JPS60184887A - Optical recording medium and recording method thereof - Google Patents

Abstract

PURPOSE:To enhance recording sensitivity, S/N and thermal stability and reduce deterioration on reproduction, by a method wherein a recording layer comprising a phthalocyanine polymer obtained by polymerizing or cross-linking two or more moleculars of phthalocyanine having a vinyl group or a composition comprising the polymer is provided on a base. CONSTITUTION:The recording layer formed from a phthalocyanine polymer obtained by cross-linking two or more molecules of phthalocyanine having a vinyl group or a composition comprising the polymer is provided on the base to obtain an optical recording medium. The phthalocyanine polymer is preferably a homopolymer or copolymer of one or more phthalocyanine coloring matters having a vinyl groups or a copolymer of one or more phthalocyanine coloring matters with one or more comonomers having one or more vinyl groups or the like. The recording medium is irradiated with writing light pulsewise to change the orientation or association state of the phthalocyanine molecules at a recorded part, thereby forming record dots having a reflectance or a transmittance or absorbance different from that of the surroundings.

Description

DETAILED DESCRIPTION OF THE INVENTION 1. Background of the Invention Technical Field The present invention relates to an optical recording medium, particularly a heat mode optical recording medium and a recording method thereof.

Prior art optical recording media have the characteristic that the recording medium does not deteriorate due to wear since the medium and the writing/reading head are not in contact with each other, and for this reason, research and development of various optical recording media are being carried out.

Among such optical recording media, heat mode optical recording media are being actively developed because they do not require image processing in a darkroom.

This heat mode optical recording medium is an optical recording medium that uses recording light as heat. One example is a heat mode optical recording medium that uses recording light such as a laser to melt or remove a part of the medium to form a pit. There is a pit-forming type in which writing is performed by forming small holes, information is recorded based on this focus, and the pits are detected during readout and read out.

Until now, most of these pit-forming type media, especially those using a semiconductor laser as a light source that can make the device smaller, have a recording layer made of a material mainly composed of Te.

However, in recent years, because Te-based materials are harmful, and there is a need to increase sensitivity and reduce manufacturing costs, organic materials, mainly dyes, are being used instead of Te-based materials. There are an increasing number of proposals and reports on media using recording layers.

For example, for He-Ne lasers, squarylium dye [JP-A-5FL-48221-V] is used.

B.Jipson and C.R.Jones, J.
Vac, Sci, Tech-nol, 1B (1
) 105 (1981)) and metal phthalocyanine dyes (JP-A-57-82094, JP-A-57-82095).
There are some that use the following.

There is also an example of using metal phthalocyanine dyes for semiconductor lasers (Japanese Patent Laid-Open No. 5El-88795).

All of these have a recording layer formed into a thin film by adhering a dye, and there is no major difference from the Te type in terms of medium production.

However, the reflection of a dye-deposited film against a laser = +2 is generally small, and the current normal method of obtaining a readout signal by changing (reducing) the reflected light due to pits cannot obtain a large S/N ratio. I can't.

In addition, if a transparent substrate having 11" recording layers is integrated with the recording layer so as to face each other and has a so-called air sand inch structure, and Jt writing and reading are performed through the substrate, Although it is advantageous in that the recording layer can be protected without lowering the writing sensitivity and the recording density can be increased, such a recording/reproducing method is also not possible with a dye-deposited film.

This is because a normal transparent resin substrate has a refractive index of a certain value (1.5 for polymethyl methacrylate).
In addition, the reflectance of one surface is relatively high (4%), and the reflectance through the substrate of the recording layer is about 60% or less for polymethyl methacrylate, for example, so it is difficult to detect a recording layer that shows only a low reflectance. Because you can't.

In order to improve the readout S/N ratio of a recording layer made of a dye-deposited film, a thin reflective film such as A-type is usually interposed between the substrate and the recording layer.

In this case, the vapor-deposited reflective film is used to partially increase the reflectance and improve the S/N ratio, and in some cases, the reflective film is exposed due to focus formation and the reflectance increases, or in some cases, the reflective film increases the reflectance. Although the film is removed to reduce the reflectance, it goes without saying that recording and reproduction cannot be performed through the substrate.

Similarly, JP-A-55L181B! No. 30 includes IR-1
32 dye (manufactured by Kodak) and polyvinyl acetate.
'-diethyl-2,2'-trivalent lupocyanine iotite and nitrocellulose;
Y, Law, et al, Appl, Phys.
.

Lett, 39 (9) 718 (1981), coats a recording layer made of a dye and a resin, such as a recording layer made of 3,3'-diethyl-12-acetylthiatetracarbocyacon and polyvinyl acetate. Media established by law are disclosed.

However, these cases also have the same drawback as the dye-deposited film in that a reflection IIN is required between the substrate and the recording layer, and recording and reproduction cannot be performed from the back side of the substrate.

In this way, recording and reproduction through the substrate is possible,
In order to realize a medium having a recording layer made of an organic material that is compatible with a medium having a recording layer made of a Te-based material, the organic material itself needs to exhibit a high reflectance.

However, conventionally, there are very few examples of a single layer of organic material exhibiting high reflectance without laminating a reflective layer.

It has been reported that a vapor-deposited film of vanadyl phthalocyanine exhibits a slightly high reflectance (P, Kimits, etal, AP
pl, Phys, Part A 213 (2)
101 (1981), JP-A-55-97033], but the writing sensitivity is low, probably due to the high sublimation temperature.

It has also been reported that cyanine dyes and merocyanine dyes such as thiazole and quinoline dyes are used [Yamaki et al., 27th
Proceedings of the Japan Society of Applied Physics 1p-F-9 (1980))
A proposal based on this was published in JP-A-58-112.
No. 790, these dyes have low solubility in solvents, tend to crystallize, and are extremely unstable against readout light, causing immediate decolorization, especially when applied as a coating film. It cannot be put to practical use.

In view of these circumstances, the present inventors first developed an indolenine-based cyanine dye that has high solubility in solvents, little crystallization, is thermally stable, and has high paint film reflectance. It is proposed to be used as a single layer film (patent application filed in 1973).
No. 7-134397, No. 57-134170).

In addition, long-chain alkyl groups can be introduced into the molecules of other cyanine dyes such as in-1ζrenine, thiazole, quinoline, and selenazole to improve solubility and prevent crystallization. (Japanese Patent Application No. 57-182588, Patent Application No. 57-17777f, etc.).

Furthermore, it has improved photostability, especially decolorization by readout light (
We have proposed adding a quencher to cyanine dyes in order to prevent regeneration and deterioration (Japanese patent application No. 57-I).
No. H832, No. 57-188048sg).

However, each of these media is desired to have even better performance in terms of recording sensitivity and IF raw S/N ratio.

II. OBJECTS OF THE INVENTION An object of the present invention is to improve the recording method of an optical recording medium using an organic coating film as the recording layer, to improve the recording sensitivity and the reproduction S/N ratio, and to improve the recording sensitivity and reproduction S/N ratio. The purpose is to reduce regeneration deterioration and improve thermal stability.

These objects are achieved by the present invention.

That is, the first invention is an optical recording medium having, on a substrate, a recording layer made of a phthalocyanine polymer formed by crosslinking two or more molecules of phthalocyanine having a vinyl group, or a composition thereof.

Further, the second invention provides a method of pulsed writing light on an optical recording medium having a recording layer on a substrate made of a 2-thalocyanine polymer formed by crosslinking 2 molecular weight of phthalocyanine having a vinyl group, or a composition thereof. A recording method for an optical recording medium, characterized in that recording is performed by irradiating the recording area to change the orientation or association state of phthalocyanine molecules in the recording area to form a recording point with a different reflectance or transmission/absorption -V from the surrounding area. be.

Further, the third invention provides two or more molecules of phthalocyanine containing (vinyl), (i4),
An optical recording medium having a recording layer made of a crosslinked phthalocyanine polymer or a composition thereof as a substrate is irradiated with writing light in a pulsed manner to form four parts on the recording layer, thereby forming recording points. This is a recording method for an optical recording medium, which is characterized in that recording is performed using the following methods.

■Specific 4vl construction of invention Hereinafter, the cooperative structure of the present invention will be explained in detail.

The recording layer of the optical recording medium in the present invention is made of a phthalocyanine polymer or a composition thereof obtained by polymerizing or crosslinking two or more molecules of phthalocyanine having a vinyl group.

In this case, the phthalocyanine polymer refers to one or two types of phthalocyanine polymers.
It refers to a polymer of phthalocyanine dye having two or more molecules of phthalocyanine dye having one or more vinyl groups, or a copolymer of a phthalocyanine dye having vinyl groups and other components.

Among these phthalocyanine polymers, one or two phthalocyanine dyes having a vinyl group are used.
A homopolymer or copolymer of more than one species, one or more phthalocyanine dyes having a vinyl group, and one or two copolymer components having one or more vinyl groups, etc. It is preferable that it is a copolymer with "species";

The vinyl phthalocyanine to be used is represented by the following formula:

Pc-←X)n In this case, X is a vinyl group-containing group, especially -L
-CR=CH2 is preferred.

In this case, R is water or a lower alkyl group.

Moreover, L is a divalent linking group.

The divalent linking group is -COO-.

-0CO-, -CONH-, -NHCO-.

-O-, -502-, -502NH-.

Preferably, it is NH302-, an alkylene group, a phenylene group, or a combination thereof.

In this case, the end of L on the vinyl X side preferably has 0CO- and is acryloyl or methacryloyl.

Further, n is an integer less than or equal to l and 1-, and may generally be any integer from l to 8, but is usually 2.4 or 8.

Pc represents a monovalent or more monovalent residue of phthalocyanine, and the vinyl-containing group represented by X is bonded to the benzene ring forming the phthalocyanine ring.

In this case, the vinyl-containing group is bonded to any position on the benzene ring of the phthalocyanine, but usually from the 3-position to the 4-position.
It is connected to the position.

Therefore, when n=2, the bonding position of the vinyl-containing group is 3.
3'-13, 4'-13, 3''-13, 4''-14,4
'-, and is a mixture of these isomers. - Also, when n=4, 3, 3', 3", 3""
-, and when n=8, 3, 4.3', 4', 3'',
Mainly 4'', 3'', and 4''.

Furthermore, there are no particular restrictions on the central atom of phthalocyanine, including Fe, Cu, Co, Ni, V, Pb, etc.
, Si, Ge, Sn, Ai.

Ru, T i , Z n , M g , M n , V
O.

A9. CM, I nBr, GaC text (Cu2
).

In addition to InBr (Br), I2 is also 11-functional.

In this case, one or two other ligands may be further coordinated to the heptad of the phthalocyanine ring.

Note that other substituted nors are usually not bound to the Pc phthalocyanine residue, but a substituted nor of a carboxy group, a sulfo group, or an amino group h9 may be bound to the Hensen ring of Pc in particular.

Next, examples of phthalocyanine having a vinyl group will be given.

In addition, in F, Mt represents the central total diagonal element of phthalocyanine or hydrogen hydride.

+6 CO-COO-C2H, 1-0fll C(CH
3) =CH2217Co -COO-C2H4-OC
OC(CH3) =CH2418Co -c(a)-〇2Hfl-0 Kasumi G(1;I3) =CH28[4C
, u −0−C4HB −coo C(CH3) =C
)12 420 Cu-CC)L':J-C3H6
-0CO-c(CH3) =C)12 221 Fe
, -CONH-02)+4-Nil O] -C(C
H3) =CH2422N i -C1il-CH2(
> -C[Il-CH=CH21623In Br
-C1l] -C2H4C) -CCD -C:H=C
H224VO-CCX3-C2H4-000-C(CH
3) =GHz 825 Co-CONH-C2H4
-NHCO<5CQ:1=CH=CI-12, 5261
nI -Coo -C3H6-0QI -C(CH3)
=CH27271nBr(Br)-G(XJ-C1
7H24-oco-C (C:H3J=CH2428Ti
O-C(Xl-C3H16-0CII-CH=CH
2929Ga1l ((42) -CONH-C/!H
4'-0111<>CI2-OCO-C(CH3) =
CI2830 I2-NHCO-C3Hb'-CO
N+-1-C(CH2) =CI241 Co-1,
:Of-'C2H4-0COC(CH3) = CH2
42Co-Q]+3;2H4-0COI:(CH31
= CH2', 83Co-+)XC2H4-t
)CoC(CH3+ = lH224Fe, -
cf]0c2H,,1-1-ICOC(CH3) =
CH225'Fe -CIICC2H4-0COC: (
C1+3)=CH246Fe-COOc2)1
4-OCOC; (CH3) = C1-1287Co
-CclII::2H4-0CI3 CH=CH228
CO-CH=CH2-1cOCH=CH249Co -
C:lXC2H4-0COCH=CH28IQ Ni
-C5JO-C2H4-1)CQC(CL3)=01
2 2It Ni -J)IQ -C2H4-(1cO
c(CI3) = C1+2 412 Ni'
1110 02H4-Of;QC(CH3)=CI2
"13Cu -coo-C)12-CH(C)13.1
-[C0C(C)I'3.1 = C1(2214Cu
-[110-CH2-(El(C1(3) -0CO
C(CH3) -CI2 415 Cu -+I)O-
CH2-IL')l(C1-13')-0COC(C
H3) = CH28 Such a phthalocyanine compound is synthesized as follows.

First, there are usually n pieces in the benzene ring, usually 2°4 to 8
Synthesize a phthalocyanine with ( ) carboxy groups.

These synthesis methods are known; for example, n-2 is P2O3, n=
4 is Makromol, Chem.

182 2429-2438 (1981), n=8,
Makromol, Chem, 18'l 5 6 5
(1980).

Alternatively, according to the Hatake method, and troxino 1 (, sulfono 1
B9. Synthesize a phthalocyanine with (functionality), (.

To these, CH2=C-L-Y (Replace L and R as above.

Y HaOH, N H2, COOHQj] functional group. ) and heat to carry out the reaction.

After re-transferring, centrifuging and adding water to the L clear solution to remove the sediment.
The phthalocyanine compound obtained in this way has an electronic spectrum almost identical to that of the phthalocyanine itself.・It is.

In addition, in the infrared absorption spectrum, 1720 cm” 1i
It has a ν of about 1610-1650 cm-' with C=O degrees.

C=C As for the melting point, it is generally thermally decomposed at 170 to 200°C.

A specific synthesis example is shown in, for example, Patent Application No. 111 of March 1980, 21J (.j).

These vinyl group-containing phthalocyanines are usually
After forming a single layer, it is polymerized or crosslinked by active width radiation such as ultraviolet radiation, electric R-rays, and X-rays.

In this case, the phthalocyanine having a vinyl group may be used alone or may be cured in combination with another compound capable of curing with the active width Q4 line.

Examples of compounds (polymers, oligomers, monomers) capable of curing + SF using active width lines that can be particularly preferably used in the present invention include those listed in F.

1. Monomers or oligomers 1. l rJj Functional monomers Examples include acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, cyclohexyl acrylate-1, and dimethylaminoethyl methacrylate!・, benzyl acrylate, calhitol acrylate I., 2-ethylhexyl acrylate I., 2
-Ethylhexyl methacrylate-1, lauryl methacrylate-1, 2-hydroxyethyl methacrylate-1, 2-
Hydroxyethyl methacrylate 5-1, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate-1, chrycidyl methacrylate-1, acrylamide, methacrylamide, N-methylolacrylamide,
N-cyase I-acrylamide, N.

N'-methylolacrylamide, styrene, acrylonitrile, vinyl acetate-1., N-vinylpyrrolidone, phenol ethylene oxide additive acrylate, dicyclopentenyloxyethyl acrylate-1., etc.

l 2 Polyfunctional acrylic monomers or oligomers include ethylene glycol cyacrylate, thiethylene glycol diacrylate-1, triethylene glycol diacrylate, polyethylene glycol cyacrylate, polyethylene glycol dimethacrylate: Polypropylene〉'Glycol cyacrylate, polypropylene glycol dimethacrylate-1, butylene glycol dimethacrylate-1, butylene glycol dimethacrylate I, neopentyl glycol diacrylate;, neopentyl glycol dimethacrylate, 1.4-butanediol diacrylate-1., 1.6-hexanethiol diacrylate, 1.6-hexanethiol dimethacrylate, pentaerythritol diacrylate-1., pentaerythritol triacrylate trillade, trimethylol Propane trimethacrylic I
・, cyacrylate with bisphenol S ethylene oxide IS+1, diacrylate-1 with bisphenol A ethylene oxide, diacrylate-1 with tris(2-hydroxyethyl) isocyanurate, ;・Lis(2-7) chloroyloxyethyl) incyanurate, etc.

1.3 Examples of allylic polyfunctional monomers include sialyl phthara-1 and sialyl isophthara.
1., sialylmalea-1., diallylchlorenta I
・, diallyl adiper 1・, diallyl diglycolate,
triallyl cyanuryl-1., diethylene glycol hisallyl carphonate, etc.

1.4 Ring-opened gold-based monomers, such as cricidyl cinnamer I, epoxy of oxychalcone, and tA 4-mer.

1.5 Urethane (reacrylic ester 1.6 Unsaturated ester of polyhydric carboxylic acid 1.7 Unsaturated amide 1 Monomers having glycisine groups 11 Diasonium salts 1.12 O-quinone azides, such as sulfonic acid esters of 0-naphthoquinone diazide.

1.13 Others, such as dihydroxychalcone, dipanylaracetin, dipanylarcyclopentanone, etc.

x, +a feeling: Vinyl monomer with l^ l) Cinnamoyl type For example, the following CH2=CH4f:>o-co-cH=co-c>C
H2=CH0C)I2CH20-GO-CH=CH<>
CH2=CH(100(J12GH20-GO-CH=
CI+<3CH2=CHC00CH(OH)CH2o-
co-co=cH<>CH2=CH<3- [8-C:
H-COO)ICH2=CH-C>C)1=C(000
)1) COOCH2=CII 0(lH=c, (ON)
GOOHCH2'=CH'! ＞CH20-GO-CH
=CH<>2) Cinnamylidene series such as the following CH2=CH-Q-0-GO-CH=CH-CH=CH
-QCH2=CH0(J21J2 o-co-cn='
co-cH=co03) Furyl acryloyl-based examples include those listed in C 4) Coumarins, such as those listed in C 5) Pyrone systems, such as those listed in F 6) Benzalacetophenone systems, such as those listed in C CH2=CH0CH2CH20<-> GO-CH=C
H<>C/)I2-, C: (,CH3)coo<>
CH=CHcoOC)+2 =C(CH3)COOCH
2G) 12 oco-<> CH==cH-co <> 7) An I-helix system, e.g. the following 8) Stilbene system, e.g. the following CH2=CHC0O-Q-CH=CH-Q9) α-phenylmaleimide For example, the following system (H=C(CH)COOCHCH(CH)OCO<l>
N32 3 2 3 C)12=G(CH3)CON)Ia-5O2N3CH
2=C)I<> 5O2N3 CH2,=C)IOc)12(H,,N311) Unsaturated system such as the following (J12 =CHC00GH2C,H= CH2CH2
= CH(> CH2GH= CH2CH2=(JOC
82CH20-GO-CH=CH212) Benzophenones such as the following CH2= C) ICONH<> GO-QC112=C
(CH3)000C112(,H(Oll)CI+20
- Go<>000 13) Benzoin series e.g. the following 14) l, 3-dioxolane series e.g. the following +5) dithiocarbamate series e.g. the following CH2=CH-5-C9=NR 16) Azadioxabicyclo Systems such as the following 17) Spiropyran systems such as the following 2, polymers or prepolymers Chemically bonded with the following photosensitive groups (and/or various photosensitive groups exemplified in the monomers).

Examples of polymers include various epoxy resins, polyurethanes, polyamides, polyacrylic butyunsaturated polyesters, polyvinyl alcohol, silicone resins, maleinyl nitrides, cellulose derivatives, vinyl sulfate-vinyl acetate esters, resinous polyol acrylics, etc. Le-I-et al.

In addition to the above, photosensitive groups include olefin, cinnamoyl, cinnamylideneacetyl, Handelace!・Phenone (chalcone), styrylpyridine, α-phenylmaleimide, phenyl azide, sulfonylazide, carbonylune; ・, diazo, 0-quinone diazil' (diasooyasi 1:), furyl acryloyl, kujarino, pyrone, an1-hracene, pentuphenone , henzin, stilbene, dithiocarbamate, xantart, I;2. ．． 3
-thiasiasol, cyclopropene, aza-dioxabicyclo, etc.

Furthermore, cyclized rubber, polycon (allyl isocyanate or allyl alcohol is reactively bonded to the end of polyurethane obtained by reaction of polyether glycol and tolylene diisocyanate, and allyl groups are introduced therein) are also useful.

These are usually 80 wt% or less based on phthalocyanine.

Furthermore, a photosensitive crosslinking agent can also be added.

Rack 4 (addition j, 1. of 4 cuts is 80w of phthalocyanine
It is set to be t% or less, particularly about 0.1 to 80wt%.

There are no particular restrictions on the crosslinking agent to be used, but those listed below are preferred.

1. An example of a dichromate is a compound of Φchromate with a water-soluble polymeric compound such as gelatin, glue, egg white, gum arabic, or polyvinyl alcohol. 2. An example of a dichromate is 4. .4'-Diazi IS stilbene, 4.4
- Compounds such as diazidochalcone, e.g., pentaerythritol tetrakis (β-mercaptopropione-1-), etc. - Compounds such as silica, for example, initiators and sensitizers can also be added.

The initiator and sensitizer additives are o.c. of phthalocyanine.
It is assumed to be approximately o'ol to lOwt%.

There are no particular restrictions on the initiator and sensitizer used, but those listed below are preferred.

■． Pentwin ethers such as inbutylhentwin ether, isopropylhentwin ether, pentwin ethyl ether, pentwin methyl ether, etc.2, α-Azyloxime esters such as 1-phenyl-1,2-pronoquinone N-2
= (0-ethoxycarbonyl)oxy L, etc. 3, Benzyl ketal systems, such as 2,2-dimethoxy-2-phenylacetophenone, ruphenyl ketone, etc. 4, Acetophenone derivative systems, such as jetoxyacetophenone, 2-hy1ζroxy2・Methyl-1#phenylbronogunacetone, etc. 5. Examples of ketone (ketone-amine) systems include hensifenone, chlorothioxanthone, 2-chlorothioxanthone, inpropylthioxanthone, 2-methylthioxanthone, chlorine-substituted Hydrocarbons such as benzophenone, halogen-substituted alkyl-aryl ketone, 6, naphthalene, an-I-racene, phenan-I-lene, chrysene, etc., nitrobenzene, p-dinitrobenzene, 1, 3
．． 5-trinitrobenzene, m-nitroaniline, 2.4-sinitroaniline picramide, 2-chloro-4-nitroaniline, 216-sinitroaniline phenol, P-nitroaniline, 2.4 -dinitrophenol, 2, 4.
8-trinitrophenol, phenol++ compound 8, henzaldehyde, 8-anthraaldehyde, acetophenone, benzophenone, dipenzalacet, benzyl, p,p'-diaminopentsuphenone,
ρ． p'-dimethylaminohensophenone, p,p'
-tetramethyldiaminobenzophenone (Michlerke i)
·hmm)'. Ketone series f 9 Bendiquinone, l,2-naphthoquinone, l,4-naphthoquinone, anthraquinone,
1.2-Benzanthraquinone'''9 Quinone series IO. Anthrone, l,9-benzanthrone, 6-
Phenyl-I,9-benzanthrone, 3-phenyl-
1.9-henzoanthrone, 2-keto-3-aza-1.

9-benzanthrone, 3-methyl-1,3-diaza-
1,9-Benzanthrone and other anion compounds 11, azobisisobutyronitrile and other ann compounds 12, mercaptans, disulfides and other organic sulfur compounds 13, various halogen compounds, and various oligomers and polymers. Various leveling agents such as silicone acrylic, water repellents, oil repellents, light stabilizers, plasticizers, surfactants, antistatic agents, various reaction catalysts,
Various pigments, fillers, thermal polymerization inhibitors, reducing agents, etc. may be added.

Phthalocyanines or compositions thereof that can be cured by such actinic radiation, especially ultraviolet rays, electron beams, and X-rays,
If necessary, it is dissolved in a solvent, coated on a substrate, and then cured using active radiation.

In this case, the solvent to be used is a chemical compound (for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.).

) 54, % group systems (e.g. toluene, xylene, etc.), non-rogen systems (e.g. dichloroethane, 1.1 nocrene, etc.), alcohol systems (e.g. methanol, ethanol, propatool, methyl cellosolve, ethyl cellosolve, etc.)
, ester type (e.g. Ii butylacetate, ethyl acetate, carpitol acetate-1, butyl carpitol acetate-1)
4), hydrogen '9 has 11 functions.

The concentration of the phthalocyanine or its composition that can be cured by active +1 radiation is less than 'lOO%, particularly about 20 to 100%.

As the '41+i force method, a spinner method, a ditube method, a graphia coat method, a spray method, etc. may be used.

The wavelength of the ultraviolet light used for curing is l: 200 to 40.
It is considered as a melon with a diameter of about 0 nm. Also, Kogyoden is a lamp powered by human power.
W/cm-I Kw/am is made to become a melon.

Further, the curing step 1111 is performed for 1 ltsec to 1 minute, and the atmosphere during the curing process may be in air, inert scum, vacuum, or the like.

If necessary, the solvent is removed by applying heat at a temperature of about 25 to 150°C before curing, or preferably before curing.

(The line is for acceleration speed, o, t-100
0keV, ! lf ma L < is 0, 5~31) 0
keV t7) is preferred.

t Ta, +Ij, r-kkA Teru Q4' Qi: I
L, d'm O, OL ~l 00, Krad41
+i Ii.

When the curing atmosphere is an inert gas atmosphere such as nitrogen, argon, heliud, or a mixed gas thereof, the effects of the present invention become even more excellent.

Note that there are no restrictions on the F-ray accelerator used.

Furthermore, Xvj can also be used.

In addition, it is preferable that about 1 to 10 million molecules of phthalocyanine dye, particularly about 3 to 1 million molecules, of the phthalocyanine dye are contained in the phthalocyanine polymer after crosslinking.

Although the recording layer of the medium of the present invention is made of such a phthalocyanine polymer, the recording layer may contain other resins separately. At this time, the coating property is
:: L, Recording sensitivity, readout S/N ratio, etc. are not good.
- to do.

Examples of such resins include, for example, Japanese Patent Application No. 58-152
Those described in No. 29 etc. are suitable.

The resin is 2% by weight based on the phthalocyanine polymer.
Contains about 0% or less.

Further, a quencher can also be contained in the recording layer. This reduces ILF biodegradation.

The quencher to be used is disclosed in Japanese Patent Application No. 58-20394.
5'i+ etc. are suitable.

To form such a recording layer, it is generally necessary to apply the coating according to the Hatake method.

The thickness of the recording layer is usually about 0.02 to 10 m.

There is no particular restriction on the material of the substrate on which such a recording layer is formed, and it may be made of any of various resins, glass, ceramics, metals, etc., but it must be substantially transparent to writing light and reading light. Preferably.

Further, its shape may be a tape, a drum, a belt, etc. depending on the intended use.

Note that the body usually has a groove for trunking.

In addition, ) 1 (Resin materials for the body include polymethyl methacrylate 1, acrylic resin, epoxy resin, polycarbonate resin, polysulfone resin, polyether sulfone, methylpentene polymer': 9, groove ζ
A substrate without scratches or grooves is preferred.

These) 1 (the body has solvent resistance, wettability, 1 surface tension,
The substrate 2 can also be coated with a primer in order to improve the thermal conductivity.

Examples of primers include titanium-based, silane-based, -
Aluminum-based coupling agents, various photosensitive resins, etc. can be used.

Further, in order to control the orientation, an orientation treatment layer and an orientation control layer may be provided.

Further, the recording layer may be provided with various types of protective layers, half-mirror layers, etc., if necessary. Further, a reflective layer may be provided on the edge of the recording layer.

Furthermore, the substrate may be subjected to various treatments, such as corona treatment.

The medium of the present invention may have the above-mentioned recording layer on one side of the body, or may have recording layers on both sides.

In addition, two substrates with recording layers coated on them are used, and the recording layers are placed facing each other with a predetermined gap between them, and they are sealed to prevent dust and scratches. You can also prevent it from sticking.

Furthermore, since the recording points have substantially no irregularities, it is possible to coat the recording layer with resin or to adhere another resin plate to the recording layer. and,
With such an electrodeposited structure, the media can be made more compact, the thickness of the media can be reduced, and the reliability of the media can also be improved.

IV. Specific Effects of the Invention The medium of the present invention utilizes recording light in a pulsed manner while traveling or rotating. At this time, the phthalocyanine polymer in the recording layer generates heat and is immediately rapidly cooled, resulting in a change in the orientation or association state of the phthalocyanines in the phthalocyanine polymer, forming a recording point that has a different reflectance or transmittance from its surroundings.

In this case, the recording point is usually recorded as a point whose reflectance or absorption rate is different from that of the surrounding area.

The recording points have substantially no unevenness.

The recording points formed in this manner are read out by detecting the movement 11 or rotation of the medium and the reflected light or transmitted light of the readout light, especially the reflected light.

In this case, recording and reading may be performed from the substrate side or from the recording layer side, but it is preferable to perform the recording and reading through the substrate.

Then, the recording points formed in the II recording layer are heated and slowly cooled using light or heat to restore the original orientation or association state of the phthalocyanine (1) and erase the recording points by making the reflectance the same as the surroundings, It is also possible to rewrite.

Note that a semiconductor laser, He--Ne laser, Ar laser, He--Cd laser, etc. can be used as the recording or reading light.

Alternatively, if the strong electric current of the recording light is made larger than in the above case, the recording point is formed as a focal point that forms a gate to the surroundings.

(2) Specific Effects of the Invention According to the present invention, since recording is not performed using a focus having irregularities unlike conventional recording layers made of organic materials, the recording sensitivity is improved by -1.

Furthermore, the reproduction S/N ratio is also improved.

Since phthalocyanine is used, it has extremely high thermal stability and stability against light.

Furthermore, compactness can be reduced, and the performance and reliability of the system is improved.

In addition, when forming four-part pits, when the light intensity of the recording light is increased by 1, there is a clear threshold of light intensity that determines the sensitivity, and the )/chi 1 from there is large. Since the optical sensitivity is saturated, the effect is that the characteristics are stable against fluctuations in recording light intensity.

■Specific embodiments of the invention Specific examples of the present invention are shown below.

Example 1 An acrylic resin body with a diameter of 30 cm and a thickness of 1.5 mm was used as a nor body.
IJ 0 , 9 rectangular grooves were formed concentrically.

Next, the following composition A was dissolved in 10% dichloroethane,
This solution was spin-coded to a thickness of 0.08 mm, dried, and then irradiated with a high-pressure mercury lamp of 80 W/Cm for 10 seconds to effect crosslinking.

Phthalocyanine, 23-tert-pentaerythritol tetraacrylate initiator, 2-tert-butylanthraquinone,
For comparison, a recording layer containing only FnBr-7 talocyanine was similarly produced.

For each sample prepared in this way, 600
While rotating at rpm, a semiconductor laser (830 nm
) was focused at NA, = 0.517) L/7, and the light focusing unit output was 10 mW), and the pulse Ill tl--; writing sensitivity was measured.

Table 2 shows the sensitivity that allows an ilf raw S/N ratio of 40 dB.

Next, writing was performed with pulse II l 00 n5ec.

As a result, recording points were formed that had no unevenness and had a different reflectance from the surrounding area.

After this, the semiconductor laser readout light of 0.6 mW was applied to the
Irradiate as a 2 μsec li, 3 KHz pulse,
The reflected light was detected and the C/N ratio was measured.

In addition, the reflectance deterioration rate (%
) are also listed in Table 1.

Table 1 The effects of the present invention are clear from the results shown in Table 1.

Example 2 Using the same substrate as in Example 1, the following composition was dissolved in a 1:1 solution of dichloroethane and cyclohexanone, and this solution was spin-coated at 0.09% and dried, followed by 60 W/L.
Crosslinking was carried out by using a cm high pressure mercury lamp for 1 second.

Phthalocyanine disintegration, 14 pentaerythritol tetraacrylate 2-ter
t-Butylanthraquinone Also, for comparison, a medium with a Cu-phthalocyanine layer was prepared.

For each sample prepared in this way, 900
While rotating at rpm, apply He-Ne from the back side of the substrate.
Focus the laser to 1 φ, focusing oil output 10 + oW),
Pulse II OOn5ect writing was performed.

As a result, in samples 8 to 13 of the present invention, substantially four recording points were formed.

After this, the same measurements as in Example 1 were performed.

The results are shown in Table 2.

Table 2 From the results shown in Table 2, the effects of the present invention are clear.

Claims (4)

[Claims] (1) An optical recording medium characterized in that the substrate F has a recording layer made of a phthalocyanine polymer obtained by polymerizing or crosslinking two or more molecules of phthalocyanine having a vinyl group, or a composition thereof. (2) irradiating an optical recording medium with a recording layer made of a phthalocyanine polymer obtained by polymerizing or crosslinking two or more molecules of phthalocyanine having a hinyl group or a composition thereof as a base with writing light in a pulsed manner; A recording method for an optical recording medium, characterized in that recording is performed by changing the orientation or association state of phthalocyanine molecules in a recording part to form a recording point having a different reflectance, transmittance, or absorption rate from the surrounding area. (3) The method for recording an optical recording medium according to claim 2, wherein the recording points have substantially no unevenness. (4) A phthalocyanine polymer obtained by polymerizing or crosslinking 2 or more phthalocyanines having a vinyl group;
Alternatively, an optical recording medium having a recording layer made of the composition on a substrate is irradiated with writing light in a pulsed manner to form four parts on the recording layer to form recording points and perform recording. Recording method for optical recording media.