
part (%) (μ) (mm /
12 sec.) X-ray 193 SiO, · P ₂ Os ■ 6 7.5 23.8 0.5 4-0.5 8th product pattern NHj ■ 3H ₂ O according to A-I according to the this description example (NH ₄ ) ₂₇ H _U P ₂ O ₇ 224, 229 (NH ₄ ) ₂ . ₇ H _U P, O ₇ 4.4 14.7 45.5 100-10 IO Comparison A (Ammo niumpoly phosphate) (NH ₄ I ₂ HPO ₄ (NH ₄ I ₂ HPO ₄ 8.2 63.9 100 100-10 15th Comparison B (Diammo- nium phosphatej

It can be seen from the above values that the finely divided, white pigment prepared according to this example is not only compared with similar white powders which were examined for comparison purposes is superior in terms of the flame resistance effect, but also differs completely in terms of the various properties. In addition, it has superior pigment properties, particularly in terms of the degree of aggregation, a property particularly required for a pigment. It as a result, this white pigment is extremely satisfactory for use as a flame-retardant pigment.

Example 10

In this example, the flame resistance results obtained when that prepared according to Example 9 are obtained white keselic acid-phosphoric acid-ammonia type pigment is mixed with various resins, described. A commercially available polyester resin and alkyd, melamine and polyamide resins which are commonly used as paint resins for coating purposes were selected.

The polyester resin, "Polymal", polyester from Takeda Chemical Company, was used.

70.50 and 30 parts by weight of the white silica-phosphoric acid-ammonia type powdery pigment prepared by the method of Bcisoiel 11 were added to each 100 parts by weight of the above polyester resin, followed by 10% by weight. Parts of chlorinated paraffin (CP 70), 0.6 part by weight of cobalt naphthenate, 1.0 part by weight of a peroxide and 0.1 part by weight of dimethylanilir. were added to each mixture. Upon mixing the individual mixes together without thorough stirring, they began to close in about 5 to 7 minutes härtn. While the glass was still in the flowable state, they were in arcs of 3 mm Poured starch and let it harden.

The sheets obtained were then tested for the Hamm resistance effect after the flame test tested according to ASTM D-635.

The alkyd resin is a commercially available alkyd resin coating material that dries at room temperature used. 50 parts by weight of the white, powdery pigment produced in Example 9 were admixed with 100 parts of this material.

The melamine resin was a solution in butanol of a butylated melamine as a precondensation product of the Melamine resin used. 50 parts by weight of the white, prepared according to Example 11, were added to this solution powdered pigment admixed.

As an application type polyamide resin solution with isano oil, linseed oil and polyamide resin as the base a paint composed of 100 parts by weight of a polyamide resin solution, 100 parts by weight of isano oil, 100 parts by weight Linseed oil, 40 parts by weight of chlorinated paraffin (70% Cl) and 0.5 parts by weight of cobalt naphthenate plus lead naphthenate used. 150 parts by weight of the white powdery pigment prepared by the method of Example 11 were mixed with the above paint.

These resin coating materials having Pigmcntzusatü were applied to pieces of a Zcichenpapieres and dried by being left to stand for 24 hours at room temperature in the case of the alkyd resin, for 1 hour at 11O ⁰ C in the case of Mclaminharzes were dried and allowed to stand for 24 hours at room temperature in the case of the polyamide resin became. As a result, film coatings of the individual marches to which the pigments were added were obtained on the pieces of paper.

The pieces of paper on the surface of which the various film coatings were formed became the Flammbesländigf cilsvcrsuch gcmiili Example I subjected.

The results of this experiment are summarized in Table XIII.

21
Table XIlI
Polyester resin 59 342 Added amount of
white pigment
(Parts) Zeil to / around Sdbst-
to extinguish the fire
(Minute, second) 70
50
30th
Paint type resins 3 sec.
7 sec.
I min., 50 sec. Type of Ilar7.cs Flume-proof wedge
attempt
(mm / 12 sec.) Alkyd resin
Melamine resin
Polyamide lumber 17th
4th
6th

From the above values, it is found that satisfactory Flammbesländigkitserfektc also in the Case where the white pigments obtainable in the present invention are incorporated into various resins and the resins mixed with the white pigments according to the invention either form a base processed or applied as a coating.

29

Claims (1)

Patent claims: 1. White phosphate-based pigment, characterized in that it consists of a phosphate with ' a composition of the formula M'O _: - .vY (ol ~ 1.5 + -Jy-) P ₂ O, consists in what M ^{1 is} one of the atoms silicon, titanium or zirconium.
Y is a nitrogenous base or an oxide of the formula M-O .. where M "is an alkali metal, alkaline earth metal, aluminum, lead, or zinc. and π the valency of this metal M ¹ darsicilen, λ a positive number up to 6 with the addition of O. and m the value 1. if Y represents a nitrogenous base, and the value «. if Y is the meaning M ¹ O. Has. mean. the phosphate pigment having a water solubility between 0.1 and 20% by weight and an amount of aggregation of not more than 50%, according to the following formula A-A ' X 100 where A is the weight of the powder passing through a mesh size of 74 μm, A 'is the weight of this powder passing through the same sieve after standing for 24 hours at room temperature in a relative humidity of 90% and Q is the degree of aggregation in percent mean. 2. White pigment according to claim I, consisting of a phosphate pigment of the formula siO; · ΝΥ · (o.l ~ 1.5 + worm Y is a nitrogenous base or an oxide of the formula M ^; O". wherein M ^; an alkali metal. F.rdalkulinietall. Aluminum, lead or zinc, and // represent the value of the metal ζ les M-, λ is a positive number up to /.u 6 under! connection of O. and m the value 1, if Y is a nitrogenous base, and the value n. if Y is the group is mean
3. White pigment according to claim 1, consisting of a phosphate pigment of the formula TiO; · (0.2 - 1.5) PO «.
a 10% aqueous suspension of the tilane phosphate having a pI value of not more than 3.5 nesit / i. 4. White pigment according to claim 1, consisting of a phosphate pigment of the formula ZrO <0.4 ~ 1.0) / P ₂ O ₅ 50 parts by weight to 500 parts by weight of the base material bathing the coating film is used The invention relates to a new white phosphate-based pigment with excellent flame and corrosion resistance and the use of this pigment for the production of initial masses for prevention mne of roasting metal surfaces. Whether colloidal silica, the so-called white carbon, is known as a filler, which has excellent abrasion resistance in rubber or synthetic resins, such as vinyl polymers. result it can be used as a white pigment or to refract the gloss of molded objects made of resin, for example Fibers are not entirely suitable because the finely divided silica usually has a transparent core. In addition, special operations are required in the manufacture of the above silica fluid ■ in an extremely fine particle size> u get ... which makes the production costs unavoidable