JPS6118576B2 - - Google Patents

Description

[Detailed description of the invention]

This invention applies to various electrical products, especially televisions,
The present invention relates to a composition for a synthetic resin filter that selectively transmits only near-infrared rays, and is used in remote control devices such as radios and stereos, speed and distance measurements for cameras and projectors, and game machines. Remote control devices that use light rays are harmless to the human body, do not generate heat, and
To prevent malfunctions, near-infrared light, which is a light beam in a wavelength range that is not commonly used, is preferably used. Therefore, a light source that emits near-infrared rays is attached to the transmitting section of the remote control device, and the light beam from this light source is directed to the receiving section attached to the electrical appliance to remotely control the electrical appliance. The environment surrounding the receiver of the remote control device is exposed to a large amount of light emitted from sunlight, incandescent bulbs, fluorescent lights, etc. In particular, the receiver of the remote control device may malfunction due to light in the visible range, where the amount of light changes rapidly. There were also things to do. Therefore,
In order to prevent this malfunction, it is necessary to attach a filter to the receiving section of the remote control device that absorbs light rays other than near-infrared rays and selectively transmits only near-infrared rays. By the way, in order to manufacture such a filter, it is necessary to coat the surface of glass or synthetic resin with good light transmittance with a substance that selectively transmits near-infrared rays, or to add a substance to the glass or synthetic resin. It is possible to add a substance that selectively transmits near-infrared rays, but in the former case, the coated surface is easily damaged, so it becomes necessary to code the surface, and the thickness of the layer of the coated substance may be changed. It is desirable to manufacture filters by adding a substance that selectively transmits near-infrared rays into glass or synthetic resin, because it requires uniformity and increases product cost. However, in the case of glass, this is difficult, so a substance that selectively transmits near-infrared rays must be selected from inorganic pigments.
In addition, inorganic pigment-based materials have the disadvantage of poor near-infrared transmittance. Therefore, in completing this invention, the present inventor took into consideration the above-mentioned difficulties, and made a material that can withstand the temperature during injection molding, using a synthetic resin with good light transmittance as a base material, and In search of a substance that substantially blocks the transmission of light rays other than near-infrared rays, especially light rays with wavelengths shorter than 750 nm, without inhibiting the transmission of near-infrared rays, especially light rays with wavelengths of 900 to 1000 nm, various studies were conducted as described below. did. (1) Neocyanine and 1.1′-Diethyl-2,2′-dicarbocyanine iodide (1.1′-Diethyl1-2,2′-dicarbocy-anine)
Carbocyanine dyes such as Iodide have light transmittance that rapidly increases from 800 nm for the former and from 750 nm for the latter, and are dyes that have characteristics suitable for the purpose of the present invention in terms of light transmittance. It was found that it had poor heat resistance and could not withstand the temperatures used during injection molding of thermoplastic resins. (2) Pigment Green 7, Pigment Green
Phthalocyanine copper-based pigments such as 36 and Pigment Green 41 (existing chemical substance list structure classification class 10 color index)
Although it blocks light rays of 750 nm or less well, it has a low light transmittance of 50 to 60% in the target near-infrared wavelength range of 900 to 1000 nm, making it unsuitable for manufacturing highly sensitive light filters. Ta. (3) We also investigated cyanic acid dyes such as Acid Green 25 and Acid Green 27, but these dyes block light at wavelengths of 750 nm or less, but have low light transmittance at 900 to 1000 nm. 40～
It was found that it was as low as 50% and was not suitable as a material for use in the present invention. (4) Also, by blending various oil-soluble dyes, 750nm
Various studies have been conducted to see if it is possible to block the following wavelengths of light and maintain a high light transmittance in the 900 to 1000 nm range, but nothing satisfactory has been obtained when heat resistance is taken into account. (5) Furthermore, we investigated compounds other than dyes, but as described below, we could not obtain any compounds suitable for the purpose of the present invention. ○A 1-methylnaphthalene (1-methylnaphthalene)
phthalene), N-ethyl-1-naphthylamine (N-ethyl-1-naphthylamine), 6-
Chloro-ortho-toluidine (6-chl-oro
-o-toluidine), 5,6,7,8-tetrahydro-1-naphthylamine (5,6,7,
We have also considered a method using organic compounds that have characteristic absorption in the wavelength range of 700 to 800 nm, such as 8-tetrahydro-1-naphthylamine, but their extinction coefficient is small and it is difficult to use them as additives to synthetic resins. There is a shortage. (B) Inorganic and organic nickel salts such as nickel acetate and nickel citrate also block light with a wavelength of 750 nm or less, but their transmittance for light in the near-infrared region is also low, so they are not suitable as substances for use in the present invention. As is clear from the above study results, most of the dyes, pigments, etc. that have been studied must be able to transmit visible light with a wavelength shorter than 750 nm, and must be added to a thermoplastic resin to manufacture a light filter.
The transmittance of light having a wavelength of 900 to 1000 nm in the near-infrared region was also not good. However, as a result of further studies on more dyes, pigments, etc., the present inventor found that Solvent Green 28, an anthraquinone-based oil-soluble dye (Existing Chemical Substances List, Classification by Structure, Class 10 Color Index, Classification by Structure) No. 10-2793, Official Gazette Publication Serial No. 5-5139) was found to be the most suitable material for use in the present invention, and the present invention was completed as shown in the first claim. This invention will be explained in detail below. Solvent Green 28 used in this invention is generally commercially available as a green dye, and representative examples include Bayer's product name "Macro-lex Green G" and Hoechst's product name "Solvaperm Green G".
There is. Although the chemical structural formula of Solvent Green 28 is unknown because it has not yet been published by the manufacturer, its light transmittance has a unique characteristic, as shown in Figure 1. Specifically, Norbent Green 28 was blended at a ratio of 0.2 wt% to colorless and transparent AS resin, which is an acrylonitrile-styrene copolymer, and the light transmittance was investigated using a test piece molded by injection molding to a thickness of 1.6 mm. As a result,
Solvent Green 28, as shown in Figure 1,
It absorbs most visible light and has almost no visible light transmittance, but it exhibits a maximum transmittance of about 6.8% for visible light with a wavelength of around 522 nm, which is part of the green region. In addition, the transmittance rises rapidly from near-infrared rays with a wavelength of 760 nm, and the light transmittance exceeds 90% for near-infrared rays with a wavelength longer than 900 nm. Therefore, when Solvent Green 28 is added to a synthetic resin with good light transmittance and molded into a filter, it has extremely low light transmittance for visible light and extremely low light transmittance for near infrared light. It has been found that it has a high light transmittance and is the most suitable material for the composition for a synthetic resin light filter, which is the object of the present invention.
Further, various studies were conducted by changing the blending ratio of Solvent Green 28, and it was found that a blend in the range of 0.1 to 1.0 wt% can be used as a filter. Next, if you need a synthetic resin light filter that completely prevents the transmission of visible light, Solvent Green can be used without inhibiting the transmission of near-infrared light.
It is sufficient to add a substance that absorbs visible light that 28 cannot absorb and can withstand the temperatures during injection molding of synthetic resins. After various studies, we found that Solvent Green 26, an anthraquinone oil-soluble dye, and Solvent Green 3, Solvent Green 20, Solvent Red 152, Solvent Red 155, Solvent Red 158, Solvent Violet 31, and Solvent Violet 34 (existing chemical substance list structure classification class 10 color index) and Verinone Oil-soluble dyes Solvent Green 5, Solvent Green 176, and Solvent Orange 78 (these are listed in Existing Chemical List Structural Classification No. 10)
It has been found that substances such as color index (similar color index) are used for this purpose. Further, as a result of various studies regarding the mixing ratio, it was found that it is appropriate to mix it in the range of 0.05 to 0.5 wt%. Furthermore, in order to prevent malfunctions of remote control devices, it is necessary to reduce the transmittance of light in the wavelength range of 750 to 850 nm, and to smooth the rise in light transmittance in the wavelength range of 750 to 850 nm. Furthermore, if a substance is added that has low light transmittance at wavelengths of 750 to 850 nm, high light transmittance at wavelengths of 900 to 1000 nm, and can withstand the temperatures during injection molding of synthetic resins. often,
As a result of examining various substances, we found that the phthalocyanine pigments Pigment Green 7, Pigment Green 36, Pigment Green 41, and Pigment Green 8 (hereinafter referred to as Existing Chemical Substances List Structure Classification Class 10 Color Index) were used for this purpose. This material was found to be suitable for this purpose. These substances can be used alone or in combination of two or more for this purpose, and as a result of various studies on the mixing ratio, it was found that it is appropriate to mix them in the range of 0.005 to 0.1 wt%. I found out something. The present invention will be described below with reference to Examples, but these Examples do not limit the present invention. The trade names and manufacturer's names of the dyes and pigments used in the color index display in the following examples are as follows.

[Table] Example 1 [A] 0.4 g of Solvent Green 28 was mixed with 100 g of AS resin, the mixture was passed through an extruder controlled at 200°C to form pellets, and the pellets were injection molded at 230°C. 1mm thickness and 2
A filter molded product [A] with a thickness of mm was obtained. Example 2 [B] 100g AS resin, 0.4g Solvent Green 28 and 0.1g Solvent Green 26
Filter molded products [B] with a thickness of 1 mm and 2 mm were obtained in the same manner as in Example 1 [A]. [C] 100g AS resin, 0.25g Solvent Green 28 and 0.05g Solvent Green,
From No. 26, filter molded products [C] with a thickness of 1 mm and a thickness of 2 mm were obtained in the same manner as in Example [A]. [D] 100g AS resin, 0.35g Solvent Green 28 and 0.05g Solvent Green
From No. 26, filter molded products [D] having a thickness of 1 mm, 2 mm, and 3 mm were obtained in the same manner as in Example 1 [A]. Example 3 [E] 100g AS resin, 0.4g Solvent Green 28, 0.1g Solvent Green 26,
From 0.05 g of Solvent Red 176, filter molded products [E] with a thickness of 1 mm, 2 mm, and 3 mm were obtained in the same manner as in Example 1 [A]. [F] 100g AS resin, 0.3g Solvent Green 28, 0.2g Solvent Green 3,
From 0.05 g of Solvent Red 176, filter molded products [F] with a thickness of 1 mm, 2 mm, and 3 mm were obtained in the same manner as in Example 1 [A]. [G] 100g AS resin, 0.45g Solvent Green 28, 0.2g Solvent Green
3 and 0.05 g of Solvent Red 176 to a thickness of 1 mm and 2 in the same manner as in Example 1 [A].
Filter molded product with mm thickness and 3 mm thickness [G]
were obtained respectively. Example 4 [H] 100g AS resin, 0.25g Solvent Green 28, 0.2g Solvent Green
26, 0.02g of Solvent Red 176, and
0.02g Pigment Green 7 to Example 1
In the same manner as [A], filter molded products [H] with a thickness of 1 mm, 2 mm, and 3 mm were obtained, respectively. [I] 100g AS resin, 0.275g Solvent Green 28, 0.1g Solvent Green
26, 0.015g of Solvent Red 176, and
From 0.0075 g of Pigment Green 7, filter molded products [I] with a thickness of 1 mm, 2 mm, and 3 mm were obtained in the same manner as in Example 1 [A]. [J] 100g AS resin, 0.3g Solvent Green 28, 0.1g Solvent Green 26,
0.04g Solven Dred 176 and 0.01
Example 1 from Pigment Green 7
In the same manner as [A], filter molded products [J] with a thickness of 1 mm, 2 mm, and 3 mm were obtained, respectively. [K] 100g AS resin, 0.3g Solvent Green 28, 0.2g Solvent Green 26,
0.05g Solvent Red 176 and 0.0075
Example 1 [A] from Pigment Green 7 of g.
In the same manner as above, filter molded products [K] with a thickness of 1 mm, 2 mm, and 3 mm were obtained, respectively. [L] 100g AS resin, 0.4g Solvent Green 28, 0.2g Solvent Green 26,
0.05g of Solvent Red 176, and
From 0.0075 g of Pigment Green 7, filter molded products [L] with a thickness of 1 mm, 2 mm, and 3 mm were obtained in the same manner as in Example 1 [A]. [M] 100g AS resin, 0.4g Solvent Green 28, 0.1g Solvent Green 26,
0.05g Solvent Red 176 and 0.01
Example 1 from Pigment Green 7
In the same manner as [A], filter molded products [M] with a thickness of 1 mm, 2 mm, and 3 mm were obtained, respectively. The above Example 1 is an example in which a synthetic resin filter composition of the present invention is formed by blending Solvent Green 28 with a synthetic resin (AS resin) having good light transmittance. Regarding the filter molded product [A] obtained in Example 1, the light transmittance was measured for a 1 mm thick one in the visible region and a 2 mm thick one in the near infrared region. As shown in Figure 2, the transmittance of visible light at 520 nm is approximately 6%, while the transmittance of near-infrared light at 900 to 1000 nm exceeds 90%, especially in the range of 900 to 1000 nm.
It has been found that it can be used as a filter in the receiving section of a remote control device that operates with light at a wavelength of 1000 nm. Next, in the above Example 2, Solvent Green 28
This is an example in which Solvent Green 26 was added as a substance that absorbs visible light that cannot be absorbed by filter molded product [B] as shown in Figure 2. The effect is noticeable, from 900 to 1000 nm
The transmittance of near-infrared rays is 90 for a molded product with a thickness of 2 mm.
It is possible to reduce the transmittance of visible light at 520 nm to a value of about a trace (around 1%) for a molded product with a thickness of 1 mm while maintaining a value close to 1%. As a result,
It can be seen that if the amount of near-infrared rays emitted from the transmitting section of the remote control device is large, it can be used satisfactorily as a filter for the receiving section. Furthermore, in the above Example 3, solvent green
This is an example in which a combination of two types of substances were added as substances that absorb visible light that 28 cannot absorb.
Filter molded product obtained in this Example 3 [E]
For [G], visible light transmission was not measured even with a 1 mm thick one, and near-infrared transmittance was measured with a 2 mm thick one, and as shown in Figure 3, the transmission of visible light was 90%. Light transmittance values of similar values were measured, making it suitable as a filter for the receiving section of a remote control device. Also, according to the light transmittance curves of each filter molded product [E] to [G] in Figure 3, the total amount of Solvent Green 28, Solvent Green 26, Solvent Green 3, or Solvent Red 176 is It was found that the effect is almost proportional to the transmittance. Further, in the above Example 4, the wavelength is 750 to 850 nm, particularly,
This is an example in which a substance that reduces the transmittance of light rays with a wavelength of 750 to 850 nm is added when it is necessary to lower the transmittance of near-infrared rays with a wavelength of 800 nm. For the filter molded products [H] to [M] obtained in Example 4, visible light transmission was not measured even with a 1 mm thickness, and near-infrared transmittance was measured with a 2 mm thickness. As shown in Fig. 4, the results show that filter molded products [J], [K] and [M] have a light transmittance of over 80% for near infrared rays of 900 to 1000 nm;
A low light transmittance of 10-20% was measured for near-infrared light at 800 nm. Therefore, by adjusting the blending ratio of Solvent Green 28, Solvent Green 26, Solvent Red 176, and Pigment Green 7, visible light can be completely blocked while maintaining near-infrared transmittance of 900 to 1000 nm at a high value. 750-850nm, especially
It has been found that the transmittance of near-infrared rays at 800 nm can be reduced to a low value. FIG. 5 shows filter molded products [D], [E], [F], [G], obtained in each of Examples 2 to 4 above.
Regarding [H], [I], [J], [K] and [L],
A light source that emits a light beam with a wavelength of 950 nm,
This shows the results of investigating the relationship between the transmittance of light from tungsten lamps and fluorescent lamps that emit a relatively large amount of light with a wavelength of 820 nm.The thickness of a filter molded product and the transmittance are inversely proportional. Regarding tungsten lamps that emit a relatively large amount of near-infrared radiation,
Filter molded products of Example 4 [H], [I],
[J], [K] and [L] are filter molded products of other Examples 2 and 3 [D], [E], [F] and [G]
It was also found that when the light source was a fluorescent lamp, each of the filter molded products [D] to [L] blocked the light rays better. As described above, the synthetic resin filter composition of the present invention can effectively block near-infrared rays and is suitable as a filter for use in the receiving section of a remote control device equipped with a light source that emits near-infrared rays. By appropriately adding a substance that absorbs visible light that cannot be absorbed by Solvent Green 28 or a substance that reduces the transmittance of light with a wavelength of 750 to 850 nm, a synthetic resin filter composition having desired properties can be created. Obtainable. In each of the above examples, AS resin was used as a synthetic resin with good light transmittance, but GP polystyrene resin, MMA (methyl methacrylate) resin, styrene MMA resin, vinyl chloride resin, polyethylene resin, polyester resin , polypropylene resin, or other synthetic resins with good light transmittance, such as polyvinyl butyral resin, can be similarly used in the synthetic resin filter composition of the present invention.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the light transmittance of Solvent Green 28 used in this invention, FIG. 2 is a graph showing the light transmittance of filter molded products according to Examples 1 and 2, and FIG. FIG. 4 is a graph showing the light transmittance of the filter molded product according to Example 4, and FIG. 5 shows the thickness and light transmittance of the filter molded product by changing the light source. This is a graph measuring the relationship between

Claims (1)

[Claims] 1. Solvent Green 28, which is an anthraquinone-based oil-soluble dye, is added to a synthetic resin with good light transmittance.
(color index name) at a ratio of 0.1 to 1.0wt%, without inhibiting the transmission of near-infrared rays.
A composition for a synthetic resin light filter, characterized in that it substantially blocks the transmission of light rays with wavelengths shorter than 750 nm. 2 Add 0.01 to 0.5wt of a substance that absorbs visible light that Solvent Green 28 (color index name) cannot absorb without interfering with near-infrared transmission.
% of the composition for a synthetic resin light filter according to claim 1. 3. Claim 1 or 2, characterized in that a substance that reduces the transmittance of light with a wavelength of 750 to 850 nm is additionally blended at a ratio of 0.005 to 0.1 wt%.
A composition for a synthetic resin light filter as described in 1.