JPH0751555B2 - Diimonium salt compound - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a diimmonium salt compound having absorption in the infrared region, and more particularly to a diimmonium salt compound which improves the light resistance of organic dye compounds.

[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 are formed in 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) is obtained.
%) 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]

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

[0006]

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

[0007]

[Outside 3]

In the above general formula (1),

[0009]

[Outside 4] X  Indicates an anion.

R ₁ to R ₈ are substituents having 1 to 8 carbon atoms, at least one of which is an alkoxyalkyl group and the rest are alkyl groups.

[0011]

[Outside 5] 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 of R ₁ to R _{8 have} 1 to 8 carbon atoms.
Which may be the same or different, but at least one is an alkoxyalkyl group.

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. (However, in the scheme below, A is

[0014]

[Outside 6] Indicates. )

[0015]

[Outside 7]

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 diimonium salt compound according to the present invention has an alkoxyalkyl group in its structure and is excellent in solvent solubility due to its polarity.

In the diimonium salt compound of the present invention, R ₁
The alkoxyalkyl group which can be used in -R _8, for example, methoxymethyl, 2-methoxyethyl, 3-methoxypropyl, 2-methoxypropyl, 4-methoxybutyl, 3-methoxybutyl, 2-methoxybutyl, 5-methoxy Pentyl, 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) are shown in the table below.
Listed in 1. Here, compound No. (1-1) to (1-
8) is a compound according to the present invention, compound No. (1-9) ~
(1-11) is a reference compound in which at least _one of R _{1 to} R ₈ is an alkynyl group. For simplification, the compound represented by formula (1) is

[Outside 10] X , (R₁ , R₂ ) (R₃ , R_Four ) (R_Five , R₆ ) (R₇ ，
R₈ ). For example, in equation (1)

[0021]

[Outside 8] X Is ClO_Four  And R₁ To R₈ Is a methoxyethyl group, ClO
_Four , (CH₂ CH₂ OCH₃ , CH₂ CH₂ OCH₃ )
_Four It is written as.

[0022]

[Table 1]

Such a diimonium salt compound has a maximum absorption wavelength of 900 nm or more and an absorption peak having a large absorption peak of tens of thousands to hundreds of thousands.

Such compounds are used for heat insulating films, sunglasses, etc., in addition to the use as materials for optical recording media.

The diimmonium 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 diimonium salt compound of the present invention as an optical recording medium, commonly known dyes are used, for example, cyanine dyes,
Examples include merocyanine dyes, croconium dyes, squarylium dyes, azulenium dyes, polymethine dyes, naphthoquinone dyes, pyrylium dyes, and phthalocyanine dyes.

The addition amount of the diimonium salt compound represented by the general formula (1) 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.
%, More preferably 10 to 30% by weight is suitable.

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, for the purpose of imparting solvent resistance, improving reflectance, and improving repetitive reproduction, the protective layer is protected from scratches, dust, dirt, etc. and environmental stability of the recording layer. 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, or a silane coupling agent.

As the substrate, polyester, polycarbonate, acrylic resin, polyolefin resin, phenol resin, epoxy resin, polyamide, polyimide or other plastic, glass or metals 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. Generally, alcohols such as methanol, ethanol, isopropanol and diacetone alcohol, acetone, methyl ethyl ketone and 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 compounds such as monochlorobenzene and dichlorobenzene or aliphatic hydrocarbons such as 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.

[0036]

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

<Synthesis Example 1> P-phenylenediamine
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 (Compound No. 1-1)> 3 parts of the above amino compound together with 18 parts of dimethylformamide, 0.7 part of anhydrous sodium hydrogen carbonate, and 3.9 parts of 2-methoxyethyl bromide at 100 ° C. to 130 ° C. The mixture was heated and stirred at ℃. 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. Acquired amount 3.4 parts The disappearance of absorption due to NH stretching vibration of amino group was confirmed by infrared absorption analysis.

1 part of this compound was dispersed in 20 parts of acetone, and 2 times mol of silver perchlorate was added with stirring. At room temperature 1
After reacting for a time, the precipitated silver was separated by filtration, and the filtrate was diluted with isopropyl ether. 0.55 parts of precipitated crystals were collected by filtration.

Compound No. 1 of Table 1 thus synthesized was used.
(1-1) was a compound having a large absorption region in the infrared region with an absorption maximum wavelength of 1040 nm. Elemental analysis value C ₅₄ H ₇₆ O ₁₆ N ₆ Cl ₂ analysis value C: 57.08%, H: 6.72%, N: 7.39% Theoretical value C: 57.09%, H: 6.74% , N: 7.40%

The example described above is for the case where 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, reference examples and use examples in which the diimonium salt compound represented by the general formula (1) is used as an optical recording material will be described.

Reference Example 1 A 50 μm pregroove layer was provided on a PMMA substrate having a diameter of 130 mmφ and a thickness of 1.2 mm, and 1,5-bis (diethylaminophenyl) -1,5-diphenyl- was formed thereon.
2,4-Pentadienol perchlorate and the compound Nos. Shown in Table-1. A liquid obtained by dissolving (1-10) 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-2.

<Comparative Example 1> In Reference Example 1, the compound No. An optical recording medium was prepared and evaluated in the same manner as in Reference Example 1 except that the diimonium salt compound of (1-10) was not used. The results are shown in Table-2.

[0050]

[Table 2]

<Use Example 1> A wallet-sized 0.4 mm thick polycarbonate (hereinafter abbreviated as "PC") substrate was provided with a pregroove by a hot press method, and an organic dye (p-dimethylaminophenyl) was formed thereon. )-(P-Tolyl) methylene-1-cyclopente-phenyl-3- (p-dimethylaminophenyl)-(p-tolyl) carbonium perchlorate and the compound Nos. Shown in Table 1. A liquid prepared by mixing the diimonium salt compound of (1-5) in diacetone alcohol at a weight ratio of 80:20 was applied by a bar coating method and then dried to obtain a recording layer of 850Å. 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 use example 1 thus prepared was mounted on a stage driven in the XY directions, and a thickness of 0.4 mm was obtained by using a semiconductor laser having an oscillation wavelength of 830 nm.
Spot size on the organic thin film recording layer from the PC substrate side of 3.
Recording pulse of 80 μs at 0 μmφ and recording power of 4.0 mW
ec, information is written in the Y-axis direction and read power is 0.
Playback at 4mW and its contrast ratio

[0053]

[Outside 9] : A → signal strength of unrecorded area, B → signal strength of recorded area) were measured.

Further, the same recording medium produced under the above conditions was subjected to a light stability test under the same conditions as in Reference Example 1, and thereafter the reflectance and the contrast ratio were measured. The results are shown in Table-3.

Comparative Example 2 An optical recording medium was prepared in the same manner as in Use Example 1 except that the diimonium salt compound in Use Example 1 was changed to tetrafluoroborate of tetrakis (p-dinormalbutylaminophenyl) phenylenediimonium. evaluated. The results are shown in Table-3.

[0056]

[Table 3]

[0057]

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

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

Claims (1)

[Claims] 1. A structure having a structure represented by the following general formula (1):
A diimonium salt compound characterized by being: [Outer 1](R in the formula₁ To R₈ Is a substituent having 1 to 8 carbon atoms.
At least one of them is an alkoxyalkyl group and the rest are
It is an alkyl group. Also [Outside 2] X  Indicates an anion. )