JPS62158779A - Infrared absorptive composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition which has good solubility ni an organic solvent, good compatibility with, e.g., a binder, a large capacity of absorbing a near-infrared light, and fastness to heat and light, by using a quaternary phosphonium salt of a specified aromatic diol nickel complex. CONSTITUTION:An infrared absorptive composition containing a quaternary phosphonium bis(1,2-benzenedithiolate)nickelate derivative of formula I (wherein R<1>-R<4> are each alkyl or aryl; R is H or CH3; n is 1-4) (e.g., compounds of formulas II and III). This composition has excellent properties such that it is highly soluble in an organic solvent, can be finely dispersed or dissolved well in a printing vehicle, and has a large capacity of absorbing a near infrared light. It also has excellent heat and light resistance. The above-mentioned compound can be easily synthesized and manufactured at a low cost. Therefore this composition can be used, e.g., as an ink for an ink jet printer, and also as a material for thermal recording and an optical disk recording material by means of a laser in which photothermalconversion is utilized.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a novel infrared absorbing composition, and more specifically, an infrared absorbing composition that absorbs far-red light or near-infrared light with a wavelength of 700 to 1500 nm. Regarding the composition.

(Prior Art) Infrared absorbers that selectively absorb far-red light with a wavelength of 700 to 1500 nm have various uses in addition to optical filter materials, as described below. Utilizing the light to heat conversion effect, it is used in ■ optical disk recording layers ■ thermosensitive color recording materials using laser ■ organic coatings for optical disks. By utilizing its light absorption effect, it can be used in inkjet printer inks, barcode inks, antihalation agents for photosensitive materials, infrared couplers that form infrared absorbing pigments for soundtracks, etc. in molds for lφ photosensors, etc. can give.

Among these, the use of an aromatic dithiol-based nickel complex having a quaternary ammonium salt is disclosed in JP-A-58-16888 and JP-A-57-11090 as a light absorbing agent for laser recording films.

Furthermore, ink for inkjet printers uses a solvent such as ethyl cellosolve and a dye that dissolves in this organic solvent as an infrared absorber. In this case, this infrared absorber is a chemical substance that is useful for reading with an optical reading device that uses an infrared light source with a wavelength of 740 to 900 nm. Conventionally, such infrared absorbers for inkjet printers include nigrosine, chromium complex salts, etc. Japanese Patent Publication No. 56-135
The compound disclosed in No. 568 has been used.

Next, silicon is mainly used in conventional photodetection devices such as cameras, or optical sensors such as optical image receiving elements, and photodiode MOS image sensors,
It is used in the form of CCD image sensors, CID image sensors, etc.

The spectral sensitivity of silicon is quite large for light of 700 to 1l100n in the infrared region, and in order to make the 1 spectral sensitivity curve similar to the specific luminous efficiency curve, the noise will increase unless the light in the infrared region is cut.

Conventionally, this type of photodetecting device has used inorganic glass or organic near-infrared absorbers (see Japanese Patent Laid-Open No. 58-9378).

(Problems to be Solved by the Invention) However, aromatic dithiol-based nickel complexes containing quaternary ammonium salts have low solubility in organic media, and the concentration of the infrared absorber in the composition when coating on a substrate is low. There were drawbacks such as the inability to increase the temperature and the limitations on the media that could be used. In addition, even if nigrosine used in jet printer ink is initially solubilized, precipitates form when left for a long period of time, and chromium complex salts cannot be dispersed or dissolved in organic solvents alone, so they must contain water or nitrogen. It was necessary to add a solubilizer. It was also used in photodetectors. The organic near-infrared absorber described in JP-A No. 58-9378 had the disadvantages of low solubility in organic solvents and insufficient light resistance, and was not satisfactory.

The purpose of the present invention is to overcome the drawbacks of these infrared absorbing compositions and to provide an infrared absorbing composition that has high solubility in organic solvents and good compatibility with binders, etc. An object of the present invention is to provide an infrared absorbing composition that has a large ability to absorb near-infrared light and is robust against heat and light.

(Means for Solving the Problems) As a result of various studies conducted by the present inventors in order to achieve the object described in h., certain types of quaternary phosphonium salts of aromatic dithiol-based nickel complexes are The inventors have discovered that the solubility in the infrared rays is extremely good and the ability to absorb near-infrared light is extremely large, and based on this knowledge, the present invention has been completed.

That is, the present invention has the following formula: (wherein R1, . . . , R4 represent an alkyl group or an aryl group, and R represents a hydrogen atom or a methyl group.

The present invention provides an infrared absorbing composition characterized by containing a quaternary phosphonium bis(1,2-benzenedithiolat) nickelate derivative represented by (n is an integer of 1 to 4). In the present invention, the term "infrared absorbing composition" means excluding optical filter materials.

In the compound represented by the above general formula CI), R1 to R4 preferably represent an alkyl group having 1 to 20 carbon atoms, and examples of the alkyl group include a methyl group, an ethyl group, and an n-butyl group.

Examples include 1so-7mil group, n-dodecyl group, and n-octadecyl group.

In this case, the alkyl group may be further substituted with 1
For example, a cyano group, an alkyl group having 1 to 20 carbon atoms (eg, methyl group, ethyl group, n-butyl group, n-octyl group, etc.), 7 aryl having 6 to 14 carbon atoms! (e.g. phenyl group, tri-l group, α-naphthyl group, etc.),
7-syloxy group having 2 to 12 carbon atoms (for example, acetoxy group, benzoyloxy group or p-methoxybenzoyloxy group), flukoxy group having 1 to 6 carbon atoms (for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.) , an aryloxy group (e.g., phenoxy group, tolyloxy group, etc.).

Aralkyl groups (e.g. benzyl, phenethyl or anisyl), alkoxycarbonyl groups (methoxycarbonyl, ethoxycarbonyl, n-butoxycarbonyl, etc.), aryloxycarbonyl groups (
phenoxycarbonyl group, tolyloxycarbonyl group, etc.), acyl group (acetyl group, benzoyl group, etc.), acylamine 7 group (acetylamino group, benzoylamide 7 group, etc.), carbamoyl group (N-ethyl group, etc.), carbamoyl group (N-ethyl group, etc.)
N-phenylsulfonylamino group, etc.), alkylsulfonylamino group (e.g., methylsulfonylamino group, phenylsulfonylamino group, etc.), sulfamoyl group, (N-ethylsulfamoyl group, N-phenylsulfamoyl group, etc.), It may be substituted with a sulfonyl group (mesyl group, tosyl group, etc.).

Examples of the aryl group represented by R1-R4 in the above general formula CI) include a phenyl group and a P-tolyl group.

Further, R1 and R4 may be a mixture of an alkyl group and a 7-aryl group.

In R1-R4, it is preferable that the number of alkyl groups is 1 or more and the number of aryl groups is 3 or less.

In general formula CI), R1-R4 are particularly preferably alkyl groups having from a4 to a16 carbon atoms. As for the alkyl group, lower alkyl groups are preferred over long chain ones, straight chain alkyl groups are preferred over branched ones, and unsubstituted alkyl groups are preferred over substituted ones.

1111 Quaternary phosphonium L represented by general formula (I)
The 1bis(l,2-benzenedithiolat)ninchelate derivative can be produced as follows.

A 1,2-benzenedithiol derivative is dissolved in absolute ethanol, and this is neutralized with KOH. To this solution is added an ethanol solution of a nickel salt, then a solution of a quaternary phosphonium salt, stirred in air (or while blowing oxygen), and the precipitate formed is filtered. Non-a-salt as a by-product (
To remove potassium salt), crude crystals are obtained by extracting with an organic solvent such as acetone and then distilling off the solvent. This is recrystallized from, for example, acetone-alcohol.

Preferred examples of the compounds represented by the general formula CI) are as follows; however, it goes without saying that the present invention is not limited to these exemplified compounds.

In addition, in the following formula, CxH2x. 1 means a linear alkyl group having X carbon atoms.

The absorption maximum (λwax) and molar absorption number (εwax, 1 mmo bi1-clI-1 unit) of these compounds are as follows.

Table 1: (The infrared absorbing composition of the invention is a composition in which the compound represented by the general formula (I) is appropriately contained in a binder.

There are no particular restrictions on the binder, and any binder can be used regardless of whether it is organic or inorganic, as long as it exhibits infrared absorbing properties as a composition. Such binders include polymeric materials such as plastics.1. Examples include inorganic vehicles such as glass.

Further, a solvent can be used in this binder if necessary. Preferred solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, chloroform, methylene chloride,
methanol, ethanol.

Examples include organic solvents such as toluene, ethyl acetate, isoamyl acetate, acetonitrile, ethyl cellosolve, and dimethylformamide.

Next, an embodiment in which the infrared absorbing composition of the present invention is used in an optical recording medium will be described.

Optical recording media (hereinafter referred to as optical recording media) consist of a substrate and a recording layer, but depending on the purpose, the substrate may be provided with a drag layer and the recording layer L may be provided with a protective layer. .

Any known substrate can be used as long as it is transparent to the laser used. Typical examples include glass or plastic, and examples of the plastic include acrylic, polycarbonate, polysulfone, polyimide, and polyester. Its shape can be various, such as a disk, card, sheet, or roll film.

A guide groove may be formed on the glass or plastic substrate to facilitate trunking during recording, and a plastic binder or a subbing layer such as an inorganic oxide or inorganic sulfide may be provided on the glass or plastic substrate. An undercoat layer having a thermal conductivity lower than that of the substrate is preferable.

The recording layer can be divided into one consisting of an infrared absorber alone or a combination thereof with other materials, and one consisting of a reflective layer and a light absorbing layer containing the infrared absorber. The recording layer composed of the infrared absorber alone or in combination with other materials can be prepared by dissolving the infrared absorber in a solvent and coating it, by vapor depositing it on the substrate, or by mixing it with a resin solution and coating it. It is formed by applying a mixed solution with other pigments, or by dissolving it together with other pigments in a resin solution and applying it.

As the resin, known resins such as PVA, PVP, polyvinyl butyral, polycarbonate, nitrocellulose, polyvinyl formal, methyl vinyl ether, maleic anhydride copolymer, and styrene-butadiene copolymer are used. The weight ratio of the infrared absorber represented by the general formula [I] to the resin is 0.
If other dyes, such as triarylmethane dyes, merocyanine dyes, cyanine dyes, azo dyes, anthraquinone dyes, etc., which have absorption outside the wavelength range of the semiconductor laser are used, it is desirable that Not only a conductor laser but also a He-Ne laser or the like can be used for recording, which is suitable.

One or more recording layers are provided.

The thickness of the recording layer is 1 usually 0, Ol gm-I ILm
.

Preferably it is in the range of 0.08 to 0.8.Bm.

In the case of reflective readout, it is particularly preferably an odd multiple of 174 of the laser wavelength used for readout.

When providing a reflective layer for a semiconductor laser or He-Ne laser, etc., (the reflective layer is provided on the plate by providing a recording layer on the next two reflective layers by the method described above, or There are two methods: providing a recording layer on the substrate and then providing a reflective layer thereon.

The reflective layer can also be formed by other methods such as vapor deposition, sputtering, and ion blating.

For example, a metal salt or a gold hA complex salt is dissolved in a water-soluble resin (PVP, PVA, etc.), and further.

Apply a solution containing a reducing agent to the substrate and heat it to 50℃~150''
C is preferably formed by heating and drying at 60°C to 100°C.

The amount of metal salt or metal complex salt to resin is 0.1-10, preferably 0.5-1.5 in terms of ffl amount ratio. In this case, the appropriate thickness of the recording layer is 0.01 to 0.1 m for the metal particle reflective layer and 0.01 to 1 m for the light absorption layer.

As the metal salt or metal complex salt, silver nitrate, potassium silver cyanide, potassium gold cyanide, silver ammine complex, silver cyanide complex, gold salt, or gold cyanide complex can be used. Formalin is used as a reducing agent.

Tartaric acid, tartrate, reducing agent primary hypophosphite, sodium borohydride, dimethylamine porane, etc. can be used. The reducing agent is 0.2 to 1 per mole of metal salt or metal complex m.
It can be used in an amount of 0 mol, preferably 0.5 to 4 mol.

In optical recording media, information is recorded by emitting a spot-shaped high-energy beam such as a laser onto the recording layer (through the plate or from the opposite side of the substrate), which is absorbed by the recording layer. The emitted light is converted into heat, forming pits (holes) in the recording layer.

Further, information is read by irradiating a laser beam with a low output power below a recording threshold energy, and detecting a change in the amount of reflected light from a pit portion and a portion where no pits are formed.

In addition, when the infrared absorbing composition of the present invention is used in a color separation filter or sensor mold,
For example, it can be carried out with reference to the description in Japanese Patent Application Laid-Open No. 57-22209.

Acrylic or methacrylic resin, phenolic resin,
Modified phenolic resin, ketone resin, polyester resin,
One or more types of urethane resin, silicone resin,
An infrared cutoff filter can be formed by dissolving it in a resin and applying it.

The weight ratio of infrared absorber to resin is 0.00 to 1 part of resin.
0.01 to 0.2ff6 is better than 1 to 0.5 parts, but this weight ratio depends on the molecular extinction coefficient of the infrared absorber in the infrared region, the compatibility between the infrared absorber and the grease coat, and the coating thickness. Or determined by the thickness of the molding.

The solvent used is one that dissolves at least one of the infrared absorber and the resin. These include chlorinated solvents such as dichloromethane and chloroform, ester solvents such as ethyl acetate and isoamyl acetate, ester solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, alcohols such as ethyl alcohol and butyl alcohol, pyridine, dimethylformamide, These include nitrogen-containing solvents such as dimethylacetamide.

Next, embodiments in which the infrared absorbing composition of the present invention is used in an inkjet ink will be described.

Inkjet inks that use organic solvents as solvents are mainly used in electrostatic acceleration type, electrostatic air flow type, etc., both of which require applying high-pressure pulses to the ink to enable ink flow or ink droplet formation. This problem involves not only the electrical properties of the ink, but also the physical properties related to fluidity such as surface tension and viscosity;
It can be carried out according to the method described in JP-A-56-135568.

Inkjet ink uses an infrared absorber,
Solvents include ethyl cellosolve, toluene, ethanol, n-butanol, ethyl methyl ketone, methyl imbutyl ketone, dichloromethane, triethanolamine,
Organic solvents such as dimethylformamide and isoamyl acetate are used, and glycerin and metallurgy are added to adjust the viscosity.

The content has a viscosity of 10 cp at room temperature and a specific resistance of lXl.
The composition ratio of the organic solvent and the viscosity modifier is selected so that it becomes 0 - IXIO"Ω·cm.

The content ratio of the infrared absorber to the solvent was 1 ffr of the solvent.

For this part, infrared absorber o, ot-o, a part,
A pigment that absorbs df visual rays may also be added to the ink, as the case may be, which should preferably be dissolved at room temperature or be finely dispersed to at least a uniform particle size of 0.81 Lm or less.

(Effects of the Invention) In the present invention, the quaternary phosphonium bis(l,2-benzenedithiolat) nickelate derivative has high solubility in organic solvents, is well finely dispersed or dissolved in printing vehicles, and has a near-red It has an excellent property of having a large ability to absorb external light.

Further, the infrared absorbing composition of the present invention has excellent heat resistance and light resistance. Furthermore, the quaternary phosphonium bis(l,
2-Benzenedithiolat) nickelate derivatives have excellent practical advantages in that they are easy to synthesize and can be produced at low cost.

Therefore, the infrared absorbing composition of the present invention can be used as an ink for inkjet printers, as well as for thermal coloring by laser using light->heat exchange, thermal recording, and optical disk recording material.

(Example) Next, the present invention will be explained in further detail based on examples.

In addition, in the following, "section" means "revised section" unless otherwise specified.

Reference Example 1 <Synthesis of Exemplified Compound (2)> 16 g of potassium water chloride was dissolved in 200 liters of absolute ethanol, 20 g of benzenedithiol was added to this solution, and the mixture was stirred at room temperature for 10 minutes. Japanese food 1
A solution of 7 g dissolved in 200 ml of absolute ethanol was added, and the mixture was further stirred at room temperature for 30 minutes. A solution of 50 g of tetra-n-butylphosphonium bromide dissolved in 200 ml of absolute ethanol is added to this solution at room temperature. After the addition was completed, the mixture was further stirred at room temperature for 2 hours, and the precipitated dark green crystals were filtered, washed first with water and then with ethanol, and air-dried.

This was recrystallized from hot acetone-ethanol to obtain Exemplary Compound (2). Yield 27g, melting point 145-148
℃.

Reference Example 2 (Synthesis of Exemplified Compound (3)) 36 g of water-ugly potassium was dissolved in 600 tnl of absolute ethanol, 50 g of toluene-3,4-dithiol was added to this solution, and 1
This was then stirred at room temperature for 0 minutes, followed by nickel chloride.
A solution of 36.8 g of hexahydrate dissolved in 400 ml of anhydrous ethal was added, and the mixture was further stirred at room temperature for 30 minutes.

A solution of 111 g of tetra-n-butylphosphonium bromide dissolved in 300 mJL of absolute ethanol is added to this solution at room temperature. After the addition was completed, the mixture was further stirred at room temperature for 2 hours, and the precipitated dark green crystals were filtered, washed first with water and then with ethanol, and air-dried. This was recrystallized from hot acetone-ethanol to obtain exemplified compound (3). Collection F
&50g, melting point 142-144°C.

Reference Example 3 (Synthesis of Exemplified Compound (6)) 36 g of potassium hydroxide was dissolved in 600 m of absolute ethanol, 50 g of toluene-3,4-dithiol was added to this solution, and the mixture was stirred at room temperature for 10 minutes. A solution of 36.8 g of nickel hexahydrate dissolved in 400 mM of anhydrous ether was added, and the mixture was further stirred at room temperature for 30 minutes.

To this solution is added a solution of 230 g of hexadecyltributylphosphonium bromide dissolved in 300 mjl of absolute ethanol at 50°C. After the addition was completed, the mixture was further stirred at room temperature for 2 hours, and the precipitated dark green crystals were filtered, washed first with water and then with ethanol, and air-dried. This was recrystallized from hot ethanol to obtain exemplified compound (6). Yield 43
g, melting point 56-60°C.

Reference Example 4 (Synthesis of Exemplified Compound (7)) 36 g of potassium hydroxide was dissolved in 600 ml of absolute ethanol, 50 g of toluene-3,4-dithiol was added to this solution, and the mixture was stirred at room temperature for 10 minutes. - After adding a solution of 36.8 g of hexahydrate dissolved in 400 mJl of anhydrous ethal, the mixture was further stirred at room temperature for 30 minutes. Add benzyltributylphosphonium bromide 12 to this solution.
7g of absolute ethanol 360m! Add the solution in L at room temperature. After adding.

After further stirring at room temperature for 2 hours, the precipitated dark green crystals were collected in i!
! filtered, washed first with water and then with ethanol, and air-dried.

This was recrystallized from hot acetone to obtain exemplified compound (7). Yield 63g, melting point 213-215°C.

Other exemplary compounds used in the present invention were also synthesized in the same manner as in Reference Examples 1 to 4.

Example 1 Exemplified Compound (2) 1 part Oil-soluble blue dye 4 o, 7p Ethylcea Solv 51 1.2-Benzinthiazolone (mold inhibitor) 0.001 part Glycerin 3 parts The above components were mixed homogeneously. , the resulting composition is.

This ink composition, which has a specific resistance of 1O3Ω・Cm and a viscosity of 4cp, was applied to an inkjet recording device, and a good image was obtained, which could be read by a reading device using a semiconductor laser (830 parts m) as a light source. .

Example 2 Inamyl acetate 7 parts Exemplary compound (2
) 0.5 parts Oil-soluble dye (Oil Black HBB) 0.5 parts Metal soap
The ink composition obtained by homogeneously mixing 0.05 part of the above components and having a specific resistance of 107 Ω·Cm and a viscosity of 5 cp was applied to an inkjet recording device to obtain a good image.

This could be read with a reading device using a semiconductor laser (830 parts m) as a light source.

Example 3 Exemplified compound (3) 1g nitrocellulose 066g dichloromethane
A solution having the above composition was spin-coated onto a glass plate and dried at 40°C to obtain a recording layer with a thickness of 0.40 gm.

The reflectance and absorption at a wavelength of 780 nm were 14% and 25%, respectively.

A wavelength of 780 nm was applied to the recording medium thus obtained.

When a signal was recorded with IMH2 using a semiconductor laser with a beam diameter of 1.6 gm and a power of 4 mW on the irradiation surface, a pit with a diameter of 1.0 pm was formed with 0.41 L seconds of irradiation (1.6 nJ/pit). This recording medium was stored for one month at a temperature of 60°C, indoor light, and humidity of 90%, but there was no change in the recording and reading characteristics.

Example 4 Exemplified Compound (J) 1g Polycarbonate resin 1. OgC, 1, 7 Seed 7 Blue 83 (C, 1, 42830) 1, 2 gl
, 2-dichloroethane 12ml A solution of the above composition was spin-coated on a surface-hardened acrylic plate/Iil,
, and dried at 60° C. to obtain a recording layer with a thickness of 0.4 gm. wave f
Reflectance at <800 nm and also wavelength 63
The absorption rates at 0 nm were 13% and 60%, respectively. This recording medium was heated at 6 mW on the irradiation surface and with a beam diameter of 1.
0.4 with a semiconductor laser beam with a wavelength of 800 nm at 6 m
When the signal was recorded at MHz, the irradiation time of t,og seconds (6,
A bit with a diameter of 1.0 pm was formed at 0 nJ/pit). In addition, using a He-Ne laser for this recording medium, the beam diameter was 1.64 m and the energy on the recording surface was 5 mW, 4 MHz.
When the signal of z was recorded, o, 4g seconds of irradiation (1,6n
A bit of 1.0 μm was formed with J/pit).

A storage test was conducted in the same manner as in Example 3, but there was no change in characteristics.

Example 5 Exemplified compound (2) l g Nitrocellulose 0.7 g dichloromethane
A coating solution of 20mfLL composition was spin-coated onto a glass plate, dried at 40°C, and a thickness of 0.401Lm was obtained.
A recording layer was obtained. The reflectance and absorption at a wavelength of 830 nm were 15% and 65%, respectively.

The thus obtained recording medium was heated to IMHz using a semiconductor laser with a wavelength of 830 nm, 4 mW on the irradiation surface, and a beam diameter of 1.6 μm.
When the signal was recorded at 0.3 ps irradiation (1,2n
A bit with a diameter of 1.01 Lm was formed. This recording medium was stored for one month at a temperature of 60°C, indoor light, and humidity of 90%, but there was no change in the recording and reading characteristics.

Example 6 Exemplified compound (2) l g Polycarbonate super fat 0.7 g C,1, Acid Blue 83 (C,1,42830) 1,2 g
, 2-dichloroethane 12m A solution of the above composition was spin-coated on a surface-hardened acrylic plate, and
It was dried at .degree. C. to obtain a recording layer with a thickness of 0.4 gm. wavelength 830
The reflectance and absorption in nm were 16% and 56%, respectively.

Moreover, the absorption rates at a wavelength of 630 nm were 13% and 68%, respectively. 6mW on the irradiated surface of this recording medium,
When a signal was recorded with a 1830 nm semiconductor laser beam with a beam diameter of 1.6 JLm at 0.4 M) IZ, the result was 0.3
After a final second of irradiation (1,8 nJ/pit), pits with a diameter of 1.0 m were formed. In addition, a 4MH2 signal was recorded on this recording medium using a He-Ne laser with a beam of 111.6JLm and an energy of 5mW on the recording surface.
．． A pit of 0 pm was formed.

A storage test was conducted in the same manner as in Example 5, but there was no change in characteristics.

Example 7 A solution with the following composition was spin-coated onto a polycarbonate disk.
A dry undercoat layer having a thickness of O-IILm was obtained.

Cellulose acetate butylene) 0.8g acetone 32m9゜To this, exemplified compounds (
Liquid exemplary compound (2) of the following composition containing 2)
l gPolyvinyl formal 0
．． A recording layer having a dry film thickness of 0.4x was obtained by spin coating 7g dichloromethane log. Furthermore, this layer is coated with silver to a thickness of 0. t4 to create a recording medium, with the silver surfaces facing each other, spacers were placed in the center and around the discs, and two disc-shaped recording media were sandwiched and joined together to obtain a recording medium. Ta.

In addition, a semiconductor laser beam with a wave of 1830 nm and a beam diameter of 1.61 parts m was applied to the irradiation surface from the polycarbonate plate side.
Irradiated with mW and irradiated for 0.7#L seconds (4.2nJ/5ec
), a pit with a diameter of 0.91 part m was formed.

This recording medium was stored in room light at 80° C. and 90% for two months, but there was almost no deterioration in the recording and reading characteristics.

Example 8 Exemplified Compound (2) 1.0 g Polyvinyl formal 0.7 g Dichloromethane 12 m A solution of the above composition was spin-coated onto a polycarbonate resin plate on which aluminum had been vapor-deposited to a thickness of 0.08 parts m. A light absorption layer of 67%m was obtained.

The reflectance and absorption at a wavelength of 830 nm were 16% and 64%. Using a semiconductor laser with a wavelength of 830 nm on this recording medium, a 2 MHz signal was recorded from the nozzle plate side with an irradiation surface energy of 6 mW and a beam diameter of 1.6 gm.
A pit with a diameter of 0.87°C was formed. Even after this recording medium was stored for one month at 60° C. and 90% humidity, the recording characteristics and the reproduction characteristics of the recorded pits did not deteriorate.

Example 9 Nitrocellulose 0.4g dichloromethane lomjL A liquid with the above composition was spin-coated on an acrylic plate to form an undercoat layer, and exemplified compound (2) was vacuum-deposited onto this to obtain a layer with a thickness of 0.2 μm. .

A protective layer having a thickness of 0.57% m was applied to this by spin coating a solution prepared by dissolving 0.5 g of gelatin in 10 ml of water. A laser beam with a wavelength of 830 nm was irradiated from the substrate side in the same manner as in Example 5, and the irradiation was performed for o, sIL seconds (2, OnJ/pit).
), a pit with a diameter of 0.91 part m was formed. This recording material was stored in room light at a temperature of 60° C. and a humidity of 90% for one month, but there was no change in characteristics.

Example 10 2-7nilino-3-methyl-6-N-cyclohexyl-
2.4 parts of N-methylaminofluorane.

2.4 parts of 2-anilino-3-chloro-6-dinithylaminofluorane (color former dileuco dye), exemplified compound (3
)0.2j'j'll of diisopropylnaphthalene24
A solution to be used as a core substance was prepared by dissolving the mixture in the following parts.

Zaraani xylylene diisocyanate/trimethylolpropane (3:l) adduct 18 parts and methylene chloride 1
7 parts were added and dissolved.

This M colorant solution was mixed with 3.5 parts of polyvinyl alcohol,
It was added to an aqueous solution containing 1.7 parts of gelatin and 2.4 parts of 1,4-di(hydroxyethoxy)benzene dissolved in 58 parts of water and emulsified and dispersed at a temperature of 20°C to obtain an average particle size of 3I.
An emulsion of Lm was obtained. 100 parts of water was added to the emulsion and heated to 60° C. by hand. After 2 hours, a microcapsule solution containing a color former, a color inhibitor, and an ultraviolet absorber in the core substance was obtained.

Separately, 20 parts of bisphenol A as a color developer was added to 100 parts of a 5% polyvinyl alcohol aqueous solution and dispersed in a sand mill for about 24 hours to obtain a dispersion of bisphenol A having an average of 3 ILm.

5 parts of f'J leaked microcapsule liquid and 3 parts of bisphenol A dispersion were mixed to prepare a coating liquid. This coating solution was applied to the surface of smooth -Laga paper (50 g/m") and dried at a temperature of 40°C for 30 minutes.
A thermosensitive recording layer of m'' was provided.

In this way, thermosensitive recording sheet A containing microcapsules was produced.

Separately, a heat-sensitive recording sheet B to which exemplified compound (3) was not added was prepared.

Next, thermal recording was performed using each of the obtained thermal recording sheets.

Load the thermal recording sheet into a G II mode thermal printer (Panafax 7200, manufactured by Hitachi, Ltd.),
When thermal recording was performed on the recording sheets by operating the thermal head, clear black images were obtained on all of the heat-sensitive recording sheets as shown below.

Thermal recording sheet) A Thermal recording sheet B (exemplified compound cloth) (No exemplified compound) Color density 1.20
1.09 coloring (turnip 0.11 0.1
0) Concentration Example 11 Illustrated in a visible light transmitting resin mixed with 70 g of hexahydrophthalic acid, 20 g of tetraglycidyl isocyanurate, 30 g of CX-221 (manufactured by Chisso Corporation, trade name), and 0.15 g of imidazole. Infrared absorber of compound (2) 0.
A silicon diode for a photodetector of a camera was molded using the resin composition (A) obtained by dissolving 3 g of the resin composition (A).

A silicon diode is set in a mold heated to about 150°C, and the resin composition (A) is poured onto the surface of the diode to a thickness of about 2 mm.
After curing for minutes, the silicon diode molded with the resin composition (A) was removed from the mold and heated to 150°C.
It was further cured for about 2 hours.

Example 12 Exemplary compound (2) on a transparent glass substrate with a thickness of 0.5 mm
A composition liquid containing a thermosetting acrylic resin and dimethylformamide in a ratio of 1.5:8:3 (tun-knee ratio) was applied to form a near-infrared absorbing resin film with a thickness of 150 m.
C. for 20 minutes to form an infrared blocking layer.

A chromium nitride layer was deposited on this infrared blocking layer to a thickness of 50 OA by sputtering, and a chromium layer was further deposited on top of this to a thickness of 150 OA. (Manufactured by Silapray, USA)
After coating, the film was exposed to light using a predetermined photomask, developed and dried, and then the exposed chromium layer and chromium nitride layer were removed by etching with a cerium ammonium nitrate based etching solution. Thereafter, the resist layer is peeled off to form a photoshield layer having a predetermined pattern on the infrared blocking layer. This photoshield layer has a reflectance of 15% or less from the glass surface, so there is no flare problem.

Next, a water-soluble photosensitive solution consisting of casein-ammonium dichromate was applied to the film H of 0.8#Lm on the infrared blocking layer with the photoshield layer, and after drying, a predetermined photomask was accurately aligned. Close contact.

It is exposed to light and developed with hot water to form a layer to be dyed with a predetermined pattern, and this layer to be dyed is dyed in a red dyeing bath.
Next, after carrying out a prescribed resist dyeing treatment, a water-soluble photosensitive solution was applied to
After coating to a thickness of 4 m, drying, exposure, and development, dyeing was performed using a green dyeing bath to form a G colored layer having a predetermined pattern, and a second color colored layer was formed. In addition, 2 colors 11
A colored layer of the third color B having a predetermined pattern was formed using a blue dyeing bath in the same manner as in the method for forming the colored layer. In this way, a color separation filter layer consisting of R, G, and B colored layers having a predetermined pattern is obtained. after that,
An acrylic resin was applied to a thickness of IILm on one layer of this color separation filter, and the chip size of the color separation filter with a protective film formed thereon was set to the size of the photosensitive area of the solid-state image sensor.

This color separation filter had an excellent ability to block long wavelength light of 700 nm or more.

The compositions of the R, G, and H dye baths used above are as follows.

Red dyeing bath Kayanol Milling Red R3 (Nippon Kapaku Co., Ltd.) 1 part acetic acid
3 parts water 100 parts Green dye bath Brilliant India Blue (manufactured by Hoechst) 1 part Suminol Yellow MR (manufactured by Sumitomo Chemical) 1 part acetic acid
3 parts water
100 parts blue dyeing bath kyanol cyanine 6B

Claims (1)

[Claims] General formula▲ Numerical formula, chemical formula, table, etc.▼ (In the formula, R^1 to R^4 represent an alkyl group or an aryl group, R represents a hydrogen atom or a methyl group, and n represents 1~
Indicates an integer of 4. ) An infrared absorbing composition comprising a quaternary phosphonium bis(1,2-benzenedithiolat) nickelate derivative represented by: