JPS60121201A - Metallic composite powder material and its production - Google Patents

Abstract

PURPOSE:To improve chemical resistance and electrical insulating characteristics and to obtain a metallic composite powder material which suppressed deterioration in shelf life by coating metallic powder with a polymer consisting of isocyanate and water and treating further the coating surface with an amine. CONSTITUTION:1-100pts.wt. isocyanate monomer such as toluylene diisocyanate or the like by 100pts. metallic powder such as Al or the like and 0.1-100pts.wt. water by 100pts. the isocyanate are added into an inert solvent. The soln. is heated under stirring to cause reaction, thereby covering the particle surface of the metallic powder with the formed polymer. An amine such as dibutyl amine or the like is then added at 0.5-50pts. to the soln. under stirring to cause reaction, thereby eliminating the residual monomer and treating simultaneously the surface of the coated polymer. The terminal isocyanate group on the surface layer of the coating polymer is brought into reaction with the amine by the above-mentioned treatment and is thus made inert, by which the stable composite body is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel powdery metal composite and a method for producing the same, and more specifically, a novel powder metal composite having acid resistance, alkali resistance, other chemical resistance, and electrical insulation properties, as well as stability during storage. More specifically, the particle surface is coated with a polymer made of a reaction product of isocyanate and water to impart chemical resistance and electrical insulation, and then the coating is coated with a polymer made of a reaction product of isocyanate and water. The present invention relates to a powdered metal composite which is provided with excellent storage stability such as suppressing changes in hue and aggregation during storage by treating the surface of the polymer with amines, and a method for producing the same.

In general, metal base metals such as zinc, aluminum, tin, iron, copper, and lead have the property of being extremely difficult to conduct electricity, and they also have the disadvantage of being chemically weak against acids and alkalis. There is. Particularly when these metals are used in the form of powder, their specific surface area becomes large and the chemical weaknesses mentioned above are further exacerbated, so their applications are limited.

Therefore, by imparting electrical insulation properties and resistance to acids, alkalis, and other chemicals to these metal powders, their uses will be further expanded.

For example, aluminum pigments have extremely excellent design features such as brightness, light reflectivity, and a metallic feel, so they can be used, for example, in metallic paints for automobiles, exteriors of light electrical equipment, and machinery. It is used for painting equipment, ships, and many other areas. however,
Since this aluminum pigment has poor insulation resistance and chemical resistance, it has the disadvantage that it cannot fully satisfy the following recent needs.

That is, in recent years, with the development of coating technology and industry needs such as resource saving and pollution-free production, the functions and characteristics required of paints have become increasingly diverse and sophisticated.

For example, in recent years, electrostatic coating has become more common in the painting of automobiles, and therefore the paint used for this painting is required to have an extremely high degree of electrical insulation (40).

Furthermore, recently, plastic bumpers, wheels, and other equipment parts have increasingly been finished with one-coat metallic finish, and in these fields, coatings are required to have a high degree of chemical resistance. Of course, the chemical resistance of this coating film is significantly affected by the chemical resistance of the varnish itself, but when aluminum pigments are used, the chemical resistance of the individual aluminum particles in the coating film is particularly important. Gender has a significant influence.

On the other hand, in the light electrical field, coating films are required to have high electrical insulation properties, moisture resistance, chemical resistance, etc.

In addition, in this field, the base material is often plastic, and these coatings are prone to color unevenness due to static electricity, so it is necessary to make the coating thinner1, and even this thin coating has sufficient protection function. In order to maintain a beautiful appearance, a high degree of chemical resistance is required.

Furthermore, high-value tags and the like are often attached to these products using cellophane tape, but the adhesive needs to be strong enough to prevent the paint film from peeling off when it is removed. The peeling in this case is not a failure at the interface between the base material and the paint film, but a peeling at the interface between the resin and aluminum pigment particles in the paint film, which is so-called cohesive failure of the paint film.

In the construction field, for example, in the field of pressure,
Cement becomes strongly alkaline due to the calcium hydroxide produced by the hydration reaction, and because it is exposed to high temperatures and rainwater, a high degree of alkali resistance is required.

Conventional aluminum pigments have not been able to satisfy these needs, and there has been a strong demand in the industry for aluminum pigments that have strong chemical properties and electrical insulation properties.

By the way, conventionally, as a pigment for metallic electrostatic coating, ≠
Aluminum pigments whose surface is coated with a kifsilane-based coupling agent are widely used, but although these have improved electrical insulation properties, they suffer from storage stability problems such as changes in hue over time and an increase in aggregates. In addition, there is a problem in that the chemical resistance is not as bad as the conventional one, and no improvements have been made.

Furthermore, as with the aluminum pigment, it is extremely meaningful to improve the chemical resistance and electrical insulation properties of bronze powder, iron powder, and other metal powders.

In view of these circumstances, the inventors of the present invention have conducted extensive research into metal powders that are chemically resistant, electrically insulating, and have excellent storage stability. After coating, it was discovered that the objective could be achieved by further treating the coating layer of the polymer with an amine, and based on this knowledge, the present invention was completed.

That is, the present invention provides a powdered metal composite characterized in that the surface of metal particles is coated with a polymer made of a reaction product of isocyanate and water, and the coating layer of the polymer is further treated with an amine. This is what we provide. Such powdered metal composites are prepared by dissolving 100 parts by weight of metal powder, 1 to 100 parts by weight of isocyanate, and 0.1 to 10 parts by weight of water based on 100 parts by weight of the isocyanate in an inert solvent.
After adding 0 parts by weight of the metal powder to cause a reaction and coating the particle surface of the metal powder with polyurethane, further adding 0.5 to 50 parts by weight of amines based on 100 parts by weight of the isocyanate to coat the surface of the coated polymer. It can be manufactured by processing.

Examples of the metal powder used in the present invention include aluminum, zinc, iron, tin, nickel, copper, lead, silver, platinum, gold,
Examples include powders such as various alloys and magnetic powders. Among these, aluminum powder, which is often used as a paint pigment, is preferred.

Examples of the inert solvent used include mineral spirits, solvent naphtha, toluene, and xylene.

The incyanate used in the present invention includes monomers having two or more incyanate groups in one molecule, prepolymers and adducts thereof, preferably monomers having two or three incyanate groups in one molecule, and Prepolymers and adducts. Examples of such substances include toluylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 4.
Diisocyanate monomers such as 4'-diphenylmethane diinocyane-1., isophorone diynnyanate,
These bifunctional sol polymers [for example, Asahi Kasei Corporation ■
Duranate D-101, D-102, etc.) manufactured by Asahi Kasei Kogyo Co., Ltd.) and billet-type brepolymers (Duranate 24A-100, manufactured by Asahi Kasei Kogyo, etc.). Particularly preferred monomers among these are toluylene diisocyanate and hexamethylene diisocyanate.

Among isocyanates, isocyanates having one incyanate group are not preferred because they do not produce a polymer even when reacting with water, so chemical resistance and electrical insulation cannot be obtained.

In the present invention, first, in the inert solvent, 100 parts by weight of the metal powder, 1 to 100 parts by weight of the incyanate,
and 0.1 to 0.1 parts of water based on 100 parts by weight of the isocyanate.
Add 100 parts by weight, further add a catalyst such as dibutyltin dilaurate if necessary, and heat with stirring until the amount of the isocyanate and incyanate added is 1.
If it is less than 1 part by weight, sufficient chemical resistance and electrical insulation cannot be obtained, while if it exceeds 100 parts by weight, no improvement in performance can be expected, and rather the adhesion of metal powder particles to each other becomes significant. This is not a good idea as it increases the number of aggregates. The preferred range in terms of performance and agglomerates is 3 to 30 parts by weight. However, if the amount of water added is less than 1 part by weight based on 100 parts by weight of the incyanate, polymerization of the isocyanate will be small, and the reaction will stop, resulting in a large amount of unreacted isocyanate, while if it exceeds 100 parts by weight. This is undesirable because it increases the occurrence of aggregates due to adhesion of metal powder particles to each other. The preferred amount of water added is from 5 to 50 parts by weight based on 100 parts by weight of the isocyanate.

This reaction is significantly influenced by temperature, and of course the reaction proceeds faster at higher temperatures, but the industrially desirable temperature is in the range of 40 to 100°C.

1. In the reaction between water and isocyanate, it is effective to add a commonly known catalyst such as dibutyltin dilaurate to increase the reaction rate.

In the present invention, the reaction is carried out in the presence of an insoluble solvent, and the solvent is desirably used in such a proportion that the residue on heating is 10 to 500 to 50 parts by weight.

In the present invention, there is no particular limitation on the order in which Isonane-1 and water are added, but methods such as dividing addition, for example, have the effect of suppressing the generation of aggregates caused by adhesion of metal powder particles to each other. Sometimes there are.

In addition, a portion of the ≠≠triple bonds coated on the surface of the metal powder particles and the unreacted incyanate groups are further three-dimensionalized by the Billet reaction to form a stronger coating layer.

In these reaction systems, isocyanate monomers and terminal isocyanate groups may remain.

In this case, during storage of the product, the incyanate groups may gradually react, causing metal powder particles to adhere to each other and cause agglomeration. Further, if the isocyanate monomer remains, it is undesirable in terms of toxicity to living organisms.

In the present invention, in order to eliminate the toxicity of such residual monomers and improve the instability during product storage, the particle surface of the metal powder is formed by a reaction between incyanate and water as described above. After coating with a polymer, amines are further reacted to eliminate residual monomers, and at the same time, the surface of the coated polymer is treated.

By treatment with amines, the remaining monomers and especially the terminal isocyanate groups on the surface layer of the coating polymer react with the amines and become inert and stabilized.

In this case, alkyl groups are imparted to the surface of the coating polymer, particularly by using alkyl amines as described below. This significantly suppresses adhesion and aggregation of particles to each other and improves storage stability.

Examples of amines used in this case include the following: Secondary amines are preferred because they significantly improve the dispersibility and storage stability of the product. Examples of the secondary amine include diptylamine, di-2-ethylhexylamine, synchlohexylamine, and diptylamine.

The appropriate amount of these amines to be added varies depending on the amount of residual monomer, but in the present invention, isocyanate 1
0.5 to 50 parts by weight based on 00 parts by weight, preferably 3
It is added in a range of 20 parts by weight. If the amount of amines added is less than 5 parts by weight, there is almost no effect, and if it exceeds 50 parts by weight, it is rather unfavorable in terms of storage stability and toxicity of the product.

The steps of these reactions can be shown as a model as follows.

(1) Reaction or adsorption of water on the surface of metal powder particles (2) Reaction of incyanate on the surface of metal powder particles (4) Three-dimensionalization by Hulett reaction.

-N N-0-N N-U'-IVV■v〜NIN y-1v
-----(5) Reaction of residual isocyanate monomer or terminal isocyanate group with amine Next, it can be confirmed that particles are present in the powdered metal composite of the present invention.

The novel powdery metal composite of the present invention is endowed with excellent chemical resistance and electrical insulation properties, and can be used as a metallic pigment in paints, for example. It is possible to save resources by using electric coating, etc.

Furthermore, the metal composite of the present invention has good storage stability and can be stored for a long period of time, making it extremely valuable industrially.

Next, the present invention will be explained in more detail with reference to Examples.0 The performance of the obtained product was evaluated according to the following method.

(1) Leak resistance (conductivity) of metallic paints Generally, when a high voltage is applied to metallic paints containing aluminum pigments, the aluminum particles become oriented and are continuous with the electrodes up to one pole, making it easier to conduct electricity. Paints that easily conduct electricity as described above are said to be unsuitable for electrostatic coating because current leaks and high voltage cannot be obtained.

In the present invention, this performance was evaluated by the following method.

That is, in the apparatus shown in Fig. 2, conductive wires W1 and W2 with a diameter of 2.5 mm are attached to both ends of glass tubes GK rubber stoppers P1 and P2 with an inner diameter of 27 mm and a length of 450 mm, and a 60 KV voltage is applied.
Apply a voltage of 430 mm to 30 + 111 mm
The conductor spacing at which current leaks was measured with an ammeter.

Acrylic resin (acrydic 47-712) and melamine resin Sunoku-Betsukamine J-820 (both manufactured by Nippon Reichhold Co., Ltd.) used for the paint composition used in this test.
Toluene/ethyl acetate/stil cellosolve was added to a mixture of 4.1 weight ratio of 100% of the mixture, and 7.5 parts by weight of the sample metal powder was added in terms of heating residue, and the mixture was thoroughly stirred and mixed with the sample. did.

(2) Electrical insulation properties of metal powder Generally, plastic is often used for the exterior of light electrical equipment, especially televisions, computer displays, etc., and high voltage is applied to these, so high static electricity is generated in the exterior material. If the paint on these exterior materials conducts electricity easily, it is said that if you touch it, you will receive a severe electric shock. Therefore, in these fields, it is said that a coating film that is difficult to conduct electricity is good.

On the other hand, the electrical insulation property of a metallic coating film is correlated with the electrical insulation property of the metallic pigment itself that is blended into the paint, and it is investigated whether dielectric breakdown occurs by applying a voltage of about IF;v to the pigment. It can be evaluated by

In the present invention, the solvent contained in the metal powder is replaced with unlubento naphtha, and the metal content is 40% to 70% by weight.
As shown in Fig. 3, the electrode spacing was fixed at lO, and while applying a pair of voltages to the electrodes with a super megohmmeter (manufactured by Toa Denpa Kogyo, model SM-5E), We touched the sample metal powder to see if it would cause dielectric breakdown (those with dielectric breakdown only show a resistance of a few megohms).

(3) Acid resistance and alkali resistance The acid resistance or alkali resistance of the coating film is determined by the alkyd resin (manufactured by Nippon Reichhold Co., Ltd., trade name Betsukosol J-524).
M-60) and melamine resin (manufactured by Nippon Reichhold Co., Ltd., trade name Super Beckamine L-117-60) in a weight ratio of 4:1 (solid content 60%) 100 parts by weight, Irgazin Yellow Mix 2 parts by weight of 3RT-N (manufactured by Ciba Geigy), 6 parts by weight of the test metal powder in terms of metal content, and a xylene/ethyl acetate mixed solvent (weight ratio 1/1) to make a total of 180 parts by weight. The paint prepared in
) and dry to the touch, then dry in a warm air circulation dryer at 120°C.
The coated plate baked for 5 minutes was immersed in a 0.1 N aqueous sodium hydroxide solution or sulfuric acid aqueous solution at 55°C for 4 hours.
The color difference △E before and after dipping was measured using SM color computer model 5.
Measured with M-2 [manufactured by Suga Test Instruments ■].

(4) Peeling resistance of Cellotape Apply cellophane tape to the same material as the leak resistance measurement specimen, press firmly with your fingertips, then peel off the cellophane rapidly.
The presence or absence of peeling of the paint film was examined.

(5) Storage stability In the sense of promoting and investigating the storage stability of metal powder samples, 3
00ml! Approximately 1002 metal powder samples were placed in a tin can, the lid was placed in a hot air circulation oven at 50°C for 7 days, and then the sample 502 was dispersed in 1 ton of mineral spirit, and then 200 mesh It is poured into a Millipore (manufactured by Millibore Co., Ltd., filtration test equipment) equipped with a nylon filter cloth, and further washed thoroughly with mineral spirit and acetone, the filtration residue is collected, and its weight is measured after drying. The heating residue 1007 and the filtration residue were calculated.

Reference Example 1 The inner diameter of an untreated aluminum pigment was 34.
5 crn, a ball mill with a length of 38.4 m and a diameter of 3.9 m.
Steel ball 42 in throat 9, atomized powder v p,
-500 (manufactured by Shiraishi Metal ■:]t, 4Kg, 1.7% mineral spirit and 102% stearylamine added, 6
After rotating at 0 rpm for 3 hours, mineral spirits)
2.87 was added and rotated for another 1 hour and 10 minutes, and then the pulverized aluminum slurry was washed with mineral spirits, extracted, and passed through a Dalton vibrating sieve [Sanei Seisakusho ■] equipped with a stainless steel wire mesh with a mesh size of 40μ. The under slurry was filtered out to obtain an untreated aluminum pigment. The metal content of this aluminum pigment was 74.0% by weight.

About this untreated aluminum pigment, it has alkali resistance,
Acid resistance, leak resistance, electrical insulation properties of metal powder, and cellophane peeling resistance were evaluated, and the results are shown in Table 1.

Reference Example 2 Preparation of Untreated Zinc Powder Paste Granular zinc powder (particle size characteristic number d' = 45μ) 200 f.

Oleic acid 5. Of, Mineral Spirit 2oornl
and an attritor loaded with 15kg of steel balls with a diameter of 5.
Manufactured by Mitsui Miike Seisakusho ■, MA-ISD type, tank capacity 4.
971 at 200 rpm for 16 hours to pulverize the zinc powder, the pulverized scale-like zinc powder was extracted and separated with mineral spirit, filtered from the mineral spirit, and phosphorus with a metal content of 60.1% by weight was obtained. A flaky zinc powder paste was obtained. The electrical insulation properties and storage stability of this product were evaluated, and the results are shown in Table 2.

Reference Example 3 Preparation of untreated copper powder paste (granular metallic copper powder (particle size characteristic number d' - 50μ) 200 g, stearic acid 5. (1), mineral spirit 200- and 15 kg of steel balls with a diameter of 5 mm were prepared in Reference Example 2) Put it in the attritor in the same way as 2.
After pulverizing at 0 rpm for 32 hours, the powder was extracted and separated using mineral spirits to obtain flaky copper powder paste with a metal content of 76.0% by weight.

The electrical insulation properties and storage stability of this product were evaluated, and the results are shown in Table 2.

Reference example 4 Preparation of untreated bronze powder paste Granular brass (weight ratio of copper and zinc 1/1) powder (particle size characteristic number a', , = 50 μ) 850 ft, stearylamine 5
．． Of, mineral spirit 700 rnl and diameter 5M
Steel ball mill (capacity 25t) in which steel balls 35 and 7 are charged
After operating at 58 rpm for 40 hours to crush the powder, it was extracted and separated using mineral spirits to obtain a scaly bronze powder paste with a metal content of 750 by weight.

The electrical insulation properties and storage stability of this product were evaluated, and the results are shown in Table 2.

(500f in terms of metal content) was placed in an all-purpose mixing and stirring container (manufactured by Sanei Seisakusho ■, vertical type 51), and pure water 51 and solvent naphtha 1324F were added and stirred at 60°C for 30 minutes, then further heated in a tolui oven. Isocyanate) 50
f, dibutyltinjilaure) 0.2 r and water 152
was added and reacted for 4 hours.

Next, the mixture was filtered using a Buchner funnel, dibutylamine 52 was added thereto, and the mixture was stirred for 15 minutes in a multipurpose stirring vessel to obtain an aluminum pigment paste with a heating residue of 51.2% by weight.

Alkali resistance of this product 1. We evaluated acid resistance, leak resistance, electrical insulation properties of metal powder, and cellophane peeling resistance.
The results are shown in Table 1. Storage stability was also evaluated, and the results are shown in Table 2 along with the evaluation of electrical insulation.

Examples 2 to 10 Using 676 g of the untreated aluminum pigment obtained in Reference Example 1, solvent naphtha, dibutyl tin dilaurate, incyanate of the type and amount shown in Table 1, and water,
The reaction was carried out in the same manner as in Example 1.

However, the amounts of solvent naphtha and dibutyltin dilaurate are as follows.

Solvent naphtha dibutyltin dilaurate example
2 9901i'2.59 # 3 990/7 0,5 /7 JL 4 990 II O,251//L 5 45
00# 1.0 /r If 6 4500 /L 3.0, /J〃7 99
Q〃l, Q tt 〃 8 4500// 2. OLL "9 4500" 1. Otr 〃1.0 4500/7 0.5 /J Next, filter the mixture using a Buchner funnel, add amine or amine and alcohol in the type and amount shown in Table 1, and stir for 30 minutes in a multipurpose stirring vessel. , an aluminum pigment paste was obtained.

The aluminum pigment paste thus obtained was evaluated for alkali resistance, acid resistance, leak resistance, electrical insulation of metal powder, and cellulose peeling resistance, and the results are shown in Table 1. In addition, for Example 2, storage stability was also evaluated, and the results are shown in Table 2 along with the evaluation of electrical insulation.

Comparative Example 1.2 Untreated aluminum pigment 6762 obtained in Reference Example 1, solvent naphtha (Comparative Example 1: 4500 g, Comparative Example 2
:99 ([') dibutyltin dilaurate (comparative example = 0
．． Comparative Example 10.25r) and the amounts of toluylene diisocyanate and water shown in Table 1 were used to react in the same manner as in Example 1. Then filtered through a Puchner funnel,
Add dibutylamine in the amount shown in Table 1 and stir for 30 minutes in an all-purpose mixing stirrer to obtain aluminum pigment paste.

The aluminum pigment paste thus obtained was evaluated for each performance, and the results are shown in Table 1.

Comparative Example 3 The untreated aluminum pigment 6767 obtained in Reference Example 1 was placed in a universal mixing stirring container, and mixed with 5 f of water and sol.
107 was added and stirred at 60°C for 4 hours. It was then filtered through a Buchner funnel to obtain a 47.0% by weight aluminum pigment paste. The performance of this product was evaluated and the results are shown in Table 1.

Comparative Example 4 The untreated aluminum pigment 6762 obtained in Reference Example 1 was placed in a universal mixing stirring vessel, and 2.57 oleic acid and 952 solvent naphtha were added thereto and stirred for 60 minutes, with a heating residue of 65.2% by weight. An aluminum pigment paste was obtained. The performance of this product was evaluated and the results are shown in Table 1.

Comparative Example 5 For comparison, aluminum paste for automobile paint) M2O3 [
[manufactured by Asahi Kasei Industries, Ltd.]] was evaluated, and the results are shown in Table 1.

Comparative example 6 A 52.0% by weight aluminum pigment paste was obtained.

The storage stability and electrical insulation properties of this product were evaluated and the results are shown in Table 2.

'An aluminum pigment paste with a heating residue of 45.8% was obtained in exactly the same manner as in Comparative Example 7.

The storage stability and electrical insulation properties of this product were evaluated and the results are shown in Table 2.

Example 11 Untreated scaly zinc powder paste 166 obtained in Reference Example 2
(metal equivalent xoor), water 11, solvent naphtha 3
341, 1°V of tolulene diisocyanate and 0.19% of dibutyltin dilaurate were placed in a four-piece rosette variable flask equipped with a Teflon ring stirrer, and the reaction was carried out for 6 hours with stirring at 40°C. Dihexylamine 22 was further added and stirred for 15 minutes. Thereafter, it was filtered using a Puchner funnel to obtain a 53.0% by weight zinc powder paste.

The storage stability and electrical insulation properties of this product were evaluated and the results are shown in Table 2.

Comparative Example 8 The same procedure as in Example 11 was carried out except that dihexylamine was not used, and 52.6% by weight was added.
A zinc powder paste was obtained.

The storage stability and electrical insulation properties of this product were evaluated and the results are shown in Table 2.

Example 12 132 g of the untreated flaky copper powder paste obtained in Reference Example 3, 21 g of water, 3682 g of solvent naphtha, ior of hexamethylene diinocyanate, and 0.1 g of dibutyl totine dilaurate were placed in a separable flask and heated to 70°C. After 10 hours of reaction, 0.21 g of dibutylamine was added and the mixture was stirred at 70° C. for 2 hours, followed by filtration using a Buchner funnel to obtain flaky copper powder paste with a heating residue of 67.0%.

The storage stability and electrical insulation properties of this product were evaluated and the results are shown in Table 2.

Comparative example 9 A scaly copper powder paste with a heat residue of 67.3% was obtained.

The storage stability and electrical insulation properties of this product were evaluated and the results are shown in Table 2.

Example 13 Untreated flaky bronze powder paste 1 obtained in Reference Example 4
331, water 2.01, toluylene diisocyanate 10
2 and dibutyltin dilaurate 0.12 were placed in a separable flask and reacted at 50°C for 4 hours. After adding 0.5f of dibutylamine and stirring at 50°C for 30 minutes, it was filtered to leave a heating residue of 68.8 % flaky bronze powder paste was obtained.

The storage stability and electrical insulation properties of this product were evaluated and the results are shown in Table 2.

Comparative Example 10 A scaly bronze powder paste with a heat residue of 68.3% by weight was obtained.

The storage stability and electrical insulation properties of this product were evaluated and the results are shown in Table 2.

[Brief explanation of the drawing]

FIG. 1 is an electron micrograph showing an example of the surface state of particles in the metal composite of the present invention. Fig. 2 is a schematic diagram of a device for measuring leak resistance, in which the symbols are the conductor spacing, d is the inner diameter, G is the glass tube, L is the length of the glass tube, and Pl and Pl are rubber. The plug, S is the paint under test, Wl and Wl are conductive wires, and H is a high voltage generator. Figure 3 is a schematic diagram of a device for measuring the electrical insulation properties of metal powder, in which symbols W1 and Wl are conductive wires, C is a conductor fixing plate, H is a high voltage generator, and S is the metal under test. It is powder. Patent Applicant: Asahi Etsukart Co., Ltd. Agent Akira Agata Figure 2 Figure 3 Procedural Amendment Showa. . January 14, 2015 1, Display of the case 1982 Patent Application No. 206745 2 Name of the invention Powdered metal composite and its manufacturing method 3 Person making amendments Relationship to the case Patent applicant address Yurakucho, Chiyoda-ku, Tokyo -Chome No. 1-2 Name Asahi Etsu Cult Co., Ltd. Representative Kunio Satake 4th Administrator 8 Contents of Amendment (1) The scope of the patent claims will be amended as shown in the attached sheet. (2) By treating the surface of the coating polymer in lines 8 to 7 from the bottom of page 4 of the specification with amines,
By inactivating the terminal isocyanate groups and residual monomers of the polymer coating the metal particles by reacting with amines, the following has been corrected. (3) P [Page 6, lines 5 to 8, "Recently...recently...requested." All the following will be corrected. ``Recently, one-coat metallic finishes have been increasingly used for plastic bumpers, wheels, and other equipment parts due to their advantages in terms of design and painting costs, but in these fields of use, the coating surface is (4) Pigment 9, lines 2 to 9, ``In an inert solvent, the pigment itself is required to have high chemical resistance.・
...can be manufactured. ” will be corrected as follows. "In an inert solvent, 1 to 100 parts by weight of isocyanate per 100 parts by weight of the metal powder and 901 to 100 parts by weight of water per 100 parts by weight of the incyanate are added and reacted, and the particles of the metal powder are reacted. It can be produced by coating the surface with a polymer consisting of incyanate and water, and then further adding 1105 to 50 parts by weight of amines per 100 parts by weight of the isocyanate to treat the surface of the coated polymer. (5) On the 9th page, 6 lines from the bottom, add the following sentence after "...is suitable." ``Also, this metal powder may be in any shape such as spherical, flaky, or acicular, but the particle size is as follows: It is practically desirable to have a range in which the residual amount is 50% or less.'' (6) At the end of page 10, after ``In the present invention,'' add ``For example,'' in its entirety. (7) On page 12, lines 3 to 5, “This reaction...
range. ” will be corrected as follows. "This reaction is usually carried out while stirring or kneading, but it is significantly influenced by temperature conditions, and the higher the temperature, the faster the reaction proceeds. When carried out industrially, a temperature in the range of 40 to 100 °C is desirable." (8) Same page 12, No. 10
~ Line 13, "It is desirable that the present invention..." is corrected as follows. "In the method of the present invention, the reaction is carried out in an inert solvent. In this case, it is desirable to use an amount of solvent such that the metal concentration is 10 to 50 weight φ." (9) Ibid. No. 12
The following correction has been made to the statement "The present invention may have some effects..." on lines 14 to 18 of the page. ``In addition, the order of addition of isocyanate and water in the method of the present invention is not particularly limited and can be carried out in any order. If it is added, it is advantageous because it can suppress the generation of agglomerates caused by adhesion of metal powder particles to each other." α0 Next to "1 Stabilizes" in the 2nd line from the bottom of page 13 of the same page: We have added the following text: ``The reaction between the residual monomer or the terminal iso7anate group and the amines proceeds relatively smoothly, so there is no need for particular heating during the reaction, but if it is carried out industrially, If desired, it can be heated to a temperature of about 80°C." αη On page 14, lines 1 to 7, [(In the formula, R1 and..., etc. are included)" was corrected as follows. A secondary amine represented by (in the formula, R1 and R2 are hydrocarbon groups having 1 to 18 carbon atoms) is preferable because it can improve the dispersibility and storage stability of the product. R1 in amine
and R2 may be any linear or branched aliphatic hydrocarbon group, alicyclic hydrocarbon group, or aromatic hydrocarbon group, and R1 and R2 may be the same or different. You can leave it there. Examples of the secondary amines are dimethylamine, diethylamine, methylethylamine, di-n-propylamine, ethylpropylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-n-hexylamine, di-n-propylamine, -octylamine, di-2-ethylhexylamine, di-n-decylamine, dilaurylamine, di-n-dodecylamine,
Examples include cimyristylamine, civalmitylamine, distearylamine, dioleylamine, diphenylamine, dibenzylamine, dicyclohexylamine, etc. (a) ``Novel invention of the present invention'' on page 18, lines 5 to 14.・It is expensive.i The following correction is made: [The novel powdered metal composite of the present invention is characterized by the fact that the surface of the powdered metal is coated with a polymer made of a reactant of incyanate and water. Improved chemical resistance and electrical insulation,
In addition, changes in hue and aggregation of powder particles are suppressed, and treatment with secondary amines suppresses biohazardousness and deterioration of storage stability caused by residual monomers and terminal isocyanate groups of the coating polymer. . Therefore, when the powdered metal composite of the present invention is used as a paint pigment, each particle is coated with a non-conductive polymer and is difficult to conduct electricity, so it exhibits excellent electrostatic coating properties. Due to the improved compatibility of
It has the effect of high adhesion between the metal powder and the metal powder, and good adhesion. ” At α, page 22, lines 2 to 5, “(4) Resistance to cellophane tape peeling... harmful effects have been investigated.” We have made 9 corrections to all of the following. [(4) Peeling resistance of cellophane adhesive tape A cellophane adhesive tape (trade name: Cellotape, manufactured by Nichiban Co., Ltd.) was affixed to the same specimen as the acid and alkali resistance test specimen, pressed firmly with the fingertips, and then rapidly peeled off. The peeling state of the paint film was examined. "Alpha force" The 4th line from the bottom of page 23 has been corrected to read "removability of cellophane tape" as "removability of self-adhesive tape". At α time, on page 24, line 6, correct "scaly flake-like" to "silky flake-like". At α time, "bronze" in the first line of page 25 will be corrected to "shinchu". Alpha Force The second line of page 25 of the same page is corrected to "weight ratio 1/li" and "weight ratio 7/3." α Time "Bronze" in line 9 of page 25 is corrected to "shinchuj". 0 "Resistance to cellophane peeling" in line 7 of page 26
1. Corrected to ``Removability of adhesive tape with seven openings.'' and cut it out. (1) In the 3rd line from the bottom of page 27, cellulose peeling resistance j has been corrected to ``cellophane adhesive tape peeling resistance.'' Q. I am correcting the text on page 33, line 10 and 5 lines from the bottom to ``J'kr flaky bronze powder paste.'' ■ In the third row from the bottom of Table 2 on page 35, in the second column, we have corrected "straight brass ends" to "shinchu ends." Claim 1: The surface of the metal particle is coated with a polymer made of a reaction product of isocyanate and water, and the surface portion of the coating polymer is a terminal isocyanate of the polymer. 2. The powder metal composite according to claim 1, wherein the powder metal composite is at least 418 selected from the group consisting of 3 monomers, prepolymers and adducts thereof. 3. The powdered metal composite according to claim 2, wherein the isocyanate monomer is at least one selected from toluylene diisocyanate and hexamethylene diisocyanate. 4. Claims 1, 2, or 3, wherein the amine is a secondary amine represented by the general formula (in which R1 and R2 are hydrocarbon groups having 1 to 18 carbon atoms) Powdered metal composite as described in . 5. The powdered metal composite according to claim 1, 2, 3, or 4, wherein the metal powder is aluminum powder. 6 In an inert solvent, 100 parts by weight of the metal powder, 11 to 100 parts by weight of iso7anate, and 0.1 to 100 parts by weight of the inocyanate, 2 water, and reacted; After the particle surface of the metal powder is coated with a polymer consisting of isocyanate and water, the surface of the coated polymer is further treated by adding 05 to 50 parts by weight of amines per 100 parts by weight of the incyanate. A method for producing a powdered metal composite. 7 Incyanate has 2 incyanate groups in one molecule.
At least one selected from monomers, prepolymers and adducts thereof having one or three monomers! two! The method according to claim 6. 8. The method according to claim 7, wherein the isocyanate monomer is at least one selected from toluylene diisocyanate and hexamethylene diisocyanate. 9. Claim 6, 7, or 8, wherein the amine is a secondary amine represented by the general formula (R1 and R2 in the formula are hydrocarbon groups having 1 to 18 carbon atoms) The method described in section. 10. The method according to claim 6, 7, 8 or 9, wherein the metal powder is aluminum powder. 11 Using 100 parts by weight of aluminum powder and 3 to 30 parts by weight of isocyanate, and using 100 parts by weight of the isocyanate.
11. The method of claim 10, wherein 95 to 50 parts by weight of water and 3 to 20 parts by weight of amines are used.

Claims (1)

[Claims] 1. A powdered metal composite characterized in that the surface of metal particles is coated with a polymer made of a reaction product of incyanate and water, and the surface of the coated polymer is further treated with an amine. . 2 Isocyanate has 2 isocyanate groups in one molecule.
The powdered metal composite according to claim 1, which is a monomer having one or three monomers, a prepolymer thereof, and an adduct thereof. 3. The powdered metal composite according to claim 2, wherein the iso7anate monomer is toluylene diisocyanate and hexamethylene diisocyanate. 4. A patent in which the amine is a secondary amine represented by the general formula (R and R2 are linear, branched, or cyclic aliphatic groups having 1 to 18 carbon atoms) A powdered metal composite according to claim 1, 2, or 3. 5. The powdered metal composite according to claim 1, 2, 3, or 4, wherein the metal powder is aluminum powder. 6 In an inert solvent, 100 parts by weight of metal powder, 1 to 100 parts by weight of isocyanate, and 100 parts by weight of incyanate
After 0.1 to 100 parts by weight of water is added and reacted to coat the particle surface of the metal powder with a polymer consisting of isocyanate and water, 05 to 50 parts of amines are added based on 100 parts by weight of the isocyanate. 1. A method for producing a powdered metal composite, which comprises adding parts by weight to treat the surface of the coating polymer. 7 Incyanate has 2 incyanate groups in one molecule.
7. The method according to claim 6, which is a monomer having 1 or 3 monomers, prepolymers and adducts thereof. 8. The method according to claim 7, wherein the incyanate monomers are toluylene diisocyanate and hexamethylene diisocyanate. 9 The amine is a secondary amine represented by the general formula (R1 and R2 in the formula are linear, branched, or cyclic aliphatic groups having 1 to 18 carbon atoms) A method according to claim 6, 7 or 8. 10. The method according to claim 6, 7, 8 or 9, wherein the metal powder is aluminum powder. 11 100 parts by weight of aluminum powder (using 3 to 30 parts by weight of ylanganate, and based on 100 parts by weight of the isocyanate, 5 to 50 parts by weight of water and 3 parts by weight of amines)
11. The method of claim 10, using ~20 parts by weight.