JPS63306091A - Optical recording medium - Google Patents

Abstract

PURPOSE:To increase maximum absorption wavelength, to enhance reflectivity, to suitably set the reversal of a writing sensitivity and to provide durability in the performance by employing both phthalocyanin compound and amine compound as a thin film on a substrate. CONSTITUTION:For example, a thin organic film having phthalocyanin compound and amine compound as main ingredients represented by a formula (where 1-16 are peripheral carbon atom position, K is substituted group, s, t, p, q are integer numbers of 0-4, K is a bonding group in which two or more of peripheral carbon atoms at positions 1, 4, 5, 8, 9, 12, 13 and 16 are represented by P, any of-NH2,-NO2-,-CN,-SO3Y,-SO2X.-X, and 3-8 of the carbon atoms 1-16 is a group represented by (Z)rR. However, Y is hydrogen or metal atom, X is halogen atom, Z is-CH2-,-CONH-,-COO-, R is alkyl group or aryl group of normal chain, branch having 4-18 of carbons, M is metal or metal oxide, hydrogen and metal halogen. r is a number of 0 or 1) is formed on a substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Wf) The present invention relates to an optical recording medium, particularly an optical recording medium having an organic recording layer for a semiconductor laser having absorption in the near-infrared region.

(Prior Art) In recent years, the development of semiconductor lasers has been remarkable, and small and stable oscillators have become available at low cost and have begun to be used as light sources for various recording devices. However, the wavelength of these 11 conductor lasers is limited to relatively long wavelengths, and 11 conductor lasers capable of oscillating short wavelength light have problems in terms of lifespan, output, etc.

Therefore, as a recording medium for conductive lasers, it is essential to use a material that absorbs in the near-infrared region as a thin film layer, and materials with a maximum absorption wavelength of 750p or less are unsuitable.

Conventionally, as a recording medium of this kind, there is one in which a thin film formed on a substrate is irradiated with laser light to form bits, and recorded information is read out based on the difference in reflectance between the bits and non-bit areas.

The groove structure of the recording layer for this recording and LRR reproduction (reading) is two or more layers consisting of a recording thin film forming layer and a reflective film!
-Although there are other possibilities, it is advantageous to have only the recording thin film layer having both of the above functions. In the case of a single-layer film for this recording thin film layer, it is necessary that the material of the recording thin film layer itself has a high reflectance in order to obtain a high S/N ratio. As this type of recording medium, inorganic ones using low melting point metals such as Te or alloys thereof are known, and organic ones using cyanine dyes and phthalocyanine compounds are known.

(Problems to be solved by the invention) Inorganic optical recording media using Te-based alloys have relatively high sensitivity, but they have problems with 7B properties, and the film formation method uses speckling, etc., so equipment costs etc. It has the drawbacks of high productivity and low productivity. Organic thin-film optical recording media using cyanine dyes have the advantage of being able to be produced using relatively inexpensive methods such as the spin-coding method, but their performance, such as storage stability (durability), is insufficient. The current situation is that it has not reached its potential. Furthermore, in the case of naphthoquinone and anthraquinone, they have poor solubility in solvents and have storage stability problems such as the formation of agglomerated structures. Furthermore, phthalocyanine compounds are also unsatisfactory due to their solvent solubility, semiconductor laser matching properties, and crystal changes during storage.

(Means for solving the problem) For recording and reproduction of optical recording media that are highly sensitive to light in the near-infrared region, have high solvent solubility, high reflectance, are free from core, and have excellent durability. In order to provide a thin film material and thereby an excellent optical recording medium, the present invention was arrived at as a result of intensive studies.

That is, the present invention is an optical recording medium characterized by forming an organic thin film containing a phthalocyanine compound and an amine compound as L components on a substrate.

As the phthalocyanine compound in the present invention, conventionally known phthalocyanine compounds, particularly phthalocyanine compounds into which various substituents have been introduced for solubilization, can be used. For example, there are phthalocyanine compounds described in JP-A No. 60-209583 and JP-A No. 61-154888.

Particularly preferably applied phthalocyanine compounds to the present invention include compounds represented by the following general formula (I) and compounds represented by the following general formula (II).

The following margins (in the formula, 1 to 16 indicate the surrounding carbon atom positions, K each indicates a substituent that may be the same or different, Ss j
*1) t Q indicates an integer from 0 to 4, K is 1°4.5
, 8, 9, 12, 13 and 16 positions, two or more of the surrounding carbon atoms are represented by P, and the bonding group is -NH
2,-No. ,-CN.

-5o3y, -5o2x, -x, and 3 to 8 of 1 to 16 peripheral carbon atoms are represented by (Z)rR. However, Y represents hydrogen or a metal atom, X represents a halogen atom, and Z represents -CH2+, -CON
H-, -COO-, R is a straight chain having 4 to 18 carbon atoms,
Indicates a branched alkyl or allyl group. M represents a metal, a metal oxide, hydrogen, or a metal halide. r is a number of 0 or 1. ) (However, n I” n a e m I-ma is 0 to
is an integer of 4 and 1≦m + “m 2”m 3+
m a≦4 and 3≦m *”m2+ln3”m4”
n tan is an integer satisfying 2+H3+n4≦8. Y represents a group bonded to a carbon atom of an organic group via an atom of Group 5 or Group 5 of the periodic table, and X represents (Z)r
Indicates a group represented by R, Zct-CH2-, -CON
Represents either H- or -COO-, R has 4 to 1 carbon atoms
8 straight chain or branched alkyl group, allyl group having 6 to 18 carbon atoms, or substituted allyl, M is hydrogen,
Indicates a metal, metal oxide, or metal halide. r is a number of 0 or 1. ) In the phthalocyanine compound of formula (I), (Z)rR in formula (I) is Z'
-R'-N-R2 is more preferably applied to the present invention.

(However, Z' is -o-, -s-, -so.-1-NR
'-, -NR' Co-, -Coo-.

One or two organic groups selected from -tkO2NR8-
R1 represents one or two of a linear or branched alkyl group having 1 to 18 carbon atoms, a polyoxyalkylene group or arylene group, and a cycloalkylene group having 4 or more carbon atoms; R2゜R3 is one or two of the following: a linear or branched alkyl group having 1 to 18 carbon atoms, an alkenyl group, a polyoxyalkylene group, an aryl group having 6 to 14 carbon atoms, and a cycloalkyl group having 4 or more carbon atoms. In the above, R4 to R8 represent one or more of hydrogen, a straight chain or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group, an acyl λ, and an alkyl succinic acid group. ) Also, at least one of the Z'-R'-N-R2 is R
Preferred are phthalocyanine compounds that form a quaternary ammonium salt with 7E. (However, R7 has 1 to 1 carbon atoms.
18 alkyl group, alkenyl group or carbon number 6-18
is an aryl group or an alkylaryl group, and E is an anion. ) Preferably applied amine compounds in the present invention include amine compounds represented by the following formula (V).

(However, R' + R2 represents a hydrogen-substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, and the aromatic group among the organic groups is an alkyl group or an alkoxy group. , halogen, or hydroxyl group, or may be unsubstituted. -B- is an alkylidene group, -S
-, -5O2- is shown. P represents a number of 1 or 2, m represents a number of 1 or 2, n represents 0, 1 or 2, and S represents a roion. ) Specific examples of these amine compounds include the following.

In the following representations of amine compounds, CH,- is M
e, C2H5- to E t+ n C* H7- to Pr
, t-C4He- is abbreviated as Butn-Co HI3- is abbreviated as Hx. In addition, each compound is given an abbreviation and is referred to by the abbreviation in the Examples. Abbreviations are written in parentheses after each compound.

([(Bu)2NO]2 NON''-(ON(Bu)2
)2) SbFo-(A-0-1) [((Et)2*Q
12 N:○:N9N(Et)2+2)2CQO4-(
A,, -2) ([(Et)2NQ 12 N OO Port 0
N(Et)2)z)BF4- (A,,,-5)[1(
Hx)2N Q 12 N ON”((3N(H
X)2)2)BF4- (A,,-fi)(((Et)
J 012 N Q N”(On(Et)212)CQ
o,t (A,.-8) It has been found that the combined use of a phthalocyanine compound and an amine compound as an organic thin film for a recording medium in the present invention has excellent performance and advantages, and these phthalocyanine compounds are more preferably used. This is a system in which a polymethine compound is further used in combination with an amine compound.

As these polymethine compounds used in the present invention, polymethine compounds represented by the following formulas (III) and (IV) are preferred.

(However, in formula (III), R'9R21R'I
R4 represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, or a heterocyclic group, and W represents a cyclohexene ring, or a condensed ring containing at least one cyclohexene ring or at least one substituted cyclohexene ring. and Q*n is 0 or an integer from 1 to 3, and 0≦(7+n≦5, m indicates the number of O or 1,
X indicates an n ion. ) (However, in formula (IV), n is 0 or 1 to 3
R', R2, and R' may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, and X is a halogen, perhalogen acid, boron tetrafluoride, toluenesulfonic acid, Indicates any alkyl sulfate, A'
1A'' represents a benzene ring or a naphthyl ring, and each ring may be substituted with any one of an alkyl group, an alkoxy group, a hydroxy group, a carboxy group, a halogen, an allyl group, and an alkylcarboxyl group.

) The present invention is an optical recording medium in which a thin film mainly composed of a phthalocyanine compound and an amine compound is formed on a substrate. It has become possible to obtain an optical recording medium that is well-balanced in terms of performance, ease of manufacture, economic efficiency, etc. Stabilizers, lubricants, antistatic agents,
A polymer compound as a binder, other dyes, and sensitizers may be used in combination. The substrate material used in the present invention may be either transparent or opaque to the laser beam used, but when recording is performed using the laser beam from the substrate side,
Must be transparent to laser light. These substrate materials include glass, acrylic resin, methacrylic resin, polyurethane, stell resin, nitrocellulose resin, polyamide resin, polycarbonate resin, polymethylpentene-1 resin, epoxy resin, vinyl chloride resin, polyparaphenylene resin, etc. Can be mentioned. These resins are
They are shaped objects such as sheets, films, disks, etc., and these shaped objects may have an undercoat layer or a layer coated with a specific metal, if necessary.

Hereinafter, the present invention will be explained in more detail with reference to Examples. The characteristics in the examples were measured and evaluated as follows.

Spell > Phthalocyanine compound (polymethine compound if necessary)
Then, an amine compound was mixed in a predetermined ratio, dissolved in dichloroethane to 1.5%, and a thin film of 70 r+m was formed on a glass substrate using a spin coater. This is UV-V
Absorption and reflection spectra were measured with an IS spectrometer (Island 711V21 OA). From this, the maximum absorption wavelength (human max) and the reflectance at 830 nm (R
%) was calculated.

The recording medium obtained in above-f2 was irradiated with an 830 nm semiconductor laser with an optical power of 10 mW and a lens diameter narrowed to one, thereby writing in the concave portions of the tracks.

Next, using the same laser light source (0.2 mW) as read light, the write light pulse width at which the S/N ratio of the reflected light was 50 dB or more was measured, and the reciprocal of the sensitivity was calculated.

After irradiating the recording medium with resistance 2 (resistance 2) or higher at 63° C. for 300 hours using a sunshine carbon arc fade meter, the reflectance and S/N ratio were measured to check for deterioration.

(Example) X-1, Various phthalocyanine compounds, amine compounds, and polymethine compounds shown in Table 2 are mixed at a predetermined ratio, then dissolved in dichloroethane, and coated on a glass substrate with a spin coater to a solid content thickness of 70 mm. A thin film was formed on the inner cloth and various characteristics and performance were evaluated. The results are shown in Table 3. The abbreviations used in compound descriptions are shown below.

Abbreviation of alkyl group Me: methyl group, Et: ethyl group.

Bu: t-butyl group tA+m: t-amyl group.

He: hexyl group, Hp: heptyl group.

Dd Nidodecyl group, Pr: n-propyl group In the table, Pc represents a phthalocyanine compound, A, 9 represents an amine compound, and Pmt represents a polymethine compound, which are indicated by their numbers, and the specifics corresponding to the numbers are , written below the table.

Table-1 Pc-1 Pmt-1 Pmt-2 Table-2 (Effects of the invention) The thin film used as an optical recording medium using the phthalocyanine compound and amine compound of the present invention (further adding a polymethine compound) has a maximum absorption wavelength It was found that the reflectance was large, the reflectance was high, the reciprocal of the aging sensitivity was appropriate, and the durability of these properties was also excellent.

Claims (6)

[Claims] (1) An optical recording medium characterized by forming an organic thin film containing a phthalocyanine compound and an amine compound as main components on a substrate. (2) The optical recording medium according to claim 1, wherein the phthalocyanine compound is a compound represented by the following formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, 1 to 16 indicate the surrounding carbon atom positions, K indicates a substituent that may be the same or different, and s, t, p
, q represents an integer from 0 to 4, K is 1, 4, 5, 8, 9,
A bonding group in which two or more of the surrounding carbon atoms at positions 12, 13, and 16 are represented by P, and the bonding group is -NH_2, -N
O_2, -CN, -SO_3Y, -SO_2X, -X and 3 to 8 of 1 to 16 surrounding carbon atoms
is a group represented by (Z)rR. However, Y represents hydrogen or a metal atom, X represents a halogen atom, Z represents -CH_2-, -CONH-, -COO-, and R represents a straight chain or branched alkyl group having 4 to 18 carbon atoms. Alternatively, M representing an allyl group represents a metal, a metal oxide, hydrogen, or a metal halide. r is a number of 0 or 1. ) (3) The optical recording medium according to claim 1, wherein the phthalocyanine compound is a compound represented by the following formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (However, n_1 to n_4, m_1 to m_4 are integers from 0 to 4, and 1≦m_1+m_2+m_3+m_4
≦4 and 3≦m_1+m_2+m_3+m_4+n
It is an integer satisfying _1+n_2+n_3+n_4≦8. Y represents a group bonded to a carbon atom of an organic group via an atom of group V_b or group VI_b of the periodic table, and X represents (
Z) represents a group represented by rR, Z is -CH_2-, -C
Represents either ONH- or -COO-, R has 4 carbon atoms
~18 straight-chain or branched alkyl group, carbon number 6-18
represents either an allyl group or a substituted allyl, and M represents any one of hydrogen, metal, metal oxide, and metal halide. r is a number of 0 or 1. ) (4) The optical recording medium according to claim 2, which has ▲a mathematical formula, a chemical formula, a table, etc.▼ of the phthalocyanine compound represented by formula (I). (However, Z' is -O-, -S-, -SO_2-, -N
R^4-, -NR^5CO-, -COO-, -SO_2
One or more organic groups selected from NR^6, R^1 is a linear or branched alkylene group having 1 to 18 carbon atoms, a polyoxyalkylene group or an arylene group, or a C4 One or two of the above cycloalkylene groups
R^2 and R^3 are linear or branched alkyl groups having 1 to 18 carbon atoms, alkenyl groups, polyoxyalkylene groups, aryl groups having 6 to 14 carbon atoms, and 4 carbon atoms.
It represents one or more of the above cycloalkyl groups,
R^4 to R^6 represent hydrogen or one or more of a linear or branched alkyl group having 1 to 10 carbon atoms, an alkenyl group, an acyl group, and an alkyl sulfate group. ) (5) The phthalocyanine compound in formula (I) has a mathematical formula, a chemical formula, a table, etc., and at least one of them is a phthalocyanine compound that forms a quaternary ammonium salt with R^7E, Claim 4 The optical recording medium described. (However, R^7 is an alkyl group having 1 to 18 carbon atoms, an alkenyl group, or an aryl group-alkylaryl group having 6 to 18 carbon atoms, and E is an anion.) (6) The optical recording medium according to claim 1, wherein the amine compound is an amine compound represented by the following formula (V). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (However, R^1 and R^2 are hydrogen, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group and A indicates ▲There are mathematical formulas, chemical formulas, tables, etc.▼ The aromatic nucleus of the organic group may be substituted with an alkyl group, an alkoxy group, a halogen, or a hydroxyl group, or may be unsubstituted. -B- is an alkylidene group, -S
-, -SO_2- is shown. p represents a number of 1 or 2, m represents a number of 1 or 2, n represents 0, 1 or 2, and S represents an anion. )