JPH05178808A - Diimonium salt compound - Google Patents

Abstract

PURPOSE:To obtain a new diimonium salt compound useful as a material for optical recording medium, having absorption in an infrared region, much improved light resistance of organic coloring matter and excellent solvent solubility. CONSTITUTION:A diimonium salt compound of formula I (R1 to R8 are 1-8C substituent group and at least one of R1 to R8 is alkoxyalkyl or alkynyl; X<-> is anion). The compound is produced by subjecting a compound of formula II (A is group of formula III) and a compound of formula IV to Ullmann reaction and reduction reaction through a compound of formula V to give an amino derivative of formula IV, alkoxyalkylating or alkynylating the amino derivative by selective substitution and oxidizing. The compound has strong absorption in an infrared region and is simply synthesized. Light resistance of an organic coloring matter can be extremely improved, for example, in the case of addition of the compound formula I to a thin film of an organic coloring matter of optical recording medium, an optical stability in repeated reproduction is obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a diimonium salt compound having absorption in the infrared region, and more particularly to a diimonium 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 on a substrate can be made into spiral or circular and linear track configurations 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 method, the laser-sensitive layer absorbs thermal energy, and small recesses (pits) can be formed in the portion by evaporation or melting. Further, in another heat mode recording method, a pit having an optically detectable density difference can be formed at that position 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, or the like 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 the 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 its 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.
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] Indicates an anion.

R ₁ to R ₈ are substituents having 1 to 8 carbon atoms, and at least one is an alkoxyalkyl group or an alkynyl group.

[0011]

[Outside 5] Is chloride ion, bromide ion, iodide ion, perchlorate ion, nitrate ion, benzenesulfonate ion, P-toluenesulfonate ion, methylsulfate ion, ethylsulfate ion, propylsulfate ion. , Tetrafluoroborate ion, Tetraphenylborate ion, Hexafluorate ion, Benzenesulfinate ion, Acetate ion, Trifluoroacetate ion, Propionacetate ion, Benzoate ion, Oxalate Salt ion, succinate ion, malonate ion, oleate ion, stearate ion,
Citrate ion, monohydrogen diphosphate ion, dihydrogen monophosphate ion, pentachlorostannate ion, chlorosulfonate ion, fluorosulfonate ion, trifluoromethanesulfonate ion, hexafluorohydroxy ion Acid salt ion, hexafluoroantimonate ion,
Anions such as molybdate ion, tungstate ion, titanate ion and zirconate ion are represented.

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 or an alkynyl group.

The method for producing the 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 reduction reaction can be alkoxyalkylated or alkynylated 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 or an alkynyl group in its structure, and is excellent in solvent solubility because of their polarities.

In the diimonium salt compound of the present invention, R ₁
Examples of the alkoxyalkyl group usable for -R ₈ include 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.

Examples of the alkynyl group include propargyl and 3-
Butynyl, 4-pentynyl, 5-hexynyl and the like.

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 X, (R ₁ R ₂ ) (R ₃ R ₄ ) (R ₅ R ₆ ).
Notated as (R ₇ R ₈ ). For example, in equation (1)

[0021]

[Outside 8] And when R ₁ to R ₈ are methoxyethyl groups, ClO
₄ , (CH ₂ CH ₂ OCH ₃ , CH ₂ CH ₂ OCH ₃ )
Notated as ₄ .

1-1 ClO ₄ , (CH ₂ CH ₂ OCH ₃ ,
_{CH 2 CH 2 OCH 3) 4} 1-2 ClO 4, (C 4 H 9, C 4 H 9) 3 (C 4 H 9, CH
_{2 CH 2 OCH 3) 1-3 ClO} 4, (C 5 H 11, C 5 H 11) 3 (C 5 H 11,
_{CH 2 CH 2 OCH 3) 1-4} ClO 4, (C 3 H 7, C 3 H 7) 3 (C 3 H 7, CH
_{2 CH 2 OC 2 H 5)} 1-5 ClO 4, (CH 2 CH 2 C 2 H 5, CH 2 CH 2 O
C ₂ H ₅ ) ₄ 1-6 AsF ₆ , (C ₄ H ₉ , C ₄ H ₉ ) ₃ (C ₄ H ₉ , CH
_{2 CH 2 OCH 3) 1-7 AsF} 6, (C 3 H 7, C 3 H 7) 3 (C 3 H 7, CH
_{2 CH 2 OC 2 H 5)} 1-8 AsF 6, (CH 2 CH 2 OC 2 H 5, CH 2 CH 2
OC ₂ H ₅ ) ₄ 1-9 ClO ₄ , (C ₄ H ₉ , C ₄ H ₉ ) ₃ (C ₄ H ₉ , CH
₂ C≡CH) 1-10 AsF ₆ , (C ₄ H ₉ , C ₄ H ₉ ) ₃ (C ₄ H ₉ , C
H ₂ C≡CH) 1-11 ClO ₄ , (CH ₂ C≡CH, CH ₂ C≡C
H) ₄

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

Such a compound is used for a heat insulating film, sunglasses, etc. in addition to the use as a material for an optical recording medium.

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 together 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 diimmonium salt compound of 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, polyvinyl pyrrolidone, 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, dirt and the like and environmental stability of the recording layer for the purpose of imparting solvent resistance, improving reflectance or improving repeated 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 may be used, for example, 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, plastic such as polyimide, glass, metals or the like 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, 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 0.
1 mol, P-nitroiodobenzene 0.6 mol, anhydrous potassium carbonate 0.25 mol, and 2 parts of copper powder were refluxed for 4 days with stirring in 150 parts of dimethylformamide. After the reaction
The reaction mixture was filtered and the product 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 an autoclave together with 1 part of 100 parts of dimethylformamide palladium-carbon hydrogenation catalyst, and 5.0 kg of hydrogen gas was added.
The mixture was stirred at 90 ° C. to 100 ° C. for cm ² 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 with 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 8H amino group at 3.37 ppm, δ 6.38
Absorption of aromatic ring 20H of doublet broad to ~ 6.50 ppm was measured.

<Synthesis of 1-1> 18 parts of dimethylformamide and 0.3 parts of anhydrous sodium hydrogen carbonate were added to 3 parts of the above amino compound.
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 2 times mol of silver perchlorate was added with stirring. At room temperature 1
After reacting for a period of 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.

1-1 synthesized in this manner 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: 7.3
9% theoretical value C: 57.09%, H: 6.74%, N: 7.4
0%

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.
In addition to this, it can also be obtained by electrolytic oxidation.

Next, examples in which the diimonium salt compound represented by the general formula (1) is used as an optical recording material will be described.

Example 1 Diameter 130 mmφ, Thickness 1.
A 50μ pregroove layer is provided on a 2mm PMMA substrate, and 1,5-bis (diethylaminophenyl) is placed on it.
A liquid having 1,5-diphenyl-2,4-pentadienol perchlorate and the diimonium salt compound 1-10 dissolved in 1,2-dichloroethane at a weight ratio of 90:10 was spin-coated to form an 800-liter recording layer. Provided. An optical recording medium having an air sandwich structure was obtained by sandwiching 0.3 mm spacers on the inner and outer peripheral sides 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 a recording frequency of 2 MHz and mW. Then, reproduction was performed at a read power of 0.9 mW, and the C / N ratio was measured by spectrum analysis. Then, the C / N ratio after reading out (repeating repeated) 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.

Comparative Example 1 An optical recording medium was prepared and evaluated in the same manner as in Example 1 except that the diimonium salt compound was not used in Example 1. The results are shown in Table-1.

[0050]

[Table 1]

Example 2 A wallet-sized 0.4 mm thick polycarbonate (hereinafter abbreviated as "PC") substrate was provided with a pregroove by a hot pressing method, and an organic dye (p-dimethylaminophenyl) was provided thereon. )-(P
-Tolyl) methylene-1-cyclopente-phenyl-3
-(P-Dimethylaminophenyl)-(p-tolyl) carbonium perchlorate and compound No. A liquid prepared by mixing the diimmonium salt compound of 1-5 in diacetone alcohol in a weight ratio of 80:20 was applied by a bar coating method and then dried to obtain a recording layer of 850 Å. Further, an optical recording medium having a contact structure was produced by a wallet-sized PC substrate having a thickness of 0.3 mm and a heat roll method with an ethylene-vinyl acetate dry film interposed therebetween.

The optical recording medium of Example 2 thus produced 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 Example 1, and thereafter the reflectance and the contrast ratio were measured. The results are shown in Table-2.

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

[0056]

[Table 2]

[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 resistance stability.

Front Page Continuation (72) Inventor Miura Kyo, Inc., Canon Co., Ltd. 3-30-2 Shimomaruko, Ota-ku, Tokyo

Claims (1)

[Claims] 1. A diimmonium salt compound having a structure represented by the following general formula (1). [Outer 1] (In the formula, R ₁ to R ₈ are substituents having 1 to 8 carbon atoms, and at least one of them is an alkoxyalkyl group or an alkynyl group. Indicates an anion. )