JPH0778182B2 - Naphthalocyanine polymer and optical recording medium using the same - Google Patents

Description

The present invention relates to a naphthalocyanine polymer useful as an optoelectronic material and an optical recording medium containing the same in a recording layer.

[Conventional technology]

In recent years, naphthalocyanine-based compounds have been used as optoelectronic materials for optical disks, optical cards, laser printers, filters, protective glasses, liquid crystal display materials and the like, and also used for agricultural films as heat ray adjusting materials.

However, since the naphthalocyanine-based compound has insufficient solvent solubility and compatibility with a resin, its range of use has been limited.
Therefore, by introducing an alkyl group into the naphthalene ring (JP-A-60-23451) or by introducing a substituent at the axial position of the central metal (Journal of American Chem).
ical Society. 106, 7404-7410, published in 1984), but the solvent or resin solubility was improved, but the improvement was not sufficient.

Examples of applying the above-mentioned compounds to optical recording media include alkylnaphthalocyanine (JP-A-61-25886) and silicon naphthalocyanine (JP-A-61-177287, -177288, -23).
2448, -235188) is known.

However, the former has the drawback of low reflectance,
The compound used in the latter case has a large wavelength dependence of reflectance when used alone and cannot be read out due to laser fluctuations, so it is mixed with a polymer to improve it and reduce the wavelength dependence. Was being tried.

[Problems to be Solved by the Invention]

The present invention has been made to solve the above problems, to obtain a compound having good compatibility with a resin or a solvent, and having a small wavelength dependence of reflectance when a thin film is formed. And an excellent optical recording medium.

[Means for solving the problem]

That is, one of the present inventions is the formula (I) [In the formula (I), Met is Si (IV), Sn (IV), Ge (I
V) and Ti (IV), and Y ¹ , Y ² , Y ³ and Y ⁴ are each independently an alkyl group, an aryl group, an aralkyl group, an amino group, an alkylamino group, an arylamino group, a hydroxy group or an alkoxy group. , An aryloxy group, an alkylthio group, an arylthio group or a heterocyclic group (each group may have a substituent), R and R ′ are each independently an alkyl group,
Represents an aryl group, P, Q, R and S are each independently 0,
Represents an integer of 1, 2, 3, 4, 5, and 6, and n and m each independently represent an integer of 1 to 30. ] A copolymer of naphthalocyanine and silicone represented by the above formula, and another invention is an optical recording medium using the same. The above-mentioned naphthalocyanine polymer of the present invention has a high solvent and resin solubility and a small wavelength dependency of the reflectance when used as an optical recording medium, so that a good optical recording medium can be obtained.

Examples of the substituted or unsubstituted alkyl group represented by Y ¹ , Y ² , Y ³ and Y ⁴ in the formula (I) include a linear or branched hydrocarbon group having 1 to 20 carbon atoms; methoxymethyl Group, ethoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, methoxybutyl group, phenoxyethyl group-containing linear or branched alkoxyalkyl group having 1 to 30 carbon atoms; methylthiomethyl group, phenylthiomethyl group Group, ethylthioethyl group, straight-chain or branched alkylthioalkyl group having 1 to 30 carbon atoms such as methylthiobutyl group; N-methylaminomethyl group, N, N-dimethylaminomethyl group, N, N-diethylaminomethyl Group, N-butylaminomethyl group, N, N-dibutylaminomethyl group, N, N-dimethylaminoethyl group or other straight or branched carbon number 1
~ 30 alkylaminoalkyl groups; carbon numbers such as chloromethyl, chloroethyl, chlorobutyl, fluoromethyl, fluoroethyl, bromomethyl, bromoethyl, bromobutyl, methyl iodide, ethyl iodide, butyl iodide, etc. 1-20 halogenoalkyl groups; perhalogenoalkyl groups such as trifluoromethyl group, trichloromethyl group, dibromomethyl group, pentafluoroethyl group, heptafluoropropyl group and the like.

Examples of the substituted or unsubstituted aryl group include phenyl derivatives such as phenyl group, naphthyl group and tolyl group, and naphthyl derivatives, and examples of the substituted or unsubstituted aralkyl group include benzyl group, phenylethyl group and the like. Is mentioned.

Examples of the substituted or unsubstituted alkylamino group or dialkylamino group include a methylamino group, an ethylamino group,
N, N-dimethylamino group, N, N-diethylamino group and other linear or branched alkyl group-substituted amito group having 1 to 30 carbon atoms; N- (hydroxyethyl) amino group, N, N-di (hydroxy) Ethyl) amino group, N, N-di (methoxyethyl)
Amino group, N, N-di (ethoxyethyl) amino group, N, N-
Hydroxylalkylamino groups such as di (methoxyethoxyethyl) amino group and N, N-di (acetoxyethyl) amino group; alkoxyalkylamino groups; arsioxyalkylamino groups, substituted or unsubstituted arylamino groups Examples thereof include anilino group, N-alkylanilino group, alkylphenylamino group, alkoxyphenylamino group, alkylaminophenylamino group and the like.

Examples of the substituted or unsubstituted alkoxy group include a branched or straight chain having 1 to 20 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group, hexyloxy group, heptyloxy group, octyloxy group. Chain carbon hydrogen oxy group; methoxyethoxy group, ethoxyethoxy group, propoxyethoxy group, butoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, methoxyethoxyethoxyethoxy group, hydroxyethyloxy group, hydroxyethoxy General formula R- (OCHK ¹ CHK ² ) _u- 0- such as ethoxy group
[In the formula, R is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, K ¹
And K ² each independently represents a hydrogen atom, a methyl group, a chloromethyl group, an alkoxymethyl group, and u represents an integer of 1 to 5].
An oligoethyloxy derivative represented by: N, N-dimethylaminoethoxy group, N, N-diethylaminoethoxy group, N, N
An alkylaminoalkoxy group such as a dimethylaminopropoxy group; and an alkylthioalkoxy group such as an ethylthioethoxy group, a methylthioethoxy group, a phenylthioethoxy group, a methylthiopropoxy group and an ethylthiopropoxy group.

Examples of the substituted or unsubstituted aryloxy group are phenyloxy group, naphthyloxy group, alkylphenyloxy group, alkylaminophenyloxy group, halogen-substituted phenyloxy group, nitrophenyloxy group, alkoxyphenyloxy group, alkylthiophenyl. An oxy group etc. are mentioned.

Examples of the substituted or unsubstituted alkylthio group include a linear or branched carbon hydrogen thio group having 1 to 30 carbon atoms such as methylthio group and ethylthio group; methoxymethylthio group, methoxyethylthio group, ethoxyethylthio group, butoxy. Oligoalkoxyalkylthio groups such as ethylthio group and ethoxyethoxyethylthio group; Oligoalkylthioalkylthio groups such as methylthiomethylthio group and ethylthioethylthio group; N, N-dimethylaminoethylthio group, N, N-diethylaminoethylthio group , An alkylaminoalkylthio group such as N-methylaminopropylthio group; a halogenated alkylthio group such as chloroethylthio group, bromethylthio group, iodoethylthio group, fluorinated ethylthio group and dichloroethylthio group. Of a substituted or unsubstituted arylthio group As it is, a phenylthio group,
Examples thereof include a naphthylthio group, an alkylphenylthio group, an aminophenylthio group, an alkylaminophenylthio group and an alkoxyphenylthio group.

Examples of the substituted or unsubstituted heterocyclic group include thiophene,
Oxazole, thiazole, thiadiazole, furan,
Heterocycles such as pyrrole, quinoline and pyridine are mentioned.

The naphthalocyanine silicone copolymer represented by the above formula (I) of the present invention can be synthesized using a known method as shown in Scheme 1 [J. Am. Chem. Soc., 10].
6,740 (1984); J. Org. Chem., 28.3379 (1963)].

That is, as shown in Scheme 1, in order to obtain the compound (I), RR'SiCl ₂ is allowed to act on the diol body (6), but as another method, The poly or oligo silicone represented by the formula (I) is reacted with the diol body (6) or the poly or oligo silicone is treated with the dichloro body (5).
It is also possible to obtain

As a method for producing an optical recording medium using the naphthalocyanine polymer dye of the present invention, there is a method of coating or vapor depositing the dye on a transparent substrate. The coating method is 20% by weight or less of a binder resin, preferably 0%. And the pigment 0.05 wt% ~
There is a method in which it is dissolved in a solvent so as to be 20% by weight, preferably 0.5% to 20% by weight, and applied by a spin coater. The vapor deposition method is 10 ^-5 to 10 ^-7 torr, 100 to 300
There is a method of placing a dye on the substrate at ℃.

The substrate may be any optically transparent resin. Examples thereof 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.

The substrate may be surface-treated with a thermosetting resin or an ultraviolet curable resin.

Examples of coating solvents include halogenated hydrocarbons (eg, dichloromethane, chloroform, carbon tetrachloride, tetrachloroethylene, dichlorodifluoroethane, etc.), ethers (eg, tetrahydrofuran, diethyl ether, etc.), ketones (eg, acetone, methyl ethyl ketone, etc.) ), Alcohols (eg, methanol, ethanol, propanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), hydrocarbons (hexane, cyclohexane, octane, benzene, toluene,
Xylene) is preferably used.

〔Example〕

Example-1 Formula (A) Silanol body 1g, dimethyldichlorosilane 5
g, butanol 500 mg and pyridine 20 g were mixed and heated under reflux. After cooling to room temperature, the mixture was discharged into 200 ml of hydrochloric acid and extracted with benzene. Chromatography with silica gel benzene gave 500 mg of the compound (B) of the following formula (n is 4 on average and m is 5 on average) from the benzene layer. Λma in CHCl ₃
x was 775 nm.

1 part by weight of the compound (B) was dissolved in 100 parts by weight of chloroform and applied on an optical disk substrate. The reflectivity of this optical recording medium is 35% at 830 nm, the sensitivity is 8 mW, and 50 d at 830 nm laser.
B, Durability did not change even after reading 1 million times with 0.5 mW reproducing light. Also, the heat resistance is 60 ° C and the humidity is 80%.
There was no change for 100 hours.

Example-2 1 g of the silanol compound of the above formula (A) and polydimethylsiloxane [the following formula (C) (wherein n is 4 on average)] 1 g and 100 mg of iron chloride were heated and reacted in 100 g of dioxane to obtain the same compound as the above formula (B).

Example-3 1 g of the silanol compound of the above formula (A), 5 g of methyl pentyldichlorosilane, 200 mg of ethanol, and 50 g of picoline were mixed and reacted by heating. The product was discharged into 300 ml of hydrochloric acid and extracted with benzene. The benzene layer was separated by silica gel chromatography to obtain 600 mg of the following formula compound (D). n was 6 on average and m was 7 on average.

1 part by weight of the compound (D) was dissolved in 200 parts by weight of carbon tetrachloride and applied on an optical disk substrate. The reflectivity of this optical recording medium is 33% at 830nm, the sensitivity is 8mW, 55dB at 830nm laser.
The stability against reproduction light was 0.5 mW or more than 1 million times, and the stability against drought heat was 60 hours at a temperature of 80% and the duration was 100 hours or more.

Example-4 1 g of tin naphthalocyanine of the following formula (E), 5 g of methylphenyldichlorosilane, octanol After heating and reacting 100 mg with picoline 50 g, the same treatment as in Example-1 was carried out to obtain a compound of the following formula (F). n was 4 on average and m was 6 on average.

Example-5 The same treatment was carried out by using germanium naphthalocyanine of the following formula (G) instead of the compound (A) of Example-1 to obtain 300 mg of the compound (H). n was 6 on average and m was 3 on average. When 2 mg of the compound (H) was dissolved in 1 chloroform and the absorbance was measured, at λmax 773 nm
It was 0.8.

Table 1 shows the characteristics of the compounds obtained in Examples 1, 3, 4, and 5 and the characteristics when these are thinned. As is clear from the table, the various properties of the thin film obtained by spin-coating the compound of the present invention on the glass substrate were better than those of the comparative compound.

(Note-1) Compound of Example-1 of JP-A-61-25886 (Note-2) Compound of Example-4 of JP-A-61-177287 (Note-3) Compound of Example-61 of JP-A-61-232448 Compound (Note-4) The maximum absorption wavelength (λmax, nm) measured with chloroform solvent 2 mg / and the absorbance (abs) at that wavelength are shown.

(Note-5) The reflectance and absorptivity at 830 nm from the substrate surface side of the film spin-coated on a glass substrate at a concentration of 22 g / in a chloroform solvent are shown.

(Note-6) The change in the reflectance of the film formed in (Note-5) after 60 hours at 90 ° C and 90% under heat is 100% (○), 20-50% (△), 50% or more was defined as (x).

(Note-7) Heat resistance and resin compatibility are
When a resin of S) or polymethylmethacrylate (PMMA) was heated and melted and molded, it was visually determined whether the dye was decomposed or dissolved.

Examples 6 to 22 Compounds represented by the following general formula were synthesized as shown in Table 2 and evaluated as an optical recording medium. All of them were evaluated for reflectance, heat resistance, heat resistance, resin compatibility, etc. Good results have been obtained.

[Effect of the invention] The naphthalocyanine polymer obtained by copolymerizing naphthalocyanine and silicone according to the present invention has good compatibility with a resin or a solvent, and
Since the wavelength dependency of the reflectance is small when it is thinned, it has become possible to provide an optical recording medium having excellent characteristics such as reflectance, heat resistance, heat resistance and resin compatibility. .

Claims (2)

[Claims] 1. A formula (I) [In the formula (I), Met is Si (IV), Sn (IV), Ge (I
V) and Ti (IV), and Y ¹ , Y ² , Y ³ and Y ⁴ are each independently an alkyl group, an aryl group, an aralkyl group, an amino group, an alkylamino group, an arylamino group, a hydroxy group or an alkoxy group. , An aryloxy group, an alkylthio group, an arylthio group or a heterocyclic group (each group may have a substituent), R and R ′ are each independently an alkyl group,
Represents an aryl group, P, Q, R and S are each independently 0,
Represents an integer of 1, 2, 3, 4, 5, and 6, and n and m each independently represent an integer of 1 to 30. ] The naphthalocyanine polymer shown by these. 2. An optical recording medium comprising a recording layer containing the naphthalocyanine polymer represented by the formula (I) according to claim 1.