JPS6255557B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides thermochromic technology that allows the temperature distribution of the coated surface to be easily confirmed by applying a coating film to buildings, mechanical equipment, heat generating equipment, chemical plants, etc. This relates to multi-colored paint.

Traditionally, methods for determining the temperature of the surface of an object include using measuring instruments such as surface thermometers that use thermocouples, or by painting paint containing a thermochromic material called thermochromic paint, and measuring the change in color. There were methods to determine the temperature using measuring instruments, but methods using measuring instruments could only determine partial temperatures, and it was nearly impossible to determine the entire temperature distribution through visual observation alone. In addition, in the method of using temperature-indicating paint, an expensive thermochromic material is mixed homogeneously into the paint at a concentration higher than that at which color change can be visually confirmed, which makes the paint extremely expensive. When the temperature distribution is not uniform, the color of the entire paint is also not uniform, resulting in poor aesthetics.

The present invention solves the above-mentioned conventional drawbacks, and by mixing an expensive thermochromic material into a certain color in a multicolored pattern, the amount used is reduced and the overall price is significantly lowered. The granular or speckled pattern formed by the pattern paint that does not contain color-changing materials exists as a fixed color, and even if this causes uneven temperature distribution on the painted surface, the painted surface will not change. As a whole, it maintains a more or less uniform aesthetic appearance.

That is, the purpose of the present invention is to apply paint to the surface of a building, mechanical device, heat generating device, chemical plant, etc. to give it a multicolored pattern and make it beautiful, and at the same time to improve the temperature distribution of the entire surface to be coated. The objective is to provide an easy and inexpensive means of knowing.

The purpose of this is to add a thermochromic material to the pattern part paint that constitutes at least one of the plural colors in a multicolored pattern paint in which the pattern part paint is composed of multiple colors in the solvent part paint. This can be achieved by containing 5 to 200 parts by weight per 100 parts by weight of the solid content.

The present invention will be explained in more detail below. The solvent paint in the present invention is composed of water-based film-forming elements such as a water-soluble resin binder, resin emulsion binder, or inorganic binder, and various additives commonly used in water-based paints. The dried paint film must be transparent in order to reveal a multicolored pattern without hiding the color of the pattern paint, which will be described later.

The above-mentioned water-soluble resin binders include water-soluble modified synthetic resins such as acrylic resins, epoxy resins, alkyd resins, polyester resins, etc., which are either individual or copolymers. (Nippon Shokubai Chemical Co., Ltd.) Watersol S-302 (Dainippon Ink Chemical Co., Ltd.), etc.

In addition, as a resin emulsion binder,
Acrylic ester, methacrylic ester,
Vinyl acetate, vinyl chloride, vinylidene chloride,
Ethylene/vinyl acetate, styrene/acrylic acid ester, vinyl acetate/versatlic acid, etc. can be used alone, as a copolymer of two or more types, or as a blend.

Furthermore, examples of the inorganic binder include colloidal silica, alumina sol, lithium silicate, various polyphosphates, and sodium silicate. Furthermore, the gist of the present invention will be impaired even if one or more of water-soluble resin binders, resin emulsion binders, and inorganic binders are used as film-forming elements in solvent-based paints, or if one or more of them are used. I will not serve you unless I am.

Various additives for the solvent part paint include surfactants such as dispersants and wetting agents, film forming aids (e.g., butyl carbitol acetate, dibutyl phthalate, etc.), freeze stabilizers (e.g., ethylene glycol),
Preservatives, thickeners, antifoaming agents, or pigments or fillers (e.g., calcium carbonate, silica powder, clay titanium oxide, iron oxide, mica, etc.) within the range that does not impair the transparency of the coating after drying. ), ultraviolet absorbers, antioxidants, etc.

The pattern paint of the present invention (a) does not contain a thermochromic material. (b) Items containing thermochromic materials. 2
There are several types, and the pattern part paint in (a) is composed of a film-forming element, a coloring material, and various additives. Various resins including Elements and which can use solvents other than water as a solvent may also be used.

Things that can be used as coloring materials include zinc white,
White pigments such as lithobon, zircon oxide, titanium oxide, red pigments such as red red, red lead, vermilion, molybdenum red, toluidine red, brown pigments such as amber, iron oxide, yellow pigments such as Hansa yellow, yellow lead, synthetic ocher, etc. Examples include green pigments such as copper phthalocyanine green and chromium oxide green, and blue pigments such as navy blue, ultramarine blue, and copper phthalocyanine blue.
Further details include those described on pages 10 to 4 of the "New Edition Pigment Handbook" edited by the Japan Pigment Technology Association. Other dyes such as direct dyes, acid dyes, basic dyes, acid mordant dyes, and reactive dyes can be used, but thermally stable dyes are preferred. Various additives for the pattern paint include additives for general paint use that can be used in the solvent paint mentioned above, but among these, fillers can be added in relatively large amounts. It is possible.

The content of (B) for the pattern paint can be considered to be almost the same as the content of (B) except for the coloring material, but a new thermochromic material has been added to the total solids content of 100 parts by weight of the pattern paint. It is necessary to contain 5 to 200 parts by weight. If the temperature is below the above range, the coloring effect of the thermochromic material is poor and temperature changes cannot be visually confirmed. Above the above range, even if the pattern paint is dispersed in the solvent part paint in the form of particles or spots, the thermochromic material will dissolve into the solvent part paint, and as a result, the coloring effect will be lost. . The coloring effect in (B) is achieved by adding a thermochromic material, but it is also possible to blend the coloring pigments listed in (B) as appropriate within a range that does not impair the coloring effect due to temperature changes. .

The composition contents of the solvent part paint and the pattern part paint have been described above, but in order to form a multicolored pattern with one coating, the pattern part paint must be stabilized in the form of particles or spots in the solvent part paint. Care must be taken to ensure that the pattern paint does not dissolve, break, or solidify during storage or painting. For this purpose, it is necessary to control the composition of the solvent part paint and the pattern part paint, and a generally known method may be used as a means for this, and an example thereof will be briefly explained below.

(1) In contrast to solvent part paints whose main component is water-based film-forming materials, pattern part paints are paints whose main component is resin with a solvent other than water such as metal soap (e.g. aluminum stearate, calcium stearate). , calcium laurate, etc.) is made into a soft gel state as a pattern part paint, and is added to the solvent part paint as appropriate and dispersed in granules or spots. A multicolored pattern is stabilized by utilizing the polarity difference in the pattern paint.

(2) Adjust the PH or ionic atmosphere of the solvent paint to gel the pattern paint, and stabilize the multicolored pattern by taking advantage of the fact that the solvent paint and the pattern paint are essentially incompatible. Something that has maintained its originality.
A specific method for this is, for example, by creating an anionic atmosphere by blending an anionic resin, an anionic surfactant, and an anionic thickener into the water-based solvent paint, and then adding a similar cationic atmosphere to the pattern paint. A cationic atmosphere is created by adding an agent, and the viscosity of the pattern paint is made higher than that of the solvent paint to prevent it from flowing out easily. In addition, as another specific example, when an electrolyte coexists in the pattern paint, a water-soluble polymer (e.g. quar gum) that gels when the pH exceeds a certain value is blended, and the solvent part paint is An example of this is to adjust the PH to a value above the above value, while adjusting the paint on the pattern part to a value below that to maintain the stability of a multicolored pattern, but see Example 1 for more details. Describe.

(3) A composition such as a very common oil-based paint or water-based paint is gelled or semi-solidified (soft gelled) as appropriate by "adding an electrolyte" or "thermal treatment". This is made by cutting the material into appropriate pieces to create a pattern paint, which is then dispersed in a solvent paint, and the pattern paint essentially gels to maintain the stability of the multicolored pattern.

As mentioned above, it is necessary to control the formulation so that the pattern part paint can be stably dispersed in the solvent part paint in the form of particles or spots, but as long as it does not impair the gist of the present invention. There is no problem in using methods other than those described above.

The thermochromic material used in the present invention is a liquid crystal, a metal complex crystal, an electron-donating color-forming organic compound, etc. as a color-forming substance, and a caking agent, a color developer, etc. are used in combination as necessary. It is something.

Such liquid crystals include cholesteric liquid crystals, terphenyl liquid crystals, nematic liquid crystals, etc., which are encapsulated in microcapsules using known microencapsulation techniques (interfacial polymerization, spray drying, phase separation, etc.) and are thermally discolored. used as a sexual material.

Examples of the metal complex crystals include a silver complex salt compound of mercury iodide (Ag ₂ HgI ₄ ) and a copper complex salt compound of mercury iodide (Cu ₂ HgI ₄ ), which can be used as they are as a thermochromic material. .

As the electron-donating color-forming organic compound,
Leuco dyes (e.g., crystal violet lactone,
malachite green lactone, benzoylleucomethylene blue, N-phenylrhodamine β-lactam), etc.

The substance can be combined with a phenolic compound (e.g., bisphenol A, novolac type phenolic resin, α-
naphthol, β-naphthol) or acid or
A solid acid such as bentonite, aluminum phosphate, or titanium oxide is used as a color developer, and a caking agent (natural resin or synthetic resin) is mixed with a thermofusible substance (urea, acetanilide, stearic acid, phthalic acid, etc.) as necessary. However, after being appropriately solidified, it can be used as a thermochromic material.

Furthermore, in order to improve the quality of thermal discoloration, we
51-31682 (name of invention, thermochromic material), JP-A-Sho
55-157677 (title of the invention, thermochromic material), for example, the above-mentioned electron-donating color-forming organic compound is combined with a metal salt of a compound having a phenolic hydroxyl group or a metal salt of a carboxylic acid and a carboxylic acid. An acidic compound may be appropriately blended and encapsulated in microcapsules, which may be used as a thermochromic material.

Other thermochromic materials include JP-A-51-
72982 (title of the invention, temperature indicating material), powder obtained by drying strontium chloride or bromide with cobalt salt; Examples include powders obtained by mixing potassium iodide with a bismuth compound solution and drying the mixture, as shown in ``Hot Materials''.

The method for producing the thermochromic multicolored paint of the present invention includes:
It basically consists of (A) the manufacturing process of the pattern part paint, (B) the manufacturing process of the solvent part paint, and (C) the manufacturing process of dispersing the pattern part paint in the solvent part paint, of which the process (A) is diverse. There are multiple steps depending on the number of colors in the pattern, and as mentioned above, at least one of the steps contains a thermochromic material in an amount of 5 to 200 parts by weight based on 100 parts by weight of the total solid content in the pattern paint. I have to keep it at bay.

For example, in the multicolored pattern paint, the number of colors of the granular or spotted pattern formed by the pattern paint is three, and one of the colors is thermally colored (thermal discoloration).
If you are trying to make the pattern part paint (a), use two types of red paint and black paint as the pattern part paint (b), one of which is a green paint that changes color from green to blue when the temperature exceeds 40℃. Since it is necessary to create different types, the manufacturing process for the pattern paint consists of a total of three steps. Of course, the number of colors and the color system described above can be changed freely. Further, by appropriately selecting a thermochromic material, it is possible to freely change the temperature at which the thermochromic color changes and the color system at which the color changes. To manufacture the pattern paint, known paint manufacturing technology can be applied, such as high-speed mill,
It can be produced using a dispersion device such as a three-roll mill or a ball mill. However, when dispersing after adding the thermochromic material, care must be taken to avoid applying shearing force to the material as much as possible, such as by stirring at a low speed so as not to destroy it and lose its effect. Known paint manufacturing techniques can be applied to manufacture solvent part paints, such as high-speed mills,
A dispersing device or stirring device such as a sand mill, colloid mill, ball mill, etc. can be used.

The method of dispersing the pattern part paint in the solvent part paint is to gradually add the pattern part paint to the solvent part paint.
Either use a dispersion device with stirring blades that applies shearing force to the pattern paint to obtain the paint while cutting it into desired granular or spot-like sizes, or use an orifice mixer, jet mixer, or injector mixer. The paint can be obtained by sending a jet of the pattern paint into the solvent paint using a polygon pump, a turbine pump, a propeller pump, There are methods such as dispersing the paint through a gear pump, screw pump, etc. to obtain the paint.

The paint according to the present invention may be applied by roller coating, trowel coating, spray coating, or the like. Furthermore, if an undercoat of a desired color is applied in advance before painting, the color of the undercoat will appear through the transparent solvent paint film of the topcoat of the present invention, which has a granular or spotty multicolored pattern. , can provide aesthetically superior and effective coloring.
As for such undercoat paint, it is appropriate to use a metal-grade paint for a metal surface, a wood-grade paint for a wooden surface, and an architectural-grade paint for a concrete or mortar surface. selected. Further, the paint may be water-based or oil-based.

In the thermochromic multicolored pattern paint of the present invention, not only can the temperature distribution of the surface of the object to be coated be easily determined by visual observation, but also the expensive thermochromic material can be dotted in a multicolored pattern. At the same time, even if there is variation in the temperature distribution on the surface to be coated, only the scattered areas containing the thermochromic material exhibit a color change, so overall the price is lower than that of conventional thermochromic paints. It does not cause uneven coloring and retains its beauty.

Next, examples will be described in detail. In addition, all compounding ratios in the examples indicate "parts by weight."

Example 1 Compounding of red pattern paint (a) Water 50.0 Dispersant 0.2 Red red 7.0 Thickener (guar gum) 1.0 3% boron trioxide aqueous solution 0.3 Antifoaming agent 0.1 5% acetic acid aqueous solution 0.1 Acrylic acid ester resin emulsion (solid) 50%) 50.0 Blending of blue pattern paint (a) Water 50.0 Dispersant 0.2 Copper/phthalocyanine blue 6.0 Thickener (guar gum) 1.0 3% boron trioxide aqueous solution 0.3 Antifoaming agent 0.1 5% acetic acid aqueous solution 0.1 Acrylic acid Ester resin emulsion (solid content 50%) 50.0 Mixture of pattern paint (b) that changes color due to heat at 35°C Water 50.0 Dispersant 0.2 Thickener 7.0 3% boron trioxide aqueous solution 0.3 Antifoaming agent 0.1 5% acetic acid aqueous solution 0.1 Acrylic Acid ester resin emulsion (solid content 50%) 50.0 Thermochromic material - D (Note 1) 8.0 Ultraviolet absorber 0.5 Note 1: Thermochromic material - D is an electron-donating color-forming organic compound of crystal violet lactone 10 Add 50 parts by weight of dichlorobiphenyl and further mix 50 parts by weight of cyclohexanecarboxylic acid, add 10 parts by weight of green spirit dye, heat melt and mix at 70°C, and mix with gelatin aqueous solution. It is encapsulated in microcapsules using an aqueous solution of gum arabic. In preliminary tests of this product itself, it turns green at temperatures below 35°C and turns yellow at temperatures above 35°C.

According to the above-mentioned compounding ratio, each of the pattern paints is manufactured using a high-speed mill.

Solvent part Paint formulation Acrylic acid ester resin emulsion (solid content 50
%) 500 Coating agent 30 Thickener (methyl cellulose) 10 Antifoaming agent 1 Aqueous ammonia 3 A solvent part paint is produced using a high-speed mill according to the above mixing ratio. Next, ~ of the pattern part paint prepared in advance was slowly added to this solvent part paint, and the mixture was stirred at low speed using a high-speed mill to disperse it in the form of particles or spots, thereby obtaining a paint.

This paint was sprayed using a ricing gun at an air pressure of 3 kg/cm ² on the inner wall surface of the mortar, which had been previously coated with a white undercoat paint (product name: "Kikusuikoto Risin Boning" manufactured by Kikusui Chemical Co., Ltd.), but it dried. Later, a multicolored pattern of red, blue, and green grains or spots ranging from the size of a grain of sand to the size of a thumb was formed on a white background.

At this time, the temperature distribution on the painted wall surface was measured using a surface thermometer (HP
-4F model (manufactured by Anritsu Keiki Co., Ltd.) at multiple locations, the temperature was 20-30℃. Furthermore, after raising the temperature in the room for a certain period of time using an air conditioner, when observing the painted surface, we found that the green patterned part of the painted surface from the center to the ceiling had turned yellow. On the other hand, from the center to the floor, the color of the pattern did not change at all from before the temperature was raised. When we measured the temperature distribution of the painted wall surface at this time using the above-mentioned surface thermometer, we found that the temperature was 35 to 40 degrees Celsius in all the areas where the green pattern turned yellow, and the temperature in the areas where the color had stopped was 30 to 40 degrees Celsius. It was 34℃.

Example 2 Blend of black pattern paint (a) Toluene 30.0 Carbon black (black pigment) 15.0 Antifoaming agent 0.1 Alkyd resin varnish (50%) 70.0 Aluminum stearate 3.0 Calcium carbonate 30.0 Green pattern paint (a) Formula Toluene 30.0 Chromium oxide (green pigment) 0.2 Antifoaming agent 0.1 Alkyd resin varnish (50%) 70.0 Aluminum stearate 3.0 Calcium carbonate 30.0 Mixture of pattern paint (b) that thermally discolors at 70°C Toluene 30.0 Antifoaming agent 0.2 Alkyd Resin varnish (50%) 70.0 Aluminum stearate 3.0 Cu ₂ HgI ₄ (thermochromic material) (Note 2) 30.0 (Note 2) Copper complex salt compound of mercury iodide (Cu ₂ HgI ₄ ) turns red 70 below 70℃ It turns brown at temperatures above ℃.

According to the above-mentioned compounding ratio, each of the pattern paints is manufactured using three rolls. Next, the above-mentioned pattern part paint was sequentially added to the solvent part paint obtained in Example 1, and dispersed in granules or spots by low-speed stirring in a high-speed mill. I spray-painted the outer skin, and after drying, a multicolored black, green, and red pattern the size of a grain of sand was formed. When the temperature distribution of the coated surface was measured in the same manner as in Example 1, it was 25 to 26°C. After that, when the electric motor was operated for 24 hours and the surface to be coated was observed while it was still operating,
I noticed that the red pattern in the center had turned brown. The surface temperature of this part was measured to be 70-80°C. Also, the number of areas where no change is seen is 50~
It was measured at 70℃.

Comparative Example 1 A paint was produced in the same manner as in Example 1 using 1 part by weight of the thermochromic material D, and observed in the same manner as in Example 1. However, at temperatures below 35°C, the green pattern also appeared. It was difficult to understand, and no color change could be observed even on painted walls that were at temperatures above 35°C.

Comparative Example 1 The amount of thermochromic material Cu ₂ HgI ₄ in Example 2 was
A paint was produced in the same manner as in Example 2 using 100 parts by weight, but when the pattern part paint (b) was dispersed in the solvent part paint, the red thermochromic material was eluted into the solvent part paint. As a result, it was not possible to stably disperse the particles in the form of particles or spots.

Claims (1)

[Claims] 1. A plurality of colored paints (hereinafter referred to as "pattern part paints") dispersed in granular or spotty form in a water-based paint solution with a transparent film after drying (hereinafter referred to as "solvent part paints"). In a multi-colored paint made up of colors, at least one of the multiple colors
A thermochromic multicolored pattern paint, characterized in that the pattern paint forming the color contains a thermochromic material in an amount of 5 to 200 parts by weight based on 100 parts by weight of the total solid content in the pattern paint.