JPH0713049B2 - Aminium salt compound - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an aminium salt compound having absorption in the infrared region, and more particularly to an aminium salt compound which improves the light resistance of an organic dye compound.

[0002]

2. Description of the Related Art Generally, optical disks and optical cards are
Optically detectable small (eg, about 1 μm) pits formed in a thin recording layer provided on a substrate can be made into spiral or circular and linear track forms to store high density information. To write information on such a disc, a laser focused on the surface of the laser-sensitive layer is scanned, and only the surface irradiated with this laser beam forms pits, and the pits form spiral or circular and linear tracks. It is formed in the form of. The laser sensitive layer can absorb laser energy to form optically detectable pits. For example, in the heat mode recording system, the laser-sensitive layer absorbs heat energy, and small recesses (pits) can be formed at the location by evaporation or melting. In another heat mode recording method, the pits having an optically detectable density difference can be formed at the spots by absorbing the irradiated laser energy.

By using an organic dye thin film as the recording layer having a high reflectance, the optical contrast of the recording pit can be set high. For example, when a polymethine dye, an azulene dye, a cyanine dye, a pyrylium dye having a large light absorption for laser light is used as the organic dye thin film, a metallic luster (reflectance of 10 to 50)
%) To obtain an optical recording medium capable of laser recording and reflective reading. In particular, when a semiconductor laser having an oscillation wavelength of 700 to 800 nm is used as a laser light source, there are advantages that the device can be downsized and the cost can be reduced. However, the organic dye thin film is generally liable to change in material with respect to heat and light.
There is a problem that recording / reproducing characteristics and storage stability are deteriorated.

With respect to such a problem, Japanese Patent Laid-Open No. Sho 60 has already been proposed.
Japanese Patent Laid-Open No. 236131 proposes a method of incorporating an aminium salt or a diimonium salt of a triarylamine compound.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aminium salt compound which further improves the light resistance of an organic dye and is excellent in solvent solubility.

[0006]

That is, the aminium salt compound of the present invention is characterized by having a structure represented by the following general formula (1).

[0007]

[Outside 4]

In the above general formula (1), A is

[0009]

[Outside 5] Indicates.

[0010]

[Outside 6] X  Indicates an anion.

R ₁ to R ₈ are all alkoxyalkyl groups.

[0012]

[Outside 7] X  Is chloride, bromide, iodide, or
Chlorate ion, nitrate ion, benzene sulfonate
Ion, P-toluenesulfonate ion, methyl sulfate
Salt ion, ethyl sulfate ion, propyl sulfate ion
Ion, tetrafluoroborate ion, tetraphenylpho
Urate, Hexafluorate, Benzene
Sulfinate ion, acetate ion, trifluoroacetic acid
Salt ion, propion acetate ion, benzoate ion
Ion, oxalate ion, succinate ion, malonate
Ion, oleate ion, stearate ion,
Citrate ion, monohydrogen diphosphate ion, dihydrogen mono
Phosphate ion, pentachlorostannate ion, chloro
Sulfonate ion, fluorosulfonate ion,
Lifluoromethanesulfonate ion, hexafluoro
Arsenate ion, hexafluoroantimonate ion,
Molybdate ion, tungstate ion, tita
Displays anions such as phosphate and zirconate.
Forget

The substituents R ₁ to R ₈ may be the same or different, but all are linear or branched alkoxyalkyl groups.

The method for producing the present compound is described in US Pat. No. 3,252,881, US Pat. No. 3,575,871, US Pat. No. 3,484,467 and JP-A-61-69.
The method described in Japanese Patent Publication No. 991, etc. can be used, and it can be produced by the following process.

[0015]

[Outside 8]

The amino product obtained by the Ullmann reaction and the reduction reaction can be alkoxyalkylated by selective substitution and then the final product can be obtained by the oxidation reaction.

The aminium salt compound according to the present invention has an alkoxyalkyl group in its structure and is excellent in solvent solubility, probably because of its polarity.

In the aminium salt compound of the present invention, R _1-
Examples of the alkoxyalkyl group that can be used for R ₈ include methoxymethyl, 2-methoxyethyl, 3-methoxypropyl, 2-methoxypropyl, 4-methoxybutyl, 3-methoxybutyl, 2-methoxybutyl, 5-methoxypentyl. , 4-methoxypentyl, 3-methoxypentyl, 2-methoxypentyl, 6-methoxyhexyl, ethoxymethyl, 2-ethoxyethyl, 3-ethoxypropyl, 2-ethoxypropyl, 4-ethoxybutyl, 3-ethoxybutyl, 5 -Ethoxypentyl, 4-
It is a linear or branched alkoxyalkyl such as ethoxypentyl, 6-ethoxyhexyl, propoxymethyl, 2-propoxyethyl, 3-propoxypropyl, 4-propoxybutyl and 5-propoxypentyl.

[0019]

Next, specific examples of the compound of the general formula (1) according to the present invention will be given. For simplification, the compound represented by the formula (1) is represented by A, X, (R ₁ R ₂ ) (R ₃ R ₄ ) (R ₅ R
₆ ) Notated as (R ₇ R ₈ ). For example, in equation (1), A is

[0021]

[Outside 9] Where R ₁ is CH ₂ CH ₂ OCH ₃ and R ₂ to R ₈ are C ₃ H
_{If 7} ,

[0022]

[Outside 10] , ClO ₄ , (C ₃ H ₇ , C ₃ H ₇ ) ₃ (C ₃ H ₇ , C
H ₂ CH ₂ OCH ₃₎ and is denoted.

[0023]

[Outside 11]

[0024]

[Outside 12]

Such an aminium salt compound has a maximum absorption wavelength of 900 nm or more and an absorption coefficient as large as about tens of thousands to hundreds of thousands.

Such compounds are used not only as materials for optical recording media but also as heat insulating films, sunglasses and the like.

The aminium salt compound of the present invention can improve the light resistance of the near-infrared absorbing dye by containing it in the organic dye thin film of the optical recording medium containing the near-infrared absorbing dye.

As the near-infrared absorbing dye used in combination with the aminium salt compound of the present invention as an optical recording medium, generally known dyes are used, for example, cyanine dyes, merocyanine dyes, croconium dyes, Examples include squarylium dyes, azurenium dyes, polymethine dyes, naphthoquinone dyes, pyrylium dyes, and phthalocyanine dyes.

The amount of the aminium salt compound of the general formula (1) added to these dyes is 1 to 60% by weight, preferably 5 to 40% by weight, based on the total solid content of the recording layer. It is preferably 10 to 30% by weight.

In addition to these compounds, a binder may be contained in the recording layer. As the binder, for example,
Nitrocellulose, cellulose phosphate, cellulose sulfate, cellulose acetate, cellulose propionate, cellulose butyrate, cellulose myristate, cellulose palmitate, cellulose acetate / propionate, cellulose acetate such as acetic acid / cellulose butyrate, methyl cellulose, ethyl cellulose, propyl cellulose , Cellulose ethers such as butyl cellulose, polystyrene,
Vinyl resins such as polyvinyl chloride, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyvinylpyrrolidone, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, styrene-butadiene-acrylonitrile copolymer, vinyl chloride-vinyl acetate copolymer, etc. Copolymer resins, polymethylmethacrylate, polymethylacrylate, polybutylacrylate, polyacrylic acid,
Acrylic resins such as polymethacrylic acid, polyacrylamide, polyacrylonitrile, polyesters such as polyethylene terephthalate, poly (4,4′-isopropylidenediphenylene-co-1,4-cyclohexylene dimethylene carbonate), poly (ethylene Dioxy-3,3'-phenylene thiocarbonate), poly (4,4'-isopropylidene diphenylene carbonate-co-terephthalate), poly (4,4'-isopropylidene diphenylene carbonate), poly (4,4 ′
-Sec-butylidene diphenylene carbonate), poly (4,4'-isopropylidene diphenylene carbonate-block-oxyethylene), or other polyarylate resins, or polyamides, polyimides, epoxy resins, phenolic resins, polyethylene Polyolefins such as polypropylene and chlorinated polyethylene can be used.

Further, the recording layer may contain a surfactant, an antistatic agent, a stabilizer, a dispersant, a flame retardant, a lubricant, a plasticizer and the like.

A subbing layer may be provided between the recording layer and the substrate, and a protective layer may be provided on the recording layer.

As the undercoat layer, a protective layer is provided for protection from scratches, dust, stains and the like and environmental stability of the recording layer for the purpose of imparting solvent resistance, improving reflectance, and improving repetitive reproduction. Used for. The materials used for these are mainly inorganic compounds, metals or organic polymer compounds. As the inorganic compound, for example, SiO ₂ ,
MgF ₂ , SiO, TiO ₂ , ZnO, TiN, SiN
As the metal, for example, Zn, Cu, Ni, Al, C
As the organic polymer compound, r, Ge, Se, Cd or the like can be used, such as an ionomer resin, a polyamide resin, a vinyl resin, a natural polymer, an epoxy resin and a silane coupling agent.

As the substrate, polyester, polycarbonate, acrylic resin, polyolefin resin, phenol resin, epoxy resin, polyamide, polyimide or other plastic, glass or metal can be used.

The organic solvent that can be used for coating varies depending on whether it is in a dispersed state or in a dissolved state, but generally, alcohols such as methanol, ethanol, isopropanol, diacetone alcohol, acetone, methyl ethyl ketone, cyclohexanone. Such as ketones, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, sulfoxides such as dimethyl sulfoxide, ethers such as tetrahydrofuran, dioxane, ethylene glycol monomethyl ether, methyl acetate, ethyl acetate, acetic acid Ester such as butyl, aliphatic halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethylene, carbon tetrachloride, trichloroethylene, benzene, toluene, xylene,
Aromatic hydrocarbons such as monochlorobenzene, dichlorobenzene aromatics, n-hexane, and cyclohexanoligroin can be used.

The coating can be carried out using a coating method such as a dip coating method, a spray coating method, a spinner coating method, a bead coating method, a wire bar coating method, a blade coating method, a roller coating method or a curtain coating method. .

The film thickness of the recording layer formed by using such a solvent is 50Å to 100 μm, preferably 200Å to 1
μm is suitable.

[0038]

EXAMPLES Next, examples of the present invention will be described.

<Example 1> P-phenylenediamine 0.
1 mol, P-nitroiodobenzene (0.6 mol), anhydrous potassium carbonate (0.25 mol) and copper powder (2 parts) were refluxed for 4 days while stirring in 150 parts of dimethylformamide. After the reaction
The reaction mixture was filtered, and the reaction mixture was filtered with dimethylformamide,
It was washed well with water and acetone and then dried. 30 parts of red-brown tetrakis (P-nitrophenyl) -P-phenylenediamine was obtained.

25 parts of the compound obtained above was added to 100 parts of 1 part of dimethylformamide palladium-carbon hydrogenation catalyst in an autoclave, and hydrogen gas was added at 5.0 kg / g.
The mixture was stirred under cm ² at 90 ° C. to 100 ° C. until hydrogen absorption stopped.

After the reaction, the reaction solution was filtered, the product was washed with dimethylformamide, and the solution was poured into 350 parts of ice water. After stirring for a while, the precipitate was collected by filtration. Recrystallization was performed using an ethanol dimethylformamide mixed solvent to obtain 14 parts of tetrakis (P-aminophenyl) -P-phenylenediamine. High-speed liquid chromatography analysis gave a purity of 98.
It was 7%.

Δ by NMR (d ₆ -DMSO) analysis
Absorption of amino group for 8H at 3.37 ppm, δ 6.38
The absorption of the aromatic ring for 20H of the doublet broad at ~ 6.50 ppm was measured.

<Synthesis of 1-4> 3 parts of the above amino compound was mixed with 18 parts of dimethylformamide and 0.
7 parts and 2-methoxyethyl bromide together with 3.9 parts were heated and stirred at 100 ° C to 130 ° C. After reacting for 36 hours, the reaction solution was poured into 100 parts of ice water and extracted with ethyl acetate. After drying, it was purified with a silica gel column. Acquisition amount 3.
The disappearance of absorption due to NH stretching vibration of the amino group was confirmed by 4-part infrared absorption analysis.

1 part of this compound was dispersed in 20 parts of acetone, and equimolar silver perchlorate was added with stirring. At room temperature 1
After reacting for a period of time, the precipitated silver was separated by filtration, the filtrate was diluted with isopropyl ether and allowed to stand, and the precipitated crystals were collected by filtration. 0.7 copies acquired

1-4 thus synthesized was a compound having a large absorption region in the infrared region with absorption maximum wavelengths of 1258 nm and 957 nm. Elemental analysis value C ₅₄ H ₇₆ O ₁₂ N ₆ Cl Analysis value C: 62.59%, H: 7.38%, N: 8.1
0% Theoretical value C: 62.57%, H: 7.39%, N: 8.1
1%

In the example described above, the anion is perchloric acid, but when using other anions, the desired compound can be easily obtained by using a silver salt corresponding thereto. For example, AgSbF ₆ , AgBF ₄ ,
AgSO ₄ , AgNO ₃ , AgSO ₃ C ₆ H ₄ CH ₃ ,
A silver salt such as AgSO ₃ CF ₃ can be used.
Alternatively, it can be obtained by electrolytic oxidation.

Next, an example of use of the aminium salt compound represented by the general formula (1) in an optical recording medium will be described.

<Application Example 1> Diameter 130 mmφ, thickness 1.
A 50 μm pregroove layer is provided on a 2 mm PMMA substrate, and a polymethine dye (IR-82 manufactured by Nippon Kayaku Co., Ltd. is formed on the pregroove layer.
0) organic dye and the infrared absorbing compound No. A liquid in which 1-4 was dissolved in 1,2-dichloroethane at a weight ratio of 90:10 was spin-coated to form a recording layer of 800 Å. An optical recording medium having an air sandwich structure was obtained by sandwiching 0.3 mm spacers on the inner and outer peripheries of the medium thus obtained and bonding it to another PMMA substrate with an ultraviolet curable adhesive.

This is rotated at 1800 rpm to obtain 830
Recording power 6 from the substrate side using a semiconductor laser of nm
Writing was performed with a spot diameter of 1.5 μmφ at mW and a recording frequency of 2 MHz. Next, reproduction was performed at a read power of 0.9 mW, and the C / N ratio was measured by spectrum analysis. Subsequently, the C / N ratio after reading (repeating and repeating) 100,000 times was measured.

Furthermore, 1K is applied to the recording medium created under the above conditions.
A light stability test was conducted by irradiating a W / m ² xenon lamp light for 100 hours, and the reflectance and the C / N ratio were measured. The results are shown in Table-1.

[0051]

[Table 1]

USE EXAMPLE 2 (p-Diethylaminophenyl)-(phenyl) methylene-1-cyclopente-2-2 was formed on the same substrate as in Use Example 1 in the same manner as in Use Example 1.
Nil-3- (p-diethylaminophenyl) (phenyl) carbonium perchlorate and No. An optical recording medium was prepared by providing a recording layer with a solution of the aminium salt compound of 1-7 in a weight ratio of 90:10, and the same test as in Use Example 1 was conducted. The results are shown in Table-2.

<Comparative Examples 1 and 2> In use example 1, the aminium salt compound was replaced by N, N, N ', N'-tetrakis (p-
An optical recording medium was prepared and evaluated in the same manner as in Use Example 1 except that aminium perchlorate and diimonium perchlorate of di-normal-butylaminophenyl) -p-phenylenediamine were used. The results are shown in Table-2.

Comparative Example 3 An optical recording medium was prepared and evaluated in the same manner as in Use Example except that the aminium salt compound was not used in Use Example 2. The results are shown in Table-2.

[0055]

[Table 2]

<Use Examples 3 and 4> Wallet-sized 0.4 mm thick polycarbonate (hereinafter abbreviated as "PC")
A pre-groove was provided on the substrate by a hot pressing method, and a liquid prepared by mixing the organic dyes and aminium salt compounds shown in Table 3 below in diacetone alcohol was applied by a bar coating method and then dried. A recording layer of 850Å was obtained. Further, an optical recording medium having a close contact structure was produced by a wallet-sized 0.3 mm thick PC substrate and a heat roll method with an ethylene-vinyl acetate dry film interposed therebetween.

The optical recording medium of the example of use thus prepared was mounted on a stage driven in the XY directions, and a semiconductor laser having an oscillation wavelength of 830 nm was used to form an organic thin film recording layer from the PC substrate side having a thickness of 0.4 mm. Spot size 3.0
80 μse recording pulse at μmφ and recording power of 4.0 mW
Information is written in the Y-axis direction with c, and the read power is 0.4.
Playback at mW and its contrast ratio

[0058]

[Outside 13] : A → signal strength of unrecorded area, B → signal strength of recorded area) were measured.

Further, the same recording medium manufactured under the above conditions was subjected to a light stability test under the same conditions as in Use Example 1, and thereafter the reflectance and the contrast ratio were measured. The results are shown in Table-4.

[0060]

[Table 3]

Comparative Example 4 An optical recording medium was prepared and evaluated in the same manner as in the use example 4, except that the aminium salt compound in use example 4 was changed to tetrafluoroborate of tetrakis (p-dinormalbutylaminophenyl) phenylene diimonium. did. The results are shown in Table-4.

[0062]

[Table 4]

[0063]

As described above, the aminium salt compound represented by the general formula (1) has a large absorption region in the infrared region and can be easily synthesized.

The aminium salt compound of the present invention can greatly improve the light resistance of organic dyes.
When the organic dye thin film of the optical recording medium contains the aminium salt compound of the present invention, it becomes possible to provide an optical recording medium having significantly improved durability in repeated reproduction and light stability.

Claims (1)

[Claims] 1. Having a structure represented by the following general formula (1):
An aminium salt compound characterized by being: [Outer 1](A in the formula is [External 2]Indicates R₁ To R₈ Are all alkoxyalkyl groups
Yes, and [Outside 3] X  Indicates an anion. )