JPS6016477B2 - anti-corrosion pigment - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an anti-corrosion pigment, specifically y-Ca2P20
The present invention relates to an anticorrosion pigment made of a powder obtained by pulverizing a sintered composite containing y-Ca2P207, and an anticorrosion pigment made of a powder obtained by pulverizing a sintered composite containing y-Ca2P207 and further containing a glassy substance.

The main object of the present invention is to provide a novel anticorrosive pigment that does not contain harmful metals such as lead and chromium, does not cause any pollution, and exhibits excellent anticorrosive power over a long period of time.

Another object of the present invention is to provide an anticorrosion pigment that has excellent pigment properties and is not likely to impair the adhesion of a coating film formed by the coating material when it is blended into a coating material.

Furthermore, another object of the present invention is to provide an anticorrosion pigment that can be incorporated not only in oil-based paints but also in water-soluble paints.

As is well known, typical anticorrosive pigments include lead compounds such as red lead and basic lead sulfate, and chromate compounds such as zinc chromate and strontium chromate.

However, in recent years, in view of the pollution problems caused by toxic metals such as lead and chromium, there has been a demand in the industry for anticorrosive pigments that do not contain these toxic metals.

Furthermore, in view of the fact that water-soluble paints have recently attracted attention from the viewpoint of resource conservation, there is a demand for anticorrosive pigments that can be incorporated into water-lacquer paints.

The above-mentioned anticorrosion pigment made of a lead-based compound exhibits strong basicity, and due to its basicity, when it is blended into a water-soluble paint, the resin will gel, so it cannot be used.
However, although anticorrosive pigments made of chromate compounds are approximately neutral, as mentioned above, they may cause pollution, so their use tends to be avoided as much as possible. Therefore, there is currently a strong desire for anticorrosive pigments that do not contain lead, chromium, etc. from the viewpoint of pollution problems, and are neutral from the viewpoint of being incorporated into water-soluble paints.

Phosphate-based anticorrosive pigments are known as anticorrosive pigments that do not contain lead, chromium, etc.
Publication No. 26291 describes barium diphosphate, zinc phosphate, antimony phosphate, lead phosphate, chromium phosphate, manganese phosphate and phosphoric acid compounds, especially divalent or trivalent metal phosphites and The use of phosphites, especially barium, magnesium and manganese phosphites, calcium and iron hypophosphites, alone or together, has been disclosed to have an anti-corrosion effect.

Phosphate-based anticorrosive pigments such as those mentioned above do not contain lead, chromium, etc., and are neutral, so they can be incorporated into water bath paints, but they do not have the ability to prevent lead from corrosion. It is inferior to anticorrosive pigments made of chromate compounds and crocate compounds, and is hardly able to meet the demand for sustaining anticorrosion effects in coatings over a particularly long period of time. That is, as is well known, the anticorrosion effect of phosphate-based anticorrosive pigments, especially those containing zinc phosphate, is due to the phosphate formation of the iron-containing metal substrate, which is the material to be protected. The protective layer is formed by the interaction between iron and the pigment, and in order to exert this anticorrosion effect over a long period of time, the anticorrosion pigment itself has an appropriate solubility, and it gradually dissolves over a long period of time. It needs to be dissolved.

However, the conventionally known phosphate-based anticorrosion pigments are easily soluble in water, and although they exhibit temporary anticorrosion effects,
It is not possible to maintain the anticorrosion effect for a long period of time. Furthermore, British Patent No. 904861 discloses a technique in which the use of calcium phosphate, zinc phosphate, lithium phosphate, and barium phosphate together with red lead, calcium leadate, zinc chromate, or iron oxide is effective for corrosion prevention. Although it has been published publicly, the amount of phosphate contained in the anticorrosive pigment shown in (a) is extremely small, and of course it is likely that it is blended with the expectation of the anticorrosion effect of the phosphate mentioned above. However, as in the former case, phosphate itself is an easy lacquer, and the anticorrosion effect of phosphate itself is not sustained over a long period of time.

Furthermore, known phosphate-based anticorrosive pigments, including the anticorrosive pigment described in Japanese Patent Publication No. 49-26291 and the anticorrosive pigment described in British Patent No. 904861, are inferior in pigment properties. Due to this, when it is blended into a paint, it cannot fully exhibit its anticorrosion function.

In other words, regardless of whether an anticorrosion pigment is added to a water-soluble paint or an oil-based paint, the pigment properties of the anticorrosion pigment have a large effect on the adhesion of the paint film. However, if the pigment properties are poor, it will deteriorate the adhesion of the paint film, causing blistering and peeling of the paint film, and the anticorrosion effect will be lower than the problem of the anticorrosion function of the anticorrosion pigment itself. As a result, you will no longer be able to obtain it. In other words, it is well known that the adhesion of coating is greatly affected by the pigment volume concentration (PVC value), which is one of the measures of pigment properties.
This pigment volume concentration (PVC value) is generally expressed by the following formula.

In case of PVC value due to linseed oil; 100pb PVC=pb+.

・〇1.0A stop ・PP What the above formula means is that a large PVC value means a small oil absorption amount, and
A VC value of 4.0 means that the oil absorption amount is large.

For pigments with a small PVC value, a large amount of the resin component is consumed to wet the surface of the pigment, and it is difficult to obtain sufficient resin component to maintain adhesion to the surface of the object to be coated.
Normally, anticorrosive paints are blended at a ratio of 1 part of resin to 1 part of pigment (anticorrosive pigment alone or anticorrosive pigment + extender pigment), but if the PVC value of the anticorrosive pigment is very small, even if Even if the pigment is not soluble in water, as shown in the above formula, sufficient resin components cannot be obtained to maintain adhesion to the surface of the object being coated, resulting in blistering and peeling of the paint film. It is a major cause of rust.

Anticorrosive paints may contain only an anticorrosive pigment or may contain an anticorrosive pigment and an extender pigment as pigment components, but in either case, the pigments blended have suitable pigment characteristics,
For example, it is necessary to have a suitable PVC value. This is because the pigments used must have suitable pigment properties in order for the anticorrosion pigments and extender pigments to exist in a sufficiently dispersed state and to obtain a strong and highly adhesive coating. This is because it will not happen. Red lead is a representative anti-corrosion pigment, and Bengara, an iron oxide pigment is a representative extender pigment, has pigment properties suitable for use as a pigment in anti-corrosion paints, and its PVC value is around 45-60%. It is something.

In practice, 45 to 60
It is said that when obtaining a PVC value of %, there is no problem in practical pigment properties, a robust and highly adhesive coating can be used, and the phenomenon of blistering and peeling of the coating does not occur. However, the conventionally known phosphate-based anticorrosion pigments do not have pigment properties comparable to those of red lead and Bengara, and for this reason, when blended into paints, the adhesion of the coating surface may be affected. This is a factor that causes deterioration in properties, making it difficult to obtain a coating film that is robust and has good adhesion. The present inventor has discovered that phosphate-based anticorrosive pigments have appropriate solubility, more specifically, the property of gradually dissolving over a long period of time, and excellent pigment properties, and more specifically, the PVC value of Bengara, etc. The research was carried out with the aim of imparting a PVC value similar to that of the above.

As disclosed in Japanese Patent Application Laid-Open No. 50-34329, the present inventor has already developed an iron oxide pigment (for example, Bengara), which is well known for its excellent pigment properties, and a calcium compound under specific conditions. Book a0・F by dawning
We have successfully obtained a Akatsuki complex containing e203 and provided an anticorrosion pigment made from a powder obtained by pulverizing the composite.

This anti-corrosion pigment exhibits the basicity required to exhibit anti-corrosion effects as the Ca content gradually dissolves over a long period of time, and has excellent pigment properties and characteristics. It is put into practical use as The present inventor made use of his experience in completing the above-mentioned anti-corrosion pigment, and discovered that by adding a phosphoric acid compound and a calcium compound to an iron oxide pigment, a new phosphate-based pigment having both moderate solubility and excellent pigment properties could be created. Thinking that it might be possible to obtain an anti-corrosion pigment, we conducted systematic experiments in which we treated iron oxide pigments with phosphoric acid compounds and calcium compounds by various means to generate a large number of compounds, and examined their anti-corrosion properties. As a result of stacking, the competitive complex obtained by mixing and firing the iron oxide pigment, phosphoric acid compound, and calcium compound under specific conditions is y-Ca2
It was learned that the powder containing P207 and pulverized has appropriate solubility and excellent pigment properties, and is excellent as an anticorrosion pigment.

Furthermore, the present inventor fired the iron oxide pigment, the phosphoric acid compound, and the calcium compound under specific conditions to produce y-Ca2.
If a specific compound that becomes a glassy substance upon firing is added to obtain a pseudo-crystalline composite containing P207, it will have even better pigment properties than the above case, and also have a more moderate solubility. I am discovering that things can be obtained.

The present invention was completed based on the above findings.

That is, the present invention has a range of 29.90 to 53.0% in terms of Ca0.
23% by weight of calcium carbonate, calcium hydroxide,
A calcium compound selected from calcium oxides and P
46.77-70.10% by weight in terms of 205 Day 3
P04, HP03, Day 4P207, (HP03)6, &
35.0 to 90.0 in terms of Fe203 for 10.0 to 65.0% by weight of a mixture with a phosphoric acid compound selected from P30, o, Ma P03, Hi 3 P02 and P205
% by weight of an iron compound selected from Fe2Q, Fe00day and Fe304 is mixed, and this mixture is mixed with 350-800q
Ca2P2Q obtained by firing at a temperature range of 5
When firing an anticorrosion pigment made of powder obtained by crushing a scale complex containing 10% by weight or more of the above mixture, Na20, K20 and S
In the three composition diagram of i02, the weight composition ratio is point A (N is also 0:
Si02=50.77:49.23), 8 points (N also 0:
Si02=25:75), point C (K20:Si02=2
5:75), point D (K20:SiQ=61.05: Shigeru.
The composition is within the range connecting each point of 95) and the melting temperature is 90
A compound that forms a Na and/or K-Si glassy material at a temperature of 0°C or lower is 0.5 to 4. This is an anticorrosive pigment made of a powder obtained by pulverizing a competitive striped composite containing 5% by weight or more of y-Ca2P207, which is obtained by adding 5% by weight or more of y-Ca2P207 and firing it in the above-mentioned temperature range. Next, the configuration and effects of the present invention will be explained.

First, y-Ca2F207, which is the most characteristic feature of the present invention, will be described. y-C contained in the anticorrosive pigment according to the present invention
a2P207 exhibits its anti-corrosion function by phosphatizing the iron-containing metal substrate, which is the material to be protected, by dissolving in water and forming a phosphoric acid protective layer under the paint film through interaction with iron. . Moreover, this y-Ca2P207
has the property of having a very slow dissolution rate in water, and because it gradually dissolves in water, it can maintain its anticorrosion function for a long period of time. Ca
As is well known, the conditions for the production of 2P207 have already been elucidated, and approximately 350 qo of a mixture of 44.14% by weight of calcium compounds in terms of Ca0 and 55.86% by weight of phosphoric acid compounds in terms of P205 is Ca2P207 is produced when calcined at a temperature above 400°C, and it is said that Ca2P207 is produced with almost 100% yield if the calcination temperature is 400°C or higher, and as the amount of calcium compounds increases, the amount of Ca2P207 produced increases. When the amount of calcium compounds decreases and the amount of calcium compounds exceeds 54.24% by weight (calculated as Ca○), no Ca2P207 is produced at all.Also, as the amount of calcium compounds decreases, the amount of C and P207 produced decreases, and the amount of calcium compounds increases. 28.32% by weight (Ca
○ conversion) It is said that Ca2P207 is not generated at all in the following cases.

In addition, C generated when a calcium compound and a phosphoric acid compound are mixed within the above range and fired under the above temperature conditions.
The crystal structure of a2P207 has already been elucidated, and in the above case, Q-type and B-type Ca2P207 are produced. Q-Ca2P207,6-Ca2P207 is insoluble in water, and even if they are used as anticorrosive pigments, they cannot exhibit anticorrosion function. However, when a calcium compound and a phosphoric acid compound are mixed in a range where Ca2P207 is produced, and in the presence of iron compound, 35
When calcining at temperatures above 0°C, y-Ca2P207 is produced as seen in the X-ray diffraction diagram in Figure 2, and as mentioned above, this substance has a slow solubility in water. , which can exhibit anti-corrosion function. Incidentally, this fact was discovered for the first time by the present inventor. That is, as seen in the X-ray diffraction diagram of FIG. 2 circles weight% (Ca○ conversion) and phosphoric acid compound 46.77 to 70.1 weight% (P205 conversion)
The y-Ca2P complex produced when mixed in the range of
207 and iron oxide, and the angle 20 of the X-ray diffraction is slightly off, indicating that y-Ca2P207 with a small amount of Fe precipitated is also a condensed complex of P207 and iron oxide. I understand. Further, as a result of numerous experiments, the present inventor has confirmed the fact that if y-Ca2P207 is contained in an amount of 5% by weight or more, a corrosion-preventing function that can be put to practical use is sufficiently exhibited.

That is, when y-Ca2P207 is less than 5% by weight, the amount of soluble phosphate is too small and it cannot be guaranteed that the anticorrosion function will be exhibited for a long time.
This can be guaranteed in the above cases. As seen in the examples below, when y-Ca2P207 is 5% by weight or more, there is no significant difference in the anticorrosion function even if the content is greater than this. Next, each starting material and its blending amount in the present invention will be explained.

The details of each starting material are as follows. The calcium compound, which is one of the starting materials, has a molecular weight of 350 to 800.
The above y-Ca2P2 reacts with a phosphoric acid compound at qo.
Any device that generates 07 may be used.

Preferably, calcium carbonate, calcium hydroxide, and calcium oxide are selected, and one or more of these may be used. As the phosphoric acid compound, Hi3P04, HP03, Hiro P207, (HP03)6, Hi5P30,o, Hi3P03, HiP02, P24, etc. are selected. When fired in a temperature range of 350 to 800 qo, these materials change to P205, and in the present invention, they function in exactly the same way as when P205 is used as the starting material. As iron compounds, Fe203, F
e304, Fe00 day is selected. Fe2Q is “bengara”
It is an iron compound well known as iron oxide, and is a typical iron oxide pigment. The reason why Bengara was selected as the starting material in the present invention is as already stated. Fe3
04 and Fe00 days are also used as iron oxide pigments, the former being well known as a black pigment and the latter as a yellow pigment. Fe3Q and Fe00 days are both Fe2
It has the same pigment characteristics as 03, and 35
When fired in a temperature range of 0 to 800 qo, it has exactly the same effect as in the case where Fe203 is used as the starting material in the present invention. Also Fe203, Fe304,
It is of course possible to use them alone or in combination up to Fe00 days'. The blending amounts of each of the above raw material mixtures are as follows.

The mixing ratio of calcium compound and phosphoric acid compound is Ca2
It is determined in relation to the generation of P207, and the former is 29.90
~53.23% by weight (calculated as CaO), the latter being 46% by weight
．． It is selected in the range of 77 to 70.1% by weight (in terms of P205). The iron compound is a mixture of the above-mentioned calcium compound and phosphoric acid compound of 10.0 to 65. Weight% (Ca○, P
205 conversion) to 35.0 to 90. Weight% of (Fe
203 equivalent).

The mixing ratio of iron compounds is important; 35. If the amount is less than 207% by weight, highly alkaline substances will be produced in addition to y-Ca207, and the basicity will be extremely high, which is not preferable. Furthermore, if the amount of the iron compound mixed is small, the pigment properties as an anticorrosion pigment will inevitably deteriorate, which is not preferable. 90. % by weight, the theoretical maximum yield of y-Ca2P207 is 1% by weight, but if there is sufficient y-Ca2P
In order to generate 207, strict control is required for the firing conditions, etc., which is not preferable, so iron compounds are 90. % by weight or less.

Roughly speaking, the calcium compound is 29.90 to 53.2% by weight in terms of Ca0 and 46.9% in terms of P205.
77-70.1% by weight of phosphoric acid, mixture 1
0.0-65. 35 as Fe203 for the weight% of
．． 0-90. When mixed with weight percent of ferrite,
It can be guaranteed that a non-setting composite containing 5% by weight or more of y-Ca2P207 can be obtained.

Next, the firing temperature in the present invention will be explained.

The firing temperature must be in the temperature range of 350-800 qo. The reason for this is as follows. In the present invention, 35
When the temperature is 0°C or lower, the reaction to produce y-Ca2P20 does not occur, and on the other hand, when the anabolic temperature exceeds 800 qo, neither the N-C nor the P-N in the scale silk complex obtained is present. turns into other calcium phosphate salts and becomes insoluble salts.

A competitively bonded composite containing 5% by weight or more of y-Ca2P207 obtained by mixing the above-mentioned calcium compound, phosphoric acid compound, and iron compound in the above-mentioned amounts and firing in the above-mentioned temperature range can be produced by ordinary pulverization means. The resulting powder has pigmentary properties comparable to well-known iron oxide pigments.

Therefore, if this powder is used as an anticorrosive pigment, its moderate solubility will provide long-term anticorrosive function, and its excellent pigment properties will not deteriorate the adhesion of the paint film when added to paint. Furthermore, since it is possible to obtain an anticorrosive pigment that is approximately neutral, it can be incorporated not only in oil-based paints but also in water-soluble paints.

As shown in the examples below, the anticorrosive pigments as described above exhibit excellent effects when used in water-soluble paints and oil-based paints, but even more excellent performance can be achieved. If required, better pigment properties and more appropriate solubility can be imparted by exploring the following technical means.

That is, in obtaining a competitively bonded composite by using the starting materials, their blending amounts, and firing temperatures as described above, a mixture 1 consisting of an iron compound, a phosphoric acid compound, and a calcium compound is prepared.
0.5 to 4.0 parts by weight of the following formulation: What we need to do is to find a technical means to add 2 parts by weight.

The added compounds are Na20, K20 shown in Figure 1.
In the three composition diagrams of Si02 and Si02, the weight composition ratio is at point A (N
a20:Si02=50.77:49.23), point B (
Na20:Si02=25:75), point C (K20:S
i02=25:75), point D (K20:Si02=61
．． 05:38.95) and which forms an Na and/or K--Si glassy material with a melting temperature of 900°C or less.

After adding the above compound, it is calcined at a temperature range of 350 to 800 qo, and then crushed to powder, so that each particle becomes N.
It is possible to obtain an anticorrosion pigment coated with a and/or K-Si glassy material.

In the anticorrosion pigment in which each particle is coated with the Na and/or K-Si glassy material, the dissolution rate of P207 is even slower due to the presence of the glassy material coating layer. Therefore, it exhibits its anti-corrosion function for a longer period of time.

In addition, when the above compound is added and baked, a part of the above compound reacts with a part of the phosphoric acid compound, resulting in NaP03
, KP03, which have a function as an inorganic dispersant, improve the dispersibility of the anticorrosive pigment.

Furthermore, when using an anticorrosion pigment, NaP03 and KP03 are dissolved in water and contribute to initial anticorrosion properties. Furthermore, when the above-mentioned compound is added and calcined, the dawn composite contains Na and/or
Alternatively, due to the presence of the K-Si glassy substance, it can be pulverized very easily, so that a powder with excellent pigment properties can be obtained by simple pulverization.

The composition range of the above compound is determined by taking into consideration the firing temperature and each effect mentioned above, and when a compound within the above range is added within the above addition amount range, the above-mentioned effect will be achieved. Each effect is guaranteed.

If the amount of the above compound added is 0.5 parts by weight or less, N
4. A and/or K-Si based glassy material coating layer is not sufficiently formed, so no significant effect can be obtained, and 4. If the amount is more than 2 parts by weight, the coating layer of Na and/or K-Si glassy material will become too thick, making it difficult to crush the resulting anti-coagulant composite, and even if it is powdered. This will excessively suppress the elution of y-Ca2P207 contained in the anticorrosive pigment. Furthermore, in specifying the composition range of the above-mentioned compound, it is stipulated that the compound should form a Na and/or K-Si glassy material with a melting temperature of 900 oo or less; When the temperature is in the temperature range of ~800 °C, the above-mentioned compound forming a Na and/or K-Si glassy substance with a melting temperature of 900 °C or less will partially melt and exhibit the above-mentioned effects. This is because it is possible. However, it is natural that the greater the melting amount of the above-mentioned compound forming the Na and/or K-Si glassy material, the greater the effect obtained, and in this sense, when the firing temperature is the lower limit of 350 qo. It is desirable to select a compound that forms a Na and/or K-Si glassy substance with a melting temperature of about 60 mm or less. If the temperature is high, it is desirable to select a compound that forms a Na and/or K-Si glassy material with a melting temperature of about 50 to 100° C. added to the firing temperature. In addition, when adding the above compound, N is 0, K20, Si02, Na2C03, K2C03
Single raw materials that decompose into oxides when heated, such as N, ○・Si02, Na20・$i02, K20・Si02
, K20, I02, etc. may be weighed out and added within the above range.

Describing the usage mode of the anticorrosive pigment according to the present invention as explained above, the anticorrosive pigment according to the present invention includes Na and/or
Alternatively, it can be used in exactly the same way with or without a K-Si glassy substance coating layer, and is used by mixing it into a known paint constituent base material by a known mixing method as explained below. However, the amount of blending depends on the amount of pigment in the base material of the paint (anticorrosion pigment alone or anticorrosion pigment + extender pigment)
It is necessary to blend the anticorrosive pigment according to the present invention so that it contains 5% or more of y-Ca2P207, and in this case, an anticorrosive paint that exhibits a sufficient anticorrosive effect over a long period of time can be obtained.

The paint constituent base material to which the anticorrosive pigment of the present invention is blended is a well-known material that is commonly used as a paint composition for anticorrosive paints, and contains a brightening agent (resin) and a solvent as essential components. Extender pigments, coloring pigments, drying accelerators, if necessary.
It contains surfactants, etc.

As the auburn agent (resin), any agent commonly used in anticorrosion paints can be used, including natural resins, synthetic resins, oil-based resins, and water-based resins.

In particular, since the anticorrosion pigment according to the present invention can be adjusted to have a mottling value of around 7, there is no risk of causing problems in the preparation of paints, such as gelation, even when used in water-soluble paints. Typical examples of the brightening agents include linseed oil, alkyd resins, vinyl chloride resins, epoxy resins, phenol resins, urethane resins, and butyral resins. The resin most used is not limited to those exemplified above, but can be selected from among known resin groups depending on the purpose of use. The solvent may be selected from a group of known solvents depending on the type of resin used.

Typical examples include acetone, toluene, diacetone alcohol, mineral spirit, and ion-exchanged water. As extender pigments and coloring pigments, all those commonly used in anticorrosion paints can be used, and they may be selected from known pigment groups depending on the purpose of use.

Typical examples are Fe2Q, Fe3Q,
Examples include iron oxide pigments such as Fe00, calcium carbonate powder, zinc hydrangea, titanium white, and clay. The drying accelerator may be selected from a group of known drying accelerators depending on the type of resin used.

Typical examples include naphthenates such as cobalt, lead, zinc, and manganese, and linolenates such as cobalt, lead, zinc, and manganese. As the surfactant, those having the ability to improve the kneading properties of anticorrosion pigments, extender pigments, and coloring pigments may be selected from a group of known surfactants as necessary.

It goes without saying that various additives generally used in anticorrosive paints, such as plasticizers, anti-settling agents, anti-color fading agents, etc., can also be added to the above-mentioned coating composition.

The auburn agent (resin) in the coating composition as described above, the solvent,
The quantitative relationships among extender pigments, coloring pigments, drying accelerators, and surfactants are similar to those in known anticorrosion paints.
Specific examples thereof are shown in Examples below.

The anticorrosive pigment according to the present invention can be incorporated into the above-mentioned coating composition in exactly the same manner as well-known coating manufacturing means, and the anticorrosive pigment according to the present invention can be incorporated into the coating composition adjusted to the desired formulation. An anticorrosive paint can be obtained by mixing anticorrosive pigments and dispersing them well using a pole mill or the like. When the anticorrosive pigment according to the present invention as explained above is used to form a coating, it has the following advantages.

Since the '1' anticorrosive pigment does not contain a lead-based compound or a chromate-based compound, an anticorrosive paint that does not have any adverse effects on the human body can be obtained.

'21 It is possible to obtain an anticorrosive paint that maintains anticorrosive power for a long period of time equal to or greater than that of an anticorrosive paint containing lead chromate, zinc chromate, or the like as an anticorrosive pigment.

Next, the present invention will be explained with reference to Examples and Comparative Examples.

Example 1 CaC03 powder 35. weight part and Fe203 powder 55.
7 parts by weight with an aqueous solution with a ratio of P0434.1 parts by weight, granulated, put in an electric furnace and fired at 60 p○ for 1 hour, and the ratio of calcium oxide to P205 to iron oxide was 19. A calcium phosphate iron monoxide bran bonded composite having a particle size of .6/24.7/55.7 was obtained.

As a result of X-ray diffraction, the above sintered composite was found to contain only y-Ca2P2Q and iron oxide dots, and y-C was P
It was confirmed that 207 contained 4% by weight.

FIG. 2 is an X-ray diffraction diagram of the sintered composite. Next, the above-mentioned Akatsuki composite was ground to a powder with an average particle size of 0.5r using a vibration mill. The PVC value of this powder was 57%. Calcium phosphate iron monoxide sintered composite powder 22 containing 4% by weight of y-Ca2P207 obtained in this)
．． The anti-corrosive pigment was mixed into a paint composition according to the following treatment for water-removal paint evaluation (hereinafter referred to as method A), and well dispersed using a paint conditioner to obtain an anti-corrosion paint.

Color vehicle: Alkyd resin (product name S-1000, NV60 purple) 29.30 ta
drug (20 soptilce per day).

Solfuni 9/,) 44.45 Takozu Foaming Agent Nobuko 803 Izumi Equipment Name) 9 Two Words '20 Hardening Agent Cobalt Naphthenate (6 Multi-Solution) 0.5 Lead Thanaphthenate (24 Purple 〃) 0.5 Ta The anticorrosive paint obtained in step) was applied to a thickness of approximately 100 mm on a degreased steel plate with no rust, and the core steel plate was immersed in running water for 2 months to make the coated surface appear inferior. Corrosion resistance was tested based on the time when blistering was observed in the coating film and the percentage of blistering occurring two months later (area where blistering occurred/coated area x 100). In the above case, blistering was observed in the coating film on the 55th day, and the blistering rate after 2 months was 5%.

Furthermore, the above y-
Calcium phosphate iron monoxide composite powder 22.0% containing 40% by weight of Ca2P207 was used as an anticorrosive pigment, mixed with a paint composition having the following formulation, and well dispersed using a paint conditioner to obtain an anticorrosive paint.

Warm Color Agent Alkyd Resin 15T
Agent Mineral Spirit (trade name) 35% drying accelerator 6% cobalt naphthenate solution 0.2 to 24 scales lead naphthenate solution o. Approximately 100% of the anticorrosive paint obtained in step 2) was applied to a rust-free, degreased steel plate.
The steel plate was coated to a thickness of Rate of occurrence of blistering phenomenon (area of blistering phenomenon/
The anticorrosion property was tested by coating area x 100).

In the above case, a blistering phenomenon was observed on the coating film after 25 days, and the rate of blistering occurring at the end of the dipping was 1.
It was 0%. Examples 2 to 8 Properties of anticorrosive pigments and evaluation of water-soluble paints in Example 1 (Method A) in the same manner as in Example 1 except that the blending amount of starting materials and firing temperature were variously changed. The anticorrosive test results of anticorrosive paints tested in the same manner are shown in Examples 2 to 8.
Shown in the table.

In Example 8, the anticorrosion pigment obtained showed high alkalinity, and gelation occurred when forming it into a water-soluble paint, making it difficult to form it into a paint. Furthermore, in Examples 7 and 8, the corrosion resistance test results of the anticorrosive paints tested in the same manner as the oil-based paint evaluation (Method B) in Example 1 are added to Table 1. Examples 9-1
9 The properties of the anti-corrosion pigment and the results of the anti-corrosion test of the anti-corrosion pigment in the case of using the same machine as in Example 1 except for various changes in the type and amount of the starting materials and the firing temperature are shown in Examples 9 to 17.
Shown in the table.

Comparative Example 1 Using Fe208 powder (Bengara) instead of the anticorrosion pigment of Example 1, water-soluble paint and oil-based paint obtained using the paint composition of the formulation shown in Example 1 were prepared using the same machine as Example 1. Table 1 shows the results of the anti-corrosion test.

Comparative Example 2 Water-soluble paint evaluation in Example 1 of a water-soluble paint obtained by using Ca3(P04)2 in place of the anticorrosive pigment of Example 1 and using a paint composition with the formulation shown in Example 1. Table 1 shows the results of the corrosion protection test conducted in the same manner as (Method A).

Comparative Example 3 Properties of an anticorrosive pigment obtained in the same manner as in Example 1 except that the firing temperature was changed to 90 pi Table 1 shows the results of the corrosion protection test conducted in the same manner as the water-soluble paint evaluation in 1.

Comparative Example 4 26.7 parts by weight of CaC03 powder and Fe as starting materials
203 powder and 50.0 parts by weight of day 3P0449. The properties of the anticorrosion pigment obtained in the same manner as in Example 1 and the properties shown in Example 1 were obtained by mixing and granulating an aqueous solution containing parts by weight of Table 1 shows the results of the anticorrosion test conducted in the same manner as the water-soluble paint evaluation in Example 1 for the water-soluble paint obtained using the paint composition having the formulation.

Comparative Example 5 78.7 parts by weight of CaC03 powder was used as a starting material.
Properties of an anticorrosive pigment obtained in the same manner as in Example 1 except that 0477.2 parts by weight of an aqueous solution was mixed and granulated, and a water-removable paint obtained using a coating composition having the formulation shown in Example 1. Table 1 shows the results of the water-soluble paint evaluation in Example 1 and the corrosion protection test conducted using the same machine.

As a result of X-ray diffraction, it was confirmed that the competitive mackerel complex did not contain y-Cayo207. FIG. 3 is an X-ray diffraction diagram of the dawn composite. Comparative Examples 6 and 7 Zinc chromate (ZTO) was used instead of the anticorrosion pigment of Example 1.
), strontium chromate, water-soluble paints and oil-based paints obtained using the paint composition shown in Example 1 in the same manner as in Example 1.
Shown in the table.

Examples 20 to 24 Anticorrosive pigment 1 obtained with the raw materials and blending amounts in Example 1
00 parts by weight converted to Na20 and Si02: 30:
The blend of C03 and Si02 has a weight ratio of 70% N to 0.5-4. The properties of the anticorrosive pigment and the coating composition of the formulation shown in Example 1 were prepared in exactly the same manner as in Example 1, except that various parts by weight were mixed and granulated, and the firing temperature was varied. Table 2 shows the results of the anti-corrosion test of the water-soluble paint obtained using the same method as in the evaluation of the water-soluble paint in Example 1.

Examples 25 to 27 The properties and properties of anticorrosive pigments were the same as in Example 20, except that the blending ratio of Na2C03, K2C03, and Si02 forming the Na and/or K-Si glassy material was varied. The second corrosion test result
Shown in the table.

Table 1 Table 1 Table 2

[Brief explanation of drawings]

FIG. 1 is a three-composition diagram of Na20-K20-Si02 in the present invention, where each value inside the line indicates temperature (°C), and each value outside the line indicates weight %. FIG. 2 is an X-ray diffraction diagram of the calcium phosphate lucium monoxide sintered composite containing y-Ca2P207 obtained in Example 1. FIG. 3 is an X-ray diffraction diagram of the calcium phosphate iron monoxide composite obtained in Comparative Example 4. Mackerel diagram 2nd calculation diagram 3

Claims (1)

[Claims] 1 Calcium compound selected from calcium carbonate, calcium hydroxide, and calcium oxide in an amount of 29.90 to 53.23% by weight in terms of CaO, and 46.77 to 53.77 in terms of P_2O_5 70.10% by weight of H_3PO_
4, HPO_3, H_4P_2O_7, (HPO_3)
_6, H_5P_3O_1_0, H_3PO_3, H_
Fe_
35.0 to 90.0 weight% Fe_ in terms of 2O_3
Consisting of powder obtained by pulverizing a sintered composite containing 5% by weight or more of γ-Ca_2P_2O_7 obtained by mixing iron compounds selected from 2O_3, FeOOH and Fe_3O_4 and firing this mixture at a temperature range of 350 to 800°C. Anticorrosion facial sulfur. 2 A calcium compound selected from calcium carbonate, calcium hydroxide, and calcium oxide in an amount of 29.90 to 53.23% by weight in terms of CaO, and 46.77 to 70.10% in terms of P_2O_5 by weight. H_3PO_
4, HPO_3, H_4P_2O_7, (HPO_3)
_6, H_5P_3O_1_0, H_3PO_3, H_
Fe_
35.0 to 90.0 weight% Fe_ in terms of 2O_3
An iron compound selected from 2O_3, FeOOH and Fe_3O_4 is mixed, and further, with respect to 100 parts by weight of this mixture, the weight composition ratio in the three composition diagram of Na_2O, K_2O and SiO_2 is at point A (Na_2O:SiO_2=
50.77:49.23), point B (Na_2O:SiO
_2=25:75), point C (K_2O:SiO_2=2
5:75), point D (K_2O:SiO_2=61.05
Addition of 0.5 to 4.0 parts by weight of a compound that forms a Na and/or K-Si glassy material with a composition within the range connecting each point of 38.95) and a melting temperature of 900°C or less. An anticorrosion pigment made of a powder obtained by pulverizing a sintered composite containing 5% by weight or more of γ-Ca_2P_2O_7 obtained by firing this mixture at a temperature range of 350 to 800°C.