JPS6018558A - Nonignitable aerosol paint composition containing metallic powder - Google Patents

Abstract

PURPOSE:To provide the titled composition having excellent storage stability and giving beautiful coating layer exhibiting the natural color of metallic powder, by compounding a specific resin vehicle, a nonflammable organic solvent, a high- boiling solvent and a specific amount of metallic powder, etc. CONSTITUTION:The objective composition is produced by compounding ( I ) 100pts.wt. of a stock liquid composition obtained by mixing (A) an acrylic resin and/or an alkyd resin having an acid value of <=2.0, (B) a nonflammable organic solvent (e.g. trichlorotrifluoroethane), (C) a high-boiling solvent (e.g. ethyl cellosolve), (D) metallic powder, and if necessary (E) a pigment, with (II) preferably 100-150pts.wt. of a propellant (e.g. dimethyl ether). The amount of the metallic powder D in the stock liquid is 5-20(wt)%, and the ratios of A:B:C(wt%) are preferably (20-30):(20-40):(20-50).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a non-flammable aerosol coating composition, and more particularly to a non-flammable, solvent-borne aerosol coating composition containing metal powder and capable of providing a metallic coating.

Aerosol paints use large amounts of flammable organic solvents to dissolve resin components, and the low flash point of these dissolved substances poses a risk of ignition and explosion, which poses a major problem in paint manufacturing and handling. Ru.

Therefore, water-dispersible resin is used as the main component of the vehicle, and a relatively small amount of a mixed solvent of organic solvent and water is used.
445) and solution-type slightly flammable aerosol paint (Japanese Patent Publication No. 58-4'945), which is a solution-type slightly flammable aerosol paint containing a propellant consisting of a specific proportion of dimethyl ether and dichlorodiphenylmethane in a nonflammable organic solvent, a high-boiling solvent, and a resin vehicle.
i, a specific proportion of trichloro1-trifluoroethane or trichloromonofluoromethane to the neutralized alkyd resin;
A non-flammable dissolved J-type aerosol coating composition containing a solvent having a flash point higher than the temperature that causes intense evaporation of the non-flammable solvent (for example, Japanese Patent Application Laid-Open Nos. 57-36158 and 57-36)
No. 36163) have been proposed.

On the other hand, in the field of paints, there is a growing desire to incorporate metal powder into paint compositions to obtain paint films with a metallic feel. However, even if you try to incorporate metal powder into an aerosol paint composition, in water-based aerosol paints, the metal powder easily reacts with water, causing discoloration, dissolution, etc., and the original hue and metallic feel of the metal powder cannot be utilized. It has not been put into practical use, and water-based aerosols suffer from hydrolysis of trichloromonofluoromethane and other substances by water, which poses storage problems, and the containers are prone to rust. This does not solve the problem in any way.

In addition, in conventionally known solvent-based aerosol coating compositions, water-soluble acrylic resins, alkyd resins, etc. are usually used as the resin vehicle, so when metal powder is blended, free carboxyl groups and hydroxyl groups remaining in the resin The metal powder reacts with the metal powder, causing discoloration, and the residual peroxide of the catalyst used in the reaction of the resin itself also reacts with the metal powder, causing discoloration.

In systems containing a resin vehicle whose pH is roughly neutralized to 6.5 to 8.0, the acrylic resin or alkyd resin is usually neutralized with an amine, but the water produced by neutralization,
Alternatively, the presence of a salt causes discoloration of the metal powder due to a reaction with the metal powder when it is blended, and also has an adverse effect on storage stability, appearance, etc., making it impossible to achieve the purpose of the invention.

Therefore, the present inventors were able to provide a coating film with the original color of the metal powder and a metallic feel without causing any discoloration even if metal powder is mixed in with a non-flammable aerosol paint.
As a result of intensive research in order to obtain an aerosol paint with excellent storage stability and appearance, we discovered that the objective could be achieved by using a solvent-based composition using an acrylic resin or alkyd resin with a specific acid value as the resin vehicle, and published this book. The invention was completed.

That is, according to the present invention, a propellant is blended into a stock solution consisting of a resin vehicle, a nonflammable FJA solvent, a high boiling point solvent, a metal powder, and if necessary a pigment, and the resin vehicle has an acid value of 2.0 or less. A non-flammable metal powder-containing aerosol coating composition is provided, which is an acrylic resin and/or an alkyd resin and contains metal powder in an amount of 5 to 20% by weight of the stock solution composition.

The aerosol composition of the present invention basically belongs to a solvent-type non-flammable aerosol composition that does not contain water, and has a non-flammable composition that is the same or similar to the above-mentioned JP-A-Sho or JP-Ko-Sho invention. . In other words, it is a solvent-type non-flammable composition consisting of a stock solution consisting of a resin vehicle, a non-flammable organic solvent, and a high-boiling solvent as main components, and pigments added as necessary, and a propellant in a non-flammable proportion. be.

Such solvents or propellants in aerosol compositions are known per se, and non-flammable compositions are also well known to those skilled in the art, but a brief explanation is as follows. First, examples of nonflammable organic solvents include trichloromonofluoromethane, trichlorotrifluoroethane, methylene chloride,
Aliphatic halogenated hydrocarbons such as methyl chloroform are usually preferably used. Among them, it is particularly preferable to use trichlorotrifluoroethane from the viewpoint of inhalation toxicity to the human body.

Any organic solvent having a flash point higher than the boiling point of the nonflammable organic solvent can be used as the high boiling point solvent, such as ethyl cellosolve, butyl cellosolve, propylene glycol methyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, aromatic Group-based high boiling point mixed solvents, such as Tsurpets #100. #
150, etc.

If a nonflammable organic solvent and a flammable high boiling point solvent are used in combination, the nonflammable organic solvent will evaporate and the latent heat of vaporization will prevent the evaporation of the high boiling point solvent, further pushing up the flash point and increasing the gas concentration of the nonflammable organic solvent. Made non-flammable and flame retardant. Lower alcohols of the Shizuki group are used as high-boiling point solvents, but they can be used in small amounts for the purpose of making them non-flammable and flame retardant, as well as improving the drying properties of aerosol paints. It can be safely added to dimethino, which is used in solvent-based aerosol paints (used as a propellant).
Chyl, dichlorodifluoromethane, etc. are preferably used, and if desired, monochlorodifluoromethane, liquefied petroleum gas, etc. can also be added in appropriate amounts.

The amount of propellant is usually 100 to 100 mm per 100 mm of the stock composition.
It is used in a proportion of 150 parts by weight. The proportions of the solvent and propellant are appropriately selected depending on the type of the solvent and the non-flammable proportion.

In the present invention, however, metal powder, such as aluminum paste 55-103, aluminum paste 53-119, can be used together with the pigment or instead of the pigment to obtain a metallic paint.
(Toyo Aluminum), Hydrolac WH60 (Etzkart Werga), Gold Powder 88-945 (Toyo Aluminum)
, gold powder 3L5.2L5.5L5 (Toyo Aluminum Co., Ltd.), bronze powder, -1 copper powder, etc., it is necessary to use a specific acrylic resin or alkyd resin as the resin vehicle of the coating composition. This is one of the most important characteristics of

The present inventors have continued their research to incorporate metal powders such as those described above into conventional non-flammable solvent-based aerosol paint compositions, but all of the conventional metal powder discoloration paint compositions have poor needle stickiness. I didn't see any success. Moreover, the primary reason for this is the free carboxyl groups remaining in the resin.
It was discovered that the metal powder was based on unreacted acrylic acid, and that when a neutralized resin was used, it was due to the water and salt produced by the neutralization reaction, and by improving the resin vehicle, metal powder could be safely incorporated. It was only after learning about scales that I was able to complete this invention.

Thus, the resin vehicle used in the present invention has an acid value of 1.
．． It must be an acrylic resin or alkyd resin of 0 or less. Such resins are not those whose acid value has been adjusted to 2.0 by neutralization, but are resins that have been originally manufactured to have an acid value of 2.0 or less through selection of raw materials, selection of reaction catalysts, reaction conditions, etc. be. In addition, other resins with low acid values, alkyd resins, natural resins, etc., are used to improve coating performance.
You can also use j.

According to the findings of the present inventors, if the acid value exceeds 2.0, the blended metal powder will change color in a short period of time, for example, 3 to 6 months, and a beautiful coating film will not be obtained, and the acid value will be less than 2.0. Those with a C value of 1.0 or less, particularly those with a C value of 1.0 or less, have extremely excellent needle stickiness
It was found that there was no discoloration of the metal powder.

Therefore, it is essential that the acrylic resin or alkyd resin that serves as the resin vehicle has an acid value of 2.0 or less, but it is more preferable to use one with as little reaction catalyst residue as possible in the polymerization of the acrylic resin from the viewpoint of adding metal powder. Of course.

Examples of resin vehicles that meet these requirements include commercially available products such as Dianal PW-289, PW-261 (manufactured by Mitsubishi Rayon), and Aloron 4557D (manufactured by Nippon Shokubai Kagaku Kogyo).

A system consisting of the above-mentioned resin vehicle, non-flammable organic solvent, and high-boiling solvent mixed with metal powder as described above is extremely stable, with no discoloration of the metal observed for a long period of time, and by adding a propellant, it is non-flammable. It is possible to provide a solvent-type metal powder-containing aerosol composition, and it is possible to provide a safe paint that fully satisfies the non-hazardous substance requirements under the Fire Service Act.

Usually, each of these components has a resin content (solid content) of 20~
A stock solution composition is obtained by blending 5 to 20 wt.% of metal powder to a resin-solvent composition containing 30 wt.% of a nonflammable organic solvent, 20 to 40 wt.% of a nonflammable organic solvent, and 20 to 50@1% of a high boiling point solvent. ,
By adding 100 to 160 parts of propellant per 100 parts of this composition, a stable and safe F1 composition of the invention is made. However, the above are merely specific examples of preferred embodiments of the present invention, and can be modified as appropriate depending on the purpose and use. However, with regard to metal powder, if it is less than 5% by weight of the resin-solvent composition, it is insufficient to achieve the objective of the present invention of obtaining a coating film with a metallic feel and hiding properties, and if it exceeds 20% by weight, it is difficult to coat. It is desirable to limit the amount within the above range since the proportion of metal powder on the film surface tends to increase, which is undesirable and tends to reduce the performance of the coating film.

The thus obtained aerosol coating composition of the present invention does not change color due to oxidation or dissolution of metal powder even when stored for 6 months at 40°C, nor does it exhibit corrosion or foreign matter generation within the color during storage, making it non-flammable and safe. It is extremely useful as a coating material, as it can be used to provide a coating film with a beautiful metallic feel.

The present invention will be explained below with reference to Examples.

Example 1 2Qwt% of propylene glycol methyl ether, 10W% of isopropyl alcohol, and 16wt% of gold powder 3L5 (manufactured by Toyo Aluminum) as metal powder were placed in a stainless steel container and dispersed and mixed using a disper. Acrylic resin (Dianal PW-289, manufactured by Mitsubishi Rayon, resin acid value 1.5) dissolved in propylene glycol methyl ether in advance
, resin content 5Qwt%) was added and uniformly dissolved. Next, 4Qwt% of trichlorotrifluoroethane was added as a nonflammable solvent and mixed thoroughly to form a paint stock solution composition of 1
It's q.

As a result of measuring the flash point of this stock solution using a JIs-2265 Clear brand open type flash point meter, no flash point was found and it was confirmed that it was non-flammable.

Pack the above stock solution composition into an aerosol can and use 100wt of stock solution.
%, 130 wt % of dimethyl ether was filled as a propellant to obtain an aerosol paint. For spraying, use a nozzle made by Spray-on Co., Ltd. (FFJL).

Ta.

Comparative Example 1 The acrylic resin of Example 1 was used as Dianal PW-289 (
(resin acid value: 2.5, resin content: 50 wt%), paint stock solution composition 1 was obtained in the same manner as in Example 1, and dimethyl ether propellant was added at 130 wt% per 100 wt% of the stock solution.
% using aerosol coating 1.

Example 2 A paint stock solution composition was obtained by changing the metal powder in Example 1 to aluminum paste 53-119 (manufactured by Toyo Aluminum Co., Ltd.) and using the same 4-pig method as in Example 1, and further adding a dimethyl ether propellant to a stock solution of 100%.
*1 process using 110wt% for t%.

I made azole paint.

Comparative Example 2 The acrylic resin of Example 1 was used as Dianal LW-106 (
A paint stock solution composition was obtained instead of a resin with an acid value of 8.7 and a resin content of 50 wt%, and an aerosol paint was made using 130 wt% of dimethyl ether propellant per 2100 wt% of the raw at.

Example 3 The acrylic resin of Example 1 was used as Alloron 4557 (manufactured by Nippon Shokubai Chemical Co., Ltd., resin acid value 1.0, resin content 5Qwt%)
Instead, a paint stock solution composition was obtained, and then an aerosol paint was prepared using 100 wt% of the stock solution and 160 wt% of the lydimethylester propellant.

Comparative Example 3 Acrylic resin Aloron 4557-D (resin acid value 7.5,
An aerosol paint was prepared in the same manner as in Example 3, except that a resin containing 150 wt%) was used.

Table 1 below shows the storage stability of the aerosol paints obtained in each Example and Comparative Example and the performance of the coating film sprayed on a test plate with each aerosol paint.

Table 1 The test method and evaluation criteria are as follows.

Stingability: After applying the aerosol paint in a constant temperature room at 40°C for 6 months, we compared the color of the paint film when spraying with the color of the paint film that was applied immediately after adjusting the aerosol coating. , see the color change.

It is judged as good, slightly poor, or poor depending on the presence or absence of color change.

Water resistance: Spray the aerosol paint on the tin plate and keep it at room temperature for 30 minutes.
The coated plate obtained by drying for 5 days was immersed in water for 5 days, and the appearance of the coating film was observed.

It is graded as good, slightly poor, or poor depending on the presence or absence of blisters and whitening.

Adhesion: Spray aerosol paint onto a polished steel plate, and after drying, subject the paint film to a cellophane tape peeling test.

95, /100 or higher is good, 94/100 to 70/1
00 is considered slightly poor, and 70/100 or less is considered poor.

Paint film appearance: Spray the aerosol paint onto the tin plate to cover the paint film appearance by visual inspection.

It is classified as good, slightly poor, and poor depending on the brightness and gloss.

Flash point: Measured using JISK-2265 Clear brand open type flash point meter.

patent application agent Patent attorney Takeo Ito 479

Claims (2)

[Claims] (1) A propellant is blended into a stock solution consisting of a resin vehicle, a nonflammable organic solvent, a high boiling point solvent, a metal powder, and if necessary a pigment, and the resin vehicle is an acrylic resin with an acid value of 2.0 or less and/or A non-flammable metal powder-containing aerosol coating composition which is an alkyd resin and contains metal powder in an amount of 5 to 20% by weight based on the stock solution composition. (2) 20 to 30% by weight of resin vehicle (solid content),
Nonflammable organic solvent 20-40% by weight, high boiling point solvent 20-5%
100 parts by weight of a propellant is added to 100 parts by weight of a stock solution consisting of 0% by weight, 5 to 20% by weight of metal powder, and pigments added as desired.
The composition according to claim 1, which contains 0 to 160 parts by weight.