JPH0343461A - Naphthalocyanine and information recording material using the same - Google Patents

Abstract

NEW MATERIAL:A compound of formula I [Met is Si(IV), Sn(IV), Ge(IV) or Ti(IV); Y<1>-Y<4> are alkyl, aryl, aralkyl, amino, etc.; R and R' are (cyclo)alkyl or aryl; P, Q, R, and S are 0-6]. EXAMPLE:A compound of formula II. USE:Useful for preparing photorecording media, photocards, etc. The compound has good compatibility with resins or solvents and is reduced in the wavelength dependency of the reflectance thereof when formed into a thin film. PREPARATION:A silanol compound of formula III is reacted with an acylating agent such as 2-ethylhexanoic acid chloride in the presence of a base such as pyridine. The compound of formula III may be prepared from the reaction product of a compound of formula IV with a compound of formula V.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to naphthalocyanine, which plays an important role in optoelectronics such as information recording, displays, sensors, and safety glasses, and an optical recording medium produced using the same. The present invention relates to optical cards, filters (including glasses) for collecting and blocking near-infrared light, and liquid crystal display devices using near-infrared light.

[Prior art] In recent years, naphthalocyanine compounds have been used as optoelectronic materials in optical disks, optical cards, laser printers, filters, safety glasses, liquid crystal display materials, etc., and also in agricultural films as heat ray control materials. .

However, naphthalocyanine compounds have limited applicability due to insufficient solvent solubility and insufficient compatibility with resins.

Therefore, by introducing an alkyl group into the naphthalene ring (Japanese Patent Application Laid-Open No. 6O-23451), and by introducing a substituent into the axial position of the central metal (Journal
al of American ChemicalSo
ciety, vol. 106, pp. 7404-7410 1
(published in 1984), attempts were made to improve the solubility of solvents or resins, but the improvements were not sufficient.

Furthermore, as an example of applying the above-mentioned compounds to information recording materials, alkylnaphthalocyanine (Japanese Patent Application Laid-Open No. 61-2588
6) , silicon naphthalocyanine (JP-A-61-17
7287, -177288, -232448, -235
188) is known.

However, the former has the disadvantage of low reflectance,
When the compound used for the latter is used alone, the reflectance has a large wavelength dependence, making it impossible to read out due to laser fluctuations, so it is improved and used in combination with a polymer to reduce the wavelength dependence. is being attempted.

[Problem to be solved by the invention]

The present invention has been made to solve the above-mentioned drawbacks, and has discovered a naphthalocyanine that has good compatibility with resins or solvents and has a small wavelength dependence of reflectance when formed into a thin film, and uses the naphthalocyanine to The purpose of this invention is to obtain optical recording media, optical cards, filters, and liquid crystal display devices with high reflectance and high sensitivity.

[Means for Solving the Problems] As a result of intensive studies to solve the problems mentioned above, the present inventors discovered a compound represented by the following formula (I).

That is, the present invention provides the following conditions: [In formula (I), Met is St (TV), Sn (
IV), represents Ge (IV), Ti (rV),
Yl, Y2, Y3, and Y4 each independently represent an alkyl group, an aryl group, an aralkyl group, an amino group, an alkylamino group, an arylamino group, a hydroxyl group, an alkoxy group,
represents an aryloxy group, an alkylthio group, an arylthio group, or a heterocyclic group (each group may have a substituent), R and R' each independently represent an alkyl group, a cycloalkyl group, or an aryl group; , Q%R, and S each independently represent an integer from 0 to 6. ] It is a naphthalocyanine represented by the following, and optical recording media, optical cards, filters, and liquid crystal display elements are produced using it.

The naphthalocyanine of the present invention has high solubility in solvents and resins, and has low wavelength dependence of reflectance when used as an information recording material, so that a good information recording material can be obtained.

Examples of substituted or unsubstituted alkyl groups represented by 'yl, Y2, Y3 and Y4 in formula (I) include straight chain, cyclic or branched hydrocarbon groups having 1 to 20 carbon atoms; methoxymethyl, ethoxy Linear or branched alkoxy or aryloxyalkyl groups having a total of 1 to 30 carbon atoms such as methyl, ethoxyethyl, propoxyethyl, methoxybutyl, and phenoxyethyl; Chain or branched alkylthio or arylthioalkyl group having a total of 1 to 30 carbon atoms: N-methylaminomethyl,
Straight chain or branched carbon atoms having a total number of 1 to 30 such as N,N-dimethylaminomethyl, N,N-diethylaminomethyl, N-butylaminomethyl, N,N-dibutylaminomethyl, N,N-dimethylaminoethyl, etc. Alkylaminoalkyl group; halogenoalkyl group having 1 to 20 carbon atoms such as chloromethyl, chloroethyl, chlorobutyl, fluoromethyl, fluoroethyl, bromomethyl, bromoethyl, methyl iodide, ethyl iodide, butyl iodide; trifluoromethyl, trichloromethyl, dibromomethyl , pentafluoroethyl, heptafluoropropyl, and other barhalogenoalkyl groups.

Examples of substituted or unsubstituted aryl groups include phenyl derivatives such as phenyl, naphthyl, and tolyl groups, and naphthyl derivatives; examples of substituted or unsubstituted aralkyl groups include benzyl and phenylethyl groups. .

Examples of substituted or unsubstituted alkylamino or dialkylamino groups include methylamino, ethylamino,
Straight chain or branched alkyl group-substituted amino group having a total of 1 to 30 carbon atoms such as N,N-dimethylamino, N,N-diethylamino group; N-(hydroxyethyl)amino, N,N
-di(hydroxyethyl)amine, N,N-di(methoxyethyl)amino,N,N-di(ethoxyethyl)amino,N,N-di(methoxyethoxyethyl)amino,N
, N-di(acetoxyethyl)amino, and hydroxy, alkoxy or acyloxyalkylamino groups.

Examples of substituted or unsubstituted arylamino groups include anili, no, N-alkylanilino, alkylphenylamino, alkoxyphenylamino, and alkylaminophenylamino groups.

Examples of substituted or unsubstituted alkoxy groups include straight-chain or branched hydrocarbon oxy groups having 1 to 20 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, and octyloxy groups; Methoxyethoxy, ethoxyethoxy, propoxyethoxy, butoxyethoxy, phenoxyethoxy, methoxyethoxyethoxy, ethoxyethoxyethoxy,
One formula A- such as methoxyethoxyethoxyethoxy, hydroxyethyloxy, hydroxyethoxyethoxy group, etc.
(OCHK'C)IK2), -0- (wherein A is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group, Kl
and 2 each independently represent a hydrogen atom, a methyl group, a chloromethyl group, or an alkoxymethyl group, and U represents an integer of 1 to 5. ] Oligoethyloxy derivatives represented by N, N-
Alkylaminoalkoxy groups such as dimethylaminoethoxy, N,N-diethylaminoethoxy, N,N-dimethylaminepropoxy groups; alkyl or awarthio groups such as ethylthioethoxy, methylthioethoxy, phenylthioethoxy, methylthiopropoxy, ethylthiopropoxy groups Examples include alkoxy groups.

Examples of substituted or unsubstituted aryloxy groups include phenyloxy, naphthyloxy, alkylphenyloxy, alkylaminophenyloxy, halogen-substituted phenyloxy, nitrophenyloxy, alkoxyphenyloxy, and alkylthiophenyloxy groups.

Examples of substituted or unsubstituted alkylthio groups include straight chain or branched hydrocarbon thio groups having 1 to 30 carbon atoms such as methylthio and ethylthio groups; methoxymethylthio, methoxyethylthio, ethoxyethylthio, butoxyethylthio, methoxy Oligoalkoxyalkylthio groups such as ethoxyethylthio: Oligoalkylthioalkylthio groups such as methylthiomethylthio and ethylthioethylthio groups: N,N-dimethylaminoethylthio, N,N-diethylaminoethylthio, N-methylaminopropylthio groups, etc. alkylaminoalkylthio groups; examples include halogenated alkylthio groups such as chloroethylthio, bromoethylthio, iodized ethylthio, fluoroethylthio, and dichloroethylthio groups; examples of substituted or unsubstituted arylthio groups include phenylthio , naphthylthio, alkylphenylthio, aminophenylthio, alkylaminophenylthio, and alkoxyphenylthio groups.

Examples of substituted or unsubstituted heterocyclic groups include heterocycles such as thiophene, oxazole, thiazole, thiadiazole, furan, virol, quinoline, and pyridine.

Examples of alkyl groups represented by R and R' include straight-chain or branched carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl, 2-ethylhexyl, and 3.5.5-trimethylhexyl groups. The number 1 to 20 hydrocarbon groups are cycloalkyl groups such as cyclohexyl, bicyclo[2,2,1]heptyl, bicyclo[2,2,
, 13hept-5-en-2-yl group, and the like. Examples of aryl groups include phenyl, naphthyl, 4-
Examples include aromatic hydrocarbon groups such as t-butylphenyl group.

The naphthalocyanine represented by formula (I) of the present invention can be prepared by known methods [e.g.
J, Am, Chem, Soc,, 106.74
0 (I984); J, Org, Chem, 2
8.3379 (I963)].

<Scheme 1> (I) (2) (3) H That is, as shown in Scheme 1, an acylating agent is allowed to act on the diol body (6) in order to obtain compound (I).

The method of manufacturing an optical recording medium using the naphthalocyanine of the present invention includes a method of coating or vapor-depositing the naphthalocyanine on a transparent substrate. and naphthalocyanine 0.05% to 20% by weight, preferably 0.5% by weight
There is a method of dissolving it in a solvent to a concentration of ~20% by weight and applying it with a spin coater. In addition, as a vapor deposition method,
There is a method of depositing naphthalocyanine on a substrate at 10-5 to 10-7 torr and 100 to 300°C.

The substrate may be any optically transparent resin. Examples include acrylic resin, polyethylene resin, vinyl chloride resin, vinylidene chloride resin, polycarbonate resin, ethylene resin, polyolefin copolymer resin, vinyl chloride copolymer resin, vinylidene chloride copolymer resin, and styrene copolymer resin.

Further, the substrate may be surface-treated with a thermosetting resin or an ultraviolet curable resin.

When producing an optical recording medium, it is preferable to use a polyacrylate substrate or a polycarbonate substrate as the substrate from the viewpoint of cost and handling by the user, and to apply the coating by a spin code method.

In view of the solvent resistance of the substrate, it is preferable that the solvent used in the spin code has a polarity lower than that of carbon tetrachloride. Such solvents include halogenated hydrocarbons (e.g., dichloromethane, chloroform, carbon tetrachloride, tetrachloroethylene, dichlorodifluoroethane, etc.), ethers (e.g., tetrahydrofuran, diethyl ether, etc.),
Ketones (e.g. acetone, methyl ethyl ketone, etc.), alcohols (e.g. methanol, ethanol,
cellosolves (methyl cellosolve, ethyl cellosolve, etc.), hydrocarbons (hexane, cyclohexane, octane, benzene, toluene, xylene, etc.) are preferably used.

In addition, in terms of cost and workability when producing a filter, important properties of the compound include having heat resistance that allows it to be kneaded with a resin, or being able to dye a resin substrate in a solvent, and The produced molded product needs to have sharp light absorption characteristics and high absorption rate.

- The method for producing a near-infrared absorbing filter using the naphthalocyanine of the formula (I) is to mix the resin and the naphthalocyanine of the general formula (I) and mold it, or to mix the naphthalocyanine of the general formula (I) with a resin monomer. Cast polymerization, dyeing a resin molded product with naphthalocyanine of general formula (I),
There is a method of coating and vapor depositing naphthalocyanine of general formula (I) on the surface of a substrate material.

The resin used as the filter base material may be any transparent resin, such as thermoplastic resins such as polystyrene, polymethyl methacrylate, polycarbonate, polyethylene, and polypropylene, CR-39 (PPG■, trade name), MR-3 ( Thermosetting resins such as Mitsui Toatsu Chemical Co., Ltd. (trade name) and MR-6 (Mitsui Toatsu Chemical Co., Ltd., trade name) are preferred.

In addition, when used with liquid crystal as a display material, it is necessary to have high solubility in the liquid crystal, and it is necessary that naphthalocyanine does not interfere with the change in the state of the liquid crystal when applying an electric field or applying heat. be.

Examples of liquid crystals used in combination as display materials include nematic liquid crystals, smectic liquid crystals, and cholesteric liquid crystals. Examples of display methods include guest-host display, liquid crystal panels (naphthalocyanine is placed in the liquid crystal, and the screen is illuminated with laser light. ), etc.

Furthermore, the optical card can be manufactured by coating or vapor-depositing on a transparent substrate made of the same material as the optical recording medium.
) is obtained by forming a recording layer made of naphthalocyanine.

[Example J The present invention will be specifically explained below using Examples.

1 g of a silanol represented by the following structural formula (A)'OH, 5 g of 2-ethylhexanoyl chloride, and 20 g of pyridine were mixed and heated to reflux.

After cooling to room temperature, the mixture was poured into hydrochloric acid water at 200 m°C and extracted with benzene. From the benzene layer, the following structural formula (I
-1) 500mg of the naphthalocyanine compound represented by
Obtained. λmax in chloroform was 775 nm.

C=O 5 =0 ) 1-Calls H9 1 part by weight of the compound (I-1) was dissolved in 100 parts by weight of chloroform and applied to a polycarbonate optical disk substrate. The reflectance of the optical recording medium produced in this way is 83.
35% at 0 part m, sensitivity is 8 mW, 50 dB in 830 part m semiconductor laser, durability is 1 at 0.5 mW of reproduction light.
There was no change even after reading it a million times. In addition, the heat and humidity resistance remained unchanged for 100 hours at a temperature of 60° C. and a humidity of 80%.

1 g of the silanol compound of formula (A), 5 g of 3,5.5-trimethylhexanoyl chloride, and 50 g of quinoline were mixed and heated to 200°C. The reaction solution was treated in the same manner as in Example 1 to obtain 600 mg of a naphthalocyanine compound represented by the following structural formula (I-2).

(CHa) 5ccLcl((C)+3) CLli=
0 elemental analysis CaaHsaNsSiO4HN Calculated value (%)? 5.12 5.54 10.62 Actual value (%) 74.98 5.38 10.12 4 parts of the above compound (I-2) were heated and mixed with 1000 parts of polystyrene resin, and the mixture was molded into a plate shape. The filter produced in this manner well absorbed light in the wavelength range of 750 to 850 nm.

Additionally, 7 parts of the above compound was added to 10 parts of a cyanobiphenyl liquid crystal mixture.
00 parts, a liquid crystal panel was prepared, and when writing was performed using laser light, a clear image was obtained.

Further, 1 part of the compound (I-2) was dissolved in 100 parts of dibutyl ether and applied onto a polycarbonate optical card substrate, and the recording layer surface was overcoated with a resin to produce an optical card. The reflectance of this optical card is 35% and the sensitivity is 7
C/N at 80 part m, 8 mW, linear velocity 2, 8 m/sec
The ratio was 50 dB. Moreover, the durability was also good.

Fruit 11 Hodan 1 g of silanol compound of the above formula (A), 100 g of benzene,
Tributylamine Ig and propionic acid chloride 10g
were mixed and heated to reflux. The reaction solution was treated in the same manner as in Example 1 to obtain 700 mg of a naphthalocyanine compound represented by the following structural formula (I-3).

C2H! 1 C=0 6・0 28S Elemental analysis C54H34NaSiO4 IIN Calculated value (%) 66.40 3.51 11.47 Actual value (%) 66.10 3.21 11.30 1 part by weight of the above compound (I-3) and 1 part by weight of polycarbonate were dissolved in 20 parts by weight of chloroform and applied to a glass substrate. Gold was deposited thereon and subsequently overcoated with a photocurable polyacrylic resin. The optical recording medium thus produced had good sensitivity and durability.

X Qidan 1 1 g of tin naphthalocyanine represented by the following structural formula (B) 0 JH, log of 2-ethylhexanoic acid, and 50 g of picoline were mixed, and after a heating reaction,
By treating in the same manner as in Example 1, the following structural formula (I-
500 mg of the naphthalocyanine compound shown in 4) was obtained.

4He CH-CzHs and・0 and・0 CI-1-C2H8 4He Elemental analysis calculated value (%) Actual value (%) Ca4HsJa04Sn CH 68,774,87 69,014,77 +0.02 10.13 The above compound (I -4) 4 parts to 1000% polystyrene resin
The mixture was mixed with heat and formed into a plate shape. The filter produced in this manner well absorbed light in the wavelength range of 750 to 1350 nm.

Additionally, 7 parts of the above compound was added to 10 parts of a cyanobiphenyl liquid crystal mixture.
00 parts, a liquid crystal panel was prepared, and when writing was performed using laser light, a clear image was obtained.

When the same treatment was performed using germanium naphthalocyanine having the following structural formula () in place of Compound (A) in Example 1, 300 mg of Compound (I-5) was obtained.

C=0 Compound (I-5) 2mg to 1f2 chloroform When dissolved and the absorbance was measured, λmax to 800nm 0.8 Met.

Example 1. 3. 4. Characteristics of the compound obtained in 5. and, Table 1 shows the characteristics when these are made into thin films.

As is clear from the table, the properties of the thin films prepared by spin-coating the compounds of the present invention on glass substrates were better than those of the comparative compounds.

(Note-1) (Note-2) (Note-3) (Note-4) (Note-5) (Note-6) (Note-7) JP-A-61-25886 Compound of Example 1 JP-A-6
1-177287 Compound of Example 4 JP-A-61-232
448 Compound of Example 1 Chloroform solution 2 mg/(
The maximum absorption wavelength (λmax, nm) measured at 150 nm and the absorbance at that wavelength (abs,) are displayed.

The reflectance and absorption at 830 nm from the substrate surface side of a film spin-coded onto a glass substrate with a chloroform solution at a concentration of 2 g/β is shown.

Change in reflectance of the film prepared in (Note-5) after 100 hours of 90% heat and humidity test at 60°C. Change rate within 20% (○), 20-50% (△), 50% or more (×)
And so.

Heat resistance and resin compatibility are Ren (ps) or polymethylmethac Heat melt the resin of Relate (PMMA). When melted and molded, the decomposition of the compound, Alternatively, dissolution was determined visually.

Compounds represented by the following formulas having the groups shown in Table 2 were synthesized according to Example 1 and evaluated as optical recording media. Good results were obtained in terms of resin compatibility and other properties.

Table 2 [Effects of the Invention] As explained above, the naphthalocyanine of the present invention has good solubility in solvents and liquid crystals, and good compatibility with resins. Furthermore, when the information recording material using the naphthalocyanine of the present invention is used as an optical recording medium or an optical card, it has a high reflectance during film formation, has good moist heat resistance, heat resistance, resin compatibility, etc., and can be used as a filter. In this case, the light absorption characteristics are sharp and the absorption rate is high, and when used as a liquid crystal display element, the contrast is good.

Claims (1)

[Claims] 1. Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In formula (I), Met is Si(IV), Sn(IV),
Represents Ge(IV), Ti(IV), Y^1, Y^2, Y
^3 and Y^4 each independently represent an alkyl group, an aryl group,
represents an aralkyl group, an amino group, an alkylamino group, an arylamino group, a hydroxyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group or a heterocyclic group (each group may have a substituent), R , R'
each independently represents an alkyl group, a cycloalkyl group, or an aryl group, and P, Q, R, and S each independently represent an integer of 0 to 6. ] Naphthalocyanine. 2. An optical recording medium containing the naphthalocyanine according to claim 1 in a recording layer. 3. An optical card containing the naphthalocyanine according to claim 1 in a recording layer. 4. A near-infrared absorption filter containing the naphthalocyanine according to claim 1. 5. A liquid crystal display element containing the naphthalocyanine according to claim 1.