JPH03111480A - Near-infrared absorptive material - Google Patents

Abstract

PURPOSE:To obtain the title material suitably used for a heat ray shielding film in agriculture, a near-infrared filter, a printer for preventing forgery, a paint for camouflage, etc., by mixing an axially coordinated iron phthalocyanine compound as a near-infrared absorbent. CONSTITUTION:The title material contains an axially coordinated iron phthalocyanine compound of formula Fe(Cl)Pc (wherein Pc is a phthalocyanine residue; 3.0-5.9wt.%, preferably 4.5-5.9wt.%, chlorine is contained in the molecule). This compound is represented by formula I wherein the theoretical value of the chlorine content is 5.9wt.%, and part of the chlorine atoms may be replaced by hydroxyl groups.

Description

Detailed Description of the Invention "Field of Industrial Application" The present invention is directed to materials that selectively absorb near-infrared rays of 750 to 2,500 ron in sunlight, such as heat ray blocking films and infrared cut filters for preventing counterfeiting. Concerning printed matter, camouflage coatings, and various heat sensitizers.

"Conventional technology" Near-infrared light (750~
2500 nm) has been greatly involved in human life as solar heat and harmful light.

Although various studies have been made on the effective use and regulation of this effect, it is still not sufficient. Carbon black, which is a typical heat ray absorber, is a black pigment whose visible light transmission is close to zero, and its uses are severely limited.

Furthermore, the conventionally used nigrosine and naphthol green, as well as the dyes and chelate compounds recently developed as near-infrared absorbers, still have problems in light resistance and heat resistance.

On the other hand, metal phthalocyanine has traditionally been widely used as a bright and robust coloring material, and in recent years, due to its functional properties, it has been used in oxidation/reduction catalysts, photoelectric conversion elements, deodorizing agents, photoreceptors for electrophotography, organic semiconductor elements, gas detection, etc. It has been studied for various uses such as devices. In particular, many patents have been filed for metal 7-talocyanine having a K absorption ability of 700 to 800 nm as an optical information recording medium.

However, the axially coordinated iron phthalocyanine compound has 750
Little was known about whether or not it selectively absorbs light in the near-infrared region of ~2500 nm.

"Problems to be Solved by the Invention and Means for Solving the Problems" The present invention aims to provide a material that can absorb heat rays in the near-infrared region, which is known as harmful light. While studying the functional properties of various metal phthalocyanines, we found that axially coordinated chlorinated iron phthalocyanine, which is a precursor of iron phthalocyanine, has high heat resistance, light resistance, and excellent near-infrared (750-2500 mm) absorption ability. Based on this discovery, the present invention is based on the general
c (In the formula, Pc represents a phthalocyanine residue, and each molecule contains 3.0 to 5.9 wt of chlorine, preferably 4.5 to 5.
This is a near-infrared light absorbing material characterized by containing an axially-coordinated iron phthalocyanine compound represented by Jwt%).

The structural formula of the axially coordinated chlorinated iron phthalocyanine of the present invention is shown below.

The theoretical content of chlorine in the axially-coordinated iron phthalocyanine compound of the present invention is 5.9 wt, and a portion of the chlorine may be a water group.

"Function" The synthetic resin colored film containing the iron phthalocyanine compound according to the present invention is used to absorb and block heat rays in the near-infrared region included in sunlight, and to prevent leaf burn and leaf fall. Cheesecloth can be used to provide a house suitable for cultivating semi-negative plants such as green and yellow vegetables whose young shoots are eaten, such as wasabi, ginseng, and honeysuckle.

Furthermore, when a paint is made using the iron phthalocyanine compound according to the present invention, it can be used as a disguise paint that absorbs near-infrared rays (heat rays) and prevents reflection of infrared rays.

In other words, conventional paints used for camouflage, such as grass blue and khaki, do not have the ability to absorb heat rays (near infrared rays) and transmit most of them.
Since it hits the object to be painted and reflects, it has the disadvantage that even though it looks like camouflage color to the naked eye, it can be easily distinguished from surrounding plants when using an infrared camera or infrared detector. In order to make the infrared reflectance similar to that of surrounding plants, it is necessary to add a substance that has infrared absorption ability. For this purpose, a heat ray absorber that does not have very high coloring power is required, and although Fg(Cl)Pc has a slightly edged blue color, it does not have much coloring power and is suitable for this purpose.

Some carbon blacks are black, which limits their range of use in such applications.

It can also be used as a heat ray absorber in various heat sensitizers and anti-counterfeiting inks.

Anti-counterfeiting ink refers to ink that allows forgery to be confirmed by the difference in infrared absorption (reflectance) even if the color is toned to a similar color to the naked eye.

"Examples, Comparative Examples" The present invention will be explained in more detail with reference to Examples below.

Production Example 1 Synthesis of Axial Coordination Chlorinated Iron Phthalocyanine Fe(CI)Pc In a reaction vessel, 113 parts by weight of phthalimide, 156 parts by weight of urea, 47 parts by weight of ferrous chloride (hydrated salt), and 70.5 parts by weight of ammonium molybdate were added. , trichlorbenzole 500VL
Prepare the quantity and heat at 130-135℃ for 1 hour, 185-19
After reacting at 5° C. for 7 hours, the solvent is distilled off and recovered by vacuum distillation.

The resulting composition was wet-pulverized, treated with 2000 parts by weight of a 70'C11° sulfuric acid solution for 3 hours, and then cooled.
By p, washing with water, drying, crushing, chlorine content 5.79
Fe(CI)Pc with weight i% and average particle size of 1.31 μm
100 parts by weight were obtained.

The results of differential thermal analysis of this product showed that it was stable at 360'C4, and decomposed at around 360°C with some heat generation.

Example I 6 parts by weight of F.(CI)Pc O and 30.0 parts by weight of polyamide/nitrocellulose ink were added to 1 part by weight of glass beads.
After dispersion treatment for 30 minutes with 00 parts by weight in a paint conditioner, the glass beads were separated and the resulting ink was spread on an OPP (biaxially oriented polypropylene) film to a thickness of 16 μm using a bar coater to form a spread film. Obtained.

Comparative Example 1 An ink was prepared in the same manner as in Example 1 using a representative metal phthalocyanine and a commercially available near-infrared absorbing and adjusting pigment in place of Fe(Cl)Pc, and OPP was applied using the obtained ink rubber coater. Spread the color on a film and measure it with a spectrophotometer (
Takashi multi-purpose self-recording spectrophotometer MPS-5000)
The near-infrared transmittance in the wavelength range of 750 to 2600 nm was measured.

The results of calculating the average transmittance using a planimeter are as follows.

*The ink using P-26 Fe(CI)Pc with a chlorine content of 0.43 wt% absorbed near-infrared rays and exhibited excellent blocking effects.

Production Example 2 F'e (CI)Pc obtained in Production Example 1 has an average particle diameter of 1.31 μm, which is slightly larger than ordinary pigments, so it is commonly used to make pigments into fine particles. I tried salt-milling.

100 parts by weight of 1.31 μm Fe(CI)Pc was put into a kneader mixer together with 850 parts by weight of anhydrous sodium sulfate and 200 parts by weight of ethylene glycol, treated at 80°C for 7 hours, and then discharged into 10,000 parts by weight of water. After thorough dispersion, the mixture was filtered, washed with water, and dried.

The obtained fine powder had an average particle diameter of 0.55 μm and a chlorine content of 4.73% by weight.

It was made into a thin film in the same manner as in Example 1, and measured in the same manner as in Comparative Example 1.

Although the coloring power as a coloring material increased three times compared to before treatment due to the atomization, its near-infrared transmittance remained almost unchanged at 79.
It showed 0chi.

Example 2 A pigment content of 101% chi master patch was made using Betrocene 9304 () - low-density polyethylene made by Thor) as a pace resin.
A colored polyethylene film with a thickness of μm was produced by an inflation method.

The transmittance of this film in the visible light region and near infrared region was measured using a spectrophotometer, and the results were as follows.

N1 S2 Blank-26 The masterbatch film using Fe(CI)Pc without using pigments has relatively high transmittance in the visible region, but the transmittance in the near-red region decreases significantly, and the absorption of heat rays decreases due to the chlorine content. It showed that it is more expensive than P-26.

Example 3 Tubatic F-131-M (manufactured by Mitsubishi Kasei, low density polyethylene) was used as a pace resin, and the pigment content was 10.
Weight % and stabilizer 10 weight t (dimethyl succinate based 5
weight%, pentaerythritol antioxidant 5% by weight)
I made a masterbatch.

80μ using this masterbatch! A colored polyethylene film with a thickness of n was created using an inflation method.

The transmittance of this film in the visible light region and infrared region was measured using a high-resolution multipurpose self-recording spectrophotometer MPS-5000, and the results were as follows.

No. 1 Na2 Blank Pigment-free Yellow 3063 (Pigme manufactured by Tokyo Ink
nt Yellow 83) N13P-26 (Double pigment iron 7 talocyanine) N14 Fe(CI)P
c Using each of the above films, a height of 17 m and a width of 3.0 m (
We constructed a cultivation room with a width of 1.7 m (east to west), a depth of 1.7 m (north to south), and a roof slope of 45 degrees, and measured its environment. The results were as follows.

The cultivation room made with Fe(CI)Pc film (Na4) absorbs and blocks sunlight's heat rays, keeping the soil temperature low while keeping the room temperature as high as a normal greenhouse.

Example 4 The heat absorption and barrier properties of each film used in Example 3 were measured using the apparatus shown in FIG.

Measurement method As shown in Fig. 1, a 40W crypto lamp held by a support 2 is prepared, and a hole 5 with a diameter of 10σ is made in the center of the top surface of a cardboard box 4 on the width 21 side, height 16c11, and depth 14eIt. Place the film on top of it, and further cover the lower part of the crypto lamp 1 with a height of 10
An aluminum plate cylinder 3 having a crns diameter of 10 cIR is placed on top of it. On the other hand, insert a thermometer 6 into the center of the side of the cardboard box 4 so that the tip of the thermometer is directly below the center of the hole 5. When U/P 1 was turned on, the temperature was measured 5 minutes and 10 minutes later. The measurement results are shown below. After the measurement was completed, the sample (film) and lamp were removed, the apparatus was cooled for 5 minutes with a hair dryer (cold), and the next sample was set and measured.

As is clear from the above (Film using Fe(CI)Pc (
NIIL4) absorbs and blocks heat rays.

"Effects of the Invention" As described above, films, inks, and paints using the near-infrared absorbent of the present invention can be used for agricultural heat ray-blocking films, near-infrared cut filters, printed materials for preventing counterfeiting, and Camo 7 Radie. It is effective in painting and is also used as a various heat-sensitive sensitizer.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing an example of a method for measuring the effectiveness of the present invention.

Claims (1)

[Claims] An axis represented by the general formula Fe(Cl)Pc (in the formula, Pc represents a phthalocyanine residue, and each molecule contains chlorine in an amount of 3.0 to 5.9 wt%, preferably 4.5 to 5.9 wt%) A near-infrared light absorbing material characterized by containing a coordinated iron phthalocyanine compound.