JPH08283623A - Electroconductive and noncombustible coating material - Google Patents

Abstract

PURPOSE: To obtain an electroconductive and noncombustible coating material capable of electrically detecting a residual amount of the coating material in a coating material tank in a large scale marking apparatus used for billets and pipes in iron and steel factories, automobile factories, etc. CONSTITUTION: This electroconductive and noncombustible coating material having 15kΩ.cm-300kΩ.cm electrical resistance comprises 100 pts.wt. of a noncombustible coating material prepared by blending at least a coloring matter, a resin and a binder in one or >=2 halogen-based solvent selected from among tetrachloroethylene, methylene chloride, dichlorofluoroethane and pentafluoropropane and 0.05-1.5 pts.wt. quaternary ammonium halide compound added as an electroconductivity donating agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-combustible paint having conductivity, and is suitable for a marking device, particularly for a large marking device used for billets and pipes in steel factories, automobile factories and the like. Is provided.

[0002]

2. Description of the Related Art As is well known, a conductive paint is mixed with a conductive filler (for example, metal powder or carbon fiber) and a conductivity-imparting agent (for example, lithium compound or ammonium compound). There are various types of paints, and paints of various formulations have been put into practical use or proposed.
The former is mainly used for forming a conductive coating film such as a radio wave shield material and a printed circuit board, and the latter is used for ink of a charge control type printer.

As is well known, there are water-based paints and halogen-based solvent-based paints as nonflammable paints, and paints having various formulations have been put into practical use or proposed.

On the other hand, as is well known, the marking device is a small one represented by a word processor generally used as office equipment and a large marking device for billets and pipes generally used as industrial equipment. (For example, Shot Marker S10: Product name: Mark Tech Co., Ltd.)
There is.

When a charge control type printer is used in the former small marking device, it is indispensable to use a conductive paint, and as the conductive paint, for example, JP-A-60-118767 is used. And JP-A-6-22
As described in Japanese Patent No. 0374, a mixture of lithium chloride, which is a lithium compound, and a quaternary ammonium salt of an organic anion, which is an ammonium compound, is used as a conductivity-imparting agent.

The latter large marking device employs an air jet type nozzle, and in this case it is not necessary to use conductive paint, and as far as the present inventors know, conductive paint is used for large marking device. There is no example.

The latter large marking device is often used in steel factories and automobile factories. In such a case, nonflammable paint is adopted from the viewpoint of safety. From the standpoint of working speed, a halogen-based solvent-based one, which has a fast drying speed, is used.

By the way, when the large marking device is in operation, it is necessary to measure the remaining amount of the paint filled in the paint tank of the device.

This is because the above-mentioned large-scale marking device is usually automated and continuously and automatically operated, so that it is necessary to avoid "paint running out" during operation as much as possible. .

Conventionally, as means for controlling the amount of paint in the large-sized marking device, means for visually checking the remaining amount by using a transparent or semi-transparent container whose contents can be seen as the paint tank and a weight scale are attached to the paint tank. A means for knowing the remaining amount by weight measurement has been put to practical use.

In addition, Japanese Utility Model No. 3003544 discloses that
There has been proposed a means for knowing the remaining amount by using an aerosol container as a paint tank and detecting a pressure change in the container with a pressure switch.

[0012]

When the above-mentioned visual means is used as the paint amount management means of the large-sized marking device, a supervisor who watches the remaining amount of the paint is required, so that labor saving is promoted. In the case of adopting the means for measuring the weight described above, there is a problem that the device itself becomes heavy due to the attachment of the weight scale, and there is a problem that the weight scale malfunctions due to the vibration of the device. is there. There is a problem in that the means described in Japanese Utility Model No. 3003544 cannot be applied unless an aerosol container is used.

The inventor of the present invention has studied to solve the above-mentioned various problems as a technical problem. On the way to this, a conductive paint is used for the large marking device to electrically manage the paint amount. I got the idea to do it.

That is, when the paint tank of the large marking device is filled with the conductive paint, the paint can be energized to easily detect the remaining amount of the paint by the detection electrode.

The present inventor has carried out research to embody the above idea. As mentioned above, in steel factories and automobile factories, halogen-based solvent-based nonflammable paints are used for large marking devices. Finding a substance that does not impair the coating properties of the non-flammable coating and obtains the required electric resistance value from among the conductive fillers and conductivity-imparting agents used in conventional conductive coatings. I couldn't.

That is, when a metal powder is mixed as the conductive filler, there is a risk of reacting with a halogen-based solvent to impair the coating properties, and when a carbon powder is mixed, such a risk is small, but the marking device is used. The viscosity of the paint used for is considerably lower than the viscosity of the conductive paint used for forming the conductive coating film such as the radio wave shield material and the printed circuit board, and therefore there is a risk that it will settle and the paint characteristics will be impaired. This sedimentation phenomenon is the same when metal powder is mixed, and also occurs when carbon fiber is mixed as a conductive filler.

When lithium chloride or a quaternary ammonium salt of an organic anion is blended as the conductivity-imparting agent, the electrical resistance value is sufficiently high in any case if the addition amount does not affect the coating properties. However, if it is added until the required electric resistance value is reached, the coating properties will be impaired. It should be noted that 0.1% of sodium fluoride, sodium chloride, sodium acetate and triammonium citrate was added to methylene chloride which is a kind of halogen-based solvent, but in each case, the electric resistance value was 2 ×. 10 ⁴ KΩ
・ It could not be less than cm.

Therefore, the present inventor has conducted numerous trials and experiments in search of a conductivity-imparting agent that can obtain a required electric resistance value without impairing the coating characteristics of the halogen-based solvent-based incombustible coating material. As a result, they discovered this and completed the present invention.

[0019]

Means for Solving the Problems That is, the present invention is one or more halogen-based solvents selected from tetrachloroethylene, methylene chloride, dichlorofluoroethane and pentafluoropropane, and at least a colorant and a resin binder. A non-combustible paint having conductivity, which is characterized by adding 0.05 to 1.5 parts by weight of a quaternary ammonium halide compound as a conductivity-imparting agent to 100 parts by weight of the non-combustible paint containing is there.

In the practice of the present invention, the quaternary ammonium halide compound is one selected from trioctylmethylammonium chloride, tetraethylammonium bromide, tetra-n-butylammonium bromide and tetra-n-butylammonium iodide. It is preferable to use two or more kinds, and the electric resistance value is 15 KΩ · cm to
It is preferably 300 KΩ · cm.

The structure of the present invention will be described in detail below. First, a non-flammable coating material prepared by blending at least a colorant and a resin binder in one or two halogen-based solvents selected from tetrachloroethylene, methylene chloride, dichlorofluoroethane and pentafluoropropane in the present invention is known. Examples of commercially available products include Tech Marker PSE75 White (trade name: Mark Tech Co., Ltd.) and Tech Marker PLE Red (trade name: Mark Tech Co., Ltd.). These are steel plants. It is widely used in large-scale marking devices in automobiles and automobile factories.

The specific formulation of the above-mentioned known non-combustible coating material in the present invention is 70 to 80% by weight of a halogen-based solvent, 5 to 25% by weight of a colorant (pigment or dye), and 3 to 5 of a resin binder.
15% by weight, if necessary, DBP, TOP, TE
A plasticizer selected from P and DBM is blended in an amount of 5 to 10% by weight.

Next, in the present invention, 0.05 to 1.5 parts by weight of a quaternary ammonium halide compound is added as a conductivity-imparting agent to 100 parts by weight of the above-mentioned known nonflammable paint. This blending ratio is important, and it is difficult to impart the required conductivity when the amount is 0.05 parts by weight, and the required conductivity is imparted even when it exceeds 1.5 parts by weight. It is difficult to do so, and there is a risk that the paint properties will be adversely affected.

Using trioctylmethylammonium chloride, trioctylmethylammonium bromide, tetraethylammonium bromide, tetra-n-butylbutylammonium bromide and tetra-n-butylammonium iodide as quaternary ammonium halides, the above When the blending ratio is set, the electric resistance value of the target product is 15 KΩ · cm to 3
It can be guaranteed that it will be 00 KΩ · cm.

The non-combustible coating material having conductivity according to the present invention (hereinafter also referred to as "the product of the present invention") can be easily prepared, and one of the above-mentioned quaternary ammonium halides or It is sufficient to add two or more kinds,
One or more of the above-mentioned quaternary ammonium halides may be added and stirred to a commercially available product of the above-mentioned known nonflammable paint. Each of the above quaternary ammonium halides is commercially available.

[0026]

Since the product of the present invention has conductivity, the well-known detection electrode is attached to the paint tank of the large-sized marking device, and the product of the present invention is filled in the tank, and the current is applied from the electrode. The electric signal obtained allows the remaining amount in the tank to be known. This will be described in more detail with reference to specific examples.

FIG. 1 is a conceptual explanatory view showing the structure of a paint remaining amount detecting mechanism attached to a paint tank of the large marking device. In FIG. 1, a cap of a paint tank 1 made of metal (usually stainless steel) is shown. 11 is a paint transport pipe 12
Is provided, the lower end of the transport pipe 12 is located near the bottom surface of the tank 1, and the other end (not shown in the figure) is connected to an air jet nozzle (not shown).

A detection electrode (usually a rod made of stainless steel having a diameter of 3 mm) 2 is attached to the cap 11 of the tank 1, and the lower end of the electrode 2 is located slightly above the lower end of the transport pipe 12. There is. The electrode 2 is covered with an insulating cover 21 made of a tetrafluoroethylene resin tube except the upper and lower ends.

An upper end of the electrode 2 is connected to an AC power source 22, and an amplification circuit and a relay drive circuit 23 are connected to the electrode 22 according to a conventional method, and the output thereof is the relay 2
An alarm output (usually an alarm lamp or an alarm buzzer) 25 is connected to the relay 24.

Since the product of the present invention has conductivity, when the tank 1 is filled with the product and used, the product 3 of the present invention is used.
When the lower end of the electrode 2 is in contact with the electrode 1, the tank 1 and the electrode 2 are in conduction. In this conductive state, the tank 1, the electrode 2, the widening circuit, and the relay drive circuit 2
3 is electrically closed and a current is flowing, but when the product 3 of the present invention is sent to the air injection type nozzle through the transport pipe 12, the liquid of the product 3 of the present invention filled in the tank 1 When the surface becomes lower than the lower end of the electrode 2 and the lower end of the electrode 2 and the product of the present invention are not in contact with each other, the conduction is cut off. This non-conducting state causes the amplifier circuit and the relay drive circuit 2
3 detects and activates the relay 24, and the activation of the relay 24 outputs the alarm output 25.

The present inventor has found that the electric resistance value of the present invention is 15
It has been confirmed by an experiment that the above-mentioned action is surely caused when KΩ · cm to 300 KΩ · cm. 300 KΩ / cm
In the case of the above electric resistance value, the flowing current becomes small, so that the measurement becomes difficult, and in the case of the electric resistance value of 15 KΩ · cm or less, the detection operation becomes unstable due to the leakage current. Practically, it is desirable to select from the range of 30 KΩ · cm to 160 KΩ · cm.

In the remaining paint amount detecting mechanism, the alternating current is used as the power source in order to avoid the polarization of the detecting electrode 2, and the insulating cover 21 covering the electrode 2 causes a malfunction. This is to prevent

[0033]

EXAMPLES Examples of the present invention will be given below. In each of the examples, the Cascaney LAB was used to measure the electric resistance value.
A conductivity meter DS-14 (trade name: Horiba, Ltd.) was used.

Example 1 45% by weight of tetrachloroethylene (manufactured by Kanto Denka Co., Ltd.), 31% by weight of methylene chloride (manufactured by Asahi Glass Co., Ltd.), 8% by weight of white pigment (titanium oxide: manufactured by Ishihara Sangyo Co., Ltd.),
A formulation consisting of 11% by weight of a resin binder (cellulosic resin: manufactured by Shin-Etsu Chemical Co., Ltd.) and 5% by weight of TOP (trioctyl phosphate: manufactured by Daihachi Chemical Industry Co., Ltd.) (Note 1).
The present invention product was obtained by adding 0.4 parts by weight of tetra-n-butylammonium bromide (manufactured by Nippon Shokubai Kagaku Co., Ltd.) to 100 parts by weight of the nonflammable paint (viscosity: 22 cp / 20 ° C) and stirring. . The electrical resistance value of the product of the present invention obtained here was measured immediately after preparation and was 143 KΩ · cm. Further, when the product of the present invention obtained here was stored indoors for 30 days and the state of paint was examined, no deterioration phenomenon such as precipitation of pigment was observed,
When the electric resistance value was measured, it was 149 KΩ · cm.

(Note 1) The formulation of the non-combustible paint used in this example is a formulation of a commercially available non-combustible paint for a large marking device (Tech Marker PSE75 White: trade name: Mark Tech Co., Ltd.).

The product of the present invention thus obtained was used for a large marking device (Shot Marker S10, trade name: Mark Tech Co., Ltd.) to mark a steel billet, which was as clear as when the above-mentioned commercial product was used. I got the mark.

Example 2 1.5 parts by weight of trioctylmethylammonium chloride (manufactured by Nippon Fine Chemical Co., Ltd.) was added to 100 parts by weight of a nonflammable paint having the same formulation as in Example 1 and stirred to obtain a product of the present invention. The electrical resistance value of the product of the present invention obtained here was measured immediately after the preparation, and it was 37 KΩ · cm. Further, the obtained product of the present invention was stored in a room for 30 days, and the state of the coating material was examined. As a result, deterioration such as precipitation of pigment was not observed, and the electric resistance value was 43 KΩ · cm.

When the steel billet was marked by using the obtained product of the present invention in the same large marking apparatus as in Example 1, it was as clear as the case of using the commercial product shown in Example 1. The mark was obtained.

Example 3 The present invention was obtained by adding 0.9 parts by weight of tetraethylammonium bromide (manufactured by Nippon Fine Chemical Co., Ltd.) to 100 parts by weight of a nonflammable coating having the same formulation as in Example 1 and stirring. The electrical resistance value of the product of the present invention obtained here was measured immediately after preparation and was found to be 63 KΩ · cm. The product of the present invention thus obtained was stored indoors for 30 days, and the state of the coating material was examined. As a result, no deterioration such as precipitation of pigment was observed, and the electric resistance value was measured and found to be 67 KΩ · cm.

When the steel billet was marked by using the obtained product of the present invention in the same large-sized marking device as in Example 1, it was as clear as when the commercially available product shown in Example 1 was used. The mark was obtained.

Example 4 46% by weight of tetrachloroethylene (manufactured by Kanto Denka Co., Ltd.), 20% by weight of methylene chloride (manufactured by Asahi Glass Co., Ltd.), 10% by weight of dichlorofluoroethane (manufactured by Mitsui DuPont Fluorochemicals Co., Ltd.), white pigment. (Titanium oxide: Ishihara Sangyo Co., Ltd.) 12% by weight, resin binder (cellulose resin: Shin-Etsu Chemical Co., Ltd.) 6% by weight, and DBP (dibutyl phthalate: Sekisui Chemical Co., Ltd.) 6% by weight (Note) Non-flammable paint of 2) (viscosity: 18 cp / 20 ° C)
0.1 parts by weight of tetra-n-butylammonium bromide (manufactured by Nippon Shokubai Kagaku Co., Ltd.) was added to 100 parts by weight and stirred to obtain a product of the present invention. The electrical resistance value of the product of the present invention obtained here was measured immediately after preparation and was 106 KΩ · cm.
In addition, after storing the product of the present invention obtained here in a room for 30 days,
When the paint state was examined, no deterioration phenomenon such as precipitation of pigment was observed, and the electric resistance value was measured to be 106 KΩ ・
It was cm.

(Note 2) The formulation of the nonflammable paint used in this example is a formulation of a commercially available nonflammable paint for large-sized marking devices (Tech Marker PLF White: trade name: Mark Tech Co., Ltd.).

The obtained product of the present invention was used in the same large-sized marking device as in Example 1 to mark a steel billet. As a result, a clear mark equivalent to the case of using the commercially available product was obtained.

Example 5 Pentafluoropropane (Asahi Glass Co., Ltd.) 50% by weight, methylene chloride (Asahi Glass Co., Ltd.) 20% by weight, blue dye (Sumitomo Fast Blue Sumitomo Chemical Co., Ltd.) 12% by weight, resin binder (Cellulose resin: manufactured by Shin-Etsu Chemical Co., Ltd.) 6% by weight and DOP (di-2-ethylhexyl phthalate: manufactured by Sekisui Chemical Co., Ltd.) 12% by weight. 0.2 parts by weight of tetra-n-butylammonium iodide (manufactured by Nippon Shokubai Kagaku Co., Ltd.) was added to 100 parts by weight of 12 cp / 20 ° C.) and stirred to obtain the product of the present invention.
The electrical resistance value of the obtained product of the present invention was measured immediately after preparation and was found to be 82 KΩ · cm. Further, when the product of the present invention obtained here was stored indoors for 30 days and the state of the paint was examined, no deterioration phenomenon such as precipitation of pigment was observed, and the electric resistance was measured and found to be 85 KΩ · cm.

(Note 3) The formulation of the non-combustible paint used in this example is a formulation of a commercially available non-combustible paint for large marking devices (Tech Marker PLF Blue: trade name: Mark Tech Co., Ltd.).

The obtained product of the present invention was used in the same large marking apparatus as in Example 1 to mark a steel pipe, and a clear mark equivalent to the case of using the commercially available product was obtained.

Example 6 58% by weight of pentafluoropropane (Asahi Glass Co., Ltd.), 20% by weight of methylene chloride (Asahi Glass Co., Ltd.), 12% by weight of red dye (Titing Red B: Sanyo Dye Co., Ltd.), resin binder (Cellulose resin:
Non-flammable paint (viscosity: 18 cp / 20 ° C) of a formulation (Note 4) consisting of 6% by weight of Shin-Etsu Chemical Co., Ltd. and 4% by weight of TEP (triethyl phosphate: manufactured by Kurogane Kasei Co., Ltd.) 1
0.5 parts by weight of tetraethylammonium bromide (manufactured by Nippon Fine Chemical Co., Ltd.) was added to 00 parts by weight and stirred to obtain a product of the present invention. The electrical resistance value of the obtained product of the present invention was measured immediately after preparation and was 130 KΩ · cm. Also, after storing the obtained product of the present invention in a room for 30 days, the state of paint was examined and no deterioration phenomenon such as pigment precipitation was observed. The electrical resistance value was measured to be 133 KΩ · cm.
Met.

(Note 4) The formulation of the nonflammable paint used in this example is a formulation of a commercially available nonflammable paint for large-sized marking devices (Tech Marker PLE red: trade name: Mark Tech Co., Ltd.).

The obtained product of the present invention was used in the same large-sized marking device as in Example 1 to mark a steel billet, and a clear mark equivalent to the case of using the commercially available product was obtained.

Example 7 Tetrachlorethylene (manufactured by Kanto Denka Co., Ltd.) 50% by weight, methylene chloride (manufactured by Asahi Glass Co., Ltd.) 30% by weight, black pigment (carbon black: manufactured by Nippon Carbon Co., Ltd.)
8% by weight, resin binder (cellulose resin: manufactured by Shin-Etsu Chemical Co., Ltd.) 6% by weight, and DBM (dibutyl maleate:
Non-flammable paint (viscosity: 18 cp / 20 ° C) of 6% by weight (manufactured by Daihachi Chemical Industry Co., Ltd.) 100%
0.5 parts by weight of tetra-n-butylammonium iodide (manufactured by Nippon Fine Chemical Co., Ltd.) was added to the parts by weight and stirred to obtain the product of the present invention. The electrical resistance value of the obtained product of the present invention was measured immediately after preparation and was 150 KΩ · cm. Further, after the obtained product of the present invention was stored indoors for 30 days, the state of paint was examined and no deterioration phenomenon such as pigment precipitation was observed. The electric resistance value was measured to be 153 K.
It was Ω · cm.

(Note 5) The formulation of the non-combustible paint used in this example is a formulation of a commercially available non-combustible paint for large-sized marking devices (Tech Marker PLF Black: trade name: Mark Tech Co., Ltd.).

The obtained product of the present invention was used in the same large-sized marking device as in Example 1 to mark an aluminum pipe, and a clear mark equivalent to the case of using the commercially available product was obtained.

(Detection test of remaining amount of paint in tank) The large amount of marking device used in each of the above-mentioned embodiments is provided with a stainless paint tank as shown in FIG. As a result of detecting the remaining amount of paint in the tank by using each of the present invention products of ~ 7, in any case,
When the liquid level of the product of the present invention filled in the tank is lower than the lower end of the detection electrode and the lower end of the electrode and the product of the present invention are not in contact with each other, the alarm output alarm lamp is turned on. . A stainless steel rod having a diameter of 3 mm was used as the detection electrode, and the AC power supply was set to 24V.

[0054]

The non-combustible paint having conductivity according to the present invention can be easily prepared, and the use of the paint can be electrically controlled by detecting the amount of paint remaining in the paint tank.

Therefore, it can be said that the product of the present invention is most suitable for a large-sized marking device used for billets and pipes in steel factories, automobile factories and the like.

[Brief description of drawings]

FIG. 1 is a conceptual explanatory view showing a paint remaining amount detection mechanism in a paint tank.

[Explanation of symbols]

1 Metal paint tank 11 Cap 12
Paint transport pipe 2 Detection electrode 21 Insulation cover 22 AC power supply 23 Amplification circuit and relay drive circuit 2
4 Relay 25 Alarm output 3 Non-combustible paint having conductivity according to the present invention

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ryusuke Yamaguchi 641 Funakuramachi, Yokosuka City, Kanagawa Marktech Co., Ltd. Kurihama Factory

Claims (3)

[Claims] 1. Tetrachloroethylene, methylene chloride,
Halogenated as a conductivity-imparting agent for 100 parts by weight of a non-flammable coating material prepared by mixing at least a coloring agent and a resin binder in one or more halogen-based solvents selected from dichlorofluoroethane and pentafluoropropane. A non-flammable paint having conductivity, which is characterized by adding 0.05 to 1.5 parts by weight of a tetraammonium compound. 2. A quaternary ammonium halide compound,
The non-combustible paint having electroconductivity according to claim 1, which is one or more selected from trioctylmethylammonium chloride, tetraethylammonium bromide, tetra-n-butylammonium bromide and tetra-n-butylammonium iodide. . 3. The electric resistance value is 15 KΩ · cm to 300 KΩ.
-The non-combustible coating material having a conductivity of cm according to claim 1 or 2.